Novel hollow microparticles made from melamine-based resin

Abstract

Each of fine hollow particles according to the present invention is composed of a resin film comprising a melamine-based resin, and is characterized in that the resin film is composed of a plurality of small-piece-like parts and binding parts that bind the small-piece-like parts to each other.　According to the present invention, fine hollow particles can be provided, which have excellent solvent resistance and heat resistance, also have satisfactory dispersibility, have large grain diameters, and are stable.

Description

[Technical Field]

[0001] The present invention relates to novel hollow microparticles made of a melamine-based resin. [Background technology]

[0002] Hollow microparticles are used in many fields, including pesticides, pharmaceuticals, fragrances, liquid crystals, adhesives, electronic materials, and building materials. In particular, hollow microparticles have been investigated in recent years for the purpose of providing pores in polyurethane (urea) CMP (Chemical Mechanical Polishing) polishing pads used in wafer polishing. These hollow microparticles are required to have excellent solvent resistance, heat resistance, and desirable particle size control. In particular, in the field of CMP polishing pads, monodisperse hollow microparticles with a relatively large particle size of approximately 20 to 50 μm are desired to achieve high removal rates and atomic-level flatness.

[0003] Therefore, Patent Document 1 discloses a method for producing hollow microparticles made of melamine resin, a thermosetting resin that has excellent heat resistance and solvent resistance. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 7-41594 Summary of the Invention [Problem to be solved by the invention]

[0005] However, although the method of Patent Document 1 provides excellent heat resistance and solvent resistance, there are problems in terms of controlling particle size and dispersibility.

[0006] SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide novel hollow microparticles which have excellent solvent resistance and heat resistance, are easily dispersible, and can be easily produced as stable large-sized hollow microparticles. [Means for solving the problem]

[0007] As a result of intensive research into solving the above-mentioned problems, the present inventors have found that novel hollow microparticles comprising a resin film made of a melamine-based resin, in which the resin film is composed of a plurality of small fragments and bonding portions bonding them together, can solve the above-mentioned problems, and have thus completed the present invention. That is, the present invention relates to the following [1] to [8].

[0008] [1] A hollow microparticle comprising a resin film made of a melamine-based resin, characterized in that the resin film comprises a plurality of small platelet-like portions and bonding portions that bond them together. [2] The hollow microparticles according to the above [1], wherein the small plate-like portions have at least one shape selected from the group consisting of a substantially circular plate shape, a substantially oval spherical shape, and a substantially spherical shape. [3] The hollow microparticles according to the above [1] or [2], wherein the longest diameter of the platelet-like portions is 1 μm to 20 μm. [4] The hollow microparticles according to any one of the above [1] to [3], wherein the particle diameter of the hollow microparticles formed of a resin film made of a melamine resin is 10 μm to 100 μm. [5] A cured product obtained by dispersing the hollow microparticles according to any one of [1] to [4] above in a polyurethane resin. [6] A CMP polishing pad comprising the cured product according to [5] above. [7] A method for producing hollow microparticles composed of a resin film made of a melamine-based resin, comprising: a first step: (a) a step of preparing an oil phase of an organic solvent; a second step: (b) a step of preparing an aqueous phase containing a surfactant; a third step: a step of mixing and stirring the oil phase and the aqueous phase to prepare an O / W emulsion in which the aqueous phase is a continuous phase and the oil phase is a dispersed phase; and a fourth step: a step of adding a melamine formaldehyde prepolymer compound as an additive phase to the O / W emulsion, and dissolving the melamine formaldehyde prepolymer compound at the interface of the O / W emulsion. a fifth step: a step of separating the microparticles from the fine particle dispersion; and a sixth step: a step of removing an oil phase from the interior of the fine particles to form hollow microparticles, wherein the weight ratio of the (a) oil phase of the organic solvent [component (a)] to the (b) aqueous phase containing a surfactant [component (b)] is 100 to 500 parts by mass when the component (a) is taken as 100 parts by mass. [8] The method according to the above [7], wherein the organic solvent used in the oil phase of the organic solvent (a) is selected from organic solvents having a boiling point of 100°C to 180°C. [Effects of the Invention]

[0009] The hollow microparticles of the present invention are characterized by being composed of a resin film made of a melamine-based resin, which is composed of a plurality of small platelet-like portions and a bonding portion that bonds them. By forming such a structure, it is possible to easily obtain large-sized, stable hollow microparticles with good dispersibility. [Brief explanation of the drawings]

[0010] [Figure 1] 1 is an image taken by a field emission scanning electron microscope showing the morphology of hollow microparticles used in the present invention. [Figure 2] 1 is an image of the hollow microparticles obtained in Example 1 taken by a field emission scanning electron microscope. [Figure 3]1 is an image of hollow microparticles obtained in Comparative Example 1 taken by a field emission scanning electron microscope. DETAILED DESCRIPTION OF THE INVENTION

[0011] The hollow microparticles of the present invention are comprised of a resin film made of a melamine-based resin, the resin film comprising a plurality of small pieces and bonding portions bonding the pieces together, and the resin film forms the outer shell (capsule shell) of the hollow microparticles. The resin film is made of a melamine-based resin, which is a resin produced by a condensation reaction between melamine and formaldehyde, such as a melamine-formaldehyde prepolymer compound produced from melamine and formaldehyde, as described below.

[0012] Figure 1 shows the morphology of hollow microparticles of the present invention as observed with a field emission scanning electron microscope. Figure 1 shows cases where the platelet-like portions are approximately circular plate-like (1a) and approximately oval spherical (1b). Specifically, the hollow microparticles shown as "1a" and "1b" have a resin film composed of a plurality of platelet-like portions "2" and connecting portions "3" that connect them. Furthermore, as shown in Figure 1, the resin film of the spherical microparticles of the present invention has a plurality of platelet-like portions "2" dispersed therein, which form irregularities in the resin film.

[0013] It is not clear whether the resin film of the hollow microparticle of the present invention is composed of such a plurality of small fragments and bonding portions that bond them together, but the present inventors consider it as follows.

[0014] Generally, large emulsions exceeding several tens of micrometers in size are less stable during emulsion formation. Therefore, when forming fine particles of several tens of micrometers, coagulation failure is likely to occur during resin film formation, resulting in low yields. Unlike conventional methods, the present invention presumes that two types of emulsion particles, large and small, are formed during emulsion formation. It is presumed that, when a shell made of a resin film forms at the interface of the large, less stable emulsion particles, it coalesces with the small emulsion particles that are simultaneously formed in the system, suppressing coagulation failure of the large emulsion particles and improving the mechanical stability of the film, resulting in the formation of fine particles of several tens of micrometers.

[0015] In the present invention, the small fragments are not particularly limited, but preferably have at least one shape selected from the group consisting of a substantially circular plate, a substantially oval sphere, and a substantially spherical shape. Furthermore, the longest diameter of the small fragments is preferably 1 μm to 20 μm. This range allows the resulting hollow microstructure to have excellent strength. In the present invention, the longest diameter refers to the longest diameter between the outer edges of the small fragments. In the present invention, the longest diameter of the small particle-like portions means the average longest diameter determined from an image observed with a scanning electron microscope, and specifically, the longest diameter of at least 20 or more individual small particle-like portions is measured and calculated as the average value.

[0016] The particle diameter of the hollow microparticles of the present invention is preferably 10 to 100 μm. With this range, when blended into, for example, a CMP polishing pad, excellent polishing properties can be exhibited. Furthermore, the particle diameter of the hollow microparticles is more preferably 20 to 50 μm. In the present invention, the particle size of hollow microparticles means the average particle size determined from an image observed under a scanning electron microscope, and specifically, the particle sizes of at least 20 or more individual hollow microparticles are measured and the average value is calculated. Note that the particle size of each hollow microparticle measured when determining the average particle size is the longest diameter of the hollow microparticles.

[0017] The bulk density of the hollow microparticles of the present invention is not particularly limited, but is preferably 0.01 to 0.5 g / cm. 3 When the molecular weight is in this range, the material can be suitably used for, for example, heat insulating materials and CMP polishing pads.

[0018] The method for producing the hollow microparticles of the present invention is not particularly limited as long as it is a method that can produce hollow microparticles having the characteristics of the present invention, but it is preferable to produce them by the following method.

[0019] The method for producing hollow microparticles of the present invention involves first forming a water-in-oil (O / W) emulsion (hereinafter also referred to as O / W emulsion) from an organic layer and an aqueous layer containing a surfactant. Then, a melamine-formaldehyde prepolymer compound consisting of melamine and formaldehyde is added to the O / W emulsion as an additive phase. The pH is adjusted to an acidic range, and the mixture is stirred and mixed under heating to induce a condensation reaction of methylolated melamine at the droplet interface of the dispersed oil phase, forming a resin film, thereby producing microparticles encapsulating the oil phase. The microparticles encapsulating the oil phase are then isolated by filtration or centrifugation, and the internal oil or aqueous phase is removed by vacuum drying to recover the hollow microparticles. Specific examples are provided below, but the production method of the present invention is not limited to these.

[0020] The method for producing hollow microparticles of the present invention can be subdivided into the following steps: Step 1: preparing (a) an oil phase of an organic solvent (hereinafter also referred to as component (a)); Step 2: preparing (b) an aqueous phase containing a surfactant (hereinafter also referred to as component (b)); Step 3: mixing and stirring component (a) and component (b) to prepare an O / W emulsion in which the aqueous phase is a continuous phase and the oil phase is a dispersed phase; Step 4: adding a melamine formaldehyde prepolymer compound as an additive phase to the O / W emulsion, and causing a condensation reaction of methylol melamine, which is a melamine formaldehyde prepolymer compound, to proceed at the interface of the O / W emulsion to form a resin film, thereby forming microparticles, thereby obtaining a microparticle dispersion in which the microparticles are dispersed; Step 5: separating the microparticles from the microparticle dispersion; and Step 6: removing the oil phase from the interior of the microparticles to form hollow microparticles.

[0021] 1st step: The first step is to prepare (a) an oil phase made of an organic solvent, which will become the dispersed phase in the O / W emulsion.

[0022] Second step: The second step is a step of preparing (b) an aqueous phase containing a surfactant and water, which will become the continuous phase in the O / W emulsion. In the second step, the pH may be adjusted as necessary. This step includes dissolving a surfactant (described later) in water and adjusting the pH as needed. The pH adjustment and other steps may be carried out by known methods.

[0023] In the present invention, the amount of surfactant used is 0.1 to 10 parts by mass, preferably 0.5 to 10 parts by mass, per 100 parts by mass of the aqueous phase. Within this range, aggregation of droplets in the dispersed phase in the O / W emulsion is avoided, and hollow microparticles can be easily obtained with a high yield.

[0024] Furthermore, when a maleic anhydride copolymer is used as the surfactant, the pH is preferably adjusted to a value at which a carboxylic acid is produced from maleic anhydride.

[0025] Third step: The third step is a step of mixing and stirring component (a) obtained in the first step with component (b) obtained in the second step to prepare an O / W emulsion in which component (a) forms the dispersed phase and component (b) forms the continuous phase.

[0026] In the present invention, the method for mixing and stirring component (a) and component (b) to prepare an O / W emulsion can be adjusted by appropriately mixing and stirring them by a known method, taking into consideration the particle size of the hollow microparticles to be produced. Furthermore, the temperature and pH can also be adjusted in the process of preparing the O / W emulsion.

[0027] Among these, a preferred method is to mix component (a) and component (b) and then disperse them using a known disperser such as a high-speed shear type, friction type, high-pressure jet type, or ultrasonic type for stirring to form an O / W emulsion, with the high-speed shear type being preferred. When using a high-speed shear type disperser, the rotation speed is preferably 500 to 20,000 rpm, more preferably 1,000 to 10,000 rpm. The dispersion time is preferably 0.1 to 30 minutes, and more preferably 1 to 10 minutes. The dispersion temperature is preferably 20 to 80°C.

[0028] In the present invention, the weight ratio of component (a) to component (b) is preferably 100 to 500 parts by mass, and more preferably 150 to 300 parts by mass, of component (b) when component (a) is taken as 100 parts by mass. Note that the weight ratio of component (a) to component (b) is the weight ratio when components (a) and (b) are mixed in the third step.

[0029] The above conditions make it easier to obtain the hollow microparticles of the present invention, which are composed of a resin membrane consisting of a plurality of small platelets and bonding portions that connect them. This is presumably because large and small emulsion particles are simultaneously generated in the O / W emulsion system.

[0030] 4th step: The fourth step is a step of adding a melamine formaldehyde prepolymer compound as an additive phase to the O / W emulsion, causing a condensation reaction of the methylolated melamine, which is the melamine formaldehyde prepolymer compound, at the droplet interface of the O / W emulsion to form a resin film, which becomes fine particles encapsulating the oil phase, thereby obtaining a fine particle dispersion in which the formed fine particles are dispersed.

[0031] It is presumed that in this process, small-sized emulsion particles coalesce at the interface of the large-sized emulsion particles, forming a resin film.

[0032] The additive phase may consist of only the melamine formaldehyde prepolymer compound, but it is preferable to use the melamine formaldehyde prepolymer compound dissolved in water or an alkaline aqueous solution.

[0033] The amount of the melamine formaldehyde prepolymer compound used in the additive phase is not particularly limited, but in order to form fine particles well, it is preferably 20 to 100 parts by mass per 100 parts by mass of the component (a) used in the first step.

[0034] As the melamine formaldehyde prepolymer compound, a commercially available melamine formaldehyde prepolymer compound described below may be added as is, or may be dissolved in water or an alkaline aqueous solution before use. Alternatively, a melamine formaldehyde prepolymer compound produced in an alkaline aqueous solution by addition reaction of melamine with formaldehyde by heating in the alkaline range in accordance with a conventional method may be used as is.

[0035] When the total amount of the melamine formaldehyde prepolymer compounds in the additive phase is 100 parts by mass, it is preferable to use water or an alkaline aqueous solution in an amount of 0 to 500 parts by mass, and more preferably in an amount of 20 to 300 parts by mass.

[0036] The pH of the aqueous phase, which is the continuous phase, may be adjusted after the addition of the additive phase. The pH of the aqueous phase, which is the continuous phase, is preferably less than 7, more preferably adjusted to a pH of 3.5 to 6.5, and most preferably adjusted to a pH of 4.0 to 5.5. The reaction is preferably carried out at a temperature in the range of 40 to 90°C. The reaction time is preferably in the range of 1 to 48 hours.

[0037] Fifth step: The fifth step is a step of separating the microparticles from the microparticle dispersion. The method for separating the microparticles from the microparticle dispersion is not particularly limited and may be selected from common separation techniques, and specifically, filtration, centrifugation, etc. may be used.

[0038] 6th step: The sixth step is a step of removing the internal oil phase from the fine particles obtained in the fifth step to form hollow fine particles. The method for removing the oil phase from the fine particles is not particularly limited and may be selected from common separation techniques, and specifically, a circulating air dryer, spray dryer, fluidized bed dryer, vacuum dryer, etc. may be used. The temperature condition for drying is preferably 40 to 250°C, more preferably 50 to 200°C.

[0039] Each component used in the present invention will be described below.

[0040] In the present invention, the organic solvent used in component (a) is not particularly limited, but an organic solvent with a boiling point of 90°C to 200°C is preferred. By using an organic solvent with a boiling point in this range, emulsion formation can be maintained even at the temperature at which the condensation reaction of methylol melamine is carried out, and the organic solvent can be easily removed from the obtained microparticles. The organic solvent more preferably has a boiling point of 100°C to 180°C. Examples of such organic solvents include the following:

[0041] Examples of hydrocarbon solvents that can be used include aliphatic hydrocarbons having 7 to 11 carbon atoms, and alicyclic hydrocarbons such as cycloheptane and cyclooctane. Examples of solvents that can be used other than hydrocarbon solvents include butyl acetate, dibutyl ether, 1,2-dichloroethane, toluene, xylene, benzaldehyde, chlorobenzene, and dichlorobenzene. These organic solvents may be used alone or in combination of two or more.

[0042] The organic solvent used in the present invention is preferably an aliphatic hydrocarbon having 8 to 11 carbon atoms, cycloheptane, cyclooctane, toluene, xylene, or chlorobenzene, and most preferably toluene, xylene, or chlorobenzene.

[0043] In the present invention, the surfactant used in component (b) is not particularly limited, and two or more types may be mixed. The surfactant of the present invention is preferably one having a carboxyl group as at least one hydrophilic group, and the carboxyl group may be generated by hydrolysis of a dicarboxylic acid anhydride. Among these, maleic anhydride copolymers such as styrene-maleic anhydride copolymer, ethylene-maleic anhydride copolymer, and isobutylene-maleic anhydride copolymer are preferably used. Of these, ethylene-maleic anhydride copolymers are preferably used. The molecular weight of the maleic anhydride copolymer described above is preferably about 30,000 to 500,000. Within this range, a stable emulsion and resin film can be formed.

[0044] The melamine-formaldehyde prepolymer compound usable in the present invention is a methylolated melamine composed of melamine and formaldehyde, and can be produced by a conventional method. For example, it can be produced by heating an alkaline aqueous solution containing melamine and formaldehyde in the alkaline range to cause an addition reaction of melamine with formaldehyde. Alternatively, commercially available melamine-formaldehyde prepolymer compounds can be used as appropriate. Examples include Beckamine APM, Beckamine M-3, Beckamine M-3(60), Beckamine MA-S, Beckamine J-101, and Beckamine J-101LF (manufactured by DIC Corporation), Nikaresin S-176, Nikaresin S-260 (manufactured by Nippon Carbide Corporation), and Milben Resin SM-800 (manufactured by Showa Polymer Co., Ltd.).

[0045] The above-mentioned methylolated melamine can be prepared in a range from monomethylolated melamine (melamine / formaldehyde molar ratio: 1 / 1) to hexamethylolated melamine (1 / 6) by adjusting the molar ratio of melamine to formaldehyde. However, from the viewpoints of both the ability to surround oil phase droplets in an O / W emulsion and condensation reactivity (crosslinkability), trimethylolated melamine (1 / 3) to pentamethylolated melamine (1 / 5) are preferred, with tetramethylolated melamine (1 / 4) being particularly preferred.

[0046] The mechanism of the formation of the hollow microparticles is presumed to be as follows: droplets of an oil phase (a) composed of an organic solvent are dispersed in an aqueous phase; methylolated melamine forms an acid amide bond with hydrophilic groups (e.g., carboxyl groups) of a surfactant coordinated at the droplet interface, resulting in the encapsulation of the droplets by methylolated melamine; adjacent methylolated melamines undergo a dehydration condensation reaction between the methylol groups in this encapsulated state, forming a capsule shell of melamine-formaldehyde resin. Furthermore, the methylolation ratio of melamine (the molar ratio of formaldehyde to melamine) is related to the density of the capsule shell; the higher the methylolation ratio, the higher the crosslinking density and the denser the shell. Therefore, it is preferable to form the methylolated melamine within the above-mentioned range.

[0047] The hollow microparticles of the present invention can be used in a variety of applications, including in many fields such as agricultural chemicals, medicines, cosmetic materials, liquid crystals, adhesives, electronic materials and components, and building materials. In particular, the hollow microparticles of the present invention can be suitably used in shoe soles and insoles, heat insulation materials, soundproofing materials, and CMP polishing pads.

[0048] As a method for using such a CMP polishing pad, any known method can be used without limitation. For example, a resin containing the microhollow particles of the present invention as a foaming agent can be cut and the surface polished to produce a CMP polishing pad having pores on the polishing surface of the resin.

[0049] The resin is not particularly limited, but in the present invention, a polyurethane resin, which will be described later, is particularly suitable. That is, it is preferable to prepare a cured product in which the hollow microparticles of the present invention are dispersed in a polyurethane resin, and to produce a CMP polishing pad from the cured product. In particular, the hollow microparticles of the present invention have good compatibility with polyurethane resins, so when used in a CMP polishing pad, the hollow microparticles are less likely to fall off, making it possible to improve scratch resistance.

[0050] The density of the CMP polishing pad of the present invention is 0.40 to 1.10 g / cm 3 It is preferable that the density is 0.50 to 1.05 g / cm 3 It is more preferable that the foaming agent is a foaming agent having a molecular weight of 100 or more. Furthermore, a cured foam obtained by combining the hollow microparticles of the present invention with a known foaming method can also be used as a CMP polishing pad. For example, in a known foaming method using a foaming agent in which water is added, in the case of a polyurethane resin, water reacts with an iso(thio)cyanate group, and then carbon dioxide and an amino group are generated. The carbon dioxide becomes a foaming gas, and the amino group further reacts with an iso(thio)cyanate group to form a urea bond and / or a thiourea bond.

[0051] The CMP polishing pad of the present invention can have any suitable hardness. The hardness in the present invention can be measured according to the Shore method, for example, according to JIS standard (hardness test) K6253. In the present invention, the Shore hardness of the CMP polishing pad is preferably 30A to 80D, and more preferably 40A to 70D (where "A" indicates hardness on the Shore "A" scale, and "D" indicates hardness on the Shore "D" scale). That is, for example, 30A to 80D means that the Shore A hardness is 30 or more and the Shore D hardness is 70 or less. The hardness can be adjusted to any desired value by changing the blending composition and blending amount as required.

[0052] Furthermore, the CMP polishing pad of the present invention preferably has a compression ratio within the following range in order to achieve flatness of the polished object. The compression ratio can be measured by a method in accordance with JIS L 1096. The compression ratio is preferably 0.5% to 50%. By keeping the compression ratio within the above range, it is possible to achieve excellent flatness of the polished object.

[0053] The abrasion resistance of the CMP polishing pad of the present invention is preferably 60 mg or less, more preferably 50 mg or less, in a Taber abrasion test. The reduced Taber abrasion amount allows the pad to exhibit excellent abrasion resistance when used as a CMP polishing pad.

[0054] The form of the CMP polishing pad of the present invention is not particularly limited, and for example, a groove structure may be formed on the surface thereof. The groove structure of the CMP polishing pad is preferably a shape that retains and renews the slurry, and specific examples thereof include X (stripe) grooves, XY lattice grooves, concentric grooves, through holes, blind holes, polygonal columns, cylinders, spiral grooves, eccentric circular grooves, radial grooves, and combinations of these grooves.

[0055] The method for producing the groove structure of the CMP polishing pad is not particularly limited. For example, the method may be a method of pouring the compound or the like into a mold having a predetermined groove structure and curing it, or a method of producing a groove structure using the obtained resin, such as a mechanical cutting method using a tool such as a cutting tool of a predetermined size, a method of pressing a resin with a press plate having a predetermined surface shape, a method of producing using photolithography, a method of producing using a printing method, or a method of producing using a laser beam such as a carbon dioxide laser.

[0056] The CMP polishing pad of the present invention may also be composed of multiple layers. In this case, the cured product of the present invention may be used in at least one of the layers. For example, when the CMP polishing pad is composed of two layers, it has a polishing layer (also referred to as the first layer) having a polishing surface that contacts the workpiece during polishing, and a base layer (also referred to as the second layer) that contacts the first layer on the surface opposite the polishing surface of the first layer. In this case, the characteristics of the CMP polishing pad can be adjusted by making the second layer and the first layer different in hardness and elastic modulus. In this case, it is preferable that the base layer has a lower hardness than the polishing layer. In the present invention, it is preferable to use the cured product of the present invention as the polishing layer, and further, the cured product of the present invention may also be used in the base layer.

[0057] The polyurethane resin used in the above-mentioned CMP polishing pad will be described in detail below. The polyurethane resin may be prepared by any known method without particular limitation, for example, by uniformly mixing and dispersing (B) a polyfunctional isocyanate compound (hereinafter also referred to as component (B)), (C) a compound having an isocyanate group and two or more active hydrogen groups capable of curing (hereinafter also referred to as component (C)), and, if necessary, other ingredients, followed by curing. Examples of the active hydrogen groups in component (C) include groups selected from the group consisting of hydroxyl groups, thiol groups, and amino groups. Furthermore, a cured product in which the hollow microparticles of the present invention are dispersed in a polyurethane resin can be produced, for example, by curing a curable composition containing components (B), (C), and the hollow microparticles of the present invention. Other components may be added to the curable composition as needed. The cured product thus produced can be processed into a desired shape and used as a CMP polishing pad.

[0058] The curing method is not particularly limited, and any known method may be used. For example, the conditions described in WO 2015 / 068798, WO 2016 / 143910, and WO 2018 / 092826 can be used. Specifically, dry methods such as the one-pot method and the prepolymer method, and wet methods using a solvent can be used. Among these, the dry method is preferably used.

[0059] The amount of the hollow microparticles of the present invention blended into the polyurethane resin is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, and even more preferably 0.5 to 8 parts by mass, per 100 parts by mass of the total of components (B) and (C). By adjusting the amount within this range, it is possible to exhibit excellent polishing properties.

[0060] In the present invention, the term "polyurethane resin" collectively refers to polyurethane resins, polyurea resins, and polyurethane urea resins. The polyurethane resins of the present invention also include polythiourethane resins and polythiourethane resins.

[0061] Each component will be described in detail below.

[0062] <(B) Polyfunctional Isocyanate Compound; Component (B)> Component (B) is a compound having at least two iso(thio)cyanate groups.

[0063] In the present invention, the term "iso(thio)cyanate group" refers to an isocyanate group (NCO group) or an isothiocyanate group (NCS group). Of course, compounds having both an isocyanate group and an isothiocyanate group can also be selected as component (B). Therefore, the number of isocyanate groups in component (B) refers to the total number of isocyanate groups and isothiocyanate groups.

[0064] Among these, compounds having 2 to 6 iso(thio)cyanate groups in the molecule are preferred, compounds having 2 to 4 are more preferred, and compounds having 2 to 3 are even more preferred.

[0065] The (B) component may also be a (B1) urethane prepolymer (hereinafter also referred to as "component (B1)") produced by reacting a (B11) bifunctional iso(thio)cyanate compound having two iso(thio)cyanate groups per molecule (hereinafter also referred to as "component (B11)") with a (C11) bifunctional active hydrogen-containing compound having two active hydrogen groups per molecule (hereinafter also referred to as "component (C11)"). The (B1) component corresponding to component (B) can be used without any restrictions as long as it contains two or more unreacted isocyanate groups or isothiocyanate groups, and a (B1) component containing two or more isocyanate groups is preferred.

[0066] The active hydrogen group in the component (C11) is a group selected from a hydroxyl group, a thiol group, and an amino group.

[0067] The (B) component can be broadly classified into aliphatic isocyanates, alicyclic isocyanates, aromatic isocyanates, isothiocyanates, other isocyanates, and (B1) components. The (B) component can be a single compound or multiple compounds. When multiple compounds are used, the reference mass is the total amount of the multiple compounds. Specific examples of these (B) components include the following:

[0068] Aliphatic isocyanate; component (B) Ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2'-dimethylpentane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-trimethylundecamethylene diisocyanate, 1,3,6-trimethyl bifunctional isocyanates such as hexamethylene diisocyanate, 1,8-diisocyanate-4-isocyanate methyl octane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyl octane, bis(isocyanate ethyl)carbonate, bis(isocyanate ethyl)ether, 1,4-butylene glycol dipropyl ether-ω,ω'-diisocyanate, lysine diisocyanate methyl ester, and 2,4,4-trimethylhexamethylene diisocyanate (corresponding to component (B11) that constitutes component (B1) described in detail below).

[0069] Alicyclic isocyanate; component (B) Isophorone diisocyanate, (bicyclo[2.2.1]heptane-2,5-diyl)bismethylene diisocyanate, (bicyclo[2.2.1]heptane-2,6-diyl)bismethylene diisocyanate, 2β,5α-bis(isocyanate)norbornane, 2β,5β-bis(isocyanate)norbornane, 2β,6α-bis(isocyanate)norbornane, 2β,6β-bis(isocyanate)norbornane, 2,6-di(isocyanatemethyl)furan, bis( Isocyanatemethyl)cyclohexane, dicyclohexylmethane-4,4'-diisocyanate, 4,4-isopropylidenebis(cyclohexylisocyanate), cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate, bis(4-isocyanato-n-butylidene)pentaerythritol, dimer acid diisocyanate, 2,5- Bis(isocyanatomethyl)-bicyclo[2,2,1]-heptane, 2,6-bis(isocyanatomethyl)-bicyclo[2,2,1]-heptane, 3,8-bis(isocyanatomethyl)tricyclodecane, 3,9-bis(isocyanatomethyl)tricyclodecane, 4,8-bis(isocyanatomethyl)tricyclodecane, 4,9-bis(isocyanatomethyl)tricyclodecane, 1,5-diisocyanatodecalin, 2,7-diisocyanatodecalin, 1,4- Diisocyanate decalin, 2,6-diisocyanate decalin, bicyclo[4.3.0]nonane-3,7-diisocyanate, bicyclo[4.3.0]nonane-4,8-diisocyanate, bicyclo[2.2.1]heptane-2,5-diisocyanate and bicyclo[2.2.1]heptane-2,6-diisocyanate, bicyclo[2,2,2]octane-2,5-diisocyanate, bicyclo[2,2,2]octane-2,6-diisocyanate, tricyclo[5.2.1.0]octane-2,5-diisocyanate, bicyclo[2,2,2]octane-2,6-diisocyanate, 2.6 ] decane-3,8-diisocyanate, tricyclo[5.2.1.0 2.6 ] Difunctional isocyanates such as decane-4,9-diisocyanate (corresponding to component (B11) constituting component (B1) described in detail below).

[0070] 2-isocyanatomethyl-3-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2,2,1]-heptane, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2,2,1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2,2,1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2,2,1]-heptane, 2-isocyanatomethyl-3-(3-isocyanatopropyl polyfunctional isocyanates such as 2-isocyanatemethyl-3-(3-isocyanatepropyl)-6-(2-isocyanateethyl)-bicyclo[2,1,1]-heptane, 2-isocyanatemethyl-2-(3-isocyanatepropyl)-5-(2-isocyanateethyl)-bicyclo[2,2,1]-heptane, 2-isocyanatemethyl-2-(3-isocyanatepropyl)-6-(2-isocyanateethyl)-bicyclo[2,2,1]-heptane, and 1,3,5-tris(isocyanatemethyl)cyclohexane.

[0071] Aromatic isocyanate; component (B) Xylylene diisocyanate (o-, m-, p-), tetrachloro-m-xylylene diisocyanate, methylenediphenyl-4,4'-diisocyanate, 4-chloro-m-xylylene diisocyanate, 4,5-dichloro-m-xylylene diisocyanate, 2,3,5,6-tetrabromo-p-xylylene diisocyanate, 4-methyl-m-xylylene diisocyanate, 4-ethyl-m-xylylene diisocyanate, bis(isocyanatoethyl)benzene, bis(isocyanatopropyl)benzene, 1,3-bis(α, α-dimethylisocyanatomethyl)benzene, 1,4-bis(α,α-dimethylisocyanatomethyl)benzene, α,α,α',α'-tetramethylxylylene diisocyanate, bis(isocyanatobutyl)benzene, bis(isocyanatomethyl)naphthalene, bis(isocyanatomethyl)diphenyl ether, bis(isocyanatoethyl)phthalate, 2,6-di(isocyanatomethyl)furan, phenylene diisocyanate (o-, m-, p-), tolylene diisocyanate, ethyl phenylene diisocyanate, isocyanate Isopropyl phenylene diisocyanate, dimethyl phenylene diisocyanate, diethyl phenylene diisocyanate, diisopropyl phenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, 1,3,5-triisocyanate methylbenzene, 1,5-naphthalene diisocyanate, methyl naphthalene diisocyanate, biphenyl diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2' -Diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, bibenzyl-4,4'-diisocyanate, bis(isocyanatophenyl)ethylene, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, phenylisocyanatomethyl isocyanate, phenylisocyanatoethyl isocyanate, tetrahydronaphthylene diisocyanate, hexahydrobenzene diisocyanate, hexahydrodiphenylmethane-4,Bifunctional isocyanates such as 4'-diisocyanate, diphenyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate, 1,3-propylene glycol diphenyl ether diisocyanate, benzophenone diisocyanate, diethylene glycol diphenyl ether diisocyanate, dibenzofuran diisocyanate, carbazole diisocyanate, ethyl carbazole diisocyanate, dichlorocarbazole diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate (corresponding to component (B11) constituting component (B1) described in detail below).

[0072] Polyfunctional isocyanate compounds such as mesitylene triisocyanate, triphenylmethane triisocyanate, polymeric MDI, naphthalene triisocyanate, diphenylmethane-2,4,4'-triisocyanate, 3-methyldiphenylmethane-4,4',6-triisocyanate, and 4-methyl-diphenylmethane-2,3,4',5,6-pentaisocyanate.

[0073] Isothiocyanate; component (B) Bifunctional isothiocyanates such as p-phenylenediisothiocyanate, xylylene-1,4-diisothiocyanate, and ethylidine diisothiocyanate (corresponding to component (B11) which constitutes component (B1) described in detail below).

[0074] Other isocyanates: Component (B) Other isocyanates include polyfunctional isocyanates having a biuret structure, a uretdione structure, or an isocyanurate structure (for example, JP 2004-534870 A discloses a method for modifying the biuret structure, uretdione structure, or isocyanurate structure of an aliphatic polyisocyanate) that are primarily made from diisocyanates such as hexamethylene diisocyanate or tolylene diisocyanate, and polyfunctional isocyanates that are made polyfunctional as adducts with trifunctional or higher polyols such as trimethylolpropane (disclosed in, for example, a book (Polyurethane Resin Handbook, edited by Iwata Keiji, Nikkan Kogyo Shimbun, 1987)).

[0075] (B1) urethane prepolymer; (B) component having iso(thio)cyanate groups at both ends; (B1) component In the present invention, the component (B1) produced by reacting the component (B11) with the component (C11) described below can also be used as the component (B). The component (B1) is a compound having iso(thio)cyanate groups at both ends.

[0076] The component (B1) is not particularly limited, but it is particularly preferable to use the following monomers as the component (B11): Specifically, it is preferable to use 1,5-naphthalene diisocyanate, xylene diisocyanate (o-, m-, p-), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, phenylene diisocyanate (o-, m-, p-), 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane-4,4'-diisocyanate, and (bicyclo[2.2.1]heptane-2,5(2,6)-diyl)bismethylene diisocyanate. It is preferable to react these with the component (C11) to obtain the component (B1) having isocyanate groups and / or isothiocyanate groups at both ends.

[0077] Furthermore, in order for the final polyurethane resin to exhibit particularly excellent properties, it is preferable to produce component (B1) using at least one type of component (C11) having a molecular weight (number average molecular weight) of 300 to 2000. The active hydrogen group refers to a hydroxyl group, a thiol group, or an amino group. Among these, in consideration of reactivity, the active hydrogen group in component (C11) is preferably a hydroxyl group.

[0078] The (C11) component having a molecular weight (number average molecular weight) of 300 to 2000 can be used in combination with different types or with different molecular weights. Furthermore, in order to adjust the hardness, strength, etc., of the final polyurethane resin, it is preferable to use a (B1) component produced by combining a (C11) component having a molecular weight (number average molecular weight) of 300 to 2000 with a (C11) component having a molecular weight (number average molecular weight) of 90 to 300. In this case, depending on the types and amounts of the (C11) and (B11) components used, the amount of the (C11) component having a molecular weight of 300 to 2000 is preferably 0 to 50 parts by mass, and more preferably 1 to 40 parts by mass, of the (C11) component having a molecular weight of 90 to 300.

[0079] Furthermore, the (B1) component must have iso(thio)cyanate groups at both ends of the molecule. Therefore, it is preferable to produce the (B1) component so that the total number of moles (n5) of iso(thio)cyanate groups in the (B11) component and the total number of moles (n6) of active hydrogen groups (hydroxyl, thiol, or amino groups) in the (C11) component satisfy the relationship 1 < (n5) / (n6) ≦ 2.3. When two or more types of (B11) components are used as molecular terminals, the number of moles (n5) of iso(thio)cyanate groups is, of course, the total number of moles of iso(thio)cyanate groups in the (B11) component. Furthermore, the number of moles (n6) of active hydrogen groups in two or more types of (C11) components is, of course, the total number of moles of active hydrogen in the active hydrogen groups. Even when the active hydrogen groups are primary amino groups, the primary amino group is considered to be 1 mole. In other words, a considerable amount of energy is required for the second amino group (-NH) in a primary amino group to react (even in a primary amino group, the second -NH is difficult to react with). Therefore, in the present invention, even if a (C11) component having a primary amino group is used, the number of primary amino groups can be calculated as 1 mole.

[0080] The iso(thio)cyanate equivalent of the (B1) component (the total amount of isocyanate equivalents and / or isothiocyanate equivalents) can be determined by quantifying the iso(thio)cyanate groups in the (B1) component in accordance with JIS K 7301. The iso(thio)cyanate groups can be quantified by the following back titration method. First, the obtained (B1) component is dissolved in a dry solvent. Next, di-n-butylamine, the concentration of which is known and clearly in excess of the amount of iso(thio)cyanate groups in the (B1) component, is added to the dry solvent, and all of the iso(thio)cyanate groups in the (B1) component are reacted with the di-n-butylamine. Next, the unconsumed di-n-butylamine (not involved in the reaction) is titrated with acid to determine the amount of di-n-butylamine consumed. Since the amount of di-n-butylamine consumed is equal to the amount of iso(thio)cyanate groups in component (B1), the iso(thio)cyanate equivalent can be calculated. Furthermore, since component (B1) is a linear urethane prepolymer with iso(thio)cyanate groups at both ends, the number-average molecular weight of component (B1) is twice the iso(thio)cyanate equivalent. This molecular weight of component (B1) is likely to coincide with the value measured by gel permeation chromatography (GPC). For example, when component (B1) and component (B11) are used in combination, a mixture of the two can be measured according to the above method.

[0081] The (B1) component is not particularly limited, but the iso(thio)cyanate equivalent is preferably 300 to 5,000, more preferably 350 to 3,000, and particularly preferably 350 to 2,000. The reason for this is not particularly clear, but is thought to be as follows: The use of the (B1) component facilitates dispersion of crosslinking points in the polyurethane resin, resulting in random and uniform distribution, which is thought to result in stable performance. Furthermore, the polyurethane resin obtained using the (B1) component is easier to control during production. For example, the curable composition used in the present invention is thought to be suitable for use as a polishing pad. When the (B1) component and the (B11) component are used in combination, this effect is thought to be exhibited even if the average iso(thio)cyanate equivalent of the polyiso(thio)cyanate compound is 300 to 5,000. However, the effect is thought to be more pronounced when the (B1) component is used alone.

[0082] The method for producing the component (B1) used in the present invention involves reacting a component (C11) having two active hydrogen groups (hydroxyl, thiol, or amino groups) in the molecule with a component (B11) to produce a component (B1) having an isocyanate group or an isothiocyanate group at the molecular terminal. There are no limitations as long as a prepolymer having an isocyanate group or an isothiocyanate group at the terminal can be obtained.

[0083] As mentioned above, the preferred (C11) component and the amount of (B11) component blended to obtain the (B1) component are as follows: Specifically, it is preferable to produce the (B11) component so that the number of moles of iso(thio)cyanate groups (n5) in the (B11) component and the number of moles of active hydrogen (n6) in the (C11) component satisfy the relationship 1<(n5) / (n6)≦2.3.

[0084] In addition, the reaction for producing component (B1) can be carried out by heating or adding a urethanization catalyst as necessary.

[0085] From the viewpoint of controlling the strength and reactivity of the polyurethane resin formed, the most preferred examples of the component (B) used in the present invention include alicyclic isocyanates such as isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, and (bicyclo[2.2.1]heptane-2,5(2,6)-diyl)bismethylene diisocyanate; aromatic isocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylylene diisocyanate (o-, m-, p-); polyfunctional isocyanates having a biuret structure, uretdione structure, or isocyanurate structure, which are made primarily from diisocyanates such as hexamethylene diisocyanate or tolylene diisocyanate; polyfunctional isocyanates as adducts with tri- or higher functional polyols; and component (B1). Of these, component (B1) is particularly preferred.

[0086] <(C) Compound Having an Isocyanate Group and Two or More Curable Active Hydrogen Groups; Component (C)> Component (C) can be any compound that has at least two groups selected from the group consisting of hydroxyl groups, thiol groups, and amino groups in one molecule, and of course, compounds that have any two or all of hydroxyl groups, thiol groups, and amino groups can also be selected.

[0087] Among these, component (C) preferably contains (CA) a compound having two or more amino groups (hereinafter also referred to as "component (CA)"), and more preferably further contains (CB) a compound having three or more hydroxyl groups and / or thiol groups (hereinafter also referred to as "component (CB)"). In the present invention, a compound having n or more hydroxyl groups and / or thiol groups means that the total number of hydroxyl groups and thiol groups in the compound is n or more, and may be a compound having hydroxyl groups but no thiol groups, a compound having thiol groups but no hydroxyl groups, or a compound having both hydroxyl groups and thiol groups.

[0088] Among these, the component (CB) is particularly preferably a compound having five or more hydroxyl groups and / or thiol groups, and the number of moles of hydroxyl groups and / or thiol groups per mass of the component (CB) is preferably 0.5 mmol / g to 35 mmol / g, more preferably 0.8 mmol / g to 20 mmol / g.

[0089] ((CA) Compound having two or more amino groups; (CA) component) The component (CA) can be any compound having two or more primary and / or secondary amino groups in one molecule. Compounds having two or more amino groups can be broadly classified into aliphatic amines, alicyclic amines, aromatic amines, and polyrotaxanes having an amino group polymerizable with an isocyanate group.

[0090] Aliphatic amine (CA) component Bifunctional amines such as ethylenediamine, hexamethylenediamine, nonamethylenediamine, undecanemethylenediamine, dodecamethylenediamine, metaxylenediamine, 1,3-propanediamine, and putrescine (corresponding to the component (C11) constituting the component (B1)).

[0091] Polyfunctional amines such as polyamines such as diethylenetriamine.

[0092] Alicyclic amine (CA) component Bifunctional amines such as isophoronediamine and cyclohexyldiamine (corresponding to the component (C11) constituting the component (B1)).

[0093] Aromatic amine (CA) component 4,4'-methylenebis(o-chloroaniline) (MOCA), 2,6-dichloro-p-phenylenediamine, 4,4'-methylenebis(2,3-dichloroaniline), 4,4'-methylenebis(2-ethyl-6-methylaniline), 3,5-bis(methylthio)-2,4-toluenediamine, 3,5-bis(methylthio)-2,6-toluenediamine, 3,5-diethyltoluene-2,4-diamine, 3,5-diethyltoluene Benzene-2,6-diamine, trimethylene glycol-di-p-aminobenzoate, polytetramethylene glycol-di-p-aminobenzoate, 4,4'-diamino-3,3',5,5'-tetraethyldiphenylmethane, 4,4'-diamino-3,3'-diisopropyl-5,5'-dimethyldiphenylmethane, 4,4'-diamino-3,3',5,5'-tetraisopropyldiphenylmethane, 1,2-bis(2-aminophenyl) (phenylthio)ethane, 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, N,N'-di-sec-butyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, m-xylylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, p-phenylenediamine, 3,3'-methylene bifunctional amines such as 2,4-diamino-4-chlorobenzoate, 2-methylpropyl 2,4-diamino-4-chlorobenzoate, isopropyl 2,4-diamino-4-chlorophenylacetate, di-(2-aminophenyl)thioethyl terephthalate, diphenylmethanediamine, tolylenediamine, and piperazine (corresponding to component (C11) which constitutes component (B1) above).

[0094] Polyfunctional amines such as 1,3,5-benzenetriamine and melamine.

[0095] Polyrotaxane with amino groups; (CA) component The polyrotaxane having an amino group used in the present invention is not particularly limited, and examples thereof include the polyrotaxanes described in WO 2018 / 092826.

[0096] Among the (CA) components used in the present invention, preferred are 4,4'-methylenebis(o-chloroaniline) (MOCA), 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, 3,5-diethyltoluene-2,4-diamine, 3,5-diethyltoluene-2,6-diamine, 3,5-bis(methylthio)-2,4-toluenediamine, 3,5-bis(methylthio)-2,6-toluenediamine, and trimethylene glycol-di-p-aminobenzoate.

[0097] Among the components (C), compounds having hydroxyl groups and / or thiol groups can be broadly classified into aliphatic alcohols, alicyclic alcohols, aromatic alcohols, polyester polyols, polyether polyols, polycaprolactone polyols, polycarbonate polyols, polyacrylic polyols, castor oil-based polyols, compounds having two or more thiol groups, OH / SH-type polymerizable group-containing monomers, side-chain-containing cyclic molecules having three or more hydroxyl groups and / or thiol groups, and polyrotaxanes having hydroxyl groups and / or thiol groups. Specific examples include the following:

[0098] ((C) Compound having two or more hydroxyl groups; (C) component) Fatty alcohol; component (C) Bifunctional polyols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 1,5-dihydroxypentane, 1,6-dihydroxyhexane, 1,7-dihydroxyheptane, 1,8-dihydroxyoctane, 1,9-dihydroxynonane, 1,10-dihydroxydecane, 1,11-dihydroxyundecane, 1,12-dihydroxydodecane, neopentyl glycol, glyceryl monooleate, monoelaidin, polyethylene glycol, 3-methyl-1,5-dihydroxypentane, dihydroxyneopentyl, 2-ethyl-1,2-dihydroxyhexane, and 2-methyl-1,3-dihydroxypropane (corresponding to component (C11) constituting component (B1) above).

[0099] Polyfunctional polyols (corresponding to the above-mentioned component (CB)) such as glycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, trimethylolpropane tripolyoxyethylene ether (for example, TMP-30, TMP-60, TMP-90, etc., manufactured by Nippon Nyukazai Co., Ltd.), butanetriol, 1,2-methylglucoside, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, erythritol, threitol, ribitol, arabinitol, xylitol, allitol, mannitol, dolcitol, iditol, glycol, inositol, hexanetriol, triglycerol, diglycerol, and triethylene glycol.

[0100] Alicyclic alcohol; component (C) Hydrogenated bisphenol A, cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, tricyclo[5,2,1,0 2,6 ]decane-dimethanol, bicyclo[4,3,0]-nonanediol, dicyclohexanediol, tricyclo[5,3,1,13,9]dodecanediol, bicyclo[4,3,0]nonanedimethanol, tricyclo[5,3,1,1 3,9 ]dodecane-diethanol, hydroxypropyltricyclo〔5,3,1,1 3,9 ]dodecanol, spiro[3,4]octanediol, butylcyclohexanediol, 1,1'-bicyclohexylidenediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, and bifunctional polyols such as o-dihydroxyxylylene (corresponding to component (C11) constituting component (B1)).

[0101] Polyfunctional polyols such as tris(2-hydroxyethyl) isocyanurate, cyclohexanetriol, sucrose, maltitol, and lactitol (corresponding to the above-mentioned component (CB)).

[0102] Aromatic alcohol; component (C) Dihydroxynaphthalene, dihydroxybenzene, bisphenol A, bisphenol F, xylylene glycol, tetrabromobisphenol A, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)-1-naphthylmethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2-(4-hydroxyphenyl) 2,2-bis(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)-3-methylbutane, 2,2-bis(4-hydroxyphenyl)pentane, 3,3-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)hexane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 2,2-bis(4-hydroxyphenyl)hexane butane, 4,4-bis(4-hydroxyphenyl)heptane, 2,2-bis(4-hydroxyphenyl)tridecane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3-ethyl-4-hydroxyphenyl)propane, 2,2-bis(3-n-propyl-4-hydroxyphenyl)propane, 2,2-bis(3-isopropyl-4-hydroxyphenyl)propane, 2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane, 2,2-bis(3- tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2-bis(3-allyl-4'-hydroxyphenyl)propane, 2,2-bis(3-methoxy-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(2,3,5,6-tetramethyl-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)cyanomethane, 1-cyano-3,3-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cycloheptane, 1,1-bis(3-methyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dichloro-4-hydroxyphenyl)cyclohexane, 1,1-bis(3-methyl-4-hydroxyphenyl)-4-methylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)norbornane, 2,2-bis(4-hydroxyphenyl)adamantane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, ethylene glycol bis(4-hydroxyphenyl) ether, 4,4'- Dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide, 3,3'-dicyclohexyl-4,4'-dihydroxydiphenyl sulfide, 3,3'-diphenyl-4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, bis(4-hydroxyphenyl) ketone, bis(4-hydroxy-3-methylphenyl) ketone, 7,7' -Dihydroxy-3,3',4,4'-tetrahydro-4,4,4',4'-tetramethyl-2,2'-spirobi(2H-1-benzopyran), trans-2,3-bis(4-hydroxyphenyl)-2-butene, 9,9-bis(4-hydroxyphenyl)fluorene, 3,3-bis(4-hydroxyphenyl)-2-butanone, 1,6-bis(4-hydroxyphenyl)-1,6-hexanedione, 4,4'-dihydroxybiphenyl, m-dihydroxyxylylene, p-dihydroxyxylylene, 1,4-bis(2-hydroxyethyl)benzene, 1,4-bis(3-hydroxypropyl)benzene, 1,4-bis(4-hydroxybutyl)benzene, 1,4-bis(5-hydroxypentyl)benzene, 1,4-bis(6-hydroxyhexyl)benzene, 2,2-bis[4-(2''-hydroxyethyloxy)phenyl]propane, and bifunctional polyols such as hydroquinone and resorcinol (corresponding to the component (C11) constituting the component (B1)).

[0103] Polyfunctional polyols such as trihydroxynaphthalene, tetrahydroxynaphthalene, benzenetriol, biphenyltetraol, pyrogallol, (hydroxynaphthyl)pyrogallol, and trihydroxyphenanthrene (corresponding to the above-mentioned component (CB)).

[0104] Polyester polyol; component (C) Examples include compounds obtained by a condensation reaction between a polyol and a compound having multiple carboxylic acids. Among these, the number average molecular weight is preferably 400 to 2000, more preferably 500 to 1500, and most preferably 600 to 1200. Note that compounds having hydroxyl groups only at both ends of the molecule (two hydroxyl groups per molecule) correspond to the component (C11) constituting the component (B1), and compounds having three or more hydroxyl groups per molecule correspond to the component (CB).

[0105] Examples of the polyol include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 3,3'-dimethylolheptane, 1,4-cyclohexanedimethanol, neopentyl glycol, 3,3-bis(hydroxymethyl)heptane, diethylene glycol, dipropylene glycol, glycerin, and trimethylolpropane. These may be used alone or in combination of two or more. Examples of the compound having multiple carboxylic acids include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid, orthophthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. These may be used alone or in combination of two or more.

[0106] These polyester polyols are available as reagents or industrially, and examples of commercially available products include the "Polylite (registered trademark)" series manufactured by DIC Corporation, the "Nippolan (registered trademark)" series manufactured by Nippon Polyurethane Industry Co., Ltd., the "Maximol (registered trademark)" series manufactured by Kawasaki Chemical Industries, Ltd., and the "Kuraray Polyol (registered trademark)" series manufactured by Kuraray Co., Ltd.

[0107] Polyether polyol; component (C) Examples include compounds obtained by ring-opening polymerization of alkylene oxide, or by the reaction of a compound having two or more active hydrogen groups in the molecule with an alkylene oxide, and modified products thereof. Among these, the number average molecular weight is preferably 400 to 2000, more preferably 500 to 1500, and most preferably 600 to 1200. Note that those having hydroxyl groups only at both ends of the molecule (two in the molecule) correspond to the component (C11) constituting the component (B1), and those having three or more hydroxyl groups in the molecule correspond to the component (CB).

[0108] Examples of the polyether polyols include polymer polyols, urethane-modified polyether polyols, and polyether ester copolymer polyols. Examples of the compounds having two or more active hydrogen groups in the molecule include water, ethylene glycol, propylene glycol, butanediol, glycerin, trimethylolpropane, hexanetriol, triethanolamine, diglycerin, pentaerythritol, trimethylolpropane, hexanetriol, and other polyol compounds having one or more hydroxyl groups in the molecule, such as glycols and glycerin. These may be used alone or in combination of two or more.

[0109] Examples of the alkylene oxide include cyclic ether compounds such as ethylene oxide, propylene oxide, and tetrahydrofuran, and these may be used alone or in combination of two or more.

[0110] Such polyether polyols are available as reagents or industrially, and examples of commercially available polyether polyols include the "EXCENOL (registered trademark)" series and "EMALSTAR (registered trademark)" manufactured by Asahi Glass Co., Ltd., and the "ADEKA POLYETHER" series manufactured by ADEKA Corporation.

[0111] Polycaprolactone polyol; component (C) Examples include compounds obtained by ring-opening polymerization of ε-caprolactone. Among these, the number average molecular weight is preferably 400 to 2000, more preferably 500 to 1500, and most preferably 600 to 1200. Note that compounds having hydroxyl groups only at both ends of the molecule (two hydroxyl groups per molecule) correspond to the component (C11) constituting the component (B1), and compounds having three or more hydroxyl groups per molecule correspond to the component (CB).

[0112] These polycaprolactone polyols are available as reagents or industrially, and examples of commercially available products include the "Placcel (registered trademark)" series manufactured by Daicel Chemical Industries, Ltd.

[0113] Polycarbonate polyol; component (C) Examples include compounds obtained by phosgenating one or more low-molecular-weight polyols, and compounds obtained by transesterification with ethylene carbonate, diethyl carbonate, diphenyl carbonate, etc. Among these, the number-average molecular weight is preferably 400 to 2000, more preferably 500 to 1500, and most preferably 600 to 1200. Note that those having hydroxyl groups only at both ends of the molecule (two in the molecule) correspond to the component (C11) constituting the component (B1), and those having three or more hydroxyl groups in the molecule correspond to the component (CB).

[0114] Examples of the low molecular weight polyol include low molecular weight polyols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 3-methyl-1,5-pentanediol, 2-ethyl-4-butyl-1,3-propanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, diol dimer acid, ethylene oxide and propylene oxide adducts of bisphenol A, bis(β-hydroxyethyl)benzene, xylylene glycol, glycerin, trimethylolpropane, and pentaerythritol.

[0115] Polyacrylic polyol; component (C) Examples include polyol compounds obtained by polymerizing (meth)acrylate esters or vinyl monomers. Those having hydroxyl groups only at both ends of the molecule (two hydroxyl groups per molecule) correspond to the component (C11) constituting the component (B1), and those having three or more hydroxyl groups per molecule correspond to the component (CB).

[0116] Castor oil-based polyol; component (C) Castor oil-based polyols include polyol compounds made from castor oil, a natural fat and oil, as a starting material. Those having hydroxyl groups only at both ends of the molecule (two hydroxyl groups per molecule) fall under the category of component (C11) constituting component (B1), while those having three or more hydroxyl groups per molecule fall under the category of component (CB).

[0117] These castor oil polyols are available as reagents or industrially, and examples of commercially available products include the "URIC (registered trademark)" series manufactured by Ito Oil Mills, Ltd.

[0118] (C) a compound having two or more thiol groups; (C) component Among the compounds of component (C), those having a thiol group that can be used are those described in International Publication No. WO2015 / 068798. Among these, particularly preferred examples include the following:

[0119] Tetraethylene glycol bis(3-mercaptopropionate), 1,4-butanediol bis(3-mercaptopropionate), 1,6-hexanediol bis(3-mercaptopropionate), 1,4-bis(mercaptopropylthiomethyl)benzene (corresponding to component (C11) which constitutes component (B1) above).

[0120] Trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), 1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane, 2,2-bis(mercaptomethyl)-1,4-butanedithiol, 2,5-bis(mercaptomethyl)-1,4-dithiane, 4-mercaptomethyl thiols (corresponding to the above-mentioned component (CB)), such as 1,8-dimercapto-3,6-dithiaoctane, 1,1,1,1-tetrakis(mercaptomethyl)methane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, and tris-{(3-mercaptopropionyloxy)ethyl}isocyanurate.

[0121] OH / SH type polymerizable group-containing monomer; component (C) Among the components (C), compounds containing both a hydroxyl group and a thiol group include the following.

[0122] 2-mercaptoethanol, 1-hydroxy-4-mercaptocyclohexane, 2-mercaptohydroquinone, 4-mercaptophenol, 1-hydroxyethylthio-3-mercaptoethylthiobenzene, 4-hydroxy-4'-mercaptodiphenyl sulfone, 2-(2-mercaptoethylthio)ethanol, dihydroxyethyl sulfide mono(3-mercaptopropionate), dimercaptoethane mono(saltylate) (corresponding to component (C11) which constitutes component (B1) above).

[0123] Polyfunctional OH / SH type polymerizable group-containing monomers (corresponding to the above-mentioned component (CB)) such as 3-mercapto-1,2-propanediol, glycerin di(mercaptoacetate), 2,4-dimercaptophenol, 1,3-dimercapto-2-propanol, 2,3-dimercapto-1-propanol, 1,2-dimercapto-1,3-butanediol, pentaerythritol tris(3-mercaptopropionate), pentaerythritol mono(3-mercaptopropionate), pentaerythritol bis(3-mercaptopropionate), pentaerythritol tris(thioglycolate), pentaerythritol pentakis(3-mercaptopropionate), hydroxymethyl-tris(mercaptoethylthiomethyl)methane, and hydroxyethylthiomethyl tris(mercaptoethylthio)methane.

[0124] A cyclic molecule containing three or more hydroxyl and / or thiol groups in a side chain; (CB) component The side chain-containing cyclic molecule is not particularly limited as long as it is a cyclic molecule having three or more side chains each having a hydroxyl group and / or a thiol group at its terminal. Examples of the cyclic molecule include cyclodextrin, crown ether, benzocrown, dibenzocrown, dicyclohexanocrown, cyclobis(paraquat-1,4-phenylene), dimethoxypillararenes, calixarenes, and phenanthrolines, among which cyclodextrin is preferred.

[0125] The cyclodextrins include α-cyclodextrins (inner ring diameter: 0.45 to 0.6 nm), β-cyclodextrins (inner ring diameter: 0.6 to 0.8 nm), and γ-cyclodextrins (inner ring diameter: 0.8 to 0.95 nm). Mixtures of these may also be used. In the present invention, α-cyclodextrin and β-cyclodextrin are particularly preferred.

[0126] Next, we will explain the side chains having hydroxyl groups and / or thiol groups at their terminals that are introduced into the cyclic molecule in at least three units. The method for introducing the side chains is not limited, but for example, they can be introduced by utilizing a reactive functional group possessed by the cyclic molecule and modifying this reactive functional group (i.e., the side chains are introduced by reacting with the reactive functional group).

[0127] Examples of such reactive functional groups include hydroxyl groups and amino groups, with hydroxyl groups being preferred. For example, α-cyclodextrin has 18 OH groups (hydroxyl groups) as reactive functional groups, and side chains are introduced by reacting with these OH groups. Therefore, a maximum of 18 side chains can be introduced into one α-cyclodextrin. In the present invention, to fully utilize the functions of the side chains described above, at least three or more side chains having hydroxyl groups and / or thiol groups introduced at their terminals must be introduced. Among these, five or more side chains having hydroxyl groups and / or thiol groups introduced at their terminals are preferred, seven or more side chains having hydroxyl groups and / or thiol groups introduced at their terminals are more preferred, and eight or more side chains having hydroxyl groups and / or thiol groups introduced at their terminals are most preferred. Side chains having terminal hydroxyl groups are particularly preferred.

[0128] The side chain is not particularly limited, but is preferably formed by repeating organic chains having a carbon number in the range of 3 to 20. The number average molecular weight of such a side chain is preferably, for example, 300 or more. More specifically, the number average molecular weight of such a side chain is in the range of 300 to 10,000, preferably 350 to 5,000, and most preferably 400 to 5,000. The number average molecular weight of this side chain can be adjusted by the amount used when introducing the side chain, and can be determined by calculation. 1 It can also be determined from H-NMR measurements.

[0129] By setting the lower limit of the number average molecular weight of the side chain as described above, excellent mechanical properties are exhibited, and when used in the CMP polishing pad of the present invention, the removal rate tends to be improved.

[0130] In the present invention, the side chain may be linear or branched. The side chain can be introduced using the methods and compounds disclosed in International Publication No. 2015 / 159875, for example, ring-opening polymerization, radical polymerization, cationic polymerization, anionic polymerization, atom transfer radical polymerization, RAFT polymerization, NMP polymerization, or other living radical polymerization. By using the above methods, a side chain of an appropriate size can be introduced by reacting an appropriately selected compound with the reactive functional group of the cyclic molecule.

[0131] Among these, ring-opening polymerization is particularly preferred, in which a cyclic compound such as a cyclic ether, a cyclic lactone, a cyclic acetal, or a cyclic carbonate is reacted with a reactive functional group of a cyclic molecule to introduce a side chain derived from the cyclic compound into the cyclic molecule.

[0132] Among the cyclic compounds, it is preferable to use cyclic ethers, cyclic lactones, and cyclic carbonates, from the viewpoints of high reactivity and ease of molecular weight adjustment.

[0133] Examples of suitable cyclic ethers, cyclic lactones, and cyclic carbonates are given below.

[0134] cyclic ethers; Ethylene oxide, 1,2-propylene oxide, epichlorohydrin, epibromohydrin, 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide, oxetane, 3-methyloxetane, 3,3-dimethyloxetane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, etc.

[0135] cyclic lactones; Four-membered ring lactones: β-propiolactone, β-methylpropiolactone, L-serine-β-lactone, etc. Five-membered ring lactones; γ-butyrolactone, γ-hexanolactone, γ-heptanolactone, γ-octanolactone, γ-decanolactone, γ-dodecanolactone, α-hexyl-γ-butyrolactone, α-heptyl-γ-butyrolactone, α-hydroxy-γ-butyrolactone, γ-methyl-γ-decanolactone, α-methylene-γ-butyrolactone, α,α-dimethyl-γ-butyrolactone, D-erythronolactone, α-methyl α-methyl-γ-butyrolactone, γ-nonanolactone, DL-pantolactone, γ-phenyl-γ-butyrolactone, γ-undecanolactone, γ-valerolactone, 2,2-pentamethylene-1,3-dioxolan-4-one, α-bromo-γ-butyrolactone, γ-crotonolactone, α-methylene-γ-butyrolactone, α-methacryloyloxy-γ-butyrolactone, β-methacryloyloxy-γ-butyrolactone, etc. 6-membered ring lactones; δ-valerolactone, δ-hexanolactone, δ-octanolactone, δ-nonanolactone, δ-decanolactone, δ-undecanolactone, δ-dodecanolactone, δ-tridecanolactone, δ-tetradecanolactone, DL-mevalonolactone, 4-hydroxy-1-cyclohexanecarboxylic acid δ-lactone, monomethyl-δ-valerolactone, monoethyl-δ-valerolactone, monohexyl-δ-valerolactone, 1,4-dioxan-2-one, 1,5-dioxepan-2-one, etc. Seven-membered ring lactones; ε-caprolactone, monomethyl-ε-caprolactone, monoethyl-ε-caprolactone, monohexyl-ε-caprolactone, dimethyl-ε-caprolactone, di-n-propyl-ε-caprolactone, di-n-hexyl-ε-caprolactone, trimethyl-ε-caprolactone, triethyl-ε-caprolactone, tri-n-ε-caprolactone, ε-caprolactone, 5-nonyl-oxepan-2-one, 4,4,6-trimethyl-oxepan-2-one, 4,6,6-trimethyl-oxepan-2-one, 5-hydroxymethyl-oxepan-2-one, etc. 8-membered lactones; ζ-enantholactone, etc. Other lactones: lactone, lactide, dilactide, tetramethylglycoside, 1,5-dioxepan-2-one, t-butylcaprolactone, etc.

[0136] cyclic carbonates; Ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, glycerol 1,2-carbonate, 4-(methoxymethyl)-1,3-dioxolan-2-one, (chloromethyl)ethylene carbonate, vinylene carbonate, 4,5-dimethyl-1,3-dioxol-2-one, 4-chloromethyl-5-methyl-1,3-dioxol-2-one, 4-vinyl-1,3-dioxolan-2-one, 4,5-diphenyl-1,3-dioxolan-2-one, 4,4-dimethyl-5-methylene-1,3-dioxolan-2-one, 1,3-dioxan-2-one, 5-methyl-5-propyl-1,3-dioxolan-2-one, 5,5-diethyl-1,3-dioxolan-2-one The above cyclic compounds can be used alone or in combination of two or more kinds.

[0137] In the present invention, the cyclic compound preferably used is a lactone compound, and particularly preferred lactone compounds are lactone compounds such as ε-caprolactone, α-acetyl-γ-butyrolactone, α-methyl-γ-butyrolactone, γ-valerolactone, and γ-butyrolactone, and most preferred is ε-caprolactone.

[0138] Furthermore, when introducing a side chain by reacting a cyclic compound by ring-opening polymerization, the reactive functional group (e.g., hydroxyl group) of the cyclic molecule may have poor reactivity, making it difficult to directly react a larger molecule, particularly due to steric hindrance. In such cases, a suitable method is to first react a low molecular weight compound such as propylene oxide with the reactive functional group of the cyclic molecule to hydroxypropylate it, thereby introducing a highly reactive functional group in advance, in order to react with the aforementioned caprolactone, etc. Then, a method can be adopted in which a side chain is introduced by ring-opening polymerization using the aforementioned cyclic compound. In this case, the hydroxypropylated portion can also be considered a side chain.

[0139] Polyrotaxane having a hydroxyl group and / or a thiol group; component (C) A polyrotaxane is a molecular complex, also known as a supramolecule, in which a chain-like axial molecule penetrates the rings of multiple cyclic molecules, and bulky groups are attached to both ends of the axial molecule, preventing the cyclic molecules from escaping from the axial molecule due to steric hindrance. Polyrotaxanes that can be used in component (C) of the present invention are polyrotaxanes having hydroxyl and / or thiol groups polymerizable with isocyanate groups, and those having three or more hydroxyl and / or thiol groups correspond to the aforementioned component (CB). The polyrotaxanes having hydroxyl and / or thiol groups that can be used in component (C) of the present invention are not particularly limited, but examples include the polyrotaxanes described in International Application Publication No. 2018 / 092826.

[0140] Among the (CB) components used in the present invention, preferred are glycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, trimethylolpropane tripolyoxyethylene ether (TMP-30 from Nippon Nyukazai Co., Ltd.), polyester polyols having three or more hydroxyl groups, polyether polyols having three or more hydroxyl groups, castor oil-based polyols having three or more hydroxyl groups, side chain-containing cyclic molecules having three or more hydroxyl groups, and polyrotaxanes having hydroxyl groups and / or thiol groups, of which side chain-containing cyclic compounds having three or more hydroxyl groups and polyrotaxanes having three or more hydroxyl groups and / or thiol groups are more preferred, and from the viewpoint of handleability, side chain-containing cyclic molecules having three or more hydroxyl groups are most preferred.

[0141] <Composition ratio of component (B) and component (C)> In the present invention, the blending ratio of components (B) and (C) is not particularly limited. To achieve excellent effects, it is preferable that the total number of moles of active hydrogen groups in component (C) be 0.8 to 2.0 moles when the total number of iso(thio)cyanate groups in component (B) is 1 mole. If the iso(thio)cyanate groups are too high or too low, the resulting polyurethane resin tends to be prone to poor curing and reduced abrasion resistance. To obtain a polyurethane resin with a better, more uniform curing state and excellent abrasion resistance, it is more preferable that the total number of moles of active hydrogen groups be 0.85 to 1.75 moles, and even more preferably 0.9 to 1.5 moles, when the total number of iso(thio)cyanate groups is 1 mole. When calculating the total number of moles of active hydrogen groups in component (C), if a compound (CA) having two or more amino groups is used, the number of moles of active hydrogen in the compound having two or more amino groups is considered to be equal to the number of moles of amino groups.

[0142] Furthermore, in the present invention, in order to exhibit excellent polishing properties, as described above, component (C) preferably contains component (CA), and more preferably contains component (CA) and component (CB).

[0143] That is, in the present invention, the composition for producing the polyurethane resin preferably contains the component (B) and the component (CA), and more preferably contains the component (B), the component (CA), and the component (CB).

[0144] For example, when the (B), (CA), and (CB) components are contained, the respective blending proportions are preferably 60 to 95 parts by mass of the (B), (CA), and (CB) components, 2 to 20 parts by mass of the (CA), and 1 to 30 parts by mass of the (CB) component per 100 parts by mass of the (B), (CA), and (CB) components combined, and more preferably 70 to 85 parts by mass of the (B), (CA), and 3 to 25 parts by mass of the (CB) component.

[0145] <Other ingredients> As other compounding components used in the present invention, various known compounding agents can be used within the scope that does not impair the effects of the present invention. For example, curing catalysts, abrasive grains, surfactants, flame retardants, plasticizers, fillers, antistatic agents, foam stabilizers, solvents, leveling agents, and other additives may be added. These additives may be used alone or in combination of two or more.

[0146] As the curing catalyst, a urethane or urea reaction catalyst can be used to rapidly accelerate the curing. Specific examples of the urethane or urea reaction catalyst that can be suitably used in the present invention include those described in WO 2015 / 068798.

[0147] These urethane or urea reaction catalysts can be used either alone or in combination of two or more. The amount used may be a so-called catalytic amount, for example, in the range of 0.001 to 10 parts by mass, particularly 0.01 to 5 parts by mass, per 100 parts by mass of the total of components (B) and (C).

[0148] Examples of the abrasive grains include particles made of a material selected from cerium oxide, silicon oxide, alumina, silicon carbide, zirconia, iron oxide, manganese dioxide, titanium oxide, and diamond, or particles made of two or more of these materials. [Example]

[0149] Next, the present invention will be described in detail using examples and comparative examples, but the present invention is not limited to these examples. The components and evaluation methods used in the following examples and comparative examples are as follows.

[0150] [Evaluation method] The obtained hollow microparticles were analyzed using a field emission scanning electron microscope (JEOL Ltd., JSM-7800FPrime) and electron micrographs thereof were analyzed using image analysis software ImageJ (National Institutes of Health).

[0151] Example 1 As the aqueous phase, 1.5 g of ethylene-maleic anhydride copolymer (average molecular weight 100,000-500,000, manufactured by Aldrich) as a surfactant was dissolved in 50 g of distilled water while heating, and the pH was then adjusted with 5 ml of 10% aqueous sodium hydroxide solution to prepare an acidic aqueous solution at 65°C and pH 4. 20 g of toluene as an oil phase was added to the aqueous phase, and the mixture was stirred with a homogenizer at 1500 rpm for 10 minutes to prepare an O / W emulsion at 45°C and pH 4. As an additive phase, 4.54 g of melamine, 11.69 ml of 37% formaldehyde aqueous solution, and 7.12 g of distilled water were mixed at 70 ° C., and then the pH was adjusted using 5 ml of 10% sodium hydroxide aqueous solution to allow an addition reaction of formaldehyde with melamine. An alkaline aqueous solution of methylol melamine at 70 ° C. and pH 12 was then prepared, and this was added to the O / W emulsion obtained above. After that, a 10% citric acid aqueous solution was added to confirm that the pH was 4 or less. The mixture was stirred and mixed at 300 rpm while reacting at a liquid temperature of 80 ° C. for 3 hours to produce microparticles. The resulting microparticles were centrifuged at 8000 rpm for 15 minutes 10 times to remove the aqueous phase, and then further vacuum dried for 48 hours to obtain hollow microparticles. As shown in Figure 2, when the obtained hollow microparticles were examined with a field emission scanning electron microscope, it was confirmed that the hollow microparticles were characterized by a resin film consisting of a plurality of small platelet-like portions and connecting portions connecting them. Furthermore, the results of image analysis showed that the average particle diameter of the hollow microparticles was 23.8 μm, with a standard deviation of particle diameter of 6.9. The longest diameter of the small platelet-like portions was 9 μm. Furthermore, as shown in Figure 2, the appearance of the obtained hollow microparticles was good. The bulk density of the obtained hollow microparticles was 0.3 g / cm. 3 Table 1 shows the ingredients used and the results.

[0152] <Comparative Example 1> Hollow microparticles were obtained in the same manner as in Example 1, except that the blending amounts shown in Table 1 were used. The obtained hollow microparticles were examined using a field emission scanning electron microscope, and it was confirmed that the resin film had no specific structure and that they were ordinary hollow microparticles. Image analysis revealed that the average particle size was 28.1 μm with a standard deviation of 8.1. Furthermore, Figure 3 confirms that the obtained hollow microparticles had holes in their appearance. The bulk density of the obtained hollow microparticles was 0.3 g / cm 3 The results are shown in Table 1.

[0153] [Table 1]

[0154] As described above, the hollow microparticles of Example 1 had a resin film composed of a plurality of small pieces and a bonding portion bonding them together. Furthermore, since the resin film of the hollow microparticles of Example 1 was a melamine-based resin, the particles had excellent heat resistance and solvent resistance, a large average particle diameter of 23.8 μm, and a small standard deviation of particle diameter of 6.9, resulting in excellent dispersibility. Furthermore, the particles had a good appearance and excellent stability. On the other hand, no small platelet-like portions were observed in the hollow microparticles of Comparative Example 1. The standard deviation of the particle size of the hollow microparticles of Comparative Example 1 was 8.1, which was a larger value than that of the hollow microparticles of Example 1, indicating poor dispersibility. Furthermore, holes were observed in the appearance, indicating poor stability.

[0155] (B) Component Pre-1: urethane prepolymer with a terminal isocyanate and an iso(thio)cyanate equivalent of 905; component (B1) (Pre-1 manufacturing method) In a flask equipped with a nitrogen inlet tube, a thermometer, and a stirrer, 50 g of 2,4-tolylene diisocyanate, 90 g of polyoxytetramethylene glycol (number average molecular weight: 1000), and 12 g of diethylene glycol were reacted at 80°C for 6 hours under a nitrogen atmosphere to obtain a terminal isocyanate urethane prepolymer with an iso(thio)cyanate equivalent of 905 (Pre-1 was obtained). (C) Component CB-1: A cyclic molecule with nine hydroxyl groups at the end of the side chain; (CB) component (CB-1 manufacturing method) 10 g of hydroxypropylated β-cyclodextrin (CycloChem Co., Ltd.) and 32.0 g of ε-caprolactone were stirred at 130°C while flowing dry nitrogen to form a homogeneous solution, and then 0.04 g of tin(II) 2-ethylhexanoate was added and reacted for 16 hours to obtain the target cyclic molecule (CB-1) with nine hydroxyl groups at the side chain terminals. The physical properties of CB-1 were as follows: Weight average molecular weight Mw (GPC): 4800 Dispersion degree (GPC): 1.05 Side chain modification degree: 0.43 (43% when expressed as a percentage) Polymerizable group at the end of the side chain: hydroxyl group Number of side chains introduced into the cyclic molecule: 9 Side chain molecular weight: Number average molecular weight approximately 550 Viscosity: 3,800mPa·s Residual tin content: 300 ppm

[0156] [Measurement method] (1) Density: Density (g / cm) measured using a Toyo Seiki (DSG-1) 3 ) was measured.

[0157] (2) Shore D hardness: Shore D hardness was measured using a durometer manufactured by Kobunshi Keiki Co., Ltd. in accordance with JIS standard (hardness test) K6253. The samples were stacked to a thickness of 6 mm and measured. Relatively low hardness samples were measured using Shore A hardness, and relatively high hardness samples were measured using Shore D hardness.

[0158] (3) Hysteresis loss: The resin was punched into a No. 8 dumbbell shape with a thickness of 2 mm and stretched 20 mm at 10 mm / min using an autograph of Shimadzu AG-SX. Then, the hysteresis loss was measured when the resin was returned to zero stress.

[0159] (4) Polishing rate: The polishing rate was measured under the following conditions. The polishing rate is the average value for three 2-inch sapphire wafers. CMP polishing pad: A pad with a diameter of 300 mm and a thickness of 1 mm, with concentric grooves formed on the surface Slurry: FUJIMI Compol 80 concentrate Pressure: 0.7 psi Rotation speed: 45 rpm Time: 1 hour

[0160] (5) Scratches: The presence or absence of scratches on the wafer when polished under the conditions described in (4) above was confirmed. Evaluation was carried out according to the following criteria. 1: All three sheets are free of scratches when viewed under a laser microscope 2: Only one sheet has a scratch that can be seen with a laser microscope 3: Scratches can be seen on both sheets using a laser microscope 4: Scratches were visible on all three sheets using a laser microscope

[0161] <Example 2> 12.5 parts by weight of CB-1, the (CB) component prepared above, and 5.7 parts by weight of 4,4'-methylenebis(o-chloroaniline) (MOCA), the (CA) component, were mixed at 120°C to form a homogeneous solution, which was then thoroughly degassed to prepare Liquid A. Separately, 81.8 parts by weight of Pre-1, the (B1) component prepared above, was heated to 70°C and 10 parts by weight of the hollow microparticles of Example 1 was added. The mixture was stirred with a planetary centrifugal mixer to prepare a homogeneous solution of Liquid B. Liquid A was added to the prepared Liquid B and mixed homogeneously to form a curable composition. The curable composition was poured into a mold, degassed under a reduced pressure of 5 kPa for 2 minutes, and then cured at 100°C for 15 hours. After curing, the mixture was removed from the mold to obtain a cured product.

[0162] Next, the obtained cured body was sliced ​​to prepare cured bodies of 2 mm and 1 mm thickness. The above-mentioned various physical properties were measured using the 2 mm thick cured body obtained by slicing. The density of the obtained cured body was 1.0 g / cm. 3 The Shore D hardness was 32D and the hysteresis loss was 25%.

[0163] In addition, a spiral groove was formed on the surface of the 1 mm thick hardened body obtained by slicing, and double-sided tape was attached to the backside to create a polishing pad made from the hardened body with a size of 300 mmφ and a thickness of 1 mm.

[0164] The polishing rate of the polishing pad made of the cured product obtained above was 1.7 μm / hr, and the scratch rating was 1. The results are shown in Table 2.

[0165] <Comparative Example 2> A cured body was produced in the same manner as in Example 2, except that 0.8 parts by mass of commercially available Microcapsule 920-40 (manufactured by Nippon Phillite Co., Ltd., hollow microparticles made of acrylonitrile resin with inorganic powder dusted on the surface) was used instead of the hollow microparticles in Example 2. The density of the obtained cured body was 0.8 g / cm. 3 The Shore D hardness was 24D, and the hysteresis loss was 31%. The hollow microparticles used in Comparative Example 2 did not have small platelet-like portions in the resin film.

[0166] <Comparative Example 3> A hardened body was produced in the same manner as in Example 2, except that the hollow microparticles of Comparative Example 1 were used instead of the hollow microparticles of Example 2. The density of the hardened body obtained was 1.05 g / cm. 3 The Shore D hardness was 33D and the hysteresis loss was 27%. The hollow microparticles used in Comparative Example 3 did not have small platelet-like portions in the resin film.

[0167] In addition, a spiral groove was formed on the surface of the 1 mm thick hardened body obtained by slicing, and double-sided tape was attached to the backside to create a polishing pad made from the hardened body with a size of 300 mmφ and a thickness of 1 mm.

[0168] The polishing rate of the polishing pad made of the cured product obtained above was 1.2 μm / hr, and the number of scratches was 1. The results are shown in Table 2.

[0169] [Table 2] [Explanation of symbols]

[0170] 1a, 1b: Microscopic hollow particles 2: Small pieces 3:Joining part

Claims

1. The hollow microparticles are made of a resin film made of a melamine-based resin, the resin film being composed of a plurality of small piece-like portions and bonding portions that bond the small piece-like portions together, and the hollow microparticles made of the resin film made of a melamine-based resin have a particle size of 10 μm to 100 μm.

2. 2. The hollow microparticle according to claim 1, wherein the small plate-like portions have at least one shape selected from the group consisting of a substantially circular plate shape, a substantially oval spherical shape, and a substantially spherical shape.

3. 3. The hollow microparticle according to claim 1, wherein the longest diameter of the small platelet-like portions is 1 μm to 20 μm.

4. A cured product obtained by dispersing the hollow microparticles according to any one of claims 1 to 3 in a polyurethane resin.

5. A CMP polishing pad comprising the cured product according to claim 4.

6. A method for producing hollow microparticles composed of a resin film made of a melamine-based resin, comprising: First step: (a) providing an oil phase of an organic solvent; Second step: (b) providing an aqueous phase containing a surfactant; A third step: mixing and stirring the oil phase and the aqueous phase to prepare an O / W emulsion in which the aqueous phase is a continuous phase and the oil phase is a dispersed phase; a fourth step: adding a melamine formaldehyde prepolymer compound as an additive phase to the O / W emulsion, and allowing a condensation reaction of the methylolated melamine, which is the melamine formaldehyde prepolymer compound, to proceed on the interface of the O / W emulsion to form a resin film into fine particles, thereby obtaining a fine particle dispersion in which the fine particles are dispersed; Fifth step: separating the microparticles from the microparticle dispersion; Sixth step: A method for producing hollow microparticles, the method including a step of removing an oil phase from the interior of the fine particles to form hollow microparticles, wherein the weight ratio of the (a) oil phase of the organic solvent [component (a)] to the (b) aqueous phase containing a surfactant [component (b)] is 100 to 500 parts by mass of component (b) when component (a) is taken as 100 parts by mass, and the particle size of the hollow microparticles composed of a resin film made of a melamine-based resin is 10 μm to 100 μm.

7. 7. The method according to claim 6, wherein the organic solvent used in the oil phase of the organic solvent (a) is selected from organic solvents having a boiling point of 100°C to 180°C.

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