Patent Application
20240199789
The present disclosure relates to a polyurethane foam and a cushioning material.
This application is based on and claims the benefit of priority of Japanese Patent Application No. 2021-085926 filed on May 21, 2021, the entire contents of which are incorporated herein by reference.
Patent Literature 1 discloses a cushioning material for a battery. The cushioning material for a battery has a foam obtained by foaming a foamable resin sheet containing an elastomer component and a foaming agent.
Patent Literature 2 also discloses a cushioning material for a battery.
In recent years, polyurethane foams have been required to have various performances, and their requirements have also become severe. For example, a polyurethane foam used as a cushioning material is assumed to be used in a wide temperature range depending on its use. There is a demand for a polyurethane foam in which cushioning properties are not easily impaired in a wide temperature range, particularly at a low temperature.
An object of the present disclosure is to provide a polyurethane foam in which cushioning properties are not easily impaired at a low temperature.
The present disclosure can be implemented in the following forms.
According to the present disclosure, it is possible to provide a polyurethane foam in which cushioning properties are not easily impaired at a low temperature.
Desirable examples of the present disclosure will now be described.
Hereinafter, the present disclosure will be described in detail. In the present specification, unless otherwise specified, the numerical value range expressed by “(value) to (value)” includes the lower limit and the upper limit of the range. For example, the expression “10 to 20” includes both a lower limit of “10” and an upper limit of “20”. That is, “10 to 20” is equivalent to “10 or more and 20 or less”.
The polyurethane foam is obtained from a composition containing a polyol and a polyisocyanate. In the polyurethane foam, when a 25% compression load measured under a condition of 25° C. is P1 (MPa) and a 25% compression load measured under a condition of −30° C. is P2 (MPa),
The polyol is not particularly limited as long as it satisfies the above conditions. As the polyol, a polyether polyol, a polymer polyol, and a polyester polyol are preferably used in combination.
The polyether polyol is preferably a polyether polyol having a weight average molecular weight of 1500 to 4500 (preferably 2000 to 4000) and three or two functional groups.
The content of the polyether polyol is not particularly limited. The content of the polyether polyol is preferably 30 parts by mass or more and 90 parts by mass or less, and more preferably 40 parts by mass or more and 85 parts by mass or less when the total amount of the polyols is 100 parts by mass.
The polymer polyol is more preferably a polymer polyol having a weight average molecular weight of 1500 to 4500 (preferably 2000 to 4000) and two or three functional groups. As the polymer polyol, for example, a polymer polyol obtained by graft copolymerization of a vinyl monomer such as acrylonitrile and styrene in a polyether polyol having two or three functional groups as a base polyol can be suitably used. The weight average molecular weight of the polymer polyol means the weight average molecular weight of the base polyol.
The polymer content of the polymer polyol (mass ratio of a portion other than the base polyol to the entire polymer polyol) is preferably 10 to 40% by mass, and more preferably 15 to 30% by mass. From the viewpoint of improving strength of the polyurethane foam, the larger polymer content is more preferable; however, when the polymer content is too large, a viscosity may be increased and workability may be deteriorated. As the polymer polyol, only one polymer polyol may be contained, or two or more polymer polyols different in the weight average molecular weight, the polymer content, the number of functional groups, and the like may be used in combination. By using the polymer polyol, hardness of the polyurethane foam can be improved.
The content of the polymer polyol is not particularly limited. The content of the polymer polyol is preferably 5 parts by mass or more and 60 parts by mass or less, and more preferably 25 parts by mass or more and 45 parts by mass or less when the total amount of the polyols is 100 parts by mass.
The polyester polyol is more preferably a polyester polyol having two functional groups. The weight average molecular weight of the polyester polyol is preferably in a range of 200 to 2500, preferably in a range of 250 to 1500, and more preferably in a range of 300 to 800. As the polyester polyol, for example, a polycaprolactone-based polyester polyol, an adipate-based polyester polyol, or the like can be used. Examples of the polycaprolactone-based polyester polyol include polyester polyols obtained by ring-opening addition polymerization of lactones such as ε-caprolactone. Examples of the adipate-based polyester polyol include a polyester polyol obtained by polycondensation of a polyfunctional carboxylic acid and a polyfunctional hydroxy compound. By using the polyester polyol, the strength of the polyurethane foam can be improved. The polyester polyol also has an action of making cells of the polyurethane foam finer and more uniform.
The content of the polyester polyol is not particularly limited. The content of the polyester polyol is preferably 1 part by mass or more and 20 parts by mass or less, and more preferably 5 parts by mass or more and 15 parts by mass or less when the total amount of the polyols is 100 parts by mass.
As the polyol, a polyol other than the above-mentioned polyol may be contained. Another polyol is not particularly limited as long as it is a polyol generally used for the polyurethane foam.
In the present disclosure, when a low molecular weight polyhydric alcohol such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, glycerin, trimethylolpropane, pentaerythritol, or sorbitol is used, these polyhydric alcohols are also included in the polyol.
The polyisocyanate is a compound having a plurality of isocyanate groups, and for example: an aromatic isocyanate such as 4,4-diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), 1,5-naphthalene diisocyanate (NDI), triphenylmethane triisocyanate, and xylylene diisocyanate (XDI); an alicyclic isocyanate such as isophorone diisocyanate (IPDI) and dicyclohexylmethane diisocyanate; an aliphatic isocyanate such as hexamethylene diisocyanate (HDI); or a modified isocyanate such as free isocyanate prepolymers and carbodiimide-modified isocyanates obtained by reaction of these polyisocyanates with a polyol can be used. These polyisocyanates may be contained alone, or may be contained in combination of two or more thereof.
The polyisocyanate may be any of an aromatic isocyanate, an alicyclic isocyanate, and an aliphatic isocyanate, and may be a bifunctional isocyanate having two isocyanate groups in one molecule, or tri- or higher isocyanates having three or more isocyanate groups in one molecule, and these isocyanates may be used alone or in combination of two or more of them.
Examples of the bifunctional isocyanate include: an aromatic isocyanate such as 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate (TDI), m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 2,4′-diphenylmethane diisocyanate (MDI), 2,2′-diphenylmethane diisocyanate (MDI), xylylene diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, and 3,3′-dimethoxy-4,4′-biphenylene diisocyanate; an alicyclic isocyanate such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, and methylcyclohexane diisocyanate; and an aliphatic isocyanate such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, and lysine isocyanate. Examples of the di- or higher functional isocyanate include polymethylene polyphenyl isocyanate (polymeric MDI). Examples of the tri- or higher functional isocyanate include 1-methylbenzol-2,4,6-triisocyanate, 1,3,5-trimethylbenzol-2,4,6-triisocyanate, biphenyl-2,4,4′-triisocyanate, diphenylmethane-2,4,4′-triisocyanate, methyldiphenylmethane-4,6,4′-triisocyanate, 4,4′-dimethyldiphenylmethane-2,2′,5,5′ tetraisocyanate, and triphenylmethane-4,4′,4″-triisocyanate. Each of the isocyanates is not limited to one type, and may be one or more types. For example, one aliphatic isocyanate and two aromatic isocyanates may be used in combination.
The number of functional groups of the polyisocyanate is preferably in a range of 2.0 to 2.8 from the viewpoint of hardness and repulsion.
An isocyanate index (INDEX) of the polyisocyanate is preferably in a range of 90 to 110. The isocyanate index is an equivalence ratio of isocyanate groups of a polyisocyanate with respect to reactive groups such as hydroxyl groups capable of reacting with an isocyanate in a polyol. Therefore, when the value is less than 100, it means that the reactive group such as a hydroxyl group is more excessive than the isocyanate group, and when the value is more than 100, it means that the isocyanate group is more excessive than the reactive group such as a hydroxyl group. When the isocyanate index is less than 90, the polyol may not sufficiently react with the polyisocyanate. On the other hand, when the isocyanate index is more than 110, there is a possibility that low repulsion is caused.
A foam stabilizer is used for smoothly foaming a composition, and the composition preferably contains the foam stabilizer. As the foam stabilizer, a known foam stabilizer usually used when a mechanical froth method is employed, for example, a silicone-based foam stabilizer, can be used. Since such a foam stabilizer has a high viscosity, the foam stabilizer is usually blended in the composition in a diluted state with a solvent such as alkylbenzene.
The content of the foam stabilizer in the composition is preferably 3 parts by mass to 6 parts by mass with respect to 100 parts by mass of the polyols. When the content is 3 parts by mass or more, this can contribute to improvement of cell uniformity and reduction of the density of the polyurethane foam. Even when the foam stabilizer is contained in an amount of more than 6 parts by mass, remarkable improvement of a foam stabilizing force cannot be expected. When the foam stabilizer is diluted with a solvent, the mass ratio (foam stabilizer:solvent) is preferably in a range of 25:75 to 75:25.
A catalyst is used mainly for promoting an urethanization reaction between a polyol and a polyisocyanate, and the composition preferably contains the catalyst. As the catalyst, a known catalyst usually used for a polyurethane foam can be used, for example, a tertiary amine such as triethylenediamine, dimethylethanolamine, or N,N′,N′-trimethylaminoethylpiperazine; an organometallic compound such as stannous octoate or tin octylate (tin octoate); an acetate; or an alkali metal alcoholate.
The content of the catalyst in the composition is preferably 0.1 parts by mass to 5.0 parts by mass with respect to 100 parts by mass of the polyols. When the content is 0.1 parts by mass or more, the urethanization reaction can be sufficiently promoted. When the content is 5.0 parts by mass or less, it is possible to prevent formation of a cell structure from being non-uniform due to excessive promotion of the urethanization reaction.
The composition may contain other components other than the above components as necessary. Examples of other components include an antioxidant, an ultraviolet absorber, a thickener, a plasticizer, an antibacterial agent, and a colorant. Examples of the antioxidant include dibutylhydroxytoluene and a hindered phenol-based antioxidant, and from the viewpoint of reducing a content of a volatile organic compound, it is particularly preferable to use a hindered phenol-based antioxidant having a molecular weight of 300 or more. Examples of the thickener include calcium carbonate, aluminum hydroxide, and magnesium hydroxide.
A polyurethane foam preferably satisfies 1000≤A for A obtained by the above formula (a). The polyurethane foam more preferably satisfies 1100≤A, and still more preferably satisfies 1150≤A. The upper limit value of A is not particularly limited. The polyurethane foam may satisfy, for example, A≤2300 for A obtained by the above formula (a).
A obtained by the formula (a) represents a weight average molecular weight per hydroxyl group in a polyol. When one polyol is included in the polyol, A can be obtained by dividing the weight average molecular weight of the polyol by the number of hydroxyl groups per molecule of the polyol. When a plurality of types of polyols are included in the polyol, A can be obtained by multiplying a value, obtained by dividing the weight average molecular weight of each polyol by the number of hydroxyl groups per molecule of each polyol, by a content rate (% by mass) of each polyol and summing these values.
For example, in Example 2 (n=12) described later, A is obtained as 1194 from the following formula (a-1):
The polyurethane foam more preferably satisfies 2400≤A×B for A obtained by the above formula (a) and B obtained by the following formula (b).
B obtained by the formula (b) represents an average number of functional groups of the polyisocyanate. When one polyisocyanate is contained in the polyisocyanate, B can be obtained as the number of functional groups thereof. When a plurality of types of polyisocyanates are contained in the polyisocyanate, B can be obtained by multiplying the number of functional groups of each polyisocyanate by the content (% by mass) of each polyisocyanate and summing these values.
For example, in Example 2 (m=2) described later, B is obtained as 2.4 from the following formula (b-1):
A and B are multiplied to obtain the weight average molecular weight of the polyol per isocyanate molecule. The fact that A×B is a predetermined value or more is an indicator that the weight average molecular weight of the polyol per isocyanate molecule is a predetermined value or more. When the weight average molecular weight of the polyol per isocyanate molecule is the predetermined value or more, cushioning properties at a low temperature can be suitably maintained. For example, in Example 2 described later, the value of A×B is obtained as 2866 from an expression of 1194×2.4.
The value of A×B may be 2500 or more, 2600 or more, or 2700 or more. The value of A×B is usually 5000 or less, and may be 4500 or less, 4000 or less, or 3500 or less.
In the polyurethane foam, when a 25% compression load measured under a condition of 25° C. is P1 (MPa) and a 25% compression load measured under a condition of −30° C. is P2 (MPa),
is satisfied.
The compression load under each temperature condition can be measured as follows based on JIS K 6254: 2010.
A test piece has a cylindrical shape with a diameter of 50 mm. The number of test pieces is three. For the measurement, a compression testing machine is used in which a mounted CLD (Compression-Load-Deflection) measuring jig comes into contact with a test piece, and at the same time, a load cell senses a repulsive force from the test piece compressed, and the repulsive force is continuously recorded.
The test piece is compressed at a rate of 1.0 mm/min until it reaches a deflection of 30%, and a relationship between a compressive force and deflection (compressive force-deformation curve) is recorded. From the recorded compressive force-deformation curve, the compressive force (25% compressive force) when the deflection is 25% with respect to the thickness of the test piece before compression is obtained. The 25% compression load is calculated by the following formula:
25% compression load [MPa]=25% compressive force [N]/area of test piece [mm2]
The value of P2/P1 is an indicator representing a rate of increase in hardness of the polyurethane foam when the temperature is changed from room temperature to −30° C. The fact that the value of P2/P1 is 100 means that the 25% compression load is the same at 25° C. (room temperature) and −30° C., that is, the hardness does not increase at low temperatures.
The value of P2/P1 may be 160 or less, 140 or less, 120 or less, or 110 or less. The value of P2/P1 is usually 95 or more, and may be 98 or more or 100 or more.
The 25% compression load P1 measured under the condition of 25° C. is preferably 0.005 MPa or more and 1 MPa or less, more preferably 0.01 MPa or more and 0.75 MPa or less, and still more preferably 0.1 MPa or more and 0.5 MPa or less.
The 25% compression load P2 measured under the condition of −30° C. is preferably 0.005 MPa or more and 1 MPa or less, more preferably 0.01 MPa or more and 0.75 MPa or less, and still more preferably 0.1 MPa or more and 0.5 MPa or less.
In addition to the above, the physical properties of the polyurethane foam can be appropriately set according to the application and the like. The polyurethane foam preferably has the following physical properties.
The glass transition point of the polyurethane foam is preferably −25° C. or lower, preferably −30° C. or lower, and more preferably −35° C. or lower. The lower limit of the glass transition point of the polyurethane foam is not particularly limited, and but usually −100° C. or higher.
In the present disclosure, the glass transition point is defined as a temperature at which a peak value of tan δ obtained when viscoelasticity is measured under conditions of a frequency of 1 Hz and a temperature rise rate of 3° C./min is obtained.
The hysteresis loss rate of the polyurethane foam is preferably 15% or less, more preferably 10% or less, and still more preferably 8% or less when measured by the following measurement method. The lower limit of the hysteresis loss rate is not particularly limited, but is usually 1% or more.
The hysteresis loss rate under can be measured as follows based on JIS K 6254: 2010.
A test piece has a cylindrical shape with a diameter of 50 mm. The number of test pieces is three. For the measurement, a compression testing machine is used in which a mounted CLD measuring jig comes into contact with a test piece, and at the same time, a load cell senses a repulsive force from the test piece compressed, and the repulsive force is continuously recorded.
The test piece is compressed at a rate of 1.0 mm/min until the test piece reaches a strain of 50%, and then the jig is returned at the same rate of 1.0 mm/min until the test piece returns to a strain of 0%. A relationship between the compressive force and the deflection (compressive force-deformation curve) is recorded. In the recorded compressive force-deformation curve, the hysteresis loss rate is obtained by the same calculation method as JIS K 6400-2.
An apparent density (JIS K 7222) of the polyurethane foam is preferably 100 kg/m3 to 900 kg/m3, more preferably 200 kg/m3 to 800 kg/m3, and still more preferably 300 kg/m3 to 700 kg/m3. When the apparent density is within the above range, suitable cushioning properties can be secured when the polyurethane foam is used as a cushioning material 10 described later.
An average cell diameter of the polyurethane foam is preferably 50 μm to 300 μm, more preferably 50 μm to 200 μm, and still more preferably 50 μm to 100 μm. When the cell diameter is within the above range, suitable cushioning properties can be secured, and it is also preferable from the viewpoint of heat insulating property.
The average cell diameter of the polyurethane foam can be calculated by dividing, by the number of cells, cumulative total of cell diameters of cells in contact with a straight line of 25 mm when a section of the polyurethane foam is observed with a scanning electron microscope (SEM) at a magnification of 200 times.
The polyurethane foam can be produced by a general method of producing a polyurethane foam used when a mechanical froth method is employed. For example, after the composition is charged into a mixing head, the composition is stirred and mixed so as to be homogeneous while being mixed with an inert gas. Subsequently, the composition mixed in the mixing head is heated and cured on a release paper or the like or in a predetermined molding die, whereby a polyurethane foam can be obtained. In order to form a desired density of foam, an amount of inert gas stirred into the composition is controlled with a gas flow meter. Increasing the amount of inert gas forming a cell decreases the density, and decreasing the amount of inert gas increases the density. As the inert gas, a gas that is a gas at ambient conditions and is substantially inert or does not react at all to any component of a liquid phase can be used, if necessary. Examples thereof include nitrogen, carbon dioxide, and dry air which is dry and usually a gas.
The polyurethane foam is suitable as a cushioning material because it has moderate flexibility and a low hysteresis loss rate. The polyurethane foam is particularly suitable as a cushioning material used for an in-vehicle component, for example, a cushioning material for a battery such as a lithium ion battery because the cushioning properties are not easily impaired at a low temperature. In addition, since the polyurethane foam has a small change in characteristics such as hardness in a wide temperature range from a low temperature to a high temperature and achieves high responsiveness, the polyurethane foam is also suitable as a cushioning material used for electronic devices and sensor sections. The high responsiveness can be realized, for example, by reducing the hysteresis loss rate.
The thickness of the cushioning material 10 is not particularly limited. The thickness of the cushioning material 10 is preferably 0.5 mm to 6 mm, more preferably 1 mm to 5 mm, and still more preferably 2 mm to 3 mm from the viewpoint of followability to the cells C, C. From the viewpoint of controlling a surface pressure of the block-shaped cells C, C, the size of the cushioning material 10 is preferably substantially the same as or slightly smaller than opposing surfaces of the adjacent cells C, C.
From the viewpoint of moldability, the cushioning material 10 can be obtained by punching a polyurethane foam molded into a sheet shape in the thickness direction.
The polyurethane foam is not limited to a cushioning material, and can be used in various applications. Examples of such a member include electronic equipment components such as mobile phones, cameras, and televisions, in-vehicle components such as batteries, vehicle lighting devices, and vehicle display devices, and sealing materials for water stop and dust prevention in toner cartridges and the like.
In recent years, polyurethane foams have been required to have various performances, and their requirements have also become severe. For example, the cushioning material 10 for a battery is required to be capable of following expansion and contraction of a cell in a wide temperature range from a low temperature to a high temperature. In particular, a polyurethane foam capable of maintaining the cushioning properties (followability) at a low temperature is required.
In the polyurethane foam of the present embodiment, the cushioning properties are not easily impaired at a low temperature. Unlike the present embodiment, a cushioning material using a conventional polyurethane foam has a high glass transition point, and thus the cushioning properties in a low temperature environment cannot be secured. In contrast, the cushioning material 10 using the polyurethane foam of the present embodiment has a small increase in hardness even in a low temperature environment. Therefore, the cushioning material 10 can secure the cushioning properties in a low temperature environment.
The polyurethane foam of the present embodiment has a low hysteresis loss rate. Therefore, it is possible to sufficiently follow displacement of surrounding members such as the cell C and to exhibit suitable cushioning properties.
Next, the above embodiment will be described more specifically with reference to Examples and Comparative Examples.
First, raw material components of the composition used in the polyurethane foam of each Example and each Comparative Example are shown below.
The numerical values of the components in Tables 1 and 2 represent parts by mass. The column “F” in Tables 1 and 2 indicates the number of hydroxyl groups in the polyols, and the number of isocyanate groups in the polyisocyanates. The column of “Mw” in Tables 1 and 2 indicates the weight average molecular weight.
The components were prepared in blending ratios shown in Tables 1 and 2 below to obtain compositions of Examples and Comparative Examples. Next, the composition was charged into a mixing head, and mixed by stirring so as to be homogeneous while an inert gas (nitrogen) was mixed in a range of 69 to 77% by volume. Thereafter, the mixed composition was supplied onto a continuously supplied film having a predetermined thickness, and was heated and cured at 120 to 200° C. to obtain a sheet-shaped polyurethane foam.
The cross sections of the sheets of Examples and Comparative Examples were observed using SEM. The average cell diameter of the polyurethane foams of Examples was 50 μm or more and 300 μm or less.
Next, the obtained polyurethane foams of Examples and Comparative Examples were evaluated as follows.
In the present example, ten types of polyols are used, and “n=12” in the above formula (a) including two types used only in Comparative Example. A was calculated based on the above formula (a). The results are shown in the column of “Average molecular weight per hydroxyl group in polyol: A” in Table 2.
In the present example, two types of polyisocyanates are used, and “m=2” in the formula (b). B was calculated based on the above formula (b). In Comparative Example 1, B is 2. In Comparative Examples 2 to 4 and Examples, B is 2.4. A value of A×B was calculated by multiplying A and B. The results are shown in the column of “Average molecular weight per isocyanate molecule” in Table 2.
The glass transition point (° C.) was measured by the method described in the embodiment. The measurement results are shown in the column of “Glass transition point” in Table 2.
The apparent density (kg/m3) was measured according to JIS K 7222. The measurement results are shown in the column of “Density” in Table 2.
Assuming that the specific gravity of the composition was 1, an amount (% by volume) of the inert gas when a total of the volume of the composition and the volume of the mixed inert gas was 100% by volume was calculated. For example, in Example 5, an amount of the inert gas mixed in the composition of 35% by volume means that 35 mL of the inert gas is mixed in 65 g of the composition prepared at the blending ratio shown in Table 1. The calculation results are shown in the column of “Amount of inert gas mixed in composition” in Table 2.
The 25% compression load (MPa) at 25° C. was measured by the method described in the embodiment. The measurement results are shown in the column of “25% compression load at 25° C.” in Table 2.
The 25% compression load (MPa) at −30° C. was measured by the method described in the embodiment. The measurement results are shown in the column of “25% compression load at −30° C.” in Table 2.
Based on the 25% compression load P1 at 25° C. and the 25% compression load P2 at −30° C., the rate of increase in hardness P2/P1×100(%) was calculated. The results are shown in the column of “Rate of increase in hardness” in Table 2, and the measurement results were evaluated according to the following criteria.
The hysteresis loss rate (%) was measured by the method described in the embodiment. The measurement results are shown in the column of “Hysteresis loss rate” in Table 2, and the measurement results were evaluated according to the following criteria.
In Examples 1 to 4, the evaluation of the rate of increase in hardness is A, and P2/P1×100≤180 is satisfied. In Comparative Examples 1 to 4, the evaluation of the rate of increase in hardness is B or C, and P2/P1×100≤180 is not satisfied. Examples 1 to 4 received a higher overall evaluation than Comparative Examples 1 to 4. In Examples 1 to 4, the cushioning properties were not easily impaired at a low temperature.
In Examples 1 to 4, the hysteresis loss rate was evaluated as A, and the cushioning properties (followability) were good as compared with Comparative Examples 1, 2, and 4.
The following invention can also be grasped from the above Examples and Comparative Examples. The above description is appropriately incorporated for the description of specific matters of the following invention.
For A obtained by the above formula (a) and B obtained by the above formula (b), 2400≤A×B is satisfied.
According to the above Examples, it is possible to provide a polyurethane foam in which the cushioning properties are not easily impaired at a low temperature.
The present disclosure is not limited to the embodiment described in detail above, and can be modified or changed in various manners within the scope of the claims of the present disclosure.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2021-085926 | May 2021 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2022/015061 | 3/28/2022 | WO |
