CN1537903A - Gas barrier coating composition and gas-barrier film - Google Patents
Gas barrier coating composition and gas-barrier film Download PDFInfo
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- CN1537903A CN1537903A CNA2004100341873A CN200410034187A CN1537903A CN 1537903 A CN1537903 A CN 1537903A CN A2004100341873 A CNA2004100341873 A CN A2004100341873A CN 200410034187 A CN200410034187 A CN 200410034187A CN 1537903 A CN1537903 A CN 1537903A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/048—Forming gas barrier coatings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
To obtain a gas barrier coating composition that contains no carboxylic acid as an odor source and can form the paint film of high adhesion and high gas barrier properties in no need of the anchor layer, even when the substrate is made of a polyester resin. In this gas barrier coating composition, he following components A, B, C, D are formulated so that the weight ratio of the component (A) to the component (B) may be A/B=2/1-1/1, the weight ratio of the component (B) to the component (C) may be B/C=20/1-2/1. A: polyvinyl alcohol; B: an alkoxysilane bearing amino group and/or imino groups; C: a glycidyl ether represented by the following formula (I) (n is an integer of 0-4); D: lower alcohol-including aqueous solution.
Description
The present invention is denomination of invention the dividing an application for No. 00134158.8 application for a patent for invention of " composition of gas barrier paint and gas-barrier films " of on December 06th, 2000 application.
Technical field
The invention relates to form and have the gas barrier coating resin combination that good gas barrier property is filmed, and use said composition to form the gas-barrier films of gas barrier layer.
Background technology
In the past, as having that the coating composition of gas barrier property has been known, constituted and calculated the composition (Japanese Patent discloses No. 255910/1997) of a/ (b+c)=9/1～1/99 by following a～d composition with weight ratio.
A: polyvinyl alcohol;
B: (part) hydrolyzate, its (part) condenses and their mixture with organoalkoxysilane of epoxy group(ing);
C: (part) hydrolyzate, (part) condenses and their mixture with organoalkoxysilane of amino and/or imino-;
D: as the water of solvent.
But if the composition of gas barrier paint of above-mentioned prior art directly uses like this, c composition wherein will be had an effect and gelationization as the condensation catalyst of b composition, can not form and film.Therefore, when reality is used, must in the c composition, add carboxylic acids such as acetic acid, form weakly acidic organic acid salt.
But, particularly be the occasion of polyester at ground, the wettability of above-mentioned prior art combinations on this ground that the interpolation carboxylic acid is made is relatively poor, is difficult to form film uniformly, is easy to generate pin hole etc., thereby can not fully obtains gas barrier property.In addition,, produce acid smell, often make the painting work environmental degradation owing to contain carboxylic acid such as acetic acid.
In addition, disclose the gas-barrier films that stacks gradually easy tack coat and polyvinyl alcohol resin floor at least one side surface that discloses in No. 296929/1998 the thermoplastic resin membrane and obtain at Japanese Patent, in this polyvinyl alcohol resin layer, contain amino silane coupling agent.
But this film must be provided with an easy tack coat (anchor layer) between ground and polyvinyl alcohol resin layer, thereby complex process not only, the production cost height, and in the occasion that anchor layer is not set, there are a lot of problems in the sticking power deficiency of ground and polyvinyl alcohol resin layer.
Summary of the invention
In view of above-mentioned problems of the prior art, the objective of the invention is, do not contain the carboxylic acids such as acetic acid that become odor source, and, even ground be the occasion of polyester do not need anchor layer just can form sticking power good, have filming of high gas barrier property.
The 1st aspect of the present invention provides composition of gas barrier paint, it is characterized in that, said composition contains following A, B, C, D composition, and the weight ratio (A/B) of A composition and B composition is 10/1-1/2, and the weight ratio (B/C) of B composition and C composition is 20/1-2/1.
A: polyvinyl alcohol;
B: as the represented organoalkoxysilane of following (I) formula with amino and/or imino-;
In the formula, R
3Expression contains the alkylene of carbon number 1～4, R
4And R
5Expression contains the alkyl of carbon number 1～4, and X represents hydrogen atom or aminoalkyl group, and n represents 1 or 0.
C: by the glycidyl ether that following (II) formula is represented, in the formula, n represents the integer of 0-4.
D: the water that has added lower alcohol.
The 1st aspect of the invention described above, its preferred scheme comprises: the A composition is the polyvinyl alcohol that has silyl in the molecule, the content of this silyl is 0.01-5 mole %; The A composition is carboxy-modified polyvinyl alcohol; Perhaps, the A composition is the mixture of modified polyvinyl alcohol and unmodified polyethylene alcohol.In addition, the invention described above the 1st aspect in, the B composition also can be to have the organoalkoxysilane of amino and/or imino-and the mixture of its (part) hydrolyzate and/or (part) condenses, and the C composition also can be by glycidyl ether shown in above-mentioned (II) formula and the mixture of its (part) hydrolyzate.In addition, the preferred version of the 1st aspect of the invention described above also comprises and contains E: fine fibrillated fibre, the weight ratio (B/E) of B composition and E composition is 100/2-100/0.05.
The 2nd aspect of the present invention provides composition of gas barrier paint, it is characterized in that, said composition is made of following A, B, D composition, and the weight ratio (A/B) of A composition and B composition is 10/1-5/4.
A: unmodified polyethylene alcohol;
B: as the represented organoalkoxysilane of following (I) formula with amino and/or imino-;
In the formula, R
3Expression contains the alkylene of carbon number 1～4, R
4And R
5Expression contains the alkyl of carbon number 1～4, and X represents hydrogen atom or aminoalkyl group, and n represents 1 or 0.
D: the water that has added lower alcohol.
The preferred version of the invention described above the 2nd aspect comprises that the weight ratio (A/B) of A composition and B composition is 20/3-5/4.
The 3rd aspect of the present invention provides composition of gas barrier paint, it is characterized in that, said composition is made of following A, B, D composition, and the weight ratio A/B of A composition and B composition is 100/7-2/1.
A: the mixture of modified polyvinyl alcohol or modified polyvinyl alcohol and unmodified polyethylene alcohol;
B: as the represented organoalkoxysilane of following (I) formula with amino and/or imino-;
In the formula, R
3Expression contains the alkylene of carbon number 1～4, R
4And R
5Expression contains the alkyl of carbon number 1～4, and X represents hydrogen atom or aminoalkyl group, and n represents 1 or 0.
D: the water that has added carbonatoms and be 1～5 alcohol.
The 3rd aspect of the invention described above, its preferred scheme comprises: the A composition is the polyvinyl alcohol that has silyl in the molecule, the content of its silyl is 0.01-5 mole %; Perhaps, the A composition is carboxy-modified polyvinyl alcohol.In addition, comprise also that the weight ratio A/B of A composition and B composition is 20/3-2/1 as preferred scheme.
The invention described above the 2nd and the 3rd aspect in, the B composition also can be to have the organoalkoxysilane of amino and/or imino-and the mixture of its hydrolyzate or partial hydrolystate and/or condenses or partial condensate.
The 4th aspect of the present invention provides the film of gas barrier property, it is characterized in that, this film has the filming of composition of gas barrier paint of the 1-3 aspect of the invention described above, and the preferred version of the present invention the 4th aspect comprises, filming of composition of gas barrier paint is set on the ground of polyester.
Embodiment
The 1st aspect of the present invention at first is described.
The composition of gas barrier paint of the 1st aspect of the present invention contains following A, B, C, D composition.
A: polyvinyl alcohol;
B: as the represented organoalkoxysilane of following (I) formula with amino and/or imino-;
In the formula, R
3Expression contains the alkylene of carbon number 1～4, R
4And R
5Expression contains the alkyl of carbon number 1～4, and X represents hydrogen atom or aminoalkyl group, and n represents 1 or 0.
C: the glycidyl ether of representing by above-mentioned (II) formula.(II) formula is expressed as follows once more, and in the formula, n represents the integer of 0-4:
D: the water that has added lower alcohol.
A composition in the present invention the 1st aspect can use the polyvinyl alcohol of selling on the market.Be used as the polyvinyl alcohol of A composition, same with the polyvinyl alcohol that uses in the past the composition of gas barrier paint, the polymerization degree is 100-5000, and jelly grade is for best more than 70%.The polymerization degree is crossed when low, reduce easily with the sticking power of ground, otherwise when the polymerization degree was too high, viscosity is excessive, and coating worsens.In addition, gelation is spent when hanging down, and gas barrier property is often insufficient.
Above-mentioned A composition can use modification or unmodified any; modified polyvinyl alcohol can be enumerated; with modified polyethylene alcohol such as carboxyl, silyl, sulfonic group, amino, phosphate, isocyanate group, oxazoline group, methylol, nitro, acetoacetyl, cation radicals; for example use the segmented copolymer of modifications such as propenyl, urethane, polyester, epoxy group(ing), polyethylene, polypropylene or graft copolymers etc.; these modified polyvinyl alcohols, unmodified polyethylene alcohol can use a kind, also can mix use more than 2 kinds.In addition, when modified polyvinyl alcohol is mixed use with unmodified polyethylene alcohol, in the total amount of A composition, preferably mix the above modified polyvinyl alcohol of 10 weight %, more preferably mix more than the 20 weight %.
Be used as the polyvinyl alcohol of A composition in aspect the of the present invention the 1st, preferentially select the polyvinyl alcohol and the carboxy-modified polyvinyl alcohol that have silyl in the molecule for use, because on ground, form dry, when solidified is filmed, even relax restriction, also be not easy to be created under the high humidity and preserve and sticking power that cause and ground reduction for drying conditions.
Here has silyl in the said molecule, be meant on the middle portion of the molecular chain of polyvinyl alcohol or end and have silyl, as long as silyl is not by being that water-disintegrable key combines with polyvinyl alcohol, its position and distribution have no particular limits.In addition, said silyl is meant reactive silyl that following (III) formula is represented.R in following (III) formula
1Be alkyl, basic metal or the alkaline-earth metal of 1-10 hydrogen, carbon atom, R
2Be the alkyl of 1-10 carbon atom, n is the integer of 1-3.
The content that has the silyl in the polyvinyl alcohol of above-mentioned silyl in the molecule is advisable at 0.01-5 mole %, preferably 0.1-1.0 mole %, preferably 0.1-0.6 mole %.The viscosity of resulting composition of gas barrier paint increased when the content of silyl surpassed 5 moles of %, gelation easily, otherwise, when the content of silyl is lower than 0.01 mole of %, on ground, form dry, when solidified is filmed, if relax restriction to drying conditions, when under high humidity, preserving with the just reduction easily of sticking power of ground.
In addition, said carboxy-modified polyvinyl alcohol, be meant that intramolecularly has the polyvinyl alcohol of carboxyl, for example, with vinyl ester monomers such as vinyl acetate, vinyl formate, propionate, tertiary ethylene carbonate, trimethylacetic acid vinyl acetate and vinylformic acid, methacrylic acid, phthalic acid (acid anhydride), toxilic acid (acid anhydride), methylene-succinic acid ethene unsaturated carboxylic acid copolymerizations such as (acid anhydrides), the random copolymers that obtains of saponification then.
Carboxy-modified amount is 0.1-50 mole %, preferably 0.5-10 mole %, preferably 0.5-5 mole %.
Be used as in aspect the of the present invention the 1st the B composition as the represented organoalkoxysilane of above-mentioned (I) formula with amino and/or imino-, for example can enumerate: the amino methyl triethoxyl silane, 2-amino-ethyl Trimethoxy silane, 2-amino-ethyl triethoxyl silane, 2-amino-ethyl tripropoxy silane, 2-amino-ethyl three butoxy silanes, 1-amino-ethyl Trimethoxy silane, 1-amino-ethyl triethoxyl silane, the 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, 3-aminopropyl tripropoxy silane, 3-aminopropyl three butoxy silanes, the 2-TSL 8330, the 2-aminopropyltriethoxywerene werene, 2-aminopropyl tripropoxy silane, 2-aminopropyl three butoxy silanes, the 1-TSL 8330, the 1-aminopropyltriethoxywerene werene, 1-aminopropyl tripropoxy silane, 1-aminopropyl three butoxy silanes, N-amino methyl amino methyltrimethoxy silane, N-amino methyl amino methyl tripropoxy silane, N-amino methyl-2-amino-ethyl Trimethoxy silane, N-amino methyl-2-amino-ethyl triethoxyl silane, N-amino methyl-2-amino-ethyl tripropoxy silane, N-amino methyl-3-TSL 8330, N-amino methyl-3-aminopropyltriethoxywerene werene, N-amino methyl-3-aminopropyl tripropoxy silane, N-amino methyl-2-TSL 8330, N-amino methyl-2-aminopropyltriethoxywerene werene, N-amino methyl-2-aminopropyl tripropoxy silane, the N-TSL 8330, the N-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-2-amino-ethyl Trimethoxy silane, N-(2-amino-ethyl)-2-amino-ethyl triethoxyl silane, N-(2-amino-ethyl)-2-amino-ethyl tripropoxy silane, N-(2-amino-ethyl)-1-amino-ethyl Trimethoxy silane, N-(2-amino-ethyl)-1-amino-ethyl triethoxyl silane, N-(2-amino-ethyl)-1-amino-ethyl tripropoxy silane, N-(2-amino-ethyl)-3-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-aminopropyl tripropoxy silane, N-(3-aminopropyl)-2-amino-ethyl Trimethoxy silane, N-(3-aminopropyl)-2-amino-ethyl triethoxyl silane, N-(3-aminopropyl)-2-amino-ethyl tripropoxy silane, N-methyl-3-TSL 8330,3-aminopropyl methyl dimethoxysilane, 3-aminopropyl methyldiethoxysilane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-Diethylenetriamine propyl-triethoxysilicane, 3-[2-(2-aminoethylamino ethylamino) propyl group] Trimethoxy silane, trimethoxy-silylpropyl Diethylenetriamine etc.
Above-mentioned B composition, can use in the above-mentioned organoalkoxysilane with amino and/or imino-more than a kind or 2 kinds.Particularly preferred B composition is Y-aminopropyltriethoxywerene werene, N-β (amino-ethyl) Y-TSL 8330.
The glycidyl ether of being represented by above-mentioned (II) formula that is used as the C composition for example can be enumerated: ethylene glycol diglycidylether, Diethylene Glycol diglycidylether, triethylene glycol diglycidylether, TEG diglycidylether, nine ethylene glycol diglycidylethers, propylene glycol diglycidylether, dipropylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, 1,6-hexanediol diglycidyl ether etc.
The C composition can use in the above-mentioned glycidyl ether more than a kind or 2 kinds.Particularly preferred C composition is an ethylene glycol diglycidylether.In addition, aspect the of the present invention the 1st in, use the glycidyl ether shown in above-mentioned (II) formula can obtain good coating, particularly preferably be m and be the integer below 9, n is the integer below 6.
Water in the D composition (distilled water) is solvent, uses behind the interpolation lower alcohol in this water, produces pin hole in the time of can preventing dried coating film.The lower alcohol that adds in water for example can be enumerated methyl alcohol, ethanol, Virahol etc.The proportioning of lower alcohol and water is calculated (lower alcohol/water) with weight ratio and is advisable at 10/90-30/70.If the addition of lower alcohol is very few, be easy to generate pin hole during dried coating film, otherwise when the addition of lower alcohol was too much, coating worsened easily.
The following describes the proportioning of above-mentioned A, B, C, D composition.
The A composition is in order to obtain the basic composition of gas barrier property, and the B composition is to be used for improving resulting composition of filming with the sticking power of ground.The proportioning of this A composition and B composition, (A/B) is calculated as 10/1-1/2, preferably 2/1-1/1 with weight ratio.If the use level of A composition is (use level that is the B composition is very few) too much, be the occasion of polyester at ground particularly, it is low with the sticking power of ground to film, otherwise, during the use level of A composition very few (use level that is the B composition is too much), resulting gas barrier property of filming is insufficient.
The proportioning of B composition and C composition, (B/C) is 20/1-2/1 in weight ratio, preferably 20/1-5/1, preferably 15/1-5/1.The C composition is to be used for giving gained to film with wet fastness, even under high humidity, also can keep filming sticking power with ground like this, but when the use level that C helps is too much, coating worsens, otherwise, when the C composition was very few, the water tolerance that gained is filmed reduced, and films under high humidity and peels off easily.
The proportioning of D composition can suitably be selected according to the application condition, the solid shape of resulting composition of gas barrier paint is divided reach 1-20 weight %, can suitably select according to coating process etc. in this scope.When the use level of D composition is too much, be difficult to obtain filming of necessary thickness, otherwise when the use level of D composition was very few, coating worsened easily.
In aspect the of the present invention the 1st, owing to make water as solvent, above-mentioned B composition promptly has the part hydrolysis lentamente sometimes of the organoalkoxysilane of amino and/or imino-, is transformed into its (part) hydrolyzate, when also having, its hydrolyzate further is transformed into (part) condenses.In addition, the glycidyl ether that above-mentioned C composition is promptly represented by above-mentioned (II) formula also is the same, and its part can be transformed into (part) hydrolyzate sometimes.In the occasion that this variation takes place, equally also can obtain the effect of the 1st aspect of the present invention.
Therefore, the B composition in the present invention the 1st aspect also can be to have the organoalkoxysilane of amino and/or imino-and the mixture of its (part) hydrolyzate and/or (part) condenses.In addition, no matter whether the B composition comprises above-mentioned (part) hydrolyzate and/or (part) condenses, the C composition in the present invention the 1st aspect can be the mixture of the glycidyl ether shown in above-mentioned (II) formula and its (part) hydrolyzate.
In addition, can contain fine fibrillated fibre as the E composition.Fine fibrillated fibre has moisture holding capacity, therefore, on ground, form dry, when solidified is filmed, no matter drying conditions how, moisture in can keeping filming promotes the hydrolysis reaction and/or the condensation reaction of B composition, therefore, under the situation of relaxing the restriction of drying conditions, resulting filming is not easy also to cause because preserve that the sticking power with ground reduces under high humidity.
The fine fibrillated fibre that is used as the E composition for example can enumerate the fine fibrillated fibre element that makes the cellulosic fibre miniaturization and obtain, make the polyolein fiber miniaturization and fine fibrillation polyolefine of obtaining etc., in order to have sufficient moisture holding capacity, do not damage the transparency of composition, number average fiber length is 0.04-0.1mm, 0.05-0.08mm preferably, axial ratio is more than 40, preferably more than 60.
Described cellulosic fibre can be enumerated: with mechanical means or chemical process by softwood tree (home-made dragon spruce for example, white fir, Korean pine, tamarack etc., exotic Picea mariana, white spruce, Pseudotsuga menziesii (Mirbel) Franco, western hemlock, the south pine, jack pine etc.) extract the paper pulp that fiber obtains out, with mechanical means or chemical process by deciduous tree (home-made white poplar for example, lime tree, Sai En (セ Application), Populus, white birch etc., exotic trembling poplar, eucalyptus etc.) extract fiber out and the paper pulp that obtains, by the cotton pulp dregs of rice, fiber crops, sisal hemp, mestha, cogongrass, paper mulberry, three forks, the wild goose skin, artificial silk, it fills in (テ Application セ Le), the paper pulp that the non-wood-fiber of regenerated celluloses such as koplon extracts.
Above-mentioned polyolein fiber for example can be enumerated, utilize flash of light (Off ラ Star シ ユ) spinning, spinning such as extrudes at for example vinyl acetate of vinyl monomer that method makes the multipolymer of alkene of 2-8 carbon atom or homopolymer and these alkene and (for example 0.5-30 mole %) on a small quantity, vinylbenzene, alkyl methacrylate or alkyl acrylate (particularly methacrylic acid or acrylic acid methyl ester or ethyl ester), the multipolymer of maleic anhydride is specifically as polyethylene, polypropylene, polybutene, polypenthylene, propylene-ethylene copolymers, butylene-ethylene copolymer, poly-(4-methylpentene-1), vinyl acetate-ethylene copolymer, maleic anhydride-ethylene copolymer, and ethylene-methyl methacrylate or acrylic acid ethyl ester or methyl ester copolymer fibreization and the fiber that obtains.
The proportioning of E composition is 100/2-100/0.05 in the weight ratio (B/E) of B composition and E composition, preferably 100/0.5-100/0.1.When the use level of E composition was too much, the transparency of filming reduced easily, otherwise, when the use level of E composition is very few, often can not get obvious effects.
The composition of gas barrier paint of the present invention the 1st aspect is to be made of above-mentioned A-D composition or A-E composition basically, in the scope of not damaging effect of the present invention, in order to improve coating, with respect to 100 parts of the total amounts (weight) of A-D composition or A-E composition, can add 10 parts (weight) following thickening material, defoamer, curing catalysts, wettability modifying agent, softening agent etc.
The composition of gas barrier paint of the present invention the 1st aspect is coated on the ground, forms filming of gas barrier property.
When on ground, being coated with, for example can adopt customary way in the past such as dip coated, spraying, flow coat, roller coat, coiling rod blade coating, rotary coating, direct notch board coating.In order to simplify the application operation, in addition,, obtain good gas-barrier properties for feasible sticking power with ground remains on the realistic scale, the thickness of filming should be at 0.2-7 μ m, preferably 0.3-1.5 μ m.
For the composition of gas barrier paint that uses unmodified polyethylene alcohol as the present invention the 1st aspect of A composition, the dry solidification of filming after the coating should carry out above under 60 ℃ the heating atmosphere in the film coated surface temperature.If the envrionment temperature during dry solidification is low excessively, when particularly preserving resulting gas-barrier films under high humidity, ground reduces easily with the bonding force of filming.The upper limit of the film coated surface temperature during above-mentioned dry solidification also depends on the thermotolerance of ground, generally is 120 ℃.
On the other hand, for the composition of gas barrier paint that uses the polyvinyl alcohol that has silyl in the molecule or carboxy-modified polyvinyl alcohol as the present invention A composition or that contain the E composition the 1st aspect, as long as reach dry solidification in the heating atmosphere more than 50 ℃, just be not easy to occur in the ground preserving under the high humidity and cause and be coated with binding force of membrane and reduce in the film coated surface temperature.Therefore, use the polyvinyl alcohol that has silyl in the molecule or carboxy-modified polyvinyl alcohol as the A composition or contain the composition of gas barrier paint of the present invention the 1st aspect of E composition, dried coating film after being coated with in the film coated surface temperature reaches heating atmosphere more than 50 ℃ solidifies just passable, and its advantage is the restriction that can relax the heat drying condition.The upper limit of film coated surface temperature is 120 ℃ with top described identical at this moment.
The following describes the of the present invention the 2nd and the 3rd aspect.
The composition of gas barrier paint of the 2nd aspect of the present invention is made of following A, B, D composition basically.
A: unmodified polyethylene alcohol;
B: as the represented organoalkoxysilane of following (I) formula with amino and/or imino-;
In the formula, R
3Expression contains the alkylene of carbon number 1～4, R
4And R
5Expression contains the alkyl of carbon number 1～4, and X represents hydrogen atom or aminoalkyl group, and n represents 1 or 0.
D: the water that has added lower alcohol.
In addition, the composition of gas barrier paint of the 3rd aspect of the present invention is made of following A, B, D composition basically.
A: the mixture of modified polyvinyl alcohol or modified polyvinyl alcohol and unmodified polyethylene alcohol;
B: as the represented organoalkoxysilane of following (I) formula with amino and/or imino-;
In the formula, R
3Expression contains the alkylene of carbon number 1～4, R
4And R
5Expression contains the alkyl of carbon number 1～4, and X represents hydrogen atom or aminoalkyl group, and n represents 1 or 0.
D: the water that has added lower alcohol.
Identical with described in the invention described above the 1st aspect of the A that uses in aspect the of the present invention the 2nd and the 3rd, B, D composition.
Here said unmodified polyethylene alcohol is meant in the A composition aspect the invention described above the 1st and does not carry out modified polyethylene alcohol.In addition, said modified polyvinyl alcohol, be meant in the A composition aspect the invention described above the 1st and carried out modified polyethylene alcohol, based on the invention described above the 1st aspect in same reason, preferentially select the polyvinyl alcohol that has silyl in the molecule, carboxy-modified polyvinyl alcohol for use.
The following describes the cooperation ratio of above-mentioned A, B, D composition.
The A composition is the basic composition that is used to obtain gas barrier property, and the B composition is to be used for improving resulting composition of filming with the sticking power of ground.
The A composition in the present invention the 2nd aspect and the proportioning of B composition are 10/1-5/4 in weight ratio (A/B), preferably 20/3-5/4, preferably 2/1-5/3.
In addition, the A composition in the present invention the 3rd aspect and the proportioning of B composition, (A/B) is 20/1-1/2 in weight ratio, ground and the sticking power of filming when under high humidity more, preserving in order to improve, 10/1-1/2 preferably, for can be at dry solidification, preferably 20/3-1/2, preferably 2/1-1/1 under the low temperature more.In addition, when the pure and mild unmodified polyethylene alcohol of modified poly ethylene was mixed use, the modified polyvinyl alcohol that mixes more than the 10 weight % in the total amount of A composition was comparatively suitable, preferably more than the 20 weight %.
The use level of A composition when (use level of B composition is very few), is under the situation of polyester at ground particularly too much, and the sticking power of filming with ground reduces.Otherwise, during the use level of A composition very few (use level of B composition is too much), resulting gas barrier property deficiency of filming.
The proportioning of D composition can preferably make the solid shape branch of resulting composition of gas barrier paint reach 1-20 weight % according to suitably selections such as application conditions, can be according to suitably selections such as coating processs in this scope.When D composition use level is too much, be difficult to obtain filming of necessary thickness, otherwise when the use level of D composition was very few, coating worsened easily.
In aspect the of the present invention the 2nd and the 3rd, owing to make water as solvent, sometimes above-mentioned B composition promptly has the also hydrolysis lentamente of a part of the organoalkoxysilane of amino and/or imino-, be transformed into its (part) hydrolyzate, this hydrolyzate can further be transformed into (part) condenses when also having.Even taking place under the situation of this variation, can obtain the of the present invention the 2nd and the effect of the 3rd aspect too.Therefore, the B composition in the of the present invention the 2nd and the 3rd aspect also can be to have the organoalkoxysilane of amino and/or imino-and the mixture of its (part) hydrolyzate and/or (part) condenses.
In addition, based on the invention described above the 1st aspect in same reason, preferably contain fine fibrillated fibre as the E composition.Identical described in the 1st aspect of E composition and proportioning thereof and the invention described above.
The composition of gas barrier paint of the present invention the 2nd and the 3rd aspect, basically be to constitute by above-mentioned A, B, D composition or A, B, D, E composition, in the scope of not damaging effect of the present invention, in order to improve coating, with respect to 100 parts of the total amounts (weight) of A, B, D composition or A, B, D, E composition, can add 10 parts (weight) following thickening material, defoamer, curing catalysts, wettability modifying agent, softening agent etc.
The composition of gas barrier paint of the present invention the 2nd and the 3rd aspect is coated on the ground, forms filming of gas barrier property.
When on ground, being coated with, for example can adopt customary way in the past such as dip coated, spraying, flow coat, roller coat, coiling rod blade coating, rotary coating, direct notch board coating.In order to simplify the application operation, in addition,, obtain good gas-barrier properties for feasible sticking power with ground remains on the realistic scale, the thickness of filming should be at 0.2-7 μ m, preferably 0.3-1.5 μ m.
For the proportioning of the composition of gas barrier paint of the present invention the 2nd aspect, the A composition composition of gas barrier paint in the present invention the 3rd aspect of weight ratio (A/B) less than 20/3, the dry solidification of filming after the coating should surpass under 60 ℃ the heating atmosphere in the film coated surface temperature and carry out.If the envrionment temperature during dry solidification is low excessively, when particularly preserving resulting gas-barrier films under high humidity, ground reduces easily with the bonding force of filming.The upper limit of the film coated surface temperature during above-mentioned dry solidification also depends on the thermotolerance of ground, generally is 120 ℃.
On the other hand, count the composition of gas barrier paint of the present invention the 3rd aspect more than 20/3 with weight ratio (A/B) for the proportioning of A composition, as long as reach dry solidification in the heating atmosphere more than 50 ℃, just be not easy to occur in the ground preserving under the high humidity and cause and be coated with binding force of membrane and reduce in the film coated surface temperature.Therefore, the proportioning of A composition in weight ratio (A/B) at the composition of gas barrier paint aspect the present invention more than 20/3 the 3rd, dried coating film after being coated with in the film coated surface temperature reaches heating atmosphere more than 50 ℃ solidifies just passable, and its advantage is the restriction that can relax the heat drying condition.The upper limit of film coated surface temperature is 120 ℃ with top described identical at this moment.
As ground, for example can use synthetic resins such as polyester, polypropylene, polycarbonate, on ground, formed by filming of constituting of composition of gas barrier paint of the present invention and the film or the thin slice that obtain, and, can be used for the purposes such as packing of gas barrier property at the film or the thin slice that have further stacked thermal synthesis layer on this film of filming or the thin slice or other layer and obtain.Composition of gas barrier paint of the present invention, formation has filming of good adhesion on the polyester substrates that can use in a large number on the packaging, thereby can obtain being particularly suitable for the film or the thin slice of gas barrier property packing purposes.
Illustrate in greater detail the present invention below by embodiment, wherein, embodiment 1-20 and comparative example 1-6 are about the 1st aspect of the present invention, and embodiment 21-31 and comparative example 7-10 are about the of the present invention the 2nd and the 3rd aspect.
Embodiment 1-4
Use PVA (A
1Composition: polyvinyl alcohol: Network ラ レ company makes " Port バ-Le 105 "), APTMS (B
1N-β (amino-ethyl) Y-TSL 8330), APTES (B composition:
2The Y-aminopropyltriethoxywerene werene), 1EDGE (C composition: ethylene glycol diglycidylether), IPA and H composition:
2O (D composition: Virahol and water) prepares the gas barrier coating resin combination according to the proportioning shown in the table 1.
At first, PVA is dissolved in IPA/H
2In the solvent of O=20/80 (weight ratio), form 5 weight % solution, press the proportioning shown in the table 1 and in this PVA solution of 100g, mix APTMS or APTES, stir then.In this mixture, add 1EDGE in the ratio shown in the table 1 again, stirred 1 hour, make composition of gas barrier paint.
Resulting composition of gas barrier paint is coated on PET (polyester) the film ground of thick 25 μ m, forms the thickness of about 1 μ m.In 80 ℃ atmosphere, kept 1 minute, dried coating film is solidified.The film coated surface temperature of this moment all is about 65 ℃.This surface temperature is to utilize the heat label on the part that is attached to ground in advance to measure.Use the resulting ground of filming that has to carry out following evaluation.The results are shown in the table 1.
(1) transparency
By visual inspection, to formation before filming ground and have the ground of filming and compare and estimate.Both transparencys do not have the situation of difference to be labeled as zero basically, and the poor slightly situation of the transparency that has the ground of filming is labeled as △.
(2) gas barrier property
In the exsiccant room temperature atmosphere, use oxygen permeability determinator (MOCON company makes " OX-TRAN TWIN ") to measure the perviousness of oxygen.
(3) sticking power
On the resulting film coated surface that has a ground of filming, the CPP (un-stretched polypropylene) of dry laminate coating thickness 25 μ m by using the polyurethanes binding agent, 40 ℃ of following burin-in process 48 hours, it is wide to be cut into 15mm then, peels off with the T type of being with the ground of filming by the CPP film and obtains stripping strength.Stripping strength is labeled as the following person of 490mN/15mm *, ground person of breaking and stripping strength are labeled as zero the above person of 1960mN/15mm.
(4) high humidity keeping quality
To carry out placing for 2 weeks in the atmosphere of 20 ℃ of temperature, humidity 90%RH with the laminate film of the same dry laminate of sticking power evaluation, it is wide to be cut into 15mm then, peels off and obtains stripping strength by the film T type of ground of CPP film and band.Stripping strength is labeled as the following person of 490mN/15mm *, ground person of breaking and stripping strength are labeled as zero the above person of 1960mN/15mm.
Embodiment 5
Use S-PVA (A
2Composition: the polyvinyl alcohol that has silyl in the molecule: Network ラ レ company makes " R-2105 "), APTES (B
2The Y-aminopropyltriethoxywerene werene), 1EDGE (C composition: ethylene glycol diglycidylether), IPA and H composition:
2O (D composition: Virahol and water) prepares the gas barrier coating resin combination according to the proportioning shown in the table 1.
At first, S-PVA is dissolved in IPA/H
2In the solvent of O=20/80 (weight ratio), form 5 weight % solution, in this S-PVA solution of 100g, mix 2.5gAPTES, stir then.In this mixture, add 0.25g 1EDGE again, stirred 1 hour, make composition of gas barrier paint.
Resulting composition of gas barrier paint is coated on PET (polyester) the film ground of thick 25 μ m, forms the thickness of about 1 μ m.In 80 ℃ atmosphere, kept 1 minute, dried coating film is solidified.The film coated surface temperature of this moment all is about 65 ℃.This surface temperature is to utilize the heat label on the part that is attached to ground in advance to measure.Use the resulting ground of filming that has to carry out the evaluation same with embodiment 1-4.The results are shown in the table 1.
Embodiment 6
Use composition of gas barrier paint similarly to Example 5, blowing hot air 1 minute makes dried coating film solidify (surface temperature of filming this moment is about 55 ℃, and this surface temperature is to utilize the heat label on the part that is attached to ground in advance to measure).In addition operation similarly to Example 5 obtains having the ground of filming, and estimates equally.The results are shown in the table 1.
Embodiment 7-10
Use PVA (A
1Composition: polyvinyl alcohol: Network ラ レ company makes " Port バ-Le 105 "), S-PVA (A
2Composition: the polyvinyl alcohol that has silyl in the molecule: Network ラ レ company makes " R-2105 "), APTES (B
2The Y-aminopropyltriethoxywerene werene), 1EDGE (C composition: ethylene glycol diglycidylether), IPA and H composition:
2O (D composition: Virahol and water), MFC1 (E
1Composition: make the fine fibrillated fibre element miniaturization of softwood tree bleached kraft pulp, number average fiber length 0.06mm, axial ratio about 60 :), MFC2 (E Gu shape divides 2.0%
2Composition: with the fine fibrillated fibre miniaturization of bleached hardwood kraft paper pulp, number average fiber length 0.07mm, axial ratio about 70: Gu shape divides 2.5%), prepare the gas barrier coating resin combination according to the proportioning shown in the table 2.MFC1 in the table 2 and the content of MFC2 are the content that divides as solid shape.
At first, PVA or S-PVA are dissolved in IPA/H
2In the solvent of O=20/80 (weight ratio), form 5 weight % solution, in this solution of 100g, add, disperse MFC1 or the MFC2 of 0.2g,, stir then then for this solution mixing of 100g 2.5gAPTES.In this mixture, add 0.25g 1EDGE again, stirred 1 hour, make composition of gas barrier paint.
Resulting composition of gas barrier paint is coated on PET (polyester) the film ground of thick 12 μ m, forms the thickness of about 1 μ m.In 80 ℃ atmosphere, kept 1 minute, dried coating film is solidified.The film coated surface temperature of this moment is about 65 ℃.This surface temperature is to utilize the heat label on the part that is attached to ground in advance to measure.Use the resulting ground of filming that has to carry out the evaluation same with embodiment 1-4.The results are shown in the table 2.
Embodiment 11-14
Use the composition of gas barrier paint identical with embodiment 7-10 respectively, blowing hot air 1 minute makes dried coating film solidify (surface temperature of filming this moment is about 55 ℃, and this surface temperature is to utilize the heat label on the part that is attached to ground in advance to measure).In addition operate equally with embodiment 7-10, obtain having the ground of filming, estimate equally.The results are shown in the table 2.
Embodiment 15-17
Use C-PVA (A
3Composition: carboxy-modified PVA: Network ラ レ company makes " KM-118 "), APTES (B
2The Y-aminopropyltriethoxywerene werene), 1EDGE (C composition: ethylene glycol diglycidylether), IPA and H composition:
2O (D composition: Virahol and water), MFC1 (E
1Composition: make the fine fibrillated fibre element miniaturization of softwood tree bleached kraft pulp, number average fiber length 0.06mm, axial ratio about 60 :), MFC2 (E Gu shape divides 2.0%
2Composition: with the fine fibrillated fibre element miniaturization of bleached hardwood kraft paper pulp, number average fiber length 0.07mm, axial ratio about 70: Gu shape divides 2.5%), prepare the gas barrier coating resin combination according to the proportioning shown in the table 3.MFC1 in the table 3 and the content of MFC2 are the content that divides as solid shape.
At first, C-PVA is dissolved in IPA/H
2In the solvent of O=20/80 (weight ratio), form 5 weight % solution, in this solution of 100g, add, disperse MFC1 or the MFC2 of 0.2g,, stir then then for this solution mixing of 100g 2.5gAPTES.In this mixture, add 0.25g 1EDGE again, stirred 1 hour, make composition of gas barrier paint.
Resulting composition of gas barrier paint is coated on PET (polyester) the film ground of thick 12 μ m, forms the thickness of about 1 μ m.In 80 ℃ atmosphere, kept 1 minute, dried coating film is solidified.The film coated surface temperature of this moment is about 65 ℃.This surface temperature is to utilize the heat label on the part that is attached to ground in advance to measure.Use the resulting ground of filming that has to carry out the evaluation same with embodiment 1-4.The results are shown in the table 3.
Embodiment 18-20
Use the composition of gas barrier paint identical with embodiment 15-17 respectively, blowing hot air 1 minute makes dried coating film solidify (surface temperature of filming this moment is about 55 ℃, and this surface temperature is to utilize the heat label on the part that is attached to ground in advance to measure).In addition operate equally with embodiment 15-17, obtain having the ground of filming, estimate equally.The results are shown in the table 3.
Reference example 1
Use the composition of gas barrier paint identical,, make and have the ground of filming, estimate equally according to dried coating film condition of cure similarly to Example 6 with embodiment 1.The results are shown in the table 1.
Comparative example 1-5
Use with embodiment 1-4 in identical PVA, APTMS, APTES, 1EDGE, IPA and H
2O makes composition by the proportioning shown in the table 4, uses resultant composition and embodiment 1-4 to estimate equally.
The results are shown in the table 4.In addition, in comparative example 4 and 5, except the PET film of thickness 25 μ m, OPP (oriented polypropylene) film that also uses thick 20 μ m is as ground, but any ground no matter, wettability is all bad, can not form to film.In coating thickness one hurdle of table 4 * be exactly to represent this situation.
Comparative example 6
The PVA that uses among the embodiment 1-4 is dissolved in the water, form 5 weight % solution, in this solution, add acetic acid, stir the back and drip the APTMS that uses among the embodiment 1-4 by the proportioning in the table 4, stirred 30 minutes, press the proportioning of table 4 again and add GPTMS (other composition: the 3-glycidoxypropyltrime,hoxysilane), make composition.Use resultant composition, estimate equally with embodiment 1-4.The results are shown in the table 4.
Embodiment 21-34, comparative example 7-10
Use PVA (A
1Composition: polyvinyl alcohol: Network ラ レ company makes " Port バ-Le 105 "), S-PVA (A
2Composition: the polyvinyl alcohol that has silyl in the molecule: Network ラ レ company makes " R-2105 "), C-PVA (A
3Composition: carboxy-modified PVA: Network ラ レ company makes " KM-118 "), APTES (B
2The Y-aminopropyltriethoxywerene werene), IPA and H composition:
2O (D composition: Virahol and water) prepares the gas barrier coating resin combination by the proportioning shown in the table 5-table 7.
At first, PVA, S-PVA or C-PVA are dissolved in IPA/H
2In the solvent of O=20/80 (weight ratio), form 5 weight % solution, in this solution of 100g, mix APTES, stirred 1 hour, make composition of gas barrier paint by the proportioning in the table 5-table 7.
Resulting composition of gas barrier paint is coated on PET (polyester) the film ground of thick 12 μ m, forms the thickness of about 1 μ m.By the desiccated surface temperature shown in the table 5-table 7 dried coating film is solidified.About 65 ℃ of desiccated surface temperature, about 55 ℃ concrete drying conditions in the table 5-table 7 be respectively, in 80 ℃ atmosphere, kept 1 minute, and blowing hot air 1 minute, surface temperature is to utilize the heat label on the part that is attached to ground in advance to measure.
Use the resulting ground of filming that has, estimate equally with embodiment 1-4.Described high humidity keeping quality B except laminate film was placed in the atmosphere of 40 ℃ of temperature, humidity 90%RH one month, estimates equally with the high humidity keeping quality of embodiment 1-4.
The results are shown in the table 5-table 7.
[table 1]
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Reference example 1 | ||
| Form ︵ weight ratio ︶ | A 1：PVA | ??5 | ??5 | ??5 | ??5 | ??0 | ??0 | ??5 |
| A 2：S-PVA | ??0 | ??0 | ??0 | ??0 | ??5 | ??5 | ??0 | |
| B 1：APTMS | ??5 | ??0 | ??2.5 | ??0 | ??0 | ??0 | ??5 | |
| B 2：APTES | ??0 | ??5 | ??0 | ??2.5 | ??2.5 | ??2.5 | ??0 | |
| C：1EDGE | ??0.5 | ??0.5 | ??0.25 | ??0.25 | ??0.25 | ??0.25 | ??0.5 | |
| D: solvent (IPA/H 2O) | ??95(20/80) | ??95(20/80) | ??95(20/80) | ??95(20/80) | ??95(20/80) | ??95(20/80) | ??95(20/80) | |
| Ground | ??PET | ??PET | ??PET | ??PET | ??PET | ??PET | ??PET | |
| Thickness (μ m) | ??～1 | ??～1 | ??～1 | ??～1 | ??～1 | ??～1 | ??～1 | |
| Estimate | The transparency | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ |
| Gas barrier property (ml/m 2·atm·day) | ??2 | ??2 | ??＜1 | ??＜1 | ??＜1 | ??＜1 | ??2 | |
| The high humidity keeping quality | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??× | |
| Sticking power | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | |
[table 2]
| Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 | ||
| Form ︵ weight ratio ︶ | A 1：PVA | ??5 | ??5 | ??0 | ??0 | ??5 | ??5 | ??0 | ??0 |
| A 2：S-PVA | ??0 | ??0 | ??5 | ??5 | ??0 | ??0 | ??5 | ??5 | |
| B 1：APTMS | ??0 | ??0 | ??0 | ??0 | ??0 | ??0 | ??0 | ??0 | |
| B 2：APTES | ??2.5 | ??2.5 | ??2.5 | ??2.5 | ??2.5 | ??2.5 | ??2.5 | ??2.5 | |
| C：1EDGE | ??0.25 | ??0.25 | ??0.25 | ??0.25 | ??0.25 | ??0.25 | ??0.25 | ??0.25 | |
| D: solvent (IPA/H 2O) | ??95(20/80) | ??95(20/80) | ??95(20/80) | ??95(20/80) | ??95(20/80) | ??95(20/80) | ??95(20/80) | ??95(20/80) | |
| E 1：MFC1 | ??0.004 | ??0 | ??0.004 | ??0 | ??0.004 | ??0 | ??0.004 | ??0 | |
| E 2：MFC2 | ??0 | ??0.005 | ??0 | ??0.005 | ??0 | ??0.005 | ??0 | ??0.005 | |
| Ground | ??PET | ??PET | ??PET | ??PET | ??PET | ??PET | ??PET | ??PET | |
| Thickness (μ m) | ??～1 | ??～1 | ??～1 | ??～1 | ??～1 | ??～1 | ??～1 | ??～1 | |
| Estimate | The transparency | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ |
| Gas barrier property (ml/m 2·atm·day) | ??2 | ??2 | ??＜1 | ??＜1 | ??＜1 | ??＜1 | ??＜1 | ??＜1 | |
| The high humidity keeping quality | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | |
| Sticking power | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | |
[table 3]
| Embodiment 15 | Embodiment 16 | Embodiment 17 | Embodiment 18 | Embodiment 19 | Embodiment 20 | ||
| Form ︵ weight ratio ︶ | A 3：C-PVA | ????5 | ????5 | ????5 | ????5 | ????5 | ????5 |
| B 2：APTES | ????2.5 | ????2.5 | ????2.5 | ????2.5 | ????2.5 | ????2.5 | |
| C：1EDGE | ????0.25 | ????0.25 | ????0.25 | ????0.25 | ????0.25 | ????0.25 | |
| D: solvent (IPA/H 2O) | ????95(20/80) | ????95(20/80) | ????95(20/80) | ????95(20/80) | ????95(20/80) | ????95(20/80) | |
| E 1：MFC1 | ????0 | ????0 | ????0.004 | ????0 | ????0.004 | ????0 | |
| E 2：MFC2 | ????0 | ????0 | ????0 | ????0.005 | ????0 | ????0.005 | |
| Ground | ????PET | ????PET | ????PET | ????PET | ????PET | ????PET | |
| Thickness (μ m) | ????～1 | ????～1 | ????～1 | ????～1 | ????～1 | ????～1 | |
| Estimate | The transparency | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ |
| Gas barrier property (ml/m 2·atm·day) | ????＜1 | ????＜1 | ????＜1 | ????＜1 | ????＜1 | ????＜1 | |
| The high humidity keeping quality | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | |
| Sticking power | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | |
[table 4]
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | ||
| Form ︵ weight ratio ︶ | A 1：PVA | ????5 | ????5 | ????5 | ????5 | ????0 | ??5 |
| A 2：S-PVA | ????0 | ????0 | ????0 | ????0 | ????0 | ??0 | |
| B 1：APTMS | ????0 | ????5 | ????0 | ????0 | ????20 | ??2 | |
| B 2：APTES | ????0 | ????0 | ????5 | ????0 | ????0 | ??- | |
| C：1EDGE | ????0 | ????0 | ????0 | ????2.5 | ????2 | ??- | |
| D: solvent (IPA/H 2O) | ????95(20/80) | ????95(20/80) | ????95(20/80) | ????95(20/80) | ????100(20/80) | ??95(0/100) | |
| He: GPTMS | ????0 | ????0 | ????0 | ????0 | ????0 | ??2 | |
| Ground | ????PET | ????PET | ????PET | ????PET ????OPP | ????PET ????OPP | ??PET | |
| Thickness (μ m) | ????～1 | ????～1 | ????～1 | ????× | ????× | ??× | |
| Estimate | The transparency | ????○ | ????△ | ????○ | ????- | ????- | ??- |
| Gas barrier property (ml/m 2·atm·day) | ????0 | ????1 | ????＜1 | ????- | ????- | ??- | |
| The high humidity keeping quality | ????× | ????× | ????× | ????- | ????- | ??- | |
| Sticking power | ????× | ????× | ????○ | ????- | ????- | ??- | |
[table 5]
| Embodiment 21 | Embodiment 22 | Embodiment 23 | Embodiment 24 | Embodiment 25 | Embodiment 26 | Embodiment 27 | Embodiment 28 | ||
| Form ︵ weight ratio ︶ | A 1：PVA | ??0 | ??0 | ??0 | ??0 | ??0 | ??0 | ??0 | ??0 |
| A 2：S-PVA | ??5 | ??5 | ??5 | ??0 | ??0 | ??0 | ??5 | ??0 | |
| A 3：C-PVA | ??0 | ??0 | ??0 | ??5 | ??5 | ??5 | ??0 | ??5 | |
| B 2：APTES | ??2.5 | ??0.75 | ??0.5 | ??2.5 | ??0.75 | ??0.5 | ??0.5 | ??0.5 | |
| D: solvent (IPA/H 2O) | ??95(20/80) | ??95(20/80) | ??95(20/80) | ??95(20/80) | ??95(20/80) | ??95(20/80) | ??95(20/80) | ??95(20/80) | |
| The desiccated surface temperature (℃) | About 55 | About 55 | About 65 | About 55 | About 55 | About 65 | About 55 | About 55 | |
| Ground | ??PET | ??PET | ??PET | ??PET | ??PET | ??PET | ??PET | ??PET | |
| Thickness (μ m) | ??～1 | ??～1 | ??～1 | ??～1 | ??～1 | ??～1 | ??～1 | ??～1 | |
| Estimate | The transparency | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ |
| Gas barrier property (ml/m 2·atm·day) | ??＜1 | ??＜1 | ??＜1 | ??＜1 | ??＜1 | ??＜1 | ??＜1 | ??＜1 | |
| The high humidity keeping quality | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | |
| High humidity keeping quality B | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??× | ??× | |
| Sticking power | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | |
[table 6]
| Embodiment 29 | Embodiment 30 | Embodiment 31 | Embodiment 32 | Embodiment 33 | Embodiment 34 | ||
| Form ︵ weight ratio ︶ | A 1：PVA | ????5 | ????0 | ????0 | ????3.5 | ????2.5 | ????1.25 |
| A 2：S-PVA | ????0 | ????5 | ????0 | ????1.5 | ????0 | ????2.5 | |
| A 3：C-PVA | ????0 | ????0 | ????5 | ????0 | ????2.5 | ????1.25 | |
| B 2：APTES | ????2.5 | ????0.35 | ????0.35 | ????1.25 | ????1.25 | ????1.25 | |
| D: solvent (IPA/H 2O) | ????95(20/80) | ????95(20/80) | ????95(20/80) | ????95(20/80) | ????95(20/80) | ????95(20/80) | |
| The desiccated surface temperature (℃) | About 65 | About 65 | About 65 | About 55 | About 55 | About 55 | |
| Ground | ????PET | ????PET | ????PET | ????PET | ????PET | ????PET | |
| Thickness (μ m) | ????～1 | ????～1 | ????～1 | ????～1 | ????～1 | ????～1 | |
| Estimate | The transparency | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ |
| Gas barrier property (ml/m 2·atm·day) | ????＜1 | ????＜1 | ????＜1 | ????＜1 | ????＜1 | ????＜1 | |
| The high humidity keeping quality | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | |
| High humidity keeping quality B | ????× | ????× | ????× | ????○ | ????○ | ????○ | |
| Sticking power | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | |
[table 7]
| Comparative example 7 | Comparative example 8 | Comparative example 9 | Comparative example 10 | ||
| Form ︵ weight ratio ︶ | A 1：PVA | ????5 | ????0 | ????0 | ????5 |
| A 2：S-PVA | ????0 | ????5 | ????0 | ????0 | |
| A 3：C-PVA | ????0 | ????0 | ????5 | ????0 | |
| B 2：APTES | ????0 | ????0 | ????0 | ????0.35 | |
| D: solvent (IPA/H 2O) | ????95(20/80) | ????95(20/80) | ????95(20/80) | ????95(20/80) | |
| The desiccated surface temperature (℃) | About 55 | About 55 | About 55 | About 65 | |
| Ground | ????PET | ????PET | ????PET | ????PET | |
| Thickness (μ m) | ????～1 | ????～1 | ????～1 | ????～1 | |
| Estimate | The transparency | ????○ | ????○ | ????○ | ????○ |
| Gas barrier property (ml/m 2·atm·day) | ????＜1 | ????＜1 | ????＜1 | ????＜1 | |
| The high humidity keeping quality | ????× | ????× | ????× | ????× | |
| High humidity keeping quality B | ????× | ????× | ????× | ????× | |
| Sticking power | ????× | ????× | ????× | ????× | |
More than describe the present invention, effect of the present invention is as follows:
(1) even for the ground of polyester, do not having to form the good gas barrier coating membrane of adhesive force in the situation of anchor layer yet. Because polyester is widely used in packaging material, thereby can obtain easily the good packaging material of gas barrier property.
(2) owing to do not use the carboxylic acid such as acetic acid, can prevent because the deterioration of the sour smelly painting work environment that causes.
(3) transparency and moisture-proof are good.
(4) proportioning of gas barrier property coating composition, A composition of using the polyvinyl alcohol that has silicyl in the molecule or the present invention carboxyl modified polyvinylalcohol or that contain the E composition the 1st aspect as the A composition by weight (A/B) meter at the gas barrier property coating composition aspect the present invention the 3rd more than 20/3, even when ground forms filming of dry solidification, relax the restriction to drying condition, also be not easy to occur under the high humility and preserve and adhesive force that cause and ground reduction, thereby form gas barrier layer at the relatively poor ground of heat resistance easily, and the Temperature Setting during dry solidification is more prone to.
Claims (14)
1. composition of gas barrier paint is characterized in that, said composition contains following A, B, C, D composition, and the weight ratio A/B of A composition and B composition is 10/1-1/2, and the weight ratio B/C of B composition and C composition is 20/1-2/1:
A: polyvinyl alcohol;
B: as the represented organoalkoxysilane of following (I) formula with amino and/or imino-;
In the formula, R
3Expression contains the alkylene of carbon number 1～4, R
4And R
5Expression contains the alkyl of carbon number 1～4, and X represents hydrogen atom or aminoalkyl group, and n represents 1 or 0;
C: by the glycidyl ether that following (II) formula is represented, in the formula, n represents the integer of 0-4;
D: the water that has added lower alcohol.
2. the described composition of gas barrier paint of claim 1 is characterized in that, described A composition is the polyvinyl alcohol that has silyl in the molecule.
3. the described composition of gas barrier paint of claim 2 is characterized in that, the content of silyl is 0.01-5 mole %.
4. the described composition of gas barrier paint of claim 1 is characterized in that, the A composition is carboxy-modified polyvinyl alcohol.
5. the described composition of gas barrier paint of claim 1 is characterized in that, the A composition is the mixture of modified polyvinyl alcohol and unmodified polyethylene alcohol.
6. each described composition of gas barrier paint among the claim 1-5 is characterized in that, the B composition is to have the organoalkoxysilane of amino and/or imino-and the mixture of its hydrolyzate or partial hydrolystate and/or condenses or partial condensate.
7. each described composition of gas barrier paint among the claim 1-5 is characterized in that, the C composition is the mixture of the glycidyl ether shown in (II) formula and its hydrolyzate or partial hydrolystate.
8. the described composition of gas barrier paint of claim 6 is characterized in that, the C composition is the mixture of the glycidyl ether shown in (II) formula and its hydrolyzate or partial hydrolystate.
9. each described composition of gas barrier paint among the claim 1-5 is characterized in that, contains E: fine fibrillated fibre, the weight ratio B/E of B composition and E composition is 100/2-100/0.05.
10. the described composition of gas barrier paint of claim 6 is characterized in that, contains E: fine fibrillated fibre, the weight ratio B/E of B composition and E composition is 100/2-100/0.05.
11. the described composition of gas barrier paint of claim 7 is characterized in that, contains E: fine fibrillated fibre, the weight ratio B/E of B composition and E composition is 100/2-100/0.05.
12. the described composition of gas barrier paint of claim 8 is characterized in that, contains E: fine fibrillated fibre, the weight ratio B/E of B composition and E composition is 100/2-100/0.05.
13. gas-barrier films is characterized in that, this film has filming of the described composition of gas barrier paint of claim 1.
14. the described gas-barrier films of claim 13 is characterized in that, filming of composition of gas barrier paint is set on the ground of polyester.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP349598/1999 | 1999-12-09 | ||
| JP34959899 | 1999-12-09 | ||
| JP183946/2000 | 2000-06-20 | ||
| JP2000183946 | 2000-06-20 | ||
| JP2000223223 | 2000-07-25 | ||
| JP223223/2000 | 2000-07-25 | ||
| JP298250/2000 | 2000-09-29 | ||
| JP2000298250A JP4758539B2 (en) | 1999-12-09 | 2000-09-29 | Coating composition and gas barrier film |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001341588A Division CN1179003C (en) | 1999-12-09 | 2000-12-06 | Composition of gas barrier paint and gas barrier film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1537903A true CN1537903A (en) | 2004-10-20 |
Family
ID=27480699
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2004100341873A Pending CN1537903A (en) | 1999-12-09 | 2000-12-06 | Gas barrier coating composition and gas-barrier film |
| CNB001341588A Expired - Fee Related CN1179003C (en) | 1999-12-09 | 2000-12-06 | Composition of gas barrier paint and gas barrier film |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001341588A Expired - Fee Related CN1179003C (en) | 1999-12-09 | 2000-12-06 | Composition of gas barrier paint and gas barrier film |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP4758539B2 (en) |
| KR (1) | KR100407027B1 (en) |
| CN (2) | CN1537903A (en) |
| HK (1) | HK1038940A1 (en) |
| TW (1) | TWI275619B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002188038A (en) * | 2000-12-21 | 2002-07-05 | Kyodo Printing Co Ltd | Gas-barrier coating composition and gas-barrier film |
| JP2004231730A (en) * | 2003-01-29 | 2004-08-19 | Mitsubishi Gas Chem Co Inc | Gas barrier coated film |
| CN100357374C (en) * | 2004-04-12 | 2007-12-26 | 刘建林 | Water insoluble modified polyvinyl alcohol coating liquid and its producing process |
| WO2006003829A1 (en) * | 2004-06-30 | 2006-01-12 | Dainippon Ink And Chemicals, Inc. | Aqueous coating composition |
| JP2009024159A (en) | 2007-04-09 | 2009-02-05 | Futura Polyesters Ltd | Polyester-based gas barrier resin and its process |
| JP5407304B2 (en) * | 2008-12-01 | 2014-02-05 | 凸版印刷株式会社 | Laminated body |
| JP6857011B2 (en) * | 2016-11-10 | 2021-04-14 | サカタインクス株式会社 | Barrier coating composition for laminating and barrier composite film for laminating |
| JP7000763B2 (en) * | 2017-09-15 | 2022-01-19 | 凸版印刷株式会社 | Barrier film laminate |
| JP7069664B2 (en) * | 2017-11-28 | 2022-05-18 | 凸版印刷株式会社 | Gas barrier film |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3018927B2 (en) * | 1994-11-11 | 2000-03-13 | 株式会社日本触媒 | Manufacturing method of coating film |
| JP3048334B2 (en) * | 1996-02-28 | 2000-06-05 | 株式会社日本触媒 | Continuous production method of coating film |
| JPH09255910A (en) * | 1996-03-25 | 1997-09-30 | Teijin Ltd | Coating composition |
| JP3772490B2 (en) * | 1996-10-09 | 2006-05-10 | 東レ株式会社 | Gas barrier film and method for producing the same |
| JP3692706B2 (en) * | 1997-04-28 | 2005-09-07 | 東レ株式会社 | Gas barrier film |
| JP3969464B2 (en) * | 1997-10-30 | 2007-09-05 | 王子製紙株式会社 | Method for producing water absorbent sheet |
| JPH11315222A (en) * | 1998-05-07 | 1999-11-16 | Sumitomo Chem Co Ltd | Water-based coating material |
| JPH11333364A (en) * | 1998-05-28 | 1999-12-07 | Sumitomo Chem Co Ltd | Production of film laminate |
| JPH11348955A (en) * | 1998-06-10 | 1999-12-21 | Kuraray Co Ltd | Container |
-
2000
- 2000-09-29 JP JP2000298250A patent/JP4758539B2/en not_active Expired - Fee Related
- 2000-12-06 CN CNA2004100341873A patent/CN1537903A/en active Pending
- 2000-12-06 CN CNB001341588A patent/CN1179003C/en not_active Expired - Fee Related
- 2000-12-08 TW TW089126202A patent/TWI275619B/en not_active IP Right Cessation
- 2000-12-08 KR KR10-2000-0074592A patent/KR100407027B1/en not_active IP Right Cessation
-
2002
- 2002-01-18 HK HK02100391A patent/HK1038940A1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JP4758539B2 (en) | 2011-08-31 |
| CN1303895A (en) | 2001-07-18 |
| KR100407027B1 (en) | 2003-11-28 |
| KR20010062265A (en) | 2001-07-07 |
| TWI275619B (en) | 2007-03-11 |
| JP2002105382A (en) | 2002-04-10 |
| HK1038940A1 (en) | 2002-04-04 |
| CN1179003C (en) | 2004-12-08 |
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