JP2017066380A - Optical active energy ray curable resin composition and optical film - Google Patents

Abstract

PURPOSE: To provide an optical active energy ray curable resin composition forming a cured coated film having high hardness, low moisture permeability, high weather resistance and high adhesiveness on a surface of a base film and hardly generating curl.SOLUTION: There is provided an optical active energy ray curable resin composition containing (A) an alicyclic poly(meth)acrylate which is at least one kind selected from a group consisting of (a1) an alicyclic polymerizable monomer having an alicyclic part containing at least 2 (meth)acryloyl groups and at least bicycle and 2 or more atoms which at least bicycle of the alicyclic part shear and (a2) alicyclic polyol having the alicyclic part containing at least 2 (meth)acryloyl groups and at least bicycle and 2 or more atoms which at least bicycle of the alicyclic part shear, polyisocyanate and urethane poly(meth)acrylate which is a reaction product of hydroxyl group-containing (meth)acrylate and/or isocyanate group-containing (meth)acrylate, (B) an acryl copolymer which is an addition reaction product of a polymerization component containing an epoxy group-containing vinyl compound (b1) and a carboxyl group-containing (meth)acryl compound (b2) and has (meth)acryloyl group equivalent of 210 to 800 g/eq, hydroxyl group value of 50 to 270 mgKOH/g and weight average molecular weight of 5,000 to 50,000 and (C) poly(meth)acrylate having at least 3 (meth)acryloyl groups and (meth)acryloyl group equivalent of 74 to 250 g/eq.SELECTED DRAWING: None

Description

  TECHNICAL FIELD The present invention relates to an optical active energy ray-curable curable resin composition that can be used as a protective film for a polarizing plate formed on a base film by forming a cured coating (hard coat layer). The composition can be suitably used when the base film is a triacetyl cellulose film. The present invention also relates to an optical film in which a cured film of the resin composition is formed on a base film.

  Conventionally, a polarizing plate used in a liquid crystal display device is manufactured by adhering a triacetylrose 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 oriented by stretching or the like. The In addition, a transparent active energy ray-curable resin composition is applied to the surface of the TAC film and cured to form a high-hardness film (hard coat layer) to protect it from scratches and the like. As such a resin composition, what uses polyfunctional urethane (meth) acrylate etc. is known, for example (patent document 1).

  In recent years, there has been a demand for polarizing plates that can withstand more severe 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.

  However, since the TAC film has high hygroscopicity, depending on the use environment, the TAC film expands and contracts due to humidity, causing display unevenness. In addition, the TAC film has poor dimensional stability due to its material characteristics, and particularly has a problem that curling tends to occur when a hard coat layer is formed because the dimensional change due to expansion and contraction is large under heat or wet heat conditions. Furthermore, since the TAC film turns yellow when used under high temperature conditions for a long period of time, the display performance of the liquid crystal display device may be deteriorated.

Japanese Patent Laid-Open No. 9-290491

  An object of the present invention is an optically active energy ray-curable resin composition for forming a cured film having high hardness, low moisture permeability, high weather resistance and high adhesion on the surface of a base film, It is to provide something that does not easily occur.

  The present inventor has intensively studied to solve the above problems, and has found that the above problems can be solved by using a reactant having a specific structure, and has completed the present invention. That is, the present invention relates to the following optical active energy ray-curable resin composition and optical film.

1. (A) An alicyclic poly (meth) acrylate having (a1) an alicyclic moiety containing at least two (meth) acryloyl groups and at least two rings, and at least two of the alicyclic moieties Having an alicyclic polymerizable monomer characterized by sharing two or more atoms, and (a2) an alicyclic moiety containing at least two (meth) acryloyl groups and at least two rings, The alicyclic polyol, polyisocyanate, and hydroxyl group-containing (meth) acrylate and / or isocyanate group-containing (meth) are characterized in that at least two of the alicyclic moieties share two or more atoms. A polymerization component comprising at least one selected from the group consisting of urethane poly (meth) acrylate which is a reaction product of acrylate, and (B) an epoxy group-containing vinyl compound ( 1) an addition reaction product of a polymer and a carboxyl group-containing (meth) acrylic compound (b2), wherein the (meth) acryloyl group equivalent is 210 to 800 g / eq, the hydroxyl value is 50 to 270 mgKOH / g, and the weight average molecular weight An acryl copolymer of 5,000 to 50,000, (C) a poly (meth) acrylate having at least three (meth) acryloyl groups and an equivalent weight of 74 to 250 g / eq of (meth) acryloyl groups; , An active energy ray-curable resin composition for optics.

2. The resin composition according to Item 1, wherein the mass ratio of the component (A), the component (B), and the component (C) is (A) :( B) :( C) = 30-80: 5-60: 15-60. object.

3. The resin composition according to Item 1 or 2, further comprising a photopolymerization initiator (D).

4). The resin composition according to any one of Items 1 to 3, further comprising an organic solvent (E).

5. The optical film in which the cured film of the resin composition in any one of said claim | item 1-4 was formed in the at least single side | surface of the base film.

6). Item 5. The optical film as described in 5 above, wherein the moisture permeability of the base film is 50 g / m ² · 24 h or more.

7). Item 7. The optical film according to Item 5 or 6, wherein the moisture permeability is 200 g / m ² · 24 h or less.

According to the optical active energy ray-curable resin composition of the present invention, a cured film having high hardness, low moisture permeability, high weather resistance, and high adhesion can be formed on the surface of the base film in a single layer. . Further, the obtained coated film hardly causes curling. Such an effect is remarkable when the base film is a triacetylcellulose film, and particularly when the moisture permeability is 50 g / m ² · 24 h or more.

  The optical active energy ray-curable resin composition of the present invention can be used not only as a hard coating agent for various base films but also as an adhesive between base films by utilizing its adhesion.

  The optical film of the present invention is provided with a cured film comprising the optical active energy ray-curable resin composition of the present invention, and is excellent in high hardness, low moisture permeability and high weather resistance, and hardly causes curling. . The optical film is particularly useful as a protective film for polarizing plates.

  The optical active energy ray-curable resin composition (hereinafter referred to as resin composition) of the present invention comprises a predetermined (A) alicyclic poly (meth) acrylate (hereinafter referred to as (A) component) and a predetermined (B) acrylic. Copolymer (hereinafter referred to as (B) component), predetermined (C) poly (meth) acrylate (hereinafter referred to as (C) component), and, if necessary, photopolymerization initiator (D) (hereinafter referred to as (D) Component) and / or organic solvent (E) (hereinafter referred to as component (E)).

  The component (A) is at least selected from the group consisting of a predetermined (a1) alicyclic monomer (hereinafter referred to as the (a1) component) and a predetermined (a2) urethane poly (meth) acrylate (hereinafter referred to as the (a2) component). It is a kind.

  The component (a1) is an alicyclic poly (meth) acrylate, and (a1) has an alicyclic part containing at least two (meth) acryloyl groups and at least two rings, and the alicyclic part It is an alicyclic monomer characterized in that at least two rings share two or more atoms, and has no aromatic ring.

  By using the component (a1), the resin composition of the present invention forms a cured coating film excellent in hardness and low moisture permeability even if there is only one layer on the surface of the base film, particularly the TAC film. On the other hand, when (meth) acrylate containing an aromatic skeleton such as a fluorene ring is used in place of the component (a1), the light resistance of the cured film is lowered. Further, when a non-polycyclic (meth) acrylate such as isocyanuric acid ethylene oxide-modified diacrylate or dioxane diglycol diacrylate is used, the moisture permeability of the cured film is increased. Further, even if the compound has two or more alicyclic moieties and at least two of the alicyclic moieties share two or more atoms, one (meth) acryloyl group has one In some cases, the hardness of the cured film decreases.

  Specific examples of the component (a1) include tricyclodecane dimethanol di (meth) acrylate, adamantanediol di (meth) acrylate, adamantane dimethanol di (meth) acrylate, dicyclopentadiene di (meth) acrylate, adamantanetriol tri (Meth) acrylate and adamantanetrimethanol tri (meth) acrylate may be mentioned, and one or more may be used. Among these, tricyclodecane dimethanol diacrylate is preferable in terms of low moisture permeability.

  The component (a2) has at least two (meth) acryloyl groups and an alicyclic moiety containing at least two rings, and at least two of the alicyclic moieties share two or more atoms. Is a reaction product of an alicyclic polyol, a polyisocyanate, a hydroxyl group-containing (meth) acrylate and / or an isocyanate group-containing (meth) acrylate, and does not have an aromatic ring as in the case of the component (a1).

  Specific examples of the alicyclic polyol include alicyclic diols such as tricyclodecane dimethanol, adamantane diol, and hydrogenated dihydroxynaphthalene, and two or more kinds can be used in combination. Among these, tricyclodecane dimethanol is preferable from the viewpoint of ease of synthesis.

  Specific examples of the polyisocyanate include aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate and lysine diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, hydrogenated xylene diisocyanate and hydrogenated tolylene diene. Examples thereof include alicyclic diisocyanates such as isocyanate, and two or more kinds can be used in combination. Among these, alicyclic diisocyanate is particularly preferable in terms of low moisture permeability.

  Specific examples of the hydroxyl group-containing (meth) acrylate include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl acrylate, 3-hydroxybutyl (meth) acrylate, 4- Examples include hydroxyl-containing mono (meth) acrylates such as hydroxybutyl (meth) acrylate and 6-hydroxyhexyl acrylate, and hydroxyl-containing poly (meth) acrylates such as glycerin diacrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate. Two or more types can be used in combination.

  Specific examples of the isocyanate-containing (meth) acrylate include 2-isocyanatoethyl (meth) acrylate and 1,1- (bisacryloyloxymethyl) ethyl isocyanate, methacrylic acid 2- (0- [1 ′ methylpropylideneamino) ] Isocyanate-containing mono (meth) acrylate such as carboxyamino) ethyl, and two or more kinds can be used in combination.

  The manufacturing method of (a2) component is not specifically limited, The manufacturing method of various well-known polyurethane (meth) acrylates is employable.

  When using the said hydroxyl-containing (meth) acrylate, the said alicyclic polyol and polyisocyanate are made to react and an isocyanate group terminal urethane prepolymer is once manufactured. The ratio of both is not particularly limited, but the ratio (NCO ′ / OH ′) of the number of moles of the former hydroxyl group to the number of moles of the latter isocyanate group is usually in the range of about 0.5 to 0.75. Good. Next, the (a2) component is obtained by reacting the isocyanate group-terminated urethane prepolymer with the hydroxyl group-containing (meth) acrylate. The ratio between the two is not particularly limited, but the ratio (NCO / OH) between the number of moles of the former isocyanate group and the number of moles of the latter hydroxyl group is usually within a range of about 0.9 to 1. In each reaction, the temperature and reaction time are not particularly limited, and are usually about 70 to 85 ° C. and about 1 to 5 hours.

  When using the said isocyanate group containing (meth) acrylate, the said alicyclic polyol and polyisocyanate are made to react and a hydroxyl-terminated urethane prepolymer is once manufactured. The ratio of both is not particularly limited, but the ratio (OH ′ / NCO ′) between the number of moles of the former isocyanate group and the number of moles of the latter hydroxyl group is usually about 0.5 to 0.75. Good. Next, the (a2) component is obtained by reacting the hydroxyl group-terminated urethane prepolymer with the isocyanate group-containing (meth) acrylate. The ratio of using both is not particularly limited, but the ratio (OH / NCO) between the number of moles of the former hydroxyl group and the number of moles of the latter isocyanate group is usually within a range of about 1.0 to 1.1. In each reaction, the temperature and reaction time are not particularly limited, and are usually about 70 to 85 ° C. and about 1 to 5 hours.

  The physical properties in the component (a2) are not particularly limited, but usually the (meth) acryloyl group equivalent (theoretical value) is about 200 to 600, and the weight average molecular weight (polystyrene conversion value by gel permeation chromatography) is usually 2000 to 10,000. Degree.

  The reaction product (B) (hereinafter referred to as component (B)) is a polymer of a polymerization component (b1) (hereinafter referred to as component (b1)) containing an epoxy group-containing vinyl compound and a carboxyl group-containing (meth) acrylic compound (b2). ) (Hereinafter referred to as component (b2)).

  Among the components (b1), the epoxy group-containing vinyl compound is not particularly limited as long as it is a compound having a vinyl group capable of radical polymerization and has one epoxy group and one vinyl group, and a known one is used. Can do. Specific examples include glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether, and one or more thereof can be used. Among these, glycidyl (meth) acrylate is preferable from the viewpoint of increasing the hardness of the cured film.

  Examples of the polymerization component other than the epoxy group-containing vinyl compound among the components (b1) include (meth) acrylic acid esters having a chain alkyl group such as methyl (meth) acrylate and ethyl (meth) acrylate, ( (Meth) acrylic esters such as isobornyl (meth) acrylate, (meth) acrylic esters including nitrogen-containing (meth) acrylic esters such as (meth) acryloylmorpholine, styrene, α-methyl Examples thereof include aromatic vinyl compounds such as styrene and vinyl toluene. Among these, methyl methacrylate and / or ethyl methacrylate are preferable in terms of water resistance and heat resistance of the cured coating.

  The use ratio of the epoxy group-containing vinyl compound and other polymerization components is not particularly limited, but is usually about 10/0 to 2/8 in terms of mass ratio, and preferably 10 in view of the balance between the hardness and heat resistance of the cured film. It is about / 0-5 / 5.

  The production method (polymerization method) of the polymer of component (b1) may be, for example, a known radical polymerization method. For example, component (b1) may be a radical polymerization initiator and optionally a chain transfer agent. It can be produced by heating in the presence. Moreover, (E) component can be used as a reaction solvent.

  It does not specifically limit as a radical polymerization initiator, A well-known thing can be used. Specifically, for example, inorganic peroxides such as hydrogen peroxide, ammonium persulfate and potassium persulfate, organic peroxides such as benzoyl peroxide, dicumyl peroxide and lauryl peroxide, 2,2′-azobis Examples thereof include azo compounds such as isobutyronitrile and dimethyl-2,2′-azobisisobutyrate, and one or more of them can be used. The usage-amount of a radical polymerization initiator is not specifically limited, It is about 0.01-8 weight part normally with respect to 100 weight part of (b1) component.

  Examples of the chain transfer agent include lauryl mercaptan, dodecyl mercaptan, 2-mercaptobenzothiazole, bromotrichloromethane, and the like, and one or more can be used. The amount of chain transfer agent used is not particularly limited, and is usually about 0.01 to 5 parts by weight per 100 parts by weight of component (b1).

  The component (b2) is not particularly limited as long as it is a (meth) acrylic compound having at least one carboxyl group in the molecule, and known components can be used. Specific examples include (meth) acrylic acid and crotonic acid, and one or more of them can be used. Among these, acrylic acid is preferable from the viewpoint of photocurability of the resin composition. Although the usage-amount of (b2) component is not specifically limited, From the viewpoint of not leaving (b2) component after active energy ray irradiation, and suppressing the gelatinization of the said polymerization reaction system, etc., with the epoxy group in (B) component, etc. It is preferable to be about a mole.

  The reaction between the polymer of component (b1) and component (b2) is an addition reaction (epoxy ring-opening reaction), and known reaction conditions can be employed. For example, it can be obtained by heating in the presence of a catalyst as required. Examples of the catalyst include phosphines such as triphenylphosphine and tricyclohexylphosphine; quaternary ammonium salts such as tetramethylammonium chloride, trimethylbenzylammonium chloride and tetramethylammonium bromide, trimethylamine, triethylamine, benzylmethylamine, tributylamine and the like. Amines; imidazoles such as 2-methylimedazole; and lauric acid esters such as dibutyltin laurate. Although the usage-amount of a catalyst is not specifically limited, Usually, it is preferable to set it as about 0.01-5 weight part with respect to 100 weight part of total weights of a polymer and (b2) component.

  In the addition reaction, a component (E) and a polymerization inhibitor described later may be used as necessary. Specific examples include methoquinone, hydroquinone, trimethylhydroquinone, N-nitrosophenylhydroxylamine, and the like. The amount of the polymerization inhibitor used is not particularly limited, but the polymerizability of the resulting coating agent may be deteriorated. Therefore, usually 1 weight per 100 weight parts of the total weight of the polymer and the component (b2). It is preferable to set it to about part or less. In order to prevent polymerization, air may be blown into the reaction system.

  The component (B) thus obtained has a (meth) acryloyl equivalent (theoretical value) of 210 to 800 g / eq, a hydroxyl value of 50 to 270 mg KOH / g, and a weight average molecular weight of 5,000 to 50,000. It is characterized by being.

  When the (meth) acryloyl equivalent is less than 210 g / eq, shrinkage occurs during curing of the resin composition, and the optical film tends to curl. Moreover, when it exceeds 800 g / eq, it exists in the tendency for the intensity | strength of a cured film to fall. From this viewpoint, it is preferably 210 to 500 g / eq.

  When the hydroxyl value is less than 50 mgKOH / g, the strength of the cured film tends to be insufficient. On the other hand, if it exceeds 270 mgKOH / g, the optical film tends to curl due to shrinkage when the resin composition is cured. From this viewpoint, it is preferably 110 to 270 mgKOH / g.

  If the weight average molecular weight is less than 5,000, the effect of reducing curing shrinkage tends to be insufficient. On the other hand, if it exceeds 50,000, the stability of the resin composition tends to be insufficient. From this viewpoint, Preferably, it is 8,000-30,000.

  Compound (C) (hereinafter referred to as component (C)) has 3 or more, preferably 3 to 15 (meth) acryloyl groups in one molecule, and has a (meth) acryloyl group equivalent of 74 to 250 g / eq. If it is a certain compound, a well-known thing can be especially used without a restriction | limiting. By using the component (C), a high hardness film can be formed, so that it can be suitably used as an optical film having low moisture permeability, high hardness, and light resistance.

  When the (meth) acryloyl group equivalent is less than 74 g / eq, shrinkage occurs during curing of the resin composition, and the optical film tends to curl. Moreover, when it exceeds 250 g / eq, it exists in the tendency for the hardness (pencil hardness) of the cured film obtained to become inadequate. From this viewpoint, the (meth) acryloyl group equivalent is preferably 88 to 200 g / eq.

  Specific examples of the component (C) include monohydroxy poly (meth) acrylates such as pentaerythritol monohydroxytri (meth) acrylate and dipentaerythritol monohydroxypenta (meth) acrylate, pentaerythritol monohydroxytriallyl ether, Examples thereof include monohydroxy polyallyl ether such as triallyl acid, and one or more of them can be used.

  Although the mass ratio of (A) component, (B) component, and (C) component is not specifically limited, Usually, it is (A) :( B) :( C) = 30-80: 5-60: 15-60. From the viewpoint of achieving both low moisture permeability while maintaining high hardness and low curing shrinkage, 50 to 75:10 to 30 to 30 to 50 is preferable.

  The component (D) can be used as necessary when the resin composition is UV-cured. 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. , It can be used one or more kinds.

  Although the usage-amount of (D) component is not specifically limited, Usually, it is about 1-10 weight part with respect to a total of 100 weight part of (A) component, (B) component, and (C) component.

  The resin composition of the present invention may further contain a polymerization component other than the component (A), the component (B), and the component (C) as necessary. Specifically, for example, isobornyl acrylate, tetrahydrofurfuryl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, lauryl acrylate, 1,4-butanediol diacrylate, 1,6-hexanediol di- Acrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, hydroxyethyl methacrylate, isobornyl methacrylate, tetrahydrofurfuryl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, lauryl methacrylate, 1,4-butane Diol dimethacrylate, 1,6-hexanediol dimethacrylate, La ethylene glycol dimethacrylate, tripropylene glycol dimethacrylate and the like, can be used alone or in combination. Although the usage-amount of this polymerization component is not specifically limited, Usually, it is 50% or less in all the solid components.

  Examples of the component (E) include alcohols such as ethyl alcohol and propanol; lower ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as toluene and benzene; butyl acetate, ethyl acetate, chloroform, dimethylformamide, and the like. 2 or more types can be used in combination.

  Although the usage-amount of (E) component is not specifically limited, Usually, what is necessary is just the range by which the solid content weight of the resin composition of this invention will be about 30 to 70%.

  The resin composition of the present invention is obtained by mixing the component (A), the component (B) and the component (C), and the component (D) and / or the above other polymerization component according to various known means. . The component (A) may be a solution of the component (E).

  The resin composition of the present invention may contain various known additives such as a photosensitizer, an antioxidant, a light stabilizer, a leveling agent, and a pigment.

  The optical film of the present invention is obtained by forming a cured film made of the resin composition of the present invention on at least one surface of a base film.

  Various known films can be used as the base film. Specifically, for example, polycarbonate film, acrylic film (polymethyl methacrylate film, etc.), polystyrene film, polyester film, polyolefin film, epoxy resin film, melamine resin film, triacetyl cellulose film, ABS film, AS film, norbornene series Resin film etc. are mentioned. Although the thickness of a base film is not specifically limited, Usually, it is about 20-100 micrometers.

By the way, although the moisture permeability of the base film is proportional to the film thickness, for example, the acrylic film is generally considered to have a low moisture permeability. However, the moisture permeability is reduced by making the film thinner in accordance with the recent downsizing and weight reduction of electronic products. May be 50 g / m ² · 24 h or more. Thus, even if it is a base film with a water vapor transmission rate of 50 g / m ² · 24 h or more, the entire water vapor transmission rate can be reduced to, for example, 200 g / m ² · 24 h or less by hard coating with the resin composition of the present invention. it can. From such viewpoints, the base moisture permeability of the film, for example 50g ^/ m 2 · 24h or more, preferably if 50~750g ^/ m 2 · 24h. Such a base film, combined with the excellent low moisture permeability of the cured film made of the resin composition of the present invention, gives an optical film excellent in the low moisture permeability.

As the base film, a triacetyl cellulose film is preferable in terms of adhesion to the cured film made of the resin composition of the present invention. In particular moisture permeability 50g ^/ m 2 · 24h or more (preferably, 50~750g ^/ m 2 · 24h) is preferred ones.

  The optical film of the present invention can be produced by various known methods. Specifically, the resin composition of the present invention may be applied to at least one surface of the base film and dried as necessary, and then irradiated with active energy rays. In addition, a laminated film can be produced by applying the resin composition of the present invention to the non-coated surface of the obtained base film and then irradiating with an active energy ray after bonding another base film thereon. it can. Any of these films can be used as an optical film.

  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 the active energy rays 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.

The optical film of the present invention is basically composed of one layer of a cured film consisting of the resin composition of the present invention and a base film. Optical film of the basic structure, moisture permeability 200g ^/ m 2 · 24h or less, preferably 30~150g ^/ m 2 · 24h, can be suitably used as a polarizing plate protective film.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated concretely, naturally the scope of the present invention is not limited by them. In each example, parts and% are based on weight.

((Meth) acryloyl group equivalent)
Calculated by the following formula.
[Equation 1]
((Meth) acrylic group equivalent) = (molecular weight of one molecule) / (number of (meth) acryloyl groups present in one molecule)

(Hydroxyl value)
Calculated by the following formula.
[Equation 2]
(Hydroxyl value) = (potassium hydroxide molecular weight: 56100) / (hydroxyl equivalent)
(Hydroxyl equivalent) = (Molecular weight of one molecule) / (Number of hydroxyl groups present in one molecule)

(Weight average molecular weight)
Gel permeation chromatography (trade name “HLC-8220” manufactured by Tosoh Corporation, column: manufactured by Tosoh Corporation, trade names “TSKgel superHZ2000”, “TSKgel superHZM-M”).

<Synthesis of component (a2)>
Synthesis example 1
A reaction vessel equipped with a stirrer, a condenser, and a dropping funnel was charged with 131 parts of hydrogenated xylene diisocyanate and 0.1 part of tin octylate and heated to 70 ° C. Subsequently, it dropped in the system over 1 hour from the dropping funnel previously charged with the mixed solution of 66 parts of tricyclodecane dimethanol and 120 parts of MIBK. After incubating for 1 hour, the mixture was cooled to 40 ° C., and 82 parts of 2-hydroxyethyl acrylate and 0.1 part of tin octylate were charged. The temperature in the system was raised to about 80 ° C., kept for 3 hours, and then cooled to obtain a solution of the reactive organism (A-1).

Synthesis example 2
In a reaction vessel equipped with a stirrer, a cooling tube, and a dropping funnel, 49 parts of hydrogenated xylene diisocyanate and 0.1 part of tin octylate were charged and heated to 70 ° C. Subsequently, it was dripped in the system over 1 hour from the dropping funnel previously charged with the mixed solution of 25 parts of tricyclodecane dimethanol and 50 parts of MIBK. After incubating for 1 hour, the mixture was cooled to 40 ° C., and 125 parts of biscoat # 300 and 0.05 part of tin octylate were charged. The temperature in the system was raised to about 80 ° C., kept for 3 hours, and then cooled to obtain a solution of a reactive organism (A-2).

<Synthesis of component (B)>
Synthesis example 3
In a reactor equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introducing tube, 250 parts of glycidyl methacrylate (hereinafter referred to as GMA), 1000 parts of methyl isobutyl ketone (hereinafter referred to as MIBK) and 2,2-azobisisobutyro After charging 7.5 parts of nitrile (hereinafter referred to as AIBN), the temperature was raised to about 116 ° C. over about 1 hour in a nitrogen stream, and the temperature was kept for 1 hour. Next, from a dropping funnel charged beforehand with a mixed liquid consisting of 750 parts of GMA and 22.5 parts of AIBN, the mixed liquid was dropped into the system over about 2 hours under a nitrogen stream and kept at the same temperature for 3 hours. After that, 10 parts of AIBN were added. Charged and kept warm for 3 hours. After cooling to 60 ° C, the nitrogen inlet tube is replaced with an air inlet tube, 507 parts of acrylic acid, 1.9 parts of methoquinone and 5.0 parts of triphenylphosphine are charged and mixed, and then to 110 ° C under air bubbling. The temperature rose. After incubating at the same temperature for 8 hours, 1.3 parts of methoquinone was charged, cooled, and MIBK was added so that the non-volatile content was 50% to obtain a solution of the reaction product (B-1). The reaction product (B-1) had a (meth) acryloyl group equivalent of 214 g / eq, a hydroxyl value of 262 mgKOH / g, and a weight average molecular weight of 15,000.

Synthesis example 4
In a reactor similar to Example 1, 125 parts of GMA, 125 parts of methyl methacrylate (hereinafter referred to as MMA), 1000 parts of MIBK and 7.5 parts of AIBN were charged, and the system temperature was about 116 under nitrogen flow for about 1 hour. The temperature was raised to 0 ° C. and kept for 1 hour. Next, from a dropping funnel charged beforehand with a mixed liquid consisting of 375 parts of GMA, 375 parts of MMA, and 22.5 parts of AIBN, the mixed liquid was dropped into the system over about 2 hours under a nitrogen stream, and kept at the same temperature for 3 hours. 10 parts of AIBN were charged and kept warm for 3 hours. After cooling to 60 ° C, the nitrogen inlet tube was replaced with an air inlet tube, 254 parts of acrylic acid, 1.9 parts of methoquinone and 5.0 parts of triphenylphosphine were charged and mixed, and then up to 110 ° C under air bubbling. The temperature rose. After incubating at the same temperature for 8 hours, 1.3 parts of methoquinone was charged and cooled, and MIBK was added so that the non-volatile content was 50% to obtain a solution of the reaction product (B-2). The reaction product (B-2) had a (meth) acryloyl group equivalent of 314 g / eq, a hydroxyl value of 179 mgKOH / g, and a weight average molecular weight of 15,000.

Synthesis Example 5 Comparative Synthesis Example of Component (B) After charging 25 parts of GMA, 225 parts of MMA, 1000 parts of MIBK and 7.5 parts of AIBN in the same reaction apparatus as in Example 1, the system was allowed to flow for about 1 hour in a nitrogen stream. The temperature was raised until the temperature reached about 116 ° C., and the temperature was kept for 1 hour. Next, from a dropping funnel charged beforehand with a mixed solution consisting of 75 parts of GMA, 675 parts of MMA, and 22.5 parts of AIBN, the mixed liquid was dropped into the system over about 2 hours under a nitrogen stream, and kept at the same temperature for 3 hours. 10 parts of AIBN were charged and kept warm for 3 hours. After cooling to 60 ° C, the nitrogen inlet tube is replaced with an air inlet tube, and after 101 parts of acrylic acid, 1.9 parts of methoquinone and 5.0 parts of triphenylphosphine are charged and mixed, the temperature is reduced to 110 ° C under air bubbling. The temperature rose. After incubating at the same temperature for 8 hours, 1.3 parts of methoquinone was charged and cooled, and MIBK was added so that the non-volatile content was 50% to obtain a solution of the reaction product (B-3). The reaction product (B-3) had a (meth) acryloyl group equivalent of 1500 g / eq, a hydroxyl value of 37 mgKOH / g, and a weight average molecular weight of 15,000.

Synthesis Example 6
A reactor equipped with a stirrer, a cooling pipe, a dropping funnel and a nitrogen introducing pipe was charged with 250 parts of GMA, 1000 parts of MIBK and 25 parts of AIBN, and then the system temperature was about 116 ° C. over about 1 hour under a nitrogen stream. The temperature was raised to 0, and the temperature was kept for 1 hour. Next, from a dropping funnel charged beforehand with a mixed liquid consisting of 750 parts of GMA and 75 parts of AIBN, the mixed liquid was dropped into the system over about 2 hours under a nitrogen stream and kept at the same temperature for 3 hours, and then 10 parts of AIBN were charged. Incubated for 3 hours. After cooling to 60 ° C, the nitrogen inlet tube is replaced with an air inlet tube, 507 parts of acrylic acid, 1.9 parts of methoquinone and 5.0 parts of triphenylphosphine are charged and mixed, and then to 110 ° C under air bubbling. The temperature rose. After incubating at the same temperature for 8 hours, 1.3 parts of methoquinone was charged, cooled, and MIBK was added so that the non-volatile content was 50% to obtain a solution of the reaction product (B-4). The reaction product (B-4) had a (meth) acryloyl group equivalent of 214 g / eq, a hydroxyl value of 262 mgKOH / g, and a weight average molecular weight of 4,900.

Synthesis example 7
After charging 141 parts of 2-isocyanatoethyl acrylate, 0.1 part of tin octylate and 428 parts of component (B-1) in a reaction vessel equipped with a stirrer and a condenser, the system was allowed to spend about 1 hour. Was raised to about 80 ° C. Next, the reaction system was maintained at the same temperature for 3 hours, and then cooled to obtain a reaction product (B-5). The reaction product (B-5) had a (meth) acryloyl group equivalent of 178 g / eq, a hydroxyl value of 0 mg KOH / g, and a weight average molecular weight of 23,000.

<Preparation of active energy ray-curable resin composition>
Example 1
50 parts of light acrylate DCP-A (tricyclodecanedimethanol diacrylate manufactured by Kyoeisha Chemical Co., Ltd.) as component (A), 20 parts of component B-1 of Synthesis Example 1 as component (B), component (C) 30 parts of biscort # 300 (pentaerythritol triacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.) The active energy ray-curable composition having a non-volatile content of 50% was prepared by blending the components at a solid content ratio and diluting with methyl ethyl ketone (MEK).

Examples 2-6, Comparative Examples 1-13
An active energy ray-curable composition having a nonvolatile content of 50% was prepared in the same manner as in Example 1, except that the types and blending amounts of the components (A) to (C) were changed to those shown in Table 1. The moisture permeability, pencil hardness, film curl and light resistance of the cured product of each composition were evaluated.

<Production of cured film>
On the triacetyl cellulose film (Fuji Film Co., Ltd., trade name “FT TD80ULM”, water vapor transmission rate: 500 g / m ² · 24 h) having a thickness of 80 μm as a base film, Example 1 shown in Table 1 The resin composition was applied with a # 16 bar coater so that the film thickness of the cured film was 10 μm, and dried at 80 ° C. for 1 minute. 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 having a cured coating film. It was. Films were similarly prepared for the resin compositions according to Examples 2 to 6 and Comparative Examples 1 to 13. The results are shown in Table 1.

<Evaluation of cured film>
(1) Moisture permeability About the plastic film which concerns on Example 1 of Table 1, according to JISZ0208, the moisture permeability of the whole film was evaluated. The same applies to the plastic films according to other examples and comparative examples. The results are shown in Table 1.

(2) Pencil hardness About the plastic film which concerns on Example 1 of Table 1, according to JISK5600-5-4, the hardness of the hardened film was evaluated by the pencil scratch test of the load of 500g. Pencil hardness was similarly evaluated about the plastic film which concerns on another Example and a comparative example.

(3) Film curl When the plastic film according to Example 1 shown in Table 1 is cut into 10 cm × 10 cm and the plastic film does not become cylindrical (in a state in which the end portions of the films overlap), “O” When it became cylindrical, it was classified as “×”. The presence or absence of curling was similarly evaluated for the plastic films according to other examples and comparative examples.

(4) Light resistance About the plastic film which concerns on Example 1 of Table 1, a plastic film is made with a carbon arc lamp with a UV auto fade meter (trade name: UV auto fade meter U48AU manufactured by Suga Test Instruments Co., Ltd.). 100 hours exposure. The plastic film after the test was measured by a transmission method of a color difference meter (trade name: ZE 6000 manufactured by Nippon Denshoku Industries Co., Ltd.). Classified as “×”. The light resistance was similarly evaluated for the plastic films according to other examples and comparative examples.

Light acrylate DCP-A: Tricyclodecane dimethanol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.)
IBXA: Isobornyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
Aronix M-215: Isocyanuric acid ethylene oxide modified diacrylate (manufactured by Toagosei Co., Ltd.)
OGSOL EA-0200: Fluorene acrylate (Osaka Gas Chemical Co., Ltd.)
Biscoat # 300: Pentaerythritol triacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
Aronix M-400: Dipentaerythritol penta and hexaacrylate (manufactured by Toagosei Co., Ltd.)
KAYARAD DPCA-30: ε-caprolactone-modified dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)
KAYARAD DPCA-60: ε-caprolactone-modified dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)
Biscote # 260: 1,9-nonanediol diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
IRGACURE 184: 1-hydroxy-cyclohexyl-phenyl ketone (manufactured by BASF Japan Ltd.)

Claims (7)

(A) an alicyclic poly (meth) acrylate,
(A1) having an alicyclic moiety containing at least two (meth) acryloyl groups and at least two rings, and at least two of the alicyclic moieties share two or more atoms, An alicyclic polymerizable monomer,
And
(A2) having an alicyclic part containing at least two (meth) acryloyl groups and at least two rings, and at least two of the alicyclic parts share two or more atoms, Alicyclic polyol, polyisocyanate, and at least one selected from the group consisting of urethane poly (meth) acrylate which is a reaction product of hydroxyl group-containing (meth) acrylate and / or isocyanate group-containing (meth) acrylate,
(B) An addition reaction product of a polymer of a polymerization component (b1) containing an epoxy group-containing vinyl compound and a carboxyl group-containing (meth) acrylic compound (b2), wherein the (meth) acryloyl group equivalent is 210 to 800 g / eq. An acrylic copolymer having a hydroxyl value of 50 to 270 mg KOH / g and a weight average molecular weight of 5,000 to 50,000,
(C) a poly (meth) acrylate having at least three (meth) acryloyl groups and having a (meth) acryloyl group equivalent weight of 74 to 250 g / eq;
An active energy ray-curable resin composition for optics containing The resin composition of Claim 1 whose mass ratio of (A) component, (B) component, and (C) component is (A) :( B) :( C) = 30-80: 5-60: 15-60. object. Furthermore, the resin composition of Claim 1 or 2 containing a photoinitiator (D). Furthermore, the resin composition in any one of Claims 1-3 containing an organic solvent (E). An optical film in which a cured film of the resin composition according to claim 1 is formed on at least one side of a base film. The optical film according to claim 5, wherein the moisture permeability of the base film is 50 g / m ² · 24 h or more. The optical film according to claim 5 or 6, wherein the moisture permeability is 200 g / m ² · 24 h or less.