JP2018002831A - Composition for foamed urethane member excellent in compressive permanent set and foamed urethane member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for foamed urethane member and a member which are excellent in a compressive permanent set, compressive creep characteristics, vibration-proof property, damping property and impact absorption property.SOLUTION: A composition for foamed urethane member is a composition formed by reaction of (A) a polyol component, (B) a polyisocyanate component and (C) water, where (A) the polyol component is formed of a mixture of (A-1) polyol having a functional group number of 2.5-3.5, a molecular weight of 3,000-7,000 and an active hydroxyl group in its terminal, (A-2) polyfunctional polyol having a functional number of 4 or more, a molecular weight of 450 or more and an active hydroxyl group in its terminal and (A-3) low molecular polyol having a functional number of 2.0 and a molecular weight of 60-125, (B) the polyisocyanate component is diphenyl-methane-diisocyanate (MDI) or its derivative, and (C) water.SELECTED DRAWING: None

Description

  The present invention relates to a foamed urethane member composition excellent in compression creep property and a foamed urethane member.

Conventionally, anti-vibration materials, vibration-damping materials, shock-absorbing materials, and the like using a soft polyurethane foam having a sponge hardness and utilizing these anti-vibration properties and shock absorption properties are known (Patent Document 1, Patent Document 2).
However, in the foam, there is a merit of weight reduction, but on the other hand, when the sponge hardness is lowered, there is a problem that the compression set and the compression creep property are further lowered as compared with the case where the rubber hardness of the non-foam is lowered. there were.

  By the way, a foamed urethane member having a sponge hardness of 50 or less and having excellent vibration set resistance and compression creep properties has not been proposed so far. The appearance of these urethane foam members was strongly expected from various industrial fields as substitute materials, new buffer materials, and the like.

JP 2009-280658 A JP 2014-37488 A

Conventionally, it is known that polyurethane foam used as a vibration isolating member is deformed when subjected to a load, and the amount of deformation increases with time.
Therefore, the object of the present invention is that it is extremely convenient as a buffer material if a urethane foam member excellent in compression set, vibration proofing property, and compression creep property is used in a place where it is used under a load for a long time. Based on knowledge, it is providing the composition for urethane foam members excellent in compression set, vibration proof property, and compression creep property.
Another object of the present invention is to solve the conventional problems and have excellent compression set, compression creep characteristics, vibration proofing, vibration damping and shock absorption while the sponge hardness is 50 or less. It is to provide a urethane foam member.

The present inventors have conducted extensive research in view of the above points. As a result, a urethane foam member obtained by reacting a specific polyol with diphenylmethane diisocyanate or a derivative thereof has a low hardness of 50 or less in sponge hardness and has vibration resistance. The present invention has been found to be excellent and excellent in compression set and compression creep properties. That is,
(1) The composition for a foamed urethane member of the present invention comprises a composition obtained by reacting the following (A) polyol component, (B) polyisocyanate component, and (C) water, and is a compression set and vibration proof property. And excellent compression creep property,
(A) the polyol component is
(A-1) a polyol having an active hydroxyl group at the terminal, having a functional group number of 2.5 to 3.5 and a molecular weight of 3000 to 7000,
(A-2) a polyfunctional polyol having 4 or more functional groups and a molecular weight of 450 or more and having an active hydroxyl group at the terminal;
(A-3) consisting of a mixture with a low molecular polyol having a functional group number of 2.0 and a molecular weight of 60 to 125,
(B) the polyisocyanate component is diphenyl-methane-diisocyanate (MDI) or a derivative thereof;
(C) It consists of water.
(2) In the composition for a urethane foam member of the present invention, in the above (1), the polyol of (A-1) is a polymer polyol having a functional group of 2.5 to 3.5 and a molecular weight of 3000 to 7000, The polymer polyol is used in an amount of 40 parts by mass or more based on 100 parts by mass of the polyol.
(3) In the composition for a foamed urethane member of the present invention according to the present invention, in the above (1), the polyfunctional polyol having an active hydroxyl group at the terminal (A-2) is sorbitol as an initiator, and alkylene oxide is used. A polyfunctional polyol having an addition-polymerized functional group of 4.5 and a molecular weight of 450 to 550 is used.
(4) The foamed urethane member composition of the present invention is the above-mentioned (1) to (3), wherein the (B) polyisocyanate component diphenyl-methane-diisocyanate (MDI) derivative is a specific polyol. It is a prepolymer having an active isocyanate group at the terminal obtained from a reaction between an oligomer and a polyisocyanate compound.
(5) The urethane foam member of the present invention is excellent in compression set, compression creep property, vibration proofing property, vibration damping property, and shock absorption property using the composition for urethane foam member described in (1) to (4) above. It is characterized by being a urethane foam member.

The foamed urethane member of the present invention is deformed in accordance with the elastic modulus when subjected to a load, but has a small increase in the amount of deformation with time, and is excellent in compression set, vibration proofing property, and compression creep property.
And if it uses for the place etc. which receive a load over a long time and it is excellent, it will be excellent as a buffer member, and can be utilized for an impact-absorbing member, a vibration isolator, etc.

  In addition, for example, in a house with two or more floors, if the urethane foam member of the present invention is placed as a cushioning material between the beam supporting the floor and under the floor, floor vibration and impact on the floor can be suppressed, so noise Excellent effect as a restraining member.

In order to produce the urethane foam member of the present invention, the composition for a urethane foam member of the present invention comprises:
It consists of a composition obtained by reacting the following (A) polyol component, (B) polyisocyanate component, and (C) water.
Here, (A) the polyol component is
(A-1) a polyol having an active hydroxyl group at the terminal, having a functional group number of 2.5 to 3.5 and a molecular weight of 3000 to 7000,
(A-2) a polyfunctional polyol having 4 or more functional groups and a molecular weight of 450 or more and having an active hydroxyl group at the terminal;
(A-3) consisting of a mixture with a low molecular polyol having a functional group number of 2.0 and a molecular weight of 60 to 125,
(B) the polyisocyanate component is diphenyl-methane-diisocyanate (MDI) or a derivative thereof;
(C) It consists of water.

<(A-1) Polyol>
One of the polyol components (A) used in the present invention, the polyol (A-1) bears the main component of the polyol component, has a functional group number of 2.5 to 3.5, a molecular weight of 3000 to 7000, and a terminal. Have an active hydroxyl group.
When the number of functional groups is less than 2.5, compression set and compression creep properties are likely to deteriorate, and when the number of functional groups is greater than 3.5, the sponge hardness is more than 50, which is not preferable.
When the molecular weight is less than 3000, the sponge hardness is more than 50, which is not preferable, and when the molecular weight is more than 7000, the degree of unsaturation at the polyol terminal is increased and reaction inhibition is caused, which is not preferable.
The type of the terminal of the polyol is not particularly limited, but it is preferable to have a primary hydroxyl group or a primary hydroxyl group at least partially in order to ensure the foaming of the polyurethane.

  In order to achieve the object described above, specific examples of the polyol (A-1) used in the present embodiment include known polyoxypolyalkylenes from the standpoint of easy adjustment of liquid viscosity, molecular weight and number of functional groups. Polyols are preferred.

As the polyoxypolyalkylene polyol, a known compound obtained by ring-opening addition polymerization of alkylene oxide using a low molecular weight active hydrogen compound as an initiator can be used.
Examples of the low molecular weight active hydrogen compounds mentioned here include polyhydric alcohols using water, ethylene glycol, propylene glycol, diethylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, or a mixture of two or more of these. be able to.

  As a representative example of the polyether polyol, in addition to the polyether polyol using the initiator, there is a polymer polyol blended with an acrylic polymer or a styrene polymer. This time, this polymer polyol is added to 40 parts by mass of the polyol. It is characterized by using more than part by mass.

  Specific examples of trade names of the polyoxypolyalkylene polyol include trade names such as Excenol (manufactured by Asahi Glass Co., Ltd.), Sunflex (Sanyo Chemical Industries), and the like. A mixture of two or more of these can also be used.

  As long as there is no hindrance, a known castor oil-based polyol, ε-caprolactone-based polyol, β-methyl-δ-valerolactone-based polyol, carbonate-based polyol, or the like may be used, and two or more of these may be used in combination. You can also.

<(A-2) Polyfunctional polyether polyol>
The polyol having an active hydroxyl group at the terminal (A-2) used in the present invention is a polyol having a functional group number of 4 or more and a molecular weight of 450 or more obtained by addition polymerization of alkylene oxide using sorbitol as an initiator.

As the polyfunctional group polyol, a hyper-branched polymer (multi-branched polymer) having an active hydroxyl group at the terminal can also be used.
Examples of the hyper-branched polymer (multi-branched polymer) include a compound obtained by self-condensation of dimethanol fatty acid as a polycondensation system of AB type ₂ monomer.
Moreover, the compound by polyaddition of diisocyanate and triol can be mentioned as a polyaddition system of A ₂ B ₃ type monomer.
A polycondensation or polyaddition hyper-branched polymer (HBP) is synthesized in one step by selecting an appropriate monomer and becomes a compound having a spherical-like molecular shape with no intramolecular vacancies (references below) 1 and 2).
(Reference 1: Yang, G; M. Macromolecules, 32, 2215 (1999))
(Reference 1: Yang, G; M. Macromolecules, 32, 2215 (1999))
(Reference 2: Jikei, M .; Chon, S .; Kakimoto, M .; Kawauchi, S .; Imase, T .; Watanabe, J .; Macromolecules, 32, 2061 (1999))

A hyper-branched polymer (HBP) having an active hydroxyl group at the terminal of the polycondensation system of the AB type ₂ monomer (represented as AB ₂ HBP) is, for example, dimethanol propionic acid or dimethanol butane. It is a compound by self-condensation such as acid.
As a specific trade name of this hyper-branch polymer (HBP), for example, Boltorn H311 and P500 (manufactured by Perstorp) can be mentioned.

The hyperbranched polymer (HBP) having an active hydroxyl group at the terminal of the polyaddition system of the A ₂ B ₃ type monomer (represented as A ₂ B ₃ HBP) is diisocyanate {(Σ2 ⁿ ) -1} (where n = 1, 2, 3... (The same applies hereinafter) mol and triol (Σ2 ⁿ ) (where n = 1, 2, 3.
In this synthesis, a total amount of diisocyanate {(Σ2 ⁿ ) -1} and triol (Σ2 ⁿ ) mol was added to 100 parts by mass, and 100 parts by mass of toluene or methyl ethyl ketone as a solvent, and slowly refluxed at room temperature for 4 hours. Next, after adding 0.0025 parts by mass of dibutyl-tin-laurate as a catalyst to the reaction vessel and performing a reflux reaction at 80 ° C. for 4 hours, the reaction solution was removed with an evaporator at 80 ° C. under vacuum. Obtained by doing.

[Synthesis of polyaddition type hyper-branched polymer (HBP) of A ₂ B ₃ type monomer]
In a four-necked separable flask equipped with a heating device equipped with a stirring blade, a reflux device, and a thermometer, 500 g of methyl ethyl ketone (MEK) was charged under a nitrogen gas atmosphere, and then 577 g (2.6 mol) of isophorone-diisocyanate was charged.
Next, a solution of 423 g (5.2 mol) of glycerin and 500 g of MEK was added dropwise at room temperature with stirring, and the reaction was continued for 4 hours while maintaining the temperature of the reaction solution at 40 ° C. or lower.
Next, 0.025 parts by mass of dibutyl-tin-laurate as a reaction catalyst was charged into the reaction vessel and refluxed at 80 ° C. for 4 hours.
After completion of the reaction, the reaction solution was placed in an eggplant-shaped flask and then de-MEKed at 80 ° C. under vacuum using an evaporator. The obtained HBP had a viscosity of 56 Pa. The s viscous liquid had 4 functional groups and a hydroxyl value of 382.

<(A-3) Low molecular polyol>
The (A-3) low molecular polyol used in the present invention is a low molecular polyol having a functional group number of 2.0 and a molecular weight of 60 to 125. When the molecular weight is less than 60, the sponge hardness exceeds 50 and cannot be used. A low molecular polyol having a molecular weight of more than 125 cannot be used because it tends to deteriorate compression set and compression creep performance.

<Mixing ratio>
In the foamed urethane member composition of the present invention,
(A) a polyol component (A-1) having a functional group number of 2.5 to 3.5 and a molecular weight of 3000 to 7000, a polyol having an active hydroxyl group at the terminal;
(A-2) a polyfunctional polyol having an active hydroxyl group at the terminal, having four or more functional groups and a molecular weight of 450 or more;
(A-3) a low molecular polyol having a functional group number of 2.0 and a molecular weight of 60 to 125;
The mixing ratio is preferably as follows.
That is,
When the total amount of (A-1) polyol, (A-2) polyfunctional polyol, and (A-3) low molecular weight polyol is 100 parts by mass,
The (A-1) polyol / (A-2) polyfunctional polyol / (A-3) low molecular polyol is preferably 92/6/3 to 91/5/4.
More preferably, it is set to 91/6/3 to 92/5/3.
Among these mixing ratios, when the ratio of (A-2) polyfunctional polyol is more than 7, it is not preferable because the sponge hardness is higher than 50, and when it is less than 4, the compression set and the compression creep deformation amount are not preferable. The effect on is not seen.
In addition, when the proportion of (A-3) the low molecular polyol exceeds 4 in the mixing ratio, it is not preferable because the sponge hardness becomes higher than 50, and when it is less than 3, the compression set and the compression creep deformation. No effect on quantity.
Therefore, out of the total amount of 100 parts by mass,
(A-2) The proportion of the polyfunctional polyol is preferably between 5 and 6 parts by mass,
(A-3) The proportion of the low molecular polyol is preferably between 3 and 4 parts by mass,
(A-1) The polyol is adjusted as the remaining amount.

<(B) Polyisocyanate component>
Examples of the (B) polyisocyanate component include diphenyl-methane-diisocyanate (MDI), carbodiimide partially modified MDI (liquid MDI), and derivatives such as MDI or liquid MDI.
Here, the derivatives of MDI or liquid MDI (in the present specification, these are referred to as prepolymers) can be obtained as a compound having a terminal isocyanate residue by a known method shown below.
This prepolymer is not an essential component in the present invention,
(A) It is preferable to add to improve the compatibility with the polyol component and to facilitate mixing with other components.
The MDI or liquid MDI derivative (prepolymer) used in the present invention is:
A polyether polyol having a functional group number less than the theoretical amount of 2.5 to 3.5 is reacted with a polyisocyanate compound using a known technique, and the remaining amount of the active isocyanate group (NCO group) is 8 to 15% by mass at the terminal. , Preferably 9-12 mass% is good.
When the remaining amount of the active isocyanate group (NCO group) exceeds 15% by mass, there is no effect of using the prepolymer, and when the remaining amount of the active isocyanate group (NCO group) is less than 8% by mass, the prepolymer The viscosity of the resin becomes high, which causes troubles in the production of urethane foam members.

  Moreover, as long as there is no trouble as said (B) polyisocyanate component, you may use isophorone diisocyanate, tolylene diisocyanate, cyclohexyl diisocyanate, hexamethylene diisocyanate, xylidene diisocyanate, etc., and use these 2 or more types together. You can also.

In the present invention, when the (A) polyol component, (B) polyisocyanate component, and (C) water are reacted, the reaction ratio of the prepolymer with respect to the hydroxyl group (OH) of (A) polyol component + (C) water is determined. The equivalent ratio of isocyanate groups (NCO groups), that is, the NCO / OH ratio (INDEX) is 1.00 to 1.10, preferably 1.03 to 1.05.
When the equivalent ratio exceeds 1.10, it is not preferable because the foamed urethane member lacks stability over time, and the sponge hardness exceeds 50, making it difficult to use. When the equivalent ratio is less than 1.00 This is not preferable because the compression set and the amount of compressive creep deformation increase.
In addition, the hardness of the foaming urethane member obtained becomes low, so that an equivalence ratio becomes small.

Here, in performing the urethanization reaction between the (B) polyisocyanate component, (A) polyol component, and (C) water, an appropriate urethanization catalyst can be used. As this urethanization catalyst, known catalysts such as tertiary amine compounds and organometallic compounds can be used. For example, triethylenediamine, N, N-dimethylhexamethylenediamine, N, N-dimethylbutanediamine, diazabicyclo (5,4,0) undecene-7 (DBU) and DBU salt, bismuth tris (2-ethylhexanoate) Diisopropoxybis (ethyl acetoacetate) titanium, lead octylate, dibutyltin laurate and the like are suitable.
However, the use of this urethanization catalyst is not an essential requirement of the present invention.

  Here, in reacting (A) the polyol component, (B) the polyisocyanate component, and (C) water, an appropriate foam stabilizer can be used. For example, organopolysiloxane, alkyl carboxylate, alkylbenzene sulfonate, and the like can be given. The compounding quantity of a foam stabilizer is 0-5 mass parts with respect to 100 mass parts of all the polyols, Preferably it is 1-2 mass parts.

  In addition, in order to improve the durability and stability of the urethane foam member, as a stabilizer, a heat stabilizer, an antioxidant, an ultraviolet absorber, an ultraviolet stabilizer, a filler, etc., as long as there is no hindrance, 1 A seed or a mixture of two or more may be used. In addition to the above, pigments, dyes, flame retardants, plasticizers, dispersants, surface modifiers, and the like can be added as appropriate.

Thus, the (A) polyol component, (B) polyisocyanate component, and (C) water used as raw materials are mixed at the normal temperature or in the heated state. Here, (C) water may be mixed with the polyol in advance, or may be added when the main components are mixed.
When the additive is mixed, it may be mixed in advance with the (A) polyol component or may be added when the main components are mixed.

After thoroughly mixing the above-mentioned components, 242 g is poured into a mold of 220 mm × 220 mm × 10 mm thickness heated to room temperature to 100 ° C., the lid is covered, and a urethanization reaction takes place at room temperature to 100 ° C. for 15 minutes. Let
After that, the foamed urethane member can be obtained by taking out from the mold and pre-reacting for 2 hours.

Hereinafter, Examples 1 to 10 and Comparative Examples 1 to 14 are shown in the table in order to describe the present invention in more detail.
(A) The following materials were prepared as polyol components.
(A-1) Polyol <Polyol 1>
Mixture of polyoxypolypropylene (terminal ethylene) triol and acrylic resin (number of functional groups 3, average hydroxyl value 30, average molecular weight 5600)
<Polyol 2>
Polyoxypolypropylene (terminal partial ethylene) triol (functional group number 3, average hydroxyl value 56, average molecular weight 3000)
<Polyol 3>
Polyoxypolypropylene (terminal partial ethylene) triol (functional group number 3, average hydroxyl value 24, average molecular weight 6700)
<Polyol 4>
Polyoxypolypropylene (terminal partial ethylene) triol (functional group number 3, average hydroxyl value 65, average molecular weight 2600)
<Polyol 5>
Mixture of polyoxypolypropylene (terminated ethylene) triol and acrylic resin (number of functional groups 3, average hydroxyl value 24, average molecular weight 7015)
<Polyol 6>
Polyoxypolypropylene (terminal partial ethylene) diol (number of functional groups 2, average hydroxyl value 28, average molecular weight 4000)
<Polyol 7>
Polyoxypolypropylene (terminal partial ethylene) tetraol (functional group number 4, average hydroxyl value 32, average molecular weight 6800)

(A-2) Polyfunctional polyol <Polyol 8>
Sorbitol-based (terminal propylene) hexaol (5 functional groups, average hydroxyl value 550, average molecular weight 510)
<Polyol 9>
Hyper-branched polymer which is a polyaddition product of isophorone diisocyanate-glycerin having an active hydrogen group at the terminal (functional group number 4, hydroxyl value 382, average molecular weight 580)
<Polyol 10>
Aliphatic amine-based polyol (functional group number 3, hydroxyl value 480, average molecular weight 350)

(A-3) Low molecular polyol <polyol 11>
1,4-butanediol (functional group 2, hydroxyl value 1,245, average molecular weight 90)
<Polyol 12>
Dipropylene glycol (functional group 2, hydroxyl value 837, average molecular weight 134)
<Polyol 13>
Ethylene glycol (functional group 2, hydroxyl value 1,808, average molecular weight 62)

Below, it describes about the isocyanate 1-4 used as (B) polyisocyanate component.
<Isocyanate 1>
A prepolymer obtained by reacting monomeric MDI (NCO mass%: 33.1) having 2 functional groups with polyether polyol (functional group 3, hydroxyl value 24, average molecular weight 6700) (residual amount of terminal active isocyanate group: 10 mass%) )
<Isocyanate 2>
A prepolymer obtained by reacting monomeric MDI (NCO mass%: 33.1) having 2 functional groups with polyether polyol (functional group 3, hydroxyl value 24, average molecular weight 6700) (residual amount of terminal active isocyanate group 8 mass%) )
<Isocyanate 3>
Monopolymer MDI (NCO mass%: 33.1) having 2 functional groups and a polyether polymer (functional group 3, hydroxyl value 24, average molecular weight 6700) reacted with a prepolymer (terminal active isocyanate group remaining amount 15 mass%) )
<Isocyanate 4>
A prepolymer obtained by reacting monomeric MDI (NCO mass%: 33.1) having 2 functional groups with polyether polyol (functional group 3, hydroxyl value 24, average molecular weight 6700) (residual amount of terminal active isocyanate group 7 mass%) )
<Isocyanate 5>
A prepolymer obtained by reacting monomeric MDI (NCO mass%: 33.1) having 2 functional groups with polyether polyol (functional group 3, hydroxyl value 24, average molecular weight 6700) (residual amount of terminal active isocyanate group 18 mass%) )

<C> Water was pure water.
The following materials were added as other materials.
<Antioxidant>
Pentaerythrityl-tetrakis <3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate <UV absorber>
2- (2′-hydroxy-3 ′, 5′-ditertiary amylphenylbenzotriazole <catalyst>
Triethyldiamine <Foam stabilizer>
Block copolymer of dimethylpolysiloxane and polyether

[Example 1]
(A-1) Polyol 1 of a polymer polyol having 3 functional groups, a hydroxyl value of 30, and a molecular weight of 5600 was used as the polyol component.
The molecular weight of polyol 1 was set to a value close to the median value of 3000 to 7000.
[Example 2]
(A-1) As a polyol component, a polyol 1 of a polymer polyol having a functional group number of 3, a hydroxyl value of 30, and a molecular weight of 5600 and a polyol of a polyether polyol having a functional group number of 3, a hydroxyl value of 56, and a molecular weight of 3000 are blended. did. At this time, the number of parts of the polymer polyol was 46.5 parts [Example 3]
(A-1) Polyol 2, which is a polyether polyol, having 3 functional groups, a hydroxyl value of 56, and a molecular weight of 3000 was used.
The molecular weight of polyol 2 was set to 3000, which is substantially equivalent to the lower limit value 3000.
[Example 4]
(A-1) Polyol 3, which is a polyether polyol, having 3 functional groups, a hydroxyl value of 24, and a molecular weight of 6700 was used.
The molecular weight of the polyol 3 was set to a value 6700 close to the upper limit value 7000.

[Comparative Example 1]
(A-1) Polyol 4 having 3 functional groups, a hydroxyl value of 65 and a molecular weight of 2600 and having an active hydroxyl group at the terminal was used as the polyol component.
The molecular weight of polyol 4 was 2600, which was below the lower limit of 3000.
[Comparative Example 2]
(A-1) Polyol 5 having 3 functional groups, a hydroxyl value of 24, and a molecular weight of 7015 and having an active hydroxyl group at the terminal was used as the polyol component.
The hydroxyl value of polyol 5 was 7015, which exceeded the upper limit of 7000.
[Comparative Example 3]
(A-1) As the polyol component, polyol 6 having an active hydroxyl group at the terminal and having a functional group number of 2, a hydroxyl value of 28, and a molecular weight of 4000 was used.
The number of functional groups of polyol 6 was set to 2 below the lower limit of 2.5.
[Comparative Example 4]
(A-1) As the polyol component, polyol 7 having an active hydroxyl group at the terminal having 4 functional groups, a hydroxyl value of 32, and a molecular weight of 6800 was used.
The number of functional groups of polyol 7 was set to 4 exceeding the upper limit of 3.5.
In Examples 1 to 4 and Comparative Examples 1 to 4 shown in Table 1,
(A-2) Polyol 8 as a polyfunctional polyol,
(A-3) Polyol 11 as a low molecular polyol,
(B) Isocyanate 1 was used as the polyisocyanate component.

[Example 5]
(A-2) Polyol 8 having a functional group number of 4.5, a hydroxyl value of 550, and a molecular weight of 459 and having an active hydroxyl group at the terminal was used as the polyfunctional polyol.
The upper limit of the mixing ratio of polyol 8 was 6. Refer to Example 1 for the mixing ratio lower limit value 5.
[Example 6]
(A-2) As a polyfunctional polyol, polyol 9, which is a hyper-branched polymer, which is a polyaddition product of isophorone diisocyanate-glycerin having an active hydrogen group at the end of 4 functional groups, a hydroxyl value of 382, and a molecular weight of 580, was used. .

[Comparative Example 5]
(A-2) As the polyfunctional polyol, polyol 8 having a functional group number of 4.5 and a hydroxyl value of 550 and having an active hydroxyl group at the terminal was used.
The lower 4 was used as the mixing ratio lower limit value 5-6 of the polyol 8.
[Comparative Example 6]
(A-2) As the polyfunctional polyol, polyol 8 having a functional group number of 4.5 and a hydroxyl value of 550 and having an active hydroxyl group at the terminal was used.
As the mixing ratio lower limit value 5 to 6 of the polyol 8, the excess 7 was used.
[Comparative Example 7]
(A-2) As the polyfunctional polyol, polyol 10 having an aliphatic amine-based number of functional groups of 3, a hydroxyl value of 480, and a molecular weight of 350 was used.
Polyol 10 was a polyol having a molecular weight of 480 and a functional group number of 3 having a molecular weight of 500 or less and a functional group number of 4 or less.
In Examples 5-6 and Comparative Examples 5-7,
(A-1) The polyol component uses a blend of polyol 1 and polyol 2,
(A-3) The polyol component uses polyol 11,
(B) Isocyanate 1 was used as the polyisocyanate component.

[Example 7]
(A-3) As a low-molecular polyol component, 4 parts by mass of an upper limit value of 4 polyols 9 having a functional group number of 2, a hydroxyl value of 1245, and a molecular weight of 90 was used.

[Comparative Example 8]
(A-3) Polyol 11 having 2 functional groups, a hydroxyl value of 1808, and a molecular weight of 62 was used as the low molecular polyol component.
With respect to the molecular weight 65 to 125, the molecular weight 62 was set lower than the lower limit.
[Comparative Example 9]
(A-3) Polyol 10 having 2 functional groups, a hydroxyl value of 837, and a molecular weight of 134 was used as the low molecular polyol component.
With respect to the molecular weight of 65 to 125, the molecular weight was set to a value exceeding the upper limit.
[Comparative Example 10]
(A-3) As a low molecular polyol component, 2 parts by mass of polyol 9 having 2 functional groups, a hydroxyl value of 1245, and a molecular weight of 90 was used.
The mixing ratio of the polyol 9 was set to a ratio 2 that was lower than the lower limit value among the mixing ratios 3 to 4 of the (A-3) low molecular polyol component in the (A) polyol component.
[Comparative Example 11]
(A-3) As a low molecular polyol component, 2 parts by mass of polyol 9 having 2 functional groups, a hydroxyl value of 1245, and a molecular weight of 90 was used.
The mixing ratio of the polyol 9 was set to a ratio 5 that exceeded the upper limit value among the mixing ratios 3 to 4 of the (A-3) low molecular polyol component in the (A) polyol component.
In Example 6 and Comparative Examples 7 to 10, (A-1) the polyol component uses a blend of polyol 1 and polyol 2, (A-2) the polyol component uses polyol 8 and (B) Isocyanate 1 was used as the polyisocyanate component.

[Example 8]
(B) As a polyisocyanate component, NCO mass% of isocyanate 1 which is a prepolymer was set to 8.0.
In the present invention, the remaining amount of the active isocyanate group (NCO group) at the terminal is 8 to 15% by mass, but the lower limit is 8.
[Example 9]
(B) As a polyisocyanate component, NCO mass% of isocyanate 1 which is a prepolymer was set to 15.0.
In the present invention, the remaining amount of the active isocyanate group (NCO group) at the terminal is 8 to 15% by mass, but the upper limit is 15.

[Comparative Example 12]
(B) As a polyisocyanate component, NCO mass% of isocyanate 1 which is a prepolymer was set to 7.0.
In the present invention, the remaining amount of the active isocyanate group (NCO group) at the terminal is 8 to 15% by mass, but is 7 below the lower limit.
[Comparative Example 13]
(B) As a polyisocyanate component, NCO mass% of isocyanate 1 which is a prepolymer was set to 18.0.
In the present invention, the remaining amount of the active isocyanate group (NCO group) at the terminal is 8 to 15% by mass, but is 18 exceeding the upper limit.
In Examples 7-8 and Comparative Examples 11-12,
(A-1) The polyol component uses a blend of polyol 1 and polyol 2,
(A-2) The polyol component uses polyol 8,
(A-3) Polyol 11 was used as the polyol component.

[Example 10]
(B) The NCO / OH ratio (INDEX) indicating the reaction ratio of the polyisocyanate component and the (A) polyol component was set to a lower limit of 1.0 among 1.0 to 1.1.
[Example 11]
The NCO / OH ratio (INDEX) indicating the reaction ratio of the (B) polyisocyanate component and the (A) polyol component was set to an upper limit of 1.1 among 1.0 to 1.1.

[Comparative Example 14]
(B) NCO / OH ratio (INDEX) indicating the reaction ratio of the polyisocyanate component and the (A) polyol component was set to 0.9, which is lower than the lower limit value 1.0 among 1.0 to 1.1.
[Comparative Example 15]
(B) NCO / OH ratio (INDEX) indicating the reaction ratio between the polyisocyanate component and the (A) polyol component was set to 1.2 exceeding the upper limit 1.1 among 1.0 to 1.1.
In Examples 9-10 and Comparative Examples 13-14,
(A-1) The polyol component uses a blend of polyol 1 and polyol 2,
(A-2) The polyol component uses polyol 8,
(A-3) Polyol 11 was used as the polyol component.
(B) Isocyanate 1 was used as the polyisocyanate component.

<Foamed urethane member>
Using the above materials, the reaction was started by mixing for 15 seconds with a homogenizer (3000 rpm / min) according to the formulations shown in Tables 1 to 4, and the mixture was added to a mold having a size of 220 × 220 mm and a thickness of 10 mm. After casting, the cap was put on, the reaction was continued at a temperature of 80 ° C. for 15 minutes and then demolded, followed by curing at 100 ° C. for 2 hours.
As a result, a sheet-like urethane foam member having a size of 220 × 220 mm, a thickness of 10 mm, and an apparent density of 0.50 g / cm ³ was obtained.

  And about the obtained sheet-like foaming urethane member, the following experiment was done and the result was shown in Table 5-Table 8. FIG.

In the table, the sponge hardness is 50 or less.
Compression set is
A: 5% or less B: Over 5 and 10% or less X: Over 10 and 20% or less XX: Antivibration performance exceeding 20%
A: 0.3 or more B: 0.2 or more and less than 0.3 x: 0.1 or more and less than 0.2 xx: Less than 0.1.
Compression creep is
A: Change rate of less than 10% B: Change rate of 10 or more and less than 20% X: Change rate of 20 or more and less than 30% XX: Change rate of 30% or more.

  In Tables 1 to 4, the unit of numerical values in the column of prescription indicates parts by mass, and INDEX (NCO / OH ratio) is (A) polyol component + (C) prepolymer based on water hydroxyl group (OH). The equivalent ratio of isocyanate groups (NCO groups) is shown.

  In Tables 5 to 8, “sponge hardness” is a numerical value as a result of measurement using a spring-type sponge hardness meter (C type) according to JIS K7312.

Further, “compression set” as an evaluation is measured according to JIS K6301 (compression rate 50%, 70 ° C., 24 hours), and is expressed as a permanent strain amount (%) with respect to the compression deformation length.
Here, the meanings of A, B, x, and xx shown as the evaluation of “compression set” are A when the permanent set is 5% or less, and B when the range is over 5% and 10% or less. Those exceeding 10% and not more than 20% were evaluated as x, and those exceeding 20% were evaluated as xx.
In addition, the natural rubber conventionally used as an anti-vibration material has a permanent strain of 30 to 50% (evaluation xx).

In addition, “15% compressive strength” as an evaluation is a compression test according to JIS K6911 and indicated by a numerical value of stress at 15% strain (unit: kg / cm ² ) (so-called compression at 15% strain). Strength).

Further, “vibration resistance” as an evaluation was measured by a dynamic bending test (viscoelasticity analyzer RSA-II, Rheometric, Inc.) using the obtained foamed urethane member as a test piece of 50 mm × 50 mm × 10 mm thickness. It is a numerical value (so-called tan δ) of the measurement result at 23 ° C.
The meanings of A, B, x, and xx shown as the evaluation of the vibration proofing property (tan δ) are as follows. And a value in the range of less than 0.2 and 0.1 or more was evaluated as x, and a value in the range of less than 0.1 was defined as xx.
In addition, the natural rubber for the vibration isolator was about 0.1 (evaluation x or less).

In addition, “compressive creep property” as an evaluation was applied to the obtained foamed urethane member under a condition of an atmospheric temperature of 70 ° C. and a compressive stress of 0.8 to 1.2 kg / cm ^2. The stress was such that the member) deformed by about 10% at the initial stage of load (instantaneous elastic deformation).
(JIS K6767 foamed plastic-polyethylene-test method or JIS K6385 anti-vibration rubber-test method)

  The meanings of A, B, XX, and XX shown as the evaluation of compression creep indicate that the initial stress (instantaneous elastic deformation) is subjected to a considerable stress that deforms about 10%, and this thickness is set to 0 hours (value before test). ), The thickness change rate is less than 10% after 1000 hours, A is the thickness change rate is 10% or more and less than 20% B, the thickness change rate is 20% or more and less than 30% Was defined as x, and the thickness change rate of 30% or more was defined as xx.

From the results shown in Tables 5 to 8, the urethane foam member molded by the formulation of each example according to the present invention is excellent in hardness, compression set, 15% compression strength, and excellent in vibration proofing (tan δ). (2 to 3 times the rubber for vibration isolation).
On the other hand, it turns out that the foaming urethane member shape | molded by the prescription of Comparative Examples 1-11 is inferior to compression set or compression creep property.

The urethane foam member of the present invention is excellent in vibration damping properties, compression set and compression creep properties, and can be used as a vibration damping member, a vibration damping member, a shock absorbing member, or the like. For example, it can be suitably used as a vibration isolating member application that receives a load and dislikes that the amount of deformation increases with time.
Furthermore, since the urethane foam member of the present invention is excellent in compression set and compression creep even when subjected to a load for a long time, it can be suitably used as a buffer member.
As another application, for example, in a two-story house or more, if the urethane foam member of the present invention is placed as a cushioning material between the beam supporting the floor and under the floor, floor vibration and impact on the floor can be suppressed. Therefore, it can be suitably used as a noise suppression member, and industrial applicability is extremely high.

Claims (5)

It is composed of a composition obtained by reacting the following (A) polyol component, (B) polyisocyanate component, and (C) water, and is excellent in compression set, compression creep properties, vibration damping properties, vibration damping properties and shock absorption properties. A composition for foamed urethane members.
(A) the polyol component is
(A-1) a polyol having an active hydroxyl group at the terminal, having a functional group number of 2.5 to 3.5 and a molecular weight of 3000 to 7000,
(A-2) a polyfunctional polyol having 4 or more functional groups and a molecular weight of 450 or more and having an active hydroxyl group at the terminal;
(A-3) consisting of a mixture with a low molecular polyol having a functional group number of 2.0 and a molecular weight of 60 to 125,
(B) the polyisocyanate component is diphenyl-methane-diisocyanate (MDI) or a derivative thereof;
(C) It consists of water. The polyol (A-1) is a polymer polyol having a functional group of 2.5 to 3.5 and a molecular weight of 3000 to 7000,
The composition for a urethane foam member according to claim 1, wherein 40 parts by mass or more of the polymer polyol is used with respect to 100 parts by mass of the polyol. The polyfunctional polyol having an active hydroxyl group at the terminal (A-2) is a polyfunctional polyol having a functional group of 4.5 by addition polymerization of alkylene oxide using sorbitol as an initiator and a molecular weight of 450 to 550. The composition for urethane foam members described in 1. (B) A derivative of diphenyl-methane-diisocyanate (MDI) as the polyisocyanate component is
The composition for a foamed urethane member according to any one of claims 1 to 3, which is a prepolymer having an active isocyanate group at a terminal obtained from a reaction between a specific polyol oligomer and a polyisocyanate compound. A foamed urethane member excellent in compression set, compression creep characteristics, vibration proofing, vibration damping and shock absorption using the composition for a foamed urethane member according to any one of claims 1 to 4.