JPS5941357A - Polyurethane polymer containing impregnation composition - 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 resin-impregnated porous sheet materials.

More particularly, the present invention relates to resin-impregnated fibrous webs of uniform density throughout that can be further processed into synthetic leather-like sheet materials.

cloth, batts, non-sized paper (water)
Porous sheets impregnated with resin, such as leaves, etc., are well known in the art. These resin-impregnated sheet materials are useful for numerous purposes, including vinyl (
vinyls), structural sheet materials such as conveyor belts, and similar products.

Conventional methods of impregnating certain webs involve impregnating or applying porous materials with polymeric resins such as polyurethane, vinyl resins, or similar materials. Polyurethanes have gained wide acceptance as coating or impregnating compositions because of their ability to vary widely in chemical and physical properties, particularly resilience and chemical resistance.

Several techniques have been used to impregnate porous sheet materials with polymer resins. One such prior art method uses a polymeric resin dissolved in an organic solvent system, and the sheet material is immersed in the bath liquid, after which the solvent is removed from the material. but.

These solvent systems are undesirable because they are often toxic and must be collected or discarded for reuse. These solvent yarns are expensive and do not necessarily provide a desirable product. The reason is,
This is because when the solvent evaporates from the impregnated porous sheet material, the resin tends to migrate resulting in uneven impregnation of the porous sheet material, resulting in uneven impregnation rather than uniform impregnation on the surface of the sheet material. This is because it becomes richer in resin. Aqueous polymer systems have been proposed to alleviate the problems associated with solvent systems. When producing impregnated sheet materials by impregnation with an aqueous polymer solution,
Water must be removed. Furthermore, heating is required and the problem of polymer migration to the impregnated sheet material surface is encountered.

One method of combining a polyurethane solution with a porous substrate involves
The polymer is dissolved in an organic solvent and used as a base material using a needle.
Bunched polyester bat (needle pun)
ched polyester batt). The polymer-substrate assembly is then mixed with a solvent for the polymer and a non-solvent for the polymer that is at least partially miscible with the solvent.
The proboscis is soaked until the layer solidifies into a vesicular structure consisting of interconnected micropores.

The solvent is removed from the coating layer along with the non-solvent, yielding a solvent-free 1) microporous layer.

According to this method, a polyurethane-impregnated fabric foil with somewhat satisfactory properties can be obtained, but it is accompanied by the disadvantages of an organic solvent system.

This disadvantage is particularly associated when utilizing high performance polyurethanes which are relatively toxic and require high boiling point solvents. An example of this method is disclosed in US Pat. No. 3,208,875.

In another method, a dispersion of polyurethane in an organic vehicle was proposed and used to coat porous substrates, as disclosed in US Pat. No. 3,100,721. In this method, two dispersions are strained onto a substrate and then condensed by adding a non-solvent. Although this method was used with some success, it had two major limitations. (1) the dispersion vehicle is substantially organic since only a relatively small amount of non-solvent (preferably water) is required to form the dispersion dV; and (2) the additive is The problem is that the reproducibility of treatment results is difficult because the useful range of nonsolvents is narrow.

Producing composite sheet materials by impregnating porous substrates1
A particularly sophisticated method for reporting
No. 1, incorporated herein by reference. In this system, a porous sheet material is impregnated with an aqueous ionic dispersion of polyurethane and the impregnation is allowed to solidify in the material.

Another method of making an impregnated porous substrate, especially a nonwoven sheet material, ff: 1 Impregnated nonwoven sheet material 1 (Impre
gnated Non-woven 5heet Ma
John McCartne
September 18, 1980 by y + M (4 sa:, h
- & US 11vjWf Publication No. 188.329. This is also incorporated by reference into Tree Specification 1:. In this vfi' venture, we need 21 dollars (need
led) A fibrous batt is impregnated by saturating it with an aqueous dispersion or emulsion of a polymeric resin. This fully impregnated twenty-one dollar batt was brought into contact with the coagulation cuttings.

The polymer resin is coagulated from the aqueous dispersion and deposited inside the second vat.

The batt is dried to form an impregnated fibrous web in which the polymer resin is distributed throughout the batt, the density IW of the web is uniform throughout, and the bulkiness of the web is smaller than the actual density of the web. This impregnated web is characterized by having both filaments coated with polymer resin and uncoated filaments, and by a concentration of polymer resin.

A particular use of the sheet materials disclosed in US Patent Application No. 188,329 is to make leather-like materials. Such a method and composition is known as "Faux Leather Sheet Material J (Si
Mulated Leather 5heat A4a
John McCartney
The name is described in detail in U.S. Patent Application No. 188.330 filed on September 18, 1980. This is also incorporated herein by reference. In the method of this application, the impregnated fibrous body is heated with heat and pressure applied to at least one surface thereof, while
The rain) layer is peeled off on the other side (5plit) layer (
(corresponding to the surface of leather), resulting in a leather-like sheet material. In both of the cited publications, as well as U.S. Pat. No. 4,171,391, the preferred polymers are high performance physical polymers.

It is a polyurethane because of its chemical properties. The present invention is an improvement on these impregnating methods by using additional polymers as the impregnating composition. These additional polymers improve the properties and also allow the properties to be tailored to the 2% constant end use.

The stable aqueous polymer compositions of the present invention are comprised of an aqueous anionic polyurethane dispersion and a -compatible (uniformly mixed) polymer dispersion or emulsion. The emulsion may be substantially neutral T)H or may be anionic or cationic. This polymer composition is useful for impregnating porous substrates to produce composite sheet materials that can be further processed to create simulated leather and the like.

The aqueous ion of the impregnating composition is added to the polyurethane part.
? One configuration is anionic and preferably has carboxylic acid groups covalently attached to the polymer backbone.

When these carboxyl groups are neutralized with an amine, preferably a water-soluble monoamine, they become dilutable with water. Note: Selection of a compound that contains a carboxyl group must be made in accordance with [note]; The reason is that incyanate, a necessary component of all polyurethane systems, generally reacts with carboxyl groups. However, U.S. Pat. No. 3,412,054, which is incorporated herein by reference.
As disclosed in issue.

The 2.2-hydroxymethyl-substituted carboxylic acid can undergo a steric hindrance reaction due to the alkyl group adjacent to the carboxyl group. According to this method, a desired carboxyl-containing polymer is obtained in which the carboxyl groups are neutralized with a tertiary monoamine.

This results in internal quaternary ammonium salts, thus also providing water dilutability.

Suitable carboxylic acids, preferably sterically hindered carboxylic acids, are well known and commercially available. for example,
These can be prepared from aldehydes having at least two hydrogens in the α-position, which are reacted with 2 equivalents of formaldehyde in the presence of a base.
Produces 2-hydroxymethylaldehyde. This aldehyde is then oxidized to the acid by methods known to those skilled in the art. Such an acid is represented by the following structural formula.

CH2'OH ■ R-C-COOH H20H [wherein R represents hydrogen or alkyl having up to 20 carbon atoms, preferably alkyl having up to 8 carbon atoms. ] A preferred acid is 2,2-di(hydroxymethyl)propionic acid. This polymer having a carboxyl group as a side group has characteristics as an anionic polyurethane polymer.

Polyurethanes useful in the practice of this invention are:

More specifically, di- or polyisocyanate;
It involves reaction with a compound having a large number of reactive hydrogens, which is suitable for the production of polyurethanes. Such diincyanates and reactive hydrogen compounds are available in the US q′! jIf 3rd,
No. 412,034 and 4. (Described in more detail in No. 146,729). Moreover, the process for making such polyurethanes is well recognized, as exemplified by the aforementioned patents. According to the present invention, aromatic, aliphatic and Cyclic diisocyanates or mixtures thereof can be utilized in polymer production. Such diisocyanates include, for example.

Toluene-2,4-diincyanate; Toluene-2,
6-diitsocyanate; metaphenylene diisocyanate; biphenylene-4,4'-diisocyanate;
Methylene-bis(4-phenylisocyarj-4); 4
-chloro-1,3-phenylene diisocyanate; naphthylene-1,5-diisocyanate; tetramethylene-1,4-diisocyanate; hexamethylene/-1,6
-diitsyanate; decamethylene-1,10-diincyanate; cyclohexylene-1,4-diisocyanate; methylene-bis(4-cyclohegylylisocyanate); tetrahydronaphthylene diisocyanate;
These include isophorone diisocyanate. Arylene and cycloaliphatic diincyanates are most advantageous in practicing this invention.

Arylene diisocyanate has the following characteristics:
Includes those in which an incyanato group is bonded to an aromatic ring. The most preferred isocyanate is due to its ready availability and its reactivity.

2,4- and 2,6-isomerisms of toluene diisocyanate and mixtures thereof. 4. Alicycloaliphatic diincyanato which can be most advantageously used in the practice of the present invention.
4'-medylene bis (cyclohexyl iso7anathora and isopholene diisocyanate).

Selection of aromatic or aliphatic diisocyanates.

Determined based on the end use of a particular material. As is well recognized by those skilled in the art, aromatic isocyanates can be used if the final product will not be exposed to significant UV radiation.

This is because ultraviolet light tends to cause yellowing of such polymer compositions. on the other hand.

Aliphatic diisonoanates can be used more advantageously in outdoor applications and have less tendency to yellow when exposed to ultraviolet light. Although these principles provide a general basis for selecting the particular incyanate for use, aromatic diisocyanates can be further stabilized by well-known UV stabilizers to improve the final properties of the polyurethane-impregnated sheet material. can be done. Furthermore, to improve the properties of the final product,
Antioxidants may be added in acceptable amounts. Typical antioxidants are thioethers and 4,4'-butyridine bis-meta-
Phenolic antioxidants such as cresol, 2,6-di-t-butyl-p-cresol.

Iso7anates are reacted with compounds with multiple reactive hydrogens such as diols, diamines or triols. When diols or triols are present, they are typically either polyalkylene ethers or polyester polyols.

Polyalkylene ether polyols are the preferred active hydrogen-containing polymeric materials for polyurethane production. The most useful polyglycols have molecular weights of 50 to io, ooo, and the most preferred in the present invention are about 400 to 7.
It is 000. In addition, the flexibility of polyether polyol increases in proportion to its molecular weight as the strength increases.

Examples of polyether polyols include, but are not limited to, polyethylene ether glycol.

Polypropylene ether glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, octamethylene ether glycol,
Polydecamethylene ether glycol, polydodecamethylene ether glycol and mixtures thereof. Polyglycols containing several different groups in their molecular chains, such as the compound HO(CH20C2HjO)nH
In the formula, n is an integer of 2 or more].

, I-'IJol may be a hydroxy-terminated polyester or a hydroxy-terminal polyester.

These can be used in place of or in combination with polyalkylene ether glycols. Examples of such polyesters are those made by reacting acids, esters or acid chlorides with glycols. Suitable glycols include ethylene,
Polymethylene glycols such as propylene, tetramethylene or dimethyl glycols; substituted methylene glycols such as 2,2-dimethyl-1,3-propane diol; cyclic glycols and aromatic glycols such as cyclohexanediol It is. Aliphatic glycols are generally preferred when bulkability is required. These glycols are reacted with aliphatic, cycloaliphatic, or aromatic dihydric carboxylic acids or lower alkyl esters or ester-forming derivatives to form relatively low molecular weight polymers, preferably having melting points below about 70°C. , yielding molecular weights as shown for polyalkylene ether glycols. Acids used to prepare such polyesters include, for example, phthalic acid, maleic acid, succinic acid, adipic acid, speric acid, and sebacic acid.

Terephthalic acid, hexahydrophthalic acid, and alkyl-substituted and halogen-substituted derivatives of these acids. Furthermore, polycaprolactone end-capped with hydroxyl groups can also be used.

One particularly useful polyurethane system is described by Andrea Rusiel entitled ``Crosslinked Polyurethane Dispersions''.
l.

No. 947.544, filed Oct. 2, 1978, is a crosslinked polyurethane system.

As used herein, "ionic dispersant" refers to.

Can form salts with solubilizers. means an ionizable acid or base. These ionic dispersants are amines, preferably water-soluble amines such as triethylamine, tripropylamine, N-ethylpiperidine, etc.;
It is also an acid, preferably a water-soluble acid such as acetate propionic acid, lactic acid, and the like.

The acid or amine is naturally chosen based on the solubilizing side groups on the polymer chain.

For desirable bullet 1.1 behavior, approximately 25% to 8% long chain polyol (
1! IIchi, 700-2,000 eq, wt.
) is necessary.

The degree of elongation and elasticity IW can vary widely from product to product depending on the desired properties of the product.

The polyurethanes useful in the practice of this invention are prepared by reacting a polyol with a molar excess of diisonoanate to form an inner anionate powder. 'l Ij'i -r: ') Generate mer. Although the specific reaction flexibility, response time, and temperature will vary within the range of the specific iso7'anate and polyol content used, we are well aware of these changes. Such reviewers believe that the reactivity of the various components involved may lead to two-color and molecular weight deterioration.
We recognize that a balance of reaction rates is required between '+IJ reactions. Typically, the reaction is carried out at about 0°C to about 120°C with stirring for about 1 to 4 hours.

To give side groups of carhokifur.

The isocyanate-terminated polymer is reacted with a minor mole of dihydroxy acid at 50°C to 120°C for 1 to 4 hours to form an isocyanate-terminated prepolymer.

The acid is 2, for example N-methyl-1,2-pyrrolidone or N-
It is preferable to add N-dimethylformamide as m7[k. The solvent for the separation will typically be the fifth largest component of all components to reduce the degree of Miso medium in the polyurethane composition to a level of 1. The dihydroxy acid was reacted into the polymer sequence (& + 11111 iJ=
The carboxyl group of the diamine is reacted with the amine for about 20 minutes at a temperature of about 58°C to 75"C. Chain extension and dispersion are then achieved by adding it to the water with stirring. jF4 further into the water as an extension All
/Jl may be used. This chain extension involves reaction of the remaining isonoanato groups with water to form urea groups and further polymerize the polymeric material. As a result, Chemistry-M'
Ai! Due to the M'i JJII of the water in the i-tai J1.4, all the isonoanato groups will be reacted. The polyurethane of the present invention is eyelid/dark heat convex plastic 1.
It should be noted that the Lord is the Lord.

That is, by applying cold force to the curing agent from the outside after it is formed (it cannot be made to harden. 10
Enough 1i° of water is used to disperse the polyurethane over a 0.00 cm void. Viscosity depends on the specific dispersed phase +
-rly, can be adjusted according to the specific properties required by the product, all of which are in accordance with the characteristics of the final product. It is noted that no emulsifier or additives are required to stabilize the dispersion.

The constructor is using the polyurethane dispersion of (a) J for final use with LiL, such as color-absorbing, bath-compatible vinyl polymer dispersion, ultraviolet 5.1-t''. I know of a method of modifying by adding a gold perride compound oxidation stabilizer and the like.

The properties of the dispersions produced according to the invention are:

The non-volatile content is expressed by grain size, viscosity measurements and the Kerr-strain relationship for cast film pieces.

Anionic polyurethane dispersions were found to produce a coagulated matrix. Although compatible polymer dispersions or emulsions can be mixed together to create a homogeneous and stable aqueous composition, adding anions to the composition will cause the entire polymer system to coagulate instantly; It was found that uniformly mixed agglomerates of polyurethane polymer and other polymers were formed.

Polymer dispersions or emulsions useful in the present invention are water-imbathable at US state VC and anionic.
Anionic, cationic 1<F or nonionic dispersion or emulsion of a polymer that is compatible with the polyurethane dispersion.

Polymers for such dispersions or emulsions include neobreite polyvinyl chloride, polyacrylate polymers, polyolefin polymers.

Elastic polymers such as polyfluoroolefin polymers can be used.

It should be appreciated that, in accordance with the present invention, polymers other than polyurethane polymers are quite often included in the aqueous compositions.

Neoprene latex useful in the practice of this invention is nonionic. That is, nonion i (b) is emulsified with an emulsifier, and 1■ is approximately 7. This is different from commercially available anionic and cationic neoprenes.

These commercially available products are not useful in the practice of this invention. Commercially supplied anionically emulsified neoprene latexes can be mixed with aqueous anionic polyurethane dispersions.
Since there is only one color, when two paints are mixed together, they coagulate and form a precipitate.

This makes it useless as a bath composition.

On the other hand, nonionic 1t1° Neograin latex is mixed with water-based anionic polyurethane liquid and phase # (Code A4J).
) yields a stable polymer of 1i14. Additionally, these nonionic non-ozolene latexes coagulate under ionic conditions only when combined with polyurethane dispersants. The result is a coagulant consisting of an ioprene polymer and a polyurethane polymer. Unexpectedly (but actually), all the nonionic neoprene coagulates with the anionic polyurethane dispersion.

Produced by polymerization of vinyl chloride, glass transition temperature IW
A polyvinyl chloride resin, which may contain J-bond vinyl+7-ten, may be included as an anionic fine particulate fraction tf&liquid in order to increase the This polyvinyl chloride dispersion was acidified to the level used in the coagulation of polyurethane dispersions, which is recognized to be very stable due to its fine particle size of about 0.2 μm. Sometimes it does not solidify.

In addition to polyvinyl resin dispersions and non-oprene latexes, aqueous polymer dispersions such as polyacrylates and polytetrafluoroethylene.

It is useful as long as the dispersion is compatible with the polyurethane dispersion and produces a stable aqueous resin composition, as long as complete coagulation of the polyurethane and other polymer is achieved to produce a uniform mass. Polymers other than polyurethane polymers can be utilized in the composition at 65% by weight on a solids basis. 6 polymers other than polyurethane polymers
If it exceeds 5% by weight.

Not all of the polymer solidifies and some remains in the aqueous phase.

Polymers other than polyurethane polymers are required to significantly modify the properties of the final product at least 30% by weight on a solids basis.

More specifically, a stable aqueous composition is produced.

The viscosity of the anionic polyurethane/dispersion and the aqueous polymer dispersion or emulsion is approximately 10-5. old) Should be at the level of 0 centivoise.

Polyurethane polymers and other polymers.

Porous sheet material, especially fiber batts, has a fibrous base material with a weight of more than 7% (l Jlj jii%) or more than about 4%. It is impregnated with about 2 (') (1 to 300 weight fractions of flotation-1 drying). Coagulation is carried out by r
(This can be achieved by contacting with an aqueous solution of an ionic medium provided.) Theoretically, (without adhering to such principles), in the case of anionically solubilized polymers, carboxyl group-containing polyurethane 1st year of junior high school
The amine containing 11 atoms is replaced by a hydrogen ion, which converts it back into an anionic carboxol ion. This returns the polymer to its original non-dilutable state. This causes coagulation of the polymer in the matrix. This stable aqueous polymer composition has concentrations ranging from 0.5% to about 7%.
Can be coagulated with 5% acidic acid aqueous solution. Furthermore, this stable aqueous polymer composition is suitable for shipping in the United States. vf 4th, 3 3 2
Coagulation can be effected by the addition of sodium or potassium silicofluoride as described in , No. 710.

To impregnate the batt with a stable aqueous polymer composition, the batt is impregnated with at least 70 wt.
(drying) of the composition at a concentration sufficient to effect dryness. After a first dipping of the vat' into an aqueous emulsion or dispersion, the vat is squeezed to remove air and refilled with a second dipping into a stable aqueous polymer composition.

The aqueous polymer system may be fully immersed within the vat. The knot sufficiently impregnated with the aqueous composition is passed through a wipe roll or the like to remove excess dispersion and/or emulsion on the surface of the impregnated cut.

The batt is then immersed in a bath containing counterions, or heated if the aqueous polymeric composition contains silicofluorides, to solidify the resin in the fibrous structure. It is noteworthy that this coagulation occurs instantaneously, and the coagulum remains stuck within the vat. When drying, the polymer does not move. After solidification, it may be allowed to dry to remove excess water and dry to form an impregnated web. This stable aqueous polymer composition is! +! Regarding the provision of fixed products, U.S. Patent No. 4,
It can also be used in the method described in No. 171, No. 391.

When sufficiently impregnated in accordance with U.S. Pat. , i.e. there are no gaps where air can be retained. After drying, the bat has a new structure. In this structure, the batt has a uniform density throughout and the bulk density of the web is less than the net density of the web. A micrograph of this structure.

Both coated and uncoated filaments as well as resin concentrations
ons) are shown together with voids. Although the bulk density is substantially uniform throughout the thickness of the material, microscopically the structure is non-uniform.

A fully impregnated batt according to the invention.

U.S. Special Issue lvI'1st]. 8 8.3 Can be processed according to No. 3 0.

That is, a fully soaked web or batt is placed on a press and heat and pressure are applied to both sides. The heat and pressure is sufficient to fuse the polymer with itself within the impregnation on the surface of the material, but is insufficient to completely melt the polymer within the sheet material. . By this method, a dense mold is generated from the inside of the moth-resistant cloth sheet material 1 to the outside 1111I surface. Gauge of heated and pressurized sheet material is determined by the pressure exerted during the heating and pressing operation or by pre-spray HL.
Adjustment can be made by inserting ilK spacers or by using a dead load press.

In another method of producing fake leather sheet material from a coagulated material of nonionic neoprene latex and aqueous polyurethane dispersion in a fiber batt, the impregnated batt is heated such that one of the plates forms a silvery layer. The press is placed in a press equipped with cold 11 plates forming the stripping layer on two opposite sides. The characteristics of this simulated leather sheet material are primarily physical in that the density variation is from one side of the sheet material to the opposite side of the sheet material. Preferably, this density is uniform.

One side of this impregnated fiber body forms a grain layer in which the actual density is equal to the bulk density.

1 and 1 as used in this specification refer to the density of the material including voids. What is “actual density”?
It refers to the density of the material t1 that does not include voids, that is, the specific gravity.

This grain surface j1 is very similar to the grain layer of natural leather.

On the opposite side of the sheet material is a surface forming a release layer. This layer has a bulk density lower than the actual density, and preferably has a uniform density distribution throughout the material.

This peel layer is somewhat fibrous and resembles the peel layer of natural leather.

Example 1 100 parts by weight (based on solid content) of an aqueous anionic crosslinked polyurethane dispersion having a solid content concentration of 25% was placed in a suitable container. This polyurethane composition is disclosed in U.S. Patent No. 4,171,
No. 391, implementation 1yll. In this polyurethane dispersion, xoozy part of fumed silica [pP
j4: lm5il 15. IllinoisMi
neral Co., manufactured by Neoprene L
E as atex 115, 1. Du Pon
(Sold by Nemours Company) (A copolymer of chloroprene and methacrylic acid, which was added to a container containing a polyvinyl alcohol dispersant. The pH of this neoprene was approximately 7.

The solid content was 47% by weight. The final pH of the neopre/latex, anionic polyurethane dispersion, and silica formulation was 7.5-8.0. To this mixture, 0.6% teal/filament polyester fiber felt 814, based on the weight of the mixture! i'/m(
24 oz/sq yd). The felt was completely filled with the stable aqueous polymer composition by dipping it into the composition for 15 seconds. This felt is
The aqueous system was impregnated with 600 parts of the same amount. Coagulation was advanced by placing the fully filled vat in a 93°C (200°F) water bath, resulting in complete coagulation of the neoprene and polyurethane. The soaking water was clear. This indicates that a substantial portion, if not all, of the resin remained solidified within the vat.

When this impregnated bat was dried with a radiant heater, the amount of neoprene, polyurethane, and silica impregnated was 125 tons.
t%.

The thickness was 6.3.5++ m (25 (+ mil)) and the bulk density was 05 g/cc.
It was compressed by pressure at 5°C (275°F) to a density of 1.2.

The final simulated leather sheet material had a soft, pliable structure suitable for conveyor belts, dress belts, and similar leather applications.

Example 2 The polyurethane dispersion used was US Pat. No. 4.17.1.
, No. 391, Example 2, and 1.0%
Example 1 was repeated except that 1.2% of sodium silicofluoride and 1.2% of borax were required. After processing under heat and pressure, the product has a durable structure and is suitable for conveyor belts and dress belts.

Example 3 In a suitable container, 100 parts by weight of an aqueous anionic dispersion of vinyl chloride/vinylidene chloride copolymer and 1 oz.
A quantity of polyurethane aqueous anionic dispersion was charged. Vinyl chloride copolymer.

Geon 46 (trademark of IX9, B, G', Goo
Sold by the Drick Company and has a TI of 50
°C1 solid content was 46%. Polyurethane dispersion is 3
2% solids, U.S. Patent No. 4,171,391
Example 1 of No. The total solids content of the final mixture was 38% in water. The mixture formed a stable aqueous composition. 18 wt %, based on the weight of the mixture, was added to the mixture under stirring. This aqueous composition was mixed with 10
Denier/filament fiber weighs 814g/yr2
It was used to impregnate 4 oz/yd 100% polyester felt. The felt was filled with liquid by dipping in the aqueous composition for 15 seconds to achieve complete immersion. The amount of spray to the web in a state where it can be talked about is 60
It was 0chi. The impregnated material was 93'C (20(1'P)
) to solidify the aqueous composition. Solidification occurred simultaneously with heat transfer. The water used for coagulation was clear, indicating that the coagulation was complete and all the vinyl chloride polymer remained in the coagulum. When the impregnated batt was dried with a radiant heater, the dry impregnation of the polymer was 220%. The dried composite was 250 mils thick and had a density of 0.69/7. This complex was plate-shaped. The composite was compacted at 275°F to a density of 1.2. This hot-pressed composite had elasticity and could be bent to follow the contours of objects. Upon cooling to room temperature, the composite became hard with a shiny surface. This composite can be placed in a mold, heated, and molded to make automotive parts, safety sports equipment, etc.

Example 4 40 parts of polytetrafluoroethylene latex having a solids content of 60 parts were mixed with 35 parts of a polyurethane dispersion having a solids content of 30 parts to form a homogeneous mixture having a total homogeneous part of 46 parts. The aforementioned polytetrafluoroethylene aqueous latexes are available under the trademarks Teflon 30, E and L.
Dll Pont de Nemours Compa
It was stabilized with a nonionic surfactant sold by NY. The polyurethane dispersion was according to Example 1 herein. One weight of sodium fluorosilicate was added to the homogeneous mixture.

Upon heating to 54.4°C (approximately 130°P), the mixture solidified and substantially complete polymer coagulation occurred to produce a stiff gel.

The leather-like sheet material produced according to the invention differs from that impregnated with a polyurethane dispersion alone in nine ways along with the impregnated product. That is, they can be engineered to have high tear strength or to have large or small town flexibility.

They can also be made to be embossable to form decorative surfaces at lower temperatures than polyurethane dispersions. However, its physical properties can be maintained. As described above, according to the present invention, a wide range of products can be provided.

Although the invention has been described with respect to particular materials and particular methods, it is not intended to be so limited. ! I' As stated in the claims.

Patent applicant: Knollwood Industries, Inc. Representative: Masahiro Matsui (1 other person)
Continuation Amendment (2) No suffix August 16, 1980 Director of the Patent Office Kazuo Wakasugi 1, Indication of the case 1988 Patent Application No. 127018 2, Title of the invention Impregnated composition containing polyurethane polymer 3, Relationship with the case by the person making the amendment Patent applicant Name: Knollwood Industries, Inc. 4, Agent 5 Date of amendment order Voluntary

Claims (1)

[Scope of Claims] J A stable aqueous polymer comprising an anionic polyurethane dispersion and a compatible polymer component 11 liquid or emulsion in which the polymer is water. TJI product. 2 Composite / Tomura's method of manufacturing 1; in which a porous substrate is coated with an aqueous anionic dispersion of polyurethane polymer and +
immersion in a polymer dispersion or emulsion in which the polymer is water-insoluble; ionically coagulating the polymer dispersion or emulsion that is compatible with the polyurethane; Impregnated complex shaped b'
y, L + and the impregnation/extraction mixture is dried and impregnated. Aft A self 7 wave method consisting of jin. 3. The method according to claim 2. 1. The porous viscous material is a fiber web. 4. The method according to claim 3. The fibrous web is a two-doled fiber batt. 5. The method according to claim 2. The presence of polymers other than polyurethane polymers is 65% by weight or less based on the market solid content of the anionic polyurethane dispersion and the solid content of the neoprene latex. 67 Claim 2: A method according to claim 2. The porous sheet material is fully impregnated when solidified. 7. The method according to claim 4. 8. The method according to claim 7, wherein the two-dold fibrous bat has a bulk density of less than 05 g/d (Oka). .2
5. ? /d. 9. The method according to claim 7. The bulk density of the two-dold fibrous batt is about 0812~
0.4. ! 9/i. 10. The method according to claim 4. The thickness of the two-dold fibrous batt is 0.76 mm (3
Those that are 0 minor or more. 11. The method according to claim 4. The two-dold fiber bond batt consists essentially of non-meltable fibers. 12. The method according to claim 2. The total amount of isomorphic components of the polymer dispersion or emulsion compatible with the aqueous anionic Polyume 77 dispersion is about 5 to 60% by weight. 13. The method according to claim 2. The above polyurethane is crosslinked. 14. The method according to claim 3. The polyurethane polymer and other polymers are present in the web in an impregnation amount of 70% by weight or more based on the weight of the fiber batt. 15. A method according to claim 14. The polyurethane polymer and other polymers are present in a pick-up amount of from about 400 to less than t% by weight based on the weight of the fiber. 16. The method according to claim 15. The polyurethane polymer and other polymers. Said t#! It is present in an amount of about 200 to 300 weight fIt% based on the weight of the fiber batt. 17. A method according to claim 3 H. The density of the impregnated fiber web is about 0.75f7/CC or less. 18. A method according to claim 17. The impregnated fibrous web has a density of about 0.4 to about 0.075 g/
What is cc. 19. Impregnated porous sheet material. Consisting of a porous substrate in which a homogeneous mixture of a coagulated polyurethane anionic dispersion and a coagulated polymer dispersion or emulsion is impregnated. 2. The material according to claim 19. Polymers other than polyurethane polymers are present in an amount of 65% by weight or less based on the weight of polyurethane and neoprene. 2. The material described in claim 19. The porous substrate is a two-doled fiber batt. 2. The material according to claim 210J. a homogeneous mixture of a coagulated polyurethane anionic dispersion and a compatible polymer dispersion or emulsion is distributed throughout the vat so that the impregnated porous material has a uniform density throughout; - the bulk density of the sheet material is less than the actual density of the sheet material, and the sheet material is porous; The impregnated web has filaments coated with polymer resin and uncoated filaments, resulting in a concentration of polymer resin. 2. Claim 22 is a self-listed material. The polyurethane and other polymers are present in an amount of 70% by weight or more based on the weight of the fibrous batt. 2. The material according to claim 23. The polyurethane and other polymers are present at an impregnation level of 400 g/w/g based on the weight of the fibrous batt. 25 A grain layer forming one surface and its cap 1W
and a peeled layer forming two opposite surfaces. In a fake leather sheet material made of a polymer-impregnated fiber body, the polymer is a coagulated anionic polyurethane dispersion. The material has a vf characteristic of being composed of the polyurethane dispersion and a coagulated polymer dispersion that is compatible with the polyurethane dispersion. 2. The material according to claim 25. Other polymers present in an amount of not more than 65% by weight, based on the combined weight of polyurethane and neoprene.