JPS5855271B2 - How to form composite products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new and improved method for forming a composite product, characterized in that the product formed by the method comprises a base sheet and a hydrophilic polyurethane foam; reacting a polyisocyanate with a polyol or a mixture of two or more polyols having a reactive functionality greater than 2 to form a hydrophilic prepolymer consisting of an isocyanate-capped polyol, said hydrophilic prepolymer comprising: At least one of the incyanate-capped polyols has a hydroxyl-terminated hydrophilic ethylene oxide homopolymer component, or a hydrophilic copolymer of 60% or more but less than 100% ethylene oxide and 40% or less propylene oxide or butylene oxide. (b) Water is mixed with the hydrophilic prepolymer, and this water has a concentration of 6.5-3 to 1 mole of -NCO in the prepolymer.
(c) the group consisting of woven, knitted, crocheted, felted, paper, leather and porous membranes of the mixture of said hydrophilic prepolymer and water; A method for forming a composite product, comprising forming a hydrophilic polyurethane foam layer having a cross-linked three-dimensional network structure on the base sheet without adding a foaming agent in contact with a base sheet selected from be.

Numerous attempts have been made to create hydrophilic polyurethanes for use as base sheet coatings.

These attempts have typically been based on incorporating additional hydrophilic additives into hydrophobic polyisocyanates.

Also used in its preparation were reactants such as polyoxyethylene polyols, polyisocyanates containing small or g-stoichiometric amounts of water, and catalysts.

In the case of products based on non-catalytic reactions, linear polyoxyethylene diol, diisocyanate and varying amounts of water were used.

Although these prior art hydrophilic polyurethanes have been used for substrate sheet coatings for a number of reasons, they suffer from several significant drawbacks.

For example, although expensive and sensitive processing conditions are required, the final product quality and moisture control are poor.

Recently, however, it has surprisingly been possible to produce cross-linked hydrophilic polyols by simply combining an incyanate-capped polyoxyethylene polyol and a base sheet component reacted with a large but predetermined amount of an aqueous reactant. It has been discovered that improved substrate sheet composite products can be made using polyurethane.

The ratio of moles of H2O to moles of NCO groups in this case is about 6.5 to about 390.

The polyurethanes made in this manner are characterized by a cross-linked or non-linear network structure, which improves a wide range of properties such as comfort, moisture control, heat resistance, and solvent resistance.

In addition, it is easy to process, and by incorporating selected additives, it is possible to create a textile composite with flame resistance, sound damping properties, and other properties.

Generally speaking, polyoxyethylene polyols are capped with polyisocyanates such that the capped product has a functionality of at least about 2.
) a cross-linked hydrophilic foam can be produced.

This capped product foams simply by combining it with an aqueous reactant.

If the capped product and/or the aqueous reactant contain suitable crosslinking agents, the functionality of the capped polyoxyethylene polyol product will be approximately 2.
However, if it does not contain it, its sensuality must exceed 2.

During capping, the polyisocyanate and the polyol are reacted such that the reaction product, i.e., the capped product, has substantially no reactive hydroxy groups but an average of more than two isocyanate groups per molecule. This is desirable.

Another method for achieving this desired result is to combine a polyisocyanate with an average of two reactive inocyanate groups per molecule with 3 to 6 or more amine, hydroxy, thiol or carboxy groups per molecule. The reaction is carried out during foaming in a reaction system containing a polyfunctional reactive component having the following properties.

These latter reactive groups are highly reactive with the former two isocyanate groups.

The polyoxyethylene polyol used in this S is a water-soluble reaction product derived by polymerizing ethylene oxide in the presence of polyfunctional starting compounds such as water, ethylene glycol, glycerol, pentaerythritol and sucrose. It is a thing.

Its molecular weight can be varied over a wide range by adjusting the relative ratio of ethylene oxide monomer to starting compound.

Preferred molecular weights range from about 200 to 20,000°, more preferably from about 600 to 6,000, with a hydroxyl functionality of 8 or less.

The polyoxyethylene polyol is terminated or capped with isocyanate groups by reacting it with a polyisocyanate.

The reaction is carried out in an inert, moisture-free atmosphere, such as a nitrogen atmosphere, at atmospheric pressure and at a temperature of about 00 to 120° C. for about 20 hours.

The reaction time is dependent on temperature and degree of agitation.

The reaction may be carried out under atmospheric conditions if the product is not exposed to excess moisture.

Polyisocyanates used to cap polyoxyethylene polyols include PAPPI-1 (U.

Polyisocyanates and polyisothiocyanates (polyallyl polyisocyanates) shown in S Patent &, 2683730, tolylene diisocyanate, triphenylmethane-4,4',4-triisocyanate, benzene 71,3,5 -triisocyanate, toluene-2,4,6-triisocyanate, diphenyl-2,4,4'-triisocyanate, hexamethylene diisocyanate, xylene diisocyanate,
Chlorophenyl diisocyanate, diphenylmethane-4,4'-diisocyanate, naphthalene-1,5-
Diisocyanate, xylene-α・α′-diisothiocyanate, 3・3′-dimethyl-4・4′-biphenylene diisocyanate, 3・3′-dimethoxy=4・4′
-biphenylene diisocyanate, 2,25,5'-tetramethyl-4,4'-biphenylene diisocyanate, r,
-4,4,4'-methylenebis(phenylisocyanate), (4,4'-sulfonylbis(phenylisocyanate), 4,47-methylenethiorthotolyl isocyanate, ethylene diisocyanate, ethylene diisothiocyanate, and trimethylene diisocyanate) .

If necessary, organic inthiocyanate as mentioned above is included□□
□Mixtures of isocyanates may also be used.

Particularly suitable aromatic diisocyanates and polyisocyanates or mixtures thereof are readily available, highly reactive and relatively low cost.

Killaping of polyoxyethylene polyols can be carried out using stoichiometric amounts of reactants.

However, it is desirable to use an excess of isocyanate to completely cap the polyol.

Therefore, the molar ratio of isocyanate groups to hydroxyl groups used for capping is about 1:4, preferably about 2:3.

For maximum strength, solvent resistance, heat resistance, and compression resistance, a reaction product of incyanate-capped polyoxyethylene polyol is formulated to provide a cross-linked three-dimensional network of polymers.

In order to obtain such an infinite network structure, the reaction components may be formulated according to any of the following methods.

First, if water is the only reactant with the inocyanate group to polymerize in chain form, the reaction product of the isocyanate-canopied polyoxyethylene polyol will vary depending on the composition of the polyol and capping agent.
It must have an average incyanate functionality of about 8 or less.

The second is when the isocyanate-capped polyoxyethylene polyol has only about 2 incyanate functional groups.

In that case, it is advisable to dissolve or disperse in the water or aqueous reactant used a cross-linking agent having two or more effective functionalities and capable of reacting with incyanate.

In this case, the cross-linking agent reacts with the capped polyoxyethylene polyol if mixed during or after the initiation of the reaction.

Alternatively, the crosslinking agent may be incorporated into the polyisocyanate and the mixture may be reacted with water or an aqueous reactant.

A cross-linking agent (dissolved or dispersed) capable of reacting with isocyanate may or may not be used to produce a hydrophilic polyurethane having an infinite cross-linked network structure.

Capped hydrophilic polyoxyethylene polyols can also be made in several other ways.

One useful method is to polymerize ethylene oxide in the presence of polyfunctional hydroxyl-containing starting compounds such as glycerol, trimethylolpropane or trimethylolethane to form polyoxyethylene triol.

The molecular weight of these polymerized triols can vary widely depending on the number of moles of ethylene oxide used in the reaction with the starting compound.

Starting compounds such as pentaerythritol and sucrose similarly treated with ethylene oxide form polymerized polyoxyethylene tetrol and hexol, respectively.

Alternatively, polyols suitable for capping with polyisocyanates can be made from diols, triols, tetrols, hexols and polycarboxylic acids as follows.

Reaction I Useful polyisocyanates can be made, for example, by reaction of excess diisocyanate with a polyol in the following manner.

Fluid Reactions Polyoxyethylene diols, triols, tetrols or hexols can also be capped with isocyanate groups by reacting them with a predetermined amount of polyisocyanate.

This end-capping reaction can be illustrated by the following equation.

Reaction ■ The exact structure of this isocyanate-capped polyoxyethylene polyol is very complex and the simplified description given in the reaction above is for illustrative purposes only.

Blends or mixtures of various polyols and/or polyisocyanates may be used if desired, provided the overall average incyanate functionality of the final reaction product containing the urethane is greater than or equal to 2.

Another method used to make a camped polyoxyethylene polyol reaction product with an average incyanate functionality greater than 2 is to combine a polyoxyethylene glycol with a functionality equal to 2 with a molar excess of diisocyanate. to form an isocyanate-capped polyurethane product (A) having an isocyanate functionality of 2.

Reaction of a polyol such as pentaerythritol having a functionality of 4 with a large molar excess of diisocyanate forms an incyanate capped polyurethane intermediate (B) having an isocyanate functionality of 4.

By blending the two capped products thus prepared, namely (4) and (B), in various molar ratios, the resulting product mixture has an average isocyanate functionality of 2 or more. treatment with an aqueous reactant results in a new improved cross-linked hydrophilic polyurethane as exemplified in this invention.

Furthermore, other monomeric or multimeric polyisocyanate crosslinkers may be used in place of the tetraisocyanate product B).

Trilene-2.4.6 triisocyanate with functionality 3 is an example of a simple monomeric triisocyanate;
This is useful for imparting an average isocyanate functionality of 2 or more.

An example of a multimeric triisocyanate that can be used for the same purpose is shown in reaction ①.

Yet another useful method of the present invention for making cross-linked hydrophilic polyurethane foams comprises inocyanate-capped polyoxyethylene polyols having an average functionality of about 2 or greater prepared as described above. It is to use.

In those cases where the average isocyanate functionality is only about 2, subsequent operations are important.

In such cases, treatment with large amounts of water during foaming produces only substantially linear, soluble thermoplastic foams, which have little practical or commercial utility.

Therefore, if it is necessary to carry out a reaction using such a method, the water or aqueous reagent used must be pretreated and then be treated with a polyfunctional compound that will react with the incyanate end groups in the capped reaction product. Contain a cross-linking agent.

Such cross-linking agents may be dissolved or dispersed in the water or aqueous reactants (i.e., they are compatible with the capped reaction product and are capable of reacting with the isocyanate groups and thus cross-linking during the reaction). It must be applied in such a way as to form an insoluble thermosetting network.

Therefore, in this method, a cross-linking agent that reacts with isocyanate groups is added to water or an aqueous reactant.

After mixing with the incyanate-capped polyoxyethylene polyol reaction product, cross-linking reactions occur after and during the initiation of the reaction.

The presence of a cross-linking agent in the water or aqueous reactant is important when the incyanate-capped reaction product has a functionality of only about 2; If the gender exceeds 2, it is optional.

The water-soluble or water-dispersible cross-linking agent used in the present invention is preferably polyfunctional and reacts with incyanate groups. Polyethyleneimine, glycerol, trimethylolpropane, pentaerythritol, tolylene-2.4°6-triamine, ethylenediamine, aminoethanol, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, ethanolamine, jetanol Amine, hydrazine, triethanolamine, benzene-1, 2, 4-
) ricarboxylic acid, nitrilotriacetic acid, citric acid, and 4
- Substances include, but are not limited to, 41-methylenebis(O-chloroaniline).

The water-soluble or water-dispersible cross-linking agent selected is such that a cross-linked network is created after the reaction has begun or during the course of the reaction.

2 used to create three-dimensional network polymers
The capped polyoxyethylene polyol having an incyanate functionality in excess of 100% must be present in the proportion necessary to ensure the formation of a three-dimensional network.

Accordingly, the amount of polyol in the component to be foamed ranges from about 3 to 100% by weight.

from 0 to about 97% by weight of the components to be reacted with a capped polyoxyethylene polyol having terminal members with isocyanate functionality of 2, i.e., diisocyanates.
It is possible to contain it in an amount of

The maximum amount of diisocyanate used is that amount necessary to cause crosslinking during the reaction and impart the desired properties to the final foam, as opposed to forming a linear polymer structure.

It is also possible, and often desirable, to include small amounts of relatively hydrophobic comonomers in the ethylene oxide-based polymerization products.

Thus, comonomers such as propylene oxide or butylene oxide can be copolymerized into random copolymers, block copolymers, or both, so that the copolymers retain their hydrophilic properties while maintaining the properties required for other applications. That is, it has improved low temperature flexibility, compression resistance, elasticity, etc.

About 40 mole percent, preferably about 25 mole percent or less, of a relatively hydrophobic comonomer may be copolymerized with the ethylene oxide monomer and this product used as a polyol intermediate in the practice of this invention. Again, a foam with a cross-linked hydrophilic network is formed.

Thus, throughout this text, the term 1'polyoxyethylene polyol 11 includes not only homopolymers of ethylene oxide, but also hydrophilic copolymers of ethylene oxide as described above, and all of these polyol derivatives include It has about 2 or more hydroxyl functionalities and an ethylene oxide content of about 60 to 100 mole percent, preferably about 75 mole percent or more.

To react to create a polymer with a cross-linked network, the components containing the isocyanate-capped polyoxyethylene polyol with functionality greater than 2 need only be combined with certain aqueous components.

For simplicity, this isocyanate-capped reactant is hereinafter referred to as the resin reactant.

The aqueous component is water, an aqueous slurry or dispersion, an aqueous emulsion, or an aqueous solution containing water-soluble substances.

For convenience, this aqueous component is referred to herein as the aqueous reactant.

For example, in contrast to typical polyurethane reactions that use catalysts or promoters (in which 1 mole of -NCQ reacts with 1/2 mole of water), the present reaction requires only a predetermined large excess of water. The reaction proceeds.

Approximately 0.5 mol H2o/1 mol NCo group to approximately 2 mol H2
If the resin reactant of the present invention and water are used in a ratio of 0/1 mole of NCO groups, the reactivity will be poor if the surfactant is absent.

A catalyst is required for amounts up to approximately 2 mol H20/1 mol NC0.

Using from about 6.5 mol H20/mol NCO groups to about 390 mol H20/mol NCO groups yields surprisingly good foams whose properties improve according to the number of moles of water added.

Therefore, the effective water content in the aqueous reactant is about 6.5-390
Preferably about 20 to 200 mol 0/NCO groups.

``Available water'' in an aqueous reactant is water that can be used for reaction with a resin reactant, and includes water that forms a reaction layer during the reaction, or water-absorbing or water-binding components or additives, and water that can be used for reaction with a resin reactant. It is not supplementary water for making the agent itself.

The reaction temperature for foaming is adjusted depending on the viscosity of the resin reactant.

The reaction proceeds either batchwise or continuously.

The resin reactant may be poured into the aqueous reactant or both may be brought together simultaneously, for example when applying a spray or bubble method.

Both an internal metered mixing spray device and an external mixing spray device can be used if desired.

The use of large molar excesses of water in the aqueous reactant offers several important advantages and represents an improvement over conventional polyurethane compositions.

For example, in conventional polyurethane compositions, the temperature of the water is carefully adjusted to the theoretical value, usually H20/N in the polyurethane reaction components.
The amount of GO groups had to be controlled to be less than about 2.0 moles.

Such low concentrations of reactants necessitate the use of catalysts to accelerate the polymerization reaction rate, requiring good mixing of reactants and catalyst to ensure a controllable and uniform cytoplasmic product. An intense mixing process is required.

In contrast, the present invention provides a predetermined amount of large excess water, i.e. about 3
Requires 90 mol H,,O/NCO of water.

Using this method, the quality and uniformity of the product is less sensitive to the stringency of metering or mixing of the aqueous reactants, and the use of polymerization reaction catalysts or promoters is optional.

Additionally, conventional polyurethanes suffer from discoloration of the resulting foam due to highly exothermic reactions during the reaction and are limited to a foam thickness of approximately 2.5 crIL or less after a single pass through the spray can. Therefore, there were restrictions on the thickness of the spray finish.

In contrast, because the compositions of the present invention contain excess water as a diluent, the heat of polymerization reaction is moderated and the finished thickness of the foam from a single pass through the spray gun is substantially 2.5 mm.
5 cm or more, and there was no discoloration or overheating of the foam.

Additionally, in conventional foam production, process equipment and spray equipment frequently and extensively use hazardous or flammable organic solvents such as acetone, tricresyl phosphate, and methylene chloride for cleaning and purification. need to be used.

The hydrophilic polyurethane compound of the present invention can be easily cleaned with a simple non-toxic, non-flammable aqueous solution.

Furthermore, conventional polyurethane consists of two symbiotic organic compounds.

However, in the present case, one of the two components is primarily an aqueous solution, thus facilitating metering and mixing during spraying and other process operations, aiding equipment cleaning, and mitigating the heat of reaction. The danger from flames is also reduced and very simple, low cost foam processing equipment can be used.

Since a large amount of water may be present in the aqueous reactant during the reaction, i.e., the present invention is not a 1 mole NGO-water type reaction, various substances can be added to the aqueous reactant that cannot be used in a reaction system with less water. A combination is also possible.

The aqueous reactant may be used at a temperature of about 10° C. to 100° C., if necessary.

Steam can be used as the aqueous component to react the resin reactants.

A quantity of water-soluble or water-dispersible material is added to the aqueous reactant in an amount up to 80% by weight, depending on the material and its weight.

Useful additives to add to aqueous reactants include sound deadeners, flame retardants,
Organic solvents, foaming agents, antistatic agents, antifouling agents, disinfectants,
Insecticides, stabilizers, thickeners, dispersants, resins, polymers,
These include fillers, biostats, and colorants.

By uniformly distributing these materials in the aqueous reactant, a broadly uniform distribution of these materials can be achieved throughout the final product.

If desired, some or all of the above additives may be added to the resin reactant, thereby creating unique and useful additives by the same or different additives present in both or either component. Something is completed.

Since the resins of this invention cross-link by reaction with large but controlled amounts of water, additives may be added to the aqueous reactants.

Therefore, it is desirable to add the additive under wet conditions;
This allows a good and uniform distribution throughout the cross-linked product.

Conversely, the introduction of additives when making conventional polyurethanes requires complete and thorough drying to avoid disrupting the stoichiometry of the system.

Preferably, the materials used with the aqueous reactant include fire retardants or flame retardants, as well as mufflers and vibration reducers.

The particle size and amount of the water-dispersible substance can be easily determined depending on the process equipment or product conditions.

Illustrative materials useful as sound deadening or vibration reducing agents include, for example, granular wood products, rock wool, glass wool, cane lees, straw, cork, blast furnace slap, cinders, expanded vermiculite, perlite, mica, sponge. There are porous materials such as rubber and expanded polystyrene.

Materials that are non-porous and yet have sound-dampening and vibration-reducing properties include materials such as granular silicon oxides, silicates, aluminates, barium sulfate, lead sulfate and lead chloride, and materials such as lead, iron, zinc and tin. There are powdered metals, etc.

Fire retardants or flame retardants useful when added with or alone to aqueous reactants include, for example, zinc borate; calcium carbonate; alum; ferrous sulfate; borax; melamine and boric acid; melamine phosphate; ammonium phosphate; ;
ammonium sulfate; ammonium sulfaminate; halides, especially oxychlorides in combination with titanium oxide and antimony oxide; aluminum hydrate; selenium hydrate; tetrakis(hydroxymethyl)phosphonium chloride; bromoform and triallyl phosphate; phosphoroxy triamide; chlorinated baraffin; tris(2-ethylhexyl) phosphate; tris(2-ethylhexyl) phosphate;
3-dibromopropyl) phosphate: such as triphenyl phosphate and cresyl diphenyl phosphate.

During synthesis, various flame-retardant elements such as halogens, nitrogen and phosphorus can also be incorporated into the backbone structure of the resin reactant.

Systems containing phosphorus in the pentavalent oxidation state as the only flame retardant are particularly effective because they are potentially inexpensive.

Many other fire-retardant or flame-retardant agents and sound-deadening and vibration-reducing agents are well known in the art and are useful in conjunction with the reactants of the present invention when incorporated into the aqueous component.

In making the composite products of the present invention, the resin reactants can be applied in either interwoven or uninterwoven forms, and may be knitted, crocheted, felted, etc. Flexible synthetic or natural fibers, paper, leather, and porous membranes may be applied to the surface or, if desired, adsorbed with resinous reactants.

By contacting the resulting material with water, water-based spray, steam, or water containing moisture, it is possible to transform the material from strong and flexible to hard, from soft to rough, from light to dense. You can make all sorts of products.

The hydrophilic material of the present invention imparts water repellency to the product, but remains breathable, allowing water vapor to pass through and providing great comfort.

Separately, pre-mixed resin reactant/
applying the aqueous reactant composition to textiles and other substrates;
Foaming may be performed at appropriate locations to create a fully bonded composite product.

The step layer is reacted with a hydrophilic composition in advance, the resulting product is cut into sheets, and the sheet is attached to textiles or other substrates using a liquid adhesive, melt adhesive method, or flame adhesive method. It can also be laminated.

The composite products of the invention are very practical and can be used for functional, reinforcing, augmenting, bonding, insulating, partitioning, absorbent, decorative or cushioning purposes, carpet filling, pine tresses, etc. Used in decorative fabrics, kimono linings, upholstery linings, blankets, absorbent padding, wall coverings, acoustic panels, sound deadening materials, protective and/or fireproof surfaces, clothing, shoe linings, separation membranes and filters. .

The composite product of the present invention also provides a removable coating to protect the product during operation and shipping.

Due to the hydrophilic nature of the polyoxyethione polyol reactant, it is possible to impart water vapor permeability to the sponge, making it attractive as a garment upper.

The composite product of the present invention is also useful as a leather substitute.

The hydrophilic foams of the present invention can be resilient, semi-rigid or rigid, and can have essentially open or closed cellular structures.

Moreover, one-shot method (0ne-shot tec
Foams of the present invention can also be made by the following methods: hnique).

To illustrate the difference between the useful processed polyoxyethylene polyols of the present invention and common polyoxypropylene polyols, one mole of polyoxypropylene having an average molecular weight of 3100 and a hydroxy content of 0.95 meq OH/P and a commercially available trilene -2,4-diisocyanate (mixture of 2,4 isomer/2,6 isomer in a ratio of 80/20) 3.0
5 mol was reacted with stirring at room temperature and atmospheric pressure for 6 hours.

An incyanate-capped polyoxypropylene glycol resin was recovered.

Analysis of this resin showed that the actual isocyanate content was 0.90 myIJ equivalent NCO/P.

In contrast, the theoretical isocyanate content was 0.88 meq NCO/f.

When 10 grams of this resin product was mixed with 10 grams of water, the reaction separated into two immiscible layers and gradually turned into a rubbery material with a few large bubbles after about 24 hours.

The resulting product was not suitable for making composite products.

The following examples are illustrative of the practice of the invention and are not intended to limit the invention thereto.

In all cases, all parts and percentages are by weight, unless otherwise indicated.

Example 1 The 2.4 isomer/2.6 The ratio of isomers is about 80/
20, tolylene diisocyanate 522? (3 mol, 6 eq. NC0) was added.

The heat of reaction was kept at 70°C by external cooling with water, and
Continued stirring for hours.

The actual isocyanate content, determined by titration with a standard n-butylamine solution in toluene, is constant 0.
．． 7.9mi! J equivalent NCO/P.

On the other hand, the theoretical value is 0.83 milliequivalent NCO/? Met.

The pale yellow syrup thus produced was found to solidify at about 30-35°C.

It is soluble in toluene and acetone, reacts easily with water, and has the formula:

The n in charcoal is 22 on average.

The theoretical average molecular weight of this resin product is approximately 3615.

Capped resin 2 with NCO content 0.016 equivalents
01 was briefly stirred and reacted with the wastewater 2Of.

The H20/NCQ molar ratio was 73.2.

The reaction mixture was immediately placed on a cotton fabric and the hydrophilic composite product thus obtained had good air permeability, good comfort and excellent moisture retention properties.

The parallel moisture content of the hydrophilic part of this composite product is the relative humidity (
According to RoHo), it was as follows.

That is, it was 5% at 50% R, H, 10% at 75% R, H1, and 30% at 100% R, H.

This is comparable to that found in naturally occurring fibers such as cotton and wool.

Example 2 Pentaerythritol 136'f! A reaction vessel containing tetrol 4131' (1 mole, 4 equivalents of OH) prepared by a sodium methoxide catalyzed reaction of ethylene oxide 4400f with a 2.4 isomer/2.6 isomer ratio of approximately 80 Tolylene diisocyanate) 696P, which is a mixture of 696P and 20%, was added.

The reaction was carried out using a 10 procedure procedure. The actual incyanate content is 0.86 milliequivalent Nco/? (Theoretical value is 0.83 meq NCO/?).

The recovered product is a colorless syrup and has a temperature of about 35-40°C.
It solidified in water, was soluble in toluene and acetone, reacted easily with water, and had the following formula:

In the formula, n has an average value of 22.

The theoretical molecular weight of this resin product is approximately 4832.

19.2f of capped resin product in this example! (0,
016 equivalents of NC0) and water 201 (approximately 1.1 mol)
was reacted with.

Results corresponding to Example 1 were observed.

Furthermore, it was found that the hydrophilic polyurethane penetrated the fibers of the fabric and acted as a reinforcing binder.

The fabric was soft and pliable.

Example 3 Glycerol 92f (1 mol, 3 equivalents of OH) and polyoxyethylene glycol-/1/(M, W, are 1000) 1
00.0? (1 mol, 2 equivalents of OH)
Degassed at 10 Torr for 2 hours.

Tolylene diisocyanate 87M' (5 mol) having a mixture of 2.4 isomers/2.6 isomers in the ratio 80/20 was added to this degassed solution.

The reaction solution was stirred at 60° C. for 4 hours, and the actual isocyanate content reached a constant 2.49 meq NCO/@ (theoretical value 2.54).

The resin product was light orange in color with a density of 1.10 and a viscosity of 13400 cps at 25°C.

The theoretical molecular weight of 31.3 parts (50 mol%) of this resin is 6
15, which has the following equation (idealized):

On the other hand, it was found that 68.7 parts (50 mol%) of this resin had the following average formula.

20 l of water containing 0.5 l of antimony trioxide and 5 g of polyvinyl chloride latex particles has an NCO equivalent content of 0.
．． 016 capped resin product 10P was mixed.

The H20/NCO molar ratio was 125.

The reaction mixture was coated onto a textured polyamide.

The resulting composite product was found to have excellent comfort, flame resistance and moisture balance properties.

Example 4 Example 1 was repeated except that resin reactant 20P was reacted with water and aqueous reactant 201 containing 1.5% by weight soft wood paper pulp.

This product is characterized by a soft open cell structure, is flexible but fairly strong, and was found to have excellent sound absorption properties.

Example 5 Example 4 was repeated except that 20 grams of resin reactant was reacted with an aqueous reactant containing 160 fl of water and 80 grams of vermiculite powder.

The product was semi-flexible and had excellent sound deadening properties.

Example 6 To demonstrate the use of polyoxyethylene polyisocyanate in making products with attractive colors, polyoxyethylene tetraisocyanate 101 made in Example 2 was added with Hansa yellow color.
1 (l) of water containing 0.5 fl (yellow color) was mixed.

A yellow colored composite product was obtained which had the same excellent properties as the product of Example 2.

Example 7 Using polyisocyanate with a functionality of 2 or more to obtain a polyisocyanate foam with higher cross-linking density, better physical properties, lower solubility and greater water stability than polyoxyethylene diisocyanate. To illustrate the case of capping 1000 g of polyoxyethylene glycol (0.25 equivalents of OH) with an average molecular weight of 4000
Gas was drawn off at 10 Torr for 2 hours.

Next, the liquid from which this gas was extracted was heated to 60°C with PAPI90
1 and its name is Upjohn Company (Upjohn).
Polymethylene polyphenylisocyanate 200f (0.5 mol, 1.5 equivalents of NC0) commercially available from Co., Ltd.) was added.

This substance called PAPI901 has approximately 3 isocyanate groups per molecule, and the isocyanate equivalent is 13
It is 3.

When the black reaction solution was stirred at 60° to 70°C for 5 hours, N
It was found that the amount of CO reaches a constant value of 0.835 meq NCO/r (theoretical value is 0.833).

The black syrup-like product thus formed solidified at 45°C to form a brown waxy raw material.

60% to the liquid polyisocyanate 11' thus created.
Addition of 10 f of water using the procedure of Example 1 at 0.degree. C. yielded a tan, soft, flexible, highly hydrophilic product.

Example 8 Illustrates the use of a copolymer of 75% ethylene oxide and 25% propylene oxide and methylene dicyclohexyl diisocyanate to create a triisocyanate that readily reacts with water to create a hydrophilic foam. for,
13.4 A mixture of P (0.1 mol) nottrimethylolpropane and 0.6 @ (0.01 mol) potassium hydroxide was heated to a temperature of 100-180 °C and a pressure of l-4-7 kg/
Stirred in the presence of 2501 cm2 of ethylene oxide.

After 3 hours, the reaction pressure was reduced to 1 atm.

Thereafter, 251' propylene oxide was added to this syrupy product at a temperature of 100-180°C and a pressure of 1.4-5. i
kg/cm2 for 4 hours.

The reaction pressure at 100°C was reduced to 1 atm.

To this brown syrupy product was added 500y of ethylene oxide.

The reaction product was stirred at 100-180°C for 12 hours, and the reaction pressure decreased to 1 atm at 100°C.

The brown oily substance thus formed is heated to 50-100℃ 1
When volatile components are removed at 0 Torr, the amount of hydroxyl is 0.
32 milliequivalent OH/? (Theoretical value is 0.31) A brown white whelk 9782 was produced.

88 to this triol 931f (0.30 equivalents of OH)
．． ([ii' (0.32 mol) dicyclohexylmethane diisocyanate was added.

When this solution was stirred at 60° C. for 8 hours, the amount of NCO reached a constant value of 0.33 milliequivalents/liter (calculated value 0.32).

The triisocyanate product is a bright amber syrup with a viscosity of 12,000 at 25°C (Brookfield).

Union Carbide
0.11 silicone surfactant commercially available from
12 g of water containing 3 g of lead oxide sound absorbing material was added to 10 S' of the above triisocyanate containing the above triisocyanate with thorough mixing.

The product exhibited excellent vibration reduction and sound absorption properties and had similar properties to the product of Example 1.

Example 9 One side of the following substrate was coated with silicone surfactant “L5”.
20" was coated with a resin made from 100 parts by weight of the triisocyanate product of Example 1 containing 1.0 part by weight.

These coated substrates were then immersed in water at 50° C. for 45 seconds, resulting in flexible foam pads.

These were firmly bonded to the substrate in all cases.

Example 10 Except for vigorously mixing 301 resin with 301 water for 3 seconds at 25°C to create a thick cream.
Example 26 was repeated using x24 crIL unlined polypropylene carpet.

This was immediately applied in an even layer over the carpet.

Within 2.5 minutes, the material expanded and cured into a 5 mm thick, free foam rug.

The foam was completely bonded to the carpet.

Example 11 One muslin sheet with a cross section of 25 x 100 crrL
The procedure of Example 26 was repeated except that it was completely covered with resin formulation No. 52 and then immersed in water at 50° C. for 60 seconds.

The 6 mπ thick flexible foam rug thus produced retained a fully bonded muslin fabric in its center.

This product is useful as a dish towel in the same way as cicada leather.

This also includes textile linings for clothing, linings and padding for shoes and boots, various types of filters for gases and liquids,
Lightweight blankets, pine tress covers, underlays, chiffle cloth, diapers, instant rugs, upholstery fabrics, pine tress linings, kimono fabrics, soundproof wall covers, carpets and underlays for ornaments, bathroom and bedroom slippers, etc. is also useful.

Example 12 Tolylene diisocyanate with 860 g (4.95 mol, 90 g equivalent NCO groups/2) of 2.4 isomer/2.6 isomer in a mixing ratio of 80/20 and 100 P (0.735 mol, 2 A slurry of .94 equivalents of OH) with pentaerythritol was stirred for 24 hours.

An orange solution was formed.

To this orange solution was added 10001 (1 mole, 2.0 equivalents of OH) degassed polyoxyethylene glycol.

When these reactants are stirred for 4 hours at about 67°C and then for an additional 16 hours at 25°C, the amount of isocyanate is constant at 2.63 meq NCO groups/2 (theoretical value 2.56).
It became.

The resulting product was orange in color and sticky at 25°C in the form of a syrup containing 31% by weight (42,
5 mol%), and about 69% by weight (57.5 mol%) of the compound of the following formula contains 83% by weight (57.5 mol%).
It has a molecular weight of 2 (theoretical value).

The NCO content of this mixture is 2.63 mi! The J equivalent NCO ratio was 1 loop/1 (theoretical value is 2.56 mequivalent NC
O group/2).

Using the procedure of Example 10, 6.11 g of this resin and 15 g of water were used (the H20/NCO molar ratio was 55.
4) product was made.

Results corresponding to Example 10 were observed.

Example 13 1030P (1 equivalent** amount of OH
) was added with 1 mol of 1,6-dicyanatohexane.

The reaction solution was stirred at 60-70°C for 6 hours, resulting in a constant isocyanate amount of 0.827 meq NGO/g (theoretical value 0.835).

The pale yellow syrupy product thus obtained is 35°
It becomes a wax-like solid at 40° C. and is thought to have the following formula (idealized):

In the formula, n is approximately 25 and the theoretical molecular weight is 3594.

This resin product was reacted with various amounts of water.

This paper shows a method for converting polyols capped with aliphatic diisocyanates into biochemicals with high cross-linking density.

This resin reactant 361 was reacted with 90 g of water.

The H20/NCO molar ratio at this time was the same as in Example 9.

Corresponding results were observed.

However, it was further found that the composite did not change color even after prolonged exposure to sunlight.

Example 14 The products were allowed to react.

This example illustrates one method of converting aliphatic diisocyanate-capped polyols into foams with a high degree of cross-linking.The results are shown in Table II.

To illustrate the use of diisocyanate-capped polyoxyethylene glycol to form foams with cross-linking and three-dimensional network structures, polyamines are used during foaming to create a series of reactive diethylenetriamine (
DETA), water, and a diisocyanate-capped polyoxyethylene glycol resin (
DPG).

The theoretical molecular weight of this resin was 1348, and the actual amount of NCO was 1.42 milliequivalent NCO,/y (theoretical value 1.49).

20 grams of this resin reactant was reacted with 20 liters of water containing 0.0341 DETA.

The H20/NCO molar ratio was 27.

Moreover, the product obtained according to the procedure of Example 9 had properties corresponding to Example 9.

Example 15 To demonstrate the use of diisocyanate-capped polyoxyethylene glycol to make cross-linked three-dimensional foams, a series of reactions were performed using glycerol, water, and diisocyanate-capped polyoxyethylene glycol resin DPG. I did it.

This resin reactant 2Of, water 201 and glycerol 0
．． 062S'.

Further, a composite product was prepared according to the procedure of Example 14, and results corresponding to Example 14 were obtained.

Example 16 To demonstrate the use of diisocyanate-capped polyoxyethylene glycol to make cross-linked three-dimensional foams, the Carlysyl chemical campa = (Car
From Lisle Chemical Co, )=
A series of reactions were carried out using tetrakis mercaptopropionate (commercially available under the trade name 1 Q 43 I+).

201 of this resin reactant, 20 g of water and 0.1 of Q43
Reacted with 2P.

The procedure of Example 10 was used to make the composite product.

Substantially the same results were obtained except that the surfaces of the unbacked carpets listed below were used in sequence.

They are: printed rayon kimono fabrics, nylon furniture fabrics, cotton muslin pine tress linings, printed flexible linen wall covering fabrics, unwoven glass fiber mats, polyester fiber fabrics, microporous Polyolefin sheeting, leather, PVC sheeting for shoes, and blotting paper.

Example 17 In order to demonstrate the simplicity and simplicity of producing foamed products by the method of the invention, the following procedure was carried out.

One liter of the capped polyoxyethylene polyol product mixture obtained in Example 3 at 60°C was added to Pingis Model 181.
N dual nozzle spray gun (Binks M
odel 181Ndual nozzle 5
I put it in one of the play gun's bowls.

Another chamber contained 1 liter of tap water.

Air pressure of 2.8 to 3.5 kg/crA was applied to both chambers.

The aerosol flow produced by spraying both at the same time is directed towards a mobile conveyor belt and fixed at a fixed position.
On the conveyor belt was placed a continuous unlined needle-stitched carpet material having a width of 45 CrIL.

The speed of the conveyor was adjusted as necessary to produce a foam of tightly bonded layers having a thickness of 0.6 CIrL.

Another variation of this operation involves passing the spray-coated carpet under a Teflon-coated doctor blade immediately after contacting the foamable composition with the carpet surface. Ta.

The use of a doctor blade provided good control over the thickness uniformity of the intumescent carpet padding.

Example 18 Dupont Freon
) Example 17 was repeated except that 11 and 12 were added.

In this operation, the curing and drying time of the carpet padding was reduced by passing a conveyor belt holding the coated carpet material through a circulating air oven that had been preheated to approximately 8090°C.

Good results were obtained with or without using a doctor blade.

Example 19 Double Knit The procedure of Example 11 was repeated, except that a polyester fabric was used instead of cotton muslin.

The saturated fabric was passed between rubber-coated pressure nip rolls to reduce the adhered resin to less than 10% by weight, and the resin-laden fabric was passed through a steam chamber to react.

It was found that the composite product obtained in this way has a relatively dense hydrophilic polyurethane network structure that binds the fibers and penetrates into the fabric.

This composite product had good moisture absorbency when made into clothing.

Additionally, the anti-static properties are improved, the whitening phenomenon that occurs due to friction at the creases is improved, and it is less prone to whitening during normal wear compared to a comparison garment made from the same fabric that has not been treated with a hydrophilic resin. It also has good resistance to fabric shedding and unraveling.

Example 20 The operations in Example 17 could be repeated with some modifications as follows.

The isocyanate-capped resin product obtained in Example 3 containing 0.5% by weight of silicone surfactant "L-520" commercially available from Union Carbide was sputtered.
Pore mixing head (5 patter pour
The mixture was placed in one of the holding tanks of a urethane foamer equipped with a mixinghead (mixing head) and an in-tank agitator.

The unit of this machine is Martin Sweet (Mart)
in Sweets) from Flefsamatic (FL)
It is commercially available under the name EXAMATIC.

The second holding tank of this unit contains 80 parts water, 1
5 parts powdered boric acid/1/-/rum (Ca (BO2)
2 6 H20) and 5 parts of B A S F Wyandotte.
An aqueous reactant slurry consisting of a dispersant "Pluronic Air 108 (Pluronic F-108)" commercially available from ) was added.

Conveyor belt unit, total straight distance 18.28m
An endless ring-shaped polypropylene-coated woven release belt runs parallel to the horizontal conveyor.
belt) from 2.5mm to 10CIfL
Alternatively, we created a continuous molding unit that can uniformly adjust the gap within a wider range if necessary.

A commercial edge printed fiberglass kimono fabric was placed printed side down into a conveyor unit at a pass speed of 4.5771/min.

The speed of the release belt was also adjusted to 4.5 m/min, and the distance between the kimono fabric and the release belt was set to 2.5 m/min.

The machine was turned on and the resin/aqueous reactant composition was dispersed onto the top unprinted backside just before entering the calender nip carrying the release belt.

The feed ratio used was resin:aqueous reactant=11.25.

The dispersion speed was exactly that required to completely fill a 2.5 mm thick 0.45 width gap at a maximum pressure of 359'/crA over the length and width of the conveyor belt.

The kimono fabric with resin on the back that comes out of the conveyor unit is elastic, soft, bulky, feels plump to the touch, and has improved resistance to abuse, making it easier to handle. The dimensional retention was also good.

This composite fiber was found to have thermal insulation, flame resistance, and sound absorption properties.

This method has been effective for foam coatings of various thicknesses on flexible substrates other than fiberglass, such as kraft paper and asphalt paper.

Example 21 Example 20 except that the conveyor surface is fed with a closely woven cotton fabric and another roll of the cotton fabric is also fed onto the surface of an endless belt to serve as the top surface of the mobile mold. The operation was repeated.

The resin/water composition of Example 1 was used.

In this example, the resin was strongly bonded to the top and bottom layers of the cotton fabric, resulting in a layered composite sandwich of cotton/hydrophilic foam/cotton at the exit of the conveyor unit.

The thickness of the hydrophilic foam layer was adjusted by adjusting the gap to 3.8 mm.

The density of the foam was approximately 48 kg/m.

After drying to remove excess moisture, the product was particularly useful in making lightweight blankets, pine tress padding, stream application media, and shoe and boot insoles.

Example 22 Tolylene diisocyanate 549P (3.15 mol, 6
．． The resin reactant was made by reacting 3 equivalents of NC0) with triol 6642 (1 mole, 3 equivalents of OH).

The triol at this time was prepared by a catalytic reaction of 1 mole of chrycerol and 13 moles of ethylene oxide with sodium hydroxide.

While stirring the recovered resin reactant 2001 at 60°C,
A silicone surfactant "L-520" 2P, commercially available from Union Carbide, was added.

This resin mixture was then reacted with an aqueous reactant while stirring vigorously.

The aqueous reactant consisted of 50 grams of bentonite clay, 150 grams of powdered melamine phosphate, and 200 grams of water.

The aqueous reactant and resin mixture was immediately poured into a polypropylene coated mold.

After about 5 minutes, a plank with a smooth surface was created in the mold.

After 15 minutes, the planks thus produced were removed from the mold and dried for 3 hours at a vacuum oven width of about 50°C.

Next, one side of the dried plank was coated with a 0.025 mm thick layer of a polyisocyanate-based aromatic diamine two-component curing adhesive.

While the adhesive is sticky, triacetate fiber “Arnel”
Celanese Fibers
Blue Floraking fiber (f
A pattern of locki fibers) was electrostatically deposited on the adhesive.

The coated plank was then placed in an oven and heated to 110° C. for the time required to set the adhesive.

The resulting thick plate was cut into four pieces of 22.8X22.8
It was cut into a board of 1.27m.

The planks thus produced could normally be used as decorative flame-resistant acoustic ceiling panels.

Example 23 Example 3 except that the following amounts of ingredients are used:
Repeat the operations described in.

Ingredients Parts by weight Water 10 Aluminum hydroxide
10 Polyvinylchloride 5 Dohomopolymer powder antimony trioxide 0.5 Resin of Example 3
1° Example 24 Example 23 was repeated except that the following materials were used.

Components Water Melamine Phosphate Calcium Metaborate Resin Weight Parts of Example 3 0 0 0 0 Example 25 Example 23 was repeated except that the following materials were used.

Ingredients water chlorinated polyethylene Calcium tetrafluoroborate antimony trioxide Example 3 resin Weight part 0 0 1.0 0.5 0

Claims (1)

[Claims] 1 (a) A hydrophilic prepolymer consisting of an incyanate-capped polyol obtained by reacting a polyol or a mixture of two or more polyols with a polyisocyanate and having a reactive functionality of more than 2. and at least one of the incyanate-capped polyols constituting the hydrophilic prepolymer has a hydroxyl-terminated hydrophilic ethylene oxide homopolymer component or a polyol with 60% or more of ethylene oxide 100%
% and less than 40% of propylene oxide or butylene oxide with a polyisocyanate; (b) mixing water with said hydrophilic prepolymer; is 6.5-3 per mole of -NGO in the prepolymer.
(e) the group consisting of woven, knitted, crocheted, felted, paper, leather and porous membranes of the hydrophilic prepolymer and water mixture; A method for forming a composite product, comprising: forming a hydrophilic polyurethane foam layer having a cross-linked three-dimensional network structure on the base sheet without adding a foaming agent in contact with a base sheet selected from the above.