KR101730055B1 - Polyurethane resin composition and polyurethane mounting pad - Google Patents

Abstract

The present invention relates to a polyurethane resin comprising a reaction product between a polyol, a polyisocyanate compound and a chain extender comprising a diol compound containing a hydrophilic functional group or a diamine compound; An organic solvent containing at least one selected from the group consisting of dimethylformamide (DMF) and methyl ethyl ketone (MEK); And a surfactant; and a polyurethane support pad comprising a wet coagulation of such a resin composition.

Description

POLYURETHANE RESIN COMPOSITION AND POLYURETHANE MOUNTING PAD BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to a polyurethane resin composition and a polyurethane support pad, and more particularly, to a polyurethane resin composition and a polyurethane support pad which can form a long and large pore uniformly in the interior thereof to provide a support pad having low hardness, A resin composition and a polyurethane support pad made from such a resin composition.

Since a substrate used for a semiconductor device or a display device requiring high integration requires a fine and precise surface, various planarization methods have been applied. Particularly, in accordance with the trend of high integration and high performance of semiconductor devices or display devices, a method of relatively moving and polishing a polishing pad and an object to be polished while supplying a slurry composition containing abrasive particles and various chemical components between the polishing pad and the object to be polished This is being commonly used. In this polishing method, the object to be polished is fixed on the supporting pad so as to maintain a predetermined position and posture in polishing or processing for more precise polishing.

On the other hand, Japanese Patent Laid-Open No. 2006-334745 discloses a polyurethane foam obtained by reacting and curing polyols, polyisocyanates, a blowing agent, a catalyst and a water repellency-imparting agent, and a polishing support pad obtained using the same. However, the polyurethane foam is obtained by using a foaming agent such as water, methylene chloride or carbonic acid gas. Such a foam has a relatively high hardness, or it is difficult to uniformly form long and large pores therein, It is not easy to secure a high compression ratio and a compressive elastic modulus.

Previously, the support pads have different sizes and irregularly distributed pores in the interior, and the cushioning performance and adsorption force of the support pads are not good. Also, since the polished body is not firmly fixed on the support pads during the polishing process, There is a problem that can not be achieved. In addition, since the former support pad exhibits uneven size and distribution of bubbles formed therein, not only the physical properties such as compression ratio and compressive elastic modulus are not good, but also the water repellent function is not sufficient and the abrasive article easily deviates during polishing or processing .

Accordingly, it is necessary to develop a new support pad that enables more precise and efficient polishing of a substrate used in a semiconductor device or a display device.

Japanese Patent Application Laid-Open No. 2006-334745

The present invention is to provide a polyurethane resin composition capable of uniformly forming long and large pores therein to provide a support pad having low hardness, excellent compression ratio and high compression modulus.

Further, the present invention is to provide a polyurethane support pad having a low hardness, an excellent compression ratio and a high compression modulus by uniformly forming long and large pores therein.

The present invention relates to a polyurethane resin comprising a reaction product between a polyol, a polyisocyanate compound and a chain extender comprising a diol compound containing a hydrophilic functional group or a diamine compound; An organic solvent containing at least one selected from the group consisting of dimethylformamide (DMF) and methyl ethyl ketone (MEK); And a surfactant. The present invention also provides a polyurethane resin composition for producing a support pad of a polishing apparatus.

The present invention also provides a polyurethane support pad comprising a wet coagulate of said polyurethane resin composition.

Hereinafter, the polyurethane resin composition and the polyurethane support pad according to a specific embodiment of the present invention will be described in more detail.

In the present specification, the term 'support pad' refers to a pad that serves to closely adhere or fix a film to be polished to a carrier in a polishing process during a substrate manufacturing process used in a semiconductor or a display device.

According to one embodiment of the invention, there is provided a polyurethane resin comprising a polyol, a polyisocyanate compound and a reactant between a chain extender comprising a diol compound or a diamine compound containing a hydrophilic functional group; An organic solvent containing at least one selected from the group consisting of dimethylformamide (DMF) and methyl ethyl ketone (MEK); And a surfactant. The polyurethane resin composition for the support pad of the polishing apparatus may be provided.

The present inventors synthesized a polyurethane resin by using a diol compound or a diamine compound containing a hydrophilic functional group as a chain extender, while using a diol compound such as ethylene glycol or butanediol as a chain extender in the course of synthesizing a polyurethane resin. It has been confirmed through experiments that the long and large pores are uniformly formed inside the support pad made of the polyurethane resin to realize low hardness, excellent compressibility and high compression modulus, and the invention is completed.

When the diol compound or the diamine compound containing the hydrophilic functional group is used as a chain extender, the reaction rate can be greatly improved in the process of synthesizing the polyurethane resin. When the polyurethane resin composition is applied to the wet coagulation process, Due to the hydrophilic functional group contained, the penetration rate of water in the solidification process is accelerated, and pores having an appropriate size and shape can be easily formed.

In addition, the polyurethane resin synthesized from the diol compound containing a hydrophilic functional group or a diamine compound as a chain extender may include a relatively long polymer chain, and the bonds in the polymer chain may be composed mostly of a single bond. Accordingly, the molecular mobility of the polyurethane resin synthesized using the specific chain extender can be increased, and the finally prepared support pad can be easily stretched or compressed, so that a high compression ratio and a compression recovery rate can be obtained Lt; / RTI >

Specifically, the polyurethane resin composition used for the production of the support pad comprises a chain extender (c) comprising a polyol (a), a polyisocyanate compound (b) and a diol compound containing a hydrophilic functional group or a diamine compound ). ≪ / RTI >

Hydrophilic functional groups may be contained in the interior of the diol compound or diamine compound molecule used as the chain extender. As described above, the hydrophilic functional group may increase the rate of synthesizing the polyurethane resin, or the chain of the synthesized polyurethane resin may be long, or may contain only a single bond, or the polyurethane resin may increase the fluidity of the molecule, The performance of the support pad can be improved.

및

을 의미한다. The hydrophilic functional group may be an oxy group (-O-), a hydroxyl group (-OH), a secondary or tertiary amine group, and preferably an oxy group. The secondary amine group and the tertiary amine group are

And

.

Specifically, the diol compound containing the hydrophilic functional group may include a compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1, X ₁ and X ₂ may be the same or different and each is an alkylene group of 1 to 5 carbon atoms, n is an integer of 1 to 10, Y is alkylene of 1 to 5 carbon atoms, Y in the unit may be the same or different from each other.

In addition, the diamine compound containing the hydrophilic functional group may include a compound represented by the following general formula (2).

(2)

In Formula 2, X ₁ and X ₂ may be the same or different and each is an alkylene group of 1 to 5 carbon atoms, n is an integer of 1 to 10, Y is alkylene of 1 to 5 carbon atoms, Y in the unit may be the same or different from each other.

The chain extender may further include at least one diol compound selected from the group consisting of ethylene glycol and 1,4-butanediol in addition to the diol compound or diamine compound containing the hydrophilic functional group.

Various polyols may be used for the synthesis of the polyurethane resin. Specifically, the polyol may be a polyester polyol containing a reactant between a polycarboxylic acid having 2 to 10 carbon atoms and a diol compound.

The polycarboxylic acid having 2 to 10 carbon atoms used for synthesizing the polyester polyol may be a dicarboxylic acid having 4 to 8 carbon atoms, and may be preferably adipic acid.

Diol compounds which may be used in the synthesis of the polyester polyols may include ethylene glycol, 1,4-butane diol, diethylene glycol or a mixture of two or more thereof.

The polyester polyol may have an average hydroxyl value of 20 to 100 mg KOH / g or a weight average molecular weight of 500 g / mol to 5,000 g / mol. If the average hydroxyl value or the weight average molecular weight of the polyester polyol is too small, the strength and hardness of the polyurethane resin to be synthesized may be significantly lowered. If the average hydroxyl value or the weight average molecular weight of the polyester polyol is too large, The hardness may be greatly increased, and the compressibility or compressive modulus of the support pad produced using the polyurethane resin may be significantly lowered.

The ratio of the number of moles of the hydroxyl group (-OH) contained in the polyester polyol and the chain extender and the number of moles of the isocyanate group of the polyisocyanate compound is 1: 0.99 to 1: 1.2, preferably 1: 1 to 1: 1.1.

When the number of moles of the polyisocyanate compound is smaller than the sum of the number of moles of the hydroxyl group (-OH) contained in the polyester polyol and the chain extender, it is difficult for the produced polyurethane resin to have an appropriate density, viscosity and weight average molecular weight However, it is difficult to increase the thickness of the support pad produced using such a polyurethane resin, and physical properties such as compression ratio, compressive elastic modulus and hardness may be significantly lowered.

If the number of moles of the polyisocyanate compound is too large as compared with the number of moles of the chain extender, the hardness, viscosity or molecular weight of the polyurethane resin to be produced may become excessively large, and the support pad produced using such a polyurethane resin may have a proper compression ratio, It may be difficult to ensure physical properties such as compression modulus and hardness.

The polyisocyanate compound means a compound having a plurality of isocyanate groups. Such a polyisocyanate compound may be a polyisocyanate containing an aliphatic, alicyclic, araliphatic, aromatic and heterocyclic functional group, and may be represented by the formula Q (NCO) n. Wherein n is an integer from 2 to 4 and Q can be an aliphatic, alicyclic, aromatic or araliphatic hydrocarbon functional group containing 2 to 18, preferably 6 to 10, C atoms. Specific examples of the polyisocyanate compound include ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 1,12-dodecane diisocyanate, cyclobutane-1,3 Diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 2,4-hexahydrotoluene diisocyanate, 2,6-hexahydrotoluene diisocyanate, hexahydro-1,3-phenylene diisocyanate, hexahydro-1,4-phenylene diisocyanate, perhydro- Diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,4-dorol diisocyanate (DDI) , 4,4'-stilbene diisocyanate, 3,3'- Methylene-4,4'-biphenylene diisocyanate (TODI), toluene 2,4-diisocyanate, toluene 2,6-diisocyanate (TDI), diphenylmethane-2,4'-diisocyanate (MDI) Diphenylmethane diisocyanate (MDI), diphenylmethane-4,4'-diisocyanate (MDI), naphthylene-1,5-isocyanate (NDI) or a mixture of two or more thereof.

The polyurethane resin may have a weight average molecular weight of 50,000 g / mol to 500,000 g / mol, preferably 100,000 g / mol to 400,000 g / mol. In addition, the polyurethane resin may have a viscosity of 100,000 cps to 500,000 cps. The weight average molecular weight and viscosity of such a polyurethane resin may be based on a solids level of 30%. In the process of producing the polyurethane support pad, dimethylformamide mixed with the polyurethane resin may dissolve in water to form pores while escaping. When a polyurethane resin having the molecular weight or viscosity within the above range is used, Can be formed with a uniform size and a uniform distribution.

The polyurethane resin composition may form a polyurethane support pad having pores formed therein through a wet solidification process. Such pore formation is due to the phase separation of the polyurethane resin, water, and organic solvent. Specifically, when the polyurethane resin dissolved in an organic solvent containing at least one selected from the group consisting of dimethylformamide (DMF) and methyl ethyl ketone (MEK) is immersed in a coagulation bath filled with a constant aqueous solution, the polyurethane The resin and the organic solvent are phase-separated and the phase-separated organic solvent is replaced with an aqueous solution or water to form pores. After the pores are formed, the polyurethane resin pads that can be used for manufacturing the support pad of the polishing apparatus can be manufactured by removing the residual organic solvent through the washing process and the drying process.

Wherein the polyurethane resin composition comprises: 1 to 80 wt% of the total weight of the polyurethane resin; 10 to 90 wt% of the DMF solvent; And 0.05 to 15 wt% of the surfactant.

The surfactant may be an anionic surfactant, a nonionic surfactant, or a mixture thereof.

The anionic surfactant can uniformly penetrate the water over the entire area of the composition to be coagulated and prevent the phase separation of the polyurethane resin, water, and organic solvent from concentrating on a certain portion, Can be formed very uniformly.

Examples of the anionic surfactant include dodecylbenzenesulfonic acid, dodecylbenzenesulfonic acid derivatives, succinic acid, succinic acid derivatives, dodecylsulfate, dodecylsulfate derivatives, and mixtures of at least one of the foregoing. The use of dodecylbenzenesulfonic acid or a derivative thereof as an anionic surfactant and succinic acid or its derivative is used to control the shape and size of the pores formed in the support pad to suitably control the physical properties of the support pad .

The nonionic surfactant can increase the adsorption force of the support pad or flatten the surface of the pad. Examples of such nonionic surfactants include silicone-based polymers, silicone oils, glycerol-based polymers, and hydrocarbon-based polymers. Such a nonionic surfactant can be used by suitably adjusting the content in consideration of the physical properties of the support pad to be produced and the process conditions.

The polyurethane resin composition may further include at least one additive selected from the group consisting of fillers, water repellents, pore size regulators and pigments.

A polyurethane resin comprising a reaction product between the polyol, a polyisocyanate compound and a chain extender comprising a diol compound or a diamine compound containing a hydrophilic functional group; An organic solvent containing at least one selected from the group consisting of dimethylformamide (DMF) and methyl ethyl ketone (MEK); And a surfactant are coagulated in a coagulation bath containing an organic solvent and water, phase separation phenomena of the resin composition components, for example, polyurethane resin, water and organic solvent phase separation phenomenon occur. In this phase separation phenomenon A polyurethane support pad having a plurality of pores formed therein can be obtained.

The support pad made of the polyurethane resin composition may be distinguished from other conventional polyurethane sheets, for example, a polyurethane polishing pad or a polyurethane synthetic leather. Specifically, the polyurethane polishing pad must have a high abrasion resistance and high hardness, and a polyurethane resin having a crosslinking reaction should be used. Also, the manufacturing method is not a wet solidification process, but a prepolymer and other monomers are mixed in situ, ) And then curing it.

On the other hand, according to another embodiment of the invention, there can be provided a polyurethane support pad comprising a wet coagulation of a polyurethane resin composition.

When a resin composition comprising a polyurethane resin synthesized by using a diol compound containing a hydrophilic functional group or a diamine compound as a chain extender, an organic solvent and a surfactant is wet-solidified, long and large pores are uniformly formed inside, And a support pad having a high compressive modulus of elasticity.

Particularly, when the diol compound or the diamine compound containing the hydrophilic functional group is used as the chain extender, the reaction rate can be greatly improved in the process of synthesizing the polyurethane resin. When the polyurethane resin composition is applied to the wet coagulation process, Due to the hydrophilic functional groups contained in the resin, the permeation rate of water in the solidification process is increased, and pores having an appropriate size and shape can be easily formed.

In addition, the polyurethane resin synthesized from the diol compound containing a hydrophilic functional group or a diamine compound as a chain extender may include a relatively long polymer chain, and the bonds in the polymer chain may be composed mostly of a single bond. Accordingly, the molecular mobility of the polyurethane resin synthesized using the specific chain extender can be increased, and the finally prepared support pad can be easily stretched or compressed, so that a high compression ratio and a compression recovery rate can be obtained Lt; / RTI >

Specific examples of the organic solvent, surfactant, and the like containing at least one selected from the group consisting of the polyurethane resin, polyol, polyisocyanate compound, chain extender, dimethylformamide (DMF) and methyl ethyl ketone (MEK) And includes the above-mentioned contents with respect to the resin composition of one embodiment of the invention.

The polyurethane support pad may be comprised of a substrate of a polyurethane resin containing a reactant between a polyol, a polyisocyanate compound and a chain extender comprising a diol compound containing a hydrophilic functional group or a diamine compound, Pores having a length of 100 to 500 mu m may be formed in the substrate. As described above, after the wet coagulation of the polyurethane resin composition of one embodiment of the present invention, the organic solvent, the surfactant, the water, and the like can be removed, and a porous polyurethane resin having many fine pores can be formed .

The polyurethane support pad may have a thickness of 0.5 to 3 mm, preferably 1 to 2.5 mm, and may have a density of 0.10 to 0.50 g / cm 3, preferably 0.15 to 0.30 g / cm 3.

In addition, the polyurethane support pad may have Asker C hardness of 20 to 25, and Asker C hardness of 21 to 23, as prepared using the particular polyurethane resin composition described above.

The polyurethane support pad may have a compressibility of 45% or more, preferably 45 to 65%, and may have a compressive modulus of 95% or more, preferably 95% to 99%.

The pores distributed within the polyurethane support pad may have a flatness ratio (ratio of length to width) of 2 to 10, preferably a flatness ratio of 3 to 7.

In addition, the polyurethane support pad may include pores having a length of 100 mu m to 500 mu m.

The length of the pores refers to a straight line distance between the highest point and the lowest point in one of the pores. The width of the pores is the shortest distance among the straight lines connecting two points on the pore boundary in a direction perpendicular to the straight line corresponding to the length of the pores. .

The long and large pores inside the polyurethane support pad can lower the hardness of the pad to produce a soft pad having a high compressibility and can easily trap the air trapped between the support pad and the film to be polished, It is possible to uniformly distribute the force applied in the polishing step to the entire support pad and the entire object to be polished, thereby minimizing defects that may occur during polishing.

Meanwhile, the polyurethane support pad may be formed by solidifying the polyurethane resin composition. Specifically, the polyurethane support pad comprises the steps of: forming the polyurethane resin composition; Coating or injecting the polyurethane resin composition into a predetermined substrate or frame to form a coating layer; Solidifying the coating layer; And a step of washing, dehydrating and drying the coagulated product of the composition.

In the step of solidifying the coating layer, a substrate or a frame on which the coating layer is formed is coagulated with an organic solvent containing at least one selected from the group consisting of dimethylformamide (DMF) and methyl ethyl ketone (MEK) Into a coagulation bath filled with a 1 to 20 wt% aqueous solution of DMF. In the solidification process, the organic solvent in the polyurethane resin is replaced with water, and the polyurethane resin gradually coagulates, thereby forming a plurality of pores. By adjusting the concentration of the organic solvent in the coagulation bath, the coagulation time and the pore size in the support pad can be controlled.

In the washing step of the solidified product, an organic solvent or an additive can be removed, and a method and an apparatus known to be usable in the method of manufacturing a supporting pad can be used without any limitation.

In the step of solidifying the coating layer, the substrate or the frame on which the coating layer is formed may be put into a coagulation tank filled with the organic solvent and water. In the solidification process, the organic solvent (dimethylformamide (DMF) or methyl ethyl ketone (MEK)) is replaced with water in the polyurethane resin so that the polyurethane resin gradually coagulates and thus a large number of pores can be formed . The concentration of the aqueous solution and the amount of the aqueous solution or the water filled in the coagulation bath are not particularly limited and can be appropriately adjusted according to the reaction conditions and physical properties of the support pad to be produced. After the solidification process, water and an organic solvent may remain in the polishing pad, and water, organic solvent, and other components may be removed from the polishing pad by washing the solidified product and drying it in an oven.

The manufacturing process of the polyurethane support pad may include polishing (or buffing) the surface of the wet coagulation product. The polishing step is a step of cutting a surface of a low hardness polyurethane film (100% moduli 1 to 10) using a roll wound with sandpaper rotated at high speed, and is a process of applying high energy.

In this polishing (or buffing) process, the polished film may be cut several hundreds of um at a time, or may be cut several times several tens of um. When a low hardness film is polished at a time, a difference in thickness or a difference in abrasion (buffing) level may occur in the machine direction (MD) direction, and the unevenly accumulated energy in the support pad may cause a polishing film, It may be unevenly transferred to the glass substrate of the display or the like to cause lines or streaks in the direction of the TD (Transverse Direction).

Further, in the manufacturing process of the polyurethane support pad, it may further include forming an adhesive layer on the surface of the buffered wet solidified product. This adhesive layer may be formed using any method and configuration known to be used to make the final product of the backing pad without any particular limitation. For example, the adhesive layer may be formed by applying a certain adhesive, for example, a pressure sensitive adhesive (PSA) or the like, to the surface of the wet coagulated material or the surface of the surface polished wet coagulated material, And laminating a pressure-sensitive double-side adhesive film on the surface of the surface-polished wet coagulation product.

According to the present invention, there is provided a polyurethane support pad including a relatively long polymer chain and having a high mobility due to almost single bonds in the polymer chain and having long and large pores uniformly formed therein .

The polyurethane support paddle can easily receive air trapped between the polishing target film and the inside of the polishing pad and uniformly distribute the force applied in the polishing step to the entire support pad and the entire object to be polished, It is possible to minimize defects that may occur.

Also, since the polyurethane support pad can be easily stretched or compressed due to its polymer properties and characteristic internal structure, an excellent compression ratio and a high compression elastic modulus can be realized. Thus, a high cushioning performance and an attractive force .

Fig. 1 is a cross-sectional SEM photograph of the polyurethane support pad obtained in Example 1. Fig.
2 is a cross-sectional SEM photograph of the polyurethane support pad obtained in Example 2. Fig.
3 is a cross-sectional SEM photograph of the polyurethane support pad obtained in Comparative Example 1. Fig.
4 is a cross-sectional SEM photograph of the polyurethane support pad obtained in Comparative Example 2. Fig.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

[ Example : Production of polyurethane resin and support pad]

One. Example 1

(1) Production of polyurethane resin

Adipic acid, ethylene glycol and 1,4-butanediol were reacted at a molar ratio of 1: 0.5: 0.5 at a temperature of 200 캜, a reduced pressure of 500 to 760 mmHg and a vacuum atmosphere to synthesize a polyester polyol.

Then, in the presence of dibutyltin dilaurate, the synthesized polyester polyol, chain extender [2,2 '- (ethylenedioxy) bis (ethylamine)] and DMF were placed in a reactor and heated to 60 ° C.

The polyisocyanate compound was added to the reactor so that the ratio of the sum of the number of moles of hydroxyl groups contained in the polyester polyol and the chain extender to the number of moles of the isocyanate group of the polyisocyanate compound was 1: , A small amount of a polyisocyanate compound was further added and polymerization was carried out.

Then, MeOH was added at the time when the polyurethane having the target viscosity and molecular weight was polymerized to react with an isocyanate group to synthesize a polyurethane resin.

(2) Production of Support Pads

A mixture of 100 g of the obtained polyurethane resin (30 wt% DMF solution), 70 g of DMF, 5 g of an anionic surfactant, 1.0 g of a nonionic surfactant, 0.3 g of PDMS additive, 6 g of a coloring agent (carbon black resin), 1.0 g of a filler, ), Stirred at a high speed for 10 minutes with a paint shaker, and centrifuged at 3000 rpm for 10 minutes to obtain a slurry polyurethane resin composition.

The obtained polyurethane resin composition was coated on a PET film to a thickness of 2.00 mm and then solidified in a coagulation bath filled with 2 to 15% aqueous DMF solution. Thereafter, the resulting coagulum was washed with water, dehydrated and dried to prepare a polyurethane support pad. A sectional SEM photograph of the prepared polyurethane support pad is shown in FIG.

2. Example 2

A polyurethane resin composition and a polyurethane support pad were prepared in the same manner as in Example 1 except that ethylenedioxy dimethanol was used as a chain extender. A sectional SEM photograph of the prepared polyurethane support pad is shown in Fig.

[ Comparative Example : Production of polyurethane resin and support pad]

One. Comparative Example 1

A polyurethane resin composition and a polyurethane support pad were prepared in the same manner as in Example 1, except that ethylene glycol was used as a chain extender. A sectional SEM photograph of the prepared polyurethane support pad is shown in FIG.

2. Comparative Example 2

A polyurethane resin composition and a polyurethane support pad were prepared in the same manner as in Example 1 except that 1,4-butanediol was used as a chain extender. A cross-sectional SEM photograph of the prepared polyurethane support pad is shown in FIG.

< Experimental Example >

Experimental Example 1 : Density measurement of supporting pads

The polyurethane support pads obtained in the above Examples and Comparative Examples were prepared in the size of 25 mm * 30 mm, and the thicknesses were measured. Then, the weights of these specimens were measured to calculate the density. Then, the weight of the specimen was measured five times repeatedly, the density values of the respective specimens were obtained, and the density of the support pads was calculated from the average values thereof.

Experimental Example 2 : Hardness measurement of supporting pad

The polyurethane support pads obtained in the above Examples and Comparative Examples were prepared in a size of 25 mm * 30 mm and hardness was measured using a Asker hardness meter.

Experimental Example 3 : Of support pads Compression ratio  And Compression recovery rate  Measure

The compressibility and the compression recovery rate of the polyurethane support pad obtained in the above Examples and Comparative Examples were measured according to JIS L1021-16.

Specifically, the polyurethane support pads obtained in the above Examples and Comparative Examples were cut to prepare specimens having a size of 25 mm * 30 mm. The initial thickness was measured using a dial gauge (T0) after the initial load of 100 g / cm2 was applied to the specimen for 30 seconds. The specimen was subjected to a load of 1120 g / cm2 for 5 minutes and then the thickness was measured under pressure (T1). After removing all the loads and leaving for 5 minutes, the thickness was measured after applying an initial load of 100 g / cm 2 for 30 seconds (T0 '). The compression ratio and the compression recovery rate were calculated by applying the following equations to each of the measured thicknesses.

[formula]

Compression ratio (%) = (T0 - T1) * 100 / T0

Compression recovery rate (%) = (T0 '- T1) * 100 / (T0 - T1)

The results of Experimental Examples 1 to 3 are shown in Table 1 below.

Asker C hardness Density (g / cm3) Compressibility (%) Compressive modulus (%) Example 1 21 0.20 48 98 Example 2 22 0.22 46 97 Comparative Example 1 24 0.25 36 92 Comparative Example 2 29 0.33 19 87

As shown in Table 1 above, it was confirmed that the Examples show compressibility of at least 45% and compressive modulus of 95% or more while having relatively low density and low Asker C hardness.

1 to 2, the support pads of Examples 1 and 2 have a plurality of support pads having a length of about 100 to 500 m and a flat ratio (ratio of length to width) of about 3 to 10 It was confirmed that the pores are uniformly distributed.

On the contrary, the support pads of Comparative Examples 1 and 2 were found to have a relatively high hardness and a compressibility and a compressive elastic modulus lower than those of the support pads of the Examples. The density and hardness of the support pad of Comparative Example 2 were too small and the compressive modulus of elasticity was also lower than that of Examples.

Claims (20)

A polyol, a polyisocyanate compound, and a reactant between a chain extender comprising a hydrophilic functional group-containing diol compound comprising a compound of formula (I) or a diamine compound containing a hydrophilic functional group comprising a compound of formula 1 to 80 wt% urethane resin;
10 to 90 wt% of an organic solvent containing at least one selected from the group consisting of dimethylformamide (DMF) and methyl ethyl ketone (MEK); And
And 0.05 to 15 wt% of a surfactant. &Lt; Desc / Clms Page number 5 &gt;
[Chemical Formula 1]

In Formula 1,
X ₁ and X ₂ may be the same or different and each is an alkylene group of 1 to 5 carbon atoms,
n is an integer of 1 to 10,
Y is alkylene having 1 to 5 carbon atoms, Y in each repeating unit may be the same or different from each other, Y is different from X ₁ and X ₂ ,
(2)

In Formula 2,
X ₁ and X ₂ may be the same or different and each is an alkylene group of 1 to 5 carbon atoms,
n is an integer of 1 to 10,
Y is alkylene having 1 to 5 carbon atoms, and Y in each repeating unit may be the same or different from each other.
The method according to claim 1,
Wherein the hydrophilic functional group is an oxy group (-O-), a hydroxyl group (-OH), a secondary or tertiary amine group.
delete delete The method according to claim 1,
Wherein the polyol is a polyester polyol comprising a reactant between a polycarboxylic acid having 2 to 10 carbon atoms and a diol compound.
6. The method of claim 5,
Wherein the diol compound comprises at least one member selected from the group consisting of ethylene glycol, 1,4-butane diol and diethylene glycol.
6. The method of claim 5,
Wherein the polyester polyol has an average hydroxyl value of from 20 to 100 mgKOH / g.
6. The method of claim 5,
Wherein the polyester polyol has a weight average molecular weight of 500 to 5,000.
The method according to claim 1,
The polyisocyanate compound may be at least one selected from the group consisting of 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, Diisocyanate, cyclohexane-1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane, 2,4-hexahydrotoluene diisocyanate , 2,6-hexahydrotoluene diisocyanate, hexahydro-1,3-phenylene diisocyanate, hexahydro-1,4-phenylene diisocyanate, perhydro-2,4'-diphenylmethane diisocyanate, 1,4-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,4-dodecyl diisocyanate (DDI), 4,4'-stilbene di Isocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate (TODI), toluene Diisocyanate (TDI), diphenylmethane-2,4'-diisocyanate (MDI), 2,2'-diphenylmethane diisocyanate (MDI), diphenylmethane -4,4'-diisocyanate (MDI) and naphthylene-1,5-isocyanate (NDI).
The method according to claim 1,
Wherein the polyurethane resin has a weight average molecular weight of 50,000 g / mol to 500,000 g / mol.
The method according to claim 1,
Wherein the surfactant comprises at least one selected from the group consisting of an anionic surfactant and a nonionic surfactant.
delete The method according to claim 1,
Wherein the chain extender further comprises at least one diol compound selected from the group consisting of ethylene glycol and 1,4-butanediol.
The method according to claim 1,
Wherein the polyurethane resin composition further comprises at least one additive selected from the group consisting of a filler, a water repellent agent, a pore size regulator and a pigment.
A polyurethane support pad comprising a wet coagulate of the polyurethane resin composition of claim 1.
16. The method of claim 15,
On a substrate of a polyurethane resin containing a reactant between a polyol, a polyisocyanate compound and a chain extender comprising a diol compound containing a hydrophilic functional group or a diamine compound,
Wherein pores having a length of 100 mu m to 500 mu m are formed.
16. The method of claim 15,
A density of 0.10 to 0.35 g / cm &lt; 3 &gt; and an Asker C hardness of 23 or less.
16. The method of claim 15,
A polyurethane support pad according to JIS L1021-16 having a compression ratio of 45% or more and a compression recovery rate of 95% or more.
16. The method of claim 15,
And a pore having a planar ratio of 3 to 10 (ratio of length to width).
The method according to claim 1,
Wherein the hydrophilic functional group-containing diol compound is (ethylenedioxy) dimethanol.

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