JP6940311B2 - Curable resin composition, laminate, and transfer laminate - Google Patents

Description

The present invention relates to a curable resin composition, a laminate having a cured product layer of the composition on a substrate, and a transfer laminate used for transfer of the cured product layer.

A curable resin composition that is cured by irradiation with active energy rays such as ultraviolet rays or electron beams cures to form a cured product having scratch resistance and chemical resistance, thereby protecting the surface of the article or imparting designability. It is used in a wide range of applications, from paints and coating agents for the purpose to optical materials that are molded into a desired shape to provide optical properties.

Furthermore, in recent years, insert molding in which a protective film or decorative film having a surface protective layer on a base material is inserted into an injection molding mold to perform injection molding, and the entire film is attached to a molded product, or surface protection A protective film or decorative film having a layer on the base material is inserted into the mold, injection molding is performed, and then the base material is peeled off to leave the surface protective layer and, in some cases, the decorative layer in the molded product. Its use in mold transfer films is expanding.

Generally, the curable resin composition is cured to increase the crosslink density to form a cured product layer having an improved surface hardness. However, since such a cured product layer has reduced flexibility and becomes brittle, cracks may occur when it is bent or pulled, or it may easily crack when an impact is applied by an external force. Further, when it is used for the insert molding or the in-mold transfer film, there is a problem that the elongation of the resin is lowered due to the curing of the surface protective layer, and the processability is deteriorated.

Patent Document 1 describes a compound having two or more ethylenically unsaturated groups and an isocyanurate ring as a decorative laminated film having excellent processability even after curing and excellent scratch resistance of the cured film (a compound having two or more ethylenically unsaturated groups and an isocyanurate ring. A composition for a photocurable decorative laminated film having an ethylenically unsaturated group concentration of 0.1 to 4.0 meq / g, which is a composition containing A) and a photopolymerization initiator (B), is disclosed. cage, wherein the compound (a) is an oxyalkylene group or / and -COC _N H _2N O-group represented by (N is an integer of from 2 to 6) have been disclosed to have.

Further, Patent Document 2 describes the component (A) as a curable resin composition having excellent scratch restoration property and surface hardness, and capable of obtaining a cured product having excellent curl resistance and bending resistance. : Urethane (meth) acrylate obtained by reacting an alkylene oxide and / or ε-caprolactone adduct (a1) of hydroxyalkyl (meth) acrylate with a polyisocyanate (a2) having an isocyanurate group and / or an allophanate group. And (B) component: a surface-modified inorganic oxide particle obtained by reacting a compound (b1) having a polymerizable unsaturated group and a hydrolyzable silyl group with an inorganic oxide particle (b2) in a specific ratio. The curable resin composition contained therein is disclosed.

Japanese Unexamined Patent Publication No. 2011-225679 Japanese Unexamined Patent Publication No. 2015-11345

In recent years, a cured product of a curable resin composition for surface protection is required to have high wear resistance and excellent tensile elongation. However, the cured product of the curable resin composition of the prior art as described in Patent Documents 1 and 2 still has insufficient wear resistance, and further improvement in tensile elongation is required.

Therefore, the present invention relates to a curable resin composition capable of obtaining a cured product having high abrasion resistance and excellent tensile elongation, a laminate having a cured product layer of the composition, and the composition. An object of the present invention is to provide a transfer laminate to be used for transfer of a cured product layer.

The curable resin composition of the present invention comprises a urethane (meth) acrylate (A) which is a reaction product of a polyisocyanate containing an isocyanurate ring and a compound represented by the following general formula (a').
Reactive irregularly shaped inorganic particles (B) having 2 to 20 substantially spherical inorganic particles having an average primary particle size of 10 nm to 100 nm connected and aggregated and having an ethylenically unsaturated bond-containing group on the surface.
Contains.

（一般式（ａ’）において、Ｒ’は水素原子又はメチル基を表し、Ｒ”は直鎖又は分岐状脂肪族炭化水素基を表し、ｊは３以上５以下の数であり、ｋは０．３以上の数である。）

(In the general formula (a'), R'represents a hydrogen atom or a methyl group, R'represents a linear or branched aliphatic hydrocarbon group, j is a number of 3 or more and 5 or less, and k is 0. .3 or more.)

In the curable resin composition of the present invention, in the urethane (meth) acrylate (A), the polyisocyanate is a polyisocyanate containing an isocyanurate ring derived from an aliphatic diisocyanate, which is stretchable. It is preferable from the point of view.

In the curable resin composition of the present invention, the urethane (meth) acrylate (A) is a polyisocyanate containing an isocyanurate ring derived from hexamethylene diisocyanate and a compound represented by the general formula (a'). Of these, a reaction product with a compound in which j is 5 is preferable from the viewpoint of tensile elongation.

In the curable resin composition of the present invention, the chemical resistance of the cured product is that the urethane (meth) acrylate (A) contains a polymer of pentamer or more as the polyisocyanate containing the isocyanurate ring. Is preferable from the viewpoint of improving.

In the curable resin composition of the present invention, in the urethane (meth) acrylate (A), in the compound represented by the general formula (a'), k is 0.4 or more and 0.7 or less. , It is preferable from the viewpoint of improving the chemical resistance of the cured product.

In the curable resin composition of the present invention, it is preferable to further contain a bisbenzotriazolylphenol compound from the viewpoint of increasing the weather resistance of the cured product.

In the curable resin composition of the present invention, further containing the bisbenzotriazolylphenol compound represented by the following general formula (1) is excellent in weather resistance and tensile elongation of the cured product. It is preferable from the point of view.

（一般式（１）中、Ｑは、メチレン基、エチリデン基、イソプロピリデン基、又はsec-ブチリデン基を表す。Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４はそれぞれ独立に、炭素数１以上６以下の直鎖又は分岐状脂肪族炭化水素基を表し、Ｒ^５及びＲ^６はそれぞれ独立に水素原子又はメチル基を表す。Ｒ^７及びＲ^８はそれぞれ独立に、水素原子、ハロゲン原子、又は炭素数１以上４以下の脂肪族炭化水素基を表す。ｎ及びｍはそれぞれ独立に、１以上１０以下の数であり、ｎ＋ｍ＝２以上２０以下である。ｐ及びｑはそれぞれ独立に、３以上５以下の数である。ｒ及びｓはそれぞれ独立に、１以上２以下の数である。）

(In the general formula (1), Q represents a methylene group, an ethylidene group, an isopropylidene group, or a sec-butylidene group. R ¹ , R ² , R ³ and R ⁴ each independently have 1 or more carbon atoms. Represents a linear or branched aliphatic hydrocarbon group of 6 or less, R ⁵ and R ⁶ independently represent a hydrogen atom or a methyl group, respectively. R ⁷ and R ⁸ independently represent a hydrogen atom, a halogen atom, or a halogen atom, respectively. Represents an aliphatic hydrocarbon group having 1 or more and 4 or less carbon atoms. N and m are independently numbers of 1 or more and 10 or less, and n + m = 2 or more and 20 or less. P and q are independently 3 and 3 respectively. or 5 in which .r及beauty s is the number of following each independently a number of 1 or more and 2 or less.)

The present invention also provides a laminate provided with a cured product layer of the curable resin composition of the present invention.
Furthermore, the present invention provides a transfer laminate provided with a cured product layer of the curable resin composition of the present invention, which is at least used for transfer of the cured product layer.

According to the present invention, a curable resin composition capable of obtaining a cured product having high abrasion resistance and excellent tensile elongation, a laminate having a cured product layer of the composition, and the composition. It is possible to provide a transfer laminate to be used for transfer of the cured product layer of the above.

FIG. 1 is a schematic cross-sectional view showing an example of the laminated body of the present invention. FIG. 2 is a schematic cross-sectional view showing another example of the laminated body of the present invention. FIG. 3 is a schematic cross-sectional view showing an example of the transfer laminate of the present invention. FIG. 4 is a schematic cross-sectional view showing another example of the transfer laminate of the present invention.

Hereinafter, embodiments of the curable resin composition of the present invention, a laminate provided with a cured product layer of the composition, and a laminate used for transfer of the cured product layer will be described.
In the present specification, the active energy ray means an energy ray capable of decomposing a compound that generates an active species to generate an active species. Examples of such active energy rays include light energy rays such as visible light, ultraviolet rays, infrared rays, X-rays, α-rays, β-rays, γ-rays, and electron beams.
In the present specification, (meth) acrylic represents each of acrylic and methacrylic, (meth) acryloyl represents each of acryloyl and methacrylic, and (meth) acrylate represents each of acrylate and methacrylate.
In the present specification, when a certain structure such as a member or a certain area is "above (or below)" another structure such as another member or another area, unless otherwise specified. This includes not only the case of being directly above (or directly below) the other configuration, but also the case of being above (or below) the other configuration, that is, another configuration in between above (or below) the other configuration. Including the case where the element is included.
Hereinafter, embodiments of the present invention will be described with reference to the drawings and the like. However, the present invention can be implemented in many different embodiments and is not construed as being limited to the description of the embodiments exemplified below. Further, in order to clarify the description, the drawings may schematically represent the width, thickness, shape, etc. of each part as compared with the embodiment, but this is just an example, and the interpretation of the present invention is used. It is not limited. Further, in the present specification and each figure, the same elements as those described above with respect to the above-mentioned figures may be designated by the same reference numerals, and detailed description thereof may be omitted as appropriate. Further, for convenience of explanation, the phrase "upper" or "lower" may be used for explanation, but the vertical direction may be reversed.

I. Curable Resin Composition The curable resin composition of the present invention is a urethane (meth) acrylate (A) which is a reaction product of a polyisocyanate containing an isocyanurate ring and a compound represented by the following general formula (a'). When,
Reactive irregularly shaped inorganic particles (B) having 2 to 20 substantially spherical inorganic particles having an average primary particle size of 10 nm to 100 nm connected and aggregated and having an ethylenically unsaturated bond-containing group on the surface.
Contains.

（一般式（ａ’）において、Ｒ’は水素原子又はメチル基を表し、Ｒ”は直鎖又は分岐状脂肪族炭化水素基を表し、ｊは３以上５以下の数であり、ｋは０．３以上の数である。）

(In the general formula (a'), R'represents a hydrogen atom or a methyl group, R'represents a linear or branched aliphatic hydrocarbon group, j is a number of 3 or more and 5 or less, and k is 0. .3 or more.)

The curable resin composition of the present invention contains a polyisocyanate containing an isocyanurate ring, a urethane (meth) acrylate (A) which is a reaction product of an ε-caprolactone adduct of a hydroxyalkyl (meth) acrylate, and an average primary order. High resistance to use in combination with reactive irregularly shaped inorganic particles (B) having 2 to 20 substantially spherical inorganic particles having a particle size of 10 nm to 100 nm connected and aggregated and having an ethylenically unsaturated bond-containing group on the surface. It is possible to obtain a cured product having excellent tensile elongation while having abrasion resistance.
The surface protective layer is required to have high wear resistance because the surface is required to be scratched and not fogged even if the same portion is repeatedly rubbed, but it has been difficult to achieve high wear resistance in the past. rice field. In particular, it has been difficult to achieve both high tensile elongation and high wear resistance of the cured product layer of the curable resin composition. That is, if a component that increases flexibility in order to increase the tensile elongation of the cured product layer is added, it is easily damaged and the wear resistance is likely to decrease. On the other hand, even if a component whose hardness is increased for wear resistance is used, it tends to become hard and brittle and the wear resistance tends to decrease.
On the other hand, in the present invention, the urethane (meth) acrylate (A), which is a reaction product of the polyisocyanate containing an isocyanurate ring and the ε-caprolactone adduct of the hydroxyalkyl (meth) acrylate, has an average primary particle. By using a combination of reactive irregularly shaped inorganic particles (B) having 2 to 20 substantially spherical inorganic particles having a diameter of 10 nm to 100 nm and having an ethylenically unsaturated bond-containing group on the surface, elasticity and high hardness are achieved. A cross-linked structure in which the above is combined is constructed, and the abrasion resistance can be improved while absorbing the impact. Further, by incorporating the reactive irregularly shaped inorganic particles (B) into the crosslinked structure, chain particles in which 2 to 20 substantially spherical inorganic particles are connected and aggregated are elongated so as to follow the pulling direction. It is presumed that cracks are less likely to occur due to the pulling force and the tensile elongation can be improved.

(1) Urethane (meth) acrylate (A)
The urethane (meth) acrylate (A) used in the curable resin composition of the present invention is obtained by subjecting a polyisocyanate containing an isocyanurate ring and a compound represented by the following general formula (a') to a urethanization reaction. It is a compound to be used.

（一般式（ａ’）において、Ｒ’は水素原子又はメチル基を表し、Ｒ”は直鎖又は分岐状脂肪族炭化水素基を表し、ｊは３以上５以下の数であり、ｋは０．３以上の数である。）

(In the general formula (a'), R'represents a hydrogen atom or a methyl group, R'represents a linear or branched aliphatic hydrocarbon group, j is a number of 3 or more and 5 or less, and k is 0. .3 or more.)

Polyisocyanates containing isocyanurate rings are derived from diisocyanates having two isocyanate groups in the molecule. Examples of the polyisocyanate containing an isocyanurate ring include a trimer represented by the following general formula (a-1), a pentamer represented by the following general formula (a-2), and the following general formula (a-3). Examples thereof include a heptameric represented by, a hexomer represented by the following general formula (a-4), and a multimer represented by more.

(In the general formulas (a-1) to (a-4), R represents a hydrocarbon group having 3 or more carbon atoms and 14 or less carbon atoms.)

In the general formulas (a-1) to (a-4), R represents a hydrocarbon group having 3 or more and 14 or less carbon atoms, and is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon. Groups and combinations thereof can be mentioned.
In the general formulas (a-1) to (a-4), R is a residue obtained by removing two isocyanate groups from diisocyanate. Examples of the diisocyanate that induces the polyisocyanate containing an isocyanurate ring include trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, and diphenylmethane. Examples thereof include diisocyanate, tolylene diisocyanate, and trizine diisocyanate.
As the diisocyanate for inducing a polyisocyanate containing an isocyanurate ring, a diisocyanate containing an aliphatic hydrocarbon group between two isocyanate groups is preferable from the viewpoint of improving tensile extensibility, and an aliphatic or alicyclic type is preferable. Diisocyanate is more preferable, aliphatic diisocyanate is further preferable, aliphatic diisocyanate having 4 or more and 9 or less carbon atoms, particularly aliphatic diisocyanate having 4 or more and 6 or less carbon atoms is more preferable, and hexamethylene diisocyanate is particularly preferable.

The method for producing a polyisocyanate containing an isocyanurate ring can be generally produced according to a known method. For example, an isocyanurate-forming catalyst such as diisocyanate or a quaternary ammonium salt and, if necessary, an organic solvent are put into the reaction vessel, and the isocyanurate-forming reaction is carried out while maintaining a predetermined temperature. Further, after the reaction, it is preferable to add a reaction terminator to stop the isocyanurate-forming reaction for the purpose of improving storage stability. For example, the amount of the multimer can be adjusted by appropriately adjusting the reaction temperature and the reaction time with reference to JP-A-2002-241458. Further, the unreacted diisocyanate is preferably removed by distillation.

In the urethane (meth) acrylate (A), it is preferable that a pentamer or more polymer is contained as the polyisocyanate containing an isocyanurate ring derived from diisocyanate from the viewpoint of improving the chemical resistance of the cured product. .. Above all, the polymer of pentamer or more is preferably 40% by mass or more, and more preferably 50% by mass or more of the total polyisocyanate containing the isocyanurate ring derived from diisocyanate. On the other hand, from the viewpoint of tensile elongation, it is preferably 70% by mass or less.
Among them, in the urethane (meth) acrylate (A), the polyisocyanate is a polyisocyanate containing an isocyanurate ring derived from an aliphatic diisocyanate from the viewpoint of improving the chemical resistance and tensile elongation of the cured product. Therefore, it is preferable that the polyisocyanate contains a polymer of pentamer or more. Among them, the pentamer or more polymer is preferably 40% by mass or more, and more preferably 50% by mass or more, of the total polyisocyanate containing the isocyanurate ring derived from the aliphatic diisocyanate. On the other hand, from the viewpoint of tensile elongation, it is preferably 70% by mass or less.
When the polyisocyanate is derived from an aliphatic diisocyanate, since the aliphatic hydrocarbon group is linked, even if it is a multimer of pentamer or more, it has flexibility in one molecule. The number of functional groups can be increased, the crosslink density can be improved, and the effect of improving the chemical resistance and tensile elongation of the cured product is high.

Further, the polyisocyanate containing an isocyanurate ring derived from the diisocyanate preferably has a weight average molecular weight of 1000 or more, and more preferably 1500 or more, from the viewpoint of improving the chemical resistance of the cured product. , 2000 or more is more preferable. On the other hand, from the viewpoint of tensile elongation, it is preferably 3000 or less, and preferably 2500 or less.
Here, the weight average molecular weight (Mw) in the present specification is determined as a standard polystyrene-equivalent value by gel permeation chromatography (GPC).
For example, a GPC HLC-8220 manufactured by Tosoh Corporation is used as a measuring device, Shodex LF-404 × 2 are connected in series to a column, a differential refractive index (RI) detector is used as a detector, and Agilent is used as standard polystyrene. Basic Type PS-2 polystyrene (molecular weight range 580 to 364,000) manufactured by Agilents can be used.
The obtained urethane acrylate was dissolved in THF so that the sample concentration was 0.2 wt%, the mobile phase was THF, the liquid feeding rate was 0.35 ml / min, the column temperature was 40 ° C., and the sample injection amount was 10 μL. Can be measured.
However, isocyanurate is not directly measured, but is measured after deactivating the isocyanate group with ethanol as a pretreatment. Therefore, the molecular weight of isocyanurate in the present specification includes the amount of ethanol added to isocyanurate. Described as the molecular weight to be included.

As the polyisocyanate containing an isocyanurate ring derived from diisocyanate, a commercially available product may be used by appropriately selecting it.

On the other hand, the compound represented by the following general formula (a') is a lactone adduct of hydroxyalkyl (meth) acrylate, using hydroxyalkyl (meth) acrylate as an initiator, γ-butyrolactone, δ-valerolactone, and It is a compound obtained by ring-opening addition polymerization of at least one lactone of ε-caprolactone.

（一般式（ａ’）において、Ｒ’は水素原子又はメチル基を表し、Ｒ”は直鎖又は分岐状脂肪族炭化水素基を表し、ｊは３以上５以下の数であり、ｋは０．３以上の数である。）

(In the general formula (a'), R'represents a hydrogen atom or a methyl group, R'represents a linear or branched aliphatic hydrocarbon group, j is a number of 3 or more and 5 or less, and k is 0. .3 or more.)

R "is preferably a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, and examples thereof include an ethylene group, a propylene group, a butylene group, and a hexamethylene group. Among these, an ethylene group is used. And Butylene groups are preferred, and ethylene groups are more preferred.

Examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate. Be done. Among these, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable, and 2-hydroxyethyl (meth) acrylate is more preferable. These hydroxyalkyl (meth) acrylates may be used alone or in combination of two or more.

k represents the degree of polymerization of ring-opening addition polymerization of at least one lactone of γ-butyrolactone, δ-valerolactone, and ε-caprolactone, that is, the average number of moles of lactone chain added, and is a number of 0.3 or more. be. Ring-opening addition polymerization of γ-butyrolactone gives a compound of j = 3, ring-opening addition polymerization of δ-valerolactone gives a compound of j = 4, and ring-opening addition polymerization of ε-caprolactone gives j = 5. The compound is obtained. Above all, a compound having j = 5 obtained by ring-opening addition polymerization of ε-caprolactone is preferable from the viewpoint of tensile elongation. When two or more kinds of lactones are mixed and used, j may be an average value.
When k is less than 1, the compound represented by the general formula (a') is a mixture of a lactone adduct of hydroxyalkyl (meth) acrylate and hydroxyalkyl (meth) acrylate, and the remainder (1-k). The hydroxyl group of is the hydroxyl group of hydroxyalkyl (meth) acrylate.

Although k is a number of 0.3 or more, it is preferably 1 or more from the viewpoint of improving tensile extensibility. On the other hand, from the viewpoint of improving wear resistance, it is preferably 6 or less, more preferably 3 or less, and even more preferably 2 or less.
On the other hand, from the viewpoint of further improving the chemical resistance of the cured product, in the compound represented by the general formula (a'), k is 0.4 mol or more and 0.7 mol or less, that is, urethane (meth). The hydroxyl group of the lactone adduct of hydroxyalkyl (meth) acrylate is contained in an amount of 0.4 mol or more and 0.7 mol or less with respect to 1 mol of the isocyanate group of the polyisocyanate containing the isocyanurate ring in the acrylate (A), and the hydroxyalkyl (meth) is contained. ) It is preferable that the hydroxyl group of the acrylate is contained in the remaining amount of 0.3 mol or more and 0.6 mol or less.
Further, in the compound represented by the general formula (a'), k is preferably 0.5 mol or more and 0.7 mol or less, that is, a poly containing an isocyanurate ring in the urethane (meth) acrylate (A). For 1 mol of isocyanate group of isocyanate, the hydroxyl group of the lactone adduct of hydroxyalkyl (meth) acrylate is contained in an amount of 0.5 mol or more and 0.7 mol or less, and the hydroxyl group of hydroxyalkyl (meth) acrylate is the remaining 0.3. It is preferably contained in an amount of 1 mol or more and 0.5 mol or less.

The compound represented by the general formula (a') can be produced according to a known method. For example, in the reaction vessel, hydroxyalkyl (meth) acrylate, at least one lactone of γ-butyrolactone, δ-valerolactone, and ε-caprolactone, and a ring-opening polymerization catalyst such as Lewis acid or alkali, if necessary. A polymerization inhibitor or an organic solvent is added to maintain a predetermined temperature for reaction. In addition, lactones such as ε-caprolactone may be reacted by dropping raw materials other than these in advance. After the reaction, the catalyst may be adsorbed using a known adsorbent to remove the adsorbent by filtration, or the salt produced by neutralizing with an acid or alkali may be removed by filtration.

The compound represented by the general formula (a') may be appropriately selected and a commercially available product may be used. For example, caprolactone-modified 2-hydroxyethyl (meth) acrylate [trade name: Praxel F series, manufactured by Daicel Corporation, average number of moles to be added 1 to 20] and the like can be mentioned.
Further, the compound represented by the general formula (a') may be used alone or in combination of two or more.

The urethane (meth) acrylate (A) used in the curable resin composition of the present invention is obtained by subjecting a polyisocyanate containing an isocyanurate ring to a compound represented by the general formula (a') in a urethanization reaction. Although it is a compound, it does not necessarily have to be a reaction product in which the hydroxyl group of the compound represented by the general formula (a') is 1 mol with respect to 1 mol of the isocyanate group of the polyisocyanate containing an isocyanurate ring.

The urethane (meth) acrylate (A) can be produced according to a generally known method. For example, a polyisocyanate containing an isocyanurate ring in a reaction vessel and a compound represented by the general formula (a') (for example, a lactone adduct of hydroxyalkyl (meth) acrylate and, in some cases, hydroxyalkyl (meth) acrylate). If necessary, a urethanization catalyst, a polymerization inhibitor, and an organic solvent are added, and the reaction is carried out while maintaining a predetermined temperature. The reaction ratio of each component is preferably such that the hydroxyl group contained in the compound represented by the general formula (a') is reacted so that the isocyanate group in the polyisocyanate is equivalent, but in the production, the hydroxyl group / The reaction is usually carried out in the range of the equivalent ratio of isocyanate groups of 0.8 / 1 to 1.1 / 1. For the polyisocyanate and the compound represented by the general formula (a'), one of the raw materials may be added in advance, and then a raw material other than the previously added raw material may be added dropwise to cause the reaction. The urethanization reaction is usually carried out in the range of 30 to 100 ° C. The end point of the urethanization reaction ^{can be confirmed by the disappearance of the infrared absorption spectrum of 2270 cm-1} showing an isocyanate group and the determination of the isocyanate group content by the method described in JIS K 7301. As the urethanization catalyst, a tin compound such as dibutyltin dilaurate or an amine such as triethylamine can be used.

(Reactive variant inorganic particles (B))
The reactive irregularly shaped inorganic particles (B) used in the curable resin composition of the present invention have 2 to 20 substantially spherical inorganic particles having an average primary particle size of 10 nm to 100 nm connected and aggregated, and are not ethylenically present on the surface. Reactive irregularly shaped inorganic particles having a saturated bond-containing group.

In the present invention, the deformed inorganic particles are composed of a group of 2 to 20 substantially spherical inorganic particles having an average primary particle size of 10 nm to 100 nm connected and aggregated. The articulated agglomeration may be regular or irregular.
The substantially spherical shape means a shape that can be approximated to a sphere including a spheroid and a polyhedron, and is a concept including a true sphere.

Examples of the inorganic particles forming the inorganic particle group include inorganic particles made of silica (colloidal silica, fumed silica, precipitated silica, etc.), and metal oxides such as alumina, zirconia, titania, and zinc oxide, which are transparent. From the viewpoint of improving properties and abrasion resistance, inorganic particles made of silica or alumina are preferable. That is, it is preferable that the deformed inorganic particles are formed by connecting and aggregating 2 to 20 substantially spherical silica particles or alumina particles having an average primary particle size of 10 nm to 100 nm.

From the viewpoint of wear resistance, the deformed inorganic particles used in the present invention preferably have 2 to 15 substantially spherical inorganic particles having an average primary particle size of 10 nm to 100 nm connected and aggregated, and further, 2 It is preferable that 10 to 10 particles are connected and aggregated.
From the viewpoint of abrasion resistance, the deformed inorganic particles used in the present invention preferably have 2 to 20 substantially spherical inorganic particles having an average primary particle size of 10 nm to 50 nm connected and aggregated, and among them, the average primary particle size. It is preferable that 2 to 15 substantially spherical inorganic particles having a particle size of 10 nm to 50 nm are connected and aggregated, and further, 2 to 10 substantially spherical inorganic particles having an average primary particle size of 10 nm to 50 nm are connected and aggregated. It is preferable to have.
The size and shape of the deformed inorganic particles can be observed using an SEM photograph or a TEM photograph.
In the case of a dispersion containing inorganic particles such as a resin composition, the particles are observed while being applied to the observation sample table so as to have a thickness equivalent to one layer of the inorganic particles, and at that time, substantially spherical inorganic particles are observed. Unlike the state in which the particles are aggregated into a large substantially spherical shape, the state in which the substantially spherical inorganic particles are connected and aggregated in a certain direction can be determined to be connected and aggregated. There may be two or more directions in which the substantially spherical inorganic particles are connected to each other. Further, in the case of a cured product of the resin composition, a cross section can be cut out and the state of the particles can be observed.

Examples of the ethylenically unsaturated bond-containing group on the surface of the deformed inorganic particles include a vinyl group, a (meth) acryloyl group, and an allyl group.

Preferable examples of such reactive irregularly shaped inorganic particles include irregularly shaped inorganic particles whose surface is decorated with a silane coupling agent having an ethylenically unsaturated bond-containing group. As a silane coupling agent having an ethylenically unsaturated bond-containing group, a known known silane coupling agent having an alkoxy group, an amino group, a vinyl group, an epoxy group, a mercapto group, a chloro group and the like in addition to the ethylenically unsaturated bond-containing group. Silane coupling agents include, more specifically, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyl dimethylethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyldimethylmethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropyl Methyldiethoxysilane, γ-acryloxypropyldimethylethoxysilane, vinyltriethoxysilane and the like are preferable, and more preferably, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxy. Examples thereof include propyldimethylmethoxysilane.

The method of surface-decorating the deformed inorganic particles with a silane coupling agent is not particularly limited and may be a known method, such as a dry method of spraying a silane coupling agent or a method of dispersing the deformed inorganic particles in a solvent and then silane. Examples thereof include a wet method in which a coupling agent is added and reacted.

The reaction ratio of the silane coupling agent having an ethylenically unsaturated bond-containing group to the deformed inorganic particles is usually 1 mass by mass when the total mass of the deformed inorganic particles and the silane coupling agent is 100 parts by mass. It is in the range of parts or more and 50 parts by mass or less, preferably in the range of 2 parts by mass or more and 30 parts by mass or less, and more preferably in the range of 5 parts by mass or more and 20 parts by mass or less.

In addition to the reactive irregularly shaped inorganic particles (B), the curable resin composition of the present invention further contains reactive inorganic particles (B') that do not correspond to the reactive irregularly shaped inorganic particles (B). Is also good. Examples of the reactive inorganic particles (B') include those having an ethylenically unsaturated bond-containing group on the surface of substantially spherical inorganic particles, and the material of the inorganic particles and the ethylenically unsaturated present on the surface of the inorganic particles. The bond-containing group is preferably the same as that of the reactive variant inorganic particle (B).
When the curable resin composition of the present invention contains reactive inorganic particles (B') that do not correspond to the reactive irregularly shaped inorganic particles (B) in addition to the reactive irregularly shaped inorganic particles (B), tension is applied. From the viewpoint of improving the extensibility and the abrasion resistance, the reactive irregularly shaped inorganic particles (B) with respect to 100 parts by mass of the total amount of the reactive irregularly shaped inorganic particles (B) and the reactive inorganic particles (B'). ) Is preferably contained in an amount of 50 parts by mass or more, more preferably 60 parts by mass or more, and further preferably 70 parts by mass or more.

In the curable resin composition of the present invention, in addition to the reactive deformed inorganic particles (B), the reactive inorganic particles (B') and other inorganic particles that do not correspond to the reactive deformed inorganic particles (B) are further included. However, the average particle size of the inorganic particles containing the reactive irregularly shaped inorganic particles (B) is preferably 20 nm or more and 500 nm or less, more preferably 20 nm or more and 300 nm or less, and more preferably 20 nm or more. It is even more preferably 200 nm or less. The average particle size is 50% particle size (d50: median size) when the particles in the solution are measured by a dynamic light scattering method and the particle size distribution is expressed as a cumulative distribution. It can be measured using a microtrack UPA150) manufactured by Japan.

In the curable resin composition of the present invention, reactive inorganic particles containing urethane (meth) acrylate (A) and reactive irregularly shaped inorganic particles (B) from the viewpoint of a balance between good wear resistance and tensile elongation. The content ratio of urethane (meth) acrylate (A) is 20% by mass in 100 parts by mass of the total amount of urethane (meth) acrylate (A) and reactive inorganic particles containing reactive irregularly shaped inorganic particles (B). It is preferably more than 30 parts by mass, and more preferably 30 parts by mass or more.
Above all, from the viewpoint of improving the abrasion resistance, in the curable resin composition of the present invention, the total amount of the urethane (meth) acrylate (A) and the reactive inorganic particles containing the reactive irregularly shaped inorganic particles (B) is 100 mass by mass. The urethane (meth) acrylate (A) is preferably 60 parts by mass or less, more preferably 55 parts by mass or less, and further preferably 50 parts by mass or less.
On the other hand, from the viewpoint of improving the tensile elongation, the total amount of the urethane (meth) acrylate (A) and the reactive inorganic particles containing the reactive irregularly shaped inorganic particles (B) in the curable resin composition of the present invention. The urethane (meth) acrylate (A) may exceed 90 parts by mass in 100 parts by mass, but it is preferably 98 parts by mass or less from the viewpoint of compatibility with wear resistance.

<Other ingredients>
The curable resin composition of the present invention may further contain an ultraviolet absorber from the viewpoint of improving weather resistance.
It has been found that the curable resin composition of the present invention can easily obtain high weather resistance by containing an ultraviolet absorber. This is because the urethane bond and ester bond contained in the urethane (meth) acrylate (A) used in the present invention are resistant to light and moisture, as compared with the case where an ether bond such as an alkylene oxide chain is contained. It is presumed that the weather resistance can be increased.
The ultraviolet absorber may be used alone or in combination of two or more.

As the ultraviolet absorber, for example, a benzotriazole-based compound, a benzophenone-based compound, a triazine-based compound, a cyanoacrylate-based compound, a benzoxazine-based compound, a benzoxazole-based compound, a merocyanine-based compound, or any combination thereof is used. Is preferable. This is because it absorbs a wide wavelength range. Among them, benzotriazole-based compounds, benzophenone-based compounds, and triazine-based compounds are more preferable.
Specific examples of these include 2- (2-hydroxy-5-methyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, and the like. 2- (2'-Hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy) -3', 5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-t-butylphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazole-2) -Il) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2'-hydroxy-3', 5'-t-pentylbenzotriazole, 2- [2'-hydroxy-5) '-(1,1,3,3-tetramethylbutyl)] benzotriazole, 2- (2'hydroxy-3'-s-butyl-5'-t-butylbenzotriazole, 2- (2'-hydroxy) -3-Dodecyl-5'-methylbenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5' -Methylphenyl) benzotriazole, 2,2-methylenebis [4-1,1,3,3-tetramethylbutyl] -6- (2H-benzotriazole-2-yl) phenol], 3- [3- (2H) -Benzotriazole-2-yl) -5-t-butyl-4-hydroxyphenyl] Bentriazoles such as a reaction product of propionate and polyethylene glycol; 2-hydroxybenzophenone, 5-chloro2-hydroxybenzophenone, 2,4- Dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'- Benzophenones such as dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone; 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-[( Methyl) oxy] -phenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-[(ethyl) oxy] -phenol, 2- (4,4) 6-Diphenyl-1,3,5-triazine-2-yl-[(propyl) oxy] -phenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-[ Triazines such as (butyl) oxy] -phenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-[(hexyl) oxy] -phenol; 2-ethylhexyl 2- Cyano-3,3-diphenylacrylate, 1,3-bis (2'-cyano-3,3'-diphenylacryloyl) oxy) -2,2-bis (((2'-cyano-3,3'-diphenyl)) Acryloyl) oxy) methyl) cyanoacrylates such as propane; 2,2'-p-phenylenebis (4H-3,1-benzoxazole-4-one), 2,2'-p-phenylenebis (6-methyl) Benzoxadinones such as -4H-3,1-benzoxazine-4-one); 2,5-thiophendiyl (5-tert-butyl-1,3-benzoxazole), 2,6-di (benzoxazole) Benoxazoles such as -2-yl) naphthalene and 4,4'-bis (benzoxazole-2-yl) furan; 1,3-dimethyl-5-[2- (3-methyloxazolidine-2-iriden) ethylidene ] Examples include merocyanines such as pyrimidine-2,4,6-trione, octyl-5-N, N-diethylamino-2-phenylsulfonyl-2,4-pentadienoate.

Among them, the curable resin composition of the present invention preferably contains a bisbenzotriazolylphenol compound as an ultraviolet absorber from the viewpoint of increasing the weather resistance of the cured product.
Since the bisbenzotriazolylphenol compound has a large molecular extinction coefficient, it has good ultraviolet absorption performance, an extremely low vapor pressure, and high thermal stability. Therefore, volatilization is suppressed even when mixed with the resin, and stable mixing can be performed without decomposition.

Further, among the bisbenzotriazolylphenol compounds, when the compound has a cross-linking group such as a (meth) acryloyl group, the ultraviolet absorber itself functions as a cross-linking agent, so that it is excellent without reducing the cross-linking density. It is preferable from the viewpoint that weather resistance and ultraviolet shielding property can be imparted.

Further, when the bisbenzotriazolylphenol compound contains a lactone chain which is a ring-opening addition polymerization chain of at least one lactone of γ-butyrolactone, δ-valerolactone, and ε-caprolactone, It is preferable because the ultraviolet absorber itself contributes to tensile elongation.

The curable resin composition of the present invention preferably contains a bisbenzotriazolylphenol compound represented by the following general formula (1) as an ultraviolet absorber.

（一般式（１）中、Ｑは、メチレン基、エチリデン基、イソプロピリデン基、又はsec-ブチリデン基を表す。Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４はそれぞれ独立に、炭素数１以上６以下の直鎖又は分岐状脂肪族炭化水素基を表し、Ｒ^５及びＲ^６はそれぞれ独立に水素原子又はメチル基を表す。Ｒ^７及びＲ^８はそれぞれ独立に、水素原子、ハロゲン原子、又は炭素数１以上４以下の脂肪族炭化水素基を表す。ｎ及びｍはそれぞれ独立に、１以上１０以下の数であり、ｎ＋ｍ＝２以上２０以下である。ｐ及びｑはそれぞれ独立に、３以上５以下の数である。ｒ及びｓはそれぞれ独立に、１以上２以下の数である。）

(In the general formula (1), Q represents a methylene group, an ethylidene group, an isopropylidene group, or a sec-butylidene group. R ¹ , R ² , R ³ and R ⁴ each independently have 1 or more carbon atoms. Represents a linear or branched aliphatic hydrocarbon group of 6 or less, R ⁵ and R ⁶ independently represent a hydrogen atom or a methyl group, respectively. R ⁷ and R ⁸ independently represent a hydrogen atom, a halogen atom, or a halogen atom, respectively. Represents an aliphatic hydrocarbon group having 1 or more and 4 or less carbon atoms. N and m are independently numbers of 1 or more and 10 or less, and n + m = 2 or more and 20 or less. P and q are independently 3 and 3 respectively. or 5 in which .r及beauty s is the number of following each independently a number of 1 or more and 2 or less.)

Since the bisbenzotriazolylphenol compound represented by the general formula (1) has 2 or more and 4 or less (meth) acryloyl groups in one molecule, the ultraviolet absorber itself serves as a cross-linking agent. Since it functions, excellent weather resistance and UV shielding property can be imparted without reducing the crosslink density.
Further, the bisbenzotriazolylphenol compound represented by the general formula (1) is used in which water is present as compared with the conventional bisbenzotriazolylphenol compound having a (meth) acryloyl group. It is difficult to bleed out in an environment, and has excellent weather resistance, that is, long-term sustainability of photostability in a usage environment where it is affected by light and moisture at the same time.
This is because the bisbenzotriazolylphenol compound represented by the general formula (1) has two long chain substituents, so that it has an advantage that it is difficult to aggregate and unevenly distributed, and one long chain. Since it has two aliphatic hydrocarbon chains and a lactone chain in the substituent of, the compatibility with the resin is improved, it is easily dispersed in the resin, and the (meth) acryloyl group present at the terminal is free. It is presumed that the degree is increased and the reaction efficiency with the ethylenically unsaturated bond-containing group of other molecules is improved.

Further, the bisbenzotriazolylphenol compound represented by the general formula (1) is not only an aliphatic hydrocarbon chain but also a caprolactone chain between the (meth) acryloyl group and the bisbenzotriazolylphenol compound. Since it has a lactone chain such as, etc., it is incorporated into the crosslinked structure without reducing the crosslinked density, thereby imparting flexibility and elasticity to the crosslinked structure. Therefore, it can be improved without impairing the tensile elongation of the cured product of the curable resin composition.

More specifically, each group represented in the general formula (1) is as follows.
Examples of the linear or branched aliphatic hydrocarbon group having 1 or more and 6 or less carbon atoms in R ¹ and R ² include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, ethylidene, propylene, propyridene, and ethylethylene. , 2-butylidene, 1-methyltrimethylene, 1,1-dimethylethylene, 1,1-dimethyltrimethylene, 2-methyltrimethylene, 2,2-dimethyltrimethylene, etc. Can be mentioned. As R ¹ and R ² , linear aliphatic hydrocarbon groups of 2 or more and 6 or less are preferable, and ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene are preferable.

When r and s are 1, respectively, R ³ and R ⁴ include straight-chain or branched aliphatic hydrocarbon groups having a divalent carbon number of 1 to 6 and are listed in R ¹ and R ² , respectively. A group similar to a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms can be preferably used.
When r and s are 2 respectively, R ³ and R ⁴ are trivalent linear or branched aliphatic hydrocarbon groups having 1 or more and 6 or less carbon atoms, respectively, and have 1 or more and 6 or less carbon atoms. Included are residues from which three hydrogen atoms have been removed from chains or branched aliphatic hydrocarbons. ^{As R 3} and R ⁴ when r and s are 2, for example, a trivalent aliphatic hydrocarbon group listed in the following chemical structural formula is preferably used.
When r and s are 2 independently, the number of polymerizable functional groups in one molecule is 3 or 4, and the reaction efficiency with the ethylenically unsaturated bond-containing group of the other molecule is improved.

R ¹ , R ² , R ³ and R ⁴ may be the same or different, respectively, but from a manufacturing point of view, R ¹ and R ² are preferably the same, and R ³ and R ^{4 are the same.} Is preferably the same.

Although R ⁵ and R ⁶ are independently hydrogen atoms or methyl groups, hydrogen atoms are preferable because the reaction efficiency is improved.

Examples of the halogen atom in R ⁷ and R ⁸ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Of these, chlorine atoms and bromine atoms are preferable.
Examples of the aliphatic hydrocarbon group having 1 or more and 4 or less carbon atoms in R ⁷ and R ⁸ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl group and the like.

p and q are independently numbers of 3 or more and 5 or less. That is, the bisbenzotriazolylphenol compound represented by the general formula (1) is a lactone chain which is a ring-opening addition polymerization chain of at least one lactone of γ-butyrolactone, δ-valerolactone, and ε-caprolactone. Includes. Ring-opening addition polymerization of γ-butyrolactone gives compounds with p and q of 3, ring-opening addition polymerization of δ-valerolactone gives compounds with p and q of 4, and ring-opening addition polymerization of ε-caprolactone. A compound having p and q of 5 is obtained. When two or more kinds of lactones are mixed and used, p and q may be average values. From the viewpoint of tensile elongation, p and q are each independently preferably a number of 4 or more and 5 or less, and more preferably 5.

n and m are independently 1 or more and 10 or less. n and m represent the degree of polymerization (number of moles added) of the lactone, respectively, and n and m may be average values, respectively. n and m are appropriately determined depending on the application, considering whether it is necessary to further improve the flexibility and tensile extensibility by the lactone chain, or whether it is necessary to increase the hardness while improving the tensile extensibility. You can choose. Above all, from the viewpoint of improving flexibility such as tensile elongation, n and m are each independently preferably having an average of 1.5 or more, and on the other hand, from the viewpoint of improving hardness, it is preferably 8 or less. It is more preferably 6 or less, and even more preferably 5 or less.
Further, n + m = 2 or more and 20 or less, but similarly, it is preferably 3 or more from the viewpoint of improving flexibility such as tensile elongation, and on the other hand, it is preferably 16 or less from the viewpoint of improving hardness. , 12 or less is more preferable, and 10 or less is even more preferable.

Specific examples of the bisbenzotriazolylphenol compound of the present invention represented by the general formula (1) include compounds in the following combinations.
In the compounds of the following combinations, there are cases where p and q are 5 and r and s are 1 respectively.
Further, in the compounds of the following combinations, there are cases where p and q are 5 and r and s are 2 respectively.
Further, in the compounds of the following combinations, there are cases where p and q are 4 and r and s are 1 each, and cases where p and q are 3 and r and s are 1 respectively. .. However, the bisbenzotriazolylphenol compound of the present invention represented by the general formula (1) is not limited to specific examples of these combinations.

The bisbenzotriazolylphenol compound of the present invention represented by the general formula (1) is, for example, a conventionally known method for the alcoholic hydroxyl group of the bisbenzotriazolylphenol compound represented by the general formula (2). It can be produced by ring-opening addition polymerization of a lactone such as ε-caprolactone, and further reacting the alcoholic hydroxyl group of the lactone chain with an isocyanate compound having a (meth) acryloyloxy group in a solvent.

（一般式（２）中、Ｑ、Ｒ^１、Ｒ^２、Ｒ^７及びＲ^８は、一般式（１）と同じである。）

(In the general formula (2), Q, R ¹ , R ² , R ⁷ and R ⁸ are the same as the general formula (1).)

The bisbenzotriazolylphenol compound represented by the general formula (2) used here can be appropriately prepared by a conventionally known method.
Examples of the isocyanate compound having a (meth) acryloyloxy group include (meth) acryloyloxymethyl isocyanate, 2- (meth) acryloyloxyethyl isocyanate, 3- (meth) acryloyloxypropyl isocyanate, and 2- (meth) acryloyloxy. Ppropyl isocyanate, 4- (meth) acryloyloxybutyl isocyanate, 1,1- (bisacryloyloxymethyl) ethyl isocyanate and the like are preferably used.

In the curable resin composition of the present invention, the content ratio of the ultraviolet absorber is 0.5 parts by mass or more and 6 parts by mass with respect to 100 parts by mass of urethane (meth) acrylate (A) from the viewpoint of improving weather resistance. It is preferably 1 part by mass or more and 5 parts by mass or less.

The curable resin composition of the present invention further obtains the effect of the present invention by using a polymerizable compound having an ethylenically unsaturated bond-containing group, which is different from the urethane (meth) acrylate (A), depending on the application. It may be contained within the range of the above.
Here, the polymerizable compound having an ethylenically unsaturated bond-containing group is not particularly limited, and compounds such as a polymer (high polymer), an oligomer (low polymer), and a monomer (monomer) can be used. It can be mentioned, and known ones can be used as appropriate. As the compound having an ethylenically unsaturated bond-containing group, one type may be used alone or two or more types may be mixed and used.
Specifically, for example, a polyfunctional polyester (meth) acrylate-based oligomer, a polyfunctional urethane (meth) acrylate-based oligomer, or a polyfunctional epoxy (meth) acrylate having at least two (meth) acryloyloxy groups in one molecule. Examples include system oligomers. Further, as the polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polytetra. Methylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 3-methyl-1,3, 5-Pentanediol di (meth) acrylate, neoventyl glycol di (meth) acrylate, dimethylol-tricyclodecanedi (meth) acrylate, neoventyl glycol di (meth) acrylate of hydroxypivalate, bisphenol A polyethoxydiol Di (meth) acrylate, bisphenol A polypropoxydiol di (meth) acrylate, trimethylolpropoxydiol di (meth) acrylate, ethoxylated trimethylol propanetri (meth) acrylate, propoxylated trimethylol brobantry (meth) acrylate, pentaerythritol Tri (meth) acrylate, glyceryl tri (meth) acrylate, propoxylated glyceryl tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylol propanetetra ( Examples thereof include, but are not limited to, meta) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

When a polymerizable compound having an ethylenically unsaturated bond-containing group, which is different from the urethane (meth) acrylate (A), is contained, the content thereof may be appropriately set within a range in which the effects of the present invention can be obtained, depending on the intended use. Select and use. For example, when emphasis is placed on elongation, a polymerizable compound having two ethylenically unsaturated bond-containing groups may be further contained in one molecule, but two ethylenically unsaturated bonds are contained in one molecule. The content of the polymerizable compound having a group is 40 parts by mass or less with respect to 100 parts by mass of the total amount of the urethane (meth) acrylate (A) and the reactive inorganic particles containing the reactive irregularly shaped inorganic particles (B). From the viewpoint of obtaining a cured product having high abrasion resistance and excellent tensile elongation, the content is preferably 30 parts by mass or less, and more preferably 20 parts by mass or less. When a polymerizable compound having three or more ethylenically unsaturated bond-containing groups is contained in one molecule, the content is not limited, but is reactive with urethane (meth) acrylate (A). From the viewpoint of improving the elongation with respect to 100 parts by mass of the total amount of the reactive inorganic particles containing the particles (B), for example, 20 parts by mass or less can be mentioned.
Above all, the content of the polymerizable compound having an ethylenically unsaturated bond-containing group, which is different from the urethane (meth) acrylate (A), from the viewpoint of improving the balance between the high elongation and the high abrasion resistance of the present invention. Is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, based on 100 parts by mass of the total amount of the urethane (meth) acrylate (A) and the reactive inorganic particles containing the reactive irregularly shaped inorganic particles (B). It is preferable that the amount is 3 parts by mass or less.

Further, the curable resin composition of the present invention may contain a solvent in order to adjust the viscosity of the composition and improve the smoothness, uniformity, adhesion to the object to be coated and the like of the cured film. .. Known solvents can be used, for example, alcohols such as ethanol, propanol, isopropanol and butanol, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, acetone, methyl ethyl ketone and methyl. Examples thereof include ketones such as isobutyl ketone, ethers such as 2-methoxyethanol, 2-ethoxyethanol, 2-ethoxypropanol, 2- (2-ethoxyethoxy) ethanol, 1,4-dioxane and tetrahydrofuran. Two or more kinds of solvents may be mixed and used.

In the curable resin composition of the present invention, the content ratio of the solvent may be appropriately adjusted according to the intended purpose and is not particularly limited, but is 30 parts by mass or more and 90 parts by mass or less in 100 parts by mass of the curable resin composition. It is preferably 40 parts by mass or more and 70 parts by mass or less.

Further, in the case where the curable resin composition of the present invention is ultraviolet-curable using ultraviolet rays for curing, the composition of the present invention is subjected to a photopolymerization initiator, a polymerization accelerator, and a photoinitiator assist in order to perform curing quickly. It is better to add an agent or the like. As the photopolymerization initiator, known ones can be used, and examples thereof include acetophenone-based compounds, benzoin ether-based compounds, benzophenone-based compounds, and thioxanthone-based compounds. The photopolymerization initiator may be used alone or in combination of two or more. The content ratio of the photopolymerization initiator is not particularly limited, but is usually 0 with respect to 100 parts by mass of the total amount of the urethane (meth) acrylate (A) and the polymerizable compound having an ethylenically unsaturated bond-containing group contained in some cases. It may be about 1 part by mass or more and about 30 parts by mass or less, preferably about 1 part by mass or more and 5 parts by mass or less. As the polymerization accelerator and photoinitiator, for example, triethanolamine, methyldiethanolamine, triisopropanolamine and the like can be used. The content ratio of the polymerization accelerator and the photoinitiator is not particularly limited, but is usually about 0.01 part by mass or more and 10 parts by mass or less, preferably 0.5 parts by mass or more and 3 parts by mass with respect to 100 parts by mass of the photopolymerization initiator. The number may be less than or equal to the number of copies.
In the case of electron beam curability using an electron beam for curing, it is not necessary to add a photopolymerization initiator, a polymerization accelerator, a photoinitiator aid, or the like. In this case, it is preferable because the content ratio of the urethane (meth) acrylate (A) and the reactive deformed inorganic particles (B) in the solid content can be increased, and the wear resistance and tensile elongation can be easily improved.

Further, if necessary, the curable resin composition of the present invention further includes, for example, a light stabilizer, an antioxidant, a plasticizer, a flame retardant, a surfactant, a leveling agent, a thermopolymerization inhibitor, an antistatic agent, and the like. Various additives such as antifogging agents, antibacterial agents, fillers, pigments, dyes, and colorants can be contained.

In the curable resin composition of the present invention, the urethane (meth) acrylate (A), the reactive irregularly shaped inorganic particles (B), and various additives and solvents as required are blended in a predetermined ratio, and a conventional method is used. Can be obtained by mixing uniformly.

The curable resin composition of the present invention can be suitably used for applications as described in the section of the laminate described later. In addition, the molded body of the curable resin composition can be suitably used for various optical products, various display members, in-vehicle interior / exterior parts, wallpaper, furniture, various residential members used for window glass, and the like. ..

II. Laminated body The laminated body of the present invention is a laminated body in which the cured product layer of the curable resin composition of the present invention is provided on a base material.
FIG. 1 is a schematic cross-sectional view showing an example of the laminated body of the present invention, and FIG. 2 is a schematic cross-sectional view showing another example of the laminated body of the present invention.
As shown in FIG. 1, the laminate 10 of the present invention has a configuration in which the cured product layer 2 of the curable resin composition of the present invention is provided on the base material 1.
The laminate 10 of the present invention may further include another layer. For example, as shown in FIG. 2, in the laminate 10 of the present invention, the adhesive layer 3, the primer layer 4, and the cured product layer 2 of the curable resin composition of the present invention are arranged in this order on the base material 1. You may have it.
Further, although not shown, the laminate 10 of the present invention may be provided with the adhesive layer 3 and the cured product layer 2 of the curable resin composition of the present invention in this order on the base material 1. Further, the laminate 10 of the present invention may further include a layer other than the adhesive layer 3 and the primer layer 4, such as a decorative layer. As another layer such as a decorative layer, a known layer can be appropriately selected and used.
Hereinafter, the structure of the laminated body of the present invention will be described in detail.

<Base material>
The base material of the laminated body is not particularly limited as long as other layers or a cured product of the curable resin composition can be laminated on the base material. The shape of the base material is not limited to the sheet shape, and may be a molded product. As the base material, various materials such as plastic, glass, metal, wood, and paper can be generally used. Among these, plastic films are preferable, and for example, polyethylene (PE) resin, polypropylene (PP) resin, polybutadiene resin, polyethylene terephthalate (PET) resin, polybutylene terephthalate resin, polyethylene naphthalate (PEN) resin, triacetyl cellulose ( Films such as TAC) resin, polymethylmethacrylate (PMMA) resin, polycarbonate (PC) resin, cycloolefin polymer, ethylene vinyl acetate copolymer (EVA) resin, polyvinyl chloride (PVA) resin, ABS resin, AS resin, etc. are listed. Be done.
In particular, when used as a substitute for glass for various window materials, polycarbonate resin, polymethylmethacrylate resin, ABS resin and the like are suitable.

Further, the base material may be surface-treated in advance for the purpose of improving adhesion. As the surface treatment, a known method may be appropriately selected and used. For example, plasma treatment, corona discharge treatment, ultraviolet irradiation treatment, flame treatment, chemical treatment, degreasing, oxidation treatment, vapor deposition treatment, blast treatment, ion treatment, etc. UV ozone treatment, EB treatment and the like can be mentioned.

<Cured material layer>
In the cured product layer of the curable resin composition of the present invention, the curable resin composition of the present invention is applied to a desired thickness on a substrate or a support as described later, and a solvent is optionally applied. When used, it can be produced by drying to remove the solvent and then irradiating with active energy rays to cure.

The method for coating the curable resin composition on the substrate is not particularly limited, and a known method can be appropriately applied. Examples of the coating method include dipping method, flow coating method, spray method, spin coating method, gravure coating method, micro gravure coating method, die coating method, slit reverse method, roll coating method, blade coating method, and air knife coating method. It can also be applied by any method such as an offset method or a bar coating method. It is also possible to apply an image by a printing method such as gravure printing, gravure offset printing, or screen printing.

The amount of coating may be appropriately selected according to the purpose of the cured product layer, and is not particularly limited. For example, when the purpose is a glass substitute, the film thickness of the cured product layer cured by irradiation with active energy rays is 0.1 μm or more and 200 μm or less, preferably 1 μm or more and 100 μm or less, and more preferably 5 μm or more and 50 μm or less. It is preferable to apply the coating as follows.

In order to evaporate the solvent added to the curable resin composition of the present invention as needed, known drying methods such as hot air heating, infrared heating, and far infrared heating can be appropriately adopted.
The drying conditions vary in a preferable range depending on the boiling point of the solvent, the material of the base material, the coating amount, and the like, but generally, the drying conditions are 30 ° C. or higher and 120 ° C. or lower for 1 minute or longer and 30 minutes or shorter.

Active energy rays include ultraviolet rays emitted from light sources such as xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, carbon arc lamps, and tungsten lamps, electron beams usually extracted from particle accelerators of 20 to 2000 kV, and α. Lines, β-rays, γ-rays and the like can be used.

The cured product layer of the curable resin composition of the present invention has excellent wear resistance. The surface of the cured product of the curable resin composition of the present invention was subjected to a taber wear test under the conditions of a wear wheel CS-10F, a load of 500 g, and a rotation speed of 1000 rotations according to JIS K5600, and a difference of ΔH% in haze values before and after the test was obtained. When measured, ΔH% is preferably less than 5.0%, more preferably less than 3.0%.

The cured product layer of the curable resin composition of the present invention has excellent tensile elongation. The cured product layer of the curable resin composition of the present invention was subjected to a tensile test using a tensile tester (AUTOGRAPH AG-X manufactured by Shimadzu Corporation) at a distance between chucks of 5 cm and a tensile speed of 50 mm / min. When the length of elongation when cracks occur in the layer is measured and the elongation is determined as described below, the elongation is preferably 30% or more, more preferably 40% or more, and 50%. It is even more preferable that it is% or more.
Elongation = (length of elongation when cracks occur in the cured product layer) / (length of the cured product layer before the test) x 100 (%)

<Adhesive layer>
As the adhesive layer, for example, any layer having a function of adhering the base material to the cured product layer or another layer can be appropriately selected and used. The adhesive layer may exist between other layers.
As the material of the adhesive layer, a known heat-sensitive adhesive that melts or softens by heating and exerts an adhesive effect can be preferably applied. Specifically, vinyl chloride resin, vinyl acetate resin, vinyl acetate vinyl acetate can be used. Polymerized resins, acrylic resins, polyester resins and the like can be used, but the present invention is not limited thereto. Examples of the resin used for the adhesive layer include acrylic resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride vinyl acetate copolymer resin, polyester resin, polyamide resin polyolefin resin and the like.
The material of the adhesive layer is preferably one having a melting point of about 50 ° C. or higher and 70 ° C. or lower, which is melt-bonded at a low temperature of about 80 ° C. and solidified and adhered at about 40 ° C.

The film thickness of the adhesive layer is not particularly limited, but is, for example, 0.1 μm or more and 10 μm or less, and preferably 1 μm or more and 5 μm or less.

<Primer layer>
The primer layer may be further provided when the adhesiveness between the cured product layer of the curable resin composition of the present invention and another layer such as the adhesive layer is insufficient.
As the material of the primer layer, for example, acrylic resin, urethane resin, vinyl chloride vinyl acetate copolymer resin, polyester resin, chlorinated polyolefin resin and the like can be used, but the material is not limited thereto.
Further, the primer layer may contain an additive that may be contained in the above-mentioned curable resin composition of the present invention.

The film thickness of the primer layer is not particularly limited, but for example, it may be 0.1 μm or more and 10 μm or less, and preferably 1 μm or more and 5 μm or less.

In the laminate of the present invention, since the cured product layer of the curable resin composition of the present invention has excellent wear resistance and tensile elongation, an insert can be obtained by appropriately selecting a resin base material as the base material. It can also be suitably used for molding.
For example, a cured product layer of the curable resin composition of the present invention is provided on one side of the base material, and a decorative layer is provided on the opposite side of the base material, and the cured product layer of the curable resin composition of the present invention is provided. A laminate laminated in the order of / base material / decorative layer is prepared as an insert molding film, the insert molding film is molded into a three-dimensional shape in advance by vacuum molding or the like, and the molding film is used for injection molding. After being inserted into the mold, the cavity is heated and melted resin is injected and filled, and then cooled and then the mold is opened. A decorative and surface protective layer can be provided by laminating the cured product layer of the curable resin composition of the present invention in this order.

When the base material of the laminate of the present invention is, for example, a molded product of synthetic resin, more specifically, for example, glass substitutes for transportation equipment such as automobiles, trains, and airplanes (front glass, rear window, opera window, etc.) (Triangular windows, sun roofs, etc.), lamps (head lamps, tail lamps, direction indicators, etc.), various meters and dials, bumpers, wheel caps, and other vehicle applications, various display applications, refrigerators, etc. Electrical appliances such as vacuum cleaners, TVs, coolers, etc., general equipment applications such as computer equipment, printers, copying machines, fax machines, optical disks, telephones, radios, etc., toys, furniture, packaging, etc. Miscellaneous goods such as sports equipment and game machine parts, lighting boards, windowpanes, window frames, wall materials, heat insulating materials, flooring materials, roofing materials, soundproofing boards and other building materials and civil engineering and construction applications, glasses, etc. Examples include optical equipment applications such as contact lenses and lenses for cameras, medical equipment applications, general industrial material applications, and nuclear-related applications.

When the base material of the laminated body of the present invention is, for example, a molded body of wood, more specific examples thereof include wood building materials for exterior use, furniture, floors, toys, and the like.

Since the laminate of the present invention has excellent flexibility such as tensile elongation, it is suitably used for applications requiring tensile elongation during manufacturing and use, and further imparts light resistance and weather resistance. It is also suitably used for applications that are directly exposed to ultraviolet rays, sunlight, and moisture. The laminate of the present invention is particularly used in, for example, building materials, window materials for transportation equipment such as automobiles, trains, and airplanes, lamp covers for traffic lights, carports, soundproof walls, agricultural and industrial films and sheets, automobiles, outer walls, and glass coatings. Demonstrate performance.

III. Laminate for transfer The laminate for transfer of the present invention is a laminate for transfer, which comprises at least the cured product layer of the curable resin composition of the present invention on a support and is used for transfer of the cured product layer. ..
FIG. 3 is a schematic cross-sectional view showing an example of the transfer laminate of the present invention, and FIG. 4 is a schematic cross-sectional view showing another example of the transfer laminate of the present invention.
As shown in FIG. 3, the transfer laminate 20 of the present invention has a configuration in which the cured product layer 2 of the curable resin composition of the present invention is provided on the support 11.
The transfer laminate 20 of the present invention may further include another layer. For example, as shown in FIG. 4, the transfer laminate 20 of the present invention has a cured product layer 2, a primer layer 4, and an adhesive layer 3 of the curable resin composition of the present invention on a support 11. You may prepare in this order.
Further, although not shown, the transfer laminate 20 of the present invention may be provided with the cured product layer 2 and the adhesive layer 3 of the curable resin composition of the present invention on the support 11 in this order.
Although not shown, the transfer laminate 20 of the present invention includes a release layer, a cured product layer 2 of the curable resin composition of the present invention, and an adhesive layer 3 on the support 11 in this order. You may.
Further, the transfer laminate 20 of the present invention may further include a layer other than the adhesive layer 3 and the primer layer 4, such as a decorative layer. As another layer such as a decorative layer, a known layer can be appropriately selected and used.

Hereinafter, the configuration of the transfer laminate of the present invention will be described in detail.
Among the transfer laminates of the present invention, the cured product layer, the adhesive layer, and the primer layer of the curable resin composition of the present invention may be the same as those of the laminate of the present invention, and thus the description thereof will be described here. Is omitted.

<Support>
The support of the transfer laminate is not particularly limited as long as it can be supported at least so as to be used for transfer of the cured product layer. The shape of the support of the transfer laminate is usually preferably a sheet or a film.
The support is generally preferably a plastic film, for example, polyethylene (PE) resin, polypropylene (PP) resin, polybutadiene resin, polyethylene terephthalate (PET) resin, polybutylene terephthalate resin, polyethylene naphthalate (PEN) resin, and the like. Triacetyl cellulose (TAC) resin, polymethyl methacrylate (PMMA) resin, polycarbonate (PC) resin, cycloolefin polymer, ethylene vinyl acetate copolymer (EVA) resin, polyvinyl chloride (PVA) resin, ABS resin, AS resin, etc. Film can be mentioned.
Above all, a film such as polyethylene terephthalate (PET) resin is preferably used from the viewpoint of dimensional stability, releasability and the like.

The support may be surface-treated to improve releasability. As such a surface treatment, a mold release agent is generally applied. Examples of the release agent include fluororesins, silicone resins, long-chain alkyl-based resin compounds, and the like.

<Release layer>
A release layer may be provided on the support of the transfer laminate at the boundary with the layer to be transferred. The release layer is not particularly limited as long as it is a material having releasability, but for example, silicone resin, organic resin modified silicone resin, fluororesin, aminoalkyd resin, melamine resin, acrylic resin, polyester resin and the like. There is. The film thickness of the release layer is not particularly limited, and examples thereof include 0.1 μm or more and 10 μm or less, and preferably 0.5 μm or more and 2 μm or less.

In the transfer laminate of the present invention, the cured product layer of the curable resin composition of the present invention has excellent wear resistance and tensile elongation. Therefore, by appropriately selecting a resin base material as a support, , Can also be suitably used for in-mold transfer.
For example, a transfer laminate in which the cured product layer and the decorative layer of the curable resin composition of the present invention are laminated in this order on the release-treated side surface of the release-treated support is prepared as an in-mold transfer film. Then, the in-mold transfer film is inserted into the injection molding mold so that the support is in contact with the mold, and then the cavity is filled with the melted resin by injection, and then cooled. By opening the mold, molding and decoration can be performed at the same time. In the case of in-mold transfer, the support can be peeled off after molding, and only the cured product layer of the curable resin composition as the decorative layer and the surface protective layer is transferred to the resin molded product.

Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention.
To measure the weight average molecular weight, GPC HLC-8220 manufactured by Tosoh Corporation is used as a measuring device, Shodex LF-404 x 2 are connected in series to the column, and the differential refractometer (RI) detector is used as the detector, standard. As the polystyrene, Basic Type PS-2 polystyrene (molecular weight range 580 to 364,000) manufactured by Agilent Technologies was used.
The obtained urethane acrylate was dissolved in THF so that the sample concentration was 0.2 wt%, the mobile phase was THF, the liquid feeding rate was 0.35 ml / min, the column temperature was 40 ° C., and the sample injection amount was 10 μL. Measurements were made.

(Synthesis Example 1: Production of Urethane (Meta) Acrylate 1>
A polyisocyanate containing an isocyanurate ring derived from hexamethylene diisocyanate in a four-necked flask equipped with a stirrer, an air introduction tube, and a thermometer (trade name: coronate HXLV, a multimer of 5 or more molecular weights, 26.2 mass). %, Weight average molecular weight 1090), 197.3 g, caprolactone-modified 2-hydroxyethyl acrylate (trade name: Praxel FA1, manufactured by Daicel Co., Ltd., R ^' = hydrogen atom, R ^" = ethylene in the general formula (a'). 252.7 g of the group, k = 1), 0.27 g of p-methoxyphenol, 1.44 g of dibutylhydroxytoluene and 111.0 g of toluene were added, mixed and heated to 60 ° C. at this time. The equivalent ratio of isocyanate groups / hydroxyl groups is 1.0. After the internal temperature became stable at 60 ° C., 1.63 g of a 10-fold toluene dilution solution of dioctyltin dineodecanoate was added. After the heat generation due to the addition of decanoate became stable, the temperature was maintained at 90 ° C. and the reaction was carried out for 4 hours, and then it was confirmed by the method of JIS K 7301 that the isocyanate group content was 0.1% or less. , 552.6 g of urethane (meth) acrylate 1 was obtained. The weight average molecular weight of the obtained urethane (meth) acrylate 1 was 2940.

(Synthesis Example 2: Production of Urethane (Meta) Acrylate 2>
In Synthesis Example 1, the amount of coronate HXLV was changed to 154.3 g, and instead of caprolactone-modified 2-hydroxyethyl acrylate (trade name: Praxel FA1), caprolactone-modified 2-hydroxyethyl acrylate (trade name: Praxel FA2D), ( Urethane (meth) in the same manner as in Synthesis Example 1, except that 295.6 g ^{of R'} = hydrogen atom, R ^" = ethylene group, k = 2) was used in the general formula (a') manufactured by Daicel Co., Ltd. 554.3 g of acrylate 2 was obtained. The weight average molecular weight of the obtained urethane (meth) acrylate 2 was 3700.

(Synthesis Example 3: Production of Urethane (Meta) Acrylate 3>
In Synthesis Example 1, the amount of coronate HXLV was changed to 229.2 g, and instead of 252.7 g of caprolactone-modified 2-hydroxyethyl acrylate (trade name: Praxel FA1), caprolactone-modified 2-hydroxyethyl acrylate (trade name: Praxel) was used. FA1) 549.8 g of urethane (meth) acrylate 3 in the same manner as in Synthesis Example 1 except that 146.7 g and 74.1 g of 2-hydroxyethyl acrylate were used to set the number of caprolactone modifications k = 0.5. Obtained. The weight average molecular weight of the obtained urethane (meth) acrylate 3 was 1970.

(Synthesis Example 4: Production of Urethane (Meta) Acrylate 4>
In Synthesis Example 1, instead of polyisocyanate containing an isocyanurate ring derived from hexamethylene diisocyanate (trade name: coronate HXLV, multimer of pentamer or more 26.2% by mass, weight average molecular weight 1090), hexamethylene Using 213.7 g of polyisocyanate containing an isocyanurate ring derived from diisocyanate (trade name: Coronate HK, 64.1% by mass of a multimer of pentamer or more, weight average molecular weight 2330), the amount of praxel FA1 was 236. 546.6 g of urethane (meth) acrylate 4 was obtained in the same manner as in Synthesis Example 1 except that the weight was changed to 3 g. The weight average molecular weight of the obtained urethane (meth) acrylate 4 was 6150.

(Synthesis Example 5: Production of Urethane (Meta) Acrylate 5>
In Synthesis Example 4, the amount of coronate HK was changed to 169.6, and instead of caprolactone-modified 2-hydroxyethyl acrylate (trade name: Praxel FA1), caprolactone-modified 2-hydroxyethyl acrylate (trade name: Praxel FA2D), ( Urethane (meth) in the same manner as in Synthesis Example 4, except that 280.4 g ^{of R'} = hydrogen atom, R ^" = ethylene group, k = 2) was used in the general formula (a') manufactured by Daicel Co., Ltd. 545.0 g of acrylate 5 was obtained. The weight average molecular weight of the obtained urethane (meth) acrylate 5 was 7650.

(Synthesis Example 6: Production of Urethane (Meta) Acrylate 6 (Comparative Compound)>
In Synthesis Example 1, instead of the polyisocyanate containing an isocyanurate ring derived from hexamethylene diisocyanate (trade name: Coronate HXLV), the polyisocyanate containing an isocyanurate ring derived from hexamethylene diisocyanate (trade name: Coronate HXR). 154.8 g of a pentamer or more multimer 47.6% by mass and a weight average molecular weight of 1540) is used, and polyethylene glycol monoacrylate (trade name: Praxel FA1) is used instead of caprolactone-modified 2-hydroxyethyl acrylate (trade name: Praxel FA1). Product name: Bremmer AE-200, manufactured by Nichiyu Co., Ltd., urethane (meth) acrylate 6 was used in the same manner as in Synthesis Example 1 except that 295.1 g of EO with an average number of repeating units n = 4.5) was used. 543.6 g was obtained. The weight average molecular weight of the obtained urethane (meth) acrylate 6 was 10640.

(Synthesis Example 7: Synthesis of bisbenzotriazolylphenol compound 1 represented by the general formula (1))
Under a nitrogen atmosphere, 2,2'-methylene-bis [6- (2H-benzotriazole-2-yl) -4- (2-hydroxyethyl) phenol] (RUVA-100: manufactured by Otsuka Chemical Co., Ltd.)
To 72.5 g (140 mmol), add 47.5 g (416 mmol) of ε-caprolactone and 6.0 mg (0.01 mmol) of mono-n-butyltin fatty acid salt (SCAT-24: manufactured by Nitto Kasei) to adjust the reaction temperature. Caprolactone-modified 2,2'-methylene-bis [6- (2H-benzotriazole-2-yl) -4- (2) represented by the following chemical formula (A) by keeping the temperature at 150 ° C. and reacting for 6 hours. -Hydroxyethyl) phenol] (m + n = 3) was obtained.

Caprolactone-modified 2,2'-methylene-bis [6- (2H-benzotriazole-2-yl) -4- (2-hydroxyethyl) phenol] represented by the chemical formula (A) (m + n = 3) 87. 27.5 g (195 mmol) of 2-isocyanatoethyl acrylate (Kalens AOI: manufactured by Showa Denko), 47.9 g of ethyl acetate, and 0.044 g of p-methoxyphenol are mixed with 5 g (98 mmol) and heated to 60 ° C. , Dioctyl tin neodecanoate (Neostan U-830: manufactured by Nitto Kasei), added 0.95 g (0.046 mmol) of ethyl acetate 30-fold diluted solution, and reacted at 75 ° C. for 4 hours, represented by the following chemical formula (B). Of the compounds, the target product (m + n = 3) was obtained.

1H-NMR (CDCl ₃ ): δ = 1.33 (m, 6H, CH ₂ ), 1.63 (m, 12H, CH ₂ ), 2.27 (m, 6H, CH ₂ ), 2.95 ( t, 4H, CH ₂ ), 3.47 (m, 4H, CH ₂ ), 4.01 (m, 6H, CH ₂ ), 4.22 (m, 4H, CH ₂ ), 4.27 (s, 2H, CH ₂ ), 4.31 (t, 4H, CH ₂ ), 5.07 (2H, NH), 5.85 (m, 2H, vinyl), 6.10 (m, 2H, vinyl) , 6.40 (m, 2H, vinyl), 7.23 (s, 2H, Ar-H), 7.49 (m, 4H, Ar-H), 7.93 (m, 4H, Ar-H) , 8.18 (s, 2H, Ar-H), 11.60 (s, 2H, Ar-OH)
Infrared absorption spectrum (KBr): 1714 cm ^-1 (urethane C = O), 1724 cm ^-1 (ester C = O)

(Example 1)
(1) Preparation of Curable Resin Composition 1 A curable resin composition having the following composition was prepared.
-Component (A); Urethane (meth) acrylate of Synthesis Example 1 1: 22.4 parts by mass-Component (B); Silica 1 (trade name: V-8803, manufactured by JGC Catalysts and Chemicals, average primary particle size 10 nm ~ Reactive irregularly shaped silica particles containing 2 to 15 substantially spherical silica particles of 100 nm connected and aggregated and having an ethylenically unsaturated bond-containing group on the surface, average particle size 25 nm, solid content 40%): 65.63 mass Parts-UV absorber; UVA1 (trade name: TINUVIN479, manufactured by BASF): 0.4 parts by mass-UV absorber; UVA2 (trade name: TINUVIN400, manufactured by BASF): 0.4 parts by mass-light stabilizer; HALS1 ( Product name: TINUVIN123, manufactured by BASF): 0.2 parts by mass, leveling agent; Leveling agent 1 (trade name: tegrad-2100, manufactured by Evonik): 0.5 parts by mass, solvent; MEK (methyl ethyl ketone): 10.77 mass Department

(2) Production of Laminated Body The curable resin composition 1 is applied onto an easily adhesive PET film (Toyobo Cosmoshine A4100) having a thickness of 100 μm so that the film thickness after drying is 5 μm, and then dried. A coating film was formed.
The coating film was irradiated with an electron beam under the conditions of 165 kV and 70 kGy to obtain a laminate having a cured product layer of the curable resin composition on the surface.

(Examples 2 to 9, Comparative Examples 1 to 4)
In each example, as shown in Table 2, a curable resin composition was prepared in the same manner as in Example 1 except that the compounding components and compounding ratios used were changed, and a laminate was obtained.

The abbreviations of each component in Table 2 are as follows.
Polyfunctional urethane (meth) acrylate 2 (k = 2); Synthesis Example 2
Polyfunctional urethane (meth) acrylate 3 (k = 0.5); Synthesis Example 3
-Polyfunctional urethane (meth) acrylate 4 (many functional groups k = 1); Synthesis Example 4
-Polyfunctional urethane (meth) acrylate 5 (many functional groups k = 2); Synthesis Example 5
-Polyfunctional urethane (meth) acrylate 6; Synthesis Example 6 (comparative compound)
Polyfunctional urethane (meth) acrylate 7; trade name Shikou UV7550B, manufactured by Nippon Synthetic Chemical Co., Ltd., urethane (meth) acrylate containing isocyanurate ring (comparative compound)
Polyfunctional urethane (meth) acrylate 8; trade name Aronix M-327, manufactured by Toagosei, ε-caprolactone-modified tris (acryloxyethyl) isocyanurate (comparative compound)
-Bifunctional (meth) acrylate 1; Urethane acrylate oligomer, trade name Aronix M-1200, manufactured by Toagosei (comparative compound)
Silica 2; (trade name: MIBK-AC-2140Z, manufactured by Nissan Chemical Industries, Ltd., reactive spherical silica particles having an ethylenically unsaturated bond-containing group on the surface, solid content 40%)
UVA3; bisbenzotriazolylphenol compound 1 of Synthesis Example 7

[Evaluation method]
(1) Abrasion resistance The laminate obtained in each example was cut into a size of 10 cm × 10 cm, and the sample was subjected to a taber under the conditions of a wear wheel CS-10F, a load of 500 g, and a rotation speed of 1000 rotations according to JIS K5600. A wear test was performed and the difference ΔH% between the haze values before and after the test was measured.
<Evaluation criteria>
◯: ΔH% is less than 3.0% Δ: ΔH% is 3.0% or more and less than 5.0% ×: ΔH% is 5.0% or more

(2) Elongation The laminate obtained in each example was cut into a size of 2.5 cm × 10 cm, and the sample was pulled using a tensile tester (AUTOGRAPH AG-X manufactured by Shimadzu Corporation) with a distance between chucks of 5 cm. A tensile test was performed at a speed of 50 mm / min. The length of elongation when cracks were generated in the cured product layer was measured, and the elongation was determined and evaluated as follows.
Elongation = (length of elongation when cracks occur in the cured product layer) / (length of the cured product layer before the test) x 100 (%)
<Evaluation criteria>
⊚: 60% or more ○: 30% or more and less than 60%
Δ: 20% or more and less than 30% ×: less than 20%

(3) Weather resistance The laminate obtained in each example was cut into a size of 5 cm × 5 cm, and the sample was subjected to a super UV weather resistance tester (Iwasaki Electric Co., Ltd. Eye Super UV Tester SUV-W161, illuminance 100 mW / cm). ^The degree of discoloration of the base material (PET film) when it was put into 2) was evaluated. In the super UV weather resistance tester, after irradiation with ultraviolet rays for 20 hours, water was sprinkled (shower) for 30 seconds, and the weather resistance test was performed with dew condensation for 4 hours as one cycle.
<Evaluation criteria>
⊚: No discoloration of the base material (PET film) even after the 200-hour weather resistance test ○: No change after the 100-hour weather resistance test, but there is discoloration of the base material (PET film) after the 200-hour weather resistance test Δ: 100-hour weather resistance After the test, there was discoloration of the base material (PET film) ×: After the weather resistance test for 100 hours, there was discoloration of the base material (PET film), and cracking of the base material was further confirmed.

(4) Chemical resistance The laminate obtained in each example was cut into a size of 5 cm × 5 cm, and a 1 cm square (1 cm ² ) waste cloth impregnated with methyl ethyl ketone was placed on the cured product layer of the sample. , Left for 24 hours.
<Evaluation criteria>
◯: No change Δ: Area without cracks is 95% or more with respect ^{to 1 cm 2} ×: Area without cracks is less than 95% with respect ^{to 1 cm 2.}

(Summary of results)
Urethane (meth) acrylate (A), which is a reaction product of a polyisocyanate containing an isocyanurate ring derived from hexamethylene diisocyanate and an ε-caprolactone adduct of hydroxyalkyl (meth) acrylate, has an average primary particle size of 10 nm. The curable resin composition of the present invention containing 2 to 20 substantially spherical inorganic particles having a diameter of about 100 nm in combination with reactive irregularly shaped inorganic particles (B) having an ethylenically unsaturated bond-containing group on the surface. It was clarified that in Examples 1 to 9 using the product, a cured product having high abrasion resistance and excellent tensile elongation can be obtained.
Among the examples, when urethane (meth) acrylate (A) containing a large number of pentamers or more in polyisocyanate and having a large number of functional groups in one molecule is used, the chemical resistance of the cured product is high. It was revealed that it would improve. It was also clarified that the chemical resistance of the cured product was improved even when the number of ε-caprolactone adducts added to the hydroxyalkyl (meth) acrylate was 0.5 mol on average. It is presumed that all of these are due to the increased crosslink density.
Further, it was clarified that when the bisbenzotriazolylphenol compound represented by the general formula (1) is used in combination as the ultraviolet absorber, the weather resistance is particularly improved.

On the other hand, it was clarified that the curable resin composition of Comparative Example 1, which corresponds to the curable resin composition of Patent Document 2, was particularly inferior in abrasion resistance and elongation. Further, similarly to the curable resin composition of Patent Document 2, the curable resin composition of Comparative Example 2 using urethane (meth) acrylate containing an ethylene oxide chain instead of the caprolactone chain is particularly inferior in abrasion resistance. It was clarified that the elongation was good when the ethylene oxide chain was contained, but the weather resistance and chemical resistance were also inferior.
Further, from Comparative Example 3, when a urethane (meth) acrylate containing an isocyanurate ring having no caprolactone chain was used, the abrasion resistance was inferior even when combined with the reactive irregularly shaped inorganic particles (B) used in the present invention. Moreover, it was clarified that the elongation was insufficient.
Further, it is clear that the curable resin composition of Comparative Example 4, which corresponds to the curable resin composition of Patent Document 1, has good elongation but poor wear resistance, and is inferior in weather resistance and chemical resistance. Was done.

Claims (10)

Urethane (meth) acrylate (A), which is a reaction product of a polyisocyanate containing an isocyanurate ring and a compound represented by the following general formula (a'),
Reactive irregularly shaped inorganic particles (B) having 2 to 20 substantially spherical inorganic particles having an average primary particle size of 10 nm to 100 nm connected and aggregated and having an ethylenically unsaturated bond-containing group on the surface.
Curable resin composition containing.

(In the general formula (a'), R'represents a hydrogen atom or a methyl group, R'represents a linear or branched aliphatic hydrocarbon group, j is a number of 3 or more and 5 or less, and k is 0. .3 or more.) The curable resin composition according to claim 1, wherein in the urethane (meth) acrylate (A), the polyisocyanate is a polyisocyanate containing an isocyanurate ring derived from an aliphatic diisocyanate. The urethane (meth) acrylate (A) is a reaction between a polyisocyanate containing an isocyanurate ring derived from hexamethylene diisocyanate and a compound represented by the general formula (a') in which j is 5. The curable resin composition according to claim 1 or 2, which is a compound. The curable resin composition according to any one of claims 1 to 3, wherein the urethane (meth) acrylate (A) contains a polymer of a pentamer or more as the polyisocyanate containing the isocyanurate ring. The curable resin composition according to any one of claims 1 to 4, wherein the polyisocyanate containing an isocyanurate ring has a weight average molecular weight of 2000 or more. The method according to any one of claims 1 to 5 , wherein in the urethane (meth) acrylate (A), k is 0.4 or more and 0.7 or less in the compound represented by the general formula (a'). Curable resin composition. The curable resin composition according to any one of claims 1 to 6 , further comprising a bisbenzotriazolylphenol compound. The curable resin composition according to any one of claims 1 to 7 , further comprising a bisbenzotriazolylphenol compound represented by the following general formula (1).

(In the general formula (1), Q represents a methylene group, an ethylidene group, an isopropylidene group, or a sec-butylidene group. R ¹ , R ² , R ³ and R ⁴ each independently have 1 or more carbon atoms. Represents a linear or branched aliphatic hydrocarbon group of 6 or less, R ⁵ and R ⁶ independently represent a hydrogen atom or a methyl group, respectively. R ⁷ and R ⁸ independently represent a hydrogen atom, a halogen atom, or a halogen atom, respectively. Represents an aliphatic hydrocarbon group having 1 or more and 4 or less carbon atoms. N and m are independently numbers of 1 or more and 10 or less, and n + m = 2 or more and 20 or less. P and q are independently 3 and 3 respectively. or 5 in which .r及beauty s is the number of following each independently a number of 1 or more and 2 or less.) A laminate comprising a cured product layer of the curable resin composition according to any one of claims 1 to 8 on a substrate. A transfer laminate provided with a cured product layer of the curable resin composition according to any one of claims 1 to 8 on a support, which is subjected to at least transfer of the cured product layer.

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