JP2002059517A - Method for manufacturing gas barrier surface coated material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a surface coated material excellent in gas barrier properties with good productivity. SOLUTION: The gas barrierf surface coated material is manufactured by forming a coating layer, which comprises a composition containing an organic polymeric compound having an amino group; an organic compound having a functional group capable of reacting with the amino group, and an SiOR1 group (wherein, R1 is a hydrogen atom or a 1-4C alkyl group) in its molecule and a solvent, on the whole or a part of a surface coating base material and drying the coated base material under a condition of 20% Rh or less.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a gas barrier coating.

[0002]

2. Description of the Related Art There is an increasing demand for gas barrier materials having extremely low permeability of gases such as oxygen, nitrogen, carbon dioxide gas and water vapor in the field of packaging materials and the like. In order to impart a gas barrier property to a substrate such as a plastic film, a molded body is made of a gas-impermeable material such as an ethylene-vinyl alcohol copolymer, a vinylidene chloride-based copolymer, and polymethaxylene adipamide. Laminating or coating these gas impermeable materials with other materials,
There are known methods such as laminating an aluminum foil on a film-like material and vapor-depositing a metal or metal oxide.

[0003] However, among the gas-impermeable materials, ethylene-vinyl alcohol copolymer and polymeta-xylylene diadipamide have a large humidity-dependent gas barrier property. And the vinylidene chloride-based copolymer contains chlorine atoms, which may cause pollution.

Further, in the case of the aluminum foil laminated film, the packaged contents cannot be seen from the outside, and the film on which the metal or metal oxide is deposited tends to cause cracks in the deposited layer, and the gas barrier property is deteriorated. Had the problem of causing

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and has as its object to provide a production method for producing a surface coating having excellent gas barrier properties. I do.

[0006]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have made intensive studies and found that an organic polymer compound (I) having an amino group on all or a part of a substrate, Composition comprising an organic compound (II) having a reactive functional group and a SiOR ¹ group (R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) in a molecule, and a solvent (III) After forming a coating layer consisting of
It has been found that by drying below, a surface coating having excellent gas barrier properties can be produced.

That is, the present invention relates to an organic polymer compound (I) having an amino group, a functional group capable of reacting with the amino group, and a SiOR ¹ group (R ¹
Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ) In the molecule and a solvent (III), and after forming a coating layer comprising the composition, the humidity is reduced to 20%.
The present invention relates to a method for producing a gas-barrier surface coating characterized by drying at Rh or less.

[0008] The composition further comprises the following general formula (1): R ² _mM (OR ³ ) _n ··· (1) (wherein, M is a metal element, and R ² is alkyl having 1 to 4 carbon atoms) An alkyl group having 1 to 4 carbon atoms having a functional group which does not react with a group or an amino group, R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n is an integer of 1 or more, and m + n is a metal element M Are the same as the valence of the organic metal compound (IV).

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The surface coating composition used in the present invention comprises an organic polymer compound (I) having an amino group, a functional group capable of reacting with the amino group, and a SiOR ¹ group (R ¹ is a hydrogen atom Or an alkyl group having 1 to 4 carbon atoms) in the molecule and a solvent (III) as essential components.

The organic polymer compound (I) is not particularly limited as long as it is an organic polymer containing an amino group, and specific examples thereof include polyallylamine, amino group-containing (meth) acrylate and other compounds. And a polyalkyleneimine and the like, and polyethyleneimine is particularly preferable.

The number average molecular weight of the organic polymer compound (I) is in the range of 250 to 200,000, preferably 250 to 100,000, more preferably 300 to 10,000. Molecular weight 25
If it is less than 0, the flexibility of the coating layer may be poor, and 2
If it is larger than 10,000, the transparency of the coating layer may be poor.

The functional group capable of reacting with the amino group in the organic compound (II) includes, for example, a (meth) acryl group,
Examples include an epoxy group, a mercapto group, an isocyanate group, and a carboxyl group.

The SiOR ¹ group (R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) in the organic compound (II) includes a gas barrier property and a reduction in shrinkage during the formation of a coating layer. Therefore, it is preferable that R ¹ is methyl or ethyl.

Specific examples of the organic compound (II) include:
γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxymethylpropyldiethoxysilane, γ -Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-isocyanopropyltrimethoxysilane, γ-isocyanopropyl G Liethoxysilane and the like can be mentioned.

The organic compound (II) preferably contains an epoxy group from the viewpoints of ease of reaction with the organic polymer compound (I), handleability at the time of work, and the like.

As the solvent (III), methanol,
Ethanol, 2-propanol, butanol, alcohols such as ethylene glycol, ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as toluene, benzene and xylene, hydrocarbons such as hexane, heptane and octane, ethyl acetate, Esters such as butyl acetate, ethers such as ethylene glycol monoethyl ether, and others, tetrahydrofuran, water and the like,
One or more of these may be used in combination. Among them, alcohols are preferred from the viewpoint of solubility of the coating composition.

The surface coating composition may contain an organometallic compound (IV) represented by the following general formula.

R ² _mM (OR ³ ) _n ·· (1) (wherein, M is a metal element, and R ² is a carbon atom having a functional group which does not react with an alkyl group having 1 to 4 carbon atoms or an amino group. The alkyl group having the number 1 to 4, R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n is an integer of 1 or more, and m + n matches the valence of the metal element M.) Is preferably at least one element selected from the group consisting of Si, Ti, Zr, and Al, and Si is particularly desirable from the viewpoint of reactivity with the organic compound (II).

Specific examples of the organometallic compound (IV) include:
For example, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane , N-propyltrimethoxysilane, n-propyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, trimethylmethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltri Ethoxysilane, N-β-
(Aminoethyl) γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-β- ( Aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β- (aminoethyl) γ-
Aminopropylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, trimethylsilanol, tetraisopropoxytitanium, tetrabutoxytitanium, tetraisopropoxyzirconium, tetrabutoxyzirconium, triethoxyaluminum,
Tributoxy aluminum and the like can be mentioned, and one or more of these can be used. Among them, tetramethoxysilane and tetraethoxysilane are preferred from the viewpoint of the heat resistance of the coating layer.

The organic compound (II) and the organometallic compound (IV) may be hydrolyzed and condensed or co-hydrolyzed and condensed by a known method.

According to the present invention, a coating layer is formed on a substrate by using the surface coating composition. Various organic and inorganic additives such as a curing catalyst, a wettability improver, a plasticizer, and an antifoaming agent may be used in the coating layer as long as the effects of the present invention are not impaired.

The method for forming the coating layer is not particularly limited, but for example, a roll coating method, a dip coating method, a bar coating method, and a die coating method can be used.

The substrate to be coated is not particularly limited. Examples thereof include polyolefins such as polyethylene and polypropylene, polyethylene terephthalate, polyethylene isophthalate, polyethylene 2,6-naphthalate, polybutylene terephthalate and copolymers thereof. And thermoplastic resins such as polyesters, polyamides, polystyrene, poly (meth) acrylates, polyacrylonitriles, polycarbonate, cellophane, polyimide, polyetherimide, polysulfone, polyetherketone, and ionomer resins, and melamine. Resin, epoxy resin, phenol resin, unsaturated polyester resin, urea resin, alkyd resin, thermosetting resin such as silicon resin, and the like. In addition, metals such as aluminum, stainless steel, and steel, and plated steels thereof, paper, and fiber products can be used as the base material.

The substrate is preferably in the form of a film, a sheet, or a bottle, but is preferably in the form of a film in terms of ease of coating.

In the present invention, after forming a coating layer comprising the surface coating composition, the coating is dried at a humidity of 20% Rh or less. The drying condition of the coating layer is preferably such that after forming the coating layer comprising the surface coating composition, 10% Rh is preferably used.
Or less, more preferably 5% Rh or less. If the humidity at the time of drying is higher than 20% Rh, S contained in the coating composition
It is difficult to control the reaction of the iOR ¹ group (R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), and there is a problem that the coating layer becomes cloudy or the gas barrier property is reduced.

The drying temperature of the coating layer in the present invention may be lower than the heat resistance temperature of the surface coating substrate, but is preferably 40 to 100 ° C, more preferably 50 to 100 ° C, and still more preferably 60 to 95 ° C. It is. When the temperature is lower than 40 ° C., it takes time for drying, and the productivity of the coating may be poor. When the temperature is higher than 100 ° C., drying is too fast, and the coating composition cannot form a dense layer, and the gas barrier property may be reduced.

In the present invention, after drying the coating layer, it is preferable to age the coating at room temperature to 80 ° C., preferably 30 to 60 ° C.

As the gas barrier properties of the surface coating obtained as described above, the oxygen permeability is preferably at 20 ° C. and 60% Rh, preferably 20 cc / m ² · 24 hrs · atm or less.
More preferably 10 cc / m ² · 24 hrs · at or less, further preferably 5 cc / m ² · 24 hrs · at
m or less. The oxygen permeability is 20 cc / m ² · 2
If it is larger than 4 hrs.atm, the gas barrier property may be insufficient.

[0029]

The present invention will be specifically described below with reference to examples.

Reference Example 1 25 g of Epomin SP-018 [polyethyleneimine, trade name of Nippon Shokubai Co., Ltd.], 50 g of γ-glycidoxypropyltrimethoxysilane, and 500 g of ethanol were mixed and reacted at 70 ° C. for 3 hours. . After cooling to room temperature, 6 g of water
And a mixture of 20 g of ethanol and react for 24 hours.
A coating composition (1) was obtained.

Reference Example 2 Epomin SP-018 [polyethyleneimine, trade name of Nippon Shokubai Co., Ltd.] 25 g, γ-glycidoxypropyltrimethoxysilane 30 g and ethanol 400 g were mixed and reacted at 70 ° C. for 3 hours. . After cooling to room temperature, 6 g of water
And a mixture of 20 g of ethanol and reacting for 1 hour, and then tetramethoxysilane oligomer [M silicate 5
1. Trade name of Tama Chemical Co., Ltd.] 120 g and ethanol 4
00 g of the mixture was added and reacted for 24 hours to obtain a coating composition (2).

Example 1 The coating composition 1 obtained in Reference Example 1 was used as a 20 μm OPP
Apply to the film so that the thickness after drying is 1 μm,
After drying at 95 ° C. and 3% Rh for 10 seconds, it was treated at 40 ° C. for 3 days to obtain a surface-coated body.

Table 1 shows the evaluation of the properties of this surface coating.

Examples 2 to 4 Surface coatings were obtained in the same manner as in Example 1 except as shown in Table 1. The characteristic evaluation is also shown in Table 1.

Comparative Examples 1 to 4 A comparative surface coating was obtained in the same manner as in Example 1 except that the results are shown in Table 1. The characteristic evaluation is also shown in Table 1.

[Table 1]

[0036]

As described above, the method for producing a gas barrier surface coating according to the present invention produces a gas barrier surface coating excellent in transparency and flexibility without impairing various physical properties. It became possible to manufacture it with good performance. In particular, when a coating layer is formed on a film, drying at a very high speed is required. However, the production method of the present invention sufficiently satisfies such requirements, and a high-performance gas barrier film can be obtained. Now you can.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C09D 183/00 C09D 183/00 185/00 185/00 201/02 201/02 C08L 101: 00 C08L 101: 00 F term (Reference) 4D075 BB24Z BB99Z CA42 DA04 DB31 DC36 EB42 4F006 AA11 AA12 AA31 AB24 AB38 AB67 AB68 BA05 CA07 DA04 4F100 AH08A AH08H AK01A AK01K AK07B AK25A AK31A AK52A AL05A2J02 BA02B02 EB02A02A10A DJ011 DJ012 DL021 DL022 DL031 DL032 DL051 DL052 DL081 DL082 DL091 DL092 DL111 DL112 DL121 DL122 DN011 DN012 JA02 JA05 JA17 JA25 JA33 JA53 KA06 MA14 NA08 NA27 PA18 PB02 PB04 PC02 PC08 PC10

Claims (2)

[Claims] 1. An organic polymer compound (I) having an amino group, a functional group capable of reacting with the amino group and a SiOR ¹ group (R ¹ is a hydrogen atom or a carbon atom After forming a coating layer composed of a composition containing an organic compound (II) having in its molecule an organic compound (II) and a solvent (III), drying is performed at a humidity of 20% Rh or less. A method for producing a gas-barrier surface coating characterized by the following. 2. The composition further comprises the following general formula (1): R ² _mM (OR ³ ) _n .. (1) (wherein, M is a metal element, and R ² is a carbon number of 1 to 4). R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms having a functional group that does not react with an alkyl group or an amino group of formula (I), n is an integer of 1 or more, and m + n is a metal The method for producing a gas-barrier coating according to claim 1, which comprises an organometallic compound (IV) represented by the following formula: