JP7082520B2 - Reactive composition - Google Patents

Description

The present invention relates to reactive compositions. More specifically, the present invention relates to a reactive composition containing a glycidic acid ester group and a (meth) acrylic acid ester group in a predetermined ratio.

Epoxy resins are used for various purposes, but there are concerns about their toxicity to the environment and living organisms, such as causing allergic symptoms such as dermatitis. In particular, various studies have been conducted on the glycidyl ether type bisphenol A type epoxy resin to prevent health hazards. The safety of the glycidyl ester type epoxy resin such as phthalic acid diglycidyl ester is improved as compared with the glycidyl ether type epoxy resin, but further improvement of safety is required. Further, when an epoxy resin is used for an adhesive or a paint, it is preferably soluble in a solvent, and an epoxy resin prepolymer having both biosafety and solubility in a solvent is required.

Patent Document 1 epoxidizes an acrylic acid functional group of a compound containing a plurality of acrylic acid functional groups to produce an epoxy resin prepolymer containing a plurality of glycidic acid functional groups. This epoxy resin prepolymer is less toxic than the glycidyl ether type epoxy resin. However, in this epoxy resin prepolymer, substantially all acrylic acid functional groups are epoxidized and converted into glycidic acid functional groups.

JP-A-2015-214497

An object of the present invention is to provide a raw material for an epoxy resin prepolymer having both biosafety and solubility in a solvent.

The inventors have found that radical polymerization of a reactive composition containing a glycidic acid ester group and a (meth) acrylic acid ester group in a predetermined ratio gives an epoxy resin prepolymer soluble in various solvents. .. Furthermore, the cured product of this epoxy resin prepolymer has a higher glass transition temperature than the cured product of an epoxy resin containing only a glycidic acid functional group, and the glass transition temperature can be arbitrarily adjusted by selecting a monomer at the time of prepolymer synthesis. We have found that it has the potential to be used in a wide range of applications, and completed the present invention.

を表し、
式（Ｉｂ）は

を表し、
Ａは（ｍ＋ｎ）価の炭素数１～２０の有機基であり、
ｍおよびｎはそれぞれ独立して０～６の整数であり、（ｍ＋ｎ）は２～６であり、
Ｒ^１、Ｒ^２、およびＲ^３は、それぞれ独立して、水素原子、炭素数１～６のアルキル、およびフェニルからなる群から選択される１価の基であり、
Ｒ^４＝Ｒ^２かつＲ^５＝Ｒ^３、またはＲ^４＝Ｒ^３かつＲ^５＝Ｒ^２である）に関する。 That is, the present invention has the following general formula (1):
(Ia) _m -A- (Ib) _n (1)
A reactive composition composed of a glycidic acid ester represented by the above, the molar ratio of the structures represented by the formulas (Ia) and (Ib) in the entire composition is as follows.
(Ia): (Ib) = 95: 5 to 70:30 The reactive composition (in the formula (1), (Ia) is

Represents
Equation (Ib) is

Represents
A is an organic group having a (m + n) valence of 1 to 20 carbon atoms.
m and n are independently integers of 0 to 6, and (m + n) is 2 to 6.
R ¹ , R ² , and R ³ are independently monovalent groups selected from the group consisting of a hydrogen atom, an alkyl having 1 to 6 carbon atoms, and a phenyl.
R ⁴ = R ² and R ⁵ = R ³ or R ⁴ = R ³ and R ⁵ = R ² ).

The present invention also relates to an epoxy resin composition obtained by radical polymerization of the reactive composition.

The epoxy resin composition may be one or more solvents selected from the group consisting of esters, halogen-containing solvents, ethers, ketones, amides, aromatics, alcohols, dimethyl sulfoxide, and mixtures thereof. It is preferably melted.

The solvent is preferably one or more selected from the group consisting of ethyl acetate, chloroform, tetrahydrofuran, acetone, dimethylformamide, dimethyl sulfoxide, and mixtures thereof.

The present invention also relates to the epoxy resin composition and a curable resin composition containing a curing agent.

The curable resin composition preferably further contains a second epoxy resin, a filler, a curing accelerator, or an organic solvent.

The present invention also relates to a cured product obtained by curing the curable resin composition.

The present invention also relates to an adhesive containing the epoxy resin composition.

The present invention also relates to a paint containing the epoxy resin composition.

Radical polymerization of the reactive composition of the present invention gives an epoxy resin prepolymer soluble in various solvents. The cured product of this epoxy resin prepolymer has a high glass transition temperature and can be used in a wide range of applications including paints and adhesives that require hardness.

It is a schematic diagram of the test piece used for the adhesive strength measurement in an Example.

を表し、
式（Ｉｂ）は

を表し、
Ａは（ｍ＋ｎ）価の炭素数１～２０の有機基であり、
ｍおよびｎはそれぞれ独立して０～６の整数であり、（ｍ＋ｎ）は２～６であり、
Ｒ^１、Ｒ^２、及びＲ^３は、それぞれ独立して、水素原子、炭素数１～６のアルキル、およびフェニルからなる群から選択される１価の基であり、
Ｒ^４＝Ｒ^２かつＲ^５＝Ｒ^３、またはＲ^４＝Ｒ^３かつＲ^５＝Ｒ^２である）に関する。 <1> Reactive composition The present invention has the following general formula (1):
(Ia) _m -A- (Ib) _n (1)
A reactive composition composed of a glycidic acid ester represented by the above, the molar ratio of the structures represented by the formulas (Ia) and (Ib) in the entire composition is as follows.
(Ia): (Ib) = 95: 5 to 70:30 The reactive composition (in the formula (1), (Ia) is

Represents
Equation (Ib) is

Represents
A is an organic group having a (m + n) valence of 1 to 20 carbon atoms.
m and n are independently integers of 0 to 6, and (m + n) is 2 to 6.
R ¹ , R ² and R ³ are independently monovalent groups selected from the group consisting of hydrogen atoms, alkyl having 1 to 6 carbon atoms, and phenyl.
R ⁴ = R ² and R ⁵ = R ³ or R ⁴ = R ³ and R ⁵ = R ² ).

In formula (1), the organic group A is a linker that binds a glycidate ester group and a (meth) acrylic acid ester group. The organic group A is an organic group having a (m + n) valence of 1 to 20 carbon atoms. The organic group has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, from the viewpoint of ease of handling when curing as a resin and ease of performing a curing reaction. The organic group has a saturated or unsaturated hydrocarbon group as its constituent main skeleton, and the hydrocarbon group may have either a branched chain structure or a linear structure, and a 1,4-cyclohexylene group. The skeleton of the hydrocarbon group may have a cyclic structure as described above. Further, the organic group A may have a heteroatom such as N, S, O or the like in the molecular chain. The methylene group other than the terminal in the organic group may be replaced with 1 to 4 heteroatoms selected from NH, S and O, an arylene group or a heteroarylene group. The hydrogen atom in the organic group may be substituted with hydroxy, cyano, amino, nitro, halogen or phenyl.

Examples of the organic group A include linear hydrocarbons such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene and nonylene, and branches of 2,2-dimethylpropylene and 2-ethyl-2-methylpropylene. Examples thereof include chain hydrocarbons, cyclic hydrocarbons such as 1,4-cyclohexylene, sugars, PEG chains and the like, and those in which these groups are trivalent or tetravalent. Of these, nonylene and 2,2-dimethylpropylene are preferable.

R ¹ , R ² , and R ³ are independently selected from hydrogen atom, C _1-6 alkyl, and phenyl. From the viewpoint of the availability of the raw material compound and the ease of curing reaction, R ¹ is methyl and R ² and R ³ are hydrogen atoms, or R ¹ , R ² , R ³ It is preferable that all of them are hydrogen atoms. R ⁴ and R ⁵ are R ⁴ = R ² and R ⁵ = R ³ , or R ⁴ = R ³ and R ⁵ = R ² .

m indicates the number of glycidate ester groups in the molecule and represents an integer of 0 to 6.

n indicates the number of (meth) acrylic acid ester groups in the molecule and represents an integer of 0 to 6. m + n is 2 to 6, preferably 2 to 4, more preferably 2 to 3, and most preferably 2.

The molar ratio of the structure represented by the above formula (Ia) to the structure represented by the formula (Ib) in the entire composition is (Ia) :( Ib) = 95: 5 to 70:30, and 95: 5 to 75. : 25 is preferable, and 90:10 to 80:20 is more preferable. If the ratio of the formula (Ia) exceeds 95, the radical polymerization property may be insufficient, and if the ratio of the formula (Ia) is less than 70, the pot life may be insufficient or cross-linking may occur during the radical polymerization. .. The molar ratio of the structure represented by the above formula (Ia) to the structure represented by the formula (Ib) in the composition can be determined by measurement by 1H-NMR.

From the viewpoint of reducing toxicity to living organisms, it is desirable to include an epoxy group as a glycidyl ester group in the compound, but depending on the application, a part of the glycidic acid ester group may be combined with the structure of glycidyl ether or glycidyl ester. It is also possible to do.

The reactive composition of the present invention may contain an alcohol or diol which is a hydrolysis product of an ester or an epoxy group moiety, or pyruvate which is an isomer of an epoxy group.

［式中、Ａ、Ｒ^１、Ｒ^４及びＲ^５は、先に定義した通りである。ｋは、括弧内の構造の個数を示す。］で示される化合物の炭素－炭素二重結合を酸化剤で酸化し、エポキシ基に転換することにより製造することができる。式（ＩＩ）中、ｋは２～６であり、２～４であることが好ましく、２～３であることがより好ましく、２であることが最も好ましい。 The glycidic acid ester represented by the general formula (1) is represented by the formula (II) :.

[In the equation, A, R ¹ , R ⁴ and R ⁵ are as defined above. k indicates the number of structures in parentheses. ] Can be produced by oxidizing the carbon-carbon double bond of the compound represented by] with an oxidizing agent and converting it into an epoxy group. In formula (II), k is 2 to 6, preferably 2 to 4, more preferably 2 to 3, and most preferably 2.

Examples of the compound represented by the formula (II) include neopentyl glycol diacrylate, 1,9-bisacryloyloxynonane, 1,6-bisacryloyloxyhexane, and tricyclo [5.2.1.0 ^2,6 ] de. Examples thereof include candimethanol diacrylate, polyethylene glycol diacrylate, and trimethylolpropane triacrylate. The compound represented by the formula (II) can be obtained, for example, by a condensation reaction between a polyol and a (meth) acrylic acid derivative. A method known to those skilled in the art can be used for the reaction itself for synthesizing an ester from a polyol and a (meth) acrylic acid derivative. The raw material polio is the following formula:
(HO) _k -A (A and k in the equation are as defined above)
Indicated by. Examples of the polyols include 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,9-nonanediol, neopentyl glycol, 1,2,3-propanetriol (glycerin), and trimethylol. Examples thereof include propane, erythritol, polyethylene glycol, sugars containing glucose, diethanolamine and the like.

The (meth) acrylic acid derivative as a raw material is a carboxylic acid having a structure represented by the above formula (Ib) as a skeleton. Examples of the carboxylic acid include acrylic acid, methacrylic acid, cis or trans-2-butenoic acid, (E) or (Z) -3-methyl-2-butenoic acid, cinnamic acid, caffeic acid and the like.

The reaction for obtaining the glycidate of the general formula (1) from the compound represented by the formula (II) can be carried out without using a solvent, particularly an organic solvent with a problem of disposal or separation, but in some cases, an organic solvent. Can be done using. It can also be carried out in an aqueous medium, for example, in the presence of a buffer solution. Since a good conversion rate can be achieved without decomposing the ester structure of the compound of the formula (II), it is preferable to carry out the method of the present invention in a system using a buffer solution. The type of buffer is not particularly limited, and any buffer known to those skilled in the art can be used as long as it does not inhibit the epoxidation reaction. An example of a preferred buffer is an aqueous sodium hydrogen carbonate solution (pH 8.2).

A phase transfer catalyst may be used in the reaction for obtaining the glycidate of the general formula (1) from the compound represented by the formula (II). As interphase transfer catalysts, trioctylmethylammonium chloride, tributylbenzylammonium chloride, tetrabutylammonium iodide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetramethylammonium chloride, tetraoctylammonium bromide, tetraheptyl ammonium bromide, tetrahexyl Quartic ammonium salts such as ammonium bromide, lauryl sulfobetaine, lauryl hydroxysulfobetaine, myristyl sulfobetaine, palmityl sulfobetaine, sulfobetaine such as stearyl sulfobetaine, sodium lauryl sulfate, sodium dodecylbenzene sulfonate, potassium oleate, etc. Organic acid salts can be mentioned. Among them, ammonium salts having an appropriate carbon chain length such as tetraoctylammonium bromide and tetraheptyl ammonium bromide, and lauryl sulfobetaine are preferable. The phase transfer catalyst is used in an amount of 1 to 100 mol% with respect to the compound of the formula (II).

In the reaction for obtaining the glycidate of the general formula (1) from the compound represented by the formula (II), an oxidizing agent for converting the carbon-carbon double bond in the compound represented by the formula (II) into an epoxy group is used. .. The oxidizing agent can be appropriately selected from known oxidizing agents and used, but sodium hypobromous acid, potassium hypobromous acid, calcium hypobromous acid, ammonium hypochlorite, hydrogen peroxide (water). , Peracetic acid, m-chloroperbenzoic acid, perbenzoic acid, t-butylhydroperoxide, oxone, metal oxide (vanadylacetylacetonate, etc.), ammonium hypobromous acid, calcium hypobromous acid, hypobromous acid Examples thereof include potassium and sodium hypobromous acid. Of these, water-soluble salts such as sodium hypochlorite and sodium hypobromous acid are preferable. The oxidizing agent is preferably used in an amount of 1 to 5 equivalents, more preferably 1.2 to 3 equivalents, with respect to the olefin in the compound of the formula (II). The molar ratio of the structures represented by the formulas (Ia) and (Ib) in the entire composition can be adjusted by adjusting the amount of the oxidizing agent as well as the reaction temperature and the reaction time.

In the reaction for obtaining the glycidic acid ester of the general formula (1) from the compound represented by the formula (II), the atmosphere at the time of the reaction is not particularly limited, and even if the atmosphere is inert such as argon or nitrogen, air at atmospheric pressure is used. You may go below. The reaction temperature and reaction time vary depending on the type of substrate used, but usually, the reaction can be carried out under the conditions of, for example, 35 to 45 ° C. and 0.5 to 2 hours.

When obtaining the glycidate of the general formula (1), a diol in which the epoxy group in the compound of the formula (I) is hydrolyzed or an alcohol in which the ester bond is hydrolyzed may be produced as a by-product. Epoxide group isomerization may form pyruvate derivatives. The impurities can be removed by a method known to those skilled in the art, for example, silica gel chromatography and the like.

<2> Epoxy resin composition The epoxy resin composition of the present invention is obtained by radical polymerization of the reactive composition. Examples of the initiator used for radical polymerization include 2,2'-azobispropane, 2,2'-dichloro-2,2'-azobispropane, 1,1'-azo (methylethyl) diacetate, and 2 , 2'-azobis (2-amidinopropane) hydrochloride, 2,2'-azobis (2-aminopropane) nitrate, 2,2'-azobisisobutane, 2,2'-azobisisobutymidamide, 2,2 '-Azobisisobutyronitrile, 2,2'-azobis-2-methylpropionate, 2,2'-dichloro-2,2'-azobisbutane, 2,2'-azobis-2-methylbutyronitrile , 2,2'-azobisisobutyrate dimethyl, 1,1'-azobis (1-methylbutyronitrile-3-sobutyrate sodium), 2- (4-methylphenylazo) -2-methylmalonodinitrile 4,4 '-Azobisisobutyric acid, 3,5-dihydroxymethylphenylazo-2-allylmaronodinitrile, 2,2'-azobis-2-methylvaleronitrile, 4,4'-azobis-4-cyanoyoshi Dimethyl grass acid, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobiscyclohexanenitrile, 2,2'-azobis-2-propylbutyronitrile, 1,1'-azobis-1 -Chlorophenylethane, 1,1'-azobis-1-cyclohexanecarbonitrile, 1,1'-azobis-1-cycloheptanenitrile, 1,1'-azobis-1-phenylethane, 1,1'-azobiscmen, 4 -Nitrophenylazobenzylcyanoethyl acetate, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitrophenylazotriphenylmethane, 1,1'-azobis-1,2-diphenylethane, poly (bisphenol A-4,4) '-Azobis-4-cyanopentanoate), azo-based radical polymerization initiators such as poly (tetraethylene glycol-2,2'-azobisisobutyrate), acetyl peroxide, cumil peroxide, tert-peroxide. Buty, propionyl peroxide, benzobis peroxide, 2-chlorobenzoyl peroxide, 3-chlorobenzoyl peroxide, 4-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 4-bromomethylbenzoyl peroxide, peroxide Lauroyl, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, hypertrif Enylacetic acid-tert-butyl, tert-butyl hydroperoxide, tert-butyl peroxide, tert-butyl peracetic acid, tert-butyl benzoate, tert-butyl perphenylacetate, tert-butyl per 4-methoxyacetate, tert-butyl per-N- (3-Truyl) tert-butyl carbamate and the like can be mentioned. Examples of the polymerization initiator include peroxide-based radical polymerization initiators such as benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, and methyl ethyl ketone peroxide. These may be used alone or in combination of two or more.

The blending amount of the initiator is preferably 0.1 to 10 mol%, more preferably 0.5 to 3 mol% with respect to the reactive composition.

The reaction temperature, reaction time, and presence / absence of light irradiation of the radical polymerization reaction are not particularly limited, but can be carried out under the conditions of, for example, room temperature to 90 ° C. and 30 seconds to 18 hours.

Since the epoxy resin composition of the present invention is obtained by polymerizing a reactive composition containing a glycidic acid ester group and a (meth) acrylic acid ester group in a predetermined ratio, esters, halogen-containing solvents, ethers, ketones, etc. It is soluble in one or more solvents selected from the group consisting of, amides, aromatics, alcohols, dimethylsulfoxides, and mixtures thereof, and can be suitably used for adhesives and paints. Specific examples of such a solvent include ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, methyl acrylate, and ethyl acrylate. , Esters such as butyl acrylate; Halogen-containing solvents such as chloroform, dichloromethane, chlorobenzene; tetrahydrofuran, 1,4-dioxane, diglyme, tetraglyme, propylene glycol monomethyl ether, propylene oxide, phenylglycidyl ether, bisphenol A diglycidyl ether Ethers such as; ketones such as acetone, ethylmethylketone, cyclohexanone; amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; aromatics such as toluene and xylene; alcohols such as ethanol, propanol and ethylene glycol. Classes; dimethylsulfoxide, or mixtures thereof. The solubility of the epoxy resin composition in the solvent can be measured by the presence or absence of precipitation when the composition is added to the solvent to a predetermined concentration (for example, 0.5% by weight), and it is possible when no precipitation occurs. It can be judged that it is melted.

The epoxy resin composition of the present invention may be a composition obtained by copolymerizing the reactive composition with other monomers. Examples of the monomer to be copolymerized include methyl (meth) acrylate, ethyl (meth) acrylate, -n-propyl (meth) acrylate, isopropyl (meth) acrylate, -n-butyl (meth) acrylate, and (meth). ) Alkyl esters of (meth) acrylic acid having 1 to 18 carbon atoms such as -t-butyl acrylate and -2-ethylhexyl (meth) acrylic acid; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate. , (Meta) acrylic acid esters containing hydroxyl groups such as hydroxybutyl (meth) acrylic acid; nitrogen-containing (meth) acrylic acid esters such as (meth) dimethylaminoethyl acrylate and diethylaminoethyl (meth) acrylic acid; (meth) ) Glycidyl acrylate, (meth) tetrahydrofurfuryl acrylate, (meth) morpholyl acrylate, (meth) isobornyl acrylate, (meth) cyclohexyl acrylate and other (meth) acrylate esters; styrene, p. -Examples include styrenes such as acetoxystyrene, chloromethylstyrene, p-methylstyrene and divinylbenzene, vinyl acetate, acrylic acid nitrile, maleic anhydride and thiols.

<3> Curable Resin Composition The curable resin composition of the present invention contains the epoxy resin composition and a curing agent. The curing agent is not particularly limited as long as it is a curing agent used for curing an epoxy resin, and for example, an amine-based curing agent, a phenol-based curing agent, a thiol-based curing agent, a carboxylic acid, an acid anhydride, an alcohol-based curing agent, etc. Can be mentioned.

Examples of the amine-based curing agent include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, metaphenylenediamine, 4,4'-diaminodiphenylmethane, diaminodiphenylsulfone, m-xylenedamine, and m-xylidiate. Rangeamine, propylamine, isophoronediamine, piperazine, N-aminoethylpiperazine, 1,3-bisaminomethylcyclohexane, dicyandiamide, polyamines synthesized by reacting epoxy resins with excess polyamines Epoxy resins Adduct, ketimine, dimer acid Examples thereof include polyamide resins synthesized by condensation of polyamines and polyamines.

Examples of the phenol-based curing agent include bisphenol A, bisphenol F, phenol novolac resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadienephenol-added resin, phenol aralkyl resin, and polyhydric hydroxy compound. Polyhydric phenol novolac resin synthesized from formaldehyde, naphthol aralkyl resin, trimethylolmethane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol phenol co-shrink novolak resin, naphthol cresol co-shrink novolak resin, biphenyl-modified phenol resin, Examples thereof include biphenyl-modified naphthol resin, aminotriazine-modified phenolic resin, and alkoxy group-containing aromatic ring-modified novolak resin.

Examples of the thiol-based curing agent include pentaerythritol tetra (3-mercaptopropionate), polymercaptan resin, polysulfide resin and the like.

Examples of the carboxylic acid include phthalic acid, maleic acid, trimellitic acid, pyromellitic acid, hexahydrophthalic acid, 3-methyl-hexahydrophthalic acid, 4-methyl-hexahydrophthalic acid, or 3-methyl-hexa. Examples include a mixture of hydrophthalic acid and 4-methyl-hexahydrophthalic acid, tetrahydrophthalic acid, nadic acid, methylnadic acid, norbornan-2,3-dicarboxylic acid, methylnorbornan-2,3-dicarboxylic acid and the like. can. Examples of the acid anhydride include the above-mentioned carboxylic acid anhydride.

Examples of the alcohol-based curing agent include polyvinyl alcohol and the like. The above curing agents may be used alone or in combination of two or more.

The amount of the curing agent blended is preferably 0.5 to 1.5 times, more preferably 0.8 to 1.2 times, the number of moles of the curing agent functional group with respect to the number of moles of the epoxy group in the epoxy resin composition. It is preferable, and the same magnification is more preferable. If the blending amount of the curing agent is less than 0.5 times, curing failure may occur due to residual epoxy groups, and if it exceeds 1.5 times, curing failure may occur due to residual curing agent.

The curable resin composition may contain a second epoxy resin, a filler, a curing accelerator, an organic solvent, or the like, in addition to the epoxy resin composition and the curing agent.

The second epoxy resin is not particularly limited, and is not particularly limited, for example, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a phenol novolac type epoxy resin, an alkylphenol novolak type epoxy resin, and a cresol novolac type epoxy resin. , Alicyclic epoxy resin, aliphatic chain epoxy resin, biphenyl type epoxy resin, biphenol type epoxy resin, aralkyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, trishydroxyphenylmethane type epoxy compound, bisphenol Diglycidyl etherified product, diglycidyl etherified product of naphthalenediol, diglycidyl etherified product of phenols, diglycidyl etherified product of alcohols, triglycidyl isocyanurate, various glycidyl ether type epoxy resins, glycidylamine type epoxy resins, glycidyl esters. Examples thereof include a type epoxy resin, an oxide type epoxy resin, and a phosphorus-modified epoxy resin. These may be used alone or in combination of two or more.

When the second epoxy resin is contained, the blending amount thereof can be adjusted according to the characteristics of the desired cured product, and is not particularly limited, but as long as the characteristics of the epoxy resin composition are not impaired, the weight of the epoxy resin composition is 100. It is preferably 100 parts by weight or less with respect to the part.

The filler is not particularly limited, and a known filler can be used. Examples thereof include metal oxides such as silica and alumina, and metal hydrates. These may be used alone or in combination of two or more.

When the curable resin composition contains the filler, the content thereof is not particularly limited, but is preferably 5 to 95% by weight, more preferably 10 to 80% by weight in the curable resin composition. If the content of the filler is less than 5% by weight, the coefficient of thermal expansion may be high, and if it exceeds 95% by weight, the viscosity may be high and the workability may be lowered.

The curing accelerator means one that does not crosslink itself when the curable resin composition is cured, but promotes the crosslinking reaction. The curing accelerator is not particularly limited, and a known curing accelerator can be used, and examples thereof include triphenylphosphine, imidazole, and tertiary amines. The imidazole is not particularly limited, and is, for example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methyl. Examples include imidazole. The tertiary amine is not particularly limited, and is, for example, benzylmethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol, triethylamine, 1,5-diazabicyclo [4]. , 3,0] -5-Nonen (San Apro Trademark: DBN), 1,8-Diazabicyclo [5,4,0] -7-Undecene (San Apro Trademark: DBU), DBU-Phenolic Salt, DBU-Octylic Acid Examples thereof include salts, DBU-p-toluenesulfonate and the like. These curing accelerators may be used alone or in combination of two or more.

When the curable resin composition contains a curing accelerator, the content thereof is not particularly limited, but is preferably 0.1 to 10% by weight, more preferably 0.3 to 7% by weight in the curable resin composition. preferable.

The organic solvent is not particularly limited, and for example, N-methylpyrrolidone; N, N-dimethylformamide; dimethylsulfoxide; ketones such as methylethylketone, cyclohexanone, cyclopentanone; aromatics such as toluene, xylene, tetramethylbenzene, etc. Hydrocarbons; Glycol ethers such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether; acetic acid. Esters such as ethyl, butyl acetate, cellosolve acetate, diethylene glycol monoethyl ether acetate and esterified products of the above glycol ethers; alcohols such as ethanol, propanol, methanol, ethylene glycol and propylene glycol; aliphatic carbonization such as octane and decane. Hydrogens; Petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha can be mentioned. These organic solvents may be used alone or in combination of two or more.

When the curable resin composition contains an organic solvent, the content thereof is not particularly limited, but is preferably 20 to 300% by weight based on the curable resin composition. If the content of the organic solvent is less than 20% by weight, the viscosity may be high, and if it exceeds 300% by weight, the curability may be lowered.

The curing conditions of the curable resin composition are not particularly limited, and can be appropriately adjusted depending on the type of the curing agent used. In the case of photocuring, UV, electron beam or the like is irradiated. For example, in the case of UV irradiation, the irradiation amount can be, for example, about 100 to 10000 mJ / cm ² . As the irradiation device, for example, an ultraviolet lamp (xenon lamp, xenon mercury lamp, metal halide lamp, etc.), an arc type irradiation device, or the like can be used. In the case of thermosetting, for example, a method of heating at room temperature to 150 ° C. for 1 to 180 minutes can be mentioned. For applications where rapid curing is not preferred, a method of curing at room temperature in 1 hour can be mentioned. Specifically, for example, an amine-based curing agent can be cured at room temperature for 1 hour, and a phenol-based curing agent, a carboxylic acid or an anhydride thereof can be cured at 80 ° C. to 150 ° C. for 1 hour.

<4> Adhesives, Paints Examples of the use of the epoxy resin composition of the present invention include adhesives, pressure-sensitive adhesives, paints, matrix resins for composite materials, casting materials, encapsulants, photoresists and the like. In particular, since the epoxy resin composition of the present invention is soluble in a solvent, it can be suitably used for adhesives and paints.

When the epoxy resin composition of the present invention is used for an adhesive or a paint, the adhesive or the paint may be a one-component type or a two-component type. In the case of the two-component type, the epoxy resin composition and the curing agent may be separated from each other.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the following examples. Hereinafter, "%" means "% by weight" unless otherwise specified.

<1> Preparation of reactive composition (Example 1)
Neopentyl glycol diacrylate (5.31 g, 25.0 mmol), lauryl sulfobetaine (2.7 g, 32 mol%) and 5 wt% NaOCl aqueous solution (178 g, 4.8 eq) were added to an eggplant flask for 1 hour at 40 ° C. Stirred. After the reaction, ethyl acetate (50 mL) and saturated aqueous trisodium citrate solution (30 mL) were added. After removing the aqueous phase by liquid separation operation, the organic phase was washed 3 times with saturated brine (30 mL) and then dried over magnesium sulfate. By removing ethyl acetate under reduced pressure, a colorless and transparent liquid hybrid monomer (1.71 g, 7.10 mmol, 28.7%) was obtained. This monomer had a pot life of 3 months or more when stored in the refrigerator. The molar ratio of the glycidate ester group (Ia) to the (meth) acrylic acid ester group (Ib) was (Ia) :( Ib) = 89: 11 as measured by 1H-NMR in a CDCl ₃ solvent. ..

(Example 2)
As acrylic acid ester, 1,6-bisacryloyloxyhexane (2.26 g, 10.0 mmol) instead of neopentyl glycol diacrylate, and tetrahexyl ammonium bromide (1.39 g, 3.20 mmol) instead of laurylsulfobetaine. , A colorless and transparent liquid hybrid monomer (0.71 g, 2.8 mmol, 28%) was obtained by the same operation as in Example 1 except that 1.4 equivalents of a 5 wt% NaOCl aqueous solution was used. This monomer had a pot life of 3 months or more when stored in the refrigerator. The molar ratio of the glycidate ester group to the (meth) acrylic acid ester group was (Ia) :( Ib) = 95: 5.

(Example 3)
Examples except that tricyclo [5.2.1.0 ^2,6 ] decandimethanol diacrylate (3.04 g, 10.0 mmol) was used instead of 1,6-bisacryloyloxyhexane as the acrylic acid ester. By the same operation as in 2, a colorless and transparent liquid hybrid monomer (1.60 g, 4.8 mmol, 48%) was obtained. This monomer had a pot life of 3 months or more when stored in the refrigerator. The molar ratio of the glycidate ester group to the (meth) acrylic acid ester group was (Ia) :( Ib) = 93: 7.

(Example 4)
As the acrylic acid ester, polyethylene glycol diacrylate (number average molecular weight 700) (0.700 g, 1.00 mmol) was used instead of 1,6-bisacryloyloxyhexane, except that tetrahexyl ammonium bromide was not added. By the same operation as in Example 2, a colorless and transparent liquid hybrid monomer (0.314 g, 0.43 mmol, 43%) was obtained. This monomer had a pot life of 3 months or more when stored in the refrigerator. The molar ratio of the glycidate ester group to the (meth) acrylic acid ester group was (Ia) :( Ib) = 95: 5.

(Example 5)
Example 2 except that trimethylolpropane triacrylate (2.96 g, 10.0 mmol) was used instead of 1,6-bisacryloyloxyhexane as the acrylic acid ester, and 1.2 equivalents of a 5 wt% NaOCl aqueous solution was used. By the same operation as above, a hybrid monomer (1.52 g, 4.41 mmol, 44%), which is a colorless and transparent liquid, was obtained. This monomer had a pot life of 3 months or more when stored in the refrigerator. The molar ratio of the glycidate ester group to the (meth) acrylic acid ester group was (Ia) :( Ib) = 83: 17.

(Comparative Example 1)
Neopentyl glycol diacrylate (0.64 g, 5.0 mmol), lauryl sulfobetaine (0.54 g, 32 mol%) and 5 wt% NaOCl aqueous solution (17.9 g, 2.4 equivalents) were added to an eggplant flask at 40 ° C. The mixture was stirred for 1 hour. After the reaction, ethyl acetate (10 mL) and saturated aqueous trisodium citrate solution (30 mL) were added. After removing the aqueous phase by liquid separation operation, the organic phase was washed 3 times with saturated brine (10 mL) and then dried over magnesium sulfate. By removing ethyl acetate under reduced pressure, a colorless and transparent liquid hybrid monomer was obtained (0.239 g, 29%). The molar ratio of the glycidate ester group to the (meth) acrylic acid ester group was (Ia) :( Ib) = 67: 33. The pot life of this monomer was less than a week.

<2> Preparation of Epoxy Resin Composition (Example 6)
AIBN (1 mol%) was added to a hybrid monomer having both a glycidic acid ester group and a (meth) acrylic acid ester group (((Ia) :( Ib) = 90: 10) 1.83 g, 7.60 mmol), and the mixture was added to toluene (1 mol%). 2M), radical polymerization was carried out under nitrogen at 80 ° C. for 12 hours. Then, toluene was removed under reduced pressure to obtain an epoxy resin composition (1.36 g, 74%).

(Comparative Example 2)
AIBN (1 mol%) was added to the hybrid monomer having both the glycidic acid ester group and the (meth) acrylic acid ester group of Comparative Example 1, and radical polymerization was carried out in toluene (2M) under nitrogen at 60 ° C. At that time, the cross-linking reaction proceeded within 30 minutes after the start of the reaction, and a gel-like substance insoluble in the organic solvent was produced.

The epoxy resin compositions obtained in Example 6 and Comparative Example 2 were added to the solvent shown in Table 1 in an amount of 0.5% by weight, and the solubility after 1 hour at room temperature was evaluated. The solubility was evaluated as ◯ when the insoluble matter was not visually confirmed, and as × when the insoluble matter was visually confirmed.

As shown in Table 1, the epoxy resin composition of Example 6 was soluble in a plurality of organic solvents, and the epoxy resin composition of Comparative Example 2 was insoluble.

<3> Preparation of cured product (Example 7)
Diethylenetriamine (DETA) as a curing agent was added to the epoxy resin composition synthesized in Example 6 (((Ia) :( Ib) = 90:10, C = C conversion rate 99%) 1.00 g) as a glycidate ester group. And amino groups were added in an equimolar amount (257 mg), and the mixture was cured at room temperature for 1 hour. The soluble part was removed from the obtained cured product by Soxhlet extraction (10 hours) using tetrahydrofuran to obtain an insoluble solid (93%).

(Example 8)
The epoxy resin composition synthesized in Example 6 (((Ia) :( Ib) = 90: 10, C = C conversion rate 99%) 0.34 g) was mixed with m-xylylenediamine as a curing agent and glycydic acid ester. The groups and amino groups were added in equal molar amounts (168 mg) and cured at room temperature.

<4> Adhesive (Example 9)
A mixture of the epoxy resin composition synthesized in Example 6 and the epoxy: amine ratio of diethylenetriamine = 1: 1 was applied to the test piece and adhered to the test piece, and then used with a tensile tester (IMC-90F0 type modified by Imoto Seisakusho) 6 The adhesive strength after the time was measured (tensile speed 5 mm / min). The aluminum plate shown in FIG. 1 was used as a test piece. The test was carried out a total of 3 times, but no peeling occurred, and it was found that the tensile shear strength was 1.6 N / mm ² or more.

(Example 10)
A similar test was performed by substituting m-xylylenediamine for diethylenetriamine of Example 9. The test was carried out a total of 3 times, but no peeling occurred, and it was found that the tensile shear strength was 1.6 N / mm ² or more.

(Comparative Example 3)
Measurement was carried out in the same manner as in Example 9 except that neopentyl glycol diglycidate (((Ia) :( Ib) = 100: 0) was used instead of the epoxy resin composition synthesized in Example 6 as the epoxy resin. As a result, peeling occurred, and the average tensile shear strength was 1.14 ± 0.08 N / mm ² .

(Comparative Example 4)
The measurement was carried out in the same manner as in Example 9 except that neopentyl glycol diglycidyl ether was used instead of the epoxy resin composition synthesized in Example 6 as the epoxy resin. As a result, peeling occurred, and the average tensile shear strength was 0.03 ± 0.08 N / mm ² .

<5> Coating film (Example 11)
A mixture of the epoxy resin composition synthesized in Example 6 and the epoxy: amine ratio of diethylenetriamine = 1: 1 was applied onto glass and allowed to stand at room temperature for 1 hour to obtain a solid cured product. This cured product could not be peeled off from the glass while maintaining its shape.

Claims (8)

An epoxy resin composition obtained by radical polymerization of a reactive composition.
The reactive composition is
The following general formula (1):
(Ia) _m -A- (Ib) _n (1)
A reactive composition composed of a glycidic acid ester represented by the above, the molar ratio of the structures represented by the formulas (Ia) and (Ib) in the entire composition is as follows.
(Ia): (Ib) = 95: 5 to 70:30 , the epoxy resin composition (in the formula (1), (Ia) is

Represents
Equation (Ib) is

Represents
A is an organic group having a (m + n) valence of 1 to 12 carbon atoms.
m and n are independently integers of 0 to 6, and (m + n) is 2 to 3 .
R ¹ , R ² , and R ³ are independently monovalent groups selected from the group consisting of a hydrogen atom, an alkyl having 1 to 6 carbon atoms, and a phenyl.
R ⁴ = R ² and R ⁵ = R ³ or R ⁴ = R ³ and R ⁵ = R ² ). Claim 1 is soluble in one or more solvents selected from the group consisting of esters, halogen-containing solvents, ethers, ketones, amides, aromatics, alcohols, dimethyl sulfoxide, and mixtures thereof. The epoxy resin composition according to. The epoxy resin composition according to claim 2 , wherein the solvent is one or more selected from the group consisting of ethyl acetate, chloroform, tetrahydrofuran, acetone, dimethylformamide, dimethyl sulfoxide, and a mixture thereof. The epoxy resin composition according to any one of claims 1 to 3 , and a curable resin composition containing a curing agent. The curable resin composition according to claim 4 , further comprising a second epoxy resin, a filler, a curing accelerator, or an organic solvent. A cured product obtained by curing the curable resin composition according to claim 4 or 5 . An adhesive containing the epoxy resin composition according to any one of claims 1 to 3 . A coating material containing the epoxy resin composition according to any one of claims 1 to 3 .

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