CN1644599A - Method for preparing Soft polyurethane foam with excellent ball elasticity - Google Patents
Method for preparing Soft polyurethane foam with excellent ball elasticity Download PDFInfo
- Publication number
- CN1644599A CN1644599A CN 200410061508 CN200410061508A CN1644599A CN 1644599 A CN1644599 A CN 1644599A CN 200410061508 CN200410061508 CN 200410061508 CN 200410061508 A CN200410061508 A CN 200410061508A CN 1644599 A CN1644599 A CN 1644599A
- Authority
- CN
- China
- Prior art keywords
- polyurethane foam
- flexible polyurethane
- polyol
- diisocyanate
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The object of this invention is to improve ball reboundability (a rebound elastic function) without reducing physical properties such as mechanical strengths, compressive strengths and the like of a flexible polyurethane foam. In a method for forming a flexible polyurethane foam using a molding composition comprising an organic diisocyanate, a high molecular polyol, a catalyst, a foam stabilizer, a foaming agent using water or water and an arbitrary foaming agent, a low molecular compound having an adjacent carbon-carbon unsaturated bond and a carbonyl group is added to the composition as a modifier in 1-20wt.% based on the high molecular polyol.
Description
Technical Field
The present invention relates to a process for producing a flexible polyurethane foam, and more particularly to a process for producing a flexible polyurethane foam having improved ball rebound resilience by using a specific modifier.
Background
Recently, plastic materials have been widely used as importantmaterials in all fields of industrial technology, and among them, polyurethane resins are used in a wide variety of applications due to their excellent physical properties, economical efficiency, moldability, and wide application range.
Polyurethane resins have a urethane bond in the molecule, are synthesized by addition polymerization of a diisocyanate and an active hydrogen-containing compound, have excellent properties such as abrasion resistance, durability, mechanical properties, and chemical resistance, and can give molded products ranging from soft to hard, and thus are widely used for synthetic leathers, paints, foams, and fiber products.
Polyurethane resin foams (materials and products of foams) are used as cushioning materials for furniture, bedding, and sheets for vehicles such as automobiles, and particularly, cushioning materials for automobiles are industrially required in a very large amount and are required to have various performances.
In the past, in order to improve the ball rebound resilience, from the viewpoint of a polyurethane production material, methods such as introducing ether units derived from ethylene oxide into the molecular chain of a polymer polyol (see patent document 1) or increasing the hydroxyl equivalent of a polymer polyol have been employed, but these methods have caused problems such as a reduction in mechanical strength such as tensile rupture strength, elongation at tensile rupture, and tensile rupture strength, and compressive strength, although the ball rebound resilience is improved. Further, as the polyisocyanate, a production method has been proposed in which the rebound resilience is improved by using an isocyanate group-terminated prepolymer obtained by reacting diphenylmethane diisocyanate with a poly (oxyalkylene) polyol (see patent document 2), but the rebound resilience and other mechanical properties cannot be sufficiently satisfied.
There have been disclosed a method for producing a flexible polyurethane foam excellent in elasticity without requiring a crushing operation by using a metaphenylene diisocyanate, a diphenylmethane diisocyanate, a long-chain polyol polyoxyethylene polyoxypropylene polyol and a blowing agent (see patent document 3), a method for specifying the air flow rate, the resistance value at the time of compression, and the like of a flexible polyurethane foam by using an oxyethylene compound such as oxyethylene random polymerization in combination with a polyol (see patent document 4), and the like, but there has been no improvement in ball rebound resilience without lowering the mechanical strength, the compressive strength, and the like.
Patent document 1: japanese table 2003-514040 (abstract)
Patent document 2: japanese patent laid-open No. 2003-147044 (abstract)
Patent document 3: japanese patent laid-open No. 8-245746 (claim 1 of abstract and patent claims)
Patent document 4: japanese patent laid-open publication No. 2003-105050 (claim 1 of abstract and patent claims)
Disclosure of Invention
As described in paragraphs 5 to 6, the flexible polyurethane foam to be used for a heavy use in a cushioning material for automobiles and the like is important not only in physical properties such as mechanical strength and compression strength but also in the function of ball rebound resilience (rebound resilience), and there is a strong demand for the development of a flexible polyurethane foam in which the ball rebound resilience is improved without lowering the physical properties such as mechanical strength and compression strength. In the prior art, the two aspects of rebound elasticity and other mechanical properties cannot be fully satisfied, so that the achievement of the full satisfaction of the two aspects is the problem to be solved by the invention.
In order to solve the above problems, the present inventors have studied a method for improving the ball rebound resilience without lowering the physical properties such as mechanical strength and compressive strength, and have studied various studies in consideration of regulations and breakings of the main raw materials of the flexible polyurethane foam, namely, organic diisocyanate and polyol, blowing agent and foam stabilizer, other auxiliary agents, polymerization conditions and polymerization catalyst, and also air permeability of the flexible polyurethane foam, and have conducted experiments and various observations many times.
Among these, as a cumulative result of experimental studies and trials, in order to solve the above problems, it was found that the problems of the present invention were effectively solved by adding a modifier to a composition for forming a flexible polyurethane foam, which is obtained by modifying a polyol, a polyisocyanate or the like in the above-mentioned background art (paragraphs 5 to 6) and has not been sufficiently achieved, and further, various modifiers were studied, and it was found that it is very effective to improve the ball rebound without lowering the physical properties such as mechanical strength and compressive strength of the flexible polyurethane foam by using a specific modifier, and the present invention was completed.
The modifier for the composition for forming a flexible polyurethane foam of the present invention is a modifier using a low molecular weight compound having an adjacent carbon-carbon unsaturated bond and a carbonyl group, such as dialkyl maleate, and is particularly effective to be added in an amount of 1 to 20% by weight based on the polymer polyol.
The present invention is a process for producing a flexible polyurethane foam, the essential constituent element of which is the addition of a low-molecular-weight compound having an adjacent carbon-carbon unsaturated bond and a carbonyl group as a modifier for a flexible polyurethane foam to a composition for molding a flexible polyurethane foam, characterized in that in the process for producing a flexible polyurethane foam from a molding composition comprising an organic diisocyanate (A), a polymer polyol (B), a catalyst (C), a foam stabilizer (D), a blowing agent (E) and other auxiliary agents, 1 to 20% by weight of a low-molecular-weight compound (α -unsaturated carbonyl compound) (F) having an adjacent carbon-carbon unsaturated bond and a carbonyl group as a modifier for the composition is added to the polymer polyol.
In the present invention, the effect is more excellent when an organic diisocyanate, a polymer polyol, a foaming agent or the like is specified.
In the present invention, it is considered that the improvement method is a novel means completely different from the idea of the conventional method, and the improvement method can obtain a result of remarkably improving the ball rebound resilience without lowering the physical properties such as mechanical strength and compressive strength, and it is said that the object of the present invention is to be met by a novel technique.
The low-molecular-weight compound having an adjacent carbon-carbon unsaturated bond and a carbonyl group used in the present invention is a generally known compound, and has been used as a raw material for a polyurethane resin or a modifier thereof in the past. In the production of a flexible polyurethane foam, for example, a monoester reaction product of an organic acid anhydride and an alkoxylated primary alcohol is used as a cell opening agent (see the patent claims of Japanese patent laid-open No. 2000-38431), thereaction product is a low molecular compound having carbon-carbon unsaturated bond and carbonyl group, which is consistent with the modified material of the invention in form, however, the purpose of use, the mode of use, and the structure of the invention itself are completely different, and the technique described in Japanese unexamined patent application publication No. 2000-38431 is not actually related to the present invention at all, and, even when used as a raw material for a general polyurethane resin or a modifier for the polyurethane resin from the past, the use purpose, the use mode, and the constitution of the invention itself are completely different, it is thus to be clearly understood that the above-identified general knowledge is not admitted to be prior art to the teaching and suggestion of the present invention.
The above is a summary description of the invention and the basic configuration of the invention, and the invention is generally constituted by the following invention unit groups, the invention of (1) is a basic invention, and the following invention is embodied or implemented (it is necessary to say that all the invention groups are collectively referred to as "the invention").
(1) A process for producing a flexible polyurethane foam, characterized in that in a process for producing a flexible polyurethane foam from a composition comprising an organic diisocyanate (A), a polymer polyol (B), a catalyst (C), a foam stabilizer (D), a blowing agent (E) comprising water or water and an optional blowing agent, and other auxiliary agents, 1 to 20% by weight of a low-molecular compound (F) having an adjacent carbon-carbon unsaturated bond and a carbonyl group is added to the composition as a modifier relative to the polymer polyol.
(2) The process for producing a flexible polyurethane foam according to (1), wherein the organic diisocyanate (A) is selected from the group consisting of diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate and tolylene diisocyanate, alone or in combination with 2 or more kinds thereof.
(3) The process for producing the flexible polyurethane foam according to (1) or (2), wherein the total content of the 2, 2 '-MDI isomers and the 2, 4' -MDI isomers is 1 to 60% by weight in the isomer composition ratio of diphenylmethane diisocyanate (MDI).
(4) The process for producing a flexible polyurethane foam according to (1) or (2), wherein the polymer polyol (B) is a polyether polyol and/or a polyester polyol having a number average molecular weight of 1,000 to 10,000 and a standard functional group number of 2 or more.
(5) The process for producing a flexible polyurethane foam according to any one of (1) to (4), wherein the modifier (F) is a dialkyl maleate.
(6) And a flexible polyurethane foam having a high ball rebound resilience, which is produced by the production method of any one of (1) to (5).
In the present invention, the soft polyurethane foam can significantly improve the ball rebound resilience (rebound performance) without lowering the physical properties such as mechanical strength and compressive strength.
The flexible polyurethane foam having a high ball rebound resilience produced by the present invention can be widely used in industrial applications mainly as a cushioning material for automobiles.
In the present invention, the basic configuration of the present invention has been discussed above as a means for solving the problems, and the following describes in detail the embodiments of the present invention group described above.
In the present invention, a specific amount of a low-molecular weight compound having an adjacent carbon-carbon unsaturated bond and a carbonyl group is used as a modifier for a composition for molding a flexible polyurethane foam, and the modifier is capable of significantly improving the ball rebound resilience (rebound resilience) without substantially reducing the physical properties such as mechanical strength and compressive strength, and obtaining the action and effect corresponding thereto, and the materials, polymerization conditions, action of polymerization reaction, and the like are described.
(1) Organic diisocyanate (A)
The organic diisocyanate (A) used in the present invention is a general diisocyanate, and examples of the aromatic diisocyanate include 2, 4-Tolylene Diisocyanate (TDI), 2, 6-tolylene diisocyanate, 4 ' -diphenylmethane diisocyanate (MDI), 2, 4 ' -diphenylmethane diisocyanate, 2 ' -diphenylmethane diisocyanate, polyphenylene polymethylene polyisocyanate (p-MDI), 1, 5-Naphthylene Diisocyanate (NDI), 1, 4-naphthylene diisocyanate, p-phenylene diisocyanate (PPDI), m-phenylene diisocyanate, o-Xylylene Diisocyanate (XDI), m-xylylene diisocyanate, 4 ' -diphenyl ether diisocyanate, 2 ' -diphenylpropane 4, 4 ' -diisocyanate, 3 ' -dimethoxydiphenyl-4, 4 ' -diisocyanate, nitrodiphenyl diisocyanate, diphenylpropane diisocyanate and the like, and examples of the aliphatic diisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, 2-methyl-1, 5-pentane diisocyanate and the like. Examples of the alicyclic diisocyanate include 1-methylcyclohexane-2, 4-diisocyanate (hydrogenated TDI), isophorone diisocyanate (IPDI), dicyclohexylmethane-4, 4' -diisocyanate (hydrogenated MDI), and various modifications such as polymers of these diisocyanates, urethane modifications, urea modifications, allophanate modifications, and biuret modifications (ビユウレツト) may be used.
The above-mentioned diisocyanates may be used in 1 kind alone or in a mixture of 2 or more kinds. It is tobe noted that, particularly when the above-mentioned MDI, a mixture of MDI and p-MDI, TDI, a mixture of TDI and MDI, and a mixture of TDI and MDI and p-MDI are used, a flexible polyurethane foam of better quality can be obtained.
3 isomers such as 2, 2 ' -MDI, 2, 4 ' -MDI and 4, 4 ' -MDI exist in diphenylmethane diisocyanate (MDI), and the total content of the isomers of 2, 2 ' -MDI and 2, 4 ' -MDI is preferably 1 to 60% by weight, more preferably 2 to 55% by weight. When the total content is less than the lower limit, the storage stability of the diisocyanate is liable to be lowered, and when the total content exceeds the upper limit, the hardness of the flexible polyurethane foam obtained is liable to be lowered.
(2) Polymer polyol (B)
The polymer polyol (B) is a polyol which is addition-polymerized with a diisocyanate to form a polyurethane, and in the present invention, a polyether polyol and/or a polyester polyol are preferable. Further, the number average molecular weight is preferably 1,000 to 10,000, and the number of standard functional groups is preferably 2 or more. If the number average molecular weight is less than the lower limit, the flexibility of the resulting foam is insufficient, and if it exceeds the upper limit, the hardness of the foam tends to decrease. The standard number of functional groups represents the average functional group (number of active hydrogen atoms per molecule) of the polyol, and in practice there are only a few due to terminal unsaturation.
As the polyether polyol, polypropylene ethylene polyol (PPG), polytetramethylene ether glycol (PTG), and the like can be used. As the polyester polyol, an ethylene adipate polyester polyol of a polycondensation type polyester polyol, a polycaprolactone polyol of a lactone type polyol, or the like can be used.
(3) Catalyst (C)
In the present invention, various urethane-forming catalysts known in the art can be used as the catalyst (C).
Examples thereof include triethylamine, tripropylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, dimethylbenzylamine, N, N, N ', N' -tetramethylhexamethylenediamine, N, N, N ', N', N "-pentamethyldiethylenetriamine, bis- (2-dimethylaminoethyl) ether, triethylenediamine, 1, 8-diazabicyclo (5, 4, 0) undecene [7], 1, 2-dimethylimidazole, dimethylethanolamine, N, N-dimethyl-N-hexanolamine, organic acid salts thereof, organic metal compounds such as スタナスオクトエ - ト and zinc naphthenate. Further, amine catalysts having active hydrogen such as N, N-dimethylethanolamine and N, N-diethylethanolamine are preferable.
The amount of the catalyst (C) added is preferably 0.01 to 10% by weight based on the polyol (B).
(4) Foam regulator (D)
As the foam stabilizer, a usual surfactant can be used, and a silicone surfactant is suitably used. Examples thereof include L-520 and L-5309 manufactured by Nippon Kogyo ユニカ -, SRX-274C, SF-2962 manufactured by Toray Corning, DC-5169 manufactured by エア - プロダクツ, and F-220 manufactured by shin-Etsu chemical industry.
The amount of the foam stabilizer (D) added is preferably 0.01 to 10% by weight based on the polyol (B).
(5) Foaming agent (E)
The blowing agent is mainly water. The water generates carbon dioxide gas by reaction with the isocyanate group, thereby foaming. In addition, water and any additional blowing agent may also be used. For example, a small amount of low-boiling organic compound such as cyclopentane or isopentane may be used together, or air, nitrogen or liquefied carbon dioxide may be mixed and dissolved in the stock solution to foam the mixture by using a gasloading apparatus (ガスロ - デング).
The amount of the blowing agent added is determined in accordance with the set density of the product to be obtained, and is usually 0.5 to 15% by weight based on the polyol (B). If the amount exceeds the upper limit, the foam is difficult to stabilize, and if the amount is less than the lower limit, the foam cannot be foamed effectively.
(6) Modifying agent
The modifier is a substance constituting a main constituent of the present invention, and is added to a composition for molding a flexible polyurethane foam to improve the physical properties of a foamed product.
The specific modifier used in the present invention is very effective for improving the ball rebound without lowering the physical properties such as mechanical strength and compressive strength of the flexible polyurethane foam. Ball rebound, also known as rebound performance, is one of the rheological properties of a foamed article. When mechanical deformation is imparted to a foamed product, the foamed product is deformed into elastic when the amount of deformation is small, and the foamed product is restored to its original state after the deformation is removed by an external force.
The ball rebound resilience value is an index of energy to the elastic limit, and is measured in accordance with JIS-K6400 in units of "%" without c.g.s.
The modifier is particularly effective when added in an amount of 1 to 20% by weight based on the weight of the polymer polyol. If the amount is less than the lower limit, the modifying effect is insufficient, and if the amount is more than the upper limit, other physical properties may be deteriorated.
In the present invention, as a modifier for a flexible polyurethane foam molding composition, a low-molecular compound (α -unsaturated carbon-based compound) having an adjacent carbon-carbon unsaturated bond and a carbonyl group is used.
The low-molecular-weight compound having an unsaturated bond between adjacent carbon and carbon atoms and a carbonyl group is a compound represented by dialkyl maleate, and is an unsaturated carboxylic acid, an ester, an anhydride, an amide or a halide of an unsaturated carboxylic acid, an unsaturated aldehyde, an unsaturated ketone, various substituted derivatives thereof, or the like.
Specific examples of the compound include maleic acid, maleic acid esters, fumaric acid esters, acrylic acid esters, methacrylic acid esters, itaconic acid, and itaconic acid esters, and various compounds such as acrolein, methacrolein, crotonic acid, benzoquinone, and isophorone can be used.
Among them, maleic acid esters are particularly preferable from the viewpoints of reaction rate with primary amines, viscosity, miscibility with organic diisocyanates or polyols, odor, safety, price, and the like.
The reason why the low-molecular weight compound having an adjacent carbon-carbon unsaturated bond and a carbonyl group is very effective for improving the ball rebound resilience without lowering the physical properties such as mechanical strength and compressive strength of the flexible polyurethane foam is not clear, but it is presumed that the low-molecular weight compound is caused by the following reaction and action in the case of maleic acid ester.
The basic compound (Base) present in the flexible polyurethane foam molding composition of the following formula acts on the carbon-carbon unsaturated bond of the dialkyl maleate of the low-molecular compound (α -unsaturated carbonyl compound) having an adjacent carbon-carbon unsaturated bond and a carbonyl group, which is added as a modifier to the flexible polyurethane foam molding composition.
Then, α -unsaturated carbonyl group undergoes Michael addition reaction as shown in the following formula.
Specifically, the amine compound represented by formula 3 derived from an organic diisocyanate present in the composition for polyurethane foam molding is subjected to Michael addition reaction. The amine compound is represented by the formulaThe organic diisocyanate reacts with the water of the foaming agent to generate [ R-NHCOOH]Intermediate, followed by formation of R-NH2。
Therefore, in the process for producing a flexible polyurethane foam by using a blowing agent (E) comprising water or water and an optional blowing agent, the present invention is characterized by combining a low-molecular compound (F) having an adjacent carbon-carbon unsaturated bond and a carbonyl group as a modifier.
The>N-H groups in the addition reaction product are then reacted with the isocyanate groups in the organic diisocyanate as shown in the following formula.
As a result, a substituted urea represented by the following formula was produced.
It is presumed that the formation of the substituted urea asdescribed above suppresses the formation of the normal urea, thereby improving the rebound resilience.
(7) Other auxiliaries
In the present invention, a chain extender in a usual addition polymerization reaction may be used as necessary.
As the chain extender in urethane polymerization, a general low molecular weight compound having 2 or more active hydrogen groups is used, and specifically, ethylene glycol, propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, diethanolamine, triethanolamine and the like can be used.
Further, as various additives, flame retardants, plasticizers, antioxidants, ultraviolet absorbers, colorants, fillers, internal mold release agents, and other processing aids can be used.
Of these auxiliaries, those having no active hydrogen which reacts with isocyanate may be used by being mixed in advance in the polyurethane foam-forming composition.
(8) Flexible polyurethane foam
In the present invention, the flexible polyurethane foam product having a ball rebound resilience (rebound resilience) significantly improved without lowering physical properties such as mechanical strength and compressive strength, which is produced by the above-described detailed process for producing a flexible polyurethane foam, is also included in the scope of the present invention, and is used as a cushioning material having an improved function as a sheet material for vehicles such as furniture, bedding, and automobiles.
(9) Preparation of foams by urethanization foaming
In the present invention, as a method for producing a polyurethane foam, a conventionally known urethanization reaction technique is used. For example, a high-molecular polyol and an organic diisocyanate are reacted with each other to increase the molecular weight and expand the product with a chain extender, thereby obtaining the desired flexible polyurethane foam.
In this reaction, it is needless to say that, as described above, a suitable amount of a tertiary amine, a polymerization catalyst known in urethanization reactions represented by organic metal salts of tin, lead, and titanium, and the like can be used.
Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, and preferred embodiments will be described in more detail. (the "ratios" and "%" described in examples and comparative examples represent weight ratios and weight%)
(preparation of raw Material)
(preparation of polyol premix)
Polyol premixes OH-1 to OH-11 were prepared in the proportions shown in Table 1.
TABLE 1
| OH -1 | OH -2 | OH -3 | OH -4 | OH -5 | OH -6 | OH -7 | OH -8 | OH -9 | OH -10 | OH -11 | |
| Polyol 1 Polyol 2 Polyol 3 Polyol 4 Catalyst 1 Catalyst 2 Catalyst 3 Catalyst 4 Catalyst 5 Foam stabilizer 1 Foam regulator 2 Foam regulator 3 Water (W) DOM Small chamber opening Releasing agent | 70 30 0.5 0.05 0.7 3.5 9.2 | 70 30 0.5 0.05 0.7 3.5 0.5 9.2 | 70 30 0.5 0.05 0.7 3.5 5 9.2 | 70 30 0.5 0.05 0.7 3.5 10 9.2 | 70 30 0.5 0.05 0.7 3.5 20 9.2 | 60 40 0.05 0.3 1 3 | 60 40 0.05 0.3 1 3 5 | 100 0.05 1.5 1 4 | 100 0.05 1.5 1 4 5 | 100 0.05 1.5 1 4 | 100 0.05 1.5 1 4 5 |
Polyol 1: FA-703 (Sanyo chemical industry polyether polyol hydroxyl value 34(mgKOH/g))
Polyol 2: FA-728R (Sanyo chemical industry polyether polyol hydroxyl value 28(mgKOH/g))
Polyol 3: n-2200 (hydroxyl value of polyester polyol 60.5(mgKOH/g) manufactured by Japan polyurethane industry)
Polyol 4: GP-3000 (hydroxyl value of polyether polyol 56(mgKOH/g) made by Sanyo chemical industry)
Catalyst 1: tertiary amine catalyst (catalyst of amine type made by Tosoh)
Catalyst 2: tertiary amine catalyst (catalyst of amine type made by Tosoh)
Catalyst 3: tertiary amine catalyst (TEDA-L33 made by Tosoh)
Catalyst 4: metal catalyst (DABCO T-9 エア - プロダクツ)
Catalyst 5: morpholine catalyst (KAOLIZER No.22 made by king flowers)
Foam stabilizer 1: silicon foam stabilizer B4113LF (ゴ - ルドシユミツト)
Foam stabilizer 2: silicon foam stabilizer B-8719 (manufactured by ゴ - ルドシユミツト)
Foam stabilizer 3: silicon foam stabilizer SE-232 (manufactured by Japan ユニカ -Inc.)
DOM: maleic acid di-2-ethylhexyl ester
(preparation of isocyanate)
The isocyanate was prepared in the proportions shown in Table 2.
TABLE 2
| NCO-1 NCO-2 NCO-3 | |
| Isocyanate A B C D | 52 30 48 70 100 |
In the context of Table 2, the following examples are,
a: diphenylmethane diisocyanate
B: MR-200 (high molecular MDI made by Japan polyurethane industry)
C: MF-24MR (high molecular MDI made by Japan polyurethane industry)
D: tolylene diisocyanate
Examples 1 to 6 and comparative examples 1 to 5
Polyol premixes and isocyanate components were compounded at the compounding ratios described in tables 1 and 2, and after adjusting the temperature to 25 ℃, they were weighed in a 2000ml beaker (ポリカツプ) and stirred with a hand mixer at 3000rpm for 10 seconds. Immediately after the stirring, the mixture was poured into an acrylic cell having an inner size of 250X 250mm to foam. After standing for 24 hours, the sheet was cut into a predetermined shape, and the items shown in Table 3 were measured. The physical properties were measured according to JIS K6400.
TABLE 3
| Multiple element Alcohol pre-treatment Mixture of | Poly (iso) form Cyanic acid Esters | Isocyanates Acid esters Index of refraction | Ball game Elasticity ％ | Apparent appearance Density of kg/m3 | 25% pressure Shrinkage strength N/100cm2 | Stretching Strength of kPa | Elongation of ％ | Pulling crack N/m | Compression Permanent Deformation of ％ | |
| Comparison Example 1 | OH-1 [0] | NCO-1 | 90 | 56 | 40.0 | 20.8 | 91 | 111 | 3.5 | 5.2 |
| Comparison Example 2 | OH-2 [0.5] | NCO-1 | 90 | 57 | 40.4 | 19.6 | 97 | 112 | 3.4 | 3.6 |
| Practice of Example 1 | OH-3 [5] | NCO-1 | 90 | 64 | 40.7 | 19.3 | 92 | 106 | 3.5 | 5.5 |
| Practice of Example 2 | OH-4 [10] | NCO-1 | 90 | 66 | 43.5 | 20.8 | 90 | 97 | 3.5 | 5.8 |
| Practice of Example 3 | OH-5 [20] | NCO-1 | 90 | 66 | 44.2 | 21.1 | 91 | 96 | 3.4 | 5.9 |
| Comparison Example 3 | OH-6 [0] | NCO-2 | 100 | 66 | 44.0 | 19.6 | 84 | 98 | 5.3 | 3.9 |
| Practice of Example 4 | OH-7 [5] | NCO-2 | 100 | 72 | 44.3 | 19.2 | 87 | 99 | 5.3 | 4.0 |
| Comparison Example 4 | OH-8 [0] | NCO-3 | 100 | 27 | 27.6 | 42.0 | 135 | 193 | 7.7 | 4.0 |
| Practice of Example 5 | OH-9 [5] | NCO-3 | 100 | 33 | 27.8 | 41.6 | 137 | 197 | 7.6 | 4.1 |
| Comparison Example 5 | OH-10 [0] | NCO-3 | 111 | 42 | 25.3 | 34.8 | 86 | 153 | 5.1 | 1.3 |
| Practice of Example 6 | OH-11 [5] | NCO-3 | 111 | 50 | 25.7 | 34.4 | 87 | 150 | 5 | 1.2 |
The isocyanate index in table 3 is the ratio of NCO groups to the number of active hydrogen atoms present in the compound. 25% compressive strength N/100cm2Measurement method (2) measurement of specimens according to JIS K6400The whole surface of the product piece is compressed by 10 multiplied by 10 cm.
The number in []in the polyol premix is the weight ratio of the modifier DOM.
Examination of the results of examples and comparative examples
As is clear from comparison between the above examples and comparative examples, in the present invention, the addition of 1 to 20% by weight of the specific modifying agent (DOM) of the present invention significantly improves the ball rebound (rebound) performance of the flexible polyurethane foam without lowering the physical properties such as mechanical strength and compressive strength of the flexible polyurethane foam.
The polyol premix and the polyisocyanate used the same raw materials, and the groups of comparative examples 1 and 2 and examples 1 to 3, the group of comparative example 3 and example 4, the group of comparative example 4 and example 5, and the group of comparative example 5 and example 6, in which the amount of the modifier DOM was changed, were compared with each other to clearly show the mechanical properties such as compressive strength, tensile and tear strength, and compression set of each example, and were almost the same as those of each comparative example.
Claims (6)
1. A process for producing a flexible polyurethane foam, which comprises adding 1 to 20% by weight of a low molecular compound (F) having an adjacent carbon-carbon unsaturated bond and a carbonyl group as a modifier to a polymer polyol in a composition comprising an organic diisocyanate (A), the polymer polyol (B), a catalyst (C), a foam stabilizer (D), a blowing agent (E) comprising water or water and an optional blowing agent, and other auxiliary agents.
2. The process for producing a flexible polyurethane foam according to claim 1, wherein the organic diisocyanate (A) is selected from the group consisting of diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, tolylene diisocyanate, alone or in combination of 2 or more.
3. The process for producing a flexible polyurethane foam according to claim 2, wherein the total content of 2, 2 '-MDI and 2, 4' -MDI isomers in the isomer composition ratio of diphenylmethane diisocyanate (MDI) is 1 to 60% by weight.
4. The process for producing a flexible polyurethane foam according to claim 1 or 2, wherein the polymer polyol (B) is a polyether polyol and/or a polyester polyol having a number average molecular weight of 1,000 to 10,000 and a standard functional group number of 2 or more.
5. The process for producing a flexible polyurethane foam according to any one of claims 1 to 4, wherein the modifier (F) is a dialkyl maleate.
6. A flexible polyurethane foam having a high ball rebound resilience, which is produced by the production method according to any one of claims 1 to 5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004004865A JP4556161B2 (en) | 2004-01-09 | 2004-01-09 | A method for producing a flexible polyurethane foam having excellent ball rebound properties. |
| JP20044865 | 2004-01-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1644599A true CN1644599A (en) | 2005-07-27 |
| CN100465205C CN100465205C (en) | 2009-03-04 |
Family
ID=34819351
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100615089A Expired - Fee Related CN100465205C (en) | 2004-01-09 | 2004-12-27 | Method for preparing Soft polyurethane foam with excellent ball elasticity |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4556161B2 (en) |
| CN (1) | CN100465205C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108530595A (en) * | 2018-04-11 | 2018-09-14 | 东莞市秦粤丰鞋材有限公司 | PU footwear materials and its manufacturing method and application |
| CN108601435A (en) * | 2016-05-30 | 2018-09-28 | 科丝美诗株式会社 | Hydridization type foam and the cosmetic agent box for using the hydridization type foam |
| CN112409560A (en) * | 2019-08-21 | 2021-02-26 | 万华化学（北京）有限公司 | High-resilience polyurethane foam and preparation method thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6214129B2 (en) * | 2011-12-13 | 2017-10-18 | 株式会社東洋クオリティワン | Manufacturing method of different hardness mold foam |
| CN104448203A (en) * | 2014-12-23 | 2015-03-25 | 金华派对乳胶工艺品有限公司 | Formula and preparation method of polyurethane soft high-resilience filling product |
| CN105131233B (en) * | 2015-07-21 | 2017-10-10 | 浙江川洋家居股份有限公司 | A kind of polyester modification sponge and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03244620A (en) * | 1990-02-23 | 1991-10-31 | Asahi Glass Co Ltd | Production of polyurethane foam |
| DE4025817A1 (en) * | 1990-08-16 | 1992-02-20 | Bayer Ag | METHOD FOR THE PRODUCTION OF OPEN CELL POLYURETHANOUS FUELS AND THEIR USE AS UPHOLSTERED MATERIAL |
| JPH0559144A (en) * | 1991-08-28 | 1993-03-09 | Asahi Glass Co Ltd | Production of flexible polyurethane foam |
| BR9902239A (en) * | 1998-06-17 | 2000-04-11 | Air Prod & Chem | Process and composition of banknote additives for rigid flexible polyurethane foams. |
-
2004
- 2004-01-09 JP JP2004004865A patent/JP4556161B2/en not_active Expired - Fee Related
- 2004-12-27 CN CNB2004100615089A patent/CN100465205C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108601435A (en) * | 2016-05-30 | 2018-09-28 | 科丝美诗株式会社 | Hydridization type foam and the cosmetic agent box for using the hydridization type foam |
| CN108530595A (en) * | 2018-04-11 | 2018-09-14 | 东莞市秦粤丰鞋材有限公司 | PU footwear materials and its manufacturing method and application |
| CN112409560A (en) * | 2019-08-21 | 2021-02-26 | 万华化学（北京）有限公司 | High-resilience polyurethane foam and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100465205C (en) | 2009-03-04 |
| JP2005194486A (en) | 2005-07-21 |
| JP4556161B2 (en) | 2010-10-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU766760B2 (en) | Improved cellular or elastomeric plastic material | |
| EP1921099A1 (en) | Composition for polyurethane foam, polyurethane foam obtained from the composition, and use thereof | |
| CN1240736C (en) | Manufacture of MDI-TDI based flexible polyurethane foams | |
| JP6703945B2 (en) | Conventional flexible foam based on PIPA polyol | |
| CN1229803A (en) | Low resilience urethane foam | |
| WO2000073368A1 (en) | Composition for use in flexible polyurethane foams | |
| JPS6067524A (en) | Improvement of heat resistance of extremely soft polyurethane elastomer | |
| JP2008274051A (en) | Polyisocyanate composition for flexible polyurethane foam and method for producing flexible polyurethane foam using the composition | |
| JP2006104404A (en) | Polyurethane pad for vehicle seat | |
| JP5346228B2 (en) | Polyol composition and use thereof | |
| JP2001002749A (en) | Flexible polyurethane slab foam and its production | |
| JP2007246904A (en) | Aromatic diacid ester diol and its substituted carbamate for minimizing deterioration of foamed polyurethane | |
| CN1847281A (en) | Polyisocyanates for soft polyurethane foam board and producing method for soft polyurethane foam board using same | |
| JP2008247996A (en) | Polyisocyanate composition and manufacturing method for soft polyurethane foam using it | |
| CN1644599A (en) | Method for preparing Soft polyurethane foam with excellent ball elasticity | |
| JP2001329042A (en) | Production method of highly resilient highly vibration absorbing soft polyurethane foam | |
| JPH11171962A (en) | Production of flexible polyurethane foam | |
| JP2002322236A (en) | Method for producing soft polyurethane slab foam | |
| JPH11171963A (en) | Production of flexible polyurethane foam | |
| CN1778828A (en) | Dispersion stabilizer made from polyfunctional isocyanic ester and acrylic hydroxyalkyl ester and used for polymer popyalcohol preparation | |
| JPH11255858A (en) | Preparation of soft polyurethane foam | |
| JP3355619B2 (en) | Method for producing skin-integrated flexible polyurethane foam | |
| JP2003342343A (en) | Foam having high impact resilience | |
| JP3885851B2 (en) | Method for producing flexible polyurethane foam | |
| JPH11255857A (en) | Preparation of soft polyurethane foam |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090304 Termination date: 20111227 |