JP4690053B2 - Resin molded body, manufacturing method thereof, and use thereof - Google Patents

Description

  The present invention relates to a resin molded product obtained by photocuring a photopolymerizable composition, and in particular, a sheet-shaped or film-shaped resin molded product having excellent optical characteristics, thermal characteristics, and mechanical characteristics. In particular, the present invention relates to a resin molding useful as a flexible plastic substrate for a display. Furthermore, the present invention relates to a wide and long roll film obtained by continuous photoforming.

  Conventionally, as a substrate for a display, a glass substrate is often used. For example, a glass substrate having a thickness of about 0.3 to 0.7 mm is widely used in liquid crystal displays and organic electroluminescence (EL) displays. In recent years, plastic substrates have begun to be used from the viewpoint of weight reduction and thickness reduction and for the purpose of manufacturing flexible displays. In fact, polycarbonate substrates are used for the LCD screen of calculators, and polyethersulfone is used as the substrate for LCD screens for mobile phones. Such plastic substrates have not only optical performance such as light transmittance and birefringence, but also thermal properties such as heat resistance and linear expansion coefficient, mechanical properties such as flexural modulus and impact resistance, water absorption and specific gravity, and High processability such as chemical resistance and solvent resistance is required.

  In order to satisfy these various properties, many resins have been proposed regardless of thermoplasticity or thermosetting. Proposals have been made to improve heat resistance by adding nanofillers, and to improve surface hardness by coating. However, the current situation is that the optical properties have decreased and the cost has been increased several times that of glass. It is.

Further, in recent proposals, a molded product obtained by photocuring a specific photopolymerizable composition can be seen. For example, it is disclosed that a polymerizable composition containing a bifunctional (meth) acrylate and a mercapto compound having two or more thiol groups in the molecule gives a resin molded article having a small birefringence (for example, , See Patent Document 1). Further, it is disclosed that a polymerizable composition containing 75 wt% or more of a trifunctional or higher functional aliphatic (meth) acrylate compound gives a resin molded body having high heat resistance and low birefringence (for example, Patent Documents). 2). Further, it is disclosed that a polymerizable composition containing a bifunctional aliphatic (meth) acrylate compound and a trifunctional or higher (meth) acrylate compound gives a molded article having high heat resistance and a small linear expansion coefficient. (For example, refer to Patent Document 3).
Furthermore, a method of photocuring in a continuous manner has been proposed (see, for example, Patent Document 4).
JP-A-9-152510 JP 2002-302517 A JP 2003-292545 A JP 2002-011742 A

However, it is hard to say that the characteristics are balanced even with these disclosed technologies. For example, in the technology disclosed in Patent Document 1, the molded product has a low birefringence due to the chain transfer effect of the mercapto compound, but conversely, the curing rate is lowered, and a degree of polymerization for expressing necessary physical properties is obtained. In addition, since the chemical structure of the monomer is rigid, the flexural modulus is too high and the inherent flexibility of the plastic is lost.
In the techniques disclosed in Patent Documents 2 and 3, the heat resistance is improved by using a polyfunctional aliphatic (meth) acrylate, but the water absorption is increased because of the use of an aliphatic monomer. The dimensional change accompanying the moisture absorption / desorption of the molded body increases. Furthermore, the molecular chain is fragile because it does not have a chemical structure that absorbs impact. In addition to light weight and thinness, crack resistance is also an important factor for plasticization. However, with these disclosed technologies, it is difficult to make the molded product thin because only the impact resistance equivalent to that of glass can be obtained.

In addition to the above-described problems such as flexibility (flexural modulus, impact resistance), water absorption rate, and curing rate, there is a problem that the surface is easily damaged. This is a general problem with plastic substrates. However, if the surface hardness of the substrate is insufficient, scratches and fine dents are generated during transportation and in the manufacturing process of the display device. For example, sheet plastic substrates are usually stacked and transported. However, if the surface hardness is low, the substrates are rubbed with each other and rubbed with interleaving paper, resulting in numerous scratches. At present, glass containers that are easy to break are transported by using a go-through box that arranges the substrates with a gap in polystyrene foam, but plastic substrates with low flexural modulus have a large deflection due to their own weight. Have difficulty. Considering the recent increase in area and resolution as represented by liquid crystal televisions, defects resulting from scratches and dents significantly impair the quality of the product. In addition, defects such as pinholes are likely to occur in a gas barrier film formed on a plastic substrate for ensuring reliability and a conductive film formed for driving a liquid crystal or an organic EL element. In order to improve the surface hardness, generally, a technique of hard-coating the substrate surface is used. However, a plastic that is easily charged tends to adhere foreign matter, and it is very difficult to eliminate foreign matter defects on the coated surface. Multi-layering with a hard coat or protective film leads to an increase in cost.
In particular, in the organic EL display, the surface smoothness of the substrate greatly affects the light emission characteristics and the lifetime of the device. Small protrusions or indentations due to scratches or foreign matter accelerate the deterioration of the element and become display defects such as black spots. Therefore, the surface hardness of the substrate is particularly important. In addition, when the surface hardness is insufficient, a minute surface roughness occurs when an electrode or an organic EL layer is formed on the substrate, and sufficient light emission characteristics cannot be obtained. In order to achieve high brightness and low power consumption, it is necessary to improve the surface hardness of the plastic substrate.

On the other hand, as a problem required for a plastic substrate, since a single-wafer resin molded body cannot continuously produce a display device and is inferior in productivity, the resin molded body can be made into a film roll.
In the technique disclosed in Patent Document 4, a high-viscosity photopolymerizable composition is extruded on a polyethylene terephthalate (PET) film by a certain amount, and another PET film is laminated thereon, and then an active energy ray. However, since the PET film is bent, the resin flatness cannot be ensured.
Considering that a general optical film is several hundred meters or longer, a long molded body of at least 100 meters or more is desired. Further, the width of the molded body needs to be wider in consideration of the recent increase in display area and the improvement of production efficiency by multi-cavity. For example, considering application to a liquid crystal television, a wide film having a width of 50 cm or more is desired.
When the molded body is used as a film roll, the surface hardness is particularly a problem. That is, when the surface hardness is low, scratches with the transport roll and scratches between the films in the winding process increase. In order to improve surface hardness, hard coat treatment, attaching a protective film, or inserting slip sheets will increase costs, so it is formed into a core roll without these treatments and processes. Preferably the body is wrapped around.

The above-mentioned problem was the reason for greatly reducing the opportunity to use a plastic substrate instead of glass.
Therefore, the present invention aims to provide a resin molded body suitable for a flexible display, and further a resin molded body that can easily be a film roll.

As a result of intensive studies by the present inventors to solve the above-mentioned problems, it is a resin molded body obtained by photocuring the (meth) acrylate photopolymerizable composition [I], and has a thickness of 50 to 400 μm. And the surface pencil hardness is 4H or more, and the (meth) acrylate photopolymerizable composition [I] contains the following components (A), (B), and (C): The present invention was completed by finding that the molded body meets the above-mentioned purpose.
(A) Polyfunctional urethane (meth) acrylate having an alicyclic structure obtained by reacting a polyisocyanate compound having an alicyclic structure and a hydroxyl group-containing (meth) acrylate (B) Bifunctional (meth) acrylate having an alicyclic structure ( (Excluding (A))
(C) Photopolymerization initiator

In the resin molding of the present invention, the flexural modulus is preferably 2.5 to 3.5 GPa (25 ° C.), and at least the surface roughness Ra on one side is more preferably 20 nm or less.
Furthermore, the mixing ratio of Ingredients (A) and component (B), 30 by weight ratio: 70 to 70: it is preferred from the viewpoint of balance among physical properties such as surface hardness and flexural modulus and heat resistance at 30.
In addition, polyfunctional here means having two or more (meth) acryloyl groups in a molecule | numerator.

The resin molded body of the present invention has a light transmittance of 90% or more, a refractive index of 1.48 to 1.54, a retardation of 10 nm or less, a glass transition point of 120 ° C. or more, and The linear expansion coefficient is particularly preferably 20 to 70 ppm / ° C.
And the resin molding of this invention can be used conveniently especially as a board | substrate for organic EL displays.

As a manufacturing method of the resin molding in this invention, (meth) acrylate type photopolymerizable composition [I] is photocured by the irradiation light quantity of 5 J / cm < ² > or less using an active energy ray with a wavelength of 200-400 nm. It is more preferable that a solution containing 30% by weight or more of the (meth) acrylate photopolymerizable composition [I] is cast on a continuous cast substrate, dried and then photocured, and more preferably It is particularly preferable to perform heat treatment at a temperature of 100 ° C. or higher after photocuring.

The present invention also relates to a gas barrier film in which a gas barrier film is formed on at least one surface of the resin molded body. The gas barrier film is preferably a silicon oxide film and / or a vinyl alcohol resin film. More preferably, it is a gas barrier film in which a vinyl alcohol-based resin film is laminated on the silicon oxide film, and is particularly formed by a layer structure of resin molded body / silicon oxide film / vinyl alcohol-based resin film. A gas barrier film is preferred.
Furthermore, the present invention relates to a transparent conductive film in which a transparent conductive film is formed on at least one surface of the gas barrier film, and an organic EL device using the transparent conductive film.

  ADVANTAGE OF THE INVENTION According to this invention, the resin molding which is excellent in an optical characteristic, a thermal characteristic, and a mechanical characteristic, has especially high surface hardness, and is suitable for the flexible substrate for a display can be manufactured easily. In particular, a wide and long resin molded body having a length of 100 m or more and a width of 50 cm or more can be obtained. Since these resin moldings have high surface hardness, high surface smoothness, and appropriate bending elastic modulus, it is easy to stack gas barrier films with excellent gas barrier properties and conductive films with excellent conductivity, and light emitting characteristics. It is suitable as a substrate for an organic EL display having excellent resistance.

Hereinafter, the present invention will be described in detail. In the present invention, “(meth) acrylate” is a general term for acrylate and methacrylate.
The resin molded body of the present invention is a resin molded body having a thickness of 50 to 400 μm obtained by photocuring the (meth) acrylate-based photopolymerizable composition [I] and having a surface pencil hardness of 4H or more. is there. Since the thickness of the resin molding directly affects the flexibility of the plastic substrate, if the thickness exceeds 400 μm, the flexibility is lost and it becomes difficult to roll the film. Conversely, if the thickness is less than 50 μm The function as a display support is poor. A more preferable range of the thickness is 70 to 300 μm, more preferably 80 to 200 μm, and particularly preferably 90 to 150 μm. Moreover, if the pencil hardness is less than 4H, the surface of the resin molded body is easily damaged in the manufacturing process of the display device. This is not only due to scratches caused by foreign objects, but also high-strength resin jigs and SUS jigs used when plastic substrates are transported, or a general hard coat layer covering these jigs has a surface hardness of about 4H. It is for having. If scratches are present on the surface of the resin molded body, sufficient gas barrier properties cannot be exhibited when a gas barrier film is formed on the surface. Also, sufficient conductivity cannot be exhibited when a conductive film is formed on the surface. In particular, when used for a substrate for an organic EL display, the light emission characteristics are also deteriorated. The pencil hardness on the surface of the molded body is preferably 5H to 8H, more preferably 6H to 7H.

  The resin molded body of the present invention preferably has a flexural modulus of 2.5 to 3.5 GPa (25 ° C.). When the flexural modulus is less than 2.5 GPa, the toughness of the resin molding is insufficient, so that the film forming process and the display device manufacturing process cause deflection and undulation, and uniform gas barrier properties and electrical conductivity tend not to be ensured. When the flexural modulus exceeds 3.5 GPa, the flexibility of the resin molded body and the display device is lost, and film rolls become difficult.

  As for the resin molding of this invention, it is more preferable that surface roughness Ra is 20 nm or less. When the surface roughness exceeds 20 nm, not only gas barrier properties and conductivity are lowered, but also display defects such as black spots are likely to occur in the display device.

The (meth) acrylate photopolymerizable composition [I] used for photocuring in the present invention satisfies the physical properties as described above and contains the following (A), (B), and (C). Is.
(A) Polyfunctional urethane (meth) acrylate having an alicyclic structure obtained by reacting a polyisocyanate compound having an alicyclic structure and a hydroxyl group-containing (meth) acrylate (B) Multifunctional (meth) acrylate having an alicyclic structure ( (Excluding (A))
(C) Photopolymerization initiator

  Component (A) is a urethane (meth) acrylate containing two or more (meth) acryloyl groups in the molecule. Since it is polyfunctional, the curing rate is improved, and a resin molded product can be obtained with high productivity. Moreover, a crosslinked resin can be formed by photocuring and a resin molded body with high heat resistance can be obtained. Usually, the higher the polyfunctionality, the more the flexural modulus of the molded body increases and the flexibility is lost. Even if the impact resistance decreases, the component (A) has a urethane group in the molecule and is obtained. Since the resin molded body has moderate toughness due to hydrogen bonding and does not become brittle, it obtains a flexible resin molded body with excellent mechanical strength such as flexural modulus and impact resistance while having a highly crosslinked structure. be able to. In general, bifunctional or higher functional (meth) acrylate compounds have large shrinkage during polymerization, and it has been difficult to obtain a resin molded product because the cured product cracks in the mold or breaks during demolding. Since the strength of the photopolymerizable composition used in the invention is improved by the urethane group, a resin molded product can be obtained with a high yield. Also noteworthy is the improvement of surface hardness. In general, polyfunctional urethane (meth) acrylate is used as a hard coating agent, and the film has high pencil hardness and scratch resistance. By using the monomer as a component of the resin molded body, the susceptibility of the plastic substrate to damage can be improved. This improvement in surface hardness is manifested particularly with a tetrafunctional or higher urethane (meth) acrylate. In addition, component (A) has an alicyclic structure in the molecule, and the water absorption rate of the resin molded product is reduced by this alicyclic structure.

Since component (B) is also a polyfunctional (meth) acrylate, a highly heat-resistant resin molded product is provided. Although the effect of improving the heat resistance is greater than that of the component (A) urethane (meth) acrylate, this monomer alone is too brittle because it becomes a glass-like crosslinked resin. By copolymerizing the component (A) with urethane (meth) acrylate at a specific ratio, a resin molded body having both heat resistance and flexibility can be obtained in addition to surface hardness. If the number of functional groups in component (B) is excessively large, the balance between heat resistance and flexibility is lost, so component (B) needs to be bifunctional and is more preferably methacrylate. The component (B) also has an alicyclic structure, and this alicyclic structure also reduces the water absorption rate of the resin molded body. An ester group or a urethane group is not necessarily preferable for reducing the water absorption rate, but the water absorption rate can be sufficiently reduced by introducing an alicyclic structure into the cured product. In addition, the curing shrinkage in the photocuring process increases as the polyfunctionality increases, but the bulky alicyclic structure greatly contributes to the reduction of shrinkage and can improve the moldability.

  The compounding ratio of the component (A) and the component (B) is 30:70 to 70:30 (weight ratio). If the component (A) is less than 30% by weight, the mechanical properties such as surface hardness and impact resistance are inferior. Conversely, if the component (A) exceeds 70% by weight, the water absorption rate is unfavorably increased. . A preferable range of the blending ratio is 40:60 to 60:40 (weight ratio), and more preferably 45:55 to 55:45 (weight ratio).

  The (meth) acrylate photopolymerizable composition [I] of the present invention preferably has a viscosity at 23 ° C. of 200 to 6000 mPa · s. More preferably, it is 1000-4000 mPa * s, More preferably, it is 2000-3000 mPa * s. If the viscosity is less than 200 mPa · s, unpolymerized monomers are likely to remain in the molding process. Conversely, if the viscosity exceeds 6000 mPa · s, it is difficult to inject into the mold when batch-type casting, and when continuous molding is performed. Retardation tends to increase due to flow unevenness, which is not preferable. Examples of the method for adjusting the viscosity include appropriately controlling the types and blending amounts of the components (A) and (B).

  The number average molecular weight of component (A) is preferably 200 to 5,000. More preferably, it is 400-3000, More preferably, it is 500-1000. When the number average molecular weight is less than 200, curing shrinkage increases and birefringence tends to occur. On the other hand, when it exceeds 5000, the crosslinkability tends to decrease and the heat resistance tends to be insufficient.

The polyfunctional urethane (meth) acrylate having an alicyclic structure as the component (A) is prepared by using a polyisocyanate compound having an alicyclic structure and a hydroxyl group-containing (meth) acrylate, if necessary, using a catalyst such as dibutyltin dilaurate. It can be obtained by reacting.
Specific examples of the polyisocyanate compound having an alicyclic structure include isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, hydrogenated xylylene diisocyanate. , Hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate trimer compound, and the like.
Specific examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-hydroxy-3- (meth) acryloyl. Examples include roxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol tri (meth) acrylate.

  Two or more polyfunctional urethane (meth) acrylates obtained by the reaction of a polyisocyanate compound having an alicyclic structure and a hydroxyl group-containing (meth) acrylate may be used in combination. Among these reactants, acrylate is preferable from the viewpoint of curing speed, tetrafunctional or higher is more preferable from the viewpoint of heat resistance, and alicyclic rings represented by the following formulas (1) to (4) from the viewpoint of surface hardness. A tetrafunctional or higher functional urethane acrylate having a structure is particularly preferred.

ここで、Ｒ_１は水素又はメチル基である。

Here, R ₁ is hydrogen or a methyl group.

Component polyfunctional (meth) acrylate having an alicyclic structure (B) (provided that (except for A).) The bis (hydroxymethyl) tricyclo [5.2.1.0 ^{2, 6]} decane = di (Meth) acrylate, bis (hydroxy) tricyclo [5.2.1.0 ^2,6 ] decane = acrylate methacrylate, bis (hydroxy) pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane = di (meth) acrylate, bis (hydroxy) pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane = acrylate methacrylate, 2,2-bis [4- (β-methacryloyloxyethoxy) cyclohexyl] propane, 1,3-bis (methacryloyloxymethyl) cyclohexane, 1,3-bis (methacryloyloxyethyl) Bifunctional (meth) acrylates such as oxymethyl) cyclohexane, 1,4-bis (methacryloyloxymethyl) cyclohexane, 1,4-bis (methacryloyloxyethyloxymethyl) cyclohexane, 1,3,5-tris (methacryloyloxymethyl) ) cyclohexane, 1,3,5-tris (methacryloyloxyethyl oxy) cyclohexane trifunctional (meth) acrylate and the like, among these, difunctional (meth) acrylate from the viewpoint of flexibility It is necessary that there is more preferred difunctional methacrylate from the viewpoint of heat resistance. Furthermore, at least one bifunctional (meth) acrylate selected from the following general formula (5), (6), or (7) is preferable from the viewpoint of optical performance, and bifunctional methacrylate is particularly preferable.

ここで、Ｒ_２は炭素数1〜６のエーテル結合を含んでも良いアルキレン基、Ｒ_３は水素又はメチル基、ａは１又は２、ｂは０又は１である。

Here, R ₂ is an alkylene group that may contain an ether bond having 1 to 6 carbon atoms, R ₃ is hydrogen or a methyl group, a is 1 or 2, and b is 0 or 1.

ここで、Ｒ_４は炭素数1〜６のエーテル結合を含んでも良いアルキレン基、Ｒ_５は水素又はメチル基である。

Here, R ₄ is an alkylene group that may contain an ether bond having 1 to 6 carbon atoms, and R ₅ is hydrogen or a methyl group.

ここで、Ｒ_６は水素又はメチル基、Ｒ_７は 炭素数1〜６のエーテル結合を含んでも良いアルキレン基、Ｒ_８は水素又はメチル基である。

Here, R ₆ is hydrogen or a methyl group, R ₇ is an alkylene group that may contain an ether bond having 1 to 6 carbon atoms, and R ₈ is hydrogen or a methyl group.

  Component (C) is a photopolymerization initiator and is not particularly limited. For example, benzophenone, benzoin methyl ether, benzoin propyl ether, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2,6-dimethylbenzoyldiphenylphosphine oxide, Examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Among these, radical-cleavage photopolymerization initiators such as 1-hydroxycyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are preferable. These photopolymerization initiators may be used alone or in combination of two or more. Although the compounding quantity of a photoinitiator is not specifically limited, 0.1-5 weight part with respect to a total of 100 weight part of a component (A) and a component (B), Furthermore, 0.2-4 weight part, In particular, the amount is preferably 0.3 to 3 parts by weight. If the blending amount exceeds 5 parts by weight, the retardation of the resin molded product increases and the light transmittance at 400 nm tends to decrease. On the other hand, if the amount is less than 0.1 parts by weight, the polymerization rate may decrease and the polymerization may not proceed sufficiently.

  In the present invention, a small amount of auxiliary components may be included as long as the physical properties of the resin molded body of the present invention are not impaired. For example, monomers having an ethylenically unsaturated bond other than components (A) and (B), polymerization inhibitors, thermal polymerization initiators, antioxidants, ultraviolet absorbers, antifoaming agents, leveling agents, blue Ingredients, dyes and pigments.

  Monomers having an ethylenically unsaturated bond other than components (A) and (B) include methyl methacrylate, 2-hydroxyethyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meta ) Monofunctional (meth) acrylate such as acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, di (meth) acrylate of tetraethylene glycol or higher polyethylene glycol, 1 , 3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-hydroxy 1,3-di (meth) acryloxypropane, Polyfunctional (meth) acrylates such as 2,2-bis [4- (meth) acryloyloxyphenyl] propane, trimethylolpropane tri (meth) acrylate, (meth) acrylic such as acrylamide, methacrylamide, acrylonitrile, methacrylonitrile Examples thereof include acid derivatives, styrene compounds such as styrene, chlorostyrene, divinylbenzene, and α-methylstyrene.

  Known compounds can be used as the thermal polymerization initiator. For example, hydroperoxide such as hydroperoxide, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide Dialkyl peroxides such as t-butyl peroxybenzoate, peroxyesters such as t-butylperoxy (2-ethylhexanoate), diacyl peroxides such as benzoyl peroxide, and peroxycarbonates such as diisopropyl peroxycarbonate And peroxides such as peroxyketal and ketone peroxide.

Thus, the (meth) acrylate photopolymerizable composition used in the present invention is obtained.
Next, the manufacturing method of the resin molding of this invention using this (meth) acrylate type photopolymerizable composition is demonstrated.

As a method for producing a resin molded body in the present invention, the (meth) acrylate photopolymerizable composition [I] is photocured with an ultraviolet ray having a wavelength of 200 to 400 nm at an irradiation light amount of 5 J / cm ² or less. Is preferred. A more preferable range of the irradiation light amount is 0.5 to 4 J / cm ² , and more preferably 1 to 3 J / cm ² . When the irradiation light quantity exceeds 5 J / cm ² , the productivity is inferior, which is not preferable. The illuminance of ultraviolet rays is 10 to 5000 mW / cm ² , preferably 100 to 1000 mW / cm ² . If the illuminance is too small, the molded body will not be cured sufficiently. On the other hand, if the illuminance is too high, polymerization will run away and birefringence will increase. It is preferable to irradiate the ultraviolet rays in a plurality of times because a resin molded body having smaller birefringence can be obtained. For example, the method of irradiating about 1/100 to 1/10 of the total irradiation amount at the first time and irradiating the necessary remaining amount after the second time can be mentioned. Examples of the ultraviolet light source include a metal halide lamp, a high-pressure mercury lamp lamp, and an electrodeless mercury lamp. In order to prevent polymerization from running away due to infrared rays generated from a light source, it is also possible to use a filter that blocks infrared rays, a mirror that does not reflect infrared rays, or the like for the lamp. The resin molded body obtained in the present invention may be heat-treated for improving the degree of polymerization or releasing stress strain, and is preferably heat-treated at 100 ° C. or higher.

  In general, photoforming is performed in a batch mode. That is, a mold in which two transparent glasses are opposed to each other through a spacer for controlling the thickness is prepared, a photopolymerizable composition is injected into the cavity, cured by irradiation with active energy rays, and removed. This is done by typing.

  The photoforming method of the present invention is not particularly limited, and may be a batch type. In particular, the continuous forming method is more preferable in that a long and wide film roll can be obtained. Further, a solution containing 30% by weight or more of (meth) acrylate photopolymerizable composition [I] or (meth) acrylate photopolymerizable composition [I] is applied to a continuous cast substrate such as a belt or a drum. The technique of continuous photo-curing after casting and drying is particularly preferred. Hereinafter, the continuous photoforming method of the present invention will be described.

  The (meth) acrylate photopolymerizable composition [I] used in this method contains the above-mentioned components (A) to (C). As necessary, the solvent may be isopropyl alcohol, ethyl acetate, acetic acid. Usual organic solvents such as butyl, methyl ethyl ketone, toluene, xylene, acetone, diacetone alcohol, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, N-methylpyrrolidone and cellosolves can be used. If the concentration of the (meth) acrylate photopolymerizable composition [I] is less than 30% by weight, the solvent drying load is large and the productivity is inferior. A more preferable range of the concentration is 50 to 95% by weight, more preferably 70 to 90% by weight, and particularly preferably 80 to 90% by weight. The viscosity of the solution is preferably 100 to 5000 mPa · s, more preferably 200 to 4000 mPa · s, still more preferably 300 to 3000 mPa · s, and particularly preferably 400 to 2000 mPa · s. When the viscosity is less than 100 mPa · s, it is difficult to control the film thickness, and when it exceeds 5000 mPa · s, the flatness tends to decrease. The solution may contain a small amount of an additive such as a release agent as required. As the release agent, a nonionic surfactant such as polyoxyethylene alkyl ether is suitable.

The concentration-adjusted solution is defoamed. Examples of the defoaming method include stationary defoaming and defoaming using a multi-screw extruder. In the production method of the present invention, defoaming is performed using a multi-screw extruder from the viewpoint of productivity. The method is preferred. The multi-screw extruder is not particularly limited as long as it is a multi-screw extruder having a vent. Usually, a twin-screw extruder having a vent is used. A gear pump is provided before and after the multi-screw extruder, the solution is supplied to the multi-screw extruder by the front gear pump, and the defoamed solution is discharged from the multi-screw extruder by the rear gear pump.
The defoamed solution is introduced into a T-shaped slit die by a certain amount and cast onto a cast substrate such as a drum-type roll or an endless belt. The temperature of the composition at the exit of the T-shaped slit die is controlled by the presence or absence of the solvent and the type and amount of the solvent used, but is preferably 0 to 150 ° C, more preferably 10 to 120 ° C, More preferably, it is 20-100 degreeC. If the solution temperature at the exit of the T-shaped slit die is less than 0 ° C., flow failure occurs, and if it exceeds 150 ° C., bubbles are likely to be generated.
The casting is performed with a smooth and flat drum-type roll or an endless belt, but is preferably performed with a drum-type roll from the viewpoints of widening, lengthening, film thickness uniformity, etc. The manufacturing method used will be described as an example.

  The diameter of the drum roll (R1) is preferably 0.5 to 5 m, more preferably 1 to 4 m, and particularly preferably 2 to 3 m. If the diameter is less than 0.5 m, the drying length is insufficient, and if it exceeds 5 m, it is difficult to manufacture the equipment. The width of the drum-type roll is preferably 0.5 to 5 m, more preferably 1 to 4 m, and particularly preferably 2 to 3 m. If the width is less than 0.5 m, the productivity is inferior, and if it exceeds 5 m, it is difficult to manufacture equipment. The rotational speed of the drum-type roll is controlled by the presence or absence of the solvent and, if used, by the type and amount of the solvent, but is preferably 1 to 30 m / min, and preferably 2 to 20 m / min. More preferred. If the rotational speed is less than 1 m / min, the productivity tends to be inferior, and if it exceeds 30 m / min, the leveling is not sufficient and the flatness of the resulting resin molded product is inferior. In particular, when a solvent is used, the solvent is dried. Tends to be insufficient. The surface temperature of the drum-type roll is controlled by the presence or absence of addition of a solvent and, when added, the type and amount of the solvent, but is preferably 0 to 150 ° C, and preferably 10 to 120 ° C. More preferred. When the surface temperature is less than 0 ° C., condensation is likely to occur on the drum-type roll, and leveling failure and drying failure are likely to occur. Conversely, if the temperature exceeds 150 ° C., bubbles are likely to be generated.

  The active energy ray is irradiated onto the (meth) acrylate photopolymerizable composition [I] on the drum roll (R1). If a solvent is used, it must be dried before irradiation. The active energy ray to be irradiated is not particularly limited as long as it has the above-described wavelength and light amount. It may be cured by irradiating the necessary light amount in one stage, or once the cured body is peeled off from the roll (R1), and then on the next roll (R2) to which the cured body is conveyed or between the rolls. Irradiation may be performed. In this case, it is preferable to irradiate the second stage from the reverse side irradiated with the active energy ray in the first stage. Furthermore, when irradiation is repeated in three or more stages, it is preferable to repeat irradiation alternately on the front and back sides. Irradiation may be performed in air or under an inert gas.

The surface temperature of the roll (R2) and subsequent transport rolls can be set for the purpose of heat treatment of the cured body. The surface temperature is not particularly limited, but 50 to 200 ° C. is preferable from the viewpoint of improving the degree of polymerization and releasing stress strain. For example, it is possible to provide a roll (R3) and heat-treat the opposite surface heated by the roll (R2) on the roll (R3), or to repeat the heat treatment on both sides with several rolls.
The resin molded body thus obtained is wound up on a winding roll to form a film roll (product).
The film roll obtained by the above-described method is excellent in flatness and thickness accuracy, can have a length of 100 m or more and a width of 50 cm or more, and is suitable for manufacturing a display device with high productivity.

  Thus, a resin molded body is obtained. In the present invention, the resin molded body has a light transmittance of 90% or more and a refractive index of 1.48 to 1.54, and a retardation of 10 nm or less. It is particularly preferable that the glass transition point is 120 ° C. or higher and the linear expansion coefficient is 20 to 70 ppm / ° C. In order to satisfy the light transmittance and refractive index in the above range, for example, the types and blending amounts of the components (A), (B) and (C) may be appropriately selected, and the retardation is satisfied in the above range. For example, the viscosity of the photopolymerizable composition and the irradiation method of the active energy ray may be appropriately selected. In order to satisfy the glass transition temperature and the linear expansion coefficient within the above ranges, for example, the components (A) and (B) What is necessary is just to select suitably the kind and compounding quantity.

  Here, the light transmittance is a spectral light transmittance at a wavelength of 400 to 700 nm, and includes reflection on both sides of the substrate. If the light transmittance is less than 90% at any wavelength in this wavelength range, the luminance of the display device cannot be ensured, and the power consumption increases when the emission intensity is increased to ensure the luminance. Normally, the resin absorbs light in the vicinity of 400 nm close to the ultraviolet region, but the resin molded body of the present invention has a light transmittance of 90% or more even at 400 nm. A more preferable range of light transmittance is 91% or more, particularly preferably 92% or more over the entire range of 400 to 700 nm. The light transmittance decreases as the refractive index of the substrate increases. On the other hand, when the refractive index is too low, interface reflection with a gas barrier layer, a transparent conductive layer or the like laminated on the substrate increases. A more preferable range of the refractive index is 1.49 to 1.54, particularly preferably 1.50 to 52.

  Retardation of the resin molding is a problem particularly in a liquid crystal display. If the retardation exceeds 10 nm, the polarized light that passes through the substrate cannot maintain its polarization characteristics, and thus the image definition tends to deteriorate. The retardation is more preferably 5 nm or less, particularly preferably 2 nm or less.

  If the glass transition temperature is less than 120 ° C., the reliability of the display device may be lacking. In recent liquid crystal televisions, since a powerful backlight is used, the temperature of the substrate also rises by nearly 120 ° C. If the glass transition temperature is less than 120 ° C., the display device may be deformed. A more preferable range of the glass transition temperature is 160 ° C. or higher, more preferably 200 ° C. or higher. Moreover, the more preferable range of a linear expansion coefficient is 30-60 ppm / degrees C, Most preferably, it is 40-50 ppm / degrees C. If it is less than 30 ppm / ° C., the difference from other optical films will be large and the fineness of the image will be reduced. Conversely, if it exceeds 70 ppm / ° C., the dimensional change during device manufacture will be large, and the pixels and wiring will be positioned. Misalignment is likely to occur.

  The resin molding obtained by this invention is suitable for producing a flexible display device. In particular, it is suitable as a substrate for an organic EL display manufactured by a technique such as a printing method. The flexibility depends on the thickness of the resin molded body and the bending elastic modulus, but when the bending elastic modulus exceeds 3.5 GPa, the flexibility is insufficient, and when it is 2.5 GPa or less, the function as a support is poor.

  Further, a gas barrier film or a transparent conductive film can be formed on the resin molded body of the present invention. Examples of the gas barrier film include an inorganic film such as a silicon oxide film and alumina, and an organic film made of a vinyl alcohol resin such as a polyvinyl alcohol resin or an ethylene-vinyl alcohol copolymer. The inorganic film is preferably a silicon oxide film having a thickness of 0.01 to 0.1 μm, and the organic film is preferably an ethylene-vinyl alcohol copolymer having a thickness of 0.5 to 5 μm. Examples of the transparent conductive film include inorganic films such as indium and tin oxide (ITO) and organic films such as poly (3,4-ethylenedioxythiophene) (PEDOT).

In the following, an organic EL element using a plastic substrate according to the present invention and its configuration will be described with reference to FIG. However, the present invention is not limited to this.
The anode 2 (corresponding to the transparent conductive film) formed on the substrate 1 plays a role of hole injection into the organic light emitting layer 3. In addition to ITO and PEDOT, the anode 2 is made of metal such as aluminum, gold, silver, platinum, nickel, palladium, platinum, metal oxide such as indium oxide, tin oxide, copper iodide, etc. Examples thereof include metal halides, carbon black, or conductive polymers such as poly (3-methylthiophene), polypyrrole, and polyaniline. The anode 2 can be formed by sputtering, vacuum deposition, spin coating, or the like. The thickness of the anode 2 varies depending on the target resistance value (conductivity), but is 0.005 to 1 μm, preferably 0.01 to 0.5 μm.
The organic light emitting layer 3 formed on the anode 2 efficiently transports and recombines holes injected from the anode 2 and electrons injected from the cathode 4 between electrodes to which an electric field is applied, and It is formed from a material that emits light efficiently by recombination. The organic light emitting layer 3 is preferably of a function separation type divided into a hole injection layer 3a, a hole transport layer 3b, and an electron transport layer 3c in order to improve luminous efficiency.

As a material used for the hole injection layer 3a, a phthalocyanine compound or a porphyrin compound is used. The film thickness of the hole injection layer 3a is usually 0.002 to 0.1 μm, preferably 0.005 to 0.05 μm. In order to form such a thin hole injection layer uniformly, it is generally preferable to employ a vacuum deposition method.
Examples of the material for the hole transport layer 3b include aromatic diamine compounds in which tertiary aromatic amine units such as 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane are linked, and 4,4′- Bis [N- (1-naphthyl) -N-phenylamino] An aromatic amine containing two or more tertiary amines represented by biphenyl and having two or more condensed aromatic rings substituted with nitrogen atoms, triphenylbenzene Aromatic triamines having a starburst structure, aromatic diamines such as N, N′-diphenyl-N, N′-bis (3-methylphenyl) biphenyl-4,4′-diamine, α, α, α ', Α'-tetramethyl-α, α'-bis (4-di-p-tolylaminophenyl) -p-xylene, a sterically asymmetric triphenylamine derivative as a whole molecule, aromatic diphenyl group Compounds in which a plurality of mino groups are substituted, aromatic diamines in which tertiary aromatic amine units are linked by ethylene groups, aromatic diamines having a styryl structure, those in which aromatic tertiary amine units are linked by thiophene groups, starburst type Aromatic triamine, benzylphenyl compound, fluorene group linked tertiary amine, triamine compound, bisdipyridylaminobiphenyl, N, N, N-triphenylamine derivative, aromatic diamine having phenoxazine structure, diaminophenyl phen Examples thereof include a nanthridine derivative, a hydrazone compound, a silazane compound, a silanamine derivative, a phosphamine derivative, and a quinacridone compound. These compounds may be used alone or in combination of two or more as required.

The hole transport layer 3b is formed by depositing these hole transport materials by a coating method or a vacuum deposition method. The thickness of the hole transport layer 3b is usually 0.01 to 0.3 μm, preferably 0.03 to 0.1 μm. In order to form such a thin hole transport layer uniformly, it is generally preferable to employ a vacuum deposition method.
Examples of the electron transporting compound used for the electron transporting layer 3c include aromatic compounds such as tetraphenylbutadiene, metal complexes such as aluminum complexes of 8-hydroxyquinoline, cyclopentadiene derivatives, perinone derivatives, oxadiazole derivatives, and bisstyrylbenzene. Derivatives, perylene derivatives, coumarin compounds, rare earth complexes, distyrylpyrazine derivatives, p-phenylene compounds, thiadiazolopyridine derivatives, pyrrolopyridine derivatives, naphthyridine derivatives, and the like. The film thickness of the electron transport layer 3c is usually 0.01 to 0.2 μm, preferably 0.03 to 0.1 μm. The electron transport layer can also be formed by the same method as the hole transport layer, but a vacuum deposition method is usually used.

The cathode 4 serves to inject electrons into the organic light emitting layer 3. The material used for the cathode 4 can be the material used for the anode 2, but a metal having a low work function is preferable for efficient electron injection, such as tin, magnesium, indium, calcium, Suitable metals such as aluminum and silver or their alloys are preferred. The film thickness of the cathode 4 is usually about the same as that of the anode 2.
For the purpose of protecting the cathode, the stability of the device can be increased by further laminating a metal layer that is stable to the atmosphere on the cathode. For the metal layer for this purpose, metals such as aluminum, silver, nickel, chromium, gold and platinum are used.
The organic electroluminescent element of the present invention can be applied to any of a single element, an element having a structure arranged in an array, and an element having a structure in which an anode and a cathode are arranged in an XY matrix. .

Hereinafter, the present invention will be described more specifically with reference to examples.
The measuring method of each physical property is as follows.

(1) Number average molecular weight of urethane (meth) acrylate Column: “Shodex GPC KF-806L” (exclusion limit molecular weight: 2 × 10 ⁷ ) in high performance liquid chromatography (“Shodex GPC system-11 type” manufactured by Showa Denko KK) , Separation range: 100 to 2 × 10 ⁷ , theoretical plate number: 10,000 plates / piece, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 μm) in series, standard polystyrene molecular weight conversion The number average molecular weight was measured.
(2) Viscosity Using a B-type viscometer “Bismetron VS-A1” manufactured by Shibaura System Co., Ltd., the viscosity was measured at a rotational speed of 60 ppmm (No. 3 rotor).
(3) Irradiation intensity of ultraviolet rays Measurement was performed using an ultraviolet ray illuminance meter “UV-M02” manufactured by Oak Seisakusho using an attachment “UV-35”.
(4) Irradiation light quantity of ultraviolet ray It measured using the UV light quantity meter "UV350" by Oak Seisakusho.

(5) Pencil hardness Measured according to JIS K-5600.
(6) Flexural modulus Ten test pieces of length 25 (mm) × width 10 (mm) were stacked and autograph AG-5kNE (distance between fulcrums 20 mm, 0.5 mm / min) manufactured by Shimadzu Corporation. Measured at 25 ° C.
(7) Surface Roughness Ra on both surfaces of the resin molded body was measured using a laser focus microscope “VK-8500” manufactured by Keyence Corporation. In the case of continuous molding in Examples 8 to 13, the contact surface with the first drum-type roll (R1) was measured. The measurement conditions are as follows.
Measurement length: 1 mm, objective lens: 50 times, cutoff: 0.8 μm, smoothing: none

(8) Scratch resistance The degree of scratches on the surface of steel wool # 0000 subjected to 1 kg load after 10 reciprocations on the surface of the molded body was visually observed. The case where no scratch was found was marked with ◯, and the one with scratch was marked with ×.
(9) Water Absorption Rate According to JIS K7209, using a 100 mm × 100 mm size test piece, the water absorption rate after being immersed in water at 23 ° C. for 24 hours was measured after drying at 50 ° C. for 24 hours.
(10) Light transmittance The light transmittance at 400 nm was measured using a spectrophotometer (manufactured by JASCO Corporation, trade name: “Ubest-35”).
(11) Retardation It measured at 25 degreeC with the birefringence measuring apparatus by an Oak company.

(12) Refractive index The refractive index was measured at 23 ° C. with an Abbe refractometer RX-2000 (NaD line).
(13) Glass transition temperature Using a test piece of length 30 × width 3 (mm), “TMA120” manufactured by Seiko Denshi Co., Ltd., tensile method TMA (distance 20 mm between fulcrums, weight 100 g, heating rate 5 ° C./min) Measured with
(14) Linear expansion coefficient: Using a test piece of length 30 (mm) × width 3 (mm), “TMA120” manufactured by Seiko Denshi Co., Ltd., tensile method TMA (distance 20 mm between fulcrums, weight 10 g, temperature increase rate 5 (° C./min). The elongation (mm) of the test piece when the temperature was raised from 25 ° C. to 100 ° C. was measured, and the linear expansion coefficient was calculated by the following equation.
Linear expansion coefficient (ppm / ° C.) = Elongation (mm) / 20 (mm) / 75 (° C.) × 10 ⁶

(15) Solvent resistance Test specimens each having a width and a length of 5 cm were immersed in N-methylpyrrolidone at 40 ° C. for 1 hour, and appearance abnormalities such as surface roughness were visually observed. The case where an abnormality occurred was indicated as x, and the case where no abnormality occurred was indicated as ◯.
(16) Chemical resistance A test piece having a width and a length of 5 cm each was immersed in hydrochloric acid with a concentration of 10% at 40 ° C. for 1 hour, and then immersed in an aqueous NaOH solution with a concentration of 10% at 40 ° C. for 1 hour to roughen the surface. The appearance abnormalities such as were observed visually. The case where an abnormality occurred was indicated as x, and the case where no abnormality occurred was indicated as ◯.
(17) Falling ball impact resistance The minimum height at which a test piece is damaged by placing a test piece of 5 cm in width and length on a support ring with an inner diameter of 4 cm and naturally dropping a 16 g steel ball in the center of the film. Was evaluated in 5 cm increments.
(18) Oxygen permeability The oxygen permeability was measured under the conditions of 23 ° C. and 80% RH with an oxygen mocon measuring device manufactured by Oxytran.
(19) Surface resistance value Measured using a 4-terminal resistance measuring instrument (Lorester MP) manufactured by Mitsubishi Chemical Corporation.

<Example 1>
[Synthesis of hexafunctional urethane acrylate (A) having isophorone structure]
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen gas inlet, 53.34 g (0.24 mol) of isophorone diisocyanate, 143.19 g ( 0.48 mol) of pentaerythritol triacrylate, hydroquinone methyl 0.02 g of ether, 0.02 g of dibutyltin dilaurate and 500 g of methyl ethyl ketone were added and reacted at 60 ° C. for 3 hours. The reaction was terminated when the residual isocyanate group became 0.3%, and the solvent was distilled off to obtain urethane acrylate. (A) was obtained. The number average molecular weight of the obtained urethane acrylate (A) was 820.

[Preparation of Photopolymerizable Composition [I]]
6 Urethane acrylate (A) 40 parts by weight of the functional with such isophorone structure of the bis (hydroxymethyl) tricyclo [5.2.1.0 2,6] decane = dimethacrylate 60 parts by weight (manufactured by Shin-Nakamura Chemical Co., Ltd. DCP ), 1 part by weight of 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba-Geigy) was stirred at 60 ° C. until uniform, to obtain a photopolymerizable composition [I]. The number of functional groups and the molecular weight are as shown in Table 1.

[Preparation of molded resin]
This composition (23 ° C.) was poured into a mold having two glass plates facing each other and a silicon plate having a thickness of 0.2 mm as a spacer, and using a metal halide lamp, the illuminance was 200 mW / cm ² , the light amount was 5 J / Ultraviolet rays were irradiated at cm ² . The cured product obtained by demolding was heated in a vacuum oven at 180 ° C. for 2 hours to obtain a resin molded body having a width of 0.3 m × length of 0.4 m × thickness of 200 μm as shown in Table 2. . The obtained resin molded body has a pencil hardness of 5H and a high surface hardness, a flexural modulus of 3.4 GPa, an appropriate flexibility, a surface roughness of 9 nm and a high surface smoothness, and an abrasion resistance. Excellent impact resistance and low water absorption of 0.5%. The other physical properties were as shown in Table 3, and had good optical properties, thermal properties, and mechanical properties.

[Production of gas barrier film]
A silicon oxide film having a thickness of 0.02 μm was formed on one side of the resin molded body obtained above by a sputtering method to obtain a gas barrier film (the oxygen permeability of such a gas barrier film is shown in Table 4). .)
[Preparation of transparent conductive film]
An ITO film having a thickness of 0.2 μm was formed on the silicon oxide film surface of the obtained gas barrier film by sputtering to obtain a transparent conductive film (the surface resistance value of the transparent conductive film is shown in Table 4). Show.)

[Production of organic EL element]
The obtained transparent conductive film was first processed into a stripe shape having a width of 2 mm using an etching solution of 6N hydrochloric acid (50 ° C.), and then the ITO substrate was washed with UV / O ₃ . Then, after installing in a vacuum deposition apparatus and exhausting using an oil diffusion pump equipped with a liquid nitrogen trap until the degree of vacuum in the apparatus is 10 ⁻⁴ Pa or less, as an organic hole injection layer material, Copper phthalocyanine was deposited on the substrate to a thickness of 20 nm. Next, as an organic hole transport material, N, N′-diphenyl-N, N ′-(α-naphthyl) -1,1′-biphenyl-4,4′-diamine is placed in a ceramic crucible, and the periphery of the crucible The tantalum wire heater was used for vapor deposition. At this time, the temperature of the crucible was controlled in the range of 160 to 170 ° C. The degree of vacuum during vapor deposition was 10 ⁻⁴ Pa, and an organic hole transport layer having a thickness of 60 nm was obtained. Next, using the 8-hydroxyquinoline complex Al (C ₉ H ₆ NO) ₃ of aluminum as the material for the electron transport layer, vapor deposition was performed in the same manner on the organic hole transport layer. At this time, the temperature of the crucible was controlled in the range of 230 to 270 ° C. The degree of vacuum at the time of deposition is 2 × 10 ⁻⁶ torr. The film thickness of the obtained electron transport layer was 75 nm. A cathode formed of an alloy electrode of magnesium and silver (Mg: Ag = 10: 1.5 (atomic ratio)) is formed on a substrate on which a hole injection layer, a hole transport layer, and an electron transport layer are formed, using a dual simultaneous vapor deposition method. Was formed by vapor deposition so as to have a film thickness of 40 nm. Deposition was performed using a molybdenum board at a vacuum degree of 2 × 10 ⁻⁴ Pa to obtain a glossy film. Further, aluminum was deposited as a protective layer to a thickness of 40 nm. The light emission luminance when a direct current voltage of 15 V was applied using the ITO electrode side of the obtained organic electroluminescence device as the positive electrode and the MgAg alloy film side as the cathode was measured using a Minolta radiance meter, 30000 cd / m ^2. It was good.

<Examples 2 to 7>
The same procedure as in Example 1 was performed except that the photopolymerizable composition [I] shown in Table 1 was used and molding was performed under the curing conditions shown in Table 2. The physical properties of the obtained resin molding were as shown in Table 3. Further, a gas barrier film and a transparent conductive film were obtained in the same manner as in Example 1. The characteristics of the obtained gas barrier film and transparent conductive film were as shown in Table 4.
The urethane acrylate (A) used in Example 4 and the urethane acrylate (A) used in Example 5 were as follows.

[Urethane acrylate (A) used in Example 4: Synthesis of bifunctional urethane acrylate having isophorone structure]
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen gas inlet, 53.34 g (0.24 mol) of isophorone diisocyanate, 55.73 g (0.48 mol) of 2-hydroxypropyl acrylate, hydroquinone 0.02 g of methyl ether, 0.02 g of dibutyltin dilaurate, and 500 g of methyl ethyl ketone were added and reacted at 60 ° C. for 3 hours. When the residual isocyanate group became 0.3%, the reaction was terminated, and the solvent was distilled off to obtain urethane. An acrylate (A) was obtained. The number average molecular weight of the obtained urethane acrylate (A) was 480.

[Urethane acrylate (A) used in Example 5: Synthesis of 9-functional urethane acrylate having isophorone diisocyanate trimer structure]
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 160.04 g (0.24 mol) of isophorone diisocyanate trimer and 214.79 g (0.72 mol) of pentaerythritol triacrylate , 0.02 g of hydroquinone methyl ether, 0.02 g of dibutyltin dilaurate and 500 g of methyl ethyl ketone were added and reacted at 60 ° C. for 3 hours. When the residual isocyanate group reached 0.3%, the reaction was terminated and the solvent was distilled off. As a result, urethane acrylate (A) was obtained. The number average molecular weight of the obtained urethane acrylate (A) was 1570.

<Example 8>

6 Urethane acrylate 50 parts by weight of the functional with the same isophorone structure as in Example 1, bis (hydroxymethyl) tricyclo [5.2.1.0 ^{2, 6]} decane = dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd. "DCP" ) 50 parts by weight, 1 part by weight of 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Geigy) was stirred at 60 ° C. until uniform, to obtain a photopolymerizable composition [I]. The photopolymerizable composition [I] was defoamed using a twin-screw extruder, and a drum-type roll (R1) having a liquid temperature of 23 ° C., a surface temperature of 23 ° C., and a rotational speed of 3 m / min from a T-type slit die. Cast to (diameter 3 m, width 4 m). Two minutes later, ultraviolet rays having an illuminance of 200 mW / cm ² and a light amount of ² J / cm ² were irradiated using a metal halide lamp. The obtained cured product film is peeled from the roll and conveyed so that the ultraviolet irradiation surface of the film is in contact with a drum-type roll (R2) (diameter 1 m, width 4 m) at a surface temperature of 23 ° C. and a rotation speed of 3 m / min. On the drum roll (R2), a metal halide lamp was used to irradiate ultraviolet rays with an illuminance of 200 mW / cm ² and a light amount of ² J / cm ² (the total irradiation light amount was 4 J / cm ² ). Next, both sides of the film are alternately turned into drum-type rolls (R3), (R4), (R5), (R6) (all with a diameter of 1 m and a width of 4 m) at a surface temperature of 180 ° C. and a rotation speed of 3 m / min Transported to contact. After heat treatment for 2 minutes on each roll (total heat treatment was 8 minutes), the resin molded body was wound up to obtain a film roll (resin molded body) shown in Table 2. The physical properties of the obtained resin molding were as shown in Table 3. A gas barrier film and a transparent conductive film were obtained from the obtained resin molded body in the same manner as in Example 1. The characteristics of the obtained gas barrier film and transparent conductive film were as shown in Table 4.

<Examples 9 and 10>
The same procedure as in Example 8 was performed except that the molding was performed under the conditions shown in Tables 1 and 2. The physical properties of the obtained resin molding were as shown in Table 3. Further, a gas barrier film and a transparent conductive film were obtained in the same manner as in Example 1. The characteristics of the obtained gas barrier film and transparent conductive film were as shown in Table 4.

<Example 11>

6 Urethane acrylate 50 parts by weight of the functional with the same isophorone structure as in Example 1, bis (hydroxymethyl) tricyclo [5.2.1.0 ^{2, 6]} decane = dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd. "DCP" ) 50 parts by weight, 1 part by weight of 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Geigy Co.) and 5 parts by weight of ethyl acetate are stirred until uniform at 60 ° C., and the photopolymerizability is 1300 mPa · s. A composition [I] solution was obtained. This solution was defoamed using a twin-screw extruder, and was a drum-type roll (R1) (diameter 3 m, width 4 m) at a liquid temperature of 23 ° C., a surface temperature of 60 ° C., and a rotational speed of 3 m / min. It was cast into. After drying for 2 minutes, ultraviolet rays with a light intensity of ² J / cm ² were irradiated at an illuminance of 200 mW / cm ² using a metal halide lamp. The obtained cured product film is peeled from the roll, and conveyed so that the ultraviolet irradiation surface of the film is in contact with a drum-type roll (R2) (diameter 1 m, width 4 m) at a surface temperature of 60 ° C. and a rotation speed of 3 m / min. On the drum roll (R2), a metal halide lamp was used to irradiate ultraviolet rays with an illuminance of 200 mW / cm ² and a light amount of ² J / cm ² (the total irradiation light amount was 4 J / cm ² ). Next, both sides of the film are alternately turned into drum-type rolls (R3), (R4), (R5), (R6) (all with a diameter of 1 m and a width of 4 m) at a surface temperature of 180 ° C. and a rotation speed of 3 m / min. Transported to contact. After heat-treating on each roll for 2 minutes, the resin molded body was wound up to obtain a film roll (resin molded body) shown in Table 2. The physical properties of the obtained resin molding were as shown in Table 3. Further, in the same manner as in Example 1, a gas barrier film and a transparent conductive film were obtained from the obtained resin molded body. The characteristics of the obtained gas barrier film and transparent conductive film were as shown in Table 4.

<Examples 12 and 13>
The same procedure as in Example 11 was performed except that the molding was performed under the conditions shown in Tables 1 and 2. The physical properties of the obtained resin molding were as shown in Table 3. Further, a gas barrier film and a transparent conductive film were obtained in the same manner as in Example 1. The characteristics of the obtained gas barrier film and transparent conductive film were as shown in Table 4.

<Example 14>
An ethylene-vinyl alcohol copolymer (“Soanol D2908” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was dissolved in isopropyl alcohol to prepare a gas barrier coating agent having a concentration of 20% by weight, and then this coating agent was obtained in Example 2. A gas barrier film was obtained in the same manner as in Example 1 except that one side of the resin molded body was spin coated to form a gas barrier film having a thickness of 3 μm. Furthermore, the transparent conductive film was obtained like Example 1 using the obtained gas-barrier film. The characteristics of the obtained gas barrier film and transparent conductive film were as shown in Table 4.

<Example 15>
An ethylene-vinyl alcohol copolymer (“Soanol D2908” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was dissolved in isopropyl alcohol to prepare a gas barrier coating agent having a concentration of 20% by weight. A gas barrier film was obtained in the same manner as in Example 1 except that a gas barrier film having a thickness of 3 μm was formed by spin coating on the film. Furthermore, the transparent conductive film was obtained like Example 1 using the obtained gas-barrier film. The characteristics of the obtained gas barrier film and transparent conductive film were as shown in Table 4.

<Comparative Example 1>
Using the photopolymerizable composition shown in Table 1, an attempt was made in the same manner as in Example 1, but it could not be injected into the mold due to high viscosity. Therefore, the liquid temperature was 60 ° C. and molding was performed under the curing conditions shown in Table 2. The physical properties of the obtained resin molding were as shown in Table 3. Further, a gas barrier film and a transparent conductive film were obtained in the same manner as in Example 1. The characteristics of the obtained gas barrier film and transparent conductive film were as shown in Table 4.

<Comparative example 2>
Using the photopolymerizable composition shown in Table 1, an attempt was made in the same manner as in Example 1, but the 200 μm thick film was cracked and could not be formed. Therefore, molding was performed under the curing conditions shown in Table 2 using a molding die having a 400 μm thick silicon plate as a spacer. An unreacted liquid composition was present when the amount of UV irradiation was 5 J / cm ² , and thus a light amount of 20 J / cm ² was irradiated. The physical properties of the obtained resin molding were as shown in Table 3. Further, a gas barrier film and a transparent conductive film were obtained in the same manner as in Example 1. The characteristics of the obtained gas barrier film and transparent conductive film were as shown in Table 4.

<Comparative Example 3>
The physical properties of a commercially available polycarbonate sheet (“Panlite” thickness 170 μm manufactured by Teijin Ltd.) are as shown in Table 3. Using this, a gas barrier film and a transparent conductive film obtained in the same manner as in Example 1 were used. The properties of the adhesive film were as shown in Table 4.

The resin molded body of the present invention can be advantageously used for various optical materials and electronic materials. For example, liquid crystal substrates, organic / inorganic EL substrates, electronic paper substrates, light guide plates, phase difference plates, touch panels, etc., various display members, optical recording substrates and film / coating applications for optical disks, thin films, etc. It can be used for energy applications such as battery substrates and solar cell substrates, optical communication applications such as optical waveguides, and various optical films, sheets and coatings such as functional films and sheets, antireflection films and optical multilayer films.

Organic EL device using transparent conductive film according to the present invention

Explanation of symbols

1: Resin molding 2: Anode 3: Organic light emitting layer 3a: Hole injection layer 3b: Hole transport layer 3c: Electron transport layer 4: Cathode

Claims (24)

A resin molded product obtained by photocuring the (meth) acrylate photopolymerizable composition [I], having a thickness of 50 to 400 μm, a surface pencil hardness of 4H or more, and (meth) A resin molded product, wherein the acrylate photopolymerizable composition [I] contains the following components (A), (B), and (C).
(A) Polyfunctional urethane (meth) acrylate having an alicyclic structure obtained by reacting a polyisocyanate compound having an alicyclic structure and a hydroxyl group-containing (meth) acrylate (B) Bifunctional (meth) acrylate having an alicyclic structure ( (Excluding (A))
(C) Photopolymerization initiator The resin molded article according to claim 1, wherein the flexural modulus is 2.5 to 3.5 GPa (25 ° C). The resin molded body according to claim 1 or 2, wherein at least one surface has a surface roughness Ra of 20 nm or less. The compounding ratio of a component (A) and a component (B) is 30: 70-70: 30 (weight ratio), The resin molding in any one of Claims 1-3 characterized by the above-mentioned. 5. The resin molded article according to claim 1, wherein the (meth) acrylate photopolymerizable composition [I] has a viscosity at 23 ° C. of 200 to 6000 mPa · s. The number average molecular weight of polyfunctional urethane (meth) acrylate (A) which has an alicyclic structure is 200-5000, The resin molding in any one of Claims 1-5 characterized by the above-mentioned. The resin molded product according to any one of claims 1 to 6, wherein the polyfunctional urethane (meth) acrylate (A) having an alicyclic structure is an acrylate. The resin molded product according to claim 7, wherein the polyfunctional urethane (meth) acrylate (A) having an alicyclic structure has 2 to 6 acryloyl groups in the molecule. The polyfunctional urethane (meth) acrylate (A) having an alicyclic structure has an alicyclic structure represented by the following formula (1), (2), (3) or (4). ~ 8 molded resin

Here, R ₁ is hydrogen or a methyl group.

The resin molded article according to any one of claims 1 to 9, wherein the bifunctional (meth) acrylate (B) having an alicyclic structure (excluding (A)) is methacrylate. The bifunctional (meth) acrylate (B) having an alicyclic structure is at least one bifunctional (meth) acrylate selected from the following general formulas (5), (6), and (7). The resin molding in any one of Claims 1-9.

Here, R ₂ is an alkylene group that may contain an ether bond having 1 to 6 carbon atoms, R ₃ is hydrogen or a methyl group, a is 1 or 2, and b is 0 or 1.

Here, R ₄ is an alkylene group that may contain an ether bond having 1 to 6 carbon atoms, and R ₅ is hydrogen or a methyl group.

Here, R ₆ is hydrogen or a methyl group, R ₇ is an alkylene group that may contain an ether bond having 1 to 6 carbon atoms, and R ₈ is hydrogen or a methyl group. The resin molded product according to any one of claims 1 to 11, which has a light transmittance of 90% or more and a refractive index of 1.48 to 1.54. Retardation is 10 nm or less, The resin molding in any one of Claims 1-12 characterized by the above-mentioned. The resin molded article according to any one of claims 1 to 13, wherein the glass transition point is 120 ° C or higher and the linear expansion coefficient is 20 to 70 ppm / ° C. It uses as a board | substrate for organic electroluminescent displays, The resin molding in any one of Claims 1-14 characterized by the above-mentioned. The (meth) acrylate photopolymerizable composition [I] is photocured at an irradiation light amount of 5 J / cm ² or less using an active energy ray having a wavelength of 200 to 400 nm. The manufacturing method of the resin molding of description. The resin molding according to claim 16, wherein a solution containing 30% by weight or more of a (meth) acrylate photopolymerizable composition [I] is cast on a continuous cast substrate, dried and then photocured. Body manufacturing method. The method for producing a resin molded body according to claim 16 or 17, further comprising heat-treating at a temperature of 100 ° C or higher after photocuring . A gas barrier film, wherein a gas barrier film is formed on at least one surface of the resin molded body according to claim 1. The gas barrier film according to claim 19, wherein the gas barrier film comprises a silicon oxide film and / or a vinyl alcohol resin film. 21. The gas barrier film according to claim 19 or 20, wherein the gas barrier film is formed by a layer structure of resin molded body / silicon oxide film / vinyl alcohol-based resin film. A transparent conductive film comprising a transparent conductive film formed on at least one surface of the gas barrier film according to claim 19. An organic electroluminescent device comprising the transparent conductive film according to claim 22. A touch panel comprising the resin molded body according to claim 1.

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