JP6948288B2 - Anchor coating agents for extruded laminates, laminate films, and packaging materials - Google Patents

Description

The present invention relates to an anchor coating agent for extrusion laminating, a laminating film, and a packaging material.

Film materials and sheet materials (hereinafter collectively referred to as film materials) may be required to have various characteristics depending on their uses and the like, and one type of film material satisfies all of the required characteristics. It is often difficult to do. Therefore, laminates satisfying various characteristics are widely used in various fields by laminating layers such as a plurality of types of film materials to make the best use of the advantages of each material and to compensate for the disadvantages. ..

For example, various packaging containers for accommodating foods, pharmaceuticals, cosmetics, etc., and packaging materials such as various packaging materials such as film materials are laminated with a plurality of layers selected from plastic films, paper, cloth, metal foil, and the like. A film-shaped or sheet-shaped laminated body (laminated film) is often used. As one method for producing this laminated film, an extruded laminating method is known in which a molten resin is extruded into a film material such as a plastic film to form a resin layer.

Generally, when a laminate film (extruded laminate film) is produced by the extrusion laminating method, it is between the material on the side where the extruded resin is laminated (the material to be laminated) and the resin layer formed of the extruded resin. Is required to have high adhesive strength. Therefore, an adhesive auxiliary agent called an anchor coating agent may be provided between the material to be laminated and the resin extruded by the extrusion laminating method so as to exhibit good adhesive strength.

As the anchor coating agent used in the production of the extruded laminated film, a suitable anchor coating agent is often selected and used according to the type and material of the material to be laminated described above, the application of the extruded laminated film, and the like. .. On the other hand, an anchor coating agent applicable to a wide variety and materials of the material to be laminated such as a plastic film and an ink layer provided on the plastic film on which the resin extruded by the extrusion laminating method is laminated has also been proposed. As such, for example, Patent Document 1 discloses an invention relating to "anchor coating agent for extrusion laminating containing a partially acid-modified polyol having a carboxyl group in the molecular chain and an organic polyisocyanate compound".

Japanese Unexamined Patent Publication No. 5-263060

As described above, the laminated film is widely used for various packaging materials. For example, in the case of a bag-shaped packaging material (packaging bag), the packaging bag can be easily opened by hand (the property is that the packaging bag can be easily opened by hand. Easy to open) may be required. Therefore, in order to obtain a laminated film that can be applied to such applications, each layer of the laminated film does not stretch so much and the laminated film can be easily torn straight by hand (easy tearing property). You will need it. This property is affected not only by the material to be laminated and the resin layer formed of the extruded resin, but also by the anchor coating agent used.

In Patent Document 1 described above, when an extruded laminate film is produced by using an anchor coating agent for a plurality of types of laminated materials, the anchor coating agent has excellent adhesive strength, and the anchor coating agent can be used as the type of the laminated material. It is evaluated to be widely applicable. However, in the anchor coating agent disclosed in Patent Document 1, the above-mentioned easy tearability is not taken into consideration.

Therefore, the present invention will provide an anchor coating agent for extrusion lamination capable of obtaining a laminate film having good adhesive strength and easy tearing property with respect to a laminated material of a wide range of organic materials such as a plastic film and an ink layer. Is to be.

According to the present invention, it contains a polyol (A) and a polyisocyanate (B), and the ratio (B / A) of the content of the polyisocyanate (B) to the content of the polyol (A) is 0.5 to 0.5. was 2.0, the polyisocyanate (B) contains adduct of xylylene diisocyanate (B _X), the content of the adduct of the diisocyanate (B _X), the polyisocyanate (B) An anchor coating agent for extrusion lamination, which is 30% by mass or more based on the total content, is provided.

According to the present invention, there is provided an anchor coating agent for extrusion laminating capable of obtaining a laminated film having good adhesive strength and easy tearing property with respect to a laminated material of a wide range of organic materials such as a plastic film and an ink layer. can do.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments.

<Anchor coating agent>
In the extruded laminate, the present inventors have widely applied an anchor coat to a plastic film used as a base material on which an extruded resin is laminated and a laminated material of various organic materials such as an ink layer provided on the base material. Diligent studies were conducted to obtain the agent. As a result, when it contains a polyol (A) and the polyisocyanate (B) in a specific ratio, by using adducts of xylylene diisocyanate (B _X) a specific amount, favorable to the laminate of various organic materials It has been found that an anchor coating agent applicable to the above can be obtained.

That is, the anchor coating agent for extrusion lamination of one embodiment of the present invention (hereinafter, may be simply referred to as “anchor coating agent”) contains a polyol (A) and a polyisocyanate (B). In this anchor coating agent, the ratio (B / A) of the content of polyisocyanate (B) to the content of polyol (A) is 0.5 to 2.0. Then, polyisocyanate (B) contains adduct of xylylene diisocyanate (B _X). The content of the adduct of xylylene diisocyanate (B _X), based on the total amount of the polyisocyanate (B), is not less than 30 mass%.

By having the above structure, the anchor coating agent is coated with various organic materials such as various plastic films as a base material on which the resin extruded by the extrusion laminating method is laminated and various ink layers provided on the base material. It can be widely applied to laminated materials. For example, by providing this anchor coating agent on the material to be laminated, even if the material to be laminated is various organic materials such as various plastic films and ink layers, a laminated film having good adhesive strength and easy tearability can be obtained. It is possible to obtain. Hereinafter, the components of the anchor coating agent according to the embodiment of the present invention will be described.

The polyol (A) contained in the anchor coating agent is a compound having two or more hydroxy groups in one molecule. As the polyol (A), either a low molecular weight polyol or a high molecular weight polyol can be used. Examples of the low molecular weight polyol include polyhydric (divalent or higher) alcohols and the like. Examples of the polymer polyol include polyether polyols, polyester polyols, polycarbonate polyols and the like. The polyol (A) is not particularly limited, and one type can be used alone or two or more types can be used in combination.

Examples of the polyhydric alcohol include ethylene glycol, 1,2-propanediol (also known as propylene glycol), 1,3-propanediol, 2-methyl-1,3-propanediol, and 2,2-dimethyl-1,3. -Propylenediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol , 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, diethylene glycol, triethylene glycol, tetraethylene glycol and other aliphatic diols; 1,4-cyclohexanedimethanol, 1 , 3-Cyclohexanedimethanol, and diols having an alicyclic structure such as 1,4-cyclohexanediol; aromatic diols such as 1,4-benzenemethanol, 1,3-benzenemethanol, and 1,4-dihydroxybenzene; Trihydric or higher polyhydric alcohols such as glycerol, trimethylolpropane, pentaerythritol, and sorbitol; and the like can be mentioned. One or more of these polyhydric alcohols can be used.

Examples of the polyester polyol include a polyester polyol or a polyester amide polyol obtained by a dehydration polycondensation reaction between a polyhydric carboxylic acid and a polyhydric alcohol or secondary or tertiary amines. Examples of polyvalent carboxylic acids that can be used in the production of polyester polyols include succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, and hexahydroortho. Examples thereof include phthalic acid and naphthalenedicarboxylic acid; and polycarboxylic acids such as trimellitic acid; and their acid esters; and their acid anhydrides, and one or more of these can be used. Examples of the polyhydric alcohol that can be used for producing the polyester polyol include the above-mentioned specific examples of the polyhydric alcohol, and one or more of them can be used. Specific examples of the secondary amines that can be used in the production of polyester polyols include low molecular weight amine compounds such as hexamethylenediamine, xylylenediamine, and isophoronediamine, and one or more of these may be used. Can be used. The polyester polyol is a lactone obtained by ring-opening polymerization of cyclic ester (lactone) monomers such as ε-caprolactone and γ-valerolactone, using, for example, a low molecular weight alcohol compound and a low molecular weight amino alcohol compound as initiators. A polyester polyol can also be used.

Examples of the polyether polyol include those obtained by addition polymerization (ring-opening polymerization) of alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide, and tetrahydrofuran and the like to an initiator. As the initiator, for example, in addition to the above-mentioned polyhydric alcohol, low molecular weight amine compounds such as triethanolamine, ethylenediamine, and diethylenetriamine can be used. Examples of the polyether polyol include polyoxyethylene diol (also known as polyethylene glycol), polyoxypropylene diol (also known as polypropylene glycol), polyoxypropylene triol, ethylene oxide-propylene oxide copolymer, and polytetramethylene ether glycol (PTMEG). , Polytetraethylene glycol, sorbitol-based polyol and the like.

Examples of the polycarbonate polyol include those obtained by the above-mentioned dehydroxation reaction of polyhydric alcohol and phosgene, and obtained by transesterification reaction of a low molecular weight alcohol compound with diethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate and the like. There are things that can be done.

The weight average molecular weight (Mw) of the polyol (A) is preferably 5,000 to 100,000, more preferably 8,000 to 80,000, still more preferably 10,000 to 60,000. In the present specification, Mw of the polyol is a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

The content of the polyol (A) in the anchor coating agent is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, still more preferably 30 to 60% by mass, based on the total solid content mass of the anchor coating agent. .. The content of the polyol (A) in the total solid content of the anchor coating agent means the total content of the solid content of the polyol (A) contained in the anchor coating agent, and the anchor coating agent is two or more kinds of polyols. When (A) is contained, it means the total solid content of the two or more kinds of polyols (A).

The anchor coating agent has a ratio (B / A) of the content (solid content) of the polyisocyanate (B) to the content (solid content) of the polyol (A) in the range of 0.5 to 2.0. Contains polyol (A) and polyisocyanate (B). In the above ratio (B / A) range, the content of polyisocyanate (B) in the anchor coating agent is preferably 10 to 80% by mass, preferably 20 to 70% by mass, based on the total solid content mass of the anchor coating agent. % Is more preferable, and 30 to 60% by mass is further preferable. The content of polyisocyanate (B) in the total solid content of this anchor coating agent means the total content of the solid content of polyisocyanate (B) contained in the anchor coating agent, and there are two or more kinds of anchor coating agents. When the polyisocyanate (B) of the above is contained, it means the total content of the two or more kinds of polyisocyanates (B).

According to a preliminary experiment by the present inventors, an extruded laminate film having good adhesive strength and easy tearability can be used by using an anchor coating agent having the above ratio (B / A) in the range of 0.5 to 2.0. Was found to be easy to obtain. The above ratio (B / A) is preferably 0.7 or more, and more preferably 0.8 or more, from the viewpoint that an extruded laminated film having better adhesive strength and easy tearability can be easily obtained. Further, it is preferably 1.4 or less, and more preferably 1.2 or less.

Polyisocyanates contained in the anchor coating agent (B) contains adduct of xylylene diisocyanate (B _X). XDI in adduct of xylylene diisocyanate (XDI) (B _X) are 1,2-xylylene diisocyanate (o-XDI), 1,3-xylylene diisocyanate (m-XDI), 1,4-xylylene diisocyanate Any of (p-XDI) may be used. Among these, 1,3-xylylene diisocyanate (m-XDI), which is easily available, is preferable.

Adduct of xylylene diisocyanate (B _X) is xylylene diisocyanate is 3 functionalized polyisocyanate. Adduct of xylylene diisocyanate (B _X) can be obtained by reacting a xylylene diisocyanate, such as trimethylolpropane (TMP) and trifunctional active hydrogen group-containing compound such as glycerol. The adduct of xylylene diisocyanate (B _X), a compound represented by the following general formula (1) are preferred.

In the general formula (1), R ¹ represents a trivalent organic group and R ² represents a xylylene group. Examples of R ¹ include a trivalent organic group derived from the above-mentioned active hydrogen group-containing compound, and a trivalent hydrocarbon group is preferable. Further, R ² represents a 1,2-xylylene group (o-xylylene group), a 1,3-xylylene group (m-xylylene group), or a 1,4-xylylene group (p-xylylene group), and 1, A 3-xylylene group is preferred. In the case of a 1,3-xylylene group, R ² can be represented by the following structural formula (2). In the following structural formula (2), * ¹ represents the bond with the nitrogen atom bonded to the carbonyl group ^{in the general formula (1), and * 2} represents the isocyanate group (-NCO) in the general formula (1). Represents a bond with.

The adduct of xylylene diisocyanate (B _X), from easy availability, trimethylolpropane (TMP) adducts are preferred xylylene diisocyanate, TMP adduct of 1,3-xylylene diisocyanate is more preferable. ^{Therefore, R 1} in the general formula (1) is preferably a group represented by the following structural formula (3). ^{Note that * 3} in the following structural formula (3) represents a bond with the oxygen atom to which ^{R 1} in the general formula (1) is bonded.

The content of the adduct of xylylene diisocyanate (B _X), based on the total amount of the polyisocyanate (B), is not less than 30 mass%. The content of the adduct of XDI (B _X) is an adduct of XDI occupied on the solid content of the polyisocyanate (B) to be contained in the anchor coating agent content (weight of the solid content of the (B _X) Content ratio). The content of the adduct of the XDI (B _X), when containing two or more of the adduct of XDI the anchor coating agent (B _X) is of two or more XDI in the polyisocyanate (B) It means the total content of the adduct (B _X). The content of an adduct of the XDI (B _X) may be 100% by weight. Therefore, as the polyisocyanate (B) to be contained in the anchor coating agent, only one or more of the adduct of XDI (B _X) may be used.

The content of the adduct of XDI in the polyisocyanate (B) (B _X) is laminate with by at least 30 mass%, for the laminated material of various organic materials, good adhesive strength and easy tear property An anchor coating agent that can contribute to the production of a film can be obtained. By the anchor coating agent, from easy in view of the laminate film is obtained having a better adhesive strength, the content of the adduct of the diisocyanate (B _X) is preferably at least 35 wt%, 40 to It is more preferably 90% by mass, and even more preferably 40 to 80% by mass.

The polyisocyanate used in the anchor coating agent (B), adduct of xylylene diisocyanate as described above with (B _X), it will be preferable to include hexamethylene diisocyanate-based bifunctional polyisocyanate (B _H). In the anchor coating agent, the combined use of adduct of xylylene diisocyanate (B _X) and hexamethylene diisocyanate-based bifunctional polyisocyanate (B _H), to increase the adhesive strength to the laminate of various organic materials It is possible.

Hexamethylene diisocyanate-based bifunctional polyisocyanate ( _BH ) is a bifunctional prepolymer having a structure in which hexamethylene diisocyanate (HDI) is urethane-bonded at both ends. Hexamethylene diisocyanate-based bifunctional polyisocyanate ( _BH ) has, for example, ^{a hydroxy group (-OH) at both ends of a diol (HO-R 3} -OH) and an isocyanate group (-NCO) of hexamethylene diisocyanate. It can be obtained by reacting. Specifically, hexamethylene diisocyanate-based bifunctional polyisocyanate ( _BH ) represented by the following general formula (4) is preferable.

In the general formula (4), R ³ represents a divalent organic group. For example, R ³ may be a divalent organic group derived from the above diol, and is preferably a divalent hydrocarbon group thereof.

Anchor coating agent, if adducts XDI with (B _X) containing HDI-based bifunctional polyisocyanate (B _H), the content of the hexamethylene diisocyanate-based bifunctional polyisocyanate (B _H) (containing solids the content of the adduct of xylylene diisocyanate to the amount) (B _X) (the ratio of solids content) (B _X / B _H) is preferably 0.5 to 9.0. This makes it possible to further increase the adhesive strength of various organic materials to the laminated lumber. From this viewpoint, the ratio (B _X / B _H) is more preferably from 0.5 to 4.0, more preferably from 0.6 to 3.0.

The polyisocyanate used in the anchor coating agent (B) may comprise other polyisocyanates other than adducts of the aforementioned XDI (B _X), and hexamethylene diisocyanate-based bifunctional polyisocyanate (B _H).

Other polyisocyanates, aromatic diisocyanates, aliphatic diisocyanates, and a diisocyanate compound such as alicyclic diisocyanate, (excluding the adduct of XDI (B _X)) and adduct of a diisocyanate compound, an isocyanurate body, biuret , And allophanate compounds and the like. One or more of these can be used.

Examples of the aromatic diisocyanate include tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), diphenylmethane diisocyanate (MDI), 1,4-phenylenediocyanate, 1,5-naphthylene diisocyanate, diphenyl ether diisocyanate, and 3,3. '-Dimethyldiphenylmethane-4,4'-diisocyanate and the like can be mentioned. Examples of the aliphatic diisocyanate include tetramethylene diisocyanate, pentamethylene diisocyanate, and hexamethylene diisocyanate (HDI). Examples of the alicyclic diisocyanate include isophorone diisocyanate (IPDI), norbornan diisocyanate (NBDI), hydrogenated tolylene diisocyanate (hydrogenated TDI), hydrogenated xylene diisocyanate (H ₆ XDI), and hydrogenated diphenylmethane diisocyanate (hydrogenated). MDI) and the like can be mentioned. Examples of the adduct, isocyanurate, biuret, and allophanate of the diisocyanate compound include TDI, HDI, IPDI, and H ₆ XDI TMP adducts; TDI, HDI, XDI, pentamethylene diisocyanate, IPDI, and H ₆ Examples thereof include an isocyanurate form of XDI; a biuret form of HDI; an allophanate form of HDI; and the like. One or more of these can be used.

The anchor coating agent of one embodiment of the present invention preferably further contains a silane coupling agent. The anchor coating agent containing the silane coupling agent makes it easy to obtain a laminated film having good adhesive strength even when the material to be laminated is an inorganic material. This effect is more likely to be exhibited when both the silane coupling agent and the hexamethylene diisocyanate-based bifunctional polyisocyanate ( _{BH) described above are contained in the anchor coating agent.} Specifically, by using such an anchor coating agent, in addition to the case where the material to be laminated is the above-mentioned organic material, a metal foil such as an aluminum foil and an inorganic material such as a vapor-deposited layer such as an aluminum-deposited layer and a silica-deposited layer are used. Even in the case of the above, it becomes easy to obtain a laminated film having good adhesive strength and easy tearing property.

As the silane coupling agent, a silane coupling agent having an alkoxysilyl group and other functional groups as a reactive group in one molecule can be preferably used. Specifically, a silane coupling agent represented by the following general formula (5) is more preferable.
R ^4- Si (R ⁵ ) _n (OR ⁶ ) _3-n・ ・ ・ (5)

^{R 4} , R ⁵ , and OR ⁶ in the general formula (5) represent groups bonded to Si. R ⁴ represents an organic group that may contain an oxygen atom. R ⁵ and R ⁶ each independently represent an alkyl group, and n represents 0, 1, or 2.

^{The organic group represented by R 4} in the general formula (5) is the above-mentioned functional group from the viewpoint of enhancing the adhesiveness between the anchor coating agent containing the silane coupling agent and the resin layer formed of the extruded resin. Is preferably included. Therefore, as R ⁴ , an organic group containing a functional group and which may contain an oxygen atom is preferable. Specifically, R ⁴ more preferably contains a vinyl group, an epoxy group, an acryloyl group, a methacryloyl group, an amino group, a mercapto group, a ureido group, or an isocyanate group as a functional group. Among these functional groups, a vinyl group, an epoxy group, an acryloyl group, a methacryloyl group, and an amino group are more preferable, and an epoxy group and an amino group are further preferable.

^{As the alkyl group represented by R 5} and R ⁶ in the general formula (5), an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group or an ethyl group is preferable. More preferred. Further, n in the general formula (5) is more preferably 0 or 1, and further preferably 0, from the viewpoint of enhancing the adhesiveness of the anchor coating agent containing the silane coupling agent to the inorganic material. preferable.

Examples of the silane coupling agent represented by the general formula (5) include the following compounds. Specific examples of the vinyl group-containing silane coupling agent include vinyltrimethoxysilane and vinyltriethoxysilane. Specific examples of the epoxy group-containing silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyl. Examples thereof include methyldimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

Specific examples of the (meth) acryloyl group-containing silane coupling agent include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, and 3- (meth) acryloxypropyltrimethoxy. Examples thereof include silane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, and the like. Specific examples of the amino group-containing silane coupling agent include N-phenyl-3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and N-2- (aminoethyl). Examples thereof include -3-aminopropyltrimethoxycisilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane.

Specific examples of the mercapto group-containing silane coupling agent include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane. Specific examples of the ureido group-containing silane coupling agent include 3-ureidopropyltrialkoxysilane. Specific examples of the isocyanate group-containing silane coupling agent include 3-isocyanatepropyltriethoxysilane. One or more of the above-mentioned silane coupling agents can be contained in the anchor coating agent.

When the anchor coating agent contains a silane coupling agent, the content of the silane coupling agent (content in terms of solid content) shall be 5% by mass or less with respect to the total solid content mass of the anchor coating agent. Is more preferable, and it is more preferably 3% by mass or less, and more preferably 0.1% by mass or more.

The anchor coating agent of one embodiment of the present invention can usually contain a solvent. The solvent contained in the anchor coating agent is not particularly limited, and is used depending on the material of the material to be laminated to which the anchor coating agent is provided, the application of the extruded laminate film produced by using the anchor coating agent, and the like. The solvent can be appropriately selected. The content of the solvent in the anchor coating agent is not particularly limited, and the content of the solvent can be adjusted so as to have an appropriate viscosity according to a method such as printing when applying the anchor coating agent to the material to be laminated. can.

Solvents include, for example, ketone solvents such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, and cyclohexanone; hydrocarbon solvents such as toluene, xylene, cyclohexane, and methylcyclohexane; ethyl acetate, propyl acetate, and butyl acetate. Etc .; ether solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether (PM), tetrahydrofuran, and dioxane; alcohol solvents such as methanol, ethanol, and isopropanol (IPA); and water and the like. Can be done. One of these may be used alone, or a mixed solvent in which two or more thereof may be used in combination may be used.

The solid content concentration of the anchor coating agent is not particularly limited. A concentrated (thick) anchor coating agent may be prepared and diluted with the above-mentioned solvent when applied to the material to be laminated. For example, the solid content concentration of the anchor coating agent when applied to the laminated lumber is preferably 5 to 20% by mass, more preferably 7 to 15% by mass, and 9 to 12% by mass. Is even more preferable.

The anchor coating agent may contain various additives depending on the purpose. Additives include, for example, pigments, dyes, dispersants, defoamers, leveling agents, thickeners, cross-linking agents, inorganic particles, UV absorbers, light stabilizers, surfactants, preservatives, and rust inhibitors. And so on. One of these additives may be used alone, or two or more of them may be used in combination.

The anchor coating agent of one embodiment of the present invention is used for extrusion laminating, and can be used for producing an extruded laminate film. Specifically, a plastic film used as a base material on which the extruded resin is laminated, a material to be laminated such as an ink layer provided on the base material, and a resin layer formed of the resin extruded by the extruded laminating method. An anchor coating agent can be applied in between.

As the material to be laminated, as described above, a plastic film used as a base material on which the resin extruded by the extrusion laminating method is laminated, and an organic material such as an ink layer provided on the base material are suitable. For example, when an ink layer is provided on a base material and the ink layer serves as a laminated material, the base material is a film material (for example, paper, cloth, metal foil, etc.) made of a material other than a plastic film. May be good. Further, the anchor coating agent may be applied to, for example, a metal foil such as an aluminum foil, and a laminated material of an inorganic material such as a vapor deposition layer such as an aluminum vapor deposition layer and a silica vapor deposition layer. In that case, it is preferable that the anchor coating agent contains the above-mentioned silane coupling agent.

Suitable plastic films for the laminate and substrate include, for example, polyethylene terephthalate (PET), amorphous polyethylene terephthalate (A-PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polylactic acid. Polyester film such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), and polyolefin film such as polypropylene (PP); cellulose film such as cellophane; polystyrene (PS) film Ethylene-vinyl acetate copolymer resin film; ethylene-vinyl alcohol copolymer resin film; polyamide film; polycarbonate film; polyimide film; polyvinyl chloride film and the like can be mentioned. Among these, polyester film and polyamide film are preferable, and PET film and nylon film are more preferable.

As the above-mentioned plastic film, either stretched or unstretched plastic film can be used, for example, a biaxially stretched PP film and a non-stretched PP film. Further, a plastic film provided with a metal vapor deposition layer such as aluminum vapor deposition, a plastic film provided with a transparent vapor deposition layer such as alumina and silica can also be used. Further, even if the surface of the plastic film is subjected to various surface treatments such as corona discharge treatment, plasma treatment, frame treatment, solvent treatment, and coating treatment, and various decorations such as printing using colored ink. good.

Examples of the ink that forms an ink layer suitable as the material to be laminated include urethane resin-based ink, acrylic resin-based ink, silicone resin-based ink, acrylic urethane resin-based ink, and acrylic silicone resin-based ink. The ink forming the ink layer may be a one-component ink or a two-component curable ink. Among these, urethane resin-based one-component ink and urethane resin-based two-component curable ink are preferable.

As the resin forming the resin layer by the extrusion lamination, polyolefins such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), and polypropylene (PP) are preferable. Among them, various polyethylenes are more preferable, and LLDPE is further preferable.

<Laminate film>
The laminate film of one embodiment of the present invention comprises a first resin layer, an anchor coat layer provided on the first resin layer, and a second resin layer provided on the anchor coat layer. Be prepared. The anchor coat layer in this laminate film is formed by the above-mentioned anchor coat agent for extrusion lamination according to the embodiment of the present invention.

As the first resin layer in the laminated film, the above-mentioned base material on which the resin extruded in the extruded laminate is laminated can be used, and preferably, the above-mentioned plastic film can be used. As the first resin layer, a polyester film and a polyamide film are more preferable. Further, as the first resin layer, a plastic film in which the above-mentioned ink layer is provided on the side where the resin extruded by the extruded laminate is laminated can also be preferably used. The thickness of the first resin layer (base material) is preferably 5 to 500 μm, more preferably 10 to 100 μm, and even more preferably 10 to 60 μm.

As the second resin layer in the laminate film, the resin extruded in the above-mentioned extruded laminate can be used. As the second resin layer, polyolefin is preferable, various PEs are more preferable, and LDPE and LLDPE are further preferable. The thickness of the second resin layer is preferably 1 to 300 μm, more preferably 5 to 200 μm, and even more preferably 10 to 100 μm.

The anchor coat layer can be formed by applying the above-mentioned anchor coat agent to the first resin layer and drying it. Examples of the method for applying the anchor coating agent include gravure roll coating, reverse roll coating, air knife coating, wire bar coating, curtain flow coating, spray coating, and immersion coating. The anchor coating agent is preferably applied by a coater (for example, a roll coater or the like) attached to the extrusion laminating equipment used when producing the extruded laminate film.

^{The amount of the anchor coating agent applied is not particularly limited, but is preferably 0.01 to 2} g / m 2 in terms of dry (solid content) mass with respect to the area of the coated surface, and is preferably 0.05 to 1 g / m. ^{It is more preferably 2} and even more preferably 0.1 to 0.5 g / m ² . The drying temperature of the anchor coating agent applied to the first resin layer is not particularly limited, and can be, for example, in the range of 40 to 200 ° C. The drying time is also not particularly limited, and can be, for example, in the range of 1 to 600 seconds. The thickness of the anchor coat layer is not particularly limited, and can be, for example, about 0.01 to 1 μm, preferably about 0.01 to 0.5 μm.

The formation of the second resin layer on the anchor coat layer provided on the first resin layer can be performed by a conventionally known extrusion laminating method. In this method, the resin (thermoplastic resin) forming the second resin layer is melted and extruded into a film, and the resin is applied to the anchor coat layer provided on the first resin layer. 2 resin layers can be formed. A method of extruding a resin forming a second resin layer onto an anchor coat layer provided on the first resin layer, and further adhering a base material such as another plastic film on the resin (so-called extruded sandwich laminating method or extrusion). It is also possible to take the tandem laminating method).

The laminate film of one embodiment of the present invention is formed by the above-mentioned anchor coating agent between a first resin layer as a base material and a second resin layer formed of a resin extruded by an extrusion laminating method. An anchor coat layer can be provided. Therefore, in this laminated film, the material to be laminated to which the anchor coat layer is provided is various organic materials such as a plastic film that can be used as the first resin layer (base material) and an ink layer provided on the base material. Even if there is, it is possible to show good adhesive strength and easy tearability. Therefore, this laminated film can be suitably used as a packaging material, and a packaging material having good easy-opening property can be obtained by the packaging material provided with this laminated film.

<Packaging material>
The packaging material of one embodiment of the present invention includes the above-mentioned laminated film. Suitable uses of the packaging material provided with the laminated film include, for example, various packaging containers containing foods, beverages, pharmaceuticals, quasi-drugs, cosmetics, detergents, chemicals and the like, and films and papers. Various packaging materials and the like can be mentioned. Applications in which packaging materials are used also include electronic parts, electric parts, electric products, automobile parts, various sheets and cards, and labels and tags provided on the products. Specific embodiments of the wrapping material include, for example, a paper box, a wrapping paper, a wrapping film, a wrapping label, a wrapping bag, and a plastic container such as a plastic case and a plastic bottle. Of these, packaging bags are more preferred. Suitable uses of the packaging bag include, for example, a food packaging bag, a pharmaceutical packaging bag, a cosmetic packaging bag, and the like.

The laminated film and the packaging material may include any layer other than the above-mentioned first resin layer (base material), second resin layer (resin layer made of extruded resin), and anchor coat layer. .. As the arbitrary layer, the above-mentioned ink layer (for example, a pattern layer, a colored layer, etc.) provided on the above-mentioned first resin layer (base material), a thin-film deposition layer, a base material such as another plastic film, or the like can be used. It can be mentioned, but is not limited to these.

As described in detail above, the anchor coating agent for extrusion lamination according to the embodiment of the present invention can adopt the following constitution.
[1] It contains a polyol (A) and a polyisocyanate (B), and the ratio (B / A) of the content of the polyisocyanate (B) to the content of the polyol (A) is 0.5 to 2.0. , and the said polyisocyanate (B) contains adduct of xylylene diisocyanate (B _X), the content of the adduct of the diisocyanate (B _X), the total content of the polyisocyanate (B) An anchor coating agent for extrusion lamination, which is 30% by mass or more based on the amount.
[2] The content of the adduct of the diisocyanate (B _X), based on the total amount of the polyisocyanate (B), for extrusion lamination according to the 40 to 90 wt% [1] Anchor coating agent.
[3] The anchor coating agent for extrusion laminating according to the above [1] or [2], wherein the polyisocyanate (B) further contains a hexamethylene diisocyanate-based bifunctional polyisocyanate ( _BH).
[4] the adducts of the diisocyanate to the content of hexamethylene diisocyanate-based bifunctional polyisocyanate (B _H) ratio of the content of _{(B X) (B X /} B H) is 0.5 The anchor coating agent for extrusion laminating according to the above [3], which is 9.0.
[5] The anchor coating agent for extrusion laminating according to any one of the above [1] to [4], which further contains a silane coupling agent.

Further, by using the anchor coating agent for extrusion lamination of one embodiment of the present invention, it is also possible to provide the following laminate film and packaging material.
[6] The anchor coat layer includes a first resin layer, an anchor coat layer provided on the first resin layer, and a second resin layer provided on the anchor coat layer. , A laminated film formed of the anchor coating agent for extrusion laminating according to any one of the above [1] to [5].
[7] A packaging material comprising the laminate film according to the above [6].

Hereinafter, the anchor coating agent for extrusion lamination, the laminate film, and the packaging material according to the embodiment of the present invention will be described in more detail with reference to test examples, but they are not limited to the following test examples. .. In the following sentences, the descriptions "part" and "%" are based on mass ("parts by mass" and "% by mass", respectively) unless otherwise specified.

(Test Examples 1 to 17)
As the components of the anchor coating agent for extrusion lamination, the following polyol (A), polyisocyanate (B), silane coupling agent and the like were used.

[Polyform (A)]
A polyester polyol having a solid content of 62.5%, a viscosity at 25 ° C. in the range of 1500 to 3000 mPa · s, a hydroxyl value in the range of 10 to 20 mgKOH / g, and an Mw in the range of 1000 to 30000.

[Polyisocyanate (B)]
Polyisocyanate (B _X): adduct of xylylene diisocyanate (XDI) (trade name "Takenate D-110N", manufactured by Mitsui Chemicals, Inc., solid content: 75%, NCO%: 11.5 %, viscosity: 500mPa · s / 25 ° C)
Polyisocyanate ( _BH ): Hexamethylene diisocyanate (HDI) -based bifunctional polyisocyanate (trade name "Duranate D101", manufactured by Asahi Kasei Corporation, solid content: 100%, NCO%: 19.7%, viscosity: 500 mPa. s / 25 ° C)

[Coupling agent]
-Silane coupling agent represented by the general formula (5)

<Preparation of anchor coating agent>
In each test example, the components (unit: part) shown in the upper part of Tables 1 and 2 below are mixed, sufficiently stirred, and each anchor coating agent (hereinafter, may be referred to as “AC agent”). Was prepared. Here, in the AC agent components shown in the upper part of Tables 1 and 2, the amounts of the polyol, polyisocyanate, and silane coupling agent represent the amount in terms of solid content. Further, in the middle of Tables 1 and 2, the ratio of the content of polyisocyanate (B) to the content of polyol (A) in the AC agent (B / A) and the total content of polyisocyanate (B) are shown. adducts of XDI content of (B _X) content ratio of _{(B X / B × 100)} , and based on HDI 2 adduct of XDI to the content of functional polyisocyanate (B _H) (B _X) The ratio ( _BX / B _H ) is shown.

<Making a laminated film>
Using each anchor coating agent, a laminated film having a laminated structure described below was produced by a melt-extruded laminating method (melt-extruded sandwich laminating method). Specifically, using an extrusion laminating facility, an AC agent is applied to the entire surface of one surface of the material to be laminated in the laminating structure described below at a coating amount of 0.3 g (dry mass) / m ² , and then a drying furnace. Ethyl acetate was evaporated at (temperature 80 ° C.) to dry the AC agent to form an anchor coat layer. Next, the linear low density polyethylene (LLDPE) in a molten state is extruded into the anchor coat layer (hereinafter, may be referred to as “AC layer”) in a film shape so as to be sandwiched between another LLDPE film. An LLDPE layer having a thickness of 50 μm was formed between the AC layer and the LLDPE film to obtain a laminated film (width 1 m, length 2 m).

[Laminated structure]
Laminated structure L1: The laminated material is a nylon film (trade name "Harden film N1102", manufactured by Toyobo Co., Ltd., thickness 15 μm), and the LLDPE layer and the LLDPE film are formed on the laminated material (nylon film) via an AC layer. Is a laminated structure.
Laminated structure L2: The laminated material is a white ink layer I ₁ provided on the nylon film by solid printing, and the LLDPE layer and the LLDPE film are formed on the laminated material (white ink layer I _{1) via an AC layer.} Is a laminated structure.
Laminated structure L3: The laminated material is a white ink layer I ₂ provided on the nylon film by solid printing, and the LLDPE layer and the LLDPE film are formed on the laminated material (white ink layer I _{2) via an AC layer.} Is a laminated structure.
Laminated structure L4: The laminated material is a PET film (trade name "Toyobo ester film E5102", manufactured by Toyobo Co., Ltd., thickness 12 μm), and the LLDPE layer and LLDPE are passed through the AC layer on the laminated material (PET film). It is a structure in which films are laminated.
Laminated structure L5: The laminated material is a white ink layer I ₁ provided on the PET film by solid printing, and the LLDPE layer and the LLDPE film are formed on the laminated material (white ink layer I _{1) via an AC layer.} Is a laminated structure.
Laminated structure L6: The laminated material is a white ink layer I ₂ provided on the PET film by solid printing, and the LLDPE layer and the LLDPE film are formed on the laminated material (white ink layer I _{2) via an AC layer.} Is a laminated structure.
Laminated structure L7: The laminated material is a transparent silica vapor-deposited layer in a transparent silica vapor-deposited PET film (trade name "Tech Barrier VX", manufactured by Mitsubishi Chemical Co., Ltd., thickness 12 μm), and this laminated material (transparent silica vapor-deposited layer). The LLDPE layer and the LLDPE film are laminated via the AC layer.
_{Laminated structure L8: The laminated material is a white ink layer I 3} provided by solid printing on the transparent silica vapor-deposited layer in the transparent silica-deposited PET film, and an AC layer is formed on the laminated material (white ink layer I _3). The LLDPE layer and the LLDPE film are laminated via the silica.
Laminated structure L9: The laminated material is an aluminum foil (thickness 7 μm) dry-laminated on the PET film via an adhesive layer, and the LLDPE layer is formed on the laminated material (aluminum foil) via an AC layer. And the LLDPE film is laminated.

The following white inks were used for the white ink layers I ₁ , I ₂ , and I _{3 in the above laminated structure, respectively.}
-White ink layer I ₁ : 1-component urethane-based ink (8.5 parts of urethane resin, 3.0 parts of vinyl chloride-vinyl acetate copolymer resin, 0.4 parts of cellulose acetate butyrate (CAB) resin, 22 parts of ethyl acetate One-component urethane-based ink containing 0.0 parts, MEK 25.0 parts, IPA 5.5 parts, PM 1.5 parts, dispersant 0.1 parts, and titanium oxide 34.0 parts)
-White ink layer I ₂ : Two-component urethane-based ink (100 parts of the above-mentioned one-component urethane-based ink is mixed with 5 parts of a curing agent (including 30% by mass of hexamethylene diisocyanate and 70% by mass of ethyl acetate) 2 Liquid urethane ink)
-White ink layer I ₃ : Three-component urethane ink (105 parts of the two-component urethane ink, silane coupling agent solution (10% by mass of the silane coupling agent, 70% by mass of ethyl acetate, and 20% by mass of IPA). (Including) 3 liquid urethane ink containing 5 parts)

The obtained laminated film was subjected to an adhesive strength test, a boiling resistance test, and an easy tear resistance test as described below. The results are shown in Tables 1 and 2 below.

(Adhesive strength test)
From each of the obtained laminated films, a sample cut into a rectangular shape having a width of 15 mm and a length of 100 mm was collected, and a T-type peeling test sample was prepared as a sample for measuring the adhesive strength. Each T-type peeling test sample was subjected to a T-type peeling test under the condition of a tensile speed of 300 mm / min using a tensile tester (trade name "Tencilon RTG-1225", manufactured by A & D Co., Ltd.). The adhesive strength (T-type peel strength) between the laminated material and the LLDPE layer in the sample was measured.

(Adhesive strength test after boiling resistance test)
From each of the obtained laminated films, one laminated film cut into a rectangular shape having a width of 100 mm and a length of 150 mm was collected. The laminated film is folded in half in the length direction with the LLDPE film inside and laminated, and the edges (area 10 mm from the edge) along the two adjacent sides are heat-sealed to prepare a seal bag with an opening. bottom. From the opening of the seal bag, 10 g of a model food in which commercially available vinegar, salad oil, and ketchup are mixed at a mass ratio of 1/1/1 is filled in the bag, and then the opening is heat-sealed in the same manner as described above to enter the model food. A three-way seal bag was prepared. The seal bag containing the model food was placed in hot water at 95 ° C. for 30 minutes, and then the model food was taken out from the seal bag. A T-type peeling test sample was prepared as a sample for measuring the adhesive strength from the seal bag from which the model food was taken out by the same method as the above-mentioned adhesive strength test. T-type peel strength) was measured.

(Easy tear test)
In the seal bag used in the boiling resistance test, a three-way seal bag was prepared by the same method except that the model food was not filled. In this seal bag, a tear line is made at one place (two places in total) for each of the seal parts along two adjacent sides, and the easy tearing property when horizontal tearing and vertical tearing are performed is as follows. According to the evaluation criteria, the evaluation was made on a 5-point scale. A horizontal tear has an upper edge of the cut line and is torn so as to pull it in the left-right direction around the cut line (also called a crotch tear), and a vertical tear has an upper edge of the cut line. Then, it tears linearly downward from the cut line so as to tear it back and forth.
5 points: The seal bag could be torn cleanly in both the horizontal and vertical tears.
4 points: The seal bag could be torn in both the horizontal and vertical tears, but a slight elongation of the LLDPE layer was observed when the seal bag was torn slowly in the middle of the tear.
3 points: In both the horizontal and vertical tears, the LLDPE layer was stretched, but the seal bag could be torn.
2 points: In both the horizontal and vertical tears, the LLDPE layer was stretched and it was difficult to tear the seal bag, but the seal bag could be torn by applying strong force.
1 point: In both cases of horizontal tear and vertical tear, elongation of the LLDPE layer was observed, and the seal bag could not be torn even if strong force was applied.

When the anchor coating agents of Test Examples 1 to 13 were used, as compared with the case where the anchor coating agents of Test Examples 14 to 17 were used, with respect to the laminated material of a wide range of organic materials such as a plastic film and an ink layer. It was confirmed that a laminated film having good adhesive strength and easy tearability was obtained.

Claims (6)

Contains polyol (A) and polyisocyanate (B),
The weight average molecular weight of the polyol (A) is 10,000 to 100,000.
The ratio (B / A) of the content of the polyisocyanate (B) to the content of the polyol (A) is 0.8 to 1.2.
The polyisocyanate (B) contains adduct of xylylene diisocyanate _(B X), and hexamethylene diisocyanate-based bifunctional polyisocyanate _(B H),
The content of the adduct of the diisocyanate (B _X), the relative total content of the polyisocyanate (B), is not less than 30 wt%, an anchor coating agent for extrusion lamination. The content of the adduct of the diisocyanate (B _X), based on the total amount of the polyisocyanate (B), an anchor coating agent for extrusion lamination according to claim 1 which is 40 to 90 mass%. The adduct of the diisocyanate to the content of hexamethylene diisocyanate-based bifunctional polyisocyanate _{(B H)} ratio of the content of _{(B X) (B X /} B H) is 0.5 to 9.0 The anchor coating agent for extrusion laminating according to claim 1 or 2. The anchor coating agent for extrusion laminating according to any one of claims 1 to 3 , further containing a silane coupling agent. The first resin layer and
Anchor coat layer provided on the first resin layer and
A second resin layer provided on the anchor coat layer is provided.
A laminate film in which the anchor coat layer is formed of the anchor coat agent for extrusion laminating according to any one of claims 1 to 4. A packaging material comprising the laminate film according to claim 5.