WO2008035515A1

WO2008035515A1 - Liquid epoxy resin composition and epoxy resin cured product

Info

Publication number: WO2008035515A1
Application number: PCT/JP2007/065693
Authority: WO
Inventors: Ami Kamada; Kazuhiko Haba
Original assignee: Maruzen Petrochemical Co., Ltd.
Priority date: 2006-09-20
Filing date: 2007-08-10
Publication date: 2008-03-27
Also published as: JP5301997B2; JPWO2008035515A1

Abstract

Disclosed is a liquid epoxy resin composition having high curing rate and excellent viscosity lowering effect, wherein physical properties of an epoxy resin serving as the base do not deteriorate much. The liquid epoxy resin composition is characterized by containing the following components (A), (B) and (C). (A) an epoxy resin (B) an α-vinyloxy-ω-glycidylether compound represented by the following general formula (1): CH2=CH-O-X-O-G (1) (In the formula, X represents a divalent linear or branched alkylene group having 2-12 carbon atoms or an alicyclic alkylene group containing a cyclohexylene group; and G represents a glycidyl group.) (C) a curing agent

Description

Specification

Liquid epoxy resin composition and cured epoxy resin

Technical field

TECHNICAL FIELD [0001] The present invention relates to a liquid epoxy resin composition and a cured product thereof, and more particularly to a liquid epoxy resin composition containing an α-buoxy _ω -glycidyl ether compound as a reactive diluent and a cured product thereof. It is.

Background art

[0002] Epoxy resins are excellent in heat resistance, adhesion, water resistance, mechanical strength, electrical properties, etc., so adhesives, paints, materials for civil engineering and construction, insulating materials for electrical and electronic parts, sealing Widely used as a material. Among these, bisphenol-type epoxy resins that are liquid or solid at room temperature are most commonly used in various applications as shown above because they are excellent in various physical properties and economically. .

[0003] Since such an epoxy resin generally has a high viscosity, in actual use, it is used in combination with various unreacted or reactive type diluents in order to improve handling properties and improve mixing with other materials. In this case, when unreacted diluent is used, changes such as migration are likely to occur after curing, whereas reactive type has the advantage of excellent stability of the cured product.

[0004] Conventionally, as a reactive diluent, distillation purified products of low molecular weight monoglycidyl ethers such as butyldaricidyl ether, allylic glycidyl ether, and phenyldaricidyl ether are known. Since ethers are very strong! / And have skin irritation and mutagenic properties, diglycidyl ethers of dihydric alcohols such as 1,6-hexanediol and neopentylglycol, which are less toxic, have recently been used. There has been a lot going on. However, since these diglycidyl ethers are obtained from the reaction of dihydric alcohol and epichlorohydrin, there is a drawback that the field of use is limited because of the large amount of residual chlorine.

[0005] For this reason, reactive diluents with a reduced chlorine content have also been studied. For example, in Patent Document 1, the purity of a diglycidyl compound purified by distillation is 90% by mass or more, and the total chlorine is 0.3% by mass. A liquid epoxy resin composition containing a% or less aliphatic epoxy compound and a curing agent for epoxy resin is disclosed. However, even diglycidyl ether with reduced residual chlorine content is not sufficiently effective in reducing the viscosity.Addition of these diglycidyl ethers may decrease the mechanical properties of the resulting cured product. There was a problem that water absorption and heat resistance were lowered.

[0006] Although conventional epoxy resin compositions are thermally cured by adding a curing agent such as an acid anhydride, there is a problem that the curing speed is slow, and this is in order to improve production efficiency. There was a strong demand for curing to be completed in a short time.

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 2003-73453

Disclosure of the invention

Problems to be solved by the invention

[0008] The present invention has been made in view of the above-described problems, and is excellent in the effect of reducing the viscosity at a high curing speed, and has low strength and physical property reduction of the base epoxy resin! /, A liquid epoxy resin composition is to be provided.

Means for solving the problem

[0009] As a result of intensive studies to solve the above-mentioned problems, the present inventor uses a compound having a bifunctional group of a bur group and a glycidyl group as a reactive diluent instead of the conventional diglycidyl ether. As a result, the inventors have found that the above-mentioned problems can be achieved and have reached the present invention.

Yes

That is, the present invention is the following liquid epoxy resin composition and cured product.

(1) The following components (A), (B) and (C)

(A) Epoxy resin

(B) The following general formula (1)

CH = CH O X O G (1)

2

(Wherein X represents a C2-C12 divalent linear or branched alkylene group or alicyclic alkylene group containing a cyclohexylene group, and G represents a glycidyl group) α— Buroxy ω-glycidyl ether compound

(C) Curing agent A liquid epoxy resin composition comprising:

[0011] (2) The liquid epoxy resin composition as described above, wherein the component (A) is an aromatic epoxy resin and / or an alicyclic epoxy.

[0012] (3) Component (A) Strength At least 1 selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin and hydrogenated bisphenol F type epoxy resin The liquid epoxy resin composition as described above, which is a kind of epoxy resin.

[0013] (4) The liquid epoxy resin composition as described above, wherein component (A) is an alicyclic epoxide containing at least one epoxycyclohexyl group.

[0014] The liquid epoxy resin composition as described above, which is (5) component (B), 4-butoxybutanol glycidyl ether or 4 (butoxymethyl) -cyclohexyl methanol glycidyl ether.

[0015] (6) The liquid epoxy resin composition described above containing 1 to 150 parts by mass of the component (B) with respect to 100 parts by mass of the component (A).

[0016] (7) A cured epoxy resin obtained by curing the liquid epoxy resin composition of (1) above! /, (6).

The invention's effect

[0017] Since the epoxy resin composition of the present invention has a low curing speed and a low viscosity, it is excellent in workability such as casting, coating, and impregnation, and contains a large amount of fillers such as inorganic fillers and conductive fillers. Even in this case, the liquid state can be maintained, and furthermore, the ability to obtain a cured product without impairing the physical properties of the main epoxy resin can be obtained. Therefore, the cured product obtained by curing the epoxy resin composition of the present invention can be suitably used for applications such as molding materials, sealing materials, electrical insulating materials, adhesives, paints, and inks for inkjet printers. .

BEST MODE FOR CARRYING OUT THE INVENTION

[0018] (A) Epoxy resin

The epoxy resin of component (A) used as the main ingredient in the liquid epoxy resin composition of the present invention is not particularly limited, but is preferably an aromatic epoxy resin or an alicyclic resin. An epoxy resin etc. are mentioned. [0019] Among these, examples of aromatic epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, biphenol type epoxy resins, and naphthalene type epoxy resins. Glycidylamine type epoxy resins obtained from glycidyl ethers, aminophenols, etc., epoxy resins obtained from phenol nopolac, epoxy resins obtained from cresol nopolac, nopolak epoxy resins of bisphenol A, phenols and hydroxy Examples thereof include polyfunctional epoxy resins such as novolak epoxy resins obtained from benzaldehydes.

[0020] Further, as an example of the alicyclic epoxy resin, an epoxy resin obtained by directly hydrogenating the aromatic ring of the above aromatic epoxy resin or a polyhydric phenol is hydrogenated and then reacted with epichlorohydrin. And epoxy resin. More specifically, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated biphenol type epoxy resin, hydrogenated phenol nopolac type epoxy resin, hydrogenated cresol nopolac epoxy resin, hydrogenated type Naphthalene type epoxy resin. In addition to these compounds, alicyclic epoxides containing at least one epoxycyclohexyl group can also be used. The alicyclic epoxide has two or more unsaturated groups, at least one of which is a cyclohexene group, and is reacted with peracetic acid to form a cyclohexene group. Epoxy resins having epoxidized heavy bonds, preferably having two or more epoxy groups in one molecule. Specifically, for example, 3,4-epoxycyclohexylmethyl-3 ′, 4 ′ epoxycyclohexanecarboxylate (trade names UVR-6110 and UVR-6105 manufactured by UCC, products manufactured by Daicel Chemical Industries, Ltd.) Name Celoxide 2021P, etc.), bis (3,4 epoxycyclohexylmethyl) adipate (trade name UVR-6128, etc., manufactured by UCC), ε-force prolatatone modification 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxy Cyclohexanecarboxylate (Daicel Chemical Industries, Ltd., trade name: Celoxide 2081, etc.), 1-methyl-4-one (2 methyloxylanyl) 7 oxabicyclo [4.4.0] heptane (Daicel Chemicals, Inc., trade name) Celoxide 3000 etc.).

[0021] Among these, bisphenol Α type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, and hydrogenated bisphenol F type epoxy resin Use of fat is preferable in that a low-viscosity epoxy resin can be obtained and a cured product having a good balance between moisture resistance and heat resistance can be obtained. In addition, an alicyclic epoxide containing an epoxycyclohexyl group is preferable in terms of excellent properties as an ink for an ink jet printer, since it has good curability and high adhesion to a base material having a high cured film strength. .

[0022] (B) a-Buroxy ω-glycidyl ether compound

In the liquid epoxy resin composition of the present invention, the α-vininoleoxy ω-glycidyl ether compound used as the component (Β) acts as a reactive diluent and is a compound represented by the following general formula (1) It is.

CH = CH Ο X Ο G (1)

2

(Wherein X represents a C2-C12 divalent linear or branched alkylene group or an alicyclic alkylene group containing a cyclohexylene group, and G represents a glycidyl group)

[0023] Specific examples of the α-vinyloxy ω-glycidyl ether compound used as component (B) in the liquid epoxy resin composition of the present invention include 2-Buroxyethanol glycidyl ether, 3-Buroxypropanol Glycidyl ether, 4-Buroxybutanol glycidyl ether, 5-Buroxypentanol darcydyl ether, 6-Buroxyhexanol glycidyl ether, 3-Buroxy 2,2 dimethyl-propanol glycidyl ether, 5-Buroxy-3 methylol Examples thereof include pentanol glycidyl ether, 4 (butoxymethyl) -cyclohexyl methanol glycidyl ether, and the like.

[0024] Among these compounds, in terms of the effect of lowering the viscosity (lowering viscosity effect), 4

4 (Buroxymethyl) -cyclohexylmethanol glycidyl ether is preferred from the standpoint that buloxybutanol glycidyl ether is preferred, and water absorption is low and heat resistance is good.

[0025] The production method of the above-mentioned α-butoxy ω-glycidyl ether compound as the component (ない) is not particularly limited. For example, α-containing a linear, branched or cyclohexylene group having 2 to 12 carbon atoms. , Ω Alkanediol monobutyl ether and epihalohydrin can be reacted. The epihalohydrins used here are epiclorehydrin, epiporphine mohydrin. Β-methinorepichronohydrin. Β-methinoreepib Epic chlorohydrin is preferred, such as oral mohydrin and β-methylepyohydrin.

[0026] The above-mentioned reaction between the monobule ether of α, ω alkanediol and epihalohydrin is, for example, (1) an acidic catalyst such as sulfuric acid, boron trifluoride ether ether, tin tetrachloride, or quaternary ammonium salts, In the presence of a phase transfer catalyst such as quaternary phosphonium salts and crown ethers, first, a halohydrin ether is produced, and then this halohydrin ether is reacted with a dehydrohalogenating agent such as sodium hydroxide. In two steps, or (2) Dehydrohalogenation in one step in the presence of alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, etc./, glycidyl It can be done by a one-step method to obtain ether.

[0027] After completion of the reaction, the α-butoxy ω-glycidyl ether compound can be isolated by a conventional method. For example, a non-aqueous solvent such as a hydrocarbon is added, followed by washing with water to elute and remove the by-product salt. After that, by removing the solvent, dehydrating, filtering the salt precipitated in a trace amount or solid-liquid separation, it is possible to obtain the target α-buoxy ω-glycidyl ether compound with the force S.

[0028] The α-butoxy ω-glycidyl ether compound thus obtained can be used as it is as a raw material for the liquid epoxy resin composition of the present invention. It can also be used after removing. By removing impurities in this way, an increase in viscosity due to crosslinking can be prevented, and the weather resistance of the resulting cured product can be improved.

[0029] Distillation purification is performed by dimerizing the liquid temperature of α-butoxy ω-glycidyl ether compound.

It is preferable to carry out under reduced pressure while maintaining a temperature at which (polymerization) does not occur. The preferable purity of the α-butoxy ω-glycidyl ether compound after purification by distillation is 90% by mass (hereinafter referred to as “%”) or more, more preferably 95% or more.

[0030] The amount of the α-butoxy ω-glycidyl ether compound as the component (Β) is preferably;! To 150 parts by mass, preferably 3 to; 120 masses with respect to 100 parts by mass of the epoxy resin as the component (Α). More preferred is 10 to 100 parts by mass. If the proportion of component (Β) is less than 1 part by mass, the effect of decreasing the viscosity may be reduced, and if it exceeds 150 parts by mass, the effect will be hard. Properties such as heat resistance of the chemical compound may deteriorate.

[0031] (C) Curing agent

As the curing agent of the component (C) used in the liquid epoxy resin composition of the present invention, those conventionally used in this field can be used without particular limitation. For example, an acid anhydride curing agent, phenol Examples thereof include a system curing agent, an amine curing agent, and a cationic polymerization catalyst. In particular, when a lower viscosity is required, an acid anhydride-based curing agent is preferable. When a higher moisture resistance or hydrolysis resistance is required, a phenol-based curing agent is preferable, and low temperature curing is preferable. If necessary, an amine curing agent is preferably a cationic polymerization catalyst.

[0032] Among the component (C), specific examples of the acid anhydride curing agent include aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and tetrahydrophthalic anhydride. , Cyclic fats such as methyltetrahydrophthalic anhydride, hexahexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, cyclododecenyl succinic anhydride, and anhydrous trialkyltetrahydrophthalic acid And aromatic anhydrides, and mixtures and modified products thereof.

[0033] As the acid anhydride curing agent, a curing accelerator generally used in this field can be used. Specific examples of curing accelerators include, for example, tertiary amines such as pendinoledimethylamine, tris (dimethylaminomethyl) phenol, dimethylcyclohexylamine; tetraethylammonium bromide, tetraptylammonium. Quaternary ammonium salts such as bromide; imidazoles such as 1-cyanoethyl-2-ethyl 4-methyl imidazole, 2-ethyl 4-methyl imidazole, 1 benzyl 2-methyl imidazole; phosphines such as triphenyl phosphine; tetra Examples include quaternary phosphonium salts such as phenylphosphonium bromide and tetra-n-butylphosphonium bromide. These curing accelerators can be used alone or in admixture of two or more.

[0034] Among the component (C), specific examples of phenolic curing agents include catechol, resorcin, hydroquinone, bisphenol F, bisphenol A, bisphenol S, biphenol, phenol novolaks, Cresolol novolacs, divalent phenol nopolacs such as bisphenolanol A, trishydroxyphenylmethanes, aralkylpolyphenols And dicyclopentadiene polyphenols.

[0035] Further, specific examples of the amine-based curing agent of component (C) include triethylamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5.4. 0) —undecene-7, 1,5-diazabicyclo (4.3.0) —nonene 7 and other tertiary amines and their salts; 1-cyanethyl-2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1 Imidazoles such as 2-methylimidazole, 2-methinoreidamidole, trisdimethylaminomethylimidazole and 2-phenylimidazole; triethylamine, benzyldimethylamine, 2,4,6-tris (dimethinoreaminomethinole ) Phenols, 1,8-Diazabicyclo (5.4.0) —Undecene 7, 1,5-Diazabicyclo (4.3.0) —No Tertiary amines such as N-7 and salts thereof; aromatic polyamines such as meta-xylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone; pentaethylenehexamine, tetraethylenepentamine, triethylenetetramine, and jet triethylenetriamine Aliphatic polyamines: cyclohexanediamine, 1,3-bis (aminomethylol) cyclohexane, norbornadiamine, isophoronediamine, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) ) Modification by alicyclic polyamines such as 2,4,8,10-tetraoxaspiro [5.5] unde force and mixtures thereof, carboxylic acids, epoxy compounds, methyl methacrylate, phenol 'formaldehyde, acrylonitrile, etc. Lifting things with power S

[0036] Furthermore, as the cation polymerization catalyst of component (C), it is possible to use noreic acid. For example, BF, PF, AsF, SbF, and these Lewis acids and methylamine,

3 5 5 6

, Complexes with organic primary amines such as n-butylamine, preferably BF with ethylamine

It is also possible to use 3 complexes and triphenylphosphine.

[0037] In addition, as a thermal cationic polymerization catalyst or a light-power thione polymerization catalyst that is decomposed by heating or irradiation with ultraviolet rays or visible light to act as a curing agent, aromatic diazonium salts, diarylhodonium Salts, triarylsulfonium salts, triarylselenium salts and the like. Specifically, aromatic diazo-yu salts such as p-chlorobenzene benzene hexafluorophosphate and p-methoxybenzene dihexafluorophosphate; diphenyl rhodium hexahexa Fluorophosphate, 4,4G t-Butyl fuel Dirhoordonium salt such as dirhodonium hexafluorophosphate; Trifen Nolesnorehonum hexaphnorenophosphate phosphate, Bis [4— (Difenenoles Norehonio) Hue Ninore] It is also possible to use triarylsulfonium salts such as snorefido bishexafluorophosphate; triaryl selenium salts such as triphenyl selenium hexafluorophosphate, and the like.

In addition, organic acid hydrazides such as dicyandiamides, adipic acid dihydrazide and phthalic acid dihydrazide can also be used. These curing agents may be used alone or in combination of two or more.

[0039] When the above acid anhydride curing agent, amine curing agent or phenol curing agent is used as the component (C), the amount used is the sum of these components (A) and (B). 50-200 parts by mass is preferable with respect to 100 parts by mass in total. 80-; 150 parts by mass is more preferable.

[0040] Further, as the component (C), when the acid anhydride curing agent and the curing accelerator are used in combination, the amount of the curing accelerator used is 100 mass in total of the component (A) and the component (B). To 10 parts by weight is more preferred 0.3 to 6 parts by weight.

[0041] Further, when the cationic polymerization catalyst is used as the component (C), the amount used is preferably 0.;! To 20 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B). 10 to 5 parts by weight is more preferable.

[0042] If the blending ratio of the component (C) as the curing agent is out of these ranges, unreacted materials remain, and various physical properties of the cured product may be impaired. When 100 parts by mass or more of curing agent (C) is used with respect to 100 parts by mass in total of component (A) and component (B), it is liquid at 25 ° C so that the viscosity of the epoxy resin composition does not increase. It is preferable to use a curing agent.

[0043] (D) Optional component

Furthermore, the liquid epoxy resin composition of the present invention has various additive components such as powdery reinforcing agents and fillers, colorants or pigments, flame retardants, and resin additives for the purpose of improving the properties of the cured product. Can be blended.

[0044] Examples of the powdery reinforcing agent and filler include metal oxides such as aluminum oxide and magnesium oxide, silicon compounds such as fine powder silica, fused silica, and crystalline silica, and glass beads. Examples include fillers such as silica, metal hydroxides such as aluminum hydroxide, kaolin, my strength, quartz powder, graphite, and molybdenum disulfide. These blends are optional. Generally, 10 to 100 parts by mass is appropriate for 100 parts by mass of the epoxy resin composition.

[0045] Examples of colorants or pigments include titanium dioxide, molybdenum red, bitumen, ultramarine blue, cadmium yellow, cadmium red, and organic dyes. In addition, flame retardants such as antimony trioxide, bromine compounds and phosphorus compounds can be mentioned. The compounding of these additives is optional. Generally, 0.0;! To 30 parts by mass is compounded with respect to 100 parts by mass of the epoxy resin composition.

[0046] Examples of the resin additive include one kind or a combination of two or more kinds of fluorine resin, acrylic resin, silicone resin and the like. The blending ratio of these resin additives is preferably 50 parts by mass or less with respect to 100 parts by mass of the epoxy resin composition of the present invention, that is, an amount in a range not impairing the original properties of the epoxy resin composition of the present invention. .

[0047] The liquid epoxy resin composition of the present invention can be obtained by mixing the above-mentioned essential component (A)! /, And (C) with optional component (D) as required. In the present invention, “liquid” means liquid at 25 ° C.

[0048] The liquid epoxy resin composition of the present invention obtained as described above is heated or activated energy rays in the same manner as in the case of an ordinary thermosetting epoxy resin composition or photocurable epoxy resin composition. Can be cured by irradiation. Curing conditions are not particularly limited, but in the case of thermosetting, it can be cured by heating at a temperature of 60 to 250 ° C, preferably 80 to 200 ° C; When an active energy ray curing catalyst is used as component (C), it is irradiated with ultraviolet rays, visible light, electron beams, etc., and cured in the range of room temperature to 150 ° C.

Example

[0049] The ability to further explain the present invention in the following examples, synthesis examples, test examples and comparative examples The present invention is not limited in any way by these examples. In addition, unless otherwise indicated, the part in an example means a mass part.

[0050] Synthesis Example 1 4 Synthesis of buroxybutanol glycidyl ether:

In a 300 ml stirred glass reactor equipped with a condenser and a water separator, 51.8 g (0.5 mol) of 4-Buluoxybutanol (also known as 1,4 butanediol monobutyl ether), 92.5 g of epichlorohydrin Then, 20 g of granular sodium hydroxide and 1.2 g of tetramethylammonium chloride were charged, and the reaction was carried out under vigorous stirring at a reaction temperature of 75 to 80 ° C. and a reduced pressure of 20 to 25 kPa for 1.5 hours. The water produced during the reaction was azeotroped with epichlorohydrin, the vapor was condensed, and the epichlorohydrin was circulated in the system with a separator, and only water was removed outside the system. The amount of water distilled off was 9 g, which was almost the theoretical amount. The reaction mixture was cooled to 30 ° C and filtered to remove the precipitate. The precipitate was washed with 50 g of epichlorohydrin and combined with the filtrate. This filtrate was distilled under reduced pressure, and epichlorohydrin was distilled off and collected. After the remaining oil is cooled to 25 ° C, the precipitate is removed by filtration, and the resulting oily product is distilled under high vacuum to give 4 butyloxybutanol glycidyl ether (hereinafter referred to as “14BD-VGE”). ) 76.5 g was obtained (top 75–80 ° C / 0.1 kPa, yield 89%, purity 99.5% by gas chromatography).

Synthesis example 2

4 (Vininore aged xymethinole)-Synthesis of cyclohexenoremethanoreglycidinoreatenore:

A 300 ml stirred glass reactor equipped with a condenser and a water separator was charged with 10-2.2 g (0.6- (Buoxymethyl) cyclohexylmethanol (also known as: 1,4-cyclohexanedimethanol monovininoreethenore). mol), 100 g of epichloronohydrin, 37.5 g of granular sodium hydroxide, and benzyl trimethylammonium chloride O.lg, and the reactor is cooled and stirred vigorously while maintaining the temperature at 40 ° C. Time reaction was performed. Next, 100 g of cyclohexane was added, the reaction mixture was filtered to remove the precipitate, and the alkaline component remaining in the filtrate was removed by repeated washing with water to obtain an oily product. After recovering cyclohexane and unreacted epichlorohydrin from the oily product, it was distilled under high vacuum, and 4- (butoxymethyl) cyclohexylmethanol glycidyl ether (hereinafter referred to as “CHDM—VGEJ”). 112.7 g was obtained (top 140—145 ° C / 0.4 kPa, yield 83%, purity by gas chromatography 99%). [0052] Example 1

14BD—VGE 10 parts obtained in Synthesis Example 1, hydrogenated bisphenol A type epoxy resin (hereinafter referred to as “HBPA-DGE”; manufactured by Maruzen Petrochemical Co., Ltd., trade name “hydrogenated bisphenol nore A diglycidyl ether”, Epoxy equivalent 200) 100 parts, 71 parts of 1-methylcyclohexane-1,2 dicarboxylic acid anhydride and 1 part of 2-ethyl-4-methylimidazole were mixed to prepare a liquid epoxy resin composition.

[0053] Example 2

A liquid epoxy resin composition was prepared in the same manner as in Example 1 except that 14BD-VGE was changed to 4-butoxybutanol glycidyl etherate (CHDM-VGE) obtained in Synthesis Example 2.

[0054] Example 3

A liquid epoxy resin composition was prepared in the same manner as in Example 1 except that 10 parts of 14BD-VGE were changed to 20 parts of CHDM-VGE.

[0055] Comparative Example 1

A liquid epoxy resin composition was prepared in the same manner as in Example 1 except that 14BD—VGE was not used! /.

[0056] Comparative Example 2

A liquid epoxy resin composition was prepared in the same manner as in Example 1 except that 10 parts of 14BD-VGE were changed to 20 parts of 1,4 butanediol diglycidyl ether (14BD-DGE).

[0057] Comparative Example 3

A liquid epoxy resin composition was prepared in the same manner as in Example 1 except that 10 parts of 14BD-VGE were changed to 20 parts of 1,4-cyclohexanedimethanol diglycidyl ether (CH DM-DGE).

[0058] Test Example 1

The characteristics of the liquid epoxy resin compositions obtained in Examples;! To 2 and Comparative Examples;! To 3 were evaluated by the following methods. The results are shown in Table 1 together with the composition.

[0059] (Evaluation method) <Viscosity>

Measured at 23 ° C using a viscometer (manufactured by A & D Co., Ltd., SV-10 type)

[0060] <Genore Time>

About 0.5 g of the epoxy resin composition was placed on a hot plate heated to 120 ° C or 150 ° C, and the state of the resin composition was observed while stirring with the tip of a spatula. After the composition was placed on a hot plate !, the time from when the resin gelled until the tackiness disappeared was measured to obtain a gel time.

[0061] <Glass transition temperature>

The prepared epoxy resin composition was put in an aluminum cup and cured with a hot air dryer at 100 ° C for 3 hours and at 150 ° C for 4 hours to obtain a cured product. The glass transition temperature was measured by differential scanning calorimetry (DSC method) using fragments of the cured product. In nitrogen, heating rate 20 ° C / min, 150

The temperature was raised to ° C.

[0062] (Result)

[table 1]

From Table 1, when an acid anhydride-based curing agent was blended as a curing agent, compared to Example 1 without reactive diluent, Examples;! To 3 a bul ω-glycidyl ether (component (Β) ) Was excellent in the ability to lower the viscosity of the epoxy resin composition and the curing speed, and in particular, the 4-butoxybutanol glycidyl ether of Example 1 showed a high viscosity reducing effect even in a small amount. Also, compared to the case where the diglycidyl ethers of Comparative Examples 2 and 3 were blended, Examples;! -3 blended with a bul ω-glycidyl ether Was excellent in dilution effect, curing rate and heat resistance.

[0064] Example 4

10 parts of 14BD-VGE obtained in Synthesis Example 1 and 90 parts of HBPA-DGE and 1 part of Adeka Opton CP-66 (trade name, manufactured by ADEKA Co., Ltd.) as a thermal cationic polymerization initiator are mixed to form a liquid epoxy resin composition. Was prepared.

[0065] Example 5

A liquid epoxy resin composition was prepared in the same manner as in Example 4 except that 14BD-VGE was changed to CHDM-VGE.

[0066] Example 6

A liquid epoxy resin composition was prepared in the same manner as in Example 4 except that 10 parts of 14BD-VGE were replaced with 20 parts of CHDM-VGE and HBPA-DGE was changed from 90 parts to 80 parts.

[0067] Comparative Example 4

A liquid epoxy resin composition was prepared in the same manner as in Example 4 except that 14BD-VGE was not used.

[0068] Comparative Example 5

A liquid epoxy resin composition was prepared in the same manner as in Example 4 except that 10 parts of 14BD-VGE were replaced with 20 parts of 14BD-DGE and HBPA-DGE was changed from 90 parts to 80 parts.

[0069] Comparative Example 6

A liquid epoxy resin composition was prepared in the same manner as in Example 4 except that 10 parts of 14BD-VGE were changed to 20 parts of CHDM-DGE and HBPA-DGE was changed from 90 parts to 80 parts.

[0070] Test example 2

For the epoxy resin compositions obtained in Examples 4 to 6 and Comparative Examples 4 to 6, the water absorption was measured by the following method. In addition, composition characteristics and cured product characteristics were evaluated in the same manner as in Test Example 1 (however, the gel temperature measurement temperature was 150 ° C.). The results are shown in Table 2 together with the composition.

[0071] (Evaluation method)

Put the prepared epoxy resin composition in an aluminum cup and use a hot air dryer at 100 ° C for 3 o'clock. In the meantime, it was cured at 120 ° C. for 4 hours to obtain a cured product. This was machined to make a square with a side of 30 mm and a thickness of 1 mm to produce a test piece. Using this test piece, the water absorption was measured according to JISK7209.

(Result)

[Table 2]

From Table 2, when a cationic polymerization initiator is blended as the curing agent for component (C), Examples 4 to 6 blended with α-bulu ω-glycidyl ether as component (B) are less viscous than epoxy resin composition of Comparative Example 4 and have a low viscosity and a curing rate. It was excellent in low water absorption. In particular, 4 buroxybutanol daricidyl ether of Example 4 showed a high low viscosity effect even in a small amount. In addition, 4 (vinyloxymethyl) cyclohexylmethanol glycidyl ether of Examples 5 and 6 was excellent in low water absorption. Furthermore, the blends of α-bul ω-glycidyl ethers of Examples 4 to 6 showed a higher glass transition temperature than the blends of diglycidyl ethers of Comparative Examples 5 and 6, and the curing speed and heat resistance. It was excellent!

[0074] Example 7

CHDM-VGE 20 parts, HBPA-DGE 100 parts obtained in Synthesis Example 2, 1-methylcyclohexane-1,2-dicarboxylic anhydride 71 parts and 2-ethyl-4-methylimidazole 1 part, and photodynamic thione polymerization started One part of IRGACURE 250 (trade name, manufactured by Ciba “Specialty” Chemicals), which is an agent, was mixed to prepare a photocurable liquid epoxy resin composition.

[0075] The obtained photo-curable epoxy resin composition was applied to an aluminum plate to a thickness of 50 m using an applicator (YOSHIMITSU Co., Ltd., Type 2), and then irradiated with ultraviolet light equipped with a DeepUV lamp. Ultraviolet rays were irradiated for 180 seconds at 4 mW / cm ² using an apparatus (trade name “Spot Cure SP-7” manufactured by Usio Electric Co., Ltd.). Next, post-curing was performed at 120 ° C. for 30 minutes with a hot air dryer to obtain a cured product. The glass transition temperature of the obtained cured product was measured by the DSC method in the same manner as in Example 1. As a result, it was 77 ° C.

[0076] Example 8

A photocurable liquid epoxy resin composition was prepared by mixing 20 parts of CHDM-VGE obtained in Synthesis Example 2, 80 parts of HBPA-DGE as an epoxy resin, and 0.46 mol% of IRGACURE250 as a photothion polymerization initiator.

[0077] Example 9

A photocurable liquid epoxy resin composition was prepared in the same manner as in Example 8 except that CHDM-VGE was 40 parts and HBPA-DGE was 60 parts.

[0078] Example 10

Same as Example 8 except 50 parts CHDM-VGE and 50 parts HBPA-DGE. Thus, a photocurable liquid epoxy resin composition was prepared.

[0079] Comparative Example 7

A photocurable liquid epoxy resin composition was prepared in the same manner as in Example 8 except that 100 parts of HBPA-DGE was used and CHDM-VGE was not used.

[0080] Test Example 3

UV irradiating apparatus (trade name, manufactured by Usio Electric Co., Ltd.) having a DeepUV lamp, which is obtained by applying the photocurable epoxy resin composition O.lg obtained in Examples 8 to 10 and Comparative Example 7 to an aluminum plate. “Spot cure SP-7”) was used to irradiate ultraviolet rays at 2.5 mW / cm ² and measured the time until the resin hardened to obtain the gel time. The results are shown in Table 3.

[0081] (Result)

[Table 3]

* 1 and * 2 are the same as above.

* 9 is a light thione polymerization initiator (Ciba ■ Specialty ■ Chemicals).

[0082] Example 11

20 parts of CHDM-VGE obtained in Synthesis Example 2 were mixed with 80 parts of Celoxide 2081 as an epoxy resin (trade name, manufactured by Daicel Chemical Industries, Ltd.) and 0.46 mol% of IRGA CURE250 as a photopower thione polymerization initiator. A photocurable liquid epoxy resin composition was prepared.

[0083] Example 12

A photocurable liquid epoxy resin composition was prepared in the same manner as in Example 11 except that 40 parts of CHDM-VGE and 60 parts of celoxide 2081 were used.

[0084] Example 13

A photocurable liquid epoxy resin composition was prepared in the same manner as in Example 11 except that 50 parts of CHDM-VGE and 50 parts of celoxide 2081 were used. [0085] Comparative Example 8

A photocurable liquid epoxy resin composition was prepared in the same manner as in Example 11 except that 100 parts of Celoxide 2081 was used and CHDM-VGE was not used.

[0086] Test example 4

The gel time was measured in the same manner as in Test Example 3 for the photocurable liquid epoxy resin compositions obtained in Examples 11 to 13 and Comparative Example 8. The results are shown in Table 4.

[0087] (Result)

[Table 4]

* 1 and * 9 are the same as above.

* 1 0 is an epoxy resin (manufactured by Daicel Chemical Industries, Ltd.).

[0088] From Tables 3 and 4, it can be seen that the compound containing CHDM-VGE as the reaction diluent has a faster curing speed than that without the reaction diluent and is useful as a curing accelerator. .

[0089] Example 14

20 parts of CHDM-VGE obtained in Synthesis Example 2, 80 parts of HBPA-DGE as an epoxy resin, 3 parts of IRGACURE250 as a photothione polymerization initiator, and Disparon 1761 as a silicone-based surface conditioner (trade name, Kashiwagi Kasei Co., Ltd.) One part was mixed to prepare a photocurable liquid epoxy resin composition.

[0090] Example 15

A photocurable liquid epoxy resin composition was prepared in the same manner as in Example 14 except that CHDM-VGE was 40 parts and HBPA-DGE was 60 parts.

[0091] Example 16

A photocurable liquid epoxy resin composition was prepared in the same manner as in Example 14 except that 50 parts of CHDM-VGE and 50 parts of HBPA-DGE were used. [0092] Example 17

A photocurable liquid epoxy resin composition was prepared in the same manner as in Example 14 except that HBPA-DGE was replaced with Celoxide 2081.

[0093] Comparative Example 9

A photocurable liquid epoxy resin composition was prepared in the same manner as in Example 14 except that 100 parts of HBPA-DGE was used and CHDM-VGE was not used.

[0094] Test Example 5

The photocurable epoxy resin composition obtained in Examples 15 to 17 and Comparative Example 9 was applied to a mild steel plate using an applicator (YOSHIMITSU, YA-2 type) to a thickness of 50 μm. The sample was applied and irradiated with ultraviolet rays at 10.6 mW / cm ² for 30 seconds using an ultraviolet irradiation device equipped with a high-pressure mercury lamp (manufactured by Sen Special Light Source Co., Ltd., trade name “Non-Dicarab”). Next, post-curing was performed at 150 ° C for 30 minutes with a hot air dryer to obtain a cured film. The characteristics evaluation of the obtained coating-film cured | curing material was performed with the following method. The results are shown in Table 5.

[0095] (Evaluation method)

The film thickness was measured using a film thickness meter (LZ900J, manufactured by Kett Scientific Laboratory).

[0096] <Appearance>

The surface condition was visually observed to check for the presence of coloring, wrinkles and cracks.

[0097] <Adhesion>

A cross-cut peel test was performed according to the JISK5400 method. The number of cells that remained without peeling out of 100 cells was shown.

[0098] <Pencil hardness>

Evaluation was performed according to JISK5400.

[0099] (Result)

[Table 5] to,

m

m ¾

^?

§5

Long

匝

S 鰂

'ヽ: Ku R D * ^

■ rt- LU O ¾ ',

_ ^ I

Η ¾ΗΛ απ

1 V 1

z *

<Q- -H- QQ O O

m □ *

R I R R *

[0100] From Table 5, it can be seen that when CHDM-VGE is blended as a reaction diluent, the hardness of the coating film is improved as compared with the case without reaction diluent.

[0101] Comparative Example 10

HBPA—DGE 80 parts into Celoxide 2081 100 parts, CHDM—VGE not used.

A photocurable liquid epoxy resin composition was prepared in the same manner as in Example 14 except for V.

[0102] Test example 6 The photocurable liquid epoxy resin composition obtained in Example 14, Example 17, Comparative Example 9 and Comparative Example 10 was 50 μm in thickness using an applicator (YOSHIMITSU, YA-2 type). It applied to PET film so that it might become. Next! /, Using a UV irradiation device equipped with a high-pressure mercury lamp (Sen Special Light Source Co., Ltd., trade name “NO, Nycyu Arab”) at 10.6 mW / cm ²

011ϊϋ ^ 1 6

A cured film was obtained by irradiating with ultraviolet rays for 30 seconds. Test the properties of the cured film

. [Fine ^ Ψ] (ΛΗ-performed in the same manner as in Experiment 5. 802. The results are shown in Table 6 together with the composition.

(Result) N ω o> I

[Table 6] sp ^ s) ¾ (υ

¾ ¾ ¾ ε ε ε mountain anovodi 9 Λ □

§5 ^ la one _ik law ± _

Is «蝴 (m) ¾

¾¾U ¾ 匝 Iίιί 6hsι i ** * ；-,,

Ye

CM

o d D ^

Ye [0104] From Table 6, the compound containing CHDM-VGE as the reaction diluent improves the hardness of the coating film as compared to the case without the reaction diluent, and has a flat appearance and shrinkage of the coating film. It can be seen that there is no wrinkle generation and the dimensional stability is excellent.

[0105] From each of the above Examples and Test Examples, the liquid epoxy resin composition of the present invention has a low viscosity, excellent workability, and a cured product obtained with a high curing speed is excellent in that the physical property value is less decreased. It was revealed that the heat resistance and the low water absorption were exhibited. In addition, the liquid epoxy resin composition of the present invention can be cured by irradiation with active energy rays as shown in Examples 7 to 17; the coating film has excellent adhesion, hardness, and surface condition. Industrial availability

[0106] The liquid epoxy resin composition of the present invention has a low viscosity with a high curing rate, excellent workability such as casting, coating and impregnation, and a large amount of fillers such as inorganic fillers and conductive fillers. However, the liquid state can be maintained, and furthermore, it is possible to obtain a cured product without damaging the physical properties of the main epoxy resin.

Therefore, the cured product obtained by curing the liquid epoxy resin composition of the present invention is suitably used for applications such as molding materials, sealing materials, electrical insulating materials, adhesives, paints, and inks for inkjet printers. be able to.

Claims

The scope of the claims

[1] Next ingredients (A), (B) and (C)

(A) Epoxy resin

(B) The following general formula (1)

CH = CH O X O G (1)

2

(Wherein X represents an alicyclic alkylene group containing 2 to 12 carbon atoms; a divalent linear or branched alkylene group having 12 carbon atoms or a cyclohexylene group, and G represents a glycidyl group). ω-glycidyl ether compound

(C) Curing agent

A liquid epoxy resin composition comprising:

[2] The liquid epoxy resin composition according to claim 1, wherein the component (成分) is an aromatic epoxy resin and / or an alicyclic epoxy resin.

[3] Ingredient (Α) force Bisphenol A bis-type epoxy resin, a bisphenol F-type epoxy resin, a hydrogenated bisphenol A-type epoxy resin and a hydrogenated bisphenol F-type epoxy resin. The liquid epoxy resin composition according to claim 1, which is an epoxy resin.

[4] Component (A) force The liquid epoxy resin composition according to claim 1 or 2, which is an alicyclic epoxide containing at least one epoxycyclohexyl group.

[5] The liquid epoxy resin composition according to any one of [1] to [4], which is Component (B), 4-Buroxybutanol glycidyl ether or 4 (Buroxymethyl) -cyclohexylmethanol glycidyl ether.

[6] The liquid epoxy resin composition according to any one of claims 1 to 5, which contains 1 to 150 parts by mass of the component (B) with respect to 100 parts by mass of the component (A).

[7] A cured epoxy resin obtained by curing the liquid epoxy resin composition according to any one of claims 1 to 6.