JP6903569B2 - Laminated glass interlayer film, laminated glass and method for manufacturing laminated glass - Google Patents

Description

The present invention relates to an interlayer film for laminated glass suitable for imparting functionality such as heat ray shielding property, conductivity, and decorative pattern to laminated glass.

For laminated glass for construction, laminated glass for surface protection of displays, windshields for automobiles, side glass, etc., a resin layer is provided between two sheets of inorganic glass or organic glass for the purpose of preventing scattering when the glass breaks. Laminated glass is mainly used. The polyvinyl acetal resin mainly used as this resin layer is produced by acetalizing a polyvinyl alcohol resin with an aldehyde. In recent years, organic compounds or inorganic compounds for imparting heat ray shielding properties and design properties, metal mesh pattern layers and transparent metal vapor deposition layers for imparting conductivity, metal vapor deposition layers for light reflection, and light rays have been added to laminated glass. A transparent metal compound film or the like for absorption is arranged.

In order to manufacture laminated glass having heat ray shielding property, conductivity, and design property, a layer having each of these functions is printed on a thin roll-shaped PET film having excellent versatility and economy. It is generally formed by a continuous and economical method such as thermal lamination or vapor deposition, and embedded between a plurality of layers of polyvinyl acetal containing a plasticizer.
In particular, in order to produce a laminated glass having a heat ray shielding property, a method of forming a layer having an IR absorbing property or an IR reflecting property on a thin PET film has been established.
Further, in order to manufacture a laminated glass having a conductive structure in particular, a method of directly printing the conductive structure on a PET film has been established. For example, a heating element or a sensor region that is almost invisible is PET. Can be made on film.
Further, in order to manufacture a laminated glass having a decorative layer such as a printed pattern layer or a semi-transparent vapor deposition layer (half mirror), a method of continuously printing or vapor deposition on a PET film has been established, for example. , A shade band pattern for sunshades, a half-mirror-like metal vapor deposition layer, and each print pattern layer according to the user's preference can be produced on it.

Other than the method using PET film, for example, a method of welding a metal filament to the surface of a standard PVB film in order to produce a laminated glass having heat ray shielding property or conductivity, or a method of welding a metal filament to the surface of a PVB film. There is a method of sewing on the surface, or a method of screen-printing and baking a conductive structure on a glass surface arranged inward in the laminate. However, in these methods, since a PVB film having a Tg lower than that of the PET film is used, the PVB film is plasticized by the heat in the laminating process with the glass, causing a problem that the metal filament is broken, or a thin heat ray shielding film. And the problem of cracks in the decorative layer is likely to occur. Therefore, a method using a PET film is generally used.

However, according to the method using a PET film, since the refractive index of the PET resin and the PVB resin are different, the transparency is likely to be impaired when both are laminated, and the laminated glass has defects such as scratches on the PET film. There was a problem that the defect was easily noticeable when it was set to. Further, in an application in which the PET film is partially used, for example, the laminated glass is partially wired with an antenna or the like, the edge portion of the PET film can be clearly seen through the laminated glass. There was a problem that PET film could not be used in the application.

Furthermore, in 3D-shaped laminated glass, which has been widely used in recent years, PET film has poor followability to 3D shape due to the characteristics of the resin and the film-forming method, and the PET film was used as the base material when manufacturing the laminated glass. There was a problem that the functional layer was prone to wrinkles and breaks and could not be used.

In view of the above problems, PET film makers are also working on the development of PET films with improved moldability. For example, Patent Document 1 describes a stretched PET film having excellent secondary moldability, and Patent Document 2 describes a multi-layer PET film having a reduced shrinkage rate during secondary moldability. .. However, these films have problems that the cost is high, the surface property and transparency of the film itself are inferior, and the refractive index is higher than that of PVB resin, so that the transparency at the time of producing laminated glass is deteriorated.

By the way, the acrylic resin film has features such as high transparency, high rigidity and surface hardness, excellent weather resistance, and easy molding, so it can be used as a display material for signboards, flat panel displays, etc. It is used in various applications such as interior and exterior materials for vehicles classified as decorative films, interior and exterior materials for building materials, and interior materials. In particular, it is used as a skin material for various members because of its excellent surface properties.

However, the acrylic resin film is very brittle and easily cracked in each process during film formation, which makes film formation difficult, and also breaks in the trimming process of unnecessary parts during secondary processing and the bonding process with other films. It is easy to cause problems such as. In order to improve the brittleness of the film made of only the acrylic resin, a method of alloying and blending various materials has been proposed.

For example, Patent Document 3 proposes an acrylic resin film in which core-shell type particles are blended. Further, in Patent Document 4, a block copolymer having at least one structure in which a highly syndiotactic polymethacrylic acid alkyl ester block is bonded to both ends of a thermoplastic resin and a polyacrylic acid alkyl ester block in the molecule. A polymer composition containing the above in a specific ratio has been proposed. Further, in Patent Document 5, a resin composition using a block copolymer having an acrylic acid ester polymer block containing a specific amount of a structural unit derived from an acrylic acid alkyl ester and a structure derived from a (meth) acrylic aromatic ester, respectively. The thing is disclosed.

Japanese Unexamined Patent Publication No. 2010-189593 (Patent No. 5257127) Japanese Unexamined Patent Publication No. 2011-073151 (Patent No. 5564875) Special Publication No. 56-27378 Special Fair 10-168271 Gazette International Publication No. 2014/073216

One of the problems to be solved by the present invention is distortion of the functional layer and deterioration of transparency of the laminated glass, which occurs when a method using a PET film is used when imparting functionality to the laminated glass. It is to provide an interlayer film for laminated glass which can suppress.

One of the problems to be solved by the present invention is to reduce visibility even when a laminated glass interlayer film to which a functional layer is partially provided is used when imparting functionality to the laminated glass. It is to provide an interlayer film for laminated glass without a shaving.

One of the problems to be solved by the present invention is to provide an interlayer film for laminated glass that facilitates use in a laminated glass having a 3D shape that is required to follow the shape.

That is, the present invention has been made in view of the above circumstances, and as a base film for imparting a functional layer to an interlayer film for laminated glass, a tensile storage elasticity E'(40) at 40 ° C. and 100 ° C. E'(100) of tensile storage elasticity and E'(120) of tensile storage at 120 ° C. satisfy the following formulas (1), (2) and (3) to form an interlayer film for laminated glass. By using a thermoplastic resin film having a refractive index difference of 0.05 or less from other different types of resins, a highly transparent laminated glass having a haze of 1.0% or less can be produced. It is an object of the present invention to provide a laminated glass interlayer film that enables partial use of a base film and facilitates use in a laminated glass having a 3D shape that is required to follow the shape. is there.
(1) E'(40) ≥ 1000 MPa
(2) E'(100) ≥ 10 MPa
(3) E'(120) ≤ 10 MPa

According to the present invention, the above object is achieved by providing [1] to [20].
[1]
An interlayer film for laminated glass laminated in the structure of B layer / A layer / B layer or B layer / A layer / C layer.
The refractive index difference between the refractive index of the A layer and the refractive index of the B layer measured based on ASTM D542 and / or the refractive index difference between the refractive index of the A layer and the refractive index of the C layer is 0.05 or less. And
The A layer has a tensile storage elastic modulus E'(40) at 40 ° C., a tensile storage elastic modulus E'(100) at 100 ° C., and a tensile storage elastic modulus E'(120) at 120 ° C. Satisfy (2) and equation (3),
The haze value based on JIS K7136 of the laminated glass in which the interlayer film for laminated glass is sandwiched between two sheets of glass is 1.0% or less.
Laminated glass interlayer film.
(1) E'(40) ≥ 1000 MPa
(2) E'(100) ≥ 10 MPa
(3) E'(120) ≤ 10 MPa;
[2]
The interlayer film for laminated glass according to the above [1], wherein the layer A is made of an acrylic resin composition;
[3]
The interlayer film for laminated glass according to the above [2], wherein the acrylic resin composition contains elastic particles;
[4]
Elastic particles are
The inner layer of at least one layer is a crosslinked thermoplastic polymer layer containing a crosslinked thermoplastic polymer having an acrylic acid alkyl ester monomer unit having an alkyl group having 1 to 8 carbon atoms and / or a conjugated diene-based monomer unit. The outermost layer is an acrylic multilayer structure polymer particle (Y) which is a thermoplastic polymer layer containing a thermoplastic polymer having a methacrylate alkyl ester monomer unit having an alkyl group having 1 to 8 carbon atoms. , The interlayer film for laminated glass of the above [3];
[5]
The interlayer film for laminated glass according to the above [4], wherein the acrylic multilayer structure polymer particles (Y) have a particle size of 0.05 to 0.25 μm;
[6]
The acrylic resin composition contains acrylic multilayer structure polymer particles (Y) and 80% by mass or more of methyl methacrylate units, and the melt flow rate is 0.5 to 10 g / 10 minutes. ), The interlayer film for laminated glass of the above [4] or [5];
[7]
The acrylic resin composition contains a block copolymer (Z) in which a methacrylic acid ester polymer block (z2) is bonded to an acrylic acid ester polymer block (z1), and a methacrylic resin (M).
The melt viscosity (η (Z)) of the block copolymer (Z) at 220 ° C. and a shear rate of 122 / sec is 75 to 1500 Pa · s.
Further, the value of the ratio (η (M) / η (Z)) of the melt viscosity (η (M)) to the melt viscosity (η (Z)) of the methacrylic resin (M) at 220 ° C. and a shear rate of 122 / sec. The interlayer film for laminated glass according to the above [2], wherein is 1 to 20;
[8]
The amount of the acrylic resin composition is 70 to 99 parts by mass of the methacrylic resin (M) and the block copolymer (Z) 1 with respect to 100 parts by mass of the total of the methacrylic resin (M) and the block copolymer (Z). The interlayer film for laminated glass according to the above [7], which contains ~ 30 parts by mass;
[9]
The interlayer film for laminated glass according to the above [7] or [8], wherein the methacrylic resin (M) contains 80% by mass or more of methyl methacrylate units and the melt flow rate is 0.5 to 10 g / 10 minutes;
[10]
The interlayer film for laminated glass according to the above [1] to [9], wherein the arithmetic mean roughness (Ra) of at least one surface of the layer A is 0.15 μm or less;
[11]
The interlayer film for laminated glass according to the above [1] to [10], wherein the layer A contains metal oxide fine particles having a heat ray-shielding function;
[12]
The interlayer film for laminated glass according to [1] to [10], which has a functional coating layer on the surface of layer A;
[13]
The interlayer film for laminated glass according to the above [12], wherein the functional coating layer is a heat ray-shielding coating having a thickness of 0.001 μm to 10 μm;
[14]
The interlayer film for laminated glass according to the above [1] to [10], which has a conductive structure on the surface of the A layer;
[15]
The interlayer film for laminated glass according to the above [14], which has a conductive structure on the surface of the A layer, and the conductive structure is formed by a printing method, an etching method, or a thin film deposition method.
[16]
The laminated glass interlayer film of the above [14] or [15], wherein the conductive structure contains at least one of gold, silver, copper or a metal oxide;
[17]
The above [1] to [16], wherein the B layer and / or the C layer contains at least one resin selected from polyvinyl acetal resin, ionomer, ethylene vinyl acetate, vinyl chloride resin, urethane resin, silicone resin and polyamide resin. Laminated glass interlayer film;
[18]
A laminated glass formed by sandwiching the interlayer film for laminated glass of [1] to [17] between two sheets of glass.
[19]
Production of laminated glass for producing laminated glass by sandwiching layer A having at least one or more functions of heat ray shielding property, conductivity or decoration between at least two layers B or at least layers B and C. It ’s a method,
The refractive index difference between the refractive index of the A layer and the refractive index of the B layer measured based on ASTM D542 and / or the refractive index difference between the refractive index of the A layer and the refractive index of the C layer is 0.05 or less. And
The tensile storage elastic modulus E'(40) at 40 ° C., the tensile storage elastic modulus E'(100) at 100 ° C., and the tensile storage elastic modulus E'(120) at 120 ° C. of the layer A are the formulas (1) and (1). A method for producing a laminated glass according to 2) and the formula (3).
(1) E'(40) ≥ 1000 MPa
(2) E'(100) ≥ 10 MPa
(3) E'(120) ≤ 10 MPa

By using the interlayer film for laminated glass according to the present invention, distortion of the functional layer and deterioration of transparency of the laminated glass caused by the method of using the PET film as the base film of the functional layer are suppressed, and followability to the shape is required. It is possible to use it for a laminated glass having a 3D shape, and it is possible to use a partial functional layer by partially using a base film.

This is an example of a cross-sectional view of the structure of the laminated glass laminate according to the present invention. This is an example of the shape of the 3D-shaped laminated glass laminate according to the present invention. This is an example of a schematic diagram in which the base film according to the present invention is partially used.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the present embodiment.

[Layer A]
The interlayer film for laminated glass of the present invention contains at least one layer A having a tensile storage elastic modulus E'satisfying the formulas (1), (2) and (3). The type of film constituting the A layer is not particularly limited as long as it satisfies the scope of the claims of the present invention, and in addition to the acrylic film, a PVA film, a PVB film, an ionomer film, a POM film, a PP film, etc. However, an acrylic film is preferably used as the A layer from the viewpoints of cost, long-term light resistance, transparency, and good processability when processed as laminated glass. These films may be unstretched films or stretched films. Unless otherwise stated, film means unstretched film.

Further, as the layer A, any one can be used as long as it satisfies the above conditions, but it may be a single layer film composed of a single thermoplastic resin composition, or a plurality of thermoplastic resin compositions. It may be a multilayer film in which layers made of objects are laminated.

Further, the layer A may be an alloy resin in which different resins are mixed at the time of melt kneading. For example, it may be an alloy resin obtained by melt-kneading a maleic acid-modified acrylic resin and an acrylic resin for the purpose of modifying the resin in order to improve the adhesiveness with the functional layer, the B layer, or the C layer. However, it may be a resin using a maleic acid-modified acrylic resin alone.

As a method for measuring the tensile storage elastic modulus E', for example, a viscoelastic spectrometer (SII EXSTAR6000 series DMS6100 manufactured by SII Nanotechnology Co., Ltd.) can be used. The measurement is performed under the following conditions in accordance with JIS K7244-4: 1999 (Plastic-Dynamic Mechanical Properties Test Method Part 4: Tensile Vibration-Resonance Method). First, both ends of the measurement sample are attached to the chuck so that the tension direction is the longitudinal direction of the measurement sample, a tensile load (static load 150 mg) is applied, a constant frequency of 10 Hz in a tension mode sine wave, and a temperature rise rate of 5 ° C. The tensile storage elastic modulus is measured from 0 ° C. to 200 ° C. at / min. At this time, the tensile storage elastic modulus E'(40) at 40 ° C., the tensile storage elastic modulus E'(100) at 100 ° C., and the tensile storage elastic modulus E'(120) at 120 ° C. are the equations (1) and (1). Examples of the method for producing a film satisfying the 2) and the formula (3) include a method of using an acrylic resin composition containing elastic particles in the A layer. The elastic particles have cross-linking elasticity in which at least one inner layer contains a cross-linked elastic polymer having an acrylic acid alkyl ester monomer unit having an alkyl group having 1 to 8 carbon atoms and / or a conjugated diene-based monomer unit. It is a polymer layer, and the outermost layer is preferably a thermoplastic polymer layer containing a thermoplastic polymer having a methacrylate alkyl ester monomer unit having an alkyl group having 1 to 8 carbon atoms.
Further, as a method for producing a film satisfying the formulas (1), (2) and (3), a methacrylic acid ester polymer block (z2) is added to the acrylic acid ester polymer block (z1) as the A layer. Examples thereof include a method using an acrylic resin composition containing the bound block copolymer (Z) and a methacrylic resin (M). In this case, the block copolymer (Z) has a melt viscosity (η (Z)) of 75 to 1500 Pa · s at 220 ° C. and a shear rate of 122 / sec, and the methacrylic resin (M) is sheared at 220 ° C. The value of the ratio (η (M) / η (Z)) of the melt viscosity (η (M)) to the melt viscosity (η (Z)) at a speed of 122 / sec is preferably 1 to 20.

The tensile storage elastic modulus E'(40) of the layer A is 1000 MPa or more, preferably 900 MPa or more, and more preferably 800 MPa or more. When the tensile storage elastic modulus E'(40) of the A layer is less than 1000 MPa, the rigidity of the film in practical use is insufficient and the handleability is deteriorated, and a functional layer is provided on the A layer by a processing method such as printing or etching. It causes deterioration of process passability in the process to be performed. The tensile storage elastic modulus E'(100) of the layer A is 10 MPa or more, preferably 30 MPa or more, and more preferably 50 MPa or more. If the tensile storage elastic modulus E'(100) of the A layer is less than 10 MPa, the A layer causes thermal sagging when it is processed into a laminated glass, which causes distortion or breakage of the functional layer. The tensile storage elastic modulus E'(120) of the layer A is 10 MPa or less, preferably 9 MPa or less, and more preferably 8 MPa or less. When the tensile storage elastic modulus E'(120) of the A layer is larger than 10 MPa, the A layer is not sufficiently softened when it is processed into a laminated glass, so that the followability to the 3D-shaped glass is deteriorated and the wrinkles of the functional layer are deteriorated. It may cause a break.

The arithmetic mean roughness (Ra) of at least one surface of the A layer before laminating the A layer with the B layer or the C layer is preferably 0.5 μm or less. The arithmetic mean roughness (Ra) is more preferably 0.45 μm or less, and further preferably 0.3 μm or less. When the arithmetic mean roughness Ra exceeds 0.5 μm, the transparency of the laminated glass after processing tends to deteriorate. As a method for setting the arithmetic mean roughness (Ra) to 0.15 μm or less, for example, in the step of forming a film by a melt extrusion film forming method using a T-die, two sufficiently smooth cooling rolls are used. A nip film formation method that imparts mirror properties by sandwiching a film discharged from a die, or a cast film formation method that forms a film discharged from a die on a roll using a sufficiently smooth cooling roll. The law etc. can be mentioned.

The arithmetic mean roughness Ra can be measured using a laser microscope. The arithmetic mean roughness Ra can be obtained as the average value of the individual arithmetic average roughness (Ra) measured at any five points on the film surface, and this value is expressed in μm. Details can be measured according to JIS B0601: 2001.

The thickness of the A layer is preferably 15 μm or more, and more preferably 30 μm or more. The thickness of the layer A is preferably 500 μm or less, more preferably 300 μm or less.

Any acrylic film can be used as long as it satisfies the above conditions, but an acrylic film formed of an acrylic resin composition containing elastic particles is preferably used, and in particular, an acrylic film is used. An acrylic film formed of an acrylic resin composition (R1) in which a multilayer structure polymer particles (Y) and a methacrylic resin (M) are mixed at an arbitrary ratio is preferably used. The acrylic resin composition (R1) may contain any additive.

Any acrylic film can be used as long as it satisfies the above conditions, but it is a block copolymer in which a methacrylic acid ester polymer block (z2) is bonded to an acrylic acid ester polymer block (z1). An acrylic film formed of an acrylic resin composition (R2) in which Z) and a methacrylic resin (M) are mixed at an arbitrary ratio is also preferably used. The acrylic resin composition (R2) may contain any additive.

(Acrylic multilayer structure polymer particles (Y))
As the acrylic multilayer structure polymer particles (Y) contained in the acrylic film, known ones can be used. From the viewpoint of impact resistance and the like, as the acrylic multilayer structure polymer particles (Y), at least one inner layer (layer inside the outermost layer) is an acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms. A crosslinked thermoplastic polymer layer containing a crosslinked thermoplastic polymer having a monomer unit and / or a conjugated diene-based monomer unit, and the outermost layer is a single amount of a methacrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms. Acrylic multilayer structure polymer particles (Y), which is a thermoplastic polymer layer containing a thermoplastic polymer having a body unit, are preferable.

In the crosslinked elastic polymer layer, the content of the resin component derived from the acrylic acid alkyl ester monomer unit having an alkyl group having 1 to 8 carbon atoms and the conjugated diene-based monomer unit is the entire content of the crosslinked elastic polymer layer. It is preferably 50% by mass or more with respect to the mass. The crosslinked elastic polymer layer contained in the crosslinked elastic polymer layer has an acrylic acid alkyl ester monomer unit having an alkyl group having 1 to 8 carbon atoms and a monomer unit other than the conjugated diene-based monomer unit. It may be a thing. Further, the crosslinked elastic polymer layer may contain a polymer other than the crosslinked elastic polymer.

The thermoplastic polymer layer has a resin component derived from a methacrylic acid alkyl ester monomer unit having an alkyl group having 1 to 8 carbon atoms in an amount of 50% by mass or more based on the total mass of the thermoplastic polymer layer. Is preferable. The thermoplastic polymer contained in the thermoplastic polymer layer may have a monomer unit other than the methacrylic acid alkyl ester monomer unit having an alkyl group having 1 to 8 carbon atoms. Further, the thermoplastic polymer layer may contain a polymer other than the thermoplastic polymer.

The acrylic multilayer structure polymer particles (Y) are so-called core / shell structure rubbers in which the inner layer of one or more layers including at least one crosslinked elastic polymer layer is covered with the outermost thermoplastic polymer layer. It is a particle.
In the acrylic multilayer structure polymer particles (Y), in the crosslinked elastic polymer layer constituting at least one inner layer excluding the outermost layer, the molecular chain of this layer and the molecular chain in the adjacent layer are bonded by a graft bond. It is preferable that it is.

Examples of the acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms used in the crosslinked elastic polymer layer include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and propyl acrylate. And so on. Examples of the conjugated diene-based monomer used in the crosslinked elastic polymer layer include 1,3-butadiene, isoprene and the like.

For the crosslinked elastic polymer layer, an acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms and / or a conjugated diene-based monomer, or a vinyl-based monomer copolymerizable with these may be used. .. Examples of copolymerizable vinyl-based monomers include methacrylic acid esters, aromatic vinyl compounds, and polyfunctional monomers.
In the present specification, the "polyfunctional monomer" is a monomer having two or more polymerizable functional groups.

From the viewpoint of impact resistance and the like of the interlayer film for laminated glass of the present invention, the acrylic acid alkyl ester unit having an alkyl group having 1 to 8 carbon atoms and / or the conjugated diene-based monomer unit in the crosslinked elastic polymer layer is used. The content of the derived resin component is preferably 60% by mass or more, more preferably 70% by mass or more, based on the total mass of the crosslinked elastic polymer layer.

In the acrylic multilayer structure polymer particles (Y), examples of the methacrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms used in the outermost thermoplastic polymer layer include methyl methacrylate and ethyl methacrylate. , Propyl methacrylate, butyl methacrylate, cyclohexyl methacrylate and the like. From the viewpoint of dispersibility of the acrylic multilayer structure polymer particles (Y), the content of the resin component derived from the methacrylic acid alkyl ester monomer unit in the thermoplastic polymer layer is the total mass of the thermoplastic polymer layer. On the other hand, it is preferably 70% by mass or more, and more preferably 80% by mass or more.

The number of layers of the acrylic multilayer structure polymer particles (Y) is not particularly limited, and is two layers, three layers, or four or more layers. From the viewpoint of thermal stability and productivity, it is particularly preferable that the acrylic multilayer structure polymer particles (Y) have a three-layer structure.

The acrylic multilayer polymer particle (Y) contains a methyl methacrylate unit, an acrylic acid alkyl ester unit having an alkyl group having 1 to 8 carbon atoms, and a polyfunctional monomer unit from the center side. A crosslinked elastic material containing a first layer composed of a crosslinked resin layer, an acrylic acid alkyl ester unit having an alkyl group having 1 to 8 carbon atoms, a methyl methacrylate unit (optional component), and a polyfunctional monomer unit. 3 Consists of a second layer composed of layers and a third layer (outermost layer) composed of a hard thermoplastic resin layer containing a methyl methacrylate unit and an acrylic acid alkyl ester unit having an alkyl group having 1 to 8 carbon atoms. Layered polymer particles (Y1) are preferred. The crosslinked resin layer of the first layer contains 30 to 99.99% by mass of methyl methacrylate units, 1 to 69.99% by mass of acrylic acid alkyl ester units having an alkyl group having 1 to 8 carbon atoms, and 0. It preferably contains 01 to 2% by mass of a polyfunctional monomer unit. The crosslinked elastic layer of the second layer consists of an acrylic acid alkyl ester unit having an alkyl group having 70 to 99.9% by mass and an alkyl group having 1 to 8 carbon atoms and a methyl methacrylate unit of 0 to 29.9% by mass (optional component). ) And 0.1 to 5% by mass of a polyfunctional monomer unit. The hard thermoplastic resin layer of the third layer preferably contains 80 to 99% by mass of methyl methacrylate units and 1 to 20% by mass of acrylic acid alkyl ester units having an alkyl group having 1 to 8 carbon atoms. ..

In the three-layer structure polymer particles (Y1), the ratio of each layer is not particularly limited, the first layer is 5 to 40% by mass, the second layer is 20 to 55% by mass, and the third layer (outermost layer). ) Is preferably 15 to 75% by mass.

The particle size of the acrylic multilayer structure polymer particles (Y) is not particularly limited, and is preferably 0.05 μm or more, more preferably 0.06 μm or more, and further preferably 0.07 μm or more. .. The particle size of the acrylic multilayer structure polymer particles (Y) is preferably 0.25 μm or less, more preferably 0.20 μm or less, and even more preferably 0.15 μm or less. If the particle size of the acrylic multilayer polymer particles (Y) is less than 0.05 μm, the handleability of the acrylic multilayer polymer particles (Y) tends to decrease. When the particle size of the acrylic multilayer polymer particles (Y) is larger than 0.25 μm, the interlayer film for laminated glass of the present invention tends to whiten when stress is applied and the transmittance tends to decrease (that is,). , Stress whitening resistance deteriorates). Further, when the addition ratio of the multilayer structure polymer particles (Y) having a large particle size is large, the haze of the obtained laminated glass tends to increase. From the viewpoint of stress whitening resistance and haze, the particle size of the acrylic multilayer structure polymer particles (Y) is preferably 0.15 μm or less. The particle size of the acrylic multilayer structure polymer particles (Y) can be appropriately adjusted by, for example, changing the amount of the surfactant added and the composition of the monomer when polymerizing by the emulsion polymerization method. it can.

The transparency of the A layer is that the acrylic multilayer structure polymer particles (Y) are composed of a polymer having a refractive index in the range of 1.485 to 1.495 as measured based on ASTM D542. It is preferable from the viewpoint of enhancing.

The polymerization method of the acrylic multilayer structure polymer particles (Y) is not particularly limited, and the emulsion polymerization method is preferable. First, one or more raw material monomers are emulsion-polymerized to form core particles, and then another one or two or more monomers are emulsion-polymerized in the presence of the core particles to form core particles. Form a shell around the. Then, if necessary, one or more types of monomers are further emulsion-polymerized in the presence of particles consisting of a core and a shell to form another shell. By repeating such a polymerization reaction, the target acrylic multilayer structure polymer particles (Y) can be produced as an emulsified latex. In the obtained latex, in addition to the acrylic multilayer structure polymer particles (Y), a linear methacrylic resin having a methyl methacrylate unit is usually present.

The content of the acrylic multilayer structure polymer particles (Y) used in the present invention is preferably 40% by mass or more, more preferably 50% by mass or more , and 62 by mass, based on the total mass of the A layer. It is particularly preferable that the content is% by mass or more. The content of the acrylic multilayer structure polymer particles (Y) is preferably 80% by mass or less, more preferably 70% by mass or less, and 67% by mass, based on the total mass of the A layer. The following is particularly preferable.
The content of the acrylic multilayer structure polymer particles (Y) shall be determined by the following method using acetone.
After the acrylic resin composition constituting the A layer is sufficiently dried to remove water, its mass (W1) is measured. Next, this acrylic resin composition is placed in a test tube, and acetone is added to dissolve the composition to remove the acetone-soluble portion. Acetone is then removed using a vacuum heater to obtain a residue. Fine particles are separated from this residue, and then the mass (W2) of the obtained residue is measured. The content of the acrylic multilayer structure polymer particles (Y) is determined based on the following formula.
[Content of acrylic multilayer polymer particles (Y)] = (W2 / W1) x 100 (%)

(Methacrylic resin (M))
The acrylic resin composition used for the acrylic film contains acrylic multilayer structure polymer particles (Y) and more than 80% by mass of methyl methacrylate units, and has a melt flow rate of 0.5 to 10 g / 10 minutes. It is preferable to contain the methacrylic resin (M). As the methacrylic resin (M), one type may be used alone, or two or more types may be used.

The methacrylic resin (M) can contain 20% by mass or less of a copolymerizable vinyl-based monomer unit, if necessary, in accordance with the methyl methacrylate unit. The vinyl-based monomer is not particularly limited, and examples thereof include an acrylic acid ester monomer such as methyl acrylate; a methacrylate ester; an aromatic vinyl compound; and the like. These can be used alone or in combination of two or more.

The melt flow rate of the methacrylic resin (M) is preferably 1 g / 10 minutes or more, and more preferably 1.2 g / 10 minutes or more. The melt flow rate of the methacrylic resin (M) is preferably 5 g / 10 minutes or less, and more preferably 3 g / 10 minutes or less. When the melt flow rate of the methacrylic resin (M) exceeds the above range, the acrylic resin composition (R1) containing the methacrylic resin (M) and the acrylic multilayer polymer particles (Y) is melt-molded. The tenacity of the particles tends to decrease. If the melt flow rate of the methacrylic resin (M) is less than the above range, the fluidity when the acrylic resin composition (R1) is melt-molded tends to decrease. For the methacrylic resin (M) having a melt flow rate of 0.5 to 10 g / 10 minutes, for example, the amount of the acrylic acid ester or chain transfer agent used in combination with the polymerization of the monomer containing methyl methacrylate is appropriately added. It can be obtained by adjusting.

The methacrylic resin (M) is preferably composed of a polymer having a refractive index in the range of 1.485 to 1.495 measured based on ASTM D542 from the viewpoint of enhancing the transparency of the A layer. ..

The blending amount of the methacrylic resin (M) in the acrylic resin composition (R1) in which the acrylic multilayer polymer particles (Y) and the methacrylic resin (M) are mixed is not particularly limited, and the acrylic multilayer structure weight is not particularly limited. It is preferably 1 part by mass or more, more preferably 5 parts by mass or more , and particularly preferably 15 parts by mass or more with respect to 100 parts by mass of the coalesced particles (Y). The blending amount of the methacrylic resin (M) is preferably 100 parts by mass or less, preferably 70 parts by mass or less, and 45 parts by mass with respect to 100 parts by mass of the acrylic multilayer structure polymer particles (Y). It is particularly preferable that the amount is less than or equal to a part. When the blending amount of the methacrylic resin (M) is more than 100 parts by mass, it tends to be difficult for the A layer to satisfy the formula (3).

As the methacrylic resin (M), a commercially available product or a specified product of ISO8257-1 can be used.
The methacrylic resin (M) can be polymerized and used by a known method. Here, the polymerization method of the methacrylic resin (M) is not particularly limited, and examples thereof include an emulsion polymerization method, a suspension polymerization method, a massive polymerization method, and a solution polymerization method.

(Acrylic block copolymer (Z))
The methacrylic acid ester polymer block (z1) has a structural unit derived from the methacrylic acid ester as a main structural unit. The proportion of the structural unit derived from the methacrylic acid ester in the methacrylic acid ester polymer block (z1) is preferably 80% by mass or more, more preferably 90% by mass or more, and 95% by mass or more. Is more preferable, and 98% by mass or more is particularly preferable.

As the methacrylic acid ester, methyl methacrylate is more preferable from the viewpoint of improving transparency and heat resistance. The methacrylic acid ester polymer block (z1) can be formed by polymerizing one type alone or in combination of two or more types.

The weight average molecular weight Mw (z1) of a single unit of the methacrylic acid ester polymer block (z1) is preferably 5,000 or more, and preferably 150,000 or less. Further, the weight average molecular weight Mw of a single unit of the methacrylic acid ester polymer block (z1) is more preferably 8,000 or more, and further preferably 12,000 or more. Further, the weight average molecular weight Mw is more preferably 120,000 or less, and further preferably 100,000 or less.

In the block copolymer (Z), when there are a plurality of methacrylic acid ester polymer blocks (z1) in one molecule, the composition ratio and molecular weight of the structural units constituting each methacrylic acid ester polymer block (z1) are , They may be the same or different from each other.

The proportion of the methacrylic acid ester polymer block (z1) in the block copolymer (Z) is preferably 10% by mass or more, preferably 25% by mass, from the viewpoint of transparency, flexibility, moldability and surface smoothness. % Or more, more preferably 70% by mass or less, and even more preferably 60% by mass or less. When the proportion of the methacrylic acid ester polymer block (z1) in the block copolymer (Z) is 10% by mass or more and 70% by mass or less, the transparency of the A layer made of the acrylic resin composition of the present invention is transparent. , Excellent in flexibility, bending resistance, impact resistance, flexibility, etc. When the block copolymer (Z) contains a plurality of methacrylic acid ester polymer blocks (z1), the above ratio is calculated based on the total mass of all the methacrylic acid ester polymer blocks (z1).

The acrylic acid ester polymer block (z2) has a structural unit derived from the acrylic acid ester as a main structural unit. The ratio of the structural unit derived from the acrylic acid ester in the acrylic acid ester polymer block (z2) is preferably 45% by mass or more, more preferably 50% by mass or more, and more preferably 60% by mass or more. Is more preferable, and 90% by mass or more is further preferable.

Examples of the acrylic acid ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, and acrylate. Amil, isoamyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, isobornyl acrylate, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, 2 acrylate -Hydroxyethyl, 2-methoxyethyl acrylate, glycidyl acrylate, allyl acrylate and the like can be mentioned. The acrylic acid ester polymer block (z2) can be formed by polymerizing one type alone or in combination of two or more types.

The acrylic acid ester polymer block (z2) is preferably composed of an acrylic acid alkyl ester and an acrylic acid aromatic ester from the viewpoint of improving the transparency of the acrylic resin composition (R2) used in the present invention. When the acrylic acid ester polymer block (z2) is composed of an acrylic acid alkyl ester and an acrylic acid aromatic ester, the acrylic acid ester polymer block (z2) is a structural unit 50 to 90 derived from the acrylic acid alkyl ester. It preferably contains 50% by mass and 50-10% by mass of structural units derived from the (meth) acrylic acid aromatic ester.

The weight average molecular weight Mw (z2) of a single unit of the acrylic acid ester polymer block (z2) is preferably 5,000 or more, more preferably 15,000 or more, and more preferably 30,000 or more. Is particularly preferred. The weight average molecular weight Mw (z2) of a single unit of the acrylic acid ester polymer block (z2) is preferably 120,000 or less, more preferably 110,000 or less, and 100,000 or less. Is particularly preferred.

The proportion of the acrylic ester polymer block (z2) in the block copolymer (Z) is preferably 10% by mass or more, preferably 20% by mass, from the viewpoint of transparency, flexibility, moldability and surface smoothness. % Or more, more preferably 60% by mass or less, and even more preferably 55% by mass or less. When the proportion of the acrylic acid ester polymer block (z2) in the block copolymer (Z) is in the range of 10% by mass or more and 60% by mass or less, the impact resistance of the A layer made of the acrylic resin composition of the present invention is high. Excellent in sex and flexibility. When the block copolymer (Z) contains a plurality of acrylic acid ester polymer blocks (z2) in one molecule, the above ratio is based on the total mass of all acrylic acid ester polymer blocks (z2). calculate.

The bond form between the methacrylic acid ester polymer block (z1) of the block copolymer (Z) and the acrylic acid ester polymer block (z2) is not particularly limited. For example, a methacrylic acid ester polymer block (z1) to which one end of an acrylic acid ester polymer block (z2) is connected (a diblock copolymer having a (z1)-(z2) structure); methacrylic acid. One end of the acrylic acid ester polymer block (z2) is connected to each of both ends of the ester polymer block (z1) (a triblock copolymer having a (z2)-(z1)-(z2) structure); A triblock copolymer having a structure ((z1)-(z2)-(z1)) in which one end of the methacrylic acid ester polymer block (z1) is connected to each of both ends of the acrylic acid ester polymer block (z2). ) And the like, and examples thereof include a block copolymer having a structure in which a methacrylic acid ester polymer block (z1) and an acrylic acid ester polymer block (z2) are connected in series.

Further, the block copolymer (Z) may have a polymer block (z3) other than the methacrylic acid ester polymer block (z1) and the acrylic acid ester polymer block (z2).

The block copolymer (Z) may have a functional group such as a hydroxyl group, a carboxyl group, an acid anhydride, or an amino group in the molecular chain or at the end of the molecular chain, if necessary.

The weight average molecular weight Mw (Z) of the block copolymer (Z) is preferably 52,000 or more, and more preferably 60,000 or more. The weight average molecular weight Mw (Z) of the block copolymer (Z) is preferably 400,000 or less, and more preferably 300,000 or less. If the weight average molecular weight of the block copolymer (Z) is small, sufficient melt tension cannot be maintained in melt extrusion molding, it is difficult to obtain a good plate-shaped molded product, and the breaking strength of the obtained plate-shaped molded product is high. There is a tendency for mechanical properties such as to decrease. On the other hand, when the weight average molecular weight of the block copolymer (Z) is large, the viscosity of the molten resin becomes high, and the surface of the plate-shaped molded product obtained by melt extrusion molding has fine grained irregularities and unmelted matter (high). There is a tendency that it is difficult to obtain a good plate-shaped molded product due to the occurrence of lumps due to (molecular weight).

Further, Mw (Z) / Mn (Z), which is the ratio of the weight average molecular weight Mw (Z) representing the molecular weight distribution of the block copolymer (Z) to the number average molecular weight Mn (Z), is 1.0 or more. It is preferably 2.0 or less, and more preferably 1.6 or less. By having the molecular weight distribution within such a range, the content of the unmelted material that causes the generation of lumps can be made extremely small in the interlayer film for laminated glass of the present invention.

The melt viscosity (η (Z)) of the block copolymer (Z) at 220 ° C. and a shear rate of 122 / sec is preferably in the range of 75 to 1500 Pa · s. The melt viscosity (η (Z)) is more preferably 150 Pa · s or more, and particularly preferably 300 Pa · s or more. The melt viscosity (η (Z)) is more preferably 1000 Pa · s or less, and particularly preferably 700 Pa · s or less. Since the melt viscosity (η (Z)) is in the range of 75 to 1500 Pa · s, it has excellent mechanical properties such as breaking strength, and is caused by fine grained irregularities on the surface and unmelted matter (high molecular weight material). It is possible to obtain a good film in which the generation of lumps is suppressed.

Further, the value of the ratio (η (M) / η (Z)) of the melt viscosity (η (M)) to the melt viscosity (η (Z)) of the methacrylic resin (M) at 220 ° C. and a shear rate of 122 / sec. Is preferably 1 or more, more preferably 5 or more, and even more preferably 6 or more. The value of (η (M) / η (Z)) is preferably 20 or less, more preferably 10 or less, and even more preferably 8 or less. When the value of η (M) / η (Z) is in the range of 1 to 20, good dispersibility can be ensured, and the film has excellent mechanical and optical characteristics.

The melt viscosities of the methacrylic resin (M) and the block copolymer (Z) at 220 ° C. and a shear rate of 122 / sec were measured at 220 ° C. using a capillograph (manufactured by Toyo Seiki Seisakusho Co., Ltd., model 1D). It can be obtained from the shear stress generated when the molten resin is extruded from a polymer having a diameter of 1 mmΦ and a length of 10 mm at a piston speed of 10 mm / min.

The refractive index of the block copolymer (Z) measured based on ASTM D542 is preferably 1.485 or higher, more preferably 1.487 or higher. The refractive index of the block copolymer (Z) is preferably 1.495 or less, and more preferably 1.493 or less. When the refractive index of the block copolymer (Z) is in the range of 1.485 to 1.495, the transparency of the A layer becomes high. In the present specification, the “refractive index” means a value measured at a measurement wavelength of 587.6 nm (d line) as in Examples described later.

The method for producing the block copolymer (Z) is not particularly limited, and a method according to a known method can be adopted. For example, a method of living-polymerizing the monomers constituting each polymer block is generally used. Such living polymerization methods include, for example, an anionic polymerization using an organic alkali metal compound as a polymerization initiator in the presence of a mineral salt such as an alkali metal or an alkaline earth metal salt, and polymerization of an organic alkali metal compound. A method of anion polymerization in the presence of an organic aluminum compound used as an initiator, a method of polymerizing using an organic rare earth metal complex as a polymerization initiator, and a method of radical polymerization in the presence of a copper compound using an α-halogen ester compound as an initiator. And so on. Further, a method of polymerizing the monomers constituting each block using a polyvalent radical polymerization initiator or a polyvalent radical chain transfer agent to produce a mixture containing the block copolymer (Z) used in the present invention. Can also be mentioned. Among these methods, in particular, since the block copolymer (Z) can be obtained with high purity, the molecular weight and composition ratio can be easily controlled, and it is economical, an organoalkali metal compound is used as a polymerization initiator. A method of anionic polymerization in the presence of an organoaluminum compound is preferable.

The acrylic resin composition (R2) used for the acrylic film contains a block copolymer (Z) and 80% by mass or more of methyl methacrylate units, and has a melt flow rate of 0.5 to 10 g / 10 minutes. It is preferable to contain the methacrylic resin (M). The content of the block copolymer (Z) in the acrylic resin composition (R2) is 1 part by mass or more with respect to 100 parts by mass in total of the methacrylic resin (M) and the block copolymer (Z). It is preferably 10 parts by mass or more, and more preferably 10 parts by mass or more. The content of the block copolymer (Z) is preferably 90 parts by mass or less, preferably 45 parts by mass or less, based on 100 parts by mass of the total of the methacrylic resin (M) and the block copolymer (Z). It is more preferable that the amount is 30 parts by mass or less. If the content of the methacrylic resin (M) in the acrylic resin composition (R2) is smaller than that of the block copolymer (Z), the surface hardness of the sheet obtained by melt extrusion molding using a T-die decreases. Tend.

(Arbitrary ingredient)
In addition to the above-mentioned components, the layer A of the present invention may contain one or more arbitrary components, if necessary, as long as the object of the present invention is not impaired.
Optional ingredients include antioxidants, heat deterioration inhibitors, UV absorbers, light stabilizers, plasticizers, lubricants, mold release agents, polymer processing aids, antistatic agents, flame retardants, dye pigments, organic pigments, etc. Examples thereof include impact resistance modifiers, foaming agents, fillers, and various additives such as phosphors.
The timing of addition of the optional component is not particularly limited, and may be added at the time of polymerization of any of the acrylic multilayer structure polymer particles (Y), the methacrylic resin (M), and the block copolymer (Z). After the polymerization, it may be added to the acrylic resin composition (R), or if necessary, it may be added at the time of kneading or after kneading any component.

(Antioxidant)
The antioxidant is effective in preventing oxidative deterioration of the resin by itself in the presence of oxygen. For example, phosphorus-based antioxidants, hindered phenol-based antioxidants, thioether-based antioxidants, and the like can be mentioned. As the antioxidant, an antioxidant containing a portion having a phosphorus-based antioxidant effect and a portion having a hindered phenol-based antioxidant effect in the same molecule can also be used. These antioxidants may be used alone or in combination of two or more. Among them, phosphorus-based antioxidants and hindered phenol-based antioxidants are preferable from the viewpoint of the effect of preventing deterioration of optical properties due to coloring, and the combined use of phosphorus-based antioxidants and hindered phenol-based antioxidants is more preferable. .. When a phosphorus-based antioxidant and a hindered phenol-based antioxidant are used in combination, it is the mass ratio of the amount of the phosphorus-based antioxidant used and the amount of the hindered phenol-based antioxidant used (of the phosphorus-based antioxidant). The amount used) / (the amount of the hindered phenol-based antioxidant used) is preferably 1/5 or more, and more preferably 1/2 or more. Further, (amount of phosphorus-based antioxidant used) / (amount of hindered phenol-based antioxidant used) is preferably 2/1 or less, and more preferably 1/1 or less.

As phosphorus-based antioxidants, 2,2-methylenebis (4,6-dit-butylphenyl) octylphosphite (manufactured by ADEKA Co., Ltd .; trade name: Adecastab HP-10), Tris (2,4-dit) -Butylphenyl) phosphite (manufactured by BASF; trade name: IRGAFOS168), and 3,9-bis (2,6-dit-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa3 9-Diphosphaspiro [5.5] Undecan (manufactured by ADEKA Co., Ltd .; trade name: Adecastab PEP-36) and the like are preferable.

Examples of the hindered phenolic antioxidant include pentaerythrityl-tetrakis [3- (3,5-dit-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF; trade name IRGANO01010) and octadecyl-3-3. (3,5-dit-butyl-4-hydroxyphenyl) propionate (manufactured by BASF; trade name IRGANO01076) and the like are preferable.

Examples of the antioxidant containing a portion having a phosphorus-based antioxidant effect and a portion having a hindered phenol-based antioxidant effect in the same molecule include 6- [3- (3-t-butyl-4-hydroxy). -5-Methyl) Propoxy] -2,4,8,10-Tetra-t-Butyldibenz [d, f] [1,3,2] -Dioxasphosfepine (manufactured by Sumitomo Chemical Co., Ltd .; trade name Sumilyzer GP) ) Etc. are preferable.

(Heat deterioration inhibitor)
The heat deterioration inhibitor can prevent the heat deterioration of the resin by capturing the polymer radicals generated when exposed to high heat under a substantially oxygen-free state. Examples of the heat deterioration inhibitor include 2-t-butyl-6- (3'-t-butyl-5'-methyl-hydroxybenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name: Sumilyzer GM). And 2,4-dit-amyl-6- (3', 5'-dit-amyl-2'-hydroxy-α-methylbenzyl) phenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name Sumilyzer GS), etc. preferable.

(UV absorber)
An ultraviolet absorber is a compound having an ability to absorb ultraviolet rays. The ultraviolet absorber is a compound that is said to have a function of mainly converting light energy into heat energy. Examples of the ultraviolet absorber include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, oxalic acid anilides, malonic acid esters, formamidines and the like. These can be used alone or in combination of two or more. Among the above, benzotriazoles, triazines, or _{an ultraviolet absorber having a maximum molar extinction coefficient ε max} of 1200 dm ³ · mol ^-1 cm ^-1 or less at a wavelength of 380 to 450 nm is preferable.

Benzotriazoles are highly effective in suppressing deterioration of optical properties such as coloring due to exposure to ultraviolet rays. Examples of benzotriazoles include 2- (2H-benzotriazole-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (manufactured by BASF; trade name TINUVIN329), 2- (2H-). Benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (manufactured by BASF; trade name TINUVIN234) and 2,2'-methylenebis [6- (2H-benzotriazole) -2-yl) -4-tert-octylphenol] (manufactured by ADEKA Co., Ltd .; LA-31) and the like are preferable.

An ultraviolet absorber having a maximum molar extinction coefficient ε _max of 1200 dm ³ · mol ^-1 cm ^-1 or less at a wavelength of 380 to 450 nm can suppress the yellowness of the obtained thermoplastic resin film. Examples of such an ultraviolet absorber include 2-ethyl-2'-ethoxy-oxalanilide (manufactured by Clariant Japan Co., Ltd .; trade name: Sandeuboa VSU).

Among the above-mentioned ultraviolet absorbers, benzotriazoles and the like are preferably used from the viewpoint of suppressing resin deterioration due to ultraviolet exposure.

Further, when it is desired to efficiently absorb a wavelength in the vicinity of 380 nm, a triazine-type ultraviolet absorber is preferably used. Examples of such an ultraviolet absorber include 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine (manufactured by ADEKA Co., Ltd .; LA-F70). And its analogs, hydroxyphenyltriazine-based ultraviolet absorbers (manufactured by BASF; TINUVIN477-D, TINUVIN460, TINUVIN479) and the like can be mentioned.

_{The maximum value ε max} of the molar extinction coefficient of the ultraviolet absorber is measured as follows. 10.00 mg of an ultraviolet absorber is added to 1 L of cyclohexane and dissolved so that there is no undissolved substance by visual observation. This solution is injected into a 1 cm × 1 cm × 3 cm quartz glass cell, and the absorbance at a wavelength of 380 to 450 nm is measured using a U-3410 spectrophotometer manufactured by Hitachi, Ltd. _{The maximum value ε max} of the molar extinction coefficient is calculated from the molecular weight ( _MVV ) of the ultraviolet absorber and the maximum value (A _{max) of the measured absorbance by the following equation.}
ε _max = [A _max / (10 × 10 ^-3 )] × M _UV

(Light stabilizer)
The light stabilizer is a compound that is said to have a function of capturing radicals mainly generated by oxidation by light. Suitable light stabilizers include hindered amines (manufactured by ADEKA Corporation; LA-52 and LA-57) (manufactured by BASF; TINUVIN622SF and TINUVIN770) such as compounds having a 2,2,6,6-tetraalkylpiperidine skeleton. Can be mentioned.

(Polymer processing aid)
As the polymer processing aid, for example, polymer particles produced by an emulsion polymerization method and composed of 60% by mass or more of methyl methacrylate and 40% by mass or less of a vinyl-based monomer unit copolymerizable therewith are used. Used. The polymer processing aid preferably has an ultimate viscosity of 3 to 6 dl / g.

The total amount of the various additives is not particularly limited, and is generally preferably 0.01% by mass or more, more preferably 0.05% by mass or more, based on 100% by mass of the thermoplastic resin film. The total amount of the various additives is preferably 20% by mass or less, more preferably 1.5% by mass or less, based on 100% by mass of the thermoplastic resin film.

(Adhesive strength adjuster)
In order to adjust the adhesive force between the A layer and the B layer, an adhesive force adjusting agent may be added to the A layer or the B layer. As the adhesive strength adjusting agent, polyolefins having an adhesive functional group such as a carboxyl group, a carboxyl group derivative group, an epoxy group, a boronic acid group, a boronic acid group derivative group, an alkoxyl group, or an alkoxyl group derivative group can be used. Can be mentioned.

In particular, when a polyvinyl acetal resin is used for the B layer, the adhesive strength between the A layer and the B layer can be suitably adjusted by adding polyolefins having an adhesive functional group to the A layer. The amount of the polyolefin having an adhesive functional group added is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and 10 parts by mass with respect to 100 parts by mass of the thermoplastic resin of the A layer. The following is more preferable. If the amount of the polyolefin having an adhesive functional group added exceeds 20 parts by mass, the haze may be deteriorated when the laminated glass is produced. Among the above-mentioned polyolefins, polypropylene containing a carboxyl group is preferable as the polyolefin having an adhesive functional group from the viewpoint of easy availability, easy adjustment of adhesiveness, and easy adjustment of haze. Is.

[Functional layer]
The interlayer film for laminated glass of the present invention preferably has a functional layer (functional coating layer) such as a heat ray-shielding structure, a conductive structure, and a printing layer on at least one side of the A layer. Of the two surfaces of the layer A, it is preferable to provide the functional layer on the surface having an arithmetic mean roughness (Ra) of 3.0 μm or less.

Examples of the method for imparting heat ray-shielding property to the A layer include a method in which the A layer contains metal oxide fine particles having a heat ray-shielding function, and a method in which a heat ray-shielding coating is provided on the surface of the A layer. The metal oxide fine particles having a heat ray shielding function are not particularly limited as long as they have a function of absorbing at least light rays in the near infrared wavelength region. For example, tin-doped indium oxide, antimony-doped tin oxide, and aluminum-doped Examples thereof include zinc oxide, indium-doped zinc oxide, gallium-doped zinc oxide, tungsten oxide, lanthanum hexaboride, cerium hexaboride, zinc anhydride antimonate, and copper sulfide. These may be used alone or in combination of two or more. Among these, it is preferable to contain anhydrous zinc antimonate from the viewpoints of performance, safety, availability of raw materials, price and the like.

When the metal oxide fine particles having a heat ray shielding function are contained in the A layer, the content of the metal oxide fine particles shall be 0.001 part by mass or more with respect to 100 parts by mass of the thermoplastic resin in the A layer. Is preferable, and 0.002 parts by mass or more is more preferable. The content of the metal oxide fine particles is preferably 2 parts by mass or less, and more preferably 1.5 parts by mass or less, based on 100 parts by mass of the thermoplastic resin in the layer A. If the content of the metal oxide fine particles is less than 0.001 part by mass, the expected heat ray shielding effect tends not to be obtained. When the content of the metal oxide fine particles is more than 2 parts by mass, the transparency of the A layer tends to decrease.

In the present invention, the conductive structure also includes a conductive structure discontinuous, and is not a flat layer but an individually identifiable structure such as a conductor path, a conducting wire, and a network structure composed of them. , Points and combinations thereof. The discontinuous conductive structure may be provided on the surface of layer A or embedded in this surface.

The discontinuous conductive structure preferably contains metals such as gold, silver, copper, indium, zinc, iron and aluminum. However, alternatives, or in combination with it, the semiconductor material can also be appropriately placed in layer A. In addition, carbon-based conductive materials such as graphite, CNTs (carbon nanotubes) or graphene may be included.

The conductive structure can be made on the surface of layer A by various variants of the printing method, such as screen printing, flexographic or gravure printing, vapor deposition, sputtering, electrodeposition. The printing method optionally uses a suitable ink that can usually still be dried prior to lamination or can be cured by heat or light. The conductive structure may be formed on the surface of the A layer in its final form only by using a laser or another processing means (engraving, etching) from a relatively coarse structure for the time being.

When using a printing method (“printed electronics”), the ink or printing ink used contains conductive particles. Conductive particles include particles of metals such as gold, silver, copper, zinc, iron or aluminum, as well as materials coated with metals such as silver-plated glass fibers, particles of glass globules, and conductive carbon black. It may be carbon nanotube, graphite or graphene particles. Further, it is a semiconductor particle, for example, a particle of a conductive metal oxide, for example, indium-doped tin oxide, indium-doped zinc oxide, or antimonated tin oxide. Among them, as the conductive particles, gold, silver, copper or a conductive metal oxide is preferable.

In general, conductive structures can be used to create electrical circuits, such as wiring or transmit and / or receive antennas, and other functions to electromagnetically shield frequency electromagnetic fields. This allows, for example, a heating element to be introduced into laminated glass, and the antenna can be used, for example, in the automotive field for radio wave reception or in vehicle-to-vehicle communication.

The conductive structure of the laminate according to the present invention may be finished as a contact sensor, which allows the production of interacting laminated glass. Therefore, for example, information input on laminated glass (for example, the windshield or side glass of a passenger car, or the glass of a door) can be used for access control.

Electronic components, i.e., multi-layered structures of conductive and dielectric structures, may further be provided with electronic circuits or entire components. This includes transistors, resistors, chips, sensors, displays, light emitting diodes (eg OLEDs) and / or smart labels in particular.

Conductive structures can be very small and may not be fully visible to the naked eye. The width of the conductive structure is preferably 1 μm or more. The width of the conductive structure is preferably 30 μm or less, more preferably 20 μm or less, and even more preferably 15 μm or less. In particular, in the case of a flat heating region (Heizfelder), the width of the filament is less than 25 μm. The heating region may be introduced only locally, eg, in front of the optical sensor system above the windshield.

The thickness of the heat ray-shielding coating used in the present invention and the thickness of the conductive structure are preferably 10 μm or less, more preferably 1 μm or less, from the viewpoint of ensuring transparency. It is more preferably 0.5 μm or less. The thickness of the conductive structure is preferably 50 μm or less, more preferably 20 μm or less, still more preferably 15 μm or less, from the viewpoint of suppressing the frequency of occurrence of defects during laminating.

[B layer]
The interlayer film for laminated glass of the present invention preferably has a B layer containing a thermoplastic resin on at least one side of the A layer, and more preferably has a B layer containing a thermoplastic resin on both sides of the A layer.

The type of the thermoplastic resin constituting the B layer is not particularly limited, and examples thereof include polyvinyl acetal resin, ionomer, ethylene vinyl acetate, vinyl chloride resin, urethane resin, silicone resin, and polyamide resin. By using the above-mentioned thermoplastic resin for the B layer, it is possible to improve the weather resistance and strength of the interlayer film for laminated glass and adjust the adhesiveness with the glass. From the viewpoint of adhesiveness to glass and transparency, polyvinyl acetal resin and ionomer are preferable as the thermoplastic resin used for the B layer.

The layer B, which is a part of the interlayer film for laminated glass of the present invention, is not particularly limited as long as the difference in refractive index from the layer A is 0.05 or less. From the viewpoint of producing safe glass having low glass scattering property when broken, it is preferable to use a polyvinyl acetal resin layer made of a composition containing a polyvinyl acetal resin.

The resin film constituting the B layer is composed of a polymer having a refractive index in the range of 1.485 to 1.495 measured based on ASTM D542 from the viewpoint of enhancing the transparency of the B layer. preferable.

The thickness of the B layer is preferably 200 μm or more, and more preferably 350 μm or more. The thickness of the B layer is preferably 3000 μm or less, more preferably 2000 μm or less.

(Polyvinyl acetal resin)
When a composition containing a thermoplastic resin such as a polyvinyl acetal resin is used as the B layer, the B layer preferably contains 40% by mass or more of the thermoplastic resin such as the polyvinyl acetal resin, and preferably 50% by mass or more. More preferably, it is more preferably 60% by mass or more, particularly preferably 80% by mass or more, further preferably 90% by mass or more, and the B layer is composed only of a thermoplastic resin such as a polyvinyl acetal resin. You may. If the content of the thermoplastic resin such as polyvinyl acetal resin in the B layer is less than 40% by mass, the adhesiveness to the glass may decrease.

The polyvinyl acetal resin preferably has an average acetalization degree of 40 mol% or more. If the average degree of acetalization of the polyvinyl acetal resin is less than 40 mol%, the compatibility with a solvent such as a plasticizer tends to decrease. The average degree of acetalization of the polyvinyl acetal resin is more preferably 60 mol% or more, and further preferably 65 mol% or more from the viewpoint of water resistance.

The polyvinyl acetal resin preferably has an average acetalization degree of 90 mol% or less. If the average degree of acetalization of the polyvinyl acetal resin exceeds 90 mol%, the reaction for obtaining the polyvinyl acetal resin takes a long time, which may be unfavorable in terms of process. The average degree of acetalization of the polyvinyl acetal resin is more preferably 85 mol% or less, and further preferably 80 mol% or less from the viewpoint of water resistance.

The polyvinyl acetal resin preferably has a vinyl acetate unit content of 30 mol% or less in the polyvinyl acetal resin. If the content of the vinyl acetate unit exceeds 30 mol%, blocking is likely to occur during the production of the resin, which makes the production difficult. The content of the vinyl acetate unit in the polyvinyl acetal resin is preferably 20 mol% or less.

The content of the vinyl alcohol unit of the polyvinyl acetal resin is preferably 15 mol% or more, more preferably 20 mol% or more, and further preferably 25 mol% or more. The content of the vinyl alcohol unit of the polyvinyl acetal resin is preferably 50 mol% or less, more preferably 45 mol% or less, and further preferably 40 mol% or less. When the content of the vinyl alcohol unit is less than 15 mol%, the adhesiveness with the glass tends to decrease, and when the content of the vinyl alcohol unit is more than 50 mol%, the water resistance tends to decrease.

The polyvinyl acetal resin is usually composed of vinyl acetal units, vinyl alcohol units and vinyl acetate units, and the amount of each of these units is determined by, for example, JIS K6728 “polyvinyl butyral test method” or nuclear magnetic resonance (NMR). Can be measured.

When the polyvinyl acetal resin contains units other than vinyl acetal units, the unit amount of vinyl alcohol and the unit amount of vinyl acetate are measured, and when both of these unit amounts do not contain units other than vinyl acetal units, vinyl acetal By subtracting from the unit amount, the remaining vinyl acetal unit amount can be calculated.

The polyvinyl acetal resin can be produced by a conventionally known method, and can be typically produced by acetalizing polyvinyl alcohol with aldehydes. Specifically, polyvinyl alcohol is dissolved in warm water, and the obtained aqueous solution is kept at a predetermined temperature, for example, 0 ° C. or higher and 90 ° C. or lower, preferably 10 ° C. or higher and 20 ° C. or lower. Acid catalysts and aldehydes are added and the acetalization reaction proceeds with stirring, then the reaction temperature is raised to 70 ° C. for aging to complete the reaction, followed by neutralization, washing with water and drying to carry out polyvinyl. Examples thereof include a method of obtaining an acetal resin powder.

The viscosity average degree of polymerization of polyvinyl alcohol, which is a raw material of the polyvinyl acetal resin, is preferably 100 or more, more preferably 300 or more, more preferably 400 or more, still more preferably 600 or more. , 700 or more is particularly preferable, and 750 or more is most preferable. If the viscosity average degree of polymerization of polyvinyl alcohol is too low, the penetration resistance and creep physical properties, particularly the creep physical properties under high temperature and high humidity conditions such as 85 ° C. and 85% RH may be deteriorated. The viscosity average degree of polymerization of polyvinyl alcohol is preferably 5000 or less, more preferably 3000 or less, further preferably 2500 or less, particularly preferably 2300 or less, and 2000 or less. Is most preferable. If the viscosity average degree of polymerization of polyvinyl alcohol exceeds 5000, it may be difficult to mold the resin film.

Further, in order to improve the laminating suitability of the obtained laminated glass interlayer film and obtain a laminated glass having a more excellent appearance, the viscosity average degree of polymerization of polyvinyl alcohol is preferably 1500 or less, and is preferably 1100 or less. Is more preferable, and 1000 or less is further preferable.

Since the viscosity average degree of polymerization of the polyvinyl acetal resin is the same as the viscosity average degree of polymerization of the raw material polyvinyl alcohol, the preferable viscosity average degree of polymerization of the above-mentioned polyvinyl alcohol is the same as the preferable viscosity average degree of polymerization of the polyvinyl acetal resin. ..

Since the vinyl acetate unit of the obtained polyvinyl acetal resin is preferably set to 30 mol% or less, it is preferable to use polyvinyl alcohol having a saponification degree of 70 mol% or more. When the saponification degree of polyvinyl alcohol is less than 70 mol%, the transparency and heat resistance of the resin may decrease, and the reactivity with aldehydes may also decrease. The saponification degree is more preferably 95 mol% or more.

The viscosity average degree of polymerization and the degree of saponification of polyvinyl alcohol can be measured based on, for example, JIS K 6726 “Polyvinyl alcohol test method”.

As the aldehydes used for acetalizing polyvinyl alcohol, aldehydes having 1 or more carbon atoms and 12 or less carbon atoms are preferable. When the number of carbon atoms of the aldehyde exceeds 12, the reactivity of acetalization is lowered, and the resin is easily blocked during the reaction, which makes it easy to synthesize the resin.

The aldehydes are not particularly limited, and for example, formaldehyde, acetaldehyde, propionaldehyde, n-butyl aldehyde, isobutyl aldehyde, barrel aldehyde, n-hexyl aldehyde, 2-ethyl butyl aldehyde, n-heptyl aldehyde, n-octyl aldehyde, Examples thereof include aliphatic, aromatic and alicyclic aldehydes such as n-nonyl aldehyde, n-decyl aldehyde, benzaldehyde and cinnam aldehyde. Among these, aliphatic aldehydes having 2 or more carbon atoms and 6 or less carbon atoms are preferable, and butyraldehyde is particularly preferable. Further, the above aldehydes may be used alone or in combination of two or more. Further, polyfunctional aldehydes and aldehydes having other functional groups may be used in combination in a small amount in a range of 20% by mass or less of all aldehydes.

(Ionomer)
The ionomer is not particularly limited, but has a structural unit derived from ethylene and a structural unit derived from α, β-unsaturated carboxylic acid, and at least a part of α, β-unsaturated carboxylic acid is neutralized by metal ions. Examples include the summed resin. Examples of the metal ion include sodium ion. In the ethylene / α, β-unsaturated carboxylic acid copolymer serving as the base polymer, the content ratio of the constituent units of α, β-unsaturated carboxylic acid is preferably 2% by mass or more, preferably 5% by mass or more. More preferably. The content ratio of the constituent units of α, β-unsaturated carboxylic acid is preferably 30% by mass or less, and more preferably 20% by mass or less. In the present invention, an ethylene / acrylic acid copolymer ionomer and an ethylene / methacrylic acid copolymer ionomer are preferable from the viewpoint of easy availability. Examples of ethylene-based ionomers include sodium ionomers, which are ethylene-acrylic acid copolymers, and sodium ionomers, which are ethylene-methacrylic acid copolymers, as particularly preferable examples.

Examples of the α, β-unsaturated carboxylic acid constituting the ionomer include acrylic acid, methacrylic acid, maleic acid, monomethyl maleate, monoethyl maleate, maleic anhydride and the like, but acrylic acid or methacrylic acid is particularly preferable. ..

In the B layer, as components other than the thermoplastic resin such as polyvinyl acetal resin, a heat shield material (for example, an inorganic heat shield fine particle or an organic heat shield material having an infrared absorbing ability), an ultraviolet absorber, a plasticizer, and an oxidation Preventive agents, light stabilizers, adhesive strength modifiers and / or various additives for adjusting adhesiveness, blocking inhibitors, pigments, dyes and the like may be added as necessary. Examples of the ultraviolet absorber, antioxidant, light stabilizer and the like include those contained in the above-mentioned A layer.

(Heat shield material)
A heat-shielding material (for example, an inorganic heat-shielding fine particle or an organic heat-shielding material having an infrared absorbing ability) may be contained in the B layer. As the heat shield material, the same material that can be contained in the A layer can be used.

When the heat shield material is contained in the B layer, the infrared absorption capacity of the heat shield material is the optical path length (m) when infrared rays pass through the B layer and the concentration of the heat shield material in the B layer (g / m ^3). ). Therefore, the infrared absorption capacity of the heat shield material is proportional to ^{the surface density (g / m 2) of the heat shield material in the B layer.}

When metal-doped tungsten oxide (cesium-doped tungsten oxide) is used as the heat-shielding material in the B layer, the surface density (g / m ² ) of the heat-shielding material is preferably 0.10 or more, preferably 0.15 or more. Is more preferable, and 0.20 or more is further preferable. ^{If the surface density (g / m 2} ) of the heat shield material in the B layer is less than 0.10, it tends to be difficult to obtain a sufficient heat shield effect. When metal-doped tungsten oxide (cesium-doped tungsten oxide) is used as the heat-shielding material in the B layer, the surface density (g / m ² ) of the heat-shielding material is preferably 1.00 or less, preferably 0.70 or less. Is more preferable, and 0.50 or less is further preferable. ^{When the surface density (g / m 2} ) of the heat shield material in the B layer exceeds 1.00, the visible light transmittance is lowered, the haze is deteriorated, and the weather resistance is lowered when the laminated glass is used. Or, the color difference change tends to increase.

When tin-doped indium oxide is used as the heat shield material in the B layer, the surface density (g / m ² ) of the heat shield material is preferably 0.50 or more, more preferably 1.00 or more. , 1.50 or more is more preferable, 2.25 or more is particularly preferable, and 3.00 or more is most preferable. When tin-doped indium oxide is used as the heat shield material in the B layer, the surface density (g / m ² ) of the heat shield material is preferably 15.00 or less, and more preferably 10.50 or less. It is preferably 7.50 or less, and more preferably 7.50 or less.

When antimony-doped tin oxide is used as the heat-shielding material in the B layer, the surface density (g / m ² ) of the heat-shielding material is preferably 1.00 or more, more preferably 1.50 or more. , 2.00 or more is more preferable. When antimony-doped tin oxide is used as the heat-shielding material in the B layer, the surface density (g / m ² ) of the heat-shielding material is preferably 10.00 or less, and more preferably 7.00 or less. It is preferably 5.00 or less, and more preferably 5.00 or less.

When a phthalocyanine compound is used as the heat shield material in the B layer, the surface density (g / m ² ) of the heat shield material is preferably 0.010 or more, more preferably 0.015 or more, and 0. It is more preferably .020 or more. When a phthalocyanine compound is used as the heat shield material in the B layer, the surface density (g / m ² ) of the heat shield material is preferably 0.100 or less, more preferably 0.070 or less. It is more preferably 0.050 or less.

When aluminum-doped zinc oxide is used as the heat shield material in the B layer, the surface density (g / m ² ) of the heat shield material is preferably 1.00 or more, more preferably 1.50 or more. , 2.00 or more is more preferable. When aluminum-doped zinc oxide is used as the heat shield material in the B layer, the surface density (g / m ² ) of the heat shield material is preferably 10.00 or less, and more preferably 7.00 or less. It is preferably 5.00 or less, and more preferably 5.00 or less.

When zinc antimonate is used as the heat shield material in the B layer, the surface density (g / m ² ) of the heat shield material is preferably 1.00 or more, more preferably 1.50 or more. It is more preferably 2.00 or more. When zinc antimonate is used as the heat shield material in the B layer, the surface density (g / m ² ) of the heat shield material is preferably 10.00 or less, more preferably 7.00 or less. , 5.00 or less is more preferable.

When lanthanum hexaboride is used as the heat shield material in the B layer, the surface density (g / m ² ) of the heat shield material is preferably 0.02 or more, more preferably 0.03 or more. , 0.04 or more is more preferable. When lanthanum hexaboride is used as the heat shield material in the B layer, the surface density (g / m ² ) of the heat shield material is preferably 0.20 or less, and more preferably 0.14 or less. It is preferably 0.10 or less, and more preferably 0.10 or less.

The interlayer film for laminated glass of the present invention may contain a heat shield material in the B layer. In this case, it is preferable that at least one type of ultraviolet absorber is contained in the B layer. By configuring the laminated glass interlayer film as described above, for example, when the A layer is the inner layer and the B layer is the outer layer, the thermoplastic elastomer of the A layer is protected from ultraviolet rays, and the laminated glass interlayer film is protected from ultraviolet rays. The heat shield can be improved.

When the interlayer film for laminated glass of the present invention has a three-layer structure of B layer / A layer / B layer with the B layer as an outer layer, the B layer is formed by containing a heat shield material in the B layer. Since infrared rays pass through the optical path lengths of two layers, the heat shielding property can be improved without impairing the visible light transmittance and haze of the laminated glass.

(UV absorber)
Examples of the ultraviolet absorber that can be used in the B layer include the same ultraviolet absorbers that may be contained in the A layer.

^{The surface density (g / m 2} ) of the ultraviolet absorber in the B layer is preferably 0.2 or more, more preferably 0.5 or more, and further preferably 0.7 or more. ^{When the surface density (g / m 2} ) of the ultraviolet absorber in the B layer is less than 0.1, haze deteriorates, weather resistance decreases, and color difference change increases when laminated glass is used. Tend to do.

^{The surface density (g / m 2} ) of the ultraviolet absorber in the B layer is preferably 10.0 or less, more preferably 5.0 or less, and further preferably 3.0 or less. When the surface density (g / m ² ) of the ultraviolet absorber in the B layer exceeds 10.0, the visible light transmittance is lowered, the haze is deteriorated, and the weather resistance is lowered when the laminated glass is used. Or, the change in color difference tends to increase.

The amount of the ultraviolet absorber added is preferably 10 ppm or more, more preferably 100 ppm or more, based on the mass of the thermoplastic resin contained in the B layer. If the amount added is less than 10 ppm, it may be difficult to exert a sufficient effect. In addition, two or more kinds of ultraviolet absorbers can be used in combination.

The amount of the ultraviolet absorber added is preferably 50,000 ppm or less, more preferably 10,000 ppm or less, based on the mass of the thermoplastic resin contained in the B layer. Even if the amount added is more than 50,000 ppm, no remarkable effect can be expected.

(Plasticizer)
The plasticizer used in the B layer of the present invention is not particularly limited, but is a carboxylic acid ester plasticizer such as a monovalent carboxylic acid ester type or a polyvalent carboxylic acid ester type; a phosphoric acid ester type plasticizer, an organic sub-layer. In addition to phosphoric acid ester plasticizers, polymer plasticizers such as carboxylic acid polyester type, carbonate polyester type, and polyalkylene glycol type, and ester compounds of hydroxycarboxylic acid and polyhydric alcohol such as castor oil; hydroxycarboxylic acid Hydroxycarboxylic acid ester-based plasticizers such as ester compounds of monovalent alcohols can also be used.

Examples of the monovalent carboxylic acid ester-based plasticizer include monovalent carboxylic acids such as butanoic acid, isobutanoic acid, hexane acid, 2-ethylbutanoic acid, heptanoic acid, octyl acid, 2-ethylhexanoic acid, and lauric acid, and ethylene. It is a compound obtained by a condensation reaction with a polyhydric alcohol such as glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, and glycerin. Specific examples of the compound include triethylene glycol di2-diethyl. Butanoate, Triethylene Glycol Diheptanoate, Triethylene Glycol Di2-Ethyl Hexanoate, Triethylene Glycol Dioctanoate, Tetraethylene Glycol Di2-Ethyl Butanoate, Tetraethylene Glycol Diheptanoate, Tetraethylene glycol di2-ethylhexanoate, tetraethylene glycol dioctanoate, diethylene glycol di2-ethylhexanoate, PEG # 400 di2-ethylhexanoate, triethylene glycol mono2-ethylhexanoate, Examples include complete or partial esterifications of glycerin or diglycerin with 2-ethylhexanoic acid. Here, PEG # 400 represents polyethylene glycol having an average molecular weight of 350 to 450.

Polycarboxylic acid ester-based plasticizers include polycarboxylic acids such as adipic acid, succinic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, and trimetic acid, and methanol, ethanol, butanol, and hexanol. Examples thereof include compounds obtained by a condensation reaction with alcohols having 1 to 12 carbon atoms such as 2-ethylbutanol, heptanol, octanol, 2-ethylhexanol, decanol, dodecanol, butoxyethanol, butoxyethoxyethanol and benzyl alcohol. Examples of specific compounds include dihexyl adipate, di-2-ethylbutyl adipate, diheptyl adipate, dioctyl adipate, di2-ethylhexyl adipate, di (butoxyethyl) adipate, di (butoxyethoxyethyl butoxyethoxyethyl) adipate. ), Mono (2-ethylhexyl) adipic acid, Dibutyl sebacate, Dihexyl sebacate, Di2-ethylbutyl sebacate, Dibutyl phthalate, Dihexyl phthalate, Di (2-ethylbutyl) phthalate, Dioctyl phthalate, Di phthalate (2-Ethylhexyl), benzylbutyl phthalate, didodecyl phthalate and the like can be mentioned.

Phosphoric acid-based plasticizers or phosphite-based plasticizers include phosphoric acid or phosphite, methanol, ethanol, butanol, hexanol, 2-ethylbutanol, heptanol, octanol, 2-ethylhexanol, decanol, dodecanol. , Butoxyethanol, butoxyethoxyethanol, or a compound obtained by a condensation reaction with an alcohol having 1 to 12 carbon atoms such as benzyl alcohol. Examples of specific compounds are trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tri (butoxyethyl) phosphate, tri (2-ethylhexyl) phosphate. ) And so on.

Glycol Polyester-based plasticizers include oxalic acid, malonic acid, succinic acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4. -Polyvalent carboxylic acids such as cyclohexanedicarboxylic acid and ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3- Butylene glycol, 1,4-butylene glycol, 1,2-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 3-methyl-1 , 5-Pentanediol, 3-Methyl-2,4-Pentanediol, 1,2-Heptanediol, 1,7-Heptanediol, 1,2-octanediol, 1,8-octanediol, 1,2-Nonan Didiol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,2-decanediol, 1,10-decanediol, 1,2-dodecanediol, 1,12-dodecanediol, 1, 2-Cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-bis (hydroxymethyl) cyclohexane, 1,3-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxymethyl) Dicarboxylic acid polyester obtained by alternating copolymerization of polyvalent alcohol such as cyclohexane, or aliphatic hydroxycarboxylic acid; glycolic acid, lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 6-hydroxyhexane. Acids, 8-hydroxyhexanoic acid, 10-hydroxydecanoic acid, 12-hydroxydodecanoic acid, hydroxycarboxylic acids with aromatic rings; hydroxycarboxylic acids such as 4-hydroxybenzoic acid, 4- (2-hydroxyethyl) benzoic acid. Polymer (hydroxycarboxylic acid polyester), aliphatic lactone compound; γ-butyrolactone, γ-valerolactone, δ-valerolactone, β-methyl-δ-valerolactone, δ-hexanolactone, ε-caprolactone, lactide, etc. , A lactone compound having an aromatic ring; a carboxylic acid polyester obtained by ring-opening polymerization of a lactone compound such as phthalide may be used. The terminal structure of these carboxylic acid polyesters is not particularly limited, and may be a hydroxyl group or a carboxyl group, or may be an ester bond formed by reacting the terminal hydroxyl group or the terminal carboxyl group with a monovalent carboxylic acid or a monohydric alcohol.

Examples of polyester carbonate-based plasticizers include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, and 1 , 4-butylene glycol, 1,2-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 3-methyl-1,5-pentane Glycol, 3-methyl2,4-pentanediol, 1,2-heptanediol, 1,7-heptanediol, 1,2-octanediol, 1,8-octanediol, 1,2-nonanediol, 1,9 -Nonandiol, 2-methyl-1,8-octanediol, 1,2-decanediol, 1,10-decanediol, 1,2-dodecanediol, 1,12-dodecanediol, 1,2-cyclohexanediol, Multivalent values such as 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-bis (hydroxymethyl) cyclohexane, 1,3-bis (hydroxymethyl) cyclohexane, and 1,4-bis (hydroxymethyl) cyclohexane. Examples thereof include polyester carbonate obtained by alternately copolymerizing alcohol with a carbonate ester such as dimethyl carbonate or diethyl carbonate by an ester exchange reaction. The terminal structure of these polyester carbonate compounds is not particularly limited, but may be a carbonic acid ester group, a hydroxyl group, or the like.

As the polyalkylene glycol-based plasticizer, alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and oxetane are ring-opened and polymerized using a monohydric alcohol, a polyhydric alcohol, a monovalent carboxylic acid, and a polyvalent carboxylic acid as an initiator. Examples thereof include the obtained polymer.

Examples of the hydroxycarboxylic acid ester-based plasticizer include monovalent alcohol esters of hydroxycarboxylic acids; methyl ricinolate, ethyl ricinolate, butyl ricinolate, methyl 6-hydroxyhexanoate, ethyl 6-hydroxyhexanoate, and 6-hydroxyhexanoic acid. Polyhydric alcohol esters of butyl and hydroxycarboxylic acids; ethylene glycol di (6-hydroxyhexanoic acid) esters, diethylene glycol di (6-hydroxyhexanoic acid) esters, triethylene glycol di (6-hydroxyhexanoic acid) esters, 3-methyl -1,5-pentanedioldi (6-hydroxyhexanoic acid) ester, 3-methyl-1,5-pentanedioldi (2-hydroxybutyric acid) ester, 3-methyl-1,5-pentanedioldi (3-hydroxybutyric acid) Hydroxybutyric acid) ester, 3-methyl-1,5-pentanedioldi (4-hydroxybutyric acid) ester, triethylene glycol di (2-hydroxybutyric acid) ester, glycerintri (ricinolic acid) ester, L-tartrate di (1) -(2-Ethylhexyl)), castor oil, and compounds in which the k hydroxycarboxylic acid-derived groups of the polyhydric alcohol ester of hydroxycarboxylic acid are replaced with hydroxyl group-free carboxylic acid-derived groups or hydrogen atoms are also used. It is possible, and as these hydroxycarboxylic acid esters, those obtained by conventionally known methods can be used.

In the present invention, these plasticizers may be used alone or in combination of two or more.

When the plasticizer is contained in the B layer, it has a melting point from the viewpoint of enhancing the compatibility between the plasticizer and the resin used in the B layer (particularly the polyvinyl acetal resin), low migration to other layers, and non-migration. Is 30 ° C. or lower and has a hydroxyl value of 15 mgKOH / g or more and 450 mgKOH / g or less, or an ester plasticizer or ether plasticizer, or is non-crystalline and has a hydroxyl value of 15 mgKOH / g or more and 450 mgKOH / g. It is preferable to use the following ester-based plasticizers or ether-based plasticizers. Here, amorphous means that a melting point is not observed at a temperature of −20 ° C. or higher. The hydroxyl value is preferably 15 mgKOH / g or more, more preferably 30 mgKOH / g or more, and most preferably 45 mgKOH / g or more. Further, the hydroxyl value is preferably 450 mgKOH / g or less, more preferably 360 mgKOH / g or less, and most preferably 280 mgKOH / g or less. Examples of the ester-based plasticizer include polyesters satisfying the above regulations (the above-mentioned carboxylic acid polyester-based plasticizer, carbonated polyester-based plasticizer, etc.) and hydroxycarboxylic acid ester compounds (the above-mentioned hydroxycarboxylic acid ester-based plasticizer, etc.). Examples of the ether-based plasticizer include polyether compounds satisfying the above-mentioned regulations (such as the above-mentioned polyalkylene glycol-based plasticizer).

The content of the plasticizer is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, further preferably 30 parts by mass or less, and 20 parts by mass with respect to 100 parts by mass of the polyvinyl acetal resin. It is particularly preferable that the content is parts by mass or less. When the content of the plasticizer exceeds 50 parts by mass with respect to 100 parts by mass of the polyvinyl acetal resin, the shear storage elastic modulus tends to decrease. Further, two or more kinds of plasticizers may be used in combination.

As the plasticizer, a compound having a hydroxyl group can be used, but the ratio of the content of the compound having a hydroxyl group to the total amount of the plasticizer used in the B layer is preferably 50% by mass or more, preferably 70% by mass. It is more preferably% or more, and further preferably 90% by mass or more. Since the compound having a hydroxyl group has high compatibility with the polyvinyl acetal resin and has low transferability to another resin layer, the compound having a hydroxyl group can be preferably used.

(Antioxidant)
As the antioxidant that may be contained in the B layer, the same antioxidant as that contained in the A layer is used.

The antioxidants can be used alone or in combination of two or more. The surface density of the antioxidant in the B layer ^{is preferably 0.1 g / m 2} or more, more preferably 0.2 g / m ² or more, and further preferably 0.5 g / m ² or more. preferable. If the surface density of the ^{antioxidant in the B layer is less than 0.1 g / m 2} , the B layer is easily oxidized, and when the laminated glass is used for a long period of time, the color difference changes greatly and the weather resistance becomes large. It tends to decrease.

The surface density of the antioxidant in the B layer ^{is preferably 2.5 g / m 2} or less, more preferably 1.5 g / m ² or less, and further preferably 2.0 g / m ² or less. preferable. If the surface density of the antioxidant in the B layer ^{exceeds 2.5 g / m 2} , the color tone of the B layer tends to be impaired and the haze of the laminated glass tends to decrease.

The blending amount of the antioxidant is preferably 0.001 part by mass or more, and more preferably 0.01 part by mass or more with respect to 100 parts by mass of the thermoplastic resin such as polyvinyl acetal resin. If the amount of the antioxidant is less than 0.001 part by mass, it may be difficult to exert a sufficient effect.

The blending amount of the antioxidant is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and 3 parts by mass or less with respect to 100 parts by mass of a thermoplastic resin such as polyvinyl acetal resin. Is the most preferable. Even if the amount of the antioxidant is increased to more than 5 parts by mass, a remarkable effect cannot be expected.

(Light stabilizer)
Examples of the light stabilizer include hindered amine-based ones, such as "ADEKA STAB LA-57 (trade name)" manufactured by ADEKA Corporation and "Tinuvin-622SF (trade name)" manufactured by Ciba Specialty Chemicals Co., Ltd. The light stabilizer can be used alone or in combination of two or more. The blending amount of the light stabilizer is preferably 0.01 part by mass or more, and more preferably 0.05 part by mass or more with respect to 100 parts by mass of the thermoplastic resin such as polyvinyl acetal resin. If the amount of the light stabilizer is less than 0.01 parts by mass, it may be difficult to exert a sufficient effect. The content of the light stabilizer is preferably 10 parts by mass or less, more preferably 5 parts by mass or less. Even if the amount of the light stabilizer is increased to more than 10 parts by mass, a remarkable effect cannot be expected. The areal density of the light stabilizer in B layer, is preferably 0.05 g / ^{m 2} or more, more preferably 0.5 g / ^{m 2} or more. The surface density is ^{preferably 70 g / m 2} or less, and ^{more preferably 30 g / m 2} or less.

(Adhesive strength adjuster)
Further, if necessary, the layer B may contain an adhesive force adjusting agent and / or various additives for adjusting the adhesiveness in order to control the adhesiveness of the interlayer film for laminated glass to glass or the like. Good.

As various additives for adjusting the adhesiveness, those disclosed in International Publication No. 03/033583 can also be used, and alkali metal salts and alkaline earth metal salts are preferably used, for example, potassium. , Sodium, magnesium and other salts. Examples of the salt include organic acids such as carboxylic acids such as octanoic acid, hexanoic acid, butyric acid, acetic acid and formic acid; and salts of inorganic acids such as hydrochloric acid and nitric acid.

The optimum amount of the adhesive strength adjusting agent and / or various additives for adjusting the adhesiveness varies depending on the additive used, but the adhesive strength of the obtained interlayer film for laminated glass to the glass is determined by the Panmel test (Pammel test). In Pummeltest (described in International Publication No. 03/033583, etc.), it is generally preferable to adjust the amount to 3 or more and 10 or less, and especially when high penetration resistance is required, 3 or more, 6 or less, high. When glass shatterproofness is required, it is preferable to adjust the amount to 7 or more and 10 or less. When high glass shatterproofness is required, it is also a useful method not to add an adhesive force adjusting agent.

[C layer]
The interlayer film for laminated glass of the present invention can have a laminated structure of B layer / A layer / C layer by using C layer having a composition and thickness different from that of B layer. As the C layer, a layer made of a known resin can be used, for example, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, polyurethane, polytetrafluoroethylene, acrylic resin, polyamide, polyacetal, polycarbonate, polyester. Among them, polyethylene terephthalate, polybutylene terephthalate, cyclic polyolefin, polyphenylensulfide, polytetrafluoroethylene, polysulfone, polyether sulfone, polyarylate, liquid crystal polymer, polyimide and the like can be used. As the C layer, a film made of these resins can be used, but it is also possible to form the C layer by applying a coating agent such as an adhesive to the A layer.

In addition, as the thermoplastic resin constituting the C layer, the same resin as that used in the B layer can be used. For example, polyvinyl acetal resin, ionomer, ethylene vinyl acetate, vinyl chloride resin, urethane resin, silicone resin, polyamide resin and the like are preferable. By using these thermoplastic resins for the C layer, it is possible to improve the weather resistance and strength of the interlayer film for laminated glass and adjust the adhesiveness with the glass. From the viewpoint of adhesiveness to glass and transparency, the thermoplastic resin used for the C layer is preferably polyvinyl acetal resin or ionomer.

The C layer is not particularly limited as long as the refractive index difference from the A layer is 0.03 or less, but for example, when it is put into practical use as an interlayer film for laminated glass, the glass scattering property at the time of breakage is low. From the viewpoint that safety glass can be produced, it is preferable to use a polyvinyl acetal resin layer made of a composition containing a polyvinyl acetal resin.

The resin film constituting the C layer is composed of a polymer having a refractive index in the range of 1.485 to 1.495 as measured based on ASTM D542, from the viewpoint of enhancing the transparency of the C layer. preferable.

The thickness of the C layer is preferably 1 μm or more, and more preferably 10 μm or more. The thickness of the C layer is preferably 300 μm or less, more preferably 250 μm or less.

In the C layer, as components other than the thermoplastic resin, a heat shield material (for example, an inorganic heat shield fine particle or an organic heat shield material having an infrared absorbing ability), an ultraviolet absorber, a plastic agent, an antioxidant, and a light stabilizer are added. Agents, adhesive strength modifiers and / or various additives for adjusting adhesiveness, anti-blocking agents, pigments, dyes and the like may be added as necessary. As these components, the same ones as those described in the above-mentioned A layer and B layer can be used.

(Polyvinyl acetal resin)
When a composition containing a thermoplastic resin such as polyvinyl acetal resin is used as the C layer, it is preferable that the C layer contains 40% by mass or more of the thermoplastic resin such as polyvinyl acetal resin from the viewpoint of the mechanical strength of the film. , 50% by mass or more, more preferably 60% by mass or more, particularly preferably 80% by mass or more, further preferably 90% by mass or more, and a thermoplastic resin such as a polyvinyl acetal resin. The C layer may be composed of only the C layer.

The polyvinyl acetal resin preferably has an average acetalization degree of 40 mol% or more. The average degree of acetalization of the polyvinyl acetal resin is more preferably 60 mol% or more, and further preferably 65 mol% or more from the viewpoint of water resistance. The polyvinyl acetal resin preferably has an average acetalization degree of 90 mol% or less. The average degree of acetalization of the polyvinyl acetal resin is more preferably 85 mol% or less, and further preferably 80 mol% or less from the viewpoint of water resistance.

From the viewpoint of heat resistance during molding, the polyvinyl acetal resin preferably has a vinyl acetate unit content of 30 mol% or less, more preferably 20 mol% or less, and particularly 15 mol% or less. The one is more preferable.

The content of the vinyl alcohol unit of the polyvinyl acetal resin is preferably 15 mol% or more, more preferably 20 mol% or more, and further preferably 25 mol% or more. The content of the vinyl alcohol unit of the polyvinyl acetal resin is preferably 50 mol% or less, more preferably 45 mol% or less, and further preferably 40 mol% or less.

From the viewpoint of mechanical strength, the viscosity average degree of polymerization of polyvinyl alcohol, which is a raw material of the polyvinyl acetal resin, is preferably 100 or more, more preferably 300 or more, more preferably 400 or more, and more than 600 or more. Is more preferable, 700 or more is particularly preferable, and 750 or more is most preferable. The viscosity average degree of polymerization of polyvinyl alcohol is preferably 3000 or less, more preferably 2500 or less, further preferably 2300 or less, particularly preferably 2000 or less, and 1800 or less. Is most preferable. If the viscosity average degree of polymerization exceeds 3000, the moldability is significantly deteriorated, which is not preferable.

As the aldehydes used for acetalizing polyvinyl alcohol, aldehydes having 1 or more carbon atoms and 12 or less carbon atoms are preferable. Among these, aliphatic aldehydes having 2 or more carbon atoms and 6 or less carbon atoms are preferable, and butyraldehyde is particularly preferable.

(Plasticizer)
The plasticizer used in the C layer of the present invention is not particularly limited, but includes carboxylic acid ester-based plasticizers, phosphoric acid ester-based plasticizers, organic subphosphate ester-based plasticizers, and carboxylic acid polyester-based plasticizers. Polymer plasticizers such as polyester carbonate and polyalkylene glycol, ester compounds of hydroxycarboxylic acid and polyhydric alcohol, and hydroxycarboxylic acid ester plasticizers can also be used. Of these, triethylene glycol di2-ethylhexanoate is preferable. The content of the plasticizer is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and further preferably 30 parts by mass or less, based on 100 parts by mass of the polyvinyl acetal resin. It is particularly preferable that the content is parts by mass or less.

[Interlayer film for laminated glass]
The laminated glass interlayer film of the present invention can be suitably used as a laminated glass interlayer film having functionality such as heat shielding property, conductivity, and design property, and having excellent visibility and transparency. The interlayer film for laminated glass has at least one A layer. Further, it is preferable that the A layer is laminated between at least two B layers.

Hereinafter, glass also includes organic glass using acrylic resin or polycarbonate resin, and the use of organic glass leads to a significant reduction in the weight of laminated glass, so that it can be preferably used, but the surface is scratch resistant and rigid. From the viewpoint of the above, inorganic glass can be more preferably used.

From the viewpoint of ensuring visibility when the laminated glass is made of clear glass, the visible light transmittance is 70% or more, more preferably 72% or more, and further preferably 73% or more. .. If the visible light transmittance in the case of laminated glass is less than 70%, the visibility of the laminated glass is impaired.

From the viewpoint of ensuring visibility when green glass is used as laminated glass, the visible light transmittance is preferably 70% or more, more preferably 72% or more, and 73% or more. Is even more preferable. If the visible light transmittance in the case of laminated glass is less than 70%, the visibility of the laminated glass tends to be impaired.

When a heat-shielding material is added to the A layer or B layer of the interlayer film for laminated glass of the present invention, at least 1 is obtained from the viewpoint of improving the color tone while achieving both transparency and heat-shielding property when the laminated glass is used. A laminated glass in which a heat-shielding material is contained in a layer and an interlayer film for laminated glass is arranged between two green glasses having a total thickness of 4 mm or less, and a visible light transmittance of 70% or more. It is preferable that the average infrared transmittance at a wavelength of 800 to 1100 nm is 32% or less.

Similarly, when a heat-shielding material is added to the A layer or B layer of the interlayer film for laminated glass of the present invention, when the laminated glass is produced using clear glass, the heat-shielding property is further improved while ensuring visibility. The average infrared transmittance at a wavelength of 800 to 1100 nm is 72% or less, preferably 70% or less, more preferably 69% or less, further preferably 68% or less, and 65% or less. It is particularly preferably 0% or less, and most preferably 60% or less. If the average infrared transmittance at a wavelength of 800 to 1100 nm in the case of laminated glass exceeds 72%, the heat shielding property is lowered. Further, as a method of setting the visible light transmittance to 70% or more in a laminated glass in which an interlayer film for laminated glass is arranged between two clear glasses having a total thickness of 4 mm or less, for example. , The surface density of the heat shield material in the A layer or the B layer is set to 10 g / m ² or less, or the surface density of the ultraviolet absorber in the A layer or the B layer is set to 10 g / m ² or less. As a method of setting the infrared average transmittance at a wavelength of 800 to 1100 nm to 72% or less in a laminated glass in which an interlayer film for laminated glass is arranged between two clear glasses having a total thickness of 4 mm or less. For example, a method of setting the surface density of the heat shield material in the A layer or the B layer to 0.10 g / m ² or more can be mentioned.

Similarly, when a heat-shielding material is added to the A layer or B layer of the interlayer film for laminated glass of the present invention, when the laminated glass is produced using green glass, the heat-shielding property is further improved while ensuring visibility. From the viewpoint of making the infrared rays, the average infrared transmittance at a wavelength of 800 to 1100 nm is preferably 32% or less, more preferably 31% or less, and further preferably 30% or less. When the average infrared transmittance at a wavelength of 800 to 1100 nm in the case of laminated glass exceeds 32%, the heat shielding property tends to decrease. In a laminated glass in which an interlayer film for laminated glass is arranged between two green glasses having a total thickness of 4 mm or less, a method of setting the visible light transmittance to 70% or more is, for example, A. Examples thereof include a method in which the surface density of the heat shield material in the layer or the B layer is 10 g / m ² or less, and the surface density of the ultraviolet absorber in the A layer or the B layer is 10 g / m ² or less. As a method of setting the infrared average transmittance at a wavelength of 800 to 1100 nm to 32% or less in a laminated glass in which an interlayer film for laminated glass is arranged between two green glasses having a total thickness of 4 mm or less. For example, a method of setting the surface density of the heat shield material in the A layer or the B layer to 0.10 g / m ² or more can be mentioned.

From the viewpoint of further improving the weather resistance of the laminated glass and further suppressing the change in color difference, the laminated glass is used under the conditions of an illuminance of 180 W / m ² , a black panel temperature of 60 ° C., and a relative humidity of 50%. The color difference change ΔE * ab (simply also referred to as color difference change) before and after the weather resistance test of exposure for 200 hours is preferably 2.0 or less, and preferably 1.8 or less. More preferably, it is 1.5 or less. If the color difference change ΔE * ab exceeds 2.0 under the above conditions, the color tone tends to change easily due to long-term use of the laminated glass. In measuring the color difference change, the glass used for the laminated glass may be clear glass or green glass.

The laminated glass interlayer film of the present invention has a haze of 1.0% or less when a laminated glass in which the laminated glass interlayer film is sandwiched between two sheets of glass is produced. From the viewpoint of producing a laminated glass having higher transparency, the haze is more preferably 0.9% or less, and further preferably 0.7% or less. If the haze exceeds 1.0% in the case of laminated glass, the transparency tends to decrease. When the haze is adjusted by the A layer, it can be determined, for example, by the refractive index, particle size, addition amount, etc. of the elastic particles added to the acrylic film. Further, it can be adjusted by the refractive index, dispersion morphology, addition amount and the like of the block copolymer. The haze can be measured based on JIS K7136. When measuring the haze, the glass used for the laminated glass may be clear glass or green glass.

As shown in FIG. 1, the laminated glass interlayer film of the present invention can have a laminated structure in which the A layer 4 is sandwiched between the B layer 2 and the B layer 5 as a B layer / A layer / B layer. .. A functional layer 3 is provided on one surface of the A layer 4, and the B layer 2 and the B layer 5 are laminated from both sides thereof to form an interlayer film for laminated glass. Further, the laminated glass can be produced by sandwiching the interlayer film for laminated glass between the two sheets of glass 1 and 6. In FIG. 1, the functional layer 3 is provided on one surface of the A layer 4, but it is also possible to provide the functionality of the A layer 4 itself without providing the functional layer 3. Is.

The laminated structure of the laminated body is determined by the purpose, but in addition to the laminated structure of B layer / A layer / B layer, B layer / A layer / B layer / A layer, B layer / A layer / B layer / A layer / It may have a laminated structure called a B layer. Among the above, it is preferable that the A layer is laminated between at least two B layers. Further, it is preferable that the B layer constitutes at least one layer of the outermost layer.

Further, the interlayer film for laminated glass of the present invention can have, for example, a laminated structure in which the A layer is sandwiched between the B layer and the C layer different from the B layer. For example, B layer / A layer / C layer, B layer / A layer / C layer / B layer, B layer / A layer / B layer / C layer, B layer / C layer / A layer / C layer / B layer, B layer / C layer / A layer / B layer / C layer, B layer / A layer / C layer / B layer / C layer, C layer / B layer / A layer / B layer / C layer, C layer / B layer A laminated structure such as / A layer / C layer / B layer / C layer, C layer / B layer / C layer / A layer / C layer / B layer / C layer may be used. Among these, it is preferable that the B layer constitutes at least one layer of the outermost layer.

When the interlayer film for laminated glass of the present invention has a laminated structure in which the A layer is laminated between at least two B layers, the difference in the refractive index between the refractive index of the A layer and the refractive index of the B layer is 0. It is 05 or less. The difference in refractive index between the refractive index of the A layer and the refractive index of the B layer is preferably 0.04 or less, and more preferably 0.03 or less. When the difference in refractive index between the refractive index of the A layer and the refractive index of the B layer is larger than 0.03, the transparency of the obtained laminated glass is lowered. As a method for reducing the difference in refractive index between the refractive index of the A layer and the refractive index of the B layer to 0.05 or less, polyvinyl composed of a composition containing an acrylic resin in the A layer and a polyvinyl acetal resin in the B layer. A method using an acetal resin layer can be mentioned. The refractive index can be measured based on ASTM D542.

When the interlayer film for laminated glass of the present invention has a laminated structure in which the A layer is laminated between the B layer and the C layer different from the B layer, the refractive index of the A layer and the refractive index of the B layer are The refractive index difference is 0.05 or less, and the refractive index difference between the refractive index of the A layer and the refractive index of the C layer is 0.05 or less. The difference in refractive index between the refractive index of the A layer and the refractive index of the B layer is preferably 0.04 or less, and more preferably 0.03 or less. The difference in refractive index between the refractive index of the A layer and the refractive index of the C layer is preferably 0.04 or less, and more preferably 0.03 or less. When the difference in refractive index between the refractive index of the A layer and the refractive index of the C layer is larger than 0.03, the transparency of the obtained laminated glass is lowered. The refractive index can be measured based on ASTM D542.

[Manufacturing method of interlayer film for laminated glass]
The method for producing the interlayer film for laminated glass of the present invention is not particularly limited, and the composition for layer A in which the thermoplastic resin constituting the layer A is mixed with other additives as necessary is uniformly kneaded. After that, the A layer is prepared by a known film forming method such as an extrusion method, a calendar method, a pressing method, a casting method, an inflation method, etc., and a B layer is prepared by the same method, and these are laminated by press molding or the like. The A layer, the B layer and other necessary layers may be formed by a coextrusion method using a multi-manifold die or a feed block method.

The film thickness of the laminate constituting the interlayer film for laminated glass of the present invention is preferably 20 μm or more, more preferably 100 μm or more. If the film thickness of the laminated body is too thin, it may not be possible to laminate well when producing laminated glass. The film thickness of the laminated body is preferably 10,000 μm or less, more preferably 3,000 μm or less. If the film thickness of the laminate is too thick, it tends to lead to high cost.

Among the known film-forming methods, a method of producing a film (sheet) using an extruder is particularly preferably adopted. In the layer A, the resin temperature at the time of extrusion is preferably 200 ° C. or higher, more preferably 220 ° C. or higher. The resin temperature at the time of extrusion is preferably 270 ° C. or lower, more preferably 250 ° C. or lower. If the resin temperature becomes too high, the thermoplastic resin constituting the A layer will decompose, and there is a concern that the resin will deteriorate. On the contrary, if the temperature is too low, the discharge from the extruder is not stable, which causes mechanical trouble. In the B layer, the resin temperature at the time of extrusion is preferably 150 ° C. or higher, more preferably 170 ° C. or higher. The resin temperature at the time of extrusion is preferably 250 ° C. or lower, more preferably 230 ° C. or lower. If the resin temperature becomes too high, the polyvinyl acetal resin will decompose, and there is concern about deterioration of the resin. On the contrary, if the temperature is too low, the discharge from the extruder is not stable, which causes mechanical trouble. Further, in order to efficiently remove the volatile substances in both the A layer and the B layer, it is preferable to remove the volatile substances from the vent port of the extruder by reducing the pressure.

Further, it is preferable to form a concavo-convex structure on the surface of the B layer of the present invention by a conventionally known method such as melt fracture or embossing. The shapes of the melt fracture and the embossing are not particularly limited, and conventionally known ones can be adopted. When the A layer, the B layer and other necessary layers are formed by the coextrusion method, a concavo-convex structure is formed on the outermost layer surface of the laminate formed by the coextrusion method by a conventionally known method such as melt fracture or embossing. It is preferable to form. The haze of the interlayer film of the present invention is defined in a state of being sandwiched between two pieces of glass to form a laminated glass so that the haze increase due to the above-mentioned uneven structure can be excluded from the measurement.

In particular, in the film constituting the A layer, since a functional film having heat shielding property, conductivity, design property, etc. is imparted in a subsequent process by an arbitrary method, the thickness accuracy of the film film thickness, high surface smoothness, and high transparency are provided. , It is necessary that there are few defects such as surface defects such as scratches and deterioration products caused by resins such as gelled carbides, and high-precision film forming technology is required.

[Manufacturing method of layer A]
The method for producing the thermoplastic resin multilayer film constituting the layer A of the present invention includes a step of putting the thermoplastic resin composition (R) into an extruder, melting the thermoplastic resin composition (R), and melt-extruding the thermoplastic resin composition (R) into a film from a T-die. A pair of cooling rolls, both of which are metal rigid rolls, or one of which is a metal rigid roll and the other of which is metal elastic. It is preferable to have a step of sandwiching between a pair of cooling rolls which are rolls.

(Melting kneading)
The thermoplastic resin composition (R) is generally used by melting and kneading a plurality of types of raw materials including the constituent resin and fine particle additives in advance to pelletize them, but it is necessary. Depending on the situation, only a part of an arbitrary ratio of the constituent resin and the fine particle additive are melt-kneaded in advance to pelletize, and each resin is dry-blended before being charged into the extruder using an extruder equipped with a plurality of feeders. It is also possible to use the masterbatch method of mixing and melt-kneading at. Further, if necessary, by using a twin-screw extruder equipped with a plurality of feeder equipment, it is possible to perform film forming at the same time as melt-kneading with the twin-screw extruder without prior melt-kneading.
The melt-kneading can be performed using, for example, a melt-kneading device such as a kneader ruder, an extruder, a mixing roll, and a Banbury mixer. The kneading temperature is appropriately adjusted according to the melting temperature of the resin component, and is usually preferably in the range of 140 ° C. to 300 ° C. Shear rate applied to the thermoplastic resin composition (Z) at the time of melt-kneading is preferably at 100 sec ^-1 or more, more preferably 200 sec ^-1 or more.
After performing melt-kneading at the above temperature, the obtained melt-kneaded product is cooled to a temperature of 120 ° C. or lower. For cooling, rapid cooling is preferable to natural cooling. Examples of the rapid cooling method include a method of immersing the molten strand in a cold water tank.
The thermoplastic resin composition (R) obtained by melt-kneading is generally in the form of pellets, but in order to enhance convenience during storage, transportation or molding, any form such as granules and powders can be used. It may be.

(Film molding)
Examples of the film molding method include an extrusion molding method, a solution casting method, a melt casting method, an inflation molding method, a blow molding method and the like. Above all, the extrusion molding method is preferable in the present invention. According to the extrusion molding method, a film having high transparency, good thickness uniformity, and good surface smoothness can be obtained with relatively high productivity.

In the extrusion molding method, an extruder with a T-die is preferably used. The extruder with a T-die heats and melts the raw material charging section such as a hopper into which the raw material thermoplastic resin composition (R) is charged and the charged thermoplastic resin composition (R) and sends it to the T-die side. It includes a screw portion and a T-die that extrudes the heat-melted thermoplastic resin composition (R) into a film.

In an extruder with a T-die, it is preferable that the molten resin is quantitatively supplied to the T-die using a gear pump. This makes it possible to produce a film with high thickness accuracy.
The molten resin is also preferably supplied to the T-die after impurities have been removed by filtration using a polymer filter or the like. The set temperature of the extruder with a T-die is not particularly limited, and is set according to the thermoplastic resin composition (R). The set temperature of the extruder with a T-die is preferably 160 ° C. or higher, more preferably 220 ° C. or higher. The set temperature of the extruder with a T-die is preferably 270 ° C. or lower, and more preferably 260 ° C. or lower. The set temperature of the extruder with a T-die is the melting temperature (processing temperature) of the thermoplastic resin composition (R).

The thermoplastic resin composition (R) melted at the above temperature is extruded in the form of a film vertically downward from the discharge port of the T-die. The temperature distribution of the T-die is preferably ± 15 ° C. or lower, more preferably ± 5 ° C. or lower, and particularly preferably ± 1 ° C. or lower. When the temperature distribution of the T-die exceeds ± 15 ° C., the molten resin may have uneven viscosity, and the obtained film may be distorted due to uneven thickness and uneven stress, which is not preferable.

Examples of the cooling method for the melt extruded from the T-die include a nip roll method, an electrostatic application method, an air knife method, a calendar method, a single-sided belt method, a double-sided belt method, and a three-roll method. In the present invention, the nip roll method is preferable.
In the nip roll method, the melt extruded from the T-die includes a plurality of cooling rolls (nip rolls) arranged adjacent to each other with a separation distance corresponding to a desired thickness of the thermoplastic resin film. Pressurized and cooled by a cooling roll unit.
Hereinafter, in the cooling roll unit, the nth cooling roll (n is an integer of 1 or more) from the upstream side is referred to as a "nth cooling roll". The cooling roll unit includes at least a first cooling roll and a second cooling roll having a separation portion below the discharge port of the T-die. The number of cooling rolls is 2 or more, preferably 3-4.

The melt extruded from the T-die is sandwiched between the first cooling roll and the second cooling roll, and is pressurized and cooled to form a thermoplastic resin film. The thermoplastic resin film is not sufficiently cooled by the cooling roll unit alone, and the thermoplastic resin film is usually not completely solidified even when it is separated from the most downstream cooling roll. After moving away from the most downstream cooling roll, the thermoplastic resin film is further cooled while flowing down.

In particular, in the present patent, it is important not to provide a gap between the melt and both cooling rolls at the moment when the melt is sandwiched between the first cooling roll and the second cooling roll. By not providing a gap, there is an effect of preventing volatile components from the melt from aggregating on the roll surface and forming a volume, and even if a large amount of additives such as an ultraviolet absorber is added to improve the light resistance performance, the roll Has the effect of not polluting.

When the first cooling roll and the second cooling roll used in the present patent require smooth surfaces on both sides of the film, the first cooling roll and the second cooling roll both have smooth surfaces. , Preferably a mirror surface. When a smooth surface is required on only one side of the film, it is preferable that one of the first cooling roll and the second cooling roll has a smooth surface, preferably a mirror surface, and the other. As the roll, a rubber roll or an embossed surface-shaped roll can be used. When a smooth surface is not required on both sides of the film, a rubber roll or an embossed surface-like roll can be used for both the first cooling roll and the second cooling roll, but a rubber roll is used for both. Since the surface of the rubber roll is too soft, the effect of adjusting the film thickness due to the pressure when the melt extruded from the die is sandwiched between the rolls is diminished, and it becomes difficult to control the film thickness, which is not preferable.

The first cooling roll and the second cooling roll used in the present patent are both metal rigid rolls or one metal rigid roll when both sides of the film require mirror-like smooth surfaces. The other is preferably a metal elastic roll.

The metal rigid body roll is a metal roll having high rigidity that does not deform during film production. As the metal rigid body roll, a known metal rigid body roll that has been generally used in extrusion molding can be used. The metal rigid body roll includes, for example, an inner roll made of a metal hollow roll such as a drilled roll or a spiral roll and a metal outer cylinder having a smooth surface, and the inner and / or inner roll and outer cylinder of the inner roll. A double-structured metal rigid body roll is used in which the cooling fluid flows down between the two. The thickness of the outer cylinder has a sufficient thickness so as not to be deformed during film production, and is, for example, about 20 mm. The material of the inner roll and the outer cylinder is not particularly limited, and examples thereof include stainless steel and chrome steel.

The metal elastic roll is a metal roll whose surface can be elastically deformed during film production. As the metal elastic roll, a known metal elastic roll that has been generally used in extrusion molding can be used. The metal elastic roll includes, for example, an inner roll made of a hollow metal roll and a metal outer cylinder having a smooth surface and elastically deformable during film production, and the inner and / or inner roll and outer cylinder of the inner roll. A double-structured metal elastic roll is used in which the cooling fluid flows down between the and. Rubber or any fluid not intended for cooling may be interposed between the inner roll and the outer cylinder. The thickness of the outer cylinder is sufficiently thin so that it can be elastically deformed without breaking during film production, and is, for example, about 2 to 8 mm. The outer cylinder preferably has a seamless structure without weld joints. The material of the inner roll and the outer cylinder is not particularly limited, and examples thereof include stainless steel and chrome steel.

When two rigid metal rolls are used, the outer cylinder of each roll is not deformed and makes point contact with the melt in cross-sectional view. On the other hand, the metal elastic roll elastically deforms as the melt is pressed. Therefore, when at least one metal elastic roll is used, the contact length between the melt and the metal elastic roll in the cross-sectional view is relatively long, and line contact can be made in the cross-sectional view, so that the melt has a more uniform linear pressure. Can be pressurized with. As a result, the air layer does not enter between the cooling roll and the melt, so that the above-mentioned accumulation of volatile matter on the roll surface due to agglutination is eliminated, and the roll can be suppressed from being contaminated.

Further, by sandwiching the melt between the first cooling roll and the second cooling roll, the film-forming property of the film is improved, and uneven thickness of the film and generation of streaks can be suppressed. It is also possible to make the film thinner.
Further, by using a metal rigid body roll or a metal elastic roll having a smooth surface, preferably a mirror surface, as the first cooling roll and the second cooling roll for sandwiching the melt, at least one film surface can be formed. A surface having high gloss at room temperature and having good printability can be obtained. Basically, both film surfaces can be surfaces having high gloss at room temperature and good printability.
It should be noted that non-metal rolls such as rubber rolls have lower surface smoothness than metal rigid body rolls or metal elastic rolls, and it is difficult to obtain a highly glossy film surface.

In the manufacturing method of the present invention, a metal rigid body roll can be used for both the first cooling roll and the second cooling roll. However, as described above, when the metal elastic roll is used, the cross-sectional visual contact length between the melt and the metal elastic roll is relatively long, and the melt can be pressurized with a more uniform linear pressure. Therefore, the effect of reducing the residual stress in the film and the effect of thinning the film can be obtained. Therefore, it is preferable to use a metal elastic roll as one of the cooling rolls (the first cooling roll or the second cooling roll).
When a metal elastic roll is used, a metal rigid body roll that supports the melt from the opposite side from the cross-sectional viewpoint is indispensable. That is, in the present invention, it is particularly preferable that one of the first cooling roll and the second cooling roll uses a metal rigid body roll and the other a metal elastic roll.

It is preferable that at least one of the first cooling roll and the second cooling roll is designed so that the outer diameter of both ends of the roll is slightly smaller than the outer diameter of the central portion of the roll. In this case, the step between both ends of the roll and the center of the roll formed on the outer peripheral surface is preferably 0.5 to 1.0 mm. When the step is formed on the outer peripheral surface of at least one of the cooling rolls, the thickness of both ends of the film can be made slightly thicker than that of the central portion, and cuts occur from both ends to reduce productivity. Can be suppressed. The shape of the step is not particularly limited, and may be vertical, tapered, or stepped. Both ends of the film, which are slightly thicker than the center of the film, can be cut and removed in a subsequent step, if necessary.

The linear pressure applied to the melt from the first cooling roll and the second cooling roll uniformly pressurizes the melt to prevent an air layer from entering between the cooling roll and the melt and volatilizes to the cooling roll. From the viewpoint of preventing the accumulation of minutes, it is preferably 10 kg / cm or more, more preferably 20 kg / cm or more, and particularly preferably 30 kg / cm or more. The upper limit of the linear pressure applied to the melt from the first cooling roll and the second cooling roll is not particularly limited, and the cooling roll can be elastically deformed and the film can be prevented from breaking. Therefore, the pressure is about 50 kg / cm.

The smaller the difference between the surface temperature of the cooling roll and the glass transition temperature of the thermoplastic resin composition (R), the better the adhesion of the melt to the cooling roll, and the smoother the surface and the glossiness of the film. In addition to improving the above, it is possible to prevent an air layer from entering between the cooling roll and the melt described above, and to prevent the accumulation of volatile matter on the cooling roll. On the other hand, the peelability of the melt from the cooling roll tends to decrease.

In the present invention, the Tg of the thermoplastic resin composition (R) is preferably 70 ° C. or higher, more preferably 90 ° C. or higher. The Tg of the thermoplastic resin composition (R) is preferably 125 ° C. or lower, more preferably 110 ° C. or lower. The temperature T2 of the second cooling roll is preferably 60 ° C. or higher, more preferably 70 ° C. or higher. The temperature T2 of the second cooling roll is preferably 90 ° C. or lower, more preferably 80 ° C. or lower. When T2 is 60 to 90 ° C., the balance between the surface smoothness and surface glossiness of the film and the peelability of the melt from the cooling roll is good, which is preferable.

Since the thermoplastic resin laminated film is sufficiently pressurized and cooled by the first cooling roll and the second cooling roll, the material thereof is not particularly limited when the cooling roll unit includes the third and subsequent cooling rolls. As the third and subsequent cooling rolls, a metal rigid body roll is preferable.
When the cooling roll unit includes a third or subsequent cooling roll, the surface temperature of the roll is not particularly limited. The surface temperature of the third and subsequent cooling rolls is preferably 50 ° C. or higher, more preferably 60 ° C. or higher. The surface temperature of the third and subsequent cooling rolls is preferably 90 ° C. or lower, more preferably 80 ° C. or lower.

The acrylic film of the present invention may be a stretched film. That is, the unstretched film may be stretched to obtain a stretched film. By the stretching treatment, the mechanical strength is increased, and a film that is not easily cracked can be obtained. The stretching method is not particularly limited, and examples thereof include a simultaneous biaxial stretching method, a sequential biaxial stretching method, and a tuber stretching method. From the viewpoint that uniform stretching can be performed and a high-strength film can be obtained, the lower limit of the stretching temperature is preferably a temperature 10 ° C. higher than the glass transition temperature (Tg) of the thermoplastic resin composition (R), and the upper limit of the stretching temperature. Is preferably a temperature 40 ° C. higher than the glass transition temperature (Tg) of the thermoplastic resin composition (R).

[B layer and C layer]
The method for producing the B layer and the C layer is not particularly limited, but when a polyvinyl acetal resin is used as the B layer and the C layer, a melt molding method is preferable. As a melt molding method, a method of melt-kneading the obtained polyvinyl acetal resin, plasticizer and other components using an extruder to form a film is preferable. The resin temperature at the time of extrusion is preferably 150 ° C. or higher, more preferably 170 ° C. or higher. The resin temperature at the time of extrusion is preferably 250 ° C. or lower, more preferably 230 ° C. or lower. If the resin temperature becomes too high, the polyvinyl acetal resin decomposes, and the content of volatile substances in the intermediate film after film formation increases. On the contrary, if the temperature is too low, the removal of volatile substances by the extruder becomes insufficient, and the content of volatile substances in the interlayer film after film formation increases. In order to efficiently remove the volatile substance, it is preferable to remove the volatile substance from the vent port by reducing the pressure inside the extruder.

As a method for producing the B layer and the C layer, another method is also used in which a polyvinyl acetal, a plasticizer and other components are dissolved or dispersed in an organic solvent to form a film, and then the organic solvent is distilled off. Can be manufactured.

[Laminated glass]
By having the structure of the interlayer film for laminated glass of the present invention inside the laminated glass, it is possible to obtain a laminated glass having excellent visibility and transparency while having functionality such as heat shielding property, conductivity and design. .. It is also possible to obtain a laminated glass having excellent weather resistance and heat-resistant creep resistance. Therefore, the laminated glass of the present invention can be suitably used for a laminated glass for construction, a laminated glass for surface protection of a display, a windshield for an automobile, a side glass for an automobile, a sun roof for an automobile, a glass for a head-up display, and the like.

When a laminated glass having the structure of a laminated glass interlayer film of the present invention is applied to a head-up display glass, the cross-sectional shape of the laminated glass interlayer film used is thick on one end face side and the other. It is preferable that the end face side has a thin shape. In that case, the cross-sectional shape may be a wedge-shaped shape as a whole such that the cross-sectional shape gradually becomes thinner from one end face side to the other end face side, or between one end face and the other end face. A part of the cross section may be wedge-shaped so as to have the same thickness up to an arbitrary position and gradually become thinner from the arbitrary position to the other end face.

Two pieces of glass are usually used for the laminated glass of the present invention. As the laminated glass of the present invention, not only inorganic glass but also organic glass can be used. The thickness of the glass constituting the laminated glass of the present invention is not particularly limited, but is preferably 100 mm or less. Further, since the interlayer film for laminated glass of the present invention is excellent in weather resistance and heat-resistant creep property, even if a laminated glass is produced using two thin glass sheets having a total glass thickness of 4 mm or less. It is possible to reduce the weight of the laminated glass without impairing the functionality such as heat insulation, conductivity, and design of the laminated glass, as well as the weather resistance and heat-resistant creep property. From the viewpoint of weight reduction, the total thickness of the glass is preferably 3.8 mm or less, and more preferably 3.6 mm or less.

The thickness of the two pieces of glass may be the same or different. For example, even if the thickness of one glass is 1.8 mm or more, the thickness of the other glass is 1.8 mm or less, and the difference in thickness of each glass is 0.2 mm or more, the heat shield and conductivity of the laminated glass, Laminated glass that is thin and lightweight can be manufactured without impairing functionality such as design, weather resistance, and heat-resistant creep property.

[Manufacturing method of laminated glass]
The laminated glass of the present invention can be produced by a conventionally known method, and examples thereof include a method using a vacuum laminator device, a method using a vacuum bag, a method using a vacuum ring, and a method using a nip roll. .. In addition, a method of charging into the autoclave process after temporary crimping can be additionally performed.

When using a vacuum laminator device, for example, using a known device, ^{under reduced pressure of 1 × 10-6} or more and 3 × ^10-2 MPa or less, 100 ° C or more, 200 ° C or less, particularly 130 ° C or more, 170 ° C or less. Laminated at the temperature of. A method using a vacuum bag or vacuum ring, for example, are described in European Patent No. 1235683, for example, under a pressure of about 2 × ¹⁰ -2 MPa, 130 ℃ or higher, is laminated at 145 ° C. or less.

Regarding the method for producing the laminated glass, when a nip roll is used, for example, a method of temporarily crimping at a temperature equal to or lower than the flow start temperature of the polyvinyl acetal resin and then temporarily crimping under conditions closer to the flow start temperature can be mentioned. .. Specifically, for example, after heating to 30 ° C. or higher and 100 ° C. or lower with an infrared heater or the like, degassing with a roll, further heating to 50 ° C. or higher and 150 ° C. or lower, and then crimping with a roll to bond or temporarily bond. There is a way to make it.

Further, the laminated glass may be formed by laminating glass coated with the B layer on both sides of the A layer so as to have the interlayer film for laminated glass of the present invention inside the laminated glass.

The autoclave step additionally performed after the temporary crimping depends on the thickness and configuration of the module, but is, for example, about 0.5 hours or more at a temperature of 130 ° C. or higher and 155 ° C. or lower under a pressure of about 1 MPa or more and 15 MPa or less. It will be carried out for 2 hours or less.

The glass used when producing the laminated glass by the interlayer film for laminated glass of the present invention is not particularly limited, and in addition to inorganic glass such as float plate glass, polished plate glass, template glass, meshed plate glass, and heat ray absorbing plate glass, polymethacryl Conventionally known organic glasses such as methyl acid and polycarbonate can be used, and these may be colorless, colored, transparent or non-transparent. These may be used alone or in combination of two or more. The thickness of the glass is not particularly limited, but is preferably 100 mm or less.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following description, unless otherwise specified, "parts" represents "parts by mass" and "%" represents "% by mass".

[Evaluation items and evaluation methods]
Various evaluations were carried out by the following methods.

(Haze measurement method)
In Examples and Comparative Examples, haze H was measured for the resin films used as the A layer, the B layer, and the C layer, and the laminated glass prepared by using these A to C layers. The laminated glass together with these resin films was cut out to a size of 30 mm × 30 mm to prepare a test piece. The test piece was set in a haze meter (manufactured by Murakami Color Technology Laboratory Co., Ltd .: HAZE METER HM-150), and haze H was measured in accordance with JIS K7136. The results are shown in Tables 1 and 2.

(Refractive index)
In Examples and Comparative Examples, the refractive index of the test piece of the resin film used as the A layer, the B layer, and the C layer was measured using "KPR-20" of Carnew Optical Industry Co., Ltd. based on ASTM D542. The results are shown in Tables 1 and 2.

With respect to the resin film used as the A layer in Examples and Comparative Examples, the tensile storage elastic moduli E'(40), E'(100) and E'(120) were measured by the following methods. The measurement was performed using a viscoelastic spectrometer (SII EXSTAR6000 series DMS6100 manufactured by SII Nanotechnology Co., Ltd.) in JIS K7244-4: 1999 (Plastic-dynamic mechanical property test method Part 4: Tension vibration-resonance method). In accordance with the following conditions. First, a sample is cut out from each resin film so that the longitudinal direction is 25 mm and the width direction is 10 mm, both ends of the measurement sample are attached to the chuck so that the tensile direction is the longitudinal direction of the measurement sample, and a tensile load (static load 150 mg) is attached. The tensile storage elastic modulus was measured from 0 ° C. to 200 ° C. at a constant frequency of 10 Hz and a heating rate of 5 ° C./min with a tensile mode sine wave. The results are shown in Tables 1 and 2.

(Evaluation method for wrinkles and cuts in 3D laminated glass laminates)
In the examples and comparative examples, the wrinkle / breakage evaluation method of the 3D shape-matched glass produced by the method described later was carried out by a visual discrimination method. The checkered pattern was regarded as a decorative layer, and the criteria for each evaluation result were as follows. The results are shown in Tables 1 and 2.
○ ・ ・ ・ No wrinkles or breaks in the interlayer film are visually observed.
×: Wrinkles and breaks in the interlayer film are visually observed.

(Method of evaluating the distortion of the intermediate layer of the 3D laminated glass laminate)
In Examples and Comparative Examples, as a method for evaluating the distortion of the 3D shape-matched glass produced by the method described later, the conductive structure layer is formed by drawing grid-like lines drawn at 2.5 mm intervals on the A layer with conductive ink. Alternatively, it was regarded as a decorative layer, and the degree to which the line was bent was visually confirmed. The criteria for each evaluation result were as follows. The results are shown in Tables 1 and 2.
○ ・ ・ ・ No distortion of grid-like lines can be seen.
Δ: Slight distortion is seen in the grid-like lines.
× ・ ・ ・ Large distortion can be seen in the grid-like lines.

(Visibility evaluation method of laminated glass laminate using layer A partially)
In the examples and comparative examples, as a method of evaluating the visibility of the laminated glass partially using the layer A produced by the method described later, the laminated glass is placed at a position 50 cm from the observer and visually confirmed. evaluated. The criteria for each evaluation result were as follows. The results are shown in Tables 1 and 2.
◯ ・ ・ ・ It is difficult to visually recognize the image corresponding to the edge portion of the A layer.
Δ: The image corresponding to the edge portion of the A layer can be slightly visually recognized.
X ... The image corresponding to the edge portion of the A layer can be clearly seen.

(Production Example 1) Polymerization of Acrylic Multilayer Polymer Particles (Y1) A monomer mixture for the innermost layer consisting of 32.91 parts of methyl methacrylate, 2.09 parts of methyl acrylate and 0.07 parts of allyl methacrylate, Next, a monomer mixture for the intermediate layer consisting of 37.00 parts of butyl acrylate, 8.00 parts of styrene and 0.90 parts of allyl methacrylate, then 18.80 parts of methyl methacrylate and 1.20 parts of methyl acrylate. The outermost monomer mixture for the outermost layer is emulsified and polymerized in this order to form an acrylic multilayer structure having a three-layer structure consisting of an innermost layer (y1-1), an intermediate layer (y1-2), and an outermost layer (y1-3). A latex containing polymer particles (Y1) was obtained. The average particle size D of the acrylic multilayer polymer particles (Y1) was 0.23 μm. The average average particle size D was measured by a light scattering method of diluted latex. Hereinafter, the average particle size D was measured by the same method.
The allyl methacrylate used in the innermost layer (y1-1) and the intermediate layer (y1-2) is a crosslinkable monomer (the same applies to the acrylic multilayer structure polymer particles (Y2)).

(Production Example 2) Polymerization of acrylic multilayer polymer particles (Y2):
A monomer mixture for the innermost layer consisting of 9.39 parts of methyl methacrylate, 0.61 part of methyl acrylate and 0.02 part of allyl methacrylate, followed by 41.11 parts of butyl acrylate, 8.89 parts of styrene and methacrylic acid. A monomer mixture for the intermediate layer consisting of 2.00 parts of allyl, then a monomer mixture for the outermost layer containing 37.61 parts of methyl methacrylate and 2.39 parts of methyl acrylate were emulsion-polymerized in this order, and the most was obtained. A latex containing a three-layered acrylic multilayer polymer particle (Y2) composed of an inner layer (y2-1), an intermediate layer (y2-2), and an outermost layer (y2-3) was obtained. The average particle size D of the acrylic multilayer polymer particles (Y2) was 0.11 μm.

(Manufacturing Example 3)
(Synthesis of block copolymer (Z))
After polymerizing the methacrylate ester polymer block (z2-1) with 20 parts by mass of methyl methacrylate by an anionic polymerization method in a toluene solution, the acrylic acid ester polymer block (z2-1) is polymerized with 50 parts by mass of n-butyl acrylate. z1) was polymerized, a methacrylate ester polymer block (z2-2) was further polymerized with 30 parts by mass of methyl methacrylate, and finally the mixture was stopped with methanol to obtain a triblock copolymer (Z). The weight average molecular weight Mw (Z) of the obtained block copolymer (Z) is 120,000, and the composition ratio of (z2-1)-(z1)-(z2-2) is 30% by mass-50% by mass. It was -20% by mass. The melt viscosity of the block copolymer (Z) at 220 ° C. and a shear rate of 122 / sec was 377 Pa · s.

(Example 1)
In the A layer, 10% by mass of pellets of the composition (Y1) containing the acrylic multilayer structure polymer particles obtained in Production Example 1, methacrylic resin (M) (“Parapet EH” manufactured by Kuraray Co., Ltd., melt flow). Pellet shape obtained by kneading 90% by mass of melt viscosity (2780 Pa · s) at a rate of 1.3 g / 10 minutes and a shear rate of 122 / sec at 220 ° C. by a known method using a twin-screw extruder. The thermoplastic resin composition (R) was used.

The thermoplastic resin composition (R) composed of the mixture of the above raw materials is put into a single-screw vent extruder having a screw diameter of 65 mm, extruded into a film from a T-die, and the extruded melt is referred to as the first to fourth. Pressurization and cooling were performed using a cooling roll unit consisting of a cooling roll (nip roll). A metal elastic roll was used as the first cooling roll, and a metal rigid body roll was used as the second cooling roll. The surface of each cooling roll was a mirror surface. After the melt was pressurized and cooled by the cooling roll unit, an unstretched thermoplastic resin film (layer A) having an average thickness of 52 μm was obtained by the same method as a known method. The arithmetic mean roughness (Ra) of one surface of the A layer was 0.07 μm.

The melt extrusion conditions were as follows.
Set temperature of extruder (melting temperature of resin composition): 260 ° C.,
T-die width: 500 mm,
T-die lip opening: 0.3 mm,
Discharge amount of molten resin from T-die: 15 kg / h
First cooling roll temperature: 64 ° C
Second cooling roll temperature: 79 ° C

The B layer contains 72% by mass of polyvinyl butyral having a viscosity average degree of polymerization of about 1700, an acetalization degree of 70 mol%, and a vinyl acetate unit content of 0.9 mol%, and triethylene glycol di-2-ethyl as a plasticizer. 28% by mass of hexanoate (3GO) was melt-kneaded with a twin-screw extruder, extruded into strands, and pelletized. The obtained pellets were put into a single-screw vent extruder having a screw diameter of 65 mm and a screw diameter of 50 mm, and extruded into a film from a T-die to obtain a thermoplastic resin film (PVB-1) having a thickness of 350 μm.

The melt extrusion conditions were as follows.
Set temperature of extruder (melting temperature of resin composition): 200 ° C,
T-die width: 500 mm,
T-die lip opening: 0.5 mm,
Discharge amount of molten resin from T-die: 15 kg / h

(Method for manufacturing laminated glass for 3D shape evaluation)
The obtained thermoplastic resin films A layer and B layer are cut out into circles having a diameter of 150 mm, respectively, and the surface of the A layer is coated with conductive ink so that the size of one lattice is 5 mm × 5 mm. I drew a grid of lines. As shown in FIG. 2, the A layer 9 having a grid pattern on the surface is sandwiched between the B layer 8 and the B layer 10 to form an interlayer film for laminated glass. Next, a disk-shaped watch glass (3D-shaped glass 11) having a diameter of 150 mm and a height of 15 mm is covered with the above-mentioned interlayer film for laminated glass consisting of the B layer / A layer / B layer, and then from above. A disk-shaped watch glass (3D-shaped glass 7) having a diameter of 150 mm and a height of 15 mm was placed on the watch glass, placed in a vacuum pack, evacuated, and allowed to stand at a temperature of 100 ° C. for 30 minutes. It was taken out from the vacuum pack and further allowed to stand in an autoclave at 140 ° C. for 60 minutes to obtain the desired laminated glass 12.

(Method for manufacturing laminated glass for optical performance evaluation)
The obtained thermoplastic resin films A layer and B layer were cut into square sizes of 150 mm × 150 mm, respectively, and the A layer was sandwiched between the B layers from the front and back surfaces to form an interlayer film for laminated glass. Subsequently, a laminated glass interlayer film composed of a B layer / A layer / B layer was sandwiched between the front and back sides of a glass having a thickness of 2 mm, placed in a vacuum pack, evacuated, and allowed to stand at a temperature of 100 ° C. for 30 minutes. It was taken out from the vacuum pack and further allowed to stand in an autoclave at 140 ° C. for 60 minutes to obtain the desired laminated glass.

(Method of manufacturing laminated glass for visibility evaluation when partially used)
The obtained thermoplastic resin film (layer A) was cut into a square size of 50 mm × 50 mm, and further, the thermoplastic resin film (layer B) was cut into a square size of 150 mm × 150 mm. As shown in FIG. 3, the A layer 15 is sandwiched between the B layer 14 and the B layer 16 from the front and back surfaces to form an interlayer film for laminated glass. Next, a laminated glass interlayer film consisting of B layer / A layer / B layer is sandwiched between glass 13 and glass 17 having a thickness of 2 mm from the front and back sides, placed in a vacuum pack and evacuated to a temperature of 100 ° C. for 30 minutes. Placed. It was taken out from the vacuum pack and further allowed to stand in an autoclave at 140 ° C. for 60 minutes to obtain a laminated glass 18 partially using the A layer.

(Example 2)
In the A layer, 20% by mass of pellets of the composition (Y1) containing the acrylic multilayer structure polymer particles obtained in Production Example 1 and a methacrylic resin (M) (“Parapet EH” manufactured by Kuraray Co., Ltd.) are used. Laminated glass in the same manner as in Example 1 except that a pellet-shaped thermoplastic resin composition (R) obtained by kneading 80% by mass by a known method using a twin-screw extruder was used. An interlayer film for use and a laminated glass were prepared. The arithmetic mean roughness (Ra) of one surface of the A layer was 0.08 μm.

(Example 3)
In the A layer, 90% by mass of pellets of the composition (Y2) containing the acrylic multilayer structure polymer particles obtained in Production Example 2 and a methacrylic resin (M) (“Parapet EH” manufactured by Kuraray Co., Ltd.) are used. Laminated glass in the same manner as in Example 1 except that a pellet-shaped thermoplastic resin composition (R) obtained by kneading 10% by mass by a known method using a twin-screw extruder was used. An interlayer film for use and a laminated glass were prepared. The arithmetic mean roughness (Ra) of one surface of the A layer was 0.05 μm.

(Example 4)
In layer A, 100% by mass of pellets of the composition (Y2) containing the acrylic multilayer structure polymer particles obtained in Production Example 2 was kneaded by a known method using a twin-screw extruder to obtain pellets. An interlayer film for laminated glass and laminated glass were prepared in the same manner as in Example 1 except that the thermoplastic resin composition (R) having a shape was used. The arithmetic mean roughness (Ra) of one surface of the A layer was 0.04 μm.

(Example 5)
In the A layer, 15% by mass of pellets of the composition (Z) containing the acrylic block copolymer particles obtained in Production Example 3 and a methacrylic resin (M) (“Parapet EH” manufactured by Kuraray Co., Ltd.) are used. For laminated glass by the same method as in Example 1 except that a pellet-shaped thermoplastic resin composition (R) obtained by kneading with 85% by mass by a known method using a twin-screw extruder was used. An interlayer film and a laminated glass were prepared. The arithmetic mean roughness (Ra) of one surface of the A layer was 0.03 μm.

(Example 6)
The ionomer film "Sentry Glass (registered trademark)" was hot-pressed under the conditions of a temperature of 200 ° C., a pressure of 10 MPa, and 15 minutes to obtain an ionomer film having a thickness of 350 mm. An interlayer film for laminated glass and a laminated glass were produced in the same manner as in Example 3 except that the obtained ionomer film was used as the B layer.

(Example 7)
PVB-2 was produced by the same method as PVB-1 except that the lip opening of the T-die was changed to 0.9 mm and the thickness was changed to 760 μm.

Polyvinyl butyral having a viscosity average degree of polymerization of about 1000, an acetalization degree of 70 mol%, and a vinyl acetate unit content of 0.9 mol% was melt-kneaded with a twin-screw extruder, extruded into strands, and pelletized. The obtained pellets were put into a single-screw vent extruder having a screw diameter of 65 mm and a screw diameter of 50 mm, and extruded into a film from a T-die to obtain a thermoplastic resin film (PVB-3) having a thickness of 50 μm.

Extruder set temperature (melting temperature of resin composition): 220 ° C,
T-die width: 500 mm,
T-die lip opening: 0.5 mm,
Discharge amount of molten resin from T-die: 15 kg / h

A laminated glass was prepared in the same manner as in Example 1 except that the obtained PVB-2 was used as a B layer, PVB-3 was used as a C layer, and an intermediate film of a B layer / A layer / C layer was used.

(Example 8)
Polyvinyl butyral with a viscosity average degree of polymerization of about 1700, an acetalization degree of 70 mol%, and a vinyl acetate unit content of 0.9 mol%, and a plasticizer, triethylene glycol di-2-ethylhexanoate (3GO) 15 The mass was changed to%, and PVB-4 having a thickness of 100 μm was prepared by the same method as PVB-1. An interlayer film for laminated glass and laminated glass were prepared in the same manner as in Example 7 except that PVB-4 was used as the C layer.

(Example 9)
An interlayer film for laminated glass and laminated glass were prepared in the same manner as in Example 7 except that Trosifol Acoustic (manufactured by Kuraray Co., Ltd.) (PVB-5) having a thickness of 840 μm was used as the B layer.

(Example 10)
As the C layer, a 50 μm film formed by forming a polyurethane resin “ESTANE AG-8451” manufactured by Lubrizol using a known film-forming machine was used, but in the same manner as in Example 7, an intermediate for laminated glass was used. A film and a laminated glass were prepared.

(Example 11)
As the C layer, a commercially available acrylic adhesive was used, the layer A was solvent-coated to a thickness of 10 μm, and dried to prepare a laminated body of the A / C layer. Using the obtained A / C laminate, a laminated glass interlayer film and a laminated glass were produced in the same manner as in Example 7 except that PVB-2 was used as the B layer.

(Comparative Example 1)
As the layer A, an interlayer film for laminated glass is used in the same manner as in Example 1 except that a PET film "Lumirror" manufactured by Toray Co., Ltd. having a thickness of 52 μm and an arithmetic mean roughness (Ra) of 0.06 μm on the surface is used. And laminated glass was prepared.

(Comparative Example 2)
An interlayer film for laminated glass and laminated glass were prepared in the same manner as in Example 1 except that the MS resin "TX-800LF" manufactured by Denka Co., Ltd. was used for the A layer. The arithmetic mean roughness (Ra) of one surface of the A layer was 0.06 μm.

(Comparative Example 3)
In the A layer, 30% by mass of pellets of the composition (Y1) containing the acrylic multilayer structure polymer particles obtained in Production Example 1 and 70 methacrylic resin (M) (“Parapet EH” manufactured by Kuraray Co., Ltd.) Laminated glass interlayer film in the same manner as in Example 1 except that the pellet-shaped thermoplastic resin composition (R) obtained by kneading with a mass% by a known method using a twin-screw extruder was used. And laminated glass was prepared. The arithmetic mean roughness (Ra) of one surface of the A layer was 0.08 μm.

(Evaluation results)
In Examples 1 to 5, an interlayer film having a B layer / A layer / B layer structure was used as the interlayer film of the laminated glass. Moreover, PVB resin was used for the B layer. For the layer A, an acrylic film satisfying claim 1 and in which an acrylic multilayer structure polymer or a block copolymer having different particle sizes was mixed at an arbitrary ratio was used. Further, in Example 6, a laminated glass was prepared by using an ionomer resin instead of PVB.
In Examples 1 to 6, highly transparent laminated glass having a haze of 1.0% or less can be obtained, and wrinkles and breakage occur even when the laminated glass is produced using 3D-shaped glass. There was no distortion of the grid pattern drawn on the A layer. Further, a laminated glass using the A layer partially was prepared, and the boundary line of the A layer could not be confirmed by observing the image obtained by irradiating the laminated glass with the light from the light source and projecting the magnified glass on the screen.

On the other hand, in Comparative Example 1 using the PET film, the haze of the laminated glass was worse than in the example, and when the laminated glass using the 3D-shaped glass was produced, the lattice-like pattern drawn on the A layer was distorted. Was not seen, but wrinkles and breaks in the film were seen as it approached the edges. Furthermore, when a laminated glass using the A layer partially was produced, the boundary line of the A layer could be visually confirmed.
In Comparative Example 2 in which MS resin was used for the A layer, when a laminated glass using 3D-shaped glass was produced, no distortion, wrinkles, or breaks in the lattice pattern were observed, but the A layer was partially formed. When the laminated glass used in the above was prepared, the boundary line of the A layer could be visually confirmed. The haze of the laminated glass also deteriorated as compared with the examples.
In Comparative Example 3 in which an acrylic multilayer polymer having a particle size of 230 μm was used and the content thereof was increased, a laminated glass using 3D-shaped glass was produced, and the lattice-like pattern was distorted, wrinkled, or cut. Even if you make a laminated glass that partially uses layer A and irradiate the laminated glass with light from a light source to magnify and project it on the screen, you cannot see the boundary line of layer A. It was. However, the haze of the laminated glass was worse than in the examples.

The present invention is not limited to the above-described embodiments and examples, and the design can be appropriately changed as long as the gist of the present invention is not deviated.

1 Glass 2 B layer 3 Functional layer 4 A layer 5 B layer 6 Glass 7 3D-shaped glass 8 B layer 9 A layer with a grid pattern on the surface 10 B layer 11 3D-shaped laminated glass 12 3D-shaped laminated glass 13 Glass 14 B layer 15 A layer 16 B layer 17 Glass 18 Laminated glass partially using A layer

Claims (19)

An interlayer film for laminated glass laminated in the structure of B layer / A layer / B layer or B layer / A layer / C layer.
The refractive index difference between the refractive index of the A layer and the refractive index of the B layer measured based on ASTM D542 and / or the refractive index difference between the refractive index of the A layer and the refractive index of the C layer is 0.05 or less. And
The A layer has a tensile storage elastic modulus E'(40) at 40 ° C., a tensile storage elastic modulus E'(100) at 100 ° C., and a tensile storage elastic modulus E'(120) at 120 ° C. Satisfy (2) and equation (3),
The haze value based on JIS K7136 of the laminated glass in which the interlayer film for laminated glass is sandwiched between two sheets of glass is 1.0% or less.
Laminated glass interlayer film.
(1) E'(40) ≥ 1000 MPa
(2) E'(100) ≥ 10 MPa
(3) E'(120) ≤ 10 MPa The interlayer film for laminated glass according to claim 1, wherein the layer A is made of an acrylic resin composition. The interlayer film for laminated glass according to claim 2, wherein the acrylic resin composition contains elastic particles. Elastic particles are
The inner layer of at least one layer is a crosslinked thermoplastic polymer layer containing a crosslinked thermoplastic polymer having an acrylic acid alkyl ester monomer unit having an alkyl group having 1 to 8 carbon atoms and / or a conjugated diene-based monomer unit. The outermost layer is an acrylic multilayer structure polymer particle (Y) which is a thermoplastic polymer layer containing a thermoplastic polymer having a methacrylate alkyl ester monomer unit having an alkyl group having 1 to 8 carbon atoms. , The interlayer film for laminated glass according to claim 3. The interlayer film for laminated glass according to claim 4, wherein the average particle size of the acrylic multilayer structure polymer particles (Y) is 0.05 to 0.25 μm. The acrylic resin composition contains acrylic multilayer structure polymer particles (Y) and 80% by mass or more of methyl methacrylate units, and the melt flow rate is 0.5 to 10 g / 10 minutes. ), The interlayer film for laminated glass according to claim 4 or 5. The acrylic resin composition contains a block copolymer (Z) in which a methacrylic acid ester polymer block (z2) is bonded to an acrylic acid ester polymer block (z1), and a methacrylic resin (M).
The melt viscosity (η (Z)) of the block copolymer (Z) at 220 ° C. and a shear rate of 122 / sec is 75 to 1500 Pa · s.
Further, the value of the ratio (η (M) / η (Z)) of the melt viscosity (η (M)) to the melt viscosity (η (Z)) of the methacrylic resin (M) at 220 ° C. and a shear rate of 122 / sec. The interlayer film for laminated glass according to claim 2, wherein the number is 1 to 20. The amount of the acrylic resin composition is 70 to 99 parts by mass of the methacrylic resin (M) and the block copolymer (Z) 1 with respect to 100 parts by mass of the total of the methacrylic resin (M) and the block copolymer (Z). The interlayer film for laminated glass according to claim 7, which contains ~ 30 parts by mass. The interlayer film for laminated glass according to claim 7 or 8, wherein the methacrylic resin (M) contains 80% by mass or more of methyl methacrylate units and the melt flow rate is 0.5 to 10 g / 10 minutes. The interlayer film for laminated glass according to any one of claims 1 to 9, wherein the arithmetic mean roughness (Ra) of at least one surface of the layer A is 0.15 μm or less. The interlayer film for laminated glass according to any one of claims 1 to 10, wherein the layer A contains metal oxide fine particles having a heat ray-shielding function. The interlayer film for laminated glass according to any one of claims 1 to 10, which has a functional coating layer on the surface of the A layer. The interlayer film for laminated glass according to claim 12, wherein the functional coating layer is a heat ray-shielding coating having a thickness of 0.01 to 50 μm. The interlayer film for laminated glass according to any one of claims 1 to 10, which has a conductive structure on the surface of the A layer. The interlayer film for laminated glass according to claim 14, wherein the interlayer film for laminated glass has a conductive structure on the surface of the layer A, and the conductive structure is formed by a printing method, an etching method, or a thin-film deposition method. The interlayer film for laminated glass according to claim 14 or 15, wherein the conductive structure contains at least one of gold, silver, copper or a metal oxide. One of claims 1 to 16, wherein the B layer and / or the C layer contains at least one resin selected from polyvinyl acetal resin, ionomer, ethylene vinyl acetate, vinyl chloride resin, urethane resin, silicone resin and polyamide resin. The described interlayer film for laminated glass. A laminated glass formed by sandwiching the laminated glass interlayer film according to any one of claims 1 to 17 between two sheets of glass. Production of laminated glass for producing laminated glass by sandwiching layer A having at least one or more functions of heat ray shielding property, conductivity or decoration between at least two layers B or at least layers B and C. It ’s a method,
The refractive index difference between the refractive index of the A layer and the refractive index of the B layer measured based on ASTM D542 and / or the refractive index difference between the refractive index of the A layer and the refractive index of the C layer is 0.05 or less. And
The tensile storage elastic modulus E'(40) at 40 ° C., the tensile storage elastic modulus E'(100) at 100 ° C., and the tensile storage elastic modulus E'(120) at 120 ° C. of the layer A are the formulas (1) and (1). A method for producing a laminated glass according to 2) and the formula (3).
(1) E'(40) ≥ 1000 MPa
(2) E'(100) ≥ 10 MPa
(3) E'(120) ≤ 10 MPa

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