JP5270510B2 - Cyclic (meth) acrylate compound, method for producing the same, and resin composition - Google Patents

Abstract

Provided are (meth)acrylate monomers which have cyclic structures and which exhibit excellent photosensitivity, good air-drying properties, high hardness, and low viscosity. Also provided are polymerizable resin compositions containing the same. Cyclic (meth)acrylates that have structures represented by general formula (1) [wherein R1s are each a hydrogen atom or (meth)acryloyl, with at least one R1 being (meth)acryloyl; A is C2-4 alkylene; and n is a number of 0 to 30].

Description

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

  When producing a polymerizable resin composition, (meth) acrylic acid esters are one component of an important copolymerization monomer and are blended for various purposes and applications. However, in general, polymerization of a single monomer often fails to provide the desired performance, and a plurality of different (meth) acrylic acid esters, oligomers, polymers, and inorganic materials are used to obtain the required physical properties. It mix | blends and the target performance is expressed by making this superpose | polymerize (patent document 1).

  For example, in coating compositions such as hard coats and ink compositions for inkjet printing, (meth) acrylates of polyfunctional alcohols typified by dipentaerythritol, pentaerythritol, ditrimethylolpropane, trimethylolpropane, pentaerythritol and the like are blended. By this, it is possible to impart mechanical strength and chemical stability of the polymerizable resin composition after curing. However, polyfunctional (meth) acrylates, in particular (pentaerythritol) (meth) acrylate itself have a very high viscosity, and there is a problem of increasing the viscosity of the composition when blended. Moreover, polyfunctional (meth) acrylate also has a problem that the coated film curls (warps) in applications such as film coating (Patent Documents 2 to 4).

  In other applications, especially dry film resists, colored resists, black resist compositions, etc., in addition to the film physical properties after curing, a low exposure amount, particularly when curing with active energy rays such as ultraviolet rays and electron beams. However, it is required to complete curing, that is, to have high sensitivity. In particular, in a highly light-shielding composition in which pigments and dyes such as colored resists and black resists are blended at a high concentration, the utility value of a material that can be cured even at a low exposure amount is considered to be extremely high (Patent Documents 5 and 6). .

JP 2003-261659 A JP 2008-081571 A JP 2009-025808 A JP 2000-336295 A JP 2001-089416 A JP 2008-046330 A

  The present invention has been made in view of the above, and has a cyclic structure that has excellent photosensitivity, good air-drying property, low viscosity, and excellent hardness and low curl properties of a cured film (meta). An object of the present invention is to provide an acrylate monomer and a composition thereof, and a method for producing the acrylate monomer from a commercially available raw material by an industrially feasible reaction.

  As a result of intensive studies to solve the above problems, the present inventors have found that the cyclic (meth) acrylate compound represented by the general formula (1) has a cyclic structure, and dipentaerythritol, pentaerythritol, ditrimethylolpropane, It has been found that it has excellent photosensitivity, good air-drying properties, etc. while having low viscosity compared to (meth) acrylates of polyfunctional alcohols typified by trimethylolpropane, pentaerythritol, etc., and its polymerizability It was confirmed that the characteristics of the composition were maintained, and the present invention was completed.

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) acryloyl group, at least one is a (meth) acryloyl group, A represents an alkylene group having 2 to 4 carbon atoms, and n is 1 to The number of 30 is represented.

  The method for producing a cyclic (meth) acrylate compound of the present invention is a method for producing a cyclic (meth) acrylate compound having the structure represented by the general formula (1), and is a (meth) acrylic acid halide or (meth) acrylic. The step of reacting an acid anhydride to acrylate the isosorbide or isosorbide alkylene oxide adduct, (meth) acrylate conversion of the isosorbide or isosorbide alkylene oxide adduct by transesterification with (meth) acrylate Or a step of reacting a (meth) acrylic anhydride in the presence of a dehydration condensing agent or an acid to acrylate the isosorbide or isosorbide alkylene oxide adduct.

  The cyclic (meth) acrylate compound of the present invention is a polymerizable resin composition containing a polyfunctional alcohol (meth) acrylate represented by conventional dipentaerythritol, pentaerythritol, ditrimethylolpropane, trimethylolpropane, pentaerythritol and the like. While having photosensitivity, air-drying property, hardness of cured film, etc. comparable to or higher than that of an object, it is possible to lower the viscosity and prevent problems such as curling of the cured film.

  Accordingly, the compound of the present invention is used as a polymerizable monomer, for example, a resist resin composition such as a dry film resist, a colored resist, a black resist and a semiconductor resist, a medical resin composition such as dentistry, and a resin composition for paints and coatings. The ink composition is suitably used for a printing ink composition.

  Moreover, since the cyclic | annular (meth) acrylate compound of this invention is obtained by using plant-derived isosorbide as a main raw material, it can provide the clean material with low dependence on a fossil resource.

  Further, according to the production method of the present invention, the compound of the present invention can be produced with high purity and high yield by an industrially simple operation.

2 is an NMR chart of isosorbide diacrylate obtained in Reference Example 1. 6 is an NMR chart of isosorbide 15EO adduct diacrylate obtained in Reference Example 7. 6 is an NMR chart of isosorbide 6EO adduct diacrylate obtained in Reference Example 8.

  Hereinafter, the present invention will be described in detail.

<Cyclic (meth) acrylate compound>
The polymerizable monomer of the present invention has a structure represented by the structure of the general formula (1). In general formula (1), R ¹ represents a hydrogen atom or a (meth) acryloyl group, at least one is a (meth) acryloyl group, A represents an alkylene group having 2 to 4 carbon atoms, and n is 0 to 0. The number of 30 is represented. n is preferably 1 to 30 in view of improvement in compatibility with the resin and the solvent, decrease in crystallinity, reactivity during the production of (meth) acrylic acid ester, physical properties of the cured product, and the like.

<Method for producing cyclic (meth) acrylate compound>
Although the manufacturing method of the cyclic (meth) acrylate compound of the present invention is not particularly limited, a (meth) acrylate reaction using the following isosorbide or isosorbide alkylene oxide adduct (hereinafter referred to as isosorbide or the like) as a raw material is performed. Can be used.

  Isosorbide can be produced by a known production method. That is, it can be produced by dehydrating sorbitol by the action of various dehydration catalysts, particularly strong acid catalysts. Examples of the catalyst include sulfuric acid, paratoluenesulfonic acid, methanesulfonic acid, hydrochloric acid, phosphoric acid and the like. These dehydration reactions are generally performed efficiently in water and other organic solvents such as toluene and xylene. Several methods are known as methods for purifying anhydrous sugar alcohols.

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

  As the (meth) acrylate reaction, a method of esterifying a hydroxyl group using (meth) acrylic acid halide or (meth) acrylic anhydride, or an ester of a lower alcohol of (meth) acrylic acid such as MMA is used. A transesterification reaction, a method of dehydration condensation with (meth) acrylic acid using a carbodiimide-based dehydration condensation agent such as DCC or WSCD, a method of dehydration condensation using an acid catalyst, or the like is used.

  Since the compound of the present invention and the raw material (meth) acrylic acid compound have high polymerizability, a polymerization inhibitor may be appropriately used so that polymerization does not proceed during production or during product storage. Polymerization inhibitors include hydroquinones such as p-benzoquinone, hydroquinone, hydroquinone monomethyl ether and 2,5-diphenylparabenzoquinone, N-oxy radicals such as tetramethylpiperidinyl-N-oxy radical (TEMPO), t -Substituted catechols such as butyl catechol, amines such as phenothiazine, diphenylamine and phenyl-β-naphthylamine, cuperone, nitrosobenzene, picric acid, molecular oxygen, sulfur, copper (II) chloride and the like. Among these, hydroquinones, phenothiazines and N-oxy radicals are preferable from the viewpoint of versatility and polymerization inhibition.

  The addition amount of the polymerization inhibitor is about 10 ppm or more, preferably 30 ppm or more, and the upper limit is usually 5000 ppm or less, preferably 1000 ppm or less with respect to the compound represented by the general formula (1) which is the target product. It is. If the amount is too small, there is a risk that polymerization will not sufficiently develop and there is a risk that polymerization will proceed during production or storage of the product, and if it is too large, the curing / polymerization reaction may be hindered. is there. For this reason, the compound of the present invention alone or its polymerizable resin composition may cause a decrease in photosensitivity, poor crosslinking of a cured product, a decrease in physical properties such as mechanical strength, and the like, which is not preferable.

<Transesterification method>
A compound that can be used as a (meth) acrylate agent in the case of (meth) acrylate-converting isosorbide or the like by a transesterification method is a lower alcohol ester of (meth) acrylic acid such as MMA. The lower alcohol is preferably a C1-C4 aliphatic alcohol, and the number of alcohol residues is selected from 1 to 3. Particularly preferred are (meth) acrylic acid methyl ester, ethyl ester, n-propyl ester and i-propyl ester. Among these, (meth) acrylic acid methyl ester, ethyl ester and the like are preferable because they can be easily operated in terms of removing alcohol by-produced during the reaction.

  The amount of (meth) acrylic acid ester used is usually 2 mol equivalents or more, preferably 4 mol equivalents or more, and the upper limit is usually 20 mol equivalents or less, preferably 10 with respect to the number of moles of raw material isosorbide. Less than molar equivalent.

  There are no particular restrictions on the method of adding these (meth) acrylic acid esters, and it is possible to carry out the reaction by adding the entire amount to isosorbide during the preparation of the reaction, or to add it in the middle of the reaction, Is possible. The reaction can be carried out without solvent or using a solvent. When using a solvent, the solvent to be used is not particularly limited, but an aromatic hydrocarbon solvent such as toluene and xylene, an aliphatic hydrocarbon solvent such as hexane and heptane, diethyl ether, tetrahydrofuran, monoethylene glycol dimethyl ether, diethylene glycol Ether solvents such as dimethyl ether, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone are preferably used. Among these, aromatic hydrocarbon solvents such as toluene and xylene, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone are preferable in terms of reactivity. These solvents may be used alone, or a plurality of arbitrary solvents may be mixed and used.

  When using a solvent, the lower limit of the concentration of the raw material, such as isosorbide, is usually 1% or more, preferably 10% or more, and the upper limit is not particularly limited, but is usually 80% or less, preferably 50% or less. . The transesterification reaction is usually performed in the presence of a catalyst. As the usable catalyst, those generally usable in transesterification can be applied, for example, transition metal compounds such as titanium tetraisopropoxysite, alkali metal or alkaline earth metal alcoholate such as sodium methoxide, and the like. Aluminum alkoxides such as aluminum triisopropoxide, alkali metal and alkaline earth metal hydroxides such as lithium hydroxide and sodium hydroxide, tin compounds such as dibutyltin oxide, dioctyltin oxide, and distanoxane compounds. . Of these, transition metal compounds such as titanium tetraisopropoxysite, alkali metals such as sodium methoxide and alcoholates of alkaline earth metals, and the like are preferable because of their catalytic activity and availability.

  The amount of these catalysts used is usually 0.01 mol% or more, preferably 0.1 mol% or more, more preferably 0.5 mol% or more, and the upper limit is the mol number of isosorbide or the like of the raw material. Usually, it is 50 mol% or less, preferably 20 mol% or less, more preferably 10 mol% or less. When the amount of the catalyst is too small, the reaction activity tends to be low and the yield of the desired ester compound tends to be low. On the other hand, when the amount is too large, the load on the post-treatment step after the transesterification reaction increases, Moreover, it is not preferable also from an economical viewpoint.

  The reaction is preferably carried out in a reactor equipped with a normal stirring device. In addition, it is preferable to carry out the reaction while transferring the equilibrium to the production system while distilling off the alcohol generated during the reaction. At this time, if the (meth) acrylic acid ester used as the reagent and the alcohol azeotropes and the (meth) acrylic acid ester is distilled off from the system, the (meth) acrylic acid ester is added as necessary. You may react by replenishing sequentially.

  It is preferable to carry out the reaction with heating in order to obtain a sufficient reaction rate. Specifically, the lower limit is usually 30 ° C. or higher, preferably 50 ° C. or higher, and the upper limit is usually 200 ° C. or lower, preferably 150 ° C. or lower. When the reaction temperature is too high, the polymerization reaction of the raw material (meth) acrylic acid ester or the target product ester tends to occur, and when it is too low, the transesterification reaction does not proceed or the reaction is extremely slow, There is a tendency to require a long reaction time. The reaction time is arbitrarily selected, but since alcohol is produced as the reaction proceeds, it is preferable to continue the reaction until a predetermined amount of alcohol is produced. In general reaction time, the lower limit is usually 10 minutes or longer, preferably 30 minutes or longer, and the upper limit is not particularly limited, but is usually 50 hours or shorter, preferably 30 hours or shorter.

<(Meth) acrylic acid halide method, (meth) acrylic anhydride method>
Isosorbide or the like can be (meth) acrylated using (meth) acrylic acid halide or (meth) acrylic anhydride as a (meth) acrylating reagent. The compounds that can be used as the (meth) acrylic acid halide in that case are (meth) acrylic acid chloride, (meth) acrylic acid bromide, and (meth) acrylic acid iodide.

  The lower limit of the amount of (meth) acrylic acid halide or (meth) acrylic anhydride used is usually 0.01 mol equivalent or more, preferably 0.05 mol equivalent or more, relative to the number of moles of raw material isosorbide and the like. More preferably, it is 0.1 mol equivalent or more, and the upper limit is usually 20 mol equivalent or less, preferably 10 mol equivalent or less, more preferably 5 mol equivalent or less.

  It is a method of adding these (meth) acrylic acid halides or (meth) acrylic anhydrides, but if these (meth) acrylic reagents and basic substances are kept from contacting for a long time before the reaction, the addition There is no particular limitation on the method. For example, isosorbide and (meth) acrylic acid halide or (meth) acrylic anhydride may be charged into the reactor at the same time, a basic substance may be added later, or a basic substance previously charged into the reactor. The reaction may be carried out by dropping (meth) acrylic acid halide or (meth) acrylic acid anhydride into the solution thereof or isosorbide.

  When the reaction is performed using (meth) acrylic acid halide or (meth) acrylic anhydride, the reaction system is preferably performed in a dehydrated state. When moisture is present in the system, it reacts with (meth) acrylic acid halide or (meth) acrylic anhydride and decomposes. The substrate used in the present invention, such as isosorbide, is a compound that is easily miscible with water, but the smaller the amount of water contained in the substrate, the better. Specifically, it is 10 mol% or less, preferably 0.1 mol% or less with respect to isosorbide or the like.

  The reaction can be carried out in either a solvent system or a solvent-free system, but a solvent system is preferred from the viewpoint of production of by-products and handling in the process. When a solvent is used, there is no particular limitation, but aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane and heptane, ethers such as diethyl ether, tetrahydrofuran, monoethylene glycol dimethyl ether, and diethylene glycol dimethyl ether Solvents, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitrile solvents such as acetonitrile and benzonitrile, ester solvents such as ethyl acetate, butyl acetate and gamma butyrolactone, dimethylformamide, dimethylacetamide and N-methylpyrrolidone An amide solvent, a halogen solvent such as chloroform and dichloroethane, and the like are preferably used. These solvents may be used alone, or a plurality of arbitrary solvents may be mixed and used.

  When using a solvent, the lower limit of the concentration of the raw material, such as isosorbide, is usually 1% or more, preferably 10% or more, and the upper limit is not particularly limited, but is usually 80% or less, preferably 60% or less. . The (meth) acrylation reaction with (meth) acrylic acid halide or (meth) acrylic anhydride is usually performed in the presence of a basic substance. Usable basic substances include metal hydroxides such as sodium hydroxide and barium hydroxide, metal carbonates such as sodium carbonate and potassium carbonate, metal phosphates such as monosodium phosphate and potassium phosphate It is possible to use salts, hydrogen phosphates, basic ion exchange resins, organic tertiary amines such as triethylamine and tributylamine, and aromatic amines such as pyridine. Of these, pyridine, triethylamine, and potassium carbonate are preferably used.

  Although it is the usage-amount of these basic substances, with respect to the (meth) acrylic acid halide or (meth) acrylic anhydride used, the lower limit is usually 1 molar equivalent, preferably 2 molar equivalents or more, and the upper limit. Is usually used in an amount of 10 mol equivalent or less, preferably 5 mol equivalent or less. When the amount of the basic substance is too small, it is not preferable because the progress of the reaction is slow or stopped, and when it is too large, there is a problem of product coloring, which is not preferable economically.

  The reaction is preferably carried out in a reactor equipped with a corrosion-resistant stirrer. The lower limit of the reaction temperature is usually −50 ° C. or higher, preferably −20 ° C. or higher, and the upper limit is usually 80 ° C. or lower, preferably 20 ° C. or lower.

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

<Esterification with condensing agent or acid>
When esterifying with (meth) acrylic acid, the reaction proceeds rapidly when a dehydrating condensing agent is allowed to coexist. As the condensing agent, a condensing agent generally known for esterification can be used without particular limitation. For example, N, N′-dicyclohexylcarbodiimide, 2-chloro-1,3-dimethylimidazolium chloride, propane Phosphonic anhydride, carbonyldiimidazole (CDI), WSCD (water-soluble carbodiimide) and the like are preferably used. In this case, an organic basic substance such as pyridine, 4-dimethylaminopyridine or triethylamine may be used in combination. Among these, N, N′-dicyclohexylcarbodiimide is preferable as the condensing agent, and pyridine and triethylamine are preferable as the basic substance from the viewpoint of condensation reactivity and availability.

  The lower limit of the reaction temperature is usually −20 ° C., preferably −10 ° C., and the upper limit is usually 100 ° C., preferably 50 ° C. The amount of the condensing agent used is theoretically sufficient if it is used in an equal amount or more with respect to isosorbide as a substrate, but it may be used in excess. Preferably, it is 1.0 molar equivalent or more, more preferably 2.0 molar equivalent or more.

  When a condensing agent is not used, (meth) acrylic acid and isosorbide are reacted in the presence of an acid while distilling off generated water. Any acid can be used without particular limitation as long as it is an acid used in a normal esterification reaction. For example, inorganic acids such as sulfuric acid and hydrochloric acid, organic sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid and camphorsulfonic acid, acid type ion exchange resins, Lewis acids such as fluorinated boron and ether complexes, lanthanide trif Examples thereof include water-soluble Lewis acids such as rate. These acids may be used alone or in combination of two or more.

  The minimum of the usage-amount of an acid is 0.1 mol% or more with respect to the isosorbide which is a substrate, Preferably it is 0.5 mol% or more. On the other hand, the upper limit is not limited and is 20 mol equivalent or less, preferably 10 mol equivalent or less. If the amount of the acid catalyst is too small, it is not preferable because the progress of the reaction is slow or stopped. On the other hand, if the amount is too large, problems such as coloring of the product, catalyst remaining, or formation of a Michael adduct are not preferable. Side reactions tend to occur.

  The reaction can be carried out in either a solvent system or a solvent-free system, but a solvent system is preferred from the viewpoint of production of by-products and handling in the process. When using a solvent, the solvent to be used is not particularly limited, but an aromatic hydrocarbon solvent such as toluene and xylene, an aliphatic hydrocarbon solvent such as hexane and heptane, diethyl ether, tetrahydrofuran, monoethylene glycol dimethyl ether, diethylene glycol Ether solvents such as dimethyl ether, halogen solvents such as methylene chloride, chloroform, carbon tetrachloride, and the like are preferably used. These solvents may be used alone, or a plurality of arbitrary solvents may be mixed and used.

  In the case of using a solvent, the concentration of isosorbide as a raw material is such that the lower limit is usually 1% or more, preferably 10% or more, and the upper limit is not particularly limited, but is usually 80% or less, preferably 70%. It is as follows. The reaction is usually carried out at or above the boiling point of the solvent used, and the reaction is carried out while distilling off the produced water. The reaction time is arbitrarily selected, but the end point of the reaction can be recognized by measuring the amount of water produced and the acid value in the system. The lower limit of the reaction time is usually 30 minutes or longer, preferably 60 minutes or longer, and the upper limit is not particularly limited, but is usually 20 hours or shorter, preferably 10 hours or shorter.

<Purification method>
Purification of the compound represented by the general formula (1) produced by the above reaction can be employed without any particular limitation. For example, a distillation method, a recrystallization method, an extraction cleaning method, an adsorption treatment method, and the like. When performing distillation, the form can be arbitrarily selected from simple distillation, precision distillation, thin film distillation, molecular distillation and the like.

<Storage method of (meth) acrylic acid ester monomer>
Since the (meth) acrylic acid ester monomer of the present invention has polymerizability, it is desirable to store it in a cool and dark place. In addition, in order to prevent polymerization, the above-described polymerization inhibitor can be used and stored.

<Polymer, polymerizable resin composition>
As an example of the application of the (meth) acrylic acid ester monomer of the present invention, a polymer, a production condition thereof, and the like when used as a raw material for a coating resin composition will be described below.

  In the case of producing a coating resin composition, in addition to the (meth) acrylic acid ester monomer of the present invention, an oligomer / polymer component such as urethane acrylate, a polymerization initiator, a solvent and the like are blended. When there is little content of the (meth) acrylic acid ester monomer of this invention, there exists a possibility that physical properties, such as the photosensitivity of a composition, a viscosity, and the hardness of a polymer, may not fully be exhibited.

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

  Examples of the radical polymerization initiator include benzoyl peroxide, methylcyclohexanone peroxide, cumene hydroperoxide, diisopropylbenzene peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, diisopropyl peroxycarbonate, t-butyl. Organic peroxides such as peroxyisopropyl monocarbonate and azo compounds such as 2,2′-azobisisobutyronitrile (AIBN) can be used.

  As photopolymerization initiators among polymerization initiators based on active energy rays, for example, aromatic ketones such as benzophenone, aromatic compounds such as anthracene and α-chloromethylnaphthalene, and sulfur compounds such as diphenyl sulfide and thiocarbamate are used. can do. Examples of polymerization initiators using active energy rays such as ultraviolet rays include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, and benzaldehyde. Fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoinpropyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1 -(4-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxa , Diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2 , 6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) and the like. . If necessary, a polymerization initiator based on active energy rays and a radical polymerization initiator may be used in combination.

  As a commercial item of the polymerization initiator by an active energy ray, for example, Ciba Specialty Chemicals Co., Ltd. product name: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, CG24-61, Darocur 1116, 1173, manufactured by BASF, Inc. Product name: Lucilin TPO, manufactured by UCB, Inc. Product name: Ubekrill P36, manufactured by Fratteri Lamberti, Inc. Product names: Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B and the like.

  What is necessary is just to select the usage-amount of the radical polymerization initiator and the polymerization initiator by an active energy ray according to a well-known polymerization reaction. For example, the polymerization initiator based on active energy rays is usually 0.001 to 20 parts by mass, preferably 0. It is appropriate to use 01 to 5 parts by mass. Moreover, a radical polymerization initiator is 0.0001-10 mass parts normally with respect to 100 mass parts of this invention compounds shown by General formula (1), or its polymeric composition, Preferably it is 0.001-5. It is appropriate to use parts by mass. The reaction temperature usually has a lower limit of 0 ° C., preferably 10 ° C., while the upper limit is 200 ° C., preferably 100 ° C.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by a following example, unless the summary is exceeded. Here, “part” is based on mass. Moreover, the analysis conditions of gas chromatography and liquid chromatography are as follows.

<Analysis of purity by gas chromatography>
Column: C-R9A CHROMAPAC DB-1 manufactured by Shimadzu Corporation 0.25 mmφ, 15 m, 0.25 μm
Carrier gas: Helium Detector: FID
Inlet temperature: 280 ° C
Column tank temperature: initial temperature 150 ° C. (2 minutes hold) → temperature increase rate 10 ° C./minute final temperature → 280 ° C. (10 minutes hold)
Injection volume: 0.5 μL

<High performance liquid chromatography (hereinafter abbreviated as HPLC) analysis conditions>
Column: GL Science insertsil ODS-2
Mobile phase: Acetonitrile: Water = 7: 3
Flow rate: 0.6 mL / min Detector: UV, RI
Column bath temperature: 40 ° C
Injection volume: 50 μL (0.5% acetonitrile solution)

1. Synthesis of cyclic (meth) acrylate compound represented by general formula (1) [ Reference Example 1] (Synthesis of isosorbide diacrylate)
A 1 L four-necked flask was charged with 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, and air was introduced. The mixture was heated to 120 ° C. in an oil bath and stirred for 10 hours. The reaction was carried out while distilling off the water that emerged as the reaction proceeded. After completion of the reaction, the mixture 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 was removed under reduced pressure to obtain a pale yellow viscous liquid.

This was analyzed by 1H-NMR, HPLC, and GC-mass spectrum, and was found to be isosorbide diacrylate. (Yield 87.4% based on raw material isosorbide, GC purity (area ratio) = 95% <, HPLC purity = 97%)
<Isosorbide diacrylate> (1H-NMR (400 MHz), CDCl3, in ppm); 6.4 (2H), 6.2 (2H), 5.8 (2H), 4.6 (2H), 3 .9-4.2 (6H)

[ Reference Example 2]
A pale yellow viscous liquid was obtained by reacting in the same manner except that the acrylic acid in Reference Example 1 was replaced with methacrylic acid.

When this product was analyzed by 1H-NMR, HPLC, and GC-mass spectrum, it was revealed to be isosorbide dimethacrylate. (Yield 85.4% based on raw material isosorbide, GC purity (area ratio) = 93% <, HPLC purity = 96%)
<Isosorbide dimethacrylate> (1H-NMR (400 MHz), CDCl3, in ppm); 6.4 (2H), 5.8 (2H), 4.6 (2H), 3.9 to 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 acrylic acid chloride, 0.15 g (0.0014 mol) of p-benzoquinone, and 700 g of toluene were charged. The mixture was cooled to 5 ° C. in an ice bath, and 202.2 g (2 mol) of triethylamine was slowly added dropwise using a dropping funnel while confirming the heat of reaction. After completion of the dropwise addition, the mixture was continuously stirred for 5 hours under ice cooling. Then, it returned to room temperature and stirred for further 3 hours, and reaction was complete | finished.

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

This was analyzed by 1H-NMR, HPLC, and GC-mass spectrum, and was found to be isosorbide diacrylate. (Yield 90.4% based on raw material isosorbide, GC purity (area ratio) = 98% <, HPLC purity = 99%)
<Isosorbide diacrylate> (1H-NMR (400 MHz), CDCl3, in ppm); 6.4 (2H), 6.2 (2H), 5.8 (2H), 4.6 (2H), 3 .9-4.2 (6H)

[ Reference Example 4]
A pale yellow viscous liquid was obtained by reacting in the same manner except that the acrylic acid chloride of Reference Example 3 was replaced with methacrylic acid chloride.

When this product was analyzed by 1H-NMR, HPLC, and GC-mass spectrum, it was revealed to be isosorbide dimethacrylate. (Yield 88.4% based on raw material isosorbide, GC purity (area ratio) = 97% <, HPLC purity = 98%)
<Isosorbide dimethacrylate> (1H-NMR (400 MHz), CDCl3, in ppm); 6.4 (2H), 5.8 (2H), 4.6 (2H), 3.9 to 4.2 ( 6H), 1.9 (6H)

[ Reference Example 5] (Synthesis of isosorbide diacrylate)
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 charged into a 2 L four-necked flask. The mixture was cooled to 5 ° C. in an ice bath, and 202.2 g (2 mol) of triethylamine was slowly added dropwise using a dropping funnel while confirming the heat of reaction. After completion of the dropwise addition, the mixture was stirred for 5 hours under ice cooling. Then, it returned to room temperature and stirred for further 3 hours, and reaction was complete | finished.

  After completion of the reaction, the mixture was washed with 100 ml of distilled water, 0.025 g of hydroquinone was added, and the solvent was removed under reduced pressure to obtain a pale yellow viscous liquid.

This was analyzed by 1H-NMR, HPLC, and GC-mass spectrum, and was found to be isosorbide diacrylate. (Yield 89.4% based on raw material isosorbide, GC purity (area ratio) = 97% <, HPLC purity = 98%)
<Isosorbide diacrylate> (1H-NMR (400 MHz), 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)
A pale yellow viscous liquid was obtained by replacing the acrylic anhydride of Reference Example 5 with methacrylic anhydride and reacting in the same manner.

  After completion of the reaction, the reaction product was washed with 100 ml of distilled water, 0.025 g of hydroquinone was added, and the solvent was removed under reduced pressure to obtain a pale yellow viscous liquid.

When this product was analyzed by 1H-NMR, HPLC, and GC-mass spectrum, it was revealed to be isosorbide dimethacrylate. (Yield 88.1% based on raw material isosorbide, GC purity (area ratio) = 96.1% <, HPLC purity = 97.5%)
<Isosorbide dimethacrylate> (1H-NMR (400 MHz), CDCl3, in ppm); 6.4 (2H), 5.8 (2H), 4.6 (2H), 3.9 to 4.2 ( 6H), 1.9 (6H)

[Example 1 ] (Synthesis of isosorbide 15EO adduct diacrylate)
Into the autoclave, 146 parts of isosorbide and 1 part of caustic soda were added to perform nitrogen substitution. Under stirring, the temperature was adjusted to 130 ° C. and dispersed uniformly. 700 parts of ethylene oxide (EO) was continuously introduced at 130 ° C. so that the internal pressure of the autoclave did not exceed 0.3 MPa. The mixture was aged for 2 hours until pressure equilibrium was reached at the same temperature to obtain an isosorbide 15 EO adduct. The number average molecular weight of the target product was 832 and the average added mole number of EO was 15.6 .

  In 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 are obtained. While charging and introducing air, the mixture was heated to 120 ° C. in an oil bath and stirred for 15 hours. The reaction was carried out while distilling off the water that emerged as the reaction proceeded. After completion of the reaction, the mixture 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 was removed under reduced pressure to obtain a pale yellow viscous liquid.

This was analyzed by 1H-NMR, HPLC, and GC-mass spectrum, and was found to be isosorbide diacrylate. (Yield 82.4% based on raw material isosorbide, GC purity (area ratio) = 94% <, HPLC purity = 95%)
<Isosorbide diacrylate> (1H-NMR (400 MHz), CDCl3, in 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)
Into the autoclave, 146 parts of isosorbide and 1 part of caustic soda were added to perform nitrogen substitution. Under stirring, the temperature was adjusted to 130 ° C. and dispersed uniformly. 260 parts of ethylene oxide (EO) were continuously introduced at 130 ° C. so that the internal pressure of the autoclave did not exceed 0.3 MPa. The mixture was aged for 4 hours until pressure equilibrium was reached at the same temperature to obtain an isosorbide 6 EO adduct. Moreover, the number average molecular weight of the target product was 344 , and the average added mole number of EO was 4.5 .

  In a 1 L four-necked flask, 410 g (1 mol) of the 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 added. While charging and introducing air, the mixture was heated to 120 ° C. in an oil bath and stirred for 13 hours. The reaction was carried out while distilling off the water that emerged as the reaction proceeded. After completion of the reaction, the reaction 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 the solvent was removed under reduced pressure to obtain a pale yellow viscous liquid.

This was analyzed by 1H-NMR, HPLC, and GC-mass spectrum, and was found to be isosorbide diacrylate. (Yield 84.4% based on raw material isosorbide, GC purity (area ratio) = 96% <, HPLC purity = 96%)
<Isosorbide diacrylate> (1H-NMR (400 MHz), CDCl3, in ppm); 6.4 (2H,), 6.2 (2H), 5.8 (2H), 4.6 (2H), 4.3 (4H), 3.5-4.0 (26H)

2. Evaluation of Physical Properties of Isosorbide Di (meth) acrylate Resin Composition Regarding isosorbide diacrylate obtained in Reference Example 1 above, KAYARAD DPHA, which is a polyfunctional monomer, and HDDA, which is the same bifunctional monomer, are compared as follows. The physical properties of the resin composition and its cured film were evaluated. The sample preparation method and the measurement / evaluation method are as follows. The results are shown in Table 1.

[ Reference Example 7 ]
A resin composition obtained by adding 5 parts of 1-hydroxy-cyclohexyl-phenyl-ketone (trade name Irgacure 184, manufactured by Ciba Specialty Chemicals) to 100 parts of isosorbide diacrylate obtained in Reference Example 1 did.

[Comparative Example 1]
100 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) and 1-hydroxy-cyclohexyl-phenyl-ketone (trade name Irgacure 184, Ciba Specialty Chemicals) (Comparative Example 2)
1-hydroxy-cyclohexyl-phenyl-ketone (trade name Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) in 100 parts of 1,6-hexanediol diacrylate (trade name: New Frontier HDDA, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) ) Was added as a resin composition.

Unless otherwise specified below, as a cured film for evaluation, the resin composition obtained in Reference Example 7 and Comparative Examples 1 and 2 was applied to a glass substrate with a film thickness of 100 μm with a bar coater, metal halide. What was hardened | cured with the integrated illumination intensity 200mj / cm < ² > in the belt conveyor type | mold UV curing device equipped with the lamp | ramp was used.

<viscosity>
Viscosity was measured using a cone-plate type rotational viscometer (E-type viscometer manufactured by Toki Sangyo Co., Ltd.) connected to a thermostatic bath and a circulation pump.

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

<Volume shrinkage>
The test sample before and after curing was measured for specific gravity based on JIS K0061-1992, and the volume shrinkage was measured by the following formula.
Volume shrinkage (%) = {(specific gravity after curing−specific gravity before curing) / specific gravity after curing} × 100

<Contact angle>
It was measured by the droplet method. The height of the apex and the radius of the water droplet were read directly, and the contact angle was determined from θ = 2 arctan (h / a).

<Curing property>
It is coated on a glass substrate with a bar coater to a film thickness of 10 μm, shielded from light with a step tablet (25 steps, manufactured by Riston), and exposed to a parallel light type exposure machine (SX-UID501H UVQ) manufactured by USHIO under air shut-off. The number of steps which are cured at an integrated illuminance of 50 mj and become tack-free is described.

<Pencil hardness>
Each resin composition was cured at a cumulative illuminance of 400 mj / cm ² using glass, PET, ABS, PC, acrylic resin as a substrate in a belt conveyor type UV curing device equipped with a metal halide lamp, and in accordance with JIS K5600-5-4, The film hardness on these substrates was measured.

<Adhesion>
Each resin composition was cured at a cumulative illuminance of 400 mj / cm ² using ABS, PC, acrylic resin as a substrate in a belt conveyor type UV curing device equipped with a metal halide lamp, and a cross-cut test in accordance with JIS-K5400 was conducted. The mass number was defined as adhesion.

<Abrasion resistance>
A PET film was coated on a PET substrate with a film thickness of 20 μm, a cured film was formed under the same conditions as the adhesion, and a Taber abrasion test was conducted. The haze was measured with a haze meter (Suga Seisakusho HGM type) when a CS-10F wear wheel was rotated at a load of 500 g and rotated a predetermined number of times.

<Contamination resistance>
The film was applied to a PET substrate with a film thickness of 10 μm using a spin coater, and a cured film was formed under the same conditions as the adhesion. On the cured film, oily magic, hair dyeing liquid and shoe ink were applied as contaminants, left to stand for 18 hours, and visually observed when wiped off with ethanol cotton, and evaluated according to the following criteria.
○: Not colored, Δ: Slightly colored, ×: Darkly colored

<chemical resistance>
A film is formed under the same conditions as in the stain resistance test, and a commercially available bleaching agent composed of hypochlorite, sodium hydroxide, surfactant (alkylamine oxide), etc. is dropped on the test film in a petri dish. Allowed to stand for 18 hours. The film was wiped off with a tissue, and the film was visually observed for change, and evaluated according to the following criteria.
○: No abnormality in the cured film, Δ: slight gloss change, x: obvious abnormality such as whitening, cracking, floating

<water resistant>
A film was formed under the same conditions as in the stain resistance test, tap water was dropped, and the appearance when wiped off after 18 hours was visually observed and evaluated according to the following criteria.
○: No abnormality in the cured film, Δ: slight gloss change, x: obvious abnormality such as whitening, cracking, floating

<Acid resistance>
A film was formed under the same conditions as in the stain resistance test, a drop of 0.1 mol / L hydrochloric acid aqueous solution was dropped on the test film, and left in a petri dish for 18 hours. The film was wiped off with a tissue, and the film was visually observed to see if it had changed.

<Alkali resistance>
A film was formed under the same conditions as in the stain resistance test, a drop of a 2% aqueous sodium hydroxide solution was dropped on the test film, and allowed to stand in a petri dish for 18 hours. The film was wiped off with a tissue, and the film was visually observed to see if it had changed.

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

<Curl properties>
The film was applied on a PET film having a thickness of 150 μm with a bar coater to a thickness of 20 μm and cured under the same conditions as the adhesion. The heights of the four corners of the film were measured, and the average value was defined as curl.

  From the results shown in Table 1, isosorbide diacrylate is a bifunctional monomer and exhibits almost the same physical properties as DPHA, which is a polyfunctional monomer, and has low viscosity and high sensitivity, and also has a low curl property of the cured film. It turns out that it has the outstanding property.

3. Preparation of polymerizable resin composition and measurement of physical properties of cured film
Isosorbide diacrylate obtained in Reference Example 1, DPHA which is a multifunctional monomer as a comparison target, HDDA of the same bifunctional monomer, a resin composition composed of urethane acrylate as follows, and a cured film thereof Physical properties and the like were measured or evaluated in the same manner as in Reference Example 7 above.

[ Reference Example 8 ]
50 parts of isosorbide diacrylate obtained in Reference Example 1 above, 50 parts of New Frontier R-1204 (urethane acrylate resin, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 1-hydroxy-cyclohexyl-phenyl-ketone 5 parts (trade name Irgacure 184, manufactured by Ciba Specialty Chemicals) were mixed to obtain a polymerizable resin composition.

[ Reference Example 9 ]
A similar resin composition was prepared by replacing the urethane acrylate resin of Reference Example 8 with New Frontier R-1302 (urethane acrylate resin, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

[Comparative Example 3]
A similar resin composition was prepared using a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) instead of the isosorbide diacrylate of Reference Example 8 . .

[Comparative Example 4]
A similar resin composition was prepared using 1,6 hexanediol diacrylate (trade name New Frontier HDDA, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) instead of isosorbide diacrylate in Reference Example 8 .

[Comparative Example 5]
In Reference Example 8 , no monomers were added, 100 parts of New Frontier R-1204 (urethane acrylate resin, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 5 parts of 1-hydroxy-cyclohexyl-phenyl-ketone (trade name Irgacure 184, Ciba Specialty Chemicals) was mixed to obtain a polymerizable resin composition.

[Comparative Example 6]
A similar resin composition was prepared using a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) instead of isosorbide di (meth) acrylate in Reference Example 9 . .

[Comparative Example 7]
A similar resin composition was prepared using 1,6 hexanediol diacrylate (trade name New Frontier HDDA, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) instead of isosorbide di (meth) acrylate in Reference Example 9 .

[Comparative Example 8]
In Reference Example 9 , no monomers were added, 100 parts of New Frontier R-1302 (urethane acrylate resin, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and 5 parts of 1-hydroxy-cyclohexyl-phenyl-ketone (trade name Irgacure 184, Ciba Specialty Chemicals) was mixed to obtain a polymerizable resin composition.

Except where otherwise specified in the above measurement / evaluation method, the cured film for evaluation was obtained by using the polymerizable resin compositions obtained in Reference Examples 8 and 9 and Comparative Examples 3 to 8 at a film thickness of 100 μm using a bar coater. It was coated on a glass substrate and cured by a belt conveyor type UV curing device equipped with a metal halide lamp at an integrated illuminance of 200 mj / cm ² .

  From the results in Table 2, it can be seen that isosorbide diacrylate significantly improves curability, curlability, and other physical properties while significantly reducing the viscosity of high-viscosity urethane acrylate as compared with DPHA. Moreover, it turns out that the hardness etc. of a hardened film improve notably compared with HDDA.

  The cured product obtained by curing the cyclic (meth) acrylate compound of the present invention and the polymerizable resin composition containing the compound has high hardness, low curl properties, and excellent curability. It can be suitably used for coating applications such as hard coat, ink compositions for ink jet printing, or resist compositions such as dry film resists, colored resists, and black resists.

Claims (4)

A cyclic (meth) acrylate compound represented by the general formula (1).

In the general formula (1), R ¹ represents a hydrogen atom or a (meth) acryloyl group, at least one is a (meth) acryloyl group, A represents an alkylene group having 2 to 4 carbon atoms, and n is It represents the number of 1 - 30. Reacting (meth) acrylic acid halide or (meth) acrylic anhydride to acrylate the isosorbide or isosorbide alkylene oxide adduct,
The step of (meth) acrylate-converting isosorbide or isosorbide alkylene oxide adduct by transesterification with (meth) acrylic acid ester, or reacting (meth) acrylic anhydride in the presence of a dehydration condensing agent or acid The method for producing a cyclic (meth) acrylate compound according to claim 1 , comprising any one of the following steps: acrylate the isosorbide or isosorbide alkylene oxide adduct. A resin composition comprising the cyclic (meth) acrylate compound according to claim 1 and a polymerization initiator. The resin composition according to claim 3, wherein the resin composition further contains a urethane acrylate compound.

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