Microballoons containing polymerizable functional groups

Abstract

Each microballoon according to the present invention: has, on a surface layer of the microballoon, a polymerizable functional group that possesses reactivity with respect to an iso(thio)cyanate group; and has a particle diameter of 10-200 µm. Employing the microballoons of the present invention in a CMP polishing pad makes it possible to realize superior polishing properties and superior durability in the polishing pad.

Description

[Technical Field]

[0001] This invention relates to a novel microballoon. [Background technology]

[0002] Microballoons have traditionally been used in many fields, including pesticides, pharmaceuticals, fragrances, liquid crystals, adhesives, electronic materials and components, as microballoons containing skincare ingredients, fragrance ingredients, dye ingredients, analgesic ingredients, deodorizing ingredients, antioxidant ingredients, antibacterial ingredients, heat-retaining ingredients, etc., or as hollow microballoons with a hollow interior.

[0003] In particular, in recent years, hollow microballoons have been considered for the purpose of creating pores in polyurethane (urea) resin polishing pads used for CMP (Chemical Mechanical Polishing) in wafer polishing.

[0004] Conventionally, microballoons used in CMP polishing pads have been known to be made of vinylidene chloride resin or the like, with inorganic particles sprinkled on the surface of the microballoon to improve dispersibility in polyurethane (urea) resin used as the base material for CMP polishing pads. However, these inorganic particles could potentially cause defects in the wafer.

[0005] Therefore, the present inventors have proposed a CMP polishing pad having excellent polishing characteristics by using microballoons formed from a polyurethane (urea) resin film that is highly elastic and has good compatibility with polyurethane (urea) resin in the CMP polishing pad (see Patent Document 1).

[0006] However, with the miniaturization of semiconductor wiring in recent years, there is a demand for even higher-performance polishing pads for CMP, and further improvements are required in the durability of microballoons and the properties of the resin. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] International Publication No. 2019 / 198675 [Overview of the project] [Problems that the invention aims to solve]

[0008] As a result of our investigation, we found that when using the microballoons described in Patent Document 1 as polishing pads for CMP, the microballoons may detach from the polishing pads during polishing, and this can be one of the causes of scratches on the workpiece.

[0009] Therefore, the object of the present invention is to provide a microballoon that can exhibit excellent polishing characteristics while preventing the microballoon from falling off the CMP polishing pad when used with a CMP polishing pad. [Means for solving the problem]

[0010] The inventors, after diligent research to solve the above problems, discovered that by using microballoons having polymerizable functional groups on their surface that are reactive with iso(thio)cyanate groups, it becomes difficult for the microballoons to detach from the polishing pad during CMP polishing. Furthermore, they found that this not only suppresses scratches caused by contact between detached microballoons and the workpiece, but also prevents wear caused by contact between the detached microballoons and the polishing pad. Moreover, by using the microballoons with a particle size of 10 to 200 μm, it is possible to achieve an excellent polishing rate. Therefore, by using the above microballoons, the inventors have found that the above problems can be solved, and have completed the present invention.

[0011] In other words, the present invention relates to a microballoon having polymerizable functional groups on its surface that are reactive with iso(thio)cyanate groups, and having a microballoon particle size of 10 to 200 μm.

[0012] Furthermore, the present invention also provides a polishing pad for CMP that includes the microballoons.

[0013] The present invention relates to the following [1] to [9]. [1] A microballoon having polymerizable functional groups on its surface that are reactive with iso(thio)cyanate groups, and having a particle size of 10 to 200 μm. [2] The microballoon according to [1], wherein the polymerizable functional group that reacts with the iso(thio)cyanate group is at least one group selected from the group consisting of a hydroxyl group, an amino group, and a thiol group. [3] The microballoon according to [1] or [2] above, wherein the amount of polymerizable functional groups that react with iso(thio)cyanate groups on the surface is 0.75 mmol / g or more per weight of the microballoon. [4] The microballoon according to any one of the above [1] to [3], wherein the microballoon is made of at least one resin selected from the group consisting of urethane (urea) resin, melamine resin, urea resin, and amide resin. [5] The microballoon according to any one of the above items [1] to [4], wherein the ash content of the microballoon is 0.5 parts by mass or less when the microballoon is 100 parts by mass. [6] The bulk density of the microballoon is 0.01 to 0.5 g / cm³ 3 A microballoon as described in any one of the above [1] to [5]. [7] A polyurethane (urea) resin comprising the microballoons described in any one of the above items [1] to [6]. [8] Polishing pad for CMP using the polyurethane (urea) resin described in [7] above. [9] The Shore hardness of the polyurethane (urea) resin is 40A to 80D, and the density is 0.60 to 0.95 g / cm 3 The CMP polishing pad according to [8] above, which has such properties.

Effects of the Invention

[0014] The microballoon of the present invention is characterized in that it has a polymerizable functional group reactive with an iso(thio)cyanate group on the surface layer of the microballoon, and the particle size of the microballoon is 10 to 200 μm.

[0015] Also, by using the CMP polishing pad containing the microballoon, it is possible to exhibit excellent polishing characteristics and excellent durability of the polishing pad. For example, it is possible to reduce a high polishing rate and defects generated on the wafer.

[0016] Furthermore, the microballoon of the present invention can be used in many fields such as heat-sensitive recording materials, agricultural chemicals, pharmaceuticals, fragrances, liquid crystals, adhesives, electronic material parts, and building materials, in addition to the use as a CMP polishing pad.

Embodiments for Carrying Out the Invention

[0017] The microballoon of the present invention is a microballoon that has a polymerizable functional group reactive with an iso(thio)cyanate group on the surface layer of the microballoon, and the particle size of the microballoon is 10 to 200 μm. In this specification, the iso(thio)cyanate group means one or both of an isocyanate group and an isothiocyanate group. The microballoon of the present invention is a particle having an outer shell. The inside of the microballoon may be hollow, or may contain an organic solvent or the like. The outer shell is formed of a resin, and preferred resins are as described later. Also, having a polymerizable functional group on the surface layer of the microballoon means that the resin constituting the outer shell of the microballoon has a polymerizable functional group.

[0018] First, the microballoon will be described. The polymerizable functional group having reactivity with an iso(thio)cyanate group on the surface layer of the microballoon of the present invention can be used without any limitation as long as it is a polymerizable functional group having reactivity with an iso(thio)cyanate group. Among them, preferred polymerizable functional groups include a hydroxyl group, an amino group, and a thiol group, and particularly preferred polymerizable functional groups include a hydroxyl group and an amino group.

[0019] In the present invention, the method for confirming the presence or absence of a polymerizable functional group having reactivity with an iso(thio)cyanate group on the surface layer of the microballoon is not particularly limited. For example, a method of adding a microballoon to a compound having an iso(thio)cyanate group and confirming whether the number of moles of the iso(thio)cyanate group changes before and after the addition of the microballoon can be mentioned. At this time, when using a polyfunctional iso(thio)cyanate compound as the compound having an iso(thio)cyanate group, it is considered that crosslinking and thickening may occur, so it is preferable to use a monofunctional isocyanate compound. Specific examples include adding a microballoon to butyl isocyanate, sufficiently stirring, and then determining by quantifying the iso(thio)cyanate group by a back titration method in accordance with JIS K 7301. Although an example using butyl isocyanate is shown here, of course, it is not limited to this, and other compounds having an iso(thio)cyanate group may be used.

[0020] To explain the above method in detail, butyl isocyanate (or a butyl isocyanate solution of known concentration) and a clearly excess amount of di-n-butylamine compared to the amount of isocyanate groups in the butyl isocyanate are added to a dry solvent that does not react with isocyanate groups, and the total isocyanate groups of the butyl isocyanate react with the di-n-butylamine. Then, the amount of di-n-butylamine that was not consumed (did not participate in the reaction) is titrated with acid to determine the amount of consumed di-n-butylamine. Since the amount of consumed di-n-butylamine is equal to the amount of isocyanate groups in the butyl isocyanate, the isocyanate equivalent can be determined. To confirm the presence or absence of polymerizable functional groups that react with iso(thio)cyanate groups on the surface of the microballoon of the present invention, butyl isocyanate (or a butyl isocyanate solution of known concentration) with a known isocyanate equivalent is mixed with the microballoon, and then the decrease in the isocyanate equivalent of the butyl isocyanate can be confirmed. For example, if the isocyanate equivalent of butyl isocyanate decreases, it can be seen that the microballoon has polymerizable functional groups on its surface that are reactive with iso(thio)cyanate groups.

[0021] In the present invention, the amount of polymerizable functional groups that react with iso(thio)cyanate groups on the surface of the microballoons per unit weight is preferably 0.75 mmol / g or more, more preferably 1 mmol / g or more, and most preferably 2 mmol / g or more. This makes it easier to prevent the microballoons from falling off the CMP polishing pad when they are used in a CMP polishing pad. The amount of polymerizable functional groups that react with iso(thio)cyanate groups on the surface of the microballoons per unit weight can be measured by back titration in accordance with JIS K 7301, as described above.

[0022] The particle size of the microballoons of the present invention must be between 10 μm and 200 μm, more preferably between 10 μm and 100 μm, and most preferably between 10 μm and 50 μm. Being within this range allows for excellent polishing properties when incorporated into CMP polishing pads. Note that the particle size of a microballoon refers to the average particle diameter of the microballoon. The average particle diameter of a microballoon can be measured using known methods; specifically, image analysis can be used. Image analysis allows for easy measurement of particle size. The average particle diameter is the average particle diameter of the primary particles. Average particle diameter measurement using image analysis can be performed, for example, using an optical microscope or a scanning electron microscope. Specifically, the individual particle diameters of multiple (at least 20) microballoons are measured using image analysis, and the average particle diameter is calculated as the average value of these measurements. Furthermore, the particle diameter of each microballoon is defined as the diameter of the observed particle if its shape is circular, or, if the observed particle has a shape other than circular, the maximum straight-line distance between any two points on the outer circumference of that particle.

[0023] The bulk density of the microballoons of the present invention, when they are hollow microballoons, is not particularly limited, but is generally 0.01 to 0.5 g / cm³. 3 Preferably, it is 0.02 to 0.3 g / cm³. 3 It is more preferable that the pore size is within this range. Being within this range allows for the formation of optimal pores on the polishing surface while ensuring the physical properties of the polishing pad for CMP.

[0024] The ash content of the microballoons of the present invention is not particularly limited, but in the methods described in the examples below, it is preferably 0.5 parts by mass or less, more preferably 0.3 parts by mass or less, more preferably 0.1 parts by mass or less, and most preferably not detectable, per 100 parts by mass of the microballoons. Being within this range makes it possible to reduce wafer defects when used in polishing pads for CMP.

[0025] Furthermore, considering the introduction of polymerizable functional groups that react with isocyanate groups on the surface of the microballoon as described above, it is preferable that the microballoon be made of at least one resin selected from the group consisting of urethane (urea) resin, melamine resin, urea resin, and amide resin. These resins constitute the outer shell of the microballoon.

[0026] In this invention, "introducing polymerizable functional groups" refers not only to cases where polymerizable functional groups are introduced separately, but also to cases where polymerizable functional groups inherently exist in the resin being used.

[0027] In the present invention, the urethane (urea) resin is a resin obtained by the reaction of a compound having an iso(thio)cyanate group with a compound having at least one group selected from the group consisting of a hydroxyl group, a thiol group, and an amino group, and is a resin having a urethane bond in the main chain, a resin having a urea bond, or a resin having both a urethane bond and a urea bond in the main chain (including cases in which the oxygen atom of the bond is substituted with a sulfur atom). The melamine resin is a resin obtained by polycondensation of a polyfunctional amine containing melamine in its main chain with formaldehyde; the urea resin is a resin obtained by polycondensation of urea (which also contains a polyfunctional amine) in its main chain with formaldehyde; and the amide resin is a resin having amide bonds in its main chain.

[0028] In the present invention, the polymerizable monomers constituting these resins include, but are not limited to, the following.

[0029] When the microballoon is made of urethane (urea) resin, a microballoon made of urethane (urea) resin can be made by using at least one compound selected from the following as polymerizable monomers: (A1) a polyfunctional iso(thio)cyanate compound having at least two iso(thio)cyanate groups (hereinafter also referred to as (A1) polyfunctional iso(thio)cyanate compound or (A1) component); (A2) a poly(thio)ol compound having at least two groups selected from the group consisting of hydroxyl groups and thiol groups in one molecule (hereinafter also referred to as (A2) poly(thio)ol compound or (A2) component); (A3) a polyfunctional amine compound having at least two amino groups (hereinafter also referred to as (A3) polyfunctional amine compound or (A3) component); and (A4) a compound having at least both hydroxyl groups and amino groups (hereinafter also referred to as (A4) component).

[0030] If the microballoon is made of melamine resin, (A5) a melamine-formaldehyde prepolymer compound can be used to produce a microballoon made of melamine resin.

[0031] If the microballoon is made of urea resin, (A6) a urea-formaldehyde prepolymer compound can be used to produce a microballoon made of urea resin.

[0032] When the microballoon is made of an amide resin, a microballoon made of an amide resin can be produced by using (A7) a polyfunctional carboxylic acid having at least two carboxyl groups and (A3) a polyfunctional amine compound having at least two amino groups.

[0033] The method for introducing polymerizable functional groups that react with isocyanate groups on the surface of the microballoon is not particularly limited, but if the microballoon is made of urethane (urea) resin, some of the hydroxyl groups, thiol groups, and amino groups of components (A2) to (A4) may be left on the surface, or isocyanate groups may be left on the surface and then modified into amino groups by reaction with water, or hydroxyl groups, thiol groups, and amino groups may be introduced by modifying the surface after the microballoon is made using components (A2) to (A4) that already have reactive active sites.

[0034] If the microballoon is made of melamine resin, unreacted amino groups derived from melamine may be used, or melamine with pre-introduced reactive sites may be used, and after microballoon formation, hydroxyl groups, amino groups, or thiol groups may be introduced using the reactive sites.

[0035] If the microballoon is made of urea resin, the unreacted amino groups derived from the urea may be used, or urea with pre-introduced reactive sites may be used, and after the microballoon is formed, hydroxyl groups, amino groups, or thiol groups may be introduced using the reactive sites.

[0036] If the microballoon is made of an amide resin, some of the amino groups of component (A3) may be left intact, or some of the amino groups of melamine may be modified in advance with a compound having hydroxyl groups, amino groups, or thiol groups, or component (A7) or component (A3) which has reaction active sites introduced in advance may be used, and after the microballoon is formed, the reaction active sites may be used to introduce hydroxyl groups, amino groups, or thiol groups.

[0037] The above-mentioned reaction active sites are not particularly limited, but examples include radical polymerizable groups.

[0038] The following are specific examples of polymerizable monomers. <(A1) Polyfunctional isocyanate compounds having at least two iso(thio)cyanate groups> The (A1) polyfunctional iso(thio)cyanate compound used in the present invention is a compound having at least two groups selected from the group consisting of isocyanate groups and isothiocyanate groups. Of course, compounds having both isocyanate groups and isothiocyanate groups are also selected. Among these, compounds having 2 to 6 iso(thio)cyanate groups in the molecule are preferred, compounds having 2 to 4 are more preferred, and compounds having 2 to 3 are even more preferred.

[0039] Furthermore, component (A1) may be a urethane prepolymer containing unreacted iso(thio)cyanate groups (hereinafter also referred to as (A12) urethane prepolymer or component (A12)) prepared by the reaction of a difunctional iso(thio)cyanate compound and a difunctional poly(thio)ol compound or difunctional amine compound, as described later. The (A12) urethane prepolymer can be used without any limitations as long as it contains unreacted isocyanate groups.

[0040] The (A1) iso(thio)cyanate compounds can be broadly classified into aliphatic isocyanates, alicyclic isocyanates, aromatic isocyanates, isothiocyanates, other isocyanates, and (A12) urethane prepolymers. Furthermore, the (A1) component may use one type of compound or multiple types of compounds. When multiple types of compounds are used, the standard mass is the total amount of the multiple types of compounds. Specific examples of these (A1) components are as follows.

[0041] (Aliphatic isocyanates) Ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2'-dimethylpentane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-trimethylundecamethylene diisocyanate, 1,3,6-trimethylhexamethylene Difunctional isocyanate monomers such as ethylene diisocyanate, 1,8-diisocyanate 4-isocyanate methyl octane, 2,5,7-trimethyl-1,8-diisocyanate 5-isocyanate methyl octane, bis(isocyanate ethyl) carbonate, bis(isocyanate ethyl) ether, 1,4-butylene glycol dipropyl ether-ω,ω'-diisocyanate, lysine diisocyanate methyl ester, and 2,4,4-trimethylhexamethylene diisocyanate (corresponding to difunctional iso(thio)cyanate compounds that constitute urethane prepolymers).

[0042] (Alicyclic isocyanates) Isophorone diisocyanate, (bicyclo[2.2.1]heptane-2,5-diyl)bismethylene diisocyanate, (bicyclo[2.2.1]heptane-2,6-diyl)bismethylene diisocyanate, 2β,5α-bis(isocyanate)norbornane, 2β,5β-bis(isocyanate)norbornane, 2β,6α-bis(isocyanate)norbornane, 2β,6β-bis(isocyanate)norbornane, 2,6-di(isocyanatemethyl)furan, 1,3-bis(isocyanatemethyl)cyclohexane, dicyclohexyl Xylmethane-4,4'-diisocyanate, 4,4-isopropylidenebis(cyclohexyl isocyanate), cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate, bis(4-isocyanate n-butylidene)pentaerythritol, diisocyanate dimer acid, 2,5-bis(isocyanate methyl)-bicyclo[2,2,1]-heptane, 2,6-bis(isocyanate methyl)-bisic Ro[2,2,1]-heptane, 3,8-bis(isocyanatemethyl)tricyclodecane, 3,9-bis(isocyanatemethyl)tricyclodecane, 4,8-bis(isocyanatemethyl)tricyclodecane, 4,9-bis(isocyanatemethyl)tricyclodecane, 1,5-diisocyanate todecalin, 2,7-diisocyanate todecalin, 1,4-diisocyanate todecalin, 2,6-diisocyanate todecalin, bicyclo[4.3.0]nonane-3,7-diisocyanate, bicyclo[4.3.0]nonane-4,8-diisocyanate Difunctional isocyanate monomers such as bicyclo[2.2.1]heptane-2,5-diisocyanate and bicyclo[2.2.1]heptane-2,6-diisocyanate, bicyclo[2,2,2]octane-2,5-diisocyanate, bicyclo[2,2,2]octane-2,6-diisocyanate, tricyclo[5.2.1.02.6]decane-3,8-diisocyanate, and tricyclo[5.2.1.02.6]decane-4,9-diisocyanate (corresponding to difunctional iso(thio)cyanate compounds that constitute urethane prepolymers).

[0043] 2-Isocyanatemethyl-3-(3-isocyanatetopropyl)-5-isocyanatemethyl-bicyclo[2,2,1]-heptane, 2-Isocyanatemethyl-3-(3-isocyanatetopropyl)-6-isocyanatemethyl-bicyclo[2,2,1]-heptane, 2-Isocyanatemethyl-2-(3-isocyanatetopropyl)-5-isocyanatemethyl-bicyclo[2,2,1]-heptane, 2-Isocyanatemethyl-2-(3-isocyanatetopropyl)-6-isocyanatemethyl-bicyclo[2,2,1]-heptane, 2-Isocyanatemethyl-3-(3-isocyanatetopropyl) Polyfunctional isocyanate monomers such as -5-(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.

[0044] (Aromatic isocyanates) Xylylene diisocyanate (o-, m-, p-), tetrachloro-m-xylylene diisocyanate, methylenediphenyl-4,4'-diisocyanate, 4-chlor-m-xylylene diisocyanate, 4,5-dichlor-m-xylylene diisocyanate, 2,3,5,6-tetrabrom-p-xylylene diisocyanate, 4-methyl-m-xylylene diisocyanate, 4-ethyl-m-xylylene 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, α,α,α',α'-tetramethylxylylene diisocyanate, bis(isocyanate butyl)benzene, bis(isocyanate methyl)naphthalene, bis(isocyanate methyl)diphenyl ether, bis(isocyanate ethyl)phthalate, 2,6-di(isocyanate methyl)furan, phenylenediisocyanate (o-,m-,p-), ethylphenylenediisocyanate, isopropyl Phenylene diisocyanate, dimethylphenyl diisocyanate, diethylphenyl diisocyanate, diisopropylphenyl diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, 1,3,5-triisocyanate methylbenzene, 1,5-naphthalene diisocyanate, methylnaphthalene diisocyanate, biphenyl diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-diphenyl Phenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, bibenzyl-4,4'-diisocyanate, bis(isocyanatephenyl)ethylene, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, phenyl isocyanate methyl isocyanate, phenyl isocyanate ethyl isocyanate, tetrahydronaphthylene diisocyanate, hexahydrobenzene diisocyanate, hexahydrodiphenylmethane-4,Difunctional isocyanate monomers such as 4'-diisocyanate, diphenyl ether diisocyanate, ethylene glycol-diphenyl ether diisocyanate, 1,3-propylene glycol-diphenyl ether diisocyanate, benzophenone diisocyanate, diethylene glycol-diphenyl ether diisocyanate, dibenzofrandiisocyanate, carbazole diisocyanate, ethylcarbazole diisocyanate, dichlorocarbazole diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate (corresponding to difunctional iso(thio)cyanate compounds that constitute urethane prepolymers).

[0045] Polyfunctional isocyanate monomers such as methylylene 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-pentaiisocyanate.

[0046] (Isothiocyanate) Difunctional isothiocyanates such as p-phenylenediisothiocyanate, xylylene-1,4-diisothiocyanate, and ethylidine diisothiocyanate (corresponding to difunctional iso(thio)cyanate compounds that constitute urethane prepolymers).

[0047] (Other isocyanates) Other isocyanates include polyfunctional isocyanates having a burette structure, uretdione structure, or isocyanurate structure (for example, Japanese Patent Publication No. 2004-534870 discloses a method for modifying the burette structure, uretdione structure, or isocyanurate structure of aliphatic polyisocyanates) using diisocyanates such as hexamethylene diisocyanate and tolylene diisocyanate as the main raw material, and polyfunctional isocyanates formed as adducts with three or more functional polyols such as trimethylolpropane (disclosed in textbooks such as "Polyurethane Resin Handbook" edited by Keiji Iwata, Nikkan Kogyo Shimbun (1987)).

[0048] ((A12) Urethane prepolymer) In the present invention, the (A12) urethane prepolymer is preferably obtained by reacting a bifunctional isocyanate compound selected from the (A1) components described above (compounds specified in the examples given as (A1) components) with the following (A21) bifunctional poly(thiol) compound or (A31) bifunctional amine compound.

[0049] Examples of the (A21) bifunctional poly(thiol) compounds mentioned above include the following:

[0050] ((A21)2-functional poly(thiol)ol (Aliphatic diols) Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 1,5-dihydroxypentane, 1,6-dihydroxyhexane, 1,7-dihydroxyheptane, 1,8-dihydroxyoctane, 1,9-dihydroxynonane, 1,10-dihydroxydecane, 1,11-dihydroxyundecane, 1,12-dihydroxydodecane, neopentyl glycol, glyceryl monooleate, monoelaidin, polyethylene glycol, 3-methyl-1,5-dihydroxypentane, dihydroxyneopentyl, 2-ethyl-1,2-dihydroxyhexane, 2-methyl-1,3-dihydroxypropane, polyester polyol (a compound having hydroxyl groups only at both ends obtained by the condensation reaction of a polyol with a polybasic acid), polyether polyol (alkylene Difunctional polyol compounds such as: ring-opening polymerization of oxides, or compounds obtained by the reaction of a compound having two or more active hydrogen-containing groups in the molecule with an alkylene oxide, and modified versions thereof, having hydroxyl groups only at both ends of the molecule; polycaprolactone polyols (compounds obtained by ring-opening polymerization of ε-caprolactone, having hydroxyl groups only at both ends of the molecule); polycarbonate polyols (compounds obtained by phosgenating one or more low molecular weight polyols, or compounds obtained by transesterification using ethylene carbonate, diethyl carbonate, diphenyl carbonate, etc., having hydroxyl groups only at both ends of the molecule); and polyacrylic polyols (polyol compounds obtained by polymerizing (meth)acrylate esters or vinyl monomers, having hydroxyl groups only at both ends of the molecule).

[0051] (Alicyclic diols) Difunctional polyol compounds such as hydrogenated bisphenol A, cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, tricyclo[5,2,1,02,6]decane-dimethanol, bicyclo[4,3,0]-nonanediol, dicyclohexanediol, tricyclo[5,3,1,13,9]dodecanediol, bicyclo[4,3,0]nonanedimethanol, tricyclo[5,3,1,13,9]dodecane-diethanol, hydroxypropyltricyclo[5,3,1,13,9]dodecanol, spiro[3,4]octanediol, butylcyclohexanediol, 1,1'-bicyclohexylidenediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, and o-dihydroxyxylylene.

[0052] (Aromatic diols) Dihydroxynaphthalene, dihydroxybenzene, bisphenol A, bisphenol F, xylylene glycol, tetrabrombisphenol A, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)-1-naphthylmethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2-(4-hydroxyphenyl 2,2-(3-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)-3-methylbutane, 2,2-bis(4-hydroxyphenyl)pentane, 3,3-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)hexane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 2,2-bis(4-hydroxyphenyl) Butane, 4,4-bis(4-hydroxyphenyl)heptane, 2,2-bis(4-hydroxyphenyl)tridecane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3-ethyl-4-hydroxyphenyl)propane, 2,2-bis(3-n-propyl-4-hydroxyphenyl)propane, 2,2-bis(3-isopropyl-4-hydroxyphenyl)propane, 2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane, 2,2-bis(3- tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2-bis(3-allyl-4'-hydroxyphenyl)propane, 2,2-bis(3-methoxy-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(2,3,5,6-tetramethyl-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)cyanomethane, 1-cyano-3,3-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cycloheptane, 1,1-bis(3-methyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dichloro-4-hydroxyphenyl)cyclohexane, 1,1-bis(3-methyl-4-hydroxyphenyl)-4-methyl Tylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)norbornane, 2,2-bis(4-hydroxyphenyl)adamantane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, ethylene glycol bis(4-hydroxyphenyl) ether, 4,4'-dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide, 3,3'-dicyclo Hexyl-4,4'-dihydroxydiphenyl sulfide, 3,3'-diphenyl-4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, bis(4-hydroxyphenyl) ketone, bis(4-hydroxy-3-methylphenyl) ketone, 7,7'-dihydroxy-3,3',4,4'-tetrahydro-4,4 4',4'-Tetramethyl-2,2'-Spirobi(2H-1-Benzopyrane), Trans-2,3-Bis(4-Hydroxyphenyl)-2-Butene, 9,9-Bis(4-Hydroxyphenyl)Fluorene, 3,3-Bis(4-Hydroxyphenyl)-2-Butanone, 1,6-Bis(4-Hydroxyphenyl)-1,6-Hexanedione, 4,4'-Dihydroxybiphenyl, m-Dihydroxyxylylene, p-Dihydroxyxylylene, 1,4-Bis(2-Hydroxyethyl)benzene, 1,4-Bis(3-Hydroxypropyl)benzene, 1,4-bis(4-hydroxybutyl)benzene, 1,4-bis(5-hydroxypentyl)benzene, 1,4-bis(6-hydroxyhexyl)benzene, 2,2-bis[4-(2"-hydroxyethyloxy)phenyl]propane, and difunctional polyol compounds such as hydroquinone and resorcinol.

[0053] (Polyester Diol) Examples include bifunctional polyol compounds obtained by the condensation reaction of a polyol with a polybasic acid. Among these, a number-average molecular weight of 400 to 2000 is preferred, more preferably 500 to 1500, and most preferably 600 to 1200.

[0054] (Polyetherdiol) Examples include bifunctional polyol compounds and their modified forms obtained by ring-opening polymerization of alkylene oxides, or by the reaction of a compound having two or more active hydrogen-containing groups in its molecule with an alkylene oxide. In particular, the number average molecular weight is preferably 400 to 2000, more preferably 500 to 1500, and most preferably 600 to 1200.

[0055] (Polycaprolactone diol) Examples include bifunctional polyol compounds obtained by ring-opening polymerization of ε-caprolactone. Among these, a number-average molecular weight of 400 to 2000 is preferred, more preferably 500 to 1500, and most preferably 600 to 1200.

[0056] (Polycarbonate diol) Examples include bifunctional polyol compounds obtained by phosgenating one or more low molecular weight polyols, or bifunctional polyol compounds obtained by transesterification using ethylene carbonate, diethyl carbonate, diphenyl carbonate, etc. Among these, a number average molecular weight of 400 to 2000 is preferred, more preferably 500 to 1500, and most preferably 600 to 1200.

[0057] (Dithiol) Difunctional polythiol compounds such as tetraethylene glycol bis(3-mercaptopropionate), 1,4-butanediol bis(3-mercaptopropionate), 1,6-hexanediol bis(3-mercaptopropionate), and 1,4-bis(mercaptopropylthiomethyl)benzene.

[0058] (Compounds containing both hydroxyl and thiol groups) Difunctional poly(thiol) compounds such as 2-mercaptoethanol, 1-hydroxy-4-mercaptocyclohexane, 2-mercaptohydroquinone, 4-mercaptophenol, 1-hydroxyethylthio-3-mercaptoethylthiobenzene, 4-hydroxy-4'-mercaptodiphenylsulfone, 2-(2-mercaptoethylthio)ethanol, dihydroxyethyl sulfide mono(3-mercaptopropionate), and dimercaptoethane mono(salchylate).

[0059] ((A31) difunctional amine compound) Examples of the (A31)2-functional amine compounds mentioned above include the following:

[0060] (Aliphatic diamines) Difunctional amine compounds such as ethylenediamine, hexamethylenediamine, nonamethylenediamine, undecanemethylenediamine, dodecamethylenediamine, metaxylenediamine, 1,3-propanediamine, and putrescine.

[0061] (Alicyclic diamines) Difunctional amine compounds such as isophorone diamine and cyclohexyl diamine.

[0062] (Aromatic diamines) 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, trimethylene glycol-di-p-aminobenzoate, polytetramethylene glycol-di-p-aminobenzoate, 4,4'-diamino-3,3',5,5'-tetraethyldiphenylmethane, 4,4'-diamino-3,3'-diisopropyl-5,5'-dimethyldiphenylmethane, 4,4'-diamino-3,3',5,5'-tetraisopropyldiphenylmethane, 1 ,2-bis(2-aminophenylthio)ethane, 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, N,N'-di-sec-butyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, m-xylylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, p-phenylenediamine, 3,3'-methylenebis(methyl-6-aminobenzoate), 2,4-diamino-4-chlorobenzoate-2-methylpropyl, 2,4-diamino-4-chlorobenzoate-isopropyl, 2,4-diamino-4-chlorophenylacetate-isopropyl, di-(2-aminophenyl)thioethyl terephthalate, diphenylmethanediamine, tolylenediamine, piperazine, and other difunctional amine compounds.

[0063] ((A12) Method for producing urethane prepolymer) (A12) The urethane prepolymer is produced by reacting the aforementioned difunctional iso(thio)cyanate compound with (A21) a difunctional poly(thio)ol compound and / or (A31) a difunctional amine compound. However, in the present invention, the (A12) urethane prepolymer must contain unreacted iso(thio)cyanate groups. The method for producing the (A12) urethane prepolymer containing iso(thio)cyanate groups is not particularly limited to known methods, and for example, a method can be used in which the number of moles of iso(thio)cyanate groups (n5) in the difunctional iso(thio)cyanate compound and the number of moles of groups with active hydrogen (n6) in the (A21) difunctional poly(thio)ol compound and / or (A31) difunctional amine compound is in the range of 1 < (n5) / (n6) ≤ 2.3. When using two or more difunctional iso(thio)cyanate compounds, the number of moles of the iso(thio)cyanate group (n5) shall be the total number of moles of iso(thio)cyanate groups in those difunctional iso(thio)cyanate compounds. Also, when using two or more (A21) difunctional poly(thio)ol compounds and / or (A31) difunctional amine compounds, the number of moles of the group having the active hydrogen (n6) shall be the total number of moles of the active hydrogen in those (A21) difunctional poly(thio)ol compounds and / or (A31) difunctional amine compounds. In this invention, even if the active hydrogen is a primary amino group, the primary amino group is calculated as 1 mole. This is because a considerable amount of energy is required for the second amino group (-NH) of a primary amino group to react (even with a primary amino group, the second -NH is difficult to react). Therefore, in this invention, even if a difunctional active hydrogen-containing compound having a primary amino group is used, the primary amino group is calculated as 1 mole.

[0064] Furthermore, although not particularly limited, the (A12) urethane prepolymer has an iso(thio)cyanate equivalent (the molecular weight of the (A12) urethane prepolymer divided by the number of iso(thio)cyanate groups in one molecule) of preferably 300 to 5000, more preferably 350 to 3000, and particularly preferably 400 to 2000. In addition, the (A12) urethane prepolymer in the present invention is preferably a linear type produced from a difunctional iso(thio)cyanate compound and a (A21) difunctional poly(thio)ol compound and / or a (A31) difunctional amine compound, in which case both ends are iso(thio)cyanate groups, and the number of iso(thio)cyanate groups in one molecule is 2.

[0065] Furthermore, the isocyanate equivalent of the (A12) urethane prepolymer can be quantified by a back titration method in accordance with the method described in JIS K 7301 or International Publication No. WO2018-092826, which specifies the isocyanate groups present in the (A12) urethane prepolymer.

[0066] Furthermore, it is preferable that the iso(thio)cyanate content ((I); molal concentration (mol / kg)) of the (A12) urethane prepolymer and the urethane bond content ((U); molal concentration (mol / kg)) present in the (A12) urethane prepolymer are 1 ≤ (U) / (I) ≤ 10. This range is the same when the (A12) urethane prepolymer is used in combination with a bifunctional iso(thio)cyanate compound.

[0067] The isocyanate content ((I); molal concentration (mol / kg)) is the reciprocal of the isocyanate equivalent multiplied by 1,000. Furthermore, the urethane bond content ((U); molal concentration (mol / kg)) present in the urethane prepolymer (A12) can be theoretically determined using the following method. In other words, if the total iso(thio)cyanate content ((aI); molality (mol / kg)) is the amount of iso(thio)cyanate groups present in the difunctional iso(thio)cyanate compound constituting the (A12) urethane prepolymer before the reaction, then the urethane bond content ((U); molality (mol / kg)) is the value obtained by subtracting the iso(thio)cyanate content ((I); molality (mol / kg)) from the total iso(thio)cyanate group content ((aI); molality (mol / kg)) of component (A1) ((U) = (aI) - (I)), which is the urethane bond content (U) present in the (A12) urethane prepolymer.

[0068] Furthermore, in the production of (A12) urethane prepolymers, heating or the addition of a urethane catalyst may be performed as needed. Any suitable urethane catalyst can be used; for example, the urethane catalysts described later can be used.

[0069] The most preferred examples of component (A1) used in the present invention include, from the viewpoint of controlling the strength and reactivity of the formed microballoons, 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-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate (o-, m-, p-), polyfunctional isocyanates with a burette structure, uretdione structure, or isocyanurate structure, using diisocyanates such as hexamethylene diisocyanate and tolylene diisocyanate as the main raw materials, polyfunctional isocyanates as adducts with trifunctional or more polyols, or (A12) urethane prepolymers.

[0070] <(A2) Poly(thiol) compounds having at least two groups selected from the group consisting of hydroxyl groups and thiol groups in one molecule> The (A2) poly(thiol) compound used in the present invention can be used without limitation as long as it has at least two groups selected from the group consisting of hydroxyl groups and thiol groups in one molecule. Of course, compounds having both hydroxyl and thiol groups can also be selected. These also include the (A21) bifunctional poly(thiol) compounds used in the production of the (A12) urethane prepolymer. Component (A2) is preferably used in microballoons made of urethane (urea) resin. Component (A2) that is particularly preferably used in the microballoons of the present invention is a water-soluble poly(thiol) compound.

[0071] In the present invention, the water-soluble poly(thiol) compound is a compound that is at least partially soluble in water and has a higher affinity in the hydrophilic phase than in the hydrophobic phase. Generally, a compound can be selected that has a solubility of at least 1 g / l in a hydrophilic solvent such as water at room temperature, and preferably a water-soluble compound that has a solubility of 20 g / l or more in a hydrophilic solvent.

[0072] Examples of these water-soluble poly(thiol) compounds include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, neopentyl glycol, trimethylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, hexylene glycol, 1,6-hexanediol, 2-butene-1,4-diol, 2-mercaptoethanol and other bifunctional poly(thiol) compounds, glycerin, trimethylolethane, trimethylolpropane, 3-mercapto-1,2-propanediol and other trifunctional poly(thiol) compounds, pentaerythritol, Examples of water-soluble polymers include tetrafunctional polyols such as erythritol, diglycerol, diglycerin, and ditrimethylolpropane; pentafunctional polyols such as arabitol; hexafunctional polyols such as dulciitol, sorbitol, mannitol, dipentaerythritol, or triglycerol; heptafunctional polyols such as boremitol; nnanofunctional polyols such as isomalt, maltitol, isomaltitol, or lactitol; cellulosic compounds (e.g., methylcellulose, ethylcellulose, hydroxyethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, hydroxypropylcellulose, and their saponified products); starch, dextrin, cyclic dextrin, chitin, polyvinyl alcohol, and polyglycerin.

[0073] <(A3) Polyfunctional amine compounds having at least two amino groups> The (A3) polyfunctional amine compound used in the present invention can be any monomer having two or more amino groups in one molecule. These also include the (A31) bifunctional amine compounds used in the production of the (A12) urethane prepolymer. Component (A3) is preferably used in microballoons made of urethane (urea) resin or amide resin. Component (A3) is particularly preferably used in the microballoons of the present invention, and is a water-soluble polyamine compound.

[0074] The preferred solubility of these water-soluble polyamine compounds is the same as that of the water-soluble polyol compounds described above. These water-soluble polyamine compounds are polyfunctional amines having two or more amino groups in their molecule, and specifically include ethylenediamine, propylenediamine, 1,4-diaminobutane, hexamethylenediamine, 1,8-diaminooctane, 1,10-diaminodecane, dipropylenetriamine, bishexamethylenetriamine, tris(2-aminoethyl)amine, tris(3-aminopropyl)amine, 3,3',3''-nitrilotris(propionamide), piperazine, 2-methylpiperazine, isophoronediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hydrazine, polyethyleneimines, and polyoxyalkyleneamines.

[0075] <(A4) Compounds that have at least both a hydroxyl group and an amino group> The compounds having at least one hydroxyl group and one amine group used in the present invention are not limited to those having at least one hydroxyl group and one amino group in their molecule. Component (A4) is preferably used in microballoons made of urethane (urea) resin. Particularly preferred is a water-soluble compound having both a hydroxyl group and an amino group in its molecule.

[0076] The preferred solubility of water-soluble compounds having both hydroxyl and amino groups in their molecules is the same as that of the water-soluble polyol compounds described above. Specifically, these water-soluble compounds having both hydroxyl and amino groups in their molecules include hydroxylamine, monoethanolamine, 3-amino-1-propanol, 2-amino-2-hydroxymethylpropane-1,3-diol, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, N,N-bis(2-hydroxyethyl)ethylenediamine, N,N-bis(2-hydroxypropyl)ethylenediamine, N,N-bis(2-hydroxypropyl)propylenediamine, N-methylethanolamine, diethanolamine, and chitosan.

[0077] In the present invention, among the components (A2) to (A4), in order to facilitate the introduction of polymerizable functional groups that react with iso(thio)cyanate groups to the surface, a compound selected from components (A2) to (A4) that has a total of three or more hydroxyl groups, thiol groups, and amino groups is preferable. Using a compound with three or more functions makes it easier for some of the polymerizable functional groups to remain on the surface.

[0078] Preferred trifunctional or more compounds include, specifically, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, erythritol, diglycerol, diglycerin, ditrimethylolpropane, arabitol, sorbitol, mannitol, dipentaerythritol, or triglycerol, boremitol, isomalt, maltitol, isomaltitol, lactitol, cellulosin compounds, starch, dextrin, cyclic dextrin, polyvinyl alcohol, polyglycerin, tris(2-aminoethyl)amine, tris(3-aminopropyl)amine, 3,3',3''-nitrilotris(propionamide), polyethyleneimines, 2-amino-2-hydroxymethylpropane-1,3-diol, N,N-bis(2-hydroxyethyl)ethylenediamine, N,N-bis(2-hydroxypropyl)ethylenediamine, N,N-bis(2-hydroxypropyl)propylenediamine, and the like.

[0079] <(A5) Melamine-formaldehyde prepolymer compound> (A5) Melamine-formaldehyde prepolymer compounds are melamine-formaldehyde initial condensates of melamine and formaldehyde, and can be manufactured according to conventional methods. Examples of melamine-formaldehyde initial condensates of melamine and formaldehyde include methylolmelamine. In addition, commercially available melamine-formaldehyde prepolymer compounds can be used as appropriate. Examples include Beccamine APM, Beccamine M-3, Beccamine M-3(60), Beccamine MA-S, Beccamine J-101, Beccamine J-101LF (manufactured by DIC Corporation), Nikarezin S-176, Nikarezin S-260 (manufactured by Nippon Carbide Co., Ltd.), Milben Resin SM-800 (manufactured by Showa Polymer Co., Ltd.), etc. Component (A5) is preferably used in microballoons made of melamine resin.

[0080] <(A6) Urea-formaldehyde prepolymer compound> (A6) Urea-formaldehyde prepolymer compounds are urea-formaldehyde initial condensates of urea and formaldehyde and can be manufactured according to conventional methods. Examples of urea-formaldehyde initial condensates of urea and formaldehyde include methylolurea. Commercially available urea-formaldehyde prepolymer compounds can also be used as appropriate. For example, 8HSP (manufactured by Showa Polymer Co., Ltd.) is one such example. Component (A6) is preferably used in microballoons made of urea resin.

[0081] <(A7) Polyfunctional carboxylic acid compound component having at least two carboxyl groups> (A7) Examples of polyfunctional carboxylic acid compounds include dicarboxylic acid compounds and dihalogenated dicarboxylic acids.

[0082] Examples of the aforementioned dicarboxylic acid compounds include succinic acid, adipic acid, sebacic acid, dodecenylsuccinic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, dodecenylsuccinic acid, pentadecenylsuccinic acid, octadecenylsuccinic acid, maleic acid, fumaric acid, and other alkenylenedicarboxylic acids, decylsuccinic acid, dodecylsuccinic acid, octadecylsuccinic acid, phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid.

[0083] Furthermore, examples of the dicarboxylic acid dihalides include aliphatic dicarboxylic acid dihalides, alicyclic dicarboxylic acid dihalides, and aromatic dicarboxylic acid dihalides.

[0084] Examples of the aliphatic dicarboxylic acid dihalides include oxalate dichloride, malonate dichloride, succinate dichloride, fumarate dichloride, glutarate dichloride, adipicate dichloride, muconate dichloride, sebacate dichloride, nonanoate dichloride, undecanoate dichloride, oxalate dibromide, malonate dibromide, succinate dibromide, and fumarate dibromide.

[0085] Examples of the alicyclic dicarboxylic acid dihalides include 1,2-cyclopropanedicarboxylic acid dichloride, 1,3-cyclobutanedicarboxylic acid dichloride, 1,3-cyclopentanedicarboxylic acid dichloride, 1,3-cyclohexanedicarboxylic acid dichloride, 1,4-cyclohexanedicarboxylic acid dichloride, 1,3-cyclopentanedicarboxylic acid dichloride, 1,2-cyclopropanedicarboxylic acid dibromide, and 1,3-cyclobutanedicarboxylic acid dibromide.

[0086] Examples of the aromatic dicarboxylic acid dihalides include phthalate dichloride, isophthalate dichloride, terephthalate dichloride, 1,4-naphthalenedicarboxylic acid dichloride, 1,5-(9-oxofluorene)dicarboxylic acid dichloride, 1,4-anthracenedicarboxylic acid dichloride, 1,4-anthraquinonedicarboxylic acid dichloride, 2,5-biphenyldicarboxylic acid dichloride, 1,5-biphenylenedicarboxylic acid dichloride, 4,4'-biphenyldicarbonyl chloride, 4,4'-methylenedibenzoic acid dichloride, and 4,4'-i Examples include sopropylidene dibenzoate dichloride, 4,4'-bibenzyl dicarboxylic acid dichloride, 4,4'-stilbenidicarboxylic acid dichloride, 4,4'-trandicarboxylic acid dichloride, 4,4'-carbonyl dibenzoate dichloride, 4,4'-oxydibenzoate dichloride, 4,4'-sulfonyl dibenzoate dichloride, 4,4'-dithiodibenzoate dichloride, p-phenylene diacetate dichloride, 3,3'-p-phenylenedipropionate dichloride, phthalate dibromide, isophthalate dibromide, terephthalate dibromide, and the like.

[0087] In the present invention, a preferred example of component (A7) is a dicarboxylic acid dihalide, from the viewpoint of polymerization rate.

[0088] <How to manufacture microballoons> The method for manufacturing microballoons of the present invention can utilize known methods without limitation. For example, microballoons can be manufactured using known techniques that utilize emulsions of aqueous and oil phases, such as interfacial polymerization, coacervation, and in-situ polymerization. Furthermore, hollow microballoons can be manufactured by removing the internal liquid as needed.

[0089] The microballoons of the present invention are preferably made of at least one resin selected from the group consisting of urethane (urea) resin, melamine resin, urea resin, and amide resin. By using microballoons made of these resins, not only are excellent properties possible, but excellent polishing properties can also be achieved when used as polishing pads for CMP.

[0090] The microballoons of the present invention can be manufactured, for example, by the following methods, but are not limited to the following methods.

[0091] <When the microballoon is made of urethane (urea) resin or amide resin> When the microballoons of the present invention are made of urethane (urea) resin or amide resin, they can be manufactured by interfacial polymerization. In the case of interfacial polymerization, microballoons can be manufactured by first preparing an oil-in-water (O / W) emulsion (hereinafter also referred to as O / W emulsion) or water-in-oil (W / O) emulsion (hereinafter also referred to as W / O emulsion), and then polymerizing it at the interface. In the present invention, either O / W emulsion or W / O emulsion can be selected, but interfacial polymerization using O / W emulsion is preferred because it can efficiently produce microballoons having polymerizable functional groups on the surface of the microballoon that have reactivity with isocyanate groups. An example of interfacial polymerization using O / W emulsion is given below. Note that the following examples are examples of basic urethane (urea) resins, and for amide resins, the note "when made of amide resin" is used.

[0092] The polymerization method in O / W emulsion can be further broken down into the following steps: Step 1: (a) Prepare an oil phase (hereinafter also referred to as component (a)) containing at least component (A1) (or component (A7) if it consists of an amide resin) and an organic solvent; Step 2: Prepare an aqueous phase (hereinafter also referred to as component (b)) containing an emulsifier; Step 3: Mix and stir component (a) and component (b) to prepare an O / W emulsion in which the aqueous phase is a continuous phase and the oil phase is a dispersed phase; Step 4: Add (A2) to (A4) to the O / W emulsion. The process is divided into the following steps: 1. Add a hydrophilic compound selected from the components (if it consists of an amide resin, components (A3) to (A4) (wherein, component (A4) in "if it consists of an amide resin" is limited to component (A4) having at least two amino groups; the same applies hereinafter)) to allow polymerization to proceed on the interface of the O / W emulsion to form a resin film to form microballoons, and obtain a microballoon dispersion in which the microballoons are dispersed; 2. Separate the microballoons from the microballoon dispersion. Furthermore, the present invention may include a 6th step: remove the organic solvent solution from inside the microballoons.

[0093] 1st step: The first step is to prepare an oil phase in the O / W emulsion that includes (a) at least component (A1) (or component (A7) if it consists of an amide resin) and an organic solvent, which will form the dispersed phase.

[0094] This step involves dissolving component (A1) (or component (A7) if it consists of an amide resin) in an organic solvent, as described later, to form an oil phase. It is sufficient to dissolve it using a known method to obtain a homogeneous solution.

[0095] When the microballoons of the present invention are made of urethane (urea) resin, the preferred amount of component (A1) used is 0.1 to 50 parts by mass, preferably 0.5 to 20 parts by mass, and more preferably 1 to 10 parts by mass, per 100 parts by mass of organic solvent. Furthermore, when the number of moles of isocyanate groups contained in component (A1) (n1) is equal to the total number of moles of hydroxyl groups, thiol groups, and amino groups of components (A2) to (A4) (n2) is (n2), the range is preferably 0.3 ≤ (n1) / (n2) ≤ 2.0, more preferably 0.3 ≤ (n1) / (n2) ≤ 1.0, and most preferably 0.3 ≤ (n1) / (n2) ≤ 0.8.

[0096] When the microballoon of the present invention is made of an amide resin, the preferred amount of component (A7) used is 0.1 to 50 parts by mass, preferably 0.5 to 20 parts by mass, and more preferably 1 to 10 parts by mass, per 100 parts by mass of organic solvent. Furthermore, when the number of moles of amino groups and hydroxyl groups in the total of components (A3) to (A4) is (n4) relative to the number of moles of carboxylic acid groups contained in component (A7) (n3), it is preferable that the range is 0.3 ≤ (n3) / (n4) ≤ 2.0, more preferably 0.3 ≤ (n3) / (n4) ≤ 1.0, and even more preferably 0.3 ≤ (n3) / (n4) ≤ 0.8.

[0097] Furthermore, a catalyst, as described later, may be added to component (a) for the purpose of promoting the interfacial polymerization reaction.

[0098] Second step: The second step is to prepare an aqueous phase containing (b) an emulsifier and water, which will be the continuous phase in the O / W emulsion.

[0099] This step involves dissolving the emulsifier, described later, in water to form an aqueous phase. It is sufficient to dissolve it using a known method to create a homogeneous solution.

[0100] In the present invention, the amount of emulsifier used is 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, per 100 parts by mass of water. Within this range, aggregation of droplets in the dispersed phase in the O / W emulsion is avoided, and microballoons with a uniform average particle size are easily obtained.

[0101] Furthermore, a catalyst, as described later, may be added to component (b) for the purpose of promoting the interfacial polymerization reaction.

[0102] Third step: The third step is to mix and stir component (a) obtained in the first step and component (b) obtained in the second step to prepare an O / W emulsion in which component (a) is the dispersed phase and component (b) is the continuous phase.

[0103] In the present invention, the method of mixing and stirring component (a) and component (b) to produce an O / W emulsion can be prepared by mixing and stirring using a known method, taking into account the desired particle size of the microballoons to be produced.

[0104] Among these methods, the method of forming an O / W emulsion by mixing component (a) and component (b) and then dispersing them using a known disperser such as a high-speed shear type, friction type, high-pressure jet type, or ultrasonic type is preferably employed, and among these, the high-speed shear type is preferred. When using a high-speed shear type disperser, the rotation speed is preferably 500 to 20,000 rpm, and more preferably 1,000 to 10,000 rpm. The dispersion time is preferably 0.1 to 60 minutes, and more preferably 0.5 to 30 minutes. The dispersion temperature is preferably 10 to 40°C.

[0105] Furthermore, in the present invention, the weight ratio of component (a) to component (b) is preferably 1 to 100 parts by mass of component (a) when component (b) is 100 parts by mass, more preferably 2 to 90 parts by mass, and most preferably 5 to 50 parts by mass. Within this range, a good emulsion can be obtained.

[0106] 4th step: The fourth step is to add at least one compound selected from components (A2) to (A4) (or components (A3) to (A4) if it consists of an amide resin) to the O / W emulsion, polymerize it at the interface of the O / W emulsion to form a resin film, and obtain a microballoon dispersion in which the microballoons are dispersed.

[0107] Furthermore, when adding components (A2) to (A4) (or components (A3) to (A4) if they consist of amide resin) to the O / W emulsion, they may be added directly or dissolved in water beforehand.

[0108] When dissolving in water beforehand, it is preferable to use water in the range of 50 to 10,000 parts by mass, when the total amount of components (A2) to (A4) (or components (A3) to (A4) if they consist of amide resin) is 100 parts by mass.

[0109] The reaction temperature is not particularly limited as long as the O / W emulsion does not break down, but it is preferable to carry out the reaction in the range of 5 to 70°C. The reaction time is also not particularly limited as long as the W / O emulsion is formed, and is usually selected from the range of 0.5 to 24 hours.

[0110] 5th step The fifth step is to separate the microballoons from the microballoon dispersion. The separation method for separating the microballoons from the microballoon dispersion is not particularly limited and can be selected from general separation methods, specifically filtration or centrifugation.

[0111] 6th step The sixth step is to remove the oil phase from the microballoons obtained in the fifth step, thereby creating hollow microballoons. The method for removing the oil phase from the microballoons is not particularly limited and can be selected from general separation methods. Specifically, a circulating air dryer, spray dryer, fluidized bed dryer, vacuum dryer, etc., can be used. The drying temperature is preferably 40 to 250°C, and more preferably 50 to 200°C.

[0112] <When the microballoon is made of melamine resin or urea resin> Even when the microballoons of the present invention are made of melamine resin or urea resin, they can be manufactured by forming an O / W emulsion and then performing interfacial polymerization or in-situ polymerization. Specific examples are shown below, but the manufacturing method of the present invention is not limited thereto.

[0113] When the polymerization method in an O / W emulsion when the microballoons are made of melamine resin or urea resin is subdivided, it can be divided into the following steps: 1st step: preparing an oil phase containing an organic solvent (hereinafter also referred to as component (c)); 2nd step: preparing an aqueous phase containing an emulsifier (hereinafter also referred to as component (d)); 3rd step: mixing and stirring component (c) and component (d) to prepare an O / W emulsion in which the aqueous phase is a continuous phase and the oil phase is a dispersed phase; 4th step: adding component (A5) or component (A6) to the O / W emulsion and allowing polymerization to proceed at the interface of the O / W emulsion to form a resin phase and obtain a microballoon dispersion in which microballoons are dispersed; 5th step: separating the microballoons from the microballoon dispersion. In the present invention, a 6th step may also be included: removing the organic solvent solution from inside the microballoons.

[0114] 1st step: The first step is to prepare an oil phase containing (c) an organic solvent, which will be the dispersed phase in the O / W emulsion.

[0115] In this step, you just need to prepare an organic solvent. Second step: The second step is to prepare an aqueous phase containing (d) an emulsifier and water, which will be the continuous phase in the O / W emulsion, and to adjust the pH.

[0116] This step includes dissolving an emulsifier, described later, in water and adjusting the pH. pH adjustment and other related steps can be performed using known methods.

[0117] In the present invention, the amount of emulsifier used is 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, per 100 parts by mass of water. Within this range, aggregation of droplets in the dispersed phase in the O / W emulsion is avoided, and microballoons with a uniform average particle size are easily obtained.

[0118] Furthermore, a preferred pH is less than 7, more preferably 3.5 to 6.5, and most preferably 4.0 to 5.5. This pH range allows the polymerization of component (A5) or component (A6), which will be described later, to proceed. Third step: The third step is to mix and stir component (c) obtained in the first step and component (d) obtained in the second step to prepare an O / W emulsion in which component (c) is the dispersed phase and component (d) is the continuous phase.

[0119] In the present invention, the method of mixing and stirring components (c) and (d) to produce an O / W emulsion can be prepared by mixing and stirring using a known method, taking into account the desired particle size of the microballoons to be produced. Furthermore, the temperature and pH can also be adjusted during the process of preparing the O / W emulsion.

[0120] Among these, the method of forming an O / W emulsion by mixing component (c) and component (d) and then dispersing them using a known disperser such as a high-speed shear type, friction type, high-pressure jet type, or ultrasonic type is preferably employed, and among these, the high-speed shear type is preferred. When using a high-speed shear type disperser, the rotation speed is preferably 500 to 20,000 rpm, and more preferably 1,000 to 10,000 rpm. The dispersion time is preferably 0.1 to 60 minutes, and more preferably 0.5 to 30 minutes. The dispersion temperature is preferably 20 to 90°C.

[0121] Furthermore, in the present invention, the weight ratio of component (c) to component (d) is preferably 1 to 100 parts by mass of component (c) when component (d) is 100 parts by mass, more preferably 2 to 90 parts by mass, and most preferably 5 to 50 parts by mass. Within this range, a good emulsion can be obtained.

[0122] 4th step: The fourth step is to add component (A5) or component (A6) to the O / W emulsion, allow polymerization to proceed at the interface of the O / W emulsion to form a resin film, and thereby obtain a microballoon dispersion in which the formed microballoons are dispersed.

[0123] The amount of component (A5) or component (A6) used is not particularly limited, but in order to form microballoons well, it is preferably 0.5 to 50 parts by mass, and more preferably 1 to 20 parts by mass, per 100 parts by mass of the organic solvent used in the first step.

[0124] Furthermore, when adding component (A5) or component (A6) to the O / W emulsion, it may be added as is or dissolved in water before use.

[0125] When dissolving in water, it is preferable to use water in an amount of 50 to 10,000 parts by mass, where the total amount of component (A5) or component (A6) is 100 parts by mass.

[0126] The pH of the continuous aqueous phase may be adjusted in the second step, or after adding component (A5) or component (A6) in the fourth step. The pH of the continuous aqueous phase is preferably less than 7. The preferred reaction temperature is in the range of 40 to 90°C. The preferred reaction time is in the range of 1 to 48 hours. 5th process, 6th process Steps 5 and 6 are the same as the steps when the microballoons are made of urethane (urea) resin (or polyamide resin).

[0127] The components used in this invention are described below.

[0128] <Emulsifier> In the present invention, the emulsifier used in component (b) or component (d) includes a dispersant, a surfactant, or a combination thereof.

[0129] Examples of dispersants include polyvinyl alcohol and its modified products (e.g., anionically modified polyvinyl alcohol), cellulosic compounds (e.g., methylcellulose, ethylcellulose, hydroxyethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, hydroxypropylcellulose and their saponified products), polyacrylamide and its derivatives, ethylene-vinyl acetate copolymer, styrene-maleic anhydride copolymer, ethylene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, polyvinylpyrrolidone, ethylene-acrylic acid copolymer, vinyl acetate-acrylic acid copolymer, sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, partially neutralized polyacrylic acid, sodium acrylate-acrylic acid ester copolymer, carboxymethylcellulose, casein, gelatin, dextrin, chitin, chitosan, starch derivatives, gum arabic, and sodium alginate.

[0130] These dispersants are preferably non-reactive or extremely reactive with the polymerizable composition used in the present invention. For example, those having reactive amino groups in their molecular chains, such as gelatin, are preferably subjected to a treatment that renders them non-reactive beforehand.

[0131] Examples of surfactants include anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants. A surfactant may also be a combination of two or more surfactants.

[0132] Examples of anionic surfactants include carboxylic acids or their salts, sulfate esters, carboxymethylated salts, sulfonates, and phosphate esters.

[0133] Examples of carboxylic acids or their salts include saturated or unsaturated fatty acids with 8 to 22 carbon atoms or their salts. Specifically, these include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, oleic acid, linoleic acid, ricinoleic acid, and mixtures of higher fatty acids obtained by saponifying coconut oil, palm kernel oil, rice bran oil, beef tallow, etc. Examples of salts include sodium, potassium, ammonium, and alkanolamine salts of these fatty acids.

[0134] Examples of sulfate ester salts include higher alcohol sulfate ester salts (sulfate ester salts of aliphatic alcohols having 8 to 18 carbon atoms), higher alkyl ether sulfate ester salts (sulfate ester salts of ethylene oxide adducts of aliphatic alcohols having 8 to 18 carbon atoms), sulfated oils (unsaturated oils or unsaturated waxes that have been sulfated and neutralized), sulfated fatty acid esters (lower alcohol esters of unsaturated fatty acids that have been sulfated and neutralized), and sulfated olefins (olefins having 12 to 18 carbon atoms that have been sulfated and neutralized). Examples of salts include sodium salts, potassium salts, ammonium salts, and alkanolamine salts.

[0135] Specific examples of higher alcohol sulfate salts include octyl alcohol sulfate, decyl alcohol sulfate, lauryl alcohol sulfate, stearyl alcohol sulfate, and sulfate salts of alcohols synthesized by the oxo process (Oxocol 900, Tridecanol: manufactured by Kyowa Hakko).

[0136] Specific examples of higher alkyl ether sulfates include lauryl alcohol ethylene oxide 2-mol adduct sulfate and octyl alcohol ethylene oxide 3-mol adduct sulfate.

[0137] Specific examples of sulfated oils include sodium, potassium, ammonium, and alkanolamine salts of sulfur oxides found in castor oil, peanut oil, olive oil, rapeseed oil, beef tallow, and mutton fat.

[0138] Specific examples of sulfated fatty acid esters include sodium, potassium, ammonium, and alkanolamine salts of sulfur oxides such as butyl oleate and butyl ricinoleate.

[0139] Examples of carboxymethylated salts include carboxymethylated salts of aliphatic alcohols having 8 to 16 carbon atoms and carboxymethylated salts of ethylene oxide adducts of aliphatic alcohols having 8 to 16 carbon atoms.

[0140] Specific examples of carboxymethylated salts of aliphatic alcohols include octyl alcohol carboxymethyl sodium salt, decyl alcohol carboxymethyl sodium salt, lauryl alcohol carboxymethyl sodium salt, and tridecanol carboxymethyl sodium salt.

[0141] Specific examples of carboxymethylated salts of ethylene oxide adducts of aliphatic alcohols include sodium carboxymethylated octyl alcohol ethylene oxide 3 molar adduct, sodium carboxymethylated lauryl alcohol ethylene oxide 4 molar adduct, and sodium carboxymethylated tridecanol ethylene oxide 5 molar adduct.

[0142] Examples of sulfonates include alkylbenzene sulfonates, alkylnaphthalene sulfonates, sulfosuccinate diesters, α-olefin sulfonates, Igepon T-type, and sulfonates of other aromatic ring-containing compounds.

[0143] Specific examples of alkylbenzene sulfonates include sodium dodecylbenzenesulfonate.

[0144] Specific examples of alkylnaphthalene sulfonates include sodium dodecylnaphthalene sulfonate.

[0145] Specific examples of sulfosuccinate diesters include sodium di-2-ethylhexyl sulfosuccinate.

[0146] Examples of sulfonates of aromatic ring-containing compounds include mono- or disulfonates of alkylated diphenyl ethers and styrene-modified phenol sulfonates.

[0147] Examples of phosphate ester salts include higher alcohol phosphate ester salts and higher alcohol ethylene oxide adduct phosphate ester salts.

[0148] Specific examples of higher alcohol phosphate ester salts include sodium lauryl alcohol phosphate disodium salt and sodium lauryl alcohol phosphate diester salt.

[0149] A specific example of a higher alcohol ethylene oxide adduct phosphate ester salt is oleyl alcohol ethylene oxide 5-mol adduct phosphate monoester disodium salt.

[0150] Examples of cationic surfactants include quaternary ammonium salts and amine salts.

[0151] Quaternary ammonium salts can be obtained by the reaction of tertiary amines with quaternizing agents (methyl chloride, methyl bromide, ethyl chloride, benzyl chloride, alkylating agents such as dimethyl sulfate, ethylene oxide, etc.). Examples include lauryltrimethylammonium chloride, didecyldimethylammonium chloride, dioctyldimethylammonium bromide, stearyltrimethylammonium bromide, lauryldimethylbenzylammonium chloride (benzalkonium chloride), cetylpyridinium chloride, polyoxyethylenetrimethylammonium chloride, and stearamidoethyldiethylmethylammonium methosulfate.

[0152] Amine salts can be obtained by neutralizing primary to tertiary amines with inorganic acids (such as hydrochloric acid, nitric acid, sulfuric acid, and hydroiodic acid) or organic acids (such as acetic acid, formic acid, oxalic acid, lactic acid, gluconic acid, adipic acid, and alkyl phosphate). For example, primary amine salts include inorganic or organic salts of aliphatic higher amines (such as laurylamine, stearylamine, cetylamine, hardened beef tallowamine, and rosinamine), and salts of lower amines with higher fatty acids (such as stearic acid and oleic acid).

[0153] Examples of secondary amine salts include inorganic or organic salts such as ethylene oxide adducts of aliphatic amines.

[0154] Examples of tertiary amine salts include, for example, inorganic or organic salts of aliphatic amines (triethylamine, ethyldimethylamine, N,N,N',N'-tetramethylethylenediamine, etc.), ethylene oxide adducts of aliphatic amines, alicyclic amines (N-methylpyrrolidine, N-methylpiperidine, N-methylhexamethyleneimine, N-methylmorpholine, 1,8-diazabicyclo(5,4,0)-7-undecene, etc.), nitrogen-containing heterocyclic aromatic amines (4-dimethylaminopyridine, N-methylimidazole, 4,4'-dipyridyl, etc.), inorganic or organic salts of tertiary amines such as triethanolamine monostearate and stearamidoethyldiethylmethylethanolamine.

[0155] Examples of amphoteric surfactants include carboxylate-type amphoteric surfactants, sulfate-type amphoteric surfactants, sulfonate-type amphoteric surfactants, and phosphate-type amphoteric surfactants. Carboxylate-type amphoteric surfactants can be further divided into amino acid-type amphoteric surfactants and betaine-type amphoteric surfactants.

[0156] Carboxylate-type amphoteric surfactants include amino acid-type amphoteric surfactants, betaine-type amphoteric surfactants, and imidazoline-type amphoteric surfactants. Of these, amino acid-type amphoteric surfactants are amphoteric surfactants that have both an amino group and a carboxyl group in their molecule. Specifically, examples include alkylaminopropionic acid-type amphoteric surfactants (such as sodium stearylaminopropionate and sodium laurylaminopropionate) and alkylaminoacetic acid-type amphoteric surfactants (such as sodium laurylaminoacetate).

[0157] Betaine-type amphoteric surfactants are amphoteric surfactants that have a quaternary ammonium salt type cationic moiety and a carboxylic acid type anionic moiety in their molecule. Examples include alkyldimethyl betaine (stearyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, etc.), amide betaine (coconut oil fatty acid amidopropyl betaine, etc.), and alkyldihydroxyalkyl betaine (lauryldihydroxyethyl betaine, etc.).

[0158] Furthermore, examples of imidazoline-type amphoteric surfactants include 2-undecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine.

[0159] Other amphoteric surfactants include, for example, glycine-type amphoteric surfactants such as sodium lauroyl glycine, sodium lauryl diaminoethylglycine, lauryl diaminoethylglycine hydrochloride, and dioctyl diaminoethylglycine hydrochloride, and sulfobetaine-type amphoteric surfactants such as pentadecyl sulfotaurine.

[0160] Examples of nonionic surfactants include alkylene oxide-added nonionic surfactants and polyhydric alcohol-type nonionic surfactants.

[0161] Alkylene oxide-added nonionic surfactants can be obtained by directly adding alkylene oxide to higher alcohols, higher fatty acids, or alkylamines, reacting polyalkylene glycols obtained by adding alkylene oxide to glycols with higher fatty acids, adding alkylene oxide to esterified products obtained by reacting polyhydric alcohols with higher fatty acids, or adding alkylene oxide to higher fatty acid amides.

[0162] Examples of alkylene oxides include ethylene oxide, propylene oxide, and butylene oxide.

[0163] Specific examples of alkylene oxide-added nonionic surfactants include oxyalkylene alkyl ethers (e.g., octyl alcohol ethylene oxide adduct, lauryl alcohol ethylene oxide adduct, stearyl alcohol ethylene oxide adduct, oleyl alcohol ethylene oxide adduct, lauryl alcohol ethylene oxide propylene oxide block adduct, etc.), polyoxyalkylene higher fatty acid esters (e.g., stearyl ethylene oxide adduct, lauryl ethylene oxide adduct, etc.), polyoxyalkylene polyhydric alcohol higher fatty acid esters (e.g., polyethylene glycol laurate diester, polyethylene glycol oleate diester, polyethylene glycol stearate diester, etc.), and polyoxyalkylene alkyl Examples include polyphenyl ethers (e.g., nonylphenol ethylene oxide adduct, nonylphenol ethylene oxide propylene oxide block adduct, octylphenol ethylene oxide adduct, bisphenol A ethylene oxide adduct, dinonylphenol ethylene oxide adduct, styrene phenol ethylene oxide adduct, etc.), polyoxyalkylene alkylamino ethers (e.g., laurylamine ethylene oxide adduct, stearylamine ethylene oxide adduct, etc.), and polyoxyalkylene alkyl alkanolamides (e.g., ethylene oxide adduct of hydroxyethyl laurate amide, ethylene oxide adduct of hydroxypropyl oleamide, ethylene oxide adduct of dihydroxyethyl laurate amide, etc.).

[0164] Examples of polyhydric alcohol-type nonionic surfactants include polyhydric alcohol fatty acid esters, polyhydric alcohol fatty acid ester alkylene oxide adducts, polyhydric alcohol alkyl ethers, and polyhydric alcohol alkyl ether alkylene oxide adducts.

[0165] Specific examples of polyhydric alcohol fatty acid esters include pentaerythritol monolaurate, pentaerythritol monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan monolaurate, sorbitan dilaurate, sorbitan diolate, and sucrose monostearate.

[0166] Specific examples of polyhydric alcohol fatty acid ester alkylene oxide adducts include ethylene glycol monooleate ethylene oxide adduct, ethylene glycol monostearate ethylene oxide adduct, trimethylolpropane monostearate ethylene oxide propylene oxide random adduct, sorbitan monolaurate ethylene oxide adduct, sorbitan monostearate ethylene oxide adduct, sorbitan distearate ethylene oxide adduct, and sorbitan dilaurate ethylene oxide propylene oxide random adduct.

[0167] Specific examples of polyhydric alcohol alkyl ethers include pentaerythritol monobutyl ether, pentaerythritol monolauryl ether, sorbitan monomethyl ether, sorbitan monostearyl ether, methyl glycoside, and lauryl glycoside.

[0168] Specific examples of polyhydric alcohol alkyl ether alkylene oxide adducts include sorbitan monostearyl ether ethylene oxide adduct, methyl glycoside ethylene oxide propylene oxide random adduct, lauryl glycoside ethylene oxide adduct, and stearyl glycoside ethylene oxide propylene oxide random adduct.

[0169] Among these, the emulsifier used in the present invention is preferably selected from dispersants and nonionic surfactants. More specifically, if the microballoons of the present invention are made of urethane (urea) resin, polyvinyl alcohol or anionic modified polyvinyl alcohol is preferred, and if the microballoons are made of amide resin, sodium acrylate-acrylic acid ester copolymer is preferred. By selecting these, a stable emulsion can be obtained.

[0170] Furthermore, when the microballoons are made of melamine resin or urea resin, the emulsifier is preferably a styrene-maleic anhydride copolymer, an ethylene-maleic anhydride copolymer, or an isobutylene-maleic anhydride copolymer. By neutralizing these with an alkaline compound such as sodium hydroxide, a high-density anionic polymer is formed, which allows the polymerization reaction of components (A5) and (A6) to proceed.

[0171] <organic solvents> In the present invention, the organic solvent used in component (a) or component (c) is not particularly limited as long as it is capable of dissolving component (A1), component (A7), or the lipophilic component (A). In the present invention, lipophilic means having a solubility in water of 1 g / 1 L or less. Examples of the organic solvent include hydrocarbon-based, halogenated, and ketone-based solvents.

[0172] In particular, when the organic solvent is removed from the inside of the microballoon to form a hollow microballoon, a boiling point of 200°C or lower is preferred, and more preferably a boiling point of 150°C or lower. Examples of these include the following.

[0173] (Hydrogen-based) Examples include aromatic hydrocarbons such as n-hexane, n-heptane, n-octane, n-hexadecane, benzene, toluene, and xylene, and alicyclic hydrocarbons such as cyclohexane, cyclopentane, and methylcyclohexane.

[0174] (Halogenated) Examples include chloroform, dichloromethane, tetrachloroethane, mono- or dichlorobenzene, etc.

[0175] (Ketones) Examples include methyl isobutyl ketone.

[0176] These organic solvents may be used individually or as a mixture of two or more solvents.

[0177] Among the organic solvents used in the present invention, n-hexane, n-heptane, n-octane, benzene, toluene, xylene, and the like are more preferred.

[0178] <Additives> In the present invention, additives may be added to the aqueous phase to further stabilize the emulsion, provided that the effects of the present invention are not impaired. Examples of such additives include water-soluble salts such as sodium carbonate, calcium carbonate, potassium carbonate, sodium phosphate, potassium phosphate, calcium phosphate, sodium chloride, and potassium chloride. These additives can be used individually or in combination of two or more.

[0179] <Catalyst> (Urethane catalyst) In the present invention, any suitable urethane catalyst can be used without limitation when synthesizing the urethane prepolymer, which is component (A12), or when the microballoons are made of urethane (urea) resin. Specifically, examples include triethylenediamine, hexamethylenetetramine, N,N-dimethyloctylamine, N,N,N′,N′-tetramethyl-1,6-diaminohexane, 4,4′-trimethylenebis(1-methylpiperidine), 1,8-diazabicyclo-(5,4,0)-7-undecene, dimethyltin dichloride, dimethyltinbis(isooctylthioglycolate), dibutyltin dichloride, dibutyltin dilaurate, dibutyltin maleate, dibutyltin maleate polymer, dibutyltin diricinolate, dibutyltinbis(dodecyl mercaptide), and dibutyltinbis(isooctyl Examples include thioglycolates, dioctyltin dichloride, dioctyltin maleate, dioctyltin maleate polymer, dioctyltin bis(butylmaleate), dioctyltin dilaurate, dioctyltin diricinoleate, dioctyltin dioleate, dioctyltin di(6-hydroxy)caproate, dioctyltin bis(isooctylthioglycolate), didodecyltin diricinoleate, and various metal salts, such as copper oleate, copper acetylacetoneate, iron acetylacetoneate, iron naphthenate, iron lactate, iron citrate, iron gluconate, potassium octanoate, and 2-ethylhexyl titanate.

[0180] (Amidation catalyst) When the microballoons are made of amide resin, any suitable amidation catalyst can be used without any limitations. Specific examples include boron and sodium dihydrogen phosphate.

[0181] <Polyurethane (urea) resin containing the aforementioned microballoons> The microballoons of the present invention can exhibit excellent durability, particularly when incorporated into polyurethane (urea) resin. In this specification, polyurethane (urea) resin refers collectively to polyurethane resin, polyurea resin, and polyurethane-urea resin.

[0182] The method for producing the polyurethane (urea) resin containing microballoons of the present invention is not particularly limited and any known method can be used. For example, a method of polymerizing a polymerizable composition containing a monomer for forming the polyurethane (urea) resin and microballoons can be used. More specifically, a method can be used in which a compound having at least two isocyanate groups, a compound having at least two active hydrogen groups (e.g., hydroxyl groups, thiol groups, amino groups, etc.) that can polymerize with isocyanate groups, and the microballoons of the present invention are uniformly mixed and dispersed to form a polymerizable composition, and then the polymerizable composition is cured. The curing method is also not particularly limited and any known method can be used. Specifically, dry methods such as the one-pot method and the prepolymer method, and wet methods using a solvent can be used. Among these, the dry method is preferably used. Furthermore, known compounding materials may be added to the polymerizable composition to the extent that they do not impair the effects of the present invention.

[0183] In the polyurethane (urea) resin containing the microballoons of the present invention, the amount of microballoons of the present invention blended into the polyurethane (urea) resin is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 20 parts by mass, and even more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the total of the compound having at least two iso(thio)cyanate groups and the compound having at least two active hydrogen groups having active hydrogens polymerizable with iso(thio)cyanate groups.

[0184] Furthermore, when the microballoons of the present invention described later are hollow microballoons, the amount of the compound is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 8 parts by mass, and even more preferably 0.5 to 8 parts by mass, per 100 parts by mass of the total of the compound having at least two iso(thio)cyanate groups and the compound having at least two active hydrogen groups having active hydrogen that can polymerize with iso(thio)cyanate groups.

[0185] By setting the range to these specifications, it becomes possible to achieve excellent polishing characteristics when used as a polishing pad for CMP, as described later.

[0186] The polyurethane (urea) resin containing microballoons of the present invention can have any desired hardness. The hardness can be measured according to the Shore hardness test, for example, according to JIS standard (hardness test) K6253. In the present invention, when the resin is used for polishing pads for CMP (Chemical Polishing) as described later, the Shore hardness is more preferably 40A to 80D, and more preferably 20D to 70D (where "A" indicates hardness on the Shore "A" scale and "D" indicates hardness on the Shore "D" scale). The hardness can be any desired hardness by changing the compound composition and compounding amount as needed.

[0187] Furthermore, the microballoons of the present invention make it easier to maintain the performance of the resin used. One criterion for evaluating such performance is to compare them based on the hysteresis loss of the resin used. Generally, a small hysteresis loss in a resin indicates excellent elastic recovery, and when used in polishing pads for CMP (Chemical Polishing) described later, it is possible to achieve flatness of the workpiece and a high polishing rate.

[0188] The hysteresis loss can be measured, for example, by a method conforming to JIS K 6251. Specifically, a dumbbell-shaped test piece can be stretched to 100% and then returned to its original shape to measure the hysteresis loss ([area of ​​elongation and stress when stretched and returned to its original shape / area of ​​elongation and stress when stretched] × 100). In the measurement of the hysteresis loss described above, the "area of ​​elongation and stress when stretched and returned to its original shape" is expressed as "area of ​​stress-strain curve during stretching - area of ​​stress-strain curve during contraction," and the "area of ​​elongation and stress when stretched" refers to the "area of ​​stress-strain curve during stretching."

[0189] In the present invention, when used in polishing pads for CMP described later, the hysteresis loss is preferably in the range of HB% ≤ H% + 8%, and more preferably in the range of HB% ≤ H% + 6%, where HB% is the hysteresis loss of the resin using microballoons and H% is the hysteresis loss of the resin without microballoons. In other words, the hysteresis loss of the resin used does not change significantly depending on the presence or absence of microballoons, making it possible to utilize the original physical properties. Of course, the only difference between the resin using microballoons and the resin without microballoons is the presence or absence of microballoons.

[0190] Furthermore, when the polyurethane (urea) resin of the present invention is used in polishing pads for CMP (Chemical Polishing) described later, it is preferable that it has a compressibility within a certain range in order to achieve flatness of the workpiece. The compressibility can be measured by a method in accordance with JIS L 1096. In the present invention, the compressibility is preferably between 0.5% and 50%. Being within this range makes it possible to achieve excellent flatness of the workpiece when used in polishing pads for CMP described later.

[0191] In addition, when the microballoon of the present invention is a hollow microballoon, the polyurethane (urea) resin of the present invention becomes a foamed polyurethane (urea) resin, and the density can be adjusted according to the blending amount and the like. In the present invention, when the foamed polyurethane (urea) resin is used for a polishing pad for CMP described later, the density of the foamed polyurethane (urea) resin is 0.60 to 0.95 g / cm 3 is preferably

[0192] The method for producing the foamed polyurethane (urea) resin is not particularly limited. Not only the method for producing the polyurethane (urea) resin using a hollow microballoon can be used, but also a method in which the sixth step described above is carried out during the production of the polyurethane (urea) resin using a microballoon in a state where an organic solvent remains inside may be adopted.

[0193] <Polishing pad for CMP> By using the polyurethane (urea) resin containing the microballoon of the present invention, a polishing pad for CMP having excellent durability and excellent polishing characteristics can be produced.

[0194] As a method for producing the polishing pad for CMP, a known method can be adopted without limitation. For example, a method of cutting and surface polishing the polyurethane (urea) resin containing the microballoon of the present invention is adopted, whereby a polishing pad for CMP having pores on the polishing surface of the resin can be obtained. The microballoon may be either a hollow microballoon or a microballoon in a state where an organic solvent remains inside.

[0195] Among them, it is preferable that the microballoon used for the polishing for CMP of the present invention is a hollow microballoon, and thus, a polishing pad for CMP using a foamed polyurethane (urea) resin is obtained.

[0196] Furthermore, when the polishing pad is composed of multiple layers, the polishing pad for CMP of the present invention can be applied to any of the layers, but it is preferable to use the polishing pad for CMP of the present invention on at least the polishing surface that comes into contact with the workpiece.

[0197] Furthermore, the polishing pad for CMP of the present invention can also be a fixed abrasive CMP polishing pad containing abrasive grains other than the microballoons of the present invention. Examples of such abrasive grains include particles made of materials selected from cerium oxide, silicon oxide, alumina, silicon carbide, zirconia, iron oxide, manganese dioxide, titanium oxide, and diamond, or two or more particles made of these materials. The method for incorporating these abrasive grains is not particularly limited, but one example is a method in which the abrasive grains are further uniformly mixed and dispersed in the polymerizable composition in the polyurethane (urea) resin manufacturing method described above, and then the polymerizable composition is cured.

[0198] The form of the polishing pad for CMP of the present invention is not particularly limited, and for example, a groove structure may be formed on its surface. The groove structure of the polishing pad for CMP is preferably shaped to retain and refresh the slurry, and specifically, examples include X (stripe) grooves, XY grid grooves, concentric grooves, through holes, non-through holes, polygonal prisms, cylinders, helical grooves, eccentric grooves, radial grooves, and combinations thereof.

[0199] Furthermore, the method for forming the groove structure of the polishing pad for CMP described above is not particularly limited. For example, it may be formed by pouring the aforementioned compound into a mold having a predetermined groove structure and curing it, or by forming the groove structure using the obtained resin, such as by mechanical cutting using a jig such as a cutting tool of a predetermined size, by pressing the resin with a press plate having a predetermined surface shape, by forming it using photolithography, by forming it using a printing method, or by forming it using laser light such as a carbon dioxide laser. [Examples]

[0200] Next, the present invention will be described in detail using examples and comparative examples, but the present invention is not limited to these examples. In the following examples and comparative examples, the above-mentioned components and evaluation methods are as follows.

[0201] [Evaluation Method] (1) Amount of polymerizable functional groups that react with iso(thio)cyanate groups: The microballoon of the present invention was added to butyl isocyanate (or a butyl isocyanate solution of known concentration), and after thorough stirring, the isocyanate groups were quantified by back titration in accordance with JIS K 7301. Specifically, the butyl isocyanate solution with the microballoon of the present invention added and thoroughly stirred, along with a clearly excess amount of di-n-butylamine compared to the amount of isocyanate groups in the butyl isocyanate, was added to a dry solvent that does not react with isocyanate groups, and the total isocyanate groups of the butyl isocyanate solution were reacted with the di-n-butylamine. Next, the amount of di-n-butylamine that was not consumed (did not participate in the reaction) was titrated with acid to determine the amount of consumed di-n-butylamine, and the amount of butyl isocyanate consumed per gram of microballoon was determined. This consumption amount was taken as the amount of polymerizable functional groups (mmol / g) that react with the isocyanate groups on the surface of the microballoon.

[0202] (2) Particle size: The average particle size of microballoons observed with an optical microscope was calculated using image analysis.

[0203] (3) Bulk density: The bulk density was determined by passing the microballoons through a 1000 μm sieve, adding them to a 100 mL graduated cylinder, and tapping it 1000 times. The bulk density [g / cm³] was then calculated from the volume and mass of the microballoons in the container. 3 ] was sought.

[0204] (4) Ash content: This is the ratio of the mass of the combustion residue after burning microballoons at a temperature of 600°C to the mass of the microballoons before combustion. Specifically, the number of parts by mass of the combustion residue was calculated when the amount of microballoons before combustion was set to 100 parts by mass.

[0205] (5) Shore stiffness: Shore hardness was measured using a durometer manufactured by Polymer Instruments, in accordance with JIS standard (hardness test) K6253.

[0206] (6) Hysteresis Loss: A hardened resin, punched into a 2mm thick dumbbell shape (size 8), was stretched 20mm at 10mm / min using a Shimadzu AG-SX autograph. The hysteresis loss was then measured when the resin was returned to its original state until the stress was zero.

[0207] (7) Abrasion resistance: A Taber abrasion test was performed on cured resin, and the amount of Taber abrasion was measured. The measurement conditions were as follows: the Taber 5130 device was used. The load was 1 kg, the rotation speed was 60 rpm, the rotation count was 1000 rpm, and the abrasion wheel was H-18. The Taber abrasion test was performed twice on the same sample at the same location, and the average value was used for evaluation. The table shows the amount of Taber abrasion (mg) as an evaluation of abrasion resistance; a lower amount of Taber abrasion indicates better durability.

[0208] (8) Polishing rate: The polishing rate was measured when polishing was performed under the following conditions. The polishing rate is the average value for 10 2-inch sapphire wafers. Polishing pad for CMP: A pad with concentric grooves formed on its surface, measuring 500mm in diameter and 1mm thick. Slurry: FUJIMI Conpol 80 Concentrate Pressure: 4 psi Rotation speed: 45 rpm Time: 1 hour

[0209] (9) Surface roughness (Ra): The surface roughness (Ra) of 10 2-inch sapphire wafers polished under the conditions described in (8) above was measured using a nanosearch microscope SFT-4500 (manufactured by Shimadzu Corporation). The surface roughness is the average value of the 10 2-inch sapphire wafers.

[0210] <Each ingredient> (polymerizable monomer) (A1) Component; a polyfunctional isocyanate compound having at least two isocyanate groups. (A12) Component; Urethane prepolymer Pre-1: Terminal isocyanate urethane prepolymer with an isocyanate equivalent of 905. Pre-2: Terminal isocyanate urethane prepolymer with an isocyanate equivalent of 423.

[0211] (Pre-1 manufacturing method) In a flask equipped with a nitrogen inlet tube, thermometer, and stirrer, 500 g of 2,4-tolylene diisocyanate, 900 g of polyoxytetramethylene glycol (number average molecular weight: 1,000), and 120 g of diethylene glycol were reacted at 80°C for 6 hours under a nitrogen atmosphere to obtain a terminal isocyanate urethane prepolymer (Pre-1) with an isocyanate equivalent of 905. (Pre-2 manufacturing method) Except for using 585g of polyoxytetramethylene glycol (number average molecular weight: 650) and 65g of diethylene glycol, the same method as in Production Example Pre-1 was used to obtain a terminal isocyanate urethane prepolymer (Pre-2) with an isocyanate equivalent of 423.

[0212] (A3) Component; polyfunctional amino compound TAEA: Tris(2-aminoethyl)amine (organic solvent) Tol; Tol (emulsifier) PVA: Polyvinyl alcohol that is fully saponified and has an average degree of polymerization of approximately 500.

[0213] <Example 1> (Microballoon-1) Component (a) was prepared by dissolving 3 parts by mass of Pre-2 of component (A1) in 20 parts by mass of toluene. Next, component (b) was prepared by dissolving 6 parts by mass of PVA in 100 parts by mass of water. Then, the prepared components (a) and (b) were mixed and stirred using a high-speed shear disperser at 1,500 rpm for 10 minutes at 25°C to prepare an O / W emulsion. To the prepared O / W emulsion, an aqueous solution prepared by dissolving 0.4 parts by mass of TAEA in 4 parts by mass of water was added dropwise at 25°C. After addition, the mixture was stirred at 60°C for 4 hours to obtain a microballoon dispersion made of urethane (urea) resin. Microballoons were extracted from the obtained microballoon dispersion by filtration, vacuum dried at 60°C for 24 hours, and then sieved using a classifier to obtain hollow microballoon-1.

[0214] The amount of polymerizable functional groups reactive with iso(thio)cyanate groups on the surface of the acquired microballoon-1 was 2.5 mmol / g. The particle size of microballoon-1 was approximately 20 μm, and its bulk density was 0.18 g / cm³. 3 Ash content was not measured.

[0215] <Example 3> (Microballoon-3) Microballoon-3 was obtained by manufacturing in the same manner as in Example 1, except that 0.32 parts by mass of TAEA was used. The amount of polymerizable functional groups reactive with iso(thio)cyanate groups on the surface of the acquired microballoon-3 was 0.9 mmol / g. The particle size of microballoon-3 was approximately 15 μm, and its bulk density was 0.20 g / cm³. 3 Ash content was not measured.

[0216] <Example 4> (Microballoon-4) Microballoon-4 was obtained by manufacturing in the same manner as in Example 1, except that 0.35 parts by mass of TAEA was used. The amount of polymerizable functional groups reactive with isothiocyanate groups on the surface of the obtained microballoon-4 was 1.7 mmol / g. The particle size of microballoon-4 was about 20 μm, and the bulk density was 0.19 g / cm 3 , and the ash content was not measured.

[0217] <Reference Example 1> (Microballoon-2) Microballoon-2 was a commercially available microcapsule 920-40 (manufactured by Nippon Fillite Co., Ltd., a hollow microballoon made of an acrylonitrile resin coated with inorganic powder on the surface), and the amount of polymerizable functional groups reactive with isothiocyanate groups was 0 mmol / g. The particle size was 40 μm, the bulk density was 0.03 g / cm 3 , and the ash content was 1.87 parts by mass.

[0218] <Example 2> (Method for manufacturing a polishing pad for CMP using microballoons) 12 parts by mass of 4,4'-methylenebis(o-chloroaniline) (MOCA) was thoroughly degassed to prepare Solution A. Separately, 3.3 parts by mass of the microballoon-1 obtained in Example 1 was added to 88 parts by mass of Pre-1 manufactured above and heated to 70°C, and the mixture was stirred with a planetary stirrer to obtain a uniform solution. Then, Solution A prepared at 100°C was added thereto, and the mixture was stirred with a planetary stirrer to obtain a uniform polymerizable composition. The polymerizable composition was injected into a mold and cured at 100°C for 15 hours to obtain a polyurethane (urea) resin containing microballoons.

[0219] The obtained polyurethane (urea) resin was sliced to obtain a polishing pad for CMP using a polyurethane (urea) resin having a thickness of 1 mm shown below.

[0220] Separately, the same operations as above were performed except that no microballoons were added to prepare a polyurethane (urea) resin without microballoons. This polyurethane (urea) resin without microballoons was not used for CMP polishing, and only the physical properties of the resin were confirmed.

[0221] The density of the polyurethane (urea) resin containing the microballoons obtained above is 0.87 g / cm³. 3 The Shore hardness was 50D, the hysteresis loss was 65%, and the abrasion resistance was 58mg. The polishing rate of the CMP polishing pad obtained above was 2.0 μm / hr, and the surface roughness of the wafer after polishing was 0.22 nm. In addition, the Shore hardness of the polyurethane (urea) resin without microballoons was 55D, the hysteresis loss was 60%, and the abrasion resistance was 50mg.

[0222] <Examples 5 and 6, Comparative Example 1> Polishing pads for CMP using polyurethane (urea) resin were prepared and evaluated in the same manner as in Example 2, except that the compositions shown in Table 1 were used. The results are shown in Table 1.

[0223] As can be seen from the results in Table 1, the CMP polishing pad using the microballoons of the present invention exhibits excellent durability, resin properties, and polishing characteristics such as a higher polishing rate and smoother polishing of the wafer to be polished.

[0224] [Table 1]

Claims

1. A microballoon having polymerizable functional groups on its surface that are reactive with iso(thio)cyanate groups, the particle size of the microballoon being 10 to 200 μm, the polymerizable functional group reactive with iso(thio)cyanate groups being at least one group selected from the group consisting of hydroxyl groups, amino groups, and thiol groups, the amount of polymerizable functional groups reactive with iso(thio)cyanate groups on the surface being 0.75 mmol / g or more per weight of the microballoon, and the microballoon being made of at least one resin selected from the group consisting of urethane (urea) resin, melamine resin, urea resin, and amide resin.

2. The microballoon according to claim 1, wherein the ash content of the microballoon is 0.5 parts by mass or less when the microballoon is 100 parts by mass.

3. The bulk density of the aforementioned microballoons is 0.01 to 0.5 g / cm³. ３ The microballoon according to claim 1 or 2.

4. A polyurethane (urea) resin comprising microballoons as described in any one of claims 1 to 3.

5. Polishing pad for CMP using polyurethane (urea) resin as described in claim 4.

6. The aforementioned polyurethane (urea) resin has a Shore hardness of 40A to 80D and a density of 0.60 to 0.95 g / cm³. ３ The polishing pad for CMP according to claim 5.

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