JP6698981B1 - A method for producing a moisture-curable terminal isocyanate prepolymer composition and a device for suppressing foaming during moisture curing. - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve a method for producing a moisture-curable terminal isocyanate prepolymer composition in which production and coating are integrated. It is to reduce or suppress the foaming of a cured product that occurs during moisture curing, which is an essential subject of the composition, and to improve safety and environmental friendliness. To suppress foaming of a cured product during moisture curing, a specific carbon dioxide absorbent which absorbs and reacts carbon dioxide economically and selectively was found and foaming was eliminated. To improve the environment during work, the problem was solved by a simple flexible local exhaust gas improvement installation in order to remove the harmful vapors of the unreacted raw materials generated in the immediate vicinity of the heated fluidized discharge. [Selection diagram]

Description

  The present invention relates to a method for producing a moisture-curable terminal isocyanate prepolymer composition, which suppresses foaming of a cured product during moisture curing. Further, the present invention relates to a manufacturing apparatus for removing residual monomeric harmful vapor generated during discharge of a fluid liquid during heating of the composition.

  Current moisture curable terminal isocyanate prepolymer curable compositions for use in products such as adhesives, sealants, coatings, among others, are in the field of moisture curable polyurethane reactive hot melt curable compositions (abbreviated as PURHM). Is especially famous. The PURHM has free-flowing properties under heating while being protected from moisture, instantaneous adhesion and solidification upon cooling at room temperature, and thermoreversible properties. However, once the fixing/adhering substance absorbs moisture (moisture) in the air or the like, a thermosetting type by moisture cross-linking (cross-linking reaction between the terminal NCO group and the NH2 group generated by the reaction of the NCO group with moisture) ( Heat irreversible). Therefore, the one-component type is excellent in operability, the high productivity is achieved by instant fixing, and the thermosetting type is excellent in function and performance and economical. The product group has penetrated the market widely and forms one area in the industry.

  Thus, while the current PURHM has the above-mentioned superiority, it requires a long time to manufacture PURHM and consumes a lot of energy, and also has problems in reaction control and safety in the mass production. In addition, when using the product, a dedicated coating machine is required, and the product is put into the melting tank, heated and remelted for use, so it is necessary to heat the entire device including piping and discharge part. , Consumes a lot of energy. Further, there remains a problem in terms of safety of foaming of a cured product at the time of moisture curing and residual monomer (isocyanate vapor) at the time of heat use.

  The present inventor has consistently studied energy-saving PURHM to solve the problems of the current law. As a result, in the invention of the prior application (abbreviated as the invention of the prior art), focusing on the rapid reactivity of polyurethane and the reaction without by-products, the moisture-curable terminal isocyanate prepolymer was directly stabilized from the raw material in a short time. We found a synthetic method and invented a new manufacturing method that integrates so-called manufacturing and product use, which can be used as a product as it is. The outline is that the main agent and the curing agent are separated at room temperature and continuously or intermittently supplied to a heated small capacity mixer/reactor while maintaining a constant ratio, and the inside of the reactor is To react in a very short time. Energy saving was realized because only a small amount of local heating is required for heating. The prior invention has already disclosed [Production device and system (Patent Document 1)] and [PURHM adhesive with reduced residual monomer (Patent Document 2)].

  The present invention aims to further improve the prior invention. Firstly, the foaming of a cured product generated during moisture curing is suppressed. The second is to improve the safety and work environment when using the product. Also, the effective use of a large amount of reaction heat generated during short-time synthesis of the prepolymer (use as a heating source of the reactor, etc.) has been confirmed to be energy saving.

The present inventor has diligently studied to solve these problems.
The first problem, improvement (reduction, suppression) of foaming at the time of moisture curing is an essential problem of moisture-curable polyurethane. The foaming phenomenon is known, and many are described in urethane chemistry textbooks, literatures, etc., including the foaming mechanism, and are known to those skilled in the art. However, various countermeasures have been implemented, but no practical countermeasures including economic efficiency have been taken. The present inventor was able to find a technique for effectively removing carbon dioxide gas (which is generated in a large amount in a short time), which causes bubbling, at low cost, and was able to solve the problem.

Regarding the improvement of safety and work environment which is the second problem, when the heated fluid of the composition of the present invention is used, the unreacted raw materials (diisocyanate etc.) remaining in the composition are heated to increase the vapor pressure. It may rise, deteriorate the working environment, and adversely affect the human body. As a result of investigating countermeasures, a work environment was improved by installing an inexpensive and simple flexible local exhaust device that can efficiently remove harmful vapors such as residual monomers in this composition in the immediate vicinity of the heated fluidized discharge product. It has become possible to significantly improve sex. In addition, they also have a feeling that they can effectively use the heat of reaction.
The terms and the like used in the present invention are defined below.
Regarding “solidification” and “fixation”; there is no strict distinction between the two. “Solidification” refers to “solidification”, that is, “solid”, and “fixation” refers to things such as “fixing force and fixing force”, which are not necessarily solid. The melting point tends to be higher in “solidification”.
Regarding "ejection" and "application"; there is no strict distinction. Application refers to application on the adherend through discharge. Regarding "crosslinked product" and "cured product": There is no strict distinction, and the cured product of the present invention refers to a thermosetting cured product.

Japanese Patent No. 5044749 Japanese Patent No. 5853295

Course of Polymer Chemistry [Minori Imoto, Ryoichi Fujishiro, Showa 42]

  The present invention is a further improvement of the method for producing a moisture-curable terminal isocyanate prepolymer composition by integrating the production and coating of the previous invention. That is, it is to reduce or suppress the foaming of a cured product generated during moisture curing, which is an essential subject of the composition, and to improve safety and environmental properties. The present invention solves these problems and provides a novel method for producing a moisture-curable terminal isocyanate prepolymer composition that suppresses foaming during moisture curing.

The present inventor diligently studied the above problems. As a result, regarding the suppression of foaming of the cured product at the time of moisture curing, it was possible to find a specific carbon dioxide absorbent that economically and selectively absorbs and reacts with carbon dioxide and eliminate foaming. Regarding the improvement of the environment during work, by removing the harmful vapor of the raw material unreacted components generated in the immediate vicinity of the heated fluidized discharge by installing a simple and flexible local exhaust device, it is easy and easy to operate. We have found that it can save space and can be removed economically and efficiently. As described above, the present invention has been solved and the present invention has been completed, that is, the present invention consists of the following inventions.
(1) A method for producing a moisture-curable terminal isocyanate prepolymer composition, which uses an apparatus for simultaneously producing, discharging and applying a prepolymer,
(i) (A) Main agent is an MDI-based polyisocyanate that is liquid at room temperature (25° C.), (B) Curing agent is a liquid polyol at room temperature, (C) Foam inhibitor is either a main agent or a curing agent. One or both of them, and (ii) the two agents are used and are constantly supplied to the heated mixer/reactor at a constant ratio, and the NCO/OH group ratio is 1.4/1 to 5.0/. 1. A composition obtained by a short-time reaction under heating is excellent in reactivity for a short time, fluidity at the time of heating and solidification at room temperature, and has an effect of suppressing foaming of a cured product at the time of moisture curing. A method for producing a curable terminal isocyanate prepolymer composition.
(2) The polyisocyanate is a diisocyanate, the diisocyanate content (based on the total amount of polyisocyanate) is 70% by mass or more, the polyol is a diol, and the diol content (based on the total amount of polyol). Is 70% by mass or more, and the method for producing a moisture-curable terminal isocyanate prepolymer composition according to (1).
(3) The method for producing a moisture-curable terminal isocyanate prepolymer composition according to (1) or (2), wherein the foaming inhibitor is a remover for absorbing carbon dioxide, reacting, and the like.
(4) The above foaming inhibitor is a dry powder of quicklime (CaO) powder, and the content of the powder in the prepolymer composition is 5 to 60% by mass ( The method for producing the moisture-curable terminal isocyanate prepolymer composition according to 3).
(5) A one-pack type moisture-curable terminal isocyanate by discharging the composition (heat-flowable composition) described in (1) above in a moisture-blocking and moisture-blocking storage container and sealingly storing the composition. The method for producing a moisture-curable terminal isocyanate prepolymer composition according to any one of (1) to (4), which is used as a prepolymer composition.
(6) A flexible local exhaust device is installed in the immediate vicinity of the heated fluid discharge of the composition according to any one of (1) to (5) above to remove harmful vapors such as residual monomers. An apparatus for producing a moisture-curable terminal isocyanate prepolymer composition, which is characterized.

As described above, the present invention has an object to further improve the production method (previous invention) of a moisture-curable terminal isocyanate prepolymer composition in which production and coating are integrated, which has not been conventionally achieved, that is, the composition. It is to reduce or suppress foaming of the cured product that occurs during moisture curing, which is an essential issue, and to improve safety and environmental friendliness. The present invention has solved these problems and was able to provide a novel method for producing a moisture-curable terminal isocyanate prepolymer composition that suppresses foaming during moisture curing. The present invention has a great need from the industrial world and is expected to contribute to the industrial world.

1. First, the prepolymer and the raw material that are the base material of the composition of the present invention will be described.
(1) prepolymer;
(B) General properties: The prepolymer is substantially free of moisture (moisture content of 500 PPM or less), and is substantially free from moisture by using an MDI diisocyanate that is liquid at room temperature and a diol that is liquid at room temperature. Instantaneous synthesis is achieved by reacting in a blocked heating/mixing container. The prepolymer is a prepolymer having a low molecular weight thermoplastic terminal NCO group. The prepolymer exhibits fluidity under heating, solidification/fixation at room temperature, and thermoreversibility under exclusion of moisture. However, once the solidified product comes into contact with air (humidity), it is converted into a thermosetting type by moisture crosslinking. Those exhibiting such properties can be used as the prepolymer of the present invention.

(B) Structure and Instant Synthesis; The prepolymer has a linear structure containing a terminal NCO group (which may partially contain a branched structure), and is a low molecular weight thermoplastic prepolymer having an average number of functional groups of 2 A polymer (including a mixture with a monomer and one having a different molecular weight distribution) composition. In the instant synthesis of the prepolymer, the above-mentioned MDI (diphenylmethane diisocyanate)-based diisocyanate and diol are used as the main raw materials, and the reaction is carried out at an extremely high speed under heating and mixing, and the reaction is stable almost instantaneously (preferably 1 to 30 seconds). Is synthesized.

(C) Flowability: The flow temperature is 70°C to 170°C. At 170° C. or higher, it exhibits superfluidity, and long-term retention may cause deterioration of the prepolymer and gelation. On the contrary, when the temperature is lower than 70°C, the fluidity is lowered and it is not suitable as a prepolymer. Suitable flow temperatures are 80°C to 150°C, more preferably 85°C to 130°C. As for the melt viscosity, which is an index of fluidity, the melt viscosity (lnη) to temperature (1/T) curve can be approximated linearly.

(D) Instantaneous solidification property: When the heated fluid in the reactor (molten prepolymer) is discharged (applied) to the base material at ambient temperature in the ambient environment, it is cooled at ambient temperature and solidified. Since the solidification rate by the cooling is high, instantaneous solidification (only the cooling time) is possible.
Although the instant solidification time is affected by the ambient temperature, it is usually evaluated at room temperature (25°C). Further, since the solidification temperature of the prepolymer is greatly influenced, the solidification temperature of the present prepolymer is generally in the range of about 60°C to 25°C. Within this range, sufficient instant solidification is secured. If it is 60 or more, the heating fluidity may be lowered, and if it is 25° C. or less, the instantaneous fixing property may be lowered.

(E) Moisture crosslinkability; The instant solidified material immediately absorbs moisture in the outside world, that is, moisture contained in the adherend, and quickly advances a moisture curing (moisture crosslinking) reaction. Then, when cured at room temperature for 1 day, thermosetting (crosslinking) progresses, and due to extension of curing time, it is converted into a tough thermosetting body (heat irreversible). The heat resistance of the cured product is also good.

  However, on the other hand, the prepolymer has the above-mentioned excellent characteristics (ro-ho), but on the other hand, the cured product tends to absorb moisture in the air and foam when moisture-cured, and the cured product has a poor appearance. However, there was a problem that the strength was reduced. There is also a problem of residual monomer vapor in the heated fluid discharge.

Main raw materials for prepolymer synthesis and NCO group/OH group ratio, and foaming inhibitor (A); polyisocyanate that is liquid at 25°C. Ideal raw material is MDI that is liquid at room temperature and has an average functionality of divalent. Is desirable. However, it is difficult to obtain the raw material due to contamination of impurities during synthesis, formation of side reaction, change during storage, etc., and normally, isomers, functional groups, structural differences or molecular weight distributions are used. To be done. Therefore, if the diisocyanate component content is 70% by mass or more in all polyisocyanate components, it can be used. It is preferably 80% by mass or more. In other words, the polyisocyanate has an average number of functional groups in the range of 2.5 to 1.8 and a number average molecular weight (Mn) of 250 to 1000, and a diisocyanate raw material that is liquid at room temperature is desirable, but a small amount of trifunctional (triisocyanate component) is used. May be included.

  The number of isocyanate functional groups is preferably 2.2 to 1.9. It is more preferably 2.1 to 1.9. If the average number of functional groups exceeds 2.3, the prepolymer may gel and stable fluidity may not be obtained upon heating. On the other hand, even when it is 1.9 or less, stable fluidity may not be obtained. As the polyisocyanate, any of aromatic, aliphatic and alicyclic monomers and prepolymers can be used as long as they have the above average number of functional groups and molecular weights. In the present invention, an aromatic system is suitable, and a liquid MDI system having a low vapor pressure at room temperature is particularly preferable.

  The reason is that since it is liquid at room temperature, operability (storage, supply of raw materials, etc.) is remarkably excellent. In addition, it is highly reactive and excellent in instant synthesizing property, and thus is most suitable for energy-saving synthesizing of the present invention. In addition, the monomer vapor pressure at room temperature is low and it is excellent in safety. Furthermore, the prepolymer obtained by the synthesis has high fluidity and flow stability, instantaneous solidification upon cooling at room temperature, moisture curability (crosslinking), and physical properties of the cured product.

Examples of the liquid MDI system are: (a) MDI (diphenylmethane diisocyanate; (4,4′MDI, 2,4′MDI, 2.2′MDI isomer or mixture of isomers), (b) carbodiimide modified isocyanate, uretdiimine modified The isocyanate (c) is a terminal MDI-containing prepolymer obtained by reacting excess MDI with a diol, or (d) a blend of the terminal MDI-containing prepolymer and a 4.4'MDI monomer. As for the terminal NCO prepolymer which is liquid at room temperature, there are many that can be easily reacted with a short-chain diol or a low-viscosity diol in the presence of excess MDI, and these are also useful as a raw material. Examples thereof include Coronate MX, Coronate MT, Coronate 1050, Millionate NM, Millionate MR200, etc. (above, Tosoh Corporation), and castor oil modified terminal NCO prepolymer (URIC N2023; Ito Oil Co., Ltd.) and the like. The commercially available products may be used alone or as a mixture, and the raw material of the present invention is not limited to these.

(B); A polyol that is liquid at room temperature (25° C.) is most preferable, but a diol having an average functionality of divalent is most preferable, but like the diisocyanate, a pure product is obtained due to impurities during synthesis, side reactions, moisture absorption during storage, etc. Difficult and usually has a distribution. It can be used if the content of the diol component is 70% by mass or more in all the polyol components. It is preferably 80% by mass or more. In other words, the average functional number (Fn) is 2.3 to 1.8, preferably 2.1 to 1.9. It does not matter if a small amount of trifunctional polyol is included. A polyol having an average molecular weight (Mn) of 62 to 2000 is desirable, and the number average molecular weight (Mn) is in the range of 62 to 2000, similarly to the above, particularly in a very short time of the prepolymer due to fast reactivity with the main agent. Due to synthesis (convergence of reaction), good fixing temperature of the prepolymer, and excellent cured physical properties (strength, heat resistance, etc.) after moisture curing.

  Further, if the molecular weight is 62 or less, it is difficult to obtain an appropriate monomer. If the molecular weight is 2,000 or more, the sticking property and the performance of the cured product may be deteriorated, and the viscosity may be increased. The viscosity is preferably low in the case of adding an antifoaming agent, an antisettling agent or the like to the diol side. The preferred molecular weight range is 90 to 1000, more preferably 90 to 800, and even more preferably 90 to 600. In particular, use of a short chain diol as a chain extender enables ultra-short time synthesis, leads to high production, and tends to obtain high fluidity under low heating and high solidification temperature. It is useful.

  As these diol raw materials, the main chain structure has a polytetramethylene ether type, a polyethylene oxide-propylene poxide polyether type, a polyester type, a polycarbonate type, a castor oil modified type, etc., and is usually described in urethane chemistry. Selected from diols. The polyether diol type is useful in that it has a low viscosity, the polycarbonate diol type is in terms of hydrolysis resistance and strength, and the polyester diol is useful in enhancing heat resistance.

  Further, as the short chain diol as a chain extender, those having 3 to 10 carbon layers are useful. They are triethylene glycol, 1.4 butane diol, 1,5 pentane diol, 1.6 hexane diol, 3 methyl pentane diol, octane diol (2 ethyl.3 hexane diol), 2.4 diethyl 1.5 pentane diol. However, a small amount of trifunctional glycerin, trimethylolpropane, etc. can also be used as long as the heating fluidity of the prepolymer is not deteriorated. These diols are used alone or as a mixed diol. However, the diol of the present invention is not limited to these.

NCO/OH stoichiometric ratio; The NCO/OH stoichiometric ratio is the basis for controlling the molecular weight of the prepolymer, and especially the combination of the main agent (A), the curing agent (B) and the NCO/OH stoichiometric ratio produces It is possible to greatly change the properties of the polymer, and particularly to greatly change the fluidity at the time of heating, the solidification property at room temperature, the moisture crosslinking property, and the like. From the polymer theory, the number average molecular weight of the prepolymer synthesized from the raw materials can be theoretically calculated if the above (A), (B) and the NCO group/OH group ratio are determined. It is known that this theoretical value agrees well with the experimental value (Non-Patent Document 1). The prepolymer suitable for the present invention is obtained with an NCO/OH group ratio of about 2/1 or a slight excess, and is mainly composed of a terminal NCO group-containing trimer (ABA) having a molecular weight distribution. Formed as.

  In the present invention, the NCO/OH group ratio is in the range of 5.0/1 to 1.4/1. The reason is that at 5.0/1 or more, an increase in the prepolymer molecular weight cannot be expected, and the unreacted diisocyanate monomer (residual monomer amount) only increases. In addition, there is a possibility that excessive carbon dioxide gas is generated during moisture curing, foaming of the cured product is increased, and the physical properties of the cured product are deteriorated. On the other hand, it has the effect of improving the instantaneous stable synthesis of the prepolymer and the reaction convergence. On the other hand, when it is 1.4/1 or less, the molecular weight of the prepolymer is increased, the fluidity may be lowered due to the increase in viscosity, and the reaction convergence of the instantaneous synthesis may be significantly lowered. The preferred NCO/OH ratio is 2.5/1 to 1.8/1, more preferably 2.3/1 to 1.9/1.

  In addition, the application range of the present invention is wide, for example, within the scope of the present invention, by appropriately adopting the main agent (A), the curing agent (B), the NCO/OH ratio, depending on the application, As an example, it is also possible to prepare a one-liquid type room temperature quick-curing moisture-curable polyurethane curable composition and the like.

(C) foam suppressant;
As an antifoaming agent at the time of moisture curing, it does not inhibit the synthesis of the prepolymer of the present invention, is stable to long-term storage, does not deteriorate the physical properties of the moisture cured product, and carbon dioxide gas. If it can absorb and suppress foaming, it can be used regardless of liquid or solid. Among them, specific powders, for example, quicklime powder (CaO), hydrophobic zeolite powder, inorganic porous powder, cement powder, calcium hydroxide, lithium carbonate, carbon dioxide-absorbing dry algae, etc. , Quicklime powder which is excellent in removal effect, operability, economy and the like is preferable.

  The function of the foam suppressor is to remove carbon dioxide gas generated during moisture curing. However, even if carbon dioxide gas is generated, for example, if the cured product is a porous material (wood, etc.) or an inorganic powder high filler addition system, etc., an escape route for carbon dioxide gas is secured, and the cured product layer is thin. In the case, when the amount of carbon dioxide gas diffused from the thin layer is small or the amount of carbon dioxide gas is small, the cured product does not foam or the foaming is so small that the adhesive layer is thin and strong like an adhesive. If sufficient is ensured, it may not be necessary to add the foaming inhibitor. However, in the rapid reaction as in the present invention, the amount of carbon dioxide gas generated is large, and when the thickness of the cured product layer is large, the harmful effects (decrease in strength, poor appearance, etc.) due to the foaming of the cured product are large, so foaming prevention The addition of agents is essential.

  The quicklime powder can be added to either the diisocyanate side or the diol side, but it is desirable to add it to the diol side because of excellent operability. As the amount of addition, the content of quick lime in the prepolymer composition is appropriately 5 to 60% by mass. If it is 5% or less, efficient absorption of carbon dioxide gas may be lacking, and the foaming prevention performance may be deteriorated. On the other hand, when the content is 60% by mass or more, the foaming-preventing effect is remarkable, but the viscosity may be increased and the fluidity may be lowered, and as a result, the coating property may be significantly lowered. Furthermore, there is a possibility that the physical properties of the cured product after moisture curing may deteriorate, and the cured product may become brittle.

  The preferable addition amount range is from 20 to less than 50% by mass. It is more preferably 25 to 45%. The particle size of the powder may be within a range that does not hinder coating, approximately 10 microns or less, and the lower limit is not particularly limited as long as good dispersibility and long-term storage plan stability are obtained. Commercially available powder can be used. However, in order to maintain excellent carbon dioxide absorption, the quicklime powder used should be sufficiently dry. Therefore, the amount of adsorbed water in the powder is best under anhydrous condition, but it can be used if it is 0.1% by mass or less. It is more preferably 0.05 mass% or less.

(D) anti-settling agent (phase separation stabilizer);
The true specific gravity of the above quicklime powder is about 3.5, the specific gravity of the diol used in the present invention is about 1.0, and if the quicklime powder is added to the diol in this state with an extreme difference in specific gravity, Immediate settling, phase separation, cake-like deposits are formed, and the composition having suitable fluidity of the present invention cannot be obtained. The use of a phase separating agent is indispensable in order to maintain good phase separation stability of the quicklime powder in the diol and maintain fluidity. As a result of searching various phase separation stabilizers, it was found that addition of commercially available fine powder silica powder (Aerosil) was very excellent. Moreover, it has been found that a relatively small amount of addition imparts a structural viscosity to the diol, prevents settling, and maintains good phase separation stability and fluidity.

  The added amount is 0.5 to 5 mass% with respect to the total amount of the added liquid agent. If it is 0.5% by mass or less, the phase separation stability tends to be impaired, and if it is 5% by mass or more, the fluidity may decrease, and the effect of increasing the addition is poor. It is preferably 1 to 5% by mass, and more preferably 1 to 3%. The finely powdered silica powder also needs to maintain the same dry state as the quicklime powder.

(E) catalyst;
Since the MDI system of the present invention reacts very quickly under heating, instantaneous synthesis (about 1 to 30 seconds or less) is possible even in a non-catalyst system, and therefore the addition of a catalyst is optional. However, another object of the present invention is to realize further energy saving and high productivity by instantaneous synthesis, so that fast curing property is essential, and there is a catalyst-free system that cannot obtain instantaneous synthesis. Is effective. The catalyst used is a known catalyst used in ordinary polyurethane chemistry. Examples of these catalysts include the following. Organometallic compounds of tin, iron, titanium or bismuth, such as dibutyltin dilaurate (DBTDL), dioctyltin dilaurate, tin(II) salts of carboxylic acids and the like are suitable as catalysts for use in the present invention. The concentration of the catalyst in the composition used is about 0.0001 to 0.5% by weight, preferably 0.005 to 0.05% by weight, more preferably 0.05 to 0.002% by weight.

(F) Other additives;
If desired, the composition of the present invention may contain a stabilizer, an adhesion promoter, a filler, a tackifier, a pigment, an antioxidant, an ultraviolet absorber and the like. In particular, addition of an inorganic powder from which substantial water has been removed as a filler lowers the prepolymer concentration in the composition, resulting in a decrease in the amount of carbon dioxide gas generated, and a route for carbon dioxide gas removal of the cured product. It is useful because it has the effect of forming foams and an indirect foaming improving effect can be expected. It is also useful for controlling (relaxing) a large amount of reaction heat during instant synthesis of a prepolymer. Also, the combined use with a foaming inhibitor (CaO powder) is useful for improving operability and safety. Further, the addition rate of the powder in the prepolymer is 70% by mass or less at the maximum including the foaming inhibitor. It is preferably 50% by mass or less.

2. The method for producing the moisture-curable polyurethane prepolymer composition of the present invention will be described.
(1) Manufacturing apparatus: An example of the apparatus configuration of the present invention is shown below. In addition, it is essential that the device configuration and operation be under a moisture barrier.
(A) Two (A liquid; diisocyanate, B liquid; diol) storage container, (A) the two precision discharge device, (C) heating mixing/reaction device/discharge unit, (D) residence exhaust device, and (E) Consists of piping, switching valve, (f) control equipment, etc.

(A) Reservoir container; Reservoir tank: Any material can be used regardless of whether it is made of metal, glass, plastics or the like as long as the moisture barrier property is maintained. The storage tank structure must be (a) always under a moisture barrier condition and capable of supplying and supplying a liquid agent and a foam suppressing agent. (B) It is desirable to provide a member capable of detecting the remaining amount of the liquid agent. (c) Usually, the foaming inhibitor is added to the B liquid side. It is desirable that the storage tank can be stirred and defoamed, but it is not necessary. d) It is necessary to maintain a nitrogen gas atmosphere or a dehumidified dry air atmosphere during the storage and operation of the main agent and the curing agent. However, it is not necessary to bring the atmosphere into a pressurized state except in special cases. (E) It is desirable, but not necessary, to provide a screen (stainless steel mesh, etc.) on the outlet side of the storage tank to remove foreign matters such as gelled material of liquid agent, excessive powder particles, and impurities.

  In addition, as another form of the storage container, a container (cartridge) is filled with an agent A (main agent), an agent B (curing agent; a system with or without addition of an antifoaming agent) manufactured in a separate step in advance. You can use one. (F) Normally, the storage tank is used at room temperature (25°C), so it is not necessary to install a heating device in particular, but it is acceptable to install a heating device in preparation for low temperature measures (decrease in fluidity) in winter. Absent. The storage tank capacity is not particularly limited.

  In order to supply both liquids in the storage container to the reactor, they are connected to the reactor via a precision metering device, directly or via a switching valve or the like. The supply of the both liquids does not usually require pressurization, and can be performed by the suction force of the precision metering device. However, in supplying the high-viscosity liquid agent, it is possible to use a pressure system or a heating system.

(A) Precision quantification device;
a) Precision metering pumps, micro gear pumps, precision metering pumps such as mohno pumps, etc., which are very useful because the discharge amount can be accurately controlled by controlling the effective discharge volume of the pump, the pump rotation speed, etc. is there. Further, b) a positive load measuring method or a volume measuring method such as a plunger measuring method is also effective. The discharge amount is precisely controlled by the cylinder volume, piston stroke length, etc. Various commercially available products are provided for both pumps, and any of them can be used. In addition to this, it is possible to use a material that can stably ensure a precise fixed amount by precision processing.

(C) Heated mixing/reaction device;
Both of these precision metering devices are connected to a heated small capacity mixer/reactor either directly or via a conduit via a switching valve. (A) Main agent, (B) Hardener liquid (including foaming inhibitor, etc.) at room temperature (may be partially heated), both liquids always maintain a constant ratio (NCO group/OH group ratio) However, it is supplied to the mixer and mixed at a high speed to form a uniform solution, and at the same time, the reaction is converged in an extremely short time (instantaneous) to obtain a thermoplastic composition exhibiting stable heat fluidity. The obtained composition is directly discharged from the discharge port at the lower end of the mixer to the adherend (normal temperature) and applied as a product.

  Further, as another form, a conduit is provided at the discharge port to discharge continuously or intermittently in a moisture impermeable container under moisture/interruption, and the discharge liquid is stored as a sealed storage liquid. Any method of preparing the one-pack type moisture-curable prepolymer composition solution can be used. The one-pack type has the advantage that it does not require a dedicated coating machine, the working place is not limited, and the coating operation can be performed easily and economically. The method of collecting, storing, and using the composition liquid is not limited.

  In the present invention, the reaction system was made small in capacity as a measure against the reaction heat that is rapidly generated, and the experimental device was implemented by using a simple model device. The reactor capacity is about 0.3 to 2 ml, but 0.5 to 1.2 ml is preferable. If it is less than 0.3 ml, it may be difficult to process the mixer. Further, when the amount is 2 ml or more, the heat of reaction becomes large, which may make temperature control difficult in the simple apparatus system of the present invention. However, the present invention is not limited to this.

  However, for reactors, there is a great need for medium to large capacity, and as a countermeasure against heat generation, safety equipment, device structure (insulation, etc.), equipment design of measurement equipment, etc. are carefully performed from the results of the present invention, It is assumed that there is no hindrance to medium to large capacity allocation of resources.

  Custom-made products and various commercially available products can be used for the heating members of the mixer/reactor. For the mixer structure, dynamic mechanical stirring/mixing method and static unstirred mixing (static mixer) can be used. (SM)) method can be used. The latter is structurally simple, as it does not require a mechanical power source. However, on the other hand, when the thermoplastic composition of the present invention has a thermal fluidity and exhibits a structural viscosity (thixotropic), the thermal conductivity of the liquid agent tends to be non-uniform, so that the fluidity has a distribution. However, it may be difficult to obtain uniform flow stability. Therefore, the dynamic mechanical stirring and mixing method is superior in the addition system of the antifoaming agent of the present invention.

  On the other hand, in the prepolymer composition of the present invention that does not exhibit thixotropy, the liquid agent containing the prepolymer has a low molecular weight, and therefore it is easy to adjust as a relatively uniform solution under heating. For these, the static mixer method, which makes the device structure simpler, is effective. At present, the commercially available SM (made of metal) has the smallest capacity and the internal volume is about 1 ml, and the SM mixing element and the outer cylinder that houses it have a separated structure. There is a restriction in the gap (handling, decrease in thermal conductivity, etc.).

  The SM with the outer cylinder/mixing element integrated structure, which has improved these drawbacks and can cope with smaller capacity and larger capacity, is excellent in energy saving and easy operability by improving thermal conductivity. .. A metal or alloy is effective as the SM material, and the SM can be manufactured by a 3D printer.

(D) Local exhaust system;
When the heated fluid of the moisture-curable prepolymer composition synthesized in the heating mixer/reactor is discharged from the discharge port provided at the lower end of the machine toward the non-bonding material at room temperature, There is a risk that the material will be exposed to high temperatures. Liquid MDI (monomer) is relatively safe at room temperature because of its low vapor pressure. However, since the temperature at the time of work (on the discharge port and on the non-adhesive) is considerably high, the vapor pressure becomes high, which may not be negligible. , There is a concern about environmental pollution and harmfulness to human body due to vapor inhalation.

  As a countermeasure for this, a flexible local exhaust system [Fig. 1] is installed in the immediate vicinity of the heated fluidized discharge (for example, a polyethylene pipe is installed) to easily remove residual monomeric toxic vapors, which is extremely useful for environmental improvement. Exert an effect on. The local exhaust device may or may not be directly attached to the manufacturing device (heating mixer).

  When directly attached, it is effective for application using a robot. Further, it is particularly effective when the exhaust port of the local exhaust machine is not connected to the draft device. It is also convenient that it can be used regardless of the work place. In addition, it is necessary to install an absorber (water, alkaline water) for absorbing isocyanate vapor or the like at the time of discharge in the local exhaust device to devaporize it. Further, as a secondary effect of the local discharge, it is expected that the suction force of the local discharge promotes cooling of the adherend-like discharge material, lowers the temperature of the discharge material, and enhances instantaneous adhesiveness. ..

(3) Prepolymer production conditions; (a) NCO group/OH group ratio; described in the above paragraphs [0027 to 0028].
(A) Reaction temperature: 60 to 170° C. is possible. The temperature is preferably 80 to 150°C, more preferably 100 to 130°C. If it exceeds 170° C., the speed becomes too high and the resulting prepolymer may be deteriorated. If the temperature is 60° C. or lower, the production rate of the product may be slow, and the product may be solidified.
(C) Reaction time: A range of 1 to 120 seconds is possible. It is preferably 1 to 30 seconds, more preferably 1 to 15 seconds, and most preferably 1 to 10 seconds. If the time exceeds 120 seconds, the reaction rate is too slow and not suitable for the present invention. If it is less than 1 second, it may be difficult to control substantially. The reaction time (instantaneous synthesis) is preferably as short as possible, but 30 seconds or less is sufficient. However, in consideration of positive utilization of reaction heat to the heating source of the reactor, 10 to 15 seconds or less is desirable.

(4) Another form of the present invention;
As described above [0043], a one-pack type RHM can be easily manufactured by using the manufacturing method of the present invention. A discharge temperature of 70 to less than 100° C. is suitable for the production. The reason for adopting such a low heating temperature is that the filling container and operability can be greatly improved. For example, the container may be a metal/plastic laminated foil or the like as a tube container for hermetically sealed storage. Further, the melting of the contents can be easily carried out by immersing in the boiling water of an electric pot, or by using a simple type low-temperature heating device or the like. The coating operation can be easily performed by hand pressure extrusion without using DISPENSER, and is very economical regardless of the work place, and can be used as an RHM having excellent operability (instantaneous solidification).

  Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. The raw materials used in the examples and the outline of the test/evaluation method and the like are shown below.

(1) [raw material]
The raw materials used in the examples are shown in [Table 1].
(2) [Test/Evaluation method]]
(A1) Drying of foam inhibitor and anti-settling agent;
A predetermined amount of the foam inhibitor and the anti-settling agent were collected in a 10 ml glass sample tube (reactor), mixed, dried and dehumidified at about 180° C. for 30 minutes in a small dryer, and sealed. The sample was used as a foam inhibitor for prepolymer synthesis. It was also used for tests for evaluating long-term storage stability (phase separation stability) and fluidity at room temperature.
(A2) Instantaneous (short time) reaction time of the prepolymer and exothermic temperature measurement;
(A1) Remove the cap of the tightly closed sample tube, enclose a stirring rod with a thermometer, set it in a heating aluminum block and dry it at 150°C for 20 minutes to dehumidify the inside of the sample tube and lower it to the standard set temperature (100-105°C). Immediately after, while blowing N2 gas, the sample tube was covered with a cap (provided with the liquid agent inlet and the N2 gas inlet) and sealed. At the same temperature, from the liquid agent inlet, a predetermined amount of raw material (pre-measured in PP disposable), agent B (hardener), agent A (main agent) were added in that order, the sealing port was closed, and then left standing for about 1 Hold for 2 minutes, during which the two liquids were in a separated state and did not react, and immediately after confirming the internal temperature (100° C.), the stirring and exothermic temperature, that is, the time to temperature were measured manually. The reaction time was defined as the reaction time with the maximum slope time of the exothermic temperature of the temperature curve.

(A3) Heated fluidity test: The fluidity was evaluated by a method based on Gardner viscosity measurement.
Preparation of various standard viscosity liquids: The following viscosity liquids were prepared from various commercially available liquids with known viscosities at 25°C (reference values). (Each adjustment liquid; viscosity at 25° C. is 70 mPa·s, 300 mPa·s, 500 mPa·s, 1,000 mPa·s, 3,000 mPa·s, 5,000 mPa·s, 10,000 mPa·s, 30, mPa·s, 30, 2,000 mPa·s, 80,000 mPa·s, about 2.0 ml of this liquid was sampled in a 10 ml glass sample tube (inner diameter 18 mmφ, height 35 mm) and sealed.
About 2. An evaluation sample synthesized under heating ml (in a 10 ml sample tube) was used, that is, the sample tube was turned over, and the migration time of the sample solution and the like were measured. Similarly, a fall test was performed on the reference liquid at 25° C., and the fluidity of the sample liquid was estimated by comparing the two. Although it was difficult for the evaluation judgment to have variations in measurement, the melt viscosity, which is an index of fluidity, showed a tendency that the melt viscosity (lnη) to temperature (1/T) curves could be approximated linearly. ..

(A4) Evaluation of solidification property at room temperature: The solidification temperature of the heated fluid of the synthesized prepolymer composition was determined by the method of Example 1 (g). The solidification temperature is the temperature at which the enclosed spatula (stirring bar) is fixed by the solidification of the fluid, and is set as the solidification temperature (the higher the temperature, the better the room-temperature solidification (instantaneous solidification).

(A5) Moisture curability (crosslinking) evaluation; The moisture curability of the coated product of Example 1(g) was determined by standing at room temperature (in air), curing, and by time measurement of moisture curing. The judgment was based on the evaluation of strength and heat resistance of the cured product.

(A6) Evaluation of foam suppression during moisture curing;
The coated product of Example 1(g) was cured at room temperature, and the foaming state of the cured product was observed over time. The evaluation was made based on the number of bubbles generated and the expansion (bulging) of the cured product.

(A7) Evaluation of physical properties of cured product (appearance); Example 1(g)) The coated product was aged at room temperature, and the appearance was observed with time.
(Strength); A test piece (about 2 mm wide, 0.2 to 0.5 mm thick and 15 mm long) was cut out from the coating material, and the piece was cured at room temperature (7 days, 30 days). The bending strength was evaluated. The evaluation was shown by the number of times the test piece was broken by repeatedly applying a bending load to both ends of the test piece.
(Heat resistance); Example 1 (g)) A small piece (about 2 mm square and a thickness of 0.2 to 0.5 mm) of the coating material is cut out, the thin piece is set on a hot plate, and the temperature rising rate is set. (10° C./min), the temperature was raised to 200° C. at a constant rate, and changes in the external shape (melted state) of the strip during the temperature rising process were observed with a loupe to determine the heat resistance evaluation. The evaluation was made based on the melting temperature.

a8) Evaluation of storage stability of main agent and curing agent;; Inorganic powder is mixed in raw materials (main agent and curing agent) for the purpose of suppressing foaming and the like. The phase separation stability (based on the difference in specific gravity between the powder and the raw material) was measured and evaluated over time.

  Details of the other test methods are described in the corresponding Examples or individually in Tables 2 and 3, and the evaluation of Examples and the like is given priority.

1. Evaluation of properties and foam suppression by short-time synthesis of prepolymer (Example 1)
a) Reaction device: A stirring rod with a thermometer is set in a 10 ml glass sample tube (outer diameter 21 mmφ height 40 mm), a cap made of polyethylene/cellophane tape composite sheet is made, and the sample tube is covered with a thermometer. The stirring bar of was sealed. In addition, the cap is provided with a N2 gas replacement/blowing port in the tube and a liquid agent (main agent, curing agent input port), and the sample tube/cap tube connection part, etc., is covered with cellophane tape and/or adhesive tape in order to avoid mixing of moisture. I closed it with.
b) Weighing and drying of foam suppressing agent: The foam suppressing agent (Table 1; quicklime powder; 1.0 g) was placed in a 10 ml glass sample tube and dried and dehumidified at about 160 to 180°C for 30 minutes.
c) Set a stirring rod with a thermometer on the sample tube, set the glass sample tube with the cap removed to the heating aluminum block (100 x 20 mm square, central sample tube installation part (outer diameter 23 mm x depth 15 mm), and place the aluminum block on it. After heating at about 150° C. for about 20 minutes to sufficiently dehumidify the inside of the reactor, the temperature was lowered, the temperature was kept at 100° C., and a cap was immediately put on and sealed. The inside of the tube was replaced with N2 while blowing.

(D) First, [Table 1] Curing agent (B1); P400/octanediol (70/30 mass%) mixed solution; 0.68 ml (1 ml PP disposable filling liquid; 4.27 mg equivalent) was dripped from the liquid agent inlet. Then, the foaming inhibitor was uniformly dispersed by stirring for about 1 minute and allowed to stand for 1 minute. Then, 1.0 ml (8.54 mg equivalent) of the main agent (A1) Coronate MX was added in the same manner, and immediately, the liquid agent charging port and the N2 blowoff port were quickly closed. Let stand for about 2 minutes. The two liquids added during this period were not mixed and the liquid temperature (internal temperature) was maintained at 100° C., and no heat generation due to the reaction was observed. The equivalent ratio (NCO/OH ratio) of the raw materials was 2/1.

(E) Then, when vigorous manual mixing and mixing of both liquids is started, the reaction is almost instantly started and heat is generated to increase the viscosity. After about 30 seconds, after confirming that the liquid temperature reaches 130°C, immediately remove the reaction tube from the heating block. Air cooled. The product solution (inside A1; 130°C) was a white, free-flowing liquid without bubbles, and the liquid temperature decreased with the extension of the air-cooling time, and the viscosity of the liquid liquid significantly increased at the liquid temperature A2 (;100°C). After about 20 minutes, it showed fluidity up to about 80°C, and a white solid was obtained at about 45°C (solidification temperature).
(F) When the reaction tube is installed again on the aluminum block and reheated, the fluidity increases with the rise of the liquid temperature, and the fluidity at the liquid temperature of 100° C. and the liquid temperature of 130° C. is the initial fluidity ( Almost the same fluidity as A2 and A1) was retained. The thermoreversibility of the fluidity of the prepolymer composition was confirmed.

"(G) Evaluation of foam-inhibiting property and cured product"; In order to recover the heated fluidized liquid after reheating (130°C) and evaluate the product, remove the fluidized liquid with a stirring rod with a cap removed. The liquid is taken out, the entire surface of the 100 mm square PP plate is applied in a strip shape (thickness, 0.1 to 2 mm, width, 3 to 10 mm) and left at room temperature (indoor) (measured with time for 1 to 30 days). Then, the moisture curability (after 1 day), the foam inhibiting property, and other cured product properties (folding strength, heat resistance) were measured. The coated product was converted to a thermosetting type, the strength was tough, and the heat resistance was 150° C. or higher (meaning formation of a crosslinked body). It was also confirmed that foaming was significantly reduced in the cured product, and the effect of the foaming inhibitor was remarkable. The test conditions and the results are shown in [Table 2].

(Example 2)
As the antifoaming agent used in Example 1, it carried out according to Example 1 except that the amount was reduced to 0.5 g. The test conditions and results are also shown in [Table 2]. From the table, although the various properties of the prepolymer were similar to those of Example 1, the tendency of the foaming inhibitory property to decrease due to the decrease in the amount of the foaming inhibitor can be seen.
(Example 3)
As the antifoaming agent used in Example 1, it carried out according to Example 1 except having increased to 1.5 g. The test conditions and results are also shown in [Table 2]. From the table, various properties of the prepolymer are on par with those of Example 1, and it can be seen that the foaming inhibitory property tends to be improved by increasing the amount of the foaming inhibitor.

(Example 4)
Prepolymer synthesis was carried out in the same manner as in Example 1 except that the reaction temperature was raised to 130°C. The result was substantially the same as in Example 1. The test results and the like are also shown in the table.
(Example 5)
Main agent (A1) Coronate MX; 1.5 ml (12.8 mg equivalent) was used, except that the NCO/OH ratio was changed to 3/1, the other conditions were the prepolymer synthesis conditions shown in [Table 2], and the operation, etc. It carried out according to Example 1. The test results and the like are also shown in the table.
(Example 6)
0.85 ml (4.27 mg equivalent) of P400 was used as a curing agent, the other conditions were the prepolymer synthesis conditions shown in [Table 2], and the operation and the like were carried out according to Example 1. The test results and the like are also shown in the table.
(Example 7)
P400; 0.85 ml (4.27 mg equivalent) and 0.02% of catalyst were used as the curing agent, and the other conditions were the prepolymer synthesis conditions shown in [Table 2]. The test results and the like are also shown in the table.
(Example 8)
The main ingredient was N-2023; 2.3 ml (8.54 mg equivalent), catalyst: 0.02% was used, the other conditions were the prepolymer synthesis conditions shown in [Table 2], and the operation and the like were carried out according to Example 1. The test results and the like are also shown in the table.
(Example 9)
The same formulation as in Example 1 was used, except that the main agent was added to the foaming inhibitor (CaO) to prepare a uniform mixed solution, and then the curing agent was added. Others were carried out according to Example 1. The test results and the like are also shown in the table.

(Comparative Example 1)
The same procedure as in Example 1 was carried out except that no foam inhibitor was used. The test conditions and results are also shown in [Table 2]. According to the table, various properties of the prepolymer composition were sufficient and exceeded those of Example 1 (there was a large amount of heat generation, a maximum of 150°C was recorded, and instantaneous synthesis was short time), but foaming of the cured product was remarkable. Regarding the suppression of foaming, the effect of the foam suppressing agent was confirmed.
(Comparative example 2)
(A1) Coronate MX; 0.65 ml (5.54 mg equivalent) was used as the main component in the absence of a foam inhibitor, the NCO/OH ratio was 1.3/1, and the other prepolymers shown in [Table 2]. Operations and the like were performed according to Comparative Example 1 under the synthesis conditions. The test results and the like are also shown in the table. A short (instantaneous) synthesis delay was observed.
(Comparative example 3)
In the absence of an effervescent suppressor, Millionate MR200; 0.94 ml (8.54 mg equivalent) was used as the main component, the other conditions were the prepolymer synthesis conditions shown in [Table 2], and the operation was performed in accordance with Comparative Example 1. Carried out. The test results and the like are also shown in the table. Subsequent tests were stopped due to gelation during the reaction.
(Comparative example 4)
Polyethylene diol T5650E; hardener, 0.5 ml (2.20 mg equivalent), HDI prepolymer D201; 1.0 ml (4.42 mg equivalent) catalyst; 0.02% It was used. The other conditions were the prepolymer synthesis conditions shown in [Table 2], and the operations and the like were carried out according to Comparative Example 1. The test results and the like are also shown in the table.

1) (Examples 1 to 9); Consideration of foam suppressor addition system
(A) Foam suppression performance: The effect of adding quick lime (CaO) as a foam suppression agent is remarkable for foam suppression performance (Examples 1 to 9).
On the other hand, it was not possible to suppress foaming in the system in which the inhibitor was not added (Comparative Examples 1 to 4).
In the foam suppressor-added system, the foam-suppressing effect tended to increase with increasing addition, while the fluidity upon heating tended to decrease. In terms of strength, the bending strength tended to decrease. It is considered that the cured product has sufficient heat resistance (150 degrees or more) and practical performance. In addition, the addition of the depressant shows a lower exothermic temperature than the non-added system (Comparative Example 1), and is expected to have an exothermic effect.

(B) Short-time synthesis of prepolymer); A short-time synthesis of 30 seconds or less was achieved in the absence of a catalyst (in Example 7, a catalyst was added, but it was slightly slower, and 30 seconds due to an increase in the amount of the catalyst). It is understood that the following is possible:
(C) Solidification/fixing property when cooled at room temperature; The solidification temperature is in the range of 35 to 45° C., and practical performance is considered sufficient.
(D) Other performance aspects are summarized in Table 2, and also from this result, it is considered that foaming is suppressed and the performance is sufficient.

2) (Comparative Examples 1 to 4); Consideration of System without Addition of Foam Inhibitor a) Comparative Example 1 is a comparison test of Example 1 without the foam inhibitor.
b) Comparative Example 2 is the one in which the effect of the NCO/OH system of Comparative Example 1 was observed (NCO/OH; 1/3) because the molecular weight of the prepolymer increased and the reaction time (reaction convergence) was delayed. Conceivable.
C) In Comparative Example 3, gelation occurred during the reaction, probably because Millionate MR200 having a function of 2.5 was used as the main component. Probably because gelation (crosslinking reaction) occurred during synthesis.
d) Comparative Example 4 is an example of HDI/T5650E system as an example of non-MDI system. Even with the addition of a catalyst (0.02%), the reaction time was long, and it was disadvantageous in terms of fast curing.

Examples and comparative examples are shown in Table 2 above, but these are merely examples, and the present invention is not limited thereto.

2. Test of compounding foaming inhibitor and anti-settling agent with liquid agent (curing agent, main agent) (Example 10)
Blending test (Experiment No. 10-1 to 10-13)
a) A foaming inhibitor (corresponding to the amount added to the curing agent of Example 1) and a predetermined amount of the anti-settling agent (shown in [Table 3]) are placed in a 10 ml glass sample tube and dried and dehumidified at about 160 to 180°C for 30 minutes. did. Next, c) set a stirring rod on the sample tube, transfer to a heating aluminum block (100 x 20 mm square, central sample tube installation part (outer diameter 23 mm x depth 15 mm), set the glass sample tube with the cap removed, and set the aluminum block After heating at about 150°C for about 20 minutes to sufficiently dehumidify the inside of the reactor, lower the temperature, hold at 100°C, add 1 ml of curing agent (diol), and mix for about 2 minutes at the same temperature. Immediately, a cap was put on and sealed.
b) The sample tube liquid agent was removed from the block plate, stored at room temperature (25 degrees), and subjected to the test. The formulation and test results are also shown in [Table 3].

The following can be said from Table 3.
c) The stability of phase separation can be controlled by adding an anti-settling agent to prevent the anti-foaming agent (quick lime powder) from settling.
The proper addition amount of the anti-settling agent is about 1 to 5% with respect to the liquid agent. When added in an amount of 5% or more, the stability is maintained, but the fluidity is conspicuously reduced, and the cost of the product is increased, which is meaningless. In addition, there was no particular difference between the anti-settling agents (hydrophobic and hydrophilic).

(Comparative example 5)
Compounding test (Experiment No. 5-1 to 5-4)
a) Using zeolite powder as a foaming inhibitor and calcium carbonate powder as a filler, a test was conducted according to the formulation shown in [Table 3] as in Example 10, and the results are also shown in the table.
The following can be said from Table 3.
Zeolite powder system has a property of adsorbing water, which is an essential component as a reaction agent of moisture crosslinking source, probably because it requires fine adjustment in operability compared to quick lime powder, and it has stable phase separation and stable fluidity. It was observed that the sex was lower than that of quicklime powder.
In addition, calcium carbonate powder was good in both phase separation stability and fluidity.

3. Curability test using a curing agent and a base compound that are pre-blended and adjusted with a foam inhibitor and an anti-settling agent;
A test was conducted to see the effect of the pre-adjusted curing agent on the curability and foam suppression.
(Example 11)
a) Compounding reagent: As a curing agent, 1,70 g of a storage solution (containing CaO≈60%) stored in Example 10 (Experiment No. 11) at room temperature for 7 days was used for the test. The curing formulation is a curing agent (P400/PD9 mixed solution): 0.70 g (0.42 mg equivalent), a main agent: Coronate MX; 1.22 g (0.84 mg equivalent), a foam inhibitor: CaO; 1.0 g. ..
b) Preliminary operations and curability tests were carried out in accordance with Example 1 using a two-component system in which the curing agent was Experiment No. 11 and the main agent was MX. As a result, substantially the same results as in Example 1 were obtained (foaming inhibiting property, good fluidity during heating, synthesis time of 30 seconds or less, and fixing temperature of 40° C.). Other physical properties of the cured product were also good. From this fact, it is considered that there is no influence of the pre-adjusted product, which supports the validity of the present invention.

  As described above, the example is a model test of the present invention (assuming correspondence with an actual tester), and shows improvement of problems such as foam inhibition, while maintaining excellent characteristics of the current technology. It is possible to understand the usefulness of the present invention.

It is a conceptual diagram of a simple type flexible residential exhaust device.

10 Heated steam inlet 11 Exhaust conduit
12 Trap tank (backflow prevention tank)
13 Absorption Tank 14 Pump for Discharge 15 Discharge Port 16 Device Pedestal (Box)
(Reference) Reaction device of the present invention (inside the dotted line)
A1 Main agent storage tank A2 Hardener storage tank B1 Main agent pump B2 Hardener pump C Mixer motor D Stirrer E Heating reactor F Discharge port G Melt coating material H Adherent

Claims (2)

A method for producing a moisture-curable terminal isocyanate prepolymer composition, which uses an apparatus for simultaneously producing, discharging and applying a prepolymer, wherein (i) (A) the main component is liquid at room temperature (25°C). of MDI-based polyisocyanate, (B) curing agent, a polyol liquid at room temperature, (C) carbon dioxide absorption, as removing agent for the reaction, a dry powder of quicklime (CaO), as blowing agents, the main agent , it is contained in either or both of the curing agent, (ii) using the said base resin and curing agent, at all times a constant ratio, and supplied to the heated mixer and reactor, reaction conditions main agent and curing agent , NCO / OH group ratio of 1.4 / 1 to 5.0 / 1, the reaction temperature is 60 to 170 ° C. and the reaction time is in the range of 1 to 120 seconds, composition obtained by the heating under short reaction time A ) the content of the antifoaming agent in the composition is 5 to 60% by mass, b ) the short-time synthesizing property, c) the fluidity upon heating, and d) the instantaneous solidification property of the fluid discharge liquid at room temperature. E) A method for producing a moisture-curable terminal isocyanate prepolymer composition, which has a foam-inhibiting property of a cured product at the time of moisture curing after solidification. The above polyisocyanate is diisocyanate, the diisocyanate content (based on the total amount of polyisocyanate) is 70% by mass or more, the polyol is diol, and the diol content (based on the total amount of polyol) is 70% by mass. The method for producing the moisture-curable terminal isocyanate prepolymer composition according to claim 1, wherein the content is at least mass %.

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