WO2020032056A1 - Curable composition containing polypseudorotaxane monomer - Google Patents

Abstract

The present invention relates to a curable composition comprising: (A) a polypseudorotaxane monomer that has a composite molecular structure composed of a ring-shaped molecule having a polymerizable functional group and an axle molecule that passes through the ring interior of the ring-shaped molecule, wherein at least one terminal of the axle molecule has no bulky groups; and (B) a polymerizable monomer other than (A) the polypseudorotaxane monomer. The present invention can provide a curable composition that can produce a high-quality material at high productivities, while incorporating a feature possessed by polyrotaxane into a cured article (the feature whereby the ring-shaped molecule moves along the axle molecule) and maintaining excellent mechanical properties. The present invention can also provide a cured article using the curable composition.

Description

Curable composition containing polypseudorotaxane monomer

The present invention relates to a novel polypseudorotaxane monomer, a novel curable composition containing the monomer, and a novel cured product obtained from the curable composition.

The polyrotaxane has a cyclic molecule, and a linear molecule (axial molecule) penetrating the cyclic molecule in a skewered manner, and is disposed at both ends of the axial molecule to separate (eliminate) the cyclic molecule from the axial molecule. ) And a bulky group (blocking group) for preventing the compound molecule. On the other hand, polypseudorotaxane has a cyclic molecule, and is composed of a linear molecule (axial molecule) penetrating the cyclic molecule in a skewered manner, and at least one of the terminal of the linear molecule has a bulky group. Have no complex molecular structure.

This polyrotaxane has various properties, particularly excellent mechanical properties, because the cyclic molecule can move on the axis molecule, and is expected to be applied to various applications.

多数 In order to impart these properties to various materials, many attempts have been made to introduce a polymerizable functional group into the polyrotaxane structure and introduce it into various polymer materials.

For example, in the field of optical materials, polyrotaxane monomers having a polymerizable functional group are used. Specifically, it is in the field of photochromic spectacle lenses. A photochromic spectacle lens is a lens that is colored quickly and functions as sunglasses outdoors when light containing ultraviolet rays such as sunlight is irradiated, and fades and clears indoors without such light irradiation. , And its demand has been increasing in recent years. Recently, a photochromic composition containing a polyrotaxane monomer has been disclosed as a photochromic composition for use in photochromic spectacles (see Patent Documents 1 to 4). In Patent Documents 1 to 4, a cured product obtained from a photochromic composition containing a polyrotaxane monomer has improved mechanical strength due to cross-linking of the polyrotaxane monomer, and excellent photochromic properties (color density and color density) due to free space formed by the polyrotaxane (monomer). (Fading rate).

ポ リ Also, application of the polyrotaxane monomer to a polishing pad material, which is a polishing member, is being studied. Specifically, it is used as a pad material (hereinafter, also referred to as a polishing pad) in a CMP (Chemical Mechanical Polishing) method. The CMP method is a polishing method for imparting excellent surface flatness, and is particularly employed in a process for manufacturing a liquid crystal display (LCD), a glass substrate for a hard disk, a silicon wafer, and a semiconductor device.

In the CMP method, a method of generally supplying a slurry (polishing liquid) in which abrasive grains are dispersed in an alkali solution or an acid solution during polishing is generally employed. That is, the object to be polished is flattened by the mechanical action by the abrasive grains in the slurry and the chemical action by the alkali solution or the acid solution. Usually, the slurry is supplied to the surface of the object to be polished, and the surface of the object to be polished is planarized by sliding the polishing pad material into contact with the surface.

研磨 As a material of such a polishing pad, an abrasive obtained from a urethane-based curable composition is known (see Patent Document 5). Recently, a polishing pad using polyrotaxane has been disclosed (see Patent Document 6). In Patent Document 6, by incorporating a polyrotaxane structure into a urethane resin, not only good wear resistance but also excellent polishing characteristics (high polishing rate, low scratch property, and high flatness) are exhibited.

Thus, it is known that polyrotaxane monomers exhibit excellent properties by reacting with other polymerizable monomers to form a cured product (polymer). However, it is generally known that the synthesis of a polyrotaxane monomer requires a multi-step synthesis process, and the yield is low. Therefore, cost reduction is required for commercial use.

WO 2015/068798 International Publication No. WO 2017/038957 International Publication No. WO 2016/143910 International Publication No. WO2018 / 030257 JP 2007-77207 A International Publication No. WO2018 / 092826 JP, 2017-222809, A

In order to simplify the production process of polyrotaxane, in the process of producing polyrotaxane from the production of polypseudorotaxinsan, the One-Pot method (to remove the polypseudorotaxane from the reaction system without removing the bulk without removing the polyrotaxane from the reaction system) A method of introducing a high group) has been proposed. For example, a method is known in which polyrotaxane composed of dimethyl-β-cyclodextrin and polyethylene glycol is converted to polyrotaxane by the One-Pot method (Patent Document 7). Further, a method is known in which a polyrotaxane composed of 2-hydroxypropyl-β-cyclodextrin and a copolymer of polyethylene glycol and polypropylene glycol is converted into a polyrotaxane by the One-Pot method (Non-patent Document 1). ).

According to this method, polyrotaxane can be obtained efficiently.

However, Patent Literature 7 and Non-Patent Literature 1 do not disclose that a cured product is produced in combination with another polymerizable monomer. Moreover, since a polyrotaxane that introduces a bulky group at the terminal is finally produced, the reaction takes time and various reagents need to be used.

の 通 り As described above, polyrotaxane monomers are capable of imparting excellent functions to cured products (polymers) using the same, and have been studied in various fields. However, it is difficult to produce the polyrotaxane monomer itself, and it takes a long time to produce the polyrotaxane monomer.

Therefore, an object of the present invention is to incorporate the properties of polyrotaxanes (the properties of moving cyclic molecules in an axis molecule) into a cured product (polymer) to maintain high mechanical properties while maintaining high productivity and high productivity. An object of the present invention is to provide a curable composition capable of producing a quality material and a cured product using the same.

発 明 The present inventors have conducted intensive studies in order to solve the above problems. Then, they have found that the above-mentioned problems can be solved by using a polypseudorotaxane obtained in the preceding step instead of using a polyrotaxane, and have completed the present invention.

That is, the first present invention
It has a complex molecular structure consisting of a cyclic molecule having a polymerizable functional group and a shaft molecule penetrating through the ring of the cyclic molecule, and has no bulky group at at least one end of the shaft molecule ( A) a polypseudorotaxane monomer, and
The curable composition contains (B) a polymerizable monomer other than the (A) polypseudorotaxane monomer.

In the present invention, in the above-mentioned polypseudorotaxane, a chain-like axis molecule penetrates the inside of a plurality of cyclic molecules, and at least one end of the axis molecule has a group larger than the inner diameter of the cyclic molecule. Refers to a complex of molecules having an unstructured structure. The (A) polypseudorotaxane monomer is a compound in which the complex has a polymerizable functional group.

In the prior art, in the case of the polypseudorotaxane monomer, there is a possibility that elimination of the cyclic molecule may occur. As a polyrotaxane monomer into which a bulky group not to be eliminated is introduced, a cured product is obtained in combination with another polymerizable monomer. On the other hand, in the present invention, a polypseudorotaxane monomer having no bulky group introduced at the terminal is used as it is in combination with another polymerizable monomer. The bulky group used in the present invention is a group having a larger inner diameter than the inner diameter calculated from the packing structure in consideration of the van der Waals radius of the cyclic molecule used in forming the polypseudorotaxane, that is, the cyclic molecule is included. Refers to a group that cannot be touched.

The second invention is a cured product obtained by curing the curable composition of the first invention.

硬化 The curable composition of the present invention contains a polypseudorotaxane monomer. The polypseudorotaxane monomer does not need to introduce a bulky group into the terminal of the shaft molecule as compared with a conventionally used polyrotaxane monomer. Therefore, the manufacturing process can be simplified and the number of reagents can be reduced, so that cost and production efficiency can be improved. As a result, the curable composition containing the polypseudorotaxane monomer is industrially very effective.

Further, in the present invention, the polypseudorotaxane monomer may have a polymerizable group at a terminal of the axis molecule. The polymerizable functional group does not need to be a sufficiently bulky group that can prevent the cyclic molecule from detaching from the axial molecule. If a polymerizable group has been introduced into the shaft molecule, the shaft molecule can be introduced into a polymer chain forming a matrix by reacting with another polymerizable monomer. And the obtained hardened | cured material improves a crosslinking density, and can suppress that a cyclic molecule remove | eliminates from an axial molecule. As a result, mechanical properties can be improved while maintaining or further improving the characteristics of the polyrotaxane as compared with a cured product using an existing polyrotaxane monomer.

Therefore, according to the present invention, not only the productivity of the curable composition is improved, but also the cured product obtained from the curable composition of the present invention can be produced while exhibiting excellent polishing properties and abrasion resistance. It becomes an excellent polishing pad with excellent properties. Further, a composition obtained by further mixing a photochromic compound with the curable composition can be a cured product having excellent photochromic properties.

BRIEF DESCRIPTION OF THE DRAWINGS Schematic which shows the molecular structure of the poly pseudorotaxane used for this invention.

The curable composition of the present invention,
It has a complex molecular structure consisting of a cyclic molecule having a polymerizable functional group and a shaft molecule penetrating through the ring of the cyclic molecule, and has no bulky group at at least one end of the shaft molecule ( A) a polypseudorotaxane monomer, and
The curable composition contains (B) a polymerizable monomer other than the (A) polypseudorotaxane monomer.

First, the (A) polypseudorotaxane monomer (hereinafter sometimes simply referred to as the component (A)) used in the present invention will be described.

<(A) Poly pseudorotaxane monomer; (A) component>
In the present invention, the polypseudorotaxane monomer (A) is, as shown in FIG. 1, a molecule of the polypseudorotaxane monomer represented by “1” as a whole and a chain axis molecule “2”. , And a cyclic molecule “3”. That is, the chain molecule “2” is included in the ring molecule “3”, and the shaft molecule “2” penetrates the inside of the ring of the ring molecule “3”.
A general polyrotaxane has bulky groups at both ends of an axis molecule. The bulky group is also referred to as a blocking group (blocking group for blocking a cyclic molecule), and is known as a component of polyrotaxane that functions as a group for preventing the release of a cyclic molecule from an axis molecule.
On the other hand, the polypseudorotaxane monomer of the present invention has no bulky group at at least one end of the axis molecule.

環状 In the (A) polypseudorotaxane monomer, the cyclic molecule “3” can slide on the axial molecule “2”. Therefore, when used for a phorocomic cured product, a free space is easily formed around the photochromic compound. Further, it is considered that the above-mentioned slidable effect can improve the abrasion resistance of the cured product and exhibit excellent mechanical properties. Therefore, when used as a polishing pad agent, excellent polishing characteristics and wear resistance can be exhibited.

In the (A) polypseudorotaxane monomer used in the present invention, various types of axial molecules are known. For example, as the axial molecule, linear or linear as long as it can penetrate the ring of the cyclic molecule. It may be branched and is generally formed by a polymer.

<Axial molecule; (A) polypseudorotaxane monomer>
Examples of the polymer forming such an axis molecule include polyvinyl alcohol, polyvinylpyrrolidone, cellulosic resins (such as carboxymethylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose), polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, and polytetramethylene ether. Glycol, polyvinyl acetal, polyvinyl methyl ether, polyamine, polyethylene imine, casein, gelatin, starch, olefin resin (polyethylene, polypropylene, etc.), polyester, polyvinyl chloride, styrene resin (polystyrene, acrylonitrile-styrene copolymer resin, etc.) , Acrylic resin (poly (meth) acrylate acid, polymethyl methacrylate Polymethyl acrylate, acrylonitrile-methyl acrylate copolymer resin), polycarbonate, polyurethane, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral, polyisobutylene, polytetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene copolymer (ABS resin) , Polyamide (such as nylon), polyimide, polydiene (such as polyisoprene and polybutadiene), polysiloxane (such as polydimethylsiloxane), polysulfone, polyimine, polyacetic anhydride, polyurea, polysulfide, polyphosphazene, polyketone polyphenylene, and polyhaloolefin And the like. These polymers may be used alone, appropriately copolymerized or modified, or may be modified.

Among the (A) polypseudorotaxane monomers used in the present invention, those suitable as a polymer forming an axis molecule include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, and poly (ethylene glycol). Tetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol or polyvinyl methyl ether. The axis molecule is more preferably a copolymer obtained by polymerizing a plurality of monomers. Among them, the axis molecule is preferably a copolymer composed of a plurality of different polyalkylene glycol moieties. Examples of the polyalkylene glycol moiety include a polyethylene glycol moiety, a polypropylene glycol moiety, and a polytetramethylene ether glycol moiety.

軸 In the present invention, the most preferably used axial molecule preferably includes at least part of a site having a structure represented by the following formula (I).

Where:
R ¹⁴ , R ¹⁵ , and R ¹⁶ are each a linear or branched alkylene group having 2 to 20 carbon atoms;
i, j, and k indicate the degree of polymerization (each repeating unit), and are each an integer of 1 to 200.

By having a structure (block copolymer) as in the above formula (I) in the shaft molecule, even if there is no bulky group at the terminal of the shaft molecule, it is difficult for the cyclic molecule to escape, and even when mixed with various monomers, It is considered that a stable polypseudorotaxane structure can be maintained.

R ¹⁴ , R ¹⁵ , and R ¹⁶ may be the same group or different groups. Among them, it is preferable that the number of carbon atoms of R ¹⁵ be larger than the number of carbon atoms of R ¹⁴ and R ¹⁶ from the viewpoint that the cyclic molecule is less likely to be eliminated. In this case, R ¹⁴ and R ¹⁶ may have the same carbon number. Specifically, R ¹⁴ is an ethylene group having 2 carbon atoms, R ¹⁵ is a propylene group having 3 carbon atoms, or a trimethylene group, and R ¹⁶ is a group such as an ethylene group having 2 carbon atoms. It is preferable that the relationship be established. ^{That, - (O-R 14)} i- (O-R 15) j- (O-R 16) k- is located between the block copolymer of - ^{(O-R 15)} - hydrophobic its Preferably, it is higher than both ends. Note that O is, of course, an oxygen atom.

Further, i, j, and k are more preferably 1 to 150, and j is 2 to 100, from the viewpoint that the productivity of the polypseudorotaxane monomer itself and the elimination of a cyclic molecule are difficult. More preferably, k is more preferably from 1 to 150. i, j, and k may be the same or different values.

The structure of the formula (I) may be present at one position or at a plurality of positions in the axis molecule. However, considering the productivity of the polypseudorotaxane monomer itself, the axis molecule itself has the structure of the formula (I). Is preferred.

Further, the (A) polypseudorotaxane monomer used in the present invention preferably has a polymerizable functional group introduced into a polymer terminal (terminal of the shaft molecule) forming a shaft molecule, and has a polymerizable functional group at both ends of the shaft molecule. It is more preferred to introduce groups. (A) The polymerizable functional group at the terminal of the axis molecule of the polypseudorotaxane monomer is not particularly limited, but preferred polymerizable functional groups include a hydroxyl group, a thiol group, an amino group, a carboxyl group, and a A) an acrylate group or an allyl group.

When the polymerizable functional group introduced into the terminal of the shaft molecule is a hydroxyl group, a thiol group, an amino group, or a carboxyl group, the other (B) polymerizable monomer described in detail below is an iso (thio) cyanate group. It is preferable to include a compound having the following formula: When the polymerizable functional group introduced into the terminal of the axis molecule is a (meth) acrylate group or an allyl group radical polymerizable group, the (B) polymerizable monomer has a radical polymerizable group. Preferably, it contains a compound.

The method for introducing the polymerizable functional group into the terminal of the -axis molecule is not particularly limited, and a known method may be employed. If the terminal of the shaft molecule is originally the polymerizable functional group, it may be used as it is, or if not, it may be introduced by modifying the terminal.

(4) By introducing a polymerizable functional group into the terminal of the above-mentioned shaft molecule, it reacts with the polymerizable monomer (B) described later, and the shaft molecule is incorporated into a part of the matrix. Thereby, excellent mechanical properties can be exhibited. In addition, the bonding allows the axial length of the shaft molecule to extend to another polymer chain via the bonding point, so that the sliding effect of the cyclic molecule can be further enhanced.

If the molecular weight of the above-mentioned axial molecule is too large, when it is mixed with other components, for example, other polymerizable monomers (B), the viscosity increases, and not only is the handling difficult, but also the compatibility is poor. Tend to be. From such a viewpoint, the weight average molecular weight Mw of the shaft molecule is preferably from 400 to 100,000, particularly preferably from 1,000 to 50,000, particularly preferably from 2,000 to 30,000. In addition, this weight average molecular weight Mw is a value measured by the GPC measurement method described in the following Examples.

In addition, one end of the axial molecule may have a bulky group having such a size that the following cyclic molecule is not eliminated, but the productivity of (A) the polypseudorotaxane monomer itself is taken into consideration. Then, it is preferable that the bulky group does not exist at both ends of the (A) polypseudorotaxane monomer.
The bulky group is not particularly limited as long as it is a group larger than the inner diameter of the cyclic molecule. A phenyl group and a pyrenyl substrate.

<Cyclic molecule; (A) polypseudorotaxane monomer>
In the present invention, the cyclic molecule (A) of the polypseudorotaxane monomer may be any as long as it has a ring having a size that can include the above-mentioned axial molecule. Examples of such a ring include a cyclodextrin ring, a crown ether ring, a benzocrown ring, a dibenzocrown ring, and a dicyclohexanocrown ring. Among them, a cyclodextrin ring is particularly preferred.

The cyclodextrin ring includes α-form (ring inner diameter 0.45 to 0.6 nm), β-form (ring inner diameter 0.6 to 0.8 nm), and γ-form (ring inner diameter 0.8 to 0.95 nm). Also, a mixture of these can be used. In the present invention, an α-cyclodextrin ring and a β-cyclodextrin ring are particularly preferred.

環状 In the cyclic molecule having a ring as described above, one or more cyclic molecules are included in one axis molecule. In general, at least one or more cyclic molecules are included per axis molecule, and when the maximum number of included cyclic molecules that can be included is 1, the maximum number of circular molecules is 0.1. 8 or less. More preferably, it is encapsulated by at least two or more cyclic molecules, and the number of inclusions of the cyclic molecules is preferably at most 0.5 or less.

If the number of inclusions of the cyclic molecule is too large, the mobility of the cyclic molecule is reduced due to the dense presence of the cyclic molecule with respect to one axis molecule. When mixed with a polymerizable monomer (B) other than the polypseudorotaxane monomer, not only does the handleability of the polymerizable composition deteriorate, but also poor molding of the cured product tends to occur.

The maximum number of inclusions of a cyclic molecule with respect to one axial molecule can be calculated from the length of the axial molecule and the thickness of the ring of the cyclic molecule. For example, taking the case where the chain portion of the axial molecule is formed of polypropylene glycol and the cyclic molecule is a β-cyclodextrin ring as an example, the maximum inclusion number is calculated as follows. That is, the two repeating units [—CH (CH ₃ ) —CH ₂ O—] of polypropylene glycol approximate the thickness of one β-cyclodextrin ring. Therefore, the number of repeating units is calculated from the molecular weight of the polyethylene glycol, and 1/2 of the number of repeating units is determined as the maximum number of inclusions of the cyclic molecule. The maximum number of clathrates is set to 1.0, and the number of clathrates of the cyclic molecule is adjusted to the above-mentioned range.

<Side chain of cyclic molecule; (A) polypseudorotaxane monomer>
In the (A) polypseudorotaxane monomer used in the present invention, the ring of the above-described cyclic molecule may have a side chain introduced. This side chain is indicated by "4" in FIG.

The side chain is not particularly limited, but is preferably formed by repeating an organic chain having 3 to 20 carbon atoms. In addition, there is no problem even if a type having a different side chain or a different number average molecular weight is introduced into the cyclic molecule. The number average molecular weight of such side chains is in the range of 45 to 10,000, preferably 55 to 5000, more preferably 55 to 1500. The number average molecular weight of the side chain can be adjusted by the amount used when introducing the side chain and can be determined by calculation, but can also be determined by ¹ H-NMR measurement.

That is, if the side chain is too small, it is difficult to form a space around the polypseudorotaxane monomer, and, for example, tends to inhibit the photochromic reversible reaction of a cured product obtained from the photochromic curable composition. Further, if the side chain is too short, the compatibility with other polymerizable monomers tends to decrease. Conversely, if the side chains are too long, the viscosity will increase when mixed with the polymerizable monomer, which will cause poor appearance of the cured product or lower the hardness of the cured product. When the cured product is used as a polishing pad, the abrasion resistance tends to decrease.

{Circle around (2)} Further, the side chain as described above is introduced by utilizing the reactive functional group of the cyclic molecule and modifying the reactive functional group (inserted by reacting with the reactive functional group). For example, a β-cyclodextrin ring has 21 OH groups (hydroxyl groups) as reactive functional groups, and a side chain is introduced via the OH groups (by reacting the OH groups). That is, a maximum of 21 side chains can be introduced into one β-cyclodextrin ring. In the present invention, it is preferable that 4% to 70% of the total number of functional groups possessed by such a ring is modified with a side chain in order to sufficiently exert the function of the side chain described above (where the ring is It is preferable that the side chain is introduced in 4% to 70% of the total number of functional groups.)

As will be described in detail below, the reactive functional group of the cyclic molecule has lower reactivity than the OH group of the side chain, so that even if the degree of modification is low, the compatibility is reduced, and the problem of bleed out is unlikely to occur. . Therefore, if the modification degree is in the above range, a more excellent effect is exhibited. Incidentally, when the side chain is bonded to 7 out of the 21 OH groups of the β-cyclodextrin ring, the modification degree (introduction degree) is 33%.

に お い て In the present invention, the side chains (organic chains) as described above may be linear or branched as long as the size is within the above-described range. Regarding the introduction of the side chain, it is possible to appropriately introduce a method or a compound disclosed in International Publication No. WO2015 / 159875, and it is possible to appropriately introduce a ring-opening polymerization; a radical polymerization; a cationic polymerization; an anion polymerization; Living radical polymerization such as RAFT polymerization and NMP polymerization can be used. By the above method, a suitably selected compound can be reacted with the functional group of the ring to introduce a side chain of an appropriate size.

For example, a side chain derived from a cyclic compound such as lactone or cyclic ether can be introduced by ring-opening polymerization. An OH group is introduced into a side chain introduced by ring-opening polymerization of a cyclic compound such as lactone or cyclic ether as a group having active hydrogen at the terminal of the side chain.

中 で も Among the cyclic compounds, it is preferable to use a cyclic ether or a lactone from the viewpoint that it is easily available, has high reactivity, and is easy to adjust the size (molecular weight). Specific examples of suitable cyclic compounds are as follows.

Cyclic ether;
Ethylene oxide, 1,2-propylene oxide, epichlorohydrin, epibromohydrin, 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide, oxetane, 3-methyloxetane, 3,3-dimethyloxetane, Tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran and the like.

Lactone compounds;
4-membered ring lactones, for example, β-propiolactone, β-methylpropiolactone, L-serine-β-lactone and the like.

5-membered ring lactones, for example, γ-butyrolactone, γ-hexanolactone, γ-heptanolactone, γ-octanolactone, γ-decanolactone, γ-dodecanolactone, α-hexyl-γ-butyrolactone, α-heptyl -Γ-butyrolactone, α-hydroxy-γ-butyrolactone, γ-methyl-γ-decanolactone, α-methylene-γ-butyrolactone, α, α-dimethyl-γ-butyrolactone, D-erythronolactone, α-methyl-γ -Butyrolactone, γ-nonanolactone, DL-pantolactone, γ-phenyl-γ-butyrolactone, γ-undecanolactone, γ-valerolactone, 2,2-pentamethylene-1,3-dioxolan-4-one, α- Bromo-γ-butyrolactone, γ-crotonolactone, α-methylene-γ-butyrolactone, α-me Tacryloyloxy-γ-butyrolactone, β-methacryloyloxy-γ-butyrolactone and the like.

6-membered ring lactones, for example, δ-valerolactone, δ-hexanolactone, δ-octanolactone, δ-nonanolactone, δ-decanolactone, δ-undecanolactone, δ-dodecanolactone, δ-tridecanolactone, δ-tetradecanolactone, DL-mevalonolactone, 4-hydroxy-1-cyclohexanecarboxylic acid δ-lactone, monomethyl-δ-valerolactone, monoethyl-δ-valerolactone, monohexyl-δ-valerolactone, 1,4-dioxane -2-one, 1,5-dioxepan-2-one and the like.

7-membered lactones such as non-alkyl-ε-caprolactone, dialkyl-ε-caprolactone, monomethyl-ε-caprolactone, monoethyl-ε-caprolactone, monohexyl-ε-caprolactone, dimethyl-ε-caprolactone, di-n-propyl- ε-caprolactone, di-n-hexyl-ε-caprolactone, trimethyl-ε-caprolactone, triethyl-ε-caprolactone, tri-n-ε-caprolactone, ε-caprolactone, 5-nonyl-oxepan-2-one, 4, 4,6-trimethyl-oxepan-2-one, 4,6,6-trimethyl-oxepan-2-one, 5-hydroxymethyl-oxepan-2-one and the like.

$ 8-membered lactones, such as ζ-enantholactone.

Other lactones, for example, lactone, lactide, dilactide, tetramethylglycoside, 1,5-dioxepan-2-one, t-butylcaprolactone and the like.

環状 The above-mentioned cyclic compounds can be used alone or in combination of two or more.

In the present invention, the side chain-introducing compound preferably used is 1,2-propylene oxide, ε-caprolactone, α-acetyl-γ-butyrolactone, α-methyl-γ-butyrolactone, γ-valerolactone, γ-butyrolactone, or the like. Is particularly preferred, and most preferred are 1,2-propylene oxide and ε-caprolactone.

In addition, when a cyclic compound is reacted by ring-opening polymerization to introduce a side chain, a reactive functional group (for example, a hydroxyl group) bonded to the ring is poor in reactivity, and particularly, a large molecule is directly reacted due to steric hindrance or the like. It can be difficult. In such a case, for example, in order to react with caprolactone or the like, a low-molecular compound such as propylene oxide is reacted with a functional group to perform hydroxypropylation, and a highly reactive functional group (hydroxyl group) is introduced. Then, a means of introducing a side chain by ring-opening polymerization using the above-described cyclic compound can be employed. In this case, the hydroxypropylated portion can also be considered as a side chain. The OH group (hydroxyl group) introduced by the hydroxypropylation naturally corresponds to the polymerizable functional group of the cyclic molecule.

In addition, introducing a side chain having an active hydrogen group by introducing a side chain derived from a cyclic compound such as a cyclic acetal, a cyclic amine, a cyclic carbonate, a cyclic imino ether, a cyclic thiocarbonate by ring-opening polymerization. Can be. Among these, specific examples of suitable cyclic compounds are those described in International Publication No. WO2015 / 068798.

方法 The method of introducing a side chain into a cyclic molecule using radical polymerization is as follows. The ring of the cyclic molecule of the polypseudorotaxane monomer does not have an active site serving as a radical initiation point. Therefore, prior to reacting the radical polymerizable compound, a compound for forming a radical starting point is reacted with a functional group (OH group) of the ring to form an active site serving as a radical starting point. It is necessary to keep.

As the compound for forming the above-mentioned radical initiation point, an organic halogen compound is representative, for example, 2-bromoisobutyryl bromide, 2-bromobutyric acid, 2-bromopropionic acid, 2-chloropropion Acid, 2-bromoisobutyric acid, epichlorohydrin, epibromohydrin, 2-chloroethyl isocyanate and the like can be mentioned. That is, such an organic halogen compound is bonded to the ring by a condensation reaction with a functional group of the ring of the cyclic molecule, and a group containing a halogen atom (residue of an organic halogen compound) is introduced into the ring. At the time of radical polymerization, radicals are generated in the organic halogen compound residue due to the movement of halogen atoms and the like, which serves as a radical polymerization starting point, whereby radical polymerization proceeds.

Further, the group having an active site (organic halogen compound residue) serving as a radical polymerization initiation point as described above includes, for example, a hydroxyl group in a ring, an amine, a carboxylic acid, an isocyanate, an imidazole, an acid anhydride and the like. A compound having a functional group may be reacted to introduce a functional group other than a hydroxyl group, and the other functional group may be introduced by reacting the above-mentioned organic halogen compound.

The radical polymerizable compound used to introduce a side chain by radical polymerization includes at least one functional group such as a group having an ethylenically unsaturated bond, such as a (meth) acrylate group, a vinyl group, and a styryl group. Compounds (hereinafter referred to as ethylenically unsaturated monomers) are preferably used. Further, as the ethylenically unsaturated monomer, an oligomer or polymer having a terminal ethylenically unsaturated bond (hereinafter, referred to as a macromonomer) can also be used. As such an ethylenically unsaturated monomer, specific examples of a suitable ethylenically unsaturated monomer include those described in International Publication No. WO2015 / 068798.

<Polymerizable functional group (polymerizable functional group of side chain); (A) polypseudorotaxane monomer>
Furthermore, after introducing the side chain by the above-described method, the functional group of the side chain can be modified to another polymerizable functional group. In the present invention, a reaction of reacting a functional group of a side chain with another compound to introduce a structure derived from the compound is referred to as “denaturation”. As the compound used for the modification, any compound that can react with the functional group of the side chain can be used. By selecting such a compound, it is possible to introduce various polymerizable functional groups into the side chain or to modify the polymer into a group having no polymerizable group.

If the modification of the side chain is exemplified, after the side chain of the terminal OH group is introduced by the above-described ring-opening polymerization, it has both a functional group capable of reacting with the OH group of the side chain and the radical polymerizable group. If a compound is used, a radical polymerizable group can be introduced. Note that, naturally, even the terminal OH group becomes a polymerizable functional group.

官能 Examples of the functional group capable of reacting with the OH group include an isocyanate group (—NCO group), a carboxyl group (—COOH), and an acid chloride group (eg, —COCl group). By reacting a compound having an isocyanate group, a radical polymerizable group is introduced via a urethane bond. Alternatively, a radical polymerizable group is introduced via an ester bond by reacting a compound having a carboxyl group, an acid chloride group, and the like.

Specific examples of the compound having a radical polymerizable group include, as compounds having an isocyanate group and a (meth) acrylate group, 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, and 1,1- (bisacryloyloxy). Methyl) ethyl isocyanate and the like.

The compound having an acid chloride (—COCl group) and a (meth) acrylate group can be synthesized by reacting a compound having a carboxyl group and a (meth) acrylate group with a chlorinating agent such as thionyl chloride. . Examples of the compound having a carboxyl group and a (meth) acrylate group include 2-methacryloyloxyethyl succinate and β-carboxyethyl acrylate.

Further, if the case where the functional group of the side chain is modified to one having no polymerizable group such as an active hydrogen group or a radical polymerizable group is exemplified, the side chain of the terminal OH group can be changed by the above-described ring-opening polymerization. After the introduction, instead of the functional group capable of reacting with the OH group in the side chain and the above-described radically polymerizable group, an alkyl group having 2 to 20 carbon atoms, an alkyleneoxy group having 2 to 30 carbon atoms, and a 6 to 20 carbon atom It is preferable to have an aryl group or the like. Specific examples of the above compounds are shown below.

As the compound having an isocyanate group, an isocyanate compound having 2 to 20 carbon atoms (excluding the carbon atom of the isocyanate group) is preferable from the viewpoint of availability of the raw material and high reactivity with the OH group, and 3 to 20 carbon atoms. Ten isocyanate compounds are particularly preferred. Specifically, examples of suitable isocyanate compounds include n-propyl isocyanate, n-butyl isocyanate, n-pentyl isocyanate, n-hexyl isocyanate, phenyl isocyanate and the like.

As the carboxylic acid chloride, a carboxylic acid chloride having 2 to 20 carbon atoms (excluding the carbon atom of the carbonyl group) is preferable from the viewpoint of availability of the raw material and high reactivity with the OH group. Particularly preferred are １０10 carboxylic acid chlorides. Specific examples of suitable acid chlorides include acetyl chloride, propionyl chloride, butyryl chloride, pivaloyl chloride, hexanoyl chloride, and benzoyl chloride.

When a side chain is introduced into a cyclic molecule using a radical polymerizable compound, if the radical polymerizable compound has another functional group, the side chain has a group having the functional group as it is. Will be. Even when only the radical polymerizable group is present in the side chain, after forming the side chain with the radical polymerizable compound, a part of the side chain may be modified with a group having a functional group other than the radical polymerizable group. For example, a functional group other than the radical polymerizable group can be introduced into the side chain.

理解 As understood from the above description, the side chain introduced into the ring of the cyclic compound may have various functional groups.

Furthermore, depending on the type of the functional group of the compound used for introducing the side chain, a part of this side chain is bonded to the functional group of the ring of the cyclic molecule of another axis molecule, A crosslinked structure may be formed.

In addition, not only the side chain but also a functional material such as a photochromic compound described later may be introduced into the ring of the present invention.

<Suitable polymerizable functional groups of the cyclic molecule and the number thereof>
The polymerizable functional group of the cyclic molecule is not particularly limited as long as it is a group capable of polymerizing with a polymerizable monomer other than the polypseudorotaxane monomer. In the present invention, preferred are a hydroxyl group, a thiol group, an amino group, a carboxyl group, a (meth) acrylate group, or an allyl group. Among them, the most preferred are a hydroxyl group and a (meth) acrylate group. In the case of a hydroxyl group, if the terminal of the side chain introduced when reacting the functional group of the cyclic molecule is a hydroxyl group, it may be used as it is as a polymerizable functional group. In the case of a (meth) acrylate group, it can be introduced into the terminal of the side chain according to the above method.

に お い て In the (A) polypseudorotaxane monomer, the number of polymerizable functional groups in the cyclic molecule is not particularly limited. In particular, the introduction of the polypseudorotaxane moiety into the resin serving as the matrix exerts an excellent effect, so that the cyclic molecule preferably contains at least two polymerizable functional groups.

The polymerizable functional group is, depending on the case, the one possessed by the above-described cyclic molecule or the one introduced using the above-mentioned side chain. Among them, in consideration of the reactivity, it is preferable that the terminal of the side chain be a polymerizable functional group, and that two or more be present. The upper limit of the number of the polymerizable functional groups is not particularly limited, but the number of moles of the polymerizable functional groups introduced into the terminal of the side chain is determined based on the weight average molecular weight of the (A) polypseudorotaxane monomer. On the other hand, the number is 10 mmol / g. As the weight average molecular weight, a value measured by gel permeation chromatography (GPC) described below is used. Depending on the GPC measurement conditions, a cyclic molecule may be eliminated. Therefore, when performing GPC measurement, first, it is confirmed whether or not a cyclic molecule is eliminated under the measurement conditions. If no desorption occurs, the measurement is performed as it is. On the other hand, in the case of elimination, as a preliminary experiment, it is also possible to measure the GPC by (A) sealing the end of the polypseudorotaxane monomer with a bulky group and taking the molecular weight of the bulky group into consideration. it can.

<Suitable (A) polypseudorotaxane monomer>
In the present invention, the (A) polypseudorotaxane monomer suitably used is:
It has an axial molecule composed of a polyalkylene glycol moiety having a hydroxyl group or an amino group (a polymerizable functional group having a size that cannot prevent elimination of a cyclic molecule) at both ends, and has an α-cyclodextrin ring or a β-cyclodextrin ring. It is preferable that a side chain (terminal is an OH group) is introduced into the ring by a hydroxypropylene group or a polycaprolactone group.

Among them, the weight average molecular weight of the axis molecule is 2,000 to 50,000, and the axis molecule is a block copolymer of PEG (polyethylene glycol) -PPG (polypropylene glycol) -PEG (polyethylene glycol) or PEG (polyethylene glycol). ) -PPG (polypropylene glycol) random copolymer, PEG (polyethylene glycol) -PTMG (polytetramethylene ether glycol) -PEG (polyethylene glycol) block copolymer, or PEG (polyethylene glycol) -PTMG (polytetraethylene) Methylene ether glycol) random copolymer, PTMG (polytetramethylene ether glycol) -PPG (polypropylene glycol) -PTMG (polytetramethylene ether) Recohol) or a random copolymer of PTMG (polytetramethylene ether glycol) -PPG (polypropylene glycol), and particularly preferably PEG (polyethylene glycol) -PPG (polypropylene). Glycol) -PEG (polyethylene glycol) block copolymers are preferred.

側 Also, it is preferable that a side chain is introduced into 4% or more and 70% or less of the hydroxyl group of the α-cyclodextrin ring or β-cyclodextrin, and the number average molecular weight of the side chain is preferably 50 to 600. Further, it is preferable that the number of the polymerizable functional groups at the terminal of the side chain is 2 or more and 10 mmol / g or less in the molecule of the pseudorotaxane.

<(A) Polymerizable monomer other than poly-pseudorotaxane monomer (B)>
In the present invention, the polymerizable monomer (B) may have at least one polymerizable compound capable of reacting with the (A) polypseudorotaxane monomer, and known compounds can be used without any limitation. As described above, various polymerizable functional groups can be introduced into the (A) polypseudorotaxane monomer. The polymerizable monomer (B) may be selected accordingly. For example, the polymerizable monomer (B) described in International Publication No. WO2015 / 068798 can be mentioned.

In the present invention, for example, when the polymerizable functional group of the (A) polypseudorotaxane monomer contains a hydroxyl group, a thiol group, a carboxyl group, or an amino group, (B) the polymerizable monomer includes, for example, (B1) An iso (thio) cyanate compound having an iso (thio) cyanate group (hereinafter may be simply referred to as “(B1) iso (thio) cyanate compound” or “(B1) component”).

Further, when the polymerizable functional group of the (A) polypseudorotaxane monomer is a hydroxyl group, an amino group, or an iso (thio) cyanate group, (B2) an epoxy group-containing monomer having an epoxy group (hereinafter, referred to as an epoxy group-containing monomer) It may be simply referred to as “(B2) epoxy group-containing monomer” or “(B2) component”).

On the other hand, when (A) the polymerizable functional group of the polypseudorotaxane monomer is an iso (thio) cyanate group, (B3) the polymer has at least one group selected from a hydroxyl group and a thiol group. An all compound (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 referred to as “(B4) amino group Monomer "or" (B4) component "). In the present invention, the iso (thio) cyanate group refers to an isocyanate group (NCO group) or an isothiocyanate group (NCS group). Therefore, when there are a plurality of iso (thio) cyanate groups, the total number of the isocyanate groups and the isothiocyanate groups may be plural.

Further, when the polymerizable functional group of the (A) polypseudorotaxane monomer is a radical polymerizable group, the polymerizable monomer (B) is preferably a monomer having a radical polymerizable group, and a (meth) acrylate group may be used. It is preferable to select from (meth) acrylate compounds and allyl compounds, and particularly preferable to select from (meth) acrylate compounds.

In the present invention, (A) the polypseudorotaxane monomer may have a polymerizable functional group at the terminal of the axial molecule in addition to the cyclic molecule. These may, of course, have a plurality of types of polymerizable functional groups in the cyclic molecule, or may have different polymerizable functional groups at the ends of the axis molecule. May be different. However, in order to facilitate the polymerization reaction and suppress by-products, the following is preferable in combination with another (B) polymerizable monomer. That is, (A) the polymerizable functional group of the polypseudorotaxane monomer is a polymerizable functional group such as a hydroxyl group, a thiol group, an amino group, and a carboxyl group, and (B) the polymerizable monomer is (B1) iso ( It is preferably a thio) cyanate compound. When the polymerizable functional group of the polypseudorotaxane monomer (A) is a radical polymerizable group, the polymerizable monomer (B) is preferably a monomer having a radical polymerizable group.

<(B) Polymerizable monomer; (B1) iso (thio) cyanate compound; (B1) component>
(B1) The iso (thio) cyanate compound is a monomer having at least one type of isocyanate group or isothiocyanate group. Of course, a monomer having two groups of an isocyanate group and an iso (thio) cyanate group is also selected. Among them, compounds having 2 to 6 iso (thio) cyanate groups in the molecule are preferable, compounds having 2 to 4 are more preferable, and compounds having 2 are more preferable.

The (B1) iso (thio) cyanate compound is prepared by reacting a bifunctional polyiso (thio) cyanate compound described below with a bifunctional poly (thio) ol compound (B12) urethane prepolymer (B12). Hereinafter, it may be simply referred to as “(B12) urethane prepolymer” or “(B12) component”). As the urethane prepolymer (B12) corresponding to the iso (thio) cyanate compound, one generally used containing an unreacted iso (thio) cyanate group can be used in the present invention without any limitation.

The (B1) iso (thio) cyanate compound can be broadly classified, for example, into aliphatic isocyanates, alicyclic isocyanates, aromatic isocyanates, isothiocyanate compounds, and (B12) urethane prepolymers. As the (B1) iso (thio) cyanate compound, one kind of compound may be used, or a plurality of kinds of compounds may be used. When a plurality of types of compounds are used, the reference mass is the total amount of the plurality of types of compounds. Specific examples of these iso (thio) cyanate compounds include the following monomers.

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-trimethyl Hexamethylene diisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 2,5,7-trimethyl-1 8-diisocyanate-5-isocyanatomethyloctane, bis (isocyanateethyl) carbonate, bis (isocyanateethyl) ether, 1,4-butyleneglycoldipropylether-ω, ω'-diisocyanate, lysine diisocyanate methyl ester, 2,4 Bifunctional isocyanate monomers such as 4, -trimethylhexamethylene diisocyanate (corresponding to (B13) a bifunctional polyiso (thio) cyanate group-containing monomer constituting a (B12) urethane prepolymer described in detail below),
Monofunctional isocyanate monomers such as ethyl isocyanate, n-propyl isocyanate, i-propyl isocyanate, butyl isocyanate and octadecyl isocyanate.

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 ( Isocyanatomethyl) furan, 1,3-bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane-4,4′-diisocyanate, 4,4-isopropylidenebis (cyclohexylisocyanate), cyclohexanediisocyanate, methylcyclohexa Diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2′-dimethyldicyclohexylmethane diisocyanate, bis (4-isocyanate-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) tricyclo Decane, 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 ^2.6 ] decane-3,8-diisocyanate, tricyclo [5.2.1.0 ^2.6 ] decane-4,9-diisocyanate Isocyanate monomer ((B12) a bifunctional polyiso (thio) cyanate group-containing monomer constituting a urethane prepolymer 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) -5- (2-isocyanatoethyl) -bicyclo [ 2,2,1] -heptane, 2-isocyanatomethyl-3- ( -Isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2,1,1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo [ 2,2,1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane, 1,3,5-tris Polyisocyanate monomers such as (isocyanatomethyl) cyclohexane,
Monofunctional isocyanate monomers such as cyclohexyl isocyanate.

Aromatic isocyanate; component (B1) xylylene diisocyanate (o-, m-, p-), tetrachloro-m-xylylene diisocyanate, methylene diphenyl-4,4'-diisocyanate, 4-chloro-m-xylylene diisocyanate 4,4-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 (isocyanatebutyl) benzene, bis (isocyanatemethyl) naphthalene, bis (isocyanatemethyl) diphenylether, bis (isocyanateethyl) phthalate, 2,6-di (isocyanatomethyl) furan, phenylenediisocyanate (o-, m- , P-), tolylene diisocyanate, ethyl phenylene diisocyanate, isopropyl phenylene diisocyanate, dimethyl phenylene diisocyanate, diethyl phenylene diisocyanate, diisopropyl phenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, 1,3,5-triisocyanate methylbenzene, , 5-naphthalenediisocyanate, methylnaphthalenediisocyanate, 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 (isocyanatephenyl) ethylene, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, phenylisocyanatemethylisocyanate, phenylisocyanateethylisocyanate, tetrahydro Naphthylene diisocyanate, hexahydrobenzene diisocyanate, hexahydrodiphenylmethane-4,4'-diisocyanate, diphenyl ether diisocyanate G, 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, 2, Bifunctional isocyanate monomer such as 1,6-tolylene diisocyanate (corresponding to (B13) a bifunctional polyiso (thio) cyanate group-containing monomer constituting (B12) a urethane prepolymer described in detail below),
Mesitylylene triisocyanate, triphenylmethane triisocyanate, polymeric MDI, naphthalene triisocyanate, diphenylmethane-2,4,4'-triisocyanate, 3-methyldiphenylmethane-4,4 ', 6-triisocyanate, 4-methyl- Polyfunctional isocyanate monomers such as diphenylmethane-2,3,4 ', 5,6-pentaisocyanate.

Monofunctional isocyanate monomers such as phenyl isocyanate, 3-i-propenyl cumyl isocyanate, 4-methoxyphenyl isocyanate, m-tolyl isocyanate, p-tolyl isocyanate, 1-naphthyl isocyanate and dimethylbenzyl isocyanate.

Isothiocyanate compound; (B1) component Bifunctional iso (thio) cyanate group-containing monomers such as p-phenylenediisothiocyanate, xylylene-1,4-diisothiocyanate, and ethylidene diisothiocyanate (described in detail below ( B12) (B13) constituting a urethane prepolymer, which corresponds to a bifunctional polyiso (thio) cyanate group-containing monomer).

<(B) Polymerizable monomer; (B12) urethane prepolymer; urethane (B1) component having terminal iso (thio) cyanate group>
In the present invention, the urethane prepolymer (B12) obtained by reacting the (B13) bifunctional polyiso (thio) cyanate group-containing monomer with the (B32) bifunctional poly (thio) ol described below is used as the (B1) It can also be used as a polyiso (thio) cyanate monomer.

When the urethane prepolymer is used as the (B12) urethane prepolymer, it is not particularly limited, but as the (B13) bifunctional polyiso (thio) cyanate group-containing monomer, it is particularly preferable to use the monomers exemplified below. . Specifically, 1,5-naphthalene diisocyanate, xylene diisocyanate (o-, m-, p-), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, phenylene diisocyanate (o-, m-, p-), 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethyl Hexamethylene diisocyanate, isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 2β, 5α-bis (isocyanate) norbornane, 2β, 5β-bis (isocyanate) norbornane, 2β, 6α- Scan (isocyanate) norbornane, 2.beta, it is preferable to use 6β- bis (isocyanate) norbornane. It is preferable to react these with a (B32) bifunctional poly (thio) ol to obtain a (B12) component having an iso (thio) cyanate group at both ends.

(B) In the urethane prepolymer (B12), both ends of the molecule must be iso (thio) cyanate groups. Therefore, the (B12) urethane prepolymer is obtained by reacting the (B13) bifunctional polyiso (thio) cyanate group-containing monomer with the number of moles (n5) of iso (thio) cyanate groups and the active hydrogen of (B32) bifunctional poly (thio) ol. It is preferable that the number of moles of the group having the formula (n6) is within the range of 1 <(n5) / (n6) ≦ 2.3. When two or more (B13) bifunctional polyiso (thio) cyanate group-containing monomers are used, the number of moles (n5) of the iso (thio) cyanate group is determined by the number of (B13) bifunctional polyiso (thio) cyanate group-containing monomers. Is the total number of moles of iso (thio) cyanate groups. When two or more (B32) bifunctional poly (thio) ols are used, the number of moles (n6) of the group having an active hydrogen is determined by the total activity of the (B32) bifunctional poly (thio) ol. It is the number of moles of hydrogen.

Although not particularly limited, the urethane prepolymer (B12) is obtained by dividing the molecular weight of the iso (thio) cyanate equivalent ((B12) urethane prepolymer by the number of iso (thio) cyanate groups in one molecule). Is preferably 300 to 5,000, more preferably 500 to 3,000, and particularly preferably 700 to 2,000. The urethane prepolymer (B12) in the present invention is preferably a linear one synthesized from (B13) a bifunctional polyiso (thio) cyanate group-containing monomer and (B32) bifunctional poly (thio) ol. Therefore, in this case, the number of iso (thio) cyanate groups in one molecule is two.
Even in this case, the equivalent of the iso (thio) cyanate is preferably 300 to 5,000. That is, the average iso (thio) cyanate equivalent in the (B1) iso (thio) cyanate compound comprising the (B12) urethane prepolymer and the (B13) bifunctional polyiso (thio) cyanate group-containing monomer is 300 to 5000. Preferably. When the average iso (thio) cyanate equivalent is 300 to 5000, a polyiso (thio) cyanate compound having a certain molecular weight is used, and it is considered that an excellent effect is exhibited.

The iso (thio) cyanate equivalent of the (B12) urethane prepolymer can be determined by quantifying the iso (thio) cyanate group of the (B12) urethane prepolymer in accordance with JIS {K} 7301. The iso (thio) cyanate group can be quantified by the following reverse titration method. First, the obtained (B12) urethane prepolymer is dissolved in a dry solvent. Next, di-n-butylamine, which is clearly in excess of the amount of iso (thio) cyanate groups contained in the urethane prepolymer (B12) and has a known concentration, is added to the dry solvent, and (B12) ) Reacting all iso (thio) cyanate groups of the urethane prepolymer with di-n-butylamine; The di-n-butylamine not consumed (not participating in the reaction) is then titrated with acid to determine the amount of di-n-butylamine consumed. Since the consumed di-n-butylamine and the iso (thio) cyanate group of the (B12) urethane prepolymer are the same, the iso (thio) cyanate equivalent can be determined. Further, since the (B12) urethane prepolymer is a linear urethane prepolymer having an iso (thio) cyanate group at both terminals, the number average molecular weight of the (B12) urethane prepolymer is equivalent to iso (thio) cyanate equivalent. Is twice as large as The molecular weight of this (B12) urethane prepolymer tends to match the value measured by gel permeation chromatography (GPC). When the (B12) urethane prepolymer and the (B13) bifunctional polyiso (thio) cyanate group-containing monomer are used in combination, the mixture of both may be measured according to the above method.

Further, the (B12) urethane prepolymer has an iso (thio) cyanate content ((I)) present in the (B12) urethane prepolymer, which is obtained from the iso (thio) cyanate equivalent of the (B12) urethane prepolymer. Molar concentration (mol / kg)) and (B12) content of (thio) urethane bond (including (thio) urea bond) present in urethane prepolymer ((U); molar concentration (mol / kg) ) Preferably satisfies 1 ≦ (U) / (I) ≦ 10. This range is the same when the (B12) urethane prepolymer and the (B13) bifunctional polyiso (thio) cyanate group-containing monomer are used in combination. The iso (thio) cyanate content ((I); molar concentration (mol / kg)) is a value obtained by multiplying the reciprocal of the iso (thio) cyanate equivalent by 1000. The theoretical value of the (thio) urethane bond (including (thio) urea bond) content (U) mass molar concentration (mol / kg) present in the urethane prepolymer can be determined by, for example, the following method. That is, the (B12) bifunctional poly (thio) ol constituting the urethane prepolymer and the (B13) bifunctional polyiso (thio) cyanate group-containing monomer present in the (B13) bifunctional polyiso (thio) cyanate group-containing monomer. Is the total isocyanate content ((aI); molar concentration (mol / kg)), the content of (thio) urethane bond (including (thio) urea bond) ((U); molar concentration ( mol / kg)) is calculated from the content of all iso (thio) cyanate groups of component (B) ((aI); molar concentration (mol / kg)) to isocyanate content ((I); molar concentration (mol) / Kg)) minus ((U) = (aI)-(I)).

((B12) Method for producing urethane prepolymer)
The method for producing a prepolymer used in the present invention is characterized in that (B32) 2 having two active hydrogen groups in the molecule and (B13) 2 having two functional poly (thio) ol and iso (thio) cyanate groups in the molecule. By reacting with a functional polyiso (thio) cyanate group-containing monomer,
The urethane prepolymer (B12) having an iso (thio) cyanate group at the terminal of the molecule may be produced. There is no limitation as long as a prepolymer having an iso (thio) cyanate group at a terminal can be obtained.
In the reaction for producing the urethane prepolymer, it can be produced by heating or adding a urethanization catalyst as necessary.

<(B) Polymerizable monomer; (B2) epoxy group-containing monomer; (B2) component>
The epoxy group-containing monomer has an epoxy group in a molecule as a polymerizable group. Particularly, (A) a hydroxyl group, an NH ₂ group, or an NCO group is introduced as a polymerizable functional group of the polypseudorotaxane monomer. It is suitable when there is.

Such epoxy compounds are roughly classified into aliphatic epoxy compounds, alicyclic epoxy monomers, and aromatic epoxy monomers, and preferred examples thereof are described in WO 2015/068798. Can be used.

<(B) Polymerizable monomer; (B3) (thio) ol compound; (B3) component>
The (thio) ol compound is a monomer having at least one group selected from the group consisting of an OH group and an SH group in one molecule. Of course, a monomer having two groups, an OH group and an SH group, is also selected.

The (thio) ol compounds can be roughly classified into aliphatic alcohols, alicyclic alcohols, aromatic alcohols, polyester polyols, polyether polyols, polycaprolactone polyols, polycarbonate polyols, polyacryl polyols, thiols, and OH / SH types. It is classified as a polymerizable group-containing monomer. The following are specific examples.

Aliphatic alcohol; component (B3) 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-dihydroxydodecan, neopentyl glycol, glyceryl monooleate, monoelaidin, polyethylene glycol, 3-methyl-1, Bifunctional polyol monomers such as 5-dihydroxypentane, dihydroxyneopentyl, 2-ethyl-1,2-dihydroxyhexane, 2-methyl-1,3-dihydroxypropane (the urethane Bifunctional poly (thio) ol (B32) constituting the repolymer (B12)),
Glycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, trimethylolpropane tripolyoxyethylene ether (for example, TMP-30, TMP-60, TMP-90, etc. of Nippon Emulsifier Co., Ltd.), butanetriol, 1,2- Methyl glucoside, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, erythritol, threitol, ribitol, arabinitol, xylitol, allitol, mannitol, dorsitol, iditol, glycol, inositol, hexanetriol, triglycerol, diglycerol, triethylene Polyfunctional polyol monomers such as glycol.

Alicyclic alcohol; (B3) component 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] nonanedi methanol, tricyclo [5,3,1,1 ^3,9] dodecane - diethanol, hydroxypropyl tricyclo [5,3,1,1 ^3,9] dodecanol, spiro [3,4] octanediol, butyl cyclohexanediol, 1,1'-bicyclohexene Bifunctional polyol monomers such as lidenediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, and o-dihydroxyxylylene (constituting the urethane prepolymer (B12)) (B32) corresponds to a bifunctional poly (thio) ol),
Polyfunctional polyol monomers such as tris (2-hydroxyethyl) isocyanurate, cyclohexanetriol, sucrose, maltitol, lactitol.

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- (3-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) butane, 2 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 3,3-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxy Phenyl) hexane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxyphenyl) heptane, 4,4 -Bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxyphenyl) tridecane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (3-methyl-4-hydroxyphenyl ) Propane, 2,2-bis (3-ethyl-4-hydroxyphenyl) propane, 2,2-bis (3-n-propyl-4-hydroxy) Phenyl) 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-hydroxy Phenyl) propane, bis (4-hydroxyphenyl) cyanomethane, 1-cyano-3,3-bis (4-hydroxyphenyl) butane, 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-hydroxy Enyl) 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'- Dihydroxydiphenylsulfoxide, 3,3'-dimethyl-4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone, bis (4-hydroxy Phenyl) ketone, (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-hydroxype Butyl) benzene, 1,4-bis (6-hydroxyhexyl) benzene, 2,2-bis [4- (2 ″ -hydroxyethyloxy) phenyl] propane, and bifunctional polyol monomers such as hydroquinone and resorcinol (the above (( B12) (B32) constituting the urethane prepolymer, which corresponds to the bifunctional poly (thio) ol)
Polyfunctional polyol monomers such as trihydroxynaphthalene, tetrahydroxynaphthalene, benzenetriol, biphenyltetraol, pyrogallol, (hydroxynaphthyl) pyrogallol and trihydroxyphenanthrene.

Polyester polyol; (B3) component A compound obtained by a condensation reaction between a polyol and a polybasic acid is exemplified. Among them, the number average molecular weight is preferably from 400 to 2,000, more preferably from 500 to 1500, and most preferably from 600 to 1200. Those having hydroxyl groups only at both ends of the molecule (two in the molecule) correspond to the (B32) bifunctional poly (thio) ol constituting the (B12) urethane prepolymer.

Polyether polyol; (B3) component A compound obtained by ring-opening polymerization of an alkylene oxide or a reaction of a compound having two or more active hydrogen-containing groups in a molecule with an alkylene oxide and a modified product thereof. Among them, the number average molecular weight is preferably from 400 to 2,000, more preferably from 500 to 1500, and most preferably from 600 to 1200. Those having hydroxyl groups only at both ends of the molecule (two in the molecule) correspond to the (B32) bifunctional poly (thio) ol constituting the (B12) urethane prepolymer.

Polycaprolactone polyol; a compound obtained by ring-opening polymerization of component (B3) ε-caprolactone. Among them, the number average molecular weight is preferably from 400 to 2,000, more preferably from 500 to 1500, and most preferably from 600 to 1200. Those having hydroxyl groups only at both ends of the molecule (two in the molecule) correspond to the (B32) bifunctional poly (thio) ol constituting the (B12) urethane prepolymer.

Polycarbonate polyol; (B3) component A compound obtained by phosgenating at least one kind of low molecular polyol or a compound obtained by transesterification using ethylene carbonate, diethyl carbonate, diphenyl carbonate or the like. Among them, the number average molecular weight is preferably from 400 to 2,000, more preferably from 500 to 1500, and most preferably from 600 to 1200. Those having hydroxyl groups only at both ends of the molecule (two in the molecule) correspond to the (B32) bifunctional poly (thio) ol constituting the (B12) urethane prepolymer.

Polyacrylic polyol; component (B3) a polyol compound obtained by polymerizing a (meth) acrylate ester or a vinyl monomer. Those having hydroxyl groups only at both ends of the molecule (two in the molecule) correspond to the (B32) bifunctional poly (thio) ol constituting the (B12) urethane prepolymer.

Thiol; Component (B3) As a preferable specific example of the thiol, those described in International Publication WO2015 / 068798 can be used. Among them, the following can be mentioned as examples of particularly preferable ones.

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 poly (thio) ol 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-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-dithi Emissions, tris - {(3-mercaptopropionyl) ethyl} - isocyanurate - such DOO thiol monomers.

OH / SH type polymerizable group-containing monomer; component (B3) 2-mercaptoethanol, 1-hydroxy-4-mercaptocyclohexane, 2-mercaptohydroquinone, 4-mercaptophenol, 1-hydroxyethylthio-3-mercaptoethylthiobenzene , 4-hydroxy-4'-mercaptodiphenylsulfone, 2- (2-mercaptoethylthio) ethanol, dihydroxyethylsulfide mono (3-mercaptopropionate), dimercaptoethane mono (sulfylate) (the (B12) urethane press (Corresponds to (B32) bifunctional poly (thio) ol constituting the polymer).

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 (thioglyco Poly (thiophene), pentaerythritol pentakis (3-mercaptopropionate), hydroxymethyl-tris (mercaptoethylthiomethyl) methane, hydroxyethylthiomethyltris (mercaptoethylthio) methane, etc. All monomer.

<(B) Polymerizable monomer; (B4) amino group-containing monomer; (B4) component>
(B4) The amino group-containing monomer is a monomer having one or more primary or secondary amino groups in one molecule. Among them, aliphatic amines, alicyclic amines, and aromatic It is classified into a group-III amine, and specific examples thereof include the following monomers.

Aliphatic amines; (B4) component Polyamines such as ethylenediamine, hexamethylenediamine, nonamethylenediamine, undecanemethylenediamine, dodecamethylenediamine, metaxylenediamine, 1,3-propanediamine, putrescine, diethylenetriamine and the like.

(4) Monofunctional amines such as monoethylamine, n-propylamine, diethylamine, di-n-propylamine, n-propylamine, di-n-butylamine and n-butylamine.

Alicyclic amines; (B4) components Polyamines such as isophoronediamine and cyclohexyldiamine.

(4) Monofunctional amines such as cyclohexylamine and N-methylcyclohexylamine.

Aromatic amine; (B4) component 4,4'-methylenebis (o-chloroaniline) (MOCA), 2,6-dichloro-p-phenylenediamine, 4,4'-methylenebis (2,3-dichloroaniline), 4,4'-methylenebis (2-ethyl-6-methylaniline), 3,5-bis (methylthio) -2,4-toluenediamine, 3,5-bis (methylthio) -2,6-toluenediamine, , 5-Diethyltoluene-2,4-diamine, 3,5-diethyltoluene-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'-dimethyldi Phenylmethane, 4,4'-diamino-3,3 ', 5,5'-tetraisopropyldiphenylmethane, 1,2-bis (2-aminophenylthio) ethane, 4,4'-diamino-3,3'- Diethyl-5,5'-dimethyldiphenylmethane, N, N'-di-sec-butyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, m-xylylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, p-phenylenediamine, 3,3'-methylenebis (methyl-6-aminobenzoate), 2,4 2-methylpropyl diamino-4-chlorobenzoate, isopropyl 2,4-diamino-4-chlorobenzoate, 2,4-diamino-4-chloro Eniru acetate - isopropyl, terephthalic acid - di - (2-aminophenyl) thioethyl, diphenylmethane diamine, tolylene diamine, piperazine, 1,3,5-benzene triamine, polyamines melamine.

(4) Monofunctional amines such as benzylamine and dibenzylamine.

Curable composition containing component (B1), component (B2), component (B3), and component (B4) In the present invention, component (B1), component (B2), component (B3), and component (B4) In other words, when the curable composition contains (A), the polymerizable functional group in the polypseudorotaxane monomer is not a radical polymerizable group, but is polymerized and cured by a polycondensation or polyaddition reaction to produce a cured product. Is preferably set to the following compounding ratio.

Specifically, the total amount of the component (B1), the component (B2), the component (B3), and the component (B4) (hereinafter, sometimes simply referred to as “the total amount of the component (B)”), and ( It is preferable that the component (A) is contained in an amount of 3 to 50 parts by mass and the total amount of the component (B) is contained in an amount of 50 to 97 parts by mass based on 100 parts by mass in total with the component (A). By including (A) the polypseudorotaxane monomer in this ratio, the obtained cured product can exhibit excellent polishing characteristics and mechanical characteristics when it is a polishing pad. In the case of a photochromic cured product containing a photochromic compound, excellent photochromic properties and mechanical properties can be exhibited. In order to exert the above effects, it is more preferable that the component (A) is in the range of 5 to 45 parts by mass and the total amount of the component (B) is in the range of 55 to 95 parts by mass.

Furthermore, assuming that the total amount of the component (B) is 100% by mass, the component (B1) is 0 to 95% by mass, the component (B2) is 0 to 100% by mass, the component (B3) is 0 to 80% by mass, and ( B4) The component is preferably set to 0 to 30% by mass in order to exhibit excellent mechanical properties. In order to exhibit this effect more, the component (B1) is 20 to 95% by mass, the component (B2) is 0 to 20% by mass, the component (B3) is 0 to 70% by mass, and the component (B4) is 0 to 25% by mass. More preferably,

に お い て In the present invention, the following compounding ratio may be used according to the use of the cured product obtained from the curable composition containing the (A) polypseudorotaxane monomer. Specifically, when used for a polishing pad such as a CMP method, the component (B1) is 40 to 95% by mass, the component (B2) is 0 to 5% by mass, the component (B3) is 0 to 35% by mass, and The component (B4) is preferably set to 0 to 20% by mass. When used for optical article applications such as spectacle lenses (for example, photochromic cured products), component (B1) 25 to 65% by mass, component (B2) 0 to 5% by mass, and component (B3) 35 to 70%. It is preferable that the content of the component (B4) is 0 to 15% by mass. In particular, it is preferable to use the urethane prepolymer (B12) in the component (B1).

Then, (A) the number of moles of all polymerizable functional groups capable of reacting with the iso (thio) cyanate group contained in the polypseudorotaxane monomer, the component (B2), the component (B3), and the component (B4); It is preferable that the ratio of the component to the total number of moles of iso (thio) cyanate groups satisfies 1: 0.8 to 1.2.

<(B) polymerizable monomer; (B5) radical polymerizable monomer>
(B5) The radically polymerizable monomer (hereinafter sometimes simply referred to as the component (B5)) is not particularly limited as long as it has a radically polymerizable group. 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.

好 適 As preferred specific examples of the (B5) radically polymerizable monomer, those described in International Publication No. WO2015 / 068798 can be used. Further, among them, the following compounds can be particularly preferably used, when a radical polymerizable compound that can be more preferably used in the present invention is exemplified.

(B51); (Meth) acrylate compound (B51) The (meth) acrylate compound (hereinafter sometimes simply referred to as “component (B51)”) is represented by, for example, the following formulas (1) to (4). Compounds.

(B511) monomer represented by formula (1); ((B51) component)

In the formula, R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and R ³ is a trivalent to hexavalent organic group having 1 to 10 carbon atoms. A is a number of 0 to 3 on average, and b is a number of 3 to 6. The alkyl group having 1 to 2 carbon atoms represented by R ² is preferably a methyl group. Examples of the organic group represented by R ³ include a group derived from a polyol, a trivalent to hexavalent hydrocarbon group, and a trivalent to hexavalent organic group containing a urethane bond.

Examples of suitable compounds in the above formula (1) include:
Trimethylolpropane trimethacrylate, ditrimethylolpropane tetramethacrylate and the like can be mentioned.

{Component (B512); {Compound represented by Formula (2)} Component (B51)

In the formula, R ⁴ and R ⁵ are each a hydrogen atom or a methyl group, and c and d are each an integer of 0 or more.

However, when R ⁴ and R ⁵ are both methyl groups, c + d is 2 to less than 7 on average, and when R ⁴ is a methyl group and R ⁵ is a hydrogen atom, c + d is 2 on average. and less than 5, in the case of R ⁴ and R ⁵ are both hydrogen atoms, c + d is 2 or more and less than 3 in average.

As an example of the most preferred compound in the above formula (2),
Tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate and the like.

{Component (B513); {Compound represented by Formula (3)} Component (B51)

Wherein R ⁶ and R ⁷ are each a hydrogen atom or a methyl group; R ⁸ and R ⁹ are each a hydrogen atom or a methyl group; R ¹⁰ is a hydrogen atom or a halogen atom; Represents —O—, —S—, — (SO ₂ ) —, —CO—, —CH ₂ —, —CH ＝ CH—, —C (CH ₃ ) 2-, —C (CH ₃ ) (C ₆ H ₅ ) —, e and f are each an integer of 1 or more, and e + f is 2 or more and 30 or less on average.

The polymerizable monomer represented by the above formula (3) is usually obtained in the form of a mixture of molecules having different molecular weights. Therefore, e and f are shown as average values.

As an example of a suitable monomer in the above formula (3),
Bisphenol A dimethacrylate, 2,2-bis (4-methacryloyloxy (polyethoxy) phenyl] propane (f + g = 2.6), 2,2-bis [4-methacryloxy (polyethoxy) phenyl] propane (a + b = 10), 2,2-bis [4-methacryloxy (polyethoxy) phenyl] propane (a + b = 17), 2,2-bis [4-methacryloxy (polyethoxy) phenyl] propane (a + b = 30) 2,2-bis (3,5 -Dibromo-4-methacryloyloxyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propane, bisphenol A diacrylate, 2,2-bis [4-acryloxy (polyethoxy) phenyl] propane (a + b) = 10), 2,2-bis [4-act Proxy (polyethoxy) phenyl] propane (a + b = 20), and the like.

{Component (B514); {Compound represented by Formula (4)} Component (B51)

In the formula, g is an average number of 1 to 20, A and A ′ may be the same or different and each is a linear or branched alkylene group having 2 to 15 carbon atoms, When a plurality of A's are present, the plurality of A's may be the same group or different groups, R ¹¹ is a hydrogen atom or a methyl group, and R ¹² is (meth) acryloyl It is an oxy group or a hydroxyl group.

化合物 The compound represented by the above formula (4) can be produced by reacting polycarbonate diol with (meth) acrylate acid.

Monomers most preferred form by the above formula (4) is a polycarbonate diol and acrylic acid having a number average molecular weight of 500 which is a mixture of pentamethylene glycol and hexamethylene glycol obtained by reacting, R ¹² is acryloyloxy group Is mentioned.

Component (B515); Silselquioxane monomer; Component (B51) The silselquioxane monomer has various molecular structures such as cage, ladder, and random, and is radically polymerizable such as (meth) acrylate group. Monomers having groups are preferred.

例 Examples of such silselquioxane compounds include those represented by the following formula (5).

In the formula, h is the degree of polymerization and is an integer of 3 to 100, and a plurality of R 13 may be the same or different from each other, and may be a radical polymerizable group, an organic group containing a radical polymerizable group, a hydrogen atom. , An alkyl group, a cycloalkyl group, an alkoxy group or a phenyl group, and at least one R ¹³ is a radical polymerizable group or an organic group containing a radical polymerizable group.

Here, the radical polymerizable group or the organic group containing a radical polymerizable group represented by R ¹³ includes a (meth) acrylate group; a (meth) acryloyloxypropyl group, and (3- (meth) acryloyloxypropyl) dimethyl. An organic group having a (meth) acrylate group such as a siloxy group is exemplified.

(B516) component; other (meth) acrylate compound (B51) component Examples of monomers other than the compounds represented by the above formulas (1) to (4) include:
Methoxypolyethylene glycol methacrylate (especially average molecular weight 293), methoxypolyethylene glycol methacrylate (especially average molecular weight 468), methoxypolyethylene glycol acrylate (especially average molecular weight 218), methoxypolyethylene glycol acrylate (especially average molecular weight 454), diethylene glycol dimethacrylate, triethylene glycol Ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, pentaethylene glycol dimethacrylate, pentapropylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaethylene glycol diacrylate, tripropylene glycol diacrylate Dimethacrylate (polyethylene having two repeating units and polypropylene having two repeating units) polyethylene glycol dimethacrylate (especially average molecular weight) comprising a mixture of polypropylene glycol and polyethylene glycol, tetrapropylene glycol diacrylate, pentapropylene glycol diacrylate, 330), polyethylene glycol dimethacrylate (especially average molecular weight 536), polytetramethylene glycol dimethacrylate (especially average molecular weight 736), tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol dimethacrylate (especially average molecular weight 536), Polyethylene glycol diacrylate (especially average molecular weight 258), polyethylene Glycol diacrylate (especially average molecular weight 308), polyethylene glycol diacrylate (especially average molecular weight 508), polyethylene glycol diacrylate (especially average molecular weight 708), polyethylene glycol methacrylate acrylate (especially average molecular weight 536), (polyethylene glycol / polypropylene glycol) Diacrylate copolymer (especially average molecular weight 330), ethoxylated cyclohexanedimethanol acrylate (especially average molecular weight 434), polyester oligomer hexaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, tetrafunctional polyester oligomer (molecular weight 2500-3500, Daicel U. CB, EB80, etc.) 4-functional polyester oligomer (molecular weight 6,000-8) 000, Daicel UCB, EB450, etc.), hexafunctional polyester oligomer (molecular weight 45,000 to 55000, Daicel UCB, EB1830, etc.), tetrafunctional polyester oligomer (particularly Daiichi Kogyo Seiyaku, molecular weight 10,000, GX8488B, etc.), ethylene Glycol bisglycidyl methacrylate, 1,4-butylene glycol dimethacrylate, 1,9-nonylene glycol dimethacrylate, neopentylene glycol dimethacrylate, bis (2-methacryloyloxyethylthioethyl) sulfide, bis (methacryloyloxyethyl) sulfide , Bis (acryloyloxyethyl) sulfide, 1,2-bis (methacryloyloxyethylthio) ethane, 1,2-bis (acryloyloxyethyl) ethane Bis (2-methacryloyloxyethylthioethyl) sulfide, bis (2-acryloyloxyethylthioethyl) sulfide, 1,2-bis (methacryloyloxyethylthioethylthio) ethane, 1,2-bis (acryloyloxyethylthioethyl) Thio) ethane, 1,2-bis (methacryloyloxyisopropylthioisopropyl) sulfide, 1,2-bis (acryloyloxyisopropylthioisopropyl) sulfide, stearyl methacrylate, lauryl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, Lauryl acrylate,
Esters of (meth) acrylate acid, for example, methyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate,
Esters of thioacrylic acid or thiomethacrylic acid, such as methylthioacrylate, benzylthioacrylate, benzylthiomethacrylate,
Polyfunctional urethane (meth) acrylates, for example, U-4HA (molecular weight 596, number of functional groups 4), U-6HA (molecular weight 1019, number of functional groups 6), U-6LPA (molecular weight 818) manufactured by Shin-Nakamura Chemical Co., Ltd. U-15HA (molecular weight 2,300, functional group number 15), U-2PPA (molecular weight 482), UA-122P (molecular weight 1100), U-122P (molecular weight 1100) manufactured by Shin-Nakamura Chemical Co., Ltd. And EB4858 (molecular weight 454) manufactured by Daicel UCB, U-108A, U-200PA, UA-511, U-412A, UA-4100, UA-4200, UA-4400 manufactured by Shin-Nakamura Chemical Co., Ltd. UA-2235PE, UA-160TM, UA-6100, UA-6200, U-108, UA-4000, UA-512 and Honkakusuri (Ltd.) UX-2201, UX3204, include the UX4101,6101,7101,8101.

Component (B52): Vinyl compound Examples of the vinyl compound include styrene, α-methylstyrene, and α-methylstyrene dimer. Examples of the silsesquioxane monomer include compounds in which R ¹³ is a vinyl group; an organic group having a vinyl group such as a vinylpropyl group and a vinyldimethylsiloxy group.

(B53) Component; Allyl Compound Examples of the allyl compound include allyl diglycol carbonate, methoxy polyethylene glycol allyl ether (especially, average molecular weight of 550), methoxy polyethylene glycol allyl ether (especially, average molecular weight of 350), and methoxy polyethylene glycol allyl ether (especially, average molecular weight). 1500). Examples of the silsesquioxane monomer include compounds in which R ¹³ is an allyl group; an organic group having an allyl group such as an allylpropyl group or an allylpropyldimethylsiloxy group.

(B54) Other Radical Polymerizable Monomer In the present invention, a composite polymerizable compound having a plurality of different types of polymerizable groups in the molecule can also be used. Examples of specific compounds include the following. In addition, here, as long as the compound has at least one radical polymerizable group in the molecule, the compound falls under this classification.

Radical polymerization / epoxy type polymer group-containing monomer; component (B54) glycidyl methacrylate, glycidyloxymethyl methacrylate, 2-glycidyloxyethyl methacrylate, 3-glycidyloxypropyl methacrylate, 4-glycidyloxybutyl methacrylate, polyethylene glycol glycidyl methacrylate, polypropylene glycol Glycidyl methacrylate, bisphenol A-monoglycidyl ether-methacrylate, polyethylene glycol glycidyl acrylate, polyethylene glycol glycidyl acrylate.

Radical polymerization / OH type polymer group-containing monomer; (B54) component 2-hydroxymethacrylate, 2-hydroxyacrylate, 2-hydroxypropyl acrylate and the like.

Radical polymerization / isocyanate group-containing monomer; (B54) component 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate and the like.

Radical polymerization / silyl group-containing monomer; (B54) component γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and the like.

In addition to the polymerizable monomers described above, other polymerizable monomers can be used without any limitation. For example, episulfide monomers, thietanyl monomers, and mono (thio) ol monomers can also be used. As preferred specific examples of the episulfide monomer, the thietanyl monomer, and the mono (thio) ol monomer, those described in International Publication No. WO2015 / 068798 can be used.

Curable composition containing component (B5) In the present invention, in the case of a curable composition containing component (B5), that is, when the polymerizable functional group in (A) the polypseudorotaxane monomer is a radical polymerizable group, Is preferably set to the following mixing ratio.

Specifically, the total amount of the component (A) is 2 to 50 parts by mass, and the total amount of the component (B5) is 50 to 98 parts by mass with respect to 100 parts by mass of the total of the component (B5) and the component (A). It is preferred to contain. By including the (A) polypseudorotaxane monomer at this ratio, a photochromic cured product containing a photochromic compound can exhibit excellent photochromic properties and mechanical properties. In order to exhibit the above effects, it is more preferable that the component (A) is in the range of 3 to 40 parts by mass and the total amount of the component (B) is in the range of 60 to 97 parts by mass.

Furthermore, when the total amount of the component (B5) is 100% by mass, 77 to 99% by mass of the component (B51), 0 to 15% by mass of the component (B52), 0 to 5% by mass of the component (B53), and ( B54) The component is preferably from 1 to 3% by mass for the moldability of the cured product. In order to exhibit this effect more, 85 to 99% by mass of the component (B51), 0 to 10% by mass of the component (B52), 0 to 3% by mass of the component (B53), and 1 to 2% by mass of the component (B54). More preferably,

Further, when the above range is satisfied, when the total amount of the component (B51) is 100% by mass, the component (B511) is 5 to 50% by mass, the component (B512) is 0 to 60% by mass, and the component (B513). 0 to 70% by mass, 0 to 20% by mass of the component (B514), 0 to 20% by mass of the component (B515), and 10 to 70% by mass of the component (B516) are preferable for excellent photochromic properties. In order to further exhibit this effect, the component (B511) is 7 to 40% by mass, the component (B512) is 0 to 50% by mass, the component (B513) is 0 to 60% by mass, the component (B514) is 0 to 15% by mass, More preferably, the content of the component (B515) is 0 to 10% by mass and the component (B516) is 15 to 60% by mass.

<Suitable curable composition>
The polymerizable monomer other than (A) the polypseudorotaxane monomer and (B) the polymerizable monomer other than the polypseudorotaxane may be appropriately selected depending on the intended use. For example, when preparing a curable composition containing a photochromic compound, (A) the polymerizable functional group of the cyclic molecule of the polypseudorotaxane monomer includes a hydroxyl group (OH group), a thiol group (SH group), an amino group, Alternatively, the polymerizable monomer is preferably selected from radically polymerizable groups, and the polymerizable monomer (B) is preferably selected from (B1) an iso (thiocyanate) compound, (B5) a radically polymerizable monomer, and the like. When (A) the polymerizable functional group of the cyclic molecule of the polypseudorotaxane monomer is an OH group or an SH group, in addition to the (B1) iso (thia) cyanate compound, the (B3) (thio) ol compound Is preferably used in combination. By doing so, excellent mechanical properties and photochromic properties can be exhibited. Among the above, a particularly high effect is obtained in the present invention when the (B1) iso (thia) cyanate compound is used as the polymerizable monomer (B).

When used for a polishing pad, (A) the polymerizable functional group of the cyclic molecule of the polypseudorotaxane monomer is preferably selected from OH groups and amino groups, and (B) the polymerizable compound is (B1) Preferably, it is selected from (iso) thiocyanate monomers. In particular, when it is used for a polishing pad material, it is preferable to include (B12) a urethane prepolymer among the (B1) poly (iso) thiocyanate compounds. By doing so, the mechanical characteristics of the polishing pad can be improved, and particularly good wear resistance characteristics can be exhibited.

(Other components to be added to the curable composition)
In the curable composition of the present invention, depending on the type of the above-mentioned (A) polypseudorotaxane monomer or (B) the polymerizable functional group introduced into the polymerizable monomer, the polymer-curable composition is rapidly accelerated. Various (C) polymerization curing accelerators can also be used.

(C) Polymerization curing accelerator For example, (A) the case where the polymerizable functional group of the polypseudorotaxane monomer is a polymerizable group such as an OH group, an amino group, an epoxy group, and an SH group; When the component (B) is selected from the (B1) iso (thia) cyanate monomer, a (C1) urethane or urea reaction catalyst or a (C2) condensing agent is used as a polymerization curing accelerator.

(A) The polymerizable functional group of the polypseudorotaxane monomer is a polymerizable functional group such as an OH group, an amino group, and an NCO group, and the component (B) is (B2) an epoxy monomer and an episulfide monomer. When selected from thietanyl monomers, (C3) an epoxy curing agent or (C4) a cationic polymerization catalyst for ring-opening polymerization of an epoxy group is used as a polymerization curing accelerator.

(A) The case where the polymerizable functional group of the polypseudorotaxane monomer is an NCO group or an NCS group, and the component (B) is (B3) a hydroxyl group (thiol group) -containing monomer, and (B4) an amine. When selected from monomers, (C1) a reaction catalyst for urethane or urea or (C2) a condensing agent is used as a polymerization curing accelerator.

(A) When the polymerizable functional group of the polypseudorotaxane monomer is a radical polymerizable group, and when the component (B) is selected from the (B5) radical polymerizable monomer, the (C5) radical A polymerization initiator is used as a polymerization curing accelerator.

重合 As the polymerization accelerators (C1) to (C5) that can be suitably used in the present invention, those described in International Publication No. WO2015 / 068798 can be used as specific examples.

Each of these various (C) polymerization curing accelerators can be used alone or in combination of two or more. However, the amount used may be a so-called catalyst amount. For example, (A) polypseudorotaxane and The amount may be a small amount in the range of 0.001 to 10 parts by mass, particularly 0.01 to 5 parts by mass, per 100 parts by mass of the polymerizable monomer (B) in total.

(D) Photochromic Compound The cured product obtained by curing the curable composition of the present invention may contain (D) a photochromic compound in the cured product depending on the use. As such a use, a photochromic cured product such as photochromic glasses obtained by curing a curable composition containing a photochromic compound is known. Known photochromic compounds can be used as the photochromic compound described above.However, when used as a composition containing a photochromic compound, indenomeric compounds are used from the viewpoint of photochromic properties such as color density, initial coloring property, durability, and fading speed. It is more preferable to use a chromene compound having a [2,1-f] naphtho [1,2-b] pyran skeleton. Particularly, a chromene compound having a molecular weight of 540 or more is preferably used because it is particularly excellent in color density and fading speed. Is done.

Each of these various (D) photochromic compounds can be used alone or in combination of two or more. The amount used may be appropriately determined according to the intended use. For example, 0.001 to 20 parts by mass, particularly 0.01 to 100 parts by mass per 100 parts by mass of the total of (A) the polypseudorotaxane and (B) the polymerizable monomer. It is preferably in the range of 10 parts by mass.

硬化 The curable composition of the present invention can also use various known compounding agents as long as the effects of the present invention are not impaired. For example, abrasives, antioxidants, ultraviolet absorbers, infrared absorbers, coloring inhibitors, fluorescent dyes, dyes, pigments, fragrances, surfactants, flame retardants, plasticizers, fillers, antistatic agents, foam stabilizers , A solvent, a leveling agent, and other additives may be added. These additives may be used alone or in combination of two or more. These additives can be contained in the curable composition, and can be contained in the cured product by polymerizing the curable composition. As for the above-mentioned abrasive grains, specifically, particles made of a material selected from cerium oxide, silicon oxide, alumina, silicon carbide, zirconia, iron oxide, manganese dioxide, titanium oxide and diamond, or two or more of these materials And the like.

A known polymerization method can be adopted. In the case of a polycondensation or polyaddition reaction, the conditions described in WO 2015/068798, WO 2016/143910, and JP-A-2017-48305 can be employed. In the case of radical polymerization, the conditions described in WO2014 / 136804 and WO2015 / 068798 can be employed.

<Cured body>
When the curable composition contains (D) a photochromic compound, a photochromic cured body can be produced by polymerizing and curing as it is.

In addition, the cured product obtained by curing the curable composition of the present invention may have pores in the cured product depending on the use. As such an application, a polishing pad is known. As a method of providing pores in a polishing pad or the like, a known and known foaming method or the like can be used without any limitation. Examples of these methods include a method of dispersing and hardening a volatile foaming agent such as a low-boiling hydrocarbon or the like, and a method of dispersing and hardening a minute hollow body (microballoon). Or a mechanical floss foaming method in which an inert gas such as air or nitrogen is blown during mixing. When a curable composition capable of forming a urethane bond is used for the curable body of the present invention, a foaming agent foaming method in which water or the like is added can also be applied. Further, as the micro hollow body (micro balloon), any known micro balloon can be used without any limitation. When foamed, the density of the matrix resin such as urethane resin is preferably 0.4 to 0.9 g / cm ³ . When a curable composition capable of forming a urethane bond is used for the cured product of the present invention, a foaming agent foaming method in which water or the like is added can also be applied.

<Curing body containing hollow particles>
When the cured product of the curable composition of the present invention is used for a polishing pad or the like, the cured product preferably contains hollow particles such as the above-described minute hollow body (microballoon). That is, it is preferable that a curable composition containing hollow particles is polymerized and cured to produce a cured product containing hollow particles. Here, the matrix resin in the cured product is preferably a urethane resin, and as the curable composition for obtaining the cured product, a curable composition capable of forming a urethane resin is preferably used.

As the hollow particles, known ones can be used without any limitation. It is preferable that the hollow particles include an outer shell and a hollow surrounded by the outer shell. The outer shell is usually formed of a resin. Specific examples thereof include vinylidene chloride resin, (meth) acrylic resin, a copolymer of acrylic monomer and vinylidene chloride, and a copolymer of acrylonitrile and vinylidene chloride. Examples thereof include polymers, epoxy resins, phenol resins, melamine resins, and urethane resins. Above all, the outer shell of the hollow particles is preferably made of a urethane-based resin, and specifically, a hollow shell composed of an outer shell made of a urethane-based resin and a hollow surrounded by the outer shell. It is preferably a particle. The urethane resin is a resin having a urethane bond and / or a urea bond. When these hollow particles are used, a uniform foam can be efficiently and easily produced, defects such as scratches are hardly generated, and hysteresis loss is reduced.

Furthermore, the hollow particles may have a hydrophilic group. For example, when a cured product made of the curable composition of the present invention, for example, a cured product in which the matrix resin is a urethane resin is used as a polishing pad, if the hollow particles have a hydrophilic group, a polishing slurry is used. Compatibility can be improved, and polishing characteristics can be improved. As the hydrophilic group, a hydroxyl group, a thiol group, or an ionic group (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) A group capable of forming).

The average particle size of the hollow particles is not particularly limited, but is preferably in the following range. Specifically, the thickness is preferably 1 μm to 500 μm, more preferably 5 μm to 200 μm.
The density of the hollow particles is not particularly limited, but is preferably in the following range. Specifically, it is preferably 0.01 g / cm ³ to 0.5 g / cm ³ , more preferably 0.02 g / cm ³ to 0.3 g / cm ³ . The density is the density of the hollow particles when expanded. If it is an unexpanded type particle, and it is a hollow particle which is mixed with the curable composition and expands by heat at the time of curing, it is preferable that the density when expanded is the above density.

配合 The blending amount of the hollow particles may be appropriately determined according to the intended use. That is, since it is not an essential component, it may not be included. When hollow particles are included, it is preferable that the amount of the hollow particles is as follows based on the total amount of each monomer component. In addition, the total amount of each monomer component refers to the total amount of the component (A) and the component (B). The compounding amount of the hollow particles is preferably from 0.001 to 20 parts by mass based on 100 parts by mass of the total amount of each monomer component. Further, in order to exhibit more excellent effects by blending the hollow particles, the following blending amount is particularly preferable. Specifically, the amount is preferably 0.02 parts by mass or more and 20 parts by mass or less, more preferably 0.03 parts by mass or more and 10 parts by mass or less based on 100 parts by mass of the total amount of each monomer component.

<Characteristics and compounding agents when used for polishing pads, etc.>
When the present invention is used for a polishing pad or the like, the cured product of the present invention can have any appropriate hardness. Hardness can be measured according to the Shore method, for example, according to JIS standard (hardness test) K6253. When the cured product of the present invention is used for a polishing pad or the like, it preferably has a Shore hardness of 20A to 90D. Further, it is preferably 30A to 70D, more preferably 40A to 50D ("A" indicates the Shore "A" scale, and "D" indicates the hardness on the Shore "D" scale). . That is, when the cured product of the present invention is used as a polishing pad, it is preferably 20 or more in Shore A hardness, more preferably 30 or more in Shore A hardness, still more preferably 40 or more in Shore A hardness, and preferably Has a Shore D hardness of 90 or less, more preferably a Shore D hardness of 70 or less, and still more preferably a Shore D hardness of 50 or less. The hardness may have any hardness by changing the blending composition and blending amount as needed.

In addition, when the cured product of the curable composition of the present invention is used for a polishing pad or the like, it is preferable that the cured product has a certain range of compressibility in order to develop the flatness of the object to be polished. The compression ratio can be measured, for example, by a method based on JIS L 1096. The compression ratio when the cured product of the present invention is used for a polishing pad or the like is preferably 0.5% to 50%. When the content is within the above range, excellent flatness of the object to be polished can be exhibited.
When the cured product of the curable composition of the present invention is used for a polishing pad or the like, the cured product preferably has a hysteresis loss of 60% or less, more preferably 50% or less, and more preferably 40% or less. More preferably, The hysteresis loss can be measured, for example, by a method based on JIS K6251. Specifically, the test piece prepared in the form of a dumbbell is stretched by 100% and then returned to its original state, thereby obtaining a hysteresis loss (elongation when stretched and returned to the original state and the area of stress / elongation when stretched. Stress area × 100) can be measured. By reducing the hysteresis loss, when used as a polishing pad, it is assumed that the kinetic energy of the abrasive grains can be uniformly used for polishing the object to be polished, so that excellent flatness and a high polishing rate are exhibited. It becomes possible. Further, it is considered that the lowering of the hysteresis loss enables a soft pad to exhibit an excellent polishing rate.

When the present invention is used for a polishing pad or the like, a polishing layer formed of a plurality of layers may be provided. For example, when the cured product of the present invention is composed of two layers, the polishing layer includes a first layer having a polishing surface that comes into contact with an object to be polished during polishing, and a surface facing the polishing surface of the first layer. And a second layer in contact with the first layer may be used. In this case, the physical properties of the first layer can be adjusted by making the second layer have a different hardness and elastic modulus from the first layer. For example, by changing the hardness of the first layer and the hardness of the second layer, it is possible to adjust the polishing property of the object to be polished.

硬化 Although the cured product of the present invention is also described above, it may be a so-called fixed abrasive cured product in which abrasive grains are contained as a component. 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 two or more kinds of particles made of these materials. Is mentioned. Furthermore, these abrasives whose surface is modified can also be used. For example, when the cured product of the present invention is used for a polishing pad or the like, by using abrasive particles having a hydrophilic group modified on the surface, the compatibility with slurry or water during polishing is improved, and the polishing characteristics are improved. Becomes possible. As the hydrophilic group, a hydroxyl group, a thiol group, or an ionic group (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) A group capable of forming). The method of holding these abrasive grains is not particularly limited. For example, the abrasive grains can be held in the urethane resin by being dispersed in the curable composition and then cured.

When the present invention is used for a polishing pad or the like, it is not particularly limited, but a groove structure can be formed on the surface thereof. The groove structure is not particularly limited as long as it holds and renews the slurry when the member to be polished is polished. For example, X (stripe) grooves, XY lattice grooves, concentric grooves, through holes , Non-through holes, polygonal columns, cylinders, helical grooves, eccentric circular grooves, radial grooves, and combinations of these grooves.
The manufacturing method of the groove structure is not particularly limited, for example, a method of mechanical cutting using a jig such as a tool of a predetermined size, pouring a resin into a mold having a predetermined surface shape, curing Using a press plate having a predetermined surface shape, a method using a photolithography method, a method using a printing method, a carbon dioxide laser, etc. A method using a laser beam may be used.

The cured product of the present invention is a nonwoven fabric urethane resin obtained by impregnating a non-woven fabric with a curable composition capable of forming the urethane resin of the present invention, for example, in addition to the photochromic cured product described above and the polishing pad, and then curing. It can also be used as a polishing pad. Further, the cured product of the present invention using the urethane resin as a matrix resin can be used as a cushioning material, a vibration damping material, a sound absorbing material, and the like in addition to the above-mentioned polishing pad. Furthermore, the curable composition used in the present invention is applied to or impregnated into a nonwoven fabric and then cured, whereby the nonwoven fabric polishing pad described above, a cushioning material, a vibration damping material, and a sound absorbing material can be applied. .

Next, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the examples. First, the measuring device used in the examples, the method for producing each component, and the like will be described.

(Molecular weight measurement; gel permeation chromatography (GPC measurement))
The GPC measurement was performed using a liquid chromatograph (manufactured by Nippon Waters Co., Ltd.). The columns are Shodex GPC KF-802 (exclusion limit molecular weight: 5000), KF802.5 (exclusion limit molecular weight: 20,000), KF-803 (exclusion limit molecular weight: 70000) according to the molecular weight of the sample to be analyzed. , KF-804 (exclusion limit molecular weight: 400000) and KF-805 (exclusion limit molecular weight: 2,000,000) were appropriately used. The measurement was performed using dimethylformamide (DMF) as a developing solution under the conditions of a flow rate of 1 ml / min and a temperature of 40 ° C. The weight average molecular weight was determined by comparison conversion using polystyrene as a standard sample. Note that a differential refractometer was used as a detector.

Production Example 1
<(A) Method for producing polypseudorotaxane monomer (pRX-1)>
(1-1) Preparation of F 108-Dinh ₂ terminal amine;
As a polymer for forming an axial molecule, a triblock copolymer (Pluronic F108) of linear polyethylene glycol (PEG) -polypropylene glycol (PPG) -polyethylene glycol (PEG) having a weight average molecular weight of 14,600 was prepared.
The following formula;
PEG-PPG-PEG (Pluronic F108) 14g
1.6 g of CDI (1,1′-carbonyldiimidazole)
Was dissolved in 30 mL of dehydrated dichloromethane, and the mixture was stirred at room temperature under a nitrogen atmosphere for 5 hours. Thereafter, 30 mL of water was slowly added dropwise to terminate the reaction. Then, after removing the aqueous layer, the resultant was washed twice with a saturated saline solution, and then water was removed with sodium sulfate. In the obtained dichloromethane solution,
0.6 g of ethylenediamine
Was added and stirred at room temperature for 15 hours. Then, after washing three times again saturated brine, removed the water with sodium sulfate, dichloromethane was distilled off, followed by drying, the F 108-Dinh ₂ with amine groups at both ends of the triblock copolymer 7.5 g were obtained.

(1-2) Preparation of polypseudorotaxane monomer;
4.2 g of F108-diNH ₂ prepared above and 11.9 g of 2-hydroxypropyl-β-cyclodextrin (HP-βCD in which 24% of the total hydroxyl groups of β-cyclodextrin are hydroxypropylated) were added, respectively. Dissolved in 30 mL aqueous solution and stirred at 4 degrees for 2 days. Thereafter, the resultant was dialyzed with a dialysis tube, and dried to obtain 9 g of a polypseudorotaxane monomer (pRX-1).

The physical properties of the obtained polypseudorotaxane monomer (pRX-1) were as follows from the result of NMR.
Axle molecule: triblock copolymer of polyethylene glycol (PEG) -polypropylene glycol (PPG) -polyethylene glycol (PEG) having amino groups (polymerizable groups) at both ends. In the formula (I), an axis molecule in which R ¹⁴ is an ethylene group, R ¹⁵ is a propylene group, and R ¹⁶ is an ethylene group, and i = 120, j = 60, and k = 120 on average.
Inclusion amount of cyclic molecules: 9% (13 β-cyclodextrins are introduced per one axis molecule).
Polymerizable group of the cyclic molecule: hydroxyl group.
Degree of modification of side chain: 0.24 (side chain introduced into 24% of all hydroxyl groups of β-cyclodextrin).
Number average molecular weight of side chain: about 59 on average.
All the terminals of the modified side chains are hydroxyl groups (polymerizable groups).

Reference Production Example 1
<Production method of polyrotaxane monomer (RX-1)>
(2-2) Preparation of polypseudorotaxane monomer;
10. 4.2 g of F108-diNH ₂ prepared in (1-1) above and 2-hydroxypropyl-β-cyclodextrin (HP-βCD in which 24% of all hydroxyl groups of β-cyclodextrin are hydroxypropylated) 9 g each was dissolved in 30 mL aqueous solution and stirred at 4 degrees for 2 days.

(2-3) Terminal Blocking; Preparation of Polyrotaxane Monomer (RX-1) Then, 350 mg of FITC-I (fluorescein isothiocyanate, isomer I type) was added to the mixed solution obtained in (2-2) with dimethylformamide ( A solution dissolved in 3.5 mL of DMF) was added dropwise, and the mixture was stirred at room temperature for 12 hours. Thereafter, the solution was filtered, the solvent was distilled off, and the mixture was dispersed in THF and filtered to obtain a solid. The solid was dissolved in water, dialyzed with a dialysis tube, and dried to obtain a polyrotaxane monomer (RX-1).
Although the end capping was performed in this way, it took more than half a day to manufacture the polypseudorotaxane monomer of Production Example 1, and the cost of the end capping agent also increased.

Physical properties of the obtained polyrotaxane monomer (RX-1) were as follows from the result of NMR.
Inclusion amount of cyclic molecules: 9% (13 β-cyclodextrins are introduced per one axis molecule).
Axle molecule: PEG-PPG-PEG triblock copolymer having fluorescein (bulky group) at both ends. In the formula (I), an axis molecule in which R ¹⁴ is an ethylene group, R ¹⁵ is a propylene group, and R ¹⁶ is an ethylene group, and i = 120, j = 60, and k = 120 on average.
Degree of modification of side chain: 0.24 (side chain introduced into 24% of all hydroxyl groups of β-cyclodextrin).
Side chain molecular weight: about 59 on average.
All the terminals of the modified side chains are hydroxyl groups (polymerizable groups).

(B) a polymerizable monomer;
(B1) Iso (thio) cyanate compound IPDI: isophorone diisocyanate.
NBDI: (bicyclo [2.2.1] heptane-2,5 (2,6) -diyl) bismethylene diisocyanate.
(B12) Prepolymer Pre-1: a terminal isocyanate urethane prepolymer having an iso (thio) cyanate equivalent of 540.
Production example of prepolymer (Pre-1)
Under a nitrogen atmosphere, a flask equipped with a nitrogen inlet tube, a thermometer, and a stirrer was charged with 500 g of 2,4-tolylene diisocyanate, 900 g of polyoxytetramethylene glycol (number average molecular weight; 1000) and 65 g of diethylene glycol at 80 ° C. for 8 hours. The reaction was carried out to obtain a terminal isocyanate urethane prepolymer having an iso (thio) cyanate equivalent of 540 (Pre-1).

(B3) Hydroxyl group (thiol group) -containing monomer TMP: trimethylolpropane.
DEG: diethylene glycol.
HP-BCD: 2-hydroxypropyl-β-cyclodextrin (HP-βCD in which 24% of all hydroxyl groups of β-cyclodextrin are hydroxypropylated).
HP-αCD: 2-hydroxypropyl-α-cyclodextrin (HP-αCD in which 19% of all hydroxyl groups of α-cyclodextrin are hydroxypropylated).
PL1: Duranol (registered trademark, polycarbonate diol, number average molecular weight 500) manufactured by Asahi Kasei Chemicals Corporation.
PELE23: polyoxyethylene lauryl ether (n ≒ 23, Mw = 1198).
PGME10: polyethylene glycol monooleyl ether (n ≒ 10, Mw = 668)

(B4) Amino group-containing monomer F108-diNH ₂ : a monomer produced by the preparation of PEG-PPG-PEG-diNH ₂ having a terminal amine prepared in Production Example (1-1).
F68-diNH ₂ : a monomer produced by the preparation of PEG-PPG-PEG-diNH ₂ having a terminal amine prepared in Production Example (6-1) below.
{PTMG-PEG} -diNH ₂ : a monomer produced by the preparation of {PTMG-PEG (random type)}-diNH ₂ having a terminal amine prepared in Production Example (4-1) below.
(C) Polymerization curing accelerator (C1) Reaction catalyst DBTD for urethane or urea: dibutyltin dilaurate.

(D) Photochromic compound PC1:

(Other)
Hollow particles: Microcapsules 920-40 (manufactured by Nippon Philite). Hollow particles made of a copolymer of an acrylic monomer and vinylidene chloride.
Hollow particles 2: hollow urethane μ balloon having a particle size of 30 μm, the production method is described below.
<Production method of hollow particles 2 / production method of micro balloon made of urethane resin>
To 650 g of polytetramethylene glycol (diol, number average molecular weight 2,000), 1,000 g of toluene was added, and 142 g of isophorone diisocyanate was further added. After cooling to room temperature, 25 g of hexamethylenediamine and 20 g of diethylenetriamine were added and reacted at 60 ° C. for 5 hours. Then, toluene was distilled off under reduced pressure to have hydroxyl groups at both ends and have urethane and urea bonds. A polyurethane resin was obtained. The obtained resin (400 g), iron oxide (12 g), n-hexane (62 g), and ethyl acetate (380 g) were mixed and dispersed dropwise in a previously prepared 2,000 g of 0.5% aqueous solution of polyvinyl alcohol. The obtained resin was taken out of the water by filter paper filtration, and dried with a 40 ° C circulating drier. This spherical body was crushed by a sonic classifier and sieved, and then subjected to a heat treatment with a circulating drier at 150 ° C. for 60 minutes to obtain hollow particles 2.

(Internal release agent)
DBP: di-n-butyltin

Example 1
Using the polypseudorotaxane monomer (pPX-1) produced in Production Example 1, a curable composition was prepared according to the following formulation. The components were mixed to form a uniform liquid (curable composition). Table 1 shows the compounding amounts.
Prescription;
(A) Polypseudorotaxane monomer: pRX-1 6 parts by mass (B12) Prepolymer: pre-1 87 parts by mass (B3) Hydroxyl group (thiol group) -containing monomer: TMP 3 parts by mass (B3) Hydroxyl group (thiol group) Monomer: 4 parts by mass of DEG The above curable composition was stirred and mixed, defoamed, poured into a mold having a thickness of 2 mm, and cured at 100 ° C. for 15 hours. After the polymerization was completed, the urethane resin was removed from the mold to obtain a urethane resin having a thickness of 2 mm.

Ａ The urethane resin obtained above had an A hardness of 35 and a Young's modulus in a tensile test of 0.5 MPa (elastic modulus) elongation of 740%. Each evaluation method is shown below.

〔Evaluation item〕
(1) A hardness: Shore A was measured with a durometer manufactured by Kobunshi Keiki according to JIS standard (hardness test) K6253. The average value was evaluated.
(2) Young's modulus (elastic modulus) and elongation: A resin punched into a dumbbell No. 8 shape having a thickness of 2 mm was subjected to a tensile test at a rate of 10 mm / min using an autograph of AG-SX manufactured by Shimadzu Corporation. The Young's modulus was calculated according to JIS K7161-1.

Comparative Example 1, Reference Example 1
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. Table 1 summarizes the mixing ratio of each component and the results.

As is evident from Example 1 and Comparative Example 1, the cured product produced using the polypseudorotaxane monomer has excellent mechanical properties that are soft and well stretched while having high surface hardness. I understand. These physical properties (physical properties of Example 1) are close to those of the reference example using a polyrotaxane (RX-1) having a bulky group introduced at the terminal, and therefore, in Example 1, as in Reference Example 1, the polypseudorotaxane was used. It can be presumed that the monomer is incorporated into the molecules forming the matrix without leaving the cyclic molecule. However, the elongation rate of Example 1 using the polypseudorotaxane was higher and exhibited an excellent effect.
Therefore, the cured product obtained in Example 1 can be suitably used as a polishing pad.

Production Example 2
<(A) Method for producing polypseudorotaxane monomer (pRX-2)>
(3-2) Preparation of polypseudorotaxane monomer;
As a polymer for forming an axial molecule, a triblock copolymer (Pluronic F108) of linear polyethylene glycol (PEG) -polypropylene glycol (PPG) -polyethylene glycol (PEG) having a weight average molecular weight of 14,600 was prepared.
4.2 g of PEG-PPG-PEG (Pluronic F108) and 11.9 g of 2-hydroxypropyl-β-cyclodextrin (HP-βCD in which 24% of all the hydroxyl groups of β-cyclodextrin are hydroxypropylated) were added, respectively. Dissolved in 30 mL aqueous solution and stirred at 4 degrees for 2 days. Thereafter, the resultant was dialyzed with a dialysis tube and dried to obtain 9 g of a polypseudorotaxane monomer (pRX-2).
The physical properties of the obtained polypseudorotaxane monomer (pRX-2) were as follows from the result of NMR.
Axial molecule: triblock copolymer of polyethylene glycol (PEG) -polypropylene glycol (PPG) -polyethylene glycol (PEG) having hydroxyl groups (polymerizable groups) at both ends. In the formula (I), an axis molecule in which R ¹⁴ is an ethylene group, R ¹⁵ is a propylene group, and R ¹⁶ is an ethylene group, and i = 120, j = 60, and k = 120 on average.
Inclusion amount of cyclic molecules: 9% (13 β-cyclodextrins are introduced per one axis molecule).
Polymerizable group of the cyclic molecule: hydroxyl group.
Degree of modification of side chain: 0.24 (side chain introduced into 24% of all hydroxyl groups of β-cyclodextrin).
Number average molecular weight of side chain: about 59 on average.
All the terminals of the modified side chains are hydroxyl groups (polymerizable groups).
Compared with Reference Production Example 1, there is no step of modifying the terminal of the shaft molecule, and the production time can be reduced even in the process in which the cyclic molecule includes the shaft molecule, and the production can be performed at low cost.

Production Example 3
<(A) Method for producing polypseudorotaxane monomer (pRX-3)>
(4-1) Preparation of {PTMG-PEG (random type)}-diNH _{2 having} terminal amine;
As a polymer for forming an axial molecule, a random copolymer of linear polyoxytetramethylene glycol (PTMG) -polyethylene glycol (PEG) having a weight average molecular weight of terminal hydroxyl group of 3000 was prepared.
The following formula;
<< PTMG-PEG (random type) >> 10g
CDI (1,1′-carbonyldiimidazole) 4 g
Was dissolved in 40 mL of dehydrated dichloromethane, and the mixture was stirred at room temperature for 6 hours under a nitrogen atmosphere. Thereafter, 100 mL of water was slowly added dropwise to terminate the reaction. Then, after removing the aqueous layer, the resultant was washed twice with a saturated saline solution, and then water was removed with sodium sulfate. In the obtained dichloromethane solution,
4 g of ethylenediamine
Was added and stirred at room temperature for 20 hours. Then, after washing three times again with a saturated saline solution, water is removed with sodium sulfate, dichloromethane is distilled off, and the residue is dried to obtain a ΔPTMG-PEG (random) having amine groups at both ends of the random copolymer. (Type) 7 g of｝ -diNH ₂ was obtained.

(4-2) Preparation of polypseudorotaxane monomer;
5 g of {PTMG-PEG (random type)}-diNH ₂ prepared above and 2-hydroxypropyl-α-cyclodextrin (HP-αCD in which 19% of all hydroxyl groups of α-cyclodextrin are hydroxypropylated) 18 6.6 g each was dissolved in 40 mL of aqueous solution and stirred at 4 degrees for 2 days. Thereafter, the resultant was dialyzed with a dialysis tube and dried to obtain 12.5 g of a polypseudorotaxane monomer (pRX-3).
The physical properties of the obtained polypseudorotaxane monomer (pRX-3) were as follows from the result of NMR.
Axial molecule: random copolymer of polyoxytetramethylene glycol (PTMG) -polyethylene glycol (PEG) having amino groups (polymerizable groups) at both ends. In the formula (I), R ¹⁴ is an ethylene group, R ¹⁵ is a butylene group, and R ¹⁶ is an ethylene group, and such a structure exists at random. Equation (I) exists severally in the axis, but when the sum of all of i, j, and k of the existing equation (I) is calculated, about i + k = 34, j = 20 A certain axis molecule.
Inclusion amount of cyclic molecules: 32% (11 α-cyclodextrins are introduced into one axis molecule).
Polymerizable group of the cyclic molecule: hydroxyl group.
Degree of modification of side chain: 0.19 (side chain introduced into 19% of all hydroxyl groups of α-cyclodextrin).
Number average molecular weight of side chain: about 59 on average.
All the terminals of the modified side chains are hydroxyl groups (polymerizable groups).

Reference Production Example 2
<Production method of polyrotaxane monomer (RX-2)>
(5-2) Preparation of polypseudorotaxane monomer;
5 g of {PTMG-PEG (random type)}-diNH ₂ prepared in the above (4-1) and 2-hydroxypropyl-β-cyclodextrin (19% of the total hydroxyl groups of α-cyclodextrin were hydroxypropylated) 18.6 g of each (HP-αCD) were dissolved in 40 mL of an aqueous solution and stirred at 4 ° C for 2 days.
(5-3) Terminal Blocking; Preparation of Polyrotaxane Monomer (RX-2) Then, 360 mg of FITC-I (fluorescein isothiocyanate, isomer I type) was added to the mixed solution obtained in (5-2), using dimethylformamide ( A solution dissolved in 3.5 mL of DMF) was added dropwise, and the mixture was stirred at room temperature for 12 hours. Thereafter, the solution was filtered, the solvent was distilled off, and the mixture was dispersed in THF and filtered to obtain a solid. The solid was dissolved in water, dialyzed with a dialysis tube, and dried to obtain a polyrotaxane monomer (RX-2).
The end-capping was performed in this manner, but compared to the polypseudorotaxane monomer of Production Example 3, the production took more than half a day, and the cost of the end-capping agent also increased.

Production Example 4
<(A) Method for producing polypseudorotaxane monomer (pRX-4)>
(6-1) Preparation of terminal amine F68-diNH ₂ ;
As a polymer for forming an axial molecule, a triblock copolymer (Pluronic F68) of linear polyethylene glycol (PEG) -polypropylene glycol (PPG) -polyethylene glycol (PEG) having a weight average molecular weight of 8300 was prepared.
The following formula;
PEG-PPG-PEG (Pluronic F68) 14g
CDI (1,1′-carbonyldiimidazole) 0.9 g
Was dissolved in 30 mL of dehydrated dichloromethane, and the mixture was stirred at room temperature under a nitrogen atmosphere for 5 hours. Thereafter, 30 mL of water was slowly added dropwise to terminate the reaction. Then, after removing the aqueous layer, the resultant was washed twice with a saturated saline solution, and then water was removed with sodium sulfate. In the obtained dichloromethane solution,
0.3 g of ethylenediamine
Was added and stirred at room temperature for 15 hours. Then, after washing again with a saturated saline solution three times, water was removed with sodium sulfate, dichloromethane was distilled off, and the residue was dried to obtain F68-diNH ₂ having amine groups at both ends of the triblock copolymer. 7.7 g were obtained.
(6-2) Preparation of polypseudorotaxane monomer;
5 g of F68-diNH ₂ prepared above and 12.6 g of 2-hydroxypropyl-β-cyclodextrin (HP-βCD in which 24% of all hydroxyl groups of β-cyclodextrin are hydroxypropylated) were each added to 30 mL of 30 mL. It was dissolved in an aqueous solution and stirred at 4 degrees for 2 days. Thereafter, the resultant was dialyzed with a dialysis tube, and dried to obtain 8.5 g of a polypseudorotaxane monomer (pRX-4).
The physical properties of the obtained polypseudorotaxane monomer (pRX-4) were as follows from the result of NMR.
Axle molecule: triblock copolymer of polyethylene glycol (PEG) -polypropylene glycol (PPG) -polyethylene glycol (PEG) having amino groups (polymerizable groups) at both ends. In the formula (I), an axial molecule in which R ¹⁴ is an ethylene group, R ¹⁵ is a propylene group, and R ¹⁶ is an ethylene group, and i = 75, j = 28, and k = 75 on average.
Inclusion amount of cyclic molecules: 8% (7 β-cyclodextrins are introduced per one axis molecule).
Polymerizable group of the cyclic molecule: hydroxyl group.
Degree of modification of side chain: 0.24 (side chain introduced into 24% of all hydroxyl groups of β-cyclodextrin).
Number average molecular weight of side chain: about 59 on average.
All the terminals of the modified side chains are hydroxyl groups (polymerizable groups).

Reference Production Example 3
<Production method of polyrotaxane monomer (RX-4)>
(7-2) Preparation of polypseudorotaxane monomer;
5 g of F68-diNH ₂ prepared in the above (6-1) and 12.6 g of 2-hydroxypropyl-β-cyclodextrin (HP-βCD in which 24% of all hydroxyl groups of β-cyclodextrin are hydroxypropylated) are added. Each was dissolved in 30 mL of an aqueous solution, and stirred at 4 degrees for 2 days.
(7-3) Terminal Blocking; Preparation of Polyrotaxane Monomer (RX-4) Thereafter, 320 mg of FITC-I (fluorescein isothiocyanate, isomer I type) was added to the mixed solution obtained in (7-2), using dimethylformamide ( A solution dissolved in 3.5 mL of DMF) was added dropwise, and the mixture was stirred at room temperature for 12 hours. Thereafter, the solution was filtered, the solvent was distilled off, and the mixture was dispersed in THF and filtered to obtain a solid. The solid was dissolved in water, dialyzed with a dialysis tube, and dried to obtain a polyrotaxane monomer (RX-4).
The end-capping was performed in this manner, but compared to the polypseudorotaxane monomer of Production Example 4, the production took more than half a day, and the cost of the end-capping agent also increased.

Examples 2-4, Comparative Examples 2-3, Reference Examples 2-3
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 2 was used. The results are shown in Table 2.

Example 5
The following mass parts of the hollow particles were added to the curable composition of Example 1 to prepare a mixture, and the polishing characteristics were confirmed.
Prescription;
(A) Polypseudorotaxane monomer: pRX-1 6 parts by mass (B12) Prepolymer: pre-1 87 parts by mass (B3) Hydroxyl group (thiol group) -containing monomer: TMP 3 parts by mass (B3) Hydroxyl group (thiol group) Monomer: DEG 4 parts by mass (others) Hollow particles: 920-40 0.8 parts by mass The above curable composition was stirred and mixed, defoamed, poured into a mold having a thickness of 10 mm, and heated at 100 ° C. for 15 hours. Cured. After the polymerization was completed, the urethane resin was removed from the mold, and then sliced to a thickness of 1 mm to obtain a urethane resin that could be used as a polishing pad for the CMP method.
The polishing rate of the urethane resin obtained above was 2.2 μm / hr, the scratch resistance was 1, and the Taber abrasion was 30 mg. Table 3 shows the curable composition and the results.

〔Evaluation item〕
(3) Polishing rate: The polishing conditions are shown below.
Polishing pad: 380φ. (A spiral groove is formed.)
Object to be polished: Three 2-inch sapphire wafers.
Slurry: FUJIMI COMPOL 80 stock solution.
Pressure: 411 g / cm ² .
Rotation speed: 60 rpm.
Time: 1 hour.
The polishing rate when polishing was performed under the above conditions was measured.

(4) Scratch (evaluation of scratch resistance): The presence or absence of scratches on the wafer when polished under the conditions described in (3) above was confirmed. The evaluation was performed according to the following criteria.
1: Scratch cannot be confirmed visually or with a laser microscope.
2: Scratch cannot be confirmed by visual observation, but can be confirmed by laser microscope.
3: One or two scratches can be visually confirmed only at the edge portion of the wafer.
4: Three or more scratches can be visually confirmed only at the wafer edge portion, or one or two scratches can be confirmed on the entire wafer.
5: Three or more scratches can be visually confirmed on the entire wafer.

(5) Taber abrasion: Measured with a 5130 type device manufactured by Taber. A Taber abrasion test was performed with a load of 1 kg, a rotation speed of 60 rpm, a rotation number of 1000 rotations, and a worn wheel of H-18.
Comparative Example 4
A cured product was prepared and evaluated in the same manner as in Example 5, except that a curable composition having the composition shown in Table 3 was used. Table 3 summarizes the mixing ratio of each component and the results.

Example 6, Reference Example 4, Comparative Example 4
A cured product was prepared and evaluated in the same manner as in Example 5, except that a curable composition having the composition shown in Table 3 was used. The results are shown in Table 3.

Example 7
According to the following formulation, each component was mixed to prepare a uniform liquid (a curable composition containing a photochromic compound). Table 4 shows the compounding amounts.
Prescription;
(A) polypseudorotaxane monomer: pRX-1 5 parts by mass (B1) iso (thio) cyanate compound: IPDI 49 parts by mass (B3) hydroxyl group (thiol group) -containing monomer: PL1 21 parts by mass (B3) hydroxyl group (thiol group) ) Containing monomer: 17 parts by mass of TMP (B3) Monomer containing hydroxyl group (thiol group): 8 parts by mass of PELE23 (D) Photochromic compound: 4 parts by mass of PC1 (Others) DBTD: 0.01 part by mass Curing containing the above photochromic compound Using the conductive composition, a photochromic laminate was obtained by the following method.
A thiourethane-based plastic lens having a center thickness of about 2 mm, a spherical power of −6.00D, and a refractive index of 1.60 was prepared as an optical base material. The thiourethane-based plastic lens was preliminarily subjected to alkaline etching at 50 ° C. for 5 minutes using a 10% aqueous sodium hydroxide solution, and then sufficiently washed with distilled water.
The curable composition was dropped on the surface of the plastic lens rotated at 2000 rpm using a spin coater (1H-DX2, manufactured by MIKASA). Thereafter, the mixture was polymerized and cured by heating at 120 ° C. for 1 hour to obtain a photochromic laminate. The thickness of the photochromic layer was about 30 μm.
The obtained photochromic laminate exhibited photochromic characteristics with a maximum absorption wavelength of 580 nm, a coloring density of 0.78, and a fading speed of 59 seconds, and had a Vickers hardness of 12. The evaluation of the maximum absorption wavelength, color density, fading speed, and Vickers hardness was performed by the following methods.

〔Evaluation item〕
(6) Maximum absorption wavelength (λmax): The obtained photochromic laminate was used as a sample, and a xenon lamp L-2480 (300 W) SHL-100 manufactured by Hamamatsu Photonics was passed through an aeromass filter (manufactured by Corning). At 120 ° C. ± 1 ° C. at a beam intensity of 365 nm = 2.4 mW / cm ² and 245 nm = 24 μW / cm ² on the surface of the laminate for 120 seconds to develop color, and a spectrophotometer manufactured by Otsuka Electronics Co., Ltd. This is the maximum absorption wavelength after color development determined by the instant multi-channel photodetector (MCPD1000). The maximum absorption wavelength is related to the color tone at the time of color development.
(7) Color density {ε (120) −ε (0)}: difference between absorbance at the maximum absorption wavelength after light irradiation for 120 seconds {ε (120)} and light absorbance before light irradiation ε (0) It is. It can be said that the higher this value is, the more excellent the photochromic property is. Further, when the color was developed outdoors, the color tone was evaluated visually.
(8) Fading speed [t1 / 2 (sec.)]: After irradiation with light for 120 seconds, when the irradiation of light is stopped, the absorbance of the sample at the maximum absorption wavelength is {ε (120) −ε (0)}. The time it takes to drop to half of It can be said that the shorter this time is, the more excellent the photochromic property is.
(9) Vickers hardness: The Vickers hardness of the obtained photochromic layer was measured using a micro Vickers hardness meter PMT-X7A (manufactured by Matsuzawa Corporation). A quadrangular pyramidal diamond indenter was used as the indenter, and the evaluation was performed under the conditions of a load of 10 gf and an indenter holding time of 30 seconds. The measurement results were shown as an average value of three measurements, excluding the first value having a large measurement error, after performing the measurement four times in total.

Reference Example 5, Comparative Example 5
A cured product was prepared and evaluated in the same manner as in Example 7, except that a curable composition having the composition shown in Table 4 was used. The results are shown in Table 4.

Example 8
According to the following formulation, each component was mixed to prepare a uniform liquid (a curable composition containing a photochromic compound). Table 5 shows the compounding amounts.
Prescription;
(A) Polypseudorotaxane monomer: 9 parts by mass of pRX-1 (B1) Iso (thio) cyanate compound: 46 parts by mass of NBDI (B3) Monomer containing hydroxyl group (thiol group): 19 parts by mass of PL1 (B3) Hydroxyl group (thiol group) ) -Containing monomer: 15 parts by mass of TMP (B3) Monomer containing hydroxyl group (thiol group): 11 parts by mass of PGME10 (D) Photochromic compound: 0.04 parts by mass of PC1 (Others): 0.1 part by mass of DBP A photochromic cured product was obtained by a kneading method using the curable composition containing the composition. The polymerization method is described below.
After the uniform liquid of the curable composition has been sufficiently defoamed, it is poured into a mold made of a mold made of a glass mold subjected to a release treatment and a gasket made of an ethylene-vinyl acetate copolymer. did. Next, the mixture was cured for 15 hours while gradually raising the temperature from 30 ° C. to 95 ° C. After the polymerization was completed, the photochromic cured product was removed from the glass mold of the mold. The obtained photochromic cured product had a maximum absorption wavelength of 580 nm, a color density of 0.76, and a fading speed of 61 seconds. Further, the handling properties of the photochromic composition and the moldability of the obtained photochromic cured product were also good. Further, the L-scale Rockwell hardness (HL) of the obtained photochromic cured product was 75. The L scale rock well hardness was measured as follows.
〔Evaluation item〕
(10) L-scale Rockwell hardness (HL): After keeping the above cured product in a room at 25 ° C. for 1 day, using an Akashi Rockwell hardness tester (model: AR-10), the L-scale of the photochromic cured product was obtained. Lurockwell hardness was measured.

Reference Example 6, Comparative Example 6
A cured product was prepared and evaluated in the same manner as in Example 8, except that a curable composition having the composition shown in Table 5 was used. Table 5 shows the results.

1: polypseudorotaxane monomer 2: axial molecule 3: cyclic molecule 4: side chain

Claims (12)

1. It has a complex molecular structure consisting of a cyclic molecule having a polymerizable functional group and a shaft molecule penetrating through the ring of the cyclic molecule, and has no bulky group at at least one end of the shaft molecule ( A) a polypseudorotaxane monomer, and
   A curable composition containing (B) a polymerizable monomer other than the (A) polypseudorotaxane monomer.
2. The curable composition according to claim 1, wherein the axis molecule of the (A) polypseudorotaxane monomer comprises a copolymer obtained by polymerizing a plurality of monomers.
3. The copolymer of the axial molecule of the (A) polypseudorotaxane monomer,
   The curable composition according to claim 2, which is a block copolymer composed of a plurality of different polyalkylene glycol moieties.
4. 4. The method according to claim 1, wherein the polymerizable functional group of the cyclic molecule of the (A) polypseudorotaxane monomer is a hydroxyl group, a thiol group, an amino group, a carboxyl group, a (meth) acrylate group, or an allyl group. The curable composition according to the above.
5. (5) The curable composition according to any one of (1) to (4), wherein a polymerizable functional group is introduced into the terminal of the axis molecule of the polypseudorotaxane monomer.
6. The curable composition according to claim 5, wherein the polymerizable group functional group of the axial molecule of the (A) polypseudorotaxane monomer is a hydroxyl group, a thiol group, an amino group, a carboxyl group, a (meth) acrylate group, or an allyl group. Composition.
7. (A) the polymerizable functional group of the cyclic molecule of the polypseudorotaxane monomer contains a hydroxyl group, a thiol group, a carboxyl group, or an amino group;
   7. The curable composition according to claim 1, wherein the polymerizable monomer (B) is (B1) an iso (thio) cyanate compound having an iso (thio) cyanate group.
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. The polishing pad according to claim 9, wherein the cured product further comprises hollow particles.
11. (8) The curable composition according to any one of (1) to (7), further comprising (C) a photochromic compound.
12. A photochromic cured product obtained by curing the curable composition according to claim 11.
    

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