JP2016121206A - Active energy ray-curable resin composition, coating material containing the same, its coating film, and laminated film having the coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray-curable resin composition capable of obtaining a cured coating film having flexibility capable of preventing cracks and antiblocking properties during storage even in a brittle base film to a high degree, in a hard coat layer formed on a plastic film; a coating material containing the same; a coating film formed by curing the same; and a laminated film having the coating layer on the substrate film.SOLUTION: An active energy ray-curable resin composition contains: urethan (meth)acrylate (A) of linear polyester (a) which is obtained from aliphatic diol (a1) and dicarboxylic acid or its acid anhydride (a2) and a weight average molecular weight of 600-3,000; an acrylic polymer (B) which has a weight average molecular weight of 2,000-50,000 and has a (meth)acryloyl group in a molecular structure; and inorganic fine particles (C).SELECTED DRAWING: None

Description

  The present invention relates to an active energy ray-curable resin composition from which a cured coating film exhibiting flexibility and anti-blocking properties that can effectively prevent cracking of a fragile substrate film, and a coating comprising the resin composition The present invention also relates to a coating film comprising the coating material and a laminated film having the coating film layer.

  A hard coat film for protecting the surface of a molded article, a display or the like from scratches can be obtained by applying a resin composition on a plastic film and installing a hard coat layer. The hard coat film needs to have a surface hardness to ensure scratch resistance against scratches and scratches, but if the coating film itself is hardened to increase the surface hardness, the plastic film as the base material In general, it is difficult to balance the surface hardness and the flexibility because the film has an insufficient crack prevention function when a base film that lacks or is fragile is used.

  As a method for imparting flexibility of a cured product, it is well known that a urethane bond is generally contained in a raw material resin. For example, a compound having a urethane bond is used as an active energy ray curable resin as a method of imparting adhesiveness to a film used as a base material and maintaining the adhesiveness even when stored in a bent state. A method has been proposed (see, for example, Patent Document 1). In this patent document 1, it is not premised on the use as a hard-coat layer, but it has been evaluated exclusively for use as an adhesive with other base film, and when a fragile base film is used. The effectiveness in terms of crack prevention is not discussed.

  As an active energy ray-curable resin composition containing urethane (meth) acrylate, it is also known that it can exhibit hard coat properties and fingerprint resistance (see, for example, Patent Document 2). However, the laminated film actually manufactured in Patent Document 2 may cause a phenomenon in which the films adhere to each other, i.e., blocking, which causes a new problem in use.

  In order to prevent blocking during film storage, a method of forming a fine concavo-convex structure on the surface of the hard coat layer, that is, a method of using inorganic fine particles in combination is known (for example, see Patent Document 3). Inorganic fine particles have poor compatibility with organic compounds that are active energy ray-curable resins, and even if blended as they are, it is difficult to uniformly disperse them, so the surface of inorganic fine particles is modified and the dispersibility is improved. It has also been proposed to use a specific polymer for this purpose (see, for example, Patent Document 4).

  However, in these documents, only a part of the function as a hard coat layer is expressed, and while maintaining the transparency and hardness of the coating film, the followability to the base film and the anti-blocking property during storage It was not something that combines at a high level.

JP 2014-009339 A WO2011 / 033405 JP 2002-322430 A WO2012 / 086373

  In view of the above circumstances, the problem to be solved by the present invention is that the hard coat layer formed on the plastic film has the flexibility to prevent cracking even if it is a fragile substrate film, and anti-blocking during storage Active energy ray-curable resin composition capable of obtaining a cured coating film having a high level of properties, a coating material containing the same, a coating film obtained by curing the coating composition, and a laminate having the coating film layer on a base film To provide a film.

  As a result of intensive studies in order to solve the above problems, the present inventor has found that an active energy ray-curable resin composition comprising a specific urethane (meth) acrylate, an acrylic polymer, and inorganic fine particles, and a cured coating thereof. The film has been found to solve the above problems, and the present invention has been completed.

  That is, the present invention relates to a urethane (meth) acrylate (A) of a linear polyester (a) having a weight average molecular weight of 600 to 3,000 obtained from an aliphatic diol (a1) and a dicarboxylic acid or an acid anhydride (a2) thereof. ), A weight average molecular weight in the range of 2,000 to 50,000, and an acrylic polymer (B) having a (meth) acryloyl group in the molecular structure and inorganic fine particles (C). An active energy ray-curable resin composition, a paint containing the same, a cured coating film thereof, and a laminated film formed by forming the coating film on a film are provided.

  According to the present invention, while maintaining the transparency of the conventional hard coat layer, it is possible to obtain a laminated film having excellent followability to the base film and exhibiting a crack preventing function of the base film. . Moreover, since this laminated film is also excellent in anti-blocking property, there is no problem in storage. Therefore, it is possible to use a fragile plastic film such as a cyclopolyolefin-based polymer film that has recently been used for various applications from the viewpoint of better transparency and the like as a hard coat film. Furthermore, when the substrate film itself has flexibility, it can also be used as a hard coat film that can be bent or wound.

  The urethane (meth) acrylate used in the present invention is a urethane of a linear polyester (a) having a weight average molecular weight of 600 to 3,000 obtained from an aliphatic diol (a1) and a dicarboxylic acid or an acid anhydride (a2) thereof. (Meth) acrylate (A). By using such a specific urethane (meth) acrylate (A), it is a hard coat layer that is excellent in compatibility with the acrylic polymer (B) described later and maintains transparency, and to the substrate. The following ability can be expressed.

  In the present invention, (meth) acrylate is a general term for acrylate alone, methacrylate alone and a mixture thereof.

  The basic skeleton of the urethane (meth) acrylate (A) is a linear polyester (a) having a weight average molecular weight of 600 to 3,000, and the linear polyester (a) is an aliphatic diol (a1) and a dicarboxylic acid. It is polyester obtained from an acid or its acid anhydride (a2). Such a linear polyester skeleton expresses the flexibility of the cured coating film, and has an ester bond, thereby exhibiting compatibility with the acrylic polymer (B) described later and thus transparent. It is thought that it becomes a good coating film. When the weight average molecular weight of the linear polyester (a) is less than 600, the followability to the substrate is insufficient, and when it exceeds 3,000, the antiblocking property of the cured coating film is impaired.

  The aliphatic diol (a1) is preferably a diol having 2 to 6 carbon atoms, and the hydrocarbon chain is a low-branched type (a side chain having 1 to 3 carbon atoms). It is preferable that it is linear.

  Specific examples of the aliphatic diol (a1) include ethylene glycol, propylene glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol and 1,6-hexanediol.

  The dicarboxylic acid or acid anhydride (a2) may be aliphatic or a compound having an aromatic ring. However, from the viewpoint of forming a cured coating film having more flexibility, an aliphatic dicarboxylic acid. Is preferably used.

  Specific examples of the dicarboxylic acid or acid anhydride (a2) include, for example, adipic acid, succinic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and terephthalic acid, and anhydrides thereof. .

  The urethane (meth) acrylate (A) used in the present invention has a weight average molecular weight of 600 to 3,000 by subjecting the aliphatic diol (a1) and the dicarboxylic acid or acid anhydride (a2) to a condensation reaction. The polyester (a) adjusted to 1 is used as a raw material. Or what is marketed may be used as it is.

  The urethane (meth) acrylate (A) is a urethane (meth) acrylate of the polyester (a) described above, and has a weight average molecular weight of 1,000 to 3,000 as the polyester (a) from the viewpoint of easy synthesis. It is preferable to use those obtained by reacting a linear polyester (a) having hydroxyl groups at both ends thereof, a polyfunctional isocyanate compound (a3), and a (meth) acrylate (a4) having a hydroxyl group.

  Examples of the polyfunctional isocyanate compound (a3) include tolylene diisocyanate, 1,6-hexane diisocyanate, 4,4′-diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, 1,6-hexane diisocyanate trimer, and hydrogenation. Tolylene diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylene diisocyanate, paraphenylene diisocyanate, tolylene diisocyanate dimer, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate mutual adduct, 4, 4'-dicyclohexylmethane diisocyanate, trimethylolpropane tris (tolylene diisocyanate) adduct and isophorone diisocyanate And the like. As the polyfunctional isocyanate compound, diisocyanate is preferably used.

  Examples of the hydroxyl group-containing (meth) acrylate (a4) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, and hydroxyhexyl. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate, hydroxyoctyl (meth) acrylate, pentaerythritol tri, di or mono (meth) acrylate, and trimethylolpropane di or mono (meth) acrylate.

  In the presence of an addition catalyst such as dibutyltin dilaurate, the polyfunctional isocyanate (a3) to be used and the linear polyester (a) component having hydroxyl groups at both ends are heated and stirred to cause addition reaction, and a (meth) acrylate having a hydroxyl group ( It can be easily obtained by adding a4), heating and stirring to cause addition reaction.

  The resin component of the active energy ray-curable resin composition of the present invention includes the urethane (meth) acrylate (A) described above, and a weight average molecular weight in the range of 2,000 to 50,000, and in the molecular structure. It is essential to use an acrylic polymer (B) having a (meth) acryloyl group. By using such an acrylic polymer (B), the flexibility and flexibility of the resulting cured coating film can be easily expressed.

  The acrylic polymer (B) having a (meth) acryloyl group in the molecular structure has a weight average molecular weight (Mw) in the range of 2,000 to 50,000. Since it can be stably dispersed, the storage stability of the resin composition is improved. When the weight average molecular weight (Mw) is less than 2,000, the dispersibility of the inorganic fine particles (C) is lowered, so that the storage stability of the resin composition and the transparency of the cured coating film are lowered. Moreover, when a weight average molecular weight (Mw) exceeds 50,000, a viscosity will become high and it will become difficult to handle as a paint use. Among them, the weight average molecular weight (Mw) is 5,000 to 40,000 because it is excellent in dispersibility of the inorganic fine particles (C) and the active energy ray-curable resin composition has a viscosity suitable for coating. More preferably, it is the range.

  In the present invention, the weight average molecular weight (Mw) is a value measured under the following conditions using a gel permeation chromatograph (GPC).

Measuring device: HLC-8220 manufactured by Tosoh Corporation
Column: Tosoh Corporation guard column HXL-H
+ Tosoh Corporation TSKgel G5000HXL
+ Tosoh Corporation TSKgel G4000HXL
+ Tosoh Corporation TSKgel G3000HXL
+ Tosoh Corporation TSKgel G2000HXL
Detector: RI (differential refractometer)
Data processing: Tosoh Corporation SC-8010
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow rate: 1.0 ml / min Standard: Polystyrene sample: 0.4 mass% tetrahydrofuran solution filtered in terms of resin solids with a microfilter (100 μl)

  In addition, the (meth) acryloyl group equivalent of the acrylic polymer (B) having a (meth) acryloyl group in the molecular structure has a high surface hardness, and a cured coating film having excellent curling resistance at the time of curing is obtained. It is preferable that it is the range of 150g / eq-1600g / eq, and what is the range of 170g / eq-1100g / eq is more preferable. Furthermore, in terms of obtaining an active energy ray-curable resin composition having excellent stability over time, a range of 220 g / eq to 750 g / eq is more preferable, and a range of 300 g / eq to 550 g / eq. Particularly preferred.

  The acrylic polymer (B) having a (meth) acryloyl group in the molecular structure is, for example, an acrylic polymer obtained by polymerizing a compound (x) having a reactive functional group and a (meth) acryloyl group as an essential component. Examples thereof include a polymer obtained by reacting the polymer (X) with a compound (y) having a (meth) acryloyl group and a functional group capable of reacting with the reactive functional group of the compound (x).

  More specifically, it has an acrylic polymer (X1) obtained by polymerizing a compound (x1) having an epoxy group and a (meth) acryloyl group as essential components, a carboxyl group, and a (meth) acryloyl group. Acrylic polymer (X2) obtained by polymerizing acrylic polymer (B1) obtained by reacting compound (y1) and compound (x2) having a carboxyl group and a (meth) acryloyl group as essential components And an acrylic polymer (B2) obtained by reacting an epoxy group and a compound (y2) having a (meth) acryloyl group, and a compound (x3) having a hydroxyl group and a (meth) acryloyl group as essential components The acrylic polymer (X3) obtained by polymerization is reacted with a compound (y3) having an isocyanate group and a (meth) acryloyl group. Resulting acrylic polymer (B3), and the like.

  Specific methods for synthesizing the acrylic polymers (B1), (B2), and (B3) are described in detail, for example, in JP2013-108209A, and can be adjusted by the same method. .

  As said acrylic polymer (B), the said acrylic polymers (B1) and (B2) are preferable at the point which is familiar with the below-mentioned inorganic fine particle (C), and is excellent in the storage stability of the dispersion obtained. Here, the hydroxyl value of the acrylic polymers (B1) and (B2) is preferably in the range of 35 to 250 mgKOH / g, more preferably 50 to 230 mgKOH / g in terms of excellent dispersibility of the inorganic fine particles (C). Is more preferably in the range of 65 to 160 mgKOH / g, and most preferably in the range of 80 to 150 mgKOH / g. Further, the acrylic polymer (B1) is preferable from the viewpoint of simpler synthesis, and acryl is obtained by using glycidyl (meth) acrylate as the compound (x1) and using (meth) acrylic acid as the compound (y1). A polymer is more preferred.

  As a blending ratio (mass ratio) (A) / (B) of the urethane (meth) acrylate (A) and the acrylic polymer (B), from the viewpoint of transparency and antiblocking property of the resulting cured coating film Therefore, it is preferably in the range of 0.18 to 8.0, particularly preferably in the range of 1.3 to 5.5.

  As the resin component in the resin composition of the present invention, the urethane (meth) acrylate (A) is from the viewpoint of easy adjustment of the flexibility of the resulting cured coating film and the viscosity when used for coatings. And it is preferable to use together (meth) acrylate (D) other than the said acrylic polymer (B).

  Examples of the (meth) acrylate (D) include various (meth) acrylate monomers and urethane (meth) acrylates other than the urethane (meth) acrylate (A).

  Examples of the (meth) acrylate monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) ) Acrylate, t-butyl (meth) acrylate, glycidyl (meth) acrylate, acryloylmorpholine, N-vinylpyrrolidone, tetrahydrofurfuryl acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) Acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate Relate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phosphoric acid (meth) acrylate, ethylene oxide modified phosphoric acid (meth) acrylate, phenoxy (meth) acrylate , Ethylene oxide modified phenoxy (meth) acrylate, propylene oxide modified phenoxy (meth) acrylate, nonylphenol (meth) acrylate, ethylene oxide modified nonylphenol (meth) acrylate, propylene oxide modified nonylphenol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, Methoxypolyethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, 2- (Meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxypropyl hydrogen phthalate, 2- ( (Meth) acryloyloxypropyl hexahydrohydrogen phthalate, 2- (meth) acryloyloxypropyl tetrahydrophthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl ( (Meth) acrylate, octafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, adamantyl Mono (meth) acrylates such as mono (meth) acrylate;

  Butanediol di (meth) acrylate, hexanediol di (meth) acrylate, ethoxylated hexanediol di (meth) acrylate, propoxylated hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate , Di (meth) acrylates such as polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate;

  Trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, tris 2-hydroxyethyl isocyanurate tri (meth) acrylate, glycerin tri (meth) acrylate Tri (meth) acrylates such as;

  Pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) Tetrafunctional or higher functional (meth) acrylates such as acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane hexa (meth) acrylate;

  And the (meth) acrylate etc. which substituted a part of above-mentioned various polyfunctional (meth) acrylate with the alkyl group and (epsilon) -caprolactone, etc. are mentioned.

  Examples of the urethane (meth) acrylate include urethane (meth) acrylate obtained by reacting a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate compound.

  Examples of the polyisocyanate compound used as a raw material for the urethane (meth) acrylate include various diisocyanate monomers and a nurate polyisocyanate compound having an isocyanurate ring structure in the molecule.

  Examples of the diisocyanate monomer include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, and m-tetramethylxylylene. Aliphatic diisocyanates such as range isocyanate;

  Cycloaliphatic diisocyanates such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate;

  1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate And aromatic diisocyanates such as 1,4-phenylene diisocyanate and tolylene diisocyanate.

  Examples of the nurate type polyisocyanate compound having an isocyanurate ring structure in the molecule include those obtained by reacting a diisocyanate monomer with a monoalcohol and / or a diol. Examples of the diisocyanate monomer used in the reaction include the various diisocyanate monomers described above, and each may be used alone or in combination of two or more. Monoalcohols used in the reaction are hexanol, octanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol, n-heptadecanol, n- Octadecanol, n-nonadecanol and the like can be mentioned, and the diol includes ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1, Examples include 3-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol. These monoalcohols and diols may be used alone or in combination of two or more.

  The hydroxyl group-containing (meth) acrylate compound used as a raw material for the urethane (meth) acrylate is, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, glycerin diacrylate, trimethylolpropane diacrylate, Aliphatic (meth) acrylate compounds such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate;

  4-hydroxyphenyl acrylate, β-hydroxyphenethyl acrylate, 4-hydroxyphenethyl acrylate, 1-phenyl-2-hydroxyethyl acrylate, 3-hydroxy-4-acetylphenyl acrylate, 2-hydroxy-3-phenoxy Examples include (meth) acrylate compounds having an aromatic ring in the molecular structure such as propyl acrylate. These may be used alone or in combination of two or more.

  Among these hydroxyl (meth) acrylate compounds, glycerin diacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate are excellent in toughness and having a high surface hardness. An aliphatic (meth) acrylate compound having two or more (meth) acryloyl groups in the molecular structure such as Furthermore, an aliphatic (meth) acrylate compound having three or more (meth) acryloyl groups in the molecular structure such as pentaerythritol triacrylate, dipentaerythritol pentaacrylate, etc. in that a cured coating film having higher surface hardness can be obtained. Is more preferable.

  The method for producing the urethane (meth) acrylate includes, for example, the polyisocyanate compound, the hydroxyl group-containing (meth) acrylate compound, the isocyanate group of the polyisocyanate compound, and the hydroxyl group-containing (meth) acrylate compound. The molar ratio [(NCO) / (OH)] with the hydroxyl group to be used is within a range of 1 / 0.95 to 1 / 1.05, within a temperature range of 20 to 120 ° C., if necessary. Examples include a method performed using a urethanization catalyst.

  When the urethane (meth) acrylate is produced from the polyisocyanate compound and the (meth) acrylate compound having one hydroxyl group in the molecular structure, the reaction is pentaerythritol tetra (meth) acrylate or dipentaerythritol hexa You may carry out by the type | system | group containing acrylate compounds, such as (meth) acrylate. Specifically, the urethane (meth) acrylate obtained by such a method is obtained by reacting a raw material containing the polyisocyanate compound, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate. Examples thereof include urethane (meth) acrylate obtained, urethane acrylate obtained by reacting a raw material containing polyisocyanate compound, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. .

  The weight average molecular weight (Mw) of the urethane (meth) acrylate thus obtained is preferably in the range of 500 to 10,000 in terms of excellent compatibility with the acrylic polymer (B), and 600 More preferably, it is in the range of ˜1,000.

  These compounds (D) may be used alone or in combination of two or more. Among these, a trifunctional or higher functional (meth) acrylate monomer or a trifunctional or higher functional urethane (meth) acrylate is preferable because a coating film with higher hardness can be obtained. As the trifunctional or higher functional (meth) acrylate monomer, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate are preferable. . The trifunctional or higher functional urethane (meth) acrylate includes a diisocyanate compound and a (meth) acryloyl group in a molecular structure such as glycerin diacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and the like. A urethane (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylate compound having two or more of these is preferable, and a diisocyanate compound and a hydroxyl group-containing (meth) acrylate compound having three or more (meth) acryloyl groups are reacted. The urethane (meth) acrylate obtained by making it let it be more preferable.

  The resin composition of the present invention contains inorganic fine particles (C) in order to impart antiblocking properties to the resulting cured coating film. By using inorganic fine particles (C) as an antiblocking agent, a cured coating film with higher surface hardness can be obtained.

  The average particle diameter of the inorganic fine particles (C) is preferably in the range of 95 to 250 nm, particularly in the range of 100 to 180 nm, from the viewpoint that the surface hardness and transparency of the resulting coating film can be combined at a high level. It is more preferable.

  In the present invention, the average particle diameter of the inorganic fine particles (C) is a value measured by using a particle diameter measuring device (“ELSZ-2” manufactured by Otsuka Electronics Co., Ltd.) as the particle diameter in the resin composition. is there.

  The inorganic fine particles (C) contained in the active energy ray-curable resin composition of the present invention are obtained by converting the inorganic fine particles as a raw material into resin components contained in the active energy ray-curable resin composition of the present invention, that is, the urethane ( It can be obtained by dispersing a meth) acrylate (A) and an acrylic polymer (B) in a resin component having essential components. Examples of the inorganic fine particles include fine particles of silica, alumina, zirconia, titania, barium titanate, antimony trioxide, and the like. These may be used alone or in combination of two or more.

  Among these inorganic fine particles, silica fine particles are preferable because they are easily available and easy to handle. Examples of the silica fine particles include wet silica fine particles and dry silica fine particles. Examples of the wet silica fine particles include silica fine particles obtained by neutralizing sodium silicate with a mineral acid. When wet silica fine particles are used as the inorganic fine particles, the average particle size is 95 to 250 nm in that it becomes easy to adjust the average particle size of the inorganic fine particles (C) in the obtained resin composition to the preferred value. It is preferable to use wet silica fine particles in the range. Examples of the dry silica fine particles include silica fine particles obtained by burning silicon tetrachloride in an oxygen or hydrogen flame. When dry silica fine particles are used as the inorganic fine particles, the average primary particle size is 3 to 100 nm in that it is easy to adjust the average particle size of the inorganic fine particles (C) in the obtained resin composition to the preferred value. It is preferable to use secondary particles in which dry silica fine particles, preferably in the range of 5 to 50 nm, are aggregated.

  Among the silica fine particles, dry silica fine particles are preferable in that a cured coating film having higher surface hardness can be obtained.

  In this invention, you may introduce | transduce a functional group to the surface of the said inorganic fine particle using various silane coupling agents. By introducing a functional group into the surface of the inorganic fine particles, miscibility with an organic component such as an acrylic polymer (B) having a (meth) acryloyl group in the molecular structure is increased, and storage stability is improved.

  Examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- Glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyl Diethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) ) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl- N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, special Aminosilane, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropylate Ethoxysilane, allyltrichlorosilane, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, trichlorovinylsilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, etc., vinyl -Based silane coupling agents;

  Diethoxy (glycidyloxypropyl) methylsilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-bridoxypropyl Epoxy-based silane coupling agents such as triethoxysilane;

  styrenic silane coupling agents such as p-styryltrimethoxysilane;

  3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. (meth) Acryloxy silane coupling agent;

  N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltri Amino-based silane couplings such as methoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane Agent;

  Ureido-based silane coupling agents such as 3-ureidopropyltriethoxysilane;

  Chloropropyl-based silane coupling agents such as 3-chloropropyltrimethoxysilane;

  Mercaptopropyl silane coupling agents, such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethinesilane;

  Sulfide-based silane coupling agents such as bis (triethoxysilylpropyl) tetrasulfide;

  Examples thereof include isocyanate-based silane coupling agents such as 3-isocyanatopropyltriethoxysilane. These silane coupling agents may be used alone or in combination of two or more. Among these, a cured coating film having excellent miscibility with an organic component such as an acrylic polymer (B) having a (meth) acryloyl group in the molecular structure, a high surface hardness and excellent transparency can be easily obtained. (Meth) acryloxy-based silane coupling agents are preferred, and 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane are more preferred.

  The active energy ray-curable resin composition of the present invention contains the (meth) acrylate (D) in addition to the urethane (meth) acrylate (A), the acrylic polymer (B), and the inorganic fine particles (C). In this case, the urethane (meth) acrylate (A), the acrylic polymer (B), and the inorganic are obtained in that the resin composition has excellent storage stability and a cured coating film having both high surface hardness and transparency is obtained. The total amount of fine particles (C) and (meth) acrylate (D) is preferably 100 to 50 parts by mass, and the inorganic fine particles (C) are preferably contained in the range of 30 to 60 parts by mass, and contained in the range of 35 to 55 parts by mass. It is more preferable.

  The resin composition of the present invention may contain a dispersion aid as necessary. Examples of the dispersion aid include phosphate ester compounds such as isopropyl acid phosphate, triisodecyl phosphite, ethylene oxide-modified phosphate dimethacrylate, and the like. These may be used alone or in combination of two or more. Among these, ethylene oxide-modified phosphoric dimethacrylate is preferable because it is excellent in dispersion assist performance.

  Examples of commercially available dispersion aids include “Kayamar PM-21” and “Kayamer PM-2” manufactured by Nippon Kayaku Co., Ltd., “Light Ester P-2M” manufactured by Kyoeisha Chemical Co., Ltd., and the like.

  When using the said dispersion | distribution adjuvant, it contains in 0.5-5.0 mass parts in 100 mass parts of resin compositions of this invention at the point used as a resin composition with higher storage stability. Is preferred.

  Moreover, the resin composition of this invention may contain the organic solvent. For example, when the acrylic polymer (B) is produced by a solution polymerization method, the organic solvent may contain the solvent used at that time as it is, or further add another solvent. May be. Or the organic solvent used at the time of manufacture of the said acrylic polymer (B) may be removed once, and another solvent may be used. Specific examples of the solvent used include ketone solvents such as acetone, methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK); cyclic ether solvents such as tetrahydrofuran (THF) and dioxolane; esters such as methyl acetate, ethyl acetate and butyl acetate; toluene Aromatic solvents such as xylene, alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, etc. These glycol ether solvents are mentioned. These may be used alone or in combination of two or more. Among these, a ketone solvent is preferable and methyl isobutyl ketone is more preferable in that the resin composition has excellent storage stability and excellent paintability when used as a paint.

  The resin composition of the present invention further comprises an ultraviolet absorber, an antioxidant, a silicon-based additive, organic beads, a fluorine-based additive, a rheology control agent, a defoaming agent, an antifogging agent, a colorant, an organic solvent, an inorganic solvent. You may contain additives, such as a filler.

  Examples of the ultraviolet absorber include 2- [4-{(2-hydroxy-3-dodecyloxypropyl) oxy} -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- [4-{(2-hydroxy-3-tridecyloxypropyl) oxy} -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3 Triazine derivatives such as 2,5-triazine, 2- (2'-xanthenecarboxy-5'-methylphenyl) benzotriazole, 2- (2'-o-nitrobenzyloxy-5'-methylphenyl) benzotriazole, 2- Xanthenecarboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, and the like.

  Examples of the antioxidant include hindered phenol-based antioxidants, hindered amine-based antioxidants, organic sulfur-based antioxidants, and phosphate ester-based antioxidants. These may be used alone or in combination of two or more.

  Examples of the silicon-based additive include dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, and fluorine-modified dimethyl. Examples include polyorganosiloxanes having alkyl groups and phenyl groups, such as polysiloxane copolymers and amino-modified dimethylpolysiloxane copolymers, polydimethylsiloxanes having polyether-modified acrylic groups, and polydimethylsiloxanes having polyester-modified acrylic groups. It is done. These may be used alone or in combination of two or more.

  Examples of the organic beads include polymethyl methacrylate beads, polycarbonate beads, polystyrene beads, polyacryl styrene beads, silicone beads, glass beads, acrylic beads, benzoguanamine resin beads, melamine resin beads, polyolefin resin beads, Examples thereof include polyester resin beads, polyamide resin beads, polyimide resin beads, polyfluorinated ethylene resin beads, and polyethylene resin beads. The preferable value of the average particle diameter of these organic beads is in the range of 1 to 10 μm. These may be used alone or in combination of two or more.

  Examples of the fluorine-based additive include DIC Corporation “Megafac” series. These may be used alone or in combination of two or more.

  The amount of the various additives used is preferably in a range where the effect is sufficiently exhibited and ultraviolet curing is not inhibited. Specifically, in each 100 parts by mass of the resin composition of the present invention, 0.01 to 40 masses are used. It is preferable to use within the range of parts.

  The resin composition of the present invention further contains a photopolymerization initiator. Examples of the photopolymerization initiator include benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4,4′-bisdimethylaminobenzophenone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, Various benzophenones such as Michler's ketone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone;

Xanthones, thioxanthones such as xanthone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone; various acyloin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether;

  Α-diketones such as benzyl and diacetyl; sulfides such as tetramethylthiuram disulfide and p-tolyl disulfide; various benzoic acids such as 4-dimethylaminobenzoic acid and ethyl 4-dimethylaminobenzoate;

  3,3′-carbonyl-bis (7-diethylamino) coumarin, 1-hydroxycyclohexyl phenyl ketone, 2,2′-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- [4 -(Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-hydroxy-2-methyl-1- Phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 1- [4- (2-hydroxyethoxy) phenyl] -2- Hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2- Tylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4-benzoyl-4'-methyldimethylsulfide, 2,2'-diethoxyacetophenone, benzyldimethyl Ketal, benzyl-β-methoxyethyl acetal, methyl o-benzoylbenzoate, bis (4-dimethylaminophenyl) ketone, p-dimethylaminoacetophenone, α, α-dichloro-4-phenoxyacetophenone, pentyl-4- Dimethylaminobenzoate, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2,4-bis-trichloromethyl-6- [di- (ethoxycarbonylmethyl) amino] phenyl-S-triazine, 2 , 4-Bis-trichloromethyl-6- (4-ethoxy Phenyl-S-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-ethoxy) phenyl-S-triazineanthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, etc. Is mentioned. These may be used alone or in combination of two or more.

  Among the photopolymerization initiators, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy- 2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2′-dimethoxy-1,2-diphenylethane-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2 , 4,6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholino One or more mixed systems selected from the group of phenyl) -butan-1-one By are more active against a broad range of wavelengths of light is preferred because highly curable coating is obtained.

  Commercially available products of the photopolymerization initiator include, for example, “Irgacure-184”, “Irgacure-149”, “Irgacure-261”, “Irgacure-369”, “Irgacure-500”, “Irgacure-” manufactured by Ciba Specialty Chemicals. "Irgacure-754", "Irgacure-784", "Irgacure-819", "Irgacure-907", "Irgacure-1116", "Irgacure-1664", "Irgacure-1700", "Irgacure-1800" "Irgacure-1850", "Irgacure-2959", "Irgacure-4043", "Darocur-1173"; "Lucirin TPO" manufactured by BASF; "Kayacure-DETX", "Kayacure-MBP" manufactured by Nippon Kayaku ”,“ Kayaki “A-DMBI”, “Kayacure-EPA”, “Kayacure-OA”; “Bicure-10”, “Bicure-55” manufactured by Stowa Chemical; “Trigonal P1” manufactured by Akzo; “Deep” manufactured by Apjon; “QuantaCure-PDO”, “QuantaCure-ITX”, “QuantaCure-EPD”, etc. manufactured by Ward Brenkinsop.

  The amount of the photopolymerization initiator used is an amount that can sufficiently exhibit the function as a photopolymerization initiator, and is preferably within a range that does not cause precipitation of crystals and physical properties of the coating film. It is preferable to use in the range of 0.05 to 20 parts by mass with respect to 100 parts by mass of the resin composition, and it is particularly preferable to use in the range of 0.1 to 10 parts by mass.

  The resin composition of the present invention may further use various photosensitizers in combination with the photopolymerization initiator. Examples of the photosensitizer include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, and other nitrogen-containing compounds.

  The method for producing the active energy ray-curable resin composition of the present invention uses, for example, a disperser having a stirring blade such as a disper or a turbine blade, a disperser such as a paint shaker, a roll mill, a ball mill, an attritor, a sand mill, or a bead mill. , A method of mixing and dispersing the inorganic fine particles (C) in the acrylic polymer (B), urethane (meth) acrylate (A) alone or in a mixture, or the inorganic fine particles (C) in the urethane (meth) The method of mixing and dispersing in the resin component which consists of an acrylate (A), an acrylic polymer (B), and the said (meth) acrylate (D) is mentioned. When the inorganic fine particles (C) are wet silica fine particles, a uniform and stable dispersion can be obtained when any of the above-described dispersers is used. On the other hand, when the inorganic fine particles (C) are dry silica fine particles, it is preferable to use a ball mill or a bead mill in order to obtain a uniform and stable dispersion.

  The ball mill that can be preferably used in producing the active energy ray-curable resin composition of the present invention includes, for example, a vessel filled with a medium inside, a rotating shaft, and a rotating shaft coaxial with the rotating shaft. A stirring blade that is rotated by the rotational drive of the rotating shaft, a raw material supply port installed in the vessel, a dispersion outlet installed in the vessel, and a portion where the rotating shaft passes through the vessel. The shaft seal device has a structure in which the shaft seal device has two mechanical seal units, and the seal portions of the two mechanical seal units are sealed with an external seal liquid. A wet ball mill is mentioned.

  That is, the method for producing the active energy ray-curable resin composition of the present invention includes, for example, a vessel filled with a medium inside, a rotating shaft, a rotating shaft coaxially with the rotating shaft, A stirring blade that is rotated by rotation driving, a raw material supply port installed in the vessel, a dispersion outlet installed in the vessel, and a shaft seal device in which the rotary shaft is disposed in a portion that passes through the vessel. A wet ball mill having a structure in which the shaft seal device has two mechanical seal units, and the seal portions of the two mechanical seal units are sealed with an external seal liquid. The inorganic fine particles (C) and the resin component are supplied to the vessel from the supply port of the rotating shaft and the stirring shaft in the vessel. The inorganic fine particles (C) are pulverized and the inorganic fine particles (C) are dispersed in the resin component by rotating the blades and stirring and mixing the medium and the raw material, and then discharged from the discharge port. The method of doing is mentioned.

  About such a manufacturing method, what was described in detail in Unexamined-Japanese-Patent No. 2013-108809 is applicable as it is, for example.

  The active energy ray-curable resin composition of the present invention can be used for coating applications. The coating material can be used as a coating layer that protects the surface of the substrate by applying the coating onto various substrates and irradiating and curing the active energy rays. In this case, the coating material of the present invention may be directly applied to the surface protection member, or a material applied on a plastic film may be used as the protective film. Or you may use what applied the coating material of this invention on the plastic film, and formed the coating film as optical films, such as an antireflection film, a diffusion film, and a prism sheet. The coating film obtained using the paint of the present invention is characterized by high surface hardness and excellent transparency, so it can be applied to various types of plastic film with a film thickness according to the application, and used as a protective film or film It can be used as a molded product.

  The plastic film is, for example, a plastic film made of polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, cycloolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin, polyimide resin, or the like. And plastic sheets.

  Among the plastic films, the triacetyl cellulose film is a film that is particularly suitably used for the polarizing plate application of a liquid crystal display. However, since the thickness is generally as thin as 40 to 100 μm, the surface even when a hard coat layer is installed. It is difficult to make the hardness sufficiently high, and there is a feature that it is easily curled. The coating film comprising the resin composition of the present invention has a high surface hardness even when a triacetyl cellulose film is used as a base material, and is excellent in curling resistance, toughness, transparency, and followability to the base material. There is an effect and it can be used suitably. When using the triacetyl cellulose film as a base material, the coating amount when applying the coating material of the present invention is such that the film thickness after drying is in the range of 1 to 20 μm, preferably in the range of 2 to 10 μm. It is preferable. Examples of the coating method at that time include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing.

  Among the plastic films, examples of the polyester film include polyethylene terephthalate, and the thickness thereof is generally about 20 to 300 μm. Although it is a cheap and easy to process film, it is a film used for various applications such as a touch panel display. However, it is very soft and has a feature that it is difficult to sufficiently increase the surface hardness even when a hard coat layer is provided. When the polyethylene film is used as a substrate, the coating amount when applying the coating material of the present invention is in the range of 1 to 100 μm, preferably 1 to 20 μm after drying, depending on the application. It is preferable to apply as described above. In general, when a paint is applied with a film thickness exceeding 20 μm, it tends to curl greatly compared to the case where it is applied with a relatively thin film thickness, but the paint of the present invention is excellent in curling resistance. Since it also has characteristics, curling hardly occurs even when it is applied with a relatively high film thickness exceeding 30 μm, and it can be suitably used. Examples of the coating method at that time include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing.

  Among the plastic films, the polymethyl methacrylate film is generally relatively thick and durable with a thickness of about 50 to 2,000 μm, so it is suitable for applications that require a particularly high surface hardness, such as applications for the front plate of liquid crystal displays. It is the film used for. When the polymethyl methacrylate film is used as a base material, the coating amount when applying the coating material of the present invention is in the range of 1 to 100 μm, preferably 1 to 20 μm in thickness after drying according to the application. It is preferable to apply so that it becomes. In general, when a coating is applied on a relatively thick film such as a polymethyl methacrylate film with a film thickness exceeding 20 μm, it becomes a laminated film having a high surface hardness, but the transparency tends to decrease. However, since the coating material of the present invention has very high transparency as compared with the conventional coating material, a laminated film having both high surface hardness and transparency can be obtained. Examples of the coating method at that time include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing.

  Of the plastic films, cycloolefin polymer films are generally weak against lateral forces such as tearing, and are known to have poor folding resistance, but in recent years from the viewpoint of transparency and heat resistance. The area of use is expanding. In particular, the cured coating film obtained from the resin composition of the present invention is excellent in followability to the film itself and has flexibility even in such a fragile film, and thus effectively breaks the film when it is bent. Can be prevented. From the viewpoint of suitably exhibiting such an effect, the thickness of the cured coating film is preferably adjusted in the range of 1 to 10 μm. Examples of the coating method at that time 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 irradiated when the coating material of the present invention is cured to form a coating film include ultraviolet rays and electron beams. In the case of curing with ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, or a metal halide lamp is used as a light source, and the amount of light, the arrangement of the light source, etc. are adjusted as necessary. When using a high-pressure mercury lamp, it is preferable to cure at a conveyance speed of 5 to 50 m / min for one lamp having a light quantity that is usually in the range of 80 to 160 W / cm. On the other hand, in the case of curing with an electron beam, it is preferably cured with an electron beam accelerator having an accelerating voltage that is usually in the range of 10 to 300 kV at a conveyance speed of 5 to 50 m / min.

  Moreover, the base material to which the paint of the present invention is applied can be suitably used not only as a plastic film but also as a surface coating agent for various plastic molded products, for example, cellular phones, electric appliances, automobile bumpers and the like. . In this case, examples of the method for forming the coating film include a coating method, a transfer method, and a sheet bonding method.

  The coating method is a method in which the paint is spray-coated or coated as a top coat on a molded product using a printing device such as a curtain coater, roll coater, gravure coater, etc., and then cured by irradiation with active energy rays. is there.

  Next, the coating film of the present invention is a coating film formed by applying and curing the coating material of the present invention on the above-described plastic film, or coating and curing the coating material of the present invention as a surface protective agent for plastic molded products. The film of the present invention is a film having a coating film formed on a plastic film.

  Among the various uses of the film, as described above, a film obtained by applying the paint of the present invention on a plastic film and irradiating an active energy ray is used as a protective film for a polarizing plate used for a liquid crystal display, a touch panel display or the like. It is preferable to use as the coating film hardness. Specifically, when the paint of the present invention is applied to a protective film of a polarizing plate used for a liquid crystal display, a touch panel display, etc., and the film is formed by irradiating and curing active energy rays, the cured coating film has a high hardness. It becomes a protective film that combines high transparency. In the use of a protective film for a polarizing plate, an adhesive layer may be formed on the traditional side of the coating layer to which the paint of the present invention is applied.

  Hereinafter, the present invention will be described more specifically with reference to specific production examples and examples, but the present invention is not limited to these examples. Unless otherwise indicated, all parts and percentages in the examples are based on mass.

  In the examples of the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured using a gel permeation chromatograph (GPC) under the following conditions.

Measuring device: HLC-8220 manufactured by Tosoh Corporation
Column: Guard column H _XL- H manufactured by Tosoh Corporation
+ Tosoh Corporation TSKgel G5000HXL
+ Tosoh Corporation TSKgel G4000HXL
+ Tosoh Corporation TSKgel G3000HXL
+ Tosoh Corporation TSKgel G2000HXL
Detector: RI (differential refractometer)
Data processing: Tosoh Corporation SC-8010
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow rate: 1.0 ml / min Standard: Polystyrene sample: 0.4 mass% tetrahydrofuran solution filtered in terms of resin solids with a microfilter (100 μl)

Synthesis Example 1 (Synthesis of urethane acrylate A1)
Nitrogen gas was blown into a 3 liter clean separable flask equipped with a stirrer, a gas introduction tube, a condenser, a dropping funnel and a thermometer, and the air in the flask was replaced with nitrogen gas. Then, 444 g of isophorone diisocyanate and dibutyl were added to the flask. Tin diacetate 0.1g and methoquinone 0.5g were added, and it heated up to 70 degreeC, stirring. Then 234 g of hydroxyethyl acrylate was added over 1 hour. After further holding for 2 hours, Crisbon CMA-244 [DIC Corporation linear polyester diol, hydroxyl value: 56, weight average molecular weight 2,000] was added to 2,004 g, and then held at 80 ° C. for 3 hours. As a result, 2,682 g of urethane acrylate having 2 acryloyl groups in the molecule [nonvolatile content: 100%] was obtained. Hereinafter, this is referred to as urethane acrylate resin (A1).

Synthesis Example 2 (Synthesis of urethane acrylate A2)
Nitrogen gas was blown into a 3 liter clean separable flask equipped with a stirrer, a gas introduction tube, a condenser, a dropping funnel and a thermometer, and the air in the flask was replaced with nitrogen gas. Then, 444 g of isophorone diisocyanate and dibutyl were added to the flask. Tin diacetate 0.1g and methoquinone 0.5g were added, and it heated up to 70 degreeC, stirring. Then 234 g of hydroxyethyl acrylate was added over 1 hour. After further holding for 2 hours, 500 g of Kuraray polyol P-510 [Kuraray Co., Ltd. polyester diol, hydroxyl value: 225, weight average molecular weight 500] was added, and then held at 80 ° C. for 3 hours to form acryloyl groups. 1,178 g of urethane acrylate having 2 in it [nonvolatile content: 100%] was obtained. Hereinafter, this is referred to as urethane acrylate resin (A2).

Synthesis Example 3 (Synthesis of urethane acrylate A3)
Nitrogen gas was blown into a 3 liter clean separable flask equipped with a stirrer, a gas introduction tube, a condenser, a dropping funnel and a thermometer, and the air in the flask was replaced with nitrogen gas. Then, 444 g of isophorone diisocyanate and dibutyl were added to the flask. Tin diacetate 0.1g and methoquinone 0.5g were added, and it heated up to 70 degreeC, stirring. Then 234 g of hydroxyethyl acrylate was added over 1 hour. After further holding for 2 hours, 500 g of Kuraray polyol P-5010 [polyester diol manufactured by Kuraray Co., Ltd., hydroxyl value: 22, weight average molecular weight 5,000] was added, and then the mixture was held at 80 ° C. for 3 hours to obtain an acryloyl group. 5,678 g of urethane acrylate (nonvolatile content: 100%) having 2 in the molecule was obtained. Hereinafter, this is referred to as urethane acrylate resin (A3).

Synthesis Example 4 (Synthesis of acrylic acrylate B1)
A reactor equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introducing tube was charged with 498 parts by mass of methyl isobutyl ketone, and the temperature was raised until the system temperature reached 110 ° C. while stirring, and then glycidyl methacrylate 136 Over a period of 2 hours, a mixed solution consisting of 31 parts by mass, 97 parts by mass of methyl methacrylate, 163 parts by mass of ethyl acrylate, and 31 parts by mass of t-butylperoxy-2-ethylhexanoate (“Perbutyl O” manufactured by Nippon Emulsifier Co., Ltd.) After dropping from the dropping funnel, it was kept at 110 ° C. for 15 hours. Next, after the temperature was lowered to 90 ° C., 0.1 part by weight of methoquinone and 70 parts by weight of acrylic acid were added, 5 parts by weight of triphenylphosphine was added, the temperature was further raised to 100 ° C. and held for 8 hours. 1000 parts by mass of a methyl isobutyl ketone solution of acrylate (B1) was obtained. Each property value of the acrylic acrylate (B1) was as follows. Nonvolatile content: 50.0% by mass, Gardner viscosity (25 ° C.): A1-A, Gardner color: 1 or less, GPC styrene conversion weight average molecular weight (Mw): 15,000, solid content conversion theoretical acryloyl equivalent: 479 g / Eq

Example 1
25 parts by mass of urethane acrylate (A1) obtained in Synthesis Example 1, 40 parts by mass of a methyl isobutyl ketone (MIBK) solution of acrylic acrylate (B1) (20 parts by mass of acrylic acrylate B1 in 40 parts by mass), urethane acrylate (A1 25 parts by mass of Aerosil R7200 (“Aerosil R7200” manufactured by Nippon Aerosil Co., Ltd., silica fine particles having an average primary particle size of 12 nm) and 100 parts by mass of MIBK are mixed to obtain a slurry having a nonvolatile content of 45% by mass. Was mixed and dispersed using a wet ball mill (Ashizawa Co., Ltd. “Star Mill LMZ015”) to obtain a dispersion.

Each condition of dispersion by the wet ball mill is as follows.
Media: Zirconia beads having a median diameter of 100 μm Filling ratio of resin composition with respect to the inner volume of the mill: 70% by volume
Peripheral speed at the tip of the stirring blade: 11 m / sec
Flow rate of resin composition: 200 ml / min
Dispersion time: 60 minutes

  To 100 parts by mass of the resulting dispersion, 3 parts by mass of a photoinitiator (“Irgacure # 184” manufactured by Ciba Specialty Chemicals) is added, and MIBK is further added to adjust the nonvolatile content to 30% by mass. A functional resin composition was obtained. The performance of the active energy ray-curable resin composition was evaluated by the following tests, and the results are shown in Table 1.

Folding resistance test of coating film Preparation method of cured coating film The coating material is applied on a cycloolefin film (film thickness 100 μm) with a bar coater (film thickness 5 μm), dried at 80 ° C. for 2 minutes, and high pressure under nitrogen A test piece having a cured coating film was obtained by passing through a mercury lamp at a dose of 500 mJ / cm ² and curing.

The cured film of the test piece was evaluated by the MIT test machine under the following conditions.
Conditions: Load 300g, bending speed 90cpm, bending radius 0.38mm
Bending speed 90 °

Anti-blocking test of coating film Preparation method of cured coating film A coating film was prepared in the same manner as in the folding resistance test.
When a coating film coated with a general-purpose ultraviolet curable resin (eg, Unidic 17-806, manufactured by DIC Corporation) and the coated surface of the above test piece are put together and rubbed together under a load to slide smoothly (anti-blocking) It was judged as “Yes” and “No slipping” (blocking).

Examples 2-6
A paint was obtained in the same manner as in Example 1 except that the composition of the composition was as shown in Table 1. About these, the test similar to Example 1 was done. The results are shown in Table 1.

Comparative Examples 1-6
A paint was obtained in the same manner as in Example 1 except that the composition was as shown in Table 2. The results are shown in Table 2.

  Compound D1: Aronix M-402 (manufactured by Toa Gosei Co., Ltd.)

Claims (14)

Urethane (meth) acrylate (A) of linear polyester (a) having a weight average molecular weight of 600 to 3,000 obtained from aliphatic diol (a1) and dicarboxylic acid or acid anhydride (a2), and weight average An active energy ray having a molecular weight in the range of 2,000 to 50,000 and containing an acrylic polymer (B) having a (meth) acryloyl group in the molecular structure and inorganic fine particles (C) Curable resin composition. The active energy ray-curable resin composition according to claim 1, further comprising (meth) acrylate (D) other than the urethane (meth) acrylate (A) and the acrylic polymer (B). The urethane (meth) acrylate (A) has a weight average molecular weight of 1,000 to 3,000 obtained from an aliphatic diol (a1) and a dicarboxylic acid or an acid anhydride (a2). The active energy according to claim 1 or 2, which is a urethane (meth) acrylate obtained by reacting a glassy polyester (a), a polyfunctional isocyanate compound (a3), and a (meth) acrylate (a4) having a hydroxyl group. A linear curable resin composition. The active energy ray-curable resin composition according to any one of claims 1 to 3, wherein the aliphatic diol (a1) is an alkylene diol having 2 to 6 carbon atoms. The dicarboxylic acid or acid anhydride (a2) thereof is one or more dicarboxylic acids selected from the group consisting of adipic acid, phthalic acid, succinic acid and tetrahydrophthalic acid or acid anhydrides thereof. The active energy ray-curable resin composition according to any one of the above. The acrylic polymer (B) obtained by polymerizing the compound (x) having a reactive functional group and a (meth) acryloyl group as an essential component, and the compound (x) The active energy ray according to any one of claims 1 to 5, which is a polymer obtained by reacting a compound (y) having a (meth) acryloyl group with a functional group capable of reacting with the reactive functional group. Curable resin composition. The active energy ray-curable resin composition according to any one of claims 1 to 6, wherein the acrylic polymer (B) has a (meth) acryloyl group equivalent in a range of 150 to 1600 eq / g. The blending ratio (mass ratio) (A) / (B) of the urethane (meth) acrylate (A) and the acrylic polymer (B) is in the range of 0.18 to 8.0. 8. The active energy ray-curable resin composition according to any one of 7 above. The active energy ray-curable resin composition according to any one of claims 1 to 8, wherein the inorganic fine particles (C) are one or more inorganic fine particles selected from the group consisting of silica, zirconia and alumina. The active energy ray-curable resin composition according to claim 1, wherein the inorganic fine particles (C) are dry silica. A paint comprising the active energy ray-curable resin composition according to any one of claims 1 to 10. A coating film obtained by curing the paint according to claim 11. A laminated film, wherein the coating film according to claim 12 is laminated on a plastic film. The laminated film according to claim 13, wherein the plastic film is a cycloolefin polymer film.