JP2019155612A - Resin laminate, and production method of resin laminate - Google Patents

Abstract

To provide a resin laminate excellent in excoriation resistance, self-recovery nature against a scratch made by a pencil of a 3H pencil hardness, and drawing processability.SOLUTION: A resin laminate has a hard coating film (B) on at least one surface of a resin substrate (A) made of a (meta) acrylic resin. The hard coating film (B) has a tensile elastic modulus of 100 MPa or more and 1,000 MPa or less. Ten scratches of at least 7 mm are made on the surface of the hard coating film (B) by a pencil of a 3H pencil hardness by a method (750±10 g load, 30-60 mm/min speed) in conformity with JIS K5600-5-4. The number of remaining scratches is two or less after a lapse of 24 hours under an environment of a temperature of 23±2°C and a humidity of (50±5)% .SELECTED DRAWING: None

Description

  The present invention relates to a resin laminate and a method for producing a resin laminate.

Conventionally, in order to protect the surface of various displays such as CRT display devices, liquid crystal televisions, mobile phones, etc., transparent glass plates and resin plates have been used as the entire display plate. In particular, recently, in the field of in-vehicle materials such as instrument panels and glazing, acrylic resin plates which are excellent in transparency, lighter than glass plates and excellent in workability have been more focused.
However, although the acrylic resin plate has high transparency, the product may be scratched by contact with a person or an object as compared with a glass plate, and thus scratch resistance is required.

Recently, acrylic resin plates are required to have so-called self-healing properties such that scratches on the surface of a resin plate attached with a pencil having a pencil hardness of 3H are recovered over time.
Recently, from the viewpoint of diversification of product design, acrylic resin plates are required to be bent and processed with a small radius of curvature, or to be processed into complicated shapes, that is, stretch workability.

Furthermore, recently, in order to satisfy both self-repairability and stretchability, a cured coating is required to have high breaking elongation and mechanical strength.
As a method for solving these problems, for example, Patent Document 1 proposes a resin laminate having a cured film formed by curing a coating material composition containing a specific polyfunctional monomer, The cured film has a cross-linked structure, thereby achieving a pencil hardness of 9H.

Patent Document 2 proposes a hard coat film having a cured coating obtained by curing a curable composition containing urethane (meth) acrylate having an isocyanuric skeleton, and the cured coating is self-healing against surface scratches. It has sex.
Patent Document 3 proposes a laminate having a cured film obtained by curing an active energy ray-curable resin composition containing a urethane acrylate containing a polycarbonate-based polymer as a constituent component, and the laminate is a cured film. It has self-healing properties and three-dimensional processability against surface scratches.

WO2014 / 184833 WO2012 / 085651 JP 2014-196430 A

However, when the resin laminate of Patent Document 1 is bent with a radius of curvature R of 40 mm, a crack occurs because the cured coating cannot follow the deformation. That is, the stretch processability was insufficient.
In addition, the hard coat film of Patent Document 2 has self-healing properties for scratches attached using a pencil with a pencil hardness of 3H, but the cured coating cannot follow the deformation of the three-dimensional processing because the crosslinking density is too high. That is, the stretch processability was insufficient.

Moreover, although the laminated body of patent document 3 is excellent in abrasion resistance and extending | stretching workability, the self-repair property of the damage | wound attached using the pencil of pencil hardness 3H was inadequate.
The present invention aims to solve these problems. That is, an object of the present invention is to provide a resin laminate having excellent scratch resistance, self-healing property against scratches formed using a pencil having a pencil hardness of 3H, and high stretch workability. It is to provide.

As a result of intensive studies to solve the above problems, the present inventor has found that the resin laminate of the present invention can solve the above problems, and has reached the present invention. That is, the gist of the present invention is as follows.
That is, the first gist of the present invention is a resin laminate including a cured coating (B) on at least one surface of a resin base material (A) made of a (meth) acrylic resin, the cured coating ( B) The tensile modulus of elasticity is 100 MPa or more and 1000 MPa or less, and the curing is performed by using a pencil having a pencil concentration of 3H by a method (load 750 ± 10 g, speed 30 to 60 mm / min) in accordance with JIS K5600-5-4. 10 scratches were formed on the surface of the coating (B) at least 7 mm, and the number of scratches after 24 hours in an environment of temperature 23 ± 2 ° C. and humidity (50 ± 5)% was 2. The present invention is related to a resin laminate.

The second gist of the present invention relates to a method for producing a resin laminate comprising sequentially performing the following steps (1) to (3).
Step (1): 100 parts by mass of a mixture containing 95.0 to 99.99% by mass of urethane (meth) acrylate oligomer (C) and 0.01 to 5.0% by mass of the surface slip agent (B2), and liquid The active energy ray-curable resin composition containing 50 to 1000 parts by mass of the organic compound (B3) is applied to at least one surface of the resin base material (A) made of (meth) acrylic resin.

Step (2): After step (1), the liquid organic compound (B3) contained in the active energy ray-curable resin composition applied to the resin base material (A) is the active energy ray-curable resin. It heats until it becomes 10 mass% or less with respect to 100 mass% of total mass of a composition.
Step (3): After the step (2), the active energy ray-curable resin composition is irradiated with an active energy ray and cured to form a cured film, and the surface of the resin substrate (A) A resin laminate having the cured coating formed thereon is obtained.

  The urethane (meth) acrylate oligomer (C) is a structural unit derived from polyisocyanate (b-1), a structural unit derived from polycarbonate polyol (b-2), and a hydroxyalkyl (meth) acrylate (b- 3) The total amount of the structural unit derived from (b-1), the structural unit derived from (b-2), and the structural unit derived from (b-3) is 100 mol%. In contrast, 30 to 50 mol% of structural units derived from (b-1), 10 to 50 mol% of structural units derived from (b-2), and 3 to 30 mol% of structural units derived from (b-3) Containing.

According to the present invention, it is possible to provide a resin laminate having excellent cured film mechanical strength, excellent scratch resistance and self-healing properties, and high stretch workability.
The resin laminate of the present invention has excellent scratch resistance and self-healing property against scratches attached using a pencil having a pencil hardness of 3H, and is highly stretchable to follow deformation during three-dimensional processing. Because it has excellent mechanical strength of cured film, it is not only a display front plate for protecting the display surface of portable information terminal devices such as mobile phones and portable game devices, but also a curved display. It is also suitable for products having complicated shapes such as full-panel boards, instrument panels, sanitary boards, and signboards.

Hereinafter, the present invention will be described in detail. In the present invention, “(meth) acrylate” means at least one selected from “acrylate” and “methacrylate”, and “(meth) acrylic acid” means “acrylic acid”. "Means at least one selected from" methacrylic acid ". The same applies to (meth) acryloyl and (meth) acryl.

In the present invention, “monomer” means an unpolymerized compound, and “repeating unit” means a unit derived from the monomer formed by polymerization of the monomer. The repeating unit may be a unit directly formed by a polymerization reaction, or may be a unit in which a part of the unit is converted into another structure by treating a polymer.
In the present invention, “mass%” indicates the content of a specific component contained in the total amount of 100 mass%.

Unless otherwise specified, “% by mass” indicates the content of a specific component contained in the total amount of 100% by mass.
Unless otherwise specified, a numerical range expressed using “to” in the present specification means a range including numerical values described before and after “to” as a lower limit value and an upper limit value, and “A to B”. Means A or more and B or less.

<Resin laminate>
The resin laminate of the present invention is a resin laminate comprising a cured coating (B) described later on at least one surface of a resin base material (A) made of a (meth) acrylic resin.
Since the resin base material (A) is made of a (meth) acrylic resin, the resin laminate of the present invention is excellent in adhesion between the resin base material (A) and the cured film (B). Moreover, since the tensile elasticity modulus of the cured resin film (B) measured by the method to be described later is 100 MPa or more and 1000 MPa or less, the resin laminate of the present invention is a pencil hardness according to JIS K5600-5-4. Using a 3H pencil, scratches are formed on the surface of the cured coating (B), and the scratches after 24 hours have excellent self-repairing properties of 2 or less.

Further, by controlling the molecular weight between the calculation network cross-linking points, the followability (molding processability) of the cured coating (B) to deformation when the resin laminate is three-dimensionally processed can be improved.
That is, since the resin laminate of the present invention has excellent self-healing properties and high stretchability, it protects the display surface of portable information terminal devices such as mobile phones and portable game devices. It is suitable not only for the front plate of the display, but also for products having complicated shapes such as a full-surface plate of curved display, instrument panel, sanitary, signboard.

<Resin substrate (A)>
The resin substrate (A) is one of the constituent components of the resin laminate of the present invention.
The resin substrate (A) in the present invention is made of a (meth) acrylic resin. The (meth) acrylic resin is a homopolymer consisting of 100% by mass of repeating units derived from methyl methacrylate (hereinafter abbreviated as “MMA”), or a total weight of 100% by mass of the (meth) acrylic resin. On the other hand, it exceeds 50% by mass and less than 100% by mass of the repeating unit derived from MMA and 0% by mass of the repeating unit derived from a monomer copolymerizable with MMA (hereinafter abbreviated as “other monomer”). Means a polymer containing 50% by mass or less.

The other monomer is not particularly limited, and examples thereof include the following a1) to a16).
a1) Methacrylic acid esters such as ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, phenyl methacrylate, benzyl methacrylate;
a2) acrylic acid esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate;
a3) unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, itaconic acid;
a4) unsaturated carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride;
a5) Maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
a6) Hydroxy group-containing vinyl monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate;
a7) Vinyl esters such as vinyl acetate and vinyl benzoate;
a8) Vinyl chloride, vinylidene chloride and derivatives thereof;
a9) nitrogen-containing vinyl monomers such as methacrylamide and acrylonitrile;
a10) Epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate;
a11) Aromatic vinyl monomers such as styrene and α-methylstyrene Further, examples of the monomer copolymerizable with the methyl methacrylate unit include the following a12) to a16) in addition to the above monomers. Can be mentioned.

a12) Alkanediol di (meth) acrylate such as ethylene glycol di (meth) acrylate, 1,2-propylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate (Meth) acrylate;
a13) Diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol di (meth) Polyoxyalkylene glycol di (meth) acrylates such as acrylates;
a14) a vinyl monomer having two or more ethylenically unsaturated bonds in a molecule such as divinylbenzene;
a15) an unsaturated polyester prepolymer obtained from at least one polycarboxylic acid containing an ethylenically unsaturated polycarboxylic acid and at least one diol;
a16) Vinyl ester prepolymer obtained by acrylic-modifying the terminal of the epoxy group These other monomers may be used alone or in combination of two or more.

  The (meth) acrylic resin is obtained by polymerizing a mixture of radical polymerizable monomers (hereinafter abbreviated as “resin base material forming composition”). The resin base material forming composition is a monomer mixture containing MMA 50% by mass to 100% by mass and the other monomer 0% by mass to 50% by mass with respect to a total mass of 100% by mass. is there. In addition, for the resin base material forming composition, if necessary, a colorant, a release agent, an antioxidant, a stabilizer, a flame retardant, an impact modifier, a light stabilizer, an ultraviolet absorber, and a polymerization prohibition. Various additives such as an agent and a chain transfer agent can be added.

Although it does not specifically limit as a polymerization method of the composition for resin base material formation, For example, a block polymerization method, a solution polymerization method, an emulsion polymerization method, and a suspension polymerization method are mentioned. From the viewpoint of the production cost of the (meth) acrylic resin composition, the environmental load due to the use of a solvent, the productivity of the (meth) acrylic resin laminate, and the transparency, the bulk polymerization method is preferred.
Moreover, as a method of shape | molding the said (meth) acrylic resin as a resin base material (A), the desired shape is obtained for the pellet-shaped (meth) acrylic resin obtained by said polymerization method using a well-known extrusion molding method. By polymerizing a method for forming a resin, a syrup obtained by polymerizing a part of the resin base material forming composition or a part of the resin base material forming composition, using the above polymerization method in a known cell casting method, The method of using a plate-shaped resin base material is mentioned.

<Hardened film (B)>
The cured coating (B) is one of the constituent components of the resin laminate of the present invention.
The cured film (B) is a cured film containing a resin (B1) having a cross-linked structure described later and a surface slip agent (B2).
Moreover, the cured film (B) in this invention is a cured film formed by hardening | curing the active energy ray-curable resin composition mentioned later.

  The said cured film (B) contains a surface slip agent (B2) in the range of 0.095 mass% or more and 5.0 mass% or less with respect to 100 mass% of total mass of this cured film (B). Is preferred. The lower limit of the content of the surface slip agent (B2) is that the self-healing property of the resin laminate is good, the frictional resistance of the cured coating (B) is reduced, and the scratch resistance of the resin laminate is good. From the viewpoint, 0.0095% by mass or more is preferable. 0.05 mass% or more is more preferable, and 0.1 mass% or more is further more preferable. The upper limit of the content of the surface slip agent (B2) is that the cured film (B) can be maintained from the viewpoint that the adhesiveness of the cured film (B) can be maintained well and the scratch resistance and self-repairing property of the resin laminate are improved. ) Is preferably 5.0% by mass or less with respect to 100% by mass. 2.0 mass% or less is more preferable, and 0.75 mass% or less is further more preferable.

  The cured film (B) contains a resin (B1) having a crosslinked structure in a range of 95.0 mass% to 99.9905 mass% with respect to 100 mass% of the total mass of the cured film (B). It is preferable to do. The lower limit of the content of the resin (B1) is preferably 95.0% by mass or more from the viewpoint of improving the scratch resistance of the resin laminate. 98.0 mass% or more is more preferable, and 99.25 mass% or more is further more preferable. The upper limit of the content of the resin (B1) is 99.9905% by mass with respect to 100% by mass of the total mass of the cured coating (B) from the viewpoint of improving the stretchability and self-recoverability of the resin laminate. The following is preferred. 99.95 mass% or less is more preferable, and 99.90 mass% or less is further more preferable.

The cured coating (B) has a tensile modulus measured by a method described later of 100 MPa to 1000 MPa. The lower limit of the tensile elastic modulus is preferably 100 MPa or more, more preferably 110 MPa or more, from the viewpoint of suppressing breakage of the cured film when a scratch is formed on the surface of the cured film (B) using a pencil having a pencil hardness of 3H. preferable. The upper limit of the tensile elastic modulus is preferably 1000 MPa or less, and more preferably 500 MPa or less, from the viewpoint of good self-repairability of scratches formed on the surface of the cured coating (B) using a pencil having a pencil hardness of 3H.
The tensile elasticity modulus of a cured film (B) can be adjusted with content of a urethane (meth) acrylate oligomer (C), the kind of arbitrary component mentioned later, its mixture ratio, etc., for example. In addition, the tensile elasticity modulus of a cured film (B) can be measured as the tensile elasticity modulus of the cured film formed by hardening | curing the active energy ray-curable resin composition mentioned later by the method mentioned later.

The cured coating (B) preferably has a breaking elongation measured by the method described later of 50% or more, more preferably 75% or more, from the viewpoint of improving the stretch processability of the resin laminate. Preferably, it is more preferably 100% or more, and particularly preferably 125% or more.
The breaking elongation of the cured coating (B) can be adjusted by, for example, the content of the urethane (meth) acrylate oligomer (C), the types of optional components described later, the blending ratio thereof, and the like. The breaking elongation of the cured film (B) can be measured as the breaking elongation of a cured film obtained by curing an active energy ray-curable resin composition described later by a method described later.

<Active energy ray-curable resin composition>
The active energy ray-curable resin composition is a raw material for the cured coating (B).
As the active energy ray curable resin composition, a resin composition containing a urethane (meth) acrylate oligomer (C) described later and a surface slip agent (B2) described later can be used.

<Resin having a crosslinked structure (B1)>
The resin (B1) having a crosslinked structure is one of the constituent components of the cured coating (B).
The resin (B1) having a crosslinked structure is a resin obtained by curing the urethane (meth) acrylate oligomer (C) by irradiating it with active energy rays.
The resin (B1) having a crosslinked structure contains 40 mass% or more of the structural unit derived from the urethane (meth) acrylate oligomer (C) with respect to 100 mass% of the total mass of the resin (B1),
The resin (B1) having a crosslinked structure is preferable because it contains a structural unit derived from the urethane (meth) acrylate oligomer (C) and the stretchability of the obtained cured film (B) tends to be improved.
The resin (B1) having a crosslinked structure is a resin having a crosslinked structure having a molecular weight between calculated network crosslinking points of 1000 or more and 15000 or less. A method for calculating the molecular weight between the calculation network crosslinking points will be described later.

  In the resin (B1) having a crosslinked structure, the structural unit derived from the urethane (meth) acrylate oligomer (C) is a scratch resistance, self-repairing property, stretch processability, mechanical property of the resin (B1) having a crosslinked structure. From the viewpoint of improving strength, a structural unit derived from polyisocyanate (b-1), a structural unit derived from polycarbonate polyol (b-2), and a structural unit derived from hydroxyalkyl (meth) acrylate (b-3) It is preferable to include.

  In the resin (B1) having a crosslinked structure, the structural unit derived from the urethane (meth) acrylate oligomer (C) is a structure derived from the (b-1) from the viewpoint of improving the mechanical properties of the resin laminate. It preferably contains 30 to 50 mol% of units, 10 to 50 mol% of structural units derived from (b-2), and 3 to 30 mol% of structural units derived from (b-3).

  The lower limit of the molecular weight between the calculated network crosslinking points is preferably 1000 or more, and more preferably 3000 or more, from the viewpoint that the stretchability of the resin laminate is good. The upper limit of the molecular weight between the calculated network cross-linking points is preferably 15000 or less, and more preferably 12000 or less, from the viewpoint of improving the scratch resistance of the resin laminate.

<Surface slip agent (B2)>
The surface slip agent (B2) is one of the components of the cured coating (B).
The surface slip agent (B2) is not particularly limited, and a compound having a siloxane bond unit (hereinafter abbreviated as “siloxane bond-containing compound”), a fluorine-based resin, and fluorine-containing waxes can be used.
Examples of the siloxane bond-containing compound include a reactive siloxane bond-containing compound having a functional group having a reactive group, or a non-reactive siloxane bond-containing compound having a functional group not having a reactive group. Examples of the reactive group of the reactive siloxane bond-containing compound include one-terminal reactive groups such as amino group, epoxy group, carboxyl group, carbinol group, methacryl group, mercapto group, or phenol group, and different functional groups. Is mentioned. As the non-reactive siloxane bond-containing compound, a polyether-modified, methylstyryl-modified, alkyl-modified, higher fatty acid ester-modified, hydrophilic special modification, higher alkoxy-modified, higher fatty acid-containing, or fluorine-modified compound can be used.

As the fluororesin, known ones can be used. Among them, a compound having a perfluoroalkyl group or a perfluoropolyether group is a viewpoint that the scratch resistance and self-repairing property of the resin laminate is good. To preferred.
Furthermore, as a compound having a perfluoroalkyl group or a perfluoropolyether group, the compound represented by the following general formula (1) is used from the viewpoint of improving the scratch resistance and self-repairing property of the resin laminate. More preferred.

[In formula (1), Rf represents a perfluoroalkyl group or a perfluoropolyether group. ]
As a commercial product, OPTOOL DAC (trade name, manufactured by Daikin Industries, Ltd.) can be used.

<Urethane (meth) acrylate oligomer (C)>
The urethane (meth) acrylate oligomer (C) is one of the constituent components of the active energy ray-curable resin composition.
As the urethane (meth) acrylate oligomer (C) in the present invention, a compound having one or more radically polymerizable (meth) acryloyl groups and at least two urethane bonds in the molecule can be used.
The cured product obtained by irradiating the resin composition containing the urethane (meth) acrylate oligomer (C) with active energy rays has an excellent balance between tensile elongation and tensile elastic modulus. The balance between the stretch processability and the self-healing property of the laminate is improved.

  Furthermore, the urethane (meth) acrylate oligomer (C) in the present invention is irradiated with active energy rays compared to active energy ray-curable oligomers such as epoxy (meth) acrylate oligomers and acrylic (meth) acrylate oligomers. The resulting resin laminate is suitable because it can suppress tack (stickiness).

The urethane (meth) acrylate oligomer (C) is a structural unit derived from polyisocyanate (b-1) described later, a structural unit derived from polycarbonate polyol (b-2) described later, and a hydroxyalkyl (meth) acrylate described later. An oligomer containing a structural unit derived from (b-3) can be used.
The urethane (meth) acrylate oligomer (C) includes a polyisocyanate (b-1) described later, a polycarbonate polyol (b-2) described later, and a hydroxyalkyl (meth) acrylate (b-3) described later. A reaction product of a raw material can be used.

Furthermore, the urethane (meth) acrylate oligomer (C) has a structural unit of 30 to 50 mol% derived from polyisocyanate (b-1), a polycarbonate polyol (b) from the viewpoint of improving the mechanical properties of the resin laminate. It is more preferable that the reaction product is a raw material containing 10 to 50 mol% of structural units derived from -2) and 3 to 30 mol% of structural units derived from hydroxyalkyl (meth) acrylate (b-3).
Hereinafter, polyisocyanate (b-1), polycarbonate polyol (b-2), and hydroxyalkyl (meth) acrylate (b-3) will be described in detail.

<Polyisocyanate (b-1)>
Polyisocyanate (b-1) is one of the constituent components of urethane (meth) acrylate oligomer (C).
The polyisocyanate (b-1) is a compound having at least one kind selected from an isocyanate group and a substituent containing an isocyanate group (hereinafter referred to as “isocyanate groups”) in one molecule. As the polyisocyanate (b-1), one type may be used, or two or more types may be used. Moreover, in 1 type of polyisocyanate, isocyanate groups may be the same and may differ.

As a substituent containing an isocyanate group, a C1-C5 alkyl group, an alkenyl group, or an alkoxyl group containing one or more isocyanate groups is mentioned, for example. The number of carbon atoms of the alkyl group or the like as a substituent containing an isocyanate group is more preferably 1 to 3.
The number average molecular weight of the polyisocyanate (b-1) is such that the lower limit of the number average molecular weight is 100 or more from the viewpoint of the balance between strength and elastic modulus as a cured product obtained by curing the active energy ray-curable resin composition. The upper limit of the number average molecular weight is preferably 1000 or less, and more preferably 500 or less.

The number average molecular weight of the polyisocyanate (b-1) is calculated from the chemical formula in the case of a polyisocyanate composed of a single monomer, and from NCO% in the case of a polyisocyanate composed of two or more monomers. It can be obtained from the calculated value of.
Examples of the polyisocyanate (b-1) include aliphatic polyisocyanates, polyisocyanates having an alicyclic hydrocarbon group, and aromatic polyisocyanates.

  An aliphatic polyisocyanate is a compound having an aliphatic structure and two or more isocyanate groups bonded thereto. An aliphatic polyisocyanate is preferable from the viewpoint of enhancing the weather resistance of the cured coating (B) and imparting flexibility. The aliphatic structure in the aliphatic polyisocyanate is not particularly limited, but is preferably a linear or branched alkylene group having 1 to 6 carbon atoms. Examples of such aliphatic polyisocyanates include aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and dimer acid diisocyanate, and aliphatic triisocyanates such as tris (isocyanatohexyl) isocyanurate. Can be mentioned.

  The polyisocyanate having an alicyclic hydrocarbon group is a compound having an alicyclic hydrocarbon group and two or more isocyanate groups bonded thereto. The polyisocyanate having an alicyclic hydrocarbon group is preferable from the viewpoint of improving the mechanical strength or weather resistance of the cured coating (B). The alicyclic hydrocarbon group in the polyisocyanate having an alicyclic hydrocarbon group is not particularly limited, but preferably has 5 to 15 carbon atoms, more preferably 6 or more carbon atoms, and 7 or more carbon atoms. It is particularly preferred that Moreover, it is more preferable that it is C14 or less, and it is especially preferable that it is C13 or less. Furthermore, the alicyclic hydrocarbon group is preferably a cycloalkylene group. Examples of the polyisocyanate having an alicyclic hydrocarbon group include diisocyanates having an alicyclic hydrocarbon group such as bis (isocyanate methyl) cyclohexane, cyclohexane diisocyanate, bis (isocyanatocyclohexyl) methane, isophorone diisocyanate, and tris ( And triisocyanate having an alicyclic hydrocarbon group such as isocyanate isophorone) isocyanurate.

  An aromatic polyisocyanate is a compound having an aromatic structure and two or more isocyanate groups bonded thereto. Aromatic polyisocyanates are preferred from the viewpoint of increasing the mechanical strength of the cured coating (B). Although the aromatic structure in aromatic polyisocyanate is not specifically limited, It is preferable that it is a C6-C13 bivalent aromatic group. Examples of such aromatic polyisocyanates include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, and naphthalene diisocyanate.

<Polycarbonate polyol (b-2)>
The polycarbonate polyol (b-2) is one of the constituent components of the urethane (meth) acrylate oligomer (C).
The polycarbonate polyol (b-2) is an effective component for improving the self-healing property and stretching processability of the resin laminate.

  The polycarbonate polyol (b-2) according to the present invention preferably contains a structural unit (X) derived from 1,4-butanediol. Furthermore, the polycarbonate polyol (b-2) may contain a structural unit (X) derived from 1,4-butanediol and a structural unit (Y) derived from 1,6-hexanediol.

  That is, the polycarbonate polyol (b-2) used in the present invention is a polycarbonate diol containing a structural unit (X) derived from 1,4-butanediol, or a structural unit (X) derived from 1,4-butanediol and 1,4 butanediol. A polycarbonate diol containing a structural unit (X) derived from 6-hexanediol. 1,4-butanediol and 1,6-hexanediol are excellent in the effects described later, but are also preferable from the viewpoint of industrial availability and handling of raw materials.

Examples of the polycarbonate polyol (b-2) include a polycarbonate diol represented by the following general formula (2).
HO — [— R—O—COO—] _n —R—OH (2)
[In the formula (2), R is an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, n is an integer of 2 or more, and a plurality of R may be the same or different. May be. ]

The polycarbonate diol (b-2) represented by the general formula (2) is, for example, one or more carbonate compounds selected from the group consisting of alkylene carbonate, diaryl carbonate, and dialkyl carbonate, and 1,4 -Obtained by reacting diols containing butanediol as essential components and / or polyether polyols.
Examples of the alkylene carbonate include ethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, and the like.
Examples of the diaryl carbonate include diphenyl carbonate, phenyl-naphthyl carbonate, dinaphthyl carbonate, 4-methyl diphenyl carbonate, 4-ethyl diphenyl carbonate, 4-propyl diphenyl carbonate, 4,4′-dimethyl-diphenyl carbonate, 4, Examples include 4'-diethyl-diphenyl carbonate, 4,4'-dipropyl-diphenyl carbonate, and the like.
Examples of the dialkyl carbonate include dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, di-t-butyl carbonate, di-n-amyl carbonate, and diisoamyl. And carbonate.

The polycarbonate polyol (b-2) represented by the general formula (2) is further diols other than 1,4-butanediol and 1,6-hexanediol (hereinafter referred to as “other diols”). And / or polyether polyols (hereinafter referred to as “other polyether polyols”) may be further used and reacted within a range of addition amounts that do not impair the performance of the resin laminate. .
Examples of the other diols include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, neo Examples include pentyl glycol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, 1,12-dodecanediol, diethylene glycol, dipropylene glycol, and polybutadiene diol.
Examples of the other polyether polyols include polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran and alkylene oxide adducts of diol compounds.

  Examples of the diol compounds include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, isomer pentanediols, isomer hexanediols or Octanediols such as 2-ethyl-1,3-hexanediol, 1,2-bis (hydroxymethyl) -cyclohexanone, 1,3-bis (hydroxymethyl) -cyclohexanone, 1,4-bis (hydroxymethyl)- Examples of alkylene oxides include ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,3-butylene oxide, 2,3-butylene oxide, tetrahydrofuran, styrene, and the like. Emissions oxide, epichlorohydrin, and the like. These may be used alone, or two or more may be used.

  Among the diols and polyether polyols described above, from the viewpoint that the resin laminate is excellent in self-healing properties, the structural unit (X) derived from 1,4-butanediol includes ethylene glycol, 1,3-propanediol, Structural units derived from linear aliphatic diols such as 1,5-pentanediol and 1,12-dodecanediol are preferred, and among these, structural units derived from 1,5-pentanediol are preferred.

  In the resin laminate of the present invention, the structural unit derived from the polycarbonate diol (b-2) is a structural unit derived from 1,4-butanediol (X from the viewpoint of improving the mechanical strength of the cured coating (B). ) As an essential component. Furthermore, the structural unit derived from the polycarbonate diol (b-2) is from the viewpoint that the mechanical strength of the cured coating (B), and the self-healing property, stretching processability, and scratch resistance of the resin laminate are good. In addition to the structural unit (X) derived from 1,4-butanediol, a structural unit (Y) derived from 1,6-hexanediol is preferably included.

In the resin laminate of the present invention, the structural unit derived from the polycarbonate polyol (b-2) includes at least a structural unit (X) derived from 1,4-butanediol, and a structural unit derived from 1,4-butanediol (X ) And the content of the structural unit (Y) derived from 1,6-hexanediol,
0.7 ≦ [(X) / [(X) + (Y)]] ≦ 1.0
Is preferably satisfied.
The lower limit of the value of [(X) / [(X) + (Y)]] is not particularly limited, but self-healing property, stretching processability, scratch resistance, mechanical property of the cured coating (B) From the viewpoint of improving the strength, 0.7 or more is preferable. On the other hand, the upper limit of the value of [(X) / [(X) + (Y)]] is not particularly limited, but the greater the value, the better the mechanical strength of the cured coating (B). There is a tendency, and the upper limit is 1.0.

  Although the minimum of the number average molecular weight of the polycarbonate polyol (b-2) used by this invention is not specifically limited, From a viewpoint from which the mechanical strength of a cured film (B) becomes favorable, 500 or more are preferable. More preferably, it is 800 or more. The upper limit of the number average molecular weight of the polycarbonate polyol (b-2) is preferably 10,000 or less from the viewpoint of improving the workability without significantly increasing the viscosity of the urethane (meth) acrylate oligomer (C). More preferably, it is 5000 or less, and further preferably 2000 or less.

  A commercially available product can also be used as the polycarbonate polyol (b-2). For example, DURANOL T4671 (trade name, manufactured by Asahi Kasei Corporation, 1,4-butanediol / 1,6-hexanediol = 7/3 (mass ratio) ), Number average molecular weight = 1000), T4691 (trade name, manufactured by Asahi Kasei Corporation, 1,4-butanediol / 1,6-hexanediol = 9/1 (mass ratio), number average molecular weight = 1000).

<Hydroxyalkyl (meth) acrylate (b-3)>
Hydroxyalkyl (meth) acrylate (b-3) is one of the components of the urethane (meth) acrylate oligomer (C).
Although the said hydroxyalkyl (meth) acrylate (b-3) is not specifically limited, The hydroxyalkyl (meth) acrylate which has a C1-C30 alkylene group between a (meth) acryloyl group and a hydroxyl group. Are preferred, and hydroxyalkyl (meth) acrylates having an alkylene group having 2 to 4 carbon atoms between the (meth) acryloyl group and the hydroxyl group are more preferred.

  As hydroxyalkyl (meth) acrylate (b-3), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, Cyclohexanedimethanol mono (meth) acrylate, addition reaction product of 2-hydroxyethyl (meth) acrylate and caprolactone, addition reaction product of 4-hydroxybutyl (meth) acrylate and caprolactone, glycidyl ether and (meth) acrylic acid Use at least one selected from the group consisting of a mono (meth) acrylate of glycol, a penta (erythritol) tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate. It can be.

1 type may be used for hydroxyalkyl (meth) acrylate (b-3), and 2 or more types may be used for it.
Among the above, the number of carbon atoms is 2 to 4 between the (meth) acryloyl group and the hydroxyl group, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like. A hydroxyalkyl (meth) acrylate having an alkylene group is particularly preferred from the viewpoint of improving the mechanical strength of the resulting cured film (B).

  The molecular weight of the hydroxyalkyl (meth) acrylate (b-3) is preferably 40 or more, more preferably 80 or more, and from the viewpoint of the mechanical strength of the resulting cured film, it is 800 or less, and further 400 or less. Is preferred. In addition, when the hydroxyalkyl (meth) acrylate (b-3) is the above addition reactant or polymer, the molecular weight is a number average molecular weight.

<Other raw material compounds>
The raw material compound for producing the urethane (meth) acrylate oligomer (C) in the present invention may further contain other components as long as the effects of the present invention are obtained. Examples of such other components include a low molecular weight polyol (b-4) having a molecular weight of less than 500, which will be described later, and another high molecular weight polyol (b-5), which will be described later (provided that the polycarbonate polyol (b- Except 2)).

<Low molecular weight polyol (b-4)>
The low molecular weight polyol (b-4) is a compound having a molecular weight of less than 500 and having two or more hydroxyl groups. 1 type may be used for a low molecular weight polyol, and 2 or more types may be used for it.
Examples of such low molecular weight polyols include:
Ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,2-butane Diol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,2,4 -Trimethyl-1,5-pentanediol, 2,3,5-trimethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl -1,6-hexanediol, 3,3-dimethylol heptane, 1,8-octanedioe , 2-methyl-1,8-octanediol, aliphatic diols such as 1,9;
Cyclopropanediol, cyclopropanedimethanol, cyclopropanediethanol, cyclopropanedipropanol, cyclopropanedibutanol, cyclopentanediol, cyclopentanedimethanol, cyclopentanediethanol, cyclopentanedipropanol, cyclopentanedibutanol, cyclohexanediol, cyclohexane Dimethanol, cyclohexanediethanol, cyclohexanedipropanol, cyclohexanedibutanol, cyclohexenediol, cyclohexenedimethanol, cyclohexenediethanol, cyclohexenedipropanol, cyclohexenedibutanol, cyclohexadienediol, cyclohexadienedimethanol, cyclohexadienediethanol, cyclohexadienedip Propanol, cyclohexadienyl engine butanol, hydrogenated bisphenol A, tricyclodecane diol, alicyclic diol such as adamantyl diol;
Aromatic diols such as bishydroxyethoxybenzene, bishydroxyethyl terephthalate, bisphenol A;
Dialkanolamines such as N-methyldiethanolamine;
Pentaerythritol;
Sorbitol;
Mannitol;
Glycerin; and
Examples include trimethylolpropane.

Among these, aliphatic diols and alicyclic diols are preferable from the viewpoint of the weather resistance of the obtained cured film. In particular, in applications where the mechanical strength of the cured product is required, for example,
Ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,2-butanediol, 1,3-butanediol, 1 Aliphatic diols having 1 to 4 carbon atoms between hydroxyl groups, such as 1,4-butanediol;
Examples thereof include alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A in which two hydroxyl groups are present at symmetrical positions with an alicyclic hydrocarbon group interposed therebetween.

  The molecular weight of the low molecular weight polyol (b-4) is preferably 50 or more from the viewpoint of the balance between elongation and elastic modulus as a cured product obtained by curing the active energy ray-curable resin composition, On the other hand, it is preferably 250 or less, and more preferably 150 or less.

<Other high molecular weight polyol (b-5)>
The other high molecular weight polyol (b-5) is a compound other than a polycarbonate diol having a number average molecular weight of 500 or more and having two or more hydroxyl groups (provided that the high molecular weight polycarbonate polyol (b-2) is except).
Although there is no restriction | limiting in particular in the upper limit of the number average molecular weight of another high molecular weight polyol (b-5), Usually, it is 10,000 or less.
1 type may be used for the said other high molecular weight polyol (b-5), and 2 or more types may be used for it.

  Examples of such other high molecular weight polyols (b-5) include polyether diols, polyester diols, polyether ester diols, polyolefin polyols, and silicone polyols. The cured film obtained is flexible. Polyether diol is particularly preferable from the viewpoint of imparting a self-healing property.

  Examples of the polyether diol include compounds obtained by ring-opening polymerization of cyclic ethers such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. These may use 1 type and may use 2 or more types.

  Examples of the polyester diol include compounds obtained by polycondensation of a dicarboxylic acid or its anhydride and a low molecular weight diol, such as polyethylene adipate, polypropylene adipate, polybutylene adipate, polyhexamethylene adipate, and polybutylene sebacate. Is mentioned. These may use 1 type and may use 2 or more types. Examples of the polyester diol include compounds obtained by ring-opening polymerization of a lactone with a low molecular weight diol, such as polycaprolactone and polymethylvalerolactone. These may use 1 type and may use 2 or more types.

  Examples of the dicarboxylic acid include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, isophthalic acid, and phthalic acid. Examples of these products include these anhydrides. Examples of the low molecular weight diol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and polytetramethylene. Glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-ethyl-1,3-hexane glycol, 2,2,4-trimethyl- Examples include 1,3-pentanediol, 3,3-dimethylolheptane, 1,9-nonanediol, 2-methyl-1,8-octanediol, cyclohexanedimethanol, and bishydroxyethoxybenzene.

Examples of the polyether ester diol include compounds obtained by ring-opening polymerization of a cyclic ether to the polyester diol, and compounds obtained by polycondensation of the polyether diol and the dicarboxylic acid. For example, poly (polytetramethylene ether) Examples include adipate. These may use 1 type and may use 2 or more types.
The polyolefin polyol is a polyolefin having two or more hydroxyl groups, and examples thereof include polybutadiene polyol, hydrogenated polybutadiene polyol, and polyisoprene polyol. These may use 1 type and may use 2 or more types.

  The silicone polyol is a silicone having two or more hydroxyl groups, and examples of the silicone polyol include polydimethylsiloxane polyol. These may use 1 type and may use 2 or more types.

<Method for producing urethane (meth) acrylate oligomer (C)>
Next, a method for producing the urethane (meth) acrylate oligomer (C) of the present invention obtained from the above raw material compound will be described.

  The urethane (meth) acrylate oligomer (C) of the present invention is obtained by adding the polycarbonate polyol (b-2) and the high molecular weight hydroxyalkyl (meth) acrylate (b-3) to the polyisocyanate (b-1). It can be produced by reacting. When the low molecular weight polyol (b-4) and other high molecular weight polyol (b-5), which are other raw material compounds, are used in combination, the urethane (meth) acrylate oligomer (C) of the present invention contains These other raw material compounds can also be produced by addition reaction with isocyanate (b-1).

In addition, the charging ratio of each raw material compound at that time is substantially equal to or the same as the composition of the target urethane (meth) acrylate oligomer (C).
These addition reactions can be performed by any known method. Examples of such a method include the following methods (a) to (c).
(A) An isocyanate-terminated urethane prepolymer obtained by reacting a component other than the hydroxyalkyl (meth) acrylate with a polyisocyanate under a condition that the isocyanate group becomes excessive is obtained, and then the isocyanate-terminated urethane prepolymer A prepolymer method in which a hydroxyalkyl (meth) acrylate is reacted.

(B) One-shot method in which all raw material compounds are added simultaneously and reacted.
(C) obtained by reacting the polyisocyanate with the hydroxyalkyl (meth) acrylate first, and synthesizing a urethane (meth) acrylate prepolymer having a (meth) acryloyl group and an isocyanate group in the molecule at the same time. A method of reacting raw material compounds other than these with a prepolymer.

  Among these, according to the method (a), the urethane prepolymer is obtained by subjecting the polyisocyanate and the polycarbonate diol to a urethanation reaction, and the resulting urethane (meth) acrylate oligomer (C) is at the end. From the viewpoint that the urethane prepolymer having an isocyanate group has a structure obtained by urethanation with the hydroxyalkyl (meth) acrylate, the molecular weight can be controlled, and an acryloyl group can be introduced at both ends. Is preferred.

In the urethane (meth) acrylate oligomer (C) of the present invention, the amount of all isocyanate groups and the amount of all functional groups that react with isocyanate groups such as hydroxyl groups and amino groups are usually equimolar.
That is, the polyisocyanate (b-1), the high-molecular-weight polycarbonate polyol (b-2), and the hydroxyalkyl (meth) acrylate (b-3) in producing the urethane (meth) acrylate oligomer (C) of the present invention. ) And other raw material compounds are used in such a manner that the amount of all isocyanate groups in the urethane (meth) acrylate oligomer (C) of the present invention and the amount of all functional groups reacting therewith are equimolar, or the amount relative to the isocyanate groups. The amount is 50 to 200 mol% in terms of mol% of all functional groups.

  When producing the urethane (meth) acrylate oligomer (C) of the present invention, the amount of hydroxyalkyl (meth) acrylate (b-3) used is hydroxyalkyl (meth) acrylate (b-3), high molecular weight polycarbonate. Polyol (b-2), and other raw material compounds used as necessary, such as low molecular weight polyol (b-4), other high molecular weight polyol (b-5) and other compounds containing functional groups that react with isocyanates Is usually 3 mol% or more, preferably 5 mol% or more, and usually 70 mol% or less, preferably 50 mol% or less, more preferably 30 mol% or less. According to this ratio, the molecular weight of the urethane (meth) acrylate oligomer (C) to be obtained can be controlled. When the proportion of hydroxyalkyl (meth) acrylate is large, the molecular weight of the urethane (meth) acrylate oligomer (C) tends to be small, and when the proportion is small, the molecular weight tends to be large.

  The use amount of the high molecular weight polycarbonate polyol (b-2) may be 25 mol% or more with respect to the total use amount of the high molecular weight polycarbonate polyol (b-2) and the other high molecular weight polyol (b-5). Preferably, it is 50 mol% or more, more preferably 70 mol% or more. When the amount of the high molecular weight polycarbonate polyol (b-2) used is larger than the lower limit, it is preferable because the resulting cured product tends to have good self-restoring properties, scratch resistance and scratch resistance.

  The amount of the high molecular weight polycarbonate polyol (b-2) used is 10% by mass or more based on the total amount of the high molecular weight polycarbonate polyol (b-2) and the other high molecular weight polyol (b-5). More preferably, it is 30 mass% or more, More preferably, it is 50 mass% or more, Most preferably, it is 70 mass% or more. When the amount of the high-molecular-weight polycarbonate polyol (b-2) used is larger than the lower limit, the resulting cured product tends to improve the self-healing property, scratch resistance and scratch resistance, which is preferable.

  Further, the total amount of the high molecular weight polycarbonate polyol (b-2), the other high molecular weight polyol (b-5), and the low molecular weight polyol (b-4) is higher than that of the high molecular weight polycarbonate polyol (b-2). The amount used is preferably 25 mol% or more, more preferably 50 mol% or more, and still more preferably 70 mol% or more. When the amount of the high-molecular-weight polycarbonate polyol (b-2) used is larger than the lower limit, the resulting cured product tends to improve the self-healing property, scratch resistance and stretch processability, which is preferable.

In the production of the urethane (meth) acrylate oligomer (C) of the present invention, the total content of the urethane (meth) acrylate oligomer (C) to be produced and its raw material compound is 20% by mass relative to the total amount of the reaction system. The above is preferable, and 40% by mass or more is more preferable. In addition, the upper limit of this total content is 100 mass%. It is preferable for the total content of the urethane (meth) acrylate oligomer (C) and the raw material compounds to be 20% by mass or more because the reaction rate tends to increase and the production efficiency tends to improve.
In the production of the urethane (meth) acrylate oligomer (C) of the present invention, an addition reaction catalyst can be used. The addition reaction catalyst can be selected from the range in which the effects of the present invention can be obtained, and examples thereof include dibutyltin laurate, dibutyltin dioctoate, dioctyltin dilaurate, and dioctyltin dioctoate. An addition reaction catalyst may be used individually by 1 type, and 2 or more types may be mixed and used for it. Of these, the addition reaction catalyst is preferably dioctyltin dilaurate from the viewpoints of environmental adaptability, catalytic activity, and storage stability.

The addition reaction catalyst has an upper limit of usually 1000 ppm by mass or less, preferably 500 ppm by mass or less, and a lower limit of usually 10 ppm, based on the total content of the urethane (meth) acrylate oligomer (C) and raw material compounds to be produced. It is used at mass ppm or more, preferably at 30 mass ppm or more.
Further, when the urethane (meth) acrylate oligomer (C) of the present invention is produced, a polymerization inhibitor can be used in combination when the reaction system contains a (meth) acryloyl group. Such a polymerization inhibitor can be selected from the range in which the effects of the present invention can be obtained, for example, phenols such as hydroquinone, methylhydroquinone, hydroquinone monoethyl ether, dibutylhydroxytoluene, amines such as phenothiazine and diphenylamine, Examples thereof include copper salts such as copper dibutyldithiocarbamate, manganese salts such as manganese acetate, nitro compounds, and nitroso compounds. A polymerization inhibitor may be used individually by 1 type, and 2 or more types may be mixed and used for it. Of these, phenols are preferable as the polymerization inhibitor.

The polymerization inhibitor has an upper limit of usually 3000 ppm by mass or less, preferably 1000 ppm by mass or less, particularly preferably 500 ppm or less, based on the total content of the urethane (meth) acrylate oligomer (C) and raw material compounds to be produced. The lower limit is usually 50 ppm by mass or more, preferably 100 ppm by mass or more.
In the production of the urethane (meth) acrylate oligomer (C) of the present invention, the reaction temperature is usually 20 ° C. or higher, preferably 40 ° C. or higher, and more preferably 60 ° C. or higher. A reaction temperature of 20 ° C. or higher is preferable because the reaction rate increases and the production efficiency tends to improve. Moreover, reaction temperature is 120 degrees C or less normally, and it is preferable that it is 100 degrees C or less. It is preferable for the reaction temperature to be 120 ° C. or lower because side reactions such as an allohanato reaction hardly occur. When the reaction system contains a solvent, the reaction temperature is preferably lower than the boiling point of the solvent. When (meth) acrylate is contained, the reaction temperature is 70 ° C. from the viewpoint of preventing the reaction of the (meth) acryloyl group. The following is preferable. The reaction time is usually about 5 to 20 hours.

The lower limit of the number average molecular weight of the urethane (meth) acrylate oligomer (C) thus obtained is that the stretchability of the resin laminate is good, and the balance between the stretchability, self-repairability, and scratch resistance is good. From the viewpoint of excellent, 500 or more is preferable. The lower limit of the number average molecular weight is more preferably 1000 or more, and further preferably 3000 or more. On the other hand, the upper limit of the number average molecular weight is preferably 15000 or less from the viewpoint of good scratch resistance of the resin laminate and excellent balance between stretch processability, self-repairability, and scratch resistance. The upper limit of the number average molecular weight is more preferably 12000 or less, and even more preferably 5000 or less. This is because the stretch processability depends on the distance between the cross-linking points in the network structure. When this distance is increased, the structure becomes flexible and easily stretched, and the stretch processability is excellent. When this distance is shortened, the network structure becomes a strong structure. It is presumed that this is because of excellent scratch resistance.
The molecular weight between calculated network crosslinking points of the resin (B1) having a crosslinked structure of the present invention is preferably 1000 or more and 15000 or less.

<Molecular weight between calculation network cross-linking points>
In the present specification, the molecular weight between the calculated network crosslinking points of the resin (B1) having a crosslinked structure constituting the cured coating (B) is an active energy ray reaction that forms a network structure in the entire composition of the resin (B1). The average value of molecular weight between groups (hereinafter sometimes referred to as “crosslinking point”) is represented. The molecular weight between the calculated network crosslinking points correlates with the network area at the time of forming the network structure, and the larger the calculated molecular weight between the crosslinking points, the lower the crosslinking density. In the reaction by active energy ray curing, when a compound having only one active energy ray reactive group (hereinafter, sometimes referred to as “monofunctional compound”) reacts, it becomes a linear polymer, while the active energy A network structure is formed when a compound having two or more linear reactive groups (hereinafter sometimes referred to as “polyfunctional compound”) reacts.

  Therefore, the active energy ray reactive group of the polyfunctional compound is a crosslinking point, and the calculation of the molecular weight between the calculated network crosslinking points is centered on the polyfunctional compound having the crosslinking point, and the monofunctional compound has the polyfunctional compound. The molecular weight between the crosslinking points is treated as having an effect of extending the molecular weight, and the molecular weight between the calculation network crosslinking points is calculated. In addition, the calculation of the molecular weight between the calculation network crosslinking points is performed on the assumption that all the active energy ray reactive groups have the same reactivity and that all the active energy ray reactive groups react by irradiation with the active energy ray. .

In a polyfunctional compound single-system composition in which only one type of polyfunctional compound reacts, the molecular weight between the calculated network cross-linking points is twice the average molecular weight per active energy ray reactive group of the polyfunctional compound. . For example, (1000/2) × 2 = 1000 for a bifunctional compound with a molecular weight of 1000, and (300/3) × 2 = 200 for a trifunctional compound with a molecular weight of 300.
In a polyfunctional compound mixed system composition in which multiple types of polyfunctional compounds react, the average value of the molecular weights between the calculated network cross-linking points of each of the above single systems with respect to the total number of active energy ray reactive groups contained in the composition is This is the molecular weight between the calculated network crosslinking points of the composition. For example, in a composition comprising a mixture of 4 moles of a bifunctional compound having a molecular weight of 1000 and 4 moles of a trifunctional compound having a molecular weight of 300, the total number of active energy ray reactive groups in the composition is 2 × 4 + 3 × 4 = 20. The molecular weight between the calculated network cross-linking points of the composition is {(1000/2) × 8 + (300/3) × 12} × 2/20 = 520.

  When a monofunctional compound is included in the composition, a molecule formed by calculation and equimolar to the active energy ray reactive group (that is, the crosslinking point) of the polyfunctional compound, and the monofunctional compound linked to the crosslinking point Assuming that the reaction takes place in the middle of the chain, the extension of the molecular chain by the monofunctional compound at one crosslinking point is the total molecular weight of the monofunctional compound, and the total active energy ray reaction of the polyfunctional compound in the composition. Half of the value divided by the radix. Here, since the molecular weight between the calculated network cross-linking points is considered to be twice the average molecular weight per cross-linking point, the amount extended by the monofunctional compound relative to the calculated molecular weight between the cross-linking points calculated for the polyfunctional compound is The value obtained by dividing the total molecular weight of the monofunctional compound by the total number of reactive energy ray reactive groups of the polyfunctional compound in the composition.

For example, in a composition comprising a mixture of 40 mol of a monofunctional compound having a molecular weight of 100 and 4 mol of a bifunctional compound having a molecular weight of 1000, the number of reactive energy ray reactive groups of the polyfunctional compound is 2 × 4 = 8. The extension due to the monofunctional compound in the molecular weight between the network crosslinking points is 100 × 40/8 = 500. That is, the molecular weight between calculated network crosslinks of the composition is 1000 + 500 = 1500.
From the above, the monofunctional compound M _A molar molecular weight W _A, the mixture of the f _B functional compound MB mole of molecular weight W _B, and f _C functional compound M _C mol molecular weight W _C, the composition The molecular weight between the calculated network crosslinking points can be expressed by the following formula.

The molecular weight between the calculated network crosslinking points of the resin (B1) having the crosslinked structure of the present invention calculated as described above is preferably 1000 or more, more preferably 3000 or more, and 15000 or less. Is more preferable and 12000 or less is particularly preferable.
When the molecular weight between the calculated network cross-linking points is 15000 or less, the surface of the cured film (B) of the obtained resin laminate has good scratch resistance, and the balance between stretch workability, self-repairing property, and scratch resistance is achieved. This is preferable because it tends to be excellent. Moreover, it is preferable that the molecular weight between calculated network cross-linking points is 1000 or more because the stretchability of the obtained cured film is good and the balance between the stretchability, self-repairability and scratch resistance tends to be excellent. This is because stretch processability and scratch resistance depend on the distance between cross-linking points in the network structure, and when this distance is increased, the structure becomes flexible and easily stretched, and the stretch processability is excellent. This is presumably because it has a strong structure and excellent scratch resistance.

Further, when the molecular weight between calculated network cross-linking points is in the range of 1000 or more and 15000 or less, it is easy to obtain an active energy ray-curable resin composition that can satisfy the elastic modulus described later, and a cured film having excellent self-repairing properties. It can be.
As a method of adjusting the molecular weight between the calculation network cross-linking points, for example, the number average molecular weight of the urethane (meth) acrylate oligomer (C) can be lowered or a polyfunctional acrylate can be added.

<Active energy ray-curable resin composition>
The active energy ray-curable resin composition of the present invention containing the urethane (meth) acrylate oligomer (C), the surface slip agent (B2), and the liquid organic compound (B3) will be described below.
The active energy ray-curable resin composition of the present invention may further contain components other than the urethane (meth) acrylate oligomer (C) of the present invention within a range where the effects of the present invention are obtained. Examples of such other components include an active energy ray-reactive monomer, an active energy ray-curable oligomer, a polymerization initiator, a photosensitizer, an epoxy compound, an additive, and a solvent.

  In the active energy ray-curable resin composition of the present invention, the lower limit of the content of the urethane (meth) acrylate oligomer (C) is the active energy ray reactivity from the viewpoint of improving the scratch resistance of the resin laminate. 95.0% by mass or more is preferable with respect to 100% of the total mass of the components. 98.0 mass% or more is more preferable, and 99.25 mass% or more is further more preferable. The upper limit of the content of the urethane (meth) acrylate oligomer (C) is based on 100% of the total mass of the active energy ray-reactive component from the viewpoint that the stretchability and self-recoverability of the resin laminate are improved. 99.9905 mass% or less is preferable. 99.95 mass% or less is more preferable, and 99.90 mass% or less is further more preferable.

  In the active energy ray-curable resin composition of the present invention, the lower limit of the content of the surface slip agent (B2) makes the self-healing property of the resin laminate good, and further reduces the frictional resistance of the cured coating (B). From the viewpoint of improving the scratch resistance of the resin laminate, 0.0095% by mass or more is preferable with respect to 100% of the total mass of the active energy ray-reactive component. 0.05 mass% or more is more preferable, and 0.1 mass% or more is further more preferable. The upper limit of the content of the surface slip agent (B2) is 5.0% by mass or less from the viewpoint that the adhesiveness of the cured coating (B) can be maintained and the scratch resistance and self-repairing property of the resin laminate can be maintained well. Is preferred. 2.0 mass% or less is more preferable, and 0.75 mass% or less is further more preferable.

  The active energy ray-curable resin composition of the present invention includes a mold release agent, a lubricant, a plasticizer, an antioxidant, an antistatic agent, a light stabilizer, an ultraviolet absorber, a flame retardant, and a flame retardant as necessary. In addition, various additives such as a polymerization inhibitor, a filler, a pigment, a dye, a silane coupling agent, a leveling agent, an antifoaming agent, a fluorescent agent, or a chain transfer agent can be contained.

  The viscosity of the active energy ray-curable resin composition of the present invention can be appropriately adjusted according to the use and usage of the composition, but from the viewpoints of handleability, coatability, moldability, three-dimensional formability, etc. The viscosity at 25 ° C. in an E-type viscometer (rotor 1 ° 34 ′ × R24) is more preferably 10 mPa · s or more and 10,000 mPa · s or less. The viscosity of the active energy ray-curable resin composition can be adjusted by, for example, the content of the urethane (meth) acrylate oligomer (C) of the present invention, the type of the optional component, the blending ratio thereof, and the like.

  The active energy ray-curable resin composition of the present invention can have a tensile elastic modulus of 100 MPa or more and 1000 MPa or less measured by a method described later. Good self-repairability can be obtained when the tensile modulus is 100 MPa or more and 1000 MPa or less. If the tensile modulus is less than 100 MPa, the cured film surface is too sticky and the friction coefficient increases, so that the load on the cured film surface increases and the wound may not be repaired. On the other hand, if it exceeds 1000 MPa, the cured film is too hard, so that it is impossible to disperse the load due to elasticity, and the wound cannot be repaired.

The tensile elastic modulus of the active energy ray-curable resin composition can be controlled by adjusting the type and amount ratio of the raw material compound used for producing the urethane (meth) acrylate oligomer (C).
For example, the elastic modulus can be increased by using a low molecular weight polyol. In adjusting the elastic modulus, the high molecular weight polycarbonate polyol (b-2) and the low molecular weight polyol should be used in the range of low molecular weight polyol / high molecular weight polycarbonate polyol (b-2) 50/50 to 0/100 (mass ratio). Is preferred. In addition, the elastic modulus can be lowered by using a polyether polyol which is another high molecular weight polyol (b-5) and / or a polyether (meth) acrylate which is an active energy ray reactive monomer.

<Polymerization initiator>
The polymerization initiator is a component for curing the curable composition, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator. As the polymerization initiator, a photo radical polymerization initiator which is a compound having a property of generating radicals by light is generally used. For example, benzophenone, 2,4,6-trimethylbenzophenone, 4,4-bis (diethylamino) Benzophenone, 4-phenylbenzophenone, methylorthobenzoylbenzoate, thioxanthone, diethylthioxanthone, isopropylthioxanthone, chlorothioxanthone, 2-ethylanthraquinone, t-butylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane- 1-one, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzo Isobutyl ether, methylbenzoylformate, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethyl Benzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and 2-hydroxy-1- [ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl] -2-methyl-propan-1-one and the like can be mentioned. A radical photopolymerization initiator may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  Furthermore, you may use together radical photopolymerization initiator and a photosensitizer. As the photosensitizer, a known photosensitizer can be used, for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, methyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid. Examples include ethyl, amyl 4-dimethylaminobenzoate, and 4-dimethylaminoacetophenone. A photosensitizer may be used individually by 1 type and may be used in mixture of 2 or more types.

<Method for producing resin laminate>
As for the resin laminated body of this invention, the following method 1 and method 2 are mentioned, for example.
(Method 1) A method of obtaining a resin laminate by applying a curable composition to the surface of a resin substrate and then curing the curable composition to form a cured film.
(Method 2) After applying a resin substrate forming composition for forming a resin substrate on the surface of a cured film formed by curing the curable composition, the resin substrate forming composition is applied. A method in which a resin laminate is obtained by cast polymerization to form a resin base layer.

In the said method, the method 1 is preferable from a viewpoint which is excellent in the balance of the surface hardness of the cured film of a resin laminated body, and the crack resistance of this cured film.
Examples of the method 1 include the following method (B-1).
<Method (B-1)>
The method for producing a resin laminate of the present invention is a method for producing a resin laminate comprising sequentially performing the following steps (1) to (3).

  Step (1): 100 parts by mass of a mixture containing 95.0 to 99.99% by mass of urethane (meth) acrylate oligomer (C) and 0.01 to 5.0% by mass of the surface slip agent (B2), and liquid The active energy ray-curable resin composition containing 50 to 1000 parts by mass of the organic compound (B3) is applied to at least one surface of the resin base material (A) made of (meth) acrylic resin.

Step (2): After step (1), the liquid organic compound (B3) contained in the active energy ray-curable resin composition applied to the resin base material (A) is the active energy ray-curable resin. It heats until it becomes 10 mass% or less with respect to the total mass of a composition.
Step (3): After the step (2), the active energy ray-curable resin composition is irradiated with active energy rays and cured to form a cured coating (B), and the resin substrate (A ) To obtain a resin laminate having the cured coating (B) formed thereon.

  The urethane (meth) acrylate oligomer (C) is a structural unit derived from polyisocyanate (b-1), a structural unit derived from polycarbonate polyol (b-2), and a hydroxyalkyl (meth) acrylate (b- 3) The total amount of the structural unit derived from (b-1), the structural unit derived from (b-2), and the structural unit derived from (b-3) is 100 mol%. In contrast, 30 to 50 mol% of structural units derived from (b-1), 10 to 50 mol% of structural units derived from (b-2), and 3 to 30 mol% of structural units derived from (b-3) Containing.

  In the step (1), the urethane (meth) acrylate oligomer (C) and the surface slip agent (B2) are the urethane (meth) acrylate oligomer (C) and the surface slip agent (B2) described above. Similar ones can be used. The liquid organic compound (B3) will be described later. The method for applying the active energy ray-curable resin composition to at least one surface of the resin substrate (A) is not particularly limited, and examples thereof include a casting method, a roller coating method, a bar coating method, and a spraying method. A known coating method such as a coating method or an air knife coating method can be used.

In the step (2), when cured with active energy rays, the applied active energy ray-curable resin composition is applied from the viewpoint of good curability and mechanical strength of the cured coating (B) obtained after curing. The content of the liquid organic compound (B3) contained therein is removed by heating until it becomes 10% by mass or less with respect to 100% by mass of the total mass of the active energy ray-curable resin composition. Is preferred.
The heating method in the step (2) is not particularly limited, and for example, a known method such as heat treatment at 50 to 100 ° C. using a steam dryer or the like can be used.

  In said process (3), it can be set as a cured film (B) by irradiating an active energy ray curable resin composition with an active energy ray. Examples of the active energy rays include infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α rays, β rays, γ rays, and the like, and ultraviolet rays or electron beams can be used from the viewpoint of apparatus cost and productivity. Ultra-high pressure mercury lamp, high pressure mercury lamp, medium pressure mercury lamp, low pressure mercury lamp, metal halide lamp, electron beam irradiation device, Ar laser, He-Cd laser, solid state laser, xenon lamp, high frequency An induction mercury lamp, sunlight, etc. are mentioned.

The irradiation amount (integrated light amount) of the active energy ray can be appropriately selected according to the type of the active energy ray. For example, when curing by irradiation with a metal halide lamp, it is preferably 50 to 1000 mJ / cm ² . When it hardens | cures by electron beam irradiation, it is preferable that the irradiation amount is 1-10 Mrad. In the curing treatment, the curable resin composition exposed to an inert gas such as air, nitrogen or argon may be irradiated with active energy rays. Moreover, you may irradiate an active energy ray to the curable resin composition enclosed with the sealed space between a film or glass, and a metal metal mold | die.

  The film thickness of the finally obtained cured film (B) is appropriately determined according to the intended use, but the lower limit is preferably 1 μm, more preferably 3 μm, and particularly preferably 5 μm. The upper limit is preferably 200 μm, more preferably 100 μm, and particularly preferably 50 μm. When the film thickness is 1 μm or more, the design properties and functionality after the stretching process are improved, and when it is 200 μm or less, the internal curability and the stretch processability are favorable. In industrial use, the lower limit is preferably 1 μm, more preferably 5 μm, and particularly preferably 10 μm. The upper limit is preferably 100 μm, more preferably 50 μm.

<Liquid organic compound (B3)>
In the present invention, the liquid organic compound (B3) is one of the components of the active energy ray-curable resin composition.
By adding the liquid organic compound (B3) to the active energy ray-curable resin composition, the viscosity of the curable resin composition can be adjusted to improve the coating property.

  As the kind of the liquid organic compound (B3), a known liquid organic compound can be used. Specific examples include known organic solvents such as toluene, xylene, ethyl acetate, butyl acetate, isopropanol, isobutanol, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, and propylene glycol monomethyl ether. These organic solvents may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  As the kind of the liquid organic compound (B3), alcohols and esters are particularly preferable from the viewpoints of solubility in the active energy ray-curable resin composition, easiness of heat removal in the step (2), safety and the like. , Ether, and ketone are preferable, and at least one selected from methyl ethyl ketone, propylene glycol monomethyl ether, and isopropanol is more preferable.

  The addition amount of the liquid organic compound (B3) is not particularly limited, and may be added according to the application method of the active energy ray-curable resin composition. Generally, a liquid organic compound (B3) can be added so that it may become the range of 50 to 1000 mass parts with respect to 100 mass parts of solid content of an active energy ray curable resin composition. .

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.

<Evaluation method>
<Number average molecular weight (1)>
The theoretical number average molecular weight of the urethane (meth) acrylate oligomer (C) was calculated according to the following method.

  The urethane (meth) acrylate oligomers (C) of Examples and Comparative Examples include structural units derived from polyisocyanate, structural units derived from polycarbonate diol, and structural units derived from hydroxyalkyl (meth) acrylate as constituent units. . Since these structural units are formed while maintaining the molecular weight of each component in the urethane (meth) acrylate oligomer (C), in this example and the comparative example, the urethane (meth) acrylate oligomer ( The number average molecular weight of the urethane (meth) acrylate oligomer (C) is determined by the sum of the product of the molar ratio of each component until the formation of C) (hydroxyalkyl (meth) acrylate is calculated by 2) and the molecular weight of each component. The number average molecular weight (1) was calculated.

<Number average molecular weight (2)>
The number average molecular weight of the urethane (meth) acrylate oligomer (C) obtained using gel permeation chromatography (GPC) was measured according to the following method.
Using a high-speed gel permeation chromatography device (device name: HLC-8120GPC, manufactured by Tosoh Corporation), using THF as a solvent, polystyrene as a standard sample, and TSKgel superH1000, H2000, and H3000 as columns, a liquid feed rate of 0.5 mL / Minute, the number average molecular weight was measured at a column oven temperature of 40 ° C., and this was defined as the number average molecular weight (2).

<Molecular weight between calculation network cross-linking points>
The molecular weight between calculated network crosslinking points of the resin (B1) having a crosslinked structure was calculated according to the following method.
The resin (B1) having a crosslinked structure in each Example and Comparative Example is obtained by curing the urethane (meth) acrylate oligomer (C) prepared by the above-described (a) prepolymer method. Since the (meth) acryloyl group present in one molecule of the (meth) acrylate oligomer (C) serves as a crosslinking point in the resin (B1), the molecular weight between calculated network crosslinking points is calculated from the following formula (2). Asked.

<Tensile strength, elongation at break, tensile modulus>
The break elongation of the cured film of the active energy ray-curable resin composition is used as an index of the stretchability of the resin laminate, and the active energy ray curability is used as an index of the self-healing property and scratch resistance of the resin laminate. The tensile strength and tensile elastic modulus of the cured film of the resin composition were measured by the following methods.
The active energy ray-curable resin composition was formed on the non-adhesive surface side of a polyethylene terephthalate film (Toyobo A4100 film 100 μm) using a bar coater so that the cured film thickness was 20 μm. Then, it was dried at 70 ° C. for 5 minutes. Next, after irradiating the dried coating film with ultraviolet rays from a metal halide lamp (output 120 W / cm ² ) under the condition of 500 mJ / cm ² , the cured film was further formed by allowing to stand at 23 ° C. for 1 day. Thereafter, the cured film was peeled off from the polyethylene terephthalate film to finally obtain a cured film having a thickness of 20 μm.

Next, the obtained cured film was cut into a width of 10 mm, and the temperature was 23 ° C., the relative humidity was 55% RH, and the tensile speed was 50 mm using an autograph precision universal testing machine (device name: AGS-X, manufactured by Shimadzu Corporation). A tensile test was performed under the conditions of / min and a distance between chucks of 50 mm, and the elongation at break, tensile strength, and tensile modulus were measured.
For the tensile modulus, the straight line (tangent line at the origin of the SS curve) connecting the stress at 0% elongation and the stress at 0.5% elongation of the obtained stress-strain curve (SS curve) is extended, The stress converted at 100% elongation was taken as the tensile modulus.

<Self-healing: pencil scratch test>
The self-healing property of the resin laminate was evaluated by a pencil scratch test described later. At least 7 mm on the surface of the cured film (B) of the resin laminate using a pencil having a pencil density of 3H by a method according to JIS K5600-5-4 (load 750 ± 10 g, speed 30-60 mm / min). Ten scratches were formed, and the scratched scratches remaining were observed by visually observing the scratched portion after 24 hours in an environment of 23 ± 2 ° C. and humidity (50 ± 5)%. Was recorded. The determination was made according to the following criteria.

○: The number of remaining scratches is 2 or less ×: The number of remaining scratches is 3 or more In addition, a scratch test is performed in the same manner as above using a pencil with a pencil concentration of 2H and a pencil with 4H. The number of scratches remaining after 24 hours was recorded.

<Abrasion resistance: Stea wool resistance>
The scratch resistance of the resin laminate was evaluated by a steel wool abrasion test described later. The haze value measured before the steel wool wear test for the resin laminate is defined as H1. On the other hand, under an atmosphere of 23 ° C. and 55% RH, a weight of 250 gf (per area of 4 cm ² ) was placed on steel wool (# 0000) manufactured by Nippon Steel Wool Co., Ltd. The measured haze value was H2.

Difference between H2 and H1: ΔH (ΔH = H2−H1) was determined.
In the above, the haze value was measured according to JIS K7105 using a haze meter (device name: NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.). The smaller the value of ΔH, the better the resin laminate is in scratch resistance.

<Cross-cut peel test>
The adhesiveness of the cured coating (B) in the resin laminate was evaluated by a cross-cut peel test in accordance with JIS K5600-5-4 and according to the following criteria.

○: No peeling of the cured coating (B) was observed in all 25 squares.
(Triangle | delta): Peeling of the cured film (B) was seen by 1-5 mass out of 25 mass.
X: Peeling of the cured coating (B) was observed at 6 squares or more out of 25 squares.

<Raw materials>
Abbreviations of the compounds used in Examples and Comparative Examples are as follows.
<Base material>
Acrylic base material: Acrylic resin board (Product name: Acrylite L # 001, board thickness 3 mm, manufactured by Mitsubishi Chemical Corporation)
PET base material: Polyester film (Product name: A4100, thickness 100 μm, manufactured by Toyobo Co., Ltd.)

<Polyisocyanate (b-1)>
IPDI: Isophorone diisocyanate (Product name: VES TANAT IPDI, manufactured by Evonik Degussa Japan)

<Polycarbonate polyol (b-2)>
T4691: Polycarbonate polyol having a number average molecular weight of 1000 (product name: Duranol T4691, manufactured by Asahi Kasei Corporation, 1,4-butanediol / 1,6-hexanediol = 9/1 (mass ratio))

<Hydroxyalkyl (meth) acrylate (b-3)>
HEA: 2-hydroxyethyl acrylate (manufactured by Osaka Organic Industry Co., Ltd.)
PETA: Pentaerythritol triacrylate (Product name: A-TTM-3, manufactured by Shin-Nakamura Chemical Co., Ltd.)

<Low molecular weight polyol (b-4)>
1,12-DD: 1,12-dodecanediol (manufactured by Ube Industries)
CHDM: 1,4-cyclohexanedimethanol (manufactured by Nippon Nippon Chemical Co., Ltd.)

<Other high molecular weight polyol (b-5)>
PCL210: Polycaprocraton polyol having a number average molecular weight of 1000 (Product name: Plaxel 210, manufactured by Daicel Chemical Industries)
PTMG1000: Polyether polyol having a number average molecular weight of 1000 (Product name: PTMG1000, manufactured by Mitsubishi Chemical Corporation)

<Surface slip agent (B2)>
Slip agent 1: polyether-modified polydimethylsiloxane (product name: BYK-378, manufactured by Big Chemie Japan)
Slip agent 2: modified polydimethylsiloxane having an acrylic group (product name: BYK-3505, manufactured by Big Chemie Japan)
Slip agent 3: System compound represented by the following general formula (1) (Product name: Optool DAC, manufactured by Daikin Industries, Ltd.)

<Liquid organic compound (B3)>
MEK: Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.)
PGM: Propylene glycol monomethyl ether (manufactured by Sankyo Chemical Co., Ltd.)
IPA: Isopropanol (manufactured by Sankyo Chemical Co., Ltd.)

<UV initiator>
UV initiator 1: (1-hydroxycyclohexyl) phenylmethanone (product name: Irgacure 184, manufactured by BASF Japan Ltd.)

[Production Example 1]
In a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 11.6 g of IPDI as polyisocyanate (b-1) and 21.6 g of T4691 as polycarbonate polyol (b-2) And 53 g of 1,12-DD as low molecular weight polyol (b-4), 560 g of MEK as liquid organic compound (B3), 0.02 g of dioctyltin dilaurate as catalyst, and heated to 80 ° C. in an oil bath. The reaction was continued for 9 hours. After cooling to 60 ° C. after completion of the reaction, 0.1 g of dioctyltin dilaurate as a catalyst, 0.2 g of methylhydroquinone, 40 g of MEK as a liquid organic compound (B3), and 25 g of PETA as a hydroxyalkyl (meth) acrylate (b-3) are added. The reaction was started dropwise. The reaction was carried out for 10 hours while heating to 70 ° C. in an oil bath, and the progress of the reaction was confirmed by a change in the intensity of the peak derived from the isocyanate (NCO) group in the infrared absorption spectrum. The oligomer (C1) was obtained as a urethane (meth) acrylate-based oligomer (C), when the peak disappeared at the end of the reaction. The number average molecular weight (2) of the oligomer (C1) determined by GPC was 11,000.

[Production Examples 2 to 4]
A urethane (meth) acrylate oligomer (C) was obtained under the same conditions as in Example 1 except that the production conditions of the urethane (meth) acrylate oligomer (C) were changed as shown in Table 1.
Table 1 shows the number average molecular weight (2) of the urethane (meth) acrylate oligomer (C) determined by GPC.

[Example 1]
In the compounding amounts shown in Table 2, the urethane (meth) acrylate oligomer (C), slip agent 1 as the surface slip agent (B2), MEK as the liquid organic compound (B3), and UV initiation as the UV initiator Agent 1 was added and mixed to obtain an active energy ray-curable resin composition 1.

The composition ratio of the raw material compounds used for the production of this urethane (meth) acrylate oligomer (C) is polyisocyanate (b-1) / polycarbonate polyol (b-2) / hydroxyalkyl (meth) acrylate (b-3) = It is 12.3 / 5.1 / 2.04 (molar ratio), and the solid content in the active energy ray-curable resin composition is 40% by mass.
The obtained active energy ray-curable resin composition was measured for tensile strength, breaking elongation, and tensile modulus according to the evaluation method described above, and the results are shown in Table 3.

The obtained active energy ray-curable resin composition was applied to one surface of an acrylic base material as a resin base material (A).
Next, the applied resin laminate is heated at 70 ° C. for 5 minutes, so that MEK contained in the active energy ray-curable resin composition is 100% by mass of the total mass of the active energy ray-curable resin composition. It heated until it became 10 mass% or less with respect to.
Next, a resin in which the cured coating film is formed on the surface of the resin base material (A) by irradiating the heated coating film with ultraviolet rays from a metal halide lamp (output 120 W / cm ² ) under the condition of 500 mJ / cm ^2. A laminate was obtained.

With respect to the obtained resin laminate, the molecular weight between calculated network crosslinking points of the resin (B1) having a crosslinked structure constituting the cured coating (B) was 3,200.
The obtained resin laminate was evaluated for self-healing property, scratch resistance (ΔH), and adhesion (cross-cut peel test) according to the evaluation method described above. The evaluation results are shown in Table 4.
[Comparative Example 1]
A resin laminate was produced under the same conditions as in Example 1 except that the surface slip agent (B2) was not used.
Table 4 shows the evaluation results of the obtained active energy ray-curable resin composition and the resin laminate.

[Examples 2 to 18, Comparative Examples 2 to 7]
Under the same conditions as in Example 1, except that the production conditions of the urethane (meth) acrylate oligomer (C) or the active energy ray-curable resin composition were changed as shown in Tables 1 to 3, the resin laminate was used. Manufactured.

  Table 4 or Table 5 shows the evaluation results of the obtained active energy ray-curable resin composition and the resin laminate.

[Comparative Example 8]
Table 5 shows the results of evaluating the self-healing property and scratch resistance (ΔH) of the acrylic base material alone according to the above-described evaluation method without forming the cured film (B) layer on the acrylic base material. Show.

[Comparative Examples 9-12]
Except for changing the resin base material (A) to a PET base material, Comparative Example 9 is the same as Example 3, Comparative Example 10 is the same as Example 5, and Comparative Example 11 is Example 7. Under the same conditions, Comparative Example 12 produced a resin laminate under the same conditions as Comparative Example 3.

In the self-healing property, scratch resistance, and cross-cut peel test, the active energy ray-curable resin composition was applied to the easily adhesive surface side of the PET base material to form a layer of the cured coating (B). .
Table 4 or Table 5 shows the evaluation results of the obtained active energy ray-curable resin composition and the resin laminate.

[Reference Example 1]
Evaluation of self-healing property and scratch resistance (ΔH) of a PET base material alone (non-adhesive surface) without forming a cured coating layer (B) on the PET base material according to the evaluation method described above. The results are shown in Table 3.
In Comparative Examples 1, 2, and 4, since the content of the surface slip agent (B2) was small, the self-healing property and scratch resistance of the resin laminate were insufficient.
In Comparative Examples 3 and 5, since the content of the surface slip agent (B2) was large, the adhesiveness of the cured film (B) was insufficient, and the self-healing property of the resin laminate was insufficient.

In Comparative Example 6, since the cured coating film (B) had a high tensile elastic modulus, the self-healing property and scratch resistance of the resin laminate were insufficient. Moreover, the elongation at break of the cured coating (B) was low, and the molding processability of the resin molding was insufficient.
In Comparative Example 7, since the tensile modulus of the cured coating (B) was low, the self-healing property and scratch resistance of the resin laminate were insufficient.

In Comparative Example 8, since the layer of the cured film (B) was not formed, the self-healing property and scratch resistance of the resin laminate were insufficient.
In Comparative Examples 9 to 12, since the resin base material (A) is not a resin base material made of a (meth) acrylic resin, the self-healing property of the resin laminate was insufficient.

Claims (19)

A resin laminate comprising a cured coating (B) on at least one surface of a resin base material (A) made of a (meth) acrylic resin,
The tensile modulus of the cured coating (B) is 100 MPa or more and 1000 MPa or less,
Ten scratches at least 7 mm on the surface of the cured coating (B) using a pencil having a pencil density of 3H by a method according to JIS K5600-5-4 (load 750 ± 10 g, speed 30-60 mm / min). A resin laminate in which scratches are formed and the number of scratches is 24 or less after 24 hours have passed in an environment of temperature 23 ± 2 ° C. and humidity (50 ± 5)%. The cured film (B) is a cured film containing a resin (B1) having a crosslinked structure and a surface slip agent (B2), and the molecular weight between calculated network crosslinking points of the resin (B1) having the crosslinked structure is 1000 or more and 15000. The resin laminate according to claim 1, which is as follows. A resin laminate comprising a cured coating (B) on at least one surface of a resin base material (A) made of a (meth) acrylic resin,
The cured film (B) is a cured film containing a resin (B1) having a crosslinked structure and a surface slip agent (B2),
The resin laminate, wherein the resin (B1) has a molecular weight between calculated network cross-linking points of 1000 or more and 15000 or less.   The cured film (B) is a cured film formed by curing an active energy ray-curable resin composition containing a urethane (meth) acrylate oligomer (C) and a surface slip agent (B2). Resin laminate.   The resin laminated body of Claim 4 whose tensile elasticity modulus of the cured film formed by hardening | curing the said active energy ray curable resin composition is 100 Mpa or more and 1000 Mpa or less. The resin (B1) having the crosslinked structure contains 40% by mass or more of a structural unit derived from the urethane (meth) acrylate oligomer (C) with respect to 100% by mass of the total mass of the resin (B1), and
The structural unit derived from the urethane (meth) acrylate oligomer (C) is a structural unit derived from a polyisocyanate (b-1), a structural unit derived from a polycarbonate polyol (b-2), and a hydroxyalkyl (meth) acrylate ( The resin laminate according to claim 4 or 5, comprising a structural unit derived from b-3).   The resin laminate according to claim 6, wherein the structural unit derived from (b-2) includes a structural unit (X) derived from 1,4-butanediol. The resin laminate according to claim 6 or 7, wherein the structural unit derived from (b-1) is a structural unit derived from polyisocyanate having an alicyclic hydrocarbon group having 5 to 15 carbon atoms.   The structural unit derived from the urethane (meth) acrylate oligomer (C) is 30 to 50 mol% of the structural unit derived from the (b-1), 10 to 50 mol% of the structural unit derived from the (b-2), and The resin laminate according to any one of claims 6 to 8, comprising 3 to 30 mol% of the structural unit derived from (b-3). The structural unit derived from (b-2) includes at least a structural unit (X) derived from 1,4-butanediol,
The content of the structural unit (X) derived from 1,4-butanediol and the content of the structural unit (Y) derived from 1,6-hexanediol are:
0.7 ≦ [(X) / [(X) + (Y)]] ≦ 1.0
The resin laminate according to any one of claims 6 to 9, wherein the resin laminate is satisfied.   The structural unit derived from (b-3) is a structural unit derived from hydroxyalkyl (meth) acrylate having an alkylene group having 2 to 4 carbon atoms between a (meth) acryloyl group and a hydroxyl group. The resin laminate according to any one of 10.   The structural unit derived from (b-3) is a repeating unit derived from 2-hydroxyethyl (meth) acrylate, a repeating unit derived from 2-hydroxypropyl (meth) acrylate, or a repeating unit derived from 4-hydroxybutyl (meth) acrylate Repeating unit derived from 6-hydroxyhexyl (meth) acrylate, repeating unit derived from cyclohexanedimethanol mono (meth) acrylate, structural unit derived from addition reaction product of 2-hydroxyethyl (meth) acrylate and caprolactone, 4-hydroxy Structural unit derived from addition reaction product of butyl (meth) acrylate and caprolactone, structural unit derived from addition reaction product of glycidyl ether and (meth) acrylic acid, structural unit derived from mono (meth) acrylate of glycol, pentaerythritol bird( Data) acrylate repeating unit derived from, and is at least one selected from the group consisting of dipentaerythritol penta (meth) acrylate repeating unit derived from the resin laminate according to any one of claims 6-11.   The said hardened film (B) contains 0.0095 mass% or more and 5.0 mass% or less of the said surface slip agent (B2) with respect to 100 mass% of total mass of this cured film (B). The resin laminated body as described in any one of -12.   The said cured film (B) contains 0.02 mass% or more and 0.75 mass% or less of the said surface slip agent (B2) with respect to 100 mass% of total mass of this cured film (B). The resin laminated body as described in any one of -12.   The resin laminate according to any one of claims 3 to 14, wherein the surface slip agent (B2) contains a compound having a siloxane bond unit in the molecule.   The resin laminate according to any one of claims 3 to 14, wherein the surface slip agent (B2) comprises a compound having a perfluoroalkyl group or a perfluoropolyether group. The resin laminate according to claim 16, wherein the surface slip agent (B2) is a compound represented by the following general formula (1).

[In formula (1), Rf represents a perfluoroalkyl group or a perfluoropolyether group. ] A method for producing a resin laminate,
The manufacturing method of the resin laminated body including performing the following process (1)-(3) sequentially.
Step (1): 100 parts by mass of a mixture containing 95.0 to 99.99% by mass of urethane (meth) acrylate oligomer (C) and 0.01 to 5.0% by mass of the surface slip agent (B2), and liquid The active energy ray-curable resin composition containing 50 to 1000 parts by mass of the organic compound (B3) is applied to at least one surface of the resin base material (A) made of (meth) acrylic resin.
Step (2): After step (1), the liquid organic compound (B3) contained in the active energy ray-curable resin composition applied to the resin base material (A) is the active energy ray-curable resin. It heats until it becomes 10 mass% or less with respect to 100 mass% of total mass of a composition.
Step (3): After the step (2), the active energy ray-curable resin composition is irradiated with an active energy ray and cured to form a cured film, and the surface of the resin substrate (A) A resin laminate having the cured coating formed thereon is obtained.
The urethane (meth) acrylate oligomer (C) is a structural unit derived from polyisocyanate (b-1), a structural unit derived from polycarbonate polyol (b-2), and a hydroxyalkyl (meth) acrylate (b- 3) The total amount of the structural unit derived from (b-1), the structural unit derived from (b-2), and the structural unit derived from (b-3) is 100 mol%. In contrast, 30 to 50 mol% of structural units derived from (b-1), 10 to 50 mol% of structural units derived from (b-2), and 3 to 30 mol% of structural units derived from (b-3) Containing. The manufacturing method of the resin laminated body of Claim 18 whose said liquid organic compound (B3) is at least 1 sort (s) chosen from alcohol, ester, ether, and a ketone.