JPS638448A - Resin composition - Google Patents

Abstract

PURPOSE:A resin composition suitable as molded articles, films, sheets and further coating agents, having improved water resistance, gas barrier properties and dimensional stability, obtained by blending a vinyl alcohol resin with a compound containing a specific functional group and an allyl group. CONSTITUTION:A vinyl alcohol resin which contains >=20mol vinyl acetate in the resin and has >=80mol% saponification degree is blended with 0.1-20wt%, preferably 0.5-15wt% compound (e.g. glycidyl allyl ether, etc.) which contains a functional group (glycidyl group or isocyanate group) capable of being added to the hydroxyl group in the vinyl alcohol resin and an allyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field 1] The present invention is particularly applicable to vinyl alcohol-based products that can be used to obtain molded products, films, sheets, and coatings with improved water resistance, gas barrier properties, and dimensional stability. The present invention relates to a resin composition.

[Conventional technology 1 Vinyl alcohol-based resins, such as saponified ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVO) I] and polyvinyl alcohol-based resins (hereinafter PVA-based ↑3 (abbreviated as fat)) have gas barrier properties. In particular, EVO is used for various molding applications as it has excellent barrier properties against oxygen.
In addition to these properties, H has excellent mechanical properties such as impact strength and tensile strength, solvent resistance, chemical resistance, fragrance retention, oil resistance, and even non-static properties, so it is recommended for food use. various packaging materials, multilayer laminated films, containers, bottle ponds, etc.
It is widely used in Isogo Kai parts and engineering plastics for electrical appliances.

However, these vinyl alcohol resins are generally inferior in water resistance, and have the disadvantages peculiar to these resins that their oxygen barrier properties rapidly decrease in a high humidity atmosphere.

For this reason, conventionally, resins with excellent water resistance, such as polyolefin resins, have been laminated to compensate for the disadvantages with the advantages of the resin. Of course, in such a method, both resins have extremely poor adhesive properties, so the adhesive properties can be improved by using an adhesive such as (anhydrous) carboxylic acid-modified polyolefin resin, or by bringing the polarities of the resins themselves closer to each other. Although this poses another technical problem of trying to improve the water resistance of vinyl alcohol resins, the current situation is that in most practical applications this method is used to solve the problem of water resistance of vinyl alcohol resins. (For example, JP-A-60-24945, JP-A-60-25748, etc.).

[Problems to be Solved by the Invention] However, in practice, there are many cases in which the above method cannot be adopted. Since it comes into direct contact with the outside air, the resin itself is required to be water resistant.

[Means for Solving the Problems 1] However, in view of this situation, the present inventors conducted various studies based on imparting water resistance to the vinyl alcohol resin itself, and as a result arrived at the present application. The gist of this is that the at
A resin composition containing a compound having an allyl group and a functional group that can be added to a hydroxyl group in fat is used.

Hereinafter, the resin composition of the present invention will be explained in more detail.

First, the vinyl alcohol resin used in the present invention refers to a resin that contains at least a portion of vinyl alcohol monomers, that is, saponified vinyl acetate units. By adding vinyl acetate into the resin, it can be expected to improve water resistance, but in practice it is required to have the various performances mentioned above, such as gas barrier properties. A material containing mol % of 80 mol % or more of which is saponified is used. Among these, the above-mentioned EV
OH or PVA-based resins are practical, and EVOH in particular is the most preferred target resin, as it has been observed that not only water resistance is improved, but also various properties of the pond are further improved.

EVOH has an ethylene content of 20 to 80 mol%, preferably 25 to 70 mol%, and a degree of saponification of the vinyl acetate portion of 9.
Examples include those having a composition of 0 mol% or more, preferably 97 mol% or more. When the ethylene content is less than 20 mol%, thermal stability is poor and melt moldability is reduced, and when the ethylene content exceeds 80 mol%, oxygen barrier properties are reduced.

If the degree of saponification of the vinyl acetate moiety is less than 90 mol%, thermal stability is poor and physical properties such as oxygen barrier properties, oil resistance, and water resistance are reduced, resulting in poor practicality. In addition, E in the present invention
In addition to ethylene and vinyl acetate (or saponified vinyl alcohol), VOH includes unsaturated carboxylic acids or their esters or salts, unsaturated sulfonic acids or their salts,
(meth)acrylamide, (meth)acrylonitrile,
It may contain a small amount of about 10 mol % or less of a third component such as α-decayed fins such as propylene, butene, α-octene, and α-octadecene, and vinyl esters other than vinyl acetate.

As PVA-based resin, polyvinyl ester partial resin (
1 or completely saponified products (i.e., polyvinyl alcohol), but are not limited to these, but also partially or fully saponified copolymers of vinyl acetate and other monomers other than ethylene, and also post-modified products of vinyl acetate and other monomers other than ethylene. It can be used depending on the purpose. Other monomers include α- with a carbon number of about 30 or less.
Olefin, unsaturated carboxylic acid or its ester/salt,
Examples include unsaturated sulfonic acids or salts thereof, (meth)acrylamide, (meth)acrylonitrile, and post-modified products include acetalized products, urethanized products, etherified products, esterified products, and grafted products.

The compound having a functional group and an allyl group that can be added to the hydroxyl group in the vinyl alcohol resin (hereinafter simply referred to as a functional group-containing allyl compound) most typically has a glycidyl group and/or an isocyanate group as a functional group. It is a compound that has an allyl group. Such compounds include, for example, epoxy compounds having groups that can react with hydroxyl groups and/or
Alternatively, it can be obtained by reacting an isocyanate compound with an allyl ether of a polyhydric alcohol in the presence of a catalyst if necessary.

Typical examples of such compounds include glycidyl allyl ether, allyl ether of ethylene glycol diglycidyl ether, allyl ether of diethylene glycol diglycidyl ether, allyl ether of triethylene glycol diglycidyl ether, and allyl ether of polyethylene glycol diglycidyl ether. Allyl etherified product, Allyl etherified product of propylene glycol diglycinole ether, Allyl etherified product of polypropylene glycol diglycidyl ether, Allyl etherified product of butylene glycol diglycidyl ether, Allyl etherified product of polybutylene glycol diglycidyl ether, Neobentyl At least one epoxy group of a polyhydric alcohol type polyglycidyl ether such as an allyl ether of glycol diglycidyl ether, an allyl ether of 1,6-hexanesiol diglycinole ether, an allyl ether of bisphenol A type diglycidyl ether, etc. or allyl ether of oxalic acid diglycidyl ester 1
, allyl ether of malonic acid diglycidyl ester, allyl ether of succinic acid diglycidyl ester, allyl ether of 7-dipic acid diglycidyl ester, allyl ether of sebacate diglycidyl ester, allyl ether of 7-talic acid diglycidyl ester, At least one epoxy group of polycarboxylic acid type polyglycidyl esters, such as allyl etherified products, allyl etherified products of isophthalic acid diglycidyl ester, allyl etherified products of terephthalic acid diglycidyl ester, allyl etherified products of cyclohexanedicarboxylic acid diglycidyl ester, etc. Examples include allyl etherification with the group remaining.

Further, as allyl etherified isocyanate compounds, monoallyl etherified tolylene diisocyanate, monoallyl etherified diphenylmethane-4,4-diisocyanate, allyl etherified 1,5-naphthylene diisocyanate, A monoallyl etherified product of hexamethylene diisocyanate, a monoallyl etherified product of isophorone diisocyanate, a more allyl etherified product of 2,2,4-trimethylhexamethylene diisocyanate, a monoallyl etherified product of lysine diisocyanate, Monoallyl etherified product of xylylene diisocyanate, ToIJ phenylmethane-4,4,4゛-
Mono(or di)allyl ether of triisocyanate, monoallyl ether of 3,3'-vitrylene-4,4'-diisocyanate, 3,3'-trimethylphenylmethane-4,4'-di Examples thereof include a monoallyl ether of isocyanate, a monoallyl ether of sul-7-onyl diisocyanate, and the like.

The allyl compounds used for the above allylation include:
Generally, allyl etherified polyhydric alcohols having at least one hydroxyl group are used. Specifically, glycerin monoallyl ether, trimethylolpropane diallyl ether, trimethylolethane monoallyl ether, trimethylolethane diallyl ether, pentaerythritol diallyl ether, pentaerythritol triaryl ether, 1Φ2,6-hexandriol monoallyl ether , 1,2,6-hexanetriol sialyl ether, sorbitan monoallyl ether, sorbitan diallyl ether, etc., but the present invention is not limited to these compounds.

In the present invention, the functional group-containing allyl compound as described above is used, and as mentioned above, the essential condition for such a compound is that the functional group in the compound has the property of undergoing an addition reaction with the hydroxyl group in the vinyl alcohol resin. Must. In other words, if a compound that undergoes a condensation reaction, such as allyl halide, is used, it cannot be used because a halide, such as hydrochloric acid (or its gas), is generated during molding or during molding.

The functional group-containing allyl compound obtained by the reaction of the above compound is blended in an amount of 0.1 to 20% by weight, preferably 0.5 to 15% by weight, based on the vinyl alcohol resin.

If it is less than 0.1% by weight, the effect of improving water resistance cannot be obtained.
If the amount is more than 20% by weight, gelation tends to occur during molding, and the resulting molded product, such as a film, will have many fish eyes, which will cause quality deterioration.

Although the compound may be added at any time, it is preferable to add the compound immediately before molding in consideration of the stability and operability of the resin composition.

The resin composition thus obtained may be added with various other known additives, such as sensitizers, curing agents, curing accelerators, thermoplastic resins for modification, and crosslinking, depending on the purpose during molding or at any other time. A rubber binder, a pigment, a filler, an abrasive, a leveling agent, a reinforcing agent, a lubricant, and the like can be added as appropriate.

Representative examples of such auxiliaries are shown below.

Examples of the sensitizer include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl diphenyl disulfide,
Tetramethylthiuram monosulfide, azobisisobutyronitrile, dibenzyl, diacetyl, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-noethoxyacetophenone, benzophenone, 2-chlorothioxanthone, 2- such as methylthioxanthone.

As a curing agent, methyl ethyl ketone peroxide,
Cyclohexane 7 peroxide, cumene hydroperoxide, benzoyl peroxide, dicumyl peroxide, t-butyl perbenzoate, etc.

Examples of curing accelerators include metal soaps such as cobalt octenoate, cobalt naphthenate, manganese octenoate, and manganese naphthenate, methylaniline, dimethylaniline, diethylaniline, methyl-p-)luidine, dimethyl-p-toluizine, and methyl. - Amines such as β-hydroxyethylaniline and non-β-hydroxyethyl-p-)luidine, or their salts such as hydrochloric acid, acetic acid, sulfuric acid, and phosphoric acid.

Thermoplastic resins include high-density, medium-density, and low-density polyethylene, polypropylene, polybutene, polypentene, and other homopolymers, ethylene-propylene copolymers, and ethylene or propylene-based polymers such as 1-butene and 1-hexene. Copolymers with α-olefins having about 2 to 20 carbon atoms, and olefin-vinyl acetate copolymers and olefins having a composition relatively similar to polyolefins, in which the content of olefins such as ethylene or propylene is 90 mol% or more. = Various polyolefin resins such as (meth)acrylic acid ester copolymers, graft-modified polyolefins obtained by graft-modifying these with unsaturated carboxyl groups, polyamide resins such as nylon-6 and nylon-6,6, vinyl chloride resins, vinylidene chloride resins, acrylic resins, acrylamide resins, styrene resins, vinyl ester resins, polyester resins and polyester elastomers, polyurethane elastomers, polycarbonates, chlorinated polyethylene resins, chlorinated polypropylene resins Such.

Examples of crosslinkable moamers include acrylic esters, methacrylic esters, glycidyl methacrylate, 2-hydroxymethacrylate glycidyl ether, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, diethylene glycol diacrylate, and unsaturated compounds having similar functional groups. monomer.

Pigments (titanium white, cyanine blue, cream yellow, watching red, benzene, carbon black, aniline black, manganese blue, iron black, ultramarine blue, Hansa red, chrome yellow, chrome green, etc.), fillers (calcium carbonate, kaolin, clay, talc, mica, alumina, asbestos powder, finely divided silica, barium sulfate, lithopone, gypsum, perlite, etc.), abrasives (zinc stearate, finely divided talc, etc.), leveling agents (silicone, xylene, methanol, ethanol, butanol, acetone, methyl isobutyl ketone, methyl ethyl ketone, cellosolves,
diacetone alcohol, etc.), reinforcing agents (plus fiber, carbon a fiber, etc.), lubricants (low molecular weight polypropylene, paraffin, flax 1' type, epoxy type, etc.).

The resin composition of the present invention, to which the additive auxiliary agent has been added according to the above purpose, has particularly excellent water resistance and gas barrier properties, so it can be used as a film or sheet by itself. There are two methods: a molded product, and a solution coating on the surface of a film, sheet, or molded product made of plastic or metal as a base material and used as a coating or paint. The conditions in such a case are described below. However, the present invention is not limited to these descriptions.

When molding the resin composition itself, use a Henschel mixer to mold the vinyl alcohol resin powder.
In a tumbler or the like, the functional group-containing allyl compound and, if necessary, its additives are blended, mixed and stirred. Thereafter, any suitable means may be employed, such as supplying the resin composition to an extruder and subjecting it to the desired molding as it is, or once forming it into a pellet and then subjecting it to the desired shaping.

The temperature conditions during melt molding are approximately 170 to 250
It is desirable to set it to °C.

In the melt molding method, during melting, the functional group of the functional group-containing allyl compound and the hydroxyl group in the vinyl alcohol resin undergo an addition reaction, resulting in a vinyl furfur resin having an allyl ether group. Note that the opening time during melt molding is usually 10 minutes at most, and generally takes less than 5 minutes, so there is no problem, but if this time is too long, there is a risk that the allyl ether group will also react and gelation will occur in the molding machine. Therefore, it is desirable to complete the process within 20 minutes at the most.

As the melt molding method, any molding method such as injection molding, compression molding, extrusion molding, etc. can be adopted. Among these, examples of extrusion molding methods include the T-Guy method, blow molding method, vibrator extrusion method, linear extrusion method, profile die extrusion method, and inflation method. The shape of the molded product is arbitrary, and not only pellets but also films, sheets, tapes, bottles, pipes, 7-filaments, irregular cross-section extrusions, etc., and multilayer laminates of these and other resins are also important.

In the case of lamination, the mating resins include low density polyethylene, medium density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, iophomer, ethylene-α-
Olefin (alpha-olefin having 3 to 20 carbon atoms) copolymer, ethylene-acrylic acid ester copolymer, polypropylene, propylene-α-olefin (carbon i number 4 to 20)
(α-olefin) copolymers, monopolymers or copolymers of olefins such as polybutene and polybentene, and monopolymers or copolymers of these olefins that have been graft-modified with unsaturated carboxylic acids or esters thereof. Resin, polyester resin, polyamide resin, copolymerized polyamide resin, vinyl chloride resin,
Examples include vinylidene chloride resin, acrylic resin, acrylamide 'JA81 resin, vinyl ester resin, polyester resin and polyester elastomer, polyurethane elastomer, polycarbonate, chlorinated polyethylene resin, and chlorinated polypropylene resin.

It is also possible to coextrude saponified ethylene-vinyl acetate copolymers with different compositions.

The layer structure is that the EVOH resin composition layer of the present application is A (A, , A2
゜01. ), the thermoplastic resin layer is B (B,,B2.,,,
), and when the adhesive layer provided as necessary is C, if it is in the form of a film, sheet, or bottle, it will not only have a two-layer structure of A/B, but also A/B/A, B/A/B, B, /B2/A,
B/A, /A2, A/B/A/B/A, A2/A, /B
/A, /A2, A/C/B, A/C/B/C/A, B/
C/A/C/B, A/C/B/C/A/C/B/C/A
Any configuration is possible, such as a filament type, where A and B are bimetallic, core (A)-sheath (B) type, or core (B) type.
)-sheath (A) type or eccentric core-sheath type, any combination is possible. In addition, a resin with a certain capacity may be blended with either or both of the above A and B, or a resin that improves the adhesion of both O (oil) may be blended.

By curing the single or laminated molded product thus obtained in the air, the allyl ether groups in the resin are further internally crosslinked, so that the intended purpose of improving water resistance can be achieved. In order to carry out a more active internal crosslinking reaction and obtain even better physical properties,
By means of heat curing or light irradiation such as ultraviolet rays or electron beams,
Post-processing is desirable. In the case of thermosetting, although there are some differences depending on the form of the molded product, the surface of the molded product is usually heated at 50 to 120°C, preferably 60 to 100°C, for 10 seconds to 30 seconds using hot air, an infrared lamp, etc. Heat for about a minute. On the other hand, when using light irradiation, the irradiation time is affected by the thickness of the molded product, the type of light source, and the conditions of the pond.
Using high-pressure mercury lamps, carbon arc lamps, xenon lamps, metalloid lamps, chemical lamps, black lights, etc., it is possible to use a lamp for several minutes at most, usually less than one minute, and in some cases less than one second, from the point of view of efficiency. Light irradiation is the most useful means.

When applying the resin composition to a molded article as a coating agent, the resin composition is usually dissolved or dispersed in a known vinyl alcohol solvent.

Examples of the solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol,
Lower alcohols such as n-butyl alcohol, isobutyl alcohol, secondary butyl alcohol, tertiary butyl alcohol, and benzyl alcohol, and these and water (
A mixture of B), and the mixture further contains formic acid or acetic acid and esters thereof such as methyl ester, ethyl ester, propyl ester, butyl ester, dimethyl or sulfoxy Y.
, N-methylpyrrolidone, etc. (C) is most preferably used. Mixed composition (weight) is (A)
/(B)=10/90 to 90/10, preferably 30
/ 70 to 70 / 30, most preferably when (C) is further used in combination, 2 to 8 based on the total weight of (A) and (B)
It is mixed so that the amount is 5% by weight, more preferably 5 to 40% by weight. Although a coating film with good water resistance can be obtained even when a mixed solvent of (A)/(B) is used, (A)/(B)
)/(C) system is even more excellent in stability of the resin solution, transparency of the coating film, etc. In addition, PVA series (3(
In the case of fats, it is also possible to use water alone as a solvent.

In the present invention, the base material to which the resin composition is applied is not particularly limited, and includes films, sheets, hollow containers or paper of various plastics such as polyethylene, polypropylene, polyester, polystyrene, and polyvinyl chloride, cellophane, cellulose acetate, Examples include natural rubber, synthetic rubber, and metal. The film thickness of such a base material is 10 to 10
Approximately 00μ is appropriate. In the present invention, the laminate obtained by applying the resin composition to such a base material is normally put into practical use as a packaging material as it is, but if necessary, the coating film obtained from such base material may be used. It can be peeled off and used as a single layer film, sheet, etc.

As the coating method, any known method such as roller coating method, spray coating method, dip coating method, etc. can be applied.

Further, depending on the type of the base material, surface oxidation treatment, flame treatment, anchor foot treatment, brimer treatment, etc. can be carried out as appropriate in order to improve the adhesive force with the resin composition.

As the anchor treatment agent, polyurethane compounds and polyester incyanate compounds can be suitably used. The practical thickness of the anchor foot layer is about O,OS to 3μ.

After applying the solution of the resin composition to the substrate, drying is performed. Drying temperature is 30~150℃, preferably 50~120℃
It is sufficient to heat it at a temperature of about C for about 3 seconds to 5 minutes.

When performing solution coating, light irradiation provides more desirable results for the physical properties of the molded product than requiring a longer drying time due to internal crosslinking of the allyl ether groups, i.e., reacting the allyl ether groups by further heating. can get.

Molded products in various forms obtained by melt molding or solution coating as described above may be subjected to cooling treatment, rolling treatment, pongee or two-wheel stretching treatment, printing treatment, r-ly lamination treatment, solution or melt coating treatment, as necessary. , bag making processing, searching processing, box processing, tube processing, split processing, etc. can be performed.

[Effect] Thus, by using the resin composition of the present invention, it is possible to significantly improve water resistance, which has traditionally been considered the biggest drawback of vinyl alcohol-based resins, and as a result, it has excellent properties even under high humidity conditions. It maintains gas barrier properties and is urethane-resistant. Of course, the molded product obtained from this resin composition also has very good other physical properties.

[Function 1] As described in detail, the resin composition of the present invention is useful for molded products such as various packaging films, containers, bottles, food trays, sheets, and various equipment parts, including those for food packaging. However, it can be widely applied to extrusion coatings of metals, paper, plastics, etc., and also to applications other than molded products, such as water-resistant adhesives and building materials.

[Example 1] Next, the composition of the present invention will be further explained by giving an example. Hereinafter, "parts" are expressed on a weight basis unless otherwise specified.

Vinyl alcohol resin (A-1) used: ethylene content 40 mol%, degree of saponification of vinyl acetate component 99.0 mol%, (at 210'C)
Same conditions below) Melt index (Ml) 3.4 E
VOH (A-2): ethylene content H2s mol%, saponification degree of vinyl acetate component 99.2 mol%, MI3.6 EVOH (A-3): ethylene content 55 mol%, saponification degree of vinyl acetate component 98.3 mol%, EVOH with MI 25 Functional group-containing allyl compound used (B-1); trimethylolpropane allyl ether monoadduct of isophorone diisocyanate (B-2)
): Pentaerythritol triallyl nythermo 7 adduct of isophorone diisocyanate (B-3): 2.2.
Glycerol allyl ether monoadduct of 4-trimethylhexamethylene diisocyanate (B-4) Nigericidyl allyl ether (B-5)
: Ethylene glycol glycidyl allyl ether Example 1 (J8 melt molding example) To 100 parts of resin (A-1), 0.5, 1.0, 2, 0 of each of the allyl compounds of (B-1) were added. , 5.0 parts, and 0.15 parts of benzoin isopropyl ether (hereinafter abbreviated as BIPE) were mixed and melt extruded under the following conditions,
A film molded product (thickness: 30 μm) was produced. It should be noted that the time required for molding was 4 minutes/Kg, and no problems with gelation or ponding, which were thought to be caused by the addition of the allyl compound, were observed.

○Molding conditions Extrusion Ill 40mm diameter extruder screw
L/D=28. Compression ratio 3.2 die
Fishtail extrusion temperature Shirirengu tip 230°C Gui
200℃Screw rotation speed 30r
pm The above film was exposed to a high pressure mercury lamp (80W/cm) at 10
Ultraviolet rays were irradiated for 5 seconds from a distance of cm.

Water resistance of the film thus obtained (20°C x 95%
Measurement of moisture absorption rate at RH), oxygen barrier property (20℃
x 96% R) (and measured at 20°C x dry state), and the hot water fusing temperature was evaluated and measured.

The results are shown in Table 1.

As a comparative example, the performance of a film obtained in the same manner except that the addition of (B-1) used above was omitted is also shown.

'N Down! A resin composition in which the vinyl alcohol resins (A-1) to (A-3) and the functional group-containing allyl compounds (B-1) to (B-5) are combined (the amount of the allyl compound is 1) 5% by weight based on fat), and processed the film as described below (light irradiation, heating, leaving at room temperature)
According to the above BIPE (in the case of light irradiation), cobalt octenoate (Octex Co manufactured by Nihon Kagaku Sangyo Co., Ltd.,
, containing 8% cobalt) and methyl ethyl ketone peroxide (Parnock-N, manufactured by Nippon Oil & Fats Co., Ltd.) (when heated or left at room temperature).
．． A film was produced in the same manner as before, adding 15% by weight.

After processing this film under the following conditions, its performance was evaluated.

・Light irradiation: Same as above ・Heating: Keeping the film temperature at 60 to 70'C
Apply hot air for 5 minutes.

- Room temperature: The results of leaving the film in an atmosphere of 20°C, 160% RH for 7 days or more are summarized in Table 2.

(Left below) Table 1 (Left below) Example 2 (Example of solution coating) 30% water, 50% isopropyl alcohol, 1120 ants
A mixture of 100 parts of vinyl alcohol resin (A-1) and 5 parts of functional group-containing allyl compound (B-4) was added to 90 parts of a mixed solvent containing %. A solution was prepared. On the other hand, polyurethane adhesive 1 was applied to a polyethylene terephthalate film with a film thickness of 50μ.
Anchor coating treatment was performed to a film thickness of 3 μm using a urethane compound solution consisting of 0.00 parts of curing agent, 6.5 parts of curing agent, and 900 parts of ethyl acetate.

The film treated in this way was immersed in the coating solution at a temperature of 25°C, and immediately dried at 70°C for 2 minutes to reduce the water content to 1.
．． A coating film was formed of a saponified ethylene-vinyl acetate copolymer (film thickness: 5 μm) containing 3% 1so-propyl alcohol, 0.1% formic acid, and 2% ethylene-vinyl acetate copolymer.

The laminate was heated with a high-pressure mercury lamp (80W/cn+) for 1
Ultraviolet light was irradiated for 5 seconds from a distance of 0clI+.

The transparency of the thus obtained laminated film has a haze value of 16.
% (base material haze value 14%, ASTM D1003-
52) and the surface properties were also good.

Furthermore, evaluation measurements were also conducted regarding water resistance, gas barrier properties, and hot water melting temperature, and the results shown in Table 3 were obtained.

100 parts of vinyl alcohol resins (A-1) to (A-3) and (B-4) and (B-5) were prepared in the same manner as above.
) are appropriately combined with 5 parts of the functional group-containing allyl compound, and the third
A coating film was formed on a polyethylene terephthalate film in the same manner as above using the solvent shown in the table, and a laminated film was obtained by further irradiating with ultraviolet rays.

The transparency of this film was also very good.

The measurement results of water resistance, gas barrier properties, and hot water melting temperature are summarized in Table 3.

(Leaving space below) Table 3 Explanation of abbreviations IP^: Isobubuil alcohol, t-BuOH:
t-Butyl alcohol.

DMS: Nomethyl sulfoxide

Claims (1)

[Claims] A resin composition comprising a vinyl alcohol resin and a compound having an allyl group and a functional group that can be added to a hydroxyl group in the resin.