JP2006219508A - Polyol composition and flexible polyurethane expansion-molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flexible polyurethane expansion-molded product satisfying both resistance to moist heat compression and resonance frequency properties at high levels, and a polyol composition capable of forming the flexible polyurethane expansion-molded product. <P>SOLUTION: The polyol composition comprises (A) a polyol providing a hydroxy group and (B) an organosilicate, where the combination of the component (A) and the component (B) is such that gives a long-period spacing (d value) of at least 35 Å when only the components (A) and (B) are mixed. The flexible polyurethane expansion-molded product is formed by expanding in a mold a polyurethane expansion stock solution comprising the polyol composition and, further incorporated therewith, (C) a polyisocyanate providing an isocyanate group. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a flexible polyurethane foam molded article excellent in resonance frequency characteristics and wet heat compression characteristics, and a polyol composition capable of forming the flexible polyurethane foam molded article.

Conventionally, in a polyurethane foam molded product used as an interior material for automobiles, it is widely known that a material with high hardness has low moisture-heat compression characteristics, and that the hardness decreases with improvement in moisture-heat compression characteristics. And a method for solving the conflicting problem of improvement in heat-and-humidity compression resistance has been desired (see Non-Patent Document 1: Macromolecules, 2001, 34, p.337-339).
The present applicant has previously found that a flexible polyurethane foam obtained by blending an inorganic filler into a polyurethane foam stock solution has high hardness and excellent wet heat compression characteristics (Patent Document 1: Special). No. 2004-210976).

  Here, a flexible polyurethane foam used as an automobile interior material is required not only to have high hardness and excellent resistance to moisture and heat compression but also to have excellent resonance frequency characteristics (low resonance frequency). It has been desired to develop a flexible polyurethane foam molded article having higher hardness, excellent resistance to wet heat compression, and excellent resonance frequency characteristics.

Ruijian Xu and three others, Macromolecules, 2001, 34, p. 337-339 JP 2004-210976 A

  The present invention has been made in view of the above circumstances, and a flexible polyurethane foam molded article having both high-temperature moisture compression resistance and resonance frequency characteristics at a high level, and a polyol composition capable of forming the flexible polyurethane foam molded article. The purpose is to provide.

As a result of intensive studies to achieve the above object, the present inventor, when forming a flexible polyurethane foam molded article using a polyurethane foam stock solution containing a polyol component and a silicate, in accordance with a specific index, the polyol component and silicic acid By selecting the combination with the salt, it is possible to adjust the heat-and-moisture compression characteristics and resonance frequency characteristics of the resulting flexible polyurethane foam molded article, and consequently the moisture-resistant heat compression characteristics and resonance frequency characteristics of the resulting flexible polyurethane foam molded article. And found that both can be achieved at a high level.
That is, when a polyol component and a silicate are mixed, a long-period structure to be described later may be observed. This long-period interval (d value) and the heat-and-moisture compression resistance characteristics of the resulting flexible polyurethane foam molded article and The inventor has found that the resonance frequency characteristics correlate well. The inventors have found that designing a flexible polyurethane foam molded article using this d value as an index is appropriate for designing a flexible polyurethane foam molded article having both of the above characteristics at a high level. Invented the invention.

Accordingly, the present invention provides the following polyol composition and flexible polyurethane foam molded article.
Claim 1:
Next (A) component and (B) component,
(A) a polyol supplying a hydroxyl group,
(B) Organosilicates,
A long cycle interval (d value) measured when the combination of the component (A) and the component (B) is a mixture of only the component (A) and the component (B). A polyol composition characterized by being a combination of at least 35%.
Claim 2:
2. The polyol composition according to claim 1, wherein the component (A) is one or more selected from the group consisting of polyether polyol, polyester polyol, and polymer polyol.
Claim 3:
The polyol composition according to claim 1 or 2, wherein the component (B) is blended in an amount of 0.1 to 30 parts by mass with respect to 100 parts by mass of the component (A).
Claim 4:
The following components (A) to (C);
(A) a polyol supplying a hydroxyl group,
(B) Organosilicates,
(C) a polyisocyanate for supplying isocyanate groups,
A foamed polyurethane foam formed by foaming a foamed polyurethane foam solution in a mold, wherein the combination of the component (A) and the component (B) is a component (A) and a component (B). A soft polyurethane foamed molded article, which is a combination having a long-period interval (d value) of 35 mm or more measured when only these are mixed.
Claim 5:
The flexible polyurethane foam molded article according to claim 4, wherein the component (A) is one or more selected from the group consisting of polyether polyol, polyester polyol, and polymer polyol.
Claim 6:
The flexible polyurethane foam molded article according to claim 4 or 5, wherein the component (B) is blended in an amount of 0.1 to 30 parts by mass with respect to 100 parts by mass of the component (A).

  ADVANTAGE OF THE INVENTION According to this invention, the polyol composition which can form the flexible polyurethane foam molded object excellent in the resonance frequency characteristic and the heat-and-humidity compression characteristic, and the said flexible polyurethane foam molded object is provided. The flexible polyurethane foam molded article of the present invention is particularly useful as a vehicle interior material or the like (including a vehicle seat material or a vehicle pad material).

The present invention will be described in further detail below.
The polyol composition of the present invention comprises the following components (A) and (B):
(A) a polyol supplying a hydroxyl group,
(B) Organosilicates,
The flexible polyurethane foam molded article of the present invention comprises the following components (A) to (C):
(A) a polyol supplying a hydroxyl group,
(B) Organosilicates,
(C) a polyisocyanate supplying an isocyanate group,
It is a soft polyurethane foam molded article formed by foaming a polyurethane foam stock solution containing
And in the present invention, both the polyol composition and the flexible polyurethane foam molded article include only the component (A) and the component (B) as a combination of the component (A) and the component (B). It is characterized by using a combination in which the long period interval (d value) measured by the method described later when mixed is 35 mm or more.

  As the polyol for supplying the hydroxyl group (A), a conventional polyol for polyurethane foam can be used, and is not particularly limited. For example, polyhydric alcohols such as divalent to hexavalent, polyoxyalkylene polyol (polyether) Polyol), polyester polyol, polymer polyol, and the like. In particular, it is preferable to use a polyether polyol or a polyester polyol, and it is more preferable to use a polyether polyol. These polyols may be used alone or in combination of two or more.

  As the polyether polyol, a polyether polyol obtained by ring-opening polymerization of alkylene oxide is preferable from the viewpoint of reactivity. Examples of such alkylene oxides include propylene oxide (PO) and ethylene oxide (EO). These may be used alone or in combination of two or more.

Among these, from the viewpoint of raw material activity, the polyether polyol is preferably a polyether polyol obtained by copolymerization of the PO and the EO. Examples of the polymerization initiator include pentaerythritol and glycerin.
The blending ratio of PO and EO during copolymerization is usually 8/92 to 18/82 (molar ratio) as EO / PO (molar ratio), preferably 13/87 to 15/85 (molar ratio). is there. When EO / PO (molar ratio) is out of the above range, it may be difficult to produce a polyether polyol.

  In addition, when the polyether polyol is obtained by polymerization of a monomer composition containing EO, the proportion of the EO-derived molecular chain unit in the polyether polyol is usually 0 to 25% by mass, preferably 10 to 20% by mass.

  The number of hydroxyl groups contained in one molecule of the polyether polyol is usually 2 to 4, particularly preferably 3. If the number of hydroxyl groups is too large, the raw material viscosity may increase, and if it is too small, the physical properties may decrease.

  As the polyether polyol, it is preferable to use one having a low degree of unsaturation. More specifically, a polyether polyol having an unsaturation degree of usually 0.07 meq / g or less, preferably 0.04 meq / g or less is used. When the degree of unsaturation in the polyether polyol exceeds 0.07 meq / g, the durability and hardness of the flexible polyurethane foam molded article of the present invention may be impaired. In the present invention, the “degree of unsaturation” refers to a method in which acetic acid released by acting mercuric acetate on unsaturated bonds in a sample is titrated with potassium hydroxide in accordance with JIS K 1557-1970. It means the total degree of unsaturation measured (milli equivalent / g).

  The number average molecular weight of the polyether polyol is usually 9000 or less, preferably 8000 or less, more preferably 6000 or less, still more preferably 5000 or less, and the lower limit is usually 1000 or more, preferably 2000 or more. When the number average molecular weight of the polyether polyol exceeds 9,000, the viscosity of the component (A) becomes too large, and the stirring efficiency of the polyurethane foam stock solution may be inferior. On the other hand, if the number average molecular weight of the polyether polyol is less than 1000, the resilience of the resulting polyurethane foam may be greatly reduced. In the present invention, the number average molecular weight is a value calculated as a polystyrene equivalent value by the GPC method.

  On the other hand, as the polymer polyol, it is possible to use a general-purpose polymer polyol for a polyurethane foam molded article. More specifically, for example, a polymer component such as polyacrylonitrile or acrylonitrile-styrene copolymer is grafted to a polyether polyol made of polyalkylene oxide, preferably having a number average molecular weight of 3,000 to 8,000, preferably 4,000 to 7,000. Examples thereof include a copolymerized polyol. The alkylene oxide used as a raw material for the polyether polyol (polyalkylene oxide) preferably includes propylene oxide, and particularly preferably includes propylene oxide alone or includes both propylene oxide and ethylene oxide. The proportion of the graft polymer component as described above in the polymer polyol is usually 25 to 50% by mass.

  In the above component (A), when a polyether polyol and a polymer polyol are blended and used, the blending ratio is usually 30/70 to 100/0 as (polyether polyol) / (polymer polyol) (mass ratio). , Preferably 40/60 to 80/20. When the blending ratio of the two deviates from the above range, the physical properties of the polyurethane foam molded article of the present invention may be deteriorated or a reaction failure may occur.

  In addition, a commercial item can be used as said (A) component, For example, KC282 (manufactured by Sanyo Chemical Co., Ltd.), KC264 (manufactured by Sanyo Chemical Co., Ltd.), etc. can be used.

  Examples of the silicate constituting the (B) organosilicate include a nesosilicate containing one silicon atom in a unit skeleton, a solosilicate containing several silicon silicates, and an isosilicate containing many silicon atoms, Examples include ferrosilicate, and specifically include magadiaite, kanemite, montmorillonite, saponite, hectorite, beidellite, stevensite, nontronite, and other smectite clay minerals, verculite, halloysite, or mica. Can be mentioned. These may be natural products or artificial synthetic products. Moreover, the organic silicate can be used alone or in combination of two or more. The component (B) is obtained by organically treating the silicate from the viewpoint of dispersibility in the polyol component.

  The organic treatment method is not particularly limited, and is a method of organically converting a silicate into an organic onium salt by ion exchange of a sodium ion as a counter ion of silicate, or a silicate by a chemical bond or an ionic bond. Examples thereof include a method of introducing an organic group on the surface. Among these, from the viewpoint of dispersibility in polyol, a method of quaternizing ammonium silicate by ion-exchange of sodium ion as a counter ion of silicic acid is preferable.

  Examples of organic onium ions include organic ammonium ions such as hexyl ammonium ion, octyl ammonium ion, 2-ethylhexyl ammonium ion, dodecyl (lauryl) ammonium ion, octadecyl (stearyl) ammonium ion, dioctyl dimethyl ammonium ion, and distearyl dimethyl ammonium ion; Examples include organic pyridinium ions such as alkylbipyridinium ions, but are not limited thereto. Among these, organic ammonium ions are preferable from the viewpoint of stability in the polyol component. These are preferably quaternary ammonium ions, but may be protonated primary, secondary, or tertiary amines.

  Moreover, as said organic ammonium ion, the thing whose organic group couple | bonded with a nitrogen atom is an alkyl group and / or a hydroxyalkyl group is preferable, and especially the di (hydroxyalkyl) dialkyl ammonium ion is preferable. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. On the other hand, the hydroxyalkyl group may be one having one OH group or two or more OH groups. Those having an OH group to be bonded, those having an OH group bonded to a carbon atom in the middle of the carbon chain, such as 2-hydroxy-n-propyl group and 2-hydroxy-n-butyl group, 1,3-dihydroxy-n- Examples thereof include those having an OH group bonded to a carbon atom at the end and in the middle of the carbon chain, such as a butyl group. Among these, those having an OH group at the terminal are preferable from the viewpoint of the strength of the flexible polyurethane foam to be produced. As an organic group couple | bonded with a nitrogen atom, you may have an ester bond, a urethane bond, etc. in the middle of carbon chains, such as an alkyl group and a hydroxyalkyl group. From the viewpoint of the stability of the dispersed state in the polyol component, it is also preferable to use a fluorinated silicate in which the OH group on the silicate surface is substituted with a fluorine atom.

  In addition, as said (B) component, you may use a commercial item, for example, Somasif MEE, Somasif ME-100, Somasif MAE, Somasif MTE (all are the Corp Chemical Co., Ltd. product).

  Although it does not specifically limit as a compounding quantity of the said (B) component, 0.1-30 mass parts normally with respect to 100 mass parts of said (A) component, Preferably it is 0.5-10 mass parts. Preferably it is 1-8 mass parts. If the amount is less than 0.1 parts by mass, the improvement of moisture heat compressibility and hardness may hardly be exhibited. In some cases, the component (B) cannot be uniformly dispersed in the urethane foam.

The polyisocyanate supplying the isocyanate group (C) preferably contains tolylene diisocyanate (TDI) and / or diphenylmethane diisocyanate (MDI) from the viewpoint of the molding density region.
Here, the TDI is not particularly limited, but is a mixture having a blending ratio of 2,4-TDI and 2,6-TDI of 80/20 to 50/50 (mass ratio). A mixture of 80/20 to 65/35 (mass ratio) is particularly preferable.
The MDI is not particularly limited, and can be used regardless of its molecular weight distribution. For example, pure (Pure) MDI (4,4'-MDI), polymeric MDI, crude MDI, etc. It can be used suitably.

  As such TDI and MDI, commercially available products can be used. As TDI, for example, T-80 (manufactured by Sumitomo Bayer Urethane Co., Ltd.), and as MDI, for example, 44V20 (manufactured by Sumitomo Bayer Urethane Co., Ltd.) MDI) can be used.

  When the TDI and MDI are used in combination, the mixing ratio of the two is usually 20/80 to 90/10 (mass ratio) as the value of TDI / MDI (mass ratio), preferably 50/50 to 80/20 ( Mass ratio).

  The proportion of the component (C) in the polyurethane foam stock solution (when two or more isocyanates are used in combination, the total amount of the isocyanate in the polyurethane foam stock solution) is an isocyanate equivalent (soft) When the amount of active hydrogen (mol) in the polyurethane foam stock solution is 100, the equivalent (mole) ratio of isocyanate groups in the flexible polyurethane foam stock solution is usually 80 or more, preferably 95 or more, and the upper limit is usually 120. Hereinafter, it is preferably 115 or less. If the isocyanate equivalent is less than 80, the resulting polyurethane foam may suffer from shrinkage, while if it exceeds 120, foam may be down.

The combination of the component (A) and the component (B) described above in the present invention includes a long period interval (d value) measured by the following method when only the component (A) and the component (B) are mixed. As a combination of 35 mm or more, preferably 35 to 80 mm, more preferably 50 to 80 mm.
Then, based on such an index of d value, the combination of the component (A) and the component (B) is selected, and further, the above-mentioned component (C) is blended to constitute a polyurethane foam stock solution. By foaming and curing to form a flexible polyurethane foamed molded product, in the present invention, a flexible polyurethane foamed molded product that achieves both high-humidity heat compression characteristics and resonance frequency characteristics at a high level can be realized. Although the details are not detailed, the present inventors have found that the d-value is well correlated with the wet heat compression resistance and resonance frequency characteristics of the obtained flexible polyurethane foam molded article.

[Measurement method of d value]
RINT2200V manufactured by Rigaku Denki Co., Ltd. is used, and the long-period interval measured by the wide-angle X-ray diffraction method with a tube of Cu, an acceleration condition of 40 kV × 50 mA, and a scanning speed of 4 ° / min is evaluated as a d value.
The “long period” refers to the period between layers of the component (B) with reference to the description in Polymer Dictionary, Polymer Society, 1971, page 431.

The polyurethane foam stock solution in the present invention may further contain a foaming agent, preferably water, as the component (D). Since water reacts with polyisocyanate to generate carbon dioxide gas, it can be used as a foaming agent in the present invention, and is also preferably used from the viewpoint of reducing environmental burden and manufacturing cost.
As a compounding quantity of (D) component in a polyurethane foam undiluted | stock solution, it is 1-7 mass parts normally with respect to 100 mass parts of polyols of the said (A) component, Preferably it is 2-5 mass parts. If the blending amount of the component (D) is out of the above range, the resulting flexible polyurethane foam molded article may be inferior in the thermal compression residual strain characteristics.

The polyurethane foam stock solution in the present invention may further contain a catalyst as the component (E) and a foam stabilizer as the component (F). Each of these components can contribute to shortening the production cycle time of the flexible polyurethane foam molded article.
As the catalyst (E), those commonly used for polyurethane foam can be used, and are not particularly limited, and examples thereof include amine catalysts such as triethylenediamine and diethanolamine. As a compounding quantity of (E) component in a polyurethane foam undiluted | stock solution, it is 0.3-2 mass parts normally with respect to 100 mass parts of polyols of the said (A) component.
A commercial item can be used as such (E) component, For example, a triethylenediamine (made by Kao Co., Ltd.), diethanolamine (made by Nippon Shokubai Co., Ltd.), etc. can be mentioned.

  As the foam stabilizer (F), general-purpose foaming agents for flexible polyurethane foamed molded articles can be used. For example, silicone foam stabilizers such as various siloxane-polyether block copolymers can be used. it can. A commercial item can be used as such a foam stabilizer, For example, L5309 (Nihon Unicar Co., Ltd. product), SRX274C (Toray Dow Corning Silicone Co., Ltd. product) etc. can be used. As a compounding quantity of the (F) component in the said polyurethane foam undiluted | stock solution, it is 0.3-2 mass parts normally with respect to 100 mass parts of polyols of the said (A) component.

  In the present invention, as a condition for obtaining a molded product by foaming a polyurethane foam stock solution in a mold, normal conditions may be used, and foam curing may be performed under normal pressure, or foam curing ( (Decompression method). The decompression method here is not particularly limited as long as it is a method in which a polyurethane foam stock solution is filled in a mold cavity and the inside of the cavity is decompressed when foamed and molded, and a known method can be applied.

The hardness (25% hardness of the skin part of the molded product, kgf) measured according to JIS K 6400 of the flexible polyurethane foam molded product of the present invention is usually 5 kgf or more, preferably 10 kgf or more, and the upper limit is usually 40 kgf or less. Preferably it is 30 kgf or less.
Further, the wet heat compression residual strain (%) measured in accordance with JIS K 6400 of the flexible polyurethane foam molded article of the present invention is usually 30% or less, preferably 25% or less, more preferably 20% or less, and still more preferably. Is 15% or less, particularly preferably 10% or less.
Furthermore, the resonance frequency (Hz) measured in accordance with JASO B 407 of the flexible polyurethane foam molded article obtained by the production method of the present invention is usually 5 Hz or less, preferably 4.5 Hz or less, more preferably 4 Hz or less. is there.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

[Examples 1-5, Comparative Examples 1-5]
Using the polyol shown in Table 1, a polyurethane foam stock solution was prepared at the compounding ratio shown in Table 2. In preparing the polyurethane foam stock solution, the components (A), (B), (E) and (F) are first blended and stirred for 10 minutes at 1800 rpm (preparation of the polyol composition), and then the component (C) (isocyanate). Composition) and (D) component (water) were blended and stirred at 5000 to 7000 rpm for 5 to 10 seconds to prepare a polyurethane foam stock solution.
The obtained polyurethane foam stock solution was poured into a cavity of a mold (mold temperature: 60 ° C., volume: 20 L) and foamed and cured under normal pressure. The amount of polyurethane foam stock solution charged was 1.2 kg.
Various physical properties of the obtained flexible polyurethane foam molded article were evaluated. The results are also shown in Table 1. 1 and 2 plot the wet heat compression residual strain ratio and the resonance frequency against the d value based on the evaluation results.

EO mass%
Content (% by mass) of molecular chain units derived from ethylene oxide (EO) in the polyol

Amine catalyst Dabco33LV (manufactured by Sankyo Air Products)
Silicone foam stabilizer SRX274C (manufactured by Toray Dow Corning Silicone Co., Ltd.)
Organic mica Somashif MEE (Co-op Chemical Co., Ltd.)
Isocyanate 1
T-80 (Mitsui Takeda Chemical Co., Ltd.)
Isocyanate 2
44V20 (manufactured by Sumitomo Bayer Urethane Co., Ltd.)

d value (Å)
A mixture (including 5% by mass of organic mica) of polyol (component (A)) and organic mica (component (B)) was used as a measurement target. A long period interval (d value) was measured by a wide angle X-ray diffraction method using RINT2200V manufactured by Rigaku Denki Co., Ltd., with the tube being Cu, the acceleration condition being 40 kV × 50 mA, and the scanning speed being 4 ° / min.
Humid heat compression residual strain (%)
The wet heat compression residual strain was measured by the compression residual strain measurement method described in JIS K 6400. However, in the measurement, the core part of the molded flexible foam was cut out by 50 × 50 × 25 mm and used as a test piece. The test piece was compressed to a thickness of 50%, sandwiched between parallel flat plates, and left under conditions of 50 ° C. and relative humidity of 95% for 22 hours. And after leaving for 22 hours, this test piece was taken out, 30 minutes later, its thickness was measured, compared with the value of the thickness before the test, the strain rate was measured, and this strain rate was defined as the wet heat compression residual strain.
Comparative example corresponding to wet heat compression residual strain ratio (Comparative example using the same component (A) (polyol). For example, Comparative Example 1 for Example 1, Comparative Example 2 for Example 2, etc. The index when the wet heat compression residual strain value of 1 is 1 was calculated.
Resonance characteristics (resonance frequency (Hz), resonance magnification)
Measured according to JASO B 407. A 41 kg pressure plate was placed on the sample, and the frequency was vibrated to 1 Hz to 10 Hz. The frequency when the maximum transmission rate was shown was the resonance frequency (Hz), and the transmission rate at the resonance frequency was the resonance magnification.

It is the graph which plotted the wet heat compression residual distortion ratio with respect to d value. It is the graph which plotted the resonant frequency with respect to d value.

Claims (6)

Next (A) component and (B) component,
(A) a polyol supplying a hydroxyl group,
(B) Organosilicates,
A long cycle interval (d value) measured when the combination of the component (A) and the component (B) is a mixture of only the component (A) and the component (B). A polyol composition characterized by being a combination of at least 35%.   2. The polyol composition according to claim 1, wherein the component (A) is one or more selected from the group consisting of polyether polyol, polyester polyol, and polymer polyol.   The polyol composition according to claim 1, wherein the component (B) is blended in an amount of 0.1 to 30 parts by mass with respect to 100 parts by mass of the component (A). The following components (A) to (C);
(A) a polyol supplying a hydroxyl group,
(B) Organosilicates,
(C) a polyisocyanate supplying an isocyanate group,
A foamed polyurethane foam formed by foaming a polyurethane foam stock solution in a mold, wherein the combination of the component (A) and the component (B) is a component (A) and a component (B). A soft polyurethane foamed molded article, which is a combination having a long-period interval (d value) of 35 mm or more measured when only these are mixed.   The flexible polyurethane foam molded article according to claim 4, wherein the component (A) is one or more selected from the group consisting of polyether polyol, polyester polyol, and polymer polyol. The flexible polyurethane foam molded article according to claim 4 or 5, wherein the component (B) is blended in an amount of 0.1 to 30 parts by mass with respect to 100 parts by mass of the component (A).