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• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
  • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
  • C08G73/0644—Poly(1,3,5)triazines
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
  • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/32—Epoxy compounds containing three or more epoxy groups
  • C08G59/3236—Heterocylic compounds
  • C08G59/3245—Heterocylic compounds containing only nitrogen as a heteroatom
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
  • C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
  • C08G59/688—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing phosphorus
• • 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
  • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
  • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
  • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
  • C07B2200/13—Crystalline forms, e.g. polymorphs
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

• the present invention relates to an ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate crystal and a method for producing the same.
• Use of this crystal provides a composition having excellent solubility when a liquid composition is formed and difficulty in precipitating a crystal during long term storage, and provides a cured product having excellent transparency, high heat resistance, and high light resistance when the composition is cured by heating.
• compositions provide a transparent coating film which is applicable to a protection film and the like.
• a transparent composite sheet and a transparent composite film can be obtained by bonding transparent substrates.
• a glass cloth-reinforced transparent substrate can be obtained by curing a glass cloth in combination with the composition whose refractive index is matched with the refractive index of the glass cloth. This glass cloth-reinforced transparent substrate can be used as a lightweight substrate for replacing glass.
• tris-(2,3-epoxypropyl)-isocyanurate can provide a cured product having excellent transparency, heat resistance, and light resistance by curing tris-(2,3-epoxypropyl)-isocyanurate with a curing agent such as a carboxylic acid anhydride.
• common tris-(2,3-epoxypropyl)-isocyanurate contains 25% by mass of ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate and 75% by mass of ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate.
• ⁇ -type is a crystal having a high melting point of about 150° C. and significantly low solubility.
• Tris-(2,3-epoxypropyl)-isocyanurate has three asymmetric carbons.
• a crystal formed of an equimolar mixture of (2R,2′R,2′′R)-tris-(2,3-epoxypropyl)-isocyanurate and (2S,2′S,2′′S)-tris-(2,3-epoxypropyl)-isocyanurate, in which the three asymmetric carbons have the same chirality, is generally called a ⁇ -type crystal. It has been known that the ⁇ -type crystal is a crystal having a high melting point of about 150° C.
• a crystal formed of a mixture of (2R,2R,2S)-tris-(2,3-epoxypropyl)-isocyanurate and (2S,2S,2R)-tris-(2,3-epoxypropyl)-isocyanurate, in which only one of the three asymmetric carbons has different optical anisotropy, is generally called an ⁇ -type crystal.
• the ⁇ -type crystal has different crystal structure from the ⁇ -type crystal described above and thus has a low melting point of about 100° C.
• This ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate and the method for producing the same are also disclosed (refer to Patent Document 2).
• Patent Document 1 Japanese Patent Application Publication No. 2000-007672 (JP 2000-007672 A)
• Patent Document 2 Japanese Patent Application Publication No. H4-264123 (JP H4-264123 A)
• the purpose of the present invention is to provide tris-(2,3-epoxypropyl)-isocyanurate having excellent workability including high solubility during use and difficulty in precipitating a crystal during storage with maintaining excellent properties of tris-(2,3-epoxypropyl)-isocyanurate, that is, an ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate crystal containing ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate in a ratio of 2% by weight to 15% by weight.
• Use of this crystal can provide a composition that is homogeneous and can be stored for a long period.
• the cured product of the composition having excellent transparency, heat resistance, and light resistance can be obtained when the composition is cured.
• the present invention provides as a first aspect, an ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate crystal containing ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate in the crystal in a ratio of 2% by mass to 15% by mass;
• the ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate crystal according to the first aspect or the second aspect, in which the crystal has a particle diameter of 1 ⁇ m to 500 ⁇ m;
• a method for producing the ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate crystal according to any one of the first aspect to the third aspect, the method comprising: (i) separating ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate contained in a tris-(2,3-epoxypropyl)-isocyanurate solution from the solution as a solid to obtain a crystal with an increased content ratio of ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate;
• the method for producing according to the fifth aspect in which the extraction in (ii) is carried out by using a heated solvent, a solvent at normal temperature, or a cooled solvent;
• the method for producing according to any one of the fourth aspect to the sixth aspect in which the solvent for the tris-(2,3-epoxypropyl)-isocyanurate solution used in (i) is methyl ethyl ketone, acetone, acetonitrile, ethyl acetate, or epichlorohydrin;
• a method for producing the ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate crystal according to any one of the first aspect to the third aspect, the method comprising (A), (B), and (i′):
• a liquid curable composition comprising the ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate crystal according to any one of the first aspect to the third aspect and a liquid cationic curable compound in a ratio of 0.2 molar equivalent to 5 molar equivalent relative to 1 molar equivalent of the crystal;
• the cured product according to the eighteenth aspect in which the attaching to the substrate is carried out by application, filling, adhesion, or impregnation.
• ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate generally has low solubility to an organic solvent and ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate may be precipitated during long term storage.
• ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate crystal of the present invention By using the ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate crystal of the present invention, a composition that is homogeneous and can be stored for a long period can be obtained. In addition, the crystal is easily dissolved into solvents and various curing agents.
• the crystal has excellent compatibility to amines, phenol-based substances, acid anhydrides, carboxylic acids, mercaptans, isocyanates, and polyvalent functional compounds and polyvalent functional macromolecules thereof, which have been known as general epoxy curing agents, and thus a curable composition containing the crystal and the curing agent provides a cured products having excellent homogeneity when the curable composition is cured with the curing agent.
• the cured product has excellent transparency, heat resistance, and light resistance.
• the present invention provides an ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate crystal containing ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate in the crystal in a ratio of 2% by mass to 15% by mass.
• the present invention provides the ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate crystal in which the ratio of contained ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate is in a range of 2% by mass to 15% by mass, 2% by mass to 10% by mass, 3% by mass to 15% by mass, 3% by mass to 10% by mass, or 4% by mass to 10% by mass.
• the content ratio of ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate in the crystal is 98% by mass to 85% by mass, 98% by mass to 90% by mass, 97% by mass to 85% by mass, 97% by mass to 90% by mass, or 96% by mass to 90% by mass.
• the crystal is the ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate crystal having a particle diameter of 1 ⁇ m to 500 ⁇ m or 1 ⁇ m to 100 ⁇ m.
• ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate is a crystal having a high melting point of about 150° C. and significantly low solubility and thus the content thereof is preferably 15% by weight or less. A content of more than 15% by weight is not preferable because the solubility of the crystal into solvents becomes significantly low.
• excessively low content of ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate results in high melting point and low solubility. This is because crystallization property is improved due to increase in the purity of ⁇ -form and thus the degree of crystallinity is increased. This causes reduction in dissolution rate and results in low solubility.
• the method for producing the crystal of the present invention includes (i) separating ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate contained in a tris-(2,3-epoxypropyl)-isocyanurate solution from the solution as a solid to obtain a crystal with an increased content ratio of ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate.
• the crystal is obtained by a method of dissolving ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate into a solvent, removing undissolved ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate by filtration, and removing the solvent from this solution.
• the solvent used in this method is not limited.
• a solvent having higher solubility to ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate and lower solubility to ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate, that is, a solvent having large solubility difference between them is preferable.
• Examples of the solvent may include methyl ethyl ketone, acetone, acetonitrile, ethyl acetate, and epichlorohydrin.
• the method for producing the crystal includes (ii) extracting ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate contained in the crystal or the solution of the ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate obtained in (i) with a solvent to obtain a crystal with an increased content ratio of ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate.
• the extraction in (ii) can be carried out by using a heated solvent, a solvent at normal temperature, or a cooled solvent.
• the heating temperature of the solvent is from a temperature of 10° C. or more higher than room temperature or normal temperature (20° C.) to a temperature equal to or lower than the boiling point of the solvent used at normal pressure.
• the temperature is preferably a temperature close to the boiling point of the solvent used at normal pressure.
• the cooled solvent can be used from a temperature 10° C. or more lower than room temperature or normal temperature (20° C.) to a temperature of about ⁇ 100° C.
• ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate is extracted from the ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate crystal containing 15% by mass or less of ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate obtained by the above method with the solvent and thus a crystal having even higher content ratio of ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate can be produced.
• fractional crystallization of ⁇ -type is carried out by using the solvent such as acetone that has a larger solubility difference of ⁇ -type and ⁇ -type of about 20:1 and then the filtrate was concentrated to obtain a crystal having a weight ratio of ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate and ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate of 94:6.
• the ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate crystal can be obtained by combining the above methods at the same time.
• ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate crystal having high purity can be finally produced through the steps for producing tris-(2,3-epoxypropyl)-isocyanurate.
• the method includes the following (A), (B), and (i′):
• the method includes the following (ii′):
• the extraction in (ii′) can be carried out by using a heated solvent, a solvent at normal temperature, or a cooled solvent.
• Methyl ethyl ketone, acetone, methanol, ethanol, water, isopropanol, or the like is used as the solvent used in (ii′).
• the ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate crystal of the present invention is easily dissolved into solvents and various types of curing agents.
• the crystal has excellent compatibility to amines, phenol-based substances, acid anhydrides, carboxylic acids, mercaptans, isocyanates, and polyvalent functional compounds and polyvalent functional macromolecules thereof, which have been known as general epoxy curing agents, and thus the crystal provides a cured products having excellent homogeneity when the crystal is cured with the curing agent.
• the crystal provides a homogeneous paint because the crystal has an excellent mixing property when the crystal is melted and kneaded with a polyester having carboxylic acid terminals and thus the paint provides a coating film having excellent flatness.
• the crystal provides a composition having excellent homogeneity when the crystal is mixed with an amine-based curing agent. Using slow crystallization rate of this compound, a transparent film made of tris-(2,3-epoxypropyl)-isocyanurate alone also can be obtained by once dissolving the composition into a solvent along with a initiator such as an acid generator, applying the resultant solution onto a substrate and thereafter removing the solvent, and curing the applied film before crystallization.
• a transparent film made of tris-(2,3-epoxypropyl)-isocyanurate alone also can be obtained by once dissolving the composition into a solvent along with a initiator such as an acid generator, applying the resultant solution onto a substrate and thereafter removing the solvent, and curing the applied film
• a transparent and homogeneous liquid composition can be obtained, even when the solvent is not used, by mixing the ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate crystal of the present invention with an acid anhydride such as a carboxylic acid anhydride that is transparent and a liquid state at room temperature and an significantly highly transparent cured product can be obtained by curing the liquid composition.
• an acid anhydride such as a carboxylic acid anhydride that is transparent and a liquid state at room temperature and an significantly highly transparent cured product can be obtained by curing the liquid composition.
• liquid carboxylic acid anhydride at room temperature may include 3-methyl-cyclohexane dicarboxylic acid anhydride, 4-methyl-cyclohexane dicarboxylic acid anhydride, and a mixture of 3-methyl-cyclohexane dicarboxylic acid anhydride and 4-methyl-cyclohexane dicarboxylic acid anhydride.
• a transparent and homogeneous liquid composition can be obtained by using a cationic curable compound that is transparent and a liquid state at room temperature even when the solvent is not used.
• a highly transparent cured product can be obtained by curing the liquid composition.
• a liquid curable composition containing the ⁇ -type tris-(2,3-epoxypropyl)-isocyanurate crystal and the liquid cationic curable compound in a ratio of 0.2 molar equivalent to 5 molar equivalent relative to 1 molar equivalent of the crystal is prepared and the liquid curable composition is attached to a substrate, whereby a transparent cured product can be obtained.
• a cationic initiator activated by heat or light allows a transparent cured product such as a coating film, an adhesive, and a molded product to be prepared.
• the cationic initiator activated by heat or light is also called a thermal acid generator or a photoacid generator. Any substance can be used as the cationic initiator as long as an acid, which is a cation source, is generated from the substance by energy such as heat or light.
• the photoacid generator or the thermal acid generator is not particularly limited as long as the substance directly or indirectly generates an acid by light irradiation or heating.
• the photoacid generator may include triazine compounds, acetophenone derivative compounds, disulfonic compounds, diazomethane compounds, sulfonic acid derivative compounds, onium salts such as iodonium salts, sulfonium salts, phosphonium salts, and selenium salts, metallocene complexes, and iron arene complexes.
• Examples of the onium salts used as the photoacid generator may include iodonium salts such as diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium mesylate, diphenyliodonium tosylate, diphenyliodonium bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis(p-tert-butylphenyl)iodonium hexafluorophosphate, bis(p-tert-butylphenyl)iodonium mesylate, bis(p-tert-butylphenyl)iodonium tosylate, bis(p-tert-butylphenyl)iodonium trifluoromethanesulfonate, bis
• sulfonium salts may include triphenylsulfonium salts such as triphenylsulfonium chloride, triphenylsulfonium bromide, tri(p-methoxyphenyl)sulfonium tetrafluoroborate, tri(p-methoxyphenyl)sulfonium hexafluorophosphonate, tri(p-ethoxyphenyl)sulfonium tetrafluoroborate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, and triphenylsulfonium hexafluorophosphate; and sulfonium salts such as (4-phenylthiophenyl)diphenylsulfonium hexafluoroantimonate, (4-phenylthiophenyl)diphenylsulfonium hexafluorophosphate, bis[
• Examples of the phosphonium salts may include phosphonium salts such as triphenylphosphonium chloride, triphenylphosphonium bromide, tri(p-methoxyphenyl)phosphonium tetrafluoroborate, tri(p-methoxyphenyl)phosphonium hexafluorophosphate, tri(p-ethoxyphenyl)phosphonium tetrafluoroborate, 4-chlorobenzenediazonium hexafluorophosphate, and benzyltriphenylphosphonium hexafluoroantimonate.
• phosphonium salts such as triphenylphosphonium chloride, triphenylphosphonium bromide, tri(p-methoxyphenyl)phosphonium tetrafluoroborate, tri(p-methoxyphenyl)phosphonium hexafluorophosphate, tri(p-ethoxyphenyl)phosphonium tetrafluoroborate, 4-
• the following compounds can also be used as the photoacid generator.
• the sulfonium salt compounds and the iodonium salt compounds are preferable for the photoacid generator.
• anions of the sulfonium salt compounds and the iodonium salt compounds may include CF 3 SO 3 ⁇ , C 4 F 9 SO 3 ⁇ , C 8 F 17 SO 3 ⁇ , camphor sulfonic acid anion, tosylate anion, BF 4 ⁇ , PF 6 ⁇ , AsF 6 ⁇ , and SbF 6 ⁇ .
• anion species such as phosphorus hexafluoride and antimony hexafluoride, which indicate strong acidity, are preferable.
• thermal acid generator may include sulfonium salts and phosphonium salts, and the sulfonium salts are preferably used.
• the following compounds can be exemplified.
• R includes a C 1-12 , alkyl group and a C 6-20 aryl group, and the C 1-12 alkyl group is particularly preferable.
• thermal acid generators can be used singly or in combination of two or more of them.
• the curable composition of the present invention can provide transparent cured products such as coating films, adhesives, and molded products by adding a curing accelerator, an antioxidant, or other additives, and applying heat.
• the thickness of the coating film can be selected in a range from about 0.01 ⁇ m to 10 mm.
• the thickness can be about 0.05 ⁇ m to 10 urn (particularly, 0.1 ⁇ m to 5 ⁇ m); when the coating film is used as a printed circuit board, the thickness can be about 10 ⁇ m to 5 mm (particularly, 100 ⁇ m to 1 mm); and when the coating film is used as an optical thin film, the thickness can be about 0.1 ⁇ m to 100 ⁇ m (particularly, 0.3 ⁇ m to 50 ⁇ m).
• the amount is about 2 mJ/cm 2 to 20,000 mJ/cm 2 , and preferably about 5 mJ/cm 2 to 5,000 mJ/cm 2 .
• the light source can be selected depending on the exposition light.
• the usable light source for ultraviolet rays may include a low-pressure mercury lamp, a high pressure mercury lamp, an ultrahigh-pressure mercury lamp, a deuterium lamp, a halogen lamp, laser light (such as helium-cadmium laser and excimer laser). Such light irradiation can promote curing reaction of the composition.
• heating of the coating film is carried out as required, for example, at about 60° C. to 250° C. and preferably at about 100° C. to 200° C.
• the heating time can be selected in a range of 3 seconds or more (for example about 3 seconds to 5 hours).
• the heating can be carried out for about 5 seconds to 2 hours and preferably about 20 seconds to 30 minutes, and usually the heating can be carried out for about 1 minute to 3 hours (for example, 5 minutes to 2.5 hours).
• pattern exposure of the coating film formed on the substrate may be carried out.
• the pattern exposure can be carried out by scanning with laser light or light irradiation through a photomask.
• the patterns or the images can be formed by developing (or dissolving) non-irradiated region (unexposed part) generated by such pattern exposure with a development agent.
• Examples of the alkaline aqueous solution may include aqueous solutions of alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate; aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine.
• alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate
• quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline
• amines such as ethanolamine, propylamine, and ethylenediamine.
• the alkali development liquid is usually an aqueous solution in a concentration of 10% by mass or less.
• An aqueous solution in a concentration of 0.1% by mass to 3.0% by mass is preferably used, for example.
• the development liquid to which alcohols and surfactants are added can be used. Each of them can be contained preferably in a concentration of 0.05 parts by mass to 10 parts by mass relative to 100 parts by mass of the development liquid.
• tetramethylammonium hydroxide aqueous solution 0.1% by mass to 2.38% by mass tetramethylammonium hydroxide aqueous solution can be used.
• a general organic solvent can be used as the organic solvent for the development liquid.
• the organic solvent may include acetone, acetonitrile, toluene, dimethylformamide, methanol, ethanol, isopropanol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate propylene glycol butyl ether acetate, ethyl lactate, and cyclohexanone.
• These organic solvents can be used singly or in combination of two or more of them.
• propylene glycol methyl ether, propylene glycol methyl ether acetate, ethyl lactate, and the like can be preferably used.
• the fluorine-containing surfactants are preferable from the viewpoint of high improvement effect for coating properties.
• Specific examples of the fluorine-containing surfactants may include Eftop EF301, EF303, and EF352 (trade name, manufactured by Tochem Products Co.), Megafac F171, F173, R-30, R-08, R-90, BL-20, and F-482 (trade name, manufactured by Dainippon Ink and Chemicals, Incorporated), Fluorad FC430 and FC431 (trade name, manufactured by Sumitomo 3M Ltd.), and AsahiGuard AG710, and Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (trade names, manufactured by Asahi Glass Co., Ltd.).
• the fluorine-containing surfactants are not particularly limited to these products.
• the particle diameter of the obtained crystal was 1 ⁇ m to 100 ⁇ m.
• the mixture was once cooled to 80° C., and 100 mg of tetra-n-butylphosphonium-o,o-diethylphosphorodithioate (manufactured by Nippon Chemical Industrial Co., Ltd., trade name HISHICOLIN PX-4ET) was added and dissolved. Thereafter, degassing and removal of volatile matters were carried out under reduced pressure for several minutes.
• tetra-n-butylphosphonium-o,o-diethylphosphorodithioate manufactured by Nippon Chemical Industrial Co., Ltd., trade name HISHICOLIN PX-4ET
• This mixture was heated at 100° C. for 2 hours. Thereafter, the temperature was raised to 150° C. and the mixture was heated at this temperature for 5 hours to obtain a cured product.
• the bending strength was 130 MPa.
• the flexural modulus was 4.000 MPa.
• the maximum amount of deflection was 7.7 mm.
• TMA thermal analysis
• Tg was 185° C.
• CTE1 linear expansion coefficient
• thermosetting plastics This cured product was evaluated in accordance with “Testing methods for thermosetting plastics” in Japanese Industrial Standards (JIS-K6911).
• the bending strength was 140 MPa.
• the flexural modulus was 4.100 MPa.
• the maximum amount of deflection was 7.7 mm.
• TMA thermal analysis
• Tg was 183° C.
• CTE1 linear expansion coefficient
• tris-(2,3-epoxypropyl)-isocyanurate crystal having excellent workability including high solubility during use and difficulty in precipitating a crystal during storage can be obtained.
• the epoxy composition using this crystal can provide a composition that is homogeneous and can be stored for a long period.
• the cured product of the composition having excellent transparency, high heat resistance, and high light resistance can be obtained when the composition is cured.

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• Polyurethanes Or Polyureas (AREA)
• Epoxy Compounds (AREA)

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