WO2022270545A1

WO2022270545A1 - Ionomer resin composition, resin sheet, and laminated glass

Info

Publication number: WO2022270545A1
Application number: PCT/JP2022/024906
Authority: WO
Inventors: 卓郎新村; 憲太竹本; 芳聡淺沼; 淳裕中原
Original assignee: 株式会社クラレ
Priority date: 2021-06-23
Filing date: 2022-06-22
Publication date: 2022-12-29
Also published as: JPWO2022270545A1

Abstract

The present invention relates to an ionomer resin composition comprising an ionomer resin and a silane coupling agent, wherein: the ionomer resin includes a (meth)acrylic acid unit (A), a (meth)acrylic acid neutralized unit (B), and an ethylene unit (C); the total content of the unit (A) and the unit (B) is 6-10 mol% with respect to the total monomer units constituting the ionomer resin; the content of a salt formed by a strong acid and a strong base in the ionomer resin composition is 1-400 mg/kg; and the content of the silane coupling agent is 0.005-0.5 parts by mass with respect to 100 parts by mass of the ionomer resin.

Description

Ionomer resin composition, resin sheet and laminated glass

This patent application claims priority under the Paris Convention of Japanese Patent Application No. 2021-104273 (filing date: June 23, 2021), which is hereby incorporated by reference in its entirety. shall be incorporated within.
The present invention relates to an ionomer resin composition, a resin sheet comprising one or more layers containing the ionomer resin composition, a laminated glass intermediate film comprising the resin sheet, and a laminated glass having the laminated glass intermediate film.

　Ionomers, which are neutralized ethylene/unsaturated carboxylic acid copolymers, are used in interlayer films for laminated glass because of their excellent transparency and adhesion to glass (for example, Patent Document 1). In recent years, the performance required for laminated glass has increased, and ionomer resins must maintain high transparency regardless of the manufacturing conditions of laminated glass, maintain high elastic modulus even at high temperatures, and reduce the strength of laminated glass. There is a growing demand for a film that does not discolor, has an excellent appearance with little coloration, and has excellent adhesiveness to glass and is less likely to separate from glass.

Patent Document 2 discloses copolymerization units of ethylene, copolymerization units of a first α,β-unsaturated carboxylic acid having 3 to 10 carbon atoms, and a second α having 3 to 10 carbon atoms. , and copolymerized units of derivatives of β-unsaturated carboxylic acids.

Patent Document 3 describes a resin composition containing a homogeneous mixture of an ionomer resin and a dialkoxysilane compound as an adhesion promoter.

U.S. Pat. No. 6,432,522 Japanese Patent Publication No. 2017-519083 Japanese Patent Publication No. 2020-529500

Patent Document 2 describes that the ionomer described in the same document exhibits improved optical properties (haze) compared to conventional ionomers. However, according to the studies of the present inventors, it has been found that ionomers such as those described in Patent Document 2 are likely to be thermally decomposed during molding, and that the resulting intermediate film is likely to have defects such as black foreign matter. rice field.

In addition, when laminated glass is used outdoors, moisture such as rain may cause separation between the glass and the laminated glass interlayer, or whitening and loss of transparency, especially at the edges of the laminated glass. There is Therefore, there is a demand for an ionomer resin capable of forming a laminated glass interlayer film having high transparency and adhesion to glass even in a wet state.

Patent Document 3 describes that the resin composition described therein has improved adhesion to glass in a wet state. However, according to the studies of the present inventors, the resin composition described in Patent Document 3 may have defects such as black foreign matter in the interlayer film that is easily thermally decomposed during molding. In addition, it was found that a crosslinked gel may be generated due to a crosslinking reaction with the dialkoxysilane compound during molding, and further improvement is necessary to obtain an intermediate film with good appearance.

Accordingly, an object of the present invention is to provide an ionomer resin composition that is excellent in transparency, thermal decomposition resistance, and adhesion to substrates such as glass in a wet state.

The present inventors arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention provides the following preferred aspects.

[1] An ionomer resin composition containing an ionomer resin and a silane coupling agent,
The ionomer resin contains (meth)acrylic acid units (A), (meth)acrylic acid neutralized units (B) and ethylene units (C), and the total content of the units (A) and the units (B) The amount is 6 to 10 mol% based on the total monomer units constituting the ionomer resin, and the content of the salt composed of a strong acid and a strong base in the ionomer resin is 1 to 400 mg/kg,
The ionomer resin composition, wherein the content of the silane coupling agent is 0.005 to 0.5 parts by mass with respect to 100 parts by mass of the ionomer resin.
[2] The ionomer resin further includes (meth)acrylic acid ester units (D), and the total content of the units (A), the units (B) and the units (D) constitutes the ionomer resin. The ionomer resin composition according to [1], which is 6 to 10 mol% based on the total monomer units.
[3] The ionomer resin composition according to [1] or [2], wherein the salt composed of a strong acid and a strong base is a metal salt of alkali metal and/or alkaline earth metal.
[4] The salt composed of a strong acid and a strong base includes at least one cation selected from the group consisting of sodium ions and potassium ions and at least one selected from the group consisting of halogen ions, nitrate ions and sulfate ions. The ionomer resin composition according to any one of [1] to [3], which is a salt consisting of the anion of
[5] The silane coupling agent is at least one silane coupling agent selected from the group consisting of amino-based compounds, glycidoxy-based compounds, sulfide-based compounds, mercapto-based compounds, vinyl-based compounds, nitro-based compounds and chloro-based compounds. The ionomer resin composition according to any one of [1] to [4], which is an agent.
[6] The silane coupling agent is at least one silane coupling agent selected from the group consisting of N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane and 3-glycidoxypropylmethyldiethoxysilane. The ionomer resin composition according to any one of [1] to [5], which is an agent.
[7] A resin sheet comprising one or more layers containing the ionomer resin composition according to any one of [1] to [6].
[8] A laminated glass intermediate film comprising the resin sheet according to [7].
[9] A laminated glass comprising two glass plates and the laminated glass interlayer of [8] disposed between the two glass plates.

According to the present invention, it is possible to provide an ionomer resin composition that is excellent in transparency, thermal decomposition resistance, and adhesion to substrates such as glass in a wet state.

[Ionomer resin composition]
The ionomer resin composition of the present invention comprises an ionomer resin containing 1 to 400 mg/kg of a salt composed of a strong acid and a strong base, and 0.005 to 0.5 parts by mass of silane coupling with respect to 100 parts by mass of the ionomer resin. agent, wherein the ionomer resin comprises (meth)acrylic acid units (A), (meth)acrylic acid neutralized units (B) and ethylene units (C), wherein the units (A) and the units (B ) is 6 to 10 mol % based on the total monomer units constituting the ionomer resin.
The inventors of the present invention have investigated an ionomer resin composition, and found that an ionomer resin containing a specific unit in a specific amount and containing 1 to 400 mg / kg of a salt composed of a strong acid and a strong base, and 100 mass of the ionomer resin When combined with 0.005 to 0.5 parts by weight of a silane coupling agent per part, surprisingly, an ionomer having excellent transparency, thermal decomposition resistance, and adhesion to substrates such as glass in a wet state It has been found that a resin composition can be obtained.

In the present specification, the term "unit" means a "derived structural unit", for example, a (meth)acrylic acid unit refers to a structural unit derived from (meth)acrylic acid, (meth)acrylic acid The acid-neutralized unit indicates a structural unit derived from a (meth)acrylic acid-neutralized product, and the ethylene unit indicates a structural unit derived from ethylene. Moreover, in this specification, "(meth)acrylic acid" indicates methacrylic acid or acrylic acid.

[Ionomer resin]
The ionomer resin of the present invention comprises (meth)acrylic acid units (A), (meth)acrylic acid neutralized units (B), and ethylene units (C), wherein the units (A) and the units (B) is 6 to 10 mol % based on the total monomer units constituting the ionomer resin. When the total content is within the above range, it is possible to improve transparency and adhesiveness to a substrate such as glass.

If the total content exceeds the above upper limit, it is difficult to suppress an increase in melt viscosity during molding of the ionomer resin composition, and as a result, moldability of the ionomer resin composition tends to decrease. Furthermore, when the total content is less than the above lower limit, the transparency of the ionomer resin composition, particularly the transparency when the crystallization of the ionomer resin composition is promoted by slow cooling (hereinafter referred to as the transparency during slow cooling (also called transparency) tends to decrease. The total content is 6 mol% or more, preferably 6.5 mol%, from the viewpoint of easily improving the transparency of the ionomer resin composition (especially the transparency during slow cooling) and the adhesion to substrates such as glass. Above, more preferably 7.0 mol% or more, more preferably 7.5 mol% or more, and from the viewpoint of easily improving moldability, 10 mol% or less, preferably 9.9 mol% or less, More preferably, it is 9.5 mol % or less.

The total content of the units (A) and the units (B) can be adjusted according to the method for producing the ionomer resin. More specifically, when an ionomer resin is produced from an ethylene-(meth)acrylic acid ester copolymer as a raw material by a method including a saponification reaction step of the copolymer, ethylene-(meth)acrylic acid ester Each reaction for converting the (meth)acrylic acid ester unit in the copolymer into the (meth)acrylic acid unit (A) and the (meth)acrylic acid neutralized product unit (B) by the saponification reaction and the demetallization reaction can be adjusted by the reactivity (conversion ratio) of

<(Meth) acrylic acid unit (A)>
Examples of monomers constituting the (meth)acrylic acid unit (A) include acrylic acid and methacrylic acid, and methacrylic acid is preferred from the viewpoint of heat resistance and adhesion to substrates. These (meth)acrylic acid units may be used alone or in combination of two.

The content of the (meth)acrylic acid unit (A) in the ionomer resin is such that the total content of the unit (A) and the unit (B) is 6 to 6 based on the total monomer units constituting the ionomer resin. There is no particular limitation as long as it is within the range of 10 mol %. In one embodiment of the present invention, the content of (meth)acrylic acid units (A) in the ionomer resin is preferably 4.5 mol% or more, based on the total monomer units constituting the ionomer resin, and more Preferably 5.0 mol% or more, more preferably 5.5 mol% or more, particularly preferably 5.8 mol% or more, and preferably 9.0 mol% or less, more preferably 8.5 mol% Below, more preferably 8.0 mol % or less, particularly preferably 7.5 mol % or less. When the content of the unit (A) is at least the above lower limit, the transparency of the ionomer resin composition and the adhesion to a substrate are likely to be improved. Further, when the content is equal to or less than the above upper limit, it is easy to improve moldability.

<(Meth)acrylic acid neutralized unit (B)>
The neutralized (meth)acrylic acid unit (B) is preferably the neutralized (meth)acrylic acid unit (A). The neutralized (meth)acrylic acid is obtained by replacing hydrogen ions of (meth)acrylic acid with metal ions. Examples of the metal ions include monovalent metal ions such as lithium, sodium and potassium, and polyvalent metal ions such as magnesium, calcium, zinc, aluminum and titanium. Such metal ions may be used singly or in combination of two or more. For example, it may be a combination of one or more monovalent metal ions and one or more divalent metal ions.

The content of the (meth)acrylic acid neutralized unit (B) in the ionomer resin is such that the total content of the unit (A) and the unit (B) is the total monomer units constituting the ionomer resin. As a standard, it is not particularly limited as long as it is within the range of 6 to 10 mol %. In one embodiment of the present invention, the content of (meth)acrylic acid neutralized units (B) is preferably 0.65 mol % or more, more preferably 0.65 mol % or more, based on the total monomer units constituting the ionomer resin. is 1.0 mol% or more, more preferably 1.3 mol% or more, even more preferably 1.5 mol% or more, particularly preferably 1.6 mol% or more, and preferably 3.0 mol% Below, it is more preferably 2.7 mol % or less, still more preferably 2.6 mol % or less, and particularly preferably 2.5 mol % or less. When the content of the unit (B) is at least the above lower limit, the transparency and elastic modulus are likely to be improved, and when it is at most the above upper limit, it is easy to suppress an increase in melt viscosity during molding.

Each content of the unit (A) and the unit (B) is obtained by using an ethylene-(meth)acrylic acid ester copolymer as a raw material, and ionomer by a method including a saponification reaction step and a demetallization reaction step of the copolymer. When producing a resin, the (meth)acrylic acid ester units in the ethylene-(meth)acrylic acid ester copolymer are converted into (meth)acrylic acid units (A) and (meth)acrylic acid units (A) and (meth) It can be adjusted by the reactivity in each reaction for converting to the neutralized acrylic acid unit (B).

<Ethylene unit (C)>
The content of the ethylene unit (C) is preferably 80 mol% or more, more preferably 85 mol, based on the total monomer units constituting the ionomer resin, from the viewpoint of easily increasing the impact resistance of the ionomer resin composition. % or more, more preferably 88 mol % or more, and preferably 94 mol % or less, more preferably 91 mol %, from the viewpoint of easily increasing the transparency of the ionomer resin composition (especially the transparency during slow cooling). It is below. When the content of ethylene units (C) is at least the above lower limit, the mechanical strength and molding processability are likely to be improved, and when it is at most the above upper limit, transparency is likely to be improved.

<(Meth) acrylic acid ester unit (D)>
In one embodiment of the present invention, the ionomer resin has (meth)acrylic acid units (A), (meth)acrylic acid neutralized units (B), and ethylene units (C) to obtain higher transparency. From the viewpoint of ease of use, it is preferable that the (meth)acrylic acid ester unit (D) is further included.

When the ionomer resin contains the (meth)acrylic acid ester unit (D), the total content of the unit (A), the unit (B) and the unit (D) is ), it is preferably 6 to 10 mol % based on the total monomer units constituting the ionomer resin. That is, in one preferred embodiment of the present invention, the ionomer resin comprises (meth)acrylic acid units (A), (meth)acrylic acid neutralized units (B), ethylene units (C), and (meth)acrylic Including the acid ester unit (D), the total content of the unit (A), the unit (B) and the unit (D) is 6 to 10 mol based on the total monomer units constituting the ionomer resin %. When the ionomer resin contains (meth)acrylic acid ester units (D), the total content of the units (A), the units (B) and the units (D) is the above upper limit or less, the ionomer resin composition It is easy to suppress the increase in the melt viscosity during the molding process of the product, thereby easily improving the moldability of the ionomer resin composition. Further, when the total content is at least the lower limit value, the transparency of the ionomer resin composition, especially during slow cooling, tends to be enhanced.
When the ionomer resin contains (meth)acrylic acid ester units (D), the total content of the units (A), the units (B) and the units (D) is From the viewpoint of easily improving transparency) and adhesion to a substrate, the content is 6 mol% or more, preferably 6.5 mol% or more, more preferably 7.0 mol% or more, and still more preferably 7.5 mol% or more. Also, from the viewpoint of moldability, it is 10 mol % or less, preferably 9.9 mol % or less, more preferably 9.5 mol % or less.

The total content of the units (A), the units (B) and the units (D) can be adjusted depending on the raw material of the ionomer resin. More specifically, when an ethylene-(meth)acrylic acid ester copolymer is used as a raw material and an ionomer resin is produced by a method including a saponification reaction step of the copolymer, ethylene- It can be adjusted by the (meth)acrylic acid ester modification amount of the (meth)acrylic acid ester copolymer. Further, as described in US Pat. No. 8,399,096, when ethylene and (meth)acrylic acid are used as raw materials and these are polymerized to produce an ionomer resin, ethylene and (meth)acrylic acid to be copolymerized It can be adjusted by the ratio.

Examples of monomers constituting the (meth)acrylate unit (D) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. , n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, ( n-hexyl meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, pentadecyl (meth)acrylate, dodecyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylic acid Phenyl, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, glycidyl (meth)acrylate, allyl (meth)acrylate etc.
Among these, preferred monomers from the viewpoint of transparency or heat resistance are methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ( meth) n-butyl acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, and more preferred monomers are methyl (meth) acrylate, ( Ethyl meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate, and more preferred monomers are (meth) Methyl acrylate, n-butyl (meth)acrylate and isobutyl (meth)acrylate, and a particularly preferred monomer is methyl (meth)acrylate. These (meth)acrylic acid esters may be used singly or in combination of two or more.

When the ionomer resin contains (meth)acrylic acid ester units (D), the content of the (meth)acrylic acid ester units (D) in the ionomer resin is not particularly limited. In one embodiment of the present invention, the content of (meth)acrylic acid ester units (D) in the ionomer resin is preferably greater than 0 mol %, more preferably more than 0 mol %, based on the total monomer units constituting the ionomer resin. is 0.01 mol% or more, more preferably 0.05 mol% or more, particularly preferably 0.08 mol% or more, and preferably 1.0 mol% or less, more preferably 0.7 mol% or less , more preferably 0.5 mol % or less. When the content of the unit (D) is at least the above lower limit and at most the above upper limit, the transparency of the ionomer resin composition is likely to be improved.

When the ionomer resin contains the (meth)acrylic acid ester unit (D), the content of the unit (D) is obtained by using an ethylene-(meth)acrylic acid ester copolymer as a raw material and saponifying the copolymer. and when producing an ionomer resin by a method including a demetallization reaction step, the (meth)acrylic acid ester unit (D) in the ethylene-(meth)acrylic acid ester copolymer is replaced with the (meth)acrylic acid unit (A) can be adjusted by the reactivity of the saponification reaction that converts to

<Other monomer units>
The ionomer resin of the present invention comprises (meth)acrylic acid units (A), (meth)acrylic acid neutralized units (B), and ethylene units (C), and optionally included (meth)acrylic acid ester units ( It may contain monomeric units other than D). Examples of other monomer units include a carboxylic acid unit (A1) other than the (meth)acrylic acid unit (A), and a neutralized carboxylic acid unit other than the (meth)acrylic acid neutralized unit (B) ( B1) and the like.
Examples of the monomer constituting the carboxylic acid unit (A1) include itaconic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, etc. Monomethyl maleate and monoethyl maleate are preferred. Examples of the monomer constituting the neutralized carboxylic acid unit (B1) include neutralized units of the neutralized carboxylic acid unit (A1). The neutralized carboxylic acid is obtained by replacing hydrogen ions of carboxylic acid with metal ions. Examples of the metal ions include those similar to the metal ions in the neutralized (meth)acrylic acid unit (B) described above, and the metal ions may be used singly or in combination of two or more.
These other monomer units may be used singly or in combination of two or more.

When the ionomer resin contains the above-mentioned other monomer units, the total content thereof, for example, the total content of (A1) and (B1), may be appropriately selected within a range that does not impair the effects of the present invention. Based on the total monomer units constituting the ionomer resin, preferably 5 mol% or less, more preferably 3 mol% or less, still more preferably 1 mol% or less, and preferably 0.01 mol% or more, More preferably, it is 0.1 mol % or more.

(meth)acrylic acid units (A), (meth)acrylic acid neutralized units (B), and ethylene units (C) in the ionomer resin, and (meth)acrylic acid ester units (D) when included, and other monomeric units (e.g., unit (A1) and unit (B1)) are determined by first identifying the monomeric units in the ionomer resin by pyrolysis gas chromatography, and then by nuclear magnetic resonance It can be determined by using spectroscopy (NMR) and elemental analysis. More specifically, it can be determined by the method described in Examples. It can also be determined by a method combining the above analysis method with IR and/or Raman analysis. Prior to these analyses, it is preferable to remove components other than the ionomer resin by a reprecipitation method or a Soxhlet extraction method.

<Salts Consisting of Strong Acids and Strong Bases>
The ionomer resin contains 1 to 400 mg/kg of a salt composed of a strong acid and a strong base (hereinafter also simply referred to as "salt"). The present inventors have found that when the ionomer resin contains 1 to 400 mg/kg of salt, the ionomer resin composition can maintain high transparency (especially transparency when absorbing water) and can improve thermal decomposition resistance. . Therefore, the ionomer resin composition of the present invention can achieve both high transparency and high thermal decomposition resistance. Although it is not clear why the ionomer resin composition of the present invention has excellent thermal decomposition resistance by containing a salt within the above range, the interaction between the salt and the (meth)acrylic acid unit (A) in the ionomer resin , the (meth)acrylic acid unit (A) in the ionomer resin can be suppressed from desorbing due to heat.

Furthermore, the inventors of the present invention have generally found that when an ionomer resin and a silane coupling agent are combined, black foreign matter and crosslinked gel are likely to be generated during molding, and it tends to be difficult to obtain a resin sheet with a good appearance. Surprisingly, it was also found that a resin sheet with a good appearance can be easily obtained when the salt content is 1 to 400 mg/kg. Although the reason for this is not clear, it is believed that the inclusion of the salt improves the thermal decomposition resistance of the ionomer resin composition.

If the content of the salt exceeds the above upper limit, the transparency of the ionomer resin composition tends to be reduced. The ionomer resin composition tends to thermally decompose. The content of the salt is 1 mg/kg or more, preferably 3 mg/kg or more, more preferably 5 mg/kg or more, from the viewpoint of easily improving the thermal decomposition resistance and the viewpoint of easily improving the appearance of the resulting resin sheet. . In addition, from the viewpoint of easily improving the transparency (especially the transparency at the time of water absorption) and the viewpoint of easily improving the appearance of the resulting resin sheet, the amount is 400 mg/kg or less, preferably 380 mg/kg or less, more preferably 350 mg/kg or less. , more preferably 320 mg/kg or less, still more preferably 300 mg/kg or less, and particularly preferably 200 mg/kg or less. The content of the salt in the ionomer resin can be appropriately selected according to the method of incorporating the salt into the ionomer resin as described later. The salt content in the ionomer resin can be measured using an ion chromatograph, for example, by the method described in Examples.

The salt consisting of a strong acid and a strong base is not particularly limited, and examples thereof include metal salts of alkali metals and/or alkaline earth metals consisting of a strong acid and a strong base. These salts may be used singly or in combination of two or more. Examples of alkali metal salts include lithium salts, sodium salts, potassium salts, rubidium salts, cesium salts and the like. Preferred alkali metal salts are lithium salts, sodium salts and potassium salts, more preferably sodium salts and potassium salts, from the viewpoints of easily increasing the thermal decomposition resistance of the ionomer resin composition and from the viewpoints of easily obtaining a resin sheet with a good appearance. , more preferably the sodium salt. Examples of alkaline earth metal salts include beryllium salts, magnesium salts, calcium salts, strontium salts, barium salts and the like. Preferred alkaline earth metal salts are magnesium salts and calcium salts from the viewpoint of easily increasing the thermal decomposition resistance of the ionomer resin composition.

A more preferable salt is at least one salt selected from the group consisting of sodium ions, potassium ions, magnesium ions and calcium ions, from the viewpoints of easily increasing the thermal decomposition resistance of the ionomer resin composition and from the viewpoint of easily obtaining a resin sheet with a good appearance. A salt consisting of a cation of a species and at least one anion selected from the group consisting of halogen ions, sulfate ions, nitrate ions and sulfonate ions, more preferably selected from the group consisting of sodium ions and potassium ions. and at least one anion selected from the group consisting of halogen ions, sulfate ions and nitrate ions.

Examples of specific preferred salts include sodium chloride, potassium chloride, magnesium chloride, calcium chloride, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, sodium nitrate, potassium nitrate, magnesium nitrate, calcium nitrate, p-toluenesulfonic acid. sodium, potassium p-toluenesulfonate, magnesium p-toluenesulfonate, and calcium p-toluenesulfonate. More preferable salts are sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, sodium nitrate, potassium nitrate, and more preferably chloride, from the viewpoint of easily improving transparency and thermal decomposition resistance and from the viewpoint of easily obtaining a resin sheet with good appearance. Sodium, sodium sulfate, sodium nitrate.

The method of adding a salt to the ionomer resin is not particularly limited, and includes, for example, (I) a method of generating and adding a salt in the ionomer resin manufacturing process, (II) a method of separately adding a salt in the ionomer resin manufacturing process, and (III) a method of producing a salt-free ionomer resin and post-adding a salt to the resin. Among these methods, from the viewpoint of facilitating uniform dispersion of the salt in the ionomer resin, thereby facilitating improvement in transparency and thermal decomposition resistance, the method of forming and containing the salt during the manufacturing process of the ionomer resin ( I) is preferred.

The method for adjusting the content of the salt composed of the strong acid and the strong base in the ionomer resin can be appropriately selected according to the method of containing the salt. For example, when a salt is added by the above method (I), it can be adjusted by the washing degree of the obtained resin. More specifically, the salt content in the ionomer resin can be adjusted by the number of washings in the step of washing the obtained resin with a washing liquid. Examples of the cleaning liquid include solvents that are good solvents for salts and poor solvents for resins, such as water, alcohols such as methanol, ketones such as acetone, and mixed solvents thereof. When a salt is added by the methods (II) and (III), the salt content in the ionomer resin can be adjusted by adjusting the amount of separately added salt and the amount of post-added salt.

The dispersion state of the salt composed of a strong acid and a strong base in the ionomer resin is not particularly limited. Distributed is preferred.

In one embodiment of the present invention, the degree of branching per 1000 carbon atoms of the ionomer resin is not particularly limited, preferably 5-30, more preferably 6-20. The degree of branching is adjusted by the temperature at which the ionomer resin is polymerized, for example, the polymerization temperature at which ethylene-(meth)acrylic acid ester (X) is synthesized when the ionomer resin is synthesized by the EMMA saponification method. can. The degree of branching per 1000 carbons can be measured by the DDMAS method using solid-state NMR.

In one embodiment of the present invention, the melting point of the ionomer resin is preferably 50° C. or higher, more preferably 60° C. or higher, and still more preferably 80° C. or higher, from the viewpoint of heat resistance and thermal decomposition resistance. is preferably 200° C. or lower, more preferably 180° C. or lower, and even more preferably 150° C. or lower, from the viewpoint that the adhesive strength with glass is likely to be exhibited when the is produced. The melting point can be measured based on JIS K7121:2012. Specifically, using a differential scanning calorimeter (DSC), measurement was performed under the conditions of a cooling rate of −10° C./min and a heating rate of 10° C./min, and from the pick-top temperature of the melting peak of the second heating can ask.

In one embodiment of the present invention, the heat of fusion of the ionomer resin is preferably 0 J/g or more and 25 J/g or less. The heat of fusion can be measured based on JIS K7122:2012. Specifically, using a differential scanning calorimeter (DSC), measurement was performed under the conditions of a cooling rate of −10° C./min and a heating rate of 10° C./min, and the area of the melting peak during the second heating was calculated. can do.

In one embodiment of the present invention, the melt flow rate (MFR) of the ionomer resin measured under the conditions of 190° C. and 2.16 kg according to JIS K7210-1:2014 is preferably 0.1 g/10 minutes or more. , more preferably 0.3 g/10 min or more, still more preferably 0.7 g/10 min or more, still more preferably 1.0 g/10 min or more, particularly preferably 1.5 g/10 min or more, preferably It is 50 g/10 minutes or less, more preferably 30 g/10 minutes or less, and particularly preferably 10 g/10 minutes or less. When the MFR is equal to or more than the lower limit and equal to or less than the upper limit, it is easy to perform molding while suppressing deterioration due to heat, and it is easy to obtain a resin sheet having excellent penetration resistance.

The melting point, heat of fusion and MFR of an ionomer resin are determined by the molecular weight of the ionomer resin and the ionomer resin's (meth)acrylic acid unit (A), neutralized (meth)acrylic acid unit (B), and ethylene unit (C), It can also be adjusted by the content of (meth)acrylic acid ester units (D) optionally included.

<Method for producing ionomer resin>
The method for producing the ionomer resin in the present invention is not particularly limited. Even if (II) is produced by adding a salt separately in the ionomer resin production process, (III) is produced by first producing a salt-free ionomer resin and then adding a salt to the resin. may Among these methods, a salt composed of a strong acid and a strong base can be easily dispersed uniformly in the ionomer resin, thereby easily improving the transparency and thermal decomposition resistance of the ionomer resin composition. The above-described method (I), in which a salt is formed and contained in is preferred. The method (I) will be described in detail below.

As the method (I), an ethylene-(meth)acrylic acid ester copolymer (X) is used as a raw material, and all or part of the (meth)acrylic acid ester units in the copolymer are replaced with (meth)acrylic acid. (meth)acrylic acid units (A), (meth)acrylic acid neutralized units (B), ethylene units (C) and optionally (meth) A crude ionomer resin containing acrylic acid ester units (D) is produced (step i), a poor solvent is added to the resulting crude ionomer resin solution to precipitate a granular resin (step ii), and then the precipitated granular resin is is washed with a washing liquid (step iii).

(Step i)
As a method for converting all or part of the (meth)acrylic acid ester units in the ethylene-(meth)acrylic acid ester copolymer (X) into (meth)acrylic acid units and neutralized (meth)acrylic acid units converts all or part of the (meth)acrylic acid ester units to neutralized (meth)acrylic acid units by saponifying the ethylene-(meth)acrylic acid ester copolymer (X) with a strong base. to obtain an ethylene-(meth)acrylic acid neutralized copolymer or an ethylene-(meth)acrylic acid ester-(meth)acrylic acid neutralized copolymer, and then A method of demetallizing (meth)acrylic acid neutralized units with a strong acid to convert them into (meth)acrylic acid units (hereinafter also referred to as method (1)) can be mentioned.
As a method other than the above method (1), the ethylene-(meth)acrylic acid neutralized copolymer or ethylene-(meth)acrylic acid ester-(meth)acrylic acid obtained by saponification in the above method (1) All of the (meth)acrylic acid neutralized units in the hydropolymer are demetallized with a strong acid, converted to (meth)acrylic acid units, and ethylene-(meth)acrylic acid copolymers or ethylene-(meth ) A method of obtaining an acrylic acid ester-(meth)acrylic acid copolymer and then neutralizing a part of the (meth)acrylic acid units in the obtained copolymer with metal ions (hereinafter, method (2) Also called).
In the above methods (1) and (2), the neutralization reaction between the strong base used for the saponification reaction and the strong acid used for demetallization produces a salt composed of a strong acid and a strong base. A crude ionomer resin containing salts is obtained.

Examples of monomers constituting the (meth)acrylate unit of the ethylene-(meth)acrylate copolymer (X) include methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylate ) n-propyl acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, (meth) ) amyl acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, pentadecyl (meth)acrylate, dodecyl (meth)acrylate , isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, Examples include glycidyl (meth)acrylate and allyl (meth)acrylate. Among these, preferred monomers are methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, ( meth)isobutyl acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, more preferred monomers are methyl (meth)acrylate, ethyl (meth)acrylate, n (meth)acrylate -propyl, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, more preferred monomers are methyl (meth) acrylate, n-butyl (meth) acrylate, (meth) ) isobutyl acrylate, particularly preferably methyl (meth)acrylate. These (meth)acrylic acid esters may be used singly or in combination of two or more.

Specific examples of the ethylene-(meth)acrylic acid ester copolymer (X) include ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacryl Ethyl acid copolymer, ethylene-n-propyl acrylate copolymer, ethylene-n-propyl methacrylate copolymer, ethylene-isopropyl acrylate copolymer, ethylene-isopropyl methacrylate copolymer, ethylene-acrylic acid n-butyl copolymer, ethylene-n-butyl methacrylate copolymer, ethylene-sec-butyl acrylate copolymer, ethylene-sec-butyl methacrylate copolymer and the like.
As these copolymers, commercially available products may be used, and those synthesized by the high-temperature, high-pressure radical polymerization method described in US2013/0274424, JP-A-2006-233059, or JP-A-2007-84743 may be used. Examples of the commercially available products include "Aclift" (registered trademark) WD301F and WH401F manufactured by Sumitomo Chemical Co., Ltd., and "Rexpearl" (registered trademark) A4250 manufactured by Japan Polyethylene Corporation.

The content of (meth)acrylate units in the ethylene-(meth)acrylate copolymer (X) is preferably 6 mol% or more, more preferably 6.5 mol% or more, and still more preferably 7 mol. % or more, particularly preferably 7.5 mol % or more, and preferably 10 mol % or less, more preferably 9.9 mol % or less, still more preferably 9.5 mol % or less. The content of (meth)acrylic acid ester units in the copolymer (X) is determined by the (meth)acrylic acid units (A) and (meth)acrylic acid neutralized units in the resulting crude ionomer resin and ionomer resin. (B), and, if included, the (meth) acrylic acid ester unit (D), so that the content of the (meth) acrylic acid ester unit in the copolymer (X) corresponds to the above lower limit value or more, the transparency of the resulting ionomer resin composition, especially during slow cooling, tends to be enhanced. easy to improve.
The content of (meth)acrylic acid ester units in the copolymer (X) can be adjusted by the copolymerization ratio of ethylene and (meth)acrylic acid ester. In addition, the content is the (meth)acrylic acid unit (A), the (meth)acrylic acid neutralized product unit (B), and the ethylene unit (C) in the ionomer resin described above, and when included (meth) As well as the contents of acrylic acid ester units (D) and other monomeric units (e.g. units (A1) and units (B1)), pyrolysis gas chromatography, nuclear magnetic resonance spectroscopy (NMR) and It can be determined by elemental analysis.

In one embodiment of the present invention, the melt flow rate (MFR ) is preferably 5 g/10 min or more, more preferably 10 g/10 min or more, still more preferably 50 g/10 min or more, still more preferably 100 g/10 min or more, preferably 400 g/10 min or less, more It is preferably 350 g/10 minutes or less, more preferably 300 g/10 minutes or less, and even more preferably 250 g/10 minutes or less. When the MFR of the ethylene-(meth)acrylic acid ester copolymer (X) is at least the above lower limit and below the above upper limit, the resulting ionomer resin composition tends to be improved in moldability and strength. The MFR of the ethylene-(meth)acrylic acid ester copolymer (X) can be adjusted by the degree of polymerization and the content of (meth)acrylic acid ester units. The MFR can be measured, for example, by the method described in Examples.

The weight-average molecular weight of the ethylene-(meth)acrylic acid ester copolymer (X) is preferably 15,000 g/mol or more, more preferably 15,000 g/mol or more, from the viewpoint of easily improving the moldability and strength of the resulting ionomer resin composition. is 20,000 g/mol or more, more preferably 30,000 g/mol or more, preferably 200,000 g/mol or less, more preferably 100,000 g/mol or less. From the same point of view, the number average molecular weight of the ethylene-(meth)acrylate copolymer (X) is preferably 5,000 g/mol or more, more preferably 10,000 g/mol or more, still more preferably 15 ,000 g/mol or more, preferably 100,000 g/mol or less, more preferably 50,000 g/mol or less. The weight average molecular weight and number average molecular weight can be adjusted by adjusting the amount of polymerization initiator and/or chain transfer agent during polymerization. The molecular weights (weight average molecular weight and number average molecular weight) of these ethylene-(meth)acrylic acid ester copolymers (X) are determined by column (TSKgel GMH _HR -H(20)HT three in series) and 1,2, Using 4-trichlorobenzene as a solvent, the measurement can be performed at a column temperature of 140° C. in terms of polystyrene.

The degree of branching per 1000 carbon atoms of the ethylene-(meth)acrylic acid ester copolymer (X) is not particularly limited, and is preferably 5-30, more preferably 6-20. The degree of branching can be adjusted by the polymerization temperature when polymerizing the copolymer (X). The degree of branching can be measured by dissolving the ethylene-(meth)acrylic acid ester copolymer (X) in deuterated ortho-dichlorobenzene and performing ¹³ C-NMR inverse gate decoupling method.

Examples of the alkali used for the saponification reaction in the above methods (1) and (2) include strong bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, and the solubility in the solvent used for the saponification reaction and From the viewpoint of economy, sodium hydroxide and potassium hydroxide are preferred.

Examples of solvents used in the saponification reaction include ethers such as tetrahydrofuran and dioxane; halogen-containing solvents such as chloroform and dichlorobenzene; ketones having 6 or more carbon atoms such as methylbutyl ketone; mixed solvents with alcohols such as 1-propanol, 2-propanol and 1-butanol; aromatic compounds such as benzene, toluene, xylene and ethylbenzene; and mixed solvents of aromatic compounds and alcohols. These solvents may be used alone or in combination of two or more.
Among these, from the viewpoint of the solubility of the resin before and after the saponification reaction, preferred solvents are mixed solvents of hydrocarbon compounds and alcohols, mixed solvents of aromatic compounds and alcohols, and more preferred solvents are toluene and the like. It is a mixed solvent of an aromatic compound and an alcohol such as methanol. The ratio of the hydrocarbon compound or aromatic compound to the alcohol in the mixed solvent may be appropriately selected according to the type of each solvent used. hydrogen compounds or aromatics/alcohols) can be from 50/50 to 90/10.

The temperature at which the saponification reaction is performed is preferably 50° C. or higher, more preferably 60° C. or higher, from the viewpoint of reactivity and solubility of the ethylene-(meth)acrylic acid ester copolymer (X). It is preferably 70° C. or higher, particularly preferably 80° C. or higher. The upper limit of the temperature is not particularly limited as long as it is lower than the temperature at which the ethylene-(meth)acrylic acid ester copolymer (X) decomposes, and is, for example, 300° C. or less.

The saponification reaction may be performed in the air or in an inert gas such as nitrogen gas or argon gas. The saponification reaction may be carried out under normal pressure, increased pressure, or reduced pressure, preferably under increased pressure.

Examples of acids used for demetallization in the above methods (1) and (2) include strong acids such as hydrochloric acid, nitric acid, sulfuric acid and toluenesulfonic acid. These acids may be used singly or in combination of two or more. Inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid are preferred from the viewpoint of easy removal of salts from the ionomer resin after demetalization. As the solvent used for the demetallization, the same solvents as those used for the saponification reaction can be selected.

The temperature at which the demetallization is performed is preferably 20° C. or higher, more preferably 30° C. or higher, still more preferably 40° C. or higher, and preferably 100° C. or lower, from the viewpoint of easily lowering the viscosity of the reaction solution. It is more preferably 80° C. or lower, still more preferably 60° C. or lower.

The above demetallization may be carried out in the air or in an inert gas such as nitrogen gas or argon gas, as in the above saponification reaction. The saponification reaction may be carried out under normal pressure, increased pressure, or reduced pressure, preferably under increased pressure.

In the above method (2), the neutralizing agent used for partially neutralizing the (meth)acrylic acid units and converting them into neutralized (meth)acrylic acid units is an ionic compound containing metal ions. There is no particular limitation if any. Examples of the metal ions include alkali metal ions such as lithium, potassium and sodium, alkaline earth metal ions such as magnesium and calcium, transition metal ions such as zinc, nickel, iron and titanium, and aluminum ions. For example, when the metal ions are sodium ions, examples of neutralizing agents include sodium hydroxide and the like.

(Step ii)
(solution of crude ionomer resin)
The crude ionomer resin obtained in step i comprises (meth)acrylic acid units (A), (meth)acrylic acid neutralized units (B) and ethylene units (C), wherein said units (A) and said units ( The total content of B) is 6 to 10 mol % based on the total monomer units constituting the crude ionomer resin. Further, the crude ionomer resin preferably contains a (meth)acrylic acid ester unit (D) in addition to the units (A), (B) and (C). When the (meth)acrylic acid ester unit (D) is included, the total content of the unit (A), the unit (B) and the unit (D) is the total monomer units constituting the crude ionomer resin. As a standard, it is preferably 6 to 10 mol %. In addition to the units (A), (B), and (C), and optionally the units (D), the crude ionomer resin further contains carboxylic acids other than (meth)acrylic acid units. Acid units (A1) and other monomer units such as neutralized carboxylic acid units (B1) other than neutralized (meth)acrylic acid units may be included.

Examples of the unit (A) and the unit (B) in the crude ionomer resin, the unit (D) which may optionally be included, and the other monomeric units (A1) and (B1) are Units (A), units (B), units (D), units (A1), and units (B1) contained in the ionomer resin of the invention include the same units as those described above, and preferred forms are the ionomers described above. Similar to resin. In addition, the content of each unit in the crude ionomer resin, the total content of the unit (A) and the unit (B), and optionally the unit (A) and the unit (B) when the unit (D) is included and the total content of units (D) are the same as those described above for the ionomer resin of the present invention, including preferred forms.

The crude ionomer resin solution can be prepared by dissolving the crude ionomer resin obtained in step i in a solvent, and the reaction solution of the crude ionomer resin obtained in step i may be used as the crude ionomer resin solution.

The solvent in the solution of the crude ionomer resin is not particularly limited as long as it can dissolve the crude ionomer resin, and the same solvents as those used in the saponification reaction are exemplified. Among them, a mixed solvent of an aromatic compound such as toluene and an alcohol such as methanol is preferable from the viewpoint of solubility of the crude ionomer resin. The ratio of the aromatic compound to the alcohol in the mixed solvent may be appropriately selected according to the type of each solvent used. For example, the mass ratio of the aromatic compound to the alcohol (aromatic compound/alcohol) is , 50/50 to 90/10, preferably 65/35 to 85/15.

The concentration of the solution of the crude ionomer resin makes it easy to obtain a granular resin with a small particle size. From the viewpoint of easily improving the properties, the content is preferably 30% by mass or less, more preferably 15% by mass or less, and preferably 1% by mass or more, more preferably 5% by mass or more.

The temperature of the solution of the crude ionomer resin makes it easy to suppress aggregation or agglutination of the precipitated granular resin, makes it easy to adjust the salt content in the ionomer resin within the range of 1 to 400 mg/kg, and increases the heat resistance of the ionomer resin composition. From the viewpoint of easily improving the decomposability, the temperature is preferably the melting point of the ionomer resin or less, more preferably 60° C. or less, and still more preferably 50° C. or less. From the viewpoint of the fluidity of the crude ionomer resin solution, the temperature is more preferably 25° C. or higher, more preferably 30° C. or higher.

(poor solvent)
The poor solvent added to the solution of the crude ionomer resin is not particularly limited as long as it is mixed with the solution of the crude ionomer resin and does not dissolve the ionomer resin. Examples include methanol, ethanol, 1-propanol, 2-propanol, alcohols such as 1-butanol; water; ketones such as acetone and methyl ethyl ketone; esters such as methyl acetate and ethyl acetate; ethers such as dimethyl ether, diethyl ether and tetrahydrofuran; compounds and the like. These may be used individually by 1 type, or may be used in combination of 2 or more type. Among these, the poor solvent is preferably methanol, 2-propanol, or the like, from the viewpoint of easy drying of the ionomer resin due to its low boiling point and easy removal of the salt in the granular resin because it can dissolve the salt. Alcohols, water, and mixed solvents thereof, more preferably alcohols such as methanol.

The amount of the poor solvent to be added may be appropriately selected according to the concentration of the crude ionomer resin solution. For example, the amount of the poor solvent to be added is preferably 30 parts by mass or more, more preferably 60 parts by mass or more, and particularly preferably 100 parts by mass or more with respect to 100 parts by mass of the crude ionomer resin solution. The upper limit of the amount of the poor solvent to be added is not particularly limited, and is usually 1000 parts by mass or less with respect to 100 parts by mass of the crude ionomer resin solution.

The method of adding the poor solvent to the solution of the crude ionomer resin is not particularly limited. good. The particle size of the granular resin is likely to be reduced, thereby easily improving the removability of the salt in the granular resin, and as a result, from the viewpoint of easily improving the transparency of the ionomer resin composition. It is preferable to carry out in a short time, and it is more preferable to add at once. When the poor solvent is added in multiple portions, the addition of the poor solvent is preferably completed within 1 hour, more preferably within 30 minutes, and even more preferably within 10 minutes.

After adding the poor solvent to the crude ionomer resin solution, it is preferable to stir the mixture of the crude ionomer resin solution and the poor solvent. The stirring speed is not particularly limited, but the faster the stirring speed, the easier it is to obtain a granular resin with a small particle size. The stirring time is not particularly limited, and for example, the granular resin may be precipitated and the mixture of the crude ionomer resin solution and the poor solvent may be stirred until it becomes a slurry. Specifically, it is preferably 1 second or longer. It is 3 hours or less, more preferably 10 seconds or more and 1 hour or less, and still more preferably 1 minute or more and 30 minutes or less.

(granular resin)
The peak top particle size of the granular resin precipitated by adding a poor solvent to the solution of the crude ionomer resin is increased by increasing the specific surface area of the granular resin, thereby making it easier to reduce the salt content in the granular resin. , From the viewpoint of easily adjusting the salt content within the range of 1 to 400 mg / kg and easily improving the thermal decomposition resistance of the ionomer resin composition, the salt content is 700 μm or less, preferably 650 μm or less, more preferably 600 μm or less, and further It is preferably 550 μm or less. From the viewpoint of easily improving the filterability of the granular resin and easily improving the production efficiency of the ionomer resin, it is preferably 50 μm or more, more preferably 70 μm or more, and preferably 80 μm or more. The peak top particle size can be determined by measuring the particle size distribution of the granular resin using, for example, a laser diffraction/scattering particle size distribution analyzer.

The peak top particle size of the granular resin precipitated by adding a poor solvent to the crude ionomer resin solution can be adjusted by the concentration and temperature of the crude ionomer resin solution. Specifically, when the concentration and/or temperature of the crude ionomer resin solution is decreased, the peak top particle size of the precipitated granular resin can be decreased, and when the concentration and/or temperature of the crude ionomer resin solution is increased, precipitation occurs. The peak top particle size of the granular resin can be increased. The peak top particle size of the granular resin can also be adjusted by the method of adding the poor solvent and the stirring speed of the mixture of the crude ionomer resin solution and the poor solvent.

(Step iii)
(washing liquid)
The washing liquid in step iii is not particularly limited as long as it does not dissolve the ionomer resin and can dissolve the salt. Examples of preferred washing liquids include alcohols such as methanol, ethanol, 1-propanol and 2-isopropanol; water; ketones such as acetone and methyl ethyl ketone; esters such as methyl acetate and ethyl acetate; and ethers of These may be used individually by 1 type, or may be used in combination of 2 or more type.

Among these washing liquids, alcohols, water, and mixed liquids thereof are preferable from the viewpoint of high solubility of salts and easy removal of salts contained in the granular resin. Furthermore, in addition to increasing the solubility of the salt, by making the specific gravity of the cleaning liquid smaller than that of the granular resin, the contact area between the cleaning liquid and the granular resin is increased, so that the removability of the salt can be easily improved. A more preferable cleaning liquid is a mixed liquid of water and alcohols from the viewpoint of facilitating removal of impurities such as organic compounds contained in the resin and facilitating drying of the ionomer resin obtained after washing. Preferred alcohols are methanol, ethanol, and more preferably methanol, since they are easy to dry and have high compatibility with water.
The ratio of water and alcohols (water/alcohols (% by mass)) in the mixture of water and alcohols is preferably 20/80 to 80/20, more preferably 30/70 to 70/30. .

An example of a method of washing the granular resin with a washing liquid is a method of filtering the granular resin from the granular resin dispersion liquid in which the granular resin is precipitated in step ii, mixing the filtered granular resin with the washing liquid, and then removing the liquid. is mentioned. More specifically, after mixing the granular resin filtered from the granular resin dispersion with a washing liquid, the granular resin is filtered from the washing liquid (hereinafter also referred to as washing step (a)), and then the filtered granular There is a method of washing by mixing the resin with a fresh washing liquid and then filtering out the granular resin from the washing liquid (hereinafter also referred to as washing step (b)). From the viewpoint of easily adjusting the content of the salt contained in the granular resin within the range of 1 to 400 mg / kg, easily improving the thermal decomposition resistance of the ionomer resin composition, and from the viewpoint of the production efficiency of the ionomer resin, cleaning of the granular resin In the case of a batch process, for example, after one washing step (a), the washing step (b) is preferably performed 1 to 10 times, and the washing step (b) after one washing step (a). is more preferably 1 to 6 times, more preferably 1 to 4 times.

The amount of the cleaning liquid used in one cleaning step may be appropriately selected according to the amount of granular resin to be cleaned. For example, the amount of the cleaning liquid used in one cleaning step is preferably 100 parts by mass to 2000 parts by mass, more preferably 200 parts by mass to 1000 parts by mass, and still more preferably 100 parts by mass of the dried granular resin. is 300 parts by mass to 700 parts by mass.

The ionomer resin obtained in step iii may be dried if necessary. The drying temperature is preferably below the melting point of the ionomer resin, more preferably below 80°C.

〔Silane coupling agent〕
The ionomer resin composition of the present invention contains 0.005 to 0.5 parts by mass of the silane coupling agent per 100 parts by mass of the ionomer resin. By including the silane coupling agent within the above range, the adhesiveness to glass, particularly the adhesiveness to glass in a wet state can be improved. This is because the silane coupling agent has a reactive group that reacts with inorganic materials such as glass and a reactive group that reacts with organic materials such as resin. Alternatively, it is considered that they can be bound by an ionic bond or the like. Further, in the present invention, even if the amount of the silane coupling agent is as small as 0.005 to 0.5 parts by mass with respect to 100 parts by mass of the ionomer resin, the adhesion between the ionomer resin composition and the glass can be enhanced. Therefore, even if a silane coupling agent is contained, formation of a crosslinked gel can be suppressed, and a resin sheet having a good appearance such as excellent surface smoothness can be obtained. On the other hand, if the content of the silane coupling agent is less than the above lower limit, the adhesiveness to glass in a wet state tends to decrease, so peeling from the glass tends to occur in a wet state. On the other hand, when the above upper limit is exceeded, gelation tends to proceed due to the cross-linking reaction by the silane coupling agent, and it tends to be difficult to obtain a resin sheet with good appearance.

In one embodiment of the present invention, the content of the silane coupling agent is 0.00 per 100 parts by mass of the ionomer resin, from the viewpoint of easily improving the adhesion to glass, particularly the adhesion to glass in a wet state. 005 mass parts or more, preferably 0.01 mass parts or more, more preferably 0.02 mass parts or more, still more preferably 0.05 mass parts or more, even more preferably 0.07 mass parts or more, particularly preferably 0.07 mass parts or more. 08 parts by mass or more. Moreover, the content is 0.5 parts by mass or less, preferably 0.5 parts by mass or less, based on 100 parts by mass of the ionomer resin, from the viewpoint of suppressing gelation of the ionomer resin composition and easily obtaining a resin sheet with a good appearance. It is 4 parts by mass or less, more preferably 0.3 parts by mass or less, still more preferably 0.2 parts by mass or less, and particularly preferably 0.18 parts by mass or less.

The silane coupling agent is not particularly limited, and examples thereof include amino-based compounds, glycidoxy-based compounds, sulfide-based compounds, mercapto-based compounds, vinyl-based compounds, nitro-based compounds, and chloro-based compounds. These silane coupling agents may be used singly or in combination of two or more.

Examples of amino compounds include N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-β-(aminoethyl)- γ-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-aminopropyltri Methoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-amino Propyltriethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, N-(2-aminomethyl)-8-aminooctyltrimethoxysilane, N-(2 -aminoethyl)-8-aminooctyltrimethoxysilane, N-(2-aminomethyl)-8-aminooctyltriethoxysilane, N-(2-aminoethyl)-8-aminooctyltriethoxysilane and the like. .

Examples of glycidoxy compounds include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane. Examples include ethoxysilane and 3-glycidoxypropyltriethoxysilane.

Examples of sulfide compounds include bis(3-triethoxysilylpropyl)tetrasulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxy silylethyl) tetrasulfide, bis(3-triethoxysilylpropyl) trisulfide, bis(3-trimethoxysilylpropyl) trisulfide, bis(3-triethoxysilylpropyl) disulfide, bis(3-trimethoxysilylpropyl) Disulfide, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 2-trimethoxysilylethyl-N,N-dimethylthiocarbamoyl Tetrasulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, 3-triethoxysilylpropylbenzothiazole tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, 3-octanoylthio-1 -propyltriethoxysilane and the like.

Mercapto-based compounds include, for example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, and 2-mercaptoethyltriethoxysilane.

Examples of vinyl compounds include vinyltriethoxysilane, vinyltrimethoxysilane, dimethoxymethylvinylsilane, and diethoxy(methyl)vinylsilane.

Examples of nitro compounds include 3-nitropropyltrimethoxysilane and 3-nitropropyltriethoxysilane.

Examples of chloro-based compounds include 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 2-chloroethyltrimethoxysilane, and 2-chloroethyltriethoxysilane.

Other compounds include, for example, diethoxydimethylsilane, 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane, dimethoxydimethylsilane, methyldiethoxysilane, diisopropyldimethoxysilane, dicyclopentyldimethoxysilane, octyltriethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, hexadecyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, N,N,N-tris(3-trimethoxysilylpropyl)triisocyanurate, etc. mentioned.

In one embodiment of the present invention, the silane coupling agent may be either trialkoxysilane or dialkoxysilane. is preferably

In one embodiment of the present invention, the silane coupling agent is preferably an amino-based compound or a glycidoxy-based compound, more preferably N-β, from the viewpoint of easily improving the adhesion to glass in a wet state among the above. -(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane Ethoxysilane, more preferably N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane and 3-glycidoxypropylmethyldiethoxysilane. These silane coupling agents can be used alone or in combination of two or more.

[Other additives]
In one embodiment of the present invention, the resin composition of the present invention may optionally contain other additives in addition to the silane coupling agent. Examples of additives include UV absorbers, anti-aging agents, antioxidants, heat deterioration inhibitors, light stabilizers, anti-sticking agents, lubricants, release agents, polymer processing aids, antistatic agents, flame retardants. , dyes and pigments, organic dyes, matting agents, phosphors, and the like. Among these additives, ultraviolet absorbers, anti-aging agents, antioxidants, heat deterioration inhibitors, light stabilizers, anti-sticking agents, lubricants, release agents, polymer processing aids and organic dyes are preferred. Additives may be used alone or in combination of two or more.

A UV absorber is a compound that has the ability to absorb UV rays, and is said to have the function of mainly converting light energy into heat energy. Examples of UV absorbers include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, oxalic acid anilides, malonic acid esters, formamidines and the like. These may be used singly or in combination of two or more.

Benzotriazoles are preferable as UV absorbers because they are highly effective in suppressing deterioration of optical properties such as coloration due to exposure to UV light. Examples of preferred benzotriazoles include 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (manufactured by BASF; trade name: TINUVIN329), 2 -(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (manufactured by BASF; trade name: TINUVIN234), 2,2'-methylenebis[6-(2H -benzotriazol-2-yl)-4-t-octylphenol] (manufactured by ADEKA Corporation; trade name: ADEKA STAB LA-31), 2-(5-octylthio-2H-benzotriazol-2-yl)-6- tert-butyl-4-methylphenol and the like. These may be used singly or in combination of two or more.

Examples of triazine UV absorbers include 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine (manufactured by ADEKA Corporation; trade name : Adekastab LA-F70) and its analogues, hydroxyphenyltriazine-based UV absorbers (manufactured by BASF; trade names: TINUVIN477 and TINUVIN460), 2,4-diphenyl-6-(2-hydroxy-4-hexyloxy phenyl)-1,3,5-triazine and the like. These may be used singly or in combination of two or more.

Well-known materials are exemplified as anti-aging agents. Examples of specific anti-aging agents include hydroquinone, hydroquinone monomethyl ether, 2,5-di-t-butylphenol, 2,6-di(t-butyl)-4-methylphenol, mono (or di, or tri ) (α-methylbenzyl)phenol and other phenolic compounds; 2,2′-methylenebis(4-ethyl-6-t-butylphenol), 4,4′-butylidenebis(3-methyl-6-t-butylphenol), bisphenol compounds such as 4,4'-thiobis (3-methyl-6-t-butylphenol); benzimidazole compounds such as 2-mercaptobenzimidazole and 2-mercaptomethylbenzimidazole; 6-ethoxy-1,2- Amine-ketone compounds such as dihydro-2,2,4-trimethylquinoline, reaction products of diphenylamine and acetone, 2,2,4-trimethyl-1,2-dihydroquinoline polymers; N-phenyl-1-naphthylamine, Aromatics such as alkylated diphenylamine, octylated diphenylamine, 4,4′-bis(α,α-dimethylbenzyl)diphenylamine, p-(p-toluenesulfonylamido)diphenylamine, N,N′-diphenyl-p-phenylenediamine Secondary amine compounds; thiourea compounds such as 1,3-bis(dimethylaminopropyl)-2-thiourea and tributylthiourea; These may be used singly or in combination of two or more.

　Antioxidants are effective by themselves to prevent oxidative deterioration of resins in the presence of oxygen. Examples include phosphorus antioxidants, hindered phenol antioxidants, thioether antioxidants, and the like. These antioxidants may be used alone or in combination of two or more. Among them, from the viewpoint of the effect of preventing deterioration of optical properties due to coloring, phosphorus-based antioxidants and hindered phenol-based antioxidants are preferable, and a combination of a phosphorus-based antioxidant and a hindered phenol-based antioxidant is more preferable. .

When a phosphorus-based antioxidant and a hindered phenol-based antioxidant are combined, the amount of phosphorus-based antioxidant used: the amount of hindered phenol-based antioxidant used is preferably 1:5 to 2 in mass ratio. :1, more preferably 1:2 to 1:1.

Examples of preferred phosphorus antioxidants include 2,2-methylenebis(4,6-di-t-butylphenyl)octylphosphite (manufactured by ADEKA Corporation; trade name: ADEKA STAB HP-10), Tris (2 ,4-di-t-butylphenyl)phosphite (manufactured by BASF; trade name: IRGAFOS168), 3,9-bis(2,6-di-t-butyl-4-methylphenoxy)-2,4,8 , 10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (manufactured by ADEKA Corporation; trade name: ADEKA STAB PEP-36). These may be used singly or in combination of two or more.

Preferred examples of hindered phenolic antioxidants include pentaerythrityl-tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (manufactured by BASF; trade name: IRGANOX1010), Octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (manufactured by BASF; trade name: IRGANOX1076) and the like. These may be used singly or in combination of two or more.

Thermal degradation inhibitors can prevent thermal degradation of resins by scavenging polymer radicals that are generated when exposed to high heat under virtually oxygen-free conditions. Examples of preferred heat deterioration inhibitors include 2-t-butyl-6-(3′-t-butyl-5′-methyl-hydroxybenzyl)-4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd.; trade name : Sumilizer GM), 2,4-di-t-amyl-6-(3′,5′-di-t-amyl-2′-hydroxy-α-methylbenzyl)phenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd.; trade name: Sumilizer GS) and the like. These may be used singly or in combination of two or more.

A light stabilizer is a compound that is said to have the function of scavenging radicals that are mainly generated by light oxidation. Examples of preferred light stabilizers include hindered amines such as compounds having a 2,2,6,6-tetraalkylpiperidine skeleton. These may be used singly or in combination of two or more.

Examples of anti-adhesion agents include salts or esters of fatty acids, esters of polyhydric alcohols, inorganic salts, inorganic oxides, and particulate resins. Examples of preferred anti-adhesion agents include calcium stearate, calcium carbonate, calcium sulfate, magnesium sulfate, barium sulfate, silicon dioxide (manufactured by Evonik; trade name: Aerosil), and particulate acrylic resins. These may be used singly or in combination of two or more.

Examples of lubricants include stearic acid, behenic acid, stearamic acid, methylenebisstearamide, hydroxystearic acid triglyceride, paraffin wax, ketone wax, octyl alcohol, and hydrogenated oil. These may be used singly or in combination of two or more.

Examples of release agents include higher alcohols such as cetyl alcohol and stearyl alcohol; glycerin higher fatty acid esters such as stearic acid monoglyceride and stearic acid diglyceride. These may be used singly or in combination of two or more.

As the polymer processing aid, polymer particles having a particle size of 0.05 to 0.5 μm, which can be produced by an emulsion polymerization method, are usually used. The polymer particles may be monolayer particles composed of a polymer having a single composition ratio and a single intrinsic viscosity, or may be multilayer particles composed of two or more polymers having different composition ratios or intrinsic viscosities. good. These may be used singly or in combination of two or more. Among these, particles having a two-layer structure having an inner layer of a polymer layer having a low intrinsic viscosity and an outer layer of a polymer layer having a high intrinsic viscosity of 5 dl/g or more are preferred. The intrinsic viscosity of the polymeric processing aid is preferably 3-6 dl/g. If the intrinsic viscosity is too low, the effect of improving the moldability tends to be low, and if the intrinsic viscosity is too high, the molding processability of the copolymer tends to deteriorate.

As an example of an organic dye, a compound that has the function of converting ultraviolet light into visible light is preferably used. The organic dyes may be used singly or in combination of two or more.

Examples of phosphors include fluorescent pigments, fluorescent dyes, fluorescent white dyes, fluorescent whitening agents, and fluorescent bleaching agents. These may be used singly or in combination of two or more.

The content of various additives can be appropriately selected within a range that does not impair the effects of the present invention, and the total content of various additives is preferably 7% by mass or less, more preferably 7% by mass or less, more preferably It is 5% by mass or less, more preferably 4% by mass or less.

[Ionomer resin composition]
The ionomer resin composition of the present invention comprises an ionomer resin and a silane coupling agent, wherein the ionomer resin contains (meth)acrylic acid units (A), (meth)acrylic acid neutralized units (B) and ethylene units (C ), the total content of the units (A) and the units (B) is 6 to 10 mol% based on the total monomer units constituting the ionomer resin, and the strong acid and the strong Since the content of the salt composed of a base is 1 to 400 mg/kg, and the content of the silane coupling agent is 0.005 to 0.5 parts by mass with respect to 100 parts by mass of the ionomer resin, high transparency , it has high thermal decomposition resistance and high adhesion to glass in a wet state, and can form a resin sheet having an excellent appearance.

In one embodiment of the present invention, the content of the ionomer resin is preferably relative to the total mass of the ionomer resin composition, from the viewpoint of easily improving transparency, thermal decomposition resistance, and particularly adhesion to glass in a wet state. is 90% by mass or more, more preferably 95% by mass or more, still more preferably 98% by mass or more, still more preferably 99% by mass or more, and preferably less than 100% by mass, more preferably 99.99% by mass It is below.

Since the ionomer resin composition of the present invention contains 1 to 400 mg/kg of salt as described above, it can have high thermal decomposition resistance. In a preferred embodiment of the present invention, the ionomer resin composition of the present invention has a 1% weight loss temperature (Td1) when heated at 10°C/min in a nitrogen atmosphere, preferably 330°C or higher, more preferably 350°C. Above, more preferably 360° C. or higher, particularly preferably 370° C. or higher, and usually 450° C. or lower. When the 1% weight loss temperature of the ionomer resin composition is at least the above lower limit, foaming and/or thermal decomposition during melt molding of the ionomer resin composition is likely to be reduced, and air bubbles and/or are generated by thermal decomposition of the resin. It is easy to obtain an intermediate film that does not have defects such as black foreign matter. In this specification, the 1% weight reduction temperature represents the temperature at which the weight reduction rate becomes 1% based on the weight at 200°C. The 1% weight loss temperature can be measured according to JIS K7120:1987, for example, by the method described in Examples.

In one embodiment of the present invention, the storage modulus (E′) at 50° C. measured by dynamic viscoelasticity measurement of the ionomer resin composition of the present invention has good self-sustainability (i.e., high elastic modulus), In particular, from the viewpoint of self-sustainability in high-temperature environments (high elastic modulus in high-temperature environments), it is preferably 20 MPa or higher, more preferably 30 MPa or higher, even more preferably 40 MPa or higher, and particularly preferably 50 MPa or higher. The storage modulus (E') upper limit is not particularly limited, and may be 1000 MPa. Said storage modulus is determined by the molecular weight of the ionomer resin and (meth)acrylic acid units (A), (meth)acrylic acid neutralized units (B), and ethylene units (C), and optionally including (meth) It can be adjusted by the content of the acrylate unit (D).

The ionomer resin composition of the present invention has high transparency. In one embodiment of the present invention, the ionomer resin composition of the present invention preferably has a haze of 2.0% or less, more preferably 1.5% or less, even more preferably 1.0% or less. Since the transparency of the ionomer resin composition increases as the haze decreases, the lower limit is not particularly limited, and may be, for example, 0.01% or more. The haze of the ionomer resin composition is measured using a haze meter according to JIS K7136:2000.

The present inventors have found that the inclusion of a salt of a strong acid and a strong base in the ionomer resin tends to improve the thermal decomposition resistance of the ionomer resin composition. In particular, the inventors have found that the transparency of the ionomer resin composition in a water-absorbing state (transparency at the time of water absorption) is reduced. As a result of further studies, the present inventors have found that if the content of salt in the ionomer resin is 400 mg/kg or less, the transparency of the ionomer resin composition in a water-absorbed state can also be enhanced. Therefore, the ionomer resin composition of the present invention having a salt content of 1 to 400 mg/kg in the ionomer resin has high transparency even when absorbing water.
In one embodiment of the present invention, the haze (water absorption haze) of the ionomer resin composition of the present invention after absorbing water is preferably 9.0% or less, more preferably 5.0% or less, further preferably 3.0%. % or less, particularly preferably 2.5% or less. The lower the water absorption haze, the higher the transparency of the ionomer resin composition in a water-absorbed state. The water absorption haze was measured by immersing the ionomer resin composition in ion-exchanged water at 23° C. for 300 hours, removing the ionomer resin composition from the ion-exchanged water, and wiping off the water adhering to the surface. Using a haze meter, it can be measured according to JIS K7136:2000, for example, it can be measured by the method described in Examples.

According to the study of the present inventors, the ionomer resin tends to whiten easily if the crystallinity of the ionomer resin is too high, so the ionomer resin composition is slowly cooled to promote the crystallization of the ionomer resin transparency (transparency during slow cooling) tends to decrease. However, in the ionomer resin of the present invention, the total content of (meth)acrylic acid units (A) and (meth)acrylic acid neutralized units (B) in the resin is 6 mol% or more, so that it is difficult to crystallize. , and has high transparency even when slowly cooled.
In a preferred embodiment of the present invention, the haze of the ionomer resin composition of the present invention in which crystallization of the ionomer resin contained in the composition is accelerated by slow cooling (slow cooling haze) is preferably 5.0. % or less, more preferably 4.5% or less, still more preferably 4.0% or less, even more preferably 3.0% or less, and particularly preferably 2.5% or less. Since the transparency of the ionomer resin composition increases as the haze decreases, the lower limit is not particularly limited, and may be, for example, 0.01% or more. Slow-cooling haze is obtained by disposing a resin sheet formed from an ionomer resin composition as an intermediate film between two glass plates to prepare a laminated glass, heating the laminated glass to 140°C, and then reducing the haze from 140°C to 0.1. Obtained by measuring the haze after slowly cooling to 23°C at a rate of °C/min with a haze meter in accordance with JIS K7136:2000.

In one embodiment of the present invention, the ionomer resin composition of the present invention has a low degree of coloring and is preferably colorless. The yellowness index (YI) of the ionomer resin composition of the present invention is preferably 2.0 or less, more preferably 1.8 or less, still more preferably 1.5 or less, and particularly preferably 1.5 or less, from the viewpoint of low coloring. 0 or less. Since the lower the yellowness index (YI), the lower the colorability of the ionomer resin composition, the lower limit is not particularly limited, and may be, for example, 0 or more. The yellowness index (YI) can be measured using a colorimetric color difference meter in accordance with JIS Z8722:2009.

In one embodiment of the present invention, the adhesive strength of the ionomer resin composition of the present invention to glass is measured by, for example, the compression shear strength test described in WO1999-058334. The compressive shear strength is preferably 15 MPa or more, more preferably 20 MPa or more, and particularly preferably 25 MPa or more, from the viewpoint of easily increasing the adhesive strength. Moreover, the compressive shear strength may be 50 MPa or less from the viewpoint of easily increasing the penetration resistance of the laminated glass.

In one embodiment of the present invention, the wet state adhesion of the ionomer resin composition of the present invention to glass is measured by a peel test performed in a wet state. It can be evaluated by force. The glass adhesive strength in a wet state is preferably 0.1 N/cm or more, more preferably 0.3 N/cm or more, still more preferably 0.7 N/cm or more, still more preferably 1.0 N/cm or more, and particularly preferably is 1.2 N/cm or more. The upper limit is not particularly limited, and may be 10 N/cm or less. The adhesive strength can be measured by a tensile tester, for example, by the method described in the Examples.

The ionomer resin composition of the present invention may be in the form of pellets or the like in order to enhance convenience during storage, transportation, or molding. When the ionomer resin composition is pelletized, it can be obtained, for example, by cutting strands obtained by a melt extrusion method. When the resin composition is pelletized by a melt extrusion method, the temperature of the resin composition during melt extrusion is preferably 150° C. or higher, more preferably 170° C. or higher, from the viewpoint of easily stabilizing the discharge from the extruder. In addition, the temperature is preferably 250° C. or lower, more preferably 230° C. or lower, from the viewpoint of suppressing thermal decomposition and deterioration of the resin. Since the ionomer resin composition of the present invention has high thermal decomposition resistance, problems such as the generation of black foreign matter due to thermal decomposition of the ionomer resin composition are less likely to occur when the ionomer resin composition is pelletized by the melt extrusion method.

The method for producing the ionomer resin composition of the present invention is not particularly limited, and it can be produced, for example, by mixing an ionomer resin, a silane coupling agent and optionally other additives.

The method of mixing the ionomer resin and the silane coupling agent is not particularly limited. For example, the silane coupling agent may be directly added to the ionomer resin and mixed. Further, in one embodiment of the present invention, a silane coupling agent is added as part of the ionomer resin masterbatch, and the masterbatch and the ionomer resin are mixed to perform silane coupling in the ionomer resin composition. The content of the agent can also be adjusted. Furthermore, the addition of the silane coupling agent may be carried out in the step of pelletizing, or in the step of forming into sheets, films, or the like.

Various additives may be added during production of the ionomer resin, may be added to the ionomer resin after production of the ionomer resin, or may be added to the process of pelletizing, forming into sheets, films, etc. good.

[Resin sheet]
The present invention also includes a resin sheet comprising one or more layers containing the ionomer resin composition of the present invention. Since the resin sheet of the present invention comprises a layer containing the resin composition of the present invention, it has excellent transparency and adhesion to substrates such as glass. is also good.

The resin sheet of the present invention includes one or more layers containing the ionomer resin composition of the present invention (hereinafter also referred to as layer (x)).
The resin sheet of the present invention may be composed of only the layer (x), or may be a laminate containing at least one layer (x). The laminate is not particularly limited, but examples thereof include a laminate containing two or more layers (x), a laminate containing one or more layers (x) and one or more other layers, and the like. be done. When layer (x) or another layer is a plurality of layers, the resin or resin composition constituting each layer may be the same or different.

A layer containing a known resin is exemplified as the other layer. Examples of the resin include polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, polytetrafluoroethylene, acrylic resin, polyamide, polyacetal, polycarbonate, polyethylene terephthalate among polyesters, polybutylene terephthalate, cyclic polyolefin, polyphenylene sulfide, Polytetrafluoroethylene, polysulfone, polyethersulfone, polyarylate, liquid crystal polymer, polyimide, thermoplastic elastomer and the like can be used. In addition, other layers, if necessary, the additives, plasticizers, pigments, dyes, heat-shielding materials (for example, inorganic heat-shielding fine particles or organic heat-shielding materials having infrared absorption ability), functional It may contain one or more additives such as inorganic compounds.

In one embodiment of the present invention, the resin sheet of the present invention has an uneven structure on the surface thereof by a conventionally known method such as melt fracture or embossing, from the viewpoint of excellent bubble removal properties when the resin sheet and the substrate are thermocompression bonded. It is preferable to have The shape of the melt fracture and embossing may be appropriately selected from conventionally known shapes.

The thickness of one layer (x) in the resin sheet of the present invention is preferably 0.1 mm or more, more preferably 0.2 mm or more, still more preferably 0.3 mm or more, and particularly preferably 0.4 mm or more, Also, it is preferably 5 mm or less, more preferably 4 mm or less, even more preferably 2 mm or less, and particularly preferably 1 mm or less. When the layer (x) in the resin sheet is a plurality of layers, the thickness of each of the layers (x) in the resin sheet may be the same or different.

The thickness of the resin sheet of the present invention is preferably 0.1 mm or more, more preferably 0.2 mm or more, still more preferably 0.3 mm or more, even more preferably 0.4 mm or more, and particularly preferably 0.5 mm or more. More preferably 0.6 mm or more, even more preferably 0.7 mm or more, particularly preferably 0.75 mm or more, and preferably 20 mm or less, more preferably 15 mm or less, still more preferably 10 mm or less, still more preferably is 5 mm or less, particularly preferably 4 mm or less, particularly more preferably 2 mm or less, and even more preferably 1 mm or less.

The thickness of the resin sheet is measured using a conventionally known method, such as a contact or non-contact thickness gauge. The resin sheet may be wound into a roll or may be in the form of individual sheets.

In a preferred embodiment of the present invention, the resin sheet of the present invention has the weight loss temperature, haze, water absorption haze, slow cooling haze, and yellow color of the ionomer resin composition of the present invention described in the [Ionomer resin composition] section. degree, storage modulus at 50° C., adhesive strength, and adhesive strength in a wet state.

The resin sheet of the present invention preferably has a low water content from the viewpoint of resistance to foaming during production of laminated glass. The water content of the resin sheet is preferably 1% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.02% by mass or less, and particularly preferably 0.01% by mass or less. The content can be measured by a coulometric titration method.

The method for manufacturing the resin sheet of the present invention is not particularly limited. For example, after uniformly kneading the ionomer resin composition of the present invention, the layer (x) can be produced by a known film-forming method such as an extrusion method, a calendar method, a press method, a solution casting method, a melt casting method, or an inflation method. . Layer (x) may be used alone as a resin sheet. Further, if necessary, two or more layers (x), or one or more layers (x) and one or more other layers may be laminated by press molding or the like to form a laminated resin sheet. Two or more layers (x), or one or more layers (x) and one or more other layers may be co-extruded to form a laminated resin sheet. When the layer (x) or other layers are a plurality of layers, the resin composition constituting each layer may be the same or different.

Among known film-forming methods, a method of producing a resin sheet using an extruder is preferably used. The resin temperature during extrusion is preferably 150° C. or higher, more preferably 170° C. or higher, from the viewpoints of easily stabilizing the discharge of the resin from the extruder and easily reducing mechanical troubles. The resin temperature during extrusion is preferably 250° C. or lower, more preferably 230° C. or lower, from the viewpoint of facilitating decomposition of the resin and deterioration of the resin accompanying the decomposition. Moreover, in order to remove the volatile substances efficiently, it is preferable to remove the volatile substances from the vent port of the extruder by reducing the pressure.

[Laminated glass intermediate film and laminated glass]
The resin sheet of the present invention can be suitably used as an intermediate film for laminated glass (simply referred to as an intermediate film). Therefore, the present invention includes a laminated glass interlayer made of the resin sheet of the present invention. The invention also includes a laminated glass comprising two glass sheets and a laminated glass interlayer of the invention arranged between the two glass sheets. Since the laminated glass of the present invention has the laminated glass intermediate film made of the resin sheet, it can have excellent transparency.

Examples of the glass plate to be laminated with the interlayer film of the present invention include inorganic glass such as float plate glass, polished plate glass, figured glass, wired plate glass, and heat-absorbing plate glass, as well as conventionally known organic glasses such as polymethyl methacrylate and polycarbonate. Glass or the like can be used. They may be either colorless or colored. These may be used alone or in combination of two or more. Moreover, the thickness of one glass plate is preferably 100 mm or less, and the thickness of the two glass plates may be the same or different.

A laminated glass obtained by sandwiching the resin sheet of the present invention between two sheets of glass can be produced by a conventionally known method. Examples thereof include a method using a vacuum laminator, a method using a vacuum bag, a method using a vacuum ring, and a method using a nip roll. Moreover, after carrying out temporary press-bonding by the said method, the method of putting into an autoclave and carrying out final adhesion is also mentioned.

When using a vacuum laminator apparatus, for example, under a reduced pressure of 1×10 ⁻⁶ to 1×10 ⁻¹ MPa, at 60 to 200° C., especially 80 to 160° C., a glass plate, an interlayer, and any layer (for example, an adhesive resin layers, etc.), laminated glass can be produced. A method using a vacuum bag or a vacuum ring is described, for example, in EP 1235683, wherein a glass plate is heated at 100-160° C. under a pressure of about 2×10 ⁻² to 3×10 ⁻² MPa. Laminated glass can be produced by laminating the interlayer and optional layers.

As an example of a manufacturing method using nip rolls, a glass plate, an intermediate film and an arbitrary layer are laminated, degassed by rolls at a temperature below the flow start temperature of the intermediate film, and then crimped at a temperature close to the flow start temperature. method of doing so. Specifically, for example, after heating to 30 to 70° C. with an infrared heater or the like, degassing with rolls, further heating to 50 to 120° C., and pressing with rolls can be mentioned.

When pressure bonding is performed by putting it into an autoclave after pressure bonding using the above method, the operating conditions of the autoclave process are appropriately selected depending on the thickness and structure of the laminated glass. It is preferable to treat at 100 to 160° C. for 0.5 to 3 hours.

Because the ionomer resin composition of the present invention and the resin sheet obtained from the resin composition have high transparency and high adhesion to glass, the laminated glass of the present invention has excellent transparency. In one embodiment of the present invention, the haze of the laminated glass of the present invention is preferably 1.0% or less, more preferably 0.8% or less, still more preferably 0.5% or less. Since the transparency of the laminated glass increases as the haze decreases, the lower limit is not particularly limited, and may be, for example, 0.01%. The haze of laminated glass is measured using a haze meter according to JIS K7136:2000.

The laminated glass of the present invention also has excellent transparency during slow cooling. The transparency during slow cooling can be evaluated by the haze during slow cooling (slow cooling haze). The slow cooling haze of the laminated glass of the present invention is preferably 5.0% or less, more preferably 4.5% or less, still more preferably 4.0% or less, still more preferably 3.0% or less, and particularly preferably 2.5% or less. The lower the haze, the higher the transparency of the laminated glass, so the lower limit is not particularly limited, and may be, for example, 0.01% or more. The slow-cooling haze of the laminated glass is obtained by heating the laminated glass to 140°C and then slowly cooling it from 140°C to 23°C at a rate of 0.1°C/min. It can be obtained by measuring according to, for example, by the method described in Examples.

The laminated glass of the present invention is less colored and is preferably colorless as much as possible. The yellowness index (YI) of the laminated glass of the present invention is preferably 3.0 or less, more preferably 2.0 or less, still more preferably 1.5 or less, particularly preferably 1.0 or less, and preferably 0 or more. can be The yellowness index (YI) can be measured using a colorimetric color difference meter in accordance with JIS Z8722.

The adhesive strength between the glass plate and the interlayer in the laminated glass of the present invention is measured by, for example, the compression shear strength test described in WO1999-058334. The compressive shear strength is preferably 15 MPa or more, more preferably 20 MPa or more, and particularly preferably 25 MPa or more, from the viewpoint of easily increasing the adhesive strength. Moreover, the compressive shear strength may be 50 MPa or less from the viewpoint of easily increasing the penetration resistance of the laminated glass.

The wet state adhesion between the glass plate and the interlayer in the laminated glass of the present invention can be evaluated by the glass adhesive strength of the interlayer measured by a peeling test performed in the wet state. The glass adhesive strength in a wet state is preferably 0.1 N/cm or more, more preferably 0.3 N/cm or more, still more preferably 0.7 N/cm or more, still more preferably 1.0 N/cm or more, and particularly preferably is 1.2 N/cm or more. The upper limit is not particularly limited, and may be 10 N/cm or less. The adhesive strength can be measured by a tensile tester, for example, by the method described in the Examples.

As described above, a resin sheet comprising one or more layers containing the ionomer resin composition of the present invention is useful as an interlayer film for laminated glass. The interlayer film for laminated glass is particularly preferable as an interlayer film for laminated glass for structural materials (for facades) because of its excellent adhesion to substrates such as glass, transparency, and self-supporting properties.

In addition, the laminated glass of the present invention is not limited to the interlayer film of laminated glass for structural materials, and can be used for automobile windshields, automobile side glasses, automobile sunroofs, automobile rear glasses, head-up display glasses, exterior walls and roofs. It can be suitably used for building materials such as laminates, panels, doors, windows, walls, roofs, sunroofs, sound insulation walls, display windows, balconies, and handrails, partition glass members for conference rooms, solar panels, and the like.

The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[Content of monomer units of resins obtained in Examples and Comparative Examples]
Regarding the ionomer resin compositions obtained in Examples and Comparative Examples, the (meth)acrylic acid unit (A), the (meth)acrylic acid neutralized product unit (B), the ethylene unit (C), and the (meth)acrylic acid unit (B) in the ionomer resin ) Analysis of the content of acrylic acid ester units (D) was carried out as follows.

The ionomer resin compositions obtained in Examples and Comparative Examples were each dissolved in a mixed solvent of dehydrated toluene/dehydrated acetic acid (75/25% by mass), reacted at 100° C. for 2 hours, and then dissolved in acetone/water (80% by mass). /20% by mass) to convert the neutralized (meth)acrylic acid unit (B) into the (meth)acrylic acid unit (A). The obtained resin was thoroughly washed with water and then dried, and the following (1) to (3) were performed on the dried resin.
(1) The component of the monomer unit constituting the resin was analyzed by pyrolysis GC-MS.
(2) The acid value of the resin was measured according to JIS K0070:1992.
(3) Using a mixed solvent of deuterated toluene and deuterated methanol, the resin was subjected to ¹ H-NMR (400 MHz, manufactured by JEOL Ltd.) measurement.
(4) In addition, the ionomer resin compositions obtained in Examples and Comparative Examples were each subjected to microwave decomposition pretreatment with nitric acid, and then analyzed by ICP emission spectrometry (Thermo Fisher Scientific iCAP6500Duo) to determine (meth)acrylic acid The type and amount of metal ions in the neutralized unit (B) were identified.
From the above (1), the types and structures of the (meth)acrylic acid ester unit (D) and the (meth)acrylic acid unit (A) were identified. From that information and the information in (2) and (3) above, ethylene unit (C) / (meth) acrylic acid ester unit (D) / ((meth) acrylic acid unit (A) and (meth) acrylic acid The ratio of the sum of hydrate units (B)) was calculated. Furthermore, from the information in (4) above, the ratio of ethylene units (C) / (meth)acrylic acid ester units (D) / (meth)acrylic acid units (A) / (meth)acrylic acid neutralized units (B) was calculated.
Further, the content of each monomer unit of the ethylene-(meth)acrylic acid ester copolymer (X) as a raw material was determined by dissolving it in heavy toluene or heavy THF, and performing ¹ H-NMR (400 MHz, (manufactured by Co., Ltd.) and calculated.

[Content of Salt Consisting of Strong Acid and Strong Base in Ionomer Resin (Amount of Residual Inorganic Salt)]
0.1 g of the ionomer resin obtained in Examples and Comparative Examples was weighed, 10 mL of ultrapure water was added to the resin, and the mixture was heated at 90° C. for 1 hour. After that, it was allowed to cool and filtered through a filter with an opening of 0.45 μm. The filtrate obtained by filtration was used as a sample liquid, and measurement was performed under the following conditions using an ion chromatograph (manufactured by Shimadzu Corporation). Chloride ions or sulfate ions were quantified from the peak area obtained by the measurement, and the amount of the chloride ions or sulfate ions was converted to the amount of sodium salt to obtain the amount of residual inorganic salt.
(Measurement condition)
Eluent: mixed solution of sodium carbonate aqueous solution (0.6 mmol/L) and sodium hydrogencarbonate aqueous solution (12 mmol/L);
Flow rate: 1.0 mL/min;
Column temperature: 40°C;
Column: IC-SA2 (250L×4.0)

[Heat decomposition resistance]
Thermal decomposition resistance of the ionomer resin compositions obtained in Examples and Comparative Examples was evaluated according to JIS K7120:1987. Specifically, using a simultaneous differential thermogravimetric analyzer TG-DTA7200 (manufactured by Hitachi High-Tech Science Co., Ltd.), each resin composition was measured under a nitrogen atmosphere at a temperature increase rate of 10 ° C./min and a flow rate of 50 mL/min. The weight loss rate was measured when heated from 20°C to 550°C. The 1% weight reduction temperature (Td1), which is the temperature at which the weight reduction rate reaches 1% based on the weight at 200° C., was used as an index of thermal decomposition resistance.

[Transparency at the time of water absorption (water absorption haze)]
The resin sheets obtained in Examples and Comparative Examples were cut into 50 mm squares, and the cut samples were immersed in deionized water at 23° C. and held for 300 hours to obtain water-absorbing samples. After wiping off the water adhering to the surface of the water-absorbing sample taken out of the deionized water, the haze of the water-absorbing sample was measured using a haze meter HZ-1 (manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS K7136:2000. did.

[Transparency during slow cooling (slow cooling haze)]
The resin sheets obtained in Examples and Comparative Examples were sandwiched between two sheets of float glass having a thickness of 2.7 mm, and a vacuum laminator (1522N manufactured by Nisshinbo Mechatronics Co., Ltd.) was used to reduce the pressure in the vacuum laminator at 100°C for 1 minute. and pressed at 30 kPa for 5 minutes while maintaining the degree of pressure reduction and temperature to obtain a temporarily bonded body. The obtained temporarily bonded body was put into an autoclave and treated at 140° C. and 1.2 MPa for 30 minutes to obtain laminated glass.
After heating the laminated glass obtained by the above-described method to 140° C., it was slowly cooled to 23° C. at a rate of 0.1° C./min. The haze of the laminated glass after slow cooling was measured using a haze meter HZ-1 (manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS K7136:2000.

[Glass Adhesion in Wet State]
A float glass having a thickness of 2.7 mm was cut into a rectangle having a width of 100 mm and a length of 200 mm, and its surface was washed. A thin polyester tape (25 um thick, 25 mm wide) with silicone adhesive was applied to the air side of the float glass in two parallel strips to give a uniform 25 mm wide adhesive area between the polyester tapes. A resin sheet (thickness: 0.8 mm, width: 150 mm, length: 200 mm) was placed on the adhesive region, and a 12 μm fluororesin film was placed on the resin sheet. After that, a glass piece different from the float glass is placed on the fluororesin film to obtain a relatively flat surface for the lamination process, and the fluororesin film is used as a peeling layer for removing the glass piece. Made the film work. The obtained temporarily bonded body was put into an autoclave and treated at 140 ° C. and 1.2 MPa for 30 minutes, the fluororesin film and the glass piece placed thereon were removed, and the two layers of the float glass and the ionomer resin sheet were bonded. A peel test piece was obtained. After that, each sample was subjected to a peel test in the direction of an angle of 90° using a tensile tester (manufactured by Shimadzu Corporation, Autograph) to measure the adhesive strength to glass. The separation between the float glass surface and the ionomer resin sheet was performed at 23° C. and 50% RH at a head speed of 1 cm/min. After peeling off a sample of about 100 mm, deionized water was applied to the peeled interface between the float glass and the resin sheet so that the interface was completely immersed in liquid water. After that, the peel speed was reduced to 0.25 mm/min, and a peel test was conducted on a sample of about 100 mm to evaluate the adhesive strength to glass. Sufficient water was present to ensure that the samples remained "wet" during this test period. The average value of the wet-state glass adhesive strength obtained was used as the value.

〔material〕
Methyl methacrylate (MMA) modified amount or ethyl acrylate (EA) modified amount of each ethylene-(meth)acrylic acid ester copolymer (X) used as a raw material for the ionomer resin in Examples and Comparative Examples, and MFR are shown in Table 1.
As EMMA1, "Aclift" (registered trademark) WH401F manufactured by Sumitomo Chemical Co., Ltd. was used, and as EEA1, "Rex Pearl" (registered trademark) A4250 manufactured by Japan Polyethylene Co., Ltd. was used.

The silane coupling agents used in Examples and Comparative Examples are shown below.
Silane coupling agent 1 (S1): 3-glycidoxypropylmethyldiethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
Silane coupling agent 2 (S2): N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

[Example 1]
100 parts by mass of EMMA2 in Table 1 was introduced into a SUS pressure vessel, 233 parts by mass of toluene was added thereto, and the mixture was stirred at 60° C. under a pressure of 0.02 MPa to dissolve EMMA2. 96 parts by mass of a methanol solution of sodium hydroxide (20% by mass) was added to the resulting solution and stirred at 100° C. for 4 hours to saponify EMMA2 to convert part of the methyl methacrylate units into sodium methacrylate units. Converted. Next, after cooling this solution to 50° C., 83 parts by mass of hydrochloric acid (20% by mass) is added and stirred at 50° C. for 1 hour to convert a part of the sodium methacrylate units to methacrylic acid, resulting in a crude ionomer. A resin solution was obtained.
A mixed solvent of toluene/methanol (75/25% by mass) was added to the resulting crude ionomer resin solution so that the concentration of the crude ionomer resin was 10% by mass to dilute the solution. Next, after adjusting the obtained diluted solution of the crude ionomer resin to 34° C., 430 parts by mass of methanol at 34° C. per 100 parts by mass of the crude ionomer resin solution was added to the diluted solution to precipitate the granular resin. rice field. Next, after filtering the obtained granular resin, 100 parts by mass of the filtered granular resin was mixed with 600 parts by mass of a mixed solvent of water/methanol (50/50% by mass). The slurry obtained by the above mixing was stirred at 40° C. for 1 hour, after which the granular resin was collected by filtration at room temperature. The granular resin was further washed three times with a mixed solvent of water/methanol (50/50 mass %) to obtain washed ionomer resin 1.
After vacuum drying the obtained ionomer resin 1 for 8 hours or more, 100 parts by mass of the ionomer resin 1 and 0.15 parts by mass of the silane coupling agent (S1) were melt-kneaded at 210°C, and the melt-kneaded product was heated to 210°C. Under heating at , compression molding was performed for 5 minutes at a pressure of 4.9 MPa (50 kgf/cm ² ) to obtain an ionomer resin sheet 1 having a thickness of 0.8 mm. Table 2 shows the analysis results and evaluation results of the ionomer resin sheet 1.

[Example 2]
Ionomer resin 2 was obtained in the same manner as in Example 1, except that EMMA3 was used instead of EMMA2 and the temperature of the diluted solution of crude ionomer resin and methanol was changed from 34°C to 37°C. 100 parts by mass of the ionomer resin 2 and 0.06 parts by mass of the silane coupling agent (S1) were melt-kneaded at 210°C, and the melt-kneaded product was heated at 210°C under a pressure of 4.9 MPa (50 kgf/cm ² ). Compression molding was performed with pressure for 5 minutes to obtain an ionomer resin sheet 2 having a thickness of 0.8 mm. Table 2 shows the analysis results and evaluation results of the obtained ionomer resin sheet 2.

[Example 3]
Ionomer resin 3 was obtained in the same manner as in Example 1, except that EMMA3 was used instead of EMMA2, and the temperature of the diluted solution of crude ionomer resin and methanol was changed from 34°C to 40°C. 100 parts by mass of the ionomer resin 3 and 0.10 parts by mass of the silane coupling agent (S2) were melt-kneaded at 210°C, and the melt-kneaded product was heated at 210°C under a pressure of 4.9 MPa (50 kgf/cm ² ). Compression molding was performed with pressure for 5 minutes to obtain an ionomer resin sheet 3 having a thickness of 0.8 mm. Table 2 shows the analysis results and evaluation results of the obtained ionomer resin sheet 3.

[Example 4]
An ionomer resin 4 was obtained in the same manner as in Example 3, except that 220 parts by mass of sulfuric acid (30% by mass) was added instead of hydrochloric acid. 100 parts by mass of the ionomer resin 4 and 0.25 parts by mass of the silane coupling agent (S2) are melt-kneaded at 210°C, and the melt-kneaded product is heated at 210°C under a pressure of 4.9 MPa (50 kgf/cm ² ). Compression molding was performed under pressure for 5 minutes to obtain an ionomer resin sheet 4 having a thickness of 0.8 mm. Table 2 shows the analysis results and evaluation results of the obtained ionomer resin sheet 4.

[Example 5]
Example 1 except that EEA1 was used instead of EMMA2, the concentration of the diluted crude ionomer resin solution was changed from 10% by weight to 6% by weight, and the temperature of the diluted crude ionomer resin solution and methanol was changed from 34°C to 41°C. An ionomer resin 5 was obtained in the same manner as above. 100 parts by mass of the ionomer resin 5 and 0.10 parts by mass of the silane coupling agent (S2) were melt-kneaded at 210°C, and the melt-kneaded product was heated at 210°C under a pressure of 4.9 MPa (50 kgf/cm ² ). Compression molding was performed under pressure for 5 minutes to obtain an ionomer resin sheet 5 having a thickness of 0.8 mm. Table 2 shows the analysis results and evaluation results of the ionomer resin sheet 5 thus obtained.

[Example 6]
EMMA1 was used instead of EMMA2, the amount of methanol solution of sodium hydroxide (20% by mass) was changed from 96 parts by mass to 73 parts by mass, and the amount of hydrochloric acid (20% by mass) was changed from 83 parts by mass to 63 parts by mass. Ionomer resin 6 was obtained in the same manner as in Example 1, except that the temperature of the dilute solution of crude ionomer resin and methanol was changed from 34°C to 37°C. 100 parts by mass of the ionomer resin 6 and 0.40 parts by mass of the silane coupling agent (S2) are melt-kneaded at 210°C, and the melt-kneaded product is heated at 210°C under a pressure of 4.9 MPa (50 kgf/cm ² ). Compression molding was performed with pressure for 5 minutes to obtain an ionomer resin sheet 6 having a thickness of 0.8 mm. Table 2 shows the analysis results and evaluation results of the obtained ionomer resin sheet 6 .

[Example 7]
After obtaining ionomer resin 3 in the same manner as in Example 3, 0.12 parts by mass of a silane coupling agent (S2) and an ultraviolet absorber [2-(2H-benzotriazole- 2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (manufactured by BASF; trade name: TINUVIN329)] 0.1 part by mass was added, melt-kneaded at 210 ° C., and melt-kneaded. The product was compression molded for 5 minutes at a pressure of 4.9 MPa (50 kgf/cm ² ) under heating at 210° C. to obtain an ionomer resin sheet 7 having a thickness of 0.8 mm. Table 2 shows the analysis results and evaluation results of the ionomer resin sheet 7.

[Example 8]
Ionomer resin 8 was obtained in the same manner as in Example 1, except that EMMA3 was used instead of EMMA2, and the temperature of the diluted solution containing the crude ionomer resin and methanol was changed from 34°C to 41°C. 100 parts by mass of the ionomer resin 8 and 0.11 parts by mass of the silane coupling agent (S1) were melt-kneaded at 210°C, and the melt-kneaded product was heated at 210°C under a pressure of 4.9 MPa (50 kgf/cm ² ). Compression molding was performed under pressure for 5 minutes to obtain an ionomer resin sheet 8 having a thickness of 0.8 mm. Table 2 shows the analysis results and evaluation results of the ionomer resin sheet 8 thus obtained.

[Example 9]
EMMA3 was used instead of EMMA2, 147 parts by weight of sulfuric acid (30% by weight) was used instead of 83 parts by weight of hydrochloric acid (20% by weight), and the temperature of the diluted solution containing the crude ionomer resin and methanol was increased from 34°C to 41°C. An ionomer resin 9 was obtained in the same manner as in Example 1, except for the change. 100 parts by mass of the ionomer resin 9 and 0.09 parts by mass of the silane coupling agent (S1) were melt-kneaded at 210°C, and the melt-kneaded product was heated at 210°C under a pressure of 4.9 MPa (50 kgf/cm ² ). Compression molding was performed with pressure for 5 minutes to obtain an ionomer resin sheet 9 having a thickness of 0.8 mm. Table 2 shows the analysis results and evaluation results of the obtained ionomer resin sheet 9.

[Comparative Example 1]
Ionomer resin 10 was obtained in the same manner as in Example 1, except that the temperature of the diluted solution of crude ionomer resin and methanol was changed from 34°C to 43°C. 100 parts by mass of the ionomer resin 10 and 0.10 parts by mass of the silane coupling agent (S1) are melt-kneaded at 210°C, and the melt-kneaded product is heated at 210°C under a pressure of 4.9 MPa (50 kgf/cm ² ). Compression molding was performed with pressure for 5 minutes to obtain an ionomer resin sheet 10 having a thickness of 0.8 mm. Table 2 shows the analysis results and evaluation results of the ionomer resin sheet 10 thus obtained.

[Comparative Example 2]
Ionomer resin 11 was obtained in the same manner as in Example 1, except that the temperature of the diluted solution of crude ionomer resin and methanol was changed from 34°C to 46°C. 100 parts by mass of the ionomer resin 11 and 0.10 parts by mass of the silane coupling agent (S1) were melt-kneaded at 210°C, and the melt-kneaded product was heated at 210°C under a pressure of 4.9 MPa (50 kgf/cm ² ). Compression molding was performed with pressure for 5 minutes to obtain an ionomer resin sheet 11 having a thickness of 0.8 mm. Table 2 shows the analysis results and evaluation results of the obtained ionomer resin sheet 11 .

[Comparative Example 3]
Ionomer resin 12 was prepared in the same manner as in Example 1, except that 220 parts by mass of sulfuric acid (30% by mass) was added instead of hydrochloric acid, and the temperature of the diluted solution of the crude ionomer resin and methanol was changed from 34°C to 50°C. Obtained. 100 parts by mass of the ionomer resin 12 and 0.10 parts by mass of the silane coupling agent (S1) were melt-kneaded at 210°C, and the melt-kneaded product was heated at 210°C under a pressure of 4.9 MPa (50 kgf/cm ² ). Compression molding was performed with pressure for 5 minutes to obtain an ionomer resin sheet 12 having a thickness of 0.8 mm. Table 2 shows the analysis results and evaluation results of the obtained ionomer resin sheet 12 .

[Comparative Example 4]
EMMA3 is used in place of EMMA2, and a granular resin is obtained by reprecipitating a crude ionomer resin solution in a mixed solvent of 500 parts by mass of acetone/water (80/20% by mass) with respect to 100 parts by mass of the crude ionomer resin. Ionomer resin 13 was obtained in the same manner as in Example 1, except that the resulting granular resin was washed three times with a mixed solvent of acetone/water (20/80% by mass). 100 parts by mass of the ionomer resin 13 and 0.10 parts by mass of the silane coupling agent (S2) were melt-kneaded at 210°C, and the melt-kneaded product was heated at 210°C under a pressure of 4.9 MPa (50 kgf/cm ² ). Compression molding was performed with pressure for 5 minutes to obtain an ionomer resin sheet 13 having a thickness of 0.8 mm. Table 2 shows the analysis results and evaluation results of the obtained ionomer resin sheet 13 .

[Comparative Example 5]
EMMA4 was used instead of EMMA2, the amount of methanol solution of sodium hydroxide (20% by mass) was changed from 96 parts by mass to 66 parts by mass, and the amount of hydrochloric acid (20% by mass) was changed from 83 parts by mass to 57 parts by mass. An ionomer resin 14 was obtained in the same manner as in Example 1, except that 100 parts by mass of the ionomer resin 14 and 0.10 parts by mass of the silane coupling agent (S2) were melt-kneaded at 210°C, and the melt-kneaded product was heated at 210°C under a pressure of 4.9 MPa (50 kgf/cm ² ). Compression molding was performed with pressure for 5 minutes to obtain an ionomer resin sheet 14 having a thickness of 0.8 mm. Table 2 shows the analysis results and evaluation results of the obtained ionomer resin sheet 14 .

[Comparative Example 6]
After obtaining ionomer resin 3 in the same manner as in Example 3, 100 parts by mass of ionomer resin 3 was melt-kneaded at 210°C, and the melt-kneaded product was heated at 210°C to 4.9 MPa (50 kgf/cm ² ) for 5 minutes to obtain an ionomer resin sheet 15 having a thickness of 0.8 mm. Table 2 shows the analysis results and evaluation results of the ionomer resin sheet 15 .

[Comparative Example 7]
After obtaining the ionomer resin 3 in the same manner as in Example 3, 100 parts by mass of the ionomer resin 3 and 1.0 parts by mass of the silane coupling agent (S2) were melt-kneaded at 210°C, and the melt-kneaded product was C. and compression molding at a pressure of 4.9 MPa (50 kgf/ ^cm.sup.2 ) for 5 minutes, but an ionomer resin sheet with a gelled and smooth surface could not be obtained.

As shown in Table 2, the ionomer resin compositions obtained in Examples 1 to 9 had a high 1% weight loss temperature (Td1), low water absorption haze and slow cooling haze, and high transparency. It was confirmed that the glass adhesive strength in the state is high. In addition, the resin sheets produced using the ionomer resin compositions obtained in Examples had little black foreign matter and gelled matter, and had good surface smoothness and appearance. In contrast, the ionomer resin compositions obtained in Comparative Examples 1 to 7 exhibited poor results in at least one of the 1% weight loss temperature, water absorption haze, slow cooling haze, and wet state glass adhesion. rice field.

Claims

An ionomer resin composition comprising an ionomer resin and a silane coupling agent,
The ionomer resin contains (meth)acrylic acid units (A), (meth)acrylic acid neutralized units (B) and ethylene units (C), and the total content of the units (A) and the units (B) The amount is 6 to 10 mol% based on the total monomer units constituting the ionomer resin, and the content of the salt composed of a strong acid and a strong base in the ionomer resin is 1 to 400 mg/kg,
The ionomer resin composition, wherein the content of the silane coupling agent is 0.005 to 0.5 parts by mass with respect to 100 parts by mass of the ionomer resin.
The ionomer resin further contains (meth)acrylic acid ester units (D), and the total content of the units (A), the units (B) and the units (D) is the total amount of monomers constituting the ionomer resin. The ionomer resin composition according to claim 1, which is 6 to 10 mol% based on body units.
The ionomer resin composition according to claim 1 or 2, wherein the salt composed of a strong acid and a strong base is a metal salt of an alkali metal and/or an alkaline earth metal.
The salt composed of a strong acid and a strong base contains at least one cation selected from the group consisting of sodium ions and potassium ions and at least one anion selected from the group consisting of halogen ions, nitrate ions and sulfate ions. The ionomer resin composition according to any one of claims 1 to 3, which is a salt consisting of
The silane coupling agent is at least one silane coupling agent selected from the group consisting of amino-based compounds, glycidoxy-based compounds, sulfide-based compounds, mercapto-based compounds, vinyl-based compounds, nitro-based compounds and chloro-based compounds. , the ionomer resin composition according to any one of claims 1 to 4.
The silane coupling agent is at least one silane coupling agent selected from the group consisting of N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane and 3-glycidoxypropylmethyldiethoxysilane. , the ionomer resin composition according to any one of claims 1 to 5.
A resin sheet comprising one or more layers containing the ionomer resin composition according to any one of claims 1 to 6.
A laminated glass intermediate film made of the resin sheet according to claim 7.
A laminated glass comprising two glass plates and the laminated glass intermediate film according to claim 8 arranged between the two glass plates.