JPH09193314A - Production of laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve pollution removal properties, resistance to platicizer migration properties in the existence of high humidity and interlaminar adhesion properties by coating a laminate consisting of a thermoplastic resin layer/a polyolefin resin layer/an ethylene-vinyl acetate copolymer saponified material layer with a specific solution at a time for producing the laminate. SOLUTION: In the case of producing a laminate consisting of a thermoplastic resin layer/a polyolefin resin layer/an ethylenevinyl acetate copolymer saponified material layer, the laminate consisting of the thermoplastic resin layer such as vinyl chloride resin/a polyolefin resin layer such as a high density polyethylene is coated with an ethylene-vinyl acetate copolymer saponified material solution. Therefore, the laminate is produced in which pollution removal properties are excellent and resistance to plasticizer migration properties in the existence of high humidity and interlaminar adhesion properties are excellent. The laminate is used for a facing sheet of wallpaper or the like, office supplies and material for the internal part of an automobile.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a thermoplastic resin layer (/ adhesive layer) based on a thermoplastic resin such as vinyl chloride resin.
/ Polyolefin resin layer (/ Adhesive layer) / Ethylene-
The present invention relates to a method for producing a laminate comprising a saponified vinyl acetate copolymer (hereinafter abbreviated as EVOH) layer. More specifically, it has excellent resistance to migration of a plasticizer in a thermoplastic resin layer, stain removability, and interlayer adhesion. The present invention relates to a method for manufacturing a laminated body.

[0002]

2. Description of the Related Art Conventionally, vinyl chloride resin sheets and films have been used as decorative sheets for finishing wallpaper and furniture for architectural interiors, agricultural materials, automotive interior materials, and daily goods (vinyl mats, umbrellas). Etc.), as well as office supplies such as desk mats, file covers, notebook covers, stationery and the like. Then, a method of laminating EVOH in order to prevent the adverse effect of the plasticizer in the vinyl chloride resin has been proposed (Japanese Utility Model Publication No. 2-47015), and in order to apply such a laminated body to a decorative sheet, JP-A-6-328635. In the publication, a laminate composed of a thermoplastic resin layer / adhesive layer / polyolefin resin layer / adhesive layer / EVOH layer by multi-layer coextrusion is described.

[0003]

However, such a vinyl chloride resin / EVOH laminate and a multilayer coextrusion thermoplastic resin layer / adhesive layer / polyolefin resin layer / adhesive layer / EVOH layer laminate As a result of a detailed study by the inventor of the present invention, although the plasticizer migration resistance is satisfactory, the stain removal property and the plasticizer migration resistance under high humidity and the interlaminar adhesion are not sufficient, and especially the interior material When used for wallpaper (decorative sheets for furniture, interior materials for automobiles, etc.), office supplies, stationery, etc., it is easy to remove stains (contamination) from foods and drinks, writing utensils, etc., and has high humidity due to dew condensation in winter. It has been found that further improvement in the plasticizer migration resistance and interlaminar adhesion below is desired.

[0004]

The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, have found that the thermoplastic resin layer (/ adhesive layer) / polyolefin resin layer (/ adhesive layer) / In producing a laminate comprising an EVOH layer, it was found that the above-mentioned problems can be solved by coating the laminate comprising a thermoplastic resin layer (/ adhesive layer) / polyolefin resin layer with EVOH, thereby completing the present invention. Came to do.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the production method of the present invention will be specifically described. Examples of the thermoplastic resin used in the thermoplastic resin layer of the present invention include vinyl chloride resin, polyester resin, acrylic resin, polystyrene resin, polyamide resin, and the like, but the effect of the present invention is most exerted. Then, vinyl chloride resin is preferably used.

As the polyolefin resin used for the polyolefin resin layer, high density polyethylene, medium density polyethylene, (linear) low density polyethylene, ultra low density polyethylene, vinyl acetate or acrylic ester, butene or hexene is used. , Polyethylene homopolymerized with α-olefins such as 4-methyl-1-pentene, polypropylene homopolymer, polypropylene grafted with ethylene, polypropylene copolymerized with α-olefins such as 4-methyl-1-pentene ,
Modified polyolefin type obtained by copolymerizing or graft-polymerizing poly-1-butene, poly-4-methyl-1-pentene and the above-mentioned polyolefin with an unsaturated carboxylic acid, an acid anhydride thereof, a vinylsilane type compound, an epoxy group-containing compound or the like. Examples of the resin include polyethylene such as high-density polyethylene, medium-density polyethylene, (linear) low-density polyethylene, ultra-low-density polyethylene, polypropylene homopolymer, polypropylene grafted with ethylene, and α-olefins. Polypropylene such as polymerized polypropylene and ethylene-vinyl acetate copolymer are preferably used.

Further, as EVOH used in the EVOH layer, ethylene content is 25 to 55 mol%, and further 28 to 4
A vinyl acetate component having a saponification degree of 8 mol% or more and 90 mol% or more, more preferably 95 mol% or more is suitably used. If the ethylene content is less than 25 mol%, water resistance becomes insufficient, while 55 mol% If it exceeds the range, the solubility at the time of solution preparation decreases, which is not preferable. On the other hand, if the saponification degree is less than 90 mol%, the water resistance and the thermal stability become insufficient, which is not preferable.
Further, the EVOH is a small amount of propylene, isobutene, α
-Α-, such as octene, α-dodecene, α-octadecene
Comonomers such as olefins, unsaturated carboxylic acids or salts thereof, partial alkyl esters, complete alkyl esters, nitriles, amides, anhydrides, unsaturated sulfonic acids or salts thereof may be contained.

In the present invention, a thermoplastic resin layer (/ adhesive layer) / polyolefin resin layer (/ adhesive layer) / EVOH layer using these resins was prepared in advance for production. The greatest feature of the present invention is to coat a laminate composed of a thermoplastic resin layer (/ adhesive layer) / polyolefin layer with EVOH in a solution state. The method will be specifically described. In the present invention, the use of the adhesive layer is optional, both adhesive layers may be adopted, or only one of the adhesive layers may be adopted, or neither may be adopted, but it is preferable. Both adhesive layers are employed.

No particular limitation is imposed on the production of the laminate comprising the thermoplastic resin layer (/ adhesive layer) / polyolefin resin layer, and it can be produced by a known method.
For example, a method of melt coextrusion of two kinds and two layers (preferably three kinds and three layers of modified polyolefin resin such as carboxylic acid modified as an adhesive layer) using a melt extruder, and laminating each film, two liquid reaction type Examples thereof include a method of dry-laminating and laminating with an adhesive such as a polyurethane-based adhesive, a method of laminating each film by heat and pressure (using a hot-melt adhesive as necessary), and the like. A method of laminating by melt coextrusion or a method of laminating by dry laminating can be adopted.

The thickness of such a laminate is not particularly limited, but the thermoplastic resin layer (/ adhesive layer) / polyolefin resin layer = 10 to 5000 μm (/0.1 to 10 μm) /
It can be arbitrarily selected from the range of 10 to 50 μm. Next, EVOH is coated on the obtained laminate comprising the thermoplastic resin layer / polyolefin resin layer. An adhesive is provided on the surface of the polyolefin resin layer coated with EVOH, if necessary. To be Examples of such an adhesive include an organic titanium-based adhesive, a two-component reactive polyurethane-based adhesive, and a polyester / isocyanate-based adhesive. A two-component reactive polyurethane-based adhesive is preferably used.

The EVOH to be coated is used as a solution, and the solvent used at that time is a mixed solvent of water and alcohol. The amount of water is 30 to 70% by weight (the amount of alcohol is 70 to 30% by weight). %), Preferably 40 to 60% by weight (the amount of alcohol is 60 to 40% by weight). If less than 30% by weight or more than 70% by weight, it is difficult to obtain a uniform solution and the coating film becomes opaque. Occurs. As alcohol, methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, s
Examples thereof include ec-butyl alcohol and tert-butyl alcohol, and n-propyl alcohol and iso-propyl alcohol are preferably used.

The EVOH concentration in the EVOH solution is not particularly limited and can be applied in an arbitrary range, and normally it is preferably about 0.5 to 40% by weight, but in order to exert the effect of the present invention efficiently, it is 10 to 10. 20% by weight is most preferred. Such EV
In coating the surface of the polyolefin resin layer of the laminate with the OH solution, a known method can be adopted, for example, a gravure coater, a reverse roll coater, an air knife coater, a spray, a brush coating,
Examples thereof include a bar coater, and preferably a gravure coater or a reverse roll coater is used.

One feature of the present invention is that the thickness of the EVOH layer (after drying) can be made very thin, and the thickness is preferably 0.5 to 20 μm, and particularly 2 to 10 μm.
It is preferable that the coating amount is m, and the amount of coating is not particularly limited as long as it has such a thickness.
It is arbitrarily selected from the range of 5 to 25 g / m ² , particularly about 2.5 to 12 g / m ² . Furthermore, in the present invention, EVOH
Solution viscosity (η) when applying the solution and subsequent drying temperature (T)
In carrying out the method of the present invention, it is necessary to take into consideration that the relationship with is 105 <T + 9 · log η <145 (where T is the drying temperature (° C.) and η is the solution viscosity (cps)). Is very important in. In such relational expression T
When the value of + 9 · log η is 105 or less, the barrier property becomes insufficient, and when it is 145 or more, the appearance is deteriorated, which is not preferable.

That is, the solution viscosity (η) and the solution viscosity (η) at the time of application of the EVOH solution in the present invention in the range of 50 to 1000 cps and the drying temperature (T) of 80 to 120 ° C. should satisfy the above relational expressions. It suffices to select the drying temperature (T). Further, the time for drying is not particularly limited, but it is usually appropriately selected from the range of 3 seconds to 10 minutes (further, 10 seconds to 5 minutes).

In the present invention, each layer of the laminate has a plasticizer (which is naturally contained in the vinyl chloride resin layer), a stabilizer, a surfactant, and a crosslinkable substance (epoxy compound, polyvalent metal, inorganic or inorganic compound). Organic polybasic acid or its salt, etc.), filler, colorant, fiber as reinforcing material (glass fiber, carbon fiber, etc.), matting agent (talc, silica-based powder, resin fine particle powder such as polyethylene, polyurethane) Etc. can be blended within a range that does not impair the effects of the present invention.

The laminate obtained by the method of the present invention is
It is also useful to form an uneven pattern by embossing at least one surface of the laminate in order to increase added value such as designability, and as the uneven pattern, a wood grain conduit pattern,
What imitated the surface of the painted board, an abstract pattern, a stone pattern, a cloth pattern, a line pattern, a wood texture, a combination thereof, and the like can be used. Further, the depth of the uneven pattern formed by embossing varies depending on the pattern, but in the case of wallpaper use, it is preferable to form it to about 20 to 100 μ, because it gives a good three-dimensional effect.

As a method for forming an uneven pattern by embossing, a method of performing embossing using a normal hot embossing machine on which an EVOH layer is formed and then forming a desired uneven pattern, or a cooling roll of an extrusion coater Using an embossing roll imparted with a desired concavo-convex pattern, etc., printing an ink containing a so-called mechanical embossing method or a so-called foaming inhibitor or a foaming accelerator, which is a so-called doubling embossing method for performing embossing at the same time as forming an EVOH layer, A chemical embossing method or the like that gives an uneven pattern in the foaming process is used.

Thus, the laminate comprising the thermoplastic resin layer / polyolefin resin layer / ethylene-vinyl acetate copolymer saponified layer obtained by the method of the present invention is used for finishing wallpaper such as interior decoration and furniture. Office supplies such as decorative sheets, desk mats, etc., stationery such as notebooks and files using PVC leather covers, interior materials for automobiles, agricultural materials such as agricultural films, daily sundries (vinyl mats, umbrellas) Etc.) and is very useful as an interior material such as a wallpaper or a decorative sheet.

When the laminate of the present invention is used as a wallpaper, a base material such as paper, Japanese paper, non-woven fabric, asbestos, paper, glass, fiber or cloth is adhered to the surface of the thermoplastic resin layer of the laminate of the present invention. It is also possible to apply (adhesion) adhesion and laminate by a method such as a calendering method or a laminating method. When such a wallpaper is attached to a wall, a commonly used known adhesive is applied to a substrate, It can be crimped to the wall.

[0020]

EXAMPLES The method of the present invention will be specifically described below with reference to examples. Unless otherwise specified, “%” and “parts” all mean on a weight basis. Example 1 A three-layer, three-layer melt extruder was used to laminate a vinyl chloride resin, polypropylene, and an ethylene-vinyl acetate copolymer-based adhesive (Mitsubishi Chemical Corporation, MODEC-AP E-300S) (vinyl chloride resin). Layer / adhesive layer / polypropylene layer = 1000 μm / 5 μm / 10 μm) was obtained. A two-component reactive polyurethane adhesive (AD-335A / ca manufactured by Toyo Morton Co., Ltd.) is formed on the surface of the polypropylene layer of the laminate.
t-10) so that the coating amount is 2 g / m ² (coating amount 0.5 g / m ² ) (thickness after drying 0.5 μm), and then EVOH solution with 12% EVOH concentration (ethylene content 30 mol% of EVOH having a saponification degree of 99.6 mol%
It was dissolved in a mixed solvent of iso-propyl alcohol weight ratio = 50/50 and had a solution viscosity of 2 when applied (40 ° C.).
00 cps) at 6 g / m ² (coating amount) and then 90 ° C
And dried for 3 minutes to form an EVOH layer having a thickness of 5 μm to obtain a laminate of the present invention. (T + 9 · log η = 90 + 9 · 2.3 = 111)

The following evaluation was performed using the obtained laminate. (Decontamination property) Lamination after applying or dripping hot coffee at about 70 ° C to a size of about 2 cm in diameter on the EVOH layer surface of the laminate and leaving it at room temperature for 24 hours and then wiping it with exposed cotton soaked with water The surface condition of the body was visually evaluated as follows. The same procedure was performed for the vinyl chloride resin sheet single layer. In addition, shoe ink, Japanese pepper and magic ink were also evaluated in the same manner. ○ −−− Completely wiped off and no trace of contamination is observed. [Delta] --- Although traces of contamination are recognized, the traces are less than in the case of the vinyl chloride resin sheet single layer. × −−− Traces equivalent to those of the vinyl chloride resin sheet single layer are recognized.

(Plasticizer migration resistance) Polystyrene plate (10
(cm × 10 cm) and then put a laminate of the same size so that the vinyl chloride resin layer is in contact with the polystyrene plate, and then 2
Evenly apply a load of 60 to 60 kg / m ^2.
The weight increase (Δα) of the polystyrene plate after being left for 30 days at 50 ° C and 50% RH was measured.
Weight increase of polystyrene plate when performed at RH (Δβ)
Was measured to calculate Δβ / Δα and evaluated as follows. ○ −−− Δβ / Δα ≦ 3 × −−− Δβ / Δα> 3

(Interlayer adhesion) Laminated body was subjected to 90% R at 20 ° C.
After being left for 10 days under the condition of H, the adhesive strength (T-type peel strength of 15 mm width) between the polypropylene layer and the EVOH layer of the laminate before and after the standing was measured to calculate the degree of decrease in adhesive strength [(before leaving. Adhesive strength-adhesive strength after leaving) / adhesive strength before leaving], and evaluated as follows. ○ --- calculated value <0.03 x --- calculated value ≥ 0.03

Example 2 In Example 1, the ethylene content of EVOH was 45 mol%, the EVOH concentration of the EVOH solution was 15%, the solution viscosity at coating (40 ° C.) was 600 cps, and an EVOH layer having a thickness of 8 μm was formed. Formed (T + 9 · log η =
(90 + 9 · 2.8 = 115) except that a laminated body was obtained in the same manner and evaluated in the same manner.

Example 3 In Example 1, the thickness of the polypropylene layer was 25 μm.
A laminate was obtained in the same manner except that the above was used, and the same evaluation was performed.

Example 4 A laminated body was obtained in the same manner as in Example 1 except that the polypropylene layer was changed to a linear low-density polyethylene layer having a thickness of 25 μm, and the same evaluation was performed.

Example 5 In Example 3, the drying temperature (T) after application of the EVOH solution was set to 110 ° C. (T + 9 · log η = 110 +).
(9.2.9 = 136) except that the laminated body is obtained in the same manner,
Evaluation was performed similarly.

Example 6 In Example 1, a vinyl chloride resin layer and a polypropylene layer were laminated to form a two-component reaction type polyurethane adhesive resin (Dainippon Ink and Chemicals, Dick Dry LX-90).
A laminate was obtained in the same manner as in 1) except that dry lamination was performed, and the same evaluation was performed.

Example 7 In Example 1, the thickness of vinyl chloride resin / adhesive resin / polypropylene / adhesive resin / EVOH was 2000 μm /
A laminate was obtained in the same manner except that the thickness was 5 μm / 25 μm / 5 μm / 10 μm, and the same evaluation was performed.

Example 8 In Example 1, the EVOH concentration of the EVOH solution was adjusted to 10
%, The solution viscosity at the time of application (40 ° C.) was set to 100 cps to form an EVOH layer having a thickness of 3 μm (T + 9 · l).
except that (og η = 90 + 9.2) = 108), a laminated body was obtained in the same manner, and the same evaluation was performed.

Example 9 In Example 1, the mixed solvent of the EVOH solution was water / n-.
Propyl alcohol weight ratio = 50/50, EVOH
The solution viscosity at the time of application (40 ° C) is set to 15% with a concentration of 16%.
0 cps (T + 9 · log η = 90 + 9 · 2.7)
= 114), a laminated body was obtained in the same manner, and the same evaluation was performed.

Comparative Example 1 Instead of EVOH solution coating in Example 1, a 15 μm thick EVOH film was used as a two-component reactive polyurethane adhesive resin (manufactured by Dainippon Ink and Chemicals, Inc.,
A laminated body was obtained in the same manner except that the dry lamination was performed using Dick Dry LX-901), and the same evaluation was performed.

Comparative Example 2 Using a vinyl chloride resin, polypropylene, EVOH and an ethylene-vinyl acetate copolymer-based adhesive (Mitsubishi Chemical Co., Model-AP E-300S), melt coextrusion of 4 layers and 5 layers was performed. , Vinyl chloride resin / adhesive resin / polypropylene / adhesive resin / EVOH = 1000 μm / 5 μm / 1
A laminate having a thickness of 0 μm / 5 μm / 10 μm (thickness) was obtained and evaluated in the same manner as in Example 1. Table 1 shows the evaluation results of the examples and the comparative examples.

[0034]

[Table 1] Contamination removal resistance Plasticizer migration resistance Interlayer adhesion Example 1 ○ ○ ○ 〃 2 ○ ○ ○ 〃 3 ○ ○ ○ 〃 4 ○ ○ ○ 〃 5 ○ ○ ○ 〃 6 ○ ○ ○ 〃 7 ○ ○ ○ 〃 8 ○ ○ ○ 〃 9 ○ ○ ○ Comparative Example 1 △ ○ × 〃 2 ○ × ×

[0035]

EFFECT OF THE INVENTION In the present invention, EVOH is solution-coated on a laminate comprising a thermoplastic resin layer / a polyolefin resin layer, so that it is excellent in stain-removing property, and further has resistance to migration of plasticizer under high humidity. Also, it is possible to obtain a laminate having excellent interlayer adhesion, and office supplies such as desk mats, wallpaper for interior decoration, decorative sheets for finishing furniture, etc., notebooks and files using PVC leather cover, etc. It is very useful for stationery, interior materials for automobiles, agricultural materials such as agricultural films, and sundries (vinyl mats, umbrellas, etc.).

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location B32B 27/32 B32B 27/32 C

Claims (6)

[Claims] 1. When producing a laminate comprising a thermoplastic resin layer / polyolefin resin layer / saponified ethylene / vinyl acetate copolymer layer, ethylene-vinyl acetate is added to the laminate comprising the thermoplastic resin layer / polyolefin layer. A method for producing a laminate, which comprises coating a solution of a saponified copolymer. 2. A thermoplastic resin layer / adhesive layer for producing a laminate comprising a thermoplastic resin layer / adhesive layer / polyolefin resin layer / adhesive layer / ethylene-vinyl acetate copolymer saponified layer. A method for producing a laminate, which comprises coating a laminate comprising a polyolefin layer with a solution of a saponified ethylene-vinyl acetate copolymer through an adhesive. 3. The method for producing a laminate according to claim 1, wherein the thermoplastic resin is vinyl chloride resin. 4. The polyolefin resin is polyethylene,
It is either polypropylene or ethylene-vinyl acetate copolymer, The manufacturing method of the laminated body in any one of Claims 1-3 characterized by the above-mentioned. 5. A laminate comprising a thermoplastic resin layer / a polyolefin resin layer is laminated by either a coextrusion method or a dry lamination method.
The method for producing a laminate according to any one of the above. 6. When coating the saponified ethylene-vinyl acetate copolymer solution, the solution viscosity (η) of the saponified ethylene-vinyl acetate copolymer and the drying temperature (T) after coating satisfy the following conditions. The method for manufacturing a laminate according to any one of claims 1 to 5, which is characterized by the following. 105 <T + 9 · log η <145 (where T is the drying temperature (° C.), η is the solution viscosity (cps)
Represents )