JP2008088154A - New alicyclic compound, method for producing the same and polymer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new alicyclic compound obtained by using a naturally derived raw material and expected to have good physical properties especially as an electronic material and optical material. <P>SOLUTION: This alicyclic compound is expressed by general formula (1) [wherein, R<SB>1</SB>is a functional group expressed by general formula (2) (wherein, R<SB>3</SB>to R<SB>5</SB>are each H or methyl; (n) is 1 to 6 integer; and (m) is 0 to 12 integer); and R<SB>2</SB>is an alicyclic backbone derived from a monoterpene compound]. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a novel alicyclic compound, a method for producing a novel alicyclic compound, and a polymer composition. More specifically, the present invention relates to a novel alicyclic compound using a natural raw material (monoterpene compound), a method for producing the novel alicyclic compound, and a polymer composition obtained by polymerizing the monomer.

Polymerizable monomers having an alicyclic structure are awarded especially in the field of electronic materials and optical materials, and various kinds of performance (heat resistance, strength, transparency, moisture resistance, etc.) of these materials are variously improved. The molecular structure of For example, a specific alicyclic imide acrylate according to Patent Document 1 is supposed to give a polymer composition excellent in heat resistance and the like. However, the conventional alicyclic polymerizable monomer has an alicyclic structure derived from petroleum-based raw materials, and has problems such as an increase in product cost due to fluctuations in crude oil prices, environmental load, and resource depletion.
JP 2000-239254 A

The main object of the present invention is to provide a novel alicyclic compound using a natural product-derived raw material.

As a result of intensive studies on alicyclic compounds derived from natural raw materials, the present inventor has found an alicyclic compound having an alicyclic skeleton derived from a monoterpene compound, and has found a method for synthesizing the compound. The present invention has been completed.

That is, the present invention provides an alicyclic compound represented by the following general formula (1);

（式中、Ｒ_１は、下記一般式（２）で示す官能基を、またＲ_２はモノテルペン化合物に由来する脂環骨格を表す。）

(In the formula, R ₁ represents a functional group represented by the following general formula (2), and R ₂ represents an alicyclic skeleton derived from a monoterpene compound.)

（式（２）中、Ｒ_３、Ｒ_４およびＲ_５はそれぞれ水素原子またはメチル基を、ｎは１〜６の整数を、ｍは０〜１２の整数を表す。）

(In formula (2), R ₃ , R ₄ and R ₅ each represent a hydrogen atom or a methyl group, n represents an integer of 1 to 6, and m represents an integer of 0 to 12.)

A process for producing an alicyclic compound represented by the following general formula (1), characterized by passing through the following steps (I) and (II);

(In the formula, R ₁ represents a functional group represented by the following general formula (2), and R ₂ represents an alicyclic skeleton derived from a monoterpene compound.)

（式（２）中、Ｒ_３、Ｒ_４およびＲ_５はそれぞれ水素原子またはメチル基を、ｎは１〜６の整数を、ｍは０〜１２の整数を表す。）

(In formula (2), R ₃ , R ₄ and R ₅ each represent a hydrogen atom or a methyl group, n represents an integer of 1 to 6, and m represents an integer of 0 to 12.)

[Process (I)]
The monoamine compound represented by the following general formula (5) is reacted with the alicyclic dicarboxylic acid represented by the following general formula (4-1) or the alicyclic dicarboxylic acid anhydride represented by the following general formula (4-2). A step of producing an alicyclic maleimide compound represented by the following general formula (6).

(In formulas (4-1) and (4-2), R ₂ is the same as described above.)

(In Formula (5), R ₃ , R ₄ , and n are the same as described above. R ₆ represents a hydroxyl group or a halogen atom.)

(In formula (6), R ₂ , R ₃ , R ₄ , n, and R ₆ are the same as above.)

[Process (II)]
A step of reacting the alicyclic maleimide compound represented by the general formula (6) with a vinyl compound represented by the following general formula (7).

(In formula (7), m and R ₅ are the same as above)

The present invention also relates to a polymer composition obtained by polymerizing the alicyclic compound.

Since the alicyclic compound of the present invention uses natural raw materials (monoterpene compounds), problems such as environmental burden are small compared to conventional alicyclic compounds using petroleum-based raw materials. In addition, this compound has a bulky bicyclo skeleton to which an alkyl group is bonded or a cyclo skeleton to which a long chain alkyl group is bonded, and has an advantageous effect different from that of a conventional alicyclic compound (for example, its heavy weight). High heat resistance, low water absorption, low moisture permeability, etc.) are expected.

In addition, the polymer composition obtained by polymerizing the alicyclic compound of the present invention includes various engineering materials such as optical materials (overcoat agents for optical disk recording media, hard coat agents, groove materials, lenses, etc.), electronic It is also expected to be useful as a material (interlayer insulating film, resist, die bond agent, adhesive such as a diode / crystal resonator, element such as a diode, mold member, die bond film, solder resist, etc.). The polymer composition is also expected to be useful as various molded products in addition to paint binders, printing ink binders, adhesives, pressure-sensitive adhesives, dental materials, papermaking chemicals, and the like. For example, lenses [Fresnel Lens, lenticular lens, prism sheet, and the like].

The alicyclic compound (hereinafter referred to as alicyclic imide acrylate) according to the present invention is represented by the following general formula (1).

（式中、Ｒ_１は、下記一般式（２）で示す官能基を、またＲ_２はモノテルペン化合物に由来する脂環骨格を表す。）

(In the formula, R ₁ represents a functional group represented by the following general formula (2), and R ₂ represents an alicyclic skeleton derived from a monoterpene compound.)

（式（２）中、Ｒ_３、Ｒ_４およびＲ_５はそれぞれ水素原子またはメチル基を、ｎは１〜６の整数を、ｍは０〜１２の整数を表す。）

(In formula (2), R ₃ , R ₄ and R ₅ each represent a hydrogen atom or a methyl group, n represents an integer of 1 to 6, and m represents an integer of 0 to 12.)

R ₂ of the alicyclic compound represented by the general formula (1) (an alicyclic skeleton derived from the monoterpene compound) is not particularly limited, but the alicyclic compound specifically includes the following general formula (3-1) ), (3-2), (3-3) and (3-4) are preferred. The alicyclic skeleton of the general formula (3-1) is α-terpinene, that of the general formula (3-2) is α-ferrandrene, that of the general formula (3-3) is myrcene, and the general formula (3 It is derived from aloomesin in -4).

(In each formula, R ₁ represents the functional group represented by the general formula (2). The broken line portion represents that the carbon-carbon bond may be an unsaturated bond.)

  Although the manufacturing method of alicyclic imide acrylate shown by the said General formula (1) is not specifically limited, For example, it can manufacture by passing through the following process (I) and process (II).

[Process (I)]
The alicyclic dicarboxylic acid represented by the following general formula (4-1) or the alicyclic dicarboxylic acid anhydride represented by the following general formula (4-2) (hereinafter referred to as alicyclic dicarboxylic acid (anhydride)) A step of producing a cycloaliphatic maleimide compound represented by the following general formula (6) by reacting a monoamine compound represented by the following general formula (5) with the monoamine compound represented by the following general formula (5).

(In formulas (4-1) and (4-2), R ₂ represents an alicyclic skeleton derived from a monoterpene compound.)

(In Formula (5), R ₃ and R ₄ each represent a hydrogen atom or a methyl group, n represents an integer of 1 to 6, and R ₆ represents a hydroxyl group or a halogen atom.)

(In formula (6), R ₂ , R ₃ , R ₄ , n, and R ₆ are the same as above.)

[Process (II)]
A step of reacting the alicyclic maleimide compound represented by the general formula (6) with a vinyl compound represented by the following general formula (7).

(In Formula (7), m represents an integer of 0 to 12, and R ₅ represents a hydrogen atom or a methyl group.)

[About step (I)]
The alicyclic dicarboxylic acid (anhydride) represented by the general formula (4-1) or (4-2) includes, for example, various known monoterpene compounds and maleic acid (anhydride) (maleic acid or maleic anhydride). Can be obtained by Diels-Alder reaction by various known methods. In addition, the alicyclic dicarboxylic acid of the general formula (4-1) can also be obtained by hydrolyzing the Diels-Alder reaction product of the monoterpene compound and the dialkyl maleate with various known methods. be able to. Moreover, the alicyclic dicarboxylic acid anhydride represented by the general formula (4-2) can also be obtained by dehydrating and condensing the alicyclic dicarboxylic acid by various known methods. The alicyclic dicarboxylic acid (anhydride) is preferably an alicyclic dicarboxylic acid anhydride because an amidation or imidation reaction described later easily proceeds.

As the monoterpene compound, specifically, a monoterpene compound having a conjugated double bond in the molecule can be used, preferably α-terpinene (the following general formula (8-1)), α-ferran Cyclic monoterpene compounds such as drain (the following general formula (8-2)) and acyclic monoterpenes such as myrcene (the following general formula (8-3)) and aloomesin (the following general formula (8-4)) Compounds can be used.
Here, alicyclic imide acrylate using α-terpinene was used in the general formula (3-1), and alicyclic imide acrylate using α-ferrandrene was used in the general formula (3-2). The alicyclic imide acrylate corresponds to the general formula (3-3), and the alicyclic imide acrylate using aloomesin corresponds to the general formula (3-4) or (3-5) (both are in an isomer relationship). To do.
In addition, as for this monoterpene compound, the high purity commercial item (usually 85% or more) can be utilized as it is. The monoterpene compound used in the present invention includes other cyclic or acyclic monoterpene compounds (for example, β-ferrandrene, β-terpinene, γ-terpinene, α-pinene, osymene, etc.) as a residue. It may be included.

The Diels-Alder reaction is not particularly limited, and various known methods can be used. Specifically, for example, 1 mol of the monoterpene compound and maleic acid (anhydride), which is usually about 0.8 to 1.2 mol, are usually used at a temperature of about room temperature to about 200 ° C. What is necessary is just to make it react for about 3 to 12 hours. In consideration of the coloring of the alicyclic dicarboxylic acid (anhydride), it is preferable that the reaction vessel has a sealed structure and further purged with an inert gas such as nitrogen. In the reaction, one kind selected from various known solvents [benzene, toluene, xylene, n-pentane, n-hexane, n-pentane, cyclopentane, methyl acetate, ethyl acetate, isobutyl acetate, etc.] They can be used alone or in combination. The alicyclic dicarboxylic acid (anhydride) thus obtained can be purified by various purification means [vacuum distillation, steam distillation, solvent extraction, recrystallization, silica gel column chromatography, etc.].

Further, when the obtained alicyclic dicarboxylic acid (anhydride) contains a carbon-carbon unsaturated bond in the alicyclic skeleton (R ₂ ) in the molecule, the alicyclic dicarboxylic acid (anhydride) is The carbon-carbon unsaturated bond can be converted to a saturated bond by subjecting it to a hydrogenation reaction. The hydrogenation reaction is not particularly limited, and various known methods can be used. Specifically, for example, the alicyclic dicarboxylic acid (anhydride) is present in various known metal catalysts (stabilized nickel, palladium, palladium carbon, platinum, etc.) and, if necessary, a solvent such as THF. The hydrogenation reaction may be carried out under conditions of a hydrogen pressure of usually 9.8 MPa or less (preferably 0.98 to 9.8 MPa), a temperature of room temperature to about 300 ° C., and a time of about 3 to 24 hours.

As the monoamine compound represented by the general formula (5), various known compounds can be used depending on the type of R _{6 in} the general formula (5). Specifically, for example, when R ₆ is a hydroxyl group, various known monoamino alcohols [ethanolamine, propanolamine, butanolamine and the like] can be exemplified. When R ₆ is a halogen atom (fluorine, chlorine, bromine, etc.), various known halogenated alkylamines [2-chloroethylamine, 2-bromoethylamine, 1-amino-2-propyl chloride, etc.] It can be illustrated. Among these, the monoamino alcohols, particularly ethanolamine is preferable from the viewpoint of availability and inexpensiveness.

The reaction between the alicyclic dicarboxylic acid (anhydride) and the monoamine compound is based on various known amidation and imidation reactions. Specifically, for example, 1 mol of the alicyclic dicarboxylic acid (anhydride) and the monoamine compound, which is usually about 0.5 to 3 mol, are usually a solvent (toluene) azeotroped with water. Etc.) in the presence of an amidation reaction, usually at a temperature of about 10 ° C. to 70 ° C., usually for about 1 to 12 hours, and further at a temperature of about 80 ° C. to 180 ° C., usually for about 3 to 20 hours. What is necessary is just to make it react (dehydration ring closure reaction).

  In the amidation reaction, various known acid or base catalysts may be used for the purpose of promoting the reaction. Specifically, for example, various known organic sulfonic acids [alkylsulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, etc.], inorganic acids [sulfuric acid, phosphorous acid, etc.], basic compounds [pyridine, trimethylamine, triethylamine, etc.] Etc.] can usually be used in an amount of about 0.0005 to 0.05 mol with respect to 1 mol of the alicyclic dicarboxylic acid (anhydride).

In the imidation reaction, various known catalysts may be used for the purpose of performing the reaction in a low temperature range of about 50 ° C to 100 ° C. Specifically, for example, a combination of a dehydrating agent such as dicyclohexylcarbodiimide or acetic anhydride and a basic compound such as pyridine, triethylamine or sodium acetate can be used. In addition, the usage-amount of the said basic compound is about 1-5 mol normally with respect to 1 mol of dehydrating agents.

In both reactions, various polymerization prohibition measures can be taken as necessary. Specifically, for example, a polymerization inhibitor (phenols, dithiocarbamates, phenothiazines, etc.) is usually about 0.0001 to 0.01 mol% with respect to 1 mol of the alicyclic dicarboxylic acid (anhydride). It can be used or the reaction system can be bubbled with air or oxygen.

The alicyclic maleimide compound represented by the general formula (6) thus obtained may be purified by the purification means. Further, when the alicyclic maleimide compound contains a carbon-carbon unsaturated bond in the alicyclic skeleton in the molecule, a hydrogenation reaction may be applied at this stage as described above.

[About Process (II)]
The method of reacting the alicyclic maleimide compound with the vinyl compound represented by the general formula (7) differs depending on the type of R _{6 in} the general formula (6). For example, when R ₆ is a hydroxyl group, the alicyclic maleimide compound and the vinyl compound may be esterified. When R ₆ is a halogen atom, the alicyclic maleimide compound and the vinyl compound may be subjected to a substitution reaction by various known methods.

  Specific examples of the vinyl compound include acrylic acid, methacrylic acid, 3-butenoic acid, 4-pentenoic acid and the like.

The esterification reaction is not particularly limited, and various known methods can be used. Specifically, for example, 1 mol of the alicyclic maleimide compound and the vinyl compound which is usually about 0.5 to 20 mol are usually 2 to 20 ° C. What is necessary is just to make it react for about 20 hours. In the reaction, it is preferable to use an aromatic solvent (preferably toluene) azeotroped with water and perform the reaction while removing water from the reaction system. If necessary, various known esterification catalysts such as acid catalysts (p-toluenesulfonic acid, sulfuric acid, etc.), metal oxides / hydroxides (lithium hydroxide, calcium oxide, magnesium oxide, etc.) Usually, about 0.001 to 0.2 mol can be used with respect to 1 mol of the compound. Moreover, the said superposition | polymerization prohibition measure can also be applied as needed. The usage-amount of a polymerization inhibitor is about 0.0001-0.01 mol% normally with respect to 1 mol of this alicyclic maleimide compound.

The substitution reaction is not particularly limited, and various known methods can be used. Specifically, for example, 1 mol of the alicyclic maleimide compound, usually about 0.8 to 2 mol of the vinyl compound, and a basic catalyst of the same mol as the vinyl compound (for example, sodium hydroxide aqueous solution) And about 1 mol of the alicyclic maleimide compound (usually dissolved in a mixed solvent consisting of toluene and methanol) in a solution consisting of various solvents as necessary over a period of usually 30 minutes to 2 hours. The reaction may be carried out by dropping, and the substitution reaction is usually about 20 ° C to 150 ° C, usually about 2 to 20 hours.

Note that the alicyclic maleimide compound, carbon in R ₂ in the general formula (6) - when carbon unsaturated bond, can be applied to the polymerization inhibiting action. The usage-amount of a polymerization inhibitor is about 0.0001-0.01 mol% normally with respect to 1 mol of this alicyclic maleimide compound.

The thus obtained alicyclic imide acrylate represented by the general formula (1) is usually highly pure as it is, but the purity can be further improved by purifying it by the purification means. Further, when the alicyclic imide acrylate contains a carbon-carbon unsaturated bond in the alicyclic skeleton in the molecule, a hydrogenation reaction may be applied as described above. A polymer using a hydrogenated alicyclic imide acrylate has characteristics such as good heat resistance and a high softening point.

  Since the alicyclic imide acrylate according to the present invention has a polymerizable double bond in the molecule, various oily or aqueous polymer compositions can be obtained by polymerizing alone or copolymerizing with other polymerizable monomers. It can be a thing.

Other polymerizable monomers include, for example, 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 [allylamine, 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 quaternized. Cationic vinyl monomers, polyfunctional vinyl monomers (divinylbenzene, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane) that are quaternized with an agent (methyl chloride, benzyl chloride, dimethyl sulfate, epichlorohydrin, etc.) Triacrylate, ditrimethylolpropane tetraacrylate, bisphenol A tetraethylene glycol diacrylate, hexamethylene glycol diacrylate, 1,9-nonanediol diacrylate , Pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, N-vinyl pyrrolidone, (meth) acrylamide N-vinylformamide, 4-hydroxybutyl vinyl ether, diethylene glycol divinyl ether, etc.], and vinyl acetate. One species can be used alone, or two or more species can be used in combination.

  In the case where the alicyclic imide acrylate of the present invention is copolymerized with the other monomer, the weight ratio between the two can be appropriately determined according to the use of the obtained polymer composition. For example, the former: the latter Is about 80:20 to 10:90.

The polymerization method is not particularly limited, and for example, a method of irradiating active energy rays (ultraviolet rays or electron beams) (photopolymerization) or heating (heat polymerization) can be employed. The polymerization can also be performed in the presence or absence of the solvent.

In the photopolymerization, various known photopolymerization initiators can be used. Specifically, for example, acetophenones [acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2- Methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one and N, N-dimethylaminoacetophenone, etc.], benzophenones [benzophenone, methylbenzophenone, 4,4′-dichlorobenzophenone, 4 , 4′-bisdiethylaminobenzophenone, Michler's ketone, 4-benzoyl-4′-methyldiphenyl sulfide, etc.], thioxanthones [2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxone] Thioxanthones such as N-tone and 2,4-diisopropylthioxanthone], anthraquinones [such as 2-methylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone], benzoins [such as benzoin, benzoin methyl ether and benzoin propyl ether] These can be used singly or in combination of two or more. Further, if necessary, photosensitizers such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, triethylamine and triethanolamine can be used in combination. In addition, both the usage-amount of this photoinitiator and this photosensitizer are about 0.01 to 10 weight% normally with respect to the solid content weight of a polymer composition.

In the thermal polymerization, various known thermal polymerization initiators can be used. Specifically, for example, organic peroxide [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 and azodi-t-butane, etc.], and these can be used alone or in combination of two or more. That. In addition, the said organic peroxide is good also as a redox-type initiator by combining with a reducing agent. The usage-amount of this thermal-polymerization initiator is about 0.01 to 10 weight% normally with respect to the solid content weight of a polymer composition.

  In addition, the polymerization inhibitor and the polymerization prohibition measure can be applied during the polymerization reaction.

  Various additives can be applied to the polymer composition of the present invention depending on its use. Specifically, for example, inorganic fillers (silica powder, alumina, zircon, calcium silicate, calcium carbonate, etc.) can be applied for the purpose of improving properties such as heat resistance, adhesion, and hardness, and colorants (phthalocyanine).・ Blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, etc.], flame retardants (antimony trioxide, phosphate esters, red phosphorus, melamine resins and other nitrogen-containing compounds) Etc.], antifoaming agents (silicone-based, fluorine-based, polymer-based, etc.), adhesion-imparting agents (imidazoles, thiazoles, triazoles, silane coupling agents, etc.), stress relieving agents (silicone oil, silicone rubber powder) Etc.), light stabilizers (hindered amine compounds, etc.), charging Or the like can be used stop, leveling agents. Moreover, the said solvent can also be used as a dilution solvent.

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. As an electron beam source,
For example, a Cockloft-Waltsin type, a bandegraph type or a resonant transformer type irradiation device may be mentioned.

Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to these examples. In addition, the following apparatus was used for the spectrum measurement.
¹ H-NMR, ¹³ C-NMR: BRUKERARX300 (manufactured by Bruker BioSpin)
_IR: AVATAR 3 60 (ThermoNicolet Co., Ltd.)
Gas chromatography (GC): 5890 SERIES II (made by HEWLETT)

Example 1
A reaction vessel equipped with a thermometer, a dropping funnel, a nitrogen gas inlet, and a stirrer was charged with 179.9 g of maleic anhydride and 350 mL of dehydrated toluene, and the system was purged with nitrogen. Next, maleic anhydride was dissolved at 50 ° C., and 277.8 g of α-terpinene (manufactured by Wako Pure Chemical Industries, Ltd., purity 90%) was stirred in a water bath so that the temperature in the system was about 60 ° C. The solution was added dropwise while suppressing the exotherm. When the temperature in the system began to drop after completion of the dropwise addition, Diels-Alder reaction was performed for 6 hours while heating and stirring at 60 ° C. After completion of the reaction, the solvent and unreacted raw material were removed by distillation under reduced pressure to collect a solid, which was dried under reduced pressure to obtain alicyclic dicarboxylic acid anhydride (hereinafter referred to as α-terpinenic acid anhydride) 417. 0.1 g was obtained. In addition, the purity (referred to as a measured value by the GC method, hereinafter the same) of this product was 96.9%.

  Next, a reaction vessel equipped with a Dean-Stark water separator (Dimroth condenser), thermometer, dropping funnel, nitrogen gas inlet, and stirrer was charged with 180.0 g of the α-terpinenic acid anhydride and 200 mL of dehydrated toluene, The system was replaced with nitrogen. Next, 45.3 g of ethanolamine was added dropwise while stirring the system at room temperature. After completion of the dropwise addition, the reaction system was heated to 106 to 110 ° C., and an imidization reaction was performed for 20 hours while distilling water from the system with a Dean-Stark water separator. At that time, imidization reaction was performed while replenishing toluene and ethanolamine azeotropically removed into the system. After completion of the reaction, the solvent was distilled off under reduced pressure, and n-hexane was added for recrystallization. Subsequently, the obtained crystal was dried under reduced pressure to obtain 207.0 g of an alicyclic maleimide compound. The purity of this product was 97.2%.

Next, 150.0 g of the alicyclic maleimide compound, 1.85 g of hydroquinone, toluene in a reaction vessel equipped with a Dean-Stark water separator (Dimroth condenser), a thermometer, a dropping funnel, an air bubbling introduction tube, and a stirrer. 300 mL was charged, and 3.70 g of p-toluenesulfonic acid and 185.1 g of acrylic acid were added and stirred. Next, the temperature of the reaction system was raised to 106 to 110 ° C. while bubbling with air, and the esterification reaction was carried out for 21 hours while water was distilled away from the system using a Dean-Stark water separator. At that time, the progress of the reaction was followed by GC. In addition, the reaction was carried out while adding p-toluenesulfonic acid into the system for the purpose of promoting and completing the reaction. Next, the reaction solution was cooled to room temperature, washed with ion-exchanged water and an aqueous sodium hydrogen carbonate solution three times using a separatory funnel, and further toluene was distilled off under reduced pressure to obtain an alicyclic imide acrylate (A-1 ) (Hereinafter referred to as Compound A-1) 128.7 g. The purity of this product was 92.4%.

¹ H-NMR (300 MHz, solvent CDCl ₃ , δ (ppm)) : 6.36, 6.10, 5.86, 4.20, 3.71, 2.93, 2.54, 1.47, 1 .27, 1.09, 0.97
¹³ C-NMR (300 MHz, solvent CDCl ₃ , δ (ppm)): 177.10, 165.61, 135.09, 135.36, 131.20, 128.00, 127.89, 60.93, 50 .09, 46.23, 43.50, 36.85, 34.18, 29.52, 22.80, 18.30, 16.78
IR (neat) : 2960, 1726, 1702, 1692, 1400, 1182 cm ⁻¹

Example 2
A reaction vessel equipped with a thermometer and a hydrogen balloon was charged with 180.0 g of α-terpinenic acid anhydride obtained in Example 1, 18.0 g of palladium carbon, and 200 mL of dehydrated THF, and hydrogenated at 50 ° C. for 30 hours with stirring. The reaction was carried out. After completion of the reaction, the reaction system was cooled to room temperature, palladium carbon was removed by filtration, and then THF was distilled off under reduced pressure. Subsequently, the obtained solid was dried under reduced pressure to obtain 163.4 g of hydrogenated α-terpinenic acid anhydride.
The purity of this product was 98.6%.

Next, 118.9 g of the hydrogenated α-terpinenic acid anhydride and 200 mL of dehydrated toluene were placed in a reaction vessel equipped with a Dean-Stark water separator (Dimroth condenser), thermometer, dropping funnel, nitrogen gas inlet, and stirrer. The system was purged with nitrogen. Thereafter, 30.7 g of ethanolamine was added dropwise to the stirred reaction system at room temperature. When the heat generation in the system settled after completion of the dropwise addition, the reaction system was heated to 106 to 110 ° C., and an imidization reaction was carried out for 8 hours while distilling water from the system with a Dean-Stark water separator. At that time, the reaction was carried out while replenishing toluene and ethanolamine distilled off together with water. After completion of the reaction, the solvent was distilled off under reduced pressure, and then n-hexane was added for recrystallization. Thereafter, the obtained crystal was dried under reduced pressure to obtain 119.6 g of an alicyclic maleimide compound. The purity of this product was 98.9%.

Next, 119.5 g of the alicyclic maleimide compound, 0.56 g of hydroquinone, toluene are added to a reaction vessel equipped with a Dean-Stark water separator (Dimroth condenser), a thermometer, a dropping funnel, an introduction tube for air bubbling, and a stirrer. 400 mL was charged, and 8.14 g of p-toluenesulfonic acid and 146.4 g of acrylic acid were added and stirred. Next, the reaction system was heated to 106 to 110 ° C. while bubbling with air, and the esterification reaction was carried out for 7 hours while distilling water from the system with a Dean-Stark water separator. Next, the reaction solution was cooled to room temperature, washed with ion-exchanged water and an aqueous sodium hydrogen carbonate solution three times using a separatory funnel, and further toluene was distilled off under reduced pressure to obtain an alicyclic imide acrylate (A-2 ) (Hereinafter referred to as Compound A-2) 109.1 g was obtained. The purity of this product was 97.0%.

¹ H-NMR (300 MHz, solvent CDCl ₃ , δ (ppm)) : 6.39, 6.10, 5.83, 4.32, 3.83, 2.94, 2.54, 1.47, 1 .13, 0.97, 0.81
¹³ C-NMR (300 MHz, solvent CDCl ₃ , δ (ppm)) : 178.19, 131.33, 131.06, 128.05, 127.86, 61.08, 59.57, 48.77, 44 .82, 37.13, 33.92, 31.07, 28.99, 26.36, 25.26, 22.93, 17.30, 16.91
IR (neat) : 2949, 1726, 1702, 1692, 1396, 1182 cm ⁻¹

Example 3
A reaction vessel equipped with a thermometer, a dropping funnel, a nitrogen gas inlet, and a stirrer was charged with 309.8 g of maleic anhydride and 250 mL of dehydrated toluene, and the system was purged with nitrogen. Next, maleic anhydride was dissolved at 50 ° C., and 503.4 g of myrcene (manufactured by Aldrich, purity 90%) was added dropwise with stirring while suppressing heat generation in a water bath so that the temperature in the system was about 60 ° C. When the temperature in the system began to drop after completion of the dropwise addition, Diels-Alder reaction was carried out for 3 hours while heating and stirring at 60 ° C. After completion of the reaction, by-products are separated by filtration, the solvent and unreacted raw material are distilled off under reduced pressure to remove a pale yellow liquid, and this is dried under reduced pressure to obtain an alicyclic dicarboxylic acid anhydride (hereinafter, 646.9 g of myrsenic anhydride was obtained. The purity of this product was 90.2%.

  Next, 175.0 g of myrsenic anhydride and 200 mL of dehydrated toluene were charged into a reaction vessel equipped with a Dean-Stark water separator (Dimroth condenser), thermometer, dropping funnel, nitrogen gas inlet, and stirrer. Was replaced with nitrogen. Next, 45.6 g of ethanolamine was added dropwise while stirring the system at room temperature. After completion of the dropwise addition, the reaction system was heated to 106 to 110 ° C., and an imidization reaction was performed for 12 hours while water was distilled away from the system using a Dean-Stark water separator. After completion of the reaction, the solvent was distilled off under reduced pressure, and the obtained pale yellow viscous solid was dried under reduced pressure to obtain 189.4 g of an alicyclic maleimide compound. The purity of this product was 88.0%.

Next, 160.0 g of the alicyclic maleimide compound, 1.73 g of hydroquinone, toluene are added to a reaction vessel equipped with a Dean-Stark water separator (Dimroth condenser), a thermometer, a dropping funnel, an air bubbling introduction tube, and a stirrer. 200 mL was charged, and 9.66 g of p-toluenesulfonic acid and 173.7 g of acrylic acid were added and stirred. Next, the reaction system was heated to 106-110 ° C. while bubbling with air, and the esterification reaction was carried out for 21 hours while water was distilled off from the system using a Dean-Stark water separator. At that time, the progress of the reaction was followed by GC. Next, the reaction solution was cooled to room temperature, washed with ion-exchanged water and an aqueous sodium hydrogen carbonate solution three times using a separatory funnel, and further toluene was distilled off under reduced pressure to obtain an alicyclic imide acrylate (A-3). ) (Hereinafter referred to as Compound A-3) 132.5 g was obtained. The purity of this product was 89.0%.

¹ H-NMR (300 MHz, solvent CDCl ₃ , δ (ppm)) : 6.40, 6.06, 5.82, 5.56, 5.02, 4.28, 3.77, 3.06, 2 .52, 2.22, 1.67, 1.58, 1.27, 1.01, 0.94, 0.76
¹³ C-NMR (300 MHz, solvent CDCl ₃ , δ (ppm)): 179.76, 165.70, 140.30, 131.30, 127.87, 123.49, 119.73, 60.98, 39 .24, 37.26, 27.49, 25.91, 24.04, 19.32, 17.65
IR (neat) : 2929, 1701, 1398, 1182 cm ⁻¹

Example 4
A reaction vessel equipped with a thermometer and a hydrogen balloon was charged with 200.0 g of myrsenic anhydride obtained in Example 3, 15.0 g of palladium carbon, and 200 mL of dehydrated THF, and the hydrogenation reaction was performed at 50 ° C. for 72 hours with stirring. Went. After completion of the reaction, the reaction system was cooled to room temperature, palladium carbon was removed by filtration, and then THF was distilled off under reduced pressure. Next, the obtained solid was dried under reduced pressure to obtain 198.0 g of hydrogenated myrsenic anhydride. The purity of this product was 90.6%.

Next, in a reaction vessel equipped with a Dean-Stark water separator (Dimroth condenser), a thermometer, a dropping funnel, a nitrogen gas inlet, and a stirrer, 198.0 g of the hydrogenated myrsenic acid anhydride and 200 mL of dehydrated toluene were charged. The system was replaced with nitrogen. Thereafter, 52.5 g of ethanolamine was added dropwise to the stirred reaction system at room temperature. When the heat generation in the system was settled after the completion of the dropping, the reaction system was heated to 106 to 110 ° C., and an imidization reaction was carried out for 6 hours while distilling water from the system with a Dean-Stark water separator. After completion of the reaction, the temperature was returned to room temperature, the nitrogen gas inlet was replaced with an air bubbling inlet, 2.19 g of hydroquinone, 11.41 g of p-toluenesulfonic acid, and 218.9 g of acrylic acid were added and stirred. Next, the temperature of the reaction system was raised to 106 to 110 ° C. while bubbling with air, and the esterification reaction was carried out for 12 hours while distilling water from the system with a Dean-Stark water separator. Next, the reaction solution was cooled to room temperature, washed with ion-exchanged water and an aqueous sodium hydrogen carbonate solution three times using a separatory funnel, and further toluene was distilled off under reduced pressure to obtain an alicyclic imide acrylate (A-4). ) (Hereinafter referred to as Compound A-4) 206.0 g. The purity of this product was 85.6%.

¹ H-NMR (300 MHz, solvent CDCl ₃ , δ (ppm)): 6.34, 6.07, 5.82, 4.33, 3.81, 2.87, 2.22, 1.67, 1 .58, 1.27, 1.22, 1.15, 0.86
¹³ C-NMR (300 MHz, solvent CDCl ₃ , δ (ppm)): 179.86, 165.68, 132.20, 127.85, 60.96, 39.70, 36.89, 34.01, 28 .73, 27.83, 24.26, 22.52
IR (neat) : 2927, 1708, 1397, 1182 cm ⁻¹

Comparative Example 1
Tetrahydrophthalic anhydride (trade name “Ricacid 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
In a reaction vessel equipped with a Dean-Stark water separator (Dimroth condenser), thermometer, dropping funnel, nitrogen gas inlet, and stirrer, 150.0 g of succinic anhydride (Wako Pure Chemical Industries, Ltd.) and 150. dehydrated toluene. 0 g was charged and the inside of 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 to obtain imidoacrylate 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.)

Example 5
50 parts of the compound A-1, 50 parts of toluene, and 0.9 part of azobisisobutyronitrile (3 mol% with respect to 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, 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 a polymer A-1. It was. The polymer A-1 was subjected to the following heat resistance test.

Examples 6-8
Polymers A-2 to A-4 were prepared for the compounds A-2 to A-4 in the same manner as in Example 5, and each was subjected to the following heat resistance test.

(Evaluation of heat resistance)
About the said polymers A-1 to A-4, using a commercially available thermogravimetric measuring device (TG-DTA) and a differential scanning calorimeter (DSC) (product name "2000S system WS002", manufactured by Mac Science). The thermal decomposition onset temperature and Tg were determined. The measurement conditions and the numerical value calculation method are as follows. The results are shown in Table 1.

TG-DTA: The temperature at the bending point that appeared on the chart when the sample was heated from room temperature at 10 ° C./min and heated to 800 ° C. was defined as the thermal decomposition start temperature.
DSC: From the second cycle curve obtained when the sample was heated from -50 ° C. at 10 ° C./min to 200 ° C., then cooled again to −50 ° C., and again heated to 200 ° C. The inflection point was calculated by the tangent method and set as Tg.

Example 9
80 parts of the compound A-3 and 20 parts of urethane acrylate (trade name “Aronix M-1600”, manufactured by Toagosei Co., Ltd.) were mixed at 60 ° C., and further 1-hydroxycyclohexyl phenyl ketone (trade name “Irgacure 184”). 3 parts of Ciba Specialty Chemicals Co., Ltd.) was added at 60 ° C. and mixed to obtain composition A ′ for photopolymerization. Subsequently, this was apply | coated to PET film mounted on the glass plate so that a film thickness might be set to about 200 micrometers after hardening. Next, while the PET film is placed on a glass plate, it is passed 10 times through an ultraviolet irradiation device (product name “UB022-5B”, manufactured by Eye Graphics Co., Ltd.) equipped with a HO2-L21 type mercury lamp to carry out ultraviolet polymerization. And polymer (cured coating) A′-3 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 . The completion of the curing was judged when the surface of the coating was rubbed with a finger after the ultraviolet irradiation pass and tack (adhesiveness) disappeared.

Example 10
In Example 9, a photopolymerizable composition A′-4 was prepared in the same manner except that A-4 was used instead of the compound A-3, and each composition was subjected to ultraviolet polymerization in the same process as described above. Polymer (cured film) A′-4 was obtained.

Comparative Examples 3-5
In Example 9, photopolymerizable compositions B ′ to D ′ were prepared in the same manner except that the compounds B to D were used in place of the compound A-3, and each composition was subjected to ultraviolet rays in the same manner as described above. Polymerization was performed to obtain polymers (cured coatings) B ′ to D ′.

(Evaluation of water absorption)
A PET film having a polymer (cured film) A′-3 was cut into strips of 45 mm in length × 6 mm in width and 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 ₁ −W ₀ ) / W ₀ × 100 was evaluated as the water absorption rate (%) of the cured coating. Further, the water absorption rate of the polymers (cured coatings) A′-3 and A′-4 and the polymers (cured coatings) B ′, C ′ and D ′ were evaluated in the same manner. The results are shown in Table 2.

Examples 11-12, Comparative Examples 6-8
1 g of the photopolymerization composition A′-3 was diluted with methyl ethyl ketone to obtain a 30% by weight solution. Next, bar coater No. 12 was applied to a PET film so that the film thickness was about 3 μm after curing, dried at 80 ° C. for 1 minute, and then UV-polymerized in the same manner as described above to obtain a polymer (cured film). A ″ -3 was created. The polymer A ″ -3 was then evaluated for pencil hardness (JIS-K-5400) and Tg. Further, for the photopolymerization compositions A′-4 and B ′ to D ′, polymers A ″ -4 and B ″ to D ″ were similarly prepared, and pencil hardness was evaluated. The results are shown in Table 3.

Claims (6)

An alicyclic compound represented by the following general formula (1).

(In the formula, R ₁ represents a functional group represented by the following general formula (2), and R ₂ represents an alicyclic skeleton derived from a monoterpene compound.)

(In formula (2), R ₃ , R ₄ and R ₅ each represent a hydrogen atom or a methyl group, n represents an integer of 1 to 6, and m represents an integer of 0 to 12.) The general formula (1) is represented by one selected from the following general formulas (3-1), (3-2), (3-3), (3-4) and (3-5). The alicyclic compound according to claim 1, characterized in that it is characterized in that

(In each formula, R ₁ represents a functional group represented by the following general formula (2). The broken line portion represents that the carbon-carbon bond may be an unsaturated bond.)

(In formula (2), R ₃ , R ₄ and R ₅ each represent a hydrogen atom or a methyl group, n represents an integer of 1 to 6, and m represents an integer of 0 to 12.) A process for producing an alicyclic compound represented by the following general formula (1), wherein the process passes through the following steps (I) and (II).

(In the formula, R ₁ represents a functional group represented by the following general formula (2), and R ₂ represents an alicyclic skeleton derived from a monoterpene compound.)

(In formula (2), R ₃ , R ₄ and R ₅ each represent a hydrogen atom or a methyl group, n represents an integer of 1 to 6, and m represents an integer of 0 to 12.)
[Process (I)]
To the alicyclic dicarboxylic acid represented by the following general formula (4-1) or the alicyclic dicarboxylic acid anhydride represented by the following general formula (4-2),
A step of reacting a monoamine compound represented by the following general formula (5) to produce an alicyclic maleimide compound represented by the following general formula (6).

(In formulas (4-1) and (4-2), R ₂ represents an alicyclic skeleton derived from a monoterpene compound.)

(In Formula (5), R ₃ and R ₄ each represent a hydrogen atom or a methyl group, n represents an integer of 1 to 6, and R ₆ represents a hydroxyl group or a halogen atom.)

(In the formula (6), R ₂ , R ₃ , R ₄ , n and R ₆ are the same as above.)
[Process (II)]
A step of reacting the alicyclic maleimide compound represented by the general formula (6) with a vinyl compound represented by the following general formula (7).

(In Formula (7), m represents an integer of 0 to 12, and R ₅ represents a hydrogen atom or a methyl group.) The general formula (1) is represented by one selected from the following general formulas (3-1), (3-2), (3-3), (3-4) and (3-5). The manufacturing method according to claim 3, wherein the manufacturing method is characterized.

(In each formula, R ₁ represents a functional group represented by the following general formula (2). The broken line portion represents that the carbon-carbon bond may be an unsaturated bond.)

(In formula (2), R ₃ , R ₄ and R ₅ each represent a hydrogen atom or a methyl group, n represents an integer of 1 to 6, and m represents an integer of 0 to 12.) A composition for polymerization comprising the alicyclic compound according to claim 1. A polymer composition obtained by polymerizing the composition for polymerization according to claim 5.