TWI287021B - Fumarate derivative and method for producing the same - Google Patents

Abstract

This invention is to provide a polymerizable composition having excellent curability and surface hardness, and a cured product thereof. A novel fumarate derivative having two or more fumarate groups within one molecule and ensuring high copolymerizability with the terminal alkenyloxy group, a method for producing the derivative, a polymerizable composition containing the derivative, and a cured product thereof are provided.

Description

1287021 A7 _ B7 V. DESCRIPTION OF THE INVENTION (Technical Field) The present invention relates to a polymer which has excellent free polymerizability, can withstand light or heat, and can be used as a crosslinking agent for various polymers, in particular A novel fumarate which can be used in coatings, adhesives, encapsulating materials, etc., in the technical field of hardening under air, a method for producing the same, a polymerizable composition containing the same, and hardening thereof Things and so on. [Technical Background] Conventionally, a polyfunctional compound having a double bond is widely used in various technical fields as a raw material of a polymerizable composition. The hardening method of such a polymerizable composition, for example, it is carried out by light or heat to carry out free polymerization, which is currently the mainstream method. Generally, as a polymerizable composition for high-speed photopolymerization, for example, a propylene-based compound or an unsaturated carboxylic acid ester-based compound is generally used. However, the above compounds still have various problems as described below. The crosslinking monomer of the propylene compound is widely used in UV hardening materials such as various coatings and coating materials because it can be hardened in a short period of time due to UV curing, but it is highly irritating to the skin. Sex, or it is very easy to block hardening due to oxygen, etc., and it is very easy to produce viscosity and other disadvantages when forming a film. Further, as the unsaturated carboxylic acid ester compound, for example, a dialkyl ester such as fumaric acid or maleic acid is known, and when it is used alone, it lacks free polymerizability, even when it is copolymerized with other resins. The strength of the hardened material produced is insufficient due to insufficient crosslinking. Moreover, when the unsaturated polyacetate is used alone, its molecular weight is too large, and the homopolymerization is not good. Therefore, the styrene monomer is generally used as the paper scale for the Chinese National Standard (CNS) A4 specification (210X 297 mm), and the batch is coated. -- (Please read the note on the back and fill in the book). Printed by the Intellectual Property Office of the Ministry of Economic Affairs. Employees' Consumer Cooperatives Printed - Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1287021 A7 B7 V. Invention Description (2) The reactive diluent is used. However, since the styrene monomer often has an odor, many alternatives are sought from the viewpoint of work. In order to solve this problem, recently, vinyl ethers of alkene ethers have been attracting attention in non-acrylic compounds. The above vinyl ethers are usually used as a cationically polymerizable curable material, and the vinyl ether itself is hardly subjected to a separate free polymerization. However, the copolymerization of maleic acid esters and vinyl ethers has been reported by Red Tech North America, 1 67 (1992). Other copolymerization systems are disclosed, for example, in U.S. Patent No. 5,334, 455 and U.S. Patent No. 5,334,456, the disclosure of which are incorporated herein by reference. A reaction product obtained by polymerizing a polyfunctional vinyl ether and a maleic acid ester, and a composition of an unsaturated polyester and a vinyl ether is described in Japanese Patent No. 27059166. Further, it is known that a vinyl ether can be reacted with an acrylate in a manner of low copolymerizability. The above vinyl ether has a characteristic of being extremely high in adhesion to a substrate at the time of curing because of its low viscosity and excellent dilution ability. However, as described above, vinyl ether lacks free polymerizability when used alone, so that the combination with an unsaturated polyester or the like is incapable of exhibiting a cured product due to incomplete polymerization of the vinyl ether group. The physical properties, and the ratio of other polymerizable groups to vinyl ether groups still need to be adjusted, and the use amount must be limited. The method for solving such problems, for example, the special document No. 5 5-3 95 53 3 This paper scale applies to the Chinese National Standard (CNS) Α 4 specification (210Χ297 mm) I nn Install II """"- Line (please read the note on the back and then fill out this page) -5- Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed 1287021 Λ7 B7 V. Inventive Note (3) is described in the end with a vinyl ether group, internal A method for producing a compound having a maleic acid ester structure, which is disclosed in British Patent No. 1,1,881, the disclosure of which has an allyl ether group at the end, an internal compound, a maleate structure or a fumarate structure. Compound. However, these polymerizable compounds have only two end groups and one polymerizable group in the end, and the ruthenium has not reached a sufficient degree of crosslinking. In addition, since these vinyl ethers or allyl ethers have alkyl ethers, the refractive index of the cured product is extremely liable to be lowered or easily caused problems such as electrical properties and heat resistance, so that the use of the genus is not The extent to which the ingredients exert physical properties. [Invention] The present invention is an invention which is capable of solving the problems of the conventional free-polymerizable compound, which is easily hindered by oxygen during curing, and the hardness of the surface of the cured product is too low. Further, a novel fumarate having a sufficient crosslinking point, a method for producing the ester, a polymerizable composition containing the ester, a cured product thereof, and the like are provided. As a result of intensive research to solve the above problems, the present inventors have found that a chain such as a vinyl ether group, a propenyl ether group, and an allyl ether machine as a crosslinking agent of a free polymerizable resin or a resin is known. When the alkenyloxy group and the fumarate are placed in the same molecule, and the polyfunctionalization with a plurality of double bonds is carried out, a novel fumarate can be obtained, and the above problem can be solved and completed. this invention. That is, the present invention (I) is a fumarate containing a terminal group of the group represented by the formula (1) and a group represented by the formula (2) as a repeating unit (the paper scale is applicable to the Chinese national standard) (CNS) A4 size (210X297 mm) -----------Install ------ order---,--1 line (please read the notes on the back and fill out this page) -6 - 1287021 - V. Description of invention (4) Including case where the number of repeating units is one; Equation (1)

Rv〇, x〆 (2)

(In the formula (1), R1 is independently a formula (3) or a formula (4), and in the formula (1) or (2), X1 and '2 are each independently 2 to 6 hydroxyl groups. An organic residue derived from a polyol having 2 to 30 carbon atoms; X1, X2 may be bonded via an ester, or the formula (1) may be used as a terminal group to form a group having a branched structure Repeat unit) (3) -----------Society II (please read the notes on the back and fill out this page)

-Line - Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing (in the formula (3), R2, R3 are independent oxygen atoms or the number of carbon numbers 1 to 5) Equation (4) R4 Γ- Ί (Formula (4) Wherein R4 is a hydrogen atom or an alkyl group having 1 to 11 carbon atoms; and the present invention (II) is a fumarate containing a formula (1) The paper size is applicable to the Chinese National Standard (CNS) A4 specification. (210×297 mm) A7 B7 5 1287021 V. Inventive Note ( ) is not based on at least one terminal group, and the group represented by formula (2) and/or the group represented by formula (5) is used as a repeating unit;

Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing system (5) h' (in the formula (1), R1 is independent of the formula (3) or formula (4), again, formula (1), formula (2) or In the formula (5), each is an organic residue derived from a polyol having 2 to 6 carbon atoms of 2 to 30, wherein X1, X2 and X3 may be via an ester bond and/or an ether. Bonding, or making the formula (1) as a terminal group, such that the group represented by the formula (2) and/or the group represented by the formula (5) form a repeating unit having a branched structure) (3)

(In formula (3), r2 and r3 are independent hydrogen atoms or carbon numbers! The alkane of this paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -8- 1287021 at B7 V. Description of invention () 〇基) Equation (4) (Please read the back note and then fill out this page) H4~1~·_1 (In the formula (4), R4 is a hydrogen atom or an alkyl group having a carbon number of 1 to n) Further, the present invention (III) is a method for producing a fumarate of the invention (I) or the invention (Η). Further, the present invention (IV) is a polymerizable composition containing the fumarate of the present invention (: [) or the present invention (π). Further, the present invention (V) is a cured product obtained by hardening the polymerizable composition of the invention (IV). [Embodiment of the Invention] Hereinafter, the present invention will be described. First, the invention (I) will be described. The invention (〗 〖) is a fumarate containing a group represented by the formula (1) as a printing end group of at least one end of the Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative, and the formula (2) The base is used as a repeating unit (including the case where the number of repeating units is one); Formula (1) Formula (2) The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -9 - A7 B7 1287021 Five, invention description (7

(In the formula (1), R1 is independently a formula (3) or a formula (4), and in the formula (1) or (2), X and X2 are each independently 2 to 6 groups. An organic residue derived from a polyhydric alcohol having 2 to 30 carbon atoms; further, X1 and X2 may be bonded via an ester, or the formula (1) may be used as a terminal group to form a group represented by the formula (2) Repeat unit of branch structure) (3) (Please read the notes on the back and fill out this page)

(In the formula (3), R2 and R3 are each an independent hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Formula (4) R4-Printed by the Ministry of Economic Affairs Intellectual Property Office employee consumption cooperative (in the formula (4), R4 is A hydrogen atom or an alkyl group having 1 to 11 carbon atoms. The present invention (I) is a terminal group containing at least one group represented by the formula (1) as a terminal group, and at least one fumarate represented by the formula (2). A repeating unit of the structure; one of its representative examples, for example, a compound represented by the formula (1 2 ). -ο

ο R1,〇,X1,〇,r1 This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) -10- Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1287021 at B7 V. Invention description (8) (In the formula (12), e is an integer of 1 to 9) In the formula (1) of the present invention, R1 is any one of the formula (3) or the formula (4), and R2 and R3 in the formula (3) are Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. In the formula (3), at least one of R2 and R3 is a hydrogen atom or a methyl group, and the other is at least one selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, and an n-propyl group. Base and iso-propyl are preferred. More preferably, at least one of r2 and R3 is a hydrogen atom, and the other is a hydrogen atom or a methyl group. Most preferably, both R2 and R3 are hydrogen atoms. The gene with a carbon number of 4 or higher has a doubt that the polymerity is lowered, so it is not preferable. Further, in the formula (4), R4 is a hydrogen atom or an alkyl group having 1 to 11 carbon atoms. In the formula (4), from the viewpoint of free polymerizability, it is preferred that R4 is at least one selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, an η-propyl group and an iso-propyl group. More preferably, R4 is a hydrogen atom or a methyl group. Since an alkyl group having 4 or more carbon atoms has a problem of lowering the polymerizability, it is not preferable. Further, each of X^X2 is an organic residue derived from a polyol having from 2 to 30 carbon atoms having 2 to 6 hydroxyl groups. Specifically, the polyol, such as ethylene glycol, neopentyl glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6·hexane An alkanediol such as an alcohol or a decanediol, and a substituted alkanediol such as 1-phenylethylene glycol, 1,2-diphenylethylene glycol, or a polyalkylene glycol thereof, 1,1- Cyclohexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethanol, 1,2- Cyclohexane diol such as cyclohexane dimethanol, 1,3-cyclohexane dimethanol, 1,4·cyclohexane dimethanol, tricyclodecane dimethanol, bisphenol A, this paper scale is applicable to Chinese national standards (CNS) A4 specification (210X29*7 mm) " ' -11 - ------Install ------ order---.--1 line (please read the notes on the back and fill in Page 7 A7 B7 1287021 V. INSTRUCTIONS (9) Aromatic diols such as bisphenol F, bisphenol S, phenyldimethanol, and ethylene oxide additions of polyhydric alcohols, propylene oxide additions, rings Hexene oxide addenda, styrene oxide addenda, and the like. Further, triols such as trimethylolethane, trimethylolpropane and glycerin, pentaerythritol, diglycerin, di-trimethylene glycol, etc., dipentaerythritol, sorbitol, etc. The alcohol or the like, and the ethylene oxide addition of the polyol, the propylene oxide addition, the cyclohexene oxide addition, the styrene oxide addition or the like may be added at a degree which is not colloidal. Wherein X1 is exoethyl (-(CH2) 2 · ), 1,3-propenyl (-(CH2) 3-), 1,2-extended propyl (-CH2-CH-CH3)-) Alkyl groups having 2 to 4 carbon atoms, 1,1_cyclohexylene, 1,2-extended cyclohexyl, 1,3-cyclohexylene, 1,4-cyclohexylene, formula (·0:Η2-0 :6Η1()-€: 有机2-) The organic residue derived from 1,1-cyclohexanedimethanol, the organic residue derived from 1,2-cyclohexanedimethanol, 1,3 - an organic residue derived from cyclohexanedimethanol or an organic residue derived from 1,4-cyclohexanedimethanol, such as a ring alkyl group having 6 to 8 carbon atoms, to be hardened by polymerization The point of view is better. Further, from the viewpoint of increasing the refractive index of the cured product, the epoxide addition product of bisphenol hydrazine and bisphenol A, 1-phenyl-ethylene glycol, and 1,2·diphenyl diol have a phenyl group. Or a phenyl alkanediol is preferred. Further, the repeating unit of the formula (2) may be used as long as it is one or more, and more preferably 1 to 10 (in the formula (12), e is an integer of 1 to 9). When the number of repeating units is 10 or more, since the viscosity is remarkably improved, colloid formation tends to occur at the time of production, which is not preferable. When X1 is a trivalent or higher polyol organic residue, it can be used in the following paper size. It is applicable to China National Standard (CNS) A4 specification (210X297 mm) -----------Install II (please Read the notes on the back and fill out this page.) Customs Department of Intellectual Property, Intellectual Property Office, Staff and Consumer Cooperatives Printed -12- 1287021 A7 B7 V. Invention Description (1()) (1 3) The chain structure shown. Formula (1 3 )

(In the formula (13), f is an integer of 〇 to 4) When X2 is a trivalent or higher polyol organic residue, it may have a branched structure represented by the following formula (14). (14) ------^-- (Please read the notes on the back and fill out this page)

Printed by the Ministry of Economic Affairs, Intellectual Property Office, Employees' Cooperatives (in the formula (14), g is an integer from 0 to 4). R1 of the terminal polymerizable group of formula (1) will lack free polymerization when it exists alone. When the copolymer is copolymerized with a fumarate group for hardening, generally, the physical properties of the hardened material are superior when the molar ratio of the R1 group/fumarate group approaches 1. . Preferably, the molar ratio of the R1 group/fumarate group is in the range of 0.2 to 2, more preferably the molar ratio of the R1 group/fumarate group is in the range of 0.8 to 1.5. This paper scale is applicable to China National Standard (CNS) A4 specification (210X297 mm) -13- 1287021 Λ7 __________B7 V. Invention description (") R1 is the independent formula (3) or formula (4). Therefore, The structure of the formula (3) and the structure of the formula (4) are present in the present invention, and may be present in the fumarate molecule. The end of the structure of the formula (4) may be all or part of the formula (3). In the formula (3), R2 and R3 are preferably a hydrogen atom or a methyl group, and both of them are preferably a gas atom. Further, R4 in the formula (4) is a The base (the whole formula (4) is a propylene group) is more preferable. Hereinafter, the invention (II) will be described. The present invention (Π) is a reverse-butylic acid diester containing the formula (1) The substrate is at least one terminal group, and the group represented by the formula (2) and/or the group represented by the formula (5) is used as a repeating unit (including the case where the number of repeating units is one); the formula (1) 2) -----------Install ------Set------1 line (please read the notes on the back and fill in this page again) Ministry of Economic Affairs Intellectual Property Bureau staff consumption Cooperative printing a standard one, a country, a country I, a 5 foot piece, a paper

b

PCT 7 9 2 -14- 1287021 A7 B7 V. Description of invention (12) (Please read the note on the back and fill out this page) (In equation (1), R1 is independent (3) or (4) Further, in the formula (Ο, formula (2) or formula (5), X^X^X3 are each independently an organic group derived from a polyol having 2 to 6 carbon atoms and having 2 to 30 carbon atoms. a residue; wherein X1, X2, and X3 may be bonded via an ester bond and/or an ether, or the formula (1) may be used as a terminal group, and the group represented by the formula (2) and/or the formula (5) may be used. The base forms a repeating unit having a branched structure) (3)

(In the formula (3), R2 and R3 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Formula (4) R4—(In the formula (4), R4 is a hydrogen atom or a carbon number of 1 to 11. The alkyl ester of the present invention (II), which contains at least one group represented by the formula (1) as a terminal group, and a transbutene represented by the formula (2) as a repeating structure. The structure of the acid ester and/or the structure of the film represented by the formula (5). In the present invention (II), the structure of the terminal group represented by the formula (1) and the repeating unit represented by the formula (2) is the same as that shown in the invention (I). . Further, X3 contained in the formula (5) is the same as X2 in the formula (1), and X2 in the formula (2) is an organic residue derived from a polyol having 2 to 6 carbon atoms and having 2 to 30 carbon atoms. base. As the polyol of X3 or as a branch structure, it is applicable to the Chinese National Standard (CNS) A4 specification (2!〇><297 mm) -15- A7 B7 1287021 DESCRIPTION OF THE INVENTION (13) X1 in the formula (1) and X2 in the formula (2) are the same. One of the representative examples of the fumarate of the present invention is, for example, a compound represented by the formula (15). Formula (15)

(In the formula (15), h, i, and k are integers of 0 to 5, and j is an integer of 1 to 5 'n is an integer of 1 to 9, and h + i + k-1.) h, i, When any of j and k exceeds 5, the double bond concentration of the polymerizability is lowered, and the hardness of the hardenability or the hardness of the cured product is lowered. The fumarate of the invention (I) and the invention (II) needs to have at least one group represented by the formula (I) as a terminal group, and the other part may be a The carboxyl group represented by the formula (8) or the hydroxyl group produced from the polyhydric alcohol may be used as the terminal group. A specific example of the carboxyl group represented by the formula (8) which is produced from fumaric acid is a compound represented by the formula (9). The fumarate represented by the formula (9) has a terminal group having a carboxyl group derived from an alkenyl group and fumaric acid, and a polymerizable compound having a fumarate skeleton inside. The enolate group and the fumarate have a high free copolymerization property. Further, the terminal carboxyl group can be formed by bonding various hydroxyl groups with an ester, and a polymerizable ester having various physical properties can be synthesized. This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) -----------Installation----Ί——1 line (please read the back Precautions and then fill out this page) Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed-16- A7 B7 1287021 V. Inventive Note (14) Further, a specific compound having a terminal group of a hydroxyl group, for example, a compound represented by the formula (10). The formula (10) has one or more selected from the group consisting of the formula (3), wherein an allyl ether is preferred, and the formula (4), wherein a propenyl ether is preferred, as a terminal group, and has a polyhydric alcohol. The resulting hydroxyl group acts as a terminal group of fumarate. In the formula (10), Z is a trivalent to hexavalent polyol organic residue. Polyhydric alcohols, such as triols such as trimethylolpropane, trimethylolethane, and glycerol, tetrahydric alcohols such as pentaerythritol, ditrimethylolpropane, and diglycerin, sorbitol, A hexahydric alcohol such as dipentaerythritol or the like, and a hydroxyl group of a trivalent to hexavalent alcohol is added by ethylene oxide or propylene oxide, or a mixture of two or more of them. Among them, trimethylolpropane, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, and ethylene oxide additions of such alcohols, all of which are monohydric alcohols, and more than two It is preferred that the mixture has a higher reactivity with respect to the ester formation reaction. Hereinafter, the invention (III) will be described. The invention (III) is a method for producing the fumarate of the invention (I) or the invention (II). The present invention (III) is a method for producing the transbutyl succinate of the invention (I) or the invention (II), and can be classified into two steps (A) and (B). That is, (A) a step of forming an ester having a fumarate as a main skeleton and forming an ester repeating unit, and (B) a terminal polymerizable group represented by the formula (4) is represented by a group represented by the formula (3) The steps of isomerization formation, the paper scale is applicable to China National Standard (CNS) A4 specification (210X297 mm) -----------parameter - (Please read the notes on the back and fill out this page. ) 彳 彳 经济 经济 经济 经济 经济 -17 -17 -17 -17 -17 -12 -17 -17 -17 -17 -17 -17 -17 -7 -7 -7 -7 The second step is not a step necessary for producing the fumarate of the invention (I) or the invention (π), and the invention (I) or the invention (II) can be produced separately in any step. The anti-butyl succinate. First, the step (A) for producing the fumarate of the present invention (I) or the present invention (π) will be described. The fumarate represented by the formula (9) of the present invention (I) is obtained by reacting an anhydrous maleic acid with an alcohol represented by the formula (16) to obtain a maleic acid monoester. The maleic acid ester is further prepared by isomerization of fumarate. In this case, the isomerization ratio of the fumarate is not limited to 100%, and it may be a mixture of maleic acid ester and fumarate. From the viewpoint of polymerizability, fumarate is preferred. Equation (16) (Please read the notes on the back and fill out this page)

Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives (in the formula (16), X4 is in the formula (16), and in each of the X4s present, each of the independent alkyl groups or the alkyl group having a carbon number of 5 to 12, Or an alkyl group represented by the formula (6), and d is any one of the integers of 1 to 5; further, R2 and R3 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.) Formula (6) The paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -18- 1287021 A7 B7 V. Description of invention (16)

The Ministry of Economic Affairs, the Intellectual Property Office, the employee consumption cooperative, prints that r5 and r6 are each a hydrogen atom or a formula (7), and (7) (in the formula (7), R7 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms). When R1 in the formula (1) of the invention (I) is a fumarate represented by the formula (3), the fumarate represented by the formula (9) may be esterified with a polyhydric alcohol. be made of. When R1 in the formula (11) is a fumarate represented by the formula (3), the fumarate represented by the formula (9) may be esterified with the alcohol represented by the formula (16), or The esterification reaction of the alcohol represented by the formula (16) with fumaric acid or the dialkyl fumarate is carried out by transesterification with an alcohol represented by the formula (16). Further, when r1 in the formula (12) of the invention (I) is a fumarate represented by the formula (3), the transesterification reaction of the fumarate represented by the formula (17) with a polyhydric alcohol can be carried out. And made. (17) ----------- Participate - (Please read the notes on the back and fill out this page) Customize the paper size for the Chinese National Standard (CNS) Α 4 specifications (210X297 mm) - 19- 1287021 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperatives Printing i, invention description (17 (in equation (17), R1 is independent (3) or (4), X1 has 2 to 6 The organic residue derived from the polyol having 2 to 30 carbon atoms of the hydroxyl group.) Further, when R1 in the formula (15) of the invention (II) is a fumarate represented by the formula (3), (18) The obtained fumarate is obtained by transesterification with a polyol represented by the formula (19). Formula (18) 0-νΐΤαΧ3 Formula (19)

OH Further, the fumarate represented by the formula (20) may be esterified with an alcohol represented by the formula (9) and an alcohol represented by the formula (16), or an alcohol represented by the formula (16) It is obtained by esterification reaction with fumaric acid. Formula (20) R2 (In the formula (20), X4 is a cycloalkyl group having an alkyl group or a carbon number of 5 to 12 in the d-existing X4 in the formula (20), or a formula (6) The paper scale shown is applicable to China National Standard (CNS) A4 specification (210X297 mm) -----------Installation-------Ί线(Please read first Precautions on the back side of this page) -20 - 1287021 A7 B7 V. Description of the invention (18) The alkyl group, d is any one of 1 to 5; in addition, R2 and R3 are independent hydrogen atoms or An alkyl group having 1 to 5 carbon atoms.) Formula (6)

R5 and R6 are each a hydrogen atom or a formula (7), and a formula (7) "0- (in the formula (7), R7 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms). First, the production formula (9) The method for producing the fumarate shown is described in detail. A specific production example of the fumarate represented by the formula (9) is obtained by reacting an anhydrous maleic acid with an alcohol of the formula (16) by an additional reaction to obtain a maleic acid monoester, and then Maleic acid esters are prepared by isomerization of fumarate. The additional reaction of anhydrous maleic acid with an alcohol of the formula (16) is carried out under the absence of a catalyst or under a catalyst. The catalyst is not particularly limited as long as it is a general esterification catalyst, and is preferably an alkaline catalyst such as triethylamine or N,N_:methylamine pyridine. The reaction temperature is 2 (TC to 150 ° C, preferably 40 ° C to 120 ° C, and when the reaction temperature is lower than 20 ° C, the reaction is slow, so a longer reaction time is required, and the reaction temperature exceeds 150 °. At C, due to excessive production of diester, there will be a standard for the production of paper. The Chinese National Standard (CNS) A4 specification (210X297 mm) -----------Applied -- (Please read first Precautions on the back side Fill in this page) Order-Ί线· Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed - 21 - Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1287021 A7 V. Inventories Explain the rate of doubts. The ratio of the addition amount of the anhydrous cis-succinic acid to the alcohol represented by the formula (16) is not particularly limited. Generally, it is a dry molar maleic acid molar to add 0.2 mole equivalent to 10 mole equivalent. The alcohol represented by the formula (16) in the above range is preferably added in an amount of from 0.5 to 5 mol equivalents, more preferably in an amount of from 9 to 2 mol equivalents of the hydrazine. The ratio of the addition amount of the alcohol represented by the formula (16) exceeds When the molar equivalent is 1 ,, the amount of residual alcohol will be too much, less than 0.2 mol equivalent, because of the reaction of anhydrous maleic acid In addition, it is also a feasible step to add a solvent when performing an additional reaction. The solvent is, for example, an aromatic hydrocarbon such as benzene, toluene or xylene, diethyl ether or dimethoxyethane. An ether such as methoxyethyl ether, tetrahydrofuran or 1,4-dioxane. R2 and R3 of the alcohol represented by the formula (16) are, for example, identical to R2 and R3 of the above formula (3). a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. In terms of polymerizability, particularly in the case where both R2 and R3 are hydrogen atoms, the specific form of the alcohol represented by the formula (16) is, for example, Alcohol monoallyl ether, propylene glycol monoene propylene ether, 1,3-butanediol monoallyl ether, 1,4-butanediol monoallyl ether, cyclohexanediol monoallyl ether, Cyclohexane dimethanol monoallyl ether, diethylene glycol monoallyl ether, dipropylene glycol monoallyl ether, 2-allyloxy-2-phenylethanol, 2-allyloxy-1 _Phenylethanol, 2-allyloxy-1,2-propenylethanol, etc. The obtained maleic acid monoester can be known as an acidic catalyst such as hydrochloric acid, malfurin, piperidine, and diethyl Alkaline touch Medium, thiourea, chlorine, bromine This paper scale applies to China National Standard (CNS) Μ Specifications (210X297 mm) -----------Approved ------1T---,- -Ί线 (Please read the notes on the back and fill out this page) -22- A7 B7 1287021 V. Description of invention (%), iodine, acid chloride and other catalysts areomerize fumarate monoester. The reaction temperature for isomerization is not particularly limited, and is usually in the range of 30 to 200 ° C, preferably in the range of 50 to 150 ° C, more preferably in the range of 70 to 120 ° C, and the reaction temperature exceeds 20 ° ° In the case of C, it is not preferable because polymerization or decomposition reaction is extremely likely to occur. Further, in the isomerization reaction, a known hindered phenol-based polymerization inhibitor or a solvent can be used. The solvent to be used is, for example, an aromatic hydrocarbon such as benzene, toluene or xylene, or an ether such as diethyl ether, dimethoxyethane, methoxyethyl ether, tetrahydrofuran or 1,4-dioxane. An ester such as ethyl acetate or butyl acetate; a ketone such as acetone or methyl ethyl ketone. The fumarate represented by the formula (9) obtained by this method can be purified by distillation, liquid separation or recrystallization. Hereinafter, a method for producing the fumarate represented by the formula (3) in which R1 of the formula (10) is used will be described. R1 of the formula (10) is a fumarate represented by the formula (3), which can be obtained by esterifying a fumarate represented by the formula (9) with a polyhydric alcohol. Specific examples of the esterification reaction are as follows: (1) A method in which a fumarate represented by the formula (9) and a polyhydric alcohol are esterified in the presence of an acid catalyst. (2) A method in which a fumarate represented by the formula (9) is subjected to a halide and then reacted with a polyol to carry out esterification. (3) A method in which a fumarate represented by the formula (9) and a polyol are subjected to esterification by a condensing agent. First, the method of (1) will be explained. This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) I----------Installation-------Ί线(Please read the back Note: Please fill out this page again) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing -23- 1287021 A7 _ B7 V. Invention description (21) -----------^ —— (Please read first Precautions on the back side. Fill in this page. It can be used in the esterification catalyst of (1) method, such as sulfuric acid, P-methylsulfonic acid, methanesulfonic acid, ion exchange resin, mixed catalyst of boric acid and sulfuric acid. Lewis acid such as polyphosphoric acid or boron trifluoride ether lactone. The reaction can be carried out under normal pressure or under reduced pressure or under reduced pressure, for example, at an absolute pressure of 15 Pa to 1 MPa. The reaction is carried out by distilling off the by-product water at a reaction temperature of 20 to 200 ° C, preferably 4 G to 150 ° C. Less than 2 〇. The reaction will be slower at 〇, and when it exceeds 200 °C, there will be doubts about excessive by-products such as polymers. A solvent may also be used during the reaction. The solvent is not particularly limited, and specific examples thereof include benzene, hexane, cyclohexane, toluene, xylene, and the like. Further, the ratio of addition of the fumaric acid to the polyhydric alcohol represented by the formula (9) is not particularly limited. Preferably, the residue (-COOH) of the fumarate represented by the formula (9), the hydroxyl group (-OH) of the polyol is in the range of 0.2 mole equivalent to 5 mole equivalents, preferably 0.5. Mohr equivalent to a range of 1.5 mole equivalents. When the addition ratio is less than 0.2 mol equivalent, the residual amount of the fumarate shown in the formula (9) is too large, and when it exceeds 5 mol equivalents, the unreacted hydroxyl group remains, which is also unfavorable. The Intellectual Property Intelligence Bureau member JL Consumer Co., Ltd. printed it again. At this time, in the reaction conditions, for example, the ester moiety of the anti-succinic acid ester represented by formula (10), the dissociation part is equivalent to R1-(OX5) a-0H. An alcohol, followed by esterification of the alcohol with a carboxyl group of the fumarate represented by the formula (9) to form a fumarate diester monomer, which can then be polymerized without further purification. Sex composition is used. After the end of the esterification reaction, purification may be carried out to remove impurities or unreacted materials. Refining method, for example, dissolving fumarate in benzene, paper size. Applicable to China National Standard (CNS) A4 specification (210X297 mm) -24-1287021 Λ7 B7 V. Invention description (22) Benzene, ring In an organic solvent such as hexane, diethyl ether or methyl acetate 'ethyl acetate, the unreacted fumarate or by-product of the formula (9) is removed by washing with water or alkali. The carboxylic acids are removed in the form of a salt. Further, the product under an organic solvent such as an aliphatic hydrocarbon such as hexane or octane is further purified by a decantation method or a reprecipitation method, or a columnar purification method using a silicone resin or the like, and a film chromatography method to refine the purity. Also. Hereinafter, the method of (2) will be described. The method (2) is a method in which a fumarate represented by the formula (9) is derived from an acid halide and then reacted with a polyol to carry out esterification. In the method of (2), the method for derivatizing the acid halide of the fumarate represented by the formula (9) is not particularly limited, and for example, sulfinium chloride, phosphorus chloride or phosphorus pentachloride may be used. A known method such as phosphorus trichloride or phosgene. In particular, in the case of using sulfinium chloride, the catalyst may be zinc chloride, pyridine, boron, triethylamine or the like. Further, it is known that a mixture of sulfinium chloride and dimethylformamide is also an excellent reagent for synthesizing acid chloride. As described above, the derivatized halide of the fumarate represented by the formula (9) and the polyol are reacted in a known manner, and then the anti-butyl group represented by the formula (5) of the present invention can be obtained. Alkylene dicarboxylate. Finally, the method of (3) will be explained. The method (3) is a method in which a fumarate represented by the formula (9) and a polyol are reacted by a condensing agent to be esterified. Specific examples of the condensing agent used in the method (3) include, for example, dicyclohexylcarbonyldiamine or anhydrous trifluoroacetate, sulfonium chloride or the like, but are not limited thereto. There is no particular limitation as long as it is a known condensing agent. This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) -----------^-- (Please read the note on the back and fill out this page) Employees' Cooperatives Printed -25- A7 B7 1287021 V. INSTRUCTIONS () In terms of convenience of handling, especially the use of sulfonium chlorides is preferred. When a sulfonate chloride is used as the condensing agent, for example, in the fumarate represented by the formula (9), a base is added in the presence of a solvent to carry out a reaction, and then, after the sulfonium chloride is added, the mixture is added. A method in which an alcohol is allowed to react. Among them, the sulfonium chloride used is, for example, P-toluenesulfonium chloride, methanesulfonium chloride, trifluoromethanesulfonium chloride or the like. The ratio of addition of the fumarate to the sulfonium chloride represented by the formula (9) is not particularly limited. Generally, an expanded metal having an equivalent amount or more can be used. More preferably, for the non-butyl succinate of the formula (9), the sulfonate chloride is added in a ratio ranging from 1 mole equivalent to 2 mole equivalents. Further, the ratio of addition of the fumarate to the polybasic acid ester represented by the formula (9) is not particularly limited. Preferably, the hydroxyl group (-OH) of the carboxyl group (-COOH) 'polyol of the fumarate represented by the formula (9) is in the range of 0.2 to 2 mol equivalents, more preferably 0.4 to 1.2 mol equivalents. The scope. In this case, the solvent to be used is not particularly limited as long as it does not hinder the reaction. Specifically, for example, ethers such as tetrahydrofuran and dioxins, aromatic hydrocarbons such as benzene, toluene, and xylene, halides such as chloroform, dichloromethane, and dichloroethane, dimethylformamide, and dimethylene. Shuo et al. A base such as an alkali metal such as sodium hydroxide, potassium hydroxide, hydrated planer, sodium carbonate, potassium carbonate, carbonic acid planer, sodium hydrogencarbonate or potassium hydrogencarbonate. The amount of alkali added varies depending on the type, but for the fumarate represented by formula (9), the range of 1 mole to 5 moles is suitable for the Chinese paper standard. (CNS) A4 specification (210X297 public) I----------装------ order---;--Ί line (please read the notes on the back and fill out this page) Printed by the Intellectual Property Office of the Ministry of Economic Affairs, Employees' Consortium -26 - A7 B7 1287021 V. INSTRUCTIONS (24) The reaction temperature is generally -20 ° C to 100 ° C, preferably 0 ° C to 50 ° C. Excessive side reactions occur at temperatures above 100 °C, and delays below -20 °C cause poor reaction. For the product obtained, a purification step can be used to remove the impurities. a purification method, for example, in an organic solvent such as benzene, toluene, xylene, cyclohexane, methyl acetate, ethyl acetate, diethyl ether, dichloroethane or chloroform, the product is dissolved therein, and then water is used. And a method of washing with an alkali or an acid, or a method of decanting or reprecipitating the product using an organic solvent such as an aliphatic hydrocarbon such as hexane or octane. Further, it is also possible to refine the film by a columnar refining method such as silicone or the like, and to improve the purity. Hereinafter, a method for producing a fumarate represented by the formula (3) in the formula (11) of the invention (I) will be described. R1 in the formula (1 1 ) is a fumarate represented by the formula (3), which is an esterification reaction of the fumarate represented by the formula (9) with an alcohol represented by the formula (16), or The fumaric acid is obtained by a manner in which an alcohol of the formula (16) is esterified with a dosage form. Specifically, for example, in the above formula (10), R1 is a method for producing a fumarate represented by the formula (3). In another method, for example, the dialkyl fumarate is transesterified with the formula (16), and the R1 in the formula (1 1 ) is a fumarate represented by the formula (3). The dialkyl fumarate and the alcohol of the formula (16) are simultaneously reacted in the presence of a known transesterification catalyst in the alcohol removal step by-product to obtain the same. Dialkyl fumarate such as dimethyl fumarate and anti-butene two paper scales applicable to China National Standard (CNS) A4 specification (210X297 mm 1 ' -27- .II n Pack II I — II. Line (please read the notes on the back and then fill out this page) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Ministry of Printing and Economy Ministry Intellectual Property Bureau Staff Consumer Cooperatives Printed 1287021 A7 B7 V. Invention Description (%) Acid B Ester, di-n-propyl fumarate, diisopropyl fumarate, di-n-butyl fumarate, di-sec-butyl fumarate, fumaric acid T-butyl ester, etc. In terms of the ease of removal of the alcohol of the by-product, dimethyl benzoate, diethyl fumarate, di- propyl fumarate, and anti-butyl Diisopropyl phthalate or the like is preferred. The transesterification catalyst used herein is not particularly limited, and specific examples thereof include alkali metals, alkaline earth metals and oxides thereof, and oxides of Zn, Sn, and Ti. Or hydroxide, alkoxide, acetamidine acetone ligand complex, etc. Further, the reaction temperature is 80 to 200 ° C, the reaction pressure can be under normal pressure or Under pressure or under reduced pressure, for example, it can be carried out at an absolute pressure of 15 Pa to 1 MPa. Further, the portion of the fumarate in the fumarate represented by the formula (11) is formed into a maleic acid. After the acid ester portion, the isomerization reaction is carried out to obtain the fumarate represented by the formula (11). The maleic acid ester is used in the isomerization reaction, and is opposite to the above formula (1 1 ). The method for producing a butyric acid ester is the same as the method of esterifying maleic acid or anhydrous maleic acid with an alcohol represented by the formula (16). The specificity of the esterification reaction is, for example, the above formula. (10) R1 is the same as the method for producing the fumarate represented by the formula (3), or, for example, a method in which a dialkyl maleate is subjected to a transesterification reaction with the formula (16). Specifically, as described above, the dialkyl maleate and the formula (1 6 ) are the same as the transesterification reaction of the method for producing the fumarate represented by the formula (3) in the formula (11). The alcohol shown is prepared by reacting in the presence of a known transesterification catalyst while removing the alcohol of the by-product. The paper scale is applicable to the Chinese national standard. Quasi (CNS) A4 specification (21〇><297 mm) IIII —- Book TM" *7— (Please read the note on the back and fill out this page) -28- Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1287021 A7 B7 V. Invention Description ( 26 a catalyst capable of changing a maleic acid ester to an isomerization reaction of a fumarate, for example, using a complex of an element such as palladium, ruthenium or iridium or a supported type using the element as a carrier Catalysts and the like are preferred. In particular, in the case of purifying the fumarate, it is preferred to use a supported catalyst from the viewpoint of removing the catalyst. The carrier which can be used as the supported catalyst is not particularly limited, and a porous material can be generally used as the carrier. Specifically, for example, ruthenium, aluminum, ruthenium aluminide, zeolite, activated carbon, titanium, magnesium or other inorganic compounds. The amount of the element supported on the carrier is preferably from 0.05% by mass to 20% by mass based on the total amount of the catalyst, and more preferably from 2% by mass to 10% by mass. When the amount of the load is less than 0.05% by mass, the reaction time is delayed. When the amount is more than 20% by mass, it is not preferable because it has too many elements which are not related to the isomerization reaction. The amount of the above-mentioned supported catalyst is preferably, for example, from 1% by mass to 50% by mass based on the maleic acid ester, and more preferably from 1% by mass to 30% by mass. When the amount is less than 0.01% by mass, the reaction time is delayed. When the amount is more than 50% by mass, it is not preferable because it has too many elements which are not related to the isomerization reaction. Further, the isomerization catalyst may be used alone or in combination of two or more kinds of catalysts. The temperature of the isomerization reaction is not particularly limited. Generally 3 (TC to 200 ° C, preferably 60 ° C to 180 ° C, more preferably 80 ° C to 160 ° C. When the reaction temperature is lower than 30 ° C, the reaction delay will occur, exceeding 200 ° C In the present invention, the isomerization reaction is carried out in a solvent. The size of the paper used is applicable to the Chinese National Standard (CNS) A4 specification. (210X297 mm) I ^, order---.--1-^ (please read the notes on the back and fill in this page) -29- Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1287021 Α7 Β7 V. Invention (27) An aromatic hydrocarbon such as benzene, toluene or xylene, an ether such as diethyl ether, dimethoxyethane, methoxyethyl ether, tetrahydrofuran or 1,4-dioxane, or acetic acid. An ester such as ethyl ester or butyl acetate; a ketone such as acetone or methyl ethyl ketone; or an alcohol such as methanol, ethanol or isopropyl alcohol; and when these solvents are used, two or more kinds of solvents may be used in combination. The isomerization reaction can be carried out under normal pressure or under pressure, for example, at 1 KPa to 1 MPa. Further, the transesterification reaction or the isomerization reaction In the process, a polymerization inhibitor may be added to suppress the polymerization reaction. Polymerization inhibitors such as p-benzoquinone, naphthoquinone, 2,5-diphenyl-P-benzoquinone, etc., hydroquinone, pt-butyl ortho Polyvalent phenols such as hydroquinone and 2,5-di-t-butylhydroquinone; phenols such as hydroquinone monomethyl ether, di-t-butyl p-cresol, and α-naphthol. In the formula (12) of the invention (I), R1 is a method for producing a fumarate represented by the formula (3). In the formula (12) of the invention (I), R1 is represented by the formula (3). The fumarate is obtained by transesterification of a fumarate represented by the formula (17) with a polyhydric alcohol, that is, R1 in the formula (12) is represented by the formula (3). The fumarate is obtained by reacting a fumarate represented by the formula (17) with a polyhydric alcohol in the presence of a known transesterification catalyst while removing the alcohol of the by-product. Specific examples of the transesterification reaction are the transesterification reaction in the method for producing a fumarate represented by the formula (3) in the above formula (1 1 ). In the reaction, the formula (17) is shown. Fumarate, due to multiple papers The scale applies to the Chinese National Standard (CNS) Α4 specification (210 X 297 mm) « Batch 1Τ--------^ (Please read the note on the back and fill out this page) -30 - A7 B7 1287021 V , invention description (28) The case where the addition ratio of the alcohol is different and there is a residual in the product, and it can be used without special removal at this time. Further, the anti-butene in the anti-succinic acid diester represented by the formula (12) After the portion of the diester is formed into a maleic acid ester moiety, the isomerization reaction is carried out to obtain a fumarate represented by the formula (12). The maleic acid ester used in the isomerization reaction may be the same as the method for producing the fumarate of the above formula (1 1 ), and may correspond to the fumarate represented by the formula (17). The maleic acid diester and the polyol are synthesized by reacting with an ester. The isomerization reaction of the maleic acid ester to the fumarate is the same as the method for producing the fumarate of the above formula (11). Hereinafter, a method for producing a fumarate represented by the formula (3) in the formula (I5) of the invention (II) will be described. In the formula (15), R1 is a fumarate represented by the formula (3), which can be obtained by transesterification of a polybutyric acid diester represented by the formula (18) with a polyol represented by the formula (19). By. Specifically, the fumarate represented by the formula (18) may correspond to an epoxy compound such as ethylene glycol allyl ether or propylene glycol allyl ether of R^OX^OH and X3 units, for example, a ring. An additional reaction such as oxyethane or propylene oxide, cyclohexene oxide, or styrene oxide to synthesize an alcohol, followed by esterification with fumaric acid or esterification with dialkyl fumarate The reaction is prepared in the same manner. An alcohol having an ether bond represented by the formula (1 9 ), such as an alcohol such as ethylene glycol or propylene glycol, can be applied to an epoxide such as ethylene oxide, propylene oxide or ring paper, and is applicable to the Chinese national standard (CNS). A4 size (210X297 mm) ------Installation-- (Please read the notes on the back and fill out this page) Customs Department of Intellectual Property Intelligence Bureau Staff Consumer Cooperative Printed -31 - Ministry of Economic Affairs Intellectual Property Bureau Employee consumption cooperative printed 1287021 A7 B7 V. Description of invention (29) Hexene oxide; styrene oxide and other additional reactions. The above is a method for forming the main skeleton of (A) fumarate as an ester, and a method for forming an ester repeating unit will be described. Subsequently, the step of (B) forming the terminal polymerizable group via isomerization will be described. R1 in the formula (10) of the invention (I) is a transbutyrate produced by the formula (4), and R1 in the formula (11) of the invention (I) is a counter-butadiene represented by the formula (4). The diester may have R1 in the above formula (10) as a fumarate represented by the formula (3), and R1 in the formula (11) is a terminal group of the fumarate represented by the formula (3). It is produced by a method of isomerization. Further, in the formula (12) of the present invention, R1 is a fumarate represented by the formula (4) and a formula (5) of the invention (1) is a compound represented by the formula (4) The enedionate can be obtained by a method in which isomerization of the fumarate represented by the formula (3) by R1 is equivalent. Hereinafter, the isomerization reaction will be described. The isomerization reaction of the formula (3) to the formula (4) is preferably, for example, a complex of an element such as palladium, rhodium or iridium or a supported catalyst having an element as a carrier. The carrier which can be used as the supported catalyst is not particularly limited, and a porous material can be generally used as the carrier. Specifically, for example, ruthenium, aluminum, ruthenium aluminide, zeolite, activated carbon, titanium, magnesium or other inorganic compounds. The amount of the element supported on the carrier is preferably 对 5 mass% to 20 mass%, more preferably 2 mass% to 1 mass%. The negative standard is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) ' -32- , Private clothing ------1T--------^ (Please read the notes on the back first) Fill in this page again) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1287021 A7 B7 V. Invention Description (3()) When the load is less than 0.05% by mass, the reaction time will be delayed, and when it exceeds 20% by mass, It is also poor because it has too many elements that are not related to the isomerization reaction. The amount of the above-mentioned supported catalyst is, for example, a fumarate represented by the formula (10), the formula (11), the formula (12) and the formula (15) (3). The mass% to 50% by mass is preferably more preferably from 1% by mass to 30% by mass. When the amount of the catalyst is less than 0.01% by mass, the reaction time is delayed, and when it exceeds 50% by mass, it is not preferable because it has too many elements which are not related to the isomerization reaction. Further, the isomerization catalyst may be used alone or in combination of two or more kinds of catalysts. The temperature of the isomerization reaction is not particularly limited. Generally, it is 30 ° C to 200 ° C, preferably 60 ° C to 18 (TC, more preferably 80 ° C to 160 ° C. When the reaction temperature is lower than 30 ° C, the reaction delay is caused, exceeding 200 ° C In the present invention, the isomerization reaction is carried out in a solvent, and the solvent to be used is, for example, an aromatic hydrocarbon such as benzene, toluene or xylene. Ethers such as diethyl ether, dimethoxyethane, methoxyethyl ether, tetrahydrofuran, 1,4-dioxane, esters such as ethyl acetate and butyl acetate, acetone, methyl ethyl ketone Ketones, alcohols such as methanol, ethanol, and isopropanol, etc. When these solvents are used, two or more solvents may be used in combination. The isomerization reaction may be carried out under normal pressure or under pressure, for example. It can be carried out at 1 KPa to IMPa. In addition, during the transesterification or isomerization reaction, a polymerization inhibitor can be added to suppress the polymerization reaction. The polymerization inhibitor, for example, p-benzoquinone, naphthoquinone, and the paper scale are applicable to the Chinese national standard. (CNS) A4 specification (210X297 mm) -----------Installation ------Booking ------ (Please read the notes on the back first) Fill in this page) -33- 1287021 A7 Β7 V. Description of invention (31) 2,5-Phenyl-p-benzene and other benzoquinones, hydrogen brewing, p_t-butyl phthalate, 2,5 a polyvalent phenol such as di-t-butylhydroquinone, a phenol such as hydroquinone monodecyl ether, di-t-butyl-p-cresol or α-naphthol. The present invention (IV) will be described below. Invention (IV) is a polymerizable composition containing the fumarate of the invention (I) or the invention (π). The polymerizable composition of the invention (IV), in addition to the invention (I) or the present invention In addition to the fumarate of the invention (II), if necessary, a compound having a free polymerizability or a free polymerization initiator may be further contained. The free polymerizable compound, for example, has an unsaturated polyester or a methacrylate group. Oligomers, free polymerizable monomers, etc. Unsaturated polyesters such as α, unsaturated polybasic acids or acid anhydrides are produced by polycondensation with a saturated polybasic acid or polyterpene alcohol. /3 - an unsaturated polybasic acid such as maleic acid, fumaric acid, itaconic acid, anhydrous maleic acid, anhydrous itaconic acid, etc. Saturated polybasic acids having an acid component such as saturated aliphatic dicarboxylic acid such as succinic acid, adipic acid or sebacic acid, anhydrous phthalic acid, phthalic acid, terephthalic acid, trimellitic acid, and anhydrous An aromatic polycarboxylic acid such as trimesic acid or 2,6-naphthalene dicarboxylic acid, anhydrous dick acid, 1,2-cyclohexanedicarboxylic acid, hexahydroanhydrous phthalic acid, iota, 4-cyclohexane An alicyclic dicarboxylic acid such as a carboxylic acid, etc. a polyhydric alcohol such as ethylene glycol, diethylene glycol, 1,2-propanediol or 1,3-propanediol, dipropylene glycol, 1,3-butanediol or 1,4-butanediol, neopentyl glycol, 2-methyl 1,3·propanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,6-fluorene Alcohol or an aliphatic diol such as i,9, decanediol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, hydrogenated bisphenol a. This paper scale is applicable to the Chinese National Standard (CNS) Α4 specification ( 210Χ297 mm), 衣衣-- (Please read the notes on the back and fill out this page) 订------------------------------------------------------------------------------------------- Employee consumption cooperative printed 1287021 A7 B7 V. Invention () 32 such as alicyclic diol, bisphenol A and other aromatic diols such as ethylene oxide and propylene oxide addenda, glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, sorbus A trivalent or higher alcohol such as a sugar alcohol or dipentaerythritol. Other unsaturated polyesters, for example, are prepared by transesterification of a saturated polybasic acid with a dialkyl ester of an unsaturated polychatty acid and a polyhydric alcohol. In this case, the alkyl group may be a methyl group, an ethyl group or a C group. Base, butyl, etc. Further, the (meth) acrylate-based compound used in the present invention has two or more (meth) acrylonitrile groups in its structure, and specifically, for example, urethane (meth) acrylate, polyhydric alcohol, and A base acid or an anhydride thereof is produced by reacting with (meth)acrylic acid. Specifically, a polyester (meth) acrylate, for example, a polyether (meth) acrylate obtained by reacting a polyol obtained by adding ethylene oxide or propylene oxide with a (meth) acrylate, and a hydroxyl group-containing compound, A lipid epoxy (meth) acrylate obtained by reacting an epoxy compound with (meth)acrylic acid or a (meth) acrylate having a carboxyl group, and ethylene glycol di(meth)acrylate, diethylene glycol II (Meth) acrylate, neopentyl glycol di(meth) acrylate, glycerol di(meth) acrylate, trimethylolethane tri(meth) acrylate, trimethylolpropane three Polyfunctional (meth) acrylate such as (meth) acrylate, pentaerythritol tetra(meth) acrylate, dipentaerythritol hexa (meth) acrylate, decane having a decyloxy group and a (meth) acrylonitrile group (Meth) acrylate, etc. The urethane (meth) acrylate of the present invention can be obtained, for example, by reacting a known polyhydric alcohol with a polyisocyanate with hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate. Polyols, such as the pre-recorded paper size, are applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). ^.tT------*— ^ (Please read the note on the back and fill out this page) - 35- 1287021 V. Description of Invention (33) The content of the polyol described in the saturated polyester. Further, the polyisocyanate is, for example, toluene diisocyanate, 4,4,-diphenylmethane isocyanate, xylene diisocyanate, hexamethyl diisocyanate or isophorone diisocyanate. The polybasic acid used in the polyester (meth) acrylate or polyether (meth) acrylate raw material of the present invention is the same as the polyhydric alcohol, for example, as described in the above-mentioned unsaturated polyester. The epoxy (meth) acrylate epoxy compound of the present invention is, for example, a bisphenol A type, a bisphenol S type, a bisphenol F-shaped bisphenol type glycidyl ether, or a novolak type glycidyl ether epoxy resin. A compound or the like. The free polymerizable monomer of the present invention is a polymerizable group having a double bond, specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (methyl). Monofunctional (meth)acrylic acid such as acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate Aromatic vinyl compounds such as ester, styrene, α-styrene, methoxystyrene, divinylbenzene, vinyl acetate, vinyl propionate, vinyl butyrate, trimethyl vinyl acetate, hard ester An aromatic vinyl ester such as a vinyl ester of an aliphatic carboxylic acid such as vinyl acetate or vinyl hexanoate or an alicyclic vinyl ester such as a vinyl cyclohexanecarboxylate; a vinyl benzoate or a vinyl t-butyl benzoate; Hydroxyalkyl vinyl esters such as hydroxyethyl vinyl ester, hydroxypropyl vinyl ester, hydroxybutyl vinyl ester, diallyl phthalate, diallyl isophthalate, diallyl diallylate Ester, diallyl maleate, diallyl fumarate, Diallyl carbonate, diallyl trimellitate, triallyl cyanurate, triallyl isopolyhydrocarbonate, diallyl carbon paper size applicable to China Standard (CNS) A4 specification (210X297 mm) -----------Applied _| (Please read the note on the back and fill out this page) ♦ Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative System-36- Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1287021 A7 B7 V. Description of Invention (34) Acid ester, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol Allyl compound such as triallyl ether, N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-lauryl maleimide , N-2-tolyl-maleimide, N-2-chlorophenylmaleimide, N-2-methoxyphenylmaleimide, N,N-4,4'-di Maleic imines such as phenylmethane bismaleimide, maleic acid, fumaric acid, anhydrous maleic acid, dimethyl maleate, maleic acid Diethyl ester, dimethyl fumarate, anti-butyl An unsaturated dibasic acid such as diethyl edeoate, dimethyl itaconate or diethyl itaconate, and a fumarate represented by the formula (17) or the formula (18). When the polymerizable composition of the present invention (IV) is blended with the fumarate represented by the formula (17) or the formula (18), it is less likely to be inhibited by oxygen during hardening, and is easily surface hardened. Good finished product. Further, such free polymerizable monomers may be used singly or in combination of plural or more, in the polymerizable composition of the invention (IV), the negative ester of the invention (I) or the invention (II) The amount used is from i% by mass to 99% by mass, preferably from 5% by mass to 80% by mass, based on the polymerizable composition. In particular, when the amount is 5% by mass or more, the influence of the hindrance of oxygen at the time of hardening can be reduced, and the surface is not made to be sticky. The free polymerization initiator which can be used in the polymerizable composition of the present invention (IV) can be used as a free polymerization initiator, for example, by heat, ultraviolet rays, electron rays or radiation. Free polymerization initiator which can be freely polymerized by heat, for example, 2, 2, - even paper scale is applicable to China National Standard (CNS) A4 specification (210X297 mm). ^II-------, - ^ ( Please read the notes on the back and fill out this page.) -37- 1287021 A7 B7 V. INSTRUCTIONS (35) Azo compounds such as nitrogen bisisobutyronitrile and 2,2'-azobisisoprene, methyl Ketone peroxides such as ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, benzamidine peroxide, sulfhydryl peroxide, lauryl peroxide, etc. Allyl peroxide 'diisopropyl peroxide, t-butyl cumyl peroxide, di-t-butyl peroxide, etc. Dialkyl peroxide, 1,1-double (i-hexyloxy) 3,3,5-trimethylcyclohexane, 1,1-di-t-butylperoxycyclohexane, 2,2-di(t-butylperoxy a peroxy ketal such as butane, t-butyl peroxytrimethyl acetate, t-butylperoxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, Di-t-butylperoxy hexahydroterephthalate, di-t-butyl peroxydiphosphate Ester, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxyacetate, t-butyl peroxybenzoate, di-t-butyl Alkyl peroxyesters such as trimethyl adipate peroxide, t-butylperoxy-2-ethylhexanoate, and t-hexylperoxy-2-ethylhexanoate, two different A percarbonate such as propyl peroxydicarboxylate or di-sec-butyl peroxy isopropyl carbonate. Further, in particular, in the process of forming a film by thermal coating, it is not necessary to use a free polymerization initiator, which can self-generate crosslinking. Free polymerization initiator for ultraviolet light or electron beam polymerization, such as acetophenone, 2,2-dimethoxy-2-phenylethyl benzene, diethoxy acetophenone, 1 _ base-ring Hexyl-benzophenone, 2-methyl-(methylthio)phenyl]-2-mafolin acetone-1,2-benzyl-2-dimethylamino-1-(4-mafolin phenyl)-butyl Ethyl ketone derivatives such as keto-1,2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzophenone, 4,4-bis(dimethylamino)benzol Benzophenone derived from ketone, 4-trimethyldecyl benzophenone, 4-benzylidene-4'-methyl-diphenyl sulfide, etc. The paper scale is applicable to China National Standard (CNS) A4 specification. (210X 297 mm) -----------Approved-- (Please read the notes on the back and fill out this page) Customs Department of Intellectual Property Intellectual Property Bureau Staff Cooperatives Printed -38 - 1287021 A7-B7 V. Description of invention (36) Benzene-derived derivatives such as benzoin, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, benzoin isopropyl ether Methyl phenylglyoxime, quinone dimethyl ketal, 2,4,6-trimethyl phenylene diphenyl phosphine oxide, etc. The amount of the polymer starter ester used is from 0. 01 to 15% by mass, preferably from 1:1 to 9% by mass, based on the weight of the polymerizable composition of the present invention (IV). Further, when the polymerization is carried out using the polymerizable composition of the present invention, various additives may be added depending on the purpose of use. For example, an ultraviolet absorber, an oxidation inhibitor, a colorant, a lubricant, an antistatic agent, an inorganic chelating agent such as ruthenium, aluminum or aluminum hydroxide. The polymerizable composition of the present invention (IV) can be cured by a curing method such as a coating method such as roll coating or spin coating, a molding method, or a photoforming method using ultraviolet rays, electron wires or heat. Further, in the method of curing the polymerizable composition of the present invention, a solvent may be used in order to lower the viscosity. The solvent to be used is an aromatic hydrocarbon such as toluene or xylene, or an acetate such as ethyl acetate, propyl acetate or butyl acetate, such as acetone, methyl ethyl ketone or methyl isobutyl ketone, tetrahydrofuran or the like. An ether such as an oxane or an alcohol such as ethyl alcohol, (iso) propyl alcohol or butyl alcohol. Finally, the invention (V) will be explained. The present invention (V) is a cured product obtained by curing the polymerizable composition of the invention (IV). The cured product of the invention (V) can be widely used for coating of woodwork, film coating, metal coating, plastic coating, inorganic coating, hard coating, film coating, gel coating, etc. Ink materials such as covering materials, painting or printing inks, and the standard of light-made paper are applicable to China National Standard (CNS) A4 specifications (210X297 mm) -----------^-- (Please read the back first Precautions and then fill out this page) Order • Department of Economics, Intellectual Property Bureau, Staff and Consumer Cooperatives Printed -39- Ministry of Economic Affairs, Intellectual Property Office, Staff and Consumer Cooperatives Printed 1287021 A7 B7 V. Inventions () Ο ί Type Materials, Glasses The technical field of curable resins such as optical materials such as lenses and enamels, adhesives, photoresists, blocking agents, and molding materials. In particular, it is extremely suitable for film coating materials that are easily blocked by oxygen. The substrate is not particularly limited in coating, and specifically, for example, metal, glass, plastic, or the like. Further, the resin which can cure the polymerizable composition of the present invention can produce a cured product having a large crosslinking density and a high surface hardness. In particular, a hardened resin of a fumarate having a trivalent to hexavalent polyol represented by the formula (1 〇) as a skeleton has an extremely high surface hardness and has a pencil hardness (JIS Κ - 5400 ) of 4 to 8 Å. Hardness, it is extremely suitable for use in technical fields requiring wear resistance or scratch resistance. EXAMPLES The present invention will be described in more detail by way of examples, but without departing from the scope of the invention, the invention is not limited by the examples. Write down the machine. (machine)

^-NMR Model: JEOL EX-400 (400 MHz) was dissolved in heavy hydrogen chloride. The internal standard was determined using tetramethyl decane and the chemical shift was calculated. This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) I----------------------, 玎------^ (please read the back first) Note: Please fill out this page again) -40- 1287021 A7 B7 V. Description of invention (38)

FT-IR

Models used: Spectrum GX manufactured by Perkins, Inc. uses a KBr plate and is measured by a liquid membrane method.

GPC model: pump Shodex DS-4 UV detector

Waters484 RI detector ShodexRI SE- 60 Use column: Shodex KG + K-8 0 1 (In addition to K-802 in Example 1,) Measurement conditions: Dissolver chloroform flow rate 1 ml/min, column temperature 4 〇 ° C, Detecting UV 2 5 4 nm GC (monomer analysis) Model: GC-14B (made by Shimadzu Corporation) Column: DB-23 0.25#x30m (manufactured by J&W) Carrier gas: nitrogen 1 ml/min Dispersion ratio: 1 : 50

Flow rate ·· 1 0 m 1 / mi η Detector: FID Injection temperature: 2 3 0 °C Detector temperature · · 230 °C Temperature process: 40 ° C (10 minutes) - (10 ° C / min) ~ ~ >200. 〇本纸标准Applicable to China National Standard (CNS) A4 Specification (210X297 mm) ------t.-- (Please read the note on the back and fill out this page) Customize the Ministry of Economic Affairs Intellectual Property Office staff consumption Cooperatives Printing -41 - Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumers Co., Ltd. Printed 1287021 A7 B7 V. Invention Description (39) Model of UV irradiation device: Toschi-401 (manufactured by Toshiba Corporation) Light source: Mercury bulb illumination intensity: Irradiation Distance l〇〇mm-70mW/cm2 Melting point measurement model: MP-500D (manufactured by Yanaco Co., Ltd.) Refractive index used: Uber refractometer 1 T (made by Yard Corporation) The refractive index (nD) was measured using the above machine. The liquid system uses α-bromo naphthalene. The measurement temperature was 25 °C. [Example 1] In a 1 liter flask equipped with a distillation apparatus, 312 g of bis(2-allyloxyethyl) maleate and 135 g of bisphenol A of 2 mol of ethylene oxide were fed. Addenda, 4 g of dibutyltin oxide, 0.1 2 g of tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate as a polymerization inhibitor] Methane (manufactured by Chemical Co., Ltd., trade name: IRGANOX 1010) was heated to 160 ° C under a reduced pressure in the reaction system, and ethylene glycol monoallyl ether as a by-product was distilled off. Finally, the pressure was reduced to about 400 Pa, and almost the theoretical amount of ethylene glycol monoallyl ether was distilled off. After the reaction solution was cooled to room temperature, 3 85 g of a product was taken. The obtained product is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) on the paper scale — , ^-------1T---------ii (please read the notes on the back first) Fill in this page) -42- 1287021 Α7 Β7 V. Inventive Note (40) j-NMR measurement confirmed that it is a double (2-allyloxyethyl) maleate and bisphenol A 2 Mo earrings a condensate of an oxyethane addition. (Please read the precautions on the back and fill out this page.) Further, by GC analysis, the product contained 30.3% of bis(2-allyloxyethyl) maleate. 5 (ppm) 7· 13 to 7.11 (m, Ph), 6.8 1 to 6.78 (m, Ph) 5 6.29 (s, -OCOCH = CHCOO-), 5.95 to 5.84 (m, CH2 = CH-CH2-), 5.3 1 to 5.25 (m5CH2 = CH-CH2-)5 5.21 to 5.17 (m, CH2 = CH-CH2·), 4.5 2 to 3.64 (m, -0-CH2-CH2-C00-, CH2 = CH-CH2- ,-0-CH2-CH2-C00-5Ph-0-CH2-CH2-0C0-C = C-),1.63(s,Ph-C(Me)2-Ph), 1.62(Ph-C(Me)2 -Ph). 62.4 g of the obtained mixture, 60 ml of toluene, 60 ml of 1-propanol, and 6.2 g of RU-C loaded with a load of 5% by mass were printed by the Ministry of Economic Affairs and Intellectual Property Office employees' cooperatives. After being replaced by nitrogen, the temperature was raised to 150. °C. Subsequent heating and stirring for 10 hours at the ketone temperature. After cooling, the reaction solution was filtered off with a solvent, and the filtrate was evaporated under reduced pressure using a solvent to obtain 59.2 g of a yellow, highly viscous liquid. The results of analysis using NMR revealed that the double bond (ά = 6.2 9 ppm) of the cis-butanic acid residue was changed to the double bond of the fumaric acid residue (5 = 6.93 to 6.86 ppm). The isomerization rate is 100%. Further, the area percentage of the obtained product as a result of GPC analysis, and the content of the product condensation degree η (the number of repeating units) are shown in Table 1. This paper scale is applicable to China National Standard (CNS) Α4 specification (210X297 mm) -43- 1287021 Δ7 Α7 Β7 V. Invention description (41) Table 1 Condensation degree η 1 2 3 4 5 Composition (area ratio %) 30.3 29.0 23.1 13.0 4.6 -----------^1 — (Please read the precautions on the back and fill out this page) [Example 2] In a 3 liter glass flask, feed 50 g of anhydrous cis. Acetyic acid, 573 g of ethylene glycol monoallyl ether, 0.05 g of hydroquinone monomethyl ether, and stirred at 50 ° C for 24 hours under a nitrogen atmosphere, and lkg of 1,4·2 was added to the obtained reactant. Oxane, 10 g of concentrated hydrochloric acid, and 0.1 g of hydroquinone monomethyl ether were stirred at 100 ° C for 1 hour. Subsequently, 1,4-dioxane was distilled off under reduced pressure, and toluene lkg and water lkg were added to the reaction mixture, followed by liquid separation. The organic layer was evaporated under reduced pressure of methylenebenzene to give a pale yellow liquid. NMR, FT-IR analysis

As a result, it was confirmed to be fumaric acid mono(2-allyloxyethyl). iH-NMR-line 6 (ppm) 10.44 (br. s, 1H, -COOH), 7.30-6.83 (m, 2H, -0C0CH=CHC00-), 5.92~5.88 (m, lH, CH2=CH-CH2- ), 5.32~5.21(m,2H, CH2=CH-CH2-), 4. 37 (br. s, 2H, -〇-CH2-CH2-CO〇-), 4.07 (br. s, Ministry of Economics, Intellectual Property) Bureau employee consumption cooperative printed 2H, CH2=CH-CH2-), 3.73 (br. s, 2H, -〇-CH2-CH2-CO〇-).

IR v (OH) = 3300~250001^, v (0)) = 1727 (: 111-1, v (allyl C=C) = 1647 cm 1 [Example 3] A stirring device, a thermometer, a condenser, In the 500 mL glass flask of the water quantitative receiver, the 154 g of the reverse-precision paper prepared in Example 2 was applied to the Chinese National Standard (CNS) A4 specification (210×297 mm) -44-126871 A7 B7. (42) Diacid-one (2-isopropyloxyethyl), pentaerythritol 21.8g, 200mL benzene ' 〇 · 25 g of p-toluenesulfonic acid fed into it. Stirring in an oil bath, the reaction temperature Raised to 80 ° C, the by-product water was distilled off during the reaction. When the distilled water reached the theoretical amount, the reaction was stopped and then cooled. The reaction solution was transferred to a separatory funnel and 300 mL of benzene was added. The mixture was subjected to liquid separation treatment using a 10% aqueous solution of sodium carbonate and water, and then concentrated under reduced pressure to obtain 120 g of product. This product was confirmed to be contained by 1H-NMR, FT-IR, GC and GPC. Condensation of pentaerythritol with fumaric acid mono(2-allyloxyethyl), bis(2-allyloxyethyl) fumarate Composition of 43% monomer (measured by GC).

IR v (CO) = 1 727 cm · 1 v v (allyl C = C) = 1 647 cm '1 [Example 4] In a 500 mL glass flask equipped with a stirring device, a thermometer, a condenser, and a water quantitative receiver, To 52 g of the fumaric acid mono(2-allyloxyethyl), trimethylolpropane 21.5 g, 200 mL of benzene, and 0.25 g of p-toluenesulfonic acid obtained in Example 2 were fed thereto. The mixture was warmed and stirred in an oil bath, and the reaction temperature was elevated to 80 t, and water of the by-product was distilled off during the reaction. When the distilled water reaches the theoretical amount, the reaction is stopped and then cooled. The reaction solution was transferred to a separatory funnel, and 300 ml of benzene was added thereto, and the mixture was treated with a 1% aqueous solution of sodium carbonate and water. Thereafter, the paper is decompressed and concentrated. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -----------Installation - (Please read the notes on the back and fill out this page. ) Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumer Cooperatives Printed -45- Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumers Cooperatives, Printing 12,807,001 A7 B7 V. Inventions (43) Get 1 18g of products. This product was confirmed to be a condensate containing trimethylolpropane and fumaric acid mono(2-allyloxyethyl) by 1H-NMR, FT-IR, GC and GPC. A composition of (2-allyloxyethyl) fumarate monomer 30% (measured by GC).

IR u (C 0) = 1 72 7 cm -1 , (allyl C = C) = 1 647 cm·1 [Example 5] In a 3 L glass flask, 500·7 g of the product obtained in Example 2 was reversed. Isoic acid mono(2-allyloxyethyl), 1.8 kg of THF was fed thereto, and after the nitrogen substitution in the reaction system, 345.5 g of potassium carbonate was added. After the end of the heat, the mixture was stirred for 1 hour, and the reaction solution was cooled with ice water. Further, 524.3 g of p-toluenesulfonium chloride was dissolved in 200 g of THF to adjust the THF solution. After the reaction temperature was adjusted to below 10 ° C, the adjusted P-toluenesulfonic acid chloride / THF solution was added thereto, followed by stirring for 30 minutes. Thereafter, 70.9 g of pentaerythritol and 69 1. 1 g of potassium carbonate were added and stirred. After the end of the heat, it was cooled with ice water, and the reaction solution was returned to room temperature and stirred for additional 2 hours. The reaction liquid was concentrated, and the concentrate was transferred to a separating funnel, and 2 kg of ethyl acetate was added thereto, followed by liquid separation using a 10% aqueous sodium carbonate solution and water. Thereafter, concentration under reduced pressure was carried out to obtain 240 g of a product. The product was identified by 1H-NMR, FT-IR, GC and GPC, and it was confirmed to contain pentaerythritol and fumaric acid (2-allyloxyethyl) according to formula (21). Standard (CNS) A4 size (210X297 mm) I Clothing ------1T--------ii (Please read the notes on the back and fill out this page) -46- Ο

1287021 A7 B7 V. Condensate of Invention (44).

R v (C0) = 1 727 cm '15 v (allyl C = C) = 1 647 (Formula (21) Further, the area percentage of the obtained product obtained by GPC analysis is expressed by s of the formula (2 1 ) The contents are shown in Table 2. Table 2 S 値 4 3 2 ^ Composition (GPC area ratio, %) 88.3 2.2 9.5 The above mixture was prepared using a thin layer chromatography analyzer containing ruthenium (Pre Coated PLC Plates SILICA manufactured by MERCK Corporation) GEL 60 F-25 4 ), using ethyl acetate / hexane = 1 / 2 as the developing solvent, s 値 as the compound of 4 and 3, and reconfirm the mixture of the above by NMR. Standard (CNS) A4 specification (210X297 mm) I---------- Participation ------1T------0 (Please read the note on the back and fill out this page) Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumer Cooperatives, Printing - 47-1287021 A7 B7 V. Inventions (45) S SS 4

iH - NMR δ (ppm) 6.92 (d, 4Hf J * 15.6Hz, -〇COCH=CHCOO-), 6.85 (d, 43⁄4 15·6Ηζ, -0C0Cfi=QiC0(H,5.96~5_86 (m, 4H, CH2) =CH-CH2-), 5·30 (dd, 4H, J = 17.3Hz, J = 1.47Ηζ, Cg2=CH-CH2-), 5.22 (dd, 4H, J : 1〇·5Ηζ, J = 1.47 Hz,QJ2=OH:H2-), 4·38 仏8H, J = 4-6Hz, -O-CHs-Qiz-COO-), 4.34 (s, 8H, C-CH2-), 4.04 (d, 8H , J- 5. 4Hz, CH2=OH:H2-), 3.70 (t. 8H, J = 4.6Hz, HXUe-CHjg-COO-)

I R v (CO) = 1727cm-1 , v (allyl 0=0=1647^1 s = 3

lH-NMR δ (ppm) 6.92 (d, 3H, J = 13.9 Hz, -OCOCH=CHCOO-), 6.87 (d, 3H, 1 = 13.91^, -0(:0(^=(^(:00-) ), 5.96~5.86 (111,3 札(:1{2=<11-^12-), 5.30 (df 3H, J = 17.1Hz, CH2=CH-CH2-), 5.22 (d, 3H, J = 10.3Hz, CH2=CH-CH2-), 4.38 (t. 6H, J = 4.6Hz? -0-CH2-CH2-C00-)r 4.31 (s, 6H. C-CH2-), 4.04 (d, 6H, J = 5.9Hz, CH2=CH-CH2-), 3.70 (t, 6H, J = 4.6Hz, -0-CH2-CH2-C00-), 3.63 (s, 2H, C-Cife-).

IR v (00)=1727^1 , v (allyl C=C) =1647 cm~l [Example 6] 500·7 g of fumaric acid obtained in Example 2 was placed in a 3 L glass flask. (2-Allyloxyethyl), 1.8 kg of THF was fed thereto, and the reaction system was replaced with nitrogen, and then 345. lg of potassium carbonate was added. After the end of the heat, the mixture was stirred for 1 hour, and the reaction solution was cooled with ice water. Further, 524.3 g of p-toluenesulfonium chloride was dissolved in 200 g of THF to adjust the THF solution. Apply the Chinese National Standard (CNS) A4 specification (210X297 mm) to the standard of the paper. ----------- Install (Please read the note on the back and fill in this page) Intellectual Property Bureau employee consumption cooperative printing -48- Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 1287021 A7 B7 V. Invention description (46) After the temperature is adjusted to below 10 ° C, the adjusted P-toluene The acid chloride/THF solution was added thereto and stirred for 30 minutes. Thereafter, 93.2 g of trimethylolpropane and 691.0 g of potassium carbonate were added, followed by stirring. After the end of the heat, the ice water was removed, and the reaction solution was returned to room temperature and stirred for another 2 hours. Subsequently, the reaction liquid was concentrated, and the concentrate was transferred to a separating funnel. After adding 2 kg of ethyl acetate, a 10% aqueous sodium carbonate solution and water were used for liquid separation. Thereafter, concentration under reduced pressure was carried out to obtain 267 g of product. The product was confirmed by W-NMR, FT-IR, GC and GPC, and it was confirmed to contain trimethylolpropane and fumaric acid mono(2-allyloxyethyl) represented by formula (22). Condensate.

I R v (CO)= 1 727cm"1, v (allyl C = C)= 1 647cm'1 (22)

s+t=3 The area percentage of the obtained product obtained by GPC analysis, and the content represented by s of formula (22) is shown in Table 3. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) ----------- ------1T-------- line (please read the back first) Note: Please fill out this page again) -49- Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed 1287021 A? B7 V. Invention Description (47) Table 3 S 値 3 2^ Composition (GPC Area Rate, %) 91.8 8.2 [Example 7] In a 1 L round bottom flask equipped with a rotator, a Dimrod cooling tube, and a nitrogen introduction tube, 118.19 g of cyclohexanediol monoallyl ether and 148.71 g of anhydrous butene were added. After diacid, 268 mg of hydroquinone monomethyl ether and 363 g of toluene, the mixture was heated and stirred at 1 1 ° C for 24 hours under a nitrogen atmosphere. After 12.6 g of concentrated hydrochloric acid and 267 mg of hydroquinone monomethyl ether were added to the obtained reaction mixture, the mixture was heated under reflux for 5 hours under nitrogen. After cooling, the white precipitate was filtered through a filter of 〇.i // m mesh, and the filtrate was separated by water (500 mL x 3 times). The obtained organic layer was dried over anhydrous magnesium sulfate, and evaporated. This product was confirmed to be a fumaric acid mono(2-allyloxycyclohexyl) by j-NMR and FT-IR analysis.

IR v (C Ο Ο H) = 3 3 0 0 c m-1 ～2 5 0 0 cm ·1,}; (C Ο ) = 1 7 2 3 C = c m-1 ^ (allyl 0 = 0) =1 6460111-1 [Example 8] In a 1 L glass flask equipped with a stirring device, a thermometer, a condenser, and a moisture quantitative receiver, 161.5 3 g of the reverse-precision paper size prepared in Example 7 was applied. China National Standard (CNS) A4 Specification (210><297 mm) -----------Approving ------1T-------^ (Please read the back first Note: Please fill out this page) -50- Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed 1287021 A? B7 V. Description of Invention (48) Acetylic acid mono (2-allyloxycyclohexyl), 1 03.37 g cyclohexanediol monoallyl ether, 262.37 g of toluene, 8.6 g of p-toluenesulfonic acid, 520 mg of polymerization inhibitor 4 [methylene-3·(3,5-di-t-butyl) Methyl-4-hydroxyphenyl)propionate]methane (manufactured by Chemicals, Inc., trade name IRGANOX 1010) was added thereto. The product was heated and refluxed in an oil bath, and the by-product water was distilled off during the reaction. When the distilled water reaches the theoretical amount, the reaction is stopped and then cooled. The reaction solution was transferred to a separatory funnel, and 300 mL of toluene was added thereto, and a 1N aqueous sodium hydroxide solution and water were used for liquid separation. Thereafter, the mixture was dried over sodium sulfate and concentrated under reduced pressure to give a product of 23 0.28 g. The obtained crude product was purified by a gum column. 1 g of dimethyl phthalate (WAKO-GEL C-200, manufactured by Wako Pure Chemical Industries, Ltd.) was added as hexane, and it was poured into a 5 cm-diameter rubber column. 20.0 g of the crude product previously prepared was placed in the upper part of the column, and the crude product was dissolved in ethyl acetate/hexane = 1/10 to TLC (Pre Coated PLC Plates SILICA GEL 60 F-254 by MERCK) A fraction having an Rf enthalpy of 0.52 was collected, which was distilled under reduced pressure using an evaporator to obtain 15.1 g of pale yellow oil. This product was confirmed to be bis(2-allyloxycyclohexyl) fumarate by 1H-NMR, FT-IR and GPC.

IR v (00)=17210111^, ^ (allyl 0 = 0)=1 6470111-1 [Example 9] Applicable to the Chinese National Standard (CNS) with a stirring device, a thermometer, a condenser, and moisture. A4 size (210X297 mm), t.------IT--------ii (please read the notes on the back and fill out this page) -51 - 1287021 A7 B7 Ministry of Economics Intellectual Property 53.9 g of fumaric acid mono(2-allyloxycyclohexyl), 6 obtained in Example 7, in a 500 mL glass flask of the invention employee's consumption cooperative. Og pentaerythritol, 50 mL of toluene '811.8 mg of ρ·toluenesulfonic acid, and 54.6 g of hydroquinone monomethyl ether were fed therein. The mixture was heated under reflux in an oil bath, and water of the by-product was distilled off while the reaction was being carried out while continuing the reaction. When the distilled water reaches the theoretical amount, the reaction is stopped and then cooled. The reaction solution was transferred to a separatory funnel, and 300 mL of ethyl acetate was added thereto, and the mixture was subjected to liquid separation using a 10% aqueous sodium carbonate solution and water. Thereafter, it was concentrated under reduced pressure using sodium sulfate to give 38.9 g of product. This product was confirmed to be a condensate containing pentaerythritol and fumaric acid mono(2-allyloxycyclohexyl) by 1H-NMR, FT-IR, GC and GPC. A composition of 40% (measured by GC) of allyloxycyclohexyl) fumarate monomer.

IR v (CO) = 1 723 cm '1 v v (allyl C = C) = 1 645 cm '1 [Example 1 〇] 60.8 obtained in Example 7 in a 3 L glass flask equipped with a stirring device g of fumaric acid mono(2-allyloxycyclohexyl) and 200 mL of THF were fed thereto, and after the nitrogen substitution in the reaction system, 22 g of potassium carbonate was added. After the end of the heat generation, the mixture was stirred for 1 hour, and the reaction liquid was cooled with ice water. Further, when the temperature of the reaction liquid fell below 1 〇 ° C, 7.6 g of P-toluenesulfonium chloride was added and stirred for 30 minutes. After the addition of 5.4g of pentaerythritol, the paper scale applies to the Chinese National Standard (CNS) VIII 4 specifications { 210X297 mm) ------Install ------ order---S--1 line ( Please read the notes on the back and fill out this page.) -52- 1287021 A7 B7 V. INSTRUCTIONS (5〇) Stir. The reaction solution was returned to room temperature and stirred for further 12 hours. Subsequently, the reaction liquid was concentrated, and the concentrate was transferred to a separating funnel, and 500 mL of ethyl acetate was added thereto, followed by liquid separation treatment using a 1% by weight aqueous sodium carbonate solution and water. Thereafter, concentration under reduced pressure was carried out to obtain 30 g of a product. This product was confirmed to be a condensate containing pentaerythritol of the formula (23) and mono(2-allyloxycyclohexyl) fumarate as determined by 1H-NMR, FT-IR and GPC.

IRV (CO)=l 723cm'1, v (allyl C = C) = 1 6 4 5 cm"1 (23) ------Women-- (Please read the notes on the back and fill in the form) Page)

Line The Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperatives, Printed, and the area percentage of the obtained product as a result of GPC analysis. The contents expressed by s of equation (23) are shown in Table 4. Table 4 S 値 4 3 2^ Composition (GPC area ratio, %) 82.2 2.0 15.8 [Example 1 1] This paper scale applies to China National Standard (CNS) A4 specification { 210X297 mm) -53- 1287021 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed A7 B7 V. Inventive Note (Μ ) 〇1 In a 3L glass flask with a dropping funnel, 1400g of allyl alcohol, 351.6g of aluminum (Alumina N Super I ICN 500 g of phenylethylene oxide injected into the dropping funnel was placed therein, and it was dropped by heating to 50 ° C under a nitrogen atmosphere. After the completion of the dropwise addition, heating and stirring were carried out for 10 hours. After cooling, the aluminum was filtered off with a filter of 〇·1 // m mesh, and the filtrate was removed by an excess of allyl alcohol using an evaporator. The obtained concentrate was subjected to reduced pressure distillation to obtain 592 g of a mixture of 2-allyloxy-1-phenylethanol and 1-allyloxy-2-phenylethanol (yield 80%).

IR v (OH) = 3443cm-1? ^(ΡΙι,εί^^Βί^ΟοΓη^ΝΒίηΟοπΓ1, v (allyl C = C) = 1 647cm'1 bp = 136〇C (13Torr) [Example 1 2] A 2 L round bottom flask equipped with an induction stirring device, a Dimrod cooling tube, and a nitrogen introduction tube was charged with 322.9 g of the 2-allyloxy-phenylethanol obtained in Example 11 and 3 54.9. g anhydrous maleic acid, 1.36 g of hydroquinone monomethyl ether, 677.5 g of toluene, and then heated and stirred at 130 ° C for 5 hours under a nitrogen atmosphere. After cooling, under a nitrogen atmosphere of adding 80 g of concentrated hydrochloric acid The mixture was stirred at an oil bath temperature of 130 ° C for 1 hour, and after cooling, the precipitated fumaric acid was filtered off, and the filtrate was dried with anhydrous sodium sulfate, and concentrated under reduced pressure using an evaporator. The obtained reaction liquid is put into hexane, and the precipitated white solid is filtered off, and then dried under reduced pressure to obtain a white solid paper scale applicable to China National Standard (CNS) A4 specification (210×297 mm) ------- ----^------1T------^ (Please read the notes on the back and fill out this page) -54- 1287021 Ministry of Economic Affairs Intellectual Property Bureau employees A7 B7 co five printed, a description of fumaric acid (2-allyloxy - phenyl-ethyl) - (52) of the invention, the body 3 75.8g (yield 75 · 1%).

I R

^(COOH) = 3400cm_1 〜2560cm-1 > (CO)=1623cm-1, v (allyl C = C) = 1 645cm-1 ιη·ρ· 71.2~71.4°C [Example 1 3] Attached 138.14 g of fumaric acid mono(2-allyloxy-phenylethyl) prepared in Example 12 in a 500 mL glass flask of a stirring device, a thermometer, a condenser, and a moisture metering receiver. 89.1 25 g of 2-allyloxy-phenylethanol, 150 mL of benzene, 2.76 g of p-toluenesulfonic acid, and 138 mg of hydroquinone monomethyl ether were fed therein. Heating under reflux in an oil bath was carried out while the water of the by-product was distilled off while the reaction was continuing. When the distilled water reaches the theoretical amount, the reaction is stopped and then cooled. The reaction solution was transferred to a separatory funnel, and 300 mL of benzene was added thereto, and the mixture was treated with a 1% aqueous sodium hydroxide solution and water. Thereafter, it was concentrated under reduced pressure using sodium sulfate to give 200 g of crude material. The obtained crude product was recrystallized from hot hexane to give a white solid. The obtained white solid was confirmed to be bis(2-allyloxy-cyclohexyl) fumarate by 1H-NMR, FT-IR and GPC. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210Χ297 mm). Installation, order--------ii (please read the note on the back and fill out this page) -55- 1287021 A7 B7 Economy Ministry of Intellectual Property Bureau employee consumption cooperative printing 5, invention description (53)

I R

2; ( P h,C Η) = 3 0 5 0 c ηΓ1 〜3 0 3 0 cm ·1 u (C = 0) = 1725cm-1, v (allyl 0 = 0)=1 6470111^ mp 68.3-68.5 〇C [Example 1 4] 75.7 g of fumaric acid mono(2-allyloxy-phenylethyl), 355.6 g of THF obtained in Example 12 were placed in a 1 L glass flask. After feeding in, the reaction system was replaced with nitrogen, and then 38 g of potassium carbonate was added. After the end of the heat, the mixture was stirred for 1 hour, and the reaction solution was cooled with ice water. Further, 5 1.5 g of p-toluenesulfonium chloride was dissolved in 89 g of THF to adjust the THF solution. After the reaction temperature s was rounded to 1 〇 C or less, the adjusted p-toluene mineral acid chloride/THF solution was added thereto, followed by stirring for 30 minutes. Thereafter, 7.5 g of pentaerythritol and 82.2 g of potassium carbonate were added and stirred. After the end of the heat generation, it was cooled with ice water, and the reaction solution was returned to room temperature and stirred for additional 5 hours. Then, the reaction liquid was concentrated, and the concentrate was transferred to a separating funnel, and 1 kg of ethyl acetate was added thereto, followed by liquid separation treatment using a 1% aqueous solution of sodium carbonate and water. Thereafter, the organic layer was concentrated under reduced pressure to give 32.5 g of product. The obtained crude product was purified by a gum column. 1 kg of tannin (WAKO-GEL C-200, manufactured by Wako Pure Chemical Industries, Ltd.) was added as hexane, and it was poured into a rubber column tube having a diameter of 10 cm. The crude product previously prepared was placed in the upper part of the column, and the crude product was dissolved in ethyl acetate/hexane = 1/20 to TLC (Precoated by MERCK). The paper was applied to the Chinese National Standard (CNS) A4. Specifications (210X297 mm) .3⁄4., order-------I^ (Please read the note on the back and fill out this page) -56- 1287021 A7 B7 V. Description of invention (54) PLC Plates SILICA GEL 60 F-254 ) A fraction of Rf 値 0.50 (eluent: ethyl acetate / hexane = 1/2) was collected and evaporated under reduced pressure to give a pale yellow oil. This product was confirmed by the results of 1H-NMR, FT-IR and G P C to be a condensate of pentaerythritol and anti-succinic acid-*(2-propenyloxy-phenyl-ethyl), S. I R v (Pl^CHHOSOcnT1 ~3 03 0cm-1 v (00)=17250111^, ^ (allyl 0 = 0)=16470111-1 (25)

I------------------------- 3 obtained mixture of 50 g, 50 g of toluene, 10 mg of hydroquinone monomethyl ether (MEHQ), 15 g of 5% Pd-Al203 was replaced by nitrogen in the reaction system, and then heated and stirred at 140 ° C. 3 After the cooling, 5% Pd-Ah 3 was removed from the reaction mixture by filtration, and the filtrate was evaporated under reduced pressure of toluene to give a pale yellow viscous liquid (48 g). It is determined by 1H-NMR, and the acryl paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -57- 1287021 V. Invention description () 55 base and propylene-based peak comparison results show that there are 98 % is isomerized to a propylene group. The mixture obtained in Example 4, Example 5, Example 6, Example 7, and Example 8 was subjected to isomerization reaction in the same manner. The results are shown in Table 5. Table 5 Addition ratio reaction result Example Reaction used in the example Raw material (g) Toluene (g) Catalyst (g) MEHQ 〇g) Isomerization ratio (%) 15 3 50 50 15 10 98 16 4 50 50 15 10 100 17 5 85 85 25 18 100 18 6 50 50 15 10 98 19 7 50 50 15 10 98 20 8 50 50 15 10 99 [Example 45]

20.0 g of fumaric acid, 37.22 g of cyclohexane oxide, 60.8 g of 1,4-dioxane, and 3.7 g of aluminum (Alumina N Super I manufactured by ICN Co., Ltd.) were added to have a cooling tube 3 In a 00 mL glass flask, after the reaction was replaced with nitrogen, the mixture was heated and stirred at an internal temperature of 60 ° C for 13.5 hours. The obtained reaction mixture was filtered through a membrane filter, and the filtrate was evaporated under reduced pressure to give 40.7 g of a liquid. With a stirring device, thermometer, condenser, moisture quantitative acceptance of this paper scale applicable to China National Standard (CNS) A4 specifications (210X297 mm), wholesale -- (please read the back of the note before filling out this page) Order-彳线· Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperative Printed-58- Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1287021 A7 A7 B7 V. Invention Description () 56 OOmL glass flask, the above will be recorded 10.3 g of a transparent oily liquid, 17 g of fumaric acid mono(2-allyloxycyclohexyl) obtained in Example 7, 26.7 g of toluene, 33 8.2 mg of p-toluenesulfonic acid, 10 ml of a polymerization inhibitor, hydroquinone monomethyl ether, was fed therein. The mixture was heated and refluxed in an oil bath, and water of the by-product was distilled off while the reaction was being carried out while continuing the reaction. When the distilled water reaches the theoretical amount, the reaction is stopped and then cooled. Toluene was distilled off from the reaction mixture by distillation under reduced pressure, and the obtained yellow viscous material was added with a small amount of ethyl acetate, and then placed in hexane to be reprecipitated. The obtained white viscous material was washed with water and then washed with hexane to yield 15 g of white solid. The obtained white solid was confirmed to be a polycondensate of 1,2-cyclohexanediol and fumaric acid and allyl alcohol by 1H-NMR, FT-IR and GPC. [Example 2 1] ^ 34 g of the crude product obtained in Example 14, 90 g of toluene, 10 mg of hydroquinone monomethyl ether (MEHQ), 3.13 g of carbonyl chlorohydride tris(triphenylphosphine) ruthenium (II) Feeding, the reaction was replaced with nitrogen, and then heated and stirred at 140 ° C for 30 minutes. After the reaction was cooled, toluene was distilled off from the reaction mixture under reduced pressure to give a pale yellow viscous liquid (33 g). As a result of comparison with the peak of the allyl group and the propylene group as determined by 1H-NMR, it was found that 98% was subjected to isomerization to a propenyl group. [Example 22-3 5] The fumarate of the present invention obtained in the above examples was applied onto a glass substrate, and after UV hardening or heat hardening, the surface of the cured film was investigated for the hardness of the paper. China National Standard (CNS) A4 Specification (21〇x297 mm) ----------- Participate in ------tT------^ (Please read the notes on the back first) Fill in this page) -59- 1287021 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description () 57 degrees. Further, the surface hardness was based on the pencil hardness of JIS K5400. The results are shown in Table 6. Table 6 Fumarate Derivatization Hardening Condition Pencil Hardness Initiator Temperature-Time/UV Irradiation Example 22 Compound Heat of Example 1 >frrr- No 1 50 °C -1 h 5H Implementation Example 23 Compound of Example 3 Heat No 1 50 ° C -1 h 6H Example 24 Compound of Example 4 Heat DCPU 2% 1 50 ° C - 0.5 h 6H Example 25 Compound of Example 5 Thermal DCP1 j2% 1 50 °C - 〇. 5 h 7H Example 26 Compound of Example 6 UV IRG1 842; 5% 900mj/cmi 6H Example 27 The compound of Example 8 is hot Μ j\\\ 1 5 0 〇C -1 h 7H Example 28 Compound of Example 9 UV IRG184Z) 5% 3 00 mj/cmz 7H Example 29 Compound of Example 10 UV IRG184Z) 5% 3 00 mj/cm 2 6H Example 30 Compound of Example 14 Heat M j\ \\ 1 50 ° C -1 h 6H Example 31 The compound of Example 17 UV IRG1 842j5% 300 mj/cm 2 7H Example 32 The heat of the compound of Example 17 >fnT ilir J\\\ 1 50 °C - 1 h 8H Example 33 Compound of Example 18 Hot 4 ml 111 II 1 50 ° C -1 h 7H Example 34 Compound of Example 20 UV IRG1 842J5% 3 00 m j/cm^7H Example 35 Compound of Example 21 Thermal 4rrr M 1 50 °C -1 h 6H Comparative Example 1 Compound of Comparative Example 1 UV IRG1 842j5% 1 200 mj/cm 2 HB Comparative Example 2 Compound of Comparative Example 2 Thermal DCPlj2% 1 50 °C -1 h 2H (1 ) DCP ··Diisopropylphenyl peroxide; (2) IRG 184 : Yaljia-184 (1-hydroxy-cyclohexyl phenyl ketone) Bajiajite company system ------ wholesale clothing -- (Please read the back note and then fill out this page) Customize the paper size for the Chinese National Standard (CNS) A4 specification (210X297 mm) -60- 1287021 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperatives Printing V. Inventive Note (Μ) 58 [Comparative Example 1] 144 g of dimethyl fumaric acid was placed in a 1 L flask equipped with a distillation apparatus. An ester, 245 g of ethylene glycol monoallyl ether, and 2 g of dibutyltin oxide were placed therein, and heated at 140 ° C under nitrogen to distill off methanol as a by-product. When the methanol reaches 70% of the theoretical amount, the reaction system is slowly depressurized, the methanol is distilled off, and finally the pressure is reduced to about 400 Pa, and the theoretical amount of methanol and the residual ethylene glycol monoallyl ether are completely distilled off. After the reaction solution was cooled to room temperature, 283 g of the product was taken. The obtained product was confirmed to be bis(2-allyloxyethyl) fumarate by h-NMR and FT-IR. The obtained product was coated on a glass substrate and passed through UV. After hardening, the surface hardness of the cured film was investigated. Further, the surface hardness was based on the pencil hardness of Jis K5400. The results are shown in Table 6. [Comparative Example 2] In a 1 L flask equipped with a distillation apparatus, 144 g of dimethyl fumarate, 279 g of hydroxybutyl vinyl ether, 0.2 g of zinc acetate, and 3 g of a polymerization inhibitor were added. The IRGANOX 1010 was fed therein and heated to 1 40 ° C under nitrogen to distill off the by-product methanol. When methanol reaches 70% of the theoretical amount, the reaction system is slowly depressurized, the methanol is distilled off, and finally the pressure is reduced to about 400 Pa, and the theoretical amount of methanol and the remaining ethylene glycol monoallyl are completely distilled off. After the reaction solution was cooled to room temperature, 297 g of bis(4-vinyloxybutyl) fumarate was obtained. This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) I^1T------η—^ (Please read the note on the back and fill out this page) -61 - 1287021 A7 __B7 V. DESCRIPTION OF THE INVENTION (μ) 59 The obtained product was applied onto a glass substrate, and after heat curing, the surface hardness of the cured film was examined. Further, the surface hardness was based on the pencil hardness of JIS K5400. The results are shown in Table 6. [Examples 36-42, 46] [Comparative Examples 3 and 4] The composition of the fumarate of the present invention was applied onto a PET film or a glass substrate, and cured by UV or heat, and then investigated for hardening. The surface hardness of the film. Further, the surface of the cured film is not adhesive and has no corrugation, and the corrugability is ◦, and the adhesion is indicated by X. Hardening is carried out according to the following conditions. (i) 1 thermosetting temperature 150 ° C - 1 hour (ii) 2 UV hardening Starting agent: Yaljia - 1 84 5% Irradiation · · 3 00 mj / cm 2 The results are shown in Table 7. 1^1T------,—^ (Please read the notes on the back and fill out this page.) Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumer Cooperatives, Printed Paper Size Applicable to China National Standard (CNS) A4 Specification (210X297)厘) -62- Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1287021 A7 B7 V. Invention Description (60) Table 7

实 实 比 比 施 施 施 施 施 施 施 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例 例50 Heavy Example 17 Compound 50 80 50 60 Amount Example 18 Compound 80 Comparative Example 45 Compound 70% pe-ta3) 50 100 80MFA4) 20 100 85245) 20 20 BPF6) 30 50 50 20 30 Hardening Method 1 1 1 1 2 2 2 1 1 2 Membrane corrugated pencil hardness 〇〇〇〇〇〇〇〇X 〇5H 6H 7H 6H 2H 2H 2H 5H - F Substrate glass glass glass PET PET PET glass PET (3) PE-ΤΑ: Pentaerythritol triacrylate (4) Epoxy ester 80MFA: Epoxy acrylate ester brand name (5) Unsaturated polyester 8524: Product name (6) made by Japan Hibiya Company BPF: Double [2- ( 1-propenyloxy)ethyl fumarate] [Example 43] The bis(2-allyloxy-phenylethyl) fumarate described in Example 13 was used. After melting at 80 ° C, the initiator 1,1-bis(t-hexyl peroxide) 3,3,5-trimethylcyclohexane to bis(2-allyloxy-benzene Base ethyl) fumarate added 2% by mass and at 110 ° C (1 hour) This paper scale applies to Chinese National Standard (CNS) A4 specification (210X297 mm) ------- ----赛------, order----- (please read the note on the back and fill out this page) -63- Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1287021 A7 A7 B7 V. Description of the invention (α)

After D I, injection molding hardening was carried out at 130 ° C (1 hour). The refractive index of the obtained cured product was measured, and it was found that nD = 1.55 73. [Example 44] The condensate of pentaerythritol and fumaric acid mono(2-allyloxy-phenylethyl) described in Example 14 was added with 1% by mass of t- as a starter. Hexylperoxy-2-ethylhexanone ester was injection-hardened at 80 ° C (1 hour) at 80 ° C (1 hour). The refractive index of the obtained cured product was measured, and it was found that nD = 1.5520. [Comparative Example 5] To the bis(allyloxyethyl) fumarate of Comparative Example 1, 2% by mass of 1, as a starter, b (t-hexyl peroxide) 3 was added. After injection molding, 3,5-trimethylcyclohexane was subjected to injection molding hardening. The refractive index of the obtained cured product was measured, and it was found that the nD was 1.5132. [Effects of the Invention] As described above, the fumarate of the present invention has a terminal amino group which is more copolymerizable with the fumarate group than the conventional one. The degree of crosslinking can be increased, so that a hardened material having excellent surface hardness can be provided. Further, even if it is a composition obtained from another polymerizable cured product, it can be used for the purpose of improving the curability and surface hardness. Further, in the case of an aromatic group-containing fumarate having an extremely high refractive index of 1.55 or more, it can be applied to a technical field requiring an extremely high refractive index. This paper scale applies to China National Standard (CNS) A4 specification (210X29? mm) I Clothing ------1T-------— ^ (Please read the back note first and then fill out this page ) -64-

Claims (1)

1287021 铋1 C8 D8 .· . . . * 'ΤΙ干·X1 &, Patent Application No. 1, a fumarate containing at least one terminal group of the group represented by formula (1), and (2) The base shown is a repeating unit; Formula (1) R1〆0" Formula (2 0 (where R1 is independent of formula (3) or formula (4), again, formula (1) Or in the formula (2), X^X2 are each independently an organic residue derived from a polyol having 2 to 6 carbon atoms and having 2 to 30 carbon atoms; X1, X2 may be bonded via an ester, or a formula (1) As a terminal group, the group represented by the formula (2) is formed into a repeating unit having a branched structure) (3) ---------^------ Al---10 (please read the news on the back of the page and fill out this page again) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed in 2 R Basic I-sheet To 11 number of carbon or sub-hydrogen mono-alcohols, each of which is a 3 R alkyl group of H 11 to 11 carbon or a sub-hydrogen of 4 R in the country of the country. 1 7 7 29 -65 - 1287021 A8 B8 C8 D8 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing VI. Patent application scope 2. A fumarate containing at least one end group of formula (丨) and formula (2) The group shown and/or the group represented by the formula (5) is used as a repeating unit; Formula (1) r1Ax Wide formula (2) Formula (5) 〆〆〇, (In the formula (1), 'R1 is independent Formula (3) or (4), in addition, in the formula (1), the formula (2) or the formula (5), each of the two groups has 2 to 6 hydroxyl groups and has a carbon number of 2 to 30. An organic residue derived from a polyol; wherein X1, X2, and X3 may be bonded via an ester bond and/or an ether, or a formula (1) may be used as a terminal group to include a group represented by the formula (2) And / or the formula (<) shows a repeating unit with a branched structure) (3) This paper scale applies to the Chinese National Standard (CNS) Α 4 specification (210X297 mm) - --------^------Book--J--- (Please read the ## on the back of the note and fill out this page) -66- 1287021 A8 B8 C8 D8 hole, patent application scope V" (In the formula (3), R2 and R3 are each independently hydrogen atom or a fluorenyl group having 1 to 5 carbon atoms. Formula (4) R4 丨一 | (In the formula (4), R4 is a hydrogen atom or a carbon number of 1 To 11 alkyl). 3. The fumarate according to claim 1 or 2, wherein the number of repeating units represented by the formula (2) is in the range of 2 to 10, 4, as in the patent application scope 2 The term of the fumarate wherein the number of repeating units represented by the formula (5) is in the range of 2 to 5. 5. The fumarate according to claim 1 or 2, wherein, in the formula (1), 80% or more of the formula (1) is the formula (4). 6. The fumarate according to claim 1 or 2, wherein R4 of the formula (4) is at least one selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, a η-propyl group and an iso- A group of butyl groups. 7. The fumarate according to item 2 of the patent application, wherein X1, X2 and X3 of the formula (1), the formula (2) and the formula (5) are each independently derived from an alkanediol or an alicyclic ring. An organic residue derived from at least one alcohol in a group of a diol and an aromatic diol. 8. For example, the fumarate in the scope of patent application No. 7, wherein the alkanediol is represented by formula (6); the paper scale is applicable to China National Standard (CNS) Α4 specification (210Χ297 mm) n I n Install """ Order -1 - τ I line (please read the note on the back of the section and then fill out this page) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed -67- 1287021 A8 B8 C8 D8 Patent application scope (6 R5 and R6 are each a hydrogen atom or a formula (7) Formula (7) (In the formula (7), R7 is a hydrogen atom or a carbon number of 1 to 3, a gamma yoghurt 9, as in claim 1 or 2 In the case of butyl sulfonate, at least one of the terminal groups is a group represented by the formula (8); wherein (0) wherein 0 0 1 〇, a fumarate represented by the formula (9)-- ----- 参 _ order---.---T- raise, (please read the notes on the back first to fill the basics) Ministry of Economic Affairs Intellectual Property Bureau employees consumption cooperatives printed (9 (In the formula (9), X4 is a compound in the formula (9), wherein each of the d X4 groups is independently an alkyl group or a cycloalkyl group having a carbon number of 5 to 12, and d is an integer of 1 to 5 In addition, R2 and R3 are independent hydrogen atoms or carbon numbers 1 to 5. The paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -68- 1287021 A8 B8 C8 D8 VI. Patent application scope Alkyl). 1. 1. In the case of the fumarate formula (9) of claim 10, X4 is an alkylene group represented by formula (6); wherein (6) wherein /R5 Each of R5 and R6 is a hydrogen atom or a formula (7): wherein R7 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms in the formula (7). 1 2. The fumarate according to claim 1 or 2, wherein at least one of the terminal groups is a hydroxyl group. 13. A fumarate represented by formula (10), formula (1 〇) #-- (please read the notes on the back and fill out this page) - Line · Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative system 0 b (in the formula (1 〇), z is a trivalent to hexavalent polyol organic residue, R1 is independently of the formula (3) or (4), and X5 is in the formula (10), a is present In X5, each independently is an alkyl group or a cycloalkyl group having a carbon number of 5 to 12, & is an integer of 1 to 5, 1) is an integer of 1 to 6, (: is a whole paper of 〇 to 5 The standard uses China National Standards (CNS) A4 specifications (210X297 mm) -69-1268711 A8 B8 C8 D8 Ministry of Economic Affairs Intellectual Property Bureau employees consumption cooperatives printed six, the number of patent applications, and b + c is 3 to 6 In the formula (3), R2 and R3 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Formula (4) R4—(-) In the formula (4), R4 is hydrogen. Atom or an alkyl group having 1 to 11 carbon atoms). 14. The fumarate according to Item 13 of the patent application, wherein, in the formula (10), X5 is an alkylene group represented by the formula (6); R5 and R6 are each a hydrogen atom or a formula (7) Formula (7) (in the formula (7), R7 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms) 15. A fubutene represented by the formula (11) Diester, this paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) * Binding: 7 lines (please note the back of the #闳#) and fill in this page -70- 1287021 A8 B8 C8 D8 Patent range (11) R1 ,〇-^-CH=CH-C-CT Ο R6 Ο. (In the formula (11), R1 is an independent formula (.3) or a formula (4 is an integer of 1 to 5 independently). (3) (In the formula (3), R2 and R3 are independent hydrogen atoms or a carbon number of 1 to 5). (4) R4-Printed by the Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative (in the formula (4), R4 is a hydrogen atom or an alkyl group having 1 to 11 carbon atoms (wherein R5 and R6 are each a hydrogen atom or a formula (7)). (7) (In the formula (7), R7 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ). 16. A method for producing a fumarate, which is applicable to the Chinese National Standard (CNS) for the scale of the anti-butyl paper according to any one of claims 1 to 9 and the scope of the patent application. A4 size (210X297 mm) ϋ n I n 11 ^ nn ΙΊ 1_ϋ n (Please read the «Precautions on the back page and fill out this page again) -71 - 1287021 A8 B8 C8 D8 VI. Application for patent range Adipic acid ester The manufacturing method is characterized in that at least one of the terminal groups is a fumarate having the formula (8) and having the formula (2) as a repeating unit, and having a carbon number of 2 to 6 hydroxyl groups of 2 to 6 A method in which an alcohol is reacted in the presence of a catalyst. 1 . A method for producing a fumarate, which is a method for producing a fumarate according to Item 13 of the patent range, wherein at least one of the terminal groups has the inverse of the formula (8). a method for producing a fumarate and a polyol having 2 to 6 carbon atoms and having 2 to 30 carbon atoms in the presence of a catalyst, and a method for producing a fumarate The method for producing a fumarate according to any one of claims 1 to 9 and the scope of claim 12, wherein at least one of the terminal groups has the formula (8) and has the formula ( 2) A method in which a fumarate as a repeating unit and a polyhydric alcohol having 2 to 6 carbon atoms of 2 to 6 hydroxyl groups are reacted in the presence of a condensing agent and a base. A method for producing a fumarate, which is a method for producing a fumarate according to Item 13 of the patent application, wherein at least one of the terminal groups has the inverse of the formula (8) A method in which a butylene diester and a polyol having 2 to 6 carbon atoms and having 2 to 30 carbon atoms are reacted in the presence of a condensing agent and a base. 20. The method of claim 18, wherein the condensing agent is sulfonium chloride. 2 1. The manufacturing method according to any one of claims 16 to 19, wherein a polyol having 2 to 6 carbon atoms and having 2 to 30 carbon atoms is applicable to the Chinese national standard ( CNS ) A4 size (210X297 mm) #-- (Please read the note on the back and fill out this page) Order i-line Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed -72- 1287021 A8 B8 C8 D8 夂, Patent application scope (please read the note on the back and fill out this page). At least one selected from the group consisting of trimethylolpropane, trimethylolethane, pentaerythritol, ditrimethylolpropane and dipentaerythritol, and It is grouped with additives such as ethylene oxide and propylene oxide. A method for producing a fumarate having a terminal group having a group represented by formula (4), which is a terminal group having a terminal group having a group represented by formula (3), wherein The reaction is carried out in the presence of a catalyst for isomerization reaction of the terminal group, and the terminal group is converted into a group represented by the formula (4). 23. The method of claim 22, wherein the terminal group has a fumarate of the formula (3), which is the inverse of any one of claims 1 to 15. Butene ester. 24. The method of claim 22, wherein the isomerization reaction is carried out in a terminal group of a fumarate represented by the formula (3), and more than 80% of the formula (3) Transform to the formula (4). The method of any one of claims 22 to 23, wherein the catalyst used in the isomerization reaction is a catalyst containing at least one of palladium, rhodium, and iridium. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, Employees' Consumption Cooperatives. 26. A polymerizable composition containing the fumarate of any one of claims 1 to 15. 27. The polymerizable composition of claim 26, which comprises, in the range of claims 1 to 15, the fumarate 1% by mass to 99% by mass and at least one selected from the group consisting of The paper size of saturated polyester and (meth) acrylate is based on the Chinese National Standard (CNS) A4 specification (210x297 mm) -73- 1287021 A8 B8 C8 D8 ~, the patent range oligomer and free polymerizable single The compound in the body group is 1% by mass to 99% by mass. 0 28. A polymerizable composition containing the polymerizable composition of claim 26 or 27 and 1 part by mass of the free polymerization initiator Parts by mass to 15 parts by mass. A cured product obtained by hardening a polymerizable composition according to any one of claims 26 to 28 of the patent application. 3 〇, a fumarate, which contains at least one terminal group represented by formula (1) of claim 1 and contains the formula (2) of claim 1 base. 3 1. A fumarate comprising at least one terminal group represented by formula (1) of claim 1 and containing the formula (2) of claim 1 Base and/or base of formula (5) of claim 2 of the patent scope. 32. A fumarate represented by formula (24); formula (24) (please read the back of the note first and then fill out this page) Order Printed by the Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative Ο R1 0, (in the formula (24), R1 is independent of the formula (3) or formula (4), p is 1 table paper size, using the Chinese National Standard (CNS) A4 specification (210X297 cm) -74-1287021 A8 B8 C8 D8 VI. Patent application range to the integer of 9) Equation (3) (In the formula (3), R2 and R3 are each independently hydrogen atom or a group having 1 to 5 carbon atoms. Formula (4) R4—«— (In the formula (4), R4 is a hydrogen atom or a carbon number of 1 to 11 Alkyl). (Please read the note on the back of the page and then fill out this page.) Printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs. This paper scale uses the Chinese National Standard (CNS) A4 specification (210X297 mm) -75-