TWI483930B - (Meth) acrylate compound having a cyclic structure and a method for producing the same - Google Patents

Description

(Meth) acrylate compound having a cyclic structure and method for producing the same Field of invention

The present invention relates to a cyclic (meth) acrylate compound and a process for producing the same.

Background of the invention

In the case of producing a polymerizable resin composition, (meth) acrylates are one of the important monomers for copolymerization, and can be used for various purposes. Use to mix. However, in general, in a single monomer polymerization, the desired properties are not obtained, and a plurality of different (meth) acrylates or oligomers, polymers, and inorganic materials are mixed for obtaining the necessary physical properties. The desired performance is achieved by such polymerization (Patent Document 1).

For example, the use of a coating composition for a hard coat layer or the like or an ink composition for inkjet printing is mixed with pentaerythritol, neopentyl alcohol, ditrimethylolpropane, trimethylolpropane, and neopentyl alcohol. The (meth) acrylate method of the polyfunctional alcohol represented by the above can impart mechanical strength and chemical stability to the polymerizable resin composition after curing. However, a polyfunctional (meth) acrylate, particularly a (meth) acrylate of dipentaerythritol, has a very high self-adhesion, and there is a problem that the viscosity of the composition rises due to mixing. Further, the use of the polyfunctional (meth) acrylate in the application of a film or the like may cause curling (bending) of the coated film (Patent Documents 2 to 4).

In addition, in other applications, particularly dry film resists, color resists, black resist compositions, etc., in addition to the physical properties of the film after hardening, When hardening is performed by an activation energy line such as an ultraviolet ray or an electron beam, it is required to perform hardening with a low amount of light, that is, high sensitivity is required. In particular, it is considered that a pigment such as a color resist or a black resist is mixed at a high concentration. In the composition having a strong light-shielding property of the dye, the use of a material which can be hardened with a low amount of light is extremely high (Patent Documents 5 and 6).

Prior technical literature Patent literature

Patent Document 1: JP-A-2003-261659

Patent Document 2: JP-A-2008-081571

Patent Document 3: JP-A-2009-025808

Patent Document 4: JP-A-2000-336295

Patent Document 5: JP-A-2001-089416

Patent Document 6: JP-A-2008-046330

Summary of invention

The present invention has been made in view of the above circumstances, and an object thereof is to provide a (meth) acrylate monomer having a cyclic structure and a composition thereof, which have excellent light sensitivity, good air drying property, low viscosity, and hardening. The hardness and low curling property of the film are also excellent, and a production method is provided in which the (meth) acrylate monomer and its composition are produced by industrially reactable raw materials.

The present inventors have conducted intensive research to solve the above problems, and The cyclic (meth) acrylate compound represented by the general formula (1) has a cyclic structure and is superior to dipentaerythritol, neopentyl alcohol, ditrimethylolpropane, trimethylolpropane, The (meth) acrylate of a polyfunctional alcohol represented by pentaerythritol or the like has a low viscosity, and has excellent light sensitivity, good air drying property, and the like, and it is confirmed that the polymerizable composition still maintains the polymerizable composition. The characteristics are completed by the present invention.

That is, the cyclic (meth) acrylate compound of the present invention has a structure represented by the following general formula (1).

In the general formula ^(1), R 1 represents a hydrogen atom or a (meth) Bing Xixi group, and at least one (meth) Bingxi Xi group; A represents a C alkylene group of 2 to 4 of; n-represents 0 A value of ~30.

Among the above compounds, in the general formula (1), n is preferably from 1 to 30.

The method for producing a cyclic (meth) acrylate compound of the present invention is a method for producing a cyclic (meth) acrylate compound having a structure represented by the above general formula (1), comprising a (meth)acrylic acid halide Or (meth)acrylic anhydride reaction, the step of acrylated isosorbide or isosorbide alkylene oxide adduct; and any of the following steps: using between (meth) acrylate Ester exchange, isosorbide or isosorbide alkylene oxide addition a step of (meth)acrylation; or, in the presence of a dehydrating condensing agent or an acid, reacting (meth)acrylic anhydride to cause an isopropyl ester or isosorbide alkylene oxide adduct to form an acrylate The steps of the process.

The cyclic (meth) acrylate compound of the present invention is represented by a combination of conventional dipentaerythritol, neopentyl alcohol, ditrimethylolpropane, trimethylolpropane, and neopentyl alcohol. The polymerizable resin composition of the (meth) acrylate of the polyfunctional alcohol has light sensitivity of the same degree or more, air drying property, hardness of the hardened film, etc., and is low in viscosity, and does not produce a hardened film. Defects such as curling.

Therefore, the compound of the present invention can be suitably used as a polymerizable monomer, for example, a resist resin composition such as a dry film resist, a color resist, a black resist, or a resist for a semiconductor, a dental product, or the like. Medical resin composition, paint. A resin composition for coating, a composition for printing ink, and the like.

Further, since the cyclic (meth) acrylate compound of the present invention is obtained by using isosorbide derived from plants as a main raw material, it is possible to provide a cleaning material which is low in dependence on fossil resources.

Further, according to the production method of the present invention, the above-described compound of the present invention can be produced with high purity and good yield because of industrially simple operation.

Simple illustration

Fig. 1 is an NMR chart of isosorbide diacrylate obtained in Reference Example 1.

Fig. 2 is an NMR chart of the isosorbide 15EO adduct diacrylate obtained in Example 1.

Fig. 3 is an NMR chart of the isosorbide 6EO adduct diacrylate obtained in Example 2.

Form for implementing the invention

Hereinafter, the present invention will be described in detail.

<cyclic (meth) acrylate compound>

The polymerizable single system of the present invention has the structure shown by the structure of the above general formula (1). In the general formula (1), R ¹ represents a hydrogen atom or a (meth) acrylonitrile group, at least one is a (meth) acryl fluorenyl group, A represents a C 2 to 4 alkylene group, and n represents 0 to 30. The value. From the viewpoint of improving the compatibility with the resin and the solvent, lowering the crystallinity, the reactivity at the time of producing the (meth) acrylate, and the physical properties of the cured product, n is preferably from 1 to 30.

<Method for Producing Cyclic (Meth)acrylate Compound>

The method for producing the cyclic (meth) acrylate compound of the present invention is not particularly limited, and an isosorbide or isosorbide alkylene oxide adduct (hereinafter referred to as isosorbide, etc.) as described below can be used. (meth) acrylated reaction of the starting material.

Isosorbide can be produced by a known production method. That is, it can be produced by dehydrating a sorbitol under the action of various dehydration catalysts, particularly a strong acid catalyst. Examples of the catalyst include sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, hydrochloric acid, phosphoric acid, and the like. These dehydration reactions are generally carried out efficiently in an organic solvent such as water or other toluene or xylene. Some methods are known for the purification of sugar alcohol anhydride.

Further, the alkylene oxide adduct of isosorbide can also be produced by a known method.

The (meth) acrylate reaction is carried out by using a (meth)acrylic acid halide or a (meth)acrylic anhydride to esterify a hydroxy group using MMA (methyl propyl methacrylate). An ester of a lower alcohol of (meth)acrylic acid such as methyl enoate is transesterified, and a carbodiimide system such as DCC (dicyclohexylcarbodiimide) or WSCD (water-soluble carbodiimide) is used. A dehydrating condensing agent, a method of dehydrating condensation with (meth)acrylic acid, or a method of dehydrating condensation using an acid catalyst.

Further, since the compound of the present invention and the (meth)acrylic compound of the raw material have high polymerizability, a polymerization inhibitor can be suitably used in the production or storage of the product so that the polymerization does not proceed. The polymerization inhibitor may be p-benzoquinone, hydroquinone, hydroquinone monomethyl ether, 2,5-diphenyl-p-benzoquinone, etc., 2,2,6,6-tetra Nitroxyl radicals such as methyl piperidine-1-oxide (TEMPO), substituted catechols such as t-butylcatechol, and thiophene (phenothiazine), amines such as diphenylamine and phenyl-β-naphthylamine, copper iron, nitrosobenzene, picric acid, molecular oxygen, sulfur, copper (II) chloride, and the like. Among them, in the point of versatility and polymerization inhibition, hydroquinone, thiophene Nitroxyl radicals are preferred.

The amount of the polymerization inhibitor added is preferably 10 ppm or more, more preferably 30 ppm or more, and the upper limit is usually 5,000 ppm or less, and suitably 1,000 ppm or less, based on the compound represented by the general formula (1) of the target. When it is too small, it will not reflect sufficient polymerization inhibition effect, and there is a risk of polymerization during manufacturing or product storage. When it is too much, it may hinder hardening. Polymerization. Therefore, when the compound of the present invention is used alone or when a polymerizable resin composition is formed, it is not suitable for causing a decrease in optical sensitivity, a poor crosslinking property of a cured product, a decrease in physical properties such as mechanical strength, and the like.

<Transesterification method>

A compound which can be used as a (meth) acrylated agent when the (meth) acrylate is esterified by a transesterification method, such as MMA or the like (A Acrylate lower alcohol ester. The lower alcohol is preferably a C1 to C4 aliphatic alcohol, and the number of alcohol residues is selected from 1 to 3. Particularly suitable are methyl, ethyl, n-propyl and isopropyl esters of (meth)acrylic acid. Among them, a methyl ester or an ethyl ester of (meth)acrylic acid can be easily handled at the point of removing the by-product alcohol in the reaction.

The amount of the (meth) acrylate to be used is preferably 2 mol or more, more preferably 4 mol or more, and the upper limit is usually 20 mol or less, based on the molar amount of the isosorbide. Suitable for 10 moles or less.

The method of adding these (meth) acrylates is not particularly limited, and the total amount may be added to the isosorbide for reaction when the reaction is mixed, or may be added in portions during the reaction. The reaction system may be carried out without a solvent or by using a solvent. When a solvent is used, the solvent to be used is not particularly limited, and an aromatic hydrocarbon solvent such as toluene or xylene, an aliphatic hydrocarbon solvent such as hexane or heptane, diethyl ether, tetrahydrofuran or monoethylene glycol can be suitably used. An ether-based solvent such as ether or diethylene glycol dimethyl ether; a ketone-based solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone; dimethylformamide or dimethylacetamide; N-methylpyrrolidine A guanamine-based solvent such as a ketone. Among them, an aromatic hydrocarbon solvent such as toluene or xylene or a ketone-based solvent such as methyl ethyl ketone or methyl isobutyl ketone is preferred at the point of reactivity. These solvents may be used singly or in combination with any of a plurality of solvents.

In the case of using a solvent, the lower limit of the concentration of isosorbide or the like of the raw material is usually 1% or more, suitably 10% or more, and the upper limit is not particularly limited, but is usually 80% or less, and suitably 50% or less. The transesterification reaction is usually carried out in the presence of a catalyst. The catalyst which can be used can be applied to a general transesterification reaction, and for example, a transition gold such as tetraisopropyl titanium oxide. An alkali metal or alkaline earth metal alkoxide such as a compound or sodium methoxide, an aluminum alkoxide such as triisopropyl aluminum oxide, or an alkali metal or alkaline earth metal hydroxide such as lithium hydroxide or sodium hydroxide. a tin compound such as dibutyltin oxide, dioctyltin oxide or distanoxane compound. Among them, a transition metal compound such as tetraisopropyl titanium oxide, an alkali metal such as sodium methoxide or an alcoholic material of an alkaline earth metal, or the like is preferable in terms of catalyst activity and availability.

The lower limit of the amount of the catalyst used relative to the molar amount of the isosorbide or the like of the raw material is usually 0.01 mol% or more, suitably 0.1 mol% or more, more preferably 0.5 mol% or more, and the upper limit is usually It is 50 mol% or less, suitably 20 mol% or less, and further suitably 10 mol% or less. When the amount of the catalyst is too small, the reactivity is lowered, and the yield of the desired ester compound tends to decrease. On the other hand, in the case of too much, the load on the post-treatment step after the transesterification reaction is increased, and the economy is economical. The point of view is also inappropriate.

The reaction is preferably carried out using a reactor equipped with a general stirring device. Further, it is preferred to carry out the reaction while the alcohol produced in the distillation reaction is moved to the formation system. In this case, when the (meth) acrylate used as the alcohol and the reagent is azeotroped and the (meth) acrylate is distilled from the system, the reaction may be carried out by sequentially replenishing the (meth) acrylate as needed.

The reaction temperature is preferably carried out by heating in order to obtain a sufficient reaction rate. Specifically, the lower limit is usually 30 ° C or higher, suitably 50 ° C or higher, and the upper limit is usually 200 ° C or lower, and is suitably carried out in the range of 150 ° C or lower. When the reaction temperature is too high, there will be a (meth) propylene which causes the raw material. The tendency of the ester of the acid ester and the target product to undergo polymerization is too low, and the transesterification reaction is not carried out, or the reaction is extremely slow, and there is a tendency that the reaction must be carried out for a long period of time. The reaction time is arbitrarily selected, but since the alcohol is produced together with the reaction, it is preferred to continue the reaction until a predetermined amount of alcohol is produced. The lower limit of the reaction time is usually 10 minutes or more, and is preferably 30 minutes or more. The upper limit is not particularly limited, but is usually 50 hours or less, and suitably 30 hours or less.

<(Meth)acrylic acid halide method, (meth)acrylic anhydride method>

When (meth)acrylic acid halide or (meth)acrylic anhydride is used as a (meth)acrylic acidizing agent, isosorbide or the like can be (meth)acrylated. The compound which can be used as the (meth)acrylic acid halide in this case is (meth) acrylonitrile, (meth) propylene ruthenium, (meth) propylene iodine.

The lower limit of the amount of the (meth)acrylic acid halide or (meth)acrylic anhydride relative to the molar amount of the isosorbide or the like of the raw material is usually 0.01 mol or more, and suitably 0.05 mol or more. Further suitable is 0.1 mol or more, and the upper limit is usually 20 mol or less, suitably 10 mol or less, and further suitably 5 mol or less.

The method of adding the (meth)acrylic acid halide or the (meth)acrylic anhydride is not particularly limited as long as the long-term contact of the (meth)acrylating agent with the basic substance before the reaction is avoided. . For example, isosorbide or the like may be mixed into the reactor simultaneously with (meth)acrylic acid halide or (meth)acrylic anhydride, and a basic substance may be added later, or an alkaline substance and isosorbide previously mixed into the reactor may be used. Etc., or the solution may be a solution of (meth)acrylic acid halide or (meth)acrylic anhydride to carry out the reaction.

In the case of carrying out a reaction using a (meth)acrylic acid halide or (meth)acrylic anhydride, it is preferred to carry out the reaction system in a dehydrated state. If water is present in the system, it will react with (meth)acrylic acid halide or (meth)acrylic anhydride to cause decomposition. The substrate used in the present invention, such as isosorbide, is a compound which is easily mixed with water, and the amount of water contained in the matrix is preferably as small as possible. Specifically, it is 10 mol% or less with respect to isosorbide or the like, and suitably 0.1 mol% or less.

The reaction can be carried out in either a solvent system or a solvent-free system. However, it is preferred to use a solvent system from the viewpoint of the formation of by-products and the treatment in the step. The solvent is not particularly limited, and an aromatic hydrocarbon solvent such as toluene or xylene, an aliphatic hydrocarbon solvent such as hexane or heptane, diethyl ether, tetrahydrofuran, monoethylene glycol dimethyl ether or diethyl ether can be suitably used. An ether solvent such as glycol dimethyl ether; a ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone; a nitrile solvent such as acetonitrile or benzonitrile; ethyl acetate, butyl acetate or γ-butyrolactone; The ester-based solvent, a guanamine-based solvent such as dimethylformamide or dimethylacetamide or N-methylpyrrolidone, or a halogen-based solvent such as chloroform or dichloroethane. These solvents may be used singly or in combination with any of a plurality of solvents.

In the case of using a solvent, the lower limit of the concentration of the isosorbide or the like of the raw material is usually 1% or more, suitably 10% or more, and the upper limit is not particularly limited, but is usually 80% or less, and suitably 60% or less. The (meth) acrylation reaction using a (meth)acrylic acid halide or (meth)acrylic anhydride is usually carried out in the presence of a basic substance. As the alkaline substance which can be used, metal hydroxide such as sodium hydroxide or barium hydroxide, gold such as sodium carbonate or potassium carbonate can be used. It is a metal phosphate or hydrogen phosphate such as carbonate, monosodium phosphate or potassium phosphate, an alkaline ion exchange resin, an organic tertiary amine such as triethylamine or tributylamine, or an aromatic amine such as pyridine. Among them, pyridine or triethylamine or potassium carbonate can be suitably used.

The amount of the basic substance to be used is usually 1 mol or less, and preferably 2 mol or more, based on the (meth)acrylic acid halide or (meth)acrylic anhydride to be used. Usually, it is 10 mol or less, and suitably 5 mol or less. When the amount of the alkaline substance is too small, the reaction proceeds slowly or stops, which is not suitable. Further, when it is too large, the problem of coloring of the product occurs, and it is not economically appropriate.

The reaction is preferably carried out using a reactor having a corrosion-resistant stirring device. The lower limit of the reaction temperature is usually -50 ° C or higher, suitably -20 ° C or higher, and the upper limit is usually 80 ° C or lower, suitably in the range of 20 ° C or lower.

The reaction time is arbitrarily selected, but it is usually 30 minutes or more, and suitably 60 minutes or more, and the upper limit is not particularly limited, but is usually 20 hours or less, and suitably 10 hours or less.

<condensation agent or acid-induced esterification>

In the case of esterification with (meth)acrylic acid, if a dehydrating condensing agent is present, the reaction proceeds rapidly. The condensing agent is not particularly limited as long as it is generally used for esterification. For example, N,N'-dicyclohexylcarbodiimide or 2-chloro-1,3-dimethyl can be suitably used. Base imidazoline, propane phosphoric anhydride, carbonyl diimidazole (CDI), WSCD (water-soluble carbodiimide), and the like. Further, in this case, an organic basic substance such as pyridine, 4-dimethylamine pyridine or triethylamine may be used in combination. Among them, from the viewpoint of condensation reactivity and easy availability The condensing agent is preferably N,N'-dicyclohexylcarbodiimide, and the basic substance is preferably pyridine or triethylamine.

The lower limit of the reaction temperature is usually -20 ° C, suitably -10 ° C, and the upper limit is usually 100 ° C, suitably 50 ° C. It is theoretically sufficient to use the condensing agent in an amount equivalent to or more than the isosorbide of the substrate, but it may be used in excess. Suitably, it is 1.0 mol or more, and further suitably 2.0 mol or more.

When a condensing agent is not used, (meth)acrylic acid and isosorbide are reacted in the presence of an acid while distilling water. The acid to be used can be used without particular limitation as long as it is an acid used in a general esterification reaction. For example, inorganic acids such as sulfuric acid or hydrochloric acid, organic sulfonic acids such as p-toluenesulfonic acid or methanesulfonic acid, camphorsulfonic acid, acid-type particle exchange resins, and boron fluoride. Water-soluble Lewis acid such as Lewis acid or lanthanide triflate such as an ether complex. These acids may be used singly or in combination of two or more kinds.

The lower limit of the amount of the acid used is 0.1 mol% or more based on the isosorbide of the substrate, and is preferably 0.5 mol% or more. On the other hand, the upper limit is not limited and is 20 mol or less, and suitably 10 mol or less. When the amount of the acid catalyst is too small, the reaction proceeds slowly or stops, which is not suitable. In addition, when there is too much, there is a problem that the product is colored, the catalyst remains, and the formation of the Michael adduct is not caused. The tendency of a suitable side reaction.

The reaction can be carried out in either a solvent system or a solvent-free system. However, it is preferred to use a solvent system from the viewpoint of the formation of by-products and the treatment in the step. The case of using a solvent is not particularly limited, and toluene and dimethyl may be suitably used. An aromatic hydrocarbon solvent such as benzene, an aliphatic hydrocarbon solvent such as hexane or heptane, an ether solvent such as diethyl ether, tetrahydrofuran, monoethylene glycol dimethyl ether or diethylene glycol dimethyl ether; A halogen-based solvent such as chloroform or carbon tetrachloride. These solvents may be used singly or in combination with any of a plurality of solvents.

In the case of using a solvent, the lower limit of the concentration of isosorbide or the like in the amount of the raw material is usually 1% or more, suitably 10% or more, and the upper limit is not particularly limited, but is usually 80% or less, and suitably 70% or less. The reaction is usually carried out at a temperature higher than the boiling point of the solvent to be used, and the reaction is carried out while distilling off the water formed. The reaction time is arbitrarily selected, and the reaction end point can be confirmed by measuring the amount of generated water and the acid value in the system. The lower limit of the reaction time is usually 30 minutes or longer, and is preferably 60 minutes or longer. The upper limit is not particularly limited, but is usually 20 hours or shorter, and suitably 10 hours or shorter.

<Refining method>

The purification of the compound represented by the general formula (1) produced by the above reaction can be carried out by a method which is not particularly limited. For example, a distillation method, a recrystallization method, an extraction washing method, a sorption treatment method, and the like. In the case of performing distillation, the form may be arbitrarily selected from single distillation, precision distillation, thin film distillation, molecular distillation, and the like.

<Method for preserving (meth) acrylate monomer>

Since the (meth) acrylate monomer of the present invention has polymerizability, it is desirable to store it in a cool dark place. Further, in order to prevent polymerization, the above-mentioned amount of the above polymerization inhibitor may be used for storage.

<Polymer, polymerizable resin composition>

As an example of the application of the (meth) acrylate monomer of the present invention, the following The polymer used in the raw material of the resin composition for coating, the production conditions thereof, and the like will be described.

In the case of producing a resin composition for coating, in addition to the (meth) acrylate monomer of the present invention, an oligomer such as urethane acrylate or the like is mixed. It is produced by a polymer component, a polymerization initiator, a solvent, or the like. When the content of the (meth) acrylate monomer of the present invention is small, physical properties such as light sensitivity, viscosity, and hardness of the polymer are not sufficiently exhibited.

Hardening of the polymerizable resin composition. The polymerization can be carried out in a generally known manner, and is not particularly limited. For example, a method of performing polymerization in the presence of a radical initiator, or a method of photopolymerization in the presence of a photopolymerization initiator, an anion polymerization method, or the like can be employed.

As the radical polymerization initiator, for example, benzammonium peroxide, methylcyclohexanone peroxide, cumene hydroperoxide, dicumyl peroxide, di-tert-butyl peroxide, tert-butyl can be used. Organic peroxide such as benzoic acid benzoate, diisopropyl peroxycarbonate, t-butylperoxyisopropyl monocarbonate, 2,2'-azobisisobutyronitrile (AIBN), etc. Azo compound.

Among the polymerization initiators of the activation energy line, for example, an aromatic ketone such as diphenyl ketone, an aromatic compound such as ruthenium or α-chloromethyl naphthalene, diphenyl sulfide or thioamine can be used. A sulfur compound such as a carbamic acid salt. The polymerization initiator which uses an activation energy line such as ultraviolet rays may, for example, be acetophenone, acetophenone benzoin ether, 1-hydroxycyclohexyl benzophenone, 2,2-dimethoxy-1,2-diphenylethane. 1-ketone, xanthone, anthrone, benzaldehyde, hydrazine, hydrazine, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorodiphenyl ketone, 4,4'-di Methoxydiphenyl ketone, 4,4'-diaminodiphenyl ketone, benzoin propyl ether, benzoin ether, An Benzil dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenyl Propane-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1-[4-(methylsulfide) Phenyl]-2-morpholinyl-propan-1-one, 2-benzyl-2-dimethylamine-1-(4-morpholinylphenyl)-butanone-1,4-(2- Hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, (2,4,6-trimethylbenzylidene)diphenylphosphine oxide, bis(2,6-dimethoxy Benzobenzine)-2,4,4-trimethylpentylphosphine oxide, oligo(2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)acetone) Wait. A polymerization initiator and a radical initiator may also be used together as needed.

Commercially available products of a polymerization initiator based on an activation energy source are, for example, Ciba Specialty Chemicals Co., Ltd., trade names: IRGACURE 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, CG24-61, DAROCURE 1116, 1173, manufactured by BASF Corporation: Lucirin TPO, UCB company name: Uvecryl P36, Fratelli Lamberti company name: Esacure KIP150, KIP 65LT, KIP 100F, KT37, KT55, KTO46, KIP75 /B and so on.

The amount of the radical polymerization initiator or the polymerization initiator which utilizes the activation energy line can be selected in accordance with a known polymerization reaction. For example, the polymerization initiator of the activation energy line is usually suitably used in an amount of from 0.001 to 20 parts by mass, preferably from 0.01 to 5, per 100 parts by mass of the compound of the present invention represented by the general formula (1) or the polymerizable composition thereof. Parts by mass. In addition, the radical polymerization initiator is usually used in an amount of 0.0001 to 10 parts by mass, and suitably 0.001 to 5 parts by mass, based on 100 parts by mass of the compound of the present invention represented by the general formula (1) or the polymerizable composition. The lower limit of the reaction temperature is usually 0 ° C, and it is suitable. 10 ° C, on the other hand, the upper limit is 200 ° C, suitably 100 ° C.

Example

In the following, the present invention will be described in more detail by way of the examples, but the invention is not limited by the following examples. Here, "parts" are quality benchmarks. Further, the analysis conditions of the gas chromatography and the liquid chromatography are as follows.

<Analysis of Purity by Gas Chromatography>

Pipe column: C-R9A CHROMATOPAC DB-1 0.25mm manufactured by Shimadzu Corporation , 15m, 0.25μm

Carrier gas: 氦

Detector: FID

Injection temperature: 280 ° C

Column temperature: initial temperature 150 ° C (for 2 minutes) → heating rate 10 ° C / min final temperature → 280 ° C (for 10 minutes)

Injection volume: 0.5μL

<High Performance Liquid Chromatography (hereinafter abbreviated as HPLC) Analysis Conditions>

Column: GL Sciences inertsil ODS-2

Mobile phase: acetonitrile: water = 7:3

Flow rate: 0.6mL/min

Detector: UV, RI

Column groove temperature: 40 ° C

Injection volume: 50 μL (0.5% acetonitrile solution)

1. Synthesis of a cyclic (meth) acrylate compound represented by the general formula (1)

[Reference Example 1] (Synthesis of isosorbide diacrylate)

In a 1 L four-necked flask, 146 g (1 mol) of isosorbide, 144 g (2 mol) of acrylic acid, 0.15 g (0.0014 mol) of p-benzoquinone, 1.5 g (0.015 mol) of methanesulfonic acid, and 700 g of toluene were introduced while introducing air into the oil. Heat to 120 ° C in the bath and stir for 10 hours. The reaction is carried out while distilling with water which occurs as the reaction proceeds. After completion of the reaction, it was cooled to room temperature, and washed with 100 ml of distilled water to remove the catalyst. Thereafter, 0.025 g of hydroquinone was added, and the solvent removal operation was carried out under reduced pressure to obtain a pale yellow viscous liquid.

The substance was analyzed by 1 H-NMR, HPLC, and gas chromatography-mass spectrometry (GC-MS) to confirm that it was isosorbide diacrylate. (The yield of the raw material isosorbide standard was 87.4%, GC purity (area ratio) = 95% <, HPLC purity = 97%)

<Isosorbide diacrylate> (1H-NMR (400MHz), CDCl3, in ppm); 6.4(2H), 6.2(2H), 5.8(2H), 4.6(2H), 3.9~4.2(6H)

[Reference Example 2]

The reaction was similarly carried out except that the acrylic acid of Reference Example 1 was replaced with methacrylic acid to obtain a pale yellow viscous liquid.

The substance was clearly analyzed to be isosorbide dimethacrylate by 1H-NMR, HPLC, and gas chromatography-mass spectrometry. (The yield of the raw material isosorbide standard was 85.4%, GC purity (area ratio) = 93% <, HPLC purity = 96%)

<Isosorbide Dimethacrylate> (1H-NMR (400MHz), CDCl3, in ppm); 6.4(2H), 5.8(2H), 4.6(2H), 3.9~4.2(6H), 1.9(6H )

[Reference Example 3] (Synthesis of isosorbide diacrylate)

In a 2 L four-necked flask, 146 g (1 mol) of isosorbide, 181.6 g (2 mol) of acrylonitrile chloride, 0.15 g (0.0014 mol) of p-benzoquinone, and 700 g of toluene were mixed. After cooling to 5 ° C in an ice bath, 202.2 g (2 mol) of triethylamine was slowly dropped using a dropping funnel while confirming the heat of reaction. After the completion of the dropping, stirring was continued for 5 hours under ice bath conditions. Thereafter, the mixture was further stirred for 3 hours after returning to room temperature to terminate the reaction.

After completion of the reaction, the mixture was returned to room temperature and washed with 100 ml of distilled water, 0.025 g of hydroquinone was added, and desolvation was carried out under reduced pressure to obtain a pale yellow viscous liquid.

The substance was clearly analyzed to be isosorbide diacrylate by 1H-NMR, HPLC, and gas chromatography-mass spectrometry. (The yield of the raw material isosorbide standard was 90.4%, GC purity (area ratio) = 98% <, HPLC purity = 99%)

<Isosorbide diacrylate> (1H-NMR (400MHz), CDCl3, in ppm); 6.4(2H), 6.2(2H), 5.8(2H), 4.6(2H), 3.9~4.2(6H)

[Reference Example 4]

The reaction was similarly carried out except that the acrylonitrile chloride of Reference Example 3 was replaced with methacrylic ruthenium chloride to obtain a pale yellow viscous liquid.

The substance was clearly analyzed to be isosorbide dimethacrylate by 1H-NMR, HPLC, and gas chromatography-mass spectrometry. (The yield of the raw material isosorbide standard was 88.4%, GC purity (area ratio) = 97% <, HPLC purity = 98%)

<isosorbide dimethacrylate> (1H-NMR (400MHz), CDCl3, in ppm); 6.4 (2H), 5.8 (2H), 4.6 (2H), 3.9~4.2 (6H), 1.9(6H)

[Reference Example 5] (Synthesis of isosorbide diacrylate)

In a 2 L four-necked flask, 146 g (1 mol) of isosorbide, 252 g (2 mol) of acrylic anhydride, 0.15 g (0.0014 mol) of p-benzoquinone, and 700 g of toluene were mixed. After cooling to 5 ° C in an ice bath, 202.2 g (2 mol) of triethylamine was slowly dropped using a dropping funnel while confirming the heat of reaction. After the completion of the dropping, stirring was continued for 5 hours under ice bath conditions. Thereafter, the mixture was further stirred for 3 hours after returning to room temperature to terminate the reaction.

After completion of the reaction, water washing was carried out with 100 ml of distilled water, 0.025 g of hydroquinone was added, and a solvent removal operation was carried out under reduced pressure to obtain a pale yellow viscous liquid.

The substance was clearly analyzed to be isosorbide diacrylate by 1H-NMR, HPLC, and gas chromatography-mass spectrometry. (The yield of the raw material isosorbide standard was 89.4%, GC purity (area ratio) = 97% <, HPLC purity = 98%)

<Isosorbide diacrylate> (1H-NMR (400MHz), CDCl3, in ppm); 6.4(2H), 6.2(2H), 5.8(2H), 4.6(2H), 3.9~4.2(6H)

[Reference Example 6] (Synthesis of isosorbide dimethacrylate)

The reaction was similarly carried out except that the acrylic anhydride of Reference Example 5 was replaced with methacrylic anhydride to obtain a pale yellow viscous liquid.

After completion of the reaction, water washing was carried out with 100 ml of distilled water, 0.025 g of hydroquinone was added, and desolvation was carried out under reduced pressure to obtain a pale yellow viscous liquid.

The substance was clearly analyzed to be isosorbide dimethacrylate by 1H-NMR, HPLC, and gas chromatography-mass spectrometry. (Materials are different The yield of pear alcohol was 88.1%, GC purity (area ratio) = 96.1% <, HPLC purity = 97.5%)

<Isosorbide Dimethacrylate> (1H-NMR (400MHz), CDCl3, in ppm); 6.4(2H), 5.8(2H), 4.6(2H), 3.9~4.2(6H), 1.9(6H )

[Example 1] (Synthesis of isosorbide 15EO adduct diacrylate)

146 parts of isosorbide and 1 part of caustic soda were placed in an autoclave and replaced with nitrogen. Under stirring, the temperature was adjusted to 130 ° C and uniformly dispersed. 700 parts of ethylene oxide (EO) was continuously introduced at 130 ° C without the internal pressure of the autoclave exceeding 0.3 MPa. The isosorbide 15EO adduct was prepared by ripening for 2 hours at the same temperature until the pressure was equilibrated. Further, the number average molecular weight of the target was 832, and the average addition mole number of EO was 15.6.

Into a 1 L four-necked flask, 806 g (1 mol) of the isosorbide 15EO adduct, 144 g (2 mol) of acrylic acid, 0.475 g (0.0044 mol) of p-benzoquinone, 4.75 g (0.044 mol) of methanesulfonic acid, and 2216 g of toluene were mixed. The mixture was heated to 120 ° C in an oil bath and stirred for 15 hours. The reaction is carried out while distilling with water which occurs as the reaction proceeds. After completion of the reaction, it was cooled to room temperature, and washed with 150 ml of distilled water to remove the catalyst. Thereafter, 0.066 g of hydroquinone was added, and the solvent removal operation was carried out under reduced pressure to obtain a pale yellow viscous liquid.

The substance was clearly analyzed to be isosorbide diacrylate by 1H-NMR, HPLC, and gas chromatography-mass spectrometry. (The yield of the raw material isosorbide standard was 82.4%, GC purity (area ratio) = 94% <, HPLC purity = 95%)

<Isosorbide diacrylate> (1H-NMR (400MHz), CDCl3, single Bits are ppm); 6.4(2H), 6.2(2H), 5.8(2H), 4.6(2H), 4.3(4H), 3.5~4.0(62H)

[Example 2] (Synthesis of isosorbide 6EO adduct diacrylate)

146 parts of isosorbide and 1 part of caustic soda were placed in an autoclave and replaced with nitrogen. Under stirring, the temperature was adjusted to 130 ° C and uniformly dispersed. 260 parts of ethylene oxide (EO) was continuously introduced at 130 ° C without causing the internal pressure of the autoclave to exceed 0.3 MPa. Isosorbide 6EO was prepared by ripening for 4 hours at the same temperature until the pressure was equilibrated. Further, the number average molecular weight of the target was 344, and the average addition mole number of EO was 4.5.

Into a 1 L four-necked flask, 410 g (1 mol) of the above isosorbide 6EO adduct, 144 g (2 mol) of acrylic acid, 0.283 g (0.0026 mol) of p-benzoquinone, 2.83 g (0.026 mol) of methanesulfonic acid, and 1293 g of toluene were mixed. The mixture was heated to 120 ° C in an oil bath and stirred for 13 hours. The reaction is carried out while distilling with water which occurs as the reaction proceeds. After completion of the reaction, the mixture was cooled to room temperature, and washed with 120 ml of distilled water to remove the catalyst. Thereafter, 0.038 g of hydroquinone was added, and a solvent removal operation was carried out under reduced pressure to obtain a pale yellow viscous liquid.

The substance was clearly analyzed to be isosorbide diacrylate by 1H-NMR, HPLC, and gas chromatography-mass spectrometry. (The yield of the raw material isosorbide standard was 84.4%, GC purity (area ratio) = 96% <, HPLC purity = 96%)

<isosorbide diacrylate> (1H-NMR (400MHz), CDCl3, in ppm); 6.4 (2H), 6.2 (2H), 5.8 (2H), 4.6 (2H), 4.3 (4H), 3.5~ 4.0(26H)

2. Physical property evaluation of isosorbide di(meth) acrylate

With respect to the isosorbide diacrylate obtained in the above Reference Example 1, the physical properties of the resin composition and the hardened film thereof were evaluated as follows by using KAYARAD DPHA of a polyfunctional monomer and HDDA of the same bifunctional. Preparation method and determination of the sample. The evaluation method is as follows. The results are shown in Table 1.

[Reference Example 7]

5 parts of 1-hydroxy-cyclohexyl-benzophenone (trade name: IRGACURE 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) was added to 100 parts of isosorbide diacrylate obtained in Reference Example 1, and the product was used as a resin composition. .

[Comparative Example 1]

5 parts of 1-hydroxy-cyclohexyl-benzophenone was added to 100 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.). The name IRGACURE 184, manufactured by Ciba Specialty Chemicals Co., Ltd., was used as a resin composition.

[Comparative Example 2]

5 parts of 1-hydroxy-cyclohexyl-benzophenone (trade name: IRGACURE 184, Ciba Specialty) was added to 100 parts of 1,6-hexanediol diacrylate (trade name: New Frontier HDDA, manufactured by Daiichi Kogyo Co., Ltd.). The product was made into a resin composition.

In the case of the hardened film for evaluation, the resin composition obtained in Reference Example 7 and Comparative Examples 1 and 2 was applied onto a glass substrate at a film thickness of 100 μm by using a bar coater. A belt-driven UV hardening device equipped with a metal halide lamp is hardened with an accumulated illuminance of 200 mj/cm ² .

<viscosity>

The viscosity was measured by a cone-and-plate type rotary viscometer (E-type viscometer manufactured by Toki Sangyo Co., Ltd.) connected to a constant temperature bath and a circulation pump.

<refractive index>

The film was coated on a glass substrate with a film thickness of 20 μm by a bar coater, and cured under the same conditions as the adhesion, and the refractive index was measured by a prism coupler (Model: 2010, manufactured by Metricon Co., Ltd.).

<Volume shrinkage rate>

The specific gravity of the test sample before and after hardening was measured based on JIS K0061-1992, and the volume shrinkage ratio was measured by the following formula.

Volume shrinkage (%) = {(specific gravity after hardening - specific gravity before hardening) / specific gravity after hardening} × 100

<contact angle>

The droplet method was used for the measurement. The height of the apex and the radius of the water droplet are directly read, and the contact angle is obtained by θ=2arctan(h/a).

<hardenability>

A film thickness of 10 μm was applied to a glass substrate by a bar coater, and light was blocked by a stage meter (25th order, manufactured by Riston), and a parallel light type lighter manufactured by USHIO Co., Ltd. was used under the condition of blocking air ( SX-UID501H UVQ) is hardened with a cumulative illuminance of 50 mj, and the order of the surface dryness is recorded.

<pencil hardness>

Each resin composition was cured with a cumulative illuminance of 400 mj/cm ² using glass, PET, ABS, PC, or acrylic resin as a substrate by a belt-driven UV curing device equipped with a metal halide lamp, and measured in accordance with JIS K5600-5-4. The hardness of the film on the substrate.

<adhesion>

The resin composition was cured with a cumulative illuminance of 400 mj/cm ² using ABS, PC, and acrylic resin as a substrate by a belt-driven UV curing device equipped with a metal halide lamp, and the grid number test prescribed in JIS-K5400 was carried out to The number is used as the adhesion.

<Abrasion resistance>

The film was coated on a PET substrate with a film thickness of 20 μm by a bar coater, and a hardened film was formed under the same conditions as the adhesion, and a TABER abrasion test was performed. The CS-10F abrasion wheel was used at a load of 500 g, and the haze at the specified number of revolutions was measured by a haze meter (HGA type manufactured by SUGA Co., Ltd.).

<Weather resistance>

The film was coated on a PET substrate with a film thickness of 10 μm by a spin coater, and a hardened film was formed under the same conditions as the adhesion. The oily marking liquid, the hair dye, and the shoe polish were applied to the hardened film and allowed to stand for 18 hours, and the appearance when rubbed with ethanol cotton was visually observed, and evaluated by the following criteria.

○: no coloring, △: slightly colored, ×: heavy coloring

<Chemical resistance>

The film was formed under the same conditions as the stain resistance, and a commercially available bleach composed of hypochlorite, sodium hydroxide, a surfactant (alkylamine oxide), and the like was dropped on the test film and allowed to stand in a petri dish. Set for 18 hours. The film was wiped with a thin paper and visually observed for changes in the film, and evaluated by the following criteria.

○: There is no abnormality in the cured film. △: The gloss is slightly changed. ×: The cured film has obvious abnormalities such as whitening, cracking, and floating.

<Water resistance>

The film was formed under the same conditions as the stain resistance test, and the tap water was tapped, and the appearance when visually rubbed off after 18 hours was evaluated by the following criteria.

○: There is no abnormality in the cured film. △: The gloss is slightly changed. ×: The cured film has obvious abnormalities such as whitening, cracking, and floating.

<acid resistance>

The film was formed under the same conditions as the stain resistance test, and a drop of 0.1 mol/L aqueous hydrochloric acid solution was dropped on the test film, and allowed to stand in a petri dish for 18 hours. Wipe with a tissue paper and visually observe whether the film has changed, and evaluate it on the same basis as the water resistance.

<Alkaline resistance>

The film was formed under the same conditions as the stain resistance test, and a drop of 2% aqueous sodium hydroxide solution was dropped on the test film, and allowed to stand in a petri dish for 18 hours. Wipe with a tissue paper and visually observe whether the film has changed, and evaluate it on the same basis as the water resistance.

<Transparency>

The film was coated on a glass substrate with a film thickness of 20 μm by a bar coater, and cured under the same conditions as the adhesion, and the haze was measured by a haze meter, and the measured value was used as the transparency.

<curlability>

It was coated on a PET film having a thickness of 150 μm by a strip coater at 20 μm, and hardened under the same conditions as the adhesion. The heights of the four corners of the film were measured, and the average value thereof was used as the curling property.

As is apparent from the results of Table 1, the isosorbide diacrylate is a bifunctional monomer and exhibits substantially the same physical properties as the DPHA of the polyfunctional monomer, and further, it has low viscosity, high sensitivity, and has a curl of the hardened film. Excellent character with low sexuality.

3. Preparation of polymerizable resin composition and determination of physical properties of hardened film

Isosorbide diacrylate prepared using Reference Example 1 and compared The polyfunctional monomer DPHA and the same bifunctional monomer HDDA which are the same as those of the above-mentioned Reference Example 7 and the like, and the physical properties of the resin composition and the hardened film which are composition-formed with the urethane acrylate as described below. Perform measurements or evaluations.

[Reference Example 8]

50 parts of isosorbide diacrylate obtained by the above Reference Example 1 were mixed, 50 parts of New Frontier R-1204 (a urethane acrylate resin, manufactured by Dai-Il Pharmaceutical Co., Ltd.), and 5 parts of 1-hydroxy- Cyclohexyl-benzophenone (trade name: IRGACURE 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) was used to prepare a polymerizable resin composition.

[Reference Example 9]

The urethane acrylate resin of Reference Example 8 was replaced with New Frontier R-1302 (urethane-based acrylate resin, manufactured by Dai-Il Pharmaceutical Co., Ltd.) to prepare the same resin composition.

[Comparative Example 3]

In place of the isosorbide diacrylate of Reference Example 8, the same resin composition was prepared by using a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.). Things.

[Comparative Example 4]

In place of the isosorbide diacrylate of Reference Example 8, the same resin composition was prepared by using 1,6-hexanediol diacrylate (trade name: New Frontier HDDA, manufactured by Dai-ichi Kogyo Co., Ltd.).

[Comparative Example 5]

In Reference Example 8, no monomer was added, but 100 parts of New were mixed. Frontier R-1204 (urethane acrylate resin, manufactured by Dai-Il Pharmaceutical Co., Ltd.), 5 parts of 1-hydroxy-cyclohexyl-benzophenone (trade name: IRGACURE 184, manufactured by Ciba Specialty Chemicals Co., Ltd.), and obtained polymerization. Resin composition.

[Comparative Example 6]

The isosorbide di(meth)acrylate of the reference example 9 was prepared by using a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.). Resin composition.

[Comparative Example 7]

In place of the isosorbide di(meth)acrylate of Reference Example 9, the same resin composition was prepared using 1,6-hexanediol diacrylate (trade name: New Frontier HDDA, manufactured by Dai-ichi Kogyo Co., Ltd.).

[Comparative Example 8]

In Reference Example 9, the monomer was not added, but 100 parts of New Frontier R-1302 (a urethane acrylate resin, manufactured by Dai-Il Pharmaceutical Co., Ltd.) and 5 parts of 1-hydroxy-cyclohexyl-benzophenone were mixed. (trade name: IRGACURE 184, manufactured by Ciba Specialty Chemicals Co., Ltd.), and a polymerizable resin composition was obtained.

The above determination. In the evaluation method, the hardened film for evaluation was coated with the polymerizable resin composition obtained in Reference Examples 8, 9 and Comparative Examples 3 to 8 by a bar coater at a film thickness of 100 μm, except for the case where it was specifically described. It was prepared by using a belt-driven UV hardening device equipped with a metal halide lamp to accumulate an illuminance of 200 mj/cm ² to harden it on a glass substrate.

From the results of Table 2, it was found that the viscosity of isosorbide diacrylate was significantly lower than that of DPHA, and the viscosity of the high viscosity urethane acrylate was greatly improved, and the hardenability, curling property, and other physical properties were greatly improved. Further, it was found that the hardness and the like of the hardened film of HDDA were remarkably improved.

Industrial availability

The cyclic (meth) acrylate compound of the present invention and the cured product obtained by curing the polymerizable resin composition containing the compound have high hardness, low curling property, and excellent hardenability, so that they can be suitably used. For example, a coating application such as a bar coater, an ink composition for inkjet printing, or a resist composition such as a dry film resist, a color resist, or a black resist.

Fig. 1 is an NMR chart of isosorbide diacrylate obtained in Reference Example 1.

Fig. 2 is an NMR chart of the isosorbide 15EO adduct diacrylate obtained in Example 1.

Fig. 3 is an NMR chart of the isosorbide 6EO adduct diacrylate obtained in Example 2.

Claims (2)

A (meth) acrylate compound having a cyclic structure, which is characterized by the general formula (1): In the general formula (1), R ¹ represents a (meth) acrylonitrile group; A represents a C 2 to 4 alkylene group; and n represents a value of 6 to 15. A method for producing a cyclic (meth) acrylate compound according to claim 1, characterized in that it comprises any one of the following steps: reacting a (meth)acrylic acid halide or (meth)acrylic anhydride And the step of acylating an isosorbide alkylene oxide adduct; using a transesterification with a (meth) acrylate, and reacting the isosorbide alkylene oxide adduct with a (meth) acrylate Or a step of acrylating the (meth)acrylic anhydride in the presence of a dehydrating condensing agent or an acid and subjecting the isosorbide alkylene oxide adduct to acylation.