TW201026712A - Silsesquioxane compound having polymerizable functional group - Google Patents

Abstract

Disclosed is a silsesquioxane compound which enables the production of a coating film having excellent heat resistance, scratch resistance and weather resistance, and has excellent compatibility with conventional polymerizable unsaturated compounds as well as polymerizable unsaturated compounds having high polarity. Also disclosed is a composition containing a silsesquioxane compound which is characterized by having organic groups each directly bound to a silicon atom in the silsesquioxane compound, wherein at least one of the organic groups is an organic group having a urea bond and one (meth)acryloyloxy group.

Description

201026712 VI. Description of the Invention: Field of the Invention The present invention relates to a sesquiterpene oxide compound having a polymerizable functional group. BACKGROUND OF THE INVENTION Sesquiterpene is a general term for a series of grid-like polyoxoxanes of a trapezoidal, cage-type, and three-dimensional network type (random type) structure. The sesquiterpene gas is different from the cerium oxide which is a completely inorganic substance represented by the general formula Si 〇 2, and is soluble in a general organic solvent, so that it is easy to handle, and is excellent in workability and formability such as film formation. Characteristics. On the other hand, as a radical polymerizable unsaturated compound, a polyfunctional acrylate and an unsaturated polyester have been widely studied and used in industry. These radically polymerizable unsaturated compounds are subjected to various studies for the purpose of imparting properties such as scratch resistance and stain resistance of the φ cured product. However, it is difficult to form a composition in which an organic polyoxo-oxygen compound such as sesquiterpene is mixed with a radically polymerizable unsaturated compound which is conventionally used, but has poor compatibility. The composition of the average sentence, the problem of the organic polymethane compound being released from the hardened material obtained. Patent Literatures 1 to 5 disclose sesintho-oxygenation of a radical polymerizable functional group having a propenoxy or methacryloyl〇Xy group, and an oxygen crystal containing the same The invention relates to ultraviolet curable compositions. However, the composition using these sesquioxaxene has a problem of compatibility with other 201026712 polymerizable unsaturated compounds, particularly in the case of insufficient compatibility with a highly polar polymerizable unsaturated compound. [PATENT DOCUMENT] [Patent Document 1] JP-A-2002-167552 (Patent Document 4) JP-A-2002-363414 [Patent Document 5] International Publication W004/85501 t SUMMARY OF INVENTION Technical Problem The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a coated coating. The film is excellent in heat resistance, scratch resistance, and weather resistance. The sesquioxane compound is excellent in compatibility with a general polymerizable unsaturated compound and a polymerizable unsaturated compound having a high polarity. . In order to solve the above-mentioned problems, the inventors of the present invention have repeatedly studied the results of the above-mentioned problems and found that an organic cycline having a urea bond and a W (meth) propyl fluorenyloxy group is introduced into a sesquioxane compound. The above problem can be solved by forming a method of directly bonding to a ruthenium atom, and the present invention has been completed. The present invention relates to 1. A sesquiterpene oxide compound which is a sesquiterpene oxide compound having an organic group of a straight atom of 201026712, characterized in that the foregoing is directly bonded to a ruthenium atom. At least one of the organic groups is an organic group having a urea bond and one (meth) propylene fluorenyloxy group. 2. The sesquiterpene oxide compound according to the item 1, wherein the organic group having a urea bond and one (meth) propylene fluorenyloxy group is an organic group represented by the following general formula (I). 1]

In the formula (I), R1 represents a hydrogen atom or a fluorenyl group, and Y represents a divalent organic group having a urea bond. ]. 3. The sesquiterpene oxide compound according to the item 2, wherein the organic group represented by the general formula (I) is an organic group represented by the following general formula (II).

In the formula (11), R2 represents a hydrogen atom or a methyl group, and R3 represents a divalent hydrocarbon group having 1 to 10 carbon atoms or is represented by the following general formula (III).

—(III) The torsion group of 201026712, and R6 represents diiso) [In the formula (III), r5 represents a divalent cyanate residue having 2 to 4 carbon atoms. The divalent group having a carbon number of 1 〇 is a divalent oxyalkylene compound as described in any of the items 3, and the weight average molecular weight of 1,000 is 1. ~1〇〇, 〇〇〇. An active energy ray-curable composition comprising the cleavage compound of any one of items 1 to 4, and a photopolymerization initiator. The active energy ray-curable composition according to the item 5, further comprising a polymerizable unsaturated compound other than the sesame oxy-compound compound. σ Effect of the Invention According to the present invention, the sesquiterpene compound is an organic group having an organic group which is directly bonded to the Shihe atom and is a urea bond and an Hg](meth)acryloxy group. It is a method of doubling the amount of money to burn and combine (4), and (4) obtaining a bismuth-Wei compound which is compatible with not only a polymerizable unsaturated compound but also a highly compatible polymerizable unsaturated compound. Further, since the compatibility with various polymerizable unsaturated compounds is excellent, the sesquiterpene 7 compound of the present invention can be used for various pure energy ray-curable compositions, and can be improved by the active energy ray hard-recording composition. The heat resistance, scratch resistance and weather resistance of the coating film. C Embodiment] The form of the invention is a sesquiterpoxy compound which has an organic group directly bonded to a cerium atom, and is directly bonded to sand 201026712. At least one of the organic groups of the atom is a sesquivalent compound of the organic ruthenium having a urea bond and a (f-based) alkoxy group (in the form of τ, sometimes omitted as a multiple of the present invention) Cut city compound"). The at least one organic group directly bonded to the cerium atom of the sesquiterpene oxide compound of the present invention is an organic group having a urea bond and a (meth) acryloxy group. The (four) organic group gj has a urea bond, and is excellent in compatibility with various polymerizable unsaturated compounds, and the (meth)pyrene which can be utilized by the organic group can be utilized in the presence of a photopolymerization initiator. ; FW active energy 'friends..., shot and hardened. Thus, the above-mentioned sesquiterpene compound of the present invention can be used to examine various energy ray-curable compositions. The sesquiterpene oxide compound of the present invention is a sesame-oxygen compound of the invention, which is a sesquiterpene oxide compound having an organic group directly bonded to a cerium atom, which is directly bonded to the original To h of the organic group of the sub-organ is a bispoly compound having an organic group of a urea bond and (10) (meth)propoxy group.

Ο 里 '本本3儿明书 "The sesquiterate compound No. J means not only the Si-OH group (hydroxyS1iyi), but also the structure of the sesquiterpene oxide compound. The sesqui can be contained in the Si. group, which has a trapezoidal structure, a non-condensed cage structure, and a random condensate. In the present invention, it is directly bonded to the organic group of the Shixia atom, and has a urine money. And the ratio of one (meth)propoxy-oxyl group is particularly limited, and is at least 莫5 mol% or more, preferably more than the other than Momo%. The ratio of sesquivalent compound of Si 〇 氧 氧 , , si 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基The above-mentioned sesquiterpene oxide compound of the present invention, for example, the above-mentioned organic group having a urea bond and one (fluorenyl) propylene fluorenyloxy group, may be exemplified by the following general formula a sesquioxane compound of an organic group represented by (I).

[In the formula (I), R1 represents a hydrogen atom or a fluorenyl group, and Y represents a divalent organic group having a urea bond. ]. Specifically, the organic group represented by the above formula (I) is, for example, an organic group represented by the following general formula (II). 【化5】

(II) In the formula (11), R2 represents a hydrogen atom or a fluorenyl group, and R3 represents a divalent hydrocarbon group having 1 to 10 carbon atoms or is represented by the following general formula (III).

—(ill) In the formula (III), R5 represents a divalent hydrocarbon group having 2 to 4 carbon atoms, and R6 represents a diisocyanate residue. ] A divalent group represented by 201026712, and R4 represents a divalent hydrocarbon group having 1 to 10 carbon atoms.卜 R3 in the above general formula (II), as long as it is carbon number 丨 ~ (7)? The hydrocarbon group of the valence or the divalent group represented by the general formula (111) is not particularly limited. Specifically, the divalent hydrocarbon group having 1 to 10 carbon atoms may, for example, be a methylene group, an ethylene group, a 1,2-propylene group, a propylene group, a 12-butylene group, a 14-butylene group, a hexylene group, or a sub- An alkylene group such as a fluorenyl group; a cycloalkylene group such as a cyclohexylene group; a subaromatic group such as a phenylene group; Among them, a divalent hydrocarbon group having a carbon number of φ 6 (reduced by a carbon number of 1 to 3), particularly an ethylene group, a 1/3 propylene group, has high heat resistance, scratch resistance, and polymerizability with high polarity. It is suitable from the viewpoint that the compatibility of the unsaturated compound is superior. R4 in the general formula (11) is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 10 carbon atoms. Specific examples thereof include a methylene group, an ethylene group, a propylene group, a fluorene group, a 3-propylene group, a 1,2-butylene group, a 1,4-butylene group, and a hexylene fluorenylene group. a ring; a ring-like thio group such as a cyclohexylene group; a phenylene group; a sub-aromatic group such as a phenyl group. Among them, a divalent hydrocarbon group having a carbon number of 6 (preferably Ο i carbon number of 1 to 3), particularly ethylene, 1,3-propylene, is rich in heat, scratch resistance and polarity. It is suitable from the viewpoint that the compatibility of the polymerizable unsaturated compound is superior. Further, R5 in the general formula (111) is specifically limited as long as it is a divalent hydrocarbon group having 2 to 4 carbon atoms. Specific examples thereof include ethylene, 1,2-propylene, anthracene, 3-propylene, 12-butylene, M-butylene and the like. R6 in the general formula (III) represents a diisocyanate residue. Diisocyanate 15/7 after removal of 2 isocyanato groups (NCO) from the isocyanate compound. Specifically, the diisocyanate compound may, for example, be m-phenylene diisocyanate, p-phenylene diisocyanate or 1-chloro-2,4-. 1-Phenyl-2,4-phenylene diisocyanate, 2,4-diisocyanate, 2,6-diisocyanate, 2,6-diisocyanate Acid toluene vinegar, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane-4,4'-diisocyanate, 3,3'-dimercapto-4,4'-biphenyl An aromatic diisocyanate compound such as a diisocyanate; ethane diisocyanate, propylene diisocyanate, butadiene diisocyanate, pentane diisocyanate, and hexane Fat of diisocyanate, heptane diisocyanate, octane diisocyanate, decane diisocyanate, decane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, etc. Group of diisocyanate compounds and the like. Among them, an aliphatic diisocyanate compound, particularly isophorone diisocyanate, is suitable from the viewpoint of excellent weather resistance. Further, the diisocyanate compound is preferably a diisocyanate compound having a molecular weight of 300 or less from the viewpoint of excellent scratch resistance and active energy ray curability. The organic group represented by the general formula (II) is superior in heat resistance, scratch resistance, compatibility with a highly polar polymerizable unsaturated compound, and active energy ray hardenability, and R 2 is A hydrogen atom, an organic group wherein R3 is an ethylene group, and R4 is an ethylene group or a 1,3-propylene group is preferred. Further, R2 is a hydrogen atom, R3 is a divalent group represented by the general formula (III), and R5 is an ethylene group, and R6 is a divalent group of an isophorone diisocyanate residue, R4 An organic group which is an ethylene group or a 1,3-propylene group is preferred. The above sesquioxaxane compound of the present invention may be a single composition of 201026712, or a mixture of compounds having different compositions. The weight average molecular weight of the cleavage compound of the present invention is not particularly limited. The weight molecular weight in the ~(10) plane is preferably the weight of the molecule in the amount of 1 Na ~ 1 (), _ better. In this amount, the viscosity of the coating film prepared by the sesquiterpene oxide compound of the present invention or the active energy ray-curable composition containing the sesquiterpene oxide compound of the present invention and the coating Sexual aspects have meaning. In the present specification, the weight average molecular weight is a weight average molecular weight measured by a light scattering method. When the weight average molecular weight was measured by a light scattering method, Zetasizer Nano Nano-ZS (manufactured by Malvern Instruments Ltd.) was used. The sample for measurement was obtained by dissolving the sesquioxalic acid compound of the present invention in propylene glycol monomethyl ether, and adjusting it to a sample having a concentration of 0.5 to 5.0% by mass. The light scattering intensities of the ten samples were measured to obtain a weight average molecular weight. The process for producing a sesquiterpene oxide compound of the present invention can be carried out by a method for producing a sesquiterpene oxide compound of the present invention, which is conventionally used in the production of a general sesquiterpene oxide. limited. Further, it can also be produced by, for example, the following production method A or production method B or the like.

Production Method A Production Method A exemplifies the use of an organic group having an organic group directly bonded to a broken atom and having a urea bond and a (meth) propylene decyloxy group, and a hydrolyzable stone. The method of manufacturing the initial substance of Xi Hyun. Specifically, for example, water addition 11 201026712 represented by the following general formula (IV), decomposability (4), and hydrolyzable material other than hydrolyzability represented by the following general formula (Iv) are used as the initial (four), (4) In the presence of (4), the method of producing the bismuth compound of the present invention is R7SiX3 (IV) wherein R in the above formula (IV) has a urea bond and (10) (meth) acrylonitrile The organic group 11 q is alkoxy groups of chlorine or carbon number 6, and x may be the same or different. The alkoxy group having 1 to 6 carbon atoms may, for example, be a linear or branched alkoxy group having a carbon number of 丨6 to 6 (preferably having a carbon number of 4 to 4). More specifically, it contains a methoxy group, an ethoxy group, a η-propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a butyloxy group, a sec-butoxy group, and an n-pentyloxy group. base,! Monoethyl propyl sulfhydryl 'isopentyloxy, neopentyloxy, η-hexyloxy, 1,2,2-trimethylpropoxy, 3,3 dioxin, butyloxy, 2- Ethylbutoxy, isohexyloxy, 3-methylpentyloxy and the like. Specifically, specific examples of X include, for example, a gas, a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like. The water-adding <0-decomposable decane other than the hydrolyzable decane represented by the general formula (IV) can be produced by hydrolyzing and condensing together with the hydrolyzable zeolitic gas represented by the above formula (IV). The semi-oxygenated compound is not particularly limited. Specific examples thereof include alkyl trialkoxysilanes such as methyltrimethoxycarbazide, methyltriethoxysulfonium, ethyltrimethoxyoxane, and ethyltriethoxydecane. In addition, the hydrolyzable decane represented by the general formula (IV) is, for example, a hydrolyzable decane represented by the following general formula (V). 12 201026712 【化7】

Y/S丨X3 —( V ) [In the general formula (V), R1, Υ and X are the same as described above. X can be the same or different. ]. Specifically, the hydrolyzable zebra calcination represented by the general formula (V) can be exemplified by the hydrolyzable zebra burn represented by the following general formula (VI). 【化8】

[In the general formula (VI), R2, R3, R4 and X are the same as described above. X can be the same or different. ]. Specifically, the hydrolyzable zeolitic gas represented by the general formula (VI), for example, may be reacted with a compound represented by the following general formula (VIII) by the hydrolyzable decane represented by the following general formula (VII). get. 【化9】

HzN\R4/SiX3 —( VII)

[In the general formula (VII), R4 and X are the same as described above. In the general formula (VIII), R2 and R3 are the same as described above. ]. 13 201026712 Specifically, the hydrolyzable sinter of the above formula (VII) may, for example, be an amine methyltrimethoxydecane, an amine decyltriethoxydecane or a 2-aminoethyltrimethoxydecane. 2-Aminoethyltriethoxydecane' 3-aminopropyltrimethoxy decane, 3-aminopropyltriethoxydecane, and the like. Specifically, the compound represented by the general formula (VIII) may, for example, be isocyanatomethyl methacrylate, (meth)·acrylic acid-2-isocyanato. Ester, (fluorenyl) 3-isocyanatopropyl acrylate, (meth)acrylic acid-isocyanatooctyl ester, and the like. Further, an addition product of a hydroxyl group-containing (meth) acrylate and a diisocyanate compound may also be mentioned. Specifically, the hydroxyl group-containing (meth) acrylate may, for example, be 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (decyl) acrylate or 3-hydroxypropyl (meth) acrylate. Ester, 4-hydroxybutyl (mercapto) acrylate, and the like. Specifically, the diisocyanate compound may, for example, be m-phenylene diisocyanate, p-phenylene diisocyanate, benzene-2,4-phenylene diisocyanate, 2,4-diisocyanate, 2,6-diiso Aromatic diisocyanate compound such as toluene cyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3,-dimethyl-4,4,-biphenyl diisocyanate Ethane diisocyanate, propylene diisocyanate, butyl diisocyanate, pentane diisocyanate, hexane diisocyanate, heptane diisocyanate, octane diisocyanate, decane diisocyanate, decane diisocyanate, dicyclohexylmethane An aliphatic diisocyanate compound such as a diisocyanate or an isophorone diisocyanate. The reaction of the hydrolyzable decane represented by the above general formula (VII) with the compound represented by the above general formula (VIII) is generally inconsistent with respect to the hydrolyzable decane represented by the above general formula (VII), and the above general formula (VIII) The expressed 201026712 compound was carried out using 1 mol or more. The reaction of the hydrolyzable decane represented by the general formula (VII) with the compound represented by the above formula (VIII) can be carried out in the usual manner of reacting an amine group with an isocyanate group. The reaction temperature is, for example, _78〇c~2〇〇. 〇, _78<>c~ °c is better, 1 (rc~4 (rc is better. In addition, although the reaction can be carried out without relying on pressure, only 〇.〇2~〇.2Mpa, especially The pressure range of 〇〇8 to 〇bMpa is preferably good. The reaction is very rapid, so the reaction is usually completed immediately at the end of the dropping. A suitable solvent may be used in the above reaction. Specifically, the solvent may, for example, be ethyl acetate. An ester of butyl acetate, methyl benzoate or methyl propionate; an ether such as tetrahydrofuran, dioxane or dimethoxyethane; propylene glycol methyl ether and propylene glycol methyl ether acetate; 3 - glycol ethers such as 3-methoxybutylacetate; methanol, ethanol, propanol, etc., aromatic hydrocarbons such as methyl bromide, xylene, etc., aliphatic hydrocarbons, etc. In the present production method, the sesquioxane compound of the present invention is produced, and specifically, the hydrolyzable decane represented by the above formula (IV) is used as the starting material, and the presence of ti is carried out in the presence of lin. Add water to decompose and condense, or use a hydrolyzable calcination method And the hydrolysis-decomposing zea-sinter of the hydrolyzed division (4) of the above-mentioned formula (IV), and the addition of water-decomposition condensation in the presence of (4). The catalyst can be used as appropriate. Specifically, the alkaline 15 201026712 catalyst may be, for example, a metal hydroxide such as potassium hydroxide, sodium hydroxide or barium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide or hydrogen. a oxyhydroxide salt such as tetrabutylammonium hydroxide or benzyltrimethylammonium hydroxide; a fluorinated salt such as tetrabutylammonium fluoride; and the like. The amount of the catalyst to be used is not particularly limited. However, too much will cost, and problems such as difficulty will be removed. On the other hand, if the amount is too small, the reaction will be slow. Therefore, the amount of catalyst used is preferably 0.0001 to 1.0 mol relative to the hydrolyzable decanthogen. The range of 0.0005~〇1 mole is preferred. Water is used for the hydrolysis and condensation. The ratio of the amount of hydrolyzed decane to water is not particularly limited. The amount of water used is 0"~_mole is better, and the ratio of 〇·5~3 mole is better. If the amount of water is too small, the reaction will be slower, and it is hoped that it will be oxidized. When the yield of the compound is lowered, if the amount of water is too large, the amount of the desired structure is reduced. In addition, when the water used is used as an aqueous solution, the water can be used. Alternatively, water may be added by other means. In the above hydrolysis and condensation, an organic solvent may be used or may not be used. The use of an organic solvent may be made in the form of a mixture from the viewpoint of preventing gelation. The viscosity of the time is appropriate. The organic solvent can be made by using a polar organic solvent or a non-polar organic solvent alone or with a 0-polar organic solvent.

Use methanol, ethanol, 2-propanol and other low-grade 16 201026712 alcohols, acetone, methyl isobutyl ketones, tetrahydro (tetra) and other mysteries, especially acetone and reading materials, and the body (four) sentence, The reactivity is improved and thus suitable. Suitable as a non-polar organic solvent is a flue-based solvent, and an organic solvent having a higher ratio of toluene or dimethyl to water, especially a mixture of water and benzene, such as toluene, can be effectively removed from the age. Water is suitable. The preparation is a polar organic solvent-nonpolar organic solvent, and the respective advantages described above can be obtained, so that a mixed solvent is suitable. The reaction temperature at the time of hydrolysis and condensation is 〇~2〇(rc, i〇~2〇(rc is better, 1G~12 (rc is better. In addition, although the reaction can be carried out without pressure, only 0.02) The pressure range of ~0.2 MPa, particularly 〇〇8~〇i5Mpa is preferred. When the hydrolysis reaction is carried out, the condensation reaction is carried out simultaneously with the hydrolysis, and the hydrolyzable group of the hydrolyzable decane is added [specifically, for example, the foregoing Most of X() in the general formula (IV) is preferably 100% hydrolyzed into a hydroxyl group (OH group), and most of the 0H group is preferably 8% or more, more preferably 9% or more. Particularly suitable is 1% by weight, and condensation occurs, which is suitable from the viewpoint of liquid stability. The alcohol, solvent and catalyst formed in the reaction can also be removed from the mixed solution after hydrolysis and condensation by a known technique. Further, the obtained product can be further purified by removing the catalyst from various purification methods such as washing, column separation, and solid absorbent, etc. From the viewpoint of efficiency, it is removed by washing with water. Catalyst is preferred. The sesquioxide of the present invention The compound is produced by the above-mentioned production method plus 17 201026712. In the case where the 100% condensation is not carried out in the hydrolyzed condensation, the product obtained by the method of the present & method is used, except for the Si-OH group ( In addition to the sesquiterpene oxide compound of the structure in which all of the force cleavage and condensation is formed, there may be a trapezoidal structure, an incomplete cage structure, and/or an irregular sigma containing Si-OH groups remaining. The sesquiterpene oxide compound of the present invention obtained by the present production method may also contain the trapezoidal structure, the incomplete cage structure and/or the random condensate. The sesquiterpene oxide compound of the present invention obtained by the present production method has a ratio of sesquivalent 7-nuclear compound of a structure in which all of the Si-OH groups are added with water θ decomposition and condensation, and (10)% by mass or more is preferably '90% by mass. Preferably, it is suitable from the viewpoint of liquid stability. Manufacturing method 0 The production method B includes, for example, a hydrolyzable sulphur-burning stone having an amine group to produce a sesquivalent oxy-acid having an amine group. Step B1 of the compound The use of amine groups and having an oxygen to burn sesqui stone Xi of the compound obtained in step No. 61

A method for producing the 02th step of the isocyanate red Q compound having a (fluorenyl) acryloxy group and an isocyanate group. In the case of the above-mentioned step (1), the hydrolyzable alkaloid represented by the following general formula (Ιχ) is exemplified. [Chem. 10] H2N\R4, SiX3 - (IX) 18 201026712 [In general formula (IX), R4 and X are the same as described above. X can be the same or different. ]. In the above step B1, in order to obtain a sesquiterpene oxide compound having an amine group, specifically, a hydrolyzable stone garden represented by the general formula (IX) is used as a starting material in the catalyst. In the presence of a catalyst, the hydrolyzable condensation is carried out, or the hydrolyzable decane represented by the above general formula (IX) and the hydrolyzable decane other than the hydrolyzable sulphur-containing sulphur having an amine group are used as a starting material in the presence of a catalyst. Add water to decompose and condense. The hydrolyzable decane other than the hydrolyzable decane having the above-described amine group is not particularly limited as long as it can be hydrolyzed and condensed together with the hydrolyzable decane having the above-mentioned amine group to produce a sesquiterpene compound. Specific examples thereof include alkyltrimethoxyoxydecane such as methyltrimethoxysulfonium, methyltriethoxydecane, ethyltrimethoxydecane, and ethyltriethoxydecane. The above catalyst can suitably use an alkaline catalyst. Specifically, the basic catalyst may, for example, be hydrogen hydrazine, hydrogen oxyhydroxide (tetra), hydroxide metal hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyl bromide. An ammonium hydroxide salt such as triammonium chloride or an ammonium fluoride salt such as tetrabutylammonium fluoride. The amount of the catalyst to be used is not particularly limited, but there are problems such as cost increase and difficulty of removal, and on the other hand, if the amount is too low, the reaction becomes slow. Therefore, compared with the hydrolyzable decane i mole, the amount of the catalyst used is 19 201026712 υ. υυυΐ • the bucket is better ‘the best is the range of New Zealand 5 gi 莫 莫. When the hydrolysis and condensation are carried out, the ratio is the same as that of Lin (4). Adding water, Wei and water, the amount of water used in the cm ~ Qing ear is good for decomposing Wei 1 Mo, if the amount of water is shot, the strain will be slow, Mo _ better. After the yield of the hydrate is lowered, the amount of water is reduced by the amount of the desired structure of the desired structure of 2 Torr. Material,: there is a form of high-quantity ‘the test makes τ Μ 红 red aqueous solution 〇

Add water in other ways. (4) The water of the towel (4) can also be added with water _ _ zhong, can be (4) H = system; the method of simmering solvent is suitable from the viewpoint of preventing gelation and from the viewpoint of sticking. The organic solvent may be: organic..._organic organic solvent alone or in the form of a mixture to make the alcohols extremely = machine = to make "alcohol, ethanol, etc. low-grade, especially class, methane, etc." Polar organic should be = A: et al: 1 = high organic solvent is preferred, especially in addition to organic solvents, because it can be: from the system: = Γ. Especially the use of mixed polar organic solvents and non-polar organic life The preparation method can obtain the former solvent is _. The reaction temperature when the water is decomposed and condensed by the existing water is 0~2 〇 (TC, to 10~20 (rc 20 201026712 is better, 10~120 ° C is better) In the hydrolyzation condensation reaction, the condensation reaction is carried out simultaneously with the hydrolysis, and the hydrolyzable group of the hydrolyzable zebra calcination [specifically, for example, X of the above general formula (IX)] is mostly Preferably, 100% is hydrolyzed into a hydroxyl group (OH group), and most of the OH group is preferably 80% or more, more preferably 90% or more, particularly preferably 100%, condensation occurs, which is stabilized from liquid. Sexuality is appropriate. Step B2

In the above-mentioned step B2, specifically, for example, the organic group having the direct bond to the ruthenium atom obtained by the above-mentioned step B1 is an organic group represented by the following general formula (X) The amine group of the hemidecane compound is reacted with an isocyanate group of the compound represented by the following general formula (XI). 【化11】

—(X) NCO ((XI) [In the general formula (X), R4 is the same as described above. In the general formula (XI), R2 and R3 are the same as described above. ]. By carrying out the reaction, a sesquiterpene-oxygen compound having an organic group directly bonded to a ruthenium atom as the above-mentioned organic group represented by the general formula (II) can be obtained. In general, the above-mentioned reaction is carried out in the general formula (parent ρ table) using the above-mentioned compound 2 mol or more with respect to the organic group 1 21 201026712 represented by the general formula (X).

The foregoing reaction can be carried out in accordance with a conventional method of reacting the face I, the amine group with the isocyanate group. The reaction temperature is, for example, -78 t to 1 Torr. 2〇〇C, to _78. (:~1〇〇. (: is better, ~l〇°C~40°C is better. In addition, 兮g# '^ reaction can be implemented without relying on pressure, but with 0.02~〇.2Mpa, a , a The fare pressure range of 0.08~〇.15Mpa is very fast, so the reaction usually ends immediately at the end of the drop.

A suitable solvent can also be used in the reaction. Specific examples of the solvent include ethyl acetate, butyl acetate, decyl benzoate, decyl propionate, and the like; tetrahydrox, diwei, dimethoxyethane, and the like; Glycol glycol mystery, propylene glycol methyl (tetra) acid lysate, 3-methoxyacetic acid butyl vinegar and other glycol ethers; methanol, ethanol, 芮 楚 >> 内 内 alcohol # alcohol, toluene, xylene and other aromatic Hydrocarbons, aliphatic cigarettes, etc. The production method of the oxime oxygen compound of the present invention is more than that.

Here, when the condensation condensation in the hydrolysis step B1 is not 1% by weight, the structure obtained by the production method B has a structure in which all of the si_〇H group (sterol group) is hydrolyzed and condensed. In the case of a sesquioxane compound containing a trapezoidal structure, an incomplete cage structure, and/or a random condensate in which Si-OH groups remain, other than the sesquiterpene oxide compound, which is obtained by the production method B The sesquiterpene oxide compound of the present invention may also contain such trapezoidal structures, incomplete cage structures and/or random condensates. Further, by using the sesquioxane compound obtained by the present production method, the Si-OH group is all _, which is added to the structure of the water-decomposed condensation of 22 201026712, and is recorded on =^9Gf _ The viewpoint of the tearing property ^ The target compound obtained by the above respective reactions can be separated by means of separation means (4) (4), and can be combined with the separation and purification means, such as steamboat and solvent extraction.

Dilution method, recrystallization method, column chromatography, ion exchange chromatography, gel chromatography, affinity chromatography, and the like. / Active energy ray-curable composition The active energy ray-curable composition of the present invention contains the sesquiterpene oxide compound of the present invention and a photopolymerization initiator. The ratio of the use of the bis(tetra) oxy-compound (the (four) aliquot) of the present invention to the non-volatile component 丨(8) by weight of the active energy ray-curable composition of the present invention is not limited to (4), and (4) the amount of 5 to 99f is preferably. 1 〇 to 8 〇 by mass is preferred. Photopolymerization initiator The photopolymerization initiator can be used without particular limitation as long as it is a starting agent that absorbs an active energy ray to generate a radical. The photopolymerization initiator may, for example, be a biphenyl group (13611211), an α-diketone such as diethylamine or the like; an acyl〇in type such as benziumin; benzoin methyl ether; Acetyl ether, benzoin, etc.; acyloin ether; thioxanthone, 2,4-diethylthioxanthone, 2-isopropyl 2-isopropylthioxanthone, thioxanthone-4· 23 201026712 sulfonic acid, etc.; benzophenone 4,4'-double (two a benzophenone such as 4,4'-di(N,N-dimethylamino)benzophenone or 4,4'-bis(diethylamino)benzophenone; Michler's ketone class; aceto-phenone, 2-(4-toluene-sulfonyl)-2-phenylacetophenone , p-dimethylaminoacetophenone, α,α'-dimethoxyacetoxybiphenyl^^(aja^dimethoxyacetoxybenzophenone) >%-2-phenylacetophenone , p-methoxyacetophenone, 2-methyl[4-(methylthio) 2-morpholine-1-propanone, 2-benzyl-2-didecylamine-1-(4-morpholinylphenyl)-1-butanone, α-isoisobutylbutyl ketone Benzene (α-isohydroxy isobutyl phenone), α,α'-dimethoxy-4-phenoxyacetophenone, 1-hydroxy-cyclohexyl-phenyl-ketone Ethylketone; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(indenyl)phosphine oxide (bis(bis) Acyl) phosphine oxide), such as sulfhydryl chloride, phenacyl chloride, etc.; anthraquinone; 1,4-naphthoquinone; Halogen compound such as trihalomethyl phenyl sulfone, tris(trihalomethyl)-s-triazine, etc.; di-tert-butyl peroxide (di -tert-butyl peroxide) and the like. These photopolymerization initiators may be used in the form of one type or a mixture of two or more types. The commercially available product of the photopolymerization initiator may, for example, be 4 small force, half α 7 (IRGACURE)-184, the same 261, the same 500, the same 651, the same 907, the same 24 201026712 - CGI-1700 (CIBA SPECIALTY CHEMICAL In the case of the system, the product name), owe, 'Porto 2' (Darocur)-l 173, the same 1116, the same 2959, the same 1664, the same 4043 (Merck Japan company, the product name), the power of a cow 2 (KAYACURE) —MBP, the same as DETX-S, the same DMBI, the same EPA, the same A (Nippon Chemical Co., Ltd., trade name), t, half two 7 (VICURE)-10, the same 55 [STAFF (STAUFFER Co.,LTD.), trade name], 卜 TRIGONAL Pl [Akzo Nobel C〇., LTD., trade name], inch > F k彳 (SANDORAY) IOOO [SANDOZ Co.'LTD., trade name], -y(DEAP)[77.夕三 >社(APJOHN Co" LTD.), the product name], force > 夕牛二 y (QUANTACURE)-PDO, the same ITX, the same EPD [々才一卜 y 卜丰 > V 7. Manufactured by WARDBLEKINSOP Co., LTD., and the like A mixture of two or more kinds is preferable, and a mixture of a methyl ethyl ketone and a mercaptophosphine oxide is particularly suitable. The amount of the photopolymerization initiator to be used is not particularly limited, but is equivalent to the sesquiterpene of the present invention. The total amount of the oxyalkyl compound and the polymerizable unsaturated compound is preferably 0.5 to 10 parts by mass, more preferably 5 parts by mass. The lower limit of the range is at the active energy ray hardenability. The improvement aspect has the meaning that the upper limit has significance in terms of cost and deep hardenability. Polymerizable unsaturated compound The active energy ray-curable composition of the present invention may contain a polymerizable unsaturated compound other than the sesquiterpene oxide compound of the present month. The polyunsaturated compound is a compound other than the sesquiterpene oxide compound of the present invention, and is not particularly limited as long as it has at least one polymerizable unsaturated double bond in its chemical structure. The polymerizable unsaturated compound may, for example, be a monofunctional polymerizable unsaturated compound or a polyfunctional polymerizable unsaturated compound. The monofunctional polymerizable unsaturated compound may, for example, be an esterified product of a monovalent alcohol and (meth)acrylic acid. Specific examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-butyl (meth)acrylate. Isobutyl (meth)acrylate, tert-butyl (meth)acrylate, neopentyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofuranyl urethane (tetrahydr〇fUrfuryl) Methacrylate), is〇b〇rnyl methacrylate, phenyl methacrylate, benzyl methacrylate, N-propene oxime Oxyethyl hexahydrophthalimide (N-acryloyloχyethylhexahydrophthalimide). Further, for example, a hydroxyl group-containing (meth) group such as ethyl (meth) methacrylate, hydroxypropyl (decyl) acrylate or hydroxybutyl (fluorenyl) acrylate may be mentioned. Acrylate; acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-reactive ethyl (meth) acrylate Carboxy-containing (meth)acrylic acid vinegar such as 2-rebupropyl (meth) acrylate or 5-carboxypentyl (meth) acrylate; glycidyl (meth) acrylate a glycidyl group-containing polymerizable unsaturated compound such as allyl glycidyl ether; a vinyl aromatic compound such as styrene, α-methylstyrene, vinyltoluene or α- 26 201026712 gas styrene (N, N-dimethylamino ethyl methacrylate), N,N-diethylaminoethyl (meth)acrylate, (mercapto)acrylic acid Nitrogen-based (mercapto)acrylic acid vinegar such as Nt-butylaminoethyl ester; acrylamide (acr) Ylamide), mercapto acrylamide, N-methyl methacrylamide, N-ethyl (meth) acrylamide, N-methyl (methyl) Acetamamine, N-methoxymethyl methacrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl A polymerizable amine such as (meth)acrylamide, N,N-dimethylaminopropyl (meth) acrylamide or N,N-dimethylamineethyl (meth) acrylamide. The polyfunctional polymerizable unsaturated compound may, for example, be an esterified product of polyvalent yeast or (meth)acrylic acid. Specific examples include ethylene glycol dimethacrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylidene. Diol (mercapto) acrylic acid vinegar, 1,3-butanediol di(methyl) acrylic acid 1,3-butanediol dimethacrylate, 1,4-butanediol di(meth) Propionate, 1,9-nonanediol di(meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane dimethacrylate , pentaerythritol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol di(meth) a bis(meth) acrylate compound such as acrylate (1,6-hexanediol dimethacrylate), pentaerythritol di(meth) acrylate, bisphenol A ethylene oxide modified di(meth) acrylate; glycerin Tris(fluorenyl) acrylate, trishydroxypropyl propane tris(曱27 201026712 based) acrylate vinegar (tr Imethyl〇lpr〇Pane trimethacrylate), together with methyl propane propylene oxide modified tri(meth) acrylate, trimethylolpropane oxyethylene modified tris(indenyl) acrylate, isovalerol tris(methyl) a tri(meth) acrylate compound such as acrylate or ε-caprolactone modified tris(propylene oxy oxy) isomeric cyanurate; and tetrapentaerythritol tetra(meth) acrylate; The methyl acrylate compound may be exemplified by diisopentylpentaerythritol penta(meth)acrylate or diisopentyltetrakis(meth)acrylate. Further, for example, a (meth) methethane methacrylate resin, an epoxy (meth) acrylate resin, a polyester (meth) acrylate resin, or the like can be given. The (meth) ® urethane acrylate resin may use, for example, a polyisocyanate compound, a hydroxyalkyl (meth) acrylate, and a polyol compound as a raw material, in an amount equivalent to a molar amount or an excess state with respect to the isocyanato group 'hydroxyl group. A reaction occurs and can be obtained. These polymerizable unsaturated compounds may be used singly or in combination of two or more. The amount of the polymerizable unsaturated compound to be used is not particularly limited. However, from the viewpoint of the physical properties of the coating film, the non-volatile content of the sesquiterpene compound of the present invention is 丨 by mass. In the 〇 1 ~ · 1000 parts by mass is better, 20 to 200 parts by mass is better. The active energy ray-curable composition of the present invention may be mixed with various additives as needed, or may be diluted with a solvent as required. The additives may, for example, be sensitizers, ultraviolet absorbers (four), photoampere (four), polymerization inhibitors, antioxidants, defoamers, surface conditioners, plasticizers, colorants, and the like. ,

Examples of the solvent to be used for the dilution include ketones such as (iv) and m-methylisoketone; esters of acetic acid, butyl acetate, benzoic acid, and esters of I 28 201026712; tetrahydrofuran; Ethers such as dioxane and dimethoxyethane; ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol methyl ether, propylene glycol methyl acid 6, and 3-methoxy acetic acid B2 class; aromatic cigarettes, such as the moon and aquarium. These may be appropriately combined and used for the purpose of adjusting the viscosity, adjusting the coating property, and the like.

The non-volatile component of the active energy ray-curable composition of the present invention is not particularly limited. For example, 2〇~%% by mass, Μ~% by mass is better "Hai and other ranges are in terms of smoothness of coating film and shortening of drying time. I apply the active energy ray-curable composition of the present invention. The method of the surface of the object to be coated is not particularly limited, and may be, for example, roll coating, roll coater coating, rotary coater coating, curtain roll coating, slit coating, spray coating, electrostatic coating, dipping Coating, screen printing, spin coating, and the like. The object to be coated is not particularly limited. Specific examples thereof include metal, glass, plastic, wood, and the like. When the coating film is formed from the active energy ray-curable composition, it can be carried out as needed. The solvent m can be removed without removing the solvent. For example, it can be (10) to just. The drying temperature of c is carried out at a drying time of 3 to 20 minutes. The film thickness of the coating film can be appropriately set for the purpose. For example, the film thickness is preferably 100/m, and is preferably 1 to 2 (^m is more preferable. When the film thickness is at least the lower limit of the ranges, the smoothness and appearance of the coating film are excellent. When the value is less than the limit, the coating film is excellent in hardenability and crack resistance. After the active energy ray-curable composition is applied to the surface of the object to be coated and dried according to 29 201026712, the active energy ray is irradiated to form a hard coating film. The irradiation source and the irradiation amount of the active energy ray irradiation are not particularly limited. For example, as the irradiation source of the active energy ray, an ultrahigh pressure, a high pressure, a medium pressure, a low pressure mercury lamp, a chemical lamp, a carbon arc lamp, a xenon lamp, The metal halide lamp, the fluorescent lamp, the tungsten lamp, the sunlight, etc. The irradiation amount is preferably 5 to 20,000 J/m2, and more preferably 100 to 10,000 J/m2.

The active energy ray irradiation can be carried out under an atmospheric atmosphere or in an inert gas atmosphere. The inert gas may, for example, be nitrogen gas or carbon dioxide. From the viewpoint of hardenability, it is preferred to irradiate the active property line under an inert gas atmosphere. Further, after the active energy ray is irradiated, the coating film may be heated as needed. By heating, the deformation of the coating film caused by the hardening of the coating film by the irradiation of the active energy ray can be alleviated. In addition, the hardness or adhesion of the coating film is sometimes increased by such heating. The heating can usually be carried out at an atmosphere temperature of 150 to 250 ° C for 1 to 30 minutes.

[Examples] Hereinafter, the present invention will be described in more detail by way of examples. In addition, "parts" and "%" mean "parts by mass" and "% by mass" unless otherwise stated. Further, the structural analysis and measurement in the present embodiment were carried out using the following analysis apparatus and measurement method in addition to the above-described analysis apparatus described in the present specification. (29Si-NMR, W-NMR analysis) Device: FT-NMR EX-400 manufactured by JEOL Co., Ltd. Solvent: CDC13 30 201026712 Internal standard material: tetramethyl decane (FT-IR analysis) Device: FT/IR-made by JASCO Corporation 610 (Measurement method of SP value) The SP value in the present embodiment means a solubility parameter, which can be measured by a simple actual measurement method by cloud point titration, and follows the formula of K.w. SUH and JM CORBETT described below (see The value calculated by journai 〇f Appiie (jp〇iymer science, 12, 2359, 1968). The formula sp = ( { Vml . §H+

Vmh · 60) / (7-yml + ^Vinh) At the time of cloud point titration, the sample 〇.5g was dissolved in acetone 1〇m丨, and n-hexane was added to read the drop amount H (ml) of the cloud point. The cloud point titer D (ml) when deionized water was added to the acetone solution was read and applied to the following formula, and Vml, Vmh, dH, and 5D were calculated. Further, the molecular volume (mol/ml) of each solvent was: acetone: 74.4, n-hexane: 130.3, deionized water: 18, SP of each solvent, acetone: 9.75, n-hexrol: 7.24, deionized water: 23.43. Vml = 74.4xl30.3/((l-VH)xl30.3+VHx74.4) Vmh=74.4xl8/((l-VD)xl8+VDx74.4) VH=H/(10+H) VD = D /(10+D) 6H=9.75xl0/(10+H)+7.24xH/(10+H) 6D = 9.75 χ 10/( 10+D)+23.43 xD/( 10+D) (Example 1) 3-Aminopropyltrimethoxy-silaney OO, 2-propanol 1,600 parts, 4 parts of tetrabutylammonium fluoride and deionized water 31 201026712 60 parts were added to the reflux cooler In a separable beaker of a thermometer, an air introduction tube, and a mixer, it was reacted at 60 C for 8 hours. After concentration by vacuum distillation until the non-volatile content became 60%, 160 parts of butyl acetate was mixed and continued. Distillation under reduced pressure to obtain a 60% solution of the non-volatile component of the product (P1). Mix 400 parts of butyl acetate and acrylic acid-2 in a separable beaker equipped with a reflux condenser, a thermometer, an air introduction tube, and a stirrer. - 310 parts of isocyanatoethyl ester, and cooled to l ° ° C while stirring under an ice bath, and 60% of the nonvolatile matter of the product (P1) was dropped while maintaining the reaction temperature below 0.001. 400 parts of solution. After stirring at 60 ° C for 1 hour, filter with 300 mesh The product was filtered to obtain a 50% solution of the non-volatile component of the product (P2). As a result of 29Si-NMR analysis of the product (P1), it was confirmed that all three oxygen atoms bonded to Si were derived from bonding with other Si. The T3 structure has a peak near -70 ppm and a peak of -59 ppm from a T2 structure having a sterol group. The integrated intensity ratio of the peaks is the peak from the T3 structure / the peak from the Τ2 structure = 90/10 In addition, the total amine value was 508 mgKOH/g. The weight average molecular weight of the product (P1) was 丨, 5 〇〇. As a result of 29Si-NMR analysis of the product (P2), it was confirmed that three oxygens bonded to Si were confirmed. The atoms are all from the peak near -70 ppm of the T3 structure bonded to the other & and the peak of -59 ppm from the butyl structure having a sterol group. The integrated intensity ratio of the peaks is from the T3 structure. The peak/peak from the T2 structure = 9〇/1〇. The total amine value is 〇mgK〇H/g, and the NCO value is OmgNCO/g. 201026712 The result of 1H-NMR analysis of the product (P2) was confirmed from Bonded to the methylene group of Si. 6ppm peak. In addition, confirmed from acetonitrile The peak of 5.9 ppm, 6.1 ppm, and 6.4 ppm of the carbon-carbon unsaturated bond of the oxy group. The molar ratio of the carbon-carbon unsaturated bond of the acryloxy group to the methylene group bonded to Si calculated using the peak intensity ratios was 1.01. The product (P2) had a weight average molecular weight of 3,000. From the results of the above-mentioned 29Si-NMR, h-NMR, and weight average molecular weight of the product (P2), it was confirmed that the product (P2) is an organic group directly bonded to a ruthenium atom, and has almost the following formula. Organic group represented by (XII) [化12] c one ο bH2

HN /so

HN CH;

CH

The weight average molecular weight of XII is 3,000 times the hemidecane compound. The SP value of the sesquiterpene oxide compound produced was 13.8. (Example 2) 455 parts of 2-hydroxyethyl acrylate, 870 parts of isophorone diisocyanate, 1 part of p-methoxyphenol and 883 parts of butyl acetate were charged. In a separable beaker of a reflux cooler, a thermometer, an air introduction tube, and a mixer, the dry air is blown at 60. (: The reaction was carried out for 24 hours to obtain a 60% solution of a nonvolatile matter of the product (P3). The product (P3) had an NCO value of 144 mg NCO/g. It was equipped with a reflux condenser, a thermometer, an air introduction tube, and a mixer. In a separable beaker, 326 parts of butyl acetate and the non-volatiles of the product (P3) were mixed. 33 201026712 60% solution of π, 230 parts, and cooled to (7)^ while stirring in an ice bath. The reaction temperature was maintained at 20 (: The following is a mixture of a non-volatile component 60% solution of the product (ρι), 4 〇 0 parts. At 60. (: After stirring for 1 hour, it is filtered through a 3 〇〇 sieve filter to obtain a product ( As a result of 29Si-NMR analysis of the product (P4), it was confirmed that all of the three oxygen atoms bonded to Si were -70 ppm from the T3 structure bonded to other Si. The nearby crests, as well as the peaks from -59 ppm from the D2 structure with a sterol group. The integrated intensity ratio of these peaks is the peak from the T3 structure / the peak from the T2 structure = 9 〇 / 1 〇. The value is 〇mgKOH/g, and the NCO value is 〇mgNCO/g. Results of 1H-NMR analysis of the product (P4) It was confirmed that the peak derived from the methylene group bonded to Si was 6 ppm. Further, the peaks of 5.9 ppm, 6.1 ppm, and 6.4 ppm of the carbon-carbon unsaturated bond derived from the acryloxy group were confirmed. The peak intensity ratio is calculated from the methylene group bonded to Si, and the molar ratio of the carbon-carbon unsaturated bond of the acryloxy group is 1.02. The weight average molecular weight of the product (P4) is 5,000. As a result of the above-mentioned 29Si-NMR, W-NMR, and weight-averaged molecular weight of the product (P4), it was confirmed that the product (Ρ4) is an organic group directly bonded to a ruthenium atom and contains almost the following formula ( Organic group represented by XIII) [Chem. 13]

34 201026712 The resulting R'R8 in U(XIII) represents the weight average molecular weight of the isophoron diisocyanate residue of 5,000 times the hemioxalate compound. The SP value of the sesquiterpene oxide compound is 12.9. (Comparative Example 1) 300 parts of Azure, tetrabutylammonium hydroxide 4% by weight methanol solution

It can be separated into a detachable cooler with a reflux cooler, a thermometer and a transfer machine. Adding tetrahydrofuran _ part to it and then adding the diluted 3_(acryloxy) propyl trimethoxy decane (3-(aCryloyl〇xy) pr〇pyltrimeth〇xysiiane) ii 在* 24 hours. The volatile component was removed by distillation under reduced pressure, and then dissolved in propylene glycol methyl acetate __ part' to obtain a nonvolatile matter 5 〇% solution of the product (P5). As a result of performing 29Si_NMR analysis on the product (P5), it was confirmed that all of the three oxygen atoms bonded to Si were from a peak near -70 ppm of the τ3 structure bonded to the other & and from a sterol group having a sterol group. The peak of the D2 structure - 59 ppm. The integrated intensity ratio of the peaks is such that the peak from the τ3 structure/the peak from the Τ2 structure = 9 〇 / 1 〇. Further, as a result of iH_NMR analysis of the product (Ρ5), a peak of 6 ppm from a methylene group bonded to Si was confirmed. Further, 5, 6. ippin, and 6.4 ppm peaks of the carbon-desaturated bond derived from the acryloxy group were confirmed. The molar ratio of the carbon-carbon unsaturated bond with respect to the 'acryloxy group bonded to the methylene group bonded to Si using the peak intensity ratio was 1.00. Further, the product (P5) had a weight average molecular weight of 1,500. From the results of the above-mentioned 29Si_NMR, 35 201026712 FT-IR, and the weight average molecular weight of the product (P5), it was confirmed that the product (p5) is an organic group having a direct bond to a ruthenium atom, and is represented by the following formula. Organic group

The weight average molecular weight is 1,500 times the semi-oxane compound. The SP value of the sesquisquid compound produced was 9.5. (Embodiment 3) One (XIV)

The non-volatile component of the product (Μ) obtained in Example 1 was mixed with a non-volatile component (5%) solution and the following polymerizable unsaturated compound (Α1) to give a product (ρ2) and a polymerizable unsaturated compound (Α1). The mass ratio becomes i : !, and the mixture is stirred at 4 ° t for 24 hours to prepare a mixed solution. The miscibility of the mixed solution was evaluated, and the compatibility in the solution state of the product (P2) silkiness*saturated compound obtained in Example 1 was evaluated. The evaluation was performed by visually observing the compatibility state and following the following criteria. The evaluation results are shown in Table 1. In the same manner as described immediately, the product (4) and the polymerizable unsaturated compound (A2) to (A8) are mixed separately to obtain each mixed solution. Further, the compatibility of the mixed solution was evaluated using the criteria of the above (10). The evaluation results are shown in Table 1. <Determination of compatibility> 〇: Uniform, transparent, good compatibility △: Slightly turbid' or readable when shaken, poor compatibility 36 201026712 χ : Very turbid, or visible separation, agglutination, sediment, gel Any one or more of them may have poor compatibility. <Polymerizable unsaturated compound>

A1 : HDDA (trade name ' DAICEL-CYTEC COMPANY LTD., 1,6-hexanediol diacrylate) A2: ARONIXM-14〇 (trade name, manufactured by Toagosei Co., Ltd., N-propylene oxyethyl hexahydro Phthaloin imine) A3 : ARONIXM-325 [trade name, manufactured by Toagosei Co., Ltd., ε_caprolactone modified tris(propylene oxyethyl) isocyanuric acid brewing] Α4: trimethylolpropane II Acrylate Α5: pentaerythritol diacrylate Α6: pentaerythritol triacrylate Α7 : ARONIXM-4〇3 (trade name, dipentaerythrit lp mail a_ /hexa-acrylate) A8: ARONIX M-1200 (trade name, difunctional amine ester acrylate oligomer manufactured by Toagosei Co., Ltd.) (Example 4, Comparative Example 2) The same treatment as in Example 3, for Example 2, Comparative Example Each of the products (P4, P5) obtained in 1 was evaluated for compatibility with the solution state of the polymerizable unsaturated compound. The results of the assessment are shown in the table. 37 201026712

(Example 5) An active energy ray having a sesquiterpene oxide compound of the present invention for 3

The chemical composition' was evaluated for compatibility when a polymerizable unsaturated compound was mixed. The test methods are shown below. 100 parts of a non-volatile content of the product (P2) obtained in Example 1 was mixed, 100 parts of a polymerizable unsaturated compound (A1), and hydroxycyclohexyl-phenyl-ketone (photopolymerization initiation) 3 parts and 2,4,6-trimethylphenyl fluorenyl _ bis-phenyl-phosphine oxide (photopolymerization initiator) 〇 5 parts, diluted with ethyl acetate to 30% after non-volatile content The mixture was mixed to prepare an active energy ray-curable composition.

Next, the active energy ray-curable composition was applied to the intermediate coated board (Note 1) with a dry film thickness of 1 〇μπΐ2 using an applicator, and a high-pressure mercury lamp (8 之后) was used after 8 (r solvent was removed after drying for 1 minute). W/cm) The ultraviolet ray (the wavelength of the peak top is 365 nm) was irradiated with an irradiation amount of 20'000 J/m 2 to cure the coating film. The appearance of the cured coating film was visually observed, and the compatibility state was evaluated in accordance with the following criteria. In addition to the above, except that the polymerizable unsaturated compound (A2) to (A8) is used in place of the polymerizable unsaturated compound (A1), respectively, the mixture is prepared in the same manner as described above. Each active energy ray-curable composition of the unsaturated compound (A2) to (A8). Next, a cured coating film was prepared under the same conditions as described above, 38 201026712, and the coating film was visually observed, following the following. The evaluation results are shown in Table 2. (Note 1) Medium-coated plate: 0.8xl5〇 chemically converted by PALBOND # 3020 (trade name, NIHON PARKERIZING CO" LTD., zinc phosphate treatment agent) On x70mm cold rolled steel sheet, The electrode was coated with elcRON GT-10 (trade name, manufactured by KANSAIPAINTCO., LTD., cationic electrodeposition coating) to form a film thickness of 2 μm, and sintered at 170 ° C for 30 minutes to form an electrodeposition coating film. The film was sprayed with wp_3 〇〇 (trade name, KANSAI PAINT CO.'LTD. 'waterborne intermediate coating paint) to make the cured film thickness 25 μηι, and then sintered and dried in an electrothermal drier for 14 〇〇 C x 3 〇 minutes.涂板. <Determination of compatibility> 〇: X : 均匀 Uniform, transparent, good compatibility, slightly turbid, poor compatibility, very turbid, or visible agglomerates, seeding and surface coating (crawling) In addition to the above, the compatibility was poor (Example 6 and Comparative Example 3), except that the solutions of the products (p4, p5) obtained in Example 2 and Comparative Example 1 were used instead of the product (P 2 ), respectively. The non-volatile component was treated in the same manner as in Example 5 except that the non-volatile content was 5 〇%, and the silky energy ray-curable composition was hardened under the same conditions as in the actual _5. Coating and evaluation of mixed polymerization Compatibility unsaturated compound after the evaluation results are shown in Table 2. Table 2 39 201 026 712

Example 5 Product (Ρ2) Polymerizability; Absolute compound Α1 A2 A3 Α4 Α5 Α6 Α7 Α8 U &quot;ο-1 〇Ο Ο η 〇〇Example 6 Product (Ρ4) 〇〇〇ο η 〇〇X Comparative Example 3 Product (Ρ5) 〇XXXXXX (Examples 7 to 10)

The active energy ray-curable composition shown in Table 3 was prepared in the same manner as in the method for producing the active energy ray-curable composition and the method for producing the cured coating film in Example 5, and was applied to the intermediate coated sheet (Note 1). A hardened coating film having a dry film thickness of ημηι was formed thereon to obtain a test plate. The scratch resistance and weather resistance of each test plate prepared were evaluated. The evaluation results are shown in Table 3. [Scratchability] Commercially available Steel wool (#0000) wipe each coating film to visually observe the coating film and evaluate it according to the following criteria. '〇: No damage, cracks, peeling, or slight damage, but no practical problems Τ △: Look To damage

X: See cracks, flaking, significant damage, etc. <Weather resistance> After performing a 1000-hour test on each of the prepared test panels using Sunshine Weather-O-Meter, visually observe the coating film and follow the following criteria. Evaluation 〇: No abnormality, or although barely see swelling, discoloration, _ _, peeling, etc., but there is no practical problem △: see swelling, discoloration, gloss change, peeling, etc. 40 201026712 X : Table 3 Example 7 Example 8 Example 9 Example 10 ί 50 50 A3 50 Α8 50 1-Hydroxy-cyclohexyl-phenyl-one 3.0 3.0 3.0 3.0 2,4,6-trimethylbenzimidyl-diphenyl-phosphine oxide 0.5 0.5 0.5 0.5 Scratch resistance The value in the 〇〇〇〇 〇〇〇〇 〇〇〇〇 mixture indicates non-volatile content [Simple description of the figure 3 (none) [Main component symbol description] (none) 41

Claims (1)

201026712 VII. Patent application scope: 1. A sesquiterpene oxide compound which is a sesquiterpene oxide compound having an organic group directly bonded to a ruthenium atom, characterized in that the aforementioned organic group directly bonded to a ruthenium atom At least one of them is an organic group having a urea bond and one (indenyl) acryloxy group. 2. The sesquiterpene oxide compound according to claim 1, wherein the organic group having a urea bond and a (meth) propylene fluorenyloxy group is an organic group represented by the following general formula (I) Mission, [Chemical 1] In the formula (I), R1 represents a hydrogen atom or a methyl group, and Y represents a divalent organic group having a urea bond. ]. 3. The sesquiterpene oxide compound according to the second aspect of the invention, wherein the organic group represented by the general formula (I) is an organic group represented by the following general formula (II). In the formula (11), R2 represents a hydrogen atom or a methyl group, and R3 represents a divalent hydrocarbon group having 1 to 10 carbon atoms or is represented by the following general formula (III) 42 201026712 [Chemical 3] - F^-OCN-R6 - (III) II vf 0 [In the formula (III), R5 represents a divalent hydrocarbon group having 2 to 4 carbon atoms, and R6 represents a diisocyanate residue. The divalent group represented by R2 represents a divalent hydrocarbon group having 1 to 10 carbon atoms. }. 4. The sesquiterpene oxide compound according to claim 1, wherein the weight average molecular weight is 1,000 to 100,000. An active energy ray-curable composition comprising the sesquiterpene oxide compound described in claim 1 and a photopolymerization initiator. 6. The active energy ray-curable composition according to claim 5, further comprising a polymerizable unsaturated compound other than the sesquiterpene oxide compound. 43 201026712 IV. Designated representative map: (1) The representative representative of the case is: ( ). (None) (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: