JP2018028035A - Method for producing insect repellent-containing polyurethane foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an insect repellent-containing polyurethane foam that effectively avoids foaming failures and discoloration in production and reduces production cost.SOLUTION: The present invention provides a method for producing an insect repellent-containing polyurethane foam that mixes an isocyanate source solution containing an isocyanate with a polyol source solution containing a polyol, an insect repellent and a flame retardant for foaming. In the method, the flame retardant is thermally mixed with the insect repellent to prepare an insect repellent-containing flame retardant, and the insect repellent-containing flame retardant is mixed into a polyol to prepare a polyol source solution.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing an insect repellent-containing polyurethane foam, and more particularly to a method for producing an insect repellent-containing polyurethane foam in which an operation of heating and mixing an insect repellent with a flame retardant is performed.

  Conventionally, in a building such as a house, a heat insulating material such as polyurethane foam has been used for the purpose of providing a heat insulating effect. In particular, polyurethane foam has been useful because it has an insecticidal effect that kills insect pests when eaten by insects such as termites. However, since this insecticidal effect is not immediately effective, an insecticidal heat insulating material made of a foamed material such as urethane foam mixed with an insecticide has been used in recent years. For example, in Patent Document 1, an insect repellent having a melting point of 35 to 150 ° C. is heated and melted in a polyol or the like to prepare a foam raw material liquid, and a foam is formed using the foam raw material liquid to manufacture an insect repellent heat insulating material. It has been proposed to do so.

  The insect repellent insulation material of Patent Document 1 is excellent in that the insect repellent is uniformly dispersed in the foam despite the fact that no organic solvent is used. However, in the insect-proof heat insulating material of this patent document 1, the foam may discolor at the time of manufacture, foaming defect may arise, and the problem that the commercial value was impaired had arisen. Furthermore, depending on the type of polyol, the insect repellent is difficult to dissolve, and heating for a long time is required, resulting in an increase in manufacturing cost.

JP 2001-3471 A

  Accordingly, an object of the present invention is to provide a method for producing an insect repellent-containing polyurethane foam in which foaming failure and discoloration during production are effectively avoided and production cost is suppressed.

  The inventors of the present invention have studied diligently about the insect-insulating heat insulating material. As a result, the insect-insulating heat insulating material is usually mixed with various auxiliary agents including a catalyst. Then, the auxiliary agent is colored, or if the auxiliary agent has a low molecular weight, the auxiliary agent condenses on the ceiling of the heating tank and the concentration in the polyol decreases, resulting in a problem such as a slow urethane reaction (curing) rate. As a result, the present invention has been completed.

  Therefore, according to the present invention, in the method for producing an insect repellent-containing polyurethane foam, the isocyanate raw material liquid containing isocyanate and the polyol raw material liquid containing polyol, insect repellent and flame retardant are mixed and foamed. A method for producing an insect repellent-containing polyurethane foam, characterized by preparing an insect repellent-containing flame retardant by heating and mixing the insect repellent with a flame retardant, and preparing a polyol raw material liquid by mixing the insect repellent-containing flame retardant into a polyol Is provided.

  A method for producing an insect repellent-containing polyurethane foam, wherein the insect repellent is bifenthrin, acetamiprid, ciphenothrin or thiacloprid is a preferred embodiment of the present invention.

  A method for producing an insect repellent-containing polyurethane foam in which the flame retardant is trichloropropyl phosphate or chlorinated paraffin is a preferred embodiment of the present invention.

  A method for producing an insect repellent-containing polyurethane foam in which an amine catalyst is further mixed into the polyol raw material liquid is a preferred embodiment of the present invention.

  A method for producing an insect-repellent-containing polyurethane foam in which the insect-repellent-containing flame retardant is mixed in a polyol at 0 to 35 ° C. is a preferred embodiment of the present invention.

  In the present invention, it is not necessary to heat the polyol by mixing the insecticide with the flame retardant to adjust the insecticide-containing flame retardant and mixing the insecticide-containing flame retardant into the polyol. Therefore, it is not necessary to heat the auxiliary agent that is weak against heat, and it is possible to effectively avoid delay in curing speed and discoloration during production.

  Furthermore, instead of mixing and heating an insect repellent in a polyol with a large amount of use, mixing the insect repellent with a flame retardant with a small amount of use and heating can greatly reduce heating energy and heating time. In addition, the production cost of the insect-repellent-containing polyurethane foam can be reduced.

  The manufacturing method of the insect-repellent-containing polyurethane foam of the present invention is to mix and foam an isocyanate raw material liquid containing an isocyanate and a polyol raw material liquid containing a polyol, an insect repellent and a flame retardant.

<Isocyanate raw material liquid>
In the present invention, conventionally known isocyanates such as TDI (tolylene diisocyanate), MDI (diphenylmethane diisocyanate and polymethylene polyphenylene polyisocyanate), or modified products thereof can be used as the isocyanate. Isocyanate is mixed with additives and the like as described below as necessary, and is provided to the production method of the present invention as an isocyanate raw material liquid.

<Polyol raw material liquid>
As the polyol, conventionally known ones such as polyether polyol, polyester polyol, polycaprolactone polyol and the like can be used, but polyether polyol is preferred from the viewpoint of being excellent in hydrolysis resistance and available at low cost. In particular, polyether polyols having 2 to 8 functional groups and a molecular weight of 60 to 3000 per the number of functional groups are preferred.

  In the present invention, an insecticide-containing flame retardant obtained by dissolving an insecticide in a flame retardant is prepared, and the polyol raw material liquid is prepared by adding the insecticide-containing flame retardant to a polyol and mixing them.

As the insect repellents, known ones such as pyrethroid insect repellents, neonicotinoid insect repellents, organophosphorus insect repellents and the like can be used, but the decomposition temperature of the flame retardant or lower (usually 200 ° C. or lower) From the viewpoint of being dissolved in a flame retardant and maintaining the insect repellent effect over a long period of time, those that are solid at room temperature (5-35 ° C.) are preferably used. Specific examples of such insect repellents include permethrin {3-phenoxybenzyl 3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate, melting point: 34-39 ° C.}, ciphenothrin. {2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylic acid = α-cyano-3-phenoxybenzyl, melting point 44 ° C.}, bifenthrin {2-methylbiphenyl-3-ylmethyl (Z) -(1RS, 3RS) -3- (2-chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethylcyclopropanecarboxylate, melting point: 71 ° C}, etofenprox {2 -(4-Ethoxyphenyl) -2-methylpropyl-3-phenoxybenzyl ether, melting point: 37.0 ° C.}, acetamipri ^{{(E) -N 1 - [} (6- chloro-3-pyridyl) methyl] -N ² - cyano -N ¹ - methyl acetamidine, mp: 98.9 ° C.}, thiacloprid {(Z) -3- ( 6-chloro-3-pyridylmethyl) -1,3-thiazolidine-2-ylidenecyanamide, melting point: 136 ° C.}, chlorpyrifos {O, O-diethyl-O-3,5,6-trichloro-2-pyridyl phosphorothioate , Melting point: 42.0 ° C.}, chloropyrifosmethyl (0,0-dimethyl-0-3,5,6-trichloro-2-pyridyl phosphorothioate, melting point: 45.5 ° C.) and the like. Bifenthrin, acetamiprid, ciphenothrin, or thiacloprid is more preferable from the viewpoint of easy availability and excellent insect repellent effect.

  Known flame retardants may be used, for example, brominated flame retardants such as decabromodiphenyl oxide and tetrabromodisphenol A; trichloropropyl phosphate (hereinafter TCPP), trichloroethyl phosphate, triethyl phosphate, red phosphorus Phosphorus flame retardants such as ammonium polyphosphate; Chlorine flame retardants such as chlorinated paraffin and anhydrous het acid; Inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide; From the viewpoint of availability, a chlorine-based flame retardant or a phosphorus-based flame retardant is preferable, and trichloropropyl phosphate or chlorinated paraffin is more preferable. From the viewpoint of excellent hydrolysis resistance and environmental considerations, trichloropropyl is preferred. Phosphate is particularly preferred.

  The amount of the insect repellent is preferably 0.5 to 20 parts by mass, particularly preferably 1 to 15 parts by mass, per 100 parts by mass of the flame retardant. When there are too few insect repellents, there exists a possibility that sufficient insect repellent effect cannot be provided to the insect repellent-containing polyurethane foam finally obtained. Moreover, when there are too many insect repellents, not only a special advantage will not be acquired, but a heating time must be lengthened, and there exists a possibility of causing the increase in manufacturing cost.

  As a means for heating and mixing the insect repellent in the flame retardant, a known means such as using a propeller stirrer equipped with temperature control equipment may be selected.

  The temperature of the flame retardant at the time of heating and mixing is appropriately determined in consideration of the decomposition temperature of the flame retardant and the type and amount of the insect repellent, but is preferably 50 to 150 ° C, particularly preferably 50 to 100 ° C. The heating and mixing may be performed by mixing an insecticide into the flame retardant that has been heated to a desired temperature, or may be performed by heating the flame retardant after mixing the insecticide.

  The fact that the insect repellent is dissolved in the flame retardant is determined by visually confirming that the liquid mixture of the insect repellent and the flame retardant has become transparent.

  The insecticide-containing flame retardant obtained as described above is mixed in a polyol to prepare a polyol raw material liquid.

  20-100 mass parts is preferable per 100 mass parts polyol, and 40-80 mass parts is especially preferable as the compounding quantity of an insecticide containing flame retardant. When there is too much quantity of an insecticide containing flame retardant, there exists a possibility of causing a foaming defect. On the other hand, if the amount is too small, there is a possibility that a sufficient insect-proofing effect and flame-retardant effect cannot be imparted to the polyurethane foam as the final object.

  In addition to the insecticide-containing flame retardant, the polyol may contain auxiliary agents such as catalysts, foaming agents, additives, and at least a catalyst from the viewpoint of maximizing the effects of the present invention. Is preferred.

  As the catalyst, known ones can be used, for example, amine-based catalysts such as triethylamine, tripropylamine, N-methylmorpholine, N-ethylmorpholine, triethylenediamine, tetramethylhexanediamine, dimethylcyclohexylamine and the like. Organic metal catalysts such as organic tin compounds, organic bismuth compounds, organic lead compounds, and organic zinc compounds can be used, but not only the resinification reaction of isocyanate and polyol, but also polyol and From the viewpoint of having a catalytic function even in the foaming reaction, an amine-based catalyst can be preferably used. The blending amount of the catalyst is preferably 0.1 to 3.0 parts by mass, more preferably 0.3 to 1.2 parts by mass per 100 parts by mass of the polyol. When the amount of the catalyst is outside the above range, it may be difficult to control the degree of curing and the time.

  A known foaming agent may be used, for example, a silicone foaming agent such as polydimethylsiloxane or siloxaneoxyalkylene copolymer may be used. The blending amount of the foaming agent is preferably 0.3 to 5 parts by mass and more preferably 0.3 to 3.0 parts by mass per 100 parts by mass of the polyol.

  As the additive, known ones such as a crosslinking agent, a curing agent, a deterioration preventing agent, a plasticizer, a stabilizer, and a colorant may be appropriately selected and used as necessary. What is necessary is just to determine a compounding quantity suitably on the conditions that the effect of this invention is not impaired.

  In addition to the insecticide-containing flame retardant and auxiliary agent, the polyol may further contain an organic solvent such as toluene, but it is preferable not to add it from the viewpoint of more reliably avoiding foaming defects.

  As a means for mixing the insecticide-containing flame retardant, various auxiliaries, and the organic solvent into the polyol, a known means may be selected such as using a propeller stirrer equipped with a temperature control facility.

  In the present invention, when the insecticide-containing flame retardant is mixed, the polyol is not heated from the viewpoint of preventing inconvenience such as discoloration in an auxiliary agent such as a catalyst. The specific polyol temperature is 0 to 35 ° C, and 10 to 30 ° C is particularly preferable. The insecticide-containing flame retardant is also preferably cooled in advance for the same reason. Specifically, it is preferably cooled to 0 to 35 ° C, particularly 10 to 30 ° C.

<Mixing and foaming>
In the present invention, an insecticide-containing polyurethane foam can be obtained by mixing and foaming the polyol raw material liquid and the isocyanate raw material liquid obtained as described above based on known methods and conditions.

  The usage amount of both raw material liquids is appropriately determined so that the polyol in the polyol raw material liquid and the isocyanate in the isocyanate raw material liquid have a ratio of 1:10 to 1: 1 (mol).

  In mixing and foaming of raw material liquids, a foaming agent is usually used. Known foaming agents include water (including moisture in the air); low boiling point compounds such as liquefied petroleum gas (LPG) and dimethyl ether (DME); fluorocarbons such as chlorofluorocarbon, hydrochlorofluorocarbon, and hydrofluorocarbon; A foaming agent may be used. Of these foaming agents, water is a so-called chemical foaming agent that reacts with isocyanate to generate carbon dioxide, and low-boiling compounds and fluorocarbons foam by being vaporized by reaction heat generated by the polyurethane-forming reaction. A so-called physical blowing agent.

  When the spray method described later is selected as a method for mixing and foaming the raw material liquid, a suitable foaming agent is water or a low-boiling point compound from the viewpoint of easy control of the foaming timing, and particularly water or liquefied petroleum gas ( LPG). When water is used as the foaming agent in the spray method, the case where water in the air is used as a so-called chemical foaming agent is also included.

  The blending amount of the foaming agent is preferably 0.05 to 1 part by mass in the case of water per 100 parts by mass of the total amount of the polyol raw material liquid and the isocyanate raw material liquid, and 10 to 10 in the case of a low boiling point compound such as LPG or fluorocarbon. 40 parts by mass is preferred.

  As a method for mixing and foaming both raw material liquids, a known method such as spray method, hand mixing foaming method, (cylinder type) simple foaming method, injection method, floss injection method, etc. can be adopted. From the viewpoint that it can be efficiently applied to gaps where insects such as termites are expected to invade, since the foaming is possible.

  In the spray method, a pressure resistant container such as a so-called spray can is filled with a polyol raw material liquid, an isocyanate raw material liquid and a foaming agent, and further filled with a propellant as necessary, and these are injected through a nozzle or discharged in a rod shape. This is a method of forming a polyurethane foam.

  As the propellant, the low-boiling compounds exemplified above as the foaming agent can be used, but other known ones can also be used under the condition that the effects of the present invention are not impaired.

  The spray method can be roughly divided into a one-component spray method and a two-component spray method. The one-component spray method is a method in which a polyol raw material liquid, an isocyanate raw material liquid and a foaming agent and, if necessary, a propellant are filled in one pressure-resistant container, and these are mixed and then injected or discharged. . With the two-component spray method, a polyol raw material liquid and an isocyanate raw material liquid are filled in separate pressure-resistant containers together with a foaming agent and an appropriately used propellant, and these raw material liquids are jetted or discharged while being mixed, A method of forming a polyurethane foam. In the present invention, the one-component spray method is preferable from the viewpoint of ease of operation.

  The temperature of each raw material liquid at the time of mixing and foaming is usually 10 to 40 ° C in the one-component spray method, preferably 15 to 30 ° C, and usually 20 to 100 ° C in the two-component spray method, and 30 to 30 ° C. 70 ° C. is preferred.

<Insecticide-containing polyurethane foam>
As the polyurethane foam obtained by the production method of the present invention, a rigid polyurethane foam, which is a polyurethane foam containing many closed cells, is preferable. The rigid polyurethane foam includes urethane modified isocyanurate foam, urea foam and the like.

  By forming the insecticidal agent-containing polyurethane foam in a building such as a house in a space where a pest such as a termite is likely to enter or a place where it is particularly desired to protect from a termite damage, a heat insulating effect can be enjoyed together with an insecticidal effect.

  Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples. The technical scope of the present invention is not limited by these.

<Example 1>
1.7 g of bifenthrin as an insect repellent was added to 54 g of TCPP as a flame retardant, dissolved by heating and stirring at 55 ° C., and then cooled to room temperature. Next, 90 g polyol {polypropylene glycol (average molecular weight 2000) mixed with 0.3% triethylamine as a urethanization catalyst and 0.5% polydimethylsiloxane surfactant as a foam stabilizer} The mixture was stirred and mixed at room temperature of 25 ° C., and 200 g of isocyanate {manufactured by Mitsui Chemicals, Inc., trade name: Cosmonate LL} and 43 g of LPG gas were mixed and urethane-reacted to produce a urethane foam. At this time, the Hazen color number of the mixed liquid of bifenthrin, TCPP and polyol was 10, and the Hunter whiteness of the obtained urethane foam was 96. Test pieces were cut out from the urethane foam, and JIS K1571 (2010) “Wood preservatives—Performance standards and test methods” -5.3 “Anti-antagonistic performance”-5.3.1 “In-house tests” —5.3.1 .1 When a forced contact test was performed on termites in accordance with “Injection treatment”, the mass reduction rate was 1.2% and the termite lethality rate was 27.6%. The following):

<Example 2>
The insect repellent of Example 1 was changed to acetamiprid, and the heat dissolution temperature in TCPP was changed to 70 ° C., and everything else was carried out in the same manner as in Example 1, and the results are shown in Table 1.

<Example 3>
The insect repellent of Example 1 was changed to cyphenothrin, and the heating and dissolving temperature in TCPP was changed to 50 ° C., and everything else was carried out in the same manner as in Example 1, and the results are shown in Table 1.

<Example 4>
The insect repellent of Example 1 was changed to thiacloprid and the heating and dissolving temperature in TCPP was changed to 75 ° C., and everything else was carried out in the same manner as in Example 1, and the results are shown in Table 1.

<Example 5>
The flame retardant of Example 1 was changed to chlorinated paraffin (Asahi Denka Kogyo Co., Ltd., Adekaiser E-450, chlorination rate 45%), and the heat dissolution temperature in TCPP was changed to 50 ° C. The test was carried out in the same manner as in Example 1, and the results are shown in Table 1.

<Comparative Example 1>
When the dissolution temperature in TCPP of Example 1 was changed to room temperature (25 ° C.), a large amount of bifenthrin crystals remained and sufficient dissolution was not possible. The rest was carried out in the same manner as in Example 1, and the results are shown in Table 1.

<Comparative example 2>
54 g of TCPP in Example 1 and 90 g of polyol (composition is the same as in Example 1) were previously mixed at room temperature, and then 1.7 g of bifenthrin was added and stirred at room temperature. A lot of bifenthrin crystals remained and could not be sufficiently dissolved. The rest was carried out in the same manner as in Example 1, and the results are shown in Table 1.

<Comparative Example 3>
In Example 1, it implemented without adding an insect repellent. The rest was carried out in the same manner as in Example 1, and the results are shown in Table 1.

<Comparative Example 4>
1.7 g of acetamiprid was added to 54 g of TCPP and 90 g of polyol (composition is the same as in Example 1) and mixed with stirring. Many crystals of acetamiprid remained and did not dissolve sufficiently. Therefore, when the mixture was heated to 80 ° C. and stirred for 3 hours, all the crystals of acetamiprid were dissolved. After cooling to room temperature, 200 g of isocyanate and 43 g of LPG gas were mixed to prepare a urethane foam. The results are shown in Table 1.

Claims (5)

In the method for producing an insect repellent-containing polyurethane foam, an isocyanate raw material liquid containing isocyanate and a polyol raw material liquid containing a polyol, an insect repellent and a flame retardant are mixed and foamed.
An insect repellent-containing polyurethane foam characterized in that the insect repellent is heated and mixed with the flame retardant to prepare an insect repellent-containing flame retardant, and a polyol raw material liquid is prepared by mixing the insect repellent-containing flame retardant into a polyol. Production method.   The method for producing an insect repellent-containing polyurethane foam according to claim 1, wherein the insect repellent is bifenthrin, acetamiprid, ciphenothrin or thiacloprid.   The method for producing an insect repellent-containing polyurethane foam according to claim 1 or 2, wherein the flame retardant is trichloropropyl phosphate or chlorinated paraffin.   The method for producing an insect-repellent-containing polyurethane foam according to any one of claims 1 to 3, wherein an amine catalyst is further mixed into the polyol raw material liquid.   The method for producing an insect repellent-containing polyurethane foam according to any one of claims 1 to 4, wherein the insect repellent-containing flame retardant is mixed in a polyol at 0 to 35 ° C.