JPS59625B2 - Fiber adhesive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fiber adhesive composition, particularly a binder composition for producing nonwoven fabrics for clothing interlining, and an adhesive used in the production of fiber base materials for artificial leather and synthetic leather. It is.

Conventionally, acrylic or SBR emulsions have been known as binders for manufacturing nonwoven fabrics, but nonwoven fabrics using these emulsions have poor normal strength, but have the drawback of poor water and solvent resistance, and require relatively large quantities. binder is required, and therefore the properties of the fibers themselves cannot be fully utilized, so the texture of the nonwoven fabric tends to be poor, and it has the disadvantage of poor rebound elasticity.
In addition, SBR type materials have the disadvantage of poor light resistance.

On the other hand, polyurethane emulsions have excellent impact resilience, and attempts have been made to use them as nonwoven fabric binders, but at present they have particularly poor processing suitability, ie, poor web separation, and also lack sufficient water resistance and solvent resistance.

In addition, ordinary polyurethane has poor light resistance, and its improvement requires aliphatic isocyanate, which causes many problems such as high cost, and is hardly ever put into practical use.

A self-emulsifying cationic polyurethane resin emulsion obtained by reacting an inorganic or organic acid with a linear polyurethane having a tertiary nitrogen atom in an organic solvent and then replacing the organic solvent with water is known. be.

(Refer to Japanese Patent Publication No. 42-5118) Although this known emulsion can be crosslinked by heating, the crosslinking is essentially ionic crosslinking, and therefore water resistance and solvent resistance are not sufficient. Furthermore, due to the oxidizing action of the inorganic or organic acids, there is a drawback that yellowing occurs during heat processing or yellowing and deterioration occurs during light resistance tests.

Furthermore, when used in the production of nonwoven fabrics, it has poor processing suitability for fibers, poor permeability, poor adhesion, and poor web separation, making line production impossible.

As a result of intensive research to eliminate the drawbacks of the binder made of the self-emulsifying cationic polyurethane resin emulsion, the present invention has been developed by adding a hindered amine stabilizer and polyoxyethylene lauryl ether to a polyurethane resin having a tertiary nitrogen atom. By reacting monochloroacetic acid in the presence of heat, it becomes easy to introduce carboxyl groups without causing discoloration, and it also improves processing suitability for fibers during nonwoven fabric production, including permeability, adhesion, and web release. In addition, by crosslinking this carboxyl group with a water-soluble epoxy compound, we have created a fiber adhesive that prevents yellowing during heat processing, prevents yellowing and deterioration during light resistance tests, and has improved water and solvent resistance. We were able to obtain a composition for this purpose.

That is, the feature of the present invention is that 0.2 to 2 parts by weight of a hindered amine stabilizer and 0.3 to 3 parts by weight of a polyoxyethylene lauryl ether surfactant are added to 100 parts by weight of a linear polyurethane resin having tertiary nitrogen. A carboxyl group-containing cationic/nonionic polyurethane emulsion obtained by reacting monochloroacetic acid in the presence of
The present invention provides a fiber adhesive composition comprising a water-soluble epoxy compound mixed in a ratio of 1 to 2 equivalents of epoxy groups to 1 equivalent of carboxyl group.

The cationic/nonionic polyurethane emulsion of the present invention is produced by reacting monochloroacetic acid with a linear polyurethane resin having tertiary nitrogen in an organic solvent at 60 to 80°C in the presence of a hindered amine stabilizer and polyoxyethylene lauryl ether. It can be obtained by replacing the above organic solvent with water.

The polyhydroxy compound used to produce the above-mentioned linear polyurethane resin is a polyether or polyester having a hydroxyl group at the end of the molecule and having an average molecular weight of 500 to 10,000, preferably 1,000 to 3,000, or a polyester or polyester thereof. It is a mixture of polyols used in the production of general polyurethane resins.

The above polyether is ethylene glycol J-ol,
Polyester has a hydroxyl group at the end by adding one or more compounds such as ethylene oxide and propylene oxide to dihydric alcohol such as propylene glycol, water, etc., and polyester has a hydroxyl group at the terminal. Condensation polymers with acid J and lactone polymers are preferred. For example, condensation polymers of butanediol and adipic acid and neopentyl glycol and adipic acid are preferred. Aromatic or tetraaliphatic isocyanate compounds are used as polyisocyanate compounds for producing linear polyurethane resins, specifically, 2,4- or 2,6-tolylene diisocyanate, 4,4' -diphenylmethane diisocyanate, isophorone diisocyanate, and the like are useful. The chain extender for extending the chain of the reaction product of the polyhydroxy compound and polyisocyanate compound is an amine having a tertiary nitrogen, and specifically, N-methyldiethanolamine, N-ethyldiethanolamine, Examples include N-n butyldiethanolamine, N-oleyldiethanolamine, etc.
Ethylene glycol, hexanediol, 1,4-butanediol, ethylenediamine, hexamethylenediamine, and the like are useful as those that can be used in combination with these amines.

Organic solvents for the above-mentioned linear polyurethane resin include ketones such as methyl ethyl ketone, esters such as methyl acetate and ethyl acetate, and other solvents commonly used in the production of polyurethane such as benzene and toluene, which are compatible with water. Acetone, methyl ethyl ketone, etc. are suitable. When the above-mentioned polyurethane having a tertiary nitrogen atom is treated with monochloroacetic acid under heating in the presence of a hindered amine stabilizer and a polyoxylauryl ether surfactant, and the solvent is replaced with water, the tertiary nitrogen atom Upon quaternization, a cationic/nonionic polyurethane emulsion into which carboxyl groups have been introduced is formed without discoloration.

The hindered amine stabilizers used above include those having a hindered tertiary amino group that is particularly difficult to react with chloroacetic acid, such as Tinupin 144 (Ciba Co., Ltd.).
(manufactured by Geigy) etc. are suitable.

Furthermore, as the polyoxyethylene lauryl ether surfactant used in the above, those having an HLBl of 5 or more, such as Emulgen 1, 20, and 147 (manufactured by Kao Atlas Co., Ltd.), are suitable.

The water-soluble epoxy compound reacted with the carboxyl group is a low molecular weight compound having two or more hydroxyl groups, such as a polyglycidyl ether compound synthesized by reacting epichlorohydrin with ethylene glycol, glycerin, diglycerin, trimethylolpropane, etc. is useful.

The amount of the hindered amine stabilizer used in combination when reacting monochloroacetic acid with the polyurethane having a tertiary nitrogen atom is 1 for the polyurethane resin having a tertiary nitrogen atom.
0.2 to 2.0 parts by weight (the same applies hereinafter), preferably 0.25 to 1.0 parts. If the amount is less than 0.2 parts, there will be no sufficient effect of preventing yellowing and deterioration caused by heating, oxidation, ultraviolet rays, etc., and if it exceeds 2.0 parts, there is a risk of blooming.

Further, the amount of the polyoxyethylene lauryl ether surfactant used in combination is 0.3 to 3 parts, preferably 0.3 parts to 100 parts of the polyurethane resin having a tertiary nitrogen atom.
．． 5 to 2 parts is good. If it is less than 0.3 parts, the processing suitability for fibers is poor due to the fragmentation of emulsion particles, and the permeability and
No improvement in adhesion or network separation was observed.

Moreover, if it exceeds 3.0 parts, water resistance will decrease. Furthermore, if the polyoxyethylene lauryl ether surfactant used has an HLB of less than 15, the above effects cannot be obtained.

In addition, the timing of addition of the hindered amine stabilizer and polyoxyethylene lauryl ether surfactant is as follows:
Before acting chloroacetic acid on polyurethane having tertiary nitrogen atoms, it is preferable to add it in advance to a solution of polyurethane having tertiary nitrogen atoms; otherwise, the effect will be greatly reduced. The amount of the water-soluble epoxy compound mixed into the cationic/nonionic polyurethane emulsion having a carboxyl group is 1.0
~2.0 equivalents, preferably 1.2 to 1.5 equivalents of epoxy groups.

If the ratio of the equivalent of epoxy group to 1 equivalent of the above carboxyl group is less than 1.0, unreacted carboxyl groups will remain, resulting in decreased water resistance and solvent resistance, discoloration during processing and heating, and yellowing during light resistance tests. , easy to cause deterioration.

On the other hand, if the equivalent ratio exceeds 2, a large amount of unreacted water-soluble epoxy compound remains, resulting in a decrease in water resistance.
The polyurethane emulsion and water-soluble epoxy compound undergo a gradual crosslinking reaction even at room temperature, but when producing a nonwoven fabric, it is preferable to carry out crosslinking by heating from 12"C3 to 140°C for 1 minute.

Furthermore, in producing a nonwoven fabric using the fiber adhesive composition of the present invention, any webbing fibers that are generally applicable to the production of nonwoven fabrics may be used, and in particular, nylon, polyester, etc. are suitable for interlining. suitable.

The fiber adhesive composition according to the present invention not only has good processing suitability for fibers and excellent permeability and adhesion when producing a nonwoven fabric, but also has extremely good web separation and does not cause discoloration during processing.

In addition, the nonwoven fabric produced using this fiber adhesive composition has good rebound resilience, excellent normal strength, water resistance and solubility resistance, and almost no yellowing or deterioration during light resistance tests.

As a result, the amount of adhesion to the fibers is only half that of conventional emulsions, and it is also possible to use very fine denier webs, resulting in a nonwoven fabric with excellent texture.

These properties are basically caused by the formation of chemical crosslinks due to the reaction between the carboxyl groups contained in polyurethane and the epoxy groups of the water-soluble epoxy compound, as shown in the formula below. It is thought that this is because water resistance and solvent resistance are improved due to the presence of , and oxidative deterioration is reduced due to the absence of carboxyl groups.

In addition, the presence of the hindered amine stabilizer is thought to prevent yellowing due to oxidative decomposition of carboxyl groups upon heating during carboxylation and crosslinking, and further reduce yellowing and deterioration during light resistance tests.

Also, during carboxylation and emulsification,
The presence of a polyoxyethylene lauryl ether surfactant improves suitability for processing into fibers by fragmenting the emulsion particles, improves penetration and adhesion to fibers, and stabilizes the emulsion particles to prevent web separation. It is thought that there is a function to improve it.

Moreover, even if other surfactants such as polyoxyethylene nonylphenol are used, there is almost no effect, and the action of the above-mentioned surfactants is recognized to be specific. This invention will be explained below according to examples.

Example 1 After dehydrating 160 gr of polyester polyol (0H value 112.2) obtained by the reaction of adipic acid and butanediol, 100 gr of 4,4'-diphenylmethane diisocyanate was added to the dehydrated polyol, and the mixture was heated at 80°C.
for 30 minutes, and then after cooling to 50°C, 100g of methyl ethyl ketone and 11g of N-methyldiethanolamine
8g) ethylene glycol (5gr) was added and reacted while maintaining the temperature at 80°C.During the reaction, 200gr of methyl ethyl ketone was added and reacted for 1 hour to obtain a tertiary nitrogen-containing polyurethane solution.

Add 1.5 g of a hindered amine stabilizer "Tinupin 144 (trade name) (manufactured by Ciba Geigy)" to this polyurethane solution.
Add R and polyoxyethylene lauryl ether surfactant, 3 gr of Emulgen 120 (trade name, manufactured by Kao Atlas Co., Ltd.), thoroughly mix and dissolve, and add 9.0 g of chloroacetic acid.
After adding gr and 300 gr of water and keeping it at 80°C for 30 minutes, methyl ethyl ketone was removed by suction using a vacuum pump to obtain a milky white stable cationic/nonionic compound with a solid content of 50% by weight and an average particle size of 0.4 microns. I got an emulsion.

To 100 parts of this emulsion, 3 parts of a water-soluble epoxy resin with an epoxy equivalent of 150 obtained by adding epichlorohydrin to glycerin was added and thoroughly mixed to prepare a fiber adhesive composition.

A web (polyester 2D x 29m) prepared in advance in a 10% resin bath diluted with water was
m50%, nylon 3D x 51mm, 50% weight 40V
/m”) was sandwiched between two sheets of stainless steel and screen conveyor and dipped, squeezed with a roller so that the amount of the composition attached to the fibers was 40%, and then pre-dried at 90°C for 15 minutes. Thereafter, curing was performed at 140° C. for 2 minutes to obtain a nonwoven fabric.

This composition had good processing suitability for web fibers, and had very good permeability, adhesion, and web release.

The results of normal strength, wet (water resistance) strength, solvent resistance, bending resistance and light resistance tests of this nonwoven fabric are shown in the table below along with other examples and comparative examples.

Example 2 Polyoxypropylene glycol (0H value 11
2) After dehydrating 180gr, add 90gr of 4,4'-diphenylmethane diisocyanate and react at 120°C for 1 hour, then cool to 50°C, then add 100gr of methyl ethyl ketone) and 21gr of N-methyldiethanolamine.
was added and reacted at 80° C. During the reaction, 200 gr of methyl ethyl ketone was added and reacted for 2 hours to obtain a tertiary nitrogen-containing polyurethane solution.

Add a hindered amine stabilizer to this polyurethane solution (trade name: Tinupin 144 (manufactured by Ciba Geigy), 1.5 gr).
and polyoxyethylene lauryl ether surfactant, “trade name Emulgen 147 (manufactured by Kao Atlas Co., Ltd.)”
Add 3g of chloroacetic acid, mix and dissolve thoroughly, and add 10g of chloroacetic acid.
After adding 300g of water and keeping it for 8 minutes,
Methyl ethyl ketone was removed by suction using a vacuum pump to obtain a cloudy, stable cationic/nonionic polyurethane emulsion with a solid content of 5.0% by weight and an average particle size of 0.6 microns.

To 100 parts of this emulsion, 3.5 parts of a water-soluble epoxy resin with an epoxy equivalent of 153 obtained by adding epichlorohydrin to diglycerin was added and thoroughly mixed to prepare a fiber adhesive composition.

Using this fiber adhesive composition, a nonwoven fabric was prepared in the same manner as in Example 1 above.

Example 3 In Example 1, cation. A nonionic emulsion was prepared in the same manner as in Example 1 except that the polyoxyethylene lauryl ether surfactant (trade name Emulgen 120) was not used, and the solid content was 50% by weight and the average particle size was 1 micron. I got an emulsion.

Using this emulsion, a fiber adhesive composition was prepared in the same manner as in Example 1, and an attempt was made to prepare a nonwoven fabric in the same manner.
The composition had poor permeability and adhesion to web fibers, did not adhere uniformly, and had difficulty in separating from the web, making it difficult to prepare a nonwoven fabric.

Example 4 In the same manner as in Example 1, except that the hindered amine stabilizer (trade name Tinupin 144) was not used,
A stable cationic/nonionic polyurethane emulsion having a solid content of 50% by weight and an average particle size of 0.4 microns was obtained.

Using this emulsion, a fiber adhesive composition was prepared in the same manner as in Example 1, and a nonwoven fabric was prepared using this composition.

Although this nonwoven fabric was slightly colored (yellow), it had good processability.

Example 5 A nonwoven fabric was prepared in the same manner as in Example 1 without adding a water-soluble epoxy resin to the cationic/nonionic polyurethane emulsion synthesized in Example 1 above.

Example 6 A nonwoven fabric was prepared in the same manner as in Example 1 using a commercially available self-crosslinking acrylic emulsion.

The results of testing the nonwoven fabrics obtained in each of the above examples are shown in the table below.

As can be seen from the above table, the nonwoven fabric treated with the fiber adhesive composition according to the present invention shows less discoloration during processing and less discoloration during the light fastness test than Example 3, and is far superior.

Furthermore, it can be seen that the water resistance and solvent resistance are improved compared to Example 5. Furthermore, compared to the nonwoven fabric treated with the Example, that is, the commercially available acrylic fiber adhesive composition, it is shown that not only normal strength but also water resistance, solvent resistance, and impact resilience are far superior.

Claims (1)

[Claims] 1 Monochloroacetic acid in the presence of 0.2 to 2 parts by weight of a hindered amine stabilizer and 0.3 to 3 parts by weight of a polyoxyethylene lauryl ether surfactant based on 100 parts by weight of a linear polyurethane resin having tertiary nitrogen. A fiber adhesive product characterized in that a carboxyl group-containing cationic/nonionic polyurethane emulsion obtained by reacting with a water-soluble epoxy compound is mixed in a ratio of 1 to 2 equivalents of epoxy groups to 1 equivalent of carboxyl groups. Composition.