JP5811374B2 - Antistatic agent for active energy ray curable resin composition, active energy ray curable resin composition, cured film and antistatic treatment optical film - Google Patents

Description

  The present invention relates to an antistatic agent for an active energy ray-curable resin composition, an active energy ray-curable resin composition containing the antistatic agent, an antistatic cured film obtained from the composition, and the cured film. The present invention relates to an antistatic optical film.

  As a hard coating agent used for a front plate of various display devices such as a liquid crystal display, a plasma display, an organic EL display (hereinafter, collectively referred to as a flat panel display), for example, pentaerythritol poly ( Compositions comprising a compound having a large number of (meth) acryloyl groups in the molecule such as (meth) acrylate and ditrimethylolpropane poly (meth) acrylate (so-called active energy ray-curable resin), a reactive diluent, and the like. Things are known. The composition is highly productive because it is instantaneously cured by irradiation with ultraviolet rays or an electron beam, and forms a cured film having excellent hardness and scratch resistance on the surface of various substrates.

  By the way, when such an active energy ray-curable resin composition is used for flat panel display applications, the cured film is not only highly transparent, but also prevents troubles caused by static electricity during display assembly and operation. In order to realize a high-definition image, good antistatic properties are required.

  As a method for imparting antistatic properties to the cured film, for example, it is conceivable to add various conductive fillers to the active energy ray-curable resin composition, but a large amount is used to obtain a sufficient antistatic effect. Since it is necessary, the transparency and hardness of the cured film may be adversely affected. Moreover, since the active energy ray-curable resin composition using, for example, zinc antimonate fine particles as the conductive filler (see Patent Document 1), coloring derived from visible light is observed in the cured film, so that the flat panel display is particularly preferable. It was unsuitable for use.

  On the other hand, it is conceivable to use organic substances (π-conjugated conductive polymers) such as poly (thiophene) and poly (aniline) as antistatic agents, but these are generally strongly colored, so There are difficulties in terms of coloring. However, even if it is a conductive polymer, the transparency of a cured film can be ensured by using a copolymer having a quaternary ammonium salt structure. However, since the copolymer has a hydrophilic structure called a quaternary ammonium salt, it is an organic compound such as an active energy ray-curable resin, particularly a poly (meth) acrylate compound having a large number of (meth) acryloyl groups. In addition, the compatibility with a high molecular weight hydroxyl group-containing poly (meth) acrylate compound is generally considered to be insufficient.

  In this regard, Patent Document 2 describes that a quaternary ammonium salt structure-containing copolymer into which an alkyl group-terminated alkylene oxide chain is introduced is excellent in compatibility with an active energy ray-curable resin. Antistatic effect per use amount was not sufficient.

  Patent Document 3 describes that compatibility with an active energy ray-curable resin is improved by introducing an organopolysiloxane unit into a quaternary ammonium salt structure-containing copolymer. The transparency (haze) of the cured film is not sufficient, and it is considered that the cured film is particularly unsuitable for the flat panel display application described above. Moreover, since the recoat property of a cured film is inadequate, it is thought that a use is also restrict | limited.

  In addition, in the case of Patent Document 4, the applicant of the present invention obtained by grafting a hydroxyl group-terminated lactone chain and an alicyclic alkyl ester chain to a quaternary ammonium salt structure-containing copolymer is an active energy ray-curable resin (poly (meta It has been proposed that it has excellent compatibility with) acrylate compounds) and can impart excellent antistatic properties to the cured film. However, since the active energy ray-curable resin composition containing the quaternary ammonium salt structure-containing copolymer has relatively high water absorption, the surface resistance value of the cured film obtained from the resin composition increases with time. Tended to be easy.

  On the other hand, as another method for imparting antistatic properties to an optical film, for example, a method of providing a transparent conductive layer on a substrate film is known, and Patent Document 5 discloses an active energy ray-curable resin and conductive fine particles. An optical film having a transparent conductive layer made of and a hard coat layer provided thereon is described. However, since such an optical film has a so-called two-coat specification, there is a difficulty in manufacturing cost.

JP-A-9-0511116 JP-A-6-73305 Japanese Patent Laid-Open No. 10-279833 JP2012-312297A Japanese Patent Laid-Open No. 11-42729

  The present invention is a composition mainly composed of an active energy ray-curable resin such as a poly (meth) acrylate compound, and is not only excellent in compatibility with the active energy ray-curable resin, but also absorbs water from the resin composition. The main object is to provide a novel antistatic agent that can suppress the deterioration of the antistatic property of the cured film obtained from the resin composition.

  The present invention also provides an active energy ray-curable resin composition that is excellent in antistatic properties over time, and that can form a cured film with excellent transparency, scratch resistance, hardness, etc., with a single coat. It is also an issue to do.

  Another object of the present invention is to provide an antistatic film having a cured film that is excellent in antistatic properties over time and has good transparency, scratch resistance, hardness, and the like.

  As a result of intensive studies, the present inventors have found that a quaternary ammonium salt structure-containing copolymer having both a predetermined branched alkyl ester structure and a polyester structure is sufficient to solve the above problems. I found out.

  The inventor has also found that an active energy ray-curable resin composition containing the antistatic agent and a specific (poly) methacrylate compound provides a cured film and an antistatic treatment film that can solve the above-mentioned problems. It was.

That is, the present invention relates to a vinyl monomer (a2) having a quaternary ammonium salt structure, a ring-opening polyaddition of a hydroxyl group-containing vinyl monomer and a lactone, and having a weight average molecular weight of 4000 to 10,000. ), And a vinyl monomer (a3) having a branched alkyl ester group having 3 to 5 carbon atoms and having no alicyclic structure, the copolymerization ratio (weight ratio) is 30-60: 15-35: 20- An antistatic agent (1) for an active energy ray-curable resin composition, which contains a copolymer (A) obtained by reacting so as to be 40 ; the antistatic agent (1), at least 5 in the molecule Active poly (meth) acrylates (2) having one (meth) acryloyl group, and optionally a reactive diluent (3) and a photopolymerization initiator (4). Energy ray-curable resin composition; the radiation-curable curable coating resin composition obtained; antistatic-treated optical film having at least one surface of the cured film substrate film relates.

    The antistatic agent of the present invention is compatible with an active energy ray-curable resin, particularly a poly (meth) acrylate compound having a large number of (meth) acryloyl groups or a poly (meth) acrylate compound having a high molecular weight and a hydroxyl value. And a transparent active energy ray-curable resin composition is obtained. In addition, according to the antistatic agent, the absorption rate of moisture in the air of the active energy ray-curable resin composition using the antistatic agent is reduced, so that problems such as poor compatibility and reduced antistatic property of the cured film arise. hard. In addition, the antistatic agent is excellent in the antistatic effect per unit use amount.

  In addition, the active energy ray-curable resin composition using the antistatic agent is excellent in transparency and has a low moisture absorption rate in the atmosphere, so that there are problems such as poor compatibility and reduced antistatic properties of the cured film. Is unlikely to occur. Further, the cured film is a smooth film excellent not only in antistatic properties, transparency, hardness, and scratch resistance but also in weather resistance, recoatability, and the like, and can be obtained by one coating. Therefore, the active energy ray-curable resin composition is useful as a coating agent for a front plate of various flat panel displays and can also be suitably used as a coating agent for a cathode ray tube.

  The antistatic treatment film of the present invention is excellent in antistatic properties, transparency, surface hardness, scratch resistance, weather resistance, etc., and is suitable for flat panel display applications such as liquid crystal displays, plasma displays, and organic EL displays. It is.

The antistatic agent (1) for active energy ray-curable resin composition of the present invention (hereinafter referred to as component (1)) is a vinyl monomer (a1) having a quaternary ammonium salt structure (hereinafter referred to as component (a1)). ), A vinyl monomer (a2) (hereinafter referred to as the (a2) component) having a weight average molecular weight of 4000 to 10,000, which is formed by ring-opening polyaddition of a hydroxyl group-containing vinyl monomer and a lactone, and having 3 carbon atoms. has a 5 branched alkyl ester group, and a vinyl monomer having no alicyclic structure (a3) (hereinafter, (a3) component called.) copolymer obtained by reacting (a) (hereinafter, (Referred to as component (A)).

As the component (a1), various known monomers can be used without particular limitation as long as they are vinyl monomers having a quaternary ammonium salt structure in the molecule. Specifically, equation ^{_{(1): CH 2 = C}} (R 1) -CO-A-B-N + (R 2) (R 3) (R 4) · X - ( wherein, ^{R 1} is H Or CH ₃ , R ^{2 to} R ⁴ represent an alkyl group having about 1 to 3 carbon atoms, A represents O or NH, B represents an alkylene group having about 1 to 3 carbon atoms, and X ⁻ represents a counter anion species) The (meth) acrylate compound represented by these is suitable and may be used individually by 1 type, or may use 2 or more types together. Examples of X ⁻ include Cl ⁻ , SO ₄ ⁻ , SO ₃ ⁻ , C ₂ H ₅ SO ₄ ⁻ , Br ^{− and the} like, and Cl ⁻ is most preferable from the viewpoint of the antistatic effect. The component (a1) is a commercially available product (“Kyoeisha Chemical Co., Ltd.“ Light Ester DQ-100 ”) (manufactured by“ Kohjin Corporation ”“ DMAEA-Q ” Etc.) can be used.

  The component (a2) is obtained by subjecting a hydroxyl group-containing vinyl monomer and a lactone to a ring-opening polyaddition reaction, and various known ones can be used without particular limitation. In addition, when other long chain monomers, for example, vinyl monomers having an alkyl group-terminated alkylene oxide structure in the molecule are used instead of the component (a2), the antistatic property of the cured film tends to be insufficient. It is in.

  Examples of the hydroxyl group-containing vinyl monomers include hydroxyl group-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and hydroxyethyl (meth) acrylamide, and hydroxyethyl vinyl ether. , Hydroxyl group-containing vinyl monomers such as hydroxybutyl vinyl ether and hydroxydiethylene glycol vinyl ether are mentioned, and one kind may be used alone, or two or more kinds may be used in combination. Among these, a hydroxyl group-containing (meth) acrylate is particularly preferable from the viewpoint of radical copolymerizability.

  Examples of lactones include β-propiolactone, γ-butyrolactone, δ-valerolactone, β-methyl-δ-valerolactone, and ε-caprolactone, and two or more of them can be used alone. May be used in combination. Among these, one selected from the group consisting of ε-caprolactone and δ-valerolactone is particularly preferable from the viewpoint of the reactivity of ring-opening polymerization.

  In addition, the component (a2) has a weight average molecular weight (referred to polystyrene conversion value by gel permeation chromatography, hereinafter the same) of 4000 to 10,000. This is because if the weight average molecular weight is less than 4000, the compatibility tends to be insufficient, or the transparency of the cured film tends to be impaired, and those exceeding 10,000 are difficult to synthesize. Because. From this viewpoint, the weight average molecular weight is preferably 5000 to 8000.

  The component (a2) can be obtained by various known methods. Specifically, for example, the lactones may be subjected to a ring-opening polyaddition reaction using the hydroxyl group-containing vinyl monomers as an initiator. Moreover, the weight average molecular weight can be adjusted by appropriately selecting the charging ratio of both, the reaction temperature, and the catalyst type / amount during the reaction.

  In the reaction, mineral acids such as sulfuric acid and phosphoric acid; alkali metals such as lithium, sodium and potassium; alkyl metal compounds such as n-butyl lithium and t-butyl lithium; metal alkoxides such as titanium tetrabutoxide; Catalysts such as tin compounds such as urilate, dibutyltin dioctrate, dibutyltin mercaptide and tin octylate can be used. The amount used is not particularly limited, but is usually about 0.01 to 10% by weight relative to 100% by weight of the total of the hydroxyl group-containing vinyl monomers and lactones.

  As the component (a3), various known monomers can be used without particular limitation as long as they are vinyl monomers having a branched alkyl ester group having 3 to 5 carbon atoms and having no alicyclic structure. Specifically, for example, one kind selected from the group consisting of iso-propyl (meth) acrylate, tert-butyl (meth) acrylate, iso-butyl (meth) acrylate, iso-pentyl (meth) acrylate and the like can be mentioned. It is done. By using the component (a3) as a raw material for the component (A), the antistatic property over time of the cured film obtained from the active energy ray-curable resin composition containing the component (A) is improved. From this viewpoint, the component (a3) is preferably one selected from the group consisting of tert-butyl (meth) acrylate and iso-butyl (meth) acrylate.

The copolymer (A) may further contain another vinyl monomer (a4) as a reaction component. Examples of the component (a4) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, and benzyl (meth) acrylate. And mono (meth) acrylates having a hydrocarbon group of about 1 to 10 carbon atoms (excluding those corresponding to the component (a3)) such as phenyl (meth) acrylate, styrene, α-methylstyrene, and Examples include aromatic ring structure vinyl monomers such as 4-methylstyrene, and one kind may be used alone, or two or more kinds may be used in combination.

  Component (A) is a radical copolymer prepared by various known methods (bulk polymerization, solution polymerization, emulsion polymerization, etc.) using the components (a1), (a2) and (a3), and if necessary, (a4). It is obtained by polymerizing. The reaction temperature is usually about 40 to 160 ° C., and the reaction time is about 2 to 12 hours.

(A1) component ~ (a 3) the copolymerization ratio of the components is not particularly limited, considering the (A) the compatibility and the component and the active energy ray curable resin, the antistatic property and transparency and the like of the cured film Usually, it is about 30-60: 15-35: 20-40 ( weight ratio) in order, Preferably it is 40-50: 15-25: 25-35 ( weight ratio). In addition, the copolymerization ratio of the components (a1) to (a4) in the case of using the component (a4) is not particularly limited, but the compatibility between the component (A) and the active energy ray curable resin, and charging of the cured film Considering prevention and transparency, it is usually about 30 to 60:15 to 35:20 to 40: 0 to 20 (weight ratio), preferably 40 to 50:15 to 25:25 to 35:35. 0 to 10 (weight ratio).

  In the reaction, 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 (isobutyrate) Rononitrile) and radical polymerization initiators such as azo compounds such as 2,2′-azobis (methylbutyronitrile) can be used. The amount used is not particularly limited, but is usually about 0.01 to 10% by weight based on the total weight of the components (a1) to (a4).

  Further, chain transfer agents such as lauryl mercaptan, dodecyl mercaptan, 2-mercaptobenzothiazole and bromotrichloromethane may be used. The amount used is not particularly limited, but is usually about 0.01 to 10% by weight based on the total weight of the components (a1) to (a4).

  In the case of solution polymerization, glycol ethers such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether; alcohols such as methanol, ethanol and n-propanol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Aromatic hydrocarbons such as toluene and xylene; Acetic esters such as ethyl acetate and butyl acetate; Organic solvents such as chloroform and dimethylformamide can be used. Among these, glycol ethers are preferable from the viewpoint of the dissolving power of the components (a1) to (a4). In the case of emulsion polymerization, various known anionic, nonionic, and cationic surfactants can be used.

  The physical properties of the component (A) thus obtained are not particularly limited. For example, the weight average molecular weight (referred to a polyethylene oxide conversion value in the gel permeation chromatography method) is usually 350,000 or less, specifically 200,000 to The range is about 350,000. When the weight average molecular weight is 100,000 or more, bleeding out of the component (A) (that is, the component (1)) from the cured film can be reduced, so that the antistatic property of the cured film is improved. Further, when the weight average molecular weight is 350,000 or less, the compatibility of the component (A) with the poly (meth) acrylates (2) and the reactive diluent (3) becomes better, and the time course It becomes easy to obtain a cured film having excellent antistatic properties. In addition, the measuring method of this weight average molecular weight is not specifically limited, Various well-known means can be employ | adopted and a commercially available measuring machine can also be utilized.

  When the component (A) is a solid, the component (1) can be used as a solution containing the organic solvent (nonvolatile content is usually about 5 to 50% by weight). When the component (A) is obtained by solution polymerization, it can be used as a solution containing the component (A) and the organic solvent (nonvolatile content is usually about 5 to 50% by weight).

  The active energy ray-curable resin composition of the present invention is (1) component, poly (meth) acrylates having at least 5 (meth) acryloyl groups in the molecule (2) (hereinafter referred to as (2) component. ), And if necessary, reactive diluent (3) (hereinafter referred to as component (3), excluding those corresponding to component (2)) and photopolymerization initiator (4) (hereinafter referred to as (4) Component)).

  As the component (2), for example, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol poly (meth) acrylate, pentaerythritol poly (meth) acrylate, etc. Non-urethane-modified poly (meth) acrylate compound (2-1) (hereinafter referred to as (2-1) component) having 5 (specifically, about 5 to 12) (meth) acryloyl groups, and the like (2-1) Urethane-modified poly (meta) having at least 5 (specifically, about 5 to 30) (meth) acryloyl groups in the molecule, obtained by reacting the component with various known polyisocyanate compounds. ) Acrylate compound (2-2) (hereinafter referred to as component (2-2)). Be used in Germany, it may be used in combination of two or more thereof. In addition, although a commercial item can be used for (2) component, this is usually a composition in which a plurality of poly (meth) acrylate compounds having different numbers of (meth) acryloyl groups are mixed.

  Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylene diisocyanate, diphenylmethane-4,4-diisocyanate, 3-methyl-diphenylmethane diisocyanate, and 1,5. -Aromatic diisocyanate compounds such as naphthalene diisocyanate; alicyclic diisocyanate compounds such as dicyclohexylmethane diisocyanate and isophorone diisocyanate; aliphatic diisocyanate compounds such as hexamethylene diisocyanate; From the viewpoint of the weather resistance of the cured film, an alicyclic diisocyanate compound is preferred.

  Among the components (2), those having a molecular weight of about 550 to 10000 (preferably about 550 to 7000) and a hydroxyl value of about 0 to 60 mgKOH / g (preferably about 15 to 50 mgKOH / g) Particularly, it is preferable because it is excellent in compatibility with the component (1) and contributes to the antistatic property, transparency, hardness, scratch resistance and the like of the cured film.

  The component (3) is an optional component, and by using this together, the compatibility between the component (2) and the component (1) is further improved. As a result, the transparency of the active energy ray-curable resin composition according to the present invention is improved, and a cured film particularly excellent in antistatic properties, transparency, hardness, scratch resistance, and the like is obtained.

  As the component (3), for example, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, etc. Poly (meth) acrylates having four (meth) acryloyl groups (hereinafter referred to as component (3-1)), 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) ) Acrylate, neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate Di (meth) acrylates having two (meth) acryloyl groups in the molecule, such as dicyclopentadiene di (meth) acrylate and bisphenol A ethylene oxide-modified di (meth) acrylate, the components (a1) to (a4), Examples thereof include the hydroxyl group-containing vinyl monomers, and the component (3-1) is particularly preferable from the viewpoint of the compatibilizing action and the cured film performance (hardness, scratch resistance, etc.).

  The content of each component in the active energy ray-curable resin composition of the present invention is not particularly limited, but is usually as follows when the total amount of the composition is 100% by weight (in terms of solid content). . By using it in such an amount, the balance of antistatic property, hardness, scratch resistance, solvent resistance, etc. of the cured film becomes good.

<When using only (a1) component, (a2) component and (a3) component>
(1) Component: About 0.3 to 20% by weight (preferably 1 to 15% by weight)
Component (2) and Component (3): about 80 to 99.7% by weight (preferably 80 to 98% by weight)
<When (a1) component, (a2) component and (a3) component, and (a4) component are used>
(1) Component: 0.3 to 20% by weight
Component (2) and Component (3): 80 to 99.7% by weight
(4) Component: 0 to 15% by weight

  Moreover, when using together (2) component and (3) component, the usage-amount ratio in particular is not restrict | limited, However, When the sum total of both is 100 weight% normally, about 20-100 weight% in order, and 0 About 80% by weight. However, when considering the transparency of the obtained active energy ray-curable resin composition, the antistatic property of the cured film, transparency, hardness, scratch resistance, etc., preferably about 50 to 95% by weight, preferably 5 to 50% in order. It is about wt%.

  In the active energy ray-curable resin composition, the above-described organic solvent can be used as a dilution solvent in consideration of coating workability and the like. Among these, considering the surface smoothness of the cured film obtained from the composition, at least one selected from the group consisting of the glycol ethers, alcohols and ketones is preferable. Moreover, the solid content concentration of the active energy ray-curable resin composition after dilution is not particularly limited, but is usually about 1 to 60% by weight.

  In addition, the active energy ray-curable resin composition includes a photosensitizer, a surface conditioner, a surfactant, an ultraviolet absorber, an inorganic filler, a silane coupling agent, colloidal silica, an adhesion improver, and an antifoaming agent. Additives such as wetting agents, rust inhibitors and stabilizers can also be used.

The cured film of the present invention is obtained from the active energy ray-curable resin composition of the present invention. Specifically, for example, the composition is applied on various substrate films so that the weight after drying is about 0.05 to 30 g / m ² , preferably about 0.1 to 20 g / m ^2. After drying, it can be obtained by irradiating with active energy rays (ultraviolet rays or electron beams) and curing.

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

  Examples of the active energy rays include ultraviolet rays and electron beams. Examples of the ultraviolet light source include an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, and a metal halide lamp. In addition, conditions such as the amount of light, the light source, and the conveyance speed may be appropriately adjusted. For example, when a high-pressure mercury lamp is used, the amount of light is usually about 80 to 160 W / cm, and the conveyance speed is usually about 5 to 50 m / min. .

  The antistatic treatment film of the present invention has the cured film on at least one side of the base film.

  Examples of the base film include polycarbonate film, polyester film, polyolefin film, polystyrene film, epoxy resin film, melamine resin film, triacetyl cellulose film, ABS resin film, AS resin film, acrylic resin film, and alicyclic polyolefin. From among these, from the viewpoint of transparency and adhesion to a cured film, the resin film is selected from the group consisting of a polycarbonate film, a triacetyl cellulose film, an acrylic resin film, and an alicyclic polyolefin resin film. One type of film is preferred. Moreover, although the average thickness of a base film is not specifically limited, Usually, about 30-1000 micrometers, Preferably it is 30-200 micrometers.

  The cured film has an average film thickness of usually about 0.05 to 30 μm, preferably 0.1 to 20 μm.

  The pencil hardness (based on JIS K 5400, load 500 g) of the cured film surface of the antistatic treatment film is usually 2H or more.

  Further, the haze value of the antistatic treatment film is usually 0.4 or less, preferably 0.2 or less.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the examples, “%” and “part” mean “% by weight” unless otherwise specified.

  Moreover, the weight average molecular weight of (A) component is the actual value measured on condition of the following using a commercially available molecular weight measuring machine.

Molecular weight measuring instrument: Product name “HLC-8220GPC”, manufactured by Tosoh Corporation Column: Product name “TSKGel G6000PW _XL- CP”, “TSKGel G3000PW _XL- CP”, developed solvent manufactured by Tosoh Corporation: 0.1 M NaNO ₃ and 0.1 M acetic acid solution flow rate: 0.5 mL / min
Sample concentration: 0.5 g / L

<Synthesis of component (a2)>
Synthesis example 1
To a reactor equipped with a stirrer and a cooling tube, add 130 parts of hydroxyethyl methacrylate, 1140 parts of ε-caprolactone and 1.3 parts of tin octylate, raise the temperature to 150 ° C., incubate for 6 hours, cool, A polyester structure-containing monofunctional vinyl monomer (hereinafter referred to as the component (a2-1)) having a weight average molecular weight of about 5,500 was obtained. In addition, the said weight average molecular weight is a commercially available molecular weight measuring machine (Body product name "HLC-8220GPC", the Tosoh Corporation make; column product name "TSKGel G1000H", "TSKGel G2000H", the Tosoh Corporation make; developing solvent) Table 1 shows the composition and weight average molecular weight (hereinafter the same).

Synthesis example 2
In a reaction apparatus similar to Synthesis Example 1, 130 parts of hydroxyethyl methacrylate, 2280 parts of δ-valerolactone and 1.3 parts of tin octylate are added, the temperature is raised to 150 ° C., the temperature is kept for 6 hours, and then cooled. A polyester structure-containing monofunctional vinyl monomer having an average molecular weight of about 7400 (hereinafter referred to as “component (a2-2)”) was obtained.

Comparative Synthesis Example 1
In the same reactor as in Synthesis Example 1, 130 parts of hydroxyethyl methacrylate, 570 parts of ε-caprolactone and 0.7 parts of tin octylate were added, the temperature was raised to 150 ° C., the temperature was kept for 6 hours, cooled, and weight averaged A polyester structure-containing monofunctional vinyl monomer having a molecular weight of about 2900 (hereinafter referred to as component (b-1)) was obtained.

<Synthesis of component (A)>
Example 1
In the same reactor as in Synthesis Example 1, methacryloyloxyethyltrimethylammonium chloride (DMC) (hereinafter referred to as component (a1-1)) 100 parts, component (a2-1) 60 parts, tert-butyl methacrylate (t -BMA) (hereinafter referred to as component (a3-1)) and 40 parts of propylene glycol monomethyl ether (hereinafter referred to as PGM) were added, and the temperature was raised to 90 ° C. Next, 8 parts of 2,2′-azobis (methylbutyronitrile) (hereinafter referred to as AMBN) and 32 parts of PGM were added, the polymerization reaction was started, the mixture was kept at 100 ° C. for 6 hours and then cooled to contain a quaternary ammonium salt structure. A solution of polymer (A-1) (non-volatile content: 20%) was obtained.

Example 2
In the same reaction apparatus as in Synthesis Example 1, (a1-1) component 100 parts, (a2-1) component 60 parts, iso-butyl methacrylate (iso-BMA) (hereinafter referred to as (a3-2) component). 40 parts and 800 parts of PGM were added, and the temperature was raised to 90 ° C. Next, 8 parts of AMBN and 32 parts of PGM were added to initiate the polymerization reaction, and the mixture was kept at 100 ° C. for 6 hours and then cooled to obtain a solution of quaternary ammonium salt structure-containing polymer (A-2) (nonvolatile content 20%).

Example 3
In a reaction apparatus similar to Synthesis Example 1, 60 parts of (a1-1) component, 60 parts of (a2-1) component, 80 parts of (a3-1) component and 800 parts of PGM were added, and the temperature was raised to 90 ° C. Next, 8 parts of AMBN and 32 parts of PGM were added to initiate the polymerization reaction, and the mixture was kept at 100 ° C. for 6 hours and then cooled to obtain a solution of quaternary ammonium salt structure-containing polymer (A-3) (nonvolatile content: 20%).

Example 4
To the same reactor as in Synthesis Example 1, 60 parts of (a1-1) component, 60 parts of (a2-1) component, 80 parts of (a3-2) component and 800 parts of PGM were added, and the temperature was raised to 90 ° C. Next, 8 parts of AMBN and 32 parts of PGM were added to initiate the polymerization reaction, and the mixture was kept at 100 ° C. for 6 hours and then cooled to obtain a solution of quaternary ammonium salt structure-containing polymer (A-4) (nonvolatile content: 20%).

Example 5
120 parts of the (a1-1) component, 60 parts of the (a2-1) component, 20 parts of the (a3-1) component and 800 parts of PGM were added to the same reactor as in Synthesis Example 1, and the temperature was raised to 90 ° C. Next, 8 parts of AMBN and 32 parts of PGM were added to initiate the polymerization reaction, and the mixture was kept at 100 ° C. for 6 hours and then cooled to obtain a solution of quaternary ammonium salt structure-containing polymer (A-5) (nonvolatile content: 20%).

Example 6
120 parts of the (a1-1) component, 60 parts of the (a2-1) component, 20 parts of the (a3-1) component and 800 parts of PGM were added to the same reactor as in Synthesis Example 1, and the temperature was raised to 90 ° C. Next, 8 parts of AMBN and 32 parts of PGM were added to initiate the polymerization reaction, and the mixture was kept at 100 ° C. for 6 hours and then cooled to obtain a solution of a quaternary ammonium salt structure-containing polymer (A-6) (nonvolatile content: 20%).

Example 7
To the same reactor as in Synthesis Example 1, 100 parts of (a1-1) component, 60 parts of (a2-2) component obtained in Synthesis Example 2, 40 parts of (a3-1) component and 800 parts of PGM were added, and 90 ° C. The temperature was raised to. Next, 8 parts of AMBN and 32 parts of PGM were added to initiate the polymerization reaction, and the mixture was kept at 100 ° C. for 6 hours and then cooled to obtain a solution of quaternary ammonium salt structure-containing polymer (A-7) (nonvolatile content: 20%).

Comparative Example 1
100 parts of (a1-1) component, 60 parts of (a2-1) component, 40 parts of cyclohexyl methacrylate (hereinafter referred to as CHMA) and 800 parts of PGM are added to the same reactor as in Synthesis Example 1, and the temperature is raised to 90 ° C. did. Next, 8 parts of AMBN and 32 parts of PGM were added to initiate the polymerization reaction, and the mixture was kept at 100 ° C. for 6 hours and then cooled to obtain a solution of quaternary ammonium salt structure-containing polymer (α-1) (nonvolatile content: 20%).

Comparative Example 2
100 parts of the (a1-1) component, 60 parts of the (a2-1) component, 40 parts of tricyclodecane methacrylate (hereinafter referred to as TCDA) and 800 parts of PGM are added to the same reactor as in Synthesis Example 1, and the mixture is heated to 90 ° C. The temperature rose. Next, 8 parts of AMBN and 32 parts of PGM were added to initiate the polymerization reaction, and the mixture was kept at 100 ° C. for 6 hours and then cooled to obtain a solution of the quaternary ammonium salt structure-containing polymer (α-2) (nonvolatile content 20%).

Comparative Example 3
In a reaction apparatus similar to Synthesis Example 1, 100 parts of (a1-1) component, 60 parts of (b-1) component obtained in Comparative Synthesis Example 1, 40 parts of (a3-1) component and 800 parts of PGM were added, The temperature was raised to ° C. Next, 8 parts of AMBN and 32 parts of PGM were added to start the polymerization reaction, and the mixture was kept at 100 ° C. for 6 hours and then cooled to obtain a solution of quaternary ammonium salt structure-containing polymer (α-3) (nonvolatile content: 20%).

Comparative Example 4
50 parts of the component (a1-1), 60 parts of the component (a2-1), 90 parts of the component (a3-1) and 800 parts of PGM were added to the same reactor as in Synthesis Example 1, and the temperature was raised to 90 ° C. Next, 8 parts of AMBN and 32 parts of PGM were added to initiate the polymerization reaction, and the mixture was kept at 100 ° C. for 6 hours and then cooled to obtain a solution of quaternary ammonium salt structure-containing polymer (α-4) (nonvolatile content 20%).

Comparative Example 5
130 parts of the component (a1-1), 60 parts of the component (a2-1), 10 parts of the component (a3-1) and 800 parts of PGM were added to the same reactor as in Synthesis Example 1, and the temperature was raised to 90 ° C. Next, 8 parts of AMBN and 32 parts of PGM were added to initiate the polymerization reaction, and the mixture was kept at 100 ° C. for 6 hours and then cooled to obtain a solution of quaternary ammonium salt structure-containing polymer (α-5) (nonvolatile content: 20%).

<Preparation of active energy ray-curable resin composition>
Example 8
3 parts of an antistatic agent comprising a solution (A-1) component, dipentaerythritol polyacrylate (DPHA) (mixture of 5 and 6 (meth) acryloyl groups: Arakawa Chemical Industries ( Co., Ltd., trade name “KU-702”) 92 parts, and 1-hydroxy-cyclohexyl-phenyl ketone (BASF Japan, trade name “Irgacure 184”, hereinafter referred to as HCPK) 5 parts, Blended at a solid content ratio and diluted with methyl ethyl ketone (MEK), an active energy ray-curable resin composition having a nonvolatile content of 50% was prepared. Further, the compatibility (appearance) of the composition was evaluated by visual inspection immediately after the preparation of the paint and after being left at 25 ° C. and 50% for 2 weeks.

Examples 9-19, Comparative Examples 6-11
Regarding the components (A-2) to (α-5), an active energy ray-curable resin composition having a nonvolatile content of 50% was prepared under the conditions of the raw materials shown in Table 2 and the blending amounts shown in Table 3. Moreover, the compatibility of each composition was visually evaluated.

In Table 2, each symbol is as follows.
N: Meaning that a compound having the integer number of (meth) acryloyl groups is mixed Mw: Weight average molecular weight OHV: Hydroxyl value DPHA: Dipentaerythritol polyacrylate (trade name “KU-702”, Arakawa Chemical) Manufactured by Kogyo Co., Ltd.)
TPPA: Tripentaerythritol polyacrylate (trade name “Biscoat # 802”, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
PEUA: Urethane-modified polyacrylate mainly composed of pentaerythritol polyacrylate (trade name “KU-PEUA”, manufactured by Arakawa Chemical Industries, Ltd.)
DPUA: urethane-modified polyacrylate mainly composed of dipentaerythritol polyacrylate (trade name “KU-DPUA”, manufactured by Arakawa Chemical Industries, Ltd.)
PETA: Pentaerythritol polyacrylate (trade name “Biscoat # 300”, manufactured by Osaka Organic Chemical Industry Co., Ltd.)

In Table 3, the evaluation criteria for compatibility (immediately after being left for 2 weeks) are as follows.
○: Transparent ×: Cloudiness, complete separation

<Preparation of cured film and antistatic film>
Examples 20-31, Comparative Examples 12-17
The composition according to Example 8 was applied with a # 9 bar coater onto a 100 μm thick polyester film (trade name “COSMO SHINE A-4100” manufactured by Toyobo Co., Ltd.) (calculated value: film thickness 5 to 5). 6 μm), dried at 80 ° C. for 1 minute, and passed twice under air in a high-pressure mercury lamp (200 mJ / cm ² ) to produce an antistatic film with a cured film for Example 20. . Similarly, the antistatic treatment films for Examples 21 to 31 and Comparative Examples 12 to 17 were prepared for the compositions according to Examples 9 to 19 and Comparative Examples 6 to 11. The results are shown in Table 4.

[Various tests on cured film]
<Surface resistance test>
The surface resistance immediately after the production of the antistatic film according to Example 20 was applied in accordance with JIS K 6911 using a commercially available resistivity meter (product name “Hiresta MCP-HT-450” manufactured by Mitsubishi Chemical Corporation). Measurement was performed at a voltage of 500V. It measured similarly about the antistatic process film for Examples 21-31 and Comparative Examples 12-17. The results are shown in Table 4.

<Measurement of transparency>
The haze value of the antistatic film according to Example 20 was measured according to JIS K 5400 using a color haze meter manufactured by Murakami Color Research Laboratory. It measured similarly about the antistatic process film for Examples 21-31 and Comparative Examples 12-17. The results are shown in Table 4. In addition, each haze value is a numerical value including the haze value of the polyester film which is a base material.

<Abrasion resistance test>
The cured film of the antistatic film according to Example 20 was rubbed 50 times with a weight of steel wool (10 mm × 10 mm) attached to the bottom, and visually evaluated based on the appearance of the coating film, but no scratch was found. . The cured films of the antistatic treatment films for Examples 21 to 31 and Comparative Examples 12 to 17 were also tested in the same manner, but no difference occurred under these conditions. The results are shown in Table 4.

<Pencil hardness test>
The cured film of the antistatic treatment film according to Example 20 was evaluated by a pencil scratch test (based on JIS K 5400) with a load of 500 g. The cured films of the antistatic treatment films for Examples 21 to 31 and Comparative Examples 12 to 17 were also tested in the same manner, but no difference occurred under these conditions. The results are shown in Table 4.

Claims (15)

A vinyl monomer (a1) having a quaternary ammonium salt structure, a vinyl monomer (a2) formed by ring-opening polyaddition of a hydroxyl group-containing vinyl monomer and a lactone, and having a weight average molecular weight of 4000 to 10,000, and a carbon number A vinyl monomer (a3) having 3 to 5 branched alkyl ester groups and not having an alicyclic structure is such that the copolymerization ratio (weight ratio) is sequentially 30 to 60:15 to 35:20 to 40. An antistatic agent (1) for an active energy ray-curable resin composition, comprising a copolymer (A) obtained by reacting. The copolymer (A) further contains another vinyl monomer (a4) as a reaction component, and the copolymerization ratio (weight ratio) of the components (a1), (a2), (a3) and (a4) Are 30-60: 15-35: 20-40: 0-20 in order, The antistatic agent (1) for active energy ray hardening-type resin compositions of Claim 1 characterized by the above-mentioned. The antistatic agent (1) according to claim 1 or 2 , wherein the lactone is one selected from the group consisting of ε-caprolactone and δ-valerolactone. The antistatic agent (1) according to any one of claims 1 to 3, comprising poly (meth) acrylates (2) having at least 5 (meth) acryloyl groups in the molecule and a reactive diluent (3), An active energy ray-curable resin composition. (2) The active energy ray-curable resin composition according to claim 4, wherein the component has a weight average molecular weight of 550 to 10,000 and a hydroxyl value of 0 to 60 mgKOH / g. The active energy ray-curable resin composition according to any one of claims 4 to 5, wherein the contents of the component (1), the component (2), and the component (3) are as follows.
(1) Component: 0.3 to 20% by weight
Component (2) and Component (3): 80 to 99.7% by weight The photopolymerization initiator (4) is further contained, and the contents of the components (1), (2) and (3), and (4) are as follows: Active energy ray-curable resin composition.
(1) Component: 0.3 to 20% by weight
Component (2) and Component (3): 80 to 99.7% by weight
(4) Component: 0 to 15% by weight The amount ratio of the component (2) and the component (3) is about 50 to 95% by weight and about 5 to 50% by weight when the total of both is 100% by weight . Any active energy ray-curable resin composition. A cured film obtained from the active energy ray-curable resin composition according to any one of claims 4 to 8 . An antistatic optical film having the cured film of claim 9 on at least one surface of a base film. The antistatic optical film according to claim 10 , wherein the base film is one selected from the group consisting of a polyester film, a triacetyl cellulose film, a polycarbonate film, an acrylic resin film, and an alicyclic polyolefin resin film. The antistatic optical film according to claim 10 or 11 , wherein the base film has an average thickness of 30 to 1000 µm. Any of the antistatic treatment optical film of claims 10 to 12 Average thickness of the cured film is 0.05～30Myuemu. The antistatic optical film according to any one of claims 10 to 13 , wherein the cured film surface has a pencil hardness (based on JIS K 5400, load 500g) of 2H or more. The antistatic treatment optical film according to any one of claims 10 to 14 , wherein the film having a cured film has a haze value of 0.4 or less.