WO2023238931A1

WO2023238931A1 - Filled structure, polyurethane foam-forming composition for filled structure, polyurethane foam for filled structure, and method for producing filled structure

Info

Publication number: WO2023238931A1
Application number: PCT/JP2023/021541
Authority: WO
Inventors: 邦生平田; 哲平小柳
Original assignee: 東ソー株式会社
Priority date: 2022-06-10
Filing date: 2023-06-09
Publication date: 2023-12-14

Abstract

Provided is a filled structure comprising an external wall and a polyurethane foam that is filled into the external wall. The polyurethane foam is a cured foam of a mixture of a polyol (A), a catalyst (B), a foam stabilizer (C), a foaming agent (D) and a polyisocyanate (E). The foaming pressure of the polyurethane foam is 30 kPa or more.

Description

Filled structure, polyurethane foam-forming composition for filled structure, polyurethane foam for filled structure, and method for producing filled structure

The present disclosure relates to a filled structure, a polyurethane foam-forming composition for a filled structure, a polyurethane foam for a filled structure, and a method for manufacturing a filled structure.

Structures such as high-rise buildings and low-rise buildings with large areas have a problem in that the cost of structural materials increases because of the large loads that are applied to them.

Here, Patent Document 1 is a structure consisting of a rigid structure having rigidity and a pressure structure that seals gas, and the rigid structure is characterized by being a truss structure, a rigid frame structure, a monocoque structure, or a shell structure, The pressure structure has a bag-like pressure structure with upper and lower surfaces of arbitrary shapes such as circles or rectangles, and if the rigid structure is a truss structure or a rigid frame structure, the pressure structure is a pressure membrane structure, and the rigid structure is a truss structure or a rigid frame structure. When the structure is a monocoque structure or a shell structure, the pressure structure is formed of a pressure membrane structure or/a part of a pressure partition structure, and the pressure structure is arranged in the internal space of the rigid structure, and the pressure structure is arranged in the internal space of the rigid structure to control the internal pressure of the pressure structure. A means for suppressing expansion of the upper and lower surfaces of the pressure structure, having a feature of being able to maintain the internal pressure of the pressure structure higher than the surrounding external pressure, and having a pressure control device for maintaining the internal pressure of the pressure structure higher than the surrounding external pressure. Discloses a pressure membrane composite structure, characterized in that the force generated by the differential pressure between the internal pressure of the pressure structure and the external pressure is transmitted to the rigid structure by means for suppressing expansion of the upper and lower surfaces of the pressure structure. There is. According to Patent Document 1, this pressure membrane composite structure can withstand larger loads with less structural material.

JP2013-23898A

However, the structure described in Patent Document 1 requires control by a pressure control device in order to increase the internal pressure, resulting in the hassle of maintaining and managing the internal pressure.

Therefore, one aspect of the present disclosure is to provide a polyurethane foam-forming composition for a filling structure and a polyurethane foam for a filling structure that contribute to the production of a filling structure having a high internal pressure, and a filling structure comprising the polyurethane foam. The present invention is directed to providing a structure and a method for manufacturing the same.

Each aspect of the present disclosure provides the following [1] to [20].
[1] Exterior wall and
a polyurethane foam filled inside the outer wall;
A filling structure comprising:
The polyurethane foam is a foamed and cured product of a mixture of polyol (A), catalyst (B), foam stabilizer (C), blowing agent (D) and polyisocyanate (E),
A filling structure in which the foaming pressure of the polyurethane foam is 30 kPa or more.
[2] The polyurethane foam has a resin part and a cell part,
The filling structure according to [1], wherein the total content of urethane groups and urea groups in the resin part is 3.85 mmol/g or less.
[3] The polyurethane foam has a resin part and a cell part,
The filled structure according to [1] or [2], wherein the total hydroxyl value of the components forming the resin part in the mixture is 220 mgKOH/g or less.
[4] The content of the blowing agent (D) in the mixture is 55 to 150 μmol/cm ³ with respect to the internal volume of the outer wall filled with the polyurethane foam, [1] to [3]. Filling structure according to any one of the items.
[5] The filled structure according to any one of [1] to [4], wherein the polyurethane foam has a molding density of 100 kg/m ³ or less.
[6] The filling structure according to any one of [1] to [5], wherein the polyol (A) contains a polyether polyol.
[7] The filling structure according to any one of [1] to [6], wherein the polyisocyanate (E) contains polyphenylene polymethylene polyisocyanate.
[8] The filling structure according to any one of [1] to [7], wherein the polyurethane foam is a flexible polyurethane foam.
[9] The filling structure according to any one of [1] to [8], wherein the polyurethane foam is sealed by the outer wall.
[10] The filling structure according to any one of [1] to [9], wherein the outer wall is selected from the group consisting of a metal wall and a reinforced concrete wall.
[11] A composition for forming the polyurethane foam in a filling structure filled with a polyurethane foam having a resin part and a cell part,
A polyol composition containing a polyol (A), a catalyst (B), a foam stabilizer (C) and a blowing agent (D), and a polyisocyanate composition containing a polyisocyanate (E),
The total hydroxyl value of the components that can form the resin part is 220 mgKOH/g or less,
A polyurethane foam-forming composition for a filled structure, wherein at least one of the seven foaming pressures measured according to the test conditions described in (1') to (5') below is 30 kPa or more.
<Test conditions>
(1') Among the polyurethane foam-forming compositions for filling structures, a sample in which the polyisocyanate composition was adjusted to 25°C ± 1°C, and a sample in which the polyol composition was adjusted to 25°C ± 1°C. A two-liquid sample consisting of .
(2') Next, the two liquid samples are mixed using a mixer at 7000 rpm for 7 seconds.
(3') The obtained mixed solution was placed in a mold with inner dimensions of 120 mm x 150 mm x 70 mm and equipped with a pressure sensor inside the upper surface, and the concentration of the blowing agent (D) was determined to be X [μmol/cm ³ ] and the injection density. Inject so that Y [kg/m ³ ] satisfies any of the seven patterns shown below (X1, Y1) to (X7, Y7).
(4') After the polyurethane foam is sufficiently foamed, the foaming pressure is measured using a pressure sensor.
(5') Repeat steps (1') to (4') to measure the foaming pressure in all seven patterns shown below (X1, Y1) to (X7, Y7).

[12] The polyurethane foam-forming composition for a filled structure according to [11], wherein the content of the blowing agent (D) is 0.2 mmol/g to 3.0 mmol/g.
[13] The polyurethane foam-forming composition for a filled structure according to [11] or [12], which has a free foam density of 25 to 45 kg/m ³ as measured based on JIS K 7222.
[14] The polyurethane foam-forming composition for a filled structure according to any one of [11] to [13], wherein the polyol (A) contains a polyether polyol.
[15] The polyurethane foam-forming composition for a filled structure according to any one of [11] to [14], wherein the polyisocyanate (E) contains polyphenylene polymethylene polyisocyanate.
[16] The polyurethane foam-forming composition for a filled structure according to any one of [11] to [15], which is for use in flexible polyurethane foam.
[17] A composition for forming the polyurethane foam in a filling structure comprising an outer wall and a polyurethane foam filled inside the outer wall,
A polyol composition containing a polyol (A), a catalyst (B), a foam stabilizer (C) and a blowing agent (D), and a polyisocyanate composition containing a polyisocyanate (E),
A polyurethane foam-forming composition for a filling structure, wherein the polyurethane foam has a foaming pressure of 30 kPa or more.
[18] A polyurethane foam for filled structures, comprising a foamed cured product of the polyurethane foam-forming composition for filled structures according to any one of [11] to [17].
[19] A method for manufacturing a filling structure according to any one of [1] to [10], comprising:
A method of manufacturing a filling structure, comprising foaming and curing the mixture inside the outer wall to form the polyurethane foam inside the outer wall.
[20] The polyurethane foam-forming composition for a filling structure according to any one of [11] to [17] is foamed and cured inside the outer wall to provide a foaming pressure of 30 kPa or more inside the outer wall. A method of manufacturing a filled structure, the method comprising forming a polyurethane foam having a polyurethane foam.

Further, each aspect of the present disclosure provides the following [1'] to [12'].
[1'] Exterior wall and
A filling structure comprising a polyurethane foam filled inside the outer wall,
The polyurethane foam includes a foam of a polyurethane foam-forming composition for filling structures;
The polyurethane foam-forming composition for filled structures comprises:
A polyol composition containing a polyol (A), a catalyst (B), a foam stabilizer (C), and a blowing agent (D);
A polyisocyanate composition containing polyisocyanate (E),
The foaming agent (D) contains water (d1) and a physical foaming agent (d2) as an optional component,
The total amount of hydroxyl groups contained in components other than the physical foaming agent (d2) in the polyol composition relative to the total mass of components other than the physical foaming agent (d2) in the polyol composition is 500 mgKOH/g or less and
The molding density of the polyurethane foam is 40 to 100 kg/m ³ ,
A filling structure in which the foaming pressure of the polyurethane foam is 30 kPa or more.
[2'] The filling structure according to [1'] above, wherein the polyol (A) contains a polyether polyol.
[3'] The filling structure according to [1'] or [2'] above, wherein the polyisocyanate (E) contains polyphenylene polymethylene polyisocyanate.
[4'] The filling structure according to any one of [1'] to [3'] above, wherein the polyurethane foam is a flexible polyurethane foam.
[5'] The filling structure according to any one of [1'] to [4'] above, wherein the polyurethane foam is sealed by the outer wall.
[6'] The filling structure according to any one of [1'] to [5'] above, wherein the outer wall is made of one or more types selected from the group consisting of metal materials and reinforced concrete.
[7'] Polyol composition containing polyol (A), catalyst (B), foam stabilizer (C), and foaming agent (D),
A polyurethane foam-forming composition for a filled structure, comprising: a polyisocyanate composition containing polyisocyanate (E);
The foaming agent (D) contains water (d1) and a physical foaming agent (d2) as an optional component,
The total amount of hydroxyl groups contained in components other than the physical foaming agent (d2) in the polyol composition relative to the total mass of components other than the physical foaming agent (d2) in the polyol composition is 500 mgKOH/g or less and
A polyurethane foam-forming composition for filled structures, which has a foaming pressure of 30 kPa or more as measured according to the test conditions described in (1) to (4) below.
<Test conditions>
(1) Among the polyurethane foam-forming compositions for filling structures, a sample in which the polyisocyanate composition was adjusted to 25°C ± 1°C, and a sample in which the polyol composition was adjusted to 25°C ± 1°C; A two-liquid sample consisting of
(2) Next, the two liquid samples are mixed using a mixer at 7000 rpm for 7 seconds.
(3) The obtained mixed solution is placed in a mold with inner dimensions of 120 mm x 150 mm x 70 mm and a pressure sensor inside the upper surface, and the concentration of the blowing agent (D) is 55 to 150 μmol/cm ³ and the injection density is Inject so that the amount is 40 to 100 kg/ ^m3 .
(4) After the polyurethane foam is sufficiently foamed, the foaming pressure is measured using a pressure sensor.
[8'] The polyurethane foam-forming composition for a filled structure according to [7'] above, which has a free foam density of 25 to 45 kg/m ³ as measured based on JIS K7222.
[9'] The polyurethane foam-forming composition for a filled structure according to [7'] or [8'] above, wherein the polyol (A) contains a polyether polyol.
[10'] The polyurethane foam-forming composition for a filled structure according to any one of [7'] to [9'] above, wherein the polyisocyanate (E) contains polyphenylene polymethylene polyisocyanate.
[11'] The polyurethane foam-forming composition for a filled structure according to any one of [7'] to [10'] above, which is for use in flexible polyurethane foam.
[12'] A polyurethane foam for a filled structure, comprising a foam of the polyurethane foam-forming composition for a filled structure according to any one of [7'] to [11'] above.

According to one aspect of the present disclosure, there is provided a polyurethane foam-forming composition for a filling structure that contributes to the production of a filling structure having a high internal pressure, and a polyurethane foam for a filling structure, and a filling comprising the polyurethane foam. A structure and a method for manufacturing the same can be provided.

Hereinafter, preferred embodiments of each aspect of the present disclosure will be described. However, each aspect of the present disclosure is not limited to the following embodiments.

Note that in this specification, a numerical range indicated using "~" indicates a range that includes the numerical values written before and after "~" as the minimum value and maximum value, respectively. In the numerical ranges described stepwise in this specification, the upper limit or lower limit of the numerical range of one step may be replaced with the upper limit or lower limit of the numerical range of another step. Further, in the numerical ranges described in this specification, the upper limit or lower limit of the numerical range may be replaced with the value shown in the Examples. Moreover, the upper limit values and lower limit values described individually can be combined arbitrarily.

A filling structure according to one embodiment of the present disclosure includes an outer wall and a polyurethane foam filled inside the outer wall.

Polyurethane foam is a foamed and cured product of a mixture of polyol (A), catalyst (B), foam stabilizer (C), blowing agent (D) and polyisocyanate (E), and the foaming pressure of polyurethane foam is 30 kPa or more. It is.

The filling structure of this embodiment has a structure with excellent load resistance due to the internal pressure caused by the foaming pressure of the polyurethane foam, and can be suitably used in applications where large loads are applied, such as buildings.

The material constituting the outer wall is not particularly limited, and may be any known material that can be used as the outer wall of a structure. The material constituting the outer wall may be, for example, a metal material, reinforced concrete, or the like. That is, the outer wall may be, for example, a metal wall, a reinforced concrete wall, or the like.
Note that the outer wall is preferably placed at the outermost side of the structure. For example, in the case of a structure placed in the atmosphere, the surface in contact with the atmosphere may constitute a part of the outer wall.

Preferably, the polyurethane foam is sealed with an outer wall. That is, it is preferable that the polyurethane foam is filled inside the space defined by the outer wall. The shape of the space defined by the outer wall is not particularly limited, and may be, for example, a cube, rectangular parallelepiped, triangular prism, cylinder, triangular pyramid, square pyramid, cone, sphere, etc. Further, the shape of the outer wall is not particularly limited, and may be, for example, a cube, a rectangular parallelepiped, a triangular prism, a cylinder, a triangular pyramid, a square pyramid, a cone, a sphere, etc., and these are hollow.

In the filling structure, the entire space defined by the outer wall may be filled with polyurethane foam, or a portion thereof may be filled with polyurethane foam.

In the filling structure, the polyurethane foam may be arranged symmetrically with respect to a center line connecting the center point of the cross section horizontal to the gravity direction from the upper end to the lower end in the gravity direction. By arranging the polyurethane foam symmetrically with respect to the centerline, the strength is increased evenly over the entire area of the outer wall, which further improves the durability of the filling structure.
Here, the centerline is, for example, in the case of a cylindrical shape whose upper and lower ends in the vertical direction are circular, an imaginary straight line passing through the center of the cylinder. And, symmetrical with respect to the center line means that the urethane foam is uniformly arranged over the circumferential direction.

Polyurethane foam is a foamed and cured product of a mixture of polyol (A), catalyst (B), foam stabilizer (C), blowing agent (D), and polyisocyanate (E). The polyurethane foam can also be referred to as a foamed and cured product of the polyurethane foam-forming composition for filling structures described below.

The foaming pressure of the polyurethane foam is 30 kPa or more, and may be, for example, 30 to 300 kPa, 30 to 250 kPa, or 35 to 250 kPa.

The polyurethane foam may have a resin part and a cell part.

The resin part may contain polyurethane formed by the reaction of polyol (A) and polyisocyanate (E). The resin portion may also contain components other than polyurethane, such as a foam stabilizer (C), a plasticizer, a flame retardant, a catalyst (B), a filler, a colorant, and an antifungal agent.

The resin part contains a urethane group and a urea group. From the viewpoint that the foaming pressure of the polyurethane foam is likely to be 30 kPa or more, the total content of urethane groups and urea groups in the resin part is preferably 3.85 mmol/g or less, more preferably 3.83 mmol/g or less. Such a resin part has excellent flexibility and can easily transmit the pressure inside the bubbles to the outer wall, so that the above-mentioned effects are more pronounced.

The total content of urethane groups and urea groups in the resin part may be, for example, 1.00 mmol/g or more, and from the viewpoint of easily ensuring sufficient strength of the polyurethane foam, it is 2.00 mmol/g or more and 2.50 mmol. /g or more or 3.00 mmol/g or more.

The total content of urethane groups and urea groups in the resin part can be adjusted by the hydroxyl value of the components that can form the resin part in the mixture (polyurethane foam-forming composition for filled structures). Components that can form the resin part include, for example, polyol (A), catalyst (B), foam stabilizer (C), polyisocyanate (E), and blowing agent (D), which are incorporated into the resin part (for example, water), other resin components, etc.

From the above viewpoint, the total hydroxyl value of the components that can form the resin part in the mixture is preferably 220 mgKOH/g or less, and may be 210 mgKOH/g or less, 200 mgKOH/g or less, or 195 mgKOH/g or less. . Further, the total hydroxyl value of the components that can form the resin part in the mixture may be, for example, 50 mgKOH/g or more, 80 mgKOH/g or more, 100 mgKOH/g or more, or 120 mgKOH/g or more.

When the polyurethane foam-forming composition for filled structures contains water (d1) and an optional physical blowing agent (d2) as the blowing agent (D), the physical blowing agent (d2) in the polyol composition The total amount of hydroxyl groups contained in the components other than the physical blowing agent (d2) in the polyol composition relative to the total mass of the other components may be, for example, 500 mgKOH/g or less, and 100 to 490 mgKOH/g. It may be 200 to 490 mgKOH/g. Here, the components other than the physical blowing agent (d2) in the polyol composition are, for example, the polyol (A), the catalyst (B), the foam stabilizer (C), and the components other than the physical blowing agent (d2). It may contain the blowing agent (D) and any other components other than these.

It is desirable that the polyurethane foam has high intracellular pressure. That is, the amount of blowing agent (D) may be adjusted in the polyurethane foam in order to obtain high intracellular pressure. For example, the pressure inside the cells can be adjusted by adjusting the amount (μmol/cm ³ ) of the blowing agent (D) in the mixture relative to the internal volume of the outer wall filled with polyurethane foam.

From the above viewpoint, the amount of blowing agent (D) in the mixture relative to the internal volume of the outer wall filled with polyurethane foam is preferably 55 μmol/cm ³ or more, more preferably 75 μmol/cm ³ or more, and 90 μmol/cm ³ The above is more preferable. In addition, the amount of blowing agent (D) in the mixture relative to the internal volume of the outer wall filled with polyurethane foam is preferably 150 μmol/cm ³ or less, and 130 μmol/cm ³ from the viewpoint of easily obtaining a more suitable foaming pressure. The following is more preferable, and 120 μmol/cm ³ or less is even more preferable.

The molding density of the polyurethane foam (the ratio of the mass of the polyurethane foam to the volume of the space filled with the polyurethane foam) may be 100 kg/m ³ or less, and may be 80 kg/m from the viewpoint of making it easier to obtain a more suitable foaming pressure. ³ or less, or 75 kg/m ³ or less. In addition, the molding density of the polyurethane foam may be 10 kg/m 3 or more, 20 kg/m ³ or more, 40 kg/m ³ or more, 45 kg/m ³ or more, from the viewpoint of easily obtaining a foam of ^better quality. Or it may be 50 kg/m ³ or more.

It is preferable that the cells of the polyurethane foam include closed cells. That is, it is preferable that at least some of the cell portions of the polyurethane foam are closed cells. When the cell portion is a closed cell, it is difficult for the internal pressure to escape when the outer wall is damaged, and excellent load-bearing properties are easily maintained. Moreover, if the cell portion is a closed cell, even if the outer wall is damaged, rainwater etc. will be less likely to enter the inside of the foam, and the foam will be less likely to deteriorate.

The polyurethane foam is preferably a flexible polyurethane foam.

A polyurethane foam-forming composition for a filled structure according to one aspect of the present disclosure includes a polyol composition containing a polyol (A), a catalyst (B), a foam stabilizer (C), and a blowing agent (D); A polyisocyanate composition containing isocyanate (E).

The polyurethane foam-forming composition for filling structures is a composition capable of forming a polyurethane foam having a foaming pressure of 30 kPa or more inside the outer wall, that is, a polyurethane foam having a foaming pressure of 30 kPa or more is formed inside the outer wall. The composition may be prepared as follows. Furthermore, the polyurethane foam-forming composition for a filling structure is a composition capable of forming a polyurethane foam having the above-mentioned characteristics, that is, a composition prepared such that a polyurethane foam having the above-mentioned characteristics is formed. good.

The polyurethane foam-forming composition for filling structures is preferably a two-component type consisting of a first part consisting of a polyol composition and a second part consisting of a polyisocyanate composition.

Polyol (A) is polyadded with polyisocyanate (E) to form polyurethane.
It is preferable that the polyol (A) contains at least one selected from the group consisting of polyether polyols and polyester polyols.

The polyol (A) preferably has a number average molecular weight of 1,000 to 10,000 and a nominal number of functional groups of 2 or more. When the number average molecular weight is above the lower limit, the flexibility of the obtained foam tends to be further improved, and when it is below the upper limit, the hardness of the foam tends to be further improved. Furthermore, when the number of nominal functional groups is 2 or more, the wet heat compression strain, which is an index of durability, tends to be better. In addition. The nominal number of functional groups refers to the theoretical average number of functional groups (the number of active hydrogen atoms per molecule) assuming that no side reactions occur during the polymerization reaction of the polyol.

As the polyether polyol, for example, polypropylene ether polyol, polyethylene polypropylene ether polyol (hereinafter also referred to as PPG), polytetramethylene ether glycol (hereinafter also referred to as PTG), etc. can be used. As the polyester polyol, for example, a polyester polyol consisting of adipic acid and a diol, which is a polycondensation type polyester polyol, and a polycaprolactone polyol, which is a lactone polyester polyol, can be used.

The polyol (A) may contain a polyether polyol having a polyoxyalkylene chain made of a copolymer of oxyethylene and oxypropylene. The number average molecular weight of the polyether polyol is preferably 4,000 to 8,000, more preferably 6,000 to 8,000. Further, it is preferable that the nominal number of functional groups is 2 to 4. Furthermore, the amount of oxyethylene units in the polyether polyol is preferably 60 to 90% by mass, more preferably 60 to 80% by mass. By setting the oxyethylene unit to 60 to 90% by mass, durability can be further improved. Further, from the viewpoint of storage stability at low temperatures, the copolymer consisting of oxyethylene and oxypropylene is preferably a random copolymer.

The amount of the polyether polyol added is preferably 0.5 to 5% by mass based on the polyol (A). If it is above the lower limit, the moldability of the foam tends to be better, and if it is below the upper limit, the elongation rate of the foam tends to be better.

The polyol (A) may contain a polymer polyol obtained by polymerizing a vinyl monomer in a polyol by a conventional method for the purpose of adjusting hardness. Examples of such polymer polyols include those obtained by polymerizing and stably dispersing a vinyl monomer in a polyalkylene polyol such as the above-mentioned PPG in the presence of a radical initiator. Examples of vinyl monomers include acrylonitrile, styrene, vinylidene chloride, hydroxyalkyl methacrylate, and alkyl methacrylate, with acrylonitrile and styrene being preferred. Examples of such polymer polyols include EL-910 and EL-923 manufactured by AGC, and FA-728R manufactured by Sanyo Chemical Industries.

As the catalyst (B), various urethanization catalysts known in the art can be used, such as triethylamine, tripropylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, dimethylbenzylamine, N , N,N',N'-tetramethylhexamethylenediamine, N,N,N',N',N''-pentamethyldiethylenetriamine, bis-(2-dimethylaminoethyl)ether, triethylenediamine, 1,8 -Diaza-bicyclo[5.4.0]undecene-7,1,2-dimethylimidazole, dimethylethanolamine, N,N-dimethyl-N-hexanolamine, and organic acid salts thereof, stannous octoate, naphthene Also included are organometallic compounds such as zinc oxide. Also preferred are amine catalysts having active hydrogen such as N,N-dimethylethanolamine and N,N-diethylethanolamine.

The amount of the catalyst added is preferably 0.01 to 10% by mass based on the polyol (A). If it is above the lower limit, insufficient curing of the polyurethane foam is unlikely to occur, and if it is below the upper limit, the moldability tends to be further improved.

As the foam stabilizer (C), ordinary surfactants are used, and organic silicon-based surfactants are preferably used. For example, Dow/Toray SZ-1919, SH-192, SRX-280A, SZ-1142, SZ-1346E, SZ-1327, SZ-1336, SZ-3601, SZ-1671, SH-193, Momentive L-540, L-580, L-818, Y-10901C, Y-10366, L-3620, L-3630, L-3639, L-5309, L-5345, L-5420, L-6164, L-6190, L-6861, L-6900, L-6952, L-6970, Evonik B-8123, B-8409, B-8443, B-8450, B-8460, B-8462, B- 8465, B-8466, B-8486, B-8487, B-8491, B-8495, B-8462, B-8534, B-8547, B-8558, B-8871, BF-2370, B-8724LF2, Examples include B-8715LF2, BF-8734LF2, BF-8737LF2, BF-8742LF2, BF-8745LF2, BF-8747LF2, and the like. The amount of these foam stabilizers added is preferably 0.1 to 3% by mass based on the polyol (A).

The foaming agent (D) may be any foaming agent that can achieve the above-mentioned foaming pressure. The blowing agent (D) may include, for example, water (d1) and a physical blowing agent (d2) as an optional component.
Water (d1) generates carbon dioxide gas by reaction with isocyanate groups, which can cause foaming.

Examples of the physical blowing agent (d2) include chlorofluorocarbons, hydrochlorofluoroolefins, hydrochlorofluorocarbons, hydrofluoroolefins, hydrofluorocarbons, perfluorocarbons, and low-boiling halogen hydrocarbons such as methylene chloride. Examples include hydrocarbons such as pentane, cyclopentane, and the like.
Among them, hydrochlorofluoroolefins and hydrofluoroolefins such as HCFO-1233zd and HFO-1336mzz are preferable because they have a small ozone depletion potential (ODP) and a small global warming potential (GWP), and have a small environmental impact.
Moreover, foaming can also be carried out by mixing and dissolving air, nitrogen gas, or liquefied carbon dioxide into the stock solution using a gas loading device.

The amount of the blowing agent (D) added is preferably such that the concentration in the polyurethane foam-forming composition for filled structures is 0.2 mmol/g to 3.0 mmol/g, and 0.3 mmol/g to 2.5 mmol. /g is more preferable. If it is less than the upper limit, foaming becomes more stable, and if it is more than the lower limit, excessive density of the foam can be further suppressed.

The total amount of hydroxyl groups possessed by components other than the physical foaming agent (d2) in the polyol composition relative to the total mass of components other than the physical foaming agent (d2) in the polyol composition is 500 mgKOH/g or less. , for example, may be 100 to 490 mgKOH/g, or may be 200 to 490 mgKOH/g. Here, the components other than the physical foaming agent (d2) in the polyol composition are the polyol (A), the catalyst (B), the foam stabilizer (C), and the foaming agent other than the physical foaming agent (d2). agent (D) and any other components other than these.

The polyurethane foam-forming composition for filled structures may further contain a crosslinking agent. As the crosslinking agent, at least one cyclic glycol (hereinafter simply referred to as " cyclic glycol). Cyclic glycols are compounds that have a ring structure, such as cyclohexanediol, cyclohexanedimethanol, hydroquinone bis(2-hydroxyethyl) ether, dihydroxydiphenylmethane, bisphenol A hydride, polyoxyethylene bisphenol ether, and Oxypropylene bisphenol ether and the like can be mentioned. Among these, 1,4-cyclohexanedimethanol and polyoxyethylene bisphenol A ether are preferred from the viewpoint of having a high effect of improving the moist heat compression strain of the resulting flexible polyurethane foam. The content of cyclic glycol is preferably 1.5 to 8% by mass, more preferably 1.5 to 6% by mass, based on the polyol (A).

Polyisocyanate (E) is diphenylmethane diisocyanate (hereinafter referred to as MDI) such as 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, polyphenylene polymethylene polyisocyanate (hereinafter referred to as P). -MDI) is preferably used as the isocyanate source. In addition, various modified products such as the above-mentioned MDI, a mixture of MDI and P-MDI, urethane modified products, urea modified products, allophanate modified products, nurate modified products, and biuret modified products can also be used.
Among these, the polyisocyanate (E) preferably contains polyphenylene polymethylene polyisocyanate.
The polyisocyanate (E) may contain polyisocyanates other than MDI and P-MDI as optional components.
Examples of polyisocyanates other than MDI and P-MDI include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthalene diisocyanate, toridine diisocyanate, xylylene diisocyanate, and 1,3-phenylene diisocyanate. , 1,4-phenylene diisocyanate, lysine diisocyanate, triphenylmethane triisocyanate, tetramethylxylene diisocyanate, 1,6-hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, norbornane Diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate 4-isocyanate methyl octane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, trimethylhexamethylene diisocyanate, etc. are mentioned, and two or more of these may be used in combination. In addition, isocyanate-containing prepolymers produced by the reaction of these polyisocyanates with polyols, and modified products of these polyisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, biuret groups, isocyanurate groups, amide groups, imide groups) group, a uretonimine group, a uretdione group, or a modified product containing an oxazolidone group).

The polyol composition may contain components other than the above-mentioned (A) to (D). Moreover, the polyisocyanate composition may contain components other than polyisocyanate (E).

When manufacturing polyurethane foam, various known additives and auxiliaries such as fillers such as calcium carbonate and barium sulfate, flame retardants, plasticizers, colorants, and antifungal agents may be used as necessary. I can do it.

The polyurethane foam-forming composition for filled structures may have a foaming pressure of 30 kPa or more as measured according to the test conditions described in (1) to (4) below. The foaming pressure may be, for example, 30 to 300 kPa, 30 to 250 kPa, or 35 to 200 kPa.
<Test conditions>
(1) Among the polyurethane foam-forming compositions for filling structures, a sample in which the polyisocyanate composition was adjusted to 25°C ± 1°C, and a sample in which the polyol composition was adjusted to 25°C ± 1°C; A two-liquid sample consisting of
(2) Next, the two liquid samples are mixed using a mixer at 7000 rpm for 7 seconds.
(3) The obtained mixed solution is placed in a mold with inner dimensions of 120 mm x 150 mm x 70 mm and a pressure sensor inside the upper surface, and the concentration of the blowing agent (D) is 55 to 150 μmol/cm ³ and the injection density is Inject so that the amount is 40 to 100 kg/ ^m3 .
(4) After the polyurethane foam is sufficiently foamed, the foaming pressure is measured using a pressure sensor.

The concentration of the blowing agent (D) in the above <test conditions> may be 55 to 150 μmol/cm ³ or 80 to 130 μmol/cm ³ .
The injection density under the above <test conditions> may be 40 to 100 kg/m ³ or 45 to 80 kg/m ³ .

The polyurethane foam-forming composition for filled structures may have at least one of the seven foaming pressures measured according to the test conditions described in (1') to (5') below of 30 kPa or more. The foaming pressure may be, for example, 30 to 300 kPa, 30 to 250 kPa, or 35 to 200 kPa.
<Test conditions>
(1') Among the polyurethane foam-forming compositions for filling structures, a sample in which the polyisocyanate composition was adjusted to 25°C ± 1°C, and a sample in which the polyol composition was adjusted to 25°C ± 1°C. A two-liquid sample consisting of .
(2') Next, the two liquid samples are mixed using a mixer at 7000 rpm for 7 seconds.
(3') The obtained mixed solution was placed in a mold with inner dimensions of 120 mm x 150 mm x 70 mm and equipped with a pressure sensor inside the upper surface, and the concentration of the blowing agent (D) was determined to be X [μmol/cm ³ ] and the injection density. Inject so that Y [kg/m ³ ] satisfies any of the seven patterns shown below (X1, Y1) to (X7, Y7).
(4') After the polyurethane foam is sufficiently foamed, the foaming pressure is measured using a pressure sensor.
(5') Repeat steps (1') to (4') to measure the foaming pressure in all seven patterns shown below (X1, Y1) to (X7, Y7).

The polyurethane foam-forming composition for filled structures preferably has a free foam density of 25 to 45 kg/m ³ as measured based on JIS K7222. The freeform density may be 30-40 kg/m ³ or 30-35 kg/m ³ .

The above-described polyurethane foam-forming composition for filling structures is suitable for use in flexible polyurethane foams.

The polyurethane foam for filling structures includes a foam (cured foam) of a polyurethane foam-forming composition for filling structures. The polyurethane foam for the filling structure is preferably a flexible polyurethane foam.

The molding density of the polyurethane foam may be, for example, 100 kg/m ³ or less, 40 to 100 kg/m ³ , 45 to 80 kg/m ³ , or 50 to 75 kg/m ³ . It's okay.

The foaming pressure of the polyurethane foam may be, for example, 30 kPa or more, for example, 30 to 300 kPa, 30 to 250 kPa, or 35 to 200 kPa.

Next, a method for manufacturing polyurethane foam for filling structures will be explained.

Polyurethane foam for filled structures is produced by reaction foaming (foaming and curing) a mixed solution of polyol (A), catalyst (B), foam stabilizer (C), blowing agent (D), and polyisocyanate (E). ) Manufactured.

The molar ratio (NCO/active hydrogen) of all the isocyanate groups in the polyisocyanate (E) and all the active hydrogen groups in the active hydrogen group-containing compound containing water is 0.7 to 1.4 ( The isocyanate index (NCO INDEX) is preferably from 70 to 140), and more preferably from 0.7 to 1.2 (NCO INDEX = 70 to 120) for good foam durability and molding cycles.
When the NCO INDEX is 70 or more, the durability is further improved, and when the NCO INDEX is 140 or less or 120 or less, the foam is less likely to collapse during foaming due to rapid polymerization, and moldability tends to be better.

As a method for producing polyurethane foam for filling structures, a foaming stock solution of a mixed solution of the polyol (A), catalyst (B), foam stabilizer (C), blowing agent (D), and polyisocyanate (E) is applied to the outer wall. A manufacturing method can be used in which the foam is injected into the foam and then foamed and cured.

It is preferable that the isocyanate component and the polyol component are mixed immediately before foaming. Other components can be mixed in advance with the isocyanate component or polyol component to the extent that they do not affect the storage stability of the raw materials or changes in reactivity over time. These mixtures may be used immediately after mixing, or may be stored and then used in the required amount as appropriate. In the case of a foaming device that can simultaneously introduce more than two components into the mixing section, polyols, blowing agents, isocyanates, catalysts, foam stabilizers, additives, etc. can also be introduced individually into the mixing section.

Further, the mixing method may be either dynamic mixing in which mixing is performed in the mixing chamber of the machine head of the foaming machine or static mixing in which mixing is performed in the liquid delivery pipe, or both may be used in combination. Mixing of a gaseous component such as a physical foaming agent and a liquid component is often performed by static mixing, and mixing of components that can be stably stored as a liquid is often performed by dynamic mixing. The foaming device is preferably a high-pressure foaming device that does not require solvent cleaning of the mixing section.

A method for manufacturing a filling structure according to one aspect of the present disclosure is a method for manufacturing the above-mentioned filling structure, which comprises foaming and curing a mixture (a polyurethane foam-forming composition for a filling structure) inside the outer wall. forming a polyurethane foam inside the exterior wall.

A method for manufacturing a filling structure according to another aspect of the present disclosure includes foaming and curing the above-mentioned polyurethane foam-forming composition for a filling structure inside an outer wall to create a foaming pressure of 30 kPa or more inside the outer wall. forming a polyurethane foam having a

In these methods for producing filled structures, the method of foaming and curing the polyurethane foam-forming composition for filled structures is not particularly limited, and may be carried out as appropriate to obtain a polyurethane foam or filled structure that satisfies each of the above-mentioned characteristics. You can adjust it. That is, the above steps involve foaming and foaming a polyurethane foam-forming composition for a filled structure so as to obtain a polyurethane foam that satisfies each of the above-mentioned characteristics, or to obtain a filled structure that satisfies each of the above-mentioned characteristics. It may also be a curing step.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, unless otherwise specified, "part" and "%" in the text are based on mass.

[Preparation of polyol composition]
(Examples 1 to 7, Comparative Examples 1 to 3)
After replacing the reactor with a stirrer, a cooling tube, a nitrogen introduction tube, and a thermometer with nitrogen, 1000 g of polyol 1, 10 g of foam stabilizer 1, 16.0 g of catalyst 1, and 56 g of water were charged, and the mixture was heated at 23°C. By stirring for 0.5 hours, a polyol composition (P-1) was obtained. Other polyol compositions (P-2 to P-9) were also prepared in the same manner as P-1.

Among the raw materials shown in Table 3 or 4, the liquid temperature of the mixture (polyol composition) of all raw materials other than the polyisocyanate component was adjusted to 24°C to 26°C, and the polyisocyanate component was adjusted to a liquid temperature of 24°C to 26°C. It was adjusted. A predetermined amount of the polyisocyanate component was added to the polyol composition, mixed for 7 seconds using a mixer (7000 revolutions per minute), and then poured into a mold to foam a polyurethane foam.

A pressure sensor was installed inside the upper part of the mold to measure the foaming pressure of the foam. Note that the NCO Index in Tables 3 and 4 is the ratio of NCO groups to the number of active hydrogen atoms present in the formulation.

[Foaming conditions]
Mold temperature: 24-26℃
Mold inner dimensions: 120mm x 150mm x 70mm
Mold volume: ^1260cm3
Mold material: aluminum

[Raw materials used]
・Polyol (1): Polyether polyol with average functional group number = 2.0 and hydroxyl value = 14 (mgKOH/g), D 280 manufactured by Kaka Kagaku Co., Ltd.
・Polyol (2): Polyether polyol with average functional group number = 3.0 and hydroxyl value = 33 (mgKOH/g), EXCENOL-823 manufactured by Asahi Glass Co., Ltd.
・Polyol (3): Polyether polyol with average functional group number = 3.0 and hydroxyl value = 112 (mgKOH/g), GP-1500 manufactured by Sanyo Chemical Industries, Ltd.
・Polyol (4): Polyether polyol with average functional group number = 3.0 and hydroxyl value = 281 (mgKOH/g), GP-600 manufactured by Sanyo Chemical Industries, Ltd.
・Polyol (5): Polyether polyol with average functional group number = 3.0 and hydroxyl value = 561 (mgKOH/g), G-303 manufactured by Kaka Kagaku Co., Ltd.
・Catalyst (1): Dipropylene glycol solution of triethylenediamine (manufactured by Tosoh Corporation, product name: TEDA-L33), hydroxyl value = 560 (mgKOH/g)
・Catalyst (2): Dimethylimidazole (manufactured by Tosoh Corporation, product name: TOYOCAT-DMI)
・Foam stabilizer (1): Silicone foam stabilizer (manufactured by Dow Toray Industries, product name: SH-192)
・Foam stabilizer (2): Silicone foam stabilizer (manufactured by Momentive, product name: Y-10366)
・Blowing agent (1): Water ・Blowing agent (2): HFO-1233zd(E) (manufactured by Honeywell, product name: Solstice LBA)
・Isocyanate: Polyphenylene polymethylene polyisocyanate (manufactured by Tosoh Corporation, product name: MR-200)

[Injection density]
The injection density was determined using the following formula.
Injection density = Amount of raw material mixture input into the mold ÷ Mold volume

[Blowing agent concentration per unit volume]
The blowing agent concentration per unit volume was determined using the following formula.
Blowing agent concentration per unit volume = Blowing agent concentration in the system (mixture) x injection density

[Free form density]
Free foam density means the density of free foam obtained by foaming without a mold lid, and was determined by the method described in JIS K7222.

[Molding density]
The molding density means the density of the foam obtained by filling the inside of the mold with the lid on, and was determined by the method described in JIS K7222.

[Foaming pressure after curing]
For the foaming pressure after curing, the foaming pressure was measured 2 hours after stirring the raw material mixture, at which the change in foaming pressure was approximately constant in this example.

[Closed cell property]
Regarding the closed-cell property, for free foam obtained by foaming without a mold lid, cases where shrinkage was observed immediately after foaming or after curing were evaluated as ``Yes'', and cases where no shrinkage was observed were rated as ``No''. .
Generally, open-celled foams do not shrink, so foams that show shrinkage indicate closed-celled foams.

Claims

outer wall and
a polyurethane foam filled inside the outer wall;
A filling structure comprising:
The polyurethane foam is a foamed and cured product of a mixture of polyol (A), catalyst (B), foam stabilizer (C), blowing agent (D) and polyisocyanate (E),
A filling structure in which the foaming pressure of the polyurethane foam is 30 kPa or more.
The polyurethane foam has a resin part and a cell part,
The filling structure according to claim 1, wherein the total content of urethane groups and urea groups in the resin part is 3.85 mmol/g or less.
The polyurethane foam has a resin part and a cell part,
The filling structure according to claim 1, wherein the total hydroxyl value of the components forming the resin part in the mixture is 220 mgKOH/g or less.
The filled structure according to claim 1, wherein the content of the blowing agent (D) in the mixture is 55 to 150 μmol/cm 3 relative to the internal volume of the outer wall filled with the polyurethane foam.
The filling structure according to claim 1, wherein the polyurethane foam has a molding density of 100 kg/m 3 or less.
The filling structure according to claim 1, wherein the polyol (A) includes a polyether polyol.
The filling structure according to claim 1, wherein the polyisocyanate (E) includes polyphenylene polymethylene polyisocyanate.
The filling structure according to claim 1, wherein the polyurethane foam is a flexible polyurethane foam.
The filling structure of claim 1, wherein the polyurethane foam is sealed with the outer wall.
The filling structure of claim 1, wherein the outer wall is selected from the group consisting of a metal wall and a reinforced concrete wall.
A composition for forming a polyurethane foam in a filling structure filled with a polyurethane foam having a resin part and a cell part, the composition comprising:
A polyol composition containing a polyol (A), a catalyst (B), a foam stabilizer (C) and a blowing agent (D), and a polyisocyanate composition containing a polyisocyanate (E),
The total hydroxyl value of the components that can form the resin part is 220 mgKOH/g or less,
A polyurethane foam-forming composition for a filled structure, wherein at least one of the seven foaming pressures measured according to the test conditions described in (1') to (5') below is 30 kPa or more.
<Test conditions>
(1') Among the polyurethane foam-forming compositions for filling structures, a sample in which the polyisocyanate composition was adjusted to 25°C ± 1°C, and a sample in which the polyol composition was adjusted to 25°C ± 1°C. A two-liquid sample consisting of .
(2') Next, the two liquid samples are mixed using a mixer at 7000 rpm for 7 seconds.
(3') The obtained mixed solution was placed in a mold with inner dimensions of 120 mm x 150 mm x 70 mm and equipped with a pressure sensor inside the upper surface, and the concentration of the blowing agent (D) was determined to be X [μmol/cm 3 ] and the injection density. Inject so that Y [kg/m 3 ] satisfies any of the seven patterns shown below (X1, Y1) to (X7, Y7).
(4') After the polyurethane foam is sufficiently foamed, the foaming pressure is measured using a pressure sensor.
(5') Repeat steps (1') to (4') to measure the foaming pressure in all seven patterns shown below (X1, Y1) to (X7, Y7).
The polyurethane foam-forming composition for a filled structure according to claim 11, wherein the content of the blowing agent (D) is 0.2 mmol/g to 3.0 mmol/g.
The polyurethane foam-forming composition for filled structures according to claim 11, which has a free foam density of 25 to 45 kg/m 3 as measured based on JIS K 7222.
The polyurethane foam-forming composition for a filled structure according to claim 11, wherein the polyol (A) contains a polyether polyol.
The polyurethane foam-forming composition for a filled structure according to claim 11, wherein the polyisocyanate (E) comprises polyphenylene polymethylene polyisocyanate.
The polyurethane foam-forming composition for a filling structure according to claim 11, which is used for flexible polyurethane foam.
A composition for forming the polyurethane foam in a filling structure comprising an outer wall and a polyurethane foam filled inside the outer wall,
A polyol composition containing a polyol (A), a catalyst (B), a foam stabilizer (C) and a blowing agent (D), and a polyisocyanate composition containing a polyisocyanate (E),
A polyurethane foam-forming composition for a filling structure, wherein the polyurethane foam has a foaming pressure of 30 kPa or more.
A polyurethane foam for a filled structure, comprising a foamed cured product of the polyurethane foam-forming composition for a filled structure according to any one of claims 11 to 17.
A method for manufacturing a filling structure according to any one of claims 1 to 10, comprising:
A method of manufacturing a filling structure, comprising foaming and curing the mixture inside the outer wall to form the polyurethane foam inside the outer wall.
The polyurethane foam-forming composition for a filling structure according to any one of claims 11 to 17 is foamed and cured inside the outer wall to form a polyurethane foam having a foaming pressure of 30 kPa or more inside the outer wall. A method of manufacturing a filling structure, comprising the step of forming.