JP6662232B2 - Resin laminate, display front panel, portable information terminal device, and glazing for moving objects - Google Patents

Description

  The present invention relates to a resin laminate excellent in impact resistance, abrasion resistance, and moldability. Further, the present invention relates to a display front plate including the resin laminate, a portable information terminal device including the display front plate, and a glazing for a moving body including the resin laminate.

In recent years, as a display front plate for protecting a display surface of a portable information terminal device such as a mobile phone, a car navigation display device, a portable game device, or a mobile vehicle such as an automobile, a railway, an airplane, and a ship. As a glazing for reducing the weight, a resin plate having transparency is used.
In the display front panel application described above, the display front panel has a thickness to prevent damage to the display front panel when the portable information terminal device collides with another object or when the portable information terminal apparatus is dropped and exposed to an impact. Even if it is thin, it must be strong against impact, and the resin plate is required to have impact resistance.
In recent years, a touch panel method has been adopted for a display front plate, and a resin plate is required to have abrasion resistance in order to suppress occurrence of scratches caused by finger nails or the like.
Further, for applications such as mobile phones, the number of cases where the display front plate is processed into a curved surface or a complicated shape is increasing, and a resin plate is required to have high moldability (bendability).
Further, in the above-mentioned glazing application for a moving body, a resin plate is required to have impact resistance and scratch resistance as a substitute material for a glass plate.
As a material of a resin plate having excellent transparency, a (meth) acrylic resin, a polycarbonate resin, a styrene resin, an MS resin, and the like are known. Among them, the (meth) acrylic resin is excellent in transparency, heat resistance and weather resistance, and has a well-balanced performance in resin properties such as moldability and mechanical strength.
However, in general, (meth) acrylic resin does not have sufficient impact resistance and abrasion resistance, and therefore, while maintaining high moldability of (meth) acrylic resin, it can be used for display front panel applications. Many proposals have been made to improve impact resistance and scratch resistance.

For example, in Patent Document 1, at least one surface of an acrylic resin plate containing an impact resistance improver (ethylene-methyl acrylate copolymer) is provided with a repeating unit derived from a urethane acrylate compound and (meth) acryloyl. Scratch resistance and scratch resistance provided with a repeating unit derived from a polyfunctional monomer having 5 to 6 groups and a repeating unit derived from a polyfunctional monomer having 2 (meth) acryloyl groups A (meth) acrylic resin laminate excellent in impact properties has been proposed.
Patent Document 2 discloses that a polymerizable compound having at least two (meth) acryloyloxy groups in a molecule is provided on a surface of a resin substrate made of an acrylic resin composition containing a rubber-containing acrylic multi-stage polymer. A (meth) acrylic resin laminate excellent in abrasion resistance and impact resistance, in which a hard coat film is formed by applying an activating energy ray such as ultraviolet rays after applying a curable composition containing the same, has been proposed. I have.

WO2015 / 093404 JP 2007-291206 A

However, according to the methods described in Patent Literature 1 and Patent Literature 2, the scratch resistance of the (meth) acrylic resin laminate itself is improved, but the impact resistance and moldability are not sufficient.
The present invention aims to solve these problems. That is, an object of the present invention is to provide a resin laminate excellent in impact resistance, scratch resistance, and moldability.

A first gist of the present invention is a resin laminate having a cured film (B1) on one surface of a sheet-shaped resin substrate (A), wherein the cured film (B1) has a radical polymerizable function. A repeating unit derived from a urethane (meth) acrylate (B1-1) having 2 to 5 groups and having a urethane bond in the molecule, and a polyfunctional (meth) acrylate having two radical polymerizable functional groups It contains a resin composition containing a repeating unit derived from (B1-2) (however, excluding the repeating unit derived from polyfunctional (meth) acrylate (B1-1)), and constitutes the cured film (B1). in each of the polyfunctional (meth) acrylate (i) having a radical polymerizable functional group of 2 or more, the average molecular weight of each of the polyfunctional (meth) acrylate (i) M _i, each of the polyfunctional (meth) acrylate The number of radically polymerizable functional groups F _i in _(i), the mass fraction of each of the polyfunctional (meth) acrylate (i) as W _{i (wt%)} constituting the cured film (B1), the following formula Satisfy (1),


[Wherein, W i _(mass%) in the cured film (B1), a polyfunctional (meth) acrylate (i) each of the mass fraction having at least two radical-polymerizable functional group, M _i is the respective average molecular weight of the polyfunctional (meth) acrylate (i), F _i is the polyfunctional (meth) acrylate the number of radically polymerizable functional groups of the respective polyfunctional (meth) acrylate (i), k is chosen (i ) Represents an integer of 2 or more. ]
The resin substrate (A) is made of a (meth) acrylic resin composition containing an impact modifier (D), and the impact modifier (D) is a multi-structure acrylic copolymer particle ( D1) or at least one resin laminate selected from acrylic block copolymers (D2).
The cured film (B1) is obtained by dividing the numerical value of the average molecular weight of the urethane (meth) acrylate (B1-1) by the number of radically polymerizable functional groups of the urethane (meth) acrylate (B1-1). It is preferable that the divided value (average molecular weight / number of functional groups) be 180 or more and 900 or less.
In addition, at the boundary between the resin substrate (A) and the cured film (B1), a mixture formed by mixing the components of the resin substrate (A) and the components of the cured film (B1) with each other. The layer (A-B1) can be formed with a thickness of 0.1 μm or more and 3.0 μm or less.
In the cured film (B1), the sum of the content of the repeating unit derived from the urethane (meth) acrylate (B1-1) and the content of the repeating unit derived from the polyfunctional (meth) acrylate (B1-2) is determined by the curing. It is preferable that the resin composition contains 92% by mass or more and 100% by mass or less with respect to the total mass of the coating (B1).
The resin laminate may be a resin laminate having a cured film (B2) on the surface on the other side of the resin base material (A). The cured film (B2) has two or more and five or less radical polymerizable functional groups and has a urethane bond in the molecule and contains a repeating unit derived from a urethane (meth) acrylate (B2-1) in an amount of 0. 0 to 90% by mass and a repeating unit derived from a polyfunctional (meth) acrylate (B2-2) having two radical polymerizable functional groups (provided that the polyfunctional (meth) acrylate (B2-1) is derived) And a repeating unit derived from a polyfunctional (meth) acrylate (B2-3) having 3 to 6 radically polymerizable functional groups (excluding the repeating unit of A resin composition containing at least 0.0% by mass and at most 80% by mass of a functional (meth) acrylate (excluding a repeating unit derived from (B2-1)).
A mixed layer (A-B2) of the components of the resin substrate (A) and the components of the cured film (B2) is provided at the boundary between the resin substrate (A) and the cured film (B2). And a thickness of 0.1 μm or more and 3.0 μm or less.
A second gist of the present invention resides in a display front plate including the resin laminate.
A third aspect of the present invention resides in a portable information terminal device including the display front panel.

According to the present invention, a resin laminate excellent in impact resistance, scratch resistance, and moldability can be provided.
The resin laminate of the present invention is suitable for a display front plate for protecting a display surface of a portable information terminal device such as a mobile phone, a car navigation display device, and a portable game device.

FIG. 1 is a schematic view showing a cross section of a resin laminate in which a cured film is laminated on one surface of a resin substrate, which is one embodiment of the present invention. FIG. 1 is a schematic view showing a cross section of a resin laminate in which a cured film is laminated on both surfaces of a resin substrate, which is one embodiment of the present invention. It is an observation image by a transmission electron microscope of a small piece cut out from a cut surface of a resin laminate, and is an example of an observation image when a three-layer structure of a layer of a resin base material / a mixed layer / a cured film layer is observed. It is. It is an image observed by a transmission electron microscope about a small piece cut out from a cut surface of a resin laminate, and is an example of an observation image when a mixed layer is not observed between a layer of a resin base material and a layer of a cured film.

Hereinafter, the present invention will be described in detail. In the present invention, “(meth) acrylate” and “(meth) acrylic acid” are at least one selected from “acrylate” and “methacrylate” and at least one selected from “acrylic acid” and “methacrylic acid”, respectively. Means
Further, “monomer” means an unpolymerized compound, and “repeating unit” means a unit derived from the monomer and formed by polymerization of the monomer. The repeating unit may be a unit directly formed by a polymerization reaction, or a unit in which a part of the unit is converted to another structure by treating the polymer.
Further, “% by mass” indicates the content of a predetermined component contained in the total amount of 100% by mass.
<Resin laminate>
The resin laminate according to one embodiment of the present invention is a resin laminate having a cured film (B1) described later on one surface of a sheet-shaped resin substrate (A) described later.
In the resin laminate of the present invention, the component of the cured film (B1) and the component of the resin substrate (A) are mixed with each other at the boundary between the cured film (B1) and the resin substrate (A). The formed mixed layer (A-B1) can be provided.

A resin laminate according to another embodiment of the present invention includes a cured resin film (B1) on one surface of a sheet-shaped resin substrate (A), and a cured film (described later) on one other surface. A resin laminate having (B2) can also be obtained.
The resin laminate of the present invention is formed by mixing the components of the cured film (B2) and the components of the resin substrate (A) at the boundary between the cured film (B2) and the resin substrate (A). Mixed layer (A-B2) can be provided.

<Curing film (B1)>
In the resin laminate of the present invention, the cured coating (B1) has a specific urethane-based polyfunctional (meth) acrylate (which will be described later) as a component in order to simultaneously improve impact resistance, scratch resistance, and moldability. It contains a resin composition containing a repeating unit derived from B1-1) and a repeating unit derived from a bifunctional (meth) acrylate (B1-2) described below, and specifies the crosslink density of the cured film (B1). The feature is that the range is
That is, the cured film (B1)
A repeating unit derived from a urethane (meth) acrylate (B1-1) having two to five radical polymerizable functional groups and having a urethane bond in the molecule;
A repeating unit derived from a polyfunctional (meth) acrylate (B1-2) having two radical polymerizable functional groups (excluding the polyfunctional (meth) acrylate (B1-1))
Is a cured film containing a resin composition containing
The radically polymerizable functional group referred to herein may be any group having a carbon-carbon double bond and capable of undergoing radical polymerization. Specifically, a vinyl group, an allyl group, a (meth) acryloyl group, And a (meth) acryloyloxy group. In particular, a (meth) acryloyl group is preferable from the viewpoint of excellent storage stability of a compound having a radical polymerizable functional group and from the viewpoint of easily controlling the polymerizability of the compound. Further, among the (meth) acryloyl groups, the acryloyl group is preferable from the viewpoint of a high curing rate when irradiated with active energy rays. In addition, “(meth) acryloyl” indicates one or both of “acryloyl” and “methacryloyl”. The radical polymerizable functional groups in the monomer having two or more radical polymerizable functional groups may be the same or different.

  In the cured film (B1), the repeating unit derived from (B1-1) contains a urethane bond, so that the adhesion between the resin substrate (A) and the cured film (B1) is increased, so that the cured film has scratch resistance. The cured film (B1) has good flexibility by having two to five radically polymerizable functional groups contained in the repeating unit, and thus forming the resin laminate. Compatibility (crack resistance) and impact resistance. Specific urethane (meth) acrylate (B1-1) will be described later.

  A resin laminate in which a cured film is laminated on the surface of a resin substrate by including, as a constituent, a polyfunctional repeating unit having two radical polymerizable functional groups in the cured film (B1). Warpage can be suppressed, and the scratch resistance of the cured film can be improved. Specific polyfunctional (meth) acrylate (B1-2) will be described later.

  Depending on the purpose for which the resin laminate is used, the cured film (B1) is a radically polymerizable polymer, excluding the repeating unit derived from (B1-1) and the repeating unit derived from (B1-2) as constituent components. It may contain a polyfunctional (meth) acrylate (B1-3) having 3 to 6 functional groups.

Further, in the resin laminate of the present invention, in each of the polyfunctional (meth) acrylates (i) having two or more radically polymerizable functional groups constituting the cured coating (B1), each polyfunctional (meth) acrylate acrylate (i) an average molecular weight M _i of _each of the polyfunctional (meth) acrylate the number of radically polymerizable functional groups F _i in _(i), polyfunctional each constituting the cured film (B1) (meth) Assuming that the mass fraction of the acrylate (i) is W _i (mass%), the sum of the values obtained by dividing the numerical value of the average molecular weight by the number of radical polymerizable functional groups (average molecular weight M _i / number of functional groups F _i ) is represented by the following formula: It is preferable to satisfy (1). Here, the “polyfunctional (meth) acrylate (i)” refers to the urethane-based (meth) acrylate (B1-1), the polyfunctional (meth) acrylate (B1-2), and the polyfunctional (meth) acrylate. ) Acrylate (B1-3).

[Wherein, W i _(mass%) in the cured film (B1), a polyfunctional (meth) acrylate (i) each of the mass fraction having at least two radical-polymerizable functional group, M _i is the respective average molecular weight of the polyfunctional (meth) acrylate (i), F _i is the polyfunctional (meth) acrylate the number of radically polymerizable functional groups of the respective polyfunctional (meth) acrylate (i), k is chosen (i ) Represents an integer of 2 or more. ]

In the above formula (1), M _i / F _i (= average molecular weight / number of functional groups) is the length of the distance between carbon-carbon double bonds when each polyfunctional (meth) acrylate (i) is polymerized and cross-linked. Therefore, the sum of (M _{i ×} W _i ) / (F _i × 100) in the formula (1) is an index value representing the crosslink density when the cured coating (B1) is viewed as a whole. As this value is larger, the distance between crosslinks is increased, so that the crosslink density of the entire cured coating (B1) is lower.
If the lower limit of the index value of the formula (1) is 170 or more, a sufficient distance between the cross-linking points of the cured coating (B1) can be ensured, so that it is possible to also have flexibility. When the resin laminate is processed into a curved surface or a complicated shape, the cured film (B1) follows the resin base material (A) and is easily deformed, or the curable composition is cured to form a cured film. The effect of lowering the curing shrinkage when performing is combined with the performance of the urethane (meth) acrylate (B1-1) itself, and the resulting resin laminate has good impact resistance and moldability (cracking resistance). It is preferable from a viewpoint which becomes, 180 or more are more preferable, and 190 or more are more preferable. When the upper limit of the index value is 650 or less, the number of cross-linking points in the cured film (B1) can be secured to a certain amount or more. Therefore, the urethane (meth) acrylate (B1-1) is used. It is preferable from the viewpoint that the abrasion resistance of the cured film is good in combination with the performance of the cured film itself, and is preferably 550 or less, more preferably 450 or less, and particularly preferably 350 or less. That is, it is possible to obtain a resin laminate having both improved moldability and impact resistance. The above upper limit and lower limit can be arbitrarily combined.

  Further, in the cured film (B1), the numerical value of the average molecular weight of the urethane (meth) acrylate (B1-1) is calculated by the number of radical polymerizable functional groups of the urethane (meth) acrylate (B1-1). If the lower limit of the divided value (average molecular weight / number of functional groups) is 180 or more, it is preferable from the viewpoint of improving impact resistance and moldability (crack resistance), preferably 200 or more, more preferably 230 or more. . On the other hand, the upper limit is not particularly limited, but is preferably at most 650 from the viewpoint of improving the scratch resistance, more preferably at most 650, even more preferably at most 550. The above upper and lower limits can be arbitrarily combined.

  When the lower limit of the content of the repeating unit derived from (B1-1) in the cured film (B1) is 35% by mass or more based on the total mass of the cured film (B1), the obtained resin laminate is obtained. Is preferable because the impact resistance and the molding processability of the resin are improved, and more preferably 40% by mass or more. The upper limit of the content is preferably 90% by mass or less based on the total mass of the cured film (B1), since the resulting resin laminate has good scratch resistance, and more preferably 80% by mass or less. . The above upper and lower limits can be arbitrarily combined.

  When the lower limit of the content of the repeating unit derived from (B1-2) in the cured film (B1) is 10% by mass or more based on the total mass of the cured film (B1), the obtained resin laminate is obtained. Is preferable because the scratch resistance of the cured film is good, and more preferably 20% by mass or more. If the upper limit of the content is 65% by mass or less with respect to the total mass of the cured film (B1), the curable composition is cured, and the curing shrinkage at the time of forming the cured film is reduced, In the obtained resin laminate, the molding processability (crack resistance) of the cured film is favorable, and is preferably 60% by mass or less. The above upper and lower limits can be arbitrarily combined.

  The lower limit of the total content of the repeating units derived from (B1-1) and the repeating units derived from (B1-2) in the cured film (B1) is based on the total mass of the cured film (B1). If it is 92% by mass or more, it is preferable from the viewpoint that the abrasion resistance, impact resistance, and moldability of the resin laminate can be compatible, more preferably 95% by mass or more, even more preferably 98% by mass or more. The upper limit of the total content is not particularly limited, and may be 100% by mass or less than 100% by mass.

  The pencil hardness of the surface of the cured film (B1) is not particularly limited. However, if it is 3H or 4H, when the resin laminate of the present invention is used as it is as a display front plate, it is scratched by a finger nail or the like of the display front plate. The generation of scratches can be suppressed, and the scratch resistance becomes good.

<Curing film (B2)>
In the resin laminate of the present invention, the scratch resistance is provided by providing the above-described cured film (B1) on one surface of the resin base material (A) and the cured film (B2) on the other surface. Can be made more excellent.
The cured film (B2) has a repeating unit derived from a urethane (meth) acrylate (B2-1) having a urethane bond in the molecule and a polyfunctional (meth) acrylate (B2) having two radical polymerizable functional groups. -2) a repeating unit derived from the polyfunctional (meth) acrylate (excluding the repeating unit derived from the polyfunctional (meth) acrylate (B2-1)) and a polyfunctional (meth) acrylate having from 3 to 6 radically polymerizable functional groups A resin composition containing a repeating unit derived from (B2-3) (excluding the repeating unit derived from polyfunctional (meth) acrylate (B2-1)) can be included.
The same radical polymerizable functional group as that used in the cured film (B1) can be used as the radical polymerizable functional group.
Further, urethane-based (meth) acrylate (B2-1), polyfunctional (meth) acrylate (B2-2), and polyfunctional (meth) acrylate (B2-3) are used for the cured coating (B1), respectively. The same urethane (meth) acrylate (B1-1), polyfunctional (meth) acrylate (B1-2), and polyfunctional (meth) acrylate (B1-3) can be used.

As one embodiment of the cured film (B2), the total mass of the cured film (B2) is:
-35 mass% or more and 90 mass% or less of the repeating unit derived from (B2-1)-A cured film containing a resin composition containing 10 mass% or more and 65 mass% or less of the repeating unit (B 2-2). be able to.
The lower limit of the total content of the repeating unit derived from (B1-1) and the repeating unit derived from (B1-2) is at least 92% by mass based on the total mass of the cured film (B2). It is preferable from the viewpoint that the abrasion resistance, impact resistance, and moldability of the resin laminate are compatible, and is preferably 95% by mass or more, more preferably 98% by mass or more. The upper limit of the total content is not particularly limited, and may be 100% by mass or less than 100% by mass.

Alternatively, as another embodiment of the cured film (B2), the total mass of the cured film (B2) is:
-10% by mass or more and 40% by mass or less of the repeating unit derived from (B2-2)-A cured film containing a resin composition containing 60% by mass or more and 90% by mass or less of the repeating unit (B2-3) be able to.

Alternatively, as another embodiment of the cured film (B2), the total mass of the cured film (B2) is:
-The repeating unit derived from (B2-1) is 5% by mass or more and 35% by mass or less-The repeating unit derived from (B2-2) is 50% by mass or more and 70% by mass or less-The repeating unit derived from (B2-3) 5 is A cured coating containing a resin composition containing not less than 15% by mass and not more than 15% by mass can be given.

  The pencil hardness of the surface of the cured film (B2) is not particularly limited. However, by setting the pencil hardness to 3H or more, such as a glazing for a moving body, which is required to have scratch resistance on both surfaces of a resin laminate. It is preferable because it can be used.

<Urethane (meth) acrylate (B1-1)>
Urethane-based (meth) acrylate (B1-1) is a constituent component of the cured film (B1) and is a monomer having two to five radical polymerizable functional groups and having a urethane bond in the molecule. is there. When the monomer has 2 to 5 (meth) acryloyl groups in the molecule, the effect of improving the scratch resistance of the obtained resin laminate is obtained.
Specific examples include the following monomers 1) to 3), but are not limited thereto.

  1) a urethane (meth) acrylate obtained by reacting 3 moles or more of an acrylic monomer having active hydrogen with 1 mole of a polyisocyanate represented by the following formula (I);

Examples of the polyisocyanate include trimethylolpropane tolylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, and trimethylhexamethylene diisocyanate. Compounds having one isocyanuric acid skeleton in the molecule, which are obtained by quantification, may be mentioned. By having one isocyanuric acid skeleton in the molecule of the monomer, an effect of improving the moldability (crack resistance) of the obtained resin laminate can be obtained.
... (I)
(Wherein, R represents a divalent hydrocarbon group having 1 to 12 carbon atoms which may contain a substituent)

Examples of the acrylic monomer having active hydrogen include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-methoxypropyl (meth) acrylate, and N-methylol (meth). Hydroxy group-containing (meth) such as acrylamide, N-hydroxy (meth) acrylamide, 1,2,3-propanetriol-1,3-di (meth) acrylate, 3-acryloyloxy-2-hydroxypropyl (meth) acrylate Acrylates and compounds obtained by modifying these hydroxy group-containing (meth) acrylates with caprolactone can be mentioned.
Examples of urethane (meth) acrylate obtained by reacting polyisocyanate with an acrylic monomer having active hydrogen include tris [(meth) acryloyloxyethyl] isocyanurate and tris [2- (meth) acryloyloxypropyl] isocyanate. Nurate, bis [(meth) acryloyloxyethyl] hydroxyethyl isocyanurate, bis [2- (meth) acryloyloxypropyl] -2-ethoxypropyl isocyanurate, tris [(meth) acryloyloxyethoxyethyl] isocyanurate and these Mixtures are mentioned.

2) poly [(meth) acryloyl] isocyanate;
For example, tris [(meth) acryloyloxyethyl] isocyanurate, tris [2- (meth) acryloyloxypropyl] isocyanurate, bis [(meth) acryloyloxyethyl] hydroxyethyl isocyanurate, bis [2- (meth) acryloyl) Oxypropyl] -2-ethoxypropyl isocyanurate, tris [(meth) acryloyloxyethoxyethyl] isocyanurate and mixtures thereof.

3) Known urethane polyacrylates Known urethane polyacrylates include a hydroxy group-containing (meth) acrylate (m1) having an acryloyloxy group and a hydroxy group in a molecule, and a diisocyanate having two isocyanate groups in a molecule ( m2).
The (meth) acrylate (m1) is not particularly limited as long as it is a hydroxy group-containing (meth) acrylate having an acryloyloxy group and a hydroxy group in a molecule. Specific examples of the above (m1) include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- (2-hydroxyethoxy) ethyl (meth) acrylate, 3-hydroxypropyl (meth) ) Acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, 2- Examples include an adduct of hydroxyethyl (meth) acrylate and caprolactone, an adduct of 4-hydroxybutyl (meth) acrylate and caprolactone, and trimethylolpropane diacrylate. These can be used alone or in combination of two or more.
Among them, from the viewpoint of reducing the viscosity of the resulting composition, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- (2-hydroxyethoxy) ethyl (meth) acrylate, Hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate are preferred.
The diisocyanate (m2) is not particularly limited as long as it is a diisocyanate having two isocyanate groups in the molecule. Specific examples of the above (m2) include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate Aromatic diisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; isophorone diisocyanate, bis (4-isocyanatocyclohexyl) methane, 1,3-bisisocyanatomethylcyclohexane, 1,4-bisisocyanatomethylcyclohexane And alicyclic diisocyanate compounds such as norbornane diisocyanate.
Among these, an alicyclic diisocyanate compound is more preferable because the obtained cured product is excellent in yellowing resistance and toughness.

  One of the above may be used alone, or two or more may be used in combination as needed. These monomers may be used as they are, or oligomers such as dimers and trimers may be used. Further, a monomer and an oligomer may be used in combination.

<Polyfunctional (meth) acrylate (B1-2)>
The polyfunctional (meth) acrylate (B1-2) is a component of the cured film (B1) and is a monomer having two radically polymerizable functional groups (however, the urethane-based (meth) acrylate (B1) -1)).
Specifically, ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylol Propane di (meth) acrylate, ethylene oxide adduct trimethylolpropane di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1 , 6-hexanediol di (meth) acrylate, polyester di (meth) acrylate, polyethylene glycol di (meth) acrylate, tricyclodecane dimethylol di (meth) acryle Neopentylglycol hydroxypivalate di (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, 1,10-decanediol di (meth) acrylate and neopentylglycol hydroxypivalate di (meth) acrylate. However, the present invention is not limited to these.
Among them, preferably, 1,6-hexanediol di (meth) acrylate is used. Further, one of the above monomers can be used alone or in combination of two or more monomers.
<Polyfunctional (meth) acrylate (B1-3)>
The polyfunctional (meth) acrylate (B1-3) is a constituent component of the cured film (B1), and is a monomer having three to six radical polymerizable functional groups (however, the urethane (meth) acrylate). (B1-1) and polyfunctional (meth) acrylate (B1-2) are excluded), and are not particularly limited.
From the viewpoint of improving the scratch resistance of the cured film, trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate and the like. One of the above monomers can be used alone or in combination of two or more.

<Urethane (meth) acrylate (B2-1)>
Urethane-based (meth) acrylate (B2-1) is a constituent component of the cured film (B2) and is a monomer having two to five radical polymerizable functional groups and having a urethane bond in the molecule. is there. As the urethane-based (meth) acrylate (B2-1), the same urethane-based (meth) acrylate (B1-1) as a component of the cured film (B1) can be used.

<Polyfunctional (meth) acrylate (B2-2)>
The polyfunctional (meth) acrylate (B2-2) is a constituent component of the cured film (B2) and is a monomer having two radically polymerizable functional groups (however, the urethane-based (meth) acrylate (B2- 1)).
As the polyfunctional (meth) acrylate (B2-2), the same polyfunctional (meth) acrylate (B1-2) as a component of the cured film (B1) can be used.

<Polyfunctional (meth) acrylate (B2-3)>
The polyfunctional (meth) acrylate (B2-3) is a constituent component of the cured film (B2), and is a monomer having 3 to 6 radical polymerizable functional groups (however, the polyfunctional (meth) ) Excluding acrylate (B2-1)).
As the polyfunctional (meth) acrylate (B2-3), the same polyfunctional (meth) acrylate (B1-3) as a component of the cured film (B1) can be used.

<Mixed layer>
In the resin laminate of the present invention, the components of the resin substrate (A) and the components of the cured film (B1) are mixed and formed at the boundary between the resin substrate (A) and the cured film (B1). Mixed layer (A-B1) can be provided. Further, a mixed layer (A-) formed by mixing the components of the resin substrate (A) and the components of the cured film (B2) at the boundary between the resin substrate (A) and the cured film (B2). B2) can be provided.
That is, the resin laminate of the present invention includes a mixed layer formed by mixing the components of the resin substrate and the components of the cured film at the boundary between the resin substrate and the cured film, and is adjacent to the mixed layer. A three-layer structure including two non-mixed layers (a resin base material layer and a cured film layer).
In the mixed layer, the concentration of the components of the cured film increases continuously from the resin substrate side to the cured film side. The continuous increase in the concentration of the components of the cured film can be confirmed by measuring the change in the refractive index on the cut surface of the resin laminate. Specifically, a change in the refractive index can be measured by measuring a reflection spectrum using an instantaneous multi-photometer (manufactured by Otsuka Electronics Co., Ltd., product name “MCPD3700”).
In order to determine the presence or absence of the mixed layer, a mixed layer and two non-mixed layers adjacent to the mixed layer (the layer of the resin substrate and the cured Layer of the coating). The thickness of the mixed layer can be measured in the same manner.

  In the resin laminate of the present invention, by forming the mixed layer, the adhesion between the resin substrate (A) and the cured film (B1) and the adhesion between the resin substrate (A) and the cured film (B2). And the impact resistance, scratch resistance, and moldability (crack resistance) of the resin laminate are improved.

The thickness of the mixed layer (A-B1) is preferably 0.1 μm or more and 3.0 μm or less. When the lower limit of the thickness is 0.1 μm or more, it is preferable from the viewpoint of improving the impact resistance and moldability (crack resistance) of the resin laminate. When the upper limit of the thickness is 3.0 μm or less, the thickness of the resin laminate is reduced. It is preferable from the viewpoint of improving the scratch resistance.
The thickness of the mixed layer (A-B2) is preferably 0.1 μm or more and 3.0 μm or less. When the lower limit of the thickness is 0.1 μm or more, it is preferable from the viewpoint of improving the impact resistance and molding workability of the resin laminate, and when the upper limit of the thickness is 3.0 μm or less, the scratch resistance of the resin laminate is good. It is preferable from the viewpoint of becoming.
A specific method for controlling the thickness of the mixed layer will be described later.

  The thickness of the mixed layer can be measured by a method described later.

<Resin base material (A)>
The resin substrate (A) is composed of a (meth) acrylic resin composition substantially containing a (meth) acrylic polymer (P) described later and an impact resistance improver (D) described later as main components. Here, “contains substantially as a main component” means that the (meth) acrylic polymer (P) and the impact resistance improver (D) are defined assuming that the total weight of the resin base material (A) is 100% by mass. ) Is 90% by mass or more.
<(Meth) acrylic resin composition>
As an example of an embodiment of the (meth) acrylic resin composition, 2.0 parts by mass or more of the impact modifier (D) is added to 100 parts by mass of the (meth) acrylic polymer (P). Resin compositions containing 0 parts by mass or less can be mentioned.
If the lower limit of the content of the impact modifier (D) is at least 2.0 parts by mass based on 100 parts by mass of the (meth) acrylic polymer, the impact resistance of the resin laminate will be good, and the value is preferably 5.0. It is more preferably at least part by mass. Further, if the upper limit of the content of the impact modifier (D) to 100 parts by mass of the (meth) acrylic polymer is 50.0 parts by mass or less, the flame retardancy and weather resistance of the resin laminate become good. It is preferably at most 30.0 parts by mass, more preferably at most 20.0 parts by mass.

<(Meth) acrylic polymer (P)>
As an example of the embodiment of the (meth) acrylic polymer (P), a homopolymer of 100% by mass of a repeating unit derived from methyl methacrylate based on the total mass of the (meth) acrylic polymer (P), or Copolymers containing 80% by mass or more and less than 100% by mass of repeating units derived from methyl methacrylate and more than 0% by mass and 20% by mass or less of repeating units derived from a monomer copolymerizable with methyl methacrylate. it can.
Examples of monomers copolymerizable with methyl methacrylate include ethyl (meth) acrylate, isopropyl (meth) acrylate, t-butyl (meth) acrylate, i-butyl (meth) acrylate, and (meth) acrylic acid. Unsaturated carboxylic acids such as n-butyl acid, (meth) acrylic acid, maleic acid, and itaconic acid; acid anhydrides such as maleic anhydride and itaconic anhydride; maleimide derivatives such as N-phenylmaleimide and N-cyclohexylmaleimide; Vinyl esters such as vinyl acetate and vinyl benzoate; vinyl chloride, vinylidene chloride and derivatives thereof; nitrogen-containing monomers such as methacrylamide and acrylonitrile; epoxy-containing monomers such as glycidyl acrylate (meth) acrylate; and styrene And aromatic vinyl compounds such as α-methylstyrene.

  Further, the (meth) acrylic polymer (P) may include a repeating unit derived from a monomer (B) having two or more vinyl groups described below.

<Monomer (B)>
The monomer (B) is a monomer having two or more radically polymerizable functional groups, and is one of the components of the (meth) acrylic polymer (P). When the (meth) acrylic polymer (P) contains a structural unit derived from the monomer (B), the scratch resistance of the resin laminate can be further improved.
The radical polymerizable functional group is the same as the radical polymerizable functional group described in the cured film (B1).
As the monomer (B), a bifunctional (meth) acrylate is preferable. For example, ethylene glycol di (meth) acrylate (EDMA), 1,2-propylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl Alkanediol di (meth) acrylates such as glycol di (meth) acrylate (NPGDMA) and tricyclodecane dimethanol di (meth) acrylate are exemplified. These can be used alone or in combination of two or more.
Among the above-mentioned monomers (B), EDMA and NPGDMA are preferable from the viewpoint that the handleability of the raw materials is excellent and the impact resistance and the moldability of the resin laminate can be further improved.
The content of the repeating unit derived from the monomer (B) contained in the (meth) acrylic polymer (P) is not particularly limited, but the impact resistance and the moldability of the resin laminate are improved. The content is preferably 0.05% by mass to 0.40% by mass, more preferably 0.12% by mass to 0.36% by mass, based on the total mass of the (meth) acrylic polymer (P).

<Impact improver (D)>
In the present invention, in order to enhance the impact resistance of the resin laminate, the (meth) acrylic resin composition is used as an impact resistance improver (D) as the multi-layer acrylic copolymer particles (D1) described later or described later. It is preferable that at least one compound selected from the acrylic block copolymer (D2) is included as one of the constituent components.

<Multi-layer acrylic copolymer particles (D1)>
The multi-layer acrylic copolymer particles (D1) used in the present invention are acrylic copolymer particles containing at least one elastomer particle (d1-1) composed of a rubbery copolymer layer having a crosslinked structure. . The composition and particle size of each layer of the multi-layer acrylic copolymer particles (D1) are not limited as long as they have a rubber-like copolymer layer having a crosslinked structure.

For example, a multi-structured acrylic copolymer particle (D1-1) having a structure in which a hard resin layer (d1-2) is formed outside the elastomer particle (d1-1) can be given.
Further, there can be mentioned a multi-structure acrylic copolymer particle (D1-2) in which a hard resin layer (d1-3) having a crosslinked structure is formed inside the elastomer particle (d1-1).
Further, a multi-structure acrylic copolymer particle in which a hard resin layer (d1-4) is further formed inside the hard resin layer (d1-2) and outside the hard resin layer (d1-2). (D1-3).

<Multilayer acrylic copolymer particles (D1-1)>
The multi-structured acrylic copolymer particles (D1-1) are obtained by graft-polymerizing a hard resin component onto the surface of elastomer particles (d1-1) made of a rubbery copolymer having a crosslinked structure, The multi-layer acrylic copolymer particles (D1-1) on which the layer (d1-2) is formed can be used.

(Elastomer particles: d1-1)
Examples of the rubbery copolymer constituting the elastomer particles (d1-1) include a (co) polymer having a repeating unit derived from an alkyl acrylate as a main component.
Specifically, 70 to 90% by mass of a repeating unit derived from an alkyl acrylate having 1 to 8 carbon atoms in an alkyl group, 10 to 30% by mass of a repeating unit derived from an aromatic vinyl monomer, and other copolymerizable compounds It is a (co) polymer containing 0 to 20% by mass of a repeating unit derived from a monomer.
Examples of the alkyl acrylate having 1 to 8 carbon atoms in the alkyl group include methyl acrylate, ethyl acrylate, i-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate. These monomers are used alone or in combination of two or more.
Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, and vinyl toluene. These monomers are used alone or in combination of two or more.
Examples of the other copolymerizable monomers include methacrylates such as methyl methacrylate, ethyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate, and vinyl cyanide compounds such as (meth) acrylonitrile. Further, it may contain the following polyfunctional monomers.
Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, 1,3-butylene di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, allyl (meth) acrylate, Crosslinking agents such as divinylbenzene, and crosslinking agents such as trimethylolpropane triacrylate, triallyl isocyanurate, and pentaerythritol tetraacrylate are exemplified. These monomers are used alone or in combination of two or more.
The mass average particle diameter of the elastomer particles (d1-1) is not particularly limited, but is generally 100 to 300 nm.

(Hard resin layer: d1-2)
The hard resin component forming the hard resin layer (d1-2) may include a (co) polymer having a repeating unit derived from a methacrylate ester as a main component.
Specifically, a repeating unit derived from an alkyl methacrylate having 1 to 4 carbon atoms in an alkyl group has a mass of 50% by mass or more and 100% by mass or less, and a repeating unit derived from an alkyl acrylate having 1 to 8 carbon atoms in an alkyl group has 0% by mass or more. It is a (co) polymer containing 50% by mass or less, and 0% by mass or more and 20% by mass or less of repeating units derived from other copolymerizable monomers.
Examples of the alkyl methacrylate having 1 to 4 carbon atoms in the alkyl group include methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacryl esters such as n-butyl methacrylate, and methyl acrylate and acrylic esters such as ethyl acrylate. Can be These monomers are used alone or in combination of two or more.
Examples of the 0 to 50% by mass of the repeating unit derived from an alkyl acrylate having 1 to 8 carbon atoms in the alkyl group include elastomer particles (d1-1) containing the above-mentioned rubbery copolymer having a crosslinked structure. Similar ones can be used.
Other copolymerizable monomers include styrene, α-methylstyrene, aromatic vinyl monomers such as vinyltoluene, non-alkyl methacrylates such as phenyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate, and non-alkyl methacrylates corresponding thereto. And alkyl acrylate. Further, the above-mentioned polyfunctional monomer may be included.

<Multilayer acrylic copolymer particles (D1-2)>
The multi-structured acrylic copolymer particles (D1) used in the present invention are obtained by forming a hard resin layer (d1-3) having a crosslinked structure inside the elastomer particles (d1-1). Polymer particles (D1-2) can be used.

(Hard resin layer having crosslinked structure: d1-3)
Examples of the hard resin component forming the hard resin layer (d1-3) include a (co) polymer having a repeating unit derived from an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms as a main component.
The hard resin component forming the hard resin layer (d1-3) may be the same resin component as the hard resin layer (d1-2) or a different resin component.
Specifically, a repeating unit derived from an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms is 40% by mass or more and 100% by mass or less, and a repeating unit derived from an alkyl acrylate having 1 to 8 carbon atoms is 0% by mass or more. (Co) weight containing 60% by mass or less, and 0 to 20% by mass of a repeating unit derived from another copolymerizable monomer and 0.1% by mass or more and 10% by mass or less of a repeating unit derived from a polyfunctional monomer. Coalescence can be mentioned. By setting the composition within the above ranges, excellent falling ball / falling weight impact strength, impact whitening resistance, and transparency can be obtained.
Alkyl methacrylate having 1 to 4 carbon atoms in the alkyl group, alkyl acrylate having 1 to 8 carbon atoms in the alkyl group, and other copolymerizable monomers used in the hard resin layer (d1-3) having the crosslinked structure. The same thing as the hard resin layer (d1-2) mentioned above can be used for a monomer and a polyfunctional monomer.

  The hard resin layer (d1-3) when the amount of the elastomer particles (d1-1) is 100 parts by mass is not particularly limited, but is generally 30 parts by mass or more and 100 parts by mass or less. .

<Multilayer acrylic copolymer particles (D1-3)>
The multi-structure acrylic copolymer particles (D1) used in the present invention are located outside the hard resin layer (d1-2) of the multi-structure acrylic copolymer particles (D1-1) or (D1-2). In addition, multi-layer acrylic copolymer particles (D1-3) on which a hard resin layer (d1-4) is further formed can be used.

(Hard resin layer: d1-4)
Examples of the hard resin component forming the hard resin layer (d1-4) include a (co) polymer having a repeating unit derived from methyl methacrylate as a main component.
Specifically, 50 to 100% by mass of a repeating unit derived from an alkyl methacrylate having 1 to 4 carbon atoms in an alkyl group, 0 to 50% by mass of a repeating unit derived from an alkyl acrylate having 1 to 8 carbon atoms in the alkyl group, and A (co) polymer containing 0 to 20% by mass of a repeating unit derived from an aromatic vinyl monomer, and a glass transition temperature (hereinafter abbreviated as “Tg”) of the hard resin layer (d1-4). Is 20 to 80 ° C. and lower than the Tg of the hard resin layer (d1-2). The above-mentioned multi-structure acrylic copolymer particles (D1) can be produced by a known method.
As the multi-layer acrylic copolymer particles (D1) other than the above, commercially available products such as W-341 manufactured by Mitsubishi Rayon Co., Ltd. and M-210 manufactured by Kaneka Corporation can be obtained.
The lower limit of the content of the multi-structured acrylic copolymer particles (D1) in the (meth) acrylic resin composition is determined from the viewpoint that the impact resistance of the resin laminate is improved. (P) It is preferably at least 2.0 parts by mass, more preferably at least 5.0 parts by mass, per 100 parts by mass. The upper limit of the content of the multi-layer acrylic copolymer particles (D1) is preferably 20 parts by mass or less, and more preferably 15 parts by mass or less, from the viewpoint of maintaining good flame retardancy and weather resistance of the resin laminate. .

<Acrylic block copolymer (D2)>
The acrylic block copolymer (D2) used in the present invention comprises an acrylic block copolymer having a methacrylate polymer block (d2-1) and an acrylate polymer block (d2-2). Specifically, an acrylic block having 10% by mass or more and 60% by mass or less of a methacrylate polymer block (d2-1) and 40% by mass or more and 90% by mass or less of an acrylate polymer block (d2-1). Copolymers can be mentioned.
Furthermore, when the acrylate polymer block (d2-2) is composed of an alkyl acrylate and an aromatic (meth) acrylate, the acrylate polymer block (d2-2) is an alkyl acrylate. And 50 to 90% by mass of a structural unit derived from an aromatic ester of (meth) acrylic acid.
As the acrylic block copolymer (D2) other than the above, for example, commercially available products such as "Kuraray" manufactured by Kuraray Co., Ltd. can be obtained.

The lower limit of the content of the acrylic block copolymer (D2) in the (meth) acrylic resin composition is determined from the viewpoint that the impact resistance of the resin laminate is improved. ) 2.0 parts by mass or more, preferably 5.0 parts by mass or more, per 100 parts by mass. The upper limit of the content of the acrylic block copolymer (D2) is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, from the viewpoint of maintaining good flame retardancy and weather resistance of the resin laminate. It is more preferably at most part by mass.
<Other additives>
Various additives may be added to the resin substrate (A), the cured film (B1) and the cured film (B2) according to the purpose. As the additives, conventionally known additives can be appropriately used, and examples thereof include a surfactant, a leveling agent, a dye, a pigment, an antioxidant, an ultraviolet absorber, a stabilizer, a flame retardant, and a plasticizer. The amount of the additive to be added can be appropriately selected within a range in which good physical properties of the hard coat film can be obtained. For example, it is preferably 10 parts by mass or less based on 100 parts by mass of the total curable composition.

<Production method of resin laminate>
Examples of the method for producing the resin laminate of the present invention include a production method including the following processes (1) to (4).
(1) After applying a curable composition (b1) described below to the surface of one mold, the curable composition (b1) exposed to an oxygen atmosphere is cured by irradiating it with an active energy ray. Then, a laminated mold (1) in which a cured film is laminated on the surface of the mold as a cured film is formed.
(2) Next, the laminated mold (X1) is arranged, and then another mold (X2) is arranged so as to face the laminated mold (X1), and the laminated mold (X1) and the mold (X2) are arranged. ), A resin mold gasket is provided on the periphery of the space formed between them, and sealing is performed to produce a laminated mold (X3) having a certain volume inside.
(3) A resin base forming composition described below for forming the resin base (A) is poured into the obtained laminated mold (X3), cast polymerization is performed, and the surface of the cured film is formed. A resin laminate in which the layers of the resin substrate (A) are laminated is formed.
(4) Next, the resin laminate of step (3) is peeled off from the mold to obtain a resin laminate in which the cured coating (B1) is laminated on the surface of the resin substrate (A).

In the present invention, the curable composition (b1) may be applied to the surface of one mold to form a cured cured film, or the curable composition may be applied to the inner surface of another mold placed opposite to the mold. The composition (b2) may be applied to form a cured cured film.
In the present specification and the claims, “casting polymerization” refers to, for example, the formation of a mold in which two molds facing each other at a predetermined interval are opposed to each other and a sealing material arranged at the periphery thereof. It means a method of injecting the resin base material forming composition into the laminated mold and polymerizing the obtained laminated mold.
Examples of the casting polymerization method of the composition for forming a resin base material include a cell casting method in which the composition for forming a resin base material is injected into a multilayer mold and then heated.
As the casting polymerization method of the composition for forming a resin base material, in addition to the above-mentioned method, a continuous casting polymerization method is also mentioned as a suitable method. The continuous casting polymerization method is a lamination stainless steel endless belt in which a cured film is laminated on the surface of an opposed stainless steel endless belt running at the same speed in the same direction, and other stainless steel endless belts. By injecting the resin substrate forming composition continuously from the upstream into the space sealed at both ends of the stainless steel endless belt with the same gasket as the above gasket and heating at a predetermined temperature and time This is a polymerization method for continuously polymerizing.

Examples of the type of the mold include a mold such as a mold and a sheet. The laminated mold is usually formed by facing two molds such that the surface on which the cured coating is laminated is the inner surface. The surface on which the cured film of the mold is laminated preferably has a smooth surface.
Examples of the material of the mold include stainless steel, glass, and resin. The mold may be a mold in which two molds of the same material are opposed to each other, or a mold in which two molds of different materials are opposed to each other.
As the active energy ray, the same energy ray as the above-mentioned active energy ray can be used, and as the curing method using the active energy ray, the same curing method as described above can be used. Although the lower limit of the integrated light quantity of the active energy ray is not particularly limited, it is preferably 200 mJ / cm ² or more because the scratch resistance and the surface hardness are good, and more preferably 400 mJ / cm ² or more. The upper limit of the integrated light amount of the active energy ray is not particularly limited, but if it is 1500 mJ / cm ² or less, the components of the cured film and the resin substrate for forming the cured film between the cured film and the resin substrate. The composition is preferably 1200 mJ / cm ² or less because a mixed layer formed by mixing the composition with each other is obtained.
Further, in the curing treatment in the step (1), it is preferable to irradiate an active energy ray in a state where the curable composition is exposed to an oxygen atmosphere. By irradiating the curable composition with an active energy ray under an oxygen atmosphere, the curable composition is susceptible to curing inhibition by oxygen during curing, so that in the finally obtained resin laminate, the cured film and the resin Since a mixed layer formed by mixing the components of the cured film and the components of the resin base material with each other is formed between the base materials, the impact resistance, scratch resistance, and moldability of the resin laminate are reduced. Can be improved. Here, the term "under an oxygen atmosphere" is not particularly limited as long as it is in the presence of a gas containing oxygen, and air is particularly excellent in consideration of economy and safety.
In the method for producing a resin laminate of the present invention, the thicknesses of the cured film (B1) and the cured film (B2) are not particularly limited, but the lower limit of the film thickness is determined by the resistance of the obtained resin laminate. 5 μm or more is preferable, 8 μm or more is more preferable, and 10 μm or more is more preferable from the viewpoint of improving abrasion and surface hardness. On the other hand, the upper limit of the film thickness is preferably 40 μm or less, more preferably 38 μm or less, and more preferably 35 μm or less, from the viewpoint of suppressing the occurrence of cracks in the cured film during handling of the obtained resin laminate and improving the workability. Is more preferred.
Furthermore, in the method for producing a resin laminate of the present invention, a mixed layer (A-B1) can be formed between the resin substrate (A) and the cured film (B1). Further, a mixed layer (A-B2) can be formed between the resin substrate (A) and the cured film (B2).
The thicknesses of the mixed layer (A-B1) and the mixed layer (A-B2) are not particularly limited, and can be set independently. The lower limit of the thickness of the mixed layer is preferably 0.1 μm or more, more preferably 0.2 μm or more, further preferably 0.5 μm or more, from the viewpoint of improving the crack resistance and adhesion of the obtained resin laminate. preferable. On the other hand, the upper limit of the film thickness of the mixed layer is preferably 3.0 μm or less, more preferably 2.5 μm or less, and more preferably 2.0 μm or less, from the viewpoint of improving the hardness and scratch resistance of the obtained resin laminate. More preferred. The film thickness of the mixed layer (A-B1) and the mixed layer (A-B2) can be controlled to desired values by appropriately selecting the composition of the curable composition and the integrated amount of active energy rays.
<Resin base material forming composition>
The raw material of the resin substrate (A) is referred to as a resin substrate forming composition. As the resin base material forming composition, a monomer copolymerizable with methyl methacrylate and 100% by mass or more than 80% by mass and less than 100% by mass based on the total mass of the (meth) acrylic resin. A radical polymerizable monomer containing more than 0.0% by mass and not more than 20% by mass, and the total amount of the methyl methacrylate and the above-mentioned monomer copolymerizable with methyl methacrylate does not exceed 100% by mass; Means a mixture containing
The resin substrate forming composition uses a syrup, which is a mixture of a partial polymer obtained by polymerizing a part of the mixture containing the above-described radical polymerizable monomer, and the remaining radical polymerizable monomer. Can also. If necessary, a (meth) acrylic polymer is dissolved as a raw material of the resin base material in the mixture of the radical polymerizable monomer containing methyl methacrylate as a main component as the resin base material forming composition. A type of syrup that has been used can also be used.
The molecular weight of the partial polymer in the syrup or the (meth) acrylic polymer as the composition for forming a resin substrate is not particularly limited, and the weight average molecular weight is 50,000 or more and 300,000 or less. Can be. The mixing ratio of the partial polymer or (meth) acrylic resin in the syrup and the radical polymerizable monomer can be from 2:98 to 50:50 by mass.
An initiator can be added to the composition for forming a resin base material. Examples of the initiator include a thermal polymerization initiator in a polymerization initiator (D) described later. The addition amount of the initiator is not particularly limited, but may be 0.005 to 5 parts by mass with respect to the total mass of 100 parts by mass of the monomers in the resin base material forming composition. .
In the composition for forming a resin base material, if necessary, a coloring agent, a release agent, an antioxidant, a stabilizer, a flame retardant, an impact resistance modifier, a light stabilizer, an ultraviolet absorber, a polymerization inhibitor, Various additives such as a chain transfer agent can be added.
<Curable composition (b1)>
The curable composition (b1) is a raw material of a cured film (B1), and in one embodiment, the urethane-based (meth) acrylate (B1-1) is at least 40.0% by mass and at most 90.0% by mass. And a curable composition containing 10.0% by mass or more and 60.0% by mass or less of the polyfunctional (meth) acrylate (B1-2).
The sum of the contents of the urethane (meth) acrylate (B1-1) and the polyfunctional (meth) acrylate (B1-2) is at least 92% by mass and not more than 100% based on the total mass of the curable composition (b1). % By mass or less.
An initiator can be added to the curable composition (b1). Examples of the initiator include a photopolymerization initiator in a polymerization initiator (D) described later. The addition amount of the polymerization initiator (D) is not particularly limited, but is 0.005 to 5 parts by mass with respect to 100 parts by mass of the total mass of the monomers in the curable composition (b1). can do.
<Curable composition (b2)>
The curable composition (b2) is a raw material of a cured film (B2). As one embodiment, the urethane-based (meth) acrylate (B2-1) has a content of 0.0% by mass or more and 90% by mass or less, A curable composition containing 10% to 60% by mass of the polyfunctional (meth) acrylate (B2-2) and 0.0% to 80% by mass of the polyfunctional (meth) acrylate (B2-3). Compositions may be mentioned.
An initiator can be added to the curable composition (b2). Examples of the initiator include a photopolymerization initiator in a polymerization initiator (D) described later. The addition amount of the polymerization initiator (D) is not particularly limited, but is 0.005 to 5 parts by mass with respect to 100 parts by mass of the total mass of the monomers in the curable composition (b2). can do.
<Polymerization initiator (D)>
The polymerization initiator (D) is a component for curing the curable composition. Examples of the polymerization initiator (D) include a thermal polymerization initiator and a photopolymerization initiator.
The content of the polymerization initiator (D) in the curable composition is not particularly limited, but is 0.1 to 10% by mass, with the total weight of the curable composition being 100% by mass. Can be. When the lower limit of the content of the polymerization initiator (D) is 0.1% by mass or more, productivity tends to be improved. When the upper limit of the content of the polymerization initiator (D) is 10% by mass or less, coloring of the cured film can be suppressed.
Examples of the thermal polymerization initiator include, for example, methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxy octoate, t-butyl peroxy benzoate, lauroyl. Organic peroxides such as peroxides; azo compounds such as azobisisobutyronitrile; and the above peroxides combined with amines such as N, N-dimethylaniline and N, N-dimethyl-p-toluidine. Redox polymerization initiators are exemplified.
Examples of the photopolymerization initiator include the following.
D-1) Thioxanthones such as benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methylorthobenzoylbenzoate, 4-phenylbenzophenone, t-butylanthraquinone and 2-ethylanthraquinone;
D-2) Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) ) Acetophenones such as propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone;
D-3) Benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether;
D-4) 2,4,6-Trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenyl Acylphosphine oxides such as phosphine oxide;
D-5) Methylbenzoyl formate;
D-6) 1,7-bisacridinyl heptane;
D-7) 9-phenylacridine.
Of the above, preferred are benzoin ethyl ether, 1-hydroxycyclohexyl-phenyl ketone, and 2-hydroxy-2-methyl-1-phenylpropan-1-one.
As the polymerization initiator (D), these one compound can be used alone or in combination of two or more compounds.

<Resin laminate>
The impact resistance of the resin laminate generally tends to decrease with the improvement of the scratch resistance. In addition, the moldability of the resin laminate generally tends to decrease with the improvement of impact resistance or scratch resistance. That is, the resin laminate of the present invention is a resin laminate having remarkable characteristics of satisfying both conflicting characteristics such as impact resistance, scratch resistance, and moldability.
Examples of the shape of the resin laminate include a sheet-like laminate (resin plate). The thickness of the laminate is not particularly limited, but generally may be 0.2 mm or more and 30 mm or less, preferably 0.5 mm or more and 10 mm or less. When the above-described casting method is used, the thickness (diameter) of the gasket can be appropriately adjusted to obtain a resin plate having a desired thickness.

<Display front panel>
In the display front plate according to one embodiment of the present invention, any one of the resin laminates according to the embodiments of the present invention described above can be used as it is as a display front plate.

<Portable information terminal device>
The portable information terminal device according to one embodiment of the present invention includes the display front panel according to the above-described embodiment of the present invention, and the display of the portable information terminal device such as a mobile phone, a car navigation display device, and a portable game device. It can be used as a display front panel to protect the surface.

<Moving glazing>
In the glazing for a moving body according to an embodiment of the present invention, any one of the resin laminates according to the embodiments of the present invention described above can be used as it is as glazing for a moving body.

Hereinafter, the present invention will be described with reference to examples. In the following, “parts” and “%” indicate “parts by mass” and “% by mass”, respectively.

The abbreviations of the compounds used in Examples and Comparative Examples are as follows.
MMA: methyl methacrylate BA: n-butyl acrylate EDMA: ethylene glycol dimethacrylate Rubber A: multi-structure acrylic copolymer particles (Production Example 1)
Block polymer B: Commercially available acrylic block copolymer (trade name: Clarity, manufactured by Kuraray Co., Ltd.)
UN2301: urethane-based (meth) acrylate having two (meth) acryloyl groups (manufactured by Negami Industry Co., Ltd., trade name: Art Resin UN2301, average molecular weight 500, number of functional groups = 2, average molecular weight / number of functional groups = 250)
UV-7550B: Urethane-based (meth) acrylate having three (meth) acryloyl groups (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: Shikko UV-7550B, average molecular weight 2400, number of functional groups = 3, average molecular weight / number of functional groups = 800)
UV-7650B: A mixture of urethane (meth) acrylates having 4 or 5 (meth) acryloyl groups (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: Purple UV-7650B, average molecular weight 2300, number of functional groups = 3, average) (Molecular weight / functional group number = 511 (average value))
U-2PPA: urethane (meth) acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK Oligo U-2PPA, number of functional groups = 2, molecular weight = 500, average molecular weight / number of functional groups = 250)
UA-122P: urethane (meth) acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK Oligo U-2PPA, number of functional groups = 2, molecular weight = 1100, average molecular weight / number of functional groups = 550)
U6HA: a urethane compound obtained by reacting 3 moles of 3-acryloyloxy-2-hydroxypropyl methacrylate with respect to 1 mole of triisocyanate comprising a trimer of hexamethylene diisocyanate (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) (NK ester U-6HA, number of functional groups = 6, molecular weight = 1019, average molecular weight / number of functional groups = 170)
C6DA: 1,6-hexanediol diacrylate (trade name: C6DA, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
Polyacrylate 1: a mixture (average molecular weight) of 30 to 40% by mass of dipentaerythritol hexaacrylate (number of functional groups = 5, molecular weight = 525) and 60 to 70% by mass of dipentaerythritol pentaacrylate (number of functional groups = 6, molecular weight = 578) / Number of functional groups = 99 (average value))
Polyacrylate 2: a mixture of pentaerythritol triacrylate (functional number = 3, molecular weight = 298) 50 to 70% by mass and pentaerythritol tetraacrylate (functional number = 4, molecular weight = 352) 30 to 50% by mass (average molecular weight / functionality) Radix = 95 (average value)
Darocure 1173: 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name, manufactured by BASF Japan Ltd.)
IRGACURE 819: bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name, manufactured by BASF Japan Ltd.)

<Evaluation method>
The evaluation in Examples and Comparative Examples was performed by the following methods.
(1) Thickness of Mixed Layer The resin laminate was cut in a direction perpendicular to the main surface. Next, a small piece for a transmission electron microscope was cut out of the cut surface of the resin laminate using a microtome. Next, a cut-away section of the small piece was observed using a transmission electron microscope (TEM: manufactured by JEOL Ltd., model: JEM-10111, acceleration voltage: 100 V, magnification: 10,000 times) to obtain a TEM observation image. did. In the obtained TEM observation image, when another layer is observed between the resin base layer and the cured coating layer, that is, in the region where the three-layer structure is observed, the layer of the resin base / the mixed layer As a layer of the cured film, the thickness (unit: μm) of the mixed layer was measured. When no mixed layer was observed, it was designated as "ND".
(2) Charpy Impact Strength A notched Charpy impact strength of a test piece of a resin laminate was measured in accordance with JIS K7111-1 / fU.
(3) Falling ball impact test A falling ball impact test of the resin laminate was performed according to the following method.
A test piece (300 mm long × 300 mm wide) of the resin laminate was allowed to stand at a temperature of 23 ± 2 ° C. and a humidity of 50 ± 5% for 48 hours. Next, the test piece was placed on a metal frame (frame width 15 mm) having a square hole (260 mm × 260 mm) in the center so that the surface of the cured film (B1) was on the upper side. A metal frame (frame width 15 mm, weight 3 kg) having a square hole (260 mm × 260 mm) in the center was placed on the test piece so that the square holes of the upper and lower metal frames coincided. . Next, an iron ball (weight: 227 g, diameter: 38 mm) was dropped to the center of the surface of the test piece from a position 200 cm vertically from the surface of the cured film (B1) of the test piece. The presence or absence of cracks in the test specimen was visually observed, and a pass / fail judgment was made based on the following criteria.
：: Out of 10 test pieces, two or less test pieces where cracks were observed.
×: Three or more test specimens in which cracks were observed were found in 10 test specimens.
(4) Pencil hardness The pencil hardness of the surface of the cured coating (B1) of the resin laminate was measured according to JIS K5400.
(5) Taber abrasion test The scratch resistance of the surface of the cured film (B1) of the resin laminate was evaluated by measuring the amount of change in the haze value before and after the abrasion treatment according to the method described below.
In accordance with ASTM D-1044, after performing a wear treatment on a test piece of the resin laminate under the conditions of a wear wheel CS-10F, a load of 500 g, and a rotation number of 500 cycles, the test piece was washed with a neutral detergent. After washing, the haze value was measured. The haze value was measured before and after abrasion treatment using a haze analyzer (manufactured by Nippon Denshoku Industries Co., Ltd., product name: HAZE METER NDH4000) according to the measurement method shown in JIS K7136. The haze value of a test piece of the resin laminate was measured. The amount of change in the haze value (ΔHAZE: unit%) was calculated from the following equation and used as an index of the scratch resistance. When ΔHAZE was 10 or less, it was judged as acceptable, and when it exceeded 10, it was judged as unacceptable.
[Haze value change (ΔHAZE) (%)] = [Haze value after abrasion treatment (%)] − [Haze value before abrasion treatment (%)]
(6) Formability (crack resistance)
The moldability of the resin laminate was evaluated by bending the resin laminate along the surface of a hemispherical bending jig and observing the occurrence of cracks by the following method.
The resin laminate was cut, and 15 strip-shaped samples (length 120 mm × width 30 mm × thickness 1 mm) were cut out, and the cut surface was polished with an end surface mirror polisher to obtain a test piece.
Next, the test piece is held in a heating furnace at 140 ° C. for 15 minutes and heat-treated, and then taken out of the heating furnace. And placed on the bending jig so as to be on the opposite side. Next, the test piece was bent while being in close contact with the surface of the bending jig, and held for 5 seconds. The test piece after holding for 5 seconds was taken out, and the cut surface was observed with a microscope. A case where no crack was observed was passed, and a case where one or more cracks were observed was failed.
For four types of bending jigs (curvature radii R of cross sections of 75 mm, 100 mm, 150 mm, and 200 mm), three samples were measured. The value of the smallest radius of curvature of the bending jig in which two of the three samples passed was recorded as forming R. When the molding R was 75 mm or 100 mm, it was accepted, and when it was 150 mm or 200 mm, it was unacceptable.

Hereinafter, Production Examples 1 to 5 and Examples 1 to 10 disclose examples of the resin laminate of the present invention.
[Production Example 1] Production of multi-layer acrylic copolymer particles (rubber A) Preparation of Mixture (a-1) 35 parts of MMA, 5 parts of BA, 1 part of BDMA, 0.15 part of AMA, 0.08 part of DBP, and 1.4 parts of emulsifier (1) were mixed to obtain mixture (a-1).
2. Preparation of Mixture (a-2) 0.2 parts of SFS and 5 parts of deionized water were mixed to obtain a mixture (a-2).
3. Preparation of Mixture (a-3) ST 10 parts, BA 50 parts, BDMA 0.2 parts, AMA 1.2 parts, CHP 0.2
And 2.0 parts of the emulsifier (1) were mixed to obtain a mixture (a-3).
4. Preparation of Mixture (a-4) 0.2 part of SFS and 5 parts of deionized water were mixed to obtain a mixture (a-4).
5. Preparation of Mixture (a-5) 57.0 parts of MMA, 3.0 parts of BA, 0.1 part of DBP, and 0.2 part of n-OM were mixed to obtain a mixture (a-5).
6. Production of multi-layered acrylic copolymer particles 300 parts of ion-exchanged water, 0.09 parts of sodium carbonate and 0.9 parts of boric acid were added to a reaction vessel equipped with a reflux condenser, and the temperature was raised to 80 ° C. with stirring. 2.6 parts of 42.63 parts of the mixture (a-1) was added and maintained for 15 minutes, and then the remaining mixture (a-1) was continuously added at a rate of 5.5 parts / hour. Thereafter, the temperature was maintained for 1 hour to carry out polymerization of the innermost layer.
Next, 5.2 parts of the mixture (a-2) was added, and the mixture was held for 15 minutes. Then, 63.6 parts of the mixture (a-3) was continuously added at a rate of 5.1 parts / hour. The polymerization of the intermediate layer was carried out by holding for 2.5 hours.
Next, 5.2 parts of the mixture (a-4) was added, and the mixture was held for 15 minutes. Then, 60.3 parts of the mixture (a-5) was continuously added at a rate of 0.6 part / hour. The outermost layer was polymerized by holding for 1 hour to obtain a multi-layer acrylic copolymer latex.
Next, the latex was coagulated with an aqueous solution of calcium acetate, washed, dehydrated, and dried to obtain particles (rubber A) of an acrylic copolymer having a multiple structure.

[Production Example 2] Production of syrup (a) A mixture consisting of 95 parts by mass of MMA and 5 parts by mass of BA was supplied to a reactor (polymerization vessel) equipped with a cooling pipe, a thermometer, and a stirrer. After stirring for minutes, the temperature was raised while stirring to a temperature of 60 ° C. Subsequently, 0.1 part by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) is added as a radical polymerization initiator, and the temperature is increased while stirring the monomer composition until the temperature reaches 100 ° C. After that, it was kept for 13 minutes. Next, the reactor was cooled until the internal temperature of the reactor reached room temperature to obtain a syrup (a). The content of the (meth) acrylic polymer (P1) in the syrup (a) was 27% by mass.

[Production Example 3] Production of Resin Base Forming Composition (A1) To 100 parts by mass of the above syrup (a), 0.15 parts by mass of EDMA as a monomer (B), and as an impact resistance improver (D), 7.5 parts by mass of the rubber A obtained in Production Example 1 was added and dissolved with stirring at room temperature for 10 minutes. Thereafter, 0.3 parts by mass of t-hexyl peroxypivalate as a polymerization initiator was added and dissolved to obtain a resin base material-forming composition (A1).

[Production Example 4] Production of resin base material-forming composition (A2) 100 parts by mass of the above syrup (a), 0.15 parts by mass of EDMA as a monomer (B) and a block as an impact resistance improver (D) 7.5 parts by mass of polymer B was added and dissolved with stirring at room temperature for 10 minutes. Thereafter, 0.3 parts by mass of t-hexyl peroxypivalate as a polymerization initiator was added and dissolved to obtain a resin base composition (A2).

[Production Example 5] Production of resin base composition (A3) To 100 parts by mass of the above syrup (a), 0.15 parts by mass of EDMA as a monomer (B) was added, and the mixture was stirred at room temperature for 10 minutes. While dissolving. Thereafter, 0.3 parts by mass of t-hexyl peroxypivalate as a polymerization initiator was added and dissolved to obtain a resin base material-forming composition (A3).

[Example 1]
(1) Production of curable composition (b1) 50 parts by mass of UN2301, 50 parts by mass of C6DA, 3 parts by mass of Darocure 1173, and 0.15 part by mass of IRGACURE819 were mixed to obtain curable composition (b1). Was.
(2) Casting polymerization Then, using a SUS plate having a mirror-finished plate surface as a mold, and using a bar coater, the curable composition (b1) is finally cured into a cured film (B1) having a film thickness. The composition was applied to the surface of the mold so as to have a thickness of 15 μm to form a layer of the curable composition (b1).
Next, while passing the mold under the metal halide lamp with the layer of the curable composition (b1) being on the upper side, the light (output: 120 W / cm ² ) of the metal halide lamp was exposed to the curable composition in air. The object (b1) was irradiated to cure the curable composition (b1) to form a cured film. A laminate (1A) in which a cured coating was laminated on the surface of the mold (SUS plate) was obtained. The obtained laminated die (1A) and the SUS plate on which the cured coating is not formed are opposed to each other so that the cured coating of the laminated die (1A) is on the inside, and the peripheral portions of these two SUS plates are fixed. It was sealed with a resin gasket to produce a laminated mold (1B).
Next, the resin base composition (A1) of Production Example 3 was injected into the above-mentioned laminated mold (1B) after removing dissolved air under reduced pressure, and completely sealed with a resin gasket. Next, the laminated mold (1B) was heated in a water bath at 80 ° C. for 1 hour, and then in an air furnace at 130 ° C. for 1 hour to polymerize the resin base composition (A1). A layer of the substrate was formed. Next, after cooling the laminated mold (1B) to room temperature, two SUS plates on both sides are peeled off from the laminated mold (1B), and a cured film (B1) is formed on one surface of one side of the resin base material layer. And a resin laminate having a thickness of 1.0 mm having the following formula:
That is, the curable composition (b1) applied to the surface of a mold (SUS plate) and exposed to an oxygen atmosphere is cured by irradiating light from a metal halide lamp to the curable composition (b1). A layer of the composition for forming a resin base material was provided on the surface of the cured film of Example 1 and polymerized (coating method: P1).
With respect to the obtained resin laminate, the thickness of the mixed layer, scratch resistance, pencil hardness, impact resistance, and moldability were evaluated by the above-described evaluation methods. Table 1 shows the evaluation results.
The cured film (B1) of the resin laminate had an abrasion resistance (ΔHaze in Taber abrasion test) of 7%, a pencil hardness of 3H, and was excellent in the abrasion resistance and surface hardness. In addition, the Charpy impact strength was 40 kJ / m ² , the drop impact strength of the resin laminate passed, and the moldability was good. Table 1 shows the evaluation results of the obtained resin laminate.
[Comparative Example 1]
At the time of casting polymerization, a methacrylic resin plate having a thickness of 1.0 mm was obtained in the same manner as in Example 1 except that the SUS plate was used as a laminated mold (1B) without forming a cured film. . Table 1 shows the evaluation results of the obtained resin plates.
[Comparative Examples 2 and 3]
A resin laminate was obtained in the same manner as in Example 1, except that the composition of the curable composition (b1) was as shown in Table 1. Table 1 shows the evaluation results of the obtained resin laminate.
[Comparative Example 4]
The curable composition (b1) obtained in the same manner as in Example 1 was applied to one surface of the methacrylic resin plate manufactured in Comparative Example 1.
Next, a commercially available PET film is bonded so as to be in contact with the surface of the resin plate to which the curable composition (b1) is applied, and then pressed by a press roll. The finally obtained cured film has a thickness of 15 μm. The thickness of the curable composition (b1) was adjusted such that
While passing the methacrylic resin plate, the layer of the curable composition (b1) and the PET film in this order under the metal halide lamp, the light (output 120 W / cm ² ) of the metal halide lamp is applied to the PET. By irradiating the curable composition (b1) via the film and performing a curing treatment, a cured laminate in which a methacrylic resin plate, a cured coating (B1), and a PET film were sequentially laminated was obtained.
That is, the curable composition (b1) applied to one surface of the methacrylic resin plate and not exposed to the oxygen atmosphere was irradiated with light from a metal halide lamp to be cured (coating method: P2).
Thereafter, the PET film was peeled from the obtained cured laminate to obtain a resin laminate in which a cured coating (B1) was laminated on one surface of a methacrylic resin plate. Table 1 shows the evaluation results of the obtained resin laminate.
[Comparative Example 5]
A resin laminate was obtained in the same manner as in Example 1 except for using the resin base composition (A3) of Production Example 5 during casting polymerization. Table 1 shows the evaluation results of the resin laminate.
[Example 2]
50 parts by mass of UN2301, 50 parts by mass of C6DA, 3 parts by mass of Darocure 1173, and 0.15 part by mass of IRGACURE819 were mixed to obtain a curable composition (b2).
Next, in the same manner as in Practical Example 1, a layer of the curable composition (b2) was provided using a SUS plate having a mirror-finished plate surface as a mold, and a metal halide lamp (output: 120 W / cm ² ) was used. Thus, the curable composition (b2) was cured to obtain a laminate (1A ′) in which a cured film having a thickness of 15 μm was laminated on the surface of the SUS plate. The obtained laminated type (1A ') and the laminated type (1A) obtained by the method of Example 1 are combined with the laminated type (1A) cured film and the laminated type (1A') cured film inside. The two SUS plates were sealed so as to face each other, and the peripheral portions of the two SUS plates were sealed with a resin gasket to produce a laminated mold (1B). Otherwise, a resin laminate was obtained in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained resin laminate.
[Comparative Example 6]
The curable composition (b2) having the composition shown in Table 1 was applied to the surface of the resin laminate manufactured in Comparative Example 4 where no cured film was formed.
Next, a commercially available PET film is bonded so as to be in contact with the surface of the resin plate to which the curable composition (b2) is applied, and then pressed by a press roll, and the finally obtained cured film has a thickness of 15 μm. The thickness of the curable composition (b2) was adjusted such that
The light (output: 120 W / cm ² ) of the metal halide lamp is passed through a laminate in which this resin laminate, the layer of the curable composition (b2), and the PET film are sequentially laminated below the metal halide lamp at a constant speed. By irradiating the curable composition (b2) via the PET film and performing a curing treatment, a cured film (B2) and a PET film are sequentially laminated on one surface of the methacrylic resin plate, and the other one side is cured. A cured laminate in which the cured coating (B1) was laminated on the surface was obtained.
That is, the curable composition (b2) that was not exposed to the oxygen atmosphere was irradiated with light from a metal halide lamp to be cured (coating method: P2).
Thereafter, the PET film is peeled off from the obtained cured laminate, and a cured film (B2) is laminated on one surface of the methacrylic resin plate, and a cured film (B1) is laminated on the other surface. I got a body. Table 1 shows the evaluation results of the obtained resin laminate.
[Comparative Example 7]
A resin laminate was obtained in the same manner as in Example 2 except that the composition (A3) for forming a resin base material of Production Example 5 was used during casting polymerization. Table 1 shows the evaluation results of the resin laminate.
[Example 3]
A resin plate was obtained in the same manner as in Example 2 except that the composition (A2) for forming a resin base material of Production Example 4 was used during casting polymerization. Table 1 shows the evaluation results of the resin plate.
[Comparative Example 8]
A resin laminate was obtained in the same manner as in Comparative Example 1, except that the composition (A2) for forming a resin base material of Production Example 4 was used during casting polymerization. Table 1 shows the evaluation results of the resin laminate.
[Examples 4 to 10, Comparative Examples 9 to 12]
A resin laminate was manufactured in the same manner as in Example 2 except that the compositions of the curable composition (b1) and the curable composition (b2) were as shown in Table 1. Table 1 shows the evaluation results of the obtained resin laminate. In Comparative Example 10, the curable composition (b1) and the curable composition (b2) could not be stably applied, and a resin laminate could not be obtained.

Compared with Example 1, the resin laminate of Comparative Example 1 did not have a cured film, and therefore had insufficient scratch resistance.
As compared with Example 1, the resin laminates of Comparative Examples 2 and 3 had a higher crosslink density of the cured film, and thus had insufficient moldability.
Compared with Example 1, the resin laminate of Comparative Example 4 did not have a mixed layer, and thus had insufficient surface hardness and moldability.
Since the resin base material of Comparative Example 5 did not contain the impact modifier (D), the impact resistance was insufficient as compared with Example 1.
Compared with Example 2, the resin laminate of Comparative Example 6 had no impact resistance, surface hardness, and moldability because it did not have a mixed layer.
Compared with Example 2, the resin laminate of Comparative Example 7 had insufficient impact resistance because the resin substrate did not contain the impact modifier (D).
Compared with Example 3, the resin laminate of Comparative Example 8 did not have a cured film, and thus had insufficient scratch resistance.
Compared with Example 4, the resin laminate of Comparative Example 9 had a higher crosslink density of the cured coating (A) and the cured coating (B), and therefore had insufficient impact resistance and moldability.
In Comparative Example 10, since the curable composition (b1) and the curable composition (b2) had high viscosities and could not be stably applied, a resin laminate could not be obtained.
As compared with Examples 2 and 7 to 10, the resin laminated body of Comparative Example 11 had a higher crosslink density of the cured film, and thus had insufficient impact resistance and moldability.
Compared with Example 7, the resin laminate of Comparative Example 12 had insufficient cross-linking density of the cured film, and thus had insufficient scratch resistance.

According to the present invention, a resin laminate excellent in impact resistance, scratch resistance, and moldability can be stably provided. Such a resin laminate is suitable for a display front plate for protecting a display surface of a portable information terminal device such as a mobile phone, a car navigation display device, and a portable game device, and a glazing for a moving object.

DESCRIPTION OF SYMBOLS 1 Resin base material 2 Cured film 3 Resin laminate 4 Layer of resin substrate 5 Mixed layer 6 Layer of cured film

Claims (10)

A resin laminate comprising a cured resin film (B1) on one surface of a sheet-shaped resin substrate (A),
The cured film (B1) has two to five radical polymerizable functional groups, and has a urethane (meth) acrylate (B1-1) -derived repeating unit having a urethane bond in the molecule, and a radical polymerizable functional group. A resin composition containing a repeating unit derived from a polyfunctional (meth) acrylate (B1-2) having two functional groups (excluding the repeating unit derived from the polyfunctional (meth) acrylate (B1-1)) Including and
In each of the polyfunctional (meth) acrylates (i) having two or more radically polymerizable functional groups constituting the cured film (B1), the average molecular weight of each polyfunctional (meth) acrylate (i) is M _i , The number of radically polymerizable functional groups of each polyfunctional (meth) acrylate (i) is F _i , and the mass fraction of each polyfunctional (meth) acrylate (i) constituting the cured coating (B1) is _Wi. (% By mass), the following expression (1) is satisfied;
[Wherein, W i _(mass%) in the cured film (B1), a polyfunctional (meth) acrylate (i) each of the mass fraction having at least two radical-polymerizable functional group, M _i is the respective average molecular weight of the polyfunctional (meth) acrylate (i), F _i is the polyfunctional (meth) acrylate the number of radically polymerizable functional groups of the respective polyfunctional (meth) acrylate (i), k is chosen (i ) Represents an integer of 2 or more. ]
The resin substrate (A) is made of a (meth) acrylic resin composition containing an impact resistance improver (D), and
A resin laminate in which the impact modifier (D) is at least one selected from the following multi-structured acrylic copolymer particles (D1) and the following acrylic block copolymers (D2).
Multi-layer acrylic copolymer particles (D1): Multi-layers having a structure in which a hard resin layer (d1-2) is formed on the surface of elastomer particles (d1-1) containing a rubbery copolymer having a crosslinked structure. Structural acrylic copolymer particles.
Acrylic block copolymer (D2): 10% by mass or more and 60% by mass or less of methacrylate polymerized block (d2-1) and 40% by mass or more and 90% by mass or less of acrylic acid ester polymerized block (d2-2). Block copolymer.   The cured film (B1) was obtained by dividing the numerical value of the average molecular weight of the urethane (meth) acrylate (B1-1) by the number of radically polymerizable functional groups of the urethane (meth) acrylate (B1-1). The resin laminate according to claim 1, wherein a value (average molecular weight / number of functional groups) is 180 or more and 900 or less.   A mixed layer (A-B1) of the components of the resin substrate (A) and the components of the cured film (B1) has a thickness of 0 at the boundary between the resin substrate (A) and the cured film (B1). The resin laminate according to claim 1, wherein the resin laminate is formed to have a thickness of 0.1 μm or more and 3.0 μm or less.   In the cured film (B1), the sum of the content of the repeating unit derived from the urethane (meth) acrylate (B1-1) and the content of the repeating unit derived from the polyfunctional (meth) acrylate (B1-2) is determined by the curing. The resin laminate according to any one of claims 1 to 3, comprising a resin composition containing 92% by mass or more and 100% by mass or less based on the total mass of the coating (B1).   The cured film (B1) has a repeating unit derived from the urethane-based (meth) acrylate (B1-1) of 35% by mass or more and 90% by mass or less based on the total mass of the cured film (B1). The resin laminate according to any one of claims 1 to 4, comprising a resin composition containing 10% by mass to 62% by mass of a repeating unit derived from a functional (meth) acrylate (B1-2). A sheet-like resin laminate comprising a cured film (B2) on the other surface of the resin substrate (A),
The cured film (B2) has two to five radical polymerizable functional groups, and has a urethane (meth) acrylate (B2-1) -based repeating unit having a urethane bond in a molecule;
A repeating unit derived from a polyfunctional (meth) acrylate (B2-2) having two radically polymerizable functional groups (however, excluding a repeating unit derived from a urethane-based (meth) acrylate (B2-1));
A repeating unit derived from a polyfunctional (meth) acrylate (B2-3) having 3 to 6 radically polymerizable functional groups (excluding a repeating unit derived from a urethane-based (meth) acrylate (B2-1))
The resin laminate according to any one of claims 1 to 5, comprising a resin composition containing:   At the boundary between the resin substrate (A) and the cured film (B2), a mixed layer (A-B2) of the components of the resin substrate (A) and the components of the cured film (B2) has a thickness of 0.1 mm. The resin laminate according to claim 6, which is formed to have a thickness of 1 µm or more and 3.0 µm or less.   A display front plate comprising the resin laminate according to claim 1.   A portable information terminal device comprising the display front panel according to claim 8. A glazing for a moving object, comprising the resin laminate according to any one of claims 1 to 7.