KR101615050B1 - Polymerizable composition and application for same - Google Patents

Abstract

(A) an isocyanate compound and (B) 4,8 or 4,7 or 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiane undecane, 4-mercapto Methyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis mercaptoacetate, pentaerythritol tetrakis mercaptopropionate, 2,5-bis (mercaptomethyl) -1,4 Dithiane, bis (mercaptoethyl) sulfide, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 4,6-bis (mercaptomethylthio) And at least one thiol compound selected from 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-dithiethane and (C) an organic strong base salt.

Description

[0001] POLYMERIZABLE COMPOSITION AND APPLICATION FOR SAME [0002]

The present invention relates to a polymerizable composition and a use thereof.

In recent years, an organic EL (ELectro Luminescence) display device is expected to be a next-generation display or illumination device because of low power consumption and low viewing angle dependence.

The light emitting element of the organic EL display device has a structure in which an electrode, an organic light emitting layer, and a transparent electrode are laminated. The light (light) emitted from the organic light emitting layer is transmitted through the optically transparent electrode and taken out from the outside.

Patent Document 1 discloses a technique for providing a light extraction layer having various shapes on a transparent electrode in order to improve the ratio of light emitted from the outside (external light emission efficiency) to light emitted from the organic emission layer . This document describes that the light-extraction layer made of a resin has a predetermined refractive index.

As a resin composition capable of obtaining a molded article having a high refractive index, Patent Document 2 discloses a urethane resin composition containing an ester compound such as an isocyanate compound, a hydroxy compound, a mercapto compound, etc., and a tertiary amine and a Lewis acid .

Further, Patent Document 3 discloses a process for producing an isocyanate compound, which comprises reacting one or more isocyanates selected from the group consisting of an isocyanate compound and an isothiocyanate compound, an active hydrogen compound having a mercapto group and a catalyst such as dimethyl tin dichloride ≪ / RTI > are disclosed. This document describes that an optical film or the like was formed using a polymerizable composition.

Patent Document 1: JP-A-2009-283349 Patent Document 2: JP-A-8-208792 Patent Document 3: International Publication No. 2011/058754 pamphlet

Summary of the Invention

However, the techniques described in Patent Documents 2 and 3 have room for improvement in the following points.

In order to use the polymerizable resin composition in a manufacturing process of an electronic part or an electronic device, it is required to have excellent port life at room temperature after preparation of a polymerizable resin composition, and at the time of use, It is also required to have excellent thermosetting property. However, in terms of their properties, in the trade-off relationship, a polymerizable resin composition that satisfies all of these properties can not be obtained.

The present invention can be shown as follows.

(A) an isocyanate compound, (B) 4,8 or 4,7 or 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4 -Mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis mercaptoacetate, pentaerythritol tetrakis mercaptopropionate, 2,5-bis (mercaptomethyl) 1,4-dithiane, bis (mercaptoethyl) sulfide, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 4,6-bis (mercaptomethylthio) A polymerizable composition comprising at least one thiol compound selected from dithiane, 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-dithiane and (C) an organic strong base salt .

(2) The polymerizable composition according to the above (1), wherein the organic strong base salt (C) has a dissociation temperature of 50 DEG C or higher in the DCS measurement.

(3) The polymerizable composition according to the above (1) or (2), wherein the organic strong base salt (C) is a tertiary amine salt.

(4) The tertiary amine salt is 1,8-diazabicyclo [5. 4. 0] undecene-7, or 1,5-diazabicyclo [4. 3. 0] nonene-5. ≪ / RTI >

(5) The isocyanate compound (A) is at least one compound selected from the group consisting of phenylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, m-xylene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,5-bis (isocyanatomethyl) -bicyclo [2. 2.1] heptane, and 2,6-bis (isocyanatomethyl) -bicyclo [2. (1) to (4) above, wherein the polymerizable composition is at least one selected from the group consisting of propylene, isobutylene, and isobutylene.

(6) The polymerizable composition according to any one of (1) to (5), further comprising an inorganic filler.

(7) An optical thin film having at least one layer comprising the polymerizable composition according to any one of (1) to (5).

(8) An encapsulating material comprising the polymerizable composition according to any one of (1) to (5).

(9) A substrate comprising the polymerizable composition according to (6).

(10) A surface-emitting device having a light-extraction layer comprising the optical thin film according to (7).

(11) An organic EL display using the surface emitting device according to (10) above.

(12) An organic EL lighting apparatus using the surface emitting device according to (10) above.

(13) An electronic device having a transparent heat radiation layer made of the substrate according to (9).

(14) A process for producing a polymerizable composition, comprising the steps of applying the polymerizable composition according to any one of the above items (1) to (5) onto an optical member, and sealing the optical member with an encapsulating material obtained by curing the applied polymerizable composition Wherein the optical member is a transparent member.

According to the present invention, it is possible to provide a polymerizable composition excellent in pot life at room temperature and excellent in the thermosetting property at a low temperature of about 100 캜 or lower. Therefore, it can be used in a production process of various electronic parts.

Further, the molded article obtained from the polymerizable composition of the present invention has a high refractive index, and is excellent in light resistance and processability. Therefore, the molded article made of the polymerizable composition of the present invention can be suitably used as various members such as a light emitting display device, a lighting device, and the like in which such characteristics are required.

Further, the molded article obtained from the polymerizable composition of the present invention has a high refractive index, so that it is possible to adjust the refractive index difference with an additive material such as an inorganic filler. Therefore, the molded article can exhibit the effect of the additive material while maintaining the transparency of the molded article. As a result, the molded article obtained from the polymerizable composition of the present invention can be suitably used for various members of electronic apparatuses in which such characteristics are required.

Carrying out the invention  Form for

The present invention is described below.

≪ Polymerizable composition >

The polymerizable composition of the present invention may contain,

(A) an isocyanate compound, (B) a predetermined thiol compound, and (C) an organic strong base salt.

[Isocyanate compound (A)]

Examples of the isocyanate compound (A) include at least one member selected from the group consisting of methyl isocyanate, ethyl isocyanate, n-propyl isocyanate, isopropyl isocyanate, n-butyl isocyanate, sec-butylisocyanate, tert- butylisocyanate, pentylisocyanate, hexylisocyanate, heptylisocyanate, octylisocyanate, decyl Isocyanate, isocyanate, lauryl isocyanate, myristyl isocyanate, octadecyl isocyanate, 3-pentyl isocyanate, 2-ethylhexyl isocyanate, 2,3-dimethyl cyclohexyl isocyanate, 2-methoxyphenyl isocyanate, Monofunctional isocyanates such as methyl benzyl isocyanate, phenyl ethyl isocyanate, phenyl isocyanate, o-, m-, p-tolyl isocyanate, cyclohexyl isocyanate, benzyl isocyanate and isocyanatomethylbicycloheptane Sites compound;

Hexamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4- Methylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 1,6,11-undecatriisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane , Aliphatic polyisocyanate compounds such as bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, lysine diisocyanato methyl ester, and lysine triisocyanate;

(Isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate , 2,2-dimethyldicyclohexylmethane isocyanate, 2,5-bis (isocyanatomethyl) bicyclo- [2,2,1] -heptane, 2,6-bis (Cyanatomethyl) bicyclo- [2,2,1] heptane, 3,8-bis (isocyanatomethyl) tricyclodecane, 3,9-bis (isocyanatomethyl) tricyclodecane, Alicyclic polyisocyanate compounds such as bis (isocyanatomethyl) tricyclodecane, 4,9-bis (isocyanatomethyl) tricyclodecane, and bis (isocyanatocyclohexyl) methane;

(Isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, α, α, α ', α'-xylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, (Isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether, phenylenediisocyanate, tolylene diisocyanate, ethylphenylenediisocyanate, isopropyl naphthalene diisocyanate, And examples thereof include aromatic diisocyanates such as phenylenediisocyanate, dimethylphenylenediisocyanate, diethylphenylenediisocyanate, diisopropylphenylenediisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, biphenyl diisocyanate, toluidine diisocyanate, 4,4'- , 3,3-dimethyldiphenylmethane-4,4-diisocyanate, 4,4-diisocyanate, bis (isocyanatophenyl) ethylene, 3,3-dimethoxybiphenyl-4,4-diisocyanate, phenylisocyanatoethyl isocyanate, hexahydrobenzene diisocyanate, hexahydrodiphenyl Aromatic polyisocyanate compounds such as methane-4,4-diisocyanate, bis (isocyanatoethyl) phthalate, mesitylene trisisocyanate, and 2,6-di (isocyanatomethyl) furan;

Bis (isocyanatomethyl) sulfide, bis (isocyanatomethyl) sulfide, bis (isocyanatomethyl) sulfide, bis (isocyanatomethyl) sulfide, bis Bis (isocyanatomethylthio) methane, bis (isocyanatomethylthio) methane, bis (isocyanatomethylthio) ethane, bis (isocyanatomethylthio) A sulfo aliphatic polyisocyanate compound such as 1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane;

Diphenylsulfide-2,4-diisocyanate, diphenylsulfide-4,4-diisocyanate, 3,3-dimethoxy-4,4-diisocyanatodibenzylthioether, bis (4- Methylbenzene) sulfide, 4,4-methoxybenzenethiethylene glycol-3,3-diisocyanate, diphenyldisulfide-4,4-diisocyanate, 2,2-dimethyldiphenyldisulfide- Diisocyanate, 3,3-dimethyl diphenyl disulfide-5,5-diisocyanate, 3,3-dimethyl diphenyl disulfide-6,6-diisocyanate, 4,4-dimethyl diphenyl disulfide- A sulfided aromatic polyisocyanate compound such as diisocyanate, 3,3-dimethoxydiphenyl disulfide-4,4-diisocyanate, and 4,4-dimethoxydiphenyl disulfide-3,3-diisocyanate;

2,5-bis (isocyanatomethyl) thiophene, 2,5-diisocyanatotetrahydrothiophene, 2,5-bis (isocyanatomethyl) tetrahydrothiophene, Dithiane, 2,4-bis (isocyanatomethyl) tetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, (Isocyanatomethyl) -1, 3-dithiolane, 4,5-bis (isocyanatomethyl) -2- Methyl-1,3-dithiolane, and the like; And the like. One or more of these may be used in combination.

In the present invention, it is preferable to use an aliphatic polyisocyanate compound, an alicyclic polyisocyanate compound, or an aromatic polyisocyanate compound. Specific examples thereof include phenylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, m-xylene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,5-bis (isocyanatomethyl) -bicyclo [ 2.1] heptane, and 2,6-bis (isocyanatomethyl) -bicyclo [2. 2.1] heptane is preferably used.

In the present invention, it is more preferable to use an aromatic polyisocyanate compound. Among them, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, phenylene diisocyanate, m-xylene diisocyanate, 2,5-bis Isocyanatomethyl) -bicyclo [2. < / RTI > 2.1] heptane, 2,6-bis (isocyanatomethyl) -bicyclo [2. 2.1] heptane is particularly preferably used. These aromatic polyisocyanate compounds can be preferably used also from the viewpoint of use as a one-pack type resin composition to be described later.

[Thiol compound (B)]

As the thiol compound (B), 4,8 or 4,7 or 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, 4-mercaptomethyl- , 8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis mercaptoacetate, pentaerythritol tetrakis mercaptopropionate, 2,5-bis (mercaptomethyl) -1,4- , Bis (mercaptoethyl) sulfide, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 4,6-bis (mercaptomethylthio) 2,2-bis (mercaptomethylthio) ethyl) -1,3-dithiane.

In the present invention, it is preferable to use 4,8 or 4,7 or 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, 4-mercaptomethyl-1,8 -Dimercapto-3,6-dithiaoctane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 4,6-bis (mercaptomethylthio) It is preferable to use at least one selected from 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-dithiethane.

From the viewpoint of use as a one-pack type resin composition described later, it is also possible to use 4,8 or 4,7 or 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane is preferably used as an essential component.

[(C) Organic Strong Base Salt]

The organic strong base salt (C) used in the present invention is a salt composed of an organic acid and a strong base, and exhibits catalytic activity when the organic acid and base are dissociated by heating, while the catalytic activity at room temperature is low. It is presumed that a polymerizable composition having both pot life and curability can be obtained by selecting a catalyst which has a dissociation temperature (dissociation temperature of salt) sufficiently higher than room temperature and which dissociates near the curing temperature of the desired polymer.

In the present invention, the " dissociation temperature " of the organic strong base salt (C) refers to the temperature at which the endotherm begins to be observed in the DSC measurement.

As the organic strong base salt (C), a dissociation temperature of 40 DEG C or higher, preferably 50 DEG C or higher can be used in DSC measurement (differential scanning calorimetry). At this dissociation temperature, dissociation of the acid-base of the organic strong base salt (C) is initiated. That is, this dissociation temperature can be considered to mean the initiation of the expression of catalytic activity.

By selecting the organic strong base salt having the range of the enumeration agreement near the predetermined curing temperature, it is possible to provide a polymerizable composition which is excellent in pot life and can be cured at a low temperature of about 100 DEG C or less by suppressing curing at room temperature .

It is also believed that the dissociation of the salt can be indirectly evaluated also by the polymerization enumeration of the (thio) urethane reaction. In this case, a starting temperature at which heat generation of polymerization is observed may be 50 占 폚 or higher, preferably 60 占 폚 or higher.

As such an organic strong base salt (C), a salt of an amine compound and an organic acid can be used.

Examples of the amine compound include 1,8-diazabicyclo [5,4,0] -7-undecene, 1,8-diazabicyclo [4,3,0] -7-nonene, 1,5-diazabicyclo [4, 3, 0] non-5-ene, N, N-dimethylaminopyridine, 1,5,7-triazabicyclo [ 4] decane-5-ene, 7-methyl-1,5,7-triazabicyclo [4. 4. 0] deca-5-ene;

Secondary amines such as 2,2,6,6-tetramethylpiperidine;

And the like.

Examples of the organic acid include phenol, octylic acid, phthalic acid, p-toluenesulfonic acid, formic acid, orthophthalic acid, oxalic acid, succinic acid, acetic acid, maleic acid, benzoic acid, dodecylbenzenesulfonic acid, octanoic acid, Acrylic acid, maleic acid, maleic anhydride, and the like.

In the present invention, it is preferable to use a tertiary amine salt as the organic strong base salt (C). Examples of such tertiary amine salts include 1,8-diazabicyclo [5. 4. 0] undecene-7, octylate, phthalate, p-toluenesulfonate;

1,5-diazabicyclo [4. 3. 0] nonene-5, octylate, phthalate, p-toluenesulfonate;

And the like, and one or more selected from these can be used in combination.

In the present invention, 1,8-diazabicyclo [5. 0.0 > undecene-7 < / RTI >

[Other components]

The polymerizable composition of the present invention may further contain other components. Depending on the application, it can be selected appropriately.

Examples of the additives include additives such as ultraviolet absorbers such as benzotriazole, reaction initiators such as external or internal release agents, light stabilizers, chain extenders, crosslinking agents, antioxidants, coloring inhibitors, antioxidants and radical reaction initiators, chain extenders, Various additives such as a coloring inhibitor, a useful dye, an inorganic filler, and an adhesion improver may be added. The inorganic filler may be subjected to a surface treatment to adjust the refractive index. These additives may be added in advance to the polymerizable composition.

For the purpose of modifying the polythiourethane resin obtained from the polymerizable composition, an olefin compound including a hydroxy compound, an amine compound, an epoxy compound, an episulfide compound, an organic acid and an anhydride thereof, a (meth) Of the resin modifier may be added. Here, the resin modifier is a compound that adjusts or improves the mechanical strength such as the physical properties such as the refractive index, the Abbe number, the heat resistance, the specific gravity, and the impact resistance of the polythiourethane resin.

In the present invention, the combination of the isocyanate compound (A) and the thiol compound (B) and other components are not limited, and may be selected depending on the process conditions such as refractive index, curing temperature, do.

In the present invention, a preferable combination of the isocyanate compound (A) and the thiol compound (B) is a combination of the isocyanate compound (A) and the thiol compound (B) Isocyanate, 4,4'-diphenylmethane diisocyanate, phenylene diisocyanate, 2,5-bis (isocyanatomethyl) -bicyclo [2. 2.1] heptane, 2,6-bis (isocyanatomethyl) -bicyclo [2. 2.1] heptane, and the thiol compound (B) is at least one selected from the group consisting of 4,8 or 4,7 or 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 4,6- Bis (mercaptomethylthio) -1,3-dithiane, and 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-dithiane.

≪ Process for producing polymerizable composition >

In the present invention, the ratio of the raw material containing the isocyanate compound (A), the thiol compound (B) and the hydroxyl compound as the modifier used as the raw material is preferably such that the molar ratio of the functional group of (NCO + NCS) / (SH + OH) Or more and 3.0 or less, preferably 0.6 or more and 2.0 or less, more preferably 0.8 or more and 1.3 or less.

The polymerizable composition of the present invention can be prepared by mixing the isocyanate compound (A), the thiol compound (B), the organic strong base salt (C) and other components in a batch. Further, after prepolymerization, the remaining components can be mixed and added.

The order of addition of the organic strong base salt (C) and other additives, which are catalysts, depends on the solubility in the monomer, but it may be added in advance to dissolve in the isocyanate compound (A), dissolve in the thiol compound (B) May be added and dissolved in a mixture of the compound (A) and the thiol compound (B). Alternatively, it may be dissolved in a part of the monomers used to prepare a master liquid, and then this master liquid may be added. The order of addition is not limited to these examples, but is appropriately selected on the basis of operability, safety, convenience, and the like.

The catalyst may be added in the form of the catalyst itself or dissolved in a part of the monomers used to prepare the master liquid and then added.

The polymerizable composition thus obtained has an initial viscosity of 20 to 50,000 mPa 占 퐏, preferably 100 to 5000 mPa 占 퐏, measured at 25 占 폚 using an E-type viscometer. The polymerizable composition is excellent in pot life at room temperature and has a viscosity magnification of 1 to 10, preferably 1 to 5 after 12 hours represented by the following formula (1).

Expression: b / a ... (One)

(a: initial viscosity at 25 캜, b: viscosity after 12 hours)

The viscosity magnification after 24 hours represented by the following formula (2) is 1 to 20, preferably 1 to 10. [

Expression: c / a ... (2)

(a: initial viscosity at 25 캜, c: viscosity after 24 hours)

The viscosity of the polymerizable composition of the present invention varies depending on the intended use, but the viscosity ratio after 12 hours and / or 24 hours is within the above range, so that the polymerizable composition can be suitably used for various electronic parts and electronic device manufacturing processes have.

The manufacturing process of various electronic parts and electronic devices reaches a number of processes. Since the polymerizable composition of the present invention is excellent in pot life at room temperature, the polymerizable composition of the present invention can be used not only as a two-liquid type requiring preparation in the field but also as a one-part type resin composition. Therefore, it can be used for an application (for example, an encapsulating material) in which a pot life is required after a daily amount, thereby avoiding troubles in the manufacturing process.

The temperature at which a polymerizable composition is prepared by mixing an isocyanate with an active hydrogen compound, a reaction catalyst, a releasing agent, and other additives is usually 25 占 폚 or less. From the viewpoint of pot life of the composition, it may be preferable to make the temperature lower. However, when the solubility of the reaction catalyst, the releasing agent, or the additive in the monomer is not good, it may be heated in advance to dissolve the monomer in a mixture of an isocyanate or an active hydrogen compound or a monomer.

<Optical Thin Film or Substrate>

The molded article obtained from the polymerizable composition of the present invention can be used as an optical thin film or a substrate.

The optical thin film of the present invention can be used as a self-supporting film or a coating film. This optical thin film can be produced by a usual method and can be obtained by cast (thin film coating-polymerization curing) method, spin coat-polymerization curing method, casting polymerization method or the like using the above-mentioned polymerizable composition.

The casting method and the spin-coat polymerization curing method can be carried out by extruding a viscosity-controlled polymerizable composition from a die and casting the composition on a substrate, or by forming a thin film by rotating the substrate at a high speed while rotating the composition, · A method of obtaining a thin film by curing. The viscosity of the mixture at the time of casting (coating) is appropriately selected depending on the coating method and the application thereof.

The casting polymerization method is a method in which a pair of inorganic glass or metal or resin plate sealed with oblique lines and partially forming a thiourethane bond and forming a thiourethane in a mold having an interval of not more than 200 mu m Which is a mixture of a compound having an isocyanate group and a compound having a thiol group, is injected into the surface of the polymerizable composition and polymerized to obtain a film. The viscosity at the time of injecting the mixture is appropriately selected by an injection method, a curing process or the like. Further, it can be obtained as a substrate by adjusting the intervals of the molds.

The thickness of the optical thin film or the substrate is suitably different depending on the application, and can be suitably adjusted.

The molded article of the present invention thus obtained has a high refractive index and a refractive index n of 1.55 or more, preferably 1.60 or more. As described later, when an optical thin film is used as the sealing material, it is preferable that the refractive index n is 1.65 or more.

<Usage>

The optical thin film may be a polarizing film, a polarizing film, a polarizing plate protective film, a polarizing plate protective film, a retardation film, an orientation film (orientation film), a viewing angle enlargement (compensation) film, a diffuser plate (film), a prism sheet, (ACF), an electromagnetic shielding (EMl) film, an antireflection (LR) film, an antiglare (AG) film, a transparent conductive ) Film, a film for an electrode substrate, a film for a color filter substrate, a barrier film, a sealing material, a color filter layer, a black matrix layer and the like. As described above, the optical thin film of the present invention may be formed inside or outside various optical members such as a liquid crystal display, an organic EL display, a plasma display, and a solar cell, and the present invention provides such an optical member.

The optical thin film of the present invention has at least one layer comprising the polymerizable composition. Specifically, the optical thin film may be composed of only the layer made of the polymerizable composition, or may be a laminate having at least one layer of the polymerizable composition.

When the optical thin film is a laminate, the layer comprising the polymerizable composition can be used as the above-mentioned film or the like, and can be further included as a coat layer. Other layers constituting the laminate include a light-transmitting layer, an antireflection layer, a conductive layer, an electromagnetic wave shielding layer, and a base layer.

The optical member can be encapsulated with the polymerizable composition of the present invention. Examples of the optical member include an organic EL device and a solar cell.

The sealing method of the optical member may include a step of applying the polymerizable composition of the present invention onto an optical member and a step of sealing the optical component with an encapsulating material obtained by curing the applied polymerizable composition.

The polymerizable composition can be applied by a roll coating method, a die coating method, a spin coating method, a screen printing method, or the like. The coating film composed of the polymerizable composition can be cured by heat or light.

The optical thin film of the present invention can be preferably used as a light extraction layer of a surface emitting device used in a light emitting display device or a lighting device. For example, an organic EL display or an organic EL lighting device including a surface emitting device in which an electrode, a light emitting layer, a transparent electrode, and a light extraction layer comprising an optical film are stacked in this order can be used. Specifically, one surface of the thin film is processed into a concavo-convex shape, and the other surface is adhered to the light emitting surface of the light emitting device to form the light emitting layer, whereby light reflected inside the light emitting element is extracted to the outside, Can be improved.

Further, when the polymerizable composition of the present invention contains an inorganic filler, since the inorganic filler functions as a heat radiation material, the substrate made of the resin can be used as a transparent heat radiation plate (layer) in an electronic device. Further, this substrate has a high refractive index, and it is possible to adjust the refractive index difference with an additive material such as an inorganic filler. Therefore, the substrate can be used for applications in which transparency of the substrate can be maintained, light is emitted or taken in, and further heat dissipation is required. Examples of the electronic component include a solar cell, an organic EL display, an organic EL lighting device, an LED, an LED lighting, and a liquid crystal display. For example, when the solar cell is used for a solar cell, the substrate can be disposed on the light-receiving surface side (light-receiving surface side) of the solar cell.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited to these examples and the like.

The characteristics of the monomer solution and the cured product obtained in this example were evaluated by the following test methods.

The viscosity a after 12 hours and the viscosity b after 12 hours at 25 ° C were measured using a TV-22 type and a BL viscometer manufactured by Toray Industries, Ltd. In the formula: b / a, 12 The viscosity magnification was measured after the lapse of time.

Refractive index: The various monomer mixtures were cast on glass and cured sufficiently using a hot plate at 100 占 폚. The refractive index of the cured resin film (film thickness 30 mu m) was measured at 20 DEG C (sodium D line: 589 nm) using a multi-wavelength Abbe refractometer manufactured by ATAGO.

Curing property: The mixture of various monomers was heated and cured on a hot plate at 100 占 폚 / 60 minutes in a nitrogen atmosphere. The cured resin molded product (film thickness 30 占 퐉) was immersed in acetone, and the state was visually evaluated based on the following criteria.

○: Insoluble in acetone

?: Partially soluble in acetone

X: completely dissolved in acetone

The components used in this example are as follows.

Diisocyanate compound

(A-1): 4,4'-diphenylmethane diisocyanate (COSMONATE-PH manufactured by Mitsui Chemicals, Inc.)

(A-2): 2,4-tolylene diisocyanate (Cosmonate T-100 manufactured by Mitsui Chemicals, Inc.)

Polythiol compound

(A-3): m-xylene diisocyanate

(A-4): 2,5-bis (isocyanatomethyl) -bicyclo [2. 2.1] heptane, and 2,6-bis (isocyanatomethyl) -bicyclo [2. 2.1] heptane

(B-1): 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane

(B-2): 4,8-, 4,7-, 5,7-dimercaptomethyl-1,11 (2-ethylhexyl) -Dimercapto-3,6,9-trithiandecane polythiol compound

(B-3): 1,1,3,3-tetrakis (mercaptomethylthio) propane synthesized in accordance with the method described in Production Example 2 of JP-A No. 2004-002820, 4,6- A mixture of bis (mercaptomethylthio) -1,3-dithiane and 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-dithiane

catalyst

(C-1): 1,8-diazabicyclo [5. 4. 0] undecene-7 (manufactured by San A Pro Co.), dissociation temperature (DSC measurement): 50 ° C

(C-2): dibutyl tin dichloride

[Example 1]

2.5 mg of the catalyst (C-1) was added to 20.8 g of the polythiol compound (B-1) and mixed well. This was added to 29.2 g of the heat-dissolved diisocyanate compound (A-1) and mixed by heating to obtain a monomer mixture solution 1. The initial viscosity of the monomer mixture solution 1 was 260 mPa · s. Using this monomer mixture solution 1, the viscosity magnification, refractive index and curability after 12 hours were confirmed by the above test method. The results are shown in Table-1.

[Example 2]

2.5 mg of the catalyst (C-1) was added to 21.8 g of the polythiol compound (B-2) and mixed well. This was added to 28.2 g of the heat-dissolved diisocyanate compound (A-1), and the mixture was heated and mixed to obtain a monomer mixture solution 2. The initial viscosity of the monomer mixture solution 2 was 250 mPa · s. Using this monomer mixture solution 2, the viscosity magnification, refractive index, and curability after 12 hours were confirmed by the above test method. The results are shown in Table-1.

[Example 3]

2.5 mg of the catalyst (C-1) was added to 27.1 g of the polythiol compound (B-2) and mixed well. This was added to 22.9 g of the diisocyanate compound (A-2) and mixed well to obtain a monomer mixture solution 3. The initial viscosity of the monomer mixture solution 3 was 20 mPa.. Using this monomer mixture solution 3, the viscosity magnification, refractive index, and curability after 12 hours were confirmed by the above test method. The results are shown in Table-1.

[Example 4]

10.8 g of the polythiol compound (B-2) containing 2.5 mg of the catalyst (C-1) was added to 27.8 g of the heat-dissolved diisocyanate compound (A-1) and heated and mixed. 27.8 g of the polythiol compound (B-3) was slowly added dropwise thereto and heated and mixed to obtain a monomer mixture solution 4. The initial viscosity of the monomer mixture solution 4 was 660 mPa s. Using this monomer mixture solution 4, the viscosity magnification, refractive index and curability after 12 hours were confirmed by the above test method. The results are shown in Table-1.

[Example 5]

13.8 g of the polythiol compound (B-3) was slowly added dropwise to 23.3 g of the heated diisocyanate compound (A-2), and the mixture was heated and mixed. 13.0 g of the polythiol compound (B-2) containing 2.5 mg of the catalyst (C-1) was added and mixed well to obtain a monomer mixture solution 5. The initial viscosity of the monomer mixture solution 5 was 70 mPa · s. Using this monomer mixture solution 5, the viscosity magnification, refractive index and curability after 12 hours were confirmed by the above test method. The results are shown in Table-1.

[Comparative Example 1]

2.5 mg of the catalyst (C-2) was added to 27.1 g of the polythiol compound (B-2) and mixed well. This was added to 22.9 g of the diisocyanate compound (A-2) and mixed well to obtain a monomer mixture solution 6. The initial viscosity of the monomer mixture solution 6 was 20 mPa.. Using this monomer mixture solution 6, viscosity and curability after 12 hours were confirmed by the above test method. Further, in the test of curability, since the resin molded article was completely dissolved in acetone, the measurement of the refractive index was not performed. The results are shown in Table-1.

[Comparative Example 2]

22.9 g of the diisocyanate compound (A-2) was added to 27.1 g of the polythiol compound (B-2) and mixed well to obtain a monomer mixture solution 7. The initial viscosity of the monomer mixture solution 7 was 20 mPa.. Using this monomer mixture solution 7, viscosity and curability after 12 hours were confirmed by the above test method. Further, in the test of curability, since the resin molded article was completely dissolved in acetone, the measurement of the refractive index was not performed. The results are shown in Table-1.

[Example 6]

2.5 mg of the catalyst (C-1) was added to 25.4 g of the polythiol compound (B-2) and mixed well. This was added to 24.6 g of the diisocyanate compound (A-3) and mixed well to obtain a monomer mixture solution 8. The initial viscosity of the monomer mixture solution 8 was 20 mPa.. Using this monomer mixture solution 8, the viscosity magnification, refractive index and curability after 12 hours were confirmed by the above test method. The results are shown in Table-1.

[Example 7]

2.5 mg of the catalyst (C-1) was added to 24.2 g of the polythiol compound (B-2) and mixed well. This was added to 25.8 g of the diisocyanate compound (A-4) and mixed well to obtain a monomer mixture solution 9. The initial viscosity of the monomer mixture solution 9 was 30 mPa · s. Using this monomer mixture solution 9, the viscosity magnification, refractive index and curability after 12 hours were confirmed by the above test method. The results are shown in Table-1.

[Comparative Example 3]

2.5 mg of the catalyst (C-2) was added to 21.8 g of the polythiol compound (B-2) and mixed well. This was added to 28.2 g of the heat-dissolved diisocyanate compound (A-1) and mixed by heating to obtain a monomer mixture solution 10. The initial viscosity of the monomer mixture solution 10 was 1000 mPa · s. Using this monomer mixture solution 10, the viscosity magnification, refractive index and curability after 12 hours were confirmed by the above test method. The results are shown in Table-1.

As shown in Table 1, the resin composition of the present invention has low viscosity magnification after 12 hours at room temperature and excellent port life at room temperature. The resin molded product obtained by heating and curing at 100 占 폚 is insoluble in acetone and excellent in thermosetting property even at a low temperature of about 100 占 폚. Thus, the polymerizable composition of the present invention can be used in a production process of various electronic parts. Further, the molded article obtained from the resin composition of this embodiment has a high refractive index and is also excellent in transparency. Therefore, the obtained thin film can be suitably used as an optical thin film of an optical device in which such characteristics are required. In addition, the resin composition of the present invention has low viscosity magnification after 24 hours at room temperature and is particularly excellent in pot life at room temperature. Therefore, it can be used as a one-part type resin composition, and it has been confirmed that it can be applied to applications (for example, sealing materials) in which a pot life is required after a single solution is obtained.

It is also contemplated that the molded article obtained from the resin composition of this embodiment has a high refractive index and that it is possible to adjust the refractive index difference with an additive material such as an inorganic filler. Therefore, the molded article can exhibit the effect of the additive material while maintaining transparency. Therefore, the molded article can be used for various members of the electronic apparatus in which such characteristics are required.

This application is based upon and claims the benefit of priority from Japanese Patent Application No. 2011-222788, filed on October 7, 2011, the entire disclosure of which is incorporated herein by reference.

The present invention includes the following contents.

[a] (A) an isocyanate compound,

(B) 4,8 or 4,7 or 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, 4-mercaptomethyl-1,8-di Mercapto-3,6-dithiaoctane, and at least one selected from mercapto-

(C) an organic strong base salt,

Based polymerizable composition.

The one-part polymerizable composition according to [a], wherein the dissociation temperature of the salt in the [b] organic strong base salt (C) is 60 ° C to 130 ° C.

[c] The one-pack type polymerizable composition according to [a] or [b], wherein the organic strong base salt (C) is a tertiary amine salt.

[d] The tertiary amine salt is 1,8-diazabicyclo [5. 4. 0] undecene-7, or 1,5-diazabicyclo [4. 3. 0] nonene-5.

[e] The isocyanate compound (A) is at least one compound selected from the group consisting of phenylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, m-xylene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,5-bis (isocyanatomethyl) -bicyclo [2. 2.1] heptane, and 2,6-bis (isocyanatomethyl) -bicyclo [2. A] to [d], wherein the polymerizable monomer is at least one selected from the group consisting of [1] to [2.1] heptane.

(f) 1,1,3,3-tetrakis (mercaptomethylthio) propane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, 2- A-1] to [e], further comprising at least one member selected from the group consisting of an alkyl group, an alkoxy group, an alkoxy group,

The one-part polymerizable composition according to any one of [a] to [f], further comprising [g] an inorganic filler.

[h] An optical thin film comprising the one-part polymerizable composition according to any one of [a] to [f].

[i] A substrate comprising the one-part polymerizable composition according to [g].

a light-emitting layer comprising an optical thin film described in [j] [h].

The organic EL display using the surface emitting device according to [k] [j].

[1] An organic EL lighting apparatus using the surface emitting device according to [j].

[m] an electronic device having a transparent heat-radiating layer made of the substrate described in [i].

Claims (15)

(A) an isocyanate compound,
(B) 4,8 or 4,7 or 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, 4-mercaptomethyl-1,8-di Mercapto-3,6-dithiaoctane, pentaerythritol tetrakis mercaptoacetate, pentaerythritol tetrakis mercaptopropionate, 2,5-bis (mercaptomethyl) -1,4-dithiane, bis (Mercaptomethylthio) -1,3-dithiane, 2- (2,2-dimethylthio) -1,3-dithiane, 1,1,3,3-tetrakis Bis (mercaptomethylthio) ethyl) -1,3-dithiane, and at least one thiol compound selected from
(C) Organic strong bases salt
A polymerizable composition for use in the production of an electronic component or an electronic device,
A polymerizable composition having a viscosity magnification of 1 to 10 after 12 hours represented by the following formula (1).
Expression: b / a ... (One)
(a: initial viscosity at 25 캜, b: viscosity after 12 hours) The method according to claim 1,
(C) the organic strong base salt has a dissociation temperature of 40 DEG C or higher in the DSC measurement. 3. The method according to claim 1 or 2,
(C) the organic strong base salt is a tertiary amine salt. The method of claim 3,
The tertiary amine salt may be 1,8-diazabicyclo [5. 4. 0] undecene-7, or 1,5-diazabicyclo [4. 3. 0] nonene-5. &Lt; / RTI &gt; 3. The method according to claim 1 or 2,
(A) the isocyanate compound is at least one compound selected from the group consisting of phenylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, m-xylene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, Bis (isocyanatomethyl) -bicyclo [2. &lt; RTI ID = 0.0 &gt; 2.1] heptane, and 2,6-bis (isocyanatomethyl) -bicyclo [2. 2.1] heptane. &Lt; / RTI &gt; 3. The method according to claim 1 or 2,
And a viscosity measured at 25 캜 using an E-type viscometer is 20 to 50,000 mPa s. 3. The method according to claim 1 or 2,
A polymerizable composition, further comprising an inorganic filler. An optical thin film having at least one layer composed of the polymerizable composition according to any one of claims 1 and 2. An encapsulating material comprising the polymerizable composition according to claim 1 or 2. A substrate comprising the polymerizable composition according to claim 7. A surface emitting device comprising a light extraction layer comprising the optical thin film according to claim 8. An organic EL display using the surface emitting device according to claim 11. An organic EL lighting apparatus using the surface emitting device according to claim 11. An electronic device having a transparent heat-radiating layer comprising the substrate according to claim 10. A process for producing a polymerizable composition, comprising the steps of: applying the polymerizable composition according to claim 1 or 2 onto an optical member;
A step of sealing the optical member with an encapsulating material obtained by curing the applied polymerizable composition
Wherein the optical member is made of a transparent material.