JP2014214986A - Mirror for solar thermal power generation and reflection device for solar thermal power generation equipped with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a mirror for solar thermal power generation which hardly causes deterioration of reflectance due to corrosion and color change of a silver reflection layer even after being exposed in the outdoors for a long term and has high adhesiveness between the silver reflection layer and other constituent layers even with a load from such as cleaning.SOLUTION: A mirror for solar thermal power generation provided with a metal reflection layer on a resin substrate is characterized in that at least one layer of layers adjacent to the metal reflection layer contains triazine thiols represented by the following general formula (1) (in the formula, R, Rand Rrespectively represent hydrogen atom or substituent and either one of substituent represented by R, Rand Rrepresents thiol group or a substituent having thiol group.).

Description

  The present invention relates to a solar power generation mirror and a solar power generation reflection device including the mirror. In more detail, even after being exposed to the outdoors for a long time, the reflectance of the metal reflective layer is small due to corrosion and discoloration, and high adhesion between the metal reflective layer and other constituent layers even under load due to cleaning work etc. The present invention relates to a solar power generation mirror having the above and a solar power generation reflection device including the mirror.

  In recent years, solar energy has been considered to be the most stable and abundant amount of natural energy that can be used as an alternative to fossil fuels. By collecting solar energy with a huge reflector, power is generated using that thermal energy as a medium. Solar power generation has been proposed.

  Since this reflector is exposed to sunlight, ultraviolet rays, heat, wind and rain, sandstorms, etc., glass mirrors have been used in the past, but recently it is light and flexible, and solar heat is low in production and transportation costs. A film mirror is being studied as a power generation mirror.

  The film mirror for solar power generation suppresses corrosion of silver by laminating a resin coat layer made of a resin and a corrosion inhibitor on a metal reflection layer provided on a film substrate, for example, a silver reflection layer. Furthermore, by laminating a resin layer containing an ultraviolet absorber on the upper layer, it is possible to suppress a decrease in reflectivity due to discoloration of the resin layer caused by UV exposure, and to suppress damage by providing a hard coat layer etc. on the outermost surface. As a result, durability is improved.

  On the other hand, since mirrors for solar thermal power generation are installed in an outdoor environment, cleaning work is regularly performed by high-pressure water discharge or brushing in order to suppress a decrease in reflectance caused by dust or the like adhering to the mirror surface. ing. However, when these film cleaning is performed on solar power generation film mirrors that have been exposed outdoors for a long period of time, peeling occurs between the silver reflective layer and the upper resin coating layer, or between the silver reflective layer and the film substrate, due to the stress generated during the cleaning. This causes a problem that the reflectivity decreases.

  As described above, in the film mirror for solar power generation, it can withstand long-term outdoor use, and high adhesion is required so that no peeling occurs between the silver reflective layer and other constituent layers due to the stress generated during the cleaning operation. Yes.

  For example, in Patent Document 1, an acrylic resin layer containing an ultraviolet absorber is provided on the outermost layer of the film, and a decrease in reflectance due to discoloration of the resin layer due to ultraviolet exposure is suppressed. However, in the case of Patent Document 1, a polyethylene terephthalate (PET) layer and an adhesive layer are sandwiched between a silver reflective layer and an acrylic resin layer, and when cleaning by brushing is performed after outdoor exposure for more than half a year, There is a problem that peeling occurs between the reflective layer and the PET layer, and the reflectance is greatly reduced.

  Further, in Patent Document 2, the resin coat layer is peeled off from the silver reflection layer by using an acrylic silicone resin made of an acrylic resin and a silane coupling agent as a resin that adheres firmly to the silver reflection layer. Is suppressed. However, a film mirror generally has a configuration in which a plurality of constituent layers are laminated. And the layer which consists of acrylic silicone resins had the problem that the adhesiveness with the other structural layer provided adjacently was weak, and it was easy to peel off by the washing | cleaning operation | work etc. by brushing.

  For this reason, even after being exposed to the outdoors for a long period of time, the reflectance of the silver reflective layer is not reduced significantly due to corrosion or discoloration, and high adhesion is achieved between the silver reflective layer and other constituent layers even when subjected to a load such as cleaning work. There is a need for a film mirror having the same.

Special table 2009-520174 JP 2004-203014 A

  The present invention has been made in view of the above problems and situations, and the solution to the problem is that the decrease in reflectance due to corrosion or discoloration of the metal reflective layer is small even after being exposed to the outdoors for a long time, and the cleaning work or the like. The object is to provide a solar thermal power generation mirror having high adhesion between the metal reflective layer and other constituent layers even when a load is applied. Moreover, it is providing the solar power generation reflective apparatus excellent in durability provided with it.

  The present inventor is a solar power generation mirror in which a metal reflective layer is provided on a resin base material in the process of studying the cause of the above problem in order to solve the above-described problem, and is adjacent to the metal reflective layer. The mirror for solar power generation, which contains a specific compound, reduces the decrease in reflectivity due to corrosion or discoloration of the metal reflective layer even after being exposed to the outdoors for a long time. It has been found that high adhesion is developed between the layer and other constituent layers, and the present invention has been achieved.

  That is, the said subject which concerns on this invention is solved by the following means.

  1. A mirror for solar power generation in which a metal reflective layer is provided on a resin base material, wherein at least one layer adjacent to the metal reflective layer contains a triazine thiol represented by the following general formula (1) Mirror for solar thermal power generation.

（式中、Ｒ_１、Ｒ_２及びＲ_３は各々水素原子又は置換基を表し、Ｒ_１、Ｒ_２及びＲ_３で表される置換基のいずれか一つはチオール基又はチオール基を有する置換基を表す。）
２．前記Ｒ_１、Ｒ_２及びＲ_３で表される置換基のいずれか一つが、チオール基であることを特徴とする第１項に記載の太陽熱発電用ミラー。

(Wherein R ₁ , R ₂ and R ₃ each represent a hydrogen atom or a substituent, and any one of the substituents represented by R ₁ , R ₂ and R ₃ has a thiol group or a thiol group) Represents a group.)
2. The solar power mirror according to claim 1, wherein any one of the substituents represented by R ₁ , R _2, and R ₃ is a thiol group.

3. The solar power mirror according to claim 1 or 2, wherein two or more of the substituents represented by R ₁ , R ₂ and R ₃ are thiol groups.

  4). Any one of Items 1 to 3, wherein the solar power generation mirror has a hard coat layer, and the hard coat layer contains a polymer-derived inorganic oxide or inorganic nitride having a metalloxane skeleton. The solar power generation mirror according to claim 1.

  5. A solar power generation reflector, wherein the solar power generation mirror according to any one of items 1 to 4 is bonded to a support base material via an adhesive layer.

  By the above means of the present invention, even after being exposed to the outdoors for a long period of time, the decrease in reflectance due to corrosion and discoloration of the metal reflective layer is small, and even when a load is applied due to cleaning work etc., between the metal reflective layer and other constituent layers A mirror for solar power generation having high adhesion can be provided. Moreover, the reflective apparatus for solar power generation excellent in durability provided with it can be provided.

  The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.

  When solar power mirrors are exposed to ultraviolet rays for a long period of time, corrosion and discoloration of the metal used in the metal reflection layer and peeling between the metal reflection layer and other constituent layers occur, resulting in a decrease in reflection performance. Cheap. In order to prevent these, the benzotriazole compound and triazine compound, which have been conventionally used as a corrosion inhibitor or an antioxidant, and a thiol compound, each of which is contained alone in another constituent layer adjacent to the metal reflective layer, Higher performance could not be obtained, and there was a problem with the adhesiveness that particularly caused delamination.

  The present inventor has added triazine thiols to a layer adjacent to the metal reflective layer so that the thiol group of the triazine thiol forms a monomolecular film or a multimolecular film with the metal of the metal reflective layer. It has been found that the adhesiveness between the layers can be greatly improved by bonding them together. Furthermore, the triazine structure possessed by triazine thiols is excellent in light resistance, so that it can maintain stable and good performance even when exposed to ultraviolet rays for a long period of time against corrosion and discoloration of metals as well as adhesion between the layers. Therefore, it is considered that a solar power generation mirror having excellent durability in terms of corrosion and discoloration of metal and adhesion between the metal reflection layer and other constituent layers can be obtained.

  Since the technique of the present invention has both adhesion and light resistance, the deformation of the layer due to peeling after long-term outdoor exposure is small. Since the outermost hard coat layer is relatively hard and fragile, there is a problem that it is easy to induce cracks and cracks due to deformation of the lower layer, but it also has a high effect on solving this problem Can do.

Explanatory drawing which shows an example of a structure of the mirror for solar power generation of this invention Explanatory drawing which shows an example of a structure of the reflective apparatus for solar thermal power generation of this invention

  The solar power generation mirror of the present invention is a solar power generation mirror in which a metal reflection layer is provided on a resin base material, and at least one layer adjacent to the metal reflection layer is represented by the general formula (1). With such a structure, it is possible to reduce the decrease in reflectivity due to corrosion or discoloration of the metal reflection layer even after being exposed to the outdoors for a long time, and even when subjected to a load due to cleaning work etc. Provided is a solar power generation mirror having high adhesion between a metal reflection layer and other constituent layers. This feature is a technical feature common to the inventions according to claims 1 to 5. As a form of the present invention, a film mirror, in particular, a mirror using a flexible resin base material is more effective. Hereinafter, it demonstrates as a film mirror.

As an embodiment of the present invention, from the viewpoint of manifesting the effect of the present invention, any one of the substituents represented by R ₁ , R ₂ and R ₃ of the triazine thiol represented by the general formula (1) is It is preferable that it is a thiol group, and that two or more of the substituents represented by R ₁ , R ₂ and R ₃ in the general formula (1) are thiol groups, It is preferable from the viewpoint of preventing discoloration and having high adhesion to the metal reflective layer.

  Furthermore, it is preferable that the film mirror for solar power generation has a hard coat layer, and that the hard coat layer contains a polymer-derived inorganic oxide or inorganic nitride having a metalloxane skeleton. In addition, the scratch resistance of the surface is improved.

  The film mirror for solar power generation according to the present invention is suitably provided in a solar power generation reflector excellent in durability.

  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 Film Mirror for Solar Power Generation and Reflector for Solar Power Generation>
The film mirror for solar power generation of the present invention (hereinafter also simply referred to as a film mirror) is a film mirror in which a metal reflective layer is provided on a resin substrate, and is at least one of the layers adjacent to the metal reflective layer. The layer is characterized by containing triazine thiols.

[1] Outline of Configuration of Film Mirror for Solar Power Generation An outline of a film mirror for solar power generation of the present invention (hereinafter sometimes simply referred to as a film mirror) will be described.

  As shown in FIG. 1 (a), the minimum functional structure of the film mirror F for solar power generation is to form a metal reflective layer (for example, a silver reflective layer) 5 on a resin base material 3, and to form an outermost layer thereon. The hard coat layer 10 is provided. Therefore, in this case, the resin base material 3 and the hard coat layer 10 correspond to the layer adjacent to the metal reflection layer in the present invention.

  It is preferable to provide various functional layers in the film mirror F for solar thermal power generation. For example, as shown in FIG. 1B, an anchor layer 4 is provided between the resin base material 3 and the metal reflective layer 5. In addition, it is also preferable to provide the resin coat layer 6 containing a corrosion inhibitor or an antioxidant on the light incident side of the metal reflective layer 5, and it is also preferable to provide the adhesive layer 7 on the resin coat layer 6.

  An acrylic resin layer 8 and an intermediate layer 9 containing an ultraviolet absorber are preferably provided on the adhesive layer 7, and a hard coat layer 10 is preferably provided as the outermost layer on the intermediate layer 9.

  The gas barrier layer 11 is preferably provided if necessary to protect the metal reflective layer and the resin coat layer.

  Moreover, it is also a preferable aspect that the adhesive layer 2 is provided on the surface of the resin base 3 opposite to the light incident side. A release layer 12 for protecting the adhesive layer is preferably formed on the adhesive layer 2.

  In the case of the configuration of FIG. 1B, the layer adjacent to the metal reflection layer 5 corresponds to the anchor layer 4 or the resin coat layer 6, and at least one of the layers contains the triazine thiols according to the present invention. To do. In order to enhance the effect of the present invention, it is preferable that both the anchor layer 4 and the resin coat layer 6 contain the triazine thiols.

  In addition, the layer adjacent to the metal reflection layer is not limited to the layer directly in contact with the metal reflection layer, the triazine thiols according to the present invention can act on the metal of the metal reflection layer, and the effects of the present invention can be expressed. If possible, there may be a thin film layer (for example, a resin layer) that does not contain the triazine thiol between layers.

  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, and still more preferably in the range of 100 to 220 μm, from the viewpoint of mirror deflection prevention, regular reflectance, handling properties, and the like. Is within.

  Hereinafter, although each structural layer which comprises the film mirror of this invention is demonstrated sequentially, the triazine thiols which are the characteristics of this invention are demonstrated first.

[2] Triazine thiols The triazine thiols according to the present invention have a triazine ring consisting of three nitrogen atoms and three carbon atoms, and one or preferably two or more thiol groups in the molecule or from this It refers to a compound having a derived group, and is a compound represented by the following general formula (1).

上記式中、Ｒ_１、Ｒ_２及びＲ_３は各々水素原子又は置換基を表し、Ｒ_１、Ｒ_２及びＲ_３で表される置換基のいずれか一つはチオール基又はチオール基を有する置換基を表す。

In the above formula, R ₁ , R ₂ and R ₃ each represent a hydrogen atom or a substituent, and any one of the substituents represented by R ₁ , R ₂ and R ₃ has a thiol group or a thiol group. Represents a group.

Although it does not specifically limit as a substituent which does not have a thiol group among R < ₁ >, R < ₂ > and R < ₃ >, An alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, an amino group, -NR < ₄ >. Examples include a group represented by R ₅ , —NHR ₆ , —OR ₇ or —SR ₈ , preferably an alkyl group or a phenyl group.

  Examples of the alkyl group include alkyl groups having 1 to 25 carbon atoms, preferably 1 to 18 carbon atoms. Such an alkyl group may be linear, branched, or cyclic. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- A butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a decyl group, a cetyl group, a stearyl group, a 1-menthyl group, etc. are mentioned, and it must be a methyl group or an ethyl group Is preferred.

  Moreover, as an alkenyl group, a C1-C20, Preferably 1-10 alkenyl group is mentioned. Examples of such an alkenyl group include a propanedienyl group, an isopropenyl group, a 3-methyl-2-butenyl group, an allyl group, and a 2-methylallyl group, and an isopropenyl group is preferable.

  Moreover, as an alkynyl group, a C1-C20, Preferably 1-10 alkynyl group is mentioned. Examples of such an alkynyl group include a propargyl group and 1-phenylpropargyl group, and a propargyl group is preferable.

  Moreover, as an aralkyl group, a C1-C20, Preferably 1-10 aralkyl group is mentioned. Examples of such an aralkyl group include a 4-phenylbutyl group.

As the aryl group, a phenyl group (C ₆ H ₅ —), a methoxyphenyl group, an o-tolyl group, a p-nitrophenyl group, a 2-nitrophenyl group, a 3-nitrophenyl group, a p-fluorophenyl group, p-methoxyphenyl group, p-aminophenyl group, N-methylaminophenyl group, p- (dimethylamino) phenyl group, 4-acetylphenyl group, p-iodophenyl group, p-chlorophenyl group, 2,4,6 -Trichlorophenyl group, 2,4,6-trimethylphenyl group, 2,4,6-tribromophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, 2,4-dimethylphenyl group, etc. And is preferably a phenyl group.

As the substituted amino group represented by -NR ₄ R _5, and substituents R ₄ and R ₅ are the same or different from each other, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or an aralkyl group, an alkyl group Or it is preferable that it is an alkenyl group.

  Here, examples of the alkyl group, alkenyl group, alkynyl group, aryl group, and aralkyl group include the same groups as described above. Here, the alkyl group is preferably a 2-piperidinoethyl group, a fluorine-substituted fluoroalkyl group, or a cyclic cycloalkyl group, in addition to the groups mentioned in the above description. Examples of the cycloalkyl group such as an ethyl group include a cyclohexyl group and a cyclopentyl group. The aralkyl group is preferably a benzyl group or a substituted benzyl group, and examples thereof include a benzyl group, a methylbenzyl group, a 1-phenylethyl group, and a 2-phenylethyl group.

In addition, as the mono-substituted amino group represented by —NHR ₆ , the substituent R ₆ is an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, an anilino group, a hydroxyanilino group, a p-methylanilino group, and A group selected from morpholino groups is shown, and among these, an alkyl group is preferred. Examples of the hydroxyanilino group include groups derived from o-, m-, p-hydroxyaniline derivatives.

  Here, examples of the alkyl group, alkenyl group, alkynyl group, aralkyl group, and aryl group include the same groups as described above.

Further, the group represented by -OR _7, represents a group substituent R ₇ is an alkyl group, an alkenyl group, aralkyl group or aryl group.

  Here, examples of the alkyl group, alkenyl group, and aralkyl group can include the same groups as described above. Examples of the aralkyl group include a 4-phenylbutyl group. Examples of the aryl group include a phenyl group, Examples thereof include a substituted phenyl group such as a halogenophenyl group, and a naphthyl group.

  Here, as the halogenophenyl group, for example, p-iodophenyl group, p-chlorophenyl group, p-bromophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, 2,4-diiodophenyl Group, 2,4,6-trichlorophenyl group, 2,4,6-tribromophenyl group and the like.

Further, the group represented by -SR _8, a substituted group R ₈ is an alkyl group, an alkenyl group, an alkynyl group, a group selected from aralkyl group or an aryl group. Examples of these groups include the same groups as the substituents described above.

In the case where the substituent represented by R ₁ , R ₂ and R ₃ is a substituent having a thiol group, it is not particularly limited, but the thiol group is bonded to the substituents mentioned in the description of the substituent. The substituent is preferably an alkyl group, an alkenyl group, an aralkyl group, an aryl group, or an amino group, and more preferably an alkyl group or an aryl group.

In the triazine thiols according to the present invention, any one of the substituents represented by R ₁ , R ₂ and R ₃ is preferably a thiol group, and further represented by R ₁ , R ₂ and R ₃ . A triazine dithiol compound in which two or more of the substituents to be used are thiol groups, or a triazine trithiol compound in which all of the substituents represented by R ₁ , R ₂ and R ₃ are thiol groups. It is preferable from the viewpoint of enhancing the effect of the present invention because it has a high affinity with, for example, silver contained in the reflective metal layer.

  Specific examples of the dithiol compound represented by the general formula (1) preferably used in the present invention include, for example, s-triazine-2,4-dithiol, 6-methyl-s-triazine-2,4-dithiol, 6 -Phenyl-s-triazine-2,4-dithiol, 6-amino-s-triazine-2,4-dithiol, 6-dihexylamino-s-triazine-2,4-dithiol, 6- [bis (2- Hexyl) amino] -s-triazine-2,4-dithiol, 6-diethylamino-s-triazine-2,4-dithiol, 6-dicyclohexylamino-s-triazine-2,4-dithiol, 6-diphenylamino- s-triazine-2,4-dithiol, 6-dibenzylamino-s-triazine-2,4-dithiol, 6-diallylamino-s-to Azine-2,4-dithiol, 6-didodecylamino-s-triazine-2,4-dithiol, 6-dibutylamino-s-triazine-2,4-dithiol, 6-dimethylamino-s-triazine-2, 4-dithiol, 6-phenylamino-s-triazine-2,4-dithiol, 2- (3,5-di-tert-butyl-4-hydroxyanilino) -s-triazine-2,4-dithiol, 6 -Stearylamino-s-triazine-2,4-dithiol, 6-ethylamino-s-triazine-2,4-dithiol, 6-hexylamino-s-triazine-2,4-dithiol, 6- (cis-9) -Octadecenylamino) -s-triazine-2,4-dithiol, 6-cyclohexylamino-s-triazine-2,4-dithiol, 6- Nilino-1,3,5-triazine-2,4-dithiol, 6- (4-anilino-N-isopropylanilino) -s-triazine-2,4-dithiol, 6-methoxy-s-triazine-2, 4-dithiol, 6- (1-naphthyloxy) -s-triazine-2,4-dithiol, 6- (m-chlorophenoxy) -s-triazine-2,4-dithiol, 6- (2,4-dimethyl) Phenoxy) -s-triazine-2,4-dithiol, 6-phenoxy-s-triazine-2,4-dithiol and the like.

  Specific examples of the trithiol compound represented by the general formula (1) include 1,3,5-triazine-2,4,6-trithiol, 1,3,5-triazine-2,4,6- Trithiol monosodium, 1,3,5-triazine-2,4,6-trithiol triethanolamine, and 1,3,5-triazine-2,4,6-trithiol di (tetrabutylammonium salt) are also preferable. As an example.

  Among these, 6-anilino-1,3,5-triazine-2,4-dithiol and 6-dibutylamino-1,3,5-triazine-2,4-dithiol are preferable because of the high effect of the present invention.

  The triazine thiols according to the present invention are used in an amount sufficient to prevent corrosion and discoloration of the metal contained in the metal reflective layer and improve adhesion, and are usually at least of the layer adjacent to the metal reflective layer. It is preferable to make it contain in the range of 0.1-5 mass% to one layer. More preferably, it exists in the range of 1-5 mass%. If it is in the said range, corrosion and discoloration of a metal can be prevented, especially adhesiveness can fully be improved, and the merit on cost is also high.

  The triazine thiols are preferably contained in the anchor layer or the resin coat layer described below, and more preferably both the anchor layer and the resin coat layer are layers containing triazine thiols.

[3] Resin base material As the resin base material, various conventionally known resin films can be used. For example, cellulose ester film, polyester film, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyethylene terephthalate, polyethylene naphthalate polyester film, polyethylene film, polypropylene film, cellophane, Cellulose diacetate film, cellulose triacetate film, cellulose acetate propionate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, polycarbonate film, norbornene resin film , Polymethylpentenef Can Lum, polyether ketone film, polyether ketone imide film, a polyamide film, a fluororesin film, a nylon film, polymethyl methacrylate film, and acrylic films. 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 resin film may be a film manufactured by melt casting film formation or a film manufactured by solution casting film formation.

  In order to contain the triazine thiols according to the present invention in a resin base material, for example, in the case of solution casting film formation, a predetermined amount of the compound is added to a dope containing an organic solvent to be prepared, and then the solution is flowed on a metal support. It is preferable to extend.

  Since the resin substrate is located farther from the light incident side than the reflective layer, ultraviolet rays hardly reach the resin substrate. In particular, it is difficult for ultraviolet rays to reach the resin base material by adding an ultraviolet absorber to the layer on the light incident side of the resin base material or providing an acrylic resin layer containing the ultraviolet absorber. In that case, even a resin that is easily deteriorated by ultraviolet rays can be used for the resin base material. From such a viewpoint, a polyester film such as polyethylene terephthalate can be used as the resin base material.

  The thickness of the resin base material is preferably an appropriate thickness according to 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.

  Moreover, it is preferable to manufacture the film mirror for solar power generation of this invention using a elongate film, it is preferable that it is 1000 m or more in length, and uses a long film of about 5000 m from a viewpoint of productivity or handling. It is preferable.

[3] Anchor layer The anchor layer is made of a resin, and adheres the resin base material and the metal reflective layer, and is a layer containing the triazine derivative according to the present invention. Therefore, the anchor layer has a close adhesion between the resin base material and the metal reflective layer, heat resistance that can withstand heat when the metal reflective layer is formed by a vacuum deposition method, etc., and high reflection inherent in the metal reflective layer. Smoothness is required to bring out performance.

  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 resins, vinyl chloride resins, vinyl chloride vinyl acetate copolymer resins, etc. can be used alone or mixed resins thereof. From the viewpoint of weather resistance, mixed resins of polyester resins and melamine resins are preferred, and isocyanates etc. 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. When the thickness is greater than 0.01 μm, the adhesion is improved, the unevenness on the surface of the resin substrate is covered and smoothness is improved, and as a result, the effect of increasing the reflectance of the metal reflective layer is exhibited. . Moreover, it is preferable that the thickness is 3 μm or less because there is no uneven formation of the anchor layer and the smoothness is high, and the anchor layer is sufficiently cured.

  The anchor layer preferably contains triazine thiols within a range of 0.1 to 5% by mass, and more preferably 1 to 5% by mass. The compound is preferably dissolved in an organic solvent such as methanol, glycols, and ketones and added to the resin material.

[4] Metal reflective layer The metal reflective layer is a layer made of metal or the like having a function of reflecting sunlight.

  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 10 to 200 nm, more preferably in the range of 30 to 150 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 method for manufacturing a film mirror for solar power generation, 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 for solar power generation. 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. .

[5] 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.

  By containing the triazine thiols according to the present invention in the resin coat layer, the adhesion between the silver reflective layer and the resin coat layer can be greatly improved, and further, corrosion and discoloration of the silver reflective layer can be prevented. it can.

  Content of the triazine thiols to the said resin coat layer is the range of 0.1-5 mass%. More preferably, it is the range of 1-5 mass%.

  In addition, the resin coat layer contains a silver corrosion inhibitor or antioxidant as long as the effect of the triazine thiols according to the present invention is not impaired, and imparts a function of preventing corrosion and deterioration of the silver reflective layer. Is also preferable.

  The resin coat layer may consist of only one layer or may consist 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.

(5-1) Corrosion inhibitor 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 having an imidazole ring It is desirable to be selected from a compound, a compound having an indazole ring, a copper chelate compound, a compound having a thiol group, a thiourea, a naphthalene-based compound, 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. It does not specifically limit as a silicone modified resin.

  As these compounds, 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.

(5-2) Antioxidant It is preferable to use a phenol-based antioxidant, a thiol-based antioxidant, or a phosphite-based antioxidant as the 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 .

[6] Adhesive layer The adhesive layer is not particularly limited as long as it has a function of enhancing the adhesion between the layers. In the example shown in FIG.1 (b), it forms in order to improve the adhesiveness of a resin coat layer and an acrylic resin layer. Therefore, the adhesive layer needs to have adhesiveness for bringing the layers into close contact with each other and smoothness for drawing out the high reflection performance inherent in the silver reflective layer.

  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 adhesiveness and smoothness conditions, polyester resin, urethane resin, acrylic resin, melamine resin, epoxy resin 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 such as isocyanate. 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.

  When the adhesive layer is a metal oxide, for example, silicon oxide, aluminum oxide, silicon nitride, aluminum nitride, lanthanum oxide, lanthanum nitride, or the like can be formed by various vacuum film forming methods to form the adhesive layer. 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.

[7] Acrylic resin layer 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 resin base material, and is preferably provided on the light incident side of the metal reflective 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.

  Moreover, in addition to providing the acrylic resin layer on the film mirror, an ultraviolet absorber is added to any one of the constituent layers provided on the light incident side of the resin substrate so that it also serves as the acrylic resin layer. Also good. For example, it is preferable to add an ultraviolet absorber to the hard coat layer.

  The ultraviolet absorber is roughly classified into an organic type and an inorganic type.

  Examples of organic ultraviolet absorbers include benzophenone, benzotriazole, phenyl salicylate, and triazine, and inorganic ultraviolet absorbers include titanium oxide, zinc oxide, cerium oxide, and iron oxide. Can be mentioned. A benzophenone compound, a benzotriazole compound and a triazine compound with little coloring are preferred. Moreover, you may use the ultraviolet absorber of Unexamined-Japanese-Patent No. 10-182621, 8-337574, and the polymeric ultraviolet absorber of Unexamined-Japanese-Patent No. 6-148430, 2003-113317. Moreover, as an ultraviolet absorber used preferably, the compound as described in Unexamined-Japanese-Patent No. 2012-232528 Paragraph (0036)-(0045) is mentioned.

  The usage-amount of a ultraviolet absorber is the range of 0.1-20 mass%, Preferably it is the range of 1-15 mass%, More preferably, it is the range of 3-10 mass%. By making it within these ranges, it becomes possible to improve the weather resistance while maintaining good adhesion of the other constituent layers.

[8] Intermediate layer The intermediate layer is a constituent layer that improves the adhesion between the acrylic resin layer and a hard coat layer described later.

  This intermediate layer contains at least one of polyvinyl alcohol resin, vinyl acetate resin, water-soluble cellulose, and water glass. Polyvinyl alcohol resin, vinyl acetate resin, water-soluble cellulose, and water glass have a hydroxy group as a reactive group.

  Examples of the method for forming the intermediate layer include a method by coating. When coating a coating film to be an intermediate layer by a coating method, various conventionally used coating methods such as spray coating, spin coating, bar coating, etc. can be used, such as polyvinyl alcohol resin, vinyl acetate. The intermediate layer can be formed by applying and applying a solution containing at least one of resin, water-soluble cellulose, and water glass on, for example, an acrylic resin layer.

  The film thickness of the intermediate layer is preferably from 0.1 to 5 μm, particularly preferably from 0.1 to 1 μm.

  The intermediate layer contains at least one of polyvinyl alcohol resin, vinyl acetate resin, water-soluble cellulose, and water glass, so that they and reactive groups on the surface of the acrylic resin layer (hydroxy group, carboxy group, etc.) And when the hard coat layer and the hard coat layer contain a polysiloxane compound, the intermediate bond between the intermediate layer and the acrylic resin layer and the interlayer between the intermediate layer and the hard coat layer are obtained by chemically bonding with the compound. The bond becomes a stronger bond. As a result, the adhesion between the acrylic resin layer and the hard coat layer via the intermediate layer is improved.

  Moreover, it is also preferable that an intermediate | middle layer contains polyisocyanate. In particular, when a polyvinyl alcohol resin and water-soluble cellulose are used, a water-dispersed polyisocyanate is preferable.

  When the intermediate layer contains polyisocyanate, the interlayer bond between the intermediate layer and the acrylic resin layer and the interlayer bond between the intermediate layer and the hard coat layer are further strengthened.

  The intermediate layer preferably contains conductive fine particles.

  When the intermediate layer contains conductive fine particles, the intermediate layer can also function as an antistatic layer.

[9] Hard coat layer The hard coat layer is a constituent layer (protective layer) provided on the outermost layer of the film mirror. When the film mirror has a minimum configuration, the hard coat layer preferably contains the triazine thiols according to the present invention in the range of 0.1 to 5% by mass.

  If the film thickness of the hard coat layer is too thick, there is a risk of cracking due to stress, and if the film thickness of the hard coat layer is too thin, the hardness cannot be maintained. Therefore, the film thickness is preferably in the range of 0.5 to 10 μm, more preferably in the range of 1 to 5 μm.

In particular, the hard coat layer used in the present invention preferably has weather resistance, scratch resistance, and antifouling properties. Regarding scratch resistance, it is preferable that the pencil hardness of the hard coat layer surface is H or more and less than 6H and 30 or less scratches in a steel wool test with a load of 500 g / cm ² . Regarding the antifouling property, it is preferable that the falling angle of the hard coat layer is larger than 0 ° and not more than 30 ° because water droplets are easily dropped and the antifouling property is excellent.

The pencil hardness is evaluated based on the pencil hardness test JIS-K5400. In the steel wool test, steel wool (# 0000) was attached as a wear material to a reciprocating abrasion tester (HEIDON-14DR manufactured by Shinto Kagaku Co., Ltd.), and each water-repellent / antifouling article was subjected to a load of 500 g / cm ² . In this test, the surface is reciprocated 10 times at a speed of 10 mm / sec to evaluate the number of scratches. The sliding angle was measured by attaching a sliding method kit DM-SA01 to a contact angle meter DM501 (Kyowa Interface Chemistry), dropping 50 μl of water, tilting the support from a horizontal state at a speed of 0.5 ° / second, The angle at which the rolls down is measured as the fall angle. A smaller rolling angle is preferable because water droplets can be easily dropped and have excellent antifouling properties.

(9-1) Polymer having a metalloxane skeleton This hard coat layer is preferably a layer containing at least a polymer-derived inorganic oxide or inorganic nitride having a metalloxane skeleton.

  The metalloxane skeleton in the present invention is a skeleton having a bond between a metal atom and an oxygen atom, that is, a MO bond, and a polymer having a metalloxane skeleton has a repeating main chain skeleton of this MO bond. A sol-gel method is preferable as a method for polymerizing the polymer compound. Examples of the polymetalloxane include polysiloxane, polytitanoxane, polyaluminoxane, polyzircoxane and the like.

  Examples of the polymer material having a metalloxane skeleton include polymethoxane such as silicon, titanium, zirconium, and aluminum, or polysilazane, perhydropolysilazane, alkoxysilane, alkylalkoxysilane, and polysiloxane. Preferably, it is a polymer having a metalloxane skeleton containing at least one element selected from silicon, aluminum, zirconium and titanium.

The binder having a metalloxane skeleton according to the present invention is preferably a polysiloxane, a polytitanoxane, a polyaluminoxane, or a polyzirconoxane composed of a polymetalloxane formed from a metal alkoxide. Metal alkoxide is Si (O
_{C 2 H 5) 4, Al} (OC 2 H 5) 4, Ti (OCH 3) 4, Ti (OC 2 H 5) 4, Ti (iso-OC 3 H 7) 4, Ti (OC 4 H 9) _{4, Zr (OC 2 H 5} ) 4, Zr (iso-OC 3 H 7) 4, Zr single metal alkoxides such as _{(OC 4 H} 9) 4 and the like.

  Among the above, polysiloxane is preferable, and polysiloxane represented by the following general formula (2) is particularly preferable. It is preferable to form the outermost layer by applying and drying a material containing these metalloxane skeletons. The outermost layer is preferably formed by a thermosetting reaction using a sol-gel method.

一般式（２）中、Ｒ^１１、Ｒ^１２は同一であっても異なっていてもよく、水素もしくはアルキル基又はアリール基等の有機基を表す。ｐは繰り返し単位を表す。

In general formula (2), R ¹¹ and R ¹² may be the same or different and each represents hydrogen, an organic group such as an alkyl group or an aryl group. p represents a repeating unit.

  Moreover, as polysiloxane, you may use any of the following, for example. Tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltoxiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycyl Sidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyl Partial hydrolysates of silane compounds having hydrolyzable silyl groups such as methyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane , It can be used such as those obtained by adding the silane compound having a radical polymerizable organo silica sol, or organosilica sol fine particles of silicic anhydride was stably dispersed in an organic solvent. However, the present invention is not limited to this.

  As the binder, it is preferable to apply a method in which an inorganic oxide is formed by a thermosetting reaction using a sol-gel method.

The sol-gel method is a method of forming an inorganic oxide from an organic metal compound that is a precursor of an inorganic oxide. In other words, a metal alkoxide, which is a kind of organometallic compound, is used as a starting material, and after the solution is hydrolyzed and polycondensed to form a sol, the reaction is further gelled by moisture in the air, etc. Things are obtained. For example, in the process of forming a silica glass film, when tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ), which is a metal alkoxide of silicon, is used, tetraethoxysilane is dissolved in a solvent such as alcohol, and a catalyst such as an acid is used. By adding a small amount of water and mixing well, a liquid polysiloxane sol is formed according to the following reaction formula.

Hydrolysis reaction Si (OC ₂ H ₅ ) ₄ + 4H ₂ O → Si (OH) ₄ + 4C ₂ H ₅ OH
Dehydration condensation reaction nSi (OH) ₄ → [SiO ₂ ] n + 2nH ₂ O
When a polysiloxane sol is applied to a resin substrate and dried, the volume of the sol shrinks with the evaporation of water and ethyl alcohol (C ₂ H ₅ OH) generated by the solvent and reaction. Residual OH groups at the ends of the polymer undergo a dehydration condensation reaction and are bonded, and the coating film becomes a gel (solidified body). Furthermore, when the obtained gel film is baked to strengthen the bond between the polysiloxane particles, a strong gel film can be obtained.

  In the sol-gel method, the above-described organometallic compound may be used for the reaction as it is, but it is preferably diluted with a solvent for easy control of the reaction. The dilution solvent may be any solvent that can dissolve the organometallic compound and can be uniformly mixed with water. Preferred examples of such a solvent for dilution include aliphatic lower alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, ethylene glycol, propylene glycol, and mixtures thereof. Further, a mixed solvent of butanol, cellosolve, and butyl cellosolve, or a mixed solvent of xylol, cellosolve acetate, methyl isobutyl ketone, and cyclohexane may be used.

  Further, as a preferable method for forming a hard coat layer, there is a method in which polysilazane is coated and formed, and is cured by heating at a temperature of about 50 to 200 ° C. to obtain a cured film. When the hard coat precursor contains polysilazane, for example, after applying a solution to which a catalyst is added if necessary in an organic solvent containing polysilazane represented by the following general formula (3), the solvent is evaporated. Thereby removing a polysilazane layer having a layer thickness in the range of 0.05 to 3.0 μm on the film mirror F. Then, a glass-like transparent hard coat film is formed on the film mirror F by locally heating the polysilazane layer in the atmosphere containing water vapor in the presence of oxygen, active oxygen, or in some cases nitrogen. It is preferable to adopt the method to do.

General formula (3)
-(SiR ¹ R ² -NR ³ ) _n-
In general formula (3), R ¹ , R ² , and R ³ are the same or different and independently of each other, hydrogen, or an optionally substituted alkyl group, aryl group, vinyl group, or (trialkoxysilyl) ) From an alkyl group, preferably hydrogen, methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, tert-butyl, phenyl, vinyl or 3- (triethoxysilyl) propyl, 3- (trimethoxysilylpropyl) Represents a group selected from the group consisting of In this case, n is an integer, and n is determined so that the polysilazane has a number average molecular weight in the range of 150 to 150,000 g / mol.

  As catalysts, preferably basic catalysts, in particular N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine or N-heterocyclic compounds are used. . The catalyst concentration is usually in the range of 0.1 to 10 mol%, preferably in the range of 0.5 to 7 mol%, based on polysilazane.

In one preferred embodiment, a solution containing perhydropolysilazane in which all of R ¹ , R ² and R ^{3 in} the general formula (3) are hydrogen atoms is used.

  In another preferred embodiment, the hard coat layer in the invention contains at least one polysilazane represented by the following general formula (4).

General formula (4)
_{^{- (SiR 1 R 2 -NR 3}} ) n - (SiR 4 R 5 -NR 6) p -
In general formula (4), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are independently of each other hydrogen, optionally substituted alkyl group, aryl group, vinyl group or ( Represents a trialkoxysilyl) alkyl group; In this case, n and p are integers, and in particular, n is determined so that polysilazane has a number average molecular weight in the range of 150 to 150,000 g / mol.

Particularly preferred are compounds in which R ¹ , R ³ and R ⁶ represent hydrogen and R ² , R ⁴ and R ⁵ represent methyl. A compound in which R ¹ , R ³ and R ⁶ represent hydrogen, R ² and R ⁴ represent methyl, and R ⁵ represents vinyl. Further, R ¹ , R ³ , R ⁴ and R ⁶ represent hydrogen, and R ² and R ⁵ represent methyl.

  Furthermore, in another preferable aspect, the hard coat layer in the present invention contains at least one polysilazane represented by the following general formula (5).

General formula (5)
_{^{- (SiR 1 R 2 -NR 3}} ) n - (SiR 4 R 5 -NR 6) p - (SiR 7 R 8 -NR 9) q -
In general formula (5), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are independently of one another hydrogen or optionally substituted alkyl. Represents a group, an aryl group, a vinyl group or a (trialkoxysilyl) alkyl group. In this case, n, p and q are integers, and in particular, n is determined so that the polysilazane has a number average molecular weight in the range of 150 to 150,000 g / mol.

Particularly preferred are R ¹ , R ³ and R ⁶ represent hydrogen and R ² , R ⁴ , R ⁵ and R ⁸ represent methyl, R ⁹ represents (triethoxysilyl) propyl and R ⁷ Is a compound in which represents alkyl or hydrogen.

  The ratio of polysilazane in the solvent is generally in the range of 1 to 80% by mass of polysilazane, preferably in the range of 5 to 50% by mass, particularly preferably in the range of 10 to 40% by mass.

  As the solvent, water and a reactive group (for example, a hydroxy group or an amine group) are not included, and an organic system that is inert to polysilazane and preferably an aprotic solvent is preferable. This includes, for example, aliphatic or aromatic hydrocarbons, halogen hydrocarbons, esters such as ethyl acetate or butyl acetate, ketones such as acetone or methyl ethyl ketone, ethers such as tetrahydrofuran or dibutyl ether, and mono- and polyalkylene glycol dialkyl ethers. (Diglymes) or a mixture of these solvents.

  Conventionally known coating methods such as a gravure coating method, a reverse coating method, and a die coating method can be used as the method for forming the hard coat.

  The contact angle of water on the surface of the hard coat layer is preferably in the range of 80 to 170 °. Preferably it is the range of 90-150 degrees. Moreover, it is preferable that the dynamic friction coefficient of the surface of a hard-coat layer is the range of 0.10-0.35.

  For example, the hard coat layer may contain a fluorine compound, a silicon compound, fluorine or silicon so that the contact angle of water on the surface of the hard coat layer is in the range of 80 to 170 °. More specifically, the surface energy is lowered by vapor deposition using a mixed gas of a fluorine compound and a silicon compound, or a compound containing fluorine and silicon, and the water contact angle of the hard coat layer is in the range of 80 to 170 °. can do.

  The hard coat layer preferably has a dynamic friction coefficient in the range of 0.10 to 0.35, more preferably in the range of 0.15 to 0.30, in order to improve the scratch resistance.

  By using a material having a metalloxane skeleton for the hard coat layer, the dynamic friction coefficient between the film surfaces can be in the range of 0.10 to 0.35.

(9-2) Ultraviolet absorber It is also preferable that the hard coat layer contains an ultraviolet absorber.

  Examples of the organic ultraviolet absorber include benzophenone-based, benzotriazole-based, phenyl salicylate-based, triazine-based, etc. mentioned in the above-mentioned acrylic resin layer.

  Examples of the inorganic ultraviolet absorber include metal oxide particles such as titanium oxide, zinc oxide, cerium oxide, and iron oxide.

  In particular, the hard coat layer preferably contains an ultraviolet absorber having an absorption maximum wavelength in the range of 250 to 300 nm. The hard coat layer containing such an ultraviolet absorber suppresses the deterioration of the interface with the intermediate layer, and can maintain the adhesion between the hard coat layer and the intermediate layer over a long period of time. Can be improved.

(9-3)
The hard coat layer according to the present invention preferably contains fine particles from the viewpoint of improving scratch resistance and slipperiness. The fine particles are not particularly limited, but are preferably inorganic fine particles composed of an inorganic oxide. As the inorganic oxide fine particles, the metal constituting the metal oxide is Li, Na, Mg, Al, Si. , K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Rb, Sr, Y, Nb, Zr, Mo, Ag, Cd, In, Sn, Sb, Cs, Ba La, Ta, Hf, W, Ir, Tl, Pb, Bi, etc., specifically, silicon oxide, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, hafnium oxide, niobium oxide, oxidation Examples include tantalum, magnesium oxide, calcium oxide, strontium oxide, barium oxide, indium oxide, tin oxide, and lead oxide. In the present invention, the inorganic oxide fine particles are silica. Alumina, titanium oxide, is preferably at least one of the transparent inorganic oxide fine particles selected from zinc oxide and zirconium oxide. The fine particles used in the present invention preferably have high transparency.

  In addition, the average particle diameter of the fine particles is preferably in the range of 10 to 180 nm from the viewpoint that the root mean square roughness Rq of the surface can be controlled in the range of 5 to 50 nm, and more preferably 10 to 100 nm. Range.

  If the average particle diameter is 10 nm or more, the root mean square roughness Rq can be 5 nm or more, and sufficient surface roughness can be ensured. Moreover, if an average particle diameter is 180 nm or less, the root mean square roughness Rq can be 50 nm or less, and the transparency of a film is not impaired.

  Moreover, in the hard-coat layer which concerns on this invention, it is preferable that it is the range of 30-90 mass% as a ratio of microparticles when the binder which has the said metalloxane skeleton is 100 mass%.

(9-4) Formation of hard coat layer By applying the above-mentioned resin material on the intermediate layer provided on the resin base material and curing it by heating, the dehydration condensation reaction is promoted and cured / crosslinked. A hard coat layer is formed.

  As a method of forming a coating film to be the hard coat layer, it can be formed by a coating method using a wire bar coating, spin coating, dip coating, or the like. The film can also be formed by a continuous coating apparatus such as a die coater, a gravure coater, or a comma coater.

[10] Gas Barrier Layer In the film mirror of the present invention, a gas barrier layer is preferably formed if necessary, and is preferably formed as the layer 11 in FIG.

  The gas barrier layer is preferably provided on the light incident side of the silver reflective layer.

  The gas barrier layer is intended to prevent the deterioration of humidity, especially the deterioration of the resin base material and each component layer supported by the resin base material due to high humidity, but with special functions and applications. As long as it has a function of preventing deterioration, a gas barrier layer of various modes can be provided.

As the moisture resistance of the gas barrier layer, the water vapor permeability at 40 ° C. and 90% RH is preferably 1 g / m ² · day or less, more preferably 0.5 g / m ² · day or less, still more preferably It is 0.2 g / m ² · day or less.

In addition, the oxygen permeability of the gas barrier layer is preferably 0.6 ml / m ² / day / atm or less under the conditions of a measurement temperature of 23 ° C. and a humidity of 90% RH.

  Examples of the method for forming the gas barrier layer include a method of forming an inorganic oxide or an inorganic nitride by a method such as vacuum deposition, sputtering, ion beam assist, chemical vapor deposition, etc., but inorganic oxidation by a sol-gel method. A method of forming an inorganic oxide film by applying a heat treatment and / or ultraviolet irradiation treatment to the coating film after applying a precursor of the product (polysilazane or the like) is preferably used.

  Regarding the details of the precursor of the inorganic oxide and the sol-gel method, paragraphs (0049) to (0072) of JP2012-047661A, the precursor of the inorganic oxide and the sol-gel method, and paragraph For (0073) to (0085), it is preferable to employ the method described for the polysilazane method.

[11] Adhesive layer The adhesive layer is a constituent layer for adhering and fixing the film mirror to the metal substrate.

  The adhesive layer is not particularly limited as long as it can adhere a film mirror to a metal 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, a polyester resin, a urethane resin, a polyvinyl acetate resin, an acrylic resin, a nitrile rubber, or the like may be used.

  The laminating method for providing the adhesive layer on the back surface of the resin substrate 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, the drying speed, and the like.

  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. An adhesive can be suitably used.

  Note that the adhesive layer is covered with the release sheet until the film mirror is bonded to the metal substrate, so that the adhesive force of the adhesive layer is maintained.

  In the adhesive layer, the aforementioned corrosion inhibitors, 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 a compound having an indazole ring, a copper chelate compound, a compound having a mercapto group, a thiourea, a naphthalene-based compound, or a mixture thereof.

[12] Release layer The film mirror of the present invention may have a release layer on the side opposite to the light incident side of the adhesive layer. For example, when a film mirror is shipped, it is shipped with the release layer attached to the adhesive layer, the film mirror having the adhesive layer is peeled off from the release layer, and is bonded to another substrate to form a solar reflective mirror. be able to.

  The release layer may be any layer that can impart protection to the silver reflective layer, for example, an acrylic film or sheet, a polycarbonate film or sheet, a polyarylate film or sheet, a polyethylene naphthalate film or sheet, a polyethylene terephthalate film or Plastic film or sheet such as sheet, fluorine film, or resin film or sheet kneaded with titanium oxide, silica, aluminum powder, copper powder, etc., coating the resin kneaded with these, metal deposition such as aluminum, etc. A resin film or sheet subjected to the above surface treatment is used.

  Although there is no restriction | limiting in particular in the thickness of a peeling layer, It is preferable that it is the range of 12-250 micrometers normally.

  In addition, it may be bonded after providing a recess or projection before bonding these release layers to the film mirror, or may be molded to have a recess or projection after bonding, You may simultaneously shape | mold so that it may have a recessed part and a convex part.

[13] Reflector for solar power generation A reflective device for solar power generation includes a film mirror and a self-supporting support base material, and the reflector is formed by bonding the film mirror to the support base material via an adhesive layer. It is.

  In addition, the "self-supporting property" referred to here is a state in which the supporting base material supports the edge portion of the film mirror in a state of being cut to a size used as a supporting base material for the solar power generation reflection device, This means that the film mirror has rigidity enough to support the film mirror. The support base material of the solar power generation reflecting device has self-supporting properties, so that it is easy to handle when installing the solar power generation reflecting device, and the holding member for holding the solar power generation reflecting device has a simple configuration. Therefore, it is possible to reduce the weight of the reflection device itself, and it is possible to suppress power consumption during solar tracking.

  For example, as shown in FIG. 2, the solar power generation reflection device R includes a film mirror F and a metal substrate 1 as a support member. Specifically, the reflective layer R for solar power generation is formed by bonding the adhesive layer 2 of the film mirror F to the metal substrate 1.

(13-1) Metal base material A metal base material is a support member for supporting the stuck film mirror and maintaining the reflective surface of a film mirror suitably.

  As a metal substrate of the solar power generation reflector, for example, a metal material such as a steel plate, a copper plate, an aluminum plate, an aluminum-plated steel plate, an aluminum-based alloy-plated steel plate, a copper-plated steel plate, a tin-plated steel plate, a chrome-plated steel plate, or a stainless steel plate. Can be used. In the present invention, it is particularly preferable to use a plated steel plate, a stainless steel plate, an aluminum plate, or the like having good corrosion resistance.

  The thickness of these metal substrates is preferably about 0.05 mm to 3 mm from the viewpoints of handleability, thermal conductivity, heat capacity, and the like.

(13-2) Holding member The solar power generation reflective device includes a holding member that holds a solar reflective mirror. The holding member preferably holds the film mirror for reflecting sunlight in a state where the sun can be tracked. Although there is no restriction | limiting in particular as a form of a holding member, For example, the form which hold | maintains several places with a rod-shaped holding member is preferable so that the film mirror for sunlight reflection can hold | maintain a desired shape. The holding member has a configuration for holding the sunlight reflecting mirror in a state in which the sun can be tracked. However, when the sun is tracked, it may be driven manually, or a separate driving device is provided to automatically track the sun. It is good also as a structure.

  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, "part by mass" or "mass%" is represented.

[Production method of film mirror]
The film mirrors of the present invention and comparative examples for verifying corrosion (discoloration), light resistance and adhesion of the silver reflective layer were prepared by the following method.

[Film Mirror 1; Comparative Example]
A biaxially stretched polyester film (polyethylene terephthalate film, thickness 25 μm) was used as the resin substrate 3. On one side of the polyethylene terephthalate film, a polyester resin (Polyester SP-181, manufactured by Nippon Synthetic Chemical), a melamine resin (manufactured by Super Becamine J-820 DIC), a TDI-based isocyanate (2,4-tolylene diisocyanate), and an HDMI system A resin mixed with isocyanate (1,6-hexamethylene diisocyanate) in a resin solid content ratio of 20: 1: 1: 2 in toluene to a solid content concentration of 10% by mass was coated by a gravure coating method. Then, an anchor layer 4 having a thickness of 0.1 μm was formed, and a silver reflective layer having a thickness of 100 nm was formed on the anchor layer 4 as a silver reflective layer 5 by a vacuum deposition method. Further, a resin in which a polyester resin and a TDI (tolylene diisocyanate) isocyanate are mixed at a resin solid content ratio of 10: 2 is coated on the silver reflective layer 5 by a gravure coating method to obtain a thickness of 3.0 μm. The resin coat layer 6 was formed.

  Next, on the resin coat layer 6, an adhesive layer 7, an acrylic film containing an ultraviolet absorber as the acrylic resin layer 8, Sumipex Technoloy S001G 75 μm (manufactured by Sumitomo Chemical Co., Ltd.) is laminated at a lamination temperature of 60 by a dry lamination process. Bonding was performed at ° C.

  Prior to the dry lamination process of the acrylic resin layer, an intermediate layer coating solution in which 5% by mass of PVA-403 (manufactured by Kuraray Co., Ltd.) was dissolved in water was applied on the acrylic resin layer 8 at 80 ° C. for 2 minutes. The intermediate layer 9 was formed by drying. The dry film thickness of the intermediate layer 8 was 0.5 μm.

  On the intermediate layer 9, using a 3% perhydropolysilazane liquid (NL120 manufactured by AZ Electric Materials Co.) in dibutyl ether, bar coating was performed so that the thickness after drying was 500 nm, followed by natural drying for 3 minutes. Thereafter, the hard coat layer 10 was formed by annealing in an oven at 90 ° C. for 30 minutes.

  Next, one side of a 25 μm thick polyester separate film as a release layer 12 was prepared by adding 1 part of a platinum catalyst to 100 parts of an addition reaction type silicone pressure-sensitive adhesive having a weight average molecular weight of 500,000 to form a 35 mass% toluene solution. After coating at 130 ° C. for 5 minutes to form a silicone adhesive layer 2 (Si system) having a thickness of 25 μm, it is laminated on the side opposite to the anchor layer and the silver reflective layer of the polyethylene terephthalate film, A film mirror of Comparative Example 1 was obtained.

[Film mirrors 2 to 5; comparative example]
In the production of the film mirror 1, comparative film mirrors 2 to 5 were produced in the same manner except that the compounds shown in Table 1 were contained in the anchor layer 4 and the resin coat layer 6 in the amounts described.

ＴＭＰＴ ：トリメチロールプロパントリス（β−チオプロピオネート） The compounds used and the abbreviations in the table are as follows.
T-234: Tinuvin 234, manufactured by BASF Japan K.K. T-1557: Tinuvin 1577, manufactured by BASF Japan K.K.

TMPT: trimethylolpropane tris (β-thiopropionate)

[Film mirrors 6 to 13; the present invention]
In the production of the film mirror 1, the film mirrors 6 to 13 of the present invention were produced in the same manner except that the compounds described in Table 1 were contained in the anchor layer 4 and the resin coat layer 6 in the amounts described.

  The structure of the compound used and the abbreviations in the table are as follows.

≪フィルムミラーの評価≫
上記のように作製したフィルムミラー１〜１３について、下記の方法に従って、銀反射層の腐食耐性、紫外線照射後の反射率と、銀反射層と樹脂コート層間、又は銀反射層とアンカー層間での密着性について評価した。 TS-1: 1,3,5-triazine-2,4,6-trithiol TS-2: 6-dibutylamino-1,3,5-triazine-2,4-dithiol TS-3: 6-anilino-1 , 3,5-Triazine-2,4-dithiol TS-4:

≪Evaluation of film mirror≫
About the film mirrors 1-13 produced as described above, according to the following method, the corrosion resistance of the silver reflective layer, the reflectance after ultraviolet irradiation, and between the silver reflective layer and the resin coat layer, or between the silver reflective layer and the anchor layer The adhesion was evaluated.

<Silver corrosion resistance>
The produced film mirror was cut into 5 cm □ with scissors, put in a sealed vial tube together with sulfur powder, and heated in a 110 ° C. oven to visually confirm damage (corrosion) of the silver reflecting surface. The ratio of the area changed to black was measured. The smaller the black area, the better the corrosion resistance.

  According to the following criteria, the ratio of the area was evaluated in five stages of 1 to 5. The larger the number, the better, and a rating of 3 or higher is practical.

5: Black discolored area area ratio is less than 5% 4: Black discolored area area ratio is 5% or more and less than 10% 3: Black discolored area area ratio is 10% or more and less than 15% 2: Black discolored area area ratio is 15% or more Less than 20% 1: Black discoloration area ratio is 20% or more <Light resistance>
Xenon lamp irradiation (using Suga Test Machine SX75, radiation intensity 180 W / m ² × 1000 hours) was performed on the sunlight incident surface side of the produced film mirror in an environment of 23 ° C. and 55% RH.

  After the xenon lamp irradiation, the regular reflectance was measured at 5 degrees by the following method.

  Using a spectrophotometer U-4100 (solid sample measurement system) manufactured by Hitachi High-Technologies Corporation, a relative reflectance measurement with respect to a reference sample having an incident angle of 5 degrees was performed. The wavelength range was measured at 250 to 2500 nm, and it was confirmed whether there was any wavelength range in which the reflectance dropped partially. The reflectance in the visible light region (400 to 800 nm) was averaged, and this was defined as a regular reflectance of 5 degrees.

  The 5-degree regular reflectance of the film mirror before the light resistance test was measured, and the smaller the fluctuation range, the better the light resistance.

  According to the following criteria, the change in reflectance was evaluated in five stages of 1 to 5. The larger the number, the better, and a rating of 3 or higher is practical.

5: The fluctuation range of the reflectance is less than 3%.
4: Reflectance fluctuation range of 3% to less than 5% 3: Reflectance fluctuation range of 5% to less than 8% 2: Reflectance fluctuation range of 8% to less than 10% 1: Reflectance fluctuation range 10% or more <Adhesion>
The film mirror produced above is irradiated with a metal halide lamp for 500 hours, stored in an environment of 60 ° C. and 90% RH for 200 hours, and then adhered to the silver reflective layer and other constituent layers using a cross-cut tape peeling method. Sex was evaluated.

  The method for measuring the adhesion of the film is based on JIS K 5600, in which the sample is scratched in a cross shape with a cutter, and a 100 square cut is made. After applying the cellophane tape to the cut portion, it was pulled in the 45 ° direction, and the number of squares where the layer adjacent to the silver reflective layer was not peeled was measured. Adhesion was evaluated according to the following criteria in five stages of 1 to 5. The larger the number, the better, and a rating of 3 or higher is practical.

5: The number of cells not peeled is 95 or more 4: The number of cells not peeled is 85 or more and less than 95 3: The number of cells not peeled is 75 or more and less than 85 2: The number of cells not peeled is 65 or more and less than 75 1: Table 1 shows the configuration of the film mirrors 1 to 13 and the evaluation results.

表１から、本発明に係るトリアジンチオール類を、銀反射層に隣接するアンカー層、又は樹脂コート層、若しくはその両層に添加したフィルムミラー６〜１３は、腐食耐性、耐光性、及び密着性が、比較例に対して優れていることが明らかである。

From Table 1, the film mirrors 6 to 13 in which the triazine thiols according to the present invention are added to the anchor layer adjacent to the silver reflecting layer, the resin coating layer, or both of them are corrosion resistant, light resistant, and adhesive. However, it is clear that it is superior to the comparative example.

  Therefore, if the film mirror for solar power generation according to the present invention is used, even in an environment where the amount of ultraviolet irradiation is very large such as a desert, the reflectance of the silver reflecting layer decreases due to corrosion or discoloration, and the silver reflecting layer and other constituent layers It is possible to provide a solar power generation reflecting device capable of solving the problem of the present invention, i.e., peeling-off.

F Film mirror for solar power generation 1 Metal base material 2 Adhesive layer 3 Resin base material 4 Anchor layer 5 Metal reflective layer 6 Resin coat layer 7 Adhesive layer 8 Acrylic resin layer (ultraviolet spherical layer)
9 Intermediate layer 10 Hard coat layer 11 Gas barrier layer 12 Release layer R Reflector for solar power generation

Claims (5)

A mirror for solar power generation in which a metal reflective layer is provided on a resin base material, wherein at least one layer adjacent to the metal reflective layer contains a triazine thiol represented by the following general formula (1) Mirror for solar thermal power generation.

(Wherein R ₁ , R ₂ and R ₃ each represent a hydrogen atom or a substituent, and any one of the substituents represented by R ₁ , R ₂ and R ₃ has a thiol group or a thiol group) Represents a group.) _2. The solar power generation mirror according to claim ₁ , wherein any one of the substituents represented by R ₁ , R _2, and R ₃ is a thiol group. The solar power generation mirror according to claim ₁ , wherein two or more of the substituents represented by R ₁ , R _2, and R ₃ are thiol groups.   4. The solar power generation mirror has a hard coat layer, and the hard coat layer contains an inorganic oxide or inorganic nitride derived from a polymer having a metalloxane skeleton. The solar power generation mirror according to claim 1.   The solar power generation reflecting device, wherein the solar power generation mirror according to any one of claims 1 to 4 is bonded to a support base material via an adhesive layer.

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