JP2006307092A - Water sealing material comprising polyurethane foam - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyurethane foam having both water sealing property and flame retardant property. <P>SOLUTION: This water sealing material contains a phosphate which is a solid at room temperature in a polyurethane foam obtainable by reacting and curing by addition of a polyol, an organic isocyanate, and an aid. According to this invention, using the phosphate which is a solid at room temperature as a flame retardant, excellent flame retardant property can be given without lowering its sealing property. Phosphorus element content in the polyurethane foam is preferably not higher than 2%. This polyurethane foam may be a polyurethane foam sheet material having its own skin. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a waterstop material comprising a polyurethane foam and a method for producing the same. In particular, the present invention relates to a waterstop material made of a polyurethane foam having flame retardancy and a method for producing the same.

The polyurethane foam is a flexible foam having excellent mechanical properties (tensile strength / elongation) and high resilience. By using a material having high water repellency as the foam raw material, water-stopping property is expressed, so that it can be used as a foam water-proofing material (foam sealing material). About the composition of the polyurethane foam used as a foam waterproofing material, and its manufacturing method, it is indicated by the following patent documents 1 and patent documents 2, and such a polyurethane foam is manufactured in the shape of a block or a sheet, Depending on the application, secondary processing such as adhesive tape processing, slit processing for adjusting to a desired shape, slicing processing, and punching processing is performed. This polyurethane foam has a high water-stopping property and is easy to process, and is used for water-stopping purposes of various products such as car air conditioners, refrigerators, prefabricated houses, and unit baths.

Conventionally, a polyurethane foam water-proof material is obtained from a hydrophobic resin, and is a material having low flame retardancy due to its properties. Therefore, in applications that require high flame retardancy, it is necessary to add a flame retardant to the polyurethane foam. This tendency becomes more prominent as the degree of foaming is higher (as the density of the polyurethane foam is lower), and it is necessary to increase the amount of flame retardant added in the case of high foams.
Japanese Patent Laid-Open No. 3-68677 JP-A-55-104330 JP-A-5-98150 JP-A-6-330022 Japanese Patent Laid-Open No. 2001-2749 JP 2004-137499 A JP-A-11-1612 JP 2005-29617 A JP-A-11-29701 JP 2002-146179 A Japanese Patent Laid-Open No. 11-24170

Therefore, conventionally, it has been proposed to use various flame retardants in order to impart flame retardancy to the polyurethane foam.

For example, brominated flame retardants and chlorinated flame retardants have been generally used to make polyurethane foam flame retardant. However, these halogen-containing flame retardants have problems in terms of environment and safety because halogen gas is generated during combustion. In addition, it has been proposed to use an antimony oxide-based flame retardant for flame retardant of polyurethane foam, but the use of this antimony oxide-based flame retardant also has problems from the viewpoint of environment and safety.

In addition, it has been proposed to use inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide for flame retardant of polyurethane foams, but these inorganic flame retardants have a low flame retardant effect and are added in amounts. There was a problem that the effect was small even if it was increased. Moreover, since these inorganic flame retardants are inferior in water resistance, it is not preferable to use it for the water stop material which consists of a polyurethane foam.

And it is disclosed by said patent document 3 to use the melamine which is a nitrogen-type flame retardant for the flame retardance of a polyurethane foam. However, nitrogen-based flame retardants such as melamine also have a problem that the flame retardant effect is low and the effect is small even if the amount added is increased.

Furthermore, it has been proposed to use a red phosphorus flame retardant for making the polyurethane foam flame retardant. However, red phosphorus flame retardants have a high risk of causing spontaneous ignition, and many of them need to be handled with care. In addition, red phosphorus flame retardants react with moisture to generate toxic phosphine gas.

Further, Patent Documents 4 to 7 disclose that a halogen-containing phosphoric ester that is liquid at room temperature is used for flame retardancy of polyurethane foam. The halogen-containing phosphate ester which is liquid at normal temperature can impart high flame retardancy to the polyurethane foam with a small amount of addition due to the synergistic effect of halogen and phosphorus. However, this halogen-containing phosphate ester which is liquid at room temperature has a problem in terms of environment and safety because halogen gas is generated during combustion. Thus, the use of non-halogen phosphates that are liquid at room temperature for flame retardancy of polyurethane foams is disclosed in Patent Documents 8 to 11 described above. However, this non-halogen phosphate that is liquid at room temperature has a low flame retardant effect, so it is necessary to increase the amount of addition, and as a result, there is a problem that the water stoppage of the polyurethane foam is lowered. .

On the other hand, if a phosphoric acid ester containing a hydroxyl group is used to make the polyurethane foam flame-retardant, the reduction in water-stopping can be reduced. However, the use of a phosphate ester that is fixed to a urethane resin by this reaction has a problem that it causes a significant reduction in the compression residual strain of the polyurethane foam.

This invention is made | formed in view of the above-mentioned problem, and it aims at providing the water stop material which consists of a polyurethane foam to which the flame retardance was provided, without causing the fall of water stop.

According to the present invention, a polyurethane foam obtained by reaction curing by adding a polyol, an organic isocyanate, and an auxiliary agent, and containing a phosphoric acid ester that is solid at room temperature, is a waterstop comprising a polyurethane foam. Material is provided.

In the polyurethane foam, the phosphorus element content is preferably 2% or less.

The polyurethane foam may be a polyurethane foam sheet material having a self-skin.

In the water-stopping material comprising the polyurethane foam of the present invention and the method for producing the same, a polyurethane foam obtained by reaction curing by adding a polyol, an organic isocyanate and an auxiliary agent, and using a highly hydrophobic raw material By adding a solid phosphate ester at room temperature, flame retardancy can be imparted without causing a decrease in water stoppage.

According to the water-stopping material comprising the polyurethane foam of the present invention and the method for producing the same, by using a phosphoric acid ester that is solid at room temperature as a flame retardant, excellent flame retardancy can be expressed without causing a decrease in water-stopping property. There is an effect.

Next, the polyurethane foam of this invention and its manufacturing method are demonstrated in detail.

The polyurethane foam of the present invention and the curable composition used in the production method thereof are polyols described later and known polyfunctional organic isocyanates, foam stabilizers, curing catalysts, foaming agents, crosslinking agents, colorants, resin modifiers. Additives such as an agent, a flame retardant, an ultraviolet absorber, and a durability improver can be added within a range not impairing the object of the present invention, but are not particularly limited thereto.

Although the polyol used for this invention is generally used with a urethane resin, it is not specifically limited.

As the polyether polyol used in the present invention, a low molecular weight polyol such as propylene glycol, glycerin or trimethylolpropane is used as an initiator, and an addition polymerized oxirane compound such as ethylene oxide, propylene oxide, butylene oxide or tetrahydrofuran is used. May be. These polyether polyols are raw materials with high hydrophobicity.

The polyester polyol used in the present invention includes, as an acid component, dimer acid, adipic acid and the like, and glycol components such as ethylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, and 2-methyl-1,3-propanediol. An esterified product obtained by polymerizing 1,4-butanediol or the like may be used. These polyester polyols are highly hydrophobic raw materials.

As other polyols used in the present invention, castor oil and castor oil-modified products, polybutadiene-based polyols and hydrogenated products thereof, polyisoprene-based polyols and hydrogenated products thereof may be used. These polyols are highly hydrophobic raw materials.

The various polyols described above can be used alone or as a mixture thereof. These polyols may be used as a hydroxyl group-terminated prepolymer or isocyanate group-terminated prepolymer previously reacted with a polyfunctional isocyanate described later, but are not limited thereto.

Moreover, as a polyfunctional isocyanate used for this invention, you may use the aromatic isocyanate and aliphatic isocyanate which contain two or more isocyanate groups in a molecule | numerator, or those modified substances. Specifically, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDAI), hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate Examples thereof include, but are not limited to, natto (TMXDI) and the like, and mixtures thereof.

Examples of the phosphoric acid ester solid at room temperature used in the present invention include, for example, an aliphatic phosphoric acid ester (SH-800 (trade name DAIGUARD-800) manufactured by Daihachi Chemical Industry Co., Ltd., a phosphorus element content of 16.0%. , Melting point 127 ° C.), aromatic phosphate ester (trade name PX-200, phosphorus element content 9.0%, melting point 95 ° C., the same shall apply hereinafter) manufactured by the same company. The structure of the aromatic phosphate ester (PX-200) is as shown in the following formula (I).

  The above-mentioned phosphoric acid ester that is solid at room temperature can be used alone or as a mixture thereof.

Examples of the foam stabilizer that can be used in the present invention include organic silicone foam stabilizers, surfactants, and the like, and mixtures thereof. It is particularly preferable to use a silicone foam stabilizer having an active group such as a hydroxyl group or an amino group that reacts with a polyfunctional isocyanate. When this silicone foam stabilizer is used, the water absorption rate is lowered and the water stop performance of the water stop material is improved. Examples of the surfactant include, but are not limited to, diethylamino oleate, sorbitan monostearate, glycerin monooleate, vinyl pyrrolidone, fluorine, organic compound, and the like, and mixtures thereof. These foam stabilizers such as organic silicone foam stabilizers and surfactants function as raw materials with high hydrophobicity.

Examples of the blowing agent that can be used in the present invention include water, inert gases such as nitrogen gas, carbon dioxide gas and air at normal pressure, halogenated alkanes such as monofluorotrichloromethane and dichloromethane, butane, Examples include, but are not limited to, low-boiling alkanes such as pentane, azobisisobutylnitrile that generates cracked nitrogen gas, and the like, and mixtures thereof.

As other additives, a catalyst, a crosslinking agent, a colorant, a resin modifier, an ultraviolet absorber, a durability improver, and the like can be arbitrarily used as necessary.

The above-mentioned various raw materials can be used for the polyurethane foam of the present invention and the production method thereof, and conventionally known one-shot methods, partial prepolymer methods, prepolymer methods and the like can be used. The polyurethane foam product of the present invention can be continuously produced by molding, slab foaming or sheet foaming.

The polyurethane foam as a water-stopping material generally has an expansion ratio of 10 to 40 times, an air permeability at a thickness of 10 mm of 20 cm ³ / cm ² · sec or less, a 50% compression residual strain of 20% or less, 50 Since the one whose% compression hardness is adjusted in the range of 2.5 to 70 kPa is used, the polyurethane foam of the present invention uses the above-mentioned raw materials, and is arbitrarily adjusted to meet these conditions. .

Next, the polyurethane foam of this invention and its manufacturing method are demonstrated, referring an Example and a comparative example.

Here, in producing the polyurethane foam of the present invention, the following two polyols (hereinafter referred to as “polyol A” and “polyol B”) were used. However, these polyols are only examples, and the production of the polyurethane foam of the present invention is not limited to these polyols.
Polyol A: Glycerin-based polyether polyol (glycerin added with propylene oxide, average functional group number 3, average molecular weight 3000, hydroxyl value 56 mgKOH / g)
Polyol B: Dimer acid polyester polyol obtained by reacting dimer acid and diethylene glycol (DEG) (average molecular weight 1500, hydroxyl value 75 mgKOH / g)

In producing the polyurethane foam of the present invention, except for Comparative Examples 1, 6 and 7 which are blanks, in each Example and each Comparative Example, six phosphate esters shown in Table 1 below were used.

  In addition, among the six phosphate esters in Table 1 above, for two phosphate esters that are solid at room temperature, the particle size is selected according to the opening distance of the sieve, and the particle size level is as shown in Table 2 below. did.

EXAMPLES Next, although an Example and a comparative example demonstrate this invention concretely, this invention is not necessarily limited only to these Examples. In each example, “parts” and “%” are based on weight. In addition, the polyurethane foam curable composition includes a hydrophobic polyol described later and a conventionally known polyfunctional isocyanate, foam stabilizer, curing catalyst, foaming agent, crosslinking agent, colorant, resin modifier, flame retardant. Additives such as ultraviolet absorbers and durability improvers can be added as long as the object of the present invention is not impaired. However, the present invention is not particularly limited thereto.

Here, first, the measurement methods of physical properties of the polyurethane foam performed in Examples and Comparative Examples are shown in Table 3 below.

In the water-stopping measurement shown in Table 3 above, the U-shaped water-stopping test 1 shown in FIG. 1 was used. In the measurement of water-stopping, a U-shaped test piece 3 having a thickness of 10 mm and a width of 15 mm shown in FIG. 1 is used. After compressing so that the thickness of the U-shaped test piece 3 is reduced to 50% by the acrylic plates 2a and 2b having two smooth surfaces through the spacer, the U-shaped test piece 3 has a predetermined water level. After 24 hours, the water level without water leakage was determined and the water was stopped.

In Example 1, a polyurethane foam was produced by slab foaming using an ether type polyol. That is, first, 100 parts of polyol A (polyether polyol obtained by addition polymerization of propylene oxide to glycerin, average functional group number 3, average molecular weight 3000, hydroxyl value 56 mg KOH / g) and 10 parts of petroleum resin at a room temperature of 300 to 500 μm in particle size. Solid phosphate ester (SH-800 (trade name DAIGUARD-800), manufactured by Daihachi Chemical Industry Co., Ltd., aliphatic phosphate ester, melting point 127 ° C., hereinafter the same), 1.0 part of silicone foam stabilizer having a hydroxyl group Then, 0.3 part of a tin catalyst and 2.0 parts of water were placed in a resin cup and stirred uniformly with a mixer. The phosphoric acid ester has a phosphorus element content (phosphorus ratio) in the obtained polyurethane foam of 0.5, 1.0, 1.5, 2.0, 2.5, and 3.0%. Added. After the stirring, toluene diisocyanate (trade name T-65, manufactured by Nippon Polyurethane Industry Co., Ltd., the same applies below) is added so that the NCO / OH ratio is 1.10. It was poured into a box-shaped container made of paper and allowed to react. The resulting block-like polyurethane foam was evaluated for performance after one week. Table 4 below summarizes the various conditions and physical properties of Example 1. As shown in Table 4 below, the obtained polyurethane foam had low air permeability, low water absorption, low compression residual strain (high resilience), and high water-stopping properties. In particular, when the phosphorus ratio in the polyurethane foam was 2% or less, higher water blocking properties were exhibited. Moreover, combustibility fell, so that the addition amount of phosphate ester (SH-800) was increased. That is, when the phosphorus ratio in the polyurethane foam is 2% or less, the flame retardancy can be improved while maintaining a higher water-stopping property. In Table 4, the flame retardancy level is ◎ when the combustion distance is less than 20 mm in the flammability measurement shown in Table 3 above, and the phosphoric acid ester is added when the combustion distance is 20 mm or more. The case where it became slower than the case where it did not do was made into (circle), and the level of the burning rate when not adding phosphate ester was made into x. This is the same in the following Tables 5 to 15 in each Example and each Comparative Example described later.

  Phosphoric acid ester (SH-800) instead of phosphoric acid ester (trade name PX-200, manufactured by Daihachi Chemical Industry Co., Ltd., aromatic phosphoric acid ester, melting point 95 ° C., hereinafter the same) ) Was used in the same manner as in Example 1 to obtain a block-like polyurethane foam. Table 5 below summarizes various conditions and physical properties of Example 2. As shown in Table 5 below, the obtained polyurethane foam had low air permeability, low water absorption, low compression residual strain (high resilience), and high water-stopping properties. In particular, when the phosphorus ratio in the polyurethane foam was 2% or less, higher water blocking properties were exhibited. Moreover, the combustibility fell, so that the addition amount of phosphate ester (PX-200) was increased. That is, when the phosphorus ratio in the polyurethane foam is 2% or less, the flame retardancy can be improved while maintaining a higher water-stopping property.

In Example 3, a polyurethane foam was produced by slab foaming using an ester type polyol. That is, first, polyol B (dimer acid polyester polyol obtained by reacting dimer acid and DEG, average molecular weight 1500, hydroxyl value 75 mgKOH / g), and phosphoric acid ester (SH-800) solid at room temperature having a particle size of 300 to 500 μm, A silicone foam stabilizer having a hydroxyl group (1.0 part), a tin catalyst (0.35 part), and water (2.0 parts) were placed in a resin cup and stirred uniformly with a mixer. The phosphoric acid ester (SH-800) is added so that the phosphorus ratio in the obtained polyurethane foam is 0.5, 1.0, 1.5, 2.0, 2.5, 3.0% did. After the stirring, toluene diisocyanate (T-65) was added so as to have an NCO / OH ratio of 1.05. After stirring rapidly with a mixer, the mixture was poured into a box-shaped container made of exfoliated process paper and reacted. I let you. The resulting block-like polyurethane foam was evaluated for performance after one week. Table 6 below summarizes various conditions and physical properties of Example 3. As shown in Table 6 below, the obtained polyurethane foam had low air permeability, low water absorption, low compression residual strain (high resilience), and high water-stopping properties. In particular, when the phosphorus ratio in the polyurethane foam was 2% or less, higher water-stopping properties and restoring properties were exhibited. Moreover, combustibility fell, so that the addition amount of phosphate ester (SH-800) was increased. That is, when the phosphorus ratio in the polyurethane foam is 2% or less, the flame retardancy can be improved while maintaining a higher water-stopping property. Note that, when the phosphorus ratio in the polyurethane foam is 2.5% or more, the compressive residual strain is increased and the restoration property is reduced. Therefore, in the polyurethane foam of the present invention, the phosphorus element content is 2%. It has been found that the following is more preferable.

  A block-like polyurethane foam in the same manner as in Example 1 except that phosphate ester (SH-800) having a particle size of 500 to 800 μm was used instead of phosphate ester (SH-800) having a particle size of 300 to 500 μm. Got. In Example 4, the phosphate ester (SH-800) was added so that the phosphorus ratio in the obtained polyurethane foam was 0.5%. Table 7 below summarizes various conditions and physical properties of Example 4. As shown in Table 7 below, the obtained polyurethane foam had low air permeability, low water absorption, low compression residual strain (high resilience), and high water-stopping properties. The flame retardancy was slightly inferior to Example 1 using a phosphoric acid ester (SH-800) having a particle size of 300 to 500 μm.

  A block-like polyurethane foam in the same manner as in Example 1 except that phosphate ester (SH-800) having a particle size of 106 to 300 μm was used instead of phosphate ester (SH-800) having a particle size of 300 to 500 μm. Got. In Example 5, the phosphate ester (SH-800) was added so that the phosphorus ratio in the obtained polyurethane foam was 0.5%. Table 7 below summarizes various conditions and physical properties of Example 5. As shown in Table 7 below, the obtained polyurethane foam had low air permeability, low water absorption, low compression residual strain (high resilience), and high water-stopping properties. Moreover, compared with Example 1 using the phosphoric acid ester (SH-800) with a particle size of 300-500 micrometers, the flame retardance improved further.

  A block-like polyurethane foam was obtained in the same manner as in Example 1 except that a phosphate ester (SH-800) having a particle size of 106 μm or less was used instead of a phosphate ester (SH-800) having a particle size of 300 to 500 μm. Obtained. In Example 6, the phosphate ester (SH-800) was added so that the phosphorus ratio in the obtained polyurethane foam was 0.5%. Table 7 below summarizes various conditions and physical properties of Example 6. As shown in Table 7 below, the obtained polyurethane foam had low air permeability, low water absorption, low compression residual strain (high resilience), and high water-stopping properties. Moreover, compared with Example 1 using the phosphoric acid ester (SH-800) with a particle size of 300-500 micrometers, the flame retardance improved further.

  In Example 7, a polyurethane foam was produced by sheet-like foaming using an ether type polyol. That is, first, 100 parts of polyol A (polyether polyol obtained by addition polymerization of propylene oxide to glycerin, average functional group number 3, average molecular weight 3000, hydroxyl value 56 mg KOH / g) and 15 parts of petroleum resin, with a particle size of 300 to 500 μm at room temperature. Solid phosphate ester (SH-800), 1.0 part of a silicone foam stabilizer having a hydroxyl group, 0.4 part of a tin catalyst, and 3.2 parts of water were placed in a resin cup and stirred uniformly with a mixer. The phosphoric acid ester (SH-800) was added so that the phosphorus ratio in the obtained polyurethane foam was 1.0, 1.5, and 2.0%. After the stirring, toluene diisocyanate (T-65) was added so as to have an NCO / OH ratio of 1.05, stirred rapidly with a mixer, and then uniformly applied onto the peeled process paper. The process paper that had been subjected to the peeling treatment was covered with air so as not to enter, and this was placed in an oven at 70 ° C. for 5 minutes and heated, and then placed in an oven at 110 ° C. for 5 minutes and heated. The process paper was removed from the oven and peeled to obtain a sheet-like polyurethane foam. The physical property measurement was started after one week. Table 8 below summarizes various conditions and physical properties of Example 7. As shown in Table 8 below, the obtained polyurethane foam had low air permeability, low water absorption, low compression residual strain (high resilience), and high water stopping properties. Moreover, combustibility fell, so that the addition amount of phosphate ester (SH-800) was increased. That is, when the phosphorus ratio in the polyurethane foam is 2% or less, flame retardancy can be improved while maintaining high water-stopping property.

(Comparative Example 1)
In Comparative Example 1, a block-like polyurethane foam was obtained under the same conditions as in Example 1 except that no phosphoric acid ester (SH-800) solid at room temperature was added. Table 9 below summarizes various conditions and physical properties of Comparative Example 1. As shown in Table 9 below, the obtained polyurethane foam had low air permeability, low water absorption, low compression residual strain (high resilience), and high water-stopping properties. However, it was highly combustible and burned at a burning rate of 97 mm / min.

(Comparative Example 2)
In Comparative Example 2, phosphate ester (trade name CR-504L, manufactured by Daihachi Chemical Industry Co., Ltd., chlorine-containing aliphatic phosphoric acid at room temperature instead of phosphate ester (SH-800) which is solid at ordinary temperature A block-like polyurethane foam was obtained under the same conditions as in Example 1 except that an ester was used. Table 10 below summarizes various conditions and physical properties of Comparative Example 2. As shown in Table 10 below, the obtained polyurethane foam was excellent in resilience and flame retardancy, but had high breathability and water absorption, and very low water-stopping properties.

(Comparative Example 3)
In Comparative Example 3, phosphate ester (SH-882 (trade name DAIGUARD-882), manufactured by Daihachi Chemical Industry Co., Ltd., fat at room temperature instead of phosphate ester (SH-800) which is solid at room temperature A block-like polyurethane foam was obtained under the same conditions as in Example 1 except that a group phosphate ester (hereinafter the same) was used. Table 11 below summarizes various conditions and physical properties of Comparative Example 3. As shown in Table 11 below, the obtained polyurethane foam was excellent in resilience and flame retardancy, but had high air permeability and water absorption and low water-stopping properties.

(Comparative Example 4)
In Comparative Example 4, a phosphate ester (trade name TCP, manufactured by Daihachi Chemical Industry Co., Ltd., aromatic phosphate ester, the same shall apply hereinafter) instead of a phosphate ester (SH-800) that is solid at ordinary temperature. ) Was used under the same conditions as in Example 1 to obtain a block-like polyurethane foam. Table 12 below summarizes the conditions and physical properties of Comparative Example 4. As shown in Table 12 below, the obtained polyurethane foam was excellent in resilience and flame retardancy, but had high air permeability and water absorption and low water-stopping properties.

(Comparative Example 5)
In Comparative Example 5, a phosphate ester (trade name DAIGUARD-610, manufactured by Daihachi Chemical Industry Co., Ltd., hydroxyl group-containing aromatic phosphoric acid at room temperature instead of a phosphate ester (SH-800) that is solid at room temperature. A block-like polyurethane foam was obtained under the same conditions as in Example 1 except that a mixture of an ester and an aliphatic phosphate ester (hereinafter the same) was used. Table 13 below summarizes the conditions and physical properties of Comparative Example 5. As shown in Table 13 below, the obtained polyurethane foam had low breathability and excellent flame retardancy. However, the higher the phosphorus ratio in the polyurethane foam, the higher the water absorption and the lower the water stoppage. Further, when the phosphorus ratio in the polyurethane foam was 2.5% or more, the compressive residual strain was increased, and the recoverability was rapidly deteriorated.

(Comparative Example 6)
In Comparative Example 6, a block-like polyurethane foam was obtained under the same conditions as in Example 3 except that no phosphoric acid ester (SH-800) solid at room temperature was added. Table 14 below summarizes various conditions and physical properties of Comparative Example 6. As shown in Table 14 below, the obtained polyurethane foam had low air permeability, low water absorption, low compression residual strain (high resilience), and high water-stopping properties. However, it was highly combustible and burned at a burning rate of 73 mm / min.

(Comparative Example 7)
In Comparative Example 7, a sheet-like polyurethane foam was obtained under the same conditions as in Example 7 except that no phosphoric acid ester (SH-800) solid at room temperature was added. Table 15 below summarizes various conditions and physical properties of Comparative Example 7. As shown in Table 15 below, the obtained polyurethane foam had low air permeability, low water absorption, low compression residual strain (high resilience), and high water-stopping properties. However, it was highly combustible and burned at a burning rate of 104 mm / min.

Here, Table 16 below summarizes the relationship between the phosphorus ratio and the density in the polyurethane foam produced by slab foaming for each type of phosphate ester from the results of the above Examples and Comparative Examples. In Table 16 below, among the phosphate esters that are solid at room temperature, for SH-800, the ether type polyol is used in the second column from the left, and the ester type polyol is used in the rightmost case. Shown in the column. Moreover, the unit of the numerical value in Table 16 is kg / m ³ .

Next, Table 17 below summarizes the relationship between the phosphorus ratio and the air permeability in the polyurethane foam produced by slab foaming for each type of phosphate ester from the results of the above Examples and Comparative Examples. In Table 17 below, among the phosphate esters that are solid at room temperature, for SH-800, the ether type polyol is used in the second column from the left, and the ester type polyol is used in the rightmost case. Shown in the column. The unit of the numerical values in Table 17 is cm ³ / cm ² · sec.

FIG. 2 shows a plot based on the results of Table 17 above, with the phosphorus ratio in the polyurethane foam plotted on the horizontal axis and the air permeability of the polyurethane foam plotted on the vertical axis.

As shown in FIG. 2, when using CR-504L, SH-882 and TCP among phosphoric acid esters which are liquid at room temperature, a highly air-permeable polyurethane having an air permeability exceeding 2.5 cm ³ / cm ² · sec. In contrast, when a phosphoric acid ester (SH-800 and PX-200) that is solid at room temperature is used, the air permeability of the polyurethane foam exceeds 2.5 cm ³ / cm ² · sec. It can be seen that a low-aeration polyurethane foam was obtained. Of the phosphoric acid esters that are liquid at room temperature, a low-aeration polyurethane foam was also obtained when DAIGUARD-610 was used. However, when DAIGUARD-610 was used, compression residual strain and water absorption An increase in water resistance and a decrease in water stoppage are observed.

Next, from the results of the above Examples and Comparative Examples, Table 18 below summarizes the relationship between the phosphorus ratio and the compression hardness in the polyurethane foam produced by slab foaming for each type of phosphate ester. . In Table 18 below, among the phosphate esters that are solid at room temperature, for SH-800, the ether type polyol is used in the second column from the left, and the ester type polyol is used in the rightmost case. Shown in the column. The unit of numerical values in Table 18 is kPa.

Next, Table 19 below summarizes the relationship between the phosphorus ratio and compression residual strain in polyurethane foams produced by slab foaming for each type of phosphate ester from the results of the above Examples and Comparative Examples. . In Table 19, the phosphate ester (SH-800) that is solid at room temperature is the second column from the left when the ether type polyol is used, and the rightmost case when the ester type polyol is used. Shown in the column. The unit of numerical values in Table 19 is%.

FIG. 3 shows a plot based on the results of Table 19 above, with the phosphorus ratio in the polyurethane foam plotted on the horizontal axis and the compression residual strain of the polyurethane foam plotted on the vertical axis.

As shown in FIG. 3, when any phosphoric acid ester was used, a low compression residual strain of 20% or less was exhibited when the phosphorus ratio in the polyurethane foam was 2% or less. Moreover, in the case of using DAIGUARD-610 among the phosphoric acid esters which are liquid at normal temperature, the compression residual strain increases when the phosphorus ratio in the polyurethane foam is 2.5% or more, and the restorability deteriorates rapidly. . In addition, when SH-800 is used among phosphoric acid esters that are solid at room temperature and an ester type polyol is used, if the phosphorus ratio in the polyurethane foam is 2.5% or more, the compressive residual strain increases. From the fact that the restoring property was lowered, it was found that the polyurethane foam of the present invention preferably has a phosphorus element content of 2% or less.

Next, Table 20 below summarizes the relationship between the phosphorus ratio and the combustion distance in the polyurethane foam produced by slab foaming for each type of phosphate ester from the results of the above Examples and Comparative Examples. In Table 20 below, among the phosphate esters that are solid at room temperature, for SH-800, the ether type polyol is used in the second column from the left, and the ester type polyol is used in the rightmost case. Shown in the column. The unit of the numerical values in Table 20 is mm.

FIG. 4 shows a plot based on the results shown in Table 20 with the phosphorus ratio in the polyurethane foam plotted on the horizontal axis and the combustion distance of the polyurethane foam plotted on the vertical axis.

As shown in FIG. 4, even when any phosphate ester was used, it was found that the addition of the phosphate ester shortened the combustion distance. In the case of using a phosphoric acid ester that is solid at room temperature, the phosphorous ratio in the polyurethane foam when PX-200 is used is 0.5% and 1.0%, and phosphoric acid that is liquid at room temperature. Among the esters, when the phosphorus ratio in the polyurethane foam when TCP and DAIGUARD-610 are used is 0.5%, the combustion distance is 100 mm. In these cases, the phosphate ester is added. Combustion speed is slower than the case where it did not, and combustibility is falling.

Next, Table 21 below summarizes the relationship between the phosphorus ratio and the water absorption rate in the polyurethane foam produced by slab foaming for each type of phosphate ester from the results of the above Examples and Comparative Examples. In Table 21 below, among the phosphate esters that are solid at room temperature, for SH-800, the ether type polyol is used in the second column from the left, and the ester type polyol is used in the rightmost case. Shown in the column. The unit of numerical values in Table 21 is vol%.

Next, Table 22 below summarizes the relationship between the phosphorus ratio and the water stoppage in the polyurethane foam produced by slab foaming for each type of phosphate ester from the results of the above Examples and Comparative Examples. In Table 22 below, among the phosphate esters that are solid at room temperature, for SH-800, the ether type polyol is used in the second column from the left, and the ester type polyol is used in the rightmost case. Shown in the column. The unit of numerical values in Table 22 is cmAq.

FIG. 5 shows a plot based on the results in Table 22 above, with the phosphorus ratio in the polyurethane foam plotted on the horizontal axis and the waterstop of the polyurethane foam plotted on the vertical axis.

As shown in FIG. 5, the phosphoric acid ester (CR-504L, SH-882, TCP, and DAIGUARD-, which are liquid at normal temperature, are used when the phosphoric acid ester (SH-800 and PX-200) that is solid at room temperature is used. It was found that the water-stopping property of the polyurethane foam tends to be higher than the case of using 610), and that the water-stopping property can be maintained when a solid phosphate ester is used at room temperature.

From the above results, it was found that the polyurethane foam of the present invention can be made flame retardant without causing a decrease in water stoppage by adding a phosphoric acid ester that is solid at room temperature.

In addition, it turned out that a flame retardance improves from the result of Example 1 and Examples 4-6, so that the particle size of solid phosphate ester at normal temperature becomes small. From this, in the polyurethane foam of this invention, it turned out that it is preferable that the particle size of solid phosphate ester contained at normal temperature is smaller.

Further, in Example 1, when the phosphorus ratio in the polyurethane foam was 2.5% or more, the water-stopping property was slightly lowered. In Example 3, when the phosphorus ratio in the polyurethane foam was 3.0%, the water-stopping property was reduced. The polyurethane foam of the present invention was slightly reduced and, in the same manner as in Example 3, when the phosphorus ratio in the polyurethane foam was 2.5% or more, the compressive residual strain was increased and the restorability was reduced. It was found that the phosphorus element content is more preferably 2% or less.

As described above, in the polyurethane foam of the present invention and the method for producing the same, flame retardancy can be achieved by adding a phosphoric acid ester that is solid at room temperature without causing a decrease in water stoppage. Therefore, the polyurethane foam of this invention can be used suitably for the water stop use of various products, such as a car air conditioner of a motor vehicle, a refrigerator, a prefab house, and a unit bath.

It is a schematic block diagram of a U-shaped water stop test. It is the graph which plotted the air permeability of the polyurethane foam, and the phosphorus ratio in a polyurethane foam according to the kind of phosphate ester. It is the graph which plotted the compression residual strain of the polyurethane foam for every kind of phosphate ester, and the phosphorus ratio in a polyurethane foam. It is the graph which plotted the combustion distance of the polyurethane foam for every kind of phosphate ester, and the phosphorus ratio in a polyurethane foam. It is the graph which plotted the water-stop property of a polyurethane foam for every kind of phosphate ester, and the phosphorus ratio in a polyurethane foam.

Explanation of symbols

1 U-shaped water stop test 3 U-shaped test piece 2a, 2b Acrylic board

Claims (3)

In the polyurethane foam obtained by reaction curing by adding a polyol, an organic isocyanate and an auxiliary agent, the polyurethane foam contains a phosphoric acid ester that is solid at room temperature, and is made of a polyurethane foam. Water material. 2. The waterstop material comprising the polyurethane foam according to claim 1, wherein the polyurethane foam has a phosphorus element content of 2% or less. The said polyurethane foam is a polyurethane foam sheet material which has a self-skin, The water stop material which consists of a polyurethane foam of Claim 1 or 2 characterized by the above-mentioned.

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