JP2017198797A - Photocurable resin molded article, and polarizing plate and transmissive liquid crystal display using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable resin molded article that is tough, can improve workability in a production process, has a low viscosity in a coating liquid state without using a dilution solvent, thereby gives good surface properties, and can enhance reactivity upon irradiation with UV rays since the coating liquid has a low viscosity.SOLUTION: The photocurable resin molded article is made of a photocured film of a coating liquid comprising a photocurable monomer and a photopolymerization initiator. The photocurable monomer comprises a (meth)acrylate (A) and a (meth)acrylate (B), in which (B) includes at least one cyclic structure or at least one aromatic ring and has an ether skeleton. A mass ratio of (A) to (B) is 30:70 to 90:10. The coating liquid contains no dilution solvent. The photocurable resin molded article shows a tensile strength of 30 N/mmor more and a tensile elongation of 0.10 or more. The coating liquid has a viscosity of 50 to 600 mPa s (25°C). The photocurable resin molded article has a double bond reaction rate of 60% or more and less than 95%.SELECTED DRAWING: None

Description

  INDUSTRIAL APPLICABILITY The present invention can be used as a protective film for liquid crystal display devices, plasma display devices, electrochromic display devices, light emitting diode display devices, EL display devices, display device parts such as touch panels, and can also be used as a functional film. The present invention relates to a photocurable resin molded body, a polarizing plate using the same, and a transmissive liquid crystal display.

  A polarizing plate protective film for a liquid crystal display and a protective film for a polarizing plate used for an organic EL display or the like are provided with a functional layer in order to have various functions. Examples of the functional layer include an antistatic layer for imparting an antistatic function, an antireflection layer for suppressing reflection, and a hard coat layer for improving surface hardness.

  In the conventional technique, a coating for the purpose of imparting each of the above functions is applied on a plastic substrate film such as a TAC film or a PET film. In patent document 1, the example which formed the hard-coat layer on the TAC film is reported.

  In recent years, proposals have been made to obtain a base film by photocuring a photopolymerizable composition (Patent Document 2). The photocurable composition has a short reaction time and can be expected to improve productivity. Also, from the viewpoint of low environmental impact, it is considered that the use in a wide range of fields will progress in the future.

  However, as a problem of the photocurable film, there is a trade-off between the balance between strength and elongation properties.Those that are excellent in strength tend to be brittle due to lack of extensibility. Many had low heat resistance and strength. Therefore, there is an example in which characteristics are improved by selecting materials to satisfy these characteristics (Patent Document 3).

Japanese Patent No. 5340591 Japanese Patent Laid-Open No. 2015-11180 Japanese Patent No. 4690053

  The technique disclosed in Patent Document 3 is characterized by using a polyisocyanate compound having an alicyclic structure and a hydroxyl group-containing (meth) acrylate. Urethane acrylate has a urethane group in the molecule, and the resulting resin molded body has appropriate toughness and does not become brittle due to hydrogen bonding, so it has a highly crosslinked structure, but also has a flexural modulus and impact resistance. Thus, a flexible resin molded article having excellent mechanical strength can be obtained. However, the viscosity of the urethane acrylate itself is high, and when a coating liquid is formed, the viscosity is reduced using a solvent. Concerns when using a solvent in the coating solution include the environmental impact of volatile organic compound (VOC) emissions, the need for large equipment required for drying, and the film due to the solvent remaining inside the film. The influence on the characteristics can be considered.

  In order to solve the above-mentioned problems, it is required to design a solvent-free coating solution. However, in the case of a solvent-free solution, the coating solution viscosity becomes high, making it difficult to achieve both film properties and surface properties. In addition, due to the high viscosity of the coating film when irradiated with ultraviolet rays, the mobility of the molecules decreases, unreacted functional groups tend to remain, and there are problems such as bleeding out, reduced solvent resistance, and blocking. It was.

  The present invention is tough, can improve the workability in the manufacturing process, has good surface properties because the coating liquid viscosity is low without using a diluting solvent, and UV irradiation is performed because the coating liquid viscosity is low. It is an object of the present invention to provide a photo-curable resin molded product capable of increasing the reactivity at the time, a polarizing plate and a transmissive liquid crystal display using the same.

The photocurable resin molding according to the present invention comprises a photocured film of a coating liquid containing a photocurable monomer and a photopolymerization initiator, and the photocurable monomer has 2 or 3 (meta ) (Meth) acrylate (A) having an acryloyl group and (meth) acrylate (B) having one or two (meth) acryloyl groups in one molecule, and at least one (meth) acrylate (B) Or a ring structure having one or more aromatic rings and having an ether skeleton, and the mass ratio of (meth) acrylate (A) to (meth) acrylate (B) is from 30:70 to 90:10 The coating liquid does not contain a diluting solvent, the tensile strength of the photocurable resin molding is 30 N / mm ² or more, and the tensile elongation defined by the following formula (I) is 0.10 or more. Yes, the viscosity of the coating liquid is 50 to 600m It is Pa * s (25 degreeC), The double bond reaction rate defined by following formula (II) of the said photocurable resin molding is 60% or more and less than 95%, It is characterized by the above-mentioned.
Tensile elongation = {(Length at break) − (Initial length before tension)} / Initial length before tension Formula (I)
Double bond reaction rate (%) = 100 × {1- (P0-P1)} Formula (II)
here,
P0: peak intensity of the absorption of 810 cm ^-1 in the infrared absorption spectrum before photocuring the coating liquid P1: the peak intensity of the absorption of 810 cm ^-1 in the infrared absorption spectrum after photocuring the coating liquid is there.

  Moreover, it is good in the thickness of a photocurable resin molded object being 15 micrometers or more and 100 micrometers or less.

  The polarizing plate which concerns on this invention is equipped with the above-mentioned photocurable resin molding.

  The transmissive display according to the present invention includes the above-described photocurable resin molded body.

  According to the present invention, it is tough, can improve the workability in the manufacturing process, has a good surface property because the coating liquid viscosity is low without using a diluting solvent, and the coating liquid viscosity is low, so that ultraviolet rays can be obtained. A photocurable resin molded body capable of increasing the reactivity during irradiation, a polarizing plate using the same, and a transmissive liquid crystal display are realized.

As a result of intensive studies, the inventor of the present application has included a photocurable monomer and a photopolymerization initiator, and the photocurable monomer has (meth) acrylate (A) having 2 or 3 (meth) acryloyl groups in one molecule. ) And (meth) acrylate (B) having one or two (meth) acryloyl groups in one molecule, and (meth) acrylate (B) is one or more cyclic structures or one or more fragrances It contains a ring and has an ether skeleton, the mass ratio of (meth) acrylate (A) to (meth) acrylate (B) is from 30:70 to 90:10, and does not contain a diluent solvent. The tensile strength of the photocurable resin molded product is 30 N / mm ² or more, the tensile elongation defined by the following formula (I) is 0.10 or more, and the photocurable resin composition is used. The following formula ( It was invented to form a photocurable resin molded product having a double bond reaction rate defined in II) of 60% or more and less than 95%. For example, using a coating liquid having a viscosity of 50 to 600 mPa · s (25 ° C.), the coating liquid is applied to a support such as a film or a metal body with a thickness of 15 μm or more and 100 μm or less, and is photocured. By obtaining as a resin molded body, it is expected to improve the compatibility and reactivity of surface properties and film characteristics.
Tensile elongation = {(Length at break) − (Initial length before tension)} / Initial length before tension Formula (I)
Double bond reaction rate (%) = 100 × {1- (P0-P1)} Formula (II)
here,
P0: peak intensity of the absorption of 810 cm ^-1 in the infrared absorption spectrum before photocuring the coating liquid P1: the peak intensity of the absorption of 810 cm ^-1 in the infrared absorption spectrum after photocuring the coating liquid is there.

  The photocurable monomer (photocurable substance) used in the present invention refers to a monomer mainly composed of a monomer that is cured through a crosslinking reaction by irradiation with active rays such as ultraviolet rays and electron beams.

  The photocurable resin molded body according to the present invention is produced by photocuring a coating liquid containing a photocurable monomer resin and a photopolymerization initiator, and the photocurable monomer includes two types of acrylate (methacrylate) series. (Meth) acrylate (A) and (meth) acrylate (B), which are monomers of

  The (meth) acrylate (A) has 2 to 3 (meth) acryloyl groups in one molecule. As the (meth) acrylate (A), Aronix M-6100 (Toagosei), Purple light UV7000B (Nippon Synthetic Chemical Industry), Aronix M-208 (Toagosei), Aronix M-211B (Toagosei), etc. may be used. it can. In this specification, (meth) acrylate refers to both acrylate and methacrylate.

  The (meth) acrylate (B) has 1 to 2 (meth) acryloyl groups in one molecule, includes a cyclic structure or an aromatic ring, and has an ether skeleton. As (meth) acrylate (B), ACMO (KJ Chemicals), Aronix M-106 (Toagosei), Light Acrylate DCP-4EO-A (Kyoeisha Chemical), AMP-20GY (Shin Nakamura Chemical), Aronix M-110S (Toagosei), light acrylate POB-A (Kyoeisha Chemical) and the like can be used.

  A (meth) acrylate monomer containing a cyclic structure or an aromatic ring and having an ether skeleton imparts a property having a relatively excellent balance between strength and elongation.

  The mass ratio of (meth) acrylate (A) to (meth) acrylate (B) is desirably from 30:70 to 90:10. When this mass ratio is not satisfied, it becomes difficult to impart strength and elongation characteristics.

  In addition, the photopolymerization initiator used in the present invention is not particularly limited, but Irg 184 with particularly little color can be used by curing the transparent resin. Further, surface-curing polymerization initiator α-hydroxy ketone, such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) -Phenyl] -2-hydroxy-2-methyl-1-propan-1-one, an α-aminoketone 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1 having a high molar extinction coefficient -Acyl phosphine oxide which is a polymerization initiator of on and internal curing system, for example, bis (2,4,6-trimethylbenzoyl) -phenyl phosphine oxide, and α-aminoketone having an absorption region in h-line, for example Combination of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and the like It may be used Te.

  In addition to those shown above, for example, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, etc., initiators having surface-curing and internal-curing characteristics Can be appropriately selected.

  The amount of the photopolymerization initiator used is preferably 0.5 to 15% by mass based on the total solid content in the coating liquid, and the film hardness tends to be low even if it is more or less than this range. In particular, when it is too much, the coating film may be colored.

  Further, n-butylamine, triethylamine, poly-n-butylphosphine or the like may be mixed and used as a photosensitizer.

  A photocurable monomer composed of the (meth) acrylate (A) and (meth) acrylate (B) described above and a photopolymerization initiator are stirred and mixed without using a diluting solvent to prepare a coating liquid. .

  In the present invention, a roll-shaped metal body, polyethylene terephthalate (PET film), or the like can be used as a support used for curing the coating liquid. After applying the coating liquid, it is particularly limited if the photocurable resin molded body made of a cured film cured after ultraviolet curing can be easily peeled without deformation of the support in a process such as ultraviolet curing. It is not a thing.

  The viscosity of the coating solution is preferably 50 to 600 mPa · s (25 ° C.). When the viscosity of the coating liquid exceeds 600 mPa · s (25 ° C.), the mobility of the molecule is lowered due to the high coating viscosity at the time of ultraviolet irradiation. For this reason, the double reaction bond rate of the photocurable resin molding mentioned later falls, and the balance of intensity | strength and extensibility worsens.

  Moreover, you may add an additive to the said coating liquid for antifouling property, slipperiness imparting, defect prevention, and a particle | grain dispersibility improvement. For example, polyether-modified polymethylalkylsiloxane, polyether-modified polydimethylsiloxane, fluorine-modified polymer, acrylic copolymer, polyester-modified acrylic-containing polydimethylsiloxane, silicon-modified polyacryl, and the like can be used.

  Moreover, a well-known method can be used as a coating method of the said coating liquid to the support body. Specifically, bar coating method, dip coating method, flow coating method, spray coating method, roll coating method, gravure roll coating method, air doctor coating method, blade coating method, wire doctor coating method, knife coating method, reverse coating A method such as a coating method, a transfer roll coating method, a micro gravure coating method, a kiss coating method, a cast coating method, a slot orifice coating method, a calendar coating method, or a die coating method can be used.

The light source for curing the coating liquid by a photocuring reaction to form a cured film is not particularly limited as long as it is a light source that generates ultraviolet rays. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, an electrodeless discharge tube, or the like can be used. As irradiation conditions, the ultraviolet irradiation amount can be set to 100 to 800 mJ / cm ² .

  The photocurable resin molded body according to the present invention can be obtained by irradiating the coating liquid applied to the support with ultraviolet rays and peeling the photocured cured film from the support.

In order to ensure the strength and extensibility as a photocurable resin film, the photocurable resin molded product has a tensile strength of 30 N / mm ² or more, and a tensile elongation defined by the above formula (I) is 0.00. It is desirable that it is 10 or more.

  Moreover, it is desirable that the double bond reaction rate defined by the above formula (II) of the photocurable resin molded body is 60% or more and less than 95%. When the double bond reaction rate is less than 60%, the balance between strength and extensibility is deteriorated due to insufficient curing of the photocurable resin molding.

  Moreover, it is preferable that the thickness of a photocurable resin molding is 15 micrometers or more and 100 micrometers or less. In the range of this film thickness, when used as a support substrate, the operability is good and the film can be formed with a stable film thickness. When the film thickness is less than 15 μm, the toughness as a film is inferior and the operability is lowered. On the other hand, when the film thickness exceeds 100 μm, the film thickness uniformity decreases in the case of a low-viscosity coating liquid, and the curability at the deep part of the film decreases.

  In addition, the photocurable resin molding may contain fine particles of an inorganic or organic compound for blocking prevention, hardness imparting, antiglare property, antistatic performance imparting, or refractive index adjustment.

  As the inorganic fine particles used, it is possible to use oxides such as silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, tin oxide, and antimony pentoxide, and composite oxides such as antimony-doped tin oxide and phosphorus-doped tin oxide. it can. In addition, calcium carbonate, talc, clay, kaolin, calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, and the like can also be used.

  The organic fine particles include polymethyl methacrylate acrylate resin powder, acrylic-styrene resin powder, polymethyl methacrylate resin powder, silicon resin powder, polystyrene powder, polycarbonate powder, melamine resin powder, polyolefin resin powder, etc. Can be used.

  The average particle size of these fine particle powders is preferably 5 nm to 20 μm, and more preferably 10 nm to 10 μm. These fine particles can be used in combination of two or more.

  The photo-curable resin molded product (photo-curable resin film) obtained in the present invention has antireflection performance, antistatic performance, antifouling performance, antiglare performance, electromagnetic wave shielding performance, infrared absorption performance, ultraviolet rays as necessary. A functional layer having absorption performance, color correction performance, or the like may be laminated. These functional layers may be a single layer or a plurality of layers. For example, the antireflection layer may be composed of a single low refractive index layer, or may be composed of a plurality of layers by repeating a low refractive index layer and a high refractive index layer. Further, the functional layer may have a plurality of functions as a single layer, such as an antireflection layer having antifouling performance.

  The photo-curing resin molded body described above has improved mechanical characteristics, can be expected to improve workability in the manufacturing process, and is expected to be mounted on a polarizing plate or a transmissive liquid crystal display. Moreover, since only a photocurable resin molding can be handled as a film, the thinning of a film can be expected. Moreover, since the viscosity of the coating solution is low without using a diluting solvent, it is possible to produce a film having good surface properties. Moreover, since the coating liquid viscosity is low, the reaction efficiency during ultraviolet irradiation is improved, and unreacted double bonds can be reduced. Therefore, effects such as prevention of bleeding out, improvement of solvent resistance, and improvement of blocking are expected.

In addition, since the double bond reaction rate is high, there is little change in the characteristics of the film over time, and the film performance can be maintained for a long time.

  Examples will be described below. However, the present invention is not limited to the following examples.

The photocurable resin molding was evaluated according to the following method.
(1) Tensile property test A 100 mm x 15 mm strip-shaped film sample is formed from the produced photocurable resin molding, and the distance between chucks at the start of measurement is set to 50 mm using a small table tester EZ-LX manufactured by Shimadzu Corporation. The test was conducted at a pulling speed of 5 mm / min. Moreover, the tensile elongation was calculated using the above formula (I).

(2) Viscosity Using a Thermo HAAKE Viscotester 550 (visco tester) rotary viscometer, the viscosity at 25 ° C. and a shear rate of 100 s ⁻¹ was measured.

(3) Double bond reaction rate 810 cm < ^-1 > when UV irradiation of the produced coating liquid was carried out with the illumination intensity of 50 mW / cm < ² > and the integrated exposure amount of 250 mJ / cm < ² > using FT / IR-6300 by JASCO Corporation. The peak intensity was traced over time, and the reaction rate was calculated. The reaction rate was calculated using the above formula (II).

(4) Blocking property The obtained photocurable resin molded product was cut out into 15 cm square, 6 sheets were stacked, and the degree of blocking when a pressure of 5 kg / cm ² was applied from above was evaluated in the following three stages. [◯ = No blocking, Δ = Blocking less than 10%, X = Blocking 10% or more].

<Example 1>
Aronix M-6100 (Toagosei Co., Ltd.) 66.67 parts by mass ACMO (KJ Chemicals) 28.57 parts by mass Irgacure 184 (BASF) 4.76 parts by mass of stirring and mixing the coating solution, PET film (Lumirror T60-75 μm) : Toray) was applied by a bar coating method so as to have a cured film thickness of 40 μm, irradiated with 400 mJ / cm ² of ultraviolet light with a metal halide lamp, and the photocured coating film was peeled off to obtain a photocurable resin molded product. . This photocurable resin molded body (film) had a tensile strength of 65 N / mm ² and a tensile elongation of 20%, and a film having good tensile properties and surface properties could be formed. Further, the double bond reaction rate was 90%, the blocking test result was 0%, and the judgment result was ◯.

<Example 2>
Aronix M-6100 (Toagosei) 66.67 parts by weight Aronix M-106 (Toagosei) 28.57 parts by weight Irgacure 184 (BASF) 4.76 parts by weight of the coating solution was mixed with PET film (Lumirror). T60-75 μm: Toray) coated with a bar coating method to a cured film thickness of 45 μm, irradiated with 400 mJ / cm ² of ultraviolet light with a metal halide lamp, peeled off the light-cured coating film, and photo-cured resin molded body Got. This photocurable resin molded body (film) had a tensile strength of 30 N / mm ² and a tensile elongation of 40%, and a film having good tensile properties and surface properties could be formed. The double bond reaction rate was 85%, the blocking test result was 0%, and the determination result was ◯.

<Example 3>
Violet UV7000B (Nippon Synthetic Chemical Industry) 28.57 parts by mass ACMO (KJ Chemicals) 66.67 parts by mass Irgacure 184 (BASF) 4.76 parts by mass of the mixed coating solution was mixed with a PET film (Lumirror T60-75 μm). : Toray) was applied by a bar coating method so as to have a cured film thickness of 40 μm, irradiated with 400 mJ / cm ² of ultraviolet light with a metal halide lamp, and the photocured coating film was peeled off to obtain a photocurable resin molded product. . This photocurable resin molding (film) had a tensile strength of 70 N / mm ² and a tensile elongation of 80%, and a film having good tensile properties and surface properties could be formed. The double bond reaction rate was 85%, the blocking test result was 0%, and the determination result was ◯.

<Example 4>
Aronix M-208 (Toagosei) 66.67 parts by weight Aronix M-106 (Toagosei) 28.57 parts by weight Irgacure 184 (BASF) 4.76 parts by weight of the coating solution was mixed with PET film (Lumirror). T60-75 μm: Toray) coated with a bar coating method to a cured film thickness of 45 μm, irradiated with 400 mJ / cm ² of ultraviolet light with a metal halide lamp, peeled off the light-cured coating film, and photo-cured resin molded body Got. This photocurable resin molded product (film) had a tensile strength of 40 N / mm ² and a tensile elongation of 30%, and a film having good tensile properties and surface properties could be formed. Further, the double bond reaction rate was 90%, the blocking test result was 0%, and the judgment result was ◯.

<Example 5>
Aronix M-208 (Toagosei Co., Ltd.) 76.19 parts by mass Light acrylate DCP-4EO-A (Kyoeisha Chemical) 19.05 parts by mass Irgacure 184 (BASF) 4.76 parts by mass It is applied to a film (Lumirror T60-75 μm: Toray) with a bar coating method to a cured film thickness of 40 μm, irradiated with 400 mJ / cm ² of ultraviolet light with a metal halide lamp, the photocured coating film is peeled off, and photocurability A resin molded body was obtained. This photocurable resin molded body (film) had a tensile strength of 30 N / mm ² and a tensile elongation of 20%, and a film having good tensile properties and surface properties could be formed. Further, the double bond reaction rate was 90%, the blocking test result was 0%, and the judgment result was ◯.

<Example 6>
Aronix M-211B (Toagosei Co., Ltd.) 76.19 parts by mass AMP-20GY (Shin-Nakamura Chemical Co., Ltd.) 19.05 parts by mass Irgacure 184 (BASF) 4.76 parts by mass of the mixture was stirred and mixed with a PET film (Lumirror). T60-75 μm: Toray) coated with a bar coating method so as to have a cured film thickness of 40 μm, irradiated with 400 mJ / cm ² of ultraviolet rays with a metal halide lamp, peeled off the photocured coating film, and photocured resin molded body Got. This photocurable resin molded product (film) had a tensile strength of 40 N / mm ² and a tensile elongation of 11%, and a film having good tensile properties and surface properties could be formed. The double bond reaction rate was 85%, the blocking test result was 0%, and the determination result was ◯.

<Example 7>
Aronix M-211B (Toagosei) 66.67 parts by weight Aronix M-106 (Toagosei) 28.57 parts by weight Irgacure 184 (BASF) 4.76 parts by weight of the coating solution was mixed with PET film (Lumirror). T60-75 μm: Toray) coated with a bar coating method so as to have a cured film thickness of 40 μm, irradiated with 400 mJ / cm ² of ultraviolet rays with a metal halide lamp, peeled off the photocured coating film, and photocured resin molded body Got. This photocurable resin molded body (film) had a tensile strength of 50 N / mm ² , a tensile elongation of 10%, and was able to form a film with good tensile properties and surface properties. Further, the double bond reaction rate was 80%, the blocking test result was 0%, and the judgment result was ◯.

<Example 8>
Aronix M-211B (Toagosei) 66.67 parts by weight Aronix M-110S (Toagosei) 28.57 parts by weight Irgacure 184 (BASF) 4.76 parts by weight of the coating solution mixed with PET film (Lumirror) T60-75 μm: Toray) coated with a bar coating method to a cured film thickness of 45 μm, irradiated with 400 mJ / cm ² of ultraviolet light with a metal halide lamp, peeled off the light-cured coating film, and photo-cured resin molded body Got. This photocurable resin molded body (film) had a tensile strength of 50 N / mm ² , a tensile elongation of 10%, and was able to form a film with good tensile properties and surface properties. The double bond reaction rate was 82%, the blocking test result was 0%, and the determination result was ◯.

<Example 9>
Aronix M-211B (Toagosei Co., Ltd.) 66.67 parts by weight Light acrylate POB-A (Kyoeisha Chemical Co., Ltd.) 28.57 parts by weight Irgacure 184 (BASF) 4.76 parts by weight of a coating solution obtained by stirring and mixing PET film ( Lumirror T60-75myuemu: the coating is a cured film thickness of 40μm by a bar coating method Toray) was irradiated with ultraviolet rays of 400 mJ / cm ² by a metal halide lamp, and separating the light cured coating, the photocurable resin molding Got the body. This photocurable resin molded body (film) had a tensile strength of 50 N / mm ² , a tensile elongation of 10%, and was able to form a film with good tensile properties and surface properties. The double bond reaction rate was 85%, the blocking test result was 0%, and the determination result was ◯.

<Example 10>
Aronix M-211B (Toagosei Co., Ltd.) 66.67 parts by weight Light acrylate DCP-4EO-A (Kyoeisha Chemical) 28.57 parts by weight Irgacure 184 (BASF) A film (Lumilar T60-75 μm: Toray) was applied by a bar coating method to a cured film thickness of 45 μm, irradiated with 400 mJ / cm ² ultraviolet rays with a metal halide lamp, the photocured coating film was peeled off, and photocurability was obtained. A resin molded body was obtained. This photocurable resin molded product (film) had a tensile strength of 40 N / mm ² , a tensile elongation of 20%, and was able to form a film with good tensile properties and surface properties. The double bond reaction rate was 85%, the blocking test result was 0%, and the determination result was ◯.

<Comparative Example 1>
Purple light UV7000B (Nippon Synthetic Chemical Industry) 47.62 parts by mass ACMO (KJ Chemicals) 47.62 parts by mass Irgacure 184 (BASF) 4.76 parts by mass of the mixture was stirred and mixed with a PET film (Lumirror T60-75 μm). : Toray) was applied by a bar coating method so as to have a cured film thickness of 40 μm, irradiated with 400 mJ / cm ² of ultraviolet light with a metal halide lamp, and the photocured coating film was peeled off to obtain a photocurable resin molded product. . The tensile strength of this photocurable resin molded product (film) was 40 N / mm ² and the tensile elongation was 70%. Since the coating liquid viscosity was as high as 800 mPa · s, the reactivity was lowered, the double bond reaction rate was 55%, the blocking test result was 20%, and the determination result was x.

<Comparative example 2>
Aronix M-208 (Toagosei) 9.52 parts by weight Aronix M-106 (Toagosei) 85.72 parts by weight Irgacure 184 (BASF) 4.76 parts by weight of the coating solution was mixed with PET film T60-75 μm: Toray) coated with a bar coating method to a cured film thickness of 45 μm, irradiated with 400 mJ / cm ² of ultraviolet light with a metal halide lamp, peeled off the light-cured coating film, and photo-cured resin molded body Got. The tensile strength of this photocurable resin molded body (film) was 10 N / mm ² and the tensile elongation was 60%. Since the amount of Aronix M-106 which is acrylate B is as large as 90%, a film having low strength was formed. The double bond reaction rate was 85%, the blocking test result was 0%, and the determination result was ◯.

<Comparative Example 3>
Aronix M-211B (Toagosei Co., Ltd.) 85.72 parts by mass Light acrylate DCP-4EO-A (Kyoeisha Chemical) 9.52 parts by mass Irgacure 184 (BASF) 4.76 parts by mass A film (Lumilar T60-75 μm: Toray) was applied by a bar coating method to a cured film thickness of 45 μm, irradiated with 400 mJ / cm ² ultraviolet rays with a metal halide lamp, the photocured coating film was peeled off, and photocurability was obtained. A resin molded body was obtained. The tensile strength of this photocurable resin molded product (film) was 60 N / mm ² and the tensile elongation was 2%. Since 90% of high-viscosity M-211B was contained, the coating liquid viscosity was as high as 1000 mPa · s, and streaky irregularities were observed on the film. The double bond reaction rate was 50%, the blocking test result was 30%, and the determination result was x.

<Comparative Example 4>
Aronix M-211B (Toagosei Co., Ltd.) 66.67 parts by weight Light acrylate 9EG-A (Kyoeisha Chemical) 28.57 parts by weight Irgacure 184 (BASF) 4.76 parts by weight of a coating solution obtained by stirring and mixing PET film ( Lumirror T60-75myuemu: the coating is a cured film thickness of 45μm by a bar coating method Toray) was irradiated with ultraviolet rays of 400 mJ / cm ² by a metal halide lamp, and separating the light cured coating, the photocurable resin molding Got the body. The tensile strength of this photocurable resin molded product (film) was 20 N / mm ² and the tensile elongation was 50%. Since light acrylate 9EG-A, which is an acrylate (B), has no cyclic structure or aromatic ring, a soft and difficult-to-peel film was obtained. The double bond reaction rate was 85%, the blocking test result was 0%, and the determination result was ◯.

  The evaluation results of Examples 1 to 10 and Comparative Examples 1 to 4 are summarized in Table 1.

  The photocurable resin molded bodies (photocurable resin films) of Examples 1 to 10 are thin films because they are peeled off from the support, and weight reduction of the display can be expected.

  Since the photocurable resin molded bodies (photocurable resin films) of Examples 1 to 10 have good tensile properties, improvement in workability in the manufacturing process can be expected.

  The photocurable resin molded bodies (photocurable resin films) of Examples 1 to 10 have a low coating solution viscosity, so that the reaction efficiency during UV irradiation is improved, the reaction components are prevented from bleeding out, and the solvent resistance is high. Effects such as improvement and blocking can be expected.

  The photocurable resin molding according to the present invention can be used as a protective film for liquid crystal display devices, plasma display devices, electrochromic display devices, light-emitting diode display devices, EL display devices, and display device parts such as touch panels. Moreover, it can utilize for the photocurable resin film etc. which can be used as a functional film.

Claims (4)

A photocurable resin molded body comprising a photocured film of a coating liquid containing a photocurable monomer and a photopolymerization initiator,
The photocurable monomer has (meth) acrylate (A) having 2 or 3 (meth) acryloyl groups in one molecule and (meth) having 1 or 2 (meth) acryloyl groups in one molecule. An acrylate (B), the (meth) acrylate (B) includes one or more cyclic structures, or one or more aromatic rings, and has an ether skeleton,
The mass ratio of the (meth) acrylate (A) and the (meth) acrylate (B) is 30:70 to 90:10,
The coating liquid does not contain a diluting solvent,
The tensile strength of the photocurable resin molding is 30 N / mm ² or more, and the tensile elongation defined by the following formula (I) is 0.10 or more,
The viscosity of the coating liquid is 50 to 600 mPa · s (25 ° C.),
The photocurable resin molded product, wherein a double bond reaction rate defined by the following formula (II) of the photocurable resin molded product is 60% or more and less than 95%.
Tensile elongation = {(Length at break) − (Initial length before tension)} / Initial length before tension Formula (I)
Double bond reaction rate (%) = 100 × {1- (P0-P1)} Formula (II)
here,
P0: peak intensity of the absorption of 810 cm ^-1 in the infrared absorption spectrum before photocuring the coating liquid P1: the peak intensity of the absorption of 810 cm ^-1 in the infrared absorption spectrum after photocuring the coating liquid is there.   The photocurable resin molded product according to claim 1, wherein the photocurable resin molded product has a thickness of 15 μm or more and 100 μm or less.   A polarizing plate comprising the photocurable resin molded product according to claim 1.   A transmissive liquid crystal display comprising the photocurable resin molded product according to claim 1.