Novel curable composition containing cyclic monomers

Abstract

This curable composition contains: (A) a cyclic monomer having both a polymerizable functional group and an ionic functional group in the molecule; and (B) a polymerizable monomer having a polymerizable functional group able to be polymerized with the polymerizable functional group in the cyclic monomer (A).　According to the present invention, it is possible to provide a curable composition which can be easily handled and which can yield a cured product that has high abrasion resistance and exhibits improved hydrophilic properties without sacrificing mechanical characteristics, and especially, a curable composition which can yield a cured product able to be advantageously used as a polishing pad.

Description

[Technical Field]

[0001] The present invention relates to a novel cyclic monomer having both an ionic functional group that forms a cation or an anion and a polymerizable functional group, and to a novel curable composition containing the cyclic monomer. [Background technology]

[0002] A polishing member is a material used to flatten a mating member (a member to be polished) with an abrasive. Specifically, the polishing member is used to flatten the surface of a member to be polished by sliding it against the surface while supplying an abrasive such as slurry to the surface. For example, a polishing pad is included.

[0003] Polyurethane resins are widely used in such polishing members. Generally, for polishing members, highly durable materials with good wear resistance over a long period of time are always desired in order to reduce costs, stabilize production, and improve productivity.

[0004] Specifically, polishing members are used as pad materials (hereinafter sometimes referred to as polishing pads) in the CMP (Chemical Mechanical Polishing) method. The CMP method is a polishing method that imparts excellent surface flatness and is particularly used in the manufacturing processes of liquid crystal displays (LCDs), glass substrates for hard disks, silicon wafers, and semiconductor devices.

[0005] In the CMP method, a method is generally adopted in which a slurry (polishing liquid) in which abrasive grains are dispersed in an alkaline or acid solution is supplied during polishing. That is, the polished material is planarized by the mechanical action of the abrasive grains in the slurry and the chemical action of the alkaline or acid solution. Usually, the slurry is supplied to the surface of the polished material, and the surface of the polished material is planarized by sliding a polishing pad against the surface. The polishing characteristics of a polishing pad used in the CMP method are required to be excellent flatness of the workpiece and a high polishing rate (removal speed).Furthermore, improved wear resistance is also desired to improve productivity.

[0006] As a material for such a polishing pad, a resin obtained by curing a urethane-based curable composition is known (see Patent Document 1). Furthermore, Patent Document 2 discloses a polishing pad in which the hydrophilicity of the resin used in the polishing pad is improved, thereby improving the slurry retention and polishing properties (see Patent Document 2). Patent Document 2 describes that excellent polishing properties are achieved by using a polyol having a hydrophilic group (e.g., an ionic functional group) as one component of a urethane-based curable composition. Furthermore, Patent Document 3 discloses that a polishing pad obtained using a polyrotaxane monomer having both a polymerizable functional group and an ionic functional group exhibits excellent wear resistance, water absorption, and other excellent polishing pad properties (see Patent Document 3). [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-77207 [Patent Document 2] Japanese Patent Application Laid-Open No. 2007-276061 [Patent Document 3] International Publication No. 2020 / 096010 Summary of the Invention [Problem to be solved by the invention]

[0008] However, in recent years, there has been a demand for further improvements in performance, particularly polishing pads that are easy to handle during production, have excellent wear resistance, and have excellent mechanical properties, and there has been room for improvement in conventional technologies.

[0009] Specifically, the polishing pad described in Patent Document 2 uses a diol compound as the polyol compound, and the polyurethane resin obtained by curing has insufficient properties such as abrasion resistance.In addition, since the polyurethane resin uses a diol compound with a low molecular weight, it is thought that the hydrophilic group introduced into the polyurethane resin to enhance hydrophilicity is likely to be present in the vicinity of the hard segment of the polyurethane resin.As a result, it may be difficult to achieve sufficient hydrophilicity, and there is room for improvement.

[0010] On the other hand, the polishing pad described in Patent Document 3 has room for improvement, as the polyrotaxane monomer used tends to have a high molecular weight due to its unique structure, making it difficult to handle and limiting its production. Therefore, an object of the present invention is to provide a curable composition that is easy to handle and that can be cured to have high abrasion resistance and improved hydrophilicity without impairing mechanical properties, particularly to provide a curable composition that can be cured to a cured product (e.g., polyurethane resin) that can be suitably used as a polishing pad. [Means for solving the problem]

[0011] The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result of their research aimed at overcoming the above-mentioned problems, they have found that by using a curable composition containing a cyclic monomer having both a polymerizable functional group and an ionic functional group in the molecule, it is possible to obtain a cured product that has good handleability and that has excellent mechanical properties by curing the cured composition, thereby completing the present invention.

[0012] That is, the first aspect of the present invention is The curable composition contains (A) a cyclic monomer having both a polymerizable functional group and an ionic functional group in the molecule, and (B) a polymerizable monomer having a polymerizable functional group that can polymerize with the polymerizable functional group of the cyclic monomer (A). In the first aspect of the present invention, it is preferred that the polymerizable functional group contained in the (A) cyclic monomer is at least one group selected from the group consisting of a radically polymerizable group, an epoxy group, a hydroxyl group, a thiol group, a primary amino group, and a secondary amino group, and that the ionic functional group contained in the (A) cyclic monomer is a group capable of forming at least one ion selected from the group consisting of a carboxyl ion, a sulfonate ion, a phosphate ion, a phosphonate ion, and a quaternary ammonium cation. The second invention relates to a cured product obtained by curing the curable composition of the first invention. The resulting cured product can be suitably used as a polishing pad. In a third aspect of the present invention, the cyclic molecule (A) is a cyclic monomer having both a polymerizable functional group and an ionic functional group.

[0013] The present invention relates to the following [1] to

[11] . [1] A curable composition containing (A) a cyclic monomer having both a polymerizable functional group and an ionic functional group in the molecule, and (B) a polymerizable monomer having a polymerizable functional group that can polymerize with the polymerizable functional group of the cyclic monomer (A). [2] The curable composition according to [1] above, wherein the polymerizable functional group of the (A) cyclic monomer is at least one group selected from the group consisting of a radically polymerizable group, an epoxy group, a hydroxyl group, a thiol group, a primary amino group, and a secondary amino group, and the ionic functional group of the (A) cyclic monomer is a group capable of forming at least one ion selected from the group consisting of a carboxyl ion, a sulfonate ion, a phosphate ion, a phosphonate ion, and a quaternary ammonium cation. [3] The curable composition according to [1] or [2] above, wherein in the (A) cyclic monomer, when the total molar ratio of the polymerizable functional group and the ionic functional group is taken as 100 mol %, the ratio of the ionic functional group is 1 mol % or more and less than 90 mol %. [4] The curable composition according to any one of the above [1] to [3], wherein the (A) cyclic monomer is a cyclic monomer in which a side chain has been introduced into a hydroxyl group of a cyclic molecule having the hydroxyl group, and the side chain has the polymerizable functional group and the ionic functional group. [5] The curable composition according to any one of the above [1] to [4], wherein the polymerizable functional group of the (A) cyclic monomer is at least one group selected from the group consisting of a hydroxyl group, a thiol group, a primary amino group, and a secondary amino group, and the (B) polymerizable monomer contains (B1) an iso(thio)cyanate compound having at least an iso(thio)cyanate group in the molecule. [6] The curable composition according to [5] above, wherein the polymerizable functional group of the (A) cyclic monomer contains at least a hydroxyl group, and the (B1) iso(thio)cyanate compound contained in the (B) polymerizable monomer contains a urethane prepolymer having iso(thio)cyanate groups at both ends of the (B12) molecule obtained by reacting (B32) a bifunctional active hydrogen-containing compound having two active hydrogen-containing groups in the molecule with (B13) a bifunctional polyiso(thio)cyanate compound having two iso(thio)cyanate groups in the molecule. [7] The curable composition according to the above [6], wherein the urethane prepolymer (B12) has an iso(thio)cyanate equivalent of 300 to 5,000. [8] The curable composition according to any one of the above [1] to [7], further comprising (D) hollow particles each having an outer shell made of a urethane resin and a hollow portion surrounded by the outer shell. [9] A cured product obtained by curing the curable composition according to any one of the above items [1] to [8].

[10] A polishing pad made of the cured product described in [9] above.

[11] (A) A cyclic monomer having both a polymerizable functional group and an ionic functional group in the molecule. [Effects of the Invention]

[0014] The curable composition of the present invention has good handleability, and the cured product obtained by curing the curable composition has excellent mechanical properties, particularly high abrasion resistance. Furthermore, the cured product has excellent hydrophilicity. Therefore, when the cured product is used for a sliding member, for example, as a polishing pad, it has good abrasion resistance. In addition, the cured product has excellent polishing properties. Specifically, the cured product can be used as a polishing pad that can exhibit a high polishing rate, low scratch resistance, and high flatness. DETAILED DESCRIPTION OF THE INVENTION

[0015] The curable composition of the present invention is a curable composition containing (A) a cyclic monomer having both a polymerizable functional group and an ionic functional group in the molecule (hereinafter, sometimes simply referred to as "(A) cyclic monomer" or "(A) component"), and (B) a polymerizable monomer having a polymerizable functional group that can polymerize with the polymerizable functional group of the (A) cyclic monomer (the polymerizable functional group possessed by the cyclic molecule) (hereinafter, sometimes simply referred to as "(B) polymerizable monomer" or "(B) component"). First, the (A) cyclic monomer will be explained.

[0016] <(A) Cyclic Monomer; Component (A)> The cyclic monomer (A) used in the present invention is not particularly limited as long as it is a cyclic molecule having both a polymerizable functional group and an ionic functional group. Examples of the cyclic molecule include cyclodextrin, crown ether, benzocrown, dibenzocrown, dicyclohexanocrown, cyclobis(paraquat-1,4-phenylene), dimethoxypillararene, calixarene, calixresorcinarene, and phenanthroline. Among them, cyclodextrin and calixarene are preferred, and cyclodextrin is most preferred.

[0017] The cyclodextrins include α-cyclodextrins (inner ring diameter: 0.45 to 0.6 nm), β-cyclodextrins (inner ring diameter: 0.6 to 0.8 nm), and γ-cyclodextrins (inner ring diameter: 0.8 to 0.95 nm). Mixtures of these may also be used. In the present invention, α-cyclodextrin and β-cyclodextrin are particularly preferred, with β-cyclodextrin being the most preferred in terms of cost and physical properties. The calixresorcinarene is a cyclic molecule obtained by cyclic condensation reaction of resorcinol with various aldehydes. The resorcinol is not limited to resorcinol, but may also be a resorcinol derivative such as 2-nitroresorcinol. The aldehyde may be any known aldehyde without any limitation, including aliphatic aldehydes such as n-butanal, isobutanal, and heptanal, and aromatic aldehydes such as benzaldehyde, vanillin, and 4-nitrobenzaldehyde. Two or more of these may be mixed and used. Heptanal, benzaldehyde, and vanillin are particularly preferred. In the present invention, the calixresorcinarene is preferably a tetramer, but is not limited thereto.

[0018] A polymerizable functional group and an ionic functional group are introduced into the (A) cyclic monomer. These functional groups may be directly bonded to the cyclic molecule, but it is preferable that a side chain is introduced into the cyclic molecule, and the polymerizable functional group and the ionic functional group are introduced into the side chain, particularly the terminal of the side chain. More specifically, it is preferable that a plurality of side chains are introduced into the (A) cyclic monomer, and the plurality of side chains preferably include a side chain having a polymerizable functional group at its terminal and a side chain having an ionic functional group at its terminal.

[0019] Next, the side chains introduced into the cyclic molecules will be described. The side chain can be introduced by, for example, utilizing a reactive functional group possessed by the cyclic molecule and modifying this reactive functional group (i.e., the side chain is introduced by reacting with the reactive functional group). Examples of the reactive functional group include a hydroxyl group and an amino group, and among these, a hydroxyl group is preferred. Therefore, the (A) cyclic monomer is preferably a cyclic monomer in which a side chain is introduced into the hydroxyl group of a cyclic molecule having a hydroxyl group, and the side chain preferably has a polymerizable functional group and an ionic functional group. For example, the β-cyclodextrin ring has 21 hydroxyl groups as reactive functional groups, and side chains are introduced by reacting with these hydroxyl groups. Therefore, up to 21 side chains can be introduced to one β-cyclodextrin ring. In the present invention, in order to fully utilize the functions of the side chains described above, it is preferable that at least three or more side chains are introduced. More preferably, the cyclic molecule has five or more side chains introduced, even more preferably, seven or more side chains introduced, and most preferably, eight or more side chains introduced. There is no particular upper limit, but if the number of side chains introduced is too large, the viscosity of the (A) cyclic monomer may increase and the handleability may decrease. Therefore, it is particularly preferable that 8 to 18 side chains are introduced. Furthermore, (A) the cyclic monomer is preferably composed only of a cyclic molecule and three or more side chains introduced into the cyclic molecule. The three or more side chains preferably include a side chain having a polymerizable functional group at its terminal and a side chain having an ionic functional group at its terminal. The three or more side chains preferably consist only of a side chain having a polymerizable functional group at its terminal and a side chain having an ionic functional group at its terminal.

[0020] The side chain is not particularly limited, but is preferably formed by repeating organic chains having a carbon number in the range of 3 to 20. The number average molecular weight of such a side chain is preferably, for example, 300 or more. More specifically, the number average molecular weight of such a side chain is in the range of 300 to 10,000, preferably 350 to 5,000, more preferably 400 to 5,000, and most preferably 400 to 1,500. By keeping it in this range, it becomes easy to adjust the hardness and physical properties of the obtained cured body. The number average molecular weight of this side chain can be adjusted by the amount used when introducing the side chain, and can be determined by calculation. 1 It can also be determined from H-NMR measurements. By setting the lower limit of the number-average molecular weight of the side chain as described above, excellent mechanical properties are exhibited, and when a cured product obtained by curing the curable composition of the present invention is used in a polishing pad, the polishing rate tends to be improved. Furthermore, compatibility with the (B) polymerizable monomer also tends to be improved. On the other hand, by setting the upper limit of the number-average molecular weight of the side chain as described above, the hardness and wear resistance of the cured product tend not to be reduced. As will be described in detail below, the reactive functional groups (e.g., hydroxyl groups) of the cyclic molecules are less reactive than the hydroxyl groups of the side chains, so even if the degree of modification is low, problems such as reduced compatibility and bleed-out are unlikely to occur.

[0021] In the present invention, when a hydroxyl group corresponds to a polymerizable functional group, it is considered as follows. For example, when the cyclic molecule is a cyclodextrin, a hydroxyl group of the cyclodextrin to which no side chain has been introduced is also considered to be a polymerizable functional group. Incidentally, when side chains are bonded to 9 of the 21 hydroxyl groups of the above-mentioned β-cyclodextrin, the degree of modification (degree of introduction) is 43%. In the present invention, the side chains described above may be linear or branched, provided that their molecular weights are within the aforementioned range. The methods and compounds disclosed in International Publication No. WO 2015 / 159875 can be used appropriately to introduce the side chains. Specifically, ring-opening polymerization, radical polymerization, cationic polymerization, anionic polymerization, and living radical polymerization such as atom transfer radical polymerization, RAFT polymerization, and NMP polymerization can be used. By using the above methods, a side chain of an appropriate size can be introduced by reacting an appropriately selected compound with the reactive functional group possessed by the cyclic molecule. For example, a side chain derived from a cyclic compound such as a lactone or a cyclic ether can be introduced by ring-opening polymerization. For example, the side chain introduced by ring-opening polymerization of a cyclic compound such as a lactone or a cyclic ether has a hydroxyl group introduced as a polymerizable functional group at the end of the side chain, as a group having an active hydrogen atom. Among the cyclic compounds, it is preferable to use cyclic ethers and lactones from the viewpoints of easy availability, high reactivity, and ease of adjusting the size (molecular weight). Suitable cyclic compounds such as cyclic ethers and lactones are disclosed, for example, in WO 2015 / 159875. The above cyclic compounds can be used alone or in combination of two or more kinds.

[0022] In the present invention, the cyclic compound into which a side chain can be introduced is preferably a lactone, and lactones such as ε-caprolactone, α-acetyl-γ-butyrolactone, α-methyl-γ-butyrolactone, γ-valerolactone, and γ-butyrolactone are particularly preferred, with ε-caprolactone being the most preferred. Furthermore, when introducing a side chain by reacting a cyclic compound via ring-opening polymerization, the reactive functional group (e.g., hydroxyl group) attached to the cyclic molecule may have poor reactivity, making it difficult to directly react with larger molecules, particularly due to steric hindrance. In such cases, for example, in order to react a cyclic compound such as ε-caprolactone, a low molecular weight compound such as propylene oxide is first reacted with the reactive functional group to hydroxypropylate it, thereby introducing a highly reactive functional group (e.g., hydroxyl group). Then, a side chain can be introduced by ring-opening polymerization using the aforementioned cyclic compound. In this case, the hydroxypropylated portion can also be considered a side chain.

[0023] In addition, by introducing a side chain derived from a cyclic compound such as a cyclic acetal, a cyclic amine, a cyclic carbonate, a cyclic iminoether, or a cyclic thiocarbonate by ring-opening polymerization, it is possible to introduce a side chain having a group having an active hydrogen as a polymerizable functional group. Among these, specific examples of suitable cyclic compounds are those described in, for example, WO 2015 / 068798.

[0024] Alternatively, a method of introducing a side chain into a cyclic molecule using radical polymerization can be employed. The cyclic molecule may not have an active site that serves as a radical initiation point. In this case, prior to reacting with a radical polymerizable compound, a compound for forming a radical initiation point may be reacted with a functional group (e.g., a hydroxyl group) possessed by the cyclic molecule to form an active site that serves as a radical initiation point. A typical example of a compound for forming the above-mentioned radical initiation point is an organic halogen compound. Examples include 2-bromoisobutyryl bromide, 2-bromobutyric acid, 2-bromopropionic acid, 2-chloropropionic acid, 2-bromoisobutyric acid, epichlorohydrin, epibromohydrin, and 2-chloroethyl isocyanate. That is, such an organic halogen compound reacts with a functional group possessed by a cyclic molecule to bond to the functional group possessed by the cyclic molecule, thereby introducing a group containing a halogen atom (organic halogen compound residue) into the cyclic molecule. During radical polymerization, a radical is generated in this organic halogen compound residue by migration of a halogen atom, etc., and this radical becomes the radical polymerization initiation point, thereby allowing the radical polymerization to proceed. Furthermore, the above-mentioned group having an active site that serves as an initiation point for radical polymerization (e.g., an organic halogen compound residue) can also be introduced by, for example, reacting a compound having a functional group such as amine, isocyanate, or imidazole with a hydroxyl group of a cyclic molecule to introduce a functional group other than a hydroxyl group, and then reacting such a functional group with the above-mentioned organic halogen compound.

[0025] In addition, as a radical polymerizable compound used to introduce a side chain by radical polymerization, a compound having at least one functional group such as a group having an ethylenically unsaturated bond, for example, a (meth)acrylate group, a vinyl group, or a styryl group (hereinafter referred to as an ethylenically unsaturated monomer) is preferably used. In addition, as the ethylenically unsaturated monomer, an oligomer or polymer having a terminal ethylenically unsaturated bond can also be used. Specific examples of suitable ethylenically unsaturated monomers include those described in International Publication No. 2015 / 068798.

[0026] <(A) Cyclic Monomer Polymerizable Functional Group (Polymerizable Functional Group on Side Chain)> The (A) cyclic monomer must have a polymerizable functional group. The polymerizable functional group is not particularly limited as long as it is directly or indirectly bonded to the cyclic molecule constituting the cyclic monomer, but in order to obtain a more effective cured product, it is preferable that it is introduced into the cyclic molecule via the side chain. Specifically, after introducing the side chain by the above method, the functional group of the side chain can be used as a polymerizable functional group as is, or the functional group of the side chain can be modified into another polymerizable functional group and used. In the present invention, the reaction of reacting a functional group of a side chain with another compound to introduce a structure derived from the other compound may be referred to as "modification." The compound used for modification can be any compound that can react with the functional group of the side chain without any particular limitation. By selecting the compound used for modification, it is possible to introduce various polymerizable functional groups into the side chain or to modify the side chain to a group that does not have a polymerizable functional group. As can be understood from the above explanation, the side chains introduced into the cyclic molecules may have various functional groups. Furthermore, depending on the type of functional group possessed by the compound used for introducing the side chain, a part of this side chain may bond to a functional group of the ring of a cyclic molecule possessed by another axis molecule, forming a crosslinked structure.

[0027] <Suitable Polymerizable Functional Groups Contained in (A) Cyclic Monomer and Their Number> The polymerizable functional group possessed by the (A) cyclic monomer is not particularly limited. In the present invention, the polymerizable functional group possessed by the (A) cyclic monomer is preferably at least one group selected from the group consisting of a radically polymerizable group, an epoxy group, a hydroxyl group, a thiol group, a primary amino group (-NH), and a secondary amino group (NHR; R is a substituent, for example, an alkyl group). Examples of the radically polymerizable group include a (meth)acrylate group, a vinyl group, and an allyl group. Note that "(meth)acrylate" refers to either or both of an acrylate and a methacrylate. Among these, a hydroxyl group is most preferred. In the case of a hydroxyl group, if the terminal of the side chain introduced when reacting the reactive functional group of the cyclic molecule is a hydroxyl group, it may be used as a polymerizable functional group as it is. Furthermore, if the cyclic molecule originally has a hydroxyl group, the hydroxyl group may be used as a polymerizable functional group as it is. However, in consideration of reactivity and the like, it is preferable that the terminal of the side chain be a polymerizable functional group (for example, a hydroxyl group).

[0028] The number of polymerizable functional groups contained in the (A) cyclic monomer is not particularly limited, but in order to exhibit excellent effects in the matrix resin, it is preferable that the (A) cyclic monomer contains at least two polymerizable functional groups. The polymerizable functional group is possessed by the cyclic molecule or the side chain introduced into the cyclic molecule. Among these, considering reactivity, it is preferable that the terminal of the side chain be the polymerizable functional group. It is also preferable that the (A) cyclic monomer has two or more polymerizable functional groups introduced into the terminal of the side chain. The upper limit of the number of polymerizable functional groups is not particularly limited. It is preferable that the number of moles of the polymerizable functional group introduced into the terminal of the side chain is 0.1 mmol / g to 10 mmol / g relative to the weight-average molecular weight (Mw) of the (A) cyclic monomer. This value is obtained by dividing the number of moles of the polymerizable functional group introduced into the terminal of the side chain by the weight-average molecular weight (Mw) of the (A) cyclic monomer. In other words, it refers to the number of moles of the polymerizable functional group introduced into the terminal of the side chain per gram of the (A) cyclic monomer.

[0029] More preferably, the number of moles of the polymerizable functional group introduced at the end of the side chain is 0.2 mmol to 8 mmol / g. Particularly preferably, the number of moles of the polymerizable functional group introduced at the end of the side chain is 0.5 mmol to 5 mmol / g. The weight average molecular weight is a value measured by gel permeation chromatography (GPC), which will be described in detail below. Furthermore, the total number of moles of polymerizable functional groups, including polymerizable functional groups not introduced into side chains (for example, polymerizable functional groups possessed by cyclic molecules) and polymerizable functional groups introduced into the side chains, is preferably within the following range. Specifically, the total number of moles of polymerizable functional groups relative to the weight-average molecular weight (Mw) of the (A) cyclic monomer is preferably 0.2 mmol to 20 mmol / g. More preferably, the total number of moles of polymerizable functional groups is 0.4 mmol to 16 mmol / g, and particularly preferably 1 mmol to 10 mmol / g. The total polymerizable functional groups include, for example, polymerizable functional groups possessed by cyclic molecules not having side chains introduced therein (specifically, for example, unmodified hydroxyl groups in cyclodextrin not having side chains introduced therein). It goes without saying that the number of moles of the polymerizable functional groups described above is an average value.

[0030] <(A) Cyclic Monomer Ionic Functional Group (Ionic Functional Group on Side Chain)> The cyclic monomer (A) must have an ionic functional group. To obtain a more effective cured product, the ionic functional group is not particularly limited as long as it is directly or indirectly bonded to the cyclic molecule constituting the cyclic monomer, but is preferably present on the side chain introduced into the cyclic molecule. It is particularly preferred that the ionic functional group be present at the end of the side chain. The method for introducing the ionic functional group is not particularly limited, but a preferred method is to introduce the side chain using the above-mentioned method and then modify the functional group on the side chain into an ionic functional group.

[0031] In the present invention, the ionic functional group refers to a group having a moiety that can become a cation or anion, and is, for example, a group that can form at least one type of ion selected from the group consisting of a carboxyl ion, a sulfonate ion, a phosphate ion, a phosphonate ion, and a quaternary ammonium cation. Specifically, it is a carboxyl group or a carboxyl base (a base of a carboxyl group), a sulfonic acid group or a sulfonate base (a base of a sulfonic acid group), a phosphoric acid group or a phosphate base (a base of a phosphoric acid group), a phosphonic acid group or a phosphonate base (a base of a phosphonic acid group), and a quaternary ammonium cation group or a quaternary ammonium base, and preferably a sulfonic acid group. In the present invention, the method for introducing an ionic functional group into a cyclic molecule is not particularly limited. An example of the introduction method is shown below. As described above, the introduction method is not limited, and an ionic functional group can also be introduced into the (A) cyclic monomer by a method other than the introduction method described below.

[0032] <Examples of introducing ionic functional groups (including their bases)> To introduce a carboxylic acid group or a sulfonic acid group, a ring-opening reaction of an acid anhydride can be used. For example, when a cyclic molecule has a hydroxyl group as a reactive functional group (the cyclic molecule may directly have a hydroxyl group, or a side chain introduced to the cyclic molecule may have a hydroxyl group), a carboxyl group can be introduced by reacting the hydroxyl group with an acid anhydride. Similarly, a sulfonic acid can be introduced by reacting the hydroxyl group with a sultone compound.

[0033] Specific examples of acid anhydride compounds include succinic anhydride, butylsuccinic anhydride, decylsuccinic anhydride, 2-dodecen-1-ylsuccinic anhydride, 2,2-dimethylsuccinic anhydride, hexadecylsuccinic anhydride, 2-hexen-1-ylsuccinic anhydride, isooctadecylsuccinic anhydride, isooctadecenylsuccinic anhydride, (2-methyl-2-propenyl)succinic anhydride, octadecylsuccinic anhydride, and 2-octenylsuccinic anhydride. Examples of the succinic anhydride include succinic anhydride, n-octyl succinic anhydride, (2,7-octadien-1-yl)succinic anhydride, tetradecenyl succinic anhydride, tetradecyl succinic anhydride, tetrapropenyl succinic anhydride, dodecyl succinic anhydride, glutaric anhydride, 3,3-dimethylglutaric anhydride, 2,2-dimethylglutaric anhydride, 3-methylglutaric anhydride, 1,4-dioxane-2,6-dione, maleic anhydride, and phthalic anhydride. These acid anhydride compounds can be reacted with hydroxyl groups of cyclic molecules to introduce carboxyl groups into the cyclic molecules, which can then be further reacted (neutralized) to form carboxyl salt groups.

[0034] Specific examples of the sultone compound include 1,3-propane sultone and 1,4-butane sultone. These sultone compounds can be reacted with hydroxyl groups of cyclic molecules to introduce sulfonic acid groups into the cyclic molecules, which can then be further reacted (neutralized) to form sulfonate salt groups.

[0035] Furthermore, examples of introducing a phosphate group, a phosphonate group, and a quaternary ammonium cation group include the formation of an ester bond or an amide bond. For example, when a cyclic molecule has a hydroxyl group as a reactive group (the cyclic molecule may directly have a hydroxyl group, or a side chain introduced into the cyclic molecule may have a hydroxyl group), the ionic functional group can be introduced via an ester bond by using a compound containing a carboxyl group or an acid chloride group (e.g., a -COCl group) in addition to the ionic group.

[0036] Specific examples of compounds containing a carboxyl group and an acid chloride group and an ionic functional group include: 4-phosphonobutyric acid, glycine-N,N-bis(methylenesulfonic acid), 2-phosphonobutane-1,2,4-tricarboxylic acid, 3-phosphonopropionic acid, and phosphoserine when introducing a phosphate group or a phosphonate group; N,N-dipropyl-alanine, N,N-dimethyl-β-alanine hydrochloride, 1-(ethoxycarbonyl)isonipecotic acid, 1-forminoisonipecotic acid, betaine anhydride, betaine hydrochloride, carnitine hydrochloride, and carnitine when introducing a quaternary ammonium salt or a quaternary ammonium cation;

[0037] Furthermore, when the cyclic molecule has a carboxyl group as a reactive group (the cyclic molecule may directly have a carboxyl group, or a side chain introduced into the cyclic molecule may have a carboxyl group), the carboxyl group or carboxyl base can be reacted with a compound having a hydroxyl group or an amino group in the molecule and an ionic functional group. Specific examples of compounds that contain a hydroxyl group or an amino group and also contain an ionic functional group are as follows:

[0038] Alendronic acid, 4-hydroxymethyl-2,6,7-trioxa-1-phosphabicyclo[2,2,2]octane 1-oxide, (1-aminoethyl)phosphonic acid, phosphoriethanolamine, N,N-dimethylethanolamine, N,N-dimethylpropanolamine, N,N-dimethylisopropanolamine, N,N-diisopropylethanolamine, 4-dimethylamino-1-butanol, 6-dimethylamino-1-hexanol, dimethylaminoneopentanol, N'-(2-hydroxyethyl)-N,N,N'-trimethylethylenediamine, 5-diethylamino-1-pentanol, 4-methylpiperazine-1-ethanol, 1-(2-hydroxyethyl)piperazine, 3,3-diaminoethanol, N,N-diethylaminopropylamine, N,N-diethylaminoethylamine, N,N-diisopropylethanolamine Examples of suitable amines include methylethylenediamine, N,N-dimethylaminopropylamine, N,N-diethyl-1,4-diaminopentane, N,N-dibutyl-1,3-diaminopropane, N,N-diethyl-N'-methylethylenediamine, N,N-dibutylethylenediamine, N,N-dimethylneopentanediamine, N,N-bis[3-(dimethylamino)propyl]amine, N,N,N'-trimethylethylenediamine, N-(2-aminoethyl)piperazine, 1-butylpiperazine, 1-ethylpiperazine, 1-methylpiperazine, 1-isopropylpiperazine, 1-(2-methoxyethyl)piperazine, β-methylcholine iodide, choline chloride, choline bromide, bis(2-hydroxyethyl)dimethylammonium chloride, bethanechol chloride, albamylcholine chloride, and trimethylacetohydrazide ammonium chloride.

[0039] In the present invention, the ionic functional group of the cyclic monomer (A) can be neutralized to form a salt structure, which allows for controlling the reactivity when an iso(thio)cyanate compound is used in the polymerizable monomer (B) described below. In the present invention, particularly preferred examples of the ionic functional group possessed by the cyclic molecule of the cyclic monomer (A) include a carboxylic acid group, a sulfonic acid group, a quaternary ammonium salt, and a quaternary ammonium cation group, with a sulfonic acid group being the most preferred.

[0040] The number of ionic functional groups contained in the (A) cyclic monomer is not particularly limited. It is preferably 0.01 to 1.0 mmol / g, and more preferably 0.05 to 0.5 mmol / g, relative to the weight-average molecular weight (Mw) of the (A) cyclic monomer. That is, if the number of ionic functional groups is too large, the mechanical strength of the cured product tends to decrease. On the other hand, if the number of ionic functional groups is too small, the hydrophilicity effect tends to decrease. This value is calculated by dividing the number of moles of ionic functional groups contained in the cyclic molecule by the weight-average molecular weight (Mw) of the (A) cyclic monomer. In other words, it refers to the number of moles of ionic functional groups contained per gram of the (A) cyclic monomer. Naturally, this number of moles of ionic functional groups is an average value. The ionic functional group may be one that the cyclic molecule has, or one that is introduced into the cyclic molecule by using the side chain. Among these, in consideration of the effect of the ionic group, it is preferable that the terminal of the side chain is an ionic functional group, and the number of ionic functional groups satisfies the above range.

[0041] (Number of polymerizable functional groups and ionic functional groups) The (A) cyclic monomer in the present invention is a cyclic molecule into which the polymerizable functional group and the ionic functional group have been introduced. Preferably, the cyclic molecule has the polymerizable functional group and the ionic functional group via a side chain. Most preferably, the terminal of the side chain is a polymerizable functional group and an ionic functional group.

[0042] In the cyclic monomer (A), the ratio of the polymerizable functional group to the ionic functional group is preferably 1 mol % or more and less than 90 mol % when the total molar ratio of the polymerizable functional group and the ionic functional group is taken as 100 mol %. In consideration of the balance of physical properties of the resulting cured body, the ratio of the ionic functional group is more preferably 2 mol % or more and 35 mol % or less, and even more preferably 2 mol % or more and 25 mol % or less. The proportion of polymerizable functional groups is the proportion of all polymerizable functional groups possessed by the cyclic molecule. For example, in the case of a cyclic molecule such as cyclodextrin, where the polymerizable functional group is a hydroxyl group, the total number of moles of hydroxyl groups on the cyclic molecule not modified with a side chain and hydroxyl groups introduced into the side chain is the number of moles of the polymerizable functional groups (the number of moles of all polymerizable functional groups). Therefore, the above part can be interpreted as follows: When the total number of moles of all polymerizable functional groups and the total mole ratio of the ionic functional groups is taken as 100 mole%, the proportion of the ionic functional groups is preferably 1 mole% or more and less than 90 mole%. Considering the balance of physical properties of the resulting cured body, the proportion of the ionic functional groups is more preferably 2 mole% or more and 35 mole% or less, and even more preferably 2 mole% or more and 25 mole% or less. However, as mentioned above, polymerizable functional groups that are not modified with side chains may have poor reactivity. Therefore, when the molar number of polymerizable functional groups introduced into the side chains is taken as the total molar ratio of the polymerizable functional groups introduced into the side chains and the ionic functional groups introduced into the side chains is 100 mol%, in order to obtain a cured product with excellent physical properties, the ratio of the ionic functional groups is more preferably 2 mol% to 90 mol%, even more preferably 3 mol% to 60 mol%, and particularly preferably 4 mol% to 40 mol%.

[0043] The molar ratio of the ionic functional groups to the total number of moles of the polymerizable functional groups and ionic functional groups introduced into the side chains is preferably 10 to 80 mol %, more preferably 20 to 60 mol %, from the viewpoint of improving the wear resistance of the cured body and improving the flatness of the object to be polished.

[0044] (Other Preferred Structures of (A) Cyclic Monomer) In the present invention, the most suitable cyclic monomer (A) is preferably a cyclic monomer in which the cyclic molecule is β-cyclodextrin. Furthermore, it is preferable that ε-caprolactone is used as the cyclic compound, and a side chain (a polycaprolactone chain with a terminal polymerizable functional hydroxyl group) is introduced into the cyclic molecule, and that an ionic functional group is further introduced by modifying a portion of the terminal hydroxyl group of the side chain. The ionic functional group is preferably a group that forms a carboxylate ion, a sulfonate ion, or a quaternary ammonium cation. In this case, the hydroxyl group of β-cyclodextrin may be hydroxypropylated, followed by ring-opening polymerization to introduce a polycaprolactone chain. The proportion of modified hydroxyl groups on the β-cyclodextrin ring (modification degree), the molecular weight of the side chain, and the number of moles of the polymerizable functional group and the ionic functional group are preferably as described above. Furthermore, it is preferable that the component (A) has a certain viscosity range. This allows for excellent handling properties. A preferred viscosity range at 60°C is 500 mPa·s to 50,000 mPa·s, more preferably 500 mPa·s to 10,000 mPa·s, and most preferably 1,000 mPa·s to 6,000 mPa·s. These values ​​can be determined, for example, using a rotational viscometer.

[0045] Furthermore, if the weight-average molecular weight Mw of the (A) cyclic monomer is too large, when mixed with other components, such as other (B) polymerizable monomers, the viscosity increases, making handling difficult. In some cases, compatibility tends to be poor. From this perspective, the weight-average molecular weight (Mw) of the (A) cyclic monomer is preferably 1,500 to 100,000, particularly 2,000 to 30,000, particularly preferably 2,500 to 10,000, and most preferably 3,000 to 8,000. Furthermore, to exhibit stable physical properties, the dispersity (weight-average molecular weight / number-average molecular weight) is preferably 1.2 or less. The weight-average molecular weight (Mw) and dispersity are values ​​measured using the GPC measurement method described in the Examples below. Furthermore, as mentioned above, if the molecular weight of the (A) cyclic monomer is too large, handling and compatibility tend to be poor. Therefore, it is preferable that the (A) cyclic monomer does not form a complex with other molecules.

[0046] <(B) Polymerizable Monomer Having a Polymerizable Functional Group Polymerizable with the Polymerizable Functional Group of the Cyclic Monomer (A)> In the present invention, the polymerizable monomer (B) is a compound having a group capable of reacting (polymerizing) with the polymerizable functional group of the cyclic monomer (A), and is, of course, a compound other than the cyclic monomer (A). The polymerizable monomer (B) can be any known compound that can be polymerized with the cyclic monomer (A) without any limitations. As described above, various polymerizable functional groups can be introduced into the cyclic monomer (A). The polymerizable monomer (B) can be selected accordingly. For example, the polymerizable monomers described in WO 2015 / 068798 can be used. In the present invention, for example, when the polymerizable functional group possessed by the (A) cyclic monomer is selected from a hydroxyl group, a thiol group, and an amino group (a primary amino group (-NH), or a secondary amino group (-NHR; R is a substituent, for example, an alkyl group)), the (B) polymerizable monomer preferably contains (B1) an iso(thio)cyanate compound having at least an iso(thio)cyanate group in the molecule (hereinafter, sometimes simply referred to as "(B1) iso(thio)cyanate compound" or "(B1) component").

[0047] Furthermore, when the polymerizable functional group possessed by the (A) cyclic monomer is a hydroxyl group, an amino group, or an iso(thio)cyanate group, the (B) polymerizable monomer can also be selected from (B2) an epoxy group-containing monomer having an epoxy group (hereinafter, sometimes simply referred to as "(B2) epoxy group-containing monomer" or "(B2) component"). On the other hand, when the polymerizable functional group possessed by the (A) cyclic monomer is an iso(thio)cyanate group, the (B) polymerizable monomer can be selected from (B3) a (thio)ol compound having at least one group selected from a hydroxyl group and a thiol group (hereinafter, sometimes simply referred to as "(B3) (thio)ol compound" or "(B3) component"), and (B4) an amino group-containing monomer having an amino group (simply "(B4) amino group-containing monomer" or "(B4) component"). In the present invention, the term "iso(thio)cyanate group" refers to an isocyanate group (NCO group) or an isothiocyanate group (NCS group). Therefore, when a plurality of isocyanate groups are present, the total number of isocyanate groups and isothiocyanate groups is the number of isocyanate groups. In the present invention, the polymerizable monomer (B) may be used alone or in combination of two or more kinds.

[0048] <Polymerization method / sequential addition polymerization> The curable composition of the present invention may contain other components as long as it contains a cyclic monomer (A) and a polymerizable monomer (B). For example, when the polymerization reaction is a step-growth addition polymerization (e.g., polycondensation / polyaddition) polymerization, if the composition contains a cyclic monomer (A) and a polymerizable monomer (B), it may contain other polymerizable monomers that do not polymerize with the cyclic monomer (A) but do polymerize with the polymerizable monomer (B). In the case of step-growth addition polymerization, if a polymerizable monomer (B) that can polymerize with component (A) is present, component (A), component (B), and other polymerizable monomers that can polymerize with component (B) can be copolymerized, even if other polymerizable monomers that do not polymerize with component (A) are present. Furthermore, both component (B) and component (A) may contain polymerizable polymerizable monomers. An example of step-growth addition polymerization will be described in more detail. Specifically, for example, when the polymerizable functional group possessed by the cyclic monomer (A) is an active hydrogen-containing group such as a hydroxyl group, if an iso(thio)cyanate compound having an iso(thio)cyanate group (B1) is included as a polymerizable monomer, the aforementioned components (B3) and (B4) can be included. That is, if the component (B1) that polymerizes with the component (A) is included, the component (B3) and the component (B4) that do not polymerize with the component (A) can be included. In the case of step-growth addition polymerization, the presence of the component (B1) allows for the production of a cured product in which the components (A), (B1), (B3), and (B4) are copolymerized. Naturally, in this case, the polymerizable monomer (B) can also include the component (B2). The polymerizable monomer (B) may consist of the component (B1) that can polymerize with the component (A). In the case of a sequential addition reaction, it is preferable to store the components that polymerize with each other (component (A) and each polymerizable monomer) separately until polymerization occurs.

[0049] <Polymerization method / chain (radical) polymerization> Furthermore, when the polymerizable functional group possessed by the (A) cyclic monomer is a radically polymerizable group, the (B) polymerizable monomer is composed of a monomer having a radically polymerizable group. In the case of radical polymerization, since it is a chain polymerization, unlike step-growth addition polymerization, all of the (B) polymerizable monomers are composed of monomers having radically polymerizable groups. Specifically, the (B) polymerizable monomer is preferably selected from (meth)acrylate compounds and allyl compounds having a (meth)acrylate group of the component (B5) described in detail below, and is particularly preferably selected from (meth)acrylate compounds.

[0050] <Polymerization method / sequential addition polymerization and chain (radical) polymerization> As described above, the cases of sequential addition polymerization and chain polymerization have been explained, but when both can be carried out, the following can also be done. For example, when the polymerizable functional group possessed by the (A) cyclic monomer has both an active hydrogen-containing group such as a hydroxyl group and a radically polymerizable group, the (B) polymerizable monomer may be only (B5) a (meth)acrylate compound or allyl compound having a (meth)acrylate group, or the (B) polymerizable monomer may contain other components (B2), (B3), (B4), and (B5) as long as it contains the (B1) iso(thio)cyanate compound.

[0051] <(B) Polymerizable Monomer> <Polymerization method / polymerizable monomer for step-growth addition polymerization> <(B1) Iso(thia)cyanate compound; (B1) component> The (B1) iso(thio)cyanate compound is a monomer having at least one type of isocyanate group or isothiocyanate group. Of course, a monomer having both an isocyanate group and an iso(thio)cyanate group can also be selected. Among these, a compound having 2 to 6 iso(thio)cyanate groups in the molecule is preferred, a compound having 2 to 4 groups is more preferred, and a compound having 2 groups is even more preferred. The (B1) iso(thio)cyanate compound may be a bifunctional polyiso(thio)cyanate compound having two iso(thio)cyanate groups in the molecule (B13) described below (hereinafter, sometimes simply referred to as "(B13) bifunctional polyiso(thio)cyanate compound" or "(B13) component"), (B32) a bifunctional active hydrogen-containing compound having two active hydrogen-containing groups in the molecule (hereinafter, sometimes simply referred to as "(B32) bifunctional active hydrogen-containing compound" or "(B32) component"); The (B12) urethane prepolymer may be a urethane prepolymer having iso(thio)cyanate groups at both ends of the (B12) molecule, which is prepared (manufactured) by the reaction of (B12) (hereinafter, this may be simply referred to as "(B12) urethane prepolymer" or "(B12) component"). As the (B12) urethane prepolymer corresponding to the iso(thio)cyanate compound, any commonly used one containing unreacted iso(thio)cyanate groups can be used in the present invention without any limitations.

[0052] The active hydrogen-containing group is a group selected from a hydroxyl group, a thiol group, a primary amino group, or a secondary amino group (e.g., —NHR; R is preferably an alkyl group). Specific examples of these (B32) components are exemplified in the (B3) (thiol) compound or (B4) amino group-containing monomer described in detail below. Considering reactivity, the active hydrogen-containing group is preferably a hydroxyl group or a thiol group. Therefore, the (B32) component is also preferably a bifunctional poly(thio)ol compound having two hydroxyl groups, two thiol groups, or one hydroxyl group and one thiol group.

[0053] The (B1) iso(thio)cyanate compounds can be broadly classified into, for example, aliphatic isocyanates, alicyclic isocyanates, aromatic isocyanates, isothiocyanate compounds, and (B12) urethane prepolymers. The (B1) iso(thio)cyanate compounds can be one type of compound or multiple types of compounds. When multiple types of compounds are used, the reference mass is the total amount of the multiple types of compounds. Specific examples of these iso(thio)cyanate compounds include the following:

[0054] Aliphatic isocyanate; component (B1) 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 diisocyanate difunctional isocyanates such as 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 the (B13) difunctional polyiso(thio)cyanate compound constituting the (B12) urethane prepolymer, which will be described in detail below); Monofunctional isocyanates such as ethyl isocyanate, n-propyl isocyanate, i-propyl isocyanate, butyl isocyanate, and octadecyl isocyanate.

[0055] Alicyclic isocyanate; component (B1) Isophorone diisocyanate, (bicyclo[2.2.1]heptane-2,5-diyl)bismethylene diisocyanate, (bicyclo[2.2.1]heptane-2,6-diyl)bismethylene diisocyanate, 2β,5α-bis(isocyanate)norbornane, 2β,5β-bis(isocyanate)norbornane, 2β,6α-bis(isocyanate)norbornane, 2β,6β-bis(isocyanate)norbornane, 2,6-di(isocyanatemethyl)furan, bis( Isocyanatemethyl)cyclohexane, dicyclohexylmethane-4,4'-diisocyanate, 4,4-isopropylidenebis(cyclohexylisocyanate), cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate, bis(4-isocyanato-n-butylidene)pentaerythritol, dimer acid diisocyanate, 2,5- Bis(isocyanatomethyl)-bicyclo[2,2,1]-heptane, 2,6-bis(isocyanatomethyl)-bicyclo[2,2,1]-heptane, 3,8-bis(isocyanatomethyl)tricyclodecane, 3,9-bis(isocyanatomethyl)tricyclodecane, 4,8-bis(isocyanatomethyl)tricyclodecane, 4,9-bis(isocyanatomethyl)tricyclodecane, 1,5-diisocyanatodecalin, 2,7-diisocyanatodecalin, 1,4- Diisocyanate decalin, 2,6-diisocyanate decalin, bicyclo[4.3.0]nonane-3,7-diisocyanate, bicyclo[4.3.0]nonane-4,8-diisocyanate, bicyclo[2.2.1]heptane-2,5-diisocyanate and bicyclo[2.2.1]heptane-2,6-diisocyanate, bicyclo[2,2,2]octane-2,5-diisocyanate, bicyclo[2,2,2]octane-2,6-diisocyanate, tricyclo[5.2.1.0]octane-2,5-diisocyanate, bicyclo[2,2,2]octane-2,6-diisocyanate, 2.6 ] decane-3,8-diisocyanate, tricyclo[5.2.1.0 2.6] Difunctional isocyanates such as decane-4,9-diisocyanate (corresponding to the difunctional polyiso(thio)cyanate compound (B13) constituting the urethane prepolymer (B12) described in detail below). 2-isocyanatomethyl-3-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2,2,1]-heptane, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2,2,1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2,2,1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2,2,1]-heptane, 2-isocyanatomethyl-3-(3-isocyanatopropyl polyfunctional isocyanates such as 2-isocyanatemethyl-3-(3-isocyanatepropyl)-6-(2-isocyanateethyl)-bicyclo[2,1,1]-heptane, 2-isocyanatemethyl-2-(3-isocyanatepropyl)-5-(2-isocyanateethyl)-bicyclo[2,2,1]-heptane, 2-isocyanatemethyl-2-(3-isocyanatepropyl)-6-(2-isocyanateethyl)-bicyclo[2,2,1]-heptane, and 1,3,5-tris(isocyanatemethyl)cyclohexane. Monofunctional isocyanates such as cyclohexyl isocyanate.

[0056] Aromatic isocyanate; component (B1) Xylylene diisocyanate (o-, m-, p-), tetrachloro-m-xylylene diisocyanate, methylenediphenyl-4,4'-diisocyanate, 4-chloro-m-xylylene diisocyanate, 4,5-dichloro-m-xylylene diisocyanate, 2,3,5,6-tetrabromo-p-xylylene diisocyanate, 4-methyl-m-xylylene diisocyanate, 4-ethyl-m-xylylene diisocyanate, bis(isocyanatoethyl)benzene, bis(isocyanatopropyl)benzene, 1,3-bis(α, α-dimethylisocyanatomethyl)benzene, 1,4-bis(α,α-dimethylisocyanatomethyl)benzene, α,α,α',α'-tetramethylxylylene diisocyanate, bis(isocyanatobutyl)benzene, bis(isocyanatomethyl)naphthalene, bis(isocyanatomethyl)diphenyl ether, bis(isocyanatoethyl)phthalate, 2,6-di(isocyanatomethyl)furan, phenylene diisocyanate (o-, m-, p-), tolylene diisocyanate, ethyl phenylene diisocyanate, isocyanate Isopropyl phenylene diisocyanate, dimethyl phenylene diisocyanate, diethyl phenylene diisocyanate, diisopropyl phenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, 1,3,5-triisocyanate methylbenzene, 1,5-naphthalene diisocyanate, methyl naphthalene diisocyanate, biphenyl diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2' -Diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, bibenzyl-4,4'-diisocyanate, bis(isocyanatophenyl)ethylene, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, phenylisocyanatomethyl isocyanate, phenylisocyanatoethyl isocyanate, tetrahydronaphthylene diisocyanate, hexahydrobenzene diisocyanate, hexahydrodiphenylmethane-4,Bifunctional isocyanates such as 4'-diisocyanate, diphenyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate, 1,3-propylene glycol diphenyl ether diisocyanate, benzophenone diisocyanate, diethylene glycol diphenyl ether diisocyanate, dibenzofuran diisocyanate, carbazole diisocyanate, ethyl carbazole diisocyanate, dichlorocarbazole diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate (corresponding to the (B13) bifunctional polyiso(thio)cyanate compound constituting the (B12) urethane prepolymer, which will be described in detail below). Polyfunctional isocyanates such as mesitylene triisocyanate, triphenylmethane triisocyanate, polymeric MDI, naphthalene triisocyanate, diphenylmethane-2,4,4'-triisocyanate, 3-methyldiphenylmethane-4,4',6-triisocyanate, and 4-methyl-diphenylmethane-2,3,4',5,6-pentaisocyanate. Monofunctional isocyanates such as phenyl isocyanate, 3-i-propenylcumyl isocyanate, 4-methoxyphenyl isocyanate, m-tolyl isocyanate, p-tolyl isocyanate, 1-naphthyl isocyanate, and dimethylbenzyl isocyanate. Isothiocyanate compound; component (B1) Bifunctional iso(thio)cyanates such as p-phenylenediisothiocyanate, xylylene-1,4-diisothiocyanate, and ethylidinediisothiocyanate (corresponding to the (B13) bifunctional polyiso(thio)cyanate compound constituting the (B12) urethane prepolymer described in detail below).

[0057] <(B12) Urethane prepolymer; urethane (B1) component having iso(thio)cyanate groups at both ends> In the present invention, a urethane prepolymer having iso(thio)cyanate groups at both ends of the molecule (B12), which is prepared by reacting the (B13) bifunctional polyiso(thio)cyanate compound with the (B32) bifunctional active hydrogen-containing compound having two active hydrogen-containing groups in the molecule, as described below, can also be used as the (B1) iso(thio)cyanate compound.

[0058] When preparing (B12) a urethane prepolymer, although not particularly limited, it is particularly preferable to use the following monomers as the (B13) bifunctional polyiso(thio)cyanate compound. Specifically, it is preferable to use 1,5-naphthalene diisocyanate, xylene diisocyanate (o-, m-, p-), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, phenylene diisocyanate (o-, m-, p-), 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and 4,4'-diphenylmethane diisocyanate. These can be reacted with (B32) a bifunctional active hydrogen-containing compound to obtain a (B12) component having iso(thio)cyanate groups at both ends.

[0059] Furthermore, in order for the final cured product (urethane resin) to exhibit particularly excellent properties, it is preferable to produce the urethane prepolymer (B12) using at least one bifunctional active hydrogen-containing compound (B32) having a molecular weight (number average molecular weight) of 300 to 2000. The active hydrogen-containing group refers to a hydroxyl group, a thiol group, a primary amino group, or a secondary amino group. In particular, in consideration of reactivity, the active hydrogen-containing group in the bifunctional active hydrogen-containing compound (B32) is preferably a hydroxyl group and / or a thiol group. The (B32) bifunctional active hydrogen-containing compound can be used in combination with other different types or with different molecular weights, as long as it contains a (B32) bifunctional active hydrogen-containing compound having a molecular weight (number average molecular weight) of 300 to 2000. Furthermore, in order to adjust the hardness, etc., of the finally obtained urethane resin, when forming the (B12) urethane prepolymer, a (B32) bifunctional active hydrogen-containing compound having a molecular weight (number average molecular weight) of 300 to 2000 and a (B32) bifunctional active hydrogen-containing compound having a molecular weight (number average molecular weight) of 90 to 300 can be used in combination. In this case, although it depends on the type of (B32) bifunctional active hydrogen-containing compound and (B13) bifunctional polyiso(thio)cyanate compound used and their amounts, when the (B32) bifunctional active hydrogen-containing compound having a molecular weight of 300 to 2000 is taken as 100 parts by mass, the (B32) bifunctional active hydrogen-containing compound having a molecular weight of 90 to 300 is preferably 0 to 50 parts by mass, and more preferably 1 to 40 parts by mass.

[0060] <(B12) component: Characteristics of urethane prepolymer> The (B12) urethane prepolymer must have iso(thio)cyanate groups at both ends of the molecule. Therefore, the (B12) urethane prepolymer is preferably produced in such a manner that the ratio (n5) of the moles of iso(thio)cyanate groups in the (B13) bifunctional polyiso(thio)cyanate compound and the ratio (n6) of the moles of active hydrogen-containing groups (hydroxyl groups, thiol groups, or amino groups (primary amino groups are considered to be 1 mole)) in the (B32) bifunctional active hydrogen-containing compound satisfy the relationship 1 < (n5) / (n6) ≦ 2.3. When two or more (B13) bifunctional polyiso(thio)cyanate compounds are used, the moles (n5) of the iso(thio)cyanate groups refers to the total moles of iso(thio)cyanate groups in the (B13) polyiso(thio)cyanate compounds. Furthermore, the number of moles (n6) of active hydrogen-containing groups in two or more types of bifunctional active hydrogen-containing compounds (B32) is the total number of moles of active hydrogen in those active hydrogen-containing groups. Even when the active hydrogen-containing group is a primary amino group, the primary amino group is considered to be 1 mole. In other words, a considerable amount of energy is required for the second amino group (-NH) in a primary amino group to react (even in a primary amino group, the second -NH is difficult to react). Therefore, in the present invention, even when a bifunctional active hydrogen-containing compound (B32) having a primary amino group is used, the primary amino group can be calculated as 1 mole.

[0061] The iso(thio)cyanate equivalent of the (B12) urethane prepolymer can be determined by quantifying the iso(thio)cyanate groups in the (B12) urethane prepolymer in accordance with JIS K 7301. The iso(thio)cyanate groups can be quantified by the following back titration method. First, the obtained (B12) urethane prepolymer is dissolved in a dry solvent. Next, di-n-butylamine, with a known concentration and in a clearly excess amount relative to the amount of iso(thio)cyanate groups in the (B12) urethane prepolymer, is added to the dry solvent, and all the iso(thio)cyanate groups in the (B12) urethane prepolymer are reacted with the di-n-butylamine. Next, the unconsumed di-n-butylamine (not involved in the reaction) is titrated with acid to determine the amount of di-n-butylamine consumed. Since the amount of di-n-butylamine consumed is the same as the amount of iso(thio)cyanate groups in the urethane prepolymer (B12), the iso(thio)cyanate equivalent can be calculated. Furthermore, since the urethane prepolymer (B12) is a linear urethane prepolymer with iso(thio)cyanate groups at both ends, the number-average molecular weight of the urethane prepolymer (B12) is twice the iso(thio)cyanate equivalent. The molecular weight of the urethane prepolymer (B12) is likely to coincide with the value measured by gel permeation chromatography (GPC). When the urethane prepolymer (B12) and a bifunctional polyiso(thio)cyanate compound (B13) are used in combination, a mixture of the two can be measured according to the above method.

[0062] The (B12) urethane prepolymer is not particularly limited, but preferably has an iso(thio)cyanate equivalent of 300 to 5,000, more preferably 350 to 3,000, and particularly preferably 350 to 2,000. The reason for this is not particularly clear, but is thought to be as follows: The reaction of the (B12) urethane prepolymer, which has a certain molecular weight, with the polymerizable functional group of the (A) cyclic monomer increases the mobility of the molecule itself, which is thought to result in easier recovery from deformation (elastic recovery; low hysteresis). Furthermore, the use of the (B12) urethane prepolymer is thought to facilitate dispersion of crosslinking points in the urethane resin, resulting in random and uniform distribution, thereby demonstrating stable performance. Furthermore, the urethane resin obtained using the (B12) urethane prepolymer is thought to be easier to control during production and to be suitable for use as a polishing pad. It is believed that such effects are exhibited when the urethane prepolymer (B12) and the bifunctional polyiso(thio)cyanate compound (B13) are used in combination, even if the average iso(thio)cyanate equivalent of the polyiso(thio)cyanate compound is 300 to 5000. However, it is believed that the effects are more pronounced when the urethane prepolymer (B12) is used alone.

[0063] (B12) Method for producing urethane prepolymer The method for producing the urethane prepolymer (B12) used in the present invention involves reacting a bifunctional active hydrogen-containing compound (B32) having two active hydrogen-containing groups in the molecule, such as a hydroxyl group, an amino group, or a thiol group, with a bifunctional polyiso(thio)cyanate compound (B13) to produce a urethane prepolymer (B12) having iso(thio)cyanate groups at both ends of the molecule. There are no limitations as long as a prepolymer having iso(thio)cyanate groups at both ends can be obtained. As mentioned above, the preferred blending amounts of the (B32) bifunctional active hydrogen-containing compound and (B13) bifunctional polyiso(thio)cyanate compound to obtain the (B12) urethane prepolymer are as follows: Specifically, it is preferred to produce the (B13) bifunctional polyiso(thio)cyanate compound in such a manner that the number of moles (n5) of iso(thio)cyanate groups in the (B13) bifunctional polyiso(thio)cyanate compound and the number of moles (n6) of active hydrogen in the (B32) bifunctional active hydrogen-containing compound satisfy the relationship 1<(n5) / (n6)≦2.3.

[0064] In addition, in the reaction for producing the urethane prepolymer (B12), heating or adding a urethane catalyst may be carried out as necessary. The most preferred examples of the component (B1) used in the present invention are, from the viewpoint of controlling the strength and reactivity of the resin formed, alicyclic isocyanates such as isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane-4,4'-diisocyanate, and (bicyclo[2.2.1]heptane-2,5(2,6)-diyl)bismethylene diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate. Examples of suitable isocyanates include aromatic isocyanates such as 4,4'-diphenylmethane diisocyanate and xylylene diisocyanate (o-, m-, p-), polyfunctional isocyanates with a biuret structure, uretdione structure, or isocyanurate structure, which are primarily made from diisocyanates such as hexamethylene diisocyanate and tolylene diisocyanate, polyfunctional isocyanates as adducts with tri- or higher functional polyols, and (B12) urethane prepolymers.

[0065] When the present invention is used for polishing pad applications, the preferred component (B1) is a urethane prepolymer (B12). The use of the urethane prepolymer (B12) makes it possible to obtain desirable resin properties. Particularly preferred is a urethane prepolymer (B12) made from an aromatic isocyanate, and most preferred is a urethane prepolymer made from 2,4-tolylene diisocyanate or 2,6-tolylene diisocyanate.

[0066] <(B2) Epoxy Group-Containing Monomer; Component (B2)> The epoxy group-containing monomer has an epoxy group in the molecule as a polymerizable group, and is particularly suitable when a hydroxyl group, an amino group, or an iso(thio)cyanate group is introduced as the polymerizable functional group of the (A) cyclic monomer. Such epoxy compounds are broadly classified into aliphatic epoxy compounds, alicyclic epoxy compounds, and aromatic epoxy compounds, and preferred specific examples thereof include those described in WO 2015 / 068798.

[0067] <(B3) (Thiol Compound; (B3) Component> The (thiol) compound is a compound having two or more groups selected from the group consisting of hydroxyl groups and thiol groups in one molecule. Of course, compounds having both hydroxyl and thiol groups are also selected. The (thiol) compounds can be broadly classified into aliphatic alcohols, alicyclic alcohols, aromatic alcohols, polyester polyols, polyether polyols, polycaprolactone polyols, polycarbonate polyols, polyacrylic polyols, castor oil-based polyols, thiols, and hydroxyl group / thiol group-type polymerizable group-containing compounds. Specific examples include the following:

[0068] Fatty alcohol; component (B3) Bifunctional polyols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 1,5-dihydroxypentane, 1,6-dihydroxyhexane, 1,7-dihydroxyheptane, 1,8-dihydroxyoctane, 1,9-dihydroxynonane, 1,10-dihydroxydecane, 1,11-dihydroxyundecane, 1,12-dihydroxydodecane, neopentyl glycol, glyceryl monooleate, monoelaidin, polyethylene glycol, 3-methyl-1,5-dihydroxypentane, dihydroxyneopentyl, 2-ethyl-1,2-dihydroxyhexane, and 2-methyl-1,3-dihydroxypropane (corresponding to the bifunctional active hydrogen-containing compound (B32) constituting the urethane prepolymer (B12)). Polyfunctional polyols such as glycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, trimethylolpropane tripolyoxyethylene ether (for example, TMP-30, TMP-60, TMP-90, etc., manufactured by Nippon Nyukazai Co., Ltd.), butanetriol, 1,2-methylglucoside, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, erythritol, threitol, ribitol, arabinitol, xylitol, allitol, mannitol, dolcitol, iditol, glycol, inositol, hexanetriol, triglycerol, diglycerol, and triethylene glycol.

[0069] Alicyclic alcohol; component (B3) Hydrogenated bisphenol A, cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, tricyclo[5,2,1,0 2,6 ]decane-dimethanol, bicyclo[4,3,0]-nonanediol, dicyclohexanediol, tricyclo[5,3,1,13,9]dodecanediol, bicyclo[4,3,0]nonanedimethanol, tricyclo[5,3,1,1 3,9]dodecane-diethanol, hydroxypropyltricyclo〔5,3,1,1 3,9 ] dodecanol, spiro[3,4]octanediol, butylcyclohexanediol, 1,1'-bicyclohexylidenediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, and o-dihydroxyxylylene (corresponding to the (B32) difunctional active hydrogen-containing compound constituting the (B12) urethane prepolymer). Polyfunctional polyols such as tris(2-hydroxyethyl) isocyanurate, cyclohexanetriol, sucrose, maltitol, and lactitol.

[0070] Aromatic alcohol; component (B3) Dihydroxynaphthalene, dihydroxybenzene, bisphenol A, bisphenol F, xylylene glycol, tetrabromobisphenol A, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)-1-naphthylmethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2-(4-hydroxyphenyl) 2,2-bis(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)-3-methylbutane, 2,2-bis(4-hydroxyphenyl)pentane, 3,3-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)hexane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 2,2-bis(4-hydroxyphenyl)hexane butane, 4,4-bis(4-hydroxyphenyl)heptane, 2,2-bis(4-hydroxyphenyl)tridecane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3-ethyl-4-hydroxyphenyl)propane, 2,2-bis(3-n-propyl-4-hydroxyphenyl)propane, 2,2-bis(3-isopropyl-4-hydroxyphenyl)propane, 2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane, 2,2-bis(3- tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2-bis(3-allyl-4'-hydroxyphenyl)propane, 2,2-bis(3-methoxy-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(2,3,5,6-tetramethyl-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)cyanomethane, 1-cyano-3,3-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cycloheptane, 1,1-bis(3-methyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dichloro-4-hydroxyphenyl)cyclohexane, 1,1-bis(3-methyl-4-hydroxyphenyl)-4-methylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)norbornane, 2,2-bis(4-hydroxyphenyl)adamantane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, ethylene glycol bis(4-hydroxyphenyl) ether, 4,4'- Dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide, 3,3'-dicyclohexyl-4,4'-dihydroxydiphenyl sulfide, 3,3'-diphenyl-4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, bis(4-hydroxyphenyl) ketone, bis(4-hydroxy-3-methylphenyl) ketone, 7,7' -Dihydroxy-3,3',4,4'-tetrahydro-4,4,4',4'-tetramethyl-2,2'-spirobi(2H-1-benzopyran), trans-2,3-bis(4-hydroxyphenyl)-2-butene, 9,9-bis(4-hydroxyphenyl)fluorene, 3,3-bis(4-hydroxyphenyl)-2-butanone, 1,6-bis(4-hydroxyphenyl)-1,6-hexanedione, 4,4'-dihydroxybiphenyl, m-dihydroxyxylylene, p-dihydroxyxylylene, 1,4-bis(2-hydroxyethyl)benzene, 1,4-bis(3-hydroxypropyl)benzene, 1,4-bis(4-hydroxybutyl)benzene, 1,4-bis(5-hydroxypentyl)benzene, 1,4-bis(6-hydroxyhexyl)benzene, 2,2-bis[4-(2'-hydroxyethyloxy)phenyl]propane, and bifunctional polyols such as hydroquinone and resorcinol (corresponding to the bifunctional active hydrogen-containing compound (B32) constituting the urethane prepolymer (B12)). Polyfunctional polyols such as trihydroxynaphthalene, tetrahydroxynaphthalene, benzenetriol, biphenyltetraol, pyrogallol, (hydroxynaphthyl)pyrogallol, and trihydroxyphenanthrene.

[0071] Polyester polyol; component (B3) Examples include compounds obtained by a condensation reaction between a polyol and a polybasic acid. Among these, the number average molecular weight is preferably 400 to 2000, more preferably 500 to 1500, and most preferably 600 to 1200. Compounds having hydroxyl groups only at both ends of the molecule (two hydroxyl groups per molecule) correspond to the bifunctional active hydrogen-containing compound (B32) that constitutes the urethane prepolymer (B12). Examples of the polyol include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 3,3'-dimethylolheptane, 1,4-cyclohexanedimethanol, neopentyl glycol, 3,3-bis(hydroxymethyl)heptane, diethylene glycol, dipropylene glycol, glycerin, and trimethylolpropane. These may be used alone or in combination. Examples of the polybasic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid, orthophthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. These may be used alone or in combination. These polyester polyols are available as reagents or industrially, and examples of commercially available products include the "Polylite (registered trademark)" series manufactured by DIC Corporation, the "Nippolan (registered trademark)" series manufactured by Nippon Polyurethane Industry Co., Ltd., the "Maximol (registered trademark)" series manufactured by Kawasaki Chemical Industries, Ltd., and the "Kuraray Polyol (registered trademark)" series manufactured by Kuraray Co., Ltd.

[0072] Polyether polyol; component (B3) Examples include compounds obtained by ring-opening polymerization of alkylene oxides, or compounds obtained by reacting a compound having two or more active hydrogen-containing groups in the molecule with an alkylene oxide, and modified compounds thereof. Among these, the number average molecular weight is preferably 400 to 2,000, more preferably 500 to 1,500, and most preferably 600 to 1,200. Compounds having hydroxyl groups only at both ends of the molecule (two in the molecule) correspond to the bifunctional active hydrogen-containing compound (B32) that constitutes the urethane prepolymer (B12). Examples of the polyether polyols include polymer polyols, urethane-modified polyether polyols, and polyether ester copolymer polyols. Examples of the compounds having two or more active hydrogen-containing groups in the molecule include polyol compounds such as water, ethylene glycol, propylene glycol, butanediol, glycerin, trimethylolpropane, hexanetriol, triethanolamine, diglycerin, pentaerythritol, glycols having one or more hydroxyl groups in the molecule, such as trimethylolpropane and hexanetriol, and glycerin. These compounds may be used alone or in combination of two or more. Examples of the alkylene oxide include cyclic ether compounds such as ethylene oxide, propylene oxide, and tetrahydrofuran, and these may be used alone or in combination of two or more. Such polyether polyols are available as reagents or industrially, and examples of commercially available polyether polyols include the "EXCENOL (registered trademark)" series and "EMALSTAR (registered trademark)" manufactured by Asahi Glass Co., Ltd., and the "ADEKA POLYETHER" series manufactured by ADEKA Corporation.

[0073] Polycaprolactone polyol; component (B3) Examples include compounds obtained by ring-opening polymerization of ε-caprolactone. Among these, the number average molecular weight is preferably 400 to 2000, more preferably 500 to 1500, and most preferably 600 to 1200. Compounds having hydroxyl groups only at both ends of the molecule (two hydroxyl groups in the molecule) correspond to the bifunctional active hydrogen-containing compound (B32) that constitutes the urethane prepolymer (B12). These polycaprolactone polyols are available as reagents or industrially, and examples of commercially available products include the "Placcel (registered trademark)" series manufactured by Daicel Chemical Industries, Ltd.

[0074] Polycarbonate polyol; component (B3) Examples include compounds obtained by phosgenating one or more low-molecular-weight polyols, and compounds obtained by transesterification with ethylene carbonate, diethyl carbonate, diphenyl carbonate, etc. Among these, the number-average molecular weight is preferably 400 to 2000, more preferably 500 to 1500, and most preferably 600 to 1200. Compounds having hydroxyl groups only at both ends of the molecule (two hydroxyl groups per molecule) correspond to the bifunctional active hydrogen-containing compound (B32) that constitutes the urethane prepolymer (B12). Examples of the low molecular weight polyol include low molecular weight polyols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 3-methyl-1,5-pentanediol, 2-ethyl-4-butyl-1,3-propanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, diol dimer acid, ethylene oxide and propylene oxide adducts of bisphenol A, bis(β-hydroxyethyl)benzene, xylylene glycol, glycerin, trimethylolpropane, and pentaerythritol.

[0075] Polyacrylic polyol; component (B3) Examples include polyol compounds obtained by polymerizing (meth)acrylate esters or vinyl monomers. Compounds having hydroxyl groups only at both ends of the molecule (two hydroxyl groups in the molecule) correspond to the bifunctional active hydrogen-containing compound (B32) that constitutes the urethane prepolymer (B12).

[0076] Castor oil-based polyol; component (B3) Examples of castor oil-based polyols include polyol compounds made from castor oil, a natural fat and oil, as a starting material. Those having hydroxyl groups only at both ends of the molecule (two hydroxyl groups per molecule) correspond to the component (B32) constituting the urethane prepolymer (B12). These castor oil polyols are available as reagents or industrially, and examples of commercially available products include the "URIC (registered trademark)" series manufactured by Ito Oil Mills, Ltd.

[0077] Thiol; component (B3) As specific examples of suitable thiols, those described in WO 2015 / 068798 can be used. Among them, particularly suitable examples include the following: Tetraethylene glycol bis(3-mercaptopropionate), 1,4-butanediol bis(3-mercaptopropionate), 1,6-hexanediol bis(3-mercaptopropionate), 1,4-bis(mercaptopropylthiomethyl)benzene (corresponding to the (B32) bifunctional active hydrogen-containing compound constituting the (B12) urethane prepolymer). Trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), 1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane, 2,2-bis(mercaptomethyl)-1,4-butanedithiol, 2,5-bis(mercaptomethyl)-1,4-dithiane, 4- Thiols such as mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 1,1,1,1-tetrakis(mercaptomethyl)methane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, and tris-{(3-mercaptopropionyloxy)ethyl}-isocyanurate.

[0078] Hydroxyl group / thiol group type polymerizable group-containing compound; component (B3) 2-mercaptoethanol, 1-hydroxy-4-mercaptocyclohexane, 2-mercaptohydroquinone, 4-mercaptophenol, 1-hydroxyethylthio-3-mercaptoethylthiobenzene, 4-hydroxy-4'-mercaptodiphenyl sulfone, 2-(2-mercaptoethylthio)ethanol, dihydroxyethyl sulfide mono(3-mercaptopropionate), dimercaptoethane mono(saltylate) (corresponding to the (B32) bifunctional active hydrogen-containing compound constituting the (B12) urethane prepolymer). Poly(thio)ols such as 3-mercapto-1,2-propanediol, glycerin di(mercaptoacetate), 2,4-dimercaptophenol, 1,3-dimercapto-2-propanol, 2,3-dimercapto-1-propanol, 1,2-dimercapto-1,3-butanediol, pentaerythritol tris(3-mercaptopropionate), pentaerythritol mono(3-mercaptopropionate), pentaerythritol bis(3-mercaptopropionate), pentaerythritol tris(thioglycolate), pentaerythritol pentakis(3-mercaptopropionate), hydroxymethyl-tris(mercaptoethylthiomethyl)methane, and hydroxyethylthiomethyl-tris(mercaptoethylthio)methane.

[0079] <(B4) Amino Group-Containing Monomer; Component (B4)> (B4) Amino group-containing monomers are monomers having two or more primary or secondary amino groups in one molecule, and are broadly classified into aliphatic amines, alicyclic amines, and aromatic amines, and specific examples thereof include the following:

[0080] Aliphatic amine; component (B4) Polyamines such as ethylenediamine, hexamethylenediamine, nonamethylenediamine, undecanemethylenediamine, dodecamethylenediamine, metaxylenediamine, 1,3-propanediamine, putrescine, and diethylenetriamine. Monofunctional amines such as monoethylamine, n-propylamine, diethylamine, di-n-propylamine, n-propylamine, di-n-butylamine, and n-butylamine.

[0081] Alicyclic amine; component (B4) Polyamines such as isophoronediamine and cyclohexyldiamine. Monofunctional amines such as cyclohexylamine and N-methylcyclohexylamine.

[0082] Aromatic amine; component (B4) 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-diethylthio Benzene-2,6-diamine, trimethylene glycol-di-p-aminobenzoate, polytetramethylene glycol-di-p-aminobenzoate, 4,4'-diamino-3,3',5,5'-tetraethyldiphenylmethane, 4,4'-diamino-3,3'-diisopropyl-5,5'-dimethyldiphenylmethane, 4,4'-diamino-3,3',5,5'-tetraisopropyldiphenylmethane, 1,2-bis(2- 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 Polyamines such as '-methylenebis(methyl-6-aminobenzoate), 2-methylpropyl 2,4-diamino-4-chlorobenzoate, isopropyl 2,4-diamino-4-chlorobenzoate, isopropyl 2,4-diamino-4-chlorophenylacetate, di-(2-aminophenyl)thioethyl terephthalate, diphenylmethanediamine, tolylenediamine, piperazine, 1,3,5-benzenetriamine, and melamine. Monofunctional amines such as benzylamine and dibenzylamine. Among these components (B4), the diamine compounds can also be considered as bifunctional active hydrogen-containing compounds (B32) having two active hydrogen-containing groups in the molecule.

[0083] In the curable composition of the present invention, the contents of components (A) and (B) are not particularly limited, but it is preferable that the content of component (A) is 5 to 45 parts by mass and the content of component (B) is 55 to 95 parts by mass per 100 parts by mass of the total of components (A) and (B).More preferably, the content of component (A) is 10 to 20 parts by mass and the content of component (B) is 80 to 90 parts by mass per 100 parts by mass of the total of components (A) and (B).

[0084] <Polymerization method / Suitable blend ratio of polymerizable monomers for step-growth addition polymerization> A polymerizable monomer containing components (B1), (B2), (B3), and (B4). In the present invention, in the case of a curable composition containing components (B1), (B2), (B3), and (B4), the following blending ratio is preferred. That is, when the polymerizable functional group in the cyclic monomer (A) is not a radically polymerizable group and a cured product is produced by curing via step-growth addition (polycondensation / polyaddition) polymerization, the blending ratios are preferably as follows. Note that when the polymerizable functional group in component (A) is an active hydrogen-containing group, component (B1) is essential.

[0085] Specifically, it is preferable to contain 3 to 50 parts by weight of component (A) and 50 to 97 parts by weight of component (B) relative to 100 parts by weight of the total of component (B1) (including components (B12) and (B13), if used), component (B2), component (B3), and component (B4) (hereinafter sometimes simply referred to as "amount of component (B)") and component (A). By containing component (A) in this proportion, the resulting cured product, in the case of a polishing pad, can exhibit excellent polishing properties and mechanical properties. To achieve these effects, it is more preferable to contain component (A) in the range of 5 to 45 parts by weight and component (B) in the range of 55 to 95 parts by weight.

[0086] Furthermore, when the amount of component (B) is taken as 100% by mass, it is preferable to have 0 to 100% by mass of component (B1), 0 to 100% by mass of component (B2), 0 to 80% by mass of component (B3), and 0 to 30% by mass of component (B4) in order to exhibit excellent mechanical properties. To further demonstrate this effect, it is more preferable to have 20 to 95% by mass of component (B1), 0 to 20% by mass of component (B2), 0 to 70% by mass of component (B3), and 0 to 25% by mass of component (B4), and most preferably to have 40 to 95% by mass of component (B1), 0 to 5% by mass of component (B2), 0 to 35% by mass of component (B3), and 0 to 20% by mass of component (B4). It is preferable that the ratio of the number of moles of all polymerizable functional groups reactive with iso(thio)cyanate groups contained in components (A), (B2), (B3), and (B4) to the number of moles of all iso(thio)cyanate groups in component (B1) satisfies 1:0.8-1.2.

[0087] <Polymerization method / polymerizable monomer for chain (radical) polymerization> <(B5) Radical Polymerizable Monomer> In the present invention, the radical polymerizable monomer (B5) (hereinafter sometimes simply referred to as component (B5)) is not particularly limited as long as it has a radical polymerizable group. In this case, the polymerizable functional group contained in the cyclic monomer (A) is a radical polymerizable group. The polymerizable monomer (B) contains at least component (B5). The (B5) radical polymerizable monomers can be broadly classified into (meth)acrylate compounds having a (meth)acrylate group, vinyl compounds having a vinyl group, and allyl compounds having an allyl group. As specific examples of suitable radical polymerizable monomers (B5), those described in WO 2015 / 068798 can be used.

[0088] <Regarding suitable curable compositions> The (A) cyclic monomer and (B) polymerizable monomer may be selected appropriately depending on the intended use. When used in a polishing pad material, the polymerizable functional group of the (A) cyclic monomer is preferably selected from a hydroxyl group, a thiol group, and an amino group, and the (B) polymerizable monomer preferably contains an (B1) iso(thio)cyanate compound. In particular, when used in a polishing pad material, it is preferable that the (B1) poly(iso)thiocyanate compound contains a (B12) urethane prepolymer. This improves the mechanical properties of the polishing pad material, and particularly favorable wear resistance can be achieved.

[0089] The curable composition of the present invention may contain a polyrotaxane monomer, but from the viewpoint of improving handleability, it is preferable to use a small amount of the polyrotaxane monomer. The content of the polyrotaxane monomer in the curable composition is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 0% by mass.

[0090] (Other ingredients to be added to the curable composition) In the curable composition of the present invention, various polymerization curing accelerators (C) can also be used to rapidly accelerate the curing depending on the type of the polymerizable functional group introduced into the above-mentioned (A) cyclic monomer or (B) polymerizable monomer.

[0091] (C) Polymerization hardening accelerator For example, when the polymerizable functional group possessed by the (A) cyclic monomer is a polymerizable group such as a hydroxyl group, an amino group, an epoxy group, or a thiol group, and the (B) component contains an (B1) iso(thio)cyanate compound, the (C1) urethane or urea reaction catalyst or the (C2) condensing agent is used as a polymerization and curing accelerator. When the polymerizable functional group possessed by the (A) cyclic monomer is a polymerizable functional group such as a hydroxyl group or an amino group, and when the (B) component contains the (B2) epoxy group-containing monomer, the (C3) epoxy curing agent or the (C4) cationic polymerization catalyst for ring-opening polymerization of the epoxy group is used as a polymerization curing accelerator. When the polymerizable functional group possessed by the cyclic monomer (A) is a radical polymerizable group and the component (B) contains a radical polymerizable monomer (B5), a radical polymerization initiator (C5) is used as a polymerization curing accelerator. Specific examples of the polymerization accelerators (C1) to (C5) that can be suitably used in the present invention include those described in WO 2015 / 068798. These various (C) polymerization curing accelerators can be used either alone or in combination of two or more. The amount used may be a so-called catalytic amount, for example, a small amount ranging from 0.001 to 10 parts by mass, particularly 0.01 to 5 parts by mass, per 100 parts by mass of the total of the (A) cyclic monomer and the (B) polymerizable monomer.

[0092] The curable composition of the present invention may further contain various known additives as long as they do not impair the effects of the present invention. For example, abrasive grains, antioxidants, ultraviolet absorbers, infrared absorbers, color inhibitors, fluorescent dyes, dyes, photochromic compounds, pigments, fragrances, surfactants, flame retardants, plasticizers, fillers, antistatic agents, foam stabilizers, solvents, leveling agents, and other additives may be added. These additives may be used alone or in combination of two or more. These additives can be incorporated into the curable composition and then polymerized to form a cured product. Specific examples of the abrasive grains include particles made of a material selected from cerium oxide, silicon oxide, alumina, silicon carbide, zirconia, iron oxide, manganese dioxide, titanium oxide, and diamond, or particles made of two or more of these materials. The polymerization method can be a known method. In the case of sequential addition (polycondensation, polyaddition) polymerization, the conditions described in WO 2015 / 068798, WO 2016 / 143910, and JP 2017-48305 can be used. In the case of chain (radical) polymerization, the conditions described in WO 2014 / 136804 and WO 2015 / 068798 can be used.

[0093] Furthermore, the cured product obtained by curing the curable composition of the present invention may be foamed by providing pores in the cured product depending on the intended use. A known example of such an application is a polishing pad. To provide pores in the cured product to form a foam for use in a polishing pad or the like, any known method can be used without any limitations. Examples of such methods include a method of dispersing and hardening a volatile blowing agent such as a low-boiling hydrocarbon or hollow microparticles (microballoons), a method of mixing thermally expandable microparticles and then heating to foam the microparticles, and a mechanical froth foaming method in which an inert gas such as air or nitrogen is blown into the mixture during mixing. When a curable composition capable of forming urethane bonds is used in the cured product of the present invention, a foaming agent foaming method in which water or the like is added can also be used. Among these, a method of dispersing and hardening hollow microparticles (microballoons) is preferably used to foam the resulting cured product. The hollow microparticles used in this method are described below.

[0094] (D) Microscopic hollow particles In the present invention, the curable composition containing the component (A) and the component (B) may further contain (D) hollow microparticles (hereinafter sometimes simply referred to as "component (D)"). Any known material can be used as the component (D) without any limitations. Specific examples include particles whose shell is made of vinylidene chloride resin, (meth)acrylate resin, acrylonitrile-vinylidene chloride copolymer, epoxy resin, phenolic resin, melamine resin, urethane resin, etc. Among these, the component (D) is preferably a hollow particle composed of a shell made of at least one resin selected from the group consisting of urethane resin and melamine resin, and a hollow space surrounded by the shell. The urethane resin is a resin containing a urethane bond and / or a urea bond. The melamine resin is a resin produced by polycondensation of melamine and formaldehyde. The use of this component (D) allows for efficient and easy production of uniform foams.

[0095] The average particle size of the component (D) is not particularly limited, but is preferably in the following range: Specifically, it is preferably 1 μm to 500 μm, and more preferably 5 μm to 200 μm. The density of component (D) is not particularly limited, but is preferably in the following range: 0.01 g / cm 3 ~0.5g / cm 3 Preferably, the density is 0.02 g / cm3 to 0.3 g / cm3, and more preferably 0.02 g / cm3 to 0.3 g / cm3. The density mentioned above is the density of component (D) when expanded. In the case of unexpanded hollow particles that expand due to the heat generated when mixed with a curable composition and cured, the density when expanded is preferably the above-mentioned density.

[0096] The amount of component (D) to be blended may be determined appropriately depending on the intended use. In particular, when the resulting cured product is used as a polishing pad, the following blending amount is preferred. Specifically, the amount of component (D) is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, and even more preferably 0.5 to 8 parts by mass per 100 parts by mass of the total of components (A) and (B).

[0097] <Cured product; polishing pad> In the present invention, when the cured composition used is one in which the polymerizable functional group of the (A) cyclic monomer is an active hydrogen-containing group containing active hydrogen, and the (B) polymerizable monomer contains (B1) an iso(thio)cyanate compound having at least an iso(thio)cyanate group in the molecule, a cured urethane resin can be obtained by curing these. The urethane resin, which is a cured product obtained from the curable composition of the present invention, can be used in polishing pads due to its excellent mechanical properties. Furthermore, the urethane resin can have any appropriate hardness. The hardness can be measured according to the Shore method, for example, JIS Standard (Hardness Test) K6253. The urethane resin preferably has a Shore hardness of 20A to 90D. The Shore hardness of the urethane resin used in the present invention and in general polishing pads is preferably 30A to 70D, more preferably 40A to 50D ("A" indicates hardness on the Shore "A" scale, and "D" indicates hardness on the Shore "D" scale). The hardness can be adjusted to any desired value by changing the formulation and blending amounts as needed. Furthermore, it is preferable that the urethane resin has a compressibility within a certain range in order to achieve flatness of the object to be polished. The compressibility can be measured, for example, by a method conforming to JIS L 1096. The compressibility of the urethane resin is preferably 0.5% to 50%. By keeping the compressibility within the above range, it is possible to achieve excellent flatness of the object to be polished.

[0098] Furthermore, because the urethane resin has low hysteresis loss or excellent elastic recovery, when used as a polishing pad, it can achieve flatness of the object to be polished and a high removal rate. Hysteresis loss can be measured, for example, by a method conforming to JIS K 6251. Specifically, a dumbbell-shaped test piece is stretched 100% and then returned to its original state, and the hysteresis loss (area of ​​elongation and stress when stretched and returned to its original state / area of ​​elongation and stress when stretched x 100) can be measured.

[0099] Although not particularly limited, the hysteresis loss of the resulting urethane resin is preferably 60% or less, more preferably 50% or less, and even more preferably 40% or less. It is presumed that a low hysteresis loss allows the kinetic energy of the abrasive grains to be uniformly utilized in polishing the workpiece when used as a polishing pad. This makes it possible to achieve excellent flatness and a high polishing rate. Furthermore, a low hysteresis loss is believed to enable an excellent polishing rate to be achieved even with a soft pad. In the measurement of hysteresis loss described above, the "area of ​​elongation and stress when stretched and restored" is expressed as "area of ​​the stress-strain curve during stretching minus area of ​​the stress-strain curve during contraction," and the "area of ​​elongation and stress when stretched" means "area of ​​the stress-strain curve during stretching." When the cured product obtained from the curable composition of the present invention is used as a polishing pad, the Taber abrasion amount, which is an index of the abrasion resistance of the cured product, is preferably 60 mg or less, more preferably 50 mg or less in the Taber abrasion test. By reducing the Taber abrasion amount, it is possible to exhibit excellent abrasion resistance when used as a polishing pad. The detailed method for carrying out the Taber abrasion test can be the method described in the Examples below.

[0100] Furthermore, a polishing pad using a urethane resin obtained by the present invention may have a polishing layer formed from multiple layers. For example, when the urethane resin is composed of two layers, the polishing layer is composed of a first layer having a polishing surface that contacts the workpiece during polishing, and a second layer that contacts the first layer on a surface opposite to the polishing surface of the first layer. In this case, the second layer can have a different hardness or elastic modulus from the first layer, thereby adjusting the physical properties of the first layer. For example, by changing the hardness of the first layer and the hardness of the second layer, the polishing properties of the workpiece can be adjusted. In particular, it is preferable that both the first and second layers are cured products obtained from the curable composition of the present invention.

[0101] Furthermore, when the resulting urethane resin is used as a polishing pad, it can be configured as follows. Specifically, abrasive grains can be contained therein to form a so-called fixed-abrasive urethane resin. Examples of abrasive grains include particles made of a material selected from cerium oxide, silicon oxide, alumina, silicon carbide, zirconia, iron oxide, manganese dioxide, titanium oxide, and diamond, or particles of two or more types of these materials. The method for retaining these abrasive grains is not particularly limited, but for example, they can be retained inside the urethane resin (cured product) by dispersing them in the curable composition and then curing the curable composition. In the present invention, a polishing pad using the obtained urethane resin (cured product) can have a groove structure formed on its surface, although this is not particularly limited. In particular, when the cured product is used as a polishing pad, the groove structure is preferably shaped to retain and renew the slurry when polishing a workpiece. Specific examples include X (stripe) grooves, XY lattice grooves, concentric grooves, through holes, blind holes, polygonal columns, cylinders, spiral grooves, eccentric circular grooves, radial grooves, and combinations of these grooves.

[0102] The method for producing the groove structure is not particularly limited, and examples thereof include a method of mechanically cutting using a jig such as a tool of a predetermined size, a method of pouring a resin into a mold having a predetermined surface shape and hardening it, a method of pressing a resin with a press plate having a predetermined surface shape, a method of producing the groove structure using photolithography, a method of producing the groove structure using a printing technique, and a method of producing the groove structure using a laser beam such as a carbon dioxide laser. In the present invention, a curable composition capable of forming a urethane resin (cured product) is impregnated into a nonwoven fabric, and then cured to form a nonwoven fabric urethane resin polishing pad. In addition to the above-mentioned polishing pads, the cured product obtained by curing the curable composition of the present invention can also be used as a buffer material, a vibration-damping material, a sound-absorbing material, etc. Furthermore, by applying or impregnating a nonwoven fabric with the cured composition of the present invention and then curing it, it is possible to apply it to the above-mentioned nonwoven fabric polishing pads, buffer materials, vibration-damping materials, and sound-absorbing materials. [Example]

[0103] Next, the present invention will be described in detail using examples and comparative examples, but the present invention is not limited to these examples. First, the measuring devices used in the present invention and the manufacturing methods of each component will be described.

[0104] (Molecular weight measurement: gel permeation chromatography (GPC measurement)) GPC measurements were performed using a liquid chromatograph (manufactured by Nihon Waters). The columns used were Shodex GPC KF-802 (exclusion limit: 5000), KF802.5 (exclusion limit: 20000), KF-803 (exclusion limit: 70000), KF-804 (exclusion limit: 400000), and KF-805 (exclusion limit: 2000000) manufactured by Showa Denko K.K., depending on the molecular weight of the sample being analyzed. Dimethylformamide (DMF) was used as the developing solution, and measurements were performed at a flow rate of 1 ml / min and a temperature of 40°C. Polystyrene was used as a standard sample, and the weight-average molecular weight was determined by comparative conversion. A differential refractometer was used as the detector.

[0105] [Each ingredient] Component (A-1): Cyclic Monomer A-1: ​​Cyclic monomer having a side chain on a cyclic molecule, and having a hydroxyl group as a polymerizable functional group and a sulfonic acid group as an ionic functional group at the end of the side chain ·Weight average molecular weight Mw (GPC): 6138 ·Dispersion degree (GPC): 1.10 Side chain modification degree: 0.43 (43% when expressed as a percentage) Side chain molecular weight: Number average molecular weight approx. 580 Polymerizable functional group content (polymerizable functional groups introduced into side chains): 1.10 mmol / g Ionic functional group (sulfonic acid group) content: 0.35 mmol / g Content of unreactive hydroxyl groups with no side chains introduced: 1.88 mmol / g Total polymerizable active group content: 2.97mmol / g (a) Molar ratio of ionic functional groups to the total number of moles of polymerizable functional groups and ionic functional groups introduced into the side chains: 22 mol% (b) Molar ratio of ionic functional groups to the total number of moles of all polymerizable functional groups and ionic functional groups: 10.5 mol%

[0106] Component (A-2): Cyclic Monomer A-2: Cyclic monomer having a side chain on a cyclic molecule, and having a hydroxyl group as a polymerizable functional group and a sulfonic acid group as an ionic functional group at the end of the side chain ·Weight average molecular weight Mw (GPC): 6738 ·Dispersion degree (GPC): 1.13 Side chain modification degree: 0.43 (43% when expressed as a percentage) Side chain molecular weight: Number average molecular weight approx. 660 Polymerizable functional group content (polymerizable functional groups introduced into side chains): 0.14 mmol / g Ionic functional group (sulfonic acid group) content: 1.13 mmol / g Content of unreactive hydroxyl groups with no side chains introduced: 1.70mmol / g Total polymerizable active group content: 1.84mmol / g (a) Molar ratio of ionic functional groups to the total number of moles of polymerizable functional groups and ionic functional groups introduced into the side chains: 88 mol% (b) Molar ratio of ionic functional groups to the total number of moles of all polymerizable functional groups and ionic functional groups: 42.0 mol%

[0107] Component (A-3): Cyclic Monomer A-3: Cyclic monomer having a side chain on a cyclic molecule, and having a hydroxyl group as a polymerizable functional group and a carboxyl group as an ionic functional group at the end of the side chain ·Weight average molecular weight Mw (GPC): 6029 ·Dispersion degree (GPC): 1.11 Side chain modification degree: 0.43 (43% when expressed as a percentage) Side chain molecular weight: Number average molecular weight approx. 570 Polymerizable functional group content (polymerizable functional groups introduced into side chains): 1.11 mmol / g Ionic functional group (carboxyl group) content: 0.35 mmol / g Content of unreactive hydroxyl groups with no side chains introduced: 1.90mmol / g Total polymerizable active group content: 3.02mmol / g (a) Molar ratio of ionic functional groups to the total number of moles of polymerizable functional groups and ionic functional groups introduced into the side chains: 22 mol% (b) Molar ratio of ionic functional groups to the total number of moles of all polymerizable functional groups and ionic functional groups: 10.5 mol%

[0108] Component (A-4): Cyclic Monomer A-4: A cyclic monomer having a side chain on a cyclic molecule, and having a hydroxyl group as a polymerizable functional group and a phosphate ion as an ionic functional group at the end of the side chain. ·Weight average molecular weight Mw (GPC): 5945 ·Dispersion degree (GPC): 1.10 Side chain modification degree: 0.43 (43% when expressed as a percentage) Side chain molecular weight: Number average molecular weight approx. 570 Polymerizable functional group content (polymerizable functional groups introduced into side chains): 1.13 mmol / g Ionic functional group (carboxyl group) content: 0.35 mmol / g Content of unreactive hydroxyl groups with no side chains introduced: 1.93 mmol / g Total polymerizable active group content: 3.06mmol / g (a) Molar ratio of ionic functional groups to the total number of moles of polymerizable functional groups and ionic functional groups introduced into the side chains: 22 mol% (b) Molar ratio of ionic functional groups to the total number of moles of all polymerizable functional groups and ionic functional groups: 10.5 mol% The method for producing the cyclic monomer A will be described below.

[0109] <Method for preparing cyclic monomer A-1> 100.0 g of hydroxypropylated β-cyclodextrin (CycloChem Co., Ltd.) and 304.2 g of ε-caprolactone were stirred at 130°C to form a homogeneous solution, which was then stirred at 130°C for 5 hours while reducing the pressure to 20 kPa. 0.41 g of tin(II) 2-ethylhexanoate was then added under a dry nitrogen atmosphere and reacted for 16 hours to obtain β-cyclodextrin containing polycaprolactone side chains with hydroxyl groups at the ends (cyclodextrin with terminal hydroxyl groups at the side chains (pre-A)). The physical properties of the obtained product were as follows: ·Weight average molecular weight Mw (GPC): 4700 ·Dispersion degree (GPC): 1.06 Side chain modification degree: 0.43 (43% when expressed as a percentage) Side chain molecular weight: Number average molecular weight 550 ·Viscosity: 3800mPa·s 20 g of the hydroxyl-terminated side chain cyclodextrin was dissolved in 40 mL of dehydrated THF, and then 0.35 g of sodium hydride was added and the mixture was stirred for 2 hours at room temperature under a nitrogen atmosphere. During this time, the hydroxyl groups of the cyclic molecules reacted with the sodium hydride, generating hydrogen. After the hydrogen generation was completely stopped, 0.89 g of 1,3-propane sultone was added and the mixture was stirred for 24 hours at room temperature. 100 mL of saturated aqueous ammonium chloride solution was then added to the reaction solution to stop the reaction, followed by extraction with ethyl acetate. The solvent was distilled off from the resulting organic phase, and the resulting organic phase was dried to obtain sulfonic acid group-containing cyclic monomer A-1. The amount of sulfonic acid group introduced was 1 The physical properties of the cyclic monomer A-1 were confirmed using a H-NMR measuring device (JNM-LA500 manufactured by JEOL Ltd.). The polymerizable functional group (hydroxyl group) content was calculated from the hydroxyl group value.

[0110] <Method for preparing cyclic monomer A-2> Cyclic Monomer A-2 was obtained in the same manner as Cyclic Monomer A-1, except that 1.28 g of sodium hydroxide and 3.25 g of 1,3-propane sultone were used.

[0111] <Method for Preparing Cyclic Monomer A-3> Cyclic monomer A-3 was obtained in the same manner as cyclic monomer A-1, except that 0.73 g of triethylamine and 0.73 g of succinic anhydride were used instead of sodium hydroxide and 1,3-propanesultone.

[0112] <Method for Preparing Cyclic Monomer A-4> Cyclic monomer A-4 was obtained in the same manner as cyclic monomer A-1, except that 1.64 g of tributylamine and 0.64 g of phosphoric acid were used instead of sodium hydroxide and 1,3-propanesultone. Other materials used are as follows.

[0113] (B) Component: Polymerizable monomer (B12) Component: Urethane prepolymer Pre-1: Terminal isocyanate urethane prepolymer with an isothiocyanate equivalent of 905 <Method for Producing Pre-1> In a flask equipped with a nitrogen introduction tube, thermometer, and stirrer, 50 g of 2,4-tolylene diisocyanate, 90 g of polyoxytetramethylene glycol (number average molecular weight; 1000), and 12 g of diethylene glycol were reacted at 80 °C for 6 hours under a nitrogen atmosphere to obtain a terminal isocyanate urethane prepolymer Pre-1 with an isothiocyanate equivalent of 905.

[0114] (B3) Component (Thio)ol compound RX-1: Ionic functional group-containing polyrotaxane monomer RX-1 was produced by the method described in Patent Document 3. The physical properties of this RX-1 were as follows. · Polyrotaxane weight average molecular weight Mw (GPC): 203000 · Degree of modification of the side chain: 0.5 (50% when expressed as a percentage) · Molecular weight of the side chain: Approximately 360 on average · Content of polymerizable functional groups (polymerizable functional groups introduced into the side chain): 1.37 mmol / g Ionic functional group (carboxyl group) content: 0.35 mmol / g Content of unreactive hydroxyl groups with no side chains introduced: 1.52 mmol / g Total polymerizable active group content: 2.89mmol / g (a) Molar ratio of ionic functional groups to the total number of moles of polymerizable functional groups and ionic functional groups introduced into side chains: 9.9 mol%. (b) Molar ratio of ionic functional groups to the total number of moles of all polymerizable functional groups and ionic functional groups: 4.9 mol %.

[0115] Component (B4) Amino group-containing monomer MOCA: 4,4'-methylenebis(o-chloroaniline).

[0116] (Other ingredients) (D) Component Micro hollow particles Hollow particle 1: Hollow microcapsule 920-40 (manufactured by Nippon Phillite Co., Ltd.)

[0117] Example 1 First, a curable composition was prepared using cyclic monomer A, which is component (A), as follows. 13.6 parts by mass of component (A-1) and 5.4 parts by mass of component (B4) MOCA were mixed at 120°C to form a homogeneous solution, which was then thoroughly degassed to obtain solution 1. Solution 1 was added to 81.0 parts by mass of component (B12) Pre-1 that had been heated to 70°C, and the mixture was mixed homogeneously using a planetary centrifugal mixer to obtain a curable composition. The curable composition was then poured into a mold and cured at 100°C for 15 hours to obtain a cured product having a thickness of 2 mm. The water absorption of the cured product obtained above was 3.3%. The evaluation method is as follows.

[0118] [Evaluation items] (1) Measurement of water absorption: The hardened specimen was thoroughly dried under reduced pressure at 100°C until it reached a constant weight. Then, it was immersed in distilled water at 25°C for 24 hours. The water absorption (%) was calculated from the weight of the sample before and after immersion using the following formula. Water absorption rate (%) = [(weight after immersion - weight before immersion) / weight before immersion] x 100. (2) Abrasion resistance (Taber abrasion amount): The Taber abrasion amount was measured using a 5130 model device manufactured by Taber Co., Ltd. The measurement was carried out under the following conditions: load 1 kg, rotation speed 60 rpm, number of rotations 1000, and abrasion wheel H-18.

[0119] Example 2 A cured product was prepared in the same manner as in Example 1, except that 20.3 parts by mass of component (A-2), 5.0 parts by mass of component (B4) MOCA, and 74.0 parts by mass of component (B12) Pre-1 were used, and then evaluated.

[0120] Example 3 A cured product was prepared in the same manner as in Example 1, except that 13.4 parts by mass of component (A-3), 5.4 parts by mass of component (B4) MOCA, and 81.2 parts by mass of component (B12) Pre-1 were used, and then evaluated.

[0121] Example 4 A cured product was prepared in the same manner as in Example 1, except that 13.2 parts by mass of component (A-4), 5.4 parts by mass of component (B4) MOCA, and 81.4 parts by mass of component (B12) Pre-1 were used, and then evaluated.

[0122] Comparative Examples 1-2 A cured product was prepared and evaluated in the same manner as in Example 1, except that a curable composition having the composition shown in Table 1 was used. The blending ratio of each component and the results are summarized in Table 1. Comparative Example 1 is an example in which an ionic functional group-containing polyrotaxane monomer (RX-1) was used instead of cyclic monomer A, and Comparative Example 2 is an example in which a terminal hydroxyl group-containing side chain cyclodextrin (pre-A) that does not have an ionic functional group was used instead of cyclic monomer A. [Table 1] The results of Examples 1 to 3 show that the cured product obtained by curing the curable composition of the present invention using a cyclic monomer having both a polymerizable functional group and an ionic functional group exhibited excellent water absorption properties while maintaining excellent abrasion resistance. The abrasion resistance (Taber abrasion) of the cured product obtained from the curable composition of Example 3 was slightly worse than that of the other Examples, but was still within an acceptable range. The curable compositions of Examples 1 to 3 were excellent in handleability, but the curable composition of Comparative Example 1 contained a large amount of polyrotaxane monomer and was therefore inferior in handleability. Comparative Example 2 had a lower water absorption rate than the Examples.

[0123] Example 5 First, a curable composition was prepared using cyclic monomer A-1, which is component (A), as follows. 13.6 parts by mass of component (A-1) and 5.4 parts by mass of component (B4) MOCA were mixed at 120°C to form a uniform solution, which was then thoroughly degassed to obtain solution 1. Separately, 81.0 parts by mass of component (B12) Pre-1 was heated to 70°C, and 0.8 parts by mass of hollow particles 1 (other components) was added, followed by stirring with a planetary centrifugal mixer to obtain uniform solution 2. Solution 1 was added to the prepared solution 2 and mixed uniformly to form a curable composition. The curable composition was then poured into a mold and cured at 100°C for 15 hours. After curing, the urethane resin was removed from the mold and sliced ​​to obtain a cured product made of urethane resin with a thickness of 1 mm. A spiral groove was formed on the surface of the cured product, and double-sided tape was attached to the backside to produce a polishing pad with a diameter of 500 mm and a thickness of 1 mm.

[0124] Example 6 A cured body and a polishing pad were prepared and evaluated in the same manner as in Example 5, except that 20.3 parts by mass of component (A-2), 5.0 parts by mass of component (B4) MOCA, and 74.0 parts by mass of component (B12) Pre-1 were used.

[0125] Example 7 A cured body and a polishing pad were prepared and evaluated in the same manner as in Example 5, except that 13.4 parts by mass of component (A-3), 5.4 parts by mass of component (B4) MOCA, and 81.2 parts by mass of component (B12) Pre-1 were used.

[0126] Example 8 A cured body and a polishing pad were prepared and evaluated in the same manner as in Example 5, except that 13.2 parts by mass of component (A-4), 5.4 parts by mass of component (B4) MOCA, and 81.4 parts by mass of component (B12) Pre-1 were used. [Evaluation method] (1) Density: Density (g / cm) measured using a Toyo Seiki (DSG-1) 3 ) was measured. (2) Hardness: Shore D hardness was measured using a durometer manufactured by Kobunshi Keiki Co., Ltd. in accordance with JIS standard (hardness test) K6253. The samples were stacked to a thickness of 6 mm and measured. Relatively low hardness samples were measured using Shore A hardness, and relatively high hardness samples were measured using Shore D hardness. (3) Hysteresis loss: The resin was punched into a No. 8 dumbbell shape with a thickness of 2 mm and stretched 20 mm at 10 mm / min using an autograph of Shimadzu AG-SX. Then, the hysteresis loss was measured when the resin was returned to zero stress. (4) Polishing rate: The polishing rate was measured under the following conditions. The polishing rate is the average value for ten 2-inch sapphire wafers. Slurry: FUJIMI Compol 80 concentrate Pressure: 4 psi Rotation speed: 45 rpm Time: 1 hour (5) Surface roughness (Ra): The surface roughness (Ra) of the surfaces of ten 2-inch sapphire wafers polished under the conditions described in (4) above was measured using a Nano Search Microscope SFT-4500 (Shimadzu Corporation). The surface roughness is the average value of the ten 2-inch sapphire wafers.

[0127] Comparative Examples 3 and 4 Cured products and polishing pads were prepared and evaluated in the same manner as in Example 5, except that the curable compositions shown in Table 2 were used. The blending ratios of each component and the results are summarized in Table 2. Comparative Example 3 is an example in which an ionic functional group-containing polyrotaxane monomer (RX-1) was used instead of cyclic monomer A, and Comparative Example 4 is an example in which a terminal hydroxyl group-containing side chain cyclodextrin (pre-A) that does not have an ionic functional group was used instead of cyclic monomer A.

[0128] From the results of Examples 5 to 8, the cured products obtained by curing the curable compositions using the cyclic monomers having both a polymerizable functional group and an ionic functional group of the present invention exhibited high polishing rates and reduced surface roughness on the polished object. Furthermore, the curable compositions of Examples 5 to 8 were excellent in handleability, while the curable composition of Comparative Example 3 was inferior in handleability. Furthermore, the cured product obtained by curing the curable composition of Comparative Example 4 had a lower polishing rate than the examples.

[0129] [Table 2]

Claims

1. (A) a cyclic monomer having both a polymerizable functional group and an ionic functional group in the molecule; (B) a polymerizable monomer having a polymerizable functional group polymerizable with the polymerizable functional group of the cyclic monomer (A), the (A) cyclic monomer has a side chain introduced into a reactive functional group selected from a hydroxyl group and an amino group, and the side chain has the polymerizable functional group and the ionic functional group, The polymerizable functional group of the cyclic monomer (A) is at least one group selected from the group consisting of a radical polymerizable group, an epoxy group, a hydroxyl group, a thiol group, a primary amino group, and a secondary amino group; The ionic functional group contained in the cyclic monomer (A) is a group capable of forming at least one ion selected from the group consisting of a carboxyl ion, a sulfonate ion, a phosphate ion, a phosphonate ion, and a quaternary ammonium cation, The curable composition, wherein the content of the polyrotaxane monomer in the curable composition is 0% by mass.

2. 2. The curable composition according to claim 1, wherein, in the cyclic monomer (A), when the total molar ratio of the polymerizable functional group and the ionic functional group is taken as 100 mol %, a ratio of the ionic functional group is 1 mol % or more and less than 90 mol %.

3. The (A) cyclic monomer is a cyclic monomer in which a side chain is introduced into a hydroxyl group of a cyclic molecule having a hydroxyl group, and The curable composition according to claim 1 or 2, wherein the side chain has the polymerizable functional group and the ionic functional group.

4. the polymerizable functional group of the cyclic monomer (A) is at least one group selected from the group consisting of a hydroxyl group, a thiol group, a primary amino group, and a secondary amino group, The curable composition according to any one of claims 1 to 3, wherein the polymerizable monomer (B) comprises an iso(thio)cyanate compound (B1) having at least an iso(thio)cyanate group in the molecule.

5. the polymerizable functional group of the cyclic monomer (A) contains at least a hydroxyl group, The iso(thio)cyanate compound (B1) contained in the polymerizable monomer (B) is (B32) a bifunctional active hydrogen-containing compound having two active hydrogen-containing groups in the molecule; The curable composition according to claim 4, comprising (B12) a urethane prepolymer having iso(thio)cyanate groups at both ends of the molecule obtained by reacting (B13) a bifunctional polyiso(thio)cyanate compound having two iso(thio)cyanate groups in the molecule with

6. The curable composition according to claim 5, wherein the urethane prepolymer (B12) has an iso(thio)cyanate equivalent of 300 to 5,000.

7. The curable composition according to any one of claims 1 to 6, further comprising (D) hollow particles each comprising an outer shell made of at least one resin selected from the group consisting of a urethane resin and a melamine resin, and a hollow portion surrounded by the outer shell.

8. A cured product obtained by curing the curable composition according to any one of claims 1 to 7.

9. A polishing pad comprising the cured product according to claim 8.

10. A cyclic monomer (A) used in the curable composition according to any one of claims 1 to 7, the cyclic monomer (A) having both a polymerizable functional group and an ionic functional group in the molecule thereof, the (A) cyclic monomer has a side chain introduced into a reactive functional group selected from a hydroxyl group and an amino group, and the side chain has the polymerizable functional group and the ionic functional group, The polymerizable functional group of the cyclic monomer (A) is at least one group selected from the group consisting of a radical polymerizable group, an epoxy group, a hydroxyl group, a thiol group, a primary amino group, and a secondary amino group; The ionic functional group contained in the cyclic monomer (A) is A cyclic monomer which is a group capable of forming at least one type of ion selected from the group consisting of a carboxyl ion, a sulfonate ion, a phosphate ion, a phosphonate ion, and a quaternary ammonium cation.

Images