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
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
  • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
  • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
  • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D317/34—Oxygen atoms
  • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
  • C07D317/38—Ethylene carbonate
• • 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
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• • 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
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • 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
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16

Definitions

• the present invention relates to a curable composition, preferably an active energy ray-curable composition, and particularly preferably a solvent-free active energy ray-curable composition, which belongs to these technical fields.
• acryloyl group and / or methacryloyl group is referred to as "(meth) acryloyl group”
• acrylate and / or methacrylate is referred to as "(meth) acrylate”
• “acrylic acid and / or methacrylic acid” "Acid” is expressed as "(meth) acrylic acid”.
• a compound having an ethylenically unsaturated group is referred to as a "curable component" in the composition.
• Curable compositions are used in a variety of applications such as coatings, adhesives, inks, and electronic materials.
• the active energy ray-curable composition has an advantage that it can be cured in a very short time, and (meth) acrylate having excellent curability is often used.
• a high-pressure mercury lamp and a metal halide are used as a light source.
• ultraviolet rays are irradiated in a nitrogen atmosphere or the composition is coated on a base material, and then a film is laminated on the coated surface and ultraviolet rays are irradiated under oxygen blocking.
• the scope of application is limited due to problems such as large size of equipment, high cost, and low productivity.
• oxygen inhibition is reduced by adding an additive such as an amine compound and a phosphorus compound to the composition, but such a relatively highly effective additive is a cured product. There is a problem of coloring.
• G. Wegner et al. (2-oxo-1,3-dioxolane-4-yl) methyl (meth) acrylate [glycerin carbonate (meth) acrylate.
• Glycarbo- (M) A Is obtained by the reaction of glycerol carbonate with (meth) acrylic acid chloride (Non-Patent Document 2).
• the manufacturing method described in the same document is based on the acid chloride method, and there is a problem in consideration of the problem of corrosion of the container and the large environmental load.
• the compound produced by the method described in the same document has a high concentration of sodium and chlorine, and therefore, when used as a component of a curable composition, the cured product has a problem of metal corrosion. There were problems such as low water resistance.
• Patent Document 1 discloses an abrasion-resistant coating composition containing a trifunctional or higher functional polyacrylate and Glycarbo- (M) A, which has a high hardness, a high curing rate, and excellent adhesion. , It is disclosed that the effect of less coloring of the cured product is obtained (Patent Document 1).
• the method for producing Glycarbo- (M) A in Patent Document 1 is also based on the acid chloride method, and the composition has the above-mentioned problems.
• the present inventors have conducted diligent studies to find a curable composition containing Glycarbo- (M) A, which has no problem of metal corrosion and has excellent water resistance. It is.
• the present inventors have prepared a curable composition containing Glycarbo- (M) A as the component (A) and reducing the chlorine concentration and the sodium concentration contained in the component (A).
• the present invention has been completed by finding that the cured product is excellent in metal corrosion resistance and water resistance.
• the present invention will be described in detail.
• the cured product can be made excellent in metal corrosion resistance and water resistance.
• the present invention is a composition containing the component (A), wherein the component (A) contains a compound represented by the formula (a) described later, and the chlorine concentration contained in the component (A) is less than 100 ppm. It is a curable composition having a sodium concentration of less than 100 ppb.
• the component (A), the curable composition, the use and the method of use will be described.
• Ra means a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
• R b means a single bond or an oxyalkylene group.
• Ra in the formula (a) means a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R a is preferably a hydrogen atom or a methyl group.
• Examples of the oxyalkylene group in R b include an ethylene oxide group, a propylene oxide group, a tetramethylene oxide group, and a mixing unit of these alkylene oxide groups, and an ethylene oxide group is preferable.
• the oxyalkylene group in R b may be an alkylene oxide group having a repeating unit, preferably 1 to 20, and more preferably 1 to 15.
• the composition containing the component (A) is less susceptible to oxygen inhibition, has excellent curability, can reduce the viscosity of the composition without a solvent, and the cured product has excellent hardness, scratch resistance, and substrate adhesion. ..
• a compound in which Ra is a hydrogen atom or a methyl group and R b is a single bond is preferable. That is, Glycarbo- (M) A [(2-oxo-1,3-dioxolane-4-yl) methyl (meth) acrylate] is preferable.
• a compound having a hydrogen atom as R in the formula (a), that is, Glycarbo-A [(2-oxo-1,3-dioxolan-4-yl) methyl acrylate] is more preferable in that it is excellent in curability.
• the compound of the formula (a) is preferably a compound in which Ra is a hydrogen atom or a methyl group, R b is an oxyalkylene group, and the repeating unit of the oxyalkylene group is 1 to 15.
• the component (A) may be a mixture of these compounds.
• the component (A) has a chlorine concentration of less than 100 ppm and a sodium concentration of less than 100 ppb.
• the chlorine concentration in the present invention means a value obtained by the quartz tube combustion-ion chromatography method.
• the sodium concentration in the present invention means a value obtained by measuring a sample with an ICP mass spectrometer and quantifying the detected element by an absolute calibration curve method.
• glycerin carbonate As a method for producing the component (A), glycerin carbonate, an alkylene oxide adduct of glycerin carbonate, or a mixture of these compounds is used in that the component (A) having the above-mentioned chlorine concentration and sodium concentration can be easily produced.
• a glycerin carbonate compound and (meth) acrylic acid are subjected to a dehydration esterification reaction
• the component (A) can be produced in good yield and with reduced chlorine concentration and sodium concentration.
• the method for producing the glycerin carbonate-based compound, the monofunctional (meth) acrylate, the catalyst, and the component (A) will be described with respect to the method for producing the component (A) by a transesterification reaction, which is a preferable method for producing the component (A).
• the glycerin carbonate-based compound used as a raw material for the glycerin carbonate-based compound (A) component is a glycerin carbonate, an alkylene oxide adduct of the glycerin carbonate, or a mixture of these compounds.
• a glycerin carbonate (4-hydroxymethyl-1,3-dioxolane-2-one)
• a commercially available product can be used.
• a compound produced by transesterifying glycerin with a carbonic acid ester compound such as ethylene carbonate, dimethyl carbonate and diethyl carbonate in the presence of a catalyst can also be used.
• an ethylene oxide adduct of glycerin carbonate an ethylene oxide adduct of glycerin and a carbonic acid ester compound such as ethylene carbonate, dimethyl carbonate and diethyl carbonate are synthesized by transesterification reaction in the presence of a catalyst. Can be done.
• a carbonic acid ester compound such as ethylene carbonate, dimethyl carbonate and diethyl carbonate
• glycerin carbonate-based compound a mixture of the above-mentioned compounds can also be used.
• a compound represented by the following general formula (1) can be mentioned.
• R 1 represents a hydrogen atom and an alkyl group having 1 to 5 carbon atoms
• R 2 represents an organic group having 1 to 50 carbon atoms.
• R 1 in the above general formula (1) a hydrogen atom or a methyl group is preferable.
• R 2 in the above general formula (1) include 1 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and a 2-ethylhexyl group.
• R 2 in the general formula (1) include the functional groups mentioned in JP-A-2017-39916, JP-A-2017-39917, and International Publication No. 2017/033732. ..
• these monofunctional (meth) acrylates can be used alone or in any combination of two or more.
• carbons such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate
• alkoxyalkyl (meth) acrylates such as 2-methoxyethyl (meth) acrylate, and N, N-dimethylaminoethyl (meth) acrylate are preferable, and glycerin carbonate is particularly preferable.
• the transesterification reaction catalyst in the method for producing the catalyst (A) component conventionally known catalysts such as tin-based catalysts, titanium-based catalysts, and sulfuric acid can be used.
• Catalyst X Cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof (hereinafter referred to as “azabicyclo compound”), amidine or a salt or complex thereof (hereinafter referred to as “amidine compound”), a compound having a pyridine ring or
• One or more compound catalyst Y a compound containing zinc selected from the group consisting of the salt or complex (hereinafter referred to as "pyridine compound”) and phosphine or a salt or complex thereof (hereinafter referred to as "phosphine compound”).
• pyridine compound a compound containing zinc selected from the group consisting of the salt or complex
• phosphine compound phosphine compound
• the catalyst X is one or more compounds selected from the group consisting of azabicyclo-based compounds, amidine-based compounds, pyridine-based compounds, and phosphine-based compounds.
• the catalyst X one or more compounds selected from the group consisting of azabicyclo-based compounds, amidine-based compounds and pyridine-based compounds are preferable among the above-mentioned compound groups. These compounds have excellent catalytic activity and can preferably produce the component (A).
• they form a complex with the catalyst Y described later after the reaction is completed they can be easily obtained from the reaction solution after the reaction by a simple method such as filtration and adsorption. Can be removed.
• the azabicyclo-based compound can be more easily removed by filtration, adsorption or the like because the complex with the catalyst Y becomes sparingly soluble in the reaction solution.
• the phosphine compound has excellent catalytic activity, it is difficult to form a complex with the catalyst Y, and most of the phosphine compound remains dissolved in the reaction solution after the reaction is completed. Difficult to remove from liquid. For this reason, the phosphine-based catalyst remains in the final product, which causes turbidity and catalyst precipitation during storage of the product, and thickening or gelation over time, resulting in storage stability. It may cause problems, and it may have similar problems when used as a component of a composition.
• the azabicyclo-based compound examples include a cyclic tertiary amine having an azabicyclo structure, a salt of the amine, and various compounds as long as they satisfy the complex of the amine, and preferred compounds include quinuclidine and 3. -Hydroxyquinuclidine, 3-quinucridinone, 1-azabicyclo [2.2.2] octane-3-carboxylic acid, and triethylenediamine (also known as 1,4-diazabicyclo [2.2.2] octane. DABCO ”) and the like.
• Specific examples of the azabicyclo-based compound include the compounds mentioned in JP-A-2017-39916, JP-A-2017-39917, WO2016 / 163208 and WO2017 / 033732. Be done.
• amidine-based compound examples include imidazole, N-methylimidazole, N-ethyl imidazole, 1-benzyl-2-methyl imidazole, 1-benzyl-2-phenyl imidazole, 1-vinyl imidazole, 1-allyl imidazole, 1 , 8-Diazabicyclo [5.4.0] Undec-7-ene (hereinafter referred to as "DBU”), 1,5-Diazabicyclo [4.3.0] Nona-5-ene (hereinafter referred to as "DBN”) , N-Methylimidazole hydrochloride, DBU hydrochloride, DBN hydrochloride, N-methylimidazole acetate, DBU acetate, DBN acetate, N-methylimidazole acrylate, DBU acrylate, DBN acrylate, and Examples include phthalimide DBU and the like.
• pyridine compounds include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, and N, N-dimethyl-. Examples thereof include 4-aminopyridine (hereinafter referred to as "DMAP").
• DMAP 4-aminopyridine
• Specific examples of the pyridine compound include the compounds mentioned in JP-A-2017-39916, JP-A-2017-39917, WO2016 / 163208 and WO2017 / 033732. Be done.
• Examples of the phosphine or a salt or complex thereof include a compound containing a structure represented by the following general formula (2).
• R 3 , R 4 and R 5 are a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 1 to 20 carbon atoms, and 6 carbon atoms. It means an aryl group of up to 24 or a cycloalkyl group having 5 to 20 carbon atoms. R 3 , R 4 and R 5 may be the same or different. ]
• phosphine compounds include triphenylphosphine, tris (4-methoxyphenyl) phosphine, tri (p-tolyl) phosphine, tri (m-tolyl) phosphine, and tris (4-methoxy-3,5-dimethylphenyl). ) Phosphine, tricyclohexylphosphine and the like.
• Specific examples of the phosphine-based compound include the compounds mentioned in JP-A-2017-39916, JP-A-2017-39917, WO2016 / 163208 and WO2017 / 033732. Be done.
• these catalysts X can be used alone or in any combination of two or more.
• quinuclidine, 3-quinuclidinone, 3-hydroxyquinuclidine, DABCO, N-methylimidazole, DBU, DBN and DMAP are preferable, and particularly good reactivity with most glycerin carbonate compounds.
• 3-Hydroxyquinuclidine, DABCO, N-methylimidazole, DBU and DMAP which are easily available, are more preferable.
• the ratio of the catalyst X used in the method for producing the component (A) is not particularly limited, but it is preferable to use 0.0001 to 0.5 mol of the catalyst X with respect to 1 mol of the total hydroxyl groups in the glycerin carbonate-based compound. , More preferably 0.0005 to 0.2 mol.
• 0.0001 mol or more of the catalyst X the amount of the component (A) produced can be increased, and by using 0.5 mol or less, the formation of by-products and the coloring of the reaction solution can be suppressed. , The purification step after the reaction is completed can be simplified.
• the catalyst Y is a compound containing zinc.
• various compounds can be used as long as they are compounds containing zinc, but zinc organic acid and zinc diketone enolate are preferable because of their excellent reactivity.
• the zinc organic acid include zinc dibasate such as zinc oxalate and a compound represented by the following general formula (3).
• R 6 and R 7 have a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 1 to 20 carbon atoms, and 6 to 24 carbon atoms. It means an aryl group or a cycloalkyl group having 5 to 20 carbon atoms. R 6 and R 7 may be the same or different.
• a compound in which R 6 and R 7 are linear or branched alkyl groups having 1 to 20 carbon atoms is preferable.
• the linear or branched alkyl group having 1 to 20 carbon atoms is a functional group having no halogen atom such as fluorine and chlorine, and the catalyst Y having the functional group has a high yield. It is preferable because the component (A) can be produced in the above.
• Examples of the zinc diketone enolate include compounds represented by the following general formula (4).
• R 8 , R 9 , R 10 , R 11 , R 12 and R 13 are hydrogen atoms, linear or branched alkyl groups having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. It means a linear or branched alkenyl group, an aryl group having 6 to 24 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms. R 8 , R 9 , R 10 , R 11 , R 12 and R 13 may be the same or different. ]
• the zinc-containing compound represented by the above general formula (3) include zinc acetate, zinc acetate dihydrate, zinc propionate, zinc octylate, zinc neodecanoate, zinc laurate, zinc myristate, and the like.
• Examples thereof include zinc stearate, zinc cyclohexane butyrate, zinc 2-ethylhexanate, zinc benzoate, zinc t-butyl benzoate, zinc salicylate, zinc naphthenate, zinc acrylate, and zinc methacrylate.
• the complex with the hydrate, solvate, and catalyst X is also a component (A). Can be used as the catalyst Y in the production method of.
• the zinc-containing compound represented by the above general formula (4) include zinc acetylacetonate, zinc acetylacetonate hydrate, bis (2,6-dimethyl-3,5-heptandionat) zinc, and bis. Examples thereof include (2,2,6,6-tetramethyl-3,5-heptandionat) zinc and bis (5,5-dimethyl-2,4-hexanedionat) zinc. If a complex with the hydrate, solvate, or catalyst X of these zinc-containing compounds is present, the complex with the hydrate, solvate, and catalyst X is also a component (A). Can be used as the catalyst Y in the production method of.
• the above-mentioned compounds can be directly used, but these compounds can also be generated and used in the reaction system.
• zinc compounds such as metallic zinc, zinc oxide, zinc hydroxide, zinc chloride and zinc nitrate (hereinafter referred to as "raw zinc compound") are used as raw materials, and in the case of organic acid zinc, the raw material zinc compound and organic acid
• raw zinc compound a method of reacting the raw material zinc compound with 1,3-diketone and the like can be mentioned.
• these catalysts Y can be used alone or in any combination of two or more.
• these catalysts Y zinc acetate, zinc propionate, zinc acrylate, zinc methacrylate, and zinc acetylacetonate are preferable, and in particular, they show good reactivity with glycerin carbonate-based compounds and are easily available.
• Zinc acetate, zinc acrylate, and zinc acetylacetonate are preferred.
• the ratio of the catalyst Y used in the method for producing the component (A) is not particularly limited, but it is preferable to use 0.0001 to 0.5 mol of the catalyst Y with respect to 1 mol of the total hydroxyl groups in the glycerin carbonate-based compound. , More preferably 0.0005 to 0.2 mol.
• 0.0001 mol or more of the catalyst Y the amount of the component (A) produced can be increased, and by using 0.5 mol or less, the formation of by-products and the coloring of the reaction solution can be suppressed. , The purification step after the reaction is completed can be simplified.
• Component (A) is preferably produced by transesterifying a glycerin carbonate-based compound with a monofunctional (meth) acrylate in the presence of a transesterification catalyst.
• a method for producing the component (A) a production method in which the catalysts X and Y are used in combination as a catalyst is preferable, and the production method will be described below.
• the ratio of the catalyst X and the catalyst Y used in the method for producing the component (A) is not particularly limited, but it is preferable to use 0.005 to 10.0 mol of the catalyst X with respect to 1 mol of the catalyst Y. It is preferably 0.05 to 2.0 mol.
• 0.005 mol or more the amount of the compound of the target formula (a) produced can be increased, and by using 10.0 mol or less, the formation of by-products and the coloring of the reaction solution are suppressed. Therefore, the purification step after the reaction is completed can be simplified.
• the catalyst X is an azabicyclo-based compound
• the catalyst Y is a compound represented by the general formula (3)
• the azabicyclo-based compound is DABCO.
• the compound represented by the general formula (3) is zinc acetate and / or zinc acrylate.
• the catalyst X and the catalyst Y used in the present invention may be added from the beginning of the above reaction or may be added from the middle. Further, the desired amount to be used may be added all at once, or may be added in divided portions.
• the reaction temperature in the method for producing the component (A) is preferably 40 to 180 ° C, more preferably 60 to 160 ° C.
• the reaction rate can be increased, and by setting the reaction temperature to 180 ° C. or lower, thermal polymerization of the (meth) acryloyl group in the raw material or product is suppressed, and the reaction solution is colored. Can be suppressed, and the purification step after the reaction is completed can be simplified.
• the reaction pressure in the method for producing the component (A) is not particularly limited as long as a predetermined reaction temperature can be maintained, and may be carried out in a reduced pressure state or in a pressurized state.
• the reaction pressure is preferably 0.000001 to 10 MPa (absolute pressure).
• a monohydric alcohol derived from a monofunctional (meth) acrylate is produced as a by-product as the transesterification reaction progresses.
• the monohydric alcohol may remain coexisting in the reaction system, but the progress of the transesterification reaction can be further promoted by discharging the monohydric alcohol out of the reaction system.
• the reaction can be carried out without using an organic solvent, but an organic solvent may be used if necessary.
• organic solvent include n-hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, n-nonane, n-decane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, amylbenzene, and diah.
• Hydrocarbons such as milbenzene, triamylbenzene, dodecylbenzene, didodecylbenzene, amyltoluene, isopropyltoluene, decalin and tetralin; diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, diethyl acetal, dihexyl Ethers such as acetal, t-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, trioxane, dioxane, anisole, diphenyl ether, dimethyl cellosolve, jiglime, triglime and tetraglime; crown ethers such as 18-crown-6; Ethers such as methyl benzoate and ⁇ -butyrolactone; ketones such as acetone, methyl
• solvents hydrocarbons, ethers, carbonate compounds and ionic liquids are preferred. These solvents may be used alone, or two or more kinds may be arbitrarily combined and used as a mixed solvent.
• an inert gas such as argon, helium, nitrogen or carbon dioxide may be introduced into the system for the purpose of maintaining a good color tone of the reaction solution, but acryloyl group polymerization may be carried out.
• Oxygen-containing gas may be introduced into the system for the purpose of prevention.
• Specific examples of the oxygen-containing gas include air, a mixed gas of oxygen and nitrogen, a mixed gas of oxygen and helium, and the like.
• a method for introducing the oxygen-containing gas there is a method of dissolving it in the reaction solution or blowing it into the reaction solution (so-called bubbling).
• a polymerization inhibitor to the reaction solution for the purpose of preventing the polymerization of the (meth) acryloyl group.
• the polymerization inhibitor include organic polymerization inhibitors, inorganic polymerization inhibitors, organic salt polymerization inhibitors and the like.
• organic polymerization inhibitor examples include hydroquinone, tert-butyl hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol and 4 Examples thereof include phenolic compounds such as -tert-butylcatechol, quinone compounds such as benzoquinone, phenothiazine, and N-nitroso-N-phenylhydroxylamineammonium.
• organic polymerization inhibitor an organic compound having a stable radical can also be used, and examples thereof include carbinoxyl and N-oxyl compounds.
• N-oxyl compound examples include 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl and 4-oxo-2,2. , 6,6-Tetramethylpiperidin-1-oxyl and 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl and the like.
• the inorganic polymerization inhibitor examples include copper chloride, copper sulfate, iron sulfate and the like.
• organic salt-based polymerization inhibitor examples include copper dibutyldithiocarbamate, N-nitroso-N-phenylhydroxylamine aluminum salt and the like.
• the polymerization inhibitor may be added alone or in combination of two or more, may be added from the beginning of the present invention, or may be added in the middle. Further, the desired amount to be used may be added all at once, or may be added in divided portions. Moreover, you may add continuously via a rectification tower.
• the addition ratio of the polymerization inhibitor is preferably 5 to 30,000 wtppm, more preferably 25 to 10,000 wtppm in the reaction solution. By setting this ratio to 5 wtppm or more, the polymerization inhibitory effect can be sufficiently exerted, and by setting it to 30,000 wtppm or less, coloring of the reaction solution can be suppressed and the purification step after the reaction is completed can be simplified. In addition, it is possible to prevent a decrease in the curing rate of the obtained component (A).
• the reaction time in the method for producing the component (A) varies depending on the type and amount of the catalyst used, the reaction temperature, the reaction pressure, etc., but is preferably 0.1 to 150 hours, more preferably 0.5 to 80 hours.
• the method for producing the component (A) can be carried out by any of a batch method, a semi-batch method and a continuous method.
• a batch method a glycerin carbonate-based compound, a monofunctional (meth) acrylate, a catalyst and a polymerization inhibitor are charged in a reactor, and the oxygen-containing gas is bubbling in the reaction solution and stirred at a predetermined temperature. After that, the monohydric alcohol produced as a by-product with the progress of the transesterification reaction can be extracted from the reactor at a predetermined pressure to produce the desired component (A).
• the separation / purification operation include a crystallization operation, a filtration operation, a distillation operation, an extraction operation, and the like, and it is preferable to combine these operations.
• the crystallization operation include cold crystallization and concentrated crystallization
• examples of the filtration operation include pressure filtration, suction filtration and centrifugal filtration
• examples of the distillation operation include simple distillation, fractional distillation and molecular distillation.
• examples of the extraction operation include solid-liquid extraction and liquid-liquid extraction.
• a solvent may be used in the separation and purification operation.
• a neutralizing agent for neutralizing the catalyst and / or polymerization inhibitor used in the present invention an adsorbent for adsorbing and removing, an acid and / or alkali for decomposing or removing by-products, and a color tone.
• Activated carbon for improving the above, silica soil for improving the filtration efficiency and the filtration rate, and the like may be used.
• the component (A) thus obtained can have a chlorine concentration of less than 100 ppm, preferably less than 10 ppm, and a sodium concentration of less than 100 ppb, preferably less than 10 ppb, and the cured product can be obtained.
• a curable composition having excellent water resistance and metal corrosion resistance can be obtained.
• component (D) When a compound having an ethylenically unsaturated group other than the component (A) described later [hereinafter referred to as "component (D)"] is blended, the content ratio of the component (A) is 100% by weight of the total curable component. In addition, 5 to 100% by weight is preferable, 5 to 95% by weight is more preferable, and 10 to 70% by weight is particularly preferable. By setting the content ratio of the component (A) to 5% by weight or more, the composition can have a low viscosity. On the other hand, when it is 95% by weight or less, the crosslink density can be increased and the heat resistance can be improved.
• the curable component is as defined above, and means the components (A) and (D).
• the present invention is a curable composition containing the above (A).
• a method for producing the composition a mixture of reaction products containing (meth) acrylate obtained by transesterifying a glycerin carbonate-based compound and a monofunctional (meth) acrylate in the presence of the catalysts X and Y.
• a production method including a step of producing the component (A) is preferable. According to the production method, the component (A) can be obtained in a high yield, so that the cost and productivity are excellent. Further, the component (A) obtained by the production method has a low viscosity and is easy to handle because there are few side reaction high molecular weight substances, and the chlorine concentration and the sodium concentration can be further reduced.
• the method for producing the component (A) described above may be followed. Further, when other components described later are blended, the component (A) and the other components may be stirred and mixed.
• the viscosity of the composition may be appropriately set according to the intended purpose, preferably 10 to 3,000 mPa ⁇ s, and more preferably 20 to 1,500 mPa ⁇ s.
• the composition of the present invention can be used as an active energy ray-curable composition or a thermosetting composition, but can be preferably used as an active energy ray-curable composition. Further, the composition of the present invention can be used in any form of a solvent-free composition containing no organic solvent, a solvent-type composition containing an organic solvent, and an aqueous composition in which the component (A) is dissolved or dispersed in water. can do. In the aqueous composition in which the component (A) is dispersed in water, an emulsifier usually used or a reactive emulsifier described later can be used as the dispersant.
• the composition of the present invention contains the component (A) as an essential component, but various components can be blended depending on the purpose.
• the other components include a photopolymerization initiator [hereinafter referred to as "(B) component”], a thermal polymerization initiator [hereinafter referred to as “(C) component”], and the above-mentioned (A).
• examples thereof include compounds having an ethylenically unsaturated group other than the components [hereinafter, referred to as “component (D)”] and the like.
• component (D) ethylenically unsaturated group other than the components
• composition of the present invention is used as an active energy ray-curable composition, particularly when ultraviolet rays and visible light are used as active energy rays, (B) from the viewpoint of easiness of curing and cost.
• Component photopolymerization initiator
• an electron beam is used as the active energy ray, it is not always necessary to blend it, but it can be blended in a small amount if necessary in order to improve the curability.
• component (B) examples include benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl.
• Acylphosphine oxide compounds as well as thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3,4-dimethyl-9-oxo-9H-thioxanthone-2 -Il-oxy] -2-hydroxypropyl-N, N, N-trimethylammonium chloride, fluorothioxanthone and other thioxanthone compounds can be mentioned.
• Examples of the compound other than the above include benzyl, methyl phenylglioxyate, ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate, ethyl anthraquinone, phenanthrenequinone, camphorquinone and the like.
• an acetophenone-based compound is preferable, and ⁇ -hydroxyphenyl ketone is preferable because it has good surface curability even in a thin film coating in the atmosphere.
• ⁇ -hydroxyphenyl ketone 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl-1-phenyl-propane-1-one are more preferable.
• acylphosphine oxide compound and the morphophosphorus compound are preferable to use in the acetphenone-based compound in combination.
• acylphosphine oxide compound in this case, Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl- (2,4,6-trimethylbenzoyl) phenylphosphine and bis (2,6- Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like can be mentioned.
• the morpholin compound include 2-methyl-1- [4- (methylthio)] phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl). Butane-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1-one and the like can be mentioned.
• the content ratio of the component (B) is preferably 0.05 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total amount of the curable components.
• Component (C) is a thermosetting initiator, and when the composition is used as a thermosetting composition, the component (C) can be blended.
• the composition of the present invention can also be heat-cured by blending a thermal polymerization initiator.
• a thermal polymerization initiator various compounds can be used, and organic peroxides and azo-based initiators are preferable.
• organic peroxide examples include 1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, and 1 , 1-bis (t-hexyl peroxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2, , 2-bis (4,4-di-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-Butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-dimethyl
• azo compounds include 1,1'-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile. , Azodi-t-octane, azodi-t-butane and the like.
• organic peroxide can be combined with a reducing agent to cause a redox reaction.
• the content ratio of the component (C) is preferably 10 parts by weight or less with respect to 100 parts by weight of the total amount of the curable component.
• the component (C) may be carried out according to the usual means of radical thermal polymerization, and in some cases, it may be used in combination with the component (B) (photopolymerization initiator), and after photocuring, the reaction rate is further increased. It is also possible to carry out thermosetting for the purpose of improving.
• Component (D) is a compound having an ethylenically unsaturated group and is a compound other than the component (A).
• a (meth) acryloyl group is preferable, and an acryloyl group is more preferable, because the composition is excellent in curability.
• the component (D) may be a compound having one or more ethylenically unsaturated groups and may be a compound other than the above (A), specifically, a compound having one ethylenically unsaturated group.
• monofunctional unsaturated compound a compound having two ethylenically unsaturated groups
• bifunctional unsaturated compound a compound having three or more ethylenically unsaturated groups
• trifunctional or higher unsaturated compound can be mentioned.
• the monofunctional unsaturated compound examples include a compound having a (meth) acryloyl group, a compound having a monofunctional (meth) acrylamide and a vinyl group.
• examples of compounds having a (meth) acryloyl group include Carboxyl and ethylenically unsaturated groups such as (meth) acrylic acid, Michael-added dimer of (meth) acrylic acid, ⁇ -carboxy-polycaprolactone mono (meth) acrylate, and monohydroxyethyl (meth) phthalate.
• a (meth) acrylate having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate;
• Carbitol (meth) acrylates such as ethyl carbitol (meth) acrylate, butyl carbitol (meth) acrylate, and 2-ethylhexyl carbitol (meth) acrylate;
• Examples of monofunctional (meth) acrylamides include N, N-dimethyl (meth) acrylamide, (meth) acryloylmorpholine, N-methyl (meth) acrylamide, Nn-propyl (meth) acrylamide, and N-isopropyl (meth) acrylamide. , Nn-butyl (meth) acrylamide, N-sec-butyl (meth) acrylamide, Nt-butyl (meth) acrylamide, and N-alkyl (meth) acrylamide such as Nn-hexyl (meth) acrylamide.
• N-hydroxyalkyl (meth) acrylamide such as N-hydroxyethyl (meth) acrylamide; as well as N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethyl ( Meta) acrylamide, N, N-diethyl (meth) acrylamide, N, N-di-n-propyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, N, N-di-n-butyl (meth) Examples thereof include N, N-dialkyl (meth) acrylamide such as acrylamide and N, N-dihexyl (meth) acrylamide.
• Examples of the compound having a vinyl group include N-vinylpyrrolidone and N-vinylcaprolactam.
• bifunctional unsaturated compound a bifunctional (meth) acrylate is preferable.
• the bifunctional (meth) acrylate include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and 3-methyl-1,5-pentanediol diacrylate.
• 2-Butyl-2-ethyl-1,3-propanediol diacrylate ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate , Polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, di (meth) acrylate of alkylene oxide adduct of bisphenol A, di (meth) acrylate of alkylene oxide adduct of bisphenol F and the like. Be done.
• oligomers such as urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate and polyether (meth) acrylate can be used in addition to the above-mentioned compounds.
• a trifunctional or higher (meth) acrylate having three or more (meth) acryloyl groups is preferable.
• Polypoly (meth) acrylates such as acrylate and dipentaerythritol tri, tetra, penta or hexa (meth) acrylate; and tri (meth) acrylates of glycerin alkylene oxide adducts, tri or tetra (pentaerythritol alkylene oxide adducts).
• Poly (meth) acrylates of polyol alkylene oxide adducts such as (meth) acrylates; and tri (meth) acrylates of isocyanuric acid alkylene oxide adducts can be mentioned.
• Examples of the above-mentioned alkylene oxide adduct include ethylene oxide adduct, propylene oxide adduct, ethylene oxide and propylene oxide adduct, and the like.
• urethane (meth) acrylate or the like can be used in addition to the above-mentioned compounds.
• pentaerythritol tri or tetra (meth) acrylate, dipentaerythritol tri, tetra, penta or hexa (meth) acrylate, and trifunctional or higher functional urethane (meth) acrylate are cured of the obtained composition. It is preferable because the product has high hardness and excellent adhesion to the base material.
• urethane (meth) acrylates having trifunctionality or higher will be described in detail.
• Examples of the trifunctional or higher functional urethane (meth) acrylate include a reaction product of a polyhydric alcohol, a polyhydric isocyanate and a hydroxyl group-containing (meth) acrylate, and a reaction product of an organic polyhydric isocyanate and a hydroxyl group-containing (meth) acrylate compound. ..
• polyhydric alcohol examples include polyether polyols such as polypropylene glycol and polytetramethylene glycol, polyester polyols obtained by reacting the polyhydric alcohol with the polybasic acid, the polyhydric alcohol, the polybasic acid and ⁇ -caprolactone.
• polyether polyols such as polypropylene glycol and polytetramethylene glycol
• polyester polyols obtained by reacting the polyhydric alcohol with the polybasic acid, the polyhydric alcohol, the polybasic acid and ⁇ -caprolactone.
• caprolactone polyol obtained by the reaction with
• polycarbonate polyol for example, polycarbonate polyol obtained by the reaction of 1,6-hexanediol and diphenyl carbonate.
• organic multivalent isocyanate examples include diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane-4,4'-diisocyanate and dicyclopentanyl diisocyanate; Examples thereof include organic polyisocyanates having three or more isocyanate groups such as hexamethylene diisocyanate trimer and isophorone diisocyanate trimer.
• hydroxyl group-containing (meth) acrylate examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate and hydroxyoctyl.
• Hydroxyl-containing mono (meth) acrylates such as (meth) acrylate, trimethylol propane mono (meth) acrylate and pentaerythritol mono (meth) acrylate; And trimethylolpropane di (meth) acrylate, pentaerythritol di or tri (meth) acrylate, trimethylolpropane di or tri (meth) acrylate and dipentaerythritol di, tri, tetra or penta (meth) acrylate, glycerinji.
• Examples thereof include hydroxyl group-containing polyfunctional (meth) acrylates such as (meth) acrylates.
• Preferred trifunctional or higher functional urethane (meth) acrylates include organic polyisocyanates having two isocyanate groups and hydroxyl group-containing polyfunctional (meth) acrylate reactants. Among them, isophorone diisocyanate and hexamethylene diisocyanate are preferable as the organic polyisocyanate having two isocyanate groups because of its low viscosity, high hardness of the cured product, and low coloration, and hydroxyl group-containing polyfunctionality (meth).
• pentaerythritol di or tri (meth) acrylate dipentaerythritol di, tri, tetra or penta (meth) acrylate, and glycerin di (meth) acrylate are preferable.
• urethane (meth) acrylate those produced by a conventional method can be used.
• an addition catalyst such as dibutyltin dilaurate
• an organic polyvalent isocyanate and a polyvalent oar are heated and stirred to carry out an addition reaction to produce an isocyanate group-containing compound, and a hydroxyl group-containing (meth) acrylate is further added to the compound and heated.
• -A method of stirring and adding reaction can be mentioned.
• urethane poly (meth) acrylates other than these include compounds as described on pages 70 to 74 of the document "UV / EB Curing Material” [CMC Co., Ltd., published in 1992]. ..
• the content ratio of the component (D) is preferably 0 to 80% by weight, more preferably 10 to 50% by weight, based on 100% by weight of the total amount of the curable components.
• the content ratio of the component (D) is preferably 0 to 80% by weight, more preferably 10 to 50% by weight, based on 100% by weight of the total amount of the curable components.
• a surface modifier may be added for the purpose of enhancing the leveling property at the time of application, increasing the slipperiness of the cured product and enhancing the scratch resistance, and the like.
• the surface modifier include a surface conditioner, a surfactant, a leveling agent, an antifoaming agent, a slipperiness-imparting agent, an antifouling agent, and the like, and these known surface modifiers can be used. .. Among them, a silicone-based surface modifier and a fluorine-based surface modifier are preferably mentioned.
• an organopolysiloxane having a polyoxyalkylene skeleton in its molecular structure an organopolysiloxane having a polyester skeleton, a fluoropolymer and an oligomer having a perfluoroalkyl group and a polyalkylene oxide chain, and a perfluoroalkyl.
• Fluorine-based polymers and oligomers having an ether chain and a polyalkylene oxide chain can be mentioned.
• a surface modifier having an ethylenically unsaturated group, preferably a (meth) acryloyl group in the molecule may be used for the purpose of enhancing the sustainability of slipperiness.
• an organopolysiloxane having a polyoxyalkylene skeleton (hereinafter referred to as “component (E)”] because it has excellent surface smoothness and can significantly improve the antistatic function described later.
• component (E) an organopolysiloxane having a polyoxyalkylene skeleton
• the oxyalkylene constituting the polyoxyalkylene skeleton include oxyethylene, oxypropylene, oxybutylene, and a combination of these oxyalkylenes.
• the form of binding of the polyoxyalkylene skeleton may be one end, both ends, or a side chain of the polysiloxane chain.
• component (E) examples include a polyoxyethylene-methylpolysiloxane copolymer, a poly (oxyethylene-oxypropylene) methylpolysiloxane copolymer, and the like.
• the component (E) is commercially available, for example, 71ADDITIVE, 74ADDITIVE, 57ADDITIVE, 8029ADDITIVE, 8054ADDITIVE, 8211ADDITIVE, 8019ADDITIVE, 8526ADDITIVE, FZ-2123, FZ-2191 [manufactured by Toray Dow Corning Co., Ltd.] TSF4440, TSF4441, TSF4445, TSF4446, TSF4450, TSF4452, TSF4460 (manufactured by Momentive Performance Materials); Silface SAG002, Silface SAG003, Silface SAG005, Silface SAG503A, Silface SAG008, Silface SJM003 [manufactured by Nissin Chemical Industry Co., Ltd.]; TEGO We
• the content ratio of the surface modifier is preferably 0.01 to 5.0 parts by weight with respect to 100 parts by weight of the total amount of the curable components.
• the composition of the present invention may be added with an antistatic agent for the purpose of imparting an antistatic function.
• the antistatic agent include various cationic antistatic agents having a cationic group such as a quaternary ammonium salt, a pyridinium salt, and a primary to tertiary amino group, a sulfonic acid base, a sulfate ester base, and a phosphoric acid.
• Anionic antistatic agents having anionic groups such as ester bases and phosphonic acid bases, amphoteric antistatic agents such as amino acid-based and aminosulfate ester-based agents, and nonionic antistatic agents such as aminoalcohol-based, glycerin-based, and polyethylene glycol-based Examples thereof include an antistatic agent and a high molecular weight antistatic agent obtained by increasing the amount of the antistatic agent as described above.
• an ionic liquid and a metal salt can be used as the antistatic agent.
• the ionic liquid and the metal salt are not particularly limited, and various commonly used ionic liquids and metal salts can be used. Since the metal salt has high ionic dissociation even in a small amount, it can exhibit excellent antistatic ability and is useful. On the other hand, since the ionic liquid exhibits excellent conductivity by itself, it is useful because it can impart sufficient antistatic ability even with a small amount of content.
• a metal salt of an anion having a fluoro group and a sulfonyl group is preferable because it has excellent antistatic ability and optical properties.
• component (F) a trifluoromethanesulfonyl group is preferable.
• the metal forming the metal salt an alkali metal, a group 2A element, a transition metal and an amphoteric metal are preferable, and an alkali metal is more preferable.
• a metal salt of bis (trifluoromethanesulfonyl) imide, an alkali metal salt of tris (trifluoromethanesulfonyl) methide, and an alkali metal salt of trifluoromethanesulfonic acid ion are preferable. That is, any one of the compounds represented by the following general formulas (D1) to (D3) is preferable.
• M means an alkali metal.
• the alkali metal salt lithium, sodium and potassium are preferable, and lithium is more preferable.
• the above components include bis (fluoroalkylsulfonyl) imide ion, tris (fluoroalkylsulfonyl) methide ion, and fluoroalkylsulfonic acid ion, and specifically, bis (trifluoromethanesulfonyl) imidelithium [Li (CF 3).
• bis (trifluoromethanesulfonyl) imide lithium, tris (trifluoromethanesulfonyl) methidolithium and lithium trifluoromethanesulfonate are preferable, and bis (trifluoromethanesulfonyl) imide lithium and lithium trifluoromethanesulfonate are particularly preferable.
• the content ratio of the antistatic agent is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the solid content in the composition.
• the composition of the present invention may contain a polymerization inhibitor for the purpose of improving storage stability such as preventing gelation of the composition.
• the polymerization inhibitor include organic polymerization inhibitors, inorganic polymerization inhibitors, and organic salt polymerization inhibitors exemplified in the method for producing the component (A) described above, and the same compounds as described above are exemplified.
• the organic compound having a stable radical is preferable as the polymerization inhibitor because it improves the storage stability and does not reduce the hardness of the cured product.
• the organic compound having a stable radical include galbinoxyl and an N-oxyl compound, and the N-oxyl compound is more preferable for the following reasons.
• the composition containing the N-oxyl compound is excellent in storage stability.
• the N-oxyl compound include 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl, 2,2,6,6-tetramethylpiperidin-1-oxyl and 4-oxo-. Examples thereof include 2,2,6,6-tetramethylpiperidine-1-oxyl and 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl.
• the polymerization inhibitor can be added to the composition, or can be used as it is when it is contained in the component (A).
• the polymerization inhibitor can be further added.
• the content ratio of the polymerization inhibitor is preferably 0.0005 to 1% by weight, more preferably 0.005 to 0.1% by weight in the composition.
• the content ratio of the polymerization inhibitor is 0.0005% by weight or more, the polymerization prohibition effect can be sufficiently exhibited, and when it is 1% by weight or less, a decrease in hardness of the cured product can be avoided.
• the composition of the present invention does not substantially require an organic solvent, but may contain an organic solvent if necessary for the purpose of adjusting the viscosity or the like.
• the organic solvent include the same compounds as those mentioned in the method for producing the component (A) described above.
• the content ratio of the organic solvent is preferably 0.1 to 1000 parts by weight, more preferably 5 to 500 parts by weight, based on 100 parts by weight of the total amount of the curable components.
• the composition can have a viscosity suitable for coating, and the composition can be easily applied by a known coating method described later.
• Antioxidants are added for the purpose of improving durability such as heat resistance and weather resistance of cured products.
• the antioxidant include phenolic antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants and the like.
• examples of the phenolic antioxidant include hindered phenols such as dit-butylhydroxytoluene.
• commercially available products include AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, and AO-80 manufactured by ADEKA CORPORATION.
• Examples of the phosphorus-based antioxidant include phosphines such as trialkylphosphine and triarylphosphine, and trialkyl phosphite and triaryl phosphite.
• sulfur-based antioxidant examples include thioether-based compounds
• examples of commercially available products include AO-23, AO-412S, and AO-503A manufactured by ADEKA CORPORATION. These may use one kind or two or more kinds.
• Preferred combinations of these antioxidants include a combination of a phenol-based antioxidant and a phosphorus-based antioxidant, and a combination of a phenol-based antioxidant and a sulfur-based antioxidant.
• the content ratio of the antioxidant may be appropriately set according to the purpose, and is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the total amount of curable components. Is.
• the durability of the composition can be improved by setting the content ratio of the antioxidant to 0.1 parts by weight or more, while improving the curability and adhesion by setting the content to 5 parts by weight or less. be able to.
• Ultraviolet absorbers are added for the purpose of improving the light resistance of the cured product.
• the ultraviolet absorber include triazine-based ultraviolet absorbers such as TINUVIN400, TINUVIN405, TINUVIN460, and TINUVIN479 manufactured by BASF, and benzotriazole-based ultraviolet absorbers such as TINUVIN900, TINUVIN928, and TINUVIN1130.
• the content ratio of the ultraviolet absorber may be appropriately set according to the purpose, and is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the total amount of the curable component. Is. When the content ratio of the ultraviolet absorber is 0.01% by weight or more, the light resistance of the cured product can be improved, while when it is 5% by weight or less, the curability of the composition can be improved. It can be excellent.
• silane coupling agent is blended for the purpose of improving the interfacial adhesive strength between the cured product and the substrate.
• the silane coupling agent is not particularly limited as long as it can contribute to improving the adhesiveness with the base material.
• silane coupling agent examples include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-.
• the content ratio of the silane coupling agent may be appropriately set according to the intended purpose, and is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the total amount of the curable component. ..
• the content ratio of the silane coupling agent may be appropriately set according to the intended purpose, and is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the total amount of the curable component. ..
• the component (A) in the present invention has excellent curability, and Glycarbo-A [(2-oxo-1,3-dioxolan-4-yl) methyl acrylate] has excellent curability, and the composition has a low viscosity. It can be preferably used in a composition containing the component (A) as a reactive diluent.
• the present invention relates to a curable composition, preferably an active energy ray-curable composition, and more preferably a solvent-free active energy ray-curable composition, and can be used for various purposes. Examples thereof include coating agents such as paints, adhesives, pressure-sensitive adhesives, inks, molding agents for forming excipient materials, and pattern forming agents such as resists.
• the composition of the present invention can be preferably used for a coating agent composition, an adhesive composition, and a shaping material composition, and more preferably an active energy ray-curable coating agent composition and an adhesive composition. It can be used for products and excipient material compositions.
• a coating agent composition an adhesive composition, and a shaping material composition
• an active energy ray-curable coating agent composition and an adhesive composition it can be used for products and excipient material compositions.
• preferred applications will be described.
• only one of the illustrated compounds may be used, or two or more of them may be used in combination.
• Coating agent composition The composition of the present invention has excellent thin film curability and high hardness of the cured product, so that it can be preferably used as a coating agent composition. Since the component (A) has a low viscosity, it is a solvent-free type. It can be more preferably used as a coating agent composition of. Further, as described above, the component (A) has a low chlorine concentration, whereby a cured film having excellent corrosion resistance can be formed, and the sodium concentration is low, whereby the water resistance is excellent. A cured film can be formed.
• the composition of the present invention can be preferably used as a coating agent for various plastics, that is, a hard coating agent, and is preferably used as a solvent-free hard coating agent. can do.
• the base material to which the hard coating agent is applied include plastic films used for polarizer protective films and antireflection films, resin molded products used for home appliances and automobile interior / exterior parts, and the like.
• the coating agent composition contains the above (A) as an essential component, but various components can be blended depending on the purpose.
• Specific examples of the other components include the above-mentioned components (B), (C), and (D), a surface modifier, an ultraviolet absorber, an antistatic agent, a polymerization inhibitor, an organic solvent, an antioxidant, and the like. And silane coupling agents.
• pigments / dyes, polymers and the like can be mentioned.
• Specific examples of pigments / dyes and polymers include compounds similar to those listed in paragraph numbers [0088] and [0094] of the International Publication WO2017 / 002964 pamphlet.
• the coating agent composition it can be preferably used as a coating agent for a metal base material.
• the component (A) used in the present invention has a low chlorine concentration, whereby a cured film of a curable composition having excellent corrosion resistance can be formed on the surface of the metal substrate. ..
• a step of applying a curable composition to a part or all of the metal base material, and a coated composition It is preferable to include a step of irradiating the metal with active energy rays or curing the metal by heating.
• the cured film of the metal substrate having the cured film obtained from the composition of the present invention has excellent water resistance and corrosion resistance
• the electrode protection material used for the electrode protection material, the substrate circuit protection material, the lithium ion battery, etc. can be suitably used as a coating agent.
• Adhesive Composition The composition of the present invention has a low viscosity and is excellent in curability, and therefore can be preferably used as an adhesive composition. Further, as described above, since the cured product is excellent in corrosion resistance and water resistance, it can be preferably used in applications requiring these physical characteristics.
• the adhesive composition contains the above (A) as an essential component, but various components can be blended depending on the purpose.
• Specific examples of the other components include the above-mentioned components (B), (C), and (D), a surface modifier, an ultraviolet absorber, a polymerization inhibitor, an organic solvent, an antioxidant, and a silane cup.
• examples include ring agents, pigments / dyes, and polymers.
• composition for Molding Material Since the composition of the present invention has a low viscosity and a high hardness of a cured product, it can be preferably used as a composition for a molding material used for mold transfer, nanoimprint, etc., and in particular, nanoimprint and the like. It can be preferably used as a shaping material used in the microfabrication application of. In the present invention, the shaping material is also included in the concept of the molding material for convenience.
• the shaping material examples include a lens sheet, a nanoimprint film, an antireflection film having a moth-eye shape, a polarizing film, an antiglare film, a light extraction film for organic EL / LED, a light confinement film for a solar cell, and a heat ray retroreflective film. It can be used for producing a shaped film having a fine uneven structure on the surface.
• the composition for a molding material contains the above (A) as an essential component, but various components can be blended depending on the purpose.
• Specific examples of the other components include the above-mentioned components (B), (C), and (D), a surface modifier, an ultraviolet absorber, a polymerization inhibitor, an organic solvent, an antioxidant, and a silane cup.
• examples include ring agents, pigments / dyes, and polymers.
• composition of the present invention has excellent thin film curability, it is a transparent overprint varnish ink printed by a printing machine after single-color or multicolor printing, or color printing such as yellow, red, indigo, and black. It can be preferably used for ink for printing.
• Printing methods include offset printing (normal flat plate that uses dampening water and waterless flat plate that does not use dampening water), letterpress printing (flat pressure letterpress, letterpress half-rotation, rotation, intermittent rotation, flexo), and concave printing.
• Various printing methods such as (gravure printing), stencil printing (screen printing), and inkjet printing can be mentioned, and since they are excellent in emulsion stability, they can be preferably used for offset printing using dampening water. Moreover, since it has a low viscosity, it can be preferably used for inkjet printing.
• the composition for ink contains the above (A) as an essential component, but various components can be blended depending on the purpose.
• Specific examples of the other components include binders, pigments, plasticizers, abrasion resistant agents, and the like, in addition to the components (B), (C), and (D) described above.
• Specific examples of the binder, pigment, plasticizer and anti-friction agent include compounds similar to the compounds listed in paragraph numbers [0101] to [0107] of the International Publication WO2017 / 002964 pamphlet.
• the conventional method for producing the composition for ink may be followed, and the component (A), the component (B) (when the active energy ray is ultraviolet rays), the binder, the pigment, and the polymerization inhibitor.
• a pigment is added and dispersed by a disperser such as a three-roll mill or a bead mill.
• composition for pattern formation The composition of the present invention has high exposure sensitivity, is extremely excellent in developability, and can form a precise and accurate pattern, and therefore can be preferably used as a composition for pattern formation.
• the pattern-forming composition contains the above (A) as an essential component, but various components can be blended depending on the purpose.
• Specific examples of other components include the above-mentioned (B) and (D), organic solvents, antioxidants, ultraviolet absorbers, silane coupling agents, surface modifiers and polymerization inhibitors, as well as alkali-soluble resins.
• Specific examples of the alkali-soluble resin include compounds similar to those listed in paragraph numbers [0110] to [0122] of the Pamphlet of International Publication WO2017 / 00264.
• a conventional method may be followed.
• a method of applying the composition to the applied substrate by a usual coating method and then irradiating it with active energy rays or heating it to cure it can be mentioned.
• a general method known as a conventional curing method may be adopted.
• the composition is adhered to the substrate by using the component (B) (photopolymerization initiator) and the component (C) (thermal polymerization initiator) in combination, irradiating them with active energy rays, and then heat-curing them.
• a method of improving the sex can also be adopted.
• Examples of the base material to which the composition of the present invention can be applied include plastics, metals, woods, inorganic materials, paper and the like, which can be applied to various materials.
• plastics include polyolefins such as polyethylene and polypropylene, ABS resin, polyvinyl alcohol, cellulose acetate resins such as triacetyl cellulose and diacetyl cellulose, acrylic resin, polyethylene terephthalate, polycarbonate, polyarylate, polyether sulfone, norbornene and the like.
• Examples thereof include cyclic polyolefin resins, polyvinyl chlorides, epoxy resins and polyurethane resins using the cyclic olefins of the above as monomers.
• Examples of the metal include steel plates, metals such as aluminum and chromium, and metal oxides such as zinc oxide (ZnO) and indium tin oxide (ITO).
• Examples of wood include natural wood and synthetic wood.
• Examples of the inorganic material include glass, mortar, concrete and stone.
• the method for applying the composition of the present invention to the substrate may be appropriately set according to the intended purpose, and is a bar coater, an applicator, a doctor blade, a dip coater, a roll coater, a spin coater, a flow coater, a knife coater, and a comma.
• a bar coater an applicator, a doctor blade, a dip coater, a roll coater, a spin coater, a flow coater, a knife coater, and a comma.
• Examples thereof include a method of coating with a coater, a reverse roll coater, a die coater, a lip coater, a spray coater, a gravure coater, a micro gravure coater and the like.
• examples of the active energy ray for curing include ultraviolet rays, visible rays, electron beams and the like, but ultraviolet rays or visible rays are preferable, and ultraviolet rays are preferable. Is particularly preferable.
• examples of the ultraviolet irradiation device include a high-pressure mercury lamp, a metal halide lamp, an ultraviolet (UV) electrodeless lamp, and a light emitting diode (LED).
• the irradiation energy may be appropriately set according to the type and compounding composition of the active energy rays.
• the irradiation energy is preferably 50 to 5,000 mJ / cm 2 , preferably 100 to 100. More preferably, 1,000 mJ / cm 2.
• the cured film can be obtained by allowing the cured film to stand in a heatable dryer or the like.
• the heating temperature may be appropriately set according to the substrate to be used and the purpose, and is preferably 40 to 180 ° C.
• the temperature is preferably 120 ° C. or lower because the base material may be deformed if the temperature is too high.
• the heating time may be appropriately set depending on the substrate to be applied and the heating temperature, and is preferably 0.5 to 60 minutes.
• composition of the present invention can be preferably used for coating agent compositions, adhesive compositions, molding material compositions, ink compositions, and pattern forming compositions, and specific examples thereof. Will be explained.
• Method of using coating agent composition As a method of using the coating agent composition, a conventional method may be followed. For example, a method of applying the composition to a base material and then curing it by irradiating it with active energy rays or heating it can be mentioned. Specifically, a method of applying the composition to the applied substrate by a usual coating method and then irradiating the active energy ray-curable composition with active energy rays to cure the composition, or a thermosetting composition. In the case of a product, a method of heating and curing may be mentioned.
• composition is adhered to the substrate by using the component (C) (photopolymerization initiator) and the component (D) (thermal polymerization initiator) in combination, irradiating the composition with active energy rays, and then heat-curing the composition.
• a method of improving the sex can also be adopted.
• Examples of the base material to which the composition of the present invention can be applied include plastics, metals, woods, inorganic materials, paper and the like, which can be applied to various materials, and specific examples thereof are as described above.
• the film thickness of the composition cured film with respect to the base material may be appropriately set according to the purpose.
• the thickness of the cured film may be selected depending on the use of the substrate to be used and the application of the produced substrate having the cured film, but is preferably 1 ⁇ m to 5 mm, more preferably 3 ⁇ m to 3 mm. ..
• the method for applying the composition of the present invention to the substrate may be appropriately set according to the purpose, and examples thereof include the methods described in detail above.
• examples of the active energy ray for curing include ultraviolet rays, visible rays, electron beams, and the like, but ultraviolet rays are preferable.
• examples of the ultraviolet irradiation device include the same devices as described above.
• the irradiation energy may be appropriately set according to the type of active energy ray and the compounding composition, and the same irradiation energy as described above can be mentioned.
• Method of using the adhesive composition As the method of using the adhesive composition, a conventional method may be followed. For example, a method in which the composition is applied to a base material, the coated surface is bonded to another base material, and then cured by irradiating or heating with active energy rays and the like can be mentioned. Specifically, a method of applying the composition to the applied substrate by a usual coating method and then irradiating the active energy ray-curable composition with active energy rays to cure the composition, or a thermosetting composition. In the case of a product, a method of heating and curing may be mentioned. In the case of the active energy ray-curable adhesive composition, at least one of the above-mentioned base materials has light transmittance.
• composition is adhered to the substrate by using the component (C) (photopolymerization initiator) and the component (D) (thermal polymerization initiator) in combination, irradiating the composition with active energy rays, and then heat-curing the composition.
• a method of improving the sex can also be adopted.
• Examples of the base material to which the composition of the present invention can be applied include plastics, metals, woods, inorganic materials, paper and the like, which can be applied to various materials, and specific examples thereof are as described above.
• the film thickness of the composition cured film with respect to the base material may be appropriately set according to the purpose.
• the thickness of the cured film may be selected depending on the use of the base material to be used and the application of the manufactured base material having the cured film, but is preferably 0.1 to 500 ⁇ m, and preferably 1 to 200 ⁇ m. More preferred.
• the method for applying the composition of the present invention to the substrate may be appropriately set according to the purpose, and examples thereof include the methods described in detail above.
• examples of the active energy ray for curing include ultraviolet rays, visible rays, electron beams, and the like, but ultraviolet rays are preferable.
• examples of the ultraviolet irradiation device include the same devices as described above.
• the irradiation energy may be appropriately set according to the type of active energy ray and the compounding composition, and the same irradiation energy as described above can be mentioned.
• composition of the present invention is used for molding material
• a conventional method may be followed. Specifically, the composition is applied to a mold called a stamper having a desired shape, laminated with a film or sheet base material (hereinafter, these are collectively referred to as "film base material"), and then the active energy is activated.
• film base material a film or sheet base material
• Film substrates that can be used in the present invention include polymethylmethacrylate, polymethylmethacrylate-styrene copolymer film, polyethylene terephthalate, polyethylene naphthalate, polyarylate, polyacrylic nitrile, polycarbonate, polysulfone, polyethersulfone, and polyetherimide. , Polyetherketone, polyimide, polymethylpentene and other plastic films are preferred, and a glass-based substrate can be used if necessary.
• the film substrate is preferably transparent or translucent (for example, milky white).
• the thickness of the film base material is preferably 20 to 500 ⁇ m.
• the film thickness of the composition cured film with respect to the base material may be appropriately set according to the purpose.
• the thickness of the cured film may be selected depending on the use of the substrate to be used and the application of the produced substrate having the cured film, but is preferably 10 nm to 100 ⁇ m, more preferably 50 nm to 50 ⁇ m. ..
• Examples of the active energy ray for curing the composition of the present invention include ultraviolet rays, visible rays, electron beams and the like, but ultraviolet rays are preferable.
• Examples of the ultraviolet irradiation device include the same devices as described above.
• the irradiation energy may be appropriately set according to the type of active energy ray and the compounding composition, and the same irradiation energy as described above can be mentioned.
• the composition of the present invention is applied to a transparent substrate, and then a mold called a stamper having a desired lens shape is brought into close contact with the transparent substrate. Next, the composition is cured by irradiating it with active energy rays from the transparent substrate side, and then peeled from the mold.
• the composition of the present invention is poured between a mold having a target lens shape and a transparent substrate. Next, the composition is cured by irradiating the active energy ray from the transparent substrate side, and then the mold is removed.
• the material of the mold is not particularly limited, and examples thereof include metals such as brass and nickel, and resins such as epoxy resin. It is preferably made of metal because the mold has a long life.
• composition of the present invention When the composition of the present invention is used for nanoimprint application, a conventional method may be followed. For example, after applying the composition to the base material, a mold having a fine processing pattern and having transparency is pressed. Next, a method of irradiating the transparent mold with active energy rays to cure the composition and then removing the mold can be used.
• the printing substrate used in the printed matter of the present invention is not particularly limited, and for example, high-quality paper, coated paper, art paper, imitation paper, thin paper, thick paper and other papers, various synthetic papers, etc.
• Polyester resin acrylic resin, vinyl chloride resin, vinylidene chloride resin, polyvinyl alcohol, polyethylene, polypropylene, polyacrylonitrile, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer, ethylene methacrylate copolymer, nylon, polylactic acid
• films or sheets such as polypropylene, cellophane, aluminum foil, and various other substrates that have been conventionally used as printing substrates.
• the film thickness of the composition cured film with respect to the base material may be appropriately set according to the purpose.
• the thickness of the cured film may be selected depending on the use of the substrate to be used and the application of the produced substrate having the cured film, but is preferably 1 to 20 ⁇ m, more preferably 1 to 10 ⁇ m. ..
• composition of the present invention when used for offset ink, it can be suitably used as a coating method on the base material by using an offset printing machine that continuously supplies water on the plate surface. Further, it can be suitably used in any paper supply method, that is, a sheet-fed offset printing machine that uses sheet-type printing paper and an offset rotary printing machine that uses reel-type printing paper.
• composition of the present invention when used for inkjet ink, it can be suitably used as a coating method on a base material by using a known inkjet recording device or the like that ejects by an inkjet method to form an image. ..
• the viscosity of the composition is 7 mPa ⁇ s to 30 mPa ⁇ s at the temperature at the time of discharge (for example, 40 ° C. to 80 ° C., preferably 25 ° C. to 30 ° C.) in consideration of the ejection property. preferable. More preferably, it is 7 mPa ⁇ s to 20 mPa ⁇ s.
• Examples of the active energy ray for curing the composition of the present invention include ultraviolet rays, visible rays, electron beams and the like, but ultraviolet rays are preferable.
• Examples of the ultraviolet irradiation device include the same devices as described above.
• the irradiation energy may be appropriately set according to the type of active energy ray and the compounding composition, and the same irradiation energy as described above can be mentioned.
• pattern-forming composition resists such as photosensitive lithographic printing plates, etching resists and solder resists, columnar spacers in liquid crystal panel manufacturing, pixels and black matrices in color filters, etc. are formed. Examples thereof include a coloring composition for this purpose, a color filter protective film, and the like.
• the composition of the present invention can be preferably used depending on the use of a columnar spacer, a coloring composition for a color filter, and a protective film for a color filter in the production of a liquid crystal panel.
• a nonionic surfactant such as polyoxyethylene lauryl ether or a fluorine-based surfactant is added to the composition. It can also be added. Further, if necessary, an adhesive aid, a storage stabilizer, an antifoaming agent and the like may be added as appropriate.
• part means a part by weight.
• HPLC High Performance Liquid Chromatography
• Viscosity Viscosity
• GPC Gel Permeation Chromatography
• GC Gas Chromatography
• APHA Chlorine Content
• Chlorine Content Chlorine Content and Sodium Containing
• Viscosity measurement conditions Using an E-type viscometer (cone plate type viscometer), the viscosity at 25 ° C was measured.
• GC measurement conditions / equipment GC-14B manufactured by Shimadzu Corporation -Detector: FID detector-Column: ZB-1 (length 60 m, inner diameter 0.32 mm, film thickness 3 ⁇ m) -Injection temperature: 230 ° C or 270 ° C ⁇ Detector temperature: 330 °C -Column temperature: After holding at 125 ° C for 5 minutes, the temperature is raised at a rate of 10 ° C / min. Hold for 20 minutes after reaching 325 ° C. ⁇ Carrier gas: Nitrogen ⁇ Injection amount: Dilute to 10% by weight with methanol or acetone and then inject 0.4 ⁇ L. ⁇ Calculation method of purity (%) Dilute among the peaks detected by GC measurement.
• ⁇ APHA APHA was measured using a color difference meter [Petroleum product color tester OME-2000 manufactured by Nippon Denshoku Kogyo Co., Ltd.].
• ⁇ Chlorine content Trace 30 mg of sample is collected in a quartz boat of a chlorine-sulfur analyzer and burned under an argon / oxygen stream, and finally burned under a pure oxygen stream. The generated combustion gas is aerated in 10 ml of an absorbing liquid (0.3% hydrogen peroxide solution), and chlorine is collected as Cl ions. The same operation is repeated three times to collect chlorine in the same absorbing solution and use it as a test solution. The test solution is measured by ion chromatography, and Cl ions are quantified by the calibration curve method.
• Sodium content 1 g of a sample is collected in a 20 ml PFA bottle (fluororesin bottle) and diluted with NMP (N-methylpyrrolidone) to a total volume of 10 g to prepare a test solution.
• the test solution is measured with an ICP mass spectrometer. Quantify the detected elements by the absolute calibration curve method.
• -Pretreatment environment Clean room G room (class 1000) and clean draft (class 100)
• NMP For the electronics industry [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.]
• -ICP mass spectrometer Agilent 7700s manufactured by Agilent Technologies, Inc. (organic solvent measurement mode: He / H2)
• the pressure in the reaction system was adjusted in the range of 140 to 180 mmHg while heating and stirring in the reaction solution temperature range of 110 to 120 ° C., and the mixed solution of MEL and MCA produced as a by-product as the transesterification reaction proceeded was rectified in the rectification column. And withdrawn from the reaction system via a cooling tube.
• MCA of the same weight as the withdrawal solution was added to the reaction system at any time.
• MCA containing MEHQ and TEMPOL was added to the reaction system at any time via a rectification column. After 17 hours from the start of heating and stirring, heating was terminated, the pressure in the reaction system was returned to normal pressure, and extraction was completed.
• Aluminum silicate as an adsorbent on the filtrate [Kyoward 700 (trade name) manufactured by Kyowa Chemical Industry Co., Ltd.). Hereinafter, the product name is abbreviated. ] was charged in 54 parts, and after contact treatment with heating and stirring under normal pressure for 1 hour at an internal temperature of 80 to 105 ° C., 3.0 parts of calcium hydroxide was added in a range of internal temperature of 20 to 40 ° C. The mixture was stirred under pressure for 1 hour. After separating the insoluble matter by pressure filtration, the filtrate is subjected to vacuum distillation for 16 hours at a temperature of 70 to 90 ° C. and a pressure of 0.001 to 100 mmHg while bubbling dry air, and contains unreacted MCA. The distillate was separated.
• this distillate contains 6% glycerin, 72% of the compound having one ethylene oxide added only to the hydroxyl group at the 1-position of glycerin, and the compound having 2 ethylene oxides added only to the hydroxyl group at the 1-position of glycerin. Was contained at 10%.
• reaction liquid temperature was 130 to 130.
• the pressure in the reaction system was adjusted in the range of 4700 to 30 Pa while heating and stirring in the range of 150 ° C., and a mixed solution of ethylene glycol and ethylene carbonate produced as a by-product as the transesterification reaction proceeded was reacted via a cooling tube. Extracted from the system. After 15 hours from the start of heating and stirring, heating was terminated, the pressure in the reaction system was returned to normal pressure, and extraction was completed.
• the kettle liquid was pressure-filtered to remove the activated alumina charged as a catalyst to obtain a filtrate.
• the weight of the filtrate is 560 parts, and as a result of GC analysis, 5% of glycerin carbonate is added, one ethylene oxide is added only to the 1st hydroxyl group of glycerin, and the 2nd and 3rd hydroxyl groups are carbonated and intramolecular. 68% of the compounds that formed a cyclic carbonate structure in glycerin, two ethylene oxides were added only to the hydroxyl group at the 1-position of glycerin, and the hydroxyl groups at the 2- and 3-positions were carbonated to form a cyclic carbonate structure in the molecule. It contained 4%.
• the pressure in the reaction system was adjusted in the range of 120 to 160 mmHg while heating and stirring in the reaction solution temperature range of 110 to 120 ° C., and the mixed solution of MEL and MCA produced as a by-product as the transesterification reaction proceeded was rectified in the rectification column. And withdrawn from the reaction system via a cooling tube.
• MCA of the same weight as the withdrawal solution was added to the reaction system at any time.
• MCA containing MEHQ and TEMPOL was added to the reaction system at any time via a rectification column. After 40 hours from the start of heating and stirring, heating was terminated, the pressure in the reaction system was returned to normal pressure, and extraction was completed.
• compound a2 (filter solution) is 630 parts, and as a result of GC analysis, 7% of glycerin carbonate acrylate, 59% of acrylate of 1 mol of ethylene oxide adduct of glycerin carbonate, and 2 mol of ethylene oxide adduct of glycerin carbonate It contained 4% of the acrylate of. Table 1 shows various analysis results of the obtained compound a2.
• the upper layer was extracted from the separatory funnel, concentrated under reduced pressure using an evaporator, and most of the normal hexane was recovered as a distillate.
• the recovered normal hexane and new normal hexane were added to the remaining separatory funnel in the lower layer, and the extraction operation was performed again. After repeating this extraction operation and the normal hexane recovery operation a total of 8 times, the lower layer of the separatory funnel was extracted, 0.105 parts of MEHQ and 0.001 parts of TEMPOL were added, and the temperature was 60 ° C. while bubbling dry air.
• compound a3 (pot solution) is 155 parts, and as a result of GC analysis, 9% of glycerin carbonate acrylate, 77% of acrylate of 1 mol of ethylene oxide adduct of glycerin carbonate, and 2 mol of ethylene oxide adduct of glycerin carbonate It contained 5% of the acrylate of.
• Table 1 shows various analysis results of the obtained compound a3.
• the water produced by the dehydration reaction was withdrawn from the diversion tube while heating and stirring for 7 hours at a reaction pressure of 370 Torr and a reaction solution temperature of 86 to 90 ° C. while bubbling. A part of the reaction solution was collected and the composition was analyzed by HPLC. As a result, it was confirmed that the reaction solution contained Glycarbo-A, which was the target product. After cooling the reaction solution to room temperature, 274.34 parts of toluene and 87.50 parts of water were added and stirred. When stirring was stopped and the mixture was allowed to stand, it was separated into three layers. The upper layer contained almost no target substance and was mainly composed of toluene. The middle layer was an aqueous layer.
• the lower layer was a layer containing the target substance.
• 250.00 parts of tetrahydrofuran and 55.48 parts of a 20% aqueous sodium hydroxide solution were added to the lower layer, and the mixture was stirred. When stirring was stopped and the mixture was allowed to stand, it was separated into two layers.
• the lower layer was an aqueous layer
• the upper layer was a layer containing the target substance.
• 87.50 parts of water was added to the upper layer and stirred. When stirring was stopped and the mixture was allowed to stand, it was separated into two layers.
• the lower layer was an aqueous layer
• the upper layer was a layer containing the target substance.
• the weight of the filtrate was 147.19 parts, and when the composition was analyzed using HPLC, it was confirmed that the filtrate contained Glycarbo-A, which was the target product. Hereinafter, it is referred to as compound a'2.
• Table 1 shows various analysis results of the obtained compound a'2 (purified product).
• Example 1 Production of active energy ray-curable composition
• the compounds shown in Tables 2 to 4 below were stirred, mixed and dissolved in a stainless steel container at the ratios shown in Table 2 to produce an active energy ray-curable composition.
• the numbers in Tables 2 to 4 mean the number of copies, and the abbreviations mean the following.
• -M1200 Urethane acrylate [manufactured by Toagosei Co., Ltd., trade name: Aronix M-1200]
• -M402 Dipentaerythritol penta / hexaacrylate mixture [manufactured by Toagosei Co., Ltd., trade name: Aronix M-402]
• -Om907 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one [manufactured by IGM Resin, trade name: Omnirad907]
• -DETX 2,4-diethylthioxanthone [manufactured by Nippon Kayaku Co., Ltd., trade name: Kayacure DETX-S]
• -TPO Phosphorus-based photopolymerization initiator (2,4,6-trimethylbenzoyl-diphenylphosphine oxide) [manufactured by IGM
• Viscosity The viscosity of the obtained composition was measured with an E-type viscometer (cone plate-type viscometer) (25 ° C.).
• the ultraviolet irradiation device uses a metal halide lamp manufactured by Eye Graphics Co., Ltd., and is ultraviolet rays in the ultraviolet region (UV-A) centered on 365 nm under the conditions of an irradiation intensity of 200 mW / cm 2 and an integrated light intensity of 2,000 mJ / cm 2. Irradiated. After irradiation with ultraviolet rays, the obtained sample was held at an atmosphere of 85 ° C. and 85% RH for 100 hours, and a moist heat test was conducted. The change in appearance of the cured film after the moist heat test was visually observed and evaluated on the following three levels. ⁇ : No change, ⁇ : Problems such as foaming and peeling occurred in some parts, ⁇ : Peeling occurred on the entire surface of the cured film
• the composition was applied to a thickness of 10 ⁇ m with a bar coater, and then irradiated with ultraviolet rays under the same conditions as in the wet heat test to cure the composition.
• the time until the resistance value becomes 100 M ⁇ or less is measured in a state where a voltage of 20 V is continuously applied in an atmosphere of 85 ° C. and 85% RH, and insulation is performed. The reliability test was evaluated.
• Adhesive strength (initial)
• the composition obtained in Table 3 is applied to a 100 ⁇ m-thick easy-adhesive polyethylene terephthalate (hereinafter referred to as “easy-adhesive PET”) film [Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.] to a thickness of 10 ⁇ m with a bar coater, and then the other.
• the easy-adhesive PET of No. 1 was laminated and irradiated with ultraviolet rays under the same conditions as in the moist heat test to cure the composition.
• the above laminate was subjected to a T-shaped peeling test according to JIS K-6854 under the conditions of a peeling width of 25 mm and a peeling width of 25 ° C. to obtain a peeling strength.
• Adhesive strength (after wet heat test) The laminate obtained in (4) was held for 100 hours in an atmosphere of 85 ° C. and 85% RH, and a T-shaped peeling test was carried out under the conditions of a peeling width of 25 mm and 25 ° C. according to JIS K-6854. The peel strength after the moist heat test was used.
• a transfer mold (hereinafter referred to as "nickel mold") in which fine processing (semicircular pattern with a diameter of 3 ⁇ m and a film thickness of 5 ⁇ m) is formed on a nickel-plated stainless steel plate is shown in the table. After applying the composition obtained in No. 4 to a thickness of 10 ⁇ m with a bar coater, the easy-adhesion PET was laminated and irradiated with ultraviolet rays under the same conditions as in the moist heat test to cure the composition.
• the dimensional change of the pattern shape of the nickel mold and the cured resin is less than 5%
• ⁇ The dimensional change is 5% or more, or the pattern is chipped.
• Nickel mold in which fine processing (a bowl pattern with a diameter of 10 ⁇ m and a film thickness of 5 ⁇ m) is formed on a corrosive nickel-plated stainless steel plate is shown in the table.
• the easy-adhesion PET was laminated and irradiated with ultraviolet rays under the same conditions as in the moist heat test to cure the composition. Then, it was held for 24 hours in an atmosphere of 40 ° C. and 80% RH, and a metal corrosiveness test was conducted. The change in appearance of the nickel mold after the metal corrosiveness test was visually observed and evaluated at the following three levels.
• ⁇ Part of the nickel mold is discolored
• ⁇ The entire surface of the nickel mold is discolored
• compositions of Examples 1 to 3 containing the components (A) (Compounds a1 to a3) obtained in Production Examples 1 to 3 have low viscosities, and have a wet heat test and insulation reliability. The properties were good, and the performance as an active energy ray-curable coating agent composition was excellent.
• compositions of Examples 4 to 6 containing the components (A) (Compounds a1 to a3) obtained in Production Examples 1 to 3 were excellent in adhesive strength and moist heat test. Therefore, it was excellent in performance as an active energy ray-curable adhesive composition.
• the compositions of Comparative Examples 3 and 4 containing the (A)'components (compounds a'2 and a'3) obtained in Comparative Production Examples 2 and 3, respectively had an adhesive strength in a moist heat test. It dropped significantly.
• the compositions of Examples 7 to 9 containing the components (A) (Compounds a1 to a3) obtained in Production Examples 1 to 3 are active energy ray-curable shaping materials.
• the curable composition of the present invention can be preferably used as an active energy ray-curable composition, and further preferably as a solvent-free active energy ray-curable composition.
• the curable composition of the present invention can be used for various purposes, and patterns such as coating agents such as paints, adhesives, adhesives, inks, molding agents for forming excipient materials, and resists are formed. Examples thereof include agents, which can be preferably used as coating agents, adhesives, and shaping materials.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Macromonomer-Based Addition Polymer (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=76575276

Family Applications (1)

Country Status (5)

Cited By (1)

Citations (7)

Family Cites Families (6)

• 2020
  • 2020-12-25 CN CN202080089727.5A patent/CN114867757B/zh active Active
  • 2020-12-25 KR KR1020227021315A patent/KR20220123397A/ko unknown
  • 2020-12-25 JP JP2021567748A patent/JPWO2021132693A1/ja active Pending
  • 2020-12-25 TW TW109146125A patent/TW202134294A/zh unknown
  • 2020-12-25 WO PCT/JP2020/049034 patent/WO2021132693A1/ja active Application Filing

Patent Citations (7)

Also Published As

Similar Documents

Legal Events