JP6565276B2 - Curable composition, cured product and laminate - Google Patents

Description

  The present invention relates to a curable composition that is excellent in coating property and curability and can give a cured product excellent in scratch resistance, transparency, hardness, flexibility, and the like even when substantially free of an organic solvent. Moreover, this invention relates to the hardened | cured material and laminated body obtained using this curable composition.

  Polycarbonate (PC) resin; Polymethyl methacrylate (PMMA) resin; Polyethylene terephthalate (PET) resin; Polybutylene terephthalate (PBT) resin, Acrylonitrile-butadiene-styrene (ABS) resin, Styrene-methyl methacrylate (MS) resin, Acrylonitrile- Styrene resins such as styrene (AS) resins; vinyl chloride resins; plastic products using various resin base materials such as cellulose acetate resins such as triacetyl cellulose are excellent in light weight, easy processability, impact resistance, etc. Therefore, they are used in various applications such as containers, instrument panels, packaging materials, various housing materials, optical disk substrates, plastic lenses, substrates of display devices such as liquid crystal displays and plasma displays. On the other hand, since these plastic products generally have low hardness, they are easily damaged and wear resistance is not sufficient, so that it is difficult to use them in fields where these performances are required. For this reason, hard coat materials (coating materials) that impart hardness and abrasion resistance to the surface of plastic products are widely used.

  Typical examples of hard coating materials are obtained by dispersing active energy ray-curable compounds such as polyfunctional (meth) acrylates and urethane (meth) acrylate oligomers, polymerization initiators, and various additives in organic solvents. Hard coat materials that can be used. Such an organic solvent-based hard coat material can be applied with an organic solvent in a state in which the coating liquid viscosity is low, and thus has an advantage that it is easy to ensure a smooth coating film appearance. However, in recent years, it has become an important issue to suppress emission of volatile organic compounds (VOC) including organic solvents due to concerns about environmental burdens.

  Against this background, it has been studied to remove the organic solvent from the coating liquid of the hard coat material. However, as a result of removing the organic solvent, the viscosity of the liquid may be increased and the coating may be hindered. In order to solve this problem, various solventless hard coat materials have been studied. In particular, a method of using a polyfunctional (meth) acrylate having a multi-branched skeleton called a dendrimer or a hyperbranched polymer has recently been used as a method for lowering the viscosity of a hard coat material for ensuring coating properties without solvent. ing. As an example of a solvent-free hard coat material using such a polyfunctional (meth) acrylate having a multi-branched skeleton, for example, in Patent Document 1, a polyfunctional (meth) acrylate having a multi-branched skeleton, a polyfunctional urethane acrylate A solvent-free hard coat material containing a polymerizable monomer is disclosed.

JP 2009-272025 A

  As a result of the study of the present inventors, it has been found that the hard coat material disclosed in Patent Document 1 has a problem that the curability and scratch resistance are insufficient.

The object of the present invention is to solve such problems of the prior art.
That is, the problem of the present invention is that the curability can provide a cured product having excellent coating properties and curability and excellent scratch resistance, transparency, hardness, flexibility, and the like even when substantially free of an organic solvent. It is providing the hardened | cured material and laminated body obtained using a composition and this curable composition.

  As a result of intensive studies by the inventor in view of the above-mentioned problems of the conventional technology, a curable composition containing a specific amount of (meth) acrylate having a dendrimer structure and / or hyperbranched polymer structure and a specific urethane (meth) acrylate It discovered that a thing could solve the said subject. That is, the gist of the present invention is as follows.

[1] Curability including the following component (A) and the following component (B), and the content of the component (B) is 1 to 45% by weight with respect to the total amount of the component (A) and the component (B) Composition.
Component (A): A (meth) acrylate component having a dendrimer structure and / or a hyperbranched polymer structure (B): having three or more (meth) acryloyl groups and a urethane bond, and a viscosity at 40 ° C. of 30 (Meth) acrylate that is 1,000 to 100,000 mPa · s

[2] The curable composition according to claim 1, wherein the component (B) has a nurate structure.

[3] The curable composition according to [1] or [2], wherein the component (A) has a weight average molecular weight (Mw) of 1000 to 20,000.

[4] The curable composition according to any one of [1] to [3], wherein the component (B) has 8 to 30 (meth) acryloyl groups.

[5] The curable composition according to any one of [1] to [4], which does not contain an organic solvent or contains an organic solvent and has a solid content concentration of 90% by weight or more.

[6] Any of [1] to [5], including a polymerization initiator and having a content of 0.1 to 10 parts by weight with respect to 100 parts by weight as a total of component (A) and component (B) A curable composition according to any one of the above.

[7] The monofunctional (meth) acrylate is not contained, or the monofunctional (meth) acrylate is contained, and the content thereof is 10% by weight or less based on the entire curable composition, [1] to [6 ] The curable composition in any one of.

[8] A cured product obtained by curing the curable composition according to any one of [1] to [7] with active energy rays.

[9] A laminate having a substrate and a hard coat layer, the hard coat layer being coated with the curable composition according to any one of [1] to [7] on the substrate. A laminate formed by irradiation with active energy rays.

[10] The laminate according to [9], wherein the substrate is a plastic substrate.

[11] The laminate according to [10], wherein the plastic substrate is at least one selected from polycarbonate resin, polyethylene terephthalate resin, and polymethyl methacrylate resin.

  According to the present invention, a curable composition that can provide a cured product that is excellent in coating property and curability and excellent in scratch resistance, transparency, hardness, flexibility, and the like even if it does not substantially contain an organic solvent. Is provided. In addition, according to the present invention, using this curable composition, a cured product having excellent scratch resistance, transparency, hardness, flexibility, etc., and excellent scratch resistance, transparency, hardness, flexibility, etc. A laminate having a hard coat layer can be produced with good workability.

  Embodiments of the present invention will be described in detail below, but the following description is an example of the embodiments of the present invention, and the present invention is limited to the following description unless it exceeds the gist. is not. In addition, when using the expression “to” in the present specification, it is used as an expression including numerical values or physical property values before and after the expression.

In the present invention, when the expression “(meth) acryl” is used, it means one or both of “acryl” and “methacryl”. “(Meth) acryloyl” and “(meth) acrylate” have the same meaning.
In the present invention, the “number of (meth) acryloyl group functional groups” refers to the number of (meth) acryloyl groups contained in one molecule of (meth) acrylate.

In the present invention, the weight average molecular weight (Mw) of the component (A) and the component (B) is a value in terms of polystyrene measured by gel permeation chromatography (GPC), and is measured under the following conditions, for example. However, catalog values can be adopted for commercial products.
<Measurement conditions of weight average molecular weight (Mw)>
Equipment: “HLC-8120GPC” manufactured by Tosoh Corporation
Column: Tosoh Corporation
"TSKgel superH1000 + H2000 + H3000"
Detector: Differential refractive index detector (RI detector / built-in)
Solvent: Tetrahydrofuran Temperature: 40 ° C
Flow rate: 0.5 mL / min Injection volume: 10 μL
Concentration: 0.2% by weight
Calibration sample: Monodispersed polystyrene Calibration method: Polystyrene conversion In the present invention, the viscosity of the component (A) and the component (B) at 40 ° C. is measured using an E-type viscometer, for example, under the following measurement conditions. However, catalog values can be adopted for commercial products.
<Measurement conditions for viscosity>
Solid content: 100% by weight
Temperature: 40 ° C
Equipment: E-type viscometer TV-20 manufactured by TOKIMEC

(Curable composition)
The curable composition of this invention contains the following component (A) and the following component (B), and content of a component (B) is 1-45 with respect to the total amount of a component (A) and a component (B). It is characterized by weight percent.
Component (A): A (meth) acrylate component having a dendrimer structure and / or a hyperbranched polymer structure (B): having three or more (meth) acryloyl groups and a urethane bond, and a viscosity at 40 ° C. of 30 (Meth) acrylates from 1,000 to 100,000

[Component (A)]
The component (A) used in the curable composition of the present invention is a (meth) acrylate having a dendrimer structure and / or a hyperbranched polymer structure, and mainly a coating property of the curable composition and a cured product obtained (cured film). ) Is a component that contributes to improvement in flexibility.

  The dendrimer structure is a structure in which a branched structure is further branched to form a multi-branched structure, and the branched structure spreads radially. The hyperbranched polymer structure is a structure in which the multi-branched structure is not radial but extends in a branched manner in a predetermined direction or two or more directions, and is a concept including a hyperbranched polymer structure and is called a dendrimer structure In some cases. A (meth) acrylate having a dendrimer structure and / or a hyperbranched polymer structure can introduce a large number of reactive functional groups on the outermost surface of the molecule at a high density. Because of its low viscosity compared to linear polymers, it contributes to improving the coatability of the curable composition and has a structure in which the cross-linking density at the center of the molecule is sparse. This contributes to improving the flexibility and suppressing warpage.

  As described above, the dendrimer structure is often used in a concept including a hyperbranched polymer structure in a broad sense. Hereinafter, the (meth) acrylate having a dendrimer structure and / or a hyperbranched polymer structure may be collectively referred to as “dendrimer (meth) acrylate”.

  Although the manufacturing method of the dendrimer (meth) acrylate of a component (A) is not restrict | limited in particular, a multiple branch structure is formed by repeating reaction represented, for example by following formula (1), Then, following formula (2) By reacting with the core compound in accordance with the reaction represented to form a dendrimer structure, by reacting the substituent R at the branch end of the dendrimer with a (meth) acrylic acid and / or (meth) acrylic acid derivative Can be manufactured.

  In addition to the above production method, the production method of the dendrimer (meth) acrylate of component (A) can also be obtained by the following production method.

  First, a hydroxy acid having at least two hydroxyl groups is successively reacted with an alcohol to obtain a compound having a multi-branched structure and having a plurality of hydroxyl groups at the terminals. The reaction time in this sequential reaction is usually 3 to 60 hours, preferably 5 to 40 hours, and the reaction temperature is usually 50 to 200 ° C, preferably 60 to 150 ° C. In addition, this reaction can be normally implemented in presence of an acid catalyst in an organic solvent.

  The alcohol that can be used in the above method is not particularly limited, and examples thereof include methanol, ethanol, propanol, butanol, ethylene glycol, glycerol, trimethylolpropane, pentaerythritol, and dipentaerythritol. These alcohols may be used alone or in combination of two or more, but it is preferable to use one alcohol from the viewpoint of obtaining a dendrimer (meth) acrylate having a regular structure.

  The hydroxy acid having two or more hydroxyl groups is not particularly limited, and examples thereof include dimethylolpropionic acid, glyceric acid, mevalonic acid, and pantoic acid. These hydroxy acids may be used alone or in combination of two or more, but it is preferable to use one hydroxy acid from the viewpoint of obtaining a regular dendrimer (meth) acrylate.

  Furthermore, the organic solvent that can be used in this reaction is not particularly limited, and examples thereof include cyclohexane, n-hexane, heptane, methylcyclohexane, toluene and the like. The acid catalyst is not particularly limited, and examples thereof include organic acids such as p-toluenesulfonic acid, methanesulfonic acid, and benzenesulfonic acid; inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, and boric acid.

  As a method for controlling the above reaction more strictly, as disclosed in JP-A-2008-81725, a hydroxyl group of a compound having a multi-branched structure and having a plurality of hydroxyl groups at the terminal is converted to benzylidene. The method of protecting by etc. is mentioned. In order to deprotect the protected hydroxyl group for the next step, a method of washing with an acid such as hydrochloric acid can be mentioned.

  A compound having a multi-branched structure obtained by the above reaction and having a plurality of hydroxyl groups at the terminal is reacted with a (meth) acrylate having a functional group capable of reacting with a hydroxyl group, and a plurality of terminals are reacted. By introducing a (meth) acryloyl group, a dendrimer (meth) acrylate can be obtained. In this reaction, the reaction time is usually 1 to 12 hours, preferably 3 to 8 hours, and the reaction temperature is usually 50 to 200 ° C, preferably 60 to 150 ° C. In addition, this reaction can be implemented in presence of the same acid catalyst in the organic solvent similar to the sequential reaction in a previous process.

  Examples of the functional group capable of reacting with a hydroxyl group include a carboxyl group, an epoxy group, and an isocyanate group. Further, the compound having a functional group capable of reacting with a hydroxyl group and a (meth) acryloyl group is not particularly limited. For example, a succinic acid adduct of (meth) acrylic acid or pentaerythritol tri (meth) acrylate is used. A compound having a carboxyl group such as methacrylic acid and a (meth) acryloyl group; a compound having an epoxy group such as glycidyl (meth) acrylate and a (meth) acryloyl group; an isocyanate group such as isocyanate ethyl (meth) acrylate and (meth And compounds having an acryloyl group. These may be used alone or in combination of two or more.

  It is preferable that the weight average molecular weight (Mw) of the dendrimer (meth) acrylate of a component (A) is 500-10,000. When the weight average molecular weight (Mw) of the dendrimer (meth) acrylate of the component (A) is 5,000 or less, the viscosity of the curable composition can be lowered and the coating property can be improved. From this viewpoint, the weight average molecular weight (Mw) of the dendrimer (meth) acrylate of the component (A) is more preferably 7,000 or less, and further preferably 4,000 or less. On the other hand, the lower limit of the weight average molecular weight (Mw) of the dendrimer (meth) acrylate of component (A) is preferably 500 or more, more preferably 800 or more, still more preferably 1,000 or more, from the viewpoint of improving flexibility. It is.

  In addition, as described above, the dendrimer (meth) acrylate of the component (A) is converted into a plurality of (meth) by introducing (meth) acryloyl groups by reacting (meth) acrylate with the tip portion of the multi-branched structure. It can have an acryloyl group, and the number of functional groups of the (meth) acryloyl group is preferably 3 or more, more preferably 5 or more, and still more preferably 7 or more from the viewpoint of curability. . On the other hand, from the viewpoint of flexibility, the number of (meth) acryloyl group functional groups is preferably 30 or less, more preferably 25 or less, and even more preferably 20 or less.

  As described above, the dendrimer (meth) acrylate usually tends to have a lower viscosity when the molecular weight is the same as that of the polyfunctional (meth) acrylate not having a dendrimer structure. The component (A) dendrimer (meth) acrylate has a viscosity at 40 ° C. of preferably 10,000 mPa · s or less, more preferably 7,000 mPa · s or less, from the viewpoint of the coating properties of the curable composition. Yes, more preferably 4,000 mPa · s or less, and from the viewpoint of curability, it is preferably 10 mPa · s or more, more preferably 50 mPa · s or more, and further preferably 100 mPa · s or more.

  A commercial item can also be used as a dendrimer (meth) acrylate of a component (A), As a commercial item of a dendrimer (meth) acrylate, Osaka Organic Chemical Industry Co., Ltd. Viscoat V # 1000, SIRIUS-501, SUBARRU, for example. -501 etc. are mentioned. Among the dendrimer (meth) acrylates of component (A), those having a hyperbranched polymer structure include SARTOMER (registered trademark) CN2302, CN2303, CN2304, etc. manufactured by Sakai Kogyo Co., Ltd.

  As a component (A), 1 type of these may be used independently, and 2 or more types may be mixed and used for it.

[Component (B)]
Component (B) used in the curable composition of the present invention has 3 or more (meth) acryloyl groups and a urethane bond, and has a viscosity at 40 ° C. of 30,000 to 100,000 mPa · s. (Meth) acrylate (hereinafter sometimes referred to as “urethane (meth) acrylate”), which mainly contributes to improving the curability of the curable composition and the scratch resistance of the resulting cured product (cured film). It is an ingredient to do.

  As described above, the component (B) has three or more (meth) acryloyl groups. For this reason, the curable composition of the present invention has good curability, flexibility, scratch resistance, and the like. It becomes. From these viewpoints, the number of (meth) acryloyl groups in component (B) is preferably 6 or more, more preferably 8 or more, and even more preferably 10 or more. On the other hand, the number of (meth) acryloyl groups in component (B) is preferably 30 or less, and more preferably 20 or less, from the viewpoint of coatability.

  In the present invention, the urethane (meth) acrylate of the component (B) includes both those having a urethane structure and those having a nurate structure, and the urethane (meth) acrylate of the component (B) There is no particular limitation as long as it has at least one of a nurate structure and three or more (meth) acryloyl groups and has a specific viscosity.

  Among the urethane (meth) acrylates of component (B), those having a urethane structure include, for example, urethane (meth) acrylates obtained by reacting an isocyanate compound with a (meth) acrylate having a hydroxy group, and many isocyanate compounds. Examples thereof include urethane (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylate with a urethane prepolymer obtained by reacting a monohydric alcohol.

  Examples of the isocyanate compound include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate. Aromatic diisocyanates such as ethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate and the like chain aliphatic diisocyanates; isophorone Alicyclic diisos such as diisocyanate, dicyclohexylmethane-4,4-diisocyanate, methylcyclohexylene diisocyanate Or alkylene arylene alkylene diisocyanate such as tetramethylxylylene diisocyanate (wherein “alkylene arylene alkylene” refers to a group bonded in the order of aliphatic hydrocarbon group-aromatic hydrocarbon group-aliphatic hydrocarbon group). Meaning).

  Of these, alicyclic diisocyanates are preferred.

  As the (meth) acrylate having a hydroxy group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned. As the (meth) acrylate having a hydroxy group, pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are particularly preferable.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, polytetramethylene glycol, 1, 5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-ethyl-1,3-hexane glycol, 2,2,4-trimethyl-1,3- Aliphatic diols such as pentanediol, 3,3-dimethylolheptane, 1,9-nonanediol, 2-methyl-1,8-octanediol; alicyclic diols such as cyclohexanedimethanol; bishydroxyethoxybenzene, bis Hydroxyethyl terephthalate, Aromatic diols such as Sphenol A; dialkanolamines such as N-methyldiethanolamine; triols such as trimethylolpropane and glycerin; polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutadiene diol, polyester diol, polycaprolactone And high molecular weight polyols such as diol and polycarbonate diol.

  Among the urethane (meth) acrylates having the urethane structure, urethane (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylate with a compound obtained by reacting an isocyanate compound with a polyhydric alcohol is preferable.

  Among these, from the viewpoint of curability and scratch resistance, alicyclic diisocyanates and alkyl diols / triols having 1 to 6 carbon atoms such as diols / triols such as ethylene glycol, 1,4-butanediol, trimethylolpropane, etc. The compound obtained by reacting at least one of the polyhydric alcohols with at least one hydroxy group in the group consisting of hydroxyethyl acrylate, pentaerythritol triacrylate and dipentaerythritol pentaacrylate (meth) Urethane (meth) acrylate obtained by reacting with acrylate is preferred.

  Specific examples of the urethane (meth) acrylate having a nurate structure include tris (acryloyloxyethyl) isocyanurate, tris (methacryloyloxyethyl) isocyanurate, tris (2-acryloyloxypropyl) isocyanurate, Examples include tris (2-methacryloyloxypropyl) isocyanurate, tris (acryloyloxyethoxyethyl) isocyanurate, tris (methacryloyloxyethoxyethyl) isocyanurate, etc., and these may be used alone or in combination of two or more. Can be used. Among these, tris (acryloyloxyethyl) isocyanurate is preferable.

  Among the urethane (meth) acrylates of the component (B), preferred are urethane (meth) acrylates having a urethane structure and a nurate structure from the viewpoint of improving scratch resistance and curability. Specific examples of urethane (meth) acrylates having a urethane structure and a nurate structure include compounds obtained by reacting a polyhydric alcohol with a compound having a nurate structure in which the above-mentioned isocyanate compound is a trimer. Can do. Furthermore, what is obtained by reacting the compound thus obtained with a (meth) acrylate having a hydroxy group is preferred.

  The polyhydric alcohol that can be used here and the (meth) acrylate having a hydroxy group are the same as those mentioned in the description of the urethane (meth) acrylate having the urethane structure.

  Specific examples of the compound having a nurate structure in which an isocyanate is trimerized include aliphatic polyisocyanates having a nurate structure such as polyhexamethylene diisocyanate (isocyanurate type), and polyisophorone diisocyanate (isocyanurate type). And alicyclic polyisocyanates having a nurate structure such as

  The viscosity of the component (B) urethane (meth) acrylate at 40 ° C. is 30,000 to 100,000 mPa · s. When the viscosity is 30,000 mPa · s or more, the curability is good. In this respect, the viscosity of the component (B) urethane (meth) acrylate at 40 ° C. is preferably 30,000 mPa · s or more, and more preferably 35,000 mPa · s or more. On the other hand, a urethane (meth) acrylate having a viscosity of 100,000 mPa · s or less is suitable for ensuring coatability. From this viewpoint, the viscosity at 40 ° C. of the urethane (meth) acrylate of the component (B) is preferably 90,000 mPa · s or less, and more preferably 85,000 mPa · s or less.

  Moreover, it is preferable that the weight average molecular weights (Mw) of the urethane (meth) acrylate of a component (B) are 1000-20,000. When the weight average molecular weight (Mw) of the urethane (meth) acrylate of the component (B) is 20,000 or less, it is preferable in terms of compatibility with the component (A). From this viewpoint, the urethane ( The weight average molecular weight (Mw) of the (meth) acrylate is more preferably 14,000 or less, and still more preferably 8,000 or less. On the other hand, the lower limit of the weight average molecular weight (Mw) of the urethane (meth) acrylate of the component (B) is preferably 800 or more, more preferably 400 or more, still more preferably 1,000 or more, from the viewpoint of obtaining viscosity. is there.

  Commercially available products may be used as the component (B) urethane (meth) acrylate, for example, U-10HA, U15HA, UA-53H, UA-33H, etc. manufactured by Shin-Nakamura Chemical Co., Ltd. may be used.

  As the component (B) urethane (meth) acrylate, one type may be used alone, or two or more types may be used in combination.

[Content Ratio of Component (A) and Component (B)]
The curable composition of this invention contains 1-45 weight% of components (B) with respect to the total amount of a component (A) and a component (B). The component (B) contributes to the curability of the curable composition and the scratch resistance of the cured product (cured film), and the component (B) is added to the total amount of the component (A) and the component (B). By containing 1% by weight or more based on this, this effect can be obtained effectively. From the viewpoint of curability and scratch resistance, the curable composition of the present invention preferably contains the component (B) in an amount of 3% by weight or more based on the total amount of the component (A) and the component (B). More preferably 5% by weight or more, and even more preferably 7% by weight or more. On the other hand, when the content of the component (B) in the curable composition of the present invention is 45% by weight or less based on the total amount of the component (A) and the component (B), the coating of the curable composition is performed. The content of the component (A) contributing to the improvement of the flexibility and the flexibility of the cured product (cured film) can be ensured, and an excellent effect of improving the coating property and the flexibility can be obtained. From this viewpoint, the curable composition of the present invention preferably contains 45% by weight or less, and 40% by weight or less of the component (B) with respect to the total amount of the component (A) and the component (B). Is more preferable, it is more preferable to contain 35% by weight or less, and particularly preferable to contain 30% by weight or less.

[Polymerization initiator]
The curable composition of the present invention preferably contains a polymerization initiator in order to be cured by active energy rays. The polymerization initiator is usually 0.1 parts by weight or more, preferably 1.0 parts by weight with respect to 100 parts by weight in total of the component (A) and the component (B) in the curable composition of the present invention. Above, more preferably 2.0 parts by weight or more, and usually 10 parts by weight or less, preferably 5.0 parts by weight or less can be added.

  As a polymerization initiator, a photoinitiator is preferable, for example, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1 , 2-diphenylethane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-hydroxy-1- {4- [4- (2-hydroxy- 2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenyl Examples include phosphine oxide. These polymerization initiators may be used alone or in a combination of two or more.

[Monofunctional (meth) acrylate]
Even when the curable composition of the present invention does not contain a monofunctional (meth) acrylate or contains a monofunctional (meth) acrylate, the content thereof is 10% by weight based on the entire curable composition. The following is preferable.

  That is, in the above-mentioned Patent Document 1, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, methoxyethyl ( (Meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, isopropoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, (meth) acrylic acid 2-vinyloxyethyl, (meth) acrylic acid 2- ( 2-vinyloxyethoxy) ethyl, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) a Relate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxydiethylene glycol (meth) acrylate, butoxydiethylene glycol (meth) acrylate, phenoxyethyl ( It is said that monofunctional (meth) acrylates such as meth) acrylate, trifluoroethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate and the like are preferably contained in an amount of 10 to 60% by weight. When it contains, there exists a tendency for the hardness of the hardened | cured material (cured film) formed to fall. The object of the present invention is to obtain a cured product (cured film) having a high hardness, and such a monofunctional (meth) acrylate is not included or, if included, the content is included in the entire curable composition. On the other hand, it is preferably 10% by weight or less, particularly preferably 10% by weight or less, particularly preferably 0 to 5% by weight.

[Organic solvent]
The curable composition of the present invention may contain an organic solvent.

  It does not specifically limit as an organic solvent, The kind of component (A) and component (B), the kind of base material to which the curable composition of this invention is applied, the coating method to a base material, etc. are considered. And can be selected as appropriate. Specific examples of the organic solvent include, for example, n-hexane, n-heptane, n-octane, n-decane, n-dodecane, 2,3-dimethylhexane, 2-methylheptane, 2-methylhexane, and 3-methyl. Saturated hydrocarbon solvents such as hexane and cyclohexane; aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, Ether solvents such as ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, phenetole; ethyl acetate, Ester solvents such as butyl acid, isopropyl acetate and ethylene glycol diacetate; amide solvents such as dimethylformamide, diethylformamide and N-methylpyrrolidone; cellosolve solvents such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; methanol, ethanol and propanol And alcohol solvents such as isopropanol and butanol; halogen solvents such as dichloromethane and chloroform, and the like. These may be used alone or in combination of two or more.

  However, since the coating property of the curable composition of the present invention can be adjusted and improved by the aforementioned component (A), the curable composition of the present invention is a solvent-free system that does not contain an organic solvent. Preferably, even when an organic solvent is included, it is preferably included so that the solid content concentration is 90% by weight or more, and more preferably included so that the solid content concentration is 95% by weight or more. The upper limit of the solid content concentration is 100% by weight, that is, the organic solvent is not included. The curable composition of the present invention can be suitably used as a solvent-free system that does not substantially contain an organic solvent as described above, but it is also excellent in an organic solvent system having a solid content concentration of 90% by weight. The embodiment of the curable composition of the present invention is not limited to a solventless system. In the present invention, “solid content” means a component excluding the solvent, and includes not only a solid component but also a semi-solid or viscous liquid material.

  Thus, even if the curable composition of the present invention does not contain an organic solvent or contains an organic solvent, the solid content concentration is as small as 90% by weight or more, After applying the curable composition of the present invention to a substrate, the drying step for removing the organic solvent can be unnecessary or shortened, and productivity can be increased.

[Other ingredients]
The curable composition of this invention may contain other components other than said component (A), (B), a polymerization initiator, etc. in the range which does not inhibit the effect of this invention. Other components include UV absorbers, hindered amine light stabilizers, leveling agents (surface conditioning agents), fillers, silane coupling agents, reactive diluents, antistatic agents, organic pigments, dispersants, and thixotropic properties. Agents (thickening agents), antifoaming agents, antioxidants and the like.

  It is preferable to add a leveling agent to the curable composition of the present invention because the hard coat layer can be further provided with antifouling property and slipperiness. Examples of the leveling agent include a fluorine leveling agent, a silicone leveling agent, an acrylic leveling agent, and the like, and these can be used in appropriate combination. Moreover, in the curable composition of this invention, when using a leveling agent, the content shall be 0.01-30 weight part with respect to a total of 100 weight part of a component (A) and a component (B). The amount is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and particularly preferably 0.5 to 5 parts by weight.

  Moreover, it is preferable to mix | blend a filler with the curable composition of this invention. Examples of the filler include organic fillers and inorganic fillers. These may be used alone or in combination of two or more. Among these, it is preferable to contain inorganic fillers, particularly inorganic particles having an average primary particle diameter of 1 μm or less. By containing such inorganic particles, it is possible to obtain a curable composition capable of forming a hard coat layer with further excellent hardness. In addition, when used in combination with the above leveling agent, the antifouling property and slipperiness of the hard coat layer surface can be further improved.

  Examples of inorganic particles include silica (including organosilica sol), alumina, titania, zeolite, mica, synthetic mica, calcium oxide, zirconium oxide, zinc oxide, magnesium fluoride, smectite, synthetic smectite, vermiculite, ITO (indium oxide) / Tin oxide), ATO (antimony oxide / tin oxide), tin oxide, indium oxide, antimony oxide and the like. Among these, silica is preferable. Moreover, the inorganic particle mentioned above may use only 1 type, and may be used in combination of 2 or more type.

  When the curable composition of the present invention contains the inorganic particles as described above, the content thereof is 0.05 parts by weight or more with respect to 100 parts by weight in total of the component (A) and the component (B). Preferably, it is 0.5 parts by weight or more, more preferably 0.8 parts by weight or more, and particularly preferably 1 part by weight or more, while component (A) and component (B) Is preferably 100 parts by weight or less, more preferably 80 parts by weight or less, still more preferably 60 parts by weight or less, and particularly preferably 40 parts by weight or less. . It is preferable that the content of the inorganic particles is not less than the above lower limit value, since the effect of using the inorganic particles can be sufficiently obtained, and is preferably not more than the above upper limit value from the viewpoint of transparency.

[Method for producing curable composition]
The method for producing the curable composition of the present invention is not particularly limited, and can be obtained, for example, by mixing components (A) and (B) and, if necessary, a polymerization initiator and other components. When mixing each component, it is preferable to mix uniformly with a disperser, a stirrer, or the like.

[Hardened product / Laminate]
The cured product of the present invention can be obtained by curing the curable composition of the present invention by irradiating it with active energy rays. In particular, by applying and curing the curable composition of the present invention on a substrate or the like, a laminate obtained by forming a cured layer of the curable composition of the present invention on the substrate is obtained. it can. Moreover, a hard coat film (hard coat layer) can be obtained by apply | coating the curable composition of this invention on a base material etc. in this way, and making it harden | cure to a film form. Moreover, the film lamination formed by apply | coating the curable composition of this invention on another resin film as a base material, making it harden | cure, and shape | molding a hard-coat film, and laminating | stacking a hard-coat film on another resin film The body is obtained.
In the present invention, “application” is used as a concept including what is generally called “coating”.

  As a base material used for said laminated body, inorganic materials, such as organic materials, such as a plastic base material; a metal base material, a glass base material, are mentioned. As a constituent material of the plastic substrate, various synthetic resins such as acrylonitrile-butadiene-styrene copolymer (ABS) resin, polycarbonate (PC) resin, polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, polymethyl One type or two or more types such as methacrylate (PMMA) resin, polystyrene (PS) resin, and polyolefin resin can be used. The metal substrate is not particularly limited. For example, a steel plate such as a hot-rolled plate or a cold-rolled plate, a hot-dip galvanized steel plate, an electrogalvanized steel plate, tinplate, tin-free steel, various other types of plating, or an alloy-plated steel plate And metal plates such as stainless steel plates and aluminum plates. Furthermore, these may be subjected to various surface treatments such as phosphate treatment, chromate treatment, organic phosphate treatment, organic chromate treatment, heavy metal substitution treatment such as nickel. As a glass substrate, in addition to normal glass, glass subjected to various chemical treatments (for example, Corning Gorilla Glass (registered trademark), Asahi Glass Dragon Trail (registered trademark), etc.) and multicomponent glass. May be used.

  In particular, the curable composition of the present invention is suitable for forming a high-hardness hard coat layer having excellent scratch resistance on a substrate without impairing transparency and flexibility. As the base material, a plastic base material that is desired to be improved in scratch resistance and abrasion resistance is preferable. Among the plastic base materials, polycarbonate (PC) resin, polyethylene terephthalate (PET) resin, polymethyl methacrylate, which are excellent in transparency. What consists of (PMMA) resin is suitable.

  The hard coat layer formed on the substrate can be formed, for example, by applying (coating) the curable composition of the present invention on the substrate and irradiating it with active energy rays. Examples of the method for coating (coating) the curable composition of the present invention on a substrate include, for example, a reverse coating method, a gravure coating method, a rod coating method, a bar coating method, a Mayer bar coating method, a die coating method, and a spray coating. Law. The form of the cured product of the present invention is not particularly limited. Usually, a cured product obtained by irradiating and curing an active energy ray on a substrate is a cured film (cured) on at least a part of one side of the substrate. Film).

  Active energy rays that can be used in curing the curable composition of the present invention include ultraviolet rays, electron beams, X-rays, infrared rays, and visible rays. Among these active energy rays, ultraviolet rays and electron beams are preferable from the viewpoints of curability and prevention of resin deterioration.

When the curable composition of the present invention is cured by ultraviolet irradiation, various ultraviolet irradiation apparatuses can be used, and a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, an LED-UV lamp, or the like is used as the light source. Can do. Irradiation amount of the ultraviolet (in mJ / cm ²⁾ is usually 10~10,000mJ / cm ^2, in view of flexibility, such as the curing of the curable composition of the present invention, a cured product (cured film) from preferably 100~5,000mJ / cm ^2, more preferably 150~3,000mJ / cm ^2. In particular, since the curable composition of the present invention is excellent in curability, a good cured product (cured film) can be obtained even with an irradiation dose of 200 mJ / cm ² or less.

  Moreover, when hardening the curable composition of this invention by electron beam irradiation, various electron beam irradiation apparatuses can be used. The irradiation amount (Mrad) of the electron beam is usually 0.5 to 20 Mrad, and preferably 1 from the viewpoints of curability of the curable composition of the present invention, flexibility of the cured product, prevention of damage to the substrate, and the like. ~ 15 Mrad.

  The film thickness of the cured product of the present invention as the hard coat layer formed in this manner varies depending on the use, but is preferably 1 μm or more, more preferably 2 μm or more, and further preferably 3 μm or more. On the other hand, it is preferably 100 μm or less, more preferably 70 μm or less, still more preferably 40 μm or less, and particularly preferably 10 μm or less.

  The laminate of the present invention formed by forming a hard coat layer of the curable composition of the present invention on a substrate such as a plastic substrate may have other functional layers. The other functional layer can be provided on the surface of the substrate opposite to the surface on which the hard coat layer is formed, between the substrate and the hard coat layer, or on the surface of the hard coat layer. Examples of the functional layer include a conductive layer having a conductive function, a cushion function, an antireflection function, and an adhesive function, a cushion layer, an antireflection layer, and an adhesive layer. These layers may express two different functions in one layer.

[Use]
Since the laminate having a hard coat layer obtained by curing the curable composition of the present invention has high hardness and excellent scratch resistance, transparency, flexibility, etc., a liquid crystal display device (liquid crystal display), LED ( It can be used as a flat panel display such as a light emitting diode display), an ELD (electroluminescence display), a VFD (fluorescence display), and a PDP (plasma display panel). Particularly suitable for touch panel films that operate devices by holding down the display on the screen, such as bank ATMs, vending machines, personal digital assistants (PDAs), copiers, facsimiles, game machines, museums, department stores, etc. It is useful for guidance display devices, car navigation systems, multimedia stations (multifunctional terminals installed in convenience stores), mobile phones, railway vehicle monitoring devices, etc.

  EXAMPLES Hereinafter, although the content of this invention is demonstrated more concretely using an Example, this invention is not limited by a following example, unless the summary is exceeded. The values of various production conditions and evaluation results in the following examples have meanings as preferred values of the upper limit or lower limit in the embodiment of the present invention, and preferred ranges are the upper limit or lower limit values described above, and It may be a range defined by a combination of values of the examples or values between the examples.

[material]
The raw materials used in the following examples and comparative examples are as follows.

<Component (A)>
A-1: Dendrimer acrylate Biscoat 1000 (V # 1000) manufactured by Osaka Organic Chemical Industry Co., Ltd.
Number of (meth) acryloyl group functional groups: ≧ 14
Weight average molecular weight (Mw): 2,000
Viscosity: 220 mPa · s (40 ° C)

<Component (B)>
B-1: Polyfunctional urethane acrylate having 15 (meth) acryloyl groups (produced by the following method)
Number of (meth) acryloyl group functional groups: 15
Weight average molecular weight (Mw): 5,900
Viscosity: 64,600 mPa · s (40 ° C)

(Production of (B-1))
The following raw materials were used as follows.
・ Tronate HDT: hexamethylene diisocyanate trimer (manufactured by Rhodia)
IRGANOX (registered trademark) 1010: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (manufactured by BASF)
DPHA: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (hydroxyl value 50 mg KOH / g) (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.)
DBTDL: Dibutyltin dilaurate (Neostan U-810 manufactured by Nitto Kasei Co., Ltd.)

  To a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 63.00 g of Tronate HDT was charged, and the system was heated to 80 ° C. and dissolved. Subsequently, after introducing air into the liquid, IRGANOX (registered trademark) 1010: 0.14 g, DPHA: 400.0 g, DBTDL: 0.019 g were charged as polymerization inhibitors, and the reaction was performed at the same temperature for 8 hours. Furthermore, DBTDL: 0.1g was added and reaction was performed at the same temperature for 8 hours. After completion of the reaction, the reaction mixture was cooled to obtain a 15-functional urethane acrylate having a solid content of 100% by weight and represented by the following formula.

b-1 (for comparative example): urethane acrylate having two (meth) acryloyl groups
UA160TM made by Shin-Nakamura Chemical Co., Ltd.
Number of (meth) acryloyl group functional groups: 2
Viscosity: 26100 mPa · s (40 ° C)

b-2 (for comparative example): polyfunctional acrylate having three (meth) acryloyl groups
Osaka Organic Chemical Industry Co., Ltd. Viscoat 300 (V # 300)
Number of (meth) acryloyl group functional groups: 3
Viscosity: 143 mPa · s (40 ° C)

<Polymerization initiator>
C-1: 1-hydroxy-cyclohexyl-phenyl-ketone Irgacure (registered trademark) 184 manufactured by BASF Japan Ltd.

[Evaluation method]
Various evaluations in the following examples and comparative examples were performed as follows.

1. Coating property A bar coater was placed on an A4 size PET film substrate, and an appropriate amount of coating solution was applied to the film substrate. Next, the bar coater was pulled at a speed of about 1 cm per second, and the coating suitability when the coating was performed was evaluated according to the following criteria.
○: Can be spread.
X: It is impossible to spread.

2. Curability The coating film after coating was cured by ultraviolet irradiation. Ultraviolet irradiation was performed using a 120 W high pressure mercury lamp (“EYE UV METER UVPF-A1, PD365” manufactured by Eye Graphic Co., Ltd.), and the illuminance was set to 100 mW / cm ² . Under these conditions, the ease of curing when the irradiation dose was changed in the range of 100 to 400 mJ / cm ² was evaluated according to the following criteria.
○: Tackiness disappears.
X: There is a feeling of tack.

3. Transparency (total light transmittance / haze)
The total light transmittance and haze of the cured film cured with ultraviolet rays were measured with a haze meter according to JIS K7136. The haze meter used is “HAZE METER HM-65W” manufactured by Murakami Color Research Laboratory.

4). Hardness (pencil hardness)
Based on JIS K5600, the pencil hardness of the cured film cured with ultraviolet rays was measured under the condition of a load of 750 g and evaluated according to the following criteria.
○: Pencil hardness is H or more.
Δ: Pencil hardness is F.
X: Pencil hardness is HB or less.

5. Scratch resistance (steel wool resistance)
The surface of the cured film cured with ultraviolet rays was visually observed for scratches after being rubbed 20 times with steel wool (Bonster # 0000) at a load of 200 g / cm ² and evaluated according to the following criteria.
○: Less than 100 scratches are present, but the transparency is hardly impaired.
Δ: Many scratches of 100 or more are visible.
X: The cured film appears whitened due to countless scratches

6). Flexibility In accordance with JIS K5600, a flex test of a PET film having a cured film formed by a mandrel was conducted and evaluated according to the following criteria.
○: The minimum diameter of the mandrel that causes cracks in the cured film is less than 2 mmφ.
(Triangle | delta): The minimum diameter of the mandrel which produces a crack in a cured film is 2 mmφ or more and less than 3 mmφ.
X: The minimum diameter of the mandrel which causes a crack in the coating film is 3 mmφ or more.

[Examples and Comparative Examples]
Example 1
In a 200 mL eggplant flask, 90.0 g of (A-1), 10.0 g of (B-1), and 2.5 g of (C-1) were blended and dispersed at 40 ° C. over 1 hour with stirring. A curable composition was obtained. The curable composition was evaluated for coatability. Further, this curable composition was applied to a 125 μm PET film (321 E125 manufactured by Mitsubishi Plastics, Inc.) using a bar coater (# 1) so that the thickness of the coating film became 5 μm, and ultraviolet curing was performed. In evaluating curability, a high-pressure mercury lamp with an output of 120 W (“EYE UV METER UVPF-A1, PD365” manufactured by Eye Graphic Co., Ltd.) was used, and the illuminance was set to 100 mW / cm ² . Under these conditions, produce an amount of ^{irradiation, 100mJ / cm 2, 150mJ /} cm 2, 200mJ / cm 2, 250mJ / cm 2, 300mJ / cm 2, 350mJ / cm 2, respectively the cured film at 400 mJ / cm ² did. In evaluating physical properties of a cured film other than the curable film, a cured film was prepared with an output of 120 W and an illuminance of 450 mW / cm ² and an irradiation amount of 500 mJ / cm ² .
The evaluation results of the curable composition and the cured film are shown in Table-1.

(Example 2 and Comparative Examples 1-8)
A curable composition and a cured film were produced in the same manner as in Example 1 except that the composition in the formulation of Example 1 was changed as shown in Table 1, and various evaluations were performed. The evaluation results are shown in Table-1.

From Table 1, the curable composition of the present invention containing the component (A) and the component (B) in a predetermined composition is excellent in coatability and curability without containing an organic solvent, and has scratch resistance and transparency. It can be seen that a cured product having excellent hardness and flexibility can be obtained.
On the other hand, it turns out that the comparative example 1 which does not contain a component (B) only with a component (A) is inferior in sclerosis | hardenability, and inferior to scratch resistance. In the comparative example 2 which does not contain a component (A) only with a component (B), coating property was bad and could not form a coating film. In Comparative Examples 3 and 4 using urethane acrylate having two (meth) acryloyl groups and low viscosity instead of component (B), the curability is poor, the hardness and scratch resistance are poor, and the haze value is high. became. Moreover, in the comparative example 5 using only this urethane acrylate, coating property was bad and the coating film could not be formed.
Comparative Examples 6 to 8 use a polyfunctional acrylate having three (meth) acryloyl groups instead of the component (B), but have poor curability and poor scratch resistance and flexibility. became.

Claims (11)

Comprising the following components (A) and the following component (B), and the total amount of components (A) and (B), the curable composition content of from 1 to 30% by weight of component (B).
Component (A): (Meth) acrylate component (B) having a dendrimer structure and / or a hyperbranched polymer structure: 6 to 30 (meth) acryloyl groups and a urethane bond, and at 40 ° C. viscosity 35 is 000~ 9 0,000mPa · s (meth) acrylate   The curable composition of Claim 1 in which a component (B) has a nurate structure.   The curable composition of Claim 1 or 2 whose weight average molecular weights (Mw) of a component (A) are 500-5,000.   The curable composition according to any one of claims 1 to 3, wherein the component (B) has 8 to 30 (meth) acryloyl groups.   The curable composition according to any one of claims 1 to 4, which does not contain an organic solvent or contains an organic solvent and has a solid content concentration of 90% by weight or more.   The polymerization initiator is included, and the content thereof is 0.1 to 10 parts by weight with respect to a total of 100 parts by weight of the component (A) and the component (B). Curable composition.   The monofunctional (meth) acrylate is not contained, or the monofunctional (meth) acrylate is contained, and the content thereof is 10% by weight or less based on the entire curable composition. The curable composition according to item.   Hardened | cured material formed by hardening the curable composition of any one of Claim 1 thru | or 7 with an active energy ray.   It is a laminated body which has a base material and a hard-coat layer, and this hard-coat layer apply | coats the curable composition of any one of Claims 1 thru | or 7 on this base material, and this is an active energy ray. A laminate that is formed by irradiating.   The laminate according to claim 9, wherein the substrate is a plastic substrate.   The laminate according to claim 10, wherein the plastic substrate is at least one selected from polycarbonate resin, polyethylene terephthalate resin, and polymethyl methacrylate resin.