JP2017031336A - Active energy ray-curable composition and film using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray-curable composition giving an excellent appearance of a coating material and having high storage stability, from which a cured coating film achieving both of an excellent appearance of the coating film and high antistatic property can be formed, and a film using the above composition.SOLUTION: The active energy ray-curable composition comprises: an active energy ray-curable compound (A); a metal oxide (B) having conductivity and having a layer treated with a hydrolyzable organic silicon compound on a particle surface; and an organic solvent (C) having a Hansen solubility parameter in which a dispersion term (δD) ranges from 15.6 to 16.1 MPa, a polarity term (δP) ranges from 7.2 to 9.8 MPa, and a hydrogen bond term (δH) ranges from 8.2 to 11.4 MPa.SELECTED DRAWING: None

Description

  The present invention is excellent in storage stability and has an excellent coating film appearance by coating and curing on the surface of the film, and an activity capable of forming a cured coating film having high antistatic properties on the film surface. The present invention relates to an energy beam curable composition and a film using the same.

  Various resin films include scratch prevention films on the surface of flat panel displays (FPD) such as liquid crystal displays (LCD), organic EL displays (OLED), plasma displays (PDP), decorative films (sheets) for interior and exterior of automobiles, It is used for various applications such as low reflection film for windows and heat ray cut film. However, since the resin film surface is soft and has low scratch resistance, a hard coat layer made of a UV curable composition or the like may be applied to the film surface and cured to provide a hard coat layer on the film surface in order to compensate for this. Generally done. The outline of the process of providing the hard coat layer is sent from the film roll wound in a roll to the coating machine, the hard coat material is applied, cured by ultraviolet irradiation to form the hard coat layer, and again It is wound up into a roll.

  In this winding process, static electricity is generated on the film surface due to the friction between the films. Therefore, when the film is unwound from the roll during reprocessing, the film surface sticks to the film surface, and dust tends to adhere to the film surface due to static electricity. There was a problem. Further, when this film is used for a liquid crystal display or the like, there is a problem that the display malfunctions due to generated static electricity.

  In order to suppress the generation of static electricity on the film surface, a method of adding an antistatic agent to the hard coat material is generally performed. For example, a method of blending metal oxide particles such as tin oxide into a hard coat material as an antistatic agent has been proposed (see, for example, Patent Documents 1 and 2). However, the hard coat material containing these metal oxide particles reduces the viscosity, and when the organic solvent content is increased, the dispersion state of the metal oxide particles changes and agglomeration occurs, resulting in a cured coating film. There was a problem that the surface resistance of the film increased and the surface resistance increased.

  Accordingly, there has been a demand for an active energy ray-curable composition that can form a hard coat layer that achieves both excellent coating film appearance and high antistatic properties.

JP 2002-294100 A JP 2007-23107 A

  The problem to be solved by the present invention is an active energy ray that has excellent coating material appearance, high storage stability, and can form a cured coating film having both excellent coating film appearance and high antistatic properties. It is to provide a curable composition and a film using the same.

  As a result of diligent research to solve the above-mentioned problems, the present inventors have applied an active energy ray-curable composition by blending an organic solvent in which three parameters in the Hansen solubility parameter are each in a specific range. The inventors have found that a hard coat layer having both a film appearance and a high antistatic property can be formed, and the present invention has been completed.

That is, the present invention relates to an active energy ray-curable compound (A), a metal oxide (B) having a treatment layer of a hydrolyzable organosilicon compound on the particle surface and conductivity, and dispersion with a Hansen solubility parameter. The term (δD) is in the range of 15.6 to 16.1 MPa ^0.5 , the polarization term (δP) is in the range of 7.2 to 9.8 MPa ^0.5 , and the hydrogen bond term (δH) is 8. An active energy ray-curable composition containing an organic solvent (C) in the range of 2 to 11.4 MPa ^0.5 and a film using the same are provided.

  The active energy ray-curable composition of the present invention can form a cured coating film having an excellent coating film appearance and high antistatic properties on the film surface by coating and curing on the film surface. . Therefore, the cured coating film of the active energy ray-curable composition of the present invention can suppress the generation of static electricity on the film surface without impairing the flat appearance of the film. Therefore, functions such as sticking prevention and adhesion of dust due to static electricity can be imparted to various films. Therefore, the film having a cured coating film of the active energy ray-curable composition of the present invention is environmentally friendly, and troubles such as sticking and adhesion of dust, etc. when winding up into a roll or unwinding from the roll. Therefore, a film excellent in subsequent handling can be provided.

  Moreover, the film which has a cured coating film of the active energy ray curable composition of this invention is a damage | wound of flat panel displays (FPD) surfaces, such as a liquid crystal display (LCD), an organic electroluminescent display (OLED), and a plasma display (PDP). It can be used in various applications such as a film for preventing sticking, a protective film for a touch panel, a decorative film (sheet) for automobile interior and exterior, a low reflection film for windows, and a heat ray cut film. Furthermore, since it has excellent antistatic properties when used in these applications, adhesion of dust and the like can be suppressed. Furthermore, when this film is used for a liquid crystal display or the like, malfunction of the display due to generated static electricity can be prevented.

The active energy ray-curable composition of the present invention includes an active energy ray-curable compound (A), a metal oxide (B) having a treatment layer of a hydrolyzable organosilicon compound on the particle surface, and conductivity. The dispersion term (δD) in the Hansen solubility parameter is in the range of 15.6 to 16.1 MPa ^0.5 , the polarization term (δP) is in the range of 7.2 to 9.8 MPa ^0.5 , and the hydrogen bond term (ΔH) contains an organic solvent (C) in the range of 8.2 to 11.4 MPa ^0.5 .

  Examples of the active energy ray-curable compound (A) include polyfunctional (meth) acrylate (A1) and urethane (meth) acrylate (A2). These can be used alone or in combination of two or more.

  In the present invention, “(meth) acrylate” refers to one or both of acrylate and methacrylate, and “(meth) acryloyl” refers to one or both of acryloyl and methacryloyl.

  The polyfunctional (meth) acrylate (A1) is a compound having two or more (meth) acryloyl groups in one molecule. Specific examples of the polyfunctional (meth) acrylate (a1) include 1,4-butanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, and 1,6-hexanediol. Di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate , Tricyclodecane dimethanol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, etc. Di (meth) acrylate of dihydric alcohol, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, di (meth) acrylate of tris (2-hydroxyethyl) isocyanurate, 4 moles per mole of neopentyl glycol Di (meth) acrylate of diol obtained by adding ethylene oxide or propylene oxide as described above, di (meth) acrylate of diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A, trimethylolpropane Tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, ditri Tyrolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Examples include tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. These polyfunctional (meth) acrylates (A1) can be used alone or in combination of two or more. Among these polyfunctional (meth) acrylates (A1), since the scratch resistance of the cured coating film of the active energy ray-curable composition of the present invention is improved, dipentaerythritol hexa (meth) acrylate, di Pentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, and pentaerythritol tri (meth) acrylate are preferred.

  The urethane (meth) acrylate (A2) is obtained by reacting a polyisocyanate (a2-1) with a (meth) acrylate (a2-2) having a hydroxyl group.

  Examples of the polyisocyanate (a2-1) include aliphatic polyisocyanates and aromatic polyisocyanates, but since the coloring of the cured coating film of the active energy ray-curable composition of the present invention can be reduced, aliphatic polyisocyanates. Isocyanates are preferred.

  The aliphatic polyisocyanate is a compound in which a portion excluding an isocyanate group is composed of an aliphatic hydrocarbon. Specific examples of the aliphatic polyisocyanate include aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate; norbornane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanato). And cycloaliphatic polyisocyanates such as methyl) cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane and 2-methyl-1,5-diisocyanatocyclohexane. A trimerized product obtained by trimming the aliphatic polyisocyanate or the alicyclic polyisocyanate can also be used as the aliphatic polyisocyanate. Moreover, these aliphatic polyisocyanates can be used alone or in combination of two or more.

  Among the aliphatic polyisocyanates, in order to improve the scratch resistance of the coating film, among the aliphatic polyisocyanates, hexamethylene diisocyanate, which is a linear aliphatic hydrocarbon diisocyanate, norbornane diisocyanate, which is an alicyclic diisocyanate, isophorone Diisocyanate is preferred.

  The (meth) acrylate (a2-2) is a compound having a hydroxyl group and a (meth) acryloyl group. Specific examples of the (meth) acrylate (a2-2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth). Divalent compounds such as acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, and hydroxypivalate neopentyl glycol mono (meth) acrylate Mono (meth) acrylate of alcohol; trimethylolpropane di (meth) acrylate, ethylene oxide (EO) modified trimethylolpropane (meth) acrylate, propylene oxide (PO) modified trimethylolpropane di (meta) Mono- or di (meth) acrylate of a trivalent alcohol such as acrylate, glycerin di (meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, or a part of these alcoholic hydroxyl groups Mono- and di (meth) acrylates having hydroxyl groups modified with ε-caprolactone; monofunctional hydroxyl groups such as pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and 3 A compound having a functional (meth) acryloyl group or a polyfunctional (meth) acrylate having a hydroxyl group obtained by further modifying the compound with ε-caprolactone; dipropylene glycol mono (meth) acrylate, diethylene group (Meth) acrylates having an oxyalkylene chain such as coal mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate; polyethylene glycol-polypropylene glycol mono (meth) acrylate, polyoxybutylene-poly (Meth) acrylate having an oxyalkylene chain having a block structure such as oxypropylene mono (meth) acrylate; poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono (meth) And (meth) acrylate having an oxyalkylene chain having a random structure such as acrylate. These (meth) acrylates (a2-2) can be used alone or in combination of two or more.

  Among the urethane (meth) acrylate (A2), since it can improve the scratch resistance of the cured coating film of the active energy ray-curable composition of the present invention, it has four or more (meth) acryloyl groups in one molecule. Those are preferred. Since the urethane (meth) acrylate (A2) has four or more (meth) acryloyl groups in one molecule, the (meth) acrylate (a2-2) has 2 (meth) acryloyl groups. Those having at least two are preferred. Examples of such (meth) acrylate (a2-2) include trimethylolpropane di (meth) acrylate, ethylene oxide-modified trimethylolpropane di (meth) acrylate, propylene oxide-modified trimethylolpropane di (meth) acrylate, Glycerin di (meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. Can be mentioned. These (meth) acrylates (a2-2) can be used alone or in combination of two or more thereof with respect to one of the aliphatic polyisocyanates. Among these (meth) acrylates (a2-2), pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferable because they can improve scratch resistance.

  The reaction of the polyisocyanate (a2-1) and the (meth) acrylate (a2-2) can be carried out by a conventional urethanization reaction. Moreover, in order to accelerate | stimulate progress of a urethanation reaction, it is preferable to perform a urethanation reaction in presence of a urethanization catalyst. Examples of the urethanization catalyst include amine compounds such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine; phosphorus compounds such as triphenylphosphine and triethylphosphine; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin Examples thereof include organic tin compounds such as diacetate and tin octylate, and organic zinc compounds such as zinc octylate.

  Moreover, as needed, as active energy ray-curable compound (A) other than said polyfunctional (meth) acrylate (A1) and urethane (meth) acrylate (A2), epoxy (meth) acrylate, polyester (meth) An acrylate, a polyether (meth) acrylate, etc. can be used. Examples of the epoxy (meth) acrylate include those obtained by reacting (meth) acrylic acid with bisphenol-type epoxy resin, novolac-type epoxy resin, polyglycidyl methacrylate and the like and esterifying it. Moreover, as said polyester (meth) acrylate, (meth) acrylic acid is made to react and esterify with the polyester which the both terminal obtained by polycondensation of polyhydric carboxylic acid and polyhydric alcohol is a hydroxyl group, for example. Or a product obtained by reacting (meth) acrylic acid with ester obtained by adding an alkylene oxide to a polyvalent carboxylic acid. Furthermore, as said polyether (meth) acrylate, what was obtained by reacting (meth) acrylic acid with polyether polyol and esterifying is mentioned, for example.

  The metal oxide (B) has conductivity and antistatic properties. Specifically, tin oxide, antimony doped tin oxide, phosphorus doped tin oxide, fluorine doped tin oxide, zinc oxide, zinc dioxide, fluorine doped zinc oxide, aluminum doped zinc oxide, boron doped zinc oxide, gallium doped zinc oxide, indium oxide , Tin-doped indium oxide, zinc oxide-doped indium oxide, tin and gallium-doped indium oxide, and the like. Among these, antimony-doped tin oxide is preferable because antistatic properties can be further improved.

  Moreover, since the dispersion stability in the active energy ray curable composition of this invention can be improved more, the said metal oxide (B) uses what processed the particle | grain surface with the hydrolyzable organosilicon compound.

  The metal oxide (B) is usually fine particles. The average particle diameter is preferably in the range of 2 to 50 nm, more preferably in the range of 5 to 40 nm, and still more preferably in the range of 4 to 10 nm. The fine particles of the metal oxide (B) are preferably connected in a chain of 2 to 10 in the coating material. If the average particle diameter of the metal oxide (B) fine particles is within the above range, the fine particles are more difficult to aggregate, and therefore the surface resistance value of the cured coating film obtained can be further reduced. Moreover, the transparency of the cured coating film obtained can also be improved. In addition, the average particle diameter in this invention is calculated | required from the result measured by the dynamic light scattering method.

  As a hydrolysable organosilicon compound used for manufacture of the said metal oxide (B), the compound of the structure represented by following General formula (1) is mentioned, for example.

（式中、Ｒ^１〜Ｒ^４は、それぞれ独立して、水素原子、ハロゲン原子、アルキル基、アルコキシ基、アミノ基、ビニル基、アリル基、アシル基、（メタ）アクリロイルオキシ基、アリール基、グリシジル基、又はＣＨ_２ＯＣ_ｎＨ_２ｎ＋１（ｎ＝１〜４）を表し、Ｒ^１〜Ｒ^４のうち、少なくとも１つはハロゲン原子又はアルコキシ基である。）

(In the formula, R ^{1 to} R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an amino group, a vinyl group, an allyl group, an acyl group, a (meth) acryloyloxy group, an aryl group, A glycidyl group or CH ₂ OC _n H _{2n + 1} (n = 1 to 4) is represented, and at least one of R ^{1 to} R ⁴ is a halogen atom or an alkoxy group.)

In the above general formula (1), when R ^{1 to} R ⁴ are halogen atoms, a chloro group is preferable, an aryl group is preferably a phenyl group, and an alkyl group or an alkoxy group has 1 to 10 carbon atoms. Those are preferred.

  Next, in order to treat the metal oxide particle surface with a hydrolyzable organosilicon compound, first, an aqueous dispersion of metal oxide fine particles is prepared by the following method.

(I) Preparation of aqueous dispersion of metal oxide fine particles First, an aqueous dispersion of the metal oxide fine particles is prepared. The concentration of the metal oxide fine particle aqueous dispersion at this time is not particularly limited, but is usually preferably in the range of 1 to 40% by mass, more preferably in the range of 10 to 40% by mass.

  Next, the pH of the aqueous dispersion of metal oxide fine particles is adjusted to 2 to 5, preferably 2.5 to 4. As a method for adjusting the pH, an ion exchange treatment using an ion exchange resin is preferable. Furthermore, you may add an acid as needed.

  As the ion exchange resin, an H-type cation exchange resin is preferable. The pH is shifted to acidic by the ion exchange treatment. In addition, since the pH may not be sufficiently lowered only by the ion exchange resin treatment, it is preferable to add an acid as necessary.

  In addition, even if only an acid is added, without performing an ion exchange process, pH can be adjusted to the said range. When ion exchange treatment is performed, deionization is also performed, so that chain-shaped metal oxide fine particles are easily obtained. In addition, by adjusting the pH within the above range, the aggregation of metal oxide fine particles can be suppressed, and when a hydrolyzable organosilicon compound is added, the formation of spherical aggregated particles can be suppressed. Fine particles can be easily obtained, and the coating film appearance and antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be improved.

  After the pH adjustment, the content ratio of the metal oxide fine particles in the aqueous dispersion is adjusted to 10 to 40% by mass, preferably 15 to 35% by mass by concentration or dilution.

  By making the content ratio of the metal oxide fine particles in the aqueous dispersion within the above range, the metal oxide fine particles are easily connected (chained), and the hydrolyzable organosilicon compound described later is oxidized by metal. It can be adsorbed uniformly on the surface of the fine particles.

(Ii) Addition of organosilicon compound Next, the hydrolyzable organosilicon compound represented by the general formula (1) is added to an aqueous dispersion of metal oxide fine particles having conductivity adjusted in concentration. Examples of such hydrolyzable organosilicon compounds include tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, methyltripropoxysilane, and ethyltrimethoxysilane. Methoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, phenyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane , Γ-chloropropyltriethoxysilane, γ-chloropropyltripropoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrie Trialkoxysilanes or triacyloxysilanes such as toxisilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane Dimethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, dimethyldiacetoxysilane, Dialkoxysilanes or diacids such as γ-methacryloxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane Rusilane; trimethylchlorosilane and the like. These hydrolyzable organosilicon compounds can be used alone or in combination of two or more.

  The amount of the hydrolyzable organosilicon compound used varies depending on the type of hydrolyzable organosilicon compound, the particle size of the metal oxide fine particles, etc., but the mass ratio between the metal oxide fine particles and the hydrolyzable organosilicon compound ( The hydrolyzable organosilicon compound / metal oxide fine particles) is preferably in the range of 0.01 to 0.5, and more preferably in the range of 0.02 to 0.3.

  When the mass ratio between the conductive metal oxide fine particles and the hydrolyzable organosilicon compound is within the above range, the chain-connected particles are chained in the active energy ray-curable composition. It is possible to maintain a state of being connected in a shape and to maintain a good dispersion state. For this reason, the transparency and antistatic property of the obtained cured coating film can be further improved.

As the hydrolyzable organosilicon compound, it is preferable to use one in which three or four of R ^{1 to} R ^{4 in} the general formula (1) are alkoxy groups. Among R ^{1 to} R ^{4 in} the general formula (1), four hydrolyzable organosilicon compounds, which are alkoxy groups, are effective in maintaining the connection of the metal oxide fine particles, and the general formula (1) Hydrolyzable organosilicon compounds in which three of R ^{1 to} R ⁴ are alkoxy groups are effective in improving the dispersibility of the chain metal oxide fine particles in the active energy ray-curable composition. It is.

In addition, as the hydrolyzable organosilicon compound, it is preferable that ^four of R ^{1 to} R ^{4 in} the general formula (1) are an alkoxy group and three are alkoxy groups. When this combination is used, when 4 are alkoxy groups, the molar ratio of 3 to alkoxy groups (alkoxy group = 4 / alkoxy group = 3) is preferably in the range of 80/20 to 20/80, The range of 70/30 to 30/70 is more preferable. Within this range, chain-shaped metal oxide fine particles can be efficiently prepared.

When the hydrolyzable organosilicon compound is added to the aqueous dispersion of metal oxide fine particles and hydrolyzed as described above, chain metal oxide fine particles that are strongly bonded can be prepared. Although the reason for this is not clear, the bonding part of the particles is highly active, so that among R ^{1 to} R ^{4 in} the general formula (1), ^four of them are easily adsorbed and hydrolyzed. It is considered that hydrolysis proceeds simultaneously with the addition of alcohol. In this case, a large amount of Si—OH is produced, and among R ^{1 to} R ^{4 in} the general formula (1), three are alkoxy groups, which have low solubility in water. dissolved to to hydrolysis proceeds, of the general formula ⁽¹⁾ R 1 ~R ⁴ in hydrolyzed by adhering the joint portion of the previously particles, the Si-OH but four is a alkoxy group Thereafter, it is considered that three of R ^{1 to} R ^{4 in} the general formula (1) react with each other, which is an alkoxy group.

Therefore, among hydrolyzable organosilicon compounds, among R ^{1 to} R ^{4 in} the general formula (1), four are alkoxy groups, and among R ^{1 to} R ^{4 in} the general formula (1) In the case where three of them are used together with an alkoxy group, first, among R ^{1 to} R ^{4 in} the general formula (1), ^four of which are alkoxy groups are added to the dispersion, and then the alcohol is added. It is preferable to add and hydrolyze those in which three of R ^{1 to} R ^{4 in} the general formula (1) are alkoxy groups.

  Next, alcohol is added to dilute, and the non-volatile content ratio (total non-volatile content including hydrolyzable organosilicon compound, hydrolyzable organosilicon compound is converted to silica) is 3 to 30% by mass, and further 5 to 25% by mass. It adjusts so that it may become a range, and hydrolyzes a hydrolysable organosilicon compound.

  Examples of the alcohol include methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, and butanol. In addition to these alcohols, organic solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether may be mixed and used.

  The temperature at which the hydrolyzable organosilicon compound is hydrolyzed is preferably in the range of 30 ° C. to the boiling point of the solvent used (approximately 100 ° C.) because hydrolysis can be efficiently performed and aggregation of particles can be suppressed. More preferably, the temperature is in the range of 40 ° C. to the boiling point of the solvent used.

  Moreover, when hydrolyzing a hydrolysable organosilicon compound, you may add an acid as a catalyst as needed. Examples of the acid include hydrochloric acid, nitric acid, acetic acid, phosphoric acid, and the like.

  Since the conductive metal oxide (B) fine particles treated with the hydrolyzable organosilicon compound obtained as described above can further improve the antistatic property of the resulting cured coating film, What the average connection number of the particle | grains becomes the range of 3-20 is preferable, and what becomes the range of 5-20 is more preferable.

  Further, the obtained aqueous dispersion of metal oxide fine particles can be used as it is for the preparation of the active energy ray-curable composition, but can be washed or deionized as necessary. When the ion concentration is reduced by deionization or the like, an aqueous dispersion of metal oxide fine particles having more excellent stability can be obtained. This deionization treatment can be performed using a known cation exchange resin, anion exchange resin, or both ion exchange resins. For the washing, an ultrafiltration membrane method or the like can be used.

  Furthermore, the obtained aqueous dispersion of metal oxide fine particles can be used after replacing water with a solvent as required. When solvent substitution is performed, the dispersibility in the active energy ray-curable composition described later is further improved and the coating property is excellent, so that it is smooth, free from streaks and unevenness, high in transparency, and antistatic. An excellent cured coating film can be obtained.

On the other hand, if necessary, water can be added to the obtained aqueous dispersion of metal oxide fine particles. When water is added, the number of linked metal oxide fine particles is increased, the antistatic property of the resulting cured coating film can be remarkably improved, and a cured coating film having a surface resistance value of 10 ² to 10 ¹² Ω / □ is obtained. Can do.

  As described above, when adding water to the obtained aqueous dispersion of metal oxide fine particles, after adding water, after storing at room temperature (about 5 to 35 ° C.) for about 1 to 48 hours, By using for an active energy ray curable composition, the cured coating film which was more excellent in antistatic property can be obtained.

  The content of the metal oxide (B) in the active energy ray-curable composition can improve the appearance, antistatic property, and transparency of the resulting cured coating film, so that the non-volatile content is 0. The range of 01-50 mass% is preferable, and the range of 1-30 mass% is more preferable.

The organic solvent (C) has a dispersion term (δD) in the Hansen solubility parameter in the range of 15.6 to 16.1 MPa ^0.5 and a polarization term (δP) of 7.2 to 9.8 MPa ^0.5. The hydrogen bond term (δH) is in the range of 8.2 to 11.4 MPa ^0.5 .

  Here, the Hansen solubility parameter is a three-dimensional space obtained by dividing the solubility parameter introduced by Hildebrand into three components: a dispersion term (δD), a polarization term (δP), and a hydrogen bond term (δH). It is shown in The dispersion term (δD) indicates the effect due to the dispersion force, the polarization term (δP) indicates the effect due to the force between the dipoles, and the hydrogen bond term (δH) indicates the effect due to the hydrogen bond force.

  The definition and calculation of Hansen solubility parameters are described in Charles M. et al. Hansen, “Hansen Solubility Parameters; A Users Handbook (CRC Press, 2007)”. Further, by using the computer software “Hansen Solubility Parameters in Practice (HSPiP)”, the Hansen solubility parameter can be estimated from the chemical structure of an organic solvent whose parameter value is not described in the literature. In the present invention, the value is used for an organic solvent whose parameter value is described in the literature, and the parameter value estimated using HSPiP version 4.1.06 is used for the organic solvent whose parameter value is not described in the literature. Use.

  The organic solvent (C) can be used as one kind of organic solvent or can be used as a mixed solvent in combination of two or more kinds of organic solvents. When using 2 or more types together, the value which carried out the weighted average of three parameters of the Hansen solubility parameter of each organic solvent can be used in the said range.

When the dispersion term (δD) is larger than the upper limit of 16.1 MPa ^0.5 among the Hansen solubility parameters of the organic solvent (C), the storage stability of the coating material tends to be lowered. On the other hand, when the polarization term (δP) is smaller than the lower limit of 7.2 MPa ^0.5 , the coating material becomes cloudy and the appearance of the coating material deteriorates, the surface resistance value of the cured coating film increases, and the antistatic property decreases. Tend. When the hydrogen bond term (δH) is larger than the upper limit of 11.4 MPa ^0.5 , the cured coating film tends to be whitened and the surface resistance value tends to be slightly higher.

When two or more organic solvents are used in combination as the organic solvent (C), a method for adjusting the Hansen solubility parameter range is, for example, ethanol (δD = 15.8 MPa ^0.5 , δP = 8 .8MPa ^0.5, δH = 19.4MPa ^0.5) and an alcohol solvent such as methyl ethyl ketone ^{(δD = 16.0MPa 0.5, δP =} 9.0MPa 0.5, δH = 5.1MPa 0.5) A combination with a ketone solvent such as In addition to combination with the alcohol solvent and a ketone solvent, further diacetone alcohol ^{(δD = 15.8MPa 0.5, δP =} 8.2MPa 0.5, δH = 10.8MPa 0.5), acetylacetone ([delta] D ^{= 16.1MPa 0.5, δP = 10.0MPa 0.5} , δH = 6.2MPa 0.5), dimethyl carbitol ^{(δD = 15.7MPa 0.5, δP =} 6.1MPa 0.5, δH = 6.5 MPa ^0.5), propylene glycol monomethyl ether acetate ^{(δD = 15.6MPa 0.5, δP =} 5.6MPa 0.5, δH = 9.8MPa 0.5) or the like having a boiling point of 100 to 180 ° C. of By containing a high boiling point solvent in the organic solvent (C) in an amount of 3 to 40% by mass, the cured coating film is prevented from cracking, and the coating film appearance is excellent. Preferable since it can Rukoto.

  Moreover, the active energy ray curable composition of this invention can be made into a cured coating film by irradiating an active energy ray after coating to a base material. The active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When irradiating ultraviolet rays as active energy rays to form a cured coating film, it is preferable to add a photopolymerization initiator (D) to the active energy ray curable composition of the present invention to improve curability. Further, if necessary, a photosensitizer (E) can be further added to improve curability. On the other hand, in the case of using ionizing radiation such as electron beam, α ray, β ray, γ ray, etc., since it cures quickly without using a photopolymerization initiator (D) or photosensitizer (E), It is not necessary to add a photopolymerization initiator (D) or a photosensitizer (E).

  Examples of the photopolymerization initiator (D) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo {2-hydroxy-2-methyl-1- [4- ( 1-methylvinyl) phenyl] propanone}, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy -2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Acetophenone compounds such as butanone; benzoin, benzoin methyl ether, benzoy Benzoin compounds such as isopropyl ether; acylphosphine oxide compounds such as 2,4,6-trimethylbenzoin diphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; benzyl (dibenzoyl) and methylphenyl Benzylic compounds such as glyoxyester, oxyphenylacetic acid 2- (2-hydroxyethoxy) ethyl ester, oxyphenylacetic acid 2- (2-oxo-2-phenylacetoxyethoxy) ethyl ester; benzophenone, methyl o-benzoylbenzoate -4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3 ', , 4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone and other benzophenone compounds; 2-isopropylthioxanthone, Thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-dichlorothioxanthone; Aminobenzophenone compounds such as Michler's ketone and 4,4'-diethylaminobenzophenone; 10-butyl-2- Chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, 1- [4- (4-benzoylphenylsulfanyl) phenyl] -2-methyl-2- (4-methylphenylsal Fonyl) Propan-1-one etc. are mentioned. These photopolymerization initiators (D) can be used alone or in combination of two or more.

  Examples of the photosensitizer (E) include tertiary amine compounds such as diethanolamine, N-methyldiethanolamine, and tributylamine, urea compounds such as o-tolylthiourea, sodium diethyldithiophosphate, and s-benzylisothiuro. And sulfur compounds such as nitro-p-toluenesulfonate.

  The photopolymerization initiator (D) and the photosensitizer (E) are used in the active energy ray-curable compound (A) and the compound (B) in the active energy ray-curable composition of the present invention. 0.05 to 20 parts by mass is preferable and 100 to 10% by mass is more preferable.

  In the active energy ray-curable composition of the present invention, in addition to the active energy ray-curable compound (A) and the resin (B) having a quaternary ammonium salt, a polymerization inhibitor, Surface conditioner, antistatic agent, antifoaming agent, viscosity modifier, light stabilizer, weathering stabilizer, heat stabilizer, UV absorber, antioxidant, leveling agent, organic pigment, inorganic pigment, pigment dispersant, silica Additives such as beads and organic beads; inorganic fillers such as silicon oxide, aluminum oxide, titanium oxide, zirconia, and antimony pentoxide can be blended. These other blends can be used alone or in combination of two or more.

  The material of the base film used in the film of the present invention is preferably a highly transparent resin, for example, a polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; polypropylene, polyethylene, polymethylpentene-1 Polyolefin resins such as cellulose acetate (diacetyl cellulose, triacetyl cellulose, etc.), cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, cellulose acetate phthalate, cellulose nitrate and other cellulose resins; poly Acrylic resins such as methyl methacrylate; Vinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride; Polyvinyl alcohol; Ethylene-vinyl acetate Polystyrene; Polyamide; Polycarbonate; Polysulfone; Polyethersulfone; Polyetheretherketone; Polyimide resin such as polyimide and polyetherimide; Norbornene resin (for example, “ZEONOR” manufactured by ZEON Corporation), modified Examples include norbornene resins (for example, “Arton” manufactured by JSR Corporation), cyclic olefin copolymers (for example, “Appel” manufactured by Mitsui Chemicals, Inc.), and the like. Furthermore, you may use what bonded together 2 or more types of base materials which consist of these resin.

  Moreover, the said base film may be a film form or a sheet form, and the thickness has the preferable range of 10-500 micrometers. Moreover, when using a film-like base film, the thickness has the preferable range of 15-200 micrometers, The range of 20-150 micrometers is more preferable, The range of 25-100 micrometers is further more preferable. By setting the thickness of the film substrate within the above range, curling can be easily suppressed even when a cured coating film is provided on one side of the film with the active energy ray-curable composition of the present invention.

  The film of the present invention is obtained by applying the active energy ray-curable composition of the present invention to at least one surface of the film and then irradiating the active energy ray to form a cured coating film. . Examples of a method for applying the active energy ray-curable composition of the present invention to a film include die coating, micro gravure coating, gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, dip coating, and spinner coating. , Brush coating, silk screen solid coating, wire bar coating, flow coating, and the like.

  In addition, the active energy ray-curable composition of the present invention is heated or dried at room temperature in order to volatilize the organic solvent (C) after being applied to the base film and before irradiation with the active energy ray. Is preferred. The conditions for heat drying are not particularly limited as long as the organic solvent volatilizes. Usually, the temperature is 50 to 100 ° C. and the time is 0.5 to 10 minutes. preferable.

  In addition, as a device for irradiating ultraviolet rays to cure the active energy ray-curable composition, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, an electrodeless lamp (fusion lamp), a chemical Lamp, black light lamp, mercury-xenon lamp, short arc lamp, helium / cadmium laser, argon laser, sunlight, LED lamp, and the like.

  The film having a cured coating film of the active energy ray-curable composition of the present invention is applicable to various applications because of its excellent anti-blocking property and excellent scratch resistance on its surface. ) And an optical film used for an image display unit of an image display device such as an organic EL display (OLED). In particular, since it has excellent scratch resistance even if it is thin, for example, electronic notebooks, mobile phones, smartphones, portable audio players, mobile personal computers, tablet terminals, etc. It can use suitably as an optical film of the image display part of this image display apparatus. Moreover, when using as an optical film, it can use as a protective film used for the outermost surface of the image display part of an image display apparatus, and a base material of a touch panel. Furthermore, when used as a protective film, for example, in an image display device having a configuration in which a transparent panel for protecting the image display module is provided on the upper part of an image display module such as an LCD module or an OLED module, the transparent panel By sticking to the front or back surface of the plate, it is effective for preventing damage and preventing scattering when the transparent panel is damaged.

  Hereinafter, the present invention will be described in more detail with reference to examples.

(Production Example 1: Production of metal oxide fine particles (1))
A solution prepared by dissolving 130 parts by mass of potassium stannate and 30 parts by mass of potassium antimonyl tartrate in 400 parts by mass of pure water, 1,000 parts by mass of pure water in which 1.0 part by mass of ammonium nitrate and 12 parts by mass of 15% by mass ammonia water were dissolved. After addition to the part, hydrolysis was carried out with stirring at 60 ° C. for 12 hours. During the hydrolysis, a 10% by mass nitric acid solution was added to keep the pH at 9.0. The precipitate formed by hydrolysis was filtered and washed, and then dispersed again in water to prepare a hydroxide dispersion of an antimony-doped tin oxide precursor having a nonvolatile content of 20% by mass. The dispersion was spray dried at a temperature of 100 ° C. The obtained powder was heat-treated at 550 ° C. for 2 hours in an air atmosphere to obtain an antimony-doped tin oxide powder. A sol was prepared by dispersing 60 parts by mass of this powder in 140 parts by mass of a 4.3% by mass aqueous potassium hydroxide solution and pulverizing it with a sand mill for 3 hours while maintaining the dispersion at 30 ° C.

Next, the sol obtained above is dealkalized with an ion exchange resin until the pH is 3.0, and then pure water is added to form a metal composed of antimony-doped tin oxide fine particles having a nonvolatile content of 20% by mass. An aqueous dispersion of oxide fine particles (1) was prepared. The pH of the aqueous dispersion of the metal oxide fine particles (1) was 3.3. The average particle size of the metal oxide fine particles (1) was 9 nm. Next, 100 parts by mass of the obtained aqueous dispersion of metal oxide fine particles (1) was adjusted to 25 ° C., and tetraethoxysilane (manufactured by Tama Chemical Co., Ltd .; normal ethyl silicate, SiO ₂ concentration of 28.8% by mass). After adding 4 parts by mass over 3 minutes, the mixture was stirred for 30 minutes. Thereafter, 100 parts by mass of a mixed solvent of ethanol (86.8% by mass), isopropyl alcohol (9.3% by mass) and methanol (3.9% by mass) (hereinafter abbreviated as “mixed ethanol”) was added over 1 minute, and 50 After heating to 30 ° C. over 30 minutes, heat treatment was performed for 15 hours. The nonvolatile content at this time was 10% by mass. Subsequently, water or the like as a dispersion medium is filtered off with an ultrafiltration membrane, and is replaced with mixed ethanol, and dispersion of chain metal oxide fine particles (1) coated with silica having a nonvolatile content of 19.4% by mass is dispersed. A liquid was prepared. The average number of connected fine particles constituting the chain metal oxide fine particles (1) was 5. This average number of connections is obtained by taking a transmission electron micrograph of chain metal oxide fine particles, obtaining the number of connections for 100 chain metal oxide fine particles, and rounding the average value to obtain the average connection number. It was a number.

Example 1
Polyfunctional acrylate mixture (dipentaerythritol hexaacrylate 64% by mass, dipentaerythritol pentaacrylate 17% by mass, dipentaerythritol tetraacrylate 19% by mass) 13.7 parts by mass, urethane acrylate (pentaerythritol triacrylate and isophorone diisocyanate Reaction product) 1.5 parts by weight, methyl ethyl ketone 47.11 parts by weight, ethanol 5.28 parts by weight, n-propanol 0.6 parts by weight, methanol 0.3 parts by weight, diacetone alcohol 9.28 parts by weight, After uniformly mixing 0.4 parts by weight of a photopolymerization initiator (0.09 parts by weight of “Irgacure 184” manufactured by BASF Japan Ltd. and 0.31 parts by mass of “Irgacure 127” manufactured by BASF Japan Ltd.) In example 1 21.63 parts by mass of the resulting dispersion of metal oxide fine particles (1) (breakdown: 4.2 parts by mass of metal oxide (1), 15.13 parts by mass of ethanol, 1.62 parts by mass of isopropyl alcohol, and 0.12 parts by mass of methanol). 68 parts by mass) and 0.2 part by mass of a leveling agent (“BYK-UV3576” manufactured by BYK Japan KK) were mixed to obtain an active energy ray-curable composition (1) having a nonvolatile content of 20% by mass.

(Examples 2-8 and Comparative Examples 1-16)
The active energy ray-curable compositions (2) to (8) and (R1) to (R16) having a nonvolatile content of 20% by mass are carried out in the same manner as in Example 1 except that the formulation shown in Tables 1 to 4 is changed. Got. In Tables 1 to 4, the blending amounts of ethanol, isopropyl alcohol, and methanol are amounts including those contained in the dispersion of metal oxide fine particles (1) obtained in Production Example 1.

  Using the active energy ray-curable compositions (1) to (8) and (R1) to (R16) obtained in Examples 1 to 8 and Comparative Examples 1 to 16, the following tests and evaluations were performed. It was.

[Evaluation of coating material appearance]
The appearance of the active energy ray-curable composition obtained above was visually observed, and the appearance of the coating material was evaluated according to the following criteria.
○: Almost no cloudiness.
Δ: Slightly cloudy.
X: There is cloudiness.

[Measurement and evaluation of viscosity]
The viscosity immediately after preparation of the active energy ray-curable composition obtained above and after standing at 25 ° C. for 1 day was measured at 25 ° C. using an E-type viscometer (Toki Sangyo Co., Ltd. “TV-20 type”). , 100 rpm, cone plate no. 1 (1 ° 34 ′ × R24 rotor) was measured, and the storage stability of the coating material was evaluated according to the following criteria.
A: Increase in viscosity after standing for 1 day is 2 mPa · s or less.
Δ: Viscosity increase after standing for 1 day exceeds 2 mPa · s and is 5 mPa · s or less.
X: Increase in viscosity after standing for 1 day exceeds 5 mPa · s.

[Preparation of sample for evaluation]
The active energy ray-curable composition obtained above was coated on a surface of the polyethylene terephthalate film (“Cosmo Shine A4100” manufactured by Toyobo Co., Ltd., thickness: 100 μm) with a bar coater to a film thickness of 2.7 μm. After being coated at 60 ° C. for 90 seconds, an ultraviolet irradiation device (“MIDN-042-C1” manufactured by Eye Graphics Co., Ltd., lamp: 120 W / cm, high-pressure mercury lamp) is used in an air atmosphere. The film having a cured coating film of the active energy ray-curable composition was obtained as an evaluation sample by irradiating ultraviolet rays with an irradiation light amount of 0.3 J / cm ² .

[Evaluation of coating appearance]
The appearance of the cured coating film of the evaluation sample obtained above was visually observed, and the coating film appearance was evaluated according to the following criteria.
○: Almost no whitening.
Δ: Slightly whitened.
X: There is whitening.

[Evaluation of antistatic properties]
The evaluation film obtained above was stored for 18 hours in an environment of a temperature of 23 ° C. and a humidity of 50% RH, and then a high resistivity meter (“Mitsubishi Chemical Analytech Co., Ltd.“ Using a Hiresta-UP MCP-HT450 "), the surface resistance value was measured with an applied voltage of 500 V and a measurement time of 10 seconds. From the obtained surface resistance value, antistatic properties were evaluated according to the following criteria.
○: The surface resistance value is 7 × 10 ⁸ Ω / □ or less.
Δ: Surface resistance value exceeds 7 × 10 ⁸ Ω / □ and is 10 × 10 ⁸ Ω / □ or less.
×: The surface resistance value exceeds 10 × 10 ⁸ Ω / □.

  The compounding composition, measurement evaluation, and evaluation result of each active energy ray curable composition are shown in Tables 1-6.

  From the evaluation results shown in Tables 1 and 2, the active energy ray-curable compositions of the present invention of Examples 1 to 8 have a coating material appearance even when diluted to a non-volatile content of 20% by mass with an organic solvent to reduce the viscosity. It was confirmed that the coating material had high storage stability. Moreover, it was confirmed that the cured coating film was excellent in coating film appearance and had a surface resistance value of 10 to the 8th power and high antistatic properties.

  On the other hand, from the evaluation results shown in Tables 3 to 6, Comparative Examples 1 to 16 show that the Hansen solubility parameter dispersion term (δD) and polarization term (δP) of the organic solvent (C) in the active energy ray-curable composition. And at least one of the hydrogen bond terms (δH) is an example outside the scope of the present invention. In these examples, it was confirmed that at least one of the coating material appearance, the storage stability of the coating material, the coating film appearance, and the antistatic property was insufficient.

Claims (4)

An active energy ray-curable compound (A), a metal oxide (B) having a treatment layer of a hydrolyzable organosilicon compound on the particle surface and conductivity, and a dispersion term (δD) with a Hansen solubility parameter of 15 0.6 to 16.1 MPa ^0.5 , the polarization term (δP) is 7.2 to 9.8 MPa ^0.5 , and the hydrogen bond term (δH) is 8.2 to 11.4 MPa ^0. An active energy ray-curable composition comprising an organic solvent (C) in the range of ^.5 .   The active energy ray-curable composition according to claim 1, wherein the metal oxide (B) is antimony-doped tin oxide.   The active energy ray-curable composition according to claim 1 or 2, wherein the organic solvent (C) contains at least one selected from the group consisting of diacetone alcohol, acetylacetone, dimethyl carbitol and propylene glycol monomethyl ether acetate.   A film comprising a cured coating film of the active energy ray-curable composition according to claim 1.