JPS58124636A - Manufacture of extensible composite body of laminated fiber material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a stretchable laminated sheet material. The stretchable sheet material laminate produced in accordance with the present invention is used to wrap objects in a soft manner, for example, for the crotch and abdominal bands of disposable diapers, the opening and exit bands of paper bags, and the like.

A rubber band is used in the crotch part of conventional disposable diapers. Rubber bands that are used as bands require vulcanization, which requires a long kneading process, and cannot be incorporated as an endless material into a continuous production line for disposable diapers, etc., and requires complicated raw material collection in the production process. It had the disadvantage of having to be replaced, and was not fully satisfactory as an elastic material.

Recently, paper diapers have been developed that use foamed cloth/tape as a band instead of the above-mentioned rubber band. Urethane foam tape is produced by slicing a large cylindrical foam from the surface to a certain thickness, like peeling an apple, and cutting it to a certain width.
It is not possible to produce endless urethane foam tape.

In addition, since it is a foam, there will be some residual non-uniform foaming, and if it is sliced into a foamed urethane band with a cross-sectional area of 1 to 3 CIn and 0.1 to 1.5 cm in thickness, the tensile strength will partially deteriorate. When stretched to 200 to 300 inches, the foamed urethane band itself had the disadvantage of breaking, making it impossible to obtain sufficiently satisfactory performance.

The present inventors have worked hard to partially adhere a material that can be endlessly incorporated into the process as a stretchable part for the production process of disposable diapers, etc. to the sheet material using 1/20 to 1/2 of the surface area of the thermoplastic urethane resin. A method for producing a stretchable sheet material laminate, characterized by:

The thermoplastic urethane resin (nidistomer) used in the present invention may be any conventionally known urethane resin that becomes liquid when heated.

When used in the present invention, a thermoplastic resin obtained by directly reacting a raw material, a compound having two or more active hydrogens in the molecule with polyincyanate, may be used, or the above raw materials may be used in combination with other materials. It may also be used by reacting it in a factory and melting it into pellets.

Compounds having two or more active hydrogens used as raw materials include polyester polyols and polyether polyols. The polyester polyols have active hydrogen measured by the Tzelevitinoff method, and the molecular weight of at least one of these active hydrogen-containing compounds is SOO.
~5060, especially SOO~3000, a relatively high-molecular polyfunctional compound, preferably hydroxyl. The average molecular weight of these mixtures is 200 to 5000, more preferably 800 to 30.
00 molecules soo to 5000 preferably 800
Adipic acid, azelaic acid, and sebacic acid are relatively high-volume polyfunctional organic compounds that have active hydrogen as determined by the γ-Erewitinoff reaction at ~300o and have at least two functional groups that can react with isocyanate groups. Polyesters made from acids, polyhydric alcohols such as propylene/glycol, dimethylpropane-1,3 ethylene glycol, trimethylolpropane, glycerol, pentanyl, polyesters made from caprolactone, and amino alcohols in these polyester components. , polyesteramides prepared by incorporating aminocarboxylic acids and polyamides, and polyhydric alcohols, which are the reaction products of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and polyamides obtained by ring-opening polymerization of tetrahydrofuran. Alkylene ethers, polyvalent polythionyls, polycarbonates, polyacetals, and hydrocarbon compounds obtained by reacting living polymers of unsaturated hydrocarbon compounds with ethylene oxide, carbon dioxide, etc. can be used. Among these, polyester with a molecular weight of 100ON5000 and a mixture of this with a low molecular weight glycol such as 1.4 phthylene gelicol or ethylene glycol with an average molecular weight of 80 are preferable.
It is between 0 and 3000.

The molecular weight of these compounds is 800 to 5000, especially SOO
-3000, it is possible to provide an excellent rubber elastic body. In addition, polyfunctional compounds having a molecular weight of 700 or less and having an active hydrogen at the end determined by the Tzelevitinoff method that can be used in the present invention include ethylene glycol, propylene gellicol, bentanediol, hexaptylene glycol, decamethylene glycol, thio diglycol,
Glycerol, penta;/erythritol, trimethylolpropane, 1,2.6-hexanediol, N, N
, N'.

Nl, polyhydric alcohols such as -tetrakis-2-hydroxypropylethylenediamine, alkanolamines such as p-aminobenzyl alcohol, ethanolamine, aminopropyl alcohol, 3,31-dinitrobenzidi/, 3,31-dichlor Diamines such as benzidine, phenyldiamine, tolylene diamine, xylene diamine, diphenylmethane diamine and the like are used. The polyether polyols have active hydrogen measured by the Zelewitino 7 method, and at least one of these active hydrogen-containing compounds has a molecular weight of 800 to 5,000, particularly 800 to 5,000.
3000 relatively high-molecular polyfunctional compound with a hydroxyl value of approximately 3
0 to 800 acid capsules of 5 or less, and in addition, it is preferable to use a similar compound with a molecular weight of 700 or less in combination.
The average molecular weight of these is 200 to 5000, more preferably 800 to 3000.
Examples of polyfunctional organic compounds with relatively high molecular weights, preferably having an active hydrogen concentration of 800 to 3000 determined by the Zelewitinoff reaction and at least two functional groups capable of reacting with isocyanate groups, include ethylene glycol, 1,2
-Propylene glycol, dimethylpropane-1,3-
Diol, 1,3-cropylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, trimethylolpropane, glycerol,
These are polyalkylene ethers such as those obtained by ring-opening polymerization of tetrahydrofuran and reaction products of polyhydric alcohols such as pentaerythritol and alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide, and tetrahydrofuran. Among these, polyesters are preferred.

Examples of the organic polyisocyanate compound used in the present invention include 1-methylphenyl-2,4-diisocyanate, 1,3-dimethylphenyl-2,4-cyisocyanate, 1-chlorophenyl-2,4-diisocyanate,
4.4'-diphenylmethane diisocyanate, p-phenyl diisocyanate), 1.5-naphthylene diisocyanate, p-xylylene diisocyanate, m-phenylene diisocyanate, 2,2'-diethyl-4,
41 diphenyl diisocyanate, 3.3'-dichloro-4,4I-diphenyl meta/diisocyanate, 3
, 3'-dimethoxy-4,41-diphenylmethane diisocyanate, diphenyl ether-4,4'-diisocyanate, stilpene diisocyanate), 4.4'
-Diphenyl sulfite diincyanate, 1.4-
Cyclohexane diisocyanate, hexamethylene diisocyanate, 4,4'-hexahydrodiphenylmethane diisonanate, dibenzyl diisocyanate, triphenylmethane diisocyanate, etc. are used. 3
The incyanate compound having a value higher than the value can be used by mixing a small amount with the diincyanate compound. Among these, 4.4' diphenylmethane diisocyanate is preferred.

The reaction ratio of these compounds is usually such that the ratio of incyanate groups to active hydrogen groups is 0.9 to 1.5, more preferably substantially 1.

Any of the above-mentioned compounds can be used in the present invention, but they must be used under conditions that allow a thermoplastic product to be obtained. Alternatively, when polyisocyanate is used, it is used under conditions that do not increase three-dimensional crosslinking.

Catalysts can be used when producing thermoplastic polyurethane plastics. For example, triethylenediami/, N-methylmorpholine, N-ethylmorpholine,
diethylethanolamine, 1-methyl-4-dimethylaminoethylpiperazine, dimethylphenylamine,
There are tertiary amines such as N-dimethyl-N-methylisopropylpropylene diamine. Other catalysts include
Tin compounds such as stannous chloride, tin salts of carboxylic acids, tin alcoholades, etc. can be used.

Although a solvent is not normally used, it may be used if necessary, such as xylene, toluene, butyl acetate, ethyl acetate, and the like. It is preferable to remove the solvent by distillation or the like after the reaction.

As a complete mixing reactor for these reactions, a reactor that performs stirring and mixing using rotary blades is generally used.
The types of rotary blades used include commonly used rotary blades such as ribbon blades, screw blades, turbine blades, propeller blades, horseshoe blades, anchor blades, cylindrical blades, and disk blades, as well as combinations of these blades. As a reactor having a piston flow function, an extruder, an extruder, a piston, etc. are used, and these are connected in contact with each other to function as one reactor. It is desirable for each reactor to avoid dead space as much as possible, and it is desirable that the wings and walls, screws and barrels, etc. be as close together as possible.

The reaction temperature is usually 50 to 210°C, and the reaction can be carried out by increasing the temperature in two or more stages.

The reaction time needs to be varied depending on the reaction raw materials and reactor, but is in the range of 1 minute to several hours.

In the present invention, the thermoplastic urethane resin obtained as described above is drawn out endlessly in the form of a tape or thread, cooled once, and used as a cured elastic material. This form is not particularly limited, and may be tape-like, rod-like, thread-like, hollow fiber-like, or non-woven fabric-like, which can be used as a band.
It is usually used in the form of a tape with a thickness of about 0.001 to 10 m111 or a thread of about 0.01 to 10 m in diameter.

The physical properties of these tape-shaped and thread-shaped thermoplastic urethane resins include tensile strength at break of 10 to soo kg/7. Too modulus 0.01 to 5 kg/cfl More preferably tensile strength at break 30 to 200 kg/cr/l too
Raw materials are selected so that the % modulus is 0.05 to 30 kg/cut.

The drawn thermoplastic urethane resin is once cooled to harden it, but this is done either by airing it in a non-stretched state or by winding it on a cooling drum.

Next, the cured thermoplastic urethane is stretched to an elongation of 1.5 to 5 times and bonded to the sheet material. It is also possible to use a sheet material made by stacking the fibers in a more stable manner. When adhering to the sheet material, the entire surface of the thermoplastic urethane resin is not adhesively fixed, but is adhered at right angles or at an angle so that the adhesive is continuous in dots or lines as uniformly as possible over the entire surface. The bonding area is usually 1/20 to 1/2, preferably 1/10 to 1/5 of the surface area, and the bonding area does not cover a part of the surface of the thermoplastic urethane used. Make sure that it is evenly distributed over the entire surface. The bonding method is not particularly limited, and any conventionally known method may be used. For example, a portion may be thermally fused using a device such as a hot press. Adhere by using a needle punch or other method to tangle the fibers. For example, using adhesive.

The adhesive used here is preferably a hot-melt adhesive, and ethylene-vinyl acetate copolymer resin-based or polyamide resin-based hot-melt adhesives can be used. Chemical industry product), Evergrip PA-73 (Sale Chillney product), etc.
Among these, those based on ethylene vinyl acetate copolymer resin are preferred.

These may be used as double-sided tapes impregnated onto a substrate.The hot-melt adhesive bonding method uses a hot-melt applicator. That is, the hot-melt adhesive is melted in a heated melting stock tank, pumped to a nozzle section, intermittently discharged from the nozzle section, dotted on the thermoplastic urethane resin or laminated sheet material, and immediately pressed to complete the bonding. do. You can sandwich the thermoplastic urethane resin and laminate sheet materials on top and bottom. If you want to obtain a stronger laminate, you can laminate two or more sheets of thermoplastic urethane resin and sheet material in sequence. .

When the adhesion is completed, it becomes a stretchable laminated composite, and when the tension is released, the part containing the thermoplastic urethane resin contracts and functions as a band.

The urethane elastic band of the present invention can be stretched over an extremely long length and has a high breaking strength, and a sufficient effect can be obtained with a very small band, so when incorporated into a diaper etc., the volume of the band portion is reduced. It has the advantage of being small and not causing discomfort when worn. Furthermore, since it has a high breaking strength, it can be operated continuously with extremely good workability without causing cuts on an endless production line. The disposable diaper production line runs at a speed of 30 to 100 fFl/min, and the band used for this requires at least several thousand meters per roll, preferably endless, but this is possible with the present invention. The unique feature is that the endless urethane resin band molding process is directly connected to the disposable diaper production line, making it possible to easily produce stretchable laminates at high speed. The present invention will be explained in more detail with reference to Examples below.

The accompanying drawings are for the purpose of making the embodiments easier to understand, and the equipment and materials are as follows.

[A]: Heat melting tank [B]: Gear pump [C]: Die [D]: Heater [E]: Drum [F] Ni guide roll [G]: Adhesive stock tank () I): Horizontal moving feed Roll [■]: Adhesive dotting device [J]: Nonwoven fabric unwinding roll (K): Polyethylene sheet unwinding roll [L] Nibbles [(4)-Cutter [N]: Feed roll (1) Thermoplastic urethane resin chip (2) Molten thermoplastic urethane resin liquid (3) Drum cooling water (4) Thermoplastic urethane resin film (5) Hot melt adhesive (6) Nonwoven fabric (7) Polyethylene film (8) Stretchable laminate (+1 Nonwoven fabric ( 11) Polyethylene sheet (■1) Thermoplastic urethane film (1v) Hot melt adhesive (a): 1.4 but 15 diol stock tank [
b]: Brepolymer stock tank [C]: Flowmeter [d] Dual flowmeter [e]: Hopper for reaction tank [f]: Extruder for reaction tank mixing [g]: Extruder for reaction tank mixing [h] : Motor [i]: Motor [J]: Reaction tank heater [k]: Reaction tank heater [L]: Pulp [m]: Gear pump [n]: Die [O] Two-roll roll [p] Ni guide roll ( 1'): ], 48G <a) Niprepolymer (35: 1.4 BG/prepolymer mixture (6:
Thermoplastic urethane resin liquid (Me: Rod-shaped thermoplastic urethane resin Example 1 Hopper of heat melting tank (A), thermoplastic urethane resin pellets (Estane 5701 manufactured by Gutdrich)
and heated to 150-200℃ with heater (D).
Allow the pellets to melt.

Gear pump CB) Feeds a fixed amount of molten thermoplastic urethane resin. The molten thermoplastic urethane resin is discharged from the die (C) onto the surface of the rotating drum [E], and the molten thermoplastic urethane tape is cooled on the surface of the rotating drum (E).The guide roll [F] and the rotating drum [E] ] Peel the thermoplastic urethane tape from the surface of the rotating drum [E] at the contact point.

The thermoplastic urethane resin tape thus produced is fed through a horizontally movable feed roll CI (), and a hot melt adhesive (Hirodyne 1800; manufactured by Hirodyne Industries, Ltd.) is dotted onto both sides of the film using an adhesive dotting device (I). Apply partially.

Nonwoven fabric unwinding roll (J) Shine woven fabric (Angel Paper Manufacturing ■
Manufactured by Angel Fushokufu 9 tsubo m 16 g/m') t,
From the polyethylene sheet unwinding roll, pull out the polyethylene sheet and use the feed roll [N] to stack it in a German pattern.

When the thermoplastic urethane tape adhesive dot area reaches the press (L) section set between the feed roll [N] and the adhesive dot device, the feed roll [N] and the horizontally movable feed roll [river rotation] Stop the adhesive dotting device and move the horizontally movable feed roll (H) horizontally as shown in the wavy line in the figure to apply tension to the thermoplastic urethane resin tape and keep it at 100% elongation. The nonwoven fabric, thermoplastic urethane resin tape, and polyethylene sheet are press-bonded using a press (L) fixed between the devices.

Remove the press (, L), feed the laminated sheet through the feed roll [N], and at the same time return the horizontally movable feed roll [H] to its original position. The complexes with the following properties were continuously produced.

A schematic process diagram of Example 1 is shown in FIG.

The thermoplastic urethane film has a thickness of 0.15 mm and a width of 1
．． It is QcIrL. Its physical properties were elongation: 600 cm, breaking strength: 550 cm, and 9/cIrL.

Example 2 1.4BG was stocked in the stock tank (5), and 80% of the prepolymer corresponding to tetramethylene adipate/44' diphenylmethane diisocyanate = 1 mol/2 mol 4 with an average molecular weight of 1200 was stocked in the stock tank (5). Stock at ℃.

1.4BG/prepolymer, : = 9/200. (6) to 1.48G and charge the prepolymer into the reaction tank hopper (5). 1.48G and prepolymer are mixed in a reaction tank mixing extruder, and 1.413G and prepolymer cause an initial reaction.

1, which was then mixed in a reaction tank mixing extruder;
The 48G/prepolymer mixture undergoes a reaction and becomes a thermoplastic urethane resin liquid. The latter part of the reaction tank mixing extruder and part of the reaction tank mixing double extruder are heated to 150℃ with the reaction tank heater θ] and 200℃ with the reaction tank heater ■.
Heat to 71°C. The thermoplastic urethane resin liquid produced above is sent to the die (B) from the gear pump i. From the die turn, it is drawn in using the thermoplastic urethane resin liquid roll (6) and guide roll (b).

The rod-shaped or hollow thermoplastic urethane resin thus produced is connected to the horizontally movable feed roll (5) of Example 1.

The subsequent steps are the same as in Example 1.

Figure 5 shows the rod-shaped or hollow rod-shaped thermoplastic urethane strength 20 of this example.
It was 0 kg/cIrL.

Comparative Example 1 70 parts of a triol (Sannix FA-103, Sanyo Kasei) with a molecular weight of 3,000 by adding ethylene oxide and propylene oxide to glycerin; −
3700M Sanyo Chemical) 30 parts, water 4 parts, D as a catalyst
abco 33 LV (manufactured by Sandai Air Products)
0.3 parts, L-520 (Nippon Unica product) 2 as a foam stabilizer
．． Mix 0 parts uniformly in a mixing tank. Next, add 0.3 parts of tin octylate (Ll-28 Nitto Kasei product) and tolylene diisocyanate (Sumidurny 80 Sumitomo Bayer product) and mix uniformly. The cylindrical foam was immediately poured into a mold preheated to 120°C and allowed to foam for 30 minutes in a heating oven at 120-130°C.Then, the cylindrical foam was removed from the mold and passed through a cutting machine and a cutter, just like peeling an apple. It was cut with a knife to a width of 1 cIIL and a thickness of 0.5 m to obtain a foamed urethane strip 50 m long. This urethane band had a tensile strength at break of 1.5 kg/d, an elongation at break of 350%, and an expansion ratio of 50. This foamed urethane band was used instead of the thermoplastic urethane film in Example 1, and the workability and product performance were compared when a stretchable composite was manufactured using horizontal method 2 of Example 1 and a comparative example. - Shown in A.

Table-A * Number of breaks The number of times the urethane band itself breaks when stretched twice after producing a stretchable laminate and consuming 100 m of the urethane band * Wood product inspection passing rate The produced stretchable laminate The band was stretched and contracted 20 times and inspected for breakage, and those that did not break were deemed to have passed.

***Urethane band permanent 499- Measurement conditions conform to vulcanized rubber physical test method JISK6301.

As mentioned above, the urethane band 8 of Example 1.2 was the same as Comparative Example 1.
Compared to urethane foams, there is no breakage during the production of stretchable laminates, the product acceptance rate is good, and excellent stretchable laminates can be obtained.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram showing the steps of Example 1, FIG. 2 is a plan view of the composite obtained in Example 1 during elongation, and FIG. 3 is a diagram along line A-A' in FIG. A cut sectional view is shown, and FIG. 4 is a sectional view of the contracted state. FIG. 5 is a schematic diagram showing the steps of Example 2. 1 blade 2

Claims (1)

[Scope of Claims] 1. Tape-shaped or thread-shaped thermoplastic urethane resin of 1.5 to
Keeping the elongation at 5 times, overlap it with the fiber sheet material and adhere it so that 1/20 to 1/2 of the surface area of the thermoplastic urethane resin is discontinuous in the direction of expansion and contraction of the sheet material. A method for producing a stretchable sheet material laminate, characterized by: 2. The method for producing a laminate according to claim 1, wherein the thermoplastic urethane resin is a resin obtained by reacting porous atoms having a molecular weight of 200 to 5000 at a ratio of 0.9 to 1.5. . 3.Tape-shaped or thread-shaped thermoplastic urethane resin has a tensile strength at break of 10 to 500 kg/be, 100-thick Duras 30k
A method for producing a laminate according to claim 1 or 2, which has physical properties of g/di or less. 4. The sheet material according to any one of claims 1 to 3, wherein one-tenth to one-fifth of the surface area of the tape-shaped or thread-shaped thermoplastic urethane resin is bonded to the sheet material by points or lines. Production method.