JP3262640B2 - Laminate structure - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate structure having improved waste paper recovery, oxygen barrier properties, curl prevention and uniform winding.

[0002]

2. Description of the Related Art Hitherto, laminates using polyethylene as a processing agent have been generally used as laminate paper and laminate cloth used for packaging books and newspapers and for packaging foods. However, in recent years, pollution of water pollution and protection of natural resources have become major problems, and reuse of textiles such as paper and cloth has been actively performed as one of the solutions. In order to reuse the textile, the laminate must be heated and stirred in water to loosen the original fibrous state. However, since polyethylene is hydrophobic, it takes a long time to regenerate, and the quality of recycled paper and cloth is deteriorated. Therefore, it is practically impossible to collect and recycle. In addition, polyethylene is not particularly suitable for packaging foods because of its low oxygen barrier property, and the appearance of new wrapping paper and packaging cloth having good oxygen barrier properties has been desired.

In order to solve these problems, the applicant of the present invention has used a water-soluble oxyalkylene group-containing polyvinyl alcohol (hereinafter sometimes abbreviated as EO-PVA) to form a laminate with paper or cloth. (Japanese Patent Application No. 4-88)
031).

However, although the recoverability and the oxygen barrier property of the laminate have been solved, the laminate has only a slight improvement in curl prevention, and the curl prevention has been improved. The sex was not yet satisfactory and there was room for improvement.

[0004]

Means for Solving the Problems However, as a result of intensive studies to solve the above problems, the present inventors have found that a laminate of an oxyalkylene group-containing polyvinyl alcohol resin layer and paper or cloth has an oxyalkylene group-containing layer. A laminated structure obtained by laminating a modified polyolefin-based resin layer further having a carboxyl group or a hydroxyl group on the polyvinyl alcohol resin layer shows more excellent curl prevention, and also has excellent winding uniformity. And completed the present invention.

In the present invention, even if a polyolefin resin having a carboxyl group or a hydroxyl group, or another hydrophobic thermoplastic resin is further laminated on the oxyalkylene group-containing polyvinyl alcohol resin layer, the waste paper can be recovered at the time of recovery. When stirred in water, the oxyalkylene group-containing polyvinyl alcohol resin layer dissolves in water, and when immersed in water, water penetrates from the paper and the oxyalkylene group-containing polyvinyl alcohol resin layer dissolves in water. The paper is easily separated from the hydrophobic resin layer such as polyolefin. Therefore, since the paper can be easily recovered by removing the polyolefin-based resin layer or the hydrophobic thermoplastic resin layer, efficient recovery can be maintained, and in practical use, the hydrophobic thermoplastic resin layer exists outside. Therefore, it also has the advantage of being able to prevent the oxygen barrier property of the oxyalkylene group-containing polyvinyl alcohol resin layer in a high-humidity atmosphere from deteriorating in oxygen barrier properties and preventing water vapor permeability. Is high. Hereinafter, the present invention will be described specifically.

The oxyalkylene group-containing polyvinyl alcohol resin used in the present invention has a general formula

Embedded image

[Where R ¹ and R ² are hydrogen or an alkyl group, X
Is hydrogen, an alkyl group, an alkyl ester group, an alkylamide group, an organic residue such as a sulfonate group, and n is 1 to 300.
Which has the structure represented by the following formula:
X is usually hydrogen. The number n is advantageously between 2 and 300,
Particularly preferably, about 5 to 300 oxyalkylene groups are practical, and polyoxypropylene groups, polyoxybutylene groups and the like are effective. The vinyl alcohol resin having an oxyalkylene group can be produced by any method.
For example, a method of polymerizing a vinyl ester in the presence of polyoxyalkylene and saponifying, a method of copolymerizing an unsaturated monomer having an oxyalkylene group with a vinyl ester, and a method of saponifying, etc. Practical in terms of manufacturing and performance. The following method is specifically described.

[0008] Examples of unsaturated monomers having an oxyalkylene group include the following. However, the present invention is not limited to only these. (Meth) acrylate type general formula

Embedded image Wherein R is hydrogen or a methyl group, A is an alkylene group, a substituted alkylene group, a phenylene group, a substituted phenylene group, m is 0 or an integer of 1 or more, and n is an integer of 1 to 100. Examples include ethylene (meth) acrylate and polyoxypropylene (meth) acrylate.

(Meth) acrylamide type general formula

Embedded image Wherein R ³ is hydrogen or an alkyl group or

Embedded image A, R, R ¹ , R ² , m, and n are the same as described above), and include polyoxyethylene (meth) acrylamide, polyoxypropylene (meth) acrylamide, and polyoxyethylene (1- (meth) Acrylamide-1,1-dimethylpropyl) ester and the like.

(Meth) allyl alcohol type general formula

Embedded image (Wherein R, R ¹ , R ² , and n are the same as those described above), and examples thereof include polyoxyethylene (meth) allyl ether and polyoxypropylene (meth) allyl ether.

General formula of vinyl ether type

Embedded image (A, R ¹ , R ² , m, and n are the same as those described above), and examples thereof include polyoxypropylene vinyl ether. Among these monomers, the (meth) alcohol type is preferably used. Further, it is also obtained by copolymerizing polyoxyalkylene allylamine such as polyoxyethylene allylamine and polyoxypropylene allylamine, polyoxyalkylene vinylamine such as polyoxyethylene vinylamine and polyoxypropylene vinylamine, and then saponifying. be able to. As the vinyl ester, vinyl formate, vinyl acetate, vinyl trifluoroacetate, vinyl propionate, vinyl butyrate, vinyl caprate, vinyl laurate, vinyl versatate, vinyl palmitate, vinyl stearate and the like are used alone or in combination. However, in practice, vinyl acetate is preferred.

In the present invention, during the polymerization, a small amount of a general monomer other than the unsaturated monomer having an oxyalkylene group and the vinyl ester as described above is added as long as the water solubility is not impaired. Polymerization may be performed. These monomers are exemplified below. Ethylenically unsaturated carboxylic acids and their alkyl esters
Etc. crotonate methyl, ethyl crotonate, methyl itaconate, ethyl itaconate, methyl sorbate, ethyl sorbate, maleic acid monoalkyl esters, dialkyl maleates, the alkyl esters of oleic acid,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, ( Meta)
Decyl acrylate, hexadecyl (meth) acrylate,
Octadecyl (meth) acrylate and the like can be mentioned.

Allyl esters of saturated carboxylic acids: allyl stearate, allyl laurate, allyl coconut oil, allyl octylate, allyl butyrate and the like. α-olefin ethylene, propylene, α-hexene, α-octene,
α-decene, α-dodecene, α-hexadecene, α-octadecene and the like. Ethylenically unsaturated carboxylic acids (meth) acrylic acid, crotonic acid, (anhydrous) maleic acid, fumaric acid, itaconic acid and alkali metal salts, ammonium salts and the like thereof.

Alkyl vinyl ether propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, tetradecyl vinyl ether, hexadecyl vinyl ether, octadecyl vinyl ether and the like. Alkyl allyl ether propyl allyl ether, butyl allyl ether, hexyl allyl ether, octyl allyl ether, decyl allyl ether, dodecyl allyl ether, tetradecyl allyl ether, hexadecyl allyl ether, octadecyl allyl ether, and the like. In addition, (meth) acrylamide, (meth) acrylonitrile, styrene, vinyl chloride and the like can be used.

The copolymerization is not particularly limited, and any known polymerization method can be used.
Solution polymerization using an alcohol such as ethanol or isopropyl alcohol as a solvent is performed. Of course, emulsion polymerization and suspension polymerization are also possible. In the solution polymerization, as a method of charging the monomers, first, the entire amount of the vinyl ester and a part of the oxyalkylene group-containing unsaturated monomer are charged, polymerization is started, and the remaining unsaturated monomers are polymerized for the polymerization period. Arbitrary means such as a method of adding them continuously or dividedly and a method of charging the former collectively may be used. The copolymerization reaction is
The reaction is carried out using a known radical polymerization catalyst such as azobisisobutyronitrile, acetyl peroxide, benzoyl peroxide, and lauroyl peroxide. The reaction temperature is selected from the range of 50 ° C. to the boiling point.

The saponification is carried out by dissolving the copolymer in alcohol and in the presence of an alkali catalyst. Examples of the alcohol include methanol, ethanol, and butanol. The concentration of the copolymer in the alcohol is between 20 and 50.
It is selected from the range of weight%. As the saponification catalyst, sodium hydroxide, potassium hydroxide, sodium methylate,
It is necessary to use an alkali catalyst such as an alkali metal hydroxide or an alcoholate such as sodium ethylate or potassium methylate. It is necessary to use the catalyst in an amount of 1 to 100 mmole equivalent to the vinyl ester.

The preferred degree of saponification is 30 to 100 mol%,
Particularly preferably, 50 to 100 mol%, more preferably 80
-100%. The method is not limited to the above method, and a method of adding an alkylene oxide to polyvinyl alcohol (partially saponified product or completely saponified product) can be used. In the polyvinyl alcohol having an oxyalkylene group of the present invention, the content of the group is not particularly limited, but is usually 1 to 50% by weight, more preferably 5 to 40% by weight based on the whole resin.

Further, as the modified polyolefin resin having a carboxyl group or a hydroxyl group used in the present invention, carboxylic acid-modified polyolefin, carboxylic acid-modified ethylene-vinyl acetate copolymer, carboxylic acid-modified ethylene-
Acrylic ester copolymers, partially or completely saponified carboxylic acid-modified ethylene-vinyl acetate copolymers may be mentioned. Ethylene as a carboxylic acid-modified polyolefin,
Copolymerization of olefin monomers such as propylene, isobutylene and 1-hexene with ethylenically unsaturated compounds having a carboxyl group, for example, acrylic acid, methacrylic acid, maleic anhydride, maleic acid, crotonic acid, itaconic acid, etc. Or a metal ion such as Na ⁺ , K ⁺ , Ca
⁺ , Mg ⁺ , Zn ⁺ ), and a so-called ionomer neutralized with a polyolefin, and a graft copolymer of an ethylenically unsaturated compound having a carboxyl group in a polyolefin.

Examples of the carboxylic acid-modified ethylene-vinyl acetate copolymer include copolymers of ethylene, vinyl acetate and an ethylenically unsaturated compound having a carboxyl group, as in the case of the above-mentioned polyolefin, and ethylene-vinyl acetate copolymer. Any one obtained by graft polymerization of an ethylenically unsaturated compound having a carboxyl group in the coalescence is included,
The content of vinyl acetate is preferably 5 to 95 mol% based on the total amount. Further, as the carboxylic acid-modified ethylene-acrylic acid copolymer, ethylene, an acrylic acid ester and a copolymer of an ethylenically unsaturated compound containing a carboxyl group or an ethylene-acrylic acid ester copolymer having a carboxyl group-containing ethylenic Includes those obtained by graft polymerization of unsaturated compounds. Here, as the acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate,
2-ethylhexyl (meth) acrylate, and the content of these acrylates is 5 to 95 with respect to the total amount.
Preferably it is mol%.

The partially or completely saponified ethylene-vinyl acetate copolymer is obtained by saponifying an ethylene-vinyl acetate copolymer having an ethylene content of 5 to 95 mol% and a vinyl acetate content of 5 to 95 mol% to reduce the hydroxyl group to 50 to 50 mol%. It contains 100 mol%. In addition, as the partially or completely saponified product of the ethylene-vinyl acetate copolymer, an ethylene-vinyl acetate copolymer obtained by copolymerizing or graft-polymerizing an ethylenically unsaturated compound having a carboxyl group and saponifying the copolymer is also used. included. Among these modified polyolefin resins having a carboxyl group or a hydroxyl group, a carboxylic acid-modified polyolefin is preferable.

The carboxyl group content of the above-mentioned modified polyolefin having a carboxyl group is 0.05 to 1.5% by weight, preferably 0.1 to 1.0% by weight in terms of COOH. When the number of carboxyl groups is small, adhesiveness is not exhibited, and when it is 2% by weight or more, it becomes difficult to form a laminated structure, which is not preferable. The content of the hydroxyl group in the modified polyolefin having a hydroxyl group, particularly in the saponified ethylene-vinyl acetate copolymer, is 5 to 100 mol%, preferably 70 to 100 mol%. When the number of hydroxyl groups is small, the adhesion to EO-PVA decreases.

The paper or cloth used in the present invention is not particularly limited. Examples of the paper include paperboard such as manila balls, white balls, and liners, and printing paper such as general high-quality paper and gravure paper. As cloth, cotton, wool,
A woven or nonwoven fabric made of natural fibers such as silk and hemp, semi-synthetic fibers such as acetate, and synthetic fibers such as nylon and acrylic is used.

The modified polyolefin resin layer of the present invention / E
The method for forming the laminate structure of the O-PVA layer / paper or cloth is not particularly limited, and a known method such as a coextrusion method, a dry lamination method, or a multilayer inflation method is used. The lamination order of the laminate structure of the present invention is not particularly limited, and a paper or cloth is used as a base material, and EO-PVA is melt-coated (extrusion coated) on the base material, or a preformed EO-PVA film is used. After dry lamination with a substrate, the modified polyolefin resin is EO
-A method of obtaining a laminated structure by laminating with a melt (extrusion) coat or dry laminating in the same manner as PVA, or a method of previously forming an EO-PVA layer and the modified polyolefin resin layer.
There is a method in which a layer laminate is prepared by a co-extrusion method or a dry lamination method, and the two-layer laminate is laminated on the substrate. Further, EO-PVA and the modified polyolefin-based resin are formed on the substrate. It can also be co-extruded to obtain a laminate structure.

In such a method, a dry lamination method using a urethane-based or epoxy-based adhesive or a method in which a resin surface (adhesion surface) is heated to about 200 ° C. for adhesion can be adopted. In the present invention, a method of coextruding and laminating EO-PVA and the modified polyolefin-based resin on the base material enables continuous production, and a layer having a large thickness can be easily obtained. Since it is possible, the strength of the laminate structure is improved and the process is simplified.

Further, in the present invention, in order to further improve the film strength, the outside of the laminate structure (the modified polyolefin resin layer having a carboxyl group or a hydroxyl group).
It is preferable to laminate a hydrophobic thermoplastic resin on the surface. Here, the hydrophobic thermoplastic resin is polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, polystyrene, butadiene-styrene copolymer, styrene-based polymer. , Polyacrylonitrile, polyvinylidene chloride, ethylene-vinyl alcohol copolymer, polyvinyl chloride, polycarbonate, polyester, polyacid, polyurethane and the like. The method for laminating the resin can be performed according to the method for laminating the modified polyolefin resin having a carboxyl group or a hydroxyl group, EO-PVA, and paper or cloth.

Further, when various laminates are produced on paper or cloth, if necessary, a waterproofing agent such as glyoxal or urea resin, an antifoaming agent, a release agent, a surfactant, a preservative, an insecticide, etc. Known additives such as an agent, a rust preventive, and a thickener can be added to each resin. The thickness of the EO-PVA layer of these laminated structures is 3 μm or more, preferably 3 to
The thickness is preferably about 20 μm. If the thickness of the EO-PVA layer is less than 3 μm, sufficient oxygen barrier properties cannot be obtained. The laminate structure thus obtained is further conditioned at a temperature of 20 to 80 ° C. and a humidity of 50 to 100% RH so as to have a water content of 5 to 30%, preferably 8 to 15%, or further hot-pressed. Or

The laminate structure obtained as described above is more excellent in the effect of preventing the occurrence of curl, and also excellent in the uniformity of winding. Further, the laminate structure is used as a laminate paper and a laminate cloth for packaging of books and newspapers and for packaging of foods (milk packs and the like).
Furthermore, the modified polyolefin-based resin layer or the hydrophobic thermoplastic resin layer of such a laminated structure can be used for a wide range of applications, such as being used as a release paper by coating the layer with a silicone resin.

[0028]

The laminate structure of the present invention is excellent in waste paper recovery of paper and cloth and can be effectively reused.
Also, it has excellent oxygen barrier properties, and can be used for packaging foods and the like that are required to maintain freshness. Further, the laminate of the present invention exhibits high winding uniformity, and is a laminate structure which is particularly excellent in preventing curling.

[0029]

The present invention will be specifically described below with reference to examples. In Examples, “parts” and “%” are based on weight unless otherwise specified. Example 1 Acid-modified low density polyethylene (hereinafter abbreviated as acid-modified LDPE), EO-PVA (210 ° C., melt flow index (MFI) at 2160 g load: 6 g / 10)
min, degree of modification: 22% by weight, degree of saponification: 98 mol%)
Are laminated by a co-extrusion method, and a liner paper (JIS
Class A product specified in P 3902-1963, basis weight 2
00g / m ² ) and laminated paper (acid-modified LDPE layer (thickness 10 μm) / EO-PVA layer (thickness 1
5 μm) / liner paper). Subsequently, the laminated paper was conditioned at a temperature of 75 ° C. and a relative humidity of 85% RH to adjust the water content to 12%, and then hot-pressed at 200 ° C. for 1 second to obtain a laminated paper of the present invention. Various physical properties of the laminated paper were measured using the following methods.

Example 2 Acid-modified polypropylene (hereinafter abbreviated as acid-modified PP),
EO-PVA (MFI: 3 g / 10 min, degree of modification: 1)
4% by weight, saponification degree: 96 mol%) were laminated by a dry lamination method, and further liner paper (same as in Example 1)
And laminated paper (acid-modified PP layer (thickness 1)
0 μm) / EO-PVA layer (thickness 15 μm) / liner paper). Then, the laminate paper of the present invention was obtained by hot pressing at 200 ° C. for 1 second without humidity control. Various physical properties of the laminated paper were measured in the same manner as in Example 1. Example 3 Acid-modified LD using LDPE as a hydrophobic thermoplastic resin
Laminated by co-extrusion with PE and EO-PVA (MFI: 6 g / 10 min, degree of modification: 14% by weight, degree of saponification: 97 mol%), and laminated on liner paper (same as in Example 1) Paper (LDPE layer (thickness 5 μm) / acid-modified LDPE layer (thickness 10 μm) / EO-
A PVA layer (thickness: 20 μm) / liner paper) was obtained. Various physical properties of the laminated paper were measured in the same manner as in Example 1.

Example 4 The laminated paper obtained in Example 3 was further heated to a temperature of 8
Humidity control under the condition of 0 ° C. and relative humidity 95% RH, moisture content 1
It was adjusted to 3% and then hot pressed at 180 ° C. for 2 seconds to obtain a laminated paper. Various physical properties of the laminated paper were measured in the same manner as in Example 1. Example 5 Using PP as a hydrophobic thermoplastic resin, acid-modified PP, E
O-PVA (MFI: 3 g / 10 min, degree of modification: 22
% By weight, saponification degree: 98 mol%), and laminated by a three-layer inflation method.
Laminated paper (PP layer (thickness 10 μm) / acid-modified PP layer (thickness 10 μm) / EO-P
A VA layer (thickness: 20 μm) / liner paper) was obtained. Subsequently, the laminated paper was conditioned at a temperature of 80 ° C. and a relative humidity of 95% RH to adjust the water content to 10%.
For 2 seconds to obtain a laminated paper. Various physical properties of the laminated paper were measured in the same manner as in Example 1.

Example 6 A high-density polyethylene (hereinafter, referred to as a hydrophobic thermoplastic resin)
HDPE. ), Acid-modified HDPE, EO-P
VA (same as in Example 1) is laminated by co-extrusion method, and further laminated on liner paper (same as in Example 1) and laminated paper (HDPE layer (thickness 10 μm) / acid-modified HDPE layer (thickness 10 μm) / EO) -PVA layer (thickness: 15 μm) / liner paper). Subsequently, the laminated paper was conditioned at a temperature of 75 ° C. and a relative humidity of 85% RH to adjust the water content to 9% to obtain a laminated paper. Various physical properties of the laminated paper were measured in the same manner as in Example 1.

Comparative Example 1 LDPE was used as a hydrophobic thermoplastic resin, and was laminated by extrusion on liner paper (same as in Example 1) (LDPE).
5 μm). Subsequently, the temperature was 20 ° C and the relative humidity was 85%.
The humidity was adjusted under the condition of RH to adjust the water content to 5%.
Hot pressing was performed at 00 ° C. for 1 second to obtain a laminated paper. Various physical properties of the laminated paper were measured in the same manner as in Example 1. Comparative Example 2 A laminated paper was produced in the same manner as in Example 1 except that the acid-modified LDPE was omitted in Example 1, and various physical properties of the laminated paper were measured in the same manner as in Example 1.

Comparative Example 3 A laminated paper was prepared in the same manner as in Example 3 except that the acid-modified LDPE was omitted in Example 3, and various physical properties of the laminated paper were measured in the same manner as in Example 1. Comparative Example 4 EO-PVA using PP as a hydrophobic thermoplastic resin
(Same as in Example 5) and laminated by a co-extrusion method, and further laminated on liner paper (same as in Example 1) and laminated paper (PP layer (thickness 10 μm) / EO-PVA layer (thickness 15 μm) / liner paper) ) Got. Subsequently, the temperature 20
8% moisture content by controlling the humidity at 85 ° C and 85% RH
Then, hot pressing was performed at 200 ° C. for 1 second to obtain a laminated paper. Various physical properties of the laminated paper were measured in the same manner as in Example 1. Tables 1 and 2 collectively show the measurement results of Examples and Comparative Examples. In addition, the measuring method is as follows.

(Oxygen permeability) Oxygen permeability measuring device (OX)
-TRAN, MODERN CONTROLS, INC
Was measured at a temperature of 20 ° C. and a relative humidity of 40% RH. (Moisture Permeability) JIS Z 0
The measurement was carried out in accordance with Example 208. In the measurement, the test piece was attached to a cup so that the paper surface of the test piece faced downward, and the measurement was performed.

(Moisture resistance) According to the moisture permeability, the temperature is 40 ° C.
The sample was left under a relative humidity of 100% RH, and after 24 hours, the laminate structure was taken out, and the film laminate surface was observed. The evaluation criteria are expressed as follows. ○ No change △ Slight swelling × Stickiness (Strength) A test piece having a width of 5 mm and a length of 50 mm was prepared and subjected to humidity control for 48 hours in an environment of a temperature of 20 ° C. and a relative humidity of 65% RH, and a chuck using Tensilon. The tensile strength was measured under the measurement conditions of a distance of 20 mm and a tensile speed of 40 mm / min.

(Recovery rate) First used liner paper 30c
The dry weight per m × 30 cm was determined (W ₁ ), and then the laminated paper (30 cm × 30 cm) was treated with a 10 liter pulper for 20 minutes, and then left for 15 minutes.
The dry weight of the pulp dried for 3 hours with a hot-air dryer set at ° C. was determined (W ₂ ), and the recovery was determined by the following equation. Recovery rate (%) = 100 × W ₂ / W ₁

(Rolling Uniformity) 100 m of laminated paper is wound around a paper tube (diameter 15 cm) having a length of 2 m, and the diameters of the wound laminated paper and the paper tube are measured at six locations (maximum value− What percentage of the minimum value corresponds to the minimum value was determined by the following equation. 100 × (maximum value−minimum value) / (minimum value) The evaluation criteria are expressed as follows. 0-5% ○ 5-10% △ 10% or more ×

(Prevention of curl generation) Laminated paper (width 20 cm, length 34.54 m) is wound around a paper tube (outer diameter 11.0 cm) with the substrate (paper) side inside,
After being left at 5 RH% for one month, 10 sheets of 20 cm × 20 cm were sampled at intervals of 1 m from the beginning of the winding of the laminated paper, and the sheets were grounded with the convex on the horizontal surface, and the height of the curled portion (top) was measured. (H) was measured, and the value obtained by subtracting the thickness of the laminated paper was used as a measured value. still,
The evaluation criteria are expressed as follows. ◎ 0 ≦ h <1 mm ○ 1 ≦ h <2 mm △ 2 ≦ h <3 mm × 3 mm ≦ h

[0040]

[Table 1] Oxygen permeability Moisture vapor permeability Moisture resistance Tensile strength (20μ / m ²・ 24hr ・ atm) (g / m ² 24hrs) (kg / mm ² ) Example 1 31 27 ○ 3.5〃227 20 ○ 3.1 〃 317 19 ７ 7.6 ４ 417 19 6.6 ５ 521 10 ８ 8.5 〃 630 7 ○ 7.9 Comparative Example 1 Unmeasurable 21 6.2 〃 231 550 × 2.9 〃 317 450 7.1 〃 430 620 ○ 7.4

[0041]

[Table 2]

[0042]

The laminate structure of the present invention is excellent in waste paper recovery of paper and cloth and can be effectively reused. Also, it has excellent oxygen barrier properties, and can be used for packaging foods and the like that are required to maintain freshness. Further, the laminate of the present invention exhibits high winding uniformity, and is a laminate structure which is particularly excellent in preventing curling.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-54-42411 (JP, A) JP-A-61-266698 (JP, A) JP-A-59-155408 (JP, A) JP-A-1- 160550 (JP, A) JP-A-63-168437 (JP, A) Japanese Utility Model Application Sho 55-39805 (JP, U) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 1/00-35 / 00 D21H 11/00-27/42

Claims (3)

(57) [Claims] 1. A laminate structure comprising at least three layers of a modified polyolefin resin layer having a carboxyl group or a hydroxyl group / a polyvinyl alcohol resin layer containing an oxyalkylene group / paper or cloth. 2. The laminated structure according to claim 1, wherein a hydrophobic thermoplastic resin layer is provided outside the modified polyolefin-based resin layer having a carboxyl group or a hydroxyl group. 3. The laminate structure according to claim 1, wherein the thickness of the oxyalkylene group-containing polyvinyl alcohol resin layer is 3 μm or more.