JP4524083B2 - Active energy ray-curable resin composition - Google Patents

Description

  The present invention relates to a novel epoxy resin useful for improving the toughness of a cured product and an active energy ray-curable resin composition containing the epoxy resin.

  Conventionally, as an active energy ray-curable resin composition, a mixture of a compound having an unsaturated double bond, for example, a (meth) acryloyl group and a photo radical polymerization initiator has been generally used. This is because the radical photopolymerization initiator is decomposed by active energy rays to generate radicals which are active species, and a (meth) acryloyl group is polymerized to obtain a cured product.

  However, the radical polymerization type curable resin having the (meth) acryloyl group or the like generally has a high viscosity. Therefore, it is necessary to add an organic solvent or a reactive diluent when used in applications such as a coating agent and an adhesive. It was. Dilution with organic solvents has been reduced due to deterioration of the working environment and global environment and economic problems, but it is difficult to avoid using it at all, and it is also harmful to the environment and the human body when using reactive diluents. Influencing was common. In addition, radical polymerization type curable resins are prone to curing inhibition by oxygen, and in order to prevent this, they must be cured in a vacuum or in the presence of an inert gas. Equipment was necessary.

  On the other hand, there is an active energy ray-curable resin composition in which a photocationic polymerization initiator is blended with an epoxy resin for the above radical photopolymerization. This is because the photocationic polymerization initiator is decomposed by active energy rays to generate cations which are active species, and the epoxy resin is polymerized to obtain a cured product. This cationic polymerization type curable resin is very useful because it can be used in a normal atmosphere because it can adjust the viscosity without using an organic solvent, has almost no odor, and has no inhibition of polymerization by oxygen.

  However, the curable resin of the cationic polymerization type has a great weakness that a cured product obtained by irradiation with active energy rays is generally hard but very brittle. The term “brittle” means that the cured product is easily broken when a large force is applied to the cured product, such as bending or pulling, and can be judged sensorily. The comparison of the brittleness of each cured product is easy to compare by measuring the strength and elongation of the cured product by a tensile test specified in JIS, whereby the brittleness can be quantified as the breaking strength and breaking elongation. Currently, there is a demand for such a non-brittle cured product, that is, a tough cured product. The “cured material having excellent toughness” as used in the present invention is not simply excellent in impact resistance and flexibility. That is, it means a cured product having a property of exhibiting a yield elongation and rupturing as a large force is applied, even though the cured product itself is strong, like a thermoplastic resin such as an ABS resin. A cured product having such properties and also having the characteristics of cationic polymerization or an epoxy resin capable of imparting such toughness has been sought for a long time, but no satisfactory one has been obtained yet.

  Under such circumstances, the epoxy resin capable of imparting toughness to the active energy ray cured product is obtained by heating both terminal carboxylated polybutadiene and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate. An alicyclic epoxy resin has been proposed (see, for example, Patent Document 1). However, the toughness of the cured product blended with the epoxy is judged only in flexibility, and nothing is mentioned about the breaking strength of the cured film or the elongation at break, and the cured film is described in JIS. When a tensile test is carried out based on the method, it cannot be determined whether or not the material exhibits fracture properties after exhibiting yield elongation, and the meaning differs from toughness in the present invention.

  In addition, the present inventors have previously proposed a method of adding toughness by blending diglycerin to which alkylene oxide is added (see Patent Document 2). According to this method, a tough active energy ray cured product as referred to in the present invention can be obtained, but a good cured product is obtained, but the strength is not yet sufficient, and in view of the balance between elongation and strength, sufficient strength is obtained. Was still a cured product.

In order to solve this problem and impart toughness to the cured product, there is a demand in particular in the fields of optical modeling, coating, and resist for flexible printed wiring boards.
JP 2001-329045 A (paragraphs 97 to 106) Japanese Patent Application No. 2002-168730 (paragraphs 25 to 30)

  The present invention uses an epoxy resin that does not use an organic solvent, has almost no odor, and does not cause oxygen inhibition, and can improve the toughness of an active energy ray cured product, and contains the epoxy resin An object of the present invention is to provide an active energy ray-curable resin composition.

  As a result of intensive research to solve the above-mentioned problems, the present inventors have synthesized a novel epoxy resin described later and found that a resin composition containing the resin as an essential component can achieve the above-described object. The present invention has been completed.

（ｍは１〜２０の自然数、ｎは１〜１４の自然数、Ｘはハロゲン原子またはＣ１〜５のアルキル基、ａおよびｂは０〜４の整数、Ｇ_１およびＧ_２はグリシジル基又は水素原子（ただし、Ｇ_１、Ｇ_２が同時に水素原子であることはない）、Ｒ_１はＣ１〜１０のアルキレン基またはアルキリデン基、Ｒ_２はアルキレン基、アルキリデン基、スルホニル基、酸素原子または原子団の存在しない直接結合を示す。）で示され、数平均分子量の範囲が６００〜５０００であるエポキシ樹脂を合成することおよび該エポキシ樹脂を含有する樹脂組成物を用いることにより上記の目的を達成しうることを見出した。 That is, the present invention is a compound obtained by reacting glycol glycidyl ether and a phenol compound,

(M is a natural number of 1 to 20, n is a natural number of 1 to 14, X is an alkyl group, a and b are integers of 0 to 4, _{G 1} and _{G 2} are glycidyl groups or a hydrogen atom a halogen atom or C1~5 (However, G ₁ and G ₂ are not simultaneously hydrogen atoms), R ₁ is a C1-10 alkylene group or alkylidene group, R ₂ is an alkylene group, alkylidene group, sulfonyl group, oxygen atom or atomic group. The above object can be achieved by synthesizing an epoxy resin having a number average molecular weight of 600 to 5000 and using a resin composition containing the epoxy resin. I found out.

  The physical properties of the novel epoxy resin of the present invention and the cured product of the active energy ray-curable resin composition containing the epoxy resin are characterized by exhibiting toughness.

（ｍは１〜２０の自然数、ｎは１〜１４の自然数、Ｘはハロゲン原子またはＣ１〜５のアルキル基、ａおよびｂは０〜４の整数、Ｇ_１およびＧ_２はグリシジル基又は水素原子（ただし、Ｇ_１、Ｇ_２が同時に水素原子であることはない）、Ｒ_１はＣ１〜１０のアルキレン基またはアルキリデン基、Ｒ_２はアルキレン基、アルキリデン基、スルホニル基、酸素原子または原子団の存在しない直接結合を示す。）で示され、数平均分子量の範囲が６００〜５０００であるエポキシ樹脂＜以下、（Ａ）成分ともいう＞はグリコールのグリシジルエーテル化合物とフェノール類化合物から合成される。このグリコールのグリシジルエーテル化合物は、少なくとも一つ好ましくは二つのグリシジルエーテルを有する化合物であり以下のものがある。すなわち、メチレングリコール，ジメチレングリコール，トリメチレングリコールおよびポリメチレングリコールのグリシジルエーテル、エチレングリコール，ジエチレングリコール，トリエチレングリコールおよびポリエチレングリコールのグリシジルエーテル、プロピレングリコール，ジプロピレングリコール，トリプロピレングリコールおよびポリプロピレングリコールのグリシジルエーテル、テトラメチレングリコール，ジテトラメチレングリコール，トリテトラメチレングリコール，ポリテトラメチレングリコールのグリシジルエーテル、１，４−ブタンジオールのグリシジルエーテル、１，６−ヘキサンジオールのグリシジルエーテル、ネオペンチルグリコールのグリシジルエーテルなどが挙げられ、好ましくはポリプロピレングリコールのジグリシジルエーテルおよびネオペンチルグリコールのグリシジルエーテルが用いられる。 In the present invention

(M is a natural number of 1 to 20, n is a natural number of 1 to 14, X is an alkyl group, a and b are integers of 0 to 4, _{G 1} and _{G 2} are glycidyl groups or a hydrogen atom a halogen atom or C1~5 (However, G ₁ and G ₂ are not simultaneously hydrogen atoms), R ₁ is a C1-10 alkylene group or alkylidene group, R ₂ is an alkylene group, alkylidene group, sulfonyl group, oxygen atom or atomic group. An epoxy resin (hereinafter also referred to as component (A)) having a number average molecular weight in the range of 600 to 5000 is synthesized from a glycol glycidyl ether compound and a phenol compound. The glycol glycidyl ether compound is a compound having at least one, preferably two glycidyl ethers. That is, glycidyl ether of methylene glycol, dimethylene glycol, trimethylene glycol and polymethylene glycol, glycidyl ether of ethylene glycol, diethylene glycol, triethylene glycol and polyethylene glycol, glycidyl of propylene glycol, dipropylene glycol, tripropylene glycol and polypropylene glycol Ether, tetramethylene glycol, ditetramethylene glycol, tritetramethylene glycol, glycidyl ether of polytetramethylene glycol, glycidyl ether of 1,4-butanediol, glycidyl ether of 1,6-hexanediol, glycidyl ether of neopentyl glycol Etc., preferably polypropylene Glycidyl ethers of diglycidyl ether and neopentyl glycol recall is used.

  The other compounds used for synthesizing the component (A) in the present invention are phenolic compounds such as biphenol, bisphenol A, bisphenol F, bisphenol S, tetramethylbiphenol, tetramethylbisphenol A, tetramethyl. Bisphenol F, tetramethylbisphenol S, tetrabromobiphenol, tetrabromobisphenol A, tetrabromobisphenol F, tetrabromobisphenol S, and the like can be mentioned, and biphenol is preferably used.

  The component (A) is synthesized using a known technique so that the number average molecular weight is usually in the range of 600 to 5000, preferably in the range of 800 to 4500, more preferably in the range of 900 to 4000. The resulting epoxy resin has a structure in which alkylene and phenolic moieties are alternately arranged. That is, since the alkylene part is excellent in flexibility and the phenolic part is excellent in strength, it has a structure in which the flexible part and the high-strength part appear alternately.

  In conventional photocationic curing, even if a compound having flexibility and a compound having high strength are blended at the time of blending, the cured product after irradiation with active energy rays has flexibility and a high strength. The reaction could not be controlled to alternate sites.

  In the present invention, by adding a compound having a structure in which a flexible part and a high-strength part appear alternately, the structure is maintained even after active energy ray curing, and contributes to improvement of toughness. When the molecular weight is smaller than 600, it becomes difficult to have a structure in which flexible portions and high-strength portions appear alternately, and toughness cannot be expressed. On the other hand, when the molecular weight is greater than 5000, the viscosity of the compound increases to several hundreds of thousands mPa · s (25 ° C.). Therefore, when a large amount of the compound is blended, the viscosity of the compounded resin increases and handling becomes difficult. When blended, the effect of toughness is not sufficiently exhibited.

  In particular, when biphenol is used as the phenolic compound, biphenyl groups having a planar structure have weak bonds due to intermolecular forces, which serve to relieve stress and greatly contribute to improvement of toughness.

  As the compound used in the active energy ray-curable resin composition of the present invention, <(A) component>, photopolymerization initiator <hereinafter also referred to as (E) component>, photocationic polymerizable resin having an oxirane ring <below , Also referred to as (B) component> as an essential component, but in addition to these, a photo-radical polymerizable resin having a (meth) acryloyl group <hereinafter also referred to as (C) component>, and a polyol compound <hereinafter, ( D) Also referred to as component>, other components can be blended.

  The blending ratio of the component (A) is usually 5 to 50% by weight, preferably 10 to 45% by weight, and more preferably 15 to 40% by weight. When the component (A) is too small, sufficient toughness is not exhibited, which is not preferable. On the other hand, an excessive amount is not preferable because the curing rate of the active energy ray-curable resin becomes slow.

  The photocationically polymerizable resin <component (B)> having an oxirane ring is an organic compound having an oxirane ring that undergoes a polymerization reaction or a crosslinking reaction when irradiated with light in the presence of a photopolymerization initiator.

  Examples of the resin that can be used as the component (B) include glycidyl ether type epoxy resins and alicyclic epoxy resins having at least one, preferably two or more oxirane rings.

  The glycidyl ether type epoxy resin is not particularly limited, but glycerin, diglycerin, polyglycerin, diethylene glycol, polyethylene glycol, polyglycidyl ether such as sorbitol, and glycerin, diglycerin, polyglycerin, diethylene glycol, polyethylene glycol. , Polyglycidyl ethers of alkylene oxide adducts such as sorbitol, butyl glycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, Trimethylolpropane polyglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogen Phenol novolac type epoxy resin, phenyl glycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, halogenated cresol Examples thereof include novolac type epoxy resins and phenol novolac type epoxy resins.

  The alicyclic epoxy resin is not particularly limited, but 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, epoxidized polybutadiene Preferably, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate is used.

  The blending ratio of component (B) is usually 45 to 90% by weight, preferably 50 to 85% by weight, and more preferably 55 to 80% by weight. When the component (B) is too small, the active energy ray-curable resin has a high viscosity and is difficult to handle. On the other hand, an excessive amount is not preferable because sufficient toughness is not exhibited.

  The photo-radically polymerizable resin <(C) component> having a (meth) acryloyl group is a radical polymerizable organic compound that undergoes a polymerization reaction or a crosslinking reaction when irradiated with light in the presence of a radical photopolymerization initiator. .

  Examples of the resin that can be used as the component (C) include resins having at least one, preferably two or more (meth) acryloyl groups.

  Specific examples of the (meth) acrylate compound include dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, alkyl modified dipenta Erythritol penta (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, alkyl-modified Pentaerythritol tri (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol penta (meth) acrylate., Preferably trimethylolpropane trimethacrylate are used.

  The above-mentioned compound is not limited to a monomer but may be an oligomerized product, and the component (C) can be constituted by one kind alone or in combination of two or more kinds. The proportion of the component (C) in the resin component of the present invention is usually 0 to 30% by weight, preferably 0 to 20% by weight. When the component (C) is excessive, the curing rate of the active energy ray-curable resin in air is not preferable because it is slow.

  The polyol compound <(D) component> is an organic compound having three or more hydroxyl groups in one molecule. This component is a component necessary for imparting mechanical properties of the resin cured product, particularly toughness, and a cured product having a characteristic in elongation can be obtained by blending.

  Examples of the resin that can be used as the component (D) include trimethylolpropane, glycerin, ethylene oxide adduct of propylene oxide or propylene oxide adduct, diglycerin, ethylene oxide adduct of propylene oxide or propylene oxide adduct, triglycerin. Ethylene oxide adducts or propylene oxide adducts, polyglycerol ethylene oxide adducts or propylene oxide adducts of glycerin tetramer or higher, and diglycerin propylene oxide adducts are preferably used.

  The component (D) can be used as a component (D) alone or in combination of two or more. The proportion of the component (D) in the resin component of the present invention is usually 0 to 30% by weight, preferably 0 to 20% by weight. When the component (D) is excessive, the curing rate becomes slow and the strength of the cured product becomes weak.

  The photopolymerization initiator <(E) component> used in the present invention is activated by irradiating active energy rays, generates cationic species or radical species, and cationically polymerizes the components (A) and (B). It is a compound that radically polymerizes the compound or component (D).

Among the photopolymerization initiators, the photocation polymerization initiator that generates a cationic species is not particularly limited, but onium salts such as aromatic iodonium salts, aromatic sulfonium salts, diazonium salts, and iron-allene complexes. And the like, and the like. The photoacid generator has the general formula (1)
_{^{(R 1 a R 2 b R}} 3 c R 4 d Z) + m (MX n-m) -m (1)
[In the formula (1), the cation is an onium salt, Z is S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, or N≡N, and R ¹ , R ² , R ³ and R ⁴ are the same or different organic groups. a, b, c, and d are each an integer of 0 to 3, and (a + b + c + d) is equal to the valence of Z. M is a metal or metalloid constituting the central atom of the halide complex. For example, B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co and the like. X is a halogen atom. m is the net charge of the halide complex ion and n is the number of atoms in the halide complex ion. It is represented by

Specific examples of the cation (R ¹ _a R ² _b R ³ _c R ⁴ _d Z) in the above general formula include aromatic sulfonium, aromatic diazonium, aromatic iodonium, aromatic ammonium, and [(1-methylethyl) benzene. ] -Iron cations and the like. Specific examples of the anion (MX _n-m ) include tetrafluoroborate (BF ₄ ), hexafluoroantimonate (SbF ₆ ), hexafluorophosphate (PF ₆ ), hexafluoroarsenate (AsF ₆ ), hexachloroantimonate (SbCl ₆ ) and the like.

Moreover, the onium salt which has the anion represented by general formula [MXn (OH) _< ^- >] can also be used. Further, tetrakispentafluorophenylborate [B (C ₆ F ₅ ) ₄ ⁻ ], perchlorate ion (ClO ₄ ⁻ ), trifluoromethanesulfonate ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ), Onium salts having other anions such as toluenesulfonate ions can also be used.

  Among such onium salts, useful onium salts are as follows. That is, aromatic sulfonium salts include bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate, bis [4- (Diphenylsulfonio) phenyl] sulfide bistetrafluoroborate, bis [4- (diphenylsulfonio) phenyl] sulfidetetrakis (pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4 -(Phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetrafluoroborate, diphenyl-4- (phenylthio) phene Rusulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bishexafluoroantimony Bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bistetrafluoroborate, bis [4- (di (4- ( -Hydroxyethoxy)) phenylsulfonio) phenyl] sulfide tetrakis (pentafluorophenyl) borate and the like; aromatic iodonium salts include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium Tetrakis (pentafluorophenyl) borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (penta Fluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) 4) phenyliodonium hexafluorophosphate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4 -Methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate and the like; aromatic diazonium salts include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, Phenyldiazonium tetrakis (pentafluorophenyl) borate, etc .; aromatic ammonium salts include 1-benzyl-2-cyanopyridinium hexafluorophosphine 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl-2-cyanopyridinium tetrakis (pentafluorophenyl) borate, 1- (naphthyl) Methyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, 1- (naphthylmethyl) -2-cyanopyridinium tetrafluoroborate, 1- (naphthylmethyl)- 2-cyanopyridinium tetrakis (pentafluorophenyl) borate and the like; (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe salt includes (2,4-cyclopentadiene-1 -Ill) [(1-Meth Ruethyl) benzene] -Fe (II) hexafluorophosphate, (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe (II) hexafluoroantimonate, (2,4- Cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe (II) tetrafluoroborate, (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe (II ) Tetrakis (pentafluorophenyl) borate and the like.

  Among the photopolymerization initiators, the photoradical polymerization initiator that generates radical species is not particularly limited. For example, acetophenone, acetophenone benzyl ketal, anthraquinone, 1- (4-isopropylphenyl) -2-hydroxy- 2-methylpropan-1-one, carbazole, xanthone, 4-chlorobenzophenone, 4,4′-diaminobenzophenone, 1,1-dimethoxydeoxybenzoin, 3,3′-dimethyl-4-methoxybenzophenone, thioxanthone compounds, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-2-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, Triphenylamine, 2,4,6-trimethylbenzo Rudiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-tri-methylpentylphosphine oxide, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- Phenylpropan-1-one, 2,2′-dimethoxy-1,2-diphenylethane-1-one, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone, Michler's ketone, 3-methylacetophenone, 3, 3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone (BTTB), and combinations of BTTB with xanthene, thioxanthene, coumarin, ketocoumarin and other dye sensitizers It can gel.

  Said photocationic polymerization initiator and radical photopolymerization initiator can comprise (E) component individually by 1 type or in combination of 2 or more types. The proportion of the component (E) in the resin component of the present invention is usually 0.1 to 10% by weight, preferably 0.2 to 7% by weight, and more preferably 0.3 to 5% by weight. . When the component (E) is too small, the curing rate is slow, which is not preferable. Moreover, when it is excessive, the curing rate is not faster than a certain value, and the cost of the compounded resin is increased, which is not preferable.

  The active energy ray-curable resin composition of the present invention may contain other components other than the components (A) to (E) as long as the photocurability is not impaired. Such components include cationically polymerizable resins such as vinyl ether and oxetane resins, photosensitizers composed of amines, thioxanthones, anthracenes, phenothiazines, and carbazoles, and decompose to generate acids such as p-toluenesulfonic acid. Acid growth agents, acid supplements such as alkali metal hydroxides, alkaline earth metal carbonates, alkaline earth metal phosphates, colorants, anti-aging agents, leveling agents, surfactants, UV absorbers, silane coupling agents , Inorganic fillers, resin particles, wettability improvers and the like.

  The active energy ray in the present invention is not particularly limited, and examples thereof include microwaves, infrared rays, visible light, ultraviolet rays, X-rays, γ rays, electron beams, etc. UV rays with relatively high energy are used.

  The ultraviolet ray is not particularly limited as a light source such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a metal halide lamp, a solid-state laser, or a gas laser, but preferably a high-pressure mercury lamp or a solid-state laser is used. Is done.

  Hereinafter, the details of the present invention will be specifically described with reference to synthesis examples and examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

<Example 1>
In a 1 L separable flask equipped with a stirrer and a thermometer, 272 g of diglycidyl ether of polypropylene glycol (m = 7) (SR-4PG (manufactured by Sakamoto Pharmaceutical Co., Ltd.)), 28 g of biphenol, triethylbenzylammonium chloride 1 0.0 g was taken and reacted at 170 ° C. for 8 hours under a nitrogen stream. After completion of the reaction, a liquid product (hereinafter abbreviated as A-1) having an epoxy equivalent of 520 g / eq and a viscosity of 1050 mPa · s (25 ° C.) was obtained. The number average molecular weight of A-1 was 1000 in terms of standard polystyrene measured by gel permeation chromatography.

<Example 2>
The reaction was conducted under the same conditions as in Example 1 except that the amount of diglycidyl ether of polypropylene glycol (m = 7) (SR-4PG (manufactured by Sakamoto Pharmaceutical Co., Ltd.)) was changed to 244 g and the amount of biphenol was changed to 56 g. And a liquid product (hereinafter abbreviated as A-2) having an epoxy equivalent of 1700 g / eq and a viscosity of 138000 mPa · s (25 ° C.) was obtained. The number average molecular weight of A-2 was 3000 in terms of standard polystyrene measured by gel permeation chromatography.

<Example 3>
Instead of diglycidyl ether of polypropylene glycol (m = 7), 270 g of dipropylidyl ether of tripropylene glycol (m = 3) (SR-TPG (manufactured by Sakamoto Pharmaceutical Co., Ltd.)) and the amount of biphenol were changed to 30 g. The reaction was conducted under the same conditions as in Example 1 to obtain a liquid product (hereinafter abbreviated as A-3) having an epoxy equivalent of 315 g / eq and a viscosity of 840 mPa · s (25 ° C.). The number average molecular weight of A-3 was 600 in terms of standard polystyrene measured by gel permeation chromatography.

<Example 4>
Example 1 except that 230 g of diglycidyl ether of neopentyl glycol (SR-NPG (manufactured by Sakamoto Pharmaceutical Co., Ltd.)) and 70 g of biphenol were substituted for the diglycidyl ether of polypropylene glycol (m = 7). The reaction was carried out under the same conditions as above to obtain a liquid product (hereinafter abbreviated as A-4) having an epoxy equivalent of 420 g / eq and a viscosity of 140,000 mPa · s (25 ° C.). The number average molecular weight of A-4 was 900 in terms of standard polystyrene measured by gel permeation chromatography.

<Comparative Example 1>
The reaction was carried out under the same conditions as in Example 3 except that the amount of diglycidyl ether of tripropylene glycol (m = 3) (SR-TPG (manufactured by Sakamoto Pharmaceutical Co., Ltd.)) was changed to 278 g and the amount of biphenol was changed to 22 g. And a liquid product (hereinafter abbreviated as A-5) having an epoxy equivalent of 285 g / eq and a viscosity of 560 mPa · s (25 ° C.) was obtained. The number average molecular weight of A-5 was 500 in terms of standard polystyrene measured by gel permeation chromatography.

<Example 5>
According to the formulation shown in Table 1, A-1 obtained in Example 1 was 19% by weight, bisphenol F type diglycidyl ether “Epicoat 807” (manufactured by Japan Epoxy Resin Co., Ltd.), 80% by weight, triarylsulfonium hexa Fluoroantimonate salt-based photocationic polymerization initiator “SP-170” (manufactured by Asahi Denka Kogyo Co., Ltd.) 1 wt% is charged into a stirring vessel and stirred at 50 ° C. for 1 hour, whereby a colorless transparent liquid composition (Resin composition of the present invention) was obtained.
The obtained resin composition was applied on a PET film with a bar coater so as to have a film thickness of about 200 μm. Subsequently, 1.0 J / cm ² (365 nm) was irradiated with a high-pressure mercury lamp, and the condition was adjusted under constant temperature and humidity at a temperature of 23 ° C. and a humidity of 50% for one day.
The physical properties of the obtained cured film were evaluated by the following evaluation methods. The results are shown in Table 1.

<Examples 6 to 10>
Example 5 except that (A), (B), (E) were mixed according to the formulation shown in Table 1, and (C), (D) and other components were mixed with stirring as required. In the same manner as above, after obtaining a liquid composition (resin composition of the present invention), a cured film was prepared, and physical properties were evaluated. The results are shown in Table 1.

<Comparative Examples 2-5>
According to the formulation shown in Table 1, a liquid composition was obtained in the same manner as in Example 5 except that each constituent component was stirred and mixed, and then a cured film was prepared and evaluated for physical properties. The results are shown in Table 1.

Below, the evaluation method in the above-mentioned Example etc. is demonstrated.
(Tensile strength, breaking elongation, yield elongation, initial elastic modulus)
Using the AUTO GRAPH S-2000 manufactured by Shimadzu Corporation, the obtained cured film was measured under the conditions of a tensile speed of 1 mm / min and a distance between marked lines of 50 mm according to JIS K7127. The initial elastic modulus was calculated using the tensile strength at an elongation of 2.5%.

  As shown in Table 1 above, the resin compositions shown in the examples are broken from the elongation at break (X) to the yield elongation (Y) (however, a cured product that does not exhibit yield elongation is broken at the maximum load. From the fact that the value obtained by subtracting the elongation at maximum load is large, it was found that the resin is excellent in impact resistance and excellent in toughness having both strength and elongation.

It can be blended and used in fields where the toughness of the cured product is required, such as the optical modeling field, coatings, resists, adhesives, paints and the like.

Claims (1)

It is a compound obtained by reacting glycidyl ether of glycol with a phenol compound,

(M is a natural number of 1 to 20, n is a natural number of 1 to 14, X is an alkyl group, a and b are integers of 0 to 4, _{G 1} and _{G 2} are glycidyl groups or a hydrogen atom a halogen atom or C1~5 (However, G ₁ and G ₂ are not simultaneously hydrogen atoms), R ₁ is a C1-10 alkylene group or alkylidene group, R ₂ is an alkylene group, alkylidene group, sulfonyl group, oxygen atom or atomic group. An epoxy resin having a number average molecular weight in the range of 600 to 5000, a photopolymerization initiator, and a photocationically polymerizable resin having an oxirane ring (shown by [Chemical Formula 1]). , Excluding epoxy resins having a number average molecular weight in the range of 600 to 5000.) .