JPS5819319A - Foaming polyurethane composition and foamed body obtained therefrom - 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 frothable thermosetting polyurethane composition, a method for producing a curable foam from the composition, and a method for applying the curable foam to a substrate. , and to cured foamed polyurethanes made from curable foams.

There are a number of methods known in the art for producing polyurethane foams. One manufacturing method is mechanical foaming. Another method is to use chemical blowing agents. Yet another foam manufacturing method involves foaming with 00=tIX gas generated by the reaction of incyanate and water. To date, all chemotactic methods utilized for the production of polyurethane foams have involved the expansion of chemical mixtures containing curable polyurethanes.

This expansion is the result of the isocyanate reacting with the water and producing foam that foams the resin. Alternatively, expansion occurs through the use of volatile blowing agents that expand the urethane into a foamed structure. A typical case of polyurethane foam production utilizes one or more of the above techniques. In almost all cases, some expansion occurs as a result of the 7 ohm foaming in the 00000 rounding. The cause of this is
During the foaming operation, check whether there is sufficient residual moisture in the foam.
Alternatively, it may be present in the atmosphere, causing reactions between the water and the free incyanate, resulting in at least some surface expansion and difficulty in controlling the foam thickness. For example, if you manufacture a round urethane foam sheet with uniform thickness,
It is necessary to use at least two facings between which the foamable composition is introduced to limit the degree of expansion of the polyurethane foam upon curing. Depositing one sheet of face material from a cured 7 Ohm leaves a relatively uniform sheet of polyurethane 7 Ohm, the surface of which absorbs the expanded 7 Ohm and has a thicker skin than the inner cell walls of the foam. . Therefore, when manufacturing polyurethane foam from expandable compound materials, it is difficult to control the thickness of the cured foam, and using mold confinement methods to control the thickness is difficult.
At least one side of the hardened 7 ohm will have a thick skin.

Thus, all of the nine hardened 7 ohms produced by chemical methods up to now had a skin, the internal bubbles were substantially flat, and/or the surface of the product was uneven.

The production of foam from froth is a well-developed technology. Foamed polyurethane foams are widely used as backing foam for carpets and textiles. These foams can contain polyurethane primers and organosilicon surfactants. For example, US Patent No.: %772,2
No. 24 describes a method for producing polyurethane foam from thermoset foams. When an inert gas is mixed into the liquid phase of polyurethane polymer and surfactant, a foam is obtained whose density at ambient pressure is about 45% less than the density of the liquid phase before foaming. This foamy substance was heated to 70°C.
Cured polyurethane foam is obtained by curing at the above temperature. This patent states that a catalyst may be used to cure the mixture and that the catalyst must be practically active in curing the mixture above 70°C.

Additionally, the patent states that substantially no chemical expansion occurs, only thermal expansion occurs during thermal curing.

However, although it is rarely considered, it can be included in the form of this method. As a result, this water reacts with the isocyanate to form a urea bond, liberating the 0000, which causes expansion of the foam foam. However, such expansion is not expected in the prescription. As a result, the resulting 7 ohm urethane is relatively non-uniform. However, the thickness is still more uniform than that obtained using chemical blowing agents. However, while this expansion is acceptable for carpet backing applications, such 7 ohms are unacceptable for many other purposes, as the thickness of the foam foam cannot be controlled during curing. This is a significant problem in applications where it is desired to pack foam into void spaces and control the surface to have a monolithic appearance.

Furthermore, in the mixtures shown in US Pat. No. 3,772,224, the density of the cured foam is necessarily lower than the density of the uncured foam. This is the result of both thermal expansion due to high temperature curing and post-expansion due to the reaction of the entrained water with the isocyanate.

In the present invention, curing is carried out at ambient temperatures that eliminate thermal expansion, using a substantially moisture-free foam that minimizes its h s 00 t production and resulting post-expansion.

Thermosetting urethane resin is a substance that causes crosslinking. As previously discussed, I-urethane 7 ohm undergoes cross-linking and can expand during its manufacture.

The product expands during curing either by the action of a chemical blowing agent or by carbon dioxide generated by reacting incyanate with water which rises during curing and expands the urethane.

In the foam 7 ohm formation method, is there air? Stirred into the urethane forming composition. Such foam polyurethane foams would be expected to actually shrink upon curing due to the natural shrinkage that occurs as a result of cross-linking;
Reacts with the isocyanate present to form a ledger bond,
It then expands to produce carbon dioxide gas. Carbon dioxide gas plays the same role as a chemical blowing agent in that it expands the polyurethane rather than shrinks it.

The degree of expansion of such cellular polyurethane foams obviously depends on the amount of free incyanate and the amount of water available. In most cases, sufficient water is present to react with the isocyanate to a substantial extent and cause a substantial amount of expansion of the oxidation product. This expansion, as pointed out above, limits the field of application of the resulting cured product. The first limitation due to this expansion is that it is difficult to control the final density of the foam. Second, the uniformity of the resulting cured 7 ohm thickness is quite difficult to control. Finally, one more important thing is that
During the curing cycle, there is considerable difficulty in controlling the surface smoothness of the 7 ohm unconfined skin. In this way, the foam mixture that is poured into the container and allowed to harden expands a significant amount.

US Patent No. 4821,130, Active Hydrogen 1
It consists of a polyether polyol terminated with at least 2 moles of ethyleneoxy P per atom (capped), a polyisocyanate-containing material, and a catalyst for producing urethane. Nine flexible polyurethane foams made from mixtures foamed with an inert gas are described. The polyether polyol and polyisocyanate are used in amounts such that the N0OCOH ratio is from about 0.85:1 to about 2.0:1. The flexible polyurethane foam has a density of about 15 Abs/f- or less.

The patent states that the foam does not require the use of volatile blowing agents or silicone oil cell control agents. In the 7-ohm structure of this patent, an inert gas is mechanically introduced into the urethane-forming composition to form a foam, which is then applied to a suitable mold or onto a suitable substrate where it is foamed. The mixture is produced by coagulating into a cellular polyurethane product. According to this patent, conventional foams obtained by mechanically introducing an inert gas into a urethane-forming composition,
It is stated that a very small amount, ie less than about 1% by volume, causes no significant subsequent expansion other than thermal expansion of the inert gas used.

Column 3 of this patent describes various methods for producing foams. These methods include mechanical stirring of air or other inert gas into the mixture of urethane-forming components using a mixer with blades designed to mechanically agitate the air or other inert gas into the mixture. Another method involves feeding a stream consisting of a mixture of urethane-forming components, or separate streams of each urethane-forming component, and a stream of air to a foam-generating mixer. % mixer into a mold or onto a substrate where the foamed composition is thermally cured into a flexible polyurethane.

Yet another method described in this patent is to feed an inert gas and all urethane-forming components other than the catalyst to a foam-generating mixer, and then pass the resulting foam into a mixer, such as a static mixer. mixing with a catalyst and then introducing the foam into a mold or onto a substrate. Examples 1-13 of this patent disclose the use of a vane to foam a polyether polyol and an incyanate-containing compound at high speed for a period of time sufficient to agitate air within the mixture and create foam, typically 2 minutes. Prepare nine honosates and put them in a blender. After the foaming is complete, the catalyst is added and the resulting foam is mixed for an additional 45 seconds and then poured into an open container to cure.

This patent states that it may be desirable to use about 1 to 20 parts by weight of a blowing agent, such as a volatile liquid, or about 0.1 to about 5 parts by weight of water per 100 parts by weight of active hydrogen-containing component. It is stated that.

The use of such blowing agents is inconsistent with the objective of the present invention, which is the desire to minimize post-foaming.

The foamed compositions made in this patent are said to be suitable for application to carpet, paper and natural fiber fabrics.

However, when repeating the procedure for producing a foam and the resulting cured polyurethane according to the procedure described in U.S. Pat. No. 3,821,130 (particularly Example 9 thereof), Protects against curing: ``Conventional foams obtained by mechanically introducing an inert gas into the urethane-forming mixture do not undergo significant expansion after use, except due to thermal expansion of the inert gas.'' , its amount is very small, i.e. less than IX in volume.'' In many applications, for example, foaming occurs at the seam formed when two wall panels are placed in contact with each other. When applying the composition, post-foaming is verified. In such applications, no post-foaming will give the wall an integral appearance.

Another important embodiment of the invention is that the size of the cells forming the surface of the teriourethane foam is approximately equal in size to the size of the cells in the central portion of the polyurethane foam. This means that the cell size of the -urethane foam is almost uniform from surface to surface, with the exception of cells adhesively bonded to and adjacent to the substrate. This uniformity reflects the average uniformity found within the polyurethane foam.

GB 1.333,088 discloses mixing an inert gas with a surfactant-containing liquid polyurethane intermediate composition to foam the intermediate polymer composition to form a stable foam. A method is described for making cellular polyurethanes by forming a polyurethane foam and then mixing a curing agent for a polyurethane intermediate polymer into the foam by electrostatic mixing means. In particular, and then the silicone surfactant is added.
Next, this prairie! - The composition is oozed with a pump. It is sent to the head of an electric mixer where air is mixed into the composition in a specific proportion. The back pressure inside the head is (i 5
Abs/i♂ is adjusted, and the foam is placed in a flexible tube (length 30f
0 and is supplied to the stationary reactor. The foamed prepolymer stream encounters a stream of liquid curing agent.

This deoxidizing agent is described as a polyfunctional amine and alcohol. If polyfunctional alcohol hardeners are used, the usual polyurethane catalysts, such as metal salts such as stannous, tin or lead, or amines are used together with the hardeners. The material coming out of the mixer is poured into a mold and cured at a temperature of 60-75°C.

The resulting nine-cell polyurethane is a solid polyurethane that is hard and is said to be useful as a replacement for solid rubber compositions used, for example, in shoe soles.

However, the foamable composition and the cellular polyurethane obtained therefrom in this British patent are quite different from the foamable composition and foamed product in the present invention.

An important component of the foamable compositions of the present invention is the thixotrope. The British patent does not mention the use of chickentrope. Attempts to produce cellular polyurethane using thixotropes using the procedure described in this British patent were unsuccessful. The composition of the British patent cannot be made thixotropic because only the isocyanate is fed in via a continuous mixer. Chintropy is obtained by adding hyproxyl-containing compounds that react with isocyanates. This causes the isocyanate to perform crosslinking at an early stage. Thus, the thixotrope can no longer effectively perform its intended function.

Cliff 1. The present invention provides foamable thermosetting polyurethane compositions, methods for producing curable foams from the compositions, methods for applying curable foams to substrates, and curable foams. The invention relates to a cured foam-urethane produced from.

Composition The composition of the present invention has a foaming property that, when cured by exposing at least one side of the foam to the atmosphere, results in a cured 7 ohm having a density essentially the same as that of the foam composition. a thermosetting polyurethane-forming composition comprising: (a) a polyol; (b) a polyincyanate; (c) a chirotroping agent; (d) an inert gas; and (e) a polyisocyanate. However, it contains an amount of water that is less than the amount that will cause the composition to cure into a cellular polyurethane having a density that is substantially different from that of the foamed composition.

The composition may optionally contain one or more catalysts, surfactants, hygroscopic substances, fillers, flame retardants, dyes,
The compositions of the present invention are free of chemical blowing agents, which may include pigments or other ingredients that do not introduce significant amounts of moisture into the composition.

In a preferred embodiment of the invention, the composition contains a catalyst as defined below.

The compositions of the present invention are preferably used as three packages: a polyol package containing a polyol, a thixotrope and one or more optional ingredients; an isocyanate containing an isocyanate; and a catalyst channel containing a catalyst and a catalytic solvent to catalyze the urethane production reaction. However, in other embodiments of the invention, the catalyst can be omitted or the polyol Since it can be placed in the arm cage, only two packages are required: the polyol cage and the incyanate package.

An inert gas is added to produce a foam.

Suitable polyols or polyol mixtures useful in the present invention have the following characteristics: an average hydroxyl number as low as possible, no greater than about 300; a viscosity at 25° C. of less than or equal to about 5 ooo centipoise, preferably about 200
Below 0 centipoise: Sensory value is equal to or greater than 2, preferably equal to or greater than 3; Hygroscopicity (% weight increase when a 30f sample is placed in a humidity control room at 26°C for 24 hours in %) ) is about 7 or less, preferably about 1 or less.

Polyols contain active hydrogen-containing components, such as: hydroxyl-terminated polyhydrocarbons (U.S. Pat. No. 2,877,212); hyproxyl-terminated polyformals (U.S. Pat. 870°097);
Fatty acid triglyceride P (U.S. Patent No. 2.833,73)
No. 0 and No. 2,878,601); hydroxy st-terminated preester (U.S. Pat. No. 2,698,838);

No. λ921,915, No. 2,591,884, No. 2
, No. 866.762.

No. 2185Q476, No. 2,602,783, No. 4
No. 729,618.

&77 Milk No. 689, No. 2,811 J493 and No. 4621,166); HyP-roxymethyl-terminated perfluoromethylene (U.S. Pat.
90λ473; British Patent No. 733.6'14); l
Realkylene arylene ether glycols (US Pat. No. 2,808,391); polyalkylene ether triols (US Pat. No. 2,866,774).

Particularly preferred polyhydroxyl-containing materials are polyether polyols obtained by chemical addition of alkyleneoxy P and water with polyhydroxy organic compounds, the alkylene oxides being, for example, ethylene oxide, propylene oxide and mixtures thereof; and # prehydroxy organic compounds are, for example: ethylene glycol, propylene glycol, trimethylene glycol, t,2-f ethylene glycol, 1.3-
Butanediol, 1. =1-f tandiol, 1.5-
Hentanediol, 1,2-hexylene glycol, 1
, 10-decanediol, 1,2-cyclohexanediol, 2-butene-1,4-diol%3-cyclohexene-1,1-')fifinor, 4-methyl-3-
cyclohexene-1,1-'))tanol, 3-methylene-1,5-bentanediol, diethylene glycol, (2-hydroxyethoxy)-1-pronobenol,
4-(2-hydroxyethoxy)-1-butanol, 5
-(2-hydroxypropoxy)-1-pentanol,
1-[2-hydroxyethoxy]-2-hequinanol,
1-(2- and do-4xypropoxy)-2-octatool, 3-allyloxy-1,5-bentanediol, 2-allyloxymethyl-2-methyl-1,3-/'lonozonediol s 3- (0-7'ropenylphenoxy)-1,
2-pro/gundiol, 4゜41-inpropylidenebis(p-phenyleneoxy)jethanol, glycerol, 1,2,6-hexane-triol, 1. ．． 1.
1-trimethylolethane, 1,1.1-)limethylolpronoethane, 3-(2-hydroxypropoxy)1.
2-Zolonogundiol, 2,4-dimethyl-2-(2
- and do-4oxyethoxy)-methylpentanedio-ru 1
, 5:1,1.1-) lis[(2- and doxyethoxyΦshi)methylcouethane, 1,1.1-tris-((2-hydroxyethoxy)methyl]ethane, 1,1.1 - Tris[(2-hydroxypropoxy)methyl]zocynogun, dipropylene glycol, pentaerythritol, sorbitol, CiNIL 9/dose, alpha methyl-glucosy F11 alpha hydroxyalkyl glucoside.

Nozelac resin, phosphoric acid, benzene phosphoric acid, polyphosphoric acid such as tritetraphosphoric acid and tetraerylic acid, ternary condensation products, caprolactone, etc. -Lioxyalkylene?
The alkyleneoxy P used in the production of liols usually has 2 to 4 carbon atoms. The above-mentioned I diols, preferably propylene oxide and mixtures of propylene oxy P and ethylene oxide, can themselves be used as active hydrogen compounds.

The preferred class of polyether polyols used in the present invention is generally represented by the formula a((oo, a
, n), OH).

[wherein B is hydrogen or a polyvalent hydrocarbon group; Hatake is an integer equal to the common valence (e.g. It or 2 to 6
from 2 to about 200, preferably from 15 to about 1
is an integer of 00].

Other active hydrogen-containing materials are polymers of cyclic esters with reduced viscosities of at least about 0.15, preferably from about 0.2 to about 15 and higher. Preferred cyclic ester polymers have a reduced viscosity of about 0.3 to about 1
It has a value of 0. These polymers are homoelimers or copolymers characterized in that they contain units of the following formula: where each R1 is individually hydrogen, alkyl, halo or alkoxy; , X is 1
Must be an integer from 1 to 4, c is an integer from 1 to 4,
bIfiot or an integer of 1, the sum of x+c+b is at least 4 and not greater than 6, and the total number of R1 groups includes methyl, ethyl, isozolobyl, n-butyl, nibutyl, tert-butyl , hexyl, chloro, furomo, iodo, methoxy, ethoxy, n-butoxy, n-hexoxy, 2-etherhexoxy, dodecoxy, etc.].

Each R is advantageously hydrogen, lower alkyl, such as methyl, ethyl, n-propyl, isobutyl, and /l or lower alkoxy, such as methoxy, ethoxy, propoxy% n-cytoxy, and the like; , it is preferred that the total number of carbon atoms in the 8-fold substituent does not exceed 8.

In one embodiment, preferred polymers of cyclic esters contain both the repeating structural unit (above) and units of the following formula: where each R is independently hydrogen, alkyl, cycloalyl, aryl or chloroalkyl, or the two R/ groups together with the ethylene moiety of the oxyethylene group of the unit form a saturated alicyclic hydrocarbon ring having 4 to 8 carbon atoms, preferably 5 to 6 carbon atoms. form, W is 1
or more, preferably an integer from 1 to 10]. Preferably, the repeating unit ■ contains 2 to 12 carbon atoms, examples of R1' groups include esters, ethyl, n-propyl, isopropyl, tert-butyl, hexyls, Fl-decyls , 2-chloroethyl, phenyl, phenethyl, ethylphenyl, cyclopentyl, cyclohexyl, cyclohexyl, etc. V is hydrogen; lower alkyl, such as methyl, ethyl, n-7'
Lopyl, isopropyl; chloroalkyl, e.g. 2-
Preferably, it is chloroethyl or the like.

The repeating unit (I) is connected to the second unit (car)d=nyl via one unit of oxy group (-0-). That is, this linkage does not include a direct bond between two car/nyl groups.

On the other hand, cyclic ester polyester with a relatively low molecular weight! -1 For example, those having a reduced viscosity of about α3 or less are characterized in that the terminal group can be hydroxyl or carboxyl. Cyclic ester polymers having an average molecular weight of about 500 to about 2000 are preferred for use herein.

The preparation of cyclic ester polyi- is described, for example, in U.S. Pat.
．． No. 021.309 to 3.821,317; 3.169.945 and 2.962.524. Briefly, the process comprises reacting a mixture containing at least one cyclic ester monomer with a functional initiator, such as the polyols described above or the polyols described in the patent, and a suitable catalyst, or The catalyst is selected depending on whether an initiator is present or not. Suitable cyclic ester monomers that can be used to prepare cyclic ester polymers are best represented by the following formula: Typical cyclic esters such as monomer, cyto, and trilactone; epsilon-casilolactone, zeta-enanthlactone; monoalkyl delta monolerolactones, such as monomethyl-, monoethyl-, and monohexyl-delta. -/rarolactone, etc. In the absence of an added functional initiator, the polymerization reaction proceeds under operating conditions and in the presence of an anionic cosolvent, as described in U.S. Pat. It is preferable to do it below. When reacting a mixture containing a cyclic ester monomer and a functional initiator having at least one active hydrogen substituent, such as carboxylic or hydroxyl, U.S. Pat.
No. 78.236, No. 890, 208, No. 3,169
, 945 and 's, z 84,417 under the operating conditions covered therein.

Suitable polyol initiators and delicalic acid initiators include those listed in U.S. Pat. It is a caruxyl compound.

Cyclic, ester polymers are also described in US Pat. No. 4,962.
It can also be produced by the method described in No. 524.

Cyclic ester/alkyleneoxy P copolymers also include mixtures containing cyclic ester monomers and alkylene oxide monomers, surfactants such as solid, relatively high molecular weight poly(vinyl stearate) or lauryl methacrylate/vinyl chloride copolymers (30'CK The reduced viscosity in cyclohexane (from about 0.3 to about 1.0) is increased in the presence of an inert, usually liquid, saturated aliphatic hydrocarbon vehicle, such as heptane, and phosphorus pentafluoride as a catalyst. at a temperature of about 80°C,
It can be prepared by reacting for a sufficient period of time to form a cyclic ester/alkylene oxide copolymer.

cyclic ester polymer t-, cyclic ester monomer,
When prepared from mixtures containing small amounts of cyclic comonomers copolymerizable therewith, such as cyclic carnates and cyclic ethers, such as alkylene oxides, ofcetanes, tetrahydropurofurans, etc., the polymer chains of the resulting copolymer products teeth.

l by said repeating linear unit (1) and by a repeating linear unit (2) (which represents the alkylene oxide monomer polymerized therein) and/or by a repeating linear unit corresponding to an additional polymerizable cyclic comonomer in the monomer mixture. ! ! f″4
1I is given. When the comonomer is alkyleneoxy r, the resulting copolymer product contains both repeating linear units (1) and repeating linear units (2) in its coelimer chain. The linkage between the linear unit I and the linear nest position (■) does not include a direct bond of two oxy groups, that is, -0-0-, in other words, the oxy group (-0-0-) of the repeating linear unit -) is bonded to the car 7p-nyl group of the repeating linear unit I or to the alkylene 7 moiety of the second oxyalkylene unit (ID).

The cyclic ester polymers described above are useful in making relatively large colored polyurethane products with strength and elongation of 75i.

As mentioned above, the intended cyclic ester polymer is described by its reduced viscosity value. As is well known in the art, the reduced viscosity value is a measure of the molecular weight of the polymer. The term "reduced viscosity" is the specific viscosity divided by the concentration of the polymer measured in durams of polymer per 100 d of solvent. Here, the specific viscosity is a value obtained by dividing the difference between the viscosity of the solution and the viscosity of the solvent by the viscosity of the solvent. Common organic solvents used herein unless otherwise specified) 100m! The measurements were taken at 30° C. at a concentration of 0.22% of the polymer in the sample.

Another type of active water-containing material useful in the present invention is British Patent No. 063, incorporated herein by reference.
, 222 and US Pat. No. 3,383,351, are polymer/polyol compositions obtained by polymerizing ethylenically unsaturated monomers in polyols. Suitable mono-i- for preparing such compositions include acrylonitrile, -dylchloride, styrene,
Phtadiene, vinylidene, and other ethylenically unsaturated monomers are described in the aforementioned British and US patents. Suitable polyols include those listed above;
There is something described in this British patent and the US patent. The polymer/polyol composition contains from about 1 to about 70% by weight of the monomers polymerized in the polyol, preferably from about 5 to about 50%, and most preferably from about 10 to about 4
It can be contained in an amount of 0% by weight. Such a composition is
By polymerizing the hexamer in a selected polyol at a temperature of 40°C to 150°C in the presence of free radical polymerization catalysts such as peroxides, persulfates, percasenates, per2lates and azo compounds. It is convenient to manufacture. Specifications for this composition and method of manufacture are described in the aforementioned British and US patents. The resulting composition is believed to be a complex mixture including free polyol, free polymer, and grafted polymer/boliol complex. Preparation Example 1 of the British patent is particularly preferred.

Mixtures of the active hydrogen-containing compounds can be used as reactants with polyisocyanates to produce polyurethanes. For example, mixtures of diols such as propylene glycol, polymer/polyol compositions and cyclic ester polymers can be used. Other examples of mixtures include polyether polyol mixtures:
Mixtures of polymers/polymers, diproflene glycols and cyclic ester polymers; mixtures of polyether polylene glycols, and the like.

Preferably, the polyol is Hi! selected from oil, polybutadiene polyol and ethyleneoxy P-terminated polyether polyol.

The polyol has an incyanate index of about 70 to about 1.
50, preferably from about 90 to about 120.

Incyanates suitable for use in the present invention have the following characteristics: liquid between about 20°C and about 40°C; a viscosity of less than about 2000 centidays measured between about 20°C and about 40°C; functionality (number of NOO groups per molecule) equal to or greater than about 2; if a polyol and catalyst are used;
These cure at temperatures of about 5° to about 40°C to a film about 10 mils thick with no residual tack in about 5 hours; mix for about 10 minutes at temperatures of about 30° to about 40°C; and be miscible with polyols.

Incyanate includes any suitable high molecular weight isocyanate composition. This includes one or more such isocyanates.

Examples of high molecular weight isocyanates are described in Geeger et al., US Pat. No. 2)683.730, issued July 31, 1954, the entire disclosure of which is incorporated herein by reference.

Representative high molecular weight isocyanates are of the following formula: i1 [In the formula, R'1 is hydrogen and/or lower alkyl.

Examples of preferred polymeric isocyanates are methyl, ethyl, propyl and butyl.
nl is 2.1 to 4. In the range of Q, Rlx is hydrogen and/l or methyl.

A particularly preferred high molecular weight isocyanate is polymethylene polyphenylisocyanate (i.e., R-
is hydrogen) and is commercially available under the trade name "PAPI".

These are usually supplied in the form of polyisocyanate mixtures having an average NOO functionality of 22 to 3.5, and more commonly about 23 to 3.0. Of course, the terms "high molecular weight incyanate" and "polymethylene polyphenylisocyanate" as used herein are intended to include mixtures containing one or more of such polyisocyanates. It should be appreciated that further details regarding high molecular weight incyanates and their preparation are provided in the aeeger et al. patents cited above. Also suitable for use herein are 2,4- and 2,6-)luene diisocyanates and mixtures thereof. Liquid methylene bis(
Phenyl isocyanate): 4,4'-methylenebis(phenylisocyanate): 214'-
Methylenebis(phenylisocyanate) ;4゜4
Mixtures of '- and 2,4'-methylene bis(phenylisocyanates): crude 4t 4'-methylene bis(phenylisocyanate); isomers of xylene isocyanate and mixtures thereof; isomers of phenylene diisocyanate and mixtures thereof; Each isomer of diisocyanate and its mixture; substituted methylene bis(phenylisocyanate) (wherein the substitution position is, for example, 31 alkoxy, 3
．． 3'-dimethyl and 3,3'-dimethoxy); substituted 2,6-) luene diisocyanates [wherein the substituents are e.g. p-methoxy, p-1-propyl, p-ON, p
-methyl, p-00-alkyl, p-N(alkyl)3
]; Halogenated incyanate, for example monochrome 0.
2,4-) Luene diisocyanate, monochloro 2
, 6-) diisocyanate):) 9 phenyl isocyanate: e.g. 4.4', 4'-) diisocyanate metatriphenyl: 4, 4/ -diisocyanate diphenyloxy r% 4.4'-diisocyanate diphenyl sulfur iP, 4.4'-diisocya $-)-
7 Phenyldisulfide p, 4°4'--physocyanate diphenylethylene-l.

2, +, <'-diisocyanates 7thalene disulfyl r and 4-incyanate phenylsulfonyl icanate: aliphatic isocyanates 29 such as 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate): 1°6-hexamethylene diisocyanate: 1,4-tetramethylene diisocyanate: 1,4-butylene (-2-) isocyanate; diisocyanate cyclohexane; triisocyanate cyclohexane, U.S. Pat. Nos. 3,493,330 and 3.4
70.248; bis(2-
Ethyl incyanate) fumarate; U.S. Patent Nos. 3 and 3
Polyoxyalkylene diisocyanates as described in U.S. Pat.
1,2-bis[p-(2-isocyanatoethyl)phenyl-1-isocyanatemethylethylene as described in US Pat. No. 611; -yenyltetrahydronaphthalene: Hydrogenated -isocyanate, e.g. 2e4-(p-isocyanatecyclohexane)-1-isocyanatecyclohexane+14,4
/-diisocyanate dicyclohexylmethane; 2,3
-bis(difluoro-2))-1,4-diincyanatebutane64,49-bis(2-isocyanatehexafluorozolobyl)diphenyloxy P: as described in U.S.% Pestle No. 3,383.400 Acylated urea polyisocyanates; Biuret I liisocyanates as described in U.S. Pat. No. 3,3503,438; U.S. Pat. No. 3,519
, No. 579.

Prepolymers derived from the following can also be used in the present invention: the diisocyanates and glycols in a molar ratio of about 3:1; the diisocyanates and polyols in a NOO:OH molar ratio. Approximately 7:1;
The above polymeric isocyanate and polydiol are N0OC
OH ratio of about 7:1 or greater.

High molecular weight incyanates are preferred in the present invention.

It has low viscosity due to the following reasons; low vapor pressure; satisfactory compatibility with polyol; flammability due to aromatic structure; high rigidity and strength due to aromatic structure; low price;
More preferred are polymeric isocyanates with low toxicity and high ortho content because they are more miscible with polyols and have better color than high molecular weight incyanates with high para content.

The isocyanate has a NOO:OH molar ratio of about 070:1.50% with the polyol, preferably about 0.9:1.
．． Used in 20.

Any thixotrope can be used in the compositions of the invention. For example, colloidal silica, hydrogenated castor oil, bentonite clay, etc. A preferred thixotrope is hydrogenated castor oil. The amount of thixotrope used is about 1 to about 15 parts, preferably about 2 to about 10 parts per 100 parts of polyol.

If a catalyst is used in the composition, a catalyst with the following zero-order properties is preferred, allowing use of various urethane-forming catalysts: high activity for the reaction between isocyanates and organic hydroxyl groups; low activity towards reactions with; high solubility in polyols;
The viscosity increase of Nornork after mixing the catalyst into the foam can be delayed; at temperatures of about 5 to about 40°C the catalytic effect is delayed for a short time (delay time of about 30 seconds to about 120 seconds). preferred): high solubility in the diluent.

These catalysts include di-alkyltin caloxylates such as dibutyltin dilaurate, diralate, diacetate, di-2-ethylhexoate, etc.; dimethyltin dithiolaurate, stannous Octoate, stannous oleate, potassium octoate,
Potassium acetate, phenylmercury sotetrabionate, iron
Acetyl heptatonate, copper acetylacetonate, zinc octoate, zinc acetate, conolate acetate, manganese acetate, isopropyl titanate, triacryl isopropyl titanate, lead naphthanate, conolate naphthanate, bismuth nitrate, iron chloride 0 , sodium silicate, alkenium acetylacetonate, zinc acetylacetonate, nickel (ID.

Acetylacetonate, methyl titanate and zinc stearate.

Particularly effective catalysts are those with tin-sulfur bonds, such as dibutyltinsulfyP, and dialkyltin dithiodialkylidene diesters of the formula: [where R1 and Rs are independently 1 carbon atom or about 20
alkyl, arylalkyl and alkylaryl, b d is an integer from 1 to 8, and d' is an integer from 1 to 10].

In the above formula, preferably R snow and Rs are carbon atoms 1 to 8
alkyl, and d is an integer from 1 to 4.

Tertiary amines can also be used as catalysts. These tertiary amines should be represented by the following formula [in the formula, s ”l
M B? and 几 and 几 independently represent aryl, alkylaryl, arylalkyl, alkyl, cycloalkyl, and alkenyl groups (wherein each of aryl, alkylaryl, and arylalkyl represents about 6 to about 2
0 carbon atoms, alkyl groups contain about 6 to 18 carbon atoms, alkenyl groups about 3 to 18 carbon atoms) and 1 to 3 nitrogen atoms. selected from the group consisting of 5- and 6-membered heterocyclic groups, where 1' is an integer from 5 to 5].

几■ or an optionally substituted monofunctional hydrocarbon group, selected from 9° and at least □ of RhR16 or R11
selected from 1 to 0.alkyl, 0.3 to 0.hydroxyalkyl, and 6 is O to 10),
Examples of optionally substituted hydrocarbon groups include morpholinoalkyl; piperi-cutualkyl, alkylaminoalkyl,
hydroxyalkyl; alkoxyalkyl and alkylcarzenyloxyalkyl. These triazine-containing compounds are known in the art, as shown, for example, in US Pat. No. 884,917.

Amines suitable for use in the present invention include nitriethylenediamine, N,N-dimethylcyclohexylamine, triethylamine, N-ethylmorpholine, N-meth2*2-dialkyl-1 , 3-oxazolidine, N-alkylbiherazine, N,N'-dialkylpiperazine, tetramethyl-1,3-butanediamine, dimethylethanolamine, bis-dimethylaminodiethyl ether, it/zole, N , N#,
N#-tris(3-dimethylaminopropyl)-8-hexahydrotriazine.

Also, mixtures of the aforementioned catalysts can also be used.

The catalyst is 0.001% by weight based on the weight of the polyol.
It is used in a small amount to 0.50% by weight.

The use of the catalyst depends on the temperature of the foam into which the catalyst is injected, the amount and alkalinity of filler present, the reactivity of the polyol, and the temperature of the substrate to which the foam is applied. for example,
When the temperature of the foam is about 4θ° C. and the temperature of the substrate (e.g., a wall panel) is about 25° C., a catalyst such as a dialkyltin dithioalkylidene diester is only used in an amount of about 0.1 part. If the foam temperature is lower than about 40°C and the substrate temperature is lower than about 25°C, use more than 0.1 part by weight and as much as 0.50 parts by weight of catalyst per 100 parts of polyol. I get something.

Catalysts are generally added in a solvent. This solvent can be selected from a wide variety of substances. The solvent may be, for example, a preol or polyamine as described above, or a plasticizer such as a surfactant, a hydroxide, or a dialkyl phthalate as described below.Generally, the catalyst is present in an amount of from about 10 to about 100 parts per part of catalyst. dissolved in a solvent.

Mix the catalyst with a solvent and add this mixture to the foam foam;
Can be mixed with foam foam. When the catalyst is added in this manner, it is dissolved in a solvent. This method is the preferred method for adding catalyst. Alternatively, bismuth- and silicate-bearing catalysts, especially Bl (NOI
) A relatively large amount of a polyol-insoluble catalyst, such as Na18i01 and Na18i01, is mixed into the polyol, followed by simple glycols such as ethylene glycol, zotetrapyrene glycol, or glycerin, or mixtures thereof. In addition, it can be solubilized. Since the catalyst is insoluble in the polyol, no gelation occurs in the foaming hose. If the catalyst is dissolved in the polyol, and such a large amount is added to the polyol cage, it is safe to assume that gelation will occur in the processing equipment and pack it.

The compositions of the invention may optionally contain one or more of the following ingredients: surfactants, moisture removers,
Fillers, flame retardants, dyes, pigments, etc.

Preferred surfactants are organosilicon copolymers, such as those described in US Pat. Nos. 4,772,224 and 4,022,722.

Other organosilicon surfactants are partially crosslinked siloxane-polyoxyalkylene block copolymers and mixtures thereof, in which the siloxane blocks and polyoxyalkylene blocks are joined by silicon-carbon or silicon-oxygen-carbon bonds. The siloxane blocks are comprised of hydrocarbon-siloxane groups and have an average valency of at least 2 silicon atoms per block attached to the bonds.

At least a portion of the polyoxyalkylene blocks consist of oxyalkylene groups and are polyvalent, ie, the carbons per block attached to the bonds and the oxygens attached to the carbons have a valence of at least 2. The remaining polyoxyalkylene blocks consist of monovalent oxyalkylene groups 9, ie, the carbon or oxygen bonded to the carbon has only one valence per block bonded to the bond.

Additionally, conventional organopolycloxane polyoxyalkyne block copolymers, such as U.S. Patent No. λ83
No. 4,748, No. 2,846,458, No. 2.868
゜r24, No. 2,917,480 and No. 3.95
7.901 can be used.

Other surfactants that can be used in the present invention include macromolecular monolinear non-hydrolyzable (λB)n siloquinane-polyoxysilane, as described in U.S. Pat. No. 4,022,722, incorporated herein by reference. It is an alkylene block copolymer.

These compounds described in U.S. Pat. cl is an integer of at least 6; f is an integer of at least 4; t is an integer of at least 4; Represents a divalent organic group bonded to a polyoxyalkylene block, provided that one Y in the formula
each siloxane block has an average molecular weight of about 500 to about 10,000.
:The average molecular weight of each polyoxyalkylene block is approximately 3
00 to about 10,000: the siloxane block comprises from about 20 to about 50% by weight of the copolymer; the polyoxyalkidine block comprises from about 80 to about 50% by weight of the copolymer; and the average molecular weight of the block copolymer is at least about 30,000.

Surfactant d, #lJ all 100 parts per 1 to about 1
0, preferably from about 1 to about 411 parts.

Hygroscopic materials that can be used in the present invention include: molecular sieves of the zeolite type, silicates such as ethyl silicate, oxazolidines, cal-diimides, inorganic materials such as sulfuric acid. Magnesium, calcium sulfate, calcium chloride and any other inorganic salts that can be hydrated with water. Molecular sieves are preferred, and the hygroscopic material is polyol 10G
It can be used in amounts of about 1 to about 15 parts by weight, preferably about 3 to about 7 parts by weight.

Suitable fillers that can be used include, for example, barium sulfate,
These include calcium carbonate and carmina trihydrate. Fillers with low hygroscopicity are preferred. In the present invention, fillers can have a catalytic effect.

Fillers can be used in amounts up to about 250 parts by weight per 100 parts of polyol, preferably from about 100 to about 200 parts by weight.

If it is desired to produce a flame retardant cured urethane foam, flame retardant compounds can be added to the composition. Suitable flame retardants include alumina trihydrate, phosphorus-containing compounds such as tricresyl phosphate, and halogenated phosphates, including tris(dichlorozorobyl) phosphate.

In the practice of this invention, the density of the uncured foam is approximately 18
45 tbs/ft", the density of the foam is approximately equal to the density of the cellular polyurethane being formed. The selection of the components of the composition ensures that the amount of water in the composition is approximately equal to the density of the cellular polyurethane formed. The compositions of the present invention, which are carried out in less than an amount resulting in a cellular polyurethane having a density not essentially the same as the density of the foam composition, form a cellular polyurethane with essentially no post-foaming.

The moisture content of the composition can be adjusted to be as low as possible by ensuring that each component does not introduce significant amounts of moisture into the composition.

This is achieved, for example, by choosing a polyol with the lowest possible average hydroxyl number (low hygroscopicity) and by choosing an incyanate that can cure with the polyol in as short a time as possible. A urethane forming catalyst can be added to speed up the curing rate. If a high hydroxyl number or highly hygroscopic polyol is selected, a hygroscopic material can be added to the composition. Thus, it can be seen that by relating the components, a composition with the lowest water content is obtained.

Method: Curable foam produced by mixing air or other gaseous substances with a polyol (containing a thixotrope and one or more optional components) and incyanate. If a catalyst is used. Preferably, the catalyst is added to a foam prepared by mixing the gas, the preol (including the thixotrope and one or more optional components), and the isocyanate.

External gaseous substances suitable for use in the present invention include any gaseous element, compound, or mixture thereof that exists in the gaseous state at standard conditions of temperature and pressure, i.e. 25° C. and 1 atm, such as helium, nitrogen, etc. , oxygen, carbon dioxide, and air, or mixtures thereof, provided that they do not react with, or are rarely soluble in, any of the urethane-forming components. Dry nitrogen or dry air are the preferred gases.

In particular, in the production of curable 7 ohms, isocyanates, thixotropic polyols, and
1 t@Makyusha or more optional ingredients are placed separately in predetermined amounts into a mixer, preferably a SKO or Oaks continuous mixer, totaling 9. The gaseous material under pressure can be metered into the polyol stream, the isocyanate stream, or both, or directly into the mixer containing the polyurethane forming components. High density foam at atmospheric pressure or higher, approx.
The foam is generated in a mixer under a pressure of from about 150 psi to about 150 psi. The foam is then fed from the mixer to a feed tube. As the foam progresses toward the outlet of the feed tube and the pressure decreases, the entrained air bubbles expand and the bubbles increase in volume (ie, become less dense).

The catalyst is injected into the foam at a point downstream of the feed pipe and the foam/
The catalytic foam is preferably dispersed through an in-line mixer and the catalyzed foam is then delivered onto the substrate.

In order to more clearly describe the many embodiments of the method of the invention, FIG. Second
Let's talk about the diagram.

In discussing FIGS. 1 and 2, the description is purely illustrative and in no way intended to be limiting.It will be appreciated by those skilled in the art to which this invention pertains that without departing from the spirit and scope of the invention. , many structural modifications and various implementations will occur.

In the method of the present invention, polyol packages (polyol containers hereinafter and for the purpose of this discussion will be referred to as "polyols") contained in containers 29 and 30 are used in containers 2 and 30.
The incyanate contained in 8 and the catalyst contained in vessel 27 are sent to each mixer by pumps 34, 33 and 32, respectively. These four engines are driven by a motor 35. One motor is used to drive each pump, so two containers
The material from 7.2 g + 29 and 30 will definitely be in fixed proportions. This is because all pumps are positive displacement type.
The polyol is drawn from the container 29, 30 by a pump 34 whose output is determined by the speed of the drive motor and is pumped at a constant speed. This pump can be a Moyno pump (manufactured by Robis & Meyer), and the displacement rate can be varied from 100 to about 100 ml per minute by varying the drive speed and by adjusting each component. 20
Of”l or more can be changed.

The incyanate is withdrawn from the tank 28 through a line 55 and optionally passed through a filter 57 for removing impurities and already reacted substances. The pump 33 can be a gear pump manufactured by Zenith, and its output 30 to 60 t/min or more is determined by the speed of the drive motor 35. This discharge is carried out in lines 59, 61 and 6.
4 and valve 62.

At several times during the foam generation process, it is desirable to stop the isocyanate flow without interrupting the flow of other systems, and this can be done in valve 62.66 and line 67.6S. When the flow through valve 62 is increased, pump 3
The pressure expansion of the discharge of 3 reaches 100100 p, which opens the check valve 66 and allows fluid to flow into the pipe [65]. This fluid then passes through the filter 57? It recirculates through pump 33 until drive motor 35 is stopped or valve 62 is reopened.

Similarly, catalyst is withdrawn from tank 27 through line 77 and metered pumped by single piston pump 32. Valve 8
1 can be closed to recirculate the exhaust flow from about 0.5 to about 5 f/min, which flows through lines 84 and 83 when the exhaust pressure automatically opens check valve 85.

Chemical supply tanks 27, 28, 29, and 30 are pressurized to minimize the possibility of contamination and to reduce power output requirements of motor 35. This moves the gas from tank l to 1
This is achieved by introducing from line 20 into the top of each tank via a set of pressure reducing valves 5.9 and control valves 11. Thus, the chemical fluid is at the same pressure as line 20, approximately 60 pal
, the fluid can easily flow through the pipes to each pump,
Thus, minimizing the possibility of cavitation and inaccurate metering.

Foam generation is carried out mechanically with a mixer 47 driven by a motor 48, from an air line tank l, which is connected to valves 5, 18, 70 and 73, and lines 17, 68, so that a constant flow rate is maintained. The air and polyol extracted through 69, 72 and 74 are introduced into the mixer through line 46. Incyanate is added through line 64 and the polyol and air are mixed and whipped into a foam. The diameter of conduit 64 is kept small to maintain high fluid velocities and to minimize reactive material backpressure that could cause blockages.

The urethane foam is sent via line 75 to catalyst injector 76 . The catalyst enters the catalyst injector via line 82.

The diameter of conduit 82 is reduced to minimize the elastic effects of the fluid entry conduit and to increase the consistency of system operation.

The catalyst-containing foam is sent to a static mixer 86 to mix the noble ingredients into a homogeneous material state. It can be applied directly to the curable foam substrate, or it can be applied with an applicator 87, the purpose of which is to distribute the foam into the desired shape.

In particular, with reference to FIG. 1, container 1 is a source of dry gaseous material, preferably dry nitrogen or dry air. Gas from vessel 1 enters lines 2 and 4 at a pressure of approximately 2700 psig.
and then through the pressure reducing valve 5 where approximately 200 p.
Depressurized to mig. A portion of the gas passes through lines 6 and 7 to the pressure reducing valve 9, whereby the pressure is reduced to approximately 60 to 70 °C.
psigt. The other portion of the gas passes through lines 6 and 17 to pressure reducing valve 18, which reduces the pressure to about 100 to 150 psig. Pressure switch 8 monitors the gas supply level. Gauge 3 displays the pressure of the gas.

The gas from the pressure reducing valve 9 passes through the conduit 10 to the directional control valve 11
and then passes through conduits 12 and 20; a portion passes through conduit 26
a portion passes through line 25 to exert pressure on the contents of vessel 28, and a portion passes through lines 21, 22 to exert pressure on the contents of vessel 29. and a portion passes through the conduits 21 and 24 to the container 30.
exert pressure on the contents of the

In a preferred embodiment, the gas flows from valve 11 to line 12.1.
4 and through pressure reducing valve 15, where it is reduced to approximately 5 psi and exerts pressure on the contents of vessel 93 through line 16, where the contents of vessel 93 emerge from the wash or 7 lashing solvent.

When the process starts, the polyol in vessels 29 and/or 30, the incyanate in vessel 28 and the vessel 27
The catalyst within is pumped by pumps 34, 33 and 32, respectively, to each mixer driven by a motor 35. If! At f, the polyol in containers 29, 30 passes through lines 36 and 31, respectively, then lines 37, 3B and 41, via pump 34 and line 42, and then to motor 4.
This leads to the puller 47 which is driven by 8. The polyols in container 29.30 can be used simultaneously or sequentially. In a preferred embodiment, the container 29,30 includes floating pistons 52 and 53, which serve to completely empty the container, especially when using viscous polyols; The piston collects the polyol supply when the container is emptied, so the second
Flow can begin from the container. Pressure switch 54 detects the pressure difference and indicates that both tanks are empty.

Container 40 is a reserve tank for Prior. This is 17
It is a 4 gallon bladder accumulator. When the pumping process is started, polyol from either container flows into accumulator 40 and fills it. When both containers 29 and 30 are empty of polyol, pressure switch 54 is actuated to stop the The polyol flows under reduced pressure to the inlet 34 and enters the mixer 47 to prevent voiding during shutdown, as described above.

The isocyanate is passed from vessel 28 through lines 55, 56, optionally through filter 57, through line 58 to pump 33, through lines 59 and 61, through valve 62 and through lines 3 and 64 to the mixer. When choosing this optional system, it is sometimes desirable to stop the flow of incyanate without stopping the flow of the other components of the system.
Flow is stopped by closing valve 62, which causes the pump 33 discharge pressure to reach approximately 100 psi, which causes valve 66 to open and pass inocyanate to line 65, which is then passed through filter 57 and pump 33.
through until motor 35 is stopped or valve 62 is re-opened.

Air is supplied to mixer 47 to produce foam. Air flows from tank 1 to pipes 2 and 4, valve 5, pipes 6 and 17, pressure regulator 18, pipes 68 and 69, directional control valve 70, pipe 7
2, through a flow regulator 73 and a conduit 74, where it meets the polyol from conduit 42 at T-joint 43, and then both substances reach mixer 47 via conduit 46. At the same time, isocyanate flows into mixer 47 as described above. The foam produced is sent from mixer 47 through line 75 to catalyst injector 76 . The catalyst is transferred from the container 27 to the conduit 77.
and 78, pump 32, lines 79 and 80, valve 81 and line 82 to catalyst injector 76. In any embodiment, the catalyst closes valve 81 and the resulting pressure automatically opens valve 85 to direct flow between valve 85 and lines 83 and 7.
8, it can be recirculated.

A preferred catalyst injector is described in Japanese Patent Application No. 56-90993, which is an apparatus for producing an admixture of chemical components, comprising an elongated nousing, the housing having: (a) a housing extending through the housing; (b) a tube having at least one inlet means for supplying at least one component to the limb canal, from which the component flows to an outlet means at the other end of the limb canal; an inlet means for supplying at least one component that reacts with one or more of the components of (1) or catalyzes the reaction of two or more of the components of (■); an inlet means in communication with an annular groove in the conical member receiving the annular groove; and (a) a plurality of inlet means in the conical member for directing the component from the annular groove into a flow of the component in the cough tract. a housing containing means t for dispensing into the grooves of.

A static mixer 86 mixes the catalyst and foam.

The foam can then be applied onto the substrate by applicator 87. Applicator 87 can position the foam into the desired shape.

In any embodiment of the invention, the solvent may be used for cleaning the following: mixer 47; line 64 transporting material from the isocyanate container; mixer 47
Conduit 75 transporting foam from: catalyst injector 76
mixer 86; and applicator 87. Air is routed from regulator 11 to pipe 12, T-joint 19, and pipe 14.
The pressure is reduced by regulator 15 to the required approximately 5 psi through line 16 to vessel 93, exerting pressure on the contents of vessel 93 and thus pressurizing the solvent therein.

To prepare the solvent cleaning system for use, air from the pipe 101 is passed through the pipe 104 by the valve 103, filling the air 1i194 in the cylinder 105 and pressurizing it.
has an inner diameter of 2 inches), which causes piston rod assembly 95 to move and increase the volume of cavity 96 within cylinder 108 (cylinder 108 has an inner diameter of 4 inches).

When the volume increases in this way, the solvent flows through the pipe 88 and the check valve 9.
0 and is extracted through line 107 to fill cavity 96. This completes the system cleaning preparation. When it is desired to clean the system, valve 103 is electrically driven to change its position, and valve 1
Air from 01 now passes through conduit 102 to cavity 97.
Fill and pressurize. The pressure exerted on 97 causes the volume of cavity 96 to decrease, so that the solvent therein passes through line 109, check valve 110, line 111.64 to mixer 47 and into the mixer. cleans the mixer by washing out the reactive substances therein and finally discharges the downstream components present through the applicator 87. Suitable solvents are halogenated hydrocarbons, such as methylene chloride, or ketones, such as acetone, methylethylketoy.

The total travel of piston rod assembly 95 between end points is 3 inches.

FIG. 2 is a side view of the container shown as 29.30 in FIG. have This top can be removed and the polyol added thereto. A Jll-ring 205 seals to prevent material from leaking between the top and @ part of the cylinder. Air population 203
Air under pressure enters through and exerts pressure on piston 206, forcing it against the contents of the container. This allows the contents to pass from the suction tube 202 to the system via the outlet 204. When the contents of the cylinder are emptied, the piston 206 is in position, sealing the suction tube 202 and sealing the system.

In the process of the present invention, it has been found that incorporating the catalyst into the foam and mixing it with the foam in a mixer significantly reduces the curing time of the foam, making this a preferred method of catalyst addition. represent. When using this technique to catalyze foam, most of the curing occurs in about 90 seconds for bulk and about 30 to about 50 minutes for thin layers. Moreover, besides promoting hardening, the addition of cough catalyst eliminates gelation or high viscosity of the hose walls, i.e. the formation of gelled substances,
Foam in the hose preserves pot life. The hose transports the foam from the building mixer to the substrate, and the foam is applied onto the substrate. Additionally, the addition of catalyst has been shown to minimize post-expansion of the foam after it is spread onto a substrate, such as a seam formed by the contact of two wall panels. Ta. Incyanate reacts with moisture and 00. When this occurs, post-foaming occurs, resulting in an uneven surface.

As mentioned above, the addition of a catalyst accelerates curing as the foam is passed through the hose and applied to the substrate, so if polyols with sufficiently low hygroscopicity are used, post-foaming can be avoided. essentially disappear.

Adding a polyol-soluble catalyst to the polyol package results in the formation of a viscous, or gelled, material on the walls of the hose, which results in the formation of a viscous, i.e. gelled, material on the walls of the hose, resulting in a viscous reaction that varies depending on the amount of catalyst added and after a relatively short working time of 30 to 60 minutes. Found that even the hose needed to be replaced.

Moreover, when adding a polyol-insoluble catalyst to the polyol package, the catalyst can be solubilized by adding Easily Hiko Glycol to the foam injected into the foam application hose prior to glycol addition. It was found that no gelation could occur. This represents another embodiment of the invention.

The method of the present invention is carried out at ambient temperatures of about 0 to about 40°C.

The foam from the construction hose is structurally stable and can be easily applied at ambient temperatures. The consistency of the foam is very close to that of shaving cream in an aerosol formulation.

The uncured foam has a density of about 18 to about 45+bV't.
TS te, approx. 20 ft, approx. 351D/ft", size.

The density of the foam is approximately equal to that of a cured 7 ohm.

The cell size of the uncured catalyzed foam depends on, for example: foam density; isocyanate;
the speed of the mixer that mixes the polyol and gas; the viscosity of the system; and the type and amount of surfactant in the formulation.

Preferably, the foam is produced in the apparatus described in U.S. Patent Application Serial No. 115.628, which is a continuous production apparatus for curable polyurethane foam, which apparatus , an isocyanate, a catalyst, and an inert gas, the polyol, incyanate, and an inert gas separately under pressure and with controlled flow rates. means comprising separate conduits feeding a mixing device having respective inlet openings for receiving and admitting an active gas, mixing the polyol, incyanate and an inert gas to produce a foam; means having an outlet for the foam; means for supplying the foam from the mixing device to a second mixing device; a conduit for supplying the catalyst under pressure and at a controlled flow rate to the second mixing device; means for mixing the substance and the catalyst;
means for mixing the foam and the catalyst, having respective inlet openings for receiving the foam and the catalyst and an outlet for the resulting catalyzed foam; It includes a means for transporting the material from the mixing device onto the substrate.

Foam foams (fr) produced by the method from the compositions of the invention
otb foam) is useful, for example: as an adhesive for gluing grooves to framing, especially drywall grooves to wooden framing; as a flame-retardant insulation material; as insulation around doors and windows. Materials: Wood repair: Concrete repair,
Repair of lightweight concrete; can be formed into temporary footpaths on soft ground; median strips on main roads; fill holes in posts to prevent them from touching the soil as they provide almost immediate support; As a material for: covering buried pipes, protective and insulating skins, e-packing materials; repairing holes and dents in cars; The present invention relates to an article comprising a surface containing a plurality of materials having an essentially unitary appearance, one such material on such surface being a cured polyurethane foam on such surface.

The catalyzed foam is preferably used as a seam sealer to seal seams formed by placing dry wall panels in contact with each other.

When constructing buildings using so-called drywall materials, it is common to apply certain compounds to the seams of the wall panels to hide the seams and create a monolithic appearance. Typical dry-type compounds containing calcium carbonate, polyvinyl acetate latex and water are most commonly used. The problem with using this type of compound is the long drying time and shrinkage, which is why it is common to apply VC powder three times a day with one night's drying time between each coat.
Needs to be coated twice. These problems are especially serious for major prefabricated builders, who can build a house in one day starting from prefabricated panel units, and require an extra three days to connect the seams. is particularly troubling.

It can be constructed quickly and smoothly in one day, and there is no shrinkage.
An improved seam material has now been discovered that solidifies (sets) to a paintable surface overnight.

As mentioned above, when this foam is applied to the joints of wall panels and e-flanks to hide the seams, it hardens quickly and to nearly stable dimensions in both thin and thick sections; its hardening is dependent on ambient conditions. Relatively unaffected, ie can be applied over a wide range of temperatures and relative humidity: good adhesion to wallboard; no sagging; trowelable; smooth surface. Once cured, it becomes elastic and easy to apply SunP finish and makeup. When the foam cures, there is little expansion or contraction, resulting in a monolithic appearance of the wall.

The 7 ohm foam can be applied to the substrate by any conventional means. When applying foam foam to hide seams created by contacting dry wall materials, the foam can be applied with an applicator to pack into the seams. For other applications, the foam can be filled to the desired extent into cavities etc. - Cured Foam The cured cellular polyurethane of the present invention has an essentially closed cell structure. The bubbles are essentially spherical, approximately 300 mm in diameter.
It is less than a micron. The diameter of the bubbles is about 5 to about 300.
Spanning the micron range. The dimensions of the cells forming the skin side of the polyurethane foam are essentially the same as the dimensions of the cells in the central interior of the foam; It is essentially uniform from surface to surface except for This uniformity reflects the average uniformity that would be found within the polyurethane foam. The density of the cured foam is approximately equal to the density of the foam before curing.

Hardened urethane is elastic, can be polished, and can be easily applied with makeup. One Example The following example is a specific illustration of the practice of the invention and is not intended to limit the scope of the invention in any way.

Comparative Example This example is essentially the same as that of Barrow et al., U.S. Pat.
．． This is a reproduction of Example 9 of No. 821.120.

The product 3 is terminally capped with about 5 moles of ethylene oxide per 0-Hts and has an OH equivalent of about 1600.
60 F, 40 t of diethylene glycol and 164 F of polymethylene glycol (polymethylene polyphenyl incyanate) with an average functionality of 26 and a N00 equivalent weight of about 134 in a Hobart Φ equipped with a wire stirrer to stir and mix air into the mixture. Place the mixture in a mixer and whisk at high speed for 2 minutes to create a foam. Once the rise is complete, add 1f of a 33% solution of triethylene diamine dissolved in dipropylene glycol as a catalyst to obtain the resulting mixture. The foam was mixed for an additional 40 seconds. This foam was cut into a 3/8 inch Ceracola board with a 4/2 inch gap cut out and a second
4 x 2
(Note: Since the foam is liquid, the mold had to be placed horizontally. Therefore, the formulation could not be applied vertically.) Filled the mold. A flat 6 steel blade was then drawn across the surface of the mold containing the foam to level the surface. Two samples were made with this formulation. One sample was cured under laboratory ambient conditions at 26° C. and 60° relative humidity; the other was cured in a controlled humidity chamber at 26° C. and 90° relative humidity.

The density of the foam was measured before catalyst addition and was 2!51b4/b.
”, this value was measured on the cured product,
&951b4/ft reported in Barren patent
” does not match the density.

Post-foaming was recorded as the difference in thickness between the cured foam and the depth of the mold. The mold depth was nominally 375 mils. Post-foaming of the cured foam was determined by measuring the thickness of the cured foam in the mold (unit: yol) and subtracting the depth of the mold cavity. Post-foaming is
Samples cured at 60° relative humidity had 81-96 mils and samples cured at 90° relative humidity had 84-91 mils.

14, column 2, 16 of the Barren et al. patent.
This is not the same as the following statement in lines 22: ``Conventional foams obtained by mechanically introducing an inert gas into a urethane-forming mixture do not have any significant subsequent effect, other than due to thermal expansion of the inert gas used.'' It does not cause significant expansion and its amount is very small.
That is, the capacity is 1% or less. The following Examples 5 to 5 are illustrative of systems in which excessive amounts of post-foaming occur.

Example 1 An I-Liol package was prepared by mixing the following in a sealed 3-gauge container under nitrogen: 80 parts by weight of a polyol, a propylene oxide adduct of glycerin and having a hydroxyl number of 240, Solpi? /) 20 parts by weight of a polyol with a hydroxyl number of 490, a propylene ox, cytoadduct of a mixture of tofropylene glycol 80/20, 5 parts by weight of hydrogenated castor oil as a thixotrope, the formula (Person B) dissolved in Kundecylbenzene. ) n (wherein is a block of dimethylsilicone units, B is a block of oxyalkylene units, and n is greater than 20), a 40 weight solution of a surfactant (hereinafter referred to as surfactant) 1 parts by weight, and 3 parts by weight of sieve.

Mix these ingredients until the temperature reaches 60°C, and then
It was allowed to cool under nitrogen. The resulting compounded polyol package is conveyed through a tube to the top of an SKG continuous mixer with a pump rim of 136.697% f
(i.e., N0O10H=1.0)? 65.8 f of rimethylene polyphenylisocyanate and a sufficient amount of nitrogen were mixed to form a foam with a density of 30 tbs/ft''.

The incyanate was fed to the mixer at a rate of 80.8 f/min with a Zenith metering pump through 0.25 inch tubing. The stream was fed into a stationary mixer of nominal inch polypropylene tubing (sold by Inc. I Rated (TAHIndus-Iriam) under the trade name "Starter Chekub").

At the inlet of the static mixer, the formula %, dissolved in the propylene oxide adduct of glycerine with a hydroxyl number of 240, is expressed as (Witc0 is an integer of 1o)
The catalyst tolHII, which is a dialkyl dimercaptide phosphoric acid ester represented by UL-24 (hereinafter referred to as "catalyst") sold by OhemicaJ, was micrometered using a micrometer and a tube. 9/min to the foam so that the concentration of catalyst in the total formulation is 90 parts per 100 parts, 25 parts based on 4 rioles.

The rate of catalyst addition was controlled to produce a foam that showed early signs of gelation 80 seconds after filling the 8 ounce paper cup. The foam was placed over an 18-inch long x 15-inch wide section of dry wall material with a recessed seam and spread over the seam with one pass of a steel blade, smoothing out the initial smooth seam. Formed. The foam did not sag when held in a vertical position.

The setting time was 40 minutes. This setting time is the time it takes for a 30 mil foam film to reach the point where it cannot be lifted from a dry wall substrate by the light touch of a 42 inch piece of wood.

A 4 x 2 x 0.070 inch casting was made of foam and placed in a controlled room at 26°C and 90% relative humidity.

After 24 hours, the thickness of the cast is measured to determine the amount by which the cast exceeds the original 70 mil thickness after it has cured in a humidity chamber to quantitatively determine the degree of post-foaming. did. Post-foaming A15
It ranged from 2 to 172 mils. In addition, the combined seams were qualitatively evaluated by examining whether the surface was smooth or swollen. The plane was swollen.

The results are summarized in Table ■.

Example 2 Using a 1O bath solution of catalyst and making it into a foam: 3.8t/
The exact same procedure as in Example 1 was repeated, except that the catalyst concentration in the total formulation was 0.31 parts per oos based on the polyol.

The results are summarized in Table IK and circled.

Example 3 The following ingredients were blended to form a polyol package: Propylene oxide adduct of glycerin with a hydroxyl number of 16 g 80 parts; 0 Propylene oxide adduct of sorbitol and propylene oxide/mixture with a hydroxyl number of 49
0 polyol 20 parts by weight: hydrogenated castor oil
5 parts by weight; surfactant
1 part by weight; 3-person molecular thief weight s
.

This polyol package was mixed with 55.0 parts by weight of polymethylene elyphenylisocyanate according to the procedure described in Example 1 to form a foam. A 10% solution of the catalytic agent described in Example 1 was added to the foam according to the procedure described in Example 1 and at the conditions shown in Table 1 to increase the concentration of the catalytic agent in the total formulation on a polyol tube basis. 0.2 per 100 copies
There were 5 parts.

Example 4 The following ingredients were blended to form an Ilior package: Propylene oxide adduct of glycerin with a hydroxyl number of 112 80 parts by weight: 0 Sorbit and propylene glycol /20 Propylene oxide adduct of a mixture with a hydroxyl number of 490
20 parts by weight of polyol: hydrogenated castor oil
5 parts by weight: Surfactant A
1 part by weight: 3 Mumo V Kieller Sieve 5
Weight part.

This product was mixed with 45.2 parts by weight of t-polymethylene I liphenyl isocyanate according to the procedure of Example 1 to form a foam. A 1O2 solution of the catalyst described in Example 1 was added to the foam according to the procedure described in Example IK and at the conditions shown in Table 1 to determine the concentration of Catalyst A in the total formulation based on polyol. 100 copies! ! I O, 2
It is shown in Part 5.

Example 5 The following ingredients were blended to form a polyol solution: 60 parts by weight of a propylene oxide adduct of glycerin with a hydroxyl value of 34; 490 polyol
40 parts by weight: hydrogenated castor oil
5 parts by weight: surfactant 2 parts by weight; 3-person molecular sieve 5 parts by weight: alumina trihydrate 100 parts by weight: 2,2-cyclo1,3-propanediyltetrakis(2-chloroethyl)phosphate flame retardant ( 10 parts by weight (hereinafter referred to as retardant).

This polyol foam was mixed with 54.4 parts by weight of polymethylene polyphenylisocyanate (polymethylene polyphenylisocyanate) according to the procedure described in Example 1 to form a foam. A 50% solution of the catalyst described in Example 1 was prepared using the procedure described in Example 1 and Table 1
In addition to the foam under the conditions given in Table 1, the degree of catalytic absorption t' of all formulations based on the polyol [7 and 100 parts fi 0.
It was set as 05 parts.

Example 6 The following components were blended to make a polyol packaging: Ethyleneoxy P was added to the end (*-pry-i'>
The hydroxyl number was set at 27. 90 parts by weight of propylene oxide adduct of glycerin; 10 parts by weight of ethylene glycol-h; hydrogenated castor oil
7 parts by weight; surfactant
1 part by weight; 3 Mumo V Kieller Sieve 5 parts by weight.

The potuol nozzle cage was mixed with 444 parts by weight of polymethylene polyphenylinocyanate according to the procedure described in Example 1 to form a foam. A 2.5% solution of the catalyst was added to the foam at *0'4-* as described in Example 1 and at the conditions shown in Table I to confirm the presence of the catalyst in the entire formulation. The standard was J90.04 parts per 100 copies.

Example 7 The following components were blended to make a polyol cage: Ethylene oxide was added to the terminal to give a hyPoxy A value t.
It was set at 27. Propylene oxide adduct of glycerin
90] 1ji part; ethylene glycol 4
10 parts by weight; hydrogenated castor M
5 parts by weight; surfactant 1
Parts by weight; Table 3 Molecular sieve 5 parts by weight.

A foam was prepared by mixing this polio-bird A tube with 4 and 6 parts by weight of polymethylene I liphenyl insinate according to the procedure of Example 10. Example 1 2SX solution of catalyst
In addition to the foam according to the procedure described in #C and the conditions shown in Table 1, the concentration of catalyst ft&&Rio-A in the total formulation is
The ratio was 0.14 parts per 100 parts.

Practical example 8 A polyol package was prepared by blending the following components: 80 parts by weight of mustard oil; polyolefin oxyP adduct of norpit and propylene glycol 80/207i compound with a hydroxyl value of 490. & 20 parts by weight; hydrogenated castor oil
5 parts by weight; 3 mm molecular sieve s weight t
s: 1 part by weight of surfactant.

This 4! A foam tube was prepared by mixing the Rio-4A cage with 57.8 parts by weight of polymethylene polyphenylene (Incyane). A 5X solution of the catalyst was added to the foam using the procedure described in Example 1 and under the conditions shown in Table 1 to determine the concentration of the catalyst in the total formulation. Based on i standard, the Zoo part was 0.11 part.

Example 9 The following components were blended to make an I-liol solution cage: 80 parts by weight of castor oil; 10 parts of polyol-A, which is a propylene oxide adduct of sorbitol and propylene glyco-h80720a compound and has a hydroxyl value of 490. ；Water-formed castor oil
5 parts by weight; 3mm molecular sieve 5
2 parts by weight of surfactant:
Alumina trihydrate 100 parts by weight; flame retardant mesh 10 parts by weight.

This 4-lion body package was mixed with 58 parts by weight of polymethylene polyphenylisocyanate as described in Example IKle and under the conditions listed in Table 1 to form a foam, except that this foam A cast product of ×2×165 mil was made.

Practical Example 10 A polyol-AA resin was prepared by blending the following ingredients: 80 parts by weight of mustard oil; 20 parts by weight of a polyol, which is a propylene oxide adduct of an 80/20 mixture of sorbitol and propylene glycol and has a human-xyl number of 490; hydrogenated castor oil
6 parts by weight; 3 parts molecular sieve 5 parts by weight; 1 part by weight interfacial agent; 100 parts by weight alumina trihydrate; 1 part by weight TS shavings.

This polyol nogage was mixed with 58 parts by weight of polymethylene polyphenylinocyanate.

A 40% solution of Catalyst was added to the foam according to the procedure described in Practical Example IK and under the conditions given in Table 1, and the concentration of Catalyst in the total formulation was adjusted to 100 parts based on Polio-1 hlk. Right,
! >0.06 parts. 2x165 to 4 with kernel foam
I made a cast molded product.

Example 11 The following ingredients were blended to make a polyol (castor oil): 80 parts by weight; a propylene oxide adduct of sorbitol and propylene glyco-A80/20a compound, a polyol with a hydrogenation value of 490, 20 parts by weight. Part: Hydrogenated castor oil
5 parts by weight; 1 part by weight of interfacial agent; 100 parts by weight of alumina trihydrate; #
5 and 10 parts by weight of refueling agent.

The ζO polyol package was mixed with 58 parts by weight of polymethylene polyphenylisocyanate.

A 5911 solution of the catalyst from Example 1 was added to the foam using the procedure described in Example 1 and at the conditions shown in Table 1.

The concentration of catalyst in all formulations is 1 based on polyol.
The ratio was 49 parts of 6O per 00 parts. With this foam, 41c2X1
I made a 65 mil cast product.

Example 12 A Polio-A package was prepared by blending the following ingredients: Castor oil 80 parts by weight; propylene oxide adduct of a 80/1G mixture of sorcery pit and propylene glyco, with a hydroxyl number of 490. -420 parts by weight; hydrogenation and mustard oil
5 parts by weight; 3 parts by weight; 5 parts by weight; surfactant; 2 parts by weight; At
100 parts by weight of trihydrate; iii.
l・0 heavy food section.

This polyol package was prepared using the procedure described in Example 1 to prepare polymethylphenyl isocyanate (57.8
9. Mix with parts by weight to form a foam.

5X solution of catalyst table as described in Example 1.

In addition to foaming under the conditions shown in Table 1, the concentration of catalyst in the entire formulation was adjusted to 100 f! based on polio-At. S
m! l 0.11 parts and 1 part.

(f/min) (f1 min) (f1 min) (I%) (℃
) (lbcl 136.6 80.8
0.1 1G 27 30.02
136.6 80.8 3.8 1
0 27 34.4B 135.0
65.2 0.1 10 29
32.04 137.4 54.6 0.
1 10 29 33.55 1G9
．． 0 27.6 0.5 5 4
9 27.06 99.6 43.4
1.5 2.5 35 25.67
1G4.4 45.6 5.4 2.5
28 32.08 116.2 57.6
2.2 5 30 32.09
183.6 44.2 0 0
42 2410 16J, 2 41.8
0.9 5 3g 26.41
1 135.6 36.8 1.1
5 39 2612 174.6 45
．． 6 1.8 5 44 229 mm = Smooth 11 side B Deep swelling surface * = Measured in a mold with a depth of 165 mils 80 40 152-172 B
7.9<60 31 11
0-132 B 7.915
45 41j B 8
．． 145 30 40 B
5.230 35 35 B
Incompatibility 30 40 - Mu 6.430 33 4-8
& 6.430 23
0-2 people 0.4*B
O14 9001Q7 70-72 38 35 2* In 0.43)
30 36-43* BO1430257
-14mu 0,4 Comparing the data regarding Examples 1 to 12 in Table 1, it can be seen that the after-foaming company decreases in the following case = (1)/v All's Hirro medium sill number decreases (Actual Example 1 and 2 with actual examples 3 to 5): (2) Hygroscopicity of #'l decreases (comparing actual example 8 with actual example f12 and I2); (3) Increase catalyst temperature f (actual example 1o Actual example 9
and (4) increasing the concentration of the hygroscopic substance (compare Example 11 with Example 10). It is affected by whether or not the Actual power example 6
71 with real power example 4, this is shown.
Ru. Although the hygroscopicity of the polyols of Working Examples 6 and 7 is higher than that of the polyol of Example 914, the amount of post-foaming is considerably lower.

Practical Example 13 A polyol package was prepared by blending the following ingredients: Castor oil 57.7 lbs.; Polyolefin with a hydroxyl value of 490, a mixture of sophite and propylene glyco-hsoizoa. -41 Table 4 Bonn) 1: Hydrogenated castor oil
Table 3 pounds; 3 mmoleki error sieve λ6/
0.7 lbs of surfactant:
aa, isu trihydrate 721ponP;Jll
Fuel & 72/nd.

This polyol package was loaded into a fire mixer containing 7 pieces of 20 cents. Fill the mixer space with nitrogen.
and sealed the mixer. The electric mixer was operated and the components were mixed until #Af reached 60° C. over about 20 minutes. I'm running out of money for this material.

Transferred to three 5 gallon containers.

'Vc%A, the kernel material was heated under pressure (approximately 30-70 ps
This nitrogen was fed into the polyol tube just before the stream entered the continuous mixer through a separate tube.

A stoichiometric amount of liquid polymethylph I9 phenyl isocyanate was delivered to a series fat mixer with a Zenith metering pump. The resulting foam was passed through an 8-foot-long, 1/2-inch ID hose to a static mixer (starter tube 2
0-65. (374 inch nominal diameter, 1/2 inch length) Hepo/Zo. Immediately before the static mixer, 5 of the dissolved catalyst mixture consisting of propyleneoxy P adduct of glycerin and having a hydroxyl number of 240/V/hfc was added.
The weight percent solution was added by injection using a micrometering pump at a ratio of 100 parts by weight of Polio-A to 0.1 part by weight of the catalyst. The catalyst was dispersed into the foam through a static mixer.

The catalyst foam was placed over the wall material joint and spread over the joint with a steel blade to smooth the joint. The density of the foam was 3 jj lbs/ft".

With the smoothed seam vertically oriented, at 26°C and relative humidity [90
% cured. The seam did not sag and foaming did not occur after 4 hours. The seam reached the gel stage within 33 minutes and could be pulled over the surface with a blade without scratching within 45 minutes.

Practical Example 14 The procedure of Practical Example 13 was repeated except that a polyol cage was prepared with the following components:
Polyol 5400f, which has a hydroxyl value of 27 by adding ethyleneoxy Ft to the propyleneoxy P adduct of glycerin, Etele 7 glycol 600f; Hydrogenated castor oil 300f; Three-person molecular sieve 300f; Surfactant M
60f.

A foam was prepared using the procedure described in Example 1O.

The foam was placed over the wall material/-4 seam and spread over the seam with a steel blade to smooth the seam.

The density of the foam was 321 bs/ft'', and the leveled seam was cured vertically at 26°C and relative humidity g9oX.The seam did not sag or post-foam. Slow to gelation stage within minutes.

Within 50 minutes, the surface could be pulled with a blade without scratching.

Examples 15-22 General Procedures Boliol, J! Place each component to prepare the cage in a 1/2 gallon container and store at 50°C under nitrogen gas.
Mixing was carried out using a Corrales Model Al-VG mixer until . Keep this container tightly sealed and store until ready to use.

*The amount of master/tsutsuchi you instructed to n? The rimethylene polyphenylinocyanate was added to the 1 bind jar with mixing, filling the jar to 273. Mixing was carried out under a nitrogen atmosphere using a Mix Master mixer with a standard beater supplied with the unit at a "beat whip" (maximum rpm) setting of K.

Each component was mixed for 10 minutes. A catalyst, if used (as described in Example 1), was added to the foam at this point with a syringe and each component was mixed with a wooden spatula for 30 seconds.

The foam was transferred to a 1 oz wax coated paper cup. Calculate the density of the foam and also calculate the gelation time t of the foam.
It was measured.

A portion of the foam was placed in a mold and post-foaming was added.

This tIi is two pieces of Cerakola attached to one plywood / -
A cavity with a width of 1/4 inch and a radius of 378 inches was formed using a hard disk. Room temperature, dry box for each equipment condition (conventional as listed in Table I), 26°C, relative humidity! [The foaming tube was fixed in a 90% humidity control room. Post-foaming is measured using a micrometer and is expressed as the percentage of expansion of the cured foam beyond the original cavity depth;
A large amount of post-foaming was used to allow for 30% expansion. However, each test sample of approximately 30X expansion is essentially monolithic to the naked eye.Other examples exhibit greater than 30% expansion in the table.

It was possible to achieve an acceptable result by using a large amount of catalyst and/or molecular sheep. However, this method greatly shortens the gelation time, which is not a desirable situation.Example 15 A polyol master notch was prepared by blending the following components: Glycerin with a hydroxyl value of 240. Propylene oxide adduct 200f; Alumina trihydrate 2G0f; Flame retardant
20t; hydrogenated castor oil
12f; Surfactant 2f
.

This polyol package 11L9f was prepared using polymethylene I (liphenylinocyanate) 2 & 1f according to the procedure described above.
A foam was created by mixing with ? To the foam of - was added a 10% solution of 0.5 F of a catalytic amount dissolved in the zo-p-pyrooxide addition of glycerin - according to the procedure described above. foam li degree, foam density.

The gelation time, post-foaming and hygroscopic properties of polyols are shown in Table 1.

Practical Example 16 The following ingredients were blended to make Polyol-H Masternotch: Adduct of glycerin with cypyrenooxide having a hypoxyl value of 240 200f; error sieve
10f; Flame retardant
20f; Hydrogenated castor oil 1
2t; containing surfactant 21° This /V all package 1114t was treated with polymethylene elyphenylisocyanate) 27. '
6r! =a! The mixture was combined to form a foam.

Add 2M of glycerin to this foam.
0.2 t of a 10'X solution of catalyst dissolved in 11-ml as described above was added. Foam warmth, foam device.

Gel time, post-foaming and polyol hygroscopicity are shown in the table.

Example 17 The following ingredients were blended to make Rioux Island Master A Tsuchi: Propylene oxide adduct of glycerine and phosphorus with a hydroxyl value of 240 2002; Aona trihydrate 200f! :5 Mumolex sieve 10IP;Flame retardant Mu
201F; Hydrogenated castor song
12f; Surfactant'
2f.

This 4 Riolunozo Tsugaji 112! , 4 ft'' was mixed with polymethylene polyphenylinosyphnate 276F to form a foam tube using the procedure described above.

To this foam was added an IX solution of catalyst dissolved in propylene oxide adduct of glycerin (as described above). 71g-like material I! Vertical, foam 1! Ff, gel time, post-foaming and hygroscopicity of polyol are shown in the system.

The following ingredients were blended to make a polyol master nozzle: Propylene oxide adduct of glycerin with hydroxyl j of 34 2001 Nia Tori Mina trihydrate 200f; Flame retardant M
2Qf: Hydrogenated castor oil
12f; Surfactant 2
f.

This polyol package 13λ7 ft-, polymethylene/41 phenyliso9ane) a
3f to form a foam. To this foam was added a 10% solution of catalyst 5 dissolved in zoquipyrene oxide adduct of glycerin as described above. Foam 1! ML foam occlusion, gel time and polyol hygroscopicity are shown in the table.

Polyolefin-4j star powder was prepared by blending the following components: Adding ethylene oxide P to the end gave a hydroxyl H value of 3
0 was set as 27. Glycerin propylene oxide adduct 200t; Amina trihydrate
200t; 5-mumoleki error sieve
109; Flame retardant A 2
09: Hydrogenated castor oil 12f:
Surfactant Foam A foam was prepared by mixing 21° of polyolefin-AA cage 13&Of with polymethylene/v7 elisocyanate aOf using the procedure described above. Foam 11f, foam density, gel time, post-foaming and polyol hygroscopicity are shown in Coalfield.

Polyol master A was prepared by blending the following components: At the end, the hydroxyl h value of 30 was changed to 27 using ethylene oxide, tfcJ, mt, and hydroxyl. Propylene oxide adduct of Daliceli/2009; A-A construction trihydrate 200f; Burning Mu
20f; Hydrogenated castor oil
12t; surfactant 21
゜This 4-lior package 135. , Of was mixed with polymethylene & Of using the procedure described above to form a foam. Add glycerin f-ropyleneoxy P to this foamy substance.
IX solution 40F of catalyst A dissolved in adduct was added as described above. Foam 1i&.

Foam density, gelling time, post-foaming and polyol hygroscopicity are shown in Table 1.

Combine the following ingredients to make one Oh 7! & Master/Tsutsuchi: Castor oil 200f; AA trihydrate 200f;
20f; Hydrogenated castor oil
121; Surfactant & 2
F.

This - Riolu Nozo Tsugaji 11 & 8 ft Polymei
The degree of foam density, gelling time, post-foaming and hygroscopicity of the polyol are shown in the table.

Example 22 The following ingredients were blended to make 9 polyols: Mustard oil 200f; Alumina trihydrate 200f;
20f; Hydrogenated castor oil
12f; Surfactant 2
t.

Konobori All Package 11 & 8 f Polymethylene Polyphenylisocyanate) 2L! f and.

A foam was made by mixing as per the procedure listed above.

Add 7J of glycerin and propylene to this foam.
40 t of a 1% solution of catalyst dissolved in IIwl was added to the top.
I added it as shown. Foam 1! [-, foam writing.

Gel time, post-foaming and hygroscopicity of the poly9ol are shown in the surface layer.゛Polyol Insia Catalyst Foam Foam
Practical Example Wj degree of temperature of child of masternate Amount of amount (f) (f) (f) ('C)
(lhs/ft”) (zu15 111J6
28.14 0.05 4G 31.0
3 (116112-3627440-02313
0-94517112J6 27.64 G,
04 32 29.5 618 133
71 6.29 0.05 31 6g,
3 -19 134.96 5 force 4
0 30 53.1 6020 13
4J6 5 force 4 0.04-- 421
118.76 21.24 0 3
0 38.0 9022 11B, 76
21-24 0.04-37.6
! j*1=100% standard)) Drying box (humidity f%) Humidity 1 (26℃) (%
)+ -100(29) 280
g-4i 29-2 133 (38)
246', 2'0.8 ・
-41, (38) 198 #16i
7 (29) ' ] 06.1 1.6
1 - 55.6 (29) r44.5
3.01 16.8 8.5 (38
) 52.5 #1 -
5 & 3 (29) 135.4 0.3・
-26,2(30) 64.0 # It is clear from these data that post-foaming increases with wet height regardless of the polyol used.

This is clear from the post-mortem foaming data obtained for any given polio-A at the various humidity levels tested.
There is a tendency for post-foaming to be much larger than that of #1. in this way.

The tendency of a polyol to absorb water, as determined by its hygroscopicity, is also an important factor, as can be seen by comparing Examples 15 and 18, which exhibit a given moisture content.

As can be seen by comparing Actual Example 19 with 20 and 21 with 22, the catalyst is also an important factor.

The presence of a catalyst reduces post-foaming, but this is not the case.

This is because the gelation time is correspondingly shortened, and therefore the time during which the moisture-sensitive incyanate is present to react with water leading to the foaming reaction is shortened.

Another way to reduce post-foaming is to include a hygroscopic material 51 in the system, such as Molecule Shiso. but,
MoVdP-S resin was also found to exhibit a catalytic effect on the gelation reaction, which is also expected to reduce post-foaming. These combined effects are clear by comparing Example 15 with the post-foaming of Examples 16 and 17.

thus,! i! Hinoki Example 15 exhibits a relatively large after-foaming even when catalyzed in the usual manner because the cypress has a high hygroscopicity and contains no hygroscopic substances. *Example 1
Although 6 contains molecular sieve t-1, the amount of conventional catalyst is less than that of Example 15. In Example 16, although the amount of catalyst is small! l! The after-foaming is smaller and the gelation time is shorter than that of Example Is. 5j# and Example 17 also contain sieves in the leakage, but the amount of normal catalyst is larger than that of Example 16, resulting in less after-foaming and gelling. The post-foaming times are further reduced. The values of post-foaming shown in Table I are larger than those shown in Table I, which is due to the fact that the values of post-foaming shown in Table I are
This is because it was cured. This was done to further emphasize the difference between the size of post-foaming. A rapid post-foaming was observed in each of the examples. This is because it contained

[Brief explanation of the drawing]

FIG. 41 schematically shows a flow chart of a preferred implementation of the invention, and FIG. 2 is a side view of the container 29-30 of FIG. 1. 1-Air tank, 27-Catalyst container, 28-Incyanate container, 29.30-/Liol container. 32.33.34-yl pump, 35-・motor. 47-Medium sensor, 76-Catalyst injector, 86-Stationary injector, 8-Front... applicator,! 93-・Solvent container, 105,108-・Siri/Goo.

Claims (1)

Scope of Claims: (1) A cured foam that, when cured by exposing at least one surface of the foam to the atmosphere, has essentially the same density as the uncured foam composition. In a foamable thermoset polyurethane forming composition: (a) a polyol; (b) a $lisocyanate. (c) a thixodraping agent; (d) an inert gas; and (a) an iron composition available for reaction with the polyisocyanate to cure the iron composition to a density that is not essentially the same as the density of the foamed composition. The composition is characterized in that it contains less water than the amount of foamed urethane foam. (2. In the composition according to claim 1,
The polyol may include raw hydrocarbons, hydroxyl-terminated polyformals, hydroxyl-containing fatty acid esters of diols and polyols, hydroxyl-terminated / hydroxyl-terminated ether polyols, The composition is characterized in that the active hydrogen-containing component is at least one selected from alkylene ether polyols or a mixture thereof. (3) The composition according to claim 1, wherein the polyol is an alkylene ether polyol. OxyP with water or PolyhyP
The composition is characterized in that it is a polyether polyol obtained by addition to a roxy organic compound. (4) The composition according to claim 1, wherein the #polyol includes castor oil. (6) The composition according to claim 4, wherein the polyol is a mixture of castor oil and polyether polyol. (6) The composition according to claim 1, wherein the I*-liol is a cyclic ester. (7) In the composition according to claim 1, the limb polyol is a polybutadiene polyol.
The composition having the # symbol. (8) In the composition according to claim 3, the polyether polyol is a mixture of two or more alkylene oxides, most of which are ethyleneoxy P-terminated polymer units. The composition is characterized by: (9) The composition according to claim 1, wherein the incyanate is a high molecular weight incyanate. o04! 10. The composition according to claim 9, wherein the high molecular weight isocyanate is polymethylene polyphenylisocyanate. αη In the composition of claim 1, the incyanate and the polyol are about 0.70:1.5.
The composition is characterized in that it is used in a NOO:OH molar ratio of 0. (b) In the composition according to claim 1,
The composition, characterized in that the thixotropic agent is hydrogenated castor oil. 2. The composition of claim 1, wherein the chicken L-zo agent is used in an amount of about 1 to about 15 parts by weight. Q4 In the composition according to claim 1,
The composition, characterized in that the inert gas is dry air or nitrogen. Qfl % A composition according to claim 1, characterized in that the composition contains a hygroscopic substance. (Transition) In the composition according to claim 15,
The composition, characterized in that the hygroscopic substance includes molecule-. (lη) The composition according to claim 15 or 16, wherein the hygroscopic material is a polyol ([1
m) The composition is used in an amount of 1 to about 10 parts by weight per 100 parts by weight. (to) The composition according to claim 1, characterized by a filler. (to) the composition according to claim 18,
The composition characterized in that the filler is alumina trihydrate. (2) The composition according to claim 1, characterized by a surfactant. (c) The composition according to claim 20, wherein the surfactant is an organosilicon or a copolymer.翰 The composition according to claim 20, wherein the surfactant is a high molecular weight linear non-hydrolyzable sheexane.
Polyoxyalkylene. The composition is characterized in that it is coated with a block copolymer. 6! I4 In the composition according to claim 1,
The density of the cured foam is about 18 to about 45 Abs/ft.
” - Claim 1 characterized by a catalyst for producing urethane
The composition according to section 1. (2) In the composition according to claim 24,
The composition characterized in that the catalyst contains a tin-sulfur bond. (e) In the composition according to claim 25,
The catalyst has the following formula [wherein Rs and R1 independently have 1 to about 2 carbon atoms]
alkyl, aryl or alkylaryl containing 0, C1' is an integer from 1 to 8, and d'
is an integer from 1 to 10]. 4. The composition according to claim 24, wherein the catalyst is a tertiary amine. (to) the composition according to claim 24,
An iron composition characterized in that the catalyst has high activity for the reaction between polyol and incyanate, low activity for the reaction between isocyanate and water, and high solubility in the polyol. 4. An iron composition according to any one of claims 1, 24, 25, 26, 27, and 28, characterized in that the catalyst is dissolved in a solvent. ■ In a method for producing a curable polyurethane foam, incyanate and a thixotropic agent-containing polyol are separately added to a mixer at a constant ratio, and a gaseous substance is added to this mixture under pressure to generate a foam. The foam is conveyed from the mixer into a tube to expand its volume to a density of about 18 to about 45 tbm/ft, and in the tube the foam is applied onto a suitable substrate. (b) The method according to claim 30, wherein a urethane-forming catalyst dissolved in a solvent is added to the foam in the tube. and mixing with the foam in a mixer, then applying it onto a suitable substrate, and curing the foam on the substrate. A method according to claim 30 or 31, carried out at an ambient temperature of °C. The polyurethane has a diameter of about 300 square meters or less. The foamed polyurethane according to claim 33, wherein the size of the bubbles forming the surface of the polyurethane is 7 ohms at the inner center. The polyurethane is characterized in that it is essentially equal in size in part. ■ In a method of concealing the seams of adjacent wallboard panels, a curable polyurethane foam is applied to the seams, where the foam is cured. The method according to claim 35, characterized in that:
36. The method of claim 35 or claim 36, wherein the cough foam has a density of about 18 to about 45 tbs/ft. A method according to claim 35, characterized in that curing is carried out at an ambient temperature of about 40° C. t4.
Is the wall panel solid? - the method. ■ A monolithic appearance wall consisting of at least two wallboard panels erected substantially edge-to-edge and forming a joint between them, the joint being filled with resilient polyurethane foam; A wrinkled wall. In the monolithic appearance wall of claim 39, the cellular polyurethane comprises about 18 to about 45 tb.
s/ft". 2) A wall with an integral appearance as claimed in claim 39 or 40, characterized in that the wall panel is made of selvedge. Wall. An article comprising at least one surface and a surface containing a plurality of materials having an essentially unitary appearance, one of such materials on such surface being such a material. The article is a polyurethane foam cured on a surface.