TW201118066A - Cyclic (meth)acrylates and process for preparation thereof - Google Patents

Abstract

Provided are (meth)acrylate monomers which have cyclic structures and which exhibit excellent photosensitivity, good air-drying properties, high hardness, and low viscosity. Also provided are polymerizable resin compositions containing the same. Cyclic (meth)acrylates that have structures represented by general formula (1) [wherein R1s are each a hydrogen atom or (meth)acryloyl, with at least one R1 being (meth)acryloyl; A is C2-4 alkylene; and n is a number of 0 to 30].

Description

201118066 VI. Description of the Invention: Field of the Invention The present invention relates to a cyclic (meth) acrylate compound and a method of the same. BACKGROUND OF THE INVENTION In the case of producing a polymerizable resin composition, a (meth) acrylate is one component of an important copolymerization monomer, and is mixed for various purposes. However, in general, in a single monomer polymerization, the desired properties are not obtained, and a plurality of different (mercapto) acrylates or oligomers, polymers, and inorganic materials are mixed for obtaining the necessary physical properties. 'Perform the desired performance by making these polymerizations (Patent Document 丨). For example, it is mixed with a coating composition for a hard coat layer or the like or an ink composition for inkjet printing, such as dipentaerythritol, neopentyl alcohol, bistrimethicone, trimethylolpropane, and neopentyl The method of (meth) acrylate of a polyfunctional alcohol represented by an alcohol or the like can impart mechanical strength and chemical stability to the polymerizable resin composition after curing. However, polyfunctional (meth) acrylates, particularly (mercapto) acrylates of dipentaerythritol, have a very high self-adhesion, and there is also a problem that the viscosity of the composition rises due to mixing. Further, the use of the polyfunctional (meth) acrylate in the application of a film or the like may cause curling (bending) of the coated film (Patent Documents 2 to 4). In addition, in other applications, especially dry film anti-insecticides, coloring anti-insecticides, black resist compositions, etc., in addition to the physical properties of the film after hardening, special 201118066 is activated by ultraviolet light, electron beam, etc. When the wire can be hardened, it is required to complete the hardening with a low amount of light, that is, high sensitivity is required. In particular, it is considered that a material having a high light-shielding property of a pigment or a dye such as a color resist or a black resist mixed at a high concentration is extremely high in the use of a material which can be cured with a low amount of light (Patent Document 5) 6). CITATION LIST Patent Literature Patent Literature No. JP-A-2008- 025 571 Patent Document No. JP-A-2009- 025 [Problem to be Solved by the Invention] The present invention has been made in view of the above circumstances, and an object thereof is to provide a ring structure. The (meth) acrylate monomer and the composition thereof have excellent light sensitivity, good air drying property and low viscosity, and the hardness and low curl property of the hardened film are also excellent, and a manufacturing method is provided. Industrially available raw materials The (meth) acrylate monomer and its composition are produced by a reaction which can be industrially carried out. Means for Solving the Problems As a result of intensive studies to solve the above problems, the inventors of the present invention have issued a ring-shaped (fluorenyl) acrylate compound represented by the general formula (1), which has a cyclic structure and is more novel. (meth) acrylate of polyfunctional alcohol represented by pentaerythritol, neopentyl alcohol, bistrihydroxymethyl propane, trimethylolpropane, neopentyl alcohol, etc., has low viscosity and excellent light sensitivity In addition, it was confirmed that the properties were maintained in the polymerizable composition, and the present invention was completed. That is, the cyclic (meth) acrylate compound of the present invention has the structure shown by the following general formula (1). [Chemical 1] General formula (1):

In the general formula (1), R1 represents a hydrogen atom or a (fluorenyl) acrylonitrile group, and at least one is a (meth) acryl fluorenyl group; A represents a C 2 to 4 alkylene group; η represents 0 〜 The value of 30. Among the above compounds, η in the general formula (1) is preferably from 1 to 30. The method for producing a cyclic (meth) acrylate compound of the present invention is a method for producing a cyclic (meth) acrylate compound having a structure represented by the above general formula (1), comprising a (meth)acrylic acid halide Or (mercapto)acrylic anhydride reaction to acylate the isosorbide or isosorbide alkylene oxide adduct; and, any of the following steps: using (hydrazino) acrylate Ester exchange, so that isosorbide or isosorbide alkylene oxide is added to 201118066 to produce the step of (meth)acrylic acid; or, under dehydrating condensing agent or acid = sub-, let (meth)acrylic anhydride The reaction is carried out by subjecting the isoamyl (tetra) or isosorbide decane adduct to a propylene oxime esterification step. Advantageous Effects of Invention The cyclic (meth)acrylic acid g-containing compound of the present invention is blended with conventional dipentaerythritol, neopentyl alcohol, bis-trimethyl propyl ketone, tri-methyl methacrylate, and new pentane. The (meth)acrylic acid-based polymerizable resin composition of the polyfunctional alcohol represented by the tetraol or the like has light sensitivity of the same degree or more, air drying property, hardened skin hardness, and the like, and is reduced, It does not cause defects such as curling of the hardened film. Further, the compound of the present invention can be suitably used as a polymerizable monomer, such as a dry film anti-side, a coloring anti-, a black anti-, a semiconductor anti-knocking agent, and the like (four) eucalyptus wax composition, dental, etc. (4) (4) A resin composition, a paint, a resin composition for coating, a composition for printing ink, and the like. Further, since the cyclic (fluorenyl) acrylate compound of the present invention is produced by using plant-derived isosorbide as a main raw material, it is possible to provide a cleaning material which is low in dependence on fossil resources. Further, according to the production method of the present invention, the above-described compound of the present invention can be produced with high purity and good yield because of industrially simple operation. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an NMR chart of isosorbide diacrylate obtained in Example 1. Fig. 2 is an NMR chart of the isosorbide 15EO adduct diacrylate obtained in Example 7. Fig. 3 is an NMR chart of the isosorbide 6EO adduct diacrylate obtained in Example 8. 201118066 c. Embodiments for carrying out the invention Hereinafter, the present invention will be described in detail. <Cyclic (meth) acrylate compound> The polymerizable single system of the present invention has the structure of the above general formula (1). In the general formula (1), R1 represents a hydrogen atom or a (meth)propanyl group; V 1 is a (meth) propyl group, and A represents a carbon number of 2 to 4, and η is not 〇 30 The value. From the viewpoint of improving the compatibility with the resin and the solvent, the stability of the product, the reactivity of the (meth)acrylic acid S, and the physical properties of the cured product, η is preferably from 1 to 30. <Ring (Method for Producing Methyl Compound)> The method for producing a cyclic (meth)propene compound of the present invention is not limited to gas. The isosorbide or isosorbide ring as described below can be used. (Responsive reaction (referred to as isosorbide, etc.) as a raw material (meth)acrylic acid * two = said:: for example, sulfuric acid, p-type; in water,,:; two:::: = Method for refining alcoholic anhydride - Some methods. Esterification of esters of lower alcohols of (meth)acrylic acid, such as medium-effective in-situ or (methyl-sound, == 201118066 methyl enoate) The reaction 'uses a carbodiimide-based dehydrating condensing agent such as DCC (dicyclohexylcarbodiimide) or WSCD (water-soluble carbodiimide), dehydration condensation with (meth)acrylic acid, or acid contact The method of dehydration condensation of the medium, etc. Further, since the compound of the present invention and the (meth)acrylic compound of the raw material have high polymerizability, a polymerization inhibitor can be suitably used in the production or storage of the product so that the polymerization does not occur. The polymerization inhibitor can be used for the benzoquinone, which is the same as the benzene. , 2,5-diphenyl-p-benzene, etc., benzodiazepines, 2,2,6,6-tetramethylpiperidine-yl-oxide (TEMPO), etc., nitroxides, tert-butyl Substituted catechols such as catechins, amines such as diphenylamine, phenyl-β-naphthylamine, ferrocene, nitrosobenzene, picric acid, molecular oxygen, sulfur, chlorination Copper (II), etc. Among them, hydroquinone, morphine, and nitroxide are preferred at the point of versatility and polymerization inhibition. The addition amount of the polymerization inhibitor is relative to the general formula of the target ( The compound represented by 丨) has a lower limit of substantially l〇PPm or more, suitably 30 ppm or more, and an upper limit of usually 5,000 ppm or less, suitably i〇00 ppm or less. When too small, sufficient polymerization inhibition effect is not exhibited. There is a risk of polymerization during production or storage of the product, and when it is too much, it may hinder hardening and polymerization. Therefore, the compound of the present invention causes light sensitivity alone or when it forms a polymerizable resin composition. It is not suitable for lowering the physical properties such as poor cross-linking of the hardened material and mechanical strength. <Transesterification method> When the (meth)acrylic acid esterification of isosorbide or the like occurs by a transesterification method, the compound which can be used as the (fluorenyl) acrylated agent is (曱201118066-based) acrylic acid The ester lower alcohol ester. The lower alcohol is preferably a C1-C4 aliphatic alcohol, and the number of alcohol residues is selected from 1 to 3. Particularly suitable are methyl, ethyl, n-propyl and isopropyl groups of (meth)acrylic acid. The ester may be suitably operated by removing the methyl ester, ethyl ester or the like of (meth)acrylic acid at the point of removing the by-product alcohol in the reaction. The amount of (meth) acrylate used is relative to the raw material isosorbide. The lower limit of the number is usually 2 mol or more, suitably 4 mol or more, and the upper limit is usually 20 mol or less, and suitably 10 mol or less. The method of adding the acid to the inside of the 丞j is not particularly limited, and the total amount may be added to the isosorbide for reaction when the reaction is mixed, or may be added in batches in the middle of the reaction. The reaction is carried out in the absence of a solvent or by using a solvent. In the case of the hearing, the residual solvent is used as a solvent, and it is possible to use the combination of benzene, dimethyl ketone, amphibious oxime, hexane, gamma, etc.

Aliphatic hydrocarbon solvent, diethyl ether, _ + Α β, J ^ tetrafurfuran, monoethylene glycol dioxime ether, diethylene glycol dimethyl ether, etc., such as solvent, acetone, methyl ethyl ketone, methyl isobutyl: Ketone system ★ medium - mercaptocarbamide or dimercaptoacetamide, N-A: Luo Pin, etc. (4) (4), solvent. The towel is preferably a reactive hydrocarbon solvent such as a == toluene or a solvent such as methyl bromide or methyl isobutylene. These soluble #i m ' media are used to make any of the plural sisters available. In the case of pure production, the concentration of isosorbide or the like of the raw material is usually 1% or more. The appropriate upper limit is not particularly limited, and the upper limit is not particularly limited, and is usually 8 (see below), and suitably 5 ()% or less. Red reversal The presence of catalyst is fine. (4) It can be considered as follows: _ = The reaction can be carried out, for example, tetra-based titanium oxide, etc. = 201118066 genus compound, sodium decyl alcohol or the like, or the metallographic alkoxide, diisopropyl Aluminium alkoxide such as aluminum oxide, metal hydroxide of alkaline earth metal such as lithium antimony oxide or sodium hydroxide, dibutyltin oxide, dioctyltin oxide, distanoxane Among them, a tin compound such as a compound or the like is preferably a transition metal compound such as tetraisopropyl oxide or an alkali metal such as sodium methoxide or an alkali earth metal alkoxide such as sodium isopropylate at a point where catalyst activity is easily obtained. The lower limit of the amount of the catalyst used relative to the molar amount of the isosorbide or the like of the raw material is usually 0.01 mol% or more, suitably 0.1 mol% or more, more preferably 0.5 mol% or more, and the upper limit is usually It is 50 mol% or less, suitably 20 mol% or less, and further suitable is 1 mol. /. the following. When the amount of the catalyst is too small, the reactivity is lowered, and the yield of the desired ester compound tends to decrease. On the other hand, in the case of too much, the load on the post-treatment step after the transesterification reaction is increased, and the economy is economical. The point of view is also inappropriate. The reaction is preferably carried out using a reactor equipped with a general stirring device. Further, it is preferred to carry out the reaction while the alcohol produced in the distillation reaction is moved to the formation system. At this time, as the (mercapto) propionate vinegar used as the alcohol and the reagent is azeotroped and the (mercapto) acrylate is distilled from the system, the reaction may be carried out by sequentially replenishing (mercapto) acrylate as needed. The reaction temperature is preferably carried out at a temperature of 0 to obtain a sufficient reaction rate. Specifically, the lower limit is usually 30T: or more, suitably 50 〇 c or more, and the upper limit is usually 200 ° C or less, and is suitably carried out in the following ranges. When the reaction temperature is too high, there will be a (methyl) propylene (2011) 066 which causes the polymerization of the ester of the product and the product of the product, and the 隹-如-仏1 is negative, when it is too low, 7 If you don't want to enter the 仃 曰 曰 换 换 换 , , , , , , , , , , , , , 换 换 换 换 换 换 换 换 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ Anti-library. The lower limit of the reaction time is usually 1 () minutes mi 咏 or more. The appropriate one is 30 points or more. The upper limit is not particularly limited, but the limit is 5 hours or less, and preferably 30 hours or less. <(indenyl)acrylic acid halide method, (mercapto)acrylic anhydride method> (meth)acrylic acid dentate or (methyl monoacid (tetra)) (meth)acrylic acid reagent can be used Isosorbide or the like is subjected to (methylation), which can be used as a (meth) propylene compound in this case (mercapto) propylene helium, (meth) propylene ruthenium bromide, (meth) propylene oxime iodine (meth)acrylic acid or (meth)acrylic acid oxime = relative to the raw material isosorbide molar number, the lower limit flux or more, suitably 0.05 moles or more, into -, ^Step is suitable for Moer's equivalent or more, the upper limit is usually 20 mol equivalent to τ ^ lower 'suitable to 10 mol equivalents or less' further suitable is 5 mol equivalents or less (methyl) Acrylic halide or (meth) propylene method 'as long as it will avoid the long-term contact between the (meth) acrylated reagent and the test substance $' Taiga, the method of addition is not particularly limited. Sorbitol and the like with (meth)acrylic acid halide or (methyl) ° 'will

Mix into the reactor, add alkaline substances later, or J to see the alkaline substance and isosorbide in the reactor, or the solution VIII / / the same solution (曱, acrylate or (曱) The reaction may be carried out by using acrylic acid anhydride. 201118066 When the reaction is carried out using (hydrazino)acrylic acid halide or (meth)acrylic anhydride, the reaction system is preferably carried out in a dehydrated state. If moisture is present in the system, it will be The (meth)acrylic acid i- or (mercapto)acrylic anhydride reacts to cause decomposition. The substrate used in the present invention, such as isosorbide, is a compound which is easily mixed with water, and the amount of water in the matrix is less. Specifically, it is preferably 1 mol% or less with respect to isosorbide or the like, and is preferably 0.1 mol% or less. The reaction can be carried out in either a solvent system or a solvent-free system, but the formation of by-products In the case of the treatment in the step, the solvent system is preferred. The use of the solvent is not particularly limited, and an aromatic hydrocarbon solvent such as toluene or diphenylbenzene or the like may be suitably used. An aliphatic hydrocarbon solvent such as heptane, an ether solvent such as diethyl ether, tetrahydrofuran, monoethylene glycol dimethyl ether or diethylene glycol dimethyl ether; or a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone. It is a solvent such as a solvent, a nitrile solvent such as acetonitrile or benzonitrile, an ester solvent such as ethyl acetate, butyl acetate or γ-butyrolactone, dimethylformamide or dimercaptoamine, or fluorenyl-fluorenyl. A guanamine-based solvent such as pyrrolidone or a solvent such as chloroform or dichloroethane. These solvents may be used singly or in combination with any of a plurality of solvents. When using a solvent, the difference in raw materials The lower limit of the concentration of sorbitol or the like is usually 1% or more, suitably 10% or more, and the upper limit is not particularly limited, but is usually 80% or less, suitably 60% or less. Using (fluorenyl)acrylic acid halide or (A) The (acrylic) acrylation reaction is usually carried out in the presence of a basic substance. The test substance which can be used may be a metal hydroxide such as sodium hydroxide or barium hydroxide, sodium carbonate or potassium carbonate. Etc. Gold 12 201118066 is a carbonate, phosphoric acid a metal phosphate such as potassium phosphate or a hydrogen phosphate, an alkaline ion exchange resin, an aromatic amine such as an organic tertiary amine such as triethylamine or tributylamine, or the like, or the like, wherein pyridine or the like may be suitably used. Ethylamine, potassium carbonate. The amount of the basic substance used is usually 1 molar equivalent to the (meth)acrylic acid halide or (fluorenyl)acrylic acid anhydride used, and suitably 2 moles. Above the equivalent amount of the ear, the upper limit is usually 10 mol or less, and suitably 5 mol or less. When the amount of the alkaline substance is too small, the reaction proceeds slowly or stops, and thus is not suitable. When it is too much, the problem of coloring of the product occurs, and it is also economically unsuitable. The reaction is preferably carried out using a reactor having a corrosion-resistant stirring device. The lower limit of the reaction temperature is usually -50 ° C or higher, suitably -20 Above °C, the upper limit is usually 80 ° C or less, and suitably 20 ° C or less. The reaction time is arbitrarily selected, but it is usually 30 minutes or longer, and is preferably 60 minutes or longer. The upper limit is not particularly limited, but is usually 20 hours or shorter, and suitably 10 hours or shorter. <Esterification by a condensing agent or an acid> In the case of esterification with (meth)acrylic acid, if a dehydrating condensing agent is present, the reaction proceeds rapidly. The condensing agent is generally used for the condensing agent known in the art, and can be used without particular limitation. For example, hydrazine, Ν'-dicyclohexylcarbodiimide, 2-gas-1,3-di can be suitably used. Mercapto group gasified imidazoline, propane phosphoric anhydride, carbonyl diimidazole (CDI), WSCD (water-soluble carbodiimide) and the like. Further, in this case, an organic basic substance such as pyridine, 4-dimercaptoamine pyridine or triethylamine may be used. Among them, from the point of view of condensation reactivity and easy availability, it is preferable to use H-agent 1Άν'-dicyclohexylcarbazone, and the test substance is preferably bite or triethylamine. The lower limit of the reaction calorie is usually -20 °c', suitably -10 °c, and the upper limit is usually 100 C, suitably 5 Torr. Hey. The amount of the condensing agent used is theoretically sufficient to use an equivalent amount or more with respect to the isoamyl alcohol of the substrate, etc., but even if it is appropriate to be more than 1.0 mol per liter, the step is suitably 2 _0 mol or more. . In the case where the condensing agent is not used, (mercapto)acrylic acid and isosorbide are reacted in the presence of 酉文. The acid to be used can be used without particular limitation as long as it is used for the acid used in the general S reaction. For example, an inorganic acid such as sulfuric acid or hydrochloric acid, an organic rheutic acid such as p-toluenesulfonic acid or methanesulfonic acid or camphoric acid, an acid-type particle exchange resin, or a fluorite-based ether 5 product. Water-soluble Lewis acid such as acid or steel lanthanide triflate. These acids may be used singly or in combination of two or more kinds. The lower limit of the amount of use of the acid is 0.1 mol 〇 / ° or more with respect to the isosorbide of the substrate, and is preferably 5% by mol or more. On the other hand, the upper limit is not limited to '20 mol or less, and suitably 10 mol or less. When the amount of acid catalyst is too small, 'the reaction proceeds slowly or stops, so it is not suitable. 'When too much, when there is too much, the residual problem of the product coloring is caused, and the generation of the Michael adduct is not caused. The tendency of a suitable side reaction. The reaction can be carried out in either a solvent-based or solvent-free system. However, it is preferred to use a solvent system from the viewpoint of the formation of the product and the treatment in the step. The case of using a bromine is not particularly limited, and an aromatic hydrocarbon solvent such as toluene or diphenyl 14 201118066 benzene, an aliphatic hydrocarbon solvent such as hexane or heptane, diethyl ether, tetrapyran, and monoethylene may be suitably used. An ether-based solvent such as an alcohol diterpenoid or diethylene glycol dimethyl ether; a halogen-based solvent such as di-methane, tri-methane or tetra-carbonized carbon. These solvents may be used singly or in combination with any of a plurality of solvents. In the case of using a solvent, the lower limit of the concentration of the isosorbide or the like of the raw material is usually 1% or more, suitably 10% or more, and the upper limit is not particularly limited, and is usually 80% or less, and suitably 70% or less. The reaction is usually carried out at a temperature higher than the boiling point of the solvent to be used, and the reaction is carried out while distilling off the water formed. The reaction time is arbitrarily selected, and the reaction end point can be confirmed by measuring the amount of water generated and the acid value in the system. The lower limit of the reaction time is usually 30 minutes or more, and suitably 60 minutes or more, and the upper limit is not particularly limited, and is usually 20 hours or shorter, and suitably 10 hours or shorter. <Refining method> The purification of the compound represented by the general formula (1) produced by the above reaction can be carried out by a method which is not particularly limited. For example, a steaming method, a recrystallization method, an extraction washing method, a sorption treatment method, and the like. In the case of performing distillation, the form may be arbitrarily selected from single distillation, precision distillation, thin film distillation, molecular distillation, and the like. <Method for Preserving (Meth)Acrylate Monomer> Since the (fluorenyl) acrylate monomer of the present invention has polymerizability, it is desirable to store it in a cool dark place. Further, in order to prevent polymerization, the above-mentioned amount of the above polymerization inhibitor may be used for storage. <Polymer, polymerizable resin composition> As an example of the application of the (fluorenyl) acrylate monomer of the present invention, the following 15 201118066 will be used as a polymer production condition for a raw material for a coating resin composition. Wait for explanation. / (4) = (4) (10) In the case of the fat composition, in the (meth) propylene-texture of the present invention, the oligomer polymer component of the mixed urethane acetoacetate or the like is polymerized. Starting from a starting agent, a solvent, and the like. If the content of the fluorene-based monomer is small, the physical properties such as the light sensitivity of the composition, the point production, and the hardness of the polymer may be insufficiently exhibited. Further, the polymerizable tree is hardened. The polymerization can be carried out by a generally known method, and is not particularly limited. For example, a method of performing polymerization in the presence of a radical initiator = or a method of photopolymerization in the presence of a photopolymerization initiator, an anion polymerization method, or the like can be employed. As the radical polymerization initiator, for example, benzammonium peroxide, methylcyclohexane oxide, cumene hydroperoxide, dicumyl peroxide, di-tert-butyl peroxide, t-butyl group can be used. Organic peroxides such as benzoic acid benzoic acid vinegar, diisopropyl peroxycarbonate, tert-butyl peroxy isopropyl carbonate, and 2,2'-azobisisobutyronitrile (AIBN) Nitrogen compounds. Among the polymerization initiators of the activation energy line, for example, an aromatic compound such as a diphenyl sulfonate, an anthracene, an α-"naphthalene or the like, a diphenyl sulfide or a thioaminocarboxylic acid can be used. An anthracene compound such as a salt. The polymerization initiator which uses an activation energy line such as ultraviolet rays may, for example, be 仏, phenethyl benzoin bond, p-cyclohexylbenzophenone, 2,2-dimethoxy-U-diphenyl Burning small, xanthone, ketone, benzophenone m, anthracene, triphenylamine, decantyl, 3-methylacetophenone, 4-chlorodiphenyl-, dimethoxydiphenyl 'benzoin ethyl ether, ketone, 4,4'-diaminodiphenyl ketone, benzoin propyl ether 16 201118066 Benzil dimethyl ketal, 1_(4_isopropylphenyl) 2 ketone - 2-mercaptopropan-1-one, 2-hydroxy-2-mercaptophenylpropanone, thioxanthone, diethylthioxanthone, 2-isopropylcarbone, 2· Gas sold: ketone, 2_mercapto-1-[4-(mercaptothio)phenyl]_2_morpholinylpropane 丨嗣, 2_benzyl-2-dimethylamine-1-(4 -morpholine phenyl)_butyl ketone ^^ hydroxyethoxy)phenyl-(2-pyridyl-2-propyl) ketone, (2,4,6-tridecyl) Diphenyl phosphine oxide, bis(2,6-dimethoxybenzhydrazide)-2,4,4-trimethylpentyl oxidized scale, oligomeric (2-hydroxy-2-indenyl) 1-(4-(1-decylvinyl)phenyl)propanone), etc. A polymerization initiator and a radical initiator which activate the energy ray can also be used as needed. Commercially available products such as Ciba Specialty Chemicals Co., Ltd., trade names: IRGACURE 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, DAROCURE 1116, 1173 Trade name of BASF Corporation: Lucirin ΤΡΟ, UCB company name: Uvecryl P36, Fratelli Lamberti Company name: Esacure KIP150, KIP 65LT, KIP l〇〇F, KT37, KT55, KT046, KIP75/B, etc. The amount of the polymerization initiator or the polymerization initiator using the activation energy line may be selected in accordance with a known polymerization reaction. For example, a polymerization initiator using an activation energy line is compared with the present invention represented by the general formula (1). 100 parts by mass of the compound or the polymerizable composition thereof is usually suitably used in an amount of 0.001 to 20 parts by mass, suitably 0.01 to 5 parts by mass. In addition, the radical polymerization initiator is usually suitably used in an amount of 0.0001 to 10 parts by mass, suitably 0.001 to 5 parts by mass based on 100 parts by mass of the compound of the present invention represented by the general formula (1) or the polymerizable composition. Share. The lower limit of the reaction temperature is usually 0 ° C, suitably 17 201118066 1 〇 c > c, and the other - + 〜 upper limit is 200 ° C, suitably loot:. The present invention will be described in detail by way of examples, but the present invention is not intended to be limited by the following examples, and is not limited by the following examples. Further, the conditions of the gas chromatography and the liquid chromatography are as follows. Analysis of the Purity of Wood by Gas Chromatography

• C-R9A CHROMATOPAC DB-1 〇 ο ^ by Shimadzu Corporation

υ·25π!ηιφ, 15m, 〇·25μηι Current-carrying gas: 氦 Detector: FID

Injection inlet temperature: 280 °C 笞column temperature: initial temperature 15 〇 it (for 2 minutes) - heating rate C / for the final temperature - 280 ° C (for 1 〇 minutes) Injection amount: 〇.5μ [ < Inductive liquid chromatography (hereinafter omitted as HPLC) analysis conditions > Column: GL Sciences inertsil ODS-2

Mobile phase: acetonitrile: water = 7:3 Flow rate: 0.6 mL / min Detector: UV, RI Column temperature: 40 ° C Injection volume: 50 μΙ ^ (0·5% acetonitrile solution) h General formula (1) Synthesis of a cyclic (meth) acrylate compound [Example 1] (Synthesis of isosorbide diacrylate) 201118066 Isosorbide 146S (lm〇l) and 144 g of acrylic acid (2 mol) were mixed in a 1 L four-necked flask. ), p-benzoquinone 0.15g (0.0014mo1), tortenoic acid 1.5g (0.015mol), abenzine 7〇〇g, while introducing air, heated to 120 ° C in an oil bath, mixing 1 hour . The steaming reaction is carried out along with the water side where the reaction occurs. After completion of the reaction, the mixture was cooled to room temperature, and washed with water of 1.0 mL of distilled water to remove the catalyst. After the addition of 0·025 § hydroquinone, the solvent was removed under reduced pressure to obtain a pale yellow viscous liquid. The substance was analyzed by1H-NMR, HPLC, and gas chromatography-mass spectrometry (GC-MS) to confirm that it was isosorbide diacrylate. (Yield of isosorbide standard material: 87.4% 'GC purity (area ratio) = 95% &lt;, HPLC purity = 97%) <isosorbide diacrylate> (1H-NMR (400 MHz) 'CDC13, The unit is ppm); 6.4 (2 Η), 6_2 (2 Η), 5.8 (2 Η), 4.6 (2H), 3_9 to 4·2 (6 Η) [Example 2] except that the acrylic acid of Example 1 was replaced with hydrazine In addition to the acrylic acid, the reaction was carried out in the same manner to obtain a pale yellow viscous liquid. The substance was analyzed by1H-NMR, HPLC, and gas chromatography-mass spectrometry to find that it was isosorbide dimercapto acrylate. (Yield of isosorbide standard of raw material: 85.4% 'GC purity (area ratio) = 93% &lt; 'HPLC purity = 96%) <isosorbide dimercapto acrylate> (lH-NMR (400 MHz) 'CDC13 , unit is ppm); 6.4 (2H), 5.8 (2H), 4.6 (2H), 3.9~4·2 (6Η), 1·9 (6Η) [Example 3] (Synthesis of isosorbide diacrylate) 19 201118066 In a 2L four-necked flask, 146 g (1 mol) of isosorbide, 181.6 g (2 mol) of acrylonitrile chloride, and 15 g of p-benzoquinone (14 mol) of terpene were mixed. Cool to 5 in an ice bath. (:, while confirming the heat of reaction, 202.2 g (2 mol) of triethylamine was slowly dropped by a dropping funnel. After the dropping was carried out, the mixture was stirred for 5 hours under ice bath conditions, and then returned to room temperature and further. The reaction was terminated by stirring for 3 hours. After the completion of the reaction, the mixture was returned to room temperature and washed with 100 ml of distilled water, 0.025 g of hydroquinone was added, and the solvent was removed under reduced pressure to obtain a pale yellow viscous liquid β. The results of 1H-NMR, HPLC, and gas chromatography-mass spectrometry confirmed that it was isosorbide diacrylate. (The yield of the isosorbide standard was 90.4%, and the GC purity (area ratio) was 98°. &lt;, HPLC purity = 99%) &lt;isosorbide diacrylate&gt; (1H-NMR (400 MHz), CDC13, in ppm); 6.4 (2 Η), 6.2 (2 Η), 5.8 (2 Η) 4·6(2Η) '3.9~4·2(6Η) [Example 4] In addition to replacing the propylene helium gas of Example 3 with mercaptopropene fluorene chloride, the reaction was carried out in the same manner to obtain a pale yellow viscous liquid. The substance was clearly analyzed as isosorbide dimethyl propylene by 1H-NMR, HPLC, gas chromatography-mass spectrometry. Ester. (The yield of the isosorbide standard of the raw material was 88.4%, GC purity (area ratio) = 97% &lt;, HPLC purity = 98%) &lt;isosorbide dimercapto acrylate&gt; (lH-NMR (400MHz) 'CDC13' is in ppm); 6·4(2Η), 5·8(2Η), 4.6(2H) ' 3_9~4·2(6Η), 20 201118066 1·9(6Η) [Example 5] (Synthesis of isosorbide diacrylate) In a 2L four-necked flask, 146 g (1 mol) of isosorbide, 252 g (2 mol) of acrylic anhydride, p-benzoquinone. 15 g (0.0014 mol), and phenylbenzene 700 g were mixed. After cooling to 5 ° C in an ice bath, 202.2 g (2 mol) of triethylamine was slowly dripped with a dropping funnel while the reaction was completed. After the completion of the dropping, the mixture was stirred for 5 hours under ice bath conditions. After that, the mixture was further stirred for 3 hours at room temperature to complete the reaction. After the completion of the reaction, water was washed with 10 ml of distilled water, 0.025 g of hydroquinone was added, and the solvent was removed under reduced pressure to obtain a pale yellow color. The viscous liquid was analyzed by 1H-NMR, HPLC, and gas chromatography-mass spectrometry, and it was confirmed that it was isoamyl alcohol-acrylic acid vinegar. (The yield of the raw material isoamyl alcohol base was 89.4%. , GC pure Degree (area ratio, HpLC purity = 98%) <isosorbide diacrylate> (1H-NMR (4〇OMHz), CDC13, in ppm); 6·4 (2Η), 6·2 (2Η) , 5.8 (2Η), 4·6 (2Η), 3 9 to 4 2 (6H) [Example 6] (Synthesis of isosorbide dimercapto acrylate) except that the acrylic acid anhydride of Example 5 was replaced with a mercapto group In addition to the acrylic needle, the reaction was carried out in the same manner to obtain a pale yellow sticky liquid. After the completion of the reaction, the mixture was washed with water, and the bismuth benzene was added thereto, and the solvent was removed under reduced pressure to obtain a yellow viscous liquid. This material was clearly found to be isosorbide dimethacrylate by m-NMR, HPLC, and gas chromatography-mass spectrometry. (Materials Isoyama 21 201118066 Pearol benchmark yield 88.1%, 〇 (: purity (area ratio) = 96.1% &lt;, 1^1^ purity = 97.5%) <isosorbide dimethacrylate> 1H-NMR (400MHz), CDC13, in ppm); 6·4(2Η), 5·8(2Η), 4.6(2H), 3.9~4·2(6Η), 1.9(6Η) [Example 7 (Synthesis of isosorbide 15 Ε〇 adduct diacrylate) 146 parts of isosorbide and 1 part of caustic soda were placed in an autoclave and replaced with nitrogen. Under stirring, the temperature was adjusted to 130 ° C and uniformly The dispersion was carried out, and 260 parts of ethylene oxide (EO) was continuously introduced at 130 ° C without causing the internal pressure of the hot pressure dad to exceed 〇 3 MPa. The mixture was aged for 2 hours at the same temperature until the pressure was balanced to obtain a difference. The sorbitol 6EO adduct. The number average molecular weight of the target was 344, and the average addition mole number of EO was 4.5. Into a 1 L four-necked flask, the above isosorbide 15EO adduct 806 g (1 mol) and acrylic acid were mixed. 144g (2mol), p-benzoquinone 0.475g (0.0044mol), methanesulfonic acid 4.75g (0_044mol), toluene 2216g, while introducing air, heated in an oil bath to 12 ° ° C 'mixed for 15 hours ° while steaming Accompanying reaction The reaction was carried out at the water edge where the line appeared. After the reaction was completed, it was cooled to room temperature. After washing with 150 ml of steaming water, the catalyst was removed to remove the catalyst. After the addition of 〇.〇66g to benzodiazepines, the solvent was removed under reduced pressure. A pale yellow copper-colored liquid was obtained. The material was analyzed by 1H-NMR, HPLC, gas chromatography-mass spectrometry, and it was clearly identified as isosorbide diacrylic acid vinegar. Rate 82.4%, GC purity (area ratio) = 94% &lt;, HPLC purity = 95%) &lt;isosorbide diacrylate&gt; (1H-NMR (400 MHz), CDC13, single 22 201118066 bit ppm) 6.4(2H), 6.2(2H), 5.8(2H), 4·6(2Η), 4·3(4Η), 3.5~4.0(62H) [Example 8] (isosorbide 6e 〇 adduct) Synthesis of diacrylate) In an autoclave, 146 parts of 'isosaccharide sodium' of 1 part of isosorbide was placed and replaced with nitrogen. Under stirring, the temperature was adjusted to 130 ° C and uniformly dispersed. 700 parts of ethylene oxide (E0) was continuously introduced at 130 ° C under a pressure of more than 0.3 MPa, and matured at the same temperature until pressure equilibrium for 4 hours to obtain isosorbide 15EO. The number average molecular weight of the target was 832, and the average addition mole number of EO was 15.6. In the 1 L four-necked flask, 410 g (lmol) of the above isosorbide 6EO adduct, 144 g (2 mol) of acrylic acid, and p-benzoquinone were mixed. 0.283 g (0.0026 mol), 2.83 g (0.026 mol) of methanesulfonic acid, and 1293 g of toluene were heated to 120 ° C in an oil bath while introducing air, and stirred for 13 hours. The reaction is carried out while distilling with water which occurs as the reaction proceeds. After completion of the reaction, the mixture was cooled to room temperature, and washed with water (120 ml) to remove the catalyst. Thereafter, 38 g of hydroquinone was added, and desolvation was carried out under reduced pressure to obtain a pale yellow viscous liquid. The substance was analyzed by1H-NMR, HPLC, and gas chromatography-mass spectrometry to find that it was isosorbide diacrylate. (Yield of isosorbide standard material: 84.4%, GC purity (area ratio) = 96% &lt;, HPLC purity = 96%) <isosorbide diacrylate> (lH-NMR (400 MHz) 'CDC13, unit MPa (ppm); 6.2 (2Η), 6.2 (2Η), 5·8 (2Η), 4.6(2H) '4.3(4H) ' 3.5 ~4·0(26Η) 2. Isosorbide di(meth)acrylic acid Evaluation of the physical properties of the esters 23 201118066 For the isosorbide diacrylate obtained by the above-mentioned Example 1, the KAYARAD DPHA of the polyfunctional monomer and the same bifunctional HDDA were used as the comparison object, and the resin composition and the resin composition were evaluated as follows. Its physical properties of the hardened film. The preparation method and measurement of the sample. The evaluation method is as follows. The results are shown in Table 1. [Example 9] 5 parts of 1-hydroxy-cyclohexyl-benzophenone (commercial sIRGACURE 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) was added to 1 part of the isosorbide diacrylate obtained in Example 1. This product was used as a resin composition. [Comparative Example 1] 5 parts of 1-hydroxyl was added to 1 part of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA, manufactured by Sakamoto Chemical Co., Ltd.) -cyclohexyl-benzophenone (trade name: irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.), and this product was used as a resin composition. [Comparative Example 2] To a solution of 1,6-hexanediol diacrylate vinegar (trade name: New Frontier HDDA, manufactured by Dai-ichi Kogyo Co., Ltd.), 5 parts of 1-hydroxy-cyclohexyl- phenyl ketone (product) The name IRGACURE 184, manufactured by Ciba Specialty Chemicals Co., Ltd., was used as a resin composition. In the case of the hardened film for evaluation, the resin composition obtained in Example 9 and Comparative Examples 1 and 2 was applied to a glass substrate by a film thickness ΙΟΟ μηη using a bar coater. A belt-driven UV hardening device equipped with a metal halide lamp is hardened with a cumulative illumination of 200 mj/cm2. 24 201118066 &lt;Viscosity&gt; The viscosity was measured by a cone-and-plate type rotary viscometer (E-type viscometer manufactured by Toki Sangyo Co., Ltd.) connected to a constant temperature bath and a circulation pump. &lt;Refractive index&gt; The film was applied to a glass substrate at a film thickness of 2 μm by a bar coater, and cured under the same conditions as the adhesion, and was measured by a prism coupler (Model: 2010, manufactured by Metricon Co., Ltd.). Refractive index. &lt;Volume Shrinkage Rate&gt; The specific gravity of the test sample before and after curing was measured based on HS K0061-1992, and the volume shrinkage ratio was measured by the following formula. Volume shrinkage ratio (%) = {(specific gravity after hardening - specific gravity before hardening) / specific gravity after hardening} xl 〇〇 &lt;contact angle &gt; Measurement by a droplet method. Directly read the height of the apex and the half of the water drop' using 0 = 2arctan(h/a) to find the contact angle. &lt;Sturability&gt; The film thickness of 1 was applied to a glass substrate by a bar coater, and it was shielded by a stage meter (25th order, manufactured by Riston Co., Ltd.), and was manufactured by USHIO under the condition of blocking air. The parallel light type exposure machine (sx_UID5〇1h UVQ) was hardened with a cumulative illuminance of 50 mj, and the order of the surface dryness was recorded. &lt;Pencil Hardness&gt; Each of the resin compositions was cured with a cumulative illuminance of 4 〇〇mj/cm2 using glass, PET, ABS, PC, or acrylic resin as a substrate by a belt-driven UV curing device equipped with a metal halide lamp, following jIS K56 〇〇_5_4 Determines the film hardness on the substrates of these 25 201118066. &lt;Adhesiveness&gt; Each of the resin compositions was cured with a cumulative illuminance of 400 mj/cm2 using ABS, PC, or acrylic resin as a substrate by JIS-K5400 using a belt-driven uv hardening device equipped with a metal halide lamp. In the number test, the residual number is used as the adhesion. &lt;Corbrid wearability&gt; A TABER abrasion test was carried out by applying a film thickness of 20 μm on a PET substrate by a bar coater and forming a hardened film under the same conditions as the adhesion. The CS-10F abrasion wheel was used at a load of 500 g, and the haze at the specified number of revolutions was measured by a haze meter (SUGA-made HGM type). &lt;Stain resistance&gt; The film was coated on a PET substrate at a film thickness of 1 μm by a spin coater, and a cured film was formed under the same conditions as the adhesion. The oily standard, the hair dye, and the shoe polish were applied to the hardened film and allowed to stand for 18 hours, and the appearance when rubbed with the cotton cotton was visually observed, and evaluated by the following criteria. 〇··No coloring, △: Slightly colored, χ: Coloring intensity &lt;Chemical resistance&gt; The film was formed under the same conditions as the contamination, and the hypo-sulfite, sodium hydroxide, and the like were dropped on the test film. A commercial bleaching agent composed of a surfactant (alkylamine oxide) or the like was allowed to stand in a petri dish for 18 hours. The film was wiped with a thin paper and visually observed for changes in the film, and evaluated by the following criteria. 〇: There is no abnormality in the cured film, △: The gloss is slightly changed, χ: The obvious abnormality such as whitening, cracking, floating, etc. of the cured film can be seen. 26 201118066 &lt;Water resistance&gt; The same as the pollution test The conditions for forming the phase, _ tap water, and the appearance when visually rubbed after 18 hours were evaluated by the following criteria. 7 ' 〇: There is no abnormality in the cured film. △: The gloss is slightly changed. X: The cured film has obvious abnormalities such as whitening, cracking, floating, etc. &lt;acid resistance&gt; The film was formed under the conditions, and a drop of 0.1 mol/L aqueous hydrochloric acid solution was dropped on the test film and allowed to stand in the culture dish for 18 hours. Wipe with a thin paper and visually observe whether there is a change in the thin enamel. The 帛 is evaluated on the same basis as the water resistance. &lt;Alkali resistance&gt; A film was formed under the same conditions as for the contamination test, and a 2% aqueous sodium hydroxide solution was dropped on the test film, and allowed to stand in a petri dish for 18 hours. The film was rubbed with 4 papers, and the film was visually observed for change, and evaluated on the same basis as the water resistance. &lt;Transparency&gt; The film was coated with a film thickness (9) (7) on a glass substrate by a bar coater, and cured under the same conditions as those of the resultant, and the haze was measured by a haze meter, and the measured value was used as the transparency. &lt;Curlability&gt; It was cured by a bar coater at a coating thickness of 20 μm on a PET film having a thickness of 150 μm under the same conditions as the adhesion. The heights of the four corners of the film were measured, and the average value thereof was used as the curling property. 27 201118066 [Table i] Example 9 Comparative Example 1 Comparative Example 2 Monomeric isosorbide diacrylate DPHA HDDA 25 ° C Viscosity (mPa.s) 350 5600 8 Refractive index (after hardening) 589 nm 1.5218 1.5255 1.5063 Volume shrinkage (%) 8.5 11.8 13.2 Contact angle (°c) Water 0.2s 60.7 38.6 53.5 5s 58.7 33.8 53.2 0.2s-5s 2 4.8 0.3 Hardenability (stage table) 13 2 5 Pencil hardness glass 4H 5H Η PET 2H 3H Η ABS B HB 2Β PC FF HB Acrylic acid 5H 6H 3H Adhesion ABS 100/100 100/100 100/100 PC 100/100 100/100 100/100 Acrylic acid 100/100 100/100 0/100 Abrasion resistance At 100 rpm 1.3 1.3 6 300 rpm 4.9 4.7 17.6 For contaminated marking liquid 〇〇〇 hair dye 〇〇 Δ Shoe polish 〇〇〇 药品 药品 药品 药品 〇〇〇 〇〇〇 才 才 才 才 才 才 才 才 才 才 才 才 才〇〇〇Transparent appearance Transparent transparent haze 0 0 0.5 Small curl (0mm large (20mm large (5mm) As shown in Table 1, isosorbide diacrylate is a bifunctional monomer, and it is displayed with polyfunctional The monomeric DPHA is roughly equivalent in physical properties, in addition, Low viscosity, high sensitivity, and excellent properties of low hardness of the hardened film. 3. Preparation of a polymerizable resin composition and physical properties of the cured film. The isosorbide diacrylate obtained in Example 1 was used, and Comparing the polyfunctional monomer DPHA and the same bifunctional monomer HDDA of the target of 201120116, the physical properties of the resin composition and the hardened film which are compositionally synthesized with the ethyl phthalate acrylate as described below, and the above-mentioned implementation The measurement or evaluation was carried out in the same manner as in Example 9. [Example 10] 5 parts of isosorbide diacrylate obtained by the above Example 1 and 50 parts of New Frontier R-1204 (ethyl urethane acrylate) were mixed. 5 parts of 1-hydroxy-cyclohexyl-benzophenone (trade name: IRGACURE 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) was prepared to obtain a polymerizable resin composition. [Example 11] The same resin composition was prepared by replacing the amine phthalate acrylate resin of Example 10 with New Frontier R-1302 (urethane acrylate resin, manufactured by Dai-Il Pharmaceutical Co., Ltd.). [Comparative Example 3] Instead of the isosorbide diacrylate of Example 10, a mixture of dipentaerythritol pentapropionate or dipentaerythritol hexaacrylate (trade name KAYARAD DPHA, Nippon Chemical Co., Ltd.) was used. The company's composition was prepared in the same manner. [Comparative Example 4] The same resin composition was prepared by using 1,6-hexanediol diacrylate (trade name: New Frontier HDDA, manufactured by Dai-ichi Kogyo Co., Ltd.) in place of the isosorbide diacrylate of Example 10. [Comparative Example 5] In Example 10, no monomer was added, but 100 parts of New 29 201118066 were mixed.

Frontier R-1204 (urethane acrylate resin, manufactured by Dai-Il Pharmaceutical Co., Ltd.), 5 parts of 1-hydroxy-cyclohexyl-benzophenone (trade name: IRGACURE 184, manufactured by Ciba Specialty Chemicals Co., Ltd.), and obtained polymerization. Resin composition. [Comparative Example 6] The isosorbide di(indenyl) acrylate of the alternative example 11 was used as a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacetic acid vinegar (trade name KAYARAD DPilA, Japan). The same resin composition was prepared by Chemicals Co., Ltd.). [Comparative Example 7] The same was prepared for the isosorbide di(meth)acrylate of the eleventh embodiment using 1,6-hexanediol diacrylic acid (trade name: New Frontier HDDA, manufactured by Dai-ichi Kogyo Co., Ltd.). Resin composition. [Comparative Example 8] In Example 11, no monomer was added, but 1 part of New Frontier Rn 2 (amino phthalate acrylate resin, manufactured by Dai-Il Pharmaceutical Co., Ltd.) was mixed, 5 parts 1 -Hydroxy-cyclohexyl-benzophenone (commercial gIRGACURE 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) to obtain a polymerizable resin composition. In the above-mentioned measurement and evaluation methods, the hardened film for evaluation was subjected to the filming of the polymerizable resin composition obtained in Example 1A, U, and Comparative Examples 3 to 8 by a bar coater unless otherwise specified. The thick 丨〇〇μηι was applied onto a glass substrate, and was obtained by hardening a illuminance of 2 〇〇mj/cm 2 by using a belt-driven sUV hardening device equipped with a metal halide lamp. 30 201118066 [(Νΐ1Comparative example 8 I R-1302 | t P 〇 inch co cd 〇- η inch IT) i/Ί Ο 00 m | 70.8 | (N 〇XX CQ u- X (N 100/100 1 100 /100 70/100 (N (N 〇X 〇〇〇〇〇 Transparent 1 〇 EE 1 Comparative Example 6 1 Comparative Example 7 HDDA 1 170 1 46.3 inch 00 00 | 59.2 I 59.4 (N 〇1 (N 1 HB X CQ _HB_ DC CM | 100/100 | ! loo/ioo 1 100/100 ^T) 23.3 1 〇X 〇〇〇〇〇Transparent 1 〇ε (Ν /&gt; DPHA 1 17000 1 34.9 (N 1 166 00 | 54.6 I 54.7 〇—X m X (N 1 hb I U. X inch 100/100 100/100 100/100 19.8 I 〇0 〇〇〇〇〇transparent 1 〇ε Ε (Ν -Β- ϊ isosorbide diacrylate 1 3800 1 69.3 ^Τ) inch 00 (N oo | 49.6 ί 1 49.6 I 〇Ο XX CQ X IX X 100/100 100/100 100/100 Γ- ΓΟ 20.6 I 〇&lt; 〇〇〇〇〇transparent| 〇 ε ε ✓ |Comparative Example 4 |Comparative Example 5 I R-1204 1 Ρ ο C/5 cd Q- 00 ΓΊ 1 19.2 in 00 Ρ; 1 70.4 | 71.1 J 〇 1 inch CQ ^T) PQ inch CQ inch PQ ΓΛ QQ inch 0/100 100/100 100/100 CN 40.4 IXX 〇〇〇〇〇transparent 丨〇ε Ε CN HDDA 1 430 1 24. 4 &lt;N 2 CN m 00 5丄7一 I | 57.7 〇CQ ΓΊ CQ X CQ m DQ QQ 100/100 100/100 100/100 00 (N 〇X 〇〇〇〇〇Transparent | 〇Ε Ε (Ν丨Comparative example 3 DPHA 1 34000 1 29.3 Ό OS OS 〇 I I 56.7 I 〇 — XX HB I U- X (N 100/100 100/100 100/100 inch (N 〇&lt;1 〇〇〇〇〇 transparent 〇£ Ε ο I Example 10 il© gas 丨 1 7700 卜 inch vd (N 〇s I 58.9 II 58.2 I 〇Ο IX X CO | HB IX 100/100 100/100 100/100 22,6 I 〇 〇〇〇〇〇Transparent | 〇Ε Ε |Amino phthalate acrylate monomer/*&quot;N in d CX E -M3 ΓίΓ) &lt;N P3 0- S s-✓ 娥-φ- 5 跻\ιψί NPH /-s 客济塄韬I 0.2s C/5 yn I 0.2s-5s /—N Ϊ w /--s Nw^ αα&gt;Goods&lt;rr | PET II ABS IU cu | Acrylic II ABS I u CL Acrylic loo turn 1 ! 300 rpm | Marking liquid | Hair dye 1 Shoe polish | Only chemical water resistance and acid resistance Appearance 1 Haze 1 Curl contact angle (°c) Water pencil hardness tightness Abrasion fiscal pollution transparency 31 201118066 From the results of Table 2 , Isosorbide diacrylate than, the viscosity of the amine south viscosity urethane acrylate of DPHA greatly reduced, while significantly improving hardenability, curling properties, other physical properties. Further, it was found that the hardness of the hardened film of HDDA was significantly improved as compared with HDDA. Industrial Applicability The cyclic (meth) acrylate compound of the present invention and the cured product obtained by curing the polymerizable resin composition containing the compound have high hardness, low curling property, and excellent hardenability. Therefore, it can be suitably applied to a coating application such as a bar coater, an ink composition for inkjet printing, or a resist composition such as a dry film resist, a color resist, or a black resist. . BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an NMR chart of isosorbide diacrylate obtained in Example 1. Fig. 2 is an NMR chart of the isosorbide 5E hydrazine adduct dipropylene decyl ester obtained in Example 7. Fig. 3 is an NMR chart of the isosorbide 6E hydrazine adduct dipropylene acrylate obtained in Example 8. I main component symbol description] (none) 32

Claims (1)

201118066 VII. Patent Application Range: L A bismuth (fluorenyl) acrylate compound characterized by the general formula (1): [Chemical Formula 1] General Formula (1): In the general formula (1), R1 represents a hydrogen atom or a (meth)acrylinyl group, and at least one is a (fluorenyl)propenyl group; A represents a C 2 to 4 alkyl group; η represents 〇~ 3 〇 value. 2. A cyclic (meth) acrylate compound according to the first aspect of the patent application, which is in the general formula (1), -30. 3. The method for producing a cyclic (fluorenyl) acrylate compound according to claim 1 or 2, characterized by comprising: reacting (meth)acrylic acid or (mercapto)acrylic anhydride to cause a step of acrylated isosorbide or isosorbide alkylene oxide adduct; and any of the following steps: using isoester exchange with (mercapto) acrylate to make isosorbide or isosorbide The alcohol alkylene oxide adduct is subjected to a (hydrazino) acrylated step; or in the presence of a dehydrating condensing agent or an acid, the (mercapto)acrylic anhydride is inverted 33 201118066 to make an isosorbide or isosorbide ring The oxane adduct is subjected to any of the steps of acrylate. 34