JP5758958B2 - Ultraviolet curable composition and cured product using the same - Google Patents

Description

  The present invention relates to an ultraviolet curable composition and a cured product using the same.

  In the processing and molding of materials, bonding, coating, and shielding processes are important, and various materials are used. In particular, from the viewpoint of workability, materials that can be added or applied at room temperature and then harden by some action have been used for a long time.

  In general, adhesives and paints use a method in which pigments and resins are dissolved in organic solvents and water, applied to the target material in a liquid state, and a cured product is obtained by volatilizing the organic solvent and water. There are many. However, when an organic solvent is used, health problems and flammability problems occur due to volatile gas, and in the case of water, there is a problem that it takes time to obtain a cured product because of low volatility. Therefore, the following methods (1) to (4) are mainly used as a mode of curing after adding and applying a liquid substance without using a solvent.

(1) A method of curing by mixing two liquid compounds having low volatility that react with each other, immediately adding and applying them, and advancing the reaction.
(2) A method in which a low-volatile liquid compound is added and applied and then cured by reaction with moisture in the air.
(3) A method in which a low volatile liquid compound is added and applied and then heated to initiate a curing reaction and cure.
(4) A method in which a low-volatile liquid compound is added and applied and then irradiated with light or an electron beam to cause a reaction and cure.

  In the curing reaction (1), an epoxy group reaction is used, and a curing agent such as polyamine or polyol is mixed with an epoxy compound such as glycidyl bisphenol A. The reason why epoxy compounds are widely used in the above curing reaction is that the cured epoxy resin has high mechanical strength and has excellent features in many respects such as electrical characteristics, heat resistance, water resistance, and chemical resistance. It is because it has.

  However, in the two-component system of (1) above, the storage stability after mixing is extremely low and must be used immediately, so it is necessary to mix every use.

  In the curing reaction (2) above, reaction of an alkoxysilyl group such as a room temperature moisture-curing modified silicone resin, reaction of an α-cyanoacrylate group such as a cyanoacrylate adhesive, isocyanate group such as an isocyanate group-containing urethane prepolymer The reaction is used and does not require mixing or heating. However, each curable composition has the following disadvantages.

  The room temperature moisture-curing modified silicone resin and the isocyanate group-containing urethane prepolymer require several tens of minutes to several tens of hours for curing, and have a disadvantage that the surface is solidified and the inside is not solidified if applied a little thicker. In addition, although the cyanoacrylate adhesive starts a curing reaction with water adsorbed on the adherend surface, the reaction with moisture in the air is slow, and as a molding or coating application not sandwiched between a pair of adherends, Curing requires several minutes to several hours, and internal curing is further slowed down.

  The above-described drawbacks relating to the curing rate and internal curing have been attempted to be improved by adding a basic compound or an organic metal as a catalyst. However, when the reactivity with water is increased, the contradiction problem that storage stability is deteriorated is caused.

  Although the epoxy group reaction is mainly used for the curing reaction of (3) above, the curing agent is heated at room temperature by increasing the melting point, introducing a heat dissociable protecting group, or microencapsulating in the system of (1) above. In the inactive state, the mixture is prepared, and the curing agent is activated by heating to cause a curing reaction. This method does not need to be mixed, and can be cured uniformly in a relatively short time only in the heated portion.

  However, the curing reaction of (3) above requires heating to cure, and in order to obtain a thick cured product or to cure in a coexisting state with an adherend, It is necessary to spread the heat to the curing start temperature as a whole, and a heating time and a special heating method are required. Moreover, since hardening progresses slowly at room temperature, it has the problem that refrigeration preservation | save is required.

  For the curing reaction (4), a radical polymerization reaction of a compound having a double bond in the molecule such as an acrylate derivative is used. That is, it is a system in which a compound that generates radicals by light or electron beam is mixed with an acrylate derivative or the like, and a curing reaction is caused by light or electron beam irradiation. Since this method uses radical species having high activity, it can be cured in a short time without the need for mixing or heating.

  However, in the method (4), the radical species has high activity, but has a very short life and is easily deactivated by oxygen or the like. Therefore, when the irradiation is stopped, the curing reaction is stopped immediately, and ultraviolet rays are stopped. There is a problem that a portion (dark part) where the irradiation light does not reach cannot be cured.

  As means for solving the above problems, techniques as described in the following Patent Documents 1 to 5 have been proposed.

JP-A-7-224133 JP-A-7-118369 Japanese Patent Laid-Open No. 11-5014 JP 2006-274240 A JP 2010-150517 A

  The method described in Patent Document 1 uses both ultraviolet curing and moisture curing, and is a method in which moisture curing is performed to the dark part after ultraviolet curing. However, it takes time to cure the moisture, and it takes the same time as the moisture-curable resin to cure the whole.

  The method described in Patent Document 2 is a method of curing an epoxy resin with a photocationic polymerization initiator that generates cations when irradiated with ultraviolet rays. A cation (Lewis acid) generated by this method has a long life unlike a radical, but has a problem of contaminating an adherend such as a metal material because it is an acid. In general, the cation generator is a special ion pair and is expensive.

  The method described in Patent Document 3 is a method in which curing starts when oxygen is blocked. In the joint surface where oxygen is cut off, the dark portion curing is exhibited, but the thickening and the curing in the open system are impossible. That is, it cannot be used for applications such as coating and sealing.

  The method described in Patent Document 4 is a method for initiating curing by near infrared rays. Near-infrared rays have a high transmittance of substances, so it is possible to cure areas where ultraviolet rays or visible light cannot reach, but it is difficult to obtain high energy, and the reaction takes several minutes. In most cases, an irradiation device that is more expensive than an ultraviolet irradiation device is required.

  The method described in Patent Document 5 is a technique in which an ultraviolet radical generator and a thermal radical generator are used in combination. Although dark parts can be cured by radicals generated from thermal radical generators, peroxides are used in thermal radical generators, so special deactivation methods are required for storage, and storage stability If you try to increase it, the reaction will not occur. Further, since the peroxide has a property of oxidatively decomposing organic substances even at room temperature, the storage stability is remarkably lowered even if the temperature is slightly increased. Further, if peroxide remains after curing, the cured product itself deteriorates.

  The present invention has been made to solve the above problems, and the present invention does not require mixing or heating, maintains the advantage of an ultraviolet curable material that cures in a short time, and allows irradiation light to reach. It aims at providing the ultraviolet curable composition which can cure | harden a site | part (dark part) which does not exist, and a hardened | cured material using the same.

  The ultraviolet curable composition of the present invention contains an ultraviolet curable material, a chain transfer agent composed of a compound containing at least one selected from a urethane bond, a urea bond, and an isocyanate group, and a metal-containing compound. The gist is that the part that cannot be reached can be cured.

  In the ultraviolet curable composition, the blending ratio of the ultraviolet curable material and the chain transfer agent is preferably in the range of 90:10 to 10:90 by mass ratio.

  In the ultraviolet curable composition, the metal-containing compound contained in the chain transfer agent is preferably a compound containing at least one metal selected from tin, copper, zinc, cobalt, and nickel.

  In the ultraviolet curable composition, the compounding ratio of the compound containing at least one selected from the urethane bond, urea bond, and isocyanate group contained in the chain transfer agent to the metal-containing compound is 100: 0. It is preferable to be within the range of 001 to 100: 10.

  Moreover, the hardened | cured material of this invention makes it a summary that said ultraviolet curable composition is hardened | cured.

  The ultraviolet curable composition of the present invention contains an ultraviolet curable material, a chain transfer agent composed of a compound containing at least one selected from a urethane bond, a urea bond, and an isocyanate group and a metal-containing compound. . When a metal-containing compound is added to a compound containing any one of urethane bonds, urea bonds, and isocyanate groups, a metal complex complex is formed via nitrogen atoms and oxygen atoms contained in the urethane bonds, urea bonds, or isocyanate groups. To do. This metal complex complex functions as a chain transfer agent, so that when curing an ultraviolet curable material, conventionally, it was difficult to cure because the ultraviolet rays did not reach. Curing is possible.

  The above chain transfer agent stabilizes the active species of the ultraviolet curing reaction and exhibits intermolecular or intramolecular transmission function. Therefore, when added to the ultraviolet curable material, the chain transfer agent is not found in existing ultraviolet curable materials. Dark part curability can be added. In other words, when the existing UV curable material is photopolymerized by irradiating UV light in a state where the chain transfer agent is mixed, the chain transfer agent generates the generated polymerization reaction active species in a portion where dark light does not reach (dark part). ) Can be instantaneously transmitted and cured (dark part curing).

  The ultraviolet curable composition of the present invention can be cured at a site where the irradiation light does not reach, and thus, conventionally required, mixing of a curing agent immediately before curing is unnecessary, and heating and moisture curing after irradiation are necessary. It is possible to cure to a dark part without requiring a process such as the above, it is possible to perform the curing operation in a short time, and the curing workability is excellent.

  The cured product of the present invention is obtained by curing the above-described ultraviolet curable composition, and it is sure to be a part where the irradiation light is difficult to be cured by the conventional ultraviolet curable composition. Can be cured to exhibit good physical properties. In addition, since it can be reliably cured even where the irradiation light does not reach, it can be cured reliably even if it has a shape that is a shadow of irradiation that could not be used in the past, so the shape of the cured product Is not limited, and can correspond to a wide range of cured products.

  Hereinafter, embodiments of the present invention will be described in detail. The ultraviolet curable composition of this invention contains (A) ultraviolet curable materials, such as conventionally well-known various ultraviolet curable resin, and (B) chain transfer agent. (B) The chain transfer agent contains a compound (Bi) containing at least one selected from a urethane bond, a urea bond and an isocyanate group in the molecule and a metal-containing compound (B-ii). ing.

(Bi) A compound containing at least one selected from a urethane bond, a urea bond, and an isocyanate group in the molecule is represented by the urethane bond part represented by the following (formula 1) and the following (formula 2). As long as it contains at least one kind selected from an isocyanate group represented by the following (formula 3) in one molecule, a conventionally known one can be used without particular limitation. it can.

(Formula 1)
-NH-COO-
(Formula 2)
-NH-CO-NH-
(Formula 3)
-N = C = O

Specific examples of the compound (Bi) include various polyurethanes, various polyureas, isocyanate-containing compounds, and the like. The above-mentioned various polyurethanes and various polyureas are obtained by reacting the following isocyanate-containing compounds, hydroxyl (—OH) -containing compounds, amine (—NH ₂ ) -containing compounds, and the like.

  The isocyanate-containing compound can be used as it is as a compound containing an isocyanate group of the above (formula 3), and the isocyanate-containing compound reacts with the following hydroxyl group, amine, etc. to form various polyurethanes and various polyureas. Can be used for

  Examples of the isocyanate-containing compound include the following compounds. Methylene diisocyanate, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate (LDI), 1,3,6-hexamethylene triisocyanate, etc. Aliphatic isocyanate. Hydrogenated-4,4′-diphenylmethane diisocyanate (hydrogenated MDI), hydrogenated-xylylene diisocyanate (hydrogenated XDI), 1,4-cyclohexane diisocyanate, hydrogenated-2,4-tolylene diisocyanate (hydrogenated TDI) , Cycloaliphatic isocyanates such as isophorone diisocyanate (IPDI) and norbornene diisocyanate (NBDI). Aromatic aliphatic isocyanates such as xylylene diisocyanate (XDI) and tetramethylxylylene diisocyanate (TMXDI); 1,4-diphenyl diisocyanate, 2,4 or 2,6-tolylene diisocyanate (TDI), 2,4 or 4,4-diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI), 3,3 ′ -Polyisocyanates such as aromatic isocyanates such as dimethyl-4,4'-diphenylmethane diisocyanate, O-tolidine diisocyanate, polyphenylmethane polyisocyanate (crude MDI), triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate. Examples of the isocyanate-containing compound include biuret-type polyisocyanates obtained by reacting these polyisocyanates with water, adduct-type polyisocyanates obtained by reacting with polyhydric alcohols such as trimethylolpropane, and some of the polyisocyanates are polyesters. Examples include liquid prepolymers polymerized with polyether derivatives, multimers obtained by isocyanuration, and the like. These may be used alone or in combination of two or more.

  The hydroxyl group-containing compound is used by reacting with an isocyanate-containing isocyanate to obtain various polyurethanes. Examples of the hydroxyl group-containing compound include alcohols having 1 to 30 carbon chains having a hydroxyl group at the terminal, (poly) ethylene glycol as a terminal diol, (poly) propylene glycol as a terminal diol, (poly) hexamethylene glycol as a terminal diol, and terminal diol. (Poly) caprolactone, (poly) ester (poly) ol of terminal diol, (poly) amide of terminal diol, (poly) ester of terminal diol, and the like.

  Various polyurethanes need only be dissolved or suspended when they are finally mixed in the UV curable composition, so they are not necessarily in a liquid state, but are in a liquid state for ease of mixing. The hydroxyl group-containing compound used in this case is preferably a liquid compound having a molecular weight of 100,000 or less.

  The amine-containing compound is used by reacting with an isocyanate-containing compound in order to obtain various polyureas. Amine-containing compounds include amines having 1 to 30 carbon chains having a primary or secondary amino group at the terminal, (poly) ethylene glycol as a terminal diamine, (poly) propylene glycol as a terminal diamine, (poly) as a terminal diamine Examples include hexamethylene glycol, (poly) caprolactone of terminal diamine, (poly) ester (poly) ol of terminal diamine, (poly) amide of terminal diamine, (poly) ester of terminal diamine, and the like.

  Various polyureas need only be dissolved or suspended when finally mixed with the curable material, so it is not always necessary to be in a liquid state, but it is preferably in a liquid state for ease of mixing, The amine-containing compound used at this time is preferably a liquid compound having a molecular weight of 100,000 or less.

  In addition, the polyurethane and polyurea compounds may have an alkyl group or a terminal group after polymerization by (thio) ether, (thio) ester, amide, (thio) urethane, (thio) urea, N-alkyl bond, etc., if necessary. Sealed with (meth) acrylic group, epoxy group, oxazolyl group, carbonyl group, thiol group, thioether group, thioester group, phosphoric acid (ester) group, phosphonic acid (ester) group, carboxylic acid (ester) group, etc. May be.

  The above-mentioned urethane bond, urea bond, and isocyanate group may be contained in the molecule by combining a plurality of types or by combining terminal groups.

  As the (B-ii) metal-containing compound, those containing at least one metal selected from tin, copper, zinc, cobalt and nickel are preferably used. As the metal-containing compound, conventionally known compounds can be used without any particular limitation as long as a plurality of kinds of the metals are contained in the constituent molecules in the form of a metal salt or a metal complex.

  As said metal salt, forms, such as carboxylate of the said metal seed | species, phosphate, sulfonate, hydrochloride, bromate, (per) (sub) chlorite, are mentioned.

  The metal complex is not particularly limited as long as it is coordinated and stabilized with an organic ligand capable of forming a coordination bond with the metal species and 1: 1 to 1: 4 (metal: ligand). A well-known thing can be used without this.

Specific examples of the (B-ii) metal-containing compound include bis (2,4-pentanedionato) tin, dibutyltin bis (trifluoromethanesulfonate), dibutyltin diacetate, dibutyltin dilaurate, and dibutyltin maleate. , Phthalocyanine tin (IV) dichloride, tetrabutylammonium difluorotriphenyl tin, phthalocyanine tin (II), tributyl (2-pyridyl) tin, tributyl (2-thienyl) tin, tributyl tin acetate, tributyl (trimethylsilylethynyl) tin, trimethyl (2-pyridyl) tin, bis (hexafluoroacetylacetonato) copper (II), bis (2,4-pentanedionato) copper (II), bis (1,3-propanediamine) copper (II) dichloride, Bis (8-quinolinolato) copper (II), bis (trifluoro-2,4-pentanedionato) copper (II), bis (2-hydroxyethyl) dithiocar Copper (II) phosphate, copper diethyldithiocarbamate, copper (II) dimethyldithiocarbamate, disodium ethylenediaminetetraacetate (II), copper (II) phthalocyanine, dichloro (1,10-phenanthroline) copper (II), phthalocyanine Copper, tetra-4-tert-butylphthalocyanine copper, tetrakis (acetonitrile) copper (I) hexafluorophosphate, copper naphthenate, bis [2- (2-benzothiazolyl) phenolato] zinc (II), bis [2- ( 2-Benzoxazolyl) phenolato] zinc (II), zinc (II) bis (2-hydroxyethyl) dithiocarbamate, bis (2,4-pentanedionato) zinc (II), bis (8-quinolinolato) zinc (II), bis (tetrabutylammonium) bis (1,3-dithiol-2-thione-4,5-dithiolato) zinc complex, disodium zinc ethylenediaminetetraacetate, zinc dibenzyldithiocarbamate (II), dibutyl Le zinc dithiocarbamate (II), zinc diethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc phthalocyanine, zinc naphthenate,
Bis (cyclopentadienyl) cobalt (III) hexafluorophosphate, [1,1′-bis (diphenylphosphino) ferrocene] cobalt (II) dichloride, bis (hexafluoroacetylacetonato) cobalt (II), ( 1R, 2R) -N, N'-bis [3-oxo-2- (2,4,6-trimethylbenzoyl) butylidene] -1,2-diphenylethylenediaminatocobalt (II), (1S, 2S)- N, N'-bis [3-oxo-2- (2,4,6-trimethylbenzoyl) butylidene] -1,2-diphenylethylenediaminatocobalt (II), bis (2,4-pentanedionato) cobalt (II), bis (trifluoro-2,4-pentanedionato) cobalt (II), phthalocyanine cobalt (II), disodium cobalt ethylenediaminetetraacetate, hexaamminecobalt (III) chloride, N, N'-disali Tyrethylenediaminecobalt (II), [5,10,15,20-tetrakis (4-methoxyphenyl) porphyrin G] Cobalt (II), Tris (2,4-pentanedionato) cobalt (III), cobalt naphthenate, [1,2-bis (diphenylphosphino) ethane] nickel (II) dichloride, bis (dithiobenzyl) Nickel (II), bis (hexafluoroacetylacetonato) nickel (II), bis (2,4-pentanedionato) nickel (II), bis (tetrabutylammonium) bis (maleonitriledithiolato) nickel (II) Complex, bis (tricyclohexylphosphine) nickel (II) dichloride, bis (triphenylphosphine) nickel (II) dichloride, bromo [(2,6-pyridindiyl) bis (3-methyl-1-imidazolyl-2-ylidene) ] Nickel bromide, ethylenediaminetetraacetic acid disodium nickel (II), nickel dibutyldithiocarbamate (II), nickel diethyldithiocarbamate and the like. These may be used alone or in combination of two or more.

  The form of the metal-containing compound (B-ii) is not necessarily required to have high solubility in organic matter because it only needs to be dissolved or suspended when it is finally mixed with the cured material. It is preferable that it is an organic acid salt or a metal complex form from the ease of carrying out.

  The (B-ii) metal-containing compound and the (Bi) compound containing at least one selected from a urethane bond, a urea bond, and an isocyanate group in the molecule combine both components. (B) constitutes a chain transfer agent. The compounding method of the component (Bi) and the component (B-ii) is not particularly limited as long as both components are mixed at room temperature or under heating conditions. A method in which the mixture is sufficiently stirred or kneaded using an agitator such as a mixing mixer at an appropriate temperature in an inert gas atmosphere and dissolved or uniformly dispersed is preferable.

  The blending ratio of the (B-i) component and the (B-ii) component is in the range of (B-i) :( B-ii) = 100: 0.001 to 100: 10 in terms of mass ratio. More preferably, it is in the range of (B−i) :( B−ii) = 100: 0.005 to 100: 5. (B-ii) When the compounding amount of the metal-containing compound is too large, the metal-containing compound becomes insoluble, and when added to the ultraviolet curable material, it inhibits the transmission of ultraviolet light, thereby inhibiting the curing reaction. There is a risk of becoming. On the other hand, if the blending amount of the metal-containing compound (B-ii) is too small, the function as a chain transfer agent may be lowered without being able to act as a composite.

  The (B) chain transfer agent prepared by the above method is used by being added to and mixed with (A) an ultraviolet curable material (described later), but the mixing method is not particularly limited, and may be reduced under reduced pressure or nitrogen. A method in which the mixture is sufficiently stirred or kneaded using an agitator such as a mixing mixer at an appropriate temperature in an inert gas atmosphere and dissolved or uniformly dispersed is preferable.

  The blending amount of (A) the ultraviolet curable material and (B) the chain transfer agent is preferably in the range of (A) :( B) = 90: 10 to 10:90, more preferably ( A) :( B) = within a range of 80:20 to 20:80. (B) When there are too many compounding quantities of a chain transfer agent, there exists a possibility that the material ratio in connection with ultraviolet curing may decrease relatively, and sufficient hardened | cured material may not be obtained. Moreover, when there are too few compounding quantities of (B) chain transfer agent, chain transfer ability may run short and there exists a possibility that the dark part hardening function of an ultraviolet curable material may become inadequate.

  (A) As the ultraviolet curable material, an existing ultraviolet curable material can be used. Specifically, a mixture of a curable monomer such as a liquid (meth) acrylate, an oligomer, and the like and a photopolymerization initiator is used as a basic composition, and any cured product can be obtained by irradiation with ultraviolet rays. be able to. In the present invention, the description of “(meth) acrylate” means acrylate and methacrylate. The curing principle of the ultraviolet curable material is that the photopolymerization initiator absorbs ultraviolet rays (ultraviolet light) to generate active species such as radical species, and the active species is a carbon-carbon double layer such as (meth) acrylate. The bond is radically polymerized and cured.

  Hereinafter, the ultraviolet curable material used in the present invention will be described in detail. The liquid (meth) acrylate compound is not particularly limited as long as it is a compound having one or more (meth) acrylate groups in the molecule, and conventionally known compounds can be used.

  Specific examples of the (meth) acrylate include isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and cyclohexyl. (Meth) acrylate, (meth) acrylic acid, benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, (meth) acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, octyl (meth) acrylate Isooctyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) Acrylate, methoxypolypropylene glycol (meth) acrylate, polyoxyethylene nonylphenyl ether acrylate , Diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7- Mono (meth) acrylates such as amino-3,7-dimethyloctyl (meth) acrylate, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, butanediol di (meth) acrylate Hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, decanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 2-hydroxy-3 − Acryloyloxypropyl methacrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tricyclodecane dimethylol di ( (Meth) acrylate, 1,4-butanepolyol di (meth) acrylate, 1,6-hexanepolyol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, polyester di (meth) acrylate, tris (2-hydroxyethyl) isocyanate Lato tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, EO adduct of bisphenol A di (meth) acrylate, EO of hydrogenated bisphenol A Di (meth) acrylate of polyol or PO adduct polyol, epoxy (meth) acrylate obtained by adding (meth) acrylate to diglycidyl ether of bisphenol A, triethylene glycol divinyl ether, trimethylolpropane tri (meth) Acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane EO adduct tri (meth) acrylate, trisacryloyloxyethyl phosphate, pentaerythritol tetra (meth) Acrylate, tetrafurfuryl alcohol oligo (meth) acrylate, ethyl carbitol oligo (meth) acrylate, 1,4-butanediol oligo (meth) acrylate, 1,6-hexanediol oligo (meth) acrylate, trimethylolpropane oligo ( Examples thereof include poly (meth) acrylates such as (meth) acrylate, pentaerythritol oligo (meth) acrylate, (poly) urethane (meth) acrylate, and (poly) butadiene (meth) acrylate. These may be used alone or in combination of two or more.

  The photopolymerization initiator added to the ultraviolet curable material is not particularly limited as long as it is a compound that absorbs ultraviolet rays and initiates radical polymerization, and conventionally known ones can be used.

  Specific examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, ethyl anthraquinone, triphenylamine, carbazole, 3 -Methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2- Hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthiol Xanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2, 6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like. These may be used individually by 1 type and may use 2 or more types together.

  As the photopolymerization initiator, commercially available products such as IRGACURE184, 369, 651, 500, 907, CGI1700, CGI1750, CGI1850, CG24-61; ) Etc. can be used.

  The ultraviolet curable composition of the present invention contains various additives as necessary within the range not impairing the object of the present invention, in addition to the above (A) ultraviolet curable material and (B) chain transfer agent. Can do. Examples of the additives include stabilizers, plasticizers, softeners, pigments, dyes, antistatic agents, flame retardants, adhesion promoters, sensitizers, dispersants, solvents, and antibacterial and antifungal agents. .

Examples of the stabilizer include an anti-aging agent, an antioxidant, and a dehydrating agent. Specifically, these include, for example, hindered phenol compounds, hindered amine compounds (anti-aging agents), butyl hydroxytoluene, butyl hydroxyanisole, triphenyl phosphate (antioxidants), maleic anhydride, phthalic anhydride, Examples thereof include acid chlorides (dehydrating agents) such as benzophenone tetracarboxylic dianhydride, quicklime, carbodiimide derivatives, and stearyl chloride. A small amount of a polymerization inhibitor such as metaquinone can also be used as a stabilizer.

Examples of the plasticizer include dioctyl adipate, dibutyl sebacate, diethylhexyl sebacate, isodecyl succinate, diethylene glycol dipenzoate, pentaerythritol ester,
Butyl oleate, methyl acetylricinoleate, tricresyl phosphate, trioctyl phosphate, propylene glycol adipate polyester, butylene glycol adipate polyester, phenol, lauric acid, stearic acid, docosanoic acid, paraffinic oil, naphthenic oil, aroma series An oil etc. are mentioned.

  Examples of the softener include vinyl group-containing lactams such as N-vinylpyrrolidone and N-vinylcaprolactam, hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, and the like.

  Examples of the pigment include inorganic pigments such as titanium dioxide, zinc oxide, ultramarine, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, sulfate, and organic pigments such as azo pigments and copper phthalocyanine pigments. Can be mentioned.

  Examples of the antistatic agent include hydrophilic compounds such as quaternary ammonium salts, polyglycols, and ethylene oxide derivatives.

Examples of the flame retardant include chloroalkyl phosphate, dimethyl / methylphosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide
Examples include polyethers and brominated polyethers.

  Examples of the adhesion-imparting agent include terpene resins, phenol resins, terpene-phenol resins, rosin resins, xylene resins, and epoxy resins.

  Examples of the sensitizer include dimethylformamide, N-methylpyrrolidone, triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, As isoamyl 4-dimethylaminobenzoate and commercially available products, Ubekryl P102, 103, 104, 105 (above, manufactured by UCB) and the like can be mentioned.

  Examples of the dispersant include surfactants such as polyoxyethylene nonylphenyl ether and polyethylene glycol octylphenyl ether.

  The solvent is not particularly limited as long as it can dissolve the solid component in the composition of the curable material. Specifically, the solvent may be a polar solvent such as tetrahydrofuran, dimethylformamide, ethyl acetate, methyl ethyl ketone, or dichloroethane. And chlorinated solvents such as trichlorobenzene.

  The above additives can be used in combination as appropriate.

  The method for producing the ultraviolet curable composition of the present invention is not particularly limited, but each of the above components is sufficiently stirred using a stirring apparatus such as a mixing mixer under reduced pressure or in an inert gas atmosphere such as nitrogen. A method of kneading and dissolving or uniformly dispersing is preferable.

  The cured product of the present invention is obtained by curing the ultraviolet curable composition by irradiation with ultraviolet rays. Irradiation light may be visible light in addition to ultraviolet rays. Various conventionally known irradiation devices can be used as the ultraviolet irradiation device. Moreover, the irradiation conditions of ultraviolet rays can be appropriately set according to each ultraviolet curable material.

Examples of the present invention and comparative examples are shown below. Among the examples shown below, examples other than Example 9 are used as reference examples. The present invention is not limited to these examples.

  Table 1 shows the compositions of preparation examples (A-1 to A-4) of ultraviolet curable materials used in Examples and Comparative Examples. Table 2 shows the compositions of Preparation Examples (B-1 to B-12) and Comparative Preparation Examples (C-1, C-2) of chain transfer agents used in Examples and Comparative Examples.

  The ultraviolet curable material was obtained by mixing and dissolving or dispersing the components shown in Table 1 with the composition (parts by mass) shown in Table 1 using a stirrer. The chain transfer agent was obtained by mixing and dissolving or dispersing the components shown in Table 2 with the composition (parts by mass) shown in Table 2 using a stirrer.

  In addition, the detail of the component shown with the abbreviation in Table 1 and Table 2 is as follows. In addition, the thing which does not describe a manufacturer name used the reagent grade thing made from Tokyo Chemical Industry.

<(Meth) acrylate>
-IBA: Isobornyl acrylate-DPGA: Dipropylene glycol diacrylate-UP-2: Synthetic product (Synthesis example 2 of urethane-containing compound will be described later)

<Ultraviolet (photo) polymerization initiator>
HCHPK: 1-hydroxycyclohexyl phenyl ketone EANT: 2-ethylanthraquinone

<Urethane-containing compound>
UP-1: synthetic product (Synthesis Example 1 will be described later)
UP-2: synthetic product (Synthesis example 2 will be described later)

<Urea-containing binding compound>
UP-3: synthetic product (Synthesis example 3 will be described later)

<Isocyanate-containing compound>
・ N3600: Sumika Bayer Urethane Co., Ltd., trade name “Death Module N3600”

<Metal-containing compounds>
BPDZ: Bis (2,4-pentanedionato) zinc (II)
CDEDTC: Diethyldithiocarbamate copper (II)
DBTDL: dibutyltin dilaurate BPDC: bis (2,4-pentanedionato) cobalt (II)
BTCN: nickel dibutyldithiocarbamate (II)

(Synthesis Example 1) Synthesis of UP-1 A reaction vessel equipped with a stirrer was charged with 80 g (200 mmol) of polypropylene glycol having a number average molecular weight of 400, 40 g (238 mmol) of hexamethylene diisocyanate and 0.05 g of dibutyltin dilaurate and stirred. The liquid temperature was raised from room temperature to 50 ° C. over 1 hour. Thereafter, a small amount was sampled, and FT-IR was measured, and stirring was continued at 50 ° C. while confirming absorption of an isocyanate group near 2300 cm ⁻¹ . The content of residual isocyanate groups was calculated from the absorption area of FT-IR, and the reaction was terminated when it decreased to about 15% compared to before the reaction and disappeared, and a colorless transparent viscous liquid was obtained. This is UP-1. UP-1 is a urethane-containing bonded compound having a molecular weight of about 3000 and an end having an isocyanate group.

(Synthesis Example 2) Synthesis of UP-2 In a reaction vessel equipped with a stirrer, 100 g (33 mmol) of UP-1 and 8.2 g (70.6 mmol) of 2-hydroxyethyl acrylate, 0.05 g of dibutyltin dilaurate, pentaerythritol 0.02 g of tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] was charged, and the liquid temperature was raised from room temperature to 50 ° C. over 1 hour with stirring. Thereafter, a small amount was sampled, FT-IR was measured, and stirring was continued at 50 ° C. while confirming the absorption of isocyanate near 2300 cm −1. The content of residual isocyanate groups was estimated from the absorption area of FT-IR, and when the absorption disappeared, the reaction was terminated, and a colorless transparent viscous liquid was obtained. This is designated as UP-2. UP-2 is a urethane-containing binding compound having a molecular weight of about 3200 and an acrylate group at the end.

Synthesis Example 3 A reaction vessel equipped with a UP-3 synthesis stirrer was charged with 40 g (208 mmol) of 1,11-diamino-3,6,9-trioxaundecane and 42 g (250 mmol) of hexamethylene diisocyanate and stirred. The liquid temperature was raised from room temperature to 50 ° C. over 1 hour. Thereafter, a small amount was sampled, and FT-IR was measured, and stirring was continued at 50 ° C. while confirming absorption of an isocyanate group near 2300 cm ⁻¹ . The content of residual isocyanate groups was calculated from the absorption area of FT-IR, and the reaction was terminated when it decreased to about 15% compared to before the reaction and disappeared, and a colorless transparent viscous liquid was obtained. This is designated as UP-3. UP-3 is a urea-containing bonding compound having a molecular weight of about 2000 and an end having an isocyanate group.

Examples 1-19, Comparative Examples 1-4
Using the ultraviolet curable material shown in Table 1 and the chain transfer agent shown in Table 2, the ultraviolet curable compositions of Examples 1 to 19 were prepared by mixing both in the blending amounts shown in Table 3. The composition was cured and measured for curability and dark part cure distance. The results are shown in Table 3, and for comparison, Comparative Example 1 using only an ultraviolet curable material, Comparative Example 2 using only a chain transfer agent, UV curable material and Comparative Preparation Examples C-1, C-2 Comparative Examples 3 and 4 in which compounds having no metal-containing compound were combined were prepared at the blending amounts shown in Table 4, and the curability and dark part curing distance were measured. The results are shown in Table 4. In addition, the preparation method of an ultraviolet curable composition, the test method of sclerosis | hardenability, and the measuring method of dark part hardening distance are as follows.

(Preparation of UV curable composition)
The components described in Table 3 or Table 4 were mixed using a stirrer so as to have the blending ratio (parts by mass) described in each table, and dissolved or dispersed, whereby UV curable compositions of Examples and Comparative Examples. A product was prepared.

(Curability test method)
The ultraviolet-curable composition, placed so that the height of the liquid level in the glass tube having an inner diameter of 5mm height 50mm is 20 mm, the ultraviolet irradiation for 10 seconds with a UV lamp (SEN special light source manufactured by 100 mW / cm ²⁾ from the side went. Then, after leaving it to stand at room temperature for 1 minute, a glass rod having a diameter of 1.5 mm was inserted from above, and it was judged by finger touch whether it was cured. At this time, if the glass rod could not be inserted below the liquid level, it was judged to be cured, and it was judged as “O”, and if the glass rod could be easily inserted below the liquid level, it was judged as uncured. It was set as “x”.

(Measurement method of dark part curing distance)
The ultraviolet curable composition was put in a glass tube having an inner diameter of 5 mm and a height of 50 mm so that the liquid level was 20 mm, and the upper half (10 mm) of the contents was wrapped with aluminum foil to create a light-shielding portion. Thereafter, UV irradiation was performed from the side surface with a UV lamp (100 mW / cm ² manufactured by SEN Special Light Company) for 10 seconds. Then, after leaving at room temperature for 20 minutes to return to room temperature, insert a glass rod with a diameter of 1.5 mm from the top and check the hardened part, so that the upper part (non-irradiated part) from the boundary between the ultraviolet irradiation surface and the light shielding surface The distance of the hardened part proceeded to was measured. In addition, it was set as the evaluation similar to the sclerosis | hardenability test whether it was hardening.

  As shown in Table 3, Examples 1 to 19 all had good curability. In addition, Examples 1 to 19 had a dark part curing distance of at least 2.4 mm (Example 16), and it was confirmed that they had dark part curability.

  On the other hand, since Comparative Example 2 did not contain an ultraviolet curable material component, curing by ultraviolet rays could not be confirmed as shown in Table 4. That is, it can be seen that the initial curability requires an ultraviolet curable material containing a (meth) acrylate component and a photopolymerization initiator, and is not cured only with a chain transfer agent. On the other hand, although Examples 1-4 are all using the chain transfer agent used in Comparative Example 2, they are combined with an ultraviolet curable material so that they are cured by ultraviolet irradiation. It was confirmed that ultraviolet curable properties were obtained by combining the ultraviolet curable material and the chain transfer agent.

  In Comparative Examples 1, 3, and 4, as shown in Table 4, the dark part curing distance is less than 0.5 mm, and it is understood that the dark part curing hardly progresses. Specifically, since Comparative Example 1 does not contain a chain transfer agent, dark part curing does not proceed. In Comparative Examples 3 and 4, since the compounds of Comparative Preparation Examples C-1 and C-2 do not contain a metal-containing compound, dark portion curing does not proceed. That is, in order to give the ultraviolet curable material dark-curing property, a chain transfer agent composed of a compound containing at least one selected from a urethane bond, a urea bond, and an isocyanate group and a metal-containing compound must be used. It turns out that dark part curability becomes inadequate. On the other hand, from Examples 1-16, according to the ultraviolet curable composition of this invention, it was confirmed that it is hardened | cured also in a dark part by ultraviolet irradiation.

  Although the embodiments of the present invention have been described in detail above, the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the gist of the present invention.

Claims (3)

Contains a chain transfer agent composed of an ultraviolet curable material, a compound containing at least one selected from a urethane bond, a urea bond, and an isocyanate group and a metal-containing compound composed of dibutyltin dilaurate, and is included in the chain transfer agent The compounding amount of the metal-containing compound is 0.0005 parts by mass or more and 0.1 parts by mass or less with respect to 100 parts by mass of the compound containing at least one selected from a urethane bond, a urea bond, and an isocyanate group. An ultraviolet curable composition characterized in that a portion that does not reach irradiation light is curable (however, a composition containing a compound having two or more isocyanate groups in the molecule, a urethane acrylate oligomer, and nonylphenoxyethyl) Acrylate, isobornyl acrylate, lauryl acrylate, dibutyltin dilaurate Except a composition containing a photopolymerization initiator).   2. The ultraviolet curable composition according to claim 1, wherein a mixing ratio of the ultraviolet curable material and the chain transfer agent is within a range of 90:10 to 10:90 in terms of mass ratio. A cured product obtained by curing the ultraviolet curable composition according to claim 1 .