JP2019001972A - Curable resin composition, laminate, and laminate for transfer - Google Patents

Abstract

To provide a curable resin composition capable of providing a cured article excellent in tensile extensibility, while having high abrasion resistance, a laminate having a cured article layer of the composition, and a laminate provided for transfer of the cured article layer.SOLUTION: There is provided a curable resin composition containing urethane (meth)acrylate (A), which is a reaction product between polyisocyanate containing an isocyanurate ring and a compound represented by the following general formula (a'), and a reactive irregular shape inorganic particle (B) in which 2 to 20 almost spherical inorganic particles having average primary particle diameter of 10 nm to 100 nm are aggregated, and which has an ethylenic unsaturated bond-containing group on a surface.SELECTED DRAWING: Figure 1

Description

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

  The curable resin composition that is cured by irradiation with active energy rays such as ultraviolet rays and electron beams cures to form a cured product having scratch resistance and chemical resistance, and thus imparts protection or design properties to the article surface. Therefore, it is used in a wide range of applications such as coating materials and coating agents, and optical materials that are molded into a desired shape to provide optical properties.

  Furthermore, in recent years, insert molding or surface protection in which a protective film or decorative film having a surface protective layer on a substrate is inserted into an injection mold, the injection molding is performed, and the entire film is attached to a molded product. Insert a protective film or decorative film provided with a layer on the base material into the mold, perform injection molding, peel off the base material, and leave the surface protective layer and, optionally, the decorative layer in the molded product. Use for mold transfer films is expanding.

  Generally, the curable resin composition is cured to form a cured product layer having improved surface hardness by increasing the crosslink density. However, since such a cured product layer is weakened due to a decrease in flexibility, there are cases where a crack is generated when it is bent or pulled, or it is easily cracked when an impact is applied by an external force. Further, when used for the insert molding or in-mold transfer film, there is a problem that the elongation of the resin is lowered due to the hardening of the surface protective layer, and the workability is deteriorated.

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

  Patent Document 2 discloses (A) component as a curable resin composition capable of obtaining a cured product having excellent flaw resilience and surface hardness, and excellent curl resistance and flex 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: surface-modified inorganic oxide particles obtained by reacting a compound (b1) having a polymerizable unsaturated group and a hydrolyzable silyl group with inorganic oxide particles (b2) at a specific ratio. A curable resin composition is disclosed.

JP2011-225679A JP, 2015-113415, A

  A cured product of a curable resin composition for surface protection in recent years is required to be excellent in tensile elongation while having high wear resistance. However, the cured products of the curable resin compositions of the prior art as described in Patent Documents 1 and 2 are still insufficient in abrasion resistance, and further improvement in tensile elongation is required.

  Therefore, the present invention provides a curable resin composition capable of obtaining a cured product excellent in tensile elongation while having high wear resistance, a laminate including a cured product layer of the composition, and the composition. It is an object of the present invention to provide a transfer laminate for use in transferring a cured product layer.

The curable resin composition of the present invention is a urethane (meth) acrylate (A) that 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;
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 to 5, 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. It is preferable from the point.

  In the curable resin composition of the present invention, the urethane (meth) acrylate (A) includes 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 wherein j is 5 is preferable from the viewpoint of tensile elongation.

  In the curable resin composition of the present invention, the urethane (meth) acrylate (A) contains a polymer of a pentamer or more as the polyisocyanate containing the isocyanurate ring. Is preferable from the viewpoint of improvement.

  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 may be 0.4 or more and 0.7 or less. From the viewpoint of improving the chemical resistance of the cured product.

  In the curable resin composition of this invention, it is preferable to contain a bisbenzotriazolyl phenol compound from the point that the weather resistance of hardened | cured material becomes high.

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

(In 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 represent 1 or more carbon atoms. 6 or less linear or branched aliphatic hydrocarbon groups, R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, R ⁷ and R ⁸ each independently represent a hydrogen atom, a halogen atom, or Represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms, n and m are each independently a number of 1 to 10 and n + m = 2 to 20; p and q are each independently 3 The number is from 5 to 5. r and s are each independently from 1 to 2.

Moreover, this invention provides the laminated body provided with the hardened | cured material layer of the said curable resin composition of this invention.
Furthermore, this invention provides the laminated body for a transfer provided with the hardened | cured material layer of the said curable resin composition of this invention at least for the transcription | transfer of the said hardened | cured material layer.

  According to the present invention, a curable resin composition capable of obtaining a cured product having high wear resistance and excellent tensile elongation, a laminate including a cured product layer of the composition, and the composition It is possible to provide a transfer laminate for use in transferring the cured product layer.

FIG. 1 is a schematic cross-sectional view showing an example of the laminate of the present invention. FIG. 2 is a schematic cross-sectional view showing another example of the laminate 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 refers to an energy ray that can generate an active species by decomposing a compound that generates an active species. Examples of such active energy rays include optical energy rays such as visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, γ rays, and electron beams.
In this specification, (meth) acryl represents each of acrylic and methacryl, (meth) acryloyl represents each of acryloyl and methacryloyl, and (meth) acrylate represents each of acrylate and methacrylate.
In this specification, when a certain configuration such as a certain member or a certain region is “above (or below)” another configuration such as another member or another region, unless otherwise limited, This includes not only when directly above (or directly below) another configuration, but also when above (or below) another configuration, i.e., another configuration above (or below) another configuration. This includes cases where elements are included.
Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the present invention can be implemented in many different modes, and should not be construed as being limited to the description of the embodiments described below. In addition, the drawings may be schematically represented with respect to the width, thickness, shape, and the like of each part as compared with the embodiments for the sake of clarity of explanation, but are merely examples, and the interpretation of the present invention is not limited thereto. It is not limited. In addition, in the present specification and each drawing, elements similar to those described above with reference to the previous drawings are denoted by the same reference numerals, and detailed description may be omitted as appropriate. Further, for convenience of explanation, the description may be made using the terms “upper” or “lower”, 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;
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 to 5, and k is 0. .3 or more.)

The curable resin composition of the present invention comprises a urethane (meth) acrylate (A) that is a reaction product of a polyisocyanate containing an isocyanurate ring and an ε-caprolactone adduct of hydroxyalkyl (meth) acrylate, and an average primary. By using a combination of reactive spherical inorganic particles (B) having 2 to 20 substantially spherical inorganic particles having a particle diameter of 10 nm to 100 nm and having an ethylenically unsaturated bond-containing group on the surface, It is possible to obtain a cured product that is excellent in tensile elongation while having wear properties.
The surface protective layer is required to be scratched and not cloudy even if the same part is repeatedly rubbed, and is required to have high wear resistance. However, it has been difficult to achieve high wear resistance. It was. In particular, it has been difficult to achieve both high tensile elongation and high wear resistance of the cured layer of the curable resin composition. That is, if a component for increasing flexibility is added in order to increase the tensile elongation of the cured product layer, it becomes easy to be damaged and the wear resistance is likely to decrease. On the other hand, even if a component that increases the hardness for wear resistance is used, it tends to be hard and brittle and the wear resistance tends to decrease.
On the other hand, in the present invention, an average primary particle is added to urethane (meth) acrylate (A) which is a reaction product of polyisocyanate containing an isocyanurate ring and an ε-caprolactone adduct of hydroxyalkyl (meth) acrylate. Elasticity and high hardness are obtained by using a combination of reactive deformed inorganic particles (B) having 2 to 20 substantially spherical inorganic particles having a diameter of 10 nm to 100 nm connected and agglomerated and having an ethylenically unsaturated bond-containing group on the surface. A cross-linked structure in which is combined is constructed to improve wear resistance while absorbing impact. Furthermore, since the reactive irregularly shaped inorganic particles (B) are incorporated into the crosslinked structure, the chain particles in which 2 to 20 approximately spherical inorganic particles are connected and aggregated extend so as to follow the tensile direction. It is estimated that cracks are less likely to be generated with respect 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 urethanizing a polyisocyanate containing an isocyanurate ring and a compound represented by the following general formula (a ′). Compound.

(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 to 5, and k is 0. .3 or more.)

  Polyisocyanates containing an isocyanurate ring are derived from diisocyanates having two isocyanate groups in the molecule. As polyisocyanate containing an isocyanurate ring, 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) , A 9-mer represented by the following general formula (a-4), and higher multimers.

  (In General Formula (a-1) to General Formula (a-4), R represents a hydrocarbon group having 3 to 14 carbon atoms.)

In General Formula (a-1) to General Formula (a-4), R represents a hydrocarbon group having 3 to 14 carbon atoms, and is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon. Groups, and combinations thereof.
In General Formula (a-1) to General Formula (a-4), R is a residue obtained by removing two isocyanate groups from diisocyanate. Examples of the diisocyanate for deriving the polyisocyanate containing an isocyanurate ring include, for example, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, diphenylmethane. Examples thereof include diisocyanate, tolylene diisocyanate, and tolidine diisocyanate.
As the diisocyanate for inducing the polyisocyanate containing an isocyanurate ring, a diisocyanate containing an aliphatic hydrocarbon group between two isocyanate groups is preferable from the viewpoint of improving tensile elongation, and aliphatic or alicyclic Diisocyanates are more preferable, aliphatic diisocyanates are more preferable, aliphatic diisocyanates having 4 to 9 carbon atoms, more preferably aliphatic diisocyanates having 4 to 6 carbon atoms, and hexamethylene diisocyanate is particularly preferable.

  Generally the manufacturing method of the polyisocyanate containing an isocyanurate ring can be manufactured in accordance with a well-known method. For example, an isocyanurate-forming catalyst such as diisocyanate or quaternary ammonium salt and an organic solvent as necessary are put into a reaction vessel, and the isocyanurate-forming reaction is carried out while maintaining a predetermined temperature. Further, after the reaction, it is preferable to stop the isocyanuration reaction by introducing a reaction terminator for the purpose of improving the storage stability. For example, referring to JP-A-2002-241458, the amount of multimers can be adjusted by appropriately adjusting the reaction temperature and reaction time. Furthermore, it is preferable to remove unreacted diisocyanate by distillation.

In the said urethane (meth) acrylate (A), it is preferable that the polymer more than a pentamer is contained as polyisocyanate containing the isocyanurate ring induced | guided | derived from diisocyanate from the point which the chemical resistance of hardened | cured material improves. . Especially, it is preferable that the polymer of a pentamer or more is 40 mass% or more of the whole polyisocyanate containing the isocyanurate ring induced | guided | derived from diisocyanate, and also it is preferable that it is 50 mass% or more. On the other hand, it is preferable that it is 70 mass% or less from the point of tensile elongation property.
Among these, in the urethane (meth) acrylate (A), the polyisocyanate is a polyisocyanate containing an isocyanurate ring derived from an aliphatic diisocyanate because the chemical resistance and tensile elongation of the cured product are improved. The polyisocyanate preferably contains a polymer of pentamer or higher. Especially, it is preferable that the polymer of a pentamer or more is 40 mass% or more of the whole polyisocyanate containing the isocyanurate ring induced | guided | derived from aliphatic diisocyanate, and also it is preferable that it is 50 mass% or more. On the other hand, it is preferable that it is 70 mass% or less from the point of tensile elongation property.
When the polyisocyanate is derived from an aliphatic diisocyanate, an aliphatic hydrocarbon group is connected to the polyisocyanate. The number of functional groups can be increased to improve the crosslinking density, and the effect of improving the chemical resistance and tensile elongation of the cured product is high.

The polyisocyanate containing an isocyanurate ring derived from the diisocyanate preferably has a weight average molecular weight of 1000 or more, more preferably 1500 or more, from the viewpoint of improving the chemical resistance of the cured product. More preferably, it is 2000 or more. On the other hand, from the viewpoint of tensile elongation, it is preferably 3000 or less, and more preferably 2500 or less.
Here, the weight average molecular weight (Mw) in this specification is determined as a standard polystyrene equivalent value by gel permeation chromatography (GPC).
For example, GPC HLC-8220 manufactured by Tosoh Corporation is used as a measuring apparatus, two columns of Shodex LF-404 are connected in series, a differential refractive index (RI) detector is used as a detector, and Agilent is used as a standard polystyrene. Technical Types PS-2 polystyrene (molecular weight range 580 to 364,000) manufactured by Technologies 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 feed rate was 0.35 ml / min, the column temperature was 40 ° C., and the sample injection amount was 10 μL. Can be measured.
However, since isocyanurate is not measured directly, but is measured after the isocyanate group is deactivated by ethanol as a pretreatment, the molecular weight of isocyanurate in this specification is the amount of ethanol added to isocyanurate. It describes as molecular weight to contain.

  The polyisocyanate containing an isocyanurate ring derived from diisocyanate may be appropriately selected and a commercially available product may be used.

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

(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 to 5, 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 And a butylene group are preferable, and an ethylene group is more preferable.

  Examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate. It is 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 added of the lactone chain, and is a number of 0.3 or more is there. A compound of j = 3 is obtained by ring-opening addition polymerization of γ-butyrolactone, a compound of j = 4 is obtained by ring-opening addition polymerization of δ-valerolactone, and j = 5 is obtained by ring-opening addition polymerization of ε-caprolactone. A compound is obtained. Especially, it is preferable from the point of tensile elongation property that it is a compound of j = 5 obtained by the ring-opening addition polymerization of (epsilon) -caprolactone. 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 hydroxyalkyl (meth) acrylate lactone adduct and a hydroxyalkyl (meth) acrylate, and the remainder (1-k) Is a hydroxyl group of hydroxyalkyl (meth) acrylate.

k is a number of 0.3 or more, but is preferably 1 or more from the viewpoint of improving tensile elongation. 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 point that the chemical resistance of the cured product is further improved, 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 0.4 mol or more and 0.7 mol or less with respect to 1 mol of the isocyanate group of the polyisocyanate containing an isocyanurate ring in the acrylate (A). ) It is preferable that the remaining hydroxyl group of acrylate is 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 polyisocyanate ring containing an isocyanurate ring in the urethane (meth) acrylate (A). The hydroxyl group of the lactone adduct of hydroxyalkyl (meth) acrylate is 0.5 mol or more and 0.7 mol or less with respect to 1 mol of isocyanate group of isocyanate, and the remaining hydroxyl group of hydroxyalkyl (meth) acrylate is 0.3 mol. It is preferable to contain from 0.5 mol to 0.5 mol.

  The compound represented by the general formula (a ′) can be produced according to a known method. For example, in a reaction vessel, hydroxyalkyl (meth) acrylate, at least one lactone of γ-butyrolactone, δ-valerolactone, and ε-caprolactone, a ring-opening polymerization catalyst such as Lewis acid and alkali, and the like A polymerization inhibitor and an organic solvent are added, and a reaction is performed while maintaining a predetermined temperature. In addition, lactones such as ε-caprolactone may be dropped and reacted after raw materials other than these are added in advance. Further, after the reaction, the catalyst may be adsorbed using a known adsorbent, and the adsorbent may be removed by filtration, or the salt generated by neutralization 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. Examples thereof include caprolactone-modified 2-hydroxyethyl (meth) acrylate [trade name: Plaxel F series, manufactured by Daicel Corporation, average added mole number 1 to 20].
Moreover, the compound represented with the said general formula (a ') may be used independently, and may use 2 or more types together.

  The urethane (meth) acrylate (A) used in the curable resin composition of the present invention is obtained by urethanizing a polyisocyanate containing an isocyanurate ring and a compound represented by the general formula (a ′). Although it is a compound, the hydroxyl group of the compound represented by the general formula (a ′) is not necessarily 1 mol of the reactant with respect to 1 mol of the isocyanate group of the polyisocyanate containing an isocyanurate ring.

In general, the urethane (meth) acrylate (A) can be produced according to a known method. For example, a polyisocyanate containing an isocyanurate ring in a reaction vessel, a compound represented by the general formula (a ′) (for example, a lactone adduct of hydroxyalkyl (meth) acrylate, and optionally a hydroxyalkyl (meth) acrylate) Then, if necessary, a urethanization catalyst, a polymerization inhibitor, and an organic solvent are added, and the reaction is performed 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 ′) and the isocyanate group in the polyisocyanate are equivalent to each other. It is made to react in the range whose equivalent ratio of an isocyanate group is 0.8 / 1-1.1 / 1 normally. The polyisocyanate and the compound represented by the general formula (a ′) may be reacted by dropping one of the raw materials in advance and then dropping raw materials other than the previously charged raw material. Moreover, a urethanation reaction is normally performed in 30-100 degreeC. The end point of the urethanization reaction can be confirmed by disappearance of the infrared absorption spectrum at 2270 cm ⁻¹ indicating the isocyanate group or by determining the content of the isocyanate group by the method described in JIS K 7301. As the urethanization catalyst, tin compounds such as dibutyltin dilaurate and amines such as triethylamine can be used.

(Reactive irregularly shaped inorganic particles (B))
The reactive irregularly shaped inorganic particles (B) used in the curable resin composition of the present invention are formed by connecting and agglomerating 2 to 20 approximately spherical inorganic particles having an average primary particle size of 10 nm to 100 nm and having no ethylenic surface. It is a reactive irregularly shaped inorganic particle having a saturated bond-containing group.

In the present invention, the irregularly shaped inorganic particles are composed of a group of inorganic particles in which 2 to 20 substantially spherical inorganic particles having an average primary particle size of 10 nm to 100 nm are connected and aggregated. Connected aggregation 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 that includes a true sphere.

  As the inorganic particles forming the inorganic particle group, inorganic particles composed of metal oxides such as silica (colloidal silica, fumed silica, precipitated silica, etc.), alumina, zirconia, titania, zinc oxide, etc. are preferably mentioned. From the viewpoint of improving the wear resistance and wear resistance, inorganic particles made of silica or alumina are preferable. That is, the irregular shaped inorganic particles are preferably those obtained by connecting and agglomerating 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 irregular shaped 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. It is preferable that 10 to 10 are connected and aggregated.
The deformed inorganic particles used in the present invention are preferably composed of 2 to 20 substantially spherical inorganic particles having an average primary particle size of 10 nm to 50 nm connected and aggregated from the viewpoint of wear resistance. It is preferable that 2 to 15 substantially spherical inorganic particles having a particle diameter of 10 nm to 50 nm are connected and aggregated, and further, 2 to 10 approximately spherical inorganic particles having an average primary particle diameter of 10 to 50 nm are connected and aggregated. Preferably it is.
The size and shape of the irregular shaped 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 in a state of being applied to an observation sample stage so as to have a thickness equivalent to one layer of inorganic particles. Unlike the state in which the particles are aggregated into a large substantially spherical shape, it is possible to determine that the substantially spherical inorganic particles are connected and aggregated in a certain direction as connected and aggregated. There may be two or more directions in which the substantially spherical inorganic particles are connected to each other. In the case of a cured product of the resin composition, the state of the particles can be observed by cutting out the cross section.

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

  Preferred 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 the silane coupling agent having an ethylenically unsaturated bond-containing group, in addition to the ethylenically unsaturated bond-containing group, a known silane coupling agent further having an alkoxy group, amino group, vinyl group, epoxy group, mercapto group, chloro group, etc. Silane coupling agents, and more specifically, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyldimethylethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyldimethylmethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acrylic Preferred examples include xylpropylmethyldiethoxysilane, γ-acryloxypropyldimethylethoxysilane, vinyltriethoxysilane, and more preferably γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ- And methacryloxypropyldimethylmethoxysilane.

  There are no particular restrictions on the method of decorating the irregularly shaped inorganic particles with the silane coupling agent, and any known method may be used. A dry method in which the silane coupling agent is sprayed, or after the irregularly shaped inorganic particles are dispersed in the solvent, 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 with respect to the irregularly shaped inorganic particles is usually 1 mass when the total mass of the irregularly shaped inorganic particles and the silane coupling agent is 100 parts by mass. Part to 50 parts by weight, preferably 2 parts to 30 parts by weight, and more preferably 5 parts to 20 parts by weight.

The curable resin composition of the present invention contains, in addition to the reactive irregularly shaped inorganic particles (B), reactive inorganic particles (B ′) that do not fall under the reactive irregularly shaped inorganic particles (B). Also good. Examples of the reactive inorganic particle (B ′) include those having an ethylenically unsaturated bond-containing group on the surface of a substantially spherical inorganic particle, and the ethylenically unsaturated material present on the surface of the inorganic particle or the inorganic particle surface. The bond-containing group is preferably the same as the reactive irregularly shaped inorganic particle (B).
When the curable resin composition of the present invention contains, in addition to the reactive irregularly shaped inorganic particles (B), reactive inorganic particles (B ′) that do not fall under the reactive irregularly shaped inorganic particles (B), tensile From the viewpoint of improving wear resistance while improving extensibility, reactive deformed inorganic particles (B) with respect to 100 parts by mass of the total amount of reactive deformed inorganic particles (B) and 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 even more preferably 70 parts by mass or more.

  The curable resin composition of the present invention includes, in addition to the reactive irregularly shaped inorganic particles (B), reactive inorganic particles (B ′) and other inorganic particles that do not fall under the reactive irregularly shaped inorganic particles (B). However, the average particle size of the inorganic particles including 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. More preferably, it is 200 nm or less. The average particle diameter is a 50% particle diameter (d50: median diameter) when the particles in the solution are measured by a dynamic light scattering method and the particle diameter distribution is expressed as a cumulative distribution. It can be measured using a microtrack UPA150).

Reactive inorganic particles containing urethane (meth) acrylate (A) and reactive irregularly shaped inorganic particles (B) in the curable resin composition of the present invention, from the viewpoint of a balance between wear resistance and tensile elongation. The content ratio of the urethane (meth) acrylate (A) and the reactive inorganic particles including the reactive irregularly shaped inorganic particles (B) is 100 parts by mass, and the urethane (meth) acrylate (A) is 20 masses. Part or more, preferably 30 parts by weight or more.
Above all, from the viewpoint of improving the wear resistance, in the curable resin composition of the present invention, the total amount of urethane (meth) acrylate (A) and reactive inorganic particles containing reactive irregularly shaped inorganic particles (B) is 100 mass. In the part, the urethane (meth) acrylate (A) is preferably 60 parts by mass or less, more preferably 55 parts by mass or less, and still more preferably 50 parts by mass or less.
On the other hand, particularly from the point of improving tensile elongation, in the curable resin composition of the present invention, the total amount of urethane (meth) acrylate (A) and reactive inorganic particles containing reactive irregularly shaped inorganic particles (B). Although 90 mass parts may be sufficient as urethane (meth) acrylate (A) in 100 mass parts, it is preferable that it is 98 mass parts or less from the point of coexistence with abrasion resistance.

<Other ingredients>
The curable resin composition of this invention may contain the ultraviolet absorber further from the point which improves a 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 is strong against light and moisture, so that it contains an ether bond such as an alkylene oxide chain. It is presumed that the weather resistance can be increased.
An ultraviolet absorber can be used individually or in combination of 2 or more types.

As an ultraviolet absorber, for example, a benzotriazole compound, a benzophenone compound, a triazine compound, a cyanoacrylate compound, a benzoxazinone compound, a benzoxazole compound, a merocyanine compound, or any combination thereof is used. It is preferable. This is because a wide wavelength range is absorbed. Of these, benzotriazole compounds, benzophenone compounds, and triazine compounds are more preferable.
Specific examples thereof include, for example, 2- (2-hydroxy-5-methyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 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 -Yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2′-hydroxy-3 ′, 5′-t-pentylbenzotriazole, 2- [2′-hydride) Roxy-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-benzotriazol-2-yl) phenol], 3- [3 -(2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl] propionate and a benzotriazole such as a reaction product of polyethylene glycol; 2-hydride Xylbenzophenone, 5-chloro 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2, Benzophenones such as 2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone; 2- (4,6-diphenyl-1, 3,5-triazin-2-yl) -5-[(methyl) oxy] -phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(ethyl) Oxy] -phenol, 2- (4,6-diphenyl-1,3,5-triazine- 2-yl-[(propyl) oxy] -phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(butyl) oxy] -phenol, 2- (4 , 6-Diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol and the like; 2-ethylhexyl 2-cyano-3, 3-diphenyl acrylate, 1,3 Cyanoacrylates such as -bis (2'-cyano-3,3'-diphenylacryloyl) oxy) -2,2-bis (((2'-cyano-3,3'-diphenylacryloyl) oxy) methyl) propane 2,2′-p-phenylenebis (4H-3,1-benzoxazin-4-one), 2,2′-p-phenylenebis (6-methyl-4H-3,1-benzoxazine-4-one) ON) etc. Benzoxazinones; 2,5-thiophenediyl (5-tert-butyl-1,3-benzoxazole), 2,6-di (benzoxazol-2-yl) naphthalene, 4,4′-bis (benzoxazole) Benzoxazoles such as 2-yl) furan; 1,3-dimethyl-5- [2- (3-methyloxazolidine-2-ylidene) ethylidene] pyrimidine-2,4,6-trione, octyl-5-N, And merocyanines such as N-diethylamino-2-phenylsulfonyl-2,4-pentadienoate.

In particular, 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.
The bisbenzotriazolylphenol compound has a high molecular absorption coefficient, and therefore has good ultraviolet absorption performance, has an extremely low vapor pressure, and has high thermal stability. Therefore, even if it mixes with resin, volatilization is suppressed and it can mix stably, without decomposing.

  In addition, among the bisbenzotriazolylphenol compounds, when having 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 of providing weather resistance and ultraviolet shielding properties.

  Furthermore, among the bisbenzotriazolylphenol compounds, when it contains a lactone chain that is a ring-opening addition polymerization chain of at least one lactone of γ-butyrolactone, δ-valerolactone, and ε-caprolactone, The ultraviolet absorber itself is preferable because it contributes to tensile elongation.

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

(In 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 represent 1 or more carbon atoms. 6 or less linear or branched aliphatic hydrocarbon groups, R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, R ⁷ and R ⁸ each independently represent a hydrogen atom, a halogen atom, or Represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms, n and m are each independently a number of 1 to 10 and n + m = 2 to 20; p and q are each independently 3 The number is from 5 to 5. r and s are each independently from 1 to 2.

Since the bisbenzotriazolylphenol compound represented by the general formula (1) has 2 to 4 (meth) acryloyl groups in one molecule, the ultraviolet absorber itself serves as a crosslinking agent. Since it functions, it is possible to impart excellent weather resistance and ultraviolet shielding properties without reducing the crosslinking density.
Furthermore, the bisbenzotriazolylphenol compound represented by the general formula (1) is used in the presence of water as compared with a bisbenzotriazolylphenol compound having a conventional (meth) acryloyl group. It is difficult to bleed out under the environment, and is excellent in weather resistance, that is, long-term sustainability of light stability in a use environment that 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, and therefore has the advantage that it is difficult to aggregate and unevenly distributed. In the substituent of the above, since it has two aliphatic hydrocarbon chains and a lactone chain, the compatibility with the resin is improved, the resin is easily dispersed in the resin, and the (meth) acryloyl group present at the terminal is free. It is estimated that the degree of reaction increases and the reaction efficiency with the ethylenically unsaturated bond-containing group of other molecules is improved.

  Furthermore, the bisbenzotriazolylphenol compound represented by the general formula (1) includes 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, it is incorporated into the crosslinked structure without reducing the crosslinking density, thereby imparting flexibility and elasticity to the crosslinked structure. Therefore, it can improve, without inhibiting the tensile elongation property of the hardened | cured material of 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 to 6 carbon atoms in R ¹ and R ² include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, ethylidene, propylene, propylidene, and ethylethylene. , 2-butylidene, 1-methyltrimethylene, 1,1-dimethylethylene, 1,1-dimethyltrimethylene, 2-methyltrimethylene, 2,2-dimethyltrimethylene, and other linear or branched groups Is mentioned. As R ¹ and R ² , a linear aliphatic hydrocarbon group of 2 to 6 is preferable, and ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene are preferable.

When r and s are each 1, R ³ and R ⁴ are each a divalent straight chain or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, and examples thereof are R ¹ and R ² . In addition, the same as the linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms can be preferably used.
When r and s are each 2, R ³ and R ⁴ are each a trivalent straight chain or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, and a straight chain having 1 to 6 carbon atoms. Examples include residues obtained by removing three hydrogen atoms from a chain or branched aliphatic hydrocarbon. As R ³ and R ⁴ when r and s are 2, respectively, for example, a trivalent aliphatic hydrocarbon group represented by the following chemical structural formula is preferably used.
When r and s are each independently 2, 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 other molecules is improved.

R ¹ , R ² , R ³ , and R ⁴ may be the same or different from each other, but from the viewpoint of production, R ¹ and R ² are preferably the same, and R ³ and R ⁴ Are preferably the same.

R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group, but a hydrogen atom is preferred from the viewpoint of improving reaction efficiency.

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, a chlorine atom and a bromine atom are preferable.
Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms in R ⁷ and R ⁸ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group.

  p and q are each independently a number of 3 or more and 5 or less. That is, the bisbenzotriazolylphenol compound represented by the general formula (1) is a lactone chain that is a ring-opening addition polymerization chain of at least one lactone among γ-butyrolactone, δ-valerolactone, and ε-caprolactone. Is included. A compound with p and q of 3 is obtained by ring-opening addition polymerization of γ-butyrolactone, a compound with p and q of 4 is obtained by ring-opening addition polymerization of δ-valerolactone, and by ring-opening addition polymerization of ε-caprolactone. A compound having p and q of 5 is obtained. When a mixture of two or more lactones is 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 each independently 1 or more and 10 or less. n and m each represent the degree of polymerization (number of added moles) of the lactone, and n and m may each be an average value. n and m are appropriately determined depending on the use in consideration of whether the lactone chain needs to improve flexibility and tensile elongation or whether it is necessary to increase hardness while improving tensile elongation. You can choose. Among these, from the viewpoint of improving flexibility such as tensile elongation, n and m are each preferably preferably independently of an average of 1.5 or more, and preferably 8 or less from the viewpoint of improving hardness. It is further preferably 6 or less, and further 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, 16 or less is preferable from the viewpoint of improving hardness. , 12 or less, more preferably 10 or less.

Specific examples of the bisbenzotriazolylphenol compound of the present invention represented by the general formula (1) include the following combinations of compounds.
In the following combination of compounds, p and q are each 5 and r and s are 1 respectively.
Furthermore, in the following combinations of compounds, p and q are each 5 and r and s are 2 respectively.
In the following combinations of compounds, p and q are each 4 and r and s are each 1, and 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 a conventionally known method, for example, to the alcoholic hydroxyl group of the bisbenzotriazolylphenol compound represented by the general formula (2). Can be produced by ring-opening addition polymerization of a lactone such as ε-caprolactone and reacting an alcoholic hydroxyl group of the lactone chain with an isocyanate compound having a (meth) acryloyloxy group in a solvent.

(In general formula (2), Q, R ¹ , R ² , R ⁷ and R ⁸ are the same as in 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. Propyl 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, from the viewpoint of improving weather resistance, the content 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 the urethane (meth) acrylate (A). The content is preferably 1 part by mass or less, and more preferably 1 part by mass or more and 5 parts by mass or less.

The curable resin composition of the present invention further has the effect of the present invention depending on the use of a polymerizable compound having an ethylenically unsaturated bond-containing group, which is different from the urethane (meth) acrylate (A). It may be contained within the range.
Here, the polymerizable compound having an ethylenically unsaturated bond-containing group is not particularly limited, and includes compounds such as a polymer (high polymer), an oligomer (low polymer), and a monomer (monomer). And publicly known ones can be used as appropriate. As a compound which has the said ethylenically unsaturated bond containing group, it can be used individually by 1 type or in mixture of 2 or more types.
Specifically, for example, polyfunctional polyester (meth) acrylate oligomer, polyfunctional urethane (meth) acrylate oligomer, polyfunctional epoxy (meth) acrylate having at least two (meth) acryloyloxy groups in one molecule. System oligomers and the like. Polyfunctional monomers include 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, 5-pentanediol di (meth) acrylate, neobentyl glycol di (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, hydroxypivalic acid neobentyl glycol di (meth) acrylate, Bisphenol A polyethoxydiol di (meth) acrylate, bisphenol A polypropoxydiol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylol brobantri (meta) ) 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, Ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol Hexa (meth) acrylate and the like, but not limited thereto.

The content in the case of containing a polymerizable compound having an ethylenically unsaturated bond-containing group, which is different from the urethane (meth) acrylate (A), is appropriately within the range in which the effect of the present invention can be obtained depending on the application. Select and use. For example, when importance is attached to elongation, it may further contain a polymerizable compound having two ethylenically unsaturated bond-containing groups in one molecule, but it contains two ethylenically unsaturated bonds 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 including the reactive irregularly shaped inorganic particles (B). In view of obtaining a cured product having high abrasion resistance and excellent tensile elongation, it is preferably 30 parts by mass or less, and more preferably 20 parts by mass or less. The content in the case of containing a polymerizable compound having three or more ethylenically unsaturated bond-containing groups in one molecule is not limited, but urethane (meth) acrylate (A) and reactive irregular inorganic From the point which makes elongation good with respect to 100 mass parts of total amounts with the reactive inorganic particle containing particle | grains (B), 20 mass parts or less are mentioned, for example.
Among them, the content of the polymerizable compound having an ethylenically unsaturated bond-containing group, which is different from the urethane (meth) acrylate (A), in order to improve the balance between high elongation and high wear resistance of the present invention. Is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, with respect to 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 preferable that it is 3 mass parts or less.

  Further, the curable resin composition of the present invention may contain a solvent in order to adjust the viscosity of the composition or to improve the smoothness, uniformity, adhesion to an object to be coated, and the like. . 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, 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 is not particularly limited as long as it is appropriately adjusted according to the purpose, 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 preferable that it is 40 mass parts or more and 70 mass parts or less.

In addition, when the curable resin composition of the present invention is UV curable using ultraviolet rays for curing, the composition of the present invention is rapidly cured. Therefore, the composition of the present invention includes a photopolymerization initiator, a polymerization accelerator, and a photoinitiator assistant. It is recommended to add an agent. Known photopolymerization initiators can be used, and examples thereof include acetophenone compounds, benzoin ether compounds, benzophenone compounds, thioxanthone compounds, and the like. A photoinitiator can be used individually by 1 type or in combination of 2 or more types. 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 optionally contained. .About 1 to 30 parts by mass, preferably about 1 to 5 parts by mass. As a polymerization accelerator and a photoinitiator aid, for example, triethanolamine, methyldiethanolamine, triisopropanolamine and the like can be used. The content ratio of the polymerization accelerator and the photoinitiator assistant is not particularly limited, but is usually about 0.01 to 10 parts by mass, preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the photoinitiator. Or less.
In addition, when setting it as the electron beam sclerosis | hardenability which uses an electron beam for hardening, it is not necessary to add a photoinitiator, a polymerization accelerator, a photoinitiator adjuvant, etc. In this case, the content ratio of the urethane (meth) acrylate (A) and the reactive irregularly shaped inorganic particles (B) in the solid content can be increased, which is preferable from the viewpoint of easily improving wear resistance and tensile elongation.

  The curable resin composition of the present invention may further include, for example, a light stabilizer, an antioxidant, a plasticizer, a flame retardant, a surfactant, a leveling agent, a thermal polymerization inhibitor, an antistatic agent, if necessary. Various additives such as an antifogging agent, an antibacterial agent, a filler, a pigment, a dye, and a colorant can be contained.

  The curable resin composition of the present invention is prepared by blending the urethane (meth) acrylate (A), the reactive irregularly shaped inorganic particles (B), and various additives and solvents as required at a predetermined ratio. Can be obtained by mixing more uniformly.

  The curable resin composition of the present invention can be suitably used for applications such as those 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 this invention is a laminated body provided with the hardened | cured material layer of the said curable resin composition of this invention on the base material.
FIG. 1 is a schematic cross-sectional view showing an example of the laminate of the present invention, and FIG. 2 is a schematic cross-sectional view showing another example of the laminate of the present invention.
As shown in FIG. 1, the laminate 10 of the present invention has a configuration in which a cured product layer 2 of the curable resin composition of the present invention is provided on a substrate 1.
The laminate 10 of the present invention may further include another layer. For example, as shown in FIG. 2, the laminate 10 of the present invention comprises an adhesive layer 3, a primer layer 4, and a cured product layer 2 of the curable resin composition of the present invention in this order on a substrate 1. You may have.
Moreover, although not shown in figure, the laminated body 10 of this invention may equip the base material 1 with the contact bonding layer 3 and the hardened | cured material layer 2 of the said curable resin composition of this invention in this order. Furthermore, 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. Another layer such as a decorative layer can be used by appropriately selecting a known layer.
Hereinafter, the structure of the laminated body of this invention is demonstrated in detail.

<Base material>
The substrate of the laminate is not particularly limited as long as other layers and a cured product of the curable resin composition can be laminated on the substrate. The shape of the substrate is not limited to a sheet shape, and may be a molded body. As the base material, various materials such as plastic, glass, metal, wood, paper and the like can be generally used. Among these, a plastic film is preferable, for example, polyethylene (PE) resin, polypropylene (PP) resin, polybutadiene resin, polyethylene terephthalate (PET) resin, polybutylene terephthalate resin, polyethylene naphthalate (PEN) resin, 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. It is done.
In particular, polycarbonate resin, polymethyl methacrylate resin, ABS resin and the like are suitable when used for various window materials as glass substitutes.

  In addition, the substrate may be subjected to surface treatment 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, Examples include UV ozone treatment and EB treatment.

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

  It does not specifically limit as a method of coating the said curable resin composition on a base material, A well-known method can be applied suitably. 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, air knife coating method, It can be applied by any method such as an offset method or a bar coating method. Moreover, it can also coat like an image by printing methods, such as gravure printing, gravure offset printing, and screen printing.

  The coating amount is not particularly limited as long as it is appropriately selected according to the purpose of the cured product layer. For example, when aiming at a glass substitute, the thickness of the cured layer cured by irradiation with active energy rays is 0.1 μm to 200 μm, preferably 1 μm to 100 μm, more preferably 5 μm to 50 μm. It is preferable to apply the coating as described above.

In order to evaporate the solvent added to the curable resin composition of the present invention as necessary, known drying methods such as hot air heating, infrared heating, far infrared heating and the like can be appropriately employed.
The preferable drying conditions vary depending on the boiling point of the solvent, the material of the base material, the coating amount, and the like, but generally include 30 ° C. or higher and 120 ° C. or lower and 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, usually electron beams extracted from particle accelerators of 20 to 2000 kV, α A line, a beta ray, a gamma ray, etc. 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 is subjected to a Taber abrasion test in accordance with JIS K5600 under the conditions of a wear wheel CS-10F, a load of 500 g, and a rotation speed of 1000 rotations. When measured, ΔH% is preferably less than 5.0%, and 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 pulling speed of 50 mm / min. The elongation when the crack is generated in the layer is measured and the elongation is calculated as described below is preferably 30% or more, more preferably 40% or more, and 50 % Or more is even more preferable.
Elongation = (Elongation length when cracks occur in cured product layer) / (Length of cured product layer before test) × 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 other layers 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 exhibits an adhesive effect can be suitably applied. Specifically, a vinyl chloride resin, a vinyl acetate resin, and a vinyl chloride vinyl acetate are used. Polymerized resins, acrylic resins, polyester resins and the like can be used, but are not limited thereto. Examples of the resin used for the adhesive layer include acrylic resins, vinyl chloride resins, vinyl acetate resins, vinyl vinyl acetate copolymer resins, polyester resins, polyamide resin polyolefin resins, and the like.
The material of the adhesive layer is preferably a material having a melting point of about 50 ° C. or more and 70 ° C. or less which is melt-bonded at a low temperature of about 80 ° C. and solidifies and adheres at about 40 ° C.

  The film thickness of the adhesive layer is not particularly limited, and examples thereof include 0.1 μm or more and 10 μm or less, preferably 1 μm or more and 5 μm or less.

<Primer layer>
A 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.
Examples of the material for the primer layer include, but are not limited to, acrylic resins, urethane resins, vinyl chloride vinyl acetate copolymer resins, polyester resins, and chlorinated polyolefin resins.
Moreover, the primer layer may contain the additive which may be contained in the above-mentioned curable resin composition of this invention.

  Although the film thickness of a primer layer is not specifically limited, For example, 0.1 micrometer or more and 10 micrometers or less are mentioned, Preferably 1 micrometer or more and 5 micrometers or less are mentioned.

Since the laminate of the present invention has a cured product layer of the curable resin composition of the present invention having excellent wear resistance and excellent tensile elongation, the resin base material can be appropriately selected as a base material by inserting It can also be suitably used for molding.
For example, the cured product layer of the curable resin composition of the present invention has a cured product layer of the curable resin composition of the present invention and a decorative layer on the opposite surface of the substrate, and the cured product layer of the curable resin composition of the present invention. A laminate that is laminated in the order of / base material / decorative layer is prepared as an insert molding film, the insert molding film is previously molded into a three-dimensional shape by vacuum molding or the like, and the molding film is injection molded gold After being inserted into the mold, the resin melted by heating in the cavity is injected and filled, and then the mold is opened after cooling, so that the decorative layer / base material / book It can laminate | stack in order of the hardened | cured material layer of the curable resin composition of invention, and can provide a decoration and a surface protective layer.

  In the laminate of the present invention, when the base material is, for example, a synthetic resin molded body, more specifically, for example, glass substitutes for transportation equipment such as automobiles, trains, and airplanes (front glass, rear window, opera window, Triangular windows, sunroofs, etc.), lamps (head lamps, tail lamps, turn indicators, etc.), various meters, dials, bumpers, wheel caps and other vehicle applications, various display applications, refrigerators, Electrical appliances represented by parts such as vacuum cleaners, TVs, coolers, etc., general equipments represented by parts such as computer equipment, printers, copiers, fax machines, optical disks, telephones, and radios, toys, furniture, packaging, Miscellaneous goods such as sports equipment, game machine parts, lighting plate, window glass, window frame, wall material, heat insulating material, flooring material, roofing material, Building materials to civil engineering applications typified by tone plates or the like, glasses, contact lenses, optical device applications typified by a lens such as a camera, etc., medical device applications, general industrial material applications, the nuclear energy applications and the like.

  In the laminate of the present invention, when the base material is, for example, a molded body of wood, more specifically, a wooden building material for exterior, furniture, a floor, a toy and the like can be mentioned.

  Since the laminate of the present invention has excellent flexibility such as tensile elongation, it is suitably used for applications that require tensile elongation at the time of production and use, and further imparts light resistance and weather resistance. Therefore, it can be suitably used for applications directly exposed to ultraviolet rays, sunlight and moisture. The laminate of the present invention is particularly useful in window materials for transportation equipment such as building materials, automobiles, trains, airplanes, lamp covers for traffic lights, carports, soundproof walls, agricultural and industrial films and sheets, automobiles and outer walls, glass coatings, etc. Demonstrate performance.

III. Transfer Laminate The transfer laminate of the present invention is a transfer laminate that is provided with a cured product layer of the curable resin composition of the present invention on a support and is used for transferring at least 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 a cured product layer 2 of the curable resin composition of the present invention is provided on a 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.
Although not shown, the transfer laminate 20 of the present invention may include a cured product layer 2 and an adhesive layer 3 of the curable resin composition of the present invention on the support 11 in this order.
Moreover, although not shown in figure, the laminated body 20 for transfer of this invention is equipped with the release layer, the hardened | cured material layer 2 of the said curable resin composition of this invention, and the contact bonding layer 3 on the support body 11 in this order. May be.
Furthermore, 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. Another layer such as a decorative layer can be used by appropriately selecting a known layer.

Hereinafter, the configuration of the transfer laminate of the present invention will be described in detail.
Of the laminate for transfer 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 the laminate of the present invention. Is omitted.

<Support>
The support for the transfer laminate is not particularly limited as long as it can support at least the transfer of the cured product layer. The shape of the support of the laminate for transfer is usually preferably a sheet or film.
In general, the support is 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, 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.
Among them, 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 subjected to a surface treatment that improves releasability. As such a surface treatment, generally, a release agent is applied. Examples of the release agent include a fluororesin, a silicone resin, and a long-chain alkyl resin compound.

<Release layer>
A release layer may be provided on the support of the transfer laminate at the boundary with the layer used for transfer. The release layer is not particularly limited as long as it is a material having releasability. For example, silicone resin, organic resin-modified silicone resin, fluororesin, aminoalkyd resin, melamine resin, acrylic resin, polyester resin, etc. There is. Although it does not restrict | limit especially as a film thickness of a mold release layer, For example, 0.1 to 10 micrometer is mentioned, Preferably 0.5 to 2 micrometer is mentioned.

The laminate for transfer of the present invention has a cured product layer of the curable resin composition of the present invention that has excellent wear resistance and excellent tensile elongation. Therefore, by appropriately selecting a resin substrate as a support, It can also be suitably used for in-mold transfer.
For example, a transfer laminate is prepared as an in-mold transfer film in which the cured layer of the curable resin composition of the present invention and the decorative layer are laminated in this order on the release-treated surface on the release-treated support. After the in-mold transfer film is inserted into the injection mold so that the support comes into contact with the mold, the molten resin is injected and filled in the cavity and then cooled. By opening the mold, molding and decoration can be performed simultaneously. 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.
The weight average molecular weight is measured by using a GPC HLC-8220 manufactured by Tosoh Corporation as a measuring device, two columns of Shodex LF-404 × are connected in series, and a differential refractive index (RI) detector is standard for the detector. As polystyrene, it was performed using Agilent Technologies PS-2 polystyrene (molecular weight range 580 to 364,000) manufactured by Agilent Technologies.
The obtained urethane acrylate was dissolved in THF so that the sample concentration was 0.2 wt%, the mobile phase was THF, the liquid feed 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 (meth) 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, 26.2 mass of a multimer or more 26.2 mass) %, Weight average molecular weight 1090) 197.3 g, caprolactone-modified 2-hydroxyethyl acrylate (trade name: Plaxel FA1, manufactured by Daicel Corporation, in general formula (a ′), R ^′ = hydrogen atom, R ^″ = ethylene Group, k = 1) 252.7 g, p-methoxyphenol 0.27 g, dibutylhydroxytoluene 1.44 g and toluene 111.0 g were added, mixed and heated to 60 ° C. The equivalent ratio of isocyanate group / hydroxyl group is 1.0, and after stabilizing the internal temperature at 60 ° C., dioctyltin dineo 1.63 g of a 10-fold diluted solution of canoate in toluene was added, and after the exotherm due to the addition of dioctyltin dineodecanoate was stabilized, the temperature was maintained at 90 ° C. and reacted for 4 hours, and then JIS K 7301 The method confirmed that the isocyanate group content was 0.1% or less, and obtained 552.6 g of urethane (meth) acrylate 1. The weight average molecular weight of the obtained urethane (meth) acrylate 1 was 2940. It was.

(Synthesis Example 2: Production of Urethane (Meth) 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: Plaxel FA1), caprolactone-modified 2-hydroxyethyl acrylate (trade name: Plaxel FA2D, ( Urethane (meth) as in Synthesis Example 1 except that 295.6 g of R ^′ = hydrogen atom, R ^″ = ethylene group, k = 2) in the general formula (a ′) manufactured by Daicel Corporation was used. 554.3 g of acrylate 2 was obtained, and the urethane (meth) acrylate 2 obtained had a weight average molecular weight of 3700.

(Synthesis Example 3: Production of Urethane (Meth) 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: Plaxel FA1), caprolactone-modified 2-hydroxyethyl acrylate (trade name: Plaxel) FA1) 549.8 g of urethane (meth) acrylate 3 in the same manner as in Synthesis Example 1 except that 146.7 g of 2-hydroxyethyl acrylate and 74.1 g of 2-hydroxyethyl acrylate were used and the caprolactone modification number k was 0.5. Obtained. The resulting urethane (meth) acrylate 3 had a weight average molecular weight of 1970.

(Synthesis Example 4: Production of Urethane (Meth) acrylate 4>
In Synthesis Example 1, hexamethylene was used instead of polyisocyanate containing an isocyanurate ring derived from hexamethylene diisocyanate (trade name: Coronate HXLV, pentamer or higher multimer 26.2% by mass, weight average molecular weight 1090). A polyisocyanate containing an isocyanurate ring derived from diisocyanate (trade name: Coronate HK, pentamer or higher polymer 64.1% by mass, weight average molecular weight 2330) 213.7 g was used, and the amount of Plaxel 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 amount was changed to 3 g. The urethane (meth) acrylate 4 obtained had a weight average molecular weight of 6,150.

(Synthesis Example 5: Production of urethane (meth) 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: Plaxel FA1), caprolactone-modified 2-hydroxyethyl acrylate (trade name: Plaxel FA2D, ( Urethane (meta) in the same manner as in Synthesis Example 4 except that 280.4 g of R ^′ = hydrogen atom, R ^″ = ethylene group, k = 2) in the general formula (a ′) manufactured by Daicel Corporation was used. 545.0 g of acrylate 5 was obtained, and the urethane (meth) acrylate 5 obtained had a weight average molecular weight of 7650.

(Synthesis Example 6: Production of urethane (meth) acrylate 6 (comparative compound)>
In Synthesis Example 1, instead of a polyisocyanate containing an isocyanurate ring derived from hexamethylene diisocyanate (trade name: Coronate HXLV), a polyisocyanate containing an isocyanurate ring derived from hexamethylene diisocyanate (trade name: Coronate HXR) 154.8 g of a polymer of 47.6% by mass of a pentamer or higher, and a weight average molecular weight of 1540) were used, and instead of caprolactone-modified 2-hydroxyethyl acrylate (trade name: Plaxel FA1), polyethylene glycol monoacrylate ( Urethane (meth) acrylate 6 was prepared in the same manner as in Synthesis Example 1 except that 295.1 g of a trade name: Blemmer AE-200, manufactured by NOF Corporation, EO average repeating unit number n = 4.5) was used. 543.6 g was obtained. The obtained urethane (meth) acrylate 6 had a weight average molecular weight of 10,640.

(Synthesis Example 7: Synthesis of bisbenzotriazolylphenol compound 1 represented by the general formula (1))
Under a nitrogen atmosphere, 2,2′-methylene-bis [6- (2H-benzotriazol-2-yl) -4- (2-hydroxyethyl) phenol] (RUVA-100: manufactured by Otsuka Chemical)
To 72.5 g (140 mmol), 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) were added, and the reaction temperature was adjusted. By keeping the reaction at 150 ° C. for 6 hours, caprolactone-modified 2,2′-methylene-bis [6- (2H-benzotriazol-2-yl) -4- (2) represented by the following chemical formula (A) -Hydroxyethyl) phenol] (m + n = 3) was obtained.

  86. Caprolactone-modified 2,2′-methylene-bis [6- (2H-benzotriazol-2-yl) -4- (2-hydroxyethyl) phenol] represented by the chemical formula (A) (m + n = 3) 27.5 g (195 mmol) of 2-isocyanatoethyl acrylate (Karenzu AOI: manufactured by Showa Denko), 47.9 g of ethyl acetate and 0.044 g of p-methoxyphenol were mixed with 5 g (98 mmol), and the temperature was raised to 60 ° C. 0.95 g (0.046 mmol) of dioctyltin neodecanoate (Neostan U-830: manufactured by Nitto Kasei) diluted with ethyl acetate 30 times and reacted at 75 ° C. for 4 hours, is represented by the following chemical formula (B). The desired 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, N-H), 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 1: 22.4 parts by mass of Synthesis Example 1-Component (B); Silica 1 (trade name: V-8803, manufactured by JGC Catalysts & Chemicals, average primary particle size of 10 nm to (2) Reactive silica particles having an ethylenically unsaturated bond-containing group on the surface, 2 to 15 approximately spherical silica particles having a size of 100 nm are aggregated, average particle diameter 25 nm, solid content 40%): 65.63 mass UVA1 (trade name: TINUVIN479, manufactured by BASF): 0.4 parts by weight UV absorber; UVA2 (trade name: TINUVIN400, manufactured by BASF): 0.4 parts by weight, light stabilizer; HALS1 ( Product name: TINUVIN123, manufactured by BASF): 0.2 parts by mass / leveling agent; Leveling agent 1 (product name: tegrad-2100, manufactured by Evonik): 0.5 mass Parts / solvent; MEK (methyl ethyl ketone): 10.77 parts by mass

(2) Manufacture of laminated body On the easy-adhesion PET film (Toyobo Cosmo Shine A4100) with a thickness of 100 μm, the curable resin composition 1 is applied and dried so that the film thickness after drying becomes 5 μm. 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 2-9, Comparative Examples 1-4)
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 blending components and blending ratios to be used were changed, and a laminate was obtained.

In addition, the abbreviation of each component of Table 2 is 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 (functional group number k = 1); Synthesis Example 4
Polyfunctional urethane (meth) acrylate 5 (functional group number k = 2); Synthesis Example 5
Polyfunctional urethane (meth) acrylate 6; Synthesis example 6 (comparative compound)
・ Polyfunctional urethane (meth) acrylate 7; Product name: Purple light UV75550B, 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 Toa Gosei, ε-caprolactone modified tris (acryloxyethyl) isocyanurate (comparative compound)
-Bifunctional (meth) acrylate 1; urethane acrylate oligomer, trade name Aronix M-1200, manufactured by Toa Gosei (Comparative compound)
Silica 2; (trade name: MIBK-AC-2140Z, manufactured by Nissan Chemical Co., 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 tabered 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% in 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 of 5 cm between chucks. A tensile test was performed at a speed of 50 mm / min. The length of elongation when cracks occurred in the cured product layer was measured, and the elongation was determined and evaluated as follows.
Elongation = (Elongation length when cracks occur in cured product layer) / (Length of cured product layer before test) × 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 super UV weather resistance tester (Iwasaki Electric Co., Ltd. Eye Super UV Tester SUV-W161, illuminance 100 mW / cm ² ) The degree of discoloration of the base material (PET film) when it was put into step ² ) was evaluated. In the super UV weather resistance tester, after 20 hours of ultraviolet irradiation, water was sprayed (shower) for 30 seconds, and the weather resistance test was performed with 4-hour condensation as one cycle.
<Evaluation criteria>
A: No change in color of substrate (PET film) even after 200-hour weather resistance test: No change after 100-hour weather resistance test, but discoloration of substrate (PET film) after 200-hour weather resistance test Δ: 100-hour weather resistance After the test, there was discoloration of the base material (PET film) x: After the weather resistance test for 100 hours, there was discoloration of the base material (PET film), and further cracking of the base material was 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 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, and an average primary particle size of 10 nm The curable resin composition of the present invention comprising 2 to 20 approximately spherical inorganic particles having a size of ˜100 nm connected and aggregated, and a combination of reactive irregularly shaped inorganic particles (B) having an ethylenically unsaturated bond-containing group on the surface. It was clarified that Examples 1 to 9 using the product can obtain a cured product having high wear resistance and excellent tensile elongation.
Among the examples, when polyisocyanate contains a large number of multimers of pentamer or more and urethane (meth) acrylate (A) having a large number of functional groups in one molecule is used, the cured product has chemical resistance. It was revealed that it improved. It was also clarified that the chemical resistance of the cured product is improved even when the ε-caprolactone adduct of the hydroxyalkyl (meth) acrylate is 0.5 mol on average. All of these are presumed to be due to an increase in the crosslinking density.
Further, it has been clarified that when the bisbenzotriazolylphenol compound represented by the general formula (1) is used in combination as an ultraviolet absorber, the weather resistance is particularly improved.

On the other hand, it was revealed that the curable resin composition of Comparative Example 1 corresponding to the curable resin composition of Patent Document 2 was particularly inferior in wear resistance and in elongation. 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 a caprolactone chain is particularly inferior in wear resistance. When ethylene oxide chains were included, the elongation was good but the weather resistance and chemical resistance were inferior.
Further, from Comparative Example 3, when urethane (meth) acrylate containing an isocyanurate ring having no caprolactone chain is used, it is inferior in wear resistance even in combination with the reactive irregularly shaped inorganic particles (B) used in the present invention. It was also revealed that the elongation was insufficient.
Moreover, although the curable resin composition of Comparative Example 4 corresponding to the curable resin composition of Patent Document 1 has good elongation, it is clearly inferior in abrasion resistance and weather resistance and chemical resistance. It was done.

Claims (9)

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;
A 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 to 5, 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 in which j is 5 among the compounds represented by the general formula (a ′). The curable resin composition according to claim 1, which is a product.   The curable resin composition according to any one of claims 1 to 3, wherein the urethane (meth) acrylate (A) includes a pentamer or more polymer as the polyisocyanate containing the isocyanurate ring.   In the said urethane (meth) acrylate (A), in the compound represented by the said general formula (a '), k is 0.4 or more and 0.7 or less, Any one of Claims 1-4. Curable resin composition.   Furthermore, the curable resin composition of any one of Claims 1-5 containing a bisbenzotriazolyl phenol compound. Furthermore, the curable resin composition of any one of Claims 1-6 containing the bisbenzotriazolyl phenol compound represented by following General formula (1).
(In 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 represent 1 or more carbon atoms. 6 or less linear or branched aliphatic hydrocarbon groups, R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, R ⁷ and R ⁸ each independently represent a hydrogen atom, a halogen atom, or Represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms, n and m are each independently a number of 1 to 10 and n + m = 2 to 20; p and q are each independently 3 The number is from 5 to 5. r and s are each independently from 1 to 2.   The laminated body provided with the hardened | cured material layer of the curable resin composition of any one of the said Claims 1-7 on the base material.   A laminate for transfer, which comprises at least a transfer of the cured product layer, comprising a cured product layer of the curable resin composition according to any one of claims 1 to 7 on a support.