JPH02225581A - Hot-melt adhesive - Google Patents

Abstract

PURPOSE:To improve the adhesion to water-repellent treated cloth by mixing a specific hot melt resin with a silicone diamine wherein both ends of the polysiloxane sheleton have an amino group. CONSTITUTION:100 pts.wt. hot-melt resin selected from the group consisting of polyester(amide) resins and polyamide resins is mixed with 0.05-10 pts.wt., preferably 0.1-5 pts.wt., silicone diamine, preferably of the given formula [wherein R is alkylene such as methylene, ethylene, propylene, butylene, (cyclo) hexylene, phenylene or tolylene; and n is 0 or more] having an average molecular weight of 300-20,000 and amino groups at both ends of the polysiloxane sheleton.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a hot-melt adhesive that can be applied to water-repellent fabrics, which have conventionally been difficult to bond.

In the production of traditional technical clothing, the sewing process occupies a considerable part of the total process. Therefore, adhesive sewing has been adopted as a method for streamlining the sewing process. Adhesive sewing includes adhesive sewing of interlining, adhesive sewing of covering cloth, adhesive sewing of lining, adhesive sewing of ordinary clothing, etc., but adhesive sewing of interlining is particularly important.

Adhesive interlining is made of woven fabric, non-woven fabric, or knitted fabric as a base fabric, and powdered hot melt adhesive is applied to one or both sides of the fabric. Known types include low-density polyethylene, ethylene-vinyl acetate copolymer, and polyvinyl chloride, and permanent adhesive types include polyamide resin 2 polyester resin and polyurethane resin. (“Adhesion Handbook”, published by Nikkan Kogyo Shimbun, July 5, 1980, No. 2)
4th edition, p. 604) JP-A-62-119284 discloses a hot melt adhesive in which powdered polyester is mixed with powdered wax consisting of a mixture of low molecular weight polyethylene and alkylene diamine diacyl. It is shown.

JP-A-51-22732 and JP-A-51-12
No. 5194 discloses a saturated polyesteramide resin containing terephthalic acid and adipic acid as acid components, 1,4-butanediol and ethylene glycol as glycol components, and q-caprolactam or ε-7 minocaproic acid as a third component. It has been shown to be used as a hot melt adhesive to bond fabrics together.

Problems to be Solved by the Invention Among conventionally used hot melt adhesives for textiles, polyester resins, polyesteramide resins, and polyamide resins are superior to other hot melt adhesives in that they have good dry cleaning resistance. However, there are problems in that the resin is easily thermally decomposed during melting and the resin deteriorates in quality under high humidity conditions. (For example, see pages 597-598 of the above-mentioned "Adhesion Handbook.") Also, even if hot melt adhesives based on these polyester resins, polyesteramide resins, and polyamide resins are used, the objects to be bonded may be organic silicon compounds. When the fabric is water-repellent treated with a water repellent such as a water repellent or a fluorine compound, the adhesive strength is extremely low and there is a problem that it cannot be put to practical use.

The present invention was made for the purpose of solving the above-mentioned problems in hot melt adhesives made of polyester resins, polyesteramide resins, or polyamide resins.

Means for Solving the Problems The hot melt adhesive of the present invention comprises polyester resin,
100 parts by weight of at least one hot melt resin (A) selected from the group consisting of polyesteramide resins and polyamide resins, and 0.05 parts by weight of silicone diamine (B) having 7 amino groups at both ends of polysiloxane. ~
It is made by blending 10 parts by weight.

The present invention will be explained in detail below.

<Hot melt tree 11 (A)> As the hot melt tree 1fi (A), polyester resin, polyester amide resin, or polyamide resin is used.

As the polyester resin, polyester consisting of a saturated dicarboxylic acid component and a glycol component is preferably used.

Here, the saturated dicarboxylic acid components include terephthalic acid,
Isophthalic acid, phthalic acid, 2.5-norbornanedicarboxylic acid, 1,4-naphthalic acid, 1.5-naphthalic acid, siphenic acid, 4.4'-oxybenzoic acid, 2.5-
Aromatic dicarboxylic acids such as naphthalene dicarboxylic acid, tetrahydrophthalic anhydride, 2,5-fluoranedicarboxylic acid, Hett's acid, oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, geltaric acid, 2,2-dimethylgeltal Acid, adipic acid, dodecanedicarboxylic acid, pimelic acid, superric acid, azelaic acid, sebacic acid, 1.3
- Non-aromatic dicarboxylic acids such as cyclohexanedicarboxylic acid. Acid anhydrides, lower alkyl esters, and halogen-substituted products of the above-mentioned saturated dicarboxylic acids can also be used. Among the above, it is preferable to use at least a portion of terephthalic acid and/or isophthalic acid from the viewpoint of physical property balance.

Glycol components include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1.2- or 1.3-propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, 1.3-11.4-
or 2.3-butylene gellicol, 1,5-bentanediol, 1.6-hexanediol, 2-ethyl-1
, 3-hexanediol, 2,2,4-trimethyl-1
, 3-bentanediol, 1,4-cyclohexane dimetatool, polytetramethylene glycol, bisphenol A, hydrogenated bisphenol 8, and the like. Trimethylolethane, trimethylolpropane, glycerin.

A small amount of a trifunctional or higher functional alcohol such as 1.3.6-hexandriol, pentaerythritol, or bisphenol dioxypropyl ether can also be used in combination.

Polyesteramide resin contains a saturated dicarboxylic acid component, a glycol component, a diamine component, a lactam component,
This is a product in which aminocarboxylic acid components and the like are introduced into borya.

As the saturated dicarboxylic acid component and the glycol component, those mentioned above are used, as the diamine component, hexamethylene diamine, metaxylylene diamine, diaminobutane, etc., and as the lactam component, ε-caprolactam, ω-laurolactam, etc., aminocarboxylate are used. As an acid component (-
Aminocaproic acid, ω-aminononylic acid, 5ω-aminoundecanoic acid, ω-aminododecanoic acid, etc. are used.

As polyamide resin, nylon 6/nylon 66
/Nylon 12, Nylon 6/Nylon 610/Nylon 12. Nylon 6/Nylon 612/Nylon 12,
Nylon 6/Nylon 66/Nylon 610/Nylon 12. Nylon 6/Nylon 66/Nylon 11/Nylon 12. Nylon 6/Nylon 69/Nylon 610
/Nylon12. Nylon 6/Isophoronediamine 6/
2,2,4-/2,4,4-trimethylhexamethylenediamine 6, nylon 6/methaxylylenediamine 6/2,2,4-/2.4-trimethylhexamethylenediamine 12, nylon Copolymerized nylon such as 6/metaxylylenediamine 6/nylon 12 is preferably used.

(Silicone Diamine (B)) Silicone diamine (B) is a compound having amine groups at both ends of polysiloxane, and those represented by the following general formula are particularly used.

In the formula, R is an alkylene group such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, a cyclohexylene group, a phenylene group, or a tolylene group, with the propylene group being the most important due to manufacturing constraints. n is 0 or a positive integer.

The average molecular weight of silicone diamine (B) is 300-20
000, especially preferably within the range of 600 to 15,000. If the average molecular weight is extremely low, the adhesion between the water-repellent fabric and the fabric is good, but the moisture resistance may decrease or the adhesive may deteriorate over time after adhesion. On the other hand, when the average molecular star becomes extremely high, the adhesion to water-repellent fabric tends to deteriorate.

<Blending ratio> The blending amount of silicone diamine (B) to the hot melt resin (A) is 0.05 to 10 parts by weight, especially 0.1 to 5 parts by weight of the latter (B) per 100 parts by weight of the former (^). Please take care to ensure that the If the ratio of the latter (B) is too small, the adhesion to the water-repellent fabric will be insufficient, resulting in -inferior latter (B)
If the ratio is too high, the fluidity of the powder will be poor, the hygroscopicity will be high, and furthermore, it will be disadvantageous in terms of cost.

Production of hot melt adhesive> Hot melt resin (A) and silicone diamine (B)
The combination with the hot melt resin (A) in a powder state, a molten state, or a state dissolved or dispersed in a solvent,
This is done by mixing silicone diamine (B) in a liquid state or in a state dissolved or dispersed in a solvent. When the hot-melt resin (A) is in a molten state, it is preferable to perform the mixing under an inert gas atmosphere.When mixing the two in the presence of a solvent, the system may be depressurized as necessary after mixing. When the mixture is to be made into blocks or granulated, freeze-pulverization or chemical pulverization is performed as appropriate to obtain a predetermined particle size. In addition, if necessary, it can also be made into a film and used for the purpose of hot melt adhesion.

It is also possible to blend the filler 1 colorant, other hot-melt resins, etc. in the manufacturing process of the above-mentioned blend or at any stage after blending.

<Applications> The hot melt adhesive of the present invention can be used for bonding fabrics together in the production of clothing, including bonding and sewing interlining, covering fabric, lining, and regular clothing. It can be suitably used for. In particular, adhesive sewing of interlining using water-repellent cloth as the outer material is important. Other applications include melt sizing, nonwoven fabric production, and carpet backing. In some cases, it can also be used for adhesion of plastics, rubber, metal, glass, leather, paper, wood, etc.

Action and Effects of the Invention By blending silicone diamine (B) with the hot melt resin (A), that is, polyester resin, polyesteramide resin, or polyamide resin, the adhesion to water-repellent fabrics is significantly improved. .

The dry cleaning resistance of these hot melt resins (A) is due to the dry cleaning resistance of silicone diamine (B).
), it not only does not deteriorate, but also tends to improve.

Note that polyester resins, polyesteramide resins, or polyamide resins can also be obtained by producing resins using saturated dicarboxylic acid components or glycol components that have silicone units in their molecules as condensation components, but water repellent In order to obtain good adhesion when applied to processed fabrics, a large amount of modification is required, which is not only disadvantageous in terms of cost, but also increases the degree of modification as a hot melt adhesive. The physical property balance will be impaired.

Example Next, the present invention will be further explained with reference to Examples.

Hereinafter, "1 part" and "1%" are expressed on a weight basis.

<Resin for hot melt (A)> A-1 polyester amide) In a reaction vessel, 0.8 mol of terephthalic acid and 0.8 mol of adipic acid were added.
4 mol, l., 0.8 mol of 4-butanediol, 0.75 mol of ethylene glycol, and 0.02% (based on the entire system) of isopropyl orthotitanate as a catalyst were charged, and the mixture was heated at 2 temperatures from 190 to 100 ml in a nitrogen stream. The mixture was reacted at 200° C. for 4 hours while distilling off the water produced. 0.8 mol of caprolactam was charged and the reaction was allowed to proceed for 2 hours at normal pressure.

Subsequently, the pressure of the system was reduced to 0.5 to 0.3 parts (m) Ig, and the reaction was carried out at 250°C for 1 hour per reaction part. This gives an acid value of 2. OKOH g/g, melt viscosity (using a flow tester manufactured by Shimadzu Corporation, 1 part diameter, 30 k load)
g/c meal, measured at a temperature of 190°C, the same applies hereafter) 80
A polyesteramide resin of 0 poise was obtained.

Next, 0.8 parts of oxazoline was added to 100 parts of this resin and reacted at 180°C for 1 hour to give an acid value of 0.8 KOH1g.
/g and a melt viscosity of 1400 poise.

A-2 polyester, ) 0.6 mol of terephthalic acid, 0.4 mol of adipic acid, 1
, 4-butanediol 0.8 mol, ethylene glycol 1.2 mol, polytetramethylene glycol 0.005
mol and 0.1% (based on the whole system) of tetraisopropyl titanate as a catalyst in a nitrogen stream at a temperature of 140°C.
The reaction was carried out at ~240° C. for 4 hours while running off the water produced. Then, 0.1% of antimony trioxide (based on the whole system) was added and heated at 220-260°C under a reduced pressure of 1 mmHH.
The mixture was allowed to react for 2 hours.

This resulted in an acid value of 0.8 KOHmg/g and a melt viscosity of 1
A polyester resin of 350 voids was obtained.

8-3) Polyamide system) A commercially available copolymerized nylon having a copolymerization ratio of nylon 6/nylon 66/nylon 12 in a weight ratio of 40/30/30 was prepared.

<Manufacture of hot melt adhesive> Example 1 In a reaction vessel equipped with a stirrer, a vacuum device, and a thermometer, silicone diamine (B) 2 with an average molecular weight of 900 in which R in formula (I) described above is a propylene group. .0 parts to n-
A solution dissolved in 7100 parts of hexane was added, and then the above polyesteramide resin (A-1) was added to the solution.
100 parts of a powder obtained by freeze-pulverizing the above to a size of 60 mesh or less was added and dispersed with stirring. This dispersion was heated to 60°C and stirred for 1 hour under a reduced pressure of 300 mi+Hg.
- Hexane was distilled off. The obtained dry solid product was frozen and ground, and the powder of 60 mesh or less was sieved.

This powder was subjected to the test described below.

Example 2 Silicone diamine (B) 4°0 with an average molecular weight of 11,800 in which R in the formula (I) described above is a propylene group
Example 1 was repeated, except that a solution in which 100% of the powder was dissolved in n-hexane was used, and the obtained powder was subjected to the tests described below.

Comparative Example 1 The above-mentioned polyesteramide resin (A-1) was freeze-pulverized to a powder of 60 mesh or less and subjected to the test described below.

Example 3 Silicone diamine (B
) A solution of 2.0 parts dissolved in 100 parts of n-hexane was prepared, and then 100 parts of the powder obtained by freeze-pulverizing the above polyester resin (A-2) to a size of 60 mesh or less was added to this solution. , dispersed under stirring. This dispersion was heated to 60° C. and stirred for 1 hour under reduced pressure of 300 mmHg (7) to distill off n-hexane. The obtained dry solid product was frozen and ground, and the powder of 60 mesh or less was sieved.

This powder was subjected to the test described below.

Comparative Example 2 The above polyester resin (A-2) was frozen and pulverized to give 6
The powder reduced to 0 mesh or less was subjected to the test described below.

Example 4 The same procedure was carried out except that instead of the powder obtained by freezing and pulverizing the polyesteramide resin (A-1), a powder obtained by freezing and pulverizing the polyamide resin (A-3) of Section E to a size of 60 mesh or less was used. Example 1 was repeated and the resulting powder was subjected to the tests described below.

Comparative Example 3 The above polyamide resin (A-3) was frozen and pulverized to 60%
The powder reduced to a mesh size or less was subjected to the test described below.

<Evaluation test, adhesion test> Handling instructions Powdered hot melt adhesives of Examples 1 to 4 and Comparative Examples 1 to 3 of Company N were applied to the cotton core at 15 g/m'', 17 boins)/25
After forming dots at a ratio of mm, the pieces were melted and temporarily bonded.

Next, a cotton cloth coated with a silicone water repellent or a polyester cloth coated with a fluorine compound water repellent was placed on the processed surface, and the temperature was set in the range of 120 to 160 °C in 10 °C increments, and the pressure was 300 g. /am for 15 seconds to adhere by thermocompression, and the initial adhesive strength was measured by a T-beer test.

IJL resistance In addition, the above sample after bonding at 150°C was bonded at 40°C.
The adhesive strength was measured after washing with hot water, 0.3% detergent, 60 minutes in a laundry meter, and dry cleaning at 40° C., perchlorethylene, 60 minutes in a laundry meter.

<Test results> The results are shown in Table 1.

As is clear from Table 1, the hot melt adhesives of each example have better temperature resistance, heat resistance, initial adhesive strength, water washing and It can be seen that the adhesion strength after dry cleaning is significantly superior in all cases.

Procedural amendment (voluntary)

Claims (1)

[Scope of Claims] 1. 100 parts by weight of at least one hot melt resin (A) selected from the group consisting of polyester resins, polyester amide resins, and polyamide resins is added with amino acids at both ends of polysiloxane. A hot melt adhesive comprising 0.05 to 10 parts by weight of silicone diamine (B) having a group. 2. The average molecular weight of silicone diamine (B) is 300~
20,000. The hot melt adhesive according to claim 1. 3. The hot melt adhesive according to claim 1, which is used for bonding cloth to cloth. 4. The hot melt adhesive according to claim 1, which is for bonding water-repellent fabric.