JP6503572B2 - Multilayer laminated film and method of manufacturing the same - Google Patents

Description

  The present invention relates to a multilayer laminated film, and more specifically, a chemical agent by laminating a fiber-containing EVOH thin layer (B), a pressure-sensitive adhesive layer (C) containing a chemical agent and an additive to a support layer (A). And suppress scattering of additives, have production stability and good handling, and are excellent in medicinal effects such as deodorizing property, insect repellent property, freshness holding property, etc. The present invention relates to a multilayer laminated film in which the skin residue of the pressure-sensitive adhesive layer (C) is significantly reduced when the laminated film is removed.

Ethylene-vinyl alcohol copolymer (hereinafter referred to as EVOH), which is generally excellent in transparency, gas barrier properties, odor retention, solvent resistance, oil resistance, etc. , Films for chemicals, films for agriculture, etc.
Above all, dangerous chemicals are volatilized and leaked to the outside, and the adherend having a curved surface and elasticity can be made to penetrate the chemicals to effectively exert medicinal effects, and easy to attach and remove. A flexible film is desired, and a multilayer laminate film has been proposed in which a chemical-containing pressure-sensitive adhesive layer is laminated on at least one side of an EVOH layer effective in terms of chemical resistance and barrier properties. .

  As a method of incorporating a large amount of the chemical into the adhesive, there is a method in which the chemical is directly added to the adhesive, but the compatibility and dispersibility of the adhesive and the chemical are poor, and the drug efficacy is efficient. Often can not be expressed. Therefore, in order to impart compatibility between the adhesive and the chemical, a method is used in which an additive containing a compatibilizer such as a plasticizer is mixed with the adhesive. However, the pressure-sensitive adhesive layer containing a large amount of chemicals, a compatibilizer and the like has a problem that sufficient adhesion with the EVOH layer can not be obtained.

  In addition, since EVOH resin having good chemical resistance is rigid, the multilayer film including the EVOH layer has a curved surface and is not only difficult to be attached to a stretchable object, but also during adhesion There is a problem that the drug effect can not be obtained sufficiently efficiently from the adherend, and dangerous chemicals scatter. Therefore, a method to make the EVOH layer as thin as possible is considered, and although it is possible to make it flexible, conversely, the flexibility causes problems of deterioration in process passability at the time of production and handleability at the time of use. Will occur.

  For example, Patent Document 1 manufactures a laminate composed of a polyolefin (hereinafter abbreviated as PO) layer / EVOH layer / sealant (melt adhesive material) layer, and a deodorizing agent and volatile matter are formed on the inner surface of the bag. By attaching resin films into which various functional chemicals such as antifungal agents and volatile antibacterial agents are incorporated and improving the atmosphere in the bag, the substances in the bag can be deodorized and the occurrence of mold and fungus can be prevented. Although it is described, because the form is a bag, there is a problem that it can not be adopted for large-scale equipment such as furniture, wood, machinery and the like.

  Further, Patent Document 2 describes a rustproof film in which an EVOH resin layer containing a volatile rustproofing agent is laminated on the surface of a polyolefin-based film. Further, Patent Document 3 discloses a rustproof film in which a polyvinyl alcohol layer and a plastic thin film having a high water vapor barrier property are formed on one side of a plastic film containing a volatile rustproofing agent. It is described that it is frequently used for transport packaging of electronic parts and automobile parts. However, in any of the anticorrosive films of Patent Documents 2 and 3, the anticorrosive agent bled out to the surface of the anticorrosive film causes a lamination failure, which makes processing difficult and causes defects such as peeling during use. There was a problem to occur.

  On the other hand, Patent Document 4 discloses an EVOH layer / PO layer / (PO + volatilization) in which an EVOH layer having good gas barrier properties is laminated on the outermost layer in order to reduce evaporation and volatilization of the volatile rust inhibitor into air. It is described that a multilayer laminated stretch film composed of an anti-corrosion agent layer / ethylene / vinyl acetate copolymer (hereinafter referred to as EVA) layer is also effective as an anti-corrosion measure for large-scale mechanical equipment There is. However, in the multilayer laminated film of Patent Document 4, it is necessary to use an adhesive, the adhesion is deteriorated due to bleeding of a chemical agent, and defects such as peeling may occur during use, and a rigid EVOH layer By laminating the layers, the stretchability is greatly reduced. For example, when small parts such as parts are wrapped, a large number of wrinkles are generated and the barrier property with the outside air becomes poor, so the corrosion resistance during long-term storage is deteriorated. Not only that, but also the appearance is not desirable as a product.

  Furthermore, Patent Document 5 discloses laminating an (EVOH + deodorant) layer / (adhesive + deodorant) layer in multiple layers and applying it to furniture, wood or the like to impart deodorant properties. However, since the (EVOH + deodorant) layer is rigid, it is necessary to make the layer thinner, and along with that, a flexible substrate (such as PVC) is further laminated for the purpose of improving the handleability, for example, Also disclosed is a multilayer laminate composed of resin (PVC etc.) layer / adhesive layer / (EVOH + deodorant) layer / (adhesive + deodorant) layer. However, if an attempt is made to improve the adherability to the adherend having a curved surface portion and an elastic portion by imparting flexibility as in the laminated film of the above-described constitution, the handleability as a film is rather deteriorated. , Can not achieve both workability and flexibility.

Unexamined-Japanese-Patent No. 2003-335376 Japanese Patent Publication No. 52-13988 Unexamined-Japanese-Patent No. 01-297241 Unexamined-Japanese-Patent No. 2000-326455 Japanese Patent Application Laid-Open No. 10-29280

As a basic composition used for a multi-layer laminated film for sticking which exhibits medicinal effects such as deodorizing property, insect repellent property, freshness holding property, and anticorrosion support layer / adhesive layer (chemicals, additives included) / protective layer (Protect the adhesive layer and remove it just before application),
a) Anti-scattering properties of chemicals and additives that greatly affect drug efficacy,
b) Stable adhesion to the adherend, in particular, stable adhesion on the curved surface and the stretchable part (partial peeling, detachment prevention),
c) peelability when removing the multilayer film, adhesive adhesive residue prevention property, and delamination resistance property of the multilayer film,
d) Stable productivity of the multilayer film, and good handleability (removability from the packaging material, operability for sticking to the object to be affixed, and removability from the object to be affixed, etc.)
Is a technical issue, and various studies have been made, but no sufficient solution has yet been found.

  As described above, the film used for the support layer is required to have anti-scattering properties of chemicals, additives and the like, and as a film satisfying this required performance, the barrier properties of chemicals and additives, There is a proposal using a PET film or EVOH film having resistance to dissolution and swelling. However, these films have difficulty in obtaining a thin film due to limitations in terms of production, and as a result, the rigidity becomes high, and partial peeling or detachment occurs in a curved portion or a bent portion when the multilayer film is attached. It caused serious problems such as reduction of medicinal effects.

In addition, when the adhesiveness between the support layer and the pressure-sensitive adhesive layer is low, when the multilayer film is peeled from the adherend, peeling between the support layer and the pressure-sensitive adhesive layer precedes, and the pressure-sensitive adhesive layer adheres Remain in the thing. Therefore, when the pressure-sensitive adhesive layer is removed from the adherend, a large problem may occur in terms of safety and health, such as the pressure-sensitive adhesive adhering to the skin such as a finger.
As a method of improving the adhesion between the support layer and the pressure-sensitive adhesive layer, a method (such as an anchor coat containing a crosslinking agent such as isocyanate) on the interface of the film forming the support layer is proposed. However, when a crosslinking agent such as isocyanate is used, the adhesive strength may be greatly reduced by the action of the chemical contained in the multilayer film, and there is also a problem in terms of safety and health.

  Therefore, according to the present invention, chemical agents and additives hardly scatter, and the followability of the curved surface and the elastic surface of the adherend is improved, and a stable medicinal effect can be ensured, and further, no adhesive residue of the pressure-sensitive adhesive layer is left when peeling off. It is an object of the present invention to provide a novel multi-layer laminated film for application, which has medicinal effects.

  As a result of intensive investigations by the present inventors to achieve the above object, it is preferable to apply an EVOH resin containing fibers on a film forming a support layer or to laminate and dry the fibers immediately after the application of the EVOH resin. In the resulting multilayer laminate film, when the multilayer laminate film is removed from the adherend after application, almost no residue of the pressure-sensitive adhesive layer is observed on the adherend, and adsorption of a chemical agent and an additive, We found that volatilization was suppressed and reached the present invention.

  That is, the present invention is a multilayer film in which an EVOH layer (B) containing fibers, an adhesive layer (C), and a protective layer (D) are sequentially laminated on a support layer (A), and the fiber containing It is a multilayer laminate film having a peel strength between the EVOH layer (B) and the pressure-sensitive adhesive layer (C) of 50 g / 15 mm width or more, preferably the fiber content in the fiber-containing EVOH layer (B) is 1 to 95 It is said multilayer laminated film which is weight%.

  Furthermore, according to the present invention, preferably, the fiber-containing EVOH layer (B) is a method of applying and drying an EVOH solution containing fibers on a support layer (A), after applying the EVOH solution, at least a part of the fibers. Manufactured by either the method of laminating and drying the fiber so as to be impregnated with the EVOH solution, or the method of extrusion laminating the molten thin layer of the fiber containing EVOH resin to the support layer (A), Multilayer laminated film.

According to the present invention, the process passability and the handling property are good, the chemicals and additives hardly scatter, and the adhesion between the EVOH layer (B) and the pressure-sensitive adhesive layer (C) is significantly improved. And when peeling off a multilayer laminated film from a to-be-adhered body, the multilayer laminated film in which residual substances, such as a paste contained in an adhesive layer (C), are hardly recognized is obtained.
It is not clear why the adhesion between the EVOH layer (B) and the pressure-sensitive adhesive layer (C) is significantly improved, but the surface of the fiber-containing EVOH layer (B) is affected by the bulkiness of the fibers. It is presumed that the adhesive (C) is easily penetrated into the EVOH layer (B) because it is presumed to be covered with fine irregularities, and as a result, the adhesiveness between the EVOH layer (B) and the adhesive layer (C) is It is thought that it is because it improved significantly.

The support layer (A) constituting the multilayer laminated film of the present invention plays a role of maintaining the form of the fiber-containing EVOH layer (B) formed by coating on one side thereof, and the process passability during production and stability It greatly contributes to productivity and easy handling. The material used for the support layer (A) is preferably a film, and specifically, polyvinyl chloride resin film, polyester resin film such as polyethylene terephthalate (PET), polyethylene, polypropylene, ethylene-acetic acid Examples include various plastic films such as polyolefin resin films such as vinyl copolymer, polyurethane (hereinafter abbreviated as PU) resin films, etc. A laminated film in which one or more of them are combined or a film in which PET is replaced by polyethylene The configuration is more preferable.
The film forming the support layer (A) is produced by a known melt extrusion film forming method. As a melt extrusion method of resin, there are a single layer film forming method, a single layer extrusion laminating method, a multilayer coextrusion method, a multilayer coextrusion laminating method and the like.

  Furthermore, in order to obtain a more flexible multilayer laminated film, a multilayer film in which a support layer (A), a fiber-containing EVOH layer (B), an adhesive layer (C) and a protective layer (D) were sequentially laminated was prepared. Thereafter, there is a method of removing the support layer (A). In that case, a support layer (A) and a fiber-containing EVOH layer (B) formed by applying a specific EVOH solution described later, which is a feature of the present invention, onto the support layer (A) It is preferred to control the peel strength. Specifically, the peel strength between the support layer (A) and the EVOH layer (B) is preferably 10 to 200 g / 15 mm width, more preferably 20 to 150 g / 15 mm width, still more preferably 30 to It is 100 g / 15 mm wide. When the peel strength is less than 10 g / 15 mm width, there may be bending during the process of multilayer laminate film production, and a step of applying and drying a solution for adhesive on the fiber-containing EVOH layer (B) side, etc. In this case, peeling occurs between the two layers, which significantly reduces the production yield or causes the support layer (A) to peel first in an attempt to peel off the protective layer (D) of the multilayer laminated film. There is a great possibility. On the other hand, if the peel strength is greater than 200 g / 15 mm width, the production stability and yield will be improved, but after peeling off the protective layer (D), the multilayer laminate film is made to adhere to the adherend and finally the support In the step of removing the layer (A), there may occur a problem that delamination may occur between the adherend / pressure-sensitive adhesive layer (C) or the pressure-sensitive adhesive layer (C) / fiber-containing EVOH layer (B) .

  The peel strength between each layer is (a) <Peel strength between EVOH film (B) / adhesive layer (C)> (a), <peel strength between adhesive layer (C) / adhered body> (b) Where <Peel strength between support layer (A) / EVOH film (B)> is (c), <Peel strength between pressure-sensitive adhesive layer (C) / protective layer (D)> is (d), It is preferable that (a)> (b)> (c)> (d).

  As a method of controlling the peel strength between the support layer (A) and the EVOH layer (B), it is preferable to process the surface of the film forming the support layer (A) on the side in contact with the EVOH layer (B) . As a processing method, a method of performing corona treatment or plasma treatment on the film surface, a method of kneading fine particles to impart anchoring properties of the film, a method of applying and drying a binder liquid containing fine particles, a film surface Embossing, blasting, or chemical coating methods such as primer treatment, anchor treatment, mold release treatment in some cases, and a combination thereof are used for the purpose of giving unevenness mechanically and uniformly. Among these, corona treatment, anchor treatment and embossing treatment are more desirable.

  The fiber-containing EVOH layer (B) used in the present invention preferably has a thickness of 5 μm or less. If it is thicker than 5 μm, the layer (B) itself becomes too hard, causing problems in the stretchability to the object after sticking. More preferably, it is 4 micrometers or less, More preferably, it is 2 micrometers or less. From the viewpoint of water resistance, strength, etc., an EVOH resin having an ethylene content of 20 to 55 mol%, particularly 25 to 50 mol%, and a saponification degree of vinyl acetate component of 90 mol% or more, particularly 95 mol% or more And those having an intrinsic viscosity in the range of 0.7 to 1.5 dl / g are preferable. If the ethylene content is less than 20 mol%, the film itself becomes hard, and a sticky feeling occurs when sticking an object to be attached, or the followability to the object to be attached is deteriorated, and the feeling of adhesion tends to be poor. On the other hand, when the ethylene content exceeds 55 mol%, the hydrophobicity is increased, so the oil additive in the pressure-sensitive adhesive layer tends to be adsorbed, which is not preferable. In addition, if the degree of saponification of the vinyl acetate component is less than 90 mol%, adsorption and migration of chemicals and additives become remarkable, which is not preferable. Furthermore, when the intrinsic viscosity is less than 0.7 dl / g, mechanical strength is insufficient, and when the intrinsic viscosity exceeds 1.5 dl / g, it often becomes difficult to manufacture. Here, the intrinsic viscosity means one measured at a temperature of 30 ° C. in a mixed solvent of water / phenol 15/85 in weight ratio.

The EVOH resin is obtained by saponification of an ethylene-vinyl acetate copolymer, but the EVOH resin can be produced by any known polymerization method such as solution polymerization, suspension polymerization, emulsion polymerization and the like. Thus, saponification of the ethylene-vinyl acetate copolymer can also be carried out by a known method. Moreover, if it is less than 50% by mass of the EVOH resin to be constituted, α-olefin, unsaturated carboxylic acid compound, unsaturated sulfonic acid compound, (meth) acrylonitrile, (meth) acrylamide, vinyl ether, vinylsilane compound, vinyl chloride It may be an EVOH resin copolymerized and modified with other comonomers such as styrene, and may be an EVOH resin modified after urethanization, acetalization, cyanoethylation and the like.
In addition, various additives such as antioxidants, ultraviolet light absorbers, inorganic fine particles, organic fine particles, thickeners, and plasticizers may be added in small amounts as long as the purpose of the present invention is not impaired.

In the present invention, the EVOH resin to be applied to the surface of the film forming the support layer (A) or a solution containing the EVOH resin and fibers (hereinafter collectively referred to as an EVOH solution) uses the EVOH resin as a solvent Dissolve and prepare. As the solvent to be used, water / alcohol is preferable. Among them, water / isopropanol, water / n-propanol, water / n-butanol, water / sea-butanol, water / isobutanol, etc. Furthermore, it is more preferable from the economical point of view. In the case of a water / alcohol solvent, the weight ratio of water / alcohol in the solvent is preferably 5/95 to 80/20 from the viewpoint of solution stability and transparency.
Further, it is further preferable to mix formic acid, phenol, dimethylformamide, N-methylpyrrolidone or the like in the above-mentioned solvent in a proportion of 1 to 30% by mass because solution stability and transparency are improved.

  The concentration of the EVOH resin in the EVOH solution is preferably in the range of 1% by mass to 20% by mass. If the concentration of the EVOH resin is less than 1% by mass, the coated layer after drying may be too thin, the surface may become cloudy, and the appearance may be impaired. On the other hand, if it exceeds 20% by mass, the concentration of the EVOH resin is too high, so the workability at the time of coating is inferior, and the gloss unevenness due to the drying unevenness of the coating layer tends to occur.

The fiber material used in the fiber-containing EVOH layer (B) is not particularly limited, but polyesters such as PET, viscose rayon, copper ammonia rayon, dicarbonate, triacetate, polyamide, polyvinylidene chloride, polyvinyl alcohol, polyvinyl chloride And various synthetic fibers such as polyacrylonitrile, polyethylene, polypropylene, PU, polyalkylene paraoxybenzoate, EVOH, and natural fibers such as cotton, wool, silk and hemp.
Among them, fibers containing polyester such as PET and fibers containing EVOH are preferable. Short fibers, non-woven fabrics, and woven fabrics made of single fibers or a blend of two or more fibers can be used. Among these, it is preferable from the viewpoints of flexibility and adhesiveness to use one having a fiber basis weight of about 5 to 100 g / m ² .

  In the fiber-containing EVOH layer (B), a resin layer (B ') having flexibility is laminated between the EVOH layer and the pressure-sensitive adhesive layer (C), and fibers are further mixed or laminated on the layer (B') side. It is preferable because the strength of the laminated film is increased while securing strong adhesiveness with the pressure-sensitive adhesive layer (C), and the problem of adhesion of a residue such as glue to the adherend at the time of peeling is significantly improved. In particular, the thickness of the layer (B ') is preferably 0.5 μm or more. If the thickness is less than 0.5 μm, the adhesion between the EVOH layer and the fiber layer is insufficient and peeling occurs during process passing. There is a problem that becomes easier.

  The resin constituting the resin layer (B ') having flexibility is not particularly limited, such as an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, and a silicone-based pressure-sensitive adhesive. The resin is preferably a resin having good dispersibility with fibers and adhesiveness, and among them, silicone-based and acrylic-based adhesives are more preferable. The resin layer (B ′) may be the same resin as the pressure-sensitive adhesive layer (C), or may have the same composition, or a completely different resin or a different composition, and is not particularly limited.

  As a method of obtaining the fiber-containing EVOH layer (B), a method of laminating the fibers such as the non-woven fabric and the woven fabric and applying final drying after applying the prepared EVOH solution to the support layer (A) or in the middle of drying A method of electrodepositing piles such as short cut fibers instead of non-woven fabric, a method of blending fibers into a coating solution and applying after strong stirring, or a blend of fibers with EVOH resin, then the fiber-containing EVOH resin as a support layer (A A method of extrusion laminating on a film forming the As a method of blending fibers into EVOH resin, for example, a method of mixing short fibers with EVOH solution and strongly stirring, a method of charging EVOH resin into a twin-screw extruder, kneading of short fibers under melting, etc. However, the present invention is not limited to these methods.

  In the fiber-containing EVOH layer (B), a resin layer (B ') having flexibility is laminated between the EVOH layer and the pressure-sensitive adhesive layer (C), and fibers are further mixed on the layer (B') side or As a method of laminating, a layer (B ') is formed by applying and drying an adhesive solution containing a resin having flexibility on a thin layer obtained by applying and drying the prepared EVOH solution on a support layer (A). And a method of dry laminating a fiber such as a non-woven fabric under heating, or a method of applying and drying a flexible pressure-sensitive adhesive solution in which a pile such as a short fiber is mixed in an EVOH layer.

The fiber content of the fiber-containing EVOH layer (B) is 1% of the total weight to strengthen the adhesion between the fiber-containing EVOH layer (B) and the pressure-sensitive adhesive layer (C). It is preferably -95 wt%, more preferably 3-90 wt%. If the fiber content is less than 1% by weight, the adhesion to the pressure-sensitive adhesive layer (C) is not sufficient, while if it is more than 95% by weight, uneven coating occurs, and on the contrary, sufficient adhesion can not be obtained, For example, when it manufactures by the extrusion lamination method, extrusion property may deteriorate and film forming may become difficult.
When the peel strength between the pressure-sensitive adhesive layer (C) and the fiber-containing EVOH layer (B) is lower than that of the pressure-sensitive adhesive layer (C) and the adherend, the fiber-containing EVOH layer (B) peels off first and There is a problem that adhesive residue is easily generated on the attached body. In order to prevent this problem in advance, the peel strength between the fiber-containing EVOH thin layer (B) and the pressure-sensitive adhesive layer (C) needs to be 50 g / 15 mm or more, preferably 100 g / 15 mm or more. More preferably, the width is 150 g / 15 mm or more and 400 g / 15 mm or less.

  In the multilayer laminate film of the present invention, the pressure-sensitive adhesive layer (C) formed on one side of the fiber-containing EVOH layer (B) contains a chemical agent and an additive, and adheres to a good adherend From the viewpoint of the property, it is formed with a thickness of usually 10 to 300 μm, preferably 15 to 250 μm.

  Chemicals are added to the pressure-sensitive adhesive layer (C), but when chemicals with different functions are further added, the functions can be more efficiently exhibited by adding the chemicals to the fiber-containing EVOH layer (B) side There is a case. For example, by adding an oxygen absorbent or an ultraviolet light inhibitor to the fiber-containing EVOH layer (B) side, oxidation or ultraviolet deterioration of a chemical added to the adhesive layer (C) can be prevented, and the medicinal effect of the chemical can be prevented. Effects such as suppressing the decrease in

  As a resin for forming the pressure-sensitive adhesive layer (C), for example, acrylic pressure-sensitive adhesives having a pressure-sensitive property at normal temperature, rubber-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, vinyl ether-based pressure-sensitive adhesives, etc. are used. It can be used in combination.

As an acrylic pressure-sensitive adhesive, for example, homopolymers having (meth) acrylic acid alkyl ester (here, (meth) acrylic acid means methacrylic acid or acrylic acid) as a main component and alkyl (meth) acrylate A copolymer of an ester and a copolymerizable monomer or a (co) polymer of an aliphatic alcohol having 4 to 18 carbon atoms and a (meth) acrylic acid alkyl ester is preferable.
Examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid isobutyl ester, (meth) Acrylic acid hexyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid isooctyl ester, (meth) acrylic acid decyl ester, (meth) acrylic acid isodecyl ester, (meth) acrylic acid lauryl ester, (meth) Acrylic acid stearyl ester etc. are mentioned.
Examples of the copolymerizable monomers include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, butyl maleate, 2-hydroxyethyl (meth) acrylate, dimethylamino acrylate, hydroxypropyl (meth ) Acrylate, acrylamide, dimethyl acrylamide, diethyl acrylamide, butoxymethyl acrylamide, ethoxymethyl acrylamide, methylol (meth) acrylamide, N-vinyl-2-pyrrolidone, vinyl acetate, vinyl propionate, styrene, α-methyl styrene, vinyl chloride, Acrylonitrile, ethylene, propylene, butadiene and the like can be mentioned.

  The rubber-based pressure-sensitive adhesive is not particularly limited, and, for example, natural rubber, polyisoprene, polyisobutylene, polybutadiene, styrene-butadiene copolymer, styrene-butadiene-styrene copolymer, styrene-isoprene copolymer, styrene-isoprene A conventionally known rubber-based pressure-sensitive adhesive based on a rubber such as styrene copolymer, styrene-isoprene-styrene block copolymer, synthetic isoprene rubber, polyvinyl ether, polyurethane and urethane rubber can be used.

  The silicone pressure-sensitive adhesive is not particularly limited, and examples thereof include silicone rubber such as polyorganosiloxane and the like.

  Examples of vinyl ether adhesives include vinyl ether, isobutyl ether, methyl isobutyl ether and ethyl isobutyl ether.

  Moreover, in the pressure-sensitive adhesive layer (C), when the cohesion of the pressure-sensitive adhesive is low, the pressure-sensitive adhesive may be cohesively broken in the pressure-sensitive adhesive layer (or inside the pressure-sensitive adhesive) and residual substances such as glue remain on the adherend. May occur. In order to increase the cohesion of such an adhesive or to increase the amount of additives retained, it is preferable to crosslink the adhesive layer (C). Specifically, physical crosslinking by radiation such as ultraviolet radiation or electron beam irradiation, or chemical crosslinking by an external crosslinking agent such as an isocyanate compound, an organic peroxide, an organic metal salt, a metal alcoholate, a metal chelate, or a polyfunctional compound. Crosslinking etc. may be mentioned, and when preparing a polymer for forming a pressure-sensitive adhesive layer by polymerization reaction, a polymer having internal crosslinking can also be obtained by copolymerizing a polyfunctional monomer.

  Among the various pressure-sensitive adhesives described above, it is easy to adjust for obtaining desired adhesion properties, improve the solubility (compatibility) of chemicals and additives, can be contained in a large amount, and is relatively easy to crosslink. Acrylic pressure-sensitive adhesives are preferred from the viewpoint of

  As additives contained in the above-mentioned pressure-sensitive adhesive layer (C), penetration accelerators, solubilizers, fillers, softening plasticizers, tackifiers, crosslinking agents, antioxidants, ultraviolet light absorbers, chemical decomposition inhibition Although an agent etc. are mentioned, it does not specifically limit and it can use combining 1 type, or 2 or more types.

  When a penetration enhancer is used as an additive contained in the above-mentioned adhesive layer (C), as a penetration enhancer, any of the compounds in which the absorption promotion effect to a body to be stuck is recognized, for example, C2-C4 Alcohols such as ethanol and isopropanol, polyethylene glycol monolaurate, polyethylene glycol 3-lauramide, dimethyl lauramide, sorbitan trioleate, fatty acids, esters of fatty acids having about 10 to about 20 carbon atoms, monoglycerides or monoesters In the case of monoesters with 10 to 20 carbon atoms, mixtures of monoglycerides of fatty acids having a total monoester content of at least 51% and mixtures of mono-, di- and tri-glycerides of fatty acids etc. are mentioned Be Fatty acids include, but are not limited to, lauric acid, myristic acid, stearyl acid, oleic acid, linoleic acid, and palmitic acid. As the monoglyceride penetration enhancer, for example, glycerol monooleate, glycerol monolaurate, glycerol monolinoleate and the like are preferable.

  When a solubilizer is used as the additive contained in the pressure-sensitive adhesive layer (C), the solubilizer is excellent in compatibility with the pressure-sensitive adhesive, sufficiently dissolves the chemical, and adheres to the chemical It may be one which has less bleeding (bleeding) from the agent layer and does not adversely affect adhesive properties and chemical release properties. Specifically, esters of fatty acids such as oleic acid, myristic acid, capric acid etc., organic acids such as adipic acid, dicarboxylic acids such as sebacic acid, and alcohols such as ethanol and 2-propanol; glycerin, propylene glycol Etc .; polyhydric alcohols and esters thereof with organic acids such as triacetin; polyethers such as polyethylene glycol, polypropylene glycol, polyoxyethylene hydrogenated castor oil, methyl ethyl ketone, N -Methyl 2- pyrrolidone; other crotamiton etc. are mentioned.

  When a filler is used as the additive contained in the pressure-sensitive adhesive layer (C), the filler is not particularly limited as long as it improves the cohesion of the pressure-sensitive adhesive in the pressure-sensitive adhesive layer, but silica and titanium oxide , Inorganic particles such as zinc oxide, magnesium oxide, iron oxide, aluminum hydroxide, talc, kaolin, bentonite, barium sulfate, calcium carbonate, etc., lactose, carbon black, polyvinyl pyrrolidone, polyester, polyolefin, polyurethane, polyamide, celluloses, acrylic Organic fine particles such as resins, etc., and fibers such as polyesters, polyolefins, polyurethanes, polyamides, celluloses, acrylic resins, glass, etc. may be mentioned.

  When using a softening plasticizer as an additive contained in the above-mentioned adhesive layer (C), as a softening plasticizer, petroleum oil, squalane, squalene, vegetable oil, silicone oil, dibasic acid ester, liquid rubber, Liquid fatty acid esters, diethylene glycol, polyethylene glycol, glycol salicylate, propylene glycol, dipropylene glycol, triacetin, triethyl citrate, crotamiton and the like can be mentioned.

  When a tackifier is used as the additive contained in the pressure-sensitive adhesive layer (C), tackifiers for rubber-based pressure-sensitive adhesives may be appropriately selected and used as the tackifier, for example, petroleum-based resins ( For example, aromatic petroleum resin, aliphatic petroleum resin), terpene resin, rosin resin, maleic acid resin, coumarone indene resin, styrene resin (for example, styrene resin, α-methylstyrene resin), hydrogenation Petroleum resin (for example, alicyclic saturated hydrocarbon resin) etc. are mentioned. Among them, alicyclic saturated hydrocarbon resins are preferable because the storage stability of chemical agents is improved. The tackifier may be used alone or in combination of two or more. When two or more are used in combination, for example, resins different in kind of resin and softening point may be combined.

  When a crosslinking agent is used as the additive contained in the above-mentioned pressure-sensitive adhesive layer (C), the crosslinking agent is not particularly limited, but such as amino resin, phenol resin, epoxy resin, alkyd resin, unsaturated polyester, etc. A thermosetting resin, an isocyanate compound, a block isocyanate compound, an organic type crosslinking agent, inorganic type crosslinking agents, such as a metal or a metal compound, etc. are mentioned.

  When an antioxidant is used as an additive contained in the pressure-sensitive adhesive layer (C), the antioxidant is not particularly limited, but tocopherol and ester derivatives thereof, ascorbic acid, ascorbic acid stearic acid ester , Nordihytrog ayaretic acid, dibutylhydroxytoluene (BHT), butylhydroxyanisole and the like.

  When an ultraviolet absorber is used as an additive contained in the above-mentioned adhesive layer (C), the ultraviolet absorber is not particularly limited, but p-aminobenzoic acid derivative, anthranilic acid derivative, salicylic acid derivative, coumarin Derivatives, amino acid compounds, imidazoline derivatives, pyrimidine derivatives, dioxane derivatives and the like can be mentioned.

  These additives contained in the pressure-sensitive adhesive layer (C) are preferably contained in the pressure-sensitive adhesive layer (C) in a range of 0.1 to 60% by weight, particularly 1 to 50% by weight. When the content is less than 0.1% by weight, the effect by containing the additive as described above may not be sufficiently exhibited, and when it is contained more than 60% by weight, the pressure-sensitive adhesive layer In some cases, the chemicals and additives can not be stably held, and the chemicals and additives may exude from the pressure-sensitive adhesive layer during storage and application to exhibit a stable effect. The adhesive layer may be crosslinked to facilitate retention of the chemical agent and the additive, but if the content of the additive is too large, the limit that can be retained by the crosslinking may be exceeded.

  The pressure-sensitive adhesive layer (C) in the multilayer laminate film of the present invention contains a chemical. Such chemical agents are not particularly limited, and, for example, oxygen absorbers, antibacterial agents, antibacterial agents, acaricides, deodorizing agents, biological repellents, mildew resistant agents, volatile mildew resistant agents, insect repellents, animal repellents Agents, rust inhibitors, corrosion inhibitors, preservatives, aldehydes adsorbents, deodorants, antioxidants, algaecides, oxygen scavengers, freshness holding components, surfactants, flame retardants, release agents, antistatic Agents, insulating agents, anti-coloring agents, UV absorbers, IR absorbers, water repellents, water absorbing agents, and volatile chemicals thereof, and chemicals such as pharmaceuticals, etc. can be used in combination of one or more kinds.

When a fungicide is used as the chemical contained in the adhesive layer (C), the fungicide is not particularly limited, but volatile fungicides, hydrophilic organic fungicides, etc. are mentioned. Be In addition, an oxygen scavenger can also be used to prevent the growth of aerobic bacteria.
When a volatile antifungal agent is used as the chemical agent contained in the adhesive layer (C), the volatile antifungal agent is not particularly limited, but organic tin compounds, organic sulfur compounds, chlorine compounds, Phenolic compounds, thymol and the like can be mentioned.
When a hydrophilic organic antifungal agent is used as the chemical agent contained in the pressure-sensitive adhesive layer (C), the hydrophilic organic antifungal agent is not particularly limited, but benzthiazole type, phenol type, isothiazoline type Examples are synthetic fungicides such as quaternary ammonium salts, phosphonium salts, benzimidazoles, phenols, isothiazolines, and pyridines, and natural fungicides such as chitosan, lysozyme, protamine and polylysine. Ru. Among these, the benzthiazole type, the phenol type and the isothiazoline type are effective in the small amount addition, and are preferable. Examples of these fungicides are 2- (4-thiazolyl) benzthiazole 2- (4-thiocyanomethyl-thio) benzthiazole, p-chloro-m-methylphenol, O-phenyl-phenol, 5- Chloro 2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one and the like can be mentioned. Among them, 2-n-octyl-4-isothiazolin-3-one is particularly preferable because the spectrum of effective fungi is broad and the toxicity is low.

When an antimicrobial agent is used as the chemical agent to be contained in the pressure-sensitive adhesive layer (C), although it is not particularly limited, inorganic antimicrobial agents, organic antimicrobial agents, volatile antimicrobial agents and the like can be mentioned. The inorganic antibacterial agent is not particularly limited, but is a halogen compound containing chlorine, bromine and iodine; copper arsenite, cuprous oxide, silver nitrate, glass containing silver and copper; crystalline silica Synthetic acid aluminum (zeolite), amorphous synthetic aluminum silicate such as aluminum silicate; Zirconium phosphate supporting ions such as Ag, Cu, Zn; Zinc oxide compounds; Magnesium oxide compounds; Calcium hydroxide compounds Etc. are included.
The organic antibacterial agent is not particularly limited, but nitrogen compounds such as amines and triazines; organometal compounds of arsenic, copper, mercury, tin and zinc; organic sulfur compounds such as isothiazolone and pyrithione thiocyanate; Quaternary ammonium compounds such as alkyldimethylbenzyl ammonium compounds; phenol compounds such as chlorinated phenol, bisphenol, o-phenylphenol and the like are included. In addition, antibacterial agents derived from natural products such as hinokitiol, wasauro and chitin chitosan can also be used. Examples of volatile antibacterial agents include, but are not limited to, isothiocyanic acid compounds, hinokitiol, bamboo extract oil, shiso extract oil, thiazolyl sulfamide compounds and the like.

  When using an anti-mite agent as the chemical agent contained in the pressure-sensitive adhesive layer (C), although not particularly limited, a volatile anti-mite agent is preferable. The volatile anticaritics are not particularly limited, and include, but are not limited to arethrin, tetramethrin, resmethrin, phenotoframethrin, permethrin, cypenothrin, tralomethrin, enpentrin, DDVP, phenithione, temephos, diflubenzuron, buprofezin, pyriproxyfen And peppermint oil etc.

  When an insect repellent is used as the chemical agent to be contained in the pressure-sensitive adhesive layer (C), although not particularly limited, a volatile insect repellent is preferable. Examples of volatile insect repellents include, but are not limited to, cresol, o-phenylphenol, parathion, imidazole and the like.

  When using an animal repellent as a chemical contained in the pressure-sensitive adhesive layer (C), although not particularly limited, a volatile animal repellent is preferable. Examples of volatile animal repellents include, but are not limited to, pyrethrin, rotenone, phthalthrin, arethrin, permethrin, cybomethrin, alphacybermethrin, phenothrin, cypenothrin, menthol, cypress oil, cedar oil, cypress oil, Examples include dithiocarbamolyl sulfide compounds, cinnamic aldehydes, linalool and the like.

  When a preservative is used as the chemical contained in the pressure-sensitive adhesive layer (C), it is not particularly limited. For example, organic iodine compounds, organic nitrogen sulfur compounds, organic bromine compounds, isothiazolone compositions, There is a bromo nitro alcohol composition and the like.

  When a deodorizing agent is used as the chemical contained in the pressure-sensitive adhesive layer (C), it is not particularly limited, but silica gel, activated alumina, titanium oxide, zinc oxide, carbon black, zeolite, activated carbon, amorphous silica, cyclodextrin And sepiolite, ceramics, etc., and activated carbon chemically treated with a substance such as amines, for example, granular white coral GAAx manufactured by Nippon EnviroChemicals, Inc. is a preferred example.

  When an aldehyde adsorbent is used as the chemical agent to be contained in the pressure-sensitive adhesive layer (C), there is no particular limitation, and examples of the organic compound having an amine group include urea, ethylene urea, propylene urea, and 5- Hydroxypropylene urea, 5-methoxypropylene urea, 5-methylpropylene urea, parabanic acid (glyoxal monourein), 4,5-dimethoxypropylene urea, hydrazine, pyrrolidine, piperidine, morpholine, dicyandiamide, 2-hydrazobenzothiazole, Or amines, such as derivatives thereof, amides, imides and the like, and among them, organic compounds of urea type and hydrazine type are preferable in view of aldehyde adsorption performance.

  When a deodorant is used as the chemical contained in the pressure-sensitive adhesive layer (C), it is not particularly limited, but polyalkyleneimines such as polyethyleneimine, vitamin E, tocophenol, titanium oxide, hydrazine derivative, amine compound (Pentaethylenehexamine, triethylenetetramine, polyvinyloxazoline, etc.), Inorganic base compounds (calcium oxide, calcium hydroxide, calcium carbonate, etc.), flavonoid deodorant, polyphenol, turpentine oil, activated aluminum oxide, magnesium silicate, silica Acid aluminum etc. are mentioned.

When a rust inhibitor is used as the chemical contained in the adhesive layer (C), there is no particular limitation, but a volatile rust inhibitor, zinc phosphate, tannic acid derivative, phosphoric acid ester, basic sulfonate, etc. And various rust preventive pigments. The volatile corrosion inhibitor is not particularly limited, and examples thereof include nitrites, ammonium compounds, urea compounds and mixtures thereof, etc., which cause hydrolysis or neutralization reaction, ammonium nitrite, ammonia And produce a highly volatile rust preventive such as nitrous acid to exhibit excellent rust preventive effect.
The nitrite is not particularly limited. For example, sodium nitrite, potassium nitrite, calcium nitrite, magnesium nitrite; the ammonium compound is not particularly limited, but is, for example, ammonium benzoate The ammonium phthalate, the ammonium stearate, the ammonium palmitate, the ammonium oleate; and the urea compound are not particularly limited, and examples thereof include urea, urotropin, phenyl carbamate and the like. Also, sodium benzoate, diisopropyl ammonium nitrite (DIPAN), dicyclohexyl ammonium nitrite (DICHAN), nitro naphthalene ammonium nitrite (NITAN), bicyclic benzoazole compound, monocyclic imidazole, Examples thereof include triazole, rosin, diisopropyl ammonium nitrite, benzoic acid, cabryllic acid, dicyclohexyl ammonium nitrite, dicyclo ammonium carbonate, nitrite and the like. Many of these volatile corrosion inhibitors are harmful to the human body, and care must be taken in their handling.
Examples of volatile corrosion inhibitors for iron include nitrites of amines, carboxylates of amines, chromates of amines, and esters of carboxylic acids.
For copper and copper alloys, there are, for example, those having a triazole ring, a pyrrole ring, a pyrazole ring, a thiazole ring, an imidazole ring, a thiourea, a mercapto group, which are heterocyclic compounds.

When an oxygen scavenger is used as the chemical contained in the pressure-sensitive adhesive layer (C), there is no particular limitation, but iron-based oxygen scavengers, non-ferrous oxygen scavengers, those which simultaneously absorb oxygen and carbon dioxide gas, etc. Metal powders such as iron and zinc, reductive lower oxides of iron such as FeO, FeTiO ₂ and Fe ₂ O ₃ , organometallic complexes, transition metal compounds, ascorbic acid, phenolic substance sulfite, hydrogen sulfite Salt, thiosulfate, oxalate, pyrogallol, catechol, Rongalite, vitamin C, nanocomposite nylon resin, polyester in which butanediol is branched into molecules, glucose and the like can be mentioned.

  When a freshness maintaining component is used as the chemical contained in the pressure-sensitive adhesive layer (C), it is not particularly limited, but isothiocyanate compound, spice extract, cinnamic aldehyde, geraniol, eugenol, carvacrol, thymol, borneol And pinene and the like, and isothiocyanate compounds are particularly useful.

In order to optimize the adhesiveness and releasability between the above-mentioned adhesive layer (C) and the object to be bonded, both the adhesiveness and releasability were made on the side of the adhesive layer (C) in contact with the protective layer (D). And re-peelable adhesive layer (C ') can be laminated.
For example, the removable pressure-sensitive adhesive layer (C ') on the side in contact with the object to be attached is made uneven and suckered to reduce the adhesion area with the object to be attached, and the adhesiveness and releasability by the suctioning function. The resin composition which makes it compatible is chosen. For example, it is effective to apply a resin having different degrees of polymerization, add a cross-linking agent, add a foaming agent, or the like, and perform an unevenness treatment.

  The multilayer laminated film of the present invention has the above-mentioned constitution, but generally it has a sheet form in which a known protective layer (D) is laminated to cover and protect the surface of the pressure-sensitive adhesive layer (C). Provided. In addition, the multilayer laminated film can ensure storage stability before use by sealing and packaging with a packaging material (E).

  The film used for the protective layer (D) is a film for covering and protecting the surface of the pressure-sensitive adhesive layer (C) until the patch is used, and the material is not particularly limited. , Polyethylene, polypropylene, ethylene-vinyl acetate copolymer, EVOH, polyvinyl chloride, polyurethane, polyethylene terephthalate, polybutylene terephthalate, polyester such as polyethylene naphthalate; polyamide such as nylon; polyacrylonitrile; cellulose or its derivative; A metal foil such as aluminum may, for example, be mentioned, and one of these may be used alone, or two or more may be used in combination. As such a film or sheet, in order to increase its releasability, the surface in contact with the pressure-sensitive adhesive layer may be previously subjected to silicone treatment, fluorine resin treatment or the like.

  As a packaging material (E), it is for sealing and storing or conveying this multilayer laminated film before use, and a heat-sealable thing is desirable from an airtight viewpoint. Specifically, a packaging material using a heat-sealable plastic sheet such as polyethylene, ionomer resin, ethylene-vinyl acetate copolymer, EVOH, polyacrylonitrile copolymer, polyvinyl alcohol copolymer, etc. is suitable. . In particular, in order to prevent contamination or oxidation decomposition of chemicals contained in the multilayer laminate film due to external air, gas impermeable films such as polyester films, EVOH films, and films or metal foils whose surfaces are vapor coated with an inorganic substance It is preferable to use a laminated film of an organic film.

  As a method for producing the multilayer laminated film of the present invention, for example, a pressure-sensitive adhesive, a chemical, a pressure-sensitive adhesive composition containing various additives is dissolved in a suitable solvent such as toluene, and the obtained solution is protected The first step of forming a pressure-sensitive adhesive layer (C) by applying to a film surface forming layer (D) and drying to form an adhesive layer (C), and applying and drying an EVOH solution on the surface of a film forming a support layer (A) There is a second step of forming a fiber-containing EVOH thin layer (B), wherein the multilayer film obtained from both steps is a thin layer composed of an adhesive layer (C) and an EVOH resin in a soft barrier thin layer. It manufactures by pressure-bonding in the direction which (B-1) faces. In the case of pressure bonding, if necessary, heat compression may be carried out to produce the multilayer laminated film. However, in the first step, the release agent on the film surface forming the protective layer (D) may transfer to the pressure-sensitive adhesive layer (C), and the adhesion between the pressure-sensitive adhesive layer and the object may be deteriorated. In the final step of pressure bonding in the direction in which the pressure-sensitive adhesive layer (C) and the EVOH layer (B) face each other, adhesion such as air biting may be deteriorated. As a countermeasure, it is also effective to apply and dry an adhesive solution directly on the fiber-containing EVOH layer (B) side after the first step, and then press-bond the protective layer (D). In particular, the method is more effective in terms of adhesiveness in order to cause the adhesive to adhere uniformly to the fiber side of the fiber-containing EVOH layer.

  After peeling a protective layer (D) and sticking this multilayer laminated film to a to-be-adhered body, when peeling a support body layer (A), the interface of a to-be-adhered body and an adhesive layer (C) comes first There is a problem such as peeling. As measures therefor, 1) a method of slightly bending the periphery of the multilayer laminate film to the support layer (A) side, 2) a support layer (A) of the periphery of the multilayer laminate film and a thin fiber containing EVOH (B) (3) a method of partially applying a release agent to the film forming the support layer (A) at the periphery of the multilayer laminate film, 4) the support The method etc. which cut layer (A) locally are mentioned, Furthermore, the method etc. which combined two or more types of these methods are mention | raise | lifted. Among these, the method of 2), or the combination of the method of 1) and the method of 2), or the combination of the method of 1) and the method of 3) is more preferable.

The multilayer laminate film of the present invention is packaged with a packaging material (E) having a chemical and additive barrier property in order to reduce the safety and health, and the decrease in efficacy due to scattering of the chemical and the additive, safety and health, And ensure long-term preservation. As a packaging method, for example, there is a method of packaging one or a plurality of laminated multilayer films in a packaging material (E), and heat-sealing and sealing the periphery thereof.
In the multilayer laminate film of the present invention, the package (E) is removed immediately before use, the protective layer (D) is peeled off, and the exposed adhesive surface is attached to the adherend, and then the support layer (A) is peeled off. It can be used.
In addition, as a material of a packaging material (E), PET, aluminum (aluminum foil, aluminum vapor deposition), polyacrylonitrile, EVOH etc. are mentioned.

  Hereinafter, the present invention will be described in more detail by way of examples. The present invention is not limited by the description of the examples.

<Examples 1 to 5 and Comparative Examples 1 to 2>
The fiber-containing EVOH layer (B) is laminated on the support layer (A) shown in Table 1, and separately, the pressure-sensitive adhesive layer (C) containing chemicals and additives is laminated on the protective layer (D). The multilayer laminated film was produced by pressure-bonding in the direction which (B) and a layer (C) face.
The details of the materials described in Table 1 and the films used for the pressure-sensitive adhesive layer (C) and the protective layer (D) are as follows.

<Film used for support layer (A)>
(1) EVOH film (manufactured by Kuraray Co., Ltd., Evar film EF-E # 15 (thickness: 15 μm, ethylene content: 44%, saponification degree: 99%)
(2) Polyester film PET-1: Unitika-made Emblet SM-50 matte-treated product (thickness = 50 μm)

<Fiber-containing EVOH layer (B)>
Kuraray Eval resin EP-E105 (ethylene content: 44%, saponification degree: 99%), 10% by mass of the EVOH resin, and 90% by mass of a 35% hydrous normal propanol solution are added, while heating and stirring The resulting mixture was dissolved in a solution to obtain a homogeneous clear EVOH solution. Next, the EVOH solution is applied to the support layer (A) using a wire bar at a coating amount of 30 g / m ² , dried at 80 ° C., and then the EVOH solution is applied using a wire bar After coating under the condition of 10 g / m ² , the following non-woven fibers or cut fibers were laminated and dried at 80 ° C. to obtain a laminated film of a support layer (A) / fiber-containing EVOH layer (B). At this time, the thickness of the EVOH layer in the fiber-containing EVOH layer was 4 μm.
A-1: Polyester-based non-woven fabric HKT-1 manufactured by Miki Special Paper Co., Ltd. Weight 9g / m ²
A-2: manufactured by Miki Specialty Paper Co., Ltd., polyester non-woven fabric C-20HR. 20g / m ^{2 of} coating amount
A-3: Sanko Chemical Industries Co., Ltd., polyester-based cut fiber (generally called pile) 1.7 T, 0.6 mm long

<Pressure-sensitive adhesive layer (C)>
A solution having the following three types of compositions was prepared, and was applied onto the protective layer (D) under the conditions described below to form an adhesive layer (C).
C-1:
79% by weight of silicone resin (Toray · Dow Corning, BIO-PSA 7-4202), converted to resin weight, 5% by weight silicone oil (Toray · Dow Corning, Q7-9120 SILICONE FLUID), Chemical The mixture was homogenized by mixing 5% by weight of diisopropyl ammonium nitrite, which is a volatile corrosion inhibitor, and 11% by weight of methyl acetate as a dilution solvent.
C-2:
9% by weight of high polymerization degree polyisobutylene (opanol B-100 by BASF), 4% by weight of low polymerization degree polyisobutylene (opanol B-12 by BASF), 11% by weight liquid paraffin (Hycor M-72 by Kaneda) As a chemical, 1% by weight of methyl hinokitiol salicylate which is a volatile antibacterial agent and 75% by weight of toluene as a diluting solvent are mixed and homogenized under boiling and stirring.
C-3:
53% by weight converted to acrylic resin (DURO-TAK 87-2196 manufactured by Henkel), 11% by weight of isopropyl myristate (hereinafter abbreviated as IPM), o-phenylphenol which is a volatile insecticidal agent as a chemical 5% by weight and 31% by weight of methyl acetate as a diluting solvent were mixed and homogenized.

<Film used for protective layer (D)>
The following two types were used.
D-1: Fujimori Kogyo SF3 (Thickness = 50 μm)
D-2: Toyobo K5104 (thickness = 50 μm)

<Lamination of Support Layer (A) and EVOH Layer (B)>
The EVOH solution prepared above is applied to the prepared support layer (A) using a wire bar so as to obtain a predetermined thickness after drying, and after laminating the polyester non-woven fabric, drying is carried out at 80 ° C. for 5 minutes Then, a laminated film of support layer (A) / EVOH layer (B) was produced.

<Lamination of pressure-sensitive adhesive layer (C) and protective layer (D)>
The adhesive solution prepared above is applied on one side of the protective layer (D) using an applicator so that it has a predetermined thickness after drying, and after drying for 5 minutes at 80 ° C., the thickness of the adhesive layer is 60 μm. A laminated film of a certain pressure-sensitive adhesive layer (C) / protective layer (D) was produced.

  The laminated film of the support layer (A) / EVOH layer (B) and the laminated film of the pressure-sensitive adhesive layer (C) / protective layer (D) prepared above were subjected to normal temperature with a DX-700 type table laminator manufactured by TOLAMI. Laminating was carried out at a laminating speed of 1 m / min to obtain a multilayer laminated film. The obtained multilayer laminated film was cut into 4 cm × 5 cm, and was put into a packaging bag (E) composed of PET / aluminum / PAN (polyacrylonitrile), and heat sealing was performed.

The following performance evaluation was performed about the obtained multilayer laminated film.
<Peeling strength, peelability of support, sticking resistance>
The protective layer (D) of the multilayer laminated film of 15 mm width × 100 mm length is peeled off and attached to Lauan wood with a 1 kg weight roller, and left for 1 hour at 23 ° C, 50% RH humidity, film strength and elongation measuring device Peeling is performed 180 degrees at a speed of 100 mm / min using a Shimadzu Autograph AG-1, 500N, and the peeling strength, the position of the peeling layer, and the presence or absence of adhesive residue derived from the adhesive layer (C) are visually observed. Observed.
The adhesive property was determined visually as “o” for none, “Δ” for slightly present, and “x” for many. Moreover, when peeling a protective film (D) visually, when a support body peelability peels a case where a support body layer (A) peels first, it is determined as "x", and a protective layer (D) leads. The case where it peeled easily was determined as "(circle)".

<Tensile strength (at 10% tensile elongation)>
The resulting multilayer laminated film is allowed to stand at 23 ° C., 50% RH humidity for 1 day, and then the packaging bag (E) is removed, and then the support layer (A) and the protective layer (D) are peeled off. The tensile strength is measured at a tensile speed of 5 mm / min using a film strength / elongation measurement device (AG-15, manufactured by Shimadzu Corporation, AG-1, 500 N) at a temperature of 23 ° C. and a humidity of 50% RH. The tensile strength at 10% elongation was determined and used as a measure of flexibility.

As is clear from the results in Tables 1 and 2, in Examples 1 to 5, the adhesion between the fiber-containing EVOH layer (B) and the pressure-sensitive adhesive layer (C) is significantly improved, and Almost no residue such as glue contained in the pressure-sensitive adhesive layer (C) is observed in the Lauan wood), and the irritation to the adherend is significantly improved. On the other hand, in Comparative Examples 1 and 2 in which no fiber is contained in the layer (B), the peel strength between the layer (B) and the layer (C) is low and the adhesion is poor. Residues such as glue contained in the layer (C) were attached.
Therefore, in the multilayer laminate film of the present invention, during storage, there is no adsorption or migration of chemicals and additives in the adhesive layer, and the stretchability of the adherend after attachment is excellent, and the multilayer laminate film is adhered It can be seen that the peeling residue of the pressure-sensitive adhesive layer (C) from the body is significantly improved.

The present invention can be applied to functional protective films of furniture, wallpaper, clothes cases, paperboard, cardboard, wood, construction materials, vegetables, fruits, medical supplies and the like.

Claims (3)

  A support layer (A) is sequentially laminated with a fiber-containing ethylene-vinyl alcohol copolymer (hereinafter referred to as EVOH) thin layer (B), an adhesive layer (C), and a protective layer (D). The multilayer laminate film, wherein the peel strength between the fiber-containing EVOH layer (B) and the pressure-sensitive adhesive layer (C) is 50 g / 15 mm or more.   The multilayer laminate film according to claim 1, wherein the fiber content in the fiber-containing EVOH layer (B) is 1 to 95% by weight. A method in which the fiber-containing EVOH layer (B) coats and dries an EVOH solution containing fibers on a support layer (A), so that at least a part of the fibers is impregnated with the EVOH solution after applying the EVOH solution The multilayer according to claim 1 or 2, which is manufactured by either of a method of laminating and drying fibers on the surface, or a method of extrusion laminating a molten thin layer of EVOH resin containing fibers on the support layer (A). Laminated film.