KR20240062527A - Binary liquid type polyurethane resin composition for potting of membrane with excellent dimensional stability and cutting performance - Google Patents

Abstract

The present invention relates to a two-part polyurethane resin composition for membrane potting with excellent dimensional stability and cutting properties, and is a two-part polyurethane resin comprising a polyol part (A) and a main part (B) composed of a polyfunctional isocyanate or a prepolymer thereof. In the composition, (a) 2 to 40% by weight of any one or more polyols selected from polyester polyols, polyether polyols, and castor oil derivatives having a number average molecular weight of 200 to 1000 and having 2 to 3 OH groups, and (b) 2 to 30% by weight of any one or more polyols selected from polyether polyols, polyester polyols, and castor oil derivatives with a number average molecular weight of 200 to 1000 having 3 to 4 OH groups, and (c) 4 to 5 OH groups. 20 to 70% by weight of at least one polyol selected from polyether polyols, polyester polyols, and castor oil derivatives with a number average molecular weight of less than 400 to 1,500, and (d) 0.1 to 0.1% of a chain extender with two functional groups and a molecular weight of 50 to 200. 5% by weight, (e) 1 to 10% by weight of plasticizer, (f) 0.1 to 7% by weight of micro hollow sphere particles, and (g) 0.1 to 5% by weight of thermoplastic polyurethane (TPU) with a melting point of 80 to 100°C. An agent that is reacted by mixing 90 to 110 parts by weight of the main part (B), which is composed of an isocyanate having two or more NCO groups or a prepolymer thereof, with respect to 100 parts by weight of the polyol part (A) consisting of the first step of mixing. It takes place in two stages. The present invention has excellent dimensional stability and durability by controlling the content of various types of polyols with different numbers of OH groups in the polyol part to form a network structure that can be quickly cured at low temperatures. In addition, micro hollow sphere particles and thermoplastic polyurethane (TPU) are used in the polyol part. ) is applied and then mixed with the main part to react, which has the effect of improving machinability during product processing.

Description

Two-part polyurethane resin composition for membrane potting with excellent dimensional stability and cutting properties {BINARY LIQUID TYPE POLYURETHANE RESIN COMPOSITION FOR POTTING OF MEMBRANE WITH EXCELLENT DIMENSIONAL STABILITY AND CUTTING PERFORMANCE}

The present invention relates to a two-component polyurethane resin composition for membrane potting with excellent dimensional stability and machinability. More specifically, it relates to a network structure capable of low-temperature rapid curing by controlling the content of various types of polyols with different numbers of OH groups in the polyol part. It improves dimensional stability and durability by forming a two-component polyurethane resin composition for membrane potting with good machinability during product processing by applying micro hollow sphere particles and thermoplastic polyurethane (TPU) and then mixing and reacting with the main part. It's about.

The hollow fiber membrane module, which has recently been applied to membrane devices in various fields, is a filtration treatment device that uses hollow fiber as a separation membrane. The hollow fiber membrane module is used in industrial fields such as water treatment membranes, blood It is used in a variety of fields such as medical fields such as ultrafiltration or microfiltration, and recently, demand for it has been rapidly increasing in applications such as household water purifiers, industrial water purifiers, artificial kidneys, and artificial lungs, and to reduce processing costs. Large hollow fiber membrane modules are required.

In the case of an external pressure type or internal pressure type hollow fiber membrane module, the hollow fiber membrane module is manufactured through the process of inserting a hollow fiber membrane into a cylindrical case and sealing both ends or one end with resin. This process is called 'potting'. Adhesives or fillers used when potting hollow fiber membrane modules include polyurethane and epoxy resin, and these are cut to form flow paths to manufacture hollow fiber membrane modules.

These hollow fiber membrane modules must maintain resistance and durability against external pressure during use or air pressure when cleaning the hollow fiber membrane, otherwise accidents such as water leakage and membrane rupture may occur. For this reason, the potted area of the hollow fiber membrane module is important in terms of resistance to external force, sealing with the hollow fiber membrane, dimensional stability, and durability.

For the above reasons, in the case of potting materials used in industrial membranes, elasticity and hardness are considered important to enhance stability at high temperatures and impact resistance to various forces. However, in general, when cured at room temperature, the viscosity of the potting material composition is too high. If it is low or high, it may be difficult to maintain the shape and the mold may not be filled sufficiently, which may result in poor shape of the molded body. Additionally, if curing and pot life are prolonged, productivity may decrease.

In addition, potting materials used in membranes are applied to various temperatures after being fully cured. If the dimensional change according to temperature is large, osmotic pressure defects may occur as a result. In particular, in the case of membranes applied to automobiles, the temperature gap is large, so dimensional stability is poor. The problem is emerging.

In addition, the polyurethane-based potting material is cured for a certain period of time after molding and is cut and applied. If the hardness of the polyurethane resin is too high, the cutter blade may be damaged during cutting or the cutting surface may not be smooth and may break. Conversely, if the hardness is too low, problems such as not being cut cleanly may occur when cutting.

Accordingly, looking at the polyurethane resin used as a conventional potting material, Korean Patent No. 10-1526478 discloses a polyurethane resin containing a main agent containing an isocyanate component and a curing agent containing a polyol component; and Lauryl Alcohol Ethoxylate, Tridecyl Alcohol Ethoxylate, sulfoxides, ethoxylated fatty acid, and glycerol ester. A polyurethane resin composition for potting material of a hollow fiber membrane module having a hardness of 80Hs to 95Hs containing an additive containing one or more compounds selected from the group, which has high adhesion to the module case and excellent durability, and prevents contamination of the module. They say it can be minimized.

In addition, Republic of Korea Patent Publication No. 10-2017-0087905 is a multi-part polyurethane composition comprising at least a first part and a second part, wherein the first part is NCO based on the total weight of the polyurethane prepolymer composition. comprising a polyurethane prepolymer composition in an amount of 15% to 24% by weight; The second part includes a polyol having 4 to 6 hydroxyl functional groups and a desiccant; The composition comprises from 1% to 30% by weight of a plasticizer based on the total weight of the composition, the plasticizer being present in any one or more of the portions; The composition discloses a multi-part polyurethane composition having a stoichiometry of 1:1 to 1.2:1, where stoichiometry is defined as the ratio of equivalents of isocyanate functionality to equivalents of hydroxyl functionality in the composition.

In addition, Republic of Korea Patent No. 10-2068114 discloses a polyurethane resin composition for hollow fiber membrane module potting with improved heat resistance and hydrolysis resistance using cast oil and butadiene polyol of a specific multifunctional group, polyol part (A) and multifunctional isocyanate. In the two-component polyurethane resin composition containing the prepolymer part (B), in order to improve heat resistance and hydrolysis resistance, the polyol part (A) includes a modified cast oil having at least 5 OH functional groups and a polybutadiene polyol. , in the polyol part (A), the polybutadiene polyol is characterized in that it has a number average molecular weight of 900 to 1200.

And Republic of Korea Patent No. 10-2101723 is a two-component polyurethane resin composition for hollow fiber separator module potting material required for manufacturing water purifier modules of hollow fiber separators, including a diisocyanate prepolymer containing an isocyanate component; and a modified castor oil hardener containing a polyol component, wherein the difference in viscosity at 25°C between the diisocyanate prepolymer and the modified castor oil hardener is a greater viscosity value at 25°C between the diisocyanate prepolymer and the modified castor oil hardener. is 10% or less based on, and the mixed viscosity of the diisocyanate prepolymer and the modified castor oil hardener at 25°C is 3,000 cps or more, and the modified castor oil hardener is made by reacting castor oil and diisocyanate, and the diisocyanate Isocyanate is contained in an amount of more than 2% by weight to less than 4% by weight of the total weight of the modified castor oil hardener.

Republic of Korea Patent Publication No. 10-1526478 (announcement date: June 5, 2015) Republic of Korea Patent Publication No. 10-2017-0087905 (publication date: July 31, 2017) Republic of Korea Patent Publication No. 10-2068114 (announcement date: January 20, 2020) Republic of Korea Patent Publication No. 10-2101723 (announcement date: April 20, 2020)

The purpose of the present invention is to improve dimensional stability and durability by controlling the content of various types of polyols with different numbers of OH groups in the polyol part to form a network structure capable of rapid curing at low temperatures, thereby improving dimensional stability and durability by forming micro hollow sphere particles and thermoplastic polyurethane ( A two-component polyurethane resin composition for membrane potting with good machinability during product processing is provided by applying TPU and then mixing and reacting with the main part.

The two-part polyurethane resin composition for membrane potting according to the present invention includes a polyol part (A) and a main part (B) composed of a polyfunctional isocyanate or a prepolymer thereof, (a) 2 to 40% by weight of at least one polyol selected from polyester polyols, polyether polyols, and castor oil derivatives with a number average molecular weight of 200 to 1000 having 2 to 3 OH groups, and (b) 3 to 4 OH groups. 2 to 30% by weight of at least one polyol selected from polyether polyols, polyester polyols, and castor oil derivatives with a number average molecular weight of less than 200 to 1,000, and (c) a number average molecular weight of 400 to 1,500 with 4 to 5 OH groups. 20 to 70% by weight of one or more polyols selected from polyether polyols, polyester polyols, and castor oil derivatives, (d) 0.1 to 5% by weight of a chain extender with two functional groups and a molecular weight of 50 to 200, and (e ) The first step of mixing 1 to 10% by weight of plasticizer, (f) 0.1 to 7% by weight of micro hollow sphere particles, and (g) 0.1 to 5% by weight of thermoplastic polyurethane (TPU) with a melting point of 80 to 100°C. The second step is to mix and react the main part (B), which is composed of an isocyanate having two or more NCO groups or a prepolymer thereof, at a ratio of 90 to 110 parts by weight with respect to 100 parts by weight of the polyol part (A).

According to a preferred embodiment of the present invention, the chain extender (d) uses at least one selected from glycols and amines, and the plasticizer (e) uses dehydrated castor oil.

In addition, the micro hollow sphere particles (e) are hollow spheres made of glass or polystyrene, surface-treated with a silane coupling agent, and have a diameter of 1 to 200 ㎛ and a specific gravity in the range of 0.5 to 1.0. The silane coupling agent is vinyl-based or epoxy. Any one selected from polyurethane-based polyurethane, methacryloxy-based, acryloxy-based, and amino-based is used, and the thermoplastic polyurethane (f) has a melting point of 100°C or less and a flow index of 50g/10min (170°C/2.16kg). ) or more.

And the subject part (B) uses at least one selected from pure isocyanate, polymeric isocyanate, and modified isocyanate having two or more NCO groups, and the NCO/OH index ( It is characterized by mixing so that INDEX) is in the range of 1.0 to 1.1.

The two-component polyurethane resin composition for membrane potting with excellent dimensional stability and machinability of the present invention provides dimensional stability and durability by controlling the content of various types of polyols with different numbers of OH groups in the polyol part to form a network structure capable of rapid curing at low temperatures. This is excellent, and by applying micro hollow sphere particles and thermoplastic polyurethane (TPU) and then mixing and reacting with the main part, there is an effect of good machinability during product processing.

Hereinafter, the two-component polyurethane resin composition for membrane potting, which has excellent dimensional stability and cutting properties according to the present invention, will be described, which allows a person skilled in the art to easily carry out the invention. It is intended to illustrate to the extent possible, but does not mean that the technical idea and scope of the present invention is limited.

The two-part polyurethane resin composition for membrane potting according to the present invention is basically a two-part polyurethane resin composition comprising a polyol part (A) and a main part (B) consisting of a polyfunctional isocyanate or a prepolymer thereof, (a) ) 2 to 40% by weight of at least one polyol selected from among polyester polyols, polyether polyols, and castor oil derivatives with a number average molecular weight of 200 to 1000 having 2 to 3 OH groups, and (b) 3 or more OH groups 4 2 to 30% by weight of at least one polyol selected from polyether polyols, polyester polyols, and castor oil derivatives with a number average molecular weight of less than 200 to 1000, and (c) a number average molecular weight of 400 to 400 or less than 5 OH groups. 20 to 70% by weight of at least one polyol selected from 1500 polyether polyol, polyester polyol, and castor oil derivative, (d) 0.1 to 5% by weight of a chain extender with two functional groups and a molecular weight of 50 to 200, ( e) 1 to 10% by weight of plasticizer, (f) 0.1 to 7% by weight of micro hollow sphere particles, and (g) 0.1 to 5% by weight of thermoplastic polyurethane (TPU) with a melting point of 80 to 100°C. The second step is to mix and react the main part (B), which is composed of an isocyanate having two or more NCO groups or a prepolymer thereof, at a ratio of 90 to 110 parts by weight with respect to 100 parts by weight of the polyol part (A).

The term 'potting' originated from the use of the shell or case surrounding a device as a pot with the introduction of liquid potting material, and the potting material was used to protect the device or component from moisture by embedding it in the potting material. Of course, electrical isolation is achieved and the device is safely protected in assembly, allowing work to proceed as designed. Currently, a variety of potting and encapsulation compounds are on the market, but the most commonly used materials include epoxy, hot melt, unsaturated polyester, and silicone, in addition to the urethane material of the present invention.

Among the various potting materials mentioned above, what type of device/part will be potted considering the amount of space and port to be filled, what is the operating environment, what is the allowable curing or gel time, and what curing mechanism is required? The potting material is selected by considering its durability, bonding strength, hardness, thermal expansion coefficient, heat resistance, and material cost for the application.

For this reason, the urethane material used in the present invention not only has excellent dimensional stability because it has hardness characteristics over a wide range of temperatures and can change the curing speed, but also has excellent dimensional stability due to the application of micro hollow sphere particles and thermoplastic polyurethane (TPU). The present invention was completed by developing a two-component polyurethane resin composition for membrane potting with good cutting properties.

First, the polyurethane resin composition according to the present invention is a two-component type, and the polyol part (A) is (a) a polyester polyol, polyether polyol, and castor oil derivative with a number average molecular weight of 200 to 1000 and having 2 to 3 OH groups. 2 to 40% by weight of one or more polyols selected from among, and (b) one or more polyols selected from polyether polyols, polyester polyols, and castor oil derivatives with a number average molecular weight of 200 to 1000 and having 3 to 4 OH groups. 2 to 30% by weight, and (c) 20 to 70% by weight of any one or more polyols selected from polyether polyols, polyester polyols, and castor oil derivatives with a number average molecular weight of 400 to 1500 and having 4 to 5 OH groups, (d) 0.1 to 5% by weight of a chain extender having two functional groups and a molecular weight of 50 to 200, (e) 1 to 10% by weight of a plasticizer, (f) 0.1 to 7% by weight of micro hollow sphere particles, and (g) The first step is to mix 0.1 to 5% by weight of thermoplastic polyurethane (TPU) with a melting point of 80 to 100°C. In the present invention, various types of polyols (a) (b) (c) with different numbers of OH groups are used. When used in combination, the curing speed is fast, dimensional stability, hardness, heat stability and moisture resistance are excellent, and moldability is good, thereby improving productivity.

Examples of the polyol component of the polyol part (A) include polyester polyol, polyether polyol, castor oil, castor oil-based polyol, castor oil fatty acid, diol-type partial dehydrate or partial acylate of castor oil, and the respective compounds. Hydrogen additives, etc. can be mentioned. The present invention focuses on the fact that the curing speed of polyol varies depending on the number of OH groups and greatly affects hardness and thermal stability, and each polyol (a) with different numbers of OH groups It should be noted that the contents of (b) and (c) are the results of numerous experiments.

In addition, the chain extender (d) is preferably used in an amount of 0.1 to 5% by weight of at least one selected from glycols and amines having two functional groups and a molecular weight of 50 to 200, specifically 1,4-BD. , MEG, or 1,6-HD can be used.

In addition, the plasticizer (e) is not particularly limited in its specific type, but in the present invention, dehydrated castor oil, which has excellent compatibility with the polyol (a) (b) (c), is used in the range of 1 to 10% by weight. It was confirmed that it is appropriate to use, and as a result, the viscosity characteristics and dimensional stability of the product are good, and in particular, molding and cutting after potting become easier.

In particular, the most characteristic technology to be implemented in the present invention is to produce two-component polyurethane by containing a certain amount of micro hollow sphere particles (f) and thermoplastic polyurethane (TPU) (g) with a melting point of 80 to 100°C in the polyol part (A). The goal is to improve the machinability, or processability, of hard potting materials formed from resin compositions.

The micro hollow sphere particles (f) are contained in the range of 0.1 to 7% by weight based on the total weight of the polyol part (A), making it easier to mold and cut while maintaining the strength at a certain level, which is made of glass or polystyrene. It is preferable to use hollow spheres made of (PS) that are surface treated with a silane coupling agent and have a diameter of 1 to 200 ㎛ and a specific gravity in the range of 0.5 to 1.0.

The micro hollow sphere particles (f) are surface treated with a silane coupling agent to improve dispersibility and storage stability in the composition and are more advantageous in maintaining the strength of the potting material. The silane coupling agent is generally vinyl-based or epoxy. It is preferable to use any one selected from the group consisting of a methacryloxy group, an acryloxy group, and an amino group. For example, micro hollow sphere particles with an average size of 35㎛, such as HOLLOWLITE's HL60S, surface treated with a silane coupling agent, can be used.

For an example of surface treating the micro hollow sphere particles (f) with a silane coupling agent, 400 ml of ethanol and 3-methacryloxypropyl triethoxysilane were added to a 1000 ml beaker and mixed to obtain 0.3 v/v. % solution is prepared. Add 100 g of S22 (HOLLOWLITE) surface-treated with O₂ plasma to the solution and stir slowly for about 20 minutes. Silane-treated micro hollow sphere particles can be manufactured by filtering the surface-treated S22 (HOLLOWLITE) as described above, going through an ethanol washing process, and then drying it in an oven at 100°C for 1 hour.

For reference, the micro hollow sphere is a particle surrounded by a porous or non-porous shell and has a micro structure with an empty center, and has characteristics such as low density, high specific surface area, and high flowability. Therefore, it can be applied to many fields such as lightweight fillers and insulation materials, sensors, catalysts, and drug carriers. These hollow sphere particles are manufactured by various methods such as core-shell, emulsion, spray drying or spray pyrolysis, self assembly, and smelting. can do.

In addition, in the present invention, thermoplastic polyurethane (TPU), which has excellent compatibility with the polyol part (A) and has weak physical properties at high temperatures, was further applied along with the micro hollow sphere particles, and thus has a melting point of 80 to 100°C and flows. 0.1 to 5% by weight of thermoplastic polyurethane (g) with a plasticity index of 50g/10min (170℃/2.16kg) or more {approximately 2000g/10min (170℃/2.16kg) or less} based on the total weight of the polyol part (A). By containing it within the range, cutting properties can be further facilitated. An example of a product that can be used is ECO 590 from Lubrizol.

The two-component polyurethane resin composition for membrane potting of the present invention contains 90 to 110 parts by weight of the main part (B) composed of isocyanate having two or more NCO groups or a prepolymer thereof for 100 parts by weight of the polyol part (A) formed as described above. It consists of a second step of mixing and reacting in a negative ratio, and the main part (B) is selected from pure isocyanate, polymeric isocyanate, and modified isocyanate having two or more NCO groups. Use one or more types, mix and cure so that the NCO/OH index is in the range of 1.0 to 1.1.

The subject part (B) includes paraphenylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), and naphthalene diisocyanate (NDI) as isocyanate components. It can be used alone or in combination of two or more, and modified MDI, polymeric MDI, etc. can be used.

In addition, the isocyanate prepolymer contains diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI), and carbodiimide modified products. It is an isocyanate group-terminated prepolymer obtained by reacting with a hydrogen group-containing compound. For example, an isocyanate-terminated prepolymer obtained by reacting MDI with polytetramethylene ether glycol (PTMEG) with a number average molecular weight of 650 to 2,000 at 80°C for 3 hours. The NCO ratio is preferably 21 to 23%, and the viscosity is It is suitable to have a viscosity between 800 and 5,000cP.

As described above, the two-component polyurethane resin composition containing the polyol part (A) and the main part (B) consisting of a polyfunctional isocyanate or a prepolymer thereof may include a moisture absorbent and a surfactant as additives, if necessary, to determine the physical properties of the polyurethane resin composition. Of course, it can be used within the range that does not deteriorate.

Next, we will look at synthesis examples, examples, and experimental examples of the two-component polyurethane resin composition for membrane potting with excellent dimensional stability and machinability according to the present invention. The following will be easily understood by those with ordinary knowledge. The present invention will be described through preferred embodiments that can be implemented.

1. Synthesis of polyol part (A)

[Synthesis Example 1]

Install a thermometer, nitrogen bubble, stirrer, impeller, and cooling condenser in a four-neck round glass flask reactor. Purge nitrogen inside the reactor, add 50g of HL60S (HOLLOWLITE) and 40g of PEARLBOND™ ECO 590 (Lubrizol) and melt them at a temperature of 80°C for 1 hour. Afterwards, polyol and raw materials GP400 (KPX green chemial) 250g, KR31 (KPX green chemial) 200g, castor oil 550g, 1,4-butanediol 10g, and dehydrated castor oil 5g were added in a vacuum oven at 100°C for 1 hour to remove moisture. Heat to 80°C and stir for 2 hours.

[Synthesis Example 2]

Install a thermometer, nitrogen bubble, stirrer, impeller, and cooling condenser in a four-neck round glass flask reactor. Purge nitrogen inside the reactor, add 50g of HL60S (HOLLOWLITE) and 40g of PEARLBOND™ ECO 590 (Lubrizol) and melt them at a temperature of 80°C for 1 hour. Afterwards, polyol and raw materials GP400 (KPX green chemial) 300g, KR31 (KPX green chemial) 200g, castor oil 500g, 1,4-butanediol 10g, and dehydrated castor oil 5g were added in a vacuum oven at 100°C for 1 hour to remove moisture. Heat to 80°C and stir for 2 hours.

[Synthesis Example 3]

Install a thermometer, nitrogen bubble, stirrer, impeller, and cooling condenser in a four-neck round glass flask reactor from which moisture was removed for 1 hour in a vacuum oven at 100°C. Purge nitrogen inside the reactor, add 50g of HL60S (HOLLOWLITE) and 40g of PEARLBOND™ ECO 590 (Lubrizol) and melt them at a temperature of 80°C for 1 hour. Afterwards, polyol and raw materials GP400 (KPX green chemial) 250g, KR31 (KPX green chemial) 220g, castor oil 530g, 1,4-butanediol 10g, and dehydrated castor oil 5g were added in a vacuum oven at 100°C for 1 hour to remove moisture. Heat to 80°C and stir for 2 hours.

[Synthesis Example 4]

Install a thermometer, nitrogen bubble, stirrer, impeller, and cooling condenser in a four-neck round glass flask reactor from which moisture was removed for 1 hour in a vacuum oven at 100°C. Purge nitrogen inside the reactor, add 40g of PEARLBOND™ ECO 590 (Lubrizol), and dissolve at a temperature of 80°C for 1 hour. Afterwards, polyol and raw materials GP400 (KPX green chemial) 250g, KR31 (KPX green chemial) 200g, castor oil 550g, 1,4-butanediol 10g, and dehydrated castor oil 5g were added in a vacuum oven at 100°C for 1 hour to remove moisture. After heating to 80°C, stir for 2 hours.

[Synthesis Example 5]

Install a thermometer, nitrogen bubble, stirrer, impeller, and cooling condenser in a four-neck round glass flask reactor from which moisture was removed for 1 hour in a vacuum oven at 100°C. Nitrogen was purged inside the reactor and moisture was removed in a vacuum oven at 100°C for 1 hour. Polyol and raw materials GP400 (KPX green chemial) 250g, KR31 (KPX green chemial) 200g, castor oil 550g, 1,4-butanediol 10g, dehydrated. Add 5g of castor oil and 50g of HL60S (HOLLOWLITE), heat to 80°C, and stir for 2 hours.

[Synthesis Example 6]

Install a thermometer, nitrogen bubble, stirrer, impeller, and cooling condenser in a four-neck round glass flask reactor from which moisture was removed for 1 hour in a vacuum oven at 100°C. Nitrogen was purged inside the reactor and moisture was removed for 1 hour in a vacuum oven at 100°C. Polyol and raw materials 250g of GP400 (KPX green chemial), 200g of KR31 (KPX green chemial), 550g of castor oil, and 10g of 1,4-butanediol were added. and heated to 80°C and stirred for 2 hours.

The mixing amount of each component for the polyol part (A) of Synthesis Examples 1 to 6 is shown in [Table 1] below (unit: g).

division Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 GP400(a) 250 300 250 250 250 250 KR31(b) 200 200 220 200 200 200 castor oil (c) 550 500 530 550 550 550 1,4-BD(d) 10 10 10 10 10 10 Dehydrated Castor Oil(e) 5 5 5 5 5 - HL60S(f) 50 50 50 - 50 - eco 590(g) 40 40 40 40 - -

2. Synthesis of thematic parts (B)

[Synthesis Example 7]

Install a thermometer, nitrogen bubble, stirrer, impeller, cooling condenser, and vacuum pump in a spherical round glass flask reactor. Purge nitrogen inside the reactor, add 901 g of MDI-50, and slowly heat to 60°C while stirring. Afterwards, 33g of castor oil is slowly added and the reaction is carried out for 30 minutes, a total of 3 times. Afterwards, it was further heated to 80°C and reacted for 3 hours to prepare an isocyanate prepolymer.

3. Preparation of polyurethane resin composition

[Examples 1 to 3]

The materials of Synthesis Examples 1 to 3 as the polyol part (A) and Synthesis Example 7 as the main part (B) were uniformly mixed so that the NCO/OH INDEX value was 1.04, and the width × length × height was 4 cm × 30 cm × 1.5. A polyurethane resin composition was synthesized by injecting it into a mold measuring cm and curing the molded product at 50°C for 24 hours.

[Comparative Examples 1 to 3]

The materials of Synthesis Examples 4 to 6 as the polyol part (A) and Synthesis Example 7 as the main part (B) were mixed uniformly so that the NCO/OH INDEX was 1.04, and the width x length x height was 4 cm x 30 cm x 1.5 cm. A polyurethane resin composition was synthesized by injecting it into a mold and curing the molded product at 50°C for 24 hours.

The mixing ratio of polyol part (A)/main part (B) for the polyurethane resin composition prepared in Examples 1 to 3 and Comparative Examples 1 to 3 is shown in [Table 2] below.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 A (part by weight) 101 98 100 98 99 96 B (part by weight) 99 102 100 102 101 104

[Experimental example]

The results of measuring the physical properties of the polyurethane resin compositions performed in Examples 1 to 3 and Comparative Examples 1 to 3 are shown in Table 3 below.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Hardness (25℃) 82 77 79 84 83 85 Dimensional change value (mm) 0 -One -0.5 -2 -2 -3 Hardness (80℃) 51 47 48 53 52 55 Machinability ◎ ◎ ◎ ○ ○ △

○ Hardness: The hardness of the cured polyurethane resin was measured on five flat surfaces using HT-6510D Shore D type at 25℃ and the average value was shown.

○ Dimensional change value: The dimensional change value of the cured polyurethane resin was measured by demolding the cured resin from a mold at 50℃ and measuring the size 7 days later.

○ Machinability: The hardness of the cured polyurethane resin was checked after being left at 80℃ for 3 hours and cut with a cutter to check the cutting condition and cut surface (neat appearance: ◎, layered: ○, broken: △, Cannot be cut: ×).

As shown in [Table 3], comparing the experimental results of measuring the physical properties of the polyurethane resin compositions prepared according to Examples 1 to 3 and Comparative Examples 1 to 3, the results of Examples 1 to 3 prepared according to the present invention Example 3 has an overall faster curing speed and relatively stable heating temperature compared to Comparative Examples 1 to 3, and has excellent hardness and good dimensional stability, as well as good formability, which can dramatically improve productivity. , Furthermore, it was confirmed that the machinability was very good.

Therefore, the two-component polyurethane resin composition for membrane potting with excellent dimensional stability and machinability manufactured according to the present invention can be substituted, modified, and changed in various ways without departing from the technical spirit of the present invention, such as the present invention. In addition to membrane devices, it can be used in a variety of purposes and forms in various industrial fields such as aerospace, automobiles, optics, lighting, PCB protection, and electronics.

Claims (7)

In the two-component polyurethane resin composition comprising a polyol part (A) and a main part (B) consisting of a polyfunctional isocyanate or a prepolymer thereof,
(a) 2 to 40% by weight of at least one polyol selected from polyester polyols, polyether polyols, and castor oil derivatives with a number average molecular weight of 200 to 1000 and having 2 to 3 OH groups,
(b) 2 to 30% by weight of at least one polyol selected from polyether polyols, polyester polyols, and castor oil derivatives with a number average molecular weight of 200 to 1000 and having 3 to 4 OH groups,
(c) 20 to 70% by weight of at least one polyol selected from polyether polyols, polyester polyols, and castor oil derivatives with a number average molecular weight of 400 to 1,500 and having 4 to 5 OH groups,
(d) 0.1 to 5% by weight of a chain extender with two functional groups and a molecular weight of 50 to 200,
(e) 1 to 10% by weight of plasticizer,
(f) 0.1 to 7% by weight of micro hollow sphere particles,
(g) With respect to 100 parts by weight of the polyol part (A) consisting of the first step of mixing 0.1 to 5% by weight of thermoplastic polyurethane (TPU) with a melting point of 80 to 100°C,
A two-component polyurethane resin composition for membrane potting, characterized in that it consists of a second step of mixing and reacting the main part (B) composed of isocyanate or a prepolymer thereof having two or more NCO groups at a ratio of 90 to 110 parts by weight. According to paragraph 1,
The chain extender (d) is a two-component polyurethane resin composition for membrane potting, characterized in that one or more types selected from glycols and amines are used. According to paragraph 1,
The plasticizer (e) is a two-component polyurethane resin composition for membrane potting, characterized in that dehydrated castor oil is used. According to paragraph 1,
The micro hollow sphere particles (e) are hollow spheres made of glass or polystyrene, surface-treated with a silane coupling agent, and have a diameter of 1 to 200 ㎛ and a specific gravity in the range of 0.5 to 1.0. A two-component polyurethane resin for membrane potting. Composition. According to clause 4,
A two-component polyurethane resin composition for membrane potting, characterized in that the silane coupling agent is one selected from vinyl-based, epoxy-based, methacryloxy-based, acryloxy-based, and amino-based. According to paragraph 1,
The thermoplastic polyurethane (f) is a two-component polyurethane resin composition for membrane potting, characterized in that the melting point is 80 to 100 ℃ and the flow index is 50 g / 10 min (170 ℃ / 2.16 kg) or more. According to paragraph 1,
The subject part (B) uses at least one selected from pure isocyanate, polymeric isocyanate, and modified isocyanate having two or more NCO groups, and the NCO/OH index (INDEX) ) A two-component polyurethane resin composition for membrane potting, characterized in that it is mixed in a range of 1.0 to 1.2.