JP2012082248A - Moisture-curing liquid composition, and cured material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a moisture-curing liquid composition which maintains an advantage of moisture curability having no necessity of being mixed or heated, can be cured homogeneously to the interior in a short time, and is excellent in storage stability; and to provide a cured material using the same.SOLUTION: The liquid composition includes: a liquid polymer or a liquid monomer having moisture curability; and an amine generating agent in which an amino group of an amine compound is protected by an amine protective group, wherein the amine protective group escapes by ultraviolet rays to generate the amine compound. The amine generating agent is preferably the one having a structure represented by -NH-COO-Rin one molecule. Ris an o-nitrobenzyl group, a substituted o-nitrobenzyl group, a ketoimino group, an α-benzoylbenzyl group, a substituted α-benzoylbenzyl group, a dimethoxybenzyl group, or a substituted dimethoxybenzyl group.

Description

  The present invention relates to a moisture curable liquid composition and a cured product using the same.

  Conventionally, processes such as adhesion, coating, and sealing are important in processing and molding of materials, and various materials are used in these processes. Of these, materials that can be added or applied at room temperature are preferred because of their ease of handling and workability.

  As such a material, an adhesive or a paint diluted with a solvent such as an organic solvent or water is generally well known. However, those using an organic solvent generate volatile gas due to the volatilization of the solvent. Moreover, the thing using water as a solvent takes too much time for drying. Therefore, materials that do not use these solvents are also used. The material that does not use a solvent is composed of a liquid at room temperature. A material which is liquid at normal temperature is cured by various methods after addition or coating in order to maintain a predetermined shape.

  Curing methods for liquid materials at room temperature are 1) curing method by mixing two liquids that react with each other, 2) curing method by heating, 3) curing method by irradiation with light or electron beam, and 4) by reaction with moisture. A curing method can be mentioned.

  Among these, in the curing method 1), since the storage stability after mixing is poor, it must be used up immediately. Therefore, it is necessary to prepare a mixture for each use. In the curing method 2), the use may be limited for adherends that are sensitive to heat. In addition, since the curing reaction proceeds slowly even at room temperature, refrigerated storage is necessary and storage stability is poor. In the curing method 3), 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. However, radical species are highly active, but have a very short lifetime and are easily deactivated by oxygen, etc., so when the irradiation is stopped, the curing reaction stops immediately, and light and electron beams are not fully irradiated. It cannot be cured at the point.

  In contrast to these curing methods, the curing method 4) does not need to be mixed and prepared for each use. Moreover, heating is not particularly required. Also, it does not use radical species with a short lifetime. Examples of the method using the curing method 4) include modified silicone resins, cyanoacrylate adhesives, urethane prepolymers, and the like.

  Modified silicone resins are widely used as adhesives, pressure-sensitive adhesives, paints, coating agents, sealants and the like. In general, a siloxane bond is formed by hydrolysis of an alkoxysilyl group, resulting in curing (Patent Document 1).

  Cyanoacrylate-based adhesives are widely used as one-component room-temperature curing instant adhesives such as metals, plastics, rubber, and wood. Cyanoacrylate is cured by a small amount of moisture adsorbed on the adherend surface (Patent Document 2).

  Urethane prepolymers are widely used as one-component moisture-curing adhesives such as building materials. The urethane prepolymer contains an isocyanate group, and the isocyanate group reacts with moisture in the air to cure by forming a urea bond (Patent Document 3).

JP 2008-248200 A JP 2010-150422 A JP 2010-090263 A

  However, the modified silicone resin and the urethane prepolymer have a problem that it takes tens of minutes to several tens of hours for curing, and the curing speed is slow. In addition, these materials absorb water from the surface of the coating and cure, so that when thickly applied, the surface only solidifies and the interior does not solidify.

  Although cyanoacrylate adhesive begins to cure with water adsorbed on the surface of the adherend, it reacts slowly with moisture in the air, and as a molding or coating application that is not sandwiched between a pair of adherends, it cures entirely. It took several minutes to several hours to complete the internal curing.

  On the other hand, for example, it is conceivable to add a catalyst for increasing the curing rate in advance. However, simply adding such a catalyst causes the curing reaction to proceed even during storage. The increased problem will cause a conflicting problem that storage stability deteriorates.

  The problem to be solved by the present invention is a moisture-curable liquid composition that maintains the advantage of moisture-curing that there is no need for mixing or heating, can be uniformly cured to the inside in a short time, and has excellent storage stability And providing a cured product using the product.

  As a result of intensive studies, the present inventors have found that a liquid polymer or a liquid monomer having moisture curable properties such as a modified silicone resin, cyanoacrylate, urethane prepolymer, etc. are cured in the presence of an amine which is an anionic species. Found to improve. In order to complete the present invention, the present inventors have reached the idea that storage stability can be improved by adding this amine as a latent amine that exhibits activity by ultraviolet irradiation, rather than simply adding it. It came.

  That is, the moisture curable liquid composition according to the present invention comprises a moisture curable liquid polymer or liquid monomer, and the amino group of the amine compound is protected by an amine protecting group, and the amine protecting group is removed by ultraviolet rays. And an amine generator that generates the amine compound at a distance.

ただし、Ｒ^１は、ｏ−ニトロベンジル基、置換ｏ−ニトロベンジル基、ケトイミノ基、α−ベンゾイルベンジル基、置換α−ベンゾイルベンジル基、ジメトキシベンジル基、置換ジメトキシベンジル基のいずれかの基である。 At this time, the amine generator desirably has a structure represented by the following general formula (1).

However, R ¹ is o- nitrobenzyl group, a substituted o- nitrobenzyl group, Ketoimino group, alpha-benzoyl benzyl group, a substituted alpha-benzoyl benzyl, dimethoxybenzyl group, any group of substituents dimethoxybenzyl group .

  The liquid polymer or liquid monomer having moisture curable property is preferably a modified silicone resin, cyanoacrylate, or urethane prepolymer.

  On the other hand, the cured resin according to the present invention is obtained by curing the moisture curable liquid composition.

  According to the moisture curable liquid composition of the present invention, since an amine generator that generates an amine compound by elimination of an amine protecting group by ultraviolet rays is used, the ultraviolet rays are applied after being applied to an adherend during use. , The amine compound is generated in the coating film, and the curing reaction rate can be improved. Thereby, it can be cured in a short time while maintaining the moisture-curing advantage that there is no need for mixing and heating. At this time, even if ultraviolet rays are not uniformly irradiated in the thickness direction of the coating film, the generated amine compound easily diffuses in the coating film, so that it can be uniformly distributed to the inside of the coating film in a short time. Can be cured. Moreover, since it is stable in a state where moisture is blocked and ultraviolet rays are not irradiated, the storage stability is excellent for a long period of time.

  And according to the hardened | cured material which concerns on this invention, since the said moisture curable liquid composition is hardened | cured, while being able to harden | cure uniformly to an inside in a short time, it is excellent also in storage stability.

  Next, an embodiment of the present invention will be described in detail.

  The moisture curable liquid composition according to the present invention (hereinafter sometimes referred to as the present composition) comprises a liquid polymer or liquid monomer having moisture curable properties and an amine generator.

  Examples of the moisture-curing liquid polymer or liquid monomer include modified silicone resins, cyanoacrylates, and urethane prepolymers. These may be used alone or in combination of two or more. These liquid polymers or liquid monomers are preferably those that are moisture-cured at room temperature.

  Examples of the modified silicone resin include those having a hydrolyzable silicone functional group in the molecular chain or at the molecular end of the molecular chain containing the oxyalkylene polymer. When the hydrolyzable silicone functional group is hydrolyzed, a siloxane bond is formed, and the molecular chains are cross-linked by the siloxane bond.

ただし、Ｘは、水素原子、ハロゲン原子、アルコキシ基、アシルオキシ基、ケトキシメート基、アミノ基、アミド基、酸アミド基、アミノオキシ基、メルカプト基、アルケニルオキシ基のいずれかである。一般式（２）に示す構造が分子鎖中に存在する場合には、ｎは、１から２の整数である。一般式（２）に示す構造が分子末端に存在する場合には、ｎは、１から３の整数である。ｎが２以上の場合には、Ｘは互いに同じであっても良いし、異なっていても良い。 Examples of such a hydrolyzable silicone functional group include those represented by the following general formula (2).

However, X is any one of a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. When the structure represented by the general formula (2) is present in the molecular chain, n is an integer of 1 to 2. When the structure represented by the general formula (2) is present at the molecular end, n is an integer of 1 to 3. When n is 2 or more, Xs may be the same or different.

  In the above general formula (2), X is more preferably a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, or an alkenyloxy group. More preferred is an alkoxy group from the viewpoint of mild hydrolyzability and easy handling.

  In the case where n is 1 when the structure represented by the general formula (2) is present in the molecular chain, or when n is 1 or 2 when the structure represented by the general formula (2) is present at the molecular end, Si Examples of the substituent other than X bonded to X include substituents such as an alkyl group, an aryl group, and an aralkyl group. Examples of the alkyl group include those having 1 to 20 carbon atoms. The alkyl group may be linear or branched. Examples of the aryl group include those having 6 to 20 carbon atoms. Examples of the aralkyl group include those having 7 to 20 carbon atoms.

  Although it does not specifically limit as carbon number of the alkylene site | part of an oxyalkylene polymer, It is preferable to exist in the range of 2-4.

  The modified silicone resin may be linear or branched. Moreover, these mixtures may be sufficient. Further, the modified silicone resin may contain other monomer structures and other polymer structures in addition to the oxyalkylene polymer structure. Examples of other monomer structures and other polymer structures include vinyl structures, ester structures, and urethane structures. In this case, it is preferable that 50 mass% or more of oxyalkylene polymer structures are contained in the molecular structure of the modified silicone resin. More preferably, it is 80 mass% or more.

  The number average molecular weight of the modified silicone resin is preferably in the range of 3,000 to 50,000. More preferably, it exists in the range of 5,000-20,000. When the number average molecular weight is in the range of 5,000 to 20,000, a liquid having sufficient fluidity can be obtained without using a solvent.

  Specific examples of the modified silicone resin include “SE9120” manufactured by Toray Dow Corning, “KE-3475” manufactured by Shin-Etsu Silicone, and the like.

式（３）中、Ｒ^２としては、アルキル基、シクロアルキル基、アルケニル基、アリール基、アルコキシアルキル基、トリアルキルシリルアルキル基などを挙げることができる。Ｒ^２の炭素数は特に限定されるものではないが、１〜８個の範囲内が好ましい。 Examples of cyanoacrylate include those represented by the following general formula (3).

In Formula (3), examples of R ² include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an alkoxyalkyl group, and a trialkylsilylalkyl group. The number of carbon atoms in R ² is not particularly limited, but is preferably in the range of 1-8.

  More specifically, cyanoacrylates include alkyl α-cyanoacrylates such as methyl α-cyanoacrylate, ethyl α-cyanoacrylate, propyl α-cyanoacrylate, butyl α-cyanoacrylate, and cyclohexane such as cyclohexyl α-cyanoacrylate. Alkenyl α-cyanoacrylate, allyl α-cyanoacrylate, alkenyl α-cyanoacrylate such as methallyl α-cyanoacrylate, cycloalkenyl α-cyanoacrylate such as cyclohexenyl α-cyanoacrylate, and alkynyl α-such as propargyl α-cyanoacrylate Aryl α-cyanoacrylates such as cyanoacrylate, phenyl α-cyanoacrylate, toluyl α-cyanoacrylate, methoxyethyl α-cyanoacrylate, Tokishiechiru α- cyanoacrylate, furfuryl α- cyanoacrylate, trimethylsilylmethyl α- cyanoacrylate, trimethylsilylethyl α- cyanoacrylate, trimethylsilylpropyl α- cyanoacrylate, dimethyl vinyl silyl methyl α- cyano acrylate. These may be used alone or in combination of two or more.

  As a urethane prepolymer, what has two or more isocyanate groups in 1 molecule is preferable. Examples of such urethane prepolymers include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, biuret-type polyisocyanates obtained by reacting these polyisocyanates with water, and polyhydric alcohols such as trimethylolpropane. And adduct-type polyisocyanates obtained by reacting with polyisocyanate, multimers obtained by isocyanuration, and the like. These may be used alone or in combination of two or more.

  Aliphatic polyisocyanates include methylene diisocyanate, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate (LDI), 1,3,6. -Hexamethylene triisocyanate can be mentioned. Examples of alicyclic polyisocyanates include hydrogenated 4,4′-diphenylmethane diisocyanate (hydrogenated MDI), hydrogenated xylylene diisocyanate (hydrogenated XDI), 1,4-cyclohexane diisocyanate, hydrogenated 2,4-tolylene diisocyanate. (Hydrogenated TDI), isophorone diisocyanate (IPDI), norbornene diisocyanate (NBDI), and the like. Aromatic polyisocyanates include xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), 1,4-diphenyl diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate (TDI). ), 2,4-diphenylmethane diisocyanate (MDI), 4,4-diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI), 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, o-tolidine Examples thereof include diisocyanate, polyphenylmethane polyisocyanate (crude MDI), triphenylmethane triisocyanate, and tris (isocyanatephenyl) thiophosphate.

  Specific examples of the urethane prepolymer include “Death Module N3200” and “Death Module N3600” manufactured by Sumika Bayer Urethane Co., Ltd., “Urehyper” manufactured by DIC Corporation, and the like.

  The amine generator is obtained by protecting the amino group of an amine compound with an amine protecting group. By irradiating with ultraviolet rays, the amine protecting group is eliminated and an amino group (amine compound) is generated.

ただし、Ｒ^１は、ｏ−ニトロベンジル基、置換ｏ−ニトロベンジル基、ケトイミノ基、α−ベンゾイルベンジル基、置換α−ベンゾイルベンジル基、ジメトキシベンジル基、置換ジメトキシベンジル基のいずれかの基である。 The amine protecting group is not particularly limited as long as it is easily removed by ultraviolet rays and does not exhibit the amine properties of the amine. For example, the thing of the structure represented by following General formula (1) can be mentioned. The structure represented by the general formula (1) may be at least one in one molecule of the amine generator, but is preferably two or more.

However, R ¹ is o- nitrobenzyl group, a substituted o- nitrobenzyl group, Ketoimino group, alpha-benzoyl benzyl group, a substituted alpha-benzoyl benzyl, dimethoxybenzyl group, any group of substituents dimethoxybenzyl group .

  The structure represented by the above general formula (1) has an amide bond. Since the amide group does not have the property as an amine, the property as an amine is not exhibited in this state. When irradiated with ultraviolet rays, the amide group changes to an amino group.

Here, in the case where R ¹ is an o-nitrobenzyl group, an example of a reaction process in which an amino group (polyamine compound) is generated is shown in the following formula (4). However, R in the formula (4) represents an amino residue, and it is shown that a monoamine is generated in the reaction process. This is shown by taking a reaction at one amino group as an example. In reality, two or more amino groups may be generated during the reaction. As shown in Formula (4), the amine protecting group is eliminated to generate an amino group (amine compound).

  The amine generator has a structure in which a molecular structure includes an alkyl structure, a cyclic alkyl structure, an aromatic ring structure, an N, N-dicarboxycarbamic acid structure, an isocyanuric bond as a structure bonded to the structure represented by the general formula (1). The thing which has various structures, such as an acid structure, can be mentioned. These structures may exist in an intermediate site in the molecular structure of the amine generator or may exist in a terminal site. In the molecular structure of the amine generator, only one kind of these structures may be contained, or two or more kinds may be contained. In addition to these structures, the molecular structure may contain, for example, binding sites such as an amide bond, an ether bond, and an ester bond.

  The alkyl structure may be linear or branched. Although it does not specifically limit as carbon number, From viewpoints, such as the availability of a raw material compound and the molecular weight of a compound, about 2-30 are preferable. More preferably, it exists in the range of 2-24. Similarly, in the cyclic alkyl structure and the aromatic ring structure, the number of carbon atoms is preferably about 2 to 30.

Preferable examples of the alkyl structure include a straight chain having 4 to 18 carbon atoms. Preferable examples of the cyclic alkyl structure include a cyclohexane structure and a methylenedicyclohexane structure. Preferable examples of the aromatic ring structure include a benzene structure, a methylbenzene structure, a methylenebisbenzene structure, and the like. Preferable examples of the structure having an N, N-dicarboxycarbamic acid structure and the structure having an isocyanuric acid structure include those having the structures shown in the following formulas (5) and (6).

  Preferred amine compounds generated from the amine generator having the structure of the preferred examples described above include monoamine compounds such as 1-butylamine, 1-hexylamine, 1-octylamine, 1-dodecylamine, cyclohexylamine, aniline, 4 -Methylaniline can be mentioned. Examples of polyamine compounds include 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, 1,3-cyclohexanediamine, 1,4. -Cyclohexanediamine, 4,4'-methylenedi (cyclohexaneamine), 2-methyl-1,5-benzenediamine, 2-methyl-1,3-benzenediamine, 4,4'-methylenebisbenzeneamine, etc. Can do.

Preferred examples of R ^{1 in} the leaving group include 2-nitrobenzyl group, α-methyl-2-nitrobenzyl group, 4,5-dimethoxy-2-nitrobenzyl group, α-methyl-4,5-dimethoxy. 2-nitrobenzyl group, 2,6-dinitrobenzyl group, α-methyl-2,6-dinitrobenzyl group, 3,4-dimethoxy-2,6-dinitrobenzyl group, α-methyl-3,4-dimethoxy -2,6-dinitrobenzyl group, methylphenylketoimino group, diphenylketoimino group, 9H-fluoren-9-oneimino group (ketoimino group obtained from 9H-fluoren-9-one oxime), methylnaphthylketoimino group, α -Benzoylbenzyl group, α-benzoyl-3,5-dimethoxybenzyl group, 3,5-dimethoxybenzyl group, α, α-dimethyl-3,5- Such as methoxybenzyl group and the like.

  Only one amine generator may be used alone, or two or more amine generators may be used in combination.

  The content of the amine generator is preferably in the range of 0.1 to 50 parts by mass with respect to 100 parts by mass of the moisture curable liquid polymer or liquid monomer. More preferably, it exists in the range of 0.2-40 mass parts, More preferably, it exists in the range of 1-40 mass parts. If the content is less than 0.1 parts by mass, the content is too small, and the curing reaction of the composition does not easily proceed under normal temperature conditions. On the other hand, when the content exceeds 50 parts by mass, the content is too large and the curing reaction tends to proceed, so that the storage stability tends to be lowered.

  In this composition, in the range which does not impair the objective of this invention, in addition to the said various components, various additives may be included as needed. Examples of additives include fillers, plasticizers, softeners, thixotropy imparting agents, pigments, dyes, anti-aging agents, antioxidants, antistatic agents, flame retardants, adhesion imparting agents, sensitizers, and dispersions. And antibacterial and antifungal agents. These can be used in combination as appropriate.

  As the filler, those having various shapes can be used. For example, calcium carbonate, fumed silica, calcined silica, precipitated silica, ground silica, fused silica, diatomaceous earth, iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide, magnesium carbonate, zinc carbonate, wax stone clay, Examples thereof include organic or inorganic fillers such as kaolin clay, calcined clay, and carbon black, these fatty acids, resin acids, fatty acid ester treated products, and fatty acid ester urethane compound treated products.

  Examples of the plasticizer or softener include diisononyl phthalate, dioctyl phthalate, dibutyl phthalate, dioctyl adipate, isodecyl succinate, diethylene glycol dipenzoate, pentaerythritol ester; butyl oleate, methyl acetylricinoleate, phosphorus Examples include petroleum softeners such as tricresyl acid, trioctyl phosphate, propylene glycol adipate polyester, butylene glycol polyester adipate, phenol, lauric acid, stearic acid, docosanoic acid, paraffinic oil, naphthenic oil, and aroma oil. be able to.

  Examples of the thixotropic property-imparting agent include dry silica, white carbon, hydrogenated castor oil, calcium carbonate, polytetrafluoroethylene, and the like. Examples of the pigment include titanium dioxide, zinc oxide, ultramarine blue, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, sulfate, and other inorganic pigments, azo pigments, copper phthalocyanine pigments, and other organic pigments. Can be mentioned. Examples of the antiaging agent include hindered phenol compounds and hindered amine compounds. Examples of the antioxidant include butylhydroxytoluene and butylhydroxyanisole.

  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 / methyl phosphate, bromine / phosphorus compound, ammonium polyphosphite, neopentyl bromide polyether, brominated polyether, and the like. Examples of the adhesion-imparting agent include terpene resins, phenol resins, terpene-phenol resins, rosin resins, xylene resins, and epoxy resins. Sensitizers include weakly basic solvents such as dimethylformamide and N-methylpyrrolidone, base proliferating agents that decompose themselves by the action of bases to produce new bases, hydrazide derivatives that exhibit basicity by heating, etc. And so on.

  The method for producing the present composition is not particularly limited, but each of the above components is sufficiently kneaded and uniformly dispersed under a reduced pressure or an inert gas atmosphere such as nitrogen using a mixing device such as a mixing mixer. The method is preferred.

  In the present composition, the amine generated from the amine generator is an anionic species. Moreover, the amine structure part has high hydrophilicity. It is inferred that these two properties are deeply related to the acceleration of the curing reaction of the composition.

  For example, for modified silicone resins, amines generated from amine generators promote the hydrolysis of reactive silicone functional groups as anionic species. Moreover, since an amine structure part has high hydrophilicity, affinity with a water | moisture content is improved as a hydrophilic group. That is, it promotes water penetration and promotes contact of the reactive silicone functional group with water. It is presumed that the curing reaction of the modified silicone resin is remarkably accelerated by the synergistic action of these actions.

  Regarding cyanoacrylate, cyanoacrylate itself has a high anionic polymerization activity, and the oxygen atom of the adhering water that normally does not exhibit anionic property is also cured as an anionic species. For cyanoacrylate, an amine having a strong anionic property is used as compared with such adhering water, so that the anionic polymerization rate is remarkably increased. In addition, the amine structure portion becomes a hydrophilic group, and the affinity for adhering water is increased. That is, the penetration of water is promoted, and the contact between cyanoacrylate and water is promoted. It is presumed that the curing reaction of cyanoacrylate is remarkably accelerated by the synergistic action of these actions.

  As for the urethane prepolymer, the isocyanate group of the urethane prepolymer reacts with moisture in the atmosphere to form a urea bond and crosslink and cure. Since the amine generated from the amine generator has high hydrophilicity, it enhances the affinity with moisture as a hydrophilic group. This promotes water penetration and accelerates the curing reaction of the urethane prepolymer with moisture. Moreover, amine itself shows the reactivity with the isocyanate group of a urethane prepolymer. An isocyanate group instantaneously undergoes an addition reaction with an amine at room temperature to form a urea bond. It is presumed that the curing reaction of the urethane prepolymer is remarkably accelerated by the synergistic action of these actions.

  This composition has a specific effect that the curing rate of the liquid polymer or liquid monomer having moisture curing property is accelerated by the amine generated from the amine generator. Moreover, since the penetration of water is promoted by the amine generated from the amine generator, even a thickly coated film can be uniformly cured to the inside in a short time. At this time, even if ultraviolet rays are not uniformly irradiated in the thickness direction of the coating film, the generated amine compound easily diffuses in the coating film, so that it can be uniformly distributed to the inside of the coating film in a short time. Can be cured. And at the time of preservation | save of this composition, since it exists in the state which is not irradiated with an ultraviolet-ray, it exists in the state which has not generate | occur | produced active amine. Therefore, since the curing rate of the liquid polymer or liquid monomer having moisture curable property during storage is not accelerated, it is stable for a long time as long as moisture is cut off.

  The cured product according to the present invention comprising the cured product of the present composition can be used for applications such as adhesives, coating agents, and sealing agents.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.

<Synthesis of amine generator>
<Synthesis of Compound A (Formula 7)>
In a 100 ml three-necked flask equipped with a cooling reflux tube and a thermometer, put 50 ml of dry toluene, and then add 2.8 g (18.3 mmol) of 2-nitrobenzyl alcohol and a drop of dibutyltin dilaurate at room temperature with a stirrer. Stir to dissolve. While continuing stirring, 1.60 g (12.5 mmol) of hexyl isocyanate was added dropwise thereto over 5 minutes. Thereafter, the temperature was raised to 70 ° C., and the reaction was continued at that temperature for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and the precipitate was collected by suction filtration. The filtered sample was recrystallized again from 10 ml of toluene and dried to obtain 3.2 g of Compound A (Formula 7), which was the target product as a white powder. (Yield 91%)

<Synthesis of Compound B (Formula 8)>
The compound was synthesized in the same manner as Compound A except that 1.50 g (12.0 mmol) of cyclohexyl isocyanate was used instead of hexyl isocyanate. (Yield 89%)

<Synthesis of Compound C (Formula 9)>
In a 100 ml three-necked flask equipped with a cooling reflux tube and a thermometer, put 50 ml of dry toluene, and then add 2.8 g (18.3 mmol) of 2-nitrobenzyl alcohol and a drop of dibutyltin dilaurate at room temperature with a stirrer. Stir to dissolve. While continuing stirring, 1.05 g (6.25 mmol) of hexamethylene diisocyanate was added dropwise thereto over 5 minutes. Thereafter, the temperature was raised to 70 ° C., and the reaction was continued at that temperature for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and the precipitate was collected by suction filtration. The filtered sample was recrystallized again from 10 ml of toluene and dried to obtain 2.8 g of Compound C (Formula 9) as a white powder. (Yield 94%)

<Synthesis of Compound D (Formula 10)>
The compound was synthesized in the same manner as Compound C, except that 1.21 g (6.22 mmol) of 1,3-bis (isocyanatomethyl) cyclohexane was used instead of hexamethylene diisocyanate. (Yield 89%)

<Synthesis of Compound E (Formula 11)>
The compound was synthesized in the same manner as Compound C except that 1.64 g (6.25 mmol) of dicyclohexylmethane-4,4′-diisocyanate was used instead of hexamethylene diisocyanate. (Yield 85%)

<Synthesis of Compound F (Formula 12)>
The compound was synthesized in the same manner as Compound C except that 1.09 g (6.26 mmol) of tolylene 2,4-diisocyanate was used instead of hexamethylene diisocyanate. (Yield 92%)

<Synthesis of Compound G (Formula 13)>
The compound was synthesized in the same manner as Compound C except that 1.56 g (6.23 mmol) of methylenediphenyl 4,4′-diisocyanate was used in place of hexamethylene diisocyanate. (Yield 81%)

<Synthesis of Compound H (Formula 14)>
In a 100 ml three-necked flask equipped with a cooling reflux tube and a thermometer, put 50 ml of dry toluene, and then add 2.8 g (18.3 mmol) of 2-nitrobenzyl alcohol and a drop of dibutyltin dilaurate at room temperature with a stirrer. Stir to dissolve. While continuing stirring, 3.16 g (6.25 mmol) of Desmodur N3600 (manufactured by Sumika Bayer Urethane Co., Ltd.) having the structure represented by the following formula (15) was dropped therein over 5 minutes. Thereafter, the temperature was raised to 70 ° C., and the reaction was continued at that temperature for 3 hours. When the reaction solution was cooled to room temperature after the completion of the reaction, the reaction solution was separated into two layers. Then, it dried in the evaporator and obtained 3.8g of light brown oil compound H. (Yield 75%)

<Synthesis of Compound I (Formula 16)>
The compound was synthesized in the same manner as Compound C except that 3.63-g (18.3 mmol) of 2,6-dinitrobenzyl alcohol was used instead of 2-nitrobenzyl alcohol. (Yield 88%)

<Synthesis of Compound J (Formula 17)>
The compound was synthesized in the same manner as Compound C except that 2.47 g (18.3 mmol) of acetophenone oxime was used instead of 2-nitrobenzyl alcohol. (Yield 81%)

<Synthesis of Compound K (Formula 18)>
The compound was synthesized in the same manner as Compound C except that 3.88 g (18.3 mmol) of benzoin was used instead of 2-nitrobenzyl alcohol. (Yield 85%)

<Synthesis of Compound L (Formula 19)>
The compound was synthesized in the same manner as Compound C except that 3.08 g (18.3 mmol) of 3,5-dimethoxybenzyl alcohol was used instead of 2-nitrobenzyl alcohol. (Yield 91%)

<Liquid polymer or liquid monomer>
・ Modified silicone resin ["SE9120" manufactured by Toray Dow Corning Co., Ltd.]
・ Cyanoacrylate [Toa Gosei Co., Ltd., Aron Alpha for general use]
・ Urethane prepolymer [“Death Module N3200” manufactured by Sumika Bayer Urethane Co., Ltd.]

(Examples 1-30)
The liquid polymer or liquid monomer and the amine generator are mixed using a stirrer and dispersed so that the blending ratio (parts by mass) shown in Table 1 or 2 is obtained. A composition was prepared.

(Comparative Examples 1-6)
A liquid composition according to a comparative example was prepared in the same manner as in the example except that the comparative additive shown in Table 3 was used instead of the amine generator.

  Using the ultraviolet curable liquid composition according to the example and the liquid composition according to the comparative example, the storage stability and the curing rate acceleration effect were examined. The results are shown in Tables 1-3. The test method and evaluation method are as follows.

(Storage stability test)
The prepared composition was put in a sample bottle protected from light by aluminum foil, and allowed to stand at room temperature for 7 days in a desiccator in which silica gel was placed and dried, and the appearance change was visually confirmed. In the appearance, the case where solidification was not confirmed was indicated as “◯”, and the case where solidification was confirmed was indicated as “x”.

(Curing test)
The prepared composition was divided into two glass sample bottles. One sample was irradiated with ultraviolet rays for 30 seconds with a UV lamp (100 mW / cm ² manufactured by SEN Special Light Company) with the lid on. The other sample was not irradiated with ultraviolet light. After that, both sample bottles are left at room temperature with the lids removed (in contact with moisture in the atmosphere), and after 1 minute, 5 minutes and 10 minutes from the start of standing, The appearance was examined by visual observation and finger touch. At this time, the case where the curing was confirmed was “◯”, and the case where the curing was not confirmed was “x”.

  From the results of Tables 1 and 2, it can be seen that the moisture-curable liquid compositions of the examples are excellent in storage stability. On the other hand, as shown in Comparative Examples 1, 3, and 5 in Table 3, instead of the amine generator, using hexamethylene diamine in the amine state from the beginning solidifies immediately after mixing, It was confirmed that it could not be prepared and stored.

  Moreover, from the results of Tables 1 and 2, it was confirmed that the curing rate was accelerated by irradiating ultraviolet rays according to the moisture-curable liquid composition of the example. On the other hand, as shown in Comparative Examples 2, 4, and 6 in Table 3, it was confirmed that when ethylenediamide that does not generate amine by ultraviolet rays was used instead of the amine generator, the curing rate was not accelerated. It was.

  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 (4)

A moisture-curing liquid polymer or monomer,
A moisture-curable liquid composition comprising: an amine compound in which an amino group of an amine compound is protected by an amine protecting group, and the amine protecting group is released by ultraviolet rays to generate the amine compound. . The moisture-curable liquid composition according to claim 1, wherein the amine generator has a structure represented by the following general formula (1).

However, R ¹ is o- nitrobenzyl group, a substituted o- nitrobenzyl group, Ketoimino group, alpha-benzoyl benzyl group, a substituted alpha-benzoyl benzyl, dimethoxybenzyl group, any group of substituents dimethoxybenzyl group .   The moisture curable liquid composition according to claim 1 or 2, wherein the moisture curable liquid polymer or monomer is a modified silicone resin, cyanoacrylate, or urethane prepolymer.   A cured product obtained by curing the moisture-curable liquid composition according to claim 1.