JP2019000984A - Self-repairing film - Google Patents

Abstract

To provide a self-repairing film in which occurrence of delamination is suppressed even after molding and which is excellent in optical performance and weather resistance.SOLUTION: A self-repairing film RF includes: a functional film 1; a self-repairing layer 5 provided on the functional film 1; and a molded adhesion layer 4 provided between the functional film 1 and the self-repairing layer 5, in which the molded adhesion layer 4 contains a polymer resulting from polymerization of a monomer composition including at least one selected from UV-stable monomers and at least one selected from UV-absorbing monomers, and has surface free energy of 50 mN/m or more and hydrogen bond components of the surface free energy of 3 mN/m or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a self-healing film. In particular, the present invention relates to a self-repairing film that suppresses the occurrence of delamination even when molded and is excellent in optical performance and weather resistance.

  In recent years, in laminated films to be bonded along curved surface bodies such as automobile window glass, automobile members, building members, and trough solar power generators, improvement in weather resistance, thermoformability, interlayer adhesion, etc. has been improved. It has been demanded.

  On the other hand, for example, a self-healing surface protective layer formed by crosslinking and curing an ionizing radiation curable resin composition containing an ionizing radiation curable resin, a light stabilizer, an ultraviolet absorber and the like is provided on a substrate. Thus, techniques for improving weather resistance and processability have been proposed (see, for example, Patent Documents 1 and 2).

  However, when the self-healing layer is disposed on the outermost surface as in the conventional technique, the self-healing layer needs to have a low activity from the viewpoint of antifouling properties. Therefore, even when the adhesiveness between the self-healing layer and the lower layer is good at the time of film production, the adhesiveness between the low-activity self-healing layer and the lower layer is reduced when molded by heat stretching, There is a problem that delamination occurs. If delamination occurs, the optical performance and weather resistance of the film after molding will decrease.

JP 2012-206375 A JP 2012-206376 A

  The present invention has been made in view of the above-mentioned problems and situations, and the problem to be solved is a self-healing film that is excellent in optical performance and weather resistance because generation of delamination is suppressed even when molded. Is to provide.

As a result of investigating the cause of the above-mentioned problems in order to solve the above-mentioned problems according to the present invention, a functional film, a self-healing layer provided on the functional film, and between the functional film and the self-healing layer In the self-healing film provided with a molded adhesion layer provided in the above, a monomer composition containing at least one selected from UV-stable monomers and at least one selected from UV-absorbing monomers is polymerized. Since the surface free energy and its hydrogen bond component satisfy the specified numerical range, the occurrence of delamination is suppressed even when molded, and self-healing properties with excellent optical performance and weather resistance are included. I found out that it could be a film.
That is, the said subject which concerns on this invention is solved by the following means.

1. A functional film;
A self-healing layer provided on the functional film;
A molding adhesion layer provided between the functional film and the self-healing layer,
The molded adhesion layer contains a polymer obtained by polymerizing a monomer composition containing at least one selected from UV-stable monomers and at least one selected from UV-absorbing monomers, and has a surface free energy of 50 mN / m or more, A self-repairing film, wherein the hydrogen bond component of the surface free energy is 3 mN / m or more.

2. The difference in hydrogen bond component of the surface free energy between the molded adhesion layer and the functional film is 2 mN / m or more,
2. The self-healing film according to claim 1, wherein a difference in hydrogen bonding components of surface free energy between the molded adhesion layer and the self-healing layer is 2 mN / m or more.

According to this invention, even if it is a case where it shape | molds, generation | occurrence | production of delamination is suppressed and the self-repairable film excellent in optical performance and a weather resistance can be provided.
The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.
Since the surface free energy of the molded adhesion layer is 50 mN / m or more, the activity of the molded adhesion layer is high and the bonding force with the adjacent resin is increased. Adhesion with the self-healing layer can be maintained in a high state.
In addition, the hydrogen bond force is stronger than the van der Waals force or the force between dipoles, and the hydrogen bond component of the surface free energy of the formed adhesion layer is 3 mN / m or more, so When the molding is performed, the self-repairing film can be stretched without breaking the bond between the resins, so that even when the molding is performed, a decrease in optical performance can be suppressed.

Schematic sectional view showing the structure of the self-repairing film of the present invention (A) Load test force at unloading holding time 0 seconds to calculate h _1- indentation depth curve, (b) Load test force at 60 seconds unloading holding time to calculate h ₂ -Indentation depth curve Schematic sectional view showing an example of the structure of a self-restoring film comprising an infrared reflective film as a functional film Schematic sectional view showing another example of the structure of a self-restoring film comprising an infrared reflective film as a functional film Schematic sectional view showing the structure of a self-repairing film comprising a film mirror as a functional film

The self-healing film of the present invention comprises a functional film, a self-healing layer provided on the functional film, and a molded adhesion layer provided between the functional film and the self-healing layer. The molded adhesive layer contains a polymer obtained by polymerizing a monomer composition containing at least one selected from UV-stable monomers and at least one selected from UV-absorbing monomers, and has a surface free energy of 50 mN / m As described above, the hydrogen bond component of the surface free energy is 3 mN / m or more. This feature is a technical feature common to or corresponding to the claims 1 to 2.
In the present invention, the difference in the hydrogen bond component of the surface free energy between the molded adhesive layer and the functional film is 2 mN / m or more, and the surface free energy of the molded adhesive layer and the self-healing layer is The difference in hydrogen bonding components is preferably 2 mN / m or more. As a result, even when molded, distortion and minute voids do not occur, and weather resistance deterioration due to residual distortion and optical performance deterioration due to voids can be prevented. As a result, the optical performance of the self-repairing film In addition, the weather resistance can be further improved.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

<< Outline of Self-Repairing Film of the Present Invention >>
The self-healing film of the present invention comprises a functional film, a self-healing layer provided on the functional film, and a molded adhesion layer provided between the functional film and the self-healing layer, The molded adhesion layer contains a polymer obtained by polymerizing a monomer composition containing at least one selected from UV-stable monomers and at least one selected from UV-absorbing monomers, and has a surface free energy of 50 mN / m or more, The hydrogen bond component of free energy is 3 mN / m or more.

<< Specific Configuration of Self-Repairing Film of the Present Invention >>
FIG. 1 shows the minimum configuration of the self-repairing film RF of the present invention.

  The self-healing film RF of the present invention includes a functional film 1 having a light reflecting layer 3 on at least one surface of a base film 2, a self-healing layer 5 on the surface having the light reflecting layer 3, and the functional film 1. And the self-healing layer 5 are arranged to form the adhesion layer 4.

  Although not shown, a functional layer may be provided on each of the interlayers and the self-healing layer 5 as necessary, and on the surface opposite to the self-healing layer 5 of the base film 2. An adhesive layer or an adhesive layer may be provided, and the self-restoring film may be bonded to another substrate.

  Hereinafter, each constituent layer will be described in detail.

[1] Self-healing layer The self-healing layer according to the present invention preferably has a repairing degree (A) of 0.02 or more. The degree of repair (A) is preferably in the range of 0.02 to 0.90, and preferably in the range of 0.20 to 0.70. If it is 0.02 or more, the self-healing layer can exhibit the self-repairing property of the present invention, and if it is 0.90 or less, the mechanical film strength such as hard coat property is excellent.

  Here, the degree of repair (A) is a value obtained by an expression defined by the indentation depth setting load-unloading test, and is obtained by the following method as an example.

FIG. 2 shows a load test force-indentation depth curve (indentation depth setting load-unloading test when the indenter is indented at the indentation depth, which is obtained by measuring the self-restoring film according to the present embodiment. is a graph showing an example of the resulting curve) to calculate the h ₁ and h _2.

2 (a) is a load test force in unloading retention time 0 seconds - represents the indentation depth curve, calculates the h _1. 2 (b) is a load test force in unloading retention time of 60 seconds - represents the indentation depth curve, calculates the h _2.

(Indentation depth setting load-unloading test)
Using a microhardness meter using a Vickers indenter and a triangular pyramid indenter with an angle between ridges of 115 degrees, the load when the indenter is pushed in at a set indentation depth h _max (μm) on the self-recoverable film surface Create a test force-indentation depth curve. Then, A = (h ₁ −h ₂ ) / h _max is calculated from the residual depth (h ₁ , h ₂ ) obtained when the self-recoverable film is measured at an unloading holding time of 0 seconds or 60 seconds. . The above measurement is performed five times at different parts of the sample, and the average value is obtained as the degree of repair (A).

  As an example of specific measurement conditions, a dynamic ultra-small hardness meter DUH-211S (manufactured by Shimadzu Corporation) can be used and measured under the following measurement conditions.

Indenter shape: Triangular pyramid indenter (edge angle 115 °)
Measurement environment: temperature 23 ° C, relative humidity 50%
Maximum test load: 196.13mN
Loading speed: 6.662 mN / 10 seconds Unloading speed: 6.662 mN / 10 seconds The magnitude of the degree of repair (A) obtained by the above formula indicates self-healing properties, and is 0.02 or more. It can be said that it has the self-repairing property referred to in the present invention. That is, the value of the residual depth h ₂ with respect to the residual depth h ₁ is smaller, the more the difference is large, it said elastic self-healing layer is high, indicating that the self-repairing large degree.

  The degree of repair (A) in the indentation depth setting load-unloading test is preferably in the range of 0.02 to 0.90, and preferably in the range of 0.20 to 0.70. If it is in a range not exceeding 0.90, it is possible to achieve both hard coat properties and a degree of self-repair.

  Such a degree of repair (A) is controlled by appropriately changing the material and thickness of the self-healing layer and the material and thickness of the lower layer of the self-healing layer (such as a functional film or a molded adhesion layer). be able to.

(Main components of self-healing layer)
The self-healing layer according to the present invention is a layer mainly composed of an actinic radiation curable resin that is cured through a crosslinking reaction upon irradiation with actinic rays (also referred to as actinic energy rays) such as ultraviolet rays and electron beams. preferable.

  As the actinic radiation curable resin that can be used in the self-healing layer according to the present invention, a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and actinic radiation such as ultraviolet rays or electron beams is irradiated. This is cured to form an actinic radiation curable resin layer. Among these, from the viewpoint of exhibiting self-healing properties, an active energy ray curable resin having an epoxy skeleton, or an active energy ray curable resin having an alkyl chain skeleton or an alkylene oxide skeleton is preferable.

  Examples of the active energy ray-curable resin having an epoxy skeleton include epoxy (meth) acrylate.

  The epoxy (meth) acrylate is obtained by reacting the tricarboxylic acid represented by the following (i) or (ii) with the (meth) acrylate having a monooxirane ring represented by the following (iii) or (iv): It is.

  The tricarboxylic acid represented by (i) and the tricarboxylic acid represented by (ii) can be used alone or in combination. The (meth) acrylate having a monooxirane ring represented by (iii) and the (meth) acrylate having a monooxirane ring represented by (iv) can be used alone or in combination.

  (I): Aliphatic tricarboxylic acid represented by the following general formula (a)

(In the general formula (a), R represents hydrogen or a hydroxy group. A, b and d each independently represents an integer of 0 to 8, c represents an integer of 0 to 9, and 0 ≦ a + b + c + d ≦ 9 and [a <D or (a = d and b ≦ c)].)

(Ii): trimellitic acid (iii): aliphatic (meth) acrylate having a monooxirane ring represented by the following general formula (b)

(In general formula (b), R represents hydrogen or a methyl group, n represents an integer of 1 to 5, and m represents an integer of 1 to 3.)

  (Iv): An alicyclic (meth) acrylate having a monooxirane ring represented by the following general formula (c)

(In general formula (c), R represents hydrogen or a methyl group, and s represents an integer of 1 to 10.)
Epoxy (meth) acrylate has a good balance between the soft segment and the hard segment, and it is easy to obtain characteristics that easily relieve external stress.

  As the tricarboxylic acid of (i), 1,2,4-butanetricarboxylic acid (R is hydrogen, a = 0, b = 0, c = 1 and d = 0), 1,3,5-hexanetricarboxylic acid ( R is hydrogen, a = 0, b = 1, c = 2 and d = 0), 1,2,4-pentanetricarboxylic acid (R is hydrogen, a = 0, b = 0, c = 1 and d = 1) ), 1,2,5-pentanetricarboxylic acid (R is hydrogen, a = 0, b = 0, c = 2 and d = 0), 1,3,4-pentanetricarboxylic acid (R is hydrogen, a = 0 B = 1, c = 0 and d = 1), 1,2,5-pentanetricarboxylic acid (R is hydrogen, a = 0, b = 1, c = 1 and d = 0), 1,2,6 -Hexanetricarboxylic acid (R is hydrogen, a = 0, b = 0, c = 3 and d = 0), 1,2,4-hexanetricarboxylic acid (R is hydrogen, a = 0, b = 0, = 1 and d = 2), 1,4,5-hexanetricarboxylic acid (R is hydrogen, a = 0, b = 2, c = 0 and d = 1), 1,3,4-hexanetricarboxylic acid (R Is hydrogen, a = 0, b = 1, c = 0 and d = 2), 1,3,6-hexanetricarboxylic acid (R is hydrogen, a = 0, b = 1, c = 2 and d = 0) 2,3,5-hexanetricarboxylic acid (R is hydrogen, a = 1, b = 0, c = 1 and d = 1), 1,4,8-octanetricarboxylic acid (R is hydrogen, a = 0, b = 2, c = 3 and d = 0), 1,5,10-nonanetricarboxylic acid (R is hydrogen, a = 0, b = 3, c = 3 and d = 0), 1,6,12- Dodecane tricarboxylic acid (R is hydrogen, a = 0, b = 4, c = 5 and d = 0), citric acid (R is a hydroxy group, a = b = c = d = 0) and the like.

  Examples of (2) trimellitic acid include 1,3,5-trimellitic acid and 1,2,3-trimellitic acid in addition to 1,2,4-trimellitic acid.

  As the aliphatic (meth) acrylate having a monooxirane ring of (iii), 4-hydroxybutyl acrylate monoglycidyl ether [4-HBAGE, a compound in which n = 4 and m = 1 in the general formula (b)], 2- And hydroxyethyl acrylate monoglycidyl ether [2-HEAGE, a compound where n = 2 and m = 1 in the general formula (b)] and the like.

  Examples of the alicyclic (meth) acrylate having a monooxirane ring represented by the general formula (c) in (iv) include alicyclic epoxy group-containing acrylate (s = 6).

Below, the synthesis example of an alicyclic epoxy group containing acrylate is given.
In a four-necked flask equipped with a stirrer, a thermometer and a condenser, 415.8 parts by mass of toluene, 100 parts by mass of 1,2,4-butanetricarboxylic acid (acid value: 886), 4-hydroxybutyl acrylate monoglycidyl ether [ Nippon Kasei Co., Ltd., 4-HBAGE] 315.8 parts by mass and hydroquinone monomethyl ether 0.1 parts by mass were charged and heated to 100 ° C. Thereafter, it was confirmed that 1,2,4-tricarboxylic acid was completely dissolved, 2 parts by mass of TPP (triphenylphosphine) was charged, and kept at the same temperature for 24 hours to complete the reaction. As a result, an epoxy acrylate having a solid content of 50% by mass and an acid value of 4.2 mgKOH / g (in terms of solid content) was obtained. The yield was 96.1%.

  Examples of the active energy ray-curable resin having an alkyl chain skeleton or an alkylene oxide skeleton include, for example, 2 to 4 carbon atoms in (meth) acrylate having one hydroxy group and three or more (meth) acryloyl groups in the molecule. (Meth) acrylate obtained by reacting (meth) acrylate having the alkylene oxide skeleton (below (P1)) obtained by adding 1 to 20 moles of the above alkylene oxide with polyisocyanate (below (P2)) Can be mentioned.

  Examples of the (meth) acrylate having one hydroxy group and three or more (meth) acryloyl groups in the molecule include pentaerythritol tri (meth) acrylate, diglycerin tri (meth) acrylate, and ditrimethylolpropane tri (meth). Examples include acrylate, xylitol tetra (meth) acrylate, triglycerin tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and sorbitol penta (meth) acrylate.

  Of these, (meth) acrylates having one hydroxy group and 3-5 (meth) acryloyl groups in the molecule are preferred, such as pentaerythritol tri (meth) acrylate, xylitol tetra (meth) acrylate, and triglycerin tetra. (Meth) acrylate and dipentaerythritol penta (meth) acrylate are mentioned. More preferred are pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate.

  As a kind of alkylene oxide used for addition polymerization, a C2-C4 alkylene oxide can be used. Specific examples include ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran and the like. These alkylene oxides may be used alone or in combination of two or more. When two or more of these alkylene oxides are used in combination, they may be subjected to addition polymerization in a random or block form. Of these, tetrahydrofuran is preferable, and the average added mole number of alkylene oxide is 1 to 20, and preferably 2 to 12.

  The method for producing the (meth) acrylate (P1) component having an alkylene oxide skeleton can be carried out in the same manner as in ordinary ring-opening polymerization. For example, after charging a reaction vessel with (meth) acrylate and catalyst having one hydroxy group and three or more (meth) acryloyl groups in the molecule, a polymerization inhibitor and an organic solvent as necessary, Is substituted with an inert gas such as nitrogen gas, and alkylene oxide is injected to carry out addition polymerization. As reaction temperature, it is -30-120 degreeC normally, Preferably it is 0-80 degreeC, More preferably, it is 20-60 degreeC. When it is lower than −30 ° C., the reaction rate is slow, and when it is higher than 120 ° C., side reaction or polymerization may proceed excessively or the product may be colored. The reaction time is usually 0.3 to 20 hours, more preferably 1 to 10 hours.

  Polyisocyanate (P2) is an aliphatic, alicyclic and aromatic isocyanate containing at least two or more isocyanate groups in the molecule. Specific examples of the bifunctional isocyanate include 1,4-tolylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,5-naphthalene diisocyanate, 4, Aliphatic and alicyclic diisocyanates such as aromatic diisocyanates such as 4'-diphenylmethane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, norbornane diisocyanate. Specific examples of the trifunctional isocyanate include 1,4-tolylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone. Isocyanurate modified by isocyanurate modification by polycondensation of diisocyanates such as diisocyanate and norbornane diisocyanate, adduct modified by adduct modification of the diisocyanate, biuret modified by diuret and trihydric alcohols such as glycerin and trimethylolpropane The body is mentioned. Specific examples of the polyfunctional isocyanate include isocyanate compounds obtained by reacting the diisocyanate with a polyol or polyamine.

  Among these, aliphatic diisocyanates and alicyclic diisocyanates, trifunctional isocyanates modified by polycondensation of aliphatic diisocyanates and alicyclic diisocyanate monomers are preferred, such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, norbornane diisocyanate, etc. Aliphatic and alicyclic diisocyanates and trifunctional isocyanates obtained by modifying these diisocyanates with isocyanurates are more preferred. These polyisocyanates may be used alone or in combination of two or more.

A synthesis example is given below.
In a stainless steel autoclave equipped with a stirrer, a thermometer, and a pressure gauge, a pentaerythritol triacrylate (hereinafter referred to as “PE3A”) / pentaerythritol tetraacrylate (hereinafter referred to as “PE4A”) mixture (mass ratio of 70 / 30 mixture, hydroxy group value: 137 mg KOH / g) 307 parts by mass, hydroquinone monomethyl ether 0.1 part by mass, tin tetrachloride 3.2 parts by mass were charged, and the inside of the reaction system was replaced with nitrogen gas. Next, 100 parts by mass of ethylene oxide (hereinafter referred to as “EO”) was introduced over 3 hours while maintaining the gauge pressure at 0.1 to 0.3 MPa at 45 ° C., and 2 hours at the same temperature. The reaction was continued. Furthermore, after reducing the pressure at 45 ° C. and holding for 30 minutes, 402 parts by mass of viscous liquid were obtained by returning to normal pressure and cooling. Thereafter, an adsorbent (KYOWARD 1000: manufactured by Kyowa Chemical Industry Co., Ltd.) was added, stirred at 70 ° C. while blowing air, and then the adsorbent was filtered to obtain 370 parts of a viscous liquid. . The resulting viscous liquid has a hydroxy group value of 106 mgKOH / g, and when calculated from the hydroxy group value, a methacrylic acid having a number average molecular weight of 430 obtained by adding 3 mol of EO to PE3A is obtained, and EO3 mol of PE3A The mass ratio of the adduct / PE4A mixture was 77/23.

  In addition to the above-mentioned resins, actinic radiation curable resins include UV curable acrylate resins, UV curable urethane acrylate resins, UV curable polyester acrylate resins, UV curable epoxy acrylate resins, and UV curable resins. Examples include polyol acrylate resins and ultraviolet curable epoxy resins.

  Among these, polyrotaxane can be used as the other actinic radiation curable resin in the self-healing layer according to the present invention. As commercially available products of the polyrotaxane, for example, SM3405P, SM1315P, SA3405P, SA2405P, SA1315P, SM3400C, SA3400C, SA2400C (above, manufactured by Advanced Soft Materials Co., Ltd.) can be preferably used.

  Further, although it is a thermosetting resin, similarly, as a commercially available product of polyrotaxane, for example, SH3400P, SH2400P, SH1310P, and thermosetting elastomer, for example, SH3400S, SH3400M (above, manufactured by Advanced Soft Materials Co., Ltd.) are preferable. It can also be used.

(Photopolymerization initiator)
The self-healing layer preferably contains a photopolymerization initiator to accelerate the curing of the actinic radiation curable resin. The amount of the photopolymerization initiator is preferably contained in a mass ratio of photopolymerization initiator: active ray curable resin = 20: 100 to 0.01: 100. Specific examples of the photopolymerization initiator include alkylphenone series, acetophenone, benzophenone, hydroxybenzophenone, Michler ketone, α-amyloxime ester, thioxanthone and the like, and derivatives thereof. In particular, it is not limited to these.

  A commercial item may be used for such a photoinitiator, for example, Irgacure 184, Irgacure 907, Irgacure 651, etc. by BASF Japan Ltd. are mentioned as a preferable example.

(Additive)
The self-healing layer may contain additives such as silicone surfactants, fluorine surfactants, anionic surfactants, fluorine-siloxane graft compounds, fluorine compounds, and acrylic copolymers.

(Fine particles)
In order to enhance the slipperiness of the surface of the self-healing layer, fine particles (matting agent) may be further contained as necessary.

  The fine particles may be inorganic fine particles or organic fine particles. Examples of inorganic fine particles include silicon dioxide (silica), titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, Examples include magnesium silicate and calcium phosphate. Among these, silicon dioxide and zirconium oxide are preferable, and silicon dioxide is more preferable in order to reduce the increase in haze of the obtained film.

  Examples of silicon dioxide fine particles include Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600, NAX50 (manufactured by Nippon Aerosil Co., Ltd.), Seahoster KE-P10, KE-P30, KE-P50, KE-P100 (manufactured by Nippon Shokubai Co., Ltd.) and the like are included. Among them, Aerosil R972V, NAX50, Seahoster KE-P30 and the like are particularly preferable because the friction coefficient is reduced while keeping the turbidity of the obtained self-repairing layer low.

  The primary particle diameter of the fine particles is preferably in the range of 5 to 50 nm, and more preferably in the range of 7 to 20 nm. A larger primary particle size has a greater effect of improving the slipperiness, but the transparency tends to decrease. Therefore, the fine particles may be contained as secondary aggregates having a particle diameter in the range of 0.05 to 0.3 μm. The size of the primary particles or the secondary aggregates of the fine particles is as follows. The primary particles or secondary aggregates are observed with a transmission electron microscope at a magnification of 50 to 2 million times, and 100 primary particles or secondary aggregates are observed. It can obtain | require as an average value of a diameter.

  The content of the fine particles is preferably in the range of 0.05 to 1.0% by mass, more preferably in the range of 0.1 to 0.8% by mass with respect to the resin forming the self-healing layer. .

(solvent)
The self-healing layer is formed by diluting the above-described components with a solvent to form a self-healing layer composition, which is applied, dried and cured on a functional film through a molding adhesion layer described later by the following method. Is preferred.

  As the solvent, ketone (methyl ethyl ketone, acetone, etc.) and / or acetate ester (methyl acetate, ethyl acetate, butyl acetate, etc.), alcohol (ethanol, methanol), propylene glycol monomethyl ether, cyclohexanone, methyl isobutyl ketone, etc. are preferable. The dry layer thickness of the self-healing layer is preferably in the range of 5 to 30 μm, more preferably in the range of 10 to 20 μm. Within this range, self-repairing properties can be exhibited and scratch resistance is also improved.

  As a method for applying the self-healing layer, known methods such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, and an ink jet method can be used.

(Method for forming self-healing layer)
After applying the self-healing layer composition, it may be dried and cured (irradiated with actinic radiation (also referred to as UV curing treatment)), and if necessary, may be heat treated after UV curing. The heat treatment temperature after UV curing is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and particularly preferably 120 ° C. or higher. By performing the heat treatment after UV curing at such a high temperature, a self-healing layer having excellent film strength can be obtained.

  In the drying, the drying temperature for 15 seconds after the coating step is in the range of 15 to 70 ° C, the drying temperature in the range of 15 to 36 seconds is in the range of 60 to 120 ° C, and the drying temperature is 36 to 40 seconds. The drying temperature is desirably in the range of 30 to 80 ° C.

Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is usually in the range of 30 to 1000 mJ / cm ² , preferably in the range of 70 to 300 mJ / cm ² . Further, in the UV curing treatment, oxygen removal (for example, replacement with an inert gas such as nitrogen purge) can be performed in order to prevent reaction inhibition by oxygen. The cured state of the surface can be controlled by adjusting the removal amount of the oxygen concentration.

  When irradiating actinic radiation, it is preferable to apply the tension while applying tension to the underlying layer of the self-healing layer because the planarity is improved.

[2] Molded Adhesion Layer The molded adhesion layer according to the present invention is preferably a monomer containing at least one selected from UV-stable monomers and at least one selected from UV-absorbing monomers from the viewpoint of improving light resistance. The composition contains a polymerized polymer.

  Further, the molded adhesion layer according to the present invention has a surface free energy of 50 mN / m or more and a hydrogen bond component of the surface free energy of 3 mN / m or more.

  Further, the difference in hydrogen bonding component of surface free energy between the molded adhesion layer and the functional film described later is 2 mN / m or more, and the difference in hydrogen bonding component of surface free energy between the molding adhesion layer and the self-healing layer is It is preferably 2 mN / m or more. As a result, even when a self-healing film is formed, distortion and minute voids do not occur, and it is possible to prevent deterioration of weather resistance due to residual distortion and optical performance deterioration due to voids. The optical performance and weather resistance of the conductive film can be further improved.

  In the present invention, the functional free film of the self-healing film, the surface free energy of the molded adhesion layer and the self-healing layer, and the hydrogen bonding component thereof can be measured as follows.

Measuring device: Solid-liquid interface analyzer (DropMaster 500, manufactured by Kyowa Interface Science Co., Ltd.)
Measuring method: Droplet method Environment: Temperature 23 ° C, 55% RH
Three standard liquids: pure water, nitromethane, methylene iodide and the contact angle between the solid to be measured (functional film, molded adhesion layer or self-healing layer) according to the method defined in JIS R3257 About 3 μL of the standard liquid is dropped on the solid to be measured, and measured five times with a solid-liquid interface analyzer (DropMaster 500, manufactured by Kyowa Interface Science Co., Ltd.), and the average contact angle is obtained from the average of the measured values. The time to contact angle measurement is measured 60 seconds after the reagent is dropped.

  Next, three components of the surface free energy of the solid are calculated based on the Young-Dupre equation and the extended Fowkes equation.

In this case, calculation can be performed using surface free energy analysis software EG-11 (manufactured by Kyowa Interface Science Co., Ltd.).
Young-Dupre equation: W _SL = γL (1 + cos θ)
W _SL : Adhesion energy between liquid / solid γL: Surface free energy of liquid θ: Contact angle of liquid / solid Extended Fowkes' formula:
W _SL = 2 {(γ _sd γL _d ) ^1/2 + (γ _sp γL _p ) ^1/2 + (γ _sh γL _h ) ^1/2 }
γL = γL _d + γL _p + γL _h : surface free energy of liquid γ _s = γ _sd + γ _sp + γ _sh : surface free energy of solid γ _sd , γ _sp , γ _sh : dispersion of surface free energy, dipole, hydrogen bond Each ingredient

Since the surface free energy component values (mN / m) of the standard liquid are known as shown in Table 1, the surface free energy components of the solid surface to be measured are solved by solving the ternary simultaneous equations from the contact angle values. Values (γ _sd , γ _sp , γ _sh ) can be determined.

  Moreover, in order to expand the elastic region of the self-healing layer, it is preferable that the ratio of the uncured monomer in the molded adhesion layer before performing the decorative molding process described later is 5% by mass or more. The ratio of the uncured monomer in the molded adhesion layer before the decorative molding process is preferably in the range of 5 to 80% by mass, and more preferably in the range of 5 to 60% by mass. Since the buffering property is increased by setting it to 5% by mass or more, the stress relaxation at the time of bonding to the curved body is good, and if it is 80% by mass or less, it is more effective in preventing plasticization of the self-healing layer. It is.

  Moreover, it is preferable that the ratio of the said non-hardened monomer in the said shaping | molding contact | adherence layer after decorating shaping | molding processing is 3 mass% or less. By setting the content to 3% by mass or less, the molded adhesive layer is cured, and when an external stress is applied, deformation of the molded adhesive layer can be suppressed, and deterioration of the optical reflectance can be prevented.

  The polymer that can be used for the molded adhesion layer is preferably a polymerizable acrylic polymer obtained by polymerizing a monomer composition containing at least one selected from UV-stable monomers and at least one selected from UV-absorbing monomers. Self-healing film while improving the self-healing property and scratch resistance of the self-healing layer by using the compound in the molded adhesion layer, rather than adding an ultraviolet absorber or a light stabilizer to the self-healing layer The overall light resistance can be improved.

  The UV-stable monomer as used in the present invention refers to a compound generally referred to as HALS (hindered amine light stabilizer), and is preferably an UV-stable monomer represented by the following general formulas (1) and (2). The polymer preferably has a polymerizable double bond in the side chain of a polymer obtained by radical polymerization of a monomer composition containing at least one selected from the monomers.

(In General Formula (1), R ¹ represents a hydrogen atom or a cyano group. R ² and R ³ each independently represent a hydrogen atom or a methyl group. R ⁴ represents a hydrogen atom or a carbon atom having 1 to 18 carbon atoms. Represents a hydrogen group, and X represents an oxygen atom or an imino group.)

(In General Formula (2), R ¹ represents a hydrogen atom or a cyano group. R ² and R ³ each independently represent a hydrogen atom or a methyl group. X represents an oxygen atom or an imino group.)

  Moreover, the polymer which concerns on this invention contains at least 1 sort (s) chosen from the monomer which a monomer composition is represented by the following general formula (3) and the ultraviolet-absorbing monomer represented by (4), and (5). It is preferable.

(In General Formula (3), R ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. R ⁶ represents a lower alkylene group. R ⁷ represents a hydrogen atom or a methyl group. Y represents a hydrogen atom. Represents a halogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a lower alkoxy group, a cyano group or a nitro group.)

(In General Formula (4), R ⁸ represents an alkylene group having 2 or 3 carbon atoms. R ⁹ represents a hydrogen atom or a methyl group.)

(In general formula (5), R ¹⁰ represents a hydrogen atom or a methyl group. Z represents a cycloalkyl group which may have a substituent.)

  The polymerizable acrylic polymer used for the molded adhesion layer according to the present invention is a monomer containing at least one selected from ultraviolet-stable monomers represented by the general formulas (1) and (2) and a monomer having a functional group It is preferable to produce the polymer obtained by radical polymerization of the composition by reacting a compound having a functional group that reacts with the functional group and a polymerizable double bond.

  The polymerizable acrylic polymer used for the molded adhesion layer exhibits excellent light resistance by containing the ultraviolet stable monomer having the specific structure. Although such an action has not yet been fully elucidated, it is likely that the alkyl radical generated in the photoinitiation reaction of the polymer is captured by the N-oxy radical generated by oxidation of the N-substituent of the piperidine skeleton. It is presumed that this is the main effect.

  Further, by using a polymerizable UV stabilizer as in the conventional case, the problem of bleeding out of the UV stabilizer from the polymerization composition can be solved. Furthermore, since the polymer has a polymerizable double bond in the side chain, it becomes a self-crosslinkable polymer and has excellent scratch resistance. Moreover, since it is an acrylic polymer, it is easy to balance physical properties depending on the length of the side chain alkyl group of the monomer to be copolymerized and the presence or absence of an aromatic ring.

  Moreover, the said polymerizable acrylic polymer has a remarkable synergistic effect in terms of light resistance by using together the ultraviolet-absorbing monomer which has the specific structure represented by General formula (3), (4). Moreover, you may further contain the unsaturated monomer of a specific structure. Since the unsaturated monomer has a sterically bulky substituent, it has the effect of reducing the internal strain of the coating film in a curing method that tends to cause internal strain in the coating film, such as curing with an electron beam or ultraviolet light. Further, long-term light resistance is further improved without causing cracks in the coating film.

In the UV-stable monomer of the general formulas (1) and (2) used in the present invention, in the formula, the substituent represented by R ¹ is constituted by a hydrogen atom or a cyano group, and the substituent represented by R ² or R ³ Each group is independently composed of a hydrogen atom or a methyl group, the substituent represented by R ⁴ is composed of a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and the substituent represented by X is an oxygen atom or imino It is a piperidine composed of a group.

In the above general formula (1), the substituent represented by R ⁴ is specifically a hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group. A chain hydrocarbon group such as hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group; cyclopropyl group, An alicyclic hydrocarbon group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; an aromatic hydrocarbon group such as a phenyl group, a tolyl group, a xylyl group, a benzyl group, and a phenethyl group.

  Specific examples of the UV-stable monomer represented by the general formula (1) include 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2. , 2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloylamino-1,2,2,6,6 -Pentamethylpiperidine, 4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-croto Noylamino-2,2,6,6-tetramethylpiperidine and the like may be mentioned, and only one of these may be used, or two or more may be used in appropriate mixture. Of course, the ultraviolet-stable monomer of General formula (1) is not limited to these compounds.

  Specific examples of the UV-stable monomer represented by the general formula (2) include 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, (Meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotoyloxy-2,2,6,6-tetramethylpiperidine These may be used, and only one of these may be used, or two or more may be appropriately mixed and used. In addition, the ultraviolet-stable monomer of General formula (2) is not limited to these.

In the formula, the ultraviolet absorbing monomer represented by the general formula (3) in the present invention is such that R ⁵ is composed of a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R ⁶ is composed of a lower alkylene group. , R ⁷ is composed of a hydrogen atom or a methyl group, and Y is a benzotriazole composed of a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a lower alkoxy group, a cyano group or a nitro group.

In the general formula (3), the substituent represented by R ⁵ is specifically a hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group. Chain hydrocarbon groups such as hexyl group, heptyl group, octyl group; alicyclic hydrocarbon groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group; phenyl group, tolyl group, xylyl An aromatic hydrocarbon group such as a group, a benzyl group, and a phenethyl group. The substituent represented by R ⁶ is specifically an alkylene group having 1 to 6 carbon atoms, and a linear alkylene group such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, or a hexylene group. And branched chain alkylene groups such as isopropylene group, isobutylene group, s-butylene, t-butylene group, isopentylene group and neopentylene group. The substituent represented by Y is a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom, an oxygen atom, or an iodine atom; a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, or t-butyl. Group, pentyl group, hexyl group, heptyl group, octyl group and other chain hydrocarbon groups: cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and other alicyclic hydrocarbon groups: phenyl group, Aromatic hydrocarbon group such as tolyl group, xylyl group, benzyl group, phenethyl group; lower alkoxy group having 1 to 6 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, heptoxy group; cyano group; Nitro group.

  Specific examples of the ultraviolet absorbing monomer represented by the general formula (3) include 2- [2′-hydroxy-5 ′-(methacryloyloxymethyl) phenyl] -2H-benzotriazole, 2-[[2 '-Hydroxy-5'-(methacryloyloxyethyl) phenyl]]-2H-benzotriazole, 2- [2'-hydroxy-3'-t-butyl-5 '-(methacryloyloxyethyl) phenyl] -2H-benzo Triazole, 2- [2'-hydroxy-5'-t-butyl-3 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxyethyl) phenyl ] -5-Chloro-2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) Phenyl] -5-methoxy-2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-cyano-2H-benzotriazole, 2- [2'-hydroxy-5' -(Methacryloyloxyethyl) phenyl] -t-butyl-2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-nitro-2H-benzotriazole, and the like. However, it is not particularly limited to these. These ultraviolet absorbing monomers represented by the general formula (3) may be used alone or in a suitable mixture of two or more.

In the ultraviolet absorbing monomer represented by the general formula (4), the substituent represented by R ⁸ is composed of an alkylene group having 2 or 3 carbon atoms, and a hydrogen atom represented by R ^9. Or it is benzotriazoles comprised by a methyl group.

In the general formula (4), the substituent represented by R ⁸ is specifically an ethylene group, trimethylene group, propylene group, or the like.

  Examples of the ultraviolet absorbing monomer represented by the general formula (4) include 2- [2′hydroxy-5 ′-(β-methacryloyloxyethoxy) -3′-t-butylphenyl] -4-t- Although butyl-2H-benzotriazole is mentioned, it is not particularly limited to this. Only one kind of these ultraviolet absorbing monomers represented by the general formula (4) may be used, or two or more kinds may be appropriately mixed.

In the unsaturated monomer represented by the general formula (5) used in the present invention, the substituent represented by R ¹⁰ is composed of a hydrogen atom or a methyl group, and the substituent represented by Z has a substituent. It is an unsaturated monomer composed of a cycloalkyl group.

  In the above general formula (5), the substituent represented by Z is a cyclohexyl group, a methylcyclohexyl group, a t-butylcyclohexyl group, a cyclododecyl group, or the like.

  Specific examples of the unsaturated monomer represented by the general formula (5) used in the present invention include cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, and cyclododecyl ( (Meth) acrylate etc. are mentioned, These 1 type (s) or 2 or more types can be used.

  The polymerizable acrylic polymer used in the present invention may be a copolymer having an acrylic monomer as a main monomer and another copolymerizable unsaturated monomer.

  Examples of acrylic monomers used in the present invention include acrylic carboxylic acids such as (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n -(Meth) acrylic acid esters such as butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryltridecyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2- Hydroxypropyl (meth) acrylate, caprolactone-modified hydroxy (meth) acrylate (for example, “Placcel FM” manufactured by Daicel Corporation), (meth) acrylic acid monoester of ester diol obtained from phthalic acid and propylene glycol, etc. Droxy group-containing (meth) acrylic acid ester; (meth) acrylonitrile, (meth) acrylamide, N-methylolacrylamide, N-butoxymethylacrylamide, diacetone acrylamide, 2-sulfonic acid ethyl (meth) acrylate, imide (meth) acrylate And other acrylic monomers such as salts thereof, and one or more of these may be used. Among these, imide (meth) acrylate can be preferably used from the viewpoint of adhesion with the functional film.

  Other copolymerizable unsaturated monomers include, for example, halogen-containing unsaturated monomers such as vinyl chloride and vinylidene chloride; aromatic unsaturated monomers such as styrene, α-methylstyrene and vinyltoluene; vinyl esters such as vinyl acetate; A vinyl ether etc. are mentioned, These 1 type (s) or 2 or more types can be used as needed.

  Although the usage-amount of various monomers is not specifically limited, The total usage-amount of the ultraviolet-stable monomer represented by General formula (1), (2) is 0.1-0.1 with respect to a polymer composition whole quantity. It is desired to be 30% by mass. A more preferable range is described below. The lower limit is preferably 0.5% by mass, and more preferably 1% by mass. The other upper limit is preferably 20% by mass, and more preferably 15% by mass. When the total amount of the UV-stable monomer is within this range, the light resistance of the polymerizable acrylic polymer is sufficient.

  The total use amount of the ultraviolet absorbing monomer represented by the general formulas (3) and (4) is desirably 0.1 to 30% by mass with respect to the total amount of the polymer composition. A more preferable range is described below. The lower limit is preferably 0.5% by mass, and more preferably 1% by mass. The other upper limit is preferably 20% by mass, and more preferably 15% by mass. Within this range, the synergistic effect with the UV-stable monomer is sufficient, and the light resistance is also sufficient. Moreover, there is no possibility of causing coloring.

  The amount of the unsaturated monomer represented by the general formula (5) is desirably 5 to 80% by mass with respect to the total amount of the polymer composition. The more preferable range is described. The lower limit is preferably 10% by mass, and more preferably 15% by mass. The other upper limit is preferably 70% by mass, and more preferably 50% by mass. Within this range, cracks are hardly generated during curing, light resistance is sufficient, and there is no possibility that the cured coating film becomes brittle.

  The polymerizable acrylic polymer of the present invention is obtained by radical polymerization of a monomer composition containing at least one selected from ultraviolet-stable monomers represented by the general formulas (1) and (2) and a monomer having a functional group. The obtained polymer can be produced by reacting a functional group that reacts with the functional group and a compound having a polymerizable double bond.

  Specific examples of the functional group used for introducing a polymerizable double bond include an epoxy group, an oxazoline group, an isocyanate group, an acid amide group (aminocarbonyl group), a carboxy group, a hydroxy group, and an amino group. Specific examples of the copolymerizable monomer having these functional groups include glycidyl (meth) acrylate, 2-isopropenyl-2-oxazoline, 4-epoxycyclohexylmethyl (meth) acrylate, ethyl isocyanate (meth) acrylate, N- Acrylamide, N-methoxymethylacrylamide, N-butoxymethylacrylamide, itaconic acid diamide, fumaric acid amide, phthalic acid amide, (meth) acrylate, itaconic acid, fumaric acid, maleic acid, 2-hydroxyethyl (meth) acrylate, 2 -Hydroxypropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, etc. are mentioned.

  Specific examples of compounds used for introducing a polymerizable functional group include compounds having a carboxy group such as (meth) acrylic acid and itaconic acid when the functional group is an epoxy group or an oxazoline group; In the case of an isocyanate group, a hydroxy group-containing monomer such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; when the functional group is a carboxy group, Epoxy group-containing monomers such as glycidyl (meth) acrylate, 2-isopropenyl-2-oxazoline, 4-epoxycyclohexylmethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4 -Hydroxybutyl (meth) acrylate Hydroxyl group-containing monomers such as G; when the functional group is a hydroxy group, isocyanate group-containing monomers such as ethyl isocyanate (meth) acrylate, carboxy group-containing monomers such as (meth) acrylate and itaconic acid; In the case of a group, an epoxy group or a hydroxy group-containing monomer such as glycidyl (meth) acrylate, 4-epoxycyclohexylmethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate; when the functional group is an amino group, Examples include carboxy group-containing monomers such as (meth) acrylic acid.

  The double bond equivalent of the acrylic polymer of the present invention is preferably 200 to 3000, more preferably 300 to 1500, and still more preferably 350 to 1000. If the double bond equivalent is 3000 or less, the hardness and scratch resistance will be sufficient. When it is 200 or more, cracks hardly occur in the cured coating film over time, and light resistance is improved.

  Moreover, the polymerization method at the time of copolymerizing a monomer component is not specifically limited, A conventionally well-known polymerization method can be employ | adopted. For example, polymerization methods such as solution polymerization, dispersion polymerization, suspension polymerization, and emulsion polymerization can be used. Solvents that can be used when polymerizing monomer components using the solution polymerization method include toluene, xylene, and other high-boiling aromatic solvents; ester solvents such as butyl acetate, ethyl acetate, and cellosolve acetate; methyl ethyl ketone, Examples thereof include ketone solvents such as methyl isobutyl ketone. Of course, the solvent which can be used is not limited to these solvents. These solvents may be used alone or in combination of two or more. It should be noted that the amount of solvent used may be appropriately determined in consideration of the concentration of the product.

  A polymerization initiator is used when the monomer composition is copolymerized. Examples of the polymerization initiator include 2,2′-azobis- (2-methylbutyronitrile), t-butylperoxy-2-ethylhexanoate, 2,2′-azobisisobutyronitrile, benzoylper Usual radical polymerization initiators such as oxide and di-t-butyl peroxide are exemplified. The amount of the polymerization initiator to be used is appropriately determined from the required characteristic values of the polymer and is not particularly limited, but is preferably in the range of 0.01 to 50% by mass with respect to the total amount of the monomer components, More preferably, it is the range of 0.05-20 mass%.

  Although reaction temperature is not specifically limited, The range of room temperature-200 degreeC is preferable, and 40-140 degreeC is more preferable. In addition, what is necessary is just to set reaction time suitably according to the composition of the monomer composition to be used, the kind of polymerization initiator, etc. so that a polymerization reaction may be completed.

(Other components of the molding adhesion layer)
As other components for forming the molded adhesion layer, a curing agent, a curing accelerator, other additives, and the like can be used. Details thereof are described, for example, in JP-A-2009-269984. Examples of the material include, but are not limited to, materials.

(Forming adhesion layer forming method)
As a method for forming the molded adhesion layer, a method in which the polymer and, if necessary, various additives are dissolved in an organic solvent or the like to form a molded adhesion layer coating solution, and the coating solution is applied onto a functional film is preferable. Coating can be performed by methods such as dipping, spraying, brushing, curtain flow coater, roll coating, spin coating, bar coating, and the like.

  The layer thickness of the formed adhesion layer is not particularly limited, but is preferably in the range of 1 to 10 μm, and preferably in the range of 3 to 7 μm. Within the above range, the stress from the outside of the self-healing layer can be relaxed by the molded adhesion layer, and the elastic deformation region of the self-healing layer is widened, so that the self-healing property can be improved even for stronger external stress Scratch resistance can be improved while maintaining the above.

  The polymerizable acrylic polymer is preferably cured by heating, and the molding adhesion layer coating solution is applied onto the functional film and then thermally cured. It is preferable to cure in a temperature range of 80 to 200 ° C. by appropriately adjusting the ratio of the kind of polymer, curing agent, curing accelerator and the like. A temperature range of 80 to 150 ° C is more preferable, and a temperature range of 80 to 120 ° C is more preferable. The time for thermosetting is appropriately adjusted, but it is preferably within the range of 0.5 to 10 minutes in order to adjust the ratio of the uncured monomer and maintain the mechanical strength of the formed adhesion layer.

  In the molded adhesion layer according to the present invention, the ratio of the uncured monomer to the molded adhesion layer before the decorative molding process is 5% by mass or more, which is effective for expanding the elastic deformation region of the self-healing layer. . In particular, from the viewpoint of improving scratch resistance in handling during decorative molding such that the self-restoring film of the present invention is stretched into a curved surface shape and bonded before the decorative molding process, the monomer component is intentionally It is preferable to make it remain, and it is preferable to control the temperature and time of the thermosetting within the above range. In addition, it is preferable to form a self-repairing layer on the molded adhesion layer without performing a post-heating step such as aging after thermosetting.

  That is, the method for producing a self-healing film of the present invention is applied without applying an aging treatment after applying a molding adhesion layer coating solution for forming the molding adhesion layer on the functional film and then thermosetting, It is preferable to form a self-healing layer on the molded adhesion layer. As used herein, the aging treatment refers to heating at a relatively low temperature for a long time after forming the molded adhesion layer, and since it is performed by a combination of heating temperature and heating time, it cannot be said unconditionally. It refers to a heat treatment performed at a temperature in the range of 50 ° C. within a range of 0.5 to 7 days.

  In addition, the self-healing film may be subjected to an aging treatment with the intention of promoting the curing of the self-healing layer after the self-healing layer is formed. It is preferable to carry out under relatively mild aging treatment conditions such that the ratio of the uncured monomer is 5% by mass or more.

  The proportion of the uncured monomer before the decorative molding process is preferably in the range of 5 to 80% by mass, and more preferably in the range of 5 to 60% by mass. Since the buffering property is increased by setting it to 5% by mass or more, the stress relaxation when bonding to a curved shape body is good, and if it is 80% by mass or less, it is more effective in preventing plasticization of the self-healing layer. Is.

  Further, the proportion of the uncured monomer after the decorative molding is preferably 3% by mass or less, and the temperature during the decorative molding is preferably 80 ° C. or higher, in order to control within the range, 80 It is preferable to carry out in a temperature range of ˜200 ° C. A temperature range of 80 to 150 ° C is more preferable, and a temperature range of 80 to 120 ° C is more preferable. It is preferable that the time for the decorative molding is appropriately adjusted so as to be the proportion of the uncured monomer.

  The proportion of the uncured monomer after the decorative molding is preferably controlled to 0.1 to 3% by mass or less by performing decorative molding within the above temperature and time range, and 0.1 to 1 More preferably, it is in the range of 0.0 mass%. If the proportion of the uncured monomer after decorative molding is 0.1% by mass or more, scratch resistance after molding is high, and if it is 3% by mass or less, light resistance after molding is improved.

  By adjusting the ratio of the uncured monomer in the molded adhesion layer before and after the decorative molding process to the specific range as described above, the elastic deformation region of the self-healing layer can be further expanded. Even during the decorative molding process where the restorative film is stretched into a curved surface and bonded, it absorbs deformation stress from the base material after molding and after molding, and the scratch resistance of the stretched part of the self-healing layer It is presumed that the deterioration of the resin can be suppressed.

<Method for quantifying uncured monomer in molded adhesion layer>
The content of the uncured monomer in the molded adhesion layer can be measured by the following method.

  A self-healing film sample is cut, and the ATR (Attenuated Total Reflection) of the formed adhesion layer is measured. As an example of the ATR apparatus, FT / IR-4100 (manufactured by JASCO Corporation) can be used.

(Method and data processing)
The self-healing film sample is cut, and the solid content of the formed adhesion layer that has come out is measured in the wave number range of 400 to 6000 cm ⁻¹ as ATR. Reflected light intensities R1 and R2 having the following wave numbers are obtained.

R1: Reflected light intensity of 2270 cm ⁻¹ : This is a peak of an isocyanate bond and a peak of an uncured component.
R2: Reflected light intensity of 2950 cm ⁻¹ : This is the peak of the C—H bond, and the peak of the material itself (which does not change with curing / uncuring).

  By calculating R1 / R2, uncured components can be quantified.

here,
A: R1 / R2 after application of the molded adhesion layer; the thermosetting resin is 100% of uncured monomer at the stage where the solvent is volatilized after application.
B: R1 / R2 after curing treatment at 150 ° C. for 30 minutes after application of the molding adhesion layer; the thermosetting resin is completely cured and the uncured monomer is 0%.

From the above data, the ratio MM of the uncured monomer can be obtained by the following equation.
(Ratio MM (mass%) of uncured monomer) = (R1 / R2-B) / (AB) × 100
In the above equation, (R1 / R2-B) represents a value obtained by subtracting the base strength from R1 / R2 at the time of measurement.
Moreover, (AB) shows the total monomer amount (total amount of polymer and monomer).
Therefore, (R1 / R2-B) / (AB) is (uncured monomer amount) / (total monomer amount) at the time of measurement.

[3] Functional film The functional film according to the present invention is laminated with the molded adhesion layer and the self-healing layer according to the present invention as an upper layer, and these layers constitute a self-healing film. The functional film preferably has a light reflectance of 50% or more in the light wavelength range of 1000 to 1500 nm. Moreover, as a functional film of another form, it is preferable that the light reflectivity in the range of light wavelength 450-650 nm is 50% or more.

  The former is a film generally referred to as an infrared reflective film that selectively reflects infrared light, and the latter is a reflective film (also called a film mirror) that selectively reflects visible light or a glossy film (a metallic glossy film). Also referred to as)), and there are various types of films.

  Hereinafter, the infrared reflective film for window pasting, the reflective film (film mirror) for solar heat reflective films, and the metallic glossy film, which are preferred embodiments as the functional film according to the present invention, will be described in detail.

[3.1] Infrared Reflective Film As the optical characteristics of the infrared reflective film which is a functional film according to the present invention, the visible light transmittance measured by JIS R3106 (1998) is preferably 60% or more, and more Preferably it is 70% or more, More preferably, it is 80% or more. Further, the reflectivity from the near infrared region to the infrared region having a wavelength of 1000 to 1500 nm is preferably 50% or more, more preferably 70% or more, still more preferably 80% or more, and 90%. The above is particularly preferable. The reflectance is a reflection in a 1000-1500 nm region of an infrared reflective film in an environment of 23 ° C. and 55% RH using a spectrophotometer (using an integrating sphere, manufactured by Hitachi High-Technologies Corporation, U-4000 type). The rate is measured, the average reflectance is obtained, and this is taken as the infrared reflectance.

  The total thickness of the infrared reflective film is not particularly limited, but is in the range of 100 to 1500 μm, preferably in the range of 100 to 1000 μm, more preferably in the range of 100 to 700 μm, particularly Preferably it exists in the range of 100-500 micrometers.

  A typical configuration example of the infrared reflective film will be described with reference to the drawings.

  The infrared reflective film preferably has an infrared reflective layer having a function of reflecting 80% or more, more preferably 90% or more of light within the light wavelength range of 1000 to 1500 nm as the functional layer. Preferably, the infrared reflective layer includes a high refractive index reflective layer containing a first water-soluble binder resin and first metal oxide particles, a second water-soluble binder resin, and a second metal oxide. In this configuration, the low-refractive-index reflective layers containing particles are alternately laminated to selectively reflect light having a specific wavelength.

  These layer configurations in the present invention are not particularly limited as long as they have at least a transparent substrate film and an infrared reflective layer, and an appropriate layer configuration can be selected according to each purpose.

  3 and 4 are cross-sectional views showing examples of the structure of the self-healing film of the present invention having an infrared reflective layer.

  The infrared reflective layer includes a high refractive index reflective layer containing a first water-soluble binder resin and first metal oxide particles, and a low refractive index containing a second water-soluble binder resin and second metal oxide particles. A reflective layer laminated body in which refractive index reflective layers are alternately laminated and selectively reflect light of a specific wavelength is preferable. For example, the configuration shown in FIG. 3 is a preferred embodiment.

In the self-healing film WF shown in FIG. 3, a high refractive index reflective layer containing a first water-soluble binder resin and first metal oxide particles as an infrared reflective layer on the base film 2; And a reflective layer laminate ML1 in which two water-soluble binder resins and a low refractive index reflective layer containing second metal oxide particles are alternately laminated. The reflective layer laminate ML1 is composed of n layers of reflective layers T _{1 to} T _n from the base film 2 side. For example, T ₁ , T ₃ , T ₅ , (omitted), T _n−2 , and T _n are low refractive index layers having a refractive index in the range of 1.10 to 1.60, and T ₂ , T ₄ , An example is a configuration in which T ₆ , (omitted), and T _n−1 are high refractive index layers having a refractive index in the range of 1.80 to 2.50. The refractive index as used in the field of this invention is the value measured in the environment of 25 degreeC.

  FIG. 4 is a schematic cross-sectional view showing an example of a configuration having an infrared reflective layer composed of a polymer layer laminate, which is a self-healing film.

In the self-healing film WF shown in FIG. 4, a polymer layer laminate ML <b> 2 as an infrared reflecting layer is formed on a base film 2 by laminating two kinds of polymer films having different materials. As an example of the configuration, from the base film 2 side, PEN ₁ formed of a polyethylene naphthalate film, PMMA ₁ , PEN ₂ , PMMA ₂ , PEN ₃ , PMMA ₃ formed of a polymethyl methacrylate film, (Omitted), PEN _n-1 , PMMA _n-1 , and PEN _n are laminated to form a polymer layer laminate ML2. The total number of laminated films is preferably in the range of 150 to 1000 layers. For details of these polymer layer laminates, for example, the contents described in US Pat. No. 6,049,419 can be referred to.

  As an infrared reflective film according to the present invention, various functional layers may be provided as necessary in addition to the above-described constituent layers.

Moreover, self-healing films of the present invention is the uppermost layer of the reflecting layer stack ML1 or polymer layer laminate ML2, directly or via another functional layer on the reflective layer T _n or a polyethylene naphthalate film PEN _n Thus, the molded adhesion layer 4 and the self-repairing layer 5 according to the present invention are formed in this order.

<Base film>
Examples of the base film applicable to the functional film according to the present invention include a transparent resin film. “Transparent” in the present invention means that the average light transmittance in the visible light region is 50% or more, preferably 60% or more, more preferably 70% or more, and particularly preferably 80% or more.

  The thickness of the base film is preferably in the range of 30 to 200 μm, more preferably in the range of 30 to 100 μm, and still more preferably in the range of 35 to 70 μm. If the thickness of the substrate film is 30 μm or more, wrinkles and the like are less likely to occur during handling, and if it is 200 μm or less, for example, when making laminated glass, the ability to follow a curved glass surface when bonded to a glass substrate. Will be better.

  The transparent resin film is preferably a biaxially oriented polyester film, but an unstretched or at least one stretched polyester film can also be used. A stretched film is preferable from the viewpoint of strength improvement and thermal expansion suppression. In particular, when the laminated glass provided with the self-healing film of the present invention is used as a windshield of an automobile, a stretched film is more preferable.

  The transparent resin film preferably has a thermal shrinkage within a range of 0.1 to 3.0% at a temperature of 150 ° C. from the viewpoint of preventing generation of wrinkles of the self-repairing film and cracking of the infrared reflective layer. The content is more preferably in the range of 1.5 to 3.0%, and still more preferably 1.9 to 2.7%.

  As described above, the transparent resin film applicable to the present invention is not particularly limited as long as it is transparent. For example, a polyolefin film (for example, polyethylene, polypropylene, etc.), a polyester film (for example, polyethylene terephthalate). , Polyethylene naphthalate, etc.), polyvinyl chloride, triacetyl cellulose film and the like can be used, and polyester film and triacetyl cellulose film are preferable.

  Although it does not specifically limit as a polyester film (henceforth only polyester), It is preferable that it is polyester which has the film formation property which has a dicarboxylic acid component and a diol component as main structural components. The main constituent dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethanedicarboxylic acid, Examples thereof include cyclohexane dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl thioether dicarboxylic acid, diphenyl ketone dicarboxylic acid, and phenylindane dicarboxylic acid. Examples of the diol component include ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, bis ( 4-Hydroxyphenyl) sulfone, bisphenol fluorene hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, cyclohexanediol and the like. Among the polyesters having these as main constituent components, from the viewpoint of transparency, mechanical strength, dimensional stability, etc., dicarboxylic acid components such as terephthalic acid, 2,6-naphthalenedicarboxylic acid, diol components such as ethylene glycol and 1 Polyester having 1,4-cyclohexanedimethanol as the main constituent is preferred. Among these, polyesters mainly composed of polyethylene terephthalate and polyethylene naphthalate, copolymerized polyesters composed of terephthalic acid, 2,6-naphthalenedicarboxylic acid and ethylene glycol, and mixtures of two or more of these polyesters are mainly used. Polyester as a constituent component is preferable.

  When using a transparent resin film for this invention, in order to handle easily, you may contain particle | grains in the range which does not impair transparency. Examples of particles that can be used for the transparent resin film include inorganic particles such as calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, and molybdenum sulfide. And organic particles such as crosslinked polymer particles and calcium oxalate. Examples of the method of adding particles include a method of adding particles in the raw polyester, a method of adding directly to an extruder, etc., and adopting one of these methods. The two methods may be used in combination. In the present invention, additives may be added in addition to the above particles as necessary. Examples of such additives include stabilizers, lubricants, cross-linking agents, anti-blocking agents, antioxidants, dyes, pigments, and ultraviolet absorbers.

  The transparent resin film can be produced by a conventionally known general method. For example, an unstretched transparent resin film that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and rapidly cooling it. The unstretched transparent resin film is uniaxially stretched, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, and other known methods such as transparent resin film flow (vertical axis) direction. Alternatively, a stretched transparent resin film can be produced by stretching in the direction perpendicular to the flow direction of the transparent resin film (horizontal axis). Although the draw ratio in this case can be suitably selected according to the resin used as the raw material of the transparent resin film, it is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction.

The transparent resin film is preferably coated with the undercoat layer coating solution in-line on one or both sides during the film forming process. Examples of resins used in the undercoat layer coating solution useful in the present invention include polyester resins, acrylic-modified polyester resins, polyurethane resins, acrylic resins, vinyl resins, vinylidene chloride resins, polyethyleneimine vinylidene resins, polyethyleneimine resins, and polyvinyl alcohol resins. , Modified polyvinyl alcohol resin, gelatin and the like, and any of them can be preferably used. The undercoat layer can be coated by a known method such as roll coating, gravure coating, knife coating, dip coating or spray coating. The coating amount of the undercoat layer is preferably about 0.01 to ² g / m ² (dry state).

<Infrared reflective layer>
As a typical configuration of the infrared reflective layer, the reflective layer laminate ML1 in which the water-soluble binder resin and the reflective layer containing metal oxide particles described with reference to FIG. A polymer layer laminate ML2 in which the described polymer layers are laminated in multiple layers is exemplified. Particularly preferred is a reflective layer laminate in which a plurality of reflective layers having different refractive indexes and containing a water-soluble binder resin and metal oxide particles are laminated.

<Reflective layer laminate: ML1>
The reflective layer laminate may have at least one reflective layer, but from the viewpoint of developing an excellent heat insulation effect against electromagnetic radiation and electromagnetic wave transparency, the reflective layer laminate is a reflective layer laminate as illustrated in FIG. It is a particularly preferable aspect.

  That is, a high refractive index reflective layer (hereinafter also referred to as a high refractive index layer) containing the first water-soluble binder resin and the first metal oxide particles on at least one surface side of the base film. A structure having a reflective layer laminate in which low refractive index reflective layers (hereinafter also referred to as low refractive index layers) containing the second water-soluble binder resin and the second metal oxide particles are alternately laminated. is there.

  In the reflective layer laminate, the thickness per layer of the high refractive index layer is preferably in the range of 20 to 800 nm, and more preferably in the range of 50 to 350 nm. The thickness per layer of the low refractive index layer is preferably in the range of 20 to 800 nm, and more preferably in the range of 50 to 350 nm.

  Here, when measuring the thickness of each layer per layer, the high refractive index layer and the low refractive index layer may have a clear interface between them or may be gradually changed. When the interface is gradually changing, the maximum refractive index-minimum refractive index = Δn in the region where the layers are mixed and the refractive index continuously changes, the minimum refractive index between two layers + Δn The point of / 2 is regarded as the layer interface.

  The metal oxide concentration profile of the reflection layer laminate formed by alternately laminating the high refractive index layer and the low refractive index layer is etched from the surface to the depth direction by using a sputtering method, and an XPS surface analyzer , The outermost surface is set to 0 nm, sputtering is performed at a rate of 0.5 nm / min, and the atomic composition ratio is measured. Moreover, it is also possible to obtain | require by cut | disconnecting a reflecting layer laminated body and measuring an atomic composition ratio with a XPS surface analyzer for a cut surface. In the mixed region, when the concentration of the metal oxide changes discontinuously, the boundary can be confirmed by a tomographic photograph taken with an electron microscope (TEM).

  The XPS surface analyzer is not particularly limited and any model can be used. For example, ESCALAB-200R manufactured by VG Scientific, Inc. can be used. Mg is used for the X-ray anode, and measurement is performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA).

  From the viewpoint of productivity, the reflective layer laminate is preferably in the range of 6 to 100 layers, more preferably in the range of 8 to 40 layers, as the range of the total number of high refractive index layers and low refractive index layers. And more preferably in the range of 9-30 layers.

  In the reflective layer laminate, it is preferable that the difference in refractive index between the high refractive index layer and the low refractive index layer is designed to be large from the viewpoint that the near infrared reflectance can be increased with a small number of layers. Therefore, the refractive index difference between the adjacent high refractive index layer and low refractive index layer is preferably 0.1 or more, more preferably 0.3 or more, still more preferably 0.35 or more, and particularly preferably 0. .4 or more. However, regarding the outermost layer and the lowermost layer, a configuration outside the above preferred range may be used.

  In the infrared reflective layer, a layer configuration in which the lowermost layer adjacent to the transparent resin film is a low refractive index layer is preferable from the viewpoint of adhesion to the transparent resin film. Further, the functional layer, for example, the uppermost layer adjacent to the molded adhesion layer according to the present invention is also preferably a low refractive index layer containing silicon dioxide in the range of 10 to 60% by mass as metal oxide particles.

  Moreover, it is preferable that the 1st and 2nd water-soluble binder resin contained in a high refractive index layer or a low refractive index layer is polyvinyl alcohol. Moreover, it is preferable that the saponification degree of the polyvinyl alcohol contained in the high refractive index layer is different from the saponification degree of the polyvinyl alcohol contained in the low refractive index layer. Furthermore, the first metal oxide particles contained in the high refractive index layer are preferably titanium oxide particles, and more preferably titanium oxide particles surface-treated with a silicon-containing hydrated oxide. .

[High refractive index layer]
The high refractive index layer contains the first water-soluble binder resin and the first metal oxide particles, and may contain a curing agent, other binder resin, a surfactant, and various additives as necessary. good.

  The refractive index of the high refractive index layer is preferably 1.80 to 2.50, more preferably 1.90 to 2.20.

<First water-soluble binder resin>
The first water-soluble binder resin is the temperature at which the water-soluble binder resin is most dissolved, and is filtered through a G2 glass filter (maximum pores 40 to 50 μm) when dissolved in water at a concentration of 0.5% by mass. In this case, the mass of the insoluble matter filtered out is within 50% by mass of the added water-soluble binder resin.

  It is preferable that the weight average molecular weight of 1st water-soluble binder resin exists in the range of 1000-200000. Furthermore, the inside of the range of 3000-40000 is more preferable.

  The weight average molecular weight referred to in the present invention can be measured by a known method, for example, static light scattering, gel permeation chromatography (GPC), time-of-flight mass spectrometry (TOF-MASS), or the like. In the present invention, it is measured by a gel permeation chromatography method which is a generally known method.

  The content of the first water-soluble binder resin in the high refractive index layer is preferably in the range of 5 to 50% by mass with respect to 100% by mass of the solid content of the high refractive index layer, and is 10 to 40% by mass. It is more preferable to be within the range

  Although there is no restriction | limiting in particular as 1st water-soluble binder resin applied to a high refractive index layer, The above-mentioned hydrophilic high molecular compound can be employ | adopted suitably, Among these, it is especially preferable that it is polyvinyl alcohol. The water-soluble binder resin applied to the low refractive index layer described later is also preferably polyvinyl alcohol.

  The high refractive index layer and the low refractive index layer preferably contain two or more kinds of polyvinyl alcohols having different saponification degrees. Here, in order to distinguish, polyvinyl alcohol as a water-soluble binder resin used in the high refractive index layer is polyvinyl alcohol (A), and polyvinyl alcohol as a water-soluble binder resin used in the low refractive index layer is polyvinyl alcohol (B). That's it. In addition, when each refractive index layer contains a plurality of polyvinyl alcohols having different saponification degrees and polymerization degrees, the polyvinyl alcohol having the highest content in each refractive index layer is changed to polyvinyl alcohol (A ) And polyvinyl alcohol (B) in the low refractive index layer.

  The “degree of saponification” as used herein refers to the ratio of hydroxy groups to the total number of acetyloxy groups (derived from the starting vinyl acetate) and hydroxy groups in polyvinyl alcohol.

  The difference in the absolute value of the degree of saponification between the polyvinyl alcohol (A) and the polyvinyl alcohol (B) is preferably 3 mol% or more, and more preferably 5 mol% or more. If it is such a range, since the interlayer mixing state of a high refractive index layer and a low refractive index layer will become a preferable level, it is preferable. Moreover, although the difference of the saponification degree of polyvinyl alcohol (A) and polyvinyl alcohol (B) is so preferable that it is separated, it is 20 mol% or less from the viewpoint of the solubility to water of polyvinyl alcohol. It is preferable.

  Moreover, it is preferable that the saponification degree of polyvinyl alcohol (A) and polyvinyl alcohol (B) is 75 mol% or more from a soluble viewpoint to water.

  In addition, the polymerization degree of two kinds of polyvinyl alcohols having different saponification degrees is preferably 1000 or more, particularly preferably those having a polymerization degree in the range of 1500 to 5000, and in the range of 2000 to 5000. Those are more preferably used. This is because when the polymerization degree of polyvinyl alcohol is 1000 or more, there is no cracking of the coating film, and when it is 5000 or less, the coating solution is stabilized.

“Degree of polymerization (P)” as used in the present application refers to the degree of viscosity average degree of polymerization, measured according to JIS K6726 (1994), completely re-saponified and purified PVA (polyvinyl alcohol), and then heated to 30 ° C. From the intrinsic viscosity [η] (cm ³ / g) measured in water, it is obtained by the following formula.

P = ([η] × 10 ³ /8.29) ^{(1 / 0.62)}
In the present invention, it is preferable that two types of polyvinyl alcohol having different saponification degrees are used between layers having different refractive indexes.

  For example, when polyvinyl alcohol (A) having a low saponification degree is used for the high refractive index layer and polyvinyl alcohol (B) having a high saponification degree is used for the low refractive index layer, the polyvinyl alcohol ( A) is preferably contained within a range of 40 to 100% by mass, more preferably within a range of 60 to 95% by mass, based on the total mass of all polyvinyl alcohols in the layer. The polyvinyl alcohol (B) is preferably contained within a range of 40 to 100% by mass, and more preferably within a range of 60 to 95% by mass with respect to the total mass of all polyvinyl alcohols in the low refractive index layer. When polyvinyl alcohol (A) having a high saponification degree is used for the high refractive index layer and polyvinyl alcohol (B) having a low saponification degree is used for the low refractive index layer, the polyvinyl alcohol ( A) is preferably contained within a range of 40 to 100% by mass, more preferably within a range of 60 to 95% by mass, based on the total mass of all polyvinyl alcohols in the layer. The polyvinyl alcohol (B) is preferably contained within a range of 40 to 100% by mass, and more preferably within a range of 60 to 95% by mass with respect to the total mass of all polyvinyl alcohols in the low refractive index layer. When the content is 40% by mass or more, interlayer mixing is suppressed, and the effect of less disturbance of the interface appears remarkably.

  As the polyvinyl alcohol (A) and (B) used in the present invention, a synthetic product or a commercially available product may be used. As an example of the commercial item used as polyvinyl alcohol (A) and (B), for example, PVA-102, PVA-103, PVA-105, PVA-110, PVA-117, PVA-120, PVA-124, PVA -203, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-235 (manufactured by Kuraray Co., Ltd.), JC-25, JC-33, JF-03, JF-04 , JF-05, JP-03, JP-04, JP-05, JP-45 (above, manufactured by Nippon Vinegar Poval Co., Ltd.) and the like.

<First metal oxide particles>
As the first metal oxide particles applicable to the high refractive index layer, metal oxide particles having a refractive index of 2.0 to 3.0 are preferable. More specifically, for example, titanium oxide, zirconium oxide, zinc oxide, synthetic amorphous silica, colloidal silica, alumina, colloidal alumina, lead titanate, red lead, yellow lead, zinc yellow, chromium oxide, second oxide Examples include iron, iron black, copper oxide, magnesium oxide, magnesium hydroxide, strontium titanate, yttrium oxide, niobium oxide, europium oxide, lanthanum oxide, zircon, and tin oxide. In addition, composite oxide particles composed of a plurality of metals, core / shell particles whose metal structure changes into a core / shell shape, and the like can also be used.

  In order to form a transparent and high refractive index layer having a higher refractive index, the high refractive index layer includes metal oxide fine particles having a high refractive index such as titanium and zirconium, that is, titanium oxide fine particles and / or zirconia oxide. It is preferable to contain fine particles. Among these, titanium oxide is more preferable from the viewpoint of the stability of the coating liquid for forming the high refractive index layer. Among titanium oxides, the rutile type (tetragonal type) has a lower catalytic activity than the anatase type, and the weather resistance of the high refractive index layer and the adjacent layer is higher, and the refractive index is higher. To preferred.

In the case where the core / shell particles are used as the first metal oxide particles in the high refractive index layer, due to the interaction between the silicon-containing hydrated oxide of the shell layer and the first water-soluble binder resin, From the effect of suppressing interlayer mixing between the high refractive index layer and the adjacent layer, core-shell particles in which titanium oxide particles are coated with a silicon-containing hydrated oxide are more preferable.
When the content of the first metal oxide particles is in the range of 15 to 80% by mass with respect to the solid content of 100% by mass of the high refractive index layer, a difference in refractive index from the low refractive index layer is imparted. It is preferable from the viewpoint. Further, it is more preferably in the range of 20 to 77% by mass, and further preferably in the range of 30 to 75% by mass. In addition, content in case metal oxide particles other than the said core-shell particle are contained in a high refractive index layer will not be specifically limited if it is a range which can have the effect of this invention.

  The volume average particle diameter of the first metal oxide particles applied to the high refractive index layer is preferably 30 nm or less, more preferably in the range of 1 to 30 nm, and in the range of 5 to 15 nm. More preferably. A volume average particle size in the range of 1 to 30 nm is preferable from the viewpoint of low haze and excellent visible light transmittance.

  The volume average particle size of the first metal oxide particles is a method of observing the particles themselves using a laser diffraction scattering method, a dynamic light scattering method, or an electron microscope, or appears on the cross section or surface of the refractive index layer. The particle diameter of 1000 arbitrary particles is measured by a method of observing the particle image with an electron microscope, and particles having particle diameters of d1, d2,. ni: In a group of nk number of particulate metal oxides, the volume average particle diameter mv = {Σ (vi · di)} / {Σ (vi )} Is the average particle size weighted by the volume.

<Curing agent>
In order to cure the first water-soluble binder resin applied to the high refractive index layer, a curing agent can also be used.

  The curing agent that can be used together with the first water-soluble binder resin is not particularly limited as long as it causes a curing reaction with the water-soluble binder resin. For example, when polyvinyl alcohol is used as the first water-soluble binder resin, boric acid and its salt are preferable as the curing agent.

  The content of the curing agent in the high refractive index layer is preferably 1 to 10% by mass and more preferably 2 to 6% by mass with respect to 100% by mass of the solid content of the high refractive index layer.

  In particular, when polyvinyl alcohol is used as the first water-soluble binder resin, the total amount of the curing agent is preferably in the range of 1 to 600 mg per gram of polyvinyl alcohol, and more preferably in the range of 100 to 600 mg per gram of polyvinyl alcohol. .

[Low refractive index layer]
The low refractive index layer contains the second water-soluble binder resin and the second metal oxide particles, and if necessary, a curing agent, a surface coating component, a particle surface protective agent, a binder resin, a surfactant, various types An additive or the like may be included.

  The refractive index of the low refractive index layer is preferably in the range of 1.10 to 1.60, more preferably in the range of 1.30 to 1.50.

<Second water-soluble binder resin>
Polyvinyl alcohol is preferably used as the second water-soluble binder resin applied to the low refractive index layer. Furthermore, it is more preferable that polyvinyl alcohol (B) different from the saponification degree of polyvinyl alcohol (A) used for the high refractive index layer is used for the low refractive index layer. In addition, description about polyvinyl alcohol (A) and polyvinyl alcohol (B), such as a preferable weight average molecular weight of 2nd water-soluble binder resin here, is demonstrated by the water-soluble binder resin of the said high refractive index layer. The description is omitted here.

  The content of the second water-soluble binder resin in the low refractive index layer is preferably within the range of 20 to 99.9% by mass with respect to 100% by mass of the solid content of the low refractive index layer. More preferably, it is in the range of mass%.

<Second metal oxide particles>
As the second metal oxide particles applied to the low refractive index layer, silica (silicon dioxide) is preferably used, and specific examples thereof include synthetic amorphous silica and colloidal silica. Among these, it is more preferable to use acidic colloidal silica sol, and it is more preferable to use colloidal silica sol dispersed in an organic solvent. In order to further reduce the refractive index, hollow fine particles having pores inside the particles can be used as the second metal oxide particles applied to the low refractive index layer, particularly silica (silicon dioxide). ) Hollow fine particles are preferred.

  The second metal oxide particles (preferably silicon dioxide) applied to the low refractive index layer preferably have an average particle size in the range of 3 to 100 nm. The average particle diameter of primary particles of silicon dioxide dispersed in a primary particle state (particle diameter in a dispersion state before coating) is more preferably in the range of 3 to 50 nm, and in the range of 3 to 40 nm. Is more preferably 3 to 20 nm, and most preferably within a range of 4 to 10 nm. Moreover, as an average particle diameter of secondary particle | grains, it is preferable from a viewpoint with few hazes and excellent visible light transmittance | permeability that it is 30 nm or less.

<Curing agent>
Similarly to the high refractive index layer, the low refractive index layer according to the present invention may further include a curing agent. In particular, boric acid and its salts and / or borax are preferred as the curing agent when polyvinyl alcohol is used as the second water-soluble binder resin applied to the low refractive index layer. In addition to boric acid and its salts, known ones can be used.

  The content of the curing agent in the low refractive index layer is preferably in the range of 1 to 10% by mass and in the range of 2 to 6% by mass with respect to 100% by mass of the solid content of the low refractive index layer. It is more preferable.

[Method for forming reflective layer laminate]
The method for forming the reflective layer laminate is preferably formed by applying a wet coating method, and further, a high refractive index containing the first water-soluble binder resin and the first metal oxide particles on the base film. A production method including a step of wet-coating the coating solution for the refractive index layer and the coating solution for the low refractive index layer containing the second water-soluble binder resin and the second metal oxide particles is preferable.

  The wet coating method is not particularly limited. For example, roll coating method, rod bar coating method, air knife coating method, spray coating method, slide curtain coating method, US Pat. No. 2,761,419, US Pat. No. 2,761791 And a slide hopper coating method, an extrusion coating method and the like described in a book. In addition, as a method of applying a plurality of layers in multiple layers, a sequential multilayer application method or a simultaneous multilayer application method may be used.

<Polymer layer laminate: ML2>
The polymer layer laminate according to the present invention forms an infrared reflective layer by laminating a number of first polymer layers having a first refractive index and second polymer layers having a second refractive index.

  The first polymer layer and the second polymer layer are laminated on top of each other to form a polymer layer laminate. Examples of the polymer material constituting the first and second polymer layers include polyester, acrylic, a blend or copolymer of polyester acrylic, and examples thereof include polyethylene-2,6-naphthalate (PEN), naphthalene dicarboxylic copolyester (coPEN). , Polymethyl methacrylate (PMMA), polybutylene-2,6-naphthalate (PBN), polyethylene terephthalate (PET), naphthalene dicarboxylic acid derivative, diol copolymer, polyetheretherketone, syndiotac polystyrene resin (SPS) and the like. Specific combinations of the first polymer layer and the second polymer layer include combinations of PEN / PMMA, PET / PMMA, PEN / coPEN, PEN / SPS, PET / SPS, and the like. Door can be.

As a specific configuration example of the polymer layer laminate, there may be mentioned a configuration in which two kinds of polymer films having different materials shown in FIG. 4 are laminated. Specifically, as shown in FIG. 4, from the lower surface side, PEN ₁ formed of a polyethylene naphthalate film, PMM ₁ , PEN ₂ , PMMM ₂ , PEN ₃ formed of a polymethyl methacrylate film, A polymer layer laminate ML2 is formed by laminating with PMMA ₃ (omitted), PEN _n−1 , PMMA _n−1 , and PEN _n .

  The total number of films to be laminated is not particularly limited, but is preferably in the range of about 150 to 1000 layers.

  For details of these polymer layer laminates, the contents described in US Pat. No. 6,049,419 can be referred to.

[3.2] Film Mirror An outline of a film mirror that reflects light in the visible light region will be described as the functional film according to the present invention.

  The film mirror, which is a functional film according to the present invention, preferably has a reflectance in the visible light range of a wavelength of 450 to 650 nm of 50% or more, more preferably 70% or more, and 80%. More preferably, it is more preferably 90% or more. The reflectance is a spectrophotometer (using an integrating sphere, manufactured by Hitachi High-Technologies Corporation, U-4000 type), and the reflectance in the region of 450 to 650 nm of the film mirror in an environment of 23 ° C. and 55% RH. The average reflectance is measured to obtain the visible light reflectance.

  As shown in FIG. 5A, the minimum functional structure of the self-repairing film MF is a functional film as a film mirror provided with a metal reflective layer (for example, a silver reflective layer) 7 on the base film 2. 1 is formed, and the adhesive layer 4 and the self-healing layer 5 according to the present invention are provided thereon.

  The functional film 1 as a film mirror is preferably provided with various functional layers in practice. For example, as shown in FIG. 5B, an anchor layer 6 is provided between the base film 2 and the metal reflective layer 7. It may be provided. Further, it is also preferable to provide a resin coat layer 8 containing a corrosion inhibitor or an antioxidant on the light incident side of the metal reflective layer 7, and it is also preferable to provide an adhesive layer 9 on the resin coat layer 8, and further to the upper layer. It is also a more preferable aspect to provide the acrylic resin layer 10.

  Moreover, it is preferable to provide the adhesion layer 11 and the peeling sheet 12 in the surface on the opposite side to the side which provides the metal reflective layer 7 of the base film 2, and it can bond with a board | substrate by this.

  The total thickness of the film mirror is preferably in the range of 75 to 250 μm, more preferably in the range of 90 to 230 μm, still more preferably in the range of 100 to 220 μm, from the viewpoints of mirror deflection prevention, regular reflectance, handling properties, and the like. Is within.

  Hereafter, each structural layer which comprises a film mirror is demonstrated sequentially.

[Base film]
It is preferable to use the transparent resin film used in the above-described infrared reflecting film, and details are as described above.

  Among these, polycarbonate films, polyester films such as polyethylene terephthalate, norbornene resin films, cellulose ester films, and acrylic films are preferable. It is particularly preferable to use a polyester film such as polyethylene terephthalate or an acrylic film.

  The thickness of the transparent resin film is preferably an appropriate thickness depending on the type and purpose of the resin. For example, generally, it is the range of 10-300 micrometers. Preferably it is the range of 20-200 micrometers, More preferably, it is the range of 30-100 micrometers.

[Anchor layer]
An anchor layer consists of resin and makes a base film and a metal reflective layer contact | adhere. The resin material used for the anchor layer is not particularly limited as long as it satisfies the above conditions of adhesion, heat resistance, and smoothness. Polyester resin, acrylic resin, melamine resin, epoxy resin, polyamide Resin, vinyl chloride resin, vinyl chloride vinyl acetate copolymer resin or the like can be used alone or a mixed resin thereof. From the viewpoint of weather resistance, a mixed resin of a polyester resin and a melamine resin is preferable. It is more preferable to use a thermosetting resin mixed with a curing agent.

  As a method for forming the anchor layer, conventionally known coating methods such as a gravure coating method in which a predetermined resin material is applied and applied, a reverse coating method, and a die coating method can be used.

  The thickness of the anchor layer is preferably in the range of 0.01 to 3 μm, more preferably in the range of 0.1 to 1 μm.

[Metal reflective layer]
The metal reflective layer is a layer made of a metal or the like having a function of reflecting 50% or more of visible light (range of 450 to 650 nm).

  The surface reflectance of the metal reflective layer is preferably 80% or more, more preferably 90% or more. This reflective layer is preferably formed of a material containing any element selected from the element group consisting of Al, Ag, Cr, Cu, Ni, Ti, Mg, Rh, Pt, and Au. Among these, aluminum (Al) or silver (Ag) is preferably the main component from the viewpoint of reflectivity, and two or more such metal thin films may be formed.

  In the present invention, it is particularly preferable to use a silver reflective layer mainly composed of silver as the metal reflective layer (hereinafter, the metal reflective layer may be referred to as a silver reflective layer).

  The thickness of the silver reflective layer is preferably in the range of 30 to 300 nm, more preferably in the range of 80 to 200 nm, from the viewpoint of reflectance and the like.

  As a method for forming this reflective layer, either a wet method or a dry method can be used. A typical example of the wet method is a plating method, in which a film is formed by depositing a metal from a solution. Specific examples include silver mirror reaction. On the other hand, as a typical example of the dry method, there is a vacuum film forming method, and concrete examples include a resistance heating vacuum deposition method, an electron beam heating vacuum deposition method, an ion plating method, an ion beam assisted vacuum deposition. Method and sputtering method. In particular, a vapor deposition method capable of a roll-to-roll method for continuously forming a film is preferably used in the present invention. For example, in a film mirror manufacturing method, a method of forming a silver reflective layer by silver vapor deposition is preferably used.

  In addition, if the thickness of a silver reflection layer shall be 30-300 nm as mentioned above, it will become possible to use the functional film which has the silver reflection layer as a film mirror. More preferably, it is in the range of 80 to 200 nm from the viewpoint of durability. By making the layer thickness of the silver reflective layer in the above range, it is possible to suppress a decrease in reflectance in the visible light region due to light transmission or light scattering due to unevenness on the surface. .

[Resin coat layer]
The resin coat layer is provided on the light incident side of the silver reflective layer, and is preferably adjacent to the silver reflective layer.

  It is also preferable that the resin coating layer has a function of preventing corrosion or deterioration of the silver reflective layer by containing a silver corrosion inhibitor or antioxidant.

  The resin coat layer may be composed of only one layer, or may be composed of a plurality of layers. The thickness of the resin coat layer is preferably in the range of 1 to 10 μm, more preferably in the range of 2 to 8 μm.

  As the binder of the resin coat layer, the following resins can be preferably used. For example, cellulose ester, polyester, polycarbonate, polyarylate, polysulfone (including polyethersulfone), polyethylene terephthalate, polyethylene naphthalate, polyester, polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate propionate , Cellulose acetate butyrate, polyvinylidene chloride, polyvinyl alcohol, ethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene, polymethylpentene, polyetherketone, polyetherketoneimide, polyamide, fluororesin, nylon, polymethyl A methacrylate, an acrylic resin, etc. can be mentioned. Among them, an acrylic resin having high resistance to ultraviolet rays is preferable from the viewpoint of light resistance.

  The corrosion inhibitor preferably has an adsorptive group for silver. Here, “corrosion” refers to a phenomenon in which a metal (silver) is chemically or electrochemically eroded or deteriorated by an environmental material surrounding it (see JIS Z0103-2004).

The optimum content of the corrosion inhibitor varies depending on the compound used, but is generally preferably in the range of 0.1 to 1.0 g / m ² .

  Corrosion inhibitors having an adsorptive group for silver include amines and derivatives thereof, compounds having a pyrrole ring, compounds having a triazole ring such as benzotriazole, compounds having a pyrazole ring, compounds having a thiazole ring, and imidazole rings. It is desirable that the compound be selected from at least one of a compound having an indazole ring, a copper chelate compound, a compound having a thiol group, a thiourea, a naphthalene, or a mixture thereof.

  In compounds such as benzotriazole, the ultraviolet absorber may also serve as a corrosion inhibitor. It is also possible to use a silicone-modified resin. The silicone-modified resin is not particularly limited.

  For these compounds, the compounds described in paragraphs 0061 to 0073 of JP2012-232538A can be preferably used.

  Examples of commercially available products include LA31 from ADEKA Corporation, Tinuvin 234 from BASF Japan Corporation, and the like.

  Moreover, it is preferable to use a phenolic antioxidant, a thiol antioxidant, and a phosphite antioxidant as an antioxidant that is a corrosion inhibitor having antioxidant ability. Moreover, a hindered amine light stabilizer and a nickel ultraviolet stabilizer can be preferably used as the light stabilizer.

  As these compounds, compounds described in paragraphs 0046 to 0053 of JP2012-232538A can be preferably used.

The optimum content of the antioxidant varies depending on the compound used, but generally it is preferably in the range of 0.1 to 1.0 g / m ² .

[Adhesive layer]
The adhesive layer is not particularly limited as long as it has a function of improving the adhesion between the layers. The thickness of the adhesive layer is preferably in the range of 0.01 to 10 μm, more preferably in the range of 0.1 to 10 μm, from the viewpoints of adhesion, smoothness, reflectance of the reflective material, and the like.

  When the adhesive layer is a resin, the resin is not particularly limited as long as it satisfies the above conditions of adhesion and smoothness, such as a polyester resin, a urethane resin, an acrylic resin, a melamine resin, An epoxy resin, a polyamide resin, a vinyl chloride resin, a vinyl chloride vinyl acetate copolymer resin, etc. can be used alone or a mixed resin thereof. From the viewpoint of weather resistance, a mixed resin of a polyester resin and a melamine resin is preferable. It is more preferable to use a thermosetting resin in which a curing agent such as isocyanate is further mixed. As a method for forming the adhesive layer, conventionally known coating methods such as a gravure coating method, a reverse coating method, and a die coating method can be used.

  In the case where the adhesive layer is a metal oxide, the adhesive layer can be formed by depositing, for example, silicon oxide, aluminum oxide, silicon nitride, aluminum nitride, lanthanum oxide, lanthanum nitride, or the like by various vacuum film forming methods. For example, a film can be formed by resistance heating vacuum deposition, electron beam heating vacuum deposition, ion plating, ion beam assisted vacuum deposition, sputtering, or the like.

[Acrylic resin layer]
For example, the acrylic resin layer is preferably a layer containing an ultraviolet absorber for the purpose of preventing deterioration of the film mirror caused by sunlight or ultraviolet rays. The acrylic resin layer is preferably provided on the light incident side of the base film, and is preferably provided on the light incident side of the metal reflective layer.

  Since the molded adhesion layer according to the present invention has ultraviolet absorbing ability, it may also serve as an acrylic resin layer, and it is also preferable to contain an ultraviolet absorbent different from the molded adhesion layer in the acrylic resin layer.

  The acrylic resin layer is a layer using an acrylic resin as a binder, and the thickness of the acrylic resin layer is preferably in the range of 1 to 200 μm.

  As the acrylic resin layer, Sumipex Technoloy S001G 75 μm (manufactured by Sumitomo Chemical Co., Ltd.), which is an acrylic film containing a commercially available ultraviolet absorber, can be preferably used.

[3.3] Metallic glossy film It is also preferable to use a metallic glossy film as the functional film according to the present invention.

  The metallic glossy film, which is a functional film according to the present invention, preferably has a reflectance in the visible light region of a light wavelength range of 450 to 650 nm of 50% or more, more preferably 70% or more, More preferably, it is 80% or more, and particularly preferably 90% or more.

  Although it does not restrict | limit especially as a metallic glossy film, As the preferable example, two polyester films are bonded together through an contact bonding layer, and are comprised. Each of the two polyester films is mainly composed of a layer mainly composed of polyester A composed of polyethylene terephthalate or polyethylene naphthalate and polyester B containing 25 to 35 mol% of a cyclohexanedimethanol component with respect to the acid component. A polyester film in which layers are regularly laminated in the thickness direction. It is preferably a metallic glossy film comprising a polyester film having a total number of layers of at least 500 to 600 layers.

  The in-plane average refractive index difference between the layer mainly composed of polyester A and the layer mainly composed of polyester B is preferably 0.03 or more. More preferably, it is 0.05 or more, More preferably, it is 0.1 or more. When the refractive index difference is smaller than 0.03, sufficient reflectance may not be obtained.

  It is important that the polyester film constituting the metallic glossy film is formed by alternately laminating 500 layers or more of layers made of polyester A (layer A) and layers made of polyester B (layer B). When it is 500 layers or more, it is possible to have a reflectance of 70% or more in the target reflection band, and two polyester films are bonded together, and the target reflection wavelength is set in the region of 350 to 750 nm. By doing so, a laminated film having a metallic appearance can be obtained.

  Further, in consideration of a decrease in wavelength selectivity accompanying a decrease in stacking accuracy due to an increase in the size of the device or an increase in the number of layers, the number of layers is preferably 600 layers or less. The method of controlling the number of layers in 500 to 600 layers is possible by changing the feed block. When the number of layers is included in the range of 500 to 600 layers, the transmittance of infrared rays is within the object range of the present invention. Balance with visible light reflectance.

  The metallic glossy film further preferably has an average reflectance at a light wavelength of 350 to 750 nm within a range of 70 to 100%, and an average transmittance at a light wavelength of 900 to 1000 nm in a range of 85 to 100%. It is preferable that Such a metallic glossy film is formed by laminating two polyester films described later.

  One of the polyester films to be bonded is one in which the average reflectance at a light wavelength of 350 to 570 nm is in the range of 70 to 100%, and the average transmittance at the light wavelength of 620 to 1000 nm is in the range of 85 to 100%. The other one is that the average reflectance of light wavelengths 570 to 750 nm is preferably in the range of 70 to 100%, and the average transmittances of light wavelengths 350 to 550 nm and 900 to 1000 nm are preferably in the range of 85 to 100%. . By laminating these two polyester films, the average reflectance at a light wavelength of 350 to 750 nm is in the range of 70 to 100%, and the average transmittance at a light wavelength of 900 to 1000 nm is in the range of 85 to 100%. Can be achieved.

  Moreover, it is preferable from a viewpoint of handleability that the thickness of a metallic glossy film is in the range of 100 to 300 μm. It is desirable that the thickness is 100 μm or more in order to prevent wrinkling during molding and improve handling properties. When the thickness is 300 μm or less, curling wrinkles are not strong, and it takes less time and effort to set the sheet on the molding apparatus frame, and the productivity is high.

  The metallic glossy film can form a molded adhesion layer and a self-healing layer according to the present invention on the surface of the polyester film having the above-described configuration, and can prevent cracks in the cured film due to surface hardness and stress such as bending.

  In addition to the molded adhesion layer and self-healing layer according to the present invention, the metallic glossy tone film includes a hard coat layer, an antistatic layer, an abrasion resistant layer, an antireflection layer, a color correction layer, an ultraviolet absorption layer, a printing layer, Functional layers such as a transparent conductive layer, a gas barrier layer, a hologram layer, a release layer, an adhesive layer, an emboss layer, an adhesive layer, and a release layer may be appropriately formed.

  A preferred production method for producing a metallic glossy film will be described below.

  First, the manufacturing method of the polyester film (henceforth a laminated film) which laminated | stacked the layer which has the said polyester A as a main component used for a metallic glossy tone film, and the layer which has the said polyester B as a main component at least 500 layers or more. Is described below.

  Two types of polyester A and polyester B are prepared in the form of pellets. If necessary, the pellets are pre-dried in hot air or under vacuum and supplied to an extruder. In the extruder, the resin that has been heated and melted to a temperature higher than the melting point is made uniform in the amount of resin extruded by a gear pump or the like, and foreign matter or denatured resin is removed through a filter or the like.

  Polyester A and polyester B fed out from different flow paths using these two or more extruders are then fed into the multilayer laminating apparatus. As the multi-layer laminating apparatus, a multi-manifold die, a field block, a static mixer, or the like can be used. Moreover, you may combine these arbitrarily. Among these, a multi-manifold die or a feed block that can individually control the layer thickness of each layer is preferable. Furthermore, in order to control the thickness of each layer with high accuracy, a feed block provided with fine slits for adjusting the flow rate of each layer in electric discharge machining and wire electric discharge machining with machining accuracy of 0.1 mm or less is preferable. At this time, in order to reduce nonuniformity of the resin temperature, heating by a heat medium circulation method is preferable. Moreover, in order to suppress the wall resistance in the feed block, the roughness of the wall surface is preferably 0.4 S or less, or the contact angle with water at room temperature is 30 ° or more.

  In order to obtain a polyester film for use in the metallic glossy film of the present invention, it is important to have an optimum laminated structure according to the spectral characteristics of the metallic glossy film to be designed. It is particularly preferable to perform film formation with a feed block having a slit.

  The molten laminate formed in a desired layer configuration in this way is formed into a desired shape with a die and then discharged. And the sheet | seat laminated | stacked in the multilayer discharged | emitted from die | dye is extruded on cooling bodies, such as a casting drum, and a casting film is obtained by cooling and solidifying. At this time, using a wire-like, tape-like, needle-like or knife-like electrode, the sheet is brought into close contact with a cooling body such as a casting drum by electrostatic force, and rapidly cooled and solidified. A method in which air is blown out from the apparatus and the sheet is brought into close contact with a cooling body such as a casting drum and rapidly cooled and solidified, and a method in which the sheet is brought into close contact with the cooling body with a nip roll and rapidly solidified.

  The casting film thus obtained is preferably biaxially stretched as necessary. Biaxial stretching refers to stretching in the longitudinal direction and the width direction. Stretching may be performed sequentially biaxially or simultaneously in two directions.

  Next, the two polyester films are bonded together via an adhesive, but the bonding of the two polyester films via an adhesive promotes the crystallization of polyester B by heating compared to an adhesive method such as heat fusion. The reflection wavelength region can be expressed as designed.

In the production method for producing a metallic glossy film, the mass per unit area of the adhesive layer formed on one side of the polyester film is preferably about 1 to 30 g / m ² . By setting the mass per unit area, an adhesive layer having a thickness of 1 to 30 μm can be obtained. When it is less than 1 g / m ² , the adhesive strength is weak and it is easy to peel off, and when it is more than 30 g / m ² , the drying property is lowered and the appearance is liable to be poor. Moreover, it is not preferable because the imprint of foreign matter is likely to remain, resulting in a decrease in design properties.

  The coating method for forming the curable adhesive layer is gravure coater, gravure reverse coater, lip coater, flexo coater, blanket coater, roll coater, knife coater, air knife coater, kiss touch coater, kiss touch reverse coater, comma Coating methods such as a coater, comma reverse coater, and micro reverse coater can be used.

  In the bonding step, an adhesive is applied to one side of one polyester film, and then the other polyester film is bonded with a laminate nip roller. At this time, after applying an adhesive to one side of one polyester film, it is preferable to heat-treat at 40 to 120 ° C., and a nip pressure of 0.2 to 1.0 MPa on a laminate nip roller heated to 40 to 120 ° C. It is preferable to laminate the other polyester film.

  In the transport zone from pasting to winding, usually there are multiple mechanisms for detecting defects and / or for absorbing tension of the sheet when adjusting tension and switching the winding roller. In order to suppress the shift in the width direction of the sheet, the sheet is conveyed at an appropriate contact angle in each conveyance roller.

  After passing through a plurality of conveying rollers, it is wound on a sheet winding core, and heat treatment is performed at 20 to 60 ° C. for 24 to 168 hours with the obtained laminated film wound on a roll for the purpose of curing the adhesive. I do. If the temperature of the heat treatment is 20 ° C. or more and the heat treatment time is 24 hours or more, the adhesive is sufficiently cured, sufficient adhesive strength can be obtained, and the film bonded in the subsequent process may be misaligned. Does not occur. Further, if the heat treatment time is 168 hours or less at 60 ° C. or less, there is not much squeezing trace of the rolled sheet, which is suitable as a decoration application.

[4] Decorative Molding Method and Use of Self-Repairing Film [4.1] Decorative Molding Method The self-healing film of the present invention is opposite to the self-healing layer with respect to the self-healing film. A decorative molding process is performed in which an adhesive layer or an adhesive layer is formed on the surface, and the self-restoring film is bonded to the substrate through the adhesive layer or the adhesive layer while being thermoformed at a temperature of 80 ° C. or higher. Is preferred.

  The substrate here is preferably a plastic material (housing) from which a curved body can be obtained.

  By the decorative molding process in which the self-restoring film of the present invention is bonded to a substrate while being thermoformed at a temperature of 80 ° C. or more, the uncured monomer of the molded adhesion layer is crosslinked and polymerized, and the uncured monomer When the content is 3% by mass or less, the strength of the molded adhesion layer itself can be improved, and the scratch resistance of the self-healing layer can be further improved.

  A preferable temperature is in the range of 80 to 200 ° C, more preferably in the range of 80 to 150 ° C, and particularly preferably in the range of 80 to 120 ° C.

[Adhesive layer]
The adhesive layer is a constituent layer for adhering and fixing the self-restoring film of the present invention to the substrate.

  The adhesive layer is not particularly limited as long as it can adhere a self-repairing film to a substrate. For example, a dry laminating agent, a wet laminating agent, an adhesive, a heat sealing agent, a hot melt agent, or the like is used. Can do. Further, polyester resin, urethane resin, polyvinyl acetate resin, acrylic resin, nitrile rubber, or the like may be used.

  The laminating method for providing the adhesive layer on the back surface of the self-healing film is not particularly limited, and for example, a roll-type continuous method is preferable from the viewpoint of economy and productivity.

  The thickness of the pressure-sensitive adhesive layer is usually preferably in the range of about 1 to 50 μm from the viewpoints of the pressure-sensitive adhesive effect and the drying speed.

  Specific materials used for the adhesive layer include, for example, “SK Dyne Series” manufactured by Soken Chemical Co., Ltd., “Oribain BPW Series”, “BPS Series” manufactured by Toyo Ink Co., Ltd., “Arcon” “Superester” “High Pale” manufactured by Arakawa Chemical Co., Ltd. The pressure-sensitive adhesive can be suitably used.

  The adhesive layer is preferably covered with a release sheet until the self-restoring film is adhered to the substrate, and it is preferable to maintain the adhesive strength of the adhesive layer.

  The adhesive layer is a corrosion inhibitor, amines and derivatives thereof, compounds having a pyrrole ring, compounds having a triazole ring such as benzotriazole, compounds having a pyrazole ring, compounds having a thiazole ring, compounds having an imidazole ring, It is also preferable to contain at least one of a compound having an indazole ring, a copper chelate compound, a compound having a mercapto group, a thiourea or a naphthalene group, or a mixture thereof.

[Adhesive layer]
Although it does not restrict | limit especially as an adhesive agent, The adhesive agent which consists of urethane type resin is preferable. An adhesive made of a urethane resin is cured by combining and reacting a polyol having a hydroxyl group at the terminal and a polyisocyanate, or a urethane prepolymer having an isocyanate group at the terminal and a polyol, and functions as an adhesive. .

  As the polyol, polyether polyol, polyester polyol, and other polyols can be used. For example, examples of the polyether polyol include polyoxyethylene polyol, polyoxypropylene polyol, polyoxyethylene-propylene copolymer polyol, polytetramethylene polyol and the like alone or a mixture thereof. Polyester polyols include dicarboxylic acids (such as adipic acid, succinic acid, maleic acid, and phthalic acid) and glycols (such as ethylene glycol, propylene glycol, 1,4-butylene glycol, 1,6-hexane glycol, and neopentyl glycol). Polyols such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polypropylene adipate, polyethylene-propylene adipate and the like, and polylactone polyols such as polycaprolactone polyol alone or A mixture thereof, polycarbonate polyol and the like can be mentioned.

  Polyisocyanates include aromatic polyisocyanates such as 2,4-tolylene diisocyanate, xylene diisocyanate, 2,6-tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, carbodiimide-modified MDI, and naphthalene diisocyanate. , Hexamethylene diisocyanate, isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate and alicyclic polyisocyanate. The above polyisocyanates can be used alone or as a mixture thereof.

  In addition, the adhesive layer has various additives such as viscosity modifiers, leveling agents, anti-gelling agents, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, lubricants, pigments, dyes, organic or Inorganic fine particles, fillers, antistatic agents, nucleating agents and the like may be contained.

[4.2] Laminated glass As a use of the self-restoring film of the present invention, it is preferably applied to laminated glass. The laminated glass is preferably constituted by sandwiching the self-repairing film of the present invention having the infrared reflective film as a functional film between two glass substrates.

That is, the laminated glass of this invention is arrange | positioned from the incident light side in order of one glass base material, the self-repairing film provided with the said infrared reflective film as a functional film, and the other glass base material. The two glass substrates may be the same type of glass substrate or different types of glass substrates.
The glass substrate may be a flat glass substrate or a curved glass substrate used for a windshield of a car. In particular, the self-healing film having the molded adhesion layer and the self-healing layer according to the present invention is excellent in applicability to a curved glass substrate.

  The laminated glass according to the present invention preferably has a visible light transmittance of 70% or more, particularly when used as a car window glass. The visible light transmittance can be measured by using, for example, a spectrophotometer (U-4000 type, manufactured by Hitachi High-Technologies Corporation) using JIS R3106 (1998) “Transmissivity / Reflectance / Solar Heat Acquisition Rate of Sheet Glasses”. It can be measured in accordance with the “Test method”.

[Glass substrate]
Examples of the glass substrate used for the laminated glass include inorganic glass (hereinafter also simply referred to as glass) and organic glass (resin glazing). Examples of the inorganic glass include float plate glass, heat ray absorbing plate glass, polished plate glass, mold plate glass, netted plate glass, lined plate glass, and colored glass such as green glass. As said organic glass, it is a synthetic resin glass substituted for inorganic glass. Examples of the organic glass include polycarbonate plates and poly (meth) acrylic resin plates. Examples of the poly (meth) acrylic resin plate include a polymethyl (meth) acrylate plate. In the present invention, inorganic glass is preferred from the viewpoint of safety when it is damaged by an external impact.

  The kind of inorganic glass is not particularly limited, but usually soda lime silica glass is preferably used. In this case, it may be a colorless transparent glass or a colored transparent glass.

  Moreover, it is preferable that the glass substrate of the outdoor side close | similar to incident light among two glass base materials is a colorless transparent glass. Moreover, it is preferable that the glass substrate of the indoor side far from the incident light side is a green-colored colored transparent glass or dark colored transparent glass. The green colored transparent glass preferably has ultraviolet absorption performance and infrared absorption performance. By using these, the solar radiation energy can be reflected as much as possible on the outdoor side, and the solar radiation transmittance of the laminated glass can be further reduced.

Although the green colored transparent glass is not particularly limited, for example, soda lime silica glass containing iron is preferable. For example, it is soda-lime silica glass containing 0.3 to 1% by mass of total iron in terms of Fe ₂ O _{3 in} a soda-lime silica-based mother glass. Furthermore, since absorption of light having a wavelength in the near-infrared region is dominated by divalent iron out of total iron, the mass of FeO (divalent iron) is calculated in terms of Fe ₂ O ₃ , It is preferable that it is 20-40 mass% of iron.

In order to impart ultraviolet absorption performance, a method of adding cerium or the like to a soda lime silica base glass can be mentioned. Specifically, it is preferable to use soda lime silica glass having the following composition substantially. SiO _2: 65 to 75 _{wt%, Al} 2 O 3: _{0.1~5 wt%, Na 2 O + K 2} O: 10~18 wt%, CaO: 5 to 15 wt%, MgO: 1 to 6 wt%, terms of Fe ₂ O ₃ were total iron: 0.3 wt%, the total cerium CeO ₂ in terms and / or _TiO 2: 0.5 to 2 mass%.

  Moreover, although dark transparent glass is not specifically limited, For example, the soda-lime silica glass which contains iron in high concentration is mentioned suitably.

  When using the laminated glass of this invention for windows, such as a vehicle, it is preferable that both the thickness of an indoor side glass base material and an outdoor side glass base material is 1.5-3.0 mm. In this case, the indoor side glass base material and the outdoor side glass base material can have the same thickness or different thicknesses. In using laminated glass for an automobile window, for example, both the indoor side glass base material and the outdoor side glass base material may have a thickness of 2.0 mm or a thickness of 2.1 mm. Moreover, when using laminated glass for an automobile window, for example, the total thickness of the laminated glass is reduced by setting the thickness of the indoor glass substrate to less than 2 mm and the thickness of the outdoor glass substrate to 2 mm or more. In addition, it can resist external forces from the outside of the vehicle. The indoor side glass substrate and the outdoor side glass substrate may be flat or curved. Since vehicles, particularly automobile windows, are often curved, the shape of the indoor side glass substrate and the outdoor side glass substrate is often curved. In this case, the self-restoring film is provided on the concave side of the outdoor glass substrate. Furthermore, if necessary, three or more glass substrates can be used.

  The manufacturing method of the laminated glass of this invention is not specifically limited. For example, after sandwiching the self-restoring film of the present invention between two glass substrates, the glass substrate is passed through a pressure roll (also referred to as a nip roll) or sucked under reduced pressure in a rubber bag. The air remaining between the material and the self-healing film according to the present invention is degassed. Then, it pre-adheres at about 70-110 degreeC, and a laminated body is obtained. Next, the laminated body is put in an autoclave or pressed, and pressed at about 120 to 150 ° C. and a pressure of 1 to 1.5 MPa. In this way, a laminated glass can be obtained.

  The laminated glass can be used for automobiles, railway vehicles, aircraft, ships, buildings, and the like. Laminated glass can be used for other purposes. The laminated glass is preferably laminated glass for buildings or vehicles. The laminated glass can be used for an automobile windshield, side glass, rear glass, roof glass, or the like.

[4.3] Curved shape body The self-restoring film of the present invention can be suitably used for surface decoration of plastic casings used in home appliances, OA equipment, mobile phones, automobile interiors, and the like. .

  In particular, a curved shape body having a high design property such as addition of metallic luster or a complicated pattern can be formed on a member having a curved shape by the following forming method.

  Since the self-healing film of the present invention includes a molded adhesion layer and a self-healing layer, the surface of the curved body is not easily scratched and has excellent characteristics such as high light resistance.

  The molding method is mainly in-mold molding of the resin used for the substrate and the self-restoring film of the present invention by injection molding. Law) etc. can also be used. In-mold molding is further classified into in-mold lamination and in-mold transfer, and is appropriately selected.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "mass part" or "mass%" is represented.

<Production of infrared reflective film>
A polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., Cosmo Shine A4300, double-sided adhesive bonding, abbreviated as PET) was used as the transparent substrate film.

  A high refractive index layer containing the first water-soluble binder resin and the first metal oxide particles, and a low refractive index layer containing the second water-soluble binder resin and the second metal oxide particles as follows. Were alternately laminated to form an infrared reflective layer, and an infrared reflective film as a functional film was produced (corresponding to FIG. 3).

(1) Formation of undercoat layer The following undercoat layer coating solution was applied to a transparent base film so as to be 15 mL / m ² with an extrusion coater, and after passing through a 50 ° C. no-air zone (1 second), The substrate was dried at 120 ° C. for 30 seconds to obtain a support with an undercoat layer.

<Preparation of undercoat layer coating solution>
10g deionized gelatin
30 mL of pure water
Acetic acid 20g
The following crosslinking agent 0.2 mol / g gelatin The following nonionic fluorine-containing surfactant 0.2 g
1000 ml of an organic solvent of methanol: acetone = 2: 8 was used as an undercoat layer coating solution. As the deionized gelatin, one prepared by the following method was used.

<Preparation of deionized gelatin>
Ocein gelatin was obtained by performing lime treatment, water washing, and neutralization treatment, and performing extraction treatment in hot water at 55 to 60 ° C. on ossein from which lime was removed. The obtained ossein gelatin aqueous solution was subjected to both ion exchanges in a mixed bed of anion exchange resin (Diaion PA-31G) and cation exchange resin (Diaion PK-218) to prepare the deionized gelatin.

(2) Formation of Infrared Reflective Layer Using a slide hopper coating apparatus (slide coater) capable of multi-layer coating, the following low refractive index layer coating liquid L1 and high refractive index layer coating liquid H1 are kept at 45 ° C. In the support with the undercoat layer heated to 0 ° C., the dry thickness of each of the low refractive index layer and the high refractive index layer is 130 nm, and the lowermost layer and the uppermost layer are low refractive index layers. In this manner, a total of 18 simultaneous multilayer coatings were alternately carried out on 10 low refractive index layers and 8 high refractive index layers.

Immediately after application, 5 ° C. cold air was blown for 5 minutes to set. Thereafter, warm air of 80 ° C. was blown and dried to form an 18-layer infrared reflection layer.
In addition, what was prepared with the following method was used as the said coating liquid L1 for low refractive index layers, and the coating liquid H1 for high refractive index layers.

<Preparation of coating liquid L1 for low refractive index layer>
First, 680 parts of a colloidal silica (manufactured by Nissan Chemical Industries, Ltd., Snowtex (registered trademark) OXS) aqueous solution as 10% by mass of second metal oxide particles, and 4.0% by mass of polyvinyl alcohol (Kuraray Co., Ltd.). (Manufactured by PVA-103: polymerization degree 300, saponification degree 98.5 mol%) 30 parts of an aqueous solution and 150 parts of a 3.0% by mass boric acid aqueous solution were mixed and dispersed. Pure water was added to prepare 1000 parts of colloidal silica dispersion L1 as a whole.

  Subsequently, the obtained colloidal silica dispersion L1 was heated to 45 ° C., and 4.0% by mass of polyvinyl alcohol (B-Polyal, JP-45: Polymerization) as polyvinyl alcohol (B) therein. Degree 4500, saponification degree 86.5-89.5 mol%) 760 parts of aqueous solution was added with stirring. Thereafter, 40 parts of a 1% by weight betaine surfactant (manufactured by Kawaken Fine Chemical Co., Ltd., Sofazoline (registered trademark) LSB-R) aqueous solution was added to prepare a coating solution L1 for a low refractive index layer.

<Preparation of coating liquid H1 for high refractive index layer>
(Preparation of rutile titanium oxide as core of core / shell particles)
An aqueous suspension of titanium oxide was prepared such that the titanium oxide hydrate was suspended in water and the concentration when converted to TiO ₂ was 100 g / L. To 10 L of the suspension, 30 L of an aqueous sodium hydroxide solution (concentration: 10 mol / L) was added with stirring, then heated to 90 ° C. and aged for 5 hours. Next, the mixture was neutralized with hydrochloric acid, washed with water after filtration. In addition, in the said reaction (process), the titanium oxide hydrate which is a raw material is obtained by the thermal hydrolysis process of the titanium sulfate aqueous solution according to a well-known method.

The base-treated titanium compound was suspended in pure water so that the concentration when converted to TiO ₂ was 20 g / L. Therein, it was added with TiO ₂ amount to stirring 0.4 mole% citric acid. Then, when the temperature of the mixed sol solution reached 95 ° C., concentrated hydrochloric acid was added so that the hydrochloric acid concentration was 30 g / L. While maintaining the liquid temperature at 95 ° C., the mixture was stirred for 3 hours to prepare a titanium oxide sol liquid.

  As described above, when the pH and zeta potential of the obtained titanium oxide sol solution were measured, the pH was 1.4 and the zeta potential was +40 mV. Moreover, when the particle size was measured with a Zetasizer Nano manufactured by Malvern, the monodispersity was 16%.

  Further, the titanium oxide sol solution was dried at 105 ° C. for 3 hours to obtain titanium oxide powder fine particles. The powder fine particles were subjected to X-ray diffraction measurement using JDX-3530 type manufactured by JEOL Datum Co., Ltd., and confirmed to be rutile titanium oxide fine particles. The volume average particle size of the fine particles was 10 nm.

  Then, rutile type titanium oxide fine particles having a volume average particle diameter of 10 nm were added to 4 kg of pure water to obtain 10.0% by mass of a titanium oxide sol aqueous dispersion.

(Preparation of core / shell particles by shell coating)
To 2 kg of pure water, 0.5 kg of 10.0 mass% titanium oxide sol aqueous dispersion was added and heated to 90 ° C. Next, 1.3 kg of an aqueous silicic acid solution prepared so that the concentration when converted to SiO ₂ was 2.0% by mass was gradually added, followed by heat treatment at 175 ° C. for 18 hours in an autoclave, and further concentrated. . As a result, a sol solution (solid content concentration 20% by mass) of core-shell particles (average particle size: 10 nm) in which the core particles are titanium oxide having a rutile structure and the coating layer is SiO ₂ is obtained.

(Preparation of coating solution)
28.9 parts of a sol solution containing core / shell particles as the first metal oxide particles having a solid content concentration of 20.0% by mass obtained above, and 10.5 parts of a 1.92% by mass citric acid aqueous solution. 10 parts by mass of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-103: polymerization degree 300, saponification degree 98.5 mol%) aqueous solution 2.0 parts, and 3% by mass boric acid aqueous solution 9.0 parts. By mixing, a core-shell particle dispersion H1 was prepared.

  Next, while stirring the core-shell particle dispersion H1, 16.3 parts of pure water and 5.0% by mass of polyvinyl alcohol (A) as polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-124: degree of polymerization 2400, (Saponification degree 98-99 mol%) 33.5 parts of aqueous solution was added. Furthermore, 0.5 part of a 1% by weight betaine surfactant (manufactured by Kawaken Fine Chemical Co., Ltd., sofazoline (registered trademark) LSB-R) aqueous solution was added, and a high refractive index of 1000 parts as a whole using pure water. A layer coating solution H1 was prepared.

<< Preparation of self-healing film 101 >>
A self-healing film 101 was produced by forming a molded adhesion layer and a self-healing layer on the light reflecting layer of the infrared reflecting film produced above according to the following steps.

(1) Formation of molded adhesion layer <Acrylic polymer polymerized from monomer composition containing UV-stable monomer and UV-absorbing monomer>
200 parts of butyl acetate was charged into a 1 L flask equipped with a stirrer, a dripping port, a thermometer, a cooling pipe and a nitrogen gas inlet, and nitrogen gas was introduced and heated to 90 ° C. while stirring. Into the flask, 45 parts by weight of 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine, 90 parts by weight of glycidyl methacrylate, 165 parts by weight of butyl methacrylate as UV-stable monomer and UV-absorbing monomer, and start A mixture of 1.5 parts by mass of 2,2′-azobis (2-methylbutyronitrile) as an agent was added dropwise over 4 hours, followed by heating for 2 hours. Next, the temperature was raised to 110 ° C. while blowing a mixed gas of nitrogen and oxygen, and 50 parts by mass of pentaerythritol triacrylate as a main component of the molded adhesion layer was dropped over 30 minutes. After dropping, the reaction was further continued for 6 hours to obtain a 65% by mass solution of an acrylic polymer having an acryloyl group in the side chain. The acid value of this obtained solution was 15 mg KOH, and the number average molecular weight was 14,300.

<Formation of layer>
The said acrylic polymer solution was apply | coated so that the dry layer thickness might be set to 5 micrometers on the infrared reflective layer of the said infrared reflective film 1, and it dried at 80 degreeC for 0.25 minute, and formed the adhesion layer.

(2) Formation of self-healing layer Next, the following self-healing layer composition was filtered through a polypropylene filter having a pore size of 0.4 μm without performing an aging treatment on the formed adhesion layer. It apply | coated to the surface of a shaping | molding contact | adherence layer using the micro gravure coater. Next, after drying at a constant-rate drying zone temperature of 80 ° C. and a reduced-rate drying zone temperature of 80 ° C., the irradiance of the irradiated part is irradiated using an ultraviolet lamp while purging with nitrogen so that the oxygen concentration becomes 1.0% by volume or less. Was 100 mW / cm ² , the irradiation amount was 0.3 J / cm ² , and the coating layer was cured to form a self-repairing layer having a dry layer thickness of 20 μm. This was wound up to produce a roll-shaped self-repairing film 101.

[Self-healing layer composition]
AUP-787 (manufactured by Tokushi Co., Ltd.) 100 parts by mass Methyl ethyl ketone 50 parts by mass Propylene glycol monomethyl ether 30 parts by mass BYK-381 (surfactant: manufactured by Big Chemie Japan) 1 part by mass AUP-787 is urethane acrylate, It is a resin composition containing a photopolymerization initiator and methyl ethyl ketone.

<< Preparation of self-healing film 102 >>
A self-healing film 102 was produced in the same manner as in the production of the self-healing film 101 except that pentaerythritol triacrylate used as the main component of the molded adhesion layer was changed to pentaerythritol tetraacrylate.

<< Preparation of self-healing film 103 >>
A self-healing film 103 was produced in the same manner as in the production of the self-healing film 101 except that pentaerythritol triacrylate used as the main component of the molded adhesion layer was changed to cyanuric acid triacrylate.

<< Preparation of self-healing film 104 >>
A self-healing film 104 was produced in the same manner as in the production of the self-healing film 101 except that pentaerythritol triacrylate used as the main component of the molded adhesion layer was changed to G13 (manufactured by Nippon Shokubai).

<< Preparation of self-healing film 105 >>
A self-healing film 105 was produced in the same manner as in the production of the self-healing film 101 except that pentaerythritol triacrylate used as a main component of the molded adhesion layer was changed to G137 (manufactured by Nippon Shokubai).

<Evaluation of self-healing film>
The following evaluations were performed on the self-restoring films 101 to 105 produced as described above. Each evaluation result is shown in Table 2.

(1) Measurement of degree of repair (A) of self-healing layer For each of the prepared self-healing films, the surface of the film was measured using a Vickers indenter and a microhardness meter using a triangular pyramid indenter with an angle between ridges of 115 degrees. A load test force-indentation depth curve when the indenter was indented at the set indentation depth h _max (μm) was prepared. Then, from the residual depths (h ₁ , h ₂ ) (see FIG. 2) obtained when each self-healing film was measured at an unloading holding time of 0 seconds or 60 seconds, A = (h ₁ -h ₂ ). ) / H _max ). The above measurement was performed five times at different locations on the film surface, and the average value thereof was obtained as the degree of repair (A).

  The specific measurement conditions were measured under the following measurement conditions using a dynamic ultra-micro hardness meter DUH-211S (manufactured by Shimadzu Corporation).

Indenter shape: Triangular pyramid indenter (edge angle 115 °)
Measurement environment: temperature 23 ° C, relative humidity 50%
Maximum test load: 196.13mN
Loading speed: 6.662 mN / 10 seconds Unloading speed: 6.662 mN / 10 seconds

(2) Measurement of surface free energy of functional film, molded adhesion layer and self-healing layer and its hydrogen bonding component The surface free energy and its hydrogen bonding component were measured as follows for the prepared self-healing film. . In addition, the measurement with respect to a functional film and a shaping | molding contact | adherence layer dropped 2 ml of surface treatment liquid (tetrahydrofuran) on the film surface layer per 100 mm x 100 mm, and remove | excluded the self-healing layer and shaping | molding contact | adherence layer of the self-healing film over predetermined time Thereafter, the surface treatment liquid is removed.

Measuring device: Solid-liquid interface analyzer (DropMaster 500, manufactured by Kyowa Interface Science Co., Ltd.)
Measuring method: Droplet method Environment: Temperature 23 ° C, 55% RH
Three standard liquids: pure water, nitromethane, methylene iodide and the contact angle between the functional film surface, the molded adhesion layer surface, and the self-healing layer surface in each self-healing film are in a method defined in JIS R3257. In conformity, about 3 μL of the standard liquid was dropped on the solid to be measured, and measured five times with a solid-liquid interface analyzer (DropMaster 500, manufactured by Kyowa Interface Science Co., Ltd.), and the average contact angle was obtained from the average of the measured values. . The time to contact angle measurement was 60 seconds after the reagent was dropped.

Next, three components of the surface free energy of the solid were calculated based on the Young-Dupre equation and the extended Fowkes equation. In addition, it calculated using surface free energy analysis software EG-11 (made by Kyowa Interface Science Co., Ltd.).
Young-Dupre equation: W _SL = γL (1 + cos θ)
W _SL : Adhesion energy between liquid / solid γL: Surface free energy of liquid θ: Contact angle of liquid / solid Extended Fowkes' formula:
W _SL = 2 {(γ _sd γL _d ) ^1/2 + (γ _sp γL _p ) ^1/2 + (γ _sh γL _h ) ^1/2 }
γL = γL _d + γL _p + γL _h : surface free energy of liquid γ _s = γ _sd + γ _sp + γ _sh : surface free energy of solid γ _sd , γ _sp , γ _sh : dispersion of surface free energy, dipole, hydrogen bond Each ingredient

By solving the ternary simultaneous equations from the contact angle values, the surface free energy component values (γ _sd , γ _sp , γ _{sh on the} surface of the functional film, the surface of the molded adhesion layer and the surface of the self-healing layer in each self-healing film are obtained. )

(3) Evaluation of optical performance The produced self-restoring film was thermoformed into a curved lens (φ200 mm, R300) shape at 150 ° C./3 min, and the regular reflectance was measured before and after the molding. For the measurement of regular reflectance, U-4000 type (manufactured by Hitachi High-Technologies Corporation) is used as a spectrophotometer, and the reflectance in the region of light wavelength of 400 to 1000 nm of each self-healing film is 23 ° C./55%. Under the RH environment, the reflectance at an incident angle of 5 ° with respect to the normal line of the reflecting surface was measured at 10 points at equal intervals in the width direction of the film. And the average value was calculated | required and this was made into the regular reflectance (%). The change rate of the regular reflectance before and after molding was calculated, and the change rate was evaluated according to the following evaluation criteria.

◎: 1% or less ○: Greater than 1%, 3% or less △: Greater than 3%, 5% or less ×: Greater than 5%

(4) Evaluation of weather resistance The prepared self-restoring film was thermoformed into a curved lens (φ200 mm, R300) shape at 150 ° C./3 min, and a weather resistance test was performed on the molded self-restoring film. In the weather resistance test, an Xe weather resistance test apparatus (Suga Test Instruments Co., Ltd., xenon weather meter NX25) was used, and exposure was performed for 2000 hours at a wavelength of 300 to 400 nm and an irradiation intensity of 60 W. Similarly to the evaluation of the optical performance, the regular reflectance of the self-restoring film was measured before and after the weather resistance test, and the rate of change was calculated. The calculated rate of change was evaluated according to the following evaluation criteria.

◎: 3% or less ○: Greater than 3%, 5% or less △: Greater than 5%, 10% or less ×: Greater than 10%

As shown in Table 2, it can be seen that the self-healing film of the present invention is superior in optical performance and weather resistance after molding to the self-healing film of the comparative example. In the self-healing film of the comparative example, it is considered that the optical performance and the weather resistance are lowered due to the occurrence of delamination when being formed.
Further, the difference in hydrogen bonding component of the surface free energy between the molded adhesion layer and the functional film is 2 mN / m or more, and the difference in hydrogen bonding component of the surface free energy between the molding adhesion layer and the self-healing layer is 2 mN / m. The self-healing films 103 and 105 that are equal to or greater than m can be formed without generating distortion or minute voids as compared with the self-healing film 104 that does not satisfy the conditions. It is possible to prevent the deterioration of the weather resistance due to the deterioration of the optical performance due to the void.

DESCRIPTION OF SYMBOLS 1 Functional film 4 Molding adhesion layer 5 Self-healing layer MF, RF, WF Self-healing film

Claims (2)

A functional film;
A self-healing layer provided on the functional film;
A molding adhesion layer provided between the functional film and the self-healing layer,
The molded adhesion layer contains a polymer obtained by polymerizing a monomer composition containing at least one selected from UV-stable monomers and at least one selected from UV-absorbing monomers, and has a surface free energy of 50 mN / m or more, A self-repairing film, wherein the hydrogen bond component of the surface free energy is 3 mN / m or more. The difference in hydrogen bond component of the surface free energy between the molded adhesion layer and the functional film is 2 mN / m or more,
2. The self-healing film according to claim 1, wherein a difference in hydrogen bonding components of surface free energy between the molded adhesion layer and the self-healing layer is 2 mN / m or more.

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