KR102390849B1 - Resin composition and its use - Google Patents

Abstract

The resin composition for a laminated glass interlayer film and the resin composition for a solar cell encapsulant of the present invention contains an ionomer (A) of an ethylene-unsaturated carboxylic acid-based copolymer and a silane coupling agent having an amino group (B), and contains ethylene/unsaturated The metal ion constituting the ionomer (A) of the carboxylic acid-based copolymer includes a monovalent metal ion and a polyvalent metal ion.

Description

Resin composition and its use

The present invention relates to a resin composition for a laminated glass interlayer film, a laminated glass interlayer film and laminated glass, and a resin composition for a solar cell encapsulant, a solar cell encapsulant, and a solar cell module.

As a laminated glass interlayer film and a solar cell sealing material, the film|membrane comprised by the ionomer of an ethylene-unsaturated carboxylic acid type copolymer is known.

As a technique related to such a laminated glass interlayer film, the thing described in patent document 1 (Unexamined-Japanese-Patent No. 2009-512763) is mentioned, for example.

In Patent Document 1, a polymer sheet having at least one layer including an ionomer or an ionomer blend having a thickness of 0.25 mm or more and introducing a partially neutralized α,β-ethylenically unsaturated carboxylic acid as a polymer sheet , wherein the ionomer or ionomer blend comprises an ion of one or more monovalent metals in an amount ranging from about 1 to about 60% based on the total amount of neutralization of the α,β-ethylenically unsaturated carboxylic acid, and about 40 Polymeric sheets are described, characterized in that they contain ions of one or more polyvalent metals in an amount ranging from about 99%.

Japanese Patent Publication No. 2009-512763

The technical level required for various properties of the laminated glass interlayer is gradually increasing. MEANS TO SOLVE THE PROBLEM The present inventors discovered the following subjects with respect to a laminated glass interlayer.

First, a laminated glass interlayer film composed of an ionomer of an ethylene/unsaturated carboxylic acid copolymer containing both monovalent metal ions and polyvalent metal ions as described in Patent Document 1 has good water resistance, but optical properties and glass adhesion performance was not satisfactory enough.

Here, according to the studies of the present inventors, it was found that the optical properties of the laminated glass interlayer film were improved to some extent when the ratio of the monovalent metal ions constituting the ionomer was increased. However, if the ratio of the monovalent metal ion constituting the ionomer is increased, this time the water resistance of the laminated glass interlayer deteriorates, and it is difficult to improve the glass adhesion.

That is, the present inventors found that there is a trade-off relationship between the optical properties and water resistance of the laminated glass interlayer made of the ionomer, and the trade-off relationship is only by adjusting the ratio of monovalent and polyvalent metal ions in the ionomer. It has been found that it is not possible to sufficiently improve by using That is, the present inventors have discovered that there is room for improvement in the conventional laminated glass interlayer film made of an ionomer in terms of improving the optical properties and water resistance in a well-balanced manner and improving the glass adhesion.

Moreover, the solar cell encapsulant also had the same subject as the said laminated glass interlayer film.

The present invention has been made in view of the above circumstances, and is to provide a resin composition for a laminated glass interlayer film and a solar cell encapsulant that is excellent in the performance balance of optical properties and water resistance, and has excellent adhesion to glass and the like.

MEANS TO SOLVE THE PROBLEM In order to achieve the said subject, the present inventors repeated earnest examination. As a result, by combining a silane coupling agent having an amino group with respect to an ionomer containing both monovalent metal ions and polyvalent metal ions, the above trade-off relationship can be improved, and optical properties and water resistance can be improved in a balanced way. It was discovered that the adhesiveness to glass or the like can be improved, and the present invention has been reached.

That is, according to the present invention, a resin composition for a laminated glass interlayer film, a laminated glass interlayer film and a laminated glass, and a resin composition for a solar cell encapsulant, a solar cell encapsulant, and a solar cell module are provided.

[One]

A resin composition used to form a laminated glass interlayer, comprising:

It contains an ionomer (A) of an ethylene-unsaturated carboxylic acid-based copolymer and a silane coupling agent (B) having an amino group,

The resin composition for a laminated glass interlayer film, wherein the metal ions constituting the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer include monovalent metal ions and polyvalent metal ions.

[2]

In the resin composition for an interlayer film for laminated glass according to the above [1],

The resin composition for a laminated glass interlayer film, wherein the molar ratio of the polyvalent metal ion to the monovalent metal ion in the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer is 0.1 or more and 10 or less.

[3]

The resin composition for an interlayer film for laminated glass according to the above [1] or [2],

The resin composition for a laminated glass interlayer, wherein the monovalent metal ion includes one or more selected from lithium ions, potassium ions, sodium ions, silver ions, mercury ions, and copper ions.

[4]

In the resin composition for an interlayer film for laminated glass according to any one of [1] to [3],

The polyvalent metal ion is selected from calcium ion, magnesium ion, zinc ion, aluminum ion, barium ion, beryllium ion, strontium ion, copper ion, cadmium ion, mercury ion, tin ion, lead ion, iron ion, cobalt ion and nickel ion. A resin composition for a laminated glass interlayer comprising one or more selected types.

[5]

In the resin composition for an interlayer film for laminated glass according to any one of [1] to [4],

The resin composition for an interlayer film for laminated glass, wherein the degree of neutralization of the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer is 5% or more and 95% or less.

[6]

In the resin composition for an interlayer film for laminated glass according to any one of [1] to [5],

A resin composition for a laminated glass interlayer film having a haze measured by the following method of less than 1.0%.

(Way)

A film of 120 mm x 75 mm x 0.4 mm constituted by the resin composition for laminated glass interlayer is obtained. Next, the obtained said film|membrane is pinched|interposed between the glass plates of 120 mm x 75 mm x 3.2 mm, 140 degreeC, vacuum holding for 5 minutes, and 0.1 MPa (gauge pressure) for 3 minutes with a vacuum laminator are performed, and laminated glass is obtained. Next, the haze of the obtained laminated glass is measured with a haze meter in accordance with JIS K7136.

[7]

In the resin composition for an interlayer film for laminated glass according to any one of [1] to [6],

The resin composition for a laminated glass interlayer film, wherein the length of the cloudy part measured by the following method is 5 mm or less.

(Way)

A film of 120 mm x 75 mm x 0.4 mm constituted by the resin composition for laminated glass interlayer is obtained. Next, the obtained said film|membrane is pinched|interposed between glass plates of 120 mm x 75 mm x 3.2 mm, 140 degreeC, vacuum holding for 5 minutes, and 0.1 MPa (gauge pressure) for 3 minutes are performed with a vacuum laminator, and laminated glass is obtained. Next, the obtained laminated glass is immersed in hot water at 90°C for 2 hours. Next, in the cloudy portion generated at the edge of the laminated glass, the length of the cloudy portion in a direction perpendicular to the cross section of the laminated glass is measured.

[8]

In the resin composition for an interlayer film for laminated glass according to any one of [1] to [7],

A resin composition for a laminated glass interlayer film having an adhesive strength to a glass plate of 10 N/15 mm or more as measured by the following method.

(Way)

A film of 120 mm x 75 mm x 0.4 mm constituted by the resin composition for laminated glass interlayer is obtained. Next, the obtained film was laminated on the non-tin surface of a glass plate of 120 mm × 75 mm × 3.9 mm, and pressed with a vacuum laminator at 140° C. for 3 minutes, vacuum holding for 30 minutes, and 0.1 MPa (gauge pressure) for 30 minutes, and the film was It is adhered to the non-tin surface of the glass plate. Then, the film is peeled off from the glass plate at a tensile rate of 100 mm/min, and the maximum stress is calculated as the adhesive strength to the glass plate (N/15 mm).

[9]

In the resin composition for an interlayer film for laminated glass according to any one of [1] to [8],

The ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer is the monovalent metal ion ionomer (A1) of the ethylene/unsaturated carboxylic acid copolymer, and the polyvalent metal ion of the ethylene/unsaturated carboxylic acid copolymer A resin composition for a laminated glass interlayer comprising an ionomer (A2).

[10]

In the resin composition for an interlayer film for laminated glass according to any one of [1] to [9],

A resin composition for a laminated glass interlayer film, wherein the unsaturated carboxylic acid constituting the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer includes at least one selected from acrylic acid and methacrylic acid.

[11]

In the resin composition for an interlayer film for laminated glass according to any one of [1] to [10],

The content of the silane coupling agent having an amino group (B) is 0.001 mass % or more and 5 mass % or less when the total amount of the resin composition for laminated glass interlayer film is 100 mass %.

[12]

In the resin composition for an interlayer film for laminated glass according to any one of [1] to [11],

In the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer, when the total amount of the structural units constituting the ethylene/unsaturated carboxylic acid copolymer is 100% by mass, a structural unit derived from an unsaturated carboxylic acid A resin composition for a laminated glass interlayer film having a value of 5% by mass or more and 35% by mass or less.

[13]

A laminated glass interlayer comprising the resin composition for a laminated glass interlayer according to any one of [1] to [12].

[14]

The laminated glass interlayer film according to the above [13];

Transparent plate-like members provided on both sides of the laminated glass interlayer

A laminated glass comprising a.

[15]

The laminated glass according to the above [14], wherein the haze measured by a haze meter in accordance with JIS K7136 is less than 1.0%.

[16]

The laminated glass according to [14] or [15], wherein the length of the cloudy part measured by the following method is 5 mm or less.

(Way)

The laminated glass is immersed in hot water at 90° C. for 2 hours. Next, in the cloudy portion generated at the edge of the laminated glass, the length of the cloudy portion in a direction perpendicular to the cross section of the laminated glass is measured.

[17]

As a resin composition used to form a solar cell encapsulant,

It contains an ionomer (A) of an ethylene-unsaturated carboxylic acid-based copolymer and a silane coupling agent (B) having an amino group,

A resin composition for a solar cell encapsulant in which the metal ion constituting the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer includes a monovalent metal ion and a polyvalent metal ion.

[18]

In the resin composition for a solar cell encapsulant according to the above [17],

A resin composition for a solar cell encapsulant wherein a molar ratio of the polyvalent metal ion to the monovalent metal ion in the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer is 0.1 or more and 10 or less.

[19]

In the resin composition for a solar cell encapsulant according to the above [17] or [18],

The monovalent metal ion is a resin composition for a solar cell encapsulant comprising one or more selected from lithium ions, potassium ions, sodium ions, silver ions, mercury ions, and copper ions.

[20]

In the resin composition for a solar cell encapsulant according to any one of [17] to [19],

The polyvalent metal ion is selected from calcium ion, magnesium ion, zinc ion, aluminum ion, barium ion, beryllium ion, strontium ion, copper ion, cadmium ion, mercury ion, tin ion, lead ion, iron ion, cobalt ion and nickel ion. A resin composition for a solar cell encapsulant comprising one or two or more selected.

[21]

In the resin composition for a solar cell encapsulant according to any one of [17] to [20],

A resin composition for a solar cell encapsulant having a degree of neutralization of the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer of 5% or more and 95% or less.

[22]

In the resin composition for a solar cell encapsulant according to any one of [17] to [21],

A resin composition for a solar cell encapsulant having a haze measured by the following method of less than 1.0%.

(Way)

A film of 120 mm x 75 mm x 0.4 mm constituted by the resin composition for solar cell encapsulants is obtained. Next, the obtained said film|membrane is pinched|interposed between the glass plates of 120 mm x 75 mm x 3.2 mm, 140 degreeC, vacuum holding for 5 minutes, and 0.1 MPa (gauge pressure) for 3 minutes are performed with a vacuum laminator, and laminated glass is obtained. Next, the haze of the obtained laminated glass is measured with a haze meter in accordance with JIS K7136.

[23]

In the resin composition for a solar cell encapsulant according to any one of [17] to [22],

The resin composition for a solar cell encapsulant whose length of the cloudiness part measured by the following method is 5 mm or less.

(Way)

A film of 120 mm x 75 mm x 0.4 mm constituted by the resin composition for solar cell encapsulants is obtained. Next, the obtained said film|membrane is pinched|interposed between glass plates of 120 mm x 75 mm x 3.2 mm, 140 degreeC, vacuum holding for 5 minutes, and 0.1 MPa (gauge pressure) for 3 minutes are performed with a vacuum laminator, and laminated glass is obtained. Next, the obtained laminated glass is immersed in hot water at 90°C for 2 hours. Next, in the cloudy portion generated at the edge of the laminated glass, the length of the cloudy portion in a direction perpendicular to the cross section of the laminated glass is measured.

[24]

In the resin composition for a solar cell encapsulant according to any one of [17] to [23],

A solar cell encapsulant resin composition having an adhesive strength of 10N/15mm or more to a glass plate measured by the following method.

(Way)

A film of 120 mm x 75 mm x 0.4 mm constituted by the resin composition for solar cell encapsulants is obtained. Next, the obtained film was laminated on the non-tin surface of a glass plate of 120 mm × 75 mm × 3.9 mm, and pressed with a vacuum laminator at 140° C. for 3 minutes, vacuum holding, and 0.1 MPa (gauge pressure) for 30 minutes, and the film was pressed on the non-casting surface of the glass plate. Adhesive to asbestos. Then, the film is peeled off from the glass plate at a tensile rate of 100 mm/min, and the maximum stress is calculated as the adhesive strength to the glass plate (N/15 mm).

[25]

In the resin composition for a solar cell encapsulant according to any one of [17] to [24],

The ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer is the monovalent metal ion ionomer (A1) of the ethylene/unsaturated carboxylic acid copolymer, and the polyvalent metal ion of the ethylene/unsaturated carboxylic acid copolymer A resin composition for a solar cell encapsulant comprising an ionomer (A2).

[26]

In the resin composition for a solar cell encapsulant according to any one of [17] to [25],

The unsaturated carboxylic acid constituting the ionomer (A) of the ethylene/unsaturated carboxylic acid-based copolymer comprises at least one selected from acrylic acid and methacrylic acid, a resin composition for a solar cell encapsulant.

[27]

In the resin composition for a solar cell encapsulant according to any one of [17] to [26],

When content of the silane coupling agent (B) which has the said amino group makes the whole of the said solar cell sealing material resin composition 100 mass %, they are 0.001 mass % or more and 5 mass % or less The resin composition for solar cell sealing materials.

[28]

In the resin composition for a solar cell encapsulant according to any one of [17] to [27],

In the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer, when the total amount of the structural units constituting the ethylene/unsaturated carboxylic acid copolymer is 100% by mass, a structural unit derived from an unsaturated carboxylic acid is 5 mass % or more and 35 mass % or less, the resin composition for solar cell sealing materials.

[29]

A solar cell encapsulant comprising the resin composition for a solar cell encapsulant according to any one of [17] to [28].

[30]

The solar cell sealing material according to the above [29], wherein the haze measured by a haze meter according to JIS K7136 is less than 1.0%.

[31]

A solar cell module comprising the solar cell encapsulant according to the above [29] in its configuration.

ADVANTAGE OF THE INVENTION According to this invention, the laminated glass interlayer film and solar cell sealing material excellent in the performance balance of glass adhesiveness, optical characteristic, and water resistance can be implement|achieved.

The objects described above and other objects, features, and advantages will become more apparent from the preferred embodiments described below and the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which showed typically an example of the structure of the laminated glass of embodiment which concerns on this invention.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described using drawings. The drawings are schematic drawings and do not correspond to actual dimensional proportions. In addition, "X to Y" in the numerical range represents X or more and Y or less, unless otherwise specified. In addition, (meth)acryl means acryl or methacryl.

1. Resin composition for laminated glass interlayer

1 is a cross-sectional view schematically showing an example of the structure of a laminated glass 10 according to an embodiment of the present invention.

The resin composition (P) for a laminated glass interlayer film according to the present embodiment is a resin composition used to form the laminated glass interlayer film 11, and includes an ionomer (A) of an ethylene/unsaturated carboxylic acid copolymer and an amino group It contains the silane coupling agent (B) which has, and the metal ion which comprises the ionomer (A) of an ethylene-unsaturated carboxylic acid type copolymer contains a monovalent|monohydric metal ion and a polyvalent metal ion.

According to the studies of the present inventors, a laminated glass interlayer made of an ionomer of an ethylene-unsaturated carboxylic acid-based copolymer containing both monovalent metal ions and polyvalent metal ions has good water resistance, but optical properties and glass adhesiveness It turned out that this was not satisfactory enough.

Further, according to the studies of the present inventors, when the ratio of monovalent metal ions constituting the ionomer is increased, the optical properties of the laminated glass interlayer film are improved to some extent, but this time the water resistance of the laminated glass interlayer film is deteriorated, and the glass adhesiveness is also improved. turned out to be insufficient.

That is, the present inventors found that there is a trade-off relationship between the optical properties and water resistance of the laminated glass interlayer made of the ionomer, and the trade-off relationship is to adjust the ratio of monovalent and polyvalent metal ions in the ionomer. It has been found that it cannot be sufficiently improved only by itself, and it has been found that it is very difficult to make good glass adhesiveness while achieving both optical properties and water resistance. That is, the present inventors have discovered that there is room for improvement in the conventional laminated glass interlayer film made of an ionomer in terms of improving the optical properties and water resistance in a well-balanced manner and improving the glass adhesion.

MEANS TO SOLVE THE PROBLEM In order to achieve the said subject, the present inventors repeated earnest examination. As a result, the above trade-off relationship is improved by combining a silane coupling agent having an amino group (B) with the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer containing a monovalent metal ion and a polyvalent metal ion. It discovered that it became possible to make it possible, and to be able to improve an optical characteristic and water resistance in good balance, and to fully express glass adhesiveness.

That is, the resin composition (P) for a laminated glass interlayer film according to the present embodiment is an ionomer (A) of an ethylene/unsaturated carboxylic acid copolymer containing a monovalent metal ion and a polyvalent metal ion, and a silane coupling agent having an amino group. By including (B), the performance balance of an optical characteristic and water resistance can be made favorable, and sufficient glass adhesiveness can be implement|achieved.

Although the reason for this is not clear, the amino group of the silane coupling agent (B) having an amino group is coordinated with a polyvalent metal in the ethylene/unsaturated carboxylic acid copolymer to determine the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer It is thought that this is because, by inhibiting growth, the optical properties are further improved while maintaining the good water resistance of the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer containing monovalent metal ions and polyvalent metal ions. . In addition, since the amino group of the silane coupling agent having an amino group (B) bonds to a carboxyl group in the ethylene/unsaturated carboxylic acid copolymer, the resin composition (P) for a laminated glass interlayer according to the present embodiment has optical properties and water resistance. It is possible to obtain a laminated glass interlayer film which is not only excellent, but also has excellent adhesion to the transparent plate-like member.

Further, according to the resin composition (P) for a laminated glass interlayer film according to the present embodiment, the ionomer (A) of the ethylene-unsaturated carboxylic acid copolymer containing a monovalent metal ion and a polyvalent metal ion has an amino group By combining the silane coupling agent (B), it is possible to improve the performance balance of glass adhesiveness, optical properties, and water resistance while maintaining good workability (film forming properties) of the resin composition (P) for laminated glass interlayer films.

Thereby, it is possible to obtain a laminated glass interlayer film and laminated glass having excellent appearance and excellent balance in performance of glass adhesion, optical properties, and water resistance.

Hereinafter, each component constituting the resin composition for laminated glass interlayer film according to the present embodiment will be described.

<Ionomer (A) of ethylene/unsaturated carboxylic acid copolymer>

The ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer according to the present embodiment is a resin obtained by neutralizing at least a part of carboxyl groups with a metal ion with respect to a polymer obtained by copolymerizing ethylene and at least one unsaturated carboxylic acid. am. As an ethylene/unsaturated carboxylic acid type copolymer, the copolymer containing ethylene and an unsaturated carboxylic acid can be illustrated.

As the unsaturated carboxylic acid constituting the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer according to the present embodiment, for example, acrylic acid, methacrylic acid, 2-ethylacrylic acid, crotonic acid, maleic acid, fumaric acid , itaconic acid, maleic anhydride, fumaric acid anhydride, itaconic acid anhydride, monomethyl maleate, monoethyl maleate, and the like.

Among these, it is preferable that the said unsaturated carboxylic acid contains at least 1 sort(s) chosen from acrylic acid and methacrylic acid from viewpoints, such as productivity and hygiene of an ethylene-unsaturated carboxylic acid type copolymer. These unsaturated carboxylic acids may be used individually by 1 type, and may be used in combination of 2 or more type. Further, an ethylene/unsaturated carboxylic acid copolymer containing, as a constituent unit, the unsaturated carboxylic acid such as acrylic acid or methacrylic acid, as a constituent unit, in addition to the ionomer of one or two or more ethylene/unsaturated carboxylic acid copolymers. can also be added to obtain an ionomer (A) of an ethylene/unsaturated carboxylic acid copolymer.

To the ionomer of the ethylene/unsaturated carboxylic acid copolymer containing a monovalent metal ion and a polyvalent metal ion, an ethylene/unsaturated carboxylic acid copolymer is further added to obtain an ionomer (A), whereby a laminated glass interlayer film Higher glass adhesiveness can be expressed, and the performance balance of an optical characteristic and water resistance can further be improved, maintaining favorable processability (film forming property) of the resin composition (P) for use.

In the present embodiment, a particularly preferable ethylene/unsaturated carboxylic acid copolymer is an ethylene/(meth)acrylic acid copolymer.

In the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer according to the present embodiment, when the total amount of structural units constituting the ethylene/unsaturated carboxylic acid copolymer is 100% by mass, structural units derived from ethylene Preferably they are 65 mass % or more and 95 mass % or less, More preferably, they are 75 mass % or more and 92 mass % or less.

When the structural unit derived from ethylene is equal to or greater than the lower limit, the heat resistance, mechanical strength, water resistance, workability, and the like of the obtained laminated glass interlayer film can be further improved. Moreover, transparency, flexibility, adhesiveness, etc. of the laminated glass interlayer obtained as a structural unit derived from ethylene are below the said upper limit can be made more favorable.

In the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer according to the present embodiment, when the total amount of structural units constituting the ethylene/unsaturated carboxylic acid copolymer is 100% by mass, derived from unsaturated carboxylic acid The structural unit used becomes like this. Preferably they are 5 mass % or more and 35 mass % or less, More preferably, they are 8 mass % or more and 25 mass % or less.

When the structural unit derived from the unsaturated carboxylic acid is equal to or more than the lower limit, the transparency, flexibility, adhesiveness, and the like of the obtained laminated glass interlayer film can be further improved. Moreover, when the structural unit derived from an unsaturated carboxylic acid is below the said upper limit, heat resistance, mechanical strength, water resistance, workability, etc. of the laminated glass interlayer obtained can be made more favorable.

In the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer according to the present embodiment, when the total amount of structural units constituting the ethylene/unsaturated carboxylic acid copolymer is 100% by mass, preferably 0% by mass or more. 30 mass % or less, More preferably, the structural unit derived from 0 mass % or more and 25 mass % or less of other copolymerizable monomers may be contained. Examples of other copolymerizable monomers include unsaturated esters such as vinyl esters such as vinyl acetate and vinyl propionate; (meth)acrylic acid esters, such as (meth)acrylate methyl, (meth)acrylate ethyl, (meth)acrylate isobutyl, (meth)acrylic acid n-butyl, and (meth)acrylic acid 2-ethylhexyl, etc. are mentioned. When the structural unit derived from other copolymer monomers is contained within the above range, it is preferable from the viewpoint of improving the flexibility of the resulting laminated glass interlayer film.

As the monovalent metal ion constituting the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer according to the present embodiment, one selected from lithium ion, potassium ion, sodium ion, silver ion, mercury ion, copper ion, etc. It is preferable to include one or two or more species or two or more, more preferably one or two or more selected from lithium ions, potassium ions, and sodium ions, and at least one selected from lithium ions and sodium ions. It is more preferable to do so, and it is particularly preferable to include sodium ions.

As polyvalent metal ions constituting the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer according to the present embodiment, calcium ions, magnesium ions, zinc ions, aluminum ions, barium ions, beryllium ions, strontium ions, copper ions , cadmium ions, mercury ions, tin ions, lead ions, iron ions, cobalt ions, nickel ions, and the like, preferably containing one or two or more selected from the group consisting of calcium ions, magnesium ions, zinc ions, aluminum ions, It is more preferable to include 1 type or 2 or more types selected from barium ion, It is more preferable to contain at least 1 type selected from a zinc ion and a magnesium ion, It is especially preferable to contain a zinc ion.

In the resin composition (P) for a laminated glass interlayer film according to the present embodiment, the molar ratio of the polyvalent metal ion to the monovalent metal ion in the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer (number of moles of polyvalent metal ions/ The number of moles of monovalent metal ions) is preferably 0.1 or more, more preferably 0.2 or more, and still more preferably 0.3 or more, from the viewpoint of improving the water resistance of the resulting laminated glass interlayer film.

In addition, in the resin composition (P) for a laminated glass interlayer film according to the present embodiment, the molar ratio of the polyvalent metal ion to the monovalent metal ion in the ionomer (A) of the ethylene/unsaturated carboxylic acid-based copolymer is the obtained laminated glass From a viewpoint of making the optical characteristic of an interlayer film more favorable, it is preferable that it is 10 or less, It is more preferable that it is 8 or less, It is more preferable that it is 5 or less, It is especially preferable that it is 3 or less.

In the resin composition (P) for laminated glass interlayer film according to the present embodiment, the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer is, for example, a monovalent metal ion of the ethylene/unsaturated carboxylic acid copolymer. It can be set as the structure containing the ionomer (A1) and the polyvalent metal ion ionomer (A2) of an ethylene-unsaturated carboxylic acid type copolymer.

Thereby, by adjusting the mixing ratio of the monovalent metal ion ionomer (A1) of the ethylene/unsaturated carboxylic acid copolymer and the polyvalent metal ion ionomer (A2) of the ethylene/unsaturated carboxylic acid copolymer, ethylene/unsaturated carboxyl The ratio of the monovalent metal ion to the polyvalent metal ion in the ionomer (A) of the acid-based copolymer can be easily adjusted.

The degree of neutralization of the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer according to the present embodiment is not particularly limited, but from the viewpoint of further improving the flexibility, adhesion, mechanical strength, workability, and the like of the obtained laminated glass interlayer film , 95% or less is preferable, 90% or less is more preferable, 80% or less is still more preferable, 70% or less is even more preferable, and 60% or less is even more preferable.

In addition, the degree of neutralization of the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer according to the present embodiment is not particularly limited, but from the viewpoint of improving the transparency, heat resistance, water resistance, etc. of the obtained laminated glass interlayer film, 5 % or more is preferable, 10% or more is more preferable, 15% or more is still more preferable, and 20% or more is particularly preferable.

Here, the degree of neutralization of the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer is the ratio (%) of the carboxyl groups neutralized by metal ions among all the carboxyl groups contained in the ethylene/unsaturated carboxylic acid copolymer. indicates

The method for producing the ethylene/unsaturated carboxylic acid copolymer constituting the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer according to the present embodiment is not particularly limited, and it can be produced by a known method. For example, it can obtain by radical copolymerizing each polymerization component under high temperature and high pressure. Moreover, the ionomer (A) of the ethylene/unsaturated carboxylic acid type copolymer which concerns on this embodiment can be obtained by making an ethylene/unsaturated carboxylic acid type copolymer and a metal compound react. In addition, as the ionomer (A) of the ethylene/unsaturated carboxylic acid-based copolymer, a commercially available one may be used.

In the present embodiment, the melt flow rate (MFR) of the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer measured at 190°C and under the conditions of a load of 2160 g in accordance with JIS K7210:1999 is 0.01 g They are preferably /10 min or more and 50 g/10 min or less, more preferably 0.1 g/10 min or more and 30 g/10 min or less, and particularly preferably 0.1 g/10 min or more and 10 g/10 min or less. When MFR is more than the said lower limit, the processability of the ionomer (A) of an ethylene-unsaturated carboxylic acid type copolymer can be made more favorable. When the MFR is equal to or less than the upper limit, the heat resistance, mechanical strength, and the like of the obtained laminated glass interlayer can be further improved.

The content of the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer in the resin composition (P) for an interlayer film for laminated glass according to the present embodiment is 100% by mass based on the total amount of the resin composition (P) for an interlayer film for laminated glass , Preferably 50 mass % or more and 99.999 mass % or less, More preferably 70 mass % or more and 99.995 mass % or less, More preferably 80 mass % or more and 99.99 mass % or less, Especially preferably 90 mass % or more and 99.95 mass % or less is below. When the content of the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer is within the above range, the optical properties of the obtained laminated glass, the interlayer adhesiveness, and the performance balance of water resistance can be further improved.

<Silane coupling agent having an amino group (B)>

As the silane coupling agent (B) having an amino group according to the present embodiment, for example, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-amino Propylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminomethyl) -3-Aminopropyltrimethoxysilane, N-(2-aminomethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminomethyl)-3-aminopropylmethyldiethoxysilane, N-(2 -Aminomethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butyli den)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxy Hydrochloride salt of silane, N-(2-aminomethyl)-8-aminooctyltrimethoxysilane, N-(2-aminoethyl)-8-aminooctyltrimethoxysilane, N-(2-aminomethyl)-8 -aminooctyltriethoxysilane, N-(2-aminoethyl)-8-aminooctyltriethoxysilane, etc. are mentioned.

In the resin composition (P) for an interlayer film for laminated glass according to the present embodiment, the content of the silane coupling agent (B) having an amino group is such that the performance balance of the optical properties, water resistance, and interlayer adhesion properties of the obtained laminated glass is better improved. From a viewpoint, when the total resin composition (P) for laminated glass interlayer film is 100 mass %, preferably 0.001 mass % or more and 5 mass % or less, more preferably 0.005 mass % or more and 2 mass % or less, further preferably 0.01 mass % or more and 1 mass % or less.

<Other ingredients>

In the resin composition (P) for laminated glass interlayer film according to the present embodiment, within the scope not impairing the object of the present invention, the ionomer (A) of the ethylene-unsaturated carboxylic acid-based copolymer and a silane coupling agent having an amino group (B) ) and other ingredients. Although it does not specifically limit as another component, For example, plasticizer, antioxidant, ultraviolet absorber, wavelength converter, antistatic agent, surfactant, colorant, light stabilizer, foaming agent, lubricant, crystal nucleating agent, crystallization accelerator, crystallization retarder, catalyst Deactivator, heat ray absorber, heat ray reflector, heat dissipator, thermoplastic resin other than the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer, thermosetting resin, inorganic filler, organic filler, impact resistance improving agent, slip agent, crosslinking agent, Crosslinking aid, tackifier, silane coupling agent other than the silane coupling agent having an amino group (B), processing aid, mold release agent, hydrolysis inhibitor, heat-resistant stabilizer, anti-blocking agent, antifogging agent, flame retardant, flame retardant aid, light diffusing agent, An antibacterial agent, an antifungal agent, a dispersing agent, other resin, etc. are mentioned. Other components may be used individually by 1 type, and may be used in combination of 2 or more type.

<Heize>

In the resin composition (P) for a laminated glass interlayer film according to the present embodiment, the haze measured by the following method is preferably less than 1.0%, more preferably 0.8% or less, and still more preferably 0.6% or less. Transparency of the laminated glass obtained as the said haze being below the said upper limit can be made more favorable.

In order to achieve such a haze, the molar ratio of the polyvalent metal ion to the monovalent metal ion in the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer, and the resin composition (P) for the laminated glass interlayer according to the present embodiment The content of the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer and the content of the silane coupling agent (B) having an amino group may be appropriately adjusted. Monovalent in the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer It becomes especially important to contain an appropriate amount of the silane coupling agent (B) which has an amino group, raising the ratio of a metal ion.

The lower limit of the haze of the resin composition (P) for laminated glass interlayer film according to the present embodiment is not particularly limited, but is, for example, 0.01% or more.

By using the resin composition (P) for a laminated glass interlayer film according to the present embodiment, the haze of the laminated glass according to the present embodiment can be made less than 1.0%. The preferred haze of the laminated glass is as described above.

(Way)

A film of 120 mm x 75 mm x 0.4 mm constituted by the resin composition (P) for laminated glass interlayer films according to the present embodiment is obtained. Next, the obtained said film|membrane is pinched|interposed between glass plates of 120 mm x 75 mm x 3.2 mm, 140 degreeC, vacuum holding for 5 minutes, and 0.1 MPa (gauge pressure) for 3 minutes are performed with a vacuum laminator, and laminated glass is obtained. Next, the haze of the obtained laminated glass is measured with a haze meter in accordance with JIS K7136.

<Length of cloudy part>

In the resin composition (P) for a laminated glass interlayer film according to the present embodiment, the length of the cloudy portion measured by the following method is preferably 5 mm or less, more preferably 2 mm or less, and particularly preferably 1 mm or less. The water resistance of the laminated glass obtained as the length of the said cloudiness part is below the said upper limit can be made more favorable.

In order to achieve the length of the cloudy portion, the molar ratio of the polyvalent metal ion to the monovalent metal ion in the ionomer (A) of the ethylene-unsaturated carboxylic acid copolymer, and the resin composition for a laminated glass interlayer according to the present embodiment (P) ), the content of the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer and the silane coupling agent (B) having an amino group in the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer may be appropriately adjusted. Increasing the proportion of polyvalent metal ions becomes particularly important.

The lower limit of the length of the cloudy portion of the resin composition for laminated glass interlayer (P) according to the present embodiment is preferably 0 mm.

By using the resin composition (P) for a laminated glass interlayer film according to the present embodiment, the length of the cloudy portion of the laminated glass according to the present embodiment can be 5 mm or less. Preferred values of the cloudy portion of the laminated glass are as described above.

(Way)

A film of 120 mm x 75 mm x 0.4 mm constituted by the resin composition (P) for laminated glass interlayer films according to the present embodiment is obtained. Next, the obtained said film|membrane is pinched|interposed between glass plates of 120 mm x 75 mm x 3.2 mm, 140 degreeC, vacuum holding for 5 minutes, and 0.1 MPa (gauge pressure) for 3 minutes are performed with a vacuum laminator, and laminated glass is obtained. Next, the obtained laminated glass is immersed in hot water at 90°C for 2 hours. Next, in the cloudy portion generated at the edge of the laminated glass, the length of the cloudy portion in a direction perpendicular to the cross section of the laminated glass is measured.

<Adhesive strength to glass plate>

In the resin composition (P) for a laminated glass interlayer film according to the present embodiment, the adhesive strength to the glass plate measured by the following method is preferably 10 N/15 mm or more, more preferably 15 N/15 mm or more, and 20 N/15 mm or more. It is particularly preferred. The interlayer adhesiveness of the laminated glass obtained as the adhesive strength with respect to the said glass plate is more than a lower limit can be made more favorable.

In order to achieve such adhesive strength to the glass plate, the ionomer (A) of the ethylene/unsaturated carboxylic acid-based copolymer in the resin composition for laminated glass interlayer (P) according to the present embodiment and a silane coupling agent having an amino group (B) What is necessary is just to adjust content etc. suitably.

(Way)

A film of 120 mm x 75 mm x 0.4 mm constituted by the resin composition (P) for laminated glass interlayer films according to the present embodiment is obtained. Next, the obtained film was laminated on the non-tin surface of a glass plate of 120 mm × 75 mm × 3.9 mm, and pressed with a vacuum laminator at 140° C. for 3 minutes, vacuum holding, and 0.1 MPa (gauge pressure) for 30 minutes, and the film was pressed on the non-casting surface of the glass plate. Adhesive to asbestos. Then, the film is peeled off from the glass plate at a tensile rate of 100 mm/min, and the maximum stress is calculated as the adhesive strength to the glass plate (N/15 mm).

Although the resin composition for laminated glass interlayer films was demonstrated above, the resin composition similar to the above can be used as a resin composition for solar cell sealing materials, and the same effect can be acquired.

2. Laminate glass interlayer

The laminated glass interlayer film 11 according to the present embodiment is made of the resin composition (P) for a laminated glass interlayer film according to the present embodiment.

The thickness of the laminated glass interlayer film 11 according to the present embodiment is, for example, 0.1 mm or more and 10 mm or less, preferably 0.2 mm or more and 5 mm or less, and more preferably 0.3 mm or more and 2 mm or less.

When the thickness of the glass interlayer film 11 is equal to or greater than the lower limit, the mechanical strength of the glass interlayer film 11 can be further improved. Moreover, when the thickness of the glass interlayer film 11 is below the said upper limit, the optical characteristic and interlayer adhesiveness of the obtained laminated glass can be made more favorable.

The manufacturing method of the laminated glass interlayer film 11 which concerns on this embodiment is not specifically limited, A conventionally well-known manufacturing method can be used.

As a method of manufacturing the laminated glass interlayer 11 according to the present embodiment, for example, a press molding method, an extrusion molding method, a T-die molding method, an injection molding method, a compression molding method, a cast molding method, a calender molding method, an inflation molding method, etc. can be used.

The solar cell encapsulant also preferably has the same thickness as the laminated glass interlayer, and can be manufactured by the same manufacturing method.

3. Laminated Glass

1 is a cross-sectional view schematically showing an example of the structure of a laminated glass 10 according to an embodiment of the present invention.

The laminated glass 10 according to the present embodiment includes the laminated glass interlayer film 11 according to the present embodiment and the transparent plate-like members 13 provided on both surfaces of the laminated glass interlayer film 11 . The laminated glass 10 according to the present embodiment is excellent in the performance balance of optical properties and water resistance by providing the laminated glass interlayer film 11 according to the present embodiment. Moreover, the interlayer adhesiveness between the glass interlayer film 11 and the transparent plate-shaped member 13 is also excellent.

Two or more laminated glass interlayer films 11 may be used, or three or more layers may be formed by sandwiching another resin layer between two laminated glass interlayer films 11 .

The transparent plate-like member 13 is not particularly limited, but, for example, generally used transparent plate glass can be used, for example, float plate glass, map plate glass, template glass, mesh plate glass, first-in plate glass, colored plate glass, Inorganic glass, such as a heat ray absorption plate glass, a heat ray reflection plate glass, and green glass, is mentioned. In addition, organic plastic plates such as polycarbonate plate, poly (meth) acrylate plate, polymethyl (meth) acrylate plate, polystyrene plate, cyclic polyolefin plate, polyethylene terephthalate plate, polyethylene naphthalate plate, polyethylene butylate plate, etc. You can also use

In addition, the transparent plate-like member 13 may be appropriately subjected to surface treatment such as corona treatment, plasma treatment, and frame treatment.

The thickness of the transparent plate-like member 13 is, for example, 1 mm or more and 20 mm or less. In the laminated glass 10 according to the present embodiment, the same transparent plate-shaped members 13 provided on both surfaces of the laminated glass interlayer film 11 may be used in combination, or different plate-shaped members may be used in combination.

The manufacturing method of the laminated glass 10 which concerns on this embodiment is not specifically limited, A conventionally well-known manufacturing method can be used.

As a method of manufacturing the laminated glass 10 according to the present embodiment, for example, as shown in FIG. 1 , the laminated glass interlayer film 11 according to the present embodiment is placed between two transparent plate-like members 13 . After clamping, the method of heating and pressurizing, etc. are used.

These laminated glass can be used for various purposes, for example, although it is used for laminated glass for construction, laminated glass for automobiles, general buildings, agricultural buildings, railway windows, etc., but is not limited to these uses.

4. Solar cell module

The solar cell module which concerns on this embodiment is equipped with the board|substrate which sunlight injects at least, a solar cell element, and the solar cell sealing material which concerns on this embodiment. The solar cell module according to the present embodiment may further include a protective material as needed. Also, a substrate on which sunlight is incident may be simply referred to as a substrate.

The solar cell module which concerns on this embodiment can be produced by fixing the solar cell element sealed with the solar cell sealing material which concerns on this embodiment on the said board|substrate.

As such a solar cell module, the thing of various types can be illustrated. For example, a substrate/encapsulant/solar cell element/encapsulant/protective material having a structure sandwiched between both sides of a solar cell element with an encapsulant; constituting a solar cell element previously formed on the surface of a substrate such as glass, like a substrate/solar cell element/encapsulant/protective material; a solar cell element formed on the inner circumferential surface of the substrate, for example, one in which a sealing material and a protective material are formed on an amorphous solar cell element produced by sputtering or the like on a fluororesin sheet; and the like.

In addition, since the said protective material is provided on the opposite side to the board|substrate side of a solar cell module, ie, the lower part, when the board|substrate on which sunlight is incident is made into the upper part of a solar cell module, it is called a lower protective material in some cases.

As a solar cell element, Silicon-type, such as monocrystalline silicon, polycrystalline silicon, amorphous silicon, III-V group, II-VI group, such as gallium-arsenic, copper-indium-selenium, copper-indium-gallium-selenium, cadmium-tellurium, etc. Various solar cell elements, such as a compound semiconductor type, can be used. The solar cell sealing material which concerns on this embodiment is especially useful for sealing of an amorphous silicon solar cell element, and the solar cell element of the heterojunction type of amorphous silicon and single crystal silicon.

Glass, acrylic resin, polycarbonate, polyester, fluorine-containing resin, etc. can be illustrated as a board|substrate which comprises the solar cell module which concerns on this embodiment.

As the protective material (lower protective material), a single or multi-layer sheet such as metal or various thermoplastic resin films, for example, metals such as tin, aluminum, stainless steel, inorganic materials such as glass, polyester, inorganic vapor deposition polyester, One-layer or multi-layered sheets such as fluorine-containing resin and polyolefin can be exemplified. The solar cell sealing material which concerns on this embodiment shows favorable adhesiveness with respect to these board|substrates or a protective material.

When the solar cell encapsulant according to the present embodiment is used and laminated and adhered together with the solar cell element, substrate, and protective material as described above, pressure and heating over a long period of time that has been achieved in the conventional ethylene/vinyl acetate copolymer system is used. Even if it does not implement a crosslinking process, the adhesive strength which can withstand actual use, and long-term stability of adhesive strength can be provided. However, from a viewpoint of providing stronger adhesive strength and adhesive strength stability, it is recommended to perform a pressurization heat process for a short time.

As mentioned above, although embodiment of this invention was described with reference to drawings, these are illustrations of this invention, and various structures other than the above can also be employ|adopted.

Example

Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to these examples.

(1) Evaluation method

[Optical Characteristics]

Films composed of the resin compositions for laminated glass interlayer films obtained in Examples and Comparative Examples were cut to a size of 120 mm x 75 mm x 0.4 mm. Next, the obtained film was sandwiched between a 120 mm x 75 mm x 3.2 mm glass plate (manufactured by Asahi Glass Inc., product name: float plate glass), and vacuum held at 140° C. for 5 minutes with a vacuum laminator, 0.1 MPa (gauge pressure) was pressed for 3 minutes to obtain laminated glass. In addition, the obtained laminated glass was cooled by slow cooling so that it might return to room temperature over about 30 minutes. Next, the haze of the obtained laminated glass was measured with a haze meter (manufactured by MURAKAMI COLOR RESEARCH LABORATORY CO., LTD., product name: haze meter HM150) in accordance with JIS K7136. Next, the optical properties of the resin compositions for laminated glass interlayer films obtained in Examples and Comparative Examples were evaluated according to the following criteria.

A (Excellent): Haze 0.6% or less

B (good): haze greater than 0.6% and less than 1.0%

C (defective): Haze of 1.0% or more

[Water resistance]

Films composed of the resin compositions for laminated glass interlayer films obtained in Examples and Comparative Examples were cut to a size of 120 mm x 75 mm x 0.4 mm. Next, the obtained film was sandwiched between a 120 mm x 75 mm x 3.2 mm glass plate (manufactured by Asahi Glass Co., Ltd., product name: float plate glass), vacuum held at 140 ° C. for 5 minutes with a vacuum laminator, and pressed at 0.1 MPa (gauge pressure) for 3 minutes. and laminated glass was obtained. Next, about the obtained laminated glass, it was immersed in 90 degreeC hot water for 2 hours. Next, in the cloudy portion generated at the edge of the laminated glass, the length of the cloudy portion in the vertical direction with respect to the cross section of the laminated glass was measured. Next, the water resistance of the resin compositions for laminated glass interlayer films obtained in Examples and Comparative Examples were evaluated according to the following criteria.

A (excellent): The length of the cloudy part is 1 mm or less

B (good): The length of the cloudy part exceeds 1 mm and less than 5 mm

C (defective): The length of the cloudy part exceeds 5 mm

[Interlayer Adhesion]

Films composed of the resin compositions for laminated glass interlayer films obtained in Examples and Comparative Examples were cut to a size of 120 mm x 75 mm x 0.4 mm. Next, the obtained film was laminated on the non-tin surface of a 120 mm x 75 mm x 3.9 mm glass plate (manufactured by Asahi Glass Co., Ltd., product name: blue plate glass), and vacuum held at 140 ° C. for 3 minutes with a vacuum laminator, 30 at 0.1 MPa (gauge pressure). Minute pressing was performed to adhere the film to the non-tin surface of the glass plate. Next, the film was peeled off from the glass plate at a tensile rate of 100 mm/min, and the maximum stress was calculated as the adhesive strength (N/15 mm) to the glass plate. Next, the interlayer adhesiveness in laminated glass of the resin compositions for laminated glass interlayer films obtained in Examples and Comparative Examples was evaluated according to the following criteria.

A (Excellent): Adhesive strength to the glass plate is 20N/15mm or more

B (good): The adhesive strength to the glass plate is 10N/15mm or more and less than 20N/15mm

C (poor): The adhesive strength to the glass plate is less than 10N/15mm

(2) material

The detail of the material used for preparation of laminated glass is as follows.

<Ionomer of ethylene/unsaturated carboxylic acid copolymer>

IO-1: ionomer of ethylene/methacrylic acid copolymer (ethylene content 81 mass%, methacrylic acid content: 19 mass%, metal ion: sodium ion, neutralization degree: 45%)

IO-2: ionomer of ethylene-methacrylic acid copolymer (ethylene content 81 mass%, methacrylic acid content: 19 mass%, metal ion: zinc ion, neutralization degree: 47%)

<Silane coupling agent>

Si-C1: Silane coupling agent having an amino group (N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.)

Si-C2: Silane coupling agent having an amino group (3-aminopropyltrimethoxysilane, KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.)

Si-C3: Silane coupling agent having an amino group (N-(2-aminomethyl)-8-aminooctyltrimethoxysilane, KBM-6803 manufactured by Shin-Etsu Chemical Co., Ltd.)

Si-C4: Silane coupling agent having a glycidyl group (3-glycidoxypropyltrimethoxysilane, KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.)

[Examples 1 to 7 and Comparative Examples 1 to 8]

At the mixing ratios shown in Tables 1 and 2, the ionomer of the ethylene/unsaturated carboxylic acid-based copolymer and the silane coupling agent were melt-kneaded at 160°C to obtain resin compositions for laminated glass interlayer films, respectively.

Next, the obtained resin composition for laminated glass interlayer film was extruded under the conditions of an extruder die outlet resin temperature of 160°C and a processing speed of 5 m/min to obtain a laminated glass interlayer film having a thickness of 0.4 mm, respectively.

The above evaluation was performed on the obtained laminated glass interlayer film, respectively. The obtained results are shown in Tables 1 and 2, respectively.

The laminated glass interlayer films of Examples 1 to 7 were excellent in the performance balance of optical properties, water resistance, interlayer adhesion, and appearance. On the other hand, the laminated glass interlayer films of Comparative Examples 1 to 8 were inferior in the performance balance of optical properties, water resistance, interlayer adhesion, and appearance.

In addition, the laminated glass interlayer film of Comparative Example 8 had protrusions on the surface, resulting in poor appearance. That is, the resin composition for laminated glass interlayer film of Comparative Example 8 was inferior in workability (film forming property). For this reason, various evaluations were not performed about the resin composition for laminated glass interlayer films of Comparative Example 8.

This application claims priority on the basis of Japanese Patent Application No. 2016-167808 for which it applied on August 30, 2016, and uses all the indications here.

Claims (19)

A resin composition for a laminated glass interlayer used for forming a laminated glass interlayer, the resin composition comprising:
It contains an ionomer (A) of an ethylene-unsaturated carboxylic acid-based copolymer and a silane coupling agent (B) having an amino group,
The metal ions constituting the ionomer (A) of the ethylene/unsaturated carboxylic acid-based copolymer include monovalent metal ions and polyvalent metal ions,
The molar ratio of the polyvalent metal ion to the monovalent metal ion in the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer is 0.1 or more and 0.35 or less,
The content of the silane coupling agent having an amino group (B) is not less than 0.001% by mass and not more than 5% by mass, when the total of the resin composition for laminated glass interlayer film is 100% by mass;
In the resin composition for laminated glass interlayer film, the haze measured by the following method is less than 1.0%,
(Way)
A film of 120 mm x 75 mm x 0.4 mm constituted by the resin composition for laminated glass interlayer is obtained. Next, the obtained said film|membrane is pinched|interposed between glass plates of 120 mm x 75 mm x 3.2 mm, 140 degreeC, vacuum holding for 5 minutes, and 0.1 MPa (gauge pressure) for 3 minutes are performed with a vacuum laminator, and laminated glass is obtained. Next, the haze of the obtained laminated glass is measured with a haze meter in accordance with JIS K7136.
In the resin composition for laminated glass interlayer, the length of the cloudy portion measured by the following method is 5 mm or less.
(Way)
A film of 120 mm x 75 mm x 0.4 mm constituted by the resin composition for laminated glass interlayer is obtained. Next, the obtained said film|membrane is pinched|interposed between glass plates of 120 mm x 75 mm x 3.2 mm, 140 degreeC, vacuum holding for 5 minutes, and 0.1 MPa (gauge pressure) for 3 minutes are performed with a vacuum laminator, and laminated glass is obtained. Next, the obtained laminated glass is immersed in hot water at 90°C for 2 hours. Next, in the cloudy portion generated at the edge of the laminated glass, the length of the cloudy portion in a direction perpendicular to the cross section of the laminated glass is measured. The method of claim 1,
The resin composition for a laminated glass interlayer, wherein the monovalent metal ion includes one or more selected from lithium ions, potassium ions, sodium ions, silver ions, mercury ions, and copper ions. 3. The method of claim 1 or 2,
The polyvalent metal ion is selected from calcium ion, magnesium ion, zinc ion, aluminum ion, barium ion, beryllium ion, strontium ion, copper ion, cadmium ion, mercury ion, tin ion, lead ion, iron ion, cobalt ion and nickel ion. A resin composition for a laminated glass interlayer comprising one or more selected types. 3. The method of claim 1 or 2,
The resin composition for a laminated glass interlayer film, wherein the degree of neutralization of the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer is 5% or more and 95% or less. 3. The method of claim 1 or 2,
A resin composition for a laminated glass interlayer film having an adhesive strength to a glass plate of 10 N/15 mm or more as measured by the following method.
(Way)
A film of 120 mm x 75 mm x 0.4 mm constituted by the resin composition for laminated glass interlayer is obtained. Next, the obtained film was laminated on the non-tin surface of a glass plate of 120 mm × 75 mm × 3.9 mm, and pressed with a vacuum laminator at 140° C. for 3 minutes, vacuum holding, and 0.1 MPa (gauge pressure) for 30 minutes, and the film was pressed on the non-casting surface of the glass plate. Adhesive to asbestos. Then, the film is peeled off from the glass plate at a tensile rate of 100 mm/min, and the maximum stress is calculated as the adhesive strength to the glass plate (N/15 mm). 3. The method of claim 1 or 2,
The ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer is the monovalent metal ion ionomer (A1) of the ethylene/unsaturated carboxylic acid copolymer, and the polyvalent metal ion of the ethylene/unsaturated carboxylic acid copolymer A resin composition for a laminated glass interlayer comprising an ionomer (A2). 3. The method of claim 1 or 2,
A resin composition for a laminated glass interlayer film, wherein the unsaturated carboxylic acid constituting the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer includes at least one selected from acrylic acid and methacrylic acid. 3. The method according to claim 1 or 2,
In the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer, when the total amount of the structural units constituting the ethylene/unsaturated carboxylic acid copolymer is 100% by mass, a structural unit derived from an unsaturated carboxylic acid A resin composition for a laminated glass interlayer film having a value of 5% by mass or more and 35% by mass or less. A laminated glass interlayer film comprising the resin composition for laminated glass interlayer film according to claim 1 or 2. The laminated glass interlayer film according to claim 9;
A laminated glass comprising transparent plate-like members provided on both surfaces of the laminated glass interlayer. 11. The method of claim 10,
Laminated glass having a haze of less than 1.0% as measured by a haze meter in accordance with JIS K7136. 11. The method of claim 10,
The laminated glass whose length of the cloudy part measured by the following method is 5 mm or less.
(Way)
The laminated glass is immersed in hot water at 90° C. for 2 hours. Next, in the cloudy portion generated at the edge of the laminated glass, the length of the cloudy portion in a direction perpendicular to the cross section of the laminated glass is measured. As a resin composition for a solar cell encapsulant used to form a solar cell encapsulant,
It contains an ionomer (A) of an ethylene-unsaturated carboxylic acid-based copolymer and a silane coupling agent (B) having an amino group,
The metal ions constituting the ionomer (A) of the ethylene/unsaturated carboxylic acid-based copolymer include monovalent metal ions and polyvalent metal ions,
The molar ratio of the polyvalent metal ion to the monovalent metal ion in the ionomer (A) of the ethylene/unsaturated carboxylic acid copolymer is 0.1 or more and 0.35 or less,
When content of the silane coupling agent (B) which has the said amino group makes the whole of the said resin composition for solar cell sealing materials 100 mass %, it is 0.001 mass % or more and 5 mass % or less,
In the resin composition for the solar cell encapsulant, the haze measured by the following method is less than 1.0%,
(Way)
A film of 120 mm x 75 mm x 0.4 mm constituted by the resin composition for solar cell encapsulants is obtained. Next, the obtained said film|membrane is pinched|interposed between glass plates of 120 mm x 75 mm x 3.2 mm, 140 degreeC, vacuum holding for 5 minutes, and 0.1 MPa (gauge pressure) for 3 minutes are performed with a vacuum laminator, and laminated glass is obtained. Next, the haze of the obtained laminated glass is measured with a haze meter in accordance with JIS K7136.
In the resin composition for a solar cell encapsulant, the length of the cloudy portion measured by the following method is 5 mm or less, the resin composition for a solar cell encapsulant.
(Way)
A film of 120 mm x 75 mm x 0.4 mm constituted by the resin composition for solar cell encapsulants is obtained. Next, the obtained said film|membrane is pinched|interposed between glass plates of 120 mm x 75 mm x 3.2 mm, 140 degreeC, vacuum holding for 5 minutes, and 0.1 MPa (gauge pressure) for 3 minutes are performed with a vacuum laminator, and laminated glass is obtained. Next, the obtained laminated glass is immersed in hot water at 90°C for 2 hours. Next, in the cloudy portion generated at the edge of the laminated glass, the length of the cloudy portion in a direction perpendicular to the cross section of the laminated glass is measured. A solar cell encapsulant comprised of the resin composition for solar cell encapsulants of Claim 13. A solar cell module comprising the solar cell encapsulant according to claim 14 in a configuration.

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