CN1121091A - Integral-skin polyurethane foam, preparation process and use of same - Google Patents
Integral-skin polyurethane foam, preparation process and use of same Download PDFInfo
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- CN1121091A CN1121091A CN95109512A CN95109512A CN1121091A CN 1121091 A CN1121091 A CN 1121091A CN 95109512 A CN95109512 A CN 95109512A CN 95109512 A CN95109512 A CN 95109512A CN 1121091 A CN1121091 A CN 1121091A
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- whipping agent
- polyurethane foam
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- ester
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
- B62D—MOTOR VEHICLES; TRAILERS
- B62D1/00—Steering controls, i.e. means for initiating a change of direction of the vehicle
- B62D1/02—Steering controls, i.e. means for initiating a change of direction of the vehicle vehicle-mounted
- B62D1/04—Hand wheels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
Abstract
The invention discloses a method for preparing integral skin polyurethane foam plastic by using a foaming system of carbon dioxide, comprising that: boric acid and/or esters thereof, or a mixture of the compound and organic carboxylic acid and/or esters thereof is taken as a foaming agent; the integral skin polyurethane foam prepared by the method which has the advantages of low free foaming density, well mouldability and no foaming phenomenon.
Description
The present invention relates to integral-skin polyurethane foam, Its Preparation Method And Use.Integral-skin polyurethane foam can be used for trolley part such as bearing circle and spoiler and furniture such as handrail and chair legs.
Integral-skin polyurethane foam is characterised in that by activeconstituents being poured in the mould, foaming, solidifying and the demoulding subsequently constitutes cortex and foam layer simultaneously.Integral-skin polyurethane foam has splendid elasticity and wear resistance, thereby is widely used as cushioning material in automobile and field of furniture.In order to form cortex, need make whipping agent with the lower boiling organic compound, Trichloromonofluoromethane (code name CFC-11) wherein commonly used especially.
Yet, be that the so-called trifluoromethane based compound (hereinafter referred is the CFC compound) of representative is considered to destroy the ozonosphere in the atmosphere in recent years with the Trichloromonofluoromethane.Thereby, formulated the law that limits the CFC compound in the world successively.
As the s-generation surrogate of CFC compound, the Hydrochlorofluorocarbons (hereinafter referred is HCFC) of (ODP hereinafter referred to as) that the someone has proposed to have the low-ozone rupture factor.
Available HCFC comprises for example monochlorodifluoromethane (code name HCFC-22), 2,2-two chloro-1,1,1-Halothane (code name HCFC-123), 1,1-two chloro-1-fluoroethanes (code name HCFC-141b) and 1-one chloro-1,1-C2H4F2 C2H4F2 (code name HCFC-142b).
In addition, as third generation surrogate, it is zero hydrogen fluorohydrocarbon (hereinafter referred is HFC) that the someone has proposed ODP.The example of HFC comprises 1,1,1,2-Tetrafluoroethane (code name HFC-134a).
Yet people think still that from the atmospheric viewpoint of preserving our planet these HCEC and HFC whipping agent still can not use with being perfectly safe.
That is to say that although HCFC has low ODP, it remains the compound that a class can damage the ozone layer.Though the ODP of HFC is zero, needn't worry that ozonosphere is destroyed, it has the intensive Greenhouse effect, and Greenhouse effect coefficient (hereinafter referred is GWP) height is so can not use relievedly.
As mentioned above, so-called Chlorofluorocarbons (CFCs) surrogate only is the short-term countermeasure to the Chlorofluorocarbons (CFCs) regulation.Therefore, people expect to develop permanent and non-completely Chlorofluorocarbons (CFCs) foaming technique, promptly so-called carbon dioxide foaming technique.
In common urethane foam field, make the carbon dioxide foaming technique that uses water as whipping agent always at flexible foam plastic, semi-rigid foamed plastics and rigid foam field independent development.In the prior art, so-called water foaming foam plastics mass production.
On the other hand, in the integral-skin polyurethane foam field, consider the mechanism that generates cortex, it is favourable using low-boiling foaming agent.Water is used as whipping agent can produces many problems, therefore can't actually use.
That is to say that " water foaming technique " is meant carbon dioxide that the reaction used by isocyanate group in water and the raw material the produces technology with foam plastic foaming.Thereby, when adopting the water foaming technique do not use CFC to implement to prepare the process of integral-skin polyurethane foam as the routine of whipping agent with CFC-11 (boiling point 27.5), produce carbon dioxide at die surface, that is to say, form foam layer and do not form cortex on the urethane foam surface.As a result, can not constitute the gross weight structure.As the countermeasure of this phenomenon, Japanese Patent discloses flat 3-32811 and proposes die temperature is remained on 15-40 ℃, uses the temperature sensitivity catalyzer that depends on temperature strongly in the reaction of water and isocyanic ester.On the other hand, propose again the catalyzer low to temperature dependency used in the reaction of isocyanic ester and hydroxy-containing compounds.Japanese Patent discloses the example that flat 3-33120 discloses the temperature sensitivity catalyzer.Yet, even use temperature susceptibility catalyzer forms the solidification delay that the high-density cortex also can make polyurethane surface owing to the reduction of mold surface temperature, and the outward appearance and the quality of infringement gained porous plastics.
In addition, closed cell content is high and gained foaming damping factor is low causes that in ejection phase urethane foam bubbles and crackle easily, the result, and the temperature sensitivity catalyzer has the shortcoming that needs long demould time.
In addition, the water foaming technique also causes the another one problem, i.e. the urea key that the reaction of water and isocyanic ester forms is formed stone segment, causes the hardness of gained urethane foam to increase, and has damaged the sense of touch of gained porous plastics.
On the other hand, people consider a kind of can be by generating carbonic acid gas like the response class of isocyanic ester but do not generate the reaction mechanism of urea key.For example, Japanese Patent discloses flat 3-24108 and discloses the method that the carbonic acid gas that makes isocyanate groups react to each other the generation carbodiimide groups and use reaction to emit is made whipping agent.Japanese Patent discloses flat 3-152111 and has proposed to make cyclic carbonate to Cheng the oxazolidone group with isocyanate reaction Xing and the carbonic acid gas that uses reaction to produce is made whipping agent.
Yet there are some problems in these methods, for example are difficult to reaction speed, use expensive catalysts and need be used in combination Chlorofluorocarbons (CFCs) for enough foaming degrees are provided.Therefore, the problem of blown with carbon dioxide technology existence can not be with these technology from solving in essence.
As mentioned above, still be unrealized, suddenly hope the problem that solves although this is those skilled in the art by the method for using the carbon dioxide foaming technique to replace Chlorofluorocarbons (CFCs) or surrogate HCFC and HFC to prepare integral-skin polyurethane foam.Its reason is that this technology compared following shortcoming with using Chlorofluorocarbons (CFCs) or surrogate HCFC with HFC:
(1) needs to prolong demould time and damaged productivity.
(2) the heavy wall moulded parts produces in ejection phase easily and bubbles and perforation.
(3) urethane foam expands in ejection phase, keeps the trace of die surface easily at product surface.
(4) porous plastics is a hard, and sense of touch is poor.
(5) cortex is thin.
Had been found that the countermeasure that overcomes each shortcoming of above-mentioned (1)-(5) respectively.Yet, the still untapped carbon dioxide foaming technique that goes out can solve simultaneously whole (1)-(5) problem and can be used in the actual production line.
Japanese Patent discloses flat 2-199136 and has proposed to make whipping agent with organic carboxyl acid.Yet, in the method, organic carboxyl acid is produced stable time dependent problem as whipping agent in the isocyanate-reactive composition.As its solution, Japanese Patent discloses flat 3-153721 and proposes to use the organic carboxylate of the nitrogen base with at least one N-H key as whipping agent.Yet this method is difficult to control the speed of response of whole system, because it is too fast to have the nitrogen base and an isocyanate reaction of N-H key.
The purpose of this invention is to provide the method for preparing integral-skin polyurethane foam with carbonic acid gas as whipping agent.
We have carried out research in depth for the whipping agent that uses carbon dioxide to make integral-skin polyurethane foam, found that the integral-skin polyurethane foam that makes as whipping agent with boric acid or its ester can eliminate all above-mentioned shortcomings, the moulded parts that productivity and mouldability are splendid and have good sense of touch is provided.Thereby finished the present invention.
That is to say that content of the present invention is:
(1) moulding product density is 0.3-0.8g/cm
3Integral-skin polyurethane foam, it is to pour in the mould by the reaction mixture with aromatic polyisocyanate, high molecular isocyanate activity compound, whipping agent and other additive to obtain, and comprises using boric acid and/or its ester to make whipping agent.
(2) integral-skin polyurethane foam of above-mentioned (1), wherein whipping agent is the mixture of boric acid and/or its ester and organic carboxyl acid and/or its ester.
(3) pour into by reaction mixture that to prepare moulding product density in the mould be 0.3-0.8g/cm with aromatic polyisocyanate, high molecular isocyanate activity compound, whipping agent and other additive
3The method of integral-skin polyurethane foam, comprise and use boric acid and/or its ester to make whipping agent.
(4) method of the integral-skin polyurethane foam of preparation above-mentioned (3), wherein whipping agent is the mixture of boric acid and/or its ester and organic carboxyl acid and/or its ester.
(5) preparation method of the integral-skin polyurethane foam of above-mentioned (1) or (2), wherein this preparation method is the reaction injection molding(RIM) method.
(6) with above-mentioned (3), vehicle steering, indoor hardware fitting or furniture that the preparation method of (4) or (5) makes.
The present invention uses:
(1) boric acid and/or its ester, perhaps
(2) mixture of boric acid and/or its ester and organic carboxyl acid and/or its ester is made whipping agent.
In making the method that uses water as whipping agent, the filling capacity of response composite that comprises aromatic polyisocyanate, high molecular isocyanate activity compound, whipping agent and other additive is relatively poor usually.As a result, for improving filling capacity, must increase amount as the water of whipping agent.Yet the consumption that increases water can produce such shortcoming: the overplumping of urethane foam keeps the trace of die surface and produces foaming and perforation in ejection phase at product surface easily.
Prolong demould time and can overcome above-mentioned shortcoming effectively, but can reduce the productivity of porous plastics, and because water and isocyanate reaction formation urea key, thus porous plastics be hard and sense of touch poor.
The response composite that comprises whipping agent of the present invention and aromatic polyisocyanate, high molecular isocyanate activity compound and other additive with the composition that uses water as whipping agent is compared have splendid filling capacity and demoulding ability.Therefore, can not make to high productivity and stay the die surface trace and do not produce the integral-skin polyurethane foam of the present invention of bubble and perforation in the molding stage at product surface.Also can obtain the splendid porous plastics of sense of touch, because the carbonic acid gas that isocyanic ester and whipping agent reaction produce forms foam and seldom forms the urea connecting key.
As mentioned above, in the present invention, water is not done the whipping agent use or is only used with making co-foaming agent on a small quantity, and therefore, the present invention can overcome the shortcoming that method had that uses water as whipping agent.
And the used whipping agent of the present invention is corroding metal not, in contrast, is that the organic carboxyl acid whipping agent of representative can corroding metal with formic acid.
Integral-skin polyurethane foam of the present invention can make with the reaction injection molding(RIM) method by the urethane raw mixture is poured in the mould.In moulding process, in the part that contacts with mould inner surface, porous plastics expands and is suppressed, and constitutes elastomerics shape cortex.Thereby cortex and foam layer form simultaneously, constitute an one-piece construction.The integral-skin polyurethane foam that the present invention obtains has splendid elasticity and sense of touch, and is suitable to automobile inner part such as bearing circle, horn knob, pressure pad, panel board, control enclosure and gloves lid, something or somebody to fall back on pad, handrail and air spoiler; Seat, leg and handrail with furniture such as chair.
Below the present invention will be described.
Known aromatic polyisocyanate can be used for the present invention.Preferred isocyanic ester is diphenylmethanediisocyanate, polymethylene polyphenyl vulcabond, above-mentioned polyisocyanates and active hydrogen-contg compound reacts the isocyanate-terminated prepolymer that obtains and the polyisocyanates of urethano imines (urethonimine) modification.
Particularly preferred aromatic polyisocyanate is the above high polymethylene multi-phenenyl isocyanates of many phenyl ring amount of three phenyl ring, more particularly, is that the content of three or three above phenyl ring is not less than the polymethylene polyphenyl isocyanate of 60% (weight).In addition, the mixture of the imine modified liquid diphenylmethanediisocyanate of the prepolymer of the also preferred diphenylmethanediisocyanate that uses itself and urethane modification or urethano.
Available high molecular isocyanate activity compound of the present invention is the polyvalent alcohol that obtains as follows: separately carry out polyaddition with propylene oxide or with the mixture of propylene oxide and ethylene oxide and active hydrogen-contg compound such as water, propylene glycol, glycerol, TriMethylolPropane(TMP), tetramethylolmethane, Sorbitol Powder, sucrose, trolamine, quadrol, tolylene diamine, diaminodiphenyl-methane or above-claimed cpd, making the averaging of income functionality is 2-4.The hydroxyl value of this polyvalent alcohol is 24-55mg KOH/g, and ethylene oxide content is the 10-25% (weight) of polyvalent alcohol, and the terminal proportion of primary OH groups is 70-95% (mole).
Also preferred by grafting ethylenically unsaturated monomers such as the resulting polymerized polyalcohol of vinylbenzene, vinyl cyanide or methyl methacrylate (trade mark) on above-mentioned polyvalent alcohol.
When ethylene oxide content was less than 10% (weight), the terminal proportion of primary OH groups was also reduced to 70% (mole) and owing to active the reduction makes the productivity variation.
On the other hand, when ethylene oxide content surpasses 25% (weight) or terminal proportion of primary OH groups and surpasses 95% (mole), then reaction is too fast, can cause the thick wall part of gained porous plastics to bubble or indenture occurs in the part that the thickness of porous plastics changes, and this is disadvantageous.
Available whipping agent of the present invention is boric acid and/or its ester, the perhaps mixture of these compounds and organic carboxyl acid and/or its ester.
Boric acid and/or its ester comprise for example boric acid, methyl-borate, ethyl-borate, trimethyl borate, boric acid diethyl ester, trimethyl borate, triethyl borate and other boric acid ester.These compounds can be used alone or as a mixture.
Described organic carboxyl acid and ester thereof comprise for example formic acid, acetate, propionic acid, lauric acid, stearic acid, oleic acid, 2 ethyl hexanoic acid, oxosuccinic acid, methylene-succinic acid, hexanodioic acid, toxilic acid, the acetyl dioctyl phthalate, acetonedicarboxylic acid, propanedioic acid, succsinic acid, tartrate, diglycollic acid, the cyclopropane diglycollic acid, propene dicarboxylic acid, tartronic acid, aconic acid, citric acid, benzene tricarboxylic acid, nitrilotriacetic acid(NTA), benzene tetracarboxylic acid and mellitic acid and propanedioic acid methyl esters, malonic ester, the propanedioic acid butyl ester, the toxilic acid methyl esters, ethyl maleate, the toxilic acid butyl ester, the oxysuccinic acid methyl esters, ethyl malate, the oxysuccinic acid butyl ester, methyl succinate, ethyl succinate, succinic acid butyl ester, the hexanodioic acid methyl esters, the hexanodioic acid ethyl ester, the hexanodioic acid butyl ester, the tartrate methyl esters, ethyl tartrate and tartrate butyl ester, methyl benzoate, ethyl benzoate, Methyl Benzene-o-dicarboxylate, ethyl phthalate(DEP).These organic carboxyl acids can be used alone or as a mixture.
The consumption of whipping agent is that per 100 weight part high molecular isocyanate activity compounds are no more than 10 weight parts, preferred 0.5-2.5 weight part.
Whipping agent of the present invention also can merge use with conventional whipping agent.The example of the conventional whipping agent of available comprises water and hydrocarbon, for example pentane.Hydrocarbon has lower boiling point, from the viewpoint of the present invention as the countermeasure that overcomes the Chlorofluorocarbons (CFCs) shortcoming, and must not chloride and fluorine.
Can use the catalyzer of various known preparation urethanes among the present invention.The example of catalyzer includes organic metal catalyst such as dibutyl tin laurate and two lauric acid tin methides, or tertiary amine such as triethylenediamine, N, N, N ', N '-tetramethyl-hexane-1, the 6-diamines, N, N, N ', N ' ', N ' ' '-five methyl diethylentriamine, N, N '-two (N "; N "-dimethyl-3-aminopropyl)-and N ', N '-dimethyl ethylene diamine, N-methyl-N '-(2-dimethylamino) ethyl piperazidine, N-ethylmorpholine, the 1-Methylimidazole, 1,2 dimethylimidazole, 3-(dimethylamino) propyl imidazole, dimethylaminoethanol, two (2-dimethyl aminoethyl) ether and 1-isobutyl--glyoxal ethylines.Particularly preferred tertiary amine is 1-isobutyl--glyoxal ethyline.These catalyzer can be used alone or as a mixture.
Also tertiary amine can be added in the reaction system with the form with the preformed salt of boric acid or its ester or organic carboxyl acid or its ester.In addition, when salt is solid, the form of salt with the solution that is dissolved in linking agent (for example glycol ether) can be added in the reaction system.
Use following linking agent, tensio-active agent and other additive in the present invention in case of necessity.
The present invention also can use the known linking agent that is commonly used to prepare integral-skin polyurethane foam.The example of linking agent comprises ethylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol and other polyalkylene glycol; Glycol ether, dipropylene glycol, triglycol and other polyoxyalkylene glycol; Diethanolamine, trolamine and other alkanolamine; The oxyalkylene that is equivalent to the 1-2mol active hydrogen group with usefulness adds to low molecular weight polyols and amine such as quadrol and 2 that obtain on polyvalent alcohol such as trimethylolpropene and the glycerol, 4-/2,6-isomers of toluenediamine mixture.These linking agents can use or mix use separately.Particularly preferred linking agent is a glycol ether.
The available tensio-active agent comprises for example Nippon Unicar ' s L-5430 and L-3601; Toray Silicone ' s SRX-274C, SF-2961 and SF-2962; With other organo-siloxane tensio-active agent.
Other available additive is tinting material, antioxidant, fire retardant, viscosity-depression agent and inner pattern releasing agent applicable.Can use known additives.
Open mold method and reaction injection molding(RIM) method all can be used for the molding of integral-skin polyurethane foam.Special preferred reaction injection moulding.
To be described in further detail the present invention by embodiment and comparative example below.
In these embodiment and comparative example, following aromatic polyisocyanate, polyvalent alcohol, linking agent, catalyzer and whipping agent have been used.
Aromatic polyisocyanate (A): NCO content is 27.5% polyisocyanates, and it is to obtain with mixture (70: 30) the urethane modification of dipropylene glycol with diphenylmethanediisocyanate and polymethylene multi-phenenyl isocyanate.Wherein the NCO content of polymethylene multi-phenenyl isocyanate is 31.5% and contains three phenyl ring or many benzene ring compounds of 70% (weight).
Aromatic polyisocyanate (B): NCO content is 29.2% polyisocyanates, and it is the diphenylmethanediisocyanate of carbodiimide modification and the mixture of polymethylene multi-phenenyl isocyanate (70: 30).Wherein the NCO content of polymethylene multi-phenenyl isocyanate is 31.5% and contains three phenyl ring or many benzene ring compounds of 70% (weight).
Polyvalent alcohol (A): average functionality is 3, molecular-weight average be 6000 and ethylene oxide content be the polyvalent alcohol of 15% (weight).
Linking agent (A): glycol ether.
Catalyzer (A): the dipropylene glycol solution of 33% triethylenediamine.
Catalyzer (B): 1-isobutyl--glyoxal ethyline.
Catalyzer (C): two (2-dimethylaminoethyl) ether.
Catalyzer (D): dibutyl tin laurate.
Whipping agent (A): boric acid.
Whipping agent (B): 2 ethyl hexanoic acid.
Whipping agent (C): methyl-borate.
Whipping agent (D): trichlorofluoromethane (CFC-11).
Whipping agent (E): water.Embodiment 1
With the mixed polyhydroxy reactant that gets of 100 parts of polyvalent alcohols (A), 10 parts of linking agents (A), 0.7 part of catalyzer (B), 0.72 part of catalyzer (C), 0.01 part of catalyzer (D) and 0.58 part of whipping agent (A).Is that 1.05 ratio mixes with above-mentioned aromatic polyisocyanate (B) and above-mentioned polyhydroxy reactant with NCO/OH.Carry out the foaming of free foaming and mould.
Measured in free foaming the time (time) that time (cream time) that foam rise begins and foam rise finish that is mixed into from polyisocyanates and polyhydroxy reactant.Also measured the density (free foaming density) of gained porous plastics.
In mould foaming, with a mould and die preheating to 40 that is of a size of 400 * 100 * 10mm ℃.
The urethane raw mix is poured in the mould, close die cap, mould was left standstill 3 minutes in room temperature.From mould, take out moulded parts then, the surface hardness when measuring the demoulding with the Asker-Type-C hardness tester.After the demoulding goods are left standstill after 24 hours and measure final hardness.The foaming phenomenon do not occur, filling capacity (with the corresponding to ability of mould inner surface configuration) is strong, is shown in Table 1.Embodiment 2
Carry out the process identical with embodiment 1, difference is to add 0.2 part of whipping agent (E).The foaming phenomenon do not occur, filling capacity is strong, is shown in Table 1.Embodiment 3
Carry out the process identical with embodiment 1, difference is that whipping agent (A) will replace with 1.0 parts of whipping agents, catalyzer (B) and (C) will be respectively with 1.0 parts of corresponding catalyzer replacements.The foaming phenomenon do not occur, filling capacity is strong, is shown in Table 1.Embodiment 4
Carry out the process identical with embodiment 1, difference is that whipping agent (A) will replace with 0.58 part of whipping agent (C), the foaming phenomenon do not occur, and filling capacity is strong, is shown in Table 1.Embodiment 5
Carry out the process identical with embodiment 1, difference is that whipping agent (A) will replace with 0.3 part of whipping agent (A), 0.47 part of catalyzer (B) and (C) will be respectively with 0.53 part of corresponding catalyzer replacement.The foaming phenomenon do not occur, filling capacity is strong, is shown in Table 1.Embodiment 6
Carry out the process identical with embodiment 1, difference is that whipping agent (A) will replace with 0.47 part of whipping agent (B), and 0.3 part of whipping agent (B) and catalyzer (C) will be respectively with 0.53 part of corresponding catalyzer replacements.The foaming phenomenon do not occur, filling capacity is strong, is shown in Table 1.Comparative example 1
Carry out the process identical with embodiment 1, difference is whipping agent (A) and catalyzer (B), (C) and (D) will replaces with 16 parts of whipping agents (D) that 1.5 parts of catalyzer (A) and 0.01 part of catalyzer (D) and aromatic polyisocyanate (B) will be used aromatic polyisocyanate (A) replacement.Free foaming density reduces.The foaming phenomenon do not occur, filling capacity is strong, is shown in Table 1.Comparative example 2
Carry out the process identical with embodiment 1, difference is whipping agent (A) and catalyzer (B), (C) and (D) will replaces with 0.3 part of whipping agent (E) and 1.0 parts of catalyzer (B), 1.0 parts of catalyzer (C) and 0.01 part of catalyzer (D).Free foaming density reduces.The foaming phenomenon do not occur, the mold filling ability is shown in Table 1.Comparative example 3
Carry out the process identical with comparative example 2, difference is that whipping agent (E) will replace with 0.6 part of whipping agent.Free foaming density reduces and the foaming phenomenon occurs in porous plastics, and the result is very poor, is shown in Table 1.
Table 1
Annotate) bubble: zero still * foaming
| Comparative example | Embodiment | ||||||||
| ?1 | ??2 | ??3 | ???1 | ??2 | ??3 | ??4 | ??5 | ??6 | |
| Polyvalent alcohol (A) | ??100 | ???100 | ???100 | ???100 | ???100 | ??100 | ??100 | ??100 | ??100 |
| Linking agent (A) | ???10 | ????10 | ????10 | ????10 | ????10 | ???10 | ???10 | ???10 | ???10 |
| (B) (C) (D) for catalyzer (A) | ??1.5 ??0.01 | ???1.0 ???1.0 ???0.01 | ???1.0 ???1.0 ???0.01 | ???0.7 ???0.72 ???0.01 | ???0.7 ???0.72 ???0.01 | ??1.0 ??1.0 ??0.01 | ??0.7 ??0.72 ??0.01 | ??0.7 ??0.53 ??0.01 | ??0.7 ??0.53 ??0.01 |
| Whipping agent (A) is (C) (D) (E) (B) | ???16 | ???0.3 | ???0.6 | ???0.58 | ???0.58 ???0.2 | ??1.0 | ??0.58 | ??0.3 ??0.47 | ??0.47 ??0.3 |
| Aromatic polyisocyanate equivalence ratio (NCO/OH) | ????(A) ??1.05 | ????(B) ???1.05 | ????(B) ???1.05 | ????(B) ???1.05 | ????(B) ???1.05 | ????(B) ??1.05 | ????(B) ??1.05 | ????(B) ??1.05 | ????(B) ??1.05 |
| Free foaming cream time (second) rises sends out time (second) density (g/cm 3) | ???14 ???30 ??0.10 | ????13 ????26 ???0.29 | ????13 ????30 ???0.20 | ????16 ????32 ???0.24 | ????16 ????34 ???0.20 | ???16 ???33 ??0.23 | ???15 ???30 ??0.22 | ???16 ???29 ??0.23 | ???16 ???33 ??0.22 |
| Molding (10mm sheet material) density (g/cm 3) final during the hardness demoulding | ??0.60 ???45 ???75 | ???0.59 ????68 ????77 | ???0.60 ????70 ????81 | ???0.63 ????73 ????83 | ???0.62 ????70 ????78 | ??0.62 ???73 ???80 | ??0.62 ???67 ???78 | ??0.60 ???67 ???76 | ??0.61 ???69 ???77 |
| Demould time (branch) | ????3 | ?????3 | ?????3 | ?????3 | ?????3 | ????3 | ????3 | ????3 | ????3 |
| Bubble | ?????○ | ????○ | ??????× | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ |
| Filling capacity | ?????○ | ????× | ??????○ | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ |
Filling capacity: zero good * poor
Claims (6)
- (1) moulding product density is 0.3-0.8g/cm 3Integral-skin polyurethane foam, it is to pour in the mould by the reaction mixture with aromatic polyisocyanate, high molecular isocyanate activity compound, whipping agent and other additive to obtain, and comprises using boric acid and/or its ester to make whipping agent.
- (2) integral-skin polyurethane foam of claim (1), wherein whipping agent is the mixture of boric acid and/or its ester and organic carboxyl acid and/or its ester.
- (3) pour into by reaction mixture that to prepare moulding product density in the mould be 0.3-0.8g/cm with aromatic polyisocyanate, high molecular isocyanate activity compound, whipping agent and other additive 3The method of integral-skin polyurethane foam, comprise and use boric acid and/or its ester to make whipping agent.
- (4) method of the integral-skin polyurethane foam of preparation claim (3), wherein whipping agent is the mixture of boric acid and/or its ester and organic carboxyl acid and/or its ester.
- (5) preparation method of the integral-skin polyurethane foam of claim (3) or (4), wherein this preparation method is the reaction injection molding(RIM) method.
- (6) vehicle steering, indoor hardware fitting or the furniture of preparation method's manufacturing of usefulness claim (3), (4) or (5).
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP181320/1994 | 1994-08-02 | ||
| JP181320/94 | 1994-08-02 | ||
| JP18132094 | 1994-08-02 | ||
| JP200840/94 | 1994-08-25 | ||
| JP20084094 | 1994-08-25 | ||
| JP200840/1994 | 1994-08-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1121091A true CN1121091A (en) | 1996-04-24 |
| CN1058030C CN1058030C (en) | 2000-11-01 |
Family
ID=26500555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95109512A Expired - Fee Related CN1058030C (en) | 1994-08-02 | 1995-08-02 | Integral-skin polyurethane foam, preparation process and use of same |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR0184030B1 (en) |
| CN (1) | CN1058030C (en) |
| MY (1) | MY121940A (en) |
| TW (1) | TW332825B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2355225A (en) * | 1999-09-30 | 2001-04-18 | Toyoda Gosei Kk | Process for moulding an integral skin foam and a polyurethane formulation for moulding the same |
| CN101541866B (en) * | 2006-09-22 | 2011-08-24 | 陶氏环球技术有限责任公司 | Polyurethane foam article |
| CN102399358A (en) * | 2010-09-03 | 2012-04-04 | Sika技术股份公司 | Heat curable epoxy resin composition with water as foaming agent |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100883514B1 (en) * | 2007-07-02 | 2009-02-11 | 주식회사 엘지화학 | Integral skin polyurethane foam composition, integral skin polyurethane foam prepared by using the same, and method for testing property of integral skin polyurethane foam |
-
1995
- 1995-07-14 MY MYPI95001990A patent/MY121940A/en unknown
- 1995-07-18 TW TW084107400A patent/TW332825B/en not_active IP Right Cessation
- 1995-07-28 KR KR1019950022789A patent/KR0184030B1/en not_active IP Right Cessation
- 1995-08-02 CN CN95109512A patent/CN1058030C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2355225A (en) * | 1999-09-30 | 2001-04-18 | Toyoda Gosei Kk | Process for moulding an integral skin foam and a polyurethane formulation for moulding the same |
| GB2355225B (en) * | 1999-09-30 | 2002-11-20 | Toyoda Gosei Kk | Process for molding an integral skin foam |
| US6569365B1 (en) | 1999-09-30 | 2003-05-27 | Toyoda Gosei, Co., Ltd. | Process for molding an integral skin foam |
| CN101541866B (en) * | 2006-09-22 | 2011-08-24 | 陶氏环球技术有限责任公司 | Polyurethane foam article |
| CN102399358A (en) * | 2010-09-03 | 2012-04-04 | Sika技术股份公司 | Heat curable epoxy resin composition with water as foaming agent |
| CN102399358B (en) * | 2010-09-03 | 2016-07-06 | Sika技术股份公司 | Water is as the thermosetting epoxy resin composition of foaming agent |
Also Published As
| Publication number | Publication date |
|---|---|
| TW332825B (en) | 1998-06-01 |
| KR960007664A (en) | 1996-03-22 |
| KR0184030B1 (en) | 1999-05-15 |
| MY121940A (en) | 2006-03-31 |
| CN1058030C (en) | 2000-11-01 |
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| C14 | Grant of patent or utility model | ||
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20001101 Termination date: 20130802 |