JP5368881B2 - Heat ray shielding laminated glass interlayer film and heat ray shielding laminated glass - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an intermediate film for a heat ray shielding laminate glass, the film suppressing degradation by discoloration and having excellent transparency, even when the film contains a (double) tungsten oxide as a heat ray shielding agent. <P>SOLUTION: The intermediate film for a heat ray shielding laminated glass includes a heat ray shielding layer 110 containing a (double) tungsten oxide interposed by an adhesive resin layer 120A in a light-receiving face side and an adhesive resin layer 120B in a back face side, and is characterized in that: the adhesive resin layer 120A in the light-receiving face side and the adhesive resin layer 120B in the back face side contain an adhesive resin and a UV absorbent; the amount of the UV absorbent in the adhesive resin layer 120A in the light-receiving face side is 0.2 to 1.5 parts by mass with respect to 100 parts by mass of the adhesive resin; the amount of the UV absorbent in the adhesive resin layer 120B in the back face side is 0.1 to 1.4 parts by mass with respect to 100 parts by mass of the adhesive resin; and a difference between the amount of the UV absorbent in the adhesive resin layer in the light-receiving face side and the amount of the UV absorbent in the adhesive resin layer in the back face side is 0.1 to 0.3. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a laminated glass excellent in heat ray (infrared ray) shielding properties used for windshields and side glasses of aircraft, automobiles, window glass of buildings, 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 in which an intermediate film in which (composite) tungsten oxide is dispersed as a heat ray shielding agent in a soft resin is sandwiched between two glass substrates.

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 (composite) tungsten oxide ensures both the heat ray cutting function and transparency. However, a laminated glass containing a heat ray shielding agent made of such a tungsten compound has a problem of discoloration to blue or the like when used for a long time.

  Accordingly, an object of the present invention is to provide an intermediate film for heat ray-shielding laminated glass that is suppressed in deterioration due to discoloration and has excellent transparency even when (composite) tungsten oxide is contained as a heat ray shielding agent.

  Tungsten compounds have an excellent near-infrared shielding effect, but an intermediate film using the tungsten compound sometimes shows a change in transmittance accompanying blue discoloration. This is probably because the film is exposed to sunlight for a long time, such as when used 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.

  Therefore, as a result of various studies by the present inventor, by arranging an adhesive resin layer containing a predetermined amount of ultraviolet absorber on each side of the heat ray shielding layer containing (composite) tungsten oxide, It was found that discoloration can be prevented at a high level.

［但し、Ｒ ¹ が、水素原子又はヒドロキシル基を表し、Ｒ ² が、水素原子又はヒドロキシル基を表し、Ｒ ³ が、水素原子、ヒドロキシル基、炭素原子数１〜１４個のアルキル基又は炭素原子数１〜１４個のアルコキシ基を表し、そしてＲ ⁴ が、水素原子、ヒドロキシル基、炭素原子数１〜１４個のアルキル基又は炭素原子数１〜１４個のアルコキシ基を表す］で示されるベンゾフェノン系紫外線吸収剤であり、且つ
前記接着樹脂が、エチレン酢酸ビニル共重合体であることを特徴とする熱線遮蔽合わせガラス用中間膜である。 That is, the present invention is an intermediate film for heat ray shielding laminated glass in which a heat ray shielding layer containing tungsten oxide and / or composite tungsten oxide is sandwiched between a light receiving surface side adhesive resin layer and a back surface side adhesive resin layer. ,
The light receiving surface side adhesive resin layer and the back surface side adhesive resin layer include an adhesive resin and an ultraviolet absorber,
The content of the ultraviolet absorber in the light-receiving surface-side adhesive resin layer, is 0.4 to 1.0 part by mass with respect to the adhesive resin 100 parts by weight,
The content of the ultraviolet absorber in the back side adhesive resin layer is 0.1 to 0.9 parts by mass with respect to 100 parts by mass of the adhesive resin ,
The content (U _L ) of the ultraviolet absorbent, which is the mass part of the ultraviolet absorbent with respect to 100 parts by mass of the adhesive resin in the light receiving surface side adhesive resin layer , and the ultraviolet ray with respect to 100 parts by mass of the adhesive resin in the back side adhesive resin layer. the difference between the content of the ultraviolet absorber is a mass of the absorbent _{(U B) (U L -U} B) is, Ri 0.1-0.3 der,
The ultraviolet absorber is represented by the following formula (I):

[However, R ¹ represents a hydrogen atom or a hydroxyl group, R ² represents a hydrogen atom or a hydroxyl group, and R ³ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 14 carbon atoms, or a carbon atom. Represents an alkoxy group having 1 to 14 carbon atoms , and R ⁴ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 14 carbon atoms, or an alkoxy group having 1 to 14 carbon atoms]. UV absorber, and
The adhesive film is an intermediate film for heat ray-shielding laminated glass , wherein the adhesive resin is an ethylene vinyl acetate copolymer .

  The intermediate film for heat ray shielding laminated glass of the present invention contains a (composite) tungsten oxide that efficiently cuts near infrared rays, and a predetermined amount of an ultraviolet absorber for suppressing the oxidative deterioration of the (composite) tungsten oxide. An adhesive resin layer containing is used. By using the ultraviolet absorber in this way, the anti-oxidation effect of the heat ray shielding agent is particularly high, and it is possible to prevent the intermediate film from changing to blue over a long period of time. Therefore, the intermediate film for heat ray shielding laminated glass of the present invention efficiently cuts heat rays (infrared rays), is highly suppressed from deterioration due to discoloration, and can maintain excellent transparency over a long period of time.

Sectional drawing of the intermediate film for heat ray shielding laminated glasses of this invention is shown. Sectional drawing of the intermediate film for heat ray shielding laminated glasses of this invention is shown. Sectional drawing of the heat ray shielding laminated glass using the intermediate film for heat ray shielding laminated glass of this invention is shown.

  First, the layer structure of the intermediate film for heat ray shielding laminated glass of the present invention will be described with reference to FIGS. 1 and 2 are sectional views of the interlayer film for heat ray shielding laminated glass of the present invention.

  In the present invention, the heat ray generally means infrared rays, particularly infrared rays having a wavelength of 780 nm or more that raises the temperature even among sunlight rays. The “light-receiving surface side” in the intermediate film for heat ray shielding laminated glass means the side on which light including infrared rays such as sunlight enters, and the “back side” in the intermediate film for heat ray shielding laminated glass means that sunlight is It means the opposite side to the incident side.

  As shown in FIG. 1, in the intermediate film for heat ray shielding laminated glass of the present invention, the heat ray shielding layer 110 containing tungsten oxide and / or composite tungsten oxide has a light receiving surface side adhesive resin layer 120A and a back surface side adhesive resin layer. It has the structure clamped by 120B. The light-receiving surface side adhesive resin layer 120A and the back surface side adhesive resin layer 120B include an adhesive resin and an ultraviolet absorber. Thus, by disposing the adhesive resin layers 120A and 120B containing the adhesive resin and the ultraviolet absorber on both sides of the heat ray shielding layer 110 containing the (composite) tungsten oxide, the oxidative deterioration of the (composite) tungsten oxide is increased. Can be suppressed.

Further, in the present invention, the content of the ultraviolet absorber in the light receiving surface side adhesive resin layer 120A and the back surface side adhesive resin layer 120B is set within a predetermined range, and the content of the ultraviolet absorber in the light receiving surface side adhesive resin layer 120A is It is characterized in that it is more than the back side adhesive resin layer 120B. Specifically, the content of the ultraviolet absorber in the light-receiving surface side adhesive resin layer is 0.4 to 1.0 part by mass with respect to 100 parts by mass of the adhesive resin, and the ultraviolet absorber in the back surface side adhesive resin layer content, adhesion was 0.9 parts by mass 0.1 relative to the resin 100 parts by mass, further UV absorber which is parts by weight of the UV absorber with respect to the adhesive resin 100 parts by weight of the light-receiving surface adhesive resin layer the content of the (U _L), the content of the ultraviolet absorber is a part by weight of UV absorber to said adhesive resin 100 parts by weight of the backside adhesive resin layer the difference between the _{(U B) (U L -U} B) Is 0.1 to 0.3. By using the ultraviolet absorber in this way, the oxidation deterioration of the (composite) tungsten oxide can be highly suppressed with the addition of a small amount of the ultraviolet absorber, and the adhesive resin layers on the light receiving surface side and the back surface side can be suppressed. It is also possible to ensure high transparency.

  The heat ray shielding layer is preferably formed on a plastic film. Specifically, as shown in FIG. 2, a configuration in which the heat ray shielding layer 210 formed on the plastic film 230 is sandwiched between the light receiving surface side adhesive resin layer 220A and the back surface side adhesive resin layer 220B is particularly preferable. The plastic film 230 may be disposed so as to be in contact with the back surface side adhesive resin layer 220B, but is preferably disposed so as to be in contact with the light receiving surface side adhesive resin layer 220A as shown in FIG. By using the plastic film 230 in this way, it is possible to suppress the ultraviolet light transmission and to further suppress the oxidative deterioration of the (composite) tungsten oxide.

  Hereinafter, each layer used for the intermediate film for heat ray shielding laminated glass of the present invention will be described.

[Adhesive resin layer]
The light receiving surface side adhesive resin layer and the back surface side adhesive resin layer include an adhesive resin and an ultraviolet absorber.

The content of the ultraviolet absorber in the light receiving surface side adhesive resin layer is 0.4 to 1.0 part by mass, preferably 0 . It is 5-1.0 mass part.

The content of the ultraviolet absorber in the back surface side adhesive resin layer is 0.1 to 0.9 parts by mass, preferably 0.3 to 0.9 parts by mass, more preferably 0.00 with respect to 100 parts by mass of the adhesive resin. 4 to 0.9 parts by mass.

  In the light-receiving surface side adhesive resin layer and the back surface side adhesive resin layer, if the content of the ultraviolet absorber is too much, the dispersibility of the ultraviolet absorber is lowered, and the adhesive resin layer may become cloudy and the transparency may be lowered. is there. In the light receiving surface side adhesive resin layer and the back surface side adhesive resin layer, if the content of the ultraviolet absorber is too small, the deterioration of the (composite) tungsten oxide cannot be sufficiently suppressed, and the intermediate film may be discolored. is there.

Furthermore the content of the ultraviolet absorbent in the light-receiving surface side adhesive resin layer (U _L), the content of the ultraviolet absorber in the back surface-side adhesive resin layer the difference between the _{(U B) (U L -U} B) is 0. 1 to 0.3, preferably 0.1 to 0.2.

As the ultraviolet absorber used in the light-receiving surface side adhesive resin layer and the back surface-side adhesive resin layer, since it is possible to prevent high oxidation of the (composite) tungsten oxide, a benzophenone compound.

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

[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- Hydroxy-4-octyloxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, and particularly 2-hydroxy-4-octyl Oxybenzophenone and 2,2′-dihydroxy-4,4′-dimethoxybenzophenone are preferred. In addition, the ultraviolet absorber mentioned above can also be used individually by 1 type, and can also use 2 or more types.

As the adhesive resin used for the light-receiving surface side adhesive resin layer and the back surface-side adhesive resin layer, an error styrene vinyl acetate copolymer (EVA). By using EVA, excellent adhesion between the respective layers can be ensured, and oxidation deterioration of the (composite) tungsten oxide can be suppressed to a high level.

  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 EVA has a melt flow index (MFR) of 1.0 to 30.0 g / 10 min, particularly 1.5 to 5.0 g / 10 min.

  The adhesive resin layer containing EVA preferably contains an organic peroxide as a crosslinking agent. The EVA-containing adhesive resin 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-butylperoxy-2-ethylhexyl monocarbonate, 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-butylperoxy) cyclohexane, 1, 1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, t-butylperoxybenzoate, 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 Oxide, chlorohexanone peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, cumyl peroxy octoate, succinic peroxide, acetyl peroxide, m-toluoyl peroxide, t-butyl peroxide isobutyl Mention may be made of leo and 2,4-dichlorobenzoyl peroxide.

  The content of the organic peroxide in the adhesive resin 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 the crosslinking aid 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.

  In order to further enhance the adhesive strength of the EVA-containing adhesive resin 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 adhesive resin 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.

  The thickness of the light-receiving surface side adhesive resin layer and the back surface side adhesive resin layer is preferably 50 μm to 2 mm, particularly 400 μm to 1 mm.

  In order to produce an adhesive resin layer using EVA, a composition containing an ultraviolet absorber, EVA, and, if necessary, an organic peroxide is mixed and then subjected to normal extrusion molding, calendar molding (calendering). ) And the like are used.

  The mixing of the composition is preferably performed by heating and kneading at a temperature of 40 to 100 ° C, particularly 60 to 90 ° 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 40-100 degreeC, especially 60-90 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.

[Heat ray shielding layer]
The heat ray shielding layer used for the intermediate film of the present invention contains tungsten oxide and / or composite tungsten oxide as a heat ray shielding agent. These (composite) tungsten oxides can impart excellent heat ray shielding properties to the intermediate film without reducing the visible light transmittance.

  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 heat ray shielding agent 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 WO ₂ crystal phase other than the objective in the heat ray shielding agent and to obtain chemical stability as a material. Therefore, it can be applied as an effective heat ray shielding agent. 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 heat ray shielding agent 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, Te, Ti, Nb, V, Mo, Ta, Re, be, Hf, Os, Bi, 1 or more elements inner shell selected in I, W is tungsten, O is oxygen, (0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3) An alkali metal is a group 1 element of the periodic table excluding hydrogen, and an alkaline earth metal is a group 2 of the periodic table. Elements, rare earth elements are Sc, Y and lanthanoid elements. From the viewpoint of improving optical properties and weather resistance as a line shielding agent, the element M 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 heat ray shielding effect can be obtained. As the amount of the element M added increases, the supply amount of free electrons increases and the heat ray shielding effect 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 oxygen amount, in the composite tungsten oxide represented by MxWyOz, in addition to the same mechanism as the heat ray shielding agent represented by WyOz described above, 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 a heat ray 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.

  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 the starting material in an inert gas atmosphere or a reducing gas atmosphere.

  The starting material is tungsten trioxide powder, tungsten oxide hydrate, tungsten hexachloride powder, ammonium tungstate powder, or tungsten obtained by dissolving tungsten hexachloride in alcohol and drying. 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 aqueous solution It is preferable that it is any one or more selected from tungsten compound powder obtained by drying and metal tungsten powder.

  Here, when manufacturing tungsten oxide, it is more preferable to use a hydrated powder of tungsten oxide or a powder obtained by drying an ammonium tungstate aqueous solution from the viewpoint of ease of the manufacturing process, When producing a composite tungsten oxide, it is more preferable to use an ammonium tungstate aqueous 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 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 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, obtaining the projected area equivalent circle diameter of at least 100 heat ray shielding agents, and the number average thereof Value.

  The content of the (composite) tungsten oxide 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 the binder resin.

  The heat ray shielding layer contains a binder resin in addition to the above-described (composite) tungsten oxide. Examples of the binder resin include fluororesin, silicone resin, olefin resin, acrylic resin, ethylene vinyl acetate copolymer (EVA), and polyvinyl butyral resin (PVB). Of these, fluorine resin, silicone resin, and acrylic resin are preferably used. These binder resins have excellent light resistance and are not easily discolored. When these binder resins are used, the heat ray shielding layer is preferably a cured layer of a resin composition containing a (composite) tungsten oxide and a binder resin. The said resin may be used individually by 1 type, and may use 2 or more types together.

  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 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). Preferable examples of commercially available fluororesins include Lumiflon (registered trademark, manufactured by Asahi Glass Co., Ltd.), Cytop (registered trademark, manufactured by Asahi Glass Co., Ltd.), Zaffle (registered trademark, manufactured by Daikin Chemical Co., Ltd.), And OPTOOL (registered trademark, manufactured by 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 monomer include polyethylene, polypropylene, and chlorinated polyethylene.

  Examples of acrylic resin monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth) acrylate. , Pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, ethylhexyl (meth) acrylate, nonyl (Meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylic , Alkyl (meth) acrylates such as stearyl (meth) acrylate and isostearyl (meth) acrylate; hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3- Hydroxyalkyl (meth) acrylates such as hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate; phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl ( Phenoxyalkyl (meth) acrylates such as (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, -Alkoxyalkyl (meth) acrylates such as butoxyethyl (meth) acrylate and 2-methoxybutyl (meth) acrylate; polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene Polyglycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, etc. Alkylene glycol (meth) acrylate; Pentaerythri Examples include tall tri (meth) acrylate, pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and glycerin di (meth) acrylate. Examples of the acrylic resin include homopolymers of these monomers, copolymers of two or more kinds, and copolymers of the monomers and other copolymerizable monomers.

  The heat ray shielding layer may contain a dye if necessary in addition to the (composite) tungsten oxide. The dye generally has an absorption maximum at a wavelength of 800 to 1200 nm. Examples include phthalocyanine dyes, metal complex dyes, nickel dithiolene complex dyes, cyanine dyes, squarylium dyes, polymethine dyes, Examples include azomethine dyes, azo dyes, polyazo dyes, diimonium dyes, aminium dyes, and anthraquinone dyes, and cyanine dyes, phthalocyanine dyes, and diimonium dyes are particularly preferable. These dyes can be used alone or in combination.

  The heat ray shielding layer preferably contains 0.1 to 20 parts by mass, more preferably 1 to 20 parts by mass, and particularly preferably 1 to 10 parts by mass with respect to 100 parts by mass of the binder resin.

  In the present invention, the heat ray shielding layer may be provided with a function of adjusting color tone by imparting a neon light emission absorbing function. For this purpose, the heat ray shielding layer may contain a neon-emitting selective absorption dye.

  Neon-emitting selective absorption dyes include cyanine dyes, squarylium dyes, anthraquinone dyes, phthalocyanine dyes, polymethine dyes, polyazo dyes, azurenium dyes, diphenylmethane dyes, and triphenylmethane dyes. it can. Such a selective absorption dye is required to have a selective absorption of neon emission near 585 nm and a small absorption at other visible light wavelengths, so that the absorption maximum wavelength is 575 to 595 nm and the absorption spectrum half width is What is 40 nm or less is preferable.

  The thickness of the heat ray shielding layer is preferably 0.1 to 15 μm, particularly 3 to 10 μm.

  The heat ray shielding layer is preferably formed on a plastic film. 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. The thickness of the plastic film is preferably 10 to 400 μm, particularly 20 to 200 μm. Further, in order to improve the adhesiveness, the plastic film surface may be subjected in advance to an adhesion treatment such as a corona treatment, a plasma treatment, a flame treatment, and a primer layer coating treatment.

  The heat ray shielding layer containing a heat ray shielding agent and a binder resin is preferably a cured layer of a resin composition containing a heat ray shielding agent, a binder resin, and, if necessary, an organic solvent. In order to produce the heat ray shielding layer, for example, a method in which the resin composition is applied onto a base material such as a plastic film and simply dried is used.

  When curing the resin composition, it is preferable to use a polymerization initiator. For example, it is preferable to use a thermal polymerization initiator in the case of thermosetting, and to use a photopolymerization initiator in the case of ultraviolet curing.

  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.

  Generally the quantity of a photoinitiator is 0.1-10 mass% with respect to a resin composition, Preferably it is 0.1-5 mass%.

  When producing a heat ray shielding layer, a resin composition containing a binder resin, a heat ray shielding agent, a polymerization initiator, and an organic solvent, if necessary, is applied onto a predetermined substrate such as a plastic film or a transparent substrate, After drying, a method of curing by heating or irradiation with light such as ultraviolet rays, X-rays, γ rays, and electron beams is preferably used as necessary. Drying is preferably performed by heating the resin composition coated on the plastic film at 60 to 150 ° C, particularly 70 to 110 ° C. The drying time may be about 1 to 10 minutes. The light irradiation can be performed by irradiating ultraviolet rays emitted from light rays such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp.

  Examples of the organic solvent used in the resin composition include aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and butyl acetate, and alcohols such as isopropyl alcohol. Can do.

[Heat ray shielding laminated glass]
The intermediate film of the present invention is preferably used as an intermediate film for heat-ray-shielding 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. .

  The heat ray shielding laminated glass using the interlayer film of the present invention has a structure in which the interlayer film is sandwiched between two transparent substrates and these are bonded and integrated.

  A preferred embodiment of such a heat ray shielding laminated glass is shown in FIG. FIG. 3 is a schematic cross-sectional view of a heat ray shielding laminated glass using the intermediate film shown in FIG. The heat ray shielding laminated glass shown in FIG. 3 has an intermediate film in which a heat ray shielding layer 310 formed on a plastic film 330 is sandwiched between a light receiving surface side adhesive resin layer 320A and a back surface side adhesive resin layer 320B. This intermediate film is further sandwiched between two transparent base materials 340, and these are bonded and integrated.

  When the heat ray shielding laminated glass is applied to an actual application, the heat ray shielding laminated glass is used so that the light receiving surface side adhesive resin layer 320A is arranged on the side irradiated with light including heat rays such as sunlight. . For example, when the heat-shielding laminated glass is used as a window glass for a building or a vehicle, the light-receiving surface side adhesive resin layer 320A is disposed on the outdoor side, and the back surface side adhesive resin layer 320B is disposed on the indoor side. To. By setting it as such arrangement | positioning, discoloration of a heat ray shielding laminated glass can be prevented highly.

  In order to produce the heat ray-shielding laminated glass using the interlayer film of the present invention, means for sandwiching the interlayer film between two transparent substrates and thermocompression-bonding the obtained laminate is used. By thermocompression bonding, the adhesive resin layer is cured, and the intermediate film and the transparent substrate can be bonded and integrated.

The thermocompression bonding is performed by, for example, pre-compressing the laminate at a temperature of 80 to 120 ° C. and heat-treating at 100 to 150 ° C. (particularly around 130 ° C.) for 10 minutes to 1 hour. Further, the heat treatment may be performed under pressure. At this time, it is preferable that the laminate is pressed while being pressurized at a pressure of 1.0 × 10 ³ Pa to 5.0 × 10 ⁷ Pa.

  In the present invention, “glass” in the heat ray-shielding laminated glass means a transparent substrate in general, and therefore “heat ray-shielding laminated glass” is obtained by sandwiching an intermediate film between transparent substrates. Means.

  Although the transparent base material used for the heat ray shielding 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 both sides of a laminated body in heat ray shielding 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.

  The heat ray-shielding laminated glass of the present invention is a window glass for buildings and vehicles (automobiles, railway vehicles, ships), electronic devices such as plasma displays, doors and walls of various devices such as refrigerators and heat insulation devices, etc. Can be used in various applications.

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

Example 1
1. Preparation of light-receiving surface-side adhesive resin layer A sheet-shaped light-receiving surface-side adhesive resin layer (thickness 0.4 mm) was obtained by a calendar molding method using the following composition as a raw material. The blend was kneaded at 80 ° C. for 15 minutes, the calender roll temperature was 80 ° C., and the processing speed was 5 m / min.

(Composition of light receiving surface side adhesive resin layer)
(1) EVA (vinyl acetate content 25 parts by mass with respect to EVA 100 parts by mass, Tosoh Corporation Ultrasen 635) 100 parts by mass,
(2) 2.5 parts by mass of a crosslinking agent (tert-butyl peroxy 2-ethylhexyl carbonate; Trigonox 117 manufactured by Kayaku Akzo Co., Ltd.)
(3) 2 parts by mass of a crosslinking aid (triallyl isocyanurate; Nippon Kasei Corporation TAIC (registered trademark)),
(4) 0.5 parts by mass of a silane coupling agent (γ-methacryloxypropyltrimethoxysilane; manufactured by Shin-Etsu Chemical Co., Ltd., KBM503)
(5) 0.5 part by mass of an ultraviolet absorber (2,2′-dihydroxy-4,4′-dimethoxybenzophenone).

2. Production of Back Side Adhesive Resin Layer A sheet-like back side adhesive resin layer (thickness 0.4 mm) was obtained by a calendar molding method using the following composition as a raw material. The blend was kneaded at 80 ° C. for 15 minutes, the calender roll temperature was 80 ° C., and the processing speed was 5 m / min.

(Composition of back side adhesive resin layer)
(1) EVA (vinyl acetate content 25 parts by mass with respect to EVA 100 parts by mass, Tosoh Corporation Ultrasen 635) 100 parts by mass,
(2) 2.5 parts by mass of a crosslinking agent (tert-butyl peroxy 2-ethylhexyl carbonate; Trigonox 117 manufactured by Kayaku Akzo Co., Ltd.)
(3) 2 parts by mass of a crosslinking aid (triallyl isocyanurate; Nippon Kasei Corporation TAIC (registered trademark)),
(4) 0.5 parts by mass of a silane coupling agent (γ-methacryloxypropyltrimethoxysilane; manufactured by Shin-Etsu Chemical Co., Ltd., KBM503)
(5) 0.3 part by mass of an ultraviolet absorber (2,2′-dihydroxy-4,4′-dimethoxybenzophenone).

3. Preparation of heat ray shielding layer A composition containing the following components is applied onto a polyethylene terephthalate (PET) film (thickness: 100 μm) using an applicator, dried, and irradiated with ultraviolet light at an accumulated light amount of 500 mJ / cm ² using a high-pressure mercury lamp. By irradiation, a heat ray shielding layer (thickness 8 μm) was produced on the PET film.

(Composition of heat ray shielding layer forming composition)
(1) 100 parts by mass of pentaerythritol triacrylate,
(2) 5 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals),
(3) 20 parts by mass of Cs _0.33 WO ₃ (average particle size 80 nm), and (4) 200 parts by mass of methyl isobutyl ketone.

4). Preparation of intermediate film and heat ray shielding laminated glass First, an intermediate film was obtained by sandwiching a heat ray shielding layer formed on a PET film between a light receiving surface side adhesive resin layer and a back surface side adhesive resin layer. The order of lamination of each member in the intermediate film was in the order of the back-side adhesive resin layer, the heat ray shielding layer, the PET film, and the light-receiving surface-side adhesive resin layer.

Next, the interlayer film was further sandwiched between two glass substrates (thickness 3 mm). The obtained laminate was subjected to temporary pressure bonding by heating at 100 ° C. 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, the adhesive resin layer was cured to obtain a heat ray shielding laminated glass (FIG. 3) in which the transparent base material and each layer were bonded and integrated.

(Example 2)
A heat ray-shielding laminated glass was produced in the same manner as in Example 1 except that the amount of the ultraviolet absorber was changed from 0.3 parts by mass to 0.4 parts by mass in the production of the back surface side adhesive resin layer.

(Example 3)
In the production of the back side adhesive resin layer, the blending amount of the ultraviolet absorber was changed from 0.3 part by mass to 0.1 part by mass. Except having changed from 5 mass parts to 0.4 mass parts, it carried out similarly to Example 1, and produced the heat ray shielding laminated glass.

Example 4
In the production of the back side adhesive resin layer, the blending amount of the ultraviolet absorber was changed from 0.3 part by mass to 0.2 part by mass. Except having changed from 5 mass parts to 0.4 mass parts, it carried out similarly to Example 1, and produced the heat ray shielding laminated glass.

(Example 5)
A heat ray-shielding laminated glass was produced in the same manner as in Example 1 except that in the production of the light-receiving surface side adhesive resin layer, the blending amount of the ultraviolet absorber was changed from 0.5 parts by mass to 0.4 parts by mass.

(Reference Example 1)
A heat ray-shielding laminated glass was produced in the same manner as in Example 1 except that in the production of the light-receiving surface side adhesive resin layer, the blending amount of the ultraviolet absorber was changed from 0.5 parts by mass to 0.3 parts by mass.

(Reference Example 2)
A heat ray-shielding laminated glass was produced in the same manner as in Example 1 except that in the production of the back surface side adhesive resin layer, the blending amount of the ultraviolet absorber was changed from 0.3 parts by mass to 0.5 parts by mass.

(Comparative Example 1)
A heat ray-shielding laminated glass was produced in the same manner as in Example 1 except that the ultraviolet absorber was not used in the production of the back surface side adhesive resin layer.

(Comparative Example 2)
A heat ray-shielding laminated glass was produced in the same manner as in Example 1 except that the amount of the ultraviolet absorber was changed from 0.3 parts by mass to 0.15 parts by mass in the production of the back surface side adhesive resin layer.

(Comparative Example 3)
A heat ray-shielding laminated glass was produced in the same manner as in Example 1 except that in the production of the back side adhesive resin layer, the blending amount of the ultraviolet absorber was changed from 0.3 parts by mass to 1.0 part by mass.

(Comparative Example 4)
A heat ray-shielding laminated glass was produced in the same manner as in Example 1 except that in the production of the back surface side adhesive resin layer, the blending amount of the ultraviolet absorber was changed from 0.3 parts by mass to 2.0 parts by mass.

(Evaluation)
The following evaluation was performed about the heat ray shielding laminated glass produced as mentioned above. The results are shown in Table 1.

1. Compatibility of UV absorber in backside adhesive resin layer In order to evaluate the compatibility of UV absorber in the backside adhesive resin layer, visual evaluation of the backside adhesive resin layer and measurement of haze value were performed.

  Regarding the visual appearance evaluation of the back surface side adhesive resin layer in Table 1, “O” indicates that the back surface side adhesive resin layer is not cloudy, and “X” indicates that the back surface side adhesive resin layer is cloudy. .

  The haze value of the back surface side adhesive resin layer was measured using a fully automatic direct reading haze computer HGM-2DP (manufactured by Suga Test Instruments Co., Ltd.) according to the method of JIS K 7105 (1981).

2. Absorbance of near-infrared light (wavelength: 800 nm) Using an accelerated weathering tester (Xenon Weather Meter X75, manufactured by Suga Test Instruments Co., Ltd.) on the heat ray-shielded laminated glass obtained in Examples and Comparative Examples, the temperature was 58 ° C. In this atmosphere, ultraviolet rays having a wavelength of 300 to 400 nm were irradiated at an intensity of 60 W / m ² for 5000 hours. Moreover, irradiation of ultraviolet rays was performed from the surface side where the light-receiving surface side adhesive resin layer of the heat ray shielding laminated glass is disposed.

  About the heat ray shielding laminated glass before and after the accelerated weathering test, the absorbance of near-infrared light (wavelength 800 nm) was measured with a spectrophotometer UV3100PC (manufactured by Shimadzu Corporation). As the absorbance of near-infrared light decreases, the heat-shielded laminated glass also turns blue.

3. Total light transmittance An accelerated weather resistance test was performed on the heat ray-shielded laminated glass obtained in the examples and comparative examples in the same manner as described above.

  The total light transmittance in the thickness direction of the heat-shielding laminated glass before and after the accelerated weathering test was measured using a fully automatic direct reading haze computer HGM-2DP (manufactured by Suga Test Instruments Co., Ltd.).

  In the heat ray shielding laminated glasses of Comparative Examples 1 and 2, the color changed to blue after the accelerated weather resistance test, and the absorbance and the total light transmittance were greatly reduced. In the heat ray shielding laminated glasses of Comparative Examples 3 and 4, the compatibility of the ultraviolet absorber in the back surface side adhesive resin layer was low, and white turbidity was generated. On the other hand, in the heat ray shielding laminated glasses of Examples 1 to 5, although the amount of the ultraviolet absorber used is small, in addition to white turbidity, a decrease in absorbance and total light transmittance due to discoloration to blue occurs. It never happened.

110, 210, 310: heat ray shielding layer,
120A, 220A, 320A: light-receiving surface side adhesive resin layer,
120B, 220B, 320B: back side adhesive resin layer,
130, 230, 330: Plastic film,
340: Transparent substrate.

Claims (7)

An intermediate film for heat ray shielding laminated glass comprising a heat ray shielding layer containing tungsten oxide and / or composite tungsten oxide sandwiched between a light receiving surface side adhesive resin layer and a back surface side adhesive resin layer,
The light receiving surface side adhesive resin layer and the back surface side adhesive resin layer include an adhesive resin and an ultraviolet absorber,
The content of the ultraviolet absorber in the light-receiving surface-side adhesive resin layer, is 0.4 to 1.0 part by mass with respect to the adhesive resin 100 parts by weight,
The content of the ultraviolet absorber in the back side adhesive resin layer is 0.1 to 0.9 parts by mass with respect to 100 parts by mass of the adhesive resin ,
The content (U _L ) of the ultraviolet absorber, which is the mass part of the ultraviolet absorber with respect to 100 parts by mass of the adhesive resin in the light receiving surface side adhesive resin layer , and the ultraviolet ray with respect to 100 parts by mass of the adhesive resin in the back surface side adhesive resin layer. the difference between the content of the ultraviolet absorber is a mass of the absorbent _{(U B) (U L -U} B) is, Ri 0.1-0.3 der,
The ultraviolet absorber is represented by the following formula (I):

[However, R ¹ represents a hydrogen atom or a hydroxyl group, R ² represents a hydrogen atom or a hydroxyl group, and R ³ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 14 carbon atoms, or a carbon atom. Represents an alkoxy group having 1 to 14 carbon atoms , and R ⁴ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 14 carbon atoms, or an alkoxy group having 1 to 14 carbon atoms]. UV absorber, and
The interlayer film for heat ray-shielding laminated glass , wherein the adhesive resin is an ethylene vinyl acetate copolymer .   2. The intermediate film for heat ray shielding laminated glass according to claim 1, wherein the heat ray shielding layer formed on the plastic film is sandwiched between the light receiving surface side adhesive resin layer and the back surface side adhesive resin layer. .   The said plastic film is arrange | positioned adjacent to the said light-receiving surface side adhesive resin layer, The intermediate film for heat ray shielding laminated glasses of Claim 2 characterized by the above-mentioned. The said light-receiving surface side adhesive resin layer and the said back surface side adhesive resin layer contain an organic peroxide, The intermediate film for heat ray shielding laminated glasses of any one of Claims 1-3 characterized by the above-mentioned. Tungsten oxide is represented by the general formula WyOz (where W is tungsten, O represents oxygen and 2.2 ≦ z / y ≦ 2.999), and the composite tungsten oxide is represented by the general formula MxWyOz. (However, 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, 1 or more elements inner shell selected in I, W is tungsten, O represents oxygen, and 0.001 ≦ x / y ≦ 1,2.2 ≦ z / y ≦ 3 any of claims 1-4, characterized by being represented by a is) Heat ray shielding laminated glass intermediate film according to item 1. The said heat ray shielding layer contains at least 1 type of binder resin selected from the group which consists of a fluororesin, a silicone resin, and an acrylic resin, The heat ray shielding match | combination of any one of Claims 1-5 characterized by the above-mentioned. Intermediate film for glass. The heat ray shielding laminated glass by which the intermediate film for heat ray shielding laminated glasses of any one of Claims 1-6 is pinched | interposed between two transparent base materials, and these are adhere | attached and integrated.

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