JPS60170672A - Coating material - Google Patents

Abstract

PURPOSE:To provide a coating material having excellent gas-barrier property, improved humidity dependence of the gas-barrier property, and improved drawability, by copolymerizing vinyl acetate, ethylene, and a specific silicon-containing monomer, and saponifying the copolymer. CONSTITUTION:The objective material is composed of saponified silicon-containing copolymer of ethylene and vinyl acetate, having a saponification degree of the vinyl acetate component of >=95%, ethylene-content of 20-60mol% and silicon-content of 0.0005-0.5mol%, and obtained by saponifying the copolymer of (A) vinyl acetate, (B) ethylene and (C) a silicon-containing olefinic unsaturated monomer of formula I , formula II and/or formula III (n is 0 or 1; m is 0-2; R<1> is lower alkyl, allyl, etc.; R<2> is 1-40C alkoxyl; R<3> is H or CH3; R<4> is H or lower alkyl; R<5> is alkylene, etc.; R<6> is H, halogen, etc.; R<7> is alkoxyl, etc.; R<8> is H, halogen, lower alkyl, etc.; R<9> is lower alkyl).

Description

Detailed Description of the Invention A1 Technical Field of the Invention The present invention is a saponified ethylene-vinyl acetate copolymer having a partially crosslinked structure, which has good solvent solubility and is resistant to corrosion. The present invention relates to a coating material made of a silicon-containing saponified ethylene-vinyl acetate/vinyl acetate copolymer that maintains gas barrier properties, has improved humidity dependence of the barrier properties, and has improved stretch formability.

B. Prior art ethylene-vinyl acetate I saponified copolymer (hereinafter referred to as EVO)
(abbreviated as H) is a useful polymeric material that has gas barrier properties (gas barrier properties) and high transparency, and has excellent oil resistance and fragrance retention properties. , coating the surface of films, sheets, containers, etc. made of other resins with EVO)I solution and applying an EVOH coating layer to improve the properties such as oil resistance and gas barrier properties of the films, sheets, containers, etc. It is suitably used in a wide range of applications. In addition, as a special case of coating operation, EVO is also used in the production of film by casting method.
A H solution is preferably used, and a film having the above-mentioned excellent properties has been obtained by the casting method. However, EV
OH does not have sufficient environmental stress cracking resistance against pesticide liquids, etc., and also has insufficient resistance to water etc., and due to its high hygroscopic nature, its gas barrier properties are highly dependent on humidity, and it cannot be used under high humidity conditions. There are drawbacks such as a decrease in the barrier properties and poor stretch formability when stretched at least uniaxially.

In an attempt to eliminate these drawbacks, many attempts have been made to modify EVO)1. In particular, with regard to eliminating the former drawback, it is well known that attempts have been made to modify EVOI using various crosslinking agents. No EVOH-based coating materials for modified coatings have been found that have been excluded.In other words, the main ones that have been attempted in the past are attempts to impart a crosslinked structure to a part of EVOH by a post-modification method. For example, EVOH is treated with a boron compound (Japanese Patent Publication No. 49-20615), an organosilicon compound such as an organosilane compound or an organosiloxane compound is reacted in the presence or absence of a peroxide, Such as those in which a crosslinked structure is imparted to a part of EVOH in the presence of water or a silanol condensation catalyst (JP-A-51
-20946 publication, Japanese Patent Application Laid-open No. 51-53541,
JP-A No. 54-20058, etc.). All of these conventional techniques have a drawback due to the fact that boron compounds, organosilicon compounds, etc. are added to EVOH to impart a crosslinked structure to a part of the resin, that is, the amount of the crosslinking agent added is small. This seems to be due to the fact that the addition, mixing, and reaction are performed by a post-modification method that is carried out in the usual manner using various mixers, rolls, extruders, etc., but from the viewpoint of uniformity of the degree of modification of EVOH. It is inevitable that the result will be even more unsatisfactory. As a result, there are variations between products in properties such as gas permeability and its humidity dependence in films produced by casting, melt coatings, and coating layers obtained by powder coating. Although it has disadvantages such as the appearance of spots and the degree of improvement in physical properties that is considered to be caused by the spots is not as expected, the EVOH resin contains parts with poor solubility in the resin agent, and the EVOH resin has a uniform solubility. In some cases, it has been difficult to obtain a resin with a 100% polyvinyl alcohol, so further modification of EVOH has been strongly desired.

C8 Objectives, structure, and effects of the present invention The inventors:
As a result of intensive research on silicon-containing EVO) obtained by saponifying a copolymer of vinyl acetate, ethylene, and a specific silicon-containing olefinically unsaturated monomer, it was surprisingly found that there were products that did not have the above-mentioned drawbacks. In addition, even within the molded product, the degree of modification is uniform, so there is no variation in the properties, and the solubility in the solvent is uniform. We have found a coating material made of silicon-containing EVOH that also has stretch formability.

The coating material made of modified EVOH according to the present invention maintains its excellent gas permeability, oil resistance, fragrance retention, and transparency, while maintaining its disadvantages of water resistance, crack resistance against agricultural chemicals, etc. The coating material has improved humidity dependence of gas barrier properties, and also has good stretch formability.
The modified EVOH retains good solvent solubility, has good solution stability, is resistant to drying after coating, and is made of a coating material that significantly improves the properties mentioned above.

D0 More detailed description of the present invention The coating material of the present invention is preferably used by coating molded products such as films, sheets, containers, etc. made of various thermoplastic resins in the form of a solution. The molded product having the coating layer has high uniformity in properties with no variation observed between products or within the molded product.

The coating materials of the present invention also include films, sheets, etc., obtained by casting methods as a special case of coating operations, for lamination or lamination; Since the sheet has excellent stretch formability and deep drawability, it is suitable for lamination or lamination.

The present invention provides a modified coating material consisting of a modified EVOH obtained by saponifying a copolymer of vinyl acetate, ethylene, and a specific olefinically unsaturated monomer containing silicon in the molecule. .

That is, the present invention relates to vinyl acetate, ethylene, and one or more silicon-containing olefinic unsaturated monomers represented by the following general formulas CI), (I[), and (I[). Saponification degree of vinyl acetate component obtained by saponifying a copolymer of 95% or more, ethylene content 20-6
0-f, /l/%, silicon content o, ooos~0.5
The coating material is made of silicon-containing EVOH having a ratio of 100% to 100%.

The coating material made of EVOH in the present invention preferably has an ethylene content of 20 to 60 mol% and a saponification degree of the vinyl acetate component of the copolymer of 95% or more. When the ethylene content is as low as 20 mol%, water resistance,
The effect of improving hot water resistance and the like is diminished, and if it exceeds 60 mol%, the gas permeation resistance and fragrance retention properties, which are the characteristics of EVOH, are reduced. If the degree of saponification is less than 95%, the barrier properties and oil resistance will decrease, and EVOH will not be able to retain its original properties, making it difficult to enjoy the effects of the present invention.

The silicon-containing olefinically unsaturated monomer used in the present invention is, for example, one or more compounds selected from the compounds represented by the following general formulas (I), (II), and (III). can be suitably used.

However, here, n is O~1, m is 0~2, R' is a lower alkyl group, an allyl group, or a lower alkyl group having an allyl group, and R2 is a saturated branched or unbranched prime number of 1 to 40. It is an alkoxyl group, and the alkoxyl group may have an oxygen-containing substituent. R3 is hydrogen or a methyl group, R4 is hydrogen or a lower alkyl group, R5 is an alkylene group, or a divalent organic residue in which chain atoms are interconnected by oxygen or nitrogen, R' is hydrogen, A halogen atom, a lower alkyl group, an allyl group, or a lower alkyl group having an allyl group; ), R8 is hydrogen, a halogen atom, a lower alkyl group, an allyl group, or a lower alkyl group having an allyl group, and lσ is a lower alkyl group.

Examples of the silicon-containing olefinically unsaturated monoparticle represented by the general formula (I) include vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinyltriethoxysilane, vinylmethyljethoxysilane, and vinyldimethylethoxysilane. Silane, allyltrimethoxysilane, allylmethyldimethoxysilane, allyldimethylmethoxysilane, allyltrimethoxysilane, allyldimethylethoxysilane, vinylfretris (β
-methoxyethoxysilane, vinylisobutyldimethoxysilane, vinylethyldimethoxysilane, vinylmethoxydigtoxysilane, vinylcymethoxygtoxine, vinyltriethoxysilane, vinylditoxydihexyloxysilane, vinyldimethoxyhexyloxysilane, vinyltrihexylsilane Siloxysilane, vinyldithoxyoctyloxysilane, vinyldimethoxyoctyloxysilane, vinyltrioctyloxysilane, vinylmethoxydioleyloxysilane, vinyldimethoxyoctyloxysilane, vinylmethoxydioleyloxysilane, vinyldimethoxyoctyloxysilane, general formula Examples include polyethylene glycol derivatives of vinylmethoxysilane represented by (where m is the same as above and X represents 1 to 20), but vinyltrimethoxysilane is preferred from an economic standpoint.

As the silicon-containing olefinic unsaturated monomer represented by the general formula (II), 3-(meth)acrylamide propyz+ztrimethoxybenCH2=CRCNH(CHz)a 5KOCH3)s(
1 3-(meth)-acrylamidoglopyltriethoxysilane CHz=CR-C-NH-(CH2)3-8i (OC
H2CHs)31 3-(meth)-acrylamido-propyltri(β-methoxyethoxy)silane CHz=CRCNH(CH2)3-8i (OCH2C
H20CH3)31 3-(meth)-acrylamido-propyltri(N-methylaminoethoxy)silane C11x=CR-C-NH(C)R2)a-8i (O
C&CHzNHCH3)a1 2-(meth)-acrylamide-ethyltrimethoxysilane CH2=CR-C-NH(CH2)2-8i COCH
3-3(1 1-(meth)acrylamide-methyltrimethoxysilane CHx=CR-C-NH-CH2-3i-(QC)R3
)a1 2-(meth)acrylamide-2-methylglopyltrimethoxysilane 2-(meth)acrylamide-isopropyltrimethoxysilane (R represents hydrogen or methyl/l/group) Chain or branched alkyltrialkoxysilane, N-(2-(meth)acrylamido-ethyl)-aminopropyltrimethoxysilane CHz=CRCNH-CH2CH2NH(CH2)! 1
-8i-(OCHs)a1 (3-(meth)acrylamide prohyde/L/)--oxyprobyltrimethoxysiphon CHz=CR-C-NH-(CH2)3-0-(CHz
)a-8i-(OCHa)a1 (R represents hydrogen or methyl group) (meth)acrylamide-nitrogen-containing or oxygen-containing alkyltrialkoxysilane, 3-(meth)acrylamide-propyltriacetoxysilane CH2=CRC -NH-(CH2)3Si(OCO
CHs)s1 2-(meth)acrylamide-ethyltriacetoxysilane CH2=CR-C-NH-(CH2)2-8i (OC
OCHi)s1 4-(meth)acrylamido-butyltriacetoxysilane CHx =CR-C-NH-(CH2)4-3i-(O
COCH3)31 3-(meth)acrylamido-propyltripropionyloxysilane CH2=CR-CNH(CI(2)a-8i (OCO
CHzCH3)a1 2-(meth)acrylamido-2-methylprohyltriacetoxysilane Ha N-(2-(meth)acrylamidoethyl/L/)aminopropyltriacetoxysilane CH2=CRCONH-CH2C(C) Box 5-8
(meth)acrylamido-alkyltriacyloxysilane such as i (OCOCHs)s (R represents hydrogen or methyl group), 3-(meth)acrylamidopropyl isobutyp dimethoxysilane CHz=CR-CONH(CH2) l-8i (OCH
sru CHa-CH-CkbCHs 2-(meth)acrylamide-ethyldimethylmethoxysilane CHa CH2=CRCONH-(CH2)z-8i-OCII
g-random3-(meth)acrylamide-propyloctyldiacetoxysilane CH2=CR-CONH(CH2)3-8i (OCO
CH3)2(CH2)7CH11 1-(meth)acrylamide-methylphenyldiacetoxysilane CH2=CRCO-NHCH2Si (OCOCH3)
2am 3-(meth)acrylamido-propylbenzyljethoxysilane 2-(meth)acrylamido-2-methylpropylmonochlorodimethoxysilane CH2=CRC0NH-C(CH3)2-CH2-8i
-(OCHs)21 2-(meth)acrylamido-2-methylpropylhydrodienemethoxysilane (, "(meth)acrylamidoalkyl di- or monoalkoxy or di- or mono- Acyloxysilane, 3-(N-methyl-(meta))
(N-alkyl-(meth)acrylamide)-alkyltrimethoxysilane such as 2-(N-ethyl-(meth)acrylamide)-ethyltriacetoxysilane (R is hydrogen or meth) V group) Alkoxy or triacetoxysilane etc. are used.

Among these, 3-(meth)acrylamidoprobyltrimethoxysilone and 3-(meth)acrylamide-
Propyltriacetoxysilane, 2-(meth)acrylamido-2-methyl-lepropyltrimethoxysilane and 2-(meth)acrylamido-2-methylpropyltriacetoxysilane have an amide bond that is extremely stable against acids or alkalis. It is preferably used in certain respects. Here, the modified silicon-containing EVOH obtained by copolymerizing the silicon-containing olefinically unsaturated monomer represented by the general formula (n) with vinyl acetate and ethylene and saponifying the resulting copolymer is , contains a copolymer unit represented by the following general formula (IV).

(　C　R2　-　CR3)-　R’　m1 CON-h’ Si-R10+a-ml (IV)4 (Here, R3, R4, R5, R6, and m are the same as above.

represents a hydroxyl group, a salt of a hydroxyl group represented by the general formula OM (M represents an alkali metal or NH4)) The silicon-containing olefinically unsaturated monom group represented by the general formula (I) is vinyltriacetoquinsilane CH2 =CH-Si (
OCOCH3)a Vinyltrizolopionyloxysilane
CH2=CH-Si (OCOCHs)a(?H3 Isof °C Hihiltriacetoxysilane CH2=C-Si
-(OCOCHs)svinylisobutyldiacetoxysilaneCHz=CH-Si (OCOCH3)2CHs
CH-CHa Vinyl methyl diacetoxin group CH2=CH Si
-(OCOCHa)2vinylphenyldiacetoxysilane CH2=CH S
i (OCOCHs)2sH5 Vinylmonochlorosifu'setoxysilaneq Seven-tone heart H-S
i-(OCOCH3)2 Vinyl compound dolodiene diacetoxysilane CH2=CH Si-(OCOCH3)2
etc., but vinyltriacetoxysilane is preferred from an economic standpoint.

The copolymerization of the above-mentioned silicon steel-containing olefinically unsaturated monomer with vinyl acetate and ethylene is preferably carried out by bath liquid polymerization in the presence of alcohol. As the alcohol, lower alcohols such as methanol, ethanol to t-getanol are usually preferred industrially. Copolymerization can be carried out either batchwise or continuously. The ethylene content of EVOH is determined mainly by the vinyl acetate present in the copolymerization system and the ethylene content dissolved in the copolymerization system, and the latter mainly depends on the ethylene pressure and temperature of the polymerization tank. In the same case, the silicon content of the modified EVOH is primarily governed by the quantitative relationship between vinyl acetate and silicon-containing olefinically unsaturated monomers present in the core system.

In the case of a batch method, it is well known that the copolymer composition changes with the polymerization rate according to the copolymerization reactivity ratio, but one or both monomers are added to keep the monomer composition constant. Therefore, in order to obtain a copolymer having a uniform copolymerization composition, it is more desirable to adopt a so-called semi-batch method. An example of a method for calculating the amount added in this case is R. J Hanna InduaLreal
andEngineering Chemistry
vol. 4 9, & 2 208-209 (
An example of this is the formula submitted in 1957). In the case of continuous method, complete mixing type 1 with stirring mixing tank and copolymerization reaction tank
A staged flow system reaction system is most suitable, and in the case of a multistage drift ice reaction system of two or more stages, the monomer composition in the copolymerization tank of each stage is constant for the same reason as above. Therefore, it is more desirable to carry out the process while adding a monomer to the nuclide in the second and subsequent stages. As a polymerization initiator, 2,2-azobis-(4methoxy-2,4-dimethylpareronitrile), 2,4.4
-) Nitriles such as limethylvaleronitrile and 2.2-azobisisobutyronitrile, di-n-probilveroxycarbonate, bis-4-t-butylcyclohexylperoxydicarbonate, bis-2- Carbonates such as ethylhexyl peroxydicarbonate, acetylcyclohexane phosphonyl peroxide,
Known radical initiators such as peroxides such as benzoyl peroxide and lauroyl peroxide can be used. In particular, a polymerization initiator with a short half-life can almost completely or largely suppress the formation of a gel-like substance that is insoluble in the polymerization system, which is observed over time during copolymerization, and is therefore useful during long-term continuous polymerization operations. Suitably used.

The modified coating material made of silicon-containing EVOH according to the present invention has new properties in addition to the original properties of EVOH resin.
In other words, it is extremely satisfactory from the viewpoint of imparting high uniformity, and the content of the silicon-containing monomer in the copolymer is varied in accordance with the improvement of the properties suitable for the purpose. A coating material suitable for this can be obtained.

For example, in order to improve water resistance, improve the humidity dependence of oxygen permeability coefficient, etc., it is better to increase the content of the silicon-containing monomer as the ethylene content decreases, in order to maintain the same water resistance, etc. desirable. If the content of the silicon-containing monomer is too low, the modification effect will not be exhibited, and if it is too high, for example, uniform solubility may be lost or the coating obtained with solution coach ink may dry out. During the process, it became difficult to form a uniform and dense coating layer, but EVO still
This is undesirable because the oxygen barrier properties, which are the original properties of the H resin, deteriorate. The content is selected depending on the purpose, but from o,ooos to 0.5 mol%, especially 0.001
A range of 0.0135 mol % is preferred.

The copolymer obtained by polymerization is then subjected to a saponification reaction. The saponification reaction is carried out using a known method using an alkaline catalyst.
That is, it is usually advantageous to carry out the reaction by alcoholysis, using the copolymer as an alcoholic solution. Among them, Japanese Patent No. 575,889 and Japanese Patent No. 611,5
The method disclosed in No. 57 using a basic reactor and removing methyl acetate, which is produced as a by-product during the saponification reaction, from the top of the column by blowing alcohol vapor into the bottom of the column can be most preferably used. As the alkaline catalyst used in the saponification reaction, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alcoholades such as sodium methylate and potassium methylate, and the like are used. Among these, sodium hydroxide is industrially and economically advantageous. The saponification temperature is suitably selected from the range of 60 to 175°C. In particular, when using the base type reactor, the reaction time can be shortened, the silicon-containing EVOH
The temperature is preferably 100° C. or higher from the viewpoint of solubility in alcohols.

In the saponification reaction, the vinyl alkoxy-77 units are also partially or highly saponified and converted into vinylsilano-p units, their alkali salts, or their otome tautomers. However, the copolymer containing the monomer represented by the above general formula (II) is stable without decomposition of the amide bond of the silicon-containing polymerizable monomer unit in the saponification reaction with an alkaline catalyst. is maintained. However, during the saponification reaction, alkoxyl groups, carboxyl groups, hydrogen, and halogens bonded to silicon in the silicon-containing monomer unit represented by general formula (n) are also partially or highly saponified, resulting in hydroxyl groups or alkali salts of hydroxyl groups. will be converted to

After the saponification reaction, in isolating the modified EVO),
Known methods can be applied, among others, Japanese Patent No. 725.
The method disclosed in No. 5209, in which the polymer is separated by precipitation in the form of strands, is preferably used. The precipitated and isolated modified EVOH is washed with water using a known method, then subjected to known heat stabilization treatment such as acid treatment if necessary, dried, and then dissolved in a solvent to be used as a coating material solution. It will be done. In addition, in the case of a water-alcoholic solvent, it is preferable from an economical point of view to dissolve it in the solvent in an undried state after removing the liquid and use it as a coating material solution. When the acid treatment is carried out, the portions where silicon-bonded alkoxyl groups, carboxyl groups, hydrogen, and halogens are converted into alkali salts of hydroxyl groups during the saponification reaction become hydroxyl groups.

Solvents for the solution of the modified coating material of the present invention include aliphatic alcohols having a prime number of 4 or less, such as dimethyl sulfoxide, dimethyl filmamide, methanol, ethanol, propyl alcohols, and butyl alcohols; Although a solvent or the like may be used, the alcohol-aqueous solvent is preferred from the viewpoints of solubility, dissolution temperature, volatility (drying rate), economical efficiency, and the like. In particular, an alcohol-aqueous solvent in which the alcohol is one or a mixture of two or more selected from n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, 860-butyl alcohol, and t-butyl alcohol. is preferably used. The optimum composition of the alcohol-aqueous solvent is determined based on solubility, stability of the solution on storage, etc., but in most cases, it is determined based on the alcohol/L/concentration range, the type of alcohol, the ethylene content, etc. YO#) Laws will be enforced as appropriate. For example, in the modified EVOH with an ethylene content of 43 mol%, 14% of n-propyl alcohol, alcohol/L'e
The concentration range is suitable for &65-75mff1%, and at an ethylene content of 33 mol%, the alcohol)V concentration is 50%.
A suitable range exists between 65% and 65% by weight. Regarding the solubility of the modified EVOH of the present invention, the silicon-containing monomer content required to obtain the effects of the present invention is in a small range, so the modified EVOH is Regarding the solubility in the solvent, a suitable solvent and further a solvent composition can be determined with reference to the solubility of known EVOH resins (for example, Japanese Patent Publication No. 47-48489, etc.). In this respect, the coating material of the present invention is modified E V O
Although it is composed of H, it has good solvent solubility. The resin concentration of the solution is 10 to 30% by weight.
is preferable, and 15 to 25% by weight is particularly preferably used. If the concentration is lower than that in this area, it is economically disadvantageous because it is necessary to repeat the coating operation to obtain a coating of a suitable thickness, and if the concentration is higher than that in this area, the viscosity will increase. This results in disadvantages such as the inability to move around on a suitable coating surface. The coating can be formed by coating by discharging from a canuting head, roll coating, doctor roll coating, etc. The coating may be carried out by any method such as coating, doctor knife coating, curtain flow coating, spraying, dipping, or brush coating. The coating formed by the coating operation is dried,
In addition, heat treatment is performed as necessary, but during the process, the expression of the crosslinked structure is completed, and the objective of the present invention, which is the improvement in the properties of the EVOH resin, is obtained. be able to.

As mentioned above, the silicon content in the paternal EVOH of the present invention is (1.0005 to (), 5 monomers, preferably,
0,001 to 0.3 mol%, but in a region where the silicon content is relatively small, for example, about 0.05 mol% or less, it shows good solubility in the solvent; When it reaches about 0.5 mol%, it becomes insoluble in, for example, a water-alcohol mixed solvent, 15% water-containing phenol, which is a good solvent for unmodified EVOH. Further, better solvent solubility and solution stability are more preferably obtained when the silicon content is 1.35 mol % or less.

The coating material made of modified EVOH of the present invention can be used not only as a coating material for solution coating on films, sheets, containers, etc. By solution coating, drying and peeling, a cast film with improved properties can be obtained. Furthermore, the coating material of the present invention can be used as a powder coating to coat fragile objects made of metals, ceramic materials, glass, etc., and to provide +)t+I rupture properties. Since it has improved affinity, it can be suitably used. In this case, since the material is used alone rather than as a solution, it is necessary to remove the silicon content in a region where the material retains its heat-melting properties. The silicon content of the coating material of the present invention for the target container is 0.0 0
0 5 to 0.2 mol%, especially 0.0 0 1 to 0,1
Mol% is preferred.

Films, except when obtaining films by casting methods;
The curve of the substrate to be coated, such as sheets, containers, etc., is determined by physical treatment such as corona treatment (if the substrate is polyolefin such as polyethylene, the surface tension of the film, etc. is 37 to 45 dyne 7 cm). ), it is preferable to apply an anchor coating agent such as polyether or polyurethane thread in order to ensure the contact between the base material surface and the coating layer. Another preferred example is a case where the film, sheet, container, etc. has a laminated structure, and the layer to be coated is a laminated adhesive resin layer. At this time, there is no need for corona treatment or the use of an anchor coating agent, even to the extent of vibration. Examples of such adhesive resins include maleic anhydride graft-modified polyethylene, maleic anhydride graft-modified polypropylene, and maleic anhydride graft-modified ethylene-ethyl acrylate, although they vary depending on the type of other thermoplastic resins adjacent to the adhesive resin layer. ,・A mixture of one or more of ethylene-vinyl acetate copolymer, maleic anhydride graft-modified ethylene-vinyl acetate copolymer, etc., or a blend of these and the modified GVOU, etc. , it can be used by escaping from among them.

The water resistance of the coating material of the present invention and the effect of improving oxygen barrier properties due to moisture absorption can be clearly seen by measuring the oxygen permeability coefficient of the film obtained by the above-mentioned casting method. Although the permeability coefficient is similar to that of EVOH, it is clear that the permeability coefficient decreases under humidity.

Next, the present invention will be explained in more detail with reference to Examples.
These examples do not limit the invention in any way.

In addition, the middle part of the example or % is the sleep weight S without any reservation.
Or ■ Indicate amount%.

Example I Continuous polymerization was carried out under the following conditions in order to obtain a silicon-containing ethylene-vinyl acetate copolymer in a polymerization tank with a capacity of 1 o (3 liters) and equipped with a stirrer and an internal cooling coil.

Vinyl acetate supply amount 4' O! / hr methanol)
L/130 f/hr r 2.2'-azobis=(2,4-dimethylvale, l'nitrile) 140 my/hr r3-acrylamide-propyltrimethoxysilane 210yg/hr Polymerization temperature 60°C Average residence time 7 hrs Polymerization Tank ethylene pressure: 39 kg/cm 2 G vinyl acetate polymerization rate was about 49%. The copolymer was confirmed by nuclear magnetic resonance analysis to contain 0.022 mol% of 3-acrylamide-propyltrimethoxysilane, 67 mol% of vinyl acetate units, and approximately 33 mol% of ethylene units. . A methanol solution of the copolymer was introduced into a formal saponification reactor, and sodium hydroxide was added at a molar ratio of 0.05 to vinyl acetate contained in the copolymer.
The reactor is supplied with dimethanol/I/steam, which is blown into the lower part of the column, methyl acetate produced as a by-product is removed from the top of the column, a saponification reaction is carried out from the gas, and methanol of the reformed EVOH is removed from the bottom of the column. A solution was obtained. After blowing steam into the methanol solution to change the solvent composition in the solution to a mixed water/methanol system, the temperature was increased to 5°C.
The EVOH was discharged in the form of a nutland into a 0% methanol-μm aqueous solution, solidified and precipitated, and cut to isolate the EVOH as a pellet. After washing thoroughly with water, it was stored in a hydrated state. The degree of saponification of the EVOH was 99.4%. After dehydration and drying, the viscosity at 30°C was measured in a new DMSO solution.
Met.

Next, extrusion blow molded polypropylene has a thickness of 0.95
Apply urethane adhesive (“AD-aooJ” manufactured by Toyo Morton) to the inner layer of a 1ftIn 500m1 container, and
After forming a film, the above EVOH was dissolved in a mixed solvent of n-propano-)v/water (55/145) at 60°C, and 15%
A solution was obtained, coated at a temperature of 40°C, and dried at 100°C for 2 minutes to obtain a 12μ EVOH membrane layer.

A crack resistance test was conducted on the obtained container as follows. DD'VP emulsion (agrochemical liquid) using xylene as a solvent 450ml! After heating the container filled with the same at 40°C for 30 days, the container was left at room temperature for 1 day and then left at -20°C for 3 days for 3 cycles, and the presence or absence of cracks that occurred was examined. Crack resistance is indicated by the number of 20 samples in which no cracking was observed when 20 samples were exposed.
This container was 19.

Comparative Example I In Example 1, conventional EVOH (ethylene content 33 mo/L/%, [η) DMSO 0.94 dt/y at 30°C] was used as υ in place of silane-modified EVOI, and the following was the same as Example 1. A container with a gvon membrane layer was obtained under these conditions. The crack resistance of the resulting container was 6.

Examples 2 to 4 and Comparative Examples 2 to 4 Various silane-modified EVO)i as shown in Table 1 were produced.
Dissolve in a suitable alcohol-water mixed solvent and add 500 ml of polypropylene with a thickness of 0.95 g in the same manner as in Example 1.
When it was applied to the inner layer of EVOI (Bo)/Shin and examined for crack resistance against organic solvents, it was found that it was improved compared to a corresponding unmodified EVOI (coating container).

Table 1 Example 5 Using the same polymerization tank as in Example 1, continuous polymerization was carried out under the conditions shown below.

Vinyl acetate supply amount 480y/hr Methanol 〃409/hr Vinylcitrimethoxysilane supply if 355mg/
h r2.2'-Azobisisobutyronitrile 33
rBg/hr Polymerization temperature 77°C Polymerization ethylene pressure 60 to 9/. m2·ra average residence time 6 hrs The polymerization rate of vinyl acetate was about 55%. According to nuclear magnetic resonance analysis, the copolymer contained 0.027 mol% of vinyltrimethoxysilane units, 59.5 mol% of vinyl acetate units,
It was confirmed that it contained about 40.5 mol% of ethylene units. After saponification, isolation, and post-treatment in the same manner as in Example 1, the modified EV OII was dried. The degree of saponification of this EVOH is 99.3% at 30°C [
ηIDMSO was 0.86 dt/9.

When the EVOI (resin was dissolved in n-propanol/water (6/4) and made into a 15% solution, the viscosity at 50°C was 3.
It was 40 cp. A urethane adhesive (
After applying 10μ of AD-335A (manufactured by Toyo Morton), it was immersed in the above EVOH solution and dried at 60°C to a thickness of 1.
A container with a 5μ layer of coach ink was obtained. The oxygen barrier property of this container at 80% RII is 0.8 cc7B2.
The carbonic acid strength was 22 cc/m2day atm.

Comparative Example 5 In the same manner as in Example 1, 11 containers were made, and this container was prepared with an ethylene content of about 40 moles, a saponification degree of 99.4%, and a 30
[η) DMSO (+, 84 at/q at °C) was immersed in a solution of n-propertool/water (6:4) to prepare a container with a coating layer of 15 μm thickness. Oxygen tank at 80% RH 1)'1.
is 1.5 cc/m2day-atm, and the carbonic acid power is 62 C (: / 777, "-d,
It was ny-atm.

Example 6 The melt intex at 2'50°C was 2.6, and 3 moles of 100 moles of ethylene glycol were replaced with cyclohexanedimethanol.The material was 4F, polymerized polyethylene terephthalate, length 160 mm, outer diameter. A preform with a diameter of 24mm and a wall thickness of 3.0mm was injection molded. This outer surface was coated with 30μ of urethane adhesive y1 1 (AD-535A, manufactured by Toyo Morton), immersed in the modified EVOHf n-propertool/water (6/4) solution prototyped in Example 5, and dried. Repeatedly, a 60μ thick EVOH layer was formed. When this preform was blown at 115°C, it was uniformly blown and had a thickness of 310μ. O
1 container was made.

In addition, the biaxial stretch blow moldability was extremely good. When the carbon dioxide gas barrier properties of this ritual vessel at 80% RH were investigated, it was found to be 4% at 9 cc/m"day-atm, and +11% by the same method. When unmodified EVOH (40 mol% ethylene-filled) was coated and similarly blown at 115°C, a container with a non-uniform EVOH coating layer was obtained, and the carbon dioxide gas barrier property was 30 CC/rn2day-atm or more. became.

Examples 7 to 12 and Comparative Examples 6 to 7 After corona treatment of a 20μ thick OPP film,
Approximately 2g/77L2 polyurethane thread adhesive for dry lamination
After coating and drying at 120°C for 20 seconds, apply silane gvou (saponification degree 99.3 to 99.5%) of each vertebra shown in Table 2.
), apply it with a coater, and apply it to 110-1
After 2 minutes at 20°C and 1 day at room temperature, 5μ of EVO
) (a layer was formed.Zo of this multilayer film.

When the oxygen gas barrier properties at %RH were evaluated, the values shown in Table 2 were obtained, which were superior to the values of the corresponding unmodified Fl:VOH.

Table 2

Claims (5)

[Claims] (1) Vinyl acetate, ethylene and the following general formula (I), (
One or two selected from the silicon-containing olefinically unsaturated monomers represented by II) and (III)
Saponification degree of vinyl acetate component obtained by saponifying more than one species of copolymer, 95% or more, ethylene content 20 to 60 mol%
, a coating material comprising a saponified silicon-containing ethylene-vinyl acetate copolymer having a silicon content of 0.0005 to 0.5 mol%. 1m cm=c■(am)n-st-a"<s-+a (I
)Cfb=C-CN-R'-8i R'(a-m)
(II) 1 R3g% 1 [where U is θ~1, m is θ~2, R1 is a lower alkyl group, an allyl group, or a lower alkyl group having an ali group, and t is a lower alkyl group having a carbon number of 1 to 40 It is a saturated branched or unbranched alkoxyl group, and the alkoxyl group may have an oxygen-containing substituent. R3 is hydrogen or a methyl group, R' is hydrogen or a lower alkyl group, R5 is an alkylene group or a divalent organic residue in which chain atoms are bonded to each other by oxygen or nitrogen, R6 is hydrogen halogen, lower An alkyl group, an allyl group, or a lower alkyl group having an allyl group, Pi is an alkoxyl group or an acyloxyl group (here, the alkoxyl group or acyloxyl group may have a substituent having oxygen or nitrogen),
R8 is hydrogen, a halogen atom, a lower alkyl group, an allyl group, or a lower alkyl group having an allyl group, and R9 is a lower alkyl group. ] (2) The coating material according to claim 1, wherein the coating material is a solution of a saponified silicon-containing ethylene-vinyl acetate copolymer. (3) The coating material according to claim 2, wherein the solvent of the solution is a water-alcohol mixed solvent. (4) The alcohol is n-propyl alcohol, is. -propyl alcohol, n-butyl alcohol, a6o
The coating material according to claim 3, which is one or more selected from -butyl alcohol and butyl alcohol. (5) Silicon content is 0.001 to 0.35 mo/l/%
A coating material according to any one of claims 1 to 4.