JP2014058409A - Intermediate film for laminated glass and laminated glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an intermediate film for laminated glass, which is excellent in transparency and adhesion to a glass sheet, and to provide laminated glass using the intermediate film.SOLUTION: The intermediate film for laminated glass has a layer (A) containing a silane coupling agent and at least one of a magnesium ionomer of an ethylene/α,β-unsaturated carboxylic acid/α,β-unsaturated carboxylic acid ester copolymer and a sodium ionomer of an ethylene/α,β-unsaturated carboxylic acid/α,β-unsaturated carboxylic acid ester copolymer. Preferably, the intermediate film for laminated glass has at least two layers (A) and at least one layer (B) containing an ethylene-based ionomer and includes a multilayered structure in which the layer (B) is arranged between the two layers (A).

Description

  The present invention relates to an interlayer film for laminated glass and laminated glass.

  It is known to use an ionomer of an ethylene / unsaturated carboxylic acid copolymer as an interlayer film for laminated glass.

  Patent Document 1 describes an interlayer film for laminated glass made of an ethylene / (meth) acrylic acid / (meth) acrylic acid ester copolymer having a specific composition ratio or an ionomer thereof.

  In Patent Document 2, an ethylene / unsaturated carboxylic acid copolymer, an ethylene / unsaturated carboxylic acid / unsaturated carboxylic acid ester copolymer, or an ionomer of these is used as a core layer, and lamination is performed by laminating glass on both sides. Glass is described.

  Patent Document 3 describes a laminated glass in which an organic peroxide and a silane coupling agent are blended in an ionomer of an ethylene / methacrylic acid copolymer, interposed between glass plates, and thermoset to be integrated. .

  Patent Document 4 describes a laminated glass in which two glass sheets are bonded using an ionomer of an ethylene / (meth) acrylic acid copolymer neutralized with a polyamine as an intermediate adhesive layer.

  Patent Document 5 describes an interlayer film for laminated glass comprising a laminated sheet of an ethylene / (meth) acrylic acid copolymer ionomer and an ethylene / vinyl acetate copolymer.

JP-A-8-295541 JP-A-8-295543 Japanese Patent Laid-Open No. 9-30846 JP-T-2002-503627 JP 2009-298046 A

As described above, ionomers are conventionally used as a component of an interlayer film of laminated glass.
However, simply using an ionomer as a component of the interlayer film for laminated glass does not necessarily provide high transparency with, for example, a general-purpose zinc ionomer. Particularly, the region from the vicinity of 400 nm to the vicinity of 600 nm, which is the center of the visible region. Then, compared with an ionomer containing sodium (Na) or magnesium (Mg), the light transmittance tends to decrease.

  In addition, Na ionomer of ethylene / α, β-unsaturated carboxylic acid binary copolymer and Mg ionomer of ethylene / α, β-unsaturated carboxylic acid binary copolymer are adhered to the glass sheet (adhesiveness). Is relatively weak and may be deteriorated (peeling, etc.) over time.

  The present invention has been made in view of the above, and provides an interlayer film for laminated glass that is excellent in transparency and adhesion to a glass sheet, and a laminated glass that is superior in durability over a long period of time compared to the past. It aims at providing and makes it a subject to achieve this objective.

Among the ionomers, the present inventor has shown that sodium (Na) ionomer and magnesium (Mg) ionomer have good transparency, but ethylene / α, β-unsaturated carboxylic acid binary copolymer Na ionomer and ethylene It was found that the Mg ionomer of the α, β-unsaturated carboxylic acid binary copolymer has weak adhesion to glass and tends to deteriorate with time due to deterioration with time.
Further examination revealed that these ethylene / α, β-unsaturated carboxylic acid binary copolymer Na ionomers and ethylene / α, β-unsaturated carboxylic acid binary copolymer Mg ionomers are silane coupling agents. It was found that the adhesion to glass (including adhesion over time) was hardly improved even when used in a mixture.
On the other hand, Mg ionomer of ethylene / α, β-unsaturated carboxylic acid / α, β-unsaturated carboxylic acid ester copolymer and ethylene / α, β-unsaturated carboxylic acid / α, β-unsaturated carboxylic acid It has been clarified that the Na ionomer of the ester copolymer is remarkably improved in adhesion to glass (including adhesion over time) when mixed with a silane coupling agent.
The present invention has been achieved based on the above findings.
That is, specific means for achieving the above-described problem are as follows.

<1> Silane coupling agent, ethylene ionomer of ethylene / α, β-unsaturated carboxylic acid / α, β-unsaturated carboxylic acid ester copolymer, and ethylene / α, β-unsaturated carboxylic acid / α / β -An interlayer film for laminated glass having a layer (A) containing at least one of sodium ionomers of unsaturated carboxylic acid ester copolymers.
<2> It has at least two layers (A) and at least one layer (B) containing an ethylene ionomer, and the (B) layer is disposed between the two (A) layers. The interlayer film for laminated glass according to <1>, including a multilayer structure.
<3> It has at least two layers (A) and at least one layer (B) containing an ethylene ionomer, and the (B) layer is disposed between the two (A) layers. Including multi-layer structure
The (B) layer is the interlayer film for laminated glass according to <1> or <2>, wherein the content of the silane coupling agent is 0.1% by mass or less of the solid content of the (B) layer. .
<4> The layer (A) contains a silane coupling agent having an amino group and an alkoxy group of 3 parts by mass or less with respect to 100 parts by mass of the total amount of the magnesium ionomer and the sodium ionomer <1>. -The interlayer film for laminated glass according to any one of <3>.
<5> The interlayer film for laminated glass according to any one of <1> to <4>, wherein the total thickness is 0.1 to 2 mm.
<6> It has at least two layers (A) and at least one layer (B) containing an ethylene ionomer, and the (B) layer is disposed between the two (A) layers. <1> to <5> in which the ratio (a / b) of the thickness a of the (A) layer and the thickness b of the (B) layer is 5/1 to 1/20 It is an intermediate film for laminated glasses as described in any one of these.
<7> It has at least two layers (A) and at least one ethylene ionomer (B) layer, and the (B) layer is disposed between the two (A) layers. A melt flow rate (MFR; JIS K7210-1999, 190 ° C., 2160 g) of at least one of the magnesium ionomer and the sodium ionomer in the layer (A) and the ethylene ionomer in the layer (B). Load) is the interlayer film for laminated glass according to any one of <1> to <6>, wherein the load is 0.1 to 150 g / 10 minutes.
<8> In a state of being sandwiched between two 3.2 mm-thick blue plate float glass, it was bonded at 150 ° C. for 8 minutes in a double vacuum tank bonding machine, and allowed to cool at an atmospheric pressure of 23 ° C. The intermediate film for laminated glass according to any one of <1> to <7>, wherein the total light transmittance in accordance with JIS-K7105 is 83% or more.
<9> A laminated glass comprising the interlayer film for laminated glass according to any one of <1> to <8>.

  According to the present invention, it is possible to provide an interlayer film for laminated glass that is excellent in transparency and adhesion to a glass sheet, and a laminated glass that is superior in durability over a long period of time as compared with the related art.

  Hereinafter, the interlayer film for laminated glass of the present invention and the laminated glass provided with the same will be described in detail.

The interlayer film for laminated glass of the present invention comprises a silane coupling agent, a magnesium ionomer of ethylene / α, β-unsaturated carboxylic acid / α, β-unsaturated carboxylic acid ester copolymer, and ethylene / α, β-unsaturated. And (A) a layer containing at least one of a sodium ionomer of a saturated carboxylic acid / α, β-unsaturated carboxylic acid ester copolymer.
The interlayer film for laminated glass of the present invention may have a single layer configuration or a multilayer configuration.
More specifically, the interlayer film for laminated glass of the present invention may be a single-layer film composed of only one (A) layer or a multilayer composed of two or more (A) layers. It may be a film having a structure, or a film having a multilayer structure having at least one (A) layer and at least one layer other than the (A) layer (for example, a (B) layer described later). There may be.
The interlayer film for laminated glass of the present invention may contain other components such as an ultraviolet absorber, a light stabilizer, and an antioxidant as necessary. Further, pigments (organic pigments, inorganic pigments), dyes and the like may be contained as colorants.

In the present invention, by using an ionomer, heat resistance, flexibility, moldability, etc. can be maintained, and in this case, at least the ethylene / α, β-unsaturated carboxylic acid / α, β-unsaturated carboxylic acid ester is used. The use of a magnesium ionomer of a polymer and a sodium ionomer of an ethylene / α, β-unsaturated carboxylic acid / α, β-unsaturated carboxylic acid ester copolymer in combination with a silane coupling agent, While being excellent in adhesiveness with the glass sheet to be obtained, high transparency can be obtained, and sound insulation properties are also excellent.
In addition, a crosslinking step using an organic peroxide or a curing aid as described in Patent Document 3 is unnecessary, and it can be formed in a short time in a simpler method compared to the prior art, and is also used as an interlayer film for laminated glass. It is suitable for.

[(A) layer]
The interlayer film for laminated glass of the present invention has at least one (A) layer.
The layer (A) is composed of a magnesium (Mg) ionomer of ethylene / α, β-unsaturated carboxylic acid / α, β-unsaturated carboxylic acid ester copolymer and ethylene / α, β-unsaturated carboxylic acid / α, β. -It contains at least one of sodium (Na) ionomer of unsaturated carboxylic acid ester copolymer.
Thereby, it is excellent in adhesiveness with an adjacent material (A glass sheet or other layers (For example, (B) layer mentioned later) used as needed), and excellent in transparency.
The layer (A) may be abbreviated as the magnesium ionomer (hereinafter sometimes abbreviated as “Mg ionomer”) and the sodium ionomer (hereinafter abbreviated as “Na ionomer”) in terms of adhesiveness and transparency. It is preferable that at least one of them is included as a main component. Here, “including as a main component” means that the total amount of the Mg ionomer and the Na ionomer is 60% by mass or more based on the entire layer (A). The total amount is preferably 80% by mass or more based on the entire layer (A).

The ionomer (at least one of the Mg ionomer and the Na ionomer, the same shall apply hereinafter) contained in the layer (A) is a structural unit derived from ethylene, a structural unit derived from an α, β-unsaturated carboxylic acid, and α , An ionomer of an ethylene / α, β-unsaturated carboxylic acid / α, β-unsaturated carboxylic acid ester copolymer having a structural unit derived from a β-unsaturated carboxylic acid ester.
The content ratio of the structural unit derived from ethylene in the ethylene / α, β-unsaturated carboxylic acid / α, β-unsaturated carboxylic acid ester copolymer which is the base polymer of the ionomer is preferably 97 to 60% by mass. More preferably, it is 95-60 mass%, More preferably, it is 94-60 mass%, Most preferably, it is 90-60 mass%.
The content ratio of the structural unit derived from the α, β-unsaturated carboxylic acid in the ethylene / α, β-unsaturated carboxylic acid / α, β-unsaturated carboxylic acid ester copolymer is 1.5 to 25 mass. % Is preferable, 3 to 25% by mass is more preferable, and 5 to 25% by mass is particularly preferable.
The content ratio of structural units derived from the α, β-unsaturated carboxylic acid ester in the ethylene / α, β-unsaturated carboxylic acid / α, β-unsaturated carboxylic acid ester copolymer is 1.5-25. % By mass is preferable, 3 to 25% by mass is more preferable, and 5 to 25% by mass is particularly preferable.
The ionomer base polymer contained in the layer (A) is composed of structural units derived from ethylene, structural units derived from α, β-unsaturated carboxylic acid, and structural units derived from α, β-unsaturated carboxylic acid ester. The ethylene / α, β-unsaturated carboxylic acid / α, β-unsaturated carboxylic acid ester terpolymer is particularly preferable.

  Hereinafter, the α, β-unsaturated carboxylic acid and the α, β-unsaturated carboxylic acid ester may be referred to as “unsaturated carboxylic acid” and “unsaturated carboxylic acid ester”, respectively.

  When the content of the structural unit derived from ethylene is 60% by mass or more, heat resistance, mechanical strength, and the like are good. On the other hand, adhesiveness etc. are favorable in the content rate of the structural unit guide | induced from ethylene being 97 mass% or less.

Examples of the α, β-unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, maleic anhydride monoester, and acrylic acid or methacrylic acid is particularly preferable.
As a particularly preferred example of Mg ionomer of ethylene / α, β-unsaturated carboxylic acid / α, β-unsaturated carboxylic acid ester copolymer in the present invention, Mg ionomer of ethylene / acrylic acid / acrylic acid ester copolymer, Mg ionomer of ethylene / acrylic acid / methacrylic acid ester copolymer, Mg ionomer of ethylene / methacrylic acid / acrylic acid ester copolymer, and Mg ionomer of ethylene / methacrylic acid / methacrylic acid ester copolymer.
As a particularly preferred example of the Na ionomer of ethylene / α, β-unsaturated carboxylic acid / α, β-unsaturated carboxylic acid ester copolymer in the present invention, Na ionomer of ethylene / acrylic acid / acrylic acid ester copolymer, Examples include Na ionomers of ethylene / acrylic acid / methacrylic acid ester copolymers, Na ionomers of ethylene / methacrylic acid / acrylic acid ester copolymers, and Na ionomers of ethylene / methacrylic acid / methacrylic acid ester copolymers.

  Examples of the ester in the unsaturated carboxylic acid ester include methyl ester, ethyl ester, n-propyl ester, isopropyl ester, n-butyl ester, isobutyl ester, and 2-ethylhexyl ester.

From the α, β-unsaturated carboxylic acid contained in the ionomer base polymer (ethylene / α, β-unsaturated carboxylic acid / α, β-unsaturated carboxylic acid ester copolymer) contained in the layer (A). The derived structural unit and the structural unit derived from the α, β-unsaturated carboxylic acid ester play an important role in adhesion to a substrate such as glass. These structural units mainly provide adhesion to the ionomer contained in the (A) layer provided in contact with a substrate such as glass.
From the viewpoint of the adhesiveness, the α, β-unsaturated amount relative to the total mass of the ethylene / α, β-unsaturated carboxylic acid / α, β-unsaturated carboxylic acid ester copolymer (or the total mass of the ionomer). It is preferable that the total content ratio of the structural unit derived from the saturated carboxylic acid and the structural unit derived from the α, β-unsaturated carboxylic acid ester is 3% by mass or more. Moreover, transparency and a softness | flexibility are favorable in the said content rate being 3 mass% or more.
On the other hand, from the viewpoint of stickiness suppression and processability improvement, with respect to the total mass of the ethylene / α, β-unsaturated carboxylic acid / α, β-unsaturated carboxylic acid ester copolymer (or the total mass of the ionomer), The total content ratio of the structural unit derived from the α, β-unsaturated carboxylic acid and the structural unit derived from the α, β-unsaturated carboxylic acid ester is preferably 40% by mass or less.

  The neutralization degree of the ionomer contained in the layer (A) is preferably 80% or less. The neutralization degree is preferably 5% or more and 80% or less from the viewpoint of workability and flexibility.

The ethylene / α, β-unsaturated carboxylic acid / α, β-unsaturated carboxylic acid ester copolymer, which is the base polymer of the ionomer contained in the layer (A), is prepared by, for example, Can be obtained by radical copolymerization.
The ionomer reacts, for example, an ethylene / α, β-unsaturated carboxylic acid / α, β-unsaturated carboxylic acid ester copolymer with a metal hydroxide, a metal oxide, a metal acetate or the like. Can be obtained.

  In view of processability and mechanical strength, the ionomer preferably has a melt flow rate (MFR; conforming to JIS K7210-1999) at 190 ° C. and a load of 2160 g of 0.1 to 150 g / 10 min. It is more preferable that it is 1-50 g / 10min.

The total amount of the Mg ionomer and the Na ionomer contained in the (A) layer is preferably 60% by mass or more, more preferably 70% by mass or more, and 80% by mass of the solid content of the (A) layer. % Or more is particularly preferable.
When the total amount of the Mg ionomer and the Na ionomer is in the above range, good adhesion and durability can be obtained while maintaining high transparency, and sound insulation characteristics are also excellent.

The (A) layer may contain a resin material other than the ionomer together with the ionomer.
As the other resin material, any resin material can be used as long as it is compatible with the ionomer and does not impair the transparency and mechanical properties of the layer (A).
As the other resin material, an ethylene / unsaturated carboxylic acid copolymer and an ethylene / unsaturated ester / unsaturated carboxylic acid copolymer are preferable.
If the other resin material is a resin material having a melting point higher than that of the ionomer, the heat resistance and durability of the layer (A) can be improved.

The (A) layer contains at least one silane coupling agent.
When the (A) layer does not contain a silane coupling agent, the adhesion to glass (including adhesion over time) tends to decrease.

Examples of the silane coupling agent include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, N- (β-amino). Ethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, etc. Can do.
Among them, as a silane coupling agent, a silane coupling agent having an amino group and an alkoxy group (for example, an amino group) is used in order to enhance adhesion and stably perform adhesion processing with a substrate such as glass or a back sheet. Alkoxysilane having

Specific examples of the silane coupling agent having an amino group and an alkoxy group include 3-aminopropyltrimethoxyxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3- Amino-trialkoxysilanes such as aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, N -(2-aminoethyl) -3-aminopropyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-phenyl-3-aminopropylmethyldimethoxysilane, N-phenyl-3- Aminopropylmethyldiethoxysilane, 3-methyl Examples include amino-dialkoxysilanes such as dimethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine and 3-methyldimethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine. .
Among these, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3- Aminopropylethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane and the like are preferable. In particular, a silane coupling agent containing an amino group and two alkoxy groups such as N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane is preferable.
When such a silane coupling agent containing an amino group and two alkoxy groups (sometimes abbreviated as dialkoxysilane) is used, the processing stability during sheet molding can be further maintained. More preferred.

  In the layer (A), the amount of the silane coupling agent (for example, a silane coupling agent containing an amino group and an alkoxy group) (the total amount in the case of two or more types) is the effect of improving adhesiveness and processing during sheet molding. From the viewpoint of stability, with respect to 100 parts by mass of the total amount of the Mg ionomer and the Na ionomer, preferably more than 0 parts by mass and 3 parts by mass or less, more preferably 0.03 parts by mass to 3 parts by mass, particularly Is 0.05 parts by mass or more and 1.5 parts by mass or less. When the silane coupling agent is contained within the above range, the adhesion with the glass sheet can be improved.

  The (A) layer can contain various additives within the range not impairing the object of the present invention. Examples of such additives include ultraviolet absorbers, light stabilizers, and antioxidants.

  In order to prevent deterioration due to exposure to ultraviolet rays, it is preferable to contain an ultraviolet absorber, a light stabilizer, an antioxidant, and the like in the layer (A).

  Examples of the ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2-carboxybenzophenone and 2-hydroxy-4-n-. Benzophenone series such as octoxybenzophenone; 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5-methylphenyl) benzotriazole and 2- ( Benzotriazoles such as 2′-hydroxy-5-t-octylphenyl) benzotriazole; salicylic acid esters such as phenyl salicylate and p-octylphenyl salicylate are used.

  As the light stabilizer, a hindered amine type is used. Examples of hindered amine light stabilizers include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2. , 2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexanoyloxy-2,2,6,6-tetramethylpiperidine, 4- ( o-chlorobenzoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenoxyacetoxy) -2,2,6,6-tetramethylpiperidine, 1,3,8-triaza-7,7, 9,9-tetramethyl-2,4-dioxo-3-noctyl-spiro [4,5] decane, bis (2,2,6,6-tetramethyl-4-piperidi ) Sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tris (2,2,6, 6-tetramethyl-4-piperidyl) benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -2-acetoxypropane-1,2,3- Tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -2-hydroxypropane-1,2,3-tricarboxylate, tris (2,2,6,6-tetramethyl- 4-piperidyl) triazine-2,4,6-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidine) phosphite, tris (2,2,6, -Tetramethyl-4-piperidyl) butane-1,2,3-tricarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) propane-1,1,2,3-tetracarboxylate And tetrakis (2,2,6,6-tetramethyl-4-piperidyl) butane-1,2,3,4-tetracarboxylate.

As the antioxidant, various hindered phenols and phosphites are used. Specific examples of the hindered phenol antioxidant include 2,6-di-t-butyl-p-cresol, 2-t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, 2 , 6-di-t-butyl-4-ethylphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4′-methylenebis (2,6-di-t-butylphenol), 2,2′-methylenebis [6- (1-methylcyclohexyl) -p-cresol], bis [3,3-bis (4-hydroxy) -3-t-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (6-t-butyl-m-cresol), 2,2′-ethylidenebis (4-sec) -Butyl-6-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butyl) Phenyl) butane, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 2,6-diphenyl-4-octadecyloxyphenol, Tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,4′-thiobis (6-tert-butyl-m-cresol), tocopherol, 3,9-bis [1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5) -Methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzylthio ) -1,3,5-triazine and the like.
Specific examples of the phosphite antioxidant include 3,5-di-t-butyl-4-hydroxybenzyl phosphinate dimethyl ester and bis (3,5-di-t-butyl-4-hydroxy). Examples thereof include ethyl benzylphosphonate and tris (2,4-di-t-butylphenyl) phosphanate.

  The antioxidant, light stabilizer, and ultraviolet absorber are each preferably 5 parts by mass or less, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the total amount of the Mg ionomer and the Na ionomer. It can be contained in an amount.

In addition to the additives described above, the layer (A) can contain additives such as a colorant, a light diffusing agent, a flame retardant, and a metal deactivator as necessary.
Examples of the colorant include pigments (organic pigments and inorganic pigments) and dyes. Various known colorants can be used.

  Examples of inorganic pigments include titanium oxide, zinc white, lead white, lithopone, barite, precipitated barium sulfate, calcium carbonate, gypsum, precipitated silica and other white inorganic pigments, carbon black, lamp black, titanium black, and synthetic iron. Black inorganic pigments such as black, gray inorganic pigments such as zinc dust, lead suboxide, slate powder, red inorganic pigments such as cadmium red, cadmium mercury red, silver vermilion, red beangar, molybden red, red lead, amber, iron oxide tea, etc. Brown inorganic pigments, cadmium yellow, zinc yellow, ocher, siena, synthetic ocher, yellow inorganic pigments such as yellow lead, titanium yellow, green inorganic pigments such as chromium oxide green, cobalt green, chromium green, ultramarine blue, bitumen, iron blue Examples thereof include blue inorganic pigments such as cobalt blue and metal powder inorganic pigments.

Examples of organic pigments include Permanent Red 4R, Para Red, First Yellow G, First Yellow 10G, Disazo Yellow G, Disazo Yellow GR, Disazo Orange, Pyrazolone Orange, Brilliant Carmine 3B, Brilliant Carmine. Carmine 6B, Brilliant Scarlet G, Brilliant Bordeaux 10B, Bordeaux 5B, Permanent Red F5R, Permanent Carmine FB, Risole Red R, Risole Red B, Rake Red C, Rake Red D, Brilliant Fast Fast Scarlet, pyrazolone red, bon maroon light, bon maroon medium, azo pigments such as fire red, nitroso pigments such as naphthol green B, nitro such as naphthol yellow S , Basic dyes such as rhodamine B lake and rhodamine 6G lake, mordant dyes such as alizarin and lake, vat dyes such as indanthrene and blue, phthalocyanine blue, phthalocyanine green, fast A phthalocyanine pigment such as sky blue and a dioxazine pigment such as dioxazine violet can be presented.
In addition, organic fluorescent pigments and pearl pigments can be used.

  Examples of the light diffusing agent include glass beads, silica beads, silicon alkoxide beads, and hollow glass beads as inorganic spherical substances. Examples of the organic spherical material include acrylic beads and vinylbenzene plastic beads.

  Examples of the flame retardant include halogen flame retardants such as bromides, phosphorus flame retardants, silicone flame retardants, metal hydrates such as magnesium hydroxide and aluminum hydroxide, and the like.

  As said metal deactivator, a well-known thing can be used as a compound which suppresses the metal damage of a thermoplastic resin. Two or more metal deactivators may be used in combination. Preferable examples of the metal deactivator include hydrazide derivatives or triazole derivatives. Specifically, decamethylene dicarboxyl-disalicyloyl hydrazide as a hydrazide derivative, 2 ′, 3-bis [3- [3,5-ditert-butyl-4-hydroxyphenyl] propionyl] propionohydrazide, A preferred example is bis (2-phenoxypropionyl-hydrazide) of isophthalic acid, and a preferred example of the triazole derivative is 3- (N-salicyloyl) amino-1,2,4-triazole. Besides hydrazide derivatives and triazole derivatives, 2,2′-dihydroxy-3,3′-di- (α-methylcyclohexyl) -5,5′-dimethyl diphenylmethane, tris- (2-methyl-4-hydroxy-) Examples include 5-tert-butylphenyl) butane, a mixture of 2-mercaptobenzimidazole and a phenol condensate.

[(B) layer]
When the interlayer film for laminated glass of the present invention is multilayer, it preferably has at least one (B) layer containing at least one ethylene ionomer.
Thereby, mechanical strength and sound insulation characteristics can be further improved.

  The (B) layer preferably contains an ethylene ionomer as a main component. Here, “including as a main component” means that the total mass of the ethylene ionomer is 60% by mass or more based on the total mass of the layer (B). The total mass is preferably 80% by mass or more.

  From the viewpoint of improving the transparency of the entire interlayer film for laminated glass, the ethylene-based ionomer is an ethylene-based magnesium ionomer (hereinafter sometimes abbreviated as “ethylene-based Mg ionomer”) and an ethylene-based sodium ionomer (hereinafter, referred to as “ethylene-based ionomer”). It may be abbreviated as “ethylene-based Na ionomer”).

The ethylene ionomer (for example, at least one of the ethylene Mg ionomer and the ethylene Na ionomer; the same shall apply hereinafter) contained in the layer (B) is a structural unit derived from ethylene and an α, β-unsaturated carboxylic acid. It is preferably an ionomer of an ethylene / α, β-unsaturated carboxylic acid copolymer having a structural unit derived from The copolymer (or the ionomer) may have a structural unit derived from an α, β-unsaturated carboxylic acid ester.
The content ratio of the structural unit derived from ethylene in the ethylene / α, β-unsaturated carboxylic acid copolymer which is the base polymer of the preferred ethylene ionomer is preferably 97 to 75% by mass, more preferably 95 to 75%. % By mass.
The content ratio of the structural unit derived from the unsaturated carboxylic acid in the ethylene / α, β-unsaturated carboxylic acid copolymer which is the base polymer of the preferred ethylene ionomer is preferably 3 to 25% by mass, more preferably 5 to 25% by mass.

  When the content of the structural unit derived from ethylene is 75% by mass or more, the heat resistance and mechanical strength of the copolymer are good. On the other hand, adhesiveness etc. are favorable in the content rate of the structural unit guide | induced from ethylene being 97 mass% or less.

Examples of the α, β-unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, maleic anhydride monoester, and acrylic acid or methacrylic acid is particularly preferable.
Particularly preferred examples of the Mg ionomer of the ethylene / α, β-unsaturated carboxylic acid copolymer include an Mg ionomer of an ethylene / acrylic acid copolymer and an Mg ionomer of an ethylene / methacrylic acid copolymer.
Particularly preferable examples of the Na ionomer of the ethylene / α, β-unsaturated carboxylic acid copolymer include an Na ionomer of an ethylene / acrylic acid copolymer and an Na ionomer of an ethylene / methacrylic acid copolymer.

The structural unit derived from an unsaturated carboxylic acid contained in the ethylene / α, β-unsaturated carboxylic acid copolymer plays an important role in adhesion to a substrate such as glass. The ethylene ionomer in the layer (B) that may not be adhered to a substrate such as glass may have relatively low adhesion, but also contributes to improvement in adhesion.
From the viewpoint of adhesiveness, the content ratio of the structural unit derived from the unsaturated carboxylic acid to the total mass of the ethylene / α, β-unsaturated carboxylic acid copolymer (or the total mass of the ethylene ionomer) is It is preferable that it is 3 mass% or more. Moreover, transparency and a softness | flexibility are favorable in the said content rate being 3 mass% or more.
On the other hand, from the viewpoint of stickiness suppression and processability improvement, it is derived from the unsaturated carboxylic acid relative to the total mass of the ethylene / α, β-unsaturated carboxylic acid copolymer (or the total mass of the ethylene ionomer). It is preferable that the content rate of a structural unit is 25 mass% or less.

In the ethylene / α, β-unsaturated carboxylic acid copolymer, the total amount of ethylene and α, β-unsaturated carboxylic acid is 100% by mass, more than 0% by mass, preferably 30% by mass or less, preferably more than 0% A structural unit derived from 25% by mass or less of other copolymerizable monomers may be contained.
Other copolymerizable monomers include unsaturated esters such as vinyl esters such as vinyl acetate and vinyl propionate; methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, And (meth) acrylic acid esters such as methyl methacrylate and isobutyl methacrylate. When the structural unit derived from other copolymer monomers is contained in the above range, it is preferable because the flexibility of the ethylene / unsaturated carboxylic acid copolymer is improved.

  The degree of neutralization of the ethylene ionomer contained in the layer (B) is preferably 80% or less. The neutralization degree is preferably 5% or more and 80% or less from the viewpoint of workability and flexibility.

  The ethylene / α, β-unsaturated carboxylic acid copolymer, which is sometimes used as a base polymer of the ethylene ionomer contained in the layer (B), is, for example, a method in which each polymerization component is radicalized at high temperature and high pressure. It can be obtained by copolymerization. The ionomer can be obtained by reacting an ethylene / α, β-unsaturated carboxylic acid copolymer with a metal hydroxide, a metal oxide, a metal acetate, or the like.

The ethylene ionomer contained in the layer (B) has a melt flow rate (MFR; conforming to JIS K7210-1999) at 190 ° C. and 2160 g load in the range of 0.1 to 150 g / 10 in consideration of workability and mechanical strength. It is preferable that it is a minute, and it is more preferable that it is especially 0.1-50 g / 10min.
When the interlayer film for laminated glass of the present invention includes the (B) layer, the ionomer contained in the (A) layer and the ethylene ionomer contained in the (B) layer from the viewpoint of workability and mechanical strength. Both the melt flow rates are preferably 0.1 to 150 g / 10 min, and more preferably 0.1 to 50 g / 10 min.

When the layer (B) contains at least one of an ethylene-based Na ionomer and an ethylene-based Mg ionomer, the total amount of the ethylene-based Na ionomer and the ethylene-based Mg ionomer is 60% by mass or more of the solid content of the (B) layer. Preferably, it is 70% by mass or more, and particularly preferably 80% by mass or more.
When the total amount of the ethylene-based Na ionomer and the ethylene-based Mg ionomer is within the above range, the transparency as a laminated glass can be dramatically improved, and the visual field recognizability as a laminated glass can be improved more effectively than before. it can.

  The layer (B) preferably contains the ethylene-based Mg ionomer from the viewpoint of more effectively improving the transparency of the interlayer film for laminated glass. It is more preferable to contain 80% by mass or more based on the total amount of the resin materials contained in the layer.

The (B) layer may contain a resin material other than the ethylene ionomer together with the ethylene ionomer.
As the other resin material, any resin material can be used as long as it is compatible with the ethylene ionomer and does not impair the transparency and mechanical properties of the layer (B).
As the other resin material, an ethylene / unsaturated carboxylic acid copolymer and an ethylene / unsaturated ester / unsaturated carboxylic acid copolymer are preferable.
Further, if the other resin material is a resin material having a melting point higher than that of the ethylene ionomer, it is possible to improve the heat resistance and durability of the layer (B).

  The layer (B) can contain various additives and colorants within a range that does not impair the object of the present invention. Examples of such additives include all those mentioned above as additives that can be contained in the layer (A). In addition, when the additive is contained in the (B) layer, the same amount of the additive as that when the additive is contained in the (A) layer can be contained.

In the present invention, the silane coupling agent is contained in the (A) layer, but when the (B) layer is used together with the (A) layer, the silane coupling agent may also be contained in the (B) layer.
However, for example, when the layer structure including the (A) layer and the (B) layer is “(A) layer / (B) layer / (A) layer” or the like, the (B) layer is other than the (A) layer. Since adhesion to the material may not be required, the layer (B) preferably does not substantially contain a silane coupling agent. Specifically, from the viewpoint of production stability, the content of the silane coupling agent in the layer (B) is preferably 0.1% by mass or less of the solid content of the layer (B). Furthermore, it is particularly preferable that the layer (B) contains no silane coupling agent (0% by mass).

The total thickness of the interlayer film for laminated glass of the present invention is not particularly limited, but the total thickness is preferably in the range of 5 μm to 2000 μm (0.005 mm to 2 mm), and is preferably 100 μm to 2000 μm (0.1 mm to 2 mm) is more preferable, and a range of 100 μm to 1500 μm (0.1 mm to 1.5 mm) is even more preferable.
When the total thickness is in the above range, it is excellent in economic efficiency (that is, at an appropriate cost as a product) and excellent in adhesiveness and transparency.

  The form of (A) layer in the present invention is preferably a single layer. However, the form of the layer (A) is not limited to a form that is a single layer. For example, the type of ionomer contained (for example, copolymerization ratio of base polymer, degree of neutralization, metal type, etc.), etc. The form which consists of a several layer from which these differ may be sufficient.

When the interlayer film for laminated glass of the present invention includes the (B) layer, the (A) layer is preferably provided so as to be superimposed on one side or both sides of the (B) layer.
Among them, from the viewpoint of adhesiveness to the glass sheet, at least two (A) layers and at least one (B) layer are provided, and the (B) layer is disposed between the two (A) layers. It is preferable to have a multilayer structure of “(A) layer / (B) layer / (A) layer”.
In addition, the interlayer film for laminated glass of the present invention may include three or more layers (A) and two or more layers (B). In this case, the layer constituting the outermost layer from which one side is exposed is provided. As long as it is a layer structure “(A) layer /... (B) layer... / (A) layer” that is a layer (A), it may be configured in any structure.
In addition, the layer (B) is preferably a single layer, like the layer (A). However, the form of the (B) layer is not limited to the form of a single layer. For example, the type of ionomer contained (for example, the copolymerization ratio of the base polymer, the degree of neutralization, the metal type, etc.), etc. The form which consists of a several layer from which these differ.

  When the intermediate film for laminated glass of the present invention is a film having a multilayer structure, the intermediate layer composed of the (B) layer and the two (A) layers formed on both sides of the intermediate layer so as to sandwich the intermediate layer. It is preferably a three-layer sheet including an outer layer, or a two-layer sheet including a layer (A) and a layer (B). The three-layer sheet is particularly preferable from the viewpoint of achieving both transparency and adhesiveness.

When the interlayer film for laminated glass of the present invention includes the (A) layer and the (B) layer, the thickness of the (A) layer is arbitrary, but the thickness a of the (A) layer is 1 μm to 500 μm. The range of 10 μm to 500 μm is more preferable, and the range of 20 μm to 300 μm is particularly preferable.
When the thickness a is 1 μm or more, the adhesive strength can be further improved, and when the thickness a is 500 μm or less, the transparency is more excellent.
Moreover, when the interlayer film for laminated glass of the present invention includes the (A) layer and the (B) layer, the thickness of the (B) layer in the total layer thickness may be large in terms of transparency. Specifically, the thickness (b) of the (B) layer can be freely set within a range obtained by subtracting the preferable thickness (a) of the (A) layer from the preferable total thickness of 5 μm to 2000 μm.

When the interlayer film for laminated glass of the present invention includes the (A) layer and the (B) layer, the thickness ratio (a / layer) of the (A) layer (thickness a) and the (B) layer (thickness b). b) is preferably 5/1 to 1/20, more preferably 3/1 to 1/10, and even more preferably 3/1 to 1/8.
When the ratio (a / b) of the thicknesses of the (A) layer and the (B) layer is within the above range, the adhesiveness and transparency are further improved.

The interlayer film for laminated glass of the present invention is molded by a known method using a single layer T-die extruder, a multilayer T-die extruder, a calendar molding machine, a single layer inflation molding machine, a multilayer inflation molding machine, or the like. be able to.
For example, the interlayer film for laminated glass of the present invention is dry blended by adding additives such as a silane coupling agent, an antioxidant, a light stabilizer, and an ultraviolet absorber to the ionomer that is a raw material as necessary. It is obtained by feeding from a hopper of a main extruder and a sub-extruder of a T-die extruder and extruding it into a sheet.

The interlayer film for laminated glass of the present invention is laminated by a double vacuum tank laminating machine in a state where the interlayer film for laminated glass is sandwiched between two 3.2 mm thick blue plate float glasses (conditions: 150 ° C., 8 minutes), and then cooled in the air at 23 ° C. (that is, cooling), the total light transmittance according to JIS-K7105 can be 83% or more. In other words, since transparency tends to deteriorate when the film is cooled after bonding, it is usual to cool rapidly after bonding, and the total light transmittance after the rapid cooling is evaluated. In the invention, the total light transmittance after the cooling is 83% or more, which shows very good transparency.
The total light transmittance is more preferably 85% or more.
The total light transmittance is a value measured according to JIS-K7105 using a haze meter (manufactured by Suga Test Instruments Co., Ltd.). The term “cooling (removal)” refers to cooling at a rate of temperature decrease of 15 ° C./min or less (calculated from the temperature 5 minutes after the start of cooling).

[Laminated glass]
The laminated glass of the present invention is constituted by fixing two glass sheets with the interlayer film for laminated glass.
As a structure of the laminated glass of this invention, the structure of a glass sheet / interlayer film for laminated glasses / glass sheet is mentioned, for example.
More specifically, the configuration includes glass sheet / (A) layer / glass sheet, glass sheet / (A) layer / (B) layer / (A) layer / glass sheet, and the like. Furthermore, among these configurations, a configuration in which a colorant is blended in at least one layer is also included.

The material of the glass sheet is not particularly limited, and soda lime glass is preferably used. Among them, highly transmissive glass (so-called white plate glass) is preferably used. High transmission glass is soda lime glass with a low iron content, and has high light transmittance. Moreover, the template glass which gave the embossed pattern on the surface is also used suitably. Further, soda lime glass (so-called blue plate glass) having a high iron content, heat ray reflective glass, heat ray absorbing glass and the like can be preferably used.
The thickness of the glass sheet (plate) is not particularly limited, but is usually 4 mm or less, preferably 2.5 mm or less. Although the lower limit is not limited, it is usually 0.1 mm or more, preferably 0.5 mm or more.

In order to produce the laminated glass of the present invention, for example, the interlayer film for laminated glass may be placed between two glass sheets and thermocompression bonded under heating and pressure. The heating temperature is, for example, about 100 to 250 ° C., and the pressure is, for example, about 0.1 to 30 kg / cm ² .

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “parts” and “ppm” are based on mass.
“Ethylene content”, “methacrylic acid content”, and “isobutyl acrylate content” are the content ratio of structural units derived from ethylene in the resin and the content ratio of structural units derived from methacrylic acid in the resin, respectively. And the content ratio of structural units derived from isobutyl acrylate in the resin.

The materials used in the following Examples and Comparative Examples, the composition of each layer, the base material, and the evaluation method are as follows.
-(1) Resin-
1. (A) Layer resin material / ionomer 1: ethylene / methacrylic acid / acrylic acid isobutyl ester copolymer (ethylene content = 75 mass%, methacrylic acid content = 8 mass%, acrylic acid isobutyl ester content = 17 mass%) Magnesium ionomer (neutralization degree 45%, MFR 5.0 g / 10 min)
Ionomer 2: Sodium ionomer (degree of neutralization 55) of ethylene / methacrylic acid / acrylic acid isobutyl ester copolymer (ethylene content = 75% by mass, methacrylic acid content = 8% by mass, acrylic acid isobutyl ester content = 17% by mass) %, MFR 2.5 g / 10 min)

2. (B) Resin material for layer / ionomer 3: Magnesium ionomer of ethylene / methacrylic acid copolymer (ethylene content = 85 mass%, methacrylic acid content = 15 mass%) (degree of neutralization 37%, MFR 5 g / 10 min)
Ionomer 4: Sodium ionomer of ethylene / methacrylic acid copolymer (ethylene content = 81 mass%, methacrylic acid content = 19 mass%) (degree of neutralization 45%, MFR 4.5 g / 10 min)

-(2) Silane coupling agent-
N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane: “KBM602” manufactured by Shin-Etsu Chemical Co., Ltd.
N-2- (aminoethyl) -3-aminopropyltriethoxysilane: “KBE603” manufactured by Shin-Etsu Chemical Co., Ltd.

-(3) Formulation-
The blending of the silane coupling agent into the layer (A) was performed by previously mixing the ionomer and the silane coupling agent at a predetermined ratio before molding.

-(4) Base material-
・ 3.2mm thick blue plate tempered glass (Asahi Glass Co., Ltd.)

[Example 1]
A resin composition obtained by adding 1500 ppm of KBE603 to ionomer 1 with respect to the mass of ionomer 1 (resin composition in which the amount of KBE603 with respect to 100 parts by mass of ionomer 1 is 0.15 parts by mass) is compression-molded. As a laminated glass interlayer film, a single-layer sheet consisting only of the layer (A) was produced.
The compression molding was performed using an automatic press molding machine manufactured by Toho Machinery Co., Ltd. under the conditions of heating at 160 ° C. for 5 minutes to dissolve the resin composition and cooling at 23 ° C. for 3 minutes.
As the single-layer sheet, a 900 μm-thick single layer sheet for transparency evaluation and a 600 μm-thick single-layer sheet for adhesive evaluation were prepared, respectively (Examples after Example 2 and later and comparative examples) Is the same).

<Evaluation>
The following various evaluation was implemented using the obtained single layer sheet. The evaluation results are shown in Table 1 below.

(transparency)
Vacuum heating bonding of 3.2 mm blue sheet tempered glass (75 mm × 120 mm), the above-obtained single layer sheet 900 μm thick, and 3.2 mm blue sheet tempered glass (75 mm × 120 mm) Using a container (LM-50x50S, double vacuum chamber bonding machine manufactured by NPC) under the condition of 160 ° C. for 8 minutes, then fix one end of the short piece and stand on a glass stand Leave in the air at a temperature of 23 ° C. to cool down (cooling rate = 13 ° C./min, surface temperature at the center of the glass 5 minutes after the start of cooling 85 ° C.), blue sheet tempered glass / single layer sheet / blue sheet tempered glass A sample having the following structure was prepared.
Using this sample, total light transmittance (%) and haze (%) were measured with a haze meter (manufactured by Suga Test Instruments Co., Ltd.) according to JIS-K7105.

(Adhesiveness)
Using a vacuum heat bonding machine (LM-50x50S, manufactured by NPC), a 3.2 mm thick blue plate tempered glass (75 mm × 120 mm) and a single layer sheet of 600 μm thickness obtained above, Bonding was performed under conditions of 8 minutes, and a sample composed of a blue sheet tempered glass / single layer sheet was produced. Using this sample, the adhesive strength (initial adhesive strength) (N) between the blue sheet tempered glass and the single layer sheet was measured. The measurement was performed under the conditions of a width of 15 mm and a tensile speed of 100 mm / min.
A sample similar to the above was aged for 1 week in an environment of 85 ° C. and 90% RH, and the adhesive strength (moisture resistant adhesive strength) (N) was similarly measured for the sample after aging.

[Example 2]
In Example 1, except that the amount of KBE603 added was changed to 5000 ppm, a single-layer sheet consisting of only the layer (A) (a single-layer sheet having a thickness of 900 μm for transparency evaluation, and A single-layer sheet having a thickness of 600 μm for evaluating adhesiveness was prepared and subjected to various evaluations. The evaluation results are shown in Table 1 below.
In the resin composition (single layer sheet) of Example 2, the amount of KBE 603 with respect to 100 parts by mass of ionomer 1 is 0.5 parts by mass.

[Example 3]
In Example 1, except that KBE 603 was changed to KBM 602 of the same mass, in the same manner as in Example 1, a single-layer sheet consisting of only the layer (A) (a single-layer sheet having a thickness of 900 μm for transparency evaluation, and A single-layer sheet having a thickness of 600 μm for evaluating adhesiveness was prepared and subjected to various evaluations. The results are shown in Table 1 below.

[Example 4]
In Example 1, except that the ionomer 1 was changed to an ionomer 2 having the same mass, the same as in Example 1, a single-layer sheet consisting of only the layer (A) (a single-layer sheet with a thickness of 900 μm for transparency evaluation) And a single-layer sheet having a thickness of 600 μm for evaluating adhesiveness) and various evaluations were performed. The results are shown in Table 1 below.

[Example 5]
In Example 2, except that the ionomer 1 was changed to the ionomer 2 having the same mass, the single-layer sheet composed of only the layer (A) (a single-layer sheet having a thickness of 900 μm for transparency evaluation) was obtained in the same manner as in Example 2. And a single-layer sheet having a thickness of 600 μm for evaluating adhesiveness) and various evaluations were performed. The results are shown in Table 1 below.

[Example 6]
A single layer consisting of only the layer (A) in the same manner as in Example 3, except that the ionomer 1 was changed to the ionomer 2 having the same mass in Example 3, and the addition amount of KBM602 was changed to 5000 ppm. Sheets (a single-layer sheet with a thickness of 900 μm for evaluating transparency and a single-layer sheet with a thickness of 600 μm for evaluating adhesiveness) were prepared and subjected to various evaluations. The results are shown in Table 1 below.

[Example 7]
A resin composition obtained by adding KBE603 to ionomer 1 and 1500 ppm relative to the mass of ionomer 1 (KBE603 (0.15 parts by mass) with respect to ionomer 1 (100 parts by mass)) was molded by a sheet molding machine. , (A) Single layer sheet (thickness 300 μm) for layer was produced.
Moreover, the ionomer 3 was shape | molded with the sheet molding machine, and the single layer sheet (300 micrometers in thickness) for (B) layers was produced.
As the sheet forming machine, a 40 mmφ single-screw extruder (manufactured by Nakatani Machinery Co., Ltd.) equipped with a die having a die width of 40 mm was used.

<Evaluation>
Evaluation was performed as follows using each single-layer sheet. The evaluation results are shown in Table 1 below.

(transparency)
3.2 mm thick blue sheet tempered glass (75 mm × 120 mm), single layer sheet for layer (A), single layer sheet for layer (B), and single layer sheet for layer (A) And 3.2 mm thick blue plate tempered glass (75 mm × 120 mm), using a vacuum heating laminator (LM-50 × 50S, NPC double vacuum tank laminating machine) at 160 ° C. for 8 minutes. After pasting in this order under conditions, one end on the short piece side is fixed and placed in a glass stand and left in the atmosphere at a temperature of 23 ° C. to remove the cooling (cooling rate = 13 ° C./min, cooling start 5 minutes) The surface temperature of the latter glass center was 85 ° C.), and a sample having a configuration of blue plate tempered glass / (A) layer / (B) layer / (A) layer / blue plate tempered glass was produced.
Using this sample, the total light transmittance (%) and haze (%) were measured in the same manner as in Example 1.
This evaluation of transparency is an evaluation assuming a multilayer sheet (interlayer film for laminated glass) of “(A) layer / (B) layer / (A) layer”.

(Adhesiveness)
A 3.2 mm thick blue sheet tempered glass (75 mm × 120 mm), a single layer sheet for the (A) layer, and a single layer sheet for the (B) layer were vacuum heated and bonded (LM-50 × 50S, NPC). Were made in this order under the conditions of 160 ° C. and 8 minutes to produce a sample for evaluating adhesiveness composed of blue sheet tempered glass / (A) layer / (B) layer.
Using the obtained sample for evaluating adhesiveness, the initial adhesive strength and the moisture-resistant adhesive strength were measured by the same method as in Example 1.
This adhesive evaluation is based on the adhesion between the (A) layer and the glass when a multilayer sheet (interlayer film for laminated glass) of “(A) layer / (B) layer / (A) layer” is used. This is an assumed evaluation.

[Example 8]
In Example 7, various evaluations were performed in the same manner as in Example 7 except that the ionomer 3 was changed to the ionomer 4. The evaluation results are shown in Table 1 below.

[Comparative Example 1]
In Example 1, various evaluations were performed in the same manner as in Example 1 except that KBE603 was not used. The evaluation results are shown in Table 2 below.

[Comparative Example 2]
In Example 4, various evaluations were performed in the same manner as in Example 4 except that KBE603 was not used. The evaluation results are shown in Table 2 below.

[Comparative Example 3]
In Example 1, various evaluations were performed in the same manner as in Example 1 except that the ionomer 1 was changed to the ionomer 3. The evaluation results are shown in Table 2 below.

[Comparative Example 4]
In Example 3, various evaluations were performed in the same manner as in Example 3 except that the ionomer 1 was changed to the ionomer 3. The evaluation results are shown in Table 2 below.

[Comparative Example 5]
In Example 1, the ionomer 1 was replaced with a magnesium ionomer (neutralized) of an ethylene / methacrylic acid copolymer (ethylene content = 92% by mass, methacrylic acid content = 8% by mass) not containing a structural unit derived from isobutyl acrylate. Degree 45%) (hereinafter referred to as “ionomer 5”), and various evaluations were performed in the same manner as in Example 1. The evaluation results are shown in Table 2 below.

  Regarding the adhesive strengths in Table 2 above, “not measurable” means that the adhesive strength was too weak to measure the adhesive strength.

  As shown in the above Tables 1 and 2, in the Examples, the adhesiveness superior to that of the Comparative Examples was exhibited while maintaining high transparency. In the examples, the moisture-resistant adhesive strength was particularly high as compared with the comparative examples.

  The interlayer film for laminated glass of the present invention is an invention that is particularly excellent in adhesiveness with a glass sheet, such as an acrylic resin sheet, a polycarbonate sheet, or a polyester sheet, although the transparency is inferior to glass, It is also possible to make a laminated glass in combination with a commercially available plastic glass.

Claims (9)

  Silane coupling agent and magnesium ionomer of ethylene / α, β-unsaturated carboxylic acid / α, β-unsaturated carboxylic acid ester copolymer and ethylene / α, β-unsaturated carboxylic acid / α, β-unsaturated An interlayer film for laminated glass having a layer (A) containing at least one of sodium ionomers of carboxylic acid ester copolymers.   A multi-layer structure in which at least two layers (A) and at least one layer (B) containing an ethylene ionomer are included, and the (B) layer is disposed between the two (A) layers. The interlayer film for laminated glass according to claim 1, comprising: A multi-layer structure in which at least two layers (A) and at least one layer (B) containing an ethylene ionomer are included, and the (B) layer is disposed between the two (A) layers. Including
The interlayer film for laminated glass according to claim 1 or 2, wherein the (B) layer has a silane coupling agent content of 0.1 mass% or less of the solid content of the (B) layer.   The said (A) layer contains 3 mass parts or less of silane coupling agents which have an amino group and an alkoxy group with respect to 100 mass parts of total amounts of the said magnesium ionomer and the said sodium ionomer. The interlayer film for laminated glass according to any one of the above.   The total thickness is 0.1-2 mm, The intermediate film for laminated glasses of any one of Claims 1-4. A multi-layer structure in which at least two layers (A) and at least one layer (B) containing an ethylene ionomer are included, and the (B) layer is disposed between the two (A) layers. Including
The ratio (a / b) of the thickness (a) of the (A) layer to the thickness (b) of the (B) layer is 5/1 to 1/20. An interlayer film for laminated glass. A multi-layer structure in which at least two layers (A) and at least one layer (B) containing an ethylene ionomer are included, and the (B) layer is disposed between the two (A) layers. Including
The melt flow rate (MFR; JIS K7210-1999, 190 ° C., 2160 g load) of at least one of the magnesium ionomer and the sodium ionomer in the layer (A) and the ethylene ionomer in the layer (B) is 0.1. It is 1-150g / 10min, The intermediate film for laminated glasses of any one of Claims 1-6.   When sandwiched between two 3.2 mm thick blue plate float glass, bonded at 150 ° C. for 8 minutes in a double vacuum tank bonding machine, and allowed to cool at 23 ° C. atmospheric pressure. The interlayer film for laminated glass according to any one of claims 1 to 7, wherein the total light transmittance in accordance with JIS-K7105 is 83% or more.   The laminated glass provided with the intermediate film for laminated glasses of any one of Claims 1-8.