Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/113—Silicon oxides; Hydrates thereof
  • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
  • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/04—Ingredients treated with organic substances
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
  • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D17/00—Pigment pastes, e.g. for mixing in paints

Definitions

• the present invention relates to a composition.
• silica particles have been usefully used because they can impart various properties such as scratch resistance to resin products.
• silica particles are used in a hard coat layer for improving the surface hardness and scratch resistance of resin base materials and the like.
• the hard coat layer can be formed by applying a composition containing silica to the monomer constituting the hard coat onto a resin base material and curing it, but the composition containing silica particles has an increased viscosity. It may be difficult to handle.
• Patent Document 1 it is essential to reduce the viscosity by adding a solvent to a composition containing silica particles and a monomer.
• the hard coat composition disclosed in Patent Document 1 has a problem in that productivity decreases because the solvent needs to be dried after being applied to the substrate.
• a hard coat composition that does not contain a solvent is desired.
• Patent Document 2 describes a silica particle-containing composition in which a viscous substance is mixed with silica particles whose 29 Si-solid NMR spectrum has a specific peak under solvent-free conditions, that is, silica particles with few residual silanol groups. things are disclosed.
• compositions to which silica particles are added may increase in viscosity and be difficult to handle, and Patent Document 2 suppresses the increase in viscosity by using silica particles with fewer residual silanol groups.
• An object of the present invention is to provide a composition containing silica particles and a monomer, the viscosity of which is reduced by a different means from Patent Document 2.
• the viscosity of the composition can be significantly reduced by including a specific amount of ammonia, and have completed the present invention.
• the invention is as follows. [1] A composition comprising silica particles (a), an ethylenically unsaturated group-containing monomer (b), and ammonia (c), A composition in which the amount of ammonia (c) in 100% by weight of the composition is 0.05 to 4.5% by weight. [2] The composition according to [1], wherein the composition does not contain a solvent or contains 3.0% by mass or less of a solvent based on 100% by mass of the composition.
• the silica particles (a) are selected from the group consisting of an aryl group, a (meth)acryloyl group, an alkyl group, a vinyl group, a styryl group, an epoxy group, a mercapto group, an amino group, an isocyanate group, and a halogenated alkyl group.
• the ethylenically unsaturated group-containing monomer (b) is A monomer having a urethane bond or a monomer having a (1-hydroxy,2-oxy)ethylene structure (b-1), A monomer having neither a urethane bond nor a (1-hydroxy,2-oxy)ethylene structure, the number of ethylenically unsaturated groups in one monomer molecule is 3 or more, and the concentration of ethylenically unsaturated groups is 4.
• composition according to any one of [1] to [4], which is at least one selected from the following.
• the ethylenically unsaturated group-containing monomer (b) is composed of at least one of monomer (b-1) and monomer (b-2), and monomer (b-3), or The composition according to [5], consisting only of (b-3). [7] The composition according to any one of [1] to [6], wherein the ethylenically unsaturated group-containing monomer (b) has a viscosity of 2000 mPa ⁇ s or less at a temperature of 25°C.
• the viscosity of the silica particle-containing monomer composition can be reduced.
• composition of the present invention includes silica particles (a), an ethylenically unsaturated group-containing monomer (b), and ammonia (c). Each will be explained below.
• silica particles are preferably nanometer-order particles, and the average primary particle diameter is, for example, 1 nm or more, preferably 5 nm or more, more preferably 10 nm or more, and, for example, 100 nm or less. It is preferably 90 nm or less, more preferably 70 nm or less (that is, 1 to 100 nm is preferable, 5 to 90 nm is more preferable, and even more preferably 10 to 70 nm).
• the average primary particle diameter as shown in the examples described below, the arithmetic mean value of the diameters of 50 arbitrary particles observed with an electron microscope can be used.
• the major axis may be measured as the diameter.
• the average sphericity ratio of silica particles is determined by observing the silica particles with an electron microscope, measuring the major axis and minor axis of each silica particle, and calculating the sphericity ratio (major axis/minor axis). It can be determined by averaging the measured sphericity ratios, and the value is preferably 1.2 to 1, more preferably 1.1 to 1, and even more preferably 1.05 to 1.
• the silica particles (a) may be surface-treated, and include aryl groups, (meth)acryloyl groups, alkyl groups, vinyl groups, styryl groups, epoxy groups, mercapto groups, amino groups, isocyanate groups, and halogenated alkyl groups. It is preferable that the surface be treated with a silane coupling agent containing at least one functional group selected from the group consisting of:
• the silica particles (a) surface-treated with such a silane coupling agent have the above-mentioned functional groups on the surface.
• the silica particles (a) are preferably surface-treated with a silane coupling agent containing at least a (meth)acryloyl group.
• the silane coupling agent is preferably a compound in which a hydrolyzable group (a group that can form a silanol group by hydrolysis) and a functional group are bonded to a central silicon atom, such as phenyltrimethoxysilane, phenyltriethoxysilane, Aryl alkoxysilane compounds such as diphenyldimethoxysilane and diphenyldiethoxysilane; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxy (meth)acryloyl group-containing alkoxysilane compounds such as silane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldimethoxysilane; methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxys
• the concentration of silica particles (a) in 100% by mass of the composition is preferably 10% by mass or more and 70% by mass or less (ie, 10 to 70% by mass).
• the silica particle concentration is more preferably 15% by mass or more, even more preferably 20% by mass or more, and more preferably 65% by mass or less, even more preferably 60% by mass or less (that is, 15 to 65% by mass is more preferred, 20% by mass or less is more preferable). ⁇ 60% by mass is more preferred).
• the concentration of the surface-treated silica particles is preferably within the above range.
• the concentration of the silica particles (a) in 100% by mass of the composition is preferably 20 to 70% by mass. , more preferably 30 to 70% by mass, and even more preferably 40 to 70% by mass.
• the ethylenically unsaturated group-containing monomer (b) is composed of at least one of (b-1) and (b-2) and (b-3), based on 100% by mass of the composition, The concentration of the silica particles (a) is preferably 20 to 60% by mass.
• Ethylenically unsaturated group-containing monomer (b) As the ethylenically unsaturated group-containing monomer (b), one type or two or more types can be used. Any crosslinking monomer having two or more in the molecule can be used.
• Monofunctional monomers include (meth)acrylic acid ester; vinyl monomers such as N-vinyl-2-pyrrolidone (NVP); styrene, p-tert-butylstyrene, ⁇ -methylstyrene, m-methyl Styrenic monomers (styrenes) such as styrene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, p-hydroxystyrene; Carboxy group-containing monomers such as (meth)acrylic acid; 2- Hydroxyl group-containing monomers such as hydroxyethyl (meth)acrylate (HEA), 3-hydroxy-2-hydroxypropyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate; cyclic trimethylolpropane formal acrylate ( CTFA), etc.
• VRP N-vinyl-2-pyrrolidone
• the above (meth)acrylic acid esters include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate (BA), isobutyl (meth)acrylic acid alkyl esters such as (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate; (meth)acrylic acid cycloalkyl esters such as cyclohexyl (meth)acrylate (CHA); 2,4-dibromo-6-sec-butylphenyl (meth)acrylate, 2,4-dibromo-6-isopropylphenyl (meth)acrylate, phenyl (meth)acrylate, 2,4,6-tribromophenyl (meth) (meth)acrylic acid aryl esters
• (meth)acrylic acid ester (meth)acrylic acid esters having an arylthiooxy group such as phenylthioethyl (meth)acrylate, 1-naphthylthioethyl (meth)acrylate, and 2-naphthylthioethyl (meth)acrylate;
• Alkylene glycol mono(meth)acrylates such as methoxypolyethylene glycol(meth)acrylate and phenoxypolyethylene glycol(meth)acrylate;
• Examples include (meth)acrylic acid esters having a glycidyl group such as glycidyl (meth)acrylate.
• Monofunctional monomers include (meth)acrylic acid ester, N-vinyl-2-pyrrolidone (NVP), cyclic trimethylolpropane formal acrylate (CTFA), 2-hydroxyethyl (meth)acrylate (HEA), 3- Hydroxy-2-hydroxypropyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, or styrenic monomers (styrenes) are preferred, particularly n-butyl (meth)acrylate (BA), cyclohexyl (Meth)acrylate (CHA) or N-vinyl-2-pyrrolidone (NVP) is preferred.
• crosslinkable monomers include tetramethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate (EGDA), diethylene glycol di(meth)acrylate (DEGDA), triethylene glycol di(meth)acrylate (TEGDA), Tetraethylene glycol di(meth)acrylate (TeEGDA), polyethylene glycol di(meth)acrylate (PEGDA), propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate (DPGDA), tripropylene glycol di(meth)acrylate acrylate (TPGDA), polypropylene glycol di(meth)acrylate (PPGDA), 1,4-butanediol di(meth)acrylate (BDDA), polybutylene glycol di(meth)acrylate (PBGDA), 1,6-hexanediol diacrylate (meth)acrylate (HDDA) and other alkylene glycol poly(meth)acrylates; Neopen
• Polyfunctional (meth)acrylates such as poly(meth)acrylates; Polyfunctional styrenic monomers such as divinylbenzene (DVB); Allyl ester monomers such as 2-(allyloxymethyl)methyl acrylate, 2-(allyloxymethyl)cyclohexyl acrylate, 2-(allyloxymethyl)acrylate derivatives; Polyfunctional allyl ester monomers such as diallyl phthalate, diallyl isophthalate, triallyl cyanurate, triallyl isocyanurate; 2-(2-vinyloxyethoxy)ethyl (meth)acrylate (VEEA); Urethane acrylate oligomers (for example, Shiko (registered trademark) series (manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd.), CN series (manufactured by Sartomer), Unidic (registered trademark) series (manufactured by DIC Corporation), KAYARAD (registered trademark)
• EBECRYL series (manufactured by Daicel Allnex Corporation), NK Oligo series (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Neopol series (manufactured by Nihon U-Pica Co., Ltd.), epoxy ester series (manufactured by Kyoeisha Chemical Co., Ltd.) Co., Ltd.));
• acrylic resin acrylate oligomers eg, HA series (manufactured by Showa Denko Materials Co., Ltd.), EBECRYL series, and KRM series (all manufactured by Daicel Allnex Co., Ltd.)
• the ethylenically unsaturated group-containing monomer (b) is used to include the above-mentioned oligomers.
• crosslinkable monomers examples include 1,4-butanediol di(meth)acrylate (BDDA), 1,6-hexanediol di(meth)acrylate (HDDA), ethylene glycol di(meth)acrylate (EGDA), and diethylene glycol.
• BDDA 1,4-butanediol di(meth)acrylate
• HDDA 1,6-hexanediol di(meth)acrylate
• EGDA ethylene glycol di(meth)acrylate
• diethylene glycol di(meth)acrylate
• the ethylenically unsaturated group-containing monomer (b) can be classified into any of the following (b-1) to (b-3).
• Monomers classified as (b-1) or (b-2) are monomers with relatively high viscosity, and monomers classified as (b-3) are monomers with relatively low viscosity.
• monomers having urethane bonds include urethane acrylate oligomers as described above.
• the (1-hydroxy,2-oxy)ethylene structure is a structure formed by ring-opening polymerization of an epoxy group and a carboxyl group. Examples of monomers having such a structure include epoxy acrylate oligomers and acrylic resin acrylate oligomers.
• Monomer (b-2) is a monomer having neither a urethane bond nor a (1-hydroxy,2-oxy)ethylene structure, the number of ethylenically unsaturated groups is 3 or more in one monomer molecule, and The monomer has an ethylenically unsaturated group concentration of 4.8 mmol/g or more.
• one having the requirements of the monomer (b-2) can be selected from the above-mentioned crosslinkable monomers, such as trimethylolpropane tri(meth)acrylate (TMPTA), ethoxylated (3) Trimethylolpropane tri(meth)acrylate, ethoxylated (3) trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, ethoxylated dipentaerythritol hexa (meth)acrylate (DPHA-EO), ditrimethylolpropane tetra(meth)acrylate (DTMPTEA), dipentaerythritol hexa(meth)acrylate (DPHA), pentaerythritol tetra(meth)acrylate (PETTA), or ethoxylated pen
• TMPTA trimethyl
• Monomer (b-3) is a monomer that does not have a urethane bond or a (1-hydroxy,2-oxy)ethylene structure, and the number of ethylenically unsaturated groups in one molecule of the monomer is less than 3.
• the monomer satisfies at least one of the requirements that the concentration of sexually unsaturated groups is less than 4.8 mmol/g.
• one having the requirements of the monomer (b-3) can be selected from the above-mentioned monofunctional monomers and crosslinkable monomers, such as 2-(allyloxymethyl)acrylic acid.
• Examples include methyl (AOMA), 1,4-butanediol di(meth)acrylate (BDDA), 1,6-hexanediol di(meth)acrylate (HDDA), or cyclic trimethylolpropane formal acrylate (CTFA). Applicable.
• the ethylenically unsaturated group-containing monomer (b) only monomer (b-1), only monomer (b-2), or only monomer (b-3) may be used, or (b-1), (although two or more of b-2) and (b-3) may be used, from the viewpoint of ease of coating the composition of the present invention on a substrate, the ethylenically unsaturated group-containing monomer (b) is It is preferable to be composed of at least one of monomer (b-1) and monomer (b-2) and monomer (b-3), or only monomer (b-3).
• the viscosity of the ethylenically unsaturated group-containing monomer (b) at a temperature of 25° C. is 2000 mPa ⁇ s or less.
• the viscosity within the above range is satisfied in a mixed state of the two or more types of monomers (b).
• the viscosity measurement of the monomer is carried out in two cases: (b-1) or (b-2), at least one of (b-1) and (b-2), and (b-3).
• the sample volume is 0.2 mL
• the rotor diameter is 1.9 cm
• the rotation speed is 20 rpm
• the range is "H".
• the sample amount is 1.1 mL
• the rotor diameter is 4.7 cm
• the rotation speed is If the viscosity is 5 rpm, and the range is "M" when the viscosity is ⁇ 100 mPa ⁇ s, "2.5M” when the viscosity is 100 to 200 mPa ⁇ s, and “5M” when the viscosity is 200 mPa ⁇ s or more, good.
• the viscosity of the ethylenically unsaturated group-containing monomer (b) at a temperature of 25° C. is preferably 1000 mPa ⁇ s or less, more preferably 500 mPa ⁇ s or less, and the lower limit is not particularly limited, but for example, 0.5 mPa ⁇ s. It may be.
• the composition of the present invention contains 0.05 to 4.5% by mass of ammonia (c) based on 100% by mass of the composition. When the composition contains ammonia (c) within the above range, an increase in the viscosity of the composition can be suppressed.
• the content of ammonia (c) in 100% by mass of the composition is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.2% by mass or more. Further, it is preferably 3% by mass or less, more preferably 1.5% by mass or less. That is, the content of ammonia (c) in 100% by mass of the composition is preferably 0.05 to 3% by mass, more preferably 0.1 to 1.5% by mass, and 0.2 to 1.5% by mass. is even more preferable. If the amount of ammonia is excessive, problems such as odor, yellowing of the cured composition, and deterioration of the appearance of the cured composition are likely to occur.
• the amount of ammonia (c) is 0.05% by mass or more based on 100% by mass of the composition, and 1% by mass or more.
• the content is preferably .5% by mass or less, more preferably 0.05% by mass or more and 0.5% by mass or less.
• ammonia (c ) The amount is preferably 0.1% by mass or more and 1% by mass or less based on 100% by mass of the composition.
• the amount of ammonia can be quantified by the calibration curve method (internal standard) using gas chromatography, as shown in the examples below.
• the composition of the present invention may contain a polymerization initiator.
• the polymerization initiator include photopolymerization initiators and thermal polymerization initiators, each of which may be used alone or in combination. Note that some photopolymerization initiators act as thermal polymerization initiators, and some thermal polymerization initiators act as photopolymerization initiators, so those that have both properties should be treated with light irradiation or heating. Accordingly, the active energy ray-curable resin composition can be cured.
• photopolymerization initiators are preferred because they do not impart thermal history to the formed film, the substrate to which the active energy ray-curable resin composition is applied, and the like.
• thermal polymerization initiator examples include 2,2'-azobis-(2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4'- oil-soluble initiators such as dimethylvaleronitrile), benzoyl peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butylperoxy-2-ethylhexanoate, Persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate; water-soluble peroxides such as hydrogen peroxide, and water-soluble azo compounds such as 2,2'-azobis(2-amidinopropane) dihydrochloride, etc.
• these thermal polymerization initiators may be used alone or in combination of two or more.
• photopolymerization initiators include benzophenone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, and oxyphenyl-acetic acid 2-[ 2-oxo-2-phenylacetoxyethoxy]-ethyl ester, oxyphenylacetic acid 2-[2-hydroxyethoxy]-ethyl ester, 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyl-diphenyl-phos Fin oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)2-hydroxy-2 -Methylpropan-1-one, 2-methyl-1-[4-(methylthio)phenyl]2-morpholinopropan-1-one, 2-morpholinopropan-1-one, iodonium, sulfonium salt,
• the amount of the polymerization initiator is, for example, 1 part by mass or more and 25 parts by mass or less, based on 100 parts by mass of the ethylenically unsaturated group-containing monomer (b).
• the composition of the present invention may contain a solvent in addition to the silica particles (a), the ethylenically unsaturated group-containing monomer (b), ammonia (c), and the preferably used polymerization initiator. Since the composition of the invention can exhibit a viscosity-reducing effect with a predetermined amount of ammonia, it is preferable that the composition does not contain a solvent or contains only a small amount of solvent. Therefore, the composition of the present invention preferably does not contain a solvent, or if it does contain a solvent, it is preferably 3.0% by mass or less, and 2.0% by mass based on 100% by mass of the composition. It is more preferable that it is below.
• the amount of solvent contained is small because the load on the environment can be reduced. Furthermore, if the solvent is contained in excess of a certain amount, a drying process will be required, which will reduce productivity.In addition, if the drying process is omitted when the solvent is contained in more than a certain amount, the appearance of the cured product of the composition will deteriorate. There is a problem that the strength decreases. From this point of view as well, it is desirable that no solvent be included or that the amount of solvent be small.
• the amount of solvent can be quantified by a calibration curve method (internal standard) using gas chromatography, as shown in the Examples below.
• composition of the present invention may contain additives other than the silica particles (a), the ethylenically unsaturated group-containing monomer (b), the ammonia (c) polymerization initiator, and the solvent,
• the content of other additives is preferably 3% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass or less based on 100% by mass of the composition.
• Viscosity of Composition Since the composition of the present invention contains ammonia (c), an increase in viscosity is suppressed.
• the ratio of the viscosity of the composition to the viscosity of the ethylenically unsaturated group-containing monomer (b) (if two or more types are used, the viscosity of the mixture) is preferably 90 or less, more preferably 70 or less, and 60 or less. More preferably, the lower limit is not particularly limited, but may be, for example, 3 or more, or 5 or more (that is, 90-3 is preferable, 70-5 is more preferable, and 60-5 is still more preferable). .
• the viscosity of the composition can be measured by using the above-mentioned measuring method suitable for the ethylenically unsaturated group-containing monomer (b) depending on the type of the ethylenically unsaturated group-containing monomer (b) contained in the composition. Just use it as is.
• the composition of the present invention can be prepared by a production method including a synthesis step (A) of silica particles (a) and a monomer substitution step (E).
• the manufacturing method may further include a surface treatment step (B) between the step (A) and the step (E), or before the monomer substitution step (E) (and the surface treatment step (B)).
• a surface treatment step (B) between the step (A) and the step (E), or before the monomer substitution step (E) (and the surface treatment step (B)).
• an ultrafiltration step (C) and an ion exchange step (D) may be included after step (B).
• Ammonia (c) contained in the composition of the present invention may be mixed at any stage.
• Synthesis step (A) of silica particles (a) In the synthesis step (A) of silica particles (a) (hereinafter also simply referred to as step (A)), silica particles are produced by hydrolyzing and condensing alkoxysilane in the presence of a basic catalyst and water.
• the alkoxysilane is a compound having an alkoxy group as a substituent on a silicon atom, and as a substituent on a silicon atom, in addition to the alkoxy group, an alkyl group having 2 to 6 carbon atoms or an aromatic group having 6 to 10 carbon atoms can be used as a substituent for the silicon atom. It may have a group hydrocarbon group. Furthermore, the hydrogen atom of the alkyl group may be substituted with a halogen atom, a vinyl group, a glycidyl group, a mercapto group, an amino group, or the like.
• alkoxysilane examples include compounds in which an alkoxy group and an unsubstituted or substituted alkyl group are bonded to a silicon atom, and mono- to tetrafunctional alkoxysilanes can be used, particularly tetramethoxysilane, tetraethoxysilane, etc. Preferred are tetrafunctional alkoxysilanes.
• the concentration of alkoxysilane is, for example, 0.1 mmol/g or more and 3 mmol/g or less.
• the concentration of alkoxysilane in the reaction solution is within this range, the reaction rate can be easily controlled and the particle size can be made uniform.
• the concentration of water in the reaction solution is preferably 2 mmol/g to 25 mmol/g based on the amount at the time of preparation (before the start of hydrolysis/condensation), and the molar ratio of water to alkoxysilane ( water/alkoxysilane) is preferably 4 to 10.
• Examples of the basic catalyst include ammonias, amines, quaternary ammonium compounds, etc. Among them, ammonias, amines, etc. Preferably. From the viewpoint of both catalytic effect and ease of removal, ammonias are preferred, and ammonia is particularly preferred.
• the concentration of the basic catalyst in the reaction solution is preferably 0.8 mmol/g to 2 mmol/g. Further, the total mass ratio of the basic catalyst and the basic catalyst and water (basic catalyst/(basic catalyst + water)) is preferably 0.2 or more and 0.32 or less.
• a diluent When hydrolyzing and condensing alkoxysilane, a diluent may be further present.
• the diluent is preferably a water-soluble organic solvent, and the water-soluble organic solvent is preferably an alcohol solvent, such as monools such as methanol, ethanol, propanol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol, or pentyl alcohol. More preferred, particularly methanol.
• the diluent content in the reaction solution is preferably 40% by mass or more and 90% by mass or less. Moreover, it is preferable that the diluent is 120 parts by mass or more and 500 parts by mass or less with respect to a total of 100 parts by mass of alkoxysilane and water. However, since the amount of alcohol changes due to hydrolysis and condensation of the alkoxysilane, the amount of the diluent is based on the amount at the time of preparation (before the start of hydrolysis and condensation).
• the reaction solution contains ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; paraffins such as isooctane and cyclohexane; ethers such as dioxane and diethyl ether; aromatic hydrocarbons such as benzene and toluene; etc.
• Hydrophobic organic solvents may also be included. When using these hydrophobic organic solvents, a surfactant may be added to improve dispersibility.
• the above components may be mixed in an appropriate order, but for example, after preparing a premixed solution in which components other than the alkoxysilane are mixed in advance, the alkoxysilane may be added to this premixed solution. Good too.
• the reaction temperature is preferably 20 to 70°C, and the duration of hydrolysis and condensation is preferably 30 minutes to 100 hours.
• step (B) The preferred manufacturing method of the present invention preferably includes a surface treatment step (B) (hereinafter also simply referred to as step (B)).
• step (B) it is preferable to mix the above-mentioned silane coupling agent and the reaction solution obtained after hydrolysis and condensation of the alkoxysilane obtained in step (A).
• step (B) it is preferable to add a silane coupling agent to the reaction solution after hydrolysis and condensation of the alkoxysilane obtained in step (A). It is preferable to add it.
• the silane coupling agent is preferably used in an amount of about 1 to 30 parts by weight, preferably 7 to 15 parts by weight, based on 100 parts by weight of the alkoxysilane used in step (A). After mixing the entire amount of the silane coupling agent and the reaction solution of step (A), it is preferable to stir the mixture for about 10 to 30 hours, for example. Preferably, step (B) is carried out at a temperature of 30 to 60°C.
• step (C) After step (A) or after step (B), it is preferable to perform an ultrafiltration step (C) (hereinafter also simply referred to as step (C)) of filtering with an ultrafiltration membrane.
• step (C) water, basic catalyst, diluent added as necessary, ketones, etc. contained in the reaction solution after hydrolysis/condensation are removed, and the step (C) is performed.
• the excess surface treatment agent that could not cover the silica particle surface in B) can be removed.
• a dispersion medium such as an alcoholic solvent different from the dispersion medium (reaction solvent) of the reaction liquid may be added while filtering through an ultrafiltration membrane.
• solvent substitution it is preferable to concentrate the silica particles (or surface-treated silica particles if surface-treated) to a concentration of about 5 to 20% by mass to form a silica particle dispersion.
• step (D) Ion exchange process
• step (D) Ion exchange step
• cation exchange resins Conventionally known cation exchange resins can be used, and either a weakly acidic cation exchange resin or a strongly acidic cation exchange resin may be used.
• Examples of weakly acidic cation exchange resins include Amberlite IRC-76 (manufactured by Organo Corporation), Diaion WK10, WK20 (manufactured by Mitsubishi Chemical Corporation), and Revachit CNP80 (manufactured by Bayer Corporation).
• Examples of strong acidic cation exchange resins include Amberlyst 16, Amberlyte IR-120B (manufactured by Organo Corporation), Diaion PK-208, PK-228, PK-216, (manufactured by Mitsubishi Chemical Corporation), Examples include Duolite C-26, Duolite ES-26 (manufactured by Sumitomo Chemical Co., Ltd.), and MSC-1, 88 (manufactured by Dow Corporation).
• step (E) In the monomer substitution step (E) (hereinafter also simply referred to as step (E)), the silica particle dispersion obtained in any of steps (A) to (D) and the ethylenically unsaturated group-containing monomer (b) and the dispersion medium contained in any one of steps (A) to (D) is distilled off.
• the dispersion medium may be removed by solid-liquid separation means such as centrifugation or distillation under reduced pressure, thereby removing the dispersion medium contained in any of steps (A) to (D). , is replaced by the ethylenically unsaturated group-containing monomer (b).
• the conditions for distilling off the dispersion medium in step (E) are not particularly limited, but for example, the temperature may be 20 to 60°C, the pressure may be 1 to 400 hPa, and the time may be 1 to 60 hours.
• ammonia (c) contained in the composition of the present invention may be ammonia used as a base catalyst in step (A), or may be ammonia used as a base catalyst in step (B) to step (E). It may also be by mixing.
• the amount of ammonia (c) depends on the amount of ammonia mixed in any of steps (A) to (E), the pH before monomer mixing in step (E), the implementation conditions of step (E), etc. Can be adjusted.
• the pH before monomer mixing in step (E) is preferably 5.5 to 11.5.
• composition of the present invention can suppress an increase in viscosity, it can be used in adhesive materials, dental materials, optical members, coating materials (for hard coats, anti-glare), nanocomposite materials, abrasives, nanoimprints, ink jets, etc. It is useful as a coating composition for forming precise microstructures such as resists.
• Measurement method Calibration curve method (internal standard) Column length: 30m Column inner diameter: 0.45mm Capillary inner membrane thickness: 0.85 ⁇ m Carrier gas: Helium Column temperature: Hold at 40°C for 2 minutes, raise the temperature to 180°C at 10°C/min, raise the temperature to 230°C at 50°C/min, hold at 230°C for 10 minutes Inlet temperature: 230°C Detector temperature: BID (230°C) Detection substance and time example: ammonia (0.4 min), anisole (6.6 min)
• Example 1 Step 1A Particle synthesis step 16,500 g of methanol, 4,200 g of water, and 2,000 g of 25% aqueous ammonia were placed in a 50 L SUS container equipped with a stirrer, a dropping port, and a thermometer, and the mixture was stirred for 30 minutes to obtain a uniform mixed solution.
• the temperature of the above mixed solution was adjusted to 49 to 51° C., and while stirring, 5700 g of tetramethyl orthosilicate (TMOS) was added dropwise from the dropping port over 90 minutes. After the dropwise addition was completed, stirring was continued for 30 minutes while maintaining the above liquid temperature to obtain an alcoholic solution suspension of silica particles (suspension 1A).
• TMOS tetramethyl orthosilicate
• Step 1B Surface treatment step The temperature of the suspension 1A obtained in the previous step was raised to 50° C. while stirring again, and while maintaining the liquid temperature and stirring, 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., 660 g of KBM-503) was added dropwise from the dropping port over 120 minutes. After the dropwise addition was completed, stirring was continued for 15 hours while maintaining the above liquid temperature to obtain an alcoholic solution suspension (suspension 1B) of silica particles having methacrylic groups on the particle surface.
• 3-methacryloxypropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd., 660 g of KBM-503
• Step 1C Ultrafiltration step The suspension 1B obtained in the above step B is filtered with methanol at room temperature using a commercially available ultrafiltration membrane equipped with a ceramic tubular ultrafiltration membrane with a molecular weight cutoff of about 10,000. By replacing the solvent with appropriate addition and concentrating until the SiO 2 concentration was about 11%, a methanol suspension (suspension 1C) of silica particles having a pH of 9.3 and a methacrylic group on the particle surface was obtained. .
• Step 1D Ion exchange process Suspension 1C is passed through a column filled with hydrogen type strongly acidic cation exchange resin Amberlite IR-120B (manufactured by Organo) at room temperature at a space velocity of 3 per hour. By passing through the solution at a high speed, a methanol suspension (suspension 1D) of silica particles having a methacrylic group having a pH of 6.1 was obtained.
• Amberlite IR-120B manufactured by Organo
• Step 1E Monomer Substitution Step Weigh 1800 g of a methanol suspension of silica particles having methacrylic groups (Suspension 1D), and add the same amount of 1,6-hexanediol diacrylate (HDDA) (monomer (b) as the silica particles contained). -3)) was added and the solvent was distilled off using a rotary evaporator to obtain an HDDA dispersion of silica particles having methacrylic groups (dispersion 1E).
• HDDA 1,6-hexanediol diacrylate
• Suspensions 2D (Example 2) and 3D (Example 3) were obtained in the same manner as in 1, and HDDA dispersions 2E (Example 2) and 3E (Example 3) of silica particles having methacrylic groups were obtained.
• Example 4 HDDA dispersion 4E (suspension 3D) of silica particles having methacrylic groups was prepared in the same manner as in Example 3, except that the time for distilling off the solvent of the methanol suspension (suspension 3D) of silica particles having methacrylic groups was changed. Example 4) was obtained.
• the average sphericity ratio of the silica particles was in the range of 1.05 to 1.

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