Composition for polishing pads, method for producing the composition, and polyurethane resin composition for polishing pads using the composition.

Abstract

To provide a polyurethane resin composition for polishing pads comprising an isocyanate group-terminated prepolymer and a polyisocyanate, a method for producing the composition, and the polyurethane resin composition for polishing pads, which can be obtained that exhibits less change in physical properties over a wide range of temperature changes than conventional compositions. [Solution] A polishing pad composition comprising an isocyanate-terminated prepolymer and polyisocyanate, wherein the ratio of NCO mass derived from the isocyanate-terminated prepolymer to the NCO mass derived from the polyisocyanate in the polishing pad composition is within a predetermined range. By using this polishing pad composition to synthesize a polyurethane resin composition for polishing pads, the loss tangent tanδ in the temperature range of -60°C to 120°C is measured, and even when the maximum value of tanδ in the range is divided by the average value of tanδ in the range, the result is kept below 200%.

Description

Technical Field

[0001] The present invention relates to a composition for a polishing pad comprising an isocyanate group-terminated prepolymer and a polyisocyanate, a method for producing the composition, and a polyurethane resin composition for a polishing pad using the composition.

Background Art

[0002] A polyurethane resin composition formed by reacting an isocyanate group-terminated prepolymer synthesized from a polyol such as a polyalkylene polyol and a polyisocyanate with a chain extender such as a polyamine to be cured is used in various applications. For example, in a chemical mechanical polishing (CMP) technique where a polishing pad is rotated at high speed and a polishing liquid containing abrasive grains such as silica, a corrosion inhibitor, a surfactant, etc. is introduced between the polishing pad and the workpiece to modify the surface of the workpiece while increasing the mechanical polishing effect of the abrasive grains, a polyurethane resin composition is used as the polishing pad for this technique. The CMP technique is used for polishing magnetic substrates, optical substrates, semiconductor substrates, etc. In particular, for semiconductor substrates, flatness of each layer is important for accurately forming multilayer wirings, and thus it is an indispensable technique.

[0003] On the other hand, the physical properties of polyurethane resin compositions change significantly depending on temperature conditions, which can have adverse effects. In the case of polishing pads mentioned above, various temperature conditions and temperature changes during polishing due to frictional heat generated by the accumulation of polishing debris are considered. It is known that temperature changes alter the balance of hardness and viscoelasticity, resulting in a decrease in flatness after polishing, without exhibiting step performance or defect performance (Patent Documents 1-3). In particular, in the semiconductor field in recent years, with the miniaturization of wiring widths, higher precision polishing is required, making the decrease in flatness an even greater problem. In addition, since polyurethane resin compositions generally exhibit a glass transition temperature in the temperature range of -100 to 200°C, brittleness occurs at low temperatures and softening occurs at high temperatures, and shrinkage rate, tensile strength, hardness, etc. change, making application design difficult (Patent Documents 4-7). As described above, polyurethane resin compositions with little change in physical properties due to a wide range of temperature changes are also in demand in a wide range of fields, and their realization has high industrial value. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2016-196067 [Patent Document 2] Japanese Patent Publication No. 2008-149458 [Patent Document 3] Japanese Patent Publication No. 2020-157415 [Patent Document 4] Japanese Patent Publication No. 2002-284834 [Patent Document 5] Japanese Patent Publication No. 2007-2118 [Patent Document 6] Japanese Patent Publication No. 2002-265550 [Patent Document 7] Special Publication No. 6-500622 [Overview of the project] [Problems that the invention aims to solve]

[0005] Therefore, the present invention aims to provide a polyurethane resin composition for polishing pads comprising an isocyanate group-terminated prepolymer and polyisocyanate, a method for producing the composition, and a polyurethane resin composition for polishing pads that can be obtained that exhibits less change in physical properties over a wide range of temperature changes than conventional polyurethane resin compositions. [Means for solving the problem]

[0006] This invention was obtained as a result of diligently studying the aforementioned problems, and its gist is as follows.

[0007] [1] A polishing pad composition comprising an isocyanate-terminated prepolymer and a polyisocyanate, wherein the ratio of the NCO mass derived from the isocyanate-terminated prepolymer to the NCO mass derived from the polyisocyanate in the composition is 80:20 to 15:85.

[0008] [2] The composition according to [1], wherein the polyisocyanate is one or a mixture selected from aromatic polyisocyanates, aliphatic polyisocyanates, and aromatic alicyclic polyisocyanates.

[0009] [3] The composition according to [1], wherein the mass concentration % of the composition is 6 to 11%.

[0010] [4] The composition according to [1], wherein the polyisocyanate used in the isocyanate-terminated prepolymer is one or a mixture selected from aromatic polyisocyanates, aliphatic polyisocyanates, and aromatic alicyclic polyisocyanates.

[0011] [5] The composition according to [1], wherein the polyol used in the isocyanate-terminated prepolymer is a polyalkylene glycol.

[0012] [6] The composition according to [1], wherein the polyol used in the isocyanate-terminated prepolymer is one or a mixture selected from polytetramethylene ether glycol or polypropylene glycol and copolymers thereof.

[0013] A polyurethane resin composition for polishing pads comprising the composition described in any one of items [7][1] to [6] and a chain extender.

[0014] [8] The polyurethane resin composition according to [7], wherein the chain extender is a polyamine.

[0015] [9] The polyurethane resin composition according to [7], wherein the chain extender is one or a mixture selected from 4,4'-methylenebis(2-chloroaniline) and its modified forms.

[0016]

[10] A polyurethane resin composition according to any one of [7] to [9], wherein the initial force amplitude is 2000 mN, the strain amplitude is 10 μm, the measurement frequency is 10 Hz, and the maximum value of the loss tangent tanδ in the temperature range from -60°C to 120°C in tensile mode is 200% or less of the average value of tanδ in the temperature range.

[0017]

[11] A polyurethane resin composition according to any one of items [7] to [9], wherein the hardness is 50 or higher.

[0018]

[12] A method for producing a polishing pad composition comprising an isocyanate-terminated prepolymer and a polyisocyanate, wherein the method involves synthesizing the isocyanate-terminated prepolymer and then adding the polyisocyanate. [Effects of the Invention]

[0019] According to the present invention, it is possible to obtain a polyurethane resin composition for a polishing pad having less physical property changes against a wide range of temperature changes than a conventional polyurethane resin composition, and to provide a composition for a polishing pad composed of an isocyanate group-terminated prepolymer and a polyisocyanate, a method for producing the composition, and the polyurethane resin composition for a polishing pad.

Brief Description of Drawings

[0020] [Figure 1] It is a diagram explaining the maximum value, average value, and maximum value / average value of the loss tangent tanδ. [Figure 2] It is a diagram explaining that by changing the ratio (NCO mass ratio) of the NCO mass derived from the isocyanate group-terminated prepolymer to the NCO mass derived from the polyisocyanate, the maximum value / average value of the loss tangent tanδ changes from Examples and Comparative Examples. [Figure 3] It is a diagram showing the actually measured values of the loss tangent tanδ in the temperature range of -60 to 120 ° C for Comparative Example 1 and Examples 1 to 5. [Figure 4] It is a diagram showing the actually measured values of the loss tangent tanδ in the temperature range of -60 to 120 ° C for Examples 6 to 10.

Modes for Carrying Out the Invention

[0021] Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following contents and can be variously modified and implemented within the scope of the gist.

[0022] <Isocyanate group-terminated prepolymer> The isocyanate group-terminated prepolymer is a reaction product of a polyol and a polyisocyanate.

[0023] The polyol component is not particularly limited and includes diols, polyols, polyoldiols, and copolymers thereof, as well as mixtures thereof. Preferably, it includes polyether polyols, polyester polyols, polylactone polyols, polycarbonate polyols, polydiene polyols, polymer polyols, polyacrylic polyols, natural oil-based polyols and their modified products, as well as copolymers thereof, as well as mixtures thereof. More preferably, it includes polytetramethylene ether glycol (also known as PTMEG), polypropylene ether glycol (also known as PPG), and copolymers thereof, as well as mixtures thereof.

[0024] The number-average molecular weight of the polyol components is not particularly limited and can be selected from a variety of options, and their molecular weight distribution is not a concern. Preferably, it is in the range of 500 to 5000, more preferably in the range of 600 to 4000, and even more preferably in the range of 1000 to 3000.

[0025] The polyisocyanate components are not particularly limited and include aromatic polyisocyanates, aliphatic polyisocyanates, aromatic aliphatic polyisocyanates, etc., and mixtures thereof may or may not be present. The aromatic polyisocyanates are not particularly limited and include 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (also known as MDI), polymethylene polyphenyl polyisocyanate (also called polymeric MDI, modified MDI, or crude MDI), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate (also known as TDI), etc., and mixtures thereof may or may not be present. Aliphatic polyisocyanates are not particularly limited and include hexamethylene diisocyanate (also known as HDI), 4,4'-methylenebiscyclohexyl isocyanate, isophorone diisocyanate (also known as IPDI), and mixtures thereof, and may or may not be denatured. Aromatic aliphatic polyisocyanates mean aliphatic isocyanates having one or more aromatic rings in the molecule and are not particularly limited, including 1,4-xylylene diisocyanate, 1,3-xylylene diisocyanate (also known as XDI), 1,2-xylylene diisocyanate, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate (also known as TMXDI), 1,2-tetramethylxylylene diisocyanate, and mixtures thereof, and may or may not be denatured. Preferably, the material includes 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and isophorone diisocyanate, or a mixture thereof, and may or may not be denatured.

[0026] The upper limit temperature during the reaction between the polyol and the polyisocyanate is not particularly limited, but is preferably 110°C or lower, more preferably 100°C or lower, and even more preferably 90°C or lower. The lower limit temperature during the reaction is not particularly limited, but is preferably 30°C or higher, more preferably 40°C or higher, and even more preferably 50°C or higher.

[0027] A polymerization catalyst may be used as needed during the reaction between polyisocyanate and polyol. The polymerization catalyst is not particularly limited and includes organic acids, metal salts of organic acids, acid anhydrides, amine compounds, and mixtures thereof. Examples of organic acids include propionic acid, 2-methylpentanoic acid, isononanoic acid, 2-ethylhexanoic acid, neodecanoic acid, naphthenic acid, oleic acid, linoleic acid, linolenic acid, and mixtures thereof. Examples of organic acid metal salts include zinc salts (e.g., K-KAT XK634 (manufactured by Kusumoto Chemical Co., Ltd.)), bismuth salts (e.g., K-KAT XK628 (manufactured by Kusumoto Chemical Co., Ltd.)), magnesium salts (e.g., magnesium 2-ethylhexanoate (manufactured by Fujifilm Wako Pharmaceutical Co., Ltd.)), zirconium salts (e.g., K-KAT 6212 (manufactured by Kusumoto Chemical Co., Ltd.)), calcium salts (e.g., Nikka Octic Calcium (manufactured by Nippon Chemical Industrial Co., Ltd.)), barium salts (e.g., barium 2-ethylhexanoate (manufactured by Fujifilm Wako Pharmaceutical Co., Ltd.)), copper salts (e.g., copper 2-ethylhexanoate (manufactured by Fujifilm Wako Pharmaceutical Co., Ltd.)), and mixtures thereof. Examples of acid anhydrides include phthalic anhydride, hexahydrophthalic anhydride, methyl-hexahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, and mixtures thereof. Examples of amines include triethylenediamine, 2-methyltriethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-pentamethyldiethylenetriamine, trimethylaminoethylpiperazine, bis-(dimethylaminoethyl) ether, N,N',N''-tris(dialkylaminoalkyl)-s-hexahydrotriazine, N,N-dimethylaminoethylmorpholine, dimethylaminopropylimidazole, hexamethyltriethylenetetramine, hexamethyltripropylenetetramine, N,N,N-tris(3-dimethylaminopropyl)amine, and mixtures thereof. By using a polymerization catalyst, the reaction rate can be increased and the reaction temperature can be lowered.

[0028] The isocyanate-terminated prepolymer may further contain viscosity modifiers such as plasticizers and solvents for viscosity adjustment. The plasticizer is not particularly limited and includes aliphatic dibasic acid esters (e.g., diisononyl adipate (DINA), bis(2-ethylhexyl) adipate (DOA), etc.), cyclohexane derivatives (e.g., diisononyl 1,2-cyclohexanedicarboxylate (DHIN), bis(2-ethylhexyl) 1,2-cyclohexanedicarboxylate (DHEH), etc.), phosphate esters, trimellitic acid esters (e.g., tri(2-ethylhexyl) trimellitic acid (TOTM)), sebacate acid esters, epoxy fatty acid esters, glycol esters, animal oil-based fatty acid esters, petroleum / mineral oil-based plasticizers, alkylene oxide polymerization-based plasticizers, etc., and mixtures thereof. Furthermore, from the viewpoint of improving finish and durability, various additives such as flame retardants, foam stabilizers, foaming agents, defoaming agents, polymer particles, inorganic fillers, film-forming stabilizers, and surfactants may be included.

[0029] The NCO mass concentration % of the isocyanate group-terminated prepolymer alone is not particularly limited, but the preferred minimum value is 1.0% by mass, more preferably 2.0% by mass, and even more preferably 4.0% by mass. The preferred maximum value is 10% by mass, more preferably 8.0% by mass, and even more preferably 7.0% by mass.

[0030] <Polyisocyanate> The polyisocyanate component is not particularly limited, similar to that used in isocyanate group-terminated prepolymers, and includes aromatic polyisocyanates, aliphatic polyisocyanates, aromatic aliphatic polyisocyanates, etc., and may or may not be modified. The aromatic polyisocyanate is not particularly limited, and includes 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (also known as MDI), polymethylene polyphenyl polyisocyanate (also called polymeric MDI, modified MDI, or crude MDI), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate (also known as TDI), etc., and may or may not be modified. Aliphatic polyisocyanates are not particularly limited and include hexamethylene diisocyanate (also known as HDI), 4,4'-methylenebiscyclohexyl isocyanate, isophorone diisocyanate (also known as IPDI), and mixtures thereof, and may or may not be denatured. Aromatic aliphatic polyisocyanates mean aliphatic isocyanates having one or more aromatic rings in the molecule and are not particularly limited, including 1,4-xylylene diisocyanate, 1,3-xylylene diisocyanate (also known as XDI), 1,2-xylylene diisocyanate, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate (also known as TMXDI), 1,2-tetramethylxylylene diisocyanate, and mixtures thereof, and may or may not be denatured. Preferably, the materials include 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and isophorone diisocyanate, or mixtures thereof, and the materials may or may not be modified.

[0031] Polyisocyanates may further contain plasticizers, solvents, etc., as viscosity modifiers for viscosity adjustment, etc. Examples of plasticizers are not particularly limited and include aliphatic dibasic acid esters (e.g., diisononyl adipate (DINA), bis(2-ethylhexyl) adipate (DOA), etc.), cyclohexane derivatives (e.g., diisononyl 1,2-cyclohexanedicarboxylate (DHIN), bis(2-ethylhexyl) 1,2-cyclohexanedicarboxylate (DHEH), etc.), phosphate esters, trimellitic acid esters (e.g., tri(2-ethylhexyl) trimellitic acid (TOTM)), sebacate acid esters, epoxy fatty acid esters, glycol esters, animal oil-based fatty acid esters, petroleum / mineral oil-based plasticizers, alkylene oxide polymerization-based plasticizers, etc., and mixtures thereof. Furthermore, from the viewpoint of improving finish and durability, various additives such as flame retardants, foam stabilizers, foaming agents, defoaming agents, polymer particles, inorganic fillers, film-forming stabilizers, and surfactants may be included.

[0032] <Composition for polishing pads consisting of an isocyanate-terminated prepolymer and polyisocyanate> The polishing pad composition, comprising an isocyanate-terminated prepolymer and polyisocyanate, is a mixture of the isocyanate-terminated prepolymer and polyisocyanate. In this case, adding the polyisocyanate after the synthesis of the isocyanate-terminated prepolymer facilitates the adjustment of the NCO mass concentration %. The NCO mass concentration % of the polishing pad composition is not particularly limited, but a preferred minimum value is 6.0% by mass, more preferably 7.0% by mass, and even more preferably 8.0% by mass. A preferred maximum value is 11.0% by mass, more preferably 10.0% by mass, and even more preferably 9.0% by mass.

[0033] As a mixed component, polyisocyanates used in isocyanate-terminated prepolymers can be combined in various ways, regardless of whether they are of the same or different type.

[0034] The mixing ratio is adjusted by the ratio of the NCO mass derived from the isocyanate group-terminated prepolymer to the NCO mass derived from the polyisocyanate (NCO mass ratio). When the NCO mass derived from the isocyanate group-terminated prepolymer increases, the change in physical properties with respect to temperature change becomes larger. When the NCO mass derived from the polyisocyanate increases, it becomes difficult to adjust the hardness and the reaction time with the chain extender. The NCO mass ratio is preferably 80:20 to 15:85, more preferably 70:30 to 20:80, and even more preferably 60:40 to 25:75.

[0035] <NCO mass> The NCO mass refers to the NCO mass concentration % of the isocyanate group-terminated prepolymer or polyisocyanate multiplied by the mass of the isocyanate group-terminated prepolymer or polyisocyanate contained in the polishing pad composition.

[0036] The mixing temperature is not particularly limited and various selections are possible. The preferable upper limit is 100 °C, more preferably 90 °C, and even more preferably 80 °C. The preferable lower limit is 20 °C, more preferably 30 °C, and even more preferably 40 °C.

[0037] During mixing, the mixture may further contain a plasticizer, solvent, etc., as a viscosity modifier for viscosity adjustment, etc. The plasticizer is not particularly limited and includes aliphatic dibasic acid esters (e.g., diisononyl adipate (DINA), bis(2-ethylhexyl) adipate (DOA), etc.), cyclohexane derivatives (e.g., diisononyl 1,2-cyclohexanedicarboxylate (DHIN), bis(2-ethylhexyl) 1,2-cyclohexanedicarboxylate (DHEH), etc.), phosphate esters, trimellitic acid esters (e.g., tri(2-ethylhexyl) trimellitic acid (TOTM)), sebacate acid esters, epoxy fatty acid esters, glycol esters, animal oil-based fatty acid esters, petroleum / mineral oil-based plasticizers, alkylene oxide polymerization-based plasticizers, etc., and mixtures thereof. Furthermore, from the viewpoint of improving finish and durability, various additives such as flame retardants, foam stabilizers, foaming agents, defoaming agents, polymer particles, inorganic fillers, film-forming stabilizers, and surfactants may be included.

[0038] <Chain extender> The chain extender is used to form a polyurethane resin composition by mixing it with a polishing pad composition consisting of an isocyanate group-terminated prepolymer and polyisocyanate, thereby curing the composition.

[0039] Chain extenders usable in the formation of polyurethane resin compositions are not particularly limited and include compounds having functional groups that can react with isocyanate groups such as primary amino groups (-NH2), secondary amino groups (-NH-), or hydroxyl groups (-OH), or water (H2O). These may have multiple types of functional groups in a single molecule, and mixtures thereof are also included. Compounds having amino groups are not particularly limited and include aromatic polyamines and aliphatic polyamines, and mixtures thereof are also included. Modification may or may not occur. Aromatic polyamines are not particularly limited, but include 4,4'-methylenebis(2-chloroaniline), diethyltoluenediamine (2,4-diethyltoluenediamine, 2,6-diethyltoluenediamine), polyalkylene ether polyol-p-aminobenzoate, polytetramethylene ether glycol aminobenzoate, 4,4'-bis(sec-butylamine)diphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane, and 3,3'-dimethyl-5,5 Examples include '-diethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetraisopropyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-5,5'-diisopropyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-5,5'-diisobutyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-5,5'-diisopropyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-5,5'-diisobutyl-4,4'-diaminodiphenylmethane, and mixtures thereof, and denaturation may or may not occur.The aliphatic polyamine is not particularly limited, and examples include N,N'-di-sec-butyl 4,4'-methylenebis(cyclohexylamine), norbornenediamine, N,N'-(dicyclohexylmethane 4,4'-diyl)-bisaspartic acid tetraethyl ester, triaminopropane, 2,2,4-trimethylhexamethylenediamine, 2-hydroxyethylethylenediamine, N,N'-(2-methylpentane-1,5-diyl)-bisaspartic acid tetraethyl ester, polyoxyalkyleneamine, polyetheramine, etc., and include mixtures thereof, and may or may not be modified. The compound having a hydroxy group is not particularly limited, and examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerin, trimethylolpropane, etc., and include mixtures thereof. Preferably it is a polyamine, more preferably an aromatic polyamine, and further preferably 4,4'-methylenebis(2-chloroaniline) and its modified products and mixtures thereof.

[0040] <Polyurethane resin composition> The polyurethane resin composition is obtained by curing the composition by mixing a composition for a polishing pad composed of an isocyanate group-terminated prepolymer and a polyisocyanate with a chain extender.

[0041] <R value> The mixing ratio is adjusted by the R value (NCO group / NH2, OH group, etc.) indicating the equivalent ratio of the NCO group in the composition for a polishing pad composed of an isocyanate group-terminated prepolymer and a polyisocyanate to the total equivalent of amino groups, hydroxy groups, etc. contained in the chain extender, and is not particularly limited. Preferably it is 0.8 to 1.5, more preferably 0.9 to 1.4, and further preferably 1.0 to 1.3.

[0042] When synthesizing polyurethane resin compositions, a polymerization catalyst may be used as needed, similar to the synthesis of isocyanate-terminated prepolymers. The polymerization catalyst is not particularly limited and includes organic acids, metal salts of organic acids, acid anhydrides, amine compounds, and mixtures thereof. Examples of organic acids include propionic acid, 2-methylpentanoic acid, isononanoic acid, 2-ethylhexanoic acid, neodecanoic acid, naphthenic acid, oleic acid, linoleic acid, linolenic acid, and mixtures thereof. Examples of organic acid metal salts include zinc salts (e.g., K-KAT XK634 (manufactured by Kusumoto Chemical Co., Ltd.)), bismuth salts (e.g., K-KAT XK628 (manufactured by Kusumoto Chemical Co., Ltd.)), magnesium salts (e.g., magnesium 2-ethylhexanoate (manufactured by Fujifilm Wako Pharmaceutical Co., Ltd.)), zirconium salts (e.g., K-KAT 6212 (manufactured by Kusumoto Chemical Co., Ltd.)), calcium salts (e.g., Nikka Octic Calcium (manufactured by Nippon Chemical Industrial Co., Ltd.)), barium salts (e.g., barium 2-ethylhexanoate (manufactured by Fujifilm Wako Pharmaceutical Co., Ltd.)), copper salts (e.g., copper 2-ethylhexanoate (manufactured by Fujifilm Wako Pharmaceutical Co., Ltd.)), and mixtures thereof. Examples of acid anhydrides include phthalic anhydride, hexahydrophthalic anhydride, methyl-hexahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, and mixtures thereof. Examples of amines include triethylenediamine, 2-methyltriethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-pentamethyldiethylenetriamine, trimethylaminoethylpiperazine, bis-(dimethylaminoethyl) ether, N,N',N''-tris(dialkylaminoalkyl)-s-hexahydrotriazine, N,N-dimethylaminoethylmorpholine, dimethylaminopropylimidazole, hexamethyltriethylenetetramine, hexamethyltripropylenetetramine, N,N,N-tris(3-dimethylaminopropyl)amine, and mixtures thereof. By using a polymerization catalyst, the reaction rate can be increased and the reaction temperature can be lowered.

[0043] When synthesizing polyurethane resin compositions, viscosity modifiers such as plasticizers and solvents may be further included to adjust viscosity. The plasticizers are not particularly limited and include aliphatic dibasic acid esters (e.g., diisononyl adipate (DINA), bis(2-ethylhexyl) adipate (DOA), etc.), cyclohexane derivatives (e.g., diisononyl 1,2-cyclohexanedicarboxylate (DHIN), bis(2-ethylhexyl) 1,2-cyclohexanedicarboxylate (DHEH), etc.), phosphate esters, trimellitic acid esters (e.g., tri(2-ethylhexyl) trimellitic acid (TOTM)), sebacate acid esters, epoxy fatty acid esters, glycol esters, animal oil-based fatty acid esters, petroleum / mineral oil-based plasticizers, alkylene oxide polymerization-based plasticizers, etc., and mixtures thereof. Furthermore, from the viewpoint of improving finish and durability, various additives such as flame retardants, foam stabilizers, foaming agents, defoaming agents, polymer particles, inorganic fillers, film-forming stabilizers, and surfactants may be included.

[0044] <Overview of Dynamic Viscoelasticity Test (DMA)> With an initial force amplitude of 2000 mN, a strain amplitude of 10 μm, and a measurement frequency of 10 Hz, E' and E'' were measured every 3 seconds in the tensile mode over a temperature range of -60°C to 120°C, and the loss tangent tаnδ was calculated.

[0045] <Loss tangent tanδ> The loss tangent tanδ is the loss modulus E'' (viscous component) relative to the storage modulus E' (elastic component). The storage modulus is a value expressed as a ratio of (minutes) and is an indicator of viscoelasticity under certain temperature conditions. The storage modulus is a measure of the energy stored and fully recovered per period when a sinusoidal stress is applied, while the loss modulus refers to the magnitude of the stress component that is π / 2 in phase ahead of the strain when a sinusoidal strain of the characteristic frequency is applied. E' and E'' can be measured by dynamic viscoelasticity testing (DMA).

[0046] <Maximum value of loss tangent tanδ> The highest value of the loss tangent tanδ refers to the highest value among the loss tangent tanδ measured every 3 seconds in the temperature range of -60°C to 120°C (Figure 1).

[0047] <Mean value of loss tangent tanδ> The average value of the loss tangent tanδ refers to the average value of the loss tangent tanδ measured every 3 seconds in the temperature range of -60°C to 120°C (Figure 1).

[0048] <Maximum value of loss tangent tanδ / Average value> The ratio of the maximum value of the loss tangent tanδ to the average value of the loss tangent tanδ refers to the ratio of the maximum value of the loss tangent tanδ to the average value of the loss tangent tanδ. A larger number indicates greater variability with respect to temperature changes, while a percentage closer to 100% indicates smaller variability with respect to temperature changes.

[0049] The maximum / average value of the loss tangent tanδ is preferably 200% or less, more preferably 180% or less, and even more preferably 160% or less.

[0050] <Overview of Hardness> Hardness was measured using a durometer type D (Ueshima Seisakusho) in accordance with JIS K 6253. Preferably, it is 50 or higher, more preferably 60 or higher, and even more preferably 65 or higher. [Examples]

[0051] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples and can be implemented with various modifications within the scope of the gist of the present invention.

[0052] In the table below, the product names and abbreviations listed in the table indicate the following ingredients. (1) Polyisocyanate • Cosmonate T-100S: 2,4-Tolylene diisocyanate (TDI, manufactured by Mitsui Chemicals, Inc.) • MR-200: Polymethylene polyphenyl polyisocyanate (MDI, manufactured by Tosoh Corporation) • Millionate NM: A mixture of 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate in a ratio of 45:55 (MDI, manufactured by Tosoh Corporation) • Vestanate IPDI: Isophorone diisocyanate (IPDI, manufactured by Evonik) (2) Polyol • PTG-1000SN: Polytetramethylene ether glycol (manufactured by Hodogaya Chemical Co., Ltd., hydroxyl value: 111.4 mg KOH / g) • PTG-650SN: Polytetramethylene ether glycol (manufactured by Hodogaya Chemical Co., Ltd., hydroxyl value: 166.4 mg KOH / g) • PTG-2900SN: Polytetramethylene ether glycol (manufactured by Hodogaya Chemical Co., Ltd., hydroxyl value: 37.7 mg KOH / g) • Actcol D-1000: Polypropylene glycol (manufactured by Mitsui Chemicals, Inc., hydroxyl value: 110.0 mg KOH / g) (3) Chain extenders • MOCA:4,4'-methylenebis(2-chloroaniline) (manufactured by Tokyo Chemical Industry Co., Ltd.) (4) Catalyst • Neostan U-100: Dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd.) • K-KAT XK-640: Bismuth carboxylate (manufactured by Kusumoto Chemical Co., Ltd.)

[0053] <Preparation of isocyanate-terminated prepolymers: Prepolymers A-F> The specified amounts of polyisocyanate listed in Table 1 were added to a 500 mL separable flask, and the specified amounts of polyol listed in Table 1 were added little by little while the reaction was carried out at a temperature of 90°C or below to obtain an isocyanate-terminated prepolymer. When preparing prepolymer F, the specified amounts of catalyst listed in Table 1 were added after the polyisocyanate was added and before the polyol was added.

[0054] <Measurement of NCO mass concentration % of isocyanate-terminated prepolymers> One g of the obtained isocyanate-terminated prepolymer was weighed into a 300 mL Erlenmeyer flask and dissolved in 15 mL of 0.2 N di-n-butylamine toluene solution. A few drops of bromophenol blue and 70 mL of methanol were added, and the resulting mixture was titrated with 0.1 N hydrochloric acid solution. The NCO concentration (mass%) can be calculated using the following formula (in accordance with the isocyanate group content test described in JIS K 7301). NCO concentration (mass%) = (42 × (blank titration value - 0.1N hydrochloric acid solution titration value) × 0.1N hydrochloric acid solution factor × 0.1 × 100) ÷ (sample mass × 1000)

[0055] [Table 1]

[0056] <Synthesis of Polyurethane Resin Compositions: Examples 1-10, Comparative Example 1> A predetermined amount of isocyanate-terminated prepolymer, as listed in Table 2, was weighed into a separable flask. A predetermined amount of polyisocyanate, as listed in Table 2, was added and the mixture was thoroughly stirred. Degassing was then performed under vacuum, and a predetermined amount of chain extender, as listed in Table 2, was added and mixed for 90 seconds. After mixing, the solution was poured onto a glass plate, leveled with an applicator to a film thickness of 2 mm, heated at 80°C for 1 hour, and then cured at 120°C for 5 hours to obtain a coating film (polyurethane resin composition). The obtained coating film was left to stand for at least 24 hours in an environment with a room temperature of 23±2°C and a humidity of 50±10% before its physical properties were evaluated. In Example 7, a predetermined amount of catalyst, as listed in Table 2, was also added and mixed.

[0057] <Hardness> The hardness of the coating film (polyurethane resin composition) was measured after being left standing for 24 hours or more under specified environmental conditions. Hardness was measured using a durometer type D (Ueshima Seisakusho) in accordance with JIS K 6253.

[0058] <Dynamic Viscoelasticity Test (DMA)> Dynamic viscoelasticity measurements were performed under the following conditions. (Measurement conditions) • Measuring device: DMS7100 (manufactured by Hitachi High-Tech Science Co., Ltd.) Sample: 10mm (height) x 5mm (width) x 2mm (thickness) • Test length: 10mm • Test mode: Tensile • Frequency: 10Hz Temperature range: -100℃ to 250℃ • Heating rate: 2°C / 60s ·Distortion amplitude: 10μm ·Minimum tension: 200mN • Tension Again: 1.5 Initial force amplitude: 2000 mN ·Measurement interval: 1point / 3s

[0059] [Table 2]

[0060] [Table 3]

[0061] As can be seen from Tables 2 and 3, in dynamic viscoelasticity measurements, the coating films of Examples 1 to 10 showed little temperature dependence, with the maximum / average value of the loss tangent tanδ being 200% or less in the temperature range of -60 to 120°C, regardless of the type of polyisocyanate used as the raw material for the isocyanate group-terminated prepolymer or the type of polyisocyanate added later. On the other hand, in Comparative Example 1, which did not contain polyisocyanate, the maximum / average value of the loss tangent tanδ exceeded 200%, indicating a high temperature dependence. Furthermore, as shown in Figure 2, when comparing the results of Examples 1 to 5, in which TDI-based prepolymers A to D were used as isocyanate group-terminated prepolymers and myrionate NM was used as the polyisocyanate to vary the NCO mass ratio, with Comparative Example 1, which used TDI-based prepolymer A as the isocyanate group-terminated prepolymer, it was found that the maximum / average value of the loss tangent tanδ decreased when the NCO mass ratio derived from the polyisocyanate was within a predetermined range. On the other hand, regarding hardness, Figure 2 shows that it exhibits a trend inverse to the maximum / average value of the loss tangent tanδ. The measured values ​​of the loss tangent tanδ for each example and comparative example are shown in Figures 3 and 4. [Industrial applicability]

[0062] The polyurethane resin composition using the polishing pad composition comprising an isocyanate group-terminated prepolymer and polyisocyanate according to the present invention is useful for polishing pads for CMP (Chemical Polishing) and the like as a polyurethane resin composition that exhibits less change in physical properties over a wide range of temperature changes than conventional polyurethane resin compositions.

Claims

1. A polishing pad composition comprising an isocyanate-terminated prepolymer and a polyisocyanate, wherein the ratio of the NCO mass derived from the isocyanate-terminated prepolymer to the NCO mass derived from the polyisocyanate in the composition is 80:20 to 15:

85.

2. The composition according to claim 1, wherein the polyisocyanate is one or a mixture selected from aromatic polyisocyanates, aliphatic polyisocyanates, and aromatic alicyclic polyisocyanates.

3. The composition according to claim 1, wherein the NCO mass concentration % of the composition is 6 to 11%.

4. The composition according to claim 1, wherein the polyisocyanate used in the isocyanate-terminated prepolymer is one or a mixture selected from aromatic polyisocyanates, aliphatic polyisocyanates, and aromatic alicyclic polyisocyanates.

5. The composition according to claim 1, wherein the polyol used in the isocyanate-terminated prepolymer is a polyalkylene glycol.

6. The composition according to claim 1, wherein the polyol used in the isocyanate-terminated prepolymer is one or a mixture selected from polytetramethylene ether glycol, polypropylene glycol, and copolymers thereof.

7. A polyurethane resin composition for polishing pads comprising the composition according to any one of claims 1 to 6 and a chain extender.

8. The polyurethane resin composition according to claim 7, wherein the chain extender is a polyamine.

9. The polyurethane resin composition according to claim 7, wherein the chain extender is one or a mixture selected from 4,4'-methylenebis(2-chloroaniline) and its modified forms.

10. A polyurethane resin composition according to any one of claims 7 to 9, wherein the initial force amplitude is 2000 mN, the strain amplitude is 10 μm, the measurement frequency is 10 Hz, and in tensile mode, the maximum value of the loss tangent tanδ in the temperature range from -60°C to 120°C is 200% or less of the average value of tanδ in the said temperature range.

11. A polyurethane resin composition according to any one of claims 7 to 9, wherein the hardness is 50 or higher.

12. A method for producing a polishing pad composition comprising an isocyanate-terminated prepolymer and a polyisocyanate, wherein the method involves synthesizing the isocyanate-terminated prepolymer and then adding the polyisocyanate.

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