CN1207142C

CN1207142C - Gas stop resin formation body

Info

Publication number: CN1207142C
Application number: CNB01137599XA
Authority: CN
Inventors: 山本哲也; 原田弘子
Original assignee: Nippon Shokubai Co Ltd
Current assignee: Nippon Shokubai Co Ltd
Priority date: 2000-08-21
Filing date: 2001-08-21
Publication date: 2005-06-22
Anticipated expiration: 2021-08-21
Also published as: KR20020015287A; CN1345658A; TWI265861B; KR100550109B1

Abstract

A resin molded product for a gas barrier are provided to allow the gas barrier characteristic to be maintained to be high under a high temperature and a high humidity.The resin molded product comprises a substrate, and a coating layer prepared from the coating composition containing an organic compound having a functional group capable of reacting a polymer having an amino group and an amino group within the molecule, wherein the oxygen transmittance after it is treated with 90% Rh at 60 deg.C for 24 hours to that before treated is 10.0 or less.

Description

Gas stop resin formation body

Technical field

The invention relates to novel gas stop resin formation body and choke transparent membrane.In more detail, the invention relates to and to be applicable to novel gas stop resin formation body and the choke transparent membrane of liquid crystal display with substrate and packing material.

Background technology

To minimum gas stop resin formation body and choke transparent membranes of gas permeability such as oxygen, nitrogen, carbon dioxide, water vapor, the needs in fields such as packing material increase.Packing material for such food, beverage product container and wrappage etc., in order to give formed body material gas barrier properties such as plastic sheeting or sheet material, present known following several method, (1) forms formed body with air impermeability raw materials such as ethylene-vinyl alcohol copolymer, vinylidene chloride analog copolymer, aromatics nylon; (2) with these air impermeability raw material laminations or be coated on other material; (3) at film like material upper strata jewelling paper tinsel; (4) method of vacuum coating metal and metal oxide etc.

Yet, in the middle of the air impermeability raw material in (1) and (2), exist the moisture-proof of ethylene-vinyl alcohol copolymer and fragrant same clan nylon poor, and rising along with temperature in the atmosphere, descend the significantly problem of (the humidity interdependence of gas barrier property is big) of gas barrier property, and, worry to become public hazards because the vinylidene chloride analog copolymer contains the chlorine atom.And, with the packing material that the aluminium foil laminate film in (3) is manufactured, can not see the content of packaging from the outside, and the metal of the vacuum coating in (4) and metal-oxide film, on vacuum coating, crack easily owing to its subduing property difference.There is the problem that causes that gas barrier property reduces.

In addition, for allowing to use gas stop resin formation body and choke food, the beverage product of transparent membrane that obtain thus as the packing material of container and wrappage etc., the consumer will endure strict scrutiny when shopping, for example, because base material and choke are bad with the adaptation between the overlayer, with subduing property problem is arranged, cause easily and peel off, transparent variation; And for the bad packing material of printing, no matter how and the no one buys the quality of food, beverage product itself, the phenomenon of not going out, return goods will occur selling.So we can say, for requiring extremely strictness of benchmark with transparent membrane as the gas stop resin formation body of the container of food, beverage product and wrappage etc. and choke.Except that gas barrier property, also seeking the performance with high requests such as base material adaptation, the transparency, subduing property, printing, moisture-proofs, so the task of top priority is exactly gas stop resin formation body and choke transparent membrane that exploitation can be had both the new raw material of above-mentioned various characteristics.

Also have, this gas stop resin formation body and choke are used as the food of the packing material of container and wrappage etc. for permission with transparent membrane, the beverage product, from the fabricator, the peasant, the transporter is between the ultimate consumer, (comprise commercial warehouse by the wholesale stage, the wholesale dealer, wholesale facility, the food market, circulations such as container warehouse, the logistics stage), the circulation number of times in retail stage is also many, also there is the consumer time and again article to be placed on evaluation on hand in the retail stage, so for the gas stop resin formation body and the choke transparent membrane that are used for container and wrappage etc., demanding flexible resistance.That is to say, because before the consumer is buying permission use gas stop resin formation body and the F﹠B product of choke usefulness transparent membrane as container and wrappage etc., following phenomenon appears sometimes: container and wrappage that gas stop resin formation body and choke are made of transparent membrane, the wrinkle that perhaps becomes gauffer pleat, perhaps when state is rolled in bending, pack, under cold insulation temperature (5 ℃ of temperature) condition, display; Perhaps when taking and when evaluation packaged food, beverage product are squeezed or bending is rolled over, the gauffer pleat of wrinkling becomes.Being in bending repeatedly and often under such low temperature environment is subjected under the folding state, when being used for the gas stop resin formation body of the container of food, beverage product and wrappage etc. and choke with the not enough situation of the flexible resistance of transparent membrane, worry duck eye and crackle etc. to occur, just can not guarantee desirable gas barrier property in the quality guarantee period (appreciating the taste time limit) at food, beverage product.Thereby cause in food, the beverage product content oxidation, variable color, cause in the shelf-life food, beverage product quality to descend.So flexible resistance just becomes one of extremely important necessary requirement performance.Especially spring rate (length growth rate), the disparity when the transparent plastic film of base material and choke are rolled over the bending between the variety classes resin material of coating seems under the big situation, even give choke with desirable bendability on the coating, the flexible resistance of gas stop resin formation body and choke usefulness transparent membrane also not enough, so must select to use with desirable choke uses the transparent plastic film of coating compatibility good (length growth rate is roughly the same) as base material, therefore, its use also is restricted.Here, when not limiting (selection) as gas stop resin formation body and choke during, need exploitation to be rich in versatility strongly, can satisfy the material of gas barrier property and other performance requirement with the base material of transparent membrane.

In addition, display device from notebook personal computer and Word message processor, also subsidiary liquid crystal on minitelevision, scavenger and radio cassette recorder, clock and watch etc., the telephone set display device that comprises mobile phone, the time showing of cooker, カ one Na PVC, game machine even, the many goods in our present daily life have all used liquid crystal indicator (liquid crystal display).Here it is because liquid crystal display is compared with other demonstrations, and it is few to have when showing the electric power of required consumption, and be easy to advantage such as miniaturization and.

Especially, for carrying end and even モバィ Le machine (mobile phone, mobile information end (PDA), carry and use notebook personal computer, pocket radio pager, automobile telephone etc.) etc., from Portability and the little viewpoint of consumed power, machine miniaturization and more just becomes the theme that important technology is developed, as wherein one encircling, with regard to liquid crystal indicator, with the display board of glass in the past, weight is big, and, developing with light-duty owing to the problem such as break of the impulsive force when falling down or run into hard thing, solid thin polymer film is as the LCD of substrate.Use this with the liquid crystal display of thin polymer film as substrate, compare with glass substrate, have very light and can make very thin, resistance to impact is also strong, can be shaped to arbitrary shape (for example being molded into curve form), also can make hyalinosis's advantages of higher, be the market at center so enlarging with mobile phone etc. significantly.In addition, mobile phone with internet connection function is popularized rapidly, in next-generation mobile phone, the sound acoustic intelligence of the high speed communication of high capacity writings and image information becomes possibility than having more originally, so, the exploitation of the large-scale liquid crystal board that more writings and image information can once show becomes the thing of the task of top priority, and the more slim and exploitation that have a thin polymer film substrate of high reliability of light weight just becomes important.

So-called liquid crystal enters layer, owing to the thickness that makes liquid crystal layer necessarily forms and extraneous negative pressure, once the substrate gas barrier property degenerates, the permeability height, oxygen and water vapor will enter in the liquid crystal, a certain amount ofly will produce bubble if enter certain, even energising is not replied yet, just become China ink and dye.Therefore, in this thin polymer film substrate, gas barrier property just becomes important factors, till up to now, develop, in the middle of the commercially available commodity, almost on base film, can form the thin polymer film substrate of gas barrier layer, usually can form with certain certain proportion under the state (below, also only be called the lower negative pressure state) of negative pressure at liquid crystal layer, just can cut off gases such as air and water vapor.Yet, in in putting into school bag and pocket etc. and in operation, can push or be extruded liquid crystal watch panel (film), when after applying load, cancelling this load, return between the speed (recovery speed) of previous status and the speed that inner liquid crystal returns to original state in surface plate and to have difference, because it is slow that liquid crystal restores speed, the liquid crystal aspect form for the moment higher negative pressure state (below, also only be called the high negative pressure state), gas permeation just occurred and had gas barrier layer surface plate (film), in the inner problem that forms bubble of liquid crystal, therefore, for such surface plate (film), remove in light weight, beyond solid, also require in gas barrier layer in the past inaccessiable, when under service conditions such as liquid crystal side is extruded, forming the high negative pressure state, gas can not see through, so higher gas barrier property is necessary.

In addition, the flat pannel display of the mode of new generation of these LCD instead, PDP (Plasma Display panel), the PDP of exchange way, plasmatron, the LED that have proposed FED (light emitting-type flat pannel display voluntarily), direct current mode show (diode displaying) or the like, also propose not use the new display of liquid crystal.Because it is few to have a consumed power, thin thickness, advantage such as answer speed is fast, and no angle of visibility is interdependent is so as long as we can say the manufacturing cost problem that solved, just containing these advantages as the extensively universal possibility of desirable display.

Even such display, though aspect substrate, also can use glass substrate, but compare with glass substrate, owing to have the very light and thin thickness of weight, impact resistance is strong, can be molded into arbitrary shape, (for example being molded into curved surface), transparency advantages of higher is so wish to utilize and the same thin polymer film substrate of LCD always.

Yet the battery with between liquid crystal replacement substrate must make plasma discharge with mercury vapour and xenon, and perhaps ejected electron makes phosphor body luminous.Therefore since in battery from outside permeate water steam and oxygen, be difficult to cause that plasma discharge and electronics emit, cause equally with liquid crystal and cause malfunction.Thereby such display and liquid crystal display are same, and it is consistent requiring that for substrate high gas barrier property aspect is arranged, if adopt the thin polymer film substrate, described gas barrier property just becomes important factors.Under various environments for use, for example under high temperature, high humidity service condition, the high gas barrier property aspect that requirement can fully be fit to, with LCD also without any different.

Summary of the invention

Therefore, the objective of the invention is, novel gas stop resin formation body and choke transparent membrane are provided in order to address the above problem.

Another object of the present invention is, uses for reference above-mentioned prior art, and gas barrier property, subduing property, gas stop resin formation body and choke transparent membrane that the transparency is good are provided.

Another purpose of the present invention still, use for reference above-mentioned prior art, provide to have good gas barrier property, not influenced by the substrate kind to have good flexible resistance, with base material adaptation, subduing property, the transparency, novel gas stop resin formation body and choke transparent membrane that printing is good.And find that above-mentioned these characteristics all are stable usually.

In addition, for above-mentioned purpose, the present invention can also comply with more various benchmark that requires, gas stop resin formation body and the gas-barrier films that can give full intensity, hardness, have characteristics such as good moisture-proof, permanance, weatherability, resistance to impact, thermotolerance, solvent resistance, water tolerance are provided except that above-mentioned various characteristics.And find that these characteristics all are stable usually.

Another object of the present invention provides the gas stop resin formation body and the air blocking thin film of very widespread use, and the packing material made from these materials.This wrappage have both good gas barrier property, thermotolerance, subduing property, the transparency, moisture-proof, solvent resistance, the container that can be used for food, beverage and packing timber.

Another object of the present invention is, be provided under any environment for use (under constant temperature and humidity, the drying regime and even from the lower negative pressure state under hot and humid dampness, and liquid crystal inside becomes high negative pressure state status etc. quickly), although very high humidity interdependence also can keep the gas stop resin formation body and the gas-barrier films of gas barrier property; And provide use their liquid crystal display substrate.

Another object of the present invention is, provide and do not rely on the humidity interdependence, can keep superior gas barrier properties, and have liquid crystal display substrate and the desired thermotolerance of other base plate for displaying, the gas stop resin formation body and the gas-barrier films of characteristics such as subduing property, the transparency, moisture-proof, solvent resistance; And provide use their liquid crystal display substrate.

So present inventors have carried out wholwe-hearted research in order to solve above-mentioned problem, the result has finished the present invention.That is to say the finishing of the projects among the present invention by following (1)-(11).

(1) a kind of gas stop resin formation body, it is characterized in that, be to have base material and have the resin-formed body that has amino macromolecular compound (I) and have the coating that can get with the coating composition of the organic compound (II) of the functional group of amino reaction in molecule by comprising; This resin-formed body is at 60 ℃, the oxygen permeability (A) after the 90%Rh condition was handled in following 24 hours with handle before the ratio (A)/(B)≤10.0 of oxygen permeability (B).

(2) a kind of choke transparent membrane, wherein this film has on the one side at least of transparent plastic film base material by comprising and has amino macromolecular compound (I) and have the coating that can get with the coating composition of the organic compound (II) of the functional group of amino reaction in molecule; After the flexible resistance of this film test 20 times, be 20ml/m at 20 ℃, oxygen permeability during 60%Rh ²Below the 24hatm.

(3) according to the gas stop resin formation body of being put down in writing in above-mentioned (1), it is characterized in that, in the coating composition in above-mentioned (1), further comprise organo-silicon compound (III) by following general formula (1) expression:

R ¹ _mSi(OR ²) _n (1)

(wherein, R in the formula ¹Represent C _1-4Alkyl, has not the C with amino reactive functional group base _1-4Alkyl or C _2-4Thiazolinyl; R ²Represent hydrogen atom or C _1-4Alkyl; N represents the integer more than 1; M represents the integer more than 0; And m+n=4).

(4) according to the choke transparent membrane of being put down in writing in above-mentioned (2), it is characterized in that, in the coating composition described in above-mentioned (2), further comprise organo-silicon compound (III) by following general formula (1) expression:

R ¹ _mSi(OR ²) _n (1)

(5) according to the gas stop resin formation body of being put down in writing in above-mentioned (3), wherein said coating composition comprise 5-90 quality % have amino macromolecular compound (I), 5-50 quality % in molecule, have can with organic compound (II), the 5-80 quality % organo-silicon compound (III) of the functional group of amino reaction.

(6) according to the choke transparent membrane of being put down in writing in above-mentioned (4), wherein said coating composition comprise 5-90 quality % have amino macromolecular compound (I), 5-50 quality % in molecule, have can with organic compound (II), the 5-80 quality % organo-silicon compound (III) of the functional group of amino reaction.

(7) a kind of gas stop resin formation body, it is characterized in that, comprise by base material and the coating (B) that is able to by coating composition, wherein coating composition comprises: have amino macromolecular compound (I), having in molecule can be with the organic compound (II) of the functional group of amino reaction, be selected from the organo-silicon compound of representing by with following general formula (1) (III)

R ¹ _mSi(OR ²) _n (1)

(wherein, R in the formula ¹Represent C _1-4Alkyl, has not the C with the functional group of amino reaction _1-4Alkyl or C _2-4Thiazolinyl; R ²Represent hydrogen atom or C _1-4Alkyl; N represents the integer more than 1; M represents the integer more than 0; And m+n=4.) and its add at least a organo-silicon compound (IIIb) and the solvent (IV) of containing in the group that water decomposition condensation product (IIIa) forms;

The above organo-silicon compound (IIIb) of 50 quality % are arranged as raw material in the total amount of coating composition (coating agent) use above-mentioned (I)+(II)+(IIIb);

Non-volatile content concentration is more than 5 quality % in this coating composition;

And the organo-silicon compound in this coating composition (III) are below the 3 quality %,

60 ℃ of this resin-formed body, the oxygen permeability (A) after 90%Rh handled in 24 hours with handle before the ratio (A)/(B)≤10.0 of oxygen permeability (B).

(8) a kind of choke transparent membrane, wherein the transparent plastic film base material on the one side coating that is obtained by coating composition is arranged at least, coating composition wherein comprises: have amino macromolecular compound (I), having in molecule can be with the organic compound (II) of the functional group of amino reaction, be selected from the organo-silicon compound of representing by with following general formula (1) (III)

R ¹ _mSi(OR ²) _n (1)

(wherein, R in the formula ¹Represent C _1-4Alkyl, has not the C with amino reactive functional group base _1-4Alkyl or C _2-4Thiazolinyl; R ²Represent hydrogen atom or C _1-4Alkyl; N represents the integer more than 1; M represents the integer more than 0; And m+n=4.) and its add at least a organo-silicon compound (IIIb) and the solvent (IV) of containing in the group that water decomposition condensation product (IIIa) forms;

The above compound (IIIb) of 50 quality % is arranged as raw material in the total amount of coating composition (coating agent) use above-mentioned (I)+(II)+(IIIb);

And the amount of the organo-silicon compound in this coating composition (III) is below the 3 quality %;

The flexible resistance of this film is tested 20 ℃ after 20 times, and the oxygen permeability during 60%Rh is 20ml/m ²Below the 24hatm.

(9), be as liquid crystal display substrate according to the purposes of the gas stop resin formation body of being put down in writing in above-mentioned (1), (3), (5) or (7).

(10), according to the purposes of the gas stop resin formation body of being put down in writing in above-mentioned (1), (3), (5) or (7), be as packing material.

(11), according to the choke put down in writing in above-mentioned (2), (4), (6) or (8) purposes with transparent membrane, be as packing material.

By gas stop resin formation body of the present invention, even under harsh environment for use, under high wet condition and high negative pressure state, also can keep fully high gas barrier property particularly, thus the high-quality of defective such as gassing not had in use, thus have the height trustworthiness.The transparency, adaptation, liquid crystal display substrate that solvent resistance is good further can be provided, and the liquid crystal display substrate that uses them.And, have in the middle of the gas stop resin formation body that the present invention constitutes, except as liquid crystal display with the substrate, also have and can be applicable to food, beverage-container and wrappage etc., the advantage of under hot conditions, using in a lot of occasions.Therefore conduct has the purposes of the gas stop resin formation body of the present invention's formation, can be widely used in requiring the various fields of gas barrier property performance, also be widely used in purposes such as the thin polymer film substrate of Food ﹠ Drink product container and wrappage (for example container of food packing film and bottle etc.), liquid crystal indicator, the electronic unit (for example thin polymer film substrate of LCD etc.) that carries end and even モバィ Le device etc., medicine equipment and medical apparatus (for example blood storage bag etc.).

In addition, handle through harsh with transparent membrane by choke of the present invention, specifically, even also can keep high performance gas barrier property 20 times in the test of process flexible resistance.Therefore, choke of the present invention can fully satisfy the requirement of the extensive uses such as display unit of used for packing foods material, liquid crystal display substrate etc. with transparent membrane.

Description of drawings

Fig. 1 is as a kind of embodiment of the liquid crystal indicator relevant with the present invention, and expression focuses on liquid crystal board, rear light, driving circuit etc. an example of the general colour-TFT liquid crystal display micromodule in the assembly.This figure is for the ease of understanding multi-ply construction, and the part of Fig. 1 is the oblique view of analysis.

Fig. 2 is as another embodiment of the liquid crystal indicator relevant with the present invention, and expression allows to use the general colour-stn liquid crystal display sectional drawing of LCD panel of the present invention.

Embodiment

Gas stop resin formation body of the present invention, it is characterized in that comprising base material and the coating that is obtained by coating composition, coating composition wherein comprises: have amino macromolecular compound (I) and in molecule, have can with the organic compound (II) of amino reactive functionality.

60 ℃ of this resin-formed body, the oxygen permeability (A) after handling in 90%Rh24 hour with handle before the ratio (A)/(B)≤10.0 of oxygen permeability (B).

As preferred gas stop resin formation body of the present invention, it is characterized in that, in aforementioned coating composition, further comprise organo-silicon compound (III) by general formula (1) expression:

R ¹ _mSi(OR ²) _n (1)

(wherein, R ¹Expression C _1-4Alkyl, has not the C with amino reactive functionality _1-4Alkyl or C _2-4Thiazolinyl; R ²Represent hydrogen atom or C _1-4Alkyl; N represents the integer more than 1; M represents the integer more than 0; And m+n=4).

Gas stop resin formation body of the present invention, can be widely used in requiring superior gas barrier properties, further require the various industries of characteristics such as thermotolerance, subduing property, the transparency, moisture-proof, solvent resistance, so can be used in for example (1) liquid crystal display substrate and other substrate for display, (2) various packing materials of representatives such as food, beverage product container and wrappage (also comprising packing, container, wrappage of medicine, medicine equipment etc.) etc., and can effectively use, be the good article that extremely have versatility.

No matter gas stop resin formation body with above-mentioned formation in (under the condition of high temperature, negative pressure state inferior) under what kind of environment for use, can both prevent seeing through from water vapour in the outside atmosphere and oxygen.Therefore, for example,, can not produce bubble owing to seeing through gas, the defectives such as malfunction of liquid crystal indicator occur, the good article with high reliability can be provided in liquid crystal inside if be used for the liquid crystal display substrate.In addition, if be used for the various packing materials of representatives such as food, beverage product container and wrappage, can improve the long preservation and the preservation and effect of food, beverage product.Particularly the organo-silicon compound (III) that above-mentioned general formula (1) is represented are when being used for above-mentioned coating composition, can appear at hot and humid superior especially gas barrier property down, so except can be under from the constant temperature temperature constant state to humid tropical condition, in broad range, further improve beyond the gas barrier property, also have high-durability, thermotolerance, water tolerance, subduing property, the transparency, moisture-proof, solvent resistance.Even and find to have with gas barrier layer in the past inaccessiable hot and humid and even liquid crystal is inner when becoming the high negative pressure state, the high gas barrier property that gas can not see through quickly.

Below illustrate in greater detail the present invention.

At first, can be used for coating of the present invention and be exactly in order to give the lining material of above-mentioned base material, require this coating to have and characteristics such as the adaptation of base material (layer when the middle layer occasion is set between base material and coating), the transparency, chemical resistance, thermotolerance, subduing property, moisture-proof, anti-solvent with high function gas barrier property purpose.As satisfying desired coating, be exactly particularly from comprise have amino macromolecular compound (I) and in molecule, have can with the organic compound (II) of the functional group of amino reaction, further also comprise the overlayer that the coating composition with the organo-silicon compound (III) of above-mentioned general formula (1) expression obtains as required.

Here, above-mentioned coating composition as long as comprise above-mentioned macromolecular compound (I) and organic compound (II), preferably also includes organic silicon compound (III) as required and uses raw material just as main.Further, in coating composition, in not damaging effective scope of the present invention, can comprise the various adjuvants of inorganic and organic class such as curing catalysts, wettability improver, plastifier, defoamer, tackifier as using raw material.In addition, the occasion at the appropriate solvent (IV) that uses these materials of dissolving when being not particularly limited, also comprises solvent (IV).In addition, after the raw material that the regulation coating composition uses, manufacture method and manufacture process according to the described coating in back, because with these raw materials, this raw material reaction thing and add water decomposition condensation product etc. and (for example mix, comprise the preceding raw material of reaction and add the water decomposition condensation product, the reactant that raw material reacts, raw material and reactant add the water decomposition condensation and obtain add the water decomposition condensation product, the adding the water decomposition condensation altogether of reactant and raw material and obtain add water decomposition condensation product etc., the composition formation changes in manufacture process), so can not carry out unique regulation.That is to say, because being grouped into manufacture method and manufacturing process, the one-tenth of this coating composition changes at any time, so following when mentioning coating composition simply, should explain the connotation of this coating composition from its description, and should not distort explanation (promptly as comprise as described above add water decomposition condensation product etc., the extensive interpretation of should trying one's best, and not should to have macromolecular compound (I), organic compound (II), further the meaning of organo-silicon compound (III) only makes an explanation to narrow sense).

Above-mentionedly have an amino macromolecular compound (I) as what above-mentioned coating composition mainly used one of raw material, be not particularly limited preferred polyalkyleneimine.This is because macromolecular compound (I), can reach make coating have subduing property, to the adaptation of base material (layer when between base material and coating, setting up the middle layer occasion), the easy purpose of system film, more preferably polyethyleneimine.

Have an amino macromolecular compound (I) as above-mentioned, can enumerate polyethyleneimine, polypropylene imines, poly--1 particularly, 2-butylene imines, poly-2,3-butylene imines, poly--1, polyalkyleneimine classes such as 1-dimethyl aziridine; The polyarylamine class; Contain amino (methyl) Voncoat R 3310, (methyl) acrylate that contains these amino and other (methyl) esters of acrylic acids, perhaps with (methyl) acrylic acid multipolymer; Zeo-karb etc.Particularly, from the transparency, the hot water resistance viewpoint of coating, preferred polyalkyleneimine, special preferably polyethylene imines.

As above-mentioned poly-alkyl imines class, can enumerate for example commercially available ェ Port ミ Application シリ one ズ here, by Nippon Shokubai Co., Ltd's manufacturing; The polyethyleneimine of ェ Port ミ Application SP-003, ェ Port ミ Application SP-006, ェ Port ミ Application SP-012, ェ Port ミ Application SP-018, ェ Port ミ Application SP-103, ェ Port ミ Application SP-110, ェ Port ミ Application SP-200, ェ Port ミ Application SP-300, ェ Port ミ Application SP-1000, ェ Port ミ Application SP-1020 (all being trade name) etc. etc.But, not limited by these, this is self-evident.

As above-mentioned polyarylamine class, also can enumerate, the PAA-L that for example commercially available Nitto Boseiki Co., Ltd. makes, PAA-H (all being trade name) etc., but not limited by these.

As above-mentioned (methyl) acrylate that contains amino, for example can enumerate (methyl) acrylic acid dimethylamino ethyl ester, (methyl) acrylic acid diethylamino ethyl ester etc.

As the example of above-mentioned other (methyl) esters of acrylic acids, except with contain amino (methyl) acrylate can the monomer of copolymerization, also can be and contain the monomer that amino (methyl) acrylate can copolymerization and the macromolecular compound of copolymerization.

The number-average molecular weight of above-mentioned macromolecular compound (I) is 250～200,000, and preferred 250～100,000, more preferably 300～10,000 scope.If number-average molecular weight is less than 250, then the subduing property of formed coating is bad, and is perhaps bad at the film forming of base material (layer the when occasion in middle layer is set between base material and coating) when going up lining; If number-average molecular weight is greater than 200,000, except the coating that forms transparent bad, the subduing property of coating is bad.But, can be used in the middle of the macromolecular compound of the present invention (I), also comprise the material of the complex structure that can not measure with above-mentioned number-average molecular weight, therefore according to from the present invention, not getting rid of these materials at the molecular weight of this regulation.

In addition, as the main use raw material of the above-mentioned coating composition of another kind---in molecule, have can with the functional group's of amino reaction organic compound (II), should not be subjected to special restriction.But preferably not only in molecule, have can with the functional group of amino reaction, and have SiOR ³Base (R ³Expression hydrogen atom or C _1-4Alkyl) compound.Owing to have this SiOR ³Base, with have amino macromolecular compound (I) reaction before or after the reaction, carry out the water decomposition condensation reaction, also cause with the water decomposition condensation reaction that adds altogether that adds water decomposition condensation base of the described organo-silicon compound in back (III) and carry out polycondensation reaction, therefore rapidly form fine and close by overlay film, thereby be considered as the good vapour lock of purpose, gas stop resin formation body and choke transparent membrane aspect with the good adaptation of base material, good with the base material adaptation, even it is further low in the humidity interdependence, the especially effectively advantage of the high gas barrier property of performance (maintenance) that also can work very effectively of (for example boiling 20 ℃ after the sterilization, under the 90%Rh condition) under the high humility etc.

At this, as can with the functional group of amino reaction, be not particularly limited, can enumerate for example epoxy radicals, carboxyl, isocyanate group, isothiocyanic acid ester group, oxazolinyl, acrylic, (CH ₂=CHCOO-), methacrylic acid group, aldehyde radical, ketone group, haloalkyl, sulfydryl etc.Handle viewpoints such as property from amino (amino that has in macromolecular compound (I) and organo-silicon compound (III) molecule) reaction easiness, hot water resistance, operation the time, preferably epoxy radicals.

In addition, above-mentioned SiOR ³R in the base ³Expression hydrogen atom, C _1-4Alkyl.Here, as C _1-4Alkyl, be not particularly limited, can be any in ring-type (alicyclic ring shape) alkyl in the branched alkyl, cyclopropyl, cyclobutyl of straight chained alkyl, isopropyl in methyl, ethyl, propyl group, the butyl.As above-mentioned R ³, shrink the reduction effect from gas barrier property, when tunicle (coating) forms, the good profitability that adds the water decomposition condensation reaction, forms fine and close tunicle (coating) aspect, preferable methyl, ethyl are considered in reaction easiness aspect.

As aforesaid in molecule, have can with the organic compound (II) of amino reactive functional group base, specifically can enumerate for example phenyl glycidyl ether, 2-ethylhexyl glycidol ether, propanetriol-diglycidyl-ether, the trimethylolpropane diglycidyl ether, resorcinolformaldehyde resin, the neopentyl ethylene glycol diglycidylether, 1, the 6-hexanediol diglycidyl ether,-condensed ethandiol diglycidyl ether, the diethylene glycol diglycidyl ether, the triethylene glycol diglycidyl ether, the TEG diglycidyl ether, propylene glycol diglycidylether, the p-dihydroxy-benzene diglycidyl ether, bisphenol A diglycidyl ether, bisphenol-S diglycidyl ether, the diglycidyl ethers of pentaerythrite four glycidol ethers etc.; The ethylene oxidic ester class of hexane diacid 2-glycidyl ether-ether, phthalic acid 2-glycidyl ether-ether etc.; β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, β-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane, β-(3, the 4-epoxycyclohexyl) ethyl three isopropoxy silane, β-(3, the 4-epoxycyclohexyl) ethyl-methyl dimethoxy silane, β-(3, the 4-epoxycyclohexyl) ethyl-methyl diethoxy silane, γ-diglycidyl oxygen propyl trimethoxy silicane, γ-diglycidyl oxygen propyl-triethoxysilicane, γ-diglycidyl oxygen propyl group three isopropoxy silane, γ-diglycidyl oxygen propyl group methyl dimethoxysilane, γ-diglycidyl oxygen propyl group methyldiethoxysilane etc. has epoxy radicals and Si (OR ³) base (R ³The expression the meaning as hereinbefore) silane coupling agent (following abbreviates the silane coupling agent that contains epoxy radicals as); γ-isocyanic acid propyl trimethoxy silicane γ-isocyanic acid propyl-triethoxysilicane, γ-isocyanic acid propyl group methyl dimethoxysilane, γ-isocyanic acid propyl group methyldiethoxysilane etc. contain isocyanate group and Si (OR ³) base (R ³The expression the meaning as hereinbefore) silane coupling agent (following abbreviates the silane coupling agent that contains isocyanate group as); γ-(methyl) propenyloxy group propyl trimethoxy silicane, γ-(methyl) propenyloxy group propyl-triethoxysilicane, γ-(methyl) propenyloxy group propyl group ethyl dimethoxy silane; γ-(methyl) propenyloxy group methyl-propyl diethoxy silane; γ-Qiu Jibingjisanjiayangjiguiwan, γ-sulfydryl propyl-triethoxysilicane; Cresylene diisocyanate, 1,4-methyl diphenylene diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, isocyanates such as the three pairs of diisocyanate, xylylene diisocyanate, dicyclohexyl methyl diisocyanate, hexamethylene diisocyanate etc.Can use one or two or more kinds in these.

In addition, in above-mentioned coating composition, wish to comprise with the organo-silicon compound (III) of following general formula (1) expression as another kind of primary raw material:

R ¹ _mSi(OR ²) _n (1)

(wherein, R in the formula ¹Represent C _1-4Alkyl, has not the C with amino reactive functional group base _1-4Alkyl or alkenyl; R ²Represent hydrogen atom or C _1-4Alkyl; N represents the integer more than 1; M represents the integer more than 0; And m+n=4).More preferably include organic silicon compound (III) and its and add at least a organosilyl compound (IIIb) that contains in the group that water decomposition condensation product (IIIa) forms.

Owing to added organo-silicon compound (III), for example, this coating composition is being used for liquid crystal display with under the occasion of substrate, even under any environment for use (for example, liquid crystal is inner to be formed for the moment than higher negative pressure state occasion or in humid tropical condition, dampness occasion etc.), can both give full play to very high gas barrier property.Also have, if this coating composition is used for various packing materials by representatives such as the container of food, beverage product and wrappage, energy improves and adaptation, the coating soundness (Ha one De コ one ト) of base material (layer when the middle layer situation is set between base material and coating), improves thermotolerance.Aspect the use of the container of food, beverage product and wrappage, though hot and humid degree etc. harsh preserve so that environment for use under, also can fully keep very high gas barrier property.This organo-silicon compound (III) are not owing to have the functional group that can react with functional group's (amino) that above-mentioned macromolecular compound (I) had.So it is different with above-mentioned organic compound (II).

R in the above-mentioned formula ¹As long as represent C _1-4Alkyl, has not the C with the functional group of amino reaction _1-4Alkyl or C _2-4Thiazolinyl just.Herein, be not particularly limited, for example can enumerate amino etc. as the functional group who does not react with amino.In addition, as C _1-4Alkyl is not particularly limited, and can be the straight chained alkyl of methyl, ethyl, propyl group, butyl, the branched alkyl of isopropyl, any one in the ring-type of cyclopropyl, cyclobutyl (alicyclic group) alkyl.But add water decomposition condensation reaction, formation densification by the profitability of overlay film, the aspect consideration of reaction easiness, as C from good _1-4Alkyl preferable methyl, ethyl.In addition, as C _2-4 thiazolinyls for example can be enumerated vinyl, allyl, propenyl, isopropenyl, 2-butenyl group etc., but from thermotolerance, anti-boiling property consideration preferred vinyl.

Particularly as R ¹, consider preferred vinyl from thermotolerance, anti-boiling property aspect.And be 2 when above at m, R ¹Can be identical, also can be different.

R in the above-mentioned formula ²Represent hydrogen atom or C _1-4Alkyl.As C _1-4Alkyl has no particular limits, and can be in ring-type (alicyclic group) alkyl of branched alkyl, cyclopropyl, cyclobutyl of straight chained alkyl, the isopropyl of methyl, ethyl, propyl group, butyl any one.As R ²,, be preferably methyl, ethyl from good adding the water decomposition condensation reaction, helping forming and fine and closely considered by the overlay film aspect.And be 2 when above at n, R ²Can be identical, also can be different.

In above-mentioned formula, n is 1 above integer, and m is 0 above integer, and m+n=4.Consider preferred m=0, n=4 from the thermotolerance of coating, anti-boiling property aspect.

Particularly as organo-silicon compound (III) as above-mentioned general formula (1) expression, can enumerate for example tetramethoxy-silicane, tetraethoxysilane, tetra isopropyl silane, four butoxy silanes, methyltrimethoxy silane, methyl triethoxysilane, the methyl tri isopropyl silane, methyl three butoxy silanes, ethyl trimethoxy silane, ethyl triethoxysilane, the ethyl tri isopropyl silane, ethyl tributyl silane, the n-pro-pyl trimethoxy silane, the n-pro-pyl triethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethyl diisopropyl silane, dimethyl dibutoxy silane, diethyl dimethoxy silane, the diethyl diethoxy silane, diethyl diisopropoxy silane, diethyl dibutyl silane, the trimethyl methoxy silane, the gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, N-β-(amino-ethyl) gamma-amino propyl trimethoxy silicane, N-β-(amino-ethyl) γ-An Jibingjisanyiyangjiguiwan, gamma-amino propyl group methyl dimethoxysilane, gamma-amino propyl group methyldiethoxysilane, N-β-(amino-ethyl) gamma-amino propyl group methyl dimethoxysilane, N-β-(amino-ethyl) gamma-amino propyl group methyldiethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl silane triisopropoxide, the alkoxyl silicone alkanes of vinyl three butoxy silanes etc., perhaps their coordination compound, methyl triacetoxysilane, trimethyl silicane alkanols etc. perhaps comprise the macromolecular organic compound class of these compounds.Can use one or two or more kinds in the above material.Wherein, present good anti-boiling property, moisture-proof, the consideration of thermotolerance aspect, preferred tetramethoxy-silicane, tetraethoxysilane from formed coating.

In addition, in preferred embodiment, adding at least a organic silicon compound (IIIb) that contains in the group of water decomposition condensation product (IIIa) composition as the organo-silicon compound (III) that are selected from above-mentioned general formula (1) expression and its, also can be the material that adds water decomposition condensation product (IIIa) that includes organic silicon compound.For above-mentioned organic compound (II) and the above-mentioned organo-silicon compound (IIIb) that contain,, wish to add in advance the water decomposition condensation reaction in order to prevent the drying when forming coating.In other words, we can say in coating composition that these add that the water decomposition condensation product can exist is desirable.These (being total to) add the water decomposition condensation reaction, can use airborne moisture to carry out, if use well-known catalysts such as acid or alkali, efficient is just higher.In addition, add the water decomposition reaction and preferably carry out in solvent (IV), the coating composition of the present invention that comprises described solvent (IV) also applies operation easily.Even the organo-silicon compound of in only adding, representing with above-mentioned general formula (1) add water decomposition condensation product (IIIa) as the situation of raw material the time, because the aforesaid competition that adds water decomposition condensation reaction and its reversed reaction, processing (operation) method that employing is carried out reversed reaction just can make organo-silicon compound (III) content in the coating composition below 3 quality %.

In addition, in above-mentioned coating composition, mainly use raw material as another kind, it is desirable further comprising solvent (IV).As solvent (IV), if can dissolve above-mentioned organic high molecular compound (I), organic compound (II) and organo-silicon compound (III), further can be dissolved with the solvent that adds water decomposition condensation product (IIIa) and other adjuvants of dissolving (and even dispersion) of organic silicon compound, just should not be subjected to special restriction.Can enumerate for example alcohols of methyl alcohol, ethanol, 2-propyl alcohol, butanols, amylalcohol, ethylene glycol, diethylene glycol, triethylene glycol, glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether etc.; Ketones such as acetone, MEK, methyl isobutyl ketone, cyclohexanone; Toluene, benzene, dimethylbenzene etc. are aromatic hydrocarbon based; Hydro carbons such as hexane, heptane, octane; The acetate esters of methyl acetate, ethyl acetate, ethyl ester propyl ester, butyl acetate etc. also can be enumerated the solvent as ethylbenzene phenolic ether, propyl ether, tetrahydrofuran and water etc. and so on.These solvents can use separately, also can mix use more than two kinds.Particularly consider alcohols materials such as particular methanol, ethanol from having good stability and storage stability aspect when adding the water decomposition reaction.Especially, in the present invention, use the kind of material compositions according in addition other of the solvent in the coating composition (IV), for the compactness of resulting coating crosslinking degree and can find desirable gas barrier property, wish the selection appropriate solvent (IV) that therefrom suits.

In the middle of above-mentioned coating composition, as required in not damaging effective scope of the present invention, also can add the various adjuvants of inorganic and even organic class such as curing catalysts, wettability improver (improving the adjuvant of wettability), plastifier, defoamer, tackifier in right amount as raw material.

Further, the use level of above-mentioned macromolecular compound (1), different owing to whether using according to organo-silicon compound (III) as any composition, and can not unify regulation.For the total amount of above-mentioned coating composition (still, desolventizing (IV) in addition), usually at 5-90 quality %, preferred 10-90 quality %, more preferably 20-80 quality %, especially preferably 25-50 quality % scope.During less than 5 quality % situations, the subduing property of resulting coating is bad in the use level of above-mentioned macromolecular compound (I), and on the other hand, when the 90 quality % situations of surpassing, the water tolerance of resulting coating is bad.

Equally, whether the use level of above-mentioned organic compound (II) is owing to using different according to the organo-silicon compound (III) as any composition and can not unifying regulation.For the total amount of above-mentioned coating composition (still, wherein desolventizing (IV) in addition), usually at 5-50 quality %, preferred 7-35 quality % is more preferably in the 10-20 quality % scope.During less than 5 quality %, the water tolerance of resulting coating is bad in the use level of above-mentioned organic compound (II); On the other hand, when surpassing 50 quality %, the gas barrier property of resulting coating is bad.

Equally, the use level of above-mentioned organo-silicon compound (III), total amount for above-mentioned coating composition (but desolventizing (IV) in addition), usually below 80 quality %, preferred 5-80% quality %, more preferably 10-80 quality %, preferred especially 20-70 quality %, more preferred 30-60 quality % scope.During greater than 80 quality %, the subduing property of resulting coating is bad in the use level of above-mentioned organo-silicon compound (III); On the other hand, as any composition, its use level lower limit is 0 quality % at organo-silicon compound (III), but in use, hope can be given full play to its action effect, and during less than 5 quality %, the water tolerance of resulting coating is bad in its use level.

The use level of above-mentioned solvent (IV), for total amount 100 mass parts of above-mentioned coating composition (wherein desolventizing (IV) in addition), usually in the 30-95 mass parts, preferred 50-90 mass parts is more preferably in the 70-85 mass parts scope.During less than 30 mass parts situations, the reaction stability of above-mentioned coating composition is bad, so be not desirable in the use level of above-mentioned solvent (IV).On the other hand, greater than 95 mass parts situations the time, the manufacturability when forming coating is bad, so be not desirable.

About the use level of other the various adjuvants except that above-mentioned, in the scope of not damaging effect of the present invention, and if in effectively bringing into play the characteristic range of adjuvant separately, should not be subjected to special qualification.In addition, about cooperating the time of adjuvant, consider the characteristic that each adjuvant has, reaching the arbitrary only time that forms coating, can be simultaneously or gradation add and cooperate, be add continuously cooperate or be interrupted add cooperate can, should not limit especially.

And comprise above-mentioned organic high molecular compound (I), organic compound (II) and organo-silicon compound (III), further comprising total use level of the coating composition (wherein desolventizing (IV) in addition) of other adjuvants, also usually is 100 quality % even carry out any assembly total amount.

Further, the present inventor finds, even the material composition of Gui Ding scope internal modulation coating composition in the above, during applying dry this coating composition on the base material, also have low boiling organo-silicon compound (III) evaporation, except that the organo-silicon compound (III) of having wasted specially colored high price purchase, owing to lose organo-silicon compound (III) (on a small quantity), the performance of product can reduce (still, can be found, as goods included in the technology of the present invention scope, with compare in the past, require very high performance, in order often to stablize the goods that better quality and superior performance are provided, this is the problem that must solve).Further wholwe-hearted research found that, its reason be in case when applying the coated words that surpass a certain amount of existence with the organo-silicon compound (III) in the composition on base material, applying between dry epoch, these organo-silicon compound (III) on base material are evaporated, and can not handle in coating.In addition, cause waste, should in being no more than a certain amount of scope, adjust the quantity of the organo-silicon compound (III) in the coating composition owing to specially spending the organo-silicon compound of giving a long price for (III) to disperse.That is to say, in optimum scope, carry out the water decomposition condensation (polymerization) that adds of the organo-silicon compound (III) of raw material and react, perhaps in raw material, use this to add the water decomposition condensation product and adjust.Organo-silicon compound (III) are suitable in the adjustment coating composition in being no more than a certain amount of scope.The polyreaction of described organo-silicon compound (III) (adding the water decomposition condensation reaction) and reaction (reversed reaction) competition that depolymerizes, in case undue inhibition adds water decomposition condensation reaction (equaling fully to carry out reversed reaction), the organo-silicon compound in the coating composition (III) exist with regard to surpassing a certain amount of; Meanwhile, on the contrary in case add the words that (equaling too to suppress reversed reaction) too carried out in the water condensation reaction, particlized will occur in the middle of coating composition, residual particles in coating, as gas stop resin formation body, compare with using only coating composition, find its gas barrier property, all bad with adaptation, the transparency, subduing property, the printing of base material.Therefore, based on suitable understanding to these technology, the inventor has found as high-performance and high-quality gas stop resin formation body, can satisfy strict performance requirement, and can be safely and form the coating composition of this gas stop resin formation body effectively, the embodiment that it is suitable is as following.

That is to say, the suitable embodiment of the coating composition that present inventors found is exactly that this coating composition comprises above-mentioned macromolecular compound (I), above-mentioned organic compound (II), and be selected from by above-mentioned organo-silicon compound (III) and its and add at least a organo-silicon compound (IIIb) in the group that water decomposition condensation product (IIIa) forms, and solvent (IV), and use in the organosilyl compound (IIIb) more than this (I)+(II)+(IIIb) total amount 50 quality % as raw material, non-volatile content concentration is more than the 5 quality % in this coating composition, and the organo-silicon compound in this coating composition (III) are below the 3 quality %.

The coating composition that above-mentioned formation is arranged for use, on base material, apply dry, carry out the resulting gas stop resin formation body of coated technology, can find to stablize regularly, has high gas barrier property, good with adaptation, the transparency, subduing property, printing, the moisture-proof of base material, enough intensity, hardness are further arranged, good permanance, weatherability, resistance to impact, thermotolerance, solvent resistance, photostability, water tolerance, flexibility or the like advantage is arranged.In addition, in coating composition, because low-boiling organo-silicon compound (III) exist to be no more than a certain amount of form, in the dry run after coating, the just not evaporation of these organo-silicon compound (III), again because can in coating, make effectively and add water decomposition condensation reaction efficient highland and carry out, not can owing to make a batch difference make form and performance variant.Also have, because the organo-silicon compound of high price (III) do not disperse, so not waste, and good economy is arranged, and in order to prevent distributing of reactive height, virose organo-silicon compound (III), except can improving operating environment significantly, also can be favourable aspect security, economy even have the treatment facility that does not increase this environmental pollutants.

In addition, raw material composition as above-mentioned coating composition, even that uses organo-silicon compound adds water decomposition condensation product (IIIa), for organo-silicon compound (III) (further above-mentioned organic compound (II)), in order to prevent that it is preferred adding the water decomposition condensation reaction in advance in the drying that forms coating.In other words, we can say in coating composition that these add that the water decomposition condensation product can exist is desirable.These (being total to) add the water decomposition condensation reaction, though can carry out in the aerial moisture, if use well-known catalysts such as acid or alkali to react, efficient is higher.In addition, it is preferred adding that water decomposition is reflected in the solvent (IV), comprises the embodiment of the suitable coating composition of the present invention of described solvent (IV), and the coating processes operation has also become easily.And, even what only be added with organic silicon compound adds the occasion of water decomposition condensation product (IIIa) as raw material, because the competition of aforesaid water decomposition condensation reaction and its reversed reaction, take method that reversed reaction is carried out, can make organo-silicon compound (III) in this suitable coating composition below 3 quality %.

In the middle of this suitable coating composition, the use level of above-mentioned organic high molecular compound (I), because according to organic compound (II) with contain the cooperation ratio of organo-silicon compound (IIIb) and whether use other adjuvants and different, therefore can not unify regulation.But for total use level of the material composition (wherein desolventizing (IV) in addition) of this suitable coating composition, usually in 5-70 quality %, preferred 10-60 quality %, more preferably 15-40 quality % scope.During less than 5 quality % situations, subduing property, the resistance to impact of coating are bad in the use level of above-mentioned organic high molecular compound (I); On the other hand the time greater than 70 quality % situations, the water tolerance of coating, moisture-proof, bad to the adaptation of base material.

In this suitable coating composition, the use level of above-mentioned organic compound (II), because according to organic high molecular compound (I) with contain the cooperation ratio of organo-silicon compound (IIIb) and whether use other adjuvants and different, therefore can not unify regulation.But for total use level of the material composition (wherein desolventizing (IV) in addition) of this coating composition that is fit to, usually at 5-50 quality %, preferred 7-35 quality %, more preferably 10-20 quality % scope.In the use level of above-mentioned organic compound (II) during less than 5 quality % situations, the water tolerance of coating, moisture-proof, bad to the adaptation of base material; On the other hand, greater than 50 quality % situations the time, the gas barrier property of coating, subduing property, resistance to impact are bad.

The above-mentioned use level that contains organo-silicon compound (IIIb) in this suitable coating composition, because according to the cooperation ratio of organic high molecular compound (I) and organic compound (II) and whether use other adjuvants and different, therefore can not unify regulation, but total use level for the material composition (wherein desolventizing (IV) in addition) of this suitable coating composition, usually at 20-90 quality %, preferred 30-80 quality %, more preferably 50-70 quality % scope.During greater than 90 quality % situations, the subduing property of coating is bad in the above-mentioned use level that contains organo-silicon compound (IIIb); On the other hand, less than 20 quality % situations the time, water tolerance, the moisture-proof of coating are bad.

The use level of the above-mentioned solvent (IV) in this suitable coating composition, be not particularly limited, but total use level for the material composition (comprising solvent (IV)) of this suitable coating composition at this, usually at 20-97 quality %, preferred 50-95 quality %, more preferably 70-90 quality % scope.During less than 20 quality % situations, the reaction stability of the coating composition that this is suitable is bad in the use level of solvent (IV), and during coating processes because the viscosity of this suitable covering composition rises, just have can not the homogeneous coating possibility; On the other hand, greater than 97 quality % situations the time, except that the productivity when forming coating is bad,, therefore just has and to guarantee necessary tectal thickness because effective constituent concentration is low excessively.

In addition, remove above-mentioned organic high molecular compound (I), organic compound (II), contain organo-silicon compound (IIIb) and solvent (IV) other curing catalysts in addition, the wettability modifying agent, plastifier, defoamer, the use level of the various adjuvants of inorganic and even organic class of tackifier etc., if can fully find the various characteristics that described adjuvant has, and based on above-mentioned organic high molecular compound (I), organic compound (II), contain in the not affected scope of invention effect of gas barrier property of the present invention etc. of organo-silicon compound (IIIb) and solvent (IV), should not be subjected to special restriction.

And, for comprising above-mentioned organic high molecular compound (I), organic compound (II) and containing organosilyl compound (IIIb), the total use level that further comprises this suitable coating composition (wherein desolventizing (IV) in addition) of other adjuvants, even with any assembly, also usually be 100 quality %.

In addition, this suitable coating composition is exactly to comprise organic high molecular compound (I), organic compound (II) as mentioned above, contain organosilyl compound (IIIb) and solvent (IV) is a raw material, the content that contains organosilyl compound (IIIb) in the total amount of wherein aforementioned (I)+(II)+(IIIb) is more than 50 quality %, preferred 50-80 quality %, more preferably 50-70 quality % is as the coating composition of raw material.In addition, the non-volatile content concentration of the coating composition that this is suitable is more than 5 quality %, preferably more than 7 quality %, more preferably more than 10 quality %, and the content of the organo-silicon compound (III) in this suitable coating composition is below 3 quality %, preferably below 2 quality %, more preferably below 1 quality %.

The content that contains organosilyl compound (IIIb) in the total amount of aforementioned (I)+(II)+(IIIb) less than 50 quality % in, the moisture-proof of coating is just bad.Should not be subjected to special restriction for the use level that contains organo-silicon compound (IIIb) in the total amount of aforementioned (I)+(II)+(IIIb) on the other hand, but in greater than 80 quality %, tectal subduing property is just bad.

When the non-volatile content concentration in this suitable coating composition less than 5 quality % the time, the explained hereafter when forming coating is bad, perhaps because effective constituent concentration is low excessively, therefore the thickness that can not guarantee necessary coating is just arranged.On the other hand, the upper limit for non-volatile content concentration, should not be subjected to special restriction, but the time greater than 30 quality % situations, the volatile matter concentration of solvent (IV) etc. is low, therefore during coating processes, when the viscosity rising of this suitable coating composition, the possibility that can not homogeneous applies is just arranged, and the reaction stability of this suitable coating composition is bad.

In addition, when the content of the organo-silicon compound (III) in this suitable coating composition greater than 3 quality % the time, apply after this suitable coating composition organo-silicon compound (III) evaporation during drying, because condensation reaction is difficult for effectively stably handling in coating.Therefore, except that the constituent of coating not necessarily, can not keep consistently the high-performance because the dispersing of the organo-silicon compound of specially giving a long price for (III), and cause waste.In addition, because the evaporation of low-boiling these organo-silicon compound (III) and dispersing, the viscosity of this suitable coating composition is also changed (be owing to make in batches, form not necessarily, also one of dissimilar reason of performance).And for the lower limit of organo-silicon compound (III) content in this suitable coating composition, should not be subjected to special restriction, according to the raw material gradation composition and the use level that contain organosilyl compound (IIIb), further according to thereafter add water decomposition condensation reaction etc., to the full dose that contains organosilyl compound (IIIb) in the resulting coating composition is to add the composition that water decomposition condensation product etc. obtains by adding water decomposition condensation product (IIIa) and organic compound (II) and (being total to), even organo-silicon compound (III) content is that 0 quality % is good.

The coating composition that this is suitable, further, the total light transmittance at optical path length 1cm place is more than 80%, and is preferred more than 85%, more preferably is desirable more than 90%.

Like this, for coating composition of the present invention, in case the polyreaction (adding the water decomposition polyreaction) and the response competition that depolymerizes, the words that polyreaction (adding the water decomposition polyreaction) is too carried out just cause and cause the particlized phenomenon.If use the coating composition that has this particle, will resulting gas barrier property be reduced with the transparency of resin-formed body owing in resulting coating, comprising heterogeneous particles.In addition, just do not have continuity as forming (tissue and even tectosome), and become inhomogeneous.Also, become the destruction face because this particle is hard.Therefore in the middle of the resin-formed body of resulting gas barrier property, with regard to adaptation, the transparency, gas barrier property, subduing property, the printing bad problem of generation with base material.So, if the optical path length of the coating composition of above-mentioned raw materials (cooperation) composition, adds the water decomposition polyreaction and carries out with regard within reason more than 80% at the total light transmittance at 1cm place, add water decomposition polyreaction appropriateness, therefore also not causing to cause the particlized phenomenon, is desirable.

In addition, as mentioned above, in the coating composition in the present invention, when comprising organic high molecular compound (I) and organic compound (II) as the situation of raw material (A), can comprise macromolecular compound (I) and organic compound (II) potpourri, organic compound (II) add any in water decomposition condensation product, macromolecular compound (I) and organic compound (II) reactant.In addition, comprising macromolecular compound (I), organic compound (II), when further including organic silicon compound (III) as the situation of raw material (B), above-mentioned organic compound (II) and organo-silicon compound (III) be add the product of water decomposition condensation reaction in advance, also be the product that adds the water decomposition condensation reaction altogether, can also comprise macromolecular compound (I) and the reactant that reacted in any.For example, when above-mentioned (A) situation, above-mentioned organic compound (II) can be with the reaction of macromolecular compound (I) before or carry out after the reaction add the material that the water decomposition condensation reaction obtains; When above-mentioned (B) situation, further, above-mentioned organic compound (II) can comprise that adding water decomposition condensation base adds the material that the water decomposition condensation reaction obtains together.

As above-mentioned by the modulator approach of coating composition, should not be subjected to special restriction, when above-mentioned (A) situation, even before the reaction of macromolecular compound (I) and organic compound (II), carry out organic compound (II) to add the water decomposition condensation reaction good, even it is good perhaps to add the water decomposition condensation reaction after the reaction of macromolecular compound (I) and organic compound (II).In addition when the situation of above-mentioned (b), even before the reaction of macromolecular compound (I) and organic compound (II), carry out organic compound (II) and organo-silicon compound (III) to add the water decomposition condensation reaction altogether good, even perhaps after the reaction of macromolecular compound (I) and organic compound (II), add organo-silicon compound (III), it is good or the like that organic compound (II) and organo-silicon compound (III) add the water decomposition condensation reaction altogether.For carrying out time and the interpolation time of each composition, the restriction especially that (I) and reaction (II) and (being total to) add the water decomposition condensation reaction.

In addition, about comprising above-mentioned macromolecular compound (I) in order to modulate conduct, organic compound (II), contain organosilyl compound (IIIb), the raw material of solvent (IV), wherein 50 quality % in (I)+(II)+(IIIb) total amount are above for containing organo-silicon compound (IIIb) reaction, and the non-volatile content concentration in the resulting coating composition is more than 5 quality %, and make organo-silicon compound (III) in this coating composition below 3 quality %, further preferred, total light transmittance at light path line 1cm place is the modulator approach of the suitable coating composition more than 80%, should not limit especially equally with above-mentioned, but in order to adjust the progress that adds the water decomposition condensation reaction of organo-silicon compound (III), according to the suitable conditioned reaction temperature of each modulator approach, reaction time is desirable.But these temperature of reaction and reaction time, except following illustrated because of its modulator approach (mainly making reaction carry out the aspect) difference, because the combination difference of the kind of use raw material etc., so can not unify regulation, but can and use according to each modulator approach and cooperate raw material, the simple preliminary experiment of the chamber level that experimentizes in advance can be understood temperature of reaction and reaction time in order to satisfy above-mentioned condition of the present invention simply.At this moment, the non-volatile content concentration in the above-mentioned coating composition of known quantivative approach simple knowledge such as available vapor-phase chromatography and the content of organo-silicon compound (III).

That is to say, adopt the modulator approach of above-mentioned suitable coating composition, the above-mentioned raw materials composition is reacted, adjust the progress that adds the water decomposition condensation reaction of organo-silicon compound (III), according to the content of non-volatile content concentration in the coating composition of afore mentioned rules and organo-silicon compound (III), suitable adjustment temperature of reaction, reaction time etc. allow.With regard to making the reaction mode (reactive mode) of carrying out, material composition is once reacted, material composition is reacted etc. stage by stage, should not limit especially.In addition, with regard to adjust the means of above-mentioned 2 necessary conditions according to reaction, be exactly according to kind and use level and the reactive mode of using material composition, the necessary temperature of reaction that decision suits, reaction time, stirring rate, raw material input speed etc.And as hereinafter described the embodiment example like that, adding water according to reaction, to make reaction be desirable.In addition, so-called " adding water carries out reaction " both just was meant and can as solvent (IV) reaction carried out separately with water, also can as solvent (IV) reaction be carried out with the mixed solvent that water and other solvents (more than one) form, as long as use (interpolation) moisture at least solvent, reaction is carried out just.Representative method in the modulator approach of the coating composition that following example is suitable (mainly being the mode that reaction is carried out).Can enumerate:

(1) simple mixing comprises above-mentioned macromolecular compound (I), above-mentioned organic compound (II), contains the above-mentioned method that contains the gradation composition (even it is good to comprise other any compositions) of organosilyl compound (IIIb) and solvent (IV);

(2) in advance in the presence of solvent (IV), make after the functional group of above-mentioned macromolecular compound (I) and above-mentioned organic compound (II) reacts, add the above-mentioned method that contains organosilyl compound (IIIb);

(3) in the presence of above-mentioned macromolecular compound (I) and solvent (IV), make above-mentioned organic compound (II) and the above-mentioned organo-silicon compound (III) that contain in the organosilyl compound (IIIb) carry out the method that (being total to) adds the water decomposition condensation reaction;

(4) in the presence of solvent (IV), making above-mentioned organic compound (II) and the above-mentioned organosilyl compound (III) that contains in the organosilyl compound (IIIb) carry out (being total to) adds after the water decomposition condensation reaction, make method of reacting or the like, in this any restriction that not given an example by these with above-mentioned organic high molecular compound (I).

In addition, wish, replenish and even append in good time above-mentioned solvent (IV) according to its stage of modulating and method.And add in the water decomposition condensation reaction above-mentioned, can use known catalyzer, and to make reaction in solvent (IV) be favourable.Especially, preferably make organo-silicon compound (III) and organic compound (II) add the water decomposition condensation reaction altogether in advance.In addition, as described later, wish to make suitable coating composition after being coated on the base material, harden, drying, add organic silicon compound (III) in the water decomposition condensation coating composition etc.

Method as the coating that above-mentioned coating composition is formed, be not particularly limited, can adopt over known coating (coating processes) method, promptly after the last coating of base material (layer when between base material and coating the middle layer being set) uses solvent (IV) to be modulated to certain density coating composition, carry out by the drying of overlay film (sclerosis), form coating, but further, the coating that preferred maturation process forms.Below, more be described in detail.

At first, as going up the painting method that applies coating composition at base material (layer when between base material and coating, the middle layer being set), should not limit especially, can suit to utilize the existing known film formation technology that is suitable for the base material shape, (coating processes or the coating) technology of coating, for example can adopt the cylinder cladding process, the immersion coating method, bar cladding process (バ one コ one ティ Application ぐ method), the nozzle cladding process, the pressing mold cladding process, the spray application method, spin coating method, curtain cladding process (カ one テ Application コ one ティ Application ぐ method), the flow coating method, reticulated printing, photogravure, the various printing processes of flexography etc. etc., perhaps these combination.Wherein, consider that with the stable aspect that applies agent the pressing mold cladding process is preferred from increasing choke.

Secondly, after applying above-mentioned coating composition, dry (sclerosis) films.For described drying (sclerosis) method,,, be preferred forming the good fine and close coating of hard conating rapidly if heat or heating, humidification.Therefore, when situation about heating, be preferred in the following heating of heat resisting temperature of base material (between base material and coating during set middle layer, base material and these layers).At this, the heat resisting temperature of so-called base material is exactly the ceiling temperature that in fact can keep substrate property, if the middle layer of plastics, organic class for example is glass temperature and Tc and decomposition point etc.

And, in dried coating film (sclerosis), organo-silicon compound (III) content of the coating composition that forms when being used for filming is during greater than the situation of 3 quality %, this organo-silicon compound (III) evaporation specially, disperse, will influence the performance of security and gained coating (and then gas stop resin formation body), but the coating composition among use the present invention, at base material (when between base material and overlayer, the middle layer being set, base material and these layer) under the following heating state of heat resisting temperature, can prevent the evaporation of organo-silicon compound (III) effectively.Especially, organo-silicon compound (III) are by reaction (condensation) in the system film, effect with the moisture-proof that improves the coating that forms, greatly also can keep sufficient gas barrier property even the humidity in the atmosphere becomes, so can prevent the evaporation of organo-silicon compound (III), be very effective.

Further, after above-mentioned dried coating film (sclerosis), it is preferred carrying out maturation process.By maturation process, reduce and reduced the SiOR in the unreacted above-mentioned organic compound (II) in the coating ³SiOR in group and the organo-silicon compound (III) ²Group, even under any environment for use (for example, in the situation that becomes the inner for the moment high negative pressure state of humid tropical condition, wet condition or liquid crystal etc.), also can bring into play high gas barrier property, be that we are desirable, so maturation process is for after above-mentioned dried coating film (sclerosis), can make the SiOR in the unreacted above-mentioned organic compound (II) in the coating ³SiOR in group and the organo-silicon compound (III) ²Radical reaction (condensation).As maturation process, for example can be used on and reduce unreacted effective thermal treatment in base aspect (for example under 40-60 ℃ of temperature, thermal treatment 1-7 days) and Corona discharge Treatment etc., if can promote the SiOR in the unreacted above-mentioned organic compound (II) in the coating ³SiOR in group and the organo-silicon compound (III) ²Radical reaction (condensation) just should not limit these especially.

And, aspect base material (layer when between base material and coating, the middle layer being set) time of last formation coating and the relation of unreacted base, as long as base material (when between base material and coating, the middle layer being set layer) go up apply add the water decomposition condensation reaction and obtain add the water decomposition condensation product, after dry (sclerosis), and then make SiOR in the unreacted organic compound (II) ³SiOR in group and the organo-silicon compound (III) ²Radical reaction (condensation), handle just, perhaps apply making to go up at base material (when between base material and coating, the middle layer being set layer) before adding the water decomposition condensation reaction, make it simultaneously to add the water decomposition condensation reaction with dry (sclerosis), and then make SiOR in the unreacted above-mentioned organic compound (II) ³SiOR in group and the organo-silicon compound (III) ²Radical reaction (condensation) is handled just, or the like, should not limit especially.

By above-mentioned drying of filming (sclerosis), further, just can on base material, form the coating that obtains by coating composition of the present invention by maturation process.

The thickness of above-mentioned coating, according to the difference of use and difference, therefore can not unify regulation, as long as can satisfy the performance requirement of gas barrier property as effect of the present invention, adaptation, the transparency, subduing property, printing, moisture-proof etc. effectively with base material, usually at 0.01-20 μ m, preferred 0.1-15 μ m, more preferably 0.5-10 mu m range.When (dried) thickness of coating is 0.01 μ m situation, except easily generation pinprick on the coating, coating is also inhomogeneous, is difficult to the performance requirement of fully satisfied gas barrier property as effect of the present invention, the adaptation with base material, the transparency, subduing property, printing, moisture-proof etc. simultaneously.On the other hand, during greater than 20 μ m situations, coating generation crackle is not so be desirable at (dried) thickness of coating.

In addition, as the base material that can be used in gas stop resin formation body of the present invention, if having thermotolerance, subduing property, the transparency, moisture-proof, solvent resistance etc. to the desired characteristic of substrate, just should not limit especially.Can use the base material of the various uses of the gas barrier property that requires, for example be used for base material of the container of the container of base material, food and drink product of the liquid crystal display substrate of LCD (panel) and other base plate for displaying and wrappage (food packing film and packaging film etc.), pharmaceuticals and medicine equipment and wrappage etc. etc.Particularly, for each such purposes, the desired characteristic of base material is required also different, so can not unify regulation, should be according to characteristic requirement separately, for example according to mechanical property, optical characteristics etc., the only base material of suitable selection is not particularly limited.If give an example particularly, can enumerate tygon, polyolefin resins such as polypropylene, polyethylene terephthalate, polyethylene glycol isophthalate, poly-2,6 naphthalenedicarboxylic acids (Na Off レ one ト) glycol ester, polybutylene terephthalate, and the polyester resin of their multipolymer etc., polyamide-based, polystyrene, polymethacrylate, polyacrylonitrile, polyvinyl acetate (PVA), polycarbonate, poly-aryl compound, cellophane, polyimide, polyetherimide, polysulfones, polyethersulfone, polyetherketone, ionomer resin, thermoplastic resins such as fluororesin, and melamine resin, urethane resin, epoxy resin, phenolic resin, unsaturated polyester resin, urea resin, alkyd resin, the thermoset resin of silicones etc. etc.Also have, optimum base material is different different because of each purposes as mentioned above, but be used in liquid crystal display substrate and other displays with in the base material, from viewpoints such as thermotolerance, physical strength, the transparency, mouldability, preventing property of reflection, optimum base material optimization polycarbonate, poly-aryl compound etc.Base material in the time of as container that gas stop resin formation body is used for the food and drink product and packing material (food packing film and packing film etc.), from physical strength, the transparency, thermotolerance, the moulding easiness, painted, viewpoints such as low heating power quantification are set out, preferred impact resistant polystyrene (HIPS), polyethylene terephthalate (PET), gas barrier resin, polyolefin resin such as tygon and polypropylene, polyacrylonitrile, polyamide, cellophane, especially from being easy to process viewpoint, more preferably polypropylene, polyamide, thermoplastic resins such as PET.These can independent a kind of use, also can more than two kinds and use.In addition, the characteristic requirement that these substrates can not obtain in order to obtain with homogenous material can make multilayer with the material of different in kind.As mentioned above, these base materials should be the most general but utilize the plastics with transparency for the master, but should not limit these according to the suitable decision of use, do not get rid of translucent or opaque plastics.Further glass, pottery, metal (comprising alloy and metal oxide) etc. also are suitable for, and for example on transparent plastic substrate (a part), vacuum metallizing etc. also belong to technical scope of the present invention.

As the shape of above-mentioned base material, not restriction especially has and can select according to use is suitable according to the feature of arbitrary shape moulding.And, should not adhere rigidly to the title of substrate, for example show occasion with base materials at liquid crystal display substrate and other, if the form that is suitable for just should be included in the scope of the present invention, except that film shape, also can be chip shape.Also have, in the middle of film shape and chip shape, can have curved surface.And the packing material base material occasion at the container of food and drink product and wrappage etc. if be applicable to the form of this purposes, just should be included in the scope of the present invention, and except that film shape, also can be chip shape, bottle shape etc.And, in the middle of film shape and chip shape, can have curved surface.

The thickness of above-mentioned base material, different different because of use, unified regulation is difficult, should select according to purposes is suitable.For example, show with in the base material that thickness is usually at 5-1000 μ m being used in liquid crystal indicator and other, preferred 10-500 μ m, more preferably 100-300 mu m range.When base material thickness is less than 5 μ m,, image bad except that surface smoothing is bad,, can not keep full intensity etc. sometimes, so be unfavorable as surperficial panel.On the other hand, when base material thickness is greater than 1000 μ m, except that the image confusion, is difficult to sometimes satisfy what is called is carried the requirement of the desired light weight slimming of apparatus, so be unfavorable.In addition, in the packing material base material of container that is used in the food and drink product and wrappage (food packing film and packing film etc.) etc., thickness is usually at 7-100 μ m, more preferably at the 10-30 mu m range.When the thickness of this base material less than 7 μ m the time, except that pinprick may take place, physical strength was also good inadequately, so be not desirable.On the other hand, when the thickness of this base material the time, except the productivity of gas stop resin formation body is bad, be difficult to sometimes satisfy to container and the desired filming requirement of wrappage, so be unfavorable greater than 100 μ m.

In addition, in the middle of the gas stop resin formation body in the present invention, between base material and coating, perhaps on coating, as required, other layers can be set.For example,, further form known in the past various gas barrier resin compositions as the gas barrier property coat, can be multilayer structured.Below, describe as an example with the gas barrier resin coat.For between above-mentioned base material and coating, perhaps on coating, form such gas barrier resin coat, particularly, in order to be easy to even film forming, may utilize by gas barrier resin being dissolved in appropriate solvent and spreading agent and even disperseing and the composition that forms, for example may utilize composition that can form and the composition that forms by making gas barrier resin emulsification etc. in water and solvent by gas barrier resin is dissolved.As gas barrier resin, for example can enumerate polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer, Vingon, polyamide etc.Refer to as the gas barrier property tree, preferably polyethylene alcohol, ethylene-vinyl alcohol copolymer, this material is not except containing the chlorine that can become the public hazards reason, even under any environment for use (for example, in the situation that becomes the inner for the moment high negative pressure state of humid tropical condition, wet condition or liquid crystal etc.), also can bring into play fully high gas barrier property, be comparatively effective, and we are desirable so can be described as.That is to say, we can say because such gas barrier resin coat can be found the good gas barrier property that known gas barrier layer had in the past for the present invention.Therefore, in the present invention, because above-mentioned coating has the abundant gas barrier property that can not obtain in the known in the past gas barrier layer, and the gas barrier property that has in humid tropical condition, wet condition or liquid crystal inside more the situation etc. of for the moment high negative pressure state, so obtain having the laminated body of very high performance gas barrier property.

In the said gas-blocking resin coating layer, except the said gas-blocking resin, also can in the scope of not damaging effect of the present invention, cooperate the various adjuvants of inorganic organic class such as curing catalysts, wettability improver, plastifier, defoamer, tackifier as required.About its use level,, and in can bringing into play the scope of the characteristic of adjuvant separately effectively, just should not limit especially if do not damaging in the scope of the invention.

The thickness of gas barrier resin coat of the present invention, different and different because of laminated layer sequence with purposes, therefore can not unify regulation, but usually at 0.3-20 μ m, preferred 0.5-10 μ m is more preferably in the 1-5 mu m range.When the thickness of gas barrier resin coat less than 0.3 μ m the time, the functions such as gas barrier property of having added the gas barrier resin coat are insufficient.On the other hand, when greater than 20 μ m the time, the productivity of gas barrier resin coat is bad.

In addition, in gas stop resin formation body of the present invention, multilayer thermoplastic film further.Owing to use this multilayer thermoplastic film, good more high-strength hot sealing, the gas stop resin formation body of security can be provided.Also have, thermoplastic film generally is used as the top overlay in the lamination gas stop resin formation body, but also can be according to use, in gas barrier laminate as the middle layer lamination.

As above-mentioned thermoplastic film, if can satisfy, just should not limit especially according to the desired characteristic requirement of use, can utilize known in the past film, consider optimization polypropylene, tygon from security, cost aspect.

Gas stop resin formation body of the present invention is by forming coating on above-mentioned base material, further as required, forms that the gas barrier resin coat constitutes.Because described formation, compare with already present gas-barrier films substrate, can further give function, but said here so-called function is different different because of use, so be not particularly limited, but for example can enumerate the environmental safety of heat seal, chemical-resistant, gas barrier property etc.Specifically, even under any damp condition, can both obtain the stable gas stop resin formation body of gas barrier property.

In addition, the gas stop resin formation body among the present invention, as long as at the above-mentioned at least coating of base material superimposed layer, further lamination gas barrier resin coat is just as required.In addition; except that above-mentioned coating and gas barrier resin coat; the coat that also can have other characteristics; transparency electrode (ITO etc.) layer for example; the common electrode layer; polarizing layer; antireflection layer; the orientation rete; the phasic difference layer; sheathcoat; color filter layers; the TFT layer; dielectric layer; protective film; fluorophor; insulation course; resistant layer; barrier film; protective film; cold cathode; ゲ one ト; negative electrode; anode; the instantaneous short burst line of anode (ァノ one De バス line); show electrode; address electrode; the aluminium-vapour deposition layer; sticking interlayers etc., lamination or the suitable coat of selecting formation to have other characteristics as required can suit to select to carry out.These coatings and gas barrier resin coat can form or lamination in the inside of formed base material side.And these need only the purposes according to its use, and suitable decision laminated layer sequence and laminated thickness are just.In addition, on these coats, can design the good chemical-resistant coat that is used as top coat in a sense, also can the above-mentioned thermoplastic film of lamination.That is to say, use thermoplastic film, can make it to have the characteristic that requires as the top coat that has existed, and can give heat seal, security, so be outstanding.

That is, in gas stop resin formation body of the present invention, between base material and coating and at the first-class place of coating, also can there be layer with other functions.And, comprise these layers of coating, can not respectively one deck (individual layer), also can be by the sandwich construction that forms of layer more than one deck as required.

With regard to the gas barrier property of gas stop resin formation body of the present invention, therefore different and different because of the structure composition of each layer and all rhythmo structure etc. can not unify regulation.Satisfy formation necessary condition of the present invention but be at least, the oxygen permeability (A) after 60 ℃ of this gas stop resin formation body, 90%Rh were handled in 24 hours can reach the ratio of the oxygen permeability (B) before handling, (A)/(B)≤10.0, and preferred≤5.0.In the ratio (A)/(B)＞10.0 of oxygen permeability (A) after 60 ℃ of gas stop resin formation body, 90%Rh were handled in 24 hours to the oxygen permeability (B) before handling, because of the environmental change gas barrier property changes (variation), therefore except not necessarily ensuring the quality of products, can not find in hot and humid sufficient gas barrier property down, so be not desirable.And, the condition when oxygen permeability (A) and measurement (B) be not hot and humid down, as long as under 20-30 ℃ usually, 85-95%Rh condition, measure (with reference to as described later embodiment 1-6 and comparative example 1-6 etc.), so should not limit especially.

In addition, the said gas-blocking resin-formed body, except because of the different desired benchmark differences of use, also different and different because of the kind of base material and the structure of all laminations etc., therefore can not unify regulation, but if for example as the use occasion with film of the container package of Food ﹠ Drink product, gas (oxygen) permeability when wishing under high humidity (20 ℃, 90% Rh) is at 30ml/m ²Below the 24hatm, preferred 20ml/m ²Below the 24hatm, more preferably 10ml/m ²Below the 24hatm.

Further, the same with transparent membrane with the following choke that will illustrate, it is exactly more suitably that the oxygen permeability the when flexible resistance of gas stop resin formation body test 20 times later 20 ℃, 60%Rh satisfies following benchmark requirement: at 20ml/m ²Below the 24hatm, preferred 10ml/m ²Below the 24hatm, more preferably 5ml/m ²Below the 24hatm.

In addition, with regard to the manufacture method of the gas stop resin formation body relevant with the present invention, should not limit especially, the known in the past various display fabrication techniques of suitable utilization, to the thin film fabrication technology on the film substrate, for example by the cylinder cladding process, the immersion coating method, the bar cladding process, the pressing mold cladding process, the integrated molding of spin coating method or base material and gas stop resin formation body (is extruded, compression, injection-molded moulding etc.) technology, coating technique, the forming technique of the container package material of lamination technology etc. etc. and the coating technology or the wet type film technique that make up these method etc., further dry masking technique of physical vapor deposition etc. etc. just can be made.In addition, in the TFT in forming gas stop resin formation body etc., need only manufacturings such as suiting to utilize semiconductor fabrication.

Suitable embodiment as the manufacture method of the gas stop resin formation body relevant with the present invention, it is characterized in that, on base material, coating comprise have amino macromolecular compound (I) and in molecule, have can with the functional group's of amino reaction organic compound (II), further comprise coating composition, make the formation coating by the organo-silicon compound (III) of above-mentioned general formula (1) expression.But in addition, also can form gas barrier resin and cover coating, transparent electrode layer, common electricity layer, polarizing layer, antireflection layer, orientation rete, phasic difference layer, sheathcoat, color filter layers, TFT layer, dielectric layer, protective film, fluorophor, insulation course, resistant layer, barrier film, opposing rete, cold cathode, グ one ト, negative electrode, anode, the instantaneous short burst line of anode (ァノ one De バス line), show electrode, address electrode, aluminium-vapour deposition layer, adhesive linkage and thermoplastic film etc.In addition, the formation method with regard to each layer should not limit especially, the method for having narrated above can utilizing etc., in this description will be omitted.

Secondly, the purposes of the gas stop resin formation body relevant with the present invention is characterized in that, as liquid crystal display substrate.Thus, even at (from constant temperature and humidity under the dried state and even under the lower negative pressure state under hot and humid wet condition and for the moment liquid crystal inside become the situation etc. of high negative pressure state) under any environment for use, also can give full play to high gas barrier property, solve in the past because the problem of the malfunction that causes because of gas-premeable difference gassing that hot and humid time Exposure to Sunlight causes etc. so can provide, provide to have high-performance and the high liquid crystal display substrate of high-quality reliability, and then use it to form liquid crystal indicator.

Represent gas stop resin formation body of the present invention can be used for the device construction that representative liquid crystal display that liquid crystal display obtains with substrate is used with diagram, these only are examples, and these should not limit the present invention.

Fig. 1 represents an example with the general colored TFT liquid crystal display model in the slim assemblies of income such as liquid crystal panel, backlighting, driving loop, in order to be easy to understand a part of sectional oblique drawing that is expressed as multi-ply construction part section part.As shown in Figure 1, the liquid crystal panel is to be made of the sandwich construction that repeats the various function thin plates of several piece.Omitted the driving chip that disposes later in the drawings.As shown in Figure 1, in the slim assembly that forms by container 101 and video screen (metal framework) 103, has from the surface in turn sandwich construction with Polarizer 105, liquid crystal display substrate 107, colored filter 109 (having omitted the electrode and the alignment films that constitute in its back the figure), liquid crystal 111, liquid crystal display substrate 113 (having omitted the TFT and the alignment films that are constituted among the figure), Polarizer 115, prismatic glasses 117, light guide plate 119 and reflecting plate 121 laminations; The structure that connects the distribution 125 in fluorescent tube 123 and driving loop etc. in the lateral parts design.At this, be illustrated in the part place that uses glass substrate over, even form the gas stop resin formation body that when hot and humid, also has the coating of good gas barrier property at its one or both sides place, as liquid crystal display substrate 107 and liquid crystal display substrate 113, either party can use gas stop resin formation body of the present invention.

Fig. 2 is that expression can be used the summary section of the general colored stn liquid crystal display of liquid crystal display substrate of the present invention with the another kind of example of the gas stop resin formation body relevant with the present invention as the liquid crystal indicator that is used for liquid crystal display substrate formation.As shown in Figure 2, basically 2 liquid crystal display substrates are overlapping, and the liquid crystal panel of place, crack inflow liquid crystal is considered as essential structure body aspect betwixt, identical with Fig. 1, from the surface is the Polarizer 201 with lamination in turn, phasic difference plate 203, liquid crystal display substrate 205, transparency electrode 207, alignment films 209, liquid crystal 211 (liner that is provided with for maintenance cell gap when 2 liquid crystal display substrates lump together up and down is certain), alignment films 215, transparency electrode 217, sheathcoat 219, chromatic filter layer 221, liquid crystal display substrate 223, phasic difference plate 225, the multi-ply construction of Polarizer 227 and light guide plate 229 is provided with the structure of fluorescent tube 231 at the lateral parts of light guide plate 229.Omitted in the drawings and driven with chip, driving circuit distribution etc.At this, be illustrated in the part place that uses glass substrate over, as liquid crystal display substrate 205 and liquid crystal display substrate 223, either party can use gas stop resin formation body of the present invention with gas stop resin formation body.And omitted in the drawings that each substrate surface place in this liquid crystal display substrate 205,223 forms, even when hot and humid, also have the overlayer of good gas barrier property.

And, for each constitutive requirements of display out of the ordinary, do not need to describe in detail, each each other display is having much of practicability, and every day new proposition all arranged, can suit to utilize in the middle of these only, form the display of desired mode.To manufacture method separately, established the whole bag of tricks is practicability also, and all have every day new manufacture method to propose, and can suit to utilize these in the middle of these, makes the display of desired mode, and this is self-evident.

Secondly, other purposes of the gas stop resin formation body relevant with the present invention is characterized in that, as packing material.Thus, even at (from constant temperature and humidity under the dried state and even inferior under the lower negative pressure state) under any environment for use to hot and humid wet condition, also can fully keep high gas barrier property, so can provide can solve in the past since hot and humid time Exposure to Sunlight cause because of the problem of the long lifetime difficulty of gas-premeable difference food quality between the bad shelf-life that causes etc., container and packing material with high food and drink product of high-performance and high-quality reliability etc. are provided.

Secondly, the choke transparent membrane relevant with the present invention, it is characterized in that, be to have the transparent plastic that has amino macromolecular compound (I) and have the coating that can obtain with the coating composition of the functional group's of amino reaction organic compound (II) in molecule by comprising on the one side at least of transparent plastic film base material;

Oxygen permeability when this film flexible resistance test 20 times later 20 ℃, 60%Rh is at 20ml/m ²Below the 24hatm.

Here, choke is with " having the coating that is obtained by coating composition " in the transparent membrane, with said gas-blocking with illustrated identical in the resin-formed body, so, omitted the explanation of described main composition important document here for fear of repetition.

As being used for the plastic film substrate of choke of the present invention with transparent membrane, so long as transparent words, just be not particularly limited, can enumerate for example polyolefin such as tygon, polypropylene, polyethylene terephthalate, polyethylene glycol isophthalate, poly-2,6-(ethylene naphthalate), polybutylene terephthalate and and the polyester of above-mentioned multipolymer etc., polyamide, polystyrene, poly-(methyl) propernoic acid ester, polyacrylonitrile, polycarbonate, cellophane, polyimide, polyetherimide, polysulfones, polyetherketone, ionomer resin etc.Consider from the versatility angle, wish to use polyolefin, polyester, polyamide.Especially, using the polyolefin occasion is being effective aspect the raising moisture resistance.These can independent a kind of use, also can use side by side more than two kinds.And, the characteristic requirement of these substrates in order to obtain obtaining by independent a kind of material itself, but do as one likes matter different materials is made multilayer.

Above-mentioned transparent plastic film base material is that total light transmittance is more than 50%, and is preferred more than 70%, more preferably the film more than 80%.During less than 50% situation, can not obtain the sufficient transparency at total light transmittance sometimes.

Above-mentioned transparent plastic film base material, in not damaging choke of the present invention scope with the transparent membrane effect, can adopt the Corona discharge Treatment film substrate or fixedly the coating known method of handling film substrate etc. handle.

The preferred 5-500 μ of above-mentioned transparent plastic film thickness m, more preferably 10-50 μ m.If thinner than 5 μ m, defectives such as pinprick may take place in the insufficient strength of film.If thicker than 500 μ m, choke is poor with the productivity of transparent membrane sometimes.

With in the middle of the transparent membrane, the thickness of above-mentioned coating is 0.1～10 μ m, preferred 0.3～5 μ m, more preferably 0.5～3 μ m at choke of the present invention.If thinner than 0.1 μ m, gas barrier property is not enough, if thicker than 10 μ m, 20 later gas barrier properties of flexible resistance test might reduce.

Oxygen permeability when the flexible resistance of choke purposes transparent membrane of the present invention test 20 times later 20 ℃, 60%Rh is 20ml/m ²Following, the preferred 10ml/m of 24hatm ²24hatm is following, more preferably 5ml/m ²Below the 24hatm air pressure.In the present invention, because by adjusting the composition of coating composition, can access and have desirable physical strength concurrently, the coating of subduing property is so the oxygen permeability can realize obtaining flexible resistance experiment 20 times later 20 ℃, 60%Rh the time is 20ml/m ²The choke transparent membrane of the good flexible resistance that 24hatm is following.

" the flexible resistance experiment " mentioned in the present invention is meant for example uses flexible resistance experiment instrument (of science industrial society make), 20 ℃, the test of mensuration during 60%Rh.

The choke relevant with the present invention is characterized in that with the purposes of transparent membrane, is as packing material.Thus, can provide and have good gas barrier property, do not have good flexible resistance, good and adaptation base material, subduing property, the transparency, printing because of the base material kind, and can find that these characteristics usually are stable, have the packing material of the container of high-performance and high-quality, food that reliability is high, beverage product etc. and wrappage etc.

Embodiment

Below, enumerate embodiment and specify the present invention, but following embodiment there is not any restriction to the present invention, before and after not departing from, change in the scope of described connotation, the scheme of being implemented all is comprised in the technology of the present invention scope.Oxygen permeability, the transparency, adaptation and solvent resistance in embodiment 1-6 and comparative example 1-6 are measured by following assay method.

" oxygen permeability assay method "

With oxygen permeability determinator (manufacturing of モダ Application ュ Application トロ one Le ズ company), 20 ℃, measure during 80%Rh, unit is ml/m ²24hatm.

" transparent assay method and determinating reference "

Range estimation (observation) lining appearance of films.

It is exactly transparent not having gonorrhoea or cloud point, represents with zero; Can find out some gonorrhoeas or cloud point, usefulness * expression are only arranged.

" adaptation assay method and determinating reference "

On the lining film, carry out the go バ Application order test of the ITO film of made film.

The usefulness of not peeling off zero is represented, finds out the usefulness * expression of peeling off.

" solvent resistance assay method and determinating reference "

In the time of 20 ℃, in gamma-butyrolacton, dipping lining film (not making the film of ITO film) 5 minutes.

Behind the dipping, the usefulness zero that the lining film not have to change represents, the usefulness * expression of peeling off with variation such as gonorrhoea is arranged.

Reference example 1

Mix 50g ェ Port ミ Application SP-200 (polyethyleneimine: the trade name of Nippon Shokubai Co., Ltd), 30g β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane and 500g ethanol, 70 ℃ of reactions 3 hours down.After being cooled to room temperature, reacted again 24 hours after the mixed liquor of adding 10g water and 300g ethanol, make coating composition 1.

Reference example 2

The trade name of Nippon Shokubai Co., Ltd), 20g β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane and 500g ethanol mix 50g ェ Port ミ Application SP-200 (polyethyleneimine:, under 70 ℃, reacted 3 hours.After being cooled to room temperature, the mixed liquor that adds 15g water and 100g ethanol, added 150g tetramethoxy-silicane oligomer (M silicate 51: the trade name of the KCC that rubs) and after the mixed liquor of 300g ethanol, reacted 24 hours more, make coating composition 2 in 1 hour later on again.

Reference example 3

Except replace the ェ Port ミ Application SP-200 in the reference example 2 with the multipolymer of dimethyl amino ethyl methacrylate, styrene and butyl acrylate cores (mass ratio is 50: 30: 20), other are identical with reference example 2, make coating composition 3.

Reference example 4

Except replacing with gamma-methyl allyl acyloxypropyl trimethoxysilane beyond β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane in the reference example 2, other are identical with reference example 2, make coating composition 4.

Reference example 5

SP-200 is dissolved in the 500g ethanol with 50g ェ Port ミ Application, makes coating composition 5.

Reference example 6

Except replace the ェ Port ミ Application SP-200 in the reference example 2 with polyvinyl alcohol (PVA), other are identical with reference example 2, make coating composition 6.

Reference example 7

Except replacing with methyltrimethoxy silane beyond β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane in the reference example 2, other are identical with reference example 2, make coating composition 7.

Reference example 8

Mix 10g ェ Port ミ Application SP-200 (polyethyleneimine: the trade name of Nippon Shokubai Co., Ltd), 200g β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane and 900g ethanol, 70 ℃ of reactions 3 hours down.After being cooled to room temperature, the mixed liquor that adds 20g water and 300g ethanol reacted 24 hours again, made coating composition 8.

Reference example 9

The trade name of Nippon Shokubai Co., Ltd), 2g β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane and 50g ethanol (polyethyleneimine:, reaction is 3 hours in the time of 70 ℃ to mix 5g ェ Port ミ Application SP-200.After being cooled to room temperature, the mixed liquor that adds 5g water and 100g ethanol, added 1500g tetramethoxy-silicane oligomer (M silicate 51: the trade name of the KCC that rubs) and after the mixed liquor of 3000g ethanol, reacted again 24 hours more, make coating composition 9 in 1 hour later on again.

Embodiment 1

Be coated in resulting coating composition 1 in the reference example 1 on the two sides of the polycarbonate film (hereinafter to be referred as the PC film) of thickness 100 μ m, making its dried thickness is 1.2 μ m, makes lining film 1-A.And then on the plane of this lining film 1-A, transparent conductivity material ITO system film is become the film of thick 500 with spraying process.The evaluation of the characteristic of gained substrate 1 is listed in the table 1.

Embodiment 2-5

Except that the content of listing in following table 1, other are identical with embodiment 1, make substrate 2-5.Evaluating characteristics is also listed in the table 1.

Comparative example 1-5

Except that the content of listing in following table 1, other are identical with embodiment 1, make comparison substrate 1-5.Evaluating characteristics is also listed in the table 1.

Table 1

	Film substrate thickness material	Coating composition	Attribute testing
			Attribute testing						The transparency	Adaptation	Solvent resistance	Oxygen permeability (A)	Oxygen permeability (B)	A/B
			Embodiment 1	100μm PC	Coating composition 1	○	○	○	The transparency	Adaptation	Solvent resistance	Oxygen permeability (A)	Oxygen permeability (B)	A/B	8.8	1.2	7.3
Embodiment 2	100μm PC	Coating composition 2	Embodiment 1	100μm PC	Coating composition 1	○	○	○	○	○	○	0.2	0.1	2.0	8.8	1.2	7.3
Embodiment 2	100μm PC	Coating composition 2	Embodiment 3	75μm PAR	Coating composition 3	○	○	○	○	○	○	0.2	0.1	2.0	3.7	0.9	4.1
Embodiment 4	100μm PC	Coating composition 4	Embodiment 3	75μm PAR	Coating composition 3	○	○	○	○	○	○	0.9	0.3	3.0	3.7	0.9	4.1
Embodiment 4	100μm PC	Coating composition 4	Embodiment 5	20μm PET	Coating composition 2	○	○	○	○	○	○	0.9	0.3	3.0	0.3	0.2	1.5
Comparative example 1	100μm PC	Coating composition 5	Embodiment 5	20μm PET	Coating composition 2	○	○	○	Be not stained with and do not form coating						0.3	0.2	1.5
Comparative example 1	100μm PC	Coating composition 5	Comparative example 2	100μm PC	Coating composition 6	○	×	×	Be not stained with and do not form coating						＞1000	120.0	＞8
Comparative example 3	100μm PC	Coating composition 7	Comparative example 2	100μm PC	Coating composition 6	○	×	×	Be not stained with and do not form coating						＞1000	120.0	＞8
Comparative example 3	100μm PC	Coating composition 7	Comparative example 4	100μm PC	Coating composition 8	○	×	×	Be not stained with and do not form coating						598.7	9.8	61.1
Comparative example 5	100μm PC	Coating composition 9	Comparative example 4	100μm PC	Coating composition 8	○	×	×	○	×	×	＞1000	214	＞46	598.7	9.8	61.1

In film substrate, PC is a polycarbonate,

PAR is poly-aryl compound,

PET is an ethylene glycol terephthalate.

Embodiment 6

To obtain liquid crystal indicator at the lining film before the system of the ITO among the embodiment 2 film as substrate in device construction shown in Fig. 1.Use the gained liquid crystal indicator, 30 ℃, use continuously during 80%Rh, do not see that bubble produces.

Comparative example 6

Will be at the lining film before the system of the ITO in the comparative example 2 film as substrate, with the embodiment 6 identical liquid crystal indicators that obtain in the formation of device shown in Fig. 1.Use the gained liquid crystal indicator, 30 ℃, use continuously during 80%Rh, see that bubble produces.

Further, the film evaluation test in embodiment 7 and the comparative example 7 is performed as follows.

" flexible resistance test "

Use flexible resistance test instrument (industrial group of science makes), 20 ℃, test during 60%Rh.

" oxygen permeability assay method "

Use oxygen permeability determinator (manufacturing of モダ Application コ Application トロ one Le ズ company), 20 ℃, measure during 60%Rh.Unit/ml/m ²24hatm.

" moisture permeability assay method "

According to JIS Z0208,40 ℃, measure during 90%Rh.

Reference example 10

Mix 52g ェ Port ミ Application SP-018 (polyethyleneimine: the trade name of Nippon Shokubai Co., Ltd), 30g γ one diglycidyl oxygen propyl trimethoxy silicane and 400g ethanol, 70 ℃ of reactions 3 hours.Behind the cool to room temperature, add the mixed liquor of 6g water and 20g ethanol, react after 1 hour, add 120g tetramethoxy-silicane oligomer (M silicate 51: the trade name of the KCC that rubs) and after the mixed liquor of 400g ethanol more again, reacted 24 hours, and made coating composition 10.

Reference example 11

Mix 25g ェ Port ミ Application SP-018 (polyethyleneimine: the trade name of Nippon Shokubai Co., Ltd), 7g γ-diglycidyl oxygen propyl trimethoxy silicane and 400g ethanol, 70 ℃ of reactions 3 hours.After being cooled to room temperature, the trade name of the KCC that rubs) and the mixed liquor of 400g ethanol add the mixed liquor of 6g water and 20g ethanol, react after 1 hour, add 120g tetramethoxy-silicane oligomer (M silicate 51: more again, reacted 24 hours, and obtained coating composition 11.

Embodiment 7

It is on the transparent OPP film of 20 μ m (two roller stretched polypropene film) that the coating composition 10 that will obtain in reference example 10 is coated on thickness, making the thickness behind this dried coating film is 1 μ m, 95 ℃, during 10%Rh after dry 10 seconds, handled 3 days at 40 ℃, film 10 obtains being covered.

This lining appearance of films range estimation is transparent, and the oxygen permeability before the flexible resistance test is 0.7ml/m ²24hatm, the oxygen permeability after the flexible resistance test is 1.2ml/m ²24hatm, moisture permeability is 4g/m ²24h.

Comparative example 7

Be used in the coating composition 11 that obtains in the reference example 11, other are the same with embodiment 7, obtain the film 11 that is covered.

Estimating this lining film has gonorrhoea, and the oxygen permeability before the flexible resistance test is 15.5ml/m ²24hatm, the oxygen permeability after the flexible resistance test is 95.7ml/m ²24hatm, moisture permeability is 5g/m ²24h.

In the evaluation test of the lining film in embodiment 8 and embodiment 9, flexible resistance test and oxygen lure the excessively assay method of (C), with identical the carrying out of evaluation test of film in the foregoing description 7 and the comparative example 7.In addition, oxygen permeability (A) and (B), the assay method of the transparency, adaptation and solvent resistance, identical with the assay method of oxygen permeability, the transparency, adaptation and solvent resistance in embodiment 1-6 and comparative example 1-6.

Embodiment 8

Make 10g ェ Port ミ Application SP-200 (polyethyleneimine: the trade name of Nippon Shokubai Co., Ltd) [organic high molecular compound (I)], the mixed liquor of 5g γ-glycidoxypropyltrimewasxysilane [organic compound (II)] and 100g ethanol [solvent (IV)] reacts after 3 hours in the time of 60 ℃, be cooled to room temperature, after adding the mixed liquor of 1.5g water and 10g ethanol [cosolvent (IV)] again, reacted 30 minutes, the mixed liquor that adds 30g tetramethoxy-silicane [organo-silicon compound (III)] and 50g ethanol [solvent (IV)] again reacts and obtains coating composition 12 after 1 hour.The evaluating characteristics of this coating composition 12 is listed in the table 2.

Gained coating composition 12 is coated on the PET film that thickness is 25 μ m, and making it apply dried thickness is 1 μ m.In the time of 100 ℃, after dry 10 seconds,, make lining film 12 again 60 ℃ of following slakings 5 days.This lining is listed in the table 3 with the evaluating characteristics of film 12.

Embodiment 9

Except do not add water in embodiment 8, other are identical with embodiment 8, get coating composition 13.The evaluating characteristics of this coating composition 13 is listed in the table 2 together.

Gained coating composition 13 is coated on the PET film that thickness is 25 μ m, and making it apply dried thickness is 1 μ m.In the time of 100 ℃, after dry 10 seconds,, make lining film 13 again 60 ℃ of following slakings 5 days.This lining is listed in the table 3 with the evaluating characteristics of film 13.

Table 2

	Organo-silicon compound (III) content	Organo-silicon compound (III) evaporation capacity	Non-volatile content concentration
	Organo-silicon compound (III) content	Organo-silicon compound (III) evaporation capacity	Non-volatile content concentration	Embodiment 8	1 quality %	Below the 1 quality %	13 quality %
Embodiment 9	8 quality %	3 quality %	12 quality %	Embodiment 8	1 quality %	Below the 1 quality %	13 quality %

The content of the organo-silicon compound in the table 2 (III):

To the coating composition full dose, the organo-silicon compound (III) that in this coating composition, comprised with the gas chromatography standard measure contain ratio (quality %).

The evaporation capacity of organo-silicon compound in the table 2 (III): making lining by coating composition during film, the amount of organo-silicon compound (III) gas that from this coating composition, is evaporated with the vapor-phase chromatography quantitative measurement.

Non-volatile content concentration in the table 2:

The quality of coating composition is (A), is (B) with this coating composition in 30 minutes later quality of 100 ℃ of heating, represents with following formula: non-volatile concentration=(B)/(A) * 100.

Table 3

	Film substrate (thickness material)	The lining constituent		Attribute testing
				Attribute testing				The transparency		Adaptation	Solvent resistance
				Embodiment 8	25μm PET	Lining becomes thing 12 with thin,tough silk		The transparency		Adaptation	Solvent resistance	○		○	○
Embodiment 9	25μm PET	Lining constituent 13		Embodiment 8	25μm PET	Lining becomes thing 12 with thin,tough silk		○		○	×	○		○	○
Embodiment 9	25μm PET	Lining constituent 13			Attribute testing
	Oxygen permeability (A)		Oxygen permeability (B)		Attribute testing							(A)/(B)	Oxygen permeability (C)
	Oxygen permeability (A)		Oxygen permeability (B)	Embodiment 8	7.1		2.3	3.1	3.9			(A)/(B)	Oxygen permeability (C)
Embodiment 9	24.2		2.5	Embodiment 8	7.1		2.3	3.1	3.9			9.7	25.1

Claims

1, a kind of gas stop resin formation body, it is characterized in that, the coating that comprises (A) base material and obtained by coating composition (B), coating composition wherein comprises: (1) has amino macromolecular compound (I), (2) and has in molecule and can be selected from the organo-silicon compound of representing by with following general formula (1) (III) with organic compound (II), (3) of the functional group of amino reaction

R ¹ _mSi(OR ²) _n (1)

Wherein, R in the formula ¹Represent C _1-4Alkyl, has not the C with the functional group of amino reaction _1-4Alkyl or C _2-4Thiazolinyl; R ²Represent hydrogen atom or C _1-4Alkyl; N represents the integer more than 1; M represents the integer more than 0; And m+n=4,

Add at least a organosilyl compound (IIIb) and (4) solvent (IV) of containing in the group that water decomposition condensation product (IIIa) forms with it;

There is the above organosilyl compound (IIIb) that contains of 50 quality % to make in the total amount of coating composition use above-mentioned (I)+(II)+(IIIb) as raw material;

And the amount of the organo-silicon compound in this coating composition (III) is below the 3 quality %,

Oxygen permeability (A) after 60 ℃ of described resin-formed body, 90%Rh were handled in 24 hours with handle before the ratio (A)/(B)≤10.0 of oxygen permeability (B).

2, a kind of choke transparent membrane, wherein the transparent plastic film base material on the one side coating that is obtained by coating composition is arranged at least, coating composition wherein comprises: have amino macromolecular compound (I), having in molecule can be with the organic compound (II) of the functional group of amino reaction, be selected from the organo-silicon compound of representing by with following general formula (1) (III)

R ¹ _mSi(OR ²) _n (1)

Add at least a organosilyl compound (IIIb) and the solvent (IV) of containing in the group that water decomposition condensation product (IIIa) forms with it;

There is the above organosilyl compound (IIIb) that contains of 50 quality % to make in the total amount of this coating composition use above-mentioned (I)+(II)+(IIIb) as raw material;

Oxygen permeability during 20 ℃ of 60%Rh after the flexible resistance of this film test 20 times is 20ml/m ²Below the 24hatm.

3,, be as liquid crystal display substrate according to the purposes of the gas stop resin formation body of being put down in writing in the claim 1.

4,, be as packing material according to the purposes of the gas stop resin formation body of being put down in writing in the claim 1.

5,, be as packing material according to the purposes of the choke of being put down in writing in the claim 2 with transparent membrane.