JP5882815B2 - Resin molded body and laminate formed using the same - Google Patents

Description

  The present invention relates to a resin molded body obtained by curing a polymerizable composition, and in particular, is a sheet-shaped or film-shaped resin molded body having excellent optical characteristics, thermal characteristics, mechanical characteristics, and electrical characteristics. In particular, the present invention relates to a resin molding useful as a plastic substrate for a capacitive touch panel.

  Conventionally, many substrates using glass as a substrate for display have been used. For example, in a cover window, a touch panel, a liquid crystal display, and an organic electroluminescence (EL) display, a glass substrate having a thickness of about 0.5 to 1 mm is widely used. In recent years, plastic substrates have begun to be used from the viewpoint of light weight and thickness reduction and safety improvement, and for the purpose of manufacturing flexible displays. Actually, a polyethylene terephthalate (PET) film in which a polymethyl methacrylate (PMMA) or polycarbonate substrate is used for the cover window or a transparent electrode such as ITO is formed on the touch panel is widely used. Such plastic substrates have optical properties such as light transmittance and birefringence, as well as thermal properties such as heat resistance and linear expansion coefficient, mechanical properties such as impact resistance, surface hardness, flexural modulus, water absorption rate and High processability such as specific gravity, chemical resistance, solvent resistance, and adhesion of inorganic film is required.

  In order to satisfy these various properties, many resins have been proposed regardless of thermoplasticity or thermosetting properties. For example, if the heat resistance of the resin is improved, the impact resistance is reduced, or nanofillers are added. When the surface hardness is improved by blending, the optical properties are lowered. Furthermore, multilayer technology such as film bonding and hard coating has led to increased costs.

  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). A polymerizable composition containing 75 wt% or more of a tri- or higher functional aliphatic (meth) acrylate compound is disclosed to give a resin molded body having high heat resistance and low birefringence (for example, Patent Documents). 2). Furthermore, it is disclosed that a polymerizable composition containing a bifunctional aliphatic (meth) acrylate compound and a tri- or higher functional (meth) acrylate compound provides a resin molded product having high heat resistance and a low linear expansion coefficient. (For example, see Patent Document 3).

  Further, it is disclosed that a photopolymerizable composition comprising a polyfunctional urethane (meth) acrylate having an alicyclic structure and a polyfunctional (meth) acrylate having an alicyclic structure gives a resin molded article having high pencil hardness. (For example, refer to Patent Document 4), monofunctional (meth) acrylate having an alicyclic structure, polyfunctional urethane (meth) acrylate having an alicyclic structure, and polyfunctional (meth) acrylate having an alicyclic structure It is disclosed that a polymerizable composition gives a resin molded article excellent in optical properties and thermomechanical properties (see, for example, Patent Document 5), a specific alicyclic skeleton bifunctional (meth) acrylate compound, a specific An aliphatic tetrafunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound having an alicyclic skeleton and a molecular weight of 200 to 2,000. The polymerizable composition is disclosed to give a resin molded product excellent in optical properties and thermomechanical properties (e.g., refer to Patent Document 6.).

JP-A-9-152510 JP 2002-302517 A JP 2003-292545 A JP 2006-193596 A JP 2007-204736 A JP 2007-56180 A

  However, it is hard to say that the characteristics are balanced even with these disclosed technologies. For example, in the technologies disclosed in Patent Documents 1 to 3, the heat resistance is improved by a highly crosslinked structure. However, since the molecular chain does not have a chemical structure that absorbs shock, it is easily broken and has the same impact resistance as glass. Only sex can be obtained. Generally, heat resistance and impact resistance are contradictory performances, and this problem is the reason for greatly reducing the opportunity for using a plastic substrate instead of glass.

  In addition, in the disclosed techniques of Patent Documents 4 to 6, although the impact resistance is improved by blending urethane (meth) acrylate, the effect is still satisfactory because only one of acrylate or methacrylate is used. For example, in the example of Patent Document 4, the result of a light drop ball impact test of 16 g is described, and further improvement is required.

  In view of the above, the present invention has an object to provide a resin molded article having both heat resistance and impact resistance and suitable for a glass substitute substrate.

  However, as a result of intensive studies by the present inventors to solve the above problems, in the polymerizable composition forming the resin molded body, a bifunctional (meth) acrylate component having a specific alicyclic structure, and an alicyclic structure It contains both polyfunctional urethane (meth) acrylate components having a alicyclic structure, and by using an acrylate component and a methacrylate component in combination as a bifunctional (meth) acrylate component, both heat resistance and impact resistance The present invention has been completed by finding that a resin molded article excellent in the above can be obtained.

That is, the gist of the present invention is a bifunctional (meth) acrylate component (A) having an alicyclic structure represented by the following general formula (1) and a polyfunctional urethane (meth) acrylate component (B) having an alicyclic structure. As a bifunctional (meth) acrylate component (A) which is a resin molded product obtained by curing a polymerizable composition [I] containing alicyclic structure, an acrylate component (a1) (R _3: hydrogen) and methacrylate component (a2) (R _3: blending ratio of the methyl group) (a1: a2) is 10: 90 to 90: a 10 (weight ratio), bifunctional methacrylate having an alicyclic structure blending ratio of the component (a) and the multifunctional urethane (meth) acrylate component having an alicyclic structure (B) (a: B) is 60: 40-95: 5 (weight ratio) and wherein der Rukoto It relates to a molded resin

  In addition, polyfunctional here means having two or more (meth) acryloyl groups in a molecule | numerator.

  The present invention also provides a laminate in which a gas barrier film is formed on at least one surface of the resin molded body, and further a transparent conductive film is formed on at least one surface of the resin molded body. In addition, the present invention also provides a laminate used as a capacitive touch panel substrate.

  According to the present invention, a resin molded body having high transparency, high heat resistance, high impact resistance, high surface hardness, high surface smoothness, and an appropriate bending elastic modulus can be obtained. Lamination with a gas barrier film having excellent properties and a conductive film having excellent conductivity is easy, and the obtained laminate is particularly suitable as a display substrate such as a touch panel.

  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 obtained by curing the polymerizable composition [I], and the polymerizable composition [I] has an alicyclic structure represented by the general formula (1). It contains a functional (meth) acrylate component (A) and a polyfunctional urethane (meth) acrylate component (B) having an alicyclic structure.

  Since both the component (A) and the component (B) used in the present invention have an alicyclic structure, it is easy to achieve high heat resistance, low water absorption, etc. of the resulting resin molded article, and curing By reducing shrinkage, there is an advantage that retardation during production can be reduced.

  The component (A) may be a bifunctional (meth) acrylate having an alicyclic structure represented by the general formula (1).

In General formula (1), R < ₂ > is the alkylene group which may contain the C1-C6 ether, and preferable carbon number is 1-3. R ₃ is hydrogen or a methyl group, n is 0 or 1, preferably 1, a is 1 or 2, and b is 0 or 1.

Specific examples of such component (A) include, for example, bis (hydroxy) tricyclo [5.2.1.0 ^2,6 ] decane = diacrylate, bis (hydroxy) tricyclo [5.2.1.0. ^2,6 ] decane dimethacrylate, bis (hydroxy) pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane diacrylate, bis (hydroxy) pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane = dimethacrylate, bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = diacrylate, bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] Decane = dimethacrylate, bis (hydroxymethyl) pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane diacrylate, bis (hydroxymethyl) pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane = dimethacrylate, bis (hydroxyethyl) tricyclo [5.2.1.0 ^2,6 ] decane = diacrylate, bis (hydroxyethyl) tricyclo [5.2.1.0 ^2,6 Decane = dimethacrylate, bis (hydroxypropyl) tricyclo [5.2.1.0 ^2,6 ] decane = diacrylate, bis (hydroxypropyl) tricyclo [5.2.1.0 ^2,6 ] decane = di And methacrylate. Among these, bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = diacrylate and bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] in terms of heat resistance. Decane = dimethacrylate is preferred, and in the present invention, it is important to use diacrylate (a1) and dimethacrylate (a2) in the di (meth) acrylate.

  As a number average molecular weight of the said component (A), 300-550 are preferable, Especially preferably, it is 310-500, More preferably, it is 320-450. If the number average molecular weight is too small, cure shrinkage tends to increase and retardation tends to occur in the resin molded product. Conversely, if the number average molecular weight is too large, crosslinkability tends to decrease and heat resistance tends to decrease.

  Since component (A) is a crosslinkable (meth) acrylate, it adds high heat resistance to the resin molded body by curing. However, acrylate (a1) alone is insufficient in heat resistance, and conversely, methacrylate (a2) alone is insufficient in impact resistance. Generally, it is known that a cured product of methacrylate has higher heat resistance than a cured product of acrylate if the chemical structure other than the (meth) acryloyl group portion is the same. The present invention achieves this effect and optimizes impact resistance by optimizing the blending ratio of the two.

  The reason why the impact resistance is improved by blending of methacrylate is not clear, but is presumed to be due to an increase in free volume in the resin. That is, although it is a crosslinked structure, it is considered that some kind of shock absorbing structure is expressed in the acrylic / methacrylic mixed resin.

It should be noted that bis (hydroxy) tricyclo [5.2.1.0 ^2,6 ] decane = acrylate methacrylate or bis (hydroxy) pentacyclo [6.] Having an acryloyl group at one end and a methacryloyl group at the other end. 5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane = acrylate methacrylate, bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = acrylate methacrylate or bis (hydroxymethyl) pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . [ ^09,13 ] Pentadecane = acrylate methacrylate can be used to achieve the same effect, but it is difficult to mass-produce and produce such a compound by accurately controlling the abundance of both groups.

The blending ratio (a1: a2) of the acrylate component (a1) (R ₃ : hydrogen) and the methacrylate component (a2) (R ₃ : methyl group) in the component (A) is 10:90 to 90:10 (weight ratio) der Ru. Good preferable range of mixing ratio, but is different depending on the use and display of the preparation, for example, in applications where high temperature processes such as a touch panel or an organic EL display is present, the preferred range is 10: 90-50: 50 (Weight ratio), more preferably 10:90 to 40:60 (weight ratio), particularly preferably 10:90 to 30:70 (weight ratio). If the blending ratio of the methacrylate component (a2) is too small, the resin It reduces the heat resistance of the molded article, the impact resistance of too large a resin molded product you decrease. Conversely, in applications where strength is important, such as cover windows, the preferred range is 50:50 to 90:10 (weight ratio), more preferably 60:40 to 90:10 (weight ratio), particularly preferably. It is 70:30 to 90:10 (weight ratio), and if the blending ratio of the acrylate component (a1) is too small, the impact resistance of the resin molded product tends to decrease, and if too large, the heat resistance of the resin molded product is low. There is a tendency to decrease.

  The component (B) may be a polyfunctional urethane (meth) acrylate having an alicyclic structure, and is a urethane (meth) acrylate containing two or more (meth) acryloyl groups in the molecule.

  Since the component (B) 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 curing, and a resin molded body having high heat resistance can be obtained. Usually, the cross-linked structure causes a drop in impact resistance, but urethane (meth) acrylate has a urethane group in the molecule, and the resulting resin molded product has moderate toughness due to hydrogen bonding, resulting in a drop in impact resistance. Can be avoided. Furthermore, it is worth mentioning that the surface hardness is improved. Generally, polyfunctional urethane (meth) acrylate is used as a hard coating agent, and the film has high pencil hardness and scratch resistance. .

  The functional group of the polyfunctional urethane (meth) acrylate is preferably an acrylate from the viewpoint of curing speed. Further, the number of functional groups varies depending on the application and the manufacturing method of the display. For example, in applications where high-temperature processes such as touch panels and organic EL displays are present, trifunctional or more is preferable, and more preferably 4 to 10 functional Particularly preferred are 5 to 8 functional groups. In the case of monofunctional (number of functional groups: 1), the heat resistance of the resin molded product tends to decrease, and when the number of functional groups is too large, the impact resistance of the resin molded product tends to decrease. On the other hand, in applications where strength is important, such as a cover window, 6 or less functional groups are preferable, 2 to 5 functional groups are more preferable, and 2 to 4 functional groups are particularly preferable. In the case of monofunctional (number of functional groups: 1), the heat resistance of the resin molded product tends to decrease, and when the number of functional groups is too large, the impact resistance of the resin molded product tends to decrease.

  It is preferable that the number average molecular weights of a component (B) are 200-5000. More preferably, it is 400-3000, More preferably, it is 500-1000. If the number average molecular weight is too small, cure shrinkage tends to increase and retardation tends to occur in the resin molded product. Conversely, if the number average molecular weight is too large, crosslinkability tends to decrease and heat resistance tends to decrease.

  The polyfunctional urethane (meth) acrylate having an alicyclic structure as the component (B) is, for example, a polyisocyanate having an alicyclic structure and a hydroxyl group-containing (meth) acrylate, using a catalyst such as dibutyltin dilaurate as necessary. Can be obtained by reaction.

Examples of the polyisocyanate having an alicyclic structure include isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, hydrogenated xylylene diisocyanate, and water. Examples thereof include diisocyanates such as added diphenylmethane diisocyanate, and trimer compounds of these diisocyanates. Among these, isophorone diisocyanate and norbornene diisocyanate are preferably used from the viewpoint of excellent impact resistance of the molded resin.
Moreover, the both terminal isocyanate group containing compound formed by making the said polyisocyanate and polyol react can also be used as needed.

  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) acryloyloxy. Examples include propyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol tri (meth) acrylate.

  Two or more polyfunctional urethane (meth) acrylates obtained by reacting a polyisocyanate having an alicyclic structure with a hydroxyl group-containing (meth) acrylate may be used in combination.

The blending ratio (A: B) of the component (A) and the component (B) is 60:40 to 95: 5 (weight ratio). When component (B) is too small to decrease the mechanical properties such as impact resistance and surface hardness, conversely, component (B) is too large, the polymerizable composition [I] becomes a high viscosity, the resin molding production that Do not difficult. A preferable range of the blending ratio (A: B) is 70:30 to 90:10 (weight ratio), more preferably 75:25 to 90:10 (weight ratio), and particularly preferably 80:20 to 90:10. (Weight ratio).

  Thus, a polymerizable composition [I] containing a bifunctional (meth) acrylate component (A) having an alicyclic structure and a polyfunctional urethane (meth) acrylate component (B) having an alicyclic structure is obtained. The polymerizable composition [I] is preferably blended with a polymerization initiator (C) in order to be cured by at least one of light and thermal polymerization to form a resin molded body. When the initiator (C1) is cured by thermal polymerization, it is preferable to blend a thermal polymerization initiator (C2). When performing both photopolymerization and thermal polymerization, a photopolymerization initiator (C1) and a thermal polymerization initiator (C2) may be used in combination. In the present invention, photopolymerization is preferred from the viewpoint of retardation reduction and productivity.

  As the photopolymerization initiator (C1), known compounds can be used. For example, benzophenone, benzoin methyl ether, benzoin propyl ether, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2,6-dimethylbenzoyldiphenylphosphine Oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. Among these, radical-cleavage photopolymerization initiators such as 1-hydroxycyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are preferable. These photopolymerization initiators (C1) may be used alone or in combination of two or more.

  The compounding quantity of a photoinitiator (C1) is 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, Especially It is preferable that it is 0.3-3 weight part. If the amount is too large, the retardation of the resin molded product increases and yellowing tends to occur. If the amount is too small, the polymerization rate decreases and the polymerization may not proceed sufficiently.

  As the thermal polymerization initiator (C2), known compounds can be used. For example, hydroperoxide, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydro Hydroperoxides such as peroxides, dialkyl peroxides such as di-t-butyl peroxide and dicumyl peroxide, peroxys such as t-butylperoxybenzoate, t-butylperoxy (2-ethylhexanoate) Examples thereof include diacyl peroxides such as esters and benzoyl peroxide, peroxycarbonates such as diisopropyl peroxycarbonate, peroxides such as peroxyketal and ketone peroxide. These thermal polymerization initiators (C2) may be used alone or in combination of two or more.

  The blending amount of the thermal polymerization initiator (C2) is 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, particularly 100 parts by weight in total of the component (A) and the component (B). It is preferable that it is 0.3-3 weight part. If the amount is too large, the retardation of the resin molded product increases and yellowing tends to occur. If the amount is too small, the polymerization rate decreases and the polymerization may not proceed sufficiently.

  In the present invention, a small amount of auxiliary components may be included within a range not impairing the physical properties of the resin molded body of the present invention. Examples of such auxiliary components include components other than components (A) and (B). And monomers having an ethylenically unsaturated bond, chain transfer agents, antioxidants, ultraviolet absorbers, polymerization inhibitors, antifoaming agents, leveling agents, bluing agents, dyes and pigments, and the like.

  Examples of the monomer having an ethylenically unsaturated bond other than the components (A) and (B) include, for example, methyl methacrylate, 2-hydroxyethyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl Monofunctional (meth) acrylates such as (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and di (meth) acrylate of polyethylene glycol higher than tetraethylene 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) acryloxyp Polyfunctional (meth) acrylates such as lopan, 2,2-bis [4- (meth) acryloyloxyphenyl] propane, trimethylolpropane tri (meth) acrylate, methacrylonitrile, methacrylonitrile, etc. ) Acrylic acid derivatives, styrene compounds such as styrene, chlorostyrene, divinylbenzene, and α-methylstyrene.

  The compounding amount of the monomer having an ethylenically unsaturated bond other than the components (A) and (B) is 30 parts by weight or less with respect to a total of 100 parts by weight of the component (A) and the component (B). It is preferably 20 parts by weight or less, particularly 10 parts by weight or less. If the amount is too large, the heat resistance and impact resistance of the resin molded product tend to decrease.

  As the chain transfer agent, a polyfunctional mercaptan compound is preferable. Examples of the polyfunctional mercaptan compound include pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, and the like. These polyfunctional mercaptan-based compounds are preferably used in a proportion of usually 10 parts by weight or less, more preferably 5 parts by weight or less, particularly 3 parts by weight, based on 100 parts by weight of the polymerizable composition [I]. The following is preferred. When there is too much this usage-amount, there exists a tendency for the heat resistance of the molded object obtained and rigidity to fall.

  Examples of the antioxidant include 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, 2,4,6-tri-t-butylphenol, 2,6-di- t-butyl-4-s-butylphenol, 2,6-di-t-butyl-4-hydroxymethylphenol, n-octadecyl-β- (4'-hydroxy-3 ', 5'-di-t-butylphenyl) ) Propionate, 2,6-di-tert-butyl-4- (N, N-dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, 2,4 -Bis (n-octylthio) -6- (4-hydroxy-3 ', 5'-di-t-butylanilino) -1,3,5-triazine, 4,4-methylene-bis (2,6-di-) t-Butylpheno ), 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide 4,4'-di-thiobis (2,6-di-t-butylphenol), 4,4'-tri-thiobis (2,6-di-t-butylphenol), 2,2-thiodiethylenebis [3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis- (3,5-di-t-butyl-4-hydroxyhydrocinnamide, N, N '-Bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, calcium (3,5-di-tert-butyl-4-hydroxybenzyl) monoethyl phosphonate 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-t-butyl-4-hydroxyphenyl) ) Isocyanurate, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris-2 [3 (3,5-di-t-butyl-4-hydroxyphenyl) ) Propionyloxy] ethyl isocyanate, tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4-hydroxyphenyl) propionate] methane, 3,5-di-t-butyl-4-hydroxybenzylphos Compounds such as phyto-diethyl ester may be mentioned, and these compounds may be used alone or in combination of two or more thereof. - (3 ', 5'-di -t- butyl-4-hydroxyphenyl) propionate] methane, particularly from the viewpoint of the effect of suppressing the hue increases.

  The blending ratio of the antioxidant is preferably usually 0.001 to 1 part by weight, particularly preferably 0.01 to 0.5 part by weight with respect to 100 parts by weight of the polymerizable composition [I]. . If the amount of such an antioxidant is too small, the light resistance of the resin molded product tends to decrease, and if it is too large, the light transmittance tends to decrease.

  Thus, the polymerizable composition [I] used in the present invention is obtained. The polymerizable composition [I] preferably has a viscosity at 23 ° C. of 100 to 10,000 mPa · s. More preferably, it is 200-5000 mPa * s, More preferably, it is 300-3000 mPa * s. If the viscosity is too low, unpolymerized monomers tend to remain in the molding step. Conversely, if the viscosity is too high, handling tends to be difficult. As a method of adjusting to such a viscosity, mainly, the types and blending amounts of the component (A) and the component (B) are appropriately controlled.

  Next, the method for producing a resin molded body of the present invention will be described by taking as an example a case where photopolymerization is performed on the polymerizable composition [I].

As a manufacturing method of the resin molding in this invention, the said polymeric composition [I] is used in the range of 1-100 J / cm < ² > of irradiation light quantities using an active energy ray, especially the ultraviolet-ray with a wavelength of 200-400 nm, for example. It is preferable to perform photocuring and molding. A more preferable range of the irradiation light amount is 5 to 70 J / cm ² , and more preferably 10 to 50 J / cm ² . When the amount of irradiation light is too small, the polymerization tends to be insufficient, and when too much, the productivity tends to decrease. The illuminance of ultraviolet rays is usually 10 to 5000 mW / cm ² , preferably 100 to 1000 mW / cm ² . If the illuminance is too small, the inside of the molded body tends to be hard to be cured sufficiently, and if the illuminance is too large, polymerization tends to run away and retardation tends to increase.

  When irradiating with ultraviolet rays, it is preferable to divide it into a plurality of times because a resin molded product with smaller retardation 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 by a batch polymerization method using an injection mold or a continuous polymerization method using a continuous cast substrate such as a belt or a drum. In the former case, a mold in which two transparent glasses are opposed to each other is manufactured through a spacer for controlling the thickness, the polymerizable composition [I] is injected into the cavity, and the active energy ray is made to be polymerizable. It is carried out by irradiating and polymerizing the composition [I] to demold the cured product. In the latter case, the polymerizable composition [I] or a solution containing the polymerizable composition [I] is cast on a continuous cast substrate such as a belt or a drum, and after drying, if necessary, continuously. Polymerization is performed by irradiating active energy rays, and the cured product is peeled off from the cast substrate. In the present invention, the photoforming method may be a batch type, but the continuous forming method is more preferable particularly in that a long and wide film roll can be obtained.

Thus, the resin molded product of the present invention is obtained.
The thickness of the resin molding directly affects the rigidity and flexibility of the plastic substrate and is optimized for each application. In the present invention, the thickness is 0.1 to 3 mm, particularly 0.2 to It is preferably 2 mm, more preferably 0.3 to 1.5 mm. Among them, for example, in applications where importance is attached to lightweight and thinning and flexibility such as organic EL displays, the preferred range is 0.1 to 1 mm, more preferably 0.2 to 0.7 mm, and particularly preferably 0.3 to 0. If the thickness is too thin, the function as a display support tends to be lowered. Conversely, if the thickness is too thick, it is difficult to reduce the weight and thickness. For example, in applications where rigidity and strength are also required, such as cover windows and touch panels, the preferred range is 0.2 to 3 mm, more preferably 0.5 to 2 mm, and particularly preferably 0.7 to 1.5 mm. If the thickness is too thin, the protective function of the display tends to be reduced. Conversely, if the thickness is too thick, it is difficult to reduce the weight and thickness.

Next, the performance of the resin molding of the present invention will be described.
The resin molded body of the present invention preferably has a relative dielectric constant of 4 or less at 1 MHz in view of normal operation of the display. When the relative dielectric constant exceeds 4, noise generated on the touch panel tends to adversely affect the driving of the liquid crystal display. A more preferable range of the dielectric constant is 1 to 3.7, particularly preferably 2 to 3.5. The relative dielectric constant can be controlled by the resin composition and additives.

  The resin molded product of the present invention preferably has a light transmittance of 90% or more from the viewpoint of increasing the brightness of the display. A more preferable range of the light transmittance is 91% or more, particularly preferably 92% or more. In general, the upper limit of the light transmittance is 99%.

  The resin molded body of the present invention preferably has a retardation of 10 nm or less from the viewpoint of the fineness of the display. A more preferable range of retardation is 5 nm or less, particularly preferably 2 nm or less. In general, the lower limit of retardation is 0.01 nm.

  The resin molded body of the present invention preferably has a surface pencil hardness of 2H or more from the viewpoint of protecting the display. A more preferable range of pencil hardness is 3H or more, particularly preferably 4H or more. If the pencil hardness is too low, the resin molded body tends to be damaged and the quality of the display tends to deteriorate.

  The resin molded body of the present invention preferably has a glass transition temperature of 200 ° C. or higher from the viewpoint of heat resistance when producing a display. A more preferable range of the glass transition temperature is 210 ° C. or higher, particularly preferably 220 ° C. or higher. If the glass transition temperature is too low, the heat resistance is low, so that it tends to be deformed when a gas barrier film or a transparent conductive film is formed.

  The resin molded body of the present invention preferably has a flexural modulus of 2 to 4 GPa (25 ° C.). If the flexural modulus is too small, the resin molded body is insufficient in toughness, so that deflection and undulation occur in the film forming process and display manufacturing process, and it tends to be difficult to ensure uniform gas barrier properties and electrical conductivity. If the flexural modulus is too large, the flexibility of the resin molding or display tends to be impaired.

  As for the resin molding of this invention, it is more preferable that surface roughness Ra is 20 nm or less. If the surface roughness is too large, gas barrier properties and conductivity tend to decrease, and display defects tend to occur in the display.

  In the present invention, a gas barrier film or a transparent conductive film is preferably formed on at least one surface of the resin molded body to form a laminate, and a film or sheet having gas barrier properties or a film or sheet with a transparent electrode It can be.

Examples of the gas barrier film include inorganic films such as a silicon oxide film and alumina, and organic films made of a vinyl alcohol resin such as a polyvinyl alcohol resin and an ethylene-vinyl alcohol resin. 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 resin film having a thickness of 0.5 to 5 μm.
In addition, the gas barrier film here includes not only a function of blocking oxygen and moisture but also a film for the purpose of reducing warpage and undulation of the resin molded body due to heat.

  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). Among these, an ITO film is preferable. The film thickness is preferably 1000 to 30000 nm, more preferably 2000 to 20000 nm, and still more preferably 3000 to 10000 nm. If the film thickness is too thick, the substrate tends to warp, and if it is too thin, the conductivity tends to be insufficient. Furthermore, the surface resistance value is preferably 1 to 1000Ω / □, more preferably 10 to 700Ω / □, and still more preferably 20 to 500Ω / □. If the surface resistance value is too high, the conductivity tends to be insufficient, and if it is too small, the position detection accuracy of the touch panel tends to decrease.

  Thus, a laminate having a transparent conductive film is obtained, and such a laminate is suitable as a touch panel substrate, particularly as a capacitive touch panel substrate.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to a following example, unless the summary is exceeded.
In the examples, “parts” and “%” mean weight basis.
The measuring method of each physical property is as follows.

(1) Glass transition temperature Using a test piece having a length of 20 mm and a width of 5 mm, using a tensile mode of a dynamic viscoelastic device “DVE-V4 type FT Rheospectr” manufactured by Rheology, a frequency of 10 Hz, a heating rate Measurement was performed at 3 ° C./min and a strain of 0.025%. The ratio (tan δ) of the imaginary part (loss elastic modulus) to the real part (storage elastic modulus) of the obtained complex elastic modulus was determined, and the maximum peak temperature of tan δ was defined as the glass transition temperature (° C.).

(2) Falling ball impact resistance A test piece with a width and length of 5 cm each is placed on a support ring with an inner diameter of 4 cm, a 130 g steel ball is naturally dropped at the center of the sheet, and the minimum height at which the test piece is damaged is 5 cm. The drop impact resistance (cm) was evaluated by measuring in steps.

(3) Light transmittance The light transmittance (%) at 550 nm was measured using a spectrophotometer (trade name: “Ubest-35” manufactured by JASCO Corporation).

(4) Retardation Retardation (nm) was measured at 25 ° C with an oak birefringence measuring apparatus.

(5) Pencil hardness Pencil hardness was measured according to JIS K-5600.

(6) Relative permittivity The relative permittivity was measured at 23 ° C. using a precision LCR meter E4980A manufactured by Agilent Technologies. The measurement frequency is 1 MHz.

(7) Oxygen permeability The oxygen permeability (cc / day · atm · m ² ) was measured under the conditions of 23 ° C. and 80% RH with an oxygen mocon measuring device manufactured by Oxytran.

(8) Surface resistance value The surface resistance value (Ω / □) was measured using a 4-terminal resistance measuring instrument (Lorestar MP) manufactured by Mitsubishi Chemical Corporation.

<Preparation of polyfunctional urethane (meth) acrylate having alicyclic structure>
[Urethane acrylate (B-1): Preparation of bifunctional urethane acrylate having an isophorone structure]
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen gas inlet, 53.34 g (0.24 mol) of isophorone diisocyanate, 62.47 g (0.48 mol) of 2-hydroxypropyl acrylate, Add 0.02 g of hydroquinone methyl ether, 0.02 g of dibutyltin dilaurate, and 500 g of methyl ethyl ketone and react at 60 ° C. for 3 hours. When the residual isocyanate group becomes 0.3%, the reaction is terminated and the solvent is distilled off. Urethane acrylate (B-1) was obtained. The number average molecular weight of the obtained urethane acrylate (B-1) was 480.

[Urethane acrylate (B-2): Preparation of hexafunctional urethane acrylate having isophorone structure]
A thermometer, a stirrer, a four-neck flask equipped with a water-cooled condenser, a nitrogen gas blowing inlet, isophorone diisocyanate 53.34g (0.24 mol) of pentaerythritol triacrylate 143.19g (0. 48 mol), 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. (B-2) was obtained. The number average molecular weight of the obtained urethane acrylate (B-2) was 820.

<Example 1>
[Preparation of polymerizable composition [I]]
As shown in Table 1, 75 parts of bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = diacrylate (a1-1) (A-DCP manufactured by Shin-Nakamura Chemical Co.), bis (hydroxymethyl) ) Tricyclo [5.2.1.0 ^2,6 ] decane = 5 parts of dimethacrylate (a2-1) (DCP manufactured by Shin-Nakamura Chemical Co., Ltd.), 20 parts of bifunctional urethane acrylate (B-1) having an isophorone structure , 1 part of 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Geigy) was stirred at 60 ° C. until uniform, to obtain a polymerizable composition [I].

[Preparation of molded resin]
The polymerizable composition [I-1] (23 ° C.) is poured into a mold using two glass plates facing each other and a 0.7 mm thick silicon plate as a spacer, and a metal halide lamp is used for illuminance. Ultraviolet rays were irradiated at 200 mW / cm ² and a light amount of 20 J / cm ² . Thereafter, 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 300 mm × length of 400 mm × thickness of 0.7 mm. As shown in Table 2, the obtained resin molded product had high heat resistance and high impact resistance, and other properties such as optical characteristics were also good.

[Production of laminate (gas barrier sheet)]
A gas barrier film made of silicon oxide having a thickness of 0.02 μm was formed on one surface of the resin molded body obtained above by a sputtering method to obtain a gas barrier sheet. Table 3 shows the oxygen permeability of the gas barrier sheet.

[Production of laminate (transparent conductive sheet)]
A transparent conductive film made of ITO having a thickness of 0.03 μm was formed on the surface opposite to the silicon oxide film-forming surface of the obtained gas barrier sheet to obtain a transparent conductive sheet having a three-layer structure. It was. Table 3 shows the surface resistance values of the transparent conductive sheet.

<Examples 2 to 7>
A polymerizable composition [I] was prepared with a blending composition as shown in Table 1, and a resin molded product was obtained in the same manner as in Example 1. The physical properties of the obtained resin molded product were as shown in Table 2.
Further, a laminate (gas barrier sheet) and a laminate (transparent conductive sheet) were obtained in the same manner as in Example 1. Table 3 shows the oxygen permeability of the obtained laminate and the surface resistance of the transparent conductive film.

<Comparative Example 1>
A polymerizable composition was prepared with a blending composition as shown in Table 1, and a resin molded body was obtained in the same manner as in Example 1. The physical properties of the obtained resin molded body were as shown in Table 2, and both heat resistance and impact resistance were low.
Further, a laminate (gas barrier sheet) and a laminate (transparent conductive sheet) were obtained in the same manner as in Example 1. The oxygen permeability of the obtained laminate and the surface resistance value of the transparent conductive film were as shown in Table 3.

<Comparative Example 2>
A polymerizable composition was prepared with a blending composition as shown in Table 1, and a resin molded body was obtained in the same manner as in Example 1. The physical properties of the obtained resin molded body are as shown in Table 2. Although excellent in heat resistance, impact resistance was low.
Further, a laminate (gas barrier sheet) and a laminate (transparent conductive sheet) were obtained in the same manner as in Example 1. The oxygen permeability of the obtained laminate and the surface resistance value of the transparent conductive film were as shown in Table 3.

  As described above, Comparative Examples 1 and 2 using only the acrylate component or only the methacrylate component as the bifunctional (meth) acrylate component (A) having an alicyclic structure satisfy both heat resistance and impact resistance in a balanced manner. No resin molded product was obtained. Furthermore, the resin molded body of Comparative Example 1 was inferior not only in pencil hardness but also in surface resistance. Therefore, it turns out that the resin moldings of Comparative Examples 1 and 2 are inappropriate as various optical materials and electronic materials.

  On the other hand, in Examples 1 to 7 in which the acrylate component and the methacrylate component were used in combination, it was possible to obtain a resin molded article having a good balance between heat resistance and impact resistance. Therefore, it turns out that these Examples 1-7 are suitable as an optical material and an electronic material. Actually, a laminate in which a gas barrier film or a transparent conductive film is formed on the resin molded bodies of Examples 1 to 7 is excellent as a capacitive touch panel substrate.

  Further, in Examples 2 to 7 in which the ratio (a1-1 / a2-1) of the acrylate component to the methacrylate component is 90/10 or less, a resin molded body that is more excellent in oxygen permeability and surface resistance value is obtained. On the other hand, in Examples 1-6 which are 10/90 or more, the resin molded product which was further excellent with the balance of both heat resistance and impact resistance was able to be obtained. Furthermore, in Examples 1-4 which used more acrylate components than the methacrylate component, it turned out that it is still more favorable in terms of impact resistance, and is very effective.

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. In particular, it is highly expected as a capacitive touch panel substrate.

Claims (7)

Polymerizable composition comprising a bifunctional (meth) acrylate component (A) having an alicyclic structure represented by the following general formula (1) and a polyfunctional urethane (meth) acrylate component (B) having an alicyclic structure A resin molded body obtained by curing the product [I], and
Mixing ratio of acrylate component (a1) (R ₃ : hydrogen) and methacrylate component (a2) (R ₃ : methyl group) as a bifunctional (meth) acrylate component (A) having an alicyclic structure (a1: a2) Is 10:90 to 90:10 (weight ratio),
The blending ratio (A: B) of the bifunctional methacrylate component (A) having an alicyclic structure and the polyfunctional urethane (meth) acrylate component (B) having an alicyclic structure is 60:40 to 95: 5 (weight ratio). ) resin molding, characterized in der Rukoto.

Resin molded body according to claim 1 Symbol placement, wherein the thickness of the resin molded body is 0.1 to 3 mm. The resin molded product according to claim 1 or 2, wherein the polymerizable composition [I] contains a photopolymerization initiator (C). Resin molded article according to claim 1 to 3 one item or, wherein the relative dielectric constant at 1MHz is 4 or less. A laminate having a gas barrier film formed on at least one surface of the resin molded body according to any one of claims 1 to 4 . A laminated body, wherein a transparent conductive film is formed on at least one surface of the resin molded body according to any one of claims 1 to 4 . The laminate according to claim 5 or 6 , wherein the laminate is used as a capacitive touch panel substrate.