Gas-barrier film

Specification

Gaspa rear film Technical field

It is related with the present invention and a new Gaspa rear film. Background art

From a viewpoint of the prevention from deterioration of flavor and freshness as a film wrapping material for foodstuffs from the former to Oxygen shielding gas rear nature, such as Interruption, carbon dioxide interception nature, and vapor interception nature, ultraviolet-rays interception nature, and Gentle While a sex etc. are required, contents can be seen from a viewpoint of the display nature in a shop front -- high Transparency is also demanded.

Conventionally, in a polyvinylidene chloride resin layer, the film which was painted on the plastic film surface as material, and was laminated the whole Gaspa rear film as a gas barrier layer Generally it was used. however, it can set in recent years at the time of incineration -- development of the Gaspa rear film wrapping material of a non-chlorine type [ problem / of generating of hydrogen chloride gas, dioxin, etc. ] It is wished strongly.

Off using gas barrier 1 resin, such as for example, an ethylene vinyl alcohol copolymer and polyvinyl alcohol, as a non-chlorine Gaspa rear film wrapping material Although there is Irumu, Under high humidity, the use which can be used since gas barrier 1 sex falls There was a problem of being restricted.

^ The indication of an invention

gas Pariya, such as the object of the present invention, oxygen interception nature, carbon dioxide interception nature, and vapor interception nature it excels in one sex -- moreover, it excelled in ultraviolet-rays interception nature, a smell retaining property, transparency, etc. -- new Gasba It is in providing a rear film.

It will become clear by the other objects and the features of the present invention, and the following statements. The present invention is the following new things of which Gaspa rear film * offer is done.

1 . To one side or both sides of plastic film layer (A), it is acid ^ ^ Gas barrier film which laminates titanium membrane layer (B). 2 . Titanium Oxide Membrane Layer (B) -- Hydrolytic Titanium Compound and Formation of Hydrolytic Titanium it is Chosen out of Low Condensation Thing of Low Condensation Thing of Compound, Titanium Hydroxide, and Titanium Hydroxide -- Few -- Both -- Titanium Content Water Liquid Produced by Mixing One Sort of Titanium Compounds with Hydrogen Peroxide Solution

About the ointment for acid Y titanium membrane formation which is (a), it is on plastic film layer (A). It applies and is 2. 0 Film given in the above-mentioned paragraph 1 laminated by making it dry at the temperature below 0 °C.

3 . Titanium content water liquid (a) are a hydrolytic titanium compound and/or its low Contraction. Film given in the above-mentioned paragraph 2 which is peroxotitanic acid solution produced by mixing Compound with hydrogen peroxide solution.

4. Hydrolytic Titanium Compound is General Formula.

T i (O R) 4 (1)

(-- the inside of a formula, and R -- it is the same or different -- the Alkyl machine of carbon number 1*5 is shown.) -- a table -- Film given in the above-mentioned paragraph 3 which is To be tetra-alkoxy titanium.

5 . Low Condensation Thing of Hydrolytic Titanium Compound is General Formula.

T i (O R) 4 (1)

(-- the inside of a formula, and R -- it is the same or different -- the Alkyl machine of carbon number 1*5 is shown.) -- a table -- The degree 2*3 of condensation to which it comes to carry out the condensation reaction of the To be tetra-alkoxy titanium of each other Conversion of 0 Film given in the above-mentioned paragraph 3 which is Compound.

6 . Mixture with a hydrolytic titanium compound and/or its low condensation thing, and hydrogen peroxide solution A rate is former 1. The latter is 0 .1* by hydrogen peroxide conversion to 0 weight section; L 0 0 weight section Film given in the above-mentioned paragraph 3 which is within the limits.

7 . Titanium content water liquid (a) is hydrolytic Chita under existence of acid Y titanium sol. Peroxo produced by mixing a A compound and/or its low condensation thing with hydrogen peroxide solution Film given in the above-mentioned paragraph 3 which is titanic acid solution.

8 . In the above-mentioned paragraph 7 whose acid Ichichi tongue sol is a water dispersion of Anatase type titanium oxide Film of a statement.

9 The Amount of . Titanium Oxide Sol Used is Hydrolytic Titanium Compound and/or Its Low Contraction. As Opposed to 1 Weight Section of Compound, It is 0.0 at solid content. 1*1 It is a statement to the above-mentioned paragraph 7 which is 0 weight section. 10. titanium oxide membrane layer (B), a hydrolytic titanium compound and hydrolytic titanium it is chosen out of the low condensation thing of the low condensation thing of a compound, titanium hydroxide, and titanium hydroxide -- few Titanium content water liquid produced by mixing one sort of titanium compounds with hydrogen peroxide solution also with To

(a) Organic base compound (b) and water organicity polymers combination stable at zero or less PHI About the ointment for titanium oxide film formation containing thing (c), it is a plastic film layer.

(A) it applies upwards -- laminating by making it dry at the temperature below 200"C Film given in the above-mentioned paragraph 1 which is.

11. titanium content water liquid (a) -- a hydrolytic titanium compound and Z -- or -- the -- low -- The above which is peroxotitanic acid solution produced by mixing a condensation thing with hydrogen peroxide solution Film given in paragraph 10.

12. Hydrolytic Titanium Compound is General Formula.

T i (OR) 4 (1)

(-- the inside of a formula, and R -- it is the same or different -- the Alkyl machine of carbon number 1*5 is shown.) -- a table -- Film given in the above-mentioned paragraph 11 which is To be tetra-alkoxy titanium.

13. Low Condensation Thing of Hydrolytic Titanium Compound is General Formula.

T i (OR) 4 (1)

(-- the inside of a formula, and R -- it is the same or different -- the Alkyl machine of carbon number 1*5 is shown.) -- a table -- Conversion of the degree 2~30 of condensation to which it comes to carry out the condensation reaction of the To be tetra-alkoxy titanium of each other Film given in the above-mentioned paragraph 11 which is Compound.

14. Mixed of a hydrolytic titanium compound and/or its low condensation thing, and hydrogen peroxide solution In Proportion, the latter is 0. 1* 100 weight by hydrogen peroxide conversion to 10 weight sections of former. Film given in the above-mentioned paragraph 11 which is within the limits of a part.

15. Titanium content water liquid (a) is hydrolytic Chi under existence of titanium oxide sol. Peroki produced by mixing a tongue compound and A, or its low condensation thing with hydrogen peroxide solution Film given in the above-mentioned paragraph 11 which is Sochi Than acid water solution.

16. The above-mentioned paragraph 1 whose titanium oxide sol is a water dispersion of Anatase type titanium oxide Film given in 5.

17. the amount of the titanium oxide sol used -- a hydrolytic titanium compound -- and/or -- the -- low -- as opposed to 1 weight section of condensation things -- the above-mentioned paragraph 15 which is 0.01*10 weight sections in solid content -- account Film of Loading.

18. A film given in the above-mentioned paragraph 10 whose organic base compound (b) is a 3001 or less-boiling point thing.

19. Phi given in the above-mentioned paragraph 10 whose amount of organic base compound (b) used is 0.001*10 weight sections to 100 weight sections of solid content of titanium content water liquid (a) Lum.

20. Water Organic Polymer Compound (C) are Epoxy System Resin and Phenol System Resin, acrylic resin, urethane system resin, polyester system resin, and polyvinyl alcohol a system -- resin, Polyoxyalkylene chain content resin and Olefin-- polymerization unsaturated Carbon The above-mentioned paragraph 1 which are at least one sort of resin chosen from the group which consists of acid copolymer system resin Film given in 0.

21. The amount of water organic polymer compound (c) used is titanium content water liquid. Solid of (a) It is Off given in the above-mentioned paragraph 10 which is 0.1*200 weight sections to 100 weight sections by type. Irumu.

22. A film given in the above-mentioned paragraph 10 whose ointment for titanium oxide film formation is a water ointment of p H 2* 10.

23. Some or all of titanium oxide that constitutes titanium oxide membrane layer (B) is Amorph. Film given in the above-mentioned paragraph 1 which is A bus titanium oxide.

24. Plastic film layer (A) is a plastic film layer for food packing. Film given in a certain above-mentioned paragraph 1.

25. When plastic film layer (A) is a polypropylene film layer Account paragraph 1 or film given in 24.

26. A film given in the above-mentioned paragraph 1 whose thickness of plastic film layer (A) is 5*100 m.

27. A film given in the above-mentioned paragraph 1 whose thickness of titanium oxide membrane layer (B) is 0. 001*10 m.

Research was repeated wholeheartedly that this artificer and the above-mentioned object should be achieved. As a result, Plastic A titanium oxide membrane layer (B) is laminated on one side or both sides of Film layer (A) as one layer of gas barriers, oxygen interception nature, carbon dioxide interception nature, vapor interception nature, etc. it excels in Gaspa rear nature -- moreover, it excelled in ultraviolet-rays interception nature, a smell retaining property, transparency, etc. -- it found out that new gas barrier 1 film was obtained. This oxidization Chita The ointment for titanium oxide film formation which is above-mentioned specific water liquid (a) on A membrane layer (B) and plastic film layer (A), or the water liquid (a) Organic base compound

(b) And it found out that it could form suitably etc. by applying and drying the ointment for titanium oxide film formation containing water organic polymer compound (c).

It is completed based on the above-mentioned present invention and the starting new knowledge. Plastic film layer (A)

as plastic film layer (A) in a present invention film -- object for packing, etc. it is a plastic film substrate used -- if titanium oxide membrane layer (B) can be made to fix and hold, each publicly known thing can be used.

As the quality of the material of film layer (A), it is polyethylene, Polypropylene, the poly Isoprene, poly butadiene, and poly acetic acid Vieru, Poly chlorination Vieru and Polyethylene terephthalate 1 A (P E T), Nylon, polystyrene, polyurethane, and polycarbonate (P C), Heat plasticity type plastics, such as polyvinyl alcohol (P VA), an ethylene vinyl alcohol copolymer, Polyase tar, A S resin, AB S resin, melamine resin, an acrylic resin, an epoxy resin, and polyester resin etc. It can mention. Especially when using it as an object for foodstuffs also in these, the polypropylene from points, such as processability and safety and hygiene, and a polyethylene rente reflex evening rate are good Up. It is by carrying out and is ..

above-mentioned plastic film layer (A) and necessity are accepted -- an ultraviolet ray absorbent, a bulking agent, heat stabilizer, colorant, etc. may be included. Surface treatments, such as corona discharge treatment, may be performed to the film layer (A) surface, for example. The Phi Coloring and a pattern may be given to the Lum layer (A) surface with ink or a paint. the thickness of a plastic film layer (A) -- usually -- abbreviation 5~1 0 0^m -- desirable -- 2 0*8 It is the range of 0 m. titanium oxide membrane layer (B) it sets on 'present invention film -- it is provided in the surface of plastic film layer (A) titanium oxide membrane layer (B), gas barrier 1 outstanding sex, ultraviolet-rays interception nature, a smell retaining property, etc. -- Issue is carried out -- moreover, it excels in transparency.

To one side or both sides of titanium oxide membrane layer (B) and plastic film layer (A), The ointment for titanium oxide film formation which is above-mentioned specific water liquid (a), or the water liquid (a) Titanium oxide containing organic base compound (b) and water organic polymer compound (c) It can laminate suitably by applying and drying the ointment for film formation.

it is an ointment for titanium oxide film formation -- a hydrolytic titanium compound and hydrolytic Chita Low condensation thing of a A compound, it is chosen out of the low condensation thing of titanium hydroxide and titanium hydroxide -- few -- Titanium content water acquired by mixing one sort of titanium compounds with hydrogen peroxide solution even if there is nothing A publicly known thing can be used as liquid (a), choosing it suitably.

the hydrolytic basis directly combined with the above-mentioned hydrolytic titanium compound and a titanium atom -- an owner -- it is a titanium compound to carry out -- reacting to moisture of water, vapor, etc. -- water oxidization Titanium is generated. it sets to a hydrolytic titanium compound -- titanium even if all the bases combined with an atom are hydrolytic bases -- again -- a part of hydrolytic basis -- Addition Neither is available even if it is the hydroxyl group by which the moisture solution was carried out.

What generates a hydroxyl group by reacting to moisture as the above-mentioned hydrolytic basis Especially if it is, it will not be restricted, but they are a lower alkoxyl group Well, titanium atom and salt. The basis etc. to form are mentioned. As a basis which forms a titanium atom and salt, it is a halogen atom. (>, such as chlorine, a hydrogen atom, a sulfuric acid ion, etc. are mentioned.)

Hydrolytic titanium compound which contains a lower alkoxyl group as a hydrolytic basis If it carries out, tetra-alkoxy titanium etc. are mentioned, for example.

Hydrolytic titanium combination which has a basis which forms titanium and salt as a hydrolytic basis It is mentioned as what has a titanium chloride, titanium sulfate typical as a thing, etc.

the low condensation thing of a hydrolytic titanium compound, and the above-mentioned hydrolytic titanium compounds -- low -- It is a condensation thing. all the bases combined with this low condensation thing and a titanium atom -- hydrolytic basis whether it is or has become the hydroxyl group in which a part of hydrolytic basis was hydrolyzed -- which But -- it does not matter.

as the low condensation thing of titanium hydroxide -- for example, aqueous [, such as a titanium chloride and titanium sulfate, ] Alt. obtained by the reaction of liquid and alkaline water solution, such as ammonia and caustic alkali of sodium Titanic acid (titanium hydroxide gel) etc. -- it can be used.

it can set in the low condensation thing of the above-mentioned hydrolytic titanium compound, or the low condensation thing of titanium hydroxide the degree of condensation -- 2*3 the compound of 0 can be used -- especially -- the degree 2*1 of condensation Thing of 0 within the limits It is preferred to use it.

The above-mentioned titanium compound and hydrogen peroxide solution are made to react as above-mentioned water liquid (a). If it is titanium content water liquid obtained by things, especially a publicly known thing will be restricted from the former. It can be used nothing. Being concrete and the following can be used.

(1) Provisional-Publication-No. 63- it describes in No. 35419 gazette and Japanese Patent Publication No. No. 224220 gazette -- water Peroxo titanium produced by the gel or sol of titanium oxide by adding hydrogen peroxide solution Acid water solution.

(2) Provisional-Publication-No. No. 71418 [ nine to ] gazette, and Provisional Publication No. 10 - It describes in No. 67516 gazette, Salt End Solution, such as Than and titanium sulfate, and alkaline water solution, such as ammonia and caustic alkali of sodium The titanium hydroxide gel which makes react and is called alt. titanic acid is settled, subsequently, Deca hydraulic water A titanium gel is separated and washed by Stations -- this -- hydrogen peroxide solution Water liquid for titanium oxide film formation which is a yellow transparent viscosity fluid obtained by adding.

(3) Provisional publication of a patent 2000 - No. 247638 gazette and provisional publication of a patent 2000 - It describes in No. 247639 gazette, Salt Hydrogen peroxide solution is added to solution of inorganic titanium compounds, such as-izing titanium and titanium sulfate, and it is What. A Luoxo titanium hydrate is formed, the solution produced by this by adding a basic substance -- Release it Place or heats and forms precipitation of a Peroxo titanium hydrate polymer -- Dissolution other than water a part -- water liquid for titanium oxide film formation produced by making hydrogen peroxide act after removing. as titanium content water liquid (a) -- a hydrolytic titanium compound -- and/or -- the -- low -- It is preferred to use peroxotitanic acid solution (a l) produced by mixing a condensation thing with hydrogen peroxide solution.

Especially as the titanium compound, it is a general formula.

T i (O R) 4 (1)

(-- the inside of a formula, and R -- it is the same or different -- the Alkyl machine of carbon number 1*5 is shown.) -- a table -- To be tetra-alkoxy titanium is preferred. Alkyl of carbon number 1*5 shown by R A methyl group, a Ethyl machine, and n -- a propyl group and i s o -- as a machine -- propyl A machine and n -- a butyl group and i s o -- a Buchir machine and s e c -- a butyl group and t e r t -- butyl group etc. -- it is mentioned.

moreover -- as the low condensation thing of the above-mentioned titanium compound -- the compound of above-mentioned general formula (1) -- The degree 2*3 of condensation which comes to carry out a condensation reaction mutually it is preferred to use the thing of 0 -- condensation Degree 2*1 It is more preferred to use the thing of 0.

The hydrolytic titanium compound and Z, or its low condensation thing of general formula (1) (the following and the thing of this and others are only abbreviated to "hydrolytic titanium compound (I)") Hydrogen peroxide solution A mixed rate is former 1. As opposed to 0 weight section, The latter is 0.1*1 by hydrogen peroxide conversion. 0 It is 1*2 especially 0 weight section. Within the limits of 0 weight section is preferred. If the latter will be less than 0.1 weight section by hydrogen peroxide conversion, formation of peroxotitanic acid will become insufficient and will form a nebula precipitate. It is not desirable at that of To. On the other hand, it is 1. When it exceeds 00 weight sections, unreacted hydrogen peroxide remains. Since active oxygen dangerous during storage is emitted that it is easy to carry out, it is not desirable.

the hydrogen peroxide concentration of hydrogen peroxide solution -- although not limited in particular -- 3*4 0% of the weight of example It is preferred from a point of the ease of dealing with it that it is in an enclosure.

The above-mentioned peroxotitanic acid solution, usual, and a hydrolytic titanium compound

(I) Temperature 1*7 It is 1 at within the limits about 0 °C. 0 minute * 2 About 0 hour and hydrogen peroxide solution It can prepare by mixing under churning. necessity is accepted the time of this mixture -- comparing The, methanol, ethanol, and n -- propanol and i s o -- iso Propano 1 Le, Ether glycol monobutyl ether, and propylene glycol mono-Methyl ae Water-soluble solvents, such as Tell, can also be used.

The above-mentioned peroxotitanic acid solution (a l) Hydrolytic titanium compound (I) It is made to mix with hydrogen peroxide solution, a hydrolytic titanium compound is hydrolysis with water it is carried out and a hydroxyl group content titanium compound is generated -- ranking next -- this hydroxyl group content titanium compound It is obtained, when hydrogen peroxide carries out at least Arrangement immediately and forms peroxotitanic acid. It is inferred as a thing. Stability is merit highly in this peroxotitanic acid solution and a room temperature region. It is equal to preservation of a term.

It is peroxidation water about hydrolytic titanium compound (I) under existence of titanium oxide sol. Peroxotitanic acid solution produced by mixing with matter water (a 2) Storage of the solution Since stability, the ultraviolet-rays interception nature of the acid Bhi titanium film obtained, corrosion resistance, etc. are improving It is desirable. it sets to manufacture of the reason and the solution -- a hydrolytic titanium compound

(I) a titanium oxide sol particle is adsorbed -- this adsorbed hydrolytic titanium combination While thing (I) carries out a condensation reaction to the hydroxyl group which arose in the particle surface and carries out a chemical bond The addition carrying out the condensation reaction of the water resolvability titanium compound itself -- polymers -- being-izing and ranking next -- hydrogen peroxide solution the obtained solution is stabilized by being mixed -- the gelling and thickening under storage What is prevented notably is presumed.

the above-mentioned titanium oxide sol, amorphous titanium oxide particulates, and announcer evening-Ze type titanium oxide -- fine -- Particles are Zosole distributed by water. As titanium oxide sol, it is announcer evening-Ze type oxidization. The water dispersion of titanium is preferred from a point of ultraviolet-rays interception nature. titanium oxide sol accepts necessity in addition to water -- for example, water, such as an alcohol system and an alcoholic ether system The organic solvent may be contained.

A thing publicly known from the former as the above-mentioned titanium oxide sol can be used. Amorphous acid which distributed for example, the titanium oxide condensation thing in water as the titanium oxide sol -izing titanium particulates and the titanium oxide condensation thing are calcinated, and it is a Anatase type titanium oxide particle. What considered it as the child and distributed this in water can be used. Glow of formless titanium oxide Formation are the temperature more than the crystallization temperature of Anatase, usual, and 2 at least. 0 Temperature more than 0 °C If it calcinates, transforming formless titanium oxide to announcer evening-Ze type titanium oxide It can do. As the above-mentioned titanium oxide condensation thing, they are (1) titanium sulfate and sulfuric acid Chita, for example. What is produced by hydrolyzing inorganic titanium compounds, such as nil, (2) Titanium Alcokey What is produced by hydrolyzing organic titanium compounds, such as Cyd, (3) titanium tetrachloride, etc. Mentioning what can obtain halogenation titanium solution by hydrolyzing or neutralizing It can do.

as the commercial item of the above-mentioned titanium oxide sol -- for example (Product made from Thika ) "TK S -- 2 0 1" Water A of a brand name and the Anatase type titanium oxide particulates of mean particle size 6 nm Le, "T K S -- 2 0 3" (Product made from Thika , and a brand name) Announcer of mean particle size 6 n m Water sol of evening-Ze type titanium oxide particulates, "TA -- 1 5" (Product made from Nissan chemicals , a brand name, and the water sol of Anatase type titanium oxide particulates) "S T S -- 1 1" (Product made from Ishihara industrial , a brand name, the water sol of Anatase type titanium oxide particulates) etc. -- mentioning -- To be. Acid made to exist when mixing hydrolytic titanium compound (I) and hydrogen peroxide solution As opposed to the amount of the-izing titanium sol used, usual, and 1 weight section of hydrolytic titanium compound (I)s 0.01*10 weight sections is the range of 0.1*8 weight sections preferably in The and solid content. effect which added acid Ichichi tongue sol called the improvement in the storage stability of an ointment, the ultraviolet-rays interception nature of the titanium oxide film obtained, etc. when the amount of the titanium oxide sol used became less than 0.01 weight sections Result is not obtained -- desirable, since the film formability of an ointment is inferior when 10 weight sections is exceeded on the other hand it is -- .

Titanium content water liquid (a) and necessity are accepted, and it is under existence of titanium oxide sol, An added water part Peroxotitanic acid produced by mixing Solvability titanium compound (I) with Peroxide hydrogen water Solution, At the temperature more than 80"C, it heat-treats or processes [ auto crepe ], and averages. It is also used after the diameter of a particle considers it as the dispersion liquid of the titanium oxide particulates below 10 nm. It can do. The appearance of these dispersion liquid is usually translucent [-like ].

The temperature of heat-treatment or Fort Clave processing is fully titanium oxide in less than 80 °C. Crystallization does not progress. The titanium oxide particulates obtained by the above-mentioned processing and the diameter of a particle are below 1 Onm, preferably the range of 1 nm* 6 nm. the diameter of a particle -- 10 nm if it becomes large, film formability will fall -- desirable, since Wow is produced above film thickness l^m it is -- .

titanium content water liquid (a) which is an ointment for titanium oxide film formation, and plus Tick it applies on Irumu -- it heats at the temperature below 200"C -- drying -- adhesion The precise titanium oxide film excellent in the sex can be formed. the minimum of drying temperature -- being limited especially There is nothing. For example, it may dry at room temperature.

They are the above-mentioned dry conditions the case where titanium content water liquid (a) is the above-mentioned water liquid (a l). In the bottom, the amorphous titanium oxide film which contains a hydroxyl group a little is usually formed. Amorph There is an advantage that a A bus titanium oxide film, gas barrier 1 sex, transparency, etc. are more excellent. It is usually a hydroxyl group under the above-mentioned dry conditions the case of titanium content water liquid (a 2). The Anatase type titanium oxide film included a little is formed.

As an ointment for titanium oxide film formation, it is titanium content water liquid. (a) Organic base combination Application containing thing (b) and water organic polymer compound (c) stable at zero or less PHI An agent is used, the adhesion over plastic film layer (A) -- further -- Mukai it stages -- friction [ in / again / the time of circulation, etc. / time of processing ], bending, etc. -- Gaspa rear nature A gas barrier film with few falls can be obtained.

case where above-mentioned organic base compound (b) and water organic polymer compound (c) are used together it can set -- the thing same as titanium content water liquid (a) as the above -- each -- use It can do.

As organic base compound (b), it is boiling point 3. 0 It is inside with the organic base compound below 0 °C. It can be used, without being limited if peace is possible. As a desirable thing It is ammonia, Dimethylethanolamine, and 2 especially. -- Amino 2 -- Methyl 1 1 1 propanol, ♪ Liethylamine, morpholine, etc. are mentioned.

The amount of organic base compound (b) used, and titanium content water liquid (a) 1 0 It is 0.0 to 0 weight section (solid content). 0 1*1 It is 0.0 preferably 0 weight section. 0 5*5 weight It is a part. It is the effect even if it uses organic base compound (b) in the quantity of less than a mentioned range. It is insufficient. a mentioned range is exceeded for organic base compound (b) -- case where it is used the ratio to which organic base compound (b) remains in the formed film becomes large -- film formation a sex falls -- it is in the tendency for performances, such as Gaspa rear nature and anti-corrosiveness, to fall.

As water organic polymer compound (c), it dissolves or distributes in water by zero or less .p H l. It is To use about a publicly known thing, without being limited if it is in The and stable A state II. To is made.

As water organic polymer compound (c), they are solution, a water dispersion, or Emulsi. What has Yong's form can be used. an organic polymer compound -- water -- water using a method publicly known as Melting-izing, decentralization, or a method of making it emulsion-ize -- line It obtains and things are made.

As the example of water organic polymer compound (c), For example, they are aqueous-izing or water at independent. Functional group which can be decentralized (for example, hydroxyl group) The thing containing at least one sort, such as a power report Xyl machine, an amino group, an imino group, a Sulphide machine, and a phosphine machine, and the compound What neutralized a part or all of the functional group it has can be used. Neutralization in this case There needs to be water organic polymer compound (c) with acidic resin, such as power report Xyl machine content resin. The, Amine compounds, such as Ethanolamine and Triethylamine; ammonia solution; water Lithium oxide alkali metal hydroxide, such as Hydroxic acid sodium and a potassium hydrate, etc. it is neutralized -- if it is basic resin, such as Amino machine content resin, again -- fat, such as acetic acid and lactic acid Acid; It is neutralized by mineral acid, such as phosphoric acid, etc.

As this water organic polymer compound (c), For example, epoxy system resin and Hue Knoll system resin and acrylic resin, Urethane system resin, polyester system resin, and Polyvi Nil alcohol system resin, Polyoxyalkylene chain content resin and Olefin single affinity Unsaturated-carboxylic-acid copolymer system resin, nylon system resin, polyglycerin, and Carboxymethyl cellulose, hydroxymethyl cellulose, and hydroxyethyl cell low A etc. are mentioned.

As the inside of above-mentioned water organic polymer compound (c), and a desirable thing, Epoxy system tree Fat, phenol system resin, acrylic resin, urethane system resin, polyester system resin, Polyphony nil alcohol system resin, polyoxyalkylene chain content resin, and Olefin 1 Polymerization unsaturated-carboxylic-acid copolymer system resin etc. are mentioned. It is especially considered as a desirable thing. The, epoxy system resin, polyester system resin, urethane system resin, and phenol system tree Fat etc. are mentioned.

cation which adds amine to an epoxy resin as the above-mentioned epoxy system resin system epoxy resin; -- a Acryl modified epoxy resin, a Urethane modified epoxy resin, etc. are strange A sex epoxy resin etc. can be used conveniently. As a cation system epoxy resin, they are an epoxy compound, and the 1st class Monod or polyamine, for example, The 2nd class Monod or poly friend A, 1 Addition with the 2nd Class Mixture Polyamine Etc. (For example, U.S. Pat. 3 9 8 4 2) 9 Nine Refer to Item Specification. ; The 2nd Class Monod Who Has Epoxy Compound and the Ketimine-Ized 1st Class Amino Group, or Addition with Polyamine (for example, U.S. Pat. 4 0 1 7 4 3 No. 8 Specification 3 Looking); Epoxy Compound and the Ketimine-Ized 1st Class Amino Group hydronalium Xylui A which it has A 1 Tell-ized reaction product with Compound (for example, refer to Provisional-Publication-No. 5 9 - 4 3 0 1 No. 3 gazette) etc. -- it is raised.

as the above-mentioned epoxy compound -- a number average molecular weight -- 4 0 0*4 and 0 0 0 -- especially -- 8 0 0*2 and 00 it is within the limits of 0 -- and an epoxy equivalent -- 1 9 0*2 and 0 0 0 -- especially -- 4 0 0*1 and 0 0 What is within the limits of 0 is suitable. Such epoxy combination It obtains by a reaction with a thing, for example, a polyphenol compound, and Epichlorchi drine compounds. To is made. As a polyphenol compound, it is screw_2 and 2 (4-Hydroxy CIF enyl). -- Propane, 4 and 4 -- dihydroxy benzophenone and screw 1 (4-hydroxyphenyl) -- 1 and 1-Ethan, screw (4 -- hydronalium Kisifue 2 Le) 1 -- 1 and 1 -- isobutane, screw (4 -- hydroxy 1 te r t -- Butyl Hue 2 Le) 1 -- 2 and 2 -- propane, Screw (2 -- hydroxy Naphthyl) Methane, 1, 5 -- Di Hydroxy Naphthalene, screw (2, 4 -- dihydroxy phenyl) methane and tetra (4-hydroxyphenyl) -- _1, 1, 2, and 2 -- Ethan, 4, and 4-dihydroxy diphenylsulfone, phenol Nopolac, cresol Nopolac, etc. raise , -- To be .

as the above-mentioned Feno 1 Le system resin -- a phenol component and formaldehyde -- anti- -- The high molecular compound which adds, makes heat and condense under existence of Catalytic converter, and is obtained was made aqueous. A thing can be used conveniently. As the above-mentioned phenol component which is a starting material 2 functionality phenolic compound, 3 functionality phenolic compound, and Off of four or more functionality A Enol compound etc. can be used. As 2 functionality phenolic compound o -- Cresol and p -- Cresol, p [ Rufhenol, 2, 3 / As a Enol compound, / -- Xylenol, 2, 5 -- Xylenol etc. and 3 functionality Off ] -- ter t -- Butylphenol and p -- Ha Phenol and m [ -- 4 functionality Fenno 1 Le combination, such as methoxy Fueno 1 Le / As a thing, screw phenol A, screw phenol F, etc. can be illustrated. To. ] -- Cresol and m -- Ethyl phenol, 3, 5 -- Xireno 1 Le and m the number of these phenolic compounds is one -- or thing which two or more sorts use mixing To include.

as the above-mentioned acrylic resin -- for example, a power report Xyl machine and an amino group -- hydroxyl group Friend with the independent polymer or copolymer with which hydrophilic radical of a It was monomer, and a hydrophilic radical The copolymer of Nomar and other copolymerizable monomers, etc. are mentioned. these resin, an emulsification polymerization, and suspension polymerization -- or solution polymerization is carried out -- necessity is accepted -- neutralizing and water-izing Obtained by. necessity is accepted in the obtained resin -- it may further denature.

As the above-mentioned carboxyl group content monomer 1, they are acrylic acid and Metacry. Le acid, maleic acid, a maleic anhydride, crotonic acid, A computer acid, etc. are mentioned. It can do.

As nitrogen-containing monomer 1, they are N and N. -- Dimethylaminoethyl (meta) Clear, N, N -- Diethylamino ethyl (meta) A Urgency rate, N [ Chill Amino ethyl (meta) Nitrogen-containing Alkyl, such as a Urgency rate (meta) Accrile - A; acryl amide, ] -- t -- The Methacrylamide and N -- Methyl (meta) Acryl amide and N -- Ethyl (meta) acryl amide, N -- Methylol (meta) Acryl amide and N -- Methoxymethyl (meta) Acryl amide, N -- Butoxy methyl (meta) Acryl amide, N, N -- Dimethyl (meta) Acryl amide, N, N -- Dimethylaminopropyl (meta) Acryl amide, N and N -- dimethylaminoethyl (meta-) Polymerization amide, such as Acryl amide; 2 -- 2 -- Biel pyridine and 1 1 vinyl 1 -- Pirro Liddon and 4 -- aromatic series nitrogen-containing monomer; Allylamine, such as Bulle pyridine, etc. It is mentioned.

As hydroxyl group content monomer 1, it is 2. -- Hydroxyethyl (meta) Urgency Rate, Hydroxypropyl (meta) A Urgency rate, 2, 3 -- DihydroXylophilic (meta) Urgency rate, 4 -- Hydroxy butyl (meta) A Urgency rate and poly Mono-[ ethylene glycol ] (meta) Accrile 1 A etc., polyhydric alcohol and acrylics monoester ghost; with acid or methacrylic acid -- the above-mentioned polyhydric alcohol and acrylic acid -- moreover -- Monoester ghost with methacrylic acid Combination which carried out ring opening polymerization of the epsilon - power pro lactone A thing etc. are mentioned.

As other copolymerizable monomers, it is methyl. (meta) Quick Relay, Ethyl (meta) A Urgency rate and eta -- Propyl (meta) Urgency rate, Isop Mouth pill (meta) A Urgency rate and eta -- Butyl (meta) Urgency rate, An iso Petitakuri (meta) rate, ter t -- Butyl (meta) Urgency rate, 2 -- It is Ix to Ethyl. Le (meta) A Urgency rate and n -- Octyl (meta) Urgency rate, Lauryl (Me evening) A Urgency rate and tridecyl (meta) Urgency rate, A Ok evening Decyl (meta) Urgency rate and isostearyl (meta) Carbon numbers 1*2, such as Accrile 1 A Four Alkyl (meta) Urgency rate; styrene, acetic acid vinyl, etc. are mentioned. These Conversion It can be used combining Compound, one sort, or two sorts or more.

in addition -- in this specification -- a "Urgency (meta-) rate" and a Urgency rate -- or -- meta--- A Urgency rate is meant.

As the above-mentioned urethane system resin, they are polyester polyol and polyether poliomyelitis. Polyurethane resin obtained from polyol and diisocyanate, such as - Le, required Low-molecular quantity combination which responds and has two or more active hydrogen, Diol, Diamine, etc., chain extension is carried out under existence of the chain extension agent which is a thing -- what was distributed or dissolved underwater stably It can be used conveniently. As this urethane system resin, it is Japanese Patent Publication No. 4. 2 -- 2 4 1 9 No. 2, Japanese Patent Publication No. 4 2 -- 2 4 19 No. 4 and Japanese Patent Publication No. 4 2 -- 5 1 1 No. 8, Japanese Patent Publication No. 4 9 -- 9 8 No. 6 and Japanese Patent Publication No. 4 91 -- 3 3 1 0 No. 4 and Japanese Patent Publication No. 5 0 -- 1 5 0 2 No. 7 and Japanese Patent Publication No. 5 3 - 2 9 1 7 The publicly known thing described in No. 5 gazette etc. can be used widely.

as the method of distributing or dissolving polyurethane resin underwater stably -- for example, -- lower -- The method of an account can be used.

(1) the side chain or end of polyurethane resin -- a hydroxyl group, an amino group, carboxyl group, etc. hydrophilicity is given by introducing an ionicity machine -- it is distribution to underwater by self-emulsification Or the method of dissolving.

(2) it is a block about the polyurethane resin which the reaction completed, or an end Anisocyanate machine using an emulsifier and mechanical shearing force for the polyurethane resin which carried out Plock by the agent -- compulsory -- The method of distributing underwater. As this Plock agent, Oxim, alcohol, and Fenno - Le, Merca butane, Amin, heavy sodium sulfite, etc. can be mentioned.

(3) polyurethane resin with an end isocyanate group -- water, an emulsifier, and chain extension it mixes with an agent -- method of performing decentralization and polymers quantification simultaneously using mechanical shearing force.

(4) as the materials polyol of polyurethane resin -- a polyethylene lender recall -- the time -- water-soluble polyol -- using it -- obtaining -- having had -- polyurethane -- resin -- underwater -- distribution -- or -- The method of dissolving.

the water resin obtained by distribution or the dissolving method of the above-mentioned Pori Ule evening A resin -- independent or two or more sorts are mixed -- it can be used.

As diisocyanate which can be used for composition of the above-mentioned polyurethane system resin, it is perfume. Diisocyanate of fellows, alicycle fellows, and a fatty series is mentioned. Being concrete, for example, Kisamachi range isocyanate, and tetramethylene di-isocyanate, 3 and 3' -- dimethoxy 4 and 4' - Bifue 2 range isocyanate, p -- Misery -- rangy Affiliation and m -- xylylene diisocyanate, 1, 3 -- (Diisocyanatome Chill) It is Xanon, 1, and 4 to cyclo. -- (Diisocyanato methyl) It is Xanon to cyclo, It is Xanon, 4, and 4' to 4 and 4'-Diisocyanato cyclo. -- Methylene screw (cyclo Xyl isocyanate) Isophorone diisocyanate, 2, 4 1 Triangle Iso , 2 6 -- Tolylene Diisocyanate and P -- Hue 2 Range Isocyanate, Jihue 2 Rethane diisocyanate and m -- Hue 2 range iso Cyanate, 2, 4 [ 4 and 4'-Bi Hue 2 range isocyanate, 4, and 4' ―Bifue 2 range isocyanate etc. are mentioned. ] -- Naff evening range isocyanate, 3, and 3' -- Dimethyl - It is 2 and 4 among these. -- Tolylene diisocyanate, 2, 6 -- Tori Wren - especially A is preferred.

as the commercial item of the above-mentioned polyurethane system resin -- for example, "Hy Derain HW -- 3 3 0" , "Hy Derain HW -- 3 4 0" (all are Products made from large Japan ink chemical industry ) "Hy Derain HW -- 3 5 0" brand name [ ] -- "-- super 1 flex-time 1 0 0" "-- The [ A - ] 1 flex-time 1 5 0" "A 1 The 1 flex time F -- 3 4 3 8 D" (all are Product made from Dai-Ichi Kogyo Seiyaku , and a brand name) etc. -- it can mention.

as the above-mentioned polyvinyl alcohol system resin -- the degree 8 of saponification Pori Vieru more than 7 % it is preferred that it is alcohol -- the degree 9 of saponification more than 8 % -- what is called full saponification It is preferred that it is especially polyvinyl alcohol. Number average molecular weights are 3 and 0. 0 0*1 0 0 and 0 0 It is preferred that it is within the limits of 0.

As the above-mentioned polyoxyalkylene chain content resin, a polyoxyethylene chain or Po what has a Rioqui Cipro pyrene chain can use it conveniently -- for example polyethylene Long A recall, polypropylene glycol, a polyoxyethylene chain, and polyoxy pro Blocking polyoxy alkylene glycol which the pyrene chain combined in the shape of a block etc. -- it can mention.

As the above-mentioned Olefin-- polymerization unsaturated-carboxylic-acid copolymer system resin, Olefin, such as ethylene and propylene (meta) Acrylic acid Polymerization unsaturated, such as maleic acid It is Addition about a polymerization unsaturated compound to the water dispersion of a copolymer with carboxylic acid, and the copolymer. An emulsification polymerization is obtained and carried out and at least one sort of water-dispersion resin or water-soluble resin chosen from two sorts of resin further crosslinked in particles can be used conveniently.

The copolymer of the above-mentioned Olefin and polymerization unsaturated carboxylic acid, and Oref more than a kind It is a copolymer of A and the polymerization unsaturated carboxylic acid more than a kind. the copolymer -- if it is -- as monomer content -- the unsaturated carboxylic acid -- 3*60 % of the weight -- good -- better It is suitable for To that it is 5*40% of the weight of within the limits. Acid radical in this copolymer It can distribute in water by neutralizing by a basic substance.

a polymerization unsaturated compound is added to the water dispersion of the above-mentioned copolymer, and an emulsification polymerization is carried out -- further -- As the polymerization unsaturated compound in the bridge construction resin which crosslinks in particles for example, -- front -- Biel monomers which were enumerated by explanation of Acryl system resin of account water-dispersion or water solubility it is mentioned -- one sort or two sorts or more can be used, choosing them suitably.

The combination rate of water organic polymer compound (c), Within the limits of 1*50 weight sections is Paint especially 0.1*200 weight sections to 100 weight sections of solid content of titanium content water liquid (a). It is desirable from points, such as the stability of a cloth agent, the gas barrier 1 sex of a titanium oxide film obtained, ultraviolet-rays interception nature, a smell retaining property, and processability-proof.

Titanium content water liquid (a) It is stable by organic base compound (b) and ten or less pH. It is preferred that they are an ointment for titanium oxide film formation containing water organic polymer compound (c) and a water ointment of pH 2*10. p the case where H is less than two -- storage stability of liquid a sediment is generated the case where it is in the tendency to fall and pH exceeds ten -- film formability It is in the tendency to fall.

it responds to the ointment for titanium oxide film formation used by the present invention at necessity -- various kinds of additives It can also contain. Titanium oxide marketed if it is considered as an additive Sol, titanium oxide powder, paints, etc. can be mentioned. As paints, for example, my power, talc, silica, barium sulfate, clay, etc. can be mentioned.

As thickness of acid^* A titanium membrane layer (B), it is usually 0. 001*10micropiiota. The range is preferred and it is 0. ; !. Especially the range of * 3 m is preferred. 0. Less than 001 m When it becomes, they are Gaspa rear nature and Keep, such as oxygen interception nature, carbon dioxide interception nature, and vapor interception nature. Since a titanium oxide film will break easily if Fragrance falls and 10/m is exceeded, it is gas. Barrier nature and a smell retaining property fall. Manufacture, the layer composition, and the use of a gas-barrier-property film

(Gas barrier 1 film (A) , for example, the plastic film layer, of the present invention On the surface) the ointment for titanium oxide film formation is applied -- ranking next -- room temperature or 2 0 below 0 C -- desirable -- 1 5 -- it heats at the following temperature -- it dries -- titanium oxide membrane layer (B) It can obtain by forming. A titanium oxide film is stiffened at the time of this dryness. The is also good. Heating temperature is 2. When 0 is exceeded, plastic film layer (A) is strange. Degradation of type, deterioration, etc. may be caused.

As a coating method of the ointment for titanium oxide formation, they are for example, roller paint and Dip coating. Seal of coating methods, such as Wear, spray coating, and brush paint, screen-stencil, Toppan Printing, etc. Conventionally publicly known means, such as Printing method, can be used.

One side or both sides of ointment for titanium oxide film formation, and plastic film layer (A) It applies and dries, and it can come, is alike, and is the film layer more. (A) and titanium oxide membrane layer

The two-layer composition of (B), or titanium oxide membrane layer (B) Film layer (A) and oxidization Chita The lamination film of the three-layer composition of a A membrane layer (B) is obtained. Thickness of each class, The above-mentioned passage, It is usually the film layer. (A) Abbreviation It is the range of 5*1 0 0 m. Titanium oxide membrane layer. (B) It is the range of 0 .0 0 1*10 m. The total thickness of a film, and two-layer lamination Off It is usually 7*1 any [ of Irumu and a three layer lamination film ] case. 0 It is a 0 j^m grade and is Ah. To.

responding to the above-mentioned two-layer lamination film and three-layer lamination film of the present invention at necessity -- This one side or both sides of a Re lamination film -- a hard court layer -- it can get damaged and can further laminate a Le [ A prevention layer and Heatsi - ] layer, an adhesives layer, etc. by a usual state method.

The gas barrier 1 film, especially oxygen interception nature of the present invention, carbon dioxide interception nature, and Water vapor It can be conveniently used for the use which needs Gaspa rear nature, such as mind interception nature, ultraviolet-rays interception nature, a smell retaining property, transparency, etc.

being concrete, a present invention film, for example, foodstuffs, medicine, medical science, electric parts, and agriculture, forestry and fishery it sets to fields of industry, such as Production, fermentation, and household articles, -- the container of various articles, packing, etc. -- To use is made. especially -- the container of a present invention film and food and drink, packing, etc. -- suitable -- use it can do -- oxygen in that the oxygen which dissolved in water, a drink, food, etc., spice, etc. shift in this case, and the air, gas, etc. can be effectively prevented from permeating into a container or packing. Brief explanation of the drawings X diffraction of ointment for titanium oxide film formation (1) obtained in Drawing 1 and example 1 of the after-mentioned manufacture It is a drawing in which a result is shown. The best form for inventing

next, the example of manufacture, an example, and a comparative example are given -- the present invention is explained more concretely. However, the present invention is not limited to the following examples. "part" given in each example and "%" are weight standards. Example of the lamination film prepared using the ointment which is titanium content water liquid (a l) Example 1 of manufacture

Tetra i s o -- Propoxytitanium 1 Zero copy and i s o -- Propanol 1 Mixture of zero copy About a thing, it is 30 % hydrogen peroxide solution 1. Zero copy and deionized water 1 0 It is 2 in the mixture of zero copy. It is 1 at 0. It time-applied, and it was dropped while agitating. after that 2 it ripes by 5 for 2 hours -- yellow -- transparent -- few -- Titanium content water liquid which is peroxotitanic acid solution of solid content 2 % which carries out and is viscous It obtained. This was made into ointment for titanium oxide film formation (1). the X diffraction result of this ointment (1) -- a figure -- it is shown in 1. Drawing 1 -- titanium oxide in this ointment -- Amorpha It turns out that it is A titanium oxide.

Example 2 of manufacture

it sets for example 1 of manufacture -- Tetra i s o -- it replaces with propoxytitanium -- Tetra n -- The an equivalent amount of Toxy titanium is used, and also it is made to be the same as that of example 1 of manufacture -- titanium of solid content 2 % Content water liquid was obtained. This was made into ointment for titanium oxide film formation (2).

Example 3 of manufacture

it sets for example 1 of manufacture -- Tetra i s 0 -- it replaces with propoxytitanium -- Tela i s o1 propoxytitanium an equivalent amount of trimers are used, and also it is made to be the same as that of example 1 of manufacture -- solid a part -- the titanium content water liquid of 2 % was obtained. This was made into ointment for titanium oxide film formation (3).

Example 4 of manufacture

it sets for example 1 of manufacture -- using triple the amount of hydrogen peroxide solution -- 5 it is dropped over 1 hour by 0 °C -- after that -- 6 it ripes by 0 °C for 3 hours, and also makes it be the same as that of example 1 of manufacture -- Chita of solid content 2 % A content water liquid was obtained. This was made into ointment for titanium oxide film formation (4).

Example 5 of manufacture

titanium oxide coating agent (2) obtained in example 2 of manufacture -- 95"C -- 6-hour heat-treatment it carries out -- titanium content water liquid of solid content 2 % which is translucent titanium oxide dispersion liquid of white yellow It obtained. This was made into ointment for titanium oxide film formation (5).

Example 6 of manufacture

10 % ammonia solution is dropped at the solution which set titanium tetrachloride 60 % solution 5 c c to 500 c c with distilled water -- Hydroxide titanium was settled. They are the washing back and 30% of hydrogen-peroxide-solution solution with distilled water about precipitation 1 Solid as for which 0 c c adds and which contains scrambling and peroxotitanic acid Titanium content water liquid 70 c c which is a yellow translucent viscosity fluid of type part 2 % was obtained. This was made into ointment for titanium oxide film formation (6).

Example 7 of manufacture

The fluid which made water distribute titanium hydroxide 0. 2 mo 1 / 1 was created. About this, it is a ratio. It was considered as ointment [ for Comparison ] for titanium oxide film formation (7).

Example 1*6 and comparative example 1

Ointment for titanium oxide film formation (1) * About (7), it is film thickness 20 xm. Polyp for biaxial Arrangement To the single surface which performed corona discharge treatment of the Ropiren film, dry film thickness -- 0. 3 m it paints in one Bako evening 1 like -- dryness is performed for 5 minutes by 120"C -- titanium oxide a film is laminated -- the lamination film was obtained. it is example 1*6 of ointment (1) -- ointment * The case where (6) is used is operation. (the case where 7> is used is comparative example 1.)

Comparative examples 2 and 3

Film thickness 20 m The polypropylene film for biaxial Arrangement, or polyethylene copolymer call The phthalate film was made into comparative examples 2 and 3, respectively.

About each film of Example 1*6 and comparative example 1*3, they are a coat state, adhesion, and a lead. The examination of brush hardness and an oxygen transmission rate was done by the following method.

(1) Coat state : see the existence of abnormalities in a coat, such as the smooth nature of a coat, transparency, and Wow, with the naked eye. It guessed. That normal was made good.

(2) adhesion: J I S K5400 Go board specified to 8.5.2 (1990) 100 grids of lmmX 1mm are created according to the eye tape method -- the surface -- Viscosity The number of Left of the grid at the time of wearing, sticking a tape, and ranking next and exfoliating was counted.

(3) Pencil hardness: J I S K5400 Lead specified to 8.4.2 (1990) The brush scratch test was done and it evaluated based on the existence of an abrasion.

(4) oxygen transmission rate: -- the IPRI type film oxygen transmission rate meter (Product made from Rika Seiki Kogyo ) it uses -- it measured by underwater [ of 25"C ]. A unit is [cm.³(STP) '^ 111²(It is;1*].)

The quality of the material and the test result of a film are shown in Table 1.

<img file="WO0202313A1_D0001.tif" />

P p shows polypropylene among front and P ET shows polyethylene Futarate. Example of the lamination film prepared using the ointment which is titanium content water liquid (a 2) Example 8 of manufacture

Tetra i s o -- Ten copies of propoxytitanium, and i s o -- Mixture of ten copies of propanol Thing, "TKS -- 201" (made in Thika and titanium oxide sol) It is 1 hour at 10 °C in the mixture of five copies (solid content), ten copies of 30 % hydrogen peroxide solution, and 100 copies of deionized water. It applied, and it was dropped while agitating. riping by 10 degreeC after that for 24 hours -- yellow -- transparent -- a few -- Viscosity The titanium content water liquid which is peroxotitanic acid solution of solid content 2 % with a sex was obtained. This was made into ointment for titanium oxide * formation (8).

Example 9 of manufacture

it sets for example 8 of manufacture -- Tetra i s o -- replacing with propoxytitanium -- Tetra n -- Bouto an equivalent amount of Xichitans are used, and also it is made to be the same as that of example 8 of manufacture -- titanium Including of 2% of solid content Owner water liquid was obtained. This was made into ointment for titanium oxide film formation (9).

it sets for example 8 of example of manufacture 10 manufacture -- Tetra i s o -- replacing with propoxytitanium -- Tetra i so -- propoxytitanium it is made to be the same as that of other Ho which use an equivalent amount of trimers, and example 8 of manufacture -- the titanium content water liquid of 2% of solid content was obtained. this -- ointment for titanium oxide film formation (it obtained ten and considered it as .)

Example 11 of manufacture

it sets for example 8 of manufacture -- it is dropped over 1 hour by 10 degreeC, using [ in / triple the amount ] hydrogen peroxide solution -- it ripes by 10 degreeC after that for 30 hours, and also makes it be the same as that of example 8 of manufacture -- Chi of 2% of solid content Than content water liquid was obtained. This was made into ointment for titanium oxide film formation (11). Example 7*; L 0

Ointment for titanium oxide film formation (8) * It is (11) Film thickness 2 O^m Poly for biaxial Arrangement To the single surface which performed corona discharge treatment of the propylene film, it paints in one Bako evening 1 so that dry film thickness may be set to 0. 3 m -- dryness is performed for 5 minutes by 120"C -- oxidization Chita a A film is laminated -- the film of example ?* 10 was obtained.

About each film of Example 7*10, they are a coat state, adhesion, pencil hardness, and oxygen. Transmissivity was examined by the above-mentioned method.

The quality of the material and the test result of a film are shown in Table 2. The result of comparative example 2 was written together for comparison.

Table 2

<img file="WO0202313A1_D0002.tif" />Titanium content water liquid (a) Organic base compound (b) and water organic polymer compound

(c) the ointment for titanium oxide film formation which Contains is used -- lamination film prepared Example

Example 12 of manufacture

the titanium content water liquid obtained in example 1 of manufacture is heat-treated by 95 for 6 hours -- white yellow -- half--- The titanium content water liquid of solid content 2 % which is transparent titanium oxide dispersion liquid was obtained.

Example 13 of manufacture

Tetra i s o -- Ten copies of propoxytitanium, and i s o -- Mixture of ten copies of propanol Thing, "TKS -- 203" (made in Thika and titanium oxide sol) It is 1 hour at 10 °C in the mixture of five copies (solid content), ten copies of 30 % hydrogen peroxide solution, and 100 copies of deionized water. It applied, and it was dropped while agitating. riping by 10 degreeC after that for 24 hours -- yellow -- transparent -- a few -- Viscosity The titanium content water liquid of solid content 2 % which is peroxotitanic acid solution with a sex was obtained. Example 14 of manufacture

Ethylene glycol monobutyl ether 1 and 200 copies are put into a reaction vessel, 1 To Inside Temperature rising(ed) and Held to 00"C, it is 400 Copies of Methacrylic Acid, 500 copies of styrene, and 100 copies of Acryl acid Ethyl, "Par butyl O" (a brand name, the product made from Nippon Oil &amp; Fats , and a Peracid ghost system polymerization initiator) The mixture of 35 copies and ethylene glycol mono-Petitle 1 Tell 140 part was dropped over 3 hours. it ripes in end back of dropping, and 100"C for 2 hours -- subsequently -- n -- 570 copies of butanol -- in addition, carboxyl group content A of 36% of solid content Krill resin solution (AC -- 1) was obtained. the number average molecular weight of the obtained resin -- abbreviation 7 and 00 it is 0 -- resin acid value was 26 OmgKOHZg.

To next, another reaction apparatus, "Aralcid AER 6129 resin (brand name)" Asahi transformation -- Epoxy Make, epoxy equivalent 2, 800 copies of epoxy resins of 600, and Di 129 copies of ethylene Glico 1 Le Mondo butyl ether is added, heated and stirred -- uniform -- Melting It understood. this solution -- above-mentioned carboxyl group content acrylic resin solution (AC -- 1) 5 56 copies are put in -- churning mixture was carried out uniformly. then, 66 copies of Dimethylethanolamine after holding to 90 in addition for 1 hour, while agitating -- water 2 and 450 copies -- 1 hour Keep it. dropping is carried out -- carboxyl group content acrylics modified epoxy resin A of 25% of solid content Marshall was obtained.

Example 15 of manufacture

To the reaction apparatus provided with agitating equipment, the reflux condenser, the thermometer, and the liquid dripping device, "A [ Epiko - ] 1009 resin" (a brand name and Product made from shell chemicals ) molecular weight 3 and Epo of 750 Ix resin 1, 880 g (0.5 mol), and methyliso Buchir ketone Z xylene = 1/1 (weight ratio) it heats and stirs, after adding mixed solvent 1 and 000 g -- uniform -- the dissolution It carried out. Di which was cooled to after that 70degreeC and isolated preparatively to the liquid dripping device (n -- proper no Le) For 30 minutes was required and Amin 70 g was dropped. It is Keep to 70 degreeC about during this period and reaction temperature. It had. The Amin modified epoxy resin of 66% of solid content was obtained by holding by 120 degreeC after the end of dropping for 2 hours, and completing a reaction. as opposed to obtained resin 1 and 000 g 25 copies of formic acid of 88% of The is mixed -- after adding water, the Amin modified epoxy resin emulsion of solid content 30 % was obtained by fully agitating.

Example 16 of manufacture

"Ho1BouzolA -- 5100X" (a brand name, Product made from Kyowa Hakko Kogyo , and solid content 6 0% of acrylic modification polyester resin solution) As opposed to 50 copies, "My coat 10 6" (a brand name and Product made from Mitsui psytec ) 77% of solid content states and it is a Shenzog anamine tree. (made in U.S. King Industries) Four copies of fat, and "NACURE 5225" a brand name, the amine neutralization solution of dodecylbenzenesulfonic acid, and Dodecylbenzenesulfur phon acid content mixes six copies 25% -- fully agitating, after adding water The, and the acrylic modification polyester / melamine Hardness resin solution of 30% of solid content were obtained. Example 17 of manufacture

as basin system urethane resin HUX -- "-- Adeka Bon Thai evening 1 -- 401" (a brand name, the product made from Asahi electrification (A), and the basin system urethane resin dispersing element of 37% of solid content) It used.

Example 18*26 of manufacture

the following table -- a composition rate given in 3 is followed -- the inside of titanium content water liquid -- organic-base-nature-izing Compound is put in and agitated -- it is oxidization by the procedure which puts in and agitates a water organic polymer compound next Ointment for titanium membrane formation (12) * (20) was prepared. Ointment (12) * (1 9) is an object for examples, and is ointment (20) and an object for comparison.

The composition rate of each ointment is shown in Table 3. Table 3

<img file="WO0202313A1_D0003.tif" />Example 11*: L 8 and comparative example 4

Ointment for titanium oxide film formation (12) * About (19), they are film thickness 20 / m. Po for biaxial Arrangement To the single surface which performed corona discharge treatment of the repro pyrene film, it paints in one Bako evening 1 so that dry film thickness may be set to 0. 3 m -- dryness is performed for 5 minutes by 120"C -- oxidization Chi the Than film is laminated -- the film of Example 11*18 was obtained. titanium oxide film type ointment for Formation (20) is used -- it is made the same -- the film of comparative example 4 was obtained.

About each film, the examination of a coat state, adhesion, pencil hardness, and an oxygen transmission rate was done by the above-mentioned method. Examination of the oxygen transmission rate after coating liquid stability and rubbing It carried out by the following method.

(5) Coating liquid stability : the separation after storing an ointment for one month by 40"C, gelling, etc. The existence of abnormalities estimated stability. The case of being normal was made good.

(6) Oxygen permeability after rubbing: The load of 500 g is applied to the film of 5 cm width, it is made for the application side of an ointment to become inside, it winds around the stainless pipe of 1 Omm, and it is Take. It is Measurement with the above-mentioned method about the oxygen transmission rate of the film after winding with Ri and repeating broth 10 times respectively. It carried out constant.

A test result is shown in Table 4. Table 4

<img file="WO0202313A1_D0004.tif" />With the present invention, On at least one side of a plastic film, Titanium oxide membrane layer It laminated. The sake, Oxygen interception nature, Carbon dioxide interception nature, Gasba, such as vapor interception nature It excels in rear nature, Moreover, it is ultraviolet-rays interception nature, Smell retaining property, Gas barrier which is excellent in transparency etc. A prominent effect that a 1 film is provided is acquired.

at least one side of a plastic film -- especially -- titanium content water liquid (a) , acid containing organic base compound (b) and water organic polymer compound (c) the ointment for-izing titanium membrane formation is used -- case where a titanium oxide membrane layer is laminated the gas Valley 1 film whose processability and adhesion of the titanium oxide film further improved -- offer -- The prominent effect of To be is acquired.

according to the gas barrier 1 film of the present invention, it can manufacture only by that special art and equipment are unnecessary and application operation -- moreover, the effect that a manufacturing cost is cheap is also acquired