JPWO2008035514A1 - Liquid curable composition and cured product thereof - Google Patents

Abstract

The following components (A) and (B) are provided for the purpose of providing a curable composition having a high curing rate, low viscosity, excellent workability, and providing a cured product having balanced heat resistance and flexibility. ) (A) The following general formula (1) CH2 = CH—O—X—O—G (1) (wherein X is a divalent linear or branched alkylene group having 2 to 12 carbon atoms or cyclohexylene) A liquid curable composition comprising an α-vinyloxy-ω-glycidyl ether compound (B) cationic polymerization initiator represented by (G represents a glycidyl group).

Description

  The present invention relates to a curable composition and a cured product thereof, and more particularly to a curable composition in which an α-vinyloxy-ω-glycidyl ether compound and a cationic polymerization initiator are blended, and a cured product thereof. The curable composition of the present invention has a high curing rate, low viscosity and excellent workability, and the cured product of the composition of the present invention has excellent heat resistance and flexibility, molding material, sealing It is useful for applications such as materials, electrical insulating materials, adhesives, paints, coating materials, and inkjet inks.

  It is known that cationic polymerization using a cationic polymerization initiator is not affected by polymerization inhibition by oxygen, and as such a cationic polymerizable resin, a bifunctional epoxy resin has been conventionally used. . The resulting epoxy resin is excellent in heat resistance, adhesiveness, water resistance, mechanical strength, electrical properties, etc., and therefore, adhesives, paints, materials for civil engineering and construction, insulating materials for electrical and electronic parts, sealing materials. Widely used as a stopping material.

  Among them, bisphenol A type epoxy resins that are liquid or solid at room temperature are excellent in various physical properties and more economically, and are therefore most frequently used in various applications as described above. Yes. Moreover, epoxy compounds having an alicyclic group such as hydrogenated bisphenol A diglycidyl ether have been proposed and put to practical use as epoxy resins having low water absorption and improved weather resistance.

  However, the conventional epoxy resin has a low reactivity with a cationic initiator, and thus has a problem that the curing rate is slow. In addition, these epoxy resins are solid or highly viscous liquids, but in recent years, they have improved the impregnation between fibers in fiber composite materials, and have been able to cope with sealing fine gaps of several μm or less. Therefore, a lower viscosity epoxy resin is desired. Furthermore, the cured epoxy resin is generally poor in flexibility, and when used as an insulating material used for flexible printed wiring boards, which has been in increasing demand in recent years, there is a problem that cracks are likely to occur and it cannot be used industrially. Therefore, a more flexible resin has been demanded.

  A curable composition containing a diglycidyl etherified product of an alicyclic dialcohol such as cyclohexanediol is known as a lower viscosity liquid epoxy resin that can solve the above problems, and various uses of the resulting cured product Application to is proposed. For example, Patent Document 1 discloses a low-viscosity curable epoxy resin composition obtained by distillation-purified low-viscosity cyclohexanediol diglycidyl ether and an acid anhydride-based curing agent, and a cured product thereof. In Patent Document 2, a liquid epoxy resin composition containing a diglycidyl etherified product of 4,4′-bis (hydroxymethyl) bicyclohexyl and a phenol novolac-based curing agent has excellent low viscosity, and its curing The product has been shown to have excellent performance in moisture resistance and flexibility.

  On the other hand, a curable epoxy resin composition having a low viscosity is obtained using a diglycidyl etherified product of a dialcohol such as 1,4-butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol as a reaction diluent. It has been reported. For example, Patent Document 3 discloses a liquid epoxy resin composition containing 1,4-cyclohexanedimethanol diglycidyl ether, a hydrogenated bisphenol A type epoxy resin, and an epoxy curing agent, and a cured product thereof. In addition, Patent Document 4 discloses a distillation-purified aliphatic epoxy compound such as 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, bisphenol A type or A liquid epoxy resin composition containing a hydrogenated bisphenol A type epoxy resin and an epoxy curing agent and a cured product thereof are disclosed. Further, Patent Document 5 discloses an epoxy resin composition using hydrogenated bisphenol A diglycidyl ether having a condensation polymer content of 5% or less and a viscosity of 1000 mPa · s or less as a reaction diluent.

  However, diglycidyl ethers such as 1,4-cyclohexanedimethanol diglycidyl ether and 1,4-butanediol diglycidyl ether are conventionally used in combination with curing agents such as acid anhydrides and other epoxy resins. Although the obtained cured product has a high glass transition temperature, there is a problem that flexibility is low. On the other hand, when these diglycidyl ethers are cured alone, the resulting cured product exhibits flexibility, but has a low glass transition temperature and a problem in heat resistance.

JP-A-11-106607 JP 2006-188606 A Japanese Patent Laid-Open No. 6-136092 JP 2003-73453 A JP 2003-26766 A

  The present invention has been made in view of the above-described problems, and is a curable composition that provides a cured product having a fast curing speed, low viscosity, excellent workability, and balanced heat resistance and flexibility. Is the issue.

  As a result of intensive studies to solve the above problems, the present inventor has achieved the above problems by using a compound having a bifunctional group of a vinyl group and a glycidyl group instead of the conventional diglycidyl ether. As a result, the present invention has been achieved.

That is, this invention is the following liquid curable composition and hardened | cured material.
(1) The following components (A) and (B)
(A) The following general formula (1),
CH ₂ = CH—O—X—O—G (1)
(In the formula, X represents an alicyclic alkylene group containing a divalent linear or branched alkylene group having 2 to 12 carbon atoms or a cyclohexylene group, and G represents a glycidyl group)
The liquid curable composition containing the (alpha) -vinyloxy-omega-glycidyl ether compound shown by (B) cationic polymerization initiator.

(2) The liquid curable composition wherein the α-vinyloxy-ω-glycidyl ether compound as component (A) is 4-vinyloxybutyl glycidyl ether or 4- (vinyloxymethyl) -cyclohexylmethanol glycidyl ether.

(3) The liquid curable composition, wherein the cationic polymerization initiator as the component (B) is an onium salt.

(4) The liquid curable composition further comprising an epoxy resin as the component (C).

(5) Liquid curable composition of said (4) whose content of component (C) is 1-50 mass parts with respect to 100 mass parts of component (A).

(6) The liquid curable composition of the above (4) or (5), wherein the epoxy resin of component (C) is an aromatic epoxy resin and / or an alicyclic epoxy resin.

(7) The epoxy resin of component (C) is at least one epoxy selected from the group consisting of bisphenol A type epoxy resins, bisphenol F type epoxy resins, hydrogenated bisphenol A type epoxy resins and hydrogenated bisphenol F type epoxy resins. The liquid curable composition according to the above (4) or (5), which is a resin.

(8) A cured product obtained by curing the liquid curable composition of (1) to (7).

  The curable composition of the present invention has a high curing rate, can be either heat cured or cured by irradiation with active energy rays, has excellent low viscosity, and is excellent in workability. In addition, the cured product of the present invention has balanced heat resistance and flexibility, and should be suitably used for molding materials, sealing materials, electrical insulating materials, adhesives, paints, inks for inkjet printers, and the like. Can do.

(A) α-vinyloxy-ω-glycidyl ether compound In the liquid curable composition of the present invention, the α-vinyloxy-ω-glycidyl ether compound used as the component (A) is represented by the following general formula (1). It is.
CH ₂ = CH—O—X—O—G (1)
(In the formula, X represents an alicyclic alkylene group containing a divalent linear or branched alkylene group having 2 to 12 carbon atoms or a cyclohexylene group, and G represents a glycidyl group)

  This component (A) acts as a curable compound, and specific compounds thereof include 2-vinyloxyethanol glycidyl ether, 3-vinyloxypropanol glycidyl ether, 4-vinyloxybutanol glycidyl ether, 5-vinyloxypentanol glycidyl ether, 6-vinyloxyhexanol glycidyl ether, 3-vinyloxy-2,2-dimethyl-propanol glycidyl ether, 5-vinyloxy-3-methylpentanol glycidyl ether, 4- (vinyloxymethyl) -Cyclohexyl methanol glycidyl ether etc. are mentioned.

  Among these components (A), 4-vinyloxybutanol glycidyl ether is preferable in that the effect of reducing the viscosity is excellent, and 4- (vinyloxymethyl)-in terms of low water absorption and heat resistance. Cyclohexyl methanol glycidyl ether is preferred.

  The production method of these components (A) is not particularly limited. For example, by reacting monovinyl ether of α, ω-alkanediol containing a linear, branched or cyclohexylene group having 2 to 12 carbon atoms with epihalohydrin. can get. As the epihalohydrin, epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, β-methylepibromohydrin β-methylepiiodohydrin, and the like are preferable, and epichlorohydrin is more preferable.

  The reaction of the above monovinyl ether of α, ω-alkanediol with epihalohydrin is, for example, (1) acidic catalyst such as sulfuric acid, boron trifluoride ethyl ether, tin tetrachloride, quaternary ammonium salts, quaternary phosphonium salts To produce a halohydrin ether body by reacting in the presence of a phase transfer catalyst such as crown ethers, and then reacting this halohydrin ether body with a dehydrohalogenating agent such as sodium hydroxide to effect ring closure. A two-step process, or (2) a one-step method for obtaining a glycidyl ether by performing a dehydrohalogenation reaction in one step in the presence of an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide. Can be performed.

  Isolation of the α-vinyloxy-ω-glycidyl ether compound after completion of the reaction can be performed by a conventional method. For example, after adding a non-aqueous solvent such as hydrocarbon and then washing with water to elute and remove by-product salts. The target α-vinyloxy-ω-glycidyl ether compound can be obtained by performing solvent removal, dehydration, filtration of a salt precipitated in a trace amount, or powder-liquid separation.

  The α-vinyloxy-ω-glycidyl ether compound thus obtained can be used as it is as a raw material of the curable composition of the present invention, but it is further used after removing impurities by distillation purification or the like. You can also. 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. The distillation purification is preferably performed under reduced pressure while maintaining the liquid temperature at a temperature at which dimerization (polymerization) of the α-vinyloxy-ω-glycidyl ether compound does not occur. The preferable purity of the α-vinyloxy-ω-glycidyl ether compound after purification by distillation is 90% by mass or more, more preferably 95% or more.

(B) Cationic polymerization initiator As the cationic polymerization initiator used as the component (B) in the liquid curable composition of the present invention, a conventionally known thermal cationic polymerization initiator that generates a cationic species or a Lewis acid by heat, or An active energy ray cationic polymerization initiator that generates a cationic species or a Lewis acid by an active energy ray can be used.

  Specific examples of the component (B) include various onium salts such as quaternary ammonium salts, phosphonium salts, sulfonium salts, aryldiazonium salts, diaryliodonium salts, sulfonic acid esters, trifluoromethanesulfonic acid salts, boron-based compounds. Compounds and the like. In addition, mixed ligand metal salts of iron compounds and silanol-aluminum complexes can also be used.

Among these, quaternary ammonium salts include PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , SbC 1 ₆ ⁻ , BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , SbF ₅ (OH) ⁻ as anions. ^{_{, HSO 4-, p-CH 3}} C 6 H 4 SO 3 -, CF 3 SO 3 - tetrabutylammonium salt with like, tetraethylammonium salts, N, N-dimethyl -N- benzyl anilinium salt, N, N -Diethyl-N- (4-methoxybenzyl) toluidinium salt and the like.

Examples of the phosphonium salt include ethyltriphenylphosphonium salt and tetrabutylphosphonium salt having PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ^{— and the} like as anions.

As the sulfonium salt, as anions, PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , SbC 1 ₆ ⁻ , BF ₄ ⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ , FSO ₃ ²⁻ , F ₂ PO ₂ ⁻ , B _(C 6 _{F 5) 4} ^-, etc. triphenylsulfonium salt having a tris (4-methoxyphenyl) sulfonium salt, diphenyl (4-phenylthiophenyl) sulfonium salt, diphenyl-4-thio-phenoxyphenyl sulfonium, bis [4- (Diphenylsulfonio) phenyl] sulfide, bis [4- (di (4- (2-hydroxyethyl) phenyl) sulfonio) phenyl] sulfide, bis- [4- (di (4- (2-hydroxyethoxy) phenylsulfone) Nio) phenyl] sulfide, dialkylphenacylsulfonium salt, dialkyl- 4-hydroxyphenylsulfonium salt etc. are mentioned.

As the aryldiazonium salt, phenyldiazonium salt having PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , SbC 1 ₆ ⁻ , BF ₄ ⁻ , SnCl ₆ ⁻ , FeCl ₄ ⁻ , BiC1 ₅ ^2−, etc. as anions, 4- A methoxyphenyl diazonium salt, 4-nitrophenyl diazonium salt, etc. are mentioned.

Examples of the diaryliodonium salts include PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , SbC 1 ₆ ⁻ , BF ₄ ⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ , FSO ₃ ²⁻ , F ₂ PO ₂ ⁻ as anions. _{, B (C 6 F 5)} 4 - such as diphenyl iodonium salt having a bis (4-methoxyphenyl) iodonium salt, bis (4-methylphenyl) iodonium salt, bis (4-tert- butylphenyl) iodonium salts, bis (Dodecylphenyl) iodonium salt, 4-methylphenyl-4- (1-methylethyl) phenyliodonium salt, 4-methylphenyl-4- (2-methylpropyl) phenyliodonium salt, and the like.

  Examples of the sulfonate ester include α-hydroxymethylbenzoin sulfonate ester, N-hydroxyimide sulfonate, α-sulfonyloxy ketone, β-sulfonyloxy ketone, and the like.

  Examples of the trifluoromethanesulfonate include diethylammonium trifluoromethanesulfonate, triethylammonium trifluoromethanesulfonate, diisopropylammonium trifluoromethanesulfonate, and ethyldiisopropylammonium trifluoromethanesulfonate.

  Examples of boron compounds include boron trifluoride etherate compounds, boron trifluoride, and triphenylborate.

Among the above components (B), preferred are onium salts excellent in handleability and curability, and particularly preferred cationic polymerization initiators are PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ and SbC 1 ₆ ² as anions. ^And sulfonium salts and diaryliodonium salts having ^— , BF ₄ ^{— and the} like.

  These onium salts are commercially available, for example, as a sulfonium salt cationic polymerization initiator, manufactured by ADEKA Co., Ltd .: trade names Adeka Opton CP series (CP-66 and CP-77, etc.), San Apro Co., Ltd .: commercial products Name CPI series (CPI-100P, CPI-101A), Sanshin Chemical Industry: trade name Sun-Aid SI series (SI-60L, SI-80L and SI-100L) and Nippon Soda: trade name CI series are preferred. Can be used.

  Moreover, as an example of a diaryliodonium salt type cationic polymerization initiator, Ciba Specialty Chemicals make: brand name IRGACURE250, Wako Pure Chemical Industries make: brand name WPI-113 etc. can be used preferably.

  The said component (B) may be used independently and may use 2 or more types together. Moreover, you may use together a thermal cationic polymerization initiator and an active energy ray cationic polymerization initiator. The usage-amount of a component (B) is 0.01-20 mass parts with respect to 100 mass parts of components (A), More preferably, it is the quantity of 0.1-10 mass parts. When the usage-amount of a component (B) remove | deviates from the said range, the heat resistance and intensity | strength of the obtained hardened | cured material may fall.

  In addition, as a component (B), when using the cationic polymerization initiator hardened | cured with light, you may use a sensitizer together. When a sensitizer is used in combination, curing can be initiated even when the cationic curing initiator component (B) is irradiated with light having a wavelength longer than the wavelength of the light that generates the acid most efficiently. . Examples of the sensitizer include benzophenone, acridine orange, perylene, anthracene, phenothiazine, and 2,4-diethylthioxanthone.

  Moreover, you may use a component (B) with a chain transfer agent. When a chain transfer agent is used in combination with the component (B), the polymerization rate increases and it is possible to prevent unreacted epoxy groups from remaining. In general, polyfunctional alcohols such as ethylene glycol, butanediol, trimethylolpropane triol, pentaerythritol, and polyvinyl alcohol can be used as the chain transfer agent. However, when a chain transfer agent is used, the hygroscopicity of the cured product is increased and the heat resistance may be lowered. Therefore, it is necessary to be careful when using the chain transfer agent.

(C) Epoxy resin In addition to the essential components (A) and (B), an epoxy resin can be used as the component (C) as necessary in the liquid curable composition of the present invention. Although it does not specifically limit as an epoxy resin which is this component (C), An aromatic epoxy resin and / or an alicyclic epoxy resin are used preferably. 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, naphthalene type epoxy resins, and other diglycidyl ethers, aminophenols, etc. Polyfunctional epoxy resins such as glycidylamine-type epoxy resins obtained from phenol, epoxy resins obtained from phenol novolac, epoxy resins obtained from cresol novolac, bisphenol A novolac epoxy resins, novolac epoxy resins obtained from phenols and hydroxybenzaldehydes Etc.

  On the other hand, examples of the alicyclic epoxy resin include an epoxy resin obtained by directly hydrogenating the aromatic ring of the above-described aromatic epoxy resin or an epoxy resin obtained by reacting polyphenols with hydrogen and then reacting with epichlorohydrin. Is mentioned. More specifically, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated biphenol type epoxy resin, hydrogenated phenol novolac type epoxy resin, hydrogenated cresol novolac epoxy resin, hydrogenated naphthalene type epoxy resin. Etc.

  Among these, using a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a hydrogenated bisphenol A type epoxy resin, and a hydrogenated bisphenol F type epoxy resin, a low viscosity epoxy resin is obtained, and moisture resistance and This is preferable in that a cured product having an excellent balance of heat resistance can be obtained.

  The usage rate of the epoxy resin which is a component (C) is 1-50 mass parts with respect to 100 mass parts of components (A), Preferably, it is 5-40 mass parts. If the proportion of component (C) used exceeds 50 parts by mass, the heat resistance and flexibility of the resulting cured product may be reduced.

(D) Optional component Furthermore, the liquid curable composition of the present invention includes various kinds of powdery reinforcing agents and fillers, colorants or pigments, flame retardants, resin additives and the like for the purpose of improving the properties of the cured product. The additive component can be blended.

  Examples of powdery reinforcing agents and fillers include metal oxides such as aluminum oxide and magnesium oxide, silicon compounds such as fine powder silica, fused silica and crystalline silica, fillers such as glass beads, and metal water such as aluminum hydroxide. Examples thereof include oxides, kaolin, mica, quartz powder, graphite, and molybdenum disulfide. These blendings are arbitrary, but generally 10 to 100 parts by mass is appropriate for 100 parts by mass of the curable composition.

  Examples of the colorant or pigment include titanium dioxide, molybdenum red, bitumen, ultramarine blue, cadmium yellow, cadmium red, and organic dyes. Moreover, a flame retardant, for example, an antimony trioxide, a bromine compound, a phosphorus compound, etc. can be mentioned. These additives may be blended arbitrarily, but generally 0.01 to 30 parts by mass is blended with respect to 100 parts by mass of the curable composition.

  As a resin additive, 1 type, or 2 or more types of combinations, such as a fluororesin, an acrylic resin, and a silicone resin, can be mentioned. The blending ratio of these resin additives is preferably 50 parts by mass or less with respect to an amount within a range not impairing the original properties of the curable composition of the present invention, that is, 100 parts by mass of the curable composition of the present invention.

  The liquid curable composition of the present invention is produced by mixing the component (A) and the component (B), which are the essential components, with the component (C) and the optional component (D) as necessary. Can be obtained as a liquid. In the present invention, “liquid” means liquid at 25 ° C.

  The curable composition of the present invention obtained as described above is cured by heating or irradiation with active energy rays, as in the case of a normal thermosetting epoxy resin composition or photocurable epoxy resin composition. Can do. Curing conditions are not particularly limited, but in the case of thermosetting, it can be cured by heating for about 1 to 24 hours at a temperature of 60 to 250 ° C, preferably in the range of 80 to 200 ° C. When an active energy ray curing catalyst is used as the curing agent (B), it can be cured by irradiation with ultraviolet rays, visible light, electron beams, etc., in a range of room temperature to 150 ° C.

  Hereinafter, the present invention will be described in more detail with reference to Examples, Synthesis Examples, and Comparative Examples, but the present invention is not limited to these Examples and the like. In addition, the part in an example means a mass part unless there is particular notice.

Synthesis example 1
Synthesis of 4-vinyloxybutanol glycidyl ether:
A 300 ml stirred glass reactor equipped with a condenser and a water separator was charged with 51.8 g (0.5 mol) of 4-vinyloxybutanol (also known as 1,4-butanediol monovinyl ether), 92.5 g of epichlorohydrin, 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. under a reduced pressure of 20 to 25 kPa for 1.5 hours. Water produced during the reaction was azeotroped with epichlorohydrin, the vapor was condensed, and only epichlorohydrin was circulated in the system by a separator and removed to the outside of the system. The amount of water distilled off was 9 g, which was a theoretical amount. The reaction mixture was cooled to 30 ° C. and then filtered to remove the precipitate. The precipitate was washed with 50 g epichlorohydrin and combined with the filtrate. This filtrate was distilled under reduced pressure, and epichlorohydrin was distilled off and collected. After cooling the residual oil to 25 ° C., the precipitate was removed by filtration, and the resulting oily product was distilled under high vacuum to give 4-vinyloxybutanol glycidyl ether (hereinafter referred to as “14BD-VGE”) 76. 0.5 g was obtained (column top 75-80 ° C./0.1 kPa, yield 89%, purity 99.5% by gas chromatography).

Synthesis example 2
Synthesis of 4- (vinyloxymethyl) -cyclohexylmethanol glycidyl ether:
To a 300 ml stirred glass reactor equipped with a condenser and a water separator, 102.2 g (0.6 mol) of 4- (vinyloxymethyl) cyclohexylmethanol (also known as 1,4-cyclohexanedimethanol monovinyl ether), Epichlorohydrin (100 g), granular sodium hydroxide (37.5 g) and benzyltrimethylammonium chloride (0.1 g) were charged, and the reactor was cooled and vigorously stirred while maintaining the temperature at 40 ° C. for 10 hours. 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 to obtain 112.7 g of 4- (vinyloxymethyl) cyclohexylmethanol glycidyl ether (hereinafter referred to as “CHDM-VGE”). (Top 140-145 ° C./0.4 kPa, yield 83%, purity by gas chromatography 99%).

Example 1
A liquid thermosetting composition was prepared by mixing 14 parts of 14BD-VGE obtained in Synthesis Example 1 and 1 part of Adeka Opton CP-66 (trade name, manufactured by ADEKA Corporation) as a thermal cationic polymerization initiator.

Example 2
A thermosetting composition was prepared in the same manner as in Example 1 except that 14BD-VGE was replaced with CHDM-VGE obtained in Synthesis Example 2.

Example 3
Example 14 except that 100 parts of 14BD-VGE is replaced with a mixture of 20 parts of the above CHDM-VGE and 80 parts of hydrogenated bisphenol A diglycidyl ether (HBPA-DGE; epoxy equivalent 200, manufactured by Maruzen Petrochemical Co., Ltd.). A thermosetting composition was prepared.

Comparative Example 1
A thermosetting composition was prepared in the same manner as in Example 1 except that 14BD-VGE was replaced with 1,4-butanediol diglycidyl ether (14BD-DGE).

Comparative Example 2
A thermosetting composition was prepared in the same manner as in Example 1 except that 14BD-VGE was replaced with 1,4-cyclohexanedimethanol diglycidyl ether (CHDM-DGE).

Comparative Example 3
A thermosetting composition was prepared by mixing 100 parts by weight of CHDM-DGE with 111 parts of 4-methylhexahydrophthalic anhydride and 1 part of 2-ethyl-4-methylimidazole as a curing agent.

Comparative Example 4
A thermosetting composition was prepared in the same manner as in Example 1 except that 14BD-VGE was replaced with HBPA-DGE.

Test example 1
About the thermosetting composition prepared in Examples 1-3 and Comparative Examples 1-4, the following composition characteristic and hardened | cured material characteristic were evaluated. The results are shown in Table 1 together with the composition.

<Viscosity>
The viscosity of each composition was measured at 23 ° C. using a viscometer (manufactured by A & D Co., Ltd., SV-10 type).

<Geltime>
About 0.5 g of the thermosetting composition was placed on a hot plate heated to 150 ° C., and the state of the resin composition was observed while stirring with the tip of a spatula. The time from when the composition was placed on the hot plate until the resin gelled and the tackiness disappeared was measured and used as the gel time.

<Flexibility>
The prepared thermosetting 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. Machining was performed to obtain a test piece of 50 mm × 20 mm and a thickness of 0.5 mm. Using a core rod having a diameter of 2 mm, a bending resistance test was performed according to JISK5600-5-1, and the presence or absence of cracks was observed.

<Glass transition temperature>
The prepared thermosetting 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, the temperature was raised to 150 ° C. at a rate of temperature rise of 20 ° C./min.

(Result)

Example 4
100 parts of 14BD-VGE obtained in Synthesis Example 1, 1 part of IRGACURE250 (trade name, manufactured by Ciba Specialty Chemicals) as a photocation polymerization initiator, and Adeka Opton CP-66 (trade name, Co., Ltd.) as a thermal cationic polymerization initiator A part of ADEKA) was mixed to prepare a liquid photocurable composition.

Example 5
A photocurable composition was prepared in the same manner as in Example 4 except that CHDM-VGE obtained in Synthesis Example 2 was used instead of 14BD-VGE.

Example 6
A photocurable composition was prepared in the same manner as in Example 4 except that instead of 100 parts of 14BD-VGE, a mixture of 80 parts of CHDM-VGE and 20 parts of HBPA-DGE was used.

Test example 2
The photocurable composition obtained in Examples 4 to 6 was applied to an aluminum plate to a thickness of 50 μm using an applicator (YOSHIMITSU Co., Ltd., YA-2 type), and an ultraviolet ray provided with a Deep UV lamp. Ultraviolet rays were irradiated at 4 mW / cm ² for 180 seconds using an irradiation apparatus (trade name “Spot Cure SP-7” manufactured by USHIO INC.). 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 DSC method as in Example 1. The results are shown in Table 2 together with the composition. In the table, the viscosity of the composition is also shown.

Example 7
To the CHDM-VGE obtained in Synthesis Example 2, 0.46 mol% IRGACURE250 (trade name, manufactured by Ciba Specialty Chemicals) as a photocationic polymerization initiator was mixed to prepare a photocurable fat composition.

Comparative Example 5
A photocurable fat composition was prepared in the same manner as in Example 7 except that CHDM-VGE was replaced with the above-mentioned CHDM-DVE.

Comparative Example 6
A photocurable fat composition was prepared in the same manner as in Example 7 except that CHDM-VGE was replaced with the above-mentioned CHDM-DGE.

Comparative Example 7
A photocurable fat composition was prepared in the same manner as in Example 7 except that 100 parts of CHDM-VGE was replaced with a mixture of 43 parts of CHDM-DVE and 57 parts of CHDM-DGE.

Test example 3
An ultraviolet irradiation device (USHIO Corporation, trade name “Spotcure SP-” manufactured by applying 0.1 g of the photocurable composition obtained in Example 7 and Comparative Examples 5 to 7 to an aluminum plate and equipped with a Deep UV lamp. 7 ”) was irradiated with ultraviolet rays at 2.5 mW / cm ² and the time until the resin was cured was measured to obtain a gel time. The results are shown in Table 3 together with the composition.

Example 8
100 parts of CHDM-VGE obtained in Synthesis Example 2, 3 parts of IRGACURE 250 (trade name, manufactured by Ciba Specialty Chemicals) as a photocationic polymerization initiator, and Disparon 1761 (trade name, Kashiwagi Kasei Co., Ltd.) as a silicone-based surface conditioner )) 1 part was mixed to prepare a liquid photocurable composition.

Comparative Example 8
A photocurable fat composition was prepared in the same manner as in Example 8 except that CHDM-VGE was replaced with the above-mentioned CHDM-DVE.

Comparative Example 9
A photocurable fat composition was prepared in the same manner as in Example 8 except that CHDM-VGE was replaced with the above-mentioned CHDM-DGE.

Comparative Example 10
A photocurable fat composition was prepared in the same manner as in Example 8 except that 100 parts of CHDM-VGE was replaced with a mixture of 43 parts of CHDM-DVE and 57 parts of CHDM-DGE.

Test example 4
The photocurable composition obtained in Example 8 and Comparative Examples 8 to 10 was applied to a mild steel plate to a thickness of 50 μm using an applicator (YOSHIMITSU Co., Ltd., YA-2 type), and a high-pressure mercury lamp. Was irradiated with ultraviolet rays at 10.6 mW / cm ² for 30 seconds using an ultraviolet irradiation device equipped with a light source (manufactured by Sen Special Light Source Co., Ltd., trade name “Handy Cure Arab”). Next, post curing was performed at 150 ° C. for 30 minutes with a hot air dryer to obtain a cured coating film. The characteristics evaluation of the obtained coating-film cured | curing material was performed with the following method. The results are shown in Table 4 together with the composition.

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

<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.

<Pencil hardness>
Evaluation was performed according to JISK5400.

Comparative Example 11
A photocurable fat composition was prepared in the same manner as in Example 8 except that CHDM-VGE was replaced with the above-described HBPA-DGE.

Test example 5
The characteristics of the cured coating film were evaluated in the same manner as in Test Example 4 except that the mild steel plate was changed to a glass plate. The results are shown in Table 5 together with the composition.

  As shown in Test Example 1, the curable composition of the present invention has a low viscosity and excellent workability, and has a very high curing rate. The obtained cured product has excellent bending resistance and is a single cured product of diglycidyl ether. The glass transition temperature was higher than that of the material, and the heat resistance was shown to be excellent. Furthermore, in Example 3, it was shown that heat resistance can be improved while maintaining flex resistance by blending 20% of hydrogenated bisphenol A type epoxy resin.

  On the other hand, as shown in Comparative Examples 1 and 2, 1,4-butanediol diglycidyl ether and 1,4-cyclohexanedimethanol diglycidyl ether alone cured products are excellent in bending resistance, but the curing rate is The glass transition temperature was low and the heat resistance was poor. Moreover, as shown in Comparative Example 3, when mixed with 1,4-cyclohexanedimethanol diglycidyl ether and an epoxy curing agent, or as shown in Comparative Example 4, hydrogenated bisphenol A type epoxy resin When used, the obtained cured product shows a high glass transition temperature, but on the contrary, the rigidity is increased and the bending resistance is insufficient, and a cured product having both excellent heat resistance and bending resistance was not obtained. .

  Moreover, the curable composition of this invention can be hardened | cured also by active energy ray irradiation as shown to the said Test Examples 3-5. In the case of curing with an active energy ray, curing is possible even with an active energy ray cationic polymerization initiator alone, but when used in combination with a thermal cationic polymerization initiator, the heat resistance becomes higher. In addition, as is clear from the comparison between the diglycidyl ether composition and the divinyl ether composition (Comparative Examples 5 to 10), the curable composition of the present invention is compared with the diglycidyl ether curable composition. The curing speed is very fast. Such an effect cannot be obtained by simply mixing diglycidyl ether and divinyl ether, and is manifested only in the curable composition of the present invention having both vinyl ether groups and glycidyl ether groups in one molecule. It is. Furthermore, it became clear that the composition of this invention gives the coating-film hardened | cured material excellent in adhesiveness also with respect to the glass plate.

The curable composition of the present invention has a high curing rate and can be cured by thermal curing or irradiation with active energy, and has excellent low viscosity and excellent workability. A cured product obtained by curing the composition has balanced heat resistance and flexibility, and is excellent in adhesion to glass and metal. Therefore, the curable composition of the present invention and the cured product thereof can be suitably used for molding materials, sealing materials, electrical insulating materials, adhesives, paints, inkjet printer inks, and the like.

Claims (8)

The following components (A) and (B)
(A) The following general formula (1),
CH ₂ = CH—O—X—O—G (1)
(In the formula, X represents an alicyclic alkylene group containing a divalent linear or branched alkylene group having 2 to 12 carbon atoms or a cyclohexylene group, and G represents a glycidyl group)
Α-vinyloxy-ω-glycidyl ether compound represented by formula (B) A liquid curable composition containing a cationic polymerization initiator.   The liquid curable composition according to claim 1, wherein the component (A) α-vinyloxy-ω-glycidyl ether compound is 4-vinyloxybutyl glycidyl ether or 4- (vinyloxymethyl) -cyclohexylmethanol glycidyl ether.   The liquid curable composition according to claim 1 or 2, wherein the cationic polymerization initiator of component (B) is an onium salt.   Furthermore, the liquid curable composition in any one of Claims 1-3 which contains an epoxy resin as a component (C).   The liquid curable composition according to claim 4, wherein the content of the component (C) is 1 to 50 parts by mass with respect to 100 parts by mass of the component (A).   The liquid curable composition according to claim 4 or 5, wherein the epoxy resin of component (C) is an aromatic epoxy resin and / or an alicyclic epoxy resin.   The component (C) epoxy resin is at least one epoxy resin selected from the group consisting of bisphenol A type epoxy resins, bisphenol F type epoxy resins, hydrogenated bisphenol A type epoxy resins and hydrogenated bisphenol F type epoxy resins. The liquid curable composition in any one of Claims 4-6. Hardened | cured material obtained by hardening | curing the liquid curable composition in any one of Claims 1-7.