TWI404739B - Flexible polyurethane low resilience foam and method for preparation - Google Patents

Abstract

A novel flexible polyurethane low resilience foam based on reaction product of isocyanate-reactive composition with isocyanate composition is invented. The flexible polyurethane low resilience foam is prepared from reacting (a) isocyanate composition containing no aromatic isocyanate which has isocyanate group attaching directly to benzene ring, (b) isocyanate-reactive composition, (c) catalyst, and optionally (e) one or more ingredients selected from following: water, surfactants, cross-linkers and auxiliaries. The flexible polyurethane low resilience foam produced according to the preparation method has isocyanate index of from 75 to 105, density range of from 16 to 160 kilograms per cubic meter, and ball resilience of less than 15%.

Description

Soft polyurethane low rebound foam and preparation method thereof

The present invention relates to an aromatic isocyanate-based polyurethane low resilience foam in which an aliphatic isocyanate and/or an alicyclic isocyanate and/or an isocyanate group are not directly bonded to a benzene ring, and a process for producing the same. It also relates to reaction systems and specific isocyanate-reactive component compositions useful in the process.

The soft low-rebound polyurethane foam has the characteristics of slow and gradual recovery after compression, and is generally called "slow rebound" foam, "viscoelastic" foam, "dead" foam, and "high damping" hair. Foam, "shape memory" foam or "slow recovery" foam. Although most of its physical properties are similar to conventional polyurethane foams, low resilience foams have much lower resilience, typically less than about 15%.

The low resilience polyurethane foam has excellent impact resistance and excellent shock absorption. It also features shape adjustment and energy attenuation, making it an ideal cushion material. The low resilience foam can be used for mattresses, pillows, car seats and furniture mats to reduce pressure points and as an impact resistant material for sports mats or helmets.

The soft low-rebound polyurethane foam has a hand-like feel similar to a human chest and can therefore be used in bra pads and shoulder pads.

Typically low resilience polyurethane foams are prepared using a polyol blend comprising a hard or semi-rigid triol having an equivalent weight of less than 450 and a soft triol having an equivalent weight of greater than 800. Most soft, low resilience polyurethane foams are prepared at a low isocyanate index (the molar ratio of isocyanate groups to isocyanate reactive groups multiplied by 100). In most cases, the index is below 90. This produces a highly crosslinked, low molecular weight foam polymer with lower mechanical properties, particularly tear strength and elongation. It also results in a narrow operating range, which usually causes the foam to shrink. Therefore, low resilience polyurethane foams are prepared by adjusting the amount and type of polyol, polyisocyanate, surfactant, crosslinking agent, catalyst or other additives to obtain low resilience, practical mechanical properties and reproducible production. Characteristic foam.

U.S. Patent 7,388,037 discloses the use of a hydroxyl value (a measure of the amount of reactive hydroxyl groups reactive in a polyol, as described in ASTM D-4274-88) to provide foam flexibility for a soft polyol of 5-15 mg KOH/g. Reduce cross-linking to improve processability.

A similar method is disclosed in U.S. Patent 6,617,369. A foam having low resilience and improved processability can be prepared by using a polyol composition composed of a polyol having an ethylene oxide content of up to 50 parts by weight based on 100 parts by weight of the total polyol composition.

U.S. Patent 6,391,935 describes the use of polyester or polyalkylene oxide monohydric alcohols and semi-rigid polyols having a number average molecular weight of greater than about 1,000 and a hydroxyl number of less than about 56 mg KOH/g to achieve a resilience of less than about 15 % while maintaining a foam having an isocyanate index of more than 90.

The use of plasticizers has been reported, for example, in U.S. Patent No. 6,790,871, which uses a paraffin wax, a (C2/C4) aliphatic polymer comprising a primary hydroxyl group (also known as a primary hydroxyl group), and mixtures thereof. Low resilience foam with good softness in cold climates.

Soft polyurethane low resilience foam was first developed in the mid-1960s as a result of the NASA (National Aeronautics and Space Administration) AMES research technology project. The purpose of this development is to redistribute the low-rebound foam to the G-Force that the astronauts receive during take-off and landing, and to provide a more comfortable seat for commercial aircraft pilots during long-term flight ( See, for example, "IN‧TOUCH", Vol. 11, No. 1, p. 1, June 2003, Periodic Publication of the Polyurethane Foam Association (PFA), PO Box 1459, Wayne, NJ). Unfortunately, due to its low index properties and the large amount of volatile amine catalyst required for formulation, the developed low resilience foam releases a large amount of volatile organic compounds (VOCs), which prevents it from being used in confined spaces. Since then, it has never been used in any spacecraft or aircraft.

With the recent concern about the safety of aromatic amines, such as toluenediamine (TDA) as a degradation reaction product of polyurethane foam prepared from toluene diisocyanate (TDI) or diphenylmethane diisocyanate (MDI) Diaminodiphenylmethane (MDA) has developed a variety of synthetic methods to reduce this emissions. TDA and MDA are highly toxic compounds and possible carcinogens of public concern. U.S. Patent 6,391,935 (issued May 21, 2002, issued to Bayer) further discloses that when a toluene diisocyanate (TDI) is used to prepare a viscoelastic foam at a low index, the resulting foam will contain an undesirably high level of toluene. Diamines, especially after the normal vulcanization process".

EUROPUR (European Association of Flexible Polyurethane Foam Manufacturers, founded in 1966) announced a voluntary project called "CertiPUR" in 2007. CertiPUR is a project that emphasizes the industry's commitment to product safety, health and environmental (SHE) performance. In order to comply with the CertiPUR standard, many hazardous substances are restricted or prohibited. According to the CertiPUR standard, the upper limit of the total amount of 2,4-TDA and 4,4'-MDA and the amount of 2,4-TDA and 4,4'-MDA in the polyurethane foam is 5 ppm, based on the weight of the foam. .

The EU officially implemented the “REACH” (Registration, Evaluation and Authorization of Chemicals) Act on June 1, 2007, and mandatory registration of all chemicals on the EU market and entering the EU market. , assessment and licensing, implementation of security monitoring. According to Article 57(1) of the Act, the European Chemicals Agency published 15 substances of Substance of Very High Concern (SVHC) on November 28, 2008, and 4,4’-MDA ranked first.

U.S. Patent Application No. 2005/0176838 A1 describes the use of a polyol composition comprising at least one acrylate polyol having a hydroxyl number of from 15 to 50 mg KOH/g to reduce hydrolytic cleavage of urethane and urea linkages. This patent describes "this fracture not only degrades significantly in performance characteristics, but also produces aromatic amines such as toluenediamine (TDA) and diaminodiphenylmethane (MDA)".

U.S. Patent No. 6,800,607 discloses the preparation of a flexible polyurethane foam by adding at least one organic or inorganic acid anhydride to the isocyanate component and then reacting the resulting isocyanate component with the polyol component. The anhydride in the polyurethane foam is further hydrolyzed to the relevant acid, especially under humid, warm conditions. These acids formed after hydrolysis block all of the amine catalyst present in the foam, thus preventing the carbamate and/or urea linkage from dissociating under warm, humid conditions. Unfortunately, this method reduces the activity of the polyurethane foam due to the increased acidity of the reaction mixture. Due to its low activity, it can only be used for more reactive aromatic isocyanates rather than aliphatic or cycloaliphatic isocyanate reactions.

A significant disadvantage of using the above treatment is that this treatment only delays the formation of TDA and MDA, and does not prevent the formation of such aromatic amines. All of the examples described in U.S. Patent Application No. US 2005/0176838 A1 and U.S. Patent No. 6,800,607 report reduced but still high levels of TDA and MDA in aged samples, even after specific treatments (refer to the examples described in the two patents, all issued) The 2,4-TDA and 4,4'-MDA content in the bubble samples far exceeds 5 ppm, which is the upper limit in the CertiPUR standard).

Since flexible polyurethane low resilience foams have unique properties that cannot be replaced by other conventional elastic foam materials, there is a need to develop a method for preparing flexible polyurethane low resilience foams without using aromatic isocyanates, based on aliphatics and/or Flexible polyurethane low resilience foams of alicyclic isocyanates provide a good solution to this need.

Since aliphatic and alicyclic isocyanates are much less active, they are rarely used to prepare polyurethane foams. Focusing on stronger catalysts, more reactive polyisocyanate compositions, polyol compositions using highly reactive polyols, or other methods of production, only a few synthetic methods have been developed to prepare aliphatic or lipids with practical physical properties. A cycloisocyanate-based polyurethane foam.

U.S. Patent Application No. US 2008/0114088 discloses a process for the preparation of a flexible polyurethane foam comprising dimerizing the polyisocyanate index in excess of 90 in the presence of a urethane forming catalyst, a blowing agent and a foam stabilizer. The alcohol mixture is reacted with a polyisocyanate compound. The polyol mixture is composed of a polyol (A) and a polyol (B), a monohydric alcohol (D) and an optional polyol (C), and the polyol (A) is a polyether polyol having an average of 2-3 a hydroxyl group having a hydroxyl value of 10 to 90 mg KOH/g, which is obtained by ring-opening addition polymerization of an alkylene oxide onto an initiator using a double metal cyanide chelate catalyst; the polyol (B) is a polyether polyol having an average of 2-3 hydroxyl groups, hydroxyl value 15-250 mg KOH / g; monohydric alcohol (D) is a polyether monool, hydroxyl value 10-200 mg KOH / g; polyol (C) has an average of 2-6 hydroxyl groups The polyol having a hydroxyl value of from 300 to 1,830 mg KOH/g is at most 10% by mass of the entire polyol mixture. It is also disclosed that suitable isocyanate compounds are selected from the group consisting of: TDI, MDI, polymethylene polyphenyl polyisocyanate (also known as crude MDI), benzene dimethylene diisocyanate (XDI), isophorone diisocyanate (IPDI) ) hexamethylene diisocyanate (HDI) and its derivatives. However, there are no examples or detailed descriptions of any of the aliphatic and alicyclic diisocyanates and aromatic isocyanates in which the isocyanate groups such as XDI are not directly bonded to the benzene ring, in any polyurethane foam preparation as described. In fact, due to the much lower activity of these aliphatic and cycloaliphatic diisocyanates, it is still difficult to practice the disclosed polyol mixtures using only aliphatic and cycloaliphatic diisocyanates (see Comparative Examples C1-C4 below).

U.S. Patent No. 5,147,897 issued to Morimoto et al. The process comprises reacting an aliphatic polyisocyanate prepolymer with from 0.4 to 5 times the isocyanate equivalent of water in the presence of a potassium or sodium salt of a C2-C10 alkanoic acid or a diazobicycloolefin catalyst. The prepolymer is an aliphatic isocyanate-terminated prepolymer obtained by addition polymerization by a polyol having an average molecular weight of 100 to 5,000 and an aliphatic polyisocyanate of 1.4 to 2.6 times the hydroxyl equivalent. The activity of the aliphatic isocyanate is generally lower than that of the aromatic isocyanate. When the aliphatic isocyanate becomes a prepolymer, molecular mobility is further lowered, resulting in further reduction in activity. Due to the reduced activity and high viscosity of the resulting prepolymer, Morimoto et al. cannot be used to prepare polyurethane foams having a density of less than 80 kg/m3 and cannot be used to prepare flexible polyurethane low resilience foams.

U.S. Patent No. 6,242,555, issued to Du Prez et al. Reaction injection molding (RIM) method for semi-flexible polyurethane. The inventive process comprises the reaction of an isophorone diisocyanate trimer/monomer mixture with an isocyanate-reactive composition having an NCO content of from 24.5 to 34% by weight in the presence of a catalyst selected from the group consisting of organic lead, organic rhodium and organotin. The isocyanate-reactive composition comprises (1) a low-unsaturation polyether polyol, as described in U.S. Patent No. 5,470,813 and U.S. Patent No. 5,498,583, which is incorporated herein by reference. , an average equivalent weight of 800-4,000 g/mol, (2) about 3 to about 20% by weight of at least one chain extender, having only an aliphatic or alicyclic OH group as a functional group, a functionality of 2, an equivalent of at most 80 g /mol, a first stage hydroxyl group content of at least 50% and (3) from about 2 to about 10% by weight of a cocatalyst system comprising from 2 to 3 functional aliphatic NH, NH2 or OH groups and an equivalent weight of up to 150 g/mol Catalyst, at least one of said catalysts being a secondary amino group (also known as a secondary amino group) or a primary amino group (also known as a primary amino group), and at least one of said The catalyst is an amine initiated catalyst. The invention provides a method of preparing a non-yellowing polyurethane material, however it can only be used in reaction injection molding and compact molded part production.

A method of preparing an alicyclic polyisocyanate-based polyurethane foam is disclosed in Japanese Patent Application No. 2003-261643A, issued Sep. 19, 2003, to Mitsui-Takeda Chemicals Inc. Novel (more expensive and limitedly produced) norbornane diisocyanate (2,5(2,6)-bis(isocyanatomethyl)bicyclo[2.2.1]heptane (produced by Mitsui-Takeda Chemicals Inc. The "Cosmonate NBDI" product is reacted with a polyether polyol and a large amount of UV stabilizer to obtain a polyurethane foam which is almost indistinct yellow. There is no description of the mechanical properties of the obtained foam, and there is no embodiment to illustrate its softness. Use in the preparation of low resilience polyurethane foams.

A method of preparing an almost invariant yellow polyurethane foam for clothing, health care or cosmetics is disclosed in Japanese Patent Application No. 2006-257187A, issued toK.S. The polyurethane foam is prepared by reacting a polyether polyol with a polyisocyanate composition comprising (isophorone diisocyanate (IPDI) and/or IPDI trimer or a derivative thereof): (The trimer and/or HDI derivative of hexamethylene diisocyanate (HDI)) is adjusted in mass to a mixture of (70-30): (30-70). It is also explained that the resulting foam has an increased foam hardness and a low wet compression set due to an increase in cross-linking. There is no description of the use of polyisocyanate compositions in the preparation of soft low resilience foams. Soft low resilience foams prepared using these polyisocyanate compositions can be hard due to a large amount of crosslinking, thus causing processing difficulties. In addition, due to the reduced isocyanate content (NCO%) in such trimers and derivatives, it is desirable to obtain any specified amount of isocyanate mixture that is much higher than the aliphatic or cycloaliphatic diisocyanate compared to the use of only diisocyanates. Isocyanate index. The cost of these polyurethane foams is increased. The increased isocyanate also means an increase in the hard segment in the polymer, which leads to an accelerated deterioration.

Japanese Patent Application No. 2001-72738A, published on March 21, 2001, to INOAC MTP KK, discloses a polyurethane foam having excellent water resistance and no discoloration under sunlight, by being selected from a diazocycloalkene or a phenyl group thereof. The aliphatic diisocyanate is reacted with a polyol having an ethylene oxide content of less than 18 parts by weight (based on 100 parts by weight of the total polyol alkylene oxide) in the presence of a salt catalyst and a weak acid alkali metal salt. Particularly useful are 1,8-diazabicyclo-(5,4,0)undecene-5 (DBU), a phenyl salt of DBU, 1,5-diazabicyclo-(4,3,0) Terpene-5 (DBN), a phenyl salt of DBN. Since these non-isocyanate-reactive diazabicycloolefins have a low boiling point, such as a boiling point of DBU of only 100 ° C at a pressure of 532 Pa, this catalyst will remain in the finished foam and gradually be discharged from the foam. Thus, the prepared polyurethane foam has a large amount of VOC emissions.

Japanese Patent Application No. 2003-012756A to INOAC MTP K.K. discloses a nearly invariant yellow polyurethane foam prepared by reacting an alicyclic diisocyanate with an amine-terminated polyol. This application also describes these polyols consisting solely of propylene oxide units. These amine-terminated polypropylene oxides are expensive and limited in supply, making it difficult to obtain useful amine-terminated polypropylene oxide molecules to make flexible polyurethane low-rebound foams.

Therefore, there is a need to develop a flexible polyurethane low resilience foam which is easily obtained by reacting an aliphatic and/or alicyclic diisocyanate with a commercially available polyether polyol. This foam can be prepared on a conventional polyurethane foam production facility without further modification of the equipment.

It is an object of the present invention to provide a process for preparing a flexible polyurethane low resilience foam based on an isocyanate-reactive component and an aromatic isocyanate directly attached to the benzene ring substantially free of isocyanate groups. The reaction product of the isocyanate component.

Another object of the present invention is to provide a novel isocyanate-reactive component composition which is suitable for aromatic isocyanates which are not directly bonded to the benzene ring with aliphatic and/or alicyclic isocyanate and/or isocyanate groups, and Or a plurality of catalysts, water, a surfactant as a cell regulator, and other additives to prepare a flexible polyurethane low resilience foam.

Another object of the present invention is to provide a process for preparing an invariable yellow flexible polyurethane low resilience foam.

Another object of the present invention is to provide a one-step process for preparing a low density non-yello polyurethane low resilience foam.

Another object of the present invention is to provide a process for preparing a molded flexible polyurethane low resilience foam.

Another object of the present invention is to provide a process for producing a flexible polyurethane low resilience foam which does not produce a toxic aromatic amine when degraded in a hot or humid environment.

Another object of the present invention is to provide a process for preparing a flexible polyurethane low resilience foam which is catalyzed by a non-volatile catalyst to release a relatively small amount of VOC.

Another object of the present invention is to provide a process for preparing a polyurethane low resilience foam having improved mechanical properties, particularly tear strength, and elongation at an isocyanate index of 75 to 105. Strength and elongation.

Another object of the present invention is to provide a flexible polyurethane low resilience foam which is excellent in low rebound and durability without using a plasticizer and which exhibits a very high temperature change. Small hardness changes with high gas permeability.

Another object of the present invention is to provide a process for preparing a biodegradable polyurethane low resilience foam using a renewable bio-sourced polyol.

Another object of the present invention is to provide a novel non-yellowing polyurethane low resilience foam which can be used in the fields of bra pads, shoulder pads, mattresses, pillows, furniture mats and car seat cushions.

Another object of the present invention is to provide a process for preparing polyurethane foams with less or no conventional and/or active tertiary amine (also known as tertiary amine) catalysts to reduce internal atomization in automobiles.

One embodiment of the present invention discloses a flexible polyurethane low resilience foam. The flexible polyurethane low resilience foam of the present invention comprises the reaction product of:

An isocyanate component substantially free of an aromatic isocyanate having an isocyanate group attached directly to the phenyl ring;

An isocyanate reactive mixture comprising:

(b1) a first isocyanate-reactive component having at least 2.6 isocyanate reactive groups, preferably from 2.6 to 6.5 isocyanate reactive groups, more preferably from 2.65 to 6.0 isocyanate reactive groups, most preferably from 2.7 to 5.5 isocyanate reactive groups, The hydroxyl equivalent is less than 800, preferably 80-800, more preferably 100-700, most preferably 110-600, and the hydroxyl value is higher than 70 mg KOH/g, preferably 70-700 mg KOH/g, more preferably 80-560 mg. KOH/g, most preferably 90-510 mg KOH/g,

(b2) a second isocyanate-reactive component having an average hydroxyl functionality of less than 6.0, preferably from 1.8 to 6.0, more preferably from 1.85 to 4.5, a hydroxyl equivalent of from 600 to 6,000, preferably from 700 to 5,000, more preferably from 800 to 4,500. a hydroxyl value of 9-94 mg KOH/g, preferably 19-80 mg KOH/g, more preferably 14-70 mg KOH/g, a first-stage hydroxyl group content of at least 30 parts by weight, preferably at least 40 parts by weight, more preferably at least 51 parts by weight, based on 100 parts by weight of the total weight of the hydroxyl groups of the second isocyanate active component,

Wherein the first isocyanate-reactive component is used in an amount of 20 to 90 parts by weight, preferably 20 to 70 parts by weight, and the second isocyanate-reactive component is used in an amount of 10 to 80 parts by weight, preferably 30 to 80 parts by weight. , all based on 100 parts by weight of the isocyanate reactive mixture;

catalyst;

Optionally one or more materials selected from the group consisting of water, surfactants, crosslinking agents, and additives;

The optional crosslinking agent has a weight average molecular weight of from 60 to 420 g/mol and has at least two isocyanate reactive functional groups; wherein, if used, the crosslinking agent is used in an amount of from 0.2 to 15 parts by weight, most preferably 1.2. 12 parts by weight based on 100 parts by weight of the isocyanate reactive mixture.

Wherein the foam is prepared at an isocyanate index of from 75 to 105.

Optionally, the isocyanate-reactive component further comprises 0-40 parts by weight (based on 100 parts by weight of the isocyanate active component) of a polymer polyol having a solid content of 5 to 55 parts by weight (at 100) The weight percentage of the polymer polyol) has a hydroxyl value of 15 to 50 mg KOH/g.

The isocyanate-reactive component may comprise 0 to 5.0 parts by weight, preferably 0 to 3.5 parts by weight (based on 100 parts by weight of the total foam mass) of polypropylene oxide (b3) as a cell opener, the polyepoxy Propane (b3) has a nominal hydroxyl functionality of 1 and a weight average molecular weight of 800-8,500 g/mol.

Another embodiment of the invention is directed to a method of making a flexible polyurethane low resilience foam. The process of the invention comprises preparing a foam formulation comprising an isocyanate reactive mixture, an isocyanate component substantially free of isocyanate groups of isocyanate groups directly attached to the benzene ring, water, a catalyst to form a carbamate in the foam formulation The ester bond and the foam stabilizer/surfactant are then foamed, after which the resulting foam formulation is cured. The isocyanate reactive mixture is selected from the above isocyanate reactive mixtures.

Another embodiment of the present invention is directed to a method of preparing a soft polyurethane low resilience foam by a one-step process.

Another embodiment of the present invention relates to a flexible polyurethane low resilience foam prepared by the above method and having a density of 16 to 160 kg/m 3 .

Another embodiment of the present invention is directed to a method of making a soft molded polyurethane low resilience foam.

In the preparation of the flexible polyurethane low resilience foam of the present invention, it is not necessary to make special changes to the existing polyurethane foam production equipment.

The isocyanate-reactive compositions of the present invention provide a greater range of formulation components in the preparation of flexible polyurethane low resilience foams of greater density and hardness.

The present invention relates to a novel flexible polyurethane low resilience foam by the isocyanate component of an aromatic isocyanate which is substantially free of isocyanate groups directly attached to the benzene ring and the disclosed isocyanate active component and catalyst, optionally water, surface The active agent, the crosslinking agent and the additive are reacted to prepare.

The isocyanate component is selected from one or more of the following isocyanates: aliphatic isocyanates, alicyclic isocyanates, and aromatic isocyanates in which the isocyanate groups are not directly attached to the phenyl ring. When an aromatic isocyanate in which an aliphatic and/or alicyclic and/or isocyanate group is not directly bonded to a benzene ring is used, the present invention provides a flexible polyurethane low resilience foam having excellent processability and low foam elasticity. . Further, the present invention discloses a one-step process for preparing a flexible polyurethane low resilience foam of a wide hardness range without using other blowing agents other than water.

The present invention discloses an aromatic aliphatic or isocyanate-based polyurethane material in which an aliphatic or alicyclic or isocyanate group is not directly bonded to a benzene ring. The polyurethane material of the invention is suitable for preparing flexible polyurethane low resilience foam, which can be used as a material for a bra pad and a shoulder pad, and is also suitable for mattresses, pillows, furniture mats, carpet sheets and seat cushion. It is especially suitable for mattresses and pillows.

In the one-step method of the present invention, the formulation material is simultaneously injected into the mixing head and then poured into the mold or on the conveyor belt. The foaming reaction proceeds very quickly. The rising foam foam is substantially completely cured in 2-7 minutes, depending on the catalyst used. The resulting foam was then post cured for 24 hours to obtain its final properties.

In the process of the invention, the reaction composition comprises an isocyanate component, an isocyanate-reactive component, a catalyst, a surfactant, water as a blowing agent and additives known per se. Other additives such as pigments/dyes, antioxidants, UV absorbers, flame retardants, fillers, recycled foam powders, stabilizers, antibacterial compounds, and antistatic agents may also be used as needed.

The isocyanate comprises an aromatic diisocyanate monomer which is aliphatic and/or cycloaliphatic and/or isocyanate groups which are not directly bonded to the phenyl ring, or the aliphatic and/or cycloaliphatic and/or isocyanate groups are not directly bonded to a blend of an aromatic diisocyanate monomer and a trimer on a benzene ring, which is an aliphatic or alicyclic or isocyanate group which is not directly attached to the aromatic diisocyanate of the benzene ring. The product, the blend having an NCO content of from 20.5 to 50.0 parts by weight based on 100 parts by weight of the total isocyanate in the isocyanate component, has a calculated functionality of 2-3. The aromatic isocyanate in which the aliphatic or alicyclic or isocyanate group is not directly bonded to the benzene ring may be at least one selected from the group consisting of, but not limited to, hexamethylene diisocyanate, hexamethylene triisocyanate, and bicycloheptane. Alkane triisocyanate, undecane diisocyanate, undecane triisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, dimethylcyclohexane diisocyanate, benzodiazepine Methyl diisocyanate, tetramethyl benzene dimethylene diisocyanate, dimers and trimers thereof. Among these isocyanates, hexamethylene diisocyanate and isophorone diisocyanate are particularly preferable.

In addition to the aliphatic and/or cycloaliphatic and/or isocyanate groups which are not directly attached to the aromatic isocyanate monomer and trimer on the phenyl ring, the isocyanate component optionally further comprises up to 35% by weight (based on the isocyanate component Total weight), an aliphatic or alicyclic or isocyanate group containing from 2 to 4 isocyanate functional groups is not directly attached to the aromatic isocyanate prepolymer on the benzene ring.

The isocyanate is generally used in an amount of from about 65 to about 110, preferably from about 70 to about 105, more preferably from about 75 to about 105.

The isocyanate reactive mixture comprises:

(b1) a first isocyanate-reactive component having at least 2.6 isocyanate reactive groups, preferably 2.6-6.5 isocyanate reactive groups, more preferably 2.65-6.0 isocyanate reactive groups, most preferably 2.7- 5.5 isocyanate reactive groups having a hydroxyl equivalent weight of less than 800, preferably 80-800, more preferably 100-700, most preferably 110-600, a hydroxyl value of more than 70 mg KOH/g, preferably 70-700 mg KOH/g, More preferably, it is 80-560 mg KOH/g, and most preferably 90-510 mg KOH/g,

(b2) a second isocyanate-reactive component having an average hydroxyl functionality of less than 6.0, preferably from 1.8 to 6.0, more preferably from 1.85 to 4.5, and a hydroxyl equivalent of from 600 to 6,000, preferably from 700 to 5,000. More preferably, it is 800-4,500, the hydroxyl value is 9-94 mg KOH/g, preferably 19-80 mg KOH/g, more preferably 14-70 mg KOH/g, and the first-stage hydroxyl group content is at least 30 parts by weight, preferably at least 40 parts by weight, more preferably at least 51 parts by weight, based on 100 parts by weight of the total weight of the hydroxyl groups of the second isocyanate active component,

Wherein the first isocyanate-reactive component is used in an amount of 20 to 90 parts by weight, preferably 20 to 70 parts by weight, and the second isocyanate-reactive component is used in an amount of 10 to 80 parts by weight, preferably 30 to 80 parts by weight. , all based on 100 parts by weight of the isocyanate reactive mixture;

An optional crosslinking agent having a weight average molecular weight of from 60 to 420 g/mol, having at least two isocyanate reactive functional groups, wherein the crosslinking agent is used in an amount of from 0.2 to 15 parts by weight, preferably from 0.5 to 15 parts by weight, if used More preferably, it is 0.5 to 12 parts by weight, most preferably 1.2 to 12 parts by weight, based on 100 parts by weight of the isocyanate-active mixture.

Optionally, the isocyanate-reactive component may further comprise 0-50 parts by weight, preferably 0-40 parts by weight (based on 100 parts by weight of the isocyanate active component) of a polymer polyol, the polymer polyol having a solid content of 5-55 parts by weight, more preferably 10-45 parts by weight (based on 100 parts by weight of the polymer polyol), the hydroxyl value is 15-50 mg KOH/g.

Optionally, the isocyanate-reactive component may comprise 0 to 5.0 parts by weight, preferably 0 to 3.5 parts by weight (based on 100 parts by weight of the total mass of the foam) of polypropylene oxide (b3) as a cell opener, the polymerization The propylene oxide has a nominal hydroxyl functionality of 1 and a weight average molecular weight of from 400 to 9,600 g/mol, preferably from 600 to 9,000 g/mol, more preferably from 800 to 8,500 g/mol.

The isocyanate-reactive components useful in the present invention include a large number of compounds. Good examples of these include, but are not limited to, the following: (a) polyether polyols, alkylene oxide adducts including polyhydroxyalkanes; (b) poly(tetramethylene ether) glycol and (c) poly (Sanya Methyl ether) diol.

Examples of the above alkylene oxide adducts of polyhydroxyalkanes include alkylene oxide adducts of ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,2-propanediol, and dibutyl Alcohol, pentanediol, tripropylene oxide adduct of glycerol, trimethylolpropane monoallyl ether, 1,1,1-trimethylolethane, 1,1,1-trimethylol Propane, 1,2,3-trimethylolhexane, glycerin, pentaerythritol, polycaprolactone, xylitol, arabitol, sorbitol, and mannitol. Among the alkylene oxides used, ethylene oxide, propylene oxide and butylene oxide are most preferred.

Polyether polyols prepared from such initiators are typically prepared by an anionic polymerization process in which an alkylene oxide is mixed with an initiator compound and a strong basic catalyst such as potassium hydroxide or some organic amine. The polymerization of alkylene oxides using these strongly basic catalysts results in an increase in the degree of unsaturation and a decrease in the average functionality of the resulting polyether polyol. These unsaturated components have a strong odor and delay the formation of urethane during the reaction of the polyol with the isocyanate.

Double metal cyanide (DMC) chelates are well known alkylene oxide polymerization catalysts. These active catalysts can be used to prepare polyether polyols having very low unsaturation compared to similar polyols prepared using strong basic catalysts. Polyether polyols having an unsaturated component content as low as 0.02 meq/g can be prepared using a DMC catalyst. A DMC-based polyether polyol, such as the product described in EP 0894108 B1, issued November 7, 2001, can be used to prepare flexible polyurethane low resilience foams with reduced odor and improved mechanical properties, and thus is preferred in the present invention. A polyether polyol.

In fact, any material having active hydrogen (as determined by the Zerewitinoff test) can be used as a component of the polyether polyol. For example, amine terminated polyether polyols are known and can be used.

In the present invention, the first isocyanate-reactive component (b1) must have at least 2.6 isocyanate reactive groups, preferably 2.6-6.5 isocyanate reactive groups, more preferably 2.65-6.0 isocyanate reactive groups, most preferably 2.7-5.5 The isocyanate reactive groups are used to satisfy the degree of crosslinking required to prepare the low resilience foam, and in the range of functional group values, the hydroxyl equivalent weight must be less than 800 in order to achieve the desired reactivity. Too high hydroxyl equivalents will render the polyol reactive too low to be suitable for reaction with low reactivity isocyanates and are not suitable for use in the present invention. If the hydroxyl equivalent is too low, the appropriate polymer molecular chain required for low rebound foam physical properties cannot be achieved. Preferred hydroxyl equivalents range from 80 to 800, more preferred hydroxyl equivalents range from 100 to 700, and most preferred hydroxyl equivalents range from 110 to 600.

In the second isocyanate-reactive component (b2) used in the present invention, the number of hydroxyl functional groups must be less than 6.0 in order to attain the demand for providing low resilience foam physical properties. Too high a number of functional groups are required to match a large hydroxyl equivalent, so that the reactivity is too low to be suitable for use in the present invention. Conversely, too low a functional group greatly detracts from the physical properties of the foam, particularly tensile strength and tear strength. The preferred number of hydroxyl functional groups is from 1.8 to 6.0, and more preferably the number of hydroxyl functional groups is from 1.85 to 4.5.

In the second isocyanate-reactive component (b2), the hydroxyl equivalent is preferably in the range of 600 to 6,000, more preferably in the range of 700 to 5,000, and most preferably in the range of 800 to 4,500. Too high a hydroxyl equivalent will result in a low reactivity, making it unsuitable for use in the present invention. Too low a hydroxyl equivalent will make the crosslink density of the foam too high, making the resulting foam too hard, and increasing the relative hardness of the foam as the temperature changes.

In the second isocyanate-reactive component (b2), in order to match the preferred number of hydroxyl functional groups and hydroxyl equivalents, it is necessary to use a highly reactive first-stage hydroxyl-terminated polyol. In order to satisfy the demand in the present invention for preparing a low-rebound foam with a low-reactivity isocyanate, the second isocyanate-reactive component (b2) selected must contain at least 30 parts by weight, preferably at least 40 parts by weight, more preferably at least 51. Parts by weight of the first stage hydroxyl groups are based on the weight of the hydroxyl groups of the second isocyanate-reactive component (b2).

Another class of polyols useful in the present invention are the above poly(tetramethylene ether) glycols. Poly(tetramethylene ether) glycol is a ring-opening polymerization product of tetrahydrofuran (THF). The poly(tetramethylene ether) glycol is a polyether polyol. It is also known as PTMEG or polytetrahydrofuran and various trade names such as "Terathane" and "PolyTHF". It is prepared by acid-catalyzed polymerization of tetrahydrofuran. The resulting polymer is suitably sized, typically having a number average molecular weight of from 250 to 3,000 g/mol. All of the hydroxyl groups in these poly(tetramethylene ether) glycols are first-order hydroxyl groups. In the present invention, poly(tetramethylene ether) glycol having an average molecular weight of 800 to 3,000, more preferably 1,200 to 2,400 g/mol is a particularly preferred poly(tetramethylene ether) glycol.

A third type of polyol useful in the present invention is poly(trimethylene ether) glycol. Poly(trimethylene ether) glycol can be prepared by a ring-opening polymerization of oxetane or a novel multi-step continuous polycondensation reaction of 1,3-propanediol, as described in July 11, 2006. It is described in U.S. Patent No. 7,074,968 to Sunkara et al. The 1,3-propanediol obtained from biomass fermentation can be used as a feed in the production process to prepare a renewable, biodegradable poly(trimethylene ether) glycol. These poly(trimethylene ether) glycols have a first-order hydroxyl group and a low melting point and high flexibility. Among the poly(trimethylene ether) glycols, those having a weight average molecular weight of 800 to 3,000, particularly 1,200 to 3,000 g/mol are most preferable to prepare a flexible polyurethane low resilience foam. Another motivation for the use of such poly(trimethylene ether) glycol comes from its biodegradable nature, which can be prepared using up to 50% by weight of the total foam weight of these bio-based poly(trimethylene ether) glycols. Degradable soft polyurethane low resilience foam.

Preferred polyols for use in the present invention include poly(propylene oxide-ethylene oxide) glycols. When used, ethylene oxide can be incorporated into the polymer chain in any manner. Ethylene oxide can be bonded to the internal segments, as end segments or randomly distributed along the polyol chain. Most preferred is an ethylene oxide-capped poly(ethylene oxide-propylene oxide) diol.

The crosslinker component may be a OH, NH or NH2 group, more particularly an aliphatic or alicyclic OH, NH or NH2 group, having a weight average molecular weight of from 40 to 640, preferably from 60 to 420 g/mol, having at least two a crosslinking agent of an isocyanate reactive functional group, wherein if used, the crosslinking agent is used in an amount of from 0.2 to 15, preferably from 0.5 to 15, more preferably from 0.5 to 12, most preferably from 1.2 to 12 parts by weight, based on 100 parts by weight Isocyanate reactive mixture.

Typical examples of crosslinking agents are: ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a number average molecular weight of less than 600, propylene glycol, propylene glycol, and a molecular weight of less than 450. Polypropylene glycol, butanediol, pentanediol, hexanediol, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, 1,2,3-trimethylol Hexane, glycerin, poly(propylene oxide-ethylene oxide), poly(propylene oxide), poly(ethylene oxide), 2-methyl-1,3-propanediol, 3-methyl-1, 5-pentanediol, 1,4-cyclohexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, ethylenediamine, monoethanolamine, diethanolamine, 2-amino-2-methyl-1 -propanol, N-methylethanolamine, isophoronediamine and hydrazine. Preferred examples of the crosslinking agent are monoethanolamine and diethanolamine. Mixtures of several crosslinkers can also be used if desired.

A stably dispersed polymer polyol may be added to the isocyanate-reactive mixture as needed for the hardness of the low resilience foam. The stably dispersed polymer polyol component can be any polyalkylene oxide polyol having a polymer of ethylenically unsaturated monomers dispersed therein. Typical examples of the stably dispersed polymer polyol include polyalkylene oxide polyols in which poly(styrene-acrylonitrile) and/or polyurea are dispersed. The stably dispersed polymer polyols are commercially available from several companies including Bayer (trade name "Polymer Polyol"), BASF (BASF) (trade name "Graft Polyol" Branch polyol)"), DOW (trade name "Copolymer Polyol") and MOBAY (trade name "PHD Polyol (PHD Polyol)"). Poly(styrene-acrylonitrile) is dispersed in a polyol according to the method described in U.S. Patent No. 4,272,619, U.S. Patent No. 4,640,935, and U.S. Patent No. 5,494,957. Examples of stable dispersed polymer polyols are listed in Table 1 below:

The stably dispersed polymer polyol can be prepared according to the procedure described by Oertel in "Polyurethane Handbook" (Polyurethane Handbook, G. Oertel, ISBN 0-02-948920-2, Hanser Publisher, 1985). Any polyalkylene oxide polyol can be used as the dispersion matrix in the preparation of such stable dispersed polymer polyols. The activity of such stable dispersed polymer polyols is primarily dependent on the activity of the matrix polyol used in the preparation of such stable dispersed polymer polyols. Since the aromatic polyisocyanate in which the aliphatic and/or alicyclic and/or isocyanate groups used in the present invention are not directly bonded to the benzene ring is less active, it is preferred that the nominal functionality is from 2.4 to 6 (more preferably 2.4-). 5.6, most preferably 2.4-5.4), an equivalent weight of 800-2,000 (more preferably 800-1,600, most preferably 1,000-1,600) g/mol, and an ethylene oxide content of 4-28 (preferably 4-24)% by weight The base polyol of the weight of the base polyol.

Depending on the operability of the low resilience foam, a cell opener may be added to the isocyanate reactive mixture to improve shrinkage of the low resilience foam. Typical examples of the cell opener include: a stably dispersed polymer polyol, a poly(ethylene oxide-propylene oxide) copolymer having an ethylene oxide content of more than 50% by weight, and a poly(ring) having a weight average molecular weight of more than 800. Oxybutane-propylene oxide copolymer, polyethylene glycol having a weight average molecular weight of more than 600, polypropylene oxide having a weight average molecular weight of more than 400, fumed silica having a particle diameter of less than 150 μm, and a particle diameter smaller than 200 micron polytetrafluoroethylene resin powder, aliphatic carboxylic acid and alkali metal or alkaline earth metal salt thereof, alicyclic carboxylic acid and alkali metal or alkaline earth metal salt thereof, aliphatic alkane, alicyclic alkane and dimethyl hydrazine oil . Preferably, the cell opener component is a stably dispersed polymer polyol, a poly(ethylene oxide-propylene oxide) copolymer having an ethylene oxide content of more than 50% by weight, and a poly(epoxy) having a weight average molecular weight of more than 800. Butane-propylene oxide copolymer and polypropylene oxide having a weight average molecular weight of more than 400. The preferred cell opener component is typically used in an amount of from 0.05 to 20 parts by weight, preferably from 0.5 to 10 parts by weight, based on 100 parts by total of the total mass of the foam. Most preferably, the cell opener component is a polypropylene oxide having a weight average molecular weight of more than 400, said polypropylene oxide cell opener having a nominal hydroxyl functionality of 1, and a weight average molecular weight of from 400 to 9,600 g/mol, preferably from 600 to 9,000. g/mol, more preferably 800-8,500 g/mol, the polypropylene oxide open cell is generally used in an amount of 0 to 5.0 parts by weight, preferably 0 to 3.5 parts by weight based on 100 parts by weight of the total mass of the foam ). Mixtures of several cell openers can also be used if desired.

A number of polyurethane catalyst commercial products are useful in the preparation of the flexible polyurethane low resilience foams of the present invention. The catalyst is usually used in an amount of from 0.05 to 2.0 php (parts by weight per 100 parts by weight of the polyol). Representative catalysts include: (1) tertiary amines such as bis(2,2'-dimethylamino)ethyl ether, bis(dimethylaminoethyl)ether, N-methylmorpholine, N -N-ethyl morpholine, N,N-dimethylbenzylamine, N,N-dimethylethanolamine, N,N,N',N'-tetramethyl-1,3-butyl Diamine, pentamethyldipropylenetriamine, trimethylamine, triethylamine, triethanolamine, triethylenediamine and pyridine oxide; (2) diazabicycloalkenes such as 1,5-diazabicyclo-( 4,3,0)decene-5,1,8-diazabicyclo-(5,4,0) undecene-7,1,8-diazabicyclo-(5,3,0) keto-7 An organic salt of 1,5-diazabicyclo-(5,4,0)undecene-5,1,4-diazabicyclo-(3,3,0)octene-4 and a diazabicycloalkene such as a phenolate; (3) strong bases such as alkali and alkaline earth metal alkoxides, hydroxides and phenates; (4) acidic metal salts of strong acids such as stannous chloride, ferric chloride, antimony trichloride, antimony chloride and nitrate; (5) Chelates of various metals such as acetoacetone, benzamidine acetone, trifluoroacetoneacetone, ethyl acetate, salicylaldehyde, cyclopentanone-2-carboxylate, acetamidine Amine, diethyl acetonide-alkylene diimide and salicylaldimine Those metals such as beryllium, magnesium, zinc, lead, titanium, zirconium, tin, bismuth, molybdenum, manganese, iron, cobalt, and nickel obtained; (6) alkoxides of various metals and phenolates such as Sn (OR) _4, Sn(OR) ₂ , Ti(OR) ₄ and Al(OR) ₃ , wherein R is an alkyl group or a phenyl group, and an alkoxide with a carboxylic acid, a β-diketone and a 2-(N,N-dialkylamino group) a reaction product of an alkanol, such as a titanium chelate obtained by such or a similar procedure; (7) a salt of an organic acid with various metals such as alkali metals and alkaline earth metals such as calcium hexanoate, stannous acetate, stannous octoate and oleic acid Stannous; (8) organometallic derivatives of tetravalent tin, trivalent and pentavalent arsenic, antimony and bismuth, and metal carbonyl compounds of iron and cobalt.

Among the above catalysts, it has been found that an organotin compound is particularly useful for preparing the flexible polyurethane low resilience foam of the present invention. Preferred organotin compounds are dialkyl tin salts of carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate, dimethyl tin dilaurate, dibutyltin maleate, dilauryl tin diacetate and diacetic acid. Dioctyl tin. Other useful organotin compounds are trialkyltin hydroxide, dialkyltin oxide, dialkyltin dialkyltin, dialkyltin dichloride, and dialkyltin dithiolate. Examples of such compounds include trimethyltin hydroxide, tributyltin hydroxide, trioctyltin hydroxide, dibutyltin oxide, dioctyltin oxide, dilauryl tin oxide, dibutyltin dichloride, dichlorodioctyl Tin, dibutyltin dithiolate and dimethyltin dithiolate. The organotin compound is generally employed in an amount of from about 0.05% to about 0.8% by weight, preferably from about 0.15% to about 0.55% by weight, based on the isocyanate-reactive mixture (b).

Another catalyst useful in the preparation of the flexible polyurethane low resilience foams of the present invention is a salt of Bronsted acid with various alkali or alkaline earth metals. It was found that sodium hydrogencarbonate or sodium carbonate is particularly useful for preparing the flexible polyurethane low resilience foam of the present invention. The alkali metal or alkaline earth metal bromide salt is generally used in an amount of from about 0.01 to about 0.8% by weight, preferably from about 0.1 to about 0.6% by weight, based on the isocyanate-reactive mixture (b).

One or more surfactants can also be used in the foaming composition. The surfactant reduces the surface tension of the body, promotes nucleation of the bubbles, stabilizes the foam and emulsifies the incompatible components. The surfactant commonly used in polyurethane foams is a polyoxyalkylene-polyalkylene oxide copolymer, usually used in an amount of from about 0.2 to about 3% by weight, preferably from about 0.6 to about 2.5% by weight, based on the total isocyanate reactive mixture. meter. Conventional surfactants for preparing aromatic diisocyanate-based polyurethane foams can also be used in the present invention.

0.5 to 6.5 parts by weight (based on 100 parts by weight of the isocyanate reactive mixture) of water is used to produce carbon dioxide by reaction with the isocyanate as a foaming agent for the foaming reaction. In addition, a combination of water and other known auxiliary blowing agents can be used if desired. It is particularly preferred to use carbon dioxide (gas or liquid) directly as an auxiliary blowing agent other than water. It has also been found that the adjustment of the gas pressure during the foaming reaction and/or the use of a mechanical foaming technique, as described in WO 93/24304, issued on Dec. 9, 1993, and U.S. Patent No. 5,194,453, issued on Mar. Foam density.

Other additives may optionally be incorporated into the foaming compositions of the present invention. These other additives include, but are not limited to, pigments, antioxidants, UV absorbers, UV stabilizers, flame retardants, fillers, recycled foam powders, stabilizers, antimicrobial compounds, and antistatic agents. This additive should not adversely affect the performance of the flexible polyurethane low resilience foam.

The flexible polyurethane low resilience foam of the present invention can be prepared by a molding method and/or a slackstock method. The molding method is a method in which an active mixture is injected, foamed, and molded in a closed mold. The block method refers to pouring the active mixture onto a conveyor belt and foaming in an open system.

The flexible polyurethane low resilience foam of the present invention has a density in the range of from about 10 to about 200 kg/m 3 , preferably from about 16 to about 160 kg per m ^ 3 , as determined according to the JIS K6400 method (1997 edition).

The soft polyurethane low resilience foam of the present invention has a falling ball resilience of not more than 20%, preferably not more than 15%, which is determined in accordance with JIS K6400 method (1997 edition).

The flexible polyurethane low resilience foam of the present invention has hardness as understood in the art for flexible polyurethane foams. In one embodiment, the flexible polyurethane low resilience foam of the present invention has a hardness of less than 150 N/314 cm2. In another embodiment, the flexible polyurethane low resilience foam of the present invention has a hardness of 6-120 N/314 cm2 or 6-90 N/314 cm2. The hardness of the flexible polyurethane low resilience foam of the present invention can be adjusted by adjusting the ratio between the first isocyanate active component (b1) and the second isocyanate active component (b2), and by selecting an appropriate isocyanate index. The IIAC 25% hardness of the flexible polyurethane low resilience foam of the present invention can be adjusted as low as 6 N/314 cm 2 by using more of the second isocyanate active component (b2) in combination with an isocyanate index of not more than 80. The IFC 25% hardness of the flexible polyurethane low resilience foam of the present invention can be adjusted up to 120 N/314 cm 2 using a larger amount of the first isocyanate active component (b1) in combination with an isocyanate index of not less than 95. The IFD 25% hardness was determined according to the JIS K6400 method (1997 edition). In general, soft polyurethane low resilience foams for pillows and mattresses require an IFD 25% hardness between 12N/314cm2 and 24N/314cm2 for both load capacity and comfort. Exercise pads or helmets require high hardness to achieve shock absorption and impact resistance.

detailed description

In the following detailed description, the symbols, terms, and abbreviations used will have the following definitions:

ISO 1 is isophorone diisocyanate, a product of Desmodur I from Bayer AG (Bayer).

ISO 2 is a mixture of 50% by weight of isophorone diisocyanate (Desmodur I) and 50% by weight of hexamethylene diisocyanate trimer (commoded by Desmodur N3600), both from Bayer AG (Bayer).

ISO 3 is toluene diisocyanate, a composition of 80% by weight of 2,4-toluene diisocyanate and 20% by weight of 2,6-toluene diisocyanate, available from Bayer AG (Bayer).

ISO 4 is hexamethylene diisocyanate, a product of Desmodur H from Bayer AG (Bayer).

ISO 5 is a trimer of hexamethylene diisocyanate prepared by trimerization of hexamethylene diisocyanate, available from Bayer AG (Bayer), Desmodur N3600.

ISO 6 is benzene dimethylene diisocyanate available from Takesu 500 of Mitsui-Takeda Chemicals Inc.

P1 is a glycerin-initiated polypropylene oxide having an average molecular weight of 550 g/mol and a hydroxyl value of 310 mg KOH/g, and is produced by SK Chemicals of Korea (YUKOL 1030).

P2 is a sorbitol initiated polypropylene oxide having an average hydroxyl equivalent weight of about 117.

P3 is poly(tetramethylene ether) glycol having a hydroxyl equivalent of about 900 and is produced by Dalian Chemical Company of Taiwan.

P4 is a poly(trimethylene ether) glycol prepared from bio-based 1,3-propanediol having an average hydroxyl equivalent weight of about 1,070 and an APHA color of about 25, available from E.I. du Pont (DuPont).

P5 is a low unsaturation polyether polyol prepared by addition polymerization of propylene oxide to a propylene glycol initiator using a DMC catalyst, followed by capping with ethylene oxide, and an average molecular weight of 4,000 g/mol, a hydroxyl value. It is about 28 mg KOH/g with a nominal functionality of 2 and a first level hydroxyl functional group content of about 87% by weight based on the total hydroxyl weight, sold by Bayer AG (Bayer) ACCLAIM POLYOL 4220N.

P6 is a low unsaturation polyether polyol prepared by the addition polymerization of propylene oxide to a propylene glycol initiator using a DMC catalyst, having an average molecular weight of 4,000 g/mol and a hydroxyl value of about 28 mg KOH/g, unsaturated. The degree is 0.005 meq/g, 100% by weight of a secondary hydroxy (also known as secondary hydroxyl) functional group having a nominal functionality of 2, available from Bayer AG (Bayer) ACCLAIM POLYOL 4220.

P7 is a low unsaturation polyether polyol prepared by the addition polymerization of propylene oxide to a 1,1,1-trimethylolpropane initiator using a DMC catalyst, having an average molecular weight of 3,000 g/mol and a hydroxyl value. Approximately 57.6 mg KOH/g, an unsaturation of 0.005 meq/g, 100% by weight of a second stage hydroxyl functional group, a nominal functionality of 3, sold by ACCLAIM POLYOL 3300N from Bayer AG (Bayer).

P8 is a low unsaturation polyether polyol prepared by addition polymerization of propylene oxide to a propylene glycol initiator using a DMC catalyst, followed by capping with ethylene oxide, and an average molecular weight of 2,000 g/mol, a hydroxyl value. It is about 56 mg KOH/g with a nominal functionality of 2 and a first level hydroxyl functional group content of about 87% by weight based on the total hydroxyl weight, available from Bayer AG (Bayer) ACCLAIM POLYOL 2220N.

P9 is a low unsaturation polyether polyol prepared by addition polymerization of propylene oxide to a propylene glycol initiator using a DMC catalyst, having an average molecular weight of 8,000 g/mol and a hydroxyl value of about 14 mgKOH/g, 100% by weight. The second-level hydroxyl functional group, nominally 2, was sold by ACCLAIM POLYOL 8200 from Bayer AG.

P10 is a poly(propylene oxide-ethylene oxide) copolymer prepared by addition polymerization of propylene oxide to a propylene glycol initiator using a potassium hydroxide catalyst, followed by capping with ethylene oxide. The alkane content is 19% by weight, the first-stage hydroxyl functional group content is about 53% by weight based on the total hydroxyl group, the average molecular weight is 2,000 g/mol, the hydroxyl value is about 56.1 mgKOH/g, and the degree of unsaturation is 0.03 meq/g. The functionality is 2.

P11 is a poly(propylene oxide-ethylene oxide) copolymer prepared by addition polymerization of propylene oxide to a sorbitol initiator using a potassium hydroxide catalyst, followed by capping with ethylene oxide, ethylene oxide The content is 28% by weight, the first stage hydroxyl functional group content is about 85% by weight based on the total hydroxyl group, the hydroxyl value is about 31.3 mg KOH/g, and the nominal functionality is 6.

P12 is a polymer polyol in which 45% by weight of a styrene-acrylonitrile copolymer is dispersed and has a hydroxyl value of about 28.5 mgKOH/g. The base polyol was a randomly fed poly(propylene oxide-ethylene oxide) triol having a hydroxyl equivalent weight of 1,050 and sold by ARCOL POLYOL HS-100 from Bayer AG.

P13 is a monohydric alcohol which is subjected to addition polymerization of propylene oxide to a butanol initiator by using a potassium hydroxide catalyst, and has a hydroxyl value of 8.5 mg KOH/g.

DEOA is diethanolamine, with a purity of more than 99% by weight, sold by Sigma-Aldrich (Sigma Aldrich).

PEG 400 is a reagent grade poly(ethylene glycol) having an average molecular weight of 400 and a purity of over 98.5%, sold by Sigma-Aldrich (Sigma Aldrich).

Glycerol is a GC reagent grade glycerol with a purity of more than 99%, sold from Sigma-Aldrich (Sigma Aldrich).

SC was a 2M aqueous solution of sodium carbonate prepared from deionized water and reagent grade sodium carbonate with a purity of over 99%, sold from Sigma-Aldrich (Sigma-Aldrich).

SBC is a 0.5 M aqueous solution of sodium bicarbonate prepared from deionized water and reagent grade sodium bicarbonate having a purity greater than 99%, sold from Sigma-Aldrich (Sigma Aldrich).

DC 5950 is a polyoxyalkylene-polyalkylene oxide copolymer surfactant available from Air Products and Chemicals Inc. (DACCO DC 5950).

DC 5179 is a low release polyoxyalkylene-polyalkylene oxide copolymer surfactant available from Air Products and Chemicals Inc. (DACCO DC 5179).

Niax A-230 is a tertiary amine mixture sold by Chemtura Corp.

SO refers to stannous octoate, DABCOT-9 sold by Air Products and Chemicals Inc. (Air Products).

DBTDL refers to dibutyltin dilaurate sold by DABCO T-12 from Air Products and Chemicals Inc. (Air Products).

UV is 2-(2'-hydroxy-3'5'-di-tert-amylphenyl)benzotriazole, Chemical Abstract No. 25973-55-1, manufactured by Taiwan Yongguang Chemical Industry Co., Ltd.

"Index" means the ratio of the total number of moles of reactive isocyanate groups in the reaction mixture divided by the total number of moles of isocyanate reactive groups in the reaction mixture multiplied by 100.

"pbw" means parts by weight.

In the following detailed description, the properties of the polyurethane foams given in the examples were determined according to the following test methods:

The "center density" is determined in accordance with the JIS K6400 method (1997 edition).

"IFD (Indentation Force Deflection) hardness of 25%" means that it is determined by a 25% compression load in accordance with JIS K6400 method (1997 edition).

"CLD (Compression Load Deflection) hardness of 25%" means that it is determined by a 25% compression load in accordance with JIS K6400 method (1997 edition).

"Hardness change" means the ratio of increase in CLD hardness (in %) measured at -5 ° C for the CLD hardness measured at 23 ° C. The CLD hardness of 25% was determined in accordance with the JIS K6400 method (1997 edition). Test samples were conditioned at the specified temperature for at least 24 hours prior to testing.

"Tensile strength" was determined in accordance with JIS K6400 method (1997 edition).

"Elongation" is determined in accordance with the JIS K6400 method (1997 edition).

The "tear strength" was determined in accordance with the JIS K6400 method (1997 edition).

The "falling ball resilience" of the center is determined in accordance with the JIS K6400 method (1997 edition).

Determined according to the JIS K6400 method (1997 edition).

"Dry compression set" refers to dry heat compression deformation determined in accordance with JIS K6400 method (1997 edition).

"Wet compression deformation" means wet heat compression deformation determined in accordance with JIS K6400 method (1997 edition).

The "UV stability" value is the color fastness measurement obtained according to the AATCC 16-1990, Option E method. The foam sample was placed under a UV lamp and exposed to ultraviolet light for 20 hours. In contrast to a standard grayscale card, the results are expressed as a rating of 1-5. Level 5 means no color change at all, and level 1 means almost dark. Values of level 4 and above indicate that there are no visual changes that are discernible by the naked eye.

"Molding processability" is a mold evaluation, and a foam having a good surface layer after foaming and having no shrinkage is rated as "good", and the foam is shrinked after foaming but recovered after rolling twice. It can be rolled, and the evaluation that the foam shrinks after foaming and does not recover after rolling twice is "poor".

The following examples are intended to illustrate the invention and are not to be construed as limiting the scope of the invention in any way. All parts and percentages are by weight and percentage by weight unless otherwise indicated.

Examples 1-30 and Comparative Examples C1-C5

Examples 1-10 and Comparative Examples C1-C5

The flexible polyurethane low resilience foams of Examples 1-10 and Comparative Examples C1 to C5 were prepared by mixing the components shown in Tables 2-1 and 2-2. Prior to foaming, all selected ingredients were conditioned for at least 24 hours in an oven controlled at 23 ± 1 °C. Prior to the addition of the organotin compound, the ingredients other than the organotin compound and the isocyanate were premixed together in a 1.5 liter stainless steel cup using a Cowles type mixer set at 1,500 rpm. After premixing, the organotin compound (if used) was then added to the cup and mixed for another 20 seconds at a rotational speed of 1,500 rpm. The selected isocyanate compound was then added to the resulting mixture and mixed with the resulting composition at 3,000 rpm for 5 seconds. The mixture was then poured into a top open 45 cm (length) X 45 cm (width) X 45 cm (height) paper-lined wooden box and foamed. After the foam reaches its final height, let it rest in the box for another ten minutes and then remove it from the box. The resulting foam was then stored in a ventilated and temperature controlled storage room at 27 ± 2 ° C for at least 72 hours.

The sample was then cut from the center of the prepared foam using a laboratory scale electric saw according to the sample size described in the JIS K6400 method (1997 edition). Next, a sample for testing tear strength, tensile strength and elongation was cut out from a foam plate of a specified thickness according to the sample size described in JIS K6400 method (1997 edition). All samples were conditioned for at least 24 hours in a constant temperature humid chamber with a temperature control of 23 ± 1 ° C and a humidity of 50% prior to physical performance testing.

Examples 1-10 compare the common standard foam formulations (Comparative Example C5) to illustrate the processability, foam mechanical properties and formulation flexibility in the preparation of flexible polyurethane low resilience foams. Both a conventional highly unsaturated polyol and a DMC low unsaturated polyol were used in Comparative Example C5. Comparative Examples C1-C4 produced only foams that collapsed or became "marstle-like" foam blocks, had no strength and could not be used for further foam physical property testing. Examples 1-10 illustrate that the isocyanate-reactive composition (b) of the present invention provides sufficient activity to react with an aliphatic or alicyclic isocyanate in an addition polymerization prepared from a flexible polyurethane low resilience foam, and the resulting flexible polyurethane The low resilience foam has better mechanical properties than the conventional low resilience foam prepared from toluene diisocyanate (Comparative Example C5).

Example 11-18

Examples 11-18 were prepared using the same procedure as used in the preparation of Examples 1-10, except that the selected polyols P3 and P4 were first melted in an oven at a temperature of 60 ± 1 ° C when the polyol was completely melted. The polyol was then transferred to a conditioning chamber at 28 ± 1 °C for 6 hours before further foaming. All other ingredients selected were conditioned for at least 24 hours in a separate incubator with a temperature control of 23 ± 1 °C prior to foaming.

The selected polyol P3 or P4 was first mixed with the other polyol at 3,000 rpm in 60 seconds using a Cowles type high shear mixer. The flexible polyurethane low resilience foams of Examples 11-18 were prepared by mixing the components shown in Table 3. Prior to the addition of the organotin compound, ingredients other than the organotin compound and isocyanate were premixed together in a 1.5 liter stainless steel cup using a Cowles type mixer set at 2,000 rpm. After premixing, the organotin compound (if used) was then added to the cup and mixed for another 20 seconds at a rotational speed of 2,000 rpm. The selected isocyanate compound was then added to the resulting mixture and mixed with the resulting composition at 3,000 rpm for 5 seconds. The mixture was then poured into a top open 45 cm (length) X 45 cm (width) X 45 cm (height) paper-lined wooden box and foamed. After the foam reaches its final height, let it rest in the box for another ten minutes and then remove it from the box. The resulting foam was then stored in a ventilated and temperature controlled storage room at 27 ± 2 ° C for at least 72 hours.

A sample was cut from the center of the prepared foam using a laboratory scale electric saw according to the sample size described in the JIS K6400 method (1997 edition). Next, a sample for testing tear strength, tensile strength and elongation was cut out from a foam plate of a specified thickness according to the sample size described in JIS K6400 method (1997 edition). All samples were conditioned for at least 24 hours in a constant temperature humid chamber with a temperature control of 23 ± 1 ° C and a humidity of 50% prior to further physical property testing.

In the case of the closed-cell foam obtained in Example 15, when the internal temperature began to decrease, the foam began to shrink. The foam was rolled by passing the foam through a pair of electric stainless steel roll-type breakers to prevent further shrinkage. Prior to further physical property testing, the milled foam was conditioned for at least 72 hours in a constant temperature and humidity chamber controlled to a temperature of 23 ± 1 ° C and a humidity of 50%. The physical properties described in Example 15 were determined using samples cut from the center of the milled foam.

Example 19-27

The flexible polyurethane low resilience foams of Examples 19-27 were prepared by mixing the components shown in Table 4. Examples 19-27 were prepared using the same procedure as described in the preparation of Examples 1-18. The UV additive is added to the resulting isocyanate reactive mixture in a premixing step.

The foam physical property tests of Examples 19-27 were carried out in the same manner as in Examples 1-18 except for the UV stability test. In the UV stability test, a sample of 10 cm long by X5 cm wide and X 0.5 cm thick was placed in an oven with an internal temperature setting of 80 ± 1 ° C. The OSRAM ULTRA-VITALUX 300 W UV lamp was mounted on the foam sample. 30 cm above. The sample was exposed to ultraviolet light for 20 hours. In contrast to a standard grayscale card, the results are expressed as a rating of 1-5. Level 5 means no color change at all, and level 1 means almost dark. Values of level 4 and above indicate that there are no visual changes that are discernible by the naked eye.

Foams Prepared in Examples 19-27 Description: The disclosed isocyanate reactive mixtures can be used to prepare invariable yellow polyurethane low resilience foams having densities as low as 24 kg/m3 (about 1.5 pcf). These low density, non-yellowing polyurethane low resilience foams are particularly useful in apparel applications such as bra pads and shoulder pads.

Example 28-30

The flexible polyurethane low resilience foams of Examples 28 to 30 were prepared by mixing the components shown in Table 5. Prior to foaming, all selected ingredients were conditioned for at least 24 hours in a box controlled at 23 ± 1 °C. Prior to the addition of the organotin compound, ingredients other than the organotin compound and the isocyanate were premixed together in a 1.5 liter stainless steel cup using a Cowles type mixer set at 1,500 rpm. After premixing, the organotin compound (if used) was then added to the cup and mixed for another 20 seconds at a rotational speed of 1,500 rpm. The selected isocyanate compound was then added to the resulting mixture and mixed with the resulting composition at 3,000 rpm for 5 seconds. Immediately pour the mixture into a 40 cm (length) X 40 cm (width) X 10 cm (high) aluminum mold preheated to 60 ° C. There are 4 small holes in the top of the mold cover to maintain the mold temperature at 60 ° C and cover. Upper cover. After the mold temperature was maintained at 60 ° C for 10 minutes, the molded flexible polyurethane low resilience foam was taken out of the mold, and then the prepared foam was kept in a ventilated and temperature-controlled manner before any further testing. Store in a storage compartment at 27 ± 2 ° C for at least 72 hours.

Industrial applicability

The polyurethane foam of the invention has low resilience and is suitable as a filling material for bra pads and shoulder pads, and is also suitable for mattresses, pillows, furniture mats and car seat cushions. It is especially suitable for mattresses and pillows.

Claims (69)

A low resilience foam comprising a reaction product having an isocyanate index of from about 65 to about 110: a. an isocyanate component substantially free of aromatics directly attached to the phenyl ring by an isocyanate group. Isocyanate; b. An isocyanate-reactive mixture comprising: (b1) a first isocyanate-reactive component having at least 2.6 isocyanate-reactive groups, a hydroxyl equivalent weight of from 80 to 800 g, and a hydroxyl value of from 70 to 700 mg KOH /g, (b2) a second isocyanate active component having an average hydroxyl functionality of from 1.8 to 6.0, a hydroxyl equivalent weight of from 600 to 6,000 g, a hydroxyl value of from 9 to 94 mg KOH/g, and a primary hydroxyl group content of At least 30 parts by weight, based on 100 parts by weight of the total weight of the second isocyanate active component hydroxyl group, wherein the first isocyanate active component is used in an amount of 20 to 90 parts by weight, the second isocyanate active component Used in an amount of 10 to 80 parts by weight, based on 100 parts by weight of the isocyanate-activated mixture; c. a catalyst; and d. optionally one or more selected from the group consisting of water, surfactant, cross-linking And additives. The foam of claim 1, wherein the first isocyanate-reactive component has from 2.6 to 6.5 isocyanate reactive groups. A foam as set forth in claim 2, wherein the first isocyanate-reactive component has from 2.7 to 5.5 isocyanate reactive groups. A foam as set forth in claim 1 wherein the first isocyanate-reactive component has a hydroxyl equivalent weight of from 100 to 700 g. a foam as shown in claim 4, wherein the first isocyanate is active The hydroxyl equivalent of the component is from 90 to 510 grams. A foam as set forth in claim 1 wherein the second isocyanate reactive component has an average hydroxyl functionality of from 1.85 to 4.5. The foam of claim 1, wherein the second isocyanate-reactive component has a hydroxyl equivalent weight of from 800 to 4,500 g. The foam according to claim 1, wherein the second isocyanate active component has a first-order hydroxyl group content of at least 40 parts by weight, based on 100 parts by weight of the total weight of the second isocyanate-reactive component hydroxyl group. . The foam according to claim 8 wherein the second isocyanate active component has a first-stage hydroxyl group content of at least 51 parts by weight based on 100 parts by weight of the total weight of the second isocyanate-reactive component hydroxyl group. . The foam according to claim 1, wherein the first isocyanate active component is used in an amount of 20 to 70 parts by weight, and the second isocyanate active component is used in an amount of 30 to 80 parts by weight. Each is based on 100 parts by weight of the isocyanate reactive mixture. The foam according to claim 1, wherein the isocyanate component comprises an isocyanate selected from one or more of the following: an aliphatic isocyanate, an alicyclic isocyanate, and an isocyanate group are not directly attached to the benzene ring. Isocyanate. The foam according to claim 11, wherein the aliphatic isocyanate comprises an aliphatic polyisocyanate monomer or a blend of an aliphatic polyisocyanate monomer and a trimer; wherein: the trimer a product obtained by trimerization of at least one polyisocyanate selected from the group consisting of aliphatic polyisocyanates, alicyclic polyisocyanates or aromatic polyisocyanates in which isocyanate groups are not directly attached to the benzene ring; NCO content in the blend 20.5-50.0 parts by weight, based on 100 parts by weight of total isocyanate in the isocyanate component; The average calculated functionality is 2-3. The foam according to claim 12, wherein the aliphatic isocyanate comprises at least one selected from the group consisting of hexamethylene diisocyanate, hexamethylene triisocyanate, undecane triisocyanate, and eleven Alkyl diisocyanate, its dimers and trimers. The foam according to claim 12, wherein the aliphatic polyisocyanate is hexamethylene diisocyanate, and the trimer is a product of trimerization of hexamethylene diisocyanate. The foam according to claim 11, wherein the alicyclic isocyanate comprises an alicyclic polyisocyanate monomer or a blend of an alicyclic polyisocyanate monomer and a trimer; wherein: The trimer is a product of the trimerization of at least one polyisocyanate selected from the group consisting of aliphatic polyisocyanates, alicyclic polyisocyanates or aromatic polyisocyanates in which the isocyanate groups are not directly bonded to the benzene ring; The NCO content is from 20.5 to 38.0 parts by weight based on 100 parts by weight of the total isocyanate in the isocyanate component; and the average calculated functionality is 2-3. The foam according to claim 15, wherein the alicyclic isocyanate comprises at least one selected from the group consisting of biscycloheptane triisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and Cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, dimers and trimers thereof. The foam according to claim 15, wherein the alicyclic polyisocyanate is isophorone diisocyanate, and the trimer is a product of trimerization of hexamethylene diisocyanate. The foam according to claim 11, wherein the aromatic isocyanate in which the isocyanate group is not directly bonded to the benzene ring contains an aromatic polyisocyanate monomer or isocyanate in which the isocyanate group is not directly bonded to the benzene ring. a blend of aromatic polyisocyanate monomers and trimers that are not directly attached to the phenyl ring; wherein: the trimer is a product of at least one polyisocyanate trimerization selected from the group consisting of aliphatic polyisocyanates , the alicyclic polyisocyanate or isocyanate group is not directly linked to the aromatic polyisocyanate on the benzene ring; the NCO content in the blend is from 20.5 to 44.0 parts by weight, based on 100 parts by weight of the total isocyanate in the isocyanate component; And the average calculated functionality is 2-3. The foam according to claim 18, wherein the aromatic isocyanate in which the isocyanate group is not directly bonded to the benzene ring is at least one selected from the group consisting of benzene dimethylene diisocyanate and tetramethyl benzene. Dimethylene diisocyanate, its dimers and trimers. A foam according to claim 18, wherein the aromatic polyisocyanate in which the isocyanate group is not directly bonded to the aromatic ring is phenylenediethylene diisocyanate or tetramethylbenzene dimethylene diisocyanate. The trimer is the product of the trimerization of hexamethylene diisocyanate. The foam according to claim 1, wherein the first isocyanate-reactive component (b1) is a polypropylene oxide having at least 3 isocyanate reactive groups and an unsaturation of less than 0.05 meq/g. The foam according to claim 1, wherein the first isocyanate active component (b1) is polypropylene oxide, and the polypropylene oxide has at least 3 isocyanate reactive groups derived from double metal cyanide Chelate-catalyzed ring-opening addition polymerization of propylene oxide with an unsaturation of less than 0.020 meq/g. The foam according to claim 1, wherein the second isocyanate active component (b2) is poly(tetramethylene ether) glycol, and the weight average molecular weight is 1,200-2,400 g/mol. All of the hydroxyl functional groups in the second isocyanate-reactive component (b2) are first-order hydroxyl groups. The foam according to claim 1, wherein the second isocyanate active component (b2) is poly(trimethylene ether) glycol and has a weight average molecular weight of 1,200 to 3,000 g/mol. All of the hydroxyl functional groups in the second isocyanate-reactive component (b2) are first-order hydroxyl groups. The foam according to claim 1, wherein the second isocyanate active component (b2) is a poly(ethylene oxide-propylene oxide) copolymer containing at least 7.5 parts by weight of ethylene oxide. , based on 100 parts by weight of the second isocyanate active component. The foam according to claim 25, wherein the second isocyanate active component (b2) is a poly(ethylene oxide-propylene oxide) copolymer diol, and the degree of unsaturation is less than 0.05 meq. /g, the first stage hydroxyl content exceeds 51% by weight, based on the weight of the total hydroxyl groups in the second isocyanate active component (b2). The foam according to claim 1, wherein the crosslinking agent has a weight average molecular weight of 60 to 420 g/mol and has at least two isocyanate reactive functional groups. The foam according to claim 1, wherein the crosslinking agent is used in an amount of from 0.2 to 15 parts by weight based on 100 parts by weight of the isocyanate-active mixture. A foam as disclosed in claim 28, wherein the crosslinking agent is used in an amount of from 1.2 to 12 parts by weight based on 100 parts by weight of the isocyanate-active mixture. A foam as set forth in claim 1, wherein the isocyanate-reactive component further comprises 0 to 40 parts by weight (based on 100 parts by weight of the isocyanate-reactive component) of a polymer polyol, the polymer-dimer The alcohol has a solid content of 5 to 55 parts by weight, and the hydroxyl value is 15 to 50 mg KOH/g based on 100 parts by weight of the polymer polyol. a foam as shown in the first aspect of the patent application, wherein the isocyanate is active The component further comprises 0 to 5.0 parts by weight (based on 100 parts by weight of the total weight of the foam) of polypropylene oxide (b3) having a nominal hydroxyl functionality of 1, as a cell opener. The average molecular weight is 800-8,500 g/mol. The foam according to claim 31, wherein the isocyanate-reactive component further comprises 0 to 3.5 parts by weight (based on 100 parts by weight of the total weight of the foam) of polypropylene oxide (b3) as an opening A pore former having a nominal hydroxyl functionality of 1 and a weight average molecular weight of from 800 to 8,500 g/mol. The foam according to claim 1, wherein the catalyst (c) is a mixture of at least one selected from the group consisting of an organic metal catalyst: a salt of Bronsted acid and an alkali metal or a cloth. a salt of a polyacid and an alkaline earth metal. A foam according to claim 33, wherein the salt of bromide acid and an alkali metal is sodium hydrogencarbonate. A foam according to claim 33, wherein the salt of bromide acid and an alkali metal is sodium carbonate. A foam as shown in claim 1, wherein the crosslinking agent is a compound of the formula I H _(3-x) -N-[(CH ₂ ) ₂ -OH] _x wherein x is 1-3 Integer. A foam as disclosed in claim 36, wherein the crosslinking agent is diethanolamine. A method of preparing a low resilience foam comprising reacting a reactant comprising the following components at an isocyanate index of from about 65 to about 110: a. an isocyanate component which is substantially free of isocyanate groups directly An aromatic isocyanate attached to the benzene ring; b. an isocyanate reactive mixture, said isocyanate active mixture package Containing: (b1) a first isocyanate active component having at least 2.6 isocyanate reactive groups, a hydroxyl equivalent weight of 80-800 g, a hydroxyl value of 70-700 mg KOH/g, (b2) a second isocyanate active component, average The hydroxyl functional group is from 1.8 to 6.0, the hydroxyl equivalent is from 600 to 6,000 g, the hydroxyl value is from 9 to 94 mg KOH/g, and the primary hydroxyl group content is at least 30 parts by weight to the second isocyanate active component. The total weight of the hydroxyl group is 100 parts by weight, wherein the first isocyanate active component is used in an amount of 20 to 90 parts by weight, and the second isocyanate active component is used in an amount of 10 to 80 parts by weight, both in 100 parts by weight. a portion of the isocyanate reactive mixture; c. a catalyst; and d. optionally one or more materials selected from the group consisting of water, surfactants, crosslinking agents, and additives. The method of claim 38, wherein the first isocyanate-reactive component has from 2.6 to 6.5 isocyanate reactive groups. The method of claim 39, wherein the first isocyanate-reactive component has from 2.7 to 5.5 isocyanate reactive groups. The method of claim 38, wherein the first isocyanate-reactive component has a hydroxyl equivalent weight of from 100 to 700 g. The method of claim 41, wherein the first isocyanate-reactive component has a hydroxyl equivalent weight of from 90 to 510 g. The method of claim 38, wherein the second isocyanate reactive component has an average hydroxyl functionality of from 1.85 to 4.5. The method of claim 38, wherein the second isocyanate-reactive component has a hydroxyl equivalent weight of from 800 to 4,500 g. The method of claim 38, wherein the second isocyanate is active The first stage hydroxyl group content of the component is at least 40 parts by weight based on 100 parts by weight of the total weight of the second isocyanate active component hydroxyl group. The method of claim 45, wherein the second isocyanate-reactive component has a first-stage hydroxyl group content of at least 51 parts by weight based on 100 parts by weight of the total weight of the second isocyanate-reactive component hydroxyl group. The method of claim 38, wherein the first isocyanate active component is used in an amount of from 20 to 70 parts by weight, and the second isocyanate active component is used in an amount of from 30 to 80 parts by weight, both It is based on 100 parts by weight of the isocyanate reactive mixture. The method of claim 38, wherein the foam is prepared at an isocyanate index of from about 75 to about 105. The method of claim 38, wherein the isocyanate component comprises an isocyanate selected from one or more of the group consisting of aliphatic isocyanates, alicyclic isocyanates, and aromatic isocyanates in which isocyanate groups are not directly attached to the benzene ring. . The method of claim 49, wherein the aliphatic isocyanate comprises an aliphatic polyisocyanate monomer or a blend of an aliphatic polyisocyanate monomer and a trimer; wherein: the trimer is selected A product of the trimerization reaction of at least one polyisocyanate: an aliphatic polyisocyanate, an alicyclic polyisocyanate or an isocyanate group is not directly bonded to the aromatic polyisocyanate on the benzene ring; the NCO content of the blend is 20.5 - 50.0 parts by weight based on 100 parts by weight of total isocyanate in the isocyanate component; and the average calculated functionality is 2-3. The method of claim 50, wherein the aliphatic isocyanate comprises at least one selected from the group consisting of hexamethylene diisocyanate, hexamethylene triisocyanate, undecane triisocyanate, undecane two Isocyanate, Its dimers and trimers. The method of claim 50, wherein the aliphatic polyisocyanate is hexamethylene diisocyanate, and the trimer is a product of trimerization of hexamethylene diisocyanate. The method of claim 49, wherein the alicyclic isocyanate comprises an alicyclic polyisocyanate monomer or a blend of an alicyclic polyisocyanate monomer and a trimer; wherein: the trimer The product is a product of at least one polyisocyanate trimerization selected from the group consisting of aliphatic polyisocyanates, alicyclic polyisocyanates or aromatic polyisocyanates in which the isocyanate groups are not directly attached to the benzene ring; NCO in the blend The content is from 20.5 to 38.0 parts by weight based on 100 parts by weight of the total isocyanate in the isocyanate component; and the average calculated functionality is 2-3. The method of claim 53, wherein the alicyclic isocyanate comprises at least one selected from the group consisting of biscycloheptane triisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, methyl ring Hexane diisocyanate, dimethylcyclohexane diisocyanate, dimers and trimers thereof. The method of claim 53, wherein the alicyclic polyisocyanate is isophorone diisocyanate, and the trimer is a product of trimerization of hexamethylene diisocyanate. The method of claim 49, wherein the aromatic isocyanate in which the isocyanate group is not directly bonded to the benzene ring comprises an aromatic polyisocyanate monomer or an isocyanate group which is not directly bonded to the benzene ring. a blend of an aromatic polyisocyanate monomer and a trimer attached to a benzene ring; wherein: the trimer is a product of at least one polyisocyanate trimerization selected from the group consisting of aliphatic polyisocyanates, alicyclic rings Polyisocyanate or isocyanate An aromatic polyisocyanate not directly attached to the benzene ring; the NCO content in the blend is from 20.5 to 44.0 parts by weight based on 100 parts by weight of the total isocyanate in the isocyanate component; and the average calculated functionality is 2-3 . The method of claim 56, wherein the aromatic isocyanate in which the isocyanate group is not directly bonded to the benzene ring is at least one selected from the group consisting of benzene dimethylene diisocyanate and tetramethyl benzodia. Methyl diisocyanate, its dimers and trimers. The method of claim 56, wherein the aromatic polyisocyanate in which the isocyanate group is not directly bonded to the aromatic ring is phenylenediethylene diisocyanate or tetramethylbenzene dimethylene diisocyanate. The trimer is the product of the trimerization of hexamethylene diisocyanate. The method of claim 38, wherein the first isocyanate-reactive component (b1) is a polypropylene oxide having at least 3 isocyanate reactive groups and an unsaturation of less than 0.05 meq/g. The method of claim 38, wherein the first isocyanate-reactive component (b1) is a polypropylene oxide having at least 3 isocyanate reactive groups, an epoxy catalyzed by a double metal cyanide chelate Propane is prepared by ring-opening addition polymerization, and the degree of unsaturation is less than 0.020 meq/g. The method of claim 38, wherein the second isocyanate-reactive component (b2) is a poly(tetramethylene ether) glycol having a weight average molecular weight of 1,200 to 2,400 g/mol, All of the hydroxyl functional groups in the diisocyanate-reactive component (b2) are first-order hydroxyl groups. The method of claim 38, wherein the second isocyanate active component (b2) is a poly(trimethylene ether) glycol having a weight average molecular weight of 1,200 to 3,000 g/mol, the second All of the hydroxyl functional groups in the isocyanate-reactive component (b2) are first-order hydroxyl groups. The method of claim 38, wherein the second isocyanate-reactive component (b2) is a poly(ethylene oxide-propylene oxide) copolymer comprising at least 7.5 parts by weight of ethylene oxide. 100 parts by weight of the second isocyanate active component. The method of claim 63, wherein the second isocyanate-reactive component (b2) is a poly(ethylene oxide-propylene oxide) copolymer diol, which is polymerized by propylene oxide to have Prepared on the two hydroxyl initiators, then capped with ethylene oxide, the degree of unsaturation is less than 0.05 meq/g, the first level hydroxyl content is more than 51% by weight, and the second isocyanate active component (b2) The weight of the total hydroxyl group. The method of claim 38, wherein the crosslinking agent has a weight average molecular weight of from 60 to 420 g/mol and has at least two isocyanate reactive functional groups. The method of claim 38, wherein the crosslinking agent is used in an amount of from 0.2 to 15 parts by weight based on 100 parts by weight of the isocyanate reactive mixture. The method of claim 66, wherein the crosslinking agent is used in an amount of from 1.2 to 12 parts by weight based on 100 parts by weight of the isocyanate-active mixture. The method of claim 38, wherein the isocyanate-reactive component further comprises 0 to 40 parts by weight (based on 100 parts by weight of the isocyanate-reactive component) of a polymer polyol, the polymer polyol The solid content is 5 to 55 parts by weight, and the hydroxyl value is 15 to 50 mg KOH/g based on 100 parts by weight of the polymer polyol. The method of claim 38, wherein the isocyanate-reactive component further comprises 0 to 5.0 parts by weight (based on 100 parts by weight of the total weight of the foam) of polypropylene oxide (b3) as a cell opener The polypropylene oxide has a nominal hydroxyl functionality of 1 and a weight average molecular weight of 800-8,500 g/mol.