Novel fine hollow particles formed from melamine-based resin

Abstract

The minute hollow particles of the present application are characterized in that they are minute hollow particles composed of a resin film formed of a melamine-based resin, the aforementioned resin film being composed of a plurality of small plate-like portions and a binding portion binding them. According to the present application, minute hollow particles having excellent solvent resistance, heat resistance, good dispersibility, a large particle diameter, and stability can be provided.

Description

Technical Field

[0001] This invention relates to novel micro-hollow particles formed from melamine-based resins. Background Technology

[0002] Tiny hollow particles are used in numerous fields, including pesticides, pharmaceuticals, fragrances, liquid crystals, adhesives, electronic components, and building materials. In recent years, in particular, tiny hollow particles have been studied for the purpose of creating fine pores in polyurethane (urea) CMP (Chemical Mechanical Polishing) grinding pads used in wafer polishing. These tiny hollow particles require excellent solvent resistance, heat resistance, and therefore optimal particle size control. Specifically, in the field of CMP grinding pads, relatively large, monodisperse tiny hollow particles of approximately 20–50 μm are ideal for achieving high polishing rates and atomic-level flatness.

[0003] Therefore, Patent Document 1 discloses a method for manufacturing tiny hollow particles formed from melamine resin, a thermosetting resin with excellent heat resistance and solvent resistance.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 7-41594 Summary of the Invention

[0007] The problem the invention aims to solve

[0008] However, while the method in Patent Document 1 has excellent heat resistance and solvent resistance, there are issues from the perspective of controlling particle size and its dispersibility.

[0009] Therefore, the object of the present invention is to provide a novel type of micro hollow particles that can be easily manufactured to have excellent solvent resistance, heat resistance, good dispersibility, and large particle size and stability.

[0010] Solution for solving the problem

[0011] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that novel micro hollow particles can solve the above-mentioned problems. The novel micro hollow particles are composed of a resin film formed from melamine-based resin, and the resin film is composed of a plurality of small sheet-like portions and a bonding portion that binds them together, thus completing the present invention.

[0012] That is, the present invention relates to the following [1] to [8].

[0013] [1] A type of small hollow particle, characterized in that it is a small hollow particle composed of a resin film formed by melamine resin, wherein the resin film is composed of a plurality of small sheet-like portions and a bonding portion that binds them together.

[0014] [2] According to the above [1], the small hollow particles are selected from at least one shape selected from the group consisting of a generally circular plate, a generally ellipsoidal sphere, and a generally spherical shape.

[0015] [3] According to the above [1] or [2], the longest diameter of the aforementioned small plate-like portion is 1 μm to 20 μm.

[0016] [4] The micro hollow particles according to any one of [1] to [3] above, wherein the particle size of the micro hollow particles composed of the resin film formed by the aforementioned melamine resin is 10 μm to 100 μm.

[0017] [5] A cured product, which is formed by dispersing tiny hollow particles in polyurethane resin as described in any one of [1] to [4].

[0018] [6] A CMP abrasive pad comprising the cured material described in [5] above.

[0019] [7] A method for manufacturing micro hollow particles, comprising manufacturing micro hollow particles composed of a resin film formed from a melamine-based resin, wherein the micro hollow particles are manufactured by a method including the following steps:

[0020] Step 1: (a) A step of preparing the oil phase of the organic solvent; Step 2: (b) A step of preparing the aqueous phase containing the surfactant; Step 3: A step of mixing / stirring the aforementioned oil phase and aqueous phase to prepare an O / W emulsion in which the aforementioned aqueous phase is the continuous phase and the aforementioned oil phase is the dispersed phase; Step 4: A step of adding a melamine-formaldehyde prepolymer compound as an additive phase to the aforementioned O / W emulsion, and carrying out a condensation reaction of hydroxymethylated melamine as the melamine-formaldehyde prepolymer compound at the interface of the aforementioned O / W emulsion. The process includes: forming a resin film, producing microparticles, and obtaining a microparticle dispersion containing microparticles; step 5: separating microparticles from the aforementioned microparticle dispersion; step 6: removing the oil phase from the interior of the aforementioned microparticles to produce micro hollow particles; and further, the weight ratio of the aforementioned (a) organic solvent oil phase [(a) component] to (b) aqueous phase containing surfactant [(b) component] is: when (a) component is set to 100 parts by mass, (b) component is 100 to 500 parts by mass.

[0021] [8] According to the manufacturing method described above [7], the organic solvent used in the oil phase of the aforementioned (a) organic solvent is selected from organic solvents with a boiling point of 100°C to 180°C.

[0022] The effects of the invention

[0023] The characteristic of the micro hollow particles of the present invention is that they are micro hollow particles composed of a resin film formed from a melamine-based resin, wherein the resin film is composed of multiple small sheet-like portions and bonding portions that bind them together. By forming such a structure, it is possible to easily produce micro hollow particles with good dispersibility, large particle size, and stability. Attached Figure Description

[0024] Figure 1 These are field emission scanning electron microscope images illustrating the morphology of the tiny hollow particles used in this invention.

[0025] Figure 2 These are field emission scanning electron microscope images of the tiny hollow particles obtained in Example 1.

[0026] Figure 3 These are field emission scanning electron microscope images of the tiny hollow particles obtained in Comparative Example 1. Detailed Implementation

[0027] The characteristic of the micro hollow particles of the present invention is that they are micro hollow particles composed of a resin film formed from melamine-based resin, wherein the resin film is composed of a plurality of small sheet-like portions and bonding portions that bind them together. The aforementioned resin film constitutes the outer shell (capsule shell) of the micro hollow particles.

[0028] The aforementioned resin film is formed from a melamine-based resin. Melamine-based resins are resins produced by the condensation reaction of melamine and formaldehyde, for example, as described later, by the condensation reaction of a melamine-formaldehyde prepolymer compound made from melamine and formaldehyde.

[0029] Figure 1 The morphology of the tiny hollow particles of the present invention is shown as observed by field emission scanning electron microscopy. Figure 1 In the example shown, the small sheet-like portions are roughly circular plates (1a), while the larger example shows a roughly ellipsoidal shape (1b). Specifically, in the tiny hollow particles represented by "1a" or "1b", the resin film is composed of multiple small sheet-like portions "2" and bonding portions "3" that bind them together. Furthermore, as... Figure 1 As shown, multiple small sheet-like portions "2" are dispersed in the resin film of the micro-spherical particles of the present invention, thereby forming an uneven surface in the resin film.

[0030] It is unclear whether the resin film of the tiny hollow particles of the present invention is composed of a plurality of small sheet-like portions and a bonding portion that binds them together, but the inventors have considered the following.

[0031] Typically, emulsions larger than tens of micrometers exhibit low stability during emulsion formation. Therefore, when forming tiny particles of tens of micrometers, aggregation and destruction easily occur during resin film formation, sometimes resulting in low yields. In this invention, it is hypothesized that, unlike conventional methods, two sizes of emulsion particles are formed during emulsion formation. In this case, when a shell formed by the resin film is created at the interface of the large, less stable emulsion particles, it merges with the small emulsion particles simultaneously generated in the system, thereby suppressing the aggregation and destruction of the large emulsion particles and improving the mechanical stability of the film. This leads to the hypothetical formation of tiny particles of tens of micrometers.

[0032] In this invention, the aforementioned small sheet-like portion is not particularly limited, but is preferably selected from at least one shape chosen from approximately circular plate-like, approximately ellipsoidal, or approximately spherical. Furthermore, the longest diameter of the aforementioned small sheet-like portion is preferably 1 μm to 20 μm. Microscopic hollow bodies obtained within this range can possess excellent strength. It should be noted that, in this invention, the longest diameter refers to the longest diameter between the outer edges of the aforementioned small sheet-like portion.

[0033] In this invention, the longest diameter of the small sheet-like portion refers to the average longest diameter obtained from images observed by a scanning electron microscope. Specifically, the longest diameter of at least 20 small sheet-like portions is measured and calculated as their average value.

[0034] The particle size of the micro-hollow particles of the present invention is preferably 10 to 100 μm. Within this range, excellent grinding characteristics can be exhibited, for example, when mixed in a CMP abrasive pad. Furthermore, the particle size of the aforementioned micro-hollow particles is more preferably 20 to 50 μm.

[0035] In this invention, the particle size of the micro-hollow particles refers to the average particle size obtained from images observed using a scanning electron microscope. Specifically, the particle size of at least 20 individual micro-hollow particles is measured and calculated as their average value. It should be noted that the particle size of each micro-hollow particle measured when calculating the average particle size is the longest diameter of the micro-hollow particle.

[0036] The bulk density of the tiny hollow particles of the present invention is not particularly limited, but is preferably 0.01 to 0.5 g / cm³. 3 Within this range, it can be suitable for applications such as thermal insulation materials and CMP abrasive pads.

[0037] The method for manufacturing the micro hollow particles of the present invention is not particularly limited as long as it is a method capable of manufacturing micro hollow particles with the characteristics of the present invention, and the following method is preferred.

[0038] As a method for manufacturing the micro-hollow particles of the present invention, the following method can be cited: First, an oil-in-water (O / W) emulsion (hereinafter also referred to as an O / W emulsion) is formed by an organic layer and an aqueous layer containing a surfactant. Then, a melamine-formaldehyde prepolymer compound composed of melamine and formaldehyde is added as an additive phase to the O / W emulsion. The pH is adjusted to an acidic region and the mixture is stirred under heating. A condensation reaction of hydroxymethylated melamine occurs at the droplet interface of the dispersed oil phase to form a resin film, thereby manufacturing micro-particles encapsulating the aforementioned oil phase. Then, after obtaining the micro-particles encapsulating the aforementioned oil phase by filtration, centrifugation, etc., the internal oil phase or aqueous phase is removed by vacuum drying and the micro-hollow particles are recovered. Specific examples are shown below, but the manufacturing method of the present invention is not limited thereto.

[0039] If the manufacturing method of the micro hollow particles of the present invention is further subdivided, it can be divided into the following steps: Step 1: (a) a step of preparing an oil phase of organic solvent (hereinafter also referred to as component (a)); Step 2: (b) a step of preparing an aqueous phase containing surfactant (hereinafter also referred to as component (b)); Step 3: a step of mixing / stirring the aforementioned component (a) and the aforementioned component (b) to prepare an O / W emulsion in which the aforementioned aqueous phase is the continuous phase and the aforementioned oil phase is the dispersed phase; Step 4: a step of adding a melamine-formaldehyde prepolymer compound as an additive phase to the aforementioned O / W emulsion, and carrying out a condensation reaction of hydroxymethylated melamine as the melamine-formaldehyde prepolymer compound at the interface of the aforementioned O / W emulsion to form a resin film as micro particles, thereby obtaining a micro particle dispersion containing micro particles; Step 5: a step of separating micro particles from the aforementioned micro particle dispersion; Step 6: a step of removing the oil phase from the interior of the aforementioned micro particles to produce micro hollow particles.

[0040] Step 1:

[0041] The first step is to prepare an oil phase, consisting of (a) an organic solvent, which will become the dispersed phase in the O / W emulsion.

[0042] Step 2:

[0043] The second step is to prepare an aqueous phase containing (b) surfactant and water as a continuous phase in the O / W emulsion. In the second step, the pH may also be adjusted as needed.

[0044] This process includes dissolving the surfactant (described later) in water and adjusting the pH as needed. pH adjustment can be performed using known methods.

[0045] In this invention, the amount of surfactant used is 0.1 to 10 parts by weight, preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of the aqueous phase. If it is within this range, droplet aggregation of the dispersed phase in the O / W emulsion can be avoided, and small hollow particles can be easily and efficiently obtained.

[0046] In addition, as a preferred pH, for example, when using maleic anhydride copolymer as a surfactant, the pH can be adjusted to a level where maleic anhydride is converted into carboxylic acid.

[0047] Step 3:

[0048] The third step is to mix / stir the (a) component obtained in the first step and the (b) component obtained in the second step to prepare an O / W emulsion in which (a) component is the dispersed phase and (b) component is the continuous phase.

[0049] In this invention, the method for mixing and stirring components (a) and (b) to prepare an O / W emulsion can be carried out by using a suitable and known method, taking into account the desired particle size of the small hollow particles. Furthermore, the temperature and pH can be adjusted during the O / W emulsion preparation process.

[0050] In this process, after mixing components (a) and (b), dispersion can be carried out using a known disperser such as a high-speed shear disperser, friction disperser, high-pressure jet disperser, or ultrasonic disperser, thereby achieving O / W emulsification. High-speed shear disperser is preferred. When using a high-speed shear disperser, the rotational speed is preferably 500–20000 rpm, more preferably 1000–10000 rpm. The dispersion time is preferably 0.1–30 minutes, more preferably 1–10 minutes. The dispersion temperature is preferably 20–80°C.

[0051] Furthermore, in this invention, the weight ratio of component (a) to component (b) is as follows: when component (a) is set to 100 parts by mass, component (b) is preferably 100 to 500 parts by mass, and more preferably 150 to 300 parts by mass. It should be noted that the above weight ratio of component (a) to component (b) refers to the weight ratio when component (a) and component (b) are mixed in the third step.

[0052] By employing the above conditions, it is easy to obtain the micro-hollow particles of the present invention, which consist of a resin film composed of multiple small sheet-like portions and bonding portions that bind them together. This is presumably because, in the O / W emulsion, both large-sized and small-sized emulsion particles are simultaneously generated within the system.

[0053] Step 4:

[0054] The fourth step is as follows: a melamine-formaldehyde prepolymer compound is added to the aforementioned O / W emulsion as an additive phase, and the condensation reaction of hydroxymethylated melamine, which is the melamine-formaldehyde prepolymer compound, is carried out at the droplet interface of the O / W emulsion to form a resin film, which becomes tiny particles that encapsulate the aforementioned oil phase, thereby obtaining a microparticle dispersion in which the formed tiny particles are dispersed.

[0055] In this process, it is speculated that small-sized emulsion particles form a resin film at the interface of the aforementioned large-sized emulsion particles.

[0056] As an additive phase, it may be only a melamine-formaldehyde prepolymer compound, but it is preferred to use a melamine-formaldehyde prepolymer compound dissolved in water or an alkaline aqueous solution.

[0057] There is no particular limitation on the amount of melamine-formaldehyde prepolymer compound used in the additive phase. In order to form fine particles well, it is preferably 20 to 100 parts by mass relative to 100 parts by mass of component (a) used in the first step.

[0058] As a melamine-formaldehyde prepolymer compound, it can be directly added to the commercially available melamine-formaldehyde prepolymer compound described later, or it can be dissolved in water or an alkaline aqueous solution for use. Alternatively, it can be used directly by heating in an alkaline aqueous solution containing melamine and formaldehyde in an alkaline region to induce an addition reaction between formaldehyde and melamine, or by using conventional methods.

[0059] When the total amount of melamine-formaldehyde prepolymer compound in the added phase is set to 100 parts by mass, water or alkaline aqueous solution is preferably used in the range of 0 to 500 parts by mass, and more preferably in the range of 20 to 300 parts by mass.

[0060] The pH of the aqueous phase, which serves as the continuous phase, can be adjusted after the addition of the additive phase. The pH of the aqueous phase as the continuous phase is preferably below 7, further preferably 3.5–6.5, and most preferably adjusted to 4.0–5.5. For the preferred reaction temperature, the reaction is preferably carried out in the range of 40–90°C. The reaction time is preferably carried out in the range of 1–48 hours.

[0061] Step 5:

[0062] The fifth step is the process of separating the microparticles from the aforementioned microparticle dispersion. The separation method for separating the microparticles from the microparticle dispersion can be selected from conventional separation methods without particular limitations. Specifically, filtration, centrifugation, etc., can be used.

[0063] Step 6:

[0064] Step 6 involves removing the internal oil phase from the aforementioned microparticles obtained in step 5, thereby producing micro-hollow particles. The method for removing the oil phase from the microparticles can be selected from conventional separation methods without particular limitation; specifically, circulating air dryers, spray dryers, fluidized bed dryers, vacuum dryers, etc., can be used. The preferred temperature conditions for drying are 40–250°C, more preferably 50–200°C.

[0065] The components used in this invention are described below.

[0066] In this invention, the organic solvent used in component (a) is not particularly limited, but preferably an organic solvent with a boiling point of 90°C to 200°C. By using an organic solvent with a boiling point in this range, the formation of the emulsion can be maintained even at the temperature of the condensation reaction of hydroxymethylated melamine, and the organic solvent can be easily removed from the resulting fine particles. An organic solvent with a boiling point of 100°C to 180°C is more preferred. Examples of such organic solvents include those listed below.

[0067] As a hydrocarbon solvent, aliphatic hydrocarbons with 7 to 11 carbon atoms, cyclopentane, cyclooctane, and other alicyclic hydrocarbons can be used. As a solvent other than a hydrocarbon solvent, butyl acetate, dibutyl ether, 1,2-dichloroethane, toluene, xylene, benzaldehyde, chlorobenzene, dichlorobenzene, etc. can be used.

[0068] These organic solvents can be used alone, or they can be a mixture of two or more solvents.

[0069] The organic solvents used in this invention are further preferably aliphatic hydrocarbons, cyclopentane, cyclooctane, toluene, xylene, and chlorobenzene with 8 to 11 carbon atoms, and in particular, toluene, xylene, and chlorobenzene are most preferred.

[0070] In this invention, the surfactant used in component (b) is not particularly limited, and two or more types can be mixed. As the surfactant of this invention, at least one surfactant having a carboxyl group as a hydrophilic group is suitable, and this carboxyl group can be generated by the hydrolysis of dicarboxylic anhydride. Styrene-maleic anhydride copolymers, ethylene-maleic anhydride copolymers, isobutylene-maleic anhydride copolymers, and other maleic anhydride copolymers are suitable. Ethylene-maleic anhydride copolymers are particularly suitable. It should be noted that the molecular weight of the aforementioned maleic anhydride copolymers can be approximately 30,000 to 500,000. Within this range, stable emulsions and resin films can be formed.

[0071] The melamine-formaldehyde prepolymer compound that can be used in this invention is a hydroxymethylated melamine formed from melamine and formaldehyde, and can be manufactured according to conventional methods. For example, it can be manufactured by heating formaldehyde and melamine in an alkaline aqueous solution containing melamine and formaldehyde to induce an addition reaction. Alternatively, commercially available melamine-formaldehyde prepolymer compounds can also be used. Examples include BECKAMINE APM, BECKAMINEM-3, BECKAMINEM-3(60), BECKAMINEMA-S, BECKAMINE J-101, BECKAMINE J-101LF (manufactured by DIC Corporation), NIGARESIN S-176, NIGARESIN S-260 (manufactured by NIPPON CARBIDE INDUSTRIES CO.,INC.), and MIRBANE RESINSM-800 (manufactured by Showa Polymer Co., Ltd.).

[0072] It should be noted that, for the above-mentioned hydroxymethylated melamine, hexahydroxymethylated melamine (same as 1 / 6) can be prepared from monohydroxymethylated melamine (melamine / formaldehyde molar ratio: 1 / 1) according to the molar ratio of melamine to formaldehyde. However, considering both the surrounding effect of droplets on the oil phase and the condensation reaction (crosslinking) in the O / W emulsion, it is more suitable to prepare pentahydroxymethylated melamine (same as 1 / 5) from trihydroxymethylated melamine (same as 1 / 3), and tetrahydroxymethylated melamine (same as 1 / 4) is particularly preferred.

[0073] The mechanism for the formation of the aforementioned tiny hollow particles is hypothesized as follows: Droplets of an oil phase formed from (a) an organic solvent are dispersed in an aqueous phase. Hydroxymethylated melamine undergoes amide bonding with the hydrophilic groups (e.g., carboxyl groups) of a surfactant coordinated at the droplet interface, thereby surrounding the droplet with hydroxymethylated melamine. In this surrounded state, adjacent hydroxymethylated melamine particles undergo a dehydration condensation reaction between their hydroxymethyl groups, forming a melamine-formaldehyde resin capsule shell. Furthermore, the hydroxymethylation ratio of melamine (the molar ratio of formaldehyde to melamine) is related to the density of the capsule shell; a higher hydroxymethylation ratio results in a higher crosslinking density and a denser capsule shell. Therefore, it is preferable to form hydroxymethylated melamine within the aforementioned range.

[0074] The tiny hollow particles of this invention can be used for a variety of applications, such as in pesticides, pharmaceuticals, cosmetic materials, liquid crystals, adhesives, electronic components, building materials, and many other fields. In particular, the tiny hollow particles of this invention are suitable for applications such as shoe soles, insoles, heat insulation materials, sound insulation materials, and CMP abrasive pads.

[0075] As a method for such CMP abrasive pad applications, known methods can be used without limitation, for example, by cutting and surface grinding a resin containing the tiny hollow particles of the present invention as a foaming agent, thereby enabling the production of a CMP abrasive pad with fine pores on the abrasive surface of the resin.

[0076] There are no particular limitations on the aforementioned resin, but in this invention, the polyurethane resin described later is suitable. That is, preferably, a cured product is prepared by dispersing the tiny hollow particles of this invention in a polyurethane resin, and the CMP abrasive pad is made from this cured product.

[0077] In particular, the micro hollow particles of the present invention have good compatibility with polyurethane resin, so when used in CMP abrasive pads, the micro hollow particles are not easy to fall off, which can improve scratch resistance.

[0078] Furthermore, the density of the CMP abrasive pad of the present invention is preferably 0.40 to 1.10 g / cm³. 3 More preferably, it is 0.50–1.05 g / cm³. 3 Alternatively, the cured product obtained by combining the micro-hollow particles of the present invention with a known foaming method can also be used as a CMP abrasive pad. As a known foaming method, such as a foaming agent foaming method using water, if the resin is polyurethane, carbon dioxide and amino groups are generated after water reacts with isocyanate groups. The aforementioned carbon dioxide becomes the foaming gas, and the aforementioned amino groups then react with the isocyanate groups to form urea bonds and / or thiourea bonds.

[0079] The CMP abrasive pad of the present invention can have any suitable hardness. The hardness in the present invention can be determined according to the Shore hardness test, for example, according to JIS standard (hardness test) K6253. In the present invention, the Shore hardness of the CMP abrasive pad is preferably 30A to 80D, more preferably 40A to 70D (it should be noted that "A" represents the hardness at the Shore "A" scale, and "D" represents the hardness at the Shore "D" scale). That is, for example, 30A to 80D means a Shore A hardness of 30 or higher and a Shore D hardness of 70 or lower.

[0080] The aforementioned hardness can be achieved by changing the blend composition and blending amount as needed to form any hardness.

[0081] Furthermore, the CMP abrasive pad of the present invention preferably has a compression ratio within the following range to exhibit flatness of the workpiece being abraded. The compression ratio can be determined according to a method based on JIS L1096. The aforementioned compression ratio is preferably 0.5% to 50%. By being within the above range, excellent flatness of the workpiece being abraded can be exhibited.

[0082] The abrasion resistance of the CMP abrasion pad of the present invention is preferably 60 mg or less in the Tiber abrasion test, and more preferably 50 mg or less. Because the Tiber abrasion amount is reduced, it exhibits excellent abrasion resistance when used as a CMP abrasion pad.

[0083] The state of the CMP polishing pad of the present invention is not particularly limited; for example, a groove structure may be formed on its surface. As the groove structure of the CMP polishing pad, it is preferable to make it into a shape that can retain / renew the slurry. Specifically, examples include X (strip) grooves, XY grid grooves, concentric circular grooves, through holes, non-through holes, polygonal prisms, cylinders, spiral grooves, eccentric circular grooves, radial grooves, and structures formed by combining these grooves.

[0084] Furthermore, there are no particular limitations on the method for manufacturing the groove structure of the aforementioned CMP polishing pad. Examples include: a method of manufacturing by flowing the aforementioned compound into a mold having a specified groove structure and then curing it; or, a method of manufacturing the groove structure using the obtained resin; a method of mechanically cutting using a mold with a specified sized tool; a method of manufacturing by pressing the resin with a pressing plate having a specified surface shape; a method of manufacturing using photolithography; a method of manufacturing using a printing method; and a method of manufacturing using a laser beam such as a carbon dioxide gas laser.

[0085] Furthermore, the CMP polishing pad of the present invention can be composed of multiple layers. In this case, at least any one layer may use the cured product of the present invention. For example, in the case where the CMP polishing pad is composed of two layers, during polishing, a polishing layer (also referred to as the first layer) having a polishing surface in contact with the workpiece is formed, and a base layer (also referred to as the second layer) that is in contact with the first layer on a surface opposite to the polishing surface of the first layer is formed. In this case, by making the second layer and the first layer have different hardness and elastic modulus, the characteristics of the CMP polishing pad can be adjusted. In this case, it is preferable that the hardness of the base layer is less than that of the polishing layer. In the present invention, it is suitable to use the cured product of the present invention as the polishing layer, and furthermore, the cured product of the present invention may also be used as the base layer.

[0086] The polyurethane resin used in the aforementioned CMP abrasive pads will be described in detail below.

[0087] Polyurethane resins can be manufactured without particular limitations using known methods. For example, one method involves uniformly mixing / dispersing a (B) polyfunctional isocyanate compound (hereinafter also referred to as component (B)), a compound having two or more active hydrogen groups capable of curing with (C) isocyanate groups (hereinafter also referred to as component (C)), and other necessary formulation components, followed by curing. The active hydrogen groups of component (C) can be, for example, groups selected from the group consisting of hydroxyl, mercapto, and amino groups.

[0088] Furthermore, a cured product consisting of the micro-hollow particles of the present invention dispersed in a polyurethane resin can be manufactured by curing, for example, a curable composition comprising component (B), component (C), and the micro-hollow particles of the present invention. Other compounding components may also be added to this curable composition as needed. The cured product thus manufactured can be processed into desired shapes and used as a CMP abrasive pad.

[0089] The curing method can also employ well-known methods without particular limitations, such as those described in International Publications No. 2015 / 068798, 2016 / 143910, and 2018 / 092826. Specifically, dry methods such as one-pot curing and prepolymer curing, as well as wet methods using solvents, can be used. Among these, dry methods are particularly suitable.

[0090] Regarding the amount of the aforementioned micro hollow particles of the present invention mixed in polyurethane resin, relative to a total of 100 parts by weight of components (B) and (C), it is preferable to set the amount of the micro hollow particles of the present invention to be 0.1 to 20 parts by weight, more preferably 0.2 to 10 parts by weight, and even more preferably 0.5 to 8 parts by weight. Within this range, excellent grinding characteristics can be exhibited.

[0091] It should be noted that, in this invention, polyurethane resin refers to the collective term for polyurethane resin, polyurea resin, and polyurethane urea resin. Furthermore, the polyurethane resin in this invention also includes polyurethane thiourea resin and polyurethane thiourea resin.

[0092] The following provides details about each ingredient.

[0093] <(B) Polyfunctional isocyanate compounds; (B) Components>

[0094] (B) Component is a compound having at least two isocyanate groups.

[0095] It should be noted that in this invention, the isocyanate group refers to either an isocyanate group (NCO group) or an isothiocyanate group (NCS group). As component (B), a compound having both an isocyanate group and an isothiocyanate group can also be selected. Therefore, the number of isocyanate groups in component (B) refers to the total number of isocyanate groups and isothiocyanate groups.

[0096] Among them, compounds having 2 to 6 isocyanate groups in the molecule are preferred, compounds having 2 to 4 isocyanate groups are more preferred, and compounds having 2 to 3 isocyanate groups are even more preferred.

[0097] Alternatively, the aforementioned component (B) can also be produced by reacting a difunctional isocyanate compound having two isocyanate groups within the (B11) molecule (hereinafter also referred to as "(B11) component") with a compound containing two active hydrogen groups within the (C11) molecule (hereinafter also referred to as "(C11) component") to produce a (B1) urethane prepolymer (hereinafter also referred to as "(B1) component"). The (B1) component, equivalent to component (B), can be used without restriction as long as it contains two or more unreacted isocyanate groups or isothiocyanate groups; preferably, it contains two or more isocyanate groups.

[0098] It should be noted that the active hydrogen groups in the aforementioned (C11) component refer to groups selected from hydroxyl, thiol, and amino groups.

[0099] As for the aforementioned component (B), it can be broadly classified into aliphatic isocyanates, alicyclic isocyanates, aromatic isocyanates, isothiocyanates, other isocyanates, and component (B1). Furthermore, component (B) can use one compound or multiple compounds. When multiple compounds are used, the mass used as a reference is the total mass of all compounds. Specific examples of these components (B) are listed below.

[0100] Aliphatic isocyanates; (B) Component

[0101] 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-trimethylundecylene diisocyanate, 1,3,6-trimethyl 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-butanediol dipropyl ether-ω,ω'-diisocyanate, lysine diisocyanate methyl ester, 2,4,4'-trimethylhexamethylene diisocyanate and other difunctional isocyanates (equivalent to component (B11) of component (B1) detailed below).

[0102] Alicyclic isocyanates; (B) Component

[0103] 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-bis(isocyanate)norbornane (Oxycyanate-methyl)furan, di(isocyanate-methyl)cyclohexane, dicyclohexylmethane-4,4'-diisocyanate, 4,4-isopropylidene bis(cyclohexyl isocyanate), cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyl dimethylmethane diisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate, bis(4-isocyanate-n-butylidene)pentaerythritol, dimer acid diisocyanate, 2,5-bis(isocyanate-methyl)furan, dicyclohexane, dicyclohexylmethane, dicyclohexylmethane, dicyclohexane ... 2,6-bis(isocyanate methyl)-bis(2,2,1)-heptane, 3,8-bis(isocyanate methyl)tricyclodecane, 3,9-bis(isocyanate methyl)tricyclodecane, 4,8-bis(isocyanate methyl)tricyclodecane, 4,9-bis(isocyanate methyl)tricyclodecane, 1,5-diisocyanate naphthane, 2,7-diisocyanate naphthane, 1,4-diisocyanate naphthane 2,6-diisocyanate naphthane, bicyclic [4.3.0]nonane-3,7-diisocyanate, bicyclic [4.3.0]nonane-4,8-diisocyanate, bicyclic [2.2.1]heptane-2,5-diisocyanate and bicyclic [2.2.1]heptane-2,6-diisocyanate, bicyclic [2,2,2]octane-2,5-diisocyanate, bicyclic [2,2,2]octane-2,6-diisocyanate, tricyclic [5.2.1.0] 2.6 ] Decane-3,8-diisocyanate, tricyclic [5.2.1.0] 2.6 ] Decane-4,9-diisocyanate and other difunctional isocyanates (equivalent to (B11) components of (B1) components detailed below).

[0104] 2-Isocyanate methyl-3-(3-isocyanate propyl)-5-isocyanate methyl-bicyclo[2,2,1]-heptane, 2-isocyanate methyl-3-(3-isocyanate propyl)-6-isocyanate methyl-bicyclo[2,2,1]-heptane, 2-isocyanate methyl-2-(3-isocyanate propyl)-5-isocyanate methyl-bicyclo[2,2,1]-heptane, 2-isocyanate methyl-2-(3-isocyanate propyl)-6-isocyanate methyl-bicyclo[2,2,1]-heptane, 2-isocyanate methyl-3-(3-isocyanate propyl) Polyfunctional isocyanates include 2-(2-isocyanate ethyl)-bicyclo[2,2,1]-heptane, 2-isocyanate methyl-3-(3-isocyanate propyl)-6-(2-isocyanate ethyl)-bicyclo[2,1,1]-heptane, 2-isocyanate methyl-2-(3-isocyanate propyl)-5-(2-isocyanate ethyl)-bicyclo[2,2,1]-heptane, 2-isocyanate methyl-2-(3-isocyanate propyl)-6-(2-isocyanate ethyl)-bicyclo[2,2,1]-heptane, and 1,3,5-tris(isocyanate methyl)cyclohexane.

[0105] Aromatic isocyanates; (B) Component

[0106] Phthalate diisocyanate (ortho, meta, para), tetrachloro-isophthalamide diisocyanate, methylene diphenyl-4,4'-diisocyanate, 4-chloro-isophthalamide diisocyanate, 4,5-dichloro-isophthalamide diisocyanate, 2,3,5,6-tetrabromo-p-phthalamide diisocyanate, 4-methyl-isophthalamide diisocyanate, 4-ethyl-isophthalamide diisocyanate, bis(isocyanate ethyl)benzene, bis(isocyanate propyl)benzene, 1,3-bis(α,α-dimethylisocyanate methyl)benzene, 1,4-bis(α,α-dimethylisocyanate methyl)benzene (Cyanide methyl)benzene, α,α,α',α'-tetramethylphenyl dimethyl diisocyanate, bis(isocyanate butyl)benzene, bis(isocyanate methyl)naphthalene, bis(isocyanate methyl)diphenyl ether, bis(isocyanate ethyl)phthalate, 2,6-di(isocyanate methyl)furan, phenylene diisocyanate (ortho, meta, para), toluene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, dimethylbenzene diisocyanate, diethylbenzene diisocyanate, diisopropylbenzene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, 1,3,5-triisocyanate Oxytomethylbenzene, 1,5-naphthalene diisocyanate, methylnaphthalene diisocyanate, biphenyl diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, biphenyl-4,4'-diisocyanate, bis(isocyanate phenyl)ethylene, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, phenyl isocyanate methyl isocyanate, phenyl isocyanate Difunctional isocyanates such as ethyl isocyanate, tetrahydronaphthyl diisocyanate, hexahydrophenyl diisocyanate, hexahydrodiphenylmethane-4,4'-diisocyanate, diphenyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate, 1,3-propanediol diphenyl ether diisocyanate, benzophenone diisocyanate, diethylene glycol diphenyl ether diisocyanate, dibenzofuran diisocyanate, carbazole diisocyanate, ethylcarbazole diisocyanate, dichlorocarbazole diisocyanate, 2,4-toluene diisocyanate, and 2,6-toluene diisocyanate (equivalent to component (B11) of component (B1) detailed below).

[0107] 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.

[0108] Isothiocyanate; (B) component

[0109] difunctional isothiocyanates such as terephthalic diisothiocyanate, phenyl dimethyl-1,4-diisothiocyanate, and ethyl diisothiocyanate (equivalent to component (B11) of component (B1) as detailed below).

[0110] Other isocyanates: (B) Component

[0111] Other isocyanates include polyfunctional isocyanates with biuret, diurea, or isocyanurate structures (e.g., Japanese Patent Application Publication No. 2004-534870 discloses a method for modifying aliphatic polyisocyanates with biuret, diurea, or isocyanurate structures) as the main raw material, and polyfunctional isocyanates that are adducts with polyols with three or more functions such as trimethylolpropane (disclosed in the book "Polyurethane Resin Handbook" edited by Keiji Iwata, Nikkan Kogyo Shimbun (1987)).

[0112] (B1) Carbamate prepolymer; component (B) with iso(thio)cyanate groups at both ends; component (B1)

[0113] In this invention, the (B1) component, which is produced by reacting the aforementioned (B11) component with the (C11) component described below, may also be used as the (B) component. The (B1) component is a compound having isocyanate groups at both ends.

[0114] The aforementioned component (B1) is not particularly limited, but monomers of the following examples are particularly preferred as component (B11). Specifically, 1,5-naphthalene diisocyanate, xylene diisocyanate (ortho, meta, para), 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, phenylene diisocyanate (ortho, meta, para), 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, 1,3-di(isocyanate methyl)cyclohexane, dicyclohexylmethane-4,4'-diisocyanate, and (bicyclo[2.2.1]heptane-2,5(2,6)-diyl)bismethylene diisocyanate are preferred. Component (C11) is preferably reacted with these monomers to prepare component (B1) having isocyanate groups and / or isothiocyanate groups at both ends.

[0115] Furthermore, for the final polyurethane resin obtained above, in order to achieve particularly superior properties, it is preferable to use at least one (C11) component with a molecular weight (number average molecular weight) of 300 to 2000 to manufacture the (B1) component. The active hydrogen group refers to hydroxyl, mercapto, or amino groups. Among these, considering reactivity, the active hydrogen group in the (C11) component is preferably hydroxyl.

[0116] The aforementioned (C11) component with a molecular weight (number average molecular weight) of 300 to 2000 can also be used in combination with different types of components and components with different molecular weights. Furthermore, in order to adjust the hardness, strength, etc., of the final polyurethane resin, the (B1) component is preferably a product manufactured by combining a (C11) component with a molecular weight (number average molecular weight) of 300 to 2000 with a (C11) component with a molecular weight (number average molecular weight) of 90 to 300. In this case, it also depends on the type of (C11) component, the (B11) component, and their amounts used. However, when the (C11) component with a molecular weight of 300 to 2000 is set at 100 parts by mass, it is preferable to set the (C11) component with a molecular weight of 90 to 300 at 0 to 50 parts by mass, and more preferably, the (C11) component with a molecular weight of 90 to 300 at 1 to 40 parts by mass.

[0117] Furthermore, the two ends of the molecule of component (B1) must be isocyanate groups. Therefore, it is preferable that the total molar number (n5) of isocyanate groups in component (B11) and the total molar number (n6) of active hydrogen groups (hydroxyl, mercapto, or amino) in component (C11) are in the range of 1 < (n5) / (n6) ≤ 2.3. When using two or more components with (B11) as the molecule ends, the molar number (n5) of the isocyanate groups is naturally the total molar number of isocyanate groups in component (B11). In addition, the molar number (n6) of active hydrogen groups in two or more (C11) components is naturally the total molar number of active hydrogen groups. Even when the active hydrogen group is a primary amino group, it can be considered that the primary amino group is 1 mole. That is, in a primary amino group, the reaction of the second amino group (-NH) requires considerable energy (even in a primary amino group, the second -NH group is difficult to react). Therefore, in this invention, even when using a (C11) component containing a primary amino group, the primary amino group can be calculated as 1 mole.

[0118] The isocyanate equivalent (the total amount of isocyanate equivalent and / or isothiocyanate equivalent) of the aforementioned component (B1) can be determined by quantifying the isocyanate groups present in component (B1) according to JIS K 7301. This isocyanate group can be quantified by the following reverse titration method. First, the obtained component (B1) is dissolved in a dry solvent. Next, di-n-butylamine, in a known concentration and in significantly excess compared to the amount of isocyanate groups present in component (B1), is added to the dry solvent, allowing all the isocyanate groups of component (B1) to react with the di-n-butylamine. Then, the unconsumed (irrelevant to the reaction) di-n-butylamine is titrated with acid to determine the amount of di-n-butylamine consumed. Since the consumed di-n-butylamine is equal in amount to the isocyanate groups present in component (B1), the isocyanate equivalent can be determined. Furthermore, component (B1) is a linear urethane prepolymer with isocyanate groups at both ends, therefore the number-average molecular weight of component (B1) is twice the isocyanate equivalent. The molecular weight of component (B1) readily matches the value measured using gel permeation chromatography (GPC). It should be noted that, for example, when component (B1) and component (B11) are used in combination, the mixture of the two can be determined using the method described above.

[0119] The aforementioned component (B1) is not particularly limited, but the isocyanate equivalent is preferably 300 to 5000, more preferably 350 to 3000, and particularly preferably 350 to 2000. The reason for this is not particularly clear, but it can be considered as follows: By using the aforementioned component (B1), the crosslinking points in the aforementioned polyurethane resin become easily dispersed and exist randomly and uniformly, thus exhibiting stable properties. Furthermore, the aforementioned polyurethane resin obtained using component (B1) is easy to control during manufacturing. For example, it is considered suitable to use the curable composition used in this invention as a polishing pad. When components (B1) and (B11) are used in combination, it is considered that such an effect is observed even when the average isocyanate equivalent of the polyisocyanate compound is 300 to 5000. Among these, the aforementioned effect is considered to be significant when only component (B1) is used.

[0120] In the manufacturing method of component (B1) used in this invention, component (C11), which has two active hydrogen groups (hydroxyl, mercapto, or amino) within its molecule, is reacted with component (B11) to produce component (B1) having an isocyanate group or an isothiocyanate group at the end of the molecule. There are no limitations as long as a prepolymer with an isocyanate group or an isothiocyanate group at the end can be obtained.

[0121] Although described above, the preferred mixing amounts of the (C11) component and the (B11) component for obtaining the (B1) component are as follows. Specifically, it is preferred that the molar number (n5) of the isocyanate group in the (B11) component and the molar number (n6) of the active hydrogen in the (C11) component are in the range of 1 < (n5) / (n6) ≤ 2.3.

[0122] In addition, to produce component (B1), it can be produced by heating or adding a carbamate catalyst as needed during the reaction.

[0123] If we list the most preferred examples of the components (B) used in this invention, from the viewpoint of controlling the strength and reactivity of the aforementioned polyurethane resin, examples that can be listed include alicyclic isocyanates such as isophorone diisocyanate, 1,3-bis(isocyanate methyl)cyclohexane, (bicyclo[2.2.1]heptane-2,5(2,6)-diyl)bismethylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, aromatic isocyanates of dimethyl diisocyanate (ortho, meta, para), hexamethylene diisocyanate, toluene diisocyanate, etc., as the main raw materials, as biuret structures, urea diketone structures, isocyanurate structures, polyfunctional isocyanates as adducts with polyols with 3 or more functions, or components (B1).

[0124] Among them, component (B1) is particularly preferred.

[0125] <(C) Compounds having two or more active hydrogen groups capable of curing with isocyanate groups; (C) Components>

[0126] (C) Any compound having at least two groups selected from the group consisting of hydroxyl, thiol, and amino groups in at least one molecule may be used without restriction. Of course, compounds having any two or all of the groups of hydroxyl, thiol, and amino groups may also be selected.

[0127] Among these components, it is suitable to include (CA) compounds having two or more amino groups (hereinafter also referred to as "(CA) components") as component (C), and it is even more suitable to include (CB) compounds having three or more hydroxyl groups and / or thiol groups (hereinafter also referred to as "(CB) components"). It should be noted that, in this invention, a compound having n or more hydroxyl groups and / or thiol groups means that the total number of hydroxyl and thiol groups in the compound is n or more. It can 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 and thiol groups.

[0128] Of these, compounds having five or more hydroxyl groups and / or thiol groups are particularly preferred as the aforementioned (CB) component. Furthermore, the molar number of hydroxyl groups and / or thiol groups relative to the mass of the (CB) component is preferably 0.5 mmol / g to 35 mmol / g, more preferably 0.8 mmol / g to 20 mmol / g.

[0129] ((CA) compounds having two or more amino groups; (CA) components)

[0130] The aforementioned (CA) components can be used without restriction as long as they are compounds having two or more primary and / or secondary amino groups in one molecule. If compounds having two or more of the aforementioned amino groups are broadly classified, they are divided into aliphatic amines, alicyclic amines, aromatic amines, and polyrotaxanes having amino groups that can polymerize with isocyanate groups.

[0131] Aliphatic amines; (CA) components

[0132] Ethylenediamine, hexamethylenediamine, nonamethylenediamine, undecylmethylenediamine, dodecamethyldiamine, m-phenylenediamine, 1,3-propanediamine, putrescine, and other difunctional amines (equivalent to the (C11) components that constitute the aforementioned (B1) component).

[0133] Diethylenetriamine and other polyamines and other polyfunctional amines.

[0134] Alicyclic amines; (CA) components

[0135] Isophorone diamine, cyclohexyl diamine and other difunctional amines (equivalent to the (C11) component that constitutes the aforementioned (B1) component).

[0136] Aromatic amines; (CA) components

[0137] 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-di Ethyltoluene-2,6-diamine, 1,3-propanediol-bis(p-aminobenzoate), polytetramethylene ether glycol-bis(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-aminophenylthio)ethane, 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, N,N'-disec-butyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, m-phenylenediamine, N,N'-disec-butyl-p-phenylenediamine, m-phenylenediamine, p-phenylenediamine, p-phenylenediamine, 3,3'-methylenediamine Difunctional amines such as bis(methyl-6-aminobenzoate), 2,4-diamino-4-chlorobenzoate-2-methylpropyl ester, 2,4-diamino-4-chlorobenzoate-isopropyl ester, 2,4-diamino-4-chlorophenylacetic acid-isopropyl ester, bis(2-aminophenyl)thioethyl terephthalate, diphenylmethanediamine, toluenediamine, piperazine, etc. (equivalent to (C11) components that constitute the aforementioned (B1) component).

[0138] Polyfunctional amines such as 1,3,5-phenyltriamine and melamine.

[0139] Polyrotaxanes containing amino groups; (CA) component

[0140] The amino-containing polyrotaxanes used in this invention are not particularly limited, for example, the polyrotaxanes described in International Publication No. 2018 / 092826 can be cited as examples.

[0141] Preferred (CA) components used in this invention include, for example, 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 1,3-propanediol-bis-para-aminobenzoate.

[0142] Compounds containing hydroxyl and / or thiol groups in component (C) can be broadly classified into aliphatic alcohols, alicyclic alcohols, aromatic alcohols, polyester polyols, polyether polyols, polycaprolactone polyols, polycarbonate polyols, polypropylene polyols, castor oil-based polyols, compounds with two or more thiol groups, monomers containing OH / SH type polymerizable groups, cyclic molecules containing side chains with three or more hydroxyl and / or thiol groups, and polyrotaxanes containing hydroxyl and / or thiol groups. Specific examples include the following substances.

[0143] (C) Compounds having two or more hydroxyl groups; (C) Components)

[0144] Aliphatic alcohols; (C) component

[0145] Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, 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, glyceryl monotransoleate, polyethylene glycol, 3-methyl-1,5-dihydroxypentane, dihydroxyneopentane, 2-ethyl-1,2-dihydroxyhexane, 2-methyl-1,3-dihydroxypropane, and other difunctional polyols (equivalent to the (C11) component constituting the aforementioned (B1) component).

[0146] Glycerin, trimethylolethane, trimethylolpropane, bis(trimethylol)propane, trimethylolpropane trimoxyethylene ether (e.g., TMP-30, TMP-60, TMP-90, etc. from Nippon Emulsifiers Co., Ltd.), glycerol, 1,2-methyl glycoside, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, erythritol tetranitrate, threitol, ribitol, arabinitol, xylitol, allitol, mannitol, eugenol, idotitol, ethylene glycol, inositol, hexanetriol, tripropylene glycol, dipropylene glycol, triethylene glycol, and other multifunctional polyols (equivalent to the aforementioned (CB) components).

[0147] Alicyclic alcohols; (C) component

[0148] Hydrogenated bisphenol A, cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanediol, hydroxypropylcyclohexanol, tricyclo[5,2,1,0] 2,6 [Decane-diethanol, bicyclo[4,3,0]-nonanediol, dicyclohexanediol, tricyclo[5,3,1,1] 3,9 Dodecanediol, bicyclic [4,3,0]nonanediethanol, tricyclic [5,3,1,1] 3,9 Dodecane-diethanol, hydroxypropyltricyclo[5,3,1,1] 3,9Dodecyl alcohol, spiro[3,4]octanediol, butylcyclohexanediol, 1,1'-bicyclohexanediol, 1,4-cyclohexanediethanol, 1,3-cyclohexanediethanol, 1,2-cyclohexanediethanol, and o-dihydroxyxylene, etc., are difunctional polyols (equivalent to the (C11) components that constitute the aforementioned (B1) component).

[0149] Tris(2-hydroxyethyl) isocyanurate, cyclohexanetriol, sucrose, maltitol, lactitol and other multifunctional polyols (equivalent to the aforementioned (CB) components).

[0150] Aromatic alcohols; (C) component

[0151] Dihydroxynaphthalene, dihydroxybenzene, bisphenol A, bisphenol F, dimethyl phthalate, 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-(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) 2,2-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)heptane, 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 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)norbornene, 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'-spirobis(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-hexanediol, 4,4'-dihydroxybiphenyl, m-dihydroxyxylene, p-dihydroxyxylene, 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 difunctional polyols such as hydroquinone and resorcinol (equivalent to components (C11) constituting the aforementioned component (B1)).

[0152] Trihydroxynaphthalene, tetrahydroxynaphthalene, phenylglycerol, biphenyltetraol, pyrogallol, (hydroxynaphthyl)pyrogallol, trihydroxyphenanthrene and other multifunctional polyols (equivalent to the aforementioned (CB) components).

[0153] Polyester polyols; (C) Components

[0154] Examples of compounds obtained by condensation reactions of polyols with compounds having multiple carboxylic acids include those obtained by condensation reactions. The number-average molecular weight is preferably 400–2000, more preferably 500–1500, and most preferably 600–1200. It should be noted that compounds having hydroxyl groups only at both ends of the molecule (two within the molecule) are equivalent to the (C11) component constituting the aforementioned (B1) component, while compounds having three or more hydroxyl groups in the molecule are equivalent to the aforementioned (CB) component.

[0155] Here, examples of polyols mentioned above include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 3,3'-dihydroxymethylpentane, 1,4-cyclohexanediethanol, neopentanediol, 3,3-bis(hydroxymethyl)pentane, diethylene glycol, dipropylene glycol, glycerol, and trimethylolpropane. These can be used alone or in mixtures of two or more. Additionally, examples of compounds containing multiple carboxylic acids mentioned above include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. These can be used alone or in mixtures of two or more.

[0156] These polyester polyols can be obtained as reagents or industrially. If commercially available examples are listed, they include the "POLYLIGHT (registered trademark)" series manufactured by DIC Corporation, the "Nipporane (registered trademark)" series manufactured by Nippon Polyurethanes Industries, Ltd., the "MAXIMOL (registered trademark)" series manufactured by Kawasaki Chemical Industries, Ltd., and the "KURARAY POLYOL (registered trademark)" series manufactured by Kuraray Co., Ltd., etc.

[0157] Polyether polyols; (C) Component

[0158] Examples include compounds and their modifications obtained by ring-opening polymerization of epoxides or by reacting compounds having two or more active hydrogen groups in the molecule with epoxides. The number-average molecular weight is preferably 400–2000, more preferably 500–1500, and most preferably 600–1200. It should be noted that compounds having hydroxyl groups only at both ends of the molecule (two within the molecule) are equivalent to the (C11) component constituting the aforementioned (B1) component, while compounds having three or more hydroxyl groups in the molecule are equivalent to the aforementioned (CB) component.

[0159] Here, the aforementioned polyether polyols can include polymer polyols, urethane-modified polyether polyols, polyether ester copolymer polyols, etc. As compounds having two or more active hydrogen groups in the above molecules, examples include water, ethylene glycol, propylene glycol, butanediol, glycerol, trimethylolpropane, hexanetriol, triethanolamine, diglycerol, pentaerythritol, trimethylolpropane, hexanetriol, etc. Polyol compounds such as ethylene glycol and glycerol having one or more hydroxyl groups in the molecule can be used alone or in mixtures of two or more.

[0160] In addition, cyclic ether compounds such as ethylene oxide, propylene oxide, and tetrahydrofuran can be listed as examples of the aforementioned epoxides. These can be used alone or in combination of two or more.

[0161] Such polyether polyols can be obtained as reagents or industrially. If commercially available examples are listed, they include the "EXCENOL (registered trademark)" series manufactured by Asahi Glass Co., Ltd., the "EMULSTAR (registered trademark)" series manufactured by Asahi Glass Co., Ltd., and the "ADEKA Polyether" series manufactured by ADEKA Co., Ltd.

[0162] Polycaprolactone polyol; (C) component

[0163] Compounds obtained by ring-opening polymerization of ε-caprolactone can be listed. The number-average molecular weight is preferably 400–2000, more preferably 500–1500, and most preferably 600–1200. It should be noted that compounds having hydroxyl groups only at both ends of the molecule (two within the molecule) are equivalent to the (C11) component constituting the aforementioned (B1) component, while compounds having three or more hydroxyl groups in the molecule are equivalent to the aforementioned (CB) component.

[0164] These polycaprolactone polyols can be obtained as reagents or industrially. If commercially available examples are cited, the "PLACCEL (registered trademark)" series manufactured by Daicel Chemical Industry Co., Ltd. can be listed.

[0165] Polycarbonate polyols; (C) Component

[0166] Examples include compounds obtained by phosgenation of one or more low-molecular-weight polyols or by transesterification using ethylene carbonate, diethyl carbonate, diphenyl carbonate, etc. The number-average molecular weight is preferably 400–2000, more preferably 500–1500, and most preferably 600–1200. It should be noted that compounds with hydroxyl groups only at both ends of the molecule (two within the molecule) are equivalent to the (C11) component constituting the aforementioned (B1) component, while compounds with three or more hydroxyl groups within the molecule are equivalent to the aforementioned (CB) component.

[0167] Here, the aforementioned low molecular weight polyols can be listed 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, neopentanediol, cyclohexane-1,4-diol, cyclohexane-1,4-diethanol, dimer glycol, ethylene oxide of bisphenol A, propylene oxide adduct, bis(β-hydroxyethyl)benzene, diphenylmethylenediol, glycerol, trimethylolpropane, pentaerythritol, and other low molecular weight polyols.

[0168] Polypropylene polyol; (C) component

[0169] Examples of polyol compounds obtained by polymerizing (meth)acrylates and vinyl monomers include those that have hydroxyl groups only at both ends of the molecule (or two within the molecule). It should be noted that compounds with hydroxyl groups are equivalent to the (C11) component that constitutes the aforementioned (B1) component, while compounds with three or more hydroxyl groups in the molecule are equivalent to the aforementioned (CB) component.

[0170] Castor oil is a polyol; (C) component

[0171] As castor oil-based polyols, examples of polyol compounds that use castor oil, a natural oil, as a starting material can be listed. It should be noted that compounds with hydroxyl groups only at both ends of the molecule (two within the molecule) are equivalent to the (C11) component that constitutes the aforementioned (B1) component, while compounds with three or more hydroxyl groups within the molecule are equivalent to the aforementioned (CB) component.

[0172] These castor oil polyols can be obtained as reagents or industrially. If commercially available examples are cited, the "URIC (registered trademark)" series manufactured by Ito Oil Co., Ltd. can be listed.

[0173] (C) Compounds having two or more thiol groups; (C) Components

[0174] As a suitable specific example of a compound having a thiol group in component (C) above, a compound described in International Publication No. WO2015 / 068798 may be used. Among them, the following compounds may be listed as particularly suitable examples.

[0175] Tetraethylene glycol bis(3-mercaptopropionate), 1,4-butanediol bis(3-mercaptopropionate), 1,6-hexanediol bis(3-mercaptopropionate), 1,4-bis(mercaptopropylthiomethyl)benzene (equivalent to component (C11) constituting component (B1) above).

[0176] Trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), dipentaerythritol hexa(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-1,8-dimercapto-3,6-dithiooctane, 1,1,1,1-tetra(mercaptomethyl)methane, 1,1,3,3-tetra(mercaptomethylthio)propane, 1,1,2,2-tetra(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, tri-{(3-mercaptopropionyloxy)ethyl}-isocyanurate and other thiols (equivalent to the aforementioned (CB) components).

[0177] Monomers containing OH / SH type polymerizable groups; (C) Component

[0178] Among the compounds in component (C) mentioned above that have both hydroxyl and thiol groups, the following compounds can be listed.

[0179] 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(salicylate) (equivalent to (C11) components constituting the aforementioned (B1) component).

[0180] Monomers containing polyfunctional OH / SH type polymerizable groups, such as 3-mercapto-1,2-propanediol, glycerol di(mercaptoacetate), 2,4-dimercaptophenol, 1,3-dimercapto-2-propanol, 2,3-dimercapto-1-propanol, 1,2-dimercapto-1,3-butanediol, pentaerythritol tri(3-mercaptopropionate), pentaerythritol mono(3-mercaptopropionate), pentaerythritol bis(3-mercaptopropionate), pentaerythritol tri(mercaptoacetate), pentaerythritol penta(3-mercaptopropionate), hydroxymethyl-tris(mercaptoethylthiomethyl)methane, and hydroxyethylthiomethyl-tris(mercaptoethylthio)methane (equivalent to the aforementioned (CB) component).

[0181] Side chains having three or more hydroxyl and / or thiol groups contain cyclic molecules; (CB) component

[0182] There are no particular restrictions on whether the side chain contains a cyclic molecule, as long as it is a cyclic molecule with three or more hydroxyl groups and / or thiol groups at the end. Examples of cyclic molecules include cyclodextrin, crown ethers, benzo[a]crown ethers, dibenzo[a]crown ethers, dicyclohexane[a]crown ethers, cyclobis(paraquat-1,4-phenylene), dimethoxy-pillar aromatics, calixarenes, and phenanthroline, with cyclodextrin being preferred.

[0183] The cyclodextrin has α-forms (inner ring diameter 0.45–0.6 nm), β-forms (inner ring diameter 0.6–0.8 nm), and γ-forms (inner ring diameter 0.8–0.95 nm). Alternatively, mixtures of these can also be used. In this invention, α-cyclodextrin and β-cyclodextrin are particularly preferred.

[0184] Next, a method for introducing at least three side chains with hydroxyl and / or thiol groups at the ends into the cyclic molecule will be described. The method of introducing the aforementioned side chains is not limited; for example, the side chains can be introduced by modifying the reactive functional groups present in the cyclic molecule (i.e., the side chains are introduced by reacting with the reactive functional groups).

[0185] Examples of reactive functional groups include hydroxyl 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 for one α-cyclodextrin. In this invention, in order to fully utilize the function of the aforementioned side chains, it is necessary to introduce side chains with at least 3 or more hydroxyl and / or thiol groups at the terminal. Preferably, side chains with 5 or more hydroxyl and / or thiol groups at the terminal are introduced; more preferably, side chains with 7 or more hydroxyl and / or thiol groups at the terminal are introduced; and most preferably, side chains with 8 or more hydroxyl and / or thiol groups at the terminal are introduced. Furthermore, side chains with hydroxyl groups at the terminal are particularly preferred.

[0186] The side chain is not particularly limited, but it is preferably formed from an organic chain with a repeating 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 calculated, or it can be obtained from... 1 It is determined by H-NMR measurement.

[0187] By adjusting the lower limit of the number-average molecular weight of the aforementioned side chains as described above, excellent mechanical properties are exhibited, and there is a tendency to improve the grinding rate when using the CMP abrasive pad of the present invention.

[0188] In this invention, the aforementioned side chain can be either linear or branched. For the introduction of the side chain, the methods and compounds disclosed in International Publication No. 2015 / 159875 can be appropriately introduced, for example, using ring-opening polymerization; free radical polymerization; cationic polymerization; anionic polymerization; atom transfer radical polymerization, RAFT polymerization, NMP polymerization, and other living radical polymerizations. According to the above methods, by reacting a suitably selected compound with the reactive functional groups of the aforementioned cyclic molecule, a side chain of suitable size can be introduced.

[0189] Among them, ring-opening polymerization is particularly preferred, in which cyclic compounds such as cyclic ethers, cyclic lactones, cyclic acetals, and cyclic carbonates react with the reactive functional groups of cyclic molecules, and it is suitable to introduce side chains derived from cyclic compounds into cyclic molecules.

[0190] From the viewpoint of high reactivity and ease of preparation of molecular weight, cyclic ethers, cyclic lactones, and cyclic carbonates are preferred among these cyclic compounds.

[0191] The following examples illustrate suitable cyclic ethers, cyclic lactones, and cyclic carbonates.

[0192] Cyclic ethers;

[0193] Ethylene oxide, 1,2-epoxypropane, epichlorohydrin, epibromopropane, 1,2-epoxybutane, 2,3-epoxybutane, isoepoxybutane, oxetane, 3-methyloxetane, 3,3-dimethyloxetane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, etc.

[0194] cyclic lactones;

[0195] 4-membered ring lactones; β-propiolactone, β-methylpropiolactone, L-serine-β-lactone, etc.

[0196] 5-membered ring lactones; γ-butyrolactone, γ-caprolactone, γ-heptanolide, γ-octanolide, γ-decanolide, γ-dodecanolide, α-hexyl-γ-butyrolactone, α-heptyl-γ-butyrolactone, α-hydroxy-γ-butyrolactone, γ-methyl-γ-decanolide, α-methylene-γ-butyrolactone, α,α-dimethyl-γ-butyrolactone, D-erythrolide, α-methyl-γ-butyrolactone, γ-nonanolide, DL-pantolytic acid lactone, γ-phenyl-γ-butyrolactone, γ-undecanolide, γ-pentanolide, 2,2-pentamethylene-1,3-dioxolane-4-one, α-bromo-γ-butyrolactone, γ-crotonic acid lactone, α-methylene-γ-butyrolactone, α-methacryloyloxy-γ-butyrolactone, β-methacryloyloxy-γ-butyrolactone, etc.

[0197] 6-membered ring lactones; δ-valerolactone, δ-caprolactone, δ-octyllactone, δ-nonanolactone, δ-decanolactone, δ-undecyllactone, δ-dodecyllactone, δ-tetrazolyllactone, δ-tetradecyllactone, DL-methylvalerolactone, 4-hydroxy-1-cyclohexanecarboxylic acid δ-lactone, monomethyl-δ-valerolactone, monoethyl-δ-valerolactone, monohexyl-δ-valerolactone, 1,4-dioxane-2-one, 1,5-dioxane-heptane-2-one, etc.

[0198] 7-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-nonyloxetane-2-one, 4,4,6-trimethyloxetane-2-one, 4,6,6-trimethyloxetane-2-one, 5-hydroxymethyloxetane-2-one, etc.

[0199] 8-membered ring lactones; ζ-heptyl lactones, etc.

[0200] Other lactones; lactones, lactide, dilactide, tetramethyl glycoside, 1,5-dioxane-2-one, tert-butylcaprolactone, etc.

[0201] Cyclic carbonates;

[0202] Ethylene carbonate, propylene carbonate, 1,2-butyleneglycerin carbonate 1,2-carbonate, 4-(methoxymethyl)-1,3-dioxolane-2-one, (chloromethyl) ethylene carbonate, vinylene carbonate, 4,5-dimethyl-1,3-dioxolane-2-one, 4-chloromethyl-5-methyl-1,3-dioxolane-2-one, 4-vinyl-1,3-dioxolane-2-one, 4,5-diphenyl-1,3-dioxolane-2-one, 4,4-dimethyl-5-methylene-1,3-dioxolane-2-one, 1,3-dioxane-2-one, 5-methyl-5-propyl-1,3-dioxolane-2-one, 5,5-diethyl-1,3-dioxolane-2-one

[0203] The aforementioned cyclic compounds can be used alone or in combination of two or more.

[0204] In this invention, the cyclic compounds suitable for use are lactone compounds, particularly suitable lactone compounds are ε-caprolactone, α-acetyl-γ-butyrolactone, α-methyl-γ-butyrolactone, γ-valerolactone, γ-butyrolactone, etc., and most preferably ε-caprolactone.

[0205] Furthermore, in cases where side chains are introduced by reacting cyclic compounds through ring-opening polymerization, sometimes the reactive functional groups (e.g., hydroxyl groups) of the cyclic molecules lack reactivity, particularly due to steric hindrance, making direct reaction with larger molecules difficult. In such cases, for example, to facilitate the reaction of the aforementioned caprolactone, it is suitable to pre-introduce reactive functional groups by reacting a low-molecular-weight compound such as propylene oxide with the reactive functional groups of the cyclic molecule to achieve hydroxypropylation. Then, the method of introducing side chains by using the aforementioned ring-opening polymerization of the cyclic compound can be employed. In this case, the hydroxypropylated portion is also considered as a side chain.

[0206] Polyrotaxanes having hydroxyl and / or thiol groups; (C) Component

[0207] Polyrotaxanes refer to complexes of molecules having the following structure: a chain-like axial molecule extends through the rings of multiple cyclic molecules, and large groups are bonded to both ends of the axial molecule, making it impossible for the cyclic molecules to be removed from the axial molecule due to steric hindrance. Polyrotaxanes are also known as supramolecules. The polyrotaxanes that can be used in component (C) of this invention are polyrotaxanes having hydroxyl and / or mercapto groups capable of polymerizing with isocyanate groups; those having three or more hydroxyl and / or mercapto groups are equivalent to the aforementioned component (CB). The polyrotaxanes having hydroxyl and / or mercapto groups used in component (C) of this invention are not particularly limited; for example, the polyrotaxane described in International Application No. 2018 / 092826 can be cited.

[0208] The preferred (CB) components used in this invention include, for example, glycerol, trimethylolethane, trimethylolpropane, bis(trimethylol)propane, trimethylolpropane trimoxyethylene ether (TMP-30 from Nippon Emulsifier 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, cyclic molecules containing side chains having three or more hydroxyl groups, and polyrotaxanes having hydroxyl and / or thiol groups. More preferably, cyclic compounds containing side chains having three or more hydroxyl groups and polyrotaxanes having three or more hydroxyl and / or thiol groups are preferred. From a processability point of view, cyclic molecules containing side chains having three or more hydroxyl groups are most preferred.

[0209] <The mixing ratio of component (B) and component (C)>

[0210] In this invention, the mixing ratio of component (B) and component (C) is not particularly limited. However, to achieve superior performance, when the total number of isocyanate groups in component (B) is set to 1 mole, the total number of moles of active hydrogen groups in component (C) is preferably 0.8 to 2.0 moles. Too many or too few isocyanate groups can easily lead to poor curing or reduced wear resistance in the resulting polyurethane resin. To further obtain a polyurethane resin with good and uniform curing and excellent wear resistance, when the total number of isocyanate groups is set to 1 mole, the total number of moles of active hydrogen groups is more preferably 0.85 to 1.75 moles, and even more preferably 0.9 to 1.5 moles. It should be noted that when calculating the total number of moles of active hydrogen groups in component (C), when using a compound having two or more amino groups (CA), the number of moles of active hydrogen groups in the compound having two or more of these amino groups is equal to the number of moles of the amino groups.

[0211] In addition, in order to exhibit excellent grinding characteristics, as mentioned above, component (C) preferably includes component (CA), and more preferably includes components (CA) and (CB).

[0212] That is, in this invention, the composition for manufacturing polyurethane resin preferably contains component (B) and component (CA), and more preferably contains component (B), component (CA), and component (CB).

[0213] For example, regarding the mixing ratio of components (B), (CA), and (CB), relative to a total of 100 parts by mass of components (B), (CA), and (CB), it is preferable that the components contain 60 to 95 parts by mass of component (B), 2 to 20 parts by mass of component (CA), and 1 to 30 parts by mass of component (CB), and more preferably 70 to 85 parts by mass of component (B), 2 to 15 parts by mass of component (CA), and 3 to 25 parts by mass of component (CB).

[0214] <Other Blending Components>

[0215] As other formulation components used in this invention, various known formulation agents may be used without impairing the effects of the invention. For example, curing catalysts, abrasives, 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.

[0216] As the aforementioned curing catalyst, urethane or urea reaction catalysts can also be used to rapidly promote curing. Specifically, as a suitable urethane or urea reaction catalyst for use in this invention, the catalyst described in International Publication No. 2015 / 068798 can be used.

[0217] These carbamates or ureas can be used alone or in combination with two or more catalysts. The amount used can be the so-called catalyst amount, for example, relative to a total of 100 parts by mass of components (B) and (C), which can be in the range of 0.001 to 10 parts by mass, particularly 0.01 to 5 parts by mass.

[0218] In addition, as the aforementioned abrasive, examples include particles formed from materials selected from cerium oxide, silicon oxide, aluminum oxide, silicon carbide, zirconium oxide, iron oxide, manganese dioxide, titanium oxide, and diamond, or particles containing two or more of these materials.

[0219] Example

[0220] 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 described below.

[0221] [Evaluation Method]

[0222] The obtained tiny hollow particles were analyzed using a field emission scanning electron microscope (JSM-7800FPrime, manufactured by JEOL Ltd.) to obtain electron micrographs, and the images were analyzed using ImageJ (National Institutes of Health) software.

[0223] <Example 1>

[0224] 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 under heating. The pH was then adjusted using 5 ml of a 10% sodium hydroxide aqueous solution to prepare an acidic aqueous solution at 65°C and pH 4. 20 g of toluene as the oil phase was added to the above aqueous phase, and the mixture was stirred at 1500 rpm for 10 minutes using a homogenizer to prepare an O / W emulsion at 45°C and pH 4. As the additive phase, 4.54 g of melamine, 11.69 ml of a 37% formaldehyde aqueous solution, and 7.12 g of distilled water were mixed at 70°C. The pH was then adjusted using 5 ml of a 10% sodium hydroxide aqueous solution, thereby causing an addition reaction between formaldehyde and melamine. Subsequently, an alkaline aqueous solution of hydroxymethylated melamine at 70°C and pH 12 was prepared and added to the O / W emulsion obtained above. Then, a 10% citric acid aqueous solution was added to confirm the pH was below 4. The mixture was stirred at 300 rpm and reacted at 80°C for 3 hours to generate microparticles. These microparticles were then added to a centrifuge and centrifuged 10 times for 15 minutes at 8000 rpm to remove the aqueous phase. Further vacuum drying for 48 hours yielded hollow microparticles. Figure 2 As shown, the obtained microscopic hollow particles were confirmed using field emission scanning electron microscopy, confirming that the resin film is characterized by being composed of multiple small plate-like portions and bonding portions that bind them together. Furthermore, based on image analysis, the average particle size of the microscopic hollow particles was 23.8 μm, with a standard deviation of 6.9. The longest diameter of the small plate-like portions was 9 μm. Furthermore, as... Figure 2 As shown, the obtained micro-hollow particles have a good appearance. The bulk density of the obtained micro-hollow particles is 0.3 g / cm³. 3 Table 1 shows the ingredients used and the results.

[0225] <Comparative Example 1>

[0226] Using the mixing amounts shown in Table 1, except otherwise specified, micro-hollow particles were prepared in the same manner as in Example 1 to obtain them. The obtained micro-hollow particles were confirmed using a field emission scanning electron microscope (FET), and the resin film showed no specific structure, confirming them as typical micro-hollow particles. Furthermore, based on image analysis, the average particle size was 28.1 μm, with a standard deviation of 8.1. Furthermore, from... Figure 3 The obtained micro-hollow particles were confirmed to have a porous appearance. The bulk density of the obtained micro-hollow particles was 0.3 g / cm³. 3 The results are shown in Table 1.

[0227] [Table 1]

[0228] Table 1

[0229]

[0230] As described above, the tiny hollow particles of Example 1 consist of a resin film composed of multiple small sheet-like portions and bonding portions that bind them together. Furthermore, since the resin film of the tiny hollow particles of Example 1 is a melamine-based resin, it exhibits excellent heat and solvent resistance, a large average particle size of up to 23.8 μm, a small standard deviation of particle size of only 6.9, and excellent dispersibility. Consequently, it also has a good appearance and excellent stability.

[0231] On the other hand, no small flake-like portions were identified in the micro-hollow particles of Comparative Example 1. The standard deviation of the particle size of the micro-hollow particles of Comparative Example 1 was 8.1, which was larger than that of the micro-hollow particles of Example 1, indicating poor dispersibility. Furthermore, the particles were confirmed to have a porous appearance and poor stability.

[0232] (B) Ingredients

[0233] •Pre-1: Terminal isocyanate urethane prepolymer with an isocyanate equivalent of 905; (B1) component

[0234] (Pre-1 manufacturing method)

[0235] In a flask equipped with a nitrogen inlet tube, thermometer, and stirrer, 50 g of 2,4-toluene 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 isocyanate equivalent of 905 (Pre-1).

[0236] (C) Components

[0237] • CB-1; a cyclic molecule with nine hydroxyl groups at the end of its side chain; (CB) component

[0238] (Manufacturing method of CB-1)

[0239] 10 g of hydroxypropylated β-cyclodextrin (CycloChem Co., Ltd.) and 32.0 g of ε-caprolactone were stirred at 130 °C under dry nitrogen flow to form a homogeneous solution. Then, 0.04 g of tin(II) 2-ethylhexanoate was added, and the reaction was carried out for 16 hours to obtain a cyclic molecule (CB-1) with nine hydroxyl groups at the end of its side chain, which is the target compound. The properties of CB-1 are described below.

[0240] Weight-average molecular weight (Mw(GPC)): 4800

[0241] Dispersion (GPC): 1.05

[0242] Side chain modification degree: 0.43 (43% if expressed as a percentage)

[0243] Polymerizable group at the end of the side chain: hydroxyl group

[0244] Number of side chains introduced into the cyclic molecule: 9

[0245] The molecular weight of the side chain is approximately 550 on a number-average basis.

[0246] Viscosity: 3800 mPa·s

[0247] Residual tin content: 300ppm

[0248] [Determination Method]

[0249] (1) Density:

[0250] Density (g / cm³) determined using DSG-1 from Toyo Seiki Corporation 3 ).

[0251] (2) Shore D hardness:

[0252] Shore D hardness was determined using a polymer instrument according to JIS standard (hardness test) K6253. Tests were performed by overlapping samples with a thickness of 6 mm. Lower hardness samples were measured using Shore A hardness, while higher hardness samples were measured using Shore D hardness.

[0253] (3) Hysteresis loss: For resin cut into dumbbell No. 8 shape with a thickness of 2mm, a universal tensile testing machine manufactured by Shimadzu AG-SX was used to stretch 20mm at 10mm / min, and then the hysteresis loss when the stress return becomes zero was measured.

[0254] (4) Grinding rate:

[0255] The grinding rate was determined under the following conditions. The grinding rate was the average of three 2-inch sapphire wafers.

[0256] CMP polishing pad: A pad with concentric circular grooves formed on its surface, 300mm in size and 1mm in thickness.

[0257] Slurry: FUJIMI COMPOL 80 concentrate

[0258] Pressure: 0.7 psi

[0259] Speed: 45 rpm

[0260] Time: 1 hour

[0261] (5) Scratches: The presence of scratches on the wafer during grinding was confirmed under the conditions described in (4) above. The evaluation was performed based on the following criteria.

[0262] All three images at a 1:3 scale showed no scratches under a laser microscope.

[0263] 2: Only one image showed a scratch that could be confirmed under a laser microscope.

[0264] 3: Both images show visible scratches under a laser microscope.

[0265] 4: All three images show visible scratches under a laser microscope.

[0266] <Example 2>

[0267] 12.5 parts by mass of CB-1 (component CB) and 5.7 parts by mass of 4,4'-methylenebis(o-chloroaniline) (MOCA) (component CA) were mixed at 120°C to prepare a homogeneous solution, which was then thoroughly degassed to prepare solution A. Separately, 10 parts by mass of the micro-hollow particles from Example 1 were added to 81.8 parts by mass of Pre-1 (component B1) prepared above, heated to 70°C, and stirred using a rotary mixer to prepare a homogeneous solution, solution B. Solution A was added to the aforementioned mixed solution B and mixed uniformly to prepare a curable composition. The curable composition was injected into a mold, degassed under reduced pressure of 5 kPa for 2 minutes, and then cured at 100°C for 15 hours. After curing, the cured product was removed from the mold.

[0268] Next, the cured material was sliced ​​to produce cured products with thicknesses of 2 mm and 1 mm. The 2 mm thick cured product was used to measure the various physical properties described above. The density of the resulting cured product was 1.0 g / cm³. 3 The Shore D hardness is 32D, and the hysteresis loss is 25%.

[0269] Additionally, spiral grooves are formed on the surface of a 1mm thick cured material obtained by slicing, and double-sided adhesive tape is adhered to the back, thereby creating a product of various sizes. Abrasive pad formed from a 1mm thick cured material.

[0270] The abrasive pad formed from the cured material obtained above had an abrasion rate of 1.7 μm / hour and a scratch evaluation of 1. The results are shown in Table 2.

[0271] <Comparative Example 2>

[0272] Instead of the tiny hollow particles of Example 2, 0.8 parts by weight of commercially available microcapsules 920-40 (manufactured by Japan Fillite Co., Ltd., consisting of tiny hollow particles formed from acrylonitrile resin with inorganic powder sprinkled on the surface) were used. The cured product was prepared in the same manner as in Example 2, and the density of the resulting cured product was 0.8 g / cm³. 3 The Shore D hardness is 24D, and the hysteresis loss is 31%. It should be noted that the tiny hollow particles used in Comparative Example 2 do not have small flake-like portions in the resin film.

[0273] <Comparative Example 3>

[0274] Instead of the micro hollow particles of Example 2, the micro hollow particles of Comparative Example 1 were used, and the cured product was manufactured in the same manner as in Example 2, except that the density of the cured product was 1.05 g / cm³. 3 The Shore D hardness is 33D, and the hysteresis loss is 27%. It should be noted that the tiny hollow particles used in Comparative Example 3 do not have small flake-like portions in the resin film.

[0275] Additionally, spiral grooves are formed on the surface of a 1mm thick cured material obtained by slicing, and double-sided adhesive tape is adhered to the back, thereby creating a product of various sizes. Abrasive pad formed from a 1mm thick cured material.

[0276] The abrasive pad formed from the cured material obtained above had an abrasive rate of 1.2 μm / hour and a scratch rating of 1. The results are shown in Table 2.

[0277] [Table 2]

[0278] Table 2

[0279]

[0280] Explanation of reference numerals in the attached figures

[0281] 1a, 1b: Tiny hollow particles

[0282] 2: Small flakes

[0283] 3: Combination Part

Claims

1. A type of tiny hollow particle, characterized in that, It is a series of tiny hollow particles composed of a resin film formed from melamine-based resin. The resin film is composed of multiple small sheet-like portions and bonding portions that bind them together. The small sheet-like portions are at least one shape selected from the group consisting of ellipsoids and spheres. The particle size of the tiny hollow particles composed of the resin film formed from melamine-based resin is 10μm to 100μm.

2. The micro hollow particles according to claim 1, wherein, The longest diameter of the small sheet-like portion is 1μm to 20μm.

3. A cured product formed by dispersing the tiny hollow particles as described in claim 1 or 2 in a polyurethane resin.

4. A CMP abrasive pad comprising the cured material of claim 3.

5. A method for manufacturing micro hollow particles, comprising manufacturing micro hollow particles composed of a resin film formed from melamine-based resin, wherein the micro hollow particles are manufactured by a method including the following steps: Step 1: (a) The process of preparing the oil phase of the organic solvent; Step 2: (b) The process of preparing the aqueous phase containing the surfactant; Step 3: The process of mixing / stirring the oil phase and the water phase to prepare an O / W emulsion in which the water phase is the continuous phase and the oil phase is the dispersed phase; Step 4: Adding a melamine-formaldehyde prepolymer compound as an additive phase to the O / W emulsion, and carrying out a condensation reaction of hydroxymethylated melamine as the melamine-formaldehyde prepolymer compound at the interface of the O / W emulsion to form a resin film, prepare microparticles encapsulating the oil phase, and obtain a microparticle dispersion containing microparticles. Step 5: The step of separating the microparticles from the microparticle dispersion; Step 6: The process of removing the oil phase from the interior of the microparticles to produce micro hollow particles. Furthermore, the weight ratio of the oil phase of the organic solvent (a), i.e., component (a), to the aqueous phase containing the surfactant (b), i.e. component (b), is: when component (a) is set to 100 parts by mass, component (b) is 100 to 500 parts by mass. The amount of the surfactant is 0.1 to 10 parts by mass relative to 100 parts by mass of the aqueous phase, the particle size of the micro hollow particles is 10 μm to 100 μm, the resin film is composed of a plurality of small sheet-like portions and a bonding portion that binds them together, and the small sheet-like portions are at least one shape selected from the group consisting of ellipsoids and spheres.

6. The manufacturing method according to claim 5, wherein, The organic solvent used in the oil phase of (a) is selected from organic solvents with a boiling point of 100°C to 180°C.

Images