JP2006077055A - Termite-proofing polyurethane foam heat-insulating material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a termite-proofing heat-insulating material having both of the performances which a foamed urethane itself has and the excellent termite-proofing activity regardless of formulation with a termite-proofing agent and capable of keeping excellent effect over a long period in the polyurethane foam heat-insulating material containing the termite-proofing agent which is friendly to environment and human bodies. <P>SOLUTION: In the polyurethane foam heat-insulating material comprising a polyol component, an isocyanate component and a foaming agent, the termite-proofing agent obtained from a natural essential oil is contained in an amount of 1.0-3.0 wt.% based on total amount of the above two components and the foaming agent. The termite-proofing agent is preferably microcapsule including the natural essential oil. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polyurethane foam heat insulating material having an ant-repellent property that exhibits an extremely high repellent action against pests such as white ants despite being friendly to the environment and the human body, and retains the original performance of polyurethane foam. The present invention relates to an ant-proofing polyurethane foam heat insulating material that has an excellent ant-proofing effect and can maintain the effect over a long period of time.

Polyurethane foam is widely used as a heat-insulating material because it has higher strength than glass wool and is less likely to contain mold because it is less likely to encapsulate water.
This heat insulating material made of polyurethane foam is used for building walls, ceilings, floors, etc. as a board or by on-site construction such as spraying or injecting a urethane raw material (liquid) to a construction site.

However, compared to mortar (such as a covering material that covers heat insulation) and concrete (such as foundations such as cloth foundations and solid foundations), plastic foams such as urethane are known to be easily damaged by white ants. It has been.
Moreover, when used as a thermal insulation for buildings, the interior is warm due to its own thermal insulation effect, so it is a perfect intrusion route for white ants as well as other pests. Say)
Therefore, the damage caused by white ants in the polyurethane foam insulation is still a problem that cannot be ignored.

  As a general countermeasure against white ants, conventionally, chemicals have been sprayed on the soil surface or the chemicals have been infiltrated into the wood, but heat insulation is one of the intrusion routes to the building from the outside. It is necessary to take measures against white ants as well, and if the heat insulating material has a function of preventing ants, formation of ant roads in the heat insulating material can be prevented.

Up to now, as a method for imparting an ant-proof function to a heat-insulating material made of polyurethane foam, for example, a polyurethane foam containing an ant-proofing agent and bitumen (Japanese Patent Laid-Open No. Sho 64-16864) or a microencapsulated pest Alternatively, an insect-insulating board (Japanese Patent Laid-Open No. 4-20631) to which a moth repellent is added has been proposed.
However, in these previously proposed ant-repellents and repellents, the ant-preventive (insect) effect is mentioned, but no pursuit has been made for non-toxicity to the environment and the human body.

On the other hand, Japanese Patent Application Laid-Open No. 2004-99536 discloses a pest repellent active adhesive or ink to which a highly safe natural product-derived repellent is added, and an example of using this repellent in a polyurethane foam. Is not listed.
In particular, when this highly safe natural product-derived repellent is blended in polyurethane, there is a concern that the urethane reaction is inhibited and a desired foam cannot be obtained, or that the obtained foam may shrink. .
With regard to such concerns, the above publication does not teach at all, and the above repellent is used in order to combine the inherent foaming properties (heat insulation properties) and durability of polyurethane with an excellent ant-repellent effect. Sufficient examination has not been made yet as to how it should be blended in the polyurethane foam.
Japanese Unexamined Patent Publication No. 64-16864 JP-A-4-20631 JP 2004-99536 A

  Therefore, in the present invention, even if a natural essential oil-derived anti-anticide is used, the urethane reaction is not inhibited, and the desired polyurethane foam can be obtained without shrinkage of the resulting foam. It is an object of the present invention to pursue a polyurethane foam technology that does not cause a decrease in temperature, and to provide a polyurethane foam heat insulating material that can maintain an environment-friendly and human-friendly ant protection over a long period of time.

In order to solve the above-mentioned problems, the present inventors used natural essential oil excellent in white ant repellent activity as a non-toxic ant repellent that is highly safe for the environment and the human body. It has been found that an ant-proofing heat insulating material having both the original performance of polyurethane and an excellent ant-proofing effect can be obtained by setting the blending amount to be optimal with respect to the entire foam raw material liquid.
As a result of further investigations under this knowledge, the present inventors have not only improved the sustained release property by encapsulating the above-mentioned antifungal agents in microcapsules using a specific shell, but also urethane. It has been found that natural essential oils that easily inhibit the reaction and natural essential oils that easily lose their ant-preventing activity due to the heat of reaction during the urethane reaction can be used.
And in the course of these studies, these various natural essential oils are blended in the polyol component instead of the isocyanate component, so that the inhibition of the urethane reaction can be minimized or eliminated, and the foaming obtained It has also been found that body contraction can be minimized or eliminated.

The present invention has been made on the basis of these findings, and is a polyurethane foam heat insulating material obtained from a polyol component, an isocyanate component, and a foaming agent. The gist is an ant-proof polyurethane foam heat-insulating material, which is contained in an amount of 1.0 to 3.0% by weight with respect to the total amount of the agent.
At this time, the termite-proofing agent may be a microcapsule containing natural essential oil, and the termite-proofing agent is preferably added to the polyol component.

The polyol in the polyol component of the present invention is not particularly limited as long as it is a polyol having one or more hydroxyl groups in the molecule, and is used for production of ordinary polyurethane foam such as polyester polyol, polyether polyol, polymer polyol and the like. Among them, polyester polyols and polyether polyols can smoothly react with the following isocyanate components (that is, urethane reactions) despite the addition of a natural essential oil-derived anti-anticide. Thus, it can be preferably used from the viewpoints of obtaining a polyurethane foam having the desired performance, availability, and cost.
These polyols can be used either alone or in admixture of two or more by an appropriate combination.

  In addition to the above polyol, the polyol component in the present invention includes water, a flame retardant, a foam stabilizer, a catalyst, a dye, a plasticizer, a filler, a crosslinking agent, an antifungal agent, a thickener, a reducing agent, if necessary. Various additives such as a sticking agent, a dispersing agent, and a surfactant are appropriately mixed and adjusted.

As the isocyanate in the isocyanate component of the present invention, tolylene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), crude MDI, hexamethylene diisocyanate (HMDI), xylylene diisocyanate (XDI), hydrogenated TDI, hydrogenated MDI, meta Xylylene diisocyanate and the like used for the production of ordinary polyurethane foams are used. Among them, MDI reacts with the above polyol component (in spite of the addition of a natural essential oil-derived termiticide) ( That is, it can be preferably used in terms of the ability to obtain a polyurethane foam having the desired performance by smoothly proceeding the urethane reaction, the performance of the product foam, the availability, and the cost.
In addition to the above-mentioned isocyanate, this isocyanate component may be a flame retardant, a foam stabilizer, a catalyst, a dye, a plasticizer, a filler, a cross-linking agent, an antifungal agent, a thickener, or a thinning agent. Various additives such as a dispersant and a surfactant are appropriately blended and adjusted.

  As the foaming agent, known foaming agents such as chlorofluorocarbon gas, carbon dioxide gas, hydrocarbon gas such as Proban and pentane, etc. can be used. In consideration of environmental problems, it is particularly preferable to use hydrocarbon gas.

  In the present invention, the blending ratio of the above polyol component, isocyanate component, and foaming agent may be the same as that in an ordinary polyurethane foam heat insulating material, specifically, 50: 100: 1 to 150 by weight ratio. : 100: 30, preferably 70: 100: 2 to 90: 100: 15 is suitable.

  The ant-proof heat insulating material of the present invention mainly comprises the polyol component, the isocyanate component, and the foaming agent in the above ratio (hereinafter, these two components and the foaming agent are also collectively referred to as “polyurethane raw material”). As a raw material, a mixture of this polyurethane raw material and a termite-preventing agent, which will be described later, is sprayed onto the face material, for example, so that the polyol component and the isocyanate component react on the face material (that is, a urethane reaction occurs) to prevent A polyurethane foam containing an ant agent and other appropriate additives can be obtained in close contact with the face material.

  As this face material, a known face material used as a face material of a heat insulating material such as paper such as kraft paper, a synthetic resin plate, a synthetic resin film, a metal plate, a metal foil, or a gypsum board can be used.

In the present invention, the ant-proof heat insulating material is a natural essential oil-derived ant-proofing agent in an amount of 1.0 to 3.0% by weight based on the total amount of polyurethane raw materials (polyol component, isocyanate component, and foaming agent). It is important to include so that
If the amount of ant preventive agent is too small, not only the desired white ant repellent effect cannot be obtained, but also when the ant proofing heat insulating material of the present invention is used as a heat insulating material for general houses, office buildings or residential buildings, etc. May not be able to maintain the white ant repellent effect over the period guaranteed by the contractor for ordinary buildings (usually 30 years for ordinary houses). Due to the natural oil-derived anti-anticide, it may cause adverse effects such as reaction inhibition and foam shrinkage.

In the present invention, the use of a natural essential oil-derived anti-anticide increases the safety to the environment and the human body, and there is no concern about toxicity.
In addition, natural essential oils generally have a large molecular weight, and once they are chemically or physically bonded to a urethane foam, they are difficult to escape, and there is no risk of escaping, and their volatility is gradual. And exhibits excellent white ant repellent effect over a long period of time.

  The natural essential oil is not particularly limited as long as it has repellent activity against pests such as white ants. Oil, thyme white oil, penny royal oil, neem oil and the like, and any one or more of these natural essential oils may be used in appropriate combination.

With respect to the method of adding the anti-anticide, it is necessary to add and mix it into the polyurethane raw material liquid at least before the foaming reaction in order to uniformly disperse the anti-anticide in the heat insulating material.
In the present invention, it is preferable to add the termite-proofing agent to the polyol component instead of the isocyanate component at once or continuously with mixing and stirring.
That is, the polyol component and the terminator are well mixed and stirred, and the terminator-containing polyol component, the isocyanate component, and the foaming agent are continuously mixed, reacted, and foamed.
By doing in this way, inhibition of the urethane reaction by the termite-proofing agent obtained from natural essential oil is hardly caused, and shrinkage of the obtained foam is hardly caused.

  The foaming agent may be added to the polyol component in advance and mixed with the above-described flame retardant and catalyst, or may be added and mixed when mixing the polyol component and the isocyanate component.

Further, in the present invention, the termite-proofing agent may be a microcapsule containing natural essential oil.
By microencapsulating the ant-proofing agent, the ant-proofing effect of the heat insulating material can be maintained over a long period of time, and the sustained release property can be further enhanced.
In addition, depending on the material used for the microcapsule shell, natural essential oils that inhibit the urethane reaction (have active hydrogen that reacts with the polyol group) and natural essential oils that are vulnerable to the heat of urethane reaction should also be used as anti-anticides. Is possible.

The material of the shell of the microcapsule may be inorganic or organic, but a known material of an organic polymer (synthetic resin) is preferably used from the viewpoints of manufacturing cost, availability, and handling.
Above all, the natural essential oil that not only prevents or eliminates the inhibition of the urethane reaction, is not damaged by the heat during the urethane reaction, and contains the product insulation as the insulation of the building. For example, melamine resin, polyamide resin, polyethylene resin, nylon resin, acrylic resin and the like are preferably used from the viewpoint of suitably releasing the derived ant preventive.
Depending on the type of these shells, microcapsules encapsulating the above-mentioned termite-proofing agent may be produced by a known method.

  The particle size of the microcapsules is not particularly limited, but if the particle size is too small, it may be difficult to manufacture or handle the microcapsule itself. If it is too large, uniform mixing with the polyurethane raw material liquid may occur. Work becomes difficult, especially in the present invention, the urethane reaction may be hindered, and it may be difficult to obtain a heat insulating material having the original performance of polyurethane foam. It is preferably about 0.5 to 10 μm.

Further, the distribution of the microcapsules in the polyurethane foam heat insulating material is preferably in a uniform state, as is the case with the termite preventer that is not microencapsulated.
Furthermore, in the present invention, an aggregation / sedimentation inhibitor may be used in order to prevent aggregation and sedimentation of the microcapsules. As this aggregation / sedimentation inhibitor, known ones such as acrylic acid polymers, proteins, inorganic substances and the like can be used.
These agglomeration / sedimentation inhibitors are mixed with water or an organic solvent to form an agglomeration / sedimentation inhibitor solution, and microcapsules containing an antifungal agent are added to the agglomeration / sedimentation inhibitor solution, mixed, and dispersed. A microcapsule dispersion (suspension) may be prepared and added to the polyurethane raw material liquid.

The ant-proof heat insulating material of the present invention can be used as a board-shaped molded plate or as a site construction method.
Moreover, there is no restriction | limiting in particular about the thickness of the ant-proof heat insulating material in this invention, The thickness about the normal polyurethane foam heat insulating material, for example, about 10-75 mm is generally used.

In the present invention, whether or not the original performance of urethane foam is maintained is based on the presence or absence of shrinkage in the polyurethane foam obtained by adding an anti-anticide.
After foaming by urethane reaction, the degree of shrinkage after standing at -20 ° C or + 50 ° C under normal pressure for 24 hours (1 day) is observed with the naked eye, or the density is measured. If there is no change, or if the change is up to about 10%, the contraction is practically absent. If a change exceeding 10% is observed, the contraction is practically contracted.

And as another standard of whether the original performance of urethane foam is maintained, it shall be judged by the measurement of the heat insulation and durability of the polyurethane foam obtained by adding the termite-proofing agent.
For insulation, for example, a gas burner set in front of an upright polyurethane foam board is ignited, the ambient temperature is measured, and the difference between this temperature and the temperature on the opposite side of the polyurethane foam (the side without the gas burner) is calculated. The determination is made by comparing the polyurethane foam added with the anti-anticide and the polyurethane foam without addition.
Durability can be measured by, for example, measuring the density of polyurethane foam added with a natural essential oil-derived antifungal agent and non-added polyurethane foam after standing for 1 week in a sunny outdoor outdoor in the summer, Alternatively, an experiment similar to the above-described measurement of heat insulation is performed, and the heat insulation is compared with that before being left for one week.

The ant-proof heat insulating material of the present invention combines the inherent performance of polyurethane foam with an excellent ant-proofing effect despite the incorporation of an ant-proofing agent that is friendly to the environment and the human body, and it also prevents the ant-proofing over a long period of time. Ants can be maintained.
For this reason, the ant-proof heat insulating material of this invention can be used conveniently for the wall body (outside heat insulating material, filling heat insulating material), a ceiling, a floor, etc. of a building.

Examples 1-2 and Comparative Examples 1-4
A polyol and other additives were mixed at the ratio shown below to prepare a polyol component (hereinafter also referred to as “premix resin”).
To this premix resin, an anti-anticide (trade name “XEI PRO / SOL” manufactured by Kiseitec Co., Ltd.) was added to each of the chemicals (total amount of premix resin, foaming agent and isocyanate) as shown in Table 1. The mixture was stirred well so as to disperse uniformly.
Next, the foaming agent was added at the ratio shown below, and stirred until well blended. Subsequently, the isocyanate was added at the ratio shown below, mixed and stirred, and sprayed with the face material (120 g / m ² of kraft). Paper) and foamed to obtain an ant-proof heat insulating material having a polyurethane foam part thickness of 50 mm.

(Premix resin raw material)
4 types of polyol * 1 111.5 parts by weight foam stabilizer * 2 1.5 parts by weight 3 types of catalyst * 3 1.26 parts by weight water 2 parts by weight (foaming agent)
Foaming agent * 4 23 parts by weight (isocyanate component)
Isocyanate * 5 182 parts by weight

* 1: (1) Asahi Glass Urethane 80% Polyether Polyol 20% Polyester Polyol Mixture (Hydroxyl Value 780), (2) Asahi Glass Urethane 78% Polyester Polyol 20% Polyester Polyol and Polymer Polyol 2% mixed product (hydroxyl value 470), (3) Dainippon Ink and Chemicals saturated polyester resin (hydroxyl value 845), (4) Sumika Bayer Urethane polyether polyol (hydroxyl value 460), Use in equal amounts * 2: Silicone foam stabilizer (trade name “L5420” manufactured by Nihon Unicar)
* 3: (1) Catalyst A; pentamethylenediethylenetriamine (trade name “Kao Riser No. 3” manufactured by Kao Corporation), (2) Catalyst B; tris (dimethylaminopropyl) hexahydro-S-triazine (product manufactured by Air Products) (“Polycat 41”), (3) Catalyst C; Lead octylate (trade name “Pb-Oc” manufactured by Dainippon Ink & Chemicals, Inc.)
* 4: Cyclopentane (Nippon Zeon Corporation)
* 5: Polymec MDI (methylene diphenyl diisocyanate) (manufactured by Sumika Bayer Urethane Co., Ltd.)

  The heat insulating properties, shrinkage properties, ant-repellent properties, and durability of the obtained heat insulating materials were evaluated as follows, and the results are shown in Table 1.

(1) Thermal insulation: Set the thermal insulation upright, ignite the gas burner installed 10 cm away from this thermal insulation, and on the side opposite to the ambient temperature of the gas burner installation side (on the side without the gas burner) The difference with the ambient temperature on the side where the face material is present was compared and evaluated according to the following criteria.
○: Before ignition of the gas burner, the ambient temperature on the gas burner installation side of the heat insulating material and the ambient temperature on the opposite side (the side without the gas burner and the side where the face material is present) were measured, and 10 minutes passed after ignition. At this point, the ambient temperature is measured again, and the ambient temperature on the opposite side does not change before or after ignition of the gas burner, or is less than 10 ° C even if there is a change.
X: The ambient temperature on the opposite side is raised by 10 ° C. or more from the temperature before the gas burner ignition.
(2) Shrinkage: After leaving at −20 ° C. under normal pressure for 24 hours (1 day) and + 50 ° C. under normal pressure for 24 hours (1 day), the density was measured and evaluated according to the following criteria.
○: There is no change in density and therefore no shrinkage is observed as compared with that before leaving.
X: Density is higher than that before leaving, and thus shrinkage is observed.
(3) Ant protection (perforation degree): Regarding the protection against ants, the following test was conducted in accordance with “Anticide effect test for soil treatment ant protection agent (Japan Wood Preservation Association Standard No. 13 1992)”. A test was conducted to determine the degree of perforation.
As shown in FIG. 1, 200 termite termite ants and 20 soldier ants are placed in A (a container containing 45 g of untreated soil (water 20%)), and inside B (a glass tube containing ant-proof polyurethane foam). Observe the progress of the termites on the surface, and measure the degree of perforation according to the following criteria.
Perforation degree 0: No perforation of the ant-proof polyurethane foam is observed.
Perforation degree 1: Perforation distance is less than 1 cm.
Perforation degree 2: Perforation distance is less than 2 cm.
Perforation degree 3: Perforation distance is less than 3 cm.
Perforation degree 4: Perforation distance is less than 4 cm.
Perforation degree 5: A perforation distance of 4 cm or more.
(4) Durability: Standing vertically with the polyurethane foam facing south in a sunny outdoor outdoors in summer, and standing in this state for 1 week, the heat insulation of (1) above and the shrinkage of (2) above , And the same experiment as the evaluation of the ant-proof property of (3) above was performed, and the evaluation was performed according to the following criteria.
○: In the evaluation of the above (1) heat insulating property, the above (2) heat insulating property, and the above (3) ant proof property, all are ○.
(Triangle | delta): In said (1) heat insulation, the heat insulation of said (2), and the evaluation of the ant-proof property of said (3), at least 1 is a thing of x.
X: In the evaluation of the above (1) heat insulation, the heat insulation of (2) above, and the ant-proof property of (3) above, all are x.

  As a result, when the addition ratio of the termite-proofing agent exceeds 3.0% by weight with respect to the total amount of the polyurethane raw material liquid, a sufficient ant-proofing effect can be obtained, but the polyurethane foam is shrunk and durable. However, when the amount is less than 1.0% by weight, the polyurethane foam does not shrink and the durability is sufficient, but the ant-proof effect is insufficient.

The ant-proof heat insulating material of the present invention combines the inherent performance of polyurethane foam with an excellent ant-proofing effect despite the incorporation of an ant-proofing agent that is friendly to the environment and the human body, and it also prevents the ant-proofing over a long period of time. Ants can be maintained.
The ant-proof heat insulating material according to the present invention having such excellent characteristics is suitable as a heat insulating material for buildings, and is suitably used for walls (outer heat insulating materials, filled heat insulating materials), ceilings, floors, etc. can do.

It is explanatory drawing which showed the test method of ant-proof property.

Explanation of symbols

A Container with 45 g of untreated soil (water 20%) B Glass tube with ant-proof polyurethane foam obtained C Container with red pine wood

Claims (3)

A polyurethane foam heat insulating material obtained from a polyol component, an isocyanate component, and a foaming agent,
An ant-proofing polyurethane foam heat insulating material comprising a natural essential oil-derived ant-proofing agent in an amount of 1.0 to 3.0% by weight based on the total amount of the two components and the foaming agent.   The ant-proofing polyurethane foam heat insulating material according to claim 1, wherein the ant-proofing agent is a microcapsule containing natural essential oil. 3. An ant-proofing polyurethane foam heat insulating material according to claim 1 or 2, wherein an ant-proofing agent is added to the polyol component.

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