JPH0985847A - Resin sheet with non-homogeneous surface characteristic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin sheet with non-homogeneous surface characteristics by arranging regularly and repeatedly a plurality of resins with different surface characteristics on the surface in a stripe-like shape. SOLUTION: Flows of molten resins A and B extruded from extruders 20a and 20b and introduced respectively into a spiral die 21 are introduced into a plurality of spiral flow path channels 24a and 24b. Thereafter, while they are advanced upward in a single cylindrical flow path between an inside die ring 22a and an outside die ring 22b as spiral flows accompanied with leakage flows along these spiral flow path channels, these resins A and B are alternately and obliquely laminated to two main surfaces of a resin sheet and are extruded from a die lip 27 through a cylindrical flow path 25 with no spiral flow path channel. The extruded cylindrical resin sheet has a cross section in the peripheral direction (a cross section in the transverse direction being orthogonal to the axis) in which the resins A and B are alternately and obliquely laminated to the two main surfaces.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin sheet having an inhomogeneous surface characteristic (note that the term "resin sheet" in the specification of the present application refers to an area that is substantially larger than an end surface, It means a resin molded product having two main surfaces and includes a so-called "resin film", and is not particularly intended to limit the thickness.

[0002]

2. Description of the Related Art Naturally, the surface characteristics of a resin sheet are mainly governed by the properties of the resin constituting the sheet. It is also known to perform surface treatment to improve the quality of the resin sheet or to improve its processability to modify the surface characteristics. Known examples of such surface treatments include etching as a pretreatment for plastic plating, flame treatment or discharge treatment as a pretreatment for printing, sustaining, and antifogging treatment. However, if the surface characteristics of the resin sheet can be modified by the constituent resin itself without using such a surface treatment, there is no better result.

[0003]

SUMMARY OF THE INVENTION The main object of the present invention is to provide a resin sheet having non-uniform surface characteristics by using different kinds of resins together.

As a result of earnest studies toward the development of a composite resin sheet, the present inventors have already formed two or more different resins and have two main surfaces, and in at least one cross section orthogonal to the two surfaces, Laminated resin molded body (patent application No. 251629 of 1994, hereinafter referred to as prior application) characterized in that layers of the plurality of resins are laminated obliquely with respect to the two surfaces, and its effect using a spiral die Manufacturing method (1994, Japanese Patent Application No. 251628) is being developed.

As a result of further studies, the inventors of the present invention have found that when a plurality of resins having different surface characteristics are used in a laminated resin molding having the above structure (hereinafter, also referred to as "oblique laminate"). It has been found that a resin sheet can be obtained in which stripes are arranged on the surface in a regular order while maintaining the surface characteristics originally possessed by the plurality of resins.

The resin sheet of the present invention is based on such knowledge. More specifically, a plurality of resins having different surface characteristics are regularly arranged in stripes on the surface of the resin sheet. It is characterized by.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described more specifically with reference to the drawings.

A conventional laminated resin sheet is shown in FIGS. 1 (a), 1 (b) and 1 (c), respectively, which is a conceptual perspective view, a longitudinal (MD) direction partial sectional view parallel to the axis, and orthogonal to the axis. As shown by the partial cross-sectional view in the transverse (TD) direction, the constituent resin layers A and B are evenly laminated in parallel to the two main surfaces to the ends.

On the other hand, the resin sheet of the present invention is obtained by using a spiral die according to an example of a preferable manufacturing method thereof, and is a conceptual perspective view, a MD direction partial sectional view and a TD direction partial sectional view of the resin sheet 1. As shown in (a), (b), and (c) of FIG. 2, respectively, the cross section in the MD direction shows a form in which the resin layers A and B are alternately laminated in parallel on the two main surfaces 1a and 1b ( In FIG. 2B, the resin layers A and B are alternately and obliquely laminated so as to reach the two main surfaces 1a and 1b in the TD cross section. However, the individual resin layers A and B are the resin sheets 1
The angle θ (°) formed between the two main surfaces 1a and 1b of FIG.
It is not so large as to be exaggeratedly expressed in (c), and is generally in the range of more than 0 ° and 4 ° or less, particularly 0.001 ° to 0.
It is in the range of 4 °. The angle θ can be expressed by the following relational expression (a development angle (ω (°)) will be described later).

Tan θ = [thickness of resin sheet (mm)]
/ [Circular length of cylindrical resin sheet (mm) x deployment angle (ω) / 360 °] The laminated structure of the resin sheet is basically the same as that of the diagonal laminated body of the prior application. is there. However, as a result of further research conducted by the present inventors, when a combination of the above-mentioned resins A and B having different surface characteristics was adopted, each of the resins A and B probably existed on the surface of the resin sheet as shown in FIG. 2 (d). Probably because the individual striped regions were formed rather clearly, it was confirmed that the striped regions in which the surface characteristics of the respective resins A and B were well maintained were formed on the two main surfaces of the resin sheet. It was issued.

Therefore, the conventional A / B / A shown in FIG.
In the laminated body, only the surface characteristic of the resin A is obtained, but in the resin sheet of the present invention, the heterogeneity due to the combination of the surface characteristics of the resin regions A and B alternately arranged as the stripe-shaped regions is obtained. Excellent surface characteristics can be obtained.

Here, the width of each of the striped resin regions A and B on the surface of the resin sheet is the spiral when the resin sheet is manufactured by using a spiral die as one preferred embodiment for manufacturing the resin sheet of the present invention described later. It is determined by the number of flow channels, the arrangement of the resin flowing in the spiral flow channels, the total sheet width, the melt viscosity of the inflowing resin, the volume ratio of the inflowing resin, and the like.

For example, a plurality of different resins (n; n is a natural number) having the same melt viscosity are provided in the same volume ratio at adjacent spiral passage grooves (m pieces; where m is a natural number) of the spiral die. Then, there is a relationship of n <m)
In order to allow different resins to flow, the arrangement is such that a plurality of different resins are repeatedly flowed in regularly, and the circumference length X
When a cylindrical resin sheet of millimeter is obtained, n kinds of resins are alternately arranged on the surface of the obtained resin sheet, and the number of stripes is m / n per resin (m / n is a natural number). .), And the width of each stripe is X /
It becomes m millimeters. That is, as one specific example, two kinds of resins A and B having the same melt viscosity are added to a spiral die having 32 spiral flow passage grooves at the same volume ratio as A / B / A /
When a cylindrical resin sheet having a circumferential length of 320 mm is manufactured by inflowing in an array of B / A / B ..., stripes of resins A and B having a width of 10 mm are alternately formed on the surface of the obtained resin sheet. 16 will be arranged.

In the above, a resin sheet (A / B / A / B / A / B) in which two kinds of resins A and B are alternately arranged on the surface is used.
...). However, the order of arranging the various resin regions on the surface of the resin sheet is arbitrary. For example, regarding the two kinds of resins A and B, A / B / B / A / B / B / A ...
Alternatively, a repeating structure such as A / B / B / A / A / B / B / A ... Is also possible. In order to obtain a resin sheet in which the inhomogeneity of the surface characteristics is uniform over the entire surface, it is preferable to perform the repetitive arrangement in a fixed order such as an arrangement in which the arrangement order is alternated rather than arbitrary one. It is also possible to arrange three or more types of resin areas on the resin sheet surface,
Of course, this is possible, and the following are examples of the arrangement order of the three resins, A, B, and C, for example.

A / B / C / A / B / C / A ...
..., A / B / C / B / A / B / C / B / A ...
., A / B / A / B / C / A / B / A / B / C ...
A / B / C / B / A / B / C / B / A ....

In general, when considering the production by the inflation method using a spiral die as a preferable production method, a plurality (n; where n is a natural number) of different resins, that is, the number of resin species for arrangement (or lamination) ( n) is 2 to 4, on the other hand, the total number of arrays (m; where m is a natural number and has a relationship of n <m), that is, the total number of spiral channel grooves 24a, 24b, etc. described later. (M), in other words, the spiral thread number (m) is 4
To 256 grooves, more preferably 8 to 128 grooves, especially about 16 to 64 grooves, and the number of laminated layers in the thickness direction at a specific surface direction position of the resin sheet is 4 to 100 layers, particularly 6 to 6.
It is preferably 20 layers. The number of laminated layers in the thickness direction is
Spiral flow channel number (spiral thread number) m and expansion angle ω
And m × ω / 360 °. For the overall thickness of the resin sheet, for example, use the melt extruded parison as it is, or the inflation ratio (stretch ratio).
It is possible to control a wide range by controlling
A thickness of 0 μm to 1 mm, particularly about 15 to 200 μm is preferable.

The resin sheet of the present invention is preferably an inflation method using a spiral die, which is the same as the above-mentioned obliquely laminated body of the prior application (itself is the patent application No. 25 of 1994).
1628), which is manufactured by the same method as described below.

First, for comparison, a method using a conventional multilayer spiral die will be described with reference to FIG. First, the resin B extruded from the extruder 10a (not shown) and introduced into the spiral die 11 is a so-called (reverse) tournament type branch arranged near the outer periphery of the first die ring (innermost ring) 12a. It is introduced into a plurality of spiral flow passage grooves 14a provided on the outer peripheral surface of the first die ring 12a while being uniformly branched by a passage 13a (only one is shown). Each of the spiral flow passage grooves 14a has a groove depth that gradually decreases as it advances in the traveling direction (upward), and the flow of the molten resin B passing therethrough overflows the groove in the gap with the second die ring 12b and leaks. A tubular flow path 15 that spirals upward while forming a flow, and finally has no groove.
a as a uniform axial tubular flow, traveling upwards, and at the confluence 1
To 6. On the other hand, the flow of the molten resin A extruded from the extruder 10b is similarly branched and goes through a spiral flow accompanied by a leakage flow,
A uniform tubular flow in the axial direction passes through the tubular flow path 15b and reaches the confluence 16. Further, the flow of the molten resin B extruded by the extruder 10c also undergoes a spiral flow accompanied by branching and leakage flow in the same manner to become a uniform axial tubular flow passing through the tubular flow passage 15c, and reaches the confluence point 16. At the confluence 16, these three cylindrical molten resin streams are laminated and extruded from the die lip 17 as a cylindrical resin sheet. As shown in FIG. 3B, the tubular resin sheet extruded from the die lip 17 constitutes a tubular resin sheet having the resin layer A as an intermediate layer and the resin layers B on both sides thereof.

On the other hand, FIG. 4 (a) is a schematic cross-sectional view of the spiral die 21 used in the preferred method for producing a resin sheet of the present invention. The spiral die 21 is extruded by the extruders 20a and 20b, respectively. The flows of the molten resins A and B introduced in the above are branched by a (reverse) tournament type branch passage (not shown, which will be described later) which is similar to 13a in FIG. 3 (a). , Are introduced into the plurality of spiral flow passage grooves 24a and 24b, respectively. Thereafter, as a spiral flow accompanied by a leakage flow along these spiral flow passage grooves, in the process of traveling upward in a single cylindrical flow passage between the inner die ring 22a and the outer die ring 22b, these molten resin A and B and B are alternately laminated obliquely on the two main surfaces of the resin sheet, and extruded from the die lip 27 through the tubular flow path 25 having no spiral flow path groove. As shown in FIG. 4B, the extruded tubular resin sheet has a circumferential cross-section in which resins A and B are alternately and obliquely laminated with respect to two main surfaces thereof (lateral (TD) orthogonal to the axis). Direction cross section).

FIG. 5 is a schematic perspective view of the frame III portion surrounded by the one-dot chain line in FIG. 4 (a) for explaining the distribution-lamination aspect of the molten resin flows A and B in more detail. That is, the molten resin flows A and B introduced into the spiral die 21 through the extruders 20a and 20b first reach the tournament branch points 23a1 and 23b1, and further branch therefrom through the branch points 23a2, 23b2. After repeating the final branch points 23a3 and 23b3, the distribution section final flow paths 28a, 28b, 28a, 28b
.. from which the spiral flow channel 24a,
The molten resin streams A and B alternately flow into 24b, 24a, 24b, .... Here, the spiral flow path groove 24a,
The start points of 24b, 24a, 24b ... (End points of the distribution section final flow paths 28a, 28b, 28a, 28b ...)
It is located on the same circumferential line of the inner die ring 22a.
The molten resin flows A and B that have entered the spiral flow passage grooves 24a and 24b are initially exclusively filled with the spiral flow passage grooves 24.
Although it progresses as a spiral flow along a and 24b, the inner die ring 22a is gradually increased, and in particular, its spiral mountain 22aa,
In the flow path 22ab, which is a gap with the outer die ring 22b, a leakage flow that goes over the spiral mountain 22aa occurs along the flow path (that is, upward). That is, as if the molten resin flow film of the resin A and the resin B is formed in the circumferential direction, it flows out from each spiral flow path groove. The molten resin flow films of the resin A and the resin B thus formed are respectively transferred to the molten resin flow films of the resin B and the resin A flowing out from the spiral grooves 24b and 24a on the downstream side, that is, the molten resin flow film A. And the molten resin flow film B are laminated so as to be alternately covered. The stacked angle corresponds to the expansion angle ω (FIG. 4B) of the resin leaking from each spiral channel. That is, the starting point of the spiral flow channel forms the outer surface side, moves toward the inner surface side as the layers are stacked, and reaches the inner surface when moved by the development angle ω. In this way, the resin A and the resin B are stacked in a state of being inclined by the respective development angles ω (FIG. 4B). Deployment angle ω (°)
Can be controlled by the initial depth of the spiral flow passage grooves 24a, 24b formed for each of the resins A, B, the ratio of gradually decreasing depth, etc.
720 ° range, preferably 80 ° -360 ° range,
More preferably, it is in the range of 130 ° to 230 °. When the expansion angle ω is less than 60 °, the resulting laminate has many thickness irregularities, while when it exceeds 720 °, the pressure in the spiral die during molding becomes large, and the molding process becomes difficult.

Returning to FIG. 4, the cylindrical resin sheet extruded from the die lip is subjected to an inflation process for expanding and thinning, and then generally cut in a direction parallel to the axis. The resin sheet of the present invention as shown in 2 (a) to (c) is obtained.

When a resin sheet is formed from two kinds of resins A and B using a spiral die, the volume ratio of the resins A and B introduced into the spiral die is 1: 0.05 to 1: 1.
The ratio is preferably 20, and more preferably 1: 0.3 to 1: 3. It should be noted that this volume ratio is in the case of using a spiral flow channel having substantially the same groove depth and width at the start point and the end point of the spiral flow channel groove in which the resin A is introduced and the spiral flow channel groove in which the resin B is introduced. This is an example, and the volume ratio is changed by changing the spiral flow path design.

Further, resin A introduced into the spiral die
And B have a melt viscosity (200 ° C., 25 sec ⁻¹ ) of 10
0-5000 Pa · s, preferably 300-2000 P
a · s, more preferably 400 to 1200 Pa · s is preferable. The melt viscosity ratio of the resin A and the resin B is, for example, a spiral flow channel groove in which the resin A is introduced and a spiral flow channel groove in which the resin B is introduced have the same groove depth and width at the start point and the end point. When using, the melt viscosity ratio at 200 ° C. and 25 sec ⁻¹ is preferably 1: 0.5 to 1: 2.0. However, the optimum value of the melt viscosity ratio can be changed by changing the spiral channel design such as the groove depth and width of the spiral channel and the processing temperature.

Next, some examples will be given of combinations of a plurality of resins having different surface characteristics which are preferably used in the present invention. For the sake of simplicity, a combination of two kinds of resins A and B will be described, but as described above, it is possible to combine three or more kinds of resins as necessary.

1. Combination of hydrophilic resin A and hydrophobic resin B
Let me.

This combination is a preferable combination example among the combinations using resins having different degrees of hydrophilicity, and this combination example is suitably used, for example, for controlling the antifogging property of the resin sheet.

(Hydrophilic Resin A) As the hydrophilic resin, saponified ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVOH), polyamide resin (hereinafter abbreviated as Ny), polyhydroxypolyether, polyvinyl alcohol, heat Plastic polyurethane and the like are preferably used.

The ethylene content in EVOH is preferably 20 to 60 mol%, particularly preferably 32 to 48 mol%. If it is less than 20 mol%, the melt moldability is poor, and if it is 60 mol% or more, the hydrophilicity is insufficient. EVOH preferably has a saponification degree of 90% or more. If it is less than 90%, the thermal stability and the hydrophilicity decrease.

EVOH may be blended with a plasticizer, a heat stabilizer, an ultraviolet absorber, an antioxidant and a filler as long as the characteristics are not impaired.

Examples of polyamide resins include nylon 6, nylon 9, nylon 11, nylon 12, nylon 46, nylon 66, nylon 69, nylon 61.
1, a binary copolymer of monomer components constituting nylon 612, nylon 6, nylon 9, nylon 1
1, Nylon 12, Nylon 46, Nylon 66, Nylon 69, Nylon 611, Nylon 612, and aromatic polyamides (Nylon MXD6, Nylon 6I-6T, Nylon 6I, etc.) or the above polyamide resin. Copolymerization, a melt blend, etc. are also mentioned as a preferable thing.

The polyamide resin may be blended with a plasticizer, a heat stabilizer, an ultraviolet absorber, an antioxidant and a filler as long as the characteristics are not impaired.

Examples of the polyhydroxy polyether include substantially linear homopolymers and copolymers represented by the following general formula.

[0033]

Embedded image [In the formula, R represents a divalent aromatic hydrocarbon group containing a p-phenylene group, an m-phenylene group, a carbonyldiphenylene group and a sulfonyldiphenylene group as a main component, and n
Is a positive number. It is conventionally known that polyhydroxypolyether is produced by a polyaddition reaction between an aromatic diol compound and an aromatic diglycidyl ether compound. The aromatic diol compound used in the production is p-phenylene,
It is a compound having a structure in which two phenolic hydroxyl groups are bonded to a divalent aromatic hydrocarbon group selected from m-phenylene, carbonyldiphenylene, sulfonyldiphenylene and the like. Examples of such aromatic diol compounds include hydroquinone, resorcin, bisphenol S (that is, 4,4'-dihydroxydiphenyl sulfone), bisphenol K (that is, 4,4'-dihydroxydiphenyl ketone), and bisphenol A (that is, ,
2,2-bis (4'-hydroxyphenylpropane)), bisphenol F, methylhydroquinone, chlorohydroquinone, 4,4'-dihydroxydiphenyl oxide, 2,6-dihydroxynaphthalene, dichlorobisphenol A, tetrachlorobisphenol A,
Tetrabromobisphenol A, bisphenol AC
P, bisphenol L, bisphenol V, etc. can be mentioned. These aromatic diol compounds can be used alone or in combination of two or more.

On the other hand, in the aromatic diglycidyl ether compound, two glycidyl ether groups are bonded to a divalent aromatic hydrocarbon group selected from p-phenylene, m-phenylene, carbonyldiphenylene, sulfonyldiphenylene and the like. It is a compound having the above structure. Examples of such aromatic diglycidyl ether compounds include hydroquinone glycidyl ether, resorging glycidyl ether, bisphenol S diglycidyl ether, bisphenol K diglycidyl ether, bisphenol A diglycidyl ether, bisphenol diglycidyl ether, bisphenol F diglycidyl ether. , Methylhydroquinone diglycidyl ether, chlorohydroquinone diglycidyl ether, 4,4'-dihydroxydiphenyl oxide diglycidyl ether, 2,6
-Dihydroxynaphthalene diglycidyl ether, dichlorobisphenol A diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, tetrabromobisphenol A diglycidyl ether, bisphenol ACP diglycidyl ether, bisphenol L
Examples thereof include diglycidyl ether and bisphenol V diglycidyl ether. These aromatic diglycidyl ether compounds can be used alone or in combination of two or more.

The hydrophilic resin has a melt viscosity (200 ° C., 25
sec ⁻¹ ) is 100 to 5000 Pa · s, preferably 300 to 2000 Pa · s, and more preferably 400 to 1
200 Pa · s is preferable.

(Hydrophobic resin B) Examples of the hydrophobic resin include high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, linear ultra low density polyethylene, polypropylene, ethylene-propylene copolymer. Ethylene with a vinyl acetate content of 5 to 45% by weight
Vinyl acetate copolymer, acrylic acid content 5-20% by weight
Ethylene-acrylic acid copolymers, and olefin polymers and olefin copolymers such as ethylene-methacrylic acid copolymers having a methacrylic acid content of 5 to 20% by weight.

Further, a graft copolymer obtained by grafting a carboxylic acid group-containing monomer such as an unsaturated carboxylic acid or a carboxylic acid anhydride onto a polyolefin containing the above-mentioned olefin polymer and olefin copolymer, or a blend thereof is also included. Suitable carboxylic acid group-containing monomers for grafting onto polyolefins include unsaturated carboxylic acids and carboxylic acid anhydrides such as maleic anhydride, citraconic acid anhydride, fumaric acid, acrylic acid, glycidyl acrylate, hydroxymethacrylate, derivatives thereof and these. A mixture of
Of these, maleic anhydride is the preferred grafting monomer. Generally, the amount of monomer grafted to the olefin homopolymer or olefin copolymer is
About 0.1 to about 10% by weight, preferably 0.5 to 5% by weight, based on the weight of ungrafted polyolefin. As other olefin-based polymers, ethylene-acrylic acid-maleic anhydride copolymers having an acrylic acid content of 5 to 20% by weight and a maleic anhydride content of less than 5% by weight are also used.

The hydrophobic resin has a melt viscosity (200 ° C., 25
sec ⁻¹ ) is 100 to 5000 Pa · s, preferably 300 to 2000 Pa · s, and more preferably 400 to 1
200 Pa · s is preferable.

2. Dyeability resin A and non (or low) dyeability
Combination of Resin B This combination is a suitable combination example among the combinations using resins having different dyeability, and the hydrophilic resin A described above is used.
The combination of and the hydrophobic resin B can also be used as the combination of the dyeable resin A and the non- (or low) dyeable resin B. If necessary, a group capable of reacting with a dye, for example, a group containing a hydroxyl group, an amino group, a carboxyl group or a salt thereof may be introduced into the main chain of the dyeable resin.

When a suitable dye is applied to the resin sheet of the present invention having such areas having different dyeability, only the easily dyeable area is selectively dyed to obtain a resin sheet having a striped colored portion.

3. Combination of high adhesive resin A and low adhesive resin B
Combined this combination is a preferred combination examples in combination using the degree of adhesion is different resins, a resin sheet made of a resin B having a resin A and a low adhesion with high adhesion to the particular resin When the above-mentioned sheet made of a specific resin is adhered, the area where the resin A is exposed functions as a high adhesive area, while the area where the resin B is exposed functions as a low adhesive area.

The following are examples of other combinations of resins having different surface characteristics.

A combination of resins having different reactivity to plasma, a combination of resins having different reactivity to radiation, a combination of resins having different surface gloss, a combination of resins having different surface hardness, and a resin having different friction coefficient Combination of resins with different heat resistance.

The resin sheet of the present invention having the inhomogeneous surface characteristics obtained as described above can of course be used as it is as various packaging materials, covering materials, etc. Further, it is possible to back it with, for example, a polyamide resin layer, a polyester resin layer, glass cloth, or the like. On the other hand, after applying patterning by utilizing the heterogeneous surface characteristics such as dyeability, surface coating is performed, and generally, the surface characteristics are appropriately controlled, or overcoating for the purpose of protection, or thin film Affixing can also be performed as needed.

Hereinafter, production examples and comparative examples of resin sheets having non-uniform surface characteristics will be described.

Example 1 (Dyeability) As shown in FIG. 4 (a), a spiral die (m = 16) for forming a slanted laminate capable of alternately inflowing two kinds of resins was used to form two kinds of resins into a cylinder. Were co-extruded into a sheet shape to obtain a resin sheet having a diagonal laminated structure. As the two kinds of resins, a copolymer of 6Ny and 12Ny as a hydrophilic resin (hereinafter referred to as “6-1
2Ny ”) and an ethylene-methacrylic acid copolymer (hereinafter abbreviated as“ EMAA ”) as a hydrophobic resin.
The obtained resin sheet has a length of 300 mm in the entire circumferential direction, and the total thickness of each layer is 6-12 Ny = 60 μm.
m, EMAA = 120 μm, and the number of laminated layers in a specific plane direction position was 6 to 7. 6-12Ny uses a copolymer composition ratio of 6Ny and 12Ny of 50/50 mol% and a melt viscosity (200 ° C., 25 sec ⁻¹ ) = 814 Pa · s (“Amilan CM6541X3” manufactured by Toray Industries Inc.), EMAA has a methacrylic acid content of 12% by weight (“Nucrel 1207C” manufactured by DuPont Mitsui Polychemicals,
Melt viscosity (200 ° C, 25sec ^-1 ) = 450Pa
s) was used. The obtained resin sheet was dyed with potassium iodide.

Example 2 As a hydrophilic resin, thermoplastic polyurethane (hereinafter referred to as "TP
A resin sheet was obtained in the same manner as in Example 1 except that "U" was abbreviated), and the dyeability was evaluated.

TPU has a melt viscosity (200 ° C., 25 sec.
⁻¹ ) = 730 Pa · s (“Kuramiron U3185” manufactured by Kuraray Co., Ltd.), and EMAA is the same as that used in Example 1.

Example 3 As shown in FIG. 4 (a), two kinds of resins were coextruded into a cylindrical shape by using a spiral die (m = 32) for forming a slanted laminate capable of alternately inflow processing two kinds of resins. A resin sheet having a diagonal laminated structure was obtained. The obtained resin sheet has a length in the entire circumferential direction of 300 mm, and the total thickness of each layer is 6-12 Ny = 100 μm and EMAA = 100 μm.
m, the number of laminated layers at a specific plane direction position was 14 to 15 layers. 6-12Ny and EMAA are the same as those used in Example 1. The obtained resin sheet was dyed with Patent Blue 5 (manufactured by Tokyo Chemical Industry Co., Ltd .: highly reactive with amino groups).

The melt viscosity in the present specification is R
A value of 25 sec ^-1 was calculated based on the result of measurement under the following conditions using a rotational viscometer "DSR" manufactured by Heometrics.

・ Test temperature 200 ° C. ・ Shear rate 0.1 to 1000 sec ^-1・ Jig parallel plate ・ Gap distance 2 mm

The specifications of the spiral die used in Examples 1 to 3 are as follows.

[Specifications of Spiral Die] (Examples 1 and 2) • Number of spiral threads (number of spiral channel grooves) 16 Hydrophilic resin side 8 Hydrophobic resin side 8 • Number of channel windings 1.5 • Spiral pitch starting point and the groove depth and width groove depth at the end of the pitch angle 19.3 ° spiral flow path groove of 6.875Mm spiral (mm) width (mm) hydrophilic resin side beginning 10 5 endpoint 0 0 hydrophobic Resin side Start point 6.5 5 End point 0 0 ・ Size of gap between spiral crest and outer die ring and its change in extrusion direction Start point 0 mm End point 1.5 mm ・ Inner die ring diameter and its extrusion direction Change start point 100 mm end point 97 mm (Example 3) -spiral stripe number (spiral channel groove number) 32 hydrophilic resin side 16 hydrophobic resin side 16-number of turns of channel 1.0 Starting point and the groove depth at the end and the width groove depth of the pitch angle 27.7 ° spiral flow path groove pitch 5.156Mm spiral of Iraru (mm) Width (mm) hydrophilic resin side start point 5 3.5 End point 0 0 Hydrophobic resin side Start point 5 3.5 End point 0 0 ・ Size of gap between spiral crest and outer die ring and its change in extrusion direction Start point 0.5 mm End point 1.25 mm ・ Inner die ring Of diameter and its change in extrusion direction Start point 100 mm End point 97.5 mm

Comparative Example 1 A normal two-layer spiral die was used to co-extrude all the layers into a cylindrical shape to produce a two-layer sheet as a control of Example 1. The length of the sheet in the entire circumferential direction was 300 mm, and the structure of the sheet was as follows.

[0055] The resin used is the same as that used in Example 1. The obtained resin sheet was dyed with potassium iodide.

The extrusion conditions in the above Examples and Comparative Examples are as shown in Table 1 below.

The evaluation results of the obtained film are summarized in Table 2 below.

[0058]

[Table 1]

[0059]

[Table 2]

Examples 4 to 6 (anti-fog property) Resin sheets obtained in Examples 1 to 3 (state before dyeing)
Was used to cover the beakers (50 cc) each containing water at 23 ° C., with the front side facing the water surface side, and the perimeter was stopped with a rubber band. After standing in an atmosphere of 5 ° C. for 24 hours, the inside of the beaker was observed through the sheet.

As a result, in any of the films, water droplets adhered only to the hydrophobic resin portion inside the film, but water droplets did not adhere to the hydrophilic resin portion, and the contents could be sufficiently confirmed. The width of the water droplet adhered portion / water droplet non-adhered portion matched the width of the colored portion / non-colored portion shown in Table 2.

Comparative Example 2 As in Examples 4 to 6, the two-layer resin sheet (before dyeing) obtained in Comparative Example 1 was covered with a beaker containing water at 23 ° C. with its hydrophobic resin (EMAA) side face inside. The antifogging property was evaluated. As a result, water droplets adhered to the entire inner surface of the film, making it impossible to visually check the contents.

Example 7 (Adhesiveness) In a normal three-layer spiral die for inflation, a third layer forming die part is an oblique laminate in which two kinds of resins can be alternately flow-processed as shown in FIG. 4 (a). Forming die (m =
32), using the obtained three-layer spiral die,
All the layers were coextruded into a cylindrical shape at the same time to produce a multilayer unstretched sheet including the resin sheet having the obliquely laminated structure of the present invention. Its length in the entire circumferential direction was 300 mm, and its structure was as follows. The manufacturing conditions are shown in Tables 3 and 4.
Shown in

Layer resin sheet / bonding resin layer / EVA thickness (μm) 120 15 120 The resin sheet (oblique laminate) has a thickness of layer EVOH =
60 μm (total), layers 6-12 Ny = 60 μm (total), and the total number of laminated layers is 14 to 15 layers. The outline of each resin is as follows.

EVA: an ethylene-vinyl acetate copolymer having a vinyl acetate content of 15% by weight (manufactured by Nippon Unicar "NUC
3753 ", melt index (190 ° C, 2160
g load) = 1.5 g / 10 min). It was used as an inner layer resin of a multilayer unstretched sheet.

Bonding resin layer: ethylene-vinyl acetate copolymer graft-modified with maleic anhydride ("MODIC E-300K" manufactured by Mitsubishi Yuka, melt viscosity (200 ° C, 2
5 sec ⁻¹ ) = 708 Pa · s) 6-12 Ny: the same as in Example 1 EVOH: ethylene content 44 mol%, saponification degree 99.
A 4% saponified ethylene-vinyl acetate copolymer having a melt viscosity (200 ° C., 25 sec ⁻¹ ) of 901 Pa · s (Kuraray's “EVAL EPE-105A”) was used.

When the adhesive force between the resin sheet (obliquely laminated body) portion and the bonding resin layer in the obtained laminate was measured, the adhesive force was measured at the portion where EVOH was exposed on the surface (width: approx. 8mm) and 6-12Ny exposed part (width about 1
1 mm). Moreover, anisotropy was shown depending on the measurement direction. The results are shown in Table 5 below.

Example 8 A multilayer unstretched sheet containing the resin sheet of the present invention was produced in the same manner as in Example 7 except that the constituent resin was changed. The composition was as follows. The manufacturing conditions are shown in Tables 3 and 4.

Layer resin sheet / EVA thickness (μm) 120 120 The resin sheet (oblique laminate) has a thickness of layer hydrogenated styrene-butadiene-styrene block copolymer (hereinafter referred to as “SE”).
Abbreviated as "BS". ) = 60 μm (total), layer polymethylmethacrylate (hereinafter abbreviated as “PMMA”) = 60
In μm (total), the number of laminated layers is 14 to 15. The outline of each resin is as follows.

EVA: The same as used in Example 7 was used.

SEBS: Asahi Kasei "Tuftec H105"
1 ”was used.

PMMA: Sumipex B manufactured by Sumitomo Chemical
MHO "was used.

When the adhesive force between the resin sheet (obliquely laminated body) portion of the obtained laminate and the EVA layer was measured, the adhesive force was measured at the portion where PMMA was exposed on the surface (width: about 9 mm). And the part where SEBS is exposed (width about 10m
m), and showed anisotropy in the measurement direction. The results are shown in Table 5 below.

Example 9 In a conventional five-layer spiral die for inflation, a die for forming a third layer, which can alternately process two kinds of resins as shown in FIG. m =
32) and using the obtained 5-layer spiral die,
All the layers were coextruded into a cylindrical shape at the same time to produce a multilayer unstretched sheet containing the resin sheet (oblique laminate) of the present invention. After that, simultaneous biaxial stretching was carried out by an inflation method to produce a multilayer stretched sheet containing the oblique laminate of the present invention. The length of the stretched film in the entire circumferential direction was 660 mm, and the configuration thereof was as follows. The manufacturing conditions are shown in Tables 5 and 6.

Layer EVA / bonding resin layer / diagonal laminate / bonding resin layer / IO thickness (μm) 20 2.5 20 2.5 2.5 45 The resin sheet (oblique laminate) part has a thickness of layer EVOH.
= 10 μm (total), layer acid-modified EEA = 10 μm (total), and the number of layers is 14 to 15 layers.

IO: An ionomer resin (“Mimil AM79082”, manufactured by DuPont Mitsui Polychemicals) was used.

EVA: The same as in Example 7 was used.

EVOH: The same as in Example 7 was used.

Acid-modified EEA: Acid-grafted ethylene-ethyl acrylate copolymer (manufactured by Nippon Synthetic Chemical Industry)
"N polymer A-1600", melt viscosity (200 ° C,
25 sec ⁻¹ ) = 730 Pa · s) was used.

Bonding resin layer: The same resin layer as in Example 7 was used.

The adhesive force between the resin sheet (obliquely laminated body) portion of the obtained laminate and the bonding resin layer was measured. The adhesive force was measured at the portion where EVOH was exposed on the surface (width: about 20 mm). ) And the acid-denatured EEA in the exposed portion (width of about 22 mm) were different, and anisotropy was exhibited in the measurement direction. The results are shown in Table 5 below.

The spiral die used in Examples 7 to 9 was the one used in Example 3.

Comparative Example 3 Using a normal two-layer spiral die, all layers were coextruded in a cylindrical shape to produce a two-layer unstretched sheet as a control of Example 7. Its manufacture was as follows.

Layer 6-12Ny / bonding resin layer / EVA thickness (μm) 120 15 120 The resin used is the same as that used in Example 1 for 6-12Ny and the bonding resin and EVA used in Example 7.

The delamination adhesion load shown in Table 5 was measured as follows.

It was measured under the following conditions using a tensile tester "Tensilon RTM-100" manufactured by Orientec.
(Based on JIS K-6854) ・ Test method T-type peeling test ・ Test temperature 23 ° C ・ Test humidity 50% RH ・ Pulling speed 200 mm / min ・ Sample size Width 15 mm Length 148 mm (Example 7, Example 8, comparison) Example 3) 325 mm (Example 9) -Measurement direction MD, TD-Method of processing measurement results Optimal linear method

[0087]

[Table 3]

[0088]

[Table 4]

[0089]

[Table 5]

[0090]

EFFECTS OF THE INVENTION Examples 1 to 9 and Comparative Examples 1 to 3 described above.
As can be seen from the comparison, according to the present invention, a resin sheet can be obtained in which stripe-shaped regions that are distinctly different in terms of surface characteristics such as dyeability, antifogging property and adhesiveness are regularly arranged.

[Brief description of drawings]

FIG. 1 is a perspective view and a bidirectional sectional view of a conventional laminated resin sheet.

FIG. 2 is a perspective view (a), a bidirectional sectional view (b), (c) and a plan view (d) of a resin sheet according to an embodiment of the present invention.

FIG. 3 is a sectional view of a conventional multi-layer spiral die and a sectional view of a product sheet.

FIG. 4 is a cross-sectional view of a spiral die suitable for manufacturing the resin sheet of the present invention and a cross-sectional view of a product sheet.

5 is a schematic perspective view of a main part of the spiral die of FIG.

[Explanation of symbols]

1: Laminated resin sheet (1a, 1b: its two main surfaces) A, B: Constituent resin 10a, 10b, 10c: Extruder 11, 21: Spiral die 12a, 12b, 22a, 22b: Die ring 22ab: Inner / outer die ring Interstitial flow paths 13a, 23a1, 23a2, 23a3, 23b1, 2
3b2, 23b3: Tournament branch part 14a, 24a, 24b: Spiral flow channel groove 15a, 15b, 15c, 25: Cylindrical flow channel 16: Confluence point 17, 27: Die lip 28a, 28b: Final flow channel of distribution part

Claims (6)

[Claims] 1. A resin sheet in which a plurality of resins having different surface characteristics are regularly and repeatedly arranged in stripes on the surface. 2. The resin sheet according to claim 1, wherein the plurality of resins are laminated obliquely in the thickness direction and are exposed on the back surface. 3. The resin sheet according to claim 1, wherein the different surface characteristics are hydrophilic and small. 4. The resin sheet according to claim 1, wherein the different surface characteristics are different in dyeability. 5. The resin sheet according to claim 1, wherein the different surface characteristics are antifogging property. 6. The resin sheet according to claim 1, wherein the different surface characteristics have different adhesiveness.