JP3451540B2 - Termite-resistant foamable styrenic resin particles, method for producing the same, and foam molded article molded using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a termite-preventive expandable styrene-based resin particle for producing a styrene-based resin foam used for heat-insulating building materials such as termites and bark beetles that are not damaged by food, under-floor heat-insulating materials, etc. , And a foam molded article molded using the same.

[0002]

2. Description of the Related Art A foam molded article obtained by in-mold foam molding of pre-expanded particles obtained by pre-expanding expandable styrenic resin particles can be molded into any shape and has excellent heat insulation performance. Because of this, it is widely used as a heat insulating material for various building materials, and these heat insulating materials are indispensable building materials in terms of energy saving for indoor cooling and heating. On the other hand, with the spread of heating, the habitat of termites has moved northward, and there is damage caused by termites in houses and other buildings throughout most of the country. The damage caused by the termites is no exception in the heat insulating material made of expanded styrene resin. When a styrene resin foam molded article for building materials used as a heat insulating material for ceiling, wall, floor, etc., obtained by foam-molding expandable styrene resin particles in a mold, is used adjacent to wood, etc.,
In particular, there is a problem that a so-called ant road is formed and heat insulation performance is deteriorated due to the harmful habit of biting the objects that the termites, the termites and the like have encountered.

As a means for solving this problem, a method of adding an anti-termite agent in the step of polymerizing the styrene resin particles, the step of impregnating the foaming agent after the completion of the polymerization, or the method of protecting the expandable styrene resin particles or the pre-expanded particles A method is known in which a dovetail is mixed and adhered and molded (JP-A-61-44934 and JP-A-63-152648). Regarding the ant repellant, as disclosed in JP-B-7-103004, conventionally used organochlorine insecticides such as dieldrin, chlordane and DDT, and CCA agents (copper / chromium / arsenic agents).
Since these are highly toxic to humans and may cause environmental pollution, their use is prohibited or restricted. For example, dieldrin and chlordane have excellent ant-preventive properties, but are highly toxic to humans, and they are persistent and persistent, so their use is prohibited as a specific chemical substance in Japan. The agent cannot be used.

Therefore, in recent years, organic phosphorus insecticides such as hoxime and chlorpyrifos, which have relatively low toxicity and little risk of environmental pollution, carbamate insecticides such as propoxer, and pyrethrin insecticides such as permethrin and cyfluthrin have been used. However, it is preferable to use these chemicals even in the case of giving the styrenic resin foam heat insulating material anti-termite property. These termite repellents have an excellent termite control effect, have low human toxicity, and have no accumulation, but are easily decomposed,
Since it is inactivated by microorganisms in the soil as well, the effect cannot be sustained over a long period of time by simply treating the soil. In particular, since these agents are easily decomposed under alkaline conditions, it was difficult to apply them to basic concrete parts such as houses. Further, all of the drugs have low animal toxicity (phoxime: LD ₅₀ rat 2000 mg / kg or more), but have the characteristic of exhibiting toxicity to fish at a low concentration. For example, the organophosphorus agent Foxime's fish toxicity (TLm
48 hr carp) is less than 1 ppm, pyrethrins are more fish-toxic, and cyfluthrin is 0.02 pp.
It is about m. Both are poorly soluble in water, but they dissolve in trace amounts and exhibit fish toxicity.

From the point of view of fish toxicity, the above-mentioned (JP-A-61-4)
4934, JP-A-63-152648), a method of adding an anti-termite agent in the polymerization step and the foaming agent impregnation step is
It is not possible to prevent the transfer of the ant-preventive agent to the reaction water, and a large amount of fish-toxic reaction water requires treatment such as adsorption of activated carbon, which is disadvantageous in industrial production. In the method of molding by mixing the expandable styrenic resin particles or the pre-expanded particles and the termite-preventing agent, the reaction water is not used, and therefore the problem of fish toxicity of the reaction water does not occur. However, simply mixing and attaching the termite control agent weakens the adhesion force, and most of the termite control agent is washed away in the cooling process by water cooling during molding, which reduces the termite control efficacy of the molded product and at the same time during cooling and drainage. However, there was a problem that the termite repellent with fish toxicity was transferred. Among the methods disclosed in JP-A-63-159451, expandable styrenic resin particles are coated with a solution in which an ant-preventive agent is dissolved in an organic solvent having a high affinity for both the styrene-based resin and the ant-preventive agent. In this method, since the termite-preventing agent is substantially impregnated in the resin particles in the process of diffusing and impregnating the organic solvent into the resin particles, the method is protected from alkaline substances such as concrete and microorganisms in the soil. It is possible to suppress the decomposition and deactivation of the ant agent. Also,
This is an advantageous method from the viewpoint of fish toxicity, since it does not cause problems such as exfoliation by cooling water during transfer of the ant-preventive agent and transfer to cooling water. However, there is a problem that the surface layer of the expandable styrene resin particles is eroded and softened by the organic solvent, and the expandable styrene resin particles are coalesced into lumps, which has not led to industrial production.

[0006] As a method for preventing the formation of coalesced lumps of expandable styrenic resin particles, JP-A-64-36629 discloses a method in which an insect repellent is dissolved or dispersed in a volatile solvent, and the solution or dispersion is made into expandable styrene. A method of spraying on the surface of the resin particles has been proposed. However, even by this method, the surface layer of the resin particles is eroded by the volatile solvent immediately after the spraying, so that it is not possible to completely prevent the coalescence of the resin particles with each other. Further, the publication discloses that after attaching an insect repellent to the resin particles, the resin particles are coated with a lubricant such as higher fatty acid, metal soap of higher fatty acid or higher fatty acid amide. This is for preventing coalescence of expanded particles during pre-expansion as described in this publication. These lubricants do not have a function of preventing the expandable styrenic resin particles from forming a cohesive lump. When the expandable styrene-based resin particles are packed in a drum or the like and are to be transported, there is a problem that the expandable styrene-based resin particles are liable to cause agglomeration of the expandable styrene-based resin particles particularly at the bottom where a load is applied.

[0007]

The expandable styrenic resin particles are coalesced and agglomerated by eroding and softening the surface layer of the expandable styrenic resin particles by the organic solvent in which the ant-preventive agent is dissolved. In order to solve the problem, the powder which is not affected by the organic solvent on the surface of the expandable styrenic resin particles and does not impair the fusion property of the molded product obtained by foam molding the expandable styrene resin particles. By coating with, it is possible to prevent the mutual adhesion of the expandable styrenic resin particles, and it is possible to obtain a good molded product by the same foam molding operation as for ordinary expandable styrene resin particles. Become. However, even if it is coated with an organic powder such as higher fatty acid ester, higher fatty acid amide, and metal soap, which is conventionally known as a surface treatment agent for expandable styrenic resin particles, agglomeration of expandable styrenic resin particles with each other does not occur. It cannot be prevented.
In addition, when a known metal oxide such as titanium oxide, magnesium oxide, or magnesium hydroxide, or a metal hydroxide is coated,
In some cases, it is possible to prevent agglomeration of the expandable styrenic resin particles with each other, but on the other hand, the fusion property of the molded product obtained by foam-molding the expandable styrene resin particles is significantly impaired, and the strength of the molded product is increased. I can't keep it. As described above, generally, when a large amount of the expandable styrene resin particles is coated with the inorganic powder, the fusion property of the molded product is greatly impaired.

[0008] Therefore, as a result of intensive studies conducted by the present inventors in view of the above problems, when aluminum hydroxide was used, the formation of coalesced lumps of expandable styrenic resin particles was completely prevented, Further, they have found that it is possible to prevent the fusion property of a molded product obtained by specifically foam-molding being prevented, thus completing the present invention. The object of the present invention is that the reaction water is not required when the styrenic resin particles are contained in the styrenic resin particles, and the ant-preventive agent is substantially contained and fixed in the resin, and the effect of the ant-preservative agent is maintained for a long time. However, the termite control agent does not peel off even with cooling water at the time of molding, so there is no risk of causing environmental pollution such as fish poison by the cooling water, and foamable styrene resin particles are dissolved in an organic solvent. The expandable styrenic resin particles are prevented from coalescing and agglomeration even if containing, and the expandable styrenic resin particles having termite-proof properties without impairing the fusion property of the molded product obtained by further foaming, It is intended to provide a method for producing the same and a foamed molded product molded using the method.

[0009]

Means for Solving the Problems The subject matter of the invention of claim 1 of the present application is that a foaming agent containing a foaming agent which is a volatile organic solvent having a boiling point lower than the softening point of the resin particles is contained in styrene resin particles. 0.1 to 2% by weight of the termite-preventing agent relative to the expandable styrene-based resin particles are fixed and adhered to the expandable styrene-based resin particles, and 0.3 to 5 relative to the expandable styrene-based resin particles. A termite-preventive, expandable styrene resin particle characterized by being coated with aluminum hydroxide in a weight percentage, wherein the termite-preventing agent is selected from organic phosphorus compounds, pyrethrin compounds, and carbamate compounds. 1
It is preferable that there are two or more species. Further, claim 3
The gist of the invention is that the styrenic resin particles are compatible with both expandable styrenic resin particles containing a volatile foaming agent having a boiling point lower than the softening point of the resin particles, and both the termite control agent and the styrene resin. Solution containing 0.1 to 2% by weight of an anti-termite agent with respect to the expandable styrenic resin particles in an organic solvent having a property, and 0.3 to 5% by weight with respect to the expandable styrene resin particles. A method for producing a termite-preventive, expandable styrenic resin particle, which comprises fixing and containing a termite-preventing agent to obtain a foamable styrene-based resin particle coated with aluminum hydroxide. In that case, one or two selected from hydrocarbons, esters, ethers or ketones as the organic solvent having an affinity for both the termite control agent and the styrene resin used.
It is preferably at least one species. The gist of the invention of claim 5 is a foamed styrenic resin molded product having an anti-termite property, which is obtained by in-mold foam molding of the pre-foamed particles obtained by pre-foaming the expandable styrenic resin particles. .

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The termite control agent according to the present invention is excellent in termite control effect, has low toxicity to humans and animals, is less likely to pollute the environment, and has a long history of use as a termite control agent, and is selected from organic phosphorus-based, pyrethrin-based and carbamate-based compounds. To be selected. That is,
Specifically, as an organophosphorus termite, so-called phoxime (O, O-diethyl-O- (α-cyanobenzylideneamino) thiophosphate), chlorpyrifos (O, O-diethyl-O-3,
5,6-Trichloro-2-pyridylthiophosphate), pyridaphenthione (O, O-diethyl-O- (3-oxo-2-phenyl-2
H-pyridazin-6-yl) thiophosphate) and the like. Pyrethrin antitermites include permethrin (3-phenoxybenzyl (1RS) -cis, trans-3- (2,2-dichlorovinyl) -2-2 dimethylcyclopropanecarboxylate), cyfluthrin (cyano (4-fluoro -3-phenoxyphenyl) -methyl-3- (2,2-dichloroethenyl) -2,2-dimethylcyclopropanecarboxylate), bifenthrin ((2-methyl [1,1-biphenyl] -3-yl) methyl = 3- (2-
And chloro-3,3,3-trifluoro-1-propenyl) -2,2-dimethylcyclopropanecarboxylate). As a carbamate termiticide, propoxer (2-
Examples include isopropoxyphenyl N-methylcarbamate) and nac (1-naphthyl N-methylcarbamate).

In the present invention, the termite-preventing agent is coated on the foamable styrene-based resin particles with an organic solvent solution of the termite-preventing agent in an amount of 0.1 to 2% by weight based on the foamable styrene-based resin particles. Contained in the expandable styrene resin particles and fixed. It is preferably 0.2 to 1% by weight. This is because if it is less than 0.1% by weight, the termite-preventing effect of the molded article tends to be insufficient, and if it exceeds 2% by weight, it becomes difficult to suppress coalescence of the expandable styrene resin particles. The method of containing and fixing the termite-preventing agent in the expandable styrene resin particles according to the present invention applies the property that the termite-preventing agent dissolves in an organic solvent such as aromatic hydrocarbon, alcohol, or acetone. That is, using an organic solvent having an affinity for both the styrene resin and the termiticide,
A solution in which an anti-termite agent is dissolved is mixed with the expandable styrene-based resin particles to contain and fix the anti-termite agent in the surface layer of the expandable styrene-based resin particles. Fixing the expandable styrene-based resin particles in the surface layer is to cover the expandable styrene-based resin particles with an anti-termite agent in the form of an organic solvent solution so that the organic solvent softens the styrene-based resin particle surface layer or It dissolves and the termite proofing agent penetrates into the resin. Hexane, cyclohexane, toluene, ethylbenzene, hydrocarbons such as decalin, ethers such as ethyl ether and dioxane, ketones such as acetone and methyl ethyl ketone, and esters such as ethyl acetate are organic solvents that dissolve the termites used. Are suitable. In particular, an aromatic petroleum solvent which has a high affinity for both the ant-preventive agent and the styrene resin and which does not adversely affect the cell structure and moldability of the foam is preferable.

In the present invention, the surface of the expandable styrene resin particles is coated with aluminum hydroxide. The particle size of aluminum hydroxide used here is preferably 1 to 50 μm, more preferably 5 to 20 μm. Particle size is 1 μm
With the following, sufficient adhesion prevention cannot be obtained and
When it exceeds m, it becomes easy to peel from the expandable styrene resin particles. The amount of aluminum hydroxide added depends on the solvent species of the termite controlling agent to be coated and the amount of the termite controlling solution added, but is 0.3-5.
Weight percent is preferred. If it is less than 0.3% by weight, the preventive property of coalescing the expandable styrenic resin particles tends to be insufficient.
This is because the amount of coating on the expandable styrenic resin particles does not increase even if it is added in excess of wt%. As a method for coating the expandable styrenic resin particles with the termite control agent in the present invention, known mixing equipment can be used. For example, by mixing a foaming styrene resin particles with a tumbler, a ribbon blender, a Nauta mixer, etc., and an organic solvent solution in which an anti-termite agent is dissolved and aluminum hydroxide, agglomeration of resin particles is formed. It is possible to contain and fix an anti-termite agent in the resin particles while preventing it. At this time, at the same time, a foamed particle bond preventing agent at the time of pre-expansion, a molding time shortening agent, a fusion-bonding accelerator for molded articles, etc. may be added. In addition, in the method of directly stirring and mixing the flaky or granular termite control agent with the expandable styrenic resin particles, the termite control agent is easily peeled off at the time of prefoaming, molding, etc. At the same time, there is a problem that the ant-terminating agent having fish toxicity migrates to the steam drain at the time of pre-expansion and the molding cooling waste water.

Examples of the resin material constituting the expandable styrene resin particles of the present invention include styrene and styrene derivatives such as α-methylstyrene, vinyltoluene and parachlorostyrene. In addition, for example,
Acrylonitrile, acrylic acid, acrylic ester,
Although a monomer copolymerizable with styrene such as methacrylic acid ester and maleic anhydride or a crosslinkable monomer such as divinylbenzene can be used in combination, the styrene component is sufficiently contained in order to fix the ant-preventive agent. A copolymer or styrene homopolymer of 50% by weight or more is preferable. Further, in order to obtain the styrene resin particles, a known method such as a general suspension polymerization method or an extrusion pellet method can be used. An expandable styrene-based resin particle can be obtained by appropriately adding an easily volatile foaming agent to these styrene-based resin particles. The method of adding the foaming agent may be a method of adding the foaming agent during or after the polymerization or a method of adding the foaming agent during the extrusion.

Suitable volatile blowing agents are organic compounds which have a boiling point not higher than the softening point of the styrenic resin particles and are gaseous or liquid at normal pressure, such as propane, butane, pentane, hexane, cyclo Hydrocarbons such as pentane are suitable. These foaming agents may be used alone or in combination of two or more. Foaming agent is 1 to 1 for styrene resin
Impregnated with 0% by weight. Further, if necessary, a plasticizer such as cyclohexane or toluene, a colorant such as a dye, an antioxidant, a lubricant (for example, liquid paraffin, fatty acid ester,
Various additives such as metal soaps), flame retardants, flame retardant aids, antistatic agents and the like can be added.

[0015]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited thereto. Example 1 n-butane (about 70%) and i-butane (about 3%) were used as blowing agents.
0%) and 5.5% by weight of a mixture thereof with 1.5% by weight of toluene as a foaming auxiliary agent, and a pyrethrin-based termite-preventing agent for expandable styrene resin particles having a particle size of 0.9 to 1.2 mm. As a petroleum-based solution of permethrin (80% by weight of active ingredient), 1% by weight of the active ingredient and 1.6% by weight of aluminum hydroxide (particle size: about 15 μm) were added and mixed to coat the surface of the expandable styrene resin particles. did. When mixing, use a tumbler with an internal volume of about 30 L, add the anti-termite solution and aluminum hydroxide in the above proportions to each 10 kg of expandable styrene resin particles, and mix at 30 rpm for about 15 minutes to prevent mixing. Expandable styrene resin particles coated with the dovetail solution and aluminum hydroxide were obtained. After confirming the fluidity of the obtained expandable styrene resin particles immediately after coating, it was kept at room temperature for 48 hours.
After allowing to stand for a period of time, the anti-termite solution was completely impregnated and diffused in the expandable styrene resin particles. In addition, when left standing, it is assumed that the expandable styrene resin particles on the bottom of the drum can (about 50 gf
/ Cm ² ). The expandable styrene resin particles were heated by steam in a small batch type pre-expanding machine under normal pressure to pre-expand to a bulk ratio of about 60 times. The pre-expanded particles obtained were aged at 23 ° C. for 24 hours, and then the mold cavity 300 was formed.
Using a foam molding machine having a size of mm x 400 mm x 50 mm (ACE-3 type manufactured by Sekisui Koki Mfg. Co., Ltd.), foaming is performed by heating with steam having a gauge pressure of 0.8 kgf / cm ² for about 30 seconds, Cooled by water cooling and removed from the mold cavity, 3
A plate-shaped foam molded article having a size of 00 mm × 400 mm × 50 mm was obtained.

Example 2 A pyrethrin antitermite was changed from permethrin to cyfluthrin (petroleum solution of 50% by weight of active ingredient), the addition amount was 0.4% by weight of the active ingredient, and the addition amount of aluminum hydroxide was 0.8. Expandable styrene resin particles were obtained in the same manner as in Example 1 except that the amount was changed to wt%. The obtained expandable styrene resin particles were pre-foamed in the same manner as in Example 1 and subjected to in-mold foam molding to obtain a plate-shaped foam molded body of 300 mm × 400 mm × 50 mm. Example 3 An ant-preventive agent was added to an organic phosphorus-based oxime (petroleum-based solution of 65% by weight of active ingredient), the addition amount was 0.2% by weight of the active ingredient, and the addition amount of aluminum hydroxide was 0.5% by weight. Expandable styrene resin particles were obtained in the same manner as in Example 1 except that the change was made. The obtained expandable styrene resin particles were pre-foamed in the same manner as in Example 1 and in-mold foam-molded to obtain 300 mm × 4.
A plate-shaped foam molded body of 00 mm × 50 mm was obtained.

Example 4 Expandable styrene resin particles were obtained in the same manner as in Example 1 except that the amount of the oxime added was changed to 0.4% by weight of the active ingredient and the amount of aluminum hydroxide was changed to 1% by weight. Obtained. The obtained expandable styrene resin particles were pre-expanded in the same manner as in Example 1 and subjected to in-mold foam molding to obtain 300 mm × 400 mm.
A 50 mm plate-shaped foamed molded product was obtained. Example 5 Expandable styrene resin particles were obtained in the same manner as in Example 1 except that the amount of the oxime added was changed to 1% by weight of the active ingredient and the amount of aluminum hydroxide was changed to 1.6% by weight. The obtained expandable styrene resin particles were pre-expanded in the same manner as in Example 1 and subjected to in-mold foam molding to obtain 300 mm × 400 mm.
A 50 mm plate-shaped foamed molded product was obtained.

Example 6 Example 1 was repeated except that the addition amount of the oxime was changed to 2% by weight of the active ingredient and the addition amount of aluminum hydroxide was changed to 3% by weight.
Expandable styrene resin particles were obtained in the same manner as in. The obtained expandable styrene resin particles were pre-expanded in the same manner as in Example 1 and subjected to in-mold foam molding to obtain 300 mm × 400 mm.
A 50 mm plate-shaped foamed molded product was obtained.

Comparative Example 1 The expandable styrene resin particles described in Example 1 without the addition of the ant-preventive agent solution and aluminum hydroxide were pre-foamed in the same manner as in Example 1 and in-mold foam-molded to 300 mm × 400.
A plate-shaped foamed molded product having a size of mm × 50 mm was obtained. Comparative Example 2 Expandable styrene resin particles were obtained in the same manner as in Example 1 except that aluminum hydroxide was not added. After being left at room temperature for 48 hours, all of the expandable styrene resin particles were coalesced into a lump and could not be pre-expanded.

Comparative Example 3 Expandable styrene resin particles were obtained in the same manner as in Example 1 except that the termite-preventing agent was added to cyfluthrin so that the amount of the active ingredient was 1% by weight and aluminum hydroxide was not added. Got After being left at room temperature for 48 hours, all of the expandable styrene resin particles were coalesced into a lump and could not be pre-expanded. Comparative Example 4 Expandable styrene resin particles were obtained in the same manner as in Example 1 except that an anti-termite agent was added to hoxime so that the amount of the active ingredient was 1% by weight and aluminum hydroxide was not added. . After being left at room temperature for 48 hours, all of the expandable styrene resin particles were coalesced into a lump and could not be pre-expanded.

Comparative Example 5 An anti-termite agent was added to hoxime so that the amount of the active ingredient added was 1% by weight, and the amount of aluminum hydroxide added was 0.1.
Expandable styrene resin particles were obtained in the same manner as in Example 1 except that the amount was changed to wt%. After standing at room temperature for 48 hours, almost all of the expandable styrene resin particles were coalesced into a lump and pre-expanding was not possible. Comparative Example 6 An antitermite was added to hoxime, the addition amount was 1% by weight of the active ingredient,
Silica gel (average particle size 1.
(8 μm) was added in the same manner as in Example 1 except that 0.8% by weight was added to obtain expandable styrene resin particles. The obtained expandable styrene resin particles were pre-foamed in the same manner as in Example 1 and in-mold foam-molded to obtain 300 mm × 400 mm × 50.
A plate-shaped foamed molded product having a size of mm was obtained.

COMPARATIVE EXAMPLE 7 An antitermite was added to hoxime, and the amount of the active ingredient added was 1% by weight.
Example 1 except that 1.6% of magnesium hydroxide (average particle size of about 40 μm) was added instead of aluminum hydroxide.
Expandable styrene resin particles were obtained in the same manner as in. The obtained expandable styrene resin particles were pre-foamed in the same manner as in Example 1 and in-mold foam-molded to obtain 300 mm × 400 mm × 5.
A 0 mm plate-shaped foam molding was obtained. Comparative Example 8 An antitermite was added to hoxime, and the amount added was 1% by weight of the active ingredient.
Titanium oxide (average particle size 7n
Expandable styrene resin particles were obtained in the same manner as in Example 1 except that 1.6% by weight of m) was added. After being left at room temperature for 48 hours, almost all of the expandable styrene resin particles were coalesced into a lump and could not be pre-expanded.

Comparative Example 9 An antitermite was added to hoxime, and the amount added was 1% by weight of the active ingredient.
Expandable styrene resin particles were obtained in the same manner as in Example 1 except that 1.6% by weight of aluminum oxide (average particle diameter of about 20 nm) was added instead of aluminum hydroxide. Room temperature 4
After standing for 8 hours, almost all of the expandable styrene resin particles were coalesced into a lump and pre-expanding was not possible. Comparative Example 10 An antitermite was added to hoxime, the addition amount was 1% by weight of the active ingredient,
Example 1 except that 1.6% by weight of calcium carbonate (average particle size of about 40 nm) was added instead of aluminum hydroxide.
Expandable styrene resin particles were obtained in the same manner as in. Room temperature 48
After standing for a period of time, almost all of the expandable styrene resin particles were coalesced into a lump and could not be pre-expanded.

COMPARATIVE EXAMPLE 11 An antitermite was added to hoxime, and the amount of the active ingredient added was 1% by weight.
Talc in place of aluminum hydroxide (particle size about 40 μm)
The expandable styrene resin particles were obtained in the same manner as in Example 1 except that 1.6% by weight of was added. After leaving it at room temperature for 48 hours,
Almost all of the expandable styrene resin particles were coalesced into a lump and could not be pre-expanded. Comparative Example 12 An antitermite was added to hoxime, the addition amount was 1% by weight of the active ingredient,
Expandable styrene resin particles were obtained in the same manner as in Example 1 except that 1.6% by weight of zinc stearate (average particle size of about 15 μm) was added instead of aluminum hydroxide. Room temperature 4
After standing for 8 hours, almost all of the expandable styrene resin particles were coalesced into a lump and pre-expanding was not possible.

Comparative Example 13 Expandable styrene resin particles were prepared in the same manner as in Example 1 except that the amount of the oxime added was changed to 0.03% by weight of the active ingredient and the amount of aluminum hydroxide was changed to 1% by weight. Obtained. The obtained expandable styrene resin particles were pre-foamed in the same manner as in Example 1 and in-mold foam-molded to 300 mm × 400 m
A plate-shaped foamed molded product of m × 50 mm was obtained. Comparative Example 14 Example 1 was repeated except that the termite-preventing agent was changed to organic phosphorus-based chlorpyrifos (crystalline powder), 1% by weight of the active ingredient was added as a powder without being dissolved in a solvent, and aluminum hydroxide was not added. In the same manner, expandable styrene resin particles whose surface was coated with an anti-termite agent were obtained. The obtained expandable styrene resin particles were pre-foamed in the same manner as in Example 1 and subjected to in-mold foam molding to obtain a plate-shaped foam molded body of 300 mm × 400 mm × 50 mm.

Examples 1 to 6 and Comparative Examples 1 to 1 described above
Table 1 shows the addition amounts of the termite-preventing agent and the anti-adhesion agent of No. 4, and the adhesion of the resin particles after coating with aluminum hydroxide.
The plate-shaped compacts obtained in Examples 1 to 6 and Comparative Examples 1 to 14 were dried at 40 ° C. for 24 hours, and the fusion degree and termite resistance of the compacts were evaluated by the following methods. The results are shown in Table 2. (Fusing degree measuring method) External shape 300 mm x 400 mm x 5
The foamed molded product having a size of 0 mm was broken at the center thereof so as to be divided into two, and the number of the particles in which the particles themselves were broken was divided by the number of all the particles in the broken surface. Then, the value multiplied by 100 was defined as the fusion degree. The number of the particles was visually measured. (Evaluation of Fusing Property) Based on the fusing degree calculated above, the following judgment was made. Evaluation ◯: The degree of fusion of the molded body is 85% or more. ×: The degree of fusion of the molded body is less than 65%.

(Terminal antagonism evaluation test method) (Company) Evaluation was carried out as follows with reference to the comprehensive test method of the termite proof effect test method defined in Japan Wood Preservation Association Standard No. 11 (1).
That is, the degreased surface is made to contain water, a gypsum plate is placed on the degreased surface so that water is supplied through the gypsum plate, and a glass ring having a diameter of 41 mm and a height of 50 mm is placed on the gypsum plate, A specimen cut out from the foamed molded product and a test sample were placed therein, and the mixture was bred for 21 days and the feeding damage was visually observed. In addition, the weight loss rate of the sample was measured. Specimen: 20 × 20 × 10 mm Sample worm: Yellow termite (Coptotermes formosanus SHIR)
AKI) 50 ants for each test condition: 28 ° C. × 21 days number of repetitions: n = 3 (visual evaluation of ant resistance) The samples tested as described above were evaluated as follows. Evaluation ○: No food damage △: Evaluation of food marks on a part of the surface of the sample ×: Damage to the inside of the sample * Visual evaluation △ or more, weight reduction rate of the sample less than 3% is judged to have anti-termite effect did.

[0028]

[Table 1]

[0029]

[Table 2]

Further, for some of the examples and comparative examples,
The fish toxicity of the cooling water during molding was evaluated by the following method, and the results are shown in Table 3. (Evaluation Method of Fish Toxicity) Cooling waste water (mixed water of steam drain water and cooling water) at the time of molding was sampled (about 40 L), and 10 gold fish each having a body length of about 5 cm were placed in each and observed for 72 hours. In addition, as a reference example, water obtained by adding 5 ppm of an organic phosphorus agent to the molding cooling waste water of a normal product (without a termite-preventing agent) was similarly observed.

[0031]

[Table 3]

[0032]

INDUSTRIAL APPLICABILITY According to the present invention, when the styrenic resin is contained in the styrenic resin particles, reaction water is not required, and the ant-preventive agent is substantially contained and fixed in the resin. The effect lasts for a long time, the ant-preventive agent does not peel off even with cooling water during molding, so there is no risk of causing environmental pollution such as fish poison due to cooling water, and expandable styrenic resin particles dissolve in organic solvents. The expandable styrenic resin particles do not coalesce into agglomerates even if they contain the termite-preventing agent, and do not impair the fusion property of the molded product obtained by foam molding. Styrene resin particles can be obtained. The molded product obtained by in-mold foam molding of the pre-expanded particles obtained by pre-expanding the expandable styrenic resin particles according to the present invention is a foamed resin that is substantially superior in terms of heat resistance and water resistance with an anti-termite agent. Since it is contained in the resin of the molded body, it is possible to prevent the decomposition and deactivation of the termite control agent due to the microorganisms in the soil and the alkalinity of concrete, and to maintain the stable efficacy of the termite control agent for a long time.
It can also be applied to concrete surfaces, which was difficult in the past. Also, unlike soil spraying, the termite control agent does not transfer to groundwater or the like, and the risk of causing environmental pollution can be greatly reduced.

Claims (5)

(57) [Claims] 1. A foamable styrene-based resin particle containing a volatile foaming agent having a boiling point lower than the softening point of the resin-based resin particle in the styrene-based resin particle. Contains 1-2% by weight of termite control agent
Furthermore, 0.3 to 5 relative to the expandable styrene resin particles
Anti-termite expandable styrenic resin particles, characterized in that they are coated with aluminum hydroxide in a weight percentage. 2. The termite-proof expandable styrene-based resin particles according to claim 1, wherein the termite-preventing agent is one or more species selected from an organic phosphorus compound, a pyrethrin compound and a carbamate compound. 3. A foamable styrene-based resin particle containing a volatile foaming agent having a boiling point lower than the softening point of the styrene-based resin particle and affinity for both the termite-preventing agent and the styrene-based resin. 0.1 to 2% by weight of an anti-termite agent with respect to the expandable styrenic resin particles in an organic solvent having an amount of 0.
Contains fixing the termiticide by mixing 3-5% by weight of aluminum hydroxide, according to claim 1 or 2, wherein the aluminum hydroxide, characterized in that to obtain a coated expandable styrene resin particles A method for producing an anti-termite expandable styrenic resin particle. 4. The organic solvent having an affinity for both the termiticide and the styrene resin is one or more selected from hydrocarbons, esters, ethers or ketones. A method for producing an anti-termite expandable styrenic resin particle. 5. A foamed styrenic resin molded article having an anti-termite property obtained by in-mold foam molding of the pre-expanded particles obtained by pre-expanding the expandable styrenic resin particles according to claim 1 or 2 .