JP5044749B2 - Thermoplastic polymer production apparatus and system, and polymer production method using the apparatus - Google Patents

Description

The present invention relates to a production apparatus and a production system for continuously producing a reactive hot melt composition or a thermoplastic polymer for the hot melt composition. More specifically, a production / coating apparatus and a system of the apparatus, wherein the product (polymer) is inspected on-line when continuously producing the thermoplastic polymer for the composition, And a method for producing the polymer using the apparatus.

In recent years, curable compositions such as adhesives, pressure-sensitive adhesives, coating agents, sealing agents, and injection / sealing agents have been increasingly improved in performance and functionality. In terms of manufacturing, there is a strong demand for a highly reliable manufacturing apparatus and management system that guarantees energy saving, high productivity, safety and easy environment, and product quality.
Conventionally, hot melts and reactive hot melts are prominent as curable compositions that satisfy both high productivity and environmental properties. Both are useful in terms of high productivity and environmental performance. However, it was not satisfactory in terms of energy saving. This is because conventional production is performed by mixing and stirring and reacting at a temperature of 80 to 100 ° C. for several hours after filling raw materials into a reaction vessel. The reaction is batch-type, and in taking out and storing the product, the product is extremely disliked by moisture, so it is necessary to completely block the moisture, and the product is stored on the basis of strict control. When the product is used (applied), the product is loaded into a melting tank of the coating device, heated and melted, and the entire device such as a pipe is heated for coating. As described above, in the conventional method, the manufacture and use of products are separated, and maintenance management such as manufacture, storage and use is complicated. In addition, there are problems such as high consumption of heat energy.

  In order to overcome the problems such as energy consumption, the present inventor, in the prior application (Patent Document 1), manufactured and applied a reactive hot melt directly from the raw material, and reacted using the apparatus. A production method for producing a thermoplastic polymer, which is the main component of a hot melt, in a very short time, and a production method in which the production and application of a polymer (product) are integrated are shown. As a result, a manufacturing method in which reactive hot melt is converted from raw materials to products in one step and applied as it is at the site of the application work is disclosed, and it is disclosed that the process is much more energy-saving and labor-saving than the conventional technology.

Thus, the manufacturing apparatus of the prior application satisfies both high productivity and energy saving, and the product manufactured by the apparatus reduces the environmental load and the product cost, and is extremely economical. However, since no means (function) for confirming the quality of the product or the like has been added to the device, it cannot be denied that the user tends to worry about the quality of the product manufactured by the device. It was. The reason is that the apparatus is excellent in high-speed production and is used in a high-speed production line. At that time, if a production trouble (for example, poor adhesion) occurs, many product defects occur in a short time due to high-speed production. Therefore, production troubles must be avoided. Today, product failure, as well as economic loss, significantly reduces corporate brands and causes fatal damage. Therefore, the device is required to ensure the quality assurance of the product while maintaining energy saving / high productivity with priority over anything.

For example, a method for measuring the temperature (for example, Non-Patent Document 1) and coloring of an applied body has been disclosed for product confirmation under high-speed production such as conventional hot melt. However, these conventional methods use a product manufactured in advance and confirmed in quality by laboratory product inspection. For this reason, the application confirmation can be made only by determining the presence or absence of the application body on the surface of the adherend. On the other hand, in the present invention, a raw material that is liquid at normal temperature is used to produce a polymer (product) on the apparatus in a very short time and used on the line. Therefore, the suitability of both polymer production and coating must be confirmed on the device. This confirmation operation is extremely difficult and is a concept that has not been known so far, and has never been known.

Japanese Patent Publication No. 4470073

Apiste Corporation, catalog (NEW ultra-compact thermal image sensor)

The present invention relates to a reactive hot melt and an apparatus for high-temperature production of thermoplastic polymer for hot melt and energy-saving production, and overcomes the quality problems of the product and maintains high productivity of polymer and energy-saving production. However, a new continuous production apparatus and system for the polymer, or a new continuous production / coating apparatus for the polymer, which can ensure the quality of the product on the production line, And providing a system. Furthermore, it is providing the novel manufacturing method, evaluation method, and composition of a thermoplastic polymer using this apparatus.

The present inventor has intensively studied to overcome the above-described problems. As a result, devices and systems with specific structures and configurations can overcome the above-mentioned problems and ensure product quality on the production line while maintaining high productivity and energy-saving production of thermoplastic polymers. It has been found to be a new continuous production apparatus and system for the polymer, or a new continuous production / coating apparatus and system, which is economical and more reliable. Furthermore, a new production method, evaluation method, and composition of a polymer using the apparatus have been found, and the present invention has been completed.
That is, the present invention provides: An apparatus and a system for continuously producing a reactive hot melt composition or a thermoplastic polymer (hereinafter abbreviated as a polymer) as a main component of the hot melt composition, the apparatus comprising: (1) the polymer A storage container for storing each of the first agent and the second agent, and (2) from the storage container, the first agent and the second agent are always supplied to the mixer at a constant ratio. 2 precision metering dispensers to supply, (3) changeover valve (4) mixer with or without heating unit, (6) having dispensing unit with heating unit, and (A (2) A thermoplastic polymer production apparatus and system comprising a means for confirming the production of the polymer and / or (B) a means for confirming the application of the polymer.

2. Furthermore, (5) it has a storage part which has a heating part between the mixer of (4) and the discharge part of (6).
3. Further, the means for confirming the production of the polymer of (A) is (a1) measurement of exothermic peak temperature or exothermic peak time, (a2) model calculation of polymer production, (a3) measurement of melt viscosity, a4) Any one or a combination of the measurement of the composition.
4). Further, the means for confirming the application of the polymer (B) is either (b1) the temperature of the applied body applied on the adherend, (b2) the appearance, (b3) the measurement of the color tone, or the It is a combination.

5. Further, signals obtained from the above measurements 3 to 4 are input to a computer, and data processing is performed in real time by the computer. (C) Inspection means for determining confirmation of polymer production and coating, and polymer production / coating Management means for managing the history is provided.
6). The thermoplastic resin as described in any one of 1 to 5 above, wherein the apparatus and system for continuously producing the thermoplastic polymer as described in 1 above can integrally perform the production and application of the polymer in the apparatus. A polymer production apparatus and system.
7). The apparatus and system for producing a thermoplastic polymer according to any one of the above 1 to 6 is a two-part production apparatus and system, and a production apparatus and system for a reactive hot melt or a thermoplastic polymer for hot melt It is.
8). The method for producing and inspecting a thermoplastic polymer, coating, characterized in that the production of the polymer, the confirmation of coating, and the history of the production / coating are managed by the means (A) to (C) described above. It is an inspection method or a management method.

9. Reactive hot melt characterized by producing a two-component reactive hot melt or a thermoplastic polymer for two-component hot melt using the thermoplastic polymer manufacturing apparatus and system described in 1 to 6 above or This is a method for producing a hot melt thermoplastic polymer.
10. (9) The reactive hot melt or hot melt polymer according to (9) above, wherein (4) the mixer temperature is 20 to 250 ° C, and (6) the discharge portion temperature is 50 to 280 ° C. It is a manufacturing method.
11. The polymer obtained by the production method according to 9 or 10 is used as a main component of a moisture curable composition, an adhesive curable composition, a photocurable composition, or a redox curable composition. A moisture curable reactive hot melt composition, an adhesive reactive hot melt composition, a photocurable reactive hot melt composition, or a redox curable reactive hot melt composition.
12 The composition of claim 11 is melt-coated (discharged) using the composition described above, and the composition is cured (cross-linked) by heating and / or irradiation with light / UV after fixing (adhesion). This is a curing acceleration method.

As described above, the present invention relates to an apparatus for high production of reactive hot melt and hot melt polymer and energy saving, overcoming the problem of product quality assurance, high productivity of thermoplastic polymer and energy saving production. A new continuous production apparatus and system for the polymer, or a new continuous production / coating apparatus and system, which can ensure excellent product quality while maintaining Obtained. Furthermore, a novel production method, evaluation method and composition of a thermoplastic polymer using the apparatus were obtained. As a result, the present invention has a great industrial advantage.

It is the schematic of a polymer manufacturing apparatus, a coating device, and a system. It is the schematic (front sectional drawing) of a mixer and a storage device. It is the schematic of the measurement sensor of a polymer production | generation and application | coating. It is a flowchart of a polymer production | generation and application | coating. It is a conceptual diagram of data processing and data management.

The present invention will be described below. First, the following terms used in the present invention are defined as follows.
“Fixed” refers to a certain type of cohesive force (adhesive force) that accompanies a change from a so-called liquid to a solid, and includes “so-called“ adhesion ”of the boundary region between the liquid and the solid.
“Crosslinking” usually refers to chemical crosslinking, but also includes physical crosslinking (where heat resistance is improved).
The “thermoplastic polymer” refers to a normal linear polymer, and includes a prepolymer having a relatively low molecular weight. In addition, a polymer (initial polymer or polymerization precursor) that retains fluidity when heated even if it is a thermosetting polymer is included.
The “polymer” in the present invention refers to the “thermoplastic polymer” in the present invention unless otherwise specified.
“Two agents” means “two liquids” and “agents” mean “liquids”, including those that are easily liquefied by slight heating (about 40 ° C.) even if they are solid at room temperature. .
“Continuously” “produce” refers to continuously supplying and reacting raw materials (two agents) at a constant ratio when a thermoplastic polymer is produced and discharged using this apparatus. This includes intermittent supply of raw materials accompanying temporary stoppage of discharge and cycle (intermittent) discharge. “Generation” refers to “synthesis”.

The “reactive hot melt” of the present invention is an initial thermoplastic polymer (a polymer immediately after production or under moisture-tight sealing) that melts and flows (thermoplastic) under heating. When the body is discharged toward room temperature, it is cooled to exhibit solidification or high adhesion, and after solidification, the solidified body is crosslinked by some means to be converted into thermosetting (thermal irreversible). A normal “reactive hot melt” is solid at room temperature and consists of one agent, and moisture in the air is used for crosslinking. A “hot melt” is a thermoreversible polymer that, when heated, exhibits fluidity like a reactive hot melt, but retains its original thermoplastic state without causing cross-linking after fixation. To do.
The “two-component reactive hot melt” of the present invention is a thermoplastic heavyweight that reacts two components in a very short time under heating with a raw material that is liquid at room temperature, and exhibits fluidity under heating. Synthesize coalescence. The subsequent steps of discharging the fluid toward room temperature are the same as the “reactive hot melt” described above. Therefore, the “two-component reactive hot melt” referred to in the present invention can also be defined as “a liquid reactive hot melt product comprising two agents”.

First, the apparatus and system of the present invention will be described.
The apparatus and system of the present invention (hereinafter simply referred to as the present apparatus) uses a raw material consisting of two liquids at room temperature, continuously produces a polymer under heating, and discharges / coats it as a product. . Furthermore, in order to eradicate product defects, a confirmation means (function) for confirming the generation, discharge, and application of a polymer (product) in real time is added on this apparatus. Specifically, the characteristics, discharge state, and application state of the produced polymer are measured and the data is analyzed by a computer (including a microcomputer) to determine the suitability of the product and to confirm the quality of the product. To do.
The present invention will be described with reference to the drawings.
FIG. 1 is a schematic view showing the basic structure of a polymer production apparatus and system (abbreviated as this apparatus) of the present invention. In FIG. 1, this apparatus includes a first agent storage container and a second agent storage container (10, 20), a precise quantitative dispenser (11, 21) for first agent feeding and a second agent feeding, Agent control valve and second agent control valve (12, 22), mixer (30), reservoir (40), heating unit (50), discharge unit (60), first agent meter side sensor (10a, 10b) , Second agent meter side sensors (20a, 20b), mixed state or composition measurement optical sensor (30b), reaction time measurement sensor (30d), reaction temperature measurement sensor (30c), polymer product optical sensor (40b) ), Reservoir temperature sensor (40c), viscosity sensor (40e), discharge temperature measurement sensor (60c), application body temperature measurement sensor (70c), discharge / application body measurement optical sensor (70b), control section (80), etc. It is comprised including. The sensors listed here are examples, and the present invention is not limited to this, and it is not always necessary to include all of them.

The first agent storage container (10) and the second agent storage container (20) store the first agent (raw material: one reactive substance) and the second agent (raw material: the other reactive substance), respectively. The first agent precise quantitative dispenser (11) and the second agent precise quantitative dispenser (21) always mix the first agent and the second agent stored in the storage container into a mixer at a constant ratio. This is a precise quantitative dispenser that has the accuracy of liquid feeding. The two dischargers need to be driven (synchronized) in order to supply the two agents at a fixed ratio. The first agent discharge amount meter side sensor (10b) and the second agent discharge amount meter side sensor (20b) are sensors for measuring the amount of liquid fed from each of the precise quantitative discharge machines. A 1st agent control valve (12) and a 2nd agent control valve (22) are control valves which switch the continuation or stop of each liquid feeding of a 1st agent and a 2nd agent. The mixer (30) is a mixer for mixing and reacting in order to react (polymer production) the first agent and the second agent that have been sent. The reservoir (40) is responsible for aging and / or completion of the polymer produced by sufficiently retaining the produced polymer. Moreover, it is a reservoir for measuring the characteristics of the produced polymer. And a polymer is discharged from a discharge part (60). A heating part (50) heats each of a mixer, a reservoir, and a discharge part, and temperature is controlled. The heating of the mixer accelerates the polymerization reaction of the first agent and the second agent and melts and flows the produced polymer. The heating of the storage part and the discharge part is for smoothly flowing the polymer. In the present invention, it is useful from the viewpoint of energy saving that a large amount of reaction heat is generated in a short time because the polymer is rapidly synthesized, and the reaction heat is actively used. The temperature control of the mixer, storage unit, and discharge unit is precisely controlled including cooling.

The first agent metering sensor (10a) and the second agent metering sensor (20a) are sensors that measure the remaining liquid amount of the raw material in the container of the first agent and the second agent, and continuously measure the remaining liquid amount. Is done. (30b) is an optical sensor for measuring the mixed state or composition mixed by the mixer. (30d) is a sensor for measuring the synthesis time of the polymer. (40e) is a sensor for measuring the melt viscosity or viscosity resistance of the produced polymer. (30c), (40c), (60c), and (70c) are the temperature at the time of polymer production, the temperature of the reservoir, the temperature of the discharge part, the temperature of the coated body on the adherend surface immediately after coating, these It is a sensor that measures temperature. (70b) is an optical sensor for measuring the application state such as discharge, appearance, and color tone of the polymer. The signals measured by each of these sensors are taken into the control system (80) and processed by a computer (including a microcomputer) to determine the suitability of the polymer generation, polymer discharge and polymer application state in real time. It is determined by. Appropriate measures are taken based on this determination. Through this series of operations, product quality control is reliably executed, and as a result, the object of the present invention can be achieved. In the figure, the power supply system, the drive system, the switch system, and the like are omitted, but this figure shows an example of the present invention and does not limit the present invention.

  FIG. 2 is a schematic view showing a specific example of the mixer (30) and the reservoir (40). The mixer may be composed of either a single machine or a plurality of machines, but a plurality of machines are desirable. FIG. 2a shows a plurality of mixer examples, using a dynamic stirring mixer-static mixer (static mixer), and is a diagram of the mixer alone. FIG. 2 b (without a discharge valve) and FIGS. 2 c and 2 d (with a discharge valve) are both examples of a combination of a mixer and a reservoir. In FIG. 2a, two raw materials are supplied to the first dynamic mixer, and the two raw materials are uniformly mixed. The mixing operation is desirably performed at room temperature, and heating is not particularly required, but a heating unit may be provided. Further, it is desirable that the mixed solution is sent to the second-stage static mixer before the reaction of the two components is started. The mixed solution reacts while moving in the heated mixer to produce a polymer, which flows out from the discharge section (60) at the lower end of the mixer and is used for coating. Here, (31) is a mixing container, and (32) is a stirring bar. (33) is a static mixer outer cylinder, and (34) is a mixing element. In order to improve the uniformity and heat transfer of the two agents, 20 elements are shown in the figure. If the number of elements is sufficient, the uniformity required for polymer production can be obtained, but the number of elements can be further increased to provide a multistage mixer. (35) shows the connection part (connector) between mixers. The connecting portion is not always necessary, but it is better to install it for flexibility such as disassembly and assembly of the mixer. In addition, the connecting portion is useful for measuring uniformity and the like, and in this case, it is desirable that the measurement location is a transparent material.

The connecting portion may be connected with a heat-resistant rubber tube. The mixers may be separated from each other by the connecting portion or may be turned in directions. The mixer is heated by the heating unit (50). In the figure, the heating temperatures of the first stage (upper part), the second stage, and the third stage are set and controlled in accordance with the respective reaction conditions. FIG. 2b shows a variation of FIG. 2a. The upper dynamic mixer in FIG. 2a is used as a static mixer, and the lower mixer is used as a storage section (40). The storage portion uses a hollow portion (pipe). Therefore, the pipe reaching the discharge part can be used as the storage part as it is. And there exists an advantage which can adjust a residence time by adjusting a pipe length. The material of the pipe needs to be transparent so that the fluid can be optically measured. Moreover, the storage part of FIG. 2c illustrates the storage part structure which attached the discharge valve (61). (36) is a connector for connecting the mixer and the reservoir. Here, it is used for measurement of characteristics of the produced polymer.

FIG. 2d shows the polymer produced in FIGS. 2a to 2b at one end. The polymer liquid is accumulated in a reservoir, and is sent to a discharger capable of quantitative discharge through a switching valve, and discharged through the discharger. The figure to be shown. Here, (41K, 61K) are switching valves on the supply side to the reservoir and on the discharge side from the reservoir, respectively. (42L) is a switch for controlling the amount of liquid in the reservoir, and (42o) indicates a dehumidifying unit. (63S, 63P) are a cylinder and a piston of the fixed amount discharger, and one shot is discharged by one reciprocating motion of the piston. The discharge amount is controlled by the cylinder diameter and / or the stroke length of the piston. (61D) is a check valve for the discharger. When the product liquid is sent to the reservoir, the switching valve (41K, 61K) delivers the liquid in a state that (41K) is open and (61K) is closed, and the amount of liquid in the reservoir is (42L). ) Ascend until the switch is activated. On the other hand, when liquid is fed from the reservoir to the discharge section, (41k) is closed and (61k) is opened. In this state, the two dischargers for supplying raw materials are in a stopped state. (42o) is always open and connected to the outside air, and includes a dehumidifier for avoiding moisture absorption from the outside air. By providing the discharger, operability such as discharge confirmation of discharge liquid and thread breakage of discharge liquid is further improved. Further, although not shown in the figure, when the polymer produced in the reservoir contains bubbles and obstructs the coating, (42o) is used as a vent port having a switching valve (connected to the decompression unit). You can also. The figures show examples of the invention and are not intended to limit the invention.

FIG. 3 is a schematic diagram showing an example of measurement of polymer production and measurement of discharge and application state.
As a method for confirming the presence of the produced polymer, a method for measuring the molecular weight and / or composition of the polymer is effective. For measuring the molecular weight of the polymer, it is effective to measure the flow viscosity (melt viscosity) of the polymer flowing in the tube. FIG. 3b shows a schematic diagram of a viscosity sensor for viscosity measurement installed on the connector (36). The connector (49u) at the upper end is connected to the mixer, and the lower end (49b) is connected to the reservoir. The viscosity sensor is a vibration viscometer, (43h) is the main body of the viscometer, (43t) is a thermometer installed in the viscometer, and (43s) is a viscosity detector. In the figure, the installation of the viscometer is arranged in the vertical direction, but it may be arranged in the horizontal direction. The reason why the vibration viscometer is preferable is that the viscometer can be reduced in size, the flow viscosity in the pipe can be measured in-line, the measurement accuracy is high, and the response speed is high.

FIG. 3c shows an example of a simpler viscosity sensor, and is a schematic diagram of a sensor for measuring the viscosity resistance of a polymer flowing through an orifice inside a reservoir. The measurement sensor includes a main body (44h), a thin tube (44o), a resistance detector (44s), and a thermometer (44t). (44t) is a thermometer. Here, (44 s) is a sensor for detecting viscous resistance, the sensor is a metal sheet or plastics film (sheet) with a strain gauge attached thereto, and (44o) the bottom (right side of the figure, It is fixed to the cantilever state. (44 s) has a structure that bends as shown in the figure due to the resistance of the viscous liquid flowing in the nozzle at a constant speed. Further, when the liquid is in a non-flowing state, the thin plate is parallel to the bottom of the nozzle, that is, the nozzle is closed, and when the liquid flows (arrow in the figure), the nozzle opens. Since the amount of deflection changes depending on the viscosity of the liquid at a constant temperature and flow velocity, the viscosity resistance can be measured from the change (electrical resistance) of the strain gauge caused by this deflection. From this measurement, the polymer molecular weight produced can be evaluated by the same operation as the viscosity measurement. The sensor can measure the viscous resistance not directly from the change in the electrical resistance of the strain gauge but directly from the measurement of the displacement of the thin plate. As another measurement sensor, a sensor that is deformed or distorted by a pressure made of a thin metal plate such as a bellophram, a diaphragm, or a Bourdon tube is useful. It is also useful to measure the density of the polymer.

FIG. 3d shows an example in which a near-infrared optical sensor is used as an optical sensor for measuring the polymer composition. (45b1) is an incident side (light source), (45b2) is an optical element on the reflection side (spectrometer / detector), and (45b3) is an optical fiber. (45) is a transparent quartz glass plate. From the measurement of the near-infrared spectrum of the polymer liquid produced in the orifice, the produced polymer composition can be confirmed directly. In addition, although it is not a method for directly confirming the production of the polymer, a polymer produced by measuring the mixed state (color tone) of the two agents from the reflection spectrum by using visible light as a light source based on the same principle. It is useful for the evaluation of the uniformity.

FIG. 3e illustrates a measurement sensor for polymer ejection and application. The left sensor (70c) is a sensor for measuring temperature, and is an infrared camera or the like, and measures the temperature distribution of the coated body. The sensor on the right side (70b) is a sensor for measuring the appearance (shape, color tone, etc.) of the coated body. The application status on the surface of the substrate is measured with a VTR camera, high sensitivity CCD camera, high speed CCD camera, etc. Video is measured over time / continuously. In addition, the viscosity of the generated polymer can be calculated by measuring the flow of the discharge / flowing liquid or the flow state of the coated body with a high-speed camera, and determine the suitability of the generated polymer. Is also possible. In addition, by measuring the flow state of the coated body after coating (spreading of coating, coating thickness, etc.) with a VTR camera, it is also possible to determine the suitability of the polymer produced as with the high-speed camera. It is. FIG. 3f schematically shows a polymer application model. The part surrounded by the dotted line in the above figure (1) is a place to be coated. FIG. (2) is an example in which the polymer is appropriately applied to the place to be applied (filled portion). FIG. 3 shows an example in which the polymer (or unreacted raw material or the like) has a low viscosity so that it flows too much and the coating is too wide. On the other hand, FIG. (4) is an example in which the coated body does not spread properly due to poor flow. Figures (3) to (4) are unfavorable application examples.

Next, the member used for FIGS. 1-3 is further demonstrated.
A commercial item can be used for the storage container (10, 20). Since each liquid agent in the container can be supplied to the mixer by the suction force of the precision quantitative discharger (11, 12), it is not necessary to pressurize or heat the container in particular. However, gentle pressurization or heating may be applied in order to make it easy to supply a liquid with a high viscosity. The outside of the container may be directly exposed to the outside air. Moreover, you may equip in the tank etc. which store this container. In order to remove moisture, bubbles and the like in the liquid agent, the tank is preferably connected to a vacuum pump. Further, since the liquid agent is a product as well as a raw material, management of the storage container is important. Since the quality of the product may deteriorate due to moisture absorption, it is desirable to keep the inside of the container in an atmosphere of nitrogen or dry air. The container material may be either metal or plastic, and in the case of plastic, a moisture barrier material is preferable. Further, it is desirable to provide a liquid level meter and a weight meter (10a, 20a) for displaying the liquid supply amount and the residual liquid amount.

Any known and commercially available precision metering dispenser (11, 21) can be used as long as it can continuously and precisely dispense two agents. Of these, volumetric dischargers such as gear pumps, piston pumps, plunger pumps, and syringe pumps are effective. In particular, it is not necessary to heat the discharger, but mild heating may be applied in order to easily supply a liquid agent having a high viscosity. In order to stably produce the polymer, the discharge accuracy of the discharger is particularly important. The discharge accuracy (discharge amount variation) is at least within ± 5%, preferably within ± 3%. In addition, the cylinder material is preferably transparent or semi-transparent so that the state of the inside of the cylinder can be observed, such as liquid supply (mixing of bubbles, etc.), driving of the piston, etc. The piston should be colored. desirable. Moreover, the discharger needs to be able to cope with a liquid agent viscosity of about several mPa · s to several hundred thousand mPa · s. Further, as the liquid switching valves (12, 22), a two-way valve (check valve) is used in FIG. 1, but a three-way valve that connects each of the storage container, the syringe, and the mixer may be used. There is no problem. Moreover, there is no restriction | limiting in particular in this valve, A well-known slide valve, a rotary valve, a non-return valve, a needle valve etc. are used.

As the mixer (30), a mechanical mixer (dynamic mixer) using a normal motor rotation or a static mixer such as a static mixer is suitable. Commercially available products can be used. Although FIG. 2 illustrates a combination of mixers, other combinations may be used. Whether to use a static mixer or a dynamic mixer is selected depending on the conditions of the polymer production site. Moreover, it is a premise that two raw materials can be mixed uniformly in any mixer. In order to obtain the uniform mixing, in the static mixer, at least about 30 mixing elements are required. Preferably 30 to 60 elements are desirable. Further, the clearance between the outer diameter of the element and the inner diameter of the outer cylinder is desirably 10 μ to 5 μ. If it is 10 μm or more, the liquid agent may move through the clearance and not be mixed. If it is 5 μm or less, there is a possibility that the element cannot be smoothly inserted into and removed from the outer cylinder. Further, it is preferable to reduce the size and shape of the mixer by controlling the heat of reaction, quick control of heat transfer, and the like. The mixer volume is preferably about 10 ml to 0.1 ml. Further, when the mixer is used under heating, the material is preferably metal, ceramics or glass. The plastic is preferably an engineering plastic with high heat resistance.

The storage part (40) can improve the thread breakage of the discharge liquid by providing a discharge valve (FIG. 2c / 61) on the discharge side of the storage part. Furthermore, the polymer can be discharged more smoothly by synchronizing the discharge valve and the two-agent supply valve (12, 22). Moreover, FIG. 2d showed the example which supplies the polymer produced | generated via the storage part to the polymer discharge cylinder (63P) provided separately, and discharges from this cylinder. It can also be used for energy-saving hot melt molding and reactive hot melt molding. The discharge section (60) is preferably a heated thin tube (nozzle) in order to precisely control the discharge temperature.

The heating unit (50) is used for heating the mixer, the reservoir, and the discharge unit. Although not shown in the figure, the two discharge machines and the path from the discharge machine to the mixer may be heated, for example, to reduce the viscosity of the liquid agent (two agents). The heating is effective for improving the mixing property and reactivity in the mixer. The heating means may be any of electric heating, infrared heating, heating liquid medium circulation, heating air circulation and the like. The temperature control is desirably precisely controlled, and the temperature control is within ± 5 ° C. of the control temperature, preferably within ± 2 ° C., and more preferably within ± 1 ° C. A cooling unit (mechanism) may be provided to speed up the temperature control response. Here, as the temperature of the heating unit, for example, it is appropriate that the temperature of the mixer is 20 to 250 ° C., the temperature of the storage unit is 50 to 250 ° C., and the temperature of the discharge unit is 50 to 280 ° C.

Next, sensors will be described.
The raw material confirmation sensor is a liquid level meter and a weight meter for measuring the amount of residual liquid in the container, and a flow meter such as an orifice flow meter and an ultrasonic flow meter for measuring the amount of liquid supply. . In addition to this, an optical sensor or the like that directly measures the appearance of the liquid agent in a liquid feeding state (such as mixing of bubbles). In addition, a timer for controlling the movement of the piston of the precise quantitative dispenser is also included in the time measurement sensor. The sensor for measuring production of a polymer is a sensor such as a time sensor, a temperature sensor, an optical sensor, a viscosity sensor, or a pressure sensor.
As the temperature sensor, an infrared camera sensor, a thermistor resistance sensor or the like is useful.
As an optical sensor, a visible light sensor is used for evaluation of mixing properties (measurement of coloring state, etc.), and a near infrared spectroscopic sensor, a laser Raman spectroscopic sensor, an infrared spectroscopic sensor, etc. are used for measurement of polymer formation (chemical composition). Of these, the near infrared sensor is preferable.

The viscosity sensor is a viscometer useful for evaluation of polymer production (molecular weight). In particular, the vibration viscometer is useful for downsizing the apparatus and installing it on an in-line. Also, the viscous resistance sensor illustrated in FIG. 3c is useful.
Further, as a simple measuring method for easily measuring the viscosity (FIG. 3f), 1). In a laboratory, using a number of different standard viscosity polymers (both temperature and viscosity are known), etc., a fixed amount of heated flowing liquid at a constant temperature and time from the nozzle tip to a substrate (100 mm below) It is dropped on a smooth aluminum plate having a corner and a thickness of 5 mm and a temperature of 25 ° C., and the spread / shape of the coated body is measured, and the relationship between the viscosity and the spread / shape of the coated body is calculated by simulation. This can be applied to an actual operating system coated body, and the viscosity of the coated body can be estimated from the spread / shape of the coated body.
Also 2). The viscosity of the polymer can be estimated from the evaluation of the fluidity of the polymer from the liquid breakability of the polymer described later (shown in Example test method (e)). The viscosity measurement method can be easily operated, and by carrying out a detailed comparison test with a standard material with a known viscosity and simulating it, the viscosity can be estimated accurately, which can be used for viscosity measurement of this device. it can.

An infrared camera is useful as a sensor for measuring the temperature (distribution) of the application body as the application body confirmation sensor. In addition, a sensor that directly measures an image such as the appearance, shape, color tone, and flow state of the coated body is useful. These sensors are cameras such as VTR cameras, high-speed digital cameras, and high-resolution digital cameras. In addition, a contact sensor that measures the degree of penetration of the probe and the stringing state by bringing the probe into contact with the surface of the application body is useful as a measurement sensor for the adhesion and / or adhesion of the application body. These contact sensors are incorporated in the line of this apparatus, are measured continuously (for each product), and can be used for discrimination of the applied body.

FIG. 4 is a flowchart showing the production of the polymer and the confirmation of the application using this apparatus.
FIG. 4a shows the overall flow and consists of the following steps. First, in the raw material supply step, the suitability of the supplied raw materials (two agents) is confirmed, then in the production step of the polymer (prepolymer), the suitability of the produced polymer is confirmed, and then the discharge / coating is performed. In the process, the suitability of polymer discharge / coating is confirmed. The confirmation in each process is such that measured data (signal) is transmitted to a computer, processed by the computer, and executed in real time. Here, (YES) in the figure indicates that the data is within the reference value and is appropriate, and (NO) indicates that the data is outside the reference value and is inappropriate. The measurement results are displayed on the display and can be monitored constantly. In addition, the data can be used for polymer production and application history management. As a result, product management is reliably performed. In this case, it is assumed that a computer is used as the confirmation means. However, even if a visual judgment or the like is used as the confirmation means in a laboratory scale or under a small scale production on a low-speed line, the present invention is disturbed. is not. In addition, this flowchart (FIG. 4) shows the example of this invention, and this invention is not limited to this.

FIG. 4b shows the flow of raw material supply and polymer production confirmation. Regarding polymer production, (a1) reaction heat method for measuring exothermic temperature, (a2) calculation method for calculating polymer model, (a3) viscosity measurement method, (a4) composition route method It is. The first raw material supply confirmation is to confirm whether the raw materials (two agents) are being supplied at a constant ratio from two precision quantitative dispensers, and to confirm uniform mixing. An equivalence criterion is defined that defines the molecular weight of the coalescence. Next, the production | generation confirmation of a polymer is performed by either of the following methods. For example, in (a1), the measurement data of the exothermic peak temperature or the exothermic peak time, and in (a2), the equivalence standard, the production temperature and the production time measurement data are processed by a computer to confirm the polymer production. The suitability is executed.
FIG. 4c is a flowchart of the discharge confirmation and the application confirmation. Image (image) data captured in the computer is confirmed during the discharge of the polymer, the confirmation of the application body, that is, the temperature measurement of the application body immediately after application, the temperature measurement, the color tone, etc. Then, image processing is executed, and whether or not application confirmation is appropriate is executed.

FIG. 5 shows a conceptual diagram of data processing, data display, data management, etc. of this apparatus and computer. The outline will be described. Although not shown in the figure, the computer may be composed of a plurality of computers or connected to the net.
(i) Data processing: A signal measured by each measurement sensor is transmitted to a computer (including a microcomputer), and a received signal is subjected to data processing (image processing) by the computer. Data processing performs pre-programmed tasks and converts signals into characteristic values (temperature, time, volume, viscosity, spectrum, etc.). Whether or not the confirmation process is appropriate is basically determined by comparing standard input data (standard value or reference value) of the standard operation system with data (measurement value) of the actual operation system. In addition, the viscosity method (a3) was shown as an example in the data processing process column of this figure.
(Ii) Data display: The operation is configured so that the operation status of all processes (each process) can be confirmed at a glance as needed based on the data processing of (i) all the work time and continuously. When an abnormality occurs in a process with actual operation, an abnormality is immediately displayed at that location and an alarm is issued. Based on this alarm, it is possible to quickly respond to inspection, interruption, trouble, etc. of work.
(Iii) Data integration management: Further, the measurement data and the result of the series of data processing are stored as data, and utilized as a system for integrated management of polymer production and application. The above data processing and data management can serve as the polymer production confirmation means and the application confirmation means of this apparatus, and a more reliable polymer production apparatus and system are constructed. Furthermore, this device can be developed to lead to the construction of an automation system.

First, the data processing for (A) polymer production confirmation will be described in detail. As described above, the polymer of the present invention refers to a polymer that exhibits fluidity at a heating temperature and exhibits fixation or tackiness at room temperature. The raw material of the present invention is a low molecular weight substance that exhibits a free-flowing liquid under heating and at room temperature. Another object of the present invention is to convert a raw material into a polymer in a short time under heating. In the present invention, there is no clear difference in molecular weight between the raw material and the polymer. In the present invention, it is only necessary that the raw material is converted into the polymer, and the raw material and the polymer satisfy the above-mentioned phase state. This conversion is always accompanied by an increase in molecular weight. In the present invention, this increase in molecular weight is defined as polymer formation (synthesis).

First, a method for determining polymer formation in the viscosity method (a3) will be described. According to the polymer theory, a relational expression is established between the molecular weight of the polymer and the melt viscosity. That is, as the molecular weight increases, the melt viscosity increases, but the relational expression depends on the molecular structure of the polymer. There is also a correlation (formation of relational expression) between the melt viscosity of the polymer and the temperature. That is, the melt viscosity decreases as the temperature increases, but this relation also depends on the molecular structure and the like. Using this relationship, it is possible to determine whether or not the polymer is suitable for production by the following steps.

Step (1) Preparation of standard polymer (determination of viscosity standard value): Using this apparatus or an apparatus equivalent to this apparatus, a standard polymer (several types) having different molecular weights is prepared in advance in a separate laboratory. Then, the viscosity at each temperature of the obtained polymer is measured. Specifically, 1) The standard polymer is prepared using a raw material (first agent, second agent) having a known molecular weight and a bifunctional number, and using an equivalent ratio (equivalent basis). ) Is determined and the reaction is completed, the molecular weight is calculated theoretically. The molecular weight of the polymer is adjusted by changing the relevant ratio.
2) The viscosity corresponding to the molecular weight of the standard polymer can be obtained by synthesizing (generating) each standard polymer of 1) above while changing the reaction temperature and reaction time, and simultaneously measuring the viscosity. At constant reaction temperature, polymer formation is also a function of reaction time. Viscosity is determined by measuring the viscosity at each reaction time and determining the viscosity at which the viscosity converges (constant). Is determined. Here, the production time of (ηs) is the standard production time (ts) of the polymer at the reaction temperature. Further, the standard viscosity (ηs) is determined from the test in which the reaction temperature is changed by the same operation. Here, if the reaction is completed for both, both (ηs) approximately match. Further, (ts) varies depending on the reaction temperature. That is, since the reaction is accelerated at a high temperature, (ts) is shortened.

(2) Creation of simulation diagram: When the viscosity is measured by changing the measurement temperature using the standard polymer, a temperature-viscosity curve of the polymer is obtained. By applying this operation to each standard polymer, the viscosity-temperature curve of each standard polymer is determined. That is, a simulation diagram showing the relationship between the molecular weight, viscosity, and temperature of the standard polymer is created, and this diagram is stored in the computer.
(3) Confirmation of polymer production: When standard polymer data (equivalent ratio, temperature, time) is input, its standard viscosity (ηs) is calculated from the diagram. Next, the viscosity measured in the production of the polymer under the actual operating system setting conditions corresponding to the production of the standard polymer, that is, the actually measured viscosity (η) is measured. By comparing the actually measured data (η) of the viscosity with the standard data (ηs), whether or not the polymer is produced in the actual operation system is determined.

(4) Criteria for determining suitability of polymer: Determination of the measured value viscosity under heating is based on the following idea for determining viscosity at room temperature (25 ° C.). As described above, the proper conditions for the polymer of the present invention are fluidity under heating and fixing or sticking at room temperature. Therefore, it is premised that the viscosity at room temperature for satisfying the polymer condition, that is, maintaining a highly adhesive state. The adhesive force required in actual work is not necessarily limited because it varies depending on the working conditions and the like, but the viscosity for maintaining the adhesive at room temperature should be about at least about 500 Pa · s. Assumed. Therefore, first, this viscosity is provisionally determined as the lower limit viscosity (ηo) for holding the adhesive at room temperature. However, when the viscosity is lower than the viscosity (ηo), stickiness (adhesiveness) may not be obtained due to variations in operation. For this reason, the sticking retention viscosity is a sticking retaining standard viscosity (ηos) having a higher viscosity than (ηo) in anticipation of safety. Here, (ηo) is within the standard deviation of (ηos) and corresponds to the lower limit value of (ηos). This (ηos) is given as the standard viscosity (ηs) at the measured temperature under heating. Therefore, by comparing the measured data (η) with the standard viscosity (ηs) from the measurement of the measured viscosity (η) under the actual operating system heating, that is, the measured data (η) becomes the standard viscosity (ηs). If they are equal or larger, stable adhesion (fixation) can be obtained at room temperature, and it is determined that the produced polymer is appropriate.

Next, although not shown in the figure, a model calculation method (a2) which is another aspect of confirmation of polymer production will be described.
First, the data used for the preparation of the standard polymer in the method step (a3) (1) is utilized and executed as follows. Step (1a): Under the standard equivalence ratio (eqs) employed to determine the convergence point of the standard polymer viscosity in Step (1), that is, the standard viscosity (ηs), the reaction temperature and reaction time are determined. From the changed test, the reaction convergence time (ts) at the standard reaction temperature (Ts) is first obtained. Here, the reaction convergence time (ts) refers to the standard reaction time (ts). Furthermore, the standard reaction time (tns) in each reaction temperature (Tn) of this polymer is calculated | required similarly to the above. From this test, a temperature (T) to time (t) diagram at standard equivalents (eqs) of standard polymer formation is obtained.
Step (2a): Polymer production by actual operation is performed under the same conditions as standard polymer production, and measured value data of the equivalence ratio (equo), reaction temperature (To), and reaction time (to) is measured. The The determination of polymer formation is determined by a computer calculation process by comparing input data of measurement data (eqo, To, to) and standard data (eqs, Ts, ts) in the actual measurement system, as in the above-described viscosity method. The Conceptually, the equivalence ratios of the measured system and the standard system are approximately equal, and the temperature and time data (To, to) of the measured system are larger than the temperature and time data (Ts, ts) of the standard system. If so, the polymer is determined to be properly produced.

Next, measurement of the heat generation temperature (a1) is useful. In the present invention, the polymer is produced in a very short time. As a result, a large amount of heat of reaction is generated in a short time during the production process, which is accompanied by a rapid temperature rise. The temperature is accurately measured over time, and the formation of the polymer can be determined from this rapid temperature rise as follows. This method is similar to the calculation method (a2), and measures the exothermic peak temperature (Tp) and the peak time (tp) during the production of the standard polymer and the actual operation polymer, and performs data processing. This is a method for confirming the formation of a polymer. First, in measuring the viscosity convergence data of a standard polymer, the temperature is measured over time under the standard reaction (set temperature). In the polymer formation reaction, after an induction period is first observed, a rapid reaction proceeds and a rapid temperature increase occurs, but then the temperature decreases and stabilizes. Here, the peak time (tp) is defined as the time from the end of the induction period after mixing the two agents to the start of the reaction until the maximum exothermic temperature (Tp). From the measurement of this exothermic curve (temperature / time), it was estimated that the time for the maximum polymer production rate was 1/2 to 1/3 of the (tp). Further, it was estimated that the majority of the reaction was completed at the (tp). Further, it was estimated that the (ts) would be 2 to 3 times or more the (tp) between the (tp) and the reaction convergence time (ts). Therefore, to complete the reaction, 1) keep the reaction solution at the set temperature and extend the reaction time from the (tp). 2) Under (tp), the reaction is performed at a temperature higher than the set temperature. The above is considered to be effective, and the present method confirms the formation of a polymer based on this idea.

The determination of the exothermic peak time (tp) is carried out by first using the same standard polymer (divided into three parts), using the first polymer, and under the set temperature (T1). The temperature of the polymer is measured, and the exothermic peak temperature (Tp1) and the peak time (tp1) are measured. Next, with the second polymer, the set temperature is raised (T2), and similarly, the exothermic peak temperature (Tp2) and the peak time (tp2) are measured. (Tp3) and (tp3) are measured under (T3) with the third polymer. As a result, (tp) is obtained for each set temperature. By plotting this, a set temperature (T) to exothermic peak time (tp) diagram of the standard polymer system is obtained. As a matter of course, the peak time (tp) is shortened if the set temperature (T) is high. The (tp) is related to the convergence (completion) time of polymer formation, and it is suggested that if the (tp) is short, the convergence time is also short.
As in the case of (a2), the determination of polymer formation is determined by comparing the both of the exothermic peak time (tp) as the standard system data and the exothermic peak time (tpo) as the actual operating system data. The That is, when the set temperature of the standard system and the actual operation system is the same, the production confirmation of the polymer is made by making (tpo) longer than (tp), and when both peak setting times are the same, This is achieved by setting the set temperature of the actual operation system higher than the set temperature of the standard system.

Furthermore, measurement of the composition method (a4) is also useful. The method is based on measurement of the near-infrared spectrum of the first agent raw material (containing NCO groups), the second agent raw material (containing OH groups) and the polymer for polymer synthesis. For example, when synthesizing a non-moisture curable polymer (terminal OH type polymer), the near-infrared spectrum of the NCO group due to the presence of the first agent isocyanate is measured before the synthesis of the polymer is started. As a result, the NCO group reacts with the OH group and is consumed, and a terminal OH type polymer is produced. That is, since the NCO group disappears in the immediate vicinity of the end point of the reaction, it is possible to determine whether or not the polymer is appropriate based on the disappearance state of the near infrared spectrum unique to this NCO group. Similarly, in the moisture curable polymer terminal NCO type polymer, the reaction opposite to the generation of the terminal OH type polymer, that is, the OH group disappears in the immediate vicinity of the end point of the reaction. It is possible to confirm the production of the polymer by the disappearance state of the near infrared spectrum. Whether the produced polymer is suitable or not is determined by comparing the standard polymer system (input memory) and the actual operation system (measurement) spectrum.

Here, when a static mixer is used, the required residence time for the production of the polymer is given by the following equation.

Residence time (to (seconds)) = [volume of reaction part of this apparatus (V (ml)) / (discharge amount of 1 cycle of two precision quantitative dispensers (v (ml))) × average time of the same cycle ( Sec)]

Here, the reaction part volume is the sum total of the internal volumes of the mixer, the reservoir, the connection part, the connection pipe, and the discharge part. In the actual operation system, the two raw materials are supplied to the mixer, the reaction of the polymer is started, the polymer is generated, and discharged from the discharge unit while moving in the apparatus. This transfer time is given as the residence time, during which the polymer reaction takes place, further ripening and approximately complete. Therefore, the residence time is given as the time obtained by adding the aging time to the standard polymer production time (ts). And it can also be defined that the residence time is substantially the reaction time (to) of the actual operation system. In order to ensure the production of the polymer, the residence time (to) is preferably at least 3 times the standard production time (ts), preferably 5 to 20 times. As mentioned above, although the production | generation confirmation method ((a1)-(a4)) of a polymer was shown, the production | generation of a polymer is determined by producing the program about these confirmation methods and running this program.

  Next, (B) application body confirmation determination will be described. A simple measurement method (paragraph 0033) in which the viscosity is easily measured has been shown, but this method is effective for confirming and determining the applied body. FIG. 3f schematically shows a polymer application model. A portion surrounded by a dotted line 3f (1) is a predetermined application location. 3f (2) indicates a state in which a predetermined portion is appropriately applied (filled portion). 3f (3) indicates an inappropriate application state, such as overcoating and 3f (4) insufficient. For determining whether or not the application state is appropriate, image data that has been appropriately applied is registered in advance as standard image data. Similarly, in the actual operation system, VTR video data and the like of the coated body are obtained, and obtained as actually measured image data subjected to image processing. Appropriateness of the coated body is determined by comparing these two images, that is, by comparing the measured image data with the registered standard image data.

Furthermore, a method based on color tone measurement is useful as another aspect of the confirmation of the applied body. It is particularly useful for redox (oxidation / reduction) type reactive hot melt compositions. The composition contains a redox catalyst (a polymerization initiator and a polymerization accelerator). The two types of catalysts have no change in color tone in the blocked state of catalytic activity (the crosslinking reaction does not proceed). However, when the catalytic activity is unblocked, the color tone changes due to the reaction between the catalysts. The change in color tone is due to a change in the oxidation state of the metal catalyst used in the polymerization accelerator. The change also suggests the start of a crosslinking reaction. Therefore, if the coloration state of the coated body is measured, the position of the coated body and the crosslinking reaction can be measured at the same time, which is an extremely effective determination method. As described above, the determination is made by comparing the actual operation system coloring with the standard system coloring.
Furthermore, as another aspect, there is measurement of the temperature distribution of the application body, and the application state is determined by comparing the image of the actual operation system and the standard system as described above. Furthermore, as another aspect, in order to directly check the adhesion and / or adhesive state of the coated body, for example, it is useful to contact the probe with the surface of the coated body and measure the degree of penetration of the probe and the stringing state. is there. In these cases, the suitability of the coated body is determined by image comparison similar to the above.

Finally, (C) application management will be described. Based on the above confirmations and inspections of (A) to (B), and by utilizing measurement data collected and stored for the inspections, polymer production inspections and coating inspections created in advance In addition, data re-verification is appropriately executed using a history (generation / application) management program. The verification may be automatically performed retroactively using a work downtime (for example, at night), or may be performed automatically by another computer during the work. Through these verification operations, continuous production, coating, and production history management of the polymer can be more reliably performed.
As mentioned above, although this invention was demonstrated using FIGS. 1-5, this figure illustrates this invention and this invention is not restrict | limited by this.

Hereafter, the polymer manufacturing method obtained using this invention apparatus is demonstrated.
1. [Polymer raw material]: The first agent, which is a raw material for polymer production, is one reactive substance, and can react with the other reactive substance to form a polymer. The second agent is the other reactive substance that reacts with the first agent, and can react with one reactive substance to form a polymer. Therefore, both reactive substances can be used as long as they can generate a polymer that exhibits fluidity under heating and solidifies at room temperature. These reactive substances are preferably liquid at room temperature. As these reactive substances, any of polyaddition type substances and addition polymerization type substances can be used, but polyaddition type substances are preferred, and monomers and / or prepolymers are particularly preferred. Alternatively, a coupling agent that uses a reaction between functional groups, a metal cation species and an organic acid anion species, a chelating agent, or the like can be used as long as the molecular weight is increased.

Among these, a reactive substance that can form polyurethane is preferable. The reasons are that it is easy to control the molecular weight of the polymer, that the production rate of the polymer is high, that no by-product is involved in the production of the polymer, and that various reactive substances can be selected. Therefore, this apparatus is optimal for producing a polymer from raw materials in a very short time and stably. One reactive material for polyurethane formation is a functional monomer and / or prepolymer having an isocyanate group (NCO group). These include aromatics such as diphenylmethane 4, '4 diisocyanate (MDI) and derivatives of MDI (including prepolymers of MDI, liquid MDI and modified MDI), castor oil modified MDI, TDI derivatives (prepolymer of TDI), etc. Diisocyanate. In addition, there are aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate (HDI), and derivatives of HDI, or alicyclic diisocyanates such as isophorone diisocyanate, xylidene diisocyanate, hydrogenated xylidene diisocyanate, and derivatives thereof. However, it is not limited to these, The well-known thing used by urethane chemistry can be used.

Among these, MDI derivatives which are advantageous in terms of safety because of a fast curing speed, excellent heat resistance, and low vapor pressure among isocyanates are suitable. The above aliphatic diisocyanates, cycloaliphatics saturated with hydrogen atoms, alicyclic diisocyanates and the like are also particularly useful in obtaining non-yellowing polyurethanes. As MDI derivatives, those having an NCO group equivalent of about 125 to 3000 and an average number of functional groups of NCO groups of about 2 to 3 are suitable, and the number of functional groups is about 2 in order to obtain a linear polymer. Is the best. However, these monomers need only react with an organic active hydrogen group to obtain the polymer of the present invention accompanied by an increase in molecular weight, and the number of functional groups is not necessarily limited thereto.

The other reactive substance is a functional monomer and / or prepolymer having an organic active hydrogen group. Examples of the organic active hydrogen group include —OH group, —COOH group, —NH 2 group, —NHR group, —SH group, and the like. Among these, —OH group (hydroxyl group) is suitable in terms of excellent reactivity with isocyanate (NCO) group, safety (low toxicity, low odor), and low price. Examples of functional monomers and / or prepolymers in which the organic active hydrogen group is —OH group include, for example, polyether polyol, polyester polyol, castor oil, castor oil modified polyol, terminal hydroxyl group-stopped liquid polybutadiene and its hydrogenated product, and terminal hydroxyl group terminated Liquid polyisoprene and hydrogenated product thereof, terminal hydroxylated modified silicone oil, terminal hydroxylated product containing silicone chain in main chain and / or side chain, terminal hydroxyl group containing organic group substituted by fluorine atom in main chain and / or side chain Such as a monster. Low molecular diols such as ethylene glycol, propylene glycol, triethylene glycol, polyethylene glycol, butanediol, hexanediol, 3methylpentanediol, and octanediol are useful as chain extenders. However, it is not limited to these, The well-known thing used by urethane chemistry can be used.

Among these, preferable monomers and / or prepolymers are polyols having an —OH group equivalent in the range of about 31 to 10,000 and an average functional group number of about 2 to 3, and a diol having an average functional group number of 2 is particularly suitable. The reason is that the number of functional groups is about 2 in terms of obtaining a linear polymer. However, these monomers need only react with isocyanate to obtain the polymer of the present invention, and are not necessarily limited to the number of these functional groups.

2. [Polymer Form]: For convenience, the polymer of the present invention is (1) a polymer without crosslinking, that is, a polymer (P1) for hot melt (abbreviated as HM) and (2) with crosslinking. The polymer is divided into polymers for reactive hot melt (abbreviated as RHM) (P2 to P5). Further, the RHM polymer of (2) is divided into moisture-curing RHM (P2, P3) and non-moisture-curing RHM (P4, P5). Further, the moisture curing type RHM is divided into a terminal NCO type RHM (P2) and a terminal silyl group type RHM (P3). The non-moisture curable RHM is divided into a redox RHM curable type (P4) and a photocurable RHM (P5). Furthermore, the difference of the main structures etc. of these polymers is as follows. In the moisture-curing RHM and the non-moisture-crosslinking type RHM, the main chain structures are different from each other because the crosslinking forms are different from each other. However, the production catalyst for polymer production is the same for both, whereas the polymer crosslinking catalyst is different for both. That is, in the former cross-linking, the polymer reacts with moisture in the air to form a cross-linked body, and the product catalyst is used as it is as the cross-linking catalyst. On the other hand, the latter further requires a crosslinking catalyst for radical crosslinking. The polymer and the like will be individually described below.

(2-1) Terminal NCO-type moisture-curing RHM (P2): The polymer is usually a linear polymer, and (i) As a raw material, diisocyanate and the above bifunctional monomers such as diol are used. Is used. The polymer is obtained by an NCO-excess system reaction.
(Ii) The preferable equivalent standard (NCO group / OH group equivalent ratio) is that the NCO / OH ratio is 2.5 / 1 to 1.3 / 1, more preferably 2.5 / 1 to 1.5 / 1. It is. Further, when the equivalent ratio is 2.5 / 1 or more, the sticking property tends to be lowered. Furthermore, the residual probability of the unreacted NCO raw material in the obtained polymer tends to increase, and it is necessary to consider measures against NCO vapor (toxicity) under heating. On the other hand, if it is 1.3 / 1 or less, the NCO group concentration of the resulting polymer is decreased, and the target moisture curability may be decreased. Moreover, since the convergence time of polymer production tends to be long, it is not a preferable direction in the present invention (short-time convergence).
(Iii) Polymer production temperature is 30 ° C to 250 ° C. Preferably it is 50 to 180 degreeC. If the temperature exceeds 250 ° C., the polymer may be deteriorated, and if it is 30 ° C. or less, it may not be possible to produce for a short time necessary for the present invention. The polymer production time (the standard reaction time (ts)) is preferably 1 to 60 seconds. If the production time exceeds 60 seconds, there is a concern that the productivity is lowered, and if it is 1 second or less, it is not necessary to make the reaction sufficiently fast. However, the production temperature and production time of the present invention are not limited to these. As the polymer production catalyst, a known polyurethane synthesis catalyst is useful. For example, a tertiary amine catalyst such as triethylenediamine, an organic tin catalyst such as dibutyltin dilaurate as a metal catalyst, iron, chromium, nickel, Examples thereof include octenoates such as zinc, naphthenates, and acetylacetone complex compounds. The addition of these catalysts can significantly shorten the polymer production time. The amount of these catalysts added is in the range of 0.005 to 5 parts by weight with respect to 100 parts by weight of the total amount of raw materials for polymer production (first agent and second agent).

(2-2) Non-moisture curable RHM (P4): In order for the polymer to perform radical crosslinking, it is necessary to introduce an ethylenically unsaturated group into the polymer main chain. The position of the unsaturated group may be either inside the polymer or at the end. Therefore, (i) functional monomers for forming a polyurethane having an ethylenically unsaturated group in the molecule are useful as raw materials, and the monomers further include monomers containing isocyanate groups, or further containing OH groups. Although any of the contained monomers may be sufficient, Monomers further containing an OH group are preferable. They are the above-mentioned liquid isoprene terminated with hydroxyl groups at both ends, liquid 1.4-type polybutadiene, 1.2-type polybutadiene, etc., and have (meth) acrylic groups in the molecule and one or two hydroxyl groups. For example, mono or diol. Monomers or diols having a (meth) acryl group in the molecule and one or two hydroxyl groups have a vapor pressure at room temperature of 0.1 Torr, more preferably from the viewpoint of the working environment. It is preferably 01 Torr or less and substantially non-volatile or odorless. Examples of the monomers include 2 hydroxyethyl (meth) acrylate, 2 proxyoxy (meth) acrylate, 2 hydroxybutyl (meth) acrylate, 2 hydroxybutyl 3 acryloyloxypropyl (meth) acrylate, 2 hydroxy3 phenoxypropyl acrylate, trimethylol Examples thereof include epoxy esters such as propanedi (meth) acrylate, pentaerythritol tri (meth) acrylate, bisphenol A diglycidyl ether (meth) acrylic acid adduct, and ethylene glycol diglycidyl ether (meth) acrylic acid adduct. However, it is not limited thereto, and those known in acrylic chemistry are used.

(Ii) The equivalent standard is obtained in an OH group-excess system when a linear polymer is produced using difunctional and difunctional monomers of diisocyanate and diol. The NCO group / OH group ratio is preferably about 1 / 1.2-1 / 2. When the equivalent ratio is 1 / 2.5 or less, the sticking property tends to be lowered. On the other hand, when the ratio is 1 / 1.2 or more, the convergence time of polymer production tends to be long, so this is not a preferred direction in the present invention (short-time convergence). Moreover, when producing a polymer using monomers having a (meth) acrylic group in the molecule and having a hydroxyl group, it is not always necessary to use difunctional and diol bifunctional monomers. The polyfunctional isocyanate monomer is reacted with an OH group-excess system using a monool having a (meth) acrylic group and one hydroxyl group (OH group) in the molecule, and is polyfunctional. A polymer having two or more ethylenically unsaturated groups in the molecule obtained by blocking (capping) the NCO group of the isocyanate is obtained. In this case, the NCO group / OH group equivalent standard is preferably a stoichiometric ratio (1/1) to a slightly OH group-excess system. Furthermore, a monofunctional isocyanate monomer containing a (meth) acrylic group in the molecule and a polyfunctional polyol are reacted in an NCO group-excess system, and OH group blocking is carried out within 2 minutes. A polymer having an ethylenically unsaturated group is obtained. In this case, the NCO group / OH group equivalent standard is preferably a stoichiometric ratio (1/1) to a slightly NCO group-excess system.
(Iii) As for the polymer synthesis temperature, since the polymer has an unsaturated double bond inside the molecule, thermal stability needs to be considered, and the synthesis temperature is 30 ° C to 180 ° C. Preferably it is 50 to 140 degreeC. If the temperature exceeds 180 ° C., the stability of the polymer may be lowered, and if it is 30 ° C. or less, the short-time curability required for the present invention may not be obtained. Further, the polymer production time, the polymer production catalyst and the amount of the catalyst added are substantially the same as in the case of the (P2) polymer. In addition, a radical crosslinking catalyst is additionally used for crosslinking the polymer.

(Iv) The radical crosslinking catalyst is a redox (oxidation / reduction) catalyst comprising a polymerization initiator and a polymerization accelerator, or a photocuring catalyst. Redox catalyst is used. As polymerization initiators, cumene hydroperoxide, methyl ethyl ketone peroxide, etc., peroxyester organic peroxides such as t-butyl peroxylaurate, and as polymerization accelerators, cobalt naphthenate and manganese naphthenate are used. Metal soaps such as copper naphthenate are useful, and any known ones are used. Moreover, the usage-amount of the amount of a polymerization initiator is 0.005-5 weight part with respect to 100 weight part of whole quantity of all the reactive substances. A preferred amount is 0.01 to 3 parts by weight. The amount of the polymerization accelerator is 0.002 to 5 parts by weight, preferably 0.01 to 2 parts by weight. It is possible to promote the crosslinking reaction with a small amount of the polymerization initiator and the polymerization accelerator. However, since the coexistence of the polymerization initiator and the polymerization accelerator impairs the stability of the polymer, either or both of the polymerization initiator and the polymerization accelerator are surface-treated with an easily meltable substance such as paraffin (v) The use of a coated catalyst is desirable.

Furthermore, (vi) a conventional known photocatalyst can be used as the photocatalyst to improve the curability (P5), and a polymer composition can be obtained. As an advantage of using the composition, there is an improvement effect on the drawbacks of the conventional light / UV curing, that is, the inhibition of curing by oxygen in the air. Normally, curing (radical polymerization) of ethylenically unsaturated group-containing liquid substances such as acrylic monomers described above inhibits curing of the liquid surface in contact with oxygen because oxygen acts as a polymerization inhibitor, and also inside the liquid due to diffusion of oxygen. Receive. Since the polymer before curing of the present invention can be a highly adhesive body (semi-solid) or a fixed body (solid), the effect of suppressing the diffusion of oxygen into the polymer can be expected. The curing catalyst is preferably a normal radical polymerization type photopolymerization initiator, and known initiators such as benzoin derivatives and benzophenone derivatives can be used. A preferable addition amount is 0.3 to 3 parts by weight based on 100 parts by weight of the total amount of the responsive substance.

(2-3) Silicone moisture-curable RHM (P3): As a moisture-curable RHM polymer in another form, a polymer (P3) containing two or more hydrolyzable silicon groups in the molecule is useful. . The hydrolyzable silicon group of the polymer is hydrolyzed by moisture, so that a moisture-crosslinking type reactive hot melt polymer can be obtained. Therefore, as the raw material monomers for polymer synthesis, for example, the above-mentioned monomers containing two or more carbon-carbon double bonds in the molecule, HSi group and hydrolyzable silicon in the molecule It is obtained by addition reaction of silane monomers containing a group. As the former monomers, known acrylic monomers are useful, and terminal alkenyl group-containing prepolymers in which an alkenyl group is introduced at the end of a known polyoxypolypropylenediol are useful. Further, as the latter monomers, known hydrolyzable diatom group-containing silane compounds, trialkoxysilanes, dialkoxysilane compounds and the like are useful. The polymer can also be obtained by reacting a silane compound containing an isocyanate group and a hydrolyzable silicon group with monomers such as diol or triol. As the silane compound, γ-isocyanatopropyltrimethoxysilane, known compounds can be used. In the polymer formation reaction, that is, the equivalence basis is desirably a stoichiometric ratio or the vicinity thereof, and the reaction temperature is desirably 60 to 140 ° C. As the catalyst, a known catalyst such as a platinum complex catalyst is used.

(2-4) HM polymer (P1): As the monomers, those used for producing the polymer (P2) are used. On the equivalent basis, the NCO / OH ratio is about 1.5 / 1 to 1 / 1.5. A range of 1.3 / 1 to 1.03 / 1 or 1 / 1.03 to 1 / 1.3 is suitable. When the amount ratio is 1.5 / 1 or more and 1 / 1.5 or less, the molecular weight required for the polymer may not be obtained. The molecular weight of the polymer is theoretically an NCO / OH ratio of 1/1 (theoretical equivalent ratio), the molecular weight obtained is maximized, and as the molecular weight increases, a polymer having excellent strength characteristics and the like is obtained. However, as a preferable range here, the reason why the range of 1.03 / 1 to 1 / 1.03 is excluded is that the polymerization reaction proceeds as much as possible when the NCO / OH ratio is close to the theoretical equivalent ratio or the theoretical ratio. Therefore, the convergence time of the polymerization reaction becomes longer. On the high molecular weight side, the increase in molecular weight significantly increases the melt viscosity, so that it is difficult to accurately control the fluidity in a short time. This is because the present invention wants to give priority to operability such as reaction convergence even if some physical properties caused by the decrease in molecular weight are sacrificed. Moreover, since the polymer is not crosslinked, it is desirable to improve the heat resistance of the polymer itself. As a result, since the flow temperature of the polymer is high, the generation temperature tends to be high. The generation temperature is about 100 ° C to 250 ° C, preferably 150 ° C to 250 ° C.

3. [Production temperature and discharge temperature of polymer (P4)]: Since the polymer has an unsaturated group in the molecule and also contains a redox catalyst, it is basically a reaction system lacking thermal stability. is there. Therefore, it is desirable that the polymer formation temperature is low. However, when a polymer obtained at a low production temperature is discharged at that temperature, the viscosity is high and the fluidity is lowered. In order to improve the fluidity, it is necessary to increase the temperature of the discharge part. Another reason is that the coexistence of the redox catalyst (polymerization initiator and polymerization accelerator) impairs the stability of the polymer. Therefore, in order to maintain the stability, either or both of the polymerization initiator and the polymerization accelerator are used as paraffin or the like. It is desirable to use a catalyst that has been surface-treated with an easily heat-meltable substance. For example, the melting point of paraffin used as a heat-fusible substance does not show a sharp melting point due to its molecular weight distribution or the like, and its melting range extends to about melting point ± 10 ° C. Therefore, the polymer production temperature is synthesized in a state where the catalytic activity is protected by the coating material, and the discharge of the polymer is higher than the melting point of the material, that is, the catalytic activity is released and the catalytic activity is released. It is desirable to discharge in a regenerated state. Therefore, the one where the difference of the production | generation temperature of a polymer and discharge temperature is large is desirable, and it is desirable that a temperature difference is 20-150 degreeC.

4). [Usefulness of two-component reactive hot melt]: The (P4) polymer containing a coating catalyst will be described as an example. The product agent system consists of two liquid agents at room temperature, and the catalyst is added separately to each of the two agents. For example, the first agent is the diisocyanate monomer, the second agent is the diol monomer having an ethylenically unsaturated group in the molecule, the second agent is a urethane synthesis catalyst, and the first agent is easier. A polymerization initiator coated with a meltable substance and a polymerization accelerator coated with a readily meltable substance are added to the second agent, respectively. The coating catalyst is prepared by the method described in Patent Document 1 (paragraphs 0090 to 0091). Thus, by using a two-component system at room temperature, the operability is facilitated, and the safety is remarkably improved by separating the catalyst. Next, the polymer is produced in an extremely short time by appropriately selecting the above-mentioned equivalent standards, reaction temperature, reaction time, etc., and carrying out the reaction temperature below the melting point of the easily meltable substance. Next, the discharge is performed at a temperature equal to or higher than the melting point of the easily meltable material, cooled at room temperature, and fixed (high adhesion) in a very short time. Subsequently, the crosslinking can be converted into a crosslinked body in a short time by regenerating the redox catalyst by heating at the melting point or higher during discharge. Further, crosslinking can be performed with high efficiency with a small amount of catalyst.

Such an excellent (P4) curing system can be obtained economically and stably only by using this apparatus. This is because when the (P4) curing system is applied as a one-component type reactive hot melt product, a redox catalyst must coexist in the product (polymer). Even if a coated catalyst is used as the catalyst, the coated surface may be destroyed due to some cause, for example, heating during transportation or destruction of the coated surface. When the surface is destroyed, even if the amount is small, the reaction is started because the redox catalyst has high catalytic efficiency. Once the reaction is initiated, it proceeds in a chain and may spontaneously ignite with the reaction heat. Therefore, frozen storage or the like is necessary for storage and transportation of products. In use, temperature control is extremely important for filling / melting into a heated coater dissolution tank. Special care must be taken when handling large quantities of products. This is the same when a large amount of products are manufactured by the conventional batch method. In response to such a problem, the problem can be solved only by using this apparatus and making the product system into a two-drug type.

Reactive hot melt adhesives, reactive hot melt pressure-sensitive adhesives, reactive hot melt curable compositions using as a main component a high-efficiency, stable and quality-assured polymer obtained by using this apparatus. Hot melt sealing agent / sealing agent, reactive hot melt coating agent, reactive hot melt injection agent or reactive hot melt molding molding material, film / sheet and the like. Moreover, it is a photocurable reactive hot-melt curable composition. In addition, by using various functional fillers in a high filling state, it is possible to obtain a highly functional material such as a high heat conductive material, a high conductive material, and a flame retardant material. In addition, as the use / use of the product, an architectural interior agent, an in-vehicle agent (interior), an environmental / sanitary agent, an electrical / electronic agent, and the like are useful. The continuous lamination (laminating) joining and B-stage curing of the same or different materials, which make use of the energy saving and high productivity characteristics of the present invention, are useful.
In particular, in the (P4) RHM system, the method of discharging at or below the melting point of the easily meltable coating material, and heating to above the melting point after discharge significantly promotes crosslinking (curing). In addition, (P5) RHM significantly promotes crosslinking (curing) by irradiation with energy rays. As described above, the method for accelerating the post-curing (crosslinking) of the polymer by applying the reactive hot-melt polymer and then heating or irradiating it with energy rays is useful for further improving the production efficiency.

The above-mentioned (meth) acrylates and other specific volatile reactive monomers can be added to the curable composition of the present invention as necessary. Various other additives can be blended. As examples of additives, liquid tackifiers such as terpene resins, rosin derivatives and dicyclopentadiene resins, particularly liquid tackifiers having reactive unsaturated groups are useful. Plasticizers such as fumarate ester, adipic acid ester and phosphate ester, and reactive plasticizers. Waxes such as montan wax and polyethylene wax. Inorganic fillers such as calcium carbonate, calcium sulfate, magnesium silicate, magnesium carbonate, alumina, zinc oxide, quartz powder, silica, hemihydrate gypsum, zeolite, cement and talc. Further, various metal powders such as copper and nickel, various organic powders such as wood powder, fibers such as glass fibers and carbon fibers, colorants, heat stabilizers, flame retardants, antioxidants, light stabilizers and the like can be added. However, it is not limited to these. In addition, polymers can be added as long as fluidity is not hindered.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not restrict | limited to these Examples.
1. The device conforms to FIG.
(Storage container for the first agent and the second agent): 50 ml of glass was used. The first agent reservoir was filled with a diisocyanate liquid. The second agent reservoir was filled with a diol and polymer synthesis catalyst mixture.
(Precision quantitative dispenser for the two agents): A translucent PP syringe was used. Two types of dispensers (first agent / second agent syringe: for 1 ml / 2.5 ml, for 5 ml / 2.5 ml) were prepared, each of which was linked with two syringes.
(Mixer): The container was provided with a discharge port (inside diameter, 3 mmφ) at the bottom of 10 ml of copper (inner diameter 20 mm, height 35 mm, thickness 1 mm), and the discharge port was closed with aluminum tape. A stirring rod (8 mm wide, 80 mm long, 2 mm thick steel flat plate) equipped with a digital thermometer was used. The lid of the mixer was replaced with a vinylidene chloride film to cover the container.
(Switching valve for the two agents): A PP three-way valve was used. The three-way valve was connected to a storage container, a syringe, and the mixer.
(Heating unit): Use aluminum block (100 mm square, 20 mm thick flat plate with a recess of diameter 23 mmφ and depth 15 mm in the center) for the heating unit, heating control is to continuously energize 600W heater Thus, a temperature rising rate of 12 to 13 ° C. per minute (temperature range of 50 ° C. to 150 ° C.) was obtained, and the temperature was controlled by turning on / off the electric heater.
(Connection piping): Translucent PE pipe was used.

2. The following commercial products were used as raw materials.
(MDI diisocyanate prepolymer): URIC N2023: manufactured by Ito Oil Co., Ltd. (number of functional groups 2, equivalent 260, light yellowish brown, viscosity 2500 mPa · s (25 ° C.), density 1.14)
(Diol): Y403: Made by Ito Oil Co., Ltd. (2 functional groups, equivalent weight 350, light yellow transparent, viscosity 250 mPa · s, density 0.95)
C1090: Kuraray Co., Ltd .: (number of functional groups 2, equivalent 500, colorless and transparent, viscosity 10,000 mPa · s, density 1.09)
(Polymer production catalyst): DBTDL (dibutyltin dilaurate, manufactured by Wako Pure Chemical Industries, Ltd.)

3. Explanation of Evaluation Test Method (Table 1) ((e) Fluidity at Discharge): The fluidity of the produced polymer in the mixer at each heated mixer temperature (at the time of discharge) is shown. The determination of fluidity was made based on the liquid breakability of the liquid adhering to the stirring bar by pulling up the stirring bar immersed in the liquid flowing in the mixer. The shorter the liquid run-out time, the easier the fluidity. Check the liquid breakability of samples with known viscosities of different viscosities (about 500 mPa · s, about 2,000 mPa · s, about 10,000 mPa · s) in advance. The liquid breakage was visually observed and the fluidity was evaluated. Judgment: +: Good fluidity, viscosity is about 10,000 mPa · s or more, ++: Excellent fluidity, viscosity is about 2,000-10,000 mPa · s, ++: Excellent fluidity, viscosity is 500-2,000 mPa • s, equivalent.
((F) Adhesiveness of the coated body at room temperature): (e) The adhesiveness (adhesiveness) of the coated body is after the aluminum plate (100 mm square, 5 mm thickness) is ejected with the (e) discharged liquid at room temperature. The probe was lightly brought into contact with the coated body after 60 seconds and pulled up. Evaluation was made from the state of penetration of the probe and the state of resistance during pulling (threading). As for the evaluation of tackiness, (◯) shows sufficient tackiness (tack), and the formation of the target polymer is recognized. (X) shows no tackiness (no polymer formation). (△) indicates that the production of the polymer is slightly insufficient.
((G) Open time): The open time (adhesion work possible time) of the coated body used for the evaluation of the adhesiveness in (f) was evaluated. In the evaluation, a steel flat plate (width 8 mm, length 80 mm, thickness 2 mm) having a length of 20 mm was pressure-bonded to the coated body, and the time when the coated body was hardened and could not be crimped was defined as the open time.
((H) Surface drying time): The surface drying time was evaluated using the evaluation sample of (f). In the evaluation, the probe was lightly brought into contact with the coated body, and the drying time was defined as the time when the surface dryness (curability) progressed and no trace of the probe was observed.
((I) Fluidity of the coated body): The fluidity of the coated body was evaluated by measuring the spread of the fluidized liquid under the flow of about 5 drops of the discharged liquid at the center of a 100 mm square, 5 mm thick aluminum flat plate. The determination was based on visual observation and digital camera photography of the spread of fluidity. (◯) indicates an appropriate flow, and the adhesiveness was maintained after the flow. The (x) mark showed overflow and did not show stickiness. (△) was slightly deficient in both fluidity and tackiness.

((J) Crosslinkability (strength) of polymer): The coated body of (h) was cured at 25 ° C. and 50% RH for 24 hours and 72 hours, and the appearance and strength of the coated body were determined. Qualitative evaluation was performed. Judgment: (O): The cured product was pale yellow and transparent, withstood 180 degrees of bending, had a tensile strength of 100 kg / mm 2 or more, and had toughness.
((K) Crosslinkability of polymer (heat resistance)): (i) Using the above-mentioned (i) cured product (cured for 72 hours), a strip (about 3 mm square, about 1 mm thick), The strips were set on a manufactured block, heated at a constant speed at 10 ° C. per minute, and the appearance (softened state, etc.) of the strips was observed with a loupe.

Example 1.
Table 1 (Experiment NO1-1 to NO1-4) for the purpose of confirmation of short-term synthesis of terminal OH type polymer under heating, evaluation of the polymer and the like, and acquisition of basic design value data of the present invention (continuous real machine production) apparatus. ) Was conducted. In the present invention, a large amount of reaction heat is generated with short-time synthesis. Therefore, a small amount reaction system was used to suppress the influence of reaction heat as much as possible. First, NO1-1 will be described. At room temperature, 0.6 ml and 2.5 ml of the first agent and the second agent filled in the storage container were sucked and sampled through a three-way valve, respectively, into a 1 ml / 2.5 ml syringe by a piston. Subsequently, the three-way valve was removed in order to avoid the measurement error of the liquid agent stored in the flow path from the syringe discharge port to the mixer, the two agents in the syringe were pushed out at a constant speed, and discharged directly into the mixer at room temperature. The mixer was then covered with a vinylidene chloride film and the vessel with the stir bar set. Then, it stirred rapidly at room temperature by manual mixing for 15 seconds. During this time, no heat of reaction was generated.
Immediately after that, a mixer was set in a preheated heating section (temperature of about 80 ° C.) and mixed at the temperature for about 15 seconds. Initially, the temperature of the liquid agent was temporarily lowered (about 60 ° C.) by setting the mixer at room temperature in the heating block. Thereafter, a rapid reaction occurred for about 15 to 30 seconds. Increased rapidly and the liquid temperature exceeded 80 ° C. Thereafter, gentle stirring is continued, the liquid temperature is maintained at about 80 ° C., and after evaluating the fluidity (e) of the product liquid in the mixer, the mixer is quickly lifted from the heating block and immediately discharged from the bottom outlet of the mixer. The aluminum tape was peeled off, and about 0.3 ml of the fluid was applied on the aluminum flat plate (room temperature). After application, the discharge port was quickly closed with aluminum tape, set again on the heating block, and the temperature was raised while continuing gentle stirring. Moreover, about the obtained application body, (f) adhesiveness and (g) open time were measured. The results are also shown in Table 1.

Experiment NO1-2: The constant heating of NO1-1 was continued up to 100 ° C. During this time, the liquid temperature was also raised at a constant rate, and it was considered that no reaction heat was observed. After rapid stirring at a temperature of about 100 ° C. for 5 seconds, (e) fluidity, (f) tackiness and (g) open time) were measured as in No. 1-1, and the results are also shown in Table 1. Similarly, the experiments NO1-3 to 1-4 were also continued to be heated, and (e) fluidity, (f) tackiness, and (g) open time at temperatures of about 120 ° C and about 140 ° C were measured. did. The results are also shown in Table 1.

Example 2
The terminal NCO type (moisture curable type) polymer was tested for the same purpose as in Example 1. NO2-1 will be described. In this test, as shown in Table 1, the terminal NCO group type polymer was produced and evaluated according to Example 1 except that the formulation of the second agent was changed and the NCO / OH ratio was changed. The results are also shown in Table 1. Also, in the test of NO2-2 to 2-3, NO2-1 was heated at a constant speed as in Example 1. With respect to NO2-3 (temperature of about 140 ° C.), (e) fluidity, (f) tackiness, and (g) open time of the produced polymer were measured, and the results are also shown in Table 1. In addition, about the exothermic behavior accompanying the production | generation of a polymer, the tendency similar to Example 1 was shown. That is, in the first heating (80 ° C .: NO. 2−1), rapid reaction heat was generated, but the liquid temperature was also raised at a constant rate when the temperature was raised to 140 ° C. It was thought that the generation of reaction heat was not observed.

Comparative Example 1
In order to evaluate the fluidity of the coated body, the non-catalytic formulation shown in Table 1 was used to determine (e) fluidity when heated, (f) adhesiveness of the coated body, and (g) fluidity of the coated body. It was measured. Comparison with Example 2 (NO2-3). As a result, the adhesiveness of the coated body could not be shown, and the fluidity of the coated body was remarkably unsuitable as the polymer of the present invention.

(Consideration of results)
1. Production of polymer / Short time synthesis under heating: From the test of Example 1 (NO1-1 to 1-4), changing the heating temperature / time in Table 1, in the first heating (80 ° C .: NO1-1) A sudden reaction was observed. After that, even when the heating temperature was further heated to 100 ° C. to 140 ° C. (NO1-2 to 1-4), generation of reaction heat was not recognized. From this, it was shown that the polymer was formed in a short time by the first heating and the reaction was converged, and as a result, the polymer could be stably formed in a short time. And it can be supported from the following tests.
That is, from the fluidity test of (e), the fluidity of the produced polymer increased as the temperature rose (80 ° C. (+) to 140 ° C. (++++)). This indicates that the viscosity of the polymer produced has decreased with increasing temperature, which is consistent with the polymer theory.
Furthermore, from the adhesiveness (adhesiveness) of the coated body of (f), the adhesiveness of NO1-1 to NO1-4 was observed to be slightly lower than that of NO1-1, but was good overall. Furthermore, in the open time of the coated body of (g), no change was observed in the adhesiveness immediately after coating and after 3 days at room temperature.
Furthermore, from the test of Example 2 (NO2-1 to 2-3) in which the heating temperature / time was changed, in the first heating (80 ° C .: NO1-1), generation of a rapid reaction was recognized, and then Even when the heating temperature was 100 ° C. to 140 ° C. (NO2-2 to 2-3), no reaction was observed. As in Example 1, it was suggested that the polymer was formed in the first heating in a short time and the reaction was converged in a short time. Also, the tackiness (adhesiveness) was sufficient. From the above, as in Example 1, it was found that the synthesis of the polymer for a short time under heating can be carried out properly.

2. Qualification of produced polymer and qualification of crosslinked product: As described above, it can be said that the polymers of Example 1 and Example 2 are appropriate in both production and performance of the polymer.
Here, for the polymer of Example 2 (NO2-3), the open time of (g) is 30 minutes and the drying time of the surface of the coated body of (h) is 60 minutes. Based on being sex. And the initial sticking property accompanying room temperature release was favorable because high adhesion was maintained. Further, since the adhesive state was maintained for about 30 minutes, workability such as adhesive bonding was good. Further, after 60 minutes, curing (crosslinking) was started and good moisture curability was exhibited. From the above, it was shown that both the open time and the drying time are appropriate.
Also, (i) the flow behavior on the adherend surface of the coated body immediately after coating was photographed with a register camera, and the video was taken into a computer and magnified and observed. By comparing this polymer image (NO2-3) with the image of Comparative Example 1, it was found that the image analysis was effective in confirming the formation of the polymer.
Furthermore, regarding the suitability of the crosslinked body in NO2-3, a tough and excellent heat resistance was obtained from the evaluation of the strength of (j) and the heat resistance of (k). From this, it was confirmed that the curing (crosslinking) of the polymer proceeds appropriately.

3. (M) Confirmation Determination of Generated Polymer: Confirmation determination of the formed polymer was performed with reference to the (a1) exothermic temperature measurement method. As an example, experiments NO1-1 and NO1-2 will be described.
(1) NO1-1 (set temperature: 80 ° C.) was considered to have converged substantially as the reaction of the produced polymer measured rapid exotherm within the temperature and the reaction time. From this, NO1-1 was satisfied as the conditions of the polymer of this invention, and it was thought that the production | generation conditions of this polymer can be employ | adopted for the production | generation conditions of a standard type polymer.
(2) NO1-2 (set temperature 100) aims to converge (complete) the reaction by heating and heating NO1-1. By this operation, no exotherm was observed, and from this, it was considered that the reaction had already converged, and it was considered that the production conditions for this polymer could be adopted as the production conditions for the actually operated polymer.
(3) Confirmation determination is made by comparing the convergence of the polymer production reaction of NO1-2 and NO1-1, that is, the production conditions for NO1-1 (standard system / input data), the production conditions for NO1-2 (actual operation) System / measurement data). And the result of the Example also showed that the confirmation method is appropriate.

4). Basic design value data of actual device for the present invention:
According to this example, it was shown that a polymer can be formed in a very short time and stably. Furthermore, it was shown that the obtained polymer has an appropriate function as the polymer of the present invention. Furthermore, it was shown to be effective for evaluation / judgment of polymers and cross-linked products, and at the same time, it was shown to be useful as basic design value data for the apparatus for the present invention. It is obvious that the actual apparatus can be obtained by adding known techniques (automation technique, measurement / control technique, computer technique, etc.) in addition to these embodiments.

DESCRIPTION OF SYMBOLS 10 1st agent storage container 11 1st agent precision fixed quantity discharge machine 12 1st agent switching valve 10a 1st agent liquid quantity remaining amount measurement sensor 10b 1st agent liquid quantity supply measurement sensor 20 2nd agent storage Container 21 Precise quantitative dispenser for second agent 22 Second agent switching valve 20a Second agent liquid amount remaining amount measuring sensor 20b Second agent liquid amount supply measuring sensor 30 Mixer 31 Mixing container 32 Mixing stirrer 33 Static Mixer outer cylinder 34 Static mixer mixing element 35-36 Connector 30b Mixability measurement sensor 30c Mixer temperature measurement sensor 30d Reaction time measurement sensor 40 Reservoir 40b Polymer composition measurement sensor 40c Reservoir temperature measurement sensor 40e Melt viscosity measurement sensor
41K, 61K switching valves 43h, 43s, 43t: Viscosity sensor main body, detection unit, thermometer 44h, 44s, 44o, 44t: Viscous resistance sensor main body, detection unit, orifice, thermometer 45, 45 (b1), 45 (B2): Translucent part of optical sensor, incident side (light source side element), reflection side detection part 50 heating part 60 discharge part 61 discharge valve 62 pedestal 60c discharge part temperature measurement sensor 61D check valve 63S discharge machine cylinder 63P discharge Machine piston 70 Application body 70b Application body optical sensor 70c Application body temperature sensor 71 Substrate 80 Control section

Claims (9)

Thermoplastic polymer is the main component of the reactive hot-melt compositions or hot melt composition (hereinafter abbreviated as polymer) a continuously generated equipment, the apparatus comprising a (1) polymer A storage container for storing each of the first agent and the second agent, which are raw materials for generation, (2) To always supply the first agent and the second agent from the storage container at a constant ratio to the mixer. 2 precision metering dispensers, (3) a switching valve, (4) a mixer with or without a heating section, (6) a dispensing section with a heating section, and (A) A means for confirming the production of the polymer, the polymer production confirmation means comprising : (a1) measurement of exothermic peak temperature or exothermic peak time, (a2) calculation of polymer production, (a3) measurement of melt viscosity, (a4) a thermoplastic polymer which is a one or combination of measurement of the composition Production equipment of. Further, during the discharge portion of the (4) mixers and of (6), (5) production equipment of a thermoplastic polymer according to claim 1, characterized in that it comprises a reservoir having a heating portion. Furthermore, (B) production equipment of a thermoplastic polymer according to claim 1 or 2, characterized in that it comprises a means for confirming the application of the polymer. The application confirmation means for the polymer in (B) is any one of or a combination of (b1) temperature, (b2) appearance, (b3) color tone measurement of the application body applied on the adherend. production equipment of the thermoplastic polymer according to claim 3, characterized in. A signal obtained from the measurement according to claim 1 ((a1) to (a4)) is input to a computer, data processing is performed in real time by the computer, and an inspection means for determining confirmation of formation of a polymer, and production equipment of a thermoplastic polymer according to claim 1, characterized in that it comprises a management means for managing the production history. 5. An inspection means for inputting a signal obtained from the measurement ((b1) to (b3)) of claim 4 to a computer, processing the data in real time by the computer, and determining confirmation of application of the polymer, and application of the polymer production equipment of the thermoplastic polymer according to claim 4, characterized in that it comprises a management means for managing the history. The thermoplastic polymer according to any one of claims 1 to 6, wherein the production apparatus according to any one of claims 1 to 6 can integrally perform the production and application of the polymer. production equipment of. A reactive hot melt or a hot melt thermoplastic polymer is produced using the thermoplastic polymer production apparatus according to any one of claims 1 to 7 . A method for producing a thermoplastic polymer. The method of manufacture according to claim 8, wherein the temperature of the mixer is 20 to 250 [° C., reactive hot-melt or hot melt according to claim 8, wherein the temperature of the discharge portion, characterized in that it is from 50 to 280 ° C. For producing a thermoplastic polymer for use.

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