Search

KR-102961314-B1 - Ionomers, resin sheets, and laminated glass

KR102961314B1KR 102961314 B1KR102961314 B1KR 102961314B1KR-102961314-B1

Abstract

The objective of the invention is to provide an ionomer that has excellent transparency, maintains a high modulus of elasticity at high temperatures, has low coloration, and reduces odor during molding processing. The solution to the objective is an ionomer comprising, based on the total monomer units constituting the resin, 0.05 to 1.0 mol% of (meth)acrylic acid ester units, 4.5 to 9.0 mol% of carboxylic acid units, 0.65 to 3.0 mol% of carboxylic acid neutralizing units, and ethylene units, and further comprising a total content of (meth)acrylic acid ester units, carboxylic acid units, and carboxylic acid neutralizing units of 7.0 to 10 mol%.

Inventors

  • 나카하라 아쓰히로
  • 니이무라 다쿠로
  • 야마구치 도모카
  • 아사누마 요시아키
  • 쓰카하라 다카히로

Assignees

  • 쿠라라이 유럽 게엠베하

Dates

Publication Date
20260508
Application Date
20200522
Priority Date
20190531

Claims (19)

  1. As an ionomer, Based on the total monomer units constituting the resin, it comprises 0.05 to 0.9 mol% of (meth)acrylate methyl units, 4.5 to 9.0 mol% of carboxylic acid units, 0.65 to 2.5 mol% of carboxylic acid neutralization units, and ethylene units, and additionally, the total content of (meth)acrylate methyl units, carboxylic acid units, and carboxylic acid neutralization units is 7.0 to 9.5 mol%, and An ionomer having a yellow index (YI) of 1.7 or less, measured using a resin sheet-shaped test specimen with a thickness of 0.8 mm.
  2. An ionomer according to claim 1, having an MFR of 0.7 g/10 min or more, measured under conditions of a measurement temperature of 190°C and a load of 2.16 Kgf.
  3. In paragraph 2, It comprises 6.5 to 10 mol% of (meth)acrylate methyl units, and An ionomer using an ethylene-(meth)methyl acrylate copolymer as a raw material, having an MFR of 90 to 400 g/10 min measured under conditions of a measurement temperature of 190°C and a load of 2.16 Kgf.
  4. In paragraph 3, A storage modulus of 30 MPa or higher, measured using a resin sheet-shaped test specimen with a thickness of 0.8 mm under conditions of a measurement temperature of 50℃ and a frequency of 1 Hz, and An ionomer having a haze of 5.0% or less, measured using laminated glass in which a resin sheet test specimen with a thickness of 0.8 mm is placed between two glass plates, heated to 140°C, and then slowly cooled to 23°C at a rate of 0.1°C/min.
  5. In paragraph 2, A storage modulus of 30 MPa or higher, measured using a resin sheet-shaped test specimen with a thickness of 0.8 mm under conditions of a measurement temperature of 50℃ and a frequency of 1 Hz, and An ionomer having a haze of 5.0% or less, measured using laminated glass in which a resin sheet test specimen with a thickness of 0.8 mm is placed between two glass plates, heated to 140°C, and then slowly cooled to 23°C at a rate of 0.1°C/min.
  6. In paragraph 1, It comprises 6.5 to 10 mol% of (meth)acrylate methyl units, and An ionomer using an ethylene-(meth)methyl acrylate copolymer as a raw material, having an MFR of 90 to 400 g/10 min measured under conditions of a measurement temperature of 190°C and a load of 2.16 Kgf.
  7. In paragraph 6, A storage modulus of 30 MPa or higher, measured using a resin sheet-shaped test specimen with a thickness of 0.8 mm under conditions of a measurement temperature of 50℃ and a frequency of 1 Hz, and An ionomer having a haze of 5.0% or less, measured using laminated glass in which a resin sheet test specimen with a thickness of 0.8 mm is placed between two glass plates, heated to 140°C, and then slowly cooled to 23°C at a rate of 0.1°C/min.
  8. In paragraph 1, A storage modulus of 30 MPa or higher, measured using a resin sheet-shaped test specimen with a thickness of 0.8 mm under conditions of a measurement temperature of 50℃ and a frequency of 1 Hz, and An ionomer having a haze of 5.0% or less, measured using laminated glass in which a resin sheet test specimen with a thickness of 0.8 mm is placed between two glass plates, heated to 140°C, and then slowly cooled to 23°C at a rate of 0.1°C/min.
  9. A resin composition containing the ionomer described in claim 1 in an amount of 93 mass% or more.
  10. A resin sheet substantially composed of the resin composition described in paragraph 9.
  11. Bonded glass having two glass plates and a resin sheet described in claim 10 as an intermediate layer disposed between the two glass plates.
  12. The ionomer of claim 1, wherein the ionomer comprises 0.65 to 2.0 mol% of carboxylic acid neutralizing units.
  13. In Paragraph 12, It comprises 6.5 to 10 mol% of (meth)acrylate methyl units, and An ionomer using an ethylene-(meth)methyl acrylate copolymer as a raw material, having an MFR of 90 to 400 g/10 min measured under conditions of a measurement temperature of 190°C and a load of 2.16 Kgf.
  14. In Paragraph 13, A storage modulus of 30 MPa or higher, measured using a resin sheet-shaped test specimen with a thickness of 0.8 mm under conditions of a measurement temperature of 50℃ and a frequency of 1 Hz, and An ionomer having a haze of 5.0% or less, measured using laminated glass in which a resin sheet test specimen with a thickness of 0.8 mm is placed between two glass plates, heated to 140°C, and then slowly cooled to 23°C at a rate of 0.1°C/min.
  15. In Paragraph 12, A storage modulus of 30 MPa or higher, measured using a resin sheet-shaped test specimen with a thickness of 0.8 mm under conditions of a measurement temperature of 50℃ and a frequency of 1 Hz, and An ionomer having a haze of 5.0% or less, measured using laminated glass in which a resin sheet test specimen with a thickness of 0.8 mm is placed between two glass plates, heated to 140°C, and then slowly cooled to 23°C at a rate of 0.1°C/min.
  16. In paragraph 1, The above (meth)acrylate methyl unit is a methyl methacrylate unit, and The above ionomer has a yellow index (YI) of 1.1 or less, measured using a resin sheet test specimen with a thickness of 0.8 mm.
  17. In Paragraph 16, It comprises 6.5 to 10 mol% of (meth)acrylate methyl units, and An ionomer using an ethylene-(meth)methyl acrylate copolymer as a raw material, having an MFR of 90 to 400 g/10 min measured under conditions of a measurement temperature of 190°C and a load of 2.16 Kgf.
  18. In Paragraph 17, A storage modulus of 30 MPa or higher, measured using a resin sheet-shaped test specimen with a thickness of 0.8 mm under conditions of a measurement temperature of 50℃ and a frequency of 1 Hz, and An ionomer having a haze of 5.0% or less, measured using laminated glass in which a resin sheet test specimen with a thickness of 0.8 mm is placed between two glass plates, heated to 140°C, and then slowly cooled to 23°C at a rate of 0.1°C/min.
  19. In Paragraph 16, A storage modulus of 30 MPa or higher, measured using a resin sheet-shaped test specimen with a thickness of 0.8 mm under conditions of a measurement temperature of 50℃ and a frequency of 1 Hz, and An ionomer having a haze of 5.0% or less, measured using laminated glass in which a resin sheet test specimen with a thickness of 0.8 mm is placed between two glass plates, heated to 140°C, and then slowly cooled to 23°C at a rate of 0.1°C/min.

Description

Ionomers, resin sheets, and laminated glass The present invention relates to an ionomer, and more specifically, to an ionomer having excellent physical and optical properties, a resin sheet using said ionomer, and a bonded glass using said resin sheet as an intermediate film. Ionomers, which are neutralized products of ethylene-unsaturated carboxylic acid copolymers, are used as intermediate films for laminated glass because they have excellent transparency and adhesion to glass (e.g., Patent Document 1). Recently, as the performance requirements for laminated glass have increased, there has been a demand for ionomers to maintain high transparency regardless of the manufacturing conditions of the laminated glass, maintain a high elastic modulus even at high temperatures without reducing the strength of the laminated glass, and have less discoloration and an excellent appearance. For example, Patent Document 2 describes an ionomer in which 5 to 15 mass% of an α,β-unsaturated carboxylic acid derivative is introduced as a third component into an ethylene-unsaturated carboxylic acid copolymer. Such an ionomer exhibits improved optical properties. However, the ionomer of Patent Document 2 is not yet sufficient to have the balanced excellent characteristics of transparency, high modulus of elasticity, and low coloration required for ionomers used as interlayers for laminated glass. In addition, a new challenge arises with the ionomer of Patent Document 2, as a strong odor originating from the third component is generated during the molding process, resulting in a high load on the worker. <Composition> The ionomer of the present invention is a resin comprising an ethylene unit, a (meth)acrylic acid ester unit (A), a carboxylic acid unit (B), and a carboxylic acid neutralizing unit (C). In one embodiment, the ionomer of the present invention is a resin composed of constituent units (A), (B), and (C) and an ethylene unit. As monomers constituting the (meth)acrylate ester unit (A), the monomers are (meth)acrylate methyl, (meth)acrylate ethyl, (meth)acrylate n-propyl, (meth)acrylate 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 phenyl, (meth)acrylate benzyl, Examples include (meth)acrylate phenoxyethyl, (meth)acrylate 2-hydroxyethyl, (meth)acrylate 2-methoxyethyl, (meth)acrylate glycidyl, (meth)acrylate allyl, etc. Among these, (meth)acrylate methyl, (meth)acrylate ethyl, (meth)acrylate n-propyl, (meth)acrylate isopropyl, (meth)acrylate n-butyl, (meth)acrylate isobutyl, (meth)acrylate sec-butyl, and (meth)acrylate t-butyl are preferred; (meth)acrylate methyl, (meth)acrylate ethyl, (meth)acrylate n-propyl, (meth)acrylate isopropyl, (meth)acrylate n-butyl, and (meth)acrylate isobutyl are more preferred; (meth)acrylate methyl, (meth)acrylate n-butyl, and (meth)acrylate isobutyl are even more preferred; and (meth)acrylate methyl is most preferred. Among methacrylic acid esters and acrylic acid esters, methacrylic acid esters are preferred because they have excellent heat decomposition resistance and low color resistance. These (meth)acrylic acid esters can be used as a single type or in combination of two or more types. The content of the (meth)acrylic acid ester unit (A) in the ionomer is 0.05 mol% or more and 1.0 mol% or less. By having the content of (A) within this range, transparency is increased and odor during molding processing is reduced. As a preferred lower limit of the above content, 0.07 mol% or more is preferred, 0.08 mol% or more is more preferred, and 0.09 mol% or more is even more preferred. As a preferred upper limit of the above content, 0.9 mol% or less is preferred, 0.8 mol% or less is more preferred, and 0.6 mol% or less is even more preferred. Examples of monomers constituting the carboxylic acid unit (B) include acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, etc. Among these, acrylic acid, methacrylic acid, monomethyl maleate, and monoethyl maleate are more preferred, acrylic acid and methacrylic acid are even more preferred, and methacrylic acid is most preferred. These carboxylic acid units can be used as a single type or in combination of two or more types. The content of the carboxylic acid unit (B) in the ionomer is 4.5 mol% or more and 9.0 mol% or less. By having the content of (B) within this range, it is possible to achieve both adhesion to glass and transparency. If the above content is too low, transparency is reduced and adhesion to glass is also reduced. If the above content is too high, moldability is reduced and there is a tendency for discoloration. As a preferred lower limit for the above content, 5.0 mol% or more is preferred, 5.5 mol% or more is mor