JP2000063158A - Laminated glass and interlayer used therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide both a laminated glass having a high visible light transmittance and transparency and excellent in durability and an interlayer used therefor. SOLUTION: This interlayer is obtained by dispersing the below-mentioned zinc oxide-based grains in a cured product thereof and the laminated glass comprises at least two sheets of transparent plates and the resin interlayer sandwiched between the two sheets of the transparent plates. The resin interlayer contains the above interlayer. The zinc oxide-based grains contain a metal element (Md) taking a valence of 3 and/or 4 and Zn as metal components, manifest X-diffractometric zinc oxide crystallinity and satisfy Ds(002)/Ds(100)<2 when the size of crystallites in the vertical direction Ds(hkl) is determined for two lattice planes (100) and (002) by using the Scherrer method (Cauchy function approximation) and further satisfy 1<Dw<30 (nm) when the size of the crystallites determined by using the Wilson method is Dw.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet / infrared ray-impermeable laminated glass and an intermediate film used for the same.

[0002]

2. Description of the Related Art A combination of at least two glass plates and a resin intermediate layer sandwiched between these two glass plates, in which particles for shielding infrared rays and ultraviolet rays are dispersed in the intermediate resin layer. Glass is used for vehicle window glasses for automobiles, railways, aircrafts, etc., architectural window glasses, crime prevention glass, and the like. For example, Japanese Unexamined Patent Publication No. 8-217500 discloses a laminated glass in which a soft resin intermediate layer containing a metal oxide infrared blocking agent and an organic ultraviolet absorber is sandwiched between two glass plates.

This known laminated glass is expensive because it uses tin oxide, indium oxide or the like as an infrared ray blocking agent, and in addition, a metal oxide reacts with an organic ultraviolet absorber to form a chelate compound. There was also a problem that the intermediate layer was formed and colored or clouded. This known laminated glass also has a problem that it has a low durability against ultraviolet rays and infrared rays at the initial stage, but has a low durability because the action of the ultraviolet absorber gradually deteriorates.

[0004]

The problem to be solved by the present invention is to provide a laminated glass and an interlayer film which have high visible light transmittance and transparency and are excellent in durability.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor has provided an intermediate film made of a cured resin obtained by curing a curable composition in a resin intermediate layer. The inventors have found that by dispersing zinc oxide-based particles having high monodispersity, which have been developed previously, in this interlayer film, both ultraviolet rays and infrared rays can be blocked, and the present invention has been completed.

That is, the ultraviolet / infrared ray impermeable intermediate film for laminated glass according to the present invention is characterized in that it contains an intermediate film in which the following zinc oxide type particles are dispersed in a resin cured product. The laminated glass is a laminated glass including at least two transparent plates and a resin intermediate layer sandwiched between the two transparent plates, wherein the resin intermediate layer includes the intermediate film according to the present invention. To do.

Zinc oxide-based particles: Zinc oxide crystallinity is observed by X-ray diffraction using a metal element (Md) having a valence of 3 and / or 4 and Zn as metal components, and two lattice planes (10
0) and (002) using the Scherrer method (Cauchy function approximation), the crystallite size Ds in the vertical direction
When (hkl) is determined, Ds (002) / Ds (100) <2 is satisfied, and when the crystallite size determined by the Wilson method is Dw, 1 <Dw <30 (nm) Zinc oxide-based particles that satisfy the requirements.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The laminated glass according to the present invention is
Including a transparent plate and a resin intermediate layer sandwiched between the transparent plates,
The resin intermediate layer includes an intermediate film in which zinc oxide particles are dispersed in a cured resin. Therefore, in the following, first, other particles that are used in combination with zinc oxide-based particles as an essential component and as needed are described, and then, intermediates obtained by dispersing the zinc oxide-based particles and other particles in a cured product. The membrane will be explained and finally the laminated glass will be explained. [Zinc oxide-based particles and other dispersed particles] In the present invention,
Zinc oxide-based particles and other dispersed particles are dispersed in the intermediate film and block infrared rays and ultraviolet rays by absorbing them. In the present invention, the dispersed particles include zinc oxide-based particles described below as essential particles, but in addition to this, tin oxide-based particles (for example, 0.1 to 20 mol% of Sb (V) (vs. S).
n) Doped SnO ₂ ), indium oxide based particles (for example, Sn (IV) 0.1 to 20 mol% (vs. In))
Doped In ₂ O ₃ ), anhydrous zinc antimonate particles, cadmium stannate particles, etc., having an average particle size of 0.1 μm or less, and infrared shielding ultrafine particles; titanium oxide, zinc oxide, cerium oxide, etc., having an average particle size of 0.1 μm The following ultra-violet ray-shielding ultrafine particles may be used in combination.

The zinc oxide type particles used as essential particles in the present invention exhibit infrared ray non-transmittance, conductivity, etc. in addition to the ultraviolet ray non-transparency and visible light transmissivity which are inherent to the zinc oxide type particles. The zinc oxide based particles contain a metal element (Md) having a valence of 3 and / or a valence of 4 and Zn as metal components. The content of Md is preferably 0.1 to 20%, more preferably 1 to 10%, further preferably 2 to 8% in terms of the ratio of the number of Md atoms to the total number of atoms of the metal component. ,
Most preferably, it is 3 to 6%. If it exceeds the above range, it becomes difficult to form fine particles having high uniformity in composition, crystal size, etc.,
When it is less than the above range, the infrared ray blocking property (infrared ray non-transmissivity) including heat rays becomes insufficient.

As the additive element Md, B, Al,
II such as Ga, In, Tl, C, Si, Ge, Sn, Pb
In addition to Group IB and Group IVB elements, Sc, Y, Ti, Z
r, Hf, V, Nb, Ta, Cr, Mo, W, Mn, T
c, Re, Fe, Rv, Os, Rh, Ir, La, C
e, Sb and the like. The zinc oxide-based particles are required to exhibit zinc oxide crystallinity by X-ray diffraction, and it is preferable that the primary particles of the zinc oxide-based particles are dispersed without secondary aggregation.

The dispersed particle diameter Dd of the zinc oxide type particles is 0.5, which has a high transparency and does not substantially affect the hue of the composition containing the zinc oxide type particles, and the infrared ray shielding efficiency.
It is preferably μm or less. More preferably 0.1
It is less than or equal to μm, and more preferably less than or equal to 0.05 μm.
It is particularly preferably 0.03 μm or less. It is preferable that the monodispersity is high in terms of transparency and infrared ray shielding property. The monodispersity is defined by the ratio R (Dd / Dw) of the crystallite diameters Dw and Dd, and R is preferably 10 or less, more preferably 3 or less, and particularly preferably 1.5 or less. .

The dispersed particle size is a weight-based average particle size which can be measured by a dynamic light scattering method, a centrifugal sedimentation method or the like. If it is less than 0.1 μm, change the former value to 0.1 μm.
When it is m or more, it is measured by the latter measuring device. As the zinc oxide particles, the polymer constitutes the matrix,
The matrix includes particles in which particles are dispersed (polymer composite particles). When the particles are hollow, light diffusion and transmission properties are excellent. The content of zinc oxide-based particles in these particles is not particularly limited, but is preferably in the range of 1 to 90% by weight based on the total amount of composite particles in terms of zinc oxide.

The polymer used for the compounding is an acrylic resin-based polymer, an alkyd resin-based polymer, an amino resin-based polymer, a vinyl resin-based polymer, an epoxy resin-based polymer, a polyamide resin-based polymer, a polyimide resin-based polymer, a polyurethane resin-based polymer. Polymer, polyester resin-based polymer, phenol resin-based polymer, organopolysiloxane-based polymer, acrylic silicone resin-based polymer, polyalkylene glycol, etc., polyolefin-based polymer such as polyethylene, polypropylene, polystyrene-based polymer, fluororesin-based heat, etc. Plastic or thermosetting resin; synthetic rubber such as ethylene-propylene copolymer rubber, polybutadiene rubber, acrylonitrile-butadiene rubber or natural rubber; polysiloxane group-containing polymer, etc. It can be mentioned.

The shape of the composite particles is preferably spherical or ellipsoidal. It is preferable that the surface be rich in unevenness regardless of the outer shape of the particles. This is because if the surface is uneven, the coating film containing the composite particles has a high affinity with the binder component and the like. The average particle size of the composite particles is not particularly limited, but is usually 0.0
It is in the range of 01 to 10 μm.

The zinc oxide particles are treated with a surface modifier for the purpose of improving dispersibility and dispersion stability in the interlayer film, reducing the photocatalytic activity of zinc oxide, and imparting weather resistance. It may be one that has been. As the preferable surface modifier, the above-mentioned polymers can be used, but for the purpose of imparting weather resistance, a compound containing an MX group can be mentioned. However, X is at least one selected from the group consisting of an alkoxy group, an acyloxy group, a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a β-dicarbonyl group (ligand), and a β-ketoester group (ligand). And M
Is preferably a metal element, especially at least one selected from the group consisting of Si, Ti, Zr, and Al. From the viewpoint of imparting dispersibility (dispersibility in paints and solvents, stability of paints, etc.), polymers having organic polymer chains are mentioned. What is preferable in terms of both weather resistance and dispersibility is a polymer containing an MX group and having an organic polymer chain, and examples thereof include a polysiloxane group-containing polymer and acrylic silicone.

The zinc oxide particles have a monovalent or divalent metal element Ma of 0.0000 in terms of the atomic ratio of Ma to Md.
It is preferable to include in the range of 1 ≦ Ma / Md <1. 0.
The range of 0001 ≦ Ma / Md ≦ 0.4 is more preferable. The atomic ratio to zinc is 0.0001-
It is preferably in the range of 2%. The existence effect of Ma is
The point is that Md is homogeneously (in a more monomeric state) contained in the ZnO crystal, the crystal surface is stabilized, and secondary aggregation and coarse crystal growth are suppressed. Therefore, fine crystals having high monodispersity are obtained. Therefore, it is possible to increase the Md amount and improve the infrared ray blocking property while having excellent transparency. If the amount of Ma is too small, the effect is not exhibited, and if the amount of Ma is too large, the weather resistance of the coating film containing the particles may decrease. Monovalent or divalent metal element M
a is an alkali metal element and / or an alkaline earth metal element, and examples thereof include lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, and barium.

The zinc oxide type particles are composed of ions and / or atoms of halogen elements other than F (that is, chlorine Cl, bromine Br, iodine I), sulfate SO ₄ ^2- and nitrate N.
O ₃ ^- total content of (hereinafter also referred to as impurities H) is the number of atoms to zinc (However, in the case of the sulfate S
The number of atoms of, and in the case of nitrate radicals, it is calculated as the number of atoms of N)
The ratio is preferably 0.5% or less. It is more preferably 0.1% or less, still more preferably 0.01% or less, and particularly preferably 0.001% or less. This includes the case where the impurity H is not contained at all. Only when the impurity H is not contained, or when the impurity H is contained, if the content does not exceed this range, particles having excellent infrared ray blocking properties can be obtained.

The zinc oxide type particles used in the present invention also show diffraction peaks on the lattice planes (100), (002) and (101), which are diffraction peaks peculiar to crystalline zinc oxide. It is important that the particles satisfy the child parameters. Using the Cauchy function approximation (Cauchy function approximation) by the Scherrer method (Scherrer method), the crystallite size Ds in the direction perpendicular to each diffraction surface (hkl)
When (hkl) is calculated, Ds (002) / Ds (10
0) <2 is satisfied. More preferably Ds (002) /
Ds (100) <1.2, more preferably 0.5 <D
s (002) / Ds (100) <1.0. Especially D
s (002) / Ds (100) <0.75 is preferable.
This is because when it is in this range, the infrared ray blocking property is excellent.

When the size of the crystallite obtained by the Wilson method is Dw, 1 <Dw <30 (n
m) is satisfied. More preferably 5 <Dw <20 (n
m), more preferably 5 <Dw <17 (nm), and most preferably 5 <Dw <15 (nm). Dw
If it is too small, the ultraviolet absorptivity and the infrared ray blocking property are lowered, and if it is too large, the transparency to visible light is lowered. D
From the viewpoint of blocking infrared rays, w preferably has a large crystallite, and from the viewpoint of visible light transparency, it is preferably small. Dw
Is preferable in that the two properties can be balanced. When Dw is in the above range, transparency,
It has excellent infrared blocking properties and ultraviolet absorption properties.

When the lattice strain of the crystallite obtained by the Wilson method is Aw, it is preferable that 0 ≦ Aw ≦ 1 (%) is satisfied, and 0 ≦ Aw ≦ 0.5 (%) is further preferable. When Aw is in the above range, it is considered that Md is contained more monomerically, but the infrared ray blocking property is the highest. The shape and particle size of the zinc oxide-based particles used in the present invention are not particularly limited.

Specific examples of the shape are spherical, elliptic spherical,
Cubic shape, rectangular parallelepiped shape, pyramid shape, needle shape, columnar shape, rod shape, cylindrical shape, flaky shape, (hexagonal) plate shape, and other flaky shape are exemplified, but the crystallite morphology is in the above range, That is, it is preferably flaky. The zinc oxide-based particles used in the present invention have a carboxyl residue (carboxylic acid group) of carboxylic acid in a weight ratio to ZnO of 0.
It is preferably contained in an amount of 01 to 10%, more preferably 0.1 to 5%. The presence of the carboxylic acid group on the surface of the particles suppresses secondary agglomeration and increases the transparency when used as a paint. On the other hand, when there are too many carboxylic acid groups, the infrared ray blocking property is deteriorated. When the amount of the carboxylic acid group is within the above range, both the monodispersity and the infrared ray shielding performance are excellent. Further, the zinc oxide-based particles have a carbonate group as ZnO.
It may be contained in a range of 10% or less, preferably 3% or less by weight ratio to.

Next, a method for producing the zinc oxide type particles used in the present invention will be described. As a method for producing the zinc oxide based particles used in the present invention, for example, the zinc oxide based particles are precipitated by heating a solution (S) containing a Zn compound, a compound of Md and, if necessary, a compound of Ma. There is a method. Examples of the Zn compound used in the method for producing zinc oxide-based particles include metallic zinc (zinc dust), zinc oxide (zinc white), zinc hydroxide, basic zinc carbonate, zinc acetate, and the like. Are preferable because they are inexpensive and easy to handle. Zinc oxide, zinc hydroxide, and zinc acetate do not substantially contain impurities that inhibit the reaction of forming zinc oxide crystals in the heating process, and it is easy to control the size and shape of crystals and particles. Therefore, it is more preferable. Zinc oxide produced by the vapor phase method (French method, American method) is particularly preferable. Not only is zinc oxide obtained by the vapor phase method available at a low price,
It is particularly preferable because even if it contains, it is extremely small.

Examples of the metal (Md) compound used in the method for producing zinc oxide-based particles include metal, oxide, hydroxide, carbonate (including acidic and basic carbonate) and acetate of metal Md. Besides, alkoxide compounds, β-diketone compounds, and the like can be cited. In all of these, the organometallic compounds containing no impurities H have less impurities H,
It is preferable in that it does not occur.

Examples of the metal (Ma) compound used in the method for producing zinc oxide-based particles include metal, oxide, hydroxide, carbonate (including acidic and basic carbonate) of metal Ma, and acetate. In addition to these, there can be mentioned organometallic compounds containing no impurity H such as alkoxide compounds and β-diketone compounds, and all of them are preferable in that they contain little or no impurities H.

The solution (S) preferably contains a monocarboxylic acid compound and an alcohol. The monocarboxylic acid compound is a compound having only one carboxyl group in the molecule. Specific examples of the compound include, for example, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, etc., all of which are preferable because particles having excellent monodispersity can be easily obtained. The saturated fatty acid is preferably used in the range of 60 to 100 mol% and more preferably in the range of 80 to 100 mol% based on the total amount of the monocarboxylic acid compound. If the amount is less than the above range, the crystallinity of zinc oxide in the obtained particles may be low.

The monocarboxylic acid compound is the Md compound M
The molar ratio to d is preferably 50 to 200 times. Also,
The molar ratio to Zn is preferably 1.90 times or more and 8 times or less. This is because it is easy to obtain particles having excellent monodispersibility and excellent infrared ray blocking performance. Alcohols used in the method for producing zinc oxide-based particles include aliphatic monohydric alcohols (methanol, ethanol, isopropyl alcohol,
n-butanol, t-butyl alcohol, stearyl alcohol, etc.), alicyclic monohydric alcohol (cyclopentanol, cyclohexanol, etc.), aromatic monohydric alcohol (benzyl alcohol, cinnamyl alcohol, methylphenylcarbinol, etc.), Monocyclic alcohols such as heterocyclic monohydric alcohols (furfuryl alcohol, etc.); alkylene glycols (ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6- Hexanediol, 1,8-octanediol, 1,10-decanediol, pinacol, diethylene glycol, triethylene glycol, etc.), aliphatic glycols having an aromatic ring (hydrobenzoin, benzpinacol, phthalyl alcohol, etc.) Alicyclic glycols (cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol), polyoxyalkylene glycols (polyethylene glycol, polypropylene glycol, etc.) glycols such as;
Propylene glycol monoethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, triethylene glycol monomethyl ether, Derivatives of monoethers and monoesters of the above glycols such as ethylene glycol monoacetate; hydroquinone, resorcin, 2,2
Aromatic diols such as bis (4-hydroxyphenyl) propane and their monoethers and monoesters; trihydric alcohols such as glycerin and their monoethers, monoesters, diethers and diesters. These alcohols are used alone or in combination of two or more.

The alcohol is preferably used in an amount of 1 to 30 times, and more preferably 15 to 25 times the weight of the charged Zn compound in terms of zinc oxide. Also,
The molar ratio of alcohol to monocarboxylic acid compound is 1
It is preferably 10 times. In the solution (S), Ma
By containing the compound (1) in the range of less than 1 (preferably less than 0.4) in the atomic ratio (Ma / Md) of Ma of Ma compound to Md of Md compound contained in the solution (S). It is possible to easily obtain zinc oxide-based particles containing various Ma. By coexisting Ma, metal Md
Regardless of the amount (addition ratio to zinc), fine particles having excellent monodispersity can be obtained. Furthermore, due to the manufacturing method, M
The amount of the solvent necessary for obtaining the solution (S) containing the d compound and the Zn compound can be reduced, and therefore the desired zinc oxide-based particles can be obtained under economically excellent conditions.

From the point of monodispersibility of the obtained particles, the coexistence of Ma varies depending on the type of metal Md when the amount of metal Md relative to Zn is high, but when Md is IIIB group or IVB group, Md / Zn ( When the atomic ratio) is 3% or more and Md is other than the above, it is particularly effective when Md / Zn (atomic ratio) is 1% or more. As a preferred method for preparing the solution (S), an Md compound is uniformly dissolved in a solvent in advance, and the obtained solution (Sa) and a zinc compound or a liquid containing the zinc compound (which may be a solution or a suspension) are prepared. Method of Mixing to Obtain Solution (S) Containing Md and Zinc The Md compound and a part of the zinc compound were dissolved in advance in a solvent to obtain a solution (Sb) and the remaining zinc compound or zinc. Examples include a method of mixing a liquid containing a compound (which may be a solution or a suspension) to obtain a solution (S) containing Md and zinc. For the above reason, the Ma compound may be added when necessary when preparing Sa or when it is preparing Sb.
In order to obtain the above solution (Sa, Sb), it is possible to usually heat at 50 ° C. or higher, and it is preferable to heat at a reflux temperature. In addition, as a suitable solvent used for Sa and Sb, one or a mixture of two or more of the above-mentioned monocarboxylic acid, an anhydride of this monocarboxylic acid, water, the above-mentioned alcohol and the like can be mentioned.

Further, the solution (S), preferably 150
By heating to ˜200 ° C. and precipitating zinc oxide-based particles, it is easy to obtain a dispersion liquid of particles having a uniform crystallite size and no aggregation. The obtained dispersion is further stored in a closed container under a non-oxidizing atmosphere in which the gas portion atmosphere has an oxygen concentration of 1% or less, preferably 0.1% or less.
By performing the heat treatment at a temperature of 0 ° C. or higher and lower than 400 ° C. for 1 minute or longer and within 24 hours, particles having higher crystallinity and higher infrared ray blocking properties can be obtained. Heat treatment temperature is 220 ~
By setting the temperature in the range of 300 ° C., particles having particularly excellent monodispersity can be obtained. In addition, when the atmosphere is an oxidizing atmosphere, the infrared ray blocking property may be deteriorated, which is not preferable.

The total content of impurities H in the solution (S) is
The ratio of the number of atoms to zinc (however, the number of S atoms in the case of sulfate radicals is calculated as the number of atoms of N in the case of nitrate radicals) is 0.5% or less, more preferably 0.1% or less, and further 0. By setting the content to be 0.01% or less, and particularly 0.001% or less, the zinc oxide-based particles having a small amount of the impurity H as described above can be easily obtained. Of course, the case where the solution (S) does not contain the impurity H at all is included.

The solution (S) contains a carbonate in an amount of 0.001 to 5% by mole ratio of CO _{3 to} Zn of the Zn compound contained in the solution (S), whereby the photocatalytic activity is suppressed. It is also possible to obtain fine particles. According to the above manufacturing method, Ds (002) / Ds (100) <2, especially 0.5
<Ds (002) / Ds (100) <1.0; 1 <Dw
<30 (nm), especially 5 <Dw <15 (nm); Aw ≦
1, particularly 0 ≦ Aw ≦ 0.5 (%) is satisfied, and the impurity H is 0.5% or less in atomic ratio to zinc, preferably 0.1.
% Or less of particles can be obtained. [Intermediate film] The intermediate film according to the present invention is obtained by curing a curable composition, and is formed by dispersing dispersed particles such as zinc oxide particles described above in a cured body of a resin. As described in detail later, the curable composition has a curable compound and zinc oxide-based particles as essential components, and when the curable compound is cured, it binds dispersed particles such as zinc oxide-based particles to provide weather resistance. , Is a component that forms an intermediate film having excellent adhesion and durability.

In this way, since the binder is a resin cured product, the interlayer film has a low solubility in a solvent at room temperature.
It is extremely lower than the curable compound as the raw material, and for example, the curable compound before curing selected from water, methanol, isopropyl alcohol, methyl ethyl ketone, toluene, etc. is 10% by weight even at 20 ° C. The above-mentioned film has no solubility in the solvent to be dissolved at room temperature. It can be said that this cured film is a film that exhibits substantially no solubility. The solubility here is, for example, by immersing the intermediate film in the solvent and comparing the dissolution rate thereof with that of the curable compound before being cured, or by rubbing the intermediate film with absorbent cotton impregnated with the solvent (usually 50%). Evaluation is performed by rubbing back and forth), and the presence or absence of peeling of the interlayer film due to dissolution is observed, and the judgment is made.

As a method for curing the curable composition,
Although it is not particularly limited, examples thereof include heat curing, moisture curing, and ultraviolet curing, and among these, heat curing and moisture curing are preferable. Examples of the curable compound that is cured by heat curing or moisture curing include acrylic polymers, polyurethane polymers, polyester polymers, fluorine polymers, vinyl polymers having reactive groups having active hydrogen such as hydroxyl groups and amino groups. And reactive group-containing polymers such as These reactive group-containing polymers can be cured with heat and / or moisture using polyisocyanates as curing agents.

As the above-mentioned reactive group, a hydroxyl group is preferable and the durability of the interlayer film is enhanced. The amount of the reactive group in the reactive group-containing polymer is not particularly limited, but is preferably 0.1 to 10 mmol, and more preferably 0.3 to 6 mmol per 1 g of the reactive group-containing polymer.
As the acrylic polymer, for example, a copolymer having (meth) acrylic acid and its ester as a main component of the main chain; a copolymer of (meth) acrylic acid ester, (meth)
A thermoplastic acrylic polymer such as a copolymer of an acrylic ester and a polymerizable monomer such as a vinyl monomer (styrene, vinyl ester, etc.); (meth) acrylic acid, (meth) as a monomer constituting the thermoplastic acrylic polymer
A thermosetting acrylic polymer, such as a hydroxyalkyl ester of acrylic acid or a glycidyl ester of (meth) acrylic acid, to which a cross-linking agent component or a heat curing component is added; styrene other than (meth) acrylic monomers, vinyltoluene, acetic acid Copolymer modified with a monomer such as vinyl; epoxy-curable acrylic polymer using an acrylic monomer having basic nitrogen as a copolymerization component and an epoxy compound as a crosslinking agent component; acrylic polymer having an oxidative polymerization function, etc. And one or more of these are used.

Examples of the polyurethane-based polymer include oil-modified type, moisture-curable type, heat-curable type, lacquer-type one-pack type polyurethane polymer; polyol-curable type (various polyols such as acrylic polyol, polyester polyol, polyether polyol and the like. And a isocyanate prepolymer), a two-component polyurethane polymer such as a catalyst-curing type, and the like, and one or more of these are used.

Examples of the fluorine-based polymer include polymers having a hydroxyl group introduced, such as an alternating copolymer of fluoroolefin and hydroxyalkyl vinyl ether represented by the following general formula (1).

[0037]

[Chemical 1]

(Wherein X is at least one selected from a halogen atom, a perfluoroalkyl group and a perfluoroalkoxy group having 1 to 3 carbon atoms; R ^a and R ^c are both a hydrogen atom or a methyl group; R ^b is an optionally substituted fluorine-substituted alkyl group having 1 to 12 carbon atoms; R ^d is an optionally substituted fluorine-substituted alkyl group having a hydroxyl group;
w, x, and y are all integers of 1 or more; z is 0
Or 1. As the vinyl-based polymer, for example, polyvinyl chloride, a vinyl chloride polymer such as a copolymer of vinyl chloride and another compatible monomer (vinyl acetate, a lower fatty acid vinyl ester such as vinyl propionate, vinylidene chloride, etc.); Polyvinyl acetate, vinyl acetate polymers such as copolymers of vinyl acetate and other polymerizable monomers (ethylene, propylene, styrene, acrylic ester, vinyl propionate, vinylidene chloride, etc.); polyvinyl alcohols of various saponification degrees, Various modifications (silicone modification, carboxyl modification, amino modification, epoxy modification, mercapto modification, etc.), polyvinyl alcohol polymers such as polyvinyl alcohol; polyvinyl butyral, vinyl butyral and other polymerizable monomers (vinyl alcohol, vinyl acetate, etc.) Butler for coalescing And the like, and one or more of them may be used.

As the polyisocyanate, for example,
Tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, naphthylene-1,5-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,
Diisocyanates such as 4′-diisocyanate; adducts of tolylene diisocyanate with trimethylolpropane, adducts of hexamethylene diisocyanate with trimethylolpropane, trimethylolpropane adducts of the above diisocyanates with adduct of isophorone diisocyanate with trimethylolpropane; Isocyanurate modified products of the above diisocyanates such as isocyanurate modified tolylene diisocyanate, isocyanurate modified hexamethylene diisocyanate, isocyanurate modified isophorone diisocyanate; Biuret modified products of the above diisocyanates such as biuret modified hexamethylene diisocyanate; Body, isocyanurate modified product, biuret modified product, etc. Modified and polymerized modified products; alcohols, phenols, oximes of isocyanate groups in the above diisocyanates, trimethylolpropane adducts, isocyanurate modified products, biuret modified products, prepolymerized and polymerized modified products And block-type polyisocyanates protected with active methylene compounds and the like, and one or more of them are used.

The curable compound which is cured by heat or moisture may be a compound other than the reactive group-containing polymer,
For example, condensable metal compounds, metal (hydr) oxide sols;
The M-OR ¹ group-containing polymer described below and the like can be mentioned. The condensable metal compound is a metal compound capable of being hydrolyzed and / or condensed, and examples thereof include organometallic compounds such as metal alkoxides and metal acyloxys, and derivatives thereof such as (partial) hydrolysis condensates. These are used alone or in combination of two or more.

As the metal alkoxides, compounds represented by the following general formula (2) are preferable. M (OR ¹ ) _mn R ² _m (2) (wherein M is a metal atom; R ¹ is a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group, an acyl group, an aralkyl group or an aryl group; at least one member selected; R ² is hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group, an acyl group, an aralkyl group, an aryl group, at least one selected from unsaturated aliphatic residues
Species; n is the valence of the metal atom M, 3 or 4; m
Is an integer in the range of 0 to 3. In the general formula (2), R ¹ is a hydrogen atom and / or an optionally substituted alkyl group, and R ² is an optionally substituted alkyl group, cycloalkyl group, acyl group or aralkyl group. , At least one selected from an aryl group and an unsaturated aliphatic residue,
¹ is a hydrogen atom and is at least one member selected from methyl and ethyl, more preferred. Also, M
Is preferably aluminum, zirconium or silicon, more preferably silicon.

Degree of condensation in metal alkoxides and derivatives thereof such as (partial) hydrolysis condensates (M-O in one molecule)
The number of bonds) is preferably 1 to 1000. As the composition of the metal alkoxides, when M has a valence of n,
The molar ratio of M (OR ¹ ) _n : R ² M (OR ¹ ) _n-1 : R ² ₂ M
(OR ¹ ) _n-2 = 100: 0 to 10000: 0 to 1000
Is preferred.

As the metal (hydr) oxide sol, silica sol, alumina sol, zirconia sol and the like are preferable and they are excellent in transparency, colorlessness and durability. Among these, silica sol is more preferable. When the metal (hydr) oxide sol is used as the curable compound, it may be used alone, but 10 parts of the metal alkoxide and its (partial) hydrolysis condensate per 100 parts by weight of the metal (hydr) oxide sol may be used. ~
It is preferable to use 1000 parts by weight together, and the intermediate film becomes a tough film.

In the M-OR ¹ group-containing polymer, the crosslinking point of the polymer is represented by the general formula M-OR ¹ (wherein R ¹ is a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group, an acyl group, At least one selected from an aralkyl group and an aryl group; M is a metal atom). However, the condensate, which is a derivative of a binding metal compound or a metal (hydr) oxide sol, is
Excluded from polymers containing M-OR ¹ groups.

R ¹ of the M-OR ¹ group is preferably a hydrogen atom and / or an optionally substituted alkyl group, more preferably a hydrogen atom and / or an alkyl group having 1 to 4 carbon atoms. As M of the M-OR ¹ group, at least one selected from silicon, aluminum and zirconium is preferable, and silicon is more preferable.

Examples of the M-OR ¹ group include a trimethoxysilyl group, a dimethoxysilyl group and a monomethoxysilyl group. The number of OR ¹ groups bonded to M is 1 to M. It is in the range of up to 1 less. The M-OR ¹ group-containing polymer contains an alkoxysilyl group and / or a silanol group, and the main chain is composed of an element mainly containing carbon.

Examples of the main chain of the M-OR ¹ group-containing polymer include main chains composed of polyurethane-based polymers, acrylic-based polymers, polyester-based polymers, polyurethane-based polymers, fluorine-based polymers, vinyl-based polymers and the like. Of these, a main chain made of an acrylic polymer is preferable, and a polymer having a number average molecular weight of 100,000 or less is more preferable,
What is 30,000 is the most preferable. M-OR ¹ group-containing acrylic polymer (acrylic silicone polymer)
As, the alkoxysilyl group may be present as one alkoxysilyl group bonded to the polymer,
Those in which an alkoxy group is present at a plurality of silicon atoms in a polysiloxane chain such as a poly (dialkoxy) siloxane chain are also included.

The cross-linking point of the M-OR ¹ group-containing polymer is M
It may be other than the —OR ¹ group and may be a reactive functional group such as a hydroxyl group, a carboxyl group, an amino group and an epoxy group.
When the cross-linking point of the polymer is a reactive functional group, M-O
It is also possible to form a crosslink by reacting with the R ¹ group, or when a curing agent that reacts with a reactive functional group such as polyisocyanate is used together, crosslinking due to a Si—O—Si bond and a reactive functional group and a curing agent are performed. It is possible to obtain an interlayer film in which crosslinking due to

Next, the curable composition used in the present invention will be described. The proportion of the zinc oxide-based particles in the curable composition is not particularly limited, but is preferably 3 with respect to the total solid content of the zinc oxide-based particles and the curable compound.
0 to 90% by weight, more preferably 40 to 80% by weight,
Most preferably, it is 50 to 75% by weight. If the proportion of zinc oxide-based particles is less than 30% by weight based on the total solid content, it is necessary to coat the thick film in order to obtain sufficient ultraviolet and infrared ray impermeability of the intermediate film. , Special coating method and equipment are required. On the other hand, when the proportion of zinc oxide-based particles exceeds 90% by weight, the weather resistance of the obtained interlayer film,
Adhesion and transparency may decrease. In order to improve this problem, it is preferable to preliminarily surface-modify the zinc oxide-based particles with the surface-hand modifier.

The curable composition may contain a solvent and is appropriately selected depending on the type of curable compound. Examples of the solvent include the solvent used in the dispersion containing zinc oxide-based particles described below. The curable composition used in the present invention has a curing catalyst such as the above-mentioned cross-linking agent, curing agent and curing aid, a plasticizer, a defoaming agent / leveling agent, a thixotropic agent, a matting agent, and an interface according to the required performance. Activator;
Flame retardant; Pigment wetting agent / dispersant; Lubricant; UV absorber; Light stabilizer; Antioxidant; Other (heat) stabilizer; Antiseptic agent; Antifungal agent; Antialgae agent; Anticorrosion / rust inhibitor; Dye; It may further contain an additive such as a pigment. When the curable composition used in the present invention further contains a light stabilizer, the weather resistance is improved.

The method for producing the curable composition is not particularly limited. For example, a curable compound is mixed with a dispersion containing dispersed particles such as the above zinc oxide particles, and the above additives are further added as appropriate. Examples thereof include a method of mixing. The dispersion containing zinc oxide-based particles contains zinc oxide-based particles and a solvent as essential components. The zinc oxide-based particles are preferably contained in a proportion of 2 to 80% by weight in terms of metal oxide based on the total amount of the dispersion. Especially 20
-60% by weight is preferred.

As the solvent used in the dispersion, water, alcohols, ketones, aliphatic and aromatic carboxylic acid esters, ethers, ether esters, aliphatic and aromatic hydrocarbons, halogenated compounds, etc. In addition to hydrocarbons, mineral oils, vegetable oils, wax oils, silicone oils and the like can be mentioned, and one or more of these solvents are used.

From the viewpoint of versatility, preferred solvents are alcohols, aliphatic and aromatic hydrocarbons, halogenated hydrocarbons, which have a boiling point of 40 ° C. to 250 ° C. under normal pressure,
Aromatic and aliphatic carboxylic acid esters, ketones,
It is one or more mixed solvents selected from (cyclic) ethers, ether esters and water. Examples of the solvent include methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol,
Ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3-methyl-3-methoxybutanol, 3- Chill-3-methoxybutyl acetate, toluene, xylene, benzene, cyclohexane,
Examples thereof include n-hexane, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, water and the like, and these solvents are used alone or in combination of two or more.

The interlayer film of the present invention can be produced by applying a curable composition to a transparent plate or an adhesive layer and then curing the composition. The method for applying the curable composition is not particularly limited, and includes dipping method, roll coater method, flow coat method, screen printing method, bar coater method, knife coater method, spin coater method, brush coating method, spray method, and the like. Can be mentioned. An intermediate film is obtained by applying the curable composition and then curing the composition. The curing method is not particularly limited, and examples thereof include heat curing (including room temperature curing), moisture curing, ultraviolet curing, electron beam curing, and the like. By curing in this manner, water resistance; solvent resistance Properties: chemical resistance such as acid resistance and alkali resistance; scratch resistance; physical properties such as durability are improved.

The thickness of the intermediate film is not particularly limited, but is preferably 0.01 to 200 μm, more preferably 0.5 to 50 μm, and most preferably 2 to 20 μm. [Laminated glass] Laminated glass has at least two transparent plates. As shown in FIG. 1, these two transparent plates 1,
The resin intermediate layer 2 is sandwiched between 1 and 2. The resin intermediate layer 2 is composed of the above-mentioned intermediate film 4 and the adhesive layer 5. The intermediate film 4 is formed by dispersing particles 3 for blocking infrared rays and ultraviolet rays in a hardened body. The dispersed particles 3 essentially include the zinc oxide type particles described above, and if necessary, 50
In the range of less than wt%, functional particles other than zinc oxide particles, pigments, etc. are also included. Examples of the functional particles and dyes include organic UV absorbers such as benzotriazole compounds; UV absorbing ultrafine particles such as titanium oxide, cerium oxide, zinc oxide; heat ray absorbing dyes such as phthalocyanine compounds. I can give you.

The intermediate film 4 may be formed on at least one surface of the transparent plate 1 and / or the adhesive layer 5. Usually, as shown in FIG. 1, an intermediate film is present at the interface between the transparent plate 1 and the adhesive layer 5, and for example, an intermediate film is formed on either one of the two transparent plates, and the surface on which the film is formed is formed. The laminated glass having the structure shown in FIG. 1 can be manufactured by superposing it on the adhesive layer. Further, an intermediate film can be present in the adhesive layer, and for example, it can be produced by forming an intermediate film at the interface between two adhesive layers and sandwiching it between two transparent plates.

The transparent plate 1 is not particularly limited and may be a glass plate or an organic resin plate such as an acrylic plate or a polycarbonate plate. These transparent plates
For example, it may have heat resistance and / or a function of blocking ultraviolet rays, such as heat ray reflective glass. As described above, the thickness of the intermediate film 4 is not particularly limited, but is preferably 0.01 to 200 μm, more preferably 0.5.
˜50 μm, most preferably 2 to 20 μm.

The adhesive layer 5 is also not particularly limited,
For example, polyvinyl butyral type, polyurethane type,
Ethylene-vinyl acetate copolymer system, ethylene- (meth)
Examples thereof include soft resins such as acrylic acid ester polymer system and hard resins. The thickness of the adhesive layer 5 is preferably 0.01 to 5 mm, more preferably 0.02.
~ 1 mm. When the transparent plate is glass, it is more preferably 0.1 to 2 mm, and most preferably 0.5 to.
It is 1 mm. On the other hand, when the transparent plate is an organic resin plate, it is more preferably 0.02 to 1 mm.

The laminated glass according to the present invention is not particularly limited, but is preferably 70% or more, more preferably 75%.
As described above, the most preferable visible light transmittance is 80% or more. The visible light transmittance is a value measured in the range of wavelengths of 380 to 780 nm and calculated using the spectral transmittance of each wavelength range and the weighting coefficient of each wavelength according to the method described in JIS R 3106-1985. . Here, the spectral transmittance is obtained by using a spectrophotometer that satisfies the conditions described in 3.2 and 4.2 of JIS R 3106-1985, and is used for measuring the spectroscopic measurement rate. Is
For simplicity, for example, an integrating sphere accessory (ISR-31
00, manufactured by Shimadzu Corporation) can be used as a self-recording spectrophotometer (UV-3100) attached to the sample chamber.

The laminated glass according to the present invention is not particularly limited, but preferably has a haze value of less than 3%, more preferably less than 2%, most preferably less than 1%. The haze value indicates the degree of transparency and is a value measured by a turbidimeter. The laminated glass according to the present invention is not particularly limited, but it is preferable to block ultraviolet rays having a wavelength of 360 nm or less (transmittance of 5% or less at a wavelength of 360 nm or less), and to block ultraviolet rays having a wavelength of 370 nm or less. It is more preferable that the transmittance at a wavelength of 370 nm or less is 5% or less.

The laminated glass according to the present invention has an infrared transmittance of 70% or less, more preferably 60% or less, most preferably 50% or less, although not particularly limited. The infrared transmittance is determined according to JIS R31 using the spectral transmittance of light in the wavelength range of 800 to 1800 nm and the weighting coefficient of each wavelength (the same weighting coefficient as used when calculating the solar radiation transmittance).
It is a value calculated according to the method described in 06-1985.

The laminated glass according to the present invention, like the conventional laminated glass, has ultraviolet rays and infrared rays (including heat rays).
Is difficult to permeate through, and is used, for example, as a window material for automobiles and trains, a window material for buildings, and the like. For reference, the above-mentioned four physical properties are shown for the interlayer film according to the present invention. The interlayer film according to the present invention is not particularly limited, but is preferably 7
5% or more, more preferably 80% or more, most preferably 85%
% Or more, preferably less than 3%, more preferably less than 2%, most preferably less than 0.5%, preferably 50% or less, more preferably less than 3%. It preferably has a UV transmittance of 20% or less, most preferably 10% or less, 7
0% or less, more preferably 60% or less, most preferably 50%
It has an infrared transmittance of not more than%.

[0063]

EXAMPLES Examples of the present invention will be shown below together with comparative examples, but the present invention is not limited to the following examples.
In addition, "%" means "weight%" and "part" means "weight part". Examples were prepared by preparing zinc oxide-based particles in Reference Examples 1 (1) to 1 (4) below, and then preparing zinc oxide-based particle-containing dispersions in Reference Examples 2 (1) to 2 (11). And used in Comparative Examples.

The zinc oxide type particles prepared in the following reference examples were evaluated by the following methods. Fine Particle Composition The composition of the metal component of the fine particles was determined by fluorescent X-ray analysis, atomic absorption analysis, plasma emission analysis, gravimetric analysis and elemental analysis. The fine particles were obtained by vacuum-drying a methyl ethyl ketone dispersion at 80 ° C. The halogen element content other than the amount F of the impurity H in the fine particles was determined by fluorescent X-ray analysis of the fine particles, and the nitrate radical and sulfate radical contents were determined by ion chromatographic analysis in the same manner as the analysis of the carboxyl group content. Crystallinity of fine particles It was evaluated by crystal X-ray diffraction. Crystallite size of fine particles, Ds
(Hkl), Dw, and lattice strain Aw were also obtained from powder X-ray diffraction measurement of fine particles.

Ds (hkl): Crystallite diameter Dw in the direction perpendicular to each diffraction plane (hkl) by the Scherrer method (by Cauchy function approximation), Aw: Crystallite size obtained by using the Wilson method And Lattice Distortion In the following examples and comparative examples, as the initial properties of the interlayer film and the laminated glass, transmission / blocking properties (visible light transparency, ultraviolet light blocking properties, infrared light blocking properties) and transparency (visible light transparency). Was evaluated. Further, its durability and curability were also evaluated. These were measured as follows. [Initial Characteristics] Visible Light Transmittance According to the method described in JIS R 3106-1985, the visible light transmittance T _V is calculated by using the spectral transmittance in each wavelength range and the weighting coefficient of each wavelength to calculate the visible light transmittance. Was evaluated according to the following evaluation criteria. ◯: T _V ≧ 70% ×: T _V <70% UV blocking property The spectral transmittance was measured, and when the transmittance at a wavelength of 360 nm was less than 10%, it was evaluated as ◯, and 10% or more was evaluated as ×. Infrared ray blocking property According to the method described in JIS R 3106-1985, the solar radiation transmittance T _h is calculated using the spectral transmittance of each wavelength range and the weighting coefficient of each wavelength, and the infrared ray blocking property is evaluated according to the following evaluation criteria. did.

The above-mentioned spectral transmittance is obtained by using an integrating sphere accessory (IS
R-3100 (manufactured by Shimadzu Corporation) was used for measurement using a self-recording spectrophotometer (UV-3100) attached to a sample chamber. ◯: T _h ≦ 70% ×: T _h > 70% Visible light transparency Commercially available turbidimeter (Nippon Denshoku Industries Co., Ltd., NDH-1001
The haze value was measured using DP), and based on the haze value H (%), the following evaluation criteria were used for evaluation. ○: H (%) <1% ×: H (%) ≧ 1% [Durability] Transparency Using a sunshine carbon arc lamp type light resistance and weather resistance tester described in JIS B 7753-93, accelerated weathering The sex test was performed for 1000 hours, the haze change ΔH was measured, and the evaluation was performed according to the following evaluation criteria. ⊚: ΔH ≦ 0.5% ○: 0.5% <ΔH ≦ 1% ×: 1% <ΔH (where ΔH = H−H ₀ , H ₀ : haze value before weather resistance test, H: weather resistance After the test, the haze value and ΔH were evaluated as ⊚ when the value was negative.) Discoloration The hue before and after the weather resistance test was visually evaluated according to the following evaluation criteria. A: No coloring or discoloration is observed. B: Coloring and discoloration are slightly observed. C: Coloring and discoloration are considerably observed. [Curing] Water, methanol, isopropyl alcohol,
A solvent selected from methyl ethyl ketone, toluene, etc., which dissolves the curable compound at 10% by weight or more at 20 ° C., is rubbed with the absorbent cotton impregnated with the solvent (rubbing 50 times). Then, the presence or absence of peeling of the interlayer film due to dissolution was observed and evaluated according to the following evaluation criteria.
For the intermediate film using the binders (B1) to (B9), methyl ethyl ketone was used as the solvent, and for the intermediate film using the binders (B10) to (B11), methanol was used as the solvent. ◯: No dissolution peeling is observed. Δ: Dissolution peeling is recognized (partial peeling). X: Almost entirely dissolved and exfoliated.

Reference Example 1 (1) -In a 20-liter glass reactor equipped with a stirrer, a dropping port, a thermometer, a distillate gas outlet and a nitrogen gas inlet, 2400 parts of acetic acid and 1800 parts of ion-exchanged water. A mixture of 488 parts of zinc oxide (French method zinc oxide), 60 parts of indium hydroxide (content of indium oxide 78.5% by weight) and 0.69 part of sodium acetate was heated at 100 ° C. for 5 hours to obtain a uniform mixture. A solution (S1) was obtained.

Next, the temperature of the solution (S1) was raised while flowing nitrogen from the nitrogen gas inlet, and the internal temperature was raised to 170 ° C. while distilling a part of the volatile components in the solution, Thirty
Hold for a while, then raise the temperature in a sealed state at 250 ° C for 10
In-containing ZnO ultrafine particles (P
8100 parts of the dispersion liquid (D1a) of 1) was obtained. -Reference Examples 1 (2) to 1 (4) -Reference Example 1 except that the kinds of raw materials and the composition of the raw materials were changed.
In the same manner as in (1), dispersions (D2a) to (D) in which ZnO ultrafine particles (P2) to (P4) containing each metal Md are dispersed.
4a) was obtained.

The dispersions (D1a) to (D4a) were centrifuged to obtain a cake. Each cake was washed with 10 volumes of acetone, dried in vacuum at 60 ° C. for 12 hours, and analyzed. The results are shown in Table 1.

[0070]

[Table 1]

-Reference Example 2 (1) -The dispersion liquid (D1a) obtained in Reference Example 1 (1) was centrifuged to obtain a cake (C1). The cake (C1) was dispersed in a toluene-methylethylketone (7: 3) mixed solvent, and the In-containing ZnO ultrafine particles (P1) had an oxide concentration of 50.
A solvent dispersion (D1) dispersed in a weight percentage was obtained.

-Reference Examples 2 (2) to 2 (11) -Dispersions (D2a) to (D) in the same manner as in Reference Example 2 (1).
4a) to solvent dispersions (D2) to (D1), respectively.
1) was obtained. Table 2 shows the type of dispersion liquid, the type of solvent, and the oxide concentration of each solvent dispersion.

[0073]

[Table 2]

-Example 1- Solvent dispersion (D1) 150 obtained in Reference Example 2 (1)
Parts, acrylic binder (B1) shown in Table 3 (solid content concentration 40% by weight, solvent: toluene-methyl ethyl ketone (7: 3)) 88 parts, polyisocyanate compound (isocyanurate-modified hexamethylene disisocyanate,
NCO group content 23.1% by weight) 5 parts and toluene 7
The parts were mixed to prepare a curable composition (C1).

Next, the curable composition (C1) was applied to one surface of a transparent glass plate using a bar coater and dried under the conditions shown in Table 7, and an ultrafine particle dispersion film (dry film thickness) as an intermediate film was obtained. A film-coated glass (g1) on which 10 μm) was formed was obtained. A PVB resin sheet (containing 30% by weight of dioctyl phthalate and having a thickness of 0.7 mm) as an adhesive layer was laminated so as to be sandwiched between this film-coated glass (g1) and a transparent glass prepared separately. Here, the film-coated glass (g
The membrane of 1) and the PVB resin sheet were superposed. After laminating, holding under reduced pressure at 100 ° C. for 1 hour, returning to normal temperature, putting in an autograve, and processing for 30 minutes at a pressure of 8 kg / cm ² and a temperature of 130 ± 7 ° C. to obtain a laminated glass (G1 ) Was produced.

Table 8 shows the evaluation results of the obtained laminated glass (G1). The laminated glass (G1) shielded infrared rays and ultraviolet rays including heat rays, and had extremely excellent transparency (haze 0.3% or less) and weather resistance. The curability was ◯. -Examples 2 to 11-The solvent dispersions (D) obtained in Reference Examples 2 (2) to 2 (11).
Curable compositions (C2) to (C11) were prepared using 2) to (D11), respectively. Tables 3 and 4 show the physical properties of the binder used for preparing the curable composition, and Tables 5 and 6 show the solvent dispersion, binder, curing agent or curing catalyst, solvent and the like used.

Then, in the same manner as in Example 1, the curable compositions (C2) to (C11) were used to obtain film-coated glasses (g2) to (g11) under the drying conditions shown in Table 7. . In addition,
Table 7 also shows the film thickness of the film-coated glasses (g2) to (g11). Each of the resin sheets (thickness 0.7 mm) shown in Table 7 as the adhesive layer was coated with the film-coated glass (g2) to
(G11) and the separately prepared transparent glass were laminated so as to be sandwiched. Here, the film of the film-coated glass and each resin sheet were superposed. After the superposition, the laminated glasses (G2) to (G1) are treated in the same manner as in Example 1, respectively.
1) was produced.

The obtained laminated glass (G2) to (G11)
Table 8 shows the evaluation results. The curability was good in all cases. -Comparative Example 1-Reference Example 2 The solvent dispersion (D4) obtained in (4) and Table 4
A non-curable composition (CC1) was prepared using the binder (CB1) shown in 1 above. The composition is shown in Table 6.

Using the non-curable composition (CC1), a film-coated glass (cg1) and a laminated glass (CG1) were obtained in the same manner as in Example 1. Table 7 shows the drying conditions after the non-curable composition (CC1) was applied and the type of the resin sheet as the adhesive layer. Table 8 shows the evaluation results of the obtained laminated glass (CG1). Curability is ×
Met.

[0080]

[Table 3]

[0081]

[Table 4]

[0082]

[Table 5]

[0083]

[Table 6]

[0084]

[Table 7]

[0085]

[Table 8]

[0086]

EFFECTS OF THE INVENTION The ultraviolet-infrared ray non-transmissive interlayer film for laminated glass according to the present invention has high visible light transparency and transparency, does not transmit ultraviolet rays and infrared rays, and is excellent in durability. Since the laminated glass according to the present invention includes the above-mentioned intermediate film, it has high visible light transparency and transparency, can block and block ultraviolet rays and infrared rays, and is excellent in durability.

[Brief description of drawings]

FIG. 1 is a sectional view of a laminated glass according to the present invention.

[Explanation of symbols]

1 transparent plate 2 Resin intermediate layer 3 dispersed particles 4 Intermediate film 5 Adhesive layer

Continued front page    F-term (reference) 4F100 AA25C AA25H AG00A AG00B                       AK01C AK23G AK25G AK51G                       AR00A AR00B BA03 BA06                       BA10A BA10B BA13 CB00                       DE01C DE01H GB90 JD09                       JD10 JL00 JN01 JN01A                       JN01B YY00C YY00H                 4G061 AA20 AA25 BA01 BA02 CB05                       CB12 CB19 CD02 CD18

Claims (4)

[Claims] 1. A laminated glass comprising at least two transparent plates and a resin intermediate layer sandwiched between these two transparent plates, wherein the resin intermediate layer is a resin cured product containing the following zinc oxide based particles. An ultraviolet and infrared non-transparent laminated glass, which comprises an interlayer film in which is dispersed. Zinc oxide-based particles: Zinc oxide crystallinity is exhibited by X-ray diffraction using a metallic element (Md) having a valence of 3 and / or a valence of 4 and Zn as metal components, and two lattice planes (100) and (0
02), when the size Ds (hkl) of the crystallite in the vertical direction is obtained by using the Scherrer method (Cauchy function approximation), Ds (002) / Ds (100) <2 is satisfied, and Wilson Zinc oxide-based particles satisfying 1 <Dw <30 (nm), where Dw is the size of the crystallite obtained by the method. 2. The zinc oxide-based particles, wherein the total content of impurities consisting of ions and / or atoms of a halogen element other than F and sulfate SO ₄ ²⁻ and nitrate NO ₃ ⁻ is an atom based on zinc. The ultraviolet ray according to claim 1, which is a zinc oxide-based particle having a number (however, calculated as the number of S atoms in the case of sulfate radicals and the number of N atoms in the case of nitrate radicals) of 0.5% or less. Infrared non-transparent laminated glass. 3. An intermediate film used to form the resin intermediate layer of a laminated glass comprising at least two transparent plates and a resin intermediate layer sandwiched between the two transparent plates, the resin comprising: An ultraviolet / infrared ray impermeable intermediate film for laminated glass, characterized in that the following zinc oxide-based particles are dispersed in a cured product. Zinc oxide particles: trivalent and / or 4
It has a valence of a metallic element (Md) and Zn as metallic components and exhibits zinc oxide crystallinity by X-ray diffraction, and has two lattice planes (10
0) and (002) using the Scherrer method (Cauchy function approximation), the crystallite size Ds in the vertical direction
When (hkl) is obtained, Ds (002) / Ds (100) <2 is satisfied, and when the crystallite size obtained using the Wilson method is Dw, 1 <Dw <30 (nm) Zinc oxide-based particles that satisfy the requirements. 4. The zinc oxide-based particles, wherein the total content of impurities consisting of ions and / or atoms of halogen elements other than F, and sulfate radical SO ₄ ²⁻ and nitrate radical NO ₃ ⁻ is an atom relative to zinc. The combination according to claim 3, which is a zinc oxide-based particle having a number (however, calculated as the number of S atoms in the case of sulfate radicals and the number of N atoms in the case of nitrate radicals) of 0.5% or less. UV and infrared impermeable interlayer film for glass.