JP2005120012A - Polymerizable hydrosilylated norbornene monomer and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide new monomers which reduce an odor and toxicity and excel in active energy ray curability. <P>SOLUTION: Polymerizable hydrosilylated norbornene monomers are obtained by reacting a hydrosilylated norbornenecarbonylic acid derivative (I) having at least one structural unit represented by formula (1) (wherein X is 1 or 2; R<SP>1</SP>and R<SP>2</SP>are each hydrogen or a carboxy group but both are not hydrogens at the same time, and R<SP>1</SP>and R<SP>2</SP>may form an acid anhydride group with each other; and R<SP>3</SP>is hydrogen or a 1-3C alkyl group) in the molecule with a polymerizable monomer (II) having an α, β-unsaturated double bond. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a hydrosilylated norbornene-based polymerizable monomer and a method for producing the same. More particularly, the present invention relates to a hydrosilylated norbornene obtained by reacting a hydrosilylated norbornene carboxylic acid or hydrosilylated norbornene dicarboxylic acid anhydride with a polymerizable monomer having an α, β-unsaturated double bond. The present invention relates to a polymerizable monomer and a method for producing the same.

  Conventionally, (meth) acrylate monomers and oligomers and polymers obtained by homopolymerizing or copolymerizing the monomers are used in various applications such as adhesives, coating agents for inks, paints, etc. Although it has been awarded as a component, recently, the required performance for the resin component has become more sophisticated as the usage environment in these applications changes. For example, in urethane acrylate, a urethane bond is introduced in order to impart flexibility. However, due to the influence of the bond, the viscosity of the acrylate tends to increase, and therefore a reduction in viscosity is required. In addition, as a hard coating material to be applied to flexible molded products, it is not only necessary to be hard, but it is also necessary to have appropriate flexibility. Therefore, (meth) acrylic monomers and oligomers that can satisfy these performances at the same time. Development is required.

  Also, in active energy ray curable coating applications, odors and various toxicities (acute toxicity, subacute toxicity, mucous membrane irritation) from the viewpoint of environmental and work safety when these monomers and oligomers are used as reactive diluents. The demand for the development of new monomers and oligomers that can reduce skin sensitization and skin sensitization is also increasing.

  In view of such a technical background, the present applicant pays attention to organosiloxane derivatives, organic-inorganic hybrid materials having active energy ray curability (hydroxyl group-containing (meth) acrylic monomers and oligomers, tetraalkoxysilanes or partial hydrolysis thereof). A reaction product with a condensate and an active energy ray-curable resin composition containing the product are proposed (see Patent Document 1).

  An invention relating to a method for producing a compound useful as an adhesion promoter for a room temperature vulcanizable organopolysiloxane composition, that is, a dianhydride-terminated polyorganosiloxane has been disclosed (see Patent Document 2).

JP 2000-191710 A

JP-A-5-86071

  An object of the present invention is to provide a novel monomer or oligomer having low odor and low toxicity and excellent in active energy ray curability.

  As a result of intensive studies to solve the problems of the prior art, the present inventor has a specific hydrosilylated norbornene polymerizable monomer having both an organosiloxane moiety, a norbornane moiety, and a (meth) acryloyl moiety. It has been found that the present invention can provide a cured product having low viscosity, low odor, excellent active energy ray curability, low curability shrinkage, excellent adhesion to a glass substrate, and excellent transparency. It came to be completed.

  That is, the present invention relates to the general formula (1):

(In the formula, X is 1 or 2, R ¹ and R ² each represent a hydrogen atom or a carboxyl group, but they are not both hydrogen atoms, and R ¹ and R ² are each an acid anhydride group. R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), and a hydrosilylated norbornenecarboxylic acid derivative (I) having at least one structural unit in the molecule, α The present invention relates to a hydrosilylated norbornene-based polymerizable monomer obtained by reacting a polymerizable monomer (II) having a .beta.-unsaturated double bond. Further, the present invention provides a hydrosilylation in which the hydrosilylated norbornene carboxylic acid derivative (I) and a polymerizable monomer (II) having an α, β-unsaturated double bond are heated and reacted in the presence of a hydrosilylation catalyst. The present invention relates to a method for producing a norbornene-based polymerizable monomer.

  The hydrosilylated norbornene-based polymerizable monomer of the present invention is not only excellent in active energy ray curability but also has good color tone and transparency, low viscosity and low odor, and curable shrinkage. There are few features such as excellent adhesion to glass. Those having a small introduction amount of (meth) acryloyl groups are suitable as reactive monomers, and those having a large introduction amount are useful as reactive crosslinking agents, reactive curing agents and the like.

  The hydrosilylated norbornene-based polymerizable monomer of the present invention comprises a raw material hydrosilylated norbornenecarboxylic acid derivative (I) (hereinafter referred to as component (I)) and a polymerization having an α, β-unsaturated double bond. Monomer (II) (hereinafter referred to as component (II)). Component (I) is usually obtained by reacting the following specific organosiloxane (hereinafter referred to as (Ia)) with a norbornenecarboxylic acid derivative (hereinafter referred to as (Ib)). Component (Ia) needs to have at least one silyl group (SiH) in the molecule in order to react with component (Ib). Component (Ia) is represented by the general formula (2):

(Wherein R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n represents an integer of 1 to 100). In the formula, among 2n + 3 R ³ , one is a hydrogen atom and the rest is preferably an alkyl group having 1 to 3 carbon atoms. Of the alkyl groups having 1 to 3 carbon atoms, those having 1 to 2 carbon atoms are preferable. As described above, the component (Ia) may be an organosiloxane having at least one silyl group (SiH) in the molecule, and the content of the silyl group is that of the component (Ib) in the component (I) to be obtained. The amount can be determined appropriately in consideration of the amount introduced, the amount of component (II) introduced in the resulting hydrosilylated norbornene polymerizable monomer, and the like. When the amount of silyl group is too small, the amount of component (Ib) introduced in component (I) obtained and the amount of component (II) introduced in the hydrosilylated norbornene-based polymerizable monomer obtained are too small. It is not possible to obtain a hydrosilylated norbornene polymerizable monomer. Usually, the content of SiH in component (Ia) is 0.5 to 1.7 (g equivalent / 100 g). In addition, since the activity of hydrosilylation with component (Ib) is high, the silyl group in component (Ia) may exist not only in the molecular end but also in the molecule. Moreover, since the chain structure in the siloxane bond can be appropriately adjusted according to the number of repeating units of the siloxane bond (—Si—O—) in the component (Ia), the resulting hydrosilylated norbornene-based polymerizable monomer The flexibility of the induced active energy ray cured film can be appropriately adjusted. The molecular weight of component (Ia) can be appropriately determined in consideration of workability such as the viscosity of the resulting hydrosilylated norbornene polymerizable monomer. Usually, the molecular weight is usually about 500 to 20000. Therefore, it is particularly preferable to use 1,1,3,3-tetramethyldisiloxane as the component (Ia).

  Component (Ib) can be easily obtained by Diels-Alder addition reaction of various known norbornene derivatives and various known unsaturated carboxylic acid derivatives. Examples of the norbornene derivative include cyclopentadiene, dicyclopentadiene, tricyclopentadiene, and the like. These can be used alone or in combination. Further, as the unsaturated carboxylic acid derivative, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated dicarboxylic acid anhydride and the like can be used. For example, (meth) acrylic acid (in this specification, (meth) acrylic is Acrylic and / or methacrylic, the same shall apply hereinafter), maleic acid, fumaric acid, itaconic acid, maleic anhydride, itaconic anhydride and the like. These may be used alone or in combination. Since component (Ib) needs to undergo a hydrosilylation reaction with component (Ia), it must have at least one unsaturated bond in the molecule of component (Ib). It is preferable to set it as 1-2. For these reasons, it is particularly preferable to use a high-mic acid or anhydrous hymic acid as the component (Ib).

The production of component (I) can be carried out, for example, as follows. By heating component (Ia) and component (Ib) in the presence of a hydrosilylation catalyst, the hydrosilylation reaction can proceed. The hydrosilylation catalyst is not particularly limited as long as it has a catalytic activity for the hydrosilylation reaction. For example, platinum having a solid platinum supported on a carrier such as simple substance of alumina, alumina, silica, carbon black, chloroplatinic acid, chloride Complexes of platinum acid with alcohols, aldehydes, ketones, and other various platinum complexes (eg, platinum-olefin complexes, platinum-vinylsiloxane complexes, platinum-phosphine complexes, platinum-phosphite complexes, dicarbonyldichloroplatinum, platinum) -Hydrocarbon complex, platinum alcoholate catalyst, platinum chloride-olefin complex, etc.), and as catalysts other than these platinum compounds, known catalysts such as palladium-based, rhodium-based, and ruthenium-based compounds can also be used. These catalysts may be used alone or in combination of two or more. Of these, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes and the like are preferable from the viewpoint of catalytic activity. The amount of the hydrosilylation catalyst is not particularly limited, usually, per mole of the SiH group in component ^(Ia), from 10 -1 ^{to 10 -8} mol, preferably about ^{10-2 to 10-6} The range of moles.

  In addition, a co-catalyst can be used in combination with the catalyst. Examples of the promoter include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl maleate, acetylene alcohol compounds such as 2-hydroxy-2-methyl-1-butyne, and simple sulfur. And sulfur-based compounds such as triethylamine.

  In the reaction, from the viewpoint of increasing the reaction rate or improving workability, the reaction can be performed in the presence of an inert organic solvent. Examples of the inert organic solvent include toluene, chlorobenzene, tetrahydrofuran, and ethylene glycol dimethyl ether. Diethylene glycol dimethyl ether can be used. The heating temperature is not particularly limited, but is usually about 50 to 120 ° C, preferably 50 to 80 ° C.

The component (I) thus obtained has a structural unit represented by the above general formula (I), but when it has two such structural units, it has an α, β-unsaturated double bond. This is preferable because the reaction point with the polymerizable monomer having an increase in the degree of crosslinking, the degree of crosslinking is increased, and the hardness is improved.

  Component (II) which is a constituent material of the hydrosilylated norbornene polymerizable monomer of the present invention is not particularly limited as long as it is a polymerizable monomer having an α, β-unsaturated double bond, and is known. However, those having a functional group capable of reacting with the functional group (carboxyl group, acid anhydride group) of component (I) are preferred. Examples of the functional group capable of reacting with the functional group (carboxyl group, acid anhydride group) of the component (I) include a hydroxyl group, an amino group, an amide group, a glycidyl group, and an isocyanate group. Preferable specific examples of component (II) include, for example, hydroxyalkyl (meth) acrylate, (meth) acrylamide, glycidyl (meth) acrylate and isocyanate group-containing acrylate, and these may be used alone or in combination. Can be used.

  The component (I) obtained as described above can be reacted with the component (II) to obtain the hydrosilylated norbornene polymerizable monomer which is the object of the present invention. The reaction ratio between component (I) and component (II) is appropriately determined in consideration of various performances of the resulting hydrosilylated norbornene polymerizable monomer. The reaction ratio between component (I) and component (II) is generally [equivalent of carboxyl group or acid anhydride group of (I)] / equivalent of reactive functional group of (II) = 10/1. Is set to be 1/1, preferably 4/1 to 1/1. By introducing a large number of acryloyl groups into the hydrosilylated norbornene-based polymerizable monomer, the degree of crosslinking is increased and the hardness is improved. In addition, by leaving a highly reactive carboxyxyl group in the hydrosilylated norbornene polymerizable monomer, modification with other concomitant monomers and oligomers is facilitated, and it can be applied to applications such as resist such as stripping and removal with alkali. Application is also possible.

  Various conditions such as reaction temperature and reaction time in the reaction are not uniquely determined and are appropriately determined mainly depending on the type of the functional group in the component (II), but the component (II) in the reaction stage In general, the reaction is preferably carried out in the presence of oxygen or in the presence of a polymerization inhibitor.

  As described above, the hydrosilylated norbornene-based polymerizable monomer of the present invention is obtained. In order to further improve the storage stability of the polymerizable monomer, a curing retarder can be added. Examples of the curing retarder include a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin-based compound, and an organic peroxide. These may be used alone or as appropriate. You may use together. Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols, ene-yne compounds, maleate esters and the like. Examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite. Examples of organic sulfur compounds include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, benzothiazole disulfide and the like. Examples of nitrogen-containing compounds include ammonia, primary to tertiary alkylamines, arylamines, urea, hydrazine and the like. Examples of tin compounds include stannous halide dihydrate and stannous carboxylate. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate. Of these curing retarders, benzothiazole, thiazole, dimethyl malate, and 3-hydroxy-3-methyl-1-butyne are preferable from the viewpoint of good delay activity and good raw material availability.

  Hereinafter, the present invention will be described more specifically with reference to production examples, examples, and comparative examples, but the present invention is not limited to these examples.

Production Example 1 [Synthesis of component (I) (hydrosilylation of hymic anhydride)]
In a reaction vessel equipped with a stirrer, a cooling tube, a calcium chloride tube, a thermometer, and a dropping funnel, 400 g (2.44 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride (common name: hymic acid), 750 ml of toluene And 4.0 g of catalyst (chloroplatinic acid hexahydrate), and 155.9 g (1.16 mol) of 1,1,3,3-tetramethyldisiloxane were added to the dropping funnel. While paying attention to heat generation in the reaction system (maintained at 60 ° C. to 70 ° C.), 1,1,3,3-tetramethyldisiloxane was dropped from the dropping funnel over 30 minutes with stirring, and then 70-80 Stirring was continued at 5 ° C. for 5 hours. After cooling, 60 g of activated carbon was added to the reaction system and stirred at room temperature for 2 hours. Subsequently, the activated carbon and the catalyst were filtered, the solvent was removed from the filtrate using an evaporator, and 1350 ml of diethyl ether was added for recrystallization, whereby white crystals were precipitated at room temperature. Furthermore, it cooled to 5 degreeC and the said crystal | crystallization was separated by filtration. By drying the crystals using a vacuum pump, 5,5 ′-(1,1,3,3-tetramethyl-1,3-disiloxanediyl) -bis-norbornane-2,3-dicarboxylic acid anhydride 280.4 g of product was obtained. The NMR measurement results of the dicarboxylic acid anhydride are as follows.

¹ H-NMR (300 MHz / CDCl ₃ ) σ 0.06 (12H, m) (a), 0.67 (2H, m) (b),
1.53-1.68 (8H, m) (c, d, e), 2.77-2.88 (4H, dd) (f), 3.23 (4H, m) (g, h)
¹³ C-NMR (300 MHz / CDCl ₃ ) σ −1.10 (1), −0.90 (1), 25.9 (2), 26.8 (3), 40.4 (4), 41. 1 (5), 41.7 (6), 49.5 (7), 52.7 (8), 171.9 (9), 172.2 (10)
In addition, assignment of chemical shift of ¹ H, ¹³ C-NMR is shown in FIG.

Example 1 (Synthesis of target product: diacrylate)
In a reaction vessel equipped with a condenser, a stirrer, and a thermometer, 5,5 ′-(1,1,3,3-tetramethyl-1,3-disiloxanediyl) -bis-norbornane-2,3-dicarbon Add 50 g (0.17 mol) of acid anhydride, 58.3 g (0.50 mol) of hydroxyethyl acrylate, 0.05 g of phenothiazine (polymerization inhibitor), 5.0 g (0.06 mol) of triethylamine, and 250 ml of toluene. After heating up to 80 degreeC over 1 hour, the heating stirring was continued for 8 hours. After cooling, the solvent was removed from the filtrate using an evaporator to obtain 108.3 g of a crude product.

50 g of the crude product was purified by silica gel column chromatography (developing solvent chloroform: ethyl acetate 10: 1 → 5: 1, silica gel: Merck Co., Ltd., trade name “silica gel 60”), 5 ′-(1,1,3,3-tetramethyl-1,3-disiloxanediyl) -bis-norbornane-2 (or 3) -carboxylethyl acrylate (diacrylate body: acryloyl equivalent 293 (theoretical amount)) 30.1 g was obtained.
From the following NMR analysis results, it was confirmed that the purified product was obtained by introducing two ethyl acrylates per molecule of the acid anhydride of Production Example 1.
¹ H-NMR (300 MHz / CDCl ₃ ) σ 0.40 (12H, m), 1.15-1.60 (10H, m), 2.40-2.70 (4H, m), 2.78-3.20 (4H M), 4.16-4.42 (8H, m), 5.83 (2H, m), 6.13 (2H, m), 6.42 (2H, m)
¹³ C-NMR (300 MHz / CDCl ₃ ) σ −1.10, −0.90, 23.3, 26.8, 39.1, 40.8, 46.2, 49.2, 49.6, 61 7, 62.4, 128.0, 131.3, 166.0, 172.0, 177.7

Example 2 (Synthesis of target product: tetraacrylate body)
In a reaction vessel equipped with a thermometer, a stirrer, a condenser tube, and a calcium chloride tube, 1.51 g (3.34 mmol) of the diacrylate body obtained in Example 1, 0.85 g (7.34 mmol) of hydroxyethyl acrylate, 4-Dimethylaminopyridine 0.65 g (5.34 mmol) and methylene chloride 50 ml were added, and the system temperature was cooled to 0 ° C. using an ice bath. To this solution, 1.52 g (7.34 mmol) of dicyclohexylcarbodiimide was added and kept at 0 ° C. for 30 minutes. Next, the ice bath was removed, and stirring in the reaction system was continued for 2 hours at room temperature. The precipitated dicyclohexylurea was filtered off, and the obtained filtrate was washed with 1M hydrochloric acid (2 × 10 ml), 1M aqueous sodium hydrogen carbonate solution (2 × 10 ml), and 20 ml of ion-exchanged water in this order. Urea precipitated during the washing operation was also filtered off, and the organic layer was dried over magnesium sulfate. Subsequently, 150 ml of hexane was added and filtered in a state where urea was precipitated, and the solution was concentrated using an evaporator to obtain 1.56 g of a crude product.

0.60 g of the crude product was purified by 10 times the amount of silica gel column chromatography (methylene chloride → chloroform), and 5,5 ′-(1,1,3,3-tetramethyl-1,3-disiloxanediyl) -0.33 g of bis-norbornane-2,3-carboxylethyl acrylate (tetraacrylate body) was obtained.
From the following NMR analysis results, it was confirmed that the purified product was obtained by introducing four ethyl acrylates per molecule of the acid anhydride of Production Example 1.
¹ H-NMR (300 MHz / CDCl ₃ ) σ 0.80 (12H, m), 0.95-1.90 (10H, m), 2.42-2.63 (4H, m), 2.85-2.94 (2H , Dd), 3.08-3.20 (2H, dd), 4.16-4.42 (16H, m), 5.83 (4H, m), 6.13 (4H, m), 6.42 (4H, m)
¹³ C-NMR (300 MHz / CDCl ₃ ) σ −1.10, −0.60, 23.3, 26.8, 39.1, 40.6, 41.4, 46.2, 49.2, 61 7, 62.4, 128.0, 131.3, 165.8, 171.9, 172.3

Example 3
100 parts of the diacrylate body obtained in Example 1, 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name “Irgacure 184” (hereinafter abbreviated as “Irg184”) as a photopolymerization initiator. )) Weighed 5 parts into a beaker and dissolved under heating at 70 ° C. to prepare an active energy ray-curable composition.

Comparative Example 1
100 parts of dimethylol tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name “DCP-A”, acryloyl equivalent 152) and 5 parts of “Irg184” are weighed in a beaker and heated at 70 ° C. An active energy ray-curable composition was prepared by dissolving.

(Performance evaluation)
1. Preparation of Specimens Various active energy ray-curable compositions obtained in the above Examples and Comparative Examples were coated on a glass plate with a bar coater # 2, and a high-pressure mercury lamp (80 W / cm, one lamp, irradiation altitude of 10 cm). Under a belt speed of 20 m / min) and repeated until it became tack-free, and it was confirmed that the film was cured.
2. Evaluation was performed by the following evaluation methods and standards. The evaluation results are shown in Table 1.
(1) UV Curing When preparing a curing test piece, the irradiation dose (mJ / cm ² ) required until the curing was completed (that is, until the coating film was not damaged even when the coating film was rubbed with a nail) was measured. . Note that the irradiation dose by one pass is 67.5 mJ / cm ² .
(2) Appearance of cured film: evaluated by visual observation.
(3) Adhesiveness The cured film part was cross-cut, and a cross cellophane tape peeling test (based on JIS K5400) was performed, and the adhesion state of the coating film after tape peeling was evaluated according to the following criteria.
○: (100 to 90) / 100, Δ: (89 to 70) / 100, ×: (69 to 0) / 100
(4) Pencil hardness (conforming to JIS K-5400)
(5) Refractive index It measured with the Abbe refractometer (nD / 20 degreeC).

The evaluation results are shown in Table 1.

The hydrosilylated norbornene-based polymerizable monomer of the present invention is a novel active energy ray-curable monomer or oligomer and can be applied to various active energy ray-curable resin compositions. Further, the hydrosilylated norbornene polymerizable monomer of the present invention can be homopolymerized or copolymerized with other monomers by a radical polymerization catalyst or the like or by irradiation with active energy rays. The polymer can be used in various applications requiring active energy ray curability, such as coating agents (inks, paints, etc.), adhesives, photographic materials, photocurable resins, optical materials, fiber treatment agents, It can be applied to optical fiber protective agents, mold release agents, molding materials, plastic modifiers, selective permeable membranes, and the like.

¹ H relating to 5,5 ′-(1,1,3,3-tetramethyl-1,3-disiloxanediyl) -bis-norbornane-2,3-dicarboxylic acid anhydride obtained in Preparation Example 1, ¹³ This is the assignment of chemical shift of C-NMR.

Claims (10)

General formula (1):

(In the formula, X is 1 or 2, R ¹ and R ² each represent a hydrogen atom or a carboxyl group, but they are not both hydrogen atoms, and R ¹ and R ² are each an acid anhydride group. R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), and a hydrosilylated norbornenecarboxylic acid derivative (I) having at least one structural unit in the molecule, α , A hydrosilylated norbornene polymerizable monomer obtained by reacting a polymerizable monomer (II) having a β-unsaturated double bond. 2. The hydrosilylated norbornene-based polymerizable monomer according to claim 1, wherein the hydrosilylated norbornene carboxylic acid derivative (I) has two of the structural units. The hydrosilylated norbornene carboxylic acid derivative (I) is obtained by hydrosilylating an organosiloxane (Ia) having at least one silyl group (SiH) in the molecule and a norbornene carboxylic acid derivative (Ib). The hydrosilylated norbornene-based polymerizable monomer according to claim 1 or 2. The hydrosilylated norbornene-based polymerizable monomer according to any one of claims 1 to 3, wherein the organosiloxane (Ia) is 1,1,3,3-tetramethyldisiloxane. The hydrosilylated norbornene-based polymerizable monomer according to any one of claims 1 to 4, wherein the norbornene carboxylic acid derivative (Ib) is a high-mic acid or a hymic anhydride.   The polymerizable monomer (II) having an α, β-unsaturated double bond is a compound having reactivity to a carboxyl group or an acid anhydride group of the hydrosilylated norbornenecarboxylic acid derivative (I). Item 6. The hydrosilylated norbornene-based polymerizable monomer according to any one of Items 1 to 5.   The polymerizable monomer (II) having an α, β-unsaturated double bond is at least selected from the group consisting of hydroxyalkyl (meth) acrylate, (meth) acrylamide, glycidyl (meth) acrylate and isocyanate group-containing acrylate. The hydrosilylated norbornene polymerizable monomer according to any one of claims 1 to 6, which is one kind of acrylic monomer.   The reaction ratio between the hydrosilylated norbornenecarboxylic acid derivative (I) and the polymerizable monomer (II) having an α, β-unsaturated double bond is [equivalent of the carboxyl group or acid anhydride group of (I). ] The equivalent of the reactive functional group of / (II) = 10/1 to 1/1 The hydrosilylated norbornene polymerizable monomer according to any one of claims 1 to 7.   Hydrosilylated norbornene-based polymerizable monomer in which the hydrosilylated norbornenecarboxylic acid derivative (I) and the polymerizable monomer (II) having an α, β-unsaturated double bond are heated and reacted in the presence of a hydrosilylation catalyst. Body manufacturing method. The hydrosilylated norbornenecarboxylic acid derivative (I) and the polymerizable monomer (II) having an α, β-unsaturated double bond are heated in the presence of a hydrosilylation catalyst and oxygen and / or a polymerization inhibitor. A process for producing a hydrosilylated norbornene polymerizable monomer.

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