Composite structure, packaging material and formed product using same, production methods thereof, and coating liquid

Patent metadata

Field	Value
Publication number	US-9840630-B2
Application number	US-201214349251-A
Country	US
Kind code	B2
Filing date	Oct 5, 2012
Priority date	Oct 5, 2011
Publication date	Dec 12, 2017
Grant date	Dec 12, 2017

Abstract

A composite structure disclosed includes a base (X) and a layer (Y). The layer (Y) includes a mixture of a metal oxide (A), a phosphorus compound (B), and a compound (L a ) (silicon compound). Examples of the phosphorus compound (B) and the compound (L a ) include a compound containing a site capable of reacting with the metal oxide (A). When the number of moles of metal atoms (M) derived from the metal oxide (A) is denoted by N M and the number of moles of Si atoms derived from the compound (L a ) is denoted by N Si , 0.01≦N Si /N M ≦0.30 is satisfied. When the number of moles of phosphorus atoms derived from the phosphorus compound (B) is denoted by N P , 0.8≦N M /N P ≦4.5 is satisfied.

First claim

The invention claimed is:

1. A composite structure comprising a base (X) and a layer (Y) stacked on the base (X), wherein
the layer (Y) comprises a mixture of a metal oxide (A), a phosphorus compound (B), and a compound (L a ),
the phosphorus compound (B) is a compound comprising a site capable of reacting with the metal oxide (A),
the layer (Y) comprises a reaction product (R) formed by a reaction at least between the metal oxide (A) and the phosphorus compound (B),
the metal oxide (A) is a hydrolytic condensate of an aluminum alkoxide,
the compound (L a ) comprises a compound (L 1 ),
the compound (L 1 ) is at least one compound selected from the group consisting of tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and derivatives thereof,
N Si and N M satisfy 0.04≦N Si /N M ≦0.25 when the number of moles of metal atoms (M) derived from the metal oxide (A) in the layer (Y) is denoted by N M and the number of moles of Si atoms derived from the compound (L a ) in the layer (Y) is denoted by N Si , and
N M and N P satisfy 0.8≦N M /N P ≦4.5 when the number of moles of phosphorus atoms derived from the phosphorus compound (B) in the layer (Y) is denoted by N P .

2. The composite structure according to claim 1 , wherein the aluminum alkoxide comprises at least one compound selected from the group consisting of aluminum triisopropoxide and aluminum tri-s-butoxide.

3. The composite structure according to claim 1 , wherein the phosphorus compound (B) is at least one compound selected from the group consisting of phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, and derivatives thereof.

4. The composite structure according to claim 1 , wherein the layer (Y) has an infrared absorption peak in a range of 1080 cm −1 to 1130 cm −1 .

5. The composite structure according to claim 1 , wherein the layer (Y) further comprises a polymer (C) comprising at least one functional group (f) selected from the group consisting of a hydroxyl group, a carboxyl group, a carboxylic acid anhydride group, and a salt of a carboxyl group.

6. The composite structure according to claim 5 , wherein the polymer (C) is at least one polymer selected from the group consisting of polyvinyl alcohol, ethylene-vinyl alcohol copolymer, a polysaccharide, polyacrylic acid, a salt of polyacrylic acid, polymethacrylic acid, and a salt of polymethacrylic acid.

7. The composite structure according to claim 1 , wherein the base (X) is in the form of a layer.

8. The composite structure according to claim 7 , wherein the base (X) comprises at least one layer selected from the group consisting of a thermoplastic resin film layer, a paper layer, and an inorganic deposited layer.

9. A packaging material comprising the composite structure according to claim 1 .

10. A formed product comprising the composite structure according to claim 1 .

11. The formed product according to claim 10 , wherein the formed product is a vertical form fill seal pouch, a vacuum packaging pouch, a spout pouch, a laminated tube container, an infusion bag, a container cover, a paper container, or a vacuum insulator.

12. A method for producing the composite structure according to claim 1 , the method comprising:
(I) mixing at least the metal oxide (A), the phosphorus compound (B) comprising a site capable of reacting with the metal oxide (A), the compound (L a ), and a solvent, to obtain a coating liquid (U) comprising the metal oxide (A), the phosphorus compound (B), the compound (L a ), and the solvent;
(II) applying the coating liquid (U) onto the base (X) to obtain a precursor layer of the layer (Y) on the base (X); and
(III) heat treating the precursor layer at a temperature of 110° C. or more.

13. The method according to claim 12 , wherein the aluminum alkoxide comprises at least one compound selected from the group consisting of aluminum triisopropoxide and aluminum tri-s-butoxide.

14. The method according to claim 12 , wherein the phosphorus compound (B) is at least one compound selected from the group consisting of phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, and derivatives thereof.

15. The method according to claim 12 , wherein the layer (Y) further comprises a polymer (C) comprising at least one functional group (f) selected from the group consisting of a hydroxyl group, a carboxyl group, a carboxylic acid anhydride group, and a salt of a carboxyl group.

16. The method according to claim 15 , wherein the polymer (C) is at least one polymer selected from the group consisting of polyvinyl alcohol, ethylene-vinyl alcohol copolymer, a polysaccharide, polyacrylic acid, a salt of polyacrylic acid, polymethacrylic acid, and a salt of polymethacrylic acid.

17. The method according to claim 12 , wherein (I) comprises:
(a) preparing a liquid (S) comprising the metal oxide (A);
(b) preparing a solution (T) comprising the phosphorus compound (B); and
(c) mixing the liquid (S) and the solution (T).

18. The method according to claim 17 , wherein
the compound (L a ) is mixed with the solution (T) in (b), or
the liquid (S), the solution (T), and the compound (L a ) are mixed in (c).

19. The method according to claim 12 , wherein a length of time of the heat treatment is in a range of 0.1 seconds to 1 hour.

20. A coating liquid suitable for use in the method according to claim 12 , comprising: a metal oxide (A); a phosphorus compound (B) comprising a site capable of reacting with the metal oxide (A); a compound (L a ); and a solvent, wherein
the metal oxide (A) is a hydrolytic condensate of an aluminum alkoxide,
the compound (L a ) is at least one compound (L 1 ) selected from the group consisting of tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and derivatives thereof,
N Si and N M satisfy 0.04≦N Si /N M ≦0.25 when the number of moles of metal atoms (M) included in the metal oxide (A) is denoted by N M and the number of moles of Si atoms included in the compound (L a ) is denoted by N Si , and
N M and N P satisfy 0.8≦N M /N P ≦4.5 when the number of moles of phosphorus atoms included in the phosphorus compound (B) is denoted by N P .

21. The composite structure according to claim 1 , wherein
the compound (L a ) further comprises a compound (L 2 ) represented by formula (II):
SiX 2 p Z q R 2 (4-p-q)   (II),

wherein:
X 2 is selected from the group consisting of F, Cl, Br, I, R 2 O—, R 2 COO—, (R 2 CO) 2 CH—, and NO 3 ;
Z is an organic group having at least one functional group selected from the group consisting of a vinyl group, an epoxy group, a styryl group, a methacryl group, an acryl group, an amino group, a ureido group, a mercapto group, a sulfide group, an isocyanate group, a hydroxyl group, and a chloro group;
R 2 is selected from the group consisting of an alkyl group, an aralkyl group, an aryl group, and an alkenyl group;
p represents an integer from 1 to 3;
q represents an integer from 1 to 3; and
2≦(p+q)≦4 is satisfied,
and wherein:
when a plurality of X 2 are included in the formula (II), the plurality of X 2 may be the same as or different from each other,
when a plurality of Z are included in the formula (II), the plurality of Z may be the same as or different from each other,
when a plurality of R 2 are included in the formula (II), the plurality of R 2 may be the same as or different from each other.

22. The composite structure according to claim 21 , wherein
Z in formula

Assignees

• Kuraray Co

Inventors

• Sasaki Ryoichi
• Yoshida Kentaro
• Omoda Mamoru
• Hirose Wataru
• Shibata Manabu
• Oshita Tatsuya

Classifications

• C09D105/00

  Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00 · CPC title

• Y10T428/1307

  Bag or tubular film [e.g., pouch, flexible food casing, envelope, etc.] · CPC title

• Y10T428/1334

  Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.] · CPC title

• Y10T428/1393

  Multilayer [continuous layer] · CPC title

• C09D185/02

  containing phosphorus · CPC title