JP2018090654A - Light transmissive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a light transmissive resin composition capable of forming a protective film that is excellent in adhesion with a functional layer and in which a resistance value after bending hardly rises, and to provide a display.SOLUTION: A light transmissive resin composition contains a resin (A) having a glass transition temperature of 30-170°C and a number average molecular weight of 2,000-140,000 and having a ring structure and a crosslinking agent (B), where a cured coating film of the light transmissive resin composition has a tensile modulus of 400-4,000 at a tensile speed of 0.01 mm/sec and a tensile stress when the cured coating film is stretched by 2% is 15-60 MPa.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a light-transmitting resin composition that can be used for protecting electronic components and the like.

In recent years, electronic devices typified by portable terminals such as smartphones and tablet terminals have been improved in various functions and reduced in thickness while maintaining the size. For this reason, electronic components such as printed wiring boards and display members mounted inside electronic devices are being studied for thinning, high density, multilayering, and high definition of wiring.
For example, in a smartphone, many members are housed in order to realize multiple functions in a limited space. As one of them, a protective film such as a wiring is required to have high flexibility and flexibility capable of realizing bending and the like, and performance such as high electrical insulation and thermal stability considering use in a narrow space. Furthermore, the touch panel, which is an essential member of the mobile terminal, has a base material and a functional layer (for example, a transparent conductive layer, a signal wiring, and an inorganic barrier layer) laminated on the touch panel, and the protective film is laminated with the functional layer. More aptitude is needed. Moreover, it is necessary to prevent and protect the transparent electrode inside the solar cell as another functional layer.

  Patent Document 1 discloses a resin composition containing an acrylic resin having no ring structure, a photopolymerizable compound, and a photopolymerization initiator.

WO2013 / 084875

  However, since a protective film using a conventional resin composition has low flexibility and flexibility, cracking occurs when stress such as bending is applied. For example, when the transparent electrode is protected, there is a problem that the resistance value increases. There is also a problem of low adhesion to the substrate.

  An object of the present invention is to provide a light-transmitting resin composition and a display that can form a protective film that is excellent in adhesion to a functional layer and hardly increases in resistance after bending.

The light transmissive resin composition of the present invention includes a resin (A) having a glass transition temperature of 30 to 170 ° C. and a number average molecular weight of 2,000 to 140,000 and a ring structure, and a crosslinking agent (B),
The cured film of the light transmissive resin composition has a tensile modulus of 400 to 4000 MPa at a tensile speed of 0.01 mm / second, and a tensile stress of 15 to 60 MPa when the cured film is stretched by 2%.

  According to the present invention, the cured film of the resin composition has an appropriate tensile elastic modulus and an appropriate tensile stress at the time of stretching, so that it is possible to obtain adhesion and an effect that cracks are hardly generated after bending.

  According to the present invention, it is possible to provide a light-transmitting resin composition and a display that can form a protective film that is excellent in adhesion to a functional layer and hardly increases in resistance after bending.

Schematic cross-sectional view of an embodiment for protecting a transparent electrode layer Schematic cross section of inorganic barrier layer Schematic diagram of tensile test sheet Schematic diagram of adhesion test sheet Schematic diagram of the flexibility test (for resistance value change rate measurement) sheet Schematic diagram of the flexibility test (water vapor transmission rate measurement) sheet Schematic diagram of sheet for solvent resistance test

The light transmissive resin composition (hereinafter referred to as a resin composition) of the present invention has a glass transition temperature (hereinafter referred to as Tg) of 30 to 170 ° C. and a number average molecular weight (hereinafter referred to as Mn) of 2,000 to 140,000. A resin (A) having a ring structure and a crosslinking agent (B). The cured film of the resin composition has a tensile modulus of 400 to 4000 MPa at a tensile speed of 0.01 mm / second and a tensile stress of 15 to 60 MPa when the cured film is stretched by 2%.
The resin composition of the present invention cures a resin (A) having a predetermined Tg, Mn and ring structure and a crosslinking agent (B) to such an extent that the cured coating satisfies a predetermined tensile elastic modulus and a predetermined tensile stress. This solves the above problem. Since both the composition surface (resin (A) and cross-linking agent (B)) and the elastic modulus (tensile modulus and tensile stress) must be satisfied, only satisfying either the composition surface or the elastic modulus The above problem cannot be solved.

  The resin composition of the present invention is preferably used, for example, as a protective film for protecting a functional layer used for various members constituting a display. Such a protective film is excellent in adhesion to a substrate having a functional layer, and can be used to protect a transparent electrode (also referred to as a transparent conductive film). When used for protection of the barrier layer, an unexpected effect is obtained that can suppress a decrease in water vapor barrier properties after bending.

<Resin (A)>
Resin (A) is a binder resin. It is preferable that Tg of resin (A) is 30-170 degreeC, and 50-150 degreeC is more preferable. When Tg is 30 ° C. or higher, the cohesive force of the cured film is further improved, and the heat and moisture resistance is further improved. Further, when Tg is 170 ° C. or lower, an appropriate cohesive force can be imparted to the cured film, and thus the adhesion is further improved. In the present specification, a protective film and a cured film are not distinguished.

  The Mn of the resin (A) is preferably 2,000 to 140,000, preferably 6,000 to 100,000, and more preferably 6,000 to 55,000. When Mn is 2,000 or more, the cohesive force of the cured film is increased and the heat and moisture resistance is further improved. Further, when the Mn is 140,000 or less, the viscosity of the resin composition can be easily adjusted, so that a protective film can be easily formed and an appropriate cohesive force can be easily obtained.

  Moreover, 2-400 mgKOH / g is preferable and, as for the hydroxyl value of resin (A), 4-350 mgKOH / g is more preferable. When the hydroxyl value is 2 mgKOH / g or more, the crosslinking density of the protective film is increased and the solvent resistance is further improved. Moreover, when the hydroxyl value is 400 mgKOH / g or less, the moisture and heat resistance of the protective film is further improved. In addition, in order for resin (A) to have a hydroxyl value, it is preferable to contain a hydroxyl group.

  The resin (A) has a ring structure. Examples of the ring structure include aromatic rings and aliphatic rings composed only of carbon, and heterocyclic rings containing atoms other than carbon.

  Since the resin (A) has a ring structure, the cured film can suppress the permeation of water vapor, and thus the adhesiveness with the functional layer is less likely to deteriorate after wet heat aging. Examples of the position of the ring structure in the resin (A) include the main chain of the resin (A), the side chain of the resin (A), or the main chain and side chain of the resin (A).

  Resin (A) is, for example, epoxy resin (excluding phenoxy resin), polyurethane, polyurethane urea, phenoxy resin, phenol resin, polycarbonate, benzoguanamine resin, polyester, aromatic polyether ketone, alkyd resin, silicone resin, styrene. Resin, styrene- (meth) acrylic resin, styrene-butadiene resin, cellulose acetate propionate (CAP) resin, cellulose acetate butyrate (CAB) resin, butyral resin, acetal resin, ketone resin, fluorine resin, polyolefin, melamine resin , Urea resin, rosin, rosin ester, maleic resin and the like. Among these, epoxy resin (excluding phenoxy resin), phenoxy resin, polyester, butyral resin, CAB resin, and polyurethane are preferable in terms of adhesion and flexibility.

  In this specification, the epoxy resin refers to a resin having an epoxy group excluding the following phenoxy resin, and a known epoxy resin can be used.

  A phenoxy resin is a resin having a polyhydroxy polyether structure having a bisphenol skeleton obtained by reacting an aromatic diol (such as bisphenol A or bisphenol F) with epichlorohydrin.

  The polyester preferably has at least one of a hydroxyl group and a carboxyl group. Polyester can be synthesized by a known reaction such as a reaction between a polybasic acid and a polyol, or a transesterification reaction between a polybasic acid ester and a polyol. In addition, a known method can be used as a method for imparting a carboxyl group to polyester. For example, after synthesizing polyester, a cyclic ester such as ε-caprolactone is post-added (ring-opening addition) at 180 to 230 ° C. to form a block Or a method of adding an acid anhydride such as trimellitic anhydride or phthalic anhydride.

Examples of the polybasic acid include aromatic dicarboxylic acids, linear aliphatic dicarboxylic acids, cycloaliphatic dicarboxylic acids, etc., trifunctional or higher carboxylic acids, and other carboxylic acids. The polybasic acid includes an acid anhydride group-containing compound.
Examples of the aromatic dicarboxylic acid include terephthalic acid and isophthalic acid. Examples of the linear aliphatic dicarboxylic acid include adipic acid, sebacic acid, azelaic acid and the like. Examples of the cycloaliphatic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid, dicarboxy hydrogenated bisphenol A, dimer acid, 4-methylhexahydrophthalic anhydride, and 3-methylhexahydrophthalic anhydride. Examples of the trifunctional or higher functional carboxylic acid include trimellitic anhydride and pyromellitic anhydride. Other carboxylic acids include, for example, unsaturated dicarboxylic acids such as fumaric acid, sulfonic acid metal salt-containing dicarboxylic acids such as sodium 5-sulfoisophthalate, and the like. Polybasic acids can be used alone or in combination of two or more.

  The polyol is preferably a diol and a compound having 3 or more hydroxyl groups. Examples of the diol include ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol and the like. Examples of the compound having three or more hydroxyl groups include tolmethylolpropane, glycerin, pentaerythritol and the like. Polyols can be used alone or in combination of two or more.

  A butyral resin is a known resin that can be synthesized, for example, by butyralizing polyvinyl alcohol obtained by saponification of a polyvinyl ester.

  The CAB resin can be synthesized by, for example, reacting a hydroxyl group of cellulose or a derivative thereof with one or more selected from carboxylic acids having 1 to 32 carbon atoms, alcohols, phenols, and derivatives thereof. A known resin can be used as the CAB resin.

Polyurethane is a resin having a hydroxyl group at the terminal, obtained by reacting, for example, a polyol, a diisocyanate, and a diol compound of a chain extender. Polyurethanes can extend molecular chains using chain extenders. The chain extender is generally preferably a diol. A known resin can be used as the polyurethane.

Further, the resin (A) may have a (meth) acryloyl group.
Resin (A) can be used alone or in combination of two or more.

<Crosslinking agent (B)>

The crosslinking agent (B) is one excluding the resin (A), and includes a so-called curing agent and a photopolymerization initiator.
When the crosslinking agent (B) is a curing agent, it reacts with the resin (A) to form a protective film. As for a crosslinking agent (B), when resin (A) has a hydroxyl group, an isocyanate compound etc. are preferable, for example. Moreover, when resin (A) has a carboxyl group, an isocyanate compound, an epoxy compound, an aziridine compound, an oxazoline compound, a carbodiimide compound etc. are preferable, for example. Furthermore, when resin (A) has an epoxy group, an amine compound, an acid anhydride group containing compound, etc. are preferable, for example.

As the isocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate are preferable.
Examples of the aromatic polyisocyanate include a trimethylolpropane adduct of tolylene diisocyanate, an isocyanurate of tolylene diisocyanate, and an oligomer of 4,4′-diphenylmethane diisocyanate.
Aliphatic polyisocyanates are, for example, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene. Aliphatic diisocyanates such as diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, methyl 2,6-diisocyanatohexanoate; 2,6-diisocyanatohexanoic acid 2 -Isocyanatoethyl, 1,6-diisocyanato-3-isocyanatomethylhexane, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-dii Aliphatic triisocyanates such as cyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane .
Examples of the alicyclic polyisocyanate include an isocyanurate of isophorone diisocyanate, an oligomer of isophorone diisocyanate, and the like.
Moreover, the blocked isocyanate which blocked the isocyanate group of the isocyanate compound is also preferable.

  A blocked isocyanate is a compound obtained by reacting an isocyanate group of an isocyanate compound with a blocking agent. When the dissociation temperature is reached by heating, it is dissociated into an isocyanate and a blocking agent, and the generated isocyanate group reacts with the hydroxyl group in the resin (A) to be cured. The base isocyanate is preferably the aromatic polyisocyanate, aliphatic polyisocyanate and alicyclic polyisocyanate already described. The base isocyanate preferably has a trifunctional or higher functional isocyanate group.

  The dissociation temperature of the blocking agent of blocked isocyanate is preferably 80 to 180 ° C, preferably 100 to 140 ° C, and more preferably less than 140 ° C. When the dissociation temperature is 80 ° C. or higher, an appropriate cohesive force can be easily obtained and the adhesion with the functional layer is further improved, and the storage stability of the resin composition is further improved. On the other hand, when the dissociation temperature is 180 ° C. or lower, the crosslink density is easily improved, so that the solvent resistance is further improved. If the dissociation temperature of the blocking agent is less than 140 ° C., a further effect of suppressing the dimensional change of the substrate can be obtained.

  Examples of the blocking agent constituting the blocked isocyanate include methyl ethyl ketone oxime (MEKO, dissociation temperature 130 ° C.), dimethylpyrazole (DMP, dissociation temperature 110 ° C.), diethyl malonate (DEM, dissociation temperature 110 ° C.), ε-caprolactam (E- CAP, dissociation temperature 170 ° C., butanone oxime (dissociation temperature 160 ° C.), phenol (dissociation temperature 170 ° C.), and active methylene compound (dissociation temperature 90 ° C.). Note that the dissociation temperature may slightly vary depending on the type of base isocyanate.

  An epoxy compound is a compound which has an epoxy group, for example. The properties of the epoxy compound include liquid and solid. Examples of the epoxy compound include a glycidyl ether type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, and a cyclic aliphatic (alicyclic type) epoxy resin.

  Examples of glycidyl ether type epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AD type epoxy resins, cresol novolac type epoxy resins, phenol novolac type epoxy resins, and cresol novolak type epoxy resins. Epoxy resin having biphenyl structure between cresol structure and cresol structure, epoxy resin having dicyclopentadiene skeleton structure between cresol structure and cresol structure of cresol novolak type epoxy resin, α-naphthol novolak type epoxy resin, bisphenol A type Novolac epoxy resin, dicyclopentadiene epoxy resin, biphenyl epoxy resin, tris (glycidyloxyphenyl) methane, and Tetrakis etc. (glycidyloxyphenyl) ethane.

  Examples of the glycidylamine type epoxy resin include tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, triglycidylmetaaminophenol, and tetraglycidylmetaxylylenediamine.

  Examples of the glycidyl ester type epoxy resin include diglycidyl phthalate, diglycidyl hexahydrophthalate, and diglycidyl tetrahydrophthalate.

  Examples of the alicyclic epoxy resin include epoxycyclohexylmethyl-epoxycyclohexanecarboxylate and bis (epoxycyclohexyl) adipate.

  Examples of the aziridine compound include trimethylolpropane-tri-β-aziridinylpropionate, tetramethylolmethane-tri-β-aziridinylpropionate, N, N-hexamethylene-1,6-bis-1- Examples include aziridinecarboxamide and 4,4-bis (ethyleneiminocarboxylamino) diphenylmethane.

  Examples of the oxazoline compound include 2,2 ′-(1,3-phenylene) -bis (2-oxazoline).

  Examples of the carbodiimide compound include dicyclohexyl carbodiimide and carbodilite.

  Examples of the amine compound include diethylenetriamine, triethylenetetramine, and tetraethylenepentamine.

Examples of the acid anhydride group-containing compound include tetrahydrophthalic anhydride, dodecenyl succinic anhydride, methyl nadic anhydride, trimellitic anhydride, and pyromellitic anhydride.
The crosslinking agent (B) can be used alone or in combination of two or more.

The crosslinking agent (B) may be a photopolymerization initiator. The photopolymerization initiator is preferably a radical photopolymerization initiator or a cationic photopolymerization initiator.
The photopolymerization initiator preferably reacts with the polymerizable compound blended in the resin composition.
Examples of the radical photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, ethylanthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2- Methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthio Sandone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2, 6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like.
In the cationic photopolymerization initiator, for example, the cation moiety is aromatic sulfonium, aromatic iodonium, aromatic diazonium, aromatic ammonium, thianthrhenium, thioxanthonium, (2,4-cyclopentadien-1-yl) [( 1-methylethyl) benzene] -Fe cation, and the anion moiety is BF ₄ −, PF ₆ −, SbF ₆ −, [BX ₄ ] ^−, where X is at least two fluorine or trifluoromethyl groups And an onium salt composed of a phenyl group substituted with

  Examples of the aromatic sulfonium salt include bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate, and bis [4- (diphenylsulfone). Nio) 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) phen 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 bishexafluoroantimonate, Bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bistetrafluoroborate, bis [4- (di (4- ( - hydroxyethoxy)) phenylsulfonio) phenyl] sulfide tetrakis (pentafluorophenyl) borate, and the like.

  Examples of aromatic iodonium salts include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (dodecyl). Phenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluorophosphate 4-methylphenyl-4- (1-methylethyl) pheny Examples include iodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate, and the like. It is done.

  Examples of the aromatic diazonium salt include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis (pentafluorophenyl) borate.

Examples of aromatic ammonium salts include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl-2- Cyanopyridinium tetrakis (pentafluorophenyl) borate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, 1- (naphthylmethyl) -2- Examples thereof include cyanopyridinium tetrafluoroborate and 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate.
Examples of the thioxanthonium salt include S-biphenyl 2-isopropyl thioxanthonium hexafluorophosphate.
The (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe salt includes (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene. ] -Fe (II) hexafluorophosphate, (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe (II) hexafluoroantimonate, 2,4-cyclopentadiene-1- Yl) [(1-methylethyl) benzene] -Fe (II) tetrafluoroborate, 2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe (II) tetrakis (pentafluorophenyl) ) Borate and the like.

  As for a crosslinking agent (B), it is preferable to use 1-30 mass parts with respect to 100 mass parts of resin (A), and 2-20 mass parts is more preferable. When the crosslinking agent (B) is 1 part by mass or more, the curability is improved and the cohesive force is increased, so that the wet heat property and the solvent resistance are improved. When the cross-linking agent (B) is 30 parts by mass or less, an appropriate cured film is obtained, thereby improving adhesion and flexibility.

<Curing accelerator>
In order to accelerate the curing reaction, the resin composition of the present invention may contain a known curing accelerator (hereinafter referred to as an accelerator).

The curing accelerator is preferably one or more compounds selected from the group consisting of tin compounds, metal chlorides, metal acetylacetonate salts, metal sulfates, amine compounds, and amine salts.
Examples of tin compounds include organic tin compounds such as stannous octoate and dibutyltin dilaurate, and inorganic tin compounds.
The metal chloride is a metal chloride composed of Cr, Mn, Co, Ni, Fe, Cu, or Al, and examples thereof include cobalt chloride, nickel chloride, and ferric chloride.
The metal acetylacetonate salt is a metal acetylacetonate salt made of Cr, Mn, Co, Ni, Fe, Cu or Al, and examples thereof include cobalt acetylacetonate, nickel acetylacetonate, iron acetylacetonate and the like. .
The metal sulfate is a metal sulfate selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu, and Al, and examples thereof include copper sulfate.
Examples of the amine compound include triethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) ether, N, N, N ′, N ″, N ″. -Pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, dimorpholinodiethyl ether, N-methylimidazole, dimethylaminopyridine, triazine, N '-(2-hydroxyethyl) -N, N, N'-trimethyl-bis (2-aminoethyl) ether, N, N-dimethylhexanolamine, N, N-dimethylaminoethoxyethanol, N, N, N'-trimethyl-N '-(2-hydroxy Ethyl) ethylenediamine, N- (2-hydroxyethyl) -N, N ′, N ″, N ″ -te Lamethyldiethylenetriamine, N- (2-hydroxypropyl) -N, N ′, N ″, N ″ -tetramethyldiethylenetriamine, N, N, N′-trimethyl-N ′-(2-hydroxyethyl) propanediamine, N -Methyl-N '-(2-hydroxyethyl) piperazine, bis (N, N-dimethylaminopropyl) amine, bis (N, N-dimethylaminopropyl) isopropanolamine, 2-aminoquinuclidine, 3-aminoquinu Klysine, 4-aminoquinuclidine, 2-quinuclidol, 3-quinuclidinol, 4-quinuclidinol, 1- (2′-hydroxypropyl) imidazole, 1- (2′-hydroxypropyl) -2-methylimidazole, 1- (2′-hydroxyethyl) imidazole, 1- (2′-hydroxyethyl) -2- Tylimidazole, 1- (2′-hydroxypropyl) -2-methylimidazole, 1- (3′-aminopropyl) imidazole, 1- (3′-aminopropyl) -2-methylimidazole, 1- (3′- Hydroxypropyl) imidazole, 1- (3′-hydroxypropyl) -2-methylimidazole, N, N-dimethylaminopropyl-N ′-(2-hydroxyethyl) amine, N, N-dimethylaminopropyl-N ′, N′-bis (2-hydroxyethyl) amine, N, N-dimethylaminopropyl-N ′, N′-bis (2-hydroxypropyl) amine, N, N-dimethylaminoethyl-N ′, N′-bis (2-hydroxyethyl) amine, N, N-dimethylaminoethyl-N ′, N′-bis (2-hydroxypropyl) amine, melamine or / and Examples include benzoguanamine. The amine compound does not contain an amine salt.
Examples of the amine salt include DBU (1,8-diaza-bicyclo [5,4,0] undecene-7) organic acid salt.
Accelerators can be used alone or in combination of two or more.

  It is preferable that 0.05-1 mass part is normally used for an accelerator with respect to 100 mass parts of resin (A). When the accelerator is used within the above range, the solvent resistance and heat resistance are further improved.

<Antifoaming agent>
The resin composition of the present invention can further contain an antifoaming agent.
Examples of the antifoaming agent include acrylic resin, vinyl ether resin, olefin resin, butadiene resin, modified siloxane resin, dimethylpolysiloxane, silicone, modified silicone (for example, fluorine-modified silicone), petroleum resin and the like (however, resin ( Except A)).
The antifoaming agent can be used alone or in combination of two or more.

  It is preferable that 0.1-3 mass parts is mix | blended with an antifoamer with respect to 100 mass parts of resin (A). When the defoaming agent is 0.1 parts by mass or more, the resin composition is less likely to foam when mixed, and air bubbles are less likely to remain in the protective film, thereby improving visibility. Moreover, when it becomes 3 mass parts or less, the transparency of a protective film will improve more.

<Solvent>
The resin composition of the present invention can further contain a solvent.
When a solvent is blended, the viscosity of the resin composition can be easily adjusted. The solvent can be appropriately selected according to the solubility of the resin (A) to be used, printing or coating method.
Examples of the solvent include ester solvents, ketone solvents, glycol ether solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, alcohol solvents, ether solvents, other solvents, water, and the like.

  Examples of ester solvents include ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, and acetic acid. (Iso) amyl, cyclohexyl acetate, ethyl lactate, 3-methoxybutyl acetate, sec-hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, isoamyl propionate , Γ-butyrolactone and the like.

  Examples of ketone solvents include acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, dipropyl ketone, diisobutyl ketone, methyl amyl ketone, acetonyl acetone, isophorone, cyclohexanone, and methylcyclohexanone. Can be mentioned.

  Examples of the glycol ether solvent include methyl isobutyl carbinol, ethylene glycol dibutyl ether, ethylene glycol monophenyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethoxymethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether. , Diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol dimethyl ether Ter, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether, 3-methyl-3-methoxy-1-butanol, ethylene glycol diethyl ether, ethylene glycol diglycidyl ether, ethylene glycol mono Examples include isopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, and dipropylene glycol monopropyl ether.

  Examples of the aliphatic hydrocarbon solvent include normal paraffin solvents, isoparaffin solvents, and cycloparaffin solvents. Examples of normal paraffin solvents include n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-dodecane, No. 0 solvent L, M, H (manufactured by Nippon Oil Corporation), normal Paraffin SL, L, M (manufactured by Nippon Oil Corporation) and the like can be mentioned. Examples of the isoparaffinic solvent include isohexane, 2,2,3-trimethylpentane, isooctane, 2,2,5-trimethylhexane, Isosol 200, 300, 400 (manufactured by Nippon Oil Corporation), Supersol FP2, 25, 30 38 (made by Idemitsu Kosan Co., Ltd.). Examples of the cycloparaffinic solvent include cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, naphthesol 160, 200, and 220 (manufactured by Nippon Oil Corporation), AF Solvent No. 4, No. 5, No. 6, and No. 7 No. (manufactured by Nippon Oil Corporation).

  Examples of the aromatic hydrocarbon solvent include toluene, xylene, ethylbenzene, naphthalene, tetralin, and solvent naphtha. Commercially available products include, for example, Swazol (manufactured by Cosmo Oil Co., Ltd., Maruzen Petrochemical Co., Ltd.) Solvesso (manufactured by ExxonMobil Corp.), Cactus Fine (manufactured by Japan Energy Corp.), and the like.

  Examples of alcohol solvents include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-amyl alcohol, sec-amyl alcohol, 1-ethyl. -1-propanol, 2-methyl-1-butanol, isoamyl alcohol, t-amyl alcohol, sec-isoamyl alcohol, neoamyl alcohol, hexyl alcohol, 2-methyl-1-pentanol, 4-methyl-2-pentanol , Heptyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, benzyl alcohol, α-terpineol, Black hexanol, 3-methoxybutanol, diacetone alcohol and the like.

Examples of ether solvents include cyclic ethers such as tetrahydrofuran and 1,3-dioxolane.
Examples of other solvents include carbonate solvents such as dimethyl carbonate, ethyl methyl carbonate, and di-n-butyl carbonate.
The solvent can be used alone or in combination of two or more.

  The usage-amount of a solvent is about 5-75 weight% out of the non volatile matter of a resin composition, and the total 100 weight% of a solvent.

The resin composition of the present invention can further contain a leveling agent. The smoothness of a protective film improves more by mix | blending a leveling agent. Examples of the leveling agent include acrylic resin, modified silicone, polyether-modified polysiloxane copolymer, dimethylpolysiloxane compound, silicone-modified copolymer, and organic-modified polysiloxane. The leveling agent is a compound other than the resin (A).
Leveling agents can be used alone or in combination of two or more.

The resin composition of the present invention can further contain fine particles. The fine particles are preferably organic fine particles, inorganic fine particles, and organic / inorganic composite fine particles.
Examples of the organic fine particles include a melamine resin, a benzoguanamine resin, a benzoguanamine / melamine / formalin condensate, an acrylic resin, a urethane resin, and a styrene resin. The organic fine particles exclude the resin (A).
The inorganic fine particles are known fine particles having, for example, a spherical shape, a flaky shape, a plate shape, a dendritic shape, and a scale shape. Inorganic fine particles include, for example, silica, mica, synthetic mica, glass flake, flaky alumina, flaky silica, flaky aluminum, flaky molybdenum disulfide, talc, wollastonite, montmorillonite, beidellite, hecrolite, saponite, stevensite, sericite. , Illite, kaolinite, vermiculite, clay, titanium oxide and the like.
The fine particles can be used alone or in combination of two or more.

  The fine particles are preferably blended in an amount of 2 to 30 parts by mass with respect to 100 parts by mass of the resin (A). When the fine particles are 2 parts by mass or more, a tough cured film is obtained, whereby the tensile elastic modulus and the tensile stress when stretched by 2% are further improved. Furthermore, since the curing shrinkage after drying is relaxed, the adhesion, particularly the adhesion after wet heat aging, is improved. Further, when the fine particles are 30 parts by mass or less, a cured film that can withstand bending stress can be obtained, so that an increase in resistance value after bending can be suppressed.

The resin composition of the present invention may contain a photocurable compound. The photocurable compound is preferably a photoradical curable compound or a photocationic curable compound.
The photo-radical curable compound is preferably, for example, a monofunctional (meth) acrylic monomer, a polyfunctional (meth) acrylic monomer, other vinyl monomers, or a polyfunctional (meth) acrylic oligomer.

  Examples of the monofunctional (meth) acrylic monomer include alkyl (meth) acrylate and a polar group-containing monofunctional (meth) acrylic monomer. The alkyl (meth) acrylate is a monofunctional (meth) acrylate having an alkyl group. The alkyl group may be linear or branched.

  Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, s-butyl (meth) acrylate, and t-butyl (meth). Acrylate, heptyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, Examples include n-decyl (meth) acrylate.

Examples of the polar group-containing monofunctional (meth) acrylic monomer include a carboxyl group-containing monofunctional (meth) acrylic monomer, a hydroxyl group-containing monofunctional (meth) acrylic monomer, an amide group-containing monofunctional (meth) acrylic monomer, and the like. Examples of the carboxyl group-containing monofunctional (meth) acrylic monomer include acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, and the like.
Examples of the hydroxyl group-containing monofunctional (meth) acrylic monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6 Hydroxyalkyl (meth) acrylates such as hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate; hydroxyethyl (meth) acrylamide, (4-hydroxymethylcyclohexyl) methyl acrylate, N-methylol (meth) acrylamide, N-hydroxy (meth) acrylamide and the like can be mentioned. Examples of the amide group-containing monofunctional (meth) acrylic monomer include N, N-dimethylaminoethyl acrylate, N, N-dimethylacrylamide, N, N-diethylacrylamide, and N-acryloylmorpholine.

Examples of the polyfunctional (meth) acrylic monomer include polyfunctional (meth) acrylates having an acryloyl group or a methacryloyl group. As for the said polyfunctional (meth) acrylate, bifunctional (meth) acrylate and trifunctional or more than (meth) acrylate are mentioned.
Examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, hexanediol (meth) acrylate, long chain aliphatic di (meth) acrylate, neopentyl glycol di (meth) acrylate, Hydroxypivalic acid neopentyl glycol di (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, propylene di (meth) acrylate, glycerol (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di ( (Meth) acrylate, tetramethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, polyester Lenglycol di (meth) acrylate, polypropylene di (meth) acrylate, triglycerol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, methoxylated cyclohexyl di ( (Meth) acrylate, acrylated isocyanurate, bis (acryloxyneopentyl glycol) adipate, bisphenol A di (meth) acrylate, tetrabromobisphenol A di (meth) acrylate, bisphenol S di (meth) acrylate, butanediol di (meth) ) Acrylate, phthalic acid di (meth) acrylate, phosphoric acid di (meth) acrylate, zinc di (meth) acrylate, and the like.
The trifunctional or higher functional (meth) acrylates include, for example, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri ( (Meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, tri (meth) acrylate phosphate, tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetraacrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, dipen Erythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, carboxylic acid-modified dipentaerythritol penta (meth) acrylate , Urethane tri (meth) acrylate, ester tri (meth) acrylate, urethane hexa (meth) acrylate, ester hexa (meth) acrylate, and the like.
Examples of other vinyl monomers include styrene, vinyl acetate, vinyl chloride, acrylic aldehyde, acrylonitrile, acrylamide, and vinyl caprolactam.

  The polyfunctional (meth) acryl oligomer is a compound having a formula weight or a weight average molecular weight of about 1000 to 20000 and having a (meth) acryloyl group of about 2 to 10. Examples of the polyfunctional (meth) acryl oligomer include urethane (meth) acrylate and epoxy (meth) acrylate.

The photocationic curable compound is preferably a compound having one or more functional groups selected from an oxetane ring, an epoxy ring, a vinyl ether group, and a vinylaryl group in one molecule.
Compounds having one or more oxetane rings in one molecule are, for example, 3,3-bis (vinyloxymethyl) oxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) Oxetane, 3-ethyl-3- (hydroxymethyl) oxetane, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (chloromethyl) ) Oxetane, 3,3-bis (chloromethyl) oxetane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis {[1-ethyl (3-oxetanyl)] methyl} ether, 4 , 4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] bicyclohexyl, 1,4-bis [( 3-ethyl-3-oxetanyl) methoxymethyl] cyclohexane, 3-ethyl-3 [[(3-ethyloxetane-3-yl) methoxy] methyl] oxetane and the like.
Compounds having one or more epoxy rings in one molecule are, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, bromine Bisphenol S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxy Cyclohexane carboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxy Chloromethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylene bis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, Epoxy hexahydrophthalic acid di-2-ethylhexyl, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylol propylene Polyglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers; polyethers obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin Polyglycidyl ethers of polyols; diglycidyl esters of aliphatic long-chain dibasic acids; monoglycidyl ethers of higher aliphatic alcohols; phenols, cresols, butylphenols, or monohydric polyether alcohols obtained by adding alkylene oxides to these Examples include glycidyl ethers; glycidyl esters of higher fatty acids.
Examples of the compound having one or more vinyl ether groups in one molecule include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether. 2-hydroxybutyl vinyl ether, 3-hydroxyisobutyl vinyl ether, 2-hydroxyisobutyl vinyl ether, 1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinyl ether, 1-hydroxymethylpropyl vinyl ether, 4-hydroxycyclohexyl Vinyl ether, 1,6-hexanediol monovinyl ether, 1,4-cyclohexanedimethanol No vinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,2-cyclohexanedimethanol monovinyl ether, p-xylene glycol monovinyl ether, m-xylene glycol monovinyl ether, o-xylene glycol monovinyl ether, diethylene glycol monovinyl ether, triethylene Glycol monovinyl ether, tetraethylene glycol monovinyl ether, pentaethylene glycol monovinyl ether, oligoethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, dipropylene glycol monovinyl ether, tripropylene glycol monovinyl ether, tetrapropylene glycol monovinyl ether, pentapropylene glycol Monovinyl ether, oligo propylene glycol monomethyl ether, polypropylene glycol monovinyl ether, and derivatives thereof.
Compounds having at least one vinylaryl group in one molecule are, for example, styrene, divinylbenzene, methoxystyrene, ethoxystyrene, hydroxystyrene, vinylnaphthalene, vinylanthracene, 4-vinylphenyl acetate, (4-vinylphenyl) dihydroxyborane. , (4-vinylphenyl) boranoic acid, (4-vinylphenyl) boronic acid, 4-ethenylphenylboronic acid, 4-vinylphenylboranoic acid, 4-vinylphenylboronic acid, p-vinylphenylboric acid, p- Examples thereof include vinylphenylboronic acid, N- (4-vinylphenyl) maleimide, N- (p-vinylphenyl) maleimide, N- (p-vinylphenyl) maleimide, and derivatives thereof.
The photocationic curable compound may be an oligomer.
A photocurable compound can be used individually or in combination of 2 or more types.

  The photocurable compound is preferably a compound having a formula weight or Mn of 5000 or less. In addition, when resin (A) has a (meth) acryloyl group, the formula amount or Mn of a photocurable compound is preferably less than 2000.

  The photocurable compound is preferably blended in an amount of 200 to 10,000 parts by mass with respect to 100 parts by mass of the resin (A).

  The resin composition of this invention can be manufactured by mix | blending the raw material demonstrated in the upper stage and mixing with a stirrer. As the stirrer, a known stirring device such as a planetary mixer and a disper can be used.

  The resin composition of the present invention is preferably printed (or coated) on a functional layer of an electronic component mounted inside a display, for example, to form a protective film cured by heating or ultraviolet irradiation. Moreover, the resin composition of this invention can form a protective film similarly to the above, in order to protect the functional layer of the transparent electrode mounted, for example inside a solar cell. The protective film (dry film) can prevent the functional layer from being deteriorated or broken.

  The cured coating formed from the resin composition preferably has a tensile modulus of 400 to 4000 MPa at a tensile speed of 0.01 mm / second, more preferably 600 MPa or more.

Further, the cured film preferably has a tensile stress of 15 to 60 MPa when stretched by 2%, more preferably 20 MPa or more.
When the cured film satisfies a predetermined tensile elastic modulus and a predetermined tensile stress at the same time, a cured film having both moderate toughness and flexibility can be obtained. Thereby, adhesiveness, heat-and-moisture resistance, and flexibility are further improved.

Furthermore, the cured film preferably has a yield point. The yield point can be defined by strain and stress. The yield point strain is preferably 2 to 10%, more preferably 3 to 8%. When the yield point strain satisfies a predetermined range, a flexible cured film can be obtained, so that flexibility is further improved.

The yield point stress is preferably 20 to 80 MPa. When the yield point stress satisfies the above range, a tough cured film is obtained, so that an increase in resistance value after bending can be suppressed.
The yield point here means the first point at which the strain increases without increasing the stress, and the strain at that time is the yield point strain and the stress is the yield point stress.

  The conditions for forming the cured coating (also referred to as a sample) for measuring the tensile modulus, tensile stress, yield point, and yield point stress are not limited as long as the predetermined tensile modulus and predetermined tensile stress are obtained. . As an example of the forming conditions, a film having a thickness of 20 μm formed by heating at 130 ° C. for 30 minutes is prepared in a size of 50 mm in length × 10 mm in width. The measurement is carried out using a small tabletop tensile tester (EZ-SX) manufactured by Shimadzu Corporation with a distance between chucks of 23 mm and a tensile speed of 0.01 mm / second to measure the tensile modulus and tensile stress.

  The storage elastic modulus at 30 ° C. of the cured film formed from the resin composition is preferably 700 to 3000 MPa, and more preferably 1000 MPa or more. When the storage elastic modulus is 700 MPa or more, a cured film having appropriate toughness and flexibility can be obtained. Thereby, adhesiveness, heat-and-moisture resistance, and flexibility are further improved.

  The conditions for forming the cured film (also referred to as a sample) for measuring the storage elastic modulus are not limited as long as a predetermined storage elastic modulus can be obtained. As an example of the forming conditions, a film having a thickness of 20 μm formed by heating at 130 ° C. for 30 minutes is prepared in a size of 28 mm in length × 5 mm in width, and a dynamic viscoelasticity measuring apparatus (DVA-225) manufactured by IT Measurement Control Co., Ltd. is used. The measurement is performed using a distance between chucks of 20 mm, a temperature increase rate of 10 ° C./second, and a measurement temperature range of 25 to 200 ° C.

  The cured film is preferably used as a protective film for the functional layer. The functional layer is a layer in which an inorganic material is formed on a substrate, and examples thereof include a transparent electrode layer and an inorganic barrier layer. The functional layer does not need to be formed on the entire surface of the substrate, and may be partially formed. Note that the functional layers need not all be inorganic materials, and may be layers formed from a mixture of organic materials and inorganic materials.

<Transparent electrode layer>
The functional layer is preferably a transparent electrode layer.
An embodiment for protecting a transparent electrode layer mounted in a touch panel display as one embodiment will be described with reference to FIG. In addition, it cannot be overemphasized that the aspect containing a transparent electrode layer is not limited to the following.
According to FIG. 1, the aspect which laminated | stacked the base material 11, IM layer 12, the transparent electrode layer 13, the protective film 14, the transparent electrode layer 13, the protective film 14, the adhesion layer 15, and the base material 11 in order is mentioned.
Examples of the substrate 11 include polyethylene terephthalate (PET), polycarbonate (PC), cycloolefin polymer (COP), and glass.

The IM (index matching) layer 12 is an optical adjustment layer for preventing (invisibility) the bone appearance of the transparent electrode pattern. A known IM layer can be used.
The thickness of the IM layer 12 is about 2 to 10 μm.

  The transparent electrode layer 13 is a thin film layer having both visible light transparency and electrical conductivity, and is widely used as a transparent electrode for liquid crystals, organic EL elements, touch panels, solar cells, and the like. The material of the transparent electrode layer 3 is made of conductive metals such as gold, silver and copper, and alloys thereof, and indium tin oxide (ITO), zinc oxide (ZnO), carbon nanotube (CNT), fullerene, graphene and the like. Conductive materials are also preferred. In addition, when using carbon materials, such as CNT, it is preferable that a transparent conductive layer contains binder resin.

  The thickness of the transparent electrode layer 13 is usually about 5 nm to 100,000 nm. For example, in the case of ITO, it is about 5 to 500 nm.

  The protective film 14 is a cured film formed from a resin composition. The thickness of the protective film 14 is usually preferably 3 to 30 μm and more preferably 4 to 10 μm. When the thickness of the cured coating is 3 μm or more, the protective function of the functional layer is improved and the flexibility is further improved. Further, when the thickness of the protective film 14 is 30 μm or less, transparency is further improved in addition to improvement in productivity and cost reduction. Moreover, it is also preferable to provide the 2nd protective film formed from the resin composition using other resin (A) on the said cured film. Thereby, flexibility is further improved.

As a method of forming the protective film 14 on the substrate having the functional layer, a known printing or coating method can be used. Examples of the printing method include screen printing, flexographic printing, offset printing, gravure printing, IJ (inkjet) printing, and gravure offset printing. Examples of the coating method include a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, and a slide coating method.
Moreover, it is preferable to perform a drying / curing process after printing or coating. Examples of the drying / curing step include known drying apparatuses such as a UV lamp (for example, a high-pressure mercury lamp), a hot air oven, an infrared oven, a microwave oven, and a composite oven in which these are combined. The conditions of heat drying / curing using a hot air oven are preferably from 80 to 180 ° C. for about 10 to 120 minutes, more preferably from 100 to 140 ° C. for about 15 to 60 minutes. Moreover, the light irradiation amount is about 10 to 3000 mJ / m ² .

  Examples of the adhesive layer 15 include an acrylic adhesive, a urethane adhesive, a polyester adhesive, a silicone adhesive, and a rubber adhesive. The thickness of the adhesive layer 15 is about 10 to 300 μm.

<Inorganic barrier layer>
The functional layer is preferably an inorganic barrier layer.
An embodiment of an organic EL display provided with an inorganic barrier layer as one embodiment will be described with reference to FIG. In addition, it cannot be overemphasized that the aspect containing an inorganic barrier layer is not limited to the following.
According to FIG. 2, the aspect which laminated | stacked the base material 21, TFT22, the organic electroluminescent light emitting layer 23, the transparent electrode layer 24, the inorganic barrier layer 25, the protective film 26, the adhesion layer 27, and the base material 21 in order is mentioned.
The transparent electrode layer 24, the protective film 26, and the adhesive layer 27 are as described above.

There is no restriction | limiting in particular in the base material 21, According to a use purpose etc., it can select suitably. The substrate is preferably, for example, cellulose ester, polyester, polyolefin, vinyl compound, acrylic resin, or other resin.
As the cellulose ester, for example, cellulose ester includes diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose and the like.
Examples of the polyester include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate. And polybutylene terephthalate.
Examples of the polyolefin include polyethylene, polypropylene (PP), polymethylpentene, polytetrafluoroethylene, and cycloolefin polymer (COP).
Examples of the vinyl compound include polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride, and polyvinyl fluoride.
Examples of the acrylic resin include polymethyl methacrylate (PMMA) and polyacrylic acid ester.
Other resins include, for example, polystyrene (PS), polycarbonate (PC), polyamide, polyimide (PI), polyurethane, polysulfone, polyethersulfone, polyetherketone, polyetherimide, polyoxyethylene, norbornene resin, AS resin ( SAN), vinylidene chloride resin (PVDC), epoxy resin and the like. Among these, polyethylene terephthalate (PET), polycarbonate (PC), cycloolefin polymer (COP), and polyimide (PI) are preferable.

  Although the thickness in particular of a base material is not restrict | limited, It is about 30-350 micrometers, and 50-250 micrometers is more preferable. The mechanical properties, shape stability, dimensional stability, handling surface, and the like of the substrate are likely to be appropriate depending on the thickness in the above range.

The TFT 22 is a thin film transistor, and a known TFT can be used.
The thickness of the TFT 22 is about 5 to 500 nm.

The organic EL (electroluminescence) light emitting layer 23 is a known layer, and is usually a layer made of an organic compound formed from one layer to multiple layers.
The thickness of the organic EL light emitting layer is about 2 to 1000 nm.

  The inorganic barrier layer 25 is a thin film layer made of a metal compound. Examples of the inorganic barrier layer forming method include physical vapor deposition methods (PVD) such as vapor deposition, sputtering, and ion plating, various chemical vapor deposition methods (CVD), plating, and sol-gel methods. There is a phase growth method. In particular, the CVD method and the sputtering method are preferable in that a dense inorganic barrier layer having excellent barrier performance can be formed.

  The metal compound is preferably, for example, silicon oxide, aluminum oxide, nitride, carbide, a mixture thereof, or a composite oxide thereof. Furthermore, other metal oxides, metal nitrides, or metal carbides can be used in combination. The inorganic barrier layer may have a single layer structure made of the above-described materials, or may have a multilayer structure made of a plurality of layers having the same composition or different compositions.

  The thickness of the inorganic barrier layer 25 is not particularly limited, but the thickness of one layer is preferably 15 to 100 nm, and more preferably 20 to 50 nm. When the thickness is 15 nm or more, the generation of pinholes during the formation of the inorganic barrier layer is reduced, and the barrier performance is greatly improved. On the other hand, when the thickness is 100 nm or less, cracking hardly occurs after bending.

As mentioned above, the resin composition of this invention demonstrated the detail about the case where it applies to the protective film on the base material which has a functional layer.
You may use the resin composition of this invention for uses, such as a rigid print, a flexible print, a semiconductor element, a solar cell, an organic EL element, a touch panel, for example.
Examples of the display obtained from the present invention include a mobile phone, a smartphone, a tablet terminal, a notebook computer, a smart watch, an electronic book, a car navigation, a game terminal, a liquid crystal display monitor, and an organic / inorganic EL display monitor. Even without a display, it can be used for digital cameras, video cameras, CDs, DVDs, players, and the like.

The display of the present invention includes a substrate and a protective film that is a cured product of the light-transmitting resin composition. The substrate preferably has a functional layer, and the protective film preferably protects the functional layer. The protective film may not need to protect all of the functional layer depending on the application.
As the display, for example, the touch panel display includes the embodiment of FIG. 1 using a surface glass plate of a liquid crystal panel as a base material.
Further, for example, an embodiment shown in FIG.
Moreover, although it is not a display, it is preferable to use as a protective film of the transparent electrode which comprises a solar cell (not shown).

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to the following examples. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”. The compounding quantity in a table | surface is a mass part.

<Resin (A)>
[Resin solution 1]

40 parts of Elitel UE-3200G (polyester, Mn 15,000, hydroxyl value 6 mg KOH / g, Tg 65 ° C., manufactured by Unitika) was dissolved in 60 parts of ethylene glycol monoethyl ether acetate to obtain a resin solution 1 having a nonvolatile content of 40%. .

[Resin solution 2]
40 parts of XA-0611 (polyester, Mn 17,000, hydroxyl value 4 mg KOH / g, Tg 65 ° C., manufactured by Unitika) was dissolved in 60 parts of ethylene glycol monoethyl ether acetate to obtain a resin solution 2 having a nonvolatile content of 40%.

[Resin solution 3]
40 parts of YP-55U (phenoxy resin, Mn 10,000, hydroxyl value 283 mg KOH / g, Tg 84 ° C., manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) is dissolved in 60 parts of ethylene glycol monoethyl ether acetate to obtain a resin solution 3 having a nonvolatile content of 40%. Obtained.

[Resin solution 4]
40 parts of FX-293 (phenoxy resin, Mn 10,500, hydroxyl value 164 mg KOH / g, Tg 158 ° C., manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) is dissolved in 60 parts of ethylene glycol monoethyl ether acetate, and resin solution 4 having a nonvolatile content of 40% is obtained. Obtained.

[Resin solution 5]
40 parts of JER1010 (epoxy resin, Mn 5,500, hydroxyl value 36 mg KOH / g, Tg 59 ° C., manufactured by Mitsubishi Chemical Corporation) was dissolved in 60 parts of ethylene glycol monoethyl ether acetate to obtain a resin solution 5 having a nonvolatile content of 40%.

[Resin solution 6]
40 parts of BL-10 (butyral resin, Mn 18,500, hydroxyl value 247 mg KOH / g, Tg 59 ° C., manufactured by Sekisui Chemical Co., Ltd.) is dissolved in 60 parts of ethylene glycol monoethyl ether acetate to obtain a resin solution 6 having a nonvolatile content of 40%. It was.

[Resin solution 7]
40 parts of BX-L (butyral resin, Mn 20,000, hydroxyl value 353 mg KOH / g, Tg 74 ° C., manufactured by Sekisui Chemical Co., Ltd.) is dissolved in 60 parts of ethylene glycol monoethyl ether acetate to obtain a resin solution 7 having a nonvolatile content of 40%. It was.

[Resin solution 8]
40 parts of BX-5 (acetal resin, Mn 130,000, hydroxyl value 321 mg KOH / g, Tg 86 ° C., manufactured by Sekisui Chemical Co., Ltd.) is dissolved in 60 parts of ethylene glycol monoethyl ether acetate to obtain a resin solution 8 having a nonvolatile content of 40%. It was.

[Resin solution 9]
40 parts of CAB-551-0.2 (cellulose acetate butyrate resin, Mn 30,000, hydroxyl value 53 mg KOH / g, Tg 101 ° C., manufactured by Eastman Chemical Japan) was dissolved in 60 parts of ethylene glycol monoethyl ether acetate and nonvolatile A resin solution 9 having a content of 40% was obtained.

[Resin solution 10]
40 parts of CAB-500-5 (cellulose acetate butyrate resin, Mn 57,000, hydroxyl value 33 mg KOH / g, Tg 96 ° C., manufactured by Eastman Chemical Japan Co.) was dissolved in 60 parts of ethylene glycol monoethyl ether acetate to give a nonvolatile content of 40 % Resin solution 10 was obtained.

[Resin solution 11]
114 parts of UR-1370 (polyurethane, Mn 30,000, hydroxyl value 3 mg KOH / g, Tg 46 ° C., non-volatile content 35%, manufactured by Toyobo Co., Ltd.) was used as the resin solution 11 as it was.

[Resin solution 12]
133 parts of UR-8200 (polyurethane, Mn 25,000, hydroxyl value 4 mg KOH / g, Tg 73 ° C., non-volatile content 30%, manufactured by Toyobo Co., Ltd.) was used as the resin solution 12 as it was.

[Resin solution 13]
CAB-551-0.01 (cellulose acetate butyrate resin, Mn 16,000, hydroxyl value 50 mg KOH / g, Tg 85 ° C., manufactured by Eastman Chemical Japan) 40 parts of monofunctional (meth) acrylic monomer (1) light acrylate It melt | dissolved in 60 parts of LA (lauryl acrylate), and the resin solution 13 of 100% of non volatile matter was obtained.

[Resin solution 14]
133 parts of UR-8300 (polyurethane, Mn 30,000, hydroxyl value 3 mg KOH / g, Tg 23 ° C., nonvolatile content 30%, manufactured by Toyobo Co., Ltd.) was used as the resin solution 14 as it was.

[Resin solution 15]
40 parts of CA-398-3 (cellulose acetate resin, Mn 50,000, hydroxyl value 116 mg KOH / g, Tg 189 ° C., manufactured by Eastman Chemical Japan) was dissolved in 60 parts of ethylene glycol monoethyl ether acetate, and the nonvolatile content was 40%. A resin solution 15 was obtained.

[Resin solution 16]
40 parts of Elitel UE-3320 (polyester, Mn 1,800, hydroxyl value 60 mg KOH / g, Tg 40 ° C., manufactured by Unitika) was dissolved in 60 parts of ethylene glycol monoethyl ether acetate to obtain a resin solution 16 having a nonvolatile content of 40%. .

[Resin solution 17]
40 parts of sorbine C (vinyl chloride / vinyl acetate copolymer resin having no ring structure, Mn 31,000, Tg 70 ° C., manufactured by Nissin Chemical Industry Co., Ltd.) is dissolved in 60 parts of ethylene glycol monoethyl ether acetate to give a nonvolatile content of 40 % Resin structure 17 having no ring structure was obtained.

  The Mn, hydroxyl value and Tg of the resins (A) of the resin solutions 1 to 17 were determined according to the following method.

<Measurement of number average molecular weight (Mn)>
Apparatus: GPC (gel permeation chromatography)
Model: Shodex GPC-101 manufactured by Showa Denko
Column: Showa Denko GPCKF-G + KF805L + KF803L + KF802
Detector: Differential refractive index detector Shodex RI-71 manufactured by Showa Denko KK
Eluent: Tetrahydrofuran (THF)
Flow rate: Sample side: 1 mL / min Reference side: 0.5 mL / min Temperature: 40 ° C.
Sample: 0.2% THF solution (injection volume 100 μL)
Calibration curve: A calibration curve was prepared using 12 standard polystyrenes with the following molecular weights manufactured by Tosoh Corporation.
F128 (1.09 X10 ⁶ ), F80 (7.06 X10 ⁵ ), F40 (4.27 X10 ⁵ ), F20 (1.90 X10 ⁵ ), F10 (9.64 X10 ⁴ ), F4 (3.79 X10 ⁴ ), F2 ( 1.81 × 10 ⁴ ), F1 (1.02 × 10 ⁴ ), A5000 (5.97 × 10 ³ ), A2500 (2.63 × 10 ³ ), A1000 (1.05 × 10 ³ ), A500 (5.0 × 10 ² ).
Baseline: The starting point of the first peak of the GPC curve was the starting point, and no peak was detected at a retention time of 25 minutes (molecular weight 3,150). And the molecular weight was calculated | required by making the line which connected both points into the base line.

<Measurement of hydroxyl value>
The measurement was performed according to JISK0070.

<Measurement of Tg>
・ Apparatus: Differential scanning calorimeter DSC-220C manufactured by Seiko Instruments Inc.
-Sample: about 10 mg (weigh to 0.1 mg)
・ Temperature increase rate: Measured to 200 ° C. at 10 ° C./min. ・ Tg temperature: Draw at the point where the gradient becomes maximum on the low temperature side of the straight line and the low temperature side curve of the melting peak. The temperature at the intersection of the broken lines was defined as Tg.

<Crosslinking agent (B)>
[Crosslinking agent A]
BI7982 (block isocyanate, base isocyanate: HDI trimer, block agent: DMP, dissociation temperature 110 ° C., non-volatile content 70%, manufactured by Baxenden Chemicals Limited [crosslinking agent B]
Duranate MF-K60B (block isocyanate, base isocyanate: HDI, blocking agent: active methylene, dissociation temperature 90 ° C., non-volatile content 60%, manufactured by Asahi Kasei Chemicals)
[Crosslinking agent C]
Death module BL1100 / 1 (block isocyanate, base isocyanate: TDI, blocking agent: ε-caprolactam, dissociation temperature 160 ° C., non-volatile content 100%, manufactured by Sumika Covestro Urethane Co., Ltd.)
[Crosslinking agent D]
EH-105L (aromatic amine, amine value 370 mgKOH / g, non-volatile content 100%, manufactured by ADEKA)
[Crosslinking agent E]
IRGACURE907 (2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, nonvolatile content 100%, BASF)

[Inorganic fine particles]
SG-95 (talc, non-volatile content 100%, manufactured by Nippon Talc)

[Monofunctional (meth) acrylic monomer (1)]
Light acrylate LA (Lauryl acrylate, manufactured by Kyoeisha Chemical Co., Ltd.)

[Multifunctional (meth) acrylic monomer (2)]
Miramer M220 (Tripropylene glycol diacrylate, MIWON)

[Curing accelerator]
XK-614 (metal complex, 100% non-volatile content, manufactured by KINGINDUSTRIES)

[Defoamer]
AC-326F (vinyl ether resin, non-volatile content 100%, manufactured by Kyoeisha Chemical Co., Ltd.)

(Preparation of resin composition)
<Example 1>
By mixing resin solution 1: 100 parts, crosslinking agent A: 3.0 parts, accelerator: 0.20 parts, antifoaming agent: 0.50 parts, solvent: 20.0 parts with a planetary mixer. A resin composition was prepared.

<Examples 2 to 20, Comparative Examples 1 to 5>
Except having changed the resin solution shown in Table 1-Table 2, a crosslinking agent, an accelerator, an antifoamer, a solvent, and a compounding ratio, it carried out similarly to Example 1, respectively Examples 2-20 and Comparative Example 1 ~ 5 resin compositions were prepared.

<Example 21>
Resin solution 1: 100 parts, crosslinking agent A: 3.0 parts, inorganic fine particles: 8.0 parts, accelerator: 0.20 parts, antifoaming agent: 0.50 parts, solvent: 20.0 parts The resin composition was prepared by mixing with a Lee mixer and then dispersing using a three roll.

<Example 22>
13: 100 parts of resin solution, 20 parts of crosslinking agent E, 180 parts of monofunctional (meth) acrylic monomer (1), and 120 parts of polyfunctional (meth) acrylic monomer (2) are mixed with a planetary mixer. Thus, a resin composition was prepared.

<Preparation of tensile modulus measurement sheet>
The obtained resin composition was coated on a peelable sheet (commercially foamed PET film) using a doctor blade so that the thickness after drying was 20 μm. Next, the test sheet 1 was obtained by curing and drying in an oven at 130 ° C. for 30 minutes. As shown in FIG. 3, the cured coating 32 of the test sheet 1 cut to a length of 50 mm and a width of 10 mm was set on a 35 mm SLIDE MOUNT 31 manufactured by Horsho, and a sample 30 was produced.
-Foamed PET film: CN100 manufactured by Toyobo Co., Ltd. (thickness 50 μm)

<Measurement of film thickness>
The thickness of the protective film in the obtained protective film sheet was measured using an MH-15M type measuring instrument (manufactured by Nikon Corporation).

<Evaluation of tensile modulus, tensile stress, and yield point>
For the sample 30, the tensile modulus, tensile stress when stretched by 2%, and yield point were measured using a small desktop tensile tester (EZ-SX, manufactured by Shimadzu Corporation). The upper part and the lower part of the sample 30 in FIG. 3 are fixed with a test piece gripper (chuck), and after cutting XY and X′-Y ′ of the sample 30 in FIG. The upper part was stretched at 01 mm / second, and the stress and yield point when stretched by 2% were measured under the following conditions. The tensile elastic modulus was evaluated according to JIS K7161. Specifically, when the stresses corresponding to the two specified strains ε1 = 0.05% and ε2 = 0.25% are σ1 and σ2, respectively, the stress difference (σ2−σ1) is strained. The value obtained by dividing by the difference (ε2−ε1) was taken as the tensile elastic modulus (E) and obtained based on the following formula.
E = (σ2−σ1) / (ε2−ε1)
E: Tensile modulus (MPa), σ: Tensile stress (MPa), ε: Tensile strain

<Preparation of storage elastic modulus test sheet>

Sample 2 was a cured coating obtained by cutting the peelable sheet after cutting into 28 mm length × 5 mm width using the test sheet 1.

<Evaluation of storage modulus>
The storage elastic modulus of Sample 2 was measured under the following conditions using a dynamic viscoelasticity measuring device (DVA-225 manufactured by IT Measurement Control Co., Ltd.).
Distance between chucks: 20 mm
Temperature increase rate: 10 ° C / second Measurement temperature range: 25-200 ° C

<Preparation of sheet for adhesion test>
A sample used for the adhesion test will be described based on FIG. The obtained resin composition was screen-printed on the ITO laminated film 41 so that the thickness after drying was 7 μm, and a protective film 42 of 15 mm length × 30 mm width was formed. Next, the test sheet 2 was obtained by drying in an oven at 130 ° C. for 30 minutes. Using the obtained test sheet 2, the adhesion of the protective film 42 to the transparent conductive film was evaluated.
-ITO laminated film: commercial product (surface resistance value of ITO layer: 150Ω / □, substrate: PET, thickness: 100 μm)

<Evaluation of adhesion>
1. Initial adhesion Using the obtained test sheet 2, a tape adhesion test was performed. The tape adhesion test was performed in accordance with JISK5600.
Specifically, it is a depth that reaches the base material but does not cut, and uses a cutter knife to make 11 cuts in the vertical direction and 11 horizontal cuts at intervals of 1 mm in width, and 10 squares × 10 squares. A total of 100 squares were formed. Next, after attaching a commercially available cellophane tape (25 mm width, manufactured by Nichiban Co., Ltd.) to the cured coating surface, the cellophane tape was rapidly peeled by hand to evaluate the state of the remaining cells.
・ Evaluation criteria ○: No change. (Good)
(Triangle | delta): Although the whole mass does not peel, a part of square is peeled. (No problem in practical use)
X: One or more squares peel. (Not practical)

2. Adhesiveness after wet heat test The obtained test sheet 2 was allowed to stand for 240 hours in an 85 ° C. and 85% atmosphere, then left for 1 hour in a 23 ° C. and 50% atmosphere, and then evaluated for adhesion in the same manner as the initial adhesiveness. did. Evaluation was performed according to the same criteria as described above.

<Resistance value>
A flexibility test was performed to evaluate the change in resistance before and after the test. A method for manufacturing a sample will be described based on FIG. 5A and a side view. Screen printed so that the film thickness after drying a conductive paste (REXALPHA RA FS074, manufactured by Toyochem Co., Ltd.) on the ITO laminated film 51 becomes 5 μm, and a resistance value measuring terminal portion of 15 mm in length × 3.5 mm in width The 52-1 and the resistance value measuring terminal portion 52-2 were formed with an interval of 75 mm, dried for 30 minutes in a 135 ° C. oven, and cured. Next, the resin composition obtained on the ITO laminated film 51 was screen-printed so that the film thickness after drying was 7 μm, and a protective film 53 of 15 mm length × 70 mm width was formed. Subsequently, it dried for 30 minutes in 130 degreeC oven, it was made to harden, and the test sheet 3 was produced.
If the resistance value is measured by directly applying a terminal to the ITO layer with a tester, the ITO layer is damaged and an accurate resistance value cannot be measured. Therefore, a resistance value measuring terminal portion is formed on the ITO with silver paste, The resistance value was measured by applying a tester.

<Evaluation of resistance value change rate>
Using the obtained test sheet 3, a flexibility test was performed. The bendability test is performed using a bend resistance tester (manufactured by Yuasa System Equipment Co., Ltd., a planar body no-load U-shaped stretch tester), and set in the apparatus so that the protective film of the test sheet 3 is on the lower side. The sample was bent by 50,000 times at a diameter of 4 mm and a speed of 30 times / minute. The change rate of the surface resistance value was calculated from the following formula.
Rate of change = (Surface resistance value after 50,000 bending bending before surface resistance test) / (Surface resistance value before test × 100)
・ Evaluation criteria ○: Change rate is less than 10% (good)
Δ: Change rate of 10% or more and less than 30% (no problem in practical use)
X: Change rate is 30% or more (not practical)

<Water vapor transmission rate>
A flexibility test was performed to evaluate the water vapor transmission rate after the test. A method for manufacturing a sample will be described based on FIG. 6A and a side view.
The resin composition obtained on the film 61 with a silica vapor deposition layer was screen-printed so that the film thickness after drying might be 7 micrometers, and the protective film 62 of length 100mm x width 100mm was formed. Next, the test sheet 4 was prepared by curing and drying in a 130 ° C. oven for 30 minutes. A flexibility test was performed using the obtained test sheet 4. The flexibility test was performed in the same manner as the above resistance value measurement method.
-Film with silica vapor deposition layer: Tech Barrier LX manufactured by Mitsubishi Plastics (base material: PET, thickness 12 μm)

<Evaluation of water vapor transmission rate>
The water vapor transmission rate after the flexibility test of the test sheet 4 was measured using a water vapor transmission rate measuring device (PERMATRAN manufactured by MOCON). The measurement conditions were 40 ° C. and 100% R.D. H. The test was conducted for 24 hours. The obtained actual measurement value was converted into a result at a thickness of 100 μm and evaluated according to the following criteria.
○: Water vapor transmission rate is less than 1.0 g / (m ² · day) (good)
Δ: Water vapor transmission rate is 1.0 g / (m ² · day) or more and less than 2.0 g / (m ² · day) (practical range)
X: Water vapor transmission rate is 2.0 g / (m ² · day) or more (not practical)

<Solvent resistance, transparency>
The solvent resistance test and the transparency test will be described with reference to FIG.
The resin composition obtained on the PET film 71 was screen-printed so that the film thickness after drying was 7 μm to form a protective film 72 of 70 mm length × 40 mm width. Subsequently, the test sheet 5 was obtained by curing and drying in a 130 ° C. oven for 30 minutes.
PET film: A4100 manufactured by Toyobo Co., Ltd. (thickness: 100 μm, easy adhesion treatment)

<Solvent resistance evaluation>
A solvent resistance test was carried out using the obtained test sheet 5. The solvent resistance of the protective film was tested by rubbing 30 times on the surface of the protective film of the test sheet 5 using a cotton swab containing propylene glycol monomethyl ether acetate (PGMAC). Evaluation was performed by visually observing the surface after the test.
-Evaluation criteria ○: The gloss of the protective film does not change before and after the test (good)
Δ: The gloss of the protective film slightly decreased. (No problem in practical use)
X: The protective film was swollen with PGMAC or peeled off from the PET film. (Not practical)

<Transparency evaluation>
A transparency test was performed using the obtained test sheet 5. Transparency was measured using a light source D65 with HAZEMETERNDH2000 (Nippon Denshoku).
・ Evaluation criteria ○: The transmittance is 90% or more (good)
Δ: Transmittance is 80% or more and less than 90% (no problem in practical use)
×: Transmittance is 80% or less (not practical)

From the results of Tables 1 and 2, Examples 1 to 22 are practically satisfactory evaluation results in the evaluation items of adhesion to the functional layer, suppression of increase in resistance value after bending, and water vapor barrier property after bending. Met.
On the other hand, from the results shown in Table 3, since Comparative Example 1 did not contain a curing agent, the curability was low and wet heat resistance and solvent resistance were poor. Comparative Examples 2 to 4 did not satisfy all the evaluation items because the numerical values of Tg and Mn of the resin (A) were not appropriate. Moreover, since Comparative Example 5 did not have a ring structure, the adhesion was poor.

11 Base material 12 IM layer 13 Transparent electrode layer 14 Protective film 15 Adhesive layer 21 Base material 22 TFT
23 Organic EL light emitting layer 24 Transparent electrode layer 25 Inorganic barrier layer 26 Protective film 27 Adhesive layer 30 Sample 31 SLIDE MOUNT
32 Protective film 41 ITO laminated film 42 Protective film 51 ITO laminated film 52-1 Resistance value measuring terminal part 52-2 Resistance value measuring terminal part 53 Protective film 61 Film with silica vapor deposition layer 62 Protective film 71 PET film 72 Protective film

<Example 22>
13: 100 parts of resin solution, 20 parts of crosslinking agent E, 180 parts of monofunctional (meth) acrylic monomer (1), and 120 parts of polyfunctional (meth) acrylic monomer (2) are mixed with a planetary mixer. Thus, a resin composition was prepared. In this specification, Example 22 is a reference example.

Claims (6)

A light-transmitting resin composition comprising a resin (A) having a glass transition temperature of 30 to 170 ° C. and a number average molecular weight of 2,000 to 140,000 and a ring structure, and a crosslinking agent (B),
The cured film of the light transmissive resin composition has a tensile modulus of 400 to 4000 MPa at a tensile speed of 0.01 mm / second, and a tensile stress of 15 to 60 MPa when the cured film is stretched by 2%. A permeable resin composition.   The light transmissive resin composition according to claim 1, wherein the resin (A) has a hydroxyl value of 2 to 400 mgKOH / g.   The light-transmitting resin composition according to claim 1, wherein the crosslinking agent (B) contains a blocked isocyanate.   The light-transmitting resin composition according to claim 3, wherein the blocked isocyanate has a dissociation temperature of the blocking agent of 80 to 180 ° C.   The light-transmitting resin composition according to any one of claims 1 to 4, comprising 1 to 30 parts by weight of the crosslinking agent (B) with respect to 100 parts by weight of the resin (A).   The display provided with the base material and the protective film which is a hardened | cured material of the light transmissive resin composition of any one of Claims 1-5.

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