JP2007197719A - New alicyclic compound and method for producing the alicyclic compound, composition for polymerization including the alicyclic compound and polymer obtained by polymerizing the composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new alicyclic compound or the like which achieves good physical properties when used as raw materials such as an electronic material and an optical material. <P>SOLUTION: The alicyclic compound (alicyclic imide acrylate) has polymerizable functional groups, which are a (meth)acroyl group and a vinylene group in a norbornene skeleton, in the molecule so that the compound may become an oily or aqueous polymer by the homopolymerization or the copolymerization with another polymerizable monomer. The polymer has good physical properties in heat-resistance, low water-absorbing property, low moisture permeability, high hardness, tightness to various substrates or the like. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a novel alicyclic compound, a method for producing the alicyclic compound, a polymerization composition containing the alicyclic compound, and a polymer obtained by polymerizing the polymerization composition.

  In recent years, various new materials have been studied in the fields of electronic materials and optical materials in order to improve various performances. In particular, alicyclic compounds have been actively researched and developed because they can be expected to have excellent characteristics in fields such as electronic materials and optical materials. The present applicant has previously proposed various novel alicyclic compounds (see, for example, Patent Documents 1 and 2), but a material capable of imparting further high performance is required.

  By the way, imide compounds have been widely used in electronic materials, optical materials, and the like due to their excellent properties such as electric resistance and solvent resistance.

Japanese Patent No. 3122282 Japanese Patent No. 3306638

The main object of the present invention is to provide a novel alicyclic compound that exhibits good physical properties when used as a raw material for electronic materials, optical materials, and the like, and a method for producing the same. Another object of the present invention is to provide a polymerization composition containing the alicyclic compound and a polymer obtained by polymerizing the polymerization composition.

  The inventor of the present invention has a novel alicyclic compound represented by the following general formula (1), and a polymer composition using the alicyclic compound as a raw material has excellent curability and is obtained from the polymer composition. It has been found that the polymer obtained is excellent in physical properties such as heat resistance, low water absorption, low moisture permeability, hardness, and adhesion to various substrates. That is, the present invention

1. The following general formula (1):

(Wherein R ¹ represents hydrogen or a methyl group, a represents an integer of 1 to 6, and b represents an integer of 0 to 6);

2. The following general formula (2-1):

Or an alicyclic dicarboxylic acid represented by the following general formula (2-2):

A monoamine represented by the general formula (3): H ₂ N— (CH ₂ ) _a —OH (where a represents an integer of 1 to 6). The compound is reacted to give the following general formula (4):

(In the formula, a represents an integer of 1 to 6), and an alicyclic imide compound represented by general formula (5): HOOC— (CH ₂ ) _b —C (R ¹ ) = The following general formula (1), characterized by reacting a vinyl compound represented by CH ₂ (wherein R ¹ is hydrogen or a methyl group, and b is an integer of 0 to 6):

(Wherein R ¹ represents hydrogen or a methyl group, a represents an integer of 1 to 6, and b represents an integer of 0 to 6);

3. 1 above. Or the alicyclic compound described in 2 above. A composition for polymerization comprising an alicyclic compound obtained by the production method described in 1);

4). 3 above. And a polymer obtained by polymerizing the composition for polymerization described in 1.

Since the alicyclic compound of the present invention has a norbornene skeleton, an imide group, and a polymerizable functional group ((meth) acryloyl group and vinylene group in the norbornene skeleton) in the molecule, it can be used in conventional electronic materials and optical materials. When incorporated, new properties are expected.
Moreover, the composition for polymerization containing the alicyclic compound is easily and quickly polymerized by various polymerization methods to give various polymers.
In addition, since the polymer has good physical properties such as heat resistance, low water absorption, low moisture permeability, high hardness, and adhesion to various substrates, it can be expected to be useful as an electronic material and an optical material.

The alicyclic compound of the present invention (hereinafter referred to as alicyclic imide acrylate) has the following general formula (1):

(Wherein R ¹ represents hydrogen or a methyl group, a represents an integer of 1 to 6, and b represents an integer of 0 to 6).

  Since the alicyclic imide acrylate according to the present invention has a polymerizable functional group ((meth) acryloyl group and vinylene group in norbornene skeleton) in the molecule, it is polymerized alone or copolymerized with other polymerizable monomers. Thus, various oily or aqueous polymers can be obtained.

Although the manufacturing method of the said alicyclic imide acrylate is not specifically limited, Specifically, for example, the following general formula (2-1):

Or an alicyclic dicarboxylic acid represented by the following general formula (2-2):

(Hereinafter, both are collectively referred to as alicyclic dicarboxylic acid (anhydride)), the general formula (3): H ₂ N— (CH ₂ ) _a —OH (formula In the formula, a represents an integer of 1 to 6) and a monoamine compound represented by the following formula (4):

(In the formula, a represents an integer of 1 to 6.)

The alicyclic imide compound represented by general formula (5): HOOC— (CH ₂ ) _b —C (R ¹ ) ═CH ₂ (wherein R ¹ is hydrogen or a methyl group, b Represents an integer of 0 to 6.) and can be obtained by reacting the vinyl compound represented by

Examples of the alicyclic dicarboxylic acid (anhydride) include maleic acid or maleic anhydride added by Diels-Alder to cyclopentadiene, and alicyclic trans-dicarboxylic acid diesters (for example, JP-A-9-20724). Etc.) can be obtained by a hydrolysis method. In addition, it is preferable to use an alicyclic dicarboxylic acid anhydride because an amidation reaction described later easily proceeds. As the alicyclic dicarboxylic acid anhydride, for example, a commercially available product can be used as a hymic anhydride.

Examples of the monoamine compound include monoamino alcohol compounds such as ethanolamine, propanolamine, and butanolamine. Among these, ethanolamine is particularly preferable from the viewpoint of availability and inexpensiveness.

The method of reacting the monoamine compound represented by the general formula (3) with the alicyclic dicarboxylic acid (anhydride) represented by the general formula (2-2) is not particularly limited, and various known methods can be used. Can be adopted. Specifically, for example, 1 mol of the alicyclic dicarboxylic acid (anhydride) and about 0.5 to 3 mol of the monoamine compound are usually used in a solvent azeotroped with water such as ethanol at 10 ° C to Examples include a method in which an amidation reaction is performed at about 70 ° C. for about 1 to 5 hours, and then an azeotropic dehydration is performed at a temperature of about 80 ° C. to 180 ° C. for about 3 to 20 hours to perform an imidization reaction.

In each reaction, various known acid catalysts or basic catalysts can be used. Specific examples include organic sulfonic acids such as alkylsulfonic acid, p-toluenesulfonic acid and benzenesulfonic acid, inorganic acids such as sulfuric acid and phosphorous acid, and basic compounds such as pyridine, trimethylamine and triethylamine. These can be used singly or in combination of two or more. In addition, although the usage-amount of this catalyst is not specifically limited, Usually, it is about 0.001-1.0 weight% with respect to alicyclic dicarboxylic acid (anhydride).

In the imidization reaction, a combination of various known dehydrating agents (dicyclohexylcarbodiimide, acetic anhydride, etc.) and a basic compound (pyridine, triethylamine, sodium acetate, etc.) is used. The reaction can be performed at a low temperature. In addition, although the usage-amount of this thing is not specifically limited, Usually, it is about 0.001-1.0 weight% with respect to alicyclic dicarboxylic acid (anhydride). Moreover, the quantity of the said basic compound with respect to 1 mol of said dehydrating agents is about 1-5 mol normally.

The alicyclic imide acrylate represented by the general formula (1) is obtained by reacting the alicyclic imide compound thus produced with the vinyl compound represented by the general formula (5).

Specific examples of the vinyl compound include acrylic acid, methacrylic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, and 6-heptenoic acid.

The reaction is not particularly limited, and various known esterification reactions can be used. Specifically, for example, 1 mol of the alicyclic imide compound and the vinyl compound which is about 0.5 to 20 mol relative to this are usually reacted at about 20 to 150 ° C. for about 2 to 20 hours. You can do it. The reaction is preferably carried out while distilling off water in the presence of a solvent azeotropic with water (aromatic solvents such as benzene, toluene and xylene are preferred). In the reaction, various known esterification catalysts (p-toluenesulfonic acid, sulfuric acid, etc.) are preferably used. In addition, the usage-amount of this esterification catalyst is about 0.001-0.1 mol normally with respect to 1 mol of said alicyclic imide compounds.

Moreover, it is preferable to take various polymerization prohibition measures (polymerization inhibitor, bubbling with air or oxygen, etc.) during the reaction. Examples of the polymerization inhibitor include hydroquinone, methoquinone, phenothiazine and the like, and the amount used is usually about 0.0001 to 0.01 mol with respect to 1 mol of the vinyl compound.

The alicyclic imide acrylate represented by the general formula (1) thus obtained is usually highly pure as it is, but can be purified by various known methods such as distillation and silica gel column chromatography as necessary. , Higher purity can be achieved.

The composition for polymerization according to the present invention includes the alicyclic compound, and includes other polymerizable compounds other than the alicyclic imide acrylate, various polymerization initiators, and various additives. be able to. In addition, the other polymerizable compound specifically includes a compound having one ethylenically unsaturated group (hereinafter referred to as a monofunctional monomer) or a compound having two or more ethylenically unsaturated groups (hereinafter referred to as “monofunctional monomer”). It is called a polyfunctional monomer.

Examples of the monofunctional monomer include alkyl acrylate esters [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, hydroxyethyl (meth) acrylate, isobornyl (meth) acrylate, etc. ], Aromatic monomers (styrene, α-methylstyrene, vinyltoluene, indene, methylindene, etc.), anionic vinyl monomers and neutralized salts thereof ((meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, Fumaric acid, muconic acid, citraconic acid, vinyl sulfonic acid, styrene sulfonic acid, (meth) allyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, etc., and neutralized salts thereof], containing tertiary amino group Vinyl monomer [N, N-dimethylaminoethyl (meth) acrylate, N, N Diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, etc.], and the tertiary amino group-containing vinyl monomer is converted into a quaternizing agent (methyl chloride, Cationic vinyl monomers quaternized with benzyl chloride, dimethyl sulfate, epichlorohydrin, etc.), hydroxyl group-containing (meth) acrylates [2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) ) Acrylate, hydroxypentyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, pentaerythritol mono (meth) ) Acrylate, trimethylolpropane mono (meth) acrylate, etc.], vinyl acetate, N-vinylpyrrolidone, etc., (meth) acrylates of phenolic alkylene oxide adducts, and halogen nucleus substitutes thereof [phenoxyethyl (meth) acrylates] , Phenol ethylene oxide modified (meth) acrylates and phenol propylene oxide modified (meth) acrylates, etc.], (meth) acrylates of alkylene oxide adducts of alkylphenols, and their halogen nucleus substitutes [nonylphenol ethylene oxide modified (meth) acrylate, nonylphenol propylene oxide Modified (meth) acrylate and paracumylphenol alkylene oxide modified (meth) acrylate, etc.], phenylphenol alkylene Xoxide-modified (meth) acrylate and its halogen substitution product, etc.], 2-hydroxy-3-phenoxypropyl (meth) acrylate and its halogen nucleus substitution product, (meth) acrylic acid adduct of phenylphenol glycidyl ether and its halogen nucleus substitution body, epoxy mono (meth) acrylates such as (meth) acrylic acid adducts of cyclohexene oxide, 2-ethylhexyl carbitol (meth) acrylate, Isobo b ← not Le? Nyl (meth) acrylate, (meth) acryloylmorpholine, etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types.

Examples of the polyfunctional monomer include divinylbenzene, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, bisphenol A tetraethylene glycol diacrylate, hexamethylene glycol diacrylate. Acrylate, 1,9-nonanediol diacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, N-vinylpyrrolidone, (meth) acrylamide, N-vinylformamide, 4-hydroxybutyl vinyl ether, diethylene glycol divinyl ether, pentaerythritol tri Or di (meth) acrylate and trimethylolpropane (Meth) acrylate, polyester poly (meth) acrylate, epoxy poly (meth) acrylate, poly (meth) acrylate of (meth) acrylic polymer, urethane poly (meth) acrylate, and the like can be mentioned. Alternatively, two or more types can be used in combination.

In addition, when the composition for polymerization according to the present invention contains the urethane poly (meth) acrylate, the elongation rate of the obtained polymer becomes high, and its flexibility, toughness, low water absorption, low It is preferable because it has excellent moisture permeability and the like. Here, the urethane poly (meth) acrylate refers to a compound obtained by reacting the hydroxyl group-containing (meth) acrylate with a reaction product of a polyol and an organic polyisocyanate.

Examples of the polyol include low molecular weight polyols (ethylene glycol, propylene glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, etc.), polyether polyols (polyalkylenes such as polyethylene glycol, polypropylene glycol, and polytetraethylene glycol). Glycols, polyethylene polypropoxy block polymer diols such as block or random polymer diols, etc.], polyester polyols [low molecular weight polyols and / or polyether polyols, and acid components (adipic acid, succinic acid, phthalic acid, tetrahydrophthalic acid) , Esterification reaction products with dibasic acids such as hexahydrophthalic acid and terephthalic acid or their anhydrides, etc.].

Examples of the organic polyisocyanate include tolylene diisocyanate, 1,6-hexane diisocyanate, 4,4'-diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, 1,6-hexane diisocyanate trimer, hydrogenated tolylene diisocyanate, hydrogenation 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, paraphenylene diisocyanate, tolylene diisocyanate dimer, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate interadduct, 4,4'-dicyclohexylmethane Examples thereof include diisocyanate, trimethylolpropane tris (tolylene diisocyanate) adduct, and isophorone diisocyanate.

In the composition for polymerization according to the present invention, the ratio of the alicyclic imide acrylate and the other polymerizable compound is not particularly limited, but usually the former is about 10 to 80% by weight (preferably 20 to 60% by weight). The latter is about 20 to 90% by weight (preferably 40 to 80% by weight). By setting the numerical value range, the curability of the polymerization composition, the heat resistance, low water absorption, low moisture permeability, hardness, flexibility, and the like of the resulting polymer, and the adhesion to various substrates are improved. .

As the polymerization initiator, various known thermal polymerization initiators are used when the polymerization composition according to the present invention is thermally polymerized, and various known radical photopolymerization initiators are used when photopolymerized. .

Specific examples of the thermal polymerization initiator include organic peroxides [1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1-bis (t-hexylperoxy)- 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (T-butylperoxy) cyclohexane etc.], azo compounds [1,1′-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2 , 4-dimethylvaleronitrile, azodi-t-octane, azodi-t-butane, and the like. These are used alone or in combination of two or more. It can be used in conjunction. In addition, the said organic peroxide is good also as a redox-type initiator by combining with various well-known reducing agents. The usage-amount of this thermal-polymerization initiator is about 0.01 to 10 weight% normally with respect to the total weight of the said alicyclic imide acrylate and the said other polymeric compound.

Specific examples of the photo radical polymerization initiator include benzoins [benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc.] and alkyl ethers thereof, acetophenones [acetophenone, 2,2- Dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone, 1-hydroxycyclohexyl phenyl ketone and 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-propan-1-one etc.] anthraquinones [anthraquinones such as 2-tert-butylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone], thiooxant [2,4-dimethylthiooxane, 2,4-diethylthiooxane, 2-chlorothiooxane, 2,4-diisopropylthiooxane, etc.], ketals [acetophenone dimethyl ketal, benzyl dimethyl ketal, etc. Ketals, benzophenones, xanthones and the like can be mentioned, and these can be used alone or in combination of two or more. The radical photopolymerization initiator can also be used in combination with a benzoic acid-based, amine-based photopolymerization initiation accelerator. The content of the radical photopolymerization initiator in the polymerization composition according to the present invention is usually about 0.1 to 10% by weight with respect to the total weight of the alicyclic imide acrylate and the other polymerizable compound. It is.

In addition to the radical photopolymerization initiator, an ultraviolet absorber [2- (5-methyl-2-hydroxyphenyl) benzotriazole and 2- (3,5-di-t-amyl-2-hydroxy) is optionally added. Phenyl) benzotriazole and the like], light stabilizers [bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and 2- (3,5-di-t-butyl-4-hydroxybenzyl)- 2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxy Benzoate and the like], antioxidants [triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] and 1,6-hexanediol-bis [3, - it can be used di -t- butyl-4-hydroxyphenyl] propionate, etc.] and the like.

Examples of the additive include inorganic fillers (silica powder, alumina, zircon, calcium silicate, calcium carbonate, etc.), coloring agents such as dyes and pigments (phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, Crystal violet, titanium oxide, carbon black, naphthalene black, etc.), flame retardants (antimony trioxide, phosphoric acid esters, red phosphorus, melamine resins and other nitrogen-containing compounds), antifoaming agents (silicone, fluorine, Polymers, etc.), adhesion promoters (imidazoles, thiazoles, triazoles, silane coupling agents, etc.), stress relieving agents (silicone oil, silicone rubber powder, etc.), antistatic agents, leveling agents, viscosity modifiers , UV blocker, treatment agent, polymerization inhibitor, etc. These may be used alone or in combinations of two or more thereof.

In the present invention, the polymerization method is not particularly limited, and for example, a method of irradiating active energy rays (photopolymerization method) or a method of heating (thermal polymerization method) can be employed. Each polymerization reaction can be carried out in various solvents such as alcohol solvents (methanol, ethanol, etc.), aromatic solvents (benzene, toluene, xylene, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), ether solvents (THF, etc.). ) In the presence or absence.

Moreover, as an active energy ray, an ultraviolet-ray and an electron beam are mentioned, for example. Examples of the ultraviolet light source include a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, an electrodeless discharge lamp, and a carbon arc lamp. Moreover, as an electron beam source, for example, a Cockloft-Waltsin type, a bandegraph type or a resonance transformer type irradiation device can be cited.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Moreover, the following apparatus was used for the spectrum measurement of each compound.
NMR: GEMINI-300 (manufactured by Varian)
IR: NEXUS670 (manufactured by Thermo Electron)
Gas chromatography (GC): GC6890 (manufactured by Agilent)

Example 1
A reaction vessel equipped with a condenser, thermometer, dropping funnel, nitrogen gas inlet and stirrer was charged with 82.1 g of hymic anhydride (trade name “HAC”, manufactured by Hitachi Chemical Co., Ltd.), and the inside of the system was purged with nitrogen did. Next, the reaction vessel was cooled in an ice bath, and 120 g of an ethanol solution containing 34.5 g of ethanolamine was added dropwise while stirring at an internal temperature of 10 ° C. or lower. After completion of the dropwise addition, the ice bath was removed and the reaction was carried out at room temperature for 4 hours. Thereafter, the mixture was heated to the reflux temperature (81 ° C.), and the reaction was carried out for 4 hours while azeotropically removing water with ethanol (in this case, the system was replenished with the same volume of ethanol as the ethanol water mixture that was removed. ). After the solvent was distilled off under reduced pressure, a mixed solvent of ethanol and n-hexane was added to perform recrystallization, and the obtained crystal was dried under reduced pressure to obtain 75.9 g of an alicyclic imide compound. This had a purity of 97.9% (according to GC method).

Subsequently, 25.0 g of the alicyclic imide compound, 0.41 g of hydroquinone, 65. toluene of 65.degree. 0 g was added, and 0.61 g of p-toluenesulfonic acid and 41.3 g of acrylic acid were further added and stirred. While bubbling air in the system, the temperature was raised to the reflux temperature (106 to 110 ° C.), and the reaction was carried out for 6 hours while water was distilled from the system with a Dean-Stark water separator. Next, the reaction solution is cooled to 40 ° C. or lower, repeatedly washed with ion-exchanged water and aqueous sodium hydrogen carbonate solution using a separatory funnel, and toluene is distilled off by concentration under reduced pressure to prepare alicyclic imide acrylate A (hereinafter referred to as compound). A). This had a purity of 96.2% (according to GC method). In addition, each spectrum measurement value and structure of the compound A are as follows.

¹ H-NMR (300 MHz, solvent CDCl ₃ , δ (ppm)): 5.86, 6.41, 6.10, 4.19, 3.68, 3.39, 3.28, 1.55, 1 .74, 6.08
¹³ C-NMR (300 MHz, solvent CDCl ₃ , δ (ppm)): 131.28, 127.89, 165.54, 60.96, 37.03, 177.23, 134.22
IR (neat): 1635, 1697, 1723, 1184
1071 cm ^-1

Comparative Example 1
Tetrahydrophthalic anhydride (trade name “Licacid TH”, manufactured by Shin Nippon Rika Co., Ltd.) 200 in a reaction vessel equipped with a Dean Stark water separator (Dimroth condenser), thermometer, dropping funnel, nitrogen gas inlet, and stirrer 0.0 g and 185.0 g of dehydrated toluene were charged, and the system was purged with nitrogen. Next, 80.3 g of ethanolamine was added dropwise while stirring the reaction vessel at room temperature. After completion of the dropwise addition, the mixture was heated to the reflux temperature (110 ° C.) and reacted for 6 hours while removing water azeotropically with toluene to obtain a cyclic imide compound. This had a purity of 99.1% (according to GC method).

Next, the reaction solution was returned to room temperature, the nitrogen gas inlet was changed to an air bubbling inlet tube, 2.57 g of methoquinone, 15 g of p-toluenesulfonic acid, and 185.9 g of acrylic acid were added and stirred. While bubbling air in the system, the temperature was raised to the reflux temperature (106 to 110 ° C.), and the reaction was carried out for 16 hours while water was distilled from the system with a Dean-Stark water separator. Next, the reaction solution is cooled to 40 ° C. or lower, washed repeatedly with ion-exchanged water and aqueous sodium hydrogen carbonate solution using a separatory funnel, and toluene was distilled off by concentration under reduced pressure to obtain alicyclic imide acrylate B (hereinafter referred to as compound). B)). This had a purity of 93.1% (by the GC method). In addition, each spectrum measurement value and structure of the compound B are as follows.

¹ H-NMR (300 MHz, solvent CDCl ₃ , δ (ppm)): 5.87, 6.37, 6.06, 4.26, 3.79, 3.10, 2.56, 2.20
IR (neat): 1653, 1703, 1725, 1182
1401 cm ^-1

Comparative Example 2
A reactor equipped with a Dean-Stark water separator (Dimroth condenser), thermometer, dropping funnel, nitrogen gas inlet, and stirrer was charged with 150.0 g of succinic anhydride (manufactured by Wako Pure Chemical Industries) and 150.0 g of dehydrated toluene, The system was replaced with nitrogen. Next, 89.7 g of ethanolamine was added dropwise while stirring the reaction vessel at room temperature. After completion of the dropwise addition, the mixture was heated to the reflux temperature (110 ° C.) and reacted for 3 hours while removing water azeotropically with toluene to obtain an imide compound. This had a purity of 97.0% (according to GC method).

Next, the reaction solution was returned to room temperature, the nitrogen gas inlet was changed to an air bubbling inlet tube, 3.0 g of methoquinone, 30.0 g of p-toluenesulfonic acid, and 378.0 g of acrylic acid were added and stirred. Next, the system was heated to reflux temperature (106 to 110 ° C.) while bubbling with air, and the reaction was carried out for 16 hours while water was distilled from the system with a Dean-Stark water separator. Next, the reaction solution is cooled to 40 ° C. or lower, repeatedly washed with ion-exchanged water and an aqueous sodium hydrogen carbonate solution using a separatory funnel, and toluene is distilled off by concentration under reduced pressure. Imide acrylate C (hereinafter referred to as Compound C) ) This had a purity of 87.0% (according to GC method). In addition, each spectrum measurement value and structure of the compound C are as follows.

¹ H-NMR (300 MHz, solvent CDCl ₃ , δ (ppm)): 6.78, 6.36, 5.87, 4.32, 3.84, 2.72
IR (neat): 1700, 1401, 1184
1112 cm ^-1

  Hereinafter, Comparative Compounds D to G are shown.

Compound D (trade name “Aronix M140”, manufactured by Toagosei Co., Ltd.)

Compound E (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.)

Compound F (trade name “FA-513A”, manufactured by Hitachi Chemical Co., Ltd.)

Compound G (trade name “FA-512AS”, manufactured by Hitachi Chemical Co., Ltd.)

Example 2
50 parts of the compound A, 50 parts of toluene, and 0.9 part of azobisisobutyronitrile (3 mol% with respect to the A) were mixed to prepare a composition A for thermal polymerization. Subsequently, this was polymerized under conditions of 80 ° C. and 5 hours in a nitrogen atmosphere. Subsequently, the polymer obtained was washed with toluene to remove unreacted compound A, and then dried under reduced pressure (1333 Pa, 80 ° C., 5 hours) to obtain polymer A containing compound A alone. The polymer A was subjected to the following heat resistance test.
In addition, since the said compound A has two polymerizable functional groups in a molecule | numerator, it is thought that a crosslinking reaction produces during superposition | polymerization.

Comparative Example 3
A thermal polymerization composition B was prepared in the same manner as in Example 2, except that the compound B was used instead of the compound A. Subsequently, the polymer B of the compound B single was obtained by the same process as the above. The polymer B was subjected to the following heat resistance test.

Comparative Examples 4-7
A composition C for thermal polymerization was prepared in the same manner as in Example 2, except that the compounds C to F were used in place of the compound A. Subsequently, each thermal polymerization composition was polymerized in the same manner as in Example 2. Subsequently, each polymer obtained was purified by reprecipitation using hexane to remove unreacted compounds, and further dried under reduced pressure (1333 Pa, 80 ° C., 5 hours) to obtain polymers C to F. It was. The polymers C to F were subjected to the following heat resistance test.

Comparative Example 8
A composition G for thermal polymerization was prepared in the same manner as in Example 2, except that the compound G was used in place of the compound A. Next, this was polymerized in the same manner as in Example 2 to obtain a polymer G. The polymer G was subjected to the following heat resistance test.

(Evaluation of heat resistance)
Using the commercially available differential thermal / thermogravimetric measuring device (TG-DTA, product name “2000S System WS002”, manufactured by Mac Science Co., Ltd.), the bending points of the polymers A to G are calculated by the tangent method. It was set as the thermal decomposition start temperature. The results are shown in Table 1.

  The polymer A is superior in heat resistance and the like as compared with the polymers B to G (particularly, the polymers B and G). This is thought to be because the vinylene group in the norbornene skeleton of Compound A is excellent in polymerizability, so that the crosslinking density of the polymer A is increased.

Example 3
80 parts of the compound A, 20 parts of urethane acrylate (trade name “Aronix M-1600”, manufactured by Toagosei Co., Ltd.) are mixed at 60 ° C., and 1-hydroxycyclohexyl phenyl ketone (trade name “Irgacure 184”, Ciba 3 parts of Specialty Chemicals Co., Ltd.) was added at 60 ° C. and mixed to obtain composition A ′ for photopolymerization. Subsequently, this was apply | coated so that a film thickness might be set to 200 micrometers on the PET film mounted on the glass plate. Next, while the PET film is placed on the glass plate, it is passed through an ultraviolet irradiation apparatus (product name “UB022-5B”, manufactured by Eye Graphics Co., Ltd.) having a HO2-L21 type mercury lamp 10 times to carry out ultraviolet polymerization. And a polymer (cured coating) A ′ was obtained.
The ultraviolet irradiation device has a lamp height of 10 cm, a conveyor speed of 10 m / min, and an ultraviolet irradiation intensity of 130 mJ / cm ² .

Comparative Examples 9-14
In Example 3, compositions B ′ to G ′ for photopolymerization were prepared in the same manner except that the compounds B to G were used in place of the compound A, and each composition was subjected to ultraviolet polymerization in the same process as described above. Polymers (cured coatings) B ′ to G ′ were obtained.

(Evaluation of curability)
In the ultraviolet polymerization, the curability of the photopolymerization composition A ′ was evaluated using the number of passes until tackiness (tack) on the cured product surface on the PET film disappeared as a tack-free time. Tack was determined by rubbing the surface of the cured product with a finger. Further, the curability was similarly evaluated for the photopolymerization compositions B ′ to G ′. The results are shown in Table 2.

(Evaluation of water absorption)
A PET film having a polymer (cured film) A ′ was cut into a strip of 45 mm length × 6 mm width, and a cured film peeled off from the PET film was used as a test piece. The test piece was dried at 120 ° C. for 24 hours and weighed (W ₀ ), then immersed in a 40 ° C. water bath for 24 hours and then thoroughly wiped to measure its weight (W ₁ ). The change (W ₀ −W ₁ ) / W ₀ × 100 was evaluated as the water absorption rate (%) of the cured coating. Further, the water absorption rate was similarly evaluated for the polymer (cured coating) C ′. The results are shown in Table 2.

(Evaluation of moisture permeability)
For the polymer (cured film) A ′, the moisture permeability of the film was measured according to JIS Z0208 (moisture permeable cup method). The moisture permeability (H ₂ O g / m ² ) was similarly measured for the polymers (cured coatings) C ′, D ′ and F ′. The results are shown in Table 2.

Example 4, Comparative Examples 15-19
1 g of the photopolymerization composition A ′ was diluted with methyl ethyl ketone to obtain a 30% by weight solution. Next, bar coater No. 12, the solution was applied to a PET film so that the film thickness was about 30 μm, dried at 80 ° C. for 1 minute, and then UV-polymerized by the same method as described above to obtain a polymer (cured film) A ′. 'created. Subsequently, pencil hardness (JIS-K-5400) was evaluated about this polymer A ''. Further, for the photopolymerization compositions C ′ to G ′, polymers C ″ to G ″ were prepared in the same manner, and pencil hardness was evaluated. The results are shown in Table 3.

Claims (4)

The following general formula (1):

(Wherein R ¹ represents hydrogen or a methyl group, a represents an integer of 1 to 6, and b represents an integer of 0 to 6). The following general formula (2-1):

Or an alicyclic dicarboxylic acid represented by the following general formula (2-2):

A monoamine represented by the general formula (3): H ₂ N— (CH ₂ ) _a —OH (where a represents an integer of 1 to 6). The compound is reacted to give the following general formula (4):

(In the formula, a represents an integer of 1 to 6), and an alicyclic imide compound represented by general formula (5): HOOC— (CH ₂ ) _b —C (R ¹ ) = The following general formula (1), characterized by reacting a vinyl compound represented by CH ₂ (wherein R ¹ is hydrogen or a methyl group, and b is an integer of 0 to 6):

(Wherein R ¹ represents hydrogen or a methyl group, a represents an integer of 1 to 6, and b represents an integer of 0 to 6). A polymerization composition comprising the alicyclic compound according to claim 1 or the alicyclic compound obtained by the production method according to claim 2. A polymer obtained by polymerizing the composition for polymerization according to claim 3.