KR20130009687A - Poly-urethane resin and poly-urethane absorbing pad using the same - Google Patents

Abstract

PURPOSE: A polyurethane resin composition capable of providing supporting pads with high compression ratio and compression recovery rate and a polyurethane adsorption pad using the same are provided to minimize surface defect, roughness, and waviness. CONSTITUTION: A polyurethane resin composition comprises first and second polyurethane resins which include a soft part which includes residue of polyol including ethylene glycol and 1,4- butanediol at the molar ratio of 2:8-8:2 and residue of polycarboxylic acid and a hard part which includes the residue of polyisocyanate compound and residue of chain extender, an organic solvent includes one or more selected from dimethylformaldehyde and methylethylketone.

Description

Polyurethane resin composition and polyurethane adsorption pad using the same {POLY-URETHANE RESIN AND POLY-URETHANE ABSORBING PAD USING THE SAME}

The present invention relates to a polyurethane resin composition and a polyurethane support pad. More specifically, the present invention relates to a polyurethane resin composition and a polyurethane support pad. More specifically, the present invention relates to a substrate or glass used in a semiconductor device or a display device. A polyurethane resin composition that can be used in a polishing process to provide a support pad that can minimize surface defects, roughness, and waviness, and a polyurethane support pad obtained from such a resin composition.

Since a substrate used in a semiconductor device or a display device requiring high integration requires a fine and precise surface, various planarization methods have been applied. In particular, according to a trend toward higher integration and higher performance of semiconductor devices or display devices, a method of relatively moving the polishing pad and the polished body while supplying a slurry composition including the abrasive particles and various chemical components between the polishing pad and the polished body is performed. This general is being used. In such a polishing method, the polished body is fixed on the support pad to maintain a constant position and posture during polishing or processing for more accurate polishing.

On the other hand, Japanese Patent Laid-Open No. 2006-334745 discloses a polyurethane foam obtained by reacting and curing polyols, polyisocyanates, blowing agents, catalysts, and water repellent imparting agents, and a polishing support pad obtained using the same. However, the polyurethane foam is obtained by using a blowing agent such as water, methylene chloride or carbon dioxide gas, such foam has a relatively high hardness, or difficult to uniformly form long and large pores therein, low hardness region It was not easy to ensure high extrusion rate and extrusion elastic modulus at.

In addition, the previous support pads have different sizes of pores therein and are irregularly distributed, so that the cushion performance and adsorption force on the polished body was not good, and the polishing body was not firmly fixed on the support pad during the polishing process. There was a problem that could not be achieved. In addition, the previous support pad has a non-uniform size and distribution of the bubbles formed therein, not only poor physical properties such as extrusion rate and extrusion modulus, but also insufficient water repellency so that the abrasive can easily be removed during polishing or processing. Had a problem.

Accordingly, there is a need for the development of new support pads that enable more accurate and efficient polishing of substrates used in semiconductor devices or display devices.

Japanese Patent Publication No. 2006-334745

The present invention has a long and large pores uniformly therein, exhibits a high compression rate and compression recovery rate and can be used in a polishing process such as a substrate or glass used in a semiconductor device or a display device to minimize surface defects, roughness, and waviness It is to provide a polyurethane resin composition capable of providing a support pad.

In addition, the present invention is to provide a polyurethane support pad formed from the polyurethane resin composition.

The present invention provides a soft portion including residues of polyol and residues of polycarboxylic acid containing 1,4-butane diol and ethylene glycol in a molar ratio of 8: 2 to 2: 8, and residues and chains of polyisocyanate compounds. A first polyurethane resin comprising a hard part including residues of an extender; A soft portion having a composition different from that of the first polyurethane resin and comprising a residue of a polyol and a residue of a polycarboxylic acid containing 1,4-butane diol and ethylene glycol in a molar ratio of 8: 2 to 2: 8, A second polyurethane resin comprising a hard part including a residue of a polyisocyanate compound and a residue of a chain extender; An organic solvent comprising at least one member selected from the group consisting of dimethylformamide (DMF) and methyl ethyl ketone (MEK); And a surfactant, wherein each of the first polyurethane resin and the second polyurethane resin comprises 20 to 32 wt% of the residue of the polyisocyanate compound.

The present invention also provides a polyurethane support pad comprising the wet coagulated product of the polyurethane resin composition.

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

As used herein, the term “support pad” refers to a pad that serves to closely adhere or fix the polishing target film to a carrier in a polishing process during a substrate manufacturing process used in a semiconductor or display device.

In addition, in the present specification, 'residue' means a certain part or unit included in the result of the chemical reaction and derived from the specific compound when the specific compound participates in the chemical reaction. For example, the 'residue of the polyol component' means a portion derived from the polyol component in the reaction product.

According to one embodiment of the invention, the soft portion including the residue of the polyol and the residue of the polyol containing 1,4-butane diol and ethylene glycol in a molar ratio of 8: 2 to 2: 8 and A first polyurethane resin comprising a hard part including a residue of a polyisocyanate compound and a residue of a chain extender; It has a composition different from that of the first polyurethane resin, and includes a residue of a polyol and a residue of a polycarboxylic acid containing 1,4-butane diol and ethylene glycol in a molar ratio of 8: 2 to 2: 8. A second polyurethane resin comprising a soft part and a hard part including a residue of a polyisocyanate compound and a residue of a chain extender; An organic solvent comprising at least one member selected from the group consisting of dimethylformamide (DMF) and methyl ethyl ketone (MEK); And a surfactant, wherein each of the first polyurethane resin and the second polyurethane resin includes 20 to 32 wt% of the residue of the polyisocyanate compound.

As a result of the researches of the present inventors, using the resin composition obtained by mixing the two or more polyurethane resins having different chemical structures with each other, a better effect than when using a single polyurethane resin, for example, long and large pores inside It has been found that the effect of providing a polyurethane adsorption pad which is uniformly formed and can exhibit good compression and high compression recovery is realized.

In addition, each of the different polyurethane resins may be resins in which specific components constituting the soft and hard portions of the polyurethane resin and their composition ratios are controlled in a specific range, and thus the polyurethane resin may have different chemical structures. Can have

Specifically, each of the first polyurethane resin and the second polyurethane resin included in the polyurethane resin composition includes 1,4-butane diol and ethylene glycol in a molar ratio of 8: 2 to 2: 8. The soft part including the residue of the polyol and the residue of the polycarboxylic acid, and the hard part including the residue of the polyisocyanate compound and the residue of the chain extender.

In addition, the first polyurethane resin and the second polyurethane resin may have different compositions, that is, residues derived from a specific compound included in the resin, or contents thereof.

Specifically, the content of the residues of the polyisocyanate compound included in each of the first polyurethane resin and the second polyurethane resin may be different. In addition, the molar ratios of the residues of the polyols of the first polyurethane resin and the residues of 1,4-butane diol and ethylene glycol included in the residues of the polyols of the second polyurethane resin may be different. In addition, when the residue of the compound forming the soft portion of each of the first polyurethane resin and the second polyurethane resin, for example, the soft portion is derived from a polyester polyol, the first polyurethane resin and the second polyurethane resin, respectively The weight average molecular weight of the polyester polyol contained in may be different.

As can be seen in the examples below, the present inventors used the first polyurethane resin and the second polyurethane resin having different compositions or configurations within the ranges of the specific components and contents described above, respectively. In the case it was confirmed through the experiment that the support pad having excellent physical properties and quality can be prepared.

That is, the present inventors use a mixture of the first polyurethane resin and the second polyurethane resin having different compositions or configurations to uniformly contain long and large pores therein and exhibit high compression ratio and compression recovery ratio. It was used in a polishing process such as a substrate or glass used in the device to produce a support pad that can minimize surface defects, roughness, waviness.

Meanwhile, each of the first polyurethane resin and the second polyurethane resin may include a soft portion and a hard portion, and the soft portion may contain 1,4-butane diol and ethylene glycol at a molar ratio of 8: 2 to 2: 8 ( molar ratio), or a moiety ratio of 6: 4 to 4: 6, and a moiety of polyol and a moiety of a polycarboxylic acid, wherein the hard part is a moiety of the polyisocyanate compound and a moiety of a chain extender. It may include. The polyurethane resin may have a constant elasticity as the soft portion and the hard portion are included.

The soft part comprises a reactant between a polyol and a polycarboxylic acid comprising 1,4-butane diol and ethylene glycol in a molar ratio of 8: 2 to 2: 8, preferably in a molar ratio of 6: 4 to 4: 6. The reactant may be a polyester polyol. Accordingly, the soft portion may include residues of the specific polyester polyol. The molar ratio of the 1,4-butane diol and ethylene glycol may range from 8: 2 to 2: 8, for example 8: 2, 7: 3, 6: 4, 5: 5, 4: 6, 3: 7, 2: 8 or a ratio between them.

The average value of the molar ratio of 1,4-butane diol: ethylene glycol in the first polyurethane resin and the molar ratio of 1,4-butane diol: ethylene glycol in the second polyurethane resin is 7: 3 to 3: 7, Or 6: 4 to 4: 6. That is, the soft part of each of the first and second polyurethane resins may include 1,4-butane diol and ethylene glycol in a molar ratio of 8: 2 to 2: 8, and the arithmetical average of these molar ratios is If it is 7: 3-3: 7, or 6: 4-4: 6, the support pad which has more preferable physical property and quality from the said polyurethane resin composition can be provided.

The polyester polyol may have a weight average molecular weight of 1000 to 4,000. The molecular weight of such polyester polyols can affect the proportion of soft parts in the polyurethane resin, and can affect the compression rate, compression recovery rate or the shape and size of the pores of the support pad.

As described above, the weight average molecular weight of the polyester polyol included in each of the first polyurethane resin and the second polyurethane resin may be the same or different. For example, when the first polyurethane resin and the second polyurethane resin are mixed, the polyester polyol included in each of the soft part of the first polyurethane resin and the soft part of the second polyurethane resin may be 1,000 to 4,000. It may have a weight average molecular weight of. Preferably, the average value (average of each weight average molecular weight value) of the weight average molecular weight of the polyester polyol contained in each of the soft portion of the first polyurethane resin and the soft portion of the second polyurethane resin is 1,200 to 2,400. Can be.

On the other hand, the polycarboxylic acid may include a dicarboxylic acid having 4 to 8 carbon atoms, preferably adipic acid (adipic acid).

The hard part of the first polyurethane resin and the second polyurethane resin may include a residue of a polyisocyanate compound and a residue of a chain extender. The polyurethane resin may comprise 20 to 32% by weight, preferably 21 to 30% by weight of the residue of the polyisocyanate compound.

As described above, the content of the residue of the polyisocyanate compound included in the hard part of each of the first polyurethane resin and the second polyurethane resin may be different. For example, when the first polyurethane resin and the second polyurethane resin are mixed, the content of the residue of the polyisocyanate compound included in the hard part of the first polyurethane resin may be 20 to 25% by weight. The content of the residue of the polyisocyanate compound included in the hard part of the second polyurethane resin may be 25 to 32% by weight. Preferably, the average value of the content of the residues of the polyisocyanate compound included in the hard part of each of the first polyurethane resin and the second polyurethane resin may be 23 to 30% by weight. .

Residues of the polyisocyanate compounds are those that affect the modulus properties of the support pads produced. If the content of the portion derived from the polyisocyanate compound in the polyurethane resin is too small, the hard portion content of the polyurethane support pad may be too small, or the pad to be manufactured may not have sufficient hardness or thickness, the inside of the pad The pores may not be sufficiently formed or the shape of the pores formed may not be appropriate in size. In addition, when the content of the portion derived from the polyisocyanate compound in the polyurethane resin is too large, the hardness of the support pad to be produced may be excessively large or its compression rate or compression recovery rate may be greatly reduced.

The polyisocyanate compound means a compound having a plurality of isocyanate groups. Such polyisocyanate-based compounds may be polyisocyanates containing aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic functional groups, and may be represented by the formula Q (NCO) n. In this case, n is an integer of 2 to 4, Q may be an aliphatic, alicyclic, aromatic or araliphatic hydrocarbon functional group containing 2 to 18, preferably 6 to 10 C atoms. Specific examples of such polyisocyanate compounds 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-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, perhydro-4,4'-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, dimeryl diisocyanate (DDI) , 4,4'-Stilbene Diisocy Anate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate (TODI), toluene 2,4-diisocyanate, toluene 2,6-diisocyanate (TDI), diphenylmethane-2,4 '-Diisocyanate (MDI), 2,2'-diphenylmethane diisocyanate (MDI), diphenylmethane-4,4'-diisocyanate (MDI), naphthylene-1,5-isocyanate (NDI) or these And mixtures of two or more thereof.

The chain extender may comprise ethylene glycol and 1,4-butanediol, preferably ethylene glycol and 1,4-butanediol in a molar ratio of 1: 9 to 9: 1, more preferably 5: 5 to It may be included in a molar ratio of 9: 1. When ethylene glycol and 1,4-butanediol are used as a chain extender, the polyurethane resin and the support pad using the polyurethane resin can have an appropriate density or hardness, And the compressibility, elastic modulus, density and hardness required in the final product can be secured.

Each of the first polyurethane resin and the second polyurethane resin may have a weight average molecular weight of 100,000 to 900,000, preferably 200,000 to 600,000. The weight average molecular weight of the polyurethane resin may be based on a solid level of 30%. When using a polyurethane resin having a molecular weight in the above range, a plurality of pores can be formed in a uniform size and uniform distribution.

Meanwhile, in the process of preparing the support pad using the resin composition, it is preferable to use a solvent having a high boiling point. Specifically, the polyurethane resin composition may include dimethylformamide (DMF), methyl ethyl ketone (MEK), or these. It may comprise an organic solvent comprising a mixture of, preferably may include dimethylformamide. As such, the organic solvent including dimethylformamide (DMF), methyl ethyl ketone (MEK), or a mixture thereof may have a relatively high boiling point to maintain the physical properties of the polyurethane resin solid. In addition, the organic solvent has a high hydrophilicity, so that it can be easily replaced with an aqueous solution during the solidification process of the pad manufacturing process, thereby allowing long and large pores to be uniformly formed inside the support pad.

 Such an organic solvent may be included in an amount of 100 to 600 parts by weight based on 100 parts by weight of the first polyurethane resin and the second polyurethane resin.

The polyurethane resin composition may form a polyurethane support pad having pores therein through a solidification process, which is formed by phase separation of the polyurethane resin, water, and an organic solvent. Specifically, when the polyurethane resin dissolved in an organic solvent including the dimethylformamide (DMF), methyl ethyl ketone (MEK), or a mixture thereof is immersed in a coagulation bath filled with a certain aqueous solution, the polyurethane resin and the organic The solvent is phase-separated, and the organic solvent in the phase-separated state forms pores while being replaced with an aqueous solution or water. Thus, by removing the organic solvent and the like remaining through the washing and drying process after the pores are formed, a polyurethane resin pad that can be used to manufacture the support pad of the polishing apparatus can be produced.

On the other hand, the polyurethane resin composition may comprise a surfactant, the surfactant comprises a nonionic surfactant, anionic surfactant or mixtures thereof known to be used in the polyurethane resin.

The anionic surfactants allow the water to penetrate uniformly over the entire area of the composition to be solidified and prevent the phase separation of the polyurethane resin, water, and the organic solvent from being concentrated in a certain portion, thereby allowing pores inside the support pad. This makes it possible to form very uniformly. Such anionic surfactant may include 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the first polyurethane resin and the second polyurethane resin. If the content of the anionic surfactant is too small, the pores may be formed too small or the form of the pores may not be long. If the content is too large, the pores may be formed too large or the distribution of pores may not be uniform. Examples of such anionic surfactants include succinic acid, alkyl benzene sulfonic acids having 9 to 15 carbon atoms or salts thereof.

In addition, the nonionic surfactant may increase the solidification rate of the polyurethane resin composition or make the pore shape uniform. Such a nonionic surfactant may be included in an amount of 0.1 to 10, preferably 0.5 to 5 parts by weight based on 100 parts by weight of the sum of the first polyurethane resin and the second polyurethane resin. If the content of the nonionic surfactant is high, the pore shape may become uneven, and if it is too low, the solidification rate may be too small. Examples of such nonionic surfactants include silicone-based polymers, silicone oils, glycerol-based polymers, or hydrocarbon-based polymers.

The polyurethane resin composition may further include a silicone-based polymer in order to increase the adsorption force of the support pad or to make the surface of the pad flat. The polyurethane resin composition may further include at least one additive selected from the group consisting of a water repellent, a filler, a water repellent, a pore size regulator, and a pigment.

On the other hand, in the synthesis of the polyurethane resin, a constant catalyst can be selectively used in the reaction between the polyester polyol, the chain extender and the polyisocyanate compound described above, for example, an amine catalyst, an organic titanium compound, an organic tin compound. System catalysts or mixtures thereof. The amount of catalyst used may be 0.01wt% to 5wt% of the total polyurethane resin. Preferred examples of the catalyst include an organic tin compound catalyst, and specifically, a carboxylic acid such as tin (II) acetate, tin (II) octoate, tin (II) ethylhexate or tin (II) laurate Tin (II) salts and tin (IV) compounds such as dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate or dioctyltin diacetate Can be mentioned.

Meanwhile, according to another embodiment of the present invention, a polyurethane support pad including a wet coagulated product of the polyurethane resin composition may be provided.

As described above, the polyurethane adsorption pad may include two or more polyurethane resins having different structures from each other, for example, the first polyurethane resin and the second polyurethane resin described above, and thus a single polyurethane Better effects can be achieved compared to adsorption pads containing resins.

In addition, the polyurethane adsorption pad not only includes two or more polyurethane resins having different structures from each other, but also controls specific components and ratios of the hard and soft segments of each polyurethane resin to a specific range. It can have a better effect than the previously known adsorption pads. Specifically, the polyurethane adsorption pad has long and large pores uniformly formed therein, and may exhibit excellent compression ratio and high compression recovery ratio, and may be adsorbed on a polishing process such as a substrate or glass used in a semiconductor device or a display device. It can be used as a pad to minimize surface defects, roughness and waviness.

In addition, the polyurethane support pad prepared from the polyurethane resin composition may have a long and large pores uniformly formed therein to have a low hardness, excellent extrusion rate and high extrusion elastic modulus. In addition, since the polyurethane support pad has long and large pores uniformly formed therein, the air generated between the film and the polishing target film can be easily transferred to the inside and uniformly dispersed throughout the entire area. Minimize defects that may occur during

The polyurethane support pad may be formed by solidifying the polyurethane resin composition. Specifically, the polyurethane support pad to form the polyurethane resin composition; Forming or coating the polyurea resin composition on a predetermined substrate or frame; Solidifying the coating layer; And it can be prepared through the step of washing, dehydrating and drying the coagulum of the composition.

In the step of solidifying the coating layer, the substrate or frame on which the coating layer is formed is filled with a dimethylformamide (DMF) aqueous solution, methyl ethyl ketone (MEK) aqueous solution, or a mixture thereof, for example, 1 to 20% aqueous DMF solution. This can be done by putting in a filled coagulation bath. In the solidification process, as the organic solvent (eg, dimethylformamide or methyl ethyl ketone) inside the polyurethane resin is replaced with water, the polyurethane resin may be gradually solidified and thus a plurality of pores may be formed. By adjusting the concentration of the organic solvent in the coagulation bath it is possible to control the coagulation time or the pore size in the support pad to be produced.

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 be manufactured using the specific polyurethane resin composition described above, and may have Asker C hardness of 20 to 25, preferably Asker C hardness of 21 to 23.

The polyurethane support pad can have a compression ratio of at least 35% and a compression modulus of at least 92%.

The polyurethane support pad may include pores having a longest diameter of 100 μm to 500 μm. The distance between adjacent outermost portions of the pores adjacent to each other may be 10 μm to 50 μm. In the polyurethane resin including the coagulum of the polyurethane resin composition, pores having a long elliptical similar shape may be uniformly distributed.

According to the present invention, long and large pores are uniformly contained therein, exhibit high compressibility and compression recovery rate, and can be used in polishing processes such as substrates or glass used in semiconductor devices or display devices to minimize surface defects, roughness and waviness. Support pads may be provided.

1 shows a cross-sectional optical micrograph of a support pad obtained from the polyurethane resin composition of Example 1. FIG.
FIG. 2 shows a cross-sectional optical micrograph of a support pad obtained from the polyurethane resin composition of Example 2. FIG.
3 shows a cross-sectional optical micrograph of a support pad obtained from the polyurethane resin composition of Example 3. FIG.
4 shows a cross-sectional optical micrograph of a support pad obtained from the polyurethane resin composition of Example 4. FIG.
5 shows a cross-sectional optical micrograph of a support pad obtained from the polyurethane resin composition of Comparative Example 1. FIG.
6 shows a cross-sectional optical micrograph of a support pad obtained from the polyurethane resin composition of Comparative Example 2. FIG.

Hereinafter, the operation and effects of the invention will be described in more detail with reference to specific examples of the invention. It is to be understood, however, that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention.

< Example  And Comparative example : Polyurethane resin and glass polishing for display Of support pad  Manufacturing>

[ Example ]

1. Preparation of Polyurethane Resin

Adipic acid, ethylene glycol and 1,4-butanediol were reacted at a temperature of 200 ° C., under reduced pressure of 500 to 760 mmHg, and under vacuum atmospheric conditions to synthesize polyester polyols. At this time, the molar ratio of ethylene glycol: 1,4-butanediol and the weight average molecular weight of the synthesized polyester polyol were as shown in Table 2 below.

At atmospheric pressure (1 atm) and at room temperature (RT), in the presence of dibutyltin dilaurate, the synthesized polyester polyol, chain extender (ethylene glycol) and DMF were placed in a reactor and heated to 80 ° C. When the temperature was raised to the reaction temperature of 80 ℃, diphenylmethane diisocyanate (MDI) was added and stirred for 2 hours to adjust the viscosity of the reaction solution to prepare a polyurethane resin.

2. Preparation of Polyurethane Resin Composition and Support Pad

The two polyurethane resins, the DMF solution, and the additives prepared in the amounts shown in Table 1 were mixed, stirred at high speed with a paint shaker for 10 minutes, and then centrifuged at 3000 rpm for 10 minutes to form a slurry. The resin composition was obtained.

After coating the obtained polyurethane resin composition to a thickness of 2.00mm on a PET film, the coagulation process was performed in a coagulation bath of 4 Brix% concentration. Thereafter, the obtained coagulum was washed with water, dehydrated and dried to prepare a polyurethane support pad.

Specific coagulation, washing and dehydration conditions were as follows.

* Coating process set

     -Solidification time (min) / temp. (℃): 30 ~ 35/35 ~ 37

     -Washing time (time) / temp. (℃): 12/65

-coating dam thickness: 2mm

 [ Comparative example ]

1. Preparation of Polyurethane Resin

Adipic acid, ethylene glycol and 1,4-butanediol were reacted at a temperature of 200 ° C., under reduced pressure of 500 to 760 mmHg, and under vacuum atmospheric conditions to synthesize polyester polyols. At this time, the molar ratio of ethylene glycol: 1,4-butanediol and the weight average molecular weight of the synthesized polyester polyol are the PU2 resin (Comparative Example 1) and the PU2 resin (Comparative Example 2) of Example 3 in Table 2 below. It was like

At atmospheric pressure (1 atm) and at room temperature (RT), in the presence of dibutyltin dilaurate, the synthesized polyester polyol, chain extender (ethylene glycol) and DMF were placed in a reactor and heated to 80 ° C. When the temperature was raised to the reaction temperature of 80 ℃, diphenylmethane diisocyanate (MDI) was added and stirred for 2 hours to adjust the viscosity of the reaction solution to prepare a polyurethane resin.

2. Preparation of Polyurethane Resin Composition and Support Pad

A polyurethane support pad was prepared in the same manner as in Example, except that the polyurethane resin was used alone.

Additive dosage PU
Suzy SD
-7 SD
-11 8I 607 CB DMF Water repellent agent
PS FAT
-7 DBSA PEG
200 Mass (g) 50 0.75 2 0.25 0.15 3.5 30 One 0.75 0.25 One

1) SD-7, SD-11: Nonionic Surfactant (Pentachem)

2) 8I, 607, CB: additive

FAT-7: Filler (Pentachem)

4) DBSA: para-dodecylbenzenesulfonic acid

5) PEG200: polyethylene glycol with a weight average molecular weight of 200

The composition of the polyurethane resin of the Example and the measurement result of the compression rate / compression recovery rate of the support pad Example division Polyol MDI Content
(%) Mixing ratio Compression ratio
(%) Compression Recovery Rate
(%) BD: EG Molecular Weight One PU resin 1 5: 5 2000 21 0.5 40 92 PU resin 2 5: 5 2000 30 0.5 2 PU resin 1 8: 2 2000 30 0.5 40 92 PU resin 2 5: 5 2000 30 0.5 3 PU resin 1 5: 5 1000 21 0.5 40 92 PU resin 2 5: 5 2000 30 0.5 4 PU resin 1 5: 5 2000 21 0.5 40 92 PU resin 2 5: 5 2000 25 0.5

As shown in Table 2, when two kinds of polyurethane resins prepared using a polyol containing 1,4-butanediol and ethylene glycol in a specific ratio and a polyisocyanate compound in a specific content are used, a high compression ratio and a compression recovery rate For example, it has been confirmed that a support pad having a compression ratio of 35% or more and a compression recovery rate of 92% or more can be manufactured.

And, as shown in Figures 1 to 4, it was confirmed that the pores having the longest diameter of 100 ㎛ to 500 ㎛ in the polyurethane support pad of the embodiment was uniformly distributed.

On the contrary, as shown in FIGS. 5 and 6, pores formed in the polyurethane support pad of the comparative example are shorter in length or smaller in number than the pores shown in the examples, and also uniform in their distribution. It was confirmed that the fall compared to the example. That is, it was confirmed that the polyurethane resin of this comparative example is difficult to secure the quality that can be applied to the actual polishing process.

Claims (17)

Soft moieties comprising residues of polyols and residues of polycarboxylic acids comprising 1,4-butane diol and ethylene glycol in a molar ratio of 8: 2 to 2: 8, residues of polyisocyanate compounds and residues of chain extenders A first polyurethane resin comprising a hard portion including;
A soft portion having a composition different from that of the first polyurethane resin and comprising a residue of a polyol and a residue of a polycarboxylic acid containing 1,4-butane diol and ethylene glycol in a molar ratio of 8: 2 to 2: 8, A second polyurethane resin comprising a hard part including a residue of a polyisocyanate compound and a residue of a chain extender;
An organic solvent comprising at least one member selected from the group consisting of dimethylformamide (DMF) and methyl ethyl ketone (MEK); And surfactants,
The polyurethane resin composition, wherein each of the first polyurethane resin and the second polyurethane resin comprises 20 to 32 wt% of the residue of the polyisocyanate compound.
The method of claim 1,
Polyurethane resin composition having a different content of the residues of the polyisocyanate compound contained in each of the first polyurethane resin and the second polyurethane resin.
The method of claim 1,
A polyurethane resin composition having a molar ratio of 1,4-butane diol and ethylene glycol, wherein the residue of the polyol of the first polyurethane resin and the residue of the polyol of the second polyurethane resin are different from each other.
The method of claim 1,
The average value of the molar ratio of 1,4-butane diol: ethylene glycol in the first polyurethane resin and the molar ratio of 1,4-butane diol: ethylene glycol in the second polyurethane resin is 7: 3 to 3: 7. , Polyurethane resin composition.
The method of claim 1,
A polyurethane resin composition comprising a residue of a polyester polyol having a weight average molecular weight of 1000 to 4,000 of the soft portion of each of the first polyurethane resin and the second polyurethane resin.
The method of claim 5,
The polyurethane resin composition which differs in the weight average molecular weight of the polyester polyol contained in each of the said 1st polyurethane resin and the 2nd polyurethane resin.
The method of claim 1,
The polycarboxylic acid is a polyurethane resin composition containing a dicarboxylic acid having 4 to 8 carbon atoms.
The method of claim 1,
The polyisocyanate compound is 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-isocyanatomethyl-cyclohexane, 2,4-hexahydro Toluene diisocyanate, 2,6-hexahydrotoluene diisocyanate, hexahydro-1,3-phenylene diisocyanate, hexahydro-1,4-phenylene diisocyanate, perhydro-2,4'-diphenylmethane di Isocyanate, perhydro-4,4'-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, dimeryl diisocyanate (DDI), 4,4'- Stilbene diisocyanate, 3,3'-dimethyl-4,4'-bipe Nylene diisocyanate (TODI), toluene 2,4-diisocyanate, toluene 2,6-diisocyanate (TDI), diphenylmethane-2,4'- diisocyanate (MDI), 2,2'-diphenylmethane di Polyurethane resin composition comprising at least one member selected from the group consisting of isocyanate (MDI), diphenylmethane-4,4'-diisocyanate (MDI) and naphthylene-1,5-isocyanate (NDI).
The method of claim 1,
The chain extender is a polyurethane resin composition comprising ethylene glycol and 1,4-butanediol.
The method of claim 1,
Polyurethane resin composition wherein each of the first polyurethane resin and the second polyurethane resin has a weight average molecular weight of 50,000 to 500,000.
The method of claim 1,
Polyurethane resin composition wherein the surfactant comprises an anionic surfactant or a nonionic surfactant.
The method of claim 1,
Polyurethane resin composition further comprising at least one additive selected from the group consisting of fillers, water repellents, pore size regulators and pigments.
The method of claim 1,
Polyurethane resin composition for producing a support pad of the polishing apparatus.
A polyurethane support pad comprising the wet coagulum of the polyurethane resin composition of claim 1.
15. The method of claim 14,
Polyurethane support pads having a compression ratio of at least 30% and a compression modulus of at least 92%.
15. The method of claim 14,
A polyurethane support pad comprising pores having a longest diameter of 100 μm to 500 μm.
15. The method of claim 14,
A polyurethane support pad having a distance of 10 μm to 50 μm between adjacent outermost portions of the pores adjacent to each other among the pores.

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