JP2002240121A - Method for producing laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a laminate which is bonded strongly without using an anchor coating agent and almost odorless. SOLUTION: The method for producing the laminate composed of a base material and an extrusion lamination resin includes a surface activation process (1) in which at least one side of the base material is activated, an ozone treatment process (2) in which the resin is extruded at 180-340 deg.C into a film, and at least one side of the film is treated with ozone, a press process (3) in which the activated surface of the base material is pressed to the ozone-treated surface of the film, and a modification process (4) in which the resin surface of the laminate obtained in the process (3) is contacted with a photocatalyst-functional film while being irradiated with light to be deodorized.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for manufacturing a laminate. More specifically, the present invention relates to a method for producing a laminate comprising a substrate and an extruded laminate resin, which is excellent in low odor.

[0002]

2. Description of the Related Art Characteristics that cannot be obtained by attaching film-shaped molded products of different materials such as plastic, paper, metal, etc. alone, such as strength, gas barrier properties, fragrance retention, moisture proofing, heat sealing properties, and appearance. It is common practice to produce a laminate with a supplemented shape and the like, and the laminate obtained in this way is widely used mainly for packaging materials and industrial materials.

[0003] As a method of manufacturing such a laminated body,
For example, there are a dry lamination method, a wet lamination method, a hot lamination method, an extrusion lamination method, a co-extrusion lamination method, and the like, and these are applied according to their characteristics. In the case of forming a heat seal layer on a base material of a packaging material or the like, an extrusion lamination method which is advantageous in cost is widely used.
As the heat seal layer, for example, polyethylene resin,
Polyolefin resins such as polypropylene resins and ethylene copolymer resins, ionomer resins, and the like are generally used, but polyolefin resins are used in a much larger amount in terms of cost.

[0004] These resins are coated with an anchor coat agent on the substrate in advance to promote adhesion to the substrate.
It is generally melt-extruded on the surface to be bonded to the substrate. As the anchor coat agent, for example, an adhesion promoter such as an organic titanate, an organic isocyanate, or a polyethyleneimine is used. These adhesion promoters
Usually, it is used after being diluted with an organic solvent such as toluene, ethyl acetate, ethanol and hexane. However,
These methods using the anchor coating agent require a complicated process of applying and drying the anchor coating agent, the organic solvent scattered during the evaporation and drying of the organic solvent contained in the anchor coating agent, and the working environment and the Due to the problem of hygiene in the surrounding environment, the danger of fire due to the use of flammable organic solvents, and the anchor coating agent components such as organic solvents remaining in the final product laminate, resulting in odor. In addition, there is a problem that the application range of the product is limited.

[0005]

As a method which does not use an anchor coating agent having many problems, a laminated body is manufactured by combining a surface oxidation treatment step or a surface activation treatment step and a ozone treatment step of a plastic base material. (Japanese Patent Application Laid-Open Nos. Hei 7-314629 and Hei 9-234845). However, although the film adhesive strength of the laminate obtained by the above method is greatly improved and has practicality, there is a case where it is desired to improve the odor, for example, particularly in applications requiring low odor among food packaging materials. Was. In view of such a situation, an object of the present invention is to provide a method for producing a laminate that is firmly bonded without using an anchor coating agent and has excellent low odor.

[0006]

The present invention relates to a method for producing a laminate comprising a substrate and an extruded laminate resin,
The present invention relates to a method for manufacturing a laminate including the following steps (1) to (4). Step (1) Surface activation treatment step: a step of performing a surface activation treatment on at least one surface of the substrate. Step (2) Ozone treatment step: Extruded laminating resin to 18
A step of melt-extruding a film at a resin temperature of 0 to 340 ° C. and subjecting at least one surface thereof to ozone treatment. Step (3) Compression bonding step: The surface activation-treated surface of the base material obtained in the step (1) is brought into contact with the ozone-treated surface of the film-shaped extruded laminate resin obtained in the step (2), and compression-bonded. Process. Step (4) Modification action step: A step of contacting the photocatalytic functional film while irradiating light to the extruded laminate resin surface of the laminate obtained in Step (3) to remove odor. Hereinafter, the present invention will be described in detail.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The substrate used in the present invention may be in the form of a film or sheet, and may be a stretched or unstretched product. Further, it may be a woven fabric, a nonwoven fabric or a foam. Further, the substrate may be made of metal or plastic, or may be a bonded product with another material, for example, aluminum foil, iron foil, paper, or the like. The thickness of the base material is not particularly limited as long as extrusion lamination can be performed.
m or less, more preferably 5 to 500 μm.

The substrate used in the present invention is preferably a plastic substrate among the above. Specific examples of such a plastic substrate include, for example, nylon resin, polyester resin, ethylene-vinyl alcohol copolymer resin, polyvinyl alcohol resin, polypropylene resin, cellophane, cellulose resin, polyvinylidene chloride resin, and polystyrene. Resin, polyvinyl chloride resin,
A simple substance such as a polycarbonate-based resin, a polymethylmethacrylate-based resin, a polyurethane-based resin, a fluorine-based resin, and a polyacrylonitrile-based resin, and a laminated film or sheet thereof, and a stretched product, a coated product, a woven fabric, and the like can be given. Among these, the substrate used in the present invention is preferably a substrate composed of a nylon resin, an ethylene-vinyl alcohol copolymer resin, a polyester resin, a polypropylene resin, or a polyethylene resin. In the present invention, these plastic substrates are bonded products with aluminum foil, iron foil, copper foil, paper, and the like, and may be a laminate in which these plastic substrates are provided on a bonding surface. Further, a plastic substrate on which an inorganic substance such as aluminum or silica is deposited may be used, and a substrate having a resin coating layer called a top coat layer on the deposition surface may be used. These plastic base materials may be printed in advance.

The extruded laminating resin used in the present invention is not particularly limited, and may be any resin that can be extruded and laminated, such as a polyethylene resin, an ethylene copolymer resin, a polypropylene resin, and poly-4-methyl-. 1 Penten resin, nylon resin, polyester resin,
Examples thereof include an ethylene-vinyl alcohol copolymer resin and an ionomer resin.

Here, the ethylene copolymer resin is a resin obtained by copolymerizing one to four types of comonomer components capable of copolymerizing with ethylene. For example, a copolymer of ethylene and (meth) acrylic acid is used. Adhesive functions such as coalescing resin, copolymer resin of ethylene and (meth) acrylic acid ester, copolymer resin of ethylene and maleic anhydride, and copolymer resin of ethylene and epoxy compound are provided. An adhesive resin can be used. Examples of the ionomer resin include resins obtained by partially or completely neutralizing these adhesive resins with metal ions such as zinc and sodium. The adhesive resin may be a resin produced by a graft polymerization method, for example, a resin obtained by graft-polymerizing an acid anhydride such as maleic anhydride to a polyethylene resin or a polypropylene resin.

Among the above-mentioned resins, polyethylene-based resins, ethylene-based copolymer resins, and polypropylene-based resins are particularly preferred in terms of productivity and cost.

The method for producing the polyethylene resin is not particularly limited, and it can be produced by, for example, a radical polymerization method or an ionic polymerization method. Examples of the polyethylene resin include low-density polyethylene produced by a radical polymerization method, high-density polyethylene produced by an ionic polymerization method, and linear low-density polyethylene obtained by copolymerizing ethylene and an α-olefin. And the like. Examples of the α-olefin here include propylene, butene-1, 4-methyl-1-pentene, 1-hexene, 1-hexene,
Α-olefins having 3 to 18 carbon atoms such as octene, 1-decene and 1-octadecene are used.
Olefins can be used alone or in combination of two or more. The content of the repeating unit derived from the α-olefin contained in the ethylene-α-olefin copolymer (linear low-density polyethylene) is preferably from 1 to 40.
%, More preferably 5 to 30% by weight. Preferably, the low-density polyethylene or the linear low-density polyethylene is used as the polyethylene resin.

Among the ethylene copolymer resins, an ethylene-vinyl ester copolymer resin or an ethylene- (meth) acrylate copolymer resin is preferred from the viewpoint of cost. The ethylene-vinyl ester copolymer-based resin and the ethylene- (meth) acrylate copolymer-based resin can each be produced by a radical polymerization method, and are obtained by copolymerizing ethylene with a radically polymerizable monomer. .

The vinyl ester used for producing the ethylene-vinyl ester copolymer resin includes, for example, vinyl acetate, vinyl propionate and the like.

The (meth) acrylate used in the production of the ethylene- (meth) acrylate copolymer-based resin includes, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, and n-acrylate. Acrylates such as -butyl, t-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n-methacrylate
Methacrylates such as -propyl, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate and isobutyl methacrylate; One or more of these comonomers can be used.

The content of the repeating unit derived from the vinyl ester or the (meth) acrylate contained in the ethylene-vinyl ester copolymer resin or the ethylene- (meth) acrylate copolymer resin is as follows:
It is preferably 30% by weight or less, more preferably 2% by weight.
0% by weight or less is preferred.

From the viewpoint of processability, the polyethylene resin, ethylene-vinyl ester copolymer resin, and ethylene- (meth) acrylate copolymer resin each have a melt flow rate (MFR) at 190 ° C. Is preferably in the range of 1 to 100 g / 10 minutes.

As the polypropylene resin, for example, a homopolymer of propylene, propylene and ethylene or 1-
Copolymers with an α-olefin such as butene are exemplified. Examples of the α-olefin referred to here include 1-butene, 1-hexene, 1-octene, and the like, and one or more of these may be used. The content of the repeating unit derived from ethylene and / or α-olefin contained in the copolymer of propylene and ethylene and / or α-olefin is preferably 0.1%.
It is 1 to 40% by weight, more preferably 1 to 30% by weight. The method for producing the polypropylene resin is not particularly limited, and for example, it can be produced by an ionic polymerization method.

The extrusion laminated resin used in the present invention includes:
As long as the effects of the present invention are not impaired, known additives such as antioxidants, antiblocking agents, weathering agents, neutralizing agents,
Flame retardants, antistatic agents, antifogging agents, lubricants, dispersants, pigments, organic or inorganic fillers, and the like may be used in combination.

The step (1) surface activation treatment step of the present invention is a step for generating a certain level or more of activation points on the adhered surface of the base material and enabling strong adhesion to the extruded laminate resin. The surface activation treatment is preferably performed by corona discharge treatment, electron beam irradiation treatment, ultraviolet irradiation treatment, flame plasma treatment, atmospheric pressure plasma treatment, or low pressure plasma treatment.

The corona discharge treatment is a treatment for performing a corona discharge treatment on at least one surface of the substrate. The corona discharge treatment is performed, for example, by passing the base material under a generated corona atmosphere using a known corona discharge treatment machine. Here, the atmosphere of the corona discharge treatment may be the atmosphere, or may be an atmosphere adjusted with an inert gas (for example, nitrogen) or the like. Corona discharge treatment is usually 10W
· Min / m ² or more, preferably 30 to 300 W · min / m ²
It is.

The electron beam irradiation treatment is performed by irradiating the surface of the substrate with an electron beam generated by an electron beam accelerator. As the electron beam irradiation apparatus, for example, an apparatus “electron curtain” (trade name) capable of irradiating a uniform electron beam in a curtain shape from a linear filament can be used. Here, the atmosphere of the electron beam irradiation treatment may be in the air, or may be in an atmosphere adjusted with an inert gas (for example, nitrogen) or the like. From the viewpoint of maintaining the film adhesive strength between the base material and the extruded laminate resin at a high level, the electron beam irradiation dose is preferably 5 kGy or more, more preferably 15 kGy or more, and still more preferably 30 kGy.
y or more. The upper limit of the amount of electron beam irradiation is not particularly limited, and is usually about 200 kGy. Here, the irradiation dose is set with respect to the line speed of the base film at the entrance side of the irradiation device. In addition, the effect of irradiation is often brought about in the thickness direction of the base material only by irradiating one surface of the base material due to the property that the electron beam is transmitted through many objects.

The ultraviolet irradiation treatment is, for example, 100 to 400
The irradiation is performed by irradiating an ultraviolet light having a wavelength of nm to the adhered surface of the substrate. Here, the atmosphere of the ultraviolet irradiation treatment may be under the air or under an inert gas (for example, nitrogen) atmosphere.

The flame plasma treatment is performed by spraying an ionized plasma flame in a flame generated when natural gas, propane gas or the like is burned onto the surface of the substrate.

Atmospheric pressure plasma treatment is performed at atmospheric pressure under argon, helium, krypton, neon, xenon, hydrogen,
The method is performed by electronically exciting a simple substance or a mixed gas such as nitrogen or air with a plasma jet, and then spraying an excited inert gas onto the surface of the base material. In particular,
Usually, an AC voltage of 3 to 5 kHz and 2 to 3000 V is applied between the electrodes to generate an excited inert gas.

The low-pressure plasma treatment is performed under reduced pressure (usually 0.1 to
5 Torr) at a power of 200 to 1000 W with argon, helium, krypton, neon, xenon, hydrogen,
After electronically exciting a single or mixed gas such as nitrogen or air with a plasma jet, the charged particles are removed, and an electrically inert excited inert gas is sprayed on the surface of the substrate. .

In the present invention, when a substrate made of a polyethylene resin, an ethylene-vinyl alcohol copolymer resin, a polyester resin or a nylon resin is used as the substrate used in the step (1), the step (1) It is preferable that the surface activation treatment is a corona discharge treatment in an air atmosphere.

In the present invention, when a substrate made of a polyester resin is used as the substrate used in the step (1), the surface activation treatment in the step (1) may be performed by corona discharge treatment in an inert gas atmosphere or The electron beam irradiation treatment in an inert gas atmosphere is more preferable.

In the present invention, when a substrate made of a polypropylene resin is used as the substrate used in the step (1), the surface activation treatment in the step (1) may be performed by flame plasma treatment or under an inert gas atmosphere. Preferably, it is a corona discharge treatment.

The step (2) of the present invention, the ozone treatment step, is a step in which the extruded laminate resin is melt-extruded into a film at a resin temperature of 180 to 340 ° C., and at least one surface thereof is subjected to an ozone treatment. The ozone treatment is performed, for example, by blowing a gas (for example, air) containing ozone onto a molten film-like extruded laminate resin from a nozzle or a slit-shaped outlet provided in an air gap below the T-die. When an ozone nozzle or the like cannot be installed under the T-die, a gas (eg, air) containing ozone is blown onto the base material immediately before the pressure bonding step, and the ozone is brought into contact with a film-like extruded laminate resin in the vicinity thereof. It may be made to act.

The amount of the ozone to be sprayed depends on the substrate and the extrusion
Especially if it can improve the adhesion to
There is no restriction, but generally the unit area of the molten film
(M ^Two ) Is preferably 0.1 to 100 mg;
More preferably, it is 1 to 50 mg.

The resin temperature at which the extruded laminate resin is melt-extruded into a film is 180 to 340 ° C. When the temperature is lower than 180 ° C., the spreadability of the resin may be poor, and it is not only difficult to obtain a molten thin film having a uniform thickness, but also the adhesiveness to the base material becomes insufficient. There is. On the other hand, the resin temperature may exceed 340 ° C., but in the case of a substrate having poor heat resistance, heat shrinkage or the like of the substrate is likely to occur in the pressure bonding step, which may cause a problem in stable production of the product, which is not preferable. . The preferred resin temperature is 2
10-330 ° C.

In the step (3) of the present invention, the pressure-bonding step comprises the step of activating the surface of the base material obtained in the step (1) and the step of treating the ozone-treated surface of the extruded laminate resin in the form of a film obtained in the step (2). And pressure bonding. In the pressure bonding step of the present invention, a known extrusion laminator can be used.

In the present invention, the step (1) of the surface activation treatment step and the step (3) of the pressure bonding step may be provided in-line or off-line. preferable. In addition, the above-mentioned "providing the surface activation treatment step and the pressure bonding step in-line"
In the extrusion lamination process, the substrate feeding process, the surface activation process, the pressure bonding process, and the product winding process are performed using an apparatus that is sequentially installed on the same line along the flow direction of the substrate. In a series of operations. In addition, offline means all processes other than in-line, for example, store the substrate after the surface activation process in another warehouse for several minutes to several months, and then guide the substrate from the unreeling process It refers to the method of applying the pressure bonding process.

In the present invention, from the viewpoint of further improving the adhesive strength to the base material, it is preferable to provide, after the pressure bonding step, a ripening step of aging the laminate obtained in the pressure bonding step while keeping the temperature of the laminate. The aging temperature is usually 30 ° C. or more and less than 50 ° C., preferably 40 to 45 ° C. When the aging temperature is too low, the improvement of the adhesive strength may be insufficient. On the other hand, if it is too high, there is no problem in improving the adhesiveness, but it is not preferable in terms of economy. The aging time is usually 1 to 120 hours, preferably 10 to 100 hours. When the aging time is short, the improvement of the adhesiveness may be insufficient, while when it is too long, it is disadvantageous in terms of productivity. In order to carry out the aging step, a normal oven or a room capable of adjusting the temperature may be used.

In the present invention, a surface activation treatment step,
By performing all of the ozone treatment step, the pressure bonding step, and the aging treatment step in combination, a stronger adhesive strength between the substrate and the extruded laminate resin can be realized.

The step (4) modifying action step of the present invention is a step of removing the odor by bringing a photocatalytic functional film into contact with the extruded laminate resin surface of the laminate obtained in the step (3). In the step (4) modifying action step of the present invention, at least three or more layers of a base material, an extruded laminate resin, and a sand fed resin base material (sealant film) manufactured by, for example, a sandwich lamination method are laminated. By contacting the photocatalytic function film with the surface of the multilayer body, it can be used in a step of removing odorous substances diffused and transmitted from the inner layer of the multilayer body to the surface.

The photocatalytic function film used in the step (4) reforming step of the present invention is not particularly limited as long as it has a photocatalytic function. For example, titanium oxide-based compounds, silicon oxide-based compounds, tungsten oxide-based compounds, oxidized A photocatalytic film containing a zinc compound, a copper oxide compound, a vanadium oxide compound, a molybdenum oxide compound, a chromium oxide compound, or an iron oxide compound as a main component is used. Further, the photocatalytic function film may be added with a metal substance (Au, Ag, Cu, etc.) in order to make the function more effective, or the photocatalytic function film may have a hybridized structure. Good.

In the present invention, the form of the photocatalytic functional film used in the step (4) is not particularly limited, but may be a form coated on a polymer resin material, a metal material, an inorganic material (eg, glass) or a paper material. Alternatively, a material obtained by kneading a compound having a photocatalytic function into a resin or the like and molding it into a woven form (for example, a net or a nonwoven fabric) may be used.

The function film is irradiated with light such as natural light or artificial light to promote the effect of the photocatalytic function film used in the (4) reforming process of the present invention. Irradiation with light is preferred.
As the ultraviolet wavelength, those containing 300 to 400 nm as a main wavelength are more preferable.

The step (4) of the present invention may be carried out in any step of handling the laminate after the pressure bonding step, for example, a slitting step of a laminated product, a product rewinding step, a product shipping inspection step, It may be performed in a bag making process, a can making process or a product filling process. Further, in the modifying step, the shape of the laminated product is not particularly limited, and may be a long product wound up in a roll shape, or may be a single-wafer plate. Further, it may be in the form of a bag after a bag making process.

In the present invention, a resin extruded and laminated on a substrate can be applied to a heat seal layer of a laminated film or sheet, or can be applied to an intermediate layer of a laminated film or sheet. Function, for example, easy heat-sealing property and moisture-proof property. Further, the present invention can be applied to a sandwich extrusion lamination method.

The laminate obtained by the present invention can be used as a packaging film, for example, a food packaging material, as a laminated film or a laminated sheet.
Applicable to packaging materials for pharmaceuticals and industrial supplies.

[0044]

Next, the present invention will be described with reference to examples. In addition, the evaluation method of the obtained laminated film is as follows.

(1) Measurement of film adhesive strength: A laminated film having a width of 15 mm was measured at 200 (or 50) mm / mi using an automatic strain type tensile tester manufactured by Toyo Seiki Co., Ltd.
The film adhesive strength was evaluated from the peel strength when peeled at 180 ° at a pulling speed of n. (Unit: g / 15mm width)

(2) Sensory evaluation of odor: The odor of the laminated film was examined by a sensory test of three panelists. The evaluation criteria are as follows. “△” indicates that application may be restricted. "O" indicates that further improvement is preferred. “◎” indicates that the product has a sufficient improvement effect and is applied to a wide range.

[Example 1] An ethylene-vinyl alcohol copolymer resin film "EVOH film EF manufactured by Kuraray Co., Ltd." was used as a base material from a main feeding device of an extrusion laminator.
−XL; 15 μm ”, and a treatment density of 88 W · min / min.
m ² , a surface activation treatment step was performed, followed by a compression bonding step, and a low-density polyethylene (LDPE; Sumikasen CE4009 manufactured by Sumitomo Chemical Co., Ltd., MFR 7 g)
/ 10 min, density 0.919 g / cm ³ )
The mixture was melted and kneaded with an extruder having a resin temperature of 315 ° C., a film width of 500 mm, a laminate layer thickness of 30 μm, and a lamination speed of 80 m / min. Further, air containing ozone was blown from a nozzle provided at a position 40 mm below the die onto the bonding surface of the molten film with the base material to ozone-treat the bonding surface of the molten film. The ozone treatment amount at this time was 30 mg / m ² . Through the above steps, a laminated film composed of two layers was wound by a winder.

The laminated film produced through the pressure bonding step is cut to the size of an A4 plate, fixed on a paperboard so that the extruded laminated resin layer becomes the surface, and a transparent photocatalytic functional film (manufactured by Nippon Soda Co., Ltd.) The viscator F) was overlaid on the extruded laminate resin layer. Further, a commercially available fluorescent lamp was used to irradiate the photocatalytic function film at a position 5 mm below the light source for 3 seconds to perform a reforming process. Thereafter, the laminated film was taken out and subjected to a sensory test by a panel to examine whether or not the odor was improved. Table 1 shows the processing conditions and evaluation results.

Example 2 A substrate was made of a biaxially stretched nylon film “biaxially stretched nylon film ON;
The same procedure as in Example 1 was performed except that the thickness was changed to 5 μm.
Table 1 shows the processing conditions and evaluation results.

Example 3 The substrate of Example 1 was changed to a biaxially stretched polyester film “Toyobo's biaxially stretched polyester film E5100; 16 μm”, and the surface activation treatment step was performed using nitrogen gas (oxygen control concentration). 50pp
m) Corona discharge treatment in an atmosphere (discharge treatment density is 80 W
Min / m ² ). Further, a laminated film was obtained in the same manner as in Example 1, except that the thickness of the laminate layer was changed from 30 μm to 25 μm and the ozone treatment amount was changed from 30 mg / m ² to 12 mg / m ² . Next, using a commercially available black light irradiation lamp, the film was brought into face-to-face contact with a photocatalytic functional film (Bistrate F) at a position 5 mm below the light source for 2 seconds to perform a reforming action step. Thereafter, a sensory test was conducted by a panelist. The film adhesion strength was evaluated by changing the take-up speed to 50 mm / min. Other conditions were the same as in Example 1. Table 1 shows the processing conditions and evaluation results.

Example 4 In the surface activation treatment step in Example 3, the base material was made of a biaxially oriented polypropylene film “Biaxially oriented polypropylene film M-
1:20 μm ”, and a laminated film was obtained in the same manner as in Example 3, except that the surface activation treatment step was performed offline using a flame plasma treatment apparatus.
Next, using a commercially available black light irradiation lamp, the film was brought into face-to-face contact with the photocatalytic function film (Bistrate F) at a position 5 mm below the light source for 5 seconds to perform a reforming action step. Thereafter, a sensory test was conducted by a panelist. Other conditions were the same as in Example 3. Table 1 shows the processing conditions and evaluation results.

[Comparative Example 1] The same operation as in Example 1 was performed except that the reforming action step was not performed. Although the film adhesive strength between the base material and the extruded laminate resin could not be peeled off and sufficient adhesive strength was obtained, it was expected that the use might be limited in some cases due to slight odor. Table 2 shows the processing conditions and the evaluation results.

Comparative Example 2 Instead of the reforming process in Example 3, the odor was improved by contacting with ultrapure water adjusted to 29 ° C. for 5 seconds. Other conditions were the same as in Example 3. As a result, the film adhesive strength between the base material and the extruded laminate resin was obtained to have practically useful strength, and the odor surface was slightly improved, but it was not sufficient yet, and it could not be said that it was sufficient. Was expected to be limited in some cases. Table 2 shows the processing conditions and the evaluation results.

[Comparative Example 3] Instead of the reforming action step in Example 4, the odor was improved by contacting with hot air adjusted to 60 ° C for 5 seconds. Other conditions were the same as in Example 4. As a result, the adhesive strength of the film between the base material and the extruded laminate resin has a practically useful strength, and a slight improvement in the odor surface has been slightly recognized, but it is still not sufficient,
It was expected that the range of application could be limited depending on the application. Table 2 shows the processing conditions and the evaluation results.

[0055]

[Table 1]

[0056]

[Table 2]

The comprehensive evaluations in Tables 1 and 2 above are the results of comprehensive evaluation of the laminated films obtained according to the following criteria. "△" indicates that application may be restricted. "O" indicates that further improvement is preferred. "◎" indicates that the product has sufficient practicality. Further,-in the table indicates a case where the process is not performed.

[0058]

As described in detail above, according to the present invention, a laminate comprising a substrate and an extruded laminate resin,
A method for producing a laminate that is firmly adhered without using an anchor coat agent having many problems and that is excellent in low odor can be provided.

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Claims (9)

[Claims] 1. A method for producing a laminate comprising a substrate and an extruded laminate resin, comprising the following steps (1) to (4):
A method for producing a laminate, comprising: Step (1) Surface activation treatment step: a step of performing a surface activation treatment on at least one surface of the substrate. Step (2) Ozone treatment step: Extruded laminating resin to 18
A step of melt-extruding a film at a resin temperature of 0 to 340 ° C and subjecting at least one surface thereof to ozone treatment. Step (3) Compression bonding step: The surface activation-treated surface of the base material obtained in the step (1) is brought into contact with the ozone-treated surface of the extruded laminate resin in the form of a film obtained in the step (2), and compression-bonded. Process. Step (4) Modification action step: A step of contacting the photocatalytic functional film while irradiating light to the extruded laminate resin surface of the laminate obtained in Step (3) to remove odor. 2. The laminate according to claim 1, wherein the surface activation treatment in step (1) is a corona discharge treatment, an electron beam irradiation treatment, an ultraviolet irradiation treatment, a flame plasma treatment, an atmospheric pressure plasma treatment or a low pressure plasma treatment. Manufacturing method. 3. The amount of ozone treatment in the step (2) is 0.1 to 10 per unit area (m ² ) of the extruded molten resin film.
3. The method for producing a laminate according to claim 1, wherein the amount is in a range of 0 mg. 4. The extruded laminate resin melt-extruded in the step (2) is a polyethylene resin, a polypropylene resin, an ethylene-vinyl ester copolymer resin and an ethylene- (meth) acrylate copolymer resin. The method for producing a laminate according to any one of claims 1 to 3, which is a resin selected from the group consisting of: 5. The photocatalytic functional film used in the step (4) is a photocatalytic functional film containing a titanium oxide compound, a silicon oxide compound, a tungsten oxide compound, a zinc oxide compound or a copper oxide compound as a main component. The method for producing a laminate according to any one of claims 1 to 4, wherein 6. The method according to claim 1, wherein the substrate used in step (1) is a plastic substrate. 7. The substrate used in the step (1) is a substrate made of a polyethylene resin, an ethylene-vinyl alcohol copolymer resin, a polyester resin or a nylon resin, and the surface activity in the step (1). The method for producing a laminate according to any one of claims 1 to 5, wherein the conversion treatment is a corona discharge treatment in an air atmosphere. 8. The substrate used in the step (1) is a substrate made of a polyester resin, and the surface activation treatment in the step (1) is a corona discharge treatment or an inert gas atmosphere under an inert gas atmosphere. 6. A lower electron beam irradiation process.
The method for producing a laminate according to any one of the above. 9. The substrate used in the step (1) is a substrate made of a polypropylene resin, and the surface activation treatment in the step (1) is a flame plasma treatment or a corona discharge treatment in an inert gas atmosphere. A method for producing a laminate according to any one of claims 1 to 5.