JP2016074884A - Photocurable resin composition and optical film using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition having excellent adhesiveness and antistatic properties to various resin films.SOLUTION: There is provided a photocurable resin composition which comprises a polymerizable unsaturated group-containing monomer (A) having no hydroxyl group, an urethane acrylate (B) and a conductive material (C), in which (A) has a solubility parameter of 9.0 to 13.0 (cal/cm), a molecular weight of 350 or less and a viscosity at 25°C of 30 mPa s, (B) is obtained by reacting a (meth)acrylate (b1) having one hydroxyl group in the molecule and an isocyanate compound (b2) having an isocyanate group in the molecule and at least one structure selected from an isocyanurate ring structure, a biuret structure or an allophanate structure and has a weight average molecular weight of 500 or more and an acryloyl group equivalent of 140 to 400 g/eg and the weight ratio (solid content) of (A):(B):(C) is 10 to 70:10 to 70:0.2 to 25.SELECTED DRAWING: None

Description

The present invention relates to a photocurable resin composition and an optical film using the same.

Conventionally, a polarizing plate used in a liquid crystal display device is obtained by attaching a triacetyl cellulose film (TAC film) as a protective film on both surfaces of a polarizer obtained by adsorbing iodine or the like on a polyvinyl alcohol film and orienting it by stretching or the like. A transparent photocurable resin composition is applied and cured to form a hard film (hard coat layer), which is protected from scratches and the like. As a material for forming such a cured film, for example, an active energy ray-curable resin composition using polyfunctional urethane (meth) acrylate or the like is known as a material for forming a hard coat layer (Patent Document). 1).

In recent years, liquid crystal devices are required to withstand severer use environments (for example, high temperature and high humidity conditions) due to the increase in size and quality of liquid crystal devices and the expansion of mobile applications, and it is clear that TAC films have limitations in terms of characteristics. Became. Under such circumstances, various studies have been made on the material of the protective film, and alternatives from a TAC film to a PET (polyethylene terephthalate) film, an acrylic resin film, and the like are being studied. However, these films have a problem that the adhesion between the film and the hard coat layer is inferior to that of the TAC film.

To deal with such problems, for example, Patent Document 2 discloses that the base film is subjected to physical treatment such as corona discharge treatment and oxidation treatment, and after applying a coating called an anchor agent or primer, It is disclosed that the adhesion between the base film and the hard coat layer is improved by forming (Patent Document 2). However, the method described in Patent Document 2 lacks productivity because the number of steps necessary for the production of the hard coat film is increased.

On the other hand, base materials made of polymer materials or glass generally have excellent insulating properties but are easily charged. Therefore, dust or the like adheres to precision machines using these base materials as protective films for deflecting plates. As a result, it may become dirty or malfunction. Therefore, an active energy ray-curable resin composition obtained by blending various antistatic agents with an active energy ray-curable resin such as a poly (meth) acrylate compound having a plurality of (meth) acryloyl groups on the surface of the base material. And an antistatic cured film (hard coat layer) is provided.

In order to deal with such a problem, for example, in the case of Patent Document 3, the applicant of the present invention has grafted a hydroxyl group-terminated lactone chain and an alicyclic alkyl ester chain on a quaternary ammonium salt structure-containing copolymer. It has been proposed that it has excellent compatibility with the curable resin and can impart excellent antistatic properties to the cured film. However, it cannot be said that the antistatic property and adhesiveness are sufficient with respect to the above-described PET film and acrylic resin-based film, and a resin composition capable of achieving both high adhesiveness and excellent antistatic property with respect to these films is still available. Not developed.

International Publication WO2010 / 146801 JP 2011-81359 A JP2012-312297A

This invention is providing the photocurable resin composition which has the outstanding adhesiveness and antistatic property with respect to various resin films. It is providing the photocurable resin composition which has high adhesiveness especially with respect to a resin film of difficult adhesion.

As a result of intensive studies to solve the above problems, the present inventor has obtained the above problems by using a resin composition containing a polymerizable unsaturated group-containing monomer having no hydroxyl group, a specific urethane acrylate, and a conductive material. The inventors have found that the problem can be solved and completed the present invention.

That is, this invention is the photocurable resin composition shown to the following items 1 to 4, and an optical film using the same.

Item 1. The polymerizable unsaturated group-containing monomer (A) containing a polymerizable unsaturated group-containing monomer (A) having no hydroxyl group, urethane acrylate (B), and conductive material (C) and having no hydroxyl group has a solubility. The parameter is 9 to 13 (cal / cm ³ ) ^1/2 , the weight average molecular weight is 350 or less, the viscosity at 25 ° C. is 30 mPa · s or less, and the urethane acrylate (B) has one hydroxyl group in the molecule. It is obtained by reacting a polymerizable unsaturated group-containing monomer (b1) having an isocyanate compound (b2) having an isocyanate group in the molecule and at least one structure selected from an isocyanurate ring structure, a biuret structure and an allophanate structure. It has a weight average molecular weight of 500 or more, an acryloyl group equivalent of 140 to 400 g / eq, and has no hydroxyl group. It is a photocurable resin composition whose solid weight part ratio of a saturated group containing monomer (A): urethane acrylate (B): conductive material (C) is 10-70: 10-70: 0.2-25.

Item 2. Item 2. The photocurable resin composition according to Item 1, wherein the conductive material (C) includes at least one of a compound containing a quaternary ammonium salt structure, a conductive polymer, and metal oxide fine particles.

Item 3. Item 3. The optical film according to Item 1 or 2, wherein a cured film of the photocurable resin composition of the present invention 1 or 2 is formed on at least one surface of the film.

Item 4. Item 4. The optical film according to Item 3, wherein the surface resistance value on the surface of the cured film is 1.0 × 10 ¹² Ω / □ or less.

According to this invention, the kind of solvent to be used is not limited with respect to various resin films, and a resin composition having excellent adhesion and antistatic properties can be provided. In particular, since it has excellent adhesion to difficult-to-adhere acrylic resin films and polyester resin films, it can be suitably used as a protective film for display applications such as optical parts and flat panel displays. it can.

The photocurable resin composition of the present invention comprises a polymerizable unsaturated group-containing monomer (A) having no hydroxyl group, urethane acrylate (B), and conductive material (C).

[Polymerically unsaturated group-containing monomer having no hydroxyl group (A)]
The polymerizable unsaturated group-containing monomer (A) having no hydroxyl group (hereinafter also referred to as “component (A)”) is particularly a polymerizable unsaturated monomer having no hydroxyl group that satisfies the conditions described later. Specifically, N-vinylformamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, methyl methacrylate, ethyl (meth) acrylate, N-vinylacetamide, N-vinylpyrrolidone, (meth) acrylic acid , Acrylics of alkyl diols such as tetrahydrofurfuryl (meth) acrylate, 4-acryloylmorpholine, benzyl acrylate, 1-4 butanediol di (meth) acrylate, acid addition products, ethylene such as tetraethylene glycol di (meth) acrylate Dipropylene, an acrylic acid adduct of glycols Such as glycol di (meth) acrylate of propylene glycol adduct of such acrylate. Moreover, as (A) component, you may use together these 1 type, or 2 or more types of compounds. When a polymerizable unsaturated monomer having a hydroxyl group is used, the surface resistance value is increased. Preferred are vinylamide-based and acrylamide-based monomers such as N-vinylformamide, dimethylacrylamide, and the like because they are excellent in the balance between molecular weight and solubility parameter, increase adhesion even in a small amount, and give a surface resistance value.

The solubility parameter of the component (A) is 9 to 13 (cal / cm ³ ) ^1/2 , the molecular weight is 350 or less, and the viscosity at 25 ° C. is 30 mPa · s or less. When the solubility parameter is less than 9 (cal / cm ³ ) ^1/2 or more than 13 (cal / cm ³ ) ^1/2 , the polarity difference from the base material becomes too large, and the paintability is inferior, resulting in poor adhesion. Results in inferior. Even when the SP value is in this range, the surface resistance value is increased when a polymerizable unsaturated group monomer having a hydroxyl group is used. Preferably it is 9-12 (cal / cm < ³ >) ^<1/2 >.

The solubility parameter δ (SP value) in the above (A) was calculated based on the following mathematical formula 1, which is a Fedors calculation method. The following mathematical formula is based on a non-patent document “Hideki Yamamoto, SP value basics / application and calculation method, information mechanism, p. 66-67”.
(However, Ecoh represents cohesive energy and V represents the molar volume of the substance.)

When the viscosity of the component (A) exceeds 30 mPa · s, this also lowers the ability to penetrate the substrate, resulting in poor adhesion. The viscosity of component (A) was measured using an E-type viscometer set at 25 ° C. Preferably, it is 25 mPa · s or less.

The molecular weight of the component (A) is 350 or less. When the molecular weight exceeds 350, the molecules are large and the ability to penetrate the substrate is lowered, resulting in poor adhesion. Preferably, it is 70-350. As the molecular weight of component (A), the theoretical molecular weight calculated from the molecular structure was used.

The component (A) preferably uses a resin film that satisfies the following requirement (1).
Requirement (1): The resin film has a volatile content at 120 ° C. per 200 mg of a measurement sample of 100 ppm or less, and a resin film having a thickness of 125 μm is immersed in a methyl butyl ketone solution at room temperature for 1 minute. In some cases, the increase in the surface haze of the film after immersion relative to that before immersion is 0.5 or less.

The methyl butyl ketone solution in the above requirement (1) means a pure solution that does not contain other components such as a solvent. Further, “as a measurement sample” is a clarification that it is a condition for measuring an increase in the surface haze of a resin film, and the embodiment of the present invention is limited to a resin film having a thickness of 125 μm. Is not to be done.

Requirement (1) specifies the application of the photocurable resin composition of the present invention, that is, the resin characteristics of a resin-based film that is a target for forming a cured film.

The amount of volatile components at 120 ° C. per 200 mg of the measurement sample defined in the requirement (1) indicates that the resin film is not easily eroded by a solvent or the like (erosion resistance). Usually, the amount of the volatile component of a general resin film exceeds 100 ppm. With such a resin film, a cured film can be formed relatively easily with a known photocurable resin composition, whereas a resin film with 100 ppm or less is a cured film with high adhesion to the surface. Is difficult to form.

As a kind of the resin film in the requirement (1), in addition to the acrylic resin film described later, polyester resin film, cycloolefin copolymer resin film, polyimide resin film, polycarbonate resin film, nylon resin film, polyether Based resin films and the like.

Specific examples of the acrylic resin include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, ( Tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) acryl One or more of (meth) acrylates such as acid 2,3,4,5,6-pentahydroxyexyl and (meth) acrylate 2,3,4,5-tetrahydroxypentyl are used as monomer components, These are obtained by polymerization reaction. Further, the acrylic resin may be one having a lactone ring structure, maleimides such as N-phenylmaleimide, maleic anhydride, glutaric anhydride, etc. introduced into the molecular chain in the acrylic resin to improve heat resistance or a crosslinkable monomer. For example, a highly cross-linked structure may be introduced to improve heat resistance and shape stability, or a mixture of two or more acrylic resins may be used. These are exemplifications of an acrylic resin film or an acrylic resin that is a raw material thereof, and in the present invention, the acrylic resin that is a raw material is not limited to these as long as the requirement (1) is satisfied. Furthermore, the acrylic resin film includes those in which an acrylic resin layer further three-dimensionally crosslinked is formed on the acrylic resin film described in JP-A-10-244629.

The measurement of the amount of volatile components is a quantitative value of all volatile components by gas chromatography mass spectrometry. Moreover, the measurement of the haze in the increase value of surface haze is a measured value based on JISK7136.

An increase in surface haze specified by requirement (1) is 0.5 or less is a resin-based film that is less susceptible to penetration by a methylbutylketone solution and does not substantially change its appearance. It is suitably used for optical films such as a protective film for a polarizing plate incorporated in an apparatus, a retardation film, a light collecting sheet, a diffusion film, a light guide plate, and a light reflecting sheet. In general, many resin-based films have various monomer compositions and structures, and many are formed and processed into films using resins of various polymer blends as raw materials, and their characteristics are various. Resin-based films that satisfy requirement (1) are usually molded from high-molecular-weight, highly-crosslinked resins as compared to resin-based films known as general-purpose products, and are tough and stable in shape due to heat resistance, thermal history, etc. Although it has excellent properties, it is difficult to be attacked by an organic solvent, and therefore has low adhesion (hard adhesion).

[Urethane acrylate (B)]
The urethane acrylate (B) used in the present invention (hereinafter also referred to as “component (B)”) is a polymerizable unsaturated group-containing monomer (b1) having one hydroxyl group in the molecule (hereinafter referred to as “component (b1)”. And an isocyanate compound (b2) (hereinafter also referred to as “component (b2)”) having an isocyanate group in the molecule and having at least one structure selected from an isocyanurate ring structure, a biuret structure and an allophanate structure. ) Having a weight average molecular weight of 500 or more and an acryloyl group equivalent of 140 to 400 g / eq. Hereinafter, the urethane acrylate obtained by reacting the component (b1) and the component (b2) will be further described.

As the component (b1), known monomers can be used as long as they are polymerizable unsaturated group-containing monomers having one hydroxyl group in the molecule. Thereby, the antistatic property of the obtained photocurable resin composition can be made excellent, and it can have high adhesiveness with respect to a base material. When a polymerizable unsaturated group-containing monomer having two or more hydroxyl groups in the molecule is used, it becomes difficult to maintain compatibility with other resin components.

As the component (b1), known compounds can be used as long as they have at least one hydroxyl group and polymerizable unsaturated group in the molecule. Specifically, as a compound having one (meth) acryloyl group, for example, monohydroxy mono (meth) acrylate [2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc.], monohydroxy mono And vinyl ether [2- (vinyloxy) ethanol, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, etc.], monohydroxy monoallyl ether [2- (allyloxy) ethanol, etc.] and the like. As the component (b1), one or more of these compounds may be used in combination.

Examples of the compound having one hydroxyl group and two polymerizable unsaturated groups in the molecule include monohydroxy di (meth) acrylate [glycerol di (meth) acrylate and the like], monohydroxy divinyl ether [trimethylolpropane divinyl ether, Triethanolamine divinyl ether, etc.), monohydroxy diallyl ether [trimethylolpropane diallyl ether, diallyl glycerol, etc.] and the like.

Monohydroxy poly (meth) acrylate [pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc.], monohydroxypoly (meth) acrylate, etc. as a compound having one hydroxyl group and three or more polymerizable unsaturated groups in the molecule. Hydroxy polyallyl ether [pentaerythritol triallyl ether, triallyl citrate, etc.] and the like.

The component (b2) is an isocyanate compound having an isocyanate group in the molecule and having at least one structure selected from an isocyanurate ring structure, a biuret structure, and an allophanate structure. By using a thing of these structures, since the shrinkage which arises at the time of hardening becomes small, it can give high adhesiveness with high hardness to the hardened film obtained. Moreover, as a (b2) component, only 1 type of the said compound may be used, and 2 or more types may be used together.

Examples of the isocyanate compound having an isocyanurate ring structure contained in the component (b2) include isophorone diisocyanate trimer (isocyanurate), 1,6-hexamethylene diisocyanate trimer (isocyanurate), and hydrogenation. A trimer of xylylene diisocyanate (isocyanurate), a reaction product of the trimer, or the like can be given.

Examples of the isocyanate compound having an allophanate structure include an adduct body of isophorone diisocyanate and an adduct body of 1,6-hexamethylene diisocyanate.

Examples of the isocyanate compound having the biuret structure include a reaction product of 1,6-hexamethylene diisocyanate.

As a method for synthesizing the component (B), a known method may be employed. For example, the component (b1) and the component (b2) may be mixed with a triethylenediamine, a non-alcohol organic solvent such as toluene, In the presence of a catalyst selected from 1,8-diazabicyclo- [5,4,0] -undecene-7, stannous octylate, lead dioctylate and the like, the reaction is usually performed at a reaction temperature of about 60 to 90 ° C. Good.

The use ratio of the component (b1) and the component (b2) is not particularly limited, but the molar ratio of the hydroxyl group of the component (b1) / the isocyanate group of the component (b2) is about 1.0 to 1.25, preferably A range of about 1.0 to 1.15 is preferable. When the molar ratio is less than 1.0, unreacted isocyanate groups remain in the finally obtained component (B), and the resulting composition has increased stability over time, such as thickening and gelation. Tend to get worse. Moreover, when the said molar ratio exceeds 1.25, an unreacted (b1) component will remain, the content rate of the obtained (B) component will fall, and sufficient coating-film intensity | strength and adhesiveness will be obtained. There is no problem.

The quantification of the residual isocyanate group can be measured according to, for example, JIS K1556, and the quantification of the number of hydroxyl equivalents can be measured, for example, according to JIS K1557.

The component (B) used in the present invention has a weight average molecular weight of 500 or more and a (meth) acryloyl group equivalent of 140 to 400 g / eq. Here, the weight average molecular weight is a polystyrene-converted value obtained by gel permeation chromatography. By making the weight average molecular weight and (meth) acryloyl group equivalent within the range of such values, there is little shrinkage that occurs during curing, and the resulting cured film has excellent hardness (pencil hardness), which is a physical film required as a protective film Basic properties as an optical film such as toughness such as strength and long-term adhesion can be ensured. From the same viewpoint, the weight average molecular weight is preferably 500 to 30,000.

When the (meth) acryloyl group equivalent is less than 140 g / eq, the adhesion tends to decrease due to curing shrinkage that occurs at the time of curing, and when the hardness exceeds 400 g / eq, the hardness (pencil hardness) of the cured film obtained is insufficient. Neither is suitable for use. From the same viewpoint, the (meth) acryloyl group equivalent is preferably 140 to 400 g / eq.

[Conductive material (C)]
The conductive material (C) (hereinafter, also referred to as “component (C)”) used in the present invention is not particularly limited as long as it is a material having an electric resistance value of 10 ⁷ Ω · cm or less. Examples thereof include fine particles of metal, metal oxide, and metal compound (conductive filler), a compound containing a quaternary ammonium salt structure, a conductive polymer, and an ionic liquid. Among these, one of a compound containing a quaternary ammonium salt structure, a conductive polymer, and carbon black / metal oxide fine particles is preferred from the viewpoint of antistatic properties with time. Particularly preferred from the viewpoint of transparency are a compound containing a quaternary ammonium salt structure and a conductive polymer.

Examples of the compound containing the quaternary ammonium salt structure include a polymerizable monomer having a quaternary ammonium salt structure and a polymerizable unsaturated group in the molecule, and a monomer having both the quaternary ammonium salt structure and a polymerizable unsaturated group. Examples thereof include copolymers of monomers having other polymerizable unsaturated groups and urethane compounds containing a reaction product of a polyhydric alcohol containing a quaternary ammonium salt structure in the molecule with an organic isocyanate. A copolymer of a monomer having both a quaternary ammonium salt structure and a polymerizable unsaturated group and another monomer having a polymerizable unsaturated group is preferable in view of compatibility with other components and antistatic properties. .

Examples of the conductive polymer include poly (3,4-ethylenedioxythiophene) (hereinafter sometimes referred to as PEDOT), polyacetylene, polyaniline, polypyrrole, and derivatives of these derivatives. Can be mentioned. PEDOT doped with polystyrene sulfonic acid (hereinafter sometimes referred to as PEDOT / PSS) is preferable from the viewpoint of compatibility with other components and antistatic properties.

Examples of the metal oxide fine particles include tin oxide, indium oxide, tin oxide-containing indium oxide (ITO), antimony-containing tin oxide (ATO), phosphorus-containing tin oxide (PTO), cerium oxide, zinc oxide, and aluminum-containing zinc oxide. Antimony-containing zinc oxide, indium-containing zinc oxide and the like. In terms of transparency and antistatic properties, phosphorus-containing tin oxide (PTO) and antimony-containing zinc oxide are preferred.

The active energy ray-curable resin composition of the present invention contains the components (A) to (C).
From the viewpoint of ensuring adhesion and strength of the cured film, the ratio of the components (A) to (C) used is such that the solid part by weight ratio of the above component (A): component (B): component (C) is 10-70. : 10-70: 0.2-25. Preferably, it is 20-60: 10-60: 0.2-20. More preferably, it is 30-60: 15-60: 0.3-20.

In addition to the components (A) to (C), the photocurable resin composition of the present invention further includes various known additives such as photosensitizers, antioxidants, light stabilizers, leveling agents, pigments, and light. A polymerization initiator (D) or the like may be contained.

The manufacturing method of the photocurable resin composition of this invention is not specifically limited, It can manufacture by mixing the said (A), (B) and (C) component. The order of mixing the components is not particularly limited, and examples thereof include a method of adding the component (C) after diluting the highly viscous component (B) with the component (A) to reduce the viscosity. When blending a dispersion of a metal oxide or a conductive polymer, it is preferable to mix them from those having a polarity at room temperature in order to prevent aggregation and sedimentation of the particles. Moreover, a solvent can also be mixed as needed.

The solvent is not particularly limited, and examples thereof include alcohol solvents, glycol solvents, and ketone solvents.

Examples of the alcohol solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tertiary butanol, 1-hexanol, 1-octanol, 2-ethyl-hexanol, 1-nonanol, 1 -Decanol, benzyl alcohol, diacetone alcohol, ethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, glycerin, and the like, and mixed solvents thereof.

Examples of the glycol solvent include 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2-phenoxyethanol, 2- (benzyloxy) ethanol, 2-allyloxy Ethanol, 3-methoxypropanol, 3-ethoxypropanol, 4-methoxybutanol, 4-ethoxybutanol, 2- (2-methoxyethoxy) ethanol, 1-methoxy-2-propanol, 2-methoxy-1-propanol, 1- Ethoxy-2-propanol, 2-ethoxy-1-propanol, 1-propoxy-2-propanol, 2-propoxy-1-propanol, 1-butoxy-2-propanol, 2-butoxy-1-propanol, 1-phenoxy- 2 Propanol, 2-phenoxy-1-propanol.

Examples of the ketone solvent include acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), diethyl ketone, diisobutyl ketone, and cyclohexanone.

[Photoinitiator (D)]
As a photoinitiator (D) (henceforth (D) component), it does not specifically limit but a well-known thing can be used. Specifically, for example, 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl -Propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphos Examples include fin oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and 4-methylbenzophenone. That. These may be used alone or in combination of two or more. In addition, although (D) component is used when performing ultraviolet curing, it is not necessarily required when performing electron beam curing. Although the usage-amount in the case of using (D) component is not specifically limited, Usually, it is preferable to set it as about 1-10 weight part with respect to 100 weight part of total amounts of (A)-(C) component.

The photocurable resin composition of the present invention is applied to at least one surface of a film, dried, and then cured to form a cured film. Thus, the cured film of the photocurable resin composition of the present invention is formed, and an optical film is also one aspect of the present invention. The optical film of the present invention is
It has high adhesion to flame retardant acrylic resin film, and has excellent antistatic properties, so it can be used as a protective film for display applications such as optical parts and flat panel displays. Is.

The substrate of the film is not particularly limited, and examples thereof include acrylic resins, polyester resins, polycycloolefin resins, and transparent polyimide resins.

The acrylic resin is not particularly limited, and examples thereof include an acrylic resin in which heat resistance, moisture resistance, solvent resistance, mechanical hardness, and molding processability are enhanced by introducing, for example, a lactone ring structure or an imide ring structure. It is done.

The surface resistance value on the surface of the cured film is preferably 1.0 × 10 ¹² Ω / □ or less from the viewpoint of imparting antistatic properties. In this case, in the precision machine using the optical film of the present invention, there is no problem that dust or the like adheres to it, and it can be used preferably. More preferably, it is 1.0 × 10 ¹¹ Ω / □ or less.

The method for forming a cured film using the photocurable resin composition of the present invention is generally such that a curing reaction is caused on the film surface by coating the substrate film, drying it, and irradiating it with active energy rays. For example, a cured film may be formed. In addition, when used as an adhesive, after being applied to an acrylic resin film and dried, the adhesive layer is cured by irradiating active energy rays after being in close contact with the other substrate to be bonded. You can do that. Moreover, when using as an adhesive agent, you may make it closely_contact | adhere with a base film, after applying and drying to the other party's base material.

Examples of the coating method include bar coater coating, wire bar coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing.

The coating amount is not particularly limited, but usually the weight after drying is about 0.1 to 30 g / m ² , preferably 1 to 20 g / m ² .

Examples of active energy rays used for the curing reaction include ultraviolet rays and electron beams. As an ultraviolet light source, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, or a metal halide lamp can be used. The light amount, light source arrangement, transport speed, etc. can be adjusted as necessary. For example, when a high-pressure mercury lamp is used, the transport speed is 5 to 50 m for one lamp having a light amount of about 80 to 160 W / cm. It is preferable to cure at about / min. On the other hand, in the case of an electron beam, it is preferable to cure at an conveyance speed of about 5 to 50 m / min with an electron beam accelerator having an acceleration voltage of about 10 to 300 kV.

Hereinafter, the method of the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these. In the examples, parts or% is based on weight.

<About (A) component>
As the polymerizable unsaturated monomer having no hydroxyl group, N-vinylformamide, tetrahydrofurfuryl acrylate, benzyl acrylate, dimethyl acrylamide, stearyl acrylate, polyethylene glycol (PEG # 400) diacrylate, and trimethylolpropane triacrylate were used.
On the other hand, as a polymerizable unsaturated monomer having a hydroxyl group, HEA (hydroxyethyl acrylate, manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate HOA (N)), PETA (pentaerythritol triacrylate, manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate PE) -3A) was used.

(Measurement of weight average molecular weight)
In this example, the weight average molecular weight was determined by gel permeation chromatography (trade name “HLC-8220” manufactured by Tosoh Corporation, column: manufactured by Tosoh Corporation, trade names “TSKgel superHZ2000”, “TSKgel superHZM-M”. The value measured by “)” is shown.

<Synthesis of component (B)>
Synthesis example 1
After charging an isocyanurate body of isophorone diisocyanate 200 parts, tin octylate 0.2 parts, and PETA 268 parts into a reaction vessel equipped with a stirrer, a cooling pipe, a dropping funnel and a nitrogen introduction pipe, the system was taken over about 1 hour. The temperature inside was raised to about 80 ° C. Next, at the same temperature, the reaction system was held for 3 hours and then cooled to obtain urethane acrylate (B-1). The (meth) acryloyl group equivalent of the component (B-1) was about 173 g / eq, and the weight average molecular weight was 1,560.

Synthesis example 2
Into a reaction vessel equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introduction tube, 200 parts of bimure of hexamethylene diisocyanate (hereinafter referred to as HDI biuret), 0.2 part of tin octylate, and 334 parts of PETA were charged. The temperature inside the system was raised to about 80 ° C. over about 1 hour. Next, at the same temperature, the reaction system was held for 3 hours and then cooled to obtain urethane acrylate (B-2). The (meth) acryloyl group equivalent of the component (B-2) was about 155 g / eq, and the weight average molecular weight was 1,400.

Synthesis example 3
In a reaction vessel equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introduction tube, 200 parts of hexamethylene diisocyanate allophanate (hereinafter referred to as HDI allophanate), 0.2 part of tin octylate, and 273 parts of PETA were charged. The temperature inside the system was raised to about 80 ° C. over about 1 hour. Next, at the same temperature, the reaction system was held for 3 hours and then cooled to obtain urethane acrylate (B-3). The (meth) acryloyl group equivalent of the component (B-3) was about 183 g / eq, and the weight average molecular weight was 1,100.

Synthesis example 4
In a reaction vessel equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introduction tube, 200 parts of isocyanurate condensate of hexamethylene diisocyanate (hereinafter referred to as HDI isocyanate condensate), 0.3 part of tin octylate, 458 parts of PETA Then, the temperature in the system was raised to about 80 ° C. over about 1 hour. Next, at the same temperature, the reaction system was held for 3 hours and then cooled to obtain urethane acrylate (B-4). The (meth) acryloyl group equivalent of the component (B-4) was about 146 g / eq, and the weight average molecular weight was 21,000.

Synthesis Example 5 Comparative Synthesis Example of Component (B) After charging 200 parts of HDI, 0.3 part of tin octylate and 709 parts of PETA in a reaction vessel equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introducing tube, about 1 Over time, the temperature in the system was raised to about 80 ° C. Next, at the same temperature, the reaction system was held for 3 hours and then cooled to obtain urethane acrylate (B-5). The acryloyl group equivalent of the component (B-5) was 127 g / eq, and the weight average molecular weight was 764.

Synthesis Example 6 Comparative Synthesis Example of Component (B) In a reaction vessel equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introduction tube, 200 parts of an isocyanurate body of isophorone diisocyanate, 0.2 part of tin octylate, 2-hydroxy After charging 205 parts of -3-phenoxypropyl acrylate (hereinafter referred to as HPPA), the temperature in the system was raised to about 80 ° C. over about 1 hour. Next, at the same temperature, the reaction system was held for 3 hours and then cooled to obtain urethane acrylate (B-6). Component (B-6) had an acryloyl group equivalent of about 440 g / eq and a weight average molecular weight of 914.

Synthesis Example 7 Comparative Comparison Example of Component (B) In a reaction vessel equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introducing tube, 200 parts of HDI, 0.2 part of tin octylate, hydroxyethyl acrylate (hereinafter referred to as HEA) After charging 276 parts, the temperature in the system was raised to about 80 ° C. over about 1 hour. Next, at the same temperature, the reaction system was maintained for 3 hours and then cooled to obtain urethane acrylate (B-7). The acryloyl group equivalent of the component (B-7) was 200 g / eq, and the weight average molecular weight was 400.

Synthesis Example 8 Comparative Synthesis Example of Component (B) In a reaction vessel equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introducing tube, 200 parts of isocyanurate of isophorone diisocyanate, 0.1 part of tin octylate, glycerin monomethacrylate After charging 80 parts (hereinafter referred to as GLM), the temperature in the system was raised, but the entire system became a gel that did not dissolve in the middle, and the target compound was not obtained.

<Synthesis of component (C)>
Synthesis Example 9 Synthesis Example of Component (C) Copolymerization Monomer (c-1) Component In a reactor equipped with a stirrer and a condenser, 130 parts of HEA, 1140 parts of ε-caprolactone, and 1 part of tin octylate .3 parts was added, the temperature was raised to 150 ° C., the temperature was kept for 6 hours, and then cooled to obtain a polyester structure-containing monofunctional vinyl monomer (“(c-1) component”) having a weight average molecular weight of about 5500.

Synthesis Example 10 Synthesis Example of Component (C-1) Methacryloyloxyethyltrimethylammonium chloride (hereinafter referred to as DMC) containing a quaternary ammonium salt structure in a reaction vessel equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introduction tube. ) 100 parts, (c-1) component 60 parts, tert-butyl methacrylate (hereinafter referred to as t-BMA) 40 parts, and propylene glycol monomethyl ether (PGM) 800 parts. Warm up. Next, 8 parts of 2,2′-azobis (methylbutyronitrile) (AMBN) and 32 parts of PGM were added, the polymerization reaction was started, the mixture was kept at 100 ° C. for 6 hours, cooled, and then the quaternary ammonium salt structure-containing copolymer was obtained. A solution (non-volatile content 20%) (“(C-1) component”) was obtained.

(C-2) As a component, Arakawa Chemical Industries, Ltd. beam set EL-1 (PEDOT / PSS other functional acrylate solution dispersion, PEDOT / PSS: about 20%), (C-3) As a component, Celnax CX-Z610M-F2 (methanol dispersion of antimony-containing zinc oxide) manufactured by Nissan Chemical Industries, Ltd. was used.

<Acrylic resin film>
As an acrylic resin film for forming a cured film, Technoloy S001 manufactured by Sumitomo Chemical Co., Ltd. having a thickness of 125 μm was used. In addition, when 200 mg of this film was sampled and the amount of volatile components at 120 ° C. was measured, it was 55 ppm, and after immersing this film in methylbutylketone 100% solution at 25 ° C. for 1 minute, the surface haze value was measured immediately. As a result, the increase in haze was 0.0%. Therefore, it has been confirmed that the above requirement (1) is satisfied.

<Polyester resin film>
As a polyester resin film for forming a cured film, Lumirror 75-T60 manufactured by Toray Industries, Inc. having a thickness of 75 μm was used. In addition, when 200 mg of this film was sampled and the amount of volatile components at 120 ° C. was measured, it was 92 ppm, and after immersing this film in a methylbutylketone 100% solution (25 ° C.) for 1 minute, the surface haze value was immediately measured. When measured, the increase in haze was 0.1%. Therefore, it has been confirmed that the above requirement (1) is satisfied.

<Manufacture of a photocurable resin composition>
Example 1
40 parts of component (A-1), 50 parts of component (B-1), 10 parts of copolymer (C-1) having the above-described quaternary salt structure as component (C), and component (D) As a blend, 5 parts of 1-hydroxy-cyclohexyl-phenyl ketone (trade name “Irgacure 184”, hereinafter referred to as HCPK) manufactured by BASF Japan Ltd.) in a solid content ratio, methyl ethyl ketone (MEK), propylene glycol monomethyl ether (PGME) was diluted with 1-propanol to prepare an active energy ray-curable composition having a nonvolatile content of 50%.

Example 2 to Example 9
A photocurable resin composition was produced in the same manner as in Example 1 except that each component and the mixing ratio were changed as described in Table 1. The component (C) of Example 5 is 1.5 parts of the solid content (including the organic oligomer / dispersant) of Beam Set-EL1, which is the component (C-2), of which the conductive material (C) The solid content of PEDOT / PSS was 0.3 part.

Examples 10-13
Except having changed the base material into the polyester-type resin film, each component and compounding ratio were changed as described in Table 1, and the photocurable resin composition was manufactured similarly to Example 1.

Comparative Example 1
40 parts of HEA as component (A), 50 parts of component (B-1), 10 parts of component (C-1), and 1-hydroxycyclohexyl-phenylketone as component (D) (BASF Japan K.K.) Product, trade name “Irgacure 184”, hereinafter referred to as HCPK) in a solid content ratio, diluted with methyl ethyl ketone (MEK), propylene glycol monomethyl ether (PGME), 1-propanol, and a non-volatile content of 50 % Active energy ray-curable composition was prepared.

Comparative Example 2 to Comparative Example 11
A photocurable resin composition was produced in the same manner as in Comparative Example 1 except that each component and the mixing ratio were changed as described in Table 1.

Comparative Examples 12 to 15
The base material was changed to a polyester resin film, each component and the compounding ratio were changed as shown in Table 1, and a photocurable resin composition was produced in the same manner as in Comparative Example 1.

<Creation of cured film>
On the said acrylic resin film, the resin composition which concerns on Example 1 of Table 1 is apply | coated with a # 10 bar coater so that the film thickness of the film after hardening may be set to 5 micrometers, and it is 1 minute at 60 degreeC. Dried. Next, the obtained film was used with an ultraviolet curing device (product name: UBT-080-7A / BM, manufactured by Multiply, high pressure mercury lamp 600 mJ / cm ² ) to obtain a plastic film provided with a cured film. It was. Films were similarly prepared for the resin compositions according to Examples 2 to 10 and Comparative Examples 1 to 15. The results are shown in Table 1.

<Evaluation of cured film>

(1) Adhesiveness About the plastic film which concerns on Example 1 of Table 1, according to JISK5600-5-4, the adhesiveness of the cured film was evaluated by the 100 square cross peel test. The same applies to the plastic films according to Examples 2 to 13 and Comparative Examples 1 to 15. The results are shown in Table 1.

(2) Surface resistance value About the plastic film which concerns on Example 1 of Table 1, surface resistance value was used for the commercially available resistivity meter (Mitsubishi Chemical Corporation make, product name "Hiresta MCP-HT-450"). According to JIS K 6911, measurement was performed at an applied voltage of 500V. The same applies to the plastic films according to Examples 2 to 13 and Comparative Examples 1 to 15. The results are shown in Table 1.

(3) Pencil hardness About the plastic film which concerns on Example 1 of Table 1, according to JISK5600-5-4, the hardness of the cured film was evaluated by the pencil scratch test of the load of 500g. The same applies to the plastic films according to Examples 2 to 13 and Comparative Examples 1 to 15. The results are shown in Table 1.

The symbols in Table 1 are as follows.
NVF: N-vinylformamide (Arakawa Chemical Industries, Ltd .: Beam Set 770)
HEA: Hydroxyethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate HOA (N))
THF-A: Tetrahydrofurfuryl acrylate (Kyoeisha Chemical Co., Ltd .: Light acrylate THF-A)
BZA: benzyl acrylate (Osaka Organic Chemical Co., Ltd .: Biscote # 160)
DMAA: dimethylacrylamide (manufactured by KJ Chemicals: DMAA)
PETA: Pentaerythritol triacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate PE-3A)
AN: Acrylonitrile (Mitsubishi Rayon: Acrylonitrile)
SA: Stearyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate SA)
9EGA: Polyethylene glycol (PEG # 400) diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate 9EGA)
TMPTA: Trimethylolpropane triacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate TMP-A)
C-2: Arakawa Chemical Industries, Ltd. Beam Set EL-1
(Dispersion of PEDOT / PSS other functional acrylate solution, PEDOT / PSS: about 20%)
C-3: Nissan Chemical Co., Ltd. Cellnax CX-Z610M-F2
(Methanol dispersion of antimony-containing zinc oxide)

Claims (4)

Including a polymerizable unsaturated group-containing monomer having no hydroxyl group (A), urethane acrylate (B), conductive material (C),
The polymerizable unsaturated group-containing monomer (A) having no hydroxyl group has a solubility parameter of 9 to 13 (cal / cm ³ ) ^1/2 , a molecular weight of 350 or less, and a viscosity at 25 ° C. of 30 mPa · s or less. Yes,
The urethane acrylate (B) has at least one structure selected from a (meth) acrylate (b1) having one hydroxyl group in the molecule and an isocyanurate ring structure, biuret structure and allophanate structure having an isocyanate group in the molecule. Having a weight average molecular weight of 500 or more and an acryloyl group equivalent of 140 to 400 g / eq,
Solid weight part ratio of polymerizable unsaturated group-containing monomer (A): urethane acrylate (B): conductive material (C) having no hydroxyl group is 10 to 70:10 to 70: 0.2 to 25 A photocurable resin composition characterized by the above. The photocurable resin composition according to claim 1, wherein the conductive material (C) contains at least one of a compound containing a quaternary ammonium salt structure, a conductive polymer, and metal oxide fine particles. An optical film in which a cured film of the photocurable resin composition according to claim 1 or 2 is formed on at least one surface of the film. The optical film according to claim 3, wherein a surface resistance value on the surface of the cured film is 1.0 × 10 ¹² Ω / □ or less.