JP2019015097A - On-site foamed urethane type termite prevention heat insulation material, its evaluation method, and raw material liquid for termite prevention heat insulation material - Google Patents

Abstract

To provide a heat insulation material which maintains termite prevention for a long term with high termite prevention performance and environment-friendly and human-friendly termite prevention.SOLUTION: A termite prevention heat insulation material is an on-site foamed urethane type termite prevention heat insulation material comprising a foam obtained by mixing a first liquid and a second liquid. The first liquid is an isocyanate component liquid and the second liquid is a mixture of a polyol component liquid, a permethrin solution and an aqueous borate solution. For the solvent constituting the permethrin solution, it is preferable to use a flame retardant usable for the polyol component liquid.SELECTED DRAWING: Figure 2

Description

  The present invention relates to an in-situ foamed urethane type ant-proof heat insulating material using polyurethane foam imparted with an ant-proofing effect, an evaluation method thereof, and a raw material liquid for the ant-proof heat insulating material.

As a method for imparting an insecticidal effect to a heat insulating material used for heat insulation of a house, techniques described in the following patent documents are known.
In Patent Document 1, an insect repellent having a melting point of 35 ° C. to 150 ° C. is mixed in at least one raw material liquid of foaming raw material liquid, heated and melted, and then cooled to recrystallize the insect repellent in a crystalline state. A method is disclosed in which an insecticide-containing raw material liquid that has been dispersed is mixed with the other foaming raw material liquid to perform foam molding.
According to the above method, the insect repellent can be uniformly dispersed in the foam without using an insect repellent solvent (such as toluene).

  In addition, Patent Document 2 discloses an insect-proof heat insulating material containing permethrin, a synergist, and a repellent in a synthetic resin foam, and the concentration of permethrin contained in the synthetic resin foam is 0. A point of 1 to 3% by weight is disclosed.

Japanese Patent No. 4156552 Japanese Patent No. 5334539

Based on these conventional techniques, the present invention aims to solve at least one of the following problems to be solved.
(1) To provide an ant-proof heat insulating material with higher ant-proof performance
(2) Maintaining ant-proofing properties that are kind to the environment and the human body over a long period of time
(3) The urethane reaction is not inhibited, the foam does not shrink, and the heat insulation performance is not affected during the addition of the termite-proofing agent.
(4) To save labor as much as possible in the manufacturing process.
(5) It is possible to estimate how the ant-proof effect has changed when the heat insulating material has changed over time.

1st invention of this application made to solve said subject is an in-situ foam urethane type ant-proof heat insulating material which consists of a foam by mixing the 1st liquid and the 2nd liquid, and the 1st liquid is It is an isocyanate component liquid, and the second liquid is characterized in that the polyol component liquid contains permethrin and borate.
The second invention of the present application is the first invention, wherein the second liquid is a polyol component liquid, a permethrin solution containing a flame retardant that can be used as the polyale component liquid, a borate aqueous solution, It is the liquid mixture of these.
The third invention of the present application is characterized in that, in the first invention or the second invention, the foaming agent is hydrofluoroolefin (HFO) or water (H20).
The fourth invention of the present application is a method for evaluating an in-situ foamed urethane type ant-proof heat insulating material, wherein a test body made of the ant-proof heat insulating material of any one of the first to third inventions is measured at an indoor temperature. Aging is performed for a predetermined time in a test chamber set at 81 ° C., and the performance of the ant-repellent effect is estimated according to the remaining amount of permethrin in the test specimen.
In addition, the fifth invention of the present application is a raw material liquid for mixing with a first liquid containing an isocyanate component liquid to produce an in-situ foamed urethane type ant-proof heat insulating material, which is a polyol component liquid and the polyol component. It is a mixed solution of a permethrin solution containing a flame retardant that can be used as a solvent and a borate aqueous solution.

According to the present invention, at least one of the following effects can be achieved.
(1) By adding two kinds of components (permethrin, borate) having an ant-proof effect, a high ant-proof performance can be imparted to a heat insulating material made of polyurethane foam. More specifically, since permethrin acts as a fast-acting ant-preventing agent and borate acts as a slow-acting ant-preventing agent, the ant-proofing effect can be exhibited for a long time.
(2) Since permethrin and borate are not VOC substances or poisonous deleterious substances, they do not affect the human body and the environment even if they are present in the urethane resin.
(3) By using a permethrin solution containing a flame retardant that can be used as a polyale component liquid as a solvent, adverse effects such as inhibition of urethane reaction, shrinkage of foam, and deterioration of heat insulation performance can be avoided.
(4) Since the second liquid can be manufactured only by the operation of mixing the liquids, the manufacturing process is simple.
(5) The ant-proof effect after aging can be easily estimated from the residual amount of permethrin after the accelerated deterioration test.

The table | surface which shows the composition of each sample of the foam in the water foaming which concerns on this invention. The table | surface which shows the mortality of each sample which concerns on FIG. The table | surface which shows the mortality of each sample after an accelerated deterioration test about the foam by water foaming. The comparison table which shows the physical property of the comparative example and case 6 which concern on FIG. The table | surface which shows the composition of the foam in HFO foaming which concerns on this invention. The table | surface which shows the mortality of each sample which concerns on FIG. 6 is a comparison table showing physical properties of the comparative example and the case 13 according to FIG.

  Embodiments of the present invention will be described below with reference to the drawings.

<1> Outline The ant-proof heat insulating material according to the present invention is made of a field blown type rigid urethane foam used as a heat insulating material for a wooden detached house or RC building.
The ant-proof heat insulating material according to the present invention is characterized by the combined use of permethrin and borate, which are excellent in white ant repellent activity, as a non-toxic ant-proofing agent with high safety to the environment and the human body.
And, by making this ant-proofing agent the optimum blending amount with respect to the entire raw material liquid of polyurethane foam, it is possible to obtain an ant-proofing heat insulating material that combines the original performance of polyurethane and the excellent ant-proofing effect. I found it.

  As a result of further investigation under this knowledge, the present inventor stored the produced urethane foam under a certain aging condition, and chemically analyzed each component of the anti-anticide in the urethane foam after a certain period of time. By doing so, it was found that the ant-proof effect after aging can be estimated from the elapsed time under the aging condition.

And, in the course of these studies, can these inhibitory ingredients be added to the second liquid side polyol component liquid instead of the first liquid side isocyanate component liquid to minimize inhibition of the urethane reaction? It was possible to eliminate the use of foam, and it was possible to construct it in a polyurethane production facility that can be foamed on-site, and the performance of the resulting foam was found to be almost equivalent to the performance of a foam that does not contain an anti-anticide. .
Details of these features will be described below.

<2> First liquid The first liquid is a raw material liquid containing an isocyanate component.
Since a well-known isocyanate component liquid can be used for the 1st liquid, detailed description is abbreviate | omitted.

<3> Second liquid The second liquid is a raw material liquid containing a polyol component.
The second liquid contains permethrin and borate, which are non-toxic anti-anticides that are highly safe for the environment and the human body relative to known polyol component liquids.

<3.1> Permethrin Permethrin is a kind of pyrethroid insecticide and is a compound represented by the molecular formula C21H20Cl2O3.
Permethrin has low toxicity to human livestock (but high toxicity to cats and fish) and is widely effective against insects and mites, so it can be used for hygiene pest control, insect control, pesticides, veterinary medicines and medicines. Widely used.

<3.1.1> Permethrin solution Permethrin is made into a solution (permethrin solution) using a solvent while heating to a melting point (34 ° C.) or higher.
In the present invention, PEL-10: permethrin (3-phenoxybenzyl = 3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate) 10%, methanol 3%, flame retardant, etc. 87% is used.

In addition, it is thought that it is more suitable to use the flame retardant which can be used for a polyol component liquid for the solvent for melt | dissolving permethrin.
This is because a flame retardant that can be used in the polyol component liquid is unlikely to have an adverse effect on the physical properties of the foam before and after the addition of the termite-proofing agent.
Therefore, the flame retardant used as a solvent for dissolving permethrin may be a flame retardant actually used in the polyol component liquid, or there is no hindrance to use as a polyol component liquid although it is not actually used. Any flame retardant may be used.
Known flame retardants that can be used as polyol component liquids for the production of polyurethane foam include halogenated phosphoric acid esters and phosphoric acid esters, and the halogenated phosphoric acid esters include TCPP (tris (β-chloropropyl) phosphate. ) Etc. are included.

<3.2> Borate Borate is a compound represented by a generic name including a salt of boric acid ((B (OH) 3)), or a salt of boric acid such as metaboric acid or polyboric acid. It is.

<3.2.1> Borate aqueous solution Borate can maintain a stable state by dissolving in water to form an aqueous solution.
In the present invention, the molecular formula Na2B8O13 · 4H2O (disodium octaborate tetrahydrate) used as a wood preservative is used as the borate.

<3.3> Production Example The second liquid can be produced by mixing and stirring a predetermined amount of permethrin solution and borate salt aqueous solution with a known polyol component liquid.
For example, when forming a foam using water as a foaming agent, a permethrin solution and an aqueous borate salt solution are added to a polyol component liquid, and mixed and stirred using a stirrer or the like to spray the second liquid on site. Can be produced on site.
On the other hand, when HFO is used as a foaming agent, foaming is likely to occur when mixing and stirring on site, so that it is preferable to produce in advance at the factory.

<4> Foam (Table 1)
The first liquid and the second liquid described above are mixed and sprayed by a spray device including a foaming machine and a spray gun to form a foam.
An example of foam molding conditions is shown in Table 1.

<5> Experimental example 1 (water foaming)
Each test was conducted by preparing samples of water foams having different permethrin concentrations and borate concentrations by changing the composition of the second liquid with respect to the ant-proof heat insulating material when water was used as the main foaming agent.

<5.1> Insecticidal test <5.1.1> Composition of water foam (FIG. 1)
In FIG. 1, the basic composition of the 1st liquid (isocyanate component liquid) and the 2nd liquid (polyol component liquid) which comprise the water foam used for an insecticidal test is shown.
The water foam according to the present composition is in a state where neither permethrin nor borate is added, and is used as a comparative example in FIG. 2 described later.

<5.1.2> Test procedure The outline of the insecticidal test method for each sample is as follows.
First, a sample cut to a diameter of 9 cm was laid on a resin petri dish, 5 cc of water was placed in the test specimen and allowed to stand for 1 day, excess water was removed with water-absorbing paper, and filter paper as feed was placed in this container. , 10 specimens of insects (termite ants) were released.
This was put together with a resin petri dish containing saturated saline in an airtight container for food preservation (approximately 18 × 25 × 4 cm, capacity 1.8 L) and allowed to stand in a high temperature period of 25 ° C.
Observe 5 times after 1 day, 3 days, 7 days, 14 days, and 21 days, and if it is difficult to judge whether it is life or death, touch it gently with a face brush to stimulate it, and An individual who was alive and alive but could not walk normally, or an individual who was upside down, was knocked down. In addition, the state was observed every 3 to 4 days during the test period, and when the filter paper was found to be dry, water was dripped in a timely manner.

<5.1.3> Test results (mortality) (Fig. 2)
FIG. 2 shows the transition of the death rate of each sample according to FIG.
In this example, PEL-10: permethrin (3-phenoxybenzyl = 3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropane) was used as a permethrin solution for the polyol component liquid having the composition shown in FIG. Carboxylate) 10%, methanol 3%, flame retardant and other 87% are used, and LEN75B: disodium octaborate 7.5% aqueous solution is used as the borate aqueous solution.
In the comparative example, neither permethrin nor borate is added.

When the comparative example and case 2 are compared, there is a large increase in the mortality rate after one day depending on the presence or absence of permethrin, and permethrin has an immediate effect. In all cases, the decrease in the weight of the specimen is very small, and the damage to the heat insulating material is small.
Comparing the comparative example with Cases 1 and 3, depending on the presence or absence of borate, there is a large increase in the death rate especially after 14 days, and the borate has a delayed effect.
When the comparative example and case 4 are compared, it is recognized that both the immediate effect and the delayed effect are exhibited in the nematode effect by the combined use of permethrin and borate.
Comparing Case 4 and Case 5, in both cases, when permethrin and borate were used in combination, an increase in the mortality rate was observed in the case where the addition amount was larger.
In addition, none of the cases adversely affected the performance as a foam.

Therefore, at least in the foam obtained by mixing and foaming each liquid, it has been found that a more suitable ant protection effect can be obtained when each concentration of permethrin and borate is 0.025% by weight or more. .
In addition, in the range which does not have a bad influence on the characteristic as a heat insulating material of a foam, the upper limit of each density | concentration of permethrin and borate seems to be about 0.5 to 1.0 weight%.

<5.2> Durability test (Fig. 3)
Next, a durability test using an accelerated deterioration test will be described.

<5.2.1> Test Procedure As in FIG. 1, the second liquid used in this test was PEL-10: permethrin (3-phenoxybenzyl = 3- (2,2-dichlorovinyl) -2 as a permethrin solution. , 2-dimethylcyclopropanecarboxylate) 10%, methanol 3%, flame retardant and other 87% are used, and as a borate aqueous solution, LEN75B: 7.5% aqueous solution of disodium octaborate hydrate is used. Yes.
Each sample was subjected to an accelerated deterioration test with varying aging time in a temperature-controlled room set at 81 ° C., component analysis and insecticidal test were performed on each sample after the aging time passed, and permethrin and boric acid The residual amount and the death rate were measured.
In Case 7, the aging time is 184 hours, and accelerated deterioration corresponding to 12 years is performed in an environment of 25 ° C.
Similarly, in case 8, the aging time was 328 hours (accelerated deterioration for 20 years), and in case 9, the aging time was 480 hours (accelerated deterioration for 30 years).

<5.2.2> Test Results As shown in FIG. 3, as the aging time becomes longer, the decrease rate of the residual amount of permethrin and the decrease rate of the mortality rate after 21 days were almost similar.
In addition, since the residual amount of boric acid (B) has already decreased to 32% at the stage of Case 7 and then remains at 20% in Cases 8 and 9, it approximates the rate of decrease in the mortality after 21 days. The result was not reached. None of these specimens showed any decrease in the weight of the specimen, and no damage to the heat insulating material was observed.

  Therefore, at least in the ant-proof heat insulating material according to the present invention, when evaluating the presence or absence of the ant-proof effect after a long period of time, the ant-proof effect is estimated by the remaining amount of permethrin after the accelerated deterioration test. It turns out that you can.

<5.3> Comparison of physical properties (FIG. 4)
FIG. 4 shows a comparison table showing the physical properties of the comparative example and case 6 according to FIG.
As shown in FIG. 4, even in the case of case 6, there was no adverse effect on the density, thermal conductivity, and combustibility.

<6> Experimental example 2 (HFO foaming)
Next, with respect to the termite-proof heat insulating material when HFO was used as the main foaming agent, samples with different compositions of the second liquid were prepared and tested.

<6.1> Insecticidal test First, an insecticidal test conducted by preparing a plurality of samples in which the composition of the HFO foam was changed will be described.

<6.1.1> HFO foam composition (FIG. 5)
In FIG. 1, the basic composition of the 1st liquid (isocyanate component liquid) and the 2nd liquid (polyol component liquid) which comprise a water foam is shown.
The HFO foam according to the present composition is in a state where neither permethrin nor borate is added, and is used as a comparative example in FIG. 6 described later.

<6.1.2> Insecticidal test method The procedure of the insecticidal test method is the same as in Experimental Example 1 described above, and a description thereof is omitted.

<6.1.3> Test results (Dead rate (FIG. 6))
FIG. 6 shows the transition of the death rate of each sample according to FIG.
As shown in FIG. 6, in this example, PEL-10: permethrin (3-phenoxybenzyl = 3- (2,2-dichlorovinyl)-as a permethrin solution with respect to the polyol component liquid having the composition shown in FIG. 2,2-dimethylcyclopropanecarboxylate) 10%, methanol 3%, flame retardant and other 87% are used, and LEN75B: disodium octaborate hydrate 7.5% aqueous solution is used as the borate aqueous solution. ing.
It should be noted that increasing the proportion of water in the borate aqueous solution may hinder foaming by HFO.
In the comparative example, neither permethrin nor borate is added.

When the comparative example and cases 10 to 12 are compared, no significant change is observed in the death rate until 7 days as the permethrin concentration increases, but an effect is observed in the death rate + knockdown rate after 14 days. .
Comparing Case 12 and Case 13, depending on the presence or absence of borate, there is a large increase in the death rate especially after 14 days, and borate has a delayed effect.
Referring to Case 14, when the permethrin concentration increases to 0.5% by weight, the cell contraction can be confirmed with a slight roughness, but an increase in the mortality rate is observed after 3 days, and the dead insects until 21 days later. It is recognized that the effect continues.
Therefore, in case 15, if it is further used in combination with borate, it seems that an increase in the death rate after 14 days can be expected.
In addition, all of these samples showed a small decrease in the weight of the specimen and almost no damage to the heat insulating material was observed.
Although not shown in FIG. 6, when the permethrin concentration was over 1.0% by weight, the foam cell was rough and the shrinkage was large, which was not suitable as a heat insulating material.

Therefore, in the HFO foam according to the present example, if the permethrin concentration is 0.3% by weight or more and less than 1.0% by weight and the borate concentration is 0.05% by weight or more, a more suitable ant protection It seems to be effective.
In addition, in the range which does not have a bad influence on the characteristic as a heat insulating material of a foam, the upper limit of borate density | concentration is considered to be about 0.5 to 1.0 weight%.

<6.2> Comparison of physical properties (FIG. 7)
FIG. 7 shows a comparison table showing the physical properties of the comparative example and the case 13 according to FIG.
As shown in FIG. 7, even in the case of Case 13, there was no adverse effect on the density, thermal conductivity, adhesive strength, compressive strength, moisture permeability, and combustibility.

<7> Summary Thus, according to the ant-proof heat insulating material according to the present invention, by using together two kinds of components (permethrin, borate) having an ant-proofing effect, the heat-insulating material made of polyurethane foam is high. Ant performance can be imparted.

<8> Other In addition, the manufacturing method of the ant-proof heat insulating material according to the present invention may be mechanical stirring molding, high-pressure injection molding, low-pressure injection molding, aerosol type molding, etc. It seems that the same results as those of the above-described examples can be obtained.
Needless to say, similar products may be used in representative compositions and components in preparing each foam.
In this invention, the performance of the termites was tested with respect to the insecticidal performance, but it seems that similar performance can be obtained not only for ants such as Yamato termites and black ants, but also for cockroaches and ticks.

Claims (5)

An in-situ foam urethane type ant-proof heat insulating material comprising a foam by mixing the first liquid and the second liquid,
The first liquid is an isocyanate component liquid,
The second liquid is characterized in that the polyol component liquid contains permethrin and borate.
In-situ urethane-type ant-proof insulation. The second liquid is a mixed liquid of a polyol component liquid, a permethrin solution using a flame retardant that can be used as the polyol component liquid, and an aqueous borate solution,
The in-situ foam urethane type ant-proof heat insulating material according to claim 1. The foaming agent is hydrofluoroolefin (HFO) or water (H20),
The in-situ foam urethane type ant-proof heat insulating material according to claim 1 or 2. It is an evaluation method for in-situ foam urethane type ant-proof heat insulating material,
The test body made of the ant-proof heat insulating material according to any one of claims 1 to 3 is aged for a predetermined time in a test chamber in which the room temperature is set to 81 ° C.
Characterized by estimating the performance of the ant-repellent effect according to the residual amount of permethrin in the test specimen,
Evaluation method for in-situ urethane foam ant-proof insulation. It is a raw material liquid for mixing with a first liquid containing an isocyanate component liquid to produce an in-situ foamed urethane type ant-proof heat insulating material,
A raw material for an in-situ foamed urethane type ant-proof heat insulating material, characterized in that it is a mixture of a polyol component liquid, a permethrin solution containing a flame retardant that can be used as the above-mentioned polyale component liquid, and an aqueous borate solution. liquid.

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