JP5322960B2 - Laminated film and method for producing the same - Google Patents

Description

  The present invention relates to a laminated film and a method for producing the same.

  For various purposes such as providing weather resistance to outdoor signboards and the like, a marking film is widely applied. Conventionally, vinyl chloride resin has been used as the constituent material of the marking film. However, for the purpose of improving antifouling properties and preventing gloss deterioration, a film of fluororesin is used on the surface of the marking film made of vinyl chloride resin. Is laminated or applied.

  On the other hand, however, laminating a fluororesin has a problem in that the flexibility of the marking film is lowered and the processing cost is increased. In addition, when a fluororesin solution is applied, the solvent in the solution may permeate and remain in the marking film resin. If the solvent remains in the marking film, the deterioration proceeds between the fluororesin layer and the vinyl chloride resin layer, causing peeling between layers, discoloration / fading, and deterioration in weather resistance. there were.

  As a technique for solving such a problem caused by laminating / coating a fluororesin on the surface of a marking film, a technique of changing the stacking order at the time of film production has been proposed (for example, see Patent Document 1). . In the technique described in Patent Document 1, first, a fluororesin-containing solution is applied onto a process paper (release sheet), dried, and then a vinyl chloride resin organosol is cast thereon, followed by heat-curing, and a fluororesin film. And a soft vinyl chloride resin film are formed. In such a laminated film, an isocyanate-based crosslinking agent is generally added to the fluororesin-containing solution for the purpose of improving the weather resistance and flexibility of the obtained fluororesin film.

JP-A-7-188624

  However, as a result of the study by the present inventors, when producing a laminated film by the method described in Patent Document 1, after forming a fluororesin layer by applying a fluororesin-containing solution on the process paper, for example, after several days have elapsed It has been found that when a vinyl chloride resin organosol is cast on the fluororesin layer to form a vinyl chloride resin layer, sufficient adhesion cannot be secured between the fluororesin layer and the vinyl chloride resin layer. As a result, the adhesiveness between the process paper and the fluororesin layer becomes relatively large, and it becomes difficult to peel off the process paper that is originally unnecessary for the marking film from the fluororesin layer. End up.

  Therefore, the present invention has been made in view of the above-described state of the art in the prior art, and in a laminated film having a configuration of process paper, a fluororesin layer, and a main layer (made of vinyl chloride resin or the like) at the time of manufacture, Even when the fluororesin layer and the main layer are laminated, it is possible to ensure sufficient adhesion between the fluororesin layer and the main layer and to allow easy peeling between the fluororesin layer and the process paper. The purpose is to provide.

  The inventors of the present invention have intensively studied to solve the above problems. In the process, an attempt was made to change the type of the crosslinking agent contained in the fluororesin layer in the laminated film having the structure of process paper, fluororesin layer and main layer (made of vinyl chloride resin or the like) during production. And finally, it discovered that the said subject could be solved by including a metal chelate crosslinking agent in a fluororesin layer, and came to complete this invention.

  The laminated film of the present invention thus completed is from the group consisting of a fluororesin layer containing a fluororesin, and a vinyl chloride resin, a urethane resin, and an acrylic resin disposed on one surface of the fluororesin layer. A main layer containing the selected resin is laminated. And the said fluororesin layer contains a metal chelate crosslinking agent, and the adhesive force between the said fluororesin layer and the said main layer measured according to JISK5600-5-6: 1999 is a classification | category 0. Has characteristics.

  According to the laminated film of the present invention, the laminated fluororesin layer and the main layer are laminated after a certain period of time in the laminated film having the structure of process paper-fluorine resin layer-main layer (made of vinyl chloride resin, etc.) at the time of manufacture. Even in this case, the adhesion between the fluororesin layer and the main layer is sufficiently secured, and it becomes possible to easily peel between the fluororesin layer and the process paper.

It is sectional drawing of the laminated | multilayer film of one Embodiment of this invention.

  Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. The dimensional ratios in the drawings are exaggerated for convenience of explanation, and may differ from actual ratios.

  FIG. 1 is a cross-sectional view of a laminated film according to an embodiment of the present invention. As shown in FIG. 1, the laminated film 1 has a fluororesin layer 10. The fluororesin layer 10 contains a fluororesin and contains a metal chelate crosslinker (for example, an aluminum chelate crosslinker). On one surface of the fluororesin layer 10 (the lower surface of the fluororesin layer 10 shown in FIG. 1), the main layer 20 of the laminated film 1 is disposed. In the present embodiment, the main layer 20 includes a vinyl chloride resin. A process paper 30 is disposed on the other surface of the fluororesin layer 10 (the upper surface of the fluororesin layer 10 shown in FIG. 1). In the present embodiment, the process paper 30 is a polyethylene terephthalate (PET) film in which a release agent is applied to the surface on the fluororesin layer 10 side. Furthermore, a pressure-sensitive adhesive layer 40 containing a pressure-sensitive adhesive is disposed on the surface of the main layer 20 opposite to the fluororesin layer 10 (the lower surface of the main layer 20 shown in FIG. 1). A release paper 50 is further disposed on the opposite surface (the lower surface of the pressure-sensitive adhesive layer 40 shown in FIG. 1). Hereinafter, the constituent members of the laminated film 1 will be described in order.

[Fluororesin layer]
As shown in FIG. 1, the laminated film 1 has a fluororesin layer 10. By setting it as such a structure, when the laminated film 1 is used for uses, such as a marking film, the weather resistance and antifouling property of the laminated film may be improved.

  As described above, the fluororesin layer 10 includes a fluororesin. In this invention, there is no restriction | limiting in particular about the specific form of the fluororesin which is a constituent material of the fluororesin layer 10, A conventionally well-known fluororesin can be used. The fluororesin is made of a polymer having a repeating unit derived from a fluorine-containing monomer. Examples of the fluorine-containing monomer include trifluoroethylene, tetrafluoroethylene, pentafluoropropylene, hexafluoropropylene, chlorotrifluoroethylene, 3,3,3-trifluoropropylene, vinylidene fluoride, vinyl fluoride, par Examples thereof include fluoroalkyl vinyl ether. The fluororesin may be a homopolymer of a fluorine-containing monomer or a copolymer of a fluorine-containing monomer. The fluororesin may be a copolymer of a fluorine-containing monomer and another monomer copolymerizable therewith.

  As the monomer copolymerizable with the fluorine-containing monomer, a hydroxy group-containing vinyl monomer is preferably used. That is, the fluororesin is preferably a fluororesin having a hydroxy group. Examples of the hydroxy group-containing vinyl monomer include hydroxyalkyl (meth) acrylate, hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether, hydroxycarboxylic acid vinyl ester, hydroxycarboxylic acid allyl ester, and N-hydroxyalkyl (meth) acrylamide. . In addition, only 1 type of these monomers may be used independently, and 2 or more types may be used together.

  Examples of the hydroxyalkyl (meth) acrylate include hydroxyalkyl (meth) acrylates having 5 to 8 carbon atoms. Specifically, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate Etc.

  Examples of the hydroxyalkyl vinyl ether include hydroxyalkyl vinyl ethers having 4 to 10 carbon atoms, specifically, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyisobutyl vinyl ether, Examples include 4-hydroxy-2-methylbutyl vinyl ether, hydroxypentyl vinyl ether, hydroxyhexyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 2- (4-hydroxycyclohexylethyl) vinyl ether, and 2,3-dihydroxypropyl vinyl ether.

  Examples of the hydroxyalkyl allyl ether include hydroxyalkyl allyl ether having 5 to 11 carbon atoms, specifically, hydroxyethyl allyl ether, hydroxypropyl allyl ether, hydroxybutyl allyl ether, hydroxyisobutyl allyl ether, hydroxyhexyl allyl ether. 4-hydroxycyclohexyl allyl ether, 2- (4-hydroxycyclohexylethyl) allyl ether, 2,3-dihydroxypropyl allyl ether, and the like.

  Examples of the hydroxycarboxylic acid vinyl ester include a hydroxycarboxylic acid vinyl ester having 4 to 10 carbon atoms, and specifically, a hydroxyvinyl acetate, a hydroxypropanoate, a hydroxybutanoate, a hydroxyhexanoate, 4-hydroxy Examples include cyclohexyl vinyl acetate.

  Examples of the hydroxycarboxylic acid allyl ester include hydroxycarboxylic acid allyl esters having 5 to 11 carbon atoms, specifically, allyl hydroxyacetate, allyl hydroxypropanoate, allyl hydroxybutanoate, allyl hydroxyhexanoate, 4-hydroxy Examples include cyclohexyl allyl acetate.

  Examples of N-hydroxyalkyl (meth) acrylamide include hydroxyalkyl (meth) acrylamide having 5 to 8 carbon atoms, specifically, N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide etc. are mentioned.

  On the other hand, a carboxy group-containing vinyl monomer is also preferably used as the monomer copolymerizable with the fluorine-containing monomer. That is, it is also preferable that the fluororesin is a fluororesin having a carboxy group. Further, the fluororesin is particularly preferably a fluororesin having both a hydroxy group and a carboxy group. Here, examples of the carboxy group-containing vinyl monomer include acrylic acid and methacrylic acid.

  In the copolymerization of the fluorine-containing monomer and the hydroxy group and / or carboxy group-containing vinyl monomer, another monomer may be further mixed and copolymerized.

  Examples of such other monomers include alkyl vinyl ether, alkyl allyl ether, carboxylic acid vinyl ester, carboxylic acid allyl ester, α-olefin, alkyl (meth) acrylate, and N-alkyl (meth) acrylamide. In addition, also as for these other monomers, only 1 type may be used independently and 2 or more types may be used together.

  Examples of the alkyl vinyl ether include alkyl vinyl ethers having 4 to 10 carbon atoms. Specific examples include ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, hexyl vinyl ether, cyclohexyl vinyl ether, cyclohexyl ethyl vinyl ether, and 2-ethylhexyl vinyl ether. Can be mentioned.

  Examples of the alkyl allyl ether include alkyl allyl ethers having 5 to 11 carbon atoms, and specifically include ethyl allyl ether, propyl allyl ether, butyl allyl ether, isobutyl allyl ether, hexyl allyl ether, cyclohexyl allyl ether, cyclohexyl ethyl. Examples include allyl ether and 2-ethylhexyl allyl ether.

  Examples of the carboxylic acid vinyl ester include carboxylic acid vinyl esters having 4 to 10 carbon atoms, and specific examples include vinyl acetate, vinyl propanoate, vinyl butanoate, vinyl hexanoate, and cyclohexyl vinyl acetate.

  Examples of the carboxylic acid allyl ester include carboxylic acid allyl esters having 5 to 11 carbon atoms, and specifically include allyl acetate, allyl propanoate, allyl butanoate, allyl hexanoate, allyl cyclohexyl acetate, and the like.

  Examples of the α-olefin include α-olefins having 2 to 8 carbon atoms, and specific examples include ethylene, propylene, butylene, isobutylene, 1-hexene, and styrene.

  Examples of the alkyl (meth) acrylate include alkyl (meth) acrylates having 5 to 8 carbon atoms. Specifically, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cyclohexylmethyl (meth) ) Acrylate and the like.

  Examples of N-alkyl (meth) acrylamides include alkyl (meth) acrylamides having 5 to 8 carbon atoms. Specifically, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl ( And (meth) acrylamide.

  The blending ratio of the above-mentioned fluorine-containing monomer in the copolymerization is preferably adjusted so as to be 10 to 60 mol% with respect to the total amount of monomers constituting the fluororesin, and 20 to 50 mol. It is more preferable to adjust so that it may become%.

  On the other hand, when the fluororesin is a fluororesin having a hydroxy group, the blending ratio of the hydroxy group-containing vinyl monomer is 5 to 50 mol% with respect to the total amount of monomers constituting the fluororesin. It is preferable to adjust, and it is more preferable to adjust so that it may become 10-40 mol%. Further, when the fluororesin is a fluororesin having a carboxy group, the blending ratio of the carboxy group-containing vinyl monomer is 5 to 50 mol% with respect to the total amount of the monomers constituting the fluororesin. It is preferable to adjust, and it is more preferable to adjust so that it may become 10-40 mol%. In addition, it is preferable to adjust so that the mixture ratio of another monomer may be 0-80 mol% with respect to the whole quantity of the monomer which comprises a fluororesin, and it may become 10-60 mol%. It is more preferable to adjust.

  The hydroxyl value (mgKOH / g) of the fluororesin is preferably 0 to 200, more preferably more than 0 and 200 or less, still more preferably 20 to 80. Moreover, the acid value (mgKOH / g) of a fluororesin becomes like this. Preferably it is 10-200, More preferably, it is 50-150, More preferably, it is 80-120. According to these configurations, when peeling the process paper, it prevents cohesive failure of the fluororesin layer, and when the laminated film of the present invention is used for applications such as a marking film, it has excellent weather resistance and solvent resistance. Can be expressed. In addition, the value of the hydroxyl value and acid value of a fluororesin is a value measured by the neutralization titration method described in JIS K0070: 1992.

  Thus, although the fluororesin layer 10 contains a fluororesin essentially, the fluororesin layer 10 may be formed by blending other resin with a fluororesin. Examples of such other resins include acrylic resins and urethane resins.

  In the laminated film 1 of the form shown in FIG. 1, the fluororesin layer 10 contains a metal chelate crosslinking agent. There is no restriction | limiting in particular about the specific form of the metal chelate crosslinking agent contained in the fluororesin layer 10, A conventionally well-known knowledge can be referred suitably. As an example, the metal chelate crosslinking agent includes a metal chelate compound in which the metal atom is aluminum, zirconium, titanium, zinc, iron, tin, etc. Among them, an aluminum chelate compound is preferable from the viewpoint of crosslinking performance. .

  Examples of the aluminum chelate compound include diisopropoxy aluminum monooleyl acetoacetate, monoisopropoxy aluminum bis oleyl acetoacetate, monoisopropoxy aluminum monooleate monoethyl acetoacetate, diisopropoxy aluminum monolauryl acetoacetate, diisopropoxy aluminum Monostearyl acetoacetate, diisopropoxyaluminum monoisostearyl acetoacetate, monoisopropoxyaluminum mono-N-lauroyl-β-alanate monolauryl acetoacetate, aluminum trisacetylacetonate, monoacetylacetonate aluminum bis (isobutylacetoacetate ) Chelate, monoacetylacetonate aluminum bis (2-ethylhexyl acetoacetate) chelate, monoacetylacetonate aluminum bis (dodecyl acetoacetate) chelate, monoacetylacetonate aluminum bis (oleyl acetoacetate) chelate and the like.

  Other metal chelate compounds include, for example, titanium tetrapropionate, titanium tetra-n-butyrate, titanium tetra-2-ethylhexanoate, zirconium sec-butylate, zirconium diethoxy-tert-butyrate, triethanolamine. Examples thereof include titanium dipropionate, ammonium lactate ammonium salt, and tetraoctylene glycol titanate.

  In this embodiment, as for the metal chelate crosslinking agent contained in the fluororesin layer 10, only 1 type may be individual and 2 or more types may be used together. The content of the metal chelate crosslinking agent in the fluororesin layer 10 is preferably 0.1 to 3.5 parts by mass, more preferably 0.8 to 2.5 parts by mass with respect to 100 parts by mass of the fluororesin. More preferably, it is 1.0-2.0 mass parts. When the content of the metal chelate crosslinking agent is within such a range, the fluororesin layer can be prevented from cohesive failure when the process paper is peeled off.

  As described above, the fluororesin layer 10 essentially contains a metal chelate crosslinking agent, but may further contain other crosslinking agents. Examples of such a crosslinking agent include aromatic diisocyanates such as tolylene diisocyanate, chlorophenylene diisocyanate, 2,4-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, and polymethylene polyphenyl isocyanate; Lower aliphatic diisocyanates such as tetramethylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, hydrogenated products of the above aromatic diisocyanates; And adduct isocyanate compounds added with polyhydric alcohols such as trimethylolpropane, isocyanurate compounds , Biuret type compounds, further polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, isocyanate crosslinking agents such as polyisoprene polyol such as an addition-reacted urethane prepolymer type polyisocyanates. Epoxy crosslinking agents such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, terephthalic acid diglycidyl ester, spiroglycol diglycidyl ether, diglycidylaminomethylcyclohexane, tetraglycidylxylenediamine, and polyglycidylmetaxylenediamine Can also be used. However, the content of the crosslinking agent other than the metal chelate crosslinking agent is preferably as small as possible with respect to the total amount of the crosslinking agent contained in the fluororesin layer 10, and specifically, preferably 0 to 1% by mass. More preferably, it is 0-0.1 mass%, Most preferably, it is 0 mass%. This is due to a mechanism (estimation) in which the effect of the present invention is manifested. That is, as will be discussed in the Examples section described later, in the present invention, by using a chelate crosslinking agent as a crosslinking agent contained in the fluororesin layer 10, the fluororesin layer 10 and the main layer 20 (described later) are used after a certain period of time. ) Are laminated, it is considered that the adhesion between these layers is ensured. And this is to some extent after the fluororesin layer 10 is formed by using a metal chelate crosslinking agent having a relatively weak crosslinking power instead of an isocyanate crosslinking agent or an epoxy crosslinking agent having a relatively strong crosslinking power. The metal chelate crosslinking agent may have contributed to improving the adhesion with the main layer 20 formed on the surface of the fluororesin layer 10 even after the time elapses. The mechanism is inferred. However, the technical scope of the present invention is not affected by this mechanism.

  Although there is no restriction | limiting in particular in the thickness of the fluororesin layer 10, Usually, it is about 0.5-20 micrometers.

[Main layer]
As shown in FIG. 1, a main layer 20 is disposed on one surface of the fluororesin layer 10. In the form shown in FIG. 1, the main layer 20 contains a vinyl chloride resin, but the constituent material of the main layer 20 is not limited to this. For example, the constituent material of the main layer 20 may be a urethane resin or an acrylic resin. There is no restriction | limiting in particular about the specific form of the material which comprises the main layer 20, A conventionally well-known knowledge can be referred suitably.

  Examples of the constituent material of the vinyl chloride resin include polyvinyl chloride having a number average degree of polymerization of about 800 to 2500, and a copolymer mainly composed of vinyl chloride (for example, ethylene-vinyl chloride copolymer, vinyl acetate-vinyl chloride copolymer). A polymer, a vinyl chloride-halogenated olefin copolymer, etc.), or other compatible resins based on these polyvinyl chlorides or vinyl chloride copolymers (eg polyester resins, epoxy resins, acrylic resins, vinyl acetate resins). , Urethane resin, acrylonitrile-styrene-butadiene copolymer, partially saponified polyvinyl alcohol, and the like, and those containing vinyl chloride resin. These polyvinyl chloride or a copolymer mainly composed of vinyl chloride may be obtained by any conventional production method such as bulk polymerization, emulsion polymerization, suspension polymerization, and solution polymerization. As for these vinyl chloride resins, only 1 type may be used independently and 2 or more types may be used together. This vinyl chloride resin can be prepared by blending, for example, about 20 to 50 parts by mass of a plasticizer (for example, a polyester plasticizer) with respect to 100 parts by mass of the vinyl chloride resin. Moreover, stabilizers, such as a lead salt stabilizer, a metal soap stabilizer, and an organic tin stabilizer, may be blended as necessary. This vinyl chloride resin is preferably employed as a constituent material of the main layer 20 from the viewpoint of balance of shape followability, workability, economy, and the like.

  On the other hand, from the viewpoint of environmental problems, urethane resin and acrylic resin may be used as the low environmental load type main layer constituent material. When these materials are used, for example, when the main layer 20 is composed of a urethane resin, the urethane resin is configured as a reaction product of a polymer such as polyester polyol or polyether polyol and a curing agent.

  Although there is no restriction | limiting in particular in the thickness of the main layer 20, Usually, it is about 10-500 micrometers.

[Process paper]
As shown in FIG. 1, process paper 30 is disposed on the other surface of the fluororesin layer 10. There is no restriction | limiting in particular about the specific form of the process paper 30, What apply | coated the release agent to resin films, such as a polyethylene terephthalate (PET) film, is used. Here, as the release agent, polyvinyl alcohol, a long-chain alkyl compound, an alkyd resin, a silicone-modified alkyd resin, silicone, or the like is used. In the laminated film of the present invention, the presence of process paper is not essential. After the laminated film is produced by the production method described later, if the process paper is not removed, a laminated film including the process paper is obtained.

  Although there is no restriction | limiting in particular in the thickness of the process paper 30, Usually, it is about 10-200 micrometers.

[Adhesive layer / release paper]
As shown in FIG. 1, an adhesive layer 40 is provided on the surface of the main layer 20 opposite to the fluororesin layer 10, and a release paper 50 is further laminated on the adhesive layer 40. .

  The pressure-sensitive adhesive layer 40 includes a pressure-sensitive adhesive. About the specific structure of the adhesive contained in the adhesive layer 40, it can employ | adopt without a restriction | limiting in particular. An example of the pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer 40 includes a base polymer composed of a (meth) acrylic acid ester (co) polymer and a crosslinking agent. Hereinafter, the embodiment will be described in more detail by taking such an example as an example, but in some cases, a pressure sensitive adhesive such as a rubber pressure sensitive adhesive, a silicone pressure sensitive adhesive, a polyurethane pressure sensitive adhesive, or a polyester pressure sensitive adhesive may be used. Of course.

  The (meth) acrylic acid ester constituting the (meth) acrylic acid ester-based (co) polymer is an ester of (meth) acrylic acid and a monoalcohol, and the alkyl group of the monoalcohol is n-octyl. Group, isooctyl group, 2-ethylhexyl group, n-butyl group, isobutyl group, methyl group, ethyl group, isopropyl group and the like. The (meth) acrylic acid ester-based (co) polymer may contain one or more of these (meth) acrylic acid esters.

  The proportion of the above-mentioned repeating units derived from the (meth) acrylic acid ester in the total repeating units of the (meth) acrylic acid ester (co) polymer is preferably 30 to 99 mol with respect to 100 mol% of all the repeating units. %, More preferably 50 to 95 mol%.

  The (meth) acrylic acid ester-based (co) polymer is derived from a (meth) acrylic acid-based monomer having an organic functional group such as a carboxy group, a hydroxy group, or a glycidyl group as a component other than those described above. Repeating units may be included. Examples of such components include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, and glycidyl (meth) acrylate. The ratio of these repeating units to all repeating units of the (meth) acrylic acid ester-based (co) polymer is preferably 0.01 to 15 mol%, more preferably 100 mol% of all repeating units. Is 0.3 to 10 mol%.

  For the purpose of increasing the cohesive strength of the pressure-sensitive adhesive, it is possible to appropriately copolymerize vinyl acetate, styrene or the like as a comonomer component. Moreover, it is also possible to add a tackifier for the purpose of increasing the adhesive strength.

  There is no particular limitation on the crosslinking agent contained in the pressure-sensitive adhesive. However, from the viewpoint of preventing yellowing of the pressure-sensitive adhesive layer 40, preferably, an aliphatic isocyanate compound, an alicyclic isocyanate compound, an epoxy compound, or a metal chelate compound is used as a crosslinking agent. Only 1 type of these crosslinking agents may be used independently, and 2 or more types may be used together. In some cases, other known cross-linking agents other than these may of course be used.

  There is no restriction | limiting in particular also about the specific form of various crosslinking agents mentioned above, A conventionally well-known knowledge can be referred suitably. An example of the crosslinking agent includes hexamethylene diisocyanate as the aliphatic isocyanate compound, and isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated xylylene diisocyanate as the alicyclic isocyanate compound. These isocyanate compounds are adducts that are reaction products of the above-described compounds with biurets, isocyanurates, and low molecular active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, and the like. It may be used in the form of a body or the like. Examples of the epoxy compound include N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, polyethylene glycol diglycidyl ether, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, and the like. . Examples of the metal chelate compound include aluminum trisacetylacetonate and diisopropoxybis (acetylacetonato) titanium.

  Although there is no restriction | limiting in particular about content of the crosslinking agent in an adhesive, Preferably it is 0.001-15 mass parts with respect to 100 mass parts of (meth) acrylic acid type (co) polymers mentioned above, More preferably 0.1 to 10 parts by mass.

  As described above, as an example of the pressure-sensitive adhesive, an example including a base polymer composed of a (meth) acrylic acid ester-based (co) polymer and a cross-linking agent has been described. Of course, it may be used.

  Although the thickness in particular of the adhesive layer 40 is not restrict | limited, Preferably it is 5-100 micrometers, More preferably, it is 15-50 micrometers. The thickness of the pressure-sensitive adhesive layer 13 is appropriately selected and set according to the size of the unevenness on the surface (attachment surface) of the adherend.

  The pressure-sensitive adhesive layer 40 may further include other conventionally known additives. Examples of such additives include tackifiers, fillers, pigments, ultraviolet absorbers, and the like. Examples of the tackifier include natural resins such as rosin resins and polyterpene resins, petroleum resins such as C5, C9, and dicyclopentadiene, and synthetic resins such as coumarone indene resin and xylene resin. . Examples of the filler include zinc white, silica, calcium carbonate and the like.

  The technical scope of the present invention should be determined based on the description of the claims. Therefore, depending on the case, the adhesive layer 40 and the thing (laminate film) which consists only of a structure which does not have the release paper 50 mentioned later for details are also contained in the technical scope of this invention.

  The release paper 50 is a layer having a function of protecting the pressure-sensitive adhesive layer 40 and preventing a decrease in adhesiveness before use of the laminated film 1 as a marking film or the like. The release paper 50 is peeled off when the laminated film 1 is used.

  The specific form of the release paper 50 is not particularly limited, and conventionally known knowledge can be referred to as appropriate. The release paper 50 is generally made of a material such as a polyester film such as polyethylene terephthalate, polybutylene terephthalate or polyethylene naphthalate, a plastic film such as a polyolefin film such as polypropylene or polyethylene; a paper such as glassine paper, kraft paper or clay coated paper. Configured as a substrate. The thickness of these base materials is usually about 10 to 400 μm. Further, a layer (not shown) made of a release agent composed of a silicone resin or the like for improving the release property of the pressure-sensitive adhesive layer 40 may be provided on the surface of the release paper 50. When such a layer is provided, the thickness of the layer is usually about 0.01 to 5 μm.

[Production method]
According to this invention, the suitable manufacturing method of the laminated film mentioned above is also provided. That is, in the method for producing a laminated film according to the present invention, first, a fluororesin-containing solution containing a metal chelate crosslinking agent is applied on a process paper, and the obtained coating film is dried to form a fluororesin layer (first) 1 step). Subsequently, a solution containing a resin selected from the group consisting of a vinyl chloride resin, a urethane resin, and an acrylic resin is applied onto the obtained fluororesin layer and dried to form a main layer (second step). Hereinafter, it demonstrates in detail in order of a process.

(First step)
In the first step, first, the process paper 30 is prepared. Since the specific form of the process paper is as described above, detailed description is omitted here.

  On the other hand, a fluororesin-containing solution (also referred to as “first solution”) is prepared. This fluororesin-containing solution is a solution in which a fluororesin (and other resins and / or additives as required) and a metal chelate crosslinking agent are dissolved and dispersed in an appropriate solvent. As the solvent, for example, toluene, ethyl acetate or the like can be used. This solution may be prepared by itself, may be a commercially available product, or may be a product obtained by appropriately modifying a commercially available product.

  In the first step, subsequently, the first solution prepared above is applied onto the process paper 30. There is no restriction | limiting in particular about the specific form of application | coating, For example, a gravure coater, a Meyer bar, a die coater, a knife coater etc. can be used as an application | coating means. Then, the obtained coating film is dried. There is no restriction | limiting in particular also about the specific form of drying, What is necessary is just to dry for about 30 second-about 3 minutes at the temperature of about 80-120 degreeC according to a conventional method. Thereby, the fluororesin layer 10 is formed on the process paper 30.

(Second step)
In the second step, first, a solution (also referred to as “second solution”) in which a resin (and other additives as necessary) constituting the main layer is dissolved and dispersed in an appropriate solvent is prepared. . As the solvent, for example, ketones such as methyl isobutyl ketone, esters such as butyl acetate, glycol ethers such as ethylene glycol monobutyl ether, and the like can be used. This solution may also be a self-prepared product or a commercial product or a modification thereof.

  In the second step, subsequently, the second solution prepared above is applied onto the fluororesin layer 10 formed in the first step described above. There is no restriction | limiting in particular about the specific form of application | coating, For example, the method demonstrated in the column of the 1st process can be employ | adopted. Then, the obtained coating film is dried. There is no restriction | limiting in particular also about the specific form of drying, What is necessary is just to dry for about 30 second-about 3 minutes at the temperature of about 80-200 degreeC according to a conventional method. Thereby, the main layer 20 is formed on the fluororesin layer 10.

  Although the essential structure of the laminated film of the present invention can be produced by the above-described method, the pressure-sensitive adhesive layer 40 and the release paper 50 can be laminated on the main layer 20 as necessary. In such a form, usually, a pressure-sensitive adhesive sheet in which the pressure-sensitive adhesive layer 40 is formed on the surface of the release paper 50 is separately prepared, and the pressure-sensitive adhesive layer 40 of the pressure-sensitive adhesive sheet is the main layer in the laminated film produced above. A method of transferring to 20 is employed. By such a technique, the laminated film 1 having the form shown in FIG. 1 can be manufactured.

  In the laminated film 1 according to the embodiment of the present invention, as described above, the adhesion between the fluororesin layer 10 and the main layer 20 is sufficiently ensured, and easily between the fluororesin layer 10 and the process paper 30. It becomes possible to peel.

  Expressing this quantitatively, in the laminated film of the present embodiment, when the adhesive force between the fluororesin layer 10 and the main layer 20 is measured according to JIS K5600-5-6: 1999 (cross cut method), It becomes classification 0. To put it simply, when a grid cut is made in the fluororesin layer 10 and then tape is applied and peeled off, the edges of the cut are completely smooth, and the grid eye Means no peeling. In the laminated film of the present embodiment, the peeling force at the interface between the process paper 30 and the fluororesin layer 10 is preferably 10 to 500 mN / 50 mm, more preferably 20 to 300 mN / 50 mm, and still more preferably. 50-200 mN / 50 mm. In addition, the value of this peeling force is a value measured according to JIS K6854-2: 1999.

  There is no restriction | limiting in particular about the use of the laminated | multilayer film 1 of this invention. However, since the laminated film 1 has such weather resistance that it can be used outdoors, for example, as a display / sign, as a danger indication tape, a line tape, a marking tape, or as a decoration, a signboard, It can be used for interiors and exteriors of show windows, buildings, decoration of cars and motorcycles, decoration of automobile door sashes, and the like.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the technical scope of the present invention should be determined based on the description of the scope of claims, and should not be limited only to the following examples.

[Production of laminated film]
<Example 1>
First, as a process paper, a polyethylene terephthalate film (thickness: 50 μm) coated with a silicone-modified alkyd resin was prepared.

  Subsequently, the main agent (solid content 30% by mass, ethylene trifluoride / butyl acrylate (BA) / 2-hydroxyethyl methacrylate (HEMA) / acrylic acid (AA) / methyl methacrylate (MMA) = 30/30/15/15 / 10, acid value 110, hydroxyl value 61) 100 parts by mass of an aluminum chelate-based cross-linking agent (manufactured by Soken Chemical Co., Ltd., M-5A, solid content 5% by mass) 10 parts by mass (functional group of the cross-linking agent / The fluororesin solution was prepared by adding (COOH = 4.4%) (main agent: crosslinking agent = 100: 1.7 by mass ratio of solid content).

  The fluororesin solution prepared above was applied onto the process paper prepared above using a knife coater, and the obtained coating film was dried at 110 ° C. for 90 seconds to form a fluororesin layer (thickness: 10 μm). Formed. Thereafter, the obtained laminate was allowed to stand for 7 days in an environment of 23 ° C. and 50% RH.

  On the other hand, 100 parts by mass of a vinyl chloride resin (manufactured by PolyOne Corporation, Geon 178), 35 parts by mass of a polyester plasticizer (manufactured by Dainichi Seika Kogyo Co., Ltd., Finesizer NS-4070), a metal soap stabilizer (manufactured by Katsuta Chemical Co., Ltd.) , B-9301) An organosol prepared by mixing 4 parts by mass and 40 parts by mass of ethylene glycol monobutyl ether as a solvent was prepared. Next, the organosol was applied onto the fluororesin layer formed above (after standing for 7 days) using a knife coater, and the resulting coating film was 90 ° C. for 90 seconds, and then 190 ° C. for 30 seconds. The film was dried for 2 seconds to form a main layer (thickness: 55 μm) made of vinyl chloride resin.

  Thereafter, the main layer and the pressure-sensitive adhesive layer are bonded to the pressure-sensitive adhesive sheet in which the pressure-sensitive adhesive layer (thickness 20 μm) mainly composed of the acrylic pressure-sensitive adhesive is formed on the release paper on the main layer formed above. Thus, a laminated film of this example was produced.

<Comparative Example 1>
When preparing the fluororesin solution, instead of 10 parts by mass of the aluminum chelate-based crosslinking agent, 2.6 parts by mass of the isocyanate-based crosslinking agent (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate HL, solid content 75% by mass) (crosslinking agent) The laminated film of this comparative example was produced by the same method as in Example 1 except that the functional group of /COOH=4.4%) was used.

[Evaluation of laminated film]
The laminated films prepared in Example 1 and Comparative Example 1 were evaluated by the following method. The evaluation results are shown in Table 1 below.

(Peeling power of process paper)
The peel strength of the process paper was measured according to the method described in JIS K6854-2: 1999.

  Specifically, the laminated film was cut into a size of 250 mm in length × 50 mm in width, the release paper was peeled off and affixed to a stainless steel plate. Thereafter, one end of the process paper was peeled off, and the peeling force of the process paper was measured by pulling in a direction of 180 degrees at a moving speed of 300 mm / min.

(Process paper peeling interface)
Further, by observing the process paper and the main layer of the laminated film subjected to the peel test, it was confirmed whether the release interface was an interface between the process paper and the fluorine resin layer or an interface between the fluororesin layer and the main layer.

(Adhesion of fluororesin layer to main layer)
The process paper was peeled off from the laminated film, and the adhesion force of the fluororesin layer to the main layer was measured according to JIS K5600-5-6: 1999. Adhesive strength was evaluated on a 6-point scale, with no peeling at all (Category 0) to a high degree of peeling (Category 5).

  As shown in Table 1, in the laminated film produced in Example 1, when the process paper was peeled off, it was peeled off at the interface between the process paper and the fluororesin layer, and its peeling force was sufficiently small so as not to hinder the work, Moreover, the fluororesin layer was not peeled off from the main layer.

  On the other hand, in the laminated film produced in Comparative Example 1, the fluororesin layer was peeled off from the main layer with a small peeling force and transferred to the process paper.

  Since Example 1 and Comparative Example 1 differ only in the crosslinking agent contained in the fluororesin layer, the difference in results as described above is brought about due to the difference in such crosslinking agent. Will be. Although the mechanism is not completely clear, it is speculated that one of the causes is a difference in crosslinking speed between the aluminum chelate-based crosslinking agent and the isocyanate-based crosslinking agent. That is, when an isocyanate-based crosslinking agent is used as in Comparative Example 1, since the crosslinking of the fluororesin layer proceeds with the passage of time, the time until the main layer is laminated after forming the fluororesin layer on the process paper It seems that the adhesion force to the main layer decreases as the length increases.

  On the other hand, when an aluminum chelate-based crosslinking agent is used as in Example 1, crosslinking is completed when the fluororesin solution is dried, so that the adhesion force to the main layer does not decrease.

1 laminated film,
10 Fluororesin layer,
20 Main layer,
30 process paper,
40 adhesive layer,
50 Release paper.

Claims (7)

A fluororesin layer containing a fluororesin;
A main layer including a resin selected from the group consisting of vinyl chloride resin, urethane resin, and acrylic resin, disposed on one surface of the fluororesin layer;
Is a laminated film formed by laminating,
The fluororesin layer includes a metal chelate crosslinking agent;
An adhesive force between the fluororesin layer and the main layer measured in accordance with JIS K5600-5-6: 1999 is a classification 0, and is a laminated film.   The laminated film according to claim 1, wherein a process paper is further disposed on a surface of the fluororesin layer opposite to the main layer.   The laminated film according to claim 1 or 2, wherein the main layer contains a vinyl chloride resin.   The laminated film according to any one of claims 1 to 3, wherein the metal chelate crosslinking agent is an aluminum chelate compound.   The laminated film according to any one of claims 1 to 4, wherein a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive is further disposed on a surface of the main layer opposite to the fluororesin layer.   The laminated film according to any one of claims 1 to 5, wherein a release paper is further disposed on a surface of the pressure-sensitive adhesive layer opposite to the main layer.   A fluororesin-containing solution containing a metal chelate cross-linking agent is applied onto the process paper, and the resulting coating film is dried to form a fluororesin layer. Subsequently, a vinyl chloride resin, a urethane resin, and A method for producing a laminated film, comprising applying a solution containing a resin selected from the group consisting of acrylic resins and drying to form a main layer.

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