JP2012001690A - Photocurable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable resin composition which excels in heat resistance and transparency, and can suppress yellowing at the time of curing, and to provide its cured product.SOLUTION: The photocurable resin composition includes (1) 100 pts.mass of a cationically polymerizable organic substance expressed by general formula (I) or the like, and (2) 0.001-10 pts.mass of an energy ray-sensitive cationically polymerizable initiator, and does not include an acrylate compound. In addition, a cured product which is obtained by curing the photocurable resin composition is disclosed. In the formula, Zdenotes a single bond or a 1-4C alkylene group, a methylene group in the alkylene group may be a straight chain, may have a branched chain, or may be annular, may be substituted by a methyl group, or may be interrupted by -CO-O- or -O-CO-, Rand Reach independently denote a halogen atom, a and b each independently denote the number of 0-10, and p denotes the number of 0-5.

Description

  The present invention relates to a photocurable resin composition and a cured product obtained by irradiating the photocurable resin composition with active energy rays. The photocurable resin composition is particularly useful for optical members.

  Photocurable resin compositions are used in the fields of inks, paints, various coating agents, adhesives, optical members, and the like.

For example, Patent Literature 1 below discloses a photocurable resin composition containing an epoxy resin, a photocationic polymerization initiator, and an acrylate component, and Patent Literature 2 below discloses an epoxy resin having a specific structure and an acryloyl group. A photocurable liquid resin composition containing a contained compound as an essential component is disclosed, and the following Patent Document 3 discloses an optical waveguide resin composition containing an epoxy resin having a specific structure. Discloses an epoxy compound having a cycloalkane skeleton, a photocationic polymerization initiator, and an adhesive for an optical component containing an aliphatic hydrocarbon compound. Patent Document 5 listed below requires a cationically polymerizable compound as an essential component. A curable resin composition including a resin composition, a cationic polymerization initiator, and metal oxide particles is disclosed.
However, none of the photocurable resin compositions described in these documents has sufficient heat resistance and transparency.

JP-A-8-73559 JP-A-11-240939 JP 2003-212961 A JP 2007-284500 A JP 2009-132934 A

  Accordingly, an object of the present invention is to provide a photocurable resin composition that is excellent in heat resistance and transparency and can suppress yellowing during curing, and a cured product thereof.

  The present invention includes (1) 100 parts by mass of a cationically polymerizable organic material represented by any one of the following general formulas (I) to (IV), and (2) 0.001 to 10 parts by mass of an energy ray-sensitive cationic polymerization initiator. The above-mentioned object is achieved by providing a photocurable resin composition containing no part and no acrylate compound.

（式中、Ｚ¹は、単結合又は炭素原子数１〜４のアルキレン基を表し、該アルキレン基中のメチレン基は直鎖であっても分岐鎖を有していても環状であってもよく、メチル基で置換されていてもよく、−ＣＯ−Ｏ−又は−Ｏ−ＣＯ−で中断されていてもよく、Ｒ¹及びＲ²は、それぞれ独立に、ハロゲン原子を表し、ａ及びｂは、それぞれ独立に、０〜１０の数であり、ｐは、０〜５の数である。）

(In the formula, Z ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms, and the methylene group in the alkylene group may be linear, branched or cyclic. It may be substituted with a methyl group, interrupted with —CO—O— or —O—CO—, and R ¹ and R ² each independently represents a halogen atom, and a and b Are each independently a number from 0 to 10, and p is a number from 0 to 5.)

（式中、Ｚ²は、単結合、−Ｏ−ＣＨ₂−ＣＯ−又は炭素原子数１〜４のアルキレン基を表し、該アルキレン基中のメチレン基はメチル基で置換されていてもよく、Ｒ³及びＲ⁴は、それぞれ独立に、ハロゲン原子を表し、ｍ及びｎは、それぞれ独立に、０〜９の数である。）

(In the formula, Z ² represents a single bond, —O—CH ₂ —CO— or an alkylene group having 1 to 4 carbon atoms, and the methylene group in the alkylene group may be substituted with a methyl group; R ³ and R ⁴ each independently represent a halogen atom, and m and n are each independently a number from 0 to 9.)

（式中、ｓは０〜１０の数である。）

(In the formula, s is a number from 0 to 10.)

  Moreover, this invention provides the hardened | cured material obtained by hardening | curing the said photocurable resin composition.

  The photocurable resin composition of the present invention is particularly useful as an optical member because it is excellent in heat resistance and transparency and can suppress yellowing during curing.

Hereinafter, the photocurable resin composition of the present invention and the cured product obtained by curing the photocurable resin composition will be described in detail.
The photocurable resin composition of the present invention contains (1) a cationic polymerizable organic substance and (2) an energy ray sensitive cationic polymerization initiator, and does not contain an acrylate compound.

  The (1) cationically polymerizable organic substance used in the present invention is a compound that is activated by light irradiation, and (2) is a compound that undergoes a polymerization or a crosslinking reaction with an energy ray-sensitive cationic polymerization initiator. ) To (IV).

Examples of the alkylene group having 1 to 4 carbon atoms represented by Z ¹ in the general formula (I) and Z ² in the general formula (II) include methylene, ethylene, propylene, methylethylene, butylene, 1- Examples include methylpropylene and 2-methylpropylene.

Examples of the halogen atom represented by R ¹ and R ² in the general formula (I) and R ³ and R ⁴ in the general formula (II) include fluorine, chlorine, bromine and iodine.

  Among the compounds represented by any one of the above general formulas (I) to (IV), the compounds represented by the above general formulas (I) and (II) are preferable from the viewpoint of production cost and transparency. The compound represented by (II) is more preferable. Moreover, you may use the compound represented by either of the said general formula (I)-(IV) individually by 1 type or in mixture of 2 or more types.

Next, (2) the energy ray sensitive cationic polymerization initiator used together with the above (1) cationic polymerizable organic substance will be described.
The energy ray-sensitive cationic polymerization initiator (2) used in the present invention is a compound capable of releasing a substance that initiates cationic polymerization upon irradiation with active energy rays as described below. Preferably, it is a double salt that is an onium salt that releases a Lewis acid upon irradiation with active energy rays, or a derivative thereof. A typical example of such a compound is represented by the general formula [A] ^{r +} [B] ^r- (wherein A represents a cationic species, B represents an anionic species, and r represents a valence). Mention may be made of the cation and anion salts represented.

Here, the cation [A] ^{r +} is preferably onium, and the structure thereof can be represented by, for example, the general formula [(R ⁷ ) _a Q] ^{r +} .

In the above formula, R ⁷ is an organic group having 1 to 60 carbon atoms and optionally containing any number of atoms other than carbon atoms. a is an integer of 1-5. The a R ^{7 s} may be the same or different independently. Further, at least one is preferably an organic group as described above having an aromatic ring. Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N = N. Further, when the valence of Q in the cation [A] ^{r +} is q, the relationship r = a−q needs to be satisfied (however, N = N is treated as a valence of 0).

The anion [B] ^r− is preferably a halide complex, and the structure can be represented by, for example, the general formula [LX _b ] ^r− .

In the above formula, L is a metal or metalloid which is a central atom of a halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, It is represented by V, Cr, Mn or Co. X is a halogen atom. b is an integer of 3-7. Further, when the valence of L in the anion [B] ^r− is p, it is necessary that the relationship r = b−p holds.

Specific examples of the anion represented by the above general formula [LX _b ] ^r- include tetrakis (pentafluorophenyl) borate, tetra (3,5-difluoro-4-methoxyphenyl) borate, tetrafluoroborate (BF ₄ ). ^-, hexafluorophosphate (PF ₆₎ ^-, hexafluoroantimonate (SbF ₆₎ ^-, hexafluoroarsenate (AsF ₆₎ ^-, hexachloroantimonate (SbCl ₆₎ ^-, and the like.

Further, as the anion [B] ^r− , _one having a structure represented by the general formula [LX _b-1 (OH)] ^r− can be preferably used. In the formula, L, X and b are the same as the above general formula [LX _b ] ^r− . Other anions [B] ^r− that can be used include perchlorate ion (ClO ₄ ) ⁻ , trifluoromethyl sulfite ion (CF ₃ SO ₃ ) ⁻ , fluorosulfonate ion (FSO ₃ ) ⁻ , Examples include toluene sulfonate anion, trinitrobenzene sulfonate anion, camphor sulfonate, nonafluorobutane sulfonate, hexadecafluorooctane sulfonate, tetraarylborate, tetrakis (pentafluorophenyl) borate, and the like. .

  In the present invention, among these onium salts, it is particularly effective to use the following aromatic onium salts (a) to (c). Among these, one of them can be used alone, or two or more can be mixed and used.

  (I) Aryl diazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate

  (B) Diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate, tricumyliodonium tetrakis (pentafluorophenyl) borate, etc. Diaryliodonium salt

  (C) Triphenylsulfonium hexafluoroantimonate, tris (4-methoxyphenyl) sulfonium hexafluorophosphate, diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate, 4, 4′-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluoroantimonate, 4,4′-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluorophosphate, 4,4′-bis [di ( β-hydroxyethoxy) phenylsulfonio] phenyl sulfide-bis-hexafluoroantimonate, 4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] pheny Sulfide-bis-hexafluorophosphate, 4- [4 ′-(benzoyl) phenylthio] phenyl-di- (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- [4 ′-(benzoyl) phenylthio] phenyl-di- Triarylsulfonium salts such as (4-fluorophenyl) sulfonium hexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) phenyl-di- (4-fluorophenyl) sulfonium hexafluoroantimonate, and diphenyl-4- Triarylsulfonium salts such as a mixture of thiophenoxyphenylsulfonium hexafluoroantimonate and 4,4′-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluorophosphate

Other preferable examples include (η ⁵ -2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene] -iron. -Iron-arene complexes such as hexafluorophosphate, aluminum complexes such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salicylaldehyde) aluminum and silanols such as triphenylsilanol The mixture of these can also be mentioned.

  Among these, it is preferable to use a diaryl iodonium salt, a triarylsulfonium salt, and an iron-arene complex from the viewpoint of practical use and photosensitivity.

  In the photocurable resin composition of the present invention, the amount of (2) the energy ray-sensitive cationic polymerization initiator used relative to (1) the cationic polymerizable organic substance is based on (1) 100 parts by mass of the cationic polymerizable organic substance. (2) Energy ray sensitive cationic polymerization initiator 0.001-10 mass parts, Preferably it is 0.1-5 mass parts, More preferably, it is 1-3 mass parts. (2) If the amount of the energy ray-sensitive cationic polymerization initiator used is less than 0.001, curing tends to be insufficient, and if it exceeds 10 parts by mass, various physical properties such as refractive index and strength of the cured product are adversely affected. May give.

  The photocurable resin composition of the present invention contains (1) a cationic polymerizable organic substance and (2) an energy ray-sensitive cationic polymerization initiator, and does not contain an acrylate compound. When an acrylate compound is contained, a problem arises in that, when a high temperature treatment such as a solder reflow process is performed, the heat resistance is low.

  The acrylate compound that is not used in the photocurable resin composition of the present invention is not particularly limited, and includes compounds generally referred to as acrylate compounds and derivatives thereof. Further, “not containing an acrylate compound” includes not only the case where no acrylate compound is contained, but also the case where it is contained less than 5% by mass in the photocurable resin composition of the present invention.

(3) Antioxidant can be used for the photocurable resin composition of this invention as needed. Examples of the antioxidant include 2,6-di-t-butylphenol, 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butyl-4-methylphenol, 2,6-di- t-butyl-4-ethylphenol, 2,4,6-tri-t-butylphenol, 2,6-di-t-butyl-4-s-butylphenol, 2-t-butyl-4-methoxyphenol, vitamin E 2,6-di-t-butyl-4-hydroxymethylphenol, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-butylphenyl) propionate, 2-t-butyl-6- (3′-t-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, propyl gallate, octyl gallate, lauryl gallate, 2,2′-methylene bis (4- Til-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'- Methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dihydroxy-3,3′-di (α-methylcyclohexyl) -5,5′-dimethyldiphenylmethane, 2,2′-ethylidene-bis (4 , 6-di-tert-butylphenol), 2,2′-butylidenebis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol- N-bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], 1,6-hexanediol bis [3- (3,5- Di-t-butyl-4-hydroxyphenyl) propionate], catechol, tert-butylcatechol, 2-butyl-4-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, 4,4′-thiobis (6-t-butyl-m-cresol), 4,4′-thiobis (3-methyl-6-t-butylphenol), 4,4′-thiobis (4-methyl-6-t-butylphenol), bis ( 3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate)] methane, 3,9- Bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,1 -Tetraoxaspiro [5,5] undecane, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [3- (3,5-di-tert -Butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester, 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5- Bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hex -Tert-butyl-a, a ', a "-(mesitylene-2,4,6-tolyl) tri-p-cresol, calcium diethylbis [[[3,5-bis (1,1-dimethylethyl)- 4-hydroxyphenyl] methyl] phosphonate, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate ] Hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)- 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris [(4-tert-butyl-3-hydroxy-2 , 6-Xylyl) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, reaction product of N-phenylbenzenamine and 2,4,6-trimethylpentene 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol, 2,6-diphenyl-4-octadecyloxyphenol, Stearyl (3,5-ditert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, 2-octylthio-4,6-di (3,5 -Di-tert-butyl-4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3-bis (4- Droxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (2,6-ditert-butylphenol), tridecyl-3,5-ditert-butyl-4-hydroxybenzylthioacetate 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl) -5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5- Di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trime Benzene, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 2-tert-butyl-4-methyl-6- (2-acryloyloxy- 3-tert-butyl-5-methylbenzyl) phenol, phenolic antioxidants such as phenolic compounds such as picric acid; triphenyl phosphite, tris (2,5-ditert-butylphenyl) phosphite, diphenylnonyl Phenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, trisnonylphenyl phosphite, tris (dinonylphenyl) phosphite, tris (mono, di-mixed nonylphenyl) phosphite, di (nonyl) Phenyl) pentaerythritol diphosphite, diphenyl acid phosphite Diphenylisooctyl phosphite, 2,2′-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, diphenyl indecyl phosphite, diphenyl mono (tridecyl) phosphite, phenyl diisodenyl phosphite Phyto, phenyl di (tridecyl) phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, tris (2-ethylhexyl) phosphite Phyto, Tris (indecyl) phosphite, Tris (tridecyl) phosphite, Dibutyl hydrogen phosphite, Trilauryl trithiophosphite, 4,4′-butylidenebis (3-methyl-6-t Butylphenyl) di-tridecyl phosphite, 3,5-di-t-butyl-4-hydroxybenzyl phosphite diethyl ester, tris [2-[[2,4,8,10-tetra-tert-butyldibenzo [ d, f] [1,3,2] dioxaphosphine-6-yl] oxy] ethyl] amine, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis ( Neopentyl glycol), 1,4-cyclohexanedimethyldiphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,5-ditert-butylphenyl) pentaerythritol diphosphite Bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetra (C12-15 mixed alkyl) -4,4'-isopropylidene diphenyl phosphite, bis [2,2'-methylenebis (4 , 6-Diamylphenyl)]-isopropylidene diphenyl phosphite, tetratridecyl 4,4'-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) 1,1,3- Tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, tris (2-[(2,4,7 , 9-Tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphosphine Pin-6-yl) oxy] ethyl) amine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-butyl-2-ethylpropanediol, 2,4,6- Tri-tert-butylphenol monophosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid, tetrakis (2,4-di-tert-butylphenyl) [1 , 1-Bisphenyl] -4,4′-diylbisphosphonite, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra -Phosphorus antioxidants such as tert-butyldibenz [d, f] [1,3,2] dioxaphosphine; dilauryl-3,3'-thiodipropionic acid ester Ditridecyl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, lauryl stearyl-3,3′- Thiodipropionic acid ester, pentaerythritol tetra (β-lauryl thiopropionate) ester, stearyl thiopropionamide, dioctadecyl disulfide, 2-mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1,1 Sulfur-based antioxidants such as' -thiobis (2-naphthol); N, N ', N ", N"'-tetrakis- (4,6-bis (butyl- (N-methyl-2,2,6, 6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,1 0-diamine, dibutylamine, 1,3,5-triazine, N, N′-bis- (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine, N- (2 , 2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2, 4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol polymer, [bisdecanoic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidyl) Ester, 1,1-dimethyl Reaction product of ethyl hydroperoxide and octane (70%)]-polypropylene (30%), bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1 -Dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, bis (2,2,6,6-tetramethyl-4- Piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2- [3- (3,5-di-tert-butyl-4-hydroxy] Phenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, -Benzoyloxy-2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2 Hindered amine antioxidants such as 1,4-dione; β-naphthoquinone, 2-methoxy-1,4-noftquinone, methylhydroquinone, hydroquinone, hydroquinone monomethyl ether, mono-tert-butylhydroquinone, 2,5-di-tert- Quinone compounds such as butyl hydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-di-tert-butyl-p-benzoquinone; alkylated diphenylamines such as 4,4′-dioctyldiphenylamine Alkylated N, N′-diallyl-p-phenylenedia , N-phenyl-β-naphthylamine, N, N′-di-2-naphthyl-p-phenylenediamine, aromatic amine-based antioxidants such as phenothiazine; citric acid, lactone-based compounds, vitamin E-based compounds, etc. Among these, from the viewpoint of colorability, a phenolic antioxidant is preferable, and a hindered phenolic antioxidant is more preferable.

  As the hindered phenol-based antioxidant, among the compounds exemplified as the phenol-based antioxidant, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-butylphenyl) propionate, 2-t-butyl-6- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 1,6-hexanediol bis [3- (3,5-di- -T-butyl-4-hydroxyphenyl) propionate], bis (3,5-di-t-butyl-4-hydroxybenzyl) sulfide, tetrakis [methylene-3- (3 ', 5'-di-t-butyl) -4-hydroxyphenyl) propionate)] methane, 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy Ci] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate], thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-) -Tert-butyl-4-hydroxyphenyl) propionamide], 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester, diethyl [[3,5-bis (1 , 1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″ -(Mesitylene-2,4,6-tolyl) tri-p-cresol, calcium diethylbis [[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, ethylenebis ( Oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1 , 3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6- Diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5 Di-tert-butyl-4-hydroxybenzyl) phosphonate, 2-octylthio-4,6-di (3,5-di-tert-butyl-4-hydroxyphenoxy) -s-triazine, tridecyl-3,5-di-tertiary Butyl-4-hydroxybenzylthioacetate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl) -4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, etc. Among these, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,5-bis ( 1,1-Dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl esters, and stearyl (3,5-ditert-butyl-4-hydroxyphenyl) propionate are preferred.

  In the photocurable resin composition of the present invention, the amount of (3) the antioxidant used relative to (1) the cationically polymerizable organic substance is preferably (1) relative to 100 parts by mass of the cationically polymerizable organic substance ( 3) It is 0-10 mass parts of antioxidant, More preferably, it is the range of 0-5 mass parts. (3) If the amount of the antioxidant used exceeds 10 parts by mass, no further effect is observed, which is not preferable.

  In order to enhance transparency while suppressing a decrease in heat resistance, (4) an alcohol compound may be added to the photocurable resin composition of the present invention. Examples of the alcohol compound include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, tert-pentanol, n-hexanol, tert-hexanol, n-heptanol, isoheptanol, tert-heptanol, n-octanol, 2-ethylhexanol, tert-octanol, n-nonyl alcohol, isononyl alcohol, tert-nonyl alcohol, n-decanol, isodecanol, lauryl alcohol, myristyl alcohol , Palmityl alcohol, stearyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl Monohydric alcohols such as ether and dipropylene glycol monobutyl ether and alkylene oxide adducts thereof; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4- Butanediol, 1,5-pentanediol, neopentyl glycol, isoprene glycol (3-methyl-1,3-butanediol), 1,2-hexanediol, 1,6-hexanediol, 3-methyl-1,5 -Pentanediol, 1,2-octanediol, octanediol (2-ethyl-1,3-hexanediol), 2-butyl-2-ethyl-1,3-propanediol, 1,2-decanediol, 1, 2-dodecanediol, 1,2- Aliphatic diols such as tradecanediol, 1,2-hexadecanediol, 1,2-octadecanediol, 1,12-octadecanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedi Divalent alcohols such as methanol, hydrogenated bisphenol A, hydrogenated bisphenol F, spiro skeleton-containing alcohols, alicyclic alcohols such as tricyclodecane dimethylol and pentacyclopentadecane dimethylol, and their alkylene oxide adducts, sorbide, methyldiethanolamine, etc. Alcohols and their alkylene oxide adducts; glycerin, polyglycerin, 1,2,3-butanetriol, 1,2,4-butanetriol, 2-methyl-1,2,3-propanetriol, 1,2,3 -Pentanetriol, 1,2,4-pentanetriol, 1,3,5-pentanetriol, 2,3,4-pentanetriol, 2-methyl-2,3,4-butanetriol, trimethylolethane, ditrimethylol Propane, 2,3,4-hexanetriol, 2-ethyl-1,2,3-butanetriol, trimethylolethane, trimethylolpropane, 4-propyl-3,4,5-heptanetriol, pentamethylglycerin (2 , 4-dimethyl-2,3,4-pentanetriol), triethanolamine, triisopropanolamine, polycaprolactone triol and other trihydric alcohols and their alkylene oxide adducts; pentaerythritol, dipentaerythritol, tetramethylolpropane, etc. Multivalent Alcohol, and these alkylene oxide adducts; oxetane compounds having a hydroxyl group such as 3-ethyl-3-oxetanemethanol, 3-methyl-3-oxetanemethanol, 3-ethyl-3-oxetaneethanol; tris-2-hydroxyethyl Isocyanurates and the like are mentioned, and among these, a compound having high heat resistance and being difficult to decompose, and having a high boiling point and being difficult to volatilize is preferable, and a dihydric alcohol has a high effect of preventing yellowing of the resulting cured product. Alternatively, a polyol such as a trihydric alcohol or an oxetane compound having a hydroxyl group is more preferred, and a trihydric alcohol is more preferred.

  In the photocurable resin composition of the present invention, the amount of (4) the alcohol compound used relative to (1) the cationic polymerizable organic substance is preferably (4) relative to 100 parts by mass of (1) the cationic polymerizable organic substance. ) Alcohol compound 0-30 parts by mass, more preferably 0-5 parts by mass. (4) If the amount of the alcohol compound used exceeds 30 parts by mass, no further effect is observed, which is not preferable.

  (5) A thermal polymerization initiator can be used for the photocurable resin composition of this invention as needed. Thermal polymerization initiators are compounds that generate cationic species or Lewis acids upon heating, and salts such as sulfonium salts, thiophenium salts, thiolanium salts, benzylammonium, pyridinium salts, hydrazinium salts; diethylenetriamine, triethylenetriamine, tetraethylene Polyalkylpolyamines such as pentamine; alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, isophoronediamine; m-xylylenediamine, diaminodiphenylmethane, diaminodiphenyl Aromatic polyamines such as sulfone; such polyamines as phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether, etc. Polyepoxy addition-modified products produced by reacting various types of epoxy resins such as glycidyl ethers or glycidyl esters of carboxylic acids by a conventional method; the polyamines and carboxylic acids such as phthalic acid, isophthalic acid, and dimer acid Amidated modified product produced by reacting acids with a conventional method; at least one aldehyde-forming reactivity in the nucleus such as phenol, cresol, xylenol, tert-butylphenol, resorcin, and the like, and aldehydes such as polyamines and formaldehyde Mannich modified product produced by reacting phenols having a site by a conventional method; polycarboxylic acid (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid , Sebacic acid, dodeca Diacid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedi Aliphatic dicarboxylic acids such as acid, hydrogenated dimer acid and dimer acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; trimellitic acid and trimesin And acid anhydrides of tricarboxylic acids such as acids and castor oil fatty acid trimers; tetracarboxylic acids such as pyromellitic acid; dicyandiamide, imidazoles, carboxylic acid esters, sulfonic acid esters, and amine imides. Among these, from the viewpoint of reactivity, sulfonium salt, thiophenium salt, thioranium salt, benzylammonium, pyridinium salt, hydrazinium salt, etc .; polyvalent carboxylic acid (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid , Pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3, Aliphatic dicarboxylic acids such as 8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid and dimer acid; Aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; cyclohexane Alicyclic dicarboxylic acids such as dicarboxylic acids; trimellitic acid, trimesic acid, Anhydride tetracarboxylic acids) such as pyromellitic acid; and tricarboxylic acids trimers such oil fatty dicyandiamide and the like are preferable, and sulfonium salts are more preferable.

  As said (5) thermal-polymerization initiator, a commercial item can also be used, for example, Adeka Opton CP77, Adeka Opton CP66 (made by ADEKA), CI-2639, CI-2624 (made by Nippon Soda Co., Ltd.), Sun-Aid SI-60L Sun Aid SI-80L, Sun Aid SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.) and the like.

In the photocurable resin composition of the present invention, the amount of the (5) thermal polymerization initiator used is not particularly limited, but is usually 100 parts by mass of the total amount of solids in the photocurable resin composition. It is in the range of 0.001 to 10 parts by mass, and preferably (5) 0.001 to 10 parts by mass of the thermal polymerization initiator, more preferably (5) with respect to 100 parts by mass of the above (1) cationic polymerizable organic substance. ) 0.1-5 parts by mass of thermal polymerization initiator. (5) If the amount of the thermal polymerization initiator used is less than 0.001 part by mass, the effect tends to be insufficient, and if it exceeds 10 parts by mass, the physical properties such as refractive index and strength of the cured product are adversely affected. There is a case.
Moreover, when using a (5) thermal-polymerization initiator, when hardening the photocurable resin composition of this invention, it is preferable to heat at 130-180 degreeC for 20 minutes-1 hour.

In the photocurable resin composition of the present invention, a solvent capable of dissolving or dispersing each of the above components (1) to (5) and a resin additive described later, for example, acetone, methyl ethyl ketone, methyl, is usually used. Isobutyl ketone, methyl cellosolve, ethyl cellosolve, chloroform, methylene chloride, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol can be added. The amount of the solvent used in this case is preferably 10 to 100 parts by mass, more preferably 25 to 70 parts by mass with respect to 100 parts by mass of the above (1) cationically polymerizable organic substance.

  In the photocurable resin composition of the present invention, in addition to the components (1) to (5) and the solvent described above, other than the component (1) as necessary, within a range not impairing the effects of the present invention. Monomers, energy ray sensitive polymerization initiators other than the component (2), colorants such as inorganic fillers, organic fillers, pigments and dyes, photosensitizers, antifoaming agents, thickeners, surfactants, leveling agents Various resin additives such as a ring agent, a flame retardant, a plasticizer, a stabilizer, a polymerization inhibitor, an ultraviolet absorber, an antistatic agent, a flow regulator, a coupling agent, and an adhesion promoter can be added. The total amount of these resin additives is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, with respect to (1) 100 parts by mass of the cationically polymerizable organic substance.

  The photocurable resin composition of the present invention is applied on a supporting substrate such as glass, metal, paper, plastic, etc. by a known means such as a roll coater, a curtain coater, various printing, and immersion. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.

  The photocurable resin composition of the present invention can be made to be a cured product of the present invention by curing by irradiation with active energy rays.

  Examples of the active energy rays include ultraviolet rays, electron beams, X-rays, radiation, high frequencies, and the like, and ultraviolet rays are the most economical. Examples of the ultraviolet light source include an ultraviolet laser, a mercury lamp, a xenon laser, and a metal halide lamp.

  The cured product of the present invention preferably has a film refractive index of 1.53 or less at 587.6 nm (d-line) because it provides a low refractive index layer in the lens. The low refractive layer can be laminated via an adhesive or glass.

  Specific uses of the photocurable resin composition and the cured product of the present invention described above include glasses, optical materials represented by imaging lenses, paints, coating agents, lining agents, inks, resists, and liquid resists. , Adhesives, printing plates, insulating varnishes, insulating sheets, laminates, printed boards, semiconductor encapsulants, molding materials, putty, glass fiber impregnating agents, sealants, prism lenses used in backlights of liquid crystal display devices Lenses of lens sheets such as Fresnel lens sheets and lenticular lens sheets used for screens of sheets and projection televisions, or backlights using such sheets, optical lenses such as micro lenses, optical elements, and optical connectors , Optical waveguides, castings for optical modeling, etc. The substrate which may may be mentioned metals, wood, rubber, plastic, glass, ceramic products and the like.

  EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated further in detail, this invention is not limited to these Examples.

  Hereinafter, the photocurable resin composition of the present invention and the cured product obtained by curing the photocurable resin composition will be specifically described with reference to examples, evaluation examples, and comparative examples. In Examples and Comparative Examples, “part” means “part by mass”.

[Examples 1 to 13 and Comparative Examples 1 to 6]
Resins were sufficiently mixed in the formulations shown in [Table 1] and [Table 2] below to obtain photocurable resin compositions of Examples and Comparative Examples. After providing a resin spacer (gap member) with a thickness of 0.5 to 1.0 mm on the glass substrate that has been subjected to the mold release treatment, the glass substrate that has been subjected to the mold release treatment is stacked via this spacer, and the resulting photocuring The functional resin composition was injected. The photocurable resin composition was photocured by irradiating both surfaces of the glass substrate with ultraviolet light using a high-pressure mercury lamp at an energy amount of 4000 mJ / cm ² in total of 2000 mJ / cm ² . This was further heated in an oven at 150 ° C. for 1 hour to perform post cure. After cooling, the glass substrate was taken out from the oven, and the cured resin film was peeled from the glass substrate.

(1) The following compounds (1) -1 to (1) -6 were used as the cationically polymerizable organic substance.
Compound (1) -1: Adeka Resin EP-4080E (epoxy resin manufactured by ADEKA) [compound in which Z ¹ = 2,2-isobutylidene and a = b = p = 0 in the above formula (I)]
Compound (1) -2: Compound represented by the following formula (1) Compound (1) -3: Celoxide 2021P (Daicel Chemical Industries alicyclic epoxy resin) [in formula (II), Z ² = —O— Compound in which CH ₂ —CO— and m = n = −]
Compound (1) -4: 2,2-bis (3,4-epoxycyclohexyl) propane [compound in which Z ² = 2,2-isobutylidene and m = n = 0 in the above formula (II)]
Compound (1) -5: EHPE-3150 (Epoxy resin manufactured by Daicel Chemical Industries) [compound represented by the above formula (III)]
Compound (1) -6: EP-4088D (epoxy resin manufactured by ADEKA) [compound represented by the above formula (IV)]

(2) The following compounds (2) -1 to (2) -4 were used as energy ray-sensitive cationic polymerization initiators.
Compound (2) -1: Compound represented by the following formula (2) Compound (2) -2: Compound represented by the following formula (3) Compound (2) -3: Represented by the following formula (4) Compound (2) -4: Compound represented by the following formula (5)

(3) The following compounds (3) -1 to (3) -2 were used as antioxidants.
Compound (3) -1: ADK STAB AO-50 (phenol antioxidant manufactured by ADEKA)
Compound (3) -2: ADK STAB AO-60 (phenolic antioxidant manufactured by ADEKA)

(4) The following compounds (4) -1 to (4) -2 were used as alcohol compounds.
Compound (4) -1: Plaxel 303 (polycaprolactone triol manufactured by Daicel Chemical Industries)
Compound (4) -2: 3-ethyl-3-oxetanemethanol

[Evaluation Examples 1 to 13 and Comparative Evaluation Examples 1 to 6]
The following evaluations (Tg, film transmittance, refractive index, and color change) were performed on the cured resin films obtained in Examples 1 to 13 and Comparative Examples 1 to 6. The results are shown in the above [Table 1] and [Table 2].
(Tg)
Using EXSTAR DMS6100 manufactured by Seiko Instruments Inc., measurement was performed under the conditions of tensile mode (10 Hz) and 20 ° C to 300 ° C. The cured resin film having a size of 0.5 × 5.0 × 30 mm was used.

(Membrane permeability)
A Hitachi spectrophotometer U-3010 was used, and the background and reference were measured with Air. A cured resin film having a size of 1.0 × 50 × 50 mm was used.
(Refractive index)
Using a digital Abbe refractometer DR-A1 manufactured by Atago Co., Ltd., the refractive index of the D line at 25 ° C. was measured. A cured resin film having a size of 1.0 × 50 × 50 mm was used.
(Color change)
Using a spectral color difference meter SE6000 manufactured by Nippon Denshoku Co., Ltd., YI (yellow index) at 25 ° C. was measured, and color change was evaluated according to the following <evaluation criteria>.
<Evaluation criteria>
A: YI ≧ 92
○: 92 <YI ≦ 90.5
Δ: 90.5 <YI ≦ 89
X: YI <89

  From the above [Table 1] and [Table 2], it was confirmed that the photocurable resin composition of the present invention has high transparency and can suppress yellowing during curing. In addition, the photocurable resin composition of the present invention has high heat resistance, and is expected to have dimensional stability without being colored even when exposed to heat for several seconds at a reflow temperature of 300 ° C. at maximum in a mounting process such as a solder reflow furnace. Is done. Furthermore, the photocurable resin composition of the present invention has a refractive index of 1.53 or less, and is suitable for a low refractive index material.

Claims (8)

(1) Contains 100 parts by mass of a cationically polymerizable organic substance represented by any one of the following general formulas (I) to (IV), and (2) 0.001 to 10 parts by mass of an energy ray-sensitive cationic polymerization initiator. And a photocurable resin composition containing no acrylate compound.

(In the formula, Z ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms, and the methylene group in the alkylene group is cyclic, whether linear or branched. May be substituted with a methyl group, interrupted with —CO—O— or —O—CO—, and R ¹ and R ² each independently represents a halogen atom, and a and b is independently a number from 0 to 10, and p is a number from 0 to 5.)

(In the formula, Z ² represents a single bond, —O—CH ₂ —CO— or an alkylene group having 1 to 4 carbon atoms, and the methylene group in the alkylene group may be substituted with a methyl group; R ³ and R ⁴ each independently represent a halogen atom, and m and n are each independently a number from 0 to 9.)

(In the formula, s is a number from 0 to 10.)

  The photocurable resin composition according to claim 1, further comprising (3) an antioxidant.   Furthermore, (4) The photocurable resin composition of Claim 1 or 2 containing an alcohol compound. (2) The energy ray sensitive cationic polymerization initiator is represented by the general formula [A] ^{r +} [B] ^r− (wherein A represents a cationic species, B represents an anionic species, and r represents a valence). The photocurable resin composition according to any one of claims 1 to 3, which is a salt of a cation and an anion represented by.   Said (3) antioxidant is a hindered phenolic antioxidant, The photocurable resin composition of any one of Claims 1-4.   The photocurable resin composition according to any one of claims 1 to 5, wherein the (4) alcohol compound is an oxetane compound having a polyol or a hydroxyl group.   Hardened | cured material obtained by hardening | curing the photocurable resin composition of any one of Claims 1-6.   The cured product according to claim 7, wherein the film refractive index at 587.6 nm (d-line) is 1.53 or less.