JP2011144287A - Multifunctional polymerizable compound, method for producing the same, and ultraviolet ray absorbing cured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable compound that has both at least two polymerizable functional groups and ultraviolet ray absorbing part, gives a product of high molecular weight, can be synthesized by a simple process, and is less likely to be colored by metal components; and to provide a method for producing the same. <P>SOLUTION: The multifunctional polymerizable compound can be obtained by reaction of a compound represented by formula (1) and a compound having an epoxy group and (meth)acrylic group, wherein R<SB>11</SB>to R<SB>15</SB>each independently represent hydrogen, hydroxyl, methyl, or methoxy, and at least one of R<SB>11</SB>to R<SB>15</SB>is a hydroxyl. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a novel polymerizable compound having an ultraviolet absorbing ability and a method for producing the same. More specifically, as UV absorbers, it is used in general polymer materials such as weather-resistant polycarbonate for outdoor use, outdoor paints for automobiles, clear top coating materials, inkjet printing materials, glasses, contact lenses, light guide plates for LCD back panels, etc. The present invention relates to a novel polymerizable compound to be used.

  Conventionally, salicylate-based, hydroxybenzophenone-based, benzotriazole-based, triazine-based and benzoate-based compounds have been used as ultraviolet absorbers for polymer materials. Since most of these compounds are low molecular weight compounds, there is a problem that they are likely to bleed out when added to a polymer material and are likely to be deposited on a film.

  Moreover, since it is a low molecule, it is easily volatilized and volatilizes during the processing of the polymer material.

  In order to solve these problems, an attempt has been made to develop a high molecular weight ultraviolet absorber by introducing a polymerizable functional group into the ultraviolet absorber and polymerizing it, and hydroxybenzophenone as an ultraviolet absorber. An ultraviolet absorber having a polymerizable functional group using a benzotriazole-based compound has already been reported (Patent Documents 1 and 2). These UV-absorbing compounds are considered to stably convert UV energy into heat by keto-enol tautomerism, and the presence of a phenolic hydroxyl group is essential for the function of UV absorption. It has become.

  However, in order to proceed with a multi-step synthesis including introduction of a polymerizable functional group while leaving a free phenolic hydroxyl group in the final product, it is necessary to distinguish the reactivity with the hydroxyl group in the reagent. Since it is necessary to precisely control the reagent amount, temperature and the like as reaction conditions, the ultraviolet absorbers described in Patent Documents 1 and 2 have disadvantages in industrial production for mass production.

  In addition, hydroxybenzophenone and benzotriazole UV absorbers cause yellowing due to oxidation of free phenolic hydroxyl groups present in their structure or reaction with residual catalyst in the resin. Things are also known.

  Accordingly, there has been a demand for an ultraviolet absorber that can be produced by a simple process without requiring special control and that can be easily changed over time such as yellowing and can be increased in molecular weight.

  In addition, many UV absorbers, including hydroxybenzophenone and benzotriazole, are synthesized using a number of steps using petroleum-derived raw materials that are depleted resources. Therefore, there has been a demand for the development of an ultraviolet absorber that can be produced by a simple process without using petroleum-derived raw materials.

  Patent Document 3 discloses ferulic acid that is easily and in large quantities obtained from nature, and that the ability to absorb UV light hardly changes even when a phenolic hydroxyl group is blocked, in order to develop a new UV absorber under such a background. A polymerizable compound in which a (meth) acrylic acid unit is bonded to the phenolic hydroxyl group side is disclosed.

  However, since the ultraviolet absorber (polymerizable compound) described in Patent Document 3 has one polymerizable functional group, it has a crosslinking system that forms a strong cured product (usually having a plurality of polymerizable functional groups). When it is used for a polyfunctional compound, the physical properties of the cured product may be impaired. From this point of view, a benzotriazole-based compound has been reported as a polyfunctional UV absorber (Patent Document 1), but the structure of the compound is complicated and a problem that a number of steps are required for synthesis. There is.

JP 2000-119262 A JP 2002-80487 A JP 2009-215189 A

  An object of the present invention is a polymerizable compound having two or more polymerizable functional groups and an ultraviolet absorbing portion and capable of increasing the molecular weight, which can be synthesized in a simple process and hardly colored by a metal component. And providing a manufacturing method thereof.

  The present invention is a polyfunctional polymerizable compound obtained by reacting a compound represented by the following general formula (1) with a compound having an epoxy group and a (meth) acryl group.

(In the formula, R _{11 to} R ₁₅ each independently represent hydrogen, a hydroxyl group, a methyl group or a methoxy group, and at least one of R _{11 to} R ₁₅ is a hydroxyl group.)
The compound represented by the general formula (1) is preferably a compound represented by the following general formula (2) or (3).

(In the formula, R ₁₁ , R ₁₂ , R ₁₄ , and R ₁₅ each independently represent hydrogen, a hydroxyl group, a methyl group, or a methoxy group.)

(In the formula, R _{12 to} R ₁₅ each independently represent hydrogen, a hydroxyl group, a methyl group or a methoxy group.)
The compound represented by the general formula (2) is a compound represented by the following general formula (4) or (5), and the compound represented by the general formula (3) is represented by the following general formula (6). It is preferable that it is a compound.

(In the formula, R ₂₁ , R ₂₂ , R ₂₄ and R ₂₅ each independently represent hydrogen, a methyl group or a methoxy group.)

(In the formula, R ₂₁ , R ₂₄ and R ₂₅ each independently represent hydrogen, methyl group or methoxy group.)

(In the formula, R _{22 to} R ₂₅ each independently represent hydrogen, a methyl group or a methoxy group.)
The compound represented by the general formula (4) is a compound represented by any one of the following general formulas (7) to (9), and the compound represented by the general formula (5) is represented by the following general formula (10). It is preferable that the compound represented by the general formula (6) is a compound represented by the following general formula (11).

  The compound having an epoxy group and a (meth) acryl group is preferably any one of compounds represented by the following general formulas (12) to (14).

(In the formula, R ₃ represents hydrogen or a methyl group.)

(In the formula, R ₃ represents hydrogen or a methyl group.)

(In the formula, R ₃ represents hydrogen or a methyl group.)
The present invention also relates to a polyfunctional polymerizable compound represented by the following general formula (15).

(In the formula, R _{41 to} R ₄₅ are each independently hydrogen, a hydroxyl group, a methyl group, a methoxy group, or a functional group represented by —O—X, and at least one of R _{41 to} R ₄₅ is —O— -X is a functional group represented by -X, wherein each X independently represents a functional group having a (meth) acryl group.
The polyfunctional polymerizable compound represented by the general formula (15) is preferably represented by the following general formula (16) or (17).

(In the formula, R ₄₁ , R ₄₂ , R ₄₄ and R ₄₅ are each independently a hydrogen, a hydroxyl group, a methyl group, a methoxy group or a functional group represented by —O—X, where X is each (The functional group which has a (meth) acryl group independently is shown.)

(In the formula, R _{42 to} R ₄₅ are each independently a hydrogen, a hydroxyl group, a methyl group, a methoxy group, or a functional group represented by —O—X, where X is independently a (meth) acrylic group. A functional group having a group is shown.)
The present invention also relates to an ultraviolet-absorbing cured product obtained by reacting the polyfunctional polymerizable compound with a polymerizable compound having a (meth) acryl group.

Furthermore, the present invention is a method for producing the polyfunctional polymerizable compound,
The present invention also relates to a method for producing a polymerizable compound including a step of reacting the compound represented by the general formula (1) with a compound having an epoxy group and a (meth) acryl group.

  Since the polyfunctional polymerizable compound of the present invention has two or more (meth) acrylic acid ester moieties that are polymerizable functional groups, it easily forms a crosslinked structure by a polymerization reaction and is a strong cured product insoluble in a solvent. It becomes. Therefore, it is possible to provide a raw material that is extremely useful for producing a very hard material having the functions (ultraviolet ray absorbing ability, photoreactivity, etc.) of hydroxycinnamic acids. Moreover, since the free phenolic hydroxyl group is blocked, it is thought that the yellowing phenomenon by a metal component is relieved. Furthermore, since the polyfunctional polymerizable compound of the present invention can be produced by a simple process without using petroleum-derived raw materials that are depleted resources, wasteful energy consumption can be suppressed.

  According to the production method of the present invention, a compound having an epoxy group such as glycidyl methacrylate can be directly reacted with a hydroxycinnamic acid such as ferulic acid, and a polyfunctional ultraviolet absorber (polyfunctional polymerizable) can be obtained in just one step. Compound).

It is a figure which shows the ultraviolet absorption spectrum of the polyfunctional polymerizable compound of Example 1, and the comparative example 2 (hydroxybenzophenone type compound). It is a figure which shows the ultraviolet absorption spectrum of the polyfunctional polymerizable compound of Example 1, and the hardened | cured material of Example 15. It is a figure which shows the ultraviolet-ray absorption spectrum of the hardened | cured material of Example 16, and the cured film of Comparative Examples 3-5.

  The present invention is a polyfunctional polymerizable compound obtained by reacting the compound represented by the general formula (1) (hydroxycinnamic acid) with a compound having an epoxy group and a (meth) acryl group.

  That is, the polyfunctional polymerizable compound of the present invention has a part derived from hydroxycinnamic acid (hydroxycinnamic acid unit) and a part derived from (meth) acrylic acid ((meth) acrylic acid unit) in the molecule. It is a polymerizable compound that does not require a free phenolic hydroxyl group in order to maintain its ability to absorb ultraviolet rays. Therefore, it is very easy to synthesize derivatives as compared with existing hydroxybenzophenone and benzotriazole compounds. In addition, yellowing due to free phenolic hydroxyl groups hardly occurs.

  Furthermore, the polymerizable compound of the present invention is a polyfunctional polymerizable compound having a combination of a hydroxycinnamic acid unit and two or more (meth) acrylic acid units. A strong cured product can be obtained.

(Hydroxycinnamic acids)
The compound represented by the general formula (1) in the present invention is a derivative (hydroxycinnamic acid) having at least one hydroxyl group in the aromatic ring of the cinnamic acid skeleton, and has a methoxy group separately from the hydroxyl group on the aromatic ring. Derivatives (such as ferulic acid) and derivatives having two or more hydroxyl groups are also included.

  The compound represented by the general formula (1) includes a hydroxyl group at the ortho or para position with respect to the 2-carboxyvinyl group on the aromatic ring as represented by the general formula (2) or (3). And cinnamic acid derivatives having a hydroxyl group at the meta position of the 2-carboxyvinyl group.

  The cinnamic acid derivative represented by the general formula (2) having a hydroxyl group at least in the para position with respect to the 2-carboxyvinyl group on the aromatic ring is particularly preferable, for example, the general formula (4) or (5). The compound represented by these is mentioned. As a compound represented by the said General formula (4), the compound represented by either of the said General formula (7)-(9) is mentioned, for example. As a compound represented by the said General formula (5), the compound represented by the said General formula (10) is mentioned, for example.

  Moreover, as a cinnamic acid derivative represented by the above general formula (3) and having a hydroxyl group at least ortho to the 2-carboxyvinyl group as an aromatic ring, for example, a compound represented by the above general formula (6) Is mentioned. As a compound represented by the said General formula (6), the compound represented by the said General formula (11) is mentioned, for example.

  Hydroxycinnamic acids such as ferulic acid have a maximum absorption wavelength near 320 nm, which causes deterioration of resins such as polycarbonate, and its absorption capacity is very high compared to existing hydroxybenzophenone compounds and the like. . That is, the polyfunctional polymerizable compound of the present invention using hydroxycinnamic acids is expected to be excellent in ability to suppress deterioration of a resin such as polycarbonate.

  The hydroxycinnamic acid used in the present invention is not particularly limited in its origin and the like. For example, it is derived from cell walls such as rice bran oil, sugar maple, pine seeds, wheat endosperm cell walls, rice endosperm cells, etc. Things. That is, in the production of the polyfunctional polymerizable compound of the present invention, it is not necessary to use a petroleum-derived raw material which is a depleted resource for the ultraviolet absorption site.

  As a method for producing ferulic acid which is one of hydroxycinnamic acids, for example, rice crude oil and black-brown viscous pitch, oil-rich alkali foods, and by-product rich in crude fatty acid called dark oil are used as raw materials. The method of taking out by a hydrolysis method using alkaline methanol, ethanol, IPA, etc. as a solvent is mentioned. As a synthesis method, a method of reacting a mixture of vanillin, malonic acid and a small amount of piperidine in pyridine can be mentioned.

  In addition to ferulic acid, 4-hydroxycinnamic acid, 3,4-dihydroxy cinnamic acid (caffeic acid), 4-hydroxy-3,5-dimethoxy cinnamic acid (sinapic acid), 2-hydroxy cinnamic acid, etc. are also naturally present. It is widely distributed and, like ferulic acid, can be extracted from natural products as a raw material by hydrolysis. These can also be produced by utilizing a condensation reaction between aromatic aldehydes and malonic acid.

(Compound having epoxy group and (meth) acryl group)
The compound having an epoxy group and a (meth) acryl group used in the present invention is not particularly limited as long as it is a compound having both functional groups. For example, compounds represented by the above general formulas (12) to (14) Is mentioned.

  The polyfunctional polymerizable compound of the present invention described above is usually a polyfunctional polymerizable compound represented by the general formula (15).

  Examples of the polyfunctional polymerizable compound represented by the general formula (15) include compounds represented by the general formula (16) or (17). In the general formulas (15) to (17), examples of X that is a functional group having a (meth) acryl group include functional groups having structures of the following general formulas (18) to (22).

(In the formula, R ₅ represents hydrogen or a methyl group.)

(In the formula, R ₅ represents hydrogen or a methyl group.)

(In the formula, R ₅ represents hydrogen or a methyl group.)

(In the formula, R ₅ represents hydrogen or a methyl group.)

(In the formula, R ₅ represents hydrogen or a methyl group.)
[Production method]
This invention is a manufacturing method of the said polyfunctional polymerizable compound, Comprising: The compound (hydroxycinnamic acid) represented by the said General formula (1), and the compound which has an epoxy group and a (meth) acryl group are made to react. The present invention also relates to a method for producing a polyfunctional polymerizable compound including steps. Below, the manufacturing method (synthesis method) of the polyfunctional polymerizable compound of this invention is explained in full detail.

  In the method for producing a polyfunctional polymerizable compound of the present invention, a (meth) acrylate compound having an epoxy group is reacted with hydroxycinnamic acid to simultaneously add a (meth) acrylate compound to the hydroxyl group and carboxyl group of hydroxycinnamic acid. Since it can be added, the desired polyfunctional polymerizable compound can be obtained from hydroxycinnamic acids in only one step, and can be suitably used for industrial production.

  More specifically, for example, the reaction is allowed to proceed while mixing the compound represented by the general formula (1) (hydroxycinnamic acid) and a compound having an epoxy group and a (meth) acrylic group for a predetermined time. By this, the method of obtaining the target polyfunctional polymerizable compound is mentioned.

(catalyst)
When a catalyst is used in the method for producing a polyfunctional polymerizable compound of the present invention, the catalyst used is not particularly limited. For example, triethylamine, dimethylbutylamine, tri-n-butylamine, diazabicycloundecene (DBU) , Amines such as diazabicyclononene (DBN) and dimethylaminopyridine (DMAP), quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, tetrabutylammonium salt and benzyltriethylammonium salt, or tetraphenylphosphonium Examples thereof include quaternary phosphonium salts such as salts, phosphines such as triphenylphosphine, and imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole. These catalysts may be used alone or in combination of several kinds as appropriate.

  In particular, as the compound represented by the general formula (1) (hydroxycinnamic acid), cinnamic acid having a hydroxyl group at the ortho or para position of the phenyl group as represented by the general formula (2) or (3). In the case of using a derivative, hydroxystyrenes (see JP 2009-57294 A and JP 2007-530548 A) are produced by decarboxylation when heated to high temperature under basic conditions. Since a decarboxylation reaction can be suppressed by using a weak compound or a neutral salt, it is preferable to use such a catalyst. More preferred catalysts are quaternary ammonium salts, quaternary phosphonium salts or phosphines, and further preferred catalysts are phosphorus catalysts such as phosphonium salts and phosphines.

  In addition, since polyfunctional epoxy acrylate compounds such as the compounds of the present invention tend to have high solution viscosity, the compounds tend to gel. However, the reductive properties of phosphorus compounds are effective by using phosphorus catalysts. It is thought that the gelation is reduced by acting on the above.

  Among the phosphorous catalysts, quaternary phosphonium salts include, for example, tetraphenylphosphonium chloride (TPPC), tetraphenylphosphonium bromide (TPPB), tetraphenylphosphonium iodide (TPPI). Tetraphenylphosphonium salts such as tetraphenylphosphonium tetra-p-tolylborate and tetraphenylphosphonium tetraphenylborate, tetrabutylphosphonium chloride (TBPC), tetrabutylphosphonium bromide (TBPB), tetrabutyl Phosphosphonium hexafluoroborate, tetrabutylphosphonium tetrafluoroborate, tetrabutylphosphonium tetraphenylborate And tetrabutylphosphonium salt, tetraethylphosphonium bromide, and tetraethylphosphonium hexafluoroborate. Examples of phosphines include triphenylphosphine (TPP), tri (2-furyl) phosphine, tri (2-thienyl) phosphine, tri-n-octylphosphine, tri-tert-butylphosphine, tributylphosphine, tributylphosphine. Examples include cyclopentylphosphine, trihexylphosphine, tris (2,6-dimethoxyphenyl) phosphine, tris (2-methylphenyl) phosphine, tris (3-methylphosphine) phosphine, and tris (4-methoxyphenyl) phosphine. Among these, quaternary phosphonium salts TPPC, TBPB, and TPPB are preferable, and TPPC having a high reaction rate is particularly preferable.

  Although the usage-amount of a catalyst is not specifically limited, It is 0.001-10 mol with respect to 1 mol of hydroxy cinnamic acids, Preferably it is 0.01-3 mol.

(Polymerization inhibitor)
In the synthesis reaction of the polyfunctional polymerizable compound, a polymerization inhibitor is preferably allowed to coexist in the reaction system in order to prevent polymerization of the (meth) acryl group. Examples of the polymerization inhibitor include dibutylhydroxytoluene (BHT), hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, 4-methylquinoline, phenothiazine and the like.

(Reaction solvent)
In the production of the polyfunctional polymerizable compound of the present invention, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, diethyl ether, 1,4-dioxane, cyclopentylmethyl Ethers such as ethers, alkyl halides such as dichloromethane, chloroform, 1,2-dichloroethane, polar aprotic solvents such as dimethylformamide, dimethyl sulfoxide, n-methyl 2-pyrrolidone, methyl cellosolve acetate, ethyl celloacetate Reaction solvents include esters such as ethyl acetate, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and aromatic compounds such as benzene, toluene, chlorobenzene and dichlorobenzene. Can be used.

  From the viewpoint of environmental load, cost, and reaction rate, it is preferable to reduce the amount of the reaction solvent as much as possible, and it is more preferable not to use the reaction solvent. By reducing the amount of the reaction solvent, it is considered that the speed of the synthesis reaction is increased and it is easy to suppress the decarboxylation reaction that is assumed as a side reaction.

  The reaction temperature in the synthesis reaction of the polyfunctional polymerizable compound of the present invention is usually room temperature to 150 ° C, preferably 50 to 100 ° C.

(UV-absorbed cured product)
The present invention also relates to a UV-absorbing cured product obtained using the polyfunctional polymerizable compound obtained by the above method. Hereinafter, a method of obtaining a UV-absorbing cured product using the polyfunctional polymerizable compound and applying it to a polymer material product or the like will be described.

  The ultraviolet-absorbing cured product of the present invention can be obtained, for example, by polymerizing a polymerizable composition containing the polyfunctional polymerizable compound of the present invention as a monomer. The polymerizable composition may be composed of only one or a plurality of polyfunctional polymerizable compounds of the present invention. Usually, for the purpose of variously adjusting the viscosity of the composition before curing and the physical properties of the cured product. It is desirable to include other polymerizable compounds.

  Examples of other polymerizable compounds include polymerizable compounds having a (meth) acrylic group such as (meth) acrylic acid ester derivatives, styrene derivatives, alkyl vinyl ethers, vinyl chloride, ethylene, propylene, butadiene, vinyl acetate, acrylonitrile. Among them, a polymerizable compound having a (meth) acryl group is preferable.

  As the polymerizable monomer having a (meth) acryl group, for example, in a monofunctional monomer, methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, t-butyl acrylate, n-amyl acrylate, acrylic acid Alkyl esters such as hexyl, cyclohexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, dodecyl acrylate, methacrylic acid such as methyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate Examples include alkyl esters.

  In order to obtain a UV-absorbing cured product having a high degree of curing, the main polymerizable compound is preferably a polyfunctional polymerizable compound having a plurality of polymerizable functional groups. Examples of such polyfunctional polymerizable compounds include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and dipropylene glycol di (meth). Acrylate, polypropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol polypropylene oxide modified di Acrylate, polytetramethylene glycol di (meth) acrylate, 2-butyl 2-ethyl 1,3-propanediol diacrylate, trimethylolpropane tri (meth) acrylate Examples thereof include rate, trimethylolpropane ethylene oxide-modified triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol penta / hexa (meth) acrylate, and tris (methacryloxyethyl) isocyanurate. Moreover, polyfunctional polymerizable oligomers, such as a urethane-type oligomer, a polyether-type oligomer, an epoxy-type oligomer, and a polyester-type oligomer, are also mentioned.

  Further, the other polymerizable compound is not limited to a so-called monomer having a relatively low molecular weight, and for example, a polymer resin having an unreacted (meth) acryl group can be used.

  The polymerizable composition containing the polyfunctional polymerizable compound of the present invention may contain a solvent. The solvent is not particularly limited, for example, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, ethers such as tetrahydrofuran, diethyl ether, 1,4-dioxane, cyclopentyl methyl ether, Alkyl halides such as dichloromethane, chloroform, 1,2-dichloroethane, esters such as methyl cellosolve acetate, ethyl celloacetate, ethyl acetate, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene, chlorobenzene, di An aromatic compound such as chlorobenzene or a mixed solvent thereof can be used.

  As a method for curing the polymerizable composition containing the polyfunctional polymerizable compound of the present invention, for example, the polymerizable composition is applied to polycarbonate, acrylic resin, wood, glass, etc., and the solvent is removed (dried). Examples of the polymerization method include irradiation with actinic rays such as ultraviolet rays and electron beams, or heating.

  As the polymerization reaction for the curing reaction, for example, radical polymerization, anionic polymerization and the like can be used, but preferably radical polymerization is used.

  In the case of polymerization after coating the polymerizable composition on the resin, for example, in the polymerizable composition, a photoinitiator such as benzophenone-based, benzoin ether-based, acetophenone-based, thioxanthone-based or peroxide (peroxide It is possible to add a thermal initiator such as benzoyl oxide and the like and apply it onto the resin, followed by polymerization by ultraviolet irradiation, heating, or the like. In addition, when an electron beam is used, polymerization can be performed without adding an initiator.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, the content of this invention is not limited by this.

In the following, the measurement of NMR data was performed using an AVANCE400 manufactured by Bruker. Moreover, the chemical shift value of ¹ HNMR is a value based on tetramethylsilane. Further, the MS spectrum was measured using Mariner manufactured by PerSeptive Biosystems or LCMS-2010EV manufactured by Shimazu.

[Synthesis of polyfunctional polymerizable compound (polyfunctional acrylate monomer)]
Example 1
Polyfunctional polymerizable compounds represented by the following general formulas (23) to (26) were synthesized.

  Here, a plurality of polyfunctional polymerizable compounds that may be synthesized from a combination of raw materials in this example are described, but the polyfunctional polymerizable compound that is mainly produced in this example is represented by the above formula (23). It is the compound shown. In the following, only the general formula of one typical polyfunctional polymerizable compound obtained in each example will be described.

  To a mixture of 776 mg of ferulic acid and 1.08 mL of glycidyl methacrylate, 167 mg of tetraphenylphosphonium bromide (TPPB) as a catalyst and a small amount of hydroquinone as a polymerization inhibitor were added and stirred at 80 ° C. for 3 hours. The progress of the reaction was monitored by TLC and NMR, and it was confirmed by NMR that the epoxy ring signal derived from glycidyl methacrylate almost disappeared and the chemical shift of the ferulic acid derived signal shifted. The reaction mixture was poured into a mixed solution of ethyl acetate and a small amount of acetone, and the organic layer was washed with a 1N aqueous sodium hydroxide solution followed by a saturated sodium chloride solution. The obtained organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 1.78 g of an oil (polyfunctional polymerizable compound).

The result of NMR and MS spectrum measurement of the obtained polyfunctional polymerizable compound is shown below.
<NMR data>
¹ H NMR (400 MHz, Acetone-d ₆ )
δ 7.0-7.1 aromatic ring proton, 7.6-7.7,
δ 6.4-6.5 7.6-7.7 Unsaturated proton from ferulic acid skeleton,
δ 5.5-5.7, 6.0-6.2 Unsaturated proton from methacrylic acid skeleton,
δ 5.2-5.4
Methine proton (-CH (O-X) - ) where X is a substituent [delta] 4.1-4.5 methylene protons which contain a carbonyl group (-CH ₂ -O-), methine proton (-CH (OH) -)
δ 3.8-4.0 Methoxy group derived from ferulic acid skeleton δ 1.8-2.0 Methyl group derived from methacrylic acid skeleton

<MS spectrum data>
ESI-TOF-MS m / e calcd for C ₂₄ H ₃₀ NaO ₁₀ (M + Na ⁺ )
501.2. found, 501.2

(Comparative Example 1)
To a mixture of 1.0 g of ferulic acid and 1.4 mL of glycidyl methacrylate, 43 mg of tetraethylbenzylammonium chloride (TEBAC) or 32 mg of 1-benzyl 2-methylimidazole (BMI) as a catalyst and 1000 ppm of hydroquinone as a polymerization inhibitor were added at 80 ° C. Stir. Although the progress of the reaction was confirmed, the reaction mixture gelled in 15 hours after the start of the reaction.

  From the results of Example 1 and Comparative Example 1, when reaction conditions in which gelation is likely to occur, such as when there is no solvent or when there is little solvent, the occurrence of gelation tends to be suppressed by using a phosphorus-based catalyst. Conceivable. However, it goes without saying that a catalyst other than a phosphorus catalyst may be used even under reaction conditions where gelation is likely to occur, such as when there is no solvent or when there are few solvents.

(Example 2)
A polyfunctional polymerizable compound represented by the following general formula (27) was synthesized.

  To a mixture of 10 g of p-hydroxycinnamic acid and 17.32 g of glycidyl methacrylate, 2.28 g of tetraphenylphosphonium chloride (TPPC) as a catalyst and 250 ppm each of hydroquinone monomethyl ether and BHT (dibutylhydroxytoluene) as a polymerization inhibitor were added. Stir at 80 ° C. for 10 hours. In the NMR spectrum, it was confirmed that the signal of the epoxy ring derived from glycidyl methacrylate almost disappeared (the conversion rate of glycidyl methacrylate was 99% or more), and the chemical shift of the signal derived from p-hydroxycinnamic acid shifted.

The result of NMR and MS spectrum measurement of the obtained polyfunctional polymerizable compound is shown below.
<NMR data>
¹ H NMR (400 MHz, Acetone-d ₆ )
δ 7.0-7.1, 7.6-7.7 Aromatic ring proton δ 6.4-6.5 7.6-7.7 Unsaturated proton from cinnamic acid skeleton,
δ 5.5-5.7, 6.0-6.2 Unsaturated proton from methacrylic acid skeleton,
δ 5.2-5.4
Methine proton (-CH (O-X)-) where X is a substituent containing a carbonyl group
δ 3.5-4.5 Methylene proton (—CH ₂ —O—), methine proton (—CH (OH) —)
δ 1.8-2.0 Methyl group derived from methacrylic acid skeleton

<MS spectrum data>
ESI-TOF-MS m / e calcd for C ₂₃ H ₂₈ NaO ₉ (M + Na ⁺ )
471.2. found, 471.1

(Example 3)
A polyfunctional polymerizable compound represented by the following general formula (28) was synthesized.

  To a mixture of 1.0 g of 2-hydroxycinnamic acid and 1.73 g of glycidyl methacrylate, 230 mg of tetraphenylphosphonium chloride (TPPC) as a catalyst and 500 ppm of hydroquinone monomethyl ether and BHT (dibutylhydroxytoluene) as a polymerization inhibitor were added, respectively. Stir at 0 ° C. for 10 hours. In the NMR spectrum, it was confirmed that the signal of the epoxy ring derived from glycidyl methacrylate almost disappeared (conversion rate of glycidyl methacrylate of 98% or more), and the chemical shift of the signal derived from 2-hydroxycinnamic acid moved.

The result of NMR and MS spectrum measurement of the obtained polyfunctional polymerizable compound is shown below.
<NMR data>
¹ H NMR (400 MHz, Acetone-d ₆ )
δ 6.9.-7.1, 7.1-7.2 7.3-7.5 Aromatic ring proton δ 6.5-6.7 7.6-7.7 Unsaturated bond derived from cinnamic acid skeleton Protons,
δ 5.5-5.7, 6.0-6.2 Unsaturated proton from methacrylic acid skeleton,
δ 5.1-5.3, 5.4-5.5 methine proton (—CH (O—X) —) where X is a substituent containing a carbonyl group δ 3.5-4.7 methylene proton (—CH ₂ -O-), methine proton (-CH (OH)-)
δ 1.8-2.0 Methyl group derived from methacrylic acid skeleton

<MS spectrum data>
ESI-TOF-MS m / e calcd for C ₂₃ H ₂₈ NaO ₉ (M + Na ⁺ )
471.2. found, 471.1

Example 4
A polyfunctional polymerizable compound represented by the following general formula (29) was synthesized.

  To a mixture of 1.0 g of 3,5-dimethoxy-4-hydroxycinnamic acid and 1.27 glycidyl methacrylate, 170 mg of tetraphenylphosphonium chloride (TPPC) as a catalyst, hydroquinone monomethyl ether and BHT (dibutylhydroxytoluene) as polymerization inhibitors 500 ppm of each was added and it stirred at 80 degreeC for 10 hours. Confirmed that the glycidyl methacrylate-derived epoxy ring signal almost disappeared in the NMR spectrum (conversion rate of glycidyl methacrylate 99% or more), and that the chemical shift of 3,5-dimethoxy-4-hydroxycinnamic acid-derived signal shifted. did.

The result of NMR and MS spectrum measurement of the obtained polyfunctional polymerizable compound is shown below.
<NMR data>
¹ H NMR (400 MHz, Acetone-d ₆ )
δ 7.0.-7.1 aromatic ring proton δ 6.5-6.6 7.6-7.7 Unsaturated proton from cinnamic acid skeleton,
δ 5.6-5.7, 6.0-6.2 Unsaturated proton from methacrylic acid skeleton,
δ 5.1-5.3, 5.4-5.5 methine proton (—CH (O—X) —) where X is a substituent containing a carbonyl group δ 3.5-4.6 methylene proton (—CH ₂ -O-), methine proton (-CH (OH)-)
δ 1.8-2.0 Methyl group derived from methacrylic acid skeleton

<MS spectrum data>
ESI-TOF-MS m / e calcd for C ₂₅ H ₃₃ O ₁₁ (M + H ⁺ )
509.2. found, 509.1

(Example 5)
A polyfunctional polymerizable compound represented by the following general formula (30) was synthesized.

  To a mixture of 1.0 g of 3,4-dihydroxycinnamic acid and 2.37 g of glycidyl methacrylate, 210 mg of tetraphenylphosphonium chloride (TPPC) as a catalyst and 1000 ppm each of hydroquinone monomethyl ether and BHT (dibutylhydroxytoluene) as a polymerization inhibitor are added. And stirred at 80 ° C. for 10 hours. In the NMR spectrum, it was confirmed that the signal of the epoxy ring derived from glycidyl methacrylate almost disappeared and the chemical shift of the signal derived from 3,4-dihydroxycinnamic acid moved.

The result of NMR and MS spectrum measurement of the obtained polyfunctional polymerizable compound is shown below.
<NMR data>
¹ H NMR (400 MHz, Acetone-d ₆ )
δ 7.0.-7.1, 7.2-7.3 7.4-7.5 Aromatic ring proton δ 6.4-6.6 7.6-7.7 Unsaturated bond derived from cinnamic acid skeleton Protons,
δ 5.6-5.7, 6.0-6.2 Unsaturated proton from methacrylic acid skeleton,
δ 5.1-5.3 methine proton (—CH (O—X) —) where X is a substituent containing a carbonyl group δ 3.5-4.6 methylene proton (—CH ₂ —O—), methine proton (-CH (OH)-)
δ 1.8-2.0 Methyl group derived from methacrylic acid skeleton

<MS spectrum data>
ESI-TOF-MS m / e calcd for C ₃₀ H ₃₈ NaO ₁₃ (M + Na ⁺ )
629.2. found, 629.1

(Example 6)
A polyfunctional polymerizable compound represented by the following general formula (31) was synthesized.

  To a mixture of 10 g of m-hydroxycinnamic acid and 17.32 g of glycidyl methacrylate, 2.28 g of tetraphenylphosphonium chloride (TPPC) as a catalyst and 250 ppm of hydroquinone monomethyl ether and BHT (dibutylhydroxytoluene) as a polymerization inhibitor were added, respectively. Stir at 0 ° C. for 10 hours. In the NMR spectrum, it was confirmed that the signal of the epoxy ring derived from glycidyl methacrylate almost disappeared (the conversion rate of glycidyl methacrylate was 99% or more), and the chemical shift of the signal derived from m-hydroxy was shifted.

The result of NMR and MS spectrum measurement of the obtained polyfunctional polymerizable compound is shown below.
<NMR data>
¹ H NMR (400 MHz, Acetone-d ₆ )
δ 7.0-7.5 aromatic ring proton δ 6.4-6.6 7.6-7.7 Unsaturated proton derived from cinnamic acid skeleton,
δ 5.6-5.7, 6.0-6.2 Unsaturated proton from methacrylic acid skeleton,
δ 5.1-5.3, 5.4-5.6
Methine proton (—CH (O—X) —) where X is a substituent containing a carbonyl group δ 3.5-4.5 Methylene proton (—CH ₂ —O—), Methine proton (—CH (OH) —)
δ 1.8-2.0 Methyl group derived from methacrylic acid skeleton

<MS spectrum data>
ESI-TOF-MS m / e calcd for C ₂₃ H ₂₈ NaO ₉ (M + Na ⁺ )
471.2. found, 471.1

(Example 7)
A polyfunctional polymerizable compound represented by the following general formula (32) was synthesized.

  To a mixture of 1.0 g of 3-hydroxy-4-methoxycinnamic acid and 1.73 g of glycidyl methacrylate, 190 mg of tetraphenylphosphonium chloride (TPPC) as a catalyst and 500 ppm of hydroquinone monomethyl ether and BHT (dibutylhydroxytoluene) as polymerization inhibitors, respectively. In addition, the mixture was stirred at 80 ° C. for 10 hours. It was confirmed that the signal of the epoxy ring derived from glycidyl methacrylate almost disappeared in the NMR spectrum (conversion rate of glycidyl methacrylate of 99% or more), and the chemical shift of the signal derived from 3-hydroxy-4-methoxycinnamic acid moved.

The result of NMR and MS spectrum measurement of the obtained polyfunctional polymerizable compound is shown below.
<NMR data>
¹ H NMR (400 MHz, Acetone-d ₆ )
δ 6.9.-7.1, 7.2-7.3 7.4-7.5 Aromatic ring proton δ 6.4-6.6 7.6-7.7 Unsaturated bond derived from cinnamic acid skeleton Protons,
δ 5.5-5.7, 6.0-6.2 Unsaturated proton from methacrylic acid skeleton,
δ 5.2-5.4, 5.4-5.6 methine proton (—CH (O—X) —) where X is a substituent containing a carbonyl group δ 3.5-4.5 methylene proton (—CH ₂ -O-), methine proton (-CH (OH)-)
δ 3.8-3.9 Methoxy group derived from cinnamic acid derivative δ 1.8-2.0 Methyl group derived from methacrylic acid skeleton

<MS spectrum data>
ESI-TOF-MS m / e calcd for C ₂₄ H ₃₀ NaO ₁₀ (M + Na ⁺ )
501.2. found, 501.1

(Example 8)
A polyfunctional polymerizable compound represented by the following general formula (33) was synthesized.

  To a mixture of 10 g of ferulic acid and 22.07 g of 4-hydroxybutyl acrylate glycidyl ether, 1.93 g of tetraphenylphosphonium chloride (TPPC) as a catalyst and 500 ppm of hydroquinone monomethyl ether and BHT (dibutylhydroxytoluene) as polymerization inhibitors were added. Stir at 80 ° C. for 10 hours. In the NMR spectrum, the signal of the epoxy ring derived from 4-hydroxybutyl acrylate glycidyl ether almost disappeared (94% conversion of 4-hydroxybutyl acrylate glycidyl ether), and the chemical shift of the signal derived from ferulic acid moved. confirmed.

The result of NMR and MS spectrum measurement of the obtained polyfunctional polymerizable compound is shown below.
<NMR data>
¹ H NMR (400 MHz, Acetone-d ₆ )
δ 7.0.-7.1, 7.1-7.2 7.3-7.4 Aromatic ring proton δ 6.4-6.5 7.6-7.7 Unsaturated bond derived from ferulic acid skeleton Protons,
δ 5.8-5.9, 6.0-6.2, 6.3-6.4, proton of unsaturated bond derived from acrylic acid skeleton,
δ 5.0-5.2 methine proton (—CH (O—X) —) where X is a substituent containing a carbonyl group δ 3.4-4.5 methylene proton (—CH ₂ —O—), methine proton (-CH (OH)-)
δ 3.8-4.0 Methoxy group derived from ferulic acid skeleton δ 1.5-1.8 Methylene proton derived from 4-hydroxybutyl group

<MS spectrum data>
ESI-TOF-MS m / e calcd for C ₃₀ H ₄₂ NaO ₁₂ (M + Na ⁺ )
617.3. found, 617.2

Example 9
A polyfunctional polymerizable compound represented by the following general formula (34) was synthesized.

  A mixture of 10 g of ferulic acid and 18.77 g of cyclomer A200 (manufactured by Daicel Chemical Industries, Ltd .: 3,4-epoxycyclohexylmethyl acrylate), 1.93 g of tetraphenylphosphonium chloride (TPPC) as a catalyst, and hydroquinone monomethyl ether as a polymerization inhibitor And 500 ppm of BHT (dibutylhydroxytoluene) were added and stirred at 80 ° C. for 10 hours. In the NMR spectrum, it was confirmed that the signal of the epoxy ring derived from cyclomer A200 almost disappeared (the conversion rate of cyclomer A200 was 91%), and the chemical shift of the signal derived from ferulic acid shifted.

The result of NMR and MS spectrum measurement of the obtained polyfunctional polymerizable compound is shown below.
<NMR data>
¹ H NMR (400 MHz, Acetone-d ₆ )
δ 7.1.-7.3, 7.3-7.4 Aromatic ring proton δ 6.4-6.5 7.6-7.7 Unsaturated proton derived from ferulic acid skeleton,
δ 5.8-6.0, 6.1-6.3, 6.3-6.4
An unsaturated bond proton derived from an acrylic acid skeleton,
δ 4.8-5.1, 4.4-4.6 methine proton (—CH (O—X) —) where X is a substituent containing an electron withdrawing group δ 3.7-4.1 methylene proton (— CH ₂ -O-), methine (-CH (OH) -)
δ 3.8-3.9 Methoxy group derived from ferulic acid skeleton δ 1.4-2.3 Cyclomer A200 Proton derived from alicyclic skeleton

<MS spectrum data>
ESI-TOF-MS m / e calcd for C ₃₀ H ₃₉ NaO ₁₀ (M + H ⁺ )
559.3 found, 559.2

(Example 10)
A mixture of 7.76 g of ferulic acid, 5.7 g of glycidyl methacrylate and 8.0 g of 4-hydroxybutyl acrylate glycidyl ether, 1.5 g of tetraphenylphosphonium bromide (TPPB) as a catalyst, hydroquinone monomethyl ether and BHT (dibutyl as a polymerization inhibitor) 500 ppm of hydroxytoluene) was added and stirred at 80 ° C. for 10 hours. In the NMR spectrum, it was confirmed that the signal of the epoxy ring derived from glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether almost disappeared, and the chemical shift of the signal derived from ferulic acid shifted.

The result of NMR and MS spectrum measurement of the obtained polyfunctional polymerizable compound is shown below.
<NMR data>
¹ H NMR (400 MHz, CDCl ₃ )
δ 6.9.-7.1 Aromatic ring proton δ 6.3-6.5 7.6-7.7 Unsaturated proton derived from ferulic acid skeleton,
δ 5.6-5.7, 5.8-5.9 6.1-6.2, 6.2-6.4 Proton of unsaturated bond derived from acrylic acid or methacrylic acid skeleton δ 5.1-5 .3 methine proton (—CH (O—X) —) where X is a substituent containing a carbonyl group δ 3.4-4.5 methylene proton (—CH ₂ —O—), methine proton (—CH (OH) −)
δ 3.8-4.0 Methoxy group derived from ferulic acid skeleton δ 1.9-2.0 Methyl group derived from methacrylic acid skeleton δ 1.6-1.8 Methylene proton derived from 4-hydroxybutyl group

<MS spectrum data>
ESI-MS m / e
(1) Product obtained by reacting ferulic acid and glycidyl methacrylate (2 molecules) calcd for C ₂₄ H ₃₀ NaO ₁₀ (M + Na ⁺ ) 501
found, 501
(2) Product obtained by reacting ferulic acid with glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether calcd for C ₂₇ H ₃₆ NaO ₁₁ (M + Na ⁺ ) 559
found, 559
(3) Product obtained by reacting ferulic acid with 4-hydroxybutyl acrylate glycidyl ether (2 molecules) calcd for C ₃₀ H ₄₂ NaO ₁₂ (M + Na ⁺ ) 617
found, 617

(Example 11)
To a mixture of 7.76 g of ferulic acid, 5.7 g of glycidyl methacrylate and 7.3 g of cyclomer A200, 1.5 g of tetraphenylphosphonium bromide (TPPB) as a catalyst, hydroquinone monomethyl ether and BHT (dibutylhydroxytoluene) as a polymerization inhibitor 500 ppm of each was added and stirred at 80 ° C. for 10 hours. In the NMR spectrum, it was confirmed that the signals of the epoxy ring derived from glycidyl methacrylate and cyclomer A200 almost disappeared, and the chemical shift of the signal derived from ferulic acid shifted.

The result of NMR and MS spectrum measurement of the obtained polyfunctional polymerizable compound is shown below.
<NMR data>
¹ H NMR (400 MHz, CDCl ₃ )
δ 6.8-7.1 Aromatic ring proton δ 6.4-6.5 7.5-7.7 Unsaturated proton derived from ferulic acid skeleton,
δ 5.6-5.7, 5.8-5.9 6.1-6.2, 6.2-6.4 Proton of unsaturated bond derived from acrylic acid, methacrylic acid skeleton δ 5.2-5 .3, 4.8-5.1 Methine proton (—CH (O—X) —) where X is a substituent containing an electron withdrawing group δ 3.6-4.1 Methylene proton (—CH ₂ —O—) , Methine proton (-CH (OH)-)
δ 3.8-3.9 Methoxy group derived from ferulic acid skeleton δ 1.9-2.0 Methyl group derived from methacrylic acid skeleton δ 1.4-2.3 Cyclomer A200 Proton derived from alicyclic skeleton

<MS spectrum data>
ESI-MS m / e
(1) Product obtained by reacting ferulic acid and glycidyl methacrylate (2 molecules) calcd for C ₂₄ H ₃₀ NaO ₁₀ (M + Na ⁺ ) 501
found, 501
(2) Product obtained by reacting ferulic acid with glycidyl methacrylate and cyclomer A200 calcd for C ₂₇ H ₃₆ NaO ₁₁ (M + Na ⁺ ) 541
found, 541
(3) Product obtained by reacting ferulic acid with cyclomer A200 (2 molecules) calcd for C ₃₀ H ₄₂ NaO ₁₂ (M + Na ⁺ ) 581
found, 581

(Example 12)
A mixture of 7.76 g of ferulic acid, 3.8 g of glycidyl methacrylate, 5.4 g of 4-hydroxybutyl acrylate glycidyl ether and 4.9 g of cyclomer A200, tetraphenylphosphonium bromide (TPPB) 1.5 as a catalyst, and polymerization inhibitor 500 ppm each of hydroquinone monomethyl ether and BHT (dibutylhydroxytoluene) were added and stirred at 80 ° C. for 10 hours. In the NMR spectrum, it was confirmed that the signal of the epoxy ring derived from glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, and cyclomer A200 almost disappeared, and the chemical shift of the signal derived from ferulic acid shifted.

The result of NMR and MS spectrum measurement of the obtained polyfunctional polymerizable compound is shown below.
<NMR data>
¹ H NMR (400 MHz, CDCl ₃ )
δ 6.9-7.1 Aromatic ring proton δ 6.4-6.5 7.6-7.7 Unsaturated proton derived from ferulic acid skeleton,
δ 5.5-5.7, 5.8-5.9 6.0-6.2, 6.2-6.4
Proton δ 5.1-5.3, 4.8-5.1 of unsaturated bond derived from acrylic acid and methacrylic acid skeleton
Methine proton (—CH (O—X) —) where X is a substituent containing an electron withdrawing group δ 3.4-4.1 Methylene proton (—CH ₂ —O—), methine proton (—CH (OH) — )
δ 3.9-4.0 Methoxy group derived from ferulic acid skeleton δ 1.9-2.0 Methyl group derived from methacrylic acid skeleton δ 1.4-2.3 Cyclomer A200 Proton derived from alicyclic skeleton 1.6 -1.8 4-hydroxybutyl group-derived methylene proton

<MS spectrum data>
ESI-MS m / e
(1) Product obtained by reacting ferulic acid and glycidyl methacrylate (2 molecules) calcd for C ₂₄ H ₃₀ NaO ₁₀ (M + Na ⁺ ) 501
found, 501
(2) Product obtained by reacting ferulic acid with glycidyl methacrylate and cyclomer A200 calcd for C ₂₇ H ₃₆ NaO ₁₁ (M + Na ⁺ ) 541
found, 541
(3) Product obtained by reacting ferulic acid with glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether calcd for C ₂₇ H ₃₆ NaO ₁₁ (M + Na ⁺ ) 559
found, 559
(4) Product obtained by reacting ferulic acid with cyclomer A200 (2 molecules) calcd for C ₃₀ H ₄₂ NaO ₁₂ (M + Na ⁺ ) 581
found, 581
(5) Product obtained by reacting ferulic acid with cyclomer A200 and 4-hydroxybutyl acrylate glycidyl ether calcd for C ₃₀ H ₄₀ NaO ₁₁ (M + Na ⁺ ) 599
found, 599
(6) Product obtained by reacting ferulic acid with 4-hydroxybutyl acrylate glycidyl ether (2 molecules) calcd for C ₃₀ H ₄₂ NaO ₁₂ (M + Na ⁺ ) 617
found, 617

(Example 13)
To a mixture of 7.76 g of ferulic acid, 10.8 mL of glycidyl methacrylate and 150 mL of methyl ethyl ketone, 1.67 g of tetraphenylphosphonium bromide (TPPB) as a catalyst and 1000 ppm of hydroquinone monomethyl ether and BHT (dibutylhydroxytoluene) as polymerization inhibitors are added. Stir at 80 ° C. for 10 hours.

  From the results of TLC and NMR spectrum measurement of the obtained reaction mixture, it was confirmed that the same compound as in Example 1 was obtained. The production of 4-hydroxy-3-methoxy-styrene produced by the decarboxylation of ferulic acid was also confirmed (vinyl proton of the compound obtained in Example 1 and vinyl of 4-hydroxy-3-methoxy-styrene). The ratio to proton was 56:44 in terms of integral ratio of NMR spectrum).

(Example 14)
To a mixture of 7.76 g of ferulic acid, 10.8 mL of glycidyl methacrylate and 150 mL of dimethylformamide, 1.28 g of tetrabutylammonium bromide (TBAB) as a catalyst and 1000 ppm each of hydroquinone monomethyl ether and BHT (dibutylhydroxytoluene) as polymerization inhibitors And stirred at 80 ° C. for 10 hours.

  From the results of TLC and NMR spectrum measurement of the obtained reaction mixture, it was confirmed that the same compound as in Example 1 was obtained. The production of 4-hydroxy-3-methoxy-styrene produced by the decarboxylation reaction of ferulic acid was also confirmed ((vinyl proton of the compound obtained in Example 1 and 4-hydroxy-3-methoxy-styrene The ratio with the vinyl proton was 4: 6 in terms of the integral ratio of the NMR spectrum).

  From the results of Example 14, under conditions where gelation is unlikely to occur, such as when a certain amount of solvent is present in the reaction system, a non-phosphorus catalyst such as a quaternary ammonium salt is used in the same manner as the phosphorous catalyst. It is considered possible.

[Evaluation of UV absorption characteristics of polyfunctional polymerizable compounds]
(Comparative Example 2)
The ultraviolet absorption spectrum of the polyfunctional polymerizable compound obtained in Example 1 and the ultraviolet absorption spectrum of a commercially available hydroxybenzophenone compound (2- (4-benzoyl-3-hydroxy-phenoxy) ethyl acrylate) as a comparison were measured. . The ultraviolet absorption spectrum was measured using a UV / visible spectrophotometer V-560 manufactured by JASCO Corporation at a data acquisition interval of 0.5 nm / min. The measurement results are shown in FIG.

  Table 1 shows the maximum absorption wavelength around 320 nm of each compound of Example 1 and Comparative Example 2, and the molar extinction coefficient at that wavelength. The solvent was ethanol.

  From FIG. 1 and Table 1, it can be seen that the peak of the absorption wavelength of the polyfunctional polymerizable compound of the present invention obtained in Example 1 is almost the same absorption wavelength as that of the hydroxybenzophenone compound. Furthermore, the molar absorbance coefficient of Example 1 is about twice that of the hydroxybenzophenone compound, and the polyfunctional polymerizable compound of the present invention has a very effective ultraviolet absorbing ability in this wavelength region. Recognize.

[Preparation of UV-absorbed cured product using polyfunctional polymerizable compound]
(Example 15: Cured product)
150 mg of polyfunctional polymerizable compound obtained by the production method of Example 1, 1.0 g of dipentaerythritol penta / hexaacrylate, 30 mg of polymerization initiator (Irgacure 819, manufactured by Ciba Geigy), 0.5 mL of toluene, 0.5 mL of methyl ethyl ketone The coating solution prepared by mixing was spin-coated on a square quartz plate having a side of 30 mm. The obtained coating film was dried under reduced pressure at room temperature for 6 hours. A cured film was formed by irradiating light (4.4 J / cm ² ) with a wavelength of 400 nm to 700 nm using a spot light source.

  The ultraviolet absorption spectrum of the cured product obtained in this example is shown in FIG. 2 (Although the ultraviolet absorption spectrum of the polyfunctional polymerizable compound obtained in Example 1 is also shown, the method for measuring each spectrum is different. Therefore, it is referred only for comparison of absorption wavelength). It turns out that it has the same ultraviolet absorption ability after hardening as before hardening.

(Example 16: Cured product)
Polyfunctional polymerizable compound 50 mg obtained by the production method of Example 1, urethane acrylate (NK Oligo U-15HA, manufactured by Shin-Nakamura Chemical Co., Ltd.) 1.0 g, polymerization initiator (Irgacure 819, manufactured by Ciba-Geigy) 30 mg Then, a coating solution prepared by mixing 1.0 mL of methyl ethyl ketone was spin-coated on a square quartz plate having a side of 30 mm. The obtained coating film was dried under reduced pressure at room temperature for 3 hours to prepare a coating film. A cured film was formed by irradiating light ( ² J / cm ² ) with light of 400 nm to 700 nm using a spot light source.

(Comparative Example 3: cured product)
A cured film was formed in the same manner as in Example 16 except that a conventional UV-absorbing monofunctional acrylate was used instead of the polyfunctional polymerizable compound obtained by the production method of Example 1. As a conventional monofunctional acrylate, a monofunctional acrylate obtained by the reaction of ferulic acid 2-ethylhexyl ester with glycidyl methacrylate (synthesized according to the method of JP-A-2009-215189) was used.

(Comparative Example 4: cured product)
A cured film was formed in the same manner as in Example 16 except that a conventional hydroxybenzophenone-based monofunctional acrylate was used instead of the polyfunctional polymerizable compound obtained by the production method of Example 1. As the monofunctional acrylate, 2- (4-benzoyl-3-hydroxy-phenoxy) ethyl acrylate was used.

(Comparative Example 5: cured product)
A cured film was formed in the same manner as in Example 16 except that instead of the polyfunctional polymerizable compound obtained by the production method of Example 1, a conventional monofunctional acrylate having no ultraviolet absorptivity was used. 1,6-hexanediol dimethacrylate was used as the monofunctional acrylate.

[UV absorption spectrum of cured film]
The ultraviolet absorption spectrum of the cured product obtained in Example 16 and Comparative Examples 3 to 5 was measured. The measurement results are shown in FIG. 3 (the film thicknesses of the respective spectra are strictly different so that they are referred to only for comparison of absorption wavelengths).

  It can be seen that Example 16 has a large absorption in the region of 300 to 400 nm as compared with Comparative Example 5, and effectively functions as a UV-absorbing cured film. Further, it can be seen that, compared with the hydroxybenzophenone series of Comparative Example 4, the absorption near 320 nm, which is effective for preventing deterioration of the material, is larger than the other absorption bands.

[Pencil hardness]
According to JIS-K5600-5-4, the pencil hardness of the cured film obtained in Example 16 and Comparative Examples 3 to 5 was measured. The results are shown in Table 2.

  Compared to Comparative Examples 3 and 4 in which a monofunctional acrylate was added, it can be seen that in Example 16, a high hardness film was maintained as in Comparative Example 5 using a bifunctional acrylate.

  It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

  The polyfunctional polymerizable compound of the present invention is a weather-resistant polycarbonate for outdoor use, an outdoor paint for automobiles, a clear top coating material, an inkjet printing material, glasses, contact lenses, a light guide plate for a liquid crystal back panel, etc. Used for For example, it is conceivable that the compound of the present invention is used not only as a single polymer but also in other diluted acrylate monomers as appropriate to form a curing composition. Moreover, since it has the above functions, application to a functional hard coat material is expected by blending with an appropriate acrylate monomer.

Claims (9)

The polyfunctional polymerizable compound obtained by reaction with the compound represented by following General formula (1), and the compound which has an epoxy group and a (meth) acryl group.

(In the formula, R _{11 to} R ₁₅ each independently represent hydrogen, a hydroxyl group, a methyl group or a methoxy group, and at least one of R _{11 to} R ₁₅ is a hydroxyl group.) The polyfunctional polymerizable compound according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2) or (3).

(In the formula, R ₁₁ , R ₁₂ , R ₁₄ , and R ₁₅ each independently represent hydrogen, a hydroxyl group, a methyl group, or a methoxy group.)

(In the formula, R _{12 to} R ₁₅ each independently represent hydrogen, a hydroxyl group, a methyl group or a methoxy group.) The compound represented by the general formula (2) is a compound represented by the following general formula (4) or (5), and the compound represented by the general formula (3) is represented by the following general formula (6). The polyfunctional polymerizable compound according to claim 2, which is a compound to be produced.

(In the formula, R ₂₁ , R ₂₂ , R ₂₄ and R ₂₅ each independently represent hydrogen, a methyl group or a methoxy group.)

(In the formula, R ₂₁ , R ₂₄ and R ₂₅ each independently represent hydrogen, methyl group or methoxy group.)

(In the formula, R _{22 to} R ₂₅ each independently represent hydrogen, a methyl group or a methoxy group.) The compound represented by the general formula (4) is a compound represented by any one of the following general formulas (7) to (9), and the compound represented by the general formula (5) is represented by the following general formula (10). The polyfunctional polymerizable compound according to claim 3, wherein the compound represented by the general formula (6) is a compound represented by the following general formula (11).

The polyfunctional polymerizable compound according to claim 1, wherein the compound having an epoxy group and a (meth) acryl group is any one of compounds represented by the following general formulas (12) to (14).

(In the formula, R ₃ represents hydrogen or a methyl group.)

(In the formula, R ₃ represents hydrogen or a methyl group.)

(In the formula, R ₃ represents hydrogen or a methyl group.) The polyfunctional polymerizable compound represented by the following general formula (15).

(In the formula, R _{41 to} R ₄₅ are each independently hydrogen, a hydroxyl group, a methyl group, a methoxy group, or a functional group represented by —O—X, and at least one of R _{41 to} R ₄₅ is —O—. It is a functional group represented by X. Here, each X independently represents a functional group having a (meth) acryl group. The polyfunctional polymerizable compound represented by the following general formula (16) or (17) is a polyfunctional polymerizable compound represented by the general formula (15).

(In the formula, R ₄₁ , R ₄₂ , R ₄₄ and R ₄₅ are each independently a hydrogen, a hydroxyl group, a methyl group, a methoxy group or a functional group represented by —O—X, where X is each (The functional group which has a (meth) acryl group independently is shown.)

(In the formula, R _{42 to} R ₄₅ are each independently a hydrogen, a hydroxyl group, a methyl group, a methoxy group, or a functional group represented by —O—X, where X is independently a (meth) acrylic group. A functional group having a group is shown.)   An ultraviolet-absorbing cured product obtained by reacting the polyfunctional polymerizable compound according to claim 1 or 6 with a polymerizable compound having a (meth) acryl group. A method for producing a polyfunctional polymerizable compound according to claim 1,
A method for producing a polyfunctional polymerizable compound, comprising a step of reacting the compound represented by the general formula (1) with a compound having an epoxy group and a (meth) acryl group.

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