Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment

Definitions

• the present invention provides a resin composition comprising a specific ionomer resin and a specific organic compound, a resin sheet having one or more layers containing the resin composition, a laminated glass intermediate film comprising the resin sheet, and the laminate It relates to a laminated glass having a glass interlayer.
• Ionomer resins 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).
• Patent Document 1 the demand for laminated glass has increased, and regardless of the production conditions of laminated glass, laminated glass having a laminated glass intermediate film using an ionomer resin has superior properties (e.g., optical properties and appearance). It is now required to have
• Patent Document 3 describes a resin composition for a molded body in which 1 to 50 parts by mass of a dimer acid is added to 100 parts by mass of an ionomer. It is described that both improvement in fluidity and suppression of bleed-out have been achieved.
• Patent Document 4 describes a method for manufacturing a laminated glass interlayer film using an ionomer, in which the moisture content contained in the laminated glass interlayer film is suppressed to 0.066 wt% or less, and in addition to transparency, It is stated that an improvement in adhesion to glass could also be achieved.
• the resin composition described in Patent Document 3 has insufficient adhesiveness to glass (hereinafter also referred to as "glass adhesiveness") and transparency, and is colored during molding. It has been found that it is difficult to obtain a molded article having an excellent appearance without foaming or streaks because the strength tends to decrease during long-term use.
• the laminated glass interlayer using the ionomer described in Patent Document 4 does not have sufficient adhesion to glass, especially under high humidity conditions, tends to be colored during molding, and loses strength when used for a long time. It was found to be easy to decrease. Accordingly, the problem to be solved by the present invention is to provide a resin composition containing an ionomer resin which is excellent in transparency, color resistance and adhesion to glass.
• a resin composition comprising an ionomer resin containing (meth)acrylic acid units (A), (meth)acrylic acid neutralized units (B), and ethylene units (C), and an organic compound.
• 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 organic compound is a liquid at 23°C.
• 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 organic compound includes toluene, xylene, ethanol, 1-butanol, methacrylic acid, acrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methyl acrylate, ethyl acrylate, and n-acrylate.
• An interlayer film for laminated glass comprising the resin sheet according to [4].
• a laminated glass comprising two glass plates and the laminated glass intermediate film according to claim 5 disposed between the two glass plates.
• a resin composition comprising the ionomer resin of the present invention (hereinafter also referred to as “ionomer resin composition”) comprises (meth)acrylic acid units (A), (meth)acrylic acid neutralized units (B), and It comprises an ionomer resin containing ethylene units (C) and a specific organic compound (hereinafter also referred to as "specific organic compound").
• the organic compound is one organic compound or two or more organic It is a combination of compounds. Moreover, the content of the specific organic compound in the ionomer resin composition is 1 ppm by mass or more and 300 ppm by mass or less.
• ionomer resin may be prone to thermal deterioration.
• a resin sheet or laminated glass is produced using such an ionomer resin, a colored resin sheet or laminated glass is obtained.
• the adhesiveness between the resin sheet and the glass is also poor.
• the inventors of the present invention have investigated the coloring resistance and glass adhesiveness of a resin sheet containing an ionomer resin, and surprisingly found that a resin sheet containing an ionomer resin and a specific organic compound in a specific ratio It was found that an ionomer resin composition having excellent color resistance and high glass adhesion. Although it is not clear why the ionomer resin composition contains a specific organic compound in a specific ratio, the ionomer resin composition is excellent in color resistance and adhesion to glass. It is presumed that this is because the is moderately plasticized.
• the present inventors have unexpectedly found that the ionomer resin composition contains a specific organic compound in a specific ratio, and thus the ionomer resin composition exhibits high adhesion to glass, particularly under high humidity conditions, excellent It was also found that the characteristics of transparency and sufficient creep resistance were exhibited. Generally, ionomer resin compositions containing components other than ionomer resins tend to be inferior to the ionomer resins themselves in adhesion to glass and transparency under high humidity conditions, and also have insufficient creep resistance. Therefore, it was unexpected that the ionomer resin composition of the present invention has the aforementioned features.
• the ionomer resin composition When the content of the specific organic compound is less than 1 ppm by mass, the ionomer resin composition is impaired in color resistance and adhesion to glass. On the other hand, when the content of the specific organic compound exceeds 300 ppm by mass, the transparency (especially the appearance) of the ionomer resin composition tends to decrease. Therefore, for example, a resin sheet obtained from the ionomer resin composition is used as an interlayer film for laminated glass. If so, the design and appearance of the laminated glass may be impaired. In addition, when the content of the specific organic compound exceeds 300 ppm by mass, the creep resistance of the ionomer resin composition tends to decrease. The strength tends to decrease when used for a long time, and there is a possibility of impairing safety. Furthermore, when the content of the specific organic compound exceeds 300 ppm by mass, the coloration resistance and thermal decomposition resistance of the ionomer resin composition tend to decrease.
• the content of the specific organic compound is preferably 2 ppm by mass or more, more preferably 3 ppm by mass or more, and still more preferably 4 ppm by mass or more, from the viewpoint of easily improving color resistance and glass adhesion.
• the content of the specific organic compound is preferably 295 mass ppm or less, more preferably 290 mass ppm or less, still more preferably 285 mass ppm or less, still more preferably 280 mass ppm or less, from the viewpoint of easily increasing transparency and creep resistance. It is mass ppm or less, particularly preferably 275 mass ppm or less.
• the content of the specific organic compound in the ionomer resin composition can be determined by gas chromatography or the like, for example, by the method described in Examples.
• the aromatic compound is not particularly limited, and examples include compounds that are liquid at 23°C, such as toluene, xylene, ethylbenzene, cumene, anisole, benzaldehyde, acetophenone, nitrobenzene, aniline, benzonitrile and styrene.
• aromatic hydrocarbons are preferable, and toluene and/or xylene are more preferable, from the viewpoint of easily improving the color resistance, glass adhesion, transparency and creep resistance of the resulting ionomer resin composition.
• the alcohols are not particularly limited, and examples include primary alcohols, secondary alcohols, and tertiary alcohols. Among these, primary alcohols are preferable, and methanol, ethanol, 1-butanol and mixtures thereof are more preferable, from the viewpoint of easily increasing the color resistance, transparency and creep resistance of the resulting ionomer resin composition. and/or 1-butanol is particularly preferred.
• the organic carboxylic acid is not particularly limited, and includes, for example, monocarboxylic acid, dicarboxylic acid, and tricarboxylic acid.
• monocarboxylic acids are preferable, and methacrylic acid and/or acrylic acid are more preferable, from the viewpoint of easily improving the color resistance, transparency and creep resistance of the resulting ionomer resin composition.
• the organic carboxylic acid ester is not particularly limited, and examples thereof include monocarboxylic acid esters, dicarboxylic acid esters, and tricarboxylic acid esters.
• monocarboxylic acid esters having 4 to 9 carbon atoms are preferable from the viewpoint of easily improving the color resistance, transparency and creep resistance of the resulting ionomer resin composition, and methyl methacrylate and ethyl methacrylate.
• n-butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate and mixtures thereof are more preferred, and methyl methacrylate, methyl acrylate and mixtures thereof are more preferred.
• the specific organic compound is toluene, xylene, ethanol, 1-butanol, methacrylic acid, acrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methyl acrylate, acrylic at least one organic compound selected from the group consisting of ethyl acetate and n-butyl acrylate;
• the ionomer resin in the present invention contains (meth)acrylic acid units (A), (meth)acrylic acid neutralized units (B), and ethylene units (C), and the units (A) and the units (B) is 6 to 10 mol % based on the total monomer units constituting the ionomer resin.
• 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
• the ethylene unit indicates a structural unit derived from ethylene.
• (meth)acrylic acid indicates methacrylic acid or acrylic acid.
• the total content is 6 mol % or more, preferably 6.5 mol % or more, more preferably 6.5 mol % or more, from the viewpoint of easily improving the transparency of the ionomer resin composition (especially the transparency during slow cooling) and the adhesion to glass. is 7.0 mol% or more, more preferably 7.5 mol% or more, and from the viewpoint of easily obtaining more suitable moldability, 10 mol% or less, preferably 9.9 mol% or less, more preferably is 9.5 mol % or less.
• the total content of the units (A) and the units (B) can be adjusted according to the preparation method of the ionomer resin. More specifically, when an ionomer resin is prepared by a method comprising an ethylene-(meth)acrylic acid ester copolymer as a raw material and a saponification reaction step and a demetallization reaction step of the copolymer, ethylene-( Saponification reaction and demetallization reaction for converting (meth)acrylic acid ester units in the meth)acrylic acid ester copolymer into (meth)acrylic acid units (A) and (meth)acrylic acid neutralized units (B) It can be adjusted by each reactivity (conversion rate). Further, as described in US Pat. No.
• 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 glass.
• the (meth)acrylic acid units may be used singly or in combination of two or more.
• 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 %.
• 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.
• the content of the unit (A) is at least the lower limit, the transparency of the ionomer resin composition and the excellent adhesion to glass are likely to be obtained. Moreover, when it is equal to or less than the above upper limit, it is easy to obtain more excellent moldability.
• 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.
• the metal ions include ions of monovalent metals such as lithium, sodium and potassium, and ions of polyvalent metals 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.
• the content of the unit (B) is at least the lower limit, better transparency and elastic modulus are likely to be obtained, and when it is at most the upper limit, an increase in melt viscosity during molding is suppressed. easy to be
• 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.
• the (meth)acrylic acid ester unit in the ethylene-(meth)acrylic acid ester copolymer is replaced with the (meth)acrylic acid unit (A) and the (meth)acrylic acid neutralized product unit (B ) can be adjusted by each reactivity of the saponification reaction and the demetallization reaction.
• the content of the ethylene unit (C) is based on the total monomer units constituting the ionomer resin, and the mechanical strength (especially impact resistance) of the ionomer resin composition can be easily increased, and excellent moldability can be obtained. From the viewpoint of easy cooling, it is preferably 80 mol% or more, more preferably 85 mol% or more, and still more preferably 88 mol% or more, and the transparency of the ionomer resin composition (especially the transparency during slow cooling) is easy to increase. From the viewpoint, it is preferably 94 mol % or less, more preferably 92 mol % or less.
• ⁇ (Meth) acrylic acid ester unit (D)> The ionomer resin in the present invention, in addition to the (meth)acrylic acid unit (A), the (meth)acrylic acid neutralized unit (B), and the ethylene unit (C), from the viewpoint of easily obtaining higher transparency, Furthermore, it is preferable that the (meth)acrylic acid ester unit (D) is included.
• 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) increases the transparency (especially during slow cooling). transparency), it is preferably 6 to 10 mol % based on the total monomer units constituting the ionomer resin.
• the ionomer resin in the present invention comprises (meth)acrylic acid units (A), (meth)acrylic acid neutralized units (B), ethylene units (C), and ( Including the meth)acrylic acid ester unit (D), the total content of the unit (A), the unit (B) and the unit (D) is 6 based on the total monomer units constituting the ionomer resin. ⁇ 10 mol%.
• 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 not more than the upper limit, the ionomer resin composition It is easy to suppress the increase in the melt viscosity during the molding process of the product, and thereby, it is easy to obtain the ionomer resin composition with better moldability. Further, when the total content is at least the lower limit, it is easy to obtain higher transparency of the ionomer resin composition (especially transparency during slow cooling).
• the total content of the units (A), the units (B) and the units (D) provides higher transparency (especially slow cooling 6 mol% or more, preferably 6.5 mol% or more, more preferably 7.0 mol% or more, still more preferably 7.5 mol%
• the content 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 prepared by a method including a saponification reaction step and a demetallization reaction step of the copolymer, the ionomer resin It can be adjusted by the (meth)acrylic acid ester modification amount of the raw material ethylene-(meth)acrylic acid ester copolymer. Further, as described in US Pat. No.
• 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, and (meth)acrylic acid allyl and the like.
• preferred monomers from the viewpoint of transparency or heat resistance are methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ( n-butyl meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, and t-butyl (meth)acrylate, 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 ( Methyl meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate, and a particularly preferred monomer is methyl (meth)acrylate. These monomers may be used
• the content of the (meth)acrylic acid ester units (D) in the ionomer resin is not particularly limited.
• 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.
• the content of the unit (D) is at least the lower limit and at most the upper limit, higher transparency of the ionomer resin composition can be easily obtained.
• 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 preparing an ionomer resin by a method including a demetallization reaction step, the (meth)acrylic acid ester units in the ethylene-(meth)acrylic acid ester copolymer are converted to (meth)acrylic acid units (A) It can be adjusted by the reactivity of the saponification reaction.
• the ionomer resin in 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 (A2) other than the (meth)acrylic acid unit (A), and a neutralized carboxylic acid unit other than the (meth)acrylic acid neutralized unit (B). (B2) and the like.
• Examples of monomers constituting the carboxylic acid unit (A2) include itaconic acid, maleic anhydride, monomethyl maleate, and monoethyl maleate, with monomethyl maleate and monoethyl maleate being preferred.
• Examples of the monomer constituting the neutralized carboxylic acid unit (B2) include neutralized units of the neutralized carboxylic acid unit (A2).
• 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.
• the total content thereof for example the total content of (A2) and (B2), may be appropriately selected within a range that does not impair the effects of the present invention.
• 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 in the present invention and (meth)acrylic acid ester units when included ( D) and other monomeric unit contents (e.g., unit (A2) and unit (B2)) are determined by first identifying the monomeric units in the ionomer resin in the ionomer resin composition by pyrolysis gas chromatography. and then determined by using nuclear magnetic resonance 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 reprecipitation or Soxhlet extraction.
• NMR nuclear magnetic resonance spectroscopy
• the content of the ionomer resin is preferably 90% by mass or more, more It is preferably 95% by mass or more, 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 or less.
• the degree of branching per 1000 carbon atoms of the ionomer resin of the present invention is not particularly limited, and is preferably 5-30, more preferably 6-20.
• the degree of branching is determined by the temperature at which the ionomer resin is polymerized, for example, an ethylene-(meth)acrylic acid ester copolymer is used as a raw material, and the ionomer resin is obtained by a method including a saponification reaction step and a demetallization reaction step of the copolymer. can be adjusted by the polymerization temperature when preparing the ethylene-(meth)acrylic acid ester copolymer.
• the degree of branching per 1000 carbons can be measured by the DDMAS method using solid-state NMR.
• the melting point of the ionomer resin is preferably 50°C or higher, more preferably 60°C or higher, and even more preferably 80°C or higher, from the viewpoint of heat resistance and thermal decomposition resistance.
• the melting point is preferably 200° C. or lower, more preferably 180° C. or lower, and even more preferably 150° C. or lower, from the viewpoint of easily exhibiting adhesive strength with glass when producing laminated glass.
• the melting point can be measured based on JIS K7121:2012.
• DSC differential scanning calorimeter
• 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.
• DSC differential scanning calorimeter
• the MFR of the ionomer resin measured under the conditions of 190°C and 2.16 kg according to JIS K7210 is preferably 0.1 g/10 min or more, more preferably 0.3 g/10. minutes or more, more preferably 0.7 g/10 minutes or more, still more preferably 1.0 g/10 minutes or more, particularly preferably 1.5 g/10 minutes or more, preferably 50 g/10 minutes or less, more preferably 50 g/10 minutes or more. 30 g/10 minutes or less, particularly preferably 10 g/10 minutes or less.
• the MFR of the ionomer resin is not less than the lower limit and not more 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 the (meth)acrylic acid ester unit (D) optionally included.
• the ionomer resin composition in the present invention may further contain additives, if necessary.
• additives that may optionally be included include UV absorbers, anti-aging agents, antioxidants, thermal degradation inhibitors, light stabilizers, anti-adhesive agents, lubricants, release agents, polymer processing aids, Examples include antistatic agents, flame retardants, dyes, pigments, organic dyes, matting agents, and phosphors.
• 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.
• the additives contained 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, with respect to the total mass of the ionomer resin composition, It is preferably 7% by mass or less, more preferably 5% by mass or less, and even more preferably 4% by mass or less.
• the various additives may be added when manufacturing the ionomer resin composition, may be added after manufacturing the ionomer resin composition, or may be added when manufacturing the resin sheet described below.
• the ionomer resin composition in the present invention may have a shape such as pellets in order to improve convenience during storage, transportation, or molding.
• the pelletization can be carried out, for example, by cutting strands obtained by a melt extrusion method.
• the temperature of the ionomer resin composition during pelletization by 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.
• the temperature is preferably 250° C. or lower, more preferably 230° C. or lower, from the viewpoint of easily suppressing thermal decomposition and deterioration of the ionomer resin. Since the ionomer resin composition of the present invention has high thermal decomposition resistance, the ionomer resin is less likely to be thermally decomposed and changed in properties when it is pelletized by the melt extrusion method.
• the ionomer resin composition of the present invention can be prepared, for example, by (1) a method comprising producing an ionomer resin and mixing the resulting ionomer resin with a specific organic compound, or (2) It can be produced by a method comprising leaving the compound and optionally mixing the obtained mixture (composition) of the residual specific organic compound and ionomer resin with a further specific organic compound.
• Method (1) is preferable from the viewpoint of ease of adjusting the ratio of the specific organic compound to a desired value and from the viewpoint of productivity.
• the manufacturing method of the ionomer resin is not particularly limited.
• (I) a step of saponifying an ethylene-(meth)acrylic acid ester copolymer (X) as a raw material (saponification step), and a step of demetallizing at least part of the obtained saponified product (demetallization and (II) a step of copolymerizing ethylene and (meth)acrylic acid as raw materials (copolymerization step), and a step of partially neutralizing the resulting copolymer (partial neutralization step), and the like.
• the production method described in US Pat. No. 8,399,096 can be referred to.
• Method (I) is preferable from the viewpoint of easily adjusting the ratio of the specific organic compound to a desired value. This method (I) will be described in detail below.
• the ethylene-(meth)acrylic acid ester copolymer (X) as a raw material is dissolved in an organic solvent to obtain an ethylene-(meth)acrylic acid ester copolymer (X) solution.
• step i) all or part of the (meth)acrylic acid ester units of the ethylene-(meth)acrylic acid ester copolymer (X) in the resulting solution are neutralized with (meth)acrylic acid by a saponification reaction; to obtain a saponified product of ethylene-(meth)acrylic acid ester copolymer (X) (step ii, saponification step), and subjecting the obtained saponified product to a demetallization reaction to obtain (meth) At least part of the neutralized acrylic acid units (B) are converted to (meth)acrylic acid units (A) to obtain a crude ionomer resin composition containing an ionomer resin and a specific organic compound (step iii, demetallization step) and separating and purifying the crude ionomer resin composition (step iv).
• Examples of monomers constituting the (meth)acrylate units of the ethylene-(meth)acrylate copolymer (X) include methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylate.
• n-propyl acrylate isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, (meth)acrylate 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 g
• preferred monomers are methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, ( Isobutyl meth)acrylate, sec-butyl (meth)acrylate, and t-butyl (meth)acrylate, more preferred monomers are methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylate, ) n-propyl acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate, and more preferred monomers are methyl (meth)acrylate, (meth) They are n-butyl acrylate and isobutyl (meth)acrylate, and a particularly preferred monomer is methyl (meth)acrylate.
• the monomers may be used
• ethylene-(meth)acrylic acid ester copolymer (X) examples 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.
• copolymer (X) a commercially available product may be used, or one 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 "Rekspearl” (registered trademark) A4250 manufactured by Nippon Polyethylene Co., Ltd., and the like.
• 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 the (meth)acrylic acid ester units in the copolymer (X) is the (meth)acrylic acid unit (A) in the ionomer resin in the resulting crude ionomer resin composition and the ionomer resin in the ionomer resin composition.
• 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.
• 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 (A2) and units (B2)), pyrolysis gas chromatography, nuclear magnetic resonance spectroscopy (NMR) and It can be determined by elemental analysis.
• acrylic acid ester units (D) and other monomeric units e.g. units (A2) and units (B2)
• NMR nuclear magnetic resonance spectroscopy
• 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.
• MFR of the ethylene-(meth)acrylic acid ester copolymer (X) is at least the lower limit and at most the upper limit, more suitable moldability and higher strength of the resulting ionomer resin composition are likely to be obtained. .
• 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 It is preferably 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.
• 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 performing a 13 C-NMR inverse gate decoupling method using an ethylene-(meth)acrylate copolymer (X) dissolved in deuterated ortho-dichlorobenzene. .
• the organic solvent for dissolving the ethylene-(meth)acrylate copolymer (X) is not particularly limited as long as it can dissolve the copolymer (X).
• examples thereof include ethers such as tetrahydrofuran and dioxane; halogen-containing solvents such as chloroform and dichlorobenzene; ketones having 6 or more carbon atoms such as methyl butyl ketone; hydrocarbon compounds such as hexane; Acetic esters; Mixed solvents of hydrocarbon compounds and alcohols such as methanol, ethanol, 1-propanol, 2-propanol and 1-butanol; Aromatic compounds such as benzene, toluene, xylene and ethylbenzene; Aromatic compounds and alcohols and a mixed solvent with These solvents may be used alone or in combination of two or more. Among these, aromatic compounds or mixed solvents of aromatic compounds and alcohols are preferred, and aromatic compounds are more preferred, from the viewpoints of solubility, recovery
• the content of the copolymer (X) in the ethylene-(meth)acrylate copolymer (X) solution obtained in step i) is preferably 5% by mass or more, more preferably 10% by mass or more, It is more preferably 20% by mass or more, preferably 80% by mass or less, more preferably 60% by mass or less, and even more preferably 40% by mass or less.
• the content is equal to or less than the upper limit, the processability tends to be good, and the reaction is easy to control.
• the productivity tends to be high.
• the temperature at which the ethylene-(meth)acrylate copolymer (X) is dissolved in the organic solvent in step i) is not particularly limited. From the viewpoint of the solubility of the ethylene-(meth)acrylic acid ester copolymer (X), the temperature is preferably 30° C. or higher, more preferably 40° C. or higher, still more preferably 50° C. or higher, and particularly preferably 55° C. or higher.
• the upper limit of the temperature is preferably 120° C. or lower, more preferably 100° C. or lower, and even more preferably 80° C. or lower.
• Step i) may be performed in the air or in an inert gas such as nitrogen gas or argon gas.
• step i) may be carried out under normal pressure, increased pressure or reduced pressure, preferably under increased pressure.
• the copolymer (X) is saponified by mixing the ethylene-(meth)acrylate copolymer (X) solution obtained in step i) with a base.
• the saponification reaction all or part of the (meth)acrylic acid ester units in the ethylene-(meth)acrylic acid ester copolymer (X) are converted to neutralized (meth)acrylic acid units, and (meth)acrylic
• a saponified product of an ethylene-(meth)acrylate copolymer (X) containing acid-neutralized units (B), ethylene units (C) and optionally (meth)acrylate units (D) is obtained.
• bases used for saponification include strong bases such as sodium hydroxide, potassium hydroxide, and calcium hydroxide.
• a base may be used alone or in combination of two or more.
• Sodium hydroxide and/or potassium hydroxide are preferred from the viewpoints of solubility in the organic solvent contained in the ethylene-(meth)acrylate copolymer (X) solution and economic efficiency.
• the amount of the base to be added is preferably 100 to 300 mol parts, more preferably 120 to 250 mol parts, per 100 mol parts of the (meth)acrylic acid ester units of the ethylene-(meth)acrylic acid ester copolymer (X). parts, more preferably 150 to 200 molar parts.
• Examples of the solvent used for saponification include solvents similar to the organic solvent for dissolving the ethylene-(meth)acrylic acid ester copolymer (X) in step i).
• preferred solvents are mixed solvents of hydrocarbon compounds and alcohols, and mixed solvents of aromatic compounds and alcohols, and more preferred solvents are toluene and the like.
• the ratio of the hydrocarbon compound or aromatic compound and alcohol in the mixed solvent may be appropriately selected according to the type of each solvent used.
• the mass ratio of the hydrocarbon compound or aromatic compound and alcohol ( hydrocarbons 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, further preferably 60° C. or higher, from the viewpoint of the reactivity and the solubility of the ethylene-(meth)acrylic acid ester copolymer (X). is 70° C. or higher, particularly preferably 80° C. or higher.
• the upper limit of the temperature is preferably 180° C. or lower, more preferably 150° C. or lower, still more preferably 120° C. or lower.
• the saponification reaction may be performed in 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.
• Step iii) By mixing the saponified product obtained in step ii) with an acid, the saponified product is subjected to a demetallization reaction. At least a part (step iii-1) or all of (step iii-1) or all (step iii-2) is converted to a (meth)acrylic acid unit (A).
• acids used for the demetallization reaction include weak acids such as acetic acid and strong acids such as hydrochloric acid, nitric acid, sulfuric acid, and toluenesulfonic acid.
• strong acids are preferred, and inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid are more preferred, from the viewpoint of facilitating washing and removal of salts produced from the base used in the saponification reaction and the acid used in the demetalization reaction.
• the same solvent as the solvent used for the saponification reaction in step ii) can be selected.
• the amount of acid added can be selected appropriately according to the amount of strong base added in order to adjust the (meth)acrylic acid neutralized unit (B) to an arbitrary value.
• the temperature at which demetallization is performed is preferably 20° C. or higher, more preferably 30° C. or higher, still more preferably 40° C. or higher, and preferably 180° C. or lower. It is preferably 150° C. or lower, more preferably 120° C. or lower, particularly preferably 100° C. or lower.
• Demetallization may be performed in the air or in an inert gas such as nitrogen gas or argon gas. Moreover, demetallization may be performed under normal pressure, under pressure, or under reduced pressure, preferably under pressure.
• step iii-2 that is, by demetallization reaction, all of the (meth)acrylic acid neutralized product units (B) in the saponified product of ethylene-(meth)acrylic acid ester copolymer (X) are When converting to (meth)acrylic acid units (A), in step iii-2), part of the (meth)acrylic acid units (A) obtained by demetallization is neutralized with metal ions ( Further comprising converting to meth)acrylic acid neutralized units (B).
• the neutralizing agent used in this neutralizing step is not particularly limited as long as it is an ionic compound containing metal ions.
• the metal ions include ions of alkali metals such as lithium, potassium and sodium, ions of alkaline earth metals such as magnesium and calcium, ions of transition metals such as zinc, nickel, iron and titanium, and aluminum ions. mentioned.
• examples of neutralizing agents include sodium hydroxide, sodium acetate, sodium bicarbonate, and the like. Polymers such as ionomer resins containing sodium (meth)acrylate units can also be used as the neutralizing agent.
• Step iii a crude ionomer resin composition containing an ionomer resin and a specific organic compound is separated from the resulting reaction solution and purified to obtain an ionomer resin in the present invention (in the case of method (1)) or The ionomer resin composition of the present invention (in the case of method (2) above) can be obtained. Separation and purification may be carried out by conventional methods such as filtration, washing, concentration, reprecipitation, recrystallization, silica gel columnography and the like.
• the separation and purification is performed from the viewpoint of easily washing and removing a salt (hereinafter also referred to as a "by-product salt”) that may be produced as a by-product from the base used in the saponification reaction and the acid used in the demetalization reaction.
• a poor solvent is added to the solution of the crude ionomer resin composition to precipitate particles containing the ionomer resin, the by-product salt and the specific organic compound (hereinafter also simply referred to as "granules”), and then the precipitated particles are separated. It is preferably carried out by washing with a washing liquid.
• a solution of the crude ionomer resin composition can be prepared by dissolving the crude ionomer resin composition obtained after step iii) in a solvent.
• the reaction solution after the demetallization step (step iii-1) or the reaction solution after the neutralization step (step iii-2) obtained in step iii) may be used as the solution of the crude ionomer resin composition.
• the solvent in the solution of the crude ionomer resin composition is not particularly limited as long as it is capable of dissolving the crude ionomer resin composition, and the same solvents as those used in the saponification reaction are exemplified.
• a mixed solvent of an aromatic compound such as toluene and an alcohol such as methanol is preferable from the viewpoint of the solubility of the crude ionomer resin composition.
• 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.
• 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 crude ionomer resin composition in the solution of the crude ionomer resin composition is preferably 30% by mass or less, more preferably 15% by mass, from the viewpoints of facilitating the production of granules with a small particle size and facilitating the removal of by-product salts. %, preferably 1% by mass or more, more preferably 5% by mass or more.
• the temperature of the solution of the crude ionomer resin composition is preferably not higher than the melting point of the ionomer resin, more preferably 60° C., from the viewpoints of easily suppressing aggregation or agglomeration of precipitated particles and easily removing by-product salts. 50° C. or less, more preferably 50° C. or less. From the viewpoint of fluidity of the solution of the crude ionomer resin composition, the temperature is more preferably 25° C. or higher, more preferably 30° C. or higher.
• the poor solvent added to the solution of the crude ionomer resin composition is not particularly limited as long as it is mixed with the solution of the crude ionomer resin composition and does not dissolve the ionomer resin.
• examples thereof include alcohols such as methanol, ethanol, 1-propanol, 2-propanol and 1-butanol; water; ketones such as acetone and methyl ethyl ketone; esters such as methyl acetate and ethyl acetate; ethers such as tetrahydrofuran; and hydrocarbon compounds such as n-hexane, cyclohexane, heptane, and the like. These may be used alone or in combination of two or more.
• the poor solvent is preferably methanol, 2 - Alcohols such as propanol, 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 solution of the crude ionomer resin composition.
• the amount of the poor solvent 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 solution of the crude ionomer resin composition.
• the upper limit of the amount of the poor solvent to be added is not particularly limited, and the upper limit of the amount of the poor solvent to be added is usually 1000 parts by mass or less with respect to 100 parts by mass of the solution of the crude ionomer resin composition.
• the method of adding the poor solvent to the solution of the crude ionomer resin composition is not particularly limited. may be added.
• the particle diameter of the granules is likely to be reduced, thereby easily improving the removability of the by-product salt, and as a result, from the viewpoint of easily improving the transparency of the resin sheet formed from the resulting ionomer resin composition.
• the addition of the poor solvent is preferably completed within 1 hour, more preferably within 30 minutes, and even more preferably within 10 minutes.
• the stirring speed is not particularly limited, but the faster the stirring speed, the easier it is to obtain granular particles with a smaller particle size.
• the stirring time is not particularly limited. Seconds or more and 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.
• the peak top particle size of the granules precipitated by adding a poor solvent to the solution of the crude ionomer resin composition is determined from the viewpoint that by-product salts in the granules can be easily removed by increasing the specific surface area of the granules. From the viewpoint of facilitating almost complete removal of the specific organic compound in the particulate matter (below the detection limit), the particle size is 700 ⁇ m or less, preferably 650 ⁇ m or less, more preferably 600 ⁇ m or less, and even more preferably 550 ⁇ m or less.
• the ionomer resin composition From the viewpoint of easily improving the filterability of the particulate matter and easily improving the production efficiency of the ionomer resin composition, it is preferably 50 ⁇ m or more, more preferably 70 ⁇ m or more, and preferably 80 ⁇ m or more.
• the peak top particle size can be measured, for example, by a laser diffraction/scattering method or a single light scattering method.
• the peak top particle size of the particulate material precipitated by adding a poor solvent to the solution of the crude ionomer resin composition can be adjusted by the concentration and temperature of the solution of the crude ionomer resin composition. Specifically, when the concentration and/or temperature of the solution of the crude ionomer resin composition are lowered, the peak top particle size of the precipitated particulate matter can be reduced, and the concentration and/or temperature of the solution of the crude ionomer resin composition is increased. Then, the peak top particle size of the precipitated particulate matter can be increased.
• the peak top particle size of the particulate matter can also be adjusted by the method of adding the poor solvent and the stirring speed of the mixture of the crude ionomer resin composition solution and the poor solvent.
• the cleaning liquid for cleaning the precipitated particulate matter is not particularly limited as long as it is a solvent in which the ionomer resin or the ionomer resin composition is not dissolved.
• 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 alone or in combination of two or more.
• washing liquids alcohols, water, and mixed liquids thereof are preferable from the viewpoint of easy removal of by-product salts and specific organic compounds. Furthermore, by making the specific gravity of the cleaning liquid smaller than that of the particulate matter, the contact area between the cleaning liquid and the particulate matter is increased, thereby making it easier to improve the removability of the by-product salt. From the viewpoint of facilitating adjustment of the content of the specific organic compound within the desired range, and/or from the viewpoint of facilitating drying of the ionomer resin or ionomer resin composition obtained after washing, a more preferable washing liquid is water and alcohols.
• 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. .
• Examples of the method of washing the particulate matter with a washing liquid include a method of filtering the particulate matter from the granular matter dispersion liquid in which the particulate matter is precipitated, mixing the filtered particulate matter with the washing liquid, and then draining the liquid. . More specifically, after mixing the granules filtered from the particulate dispersion and the washing liquid, the granules are filtered from the washing liquid (hereinafter also referred to as washing step (a)), and then the filtered granules There is a method of washing by mixing the substance with a fresh washing liquid and then filtering the particulate matter from the washing liquid (hereinafter also referred to as washing step (b)).
• the particulate matter is washed in a batch process, for example, after one washing step (a). It is preferred to carry out step (b) preferably 1 to 10 times, more preferably 1 to 8 times, even more preferably 1 to 6 times.
• the content of the organic carboxylic acid and/or organic carboxylic acid ester (specific organic compound) in the granules can be adjusted by the number of washings.
• the washing step (b) preferably 4 to 10 times, more preferably 6 to 8 times, the content of the organic carboxylic acid and/or organic carboxylic acid ester in the granules after washing is reduced to 1 mass can be adjusted to less than ppm.
• the washing step (b) preferably 1 to 3 times, more preferably 1 to 2 times, the content of the organic carboxylic acid and/or organic carboxylic acid ester in the washed granules can be reduced to It can be adjusted to 1 mass ppm or more and 300 mass ppm.
• the amount of the cleaning liquid used in one cleaning step may be appropriately selected according to the amount of granular material to be cleaned.
• the amount of the cleaning liquid used in one cleaning process 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 material. is 300 parts by mass to 700 parts by mass.
• the temperature is preferably below the melting point of the ionomer resin, more preferably below 80°C.
• drying may be carried out under normal pressure, under pressure, or under reduced pressure, preferably under reduced pressure.
• the content of aromatic compounds and/or alcohols (specific organic compounds) in the granules can be adjusted by the drying conditions. For example, by drying under vacuum for 24 hours or more, the content of aromatic compounds and/or alcohols in the dried granules can be adjusted to less than 1 ppm by mass. Further, for example, by drying under vacuum for 1 hour to about 8 hours, the content of aromatic compounds and/or alcohols in the dried granules can be adjusted to 1 mass ppm or more and 300 mass ppm. .
• the content of the specific organic compound in the granules can be adjusted by mixing the granules after drying with the specific organic compound as necessary. From the viewpoint of easy adjustment of the content of the specific organic compound to the desired value, and from the viewpoint of productivity and quality stability, the content of the specific organic compound in the dried granules is substantially zero (e.g.
• a mixing method is not particularly limited. For example, it may be mixed using a batch melt kneader, a vented single screw extruder, or a vented twin screw extruder.
• the mixing temperature is preferably 220° C. or lower, more preferably 210° C.
• the mixing temperature is preferably 160° C. or higher, more preferably 170° C. or higher, and even more preferably 180° C. or higher, from the viewpoint of productivity.
• the dispersion state of the specific organic compound in the ionomer resin composition is not particularly limited, it is preferably dispersed uniformly in the ionomer resin composition from the viewpoint of easily obtaining the better effects of the present invention. Therefore, mixing is preferably carried out until a homogeneous ionomer resin composition is obtained.
• the ionomer resin composition of the present invention has excellent transparency.
• the haze of the sheet of the ionomer resin composition of the present invention at a thickness of 0.8 mm is preferably 2.0% or less, more preferably 1.5% or less, still 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%.
• the haze of the ionomer resin composition is measured using, for example, a haze meter according to JIS K7136:2000.
• 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. Also, the resin is difficult to crystallize.
• the ionomer resin composition of the present invention containing such an ionomer resin can have high transparency even in a state in which crystallization of the ionomer resin is promoted by slow cooling.
• the haze (gradual cooling haze) of the ionomer resin composition in the present invention in a state in which crystallization of the ionomer resin is promoted by slow cooling is preferably 5.0% or less, more preferably 4.5% or less, and even more preferably 4.5% or less. is 4.0% or less, 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%.
• Slow-cooling haze is obtained by disposing a sheet of an ionomer resin composition having a thickness of 0.8 mm between two glass plates to prepare a laminated glass, heating the laminated glass to 140 ° C., and then reducing the haze from 140 ° C.
• the haze after slowly cooling to 23°C at a rate of 1/min can be measured by measuring with a haze meter in accordance with JIS K7136:2000.
• the ionomer resin composition of the present invention has excellent color resistance and is less likely to be colored during molding.
• the yellowness index (YI) at a sheet thickness of 0.8 mm of the ionomer resin composition of the present invention is preferably 1.1 or less, more preferably 0.9 or less, and still more preferably 0.9 or less, from the viewpoint of easily improving color resistance. is 0.7 or less. Since the color resistance of the ionomer resin composition increases as the yellowness index (YI) decreases, the lower limit value 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, for example, by the method described in Examples.
• the adhesion between the ionomer resin composition of the present invention and glass can be evaluated by the peel energy between the ionomer resin composition and glass measured by a peel test.
• the peel energy between the ionomer resin composition and glass measured under standard conditions is preferably 2.0 kJ/m 2 or more, more preferably 2.5 kJ/m 2 or more, and still more preferably is at least 3.0 kJ/m 2 , particularly preferably at least 3.5 kJ/m 2 .
• the adhesion between the ionomer resin composition and glass under high humidity conditions can be evaluated by the peel energy between the ionomer resin composition and glass measured by a peel test under wet conditions.
• This peeling energy is preferably 0.05 kJ/m 2 or more, more preferably 0.10 kJ/m 2 or more, still more preferably 0.15 kJ/m 2 or more, still more preferably 0.17 kJ/m 2 or more, especially It is preferably 0.20 kJ/m 2 or more.
• the upper limit of the peeling energy under standard conditions and high humidity conditions is not particularly limited, and may be 10 kJ/m 2 or less.
• the peel test can be carried out, for example, by the method described in WO 2019-027865 as a peel adhesion measurement method.
• the peel energy measured under the standard conditions and wet conditions can be measured, for example, by the method described in the Examples.
• the ionomer resin composition of the present invention has sufficient creep resistance. Therefore, when a resin sheet having one or more layers containing the ionomer resin composition of the present invention, which will be described later, is used as an interlayer for laminated glass, the strength is unlikely to decrease even after long-term use, ensuring safety. Cheap.
• the creep resistance of the ionomer resin composition is determined by the relaxation modulus after a long period of time (long-term relaxation modulus), for example, 2.6 ⁇ 10 6 seconds (about 1 month) after creating a master curve at 50°C. ) can be evaluated by the relaxation modulus. In one embodiment of the present invention, the relaxation modulus after 2.6 ⁇ 10 6 seconds when creating a master curve at 50° C.
• the relaxation modulus is preferably 0.00, from the viewpoint of easily increasing the creep resistance of the ionomer resin composition. It is 40 MPa or more, more preferably 0.45 MPa or more, and still more preferably 0.50 MPa or more.
• the relaxation modulus may be 5.0 MPa or less, preferably 2.5 or less, from the viewpoint of handleability of the resin sheet.
• the relaxation modulus of elasticity is measured by dynamic viscoelasticity measurement using a dynamic viscoelasticity measuring device after allowing a resin sheet made of the ionomer resin composition to stand in an atmosphere of 23° C. and 50% RH for one week or longer. It can be obtained from a synthetic curve (referred to as a master curve) at a reference temperature of 50° C. obtained from the time-temperature conversion rule, and can be obtained, for example, by the method described in Examples.
• the present invention also relates to a resin sheet having one or more layers containing the ionomer resin composition of the present invention (hereinafter also referred to as layer (x)).
• layer (x) is composed of the ionomer resin composition of the invention.
• the resin sheet of the present invention may be composed of only one layer (x), or may be a laminate containing at least one layer (x).
• the structure of the laminate is not particularly limited. Examples thereof include a laminate consisting of two or more layers (x), a laminate including one or more layers (x) and one or more other layers, and the like. When the laminate includes multiple layers (x) or multiple other layers, the resin or resin composition that constitutes each layer (x) or each other layer may be the same or different.
• a layer containing a known resin can be used as the other layer.
• 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, Examples include polysulfone, polyethersulfone, polyarylate, liquid crystal polymer, polyimide, and thermoplastic elastomer.
• the other layer may include the additives exemplified in the section [Additives] above, as well as a plasticizer, a heat-shielding material (for example, inorganic heat-shielding fine particles having infrared absorption ability or an organic It may contain one or more additives such as heat shielding materials) and functional inorganic compounds.
• a heat-shielding material for example, inorganic heat-shielding fine particles having infrared absorption ability or an organic It may contain one or more additives such as heat shielding materials
• functional inorganic compounds for example, a plasticizer, a plasticizer, a plasticizer, a heat-shielding material (for example, inorganic heat-shielding fine particles having infrared absorption ability or an organic It may contain one or more additives such as heat shielding materials) and functional inorganic compounds.
• At least one surface, preferably both surfaces, of the resin sheet of the present invention is coated with a melt from the viewpoint of excellent defoaming properties when the resin sheet and glass are thermocompression bonded. It is preferable to have an uneven structure imparted by a conventionally known method such as a fracture method or an embossing method.
• the shape of the melt fracture and emboss is not particularly limited, and conventionally known shapes may be appropriately selected.
• 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.
• the thickness of each layer (x) 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 in the state of being wound into a roll, or may be in the state of individual sheets.
• the content of the ionomer resin composition of the present invention contained in the resin sheet of the present invention is adjusted from the viewpoint of easily increasing the transparency, color resistance and creep resistance of the resulting resin sheet. It is preferably 90% by mass or more, more preferably 93% by mass or more, still more preferably 95% by mass or more, still more preferably 98% by mass or more, and preferably 100% by mass or less based on the mass of the resin sheet. .
• the resin sheet of the present invention Due to the properties of the ionomer resin composition of the present invention, the resin sheet of the present invention has transparency, transparency during slow cooling, color resistance, adhesion to glass (under standard conditions and wet conditions), and excellent resistance to thermal decomposition and sufficient creep resistance.
• the resin sheet of the present invention has the same haze, slow cooling haze, yellowness, adhesion to glass, thermal decomposition resistance and creep resistance as those of the ionomer resin composition of the present invention. have.
• the method for producing the resin sheet of the present invention is not particularly limited.
• 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.
• two or more layers (x), or one or more layers (x) and one or more other layers are laminated by press molding or the like to obtain a laminate, or two At least one layer (x), or at least one layer (x) and at least one other layer may be formed by a coextrusion method to obtain a laminate, and this laminate may be used as a resin sheet. good.
• the laminate includes multiple layers (x) or multiple other layers, the resin or resin composition that constitutes each layer (x) or each other layer may be the same or different.
• the resin temperature or the resin composition 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 temperature 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.
• the resin sheet of the present invention can be suitably used as an intermediate film for laminated glass (also 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 and color resistance, and has excellent adhesiveness between the intermediate film and the glass.
• Examples of the glass plate to be laminated with the interlayer film of the present invention include inorganic glass such as float glass, polished plate glass, figured glass, wired plate glass, and heat-absorbing plate glass, as well as conventionally known organic glass such as polymethyl methacrylate and polycarbonate. Glass or the like may be used. They may be either colorless or colored. These may use 1 type and may use 2 or more types together. 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.
• the laminated glass of the present invention can be produced by a conventionally known method. Examples thereof include a method using a vacuum laminator device, a method using a vacuum bag, a method using a vacuum ring, and a method using a nip roll. Moreover, after crimping
• a vacuum laminator device 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, adhesiveness A laminated glass can be manufactured by laminating a resin layer, etc.).
• a method using a vacuum bag or a vacuum ring is described, for example, in EP 1235683 , wherein a glass plate and a A laminated glass can be produced by laminating the intermediate film.
• 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.
• the operating conditions of the autoclave process are appropriately selected depending on the thickness and/or structure of the laminated glass. is preferably treated for 0.5 to 3 hours.
• the laminated glass of the present invention Due to the properties of the ionomer resin composition of the present invention, the laminated glass of the present invention has transparency, transparency during slow cooling, color resistance, and adhesion to glass (under standard conditions and under wet conditions). and has sufficient creep resistance. In a preferred embodiment of the present invention, the laminated glass of the present invention has haze, slow cooling haze, yellowness, adhesion to glass, and creep resistance equivalent to those of the ionomer resin composition of the present invention.
• the neutralized (meth)acrylic acid unit (B) was converted to the (meth)acrylic acid unit (A). Then, after thoroughly washing with water and drying, the following (1) to (3) were carried out.
• (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.
• 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.
• Headspace conditions heating temperature 120 ° C., heating time 30 minutes GC conditions: column; DB-WaxUI (30 m-0.25 mm-0.5 ⁇ m), oven; after holding at 40 ° C. for 5 minutes, 240 at 10 ° C./min C. and held at 240.degree. C. for 15 minutes, inlet: 200.degree. C., split injection (20:1) Measurement was performed five times in succession, and the total peak area of the target component was obtained by simulation from the obtained data. Compounds that did not reach gas-solid equilibrium under the above conditions were quantified by a one-point calibration method from the peak area obtained from the first measurement.
• Water content in ionomer resin composition and resin sheet The water content of the ionomer resin composition and the resin sheet obtained in Comparative Example 2 was quantified by the Karl Fischer titration method. Specifically, using a moisture vaporizer VA-121 (manufactured by Mitsubishi Chemical Corporation) and a trace moisture content analyzer CA-200 (manufactured by Mitsubishi Chemical Corporation), 1 g of each sample was placed on a quartz cell in the furnace of the moisture vaporizer. The water vapor generated during heating at 200° C. was introduced into the electrolysis cell of the trace moisture content measuring device by nitrogen gas, and the moisture content was measured.
• VA-121 manufactured by Mitsubishi Chemical Corporation
• CA-200 trace moisture content analyzer
• 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 thermal thermogravimetric analyzer TG-DTA7200 (manufactured by Hitachi High-Tech Science Co., Ltd.), a temperature increase rate of 10 ° C./min and a flow rate of 50 mL/min under a nitrogen atmosphere were prepared from each resin composition. The weight reduction rate was measured when each resin sheet was heated to 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.
• Td1 The 1% weight reduction temperature
• 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.
• the adhesion to glass under high humidity conditions was evaluated by measuring the peel energy under wet conditions by the following method.
• MMA Methyl methacrylate
• EA ethyl acrylate
• X ethylene-(meth)acrylic acid ester copolymer
• MFR MFR
• EMMA1 "Aclift” (registered trademark) WH401F manufactured by Sumitomo Chemical Co., Ltd. was used
• EEA1 "Rexpearl” (registered trademark) A4250 manufactured by Japan Polyethylene Co., Ltd. was used.
• the MFR was measured according to JIS K7210-1:2014.
• each raw material resin is melted in a cylinder and extruded from a die with a nominal hole diameter of 2.095 mm installed at the bottom of the cylinder under a load of 2.16 kg at 190 ° C. Resin extruded per 10 minutes The amount (g/10 min) was measured and the value was taken as the MFR.
• Example 1 100 parts by mass of EMMA2 shown in Table 1 was introduced into the reactor, and 233 parts by mass of toluene was added thereto and stirred at 60° C. under a pressure of 0.02 MPa to dissolve EMMA2. 100 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) was added to the reaction solution and stirred at 50°C for 1 hour to convert part of the sodium methacrylate units into methacrylic acid.
• Example 2 An ionomer resin, an ionomer resin composition and a resin sheet were prepared in the same manner as in Example 1, except that EMMA3 was used instead of EMMA2, and 0.0045 parts by mass of xylene was used instead of 0.0015 parts by mass of toluene during melt-kneading. were obtained, analyzed and evaluated. Table 2 shows the results.
• Example 3 An ionomer resin, an ionomer resin composition and a resin were prepared in the same manner as in Example 1 except that EMMA3 was used instead of EMMA2, and 0.0008 parts by mass of methacrylic acid was used instead of 0.0015 parts by mass of toluene during melt-kneading. Sheets were obtained, analyzed and evaluated. Table 2 shows the results.
• Example 4 An ionomer resin, an ionomer resin composition and A resin sheet was obtained and analyzed and evaluated. Table 2 shows the results.
• Example 5 An ionomer resin, an ionomer resin composition and A resin sheet was obtained and analyzed and evaluated. Table 2 shows the results.
• EMMA1 was used instead of EMMA2, the amount of methanol solution of sodium hydroxide (20% by mass) and the amount of hydrochloric acid (20% by mass) added were changed to 80 parts by mass and 66 parts by mass, respectively, and toluene 0 was added during melt kneading.
• An ionomer resin, an ionomer resin composition and a resin sheet were obtained, analyzed and evaluated in the same manner as in Example 1 except that 0.0300 parts by mass of methanol was used instead of 0.0015 parts by mass. Table 2 shows the results.
• Example 7 An ionomer resin, an ionomer resin composition and a resin were prepared in the same manner as in Example 1 except that EEA1 was used instead of EMMA2 and 0.0030 parts by mass of acrylic acid was used instead of 0.0015 parts by mass of toluene during melt-kneading. Sheets were obtained, analyzed and evaluated. Table 2 shows the results.
• Example 8 An ionomer resin, an ionomer resin composition and a resin sheet were obtained, analyzed and evaluated in the same manner as in Example 1 except that 0.0350 parts by mass of toluene was used instead of 0.0015 parts by mass of toluene during melt-kneading. rice field. Table 2 shows the results.
• Example 9 An ionomer resin, an ionomer resin composition and a resin sheet were prepared in the same manner as in Example 1 except that EMMA3 was used instead of EMMA2 and 0.0340 parts by mass of methanol was used instead of 0.0015 parts by mass of toluene during melt-kneading. were obtained, analyzed and evaluated. Table 2 shows the results.
• EMMA4 was used instead of EMMA2, and the amount of methanol solution of sodium hydroxide (20% by mass) and the amount of hydrochloric acid (20% by mass) added were changed to 72 parts by mass and 59 parts by mass, respectively.
• An ionomer resin, an ionomer resin composition and a resin sheet were obtained, analyzed and evaluated in the same manner as in Example 1 except that 0.0120 parts by mass of methanol was used instead of 0.0015 parts by mass. Table 2 shows the results.
• the ionomer resin compositions obtained in Examples 1 to 9 were confirmed to have high transparency and adhesion to glass, and low colorability. Moreover, it was confirmed that the ionomer resin compositions obtained in Examples 1 to 9 had high thermal decomposition resistance and sufficient creep resistance. In contrast, the ionomer resin obtained in Comparative Example 1 and the ionomer resin compositions obtained in Comparative Examples 2 to 4 were inferior in at least one of transparency, glass adhesion and color resistance.
• this resin sheet can be used as an interlayer film for laminated glass, for example, for architectural and structural applications (for example, laminates for facades, exterior walls or roofs, panels, doors, windows, walls, roofs, sunroofs, sound insulation walls, display windows, balconies, etc.). , building materials such as handrail walls, partition glass members for conference rooms, solar panels, etc.), or laminated glass for vehicle applications (e.g., automobile windshield, automobile side glass, automobile sunroof, automobile rear glass, head-up display glass, etc.).
• the laminated glass of the present invention can be suitably used as laminated glass for architectural/structural use or vehicle use.

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• 2022
  • 2022-06-22 JP JP2023530093A patent/JPWO2022270542A1/ja active Pending
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