JP2010089452A - Laminated body and heat ray insulating laminated glass using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated body prevented from the deterioration due to discoloration even when a tungsten compound is contained. <P>SOLUTION: The laminated body includes a heat ray insulating layer 110 containing the tungsten compound, an ultraviolet ray absorbing layer 120 containing an ultraviolet ray absorbing agent and a radical insulating layer 130 containing an organic resin, wherein at least one layer of the radical insulation layer 120 is arranged between the heat ray insulating layer 110 and the ultraviolet ray absorbing layer 130. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a laminate including at least a heat ray shielding layer, which is preferably used for laminated glass having excellent impact resistance, penetration resistance, crime prevention property, and the like.

  Generally, laminated glass having a structure in which a transparent adhesive layer (intermediate film) is sandwiched between glass plates is used for glass used for automobiles, particularly windshields. The transparent adhesive layer is formed of, for example, a PVB film, an EVA film, or the like, and the presence of the transparent adhesive layer improves the penetration resistance of the laminated glass. In addition, broken glass fragments remain attached to the transparent adhesive layer in response to an impact from the outside, thus preventing scattering. For this reason, for example, even if a laminated glass of an automobile is broken for the purpose of theft or intrusion, the window cannot be opened freely, so that it is useful as a security glass.

  On the other hand, for example, automobile door glass and fitted glass are generally less likely to be destroyed in an accident, and therefore do not require the penetration resistance or the like of the windshield, so a slightly reinforced low-strength glass. A board is used. However, when only such a single glass plate is used, there are the following drawbacks. That is, (1) Inferior to laminated glass in terms of impact resistance, penetration resistance, etc. (2) If broken for the purpose of theft or intrusion, it breaks into many pieces and the window is opened freely And so on. For this reason, it is also considered to use glass having characteristics such as laminated glass for the door glass and the fitted glass. As glass suitable for such applications, film tempered glass in which a glass plate and a plastic film are bonded via a transparent adhesive layer is described in Patent Documents 1 and 2, for example.

  The transparent adhesive layer that bonds the two glass plates of such laminated glass or the glass plate of the film tempered glass and the plastic film is required to have excellent adhesion and penetration resistance as described above. Yes.

  The laminated glass generally has excellent adhesion and penetration resistance and is excellent in safety, but does not take into account heat ray blocking properties. As glass having a heat ray blocking function, for example, heat ray cut glass is commercially available. This heat ray cut glass is obtained by applying a metal / metal oxide multi-layer coating on the surface of a glass plate by vapor deposition of metal or the like and sputtering processing for the purpose of directly blocking sunlight. This multilayer coating is vulnerable to external scratches and has poor chemical resistance. Such glass is generally used as laminated glass by laminating an intermediate film made of EVA or the like.

  Moreover, since the said heat ray cut glass uses a metal, there exists a problem that transparency falls, obstructs permeation | transmission of electromagnetic waves, and exerts a bad influence on communication functions, such as a mobile telephone and a car navigation system. Furthermore, since the above-mentioned heat ray cut glass uses a multilayer coating, there is a problem that it becomes expensive.

  Thus, a laminated glass in which a heat ray shielding agent is dispersed in an intermediate film has been proposed. For example, Patent Document 3 proposes a laminated glass using an intermediate film in which tungsten oxide is dispersed as a heat ray shielding agent in a soft resin.

JP 2002-046217 A JP 2002-068785 A WO2005 / 087680

  In the laminated glass having the intermediate film described in Patent Document 3, the use of tungsten oxide ensures both the heat ray cutting function and transparency. However, a laminated glass containing such a tungsten compound as a heat ray shielding agent has a problem that when used for a long period of time, the color changes to blue or the like, and the transmittance decreases.

  Then, an object of this invention is to provide the laminated body by which deterioration by discoloration was suppressed even if it contained the tungsten compound.

  Tungsten compounds are excellent in the near-infrared shielding effect, but a film using the tungsten compound may show a change in transmittance accompanying discoloration. This is considered to be because the film is exposed to sunlight for a long time, for example, outdoors. That is, it is considered that the tungsten compound is deteriorated by being irradiated with sunlight, particularly ultraviolet rays for a long time to produce pentavalent tungsten, and thereby, the color is changed to blue.

  Such deterioration of the tungsten compound can be suppressed by an ultraviolet absorber. However, when ultraviolet rays are irradiated for a longer time, the ultraviolet absorber itself is also deteriorated, and thus blue discoloration of a film containing a tungsten compound may not be sufficiently suppressed.

  As described above, not only the tungsten compound but also the ultraviolet absorber is deteriorated by ultraviolet rays, and the present inventors have conducted various studies in view of these problems. As a result, the film containing the tungsten compound and the ultraviolet absorber is irradiated with ultraviolet rays. It has been found that the deteriorated ultraviolet absorber generates radicals, and the radicals may deteriorate the tungsten compound. Therefore, the tungsten compound and the UV absorber are contained in separate layers, and further, radicals caused by UV degradation of the UV absorber between these layers are prevented from affecting the layer containing the tungsten compound. By disposing a layer for this purpose, it is possible to prevent discoloration due to deterioration of the tungsten compound.

That is, the present invention has a heat ray shielding layer containing a tungsten compound, an ultraviolet absorbing layer containing an ultraviolet absorber, and a radical blocking layer containing an organic resin,
The above-mentioned problem is solved by a laminate in which at least one radical blocking layer is disposed between the heat ray blocking layer and the ultraviolet absorbing layer.

  The laminated body of this invention can cut near infrared rays efficiently by including the heat ray shielding agent which consists of a tungsten compound. Moreover, the functional film can prevent deterioration of the tungsten compound by providing a layer containing an ultraviolet absorber separately from the heat ray shielding layer. Furthermore, between the heat ray shielding layer and the ultraviolet ray absorbing layer, by providing a radical shielding layer for preventing radicals generated by the ultraviolet absorber deteriorated by the irradiation of ultraviolet rays from affecting the heat ray shielding layer, Further, discoloration due to oxidative deterioration of the tungsten compound can be prevented in use over a long period of time. Therefore, the laminate of the present invention efficiently cuts heat rays (infrared rays), is highly suppressed from discoloration due to deterioration, and can maintain excellent transparency over a long period of time.

  A cross-sectional view of the laminate of the present invention is shown in FIG. The laminate of the present invention has a heat ray shielding layer 110 containing a tungsten compound and an ultraviolet absorbing layer 120 containing an ultraviolet absorber, and further includes a radical blocking layer containing an organic resin between these layers 110 and 120. 130.

(Radical blocking layer)
The radical blocking layer is a layer for preventing the radical formed by irradiation of ultraviolet rays by the ultraviolet absorbent contained in the ultraviolet absorbing layer from moving to the heat ray shielding layer.

  The radical blocking layer contains at least an organic resin. Preferred examples of the organic resin include fluororesins, silicone resins, olefin resins, acrylic resins, ethylene vinyl acetate copolymers, polyester resins, cellulose resins, and polycarbonate resins. Particularly preferred are fluororesin, ethylene vinyl acetate copolymer, and polyethylene terephthalate. According to these organic resins, the influence of radicals can be prevented to a high degree.

  Examples of fluororesins include polytetrafluoroethylene (PTFE), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), and polyvinylidene fluoride (PVDF). ), Polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene-ethylene copolymer (ETFE), fluoroethylene vinyl ether (FEVE) and ethylene chlorotrifluoroethylene copolymer (ECTFE), the following structure:

（ｎ＝１０〜１０００）
を有する重合体Ａを挙げることができる。これらの中で、上記重合体Ａ、フルオロエチレンビニルエーテル（ＦＥＶＥ）が好ましい。これらの（共）重合体は、さらに官能基（例、アルコキシシリル基、ヒドロキシル基、アミノ基、イミノ基、（メタ）アクリロイロキシ基、エポキシ基、カルボキシル基、スルホニル基、アクリレート型イソシアヌレート基、硫酸塩基）を有していても良い。市販されているフッ素樹脂の好ましい例としては、サイトップ（旭硝子（株）製）、ゼッフル（ダイキン化学（株）製）、オプツール（ダイキン化学（株）製）を挙げることができる。

(N = 10 to 1000)
The polymer A which has this can be mentioned. Among these, the polymer A and fluoroethylene vinyl ether (FEVE) are preferable. These (co) polymers further have functional groups (eg, alkoxysilyl groups, hydroxyl groups, amino groups, imino groups, (meth) acryloyloxy groups, epoxy groups, carboxyl groups, sulfonyl groups, acrylate type isocyanurate groups, sulfuric acid groups. Base). Preferred examples of commercially available fluororesins include CYTOP (Asahi Glass Co., Ltd.), Zeffle (Daikin Chemical Co., Ltd.), and OPTOOL (Daikin Chemical Co., Ltd.).

  Examples of silicone resins include straight silicone varnish and modified silicone varnish. Straight silicone varnish is usually produced by hydrolysis polymerization of phenyltrichlorosilane, diphenyldichlorosilane, methyltrichlorosilane, and dimethyldichlorosilane (when used, it is generally cured at 100 ° C. or higher after application). The modified silicone varnish is obtained by reacting a silicone varnish with a resin such as alkyd, polyester, acrylic, or epoxy. Preferable examples of commercially available silicone resins include silicone varnish KR series (manufactured by Shin-Etsu Chemical Co., Ltd.).

  Examples of the olefin resin include polyethylene, polypropylene, and chlorinated polyethylene.

  Examples of the acrylic resin include thermoplastic acrylic resins such as acrylonitrile ethylene propylene rubber styrene copolymer (AES) and acrylonitrile styrene acrylate (ASA), or thermosetting acrylic resins (self-curing type, polyisocyanate, amino resin, polyester or Crosslinking type by epoxy resin).

  The vinyl acetate content in the ethylene vinyl acetate copolymer is 23 to 38 parts by mass, particularly preferably 23 to 28 parts by mass with respect to 100 parts by mass of EVA. If the vinyl acetate content is less than 23 parts by mass, the transparency of the resin obtained when crosslinking and curing at a high temperature is not sufficient. Conversely, if it exceeds 38 parts by mass, the moldability may decrease. Moreover, it is preferable that the melt flow index (MFR) of EVA is 4.0-30.0 g / 10min, especially 8.0-18.0g / 10min.

  The radical blocking layer containing EVA as an organic resin preferably contains an organic peroxide as a crosslinking agent. The EVA-containing radical blocking layer may further contain various additives such as a crosslinking aid, an adhesion improver, and a plasticizer as necessary.

  Any organic peroxide may be used in combination as long as it decomposes at a temperature of 100 ° C. or higher and generates radicals. The organic peroxide is generally selected in consideration of the film formation temperature, the adjustment conditions of the composition, the curing (bonding) temperature, the heat resistance of the adherend, and the storage stability. In particular, the one having a decomposition temperature of 70 ° C. or more with a half-life of 10 hours is preferable.

  Examples of the organic peroxide include t-butyl peroxyisopropyl carbonate, t-butyl peroxy-2-ethylhexyl carbonate, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl. -2,5-di (t-butylperoxy) hexane-3-di-t-butyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) Hexane, dicumyl peroxide, α, α′-bis (t-butylperoxyisopropyl) benzene, n-butyl-4,4-bis (t-butylperoxy) valerate, 1,1-bis (t-butyl) Peroxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, t-butylpero Xylbenzoate, benzoyl peroxide, t-butyl peroxyacetate, methyl ethyl ketone peroxide, 2,5-dimethylhexyl-2,5-bisperoxybenzoate, butyl hydroperoxide, p-menthane hydroperoxide, p-chlorobenzoyl Peroxide, hydroxyheptyl peroxide, chlorohexanone peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, cumyl peroxy octoate, succinic peroxide, acetyl peroxide, m-toluoyl peroxide, t Mention may be made of -butyl peroxyisobutyleo and 2,4-dichlorobenzoyl peroxide.

  The content of the organic peroxide in the radical blocking layer is preferably 1 to 10 parts by mass, particularly 1 to 5 parts by mass with respect to 100 parts by mass of EVA.

  Examples of polyfunctional compounds (crosslinking aids) include esters obtained by esterifying a plurality of acrylic acid or methacrylic acid with glycerin, trimethylolpropane, pentaerythritol, and the like, and the aforementioned triallyl cyanurate and triallyl isocyanurate. it can.

  In order to further enhance the adhesive force of the EVA-containing radical blocking layer, a silane coupling agent can be added as an adhesion improver. Examples of silane coupling agents include γ-chloropropylmethoxysilane, vinylethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxy. Silane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β Mention may be made of-(aminoethyl) -γ-aminopropyltrimethoxysilane. These silane coupling agents may be used alone or in combination of two or more. Moreover, it is preferable that content of the said compound is 5 mass parts or less with respect to 100 mass parts of EVA.

  The plasticizer is not particularly limited, but polybasic acid esters and polyhydric alcohol esters are generally used. Examples thereof include dioctyl phthalate, dihexyl adipate, triethylene glycol-di-2-ethylbutyrate, butyl sebacate, tetraethylene glycol diheptanoate, and triethylene glycol dipelargonate. One type of plasticizer may be used, or two or more types may be used in combination. The content of the plasticizer is preferably in the range of 5 parts by mass or less with respect to 100 parts by mass of EVA.

  EVA-containing radical blocking layer improves or adjusts various physical properties of the film (optical properties such as mechanical strength, adhesiveness and transparency, heat resistance, light resistance, cross-linking speed, etc.), especially improvement of mechanical strength. For this reason, it is preferable that an acryloxy group-containing compound, a methacryloxy group-containing compound, and / or an epoxy group-containing compound are included.

  The acryloxy group-containing compound and methacryloxy group-containing compound to be used are generally acrylic acid or methacrylic acid derivatives, and examples thereof include acrylic acid or methacrylic acid esters and amides. Examples of ester residues include linear alkyl groups such as methyl, ethyl, dodecyl, stearyl, lauryl, cyclohexyl group, tetrahydrofurfuryl group, aminoethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group. Group, 3-chloro-2-hydroxypropyl group. In addition, polyhydric alcohols such as ethylene glycol, triethylene glycol, polypropylene glycol, polyethylene glycol, trimethylolpropane, and pentaerythritol, and esters of acrylic acid or methacrylic acid can also be used. Examples of amides include diacetone acrylamide.

Examples of epoxy-containing compounds include triglycidyl tris (2-hydroxyethyl) isocyanurate, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and phenol. (Ethyleneoxy) ₅ glycidyl ether, pt-butylphenyl glycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, glycidyl methacrylate, butyl glycidyl ether can be mentioned.

  Polyester resins used for the radical blocking layer include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), and polyethylene- 1,2-bis (phenoxy) ethane-4,4′-dicarboxylate and the like. Of these, PET is preferable.

  The radical blocking layer preferably further contains a hindered amine light stabilizer in addition to the organic resin described above. Thereby, the migration of radicals can be further prevented. The hindered amine light stabilizer supplements radical species harmful to the organic resin and prevents generation of new radicals.

  Low molecular weight hindered amine light stabilizers include decanedioic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester, 1,1-dimethylethyl hydroperoxide and Consists of 70% by weight of a reaction product of octane (molecular weight 737) and 30% by weight of polypropylene; bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1 -Dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate (molecular weight 685); bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl-1,2,2,6 6-pentamethyl-4-piperidyl sebacate mixture (molecular weight 509); bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate ( 481); tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate (molecular weight 791); tetrakis (1,2,2,6, 6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate (molecular weight 847); 2,2,6,6-tetramethyl-4-piperidyl-1,2,3,4-butane Mixture of tetracarboxylate and tridecyl-1,2,3,4-butanetetracarboxylate (molecular weight 900); 1,2,2,6,6-pentamethyl-4-piperidyl-1,2,3,4-butane Examples thereof include a mixture (molecular weight 900) of tetracarboxylate and tridecyl-1,2,3,4-butanetetracarboxylate.

  As the high molecular weight hindered amine light stabilizer, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2, 2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] (molecular weight 2,000-3,100); succinic acid Polymer of dimethyl and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol (molecular weight 3,100 to 4,000); N, N ′, N ″, N ″ ′-tetrakis- ( 4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10- Diamine (molecular weight 2,286) and above Mixture of polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol; dibutylamine, 1,3,5-triazine, N, N′-bis (2,2 , 6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate (molecular weight 2,600-3) 400), etc. The above-mentioned hindered amine light stabilizers may be used alone or in a combination of two or more.

  Among these, as hindered amine light stabilizers, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl-1,2,2,6,6-pentamethyl-4-piperidyl It is preferred to use sebacate, methyl-4-piperidyl sebacate, and bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate. Moreover, it is preferable to use a hindered amine light stabilizer having a melting point of 60 ° C. or higher.

  The content of the hindered amine light stabilizer is 0.1 to 5.0 parts by mass, more preferably 0.1 to 2.5 parts by mass with respect to 100 parts by mass of the organic resin. Thereby, the stabilization effect by the hindered amine light stabilizer is sufficiently obtained.

  As a method for producing the radical blocking layer, a known method can be used depending on the organic resin. For example, when fluorine resin, silicone resin, olefin resin, acrylic resin, polyester resin, or the like is used as the organic resin, a coating liquid in which the organic resin and, if necessary, a hindered amine light stabilizer are dispersed in an organic solvent is used. The radical blocking layer is obtained by applying and drying on a plastic film or the like.

  In addition, when an acrylic resin or the like is used as the organic resin, a polymerizable monomer or oligomer of the resin, and, if necessary, a hindered amine light stabilizer, a polymerization initiator (thermal polymerization initiator or photopolymerization initiator) Is applied to a plastic film or the like and cured by heating or light irradiation to obtain a radical blocking layer. Light irradiation may be performed using ultraviolet rays, X-rays, γ rays, electron beams, or the like.

  Thermal polymerization initiators include t-butyl hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, dimyristyl peroxydicarbonate, t-butyl peroxyacetate, t-butyl peroxy (2 -Ethyl hexanoate), organic peroxides such as cumyl peroxy octoate, and azo compounds such as azobisisobutyronitrile and azobiscyclohexanenitrile.

  As the photopolymerization initiator, any compound suitable for the properties of the resin can be used. For example, acetophenone such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1 Benzoin series such as benzyl dimethyl ketal, benzophenone, 4-phenylbenzophenone, benzophenone series such as hydroxybenzophenone, thioxanthone series such as isopropylthioxanthone, 2-4-diethylthioxanthone, and other special types include methylphenyl glyoxylate Etc. can be used. Particularly preferably, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1, Examples include benzophenone. These photopolymerization initiators may be optionally selected from one or more known photopolymerization accelerators such as benzoic acid type or tertiary amine type such as 4-dimethylaminobenzoic acid. It can be used by mixing at a ratio. Moreover, a photoinitiator can be used individually by 1 type or in mixture of 2 or more types. In particular, 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals, Irgacure 184) is preferable.

  In addition, when EVA is used as the organic resin, a composition containing EVA and, if necessary, an organic peroxide and a hindered amine light stabilizer, etc., is subjected to normal extrusion molding, calendar molding (calendering). The radical blocking layer can be obtained by molding with the above.

  The composition is preferably mixed by heating and kneading at a temperature of 40 to 90 ° C, particularly 60 to 80 ° C. Moreover, it is preferable that the heating temperature at the time of film formation is a temperature at which the organic peroxide does not react or hardly reacts. For example, it is preferable to set it as 40-90 degreeC, especially 50-80 degreeC.

  Alternatively, a layered product may be obtained by dissolving the above-mentioned composition containing EVA in an organic solvent, applying this solution onto an appropriate support with an appropriate coater, and drying to form a coating film. it can.

  When a polyester resin is used as the organic resin, the radical blocking layer can be obtained by pelletizing the polyester resin and, if necessary, a hindered amine light stabilizer, melt-extruding, and molding. Moreover, the commercially available polyester resin film etc. can also be used.

  In the laminate of the present invention, at least one radical blocking layer is used. The radical blocking layer may be used alone or in a laminate of two or more layers.

  The radical blocking layer is particularly preferably a radical blocking layer (A) containing an ethylene-vinyl acetate copolymer and a radical blocking layer (B) containing polyethylene terephthalate because the effects of radicals can be prevented to a high degree. These radical blocking layers (A) or (B) can be used alone as a radical blocking layer 130 as shown in FIG. Further, as shown in FIG. 2, a radical blocking layer (A) 230A containing an ethylene vinyl acetate copolymer and a radical blocking layer (B) 230B containing polyethylene terephthalate are interposed between the heat ray shielding layer 210 and the ultraviolet absorbing layer 220. Can also be used in a stacked manner.

  The thickness of the radical blocking layer is preferably 0.1 to 500 μm, particularly preferably 50 to 200 μm. Moreover, when using radical blocking layer (A) and (B), the thickness of a radical blocking layer (A) becomes like this. Preferably it is 10-1000 micrometers, Most preferably, it is 100-500 micrometers. The thickness of the radical blocking layer (B) is preferably 25 to 250 μm, particularly preferably 50 to 200 μm.

(UV absorbing layer)
The ultraviolet absorbing layer used in the laminate of the present invention contains an ultraviolet absorber in order to prevent the tungsten compound contained in the heat ray shielding layer from being deteriorated by irradiation with sunlight, particularly ultraviolet rays.

  Examples of the ultraviolet absorber used in the ultraviolet absorbing layer include benzophenone compounds, triazine compounds, and benzoate compounds. Among them, a benzophenone-based compound is preferable because the tungsten compound has a particularly high antioxidant effect and can prevent the laminate from being discolored to blue over a long period of time.

  As the benzophenone ultraviolet absorber, the following formula (I):

［但し、Ｒ¹が、水素原子又はヒドロキシル基を表し、Ｒ²が、水素原子又はヒドロキシル基を表し、Ｒ³が、水素原子、ヒドロキシル基、炭素原子数１〜１４個（特に１〜８個）のアルキル基又は炭素原子数１〜１４個（特に５〜８個）のアルコキシ基を表し、そしてＲ⁴が、水素原子、ヒドロキシル基、炭素原子数１〜１４個（特に１〜８個）のアルキル基又は炭素原子数１〜１４（特に５〜８個）のアルコキシ基を表す］で示される化合物が好ましく用いられる。

[However, R ¹ represents a hydrogen atom or a hydroxyl group, R ² represents a hydrogen atom or a hydroxyl group, R ³ represents a hydrogen atom, a hydroxyl group, 1 to 14 carbon atoms (particularly 1 to 8 carbon atoms). ) Alkyl group or an alkoxy group having 1 to 14 carbon atoms (especially 5 to 8 carbon atoms), and R ⁴ is a hydrogen atom, a hydroxyl group or 1 to 14 carbon atoms (especially 1 to 8 carbon atoms). Or an alkoxy group having 1 to 14 carbon atoms (especially 5 to 8 carbon atoms)] is preferably used.

R ¹ represents a hydroxyl group, R ² represents a hydrogen atom or a hydroxyl group, in particular a hydroxyl group, R ³ represents a hydrogen atom, a hydroxyl group or an alkoxy group, in particular a methoxy group or an octyloxy group, and R ⁴ preferably represents a hydrogen atom, a hydroxyl group, or an alkoxy group, particularly a methoxy group or an octyloxy group. In particular, it is preferable that R ¹ and R ² are both hydroxyl groups, and R ³ and R ⁴ are both alkoxy groups having 5 to 8 carbon atoms, particularly octyloxy groups.

  Preferred examples of the benzophenone ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-n-octylbenzophenone, 2 , 2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, and in particular, 2-hydroxy-4-n-octylbenzophenone, 2,2'- Dihydroxy-4,4′-dimethoxybenzophenone is preferred.

  In addition, the ultraviolet absorber mentioned above can also be used individually by 1 type, and can also use 2 or more types.

  The ultraviolet absorber further contains a binder resin in addition to the above-described ultraviolet absorber. As the binder resin, fluorine resin, silicone resin, olefin resin, acrylic resin, ethylene vinyl acetate copolymer (EVA), and polyvinyl butyral resin (PVB) are preferable, EVA and PVB are more preferable, and EVA is particularly preferable. Since these binder resins are the same as the organic resin in the radical blocking layer described above, detailed description thereof is omitted here.

  The content of the ultraviolet absorber in the ultraviolet absorbing layer is preferably 0.5 to 3 parts by mass, particularly 0.5 to 1 part by mass with respect to 100 parts by mass of the binder resin. Thus, even with a small amount of ultraviolet absorber, an excellent anti-discoloration effect can be exhibited.

  The vinyl acetate content in EVA used for the ultraviolet absorbing layer is 23 to 38 parts by mass, and particularly preferably 23 to 28 parts by mass with respect to 100 parts by mass of EVA. If the vinyl acetate content is less than 23 parts by mass, the transparency of the resin obtained when crosslinking and curing at a high temperature is not sufficient. Conversely, if it exceeds 38 parts by mass, the moldability is lowered and the ultraviolet absorber is reduced. There is a risk that it cannot be highly dispersed. Moreover, it is preferable that the melt flow index (MFR) of EVA is 4.0-30.0 g / 10min, especially 8.0-18.0g / 10min. Pre-crimping becomes easy.

  The EVA-containing ultraviolet absorbing layer contains an ultraviolet absorber and an organic peroxide in addition to the above EVA, and further includes a crosslinking aid, an adhesion improver, a plasticizer, an acryloxy group-containing compound, a methacryloxy group-containing compound, Various additives such as an epoxy group-containing compound and a silane coupling agent can be contained. Since these additives and the method for producing the ultraviolet absorbing layer are the same as those of the radical blocking layer described above, detailed description thereof is omitted here.

(Heat ray shielding layer)
The heat ray shielding layer used in the laminate of the present invention contains a tungsten compound as a heat ray shielding agent. As the tungsten compound, tungsten oxide and / or composite tungsten oxide is preferable because near infrared rays can be efficiently cut.

  Tungsten oxide is an oxide represented by the general formula WyOz (where W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999). In addition, the composite tungsten oxide is the same as the above tungsten oxide, except that the element M (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co , Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br , Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I). As a result, free electrons are generated in WyOz, including the case of z / y = 3.0, and free electron-derived absorption characteristics are expressed in the near infrared region, which is effective as a near infrared absorbing material near 1000 nm. . In the present invention, composite tungsten oxide is preferable.

In the tungsten oxide represented by the general formula WyOz (W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999), a preferable composition range of tungsten and oxygen is oxygen with respect to tungsten. When the infrared shielding material is described as WyOz, 2.2 ≦ z / y ≦ 2.999. If the value of z / y is 2.2 or more, it is possible to avoid the appearance of a crystal phase of WO ₂ which is not intended in the infrared shielding material and to obtain chemical stability as a material. Therefore, it can be applied as an effective infrared shielding material. On the other hand, if the value of z / y is 2.999 or less, a required amount of free electrons is generated and an efficient infrared shielding material can be obtained.

  From the viewpoint of stability, the composite tungsten oxide is generally MxWyOz (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, One or more elements selected from Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, W is tungsten, O is oxygen, (0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3) The alkali metal is a periodic table group 1 element excluding hydrogen, and the alkaline earth metal is a periodic table group 2 element. , Rare earth elements are Sc, Y and lanthanoid elements, especially red From the viewpoint of improving optical characteristics and weather resistance as a line shielding material, the M element is one or more of Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn. Is preferred.

  The composite tungsten oxide is preferably treated with a silane coupling agent. Excellent dispersibility is obtained, and an excellent infrared cut function and transparency are obtained.

  If the value of x / y indicating the added amount of the element M is larger than 0.001, a sufficient amount of free electrons is generated, and a sufficient infrared shielding effect can be obtained. As the amount of the element M added increases, the supply amount of free electrons increases and the infrared shielding effect also increases, but the value of x / y is saturated at about 1. Moreover, if the value of x / y is smaller than 1, it is preferable because an impurity phase can be prevented from being generated in the heat ray shielding layer.

  Regarding the value of z / y indicating the control of the amount of oxygen, in the composite tungsten oxide represented by MxWyOz, the same mechanism as that of the infrared shielding material represented by WyOz described above works, and z / y = Even in 3.0, since there is a supply of free electrons due to the addition amount of the element M described above, 2.2 ≦ z / y ≦ 3.0 is preferable, and 2.45 ≦ z / y ≦ 3.0 is more preferable. It is.

  Further, when the composite tungsten oxide has a hexagonal crystal structure, transmission of the oxide in the visible light region is improved, and absorption in the near infrared region is improved.

When the cation of the element M is added to the hexagonal void, the transmission in the visible light region is improved and the absorption in the near infrared region is improved. Here, generally, when the element M having a large ionic radius is added, the hexagonal crystal is formed. Specifically, Cs, K, Rb, Tl, In, Ba, Sn, Li, Ca, Sr, When Fe is added, hexagonal crystals are easily formed. Of course, other elements may be added as long as the additive element M exists in the hexagonal void formed by the WO ₆ unit, and is not limited to the above elements.

  When the composite tungsten oxide having a hexagonal crystal structure has a uniform crystal structure, the addition amount of the additive element M is preferably 0.2 or more and 0.5 or less in terms of x / y, more preferably 0.8. 33. When the value of x / y is 0.33, it is considered that the additive element M is arranged in all of the hexagonal voids.

  Besides hexagonal crystals, tetragonal and cubic tungsten bronzes also have an infrared shielding effect. These crystal structures tend to change the absorption position in the near infrared region, and the absorption position tends to move to the longer wavelength side in the order of cubic <tetragonal <hexagonal. Further, the accompanying absorption in the visible light region is small in the order of hexagonal crystal <tetragonal crystal <cubic crystal. For this reason, it is preferable to use hexagonal tungsten bronze for applications that transmit light in the visible light region and shield light in the infrared region.

  The average particle diameter of the heat ray shielding agent used in the present invention is preferably 10 to 800 nm, particularly preferably 10 to 400 nm, from the viewpoint of maintaining transparency. This is because particles smaller than 800 nm do not completely block light due to scattering, can maintain visibility in the visible light region, and at the same time can efficiently maintain transparency. In particular, when importance is attached to transparency in the visible light region, it is preferable to further consider scattering by particles. When importance is attached to the reduction of scattering by the particles, the average particle size is preferably 20 to 200 nm, particularly preferably 20 to 100 nm. In addition, the average particle diameter of the heat ray shielding agent is a number average value obtained by observing the cross section of the heat ray shielding layer with a transmission electron microscope at a magnification of about 1,000,000 times, and calculating the area circle equivalent diameter of at least 100 heat ray shielding agents. To do.

  The content of the heat ray shielding agent in the heat ray shielding layer is preferably 10 to 500 parts by mass, more preferably 20 to 500 parts by mass, and particularly preferably 30 to 300 parts by mass with respect to 100 parts by mass of a binder resin described later.

  Moreover, it is preferable from the viewpoint of improving the weather resistance that the surface of the composite tungsten oxide of the present invention is coated with an oxide containing one or more of Si, Ti, Zr, and Al.

  The composite tungsten oxide of the present invention is produced, for example, as follows.

  The tungsten oxide represented by the general formula WyOz and / or the composite tungsten oxide represented by MxWyOz can be obtained by heat-treating a tungsten compound starting material in an inert gas atmosphere or a reducing gas atmosphere. .

  The tungsten compound starting material is obtained by dissolving tungsten trioxide powder, tungsten oxide hydrate, tungsten hexachloride powder, ammonium tungstate powder, or tungsten hexachloride in alcohol and then drying. Tungsten oxide hydrate powder, or tungsten oxide hydrate powder obtained by dissolving tungsten hexachloride in alcohol and then adding water to precipitate and drying it, or ammonium tungstate It is preferable that it is at least one selected from a tungsten compound powder obtained by drying an aqueous solution and a metal tungsten powder.

  Here, in the case of producing tungsten oxide, it is further preferable to use tungsten oxide hydrate powder or tungsten compound powder obtained by drying ammonium tungstate aqueous solution from the viewpoint of ease of production process. Preferably, when producing a composite tungsten oxide, it is more preferable to use an aqueous ammonium tungstate solution or a tungsten hexachloride solution from the viewpoint that each element can be easily and uniformly mixed when the starting material is a solution. By using these raw materials and heat-treating them in an inert gas atmosphere or a reducing gas atmosphere, tungsten oxide and / or composite tungsten oxide having the above-described particle diameter can be obtained.

  The composite tungsten oxide represented by the general formula MxWyOz containing the element M is the same as the tungsten compound starting material of the tungsten oxide represented by the general formula WyOz described above. A tungsten compound contained in the form of a compound is used as a starting material. Here, in order to produce a starting material in which each component is uniformly mixed at the molecular level, it is preferable to mix each material with a solution, and the tungsten compound starting material containing the element M is dissolved in a solvent such as water or an organic solvent. Preferably it is possible. Examples thereof include tungstate, chloride, nitrate, sulfate, oxalate, oxide, and the like containing element M, but are not limited to these and are preferably in the form of a solution.

Here, the heat treatment condition in the inert atmosphere is preferably 650 ° C. or higher. The starting material heat-treated at 650 ° C. or higher has a sufficient coloring power and is efficient as a heat ray shielding agent. As the inert gas, an inert gas such as Ar or N ₂ is preferably used. As the heat treatment conditions in the reducing atmosphere, first, the starting material is heat-treated at 100 to 650 ° C. in a reducing gas atmosphere, and then heat-treated at a temperature of 650 to 1200 ° C. in an inert gas atmosphere. . The reducing gas at this time is not particularly limited, but H ₂ is preferable. When H ₂ is used as the reducing gas, the volume ratio of H ₂ is preferably 0.1% or more, more preferably 2% or more, as the composition of the reducing atmosphere. If it is 0.1% or more, the reduction can proceed efficiently.

The raw material powder reduced with hydrogen contains a magnetic phase, exhibits good infrared shielding properties, and can be used as a heat ray shielding agent in this state. However, since hydrogen contained in tungsten oxide is unstable, application may be limited in terms of weather resistance. Therefore, a more stable heat ray shielding agent can be obtained by heat-treating the tungsten oxide compound containing hydrogen at 650 ° C. or higher in an inert atmosphere. The atmosphere during the heat treatment at 650 ° C. or higher is not particularly limited, but N ₂ and Ar are preferable from an industrial viewpoint. By the heat treatment at 650 ° C. or higher, a Magneli phase is obtained in the heat ray shielding agent, and the weather resistance is improved.

  The composite tungsten oxide of the present invention is preferably surface-treated with a coupling agent such as a silane coupling agent, a titanate coupling agent, or an aluminum coupling agent. Silane coupling agents are preferred. Thereby, the affinity with the binder resin is improved, and various physical properties are improved in addition to transparency and heat ray cutting property.

  Examples of silane coupling agents include γ-chloropropylmethoxysilane, vinylethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxy. Silane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β -(Aminoethyl) -γ-aminopropyltrimethoxysilane and trimethoxyacrylsilane can be mentioned. Vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, and trimethoxyacrylsilane are preferred. These silane coupling agents may be used alone or in combination of two or more. Moreover, it is preferable to use content of the said compound at 5-20 mass parts with respect to 100 mass parts of composite tungsten oxides.

  The heat ray shielding layer further contains a binder resin in addition to the tungsten compound. As the binder resin, fluorine resin, silicone resin, olefin resin, acrylic resin, ethylene vinyl acetate copolymer (EVA), and polyvinyl butyral resin (PVB) are preferable, and fluorine resin is particularly preferable. Since these binder resins are the same as the organic resin in the radical blocking layer described above, detailed description thereof is omitted here.

  The thickness of the heat ray shielding layer is preferably from 0.1 to 50 μm, particularly preferably from 1 to 10 μm.

  In the laminate of the present invention, the radical blocking layer is disposed at least between the heat ray shielding layer and the ultraviolet ray absorbing layer, but the ultraviolet ray absorbing layer and the radical blocking layer may be laminated on both surfaces of the heat ray shielding layer. . That is, as shown in FIG. 3, the radical blocking layer 330 and the ultraviolet absorbing layer 320 are preferably laminated on both surfaces of the heat ray shielding layer 310. According to the laminated body having such a configuration, the deterioration of the tungsten compound can be prevented more highly.

  Moreover, in the laminated body 400 of this invention, as shown in FIG. 4, although the radical shielding layer 420 is arrange | positioned at least between the heat ray shielding layer 310 and the ultraviolet absorption layer 430, the radical shielding layer 420 of the heat ray shielding layer 410 is shown. It is preferable that an adhesive resin layer 440 is further laminated on the surface opposite to the surface on which the ultraviolet absorbing layer 430 is laminated. Such a laminate 400 is particularly preferably used as a heat ray-shielding laminated glass by being sandwiched between two transparent base materials 450.

(Adhesive resin layer)
The adhesive resin layer is a layer containing an adhesive resin. As the adhesive resin, fluorine resin, silicone resin, olefin resin, acrylic resin, ethylene vinyl acetate copolymer (EVA), and polyvinyl butyral resin (PVB) are preferable, EVA and PVB are more preferable, and EVA is particularly preferable. Since these adhesive resins are the same as the organic resins in the radical blocking layer described above, detailed description thereof is omitted here.

  The EVA-containing adhesive resin layer contains an organic peroxide in EVA, and further includes a crosslinking aid, an adhesion improver, a plasticizer, an acryloxy group-containing compound, a methacryloxy group-containing compound, an epoxy group-containing compound, if necessary. In addition, various additives such as a silane coupling agent can be contained. Since these additives and the method for producing the adhesive resin layer are the same as those of the radical blocking layer described above, detailed description thereof is omitted here.

(Heat ray shielding laminated glass)
The laminate of the present invention is preferably used as an interlayer film for laminated glass because it has high heat ray shielding properties, is highly suppressed from deterioration due to discoloration, and can maintain excellent transparency over a long period of time. A heat ray shielding laminated glass can be provided by the laminate.

  The laminated glass using the laminate of the present invention is a laminated glass in which an intermediate film is sandwiched between two transparent substrates and these are bonded and integrated, and the laminated film of the present invention described above as the intermediate film. The thing using a laminated body is mentioned.

  A preferred embodiment of such a heat ray shielding laminated glass is shown in FIGS. 4 and 5 are sectional views of the heat ray shielding laminated glass of the present invention. In the laminated glass shown in FIG. 4, the radical blocking layer 420 and the ultraviolet absorbing layer 430 are laminated on one surface of the heat ray shielding layer 410, and the adhesive resin layer 440 is laminated on the other surface of the heat ray shielding layer 410. The laminated body 400 is further sandwiched between two transparent substrates 450, and has a structure in which these are bonded and integrated.

  In the laminated glass shown in FIG. 5, a radical blocking layer (A) 530A containing an ethylene vinyl acetate copolymer, a radical blocking layer 530B containing polyethylene terephthalate, and an ultraviolet absorbing layer 520 on one surface of the heat ray blocking layer 510. Is laminated, and the laminated body 500 in which the adhesive resin layer 540 is laminated on the other surface of the heat ray shielding layer 510 is further sandwiched between two transparent base materials 450, and these are bonded and integrated. .

  When the laminated glass of the present invention is used as a window glass for aircraft, automobile windshields and side glasses, or buildings, an ultraviolet absorbing layer is arranged on the outdoor side, and a heat ray shielding layer is arranged on the indoor side, Laminated glass is preferably used. Thereby, the high discoloration prevention effect can be exhibited. In addition, in the laminated glass using the laminated body by which the radical blocking layer and the ultraviolet absorption layer were laminated | stacked on both surfaces of the heat ray shielding layer, it is not restrict | limited to such arrangement | positioning.

  In order to produce a laminated glass using the laminate of the present invention, each layer used in the laminate is produced, and the laminate obtained by laminating these is sandwiched between two transparent substrates. For example, a means for thermocompression bonding is used. The functional film and the transparent substrate can be bonded and integrated by thermocompression bonding.

  The thermocompression bonding is performed by, for example, pre-compression bonding at a temperature of 80 to 120 ° C. and heat treatment at 100 to 150 ° C. (particularly around 130 ° C.) for 10 minutes to 1 hour. Further, the heat treatment may be performed under pressure.

  In the present invention, “glass” in the laminated glass means the whole transparent substrate, and therefore “laminated glass” means a laminate formed by sandwiching the laminate as an intermediate film on the transparent substrate. .

  Although the transparent base material used for the laminated glass of this invention is not specifically limited, For example, plastic films other than glass plates, such as a silicate glass, an inorganic glass plate, a non-colored transparent glass plate, may be used. Examples of the plastic film include a polyethylene terephthalate (PET) film, a polyethylene aphthalate (PEN) film, and a polyethylene butyrate film, and a PET film is preferred. As for the thickness of a transparent base material, about 1-20 mm is common.

  The same transparent base material may be used for each transparent base material arrange | positioned at the both sides of a laminated body in a laminated glass, and a different transparent base material may be used in combination. It is preferable to determine the combination of the transparent substrates in consideration of the strength of the transparent substrates and the use of the laminated glass.

  When the transparent substrate in the laminated glass of the present invention is a glass plate on one side and a plastic film on the other side, it can be designed to have appropriate performance in impact resistance, penetration resistance, transparency and the like. For this reason, for example, it can be used for glass such as window glass equipped in various vehicle bodies and buildings, or glass such as showcases and show windows.

  Moreover, when both transparent substrates are glass plates, they can be designed to exhibit particularly excellent impact resistance and improved penetration resistance, and can be used for various applications including laminated glass.

  On the other hand, in the case of laminated glass of plastic film, for example, side glass and embedded glass of an automobile, the thickness of the plastic film is generally in the range of 0.02 to 2 mm because the thickness of the windshield is not required. A range of 0.02 to 1.2 mm is preferred. The thicknesses of the intermediate film and the plastic film can be changed according to the place where the glass is used.

  The glass plate used in the present invention is usually silicate glass. In the case of film tempered glass, the glass plate thickness varies depending on the place where it is installed. For example, when it is used for a side glass and a fitted glass of an automobile, it is not necessary to make it thick like a windshield, generally 0.1 to 10 mm, and preferably 0.3 to 5 mm. The one glass plate 1 is reinforced chemically or thermally.

  In the case of a laminated glass that is both a glass plate suitable for an automobile windshield or the like, the thickness of the glass plate is generally 0.5 to 10 mm, and preferably 1 to 8 mm.

  Hereinafter, the present invention will be described with reference to examples. The present invention is not limited by the following examples.

[Example 1]
A PET film (thickness: 100 μm) was used as the radical blocking layer. On the PET film, a coating solution for forming a heat ray shielding layer having the following composition was applied by a bar coater and dried at 80 ° C. for 30 seconds to form a heat ray shielding layer (thickness: 2 μm).

(Combination)
Functional group-containing fluororesin (solid content 15% by mass, MIBK 85% by mass, OPTOOL AR-110 (polymer A), manufactured by Daikin Industries, Ltd.) 100 parts by mass,
100 parts by mass of cesium tungsten oxide (Cs _0.33 WO ₃ , solid content 20% by mass, MIBK 80% by mass).

  Next, an ultraviolet absorbing layer (thickness: 500 μm) was obtained by a calendar molding method using the following composition as a raw material. The kneading of the blend was carried out at 80 ° C. for 15 minutes, the calender roll temperature was 80 ° C., and the processing speed was 5 m / min.

(Combination)
EVA (vinyl acetate content 25% by mass, Ultrasen 635, manufactured by Tosoh Corporation) 100 parts by mass,
3 parts by mass of a crosslinking agent (perbutyl E; t-butyl peroxy-2-ethylhexyl monocarbonate, manufactured by NOF Corporation),
1 part by mass of a silane coupling agent (KBM503; manufactured by Shin-Etsu Chemical Co., Ltd.)
1 part by mass of an ultraviolet absorber (2,2′-dihydroxy-4,4′-dimethoxybenzophenone; manufactured by BASF Ubinar 3049; manufactured by BASF Japan Ltd.).

  Next, an adhesive resin layer (thickness: 500 μm) was obtained in the same manner as the ultraviolet absorbing layer except that no ultraviolet absorber was used.

Then, the heat ray shielding layer, the ultraviolet ray absorbing layer and the adhesive resin layer formed on the radical shielding layer produced above are used, and these are in the order of the ultraviolet ray absorbing layer / radical shielding layer / heat ray shielding layer / adhesive resin layer. After obtaining a laminate by laminating in this manner, the laminate was further sandwiched between two glass substrates (thickness 2.5 mm) and subjected to temporary pressure bonding by heating at 100 ° C. for 30 minutes, and then in an autoclave. Heating was performed for 30 minutes under conditions of a pressure of 13 × 10 ⁵ Pa and a temperature of 140 ° C. Thereby, EVA contained in the adhesive resin layer and the ultraviolet absorbing layer was cross-linked and cured to obtain a laminated glass in which the transparent substrate and each layer were bonded and integrated.

[Example 2]
A radical blocking layer (A) (thickness: 500 μm) was obtained by a calendar molding method using the following composition as a raw material. The kneading of the blend was performed at 80 ° C. for 15 minutes, the temperature of the calender roll was 80 ° C., and the processing speed was 5 m / min.

(Combination)
EVA (vinyl acetate content 25% by mass, Ultrasen 635, manufactured by Tosoh Corporation) 100 parts by mass,
3 parts by mass of a crosslinking agent (perbutyl E; t-butyl peroxy-2-ethylhexyl monocarbonate, manufactured by NOF Corporation),
1 part by mass of a silane coupling agent (KBM503; manufactured by Shin-Etsu Chemical Co., Ltd.).

  Furthermore, a PET film (thickness: 100 μm) was used as the radical blocking layer (B). A radical blocking layer (A) is laminated on a PET film, and the following coating solution for forming a heat ray shielding layer is applied onto the radical blocking layer (A) with a bar coater, dried at 80 ° C. for 30 seconds, and a heat ray shielding layer ( 2 μm thick) was formed.

(Combination)
Functional group-containing fluororesin (solid content 15% by mass, MIBK 85% by mass, OPTOOL AR-110 (polymer A), manufactured by Daikin Industries, Ltd.) 100 parts by mass,
100 parts by mass of cesium tungsten oxide (Cs _0.33 WO ₃ , solid content 20% by mass, MIBK 80% by mass).

  Next, an ultraviolet absorbing layer and an adhesive resin layer were produced in the same manner as in Example 1.

Then, the radical blocking layers (A) and (B) prepared above, the heat ray blocking layer, the ultraviolet absorbing layer and the adhesive resin layer are used, and these are combined with the ultraviolet absorbing layer / radical blocking layer (B) / radical blocking layer (A). After laminating in order of / heat ray shielding layer / adhesive resin layer to obtain a laminate, these are further sandwiched between two glass substrates (thickness 2.5 mm) and heated at 100 ° C. for 30 minutes. After performing temporary pressure bonding by heating, it was heated in an autoclave for 30 minutes under conditions of a pressure of 13 × 10 ⁵ Pa and a temperature of 140 ° C. Thereby, EVA contained in the adhesive resin layer and the ultraviolet absorbing layer was cross-linked and cured to obtain a laminated glass in which the transparent substrate and each layer were bonded and integrated.

[Example 3]
An adhesive resin layer (thickness: 500 μm) was obtained by a calendar molding method using the following composition as a raw material. The kneading of the blend was performed at 80 ° C. for 15 minutes, the temperature of the calender roll was 80 ° C., and the processing speed was 5 m / min.

(Combination)
EVA (vinyl acetate content 25% by mass, Ultrasen 635, manufactured by Tosoh Corporation) 100 parts by mass,
3 parts by mass of a crosslinking agent (perbutyl E; t-butyl peroxy-2-ethylhexyl monocarbonate, manufactured by NOF Corporation),
1 part by mass of a silane coupling agent (KBM503; manufactured by Shin-Etsu Chemical Co., Ltd.).

  On the adhesive resin layer, a coating solution for forming a heat ray shielding layer having the following composition was applied by a bar coater and dried at 80 ° C. for 30 seconds to form a heat ray shielding layer (thickness: 2 μm).

(Combination)
Functional group-containing fluororesin (solid content 15% by mass, MIBK 85% by mass, OPTOOL AR-110 (polymer A), manufactured by Daikin Industries, Ltd.) 100 parts by mass,
100 parts by mass of cesium tungsten oxide (Cs _0.33 WO ₃ , solid content 20% by mass, MIBK 80% by mass).

  Next, a coating solution for forming a radical blocking layer having the following composition was applied onto the heat ray shielding layer with a bar coater and dried at 80 ° C. for 30 seconds to form a radical blocking layer (thickness: 2 μm).

(Combination)
Functional group-containing fluororesin (solid content 15% by mass, MIBK 85% by mass, OPTOOL AR-110 (polymer A), manufactured by Daikin Industries, Ltd.) 100 parts by mass,
2 parts by mass of a hindered amine light stabilizer (TINUVIN (registered trademark) 770 DF; manufactured by Ciba Specialty Chemicals Co., Ltd.).

Next, after the ultraviolet absorbing layer produced in the same manner as in Example 1 was laminated on the radical blocking layer produced above to obtain a laminate, these were further laminated with two glass substrates (thickness 2.5 mm). ) And heated at 100 ° C. for 30 minutes to perform temporary pressure bonding, and then heated in an autoclave at a pressure of 13 × 10 ⁵ Pa and a temperature of 140 ° C. for 30 minutes. Thereby, EVA contained in the adhesive resin layer and the ultraviolet absorbing layer was cross-linked and cured to obtain a laminated glass in which the transparent substrate and each layer were bonded and integrated.

[Comparative Example 1]
In the same manner as in Example 1, a heat ray shielding layer was formed on the PET film. Further, an adhesive resin layer and an ultraviolet absorbing layer were produced in the same manner as in Example 1. And after laminating these in order of adhesive resin layer / PET film / heat ray shielding layer / ultraviolet absorption layer to obtain a laminate, this was further added with two glass substrates (thickness 2.5 mm). After sandwiching and heating at 100 ° C. for 30 minutes, pressure bonding was performed, followed by heating in an autoclave for 30 minutes under conditions of a pressure of 13 × 10 ⁵ Pa and a temperature of 140 ° C. Thereby, EVA contained in the adhesive resin layer and the ultraviolet absorbing layer was cross-linked and cured to obtain a laminated glass in which the transparent substrate and each layer were bonded and integrated.

[Comparative Example 2]
An adhesive resin layer (thickness: 500 μm) was obtained by a calendar molding method using the following composition as a raw material. The kneading of the blend was performed at 80 ° C. for 15 minutes, the temperature of the calender roll was 80 ° C., and the processing speed was 5 m / min.

(Combination)
EVA (vinyl acetate content 25% by mass, Ultrasen 635, manufactured by Tosoh Corporation) 100 parts by mass,
3 parts by mass of a crosslinking agent (perbutyl E; t-butyl peroxy-2-ethylhexyl monocarbonate, manufactured by NOF Corporation),
1 part by mass of a silane coupling agent (KBM503; manufactured by Shin-Etsu Chemical Co., Ltd.).

  On the adhesive resin layer, a coating solution for forming a heat ray shielding layer having the following composition was applied by a bar coater and dried at 80 ° C. for 30 seconds to form a heat ray shielding layer (thickness: 2 μm).

(Combination)
Functional group-containing fluororesin (solid content 15% by mass, MIBK 85% by mass, OPTOOL AR-110 (polymer A), manufactured by Daikin Industries, Ltd.) 100 parts by mass,
100 parts by mass of cesium tungsten oxide (Cs _0.33 WO ₃ , solid content 20% by mass, MIBK 80% by mass).

Next, an ultraviolet absorbing layer produced in the same manner as in Example 1 was laminated. This ultraviolet absorbing layer was laminated on the heat ray shielding layer produced on the adhesive resin layer to obtain a laminate, and these were further sandwiched between two glass substrates (thickness 2.5 mm), and 100 ° C. Was subjected to temporary pressure bonding by heating for 30 minutes, and then heated in an autoclave for 30 minutes under conditions of a pressure of 13 × 10 ⁵ Pa and a temperature of 140 ° C. Thereby, EVA contained in the adhesive resin layer and the ultraviolet absorbing layer was cross-linked and cured to obtain a laminated glass in which the transparent substrate and each layer were bonded and integrated.

[Evaluation]
1. Initial luminous transmittance The luminous transmittance of each laminated glass produced above was measured according to the following procedure.

  Using the transmission spectrum of the filter measured by a spectrophotometer UV3100PC (trade name) manufactured by Shimadzu Corporation, Y of the tristimulus value of the XYZ color system was calculated and used as luminous transmittance (Y). The calculation method was in accordance with JIS Z8722-2000. The results are shown in Table 1.

2. Luminous transmittance after weather resistance test Using each of the laminated glasses prepared above, an accelerated weather resistance tester (Super UV tester SUV-F11, manufactured by Iwasaki Electric Co., Ltd.), wavelength in an atmosphere of 25 ° C. Ultraviolet rays of 295 to 450 nm were irradiated for 500 hours at an intensity of 100 mW / cm ² . Moreover, the ultraviolet irradiation was performed from the side of the laminated glass on which the ultraviolet absorbing layer was formed. Thereafter, the luminous transmittance of the laminated glass was measured in the same manner as described above. The results are shown in Table 1.

このように本発明の積層体を用いた合わせガラスでは、長時間に亘る紫外線照射後であっても視感透過率の低下が低く、変色が高く防止されていることがわかる。

Thus, in the laminated glass using the laminated body of the present invention, it can be seen that even after ultraviolet irradiation for a long time, the decrease in luminous transmittance is low and discoloration is highly prevented.

Sectional drawing of the laminated body of this invention is shown. Sectional drawing of the laminated body of this invention is shown. Sectional drawing of the laminated body of this invention is shown. Sectional drawing of the heat ray shielding laminated glass using the laminated body of this invention is shown. Sectional drawing of the heat ray shielding laminated glass using the laminated body of this invention is shown.

Explanation of symbols

110, 210, 310, 410, 510: heat ray shielding layer,
120, 220, 320, 420, 520: UV absorbing layer,
130, 330, 430: radical blocking layer,
230A, 530A: radical blocking layer containing EVA,
230B, 530B: radical blocking layer containing PET,
400, 500: Laminate,
440, 540: adhesive resin layer,
450, 550: Transparent substrate.

Claims (9)

It has a heat ray shielding layer containing a tungsten compound, an ultraviolet absorbing layer containing an ultraviolet absorber, and a radical blocking layer containing an organic resin,
A laminate comprising at least one radical blocking layer disposed between the heat ray blocking layer and the ultraviolet absorbing layer.   The organic resin is at least one selected from the group consisting of a fluororesin, a silicone resin, an olefin resin, an acrylic resin, an ethylene vinyl acetate copolymer, a polyester resin, a cellulose resin, and a polycarbonate resin. Item 2. The laminate according to Item 1.   The laminate according to claim 1 or 2, wherein the radical blocking layer further contains a hindered amine light stabilizer.   A radical blocking layer (A) containing an ethylene vinyl acetate copolymer and / or a radical blocking layer (B) containing polyethylene terephthalate is disposed between the heat ray blocking layer and the ultraviolet absorbing layer. The laminated body of any one of Claims 1-3.   The laminate according to any one of claims 1 to 4, wherein the ultraviolet absorber is a benzophenone ultraviolet absorber.   The laminate according to any one of claims 1 to 5, wherein the ultraviolet absorbing layer further contains an ethylene vinyl acetate copolymer.   The laminate according to any one of claims 1 to 6, wherein the tungsten compound is made of tungsten oxide and / or composite tungsten oxide.   The adhesive resin layer is further laminated | stacked on the surface on the opposite side to the surface where the said ultraviolet-ray absorption layer and radical blocking layer of the said heat ray shielding layer are laminated | stacked, The any one of Claims 1-7 characterized by the above-mentioned. The laminated body as described in. An intermediate film is sandwiched between two transparent base materials, and these are heat ray-shielding laminated glasses in which these are bonded and integrated,
The said intermediate film is a laminated body of any one of Claims 1-8, The heat ray shielding laminated glass characterized by the above-mentioned.

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