JP2018167574A - Self-repairing laminate and protective film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a self-repairing laminate having good scratch resistance and good adhesion between a polyurethane resin film and a self-repairing resin layer made of an active energy ray-curable composition, or the self-repairing laminate. A protective film using a body is provided. SOLUTION: A self-repairing resin layer (A) and a self-repairing resin layer (B) composed of an active energy ray-curable composition are provided on a polyurethane resin film in this order. Sex laminate. Further, a protective film for a vehicle exterior coating film or a screen protective film for a display, which is made of the self-healing laminate. [Selection diagram] Fig. 1

Description

  The present invention relates to a self-healing laminate in which an intermediate resin layer and a self-healing resin layer are provided in this order on a polyurethane resin film, and a protective film for a vehicle exterior coating film using the self-healing laminate And a screen protection film for display devices.

  Protective adhesive film in which an adhesive layer is laminated on a polyurethane resin film (for example, Patent Documents 1 and 2) or polyurethane resin to protect the exterior coating surface of a vehicle body such as an automobile or motorcycle from a stepping stone A protective adhesive film having a thermosetting topcoat layer on one surface of the film and an adhesive layer on the other surface is known (for example, Patent Documents 3 and 4).

  In addition, automobile interior parts (instrument panels, console boxes, door trims, etc.), electronic equipment housings (portable personal computers, mobile devices, mobile phones, electronic notebooks, etc.), home appliances (TVs, refrigerators, washing machines, etc.), etc. In order to prevent the outer surface of the resin molded product from being scratched, the outer surface of the resin molded product may be coated (applied) with a self-healing resin layer having a self-healing function (self-healing function) It has been proposed (Patent Documents 5 and 6).

Japanese Patent Laid-Open No. 2005-133013 JP 2005-272558 A JP 2003-27016 A JP 2009-299035 A JP 2011-207909 A JP 2013-27998 A

  Polyurethane resin films are relatively flexible and have excellent followability to the curved surface of the vehicle body, but on the other hand, they are easily scratched by external forces and swell and dissolve in general organic solvents such as ketones and alcohols. Therefore, there is a problem that the physical properties tend to decrease. The organic solvent resistance tends to be improved by providing a thermosetting topcoat layer on the polyurethane resin film, but the scratch resistance is not sufficiently satisfactory.

  On the other hand, when a self-healing resin layer composed of an active energy ray-curable composition is laminated on the polyurethane resin film in order to impart scratch resistance to the polyurethane resin film, the polyurethane resin film and the self-healing resin layer There was a problem with adhesion.

  Therefore, in view of the above-described problems, the object of the present invention is to provide self-scratch resistance and good adhesion between the polyurethane resin film and the self-healing resin layer made of the active energy ray-curable composition. It is to provide a restorative laminate. Another object of the present invention is to provide a protective film using the self-healing laminate.

The above problem can be solved by the invention described below.
[1] A self-healing property characterized in that an intermediate resin layer (A) and a self-healing resin layer (B) made of an active energy ray-curable composition are provided in this order on a polyurethane resin film. Laminated body.
[2] The self-repairing laminate according to [1], wherein the intermediate resin layer (A) contains a resin having a urethane bond in the molecule.
[3] The self-healing laminate according to [1] or [2], wherein the intermediate resin layer (A) is a resin layer made of a thermosetting composition or a resin layer made of a lacquer composition.
[4] The self-healing laminate according to [3], wherein the thermosetting composition contains a compound containing a hydroxyl group and a compound containing an isocyanate group.
[5] The contact angle with respect to water of the surface of the self-healing resin layer (B) is 75 ° or more, and the contact angle with respect to oleic acid on the surface of the self-healing resin layer (B) is 35 ° or more. [1] A self-repairing laminate according to any one of [4].
[6] The self-healing laminate according to any one of [1] to [5], wherein the active energy ray-curable composition contains a fluorine compound.
[7] The self-healing laminate according to [6], wherein the fluorine compound is composed of a compound containing a polymerizable double bond group in the molecule.
[8] The self-repairing laminate according to any one of [1] to [7], wherein the intermediate resin layer (A) has a thickness of 0.1 μm or more and less than 10 μm.
[9] The self-healing laminate according to any one of [1] to [8], wherein the self-healing resin layer (B) has a thickness of 5 μm or more and 50 μm or less.
[10] The polyurethane resin film has an adhesive layer on the surface opposite to the surface on which the intermediate resin layer (A) and the self-repairing resin layer (B) are provided. [9] The self-healing laminate according to any one of [9].
[11] A protective film for a vehicle exterior coating film, comprising the self-healing laminate according to any one of [1] to [10].
[12] A screen protective film for a display comprising the self-healing laminate according to any one of [1] to [10].

  According to the present invention, there is provided a self-healing laminate having good scratch resistance and good adhesion between a polyurethane resin film and a self-healing resin layer comprising an active energy ray-curable composition. Can do. Moreover, according to the preferable aspect of this invention, the self-repairing laminated body with favorable water repellency and oil repellency can be provided. Moreover, according to the preferable aspect of this invention, a self-repairing laminated body with favorable weather resistance can be provided. The self-healing laminate according to the present invention is suitable for a protective film for a vehicle exterior coating film and a screen protection film for a display device, and particularly suitable for a protective film for a vehicle exterior coating film.

FIG. 1 is a schematic cross-sectional view of an example of the self-healing laminate of the present invention.

  The self-healing laminate according to the present invention has an intermediate resin layer (A) and a self-healing resin layer (B) made of an active energy ray-curable composition in this order on a polyurethane resin film. Hereinafter, the self-healing resin layer (B) made of the active energy ray-curable composition may be referred to as “self-healing resin layer (B)”.

  FIG. 1 is a schematic cross-sectional view of an example of a self-healing laminate according to the present invention. The self-healing laminate 1 includes a polyurethane resin film 2, an intermediate resin layer (A) 3 laminated thereon, and a self-healing resin layer (B) 4 laminated thereon.

  By providing the self-healing resin layer (B) made of the active energy ray-curable composition on the polyurethane resin film, the scratch resistance is improved. However, the adhesion between the polyurethane resin film and the self-healing resin layer (B) made of the active energy ray-curable composition is not sufficient, and film peeling may occur. In addition, this adhesion problem may promote the generation of cracks when the self-healing laminate is stretched. This problem is solved by disposing the intermediate resin layer (A) between the polyurethane resin film and the self-restoring resin layer (B).

[Polyurethane resin film]
The polyurethane resin film is a resin film containing at least a polyurethane resin. The polyurethane resin film may be a polyurethane single resin film made of only a polyurethane resin, or may be a composite film of a polyurethane resin and another resin, such as an acrylic resin, a polycarbonate resin, a polyester resin, or a polyolefin resin. . Moreover, the laminated film of a polyurethane resin film and other resin films (For example, an acrylic resin film, a polycarbonate resin film, a polyester resin film, a polyolefin resin film etc.) may be sufficient. The polyurethane resin film in the present invention is preferably a polyurethane single resin film from the viewpoint of moldability.

  Examples of the material of the polyurethane resin film include a polycarbonate skeleton polyurethane resin, a polyester skeleton polyurethane resin, and a polyether skeleton polyurethane resin. These polyurethane resins are preferably thermoplastic resins.

  The above-mentioned polyurethane resin having a polycarbonate skeleton is obtained by a reaction between a polycarbonate polyol and a polyisocyanate, and the above polyurethane resin having a polyester skeleton is obtained by a reaction between a polyester polyol (including polycaprolactone polyol) and a polyisocyanate. Can be obtained by reaction of a polyether polyol and a polyisocyanate.

  Among the polyurethane resin films described above, from the viewpoint of weather resistance (anti-yellowing property), an aliphatic polyurethane resin film is preferable, an aliphatic polyurethane resin film having a polyester skeleton is more preferable, and a fat having a polycaprolactone skeleton is particularly preferable. A group polyurethane resin film is preferred.

  The above aliphatic polyurethane resin is obtained by a reaction between a polyol compound having no aromatic ring and a polyisocyanate compound having no aromatic ring.

  Since the aliphatic polyurethane resin film is excellent in weather resistance, the self-healing laminate using the aliphatic polyurethane resin film is suitable as a protective film for a vehicle exterior coating film used outdoors.

  Moreover, an aromatic polyurethane resin film can be used as a polyurethane resin film. The aromatic polyurethane resin film is relatively inferior in weather resistance to the aliphatic polyurethane resin film, but is excellent in solvent resistance. Since the self-repairing laminate using an aromatic polyurethane resin film has good solvent resistance, it is suitable as a protective film for a vehicle exterior coating film on which adhesion of engine oil or its cleaner is assumed. The weak point of the weather resistance of the self-healing laminate using the aromatic polyurethane resin film is that the self-healing resin layer (B) and / or the intermediate resin layer (A) contains an ultraviolet absorber as described later. This is further suppressed by containing an ultraviolet absorber and a light stabilizer.

  The thickness of the polyurethane resin film is not particularly limited, but is preferably in the range of 30 to 300 μm, more preferably in the range of 50 to 250 μm, and particularly preferably in the range of 75 to 200 μm from the viewpoints of strength and processability.

  Polyurethane resin films may be transparent, translucent or opaque, depending on their application site and desired effects. Moreover, a coloring pattern, a pattern, etc. may be given. In general, a transparent state is preferably used for the polyurethane resin film.

  Polyurethane resin film optionally contains light stabilizers, UV absorbers, catalysts, solvents, flow agents, leveling agents, colorants, gloss modifiers, etc. in order to improve the appearance, weather resistance, and other decorative properties. You can also

  The polyurethane resin film can be formed by various methods such as a melt extrusion method, an inflation method, and a casting method.

[Intermediate resin layer (A)]
The intermediate resin layer (A) is provided between the polyurethane resin film and the self-healing resin layer (B), and has a function of improving the adhesion between the polyurethane resin film and the self-healing resin layer (B). Furthermore, the intermediate resin layer (A) preferably has a function of improving the solvent resistance of the polyurethane resin film.

  The thickness of the intermediate resin layer (A) is preferably from 0.1 μm to less than 10 μm, more preferably from 0.5 μm to 5 μm, and particularly preferably from 1 μm to 3 μm.

  If the thickness of the intermediate resin layer (A) is less than 0.1 μm, it will not contribute sufficiently to improving the adhesion between the polyurethane resin film and the self-repairing resin layer (B), or improve the solvent resistance of the polyurethane resin film. It may not contribute enough.

  On the other hand, when the thickness of the intermediate resin layer (A) is larger than 10 μm, the flexibility is lowered, and the curved surface followability at the time of application may be lowered.

  The intermediate resin layer (A) is a resin layer (thermosetting resin layer) or lacquer property made of a thermosetting composition from the viewpoint of improving the adhesion between the polyurethane resin film and the self-restoring resin layer (B). A resin layer (lacquer resin layer) made of the composition is preferred. Moreover, it is more preferable that it is a resin layer which consists of a thermosetting composition from a viewpoint of the solvent resistance improvement of a polyurethane resin film. That is, the intermediate resin layer (A) is preferably not a resin layer made of an active energy ray-curable composition from the viewpoint of improving the adhesion between the polyurethane resin film and the self-restoring resin layer (B). When the intermediate resin layer (A) is a resin layer made of an active energy ray-curable composition, the adhesion between the polyurethane resin film and the self-healing resin layer (B) cannot be sufficiently improved.

  Here, the resin layer composed of a lacquer composition refers to a composition in which the composition does not contain a crosslinking agent or a curing agent and a relatively strong film is formed by volatilization of the solvent.

  Examples of the resin constituting the intermediate resin layer (A) include acrylic resins, polyurethane resins, acrylic / urethane resins, polyester resins, polyolefin resins, epoxy resins, and composite resins thereof. Among the above resins, a resin having a urethane bond in the molecule is preferable, and examples of the resin include a polyurethane resin and an acrylic / urethane resin. A resin having a urethane bond in the molecule can be obtained, for example, by a reaction between a compound containing a hydroxyl group and a compound containing an isocyanate group.

  Examples of the aspect in which the intermediate resin layer (A) contains a resin having a urethane bond in the molecule include the following aspects.

(I) A mode in which a composition (thermosetting composition) containing a compound having a hydroxyl group and a compound having an isocyanate group is coated on a polyurethane resin film, dried and heated (ii) urethane in the molecule A mode in which a composition containing a resin having a bond (lacquer composition) is applied on a polyurethane resin film and dried (iii) A mode in which the above (i) and (ii) are combined (composite type)

  Among the above embodiments, the embodiment (i) is preferable. In the embodiment (i), the composition (thermosetting composition) containing a compound having a hydroxyl group and a compound having an isocyanate group is a compound having a hydroxyl group and an isocyanate group having a hydroxyl group by applying heat. The isocyanate group causes a urethane bond to produce a resin having a urethane bond in the molecule.

Hereinafter, the aspect (thermosetting composition) of the above (i) will be described in detail.
Examples of the compound having a hydroxyl group include acrylic polyols, polyether polyols, polyester polyols, polyolefin polyols, polycarbonate polyols, urethane polyols, etc., and these may be one kind or a blend of two or more kinds.

  The acrylic polyol having a hydroxyl group can be obtained, for example, by copolymerizing a (meth) acrylic monomer and a hydroxyl group-containing (meth) acrylic monomer. Here, “(meth) acryl” is a general term for “acryl” and “methacryl”. In the following description, “... (Meth) acrylate” is a general term for “... Acrylate” and “.

  Examples of (meth) acrylic monomers include (meth) acrylic acid alkyl ester monomers. Examples of such compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and tert-butyl (meth) acrylate. , Lauryl (meth) acrylate, stearyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, methylhexyl (meth) acrylate, cyclododecyl (meth) acrylate, isobornyl (meth) acrylate, and the like. .

  Examples of hydroxyl group-containing (meth) acrylic monomers include hydroxyethyl (meth) acrylate, polyoxyethylene (meth) acrylate, polyoxypropylene (meth) acrylate, polycaprolactone-modified (meth) acrylate, and polycarbonate polyol-modified (meth) acrylate. And polyester polyol-modified (meth) acrylate.

Examples of the acrylic polyol having a hydroxyl group include DIC Corporation; (trade name “Acridic” (registered trademark) series, etc.), Taisei Fine Chemical Co., Ltd. (trade name “Acrit” (registered trademark) series, etc.), Nippon Shokubai; (trade name “Akreset” (registered trademark) series, etc.), Mitsui Chemicals, Inc. (trade name “Takelac” (registered trademark) UA series), etc. Can do.
Polyether polyols having a hydroxyl group include polyethylene glycol or triol, polypropylene glycol or triol, polybutylene glycol or triol, polytetramethylene glycol or triol, and addition polymers or block copolymers of these oxyalkylene compounds having different carbon numbers. A polymer etc. are mentioned. Polyether polyols having such hydroxyl groups include Asahi Glass Co., Ltd. (trade name “Excenol” (registered trademark) series, etc.), Mitsui Chemicals Co., Ltd. (trade name “Accor” (registered trademark) series, etc.) These products can be used.

  Examples of the polyester polyol having a hydroxyl group include aliphatic glycols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, decanediol, cyclohexanedimethanol and caprolactone diol, and succinic acid and adipic acid. An aliphatic polyester polyol reacted as an essential raw material component with an aliphatic dibasic acid such as sebacic acid, fumaric acid, suberic acid, azelaic acid, 1,10-decamethylene dicarboxylic acid, cyclohexane dicarboxylic acid, ethylene glycol, Fragrance produced by reacting aliphatic glycols such as propylene glycol and butanediol with aromatic dibasic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid as essential raw material components And polyester polyols.

  Examples of the polyester polyol having a hydroxyl group include DIC Corporation (trade name “Polylite” (registered trademark) series, etc.), Kuraray Co., Ltd. (trade name “Kuraray polyol” (registered trademark) series, etc.), Takeda Pharmaceutical Company Limited. (Trade name “Takelac” (registered trademark) U series), and these products can be used.

  Examples of the polyolefin-based polyol having a hydroxyl group include polymers and copolymers of diolefins having 4 to 12 carbon atoms such as butadiene and isoprene, diolefins having 4 to 12 carbon atoms, and α-olefins having 2 to 22 carbon atoms. Among these types of copolymers, it is a compound containing a hydroxyl group. The method for containing a hydroxyl group is not particularly limited, and for example, there is a method of reacting a diene monomer with hydrogen peroxide. Furthermore, you may make it saturated aliphatic by hydrogen-bonding the remaining double bond. Examples of such polyolefin-based polyols containing hydroxyl groups include Nippon Soda Co., Ltd. (trade name “NISSO-PB” (registered trademark) G series, etc.), Idemitsu Kosan Co., Ltd .; (trade name “Poly bd” (registered trademark). ) Series, “Epaul” (registered trademark) series, etc.), and these products can be used.

  As the polycarbonate polyol having a hydroxyl group, for example, a polycarbonate polyol obtained by using only dialkyl carbonate and 1,6-hexanediol can be used. However, in terms of lower crystallinity, 1,6-hexane is used as the diol. It is preferable to use a polycarbonate polyol obtained by copolymerizing a diol with 1,4-butanediol, 1,5-pentanediol or 1,4-cyclohexanedimethanol.

  As the polycarbonate polyol having a hydroxyl group, Asahi Kasei Chemicals Co., Ltd., which is a copolymerized polycarbonate polyol; (trade names “T5650J”, “T5652”, “T4671”, “T4672”, etc.), Ube Industries, Ltd .; (trade name “ETERRNACLL”) "(Registered trademark) UM series, etc.)", and these products can be used.

  The urethane polyol having a hydroxyl group is obtained, for example, by reacting a polyisocyanate compound and a compound having at least two hydroxyl groups in one molecule at a ratio such that the hydroxyl group is excessive with respect to the isocyanate group. Examples of the polyisocyanate compound used at that time include hexamethylene diisocyanate, toluene diisocyanate, m-xylene diisocyanate, and isophorone diisocyanate. Examples of the compound having at least two hydroxyl groups in one molecule include polyhydric alcohols, polyester diol, polyethylene glycol, polypropylene glycol, polycarbonate diol and the like.

  As the compound having an isocyanate group, a polyisocyanate compound containing two or more isocyanate groups in the molecule is preferably used.

  Examples of the polyisocyanate compound include methylene bis-4-cyclohexyl isocyanate, trimethylol propane adduct of tolylene diisocyanate, trimethylol propane adduct of hexamethylene diisocyanate, trimethylol propane adduct of isophorone diisocyanate, isocyanurate of tolylene diisocyanate. And (poly) isocyanate such as isocyanurate of hexamethylene diisocyanate, burette of hexamethylene isocyanate, and block of the above isocyanate. Examples of such polyisocyanate compounds include Mitsui Chemicals Co., Ltd. (trade name “Takenate” (registered trademark) series, etc.), Nippon Polyurethane Industry Co., Ltd. (trade name “coronate” (registered trademark) series, etc.), Asahi Kasei Chemicals Corporation. (Trade name “Duranate” (registered trademark) series, etc.), DIC Corporation (trade name “Burnock” (registered trademark) series, etc.), and these products can be used.

  It is preferable that an intermediate | middle resin layer (A) contains a ultraviolet absorber from a viewpoint of improving the weather resistance (yellowing prevention property) of a self-restoring laminated body. The intermediate resin layer preferably further contains a light stabilizer. As the ultraviolet absorber and the light stabilizer, the same compounds as those used for the self-restoring resin layer (B) described later can be used.

[Self-healing resin layer (B)]
The self-healing resin layer (B) in the present invention is a self-healing resin layer made of an active energy ray-curable composition. That is, the self-healing resin layer (B) is a resin layer obtained by irradiating the active energy ray-curable composition with active energy rays and curing it. Examples of such active energy rays include ultraviolet rays, visible rays, infrared rays, electron beams, β rays, and γ rays. Among these active energy rays, ultraviolet rays and electron beams are preferable, and ultraviolet rays are particularly preferably used.

  Although it does not specifically limit as a light source for irradiating an ultraviolet-ray, For example, an ultraviolet fluorescent lamp, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp etc. can be used. . An ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation, or the like can also be used. Among these, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp are preferably used. In addition, when irradiating with ultraviolet rays, it is preferable to perform irradiation in an atmosphere having a low oxygen concentration, for example, an atmosphere having an oxygen concentration of 500 ppm or less because it can be cured efficiently.

Irradiation light amount of the ultraviolet rays is preferably from 50 mJ / cm ² or more, 100 mJ / cm ² or more, and particularly 150 mJ / cm ² or more. The upper limit is preferably 2,000 mJ / cm ² or less, 1,000 mJ / cm ² or less being more preferred.

  The self-repairing resin layer (B) has a function (scratch repairing function) in which a scratch attached to the surface of the self-recovering resin layer (B) self-repairs. Here, having a wound repair function means that, for example, scratches attached to the surface of the self-repairing resin layer (B) by a metal brush (brass brush) in a normal temperature (23 ° C.) environment disappear over time. Means.

  In this specification, the time when the scratch attached to the surface of the self-repairing resin layer (B) disappears with a brass brush under the following conditions in a normal temperature (23 ° C.) environment is defined as “scratch disappearance time” (measurement) Details of the conditions are described in the section of the evaluation method in the examples).

  The wound disappearance time is preferably less than 24 hours, more preferably less than 30 minutes, even more preferably less than 3 minutes, and particularly preferably less than 10 seconds. The lower limit of the disappearance time is not particularly limited, but the time for visually confirming the disappearance of the scratch is about 0.1 seconds.

  Whether or not the scratch attached to the surface of the self-restoring resin layer (B) with the brass brush has disappeared (whether or not it has a scratch repair function) can be determined by visual observation or measuring a haze value.

  The flaw repair function of the self-healing resin layer (B) can be expressed, for example, by balancing the soft segment and the hard segment of the resin constituting the self-healing resin layer (B). The soft segment acts to cushion the external force by acting as a cushion and functions to elastically recover the wound, and the hard segment functions to resist the external force. If only the soft segment is used, the elasticity becomes weak and it becomes difficult to maintain the shape, and the recoverability of the wound is lowered. On the other hand, the hard segment alone may not recover the scratch.

  From the above viewpoint, it is preferable to contain a urethane compound in the active energy ray-curable composition in order to develop a wound repair function. Examples of the urethane compound include a urethane compound having a polycaprolactone skeleton, a urethane compound having a polycarbonate skeleton, and a urethane compound having a polyether skeleton (polyalkylene glycol skeleton). In these urethane compounds, a polycaprolactone structure, a polycarbonate structure, and a polyether structure (polyalkylene glycol structure) function as a soft segment, and a urethane bond functions as a hard segment. Details will be described later.

  The surface of the self-restoring resin layer (B) preferably has high water repellency. Specifically, the contact angle of water on the surface of the self-restoring resin layer (B) is preferably 75 ° or more, more preferably 100 ° or more, further preferably 105 ° or more, and 110 ° or more. Particularly preferred. Further, the surface of the self-repairing resin layer (B) preferably has high oil repellency. Specifically, the contact angle to the oleic acid on the surface of the self-restoring resin layer (B) is preferably 35 ° or more, more preferably 50 ° or more, still more preferably 60 ° or more, and particularly preferably 70 ° or more. When the contact angle between water and oleic acid on the surface of the self-healing resin layer (B) is in the above range, it is possible to provide antifouling properties against hydrophilic and lipophilic contamination components. For example, when used outdoors. Also, the adhesion of various contaminants to the surface of the self-healing laminate can be suppressed over a long period.

  In order to increase the water repellency of the surface of the self-restoring resin layer (B), the active energy ray-curable composition preferably contains a fluorine-containing compound and / or a silicon-containing organic compound. Moreover, in order to improve the oil repellency on the surface of the self-restoring resin layer (B), the active energy ray-curable composition preferably contains a fluorine-containing compound. Details will be described later.

  The thickness of the self-healing resin layer (B) is preferably 5 μm or more, more preferably 10 μm or more, and particularly preferably 15 μm or more from the viewpoint of sufficiently exhibiting the wound repair function. On the other hand, if the thickness of the self-restoring resin layer (B) becomes too large, the moldability may be lowered. Therefore, the upper limit thickness is preferably 50 μm or less, more preferably 40 μm or less, and particularly preferably 30 μm or less.

[Active energy ray-curable composition]
The self-healing resin layer (B) in the present invention is a resin layer made of an active energy ray-curable composition. Hereinafter, the active energy ray-curable composition will be described in detail.

  The active energy ray-curable composition contains a compound that is polymerized and cured by active energy rays (hereinafter sometimes referred to as an active energy ray-curable compound). Examples of such active energy ray-curable compounds include compounds (monomers and oligomers) containing a polymerizable double bond group in the molecule. Here, examples of the polymerizable double bond group include an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an allyl group, and a vinyl group.

  As the active energy ray-curable compound, a urethane (meth) acrylate compound is preferably used from the viewpoint of imparting a wound repair function and flexibility. Examples of the urethane (meth) acrylate compound include a urethane (meth) acrylate compound having a polyether skeleton, a urethane (meth) acrylate compound having a polycaprolactone skeleton, and a urethane (meth) acrylate compound having a polycarbonate skeleton. Two or more kinds can be used in combination. Further, these compounds may be monomers or oligomers.

  The active energy ray-curable composition contains at least one selected from the group consisting of a urethane (meth) acrylate compound having a polyether skeleton, a urethane (meth) acrylate compound having a polycaprolactone skeleton, and a urethane (meth) acrylate compound having a polycarbonate skeleton. It is preferable to contain at least a urethane (meth) acrylate compound having a polyether skeleton. Moreover, it is preferable that an active energy ray-curable composition contains the urethane (meth) acrylate compound of polycarbonate frame | skeleton from a viewpoint of enlarging the crack elongation of the self-restoring laminated body mentioned later.

  Examples of the urethane (meth) acrylate compound having a polyether skeleton include the following compounds.

(1a): Compound (1b) obtained by reacting a polyalkylene glycol (meth) acrylate and an isocyanate compound; reacting the polyalkylene glycol and the isocyanate compound in a ratio such that the isocyanate group is excessive with respect to the hydroxyl group. Compound obtained by further reacting a (meth) acrylate compound containing a hydroxyl group with the compound obtained

  Examples of the polyalkylene glycol (meth) acrylate compound used in the synthesis of (1a) include polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polybutylene glycol (meth) acrylate, and the like.

  As the isocyanate compound used for the synthesis of (1a) above, a polyisocyanate compound containing two or more isocyanate groups in the molecule is preferable. For example, tolylene diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, Tetramethylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, methyl-2,6-diisocyanate hexanoate, norbonane diisocyanate, methylene bis-4-cyclohexyl isocyanate, tolylene diisocyanate Methylolpropane adduct, hexamethylene diisocyanate (Poly) isocyanate such as methylolpropane adduct, trimethylolpropane adduct of isophorone diisocyanate, isocyanurate of tolylene diisocyanate, isocyanurate of hexamethylene diisocyanate, burette of hexamethylene isocyanate, and block of said isocyanate And so on.

  Examples of the polyalkylene glycol used in the synthesis of (1b) include polyethylene glycol, polypropylene glycol, polybutylene glycol, and the like.

  As the isocyanate compound used for the synthesis of (1b), the same compound as the isocyanate compound used for the synthesis of (1a) can be used.

  Examples of the (meth) acrylate compound containing a hydroxyl group used in the synthesis of (1b) above include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl-phthalic acid, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, polyethylene glycol mono ( (Meth) acrylate, polypropylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, polycaprolactone Such as alkyl (meth) acrylate.

  Examples of the urethane (meth) acrylate compound having a polycaprolactone skeleton include the following compounds.

(2a): Compound (2b) obtained by reacting polycaprolactone-modified alkyl (meth) acrylate and an isocyanate compound; Compound (2c) obtained by reacting polycaprolactone-modified hydroxyalkyl (meth) acrylate and an isocyanate compound ); Compound obtained by reacting long-chain alkyl alcohol, polycaprolactone-modified hydroxyethyl (meth) acrylate and isocyanate compound

  Here, as an isocyanate compound, the same compound as the isocyanate compound used for the synthesis of the above-mentioned (1a) can be used.

  The urethane (meth) acrylate compound having a polycarbonate skeleton can be synthesized by reacting a polycarbonate polyol, an isocyanate compound, and a (meth) acrylate containing a hydroxyl group.

  The polycarbonate polyol can be produced by a transesterification reaction between an alkylene glycol and a carbonate ester or a reaction between phosgene or chloroformate ester and an alkylene glycol.

  Examples of the alkylene glycol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, and neopentyl. Glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 1,4-cyclohexanediol, bisphenol A, glycerin, trimethylol Examples include propane and pentaerythritol.

  Examples of the carbonate ester include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, n-propyl carbonate, di-n-propyl carbonate, isopropyl carbonate, diisopropyl carbonate, n-butyl carbonate, di-n-butyl carbonate, and isobutyl. Examples include carbonate, diisobutyl carbonate, cyclocarbonate, diphenyl carbonate, methyl diphenyl carbonate, ethylene carbonate, 1,2-propylene carbonate, and 1,2-butylene carbonate.

  The polycarbonate polyol is preferably a polycarbonate diol, and more preferably a polycarbonate diol having hydroxyl groups at both ends of the molecule.

  A commercially available product can be used as the polycarbonate polyol. For example, “Placcel CD” series manufactured by Daicel Corporation, “Kuraray polyol” series manufactured by Kuraray Co., Ltd., “Nipporan” series manufactured by Nippon Polyurethane Industry Co., Ltd., “Duranol” series manufactured by Asahi Kasei Chemicals Corporation Etc.

  The number average molecular weight of the polycarbonate polyol is preferably in the range of 300 to 7,000, more preferably in the range of 500 to 5,000, and particularly preferably in the range of 700 to 3,000.

  As the isocyanate compound, a compound similar to the isocyanate compound used in the synthesis of the above (1a) can be used.

  As the (meth) acrylate compound containing a hydroxyl group, the same compound as the (meth) acrylate compound containing a hydroxyl group used in the synthesis of (1b) described above can be used.

  The active energy ray-curable composition preferably further contains a polymerizable monomer or polymerizable oligomer other than the urethane (meth) acrylate compound.

  As a polymerizable monomer, 2-ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-ethoxyethoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2 -Monofunctional such as hydroxypropyl (meth) acrylate, polycaprolactone-modified hydroxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, N-vinylpyrrolidone, acryloylmorpholine, isobornyl acrylate, vinyl acetate, styrene Neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) arylate, 1,6-hexanediol di (meth) acrylate, 1,4-butanediol di (me ) Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol (meth) diacrylate, dipropylene glycol diacrylate, etc., trimethylolpropane tri (meth) acrylate, penta Erythritol tri (meth) acrylate, tri (meth) acrylate of 3 mol propylene oxide adduct of trimethylolpropane, tri (meth) acrylate of 6 mol ethylene oxide adduct of trimethylolpropane, glycerin propoxytri (meth) acrylate, di Polyfunctional ones such as pentaerythritol hexa (meth) acrylate and hexa (meth) acrylate of caprolactone adduct of dipentaerythritol

  Examples of the polymerizable oligomer include unsaturated polyester, polyester (meth) acrylate, polyether (meth) acrylate, acrylic (meth) acrylate, and epoxy (meth) acrylate.

  The active energy ray-curable composition preferably further contains a photopolymerization initiator. Examples of the photopolymerization initiator include isopropyl benzoin ether, isobutyl benzoin ether, benzophenone, Michler ketone, o-benzoylmethyl benzoate, acetophenone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, ethyl anthraquinone, p-dimethylaminobenzoic acid. Isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane 1-one, 2-benzyl-2-dimethylamino-1 (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Jiruhorumeto and the like.

  Moreover, from the viewpoint of enhancing the water repellency and oil repellency of the surface of the self-restoring resin layer (B), the active energy ray-curable composition preferably contains a fluorine compound.

  The fluorine compound is not particularly limited, but the number of fluorine atoms in one molecule of the fluorine compound is preferably 3 or more, more preferably 4 or more, from the viewpoint of improving water and oil repellency. One or more is more preferable, and six or more is particularly preferable. If the number of fluorine atoms increases too much, the applicability and adhesion of the active energy ray-curable composition may decrease, so the upper limit number of fluorine atoms is preferably 25 or less, more preferably 20 or less, 17 or less is particularly preferable.

  The structure of the fluorine compound is not particularly limited, but a compound containing a polymerizable double bond group in the molecule is preferable from the viewpoint of developing performance over a long period of time. The self-healing resin layer (B) obtained by curing the active energy ray-curable composition containing a fluorine compound containing a polymerizable double bond group in the molecule has a fluorine atom localized near the surface, resulting in water repellency. And oil repellency becomes high. In particular, when the active energy ray-curable composition is used in combination with the urethane (meth) acrylate compound described above and a fluorine compound containing a polymerizable double bond group in the molecule, fluorine atoms are likely to be localized near the surface. .

  The number of polymerizable double bond groups in one molecule of the fluorine compound is preferably 1 to 3, particularly preferably 1 to 2. On the other hand, if the number of polymerizable double bond groups in one molecule is more than 3, the compatibility in the active energy ray-curable resin layer may deteriorate.

  Examples of the polymerizable double bond group include a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, and a methacryloyloxy group. Among these, an acryloyloxy group and a methacryloyloxy group are preferable.

  Examples of the fluorine compound containing a polymerizable double bond group in the molecule include trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, pentafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octa Fluoropentyl (meth) acrylate, perfluorobutylethyl (meth) acrylate, perfluorobutylhydroxypropyl (meth) acrylate, perfluorohexylethyl (meth) acrylate, perfluorohexylhydroxypropyl (meth) acrylate, perfluorooctylethyl ( (Meth) acrylate, perfluorooctylhydroxypropyl (meth) acrylate, perfluorodecylethyl (meth) acrylate, heptadecafluorodecyl ( Data) acrylate, divinyl dodecafluoro hexane, divinyl hexadecafluoro octane.

  The content of the fluorine compound in the active energy ray-curable composition is 100% by mass of the total solid content of the active energy ray-curable composition (all components excluding the solvent) from the viewpoint of sufficiently exhibiting water repellency and oil repellency. 0.3 mass% or more is preferable, 0.5 mass% or more is more preferable, 1.0 mass% or more is more preferable, and 2.0 mass% or more is particularly preferable. On the other hand, when the amount of the fluorine compound is increased, the wound repair function of the self-healing resin layer (B) may be lowered. Therefore, the upper limit is preferably 20% by mass or less, more preferably 10% by mass or less. 5 mass% or less is especially preferable.

  From the viewpoint of increasing the water repellency of the surface of the self-restoring resin layer (B), the active energy ray-curable composition preferably contains a silicon-containing organic compound. Moreover, by containing a silicon-containing organic compound, the slip property of the self-restoring resin layer (B) is improved and scratch resistance is improved. The self-repairing resin layer (B) is preferably formed of a relatively soft resin from the viewpoint of developing a flaw repair function and increasing the crack elongation described later. This tackiness is improved by the silicon-containing organic compound.

  The silicon-containing organic compound is not particularly limited, but a polydimethylsiloxane copolymer is preferably used from the viewpoint of performance and availability.

  The polydimethylsiloxane copolymer may be any of a block copolymer, a graft copolymer, and a random copolymer, but a block copolymer and a graft copolymer are preferable.

  Polydimethylsiloxane copolymers can be produced by the living polymerization method, polymer initiator method, polymer chain transfer method, etc., but considering the productivity, the polymer initiator method, polymer chain transfer method can be used. It is preferable to use it.

  When the polymer initiator method is used, a block copolymer is efficiently synthesized by copolymerizing with another vinyl monomer using a polymer azo radical polymerization initiator represented by Chemical Formula 1 below. be able to.

  In addition, a two-stage polymerization is carried out by synthesizing a prepolymer in which a peroxide group is introduced into the side chain by copolymerizing a peroxy monomer and polydimethylsiloxane having an unsaturated group at a low temperature, and then copolymerizing the prepolymer with a vinyl monomer. Can also be done.

When using the polymer chain transfer method, for example, after adding HS—CH ₂ COOH or HS—CH ₂ CH ₂ COOH to a silicone oil as shown in Chemical Formula 2 below to obtain a compound having an SH group, A block copolymer can be synthesized by copolymerizing the silicone compound and a vinyl monomer using the chain transfer of the SH group.

  Further, in order to synthesize a polydimethylsiloxane graft copolymer, for example, a graft copolymer can be easily obtained by copolymerizing a compound shown in the following chemical formula 3, that is, a methacrylic ester of polydimethylsiloxane and a vinyl monomer. be able to.

  Examples of the vinyl monomer used in the copolymer with polydimethylsiloxane include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, octyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, ethyl methacrylate, n- Butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, styrene, α-methyl styrene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, Vinyl fluoride, vinylidene fluoride, glycidyl acrylate, Lysidyl methacrylate, allyl glycidyl ether, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride, acrylamide, methacrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, N, N-dimethylamino Examples thereof include ethyl methacrylate, N, N-diethylaminoethyl methacrylate, diacetylone acrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and allyl alcohol.

  The polydimethylsiloxane copolymer is usually produced by solution polymerization. In such solution polymerization, aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, propyl acetate, isobutyl acetate and butyl acetate, ethanol Alcohol solvents such as isopropanol, butanol and isobutanol are used alone or as a mixed solvent.

  Further, if necessary, a polymerization initiator such as benzoyl peroxide or azobisisobutylnitrile is used in combination. The polymerization reaction is preferably performed at 50 to 150 ° C. for 3 to 12 hours.

  Examples of the polysiloxane include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltoxioxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyl. Triethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxy Has hydrolyzable silyl groups such as silane, γ-methacryloxypropylmethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, and γ-acryloxypropylmethyldimethoxysilane. Silane compound partial hydrolysates, organosilica sols in which silicic acid fine particles are stably dispersed in an organic solvent, or those obtained by adding the radically polymerizable silane compound to the organosilica sol, etc. be able to.

  The content of the silicon-containing organic compound is preferably in the range of 0.1 to 10% by mass with respect to 100% by mass of the total solid content (all components excluding the solvent) of the active energy ray-curable composition, 0.5 to 7 The range of mass% is more preferable, and the range of 1 to 5 mass% is particularly preferable.

  The active energy ray-curable composition preferably contains an ultraviolet absorber. This improves the weather resistance (such as yellowing prevention) of the self-healing laminate.

  A known compound can be used as the ultraviolet absorber. Examples include benzotriazole-based UV absorbers, benzophenone-based UV absorbers, benzoate-based UV absorbers, and triazine-based UV absorbers, and these UV absorbers can be used alone or in combination of two or more.

  Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) -5. -Chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzo Triazole, 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl) benzotriazole, 2,2 2- (2'-hydroxyphenyl) benzotriazole such as' -methylenebis (4-tert-octyl-6-benzotriazolyl) phenol Etc. The.

  Examples of benzophenone-based ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5′-methylenebis (2-hydroxy-4-methoxy). 2-hydroxybenzophenones such as benzophenone).

  Examples of the benzoate ultraviolet absorber include phenyl salicylate, resorcinol monobenzoate, 2,4-ditertiarybutylphenyl-3,5-ditertiarybutyl-4-hydroxybenzoate, 2,4-ditertiary amylphenyl -3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate and the like.

  Examples of triazine ultraviolet absorbers include 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- (2-hydroxy-4-hexyl). Oxyphenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2 -(2-hydroxy-4-hexyloxyphenyl) -4,6-dibiphenyl-s-triazine, 2,4-bis (2-hydroxy-4-octoxyphenyl) -6- (2,4-dimethylphenyl) ) -S-triazine, 2,4,6-tris (2-hydroxy-4-octoxyphenyl) -s-triazine, 2- (4-isooctyloxycarbonylethoxy) Eniru) -4,6-triaryl triazines such as diphenyl -s- triazine.

  Moreover, as the ultraviolet absorber, an ultraviolet absorber having a polymerizable double bond group in the molecule is also preferably used.

  Examples of reactive benzotriazole-based ultraviolet absorbers include 2- (2′-hydroxy-5 ′ (meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5 ′-(meta). ) Acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-5 '-(meth) acryloyloxypropylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5) '-(Meth) acryloyloxypropylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-(meth) acryloyloxyethylphenyl) -2H-benzo Triazole, 2- (2′-hydroxy-3′-tert-butyl-5 ′-(meta Acryloyloxyethyl phenyl) -5-chloro -2H- benzotriazole.

  Examples of the reactive benzophenone-based ultraviolet absorber include 2-hydroxy-4- (2- (meth) acryloyloxyethoxy) benzophenone, 2-hydroxy-4- (2- (meth) acryloyloxy) benzophenone, 2,2 '-Dihydroxy-4- (2- (meth) acryloyloxy) benzophenone, 2,2'-dihydroxy-4- (2- (meth) acryloyloxyethoxy) benzophenone, 2,2'-dihydroxy-4,4'- Examples include di (2- (meth) acryloyloxy) benzophenone and 2,2′-dihydroxy-4,4′-di (2- (meth) acryloyloxyethoxy) benzophenone.

  Examples of the reactive triazine-based UV absorber include 2,4-diphenyl-6- [2-hydroxy-4- (2- (meth) acryloyloxyphenyl)]-1,3,5-triazine, 2,4 -Diphenyl-6- [2-hydroxy-4- (2- (meth) acryloyloxyethoxyphenyl)]-1,3,5-triazine, 2,4,6-tri [2-hydroxy-4- (2- (Meth) acryloyloxyphenyl)]-1,3,5-triazine, 2,4,6-tri [2-hydroxy-4- (2- (meth) acryloyloxyethoxyphenyl)]-1,3,5- Examples include triazine.

  The content of the ultraviolet absorber is preferably in the range of 0.1 to 20% by mass with respect to 100% by mass of the total solid content (all components excluding the solvent) of the active energy ray-curable composition, and 0.3 to 15 The range of mass% is more preferable, and the range of 0.5 to 12 mass% is particularly preferable.

  The active energy ray-curable composition preferably further contains a light stabilizer. This improves the weather resistance (such as yellowing prevention) of the self-healing laminate. Examples of such light stabilizers include hindered amine light stabilizers and hindered phenol light stabilizers.

  Examples of hindered amine light stabilizers include bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl]. Methyl] butyl malonate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-popperidinyl) sebacate, bis-decanedioic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester, etc., and mixtures, modified products, polymers, derivatives, etc. thereof can be used.

  Moreover, the reactive hindered amine light stabilizer which contains a polymerizable double bond group in a molecule | numerator can also be used preferably. Examples of such compounds include 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-acryloyloxy-1- Ethyl-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-1-propyl-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-1-butyl-2,2,6 6-tetramethylpiperidine, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-1,2,2,6,6-pentamethylperidine, 4-methacryloyloxy-1- Ethyl-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-1-butyl-2,2,6,6-tetramethyl Rupiperijin, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-oxy-1-propyl-2,2,6,6-tetramethylpiperidine and the like.

  Examples of the hindered phenol light stabilizer include 1,1,3-tris- (2-methyl-4-hydroxy-5-tert-butylphenylbutane, 4,4′-butylidenebis- (3-methyl-6). -T-butylphenol), 2,2-thiobis (4-methyl-6-t-butylphenol), 7-octadecyl-3- (4'-hydroxy-3 ', 5'-di-t-butylphenyl) propionate, Tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate methane, pentaerythritol-tetrakis [3- (3,5-di-t-butyl-4 -Hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-he Xanthdiol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di- t-butylanilino) -1,3,5-triazine, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 2,2-thio-diethylenebis [3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy) -hydrocinnamide, 2,4-bis [( Octylthio) methyl] -o-cresol, 3,5-di-t-butyl-4-hydroxybenzyl-phosphonate-diethyl ester, tetrakis [methylene (3,5-di-t-butyl-4- Droxyhydrocinnamate)] methane, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) proonate, 3,9-bis [2- {3- (3-t-butyl) -4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, etc. Among them, especially penta. Erythritol-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) proonate is preferred .

  The content of the light stabilizer is preferably in the range of 0.1 to 10% by mass with respect to 100% by mass of the total solid content (all components excluding the solvent) of the active energy ray-curable composition, and 0.3 to 7 The range of mass% is more preferable, and the range of 0.5 to 5 mass% is particularly preferable.

  The active energy ray-curable composition preferably contains a combination of the above-described ultraviolet absorber and light stabilizer. The weather resistance of the self-healing laminate is further improved. From the above viewpoint, it is more preferable to contain a combination of a benzotriazole ultraviolet absorber and a hindered amine light stabilizer, and it is particularly preferable to contain a combination of a reactive benzotriazole ultraviolet absorber and a hindered amine light stabilizer. .

[Adhesive layer]
The self-healing laminate according to the present invention has a pressure-sensitive adhesive layer laminated on the surface opposite to the surface on which the intermediate resin layer (A) and the self-healing resin layer (B) of the polyurethane resin film are laminated. Is preferred. The self-healing laminate is affixed to a vehicle body, a display screen of a display device, or the like via an adhesive layer.

  As the pressure-sensitive adhesive layer, various tackifiers are preferably used. For example, acrylic resin, terpene resin, phenol resin, terpene phenol resin, silicone resin, coumarone resin, rosin compound (rosin or rosin ester, hydrogenated rosin ester), petroleum resin, xylene resin, Or a styrene resin etc. can be mentioned. Among these, acrylic pressure-sensitive adhesives are preferably used.

  As the acrylic pressure-sensitive adhesive, for example, an acrylic pressure-sensitive adhesive in which a monomer component mainly composed of an acrylate ester is copolymerized with a monomer component having a functional group such as a carboxyl group can be used.

  An acrylic pressure-sensitive adhesive obtained by copolymerizing a carboxyl group-containing ethylenically unsaturated monomer as the acrylic ester monomer component can be used.

  Although it does not specifically limit as thickness of an adhesive layer, The range of 10-200 micrometers is preferable, The range of 20-100 micrometers is more preferable, The range of 30-70 micrometers is especially preferable. The pressure-sensitive adhesive layer is preferably non-yellowing.

  Examples of acrylic ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl ( (Meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, 2-methoxyethyl (meth) ) Acrylate, butoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, etc., among which the alkyl ester moiety has 1 to 12 carbon atoms. Meth) acrylic acid alkyl esters are preferred, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, the use of 2-ethylhexyl (meth) acrylate preferred.

  Examples of the carboxyl group-containing ethylenically unsaturated monomer include (meth) acrylic acid, acrylic acid dimer, crotonic acid, maleic acid, fumaric acid, citraconic acid, glutaconic acid, itaconic acid, acrylamide N-glycolic acid, and cinnamic acid. Among them, it is preferable to use (meth) acrylic acid.

[Self-healing laminate]
When the self-healing laminate according to the present invention is attached to an adherend having a curved surface such as a vehicle body, the curved surface followability is preferably good. That is, it is preferable that the crack elongation is large. Here, the crack elongation means that when one side of the self-healing laminate is fixed and the self-healing laminate is pulled at a tensile speed of 50 mm / min, a crack occurs in the self-healing resin layer (B). The rate of growth.

  In the self-healing laminate according to the present invention, the crack elongation is preferably 50% or more, more preferably 70% or more, and particularly preferably 80% or more. The upper limit is not particularly limited, but is about 500%.

The self-healing laminate according to the present invention preferably has good weather resistance (anti-yellowing property) when applied to an outdoor adherend such as a vehicle body. That is, it is preferable that the change amount (Δb value) of the b value in the Lab color system after the weather resistance test is small. Here, the Δb value is a value obtained by subtracting the b ₀ value before the test from the b ₁ value after the weather resistance test.

  In the self-healing laminate of the present invention, the b value change amount (Δb value) before and after the weather resistance test shown in the examples is preferably 2.5 or less, more preferably 2.0 or less, and further 1.5. The following is preferable, and 1.0 or less is particularly preferable.

[Application examples of self-healing laminates]
The self-healing laminate according to the present invention can be applied as a surface protective film for various objects. For example, protective films for interior and exterior of vehicles such as ships, airplanes, railway vehicles, automobiles, and motorcycles, marking films for imparting design properties to the vehicles, screen protection films for display devices, protection of electronic equipment casings, etc. It can be applied to films, protective films such as buildings and signboards.

  Since the self-healing laminate according to the present invention is excellent in scratch resistance, it is suitable as a protective film for a vehicle body or a screen protective film for a display. In particular, it is suitable as a protective film for protecting the exterior coating film of vehicles such as automobiles and motorcycles from stepping stones.

  Furthermore, the self-healing laminate according to the present invention has high water repellency and oil repellency, good adhesion suppression and wiping properties such as rainwater, muddy water or engine oil, and good weather resistance. It is suitable for outdoor use and is particularly suitable as a protective film for the above-described vehicle exterior coating film.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples. In addition, the measuring method and evaluation method in a present Example are shown below.

(1) Evaluation of adhesion of self-healing resin layer (B) The self-healing laminate was cut into a size of 100 mm x 100 mm to prepare a test sample.

In an atmosphere of 23 ° C. and 45% RH, on the self-repairing resin layer (B) of the test sample, 11 linear cuts with an interval of 1 mm in each of the vertical direction and the horizontal direction are put, and a 1 mm ² cross cut grid is formed. 100 pieces were produced. A cellophane adhesive tape (cellophane tape CT405AP-24 manufactured by Nichiban Co., Ltd.) was applied on the crosscut grid, and then the cellophane adhesive tape was peeled in the direction of 90 degrees to leave the self-repairing resin layer (B). Evaluation was made according to the following criteria according to the number obtained.

<Evaluation of adhesion>
S: 100 remaining A; 90 or more, less than 100 remaining B; 50 or more, less than 90 remaining C; less than 50 remaining

(2) Evaluation of scratch resistance of self-healing resin layer (B) The self-healing laminate was cut into a size of 150 mm x 50 mm to prepare a test sample.

  The test sample is placed on a moving table of a Gakushin type friction fastness tester ("AB-301" manufactured by Tester Sangyo Co., Ltd.) with an adhesive tape so that the self-healing resin layer (B) is on the upper side. Fix both ends. Next, it fixes so that it may not move to a horizontal direction in the state which mounted the brass brush (made by Trusco Nakayama Co., Ltd.) on the test sample. A further 500 g of load is placed on the brass brush. In this state, the self-repairing resin layer (B) is scratched with a brass brush by reciprocating the moving table horizontally 500 times. The test conditions are as follows.

・ Movement speed of moving table: 300mm / min ・ Movement distance of moving table: 120mm one way
・ Measurement environment: 23 ℃, 55% RH

  The haze value (Hz0) before the test and the haze value (Hz1) after the test were measured, respectively. Next, the difference (ΔHz) between the haze value before the test (Hz0) and the haze value after the test (Hz1) was obtained by the following formula 1, and judged according to the following criteria. The unit of haze value is [%].

  ΔHz = (Hz1) − (Hz0) Equation 1

<Evaluation of scratch resistance>
S; ΔHz is less than 0.50% (having good scratch resistance)
A: ΔHz is 0.50% or more and less than 1.00% (has scratch resistance)
B: ΔHz2 is 1.00% or more and less than 3.00% (does not have scratch resistance)
C: ΔHz3 is 3.00% or more (does not have scratch resistance)

<Measurement of haze value>
Based on JIS K 7136 (2000), it measured using the turbidimeter "NDH-2000" by Nippon Denshoku Industries Co., Ltd. In the measurement, the self-healing laminate was disposed so that light was incident on the surface on the side where the self-healing resin layer (B) was provided.

(3) Evaluation of water repellency of self-healing resin layer (B) The self-healing laminate was cut into a size of 100 mm x 50 mm to prepare a test sample.

  In an atmosphere of 23 ° C. and 45% RH, the test sample was adhered to the test stand of a contact angle meter (“DM500” manufactured by Kyowa Interface Science Co., Ltd.) so that the self-healing resin layer (B) was on the upper side. Fix both ends of the test sample with tape. 2 μL of pure water was dropped on the sample, the contact angle between the sample surface and pure water was measured, and the following criteria were used for evaluation.

<Evaluation of water repellency>
S: Contact angle of 100 ° or more A; Contact angle of 75 ° or more and less than 100 ° B; Contact angle of 50 ° or more and less than 75 ° C; Contact angle of less than 50 °

(4) Evaluation of oil repellency of self-healing resin layer (B) The self-healing laminate was cut into a size of 100 mm × 50 mm to prepare a test sample.

  In an atmosphere of 23 ° C. and 45% RH, the test sample was adhered to the test stand of a contact angle meter (“DM500” manufactured by Kyowa Interface Science Co., Ltd.) so that the self-healing resin layer (B) was on the upper side. Fix both ends of the test sample with tape. 2 μL of oleic acid was dropped on the sample, and the contact angle between the sample surface and oleic acid was measured and evaluated according to the following criteria.

<Evaluation of oil repellency>
S: Contact angle is 50 ° or more A; Contact angle is 35 ° or more and less than 50 ° B; Contact angle is 20 ° or more and less than 35 ° C; Contact angle is less than 20 °

(5) Measurement of the wound disappearance time of the self-healing resin layer (B) The self-healing laminate was cut into a size of 150 mm x 50 mm, and the back surface (the surface opposite to the surface on which the self-healing resin layer (B) was laminated) A test sample was prepared by sticking a black adhesive tape almost over the entire surface.

  The test sample is placed on a moving table of a Gakushin type friction fastness tester ("AB-301" manufactured by Tester Sangyo Co., Ltd.) with an adhesive tape so that the self-healing resin layer (B) is on the upper side. Fix both ends. Next, it fixes so that it may not move to a horizontal direction in the state which mounted the brass brush (made by Trusco Nakayama Co., Ltd.) on the test sample. A further 500 g of load is placed on the brass brush. In this state, the movable table was reciprocated horizontally five times to scratch the self-recoverable resin layer (B) with a brass brush, and the time for the scratch to disappear was measured. Whether the scratches disappeared was visually evaluated. The measurement was performed 5 times under the following conditions, averaged, and evaluated according to the following criteria.

・ Movement speed of moving table: 300mm / min ・ Movement distance of moving table: 120mm one way
・ Measurement environment: 23 ℃, 55% RH

<Evaluation criteria for wound disappearance time>
S: Scratch disappearance time is less than 10 seconds A; Scratch disappearance time is 10 seconds or more and less than 3 minutes B; Scratch disappearance time is 3 minutes or more and less than 30 minutes C; Scratch disappearance time is 30 minutes or more and 24 hours Less than D; scratches do not disappear even after 24 hours

(6) Weather resistance test A weather resistance test was performed under the following conditions using an ultraviolet deterioration accelerating tester (Isuper UV Tester SUV-W151 manufactured by Iwasaki Electric Co., Ltd.).

Illuminance: 100 mW / cm ²
Temperature: 60 ° C
Relative humidity: 50% RH
Irradiation time: 90 hours

<Measurement of color difference change Δb>
Based on JIS Z8781-4 (2013), the transmission b value before and after the weather resistance test was measured using a spectrophotometer (“UV3600” manufactured by Shimadzu Corporation), and the difference Δb value was obtained. Here, the Δb value is a value obtained by subtracting the b ₀ value before the test from the b ₁ value after the weather resistance test.

(7) Measurement of crack elongation A self-healing laminate was cut into a short shape having a length of 110 mm and a width of 20 mm to prepare a test sample. Using a tensile tester (“Autograph AGS-500NX” manufactured by Shimadzu Corporation), the crack occurrence state of the self-recoverable resin layer (B) was visually confirmed at a chuck distance of 50 mm and a tensile speed of 50 mm / min. Then, the tensile test was performed, and the dimension (L ₁ ) when the crack occurred was measured. Each was measured 5 times and averaged. The environment at the time of measurement is 23 ° C. ± 2 ° C. and relative humidity 55% ± 5%. The crack elongation was calculated by the following formula 2 from the dimension when the crack occurred (L ₁ ) and the dimension before the tensile test (L ₀ ).

Crack elongation (%) = (L ₁ −L ₀ ) / L ₀ × 100 Formula 2

[Example 1]
A self-healing laminate was produced in the following manner.

<Lamination of intermediate resin layer (A)>
On one surface of a polyurethane resin film 1 having a thickness of 150 μm (aliphatic thermoplastic polyurethane resin film; Esmer URS PX manufactured by Nihon Matai Co., Ltd.), the thickness (the thickness after dry curing) ) Was applied with a gravure coater so as to be 2.0 μm, and then dried and cured at 100 ° C. to form an intermediate resin layer (A).

<Thermosetting composition 1>
18.8 parts by mass of tolylene diisocyanate (Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) is added to 100 parts by mass of an acrylic polyol having a hydroxyl group (“Takelac” (registered trademark) UA-702, manufactured by Mitsui Chemicals, Inc.). Furthermore, 9.6 parts by mass of an acrylic polyol containing a hydroxyl group (Acridic A-823, manufactured by DIC Corporation) is added, and then diluted with methyl ethyl ketone to obtain a thermosetting composition having a solid content concentration of 20% by mass. 1 was prepared.

<Lamination of self-healing resin layer (B)>
On the intermediate resin layer (A) laminated on the polyurethane resin film 1, the following active energy ray-curable composition 2 is applied with a slit die coater so that the thickness (thickness after drying and curing) is 20 μm, After drying at 120 ° C., ultraviolet rays (300 mJ / cm ² ) were irradiated and cured to form a self-repairing resin layer (B).

<Active energy ray-curable composition 2>
50 parts by mass of a methyl ethyl ketone solution of urethane acrylate 2 prepared below is mixed with 50 parts by mass of a methyl ethyl ketone solution of urethane acrylate 1 prepared below, and a fluorine-modified acrylate compound (Daicel Ornex Co., Ltd.) is used as the fluorine compound. 6 parts by mass of EBECRYL8110), 1 part by mass of polydimethylsiloxane compound (EBECRYL350 manufactured by Daicel Ornex Co., Ltd.), and 1.5 parts by mass of photopolymerization initiator (Irgacure 184, manufactured by BASF Japan Ltd.) In addition, the active energy ray-curable composition 2 having a solid content of 40% by mass was prepared by diluting with methyl ethyl ketone.

<Preparation of Methyl Ethyl Ketone Solution of Urethane Acrylate 1>
50 parts by mass of toluene, 50 parts by mass of isocyanurate-modified type of hexamethylene diisocyanate (Takenate D-170N manufactured by Mitsui Chemicals, Inc.), 76 parts by mass of polycaprolactone-modified hydroxyethyl acrylate (Placcel FA5 manufactured by Daicel Chemical Industries, Ltd.) 0.02 part by mass of dibutyltin laurate and 0.02 part by mass of hydroquinone monomethyl ether were mixed and held at 70 ° C. for 5 hours. Thereafter, 79 parts by mass of methyl ethyl ketone was added to obtain a methyl ethyl ketone solution of urethane acrylate 1 having a solid concentration of 50% by mass.

<Preparation of Methyl Ethyl Ketone Solution of Urethane Acrylate 2>
Hexamethylene diisocyanate isocyanurate-modified type (Takenate D-170N manufactured by Mitsui Chemicals, Inc.), 50 parts by mass, polyethylene glycol monoacrylate (Blenmer AE-150 manufactured by NOF CORPORATION), dibutyltin laurate 0.02 Part by mass and 0.02 part by mass of hydroquinone monomethyl ether were mixed and held at 70 ° C. for 5 hours. Thereafter, 102 parts by mass of methyl ethyl ketone was added to obtain a methyl ethyl ketone solution of urethane acrylate 2 having a solid concentration of 50% by mass.

[Example 2]
A self-healing laminate was produced in the same manner as in Example 1 except that the thickness was changed to a polyurethane resin film 2 having a thickness of 100 μm (aromatic thermoplastic polyurethane resin film; Higres DUS605-CER manufactured by Seadam Co., Ltd.).

[Example 3]
A self-recoverable laminate was produced in the same manner as in Example 1 except that the thickness of the intermediate resin layer (A) was changed to 0.3 μm.

[Example 4]
A self-recoverable laminate was produced in the same manner as in Example 1 except that the thickness of the intermediate resin layer (A) was changed to 0.5 μm.

[Example 5]
A self-recoverable laminate was produced in the same manner as in Example 1 except that the thickness of the intermediate resin layer (A) was changed to 1.0 μm.

[Example 6]
A self-recoverable laminate was produced in the same manner as in Example 1 except that the thickness of the intermediate resin layer (A) was changed to 5.0 μm.

[Example 7]
A self-healing laminate was produced in the same manner as in Example 1 except that the thickness of the self-healing resin layer (B) was changed to 8 μm.

[Example 8]
A self-healing laminate was produced in the same manner as in Example 1 except that the thickness of the self-healing resin layer (B) was changed to 5 μm.

[Example 9]
A self-healing laminate was produced in the same manner as in Example 1 except that the thickness of the self-healing resin layer (B) was changed to 10 μm.

[Example 10]
A self-healing laminate was produced in the same manner as in Example 1 except that the thickness of the self-healing resin layer (B) was changed to 30 μm.

[Comparative Example 1]
In contrast to Example 1, the polyurethane resin film 1 was not coated with the intermediate resin layer (A), and a self-healing laminate was produced.

[Comparative Example 2]
For Example 2, a self-recoverable laminate was produced without applying the intermediate resin layer (A) to the urethane resin film 2.

[Comparative Example 3]
With respect to Example 1, the active energy ray-curable composition 2 was not applied on the intermediate resin layer (A), and a self-recoverable laminate was produced.

[Comparative Example 4]
In contrast to Example 2, the active energy ray-curable composition 2 was not applied on the intermediate resin layer (A), and a self-healing laminate was produced.

[Comparative Example 5]
It was produced in the same manner as in Example 1 except that the following hard coat layer was laminated instead of the self-healing resin layer in Example 1.

<Lamination of hard coat layer>
The UV-curable hard coating agent (Arakawa Chemical Industries, Ltd. "Beamset 1200", was applied by a gravure coater so that the dry thickness becomes 7 [mu] m, followed by drying, ultraviolet 400 mJ / cm ² irradiation at 90 ° C. cured To form a hard coat layer.

[Example 11]
A self-healing laminate was prepared in the same manner as in Example 1 except that the active energy ray-curable composition 3 was changed to the following.

<Active energy ray-curable composition 3>
The active energy ray-curable composition 1 was prepared in the same manner as the active energy ray-curable composition 1 except that a fluorine-modified acrylate compound (EBECRYL8110 manufactured by Daicel Ornex Co., Ltd.) was not added.

[Example 12]
A self-healing laminate was prepared in the same manner as in Example 1 except that the active energy ray-curable composition 4 was changed to the following.

<Active energy ray-curable composition 4>
The active energy ray-curable composition 1 was prepared in the same manner except that the addition amount of the fluorine-modified acrylate compound (EBECRYL8110 manufactured by Daicel Ornex Co., Ltd.) was changed to 0.3 parts by mass.

[Example 13]
A self-healing laminate was produced in the same manner as in Example 1 except that the active energy ray-curable composition 5 was changed to the following.

<Active energy ray-curable composition 5>
The active energy ray-curable composition 1 was prepared in the same manner except that the addition amount of the fluorine-modified acrylate compound (EBECRYL8110 manufactured by Daicel Ornex Co., Ltd.) was changed to 0.5 parts by mass.

[Example 14]
A pressure-sensitive adhesive layer was laminated on the self-healing laminate obtained in Example 1 in the following manner to produce a self-healing laminate with an adhesive layer.

<Preparation of adhesive>
As a monomer component, 100 parts by weight of a copolymer formed from 2-ethylhexyl acrylate / acrylic acid (weight component ratio = 90.0 / 10.0) and 0.2 parts by weight of aluminum tris (acetylacetonate) (dried) The pressure-sensitive adhesive was adjusted by adding the latter weight ratio).

<Lamination of adhesive layer>
The pressure-sensitive adhesive prepared above was applied to a release-treated PET film so that the thickness after drying was 50 μm to form a pressure-sensitive adhesive layer. This pressure-sensitive adhesive layer is the opposite surface of the polyurethane resin film 1 of the self-healing laminate obtained in Example 1 (the surface on which the intermediate resin layer (A) and the self-healing resin layer (B) are provided). Transfer to the opposite side) and laminated.

[Evaluation]
About the self-healing laminate and the self-healing laminate with the pressure-sensitive adhesive layer produced in the above examples and comparative examples, adhesion, scratch resistance, water repellency, oil repellency, scratch disappearance time, crack elongation and weather resistance Evaluated. The results are shown in Table 1.

[Example 21]
A self-healing laminate was produced in the following manner.

<Lamination of intermediate resin layer (A)>
On one surface of a polyurethane resin film 1 having a thickness of 150 μm (aliphatic thermoplastic polyurethane resin film; Esmer URS PX manufactured by Nihon Matai Co., Ltd.), the thickness (thickness after drying and curing) is as follows. ) Was applied with a gravure coater so as to be 2.0 μm, and then dried and cured at 100 ° C. to form an intermediate resin layer (A).

<Thermosetting composition 2>
18.8 parts by mass of tolylene diisocyanate (Coronate L manufactured by Nippon Polyurethane Industry Co., Ltd.) is added to 100 parts by mass of an acrylic polyol having a hydroxyl group (“Acridic” (registered trademark) A-823 manufactured by DIC Corporation). Furthermore, 9.6 parts by mass of an acrylic polyol containing a hydroxyl group (Acridic A-823, manufactured by DIC Corporation) is added, and then diluted with methyl ethyl ketone to obtain a thermosetting composition having a solid content concentration of 20% by mass. 2 was prepared.

<Lamination of self-healing resin layer (B)>
On the intermediate resin layer (A) laminated on the polyurethane resin film 1, the following active energy ray-curable composition 6 is applied with a slit die coater so that the thickness (thickness after drying and curing) is 15 μm, After drying at 120 ° C., ultraviolet rays (300 mJ / cm ² ) were irradiated and cured to form a self-repairing resin layer (B).

<Active energy ray-curable composition 6>
100 parts by weight of a methyl ethyl ketone solution of urethane acrylate 3 prepared below, 6 parts by weight of a fluorine-modified acrylate compound (EBECRYL8110 manufactured by Daicel Ornex Co., Ltd.) as a fluorine compound, and EBECRYL350 manufactured by Daicel Ornex Co., Ltd. ) 1 part by mass, 6 parts by mass of a reactive benzotriazole UV absorber (“RUVA-93” manufactured by Otsuka Chemical Co., Ltd.), and a hindered amine light stabilizer (“TINUVIN 123” manufactured by BASF Japan Ltd.) 0.5 parts by mass, 1.5 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by BASF Japan Ltd.) is added, and then diluted with methyl ethyl ketone, and an active energy ray-curable composition having a solid content concentration of 40% by mass. Product 6 was prepared.

<Preparation of Methyl Ethyl Ketone Solution of Urethane Acrylate 3>
Hexamethylene diisocyanate isocyanurate-modified type (Takenate D-170N manufactured by Mitsui Chemicals, Inc.) 50 parts by mass, polypropylene glycol monoacrylate (manufactured by NOF Corporation; Bremer AP-400) 53 parts by mass, dibutyltin laurate 0.02 Part by mass and 0.02 part by mass of hydroquinone monomethyl ether were mixed and held at 70 ° C. for 5 hours. Thereafter, 102 parts by mass of methyl ethyl ketone was added to obtain a methyl ethyl ketone solution of urethane acrylate 3 having a solid concentration of 50% by mass.

<Lamination of adhesive layer>
In the same manner as in Example 14, the pressure-sensitive adhesive layer was transferred to the opposite surface of the polyurethane resin film 1 (the surface opposite to the surface on which the intermediate resin layer (A) and the self-repairing resin layer (B) were provided). And laminated.

[Example 22]
A self-healing laminate was produced in the same manner as in Example 21 except that the active energy ray-curable composition 7 was changed to the following.

<Active energy ray-curable composition 7>
50 parts by mass of a methyl ethyl ketone solution of urethane acrylate 3 prepared above, 25 parts by mass of the following urethane acrylate 4 in terms of solid content, and 6 parts by mass of a fluorine-modified acrylate compound (EBECRYL8110 manufactured by Daicel Ornex Co., Ltd.) as the fluorine compound. , 1 part by mass of a polydimethylsiloxane compound (EBECRYL350 manufactured by Daicel Ornex Co., Ltd.), 6 parts by mass of a reactive benzotriazole UV absorber (“RUVA-93” manufactured by Otsuka Chemical Co., Ltd.), a hindered amine light stabilizer 0.5 parts by weight of the agent (“TINUVIN 123” manufactured by BASF Japan K.K.) and 1.5 parts by mass of the photopolymerization initiator (Irgacure 184 manufactured by BASF Japan K.K.) are added, and then diluted with methyl ethyl ketone. Active energy with a solid content of 40% by mass The curable composition 7 was prepared.

<Synthesis of urethane acrylate 4>
100 parts by mass of toluene, 50 parts by mass of methyl-2,6-diisocyanatohexanoate (“LDI” manufactured by Kyowa Hakko Kogyo Co., Ltd.) and polycarbonate diol (“Placcel CD-210HL” manufactured by Daicel Co., Ltd.), number average molecular weight 1 , 119) 119 parts by mass, heated to 40 ° C. and held for 8 hours. Next, 28 parts by mass of 2-hydroxyethyl acrylate (“Kyoeisha Chemical Co., Ltd.“ Light Ester HOA ”) and 0.02 parts by mass of hydroquinone monomethyl ether were added and maintained at 70 ° C. for 30 minutes, 02 parts by mass was added and the mixture was kept at 80 ° C. for 6 hours. And finally 97 mass parts of toluene was added and it adjusted so that solid content concentration might be 50 mass%.

[Example 23]
A self-healing laminate was produced in the same manner as in Example 21 except that the active energy ray-curable composition 8 was changed to the following.

<Active energy ray-curable composition 8>
33 parts by mass of the methyl ethyl ketone solution of urethane acrylate 1 prepared above, 33 parts by mass of the methyl ethyl ketone solution of urethane acrylate 3 prepared above, 17 parts by mass of the urethane acrylate 4 in terms of solid content, fluorine-modified acrylate as a fluorine compound 6 parts by mass of a compound (EBECRYL8110 manufactured by Daicel Ornex Co., Ltd.), 1 part by mass of a polydimethylsiloxane compound (EBECRYL350 manufactured by Daicel Ornex Co., Ltd.), a reactive benzotriazole ultraviolet absorber (Otsuka Chemical Co., Ltd.) 6 parts by mass of “RUVA-93”), 0.5 parts by mass of hindered amine light stabilizer (“TINUVIN 123” manufactured by BASF Japan), and photopolymerization initiator (Irgacure 184 manufactured by BASF Japan) Add 1.5 parts by weight In diluted with methyl ethyl ketone to prepare a solid concentration of 40% by mass of the active energy ray curable composition 8.

[Example 24]
A self-recoverable laminate was produced in the same manner as in Example 21 except that the active energy ray-curable composition 9 was changed to the following.

<Active energy ray-curable composition 9>
The active energy ray-curable composition 8 was prepared in the same manner as the active energy ray-curable composition 8 except that a hindered amine light stabilizer (“TINUVIN 123” manufactured by BASF Japan Ltd.) was not added.

[Example 25]
In Example 23, a self-healing laminate was produced in the same manner as in Example 23 except that the thermoplastic composition 2 of the intermediate resin layer (A) was changed to the following thermoplastic composition 3.

<Thermosetting composition 3>
18.8 parts by mass of tolylene diisocyanate (Coronate L manufactured by Nippon Polyurethane Industry Co., Ltd.) is added to 100 parts by mass of an acrylic polyol having a hydroxyl group (“Acridic” (registered trademark) A-823 manufactured by DIC Corporation). Then, 9.6 parts by mass of an acrylic polyol containing hydroxyl group (Acridic A-823 manufactured by DIC Corporation) was added, and a reactive benzotriazole-based ultraviolet absorber (“RUVA-93” manufactured by Otsuka Chemical Co., Ltd.) was added. 10 parts by mass, and then diluted with methyl ethyl ketone to prepare thermosetting composition 3 having a solid content concentration of 20% by mass.

[Examples 31 to 35]
In Examples 21 to 25, Example 21 was performed except that the polyurethane resin film 1 was changed to a polyurethane resin film 2 having a thickness of 100 μm (aromatic thermoplastic polyurethane resin film; Highgress DUS605-CER manufactured by Seadom Co., Ltd.). ˜25, self-recoverable laminates of Examples 31 to 35 were obtained.

[Evaluation]
The self-healing laminate with the pressure-sensitive adhesive layer produced in the above Examples and Comparative Examples was evaluated for adhesion, scratch resistance, water repellency, oil repellency, scratch disappearance time, crack elongation and weather resistance. The results are shown in Table 2.

  The self-healing laminate according to the present invention can be used as a protective film for protecting a vehicle exterior coating film or a screen of a display device.

1 Self-healing laminate 2 Polyurethane resin film 3 Intermediate resin layer (A)
4 Self-healing resin layer (B)

Claims (12)

  A self-healing laminate, wherein an intermediate resin layer (A) and a self-healing resin layer (B) made of an active energy ray-curable composition are provided in this order on a polyurethane resin film.   The self-recoverable laminate according to claim 1, wherein the intermediate resin layer (A) contains a resin having a urethane bond in the molecule.   The self-recoverable laminate according to claim 1 or 2, wherein the intermediate resin layer (A) is a resin layer made of a thermosetting composition or a resin layer made of a lacquer composition.   The self-recoverable laminate according to claim 3, wherein the thermosetting composition contains a compound containing a hydroxyl group and a compound containing an isocyanate group.   The contact angle with respect to water of the surface of the self-healing resin layer (B) is 75 ° or more, and the contact angle with respect to oleic acid on the surface of the self-healing resin layer (B) is 35 ° or more. The self-healing laminated body in any one of 1-4.   The self-recoverable laminate according to any one of claims 1 to 5, wherein the active energy ray-curable composition contains a fluorine compound.   The self-healing laminate according to claim 6, wherein the fluorine compound comprises a compound containing a polymerizable double bond group in the molecule.   The self-recoverable laminate according to any one of claims 1 to 7, wherein the intermediate resin layer (A) has a thickness of 0.1 µm or more and less than 10 µm.   The self-healing laminate according to any one of claims 1 to 8, wherein the self-healing resin layer (B) has a thickness of 5 µm to 50 µm.   The polyurethane resin film according to any one of claims 1 to 9, wherein the polyurethane resin film has a pressure-sensitive adhesive layer on a surface opposite to a surface on which the intermediate resin layer (A) and the self-restoring resin layer (B) are provided. A self-healing laminate as described in 1.   The protective film of a vehicle exterior coating film which uses the self-restoring laminated body in any one of Claims 1-10.   The screen protection film of a display which uses the self-repairing laminated body in any one of Claims 1-10.

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