Film, eyeglass lens, composition

Abstract

The present invention addresses the problem of providing a film which has low haze and exhibits excellent adhesion to a primer layer. This film contains core-shell particles having: a core part; a first shell part that covers the core part; and a second shell part that covers the first shell part. The core part contains an inorganic oxide particle or a silsesquioxane. The first shell part contains a polymer chain A that contains one or more types selected from the group consisting of an acrylate-based polymer chain and a methacrylate-based polymer chain. The second shell part contains a polymer chain B obtained by cationic polymerization of oxetanyl groups in an oxetanyl group-containing compound.

Description

[Technical Field]

[0001] The present disclosure relates to films, eyeglass lenses, and compositions. [Background technology]

[0002] Patent Document 1 discloses a hard coat layer formed by curing a composition containing inorganic oxide particles, an organic silicon compound, and the like. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2015 / 163465 Summary of the Invention

[0004] The present disclosure relates to a film comprising a core-shell particle having a core, a first shell covering the core, and a second shell covering the first shell, wherein the core comprises an inorganic oxide particle or a silsesquioxane, the first shell comprises a polymer chain A including one or more selected from the group consisting of acrylate polymer chains and methacrylate polymer chains, and the second shell comprises a polymer chain B obtained by cationic polymerization of the oxetanyl group of a compound having an oxetanyl group. [Brief explanation of the drawings]

[0005] [Figure 1] 1 is an example showing a presumed cross-sectional structure of a core-shell particle. [Figure 2] 1 is an example showing a cross section of a spectacle lens. DETAILED DESCRIPTION OF THE INVENTION

[0006] The membranes of the present disclosure are described in detail below. The film of the present disclosure is preferably used, for example, as a hard coat layer for eyeglass lenses. The hard coat layer of an eyeglass lens is required to have low haze and excellent adhesion to a primer layer. The film of the present disclosure can be used as a hard coat layer having the above properties.

[0007] In this specification, the symbol "to" means that the numerical values ​​before and after it are included as the lower limit and upper limit. In this specification, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. As used herein, halogenation includes, for example, fluorination, chlorination, bromination and iodination. In this specification, "(meth)acrylic" is a concept that encompasses both acrylic and methacrylic, and "(meth)acryloyl group" is a concept that encompasses both acryloyl group and methacryloyl group.

[0008] In this specification, the solid content refers to components other than the solvent, and is calculated as the solid content even if the component is liquid at room temperature and normal pressure (25°C, 101.3 kPa). The solid content may also be a component that undergoes chemical changes during the curing process. However, when the composition, living polymerization mixture, and cationic polymerization mixture described below contain a specific compound selected from the group consisting of a surfactant that is liquid at room temperature and normal pressure, a living polymerization catalyst that is liquid at room temperature and normal pressure, and a co-catalyst that is liquid at room temperature and normal pressure, the solid content of the composition, living polymerization mixture, and cationic polymerization mixture described below does not include the amount of the specific compound. For example, in a composition consisting of core-shell particles, a surfactant that is liquid at room temperature and normal pressure, and a solvent, only the amount of the core-shell particles corresponds to the solid content of the composition.

[0009] The various components contained in the film will be described in detail below.

[0010] [film] <Core-shell particles> The film comprises core-shell particles. The core-shell particle has a core portion, a first shell portion, and a second shell portion. FIG. 1 shows an example of a presumed cross-sectional structure of a core-shell particle. The core-shell particle 100 is a particle having a core-shell structure, and has a core portion 102, a first shell portion 104 covering the core portion, and a second shell portion 106 covering the first shell portion. Note that in FIG. 1, the relationship in thickness between the various portions is not limited to the relationship shown in FIG. 1 and can be adjusted as appropriate. Also, in FIG. 1, the entire surface of the core portion is covered with the first shell portion, and the entire surface of the first shell portion is covered with the second shell portion, but it is also possible for only a portion of the surface of the core portion to be covered with the first shell portion, and only a portion of the surface of the first shell portion to be covered with the second shell portion.

[0011] (Core part) The core-shell particles have a core portion. The core portion contains inorganic oxide particles or silsesquioxane (hereinafter also referred to as "inorganic oxide particles, etc."). Silsesquioxane, which will be described later, is not included in the inorganic oxide particles. Furthermore, as will be described later, inorganic oxide particles and the like may have functional groups and / or initiation sites, and when these functional groups and initiation sites constitute part of the polymer chain A, these functional groups and initiation sites are classified as the first shell portion. In other words, the core portion may be composed essentially of metal and metal oxide only. Specifically, the content of metal and metal oxide may be 90 to 100 mass% of the total mass of the core portion, and more preferably 99 to 100 mass%.

[0012] Inorganic oxide particles As the inorganic oxide particles, metal oxide particles are preferred. Examples of inorganic oxide particles include oxide particles of one or more metals selected from the group consisting of Ti, Zr, Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, and In, as well as composite oxide particles thereof. Composite oxide particles are oxide particles containing two or more metals (metal atoms). The inorganic oxide particles may contain one or more selected from the group consisting of SiO2 (silicon dioxide), Al2O3 (aluminum oxide), SnO2 (tin oxide), ZrO2 (zirconium oxide) and TiO2 (titanium oxide), more preferably contain one or more selected from the group consisting of SiO2 and ZrO2, and even more preferably contain SiO2. The inorganic oxide particles may be commercially available products, such as a sol in which one or more inorganic oxide particles selected from the group consisting of SiO, AlO, SnO, ZrO, TiO, and composite oxide particles thereof are dispersed in water or an organic solvent. The inorganic oxide particles may be surface-treated. Examples of surface treatments include the introduction of various functional groups and treatments using known surface modifiers. Examples of surface-treated inorganic oxide particles include inorganic oxide particles having initiation sites on the surface, which will be described later.

[0013] The inorganic oxide particles may have an average particle size of 0.5 to 70 nm, more preferably 1 to 50 nm. Examples of methods for measuring the average particle size include a method in which the particle sizes of 100 random inorganic oxide particles are measured using a scanning electron microscope and then the arithmetic average is calculated, and a method in which the particle size is measured using a dynamic light scattering method under the following conditions. Measurement equipment: Zeta potential and particle size measurement system ELS-Z2 (Otsuka Electronics Co., Ltd.) Measurement cell: particle size cell unit (scattering angle 165°) Measurement temperature: 25℃ Particle size analysis method: Contin method During measurement, the inorganic oxide particles to be measured or a dispersion containing the inorganic oxide particles to be measured is diluted with a dilution solvent as needed. For example, MEK (methyl ethyl ketone) is used as the dilution solvent. If the use of MEK causes problems such as aggregation of the inorganic oxide particles, another appropriate dilution solvent is used. In addition, in the present disclosure, unless otherwise specified, the average particle size refers to the average particle size on a volume distribution basis.

[0014] Silsesquioxane Silsesquioxane is a silane compound having a basic skeleton represented by formula (Q) that can be obtained by hydrolyzing a trifunctional silane compound such as an alkoxysilane, a chlorosilane, or a silanol. Examples of the silsesquioxane structure include irregular structures such as random structures, ladder structures, cage (fully condensed cage) structures, and incomplete cage structures (partially cleaved cage structures in which some of the silicon atoms are missing from the cage structure and some of the silicon-oxygen bonds in the cage structure are broken).

[0015] R Q -SiO 3 / 2 (Q) In formula (Q), R Q represents a monovalent organic group.

[0016] Examples of silsesquioxanes include the SQ series (for example, AC-SQ series and MAC-SQ series, manufactured by Toagosei Co., Ltd.).

[0017] The average particle size of the silsesquioxane may be 0.5 to 200 nm, more preferably 1 to 50 nm. The average particle size can be measured in the same manner as for the inorganic oxide particles.

[0018] The content of the core part may be 10 to 90% by mass, more preferably 60 to 90% by mass, based on the total mass of the core-shell particles. The content of the inorganic oxide particles or the content of the silsesquioxane may be within the above-mentioned preferred ranges based on the total mass of the core-shell particles.

[0019] (First shell part) The core-shell particles have a first shell portion that covers a core portion. The first shell portion contains polymer chains A and covers part or all of the core portion. In other words, at least a part of the surface of the inorganic oxide particle or silsesquioxane that forms the core portion is modified with polymer chains A.

[0020] ·Polymer chain A The first shell portion includes a polymer chain A. The polymer chain A is a polymer chain containing at least one selected from the group consisting of acrylate-based polymer chains and methacrylate-based polymer chains. The polymer chain A may cover the core portion by any of, for example, a covalent bond, a coordinate bond, an ionic bond, a hydrogen bond, a van der Waals bond, and a metallic bond, and a covalent bond is more preferred.

[0021] The acrylate polymer chain is a polymer chain having a repeating unit derived from a compound X1 having an acryloyl group, and the methacrylate polymer chain is a polymer chain having a repeating unit derived from a compound X2 having a methacryloyl group. Hereinafter, compound X1 and compound X2 will also be collectively referred to as "compound X."

[0022] The compound X may be a monofunctional compound X or a polyfunctional compound X, and a polyfunctional compound X is more preferred. When a polyfunctional compound X is used, a branched structure and / or a network structure (crosslinked structure) can be introduced into the polymer chain A to be formed, resulting in excellent scratch resistance. The number of (meth)acryloyl groups that the compound X has may be 1 or 2 or more, and 2 to 5 is more preferred. The compound X may have other functional groups in addition to the (meth)acryloyl group, such as a hydroxy group and ethylenically unsaturated groups such as a vinyl group and a styryl group.

[0023] The compound X may be a compound represented by formula (X).

[0024] [ka]

[0025] In formula (X), R Xrepresents a hydrogen atom or a substituent. The substituent may be an organic group, and a methyl group is more preferable. X They may be the same or different. k represents an integer of 2 or more, and may be an integer of 2 to 10, more preferably 2 or 3, and even more preferably 3.

[0026] Z represents a k-valent linking group, provided that when k is 2, Z may be a single bond. The k-valent linking group may have 1 to 500 atoms other than hydrogen atoms. Examples of the k-valent linking group include an ether group (-O-), a carbonyl group (-CO-), an ester group (-COO-), a thioether group (-S-), a urethane group (-NHCOO-), -SO2-, and -NR N -(R N represents a hydrogen atom or a substituent), divalent linking groups such as alkylene groups (preferably having 1 to 10 carbon atoms), alkenylene groups (preferably having 2 to 10 carbon atoms), and alkynylene groups (preferably having 2 to 10 carbon atoms); trivalent linking groups having a group represented by "-N<" and trivalent linking groups having a group represented by "-CH<"; tetravalent linking groups having a group represented by ">C<"; k-valent linking groups having a cyclic group such as an aromatic ring group or an alicyclic group (preferably a k-valent cyclic group); and groups combining these. The ring group constituting the k-valent linking group having the ring group may contain a heteroatom. Examples of the aromatic ring group include a benzene ring group, a naphthalene ring group, and a bisphenol ring group such as a ring group formed by removing any hydrogen atom from a bisphenol compound such as bisphenol A. Examples of the alicyclic group include cycloalkane ring groups such as a cyclohexane ring group, a cyclopentane ring group, and a tricyclodecane ring group, a dioxane ring group, and an isocyanuric ring group, with an isocyanuric ring group being more preferred. The alkylene group, alkenylene group, alkynylene group and cyclic group may further have a substituent, if possible.

[0027] When Z is a divalent linking group, Z may have one or more groups selected from the group consisting of an alkylene group, a (poly)oxyalkylene group, and a urethane group. Also, there are k instances of "R X The atom directly bonded to the group represented by "-C(=CH2)-CO-" (the group in parentheses in formula (A)) may be an oxygen atom.

[0028] The compound X is not particularly limited as long as it is a compound having a (meth)acryloyl group. Examples of the compound X include tris(2-acryloxyethyl)isocyanurate, caprolactone-modified tris-(2-acryloxyethyl)isocyanurate, 2-hydroxy-3-methacrylpropyl acrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, and tricyclodecane dimethanol diacrylate.

[0029] The polymer chain A may have other repeating units in addition to the repeating units derived from the compound X.

[0030] When the polymer chain A contains a repeating unit derived from a polyfunctional compound X (preferably a compound represented by formula (X)), the content thereof may be 10 to 100 mass %, more preferably 50 to 100 mass %, based on the total mass of the polymer chain A.

[0031] The content of the first shell portion may be 5 to 80 mass % relative to the total mass of the core-shell particle, and more preferably 20 to 80 mass %. The content of the polymer chain A may be 30 to 100% by mass, more preferably 30 to 90% by mass, based on the total mass of the first shell portion.

[0032] The polymer chain A may be a polymer chain obtained by living radical polymerization. An example of living radical polymerization is step 1 described below. If polymer chain A is synthesized by living radical polymerization, the molecular weight distribution of polymer chain A can be narrowed, and the core-shell particles can be uniformly dispersed in the film and composition, resulting in lower haze and better film hardness.

[0033] (Second shell part) The core-shell particle has a second shell portion covering the first shell portion. The second shell portion contains polymer chain B and covers part or all of the second shell portion. In other words, at least a part of the surface of the first shell portion opposite to the core portion side is modified with polymer chain B.

[0034] ·Polymer chain B The second shell portion includes a polymer chain B. The polymer chain B is a polymer chain B obtained by cationic polymerization of the oxetanyl group of a compound having an oxetanyl group (hereinafter also referred to as "compound Y"). Compound Y is reacted with a cationic polymerization initiator or the like to generate an oxonium cation derived from the oxetanyl group of compound Y, and the oxonium cation causes cationic polymerization of compounds Y together to obtain polymer chain B. In other words, polymer chain B has a polyether structure generated by ring-opening of the oxetanyl group of compound Y. As will be described later, when first shell particles having a cationically polymerizable group are used, the cationically polymerizable group can be involved in the cationic polymerization. The polymer chain B may cover the first shell portion by any of, for example, a covalent bond, a coordinate bond, an ionic bond, a hydrogen bond, a van der Waals bond, and a metallic bond, and a covalent bond is more preferable.

[0035] ·Compound Y Compound Y is a compound having an oxetanyl group, and polymer chain B can be synthesized by cationic polymerization of compound Y. The polymer chain B may have a repeating unit formed by cationic polymerization of the oxetanyl group of the compound Y.

[0036] The compound Y may be a monofunctional compound Y or a polyfunctional compound Y, and a polyfunctional compound Y is more preferred. When a polyfunctional compound Y is used, a branched structure and / or a network structure (crosslinked structure) can be introduced into the polymer chain B to be formed, resulting in excellent scratch resistance. The number of oxetanyl groups that compound Y has may be 1 or 2 or more, more preferably 2 to 5, and even more preferably 2 or 3. Compound Y may have a functional group other than an oxetanyl group, such as a hydroxy group, or an ethylenically unsaturated group such as a (meth)acryloyl group, a vinyl group, or a styryl group. Examples include:

[0037] The compound Y may be a compound represented by formula (Y).

[0038] [ka]

[0039] In formula (Y), R Y represents a hydrogen atom or an alkyl group. Y is n Y represents an n-valent linking group. Y represents an integer of 2 or more, where n Y If is 2, L Y may be a single bond. Y They may be the same or different.

[0040] R Y represents a hydrogen atom or an alkyl group. The alkyl group may be linear, branched, or cyclic. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, with an ethyl group being more preferred.

[0041] LY is n Y represents a valent linking group. Above n Y Examples of the k-valent linking group include k-valent linking groups, which may be -O-, an alkylene group, an aromatic ring group, or a group formed by combining these. Examples of the above groups formed by combining these include -alkylene group-O-alkylene group-.

[0042] n Y represents an integer of 2 or more, where n Y If is 2, L Y may be a single bond. n Y may be an integer of 2 to 5, with 2 or 3 being more preferred.

[0043] Examples of compound Y include xylylene bisoxetane, compound S described below, and 3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane.

[0044] L in compound S S represents a benzene ring or an alkylene group. The benzene ring may have at least one selected from the group consisting of an alkyl group, an amino group, and a hydroxy group. The alkylene group may have at least one selected from the group consisting of an amino group and a hydroxy group. The alkyl group and the alkylene group preferably have 1 to 3 carbon atoms.

[0045] [ka]

[0046] The polymer chain B may have other repeating units in addition to the repeating units formed by cationic polymerization of the oxetanyl groups of the compound Y. Examples of other repeating units include repeating units that the polymer chain A may have.

[0047] The content of the repeating unit formed by cationic polymerization of the oxetanyl group of compound Y (preferably a compound represented by formula (Y)) may be 50 to 100 mass % relative to the total mass of polymer chain B, and more preferably 80 to 100 mass %.

[0048] <Other ingredients> The film may contain other components in addition to the core-shell particles. Examples of other components include particles other than core-shell particles; various components contained in the composition described below, their reaction products and decomposition products; and polymer compounds. Examples of the polymer compound include a polymer compound obtained by polymerizing a compound X and / or a compound Y, and a polymer compound containing a polymer chain A and / or a polymer chain B.

[0049] <Method of manufacturing core-shell particles> The core-shell particles can be produced by, for example, a known method. Specifically, the method for producing core-shell particles having a core portion, a first shell portion covering the core portion, and a second shell portion covering the first shell portion includes the steps of: Step 1 of forming a first shell portion by reacting inorganic oxide particles or the like having initiation sites on their surfaces with compound X; and step 2, in which the oxetanyl group of a compound having an oxetanyl group (compound Y) is cationic polymerized to form a second shell portion that covers the first shell portion.

[0050] (Process 1) Step 1 is a step of synthesizing a polymer chain A by reacting an initiation site of an inorganic oxide particle or the like with a compound X, and then covering the core with a first shell containing the polymer chain A. Step 1 may be, for example, a step of synthesizing polymer chain A by living polymerization of an initiation site on inorganic oxide particles or the like with compound X, and covering the core portion with polymer chain A.

[0051] Step 1 may be a step of reacting a mixture for living polymerization, which will be described later. The living polymerization may be living radical polymerization, and the living radical polymerization may be atom transfer radical polymerization.

[0052] The living polymerization mixture may include compound X and a living polymerization catalyst, such as inorganic oxide particles having initiation sites on their surfaces. As one embodiment of Step 1, Step 1 in which the above-mentioned mixture for living polymerization is reacted will be described in detail below.

[0053] Inorganic oxide particles with initiation sites on the surface The inorganic oxide particles or the like having an initiation site on the surface are inorganic oxide particles or the like having groups on the surface that serve as initiation sites for living radical polymerization. The inorganic oxide particles and the like are as described above.

[0054] The initiation site may be, for example, a halogenated organic group. The initiation site may be, for example, a site having a group represented by formula (S1), and is more preferably a site having a group represented by formula (S2).

[0055] [ka]

[0056] In formula (S1), * represents a bonding position, and X represents a halogen atom. R S1 and R S2 each independently represents a hydrogen atom or a substituent. The substituent may be an organic group, and is preferably a hydrocarbon group. The substituent preferably has 1 to 20 carbon atoms.

[0057] L S1 represents a divalent linking group. Examples of the divalent linking group include an ether group, a carbonyl group, an ester group, a thioether group, -SO2-, and -NR N-(R N represents a hydrogen atom or a substituent), alkylene groups (preferably having 1 to 10 carbon atoms), alkenylene groups (preferably having 2 to 10 carbon atoms), alkynylene groups (preferably having 2 to 10 carbon atoms), aromatic ring groups (for example, a benzene ring group), alicyclic groups, and groups formed by combining these groups. The alkylene group, the alkenylene group, the alkynylene group, the aromatic ring group and the alicyclic group may further have a substituent (for example, a hydroxy group, etc.) if possible.

[0058] In formula (S2), * represents a bonding position, and X represents a halogen atom. R S1 and R S2 each independently represents a hydrogen atom or a substituent. The substituent may be an organic group, more preferably a hydrocarbon group, and may have 1 to 20 carbon atoms. L S2 represents an alkylene group which may have a substituent. The alkylene group may be linear or branched and may have 1 to 12 carbon atoms. An example of the substituent that the alkylene group may have is a hydroxy group.

[0059] Examples of methods for producing inorganic oxide particles or the like having initiation sites on their surfaces include a method in which inorganic oxide particles or the like having groups having ethylenically unsaturated groups (e.g., (meth)acryloyl groups, etc.) fixed to the surfaces of the inorganic oxide particles or the like are reacted with epihalogenhydrin (e.g., epichlorohydrin, etc.) in the presence of aluminum trichloride.

[0060] In this case, the content of the inorganic oxide particles, etc. having ethylenically unsaturated groups fixed to their surfaces may be 70 to 99.9 mass%, more preferably 90 to 99 mass%, based on the total content of the inorganic oxide particles, etc. having ethylenically unsaturated groups fixed to their surfaces, aluminum trichloride, and epihalogenhydrin. The content of aluminum trichloride relative to the total content may be 0.01 to 5 mass %, more preferably 0.05 to 1 mass %. The content of epihalogenhydrin relative to the total content may be 0.05 to 30 mass %, more preferably 0.5 to 10 mass %. After carrying out a reaction to produce inorganic oxide particles having initiation sites on their surfaces using a composition containing inorganic oxide particles or the like having groups having ethylenically unsaturated groups fixed to their surfaces, aluminum trichloride, and epihalohydrin, the composition that has undergone the reaction may be used as is to prepare a mixture for living polymerization.

[0061] The inorganic oxide particles or the like having groups having an ethylenically unsaturated group fixed to the surface thereof may be prepared, for example, by reacting inorganic oxide particles or the like with a silane coupling agent having an ethylenically unsaturated group (e.g., a (meth)acryloyl group, etc.), or commercially available products may be used.

[0062] The inorganic oxide particles having initiation sites on the surface may be used alone or in combination of two or more kinds. The content of inorganic oxide particles or the like having initiation sites on the surface may be 20 to 99.5 mass % relative to the total solid content of the mixture for living polymerization, and more preferably 30 to 96 mass %.

[0063] ·Compound X Examples of the compound X include the compounds X described in the first shell portion and the polymer chain A, and preferred embodiments are also the same. The compound X may be used alone or in combination of two or more. The content of compound X may be 0.1 to 60 mass %, more preferably 0.2 to 50 mass %, based on the total solid content of the mixture for living polymerization. The content of compound X may be 0.01 to 110 mass %, more preferably 0.05 to 40 mass %, based on the total mass of the inorganic oxide particles having initiation sites on the surface thereof.

[0064] Living polymerization catalyst Living polymerization catalysts include, for example, transition metals and transition metal compounds. Examples of the transition metal in the transition metal and transition metal compound include copper, iron, cobalt, chromium, manganese, molybdenum, silver, zinc, palladium, rhodium, platinum, ruthenium, iridium, ytterbium, samarium, rhenium, and nickel, and may be copper, iron, or ruthenium. The transition metal compound may be a transition metal complex comprising the transition metal and a ligand.

[0065] The living polymerization catalyst may be an iron compound (eg, ferrocenes, etc.). The iron compound may be a compound represented by formula (F1) or a compound represented by formula (F2). CP 1 -Fe-CP 2 (F1) CP 1 -Fe-(R Q )3(F2)

[0066] In formula (F1), CP 1 and CP 2 each independently represents a cyclopentadienyl ring which may have a substituent. The cyclopentadienyl ring may have 0 to 5 substituents, and 1 is more preferred. The substituent that the cyclopentadienyl ring may have is —P(R P )2 may also be used. The above "-P(R P )2" P is a phosphorus atom, and two R P each independently represents a hydrogen atom or a substituent. The substituent may be an organic group, more preferably an alkyl group or a phenyl group. The alkyl group may be linear or branched and may have 1 to 3 carbon atoms.

[0067] In formula (F2), CP 1 represents a cyclopentadienyl ring which may have a substituent. 1is the CP in equation (F1) 1 is the same as: In formula (F2), three R Q each independently represents -CO, a halogen atom, or -PPh3. In the above "-PPh3," P is a phosphorus atom, and Ph is a phenyl group which may have a substituent. The substituent which the phenyl group may have may be an alkyl group. The alkyl group may be linear or branched, and may have 1 to 3 carbon atoms. The phenyl group may have 0 to 5 substituents.

[0068] The living polymerization catalyst may be copper or a copper compound. Examples of the copper compound include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, and cuprous perchlorate.

[0069] The living polymerization catalysts may be used alone or in combination of two or more. The content of the living polymerization catalyst may be 0.0001 to 1 mass % relative to the total solid content of the mixture for living polymerization, and more preferably 0.005 to 0.1 mass %.

[0070] ·solvent The living polymerization mixture may further contain a solvent. Examples of the solvent include ethyl acetate, toluene, acetone, dimethylformamide, ketones, alcohols, and water. The solvent may be used alone or in combination of two or more. When the living polymerization mixture contains inorganic oxide particles having initiation sites on their surfaces and a solvent, the content of the solvent may be 20 to 90 mass %, more preferably 20 to 80 mass %, based on the total mass of the living polymerization mixture.

[0071] Co-catalyst The living polymerization mixture may further contain a cocatalyst. Examples of the co-catalyst include triazine compounds, benzotriazole compounds, and imidazole compounds.

[0072] The triazine compound is a compound having at least one triazine ring. The benzotriazole compound is a compound having at least one benzotriazole ring. The imidazole compound is a compound having at least one imidazole ring.

[0073] The co-catalyst may be a compound represented by formula (P1), a compound represented by formula (P2) or a compound represented by formula (P3), with the compound represented by formula (P3) being more preferred.

[0074] [ka]

[0075] In formula (P1), three R T each independently represents a hydrogen atom or a substituent, and may be a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent. The alkyl group may be linear or branched, and may have a carbon number of 1 to 15. The alkyl group may be a methyl group or an ethyl group, with a methyl group being more preferred. The phenyl group may have, for example, 0 to 5 substituents. The substituent that the phenyl group may have may be an alkyl group (preferably having 1 to 15 carbon atoms), a hydroxy group, a carboxy group, or a combination thereof. One or more -CH2- (methylene groups) constituting the alkyl group that the phenyl group may have may be replaced with an ester group. Examples of groups that combine these include alkoxy groups that may have a hydroxy group as a substituent.

[0076] In formula (P2), four RB1 each independently represents a hydrogen atom or a substituent. In formula (P2), R B2 represents a hydrogen atom or a substituent, and may be a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent. R in formula (P2) B2 is, for example, R in formula (P1) T is the same as:

[0077] In formula (P3), three R I1 each independently represents a hydrogen atom or a substituent, and may be a hydrogen atom, an alkyl group which may have a substituent, a phenyl group which may have a substituent, a hydroxy group, or a carboxy group. Examples of the alkyl group include R T The alkyl groups are the same as those that can be represented by the above alkyl groups. Examples of the phenyl group include R T This is similar to the above phenyl group which can be represented by the following formula: In formula (P3), R I2 represents a hydrogen atom or a substituent, and may be a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent. R in formula (P3) I2 is, for example, R in formula (P1) T is the same as: An example of the compound represented by formula (P3) is 1-methylimidazole.

[0078] Commercially available promoters include, for example, Tinuvin 400, Tinuvin 384-2, and Tinuvin 477 (all manufactured by BASF).

[0079] The promoter may be used alone or in combination of two or more. When the mixture for living polymerization contains a co-catalyst, the content thereof may be 0.0001 to 10% by mass, more preferably 0.0001 to 5% by mass, based on the total solid content of the mixture for living polymerization.

[0080] When the mixture for living polymerization contains a living polymerization catalyst, the content thereof may be 50 to 99.99 mass %, more preferably 80 to 99.99 mass %, based on the total content of the co-catalyst and living polymerization catalyst.

[0081] The reaction time for living polymerization is, for example, 1 to 10 hours. The reaction temperature for living polymerization is, for example, 25 to 60°C.

[0082] (Process 2) Step 2 is a step of synthesizing polymer chain B by cationic polymerization of the oxetanyl group of compound Y, thereby forming a second shell portion that covers the first shell portion.

[0083] Step 2 may be a step of reacting a mixture for cationic polymerization, which will be described later. The cationic polymerization may be living cationic polymerization.

[0084] The cationic polymerization mixture may be prepared by reacting the living polymerization mixture in step 1 and then adding various components described below to the resulting mixture. In other words, the cationic polymerization mixture may contain the various components contained in the living polymerization mixture, their reactants, and mixtures thereof. The mixture for cationic polymerization may contain first shell particles having cationic polymerizable groups, which will be described later, and a cationic polymerization initiator. Hereinafter, as one embodiment of Step 2, Step 2 in which the mixture for cationic polymerization is reacted will be described in detail.

[0085] First shell particles with cationic polymerizable groups The first shell particles having cationically polymerizable groups are particles obtained by step 1 that further have cationically polymerizable groups, and the first shell particles have a core portion and a first shell portion covering the core portion and further have cationically polymerizable groups. The cationically polymerizable group may be, for example, an alicyclic ether group such as an epoxy group or an oxetanyl group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester group, or a vinyloxy group, and an epoxy group or an oxetanyl group is more preferred.

[0086] An example of a method for producing first shell particles having a cationically polymerizable group is a method in which a compound having a cationically polymerizable group is reacted with the first shell particles. Step 2 may include a step of reacting a compound having the above-mentioned cationically polymerizable group. The compound having the cationically polymerizable group may further have an ethylenically unsaturated group different from the cationically polymerizable group. The ethylenically unsaturated group may be, for example, a (meth)acryloyl group.

[0087] An example of the compound having a cationically polymerizable group is Compound T. In the compound T, n represents an integer of 1 to 10. n may be 1 or 2.

[0088] [ka]

[0089] The content of the first shell particles may be 1 to 90 mass %, more preferably 5 to 80 mass %, based on the total content of the first shell particles and the compound having a cationically polymerizable group. The content of the compound having a cationically polymerizable group relative to the total content may be 5 to 80 mass %, and more preferably 5 to 50 mass %.

[0090] Cationic polymerization initiator Examples of the cationic polymerization initiator include known cationic polymerization initiators. Specifically, it may be a cationic polymerization initiator among the polymerization initiators that can be contained in the composition described below.

[0091] The cationic polymerization initiators may be used alone or in combination of two or more. The content of the cationic polymerization initiator may be 0.05 to 5.0 mass % relative to the total solid content of the mixture for cationic polymerization, and more preferably 0.1 to 3.0 mass %.

[0092] The reaction conditions of the cationic polymerization, such as the reaction time and reaction temperature, can be adjusted as appropriate.

[0093] The above-mentioned film may be used as a hard coat layer, which will be described later, and is more preferably used as a hard coat layer disposed on a spectacle lens substrate.

[0094] The various components that can be contained in the mixture for living polymerization or the mixture for cationic polymerization preferably have the following aspects. The mass ratio of the content of compound Y to the content of compound X (content of compound Y / content of compound X) may be 0.01 to 2.00.

[0095] [Composition] The composition contains the core-shell particles described above, and the composition can be used to form the film described above. The composition may further contain a polymerizable compound and / or a polymerization initiator, and more preferably contains a polymerizable compound and a polymerization initiator. The various components that the composition may contain are described in detail below.

[0096] <Core-shell particles> The composition includes the core-shell particles described above. The core-shell particles are as described above in the membrane. The core-shell particles may be used alone or in combination of two or more types. The content of the core-shell particles may be 25 to 90 mass % relative to the total solid content of the composition, and more preferably 30 to 85 mass %.

[0097] <Polymerizable compound> The composition may include a polymerizable compound. The polymerizable compound may be, for example, a compound having a polymerizable group, and more preferably a radically polymerizable group or a cationically polymerizable group. The radically polymerizable group may be, for example, a (meth)acryloyl group. The cationically polymerizable group may be, for example, an alicyclic ether group such as an epoxy group or an oxetanyl group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester group, or a vinyloxy group, and more preferably an epoxy group or an oxetanyl group.

[0098] The polymerizable compound may be the above-mentioned compound X, the above-mentioned compound Y, or the compound having a cationically polymerizable group in step 2. When the mixture after the reaction for obtaining the polymer chain A is used for preparing the composition of the present disclosure, a part or all of the compound X contained in the composition of the present disclosure may be the unreacted portion of the compound X contained in the mixture. When the mixture after the reaction for obtaining the polymer chain B is used for preparing the composition of the present disclosure, a part or all of the compound Y contained in the composition of the present disclosure may be the unreacted portion of the compound Y contained in the mixture. In step 2, when the mixture after the reaction to obtain the first shell particles is used to prepare the composition of the present disclosure, some or all of the compound having a cationically polymerizable group contained in the composition of the present disclosure may be the unreacted portion of the compound having a cationically polymerizable group contained in the mixture.

[0099] The polymerizable compounds may be used alone or in combination of two or more. When the composition contains a polymerizable compound, the content of the polymerizable compound may be 0.01 to 50 mass %, more preferably 1 to 40 mass %, based on the total solid content of the composition.

[0100] <Polymerization initiator> The composition may also include a polymerization initiator. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator, and may be a radical polymerization initiator or a photopolymerization initiator. Examples of the polymerization initiator include Omnirad 127, 184, 907, 651, 1700, 1800, 819, 369, and TPO (manufactured by IGM Resins BV); DAROCUR1173 (manufactured by Sigma-Aldrich); Ezacure KIP150 and TZT (manufactured by Nippon SiberHegner AG); Kayacure BMS and Kayacure DMBI (manufactured by Nippon Kayaku Co., Ltd.); Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 477, Tinuvin 479, and Tinuvin 1577 (manufactured by BASF). The cationic polymerization initiator may be, for example, a compound containing one or more cations selected from the group consisting of aromatic sulfonium, aromatic iodonium, aromatic diazonium, and pyridinium, and BF4 - , P.F. 6- , SbF 6- , AsF 6- , CF3SO 3- , (CF3SO2)2N - and B(C6F5) 4- and one or more anions selected from the group consisting of: and an onium salt composed of: and an aluminum complex such as aluminum chloride; and The polymerization initiator may be used alone or in combination of two or more. When the composition contains a polymerization initiator, the content thereof may be 0.001 to 5 mass %, more preferably 0.01 to 5 mass %, based on the total solid content of the composition.

[0101] <Sensitizer> The composition may also include a sensitizer. When the composition contains a polymerization initiator, it is preferred that the composition further contains a sensitizer. Examples of the sensitizer include the Anthracure series (manufactured by Kawasaki Chemical Industries, Ltd.). The sensitizers may be used alone or in combination of two or more. When the composition contains a sensitizer, the content thereof may be 0.001 to 5 mass %, more preferably 0.05 to 2 mass %, based on the total solid content of the composition.

[0102] <Surfactant> The composition may also include a surfactant. Examples of surfactants include silicone compounds such as silicone oil. Examples of surfactants include the DOWSIL series (manufactured by Dow Chemical). The surfactants may be used alone or in combination of two or more. When the composition contains a surfactant, the content thereof may be 0.001 to 5 mass %, more preferably 0.01 to 0.5 mass %, based on the total solid content of the composition.

[0103] <UV absorber> The composition may also include an ultraviolet absorber. Examples of ultraviolet absorbers include triazine compounds and benzotriazole compounds. Examples of the triazine compound and benzotriazole compound include the triazine compound (e.g., the compound represented by formula (P1)) and benzotriazole compound (e.g., the compound represented by formula (P2)) that can be contained in the above-mentioned mixture for living polymerization. Therefore, when a mixture for living polymerization is used to prepare a composition, the triazine compound and benzotriazole compound contained in the mixture for living polymerization may be used as an ultraviolet absorber in the composition. The ultraviolet absorbents may be used alone or in combination of two or more. When the composition contains an ultraviolet absorber, the content thereof may be 0.01 to 5 mass %, more preferably 0.1 to 3 mass %, based on the total solid content of the composition.

[0104] <Solvent> The composition may include a solvent. The solvent may be, for example, water or an organic solvent. Examples of the organic solvent include alcohol solvents, ketone solvents, ether solvents, ester solvents, hydrocarbon solvents, halogenated hydrocarbon solvents, amide solvents, sulfone solvents, and sulfoxide solvents. The solvent may be used alone or in combination of two or more. When the composition contains a solvent, the content thereof may be 10 to 90 mass %, more preferably 20 to 60 mass %, based on the total mass of the composition.

[0105] <Other ingredients> Living polymerization mixtures and cationic polymerization mixtures may be used to prepare the compositions. The composition may include various components, reactants thereof, and decomposition products thereof that living polymerization mixtures and cationic polymerization mixtures may contain. In addition to the various components described above, the composition may contain additives such as anti-aging agents, coating film modifiers, light stabilizers, antioxidants, color inhibitors, dyes, fillers, and internal mold release agents, as necessary.

[0106] <Method of producing the composition> As a method for producing the composition, for example, the various components that can be contained in the composition described above may be mixed all at once, or the various components may be mixed in stages in separate batches.

[0107] The composition is suitably used as a composition (composition for forming a hard coat layer) for forming a hard coat layer (the above-mentioned film) on a substrate. The substrate may be a plastic substrate. Examples of plastic substrates include plastic eyeglass lens substrates and plastic films. In the latter part, an embodiment in which the composition for forming a hard coat layer is applied to a plastic eyeglass lens substrate will be described in detail as an example.

[0108] [Eyeglass lenses] The film may be used on eyeglass lenses. Examples of the spectacle lenses produced include spectacle lenses that include a spectacle lens substrate (e.g., a plastic spectacle lens substrate, etc.) and the above-mentioned film (hard coat layer) disposed on the spectacle lens substrate. FIG. 2 is a cross-sectional view of one embodiment of an eyeglass lens. The eyeglass lens 10 shown in Figure 2 includes a plastic eyeglass lens substrate 12 and a film 14 disposed on both sides of the plastic eyeglass lens substrate 12. The film (hard coat layer) 14 is a layer formed using the composition described above. 2, the film 14 is arranged so as to be in direct contact with the plastic eyeglass lens substrate 12, but the present invention is not limited to this form, and another layer (e.g., a primer layer) may be arranged between the plastic eyeglass lens substrate 12 and the film 14. In other words, the film 14 may be arranged directly on the plastic eyeglass lens substrate 12, or may be arranged indirectly on the plastic eyeglass lens substrate 12 via another layer. In addition, although the film 14 is disposed on both sides of the plastic eyeglass lens substrate 12 in FIG. 2, the film 14 may be disposed on only one side of the plastic eyeglass lens substrate 12 . Each of the components that may be included in the eyeglass lens 10 will be described in detail below.

[0109] <Plastic eyeglass lens substrate> One type of plastic eyeglass lens substrate is a finished lens, which is optically finished on both the convex and concave surfaces and molded to a desired power. Examples of types of plastics (so-called resins) that constitute plastic eyeglass lens substrates include (meth)acrylic resins, thiourethane resins, allyl resins, episulfide resins, polycarbonate resins, polyurethane resins, polyester resins, polystyrene resins, polyethersulfone resins, poly-4-methylpentene-1 resins, diethylene glycol bisallyl carbonate resins (CR-39), and polyvinyl chloride resins.

[0110] The thickness of plastic eyeglass lens substrates is often 1 to 30 mm from the viewpoint of ease of handling. The refractive index of the plastic eyeglass lens substrate is not particularly limited. The plastic spectacle lens substrate may be opaque or colored, provided that it is translucent.

[0111] <Membrane> The film may function as a so-called hard coat layer. The hard coat layer is a layer disposed on a plastic eyeglass lens substrate, and is a layer that imparts scratch resistance to the plastic eyeglass lens substrate. The hard coat layer is the above-mentioned film, and is a layer formed from a composition.

[0112] The hard coat layer can be formed, for example, by applying the above-described composition to a plastic eyeglass lens substrate to form a coating film, and then subjecting the coating film to a curing treatment such as light irradiation treatment. After forming the coating film, if necessary, a drying treatment such as a heating treatment may be carried out to remove the solvent from the coating film.

[0113] Methods for applying the composition onto a plastic eyeglass lens substrate include known methods (for example, dipping coating, spin coating, spray coating, inkjet coating, and flow coating). For example, when using a dip coating method, a plastic eyeglass lens substrate is immersed in the composition, and then the plastic eyeglass lens substrate is pulled out and dried, thereby forming a coating film of a predetermined thickness on the plastic eyeglass lens substrate. The thickness of the coating film formed on the plastic eyeglass lens substrate can be adjusted as appropriate.

[0114] The conditions for the light irradiation treatment can be selected appropriately depending on the type of polymerization initiator used. The type of light used for the light irradiation may be, for example, ultraviolet light or visible light, and the light source may be, for example, a high-pressure mercury lamp. The cumulative light amount during light irradiation is 100 to 3000 mJ / cm from the viewpoint of productivity and curing of the coating film. 2 and may be 100 to 1500 mJ / cm 2 is more preferred.

[0115] The thickness of the hard coat layer may be 1 μm or more, more preferably 5 μm or more, and even more preferably 10 μm or more, and the upper limit may be 30 μm or less. The above film thickness is an average film thickness, and is measured by measuring the film thickness at any five points on the hard coat layer and calculating the arithmetic average of the measured values.

[0116] <Primer layer> The spectacle lens may further include a primer layer disposed between the substrate and the hard coat layer. The primer layer is a layer that improves the adhesion of the hard coat layer to the substrate. Examples of materials that can be used to form the primer layer include resins. Specific examples include urethane resins, epoxy resins, phenol resins, polyimide resins, polyester resins, bismaleimide resins, and polyolefin resins.

[0117] The primer layer may be formed by any known method. Specifically, a method of forming a primer layer by applying a primer layer-forming composition containing a predetermined resin onto a substrate and subjecting the composition to a curing treatment as necessary can be mentioned. The thickness of the primer layer may be 0.3 to 2 μm.

[0118] The plastic eyeglass lens may further include an anti-reflective coating disposed on the hard coat layer. The anti-reflection film is a layer that has the function of preventing the reflection of incident light. Specifically, it can have low reflectance characteristics (broadband low reflectance characteristics) over the entire visible range of 400 to 700 nm.

[0119] <Anti-reflective film> The eyeglass lenses may include an anti-reflective coating. The anti-reflection film may have a single layer structure or a multi-layer structure. The anti-reflection film is preferably an inorganic anti-reflection film, which means an anti-reflection film made of an inorganic compound. The multi-layered anti-reflection film may have a structure in which low refractive index layers and high refractive index layers are alternately laminated. Examples of materials that can be used to form the high refractive index layer include titanium, zirconium, aluminum, niobium, tantalum, and lanthanum oxide, and examples of materials that can be used to form the low refractive index layer include silica oxide. Examples of methods for producing an anti-reflective film include dry methods such as vacuum deposition, sputtering, ion plating, ion beam assisted deposition, and CVD. [Example]

[0120] The membrane of the present disclosure will be explained in more detail below with reference to examples and comparative examples, but the membrane is not limited by these examples in any way.

[0121] Example 1 (Formation of primer layer) Preparation of primer layer forming composition To pure water (289 parts by mass), surfactants Silwet L-77 (manufactured by Momentive) (0.2 parts by mass) and DOWSIL L-7604 (manufactured by Dow) (0.2 parts by mass), propylene glycol monomethyl ether (10.6 parts by mass), and an aqueous urethane dispersion (Evaphanol HA170, manufactured by Nicca Chemical Co., Ltd., solids content 37% by mass) (200 parts by mass) were added and stirred to prepare a primer layer-forming composition 1 with a solids content of 14.8% by mass.

[0122] - Formation of primer layer As the plastic eyeglass lens substrate, a lens with a refractive index of 1.60 (Nikon-Essilor: Nikon Light 3AS Material S-2.00D) or a lens with a refractive index of 1.74 (Nikon-Essilor, S-7.00) was used. Specifically, when preparing a plastic eyeglass lens substrate with a hard coat layer for evaluating haze, which will be described later, a lens having a refractive index of 1.60 was used as the plastic eyeglass lens substrate, and when preparing a plastic eyeglass lens substrate with a hard coat layer for evaluating pencil hardness, which will be described later, a lens having a refractive index of 1.74 was used as the plastic eyeglass lens substrate. The plastic eyeglass lens substrate was dipped into primer layer-forming composition 1 at 90 mm / min and baked at 90° C. for 20 minutes to form a primer layer.

[0123] (film formation) Preparation of the composition ··Chlorination of SiO2 particles Acrylic group-coated SiO2 nanoparticle dispersion (MEK-AC-4130Y) (Nissan Chemical Industries, Ltd.) (232.00 parts by mass, solid content 69.60 parts by mass), AlCl3 (Tokyo Chemical Industry Co., Ltd.) (0.12 parts by mass), and epichlorohydrin (Tokyo Chemical Industry Co., Ltd.) (1.24 parts by mass) were mixed in this order and stirred at 40°C for 4 hours. The resulting solution was designated SiO2 solution A1. The above reaction yielded SiO2 nanoparticles having Cl groups (more specifically, SiO2 nanoparticles having groups represented by formula (S1) where X is Cl). The solid content (content of nanoparticles) of MEK-AC-4130Y is 30 mass %.

[0124] Living Radical Polymerization The obtained SiO2 solution A1 (total mass parts), 80 mass% A9300 solution (13.88 mass parts, solid content 11.10 mass parts), and 1 mass% Fe solution (3.1 mass parts, solid content 0.31 × 10 -1 parts by mass) and 0.02% by mass MeIm solution (3.1 parts by mass, active ingredient is 0.62 × 10 -3 Parts by mass) were mixed and stirred for 2 hours at 40° C. The resulting solution was designated LRP-SiO2 solution A1.

[0125] Preparation of 80% by mass A9300 solution NK Ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.) (80 parts by mass) and MEK (methyl ethyl ketone) (20 parts by mass) were mixed and thoroughly stirred, and the resulting solution was designated as an 80% by mass A9300 solution.

[0126] Preparation of 1 mass% Fe solution 1,1-bis(diisopropylphosphino)ferrocene (Tokyo Chemical Industry Co., Ltd.) (1.0 part by mass) and MEK (99.0 parts by mass) were mixed and stirred thoroughly, and the resulting solution was used as a 1% by mass Fe solution.

[0127] Preparation of 0.02 mass% MeIm solution 1-Methylimidazole (Tokyo Chemical Industry Co., Ltd.) (2 parts by mass) and MEK (98 parts by mass) were mixed and stirred thoroughly. This mixture was diluted 10-fold twice. The resulting solution was used as a 0.02% by mass MeIm solution.

[0128] Epoxy group addition reaction 1,2-Epoxy-5-hexene (0.80 parts by mass) was added to the obtained LRP-SiO2 solution A1 (total parts by mass), and the mixture was stirred at 30°C for 2 hours.

[0129] ··Addition reaction of oxetanyl group Aron Oxetane OXT-221 (manufactured by Toagosei Co., Ltd.) (15.19 parts by mass) was added to the solution after the addition reaction of the epoxy groups, and the mixture was stirred for 1 hour at 40° C. The resulting solution was designated as Ox-SiO2 solution A1.

[0130] Solvent substitution Using an evaporator (NE-1101, manufactured by Tokyo Rikakikai Co., Ltd.), MEK (151.1 parts by mass) was removed from the obtained Ox-SiO2 solution A1 (total parts by mass). The residue was then placed in a container, and the residue remaining in the flask was washed three times with propylene glycol monomethyl ether acetate (PGMEA) and transferred to the container. A total of 24.1 parts by mass of PGMEA was used. The solution in the container was thoroughly stirred.

[0131] ··Addition of other ingredients To the solvent-substituted solution were further added Ominirad819 (manufactured by IGM Resins BV) (0.70 parts by mass), Ominirad127 (manufactured by IGM Resins BV) (0.06 parts by mass), Tinuvin400 (manufactured by BASF) (1.00 parts by mass), SP-172 (manufactured by ADEKA) (0.58 parts by mass), and 10% by mass L7604 solution (manufactured by Dow) (0.58 parts by mass) to prepare Composition A1.

[0132] Preparation of 10% by mass L7604 solution DOWSIL L-7604 (manufactured by Dow) was diluted 10 times by mass with PGMEA, and the resulting solution was used as a 10 mass% L7604 solution.

[0133] Membrane formation Composition A1 (2.0 mL) was dropped onto the primer layer of the plastic eyeglass lens substrate with the primer layer formed thereon obtained above, and then spin-coated. In the spin-coating, the plastic eyeglass lens substrate with Composition A1 applied thereto was rotated in this order at 400 rpm for 10 seconds, at 2000 rpm for 0.5 seconds, and finally at 0 rpm over 1 second. Next, the obtained plastic eyeglass lens substrate was heated at 100°C for 20 minutes, and then heated under a high-pressure mercury lamp (100 mW / cm) as a light source. 2 ) was used to irradiate the coating film formed using composition A1 with UV light (integrated light amount: 0.8 J / cm 2 )did. The other surface of the plastic eyeglass lens substrate was also subjected to the same treatment as above. After UV irradiation on both surfaces, it was baked at 100°C for 10 minutes to form film A1, and a plastic eyeglass lens substrate with a film was obtained.

[0134] <Example 2> During the chloroaddition of SiO particles in Example 1, a UV-polymerizable group-coated SiO nanoparticle dispersion (MEK-AC-4130Y) (Nissan Chemical Industries, Ltd.) (232.00 parts by weight, solids content: 69.60 parts by weight), an 80% by weight (meth)acrylic group-containing silsesquioxane solution (AC-SQ TA-100) (Toagosei Co., Ltd.) (16.70 parts by weight, solids content: 13.36 parts by weight), AlCl (Tokyo Chemical Industry Co., Ltd.) (0.10 parts by weight), and epichlorohydrin (Tokyo Chemical Industry Co., Ltd.) (0.98 parts by weight) were mixed in this order and stirred at 40 °C for 4 hours. The resulting solution was designated SiO-TA100 solution A1. A film of Example 2 was formed using the same procedure as in Example 1, except as described above. The UV-polymerizable group is an ethylenically unsaturated group (acrylic group). The solid content (nanoparticle content) of MEK-AC-4130Y is 30% by mass.

[0135] Preparation of 80% by mass (meth)acrylic group-containing silsesquioxane solution AC-SQ TA-100 (manufactured by Toagosei Co., Ltd.) (80 parts by mass) and MEK (20 parts by mass) were mixed and thoroughly stirred, and the resulting solution was used as an 80% by mass (meth)acrylic group-containing silsesquioxane solution.

[0136] In Examples 3 to 6 and Comparative Example 1, compositions were prepared using the components in the table below with reference to the above-mentioned Example 1, and films were formed. In Examples 7 to 13 and Comparative Example 2, compositions were prepared using the components in the table below with reference to the above-mentioned Example 2, and films were formed. In Comparative Examples 1 and 2, no heat treatment was performed in either the addition reaction of the epoxy group or the addition reaction of the oxetanyl group. That is, although the compositions of Comparative Examples 1 and 2 contain 1,2-epoxy-5-hexene and Aronoxetane OXT-221, no heat treatment was performed in either the addition reaction of the epoxy group or the addition reaction of the oxetanyl group. Therefore, the second shell portion is not formed, and the films of Comparative Examples 1 and 2 do not contain the specified core-shell particles.

[0137] The meaning of each item in the table is as follows: The column "(A) / (B)" indicates the mass ratio of the content of compound X (A9300) to the content of compound Y (Aronoxetane OXT-221). The column "(A) / (C1+C2)" indicates the mass ratio of the content of compound X (A9300) to the total content of the inorganic oxide particles (MEK-AC-4130Y) and the silsesquioxane (AC-SQ TA-100). The column "(D1):(D2)" indicates the mass ratio of Ominirad819:Ominirad127. The column "(F):(E)" indicates the mass ratio of AlCl3:epichlorohydrin. The column "(G) / (E)" indicates the mass ratio of the Fe content to the epichlorohydrin content. The column "(B):(H):(I)" indicates the mass ratio of compound Y (Aronoxetane OXT-221): compound having a cationically polymerizable group (1,2-epoxy-5-hexene): SP-172.

[0138] [Table 1]

[0139] The values ​​in the table indicate the parts by weight of the solid content of each component. MEK-AC-4130Y: The above-mentioned 30% by mass acrylic group-coated SiO2 nanoparticle dispersion. However, the values ​​in the table indicate the solid content (parts by mass) of "MEK-AC-4130Y," not the part by mass of the dispersion. AC-SQ TA-100: The above-mentioned 80% by mass (meth)acrylic group-containing silsesquioxane solution. However, the values ​​in the table indicate the solid content (parts by mass) of the "80% by mass (meth)acrylic group-containing silsesquioxane solution," not the parts by mass of the solution. Epichlorohydrin: the epichlorohydrin mentioned above AlCl3: the above-mentioned AlCl3 A9300: The above-mentioned 80% by mass A9300 solution. However, the values ​​in the table indicate the solid content (parts by mass) of the "80% by mass A9300 solution," not the part by mass of the solution. Fe: the 1 mass % Fe solution described above. However, the values ​​in the table indicate the solid content (parts by mass) of the "1 mass % Fe solution," not the parts by mass of the solution. MeIm: the above-mentioned 0.02 mass % MeIm solution. However, the values ​​in the table indicate the solid content (parts by mass) of the "0.02 mass % MeIm solution," not the part by mass of the solution. 1,2-epoxy-5-hexene: the above-mentioned 1,2-epoxy-5-hexene Aron Oxetane OXT-221: Aron Oxetane OXT-221 as mentioned above Ominirad819: The above Ominirad819 Ominirad127: the above Ominirad127 Tinuvin400: The above Tinuvin400 SP-172: The above-mentioned SP-172 L7604: The above-mentioned 10% by mass L7604 solution. However, the values ​​in the table indicate the solid content (parts by mass) of the "10% by mass L7604 solution," not the parts by mass of the solution.

[0140] <Evaluation> The following evaluations were carried out using the film-coated plastic eyeglass lens substrates obtained in the above Examples and Comparative Examples.

[0141] (Haze) The film-attached plastic eyeglass lens substrate was placed on the light-receiving side of a haze meter (NDH7000II, Nippon Denshoku Industries Co., Ltd.), and measurements were taken three times, with the average value calculated as the haze value. A: Haze value is less than 1.0 B: Haze value is 1.0 or more

[0142] (Scratch resistance (pencil hardness)) Using a film-coated plastic eyeglass lens substrate, the hardness of the film is measured with a pencil.While gradually increasing the hardness of the pencil, the pencil is inserted obliquely into the film, and the hardness just before the hardness that causes scratches is taken as the hardness of the film.For example, if the hardness of 6H is not scratched, but the hardness of 7H is scratched, the hardness of the hard coat layer is taken as 6H. A: Hardness is 6H or higher B: Hardness is less than 5H

[0143] (adhesion) The adhesion of the film to the primer layer was evaluated by a cross-cut tape test in accordance with JIS-K5600. That is, using a knife, slits were made on the film surface of the film-coated plastic eyeglass lens substrate at 1 mm intervals, reaching down to the plastic eyeglass lens substrate, forming 100 grids. Next, Scotch tape (manufactured by 3M) was pressed firmly onto the slit hard coat layer. After that, the Scotch tape was quickly pulled at a 45° angle from the film surface with a load of 4 kg, and after peeling, the number of grids remaining on the plastic eyeglass lens substrate was counted. AA: 85 or more squares remaining A: The number of remaining squares is between 70 and 85. B: The number of remaining squares is less than 70

[0144] [Table 2]

[0145] "SiO2" refers to silicon dioxide (SiO2) that forms the core. "SQ" indicates cis-sesquioxane that forms the core portion. The numerical values ​​or notations in parentheses for each evaluation in the "Evaluation Results" section indicate the respective evaluation results.

[0146] As shown in Table 1, it was confirmed that the membrane of the present disclosure provides the desired effects. [Explanation of symbols]

[0147] 100 core-shell particles 102 Core 104 First Shell Section 106 Second shell part 10 Eyeglass lenses 12 Plastic eyeglass lens substrate 14 Film (hard coat layer)

Claims

1. A film comprising a core-shell particle having a core portion, a first shell portion covering the core portion, and a second shell portion covering the first shell portion, the core portion contains inorganic oxide particles or silsesquioxane, the first shell portion includes a polymer chain A including at least one selected from the group consisting of an acrylate-based polymer chain and a methacrylate-based polymer chain; the second shell portion includes a polymer chain B obtained by cationic polymerization of the oxetanyl group of a compound having an oxetanyl group, The compound having an oxetanyl group has 2 to 5 oxetanyl groups.

2. The film described in claim 1, wherein the content of the first shell portion is 20 to 80 mass% relative to the total mass of the core-shell particle.

3. The inorganic oxide particles are SiO ２ , Al ２ O ３ , SnO ２ , ZrO ２ and TiO ２ The membrane according to claim 1 or 2, comprising one or more selected from the group consisting of:

4. The membrane according to claim 1 or 2, further comprising a polymer compound.

5. The membrane according to claim 1 or 2, wherein the polymer chain A is a polymer chain obtained by living radical polymerization.

6. A spectacle lens substrate; A spectacle lens comprising: the film according to claim 1 or 2 disposed on the spectacle lens substrate.

7. A composition comprising a core-shell particle having a core portion, a first shell portion covering the core portion, and a second shell portion covering the first shell portion, the core portion contains inorganic oxide particles or silsesquioxane, the first shell portion includes a polymer chain A including at least one selected from the group consisting of an acrylate-based polymer chain and a methacrylate-based polymer chain; the second shell portion includes a polymer chain B obtained by cationic polymerization of the oxetanyl group of a compound having an oxetanyl group, The composition, wherein the number of oxetanyl groups contained in the compound having an oxetanyl group is 2 to 5.

8. The composition described in Claim 7, wherein the content of the first shell portion is 20 to 80 mass% relative to the total mass of the core-shell particle.

9. The composition according to claim 7 or 8, further comprising a polymerizable compound.

10. The composition according to claim 7 or 8, further comprising a polymerization initiator.

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