WO2018174102A1 - Curable composition for sheets, cured product and method for producing same, sheet for three-dimensional shaping, optical member, lenticular sheet and three-dimensional structure - Google Patents

Abstract

One embodiment of the present invention provides: a curable composition for sheets to be used for three-dimensional shaping, which contains a polymerizable compound that comprises a polymerizable group and a functional group containing a nitrogen atom, while having a molecular weight of 300 or less, a polyfunctional monomer other than the polymerizable compound, said monomer comprising two or more (meth)acryloyl groups, and a radical photopolymerization initiator, and which does not contain a urethane (meth)acrylate compound or contains a urethane (meth)acrylate compound in an amount of more than 0% by mass but less than 4% by mass relative to the total mass of this curable composition for sheets; and applications of this curable composition for sheets.

Description

Curable composition for sheet, cured product and production method thereof, three-dimensional molding sheet, optical member, lenticular sheet, and three-dimensional structure

The present disclosure relates to a curable composition for a sheet, a cured product and a method for producing the same, a sheet for three-dimensional molding, an optical member, a lenticular sheet, and a three-dimensional structure.

Conventionally, a curable composition contains a polymerizable resin and an initiator, is cured by causing a polymerization reaction by heat or light, and is widely used in various applications. Moreover, the laminated sheet which laminated | stacked the hardened | cured material obtained by hardening | curing a curable composition is utilized widely, such as an optical member, a gas barrier film, a protective film, an optical filter, an antireflection film.
Furthermore, the cured product obtained by curing the curable composition is used for various members such as an antireflection film, a transparent pixel, a transparent insulating film, and a planarization film.

In recent years, there are a wide variety of optical members, and the optical structure of the optical member is not limited to a flat surface shape, for example, and is used for a brightness enhancement lens and a diffusion lens of a liquid crystal backlight, and a screen of a video projection television. Examples include Fresnel lenses and micro lenses. In such a device, a desired geometrical optical performance is obtained mainly by forming a fine structure with a resin material.

As an optical structure, a lenticular sheet using a lenticular lens in which convex lenses having a semicylindrical surface are arranged in parallel is known as a medium for displaying different images depending on viewing angles.
In a lenticular sheet, generally, an image sequence group (lenticular image) in which a plurality of interlaced images are combined is arranged on the back side of the lenticular lens (the surface opposite to the semi-cylindrical surface of the convex lens). When the row group is observed through a lenticular lens, one or more images in the image row group can be displayed depending on the viewing angle.

Therefore, optical materials and optical screens are expected to be used for various commercial purposes. However, the applications proposed heretofore are mostly used in a two-dimensional form such as a sheet or a film, and are not often applied to a three-dimensional form formed into a three-dimensional shape.

As a technique that has been attempted to be applied to a three-dimensional form, for example, an ultraviolet curable resin composition for Fresnel lenses containing ethylene dimethacrylate, tetrahydrofurfuryl methacrylate, and a polymerization initiator is applied to a mold and irradiated with ultraviolet rays. A technique for producing a Fresnel lens that is taken out of a mold and has excellent adhesion to a substrate has been described (see, for example, JP-A-08-165316).
In addition, an ultraviolet curable composition for an optical sheet containing phenoxyethyl acrylate, neopentyl glycol-modified trimethylolpropane diacrylate, and a radical polymerization initiator is supplied to a prism mold, and after being irradiated with ultraviolet rays, peeled from the mold, A technique for producing a prism sheet excellent in adhesion to a substrate as an optical sheet has been disclosed (see, for example, JP-A-2001-226418).

On the other hand, a composition containing a polymerizable unsaturated group-containing monomer having no hydroxyl group, urethane acrylate, and a conductive material amount is disclosed as a photo-curable resin composition having excellent adhesion to a resin film (for example, a special feature) No. 2016-74884). Further, as an example of applying a curable composition in film applications, there is a disclosure relating to a technique for imparting hard coat properties by a composition containing polyfunctional acrylates, silica particles, high molecular weight monomers, etc. No. 287308).

However, in recent years, application to a three-dimensional shape molded into a three-dimensional shape is expected as a usage mode of an optical material and an optical screen. For example, a sheet on which a cured product of a curable composition is arranged, etc. When three-dimensionalization is realized by a method such as molding, it is required that the cured product has excellent adhesion to the substrate and excellent rub resistance after stretching.
Among the prior arts, Japanese Patent Application Laid-Open Nos. 08-165316 and 2001-226418 indicate that the produced Fresnel lens or prism sheet is excellent in adhesion to the base material. It is not obtained, and is inferior in terms of abrasion resistance after stretching.
In addition, the photocurable resin composition described in Japanese Patent Application Laid-Open No. 2016-74884 contains a relatively high molecular weight urethane compound, so that the hardness cannot be secured, and as a result, there is a problem with the abrasion resistance after stretching. . Furthermore, the composition described in Japanese Patent Application Laid-Open No. 2001-287308 has poor adhesion to the substrate even if high hardness is obtained, and as a result, it is easily peeled off by stretching, and the rub resistance after stretching cannot be ensured.

The problem to be solved by one embodiment of the present invention is to provide a curable composition for a sheet that is excellent in adhesion of the resulting cured product to a substrate and excellent in abrasion resistance after stretching.
Other embodiment of this invention is providing the hardened | cured material excellent in the adhesiveness to a base material, and extending | stretching abrasion resistance, and its manufacturing method.
Another embodiment of the present invention is to provide a three-dimensional molding sheet, a lenticular sheet, an optical member, and a three-dimensional structure having a cured product excellent in adhesion to a base material and stretch rub resistance.

In the present disclosure, the stretch rub resistance means scratch resistance after stretching a cured product of the curable composition (hereinafter also referred to as “rubbing resistance after stretching”).
In the present disclosure, adhesion to a substrate (hereinafter, also referred to as “substrate adhesion”) refers to the difficulty of peeling a cured product obtained by curing the curable composition to the substrate, and resistance to tape peeling. Refers to the adhesion evaluated by The base material adhesion in the present disclosure is further evaluated by bending resistance that does not peel off the cured product when the sheet is bent and bent by 180 ° when a sheet having a cured product obtained by curing the curable composition is produced. It is preferable to indicate the adhesiveness.

Means for solving the above problems include the following aspects.
<1> A functional compound containing a nitrogen atom and a polymerizable group, a polymerizable compound having a molecular weight of 300 or less, a polyfunctional monomer having two or more (meth) acryloyl groups other than the polymerizable compound, and light A radical polymerization initiator,
Three-dimensional molding which does not contain a urethane (meth) acrylate compound, or the content of the urethane (meth) acrylate compound is more than 0% by mass and less than 4% by mass with respect to the total mass of the curable composition for sheets. It is a curable composition for sheet | seats used for.

<2> The curable composition for sheets according to <1>, wherein the polymerizable compound is a compound represented by the following general formula (I) or the following general formula (II).

 

In the general formula (I), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ³ and R ⁴ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. X ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. R ¹ , R ² , R ³ , R ⁴ and X ¹ may be the same or different and may form a ring with each other.

 

In the general formula (II), R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ⁷ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. X ² represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. At least one of R ⁵ , R ⁶ and R ⁷ contains a nitrogen atom bonded to a carbon atom of the hydrocarbon group. X ² , R ⁵ , R ⁶ and R ⁷ may be the same or different and may form a ring with each other.

<3> The polymerizable compound is a sheet curability according to <1> or <2>, wherein the polar value component (δp) of the SP value is in the range of 5 MPa ^(1/2) to 15 MPa ^(1/2) . It is a composition.
<4> The content of the polymerizable compound is 15% by mass to 50% by mass with respect to the solid content of the curable composition for sheets, and the content for a sheet according to any one of <1> to <3> It is a curable composition.
<5> The polyfunctional monomer according to any one of <1> to <4>, wherein the polyfunctional monomer is at least one polyfunctional monomer selected from the group consisting of a bifunctional monomer, a trifunctional monomer, and a tetrafunctional monomer. It is a curable composition for sheets.
<6> A cured product obtained by curing the curable composition for sheets according to any one of <1> to <5>.

<7> A step of preparing the curable composition for a sheet according to any one of <1> to <5>, and a step of curing the curable composition for a sheet by irradiation with active energy rays. It is a manufacturing method of hardened | cured material.
<8> A sheet for three-dimensional molding having a cured product of the curable composition for a sheet according to any one of <1> to <5>.
<9> An optical member having a cured product of the curable composition for sheets according to any one of <1> to <5>.
<10> A lenticular sheet having a cured product of the curable composition for a sheet according to any one of <1> to <5>.
<11> A three-dimensional structure which is a three-dimensional molded product of the solid molding sheet according to <8> or the lenticular sheet according to <10>.

According to one embodiment of the present invention, there is provided a curable composition for a sheet that is excellent in adhesion of the obtained cured product to a substrate and stretch rub resistance.
According to other embodiment of this invention, the hardened | cured material excellent in the adhesiveness to a base material and extending | stretching abrasion resistance, and its manufacturing method are provided.
According to another embodiment of the present invention, there are provided a three-dimensional molding sheet, a lenticular sheet, an optical member, and a three-dimensional structure having a cured product excellent in adhesion to a substrate and stretch rub resistance.

It is the schematic which shows an example of the display body provided with the lenticular sheet.

Hereinafter, the curable composition for sheets, the cured product and the production method thereof, the three-dimensional molding sheet, the optical member, the lenticular sheet, and the three-dimensional structure will be described in detail.

In this specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value. In a numerical range described in stages in the present disclosure, an upper limit value or a lower limit value described in a numerical range may be replaced with an upper limit value or a lower limit value in another numerical range. Further, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the values shown in the examples.

The term “process” in the present specification is not limited to an independent process, and is included in this term if the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes. .

In this specification, “(meth) acryl” is a term used in a concept including both acryl and methacryl, and “(meth) acryloyl” is a term used as a concept including both acryloyl and methacryloyl. It is.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure are TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation) unless otherwise specified. The molecular weight is detected by a gel permeation chromatography (GPC) analyzer with a solvent THF (tetrahydrofuran) and a differential refractometer and converted using polystyrene as a standard substance.

<Curable composition for sheet>
The curable composition for a sheet of the present disclosure is a curable composition applied to the production of a sheet used for three-dimensional molding. The curable composition for a sheet of the present disclosure includes a functional group containing a nitrogen atom and a polymerizable group, a polymerizable compound having a molecular weight of 300 or less, and two or more (meth) acryloyl groups other than the polymerizable compound. A polyfunctional monomer having a radical photopolymerization initiator and no urethane (meth) acrylate compound, or the urethane (meth) acrylate compound content of the curable composition for sheets It is set as the range exceeding 0 mass% and less than 4 mass% with respect to the total mass.
The curable composition for sheets of the present disclosure may contain other components other than the urethane (meth) acrylate compound as necessary.

Conventionally, the use of optical materials, optical screens, and the like has been mainly used in a two-dimensional form such as a sheet shape, but in recent years, application to a three-dimensional form formed into a three-dimensional shape is expected. Has been. In order to realize the three-dimensionalization, for example, a method in which a sheet or the like on which a cured product of the curable composition is arranged is placed in a mold and molded.
However, when molding a sheet having a cured product that is already cured, if the adhesion of the cured product to the substrate is insufficient, the cured product is peeled off from the substrate and the desired three-dimensional molded product. Cannot be obtained. In addition, even when the cured product does not peel from the base material at the time of molding, if the cured product is poorly adhered to the base material, the cured product easily peels off when the three-dimensional molded product is subjected to a rubbing force from the outside. The quality of the molded product will be significantly impaired.
In this regard, in Japanese Patent Application Laid-Open Nos. 08-165316 and 2001-226418, even if the produced Fresnel lens or prism sheet has a certain degree of adhesion to the substrate, the adhesion required for three-dimensional molding is required. Therefore, improvement in the abrasion resistance after drawing is also required. On the other hand, as disclosed in JP-A-2016-74884, a photocurable resin composition containing a relatively high molecular weight urethane compound is inferior in abrasion resistance after stretching because the hardness cannot be ensured. Further, in the composition described in JP-A-2001-287308, high hardness is expected, but the adhesion to the substrate is poor, and therefore it is easy to peel off by stretching, and it is possible to ensure the rub resistance after stretching. Can not.

The present disclosure has been made in view of the above, and includes a relatively low molecular weight (molecular weight 300 or less) polymerizable compound having a functional group containing a nitrogen atom, and a bifunctional or higher (meth) acrylic monomer, And it is set as the composition which does not contain a urethane (meth) acrylate compound or contains only in a small range. As a result, the cured product obtained by curing the curable composition for sheets has a nitrogen atom, so that it interacts with the substrate, contributes to improving the adhesion of the cured product to the substrate, and further has a hardness. The adhesiveness of hardened | cured material is further improved because it is high and the content rate of a urethane (meth) acrylate compound is small. As a result, the adhesion to the substrate (substrate adhesion) is improved, and the rub resistance after stretching (stretch rub resistance) is drastically improved.
That is, the curable composition for a sheet of the present disclosure is compatible with substrate adhesion and stretch rub resistance. Moreover, the curable composition for sheet | seats of this indication is excellent also in hardness, while being excellent in base-material adhesiveness and extending | stretching abrasion resistance.

-(A) a polymerizable compound having a functional group containing a nitrogen atom and having a molecular weight of 300 or less-
The curable composition for a sheet of the present disclosure contains at least one of a polymerizable compound having a functional group containing a nitrogen atom and a polymerizable group and having a molecular weight of 300 or less (hereinafter also referred to as a specific polymerizable compound). .

Since the specific polymerizable compound has a polymerizable group, a polymer is formed by an addition polymerization reaction between the specific polymerizable compounds and an addition polymerization reaction with a “polyfunctional monomer having two or more (meth) acryloyl groups” described later. To form a cured product having a functional group containing a nitrogen atom bonded thereto. Thereby, when the hardened | cured material which the curable composition for sheets hardened | cured has a nitrogen atom, it interacts between base materials and contributes to the improvement of the adhesiveness to the base material of hardened | cured material. In this regard, it is considered that a compound containing a nitrogen atom in the molecule has a stronger interaction with the substrate than a compound containing an oxygen atom in the molecule, for example.

Here, the “polymerizable group” is preferably a group having an ethylenically unsaturated double bond.
The “functional group containing a nitrogen atom” is not particularly limited as long as it is a group containing a nitrogen atom. For example, an amino group, an amide group, an imino group, a cyano group, etc., and an imidazole ring group or an imidazoline ring. And heterocyclic groups such as a group, a pyrrolidine ring group, a pyrazole ring group, a morpholine ring group, and a triazine ring group.

Moreover, since there exists a tendency for the adhesiveness to a base material to fall when the molecular weight of a specific polymerizable compound becomes large, the molecular weight of the specific polymerizable compound of this indication is 300 or less. When the molecular weight is 300 or less, the curable composition for sheets can form a cured product having excellent adhesion to the substrate. By being excellent in adhesion, the rub resistance after subsequent stretching is also improved.
The molecular weight of the specific polymerizable compound is preferably 250 or less, more preferably 150 or less, and still more preferably 100 or less, from the same viewpoint as described above. The lower limit of the molecular weight of the specific polymerizable compound is not particularly limited, but is preferably 50 or more.
The molecular weight of the specific polymerizable compound is determined by arithmetic calculation from the chemical formula.

The specific polymerizable compound preferably has a SP value polar term component (δp ^{) in} the range of 5 MPa ^(1/2) to 15 MPa ^(1/2) . When the δp of the polymerizable compound is close to the δp of the base material, excellent adhesion is exhibited. In this case, the substrate is preferably a resin substrate having a δp of 5 MPa ^(1/2) to 15 MPa ^(1/2) . Details of the resin substrate will be described later. When the substrate is, for example, polymethyl methacrylate (PMMA), since the δp of PMMA is 10.5 MPa ^(1/2) , the effect of improving the adhesion of the cured product to the substrate by including the specific polymerizable compound is effective. high.
The δp of the specific polymerizable ^compound, preferably ^{7MPa (1/2) ~ 13MPa (1/2} ) ^{is, 10.5MPa (1/2) ~ 11MPa (} 1/2) is more preferable.
The polar term component (δp) of the SP value is a value calculated by the Hansen solubility parameter. The Hansen solubility parameter is composed of intermolecular dispersion energy (δd), intermolecular polarity energy (δp), and intermolecular hydrogen bonding energy (δh). For the calculation, HSPiP (version 4.1.07) software is used.

Favorable examples of the specific polymerizable compound include compounds represented by the following general formula (I) or general formula (II). Among the specific polymerizable compounds, when the compound represented by the general formula (I) or the general formula (II) is contained, the effect of improving the adhesion of the cured product to the substrate and the rub resistance after stretching is large, and the hardness The improvement effect is also high.

 

In the general formula (I), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent. R ³ and R ⁴ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. X ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms which may have a substituent. R ¹ , R ² , R ³ , R ⁴ and X ¹ may be the same or different and may form a ring with each other.

Examples of the hydrocarbon group having 1 to 6 carbon atoms which may have a substituent in R ¹ and R ² include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. . Among these, a hydrocarbon group having 1 to 4 carbon atoms is preferable, and a hydrocarbon group having 1 to 2 carbon atoms is more preferable. As the hydrocarbon group, an alkyl group is preferable.
Among the above, R ¹ and R ² are each independently preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and more preferably a hydrogen atom.
Examples of the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent in R ³ and R ⁴ include alkyl groups such as a methyl group, an ethyl group, an isopropyl group, a t-butyl group, and a hexyl group. And cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group. R ³ and R ⁴ may be bonded to each other to form a ring. The ring formed by combining R ³ and R ⁴ is preferably a saturated heterocyclic ring.

Examples of the substituent that the hydrocarbon group may have include groups in the substituent group T shown below.
(Substituent group T)
An alkyl group (preferably having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, particularly preferably 1 to 6 carbon atoms such as methyl group, ethyl group, isopropyl group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl, cyclohexyl group, etc.), alkenyl group (preferably having 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, particularly preferably 2 to 6 carbon atoms). For example, a vinyl group, an allyl group, a 2-butenyl group, a 3-pentenyl group, etc.), an alkynyl group (preferably having 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, particularly preferably 2 to 8 carbon atoms). 6 such as propargyl group and 3-pentynyl group), aryl group (preferably having 6 to 20 carbon atoms, more preferably To 15 and particularly preferably 6 to 12, for example, phenyl group, biphenyl group, naphthyl group, etc.), amino group (preferably having 0 to 15 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6, for example, amino group, methylamino group, dimethylamino group, diethylamino group, dibenzylamino group, etc.), alkoxy group (preferably having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms) Particularly preferably 1 to 6, for example, methoxy group, ethoxy group, butoxy group, etc.), aryloxy group (preferably having 6 to 20 carbon atoms, more preferably 6 to 15 and particularly preferably 6). To 12 such as phenyloxy group and 2-naphthyloxy group), acyl group (preferably having 1 to 15 carbon atoms) More preferably, it is 1 to 10, particularly preferably 1 to 8, and examples thereof include an acetyl group, a benzoyl group, a formyl group, a pivaloyl group, etc.), an alkoxycarbonyl group (preferably having 2 to 15 carbon atoms, more preferably Is 2 to 10, particularly preferably 2 to 8, and examples thereof include a methoxycarbonyl group and an ethoxycarbonyl group.), An aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16, Particularly preferred is 7 to 10, for example, a phenyloxycarbonyl group, etc.), an acyloxy group (preferably having 2 to 15 carbon atoms, more preferably 2 to 10 and particularly preferably 2 to 8; An acetoxy group, a benzoyloxy group, etc.), an acylamino group (preferably the number of carbon atoms) It is 2 to 15, more preferably 2 to 10, particularly preferably 2 to 8, and examples thereof include an acetylamino group and a benzoylamino group. ),

An alkoxycarbonylamino group (preferably having 2 to 15 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably 2 to 8 carbon atoms such as a methoxycarbonylamino group), an aryloxycarbonylamino group (preferably 7 to 15 carbon atoms, more preferably 7 to 13 carbon atoms, particularly preferably 7 to 10 carbon atoms such as a phenyloxycarbonylamino group), sulfonylamino groups (preferably 1 to 15 carbon atoms, more Preferably, it is 1 to 10, particularly preferably 1 to 8, and examples thereof include methanesulfonylamino group, benzenesulfonylamino group, etc.), sulfamoyl group (preferably having 0 to 15 carbon atoms, more preferably 0 to 10 carbon atoms). And particularly preferably 0 to 8, such as sulfamoyl group, methylsulfamo Group, dimethylsulfamoyl group, phenylsulfamoyl group, etc.), carbamoyl group (preferably having 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 8 carbon atoms. A carbamoyl group, a methylcarbamoyl group, a diethylcarbamoyl group, a phenylcarbamoyl group, etc.), an alkylthio group (preferably having 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 8 carbon atoms. Methylthio group, ethylthio group and the like), arylthio group (preferably having 6 to 20, more preferably 6 to 15 and particularly preferably 6 to 12 carbon atoms, such as phenylthio group). A sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably -12, such as a mesyl group, a tosyl group, etc.), a sulfinyl group (preferably having a carbon atom number of 1-20, more preferably 1-16, particularly preferably 1-12, such as a methanesulfinyl group). , Benzenesulfinyl groups, etc.), ureido groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms such as ureido group, methylureido group, phenylureido group). Phosphoric acid amide groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms such as diethyl phosphoric acid amide and phenylphosphoric acid amide). Hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom) , A cyano group, a sulfo group, a carboxyl group, a nitro group, a sulfino group, a hydrazino group, an imino group, a heterocyclic group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, Nitrogen atom, oxygen atom, sulfur atom, specifically, imidazolyl group, pyridyl group, quinolyl group, furyl group, piperidyl group, morpholino group, benzoxazolyl group, benzimidazolyl group, benzthiazolyl group and the like can be mentioned. ).

R ³ and R ⁴ are preferably a hydrocarbon group having 1 to 15 carbon atoms, more preferably a hydrocarbon group having 1 to 10 carbon atoms, and still more preferably a hydrocarbon group having 1 to 6 carbon atoms. As the hydrocarbon group, an alkyl group is preferable. Examples of the saturated heterocyclic ring include a pyrrolidine ring, a piperidine ring, and a morpholine ring.
Among the above, R ³ and R ⁴ are each independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and R ³ and R ⁴ are bonded to each other. Also preferred are morpholine rings formed in this manner.
Examples of the hydrocarbon group having 1 to 5 carbon atoms that may have a substituent in X ¹ include alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group. Among these, a hydrocarbon group having 1 to 4 carbon atoms is preferable, and a hydrocarbon group having 1 to 2 carbon atoms is more preferable. As the hydrocarbon group, an alkyl group is preferable. Examples of the substituent that the hydrocarbon group may have include the group in the substituent group T described above.
Among the above, X ¹ is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.

 

In the general formula (II), R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent. R ⁷ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. X ² represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms which may have a substituent. At least one of R ⁵ , R ⁶ and R ⁷ contains a nitrogen atom bonded to a carbon atom of the hydrocarbon group. X ² , R ⁵ , R ⁶ and R ⁷ may be the same or different and may form a ring with each other.

Examples of the hydrocarbon group having 1 to 6 carbon atoms which may have a substituent in R ⁵ and R ⁶ include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. . Among these, a hydrocarbon group having 1 to 4 carbon atoms is preferable, and a hydrocarbon group having 1 to 2 carbon atoms is more preferable. As the hydrocarbon group, an alkyl group is preferable.
Among the above, R ⁵ and R ⁶ are preferably each independently a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.
Examples of the hydrocarbon group having 1 to 20 carbon atoms that may have a substituent in R ⁷ include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. . Among them, R ⁷ is preferably a hydrocarbon group having 1 to 15 carbon atoms, more preferably a hydrocarbon group having 1 to 10 carbon atoms. As the hydrocarbon group, an alkyl group is preferable.
Among the above, R ⁷ is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
Examples of the substituent that the hydrocarbon group may have include the group in the substituent group T described above.

Here, at least one of R ⁵ , R ⁶ and R ⁷ is a group containing a nitrogen atom, and at least one of R ⁵ , R ⁶ and R ⁷ is a hydrocarbon group substituted with a nitrogen-containing group, Or a cyano group is preferable. The hydrocarbon group substituted with a nitrogen-containing group is preferably an alkyl group having 1 to 10 carbon atoms substituted with a nitrogen-containing group.
Preferred examples of the hydrocarbon group substituted with a nitrogen-containing group in R ⁵ , R ⁶ and R ⁷ include —C _n H _2n NR ¹¹ R ¹² . R ¹¹ and R ¹² each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or —COOR ¹³ , and R ¹³ represents an alkyl group having 1 to 4 carbon atoms. R ¹¹ and R ¹² may be bonded to each other to form a ring. Examples of the alkyl group having 1 to 4 carbon atoms in R ¹¹ , R ¹² and R ¹³ include a methyl group, an ethyl group, an isopropyl group and a t-butyl group.
Examples of the alkyl group having 1 to 10 carbon atoms substituted with a nitrogen-containing group include 1-cyanoethyl group, cyanomethyl group, N, N-dimethylaminoethyl group, methoxycarbonylaminoethyl group and the like.
Examples of the hydrocarbon group having 1 to 5 carbon atoms that may have a substituent in X ² include alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group. A hydrocarbon group having 4 to 4 carbon atoms is preferable, and a hydrocarbon group having 1 to 2 carbon atoms is more preferable. As the hydrocarbon group, an alkyl group is preferable.
Among the above, X ² is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.

Specific examples of the specific polymerizable compound of the present disclosure are shown below. However, the specific polymerizable compound in the present disclosure is not limited to the following specific examples.

 

 

 

The content of the specific polymerizable compound in the curable composition for sheets is preferably in the range of 15% by mass to 50% by mass with respect to the solid content of the curable composition for sheets. When the content of the specific polymerizable compound is 15% by mass or more, the substrate adhesion and the stretch rub resistance are excellent. Further, when the content of the specific polymerizable compound is 50% by mass or less, the shape retention of the cured product is more stably imparted, and it is suitable for avoiding crushing of the three-dimensional portion.
Among them, the content of the specific polymerizable compound is more preferably 20% by mass to 50% by mass, and more preferably 25% by mass to 50% by mass because the effect of improving the adhesion to the base material and the stretch abrasion resistance is remarkable and the hardness is excellent. More preferred is mass%.

-(B) Polyfunctional monomer having two or more (meth) acryloyl groups The curable composition for a sheet of the present disclosure contains at least one multifunctional monomer having two or more (meth) acryloyl groups. Since it contains a polyfunctional monomer, it has excellent rub resistance after stretching and excellent hardness.
The polyfunctional monomer in the present disclosure does not include the specific polymerizable compound described above.

Specific examples of the bifunctional monomer having two (meth) acryloyl groups include tricyclodecane dimethanol di (meth) acrylate, diethylene glycol monoethyl ether di (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, Di (meth) acrylated isocyanurate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, ethylene oxide (hereinafter abbreviated as “EO”) modified 1,6- Hexanediol di (meth) acrylate, epichlorohydrin (hereinafter referred to as “ECH”) modified 1,6-hexanediol di (meth) acrylate, allyloxy polyethylene glycol (meth) acrylate, 1,9-nonanediol di (meth) ) Acrylate, EO Bisphenol A di (meth) acrylate, propylene oxide (hereinafter referred to as “PO”) modified bisphenol A di (meth) acrylate, modified bisphenol A di (meth) acrylate, EO modified bisphenol F di (meth) acrylate, ECH modified hexa Hydrophthalic acid di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, EO modified neopentyl glycol di (meth) acrylate, PO modified neopentyl glycol di (meth) Acrylate, stearic acid modified pentaerythritol di (meth) acrylate, ECH modified phthalic acid di (meth) acrylate, ECH modified propylene glycol di (meth) acrylate, silicone di ( Acrylate), triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, neopentyl glycol modified trimethylol propane di (meth) acrylate, tripropylene glycol di (Meth) acrylate, EO-modified tripropylene glycol di (meth) acrylate, triglycerol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and the like. Examples of commercially available products are A-DCP (tricyclodecane methanol diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., and A-HD-N (1,9-nonane manufactured by Shin-Nakamura Chemical Co., Ltd.). Diol di (meth) acrylate) or the like can be used.

Specific examples of the trifunctional monomer having three (meth) acryloyl groups include isocyanuric acid ethylene oxide (EO) modified tri (meth) acrylate, ECH modified glycerol tri (meth) acrylate, EO modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, EO-modified phosphate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, EO-modified tri Examples include methylolpropane tri (meth) acrylate and PO-modified trimethylolpropane tri (meth) acrylate. Examples of commercially available products are M-315 (isocyanuric acid ethylene oxide (EO) -modified triacrylate) manufactured by Toagosei Co., Ltd., and A-TMPT (trimethylolpropane tri (manufactured by Shin-Nakamura Chemical Co., Ltd.). (Meth) acrylate) and the like can be used.

Specific examples of tetrafunctional monomers having four (meth) acryloyl groups include pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, diglycerin ethylene oxide ( EO) wrinkled modified (meth) acrylate and the like. Examples of commercially available products are A-TMMT (pentaerythritol tetraacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., AD-TMP (ditrimethylolpropane tetra (meth) acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd. Etc. can be used.

Specific examples of the pentafunctional or higher functional monomer having 5 or more (meth) acryloyl groups include pentafunctional monomers such as dipentaerythritol pentaacrylate, hexafunctional monomers such as dipentaerythritol hexaacrylate, and mixtures thereof. Can be mentioned. As an example of a commercially available product on the market, kayarad DPHA (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd. can be used.

The number of functional groups of the polyfunctional monomer of the present disclosure is preferably 2 to 4, more preferably 2 to 3. That is, the polyfunctional monomer of the present disclosure is preferably a polyfunctional monomer selected from the group consisting of a bifunctional monomer, a trifunctional monomer, and a tetrafunctional monomer.
When the number of functional groups of the polyfunctional monomer is 4 or less, the uniformity of the cross-linking density can be maintained more favorably, and cracks are hardly generated, and more excellent stretchability can be ensured.
In addition, it is not a composition containing only a monofunctional monomer but a composition containing a polyfunctional monomer, so that hardness can be ensured, shape retention is stably imparted, and collapse of a three-dimensional part is avoided. Can do.

Among the above, from the viewpoints of substrate adhesion of the obtained cured product and abrasion resistance after stretching, a bifunctional or trifunctional (meth) acrylate compound having an isocyanuric ring structure is preferable. Among these, from the viewpoint of scratch resistance, a trifunctional (meth) acrylate compound having an isocyanuric ring structure is more preferable.

Specific examples of the bifunctional or trifunctional (meth) acrylate compound having an isocyanuric ring structure include di (meth) acrylated isocyanurate, isocyanuric acid ethylene oxide (hereinafter also referred to as “EO”) modified tri (meth). Examples thereof include acrylate and isocyanuric acid ethylene oxide-modified di (meth) acrylate. Among these, isocyanuric acid ethylene oxide-modified tri (meth) acrylate is particularly preferable.

As the bifunctional or trifunctional (meth) acrylate compound having an isocyanuric ring structure, a compound represented by the following formula ICT or formula ICD from the viewpoint of the substrate adhesion of the obtained cured product and the abrasion resistance after stretching. Are more preferable, and a compound represented by the formula ICT is particularly preferable.

 

In formula ICT and formula ICD, L ^1C , L ^2C and L ^3C each independently represent an alkylene group or -L ^4C- (OL-5 ^C ) _nt- , and L ^4C and L ^5C each independently Represents an alkylene group, nt represents an integer of 1 or more, R ^1C , R ^2C and R ^3C each independently represents a hydrogen atom or a methyl group, and R ^4C represents a hydrogen atom, an alkyl group or a hydroxyalkyl group. Or -L ^6C- ( _OL ^{7 C} ) _nd -OH, L ^6C and L ^7C each independently represent an alkylene group, and nd represents an integer of 1 or more.

L ^1C , L ^2C and L ^3C are each independently preferably an alkylene group, more preferably an alkylene group having 2 to 8 carbon atoms, and particularly preferably an ethylene group.
L ^4C and L ^6C are each independently preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an ethylene group.
L ^5C and L ^7C are each independently preferably an ethylene group or a propylene group, more preferably an ethylene group or a 1,2-propylene group, and particularly preferably an ethylene group. .
Nt and nd are each independently preferably an integer of 1 to 20, more preferably an integer of 1 to 8, and particularly preferably an integer of 1 to 4.
R ^1C , R ^2C and R ^3C are preferably hydrogen atoms.
R ^4C is preferably an alkyl group, a hydroxyalkyl group, or —L ^6C — ( _OL ^{7 C} ) _nd —OH, and is preferably a hydroxyalkyl group or —L ^6C — ( _OL ^{7 C} ) _nd It is more preferably —OH, further preferably a hydroxyalkyl group, and particularly preferably a hydroxyethyl group.

Specific examples of the bifunctional or trifunctional (meth) acrylate compound having an isocyanuric ring structure include isocyanuric acid alkylene oxide-modified tri (meth) acrylate, isocyanuric acid alkylene oxide-modified di (meth) acrylate, and tri (meth) acryloxy. Examples thereof include alkylated isocyanurates and di (meth) acryloxyalkylated isocyanurates.
Among them, at least one compound selected from the group consisting of isocyanuric acid ethylene oxide-modified tri (meth) acrylate and isocyanuric acid ethylene oxide-modified di (meth) acrylate is preferable, and isocyanuric acid ethylene oxide-modified tri (meth) acrylate. Is particularly preferred.

A commercially available product may be used for the bifunctional or trifunctional (meth) acrylate compound having an isocyanuric ring structure. As an example of a commercially available product, Aronix series manufactured by Toagosei Co., Ltd. ( For example, M-315, M-313, M-215, etc.) can be preferably used.

The sheet curable composition of the present disclosure may include one or more polyfunctional monomers having two or more (meth) acryloyl groups, or may include two or more.
The content of the polyfunctional monomer having two or more (meth) acryloyl groups in the curable composition for sheets is preferably 1% by mass to 80% by mass with respect to the total mass of the curable composition for sheets. 10 mass% to 50 mass% is more preferable, and 30 mass% to 50 mass% is more preferable.
When the content of the polyfunctional monomer is 1% by mass or more, the hardness becomes better and the stretching abrasion resistance becomes better. Moreover, the shape retainability of the cured product is stably imparted, and the collapse of the three-dimensional portion can be avoided. Moreover, stretchability is favorable in content of a polyfunctional monomer being 50 mass% or less, and generation | occurrence | production of the crack of the hardened | cured material at the time of shaping | molding can be suppressed.

-(C) Photoradical polymerization initiator-
The sheet curable composition of the present disclosure contains at least one radical photopolymerization initiator. The photopolymerization initiator is preferable to the thermal polymerization initiator from the viewpoint of scratch resistance and high-temperature stretchability of the resulting cured product, and among these, the photo radical polymerization initiator is more preferable.

The radical photopolymerization initiator is not particularly limited in structure. For example, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 1-hydroxy-cyclohexyl-phenyl-ketone, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-Hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl -Propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropa 1-one and the like.

Commercially available products that are commercially available may be used as the photoradical polymerization initiator. As specific examples of commercially available products, IRGACURE series (example: IRGACURE TPO, IRGACURE 819, IRGACURE 651, IRGACURE 184, IRGACURE 1173 manufactured by BASF) may be used. IRGACURE 2959, IRGACURE 127, IRGACURE 907, etc.).

The curable composition for a sheet of the present disclosure may contain one type of radical photopolymerization initiator, or may contain two or more types.
As the content of the radical photopolymerization initiator in the curable composition for a sheet, from the viewpoint of the base material adhesion and the stretch rub resistance of the obtained cured product, the total mass of the curable composition for the sheet, 0.05 mass% to 10 mass% is preferable, 0.1 mass% to 10 mass% is more preferable, 0.1 mass% to 5 mass% is still more preferable, and 0.5 mass% to 3 mass% is particularly preferable. .
When the content of the radical photopolymerization initiator is 0.05% by mass (preferably 0.1% by mass) or more, the curing reaction proceeds more favorably and the hardness and the stretch rub resistance are excellent. Moreover, although content of radical photopolymerization initiator may exceed 10 mass%, the effect by setting it as content exceeding 10 mass% is small.

-(D) Urethane (meth) acrylate compound-
The curable composition for a sheet of the present disclosure does not contain a urethane (meth) acrylate compound, or the content of the urethane (meth) acrylate compound is 0% by mass with respect to the total mass of the curable composition for a sheet. Over 4% by mass.

Since the urethane (meth) acrylate compound is a relatively high molecular weight compound, if it contains a urethane (meth) acrylate compound, the hardness tends to decrease, and the adhesion of the cured product to the substrate tends to decrease. is there. Decrease in the adhesion of the cured product to the base material causes peeling of the cured product and impairs the abrasion resistance after stretching.

“Not containing a urethane (meth) acrylate compound” means that the content of the urethane (meth) acrylate compound in the curable composition for a sheet of the present disclosure is 0 (zero) mass%. Further, when the content of the urethane (meth) acrylate compound is not 0% by mass (when the content exceeds 0% by mass), the content is less than 4% by mass. It is intended to permit the case where it is inevitably contained to such an extent that the effect is not significantly impaired.

Sheet of (A) specific polymerizable compound, (B) polyfunctional monomer having two or more (meth) acryloyl groups, (C) photoradical polymerization initiator, and (D) urethane (meth) acrylate compound Each content in the curable composition for use is such that (A) the specific polymerizable compound is 15% by mass to 50% by mass with respect to the solid content of the curable composition for sheet, and (B) two or more The polyfunctional monomer having a (meth) acryloyl group is 1% by mass to 80% by mass, (C) the radical photopolymerization initiator is 0.1% by mass to 5% by mass, and (D) urethane (meta ) The acrylate compound is preferably 0% by mass to 4% by mass, and further, (A) the specific polymerizable compound is 25% by mass to 50% by mass, and (B) two or more (meth) acryloyl groups A polyfunctional monomer having 0% by mass to 50% by mass, (C) 0.1% by mass to 5% by mass of a radical photopolymerization initiator, and (D) 0% by mass to 3% by mass of a urethane (meth) acrylate compound. Is preferred.

-(E) Other ingredients-
The sheet curable composition of the present disclosure may include other components in addition to the above components.
The curable composition for a sheet of the present disclosure may contain other components such as an organic solvent and inorganic particles, if necessary, in addition to the above components.
Examples of the organic solvent include toluene and methyl ethyl ketone. Since the curable composition for a sheet of the present disclosure contains the above-described specific polymerizable compound, the polymerizable compound also functions as a solvent and does not need to contain an organic solvent separately.
Examples of the inorganic particles include so-called filler particles such as silicon dioxide (silica). Examples of the inorganic particles include commercially available organosilica sol MEK-ST series (eg, MEK-ST-40, MEK-ST-L, etc.) manufactured by Nissan Chemical Industries.

The curable composition for a sheet of the present disclosure is preferably a composition that can be cured by active energy rays. “Active energy rays” are radiation that can give energy to generate polymerization initiation species in the curable composition by irradiation, and include α rays, γ rays, X rays, ultraviolet rays, visible rays, electron rays, etc. To do. Among these, from the viewpoint of curing sensitivity and device availability, ultraviolet rays and electron beams are preferable, and ultraviolet rays are more preferable.
Moreover, the curable composition for a sheet of the present disclosure is preferably an active energy ray-curable curable composition, and more preferably an oil-based polymerizable composition. It is preferable that the curable composition for a sheet of the present disclosure does not contain water and a volatile solvent as much as possible, and even if it is contained, it is preferably 5% by mass or less based on the total mass of the curable composition. It is more preferably 1% by mass or less, and further preferably 0.5% by mass or less.

In addition, in the curable composition for a sheet of the present disclosure, the glass transition temperature (Tg) of the obtained cured product may exceed 90 ° C. from the viewpoint of the substrate adhesion and the stretch rub resistance of the obtained cured product. Preferably, it is 95 ° C. or more and 200 ° C. or less, and more preferably 100 ° C. or more and 180 ° C. or less.

<Hardened product and manufacturing method thereof, and optical member>
The cured product of the present disclosure is obtained by curing the curable composition for a sheet of the present disclosure described above. Moreover, the optical member of this indication has a hardened | cured material of the curable composition for sheets of this indication mentioned above.

The cured product of the present disclosure can be suitably used as an optical member, and a cylindrical lens, a prism, a hemispherical microlens, a Fresnel lens, or the like can be more suitably used as a convex lens, and a plurality of convex lenses ( It can be particularly preferably used as a lenticular lens in which a cylindrical lens) is arranged in parallel.
The method for producing the cured product of the present disclosure is not particularly limited. For example, the curing of the curable composition for a sheet of the present disclosure may be photocuring (curing by irradiation with active energy rays) or thermosetting. However, photocuring is preferable.

The cured product of the present disclosure is not particularly limited as long as it is a cured product using the above-described curable composition for a sheet of the present disclosure. It is manufactured by the manufacturing method of an object.

The method for producing a cured product of the present disclosure includes a step of preparing the above-described curable composition for a sheet of the present disclosure (hereinafter, also referred to as “composition preparing step”), and an activity energy of the curable composition for a sheet. A step of curing by irradiation with a line (hereinafter also referred to as “curing step”), and may include other steps as necessary.

-Composition preparation process-
In the composition preparation step, the curable composition for a sheet of the present disclosure described above is prepared. Specifically, the specific polymerizable compound, the polyfunctional monomer having two or more (meth) acryloyl groups, and the radical photopolymerization initiator are included, and the urethane (meth) acrylate compound is not contained. Or the content of the urethane (meth) acrylate compound is 0% by mass or less and less than 4% by mass with respect to the total mass of the sheet curable composition, or a sheet curable composition is prepared, Or the said curable composition prepared previously is prepared.
Details of each component of the curable composition for a sheet of the present disclosure are as described above, and preferred embodiments are also the same.
Specifically, for example, a curable composition for a sheet can be prepared by mixing a specific polymerizable compound, a polyfunctional monomer having two or more (meth) acryloyl groups, and a radical photopolymerization initiator. .

-Curing process-
In the curing step, the curable composition for sheets is cured by irradiation with active energy rays. By curing, a cured product of the curable composition for sheets is obtained.
As light sources for generating active energy rays, mercury lamps, metal halide lamps, ultraviolet (UV) fluorescent lamps, gas lasers, solid lasers, and the like are widely known. Further, a semiconductor ultraviolet light emitting device may be applied as a light source, and an LED (Light Emitting Diode) and an LD (Laser Diode) are also suitable in terms of small size, long life, high efficiency, and low cost.
As the light source, a metal halide lamp, an ultra high pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a mercury xenon lamp, an LED or a blue-violet laser is preferable. Among them, an ultra-high pressure mercury lamp capable of irradiating light with a wavelength of 365 nm, 405 nm, or 436 nm, a high-pressure mercury lamp capable of irradiating light with a wavelength of 365 nm, 405 nm, or 436 nm, and a mercury xenon lamp capable of irradiating with a wavelength of 365 nm, 405 nm, or 436 nm. Alternatively, an LED capable of light irradiation with a wavelength of 355 nm, 365 nm, 385 nm, 395 nm, or 405 nm is more preferable, and an LED capable of light irradiation with a wavelength of 355 nm, 365 nm, 385 nm, 395 nm, or 405 nm is particularly preferable.

The dose of the active energy ray may be appropriately selected depending on the composition and amount of the sheet for the curable composition, 0.3 J / cm ² or more 5 J / cm ² or less.

The irradiation with the active energy ray can be performed by selecting a known device including a light source capable of irradiating the active energy ray. For example, an ultraviolet (UV) irradiation device such as EXECULE 3000 manufactured by HOYA CANDEO OPTRONICS may be used.

<Three-dimensional molding sheet>
The sheet for three-dimensional molding of the present disclosure may be a sheet having a cured product of the curable composition for sheet of the present disclosure described above, and specifically, the curable composition of the present disclosure on the substrate and the substrate. A laminated sheet having at least a cured product is preferable.
Especially, it is preferable that the sheet | seat for three-dimensional shaping | molding of this indication has a resin base material and the hardened | cured material of the curable composition for sheet | seats of this indication provided in the at least one surface of the resin base material.
As the resin substrate, from the viewpoint of improving the adhesion of the cured product, the component of the polarity term of SP values (.delta.p) there is ^{5MPa (1/2) ~ 15MPa (1/2} ) resin substrate is in the range of preferable. The resin base material will be described later.

There is no restriction | limiting in particular in the shape of the hardened | cured material which the sheet | seat for three-dimensional shaping | molding of this indication has, if it is a desired shape, a film | membrane shape may be sufficient, and a semi-cylindrical thing like the cylindrical lens mentioned later May be in a parallel shape, or may be a shape in which hemispherical objects are arranged like a microlens.

The three-dimensional molding sheet of the present disclosure is preferably a three-dimensional molding laminated sheet. Specifically, a laminated sheet having a hard coat film, a laminated sheet having a brightness enhancement film, a lenticular sheet, a prism sheet, a microlens sheet, and a Fresnel lens. It can be suitably used as a sheet, a fly-eye lens or the like.

-Lenticular sheet-
The lenticular sheet of the present disclosure has a cured product of the curable composition for a sheet of the present disclosure. The cured product in the lenticular sheet is preferably a lenticular lens.
Further, the lenticular sheet of the present disclosure preferably includes a resin base material and a cylindrical lens disposed on at least one surface of the resin base material, and further has an image on the side opposite to the side having the cylindrical lens of the resin base material. It is more preferable to have.
The form having an image may be an aspect in which an image is directly applied to the surface of a resin base material, or a recording layer is provided, and an image (hereinafter referred to as a decorative image) is formed on the recording layer by a known recording method such as an inkjet method. It is also possible to use an embodiment with a

The lenticular sheet of the present disclosure may be a lenticular decorative sheet in which a lenticular image is formed directly on the surface of the resin base opposite to the side having the cylindrical lens, for example, as shown in FIG.
The lenticular decorative sheet has a lenticular lens in which convex cylindrical lenses having a semicylindrical surface are arranged on an image suitable for lenticular display, thereby displaying a different image depending on the viewing angle (lenticular display). Body).

An example of a lenticular decorative sheet (lenticular sheet) is shown in FIG.
The lenticular decorative sheet (lenticular display) 10 has a semi-cylindrical shape of a lenticular lens 12 in which a plurality of convex lenses (cylindrical lenses) 12A having a semi-cylindrical surface are arranged in parallel, and a convex lens 12A of the lenticular lens 12. And a lenticular image 14 disposed on the side opposite to the front side (also referred to as the back side).
The x direction indicates the width direction of the lens, and the y direction indicates the longitudinal direction of the lens.

The lenticular sheet of the present disclosure preferably includes a lenticular lens layer in which a plurality of convex lenses (cylindrical lenses) having a semicylindrical surface are arranged in parallel. The width per cylindrical lens is not particularly limited, and the pitch width of the lenses may be selected depending on the purpose. The width per cylindrical lens is usually often expressed by LPI (Line Per Inch) representing the number of lenses per inch (2.54 cm). For example, 100 LPI indicates that 100 cylindrical lenses (100 rows) per inch are arranged in parallel, and the pitch of the lenses is 254 μm. The larger the value of the number of lines per inch (number of lenses arranged), the smaller the lens pitch, and the higher the definition.
A low-definition lenticular sheet (for example, 60 LPI) is suitable for use in a poster or the like that displays a pattern whose observation position is relatively far. For the purpose of reading small text information such as a business card, it is preferable that the lenses constituting the lenticular lens layer are arranged in 100 rows or more per 2.54 cm (1 inch). On the other hand, from the viewpoint of the resolution of the lenticular image, the number of convex lenses constituting the lenticular lens layer is more preferably 200 rows (2.5 LPI) or less per 2.54 cm.

Conventionally, lenticular materials are often used in the form of sheets or films, and there are few attempts to use them in a three-dimensional shape. However, the conventional lenticular sheet has a weak adhesion to the substrate, tends to be peeled off by molding, and tends to have low resistance due to abrasion.
On the other hand, the lenticular sheet of the present disclosure has a lenticular lens that is a three-dimensional molding sheet formed by curing the curable composition for a sheet of the present disclosure, and thus has excellent substrate adhesion and stretch rub resistance, Excellent three-dimensional moldability.

(Resin base material)
The resin base material in the present disclosure is a base material as a support material, and any resin can be selected according to the purpose or the like. As the resin substrate, a sheet-like or film-like substrate can be suitably used.
Examples of the resin substrate include sheets or films of acrylic resin, polyester resin, polycarbonate resin, and the like.
Examples of the acrylic resin include polymethyl methacrylate.
Examples of the polyester resin include polyethylene terephthalate (PET) and polyethylene naphthalate (PEN).

The resin base material is preferably a resin base material in which the SP value polar term component (δp) is in the range of 5 MPa ^(1/2) to 15 MPa ^(1/2) . For example, polymethyl methacrylate (PMMA; δp) = 10.5), polyethylene terephthalate (PET; δp = 6.4), polycarbonate (PC; δp = 5.9) and the like are suitable. By selecting a resin substrate having a δp in the above range and bringing the δp of the resin substrate close to the δp of the cured product, the adhesion of the cured product to the substrate can be further improved.

The thickness of the resin substrate is not particularly limited and is preferably in the range of 50 μm to 300 μm, and more preferably in the range of 50 μm to 200 μm from the viewpoint of uniform molding (shaping) at high temperatures. When it is in the above range, the resin base material is not easily torn, and cracks are hardly generated during handling (for example, during transportation) during molding processing, and are also difficult to crack during three-dimensional molding.

Commercially available products may be used as the resin substrate. For example, acrylic resin film (Acryprene HBS010P (PMMA film), thickness: 125 μm) manufactured by Mitsubishi Rayon Co., Ltd., polyethylene terephthalate manufactured by Toray Industries, Inc. A resin film (Lumirror S10, thickness: 100 μm), a polycarbonate resin film (Iupilon H-3000, thickness 125 μm) manufactured by Teijin Chemicals Ltd. can be used.

(image)
In the lenticular sheet of the present disclosure, a mode in which an image (lenticular image) displayed in a lenticular manner is formed on the side opposite to the side having the cylindrical lens of the resin base material is preferable. The lenticular image may be directly formed on the surface of the resin base material of the lenticular sheet. Further, the lenticular image may be an aspect in which a recording layer for recording the lenticular image is provided and the lenticular image is formed on the recording layer.
The surface of the resin substrate on which the lenticular image is formed may be subjected to surface treatment (for example, corona discharge treatment) from the viewpoint of increasing the adhesive force between the resin substrate and the recording layer.
The lenticular image may be formed, for example, by applying a colored liquid (for example, ink) for forming a lenticular image to a resin base material. The application of the coloring liquid (formation of a lenticular image) can be performed by, for example, a printing method such as offset printing, a coating method, an ink jet method, or the like.
The coloring liquid preferably contains a solid component and a solvent for forming a lenticular image. The lenticular image preferably contains a resin, and at least a part of the resin is preferably crosslinked with a crosslinking agent. Therefore, the aspect containing resin and a crosslinking agent as a solid component contained in a coloring liquid is preferable.
The resin is preferably at least one resin selected from the group consisting of polyester, acrylic resin and urethane resin, and is particularly advantageous when a parallax image is formed by offset printing.

In FIG. 1, a lenticular image 14 includes display image sequences 14A and 14B for separately displaying two display images, and an interpolated image sequence 14C inserted between adjacent display image sequences 14A and 14B. And an image sequence group including
Specifically, the display image rows 14A and 14B extracted from each display image in a stripe shape are arranged adjacent to each other at the corresponding convex lens 12A, and the adjacent display image rows 14A and 14A are arranged. A color (interpolation color) between one color and the other color of the adjacent display image rows 14A and 14B at a position where the colors of the adjacent display image rows 14A and 14B are different from each other during 14B. The interpolated image sequence 14c is inserted.

-Manufacturing method of sheet for solid molding-
The three-dimensional molding sheet of the present disclosure can be manufactured by a method according to the above-described manufacturing method of the cured product of the present disclosure.
Specifically, the step of preparing the curable composition for sheets of the present disclosure described above (composition preparing step), the curable composition for sheets is cured by irradiation with active energy rays, and a three-dimensionally molded sheet is formed. A manufacturing process (sheet manufacturing process), and may include other processes as necessary.
The composition preparation step is as described above.
In the sheet production process, the sheet curable composition is cured by irradiation with active energy rays to produce a three-dimensional molding sheet, and the process for producing a lenticular sheet (lenticular sheet production process) is described below as an example. To do.

(Lenticular sheet production process)
In the lenticular sheet manufacturing step, the curable composition according to the present disclosure is molded and cured by irradiation with active energy rays to prepare a lenticular sheet having a cylindrical lens on the resin base material.
The details of the curable composition according to the present disclosure are as described above, and the preferred embodiments are also the same.

In this step, first, the curable composition is molded into the shape of the target cylindrical lens before curing. The molding is not particularly limited as long as the target shape can be obtained, but from the viewpoint of molding efficiency and molding accuracy, molding using a mold such as a mold or a wooden mold is preferable.
Specifically, for example, a mold processed into a desired lens shape is prepared, the curable composition is poured into the mold, dried as necessary, and then the curable composition is cured. Good. Thereby, the molded object shape | molded by the target shape is obtained stably.

Next, radicals are generated by irradiating active energy rays, and the polymer is cured by a polymerization reaction of the polymerizable compound. Thereby, a cylindrical lens that is a cured product of the curable composition according to the present disclosure is formed.
In molding the cylindrical lens, the curable composition may be cured after the resin substrate is brought into contact with the curable composition in advance before the curable composition is cured. By curing in a state where the resin base material and the curable composition are in contact with each other, an improvement in adhesion due to curing shrinkage can be expected, and in addition to the adhesion effect derived from the composition, the improvement in the adhesion to the resin base material is achieved. More effective.
From the viewpoint of adhesion of the cylindrical lens to the resin base material, a lenticular sheet having a cylindrical lens having superior adhesion can be obtained by curing the curable composition in contact with the resin base material.

The light source for generating the active energy rays and the irradiation with the active energy rays are the same as those in the above-described method for producing a cured product, and the preferred embodiments are also the same.

<Three-dimensional structure>
The three-dimensional structure of the present disclosure is a three-dimensional molded product (preferably three-dimensionally molded by a technique such as thermoforming or vacuum molding) of the three-dimensionally molded sheet of the present disclosure described above. The three-dimensional structure of the present disclosure is preferably a three-dimensional molded product of the lenticular sheet of the present disclosure.
Since the three-dimensional molding sheet of the present disclosure that is excellent in three-dimensional moldability is used in molding that is exposed to a relatively high temperature, a three-dimensional structure that is excellent in substrate adhesion and excellent in stretch-rubbing resistance is obtained.

-3D manufacturing method
The three-dimensional structure of the present disclosure is not particularly limited to the method of three-dimensional molding as long as the three-dimensional structure of the present disclosure is manufactured using the three-dimensional molding sheet of the present disclosure.
As a method for producing a three-dimensional structure using the three-dimensionally shaped sheet of the present disclosure, for example, the curable composition of the present disclosure is molded and cured by irradiation with active energy rays, and an optical member is formed on the resin substrate. A step of producing a three-dimensionally formed sheet (three-dimensionally formed sheet producing step), and a step of obtaining a three-dimensionally molded article by three-dimensionally molding (preferably vacuum forming or pressure forming) the produced three-dimensionally formed sheet , Also referred to as “three-dimensional molding step”).

Hereinafter, a case where three-dimensional molding is performed using a lenticular sheet as a three-dimensional molding sheet will be described as an example. That is,
In the method for producing a three-dimensional structure, for example, the curable composition of the present disclosure is molded, cured by irradiating active energy rays, and a lenticular sheet having a cylindrical lens (optical member) on a resin substrate is produced. A method comprising a step (a lenticular sheet production step) and a step (three-dimensional molding step) of obtaining a lenticular three-dimensional molded body by three-dimensional molding (preferably vacuum molding or pressure molding) of the produced lenticular sheet. Can be mentioned.
The lenticular sheet manufacturing process is as described above.

(Three-dimensional molding process)
In the three-dimensional molding process, the three-dimensional molding sheet (for example, lenticular sheet) manufactured in the three-dimensional molding sheet manufacturing process is three-dimensionally molded. In this step, it is sufficient that a three-dimensional molding sheet (for example, a lenticular sheet) can be molded, and it may be subjected to molding processing using a mold such as a mold.

Suitable examples of the three-dimensional molding include thermal molding and vacuum molding.
The method of vacuum forming is not particularly limited, but a method of performing three-dimensional molding in a heated state under vacuum is preferable.
The vacuum refers to a state in which the room is evacuated to a degree of vacuum of 100 Pa or less.
The temperature at the time of three-dimensional molding is preferably 60 ° C. or higher, more preferably 80 ° C. or higher, and even more preferably 100 ° C. or higher. The upper limit of the temperature at the time of three-dimensional molding is generally preferably 200 ° C.
The temperature at the time of three-dimensional molding refers to the temperature of a three-dimensional molding sheet (for example, a lenticular sheet) subjected to three-dimensional molding, and is measured by attaching a thermocouple to the surface of the three-dimensional molding sheet.

The vacuum molding can be performed using a vacuum molding technique widely known in the molding field. For example, vacuum molding may be performed using Formech 508FS manufactured by Nihon Zokki Kogyo Co., Ltd.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.
In this example, a case where a lenticular sheet having a cylindrical lens which is an optical member is produced as a three-dimensional molding sheet and three-dimensionally molded is shown as an example.

(Examples 1 to 15, Comparative Examples 1 to 7)
-Preparation of curable composition-
Components in the composition shown in Table 1 below were mixed to prepare a cured composition (cured composition for sheet) for producing a cylindrical lens as an optical member (composition preparing step).

-Production of lenticular lens sheet-
As shown in FIG. 1, the shape of a lenticular lens in which a plurality of convex lenses having a semi-cylindrical surface are arranged in parallel [height 60 μm, length 80 mm in the longitudinal direction y, one lens width (lens pitch) 100 LPI (Line Per Inch)] was poured into a mold (width 100 mm × depth 100 mm), and 2 g of the curable composition was poured into the mold, and an acrylic resin film (Acryprene HBS010P (PMMA film, thickness: 125 μm, SP The polar term component δp: 10.5 MPa ^(1/2) ), manufactured by Mitsubishi Rayon Co .; resin base material) was placed and fixed. Next, the curable composition poured into the mold was irradiated with ultraviolet rays (UV) through an acrylic resin film (UV irradiation). UV irradiation was performed using an ultraviolet (UV) irradiation apparatus (EXECURE 3000, manufactured by HOYA CANDEO OPTRONICS) under the condition of a UV irradiation amount of 1.0 J / cm ² until the curable composition was cured ( Curing step). After UV irradiation, the UV-irradiated curable composition was demolded to obtain a lenticular lens sheet (three-dimensional molding sheet) having a lenticular lens (cylindrical lens (optical member)) as a cured product.

In addition, since the lenticular lens of the lenticular lens sheet is a cured product cured by a polymerization reaction of a polyfunctional monomer, the lenticular lens has a cross-linked structure.

-Fabrication of single film-
The curable composition described above is sandwiched between two glass plates that have been subjected to hydrophobic treatment, cured by UV irradiation under the same conditions as described above (curing step), and peeled off from the glass plate to a thickness of 50 μm. A film (single film) was produced.

(Evaluation)
The following evaluation was performed on the obtained lenticular lens sheet. The evaluation results are shown in Table 2.

-1. Substrate adhesion
The adhesion of the cured product to the substrate in the lenticular lens sheet was evaluated by two test methods.

[A. Tape peeling test]
In the lenticular lens sheet, 11 incisions reaching the resin base material from the surface of the lenticular lens, which is a cured resin film (cured product), are made in parallel by a method in accordance with JIS K5600-5-6 (1999). The cured resin film was partitioned into a grid by changing the direction and making eleven parallel cuts. A cellophane adhesive tape (CT-24, manufactured by Nichiban Co., Ltd.) is applied to the surface of each film partitioned in a grid, and then the cellophane adhesive tape is gripped and pulled in a direction perpendicular to the surface direction. The presence or absence of the peeled part was confirmed visually. Evaluation was according to the following criteria.
<Evaluation criteria>
A: There is no peeling part.
B: The ratio of the peeled portion to the entire surface is more than 0% and less than 15%.
C: The ratio of the peeled portion to the entire surface is 15% or more.

[B. Bending test]
The lenticular lens, which is a cured product, is peeled off when the lenticular lens sheet is bent 90 ° using a mandrel testing machine (type I type, mandrel diameter 20 mm) by a method according to JIS K5600-5-1 (1999). Evaluation was performed according to the following evaluation criteria.
<Evaluation criteria>
A: Peeling is not recognized.
B: Peeling is recognized.

-2. hardness-
An operation in which a pencil (Mitsubishi Unipencil: hardness H) tilted at 45 ° is pressed against the lenticular lens of the lenticular lens sheet and moved 1 cm at a speed of 1 mm / second by a method according to JIS K5600-5-4 (1999). The test was conducted at five locations, and the presence or absence of scratches was visually examined, and evaluated according to the following evaluation criteria.
<Evaluation criteria>
A: 0 to 1 scratch was observed.
B: Two to three scratches were observed.
C: Four to five scratches were observed.

-3. Stretch resistance-
An image obtained by synthesizing alphabet “A” and alphabet “B” as 200 LPI (Line Per Inch) as a recording layer was formed by offset UV printing on the surface opposite to the side having the cylindrical lens of the lenticular sheet. The lenticular sheet on which the recording layer was formed was heated to 100 ° C. and stretched by 15% with a tensile tester, and then the sheet was cooled in a room temperature environment. After stretching, the surface of the lenticular lens of the lenticular sheet is reciprocated 2000 times with a load of 200 g at room temperature (25 ° C.) using a wear resistance tester under a load of 200 g. By rubbing the surface of the lenticular lens. Next, the degree of scratches on the surface of the lenticular lens was visually confirmed and evaluated according to the following evaluation criteria. The rubbing direction was parallel to the surface of the lenticular sheet.
<Evaluation criteria>
A: The lenticular sheet is not damaged at all.
B: Scratches can be confirmed on the lenticular sheet, but there is no effect on switching of images when the viewing angle is changed.
C: The lenticular sheet is severely scratched, and the lenticular sheet is whitened, which affects the switching of images when the viewing angle is changed, and an abnormality in which different images are visually recognized occurs.

 

Details of each component in Table 1 are as follows. In Table 1, “-” indicates that the component is not contained.

(A) Polymerizable compound having a functional group containing a nitrogen atom and having a molecular weight of 300 or less NVP: N-vinylpyrrolidone, Wako Pure Chemical Industries, Ltd. NVC: N-vinyl-ε-caprolactam, Tokyo Chemical Industry Co., Ltd. ALC: allyl cyanide, Tokyo Chemical Industry Co., Ltd. TALC: triallyl cyanurate, Tokyo Chemical Industry Co., Ltd. CEA: cyanoethyl acrylate, Tokyo Chemical Industry Co., Ltd. DMAA: dimethylacrylamide, Wako Pure Chemical Industries, Ltd. ACMO: acryloylmorpholine, Wako Pure Chemical Industries, Ltd.

(B) a polyfunctional monomer having two or more (meth) acryloyl groups M-315: isocyanuric acid ethylene oxide (EO) modified triacrylate (trifunctional acrylate compound having isocyanuric ring structure), Toagosei Co., Ltd. A-DCP : Tricyclodecane dimethanol diacrylate (bifunctional acrylate compound), Shin-Nakamura Chemical Co., Ltd. A-TMPT: Trimethylolpropane triacrylate (trifunctional acrylate compound), Shin-Nakamura Chemical Co., Ltd. PETA: Light acrylate PE-3A (Pentaerythritol triacrylate, trifunctional acrylate compound), Kyoeisha Chemical Co., Ltd. DPHA: kayarad DPHA (dipentaerythritol hexaacrylate, hexafunctional acrylate compound), Nippon Kayaku Co., Ltd.

(C) Photoradical polymerization initiator Irgacure TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, BASF (D) urethane acrylate compound:
Urethane acrylate (B-1) described in Synthesis Example 1 in paragraph 0067 of JP-A-2016-74884

(E) Other components THF-A: Tetrahydrofurfuryl acrylate (Nitrogen atom-free; Light acrylate THF-A, Kyoeisha Chemical Co., Ltd. HEA: Hydroxyethyl acrylate (Nitrogen atom-free; Light acrylate HOA (N), Osaka Organic Chemistry) Industrial Co., Ltd.)
Stearyl acrylamide: synthesized using N-octylamine (Tokyo Chemical Industry Co., Ltd.) and acryloyl (Wako Pure Chemical Industries, Ltd.) with reference to the method described in the literature (J. Am. Chem. Soc., 125, 6254). . Yield 76% (molecular weight: 324)
FA-513AS (monofunctional monomer): Fancryl FA-513AS (dicyclopentanyl acrylate, homopolymer glass transition temperature: 120 ° C.), Hitachi Chemical Co., Ltd. AA-6 (thickener): polymethyl methacrylate (terminal) Methacryloyl group-containing methacrylic resin, number average molecular weight (Mn): 6,000), Toagosei Co., Ltd. C-1 (conductive material): C-1 component described in paragraph 0075 of JP-A-2016-74884 The synthesis was performed with reference to the synthesis method.
AN-6S (macromonomer): styrene-acrylonitrile copolymer having a methacryloyl group at the terminal (number average molecular weight (Mn): 6,000), Toagosei Co., Ltd. MEK-ST (colloidal silica): Nissan Chemical Industries, Ltd. Silica particles having an average particle size of 10 nm to 15 nm Toluene (organic solvent): Tokyo Chemical Industry Co., Ltd. MEK (organic solvent): Methyl ethyl ketone, Tokyo Chemical Industry Co., Ltd.

 

As shown in Table 2, in Examples, a urethane (meth) acrylate compound containing a polymerizable compound having a functional group containing a nitrogen atom and a molecular weight of 300 or less and a polyfunctional monomer and having a relatively high molecular weight is used. In the curable composition which is not contained or the content of which is suppressed to less than 4% by mass, the adhesiveness of the cured product to the base material and the rub resistance after stretching were excellent as compared with the comparative example. Also, the hardness was good.
Among the above, as shown in Examples 2 to 8, among the polymerizable compounds having a functional group containing a nitrogen atom, the compounds represented by the general formula (I) or the general formula (II) described above were used. In particular, the adhesion of the cured product to the substrate and the abrasion resistance after stretching were particularly excellent, and the hardness was also better.
Further, as shown in Example 1 and Examples 9 to 11, compared to Example 9 including a bifunctional monomer, Examples 1, 10 and 11 including a trifunctional monomer are superior in the abrasion resistance after stretching. Hardness also improved.
In Example 15, a relatively high molecular weight urethane acrylate compound is contained, but since the content of the urethane acrylate compound is suppressed to be as small as 3% by mass, the adhesion to the substrate and the abrasion resistance after stretching are good. Met.
On the other hand, since Comparative Examples 1 and 7 do not contain a polymerizable compound having a functional group containing a nitrogen atom, the adhesion to the base material is low and the film is easily peeled off, resulting in poor abrasion resistance after stretching. It was a thing. Further, Comparative Example 6 containing no polyfunctional monomer contained a polymerizable compound having a functional group containing a nitrogen atom, so that the adhesion to the substrate was relatively good, but the abrasion resistance after stretching was poor.
Moreover, in the composition using a polymerizable compound containing a nitrogen atom but having a large molecular weight as in Comparative Example 2, the adhesion deteriorated and the rub resistance after stretching also decreased.
As in Comparative Examples 3 to 4, in the composition using a polymerizable compound that does not contain a nitrogen atom in the molecule, the interaction with the substrate is insufficient and the adhesion is weak, and as a result, the rub resistance after stretching is also reduced. It became inferior.
As in Comparative Example 5, even in a composition containing a polymerizable compound having a functional group containing a nitrogen atom and a molecular weight of 300 or less and a polyfunctional monomer, when the content of a relatively high molecular weight urethane acrylate compound is large, It was difficult to achieve both the adhesion of the cured product to the substrate and the rub resistance after stretching.

The disclosure of Japanese Patent Application No. 2017-058275 filed on Mar. 23, 2017 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually stated to be incorporated by reference, Incorporated herein by reference.

Claims (11)

1. A polymerizable compound having a functional group and a polymerizable group containing a nitrogen atom and having a molecular weight of 300 or less;
   A polyfunctional monomer having two or more (meth) acryloyl groups other than the polymerizable compound;
   A radical photopolymerization initiator;
   Including
   Three-dimensional molding which does not contain a urethane (meth) acrylate compound, or the content of the urethane (meth) acrylate compound is more than 0% by mass and less than 4% by mass with respect to the total mass of the curable composition for sheets. A curable composition for a sheet used for a sheet.
2. The curable composition for sheets according to claim 1, wherein the polymerizable compound is a compound represented by the following general formula (I) or the following general formula (II).
   

   

   
   
   In the formula, R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ³ and R ⁴ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. X ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. R ¹ , R ² , R ³ , R ⁴ and X ¹ may be the same or different and may form a ring with each other.
   

   

   
   
   In the formula, R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ⁷ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. X ² represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. At least one of R ⁵ , R ⁶ and R ⁷ contains a nitrogen atom bonded to a carbon atom of the hydrocarbon group. X ² , R ⁵ , R ⁶ and R ⁷ may be the same or different and may form a ring with each other.
3. The curable composition for sheets according to claim 1 or 2, wherein the polymerizable compound has a component δp of an SP value polar term in a range of 5 MPa ^(1/2) to 15 MPa ^(1/2) .
4. The sheet curability according to any one of claims 1 to 3, wherein a content of the polymerizable compound is 15% by mass to 50% by mass with respect to a solid content of the sheet curable composition. Composition.
5. The sheet according to any one of claims 1 to 4, wherein the polyfunctional monomer is at least one polyfunctional monomer selected from the group consisting of a bifunctional monomer, a trifunctional monomer, and a tetrafunctional monomer. Curable composition.
6. A cured product obtained by curing the curable composition for sheets according to any one of claims 1 to 5.
7. Preparing a curable composition for a sheet according to any one of claims 1 to 5,
   Curing the sheet curable composition by irradiation with active energy rays;
   The manufacturing method of the hardened | cured material containing this.
8. A three-dimensional molding sheet having a cured product of the curable composition for a sheet according to any one of claims 1 to 5.
9. An optical member having a cured product of the curable composition for sheets according to any one of claims 1 to 5.
10. A lenticular sheet comprising a cured product of the curable composition for sheets according to any one of claims 1 to 5.
11. A three-dimensional structure which is a three-dimensional molded product of the solid molding sheet according to claim 8 or the lenticular sheet according to claim 10.

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