JP2014188937A - Laminated film and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated film which has a resin layer excellent in adhesion with various hard coat agents and having an excellent ability to suppress the precipitation of an oligomer from a polyester film.SOLUTION: The laminated film includes a polyester film and a resin layer (X) which is provided on at least one surface of the polyester film and formed by using a resin (α) obtained from a resin composition containing a resin (A) having at least hydroxyl group and acryloyl group and a melamine compound (B) having methylol group. In the laminated film, the surface energy (x) of the resin layer (X) and the functional group index (y) satisfy following formula (1): y>-0.8x+55, where, 35≤x≤65 (unit: mN/m) and 10≤y≤35 (unit: %).

Description

  The present invention relates to a laminated film in which a resin layer is laminated on a thermoplastic resin film, particularly a polyester film. More specifically, the present invention relates to an easy-adhesion film that suppresses oligomers precipitated from a polyester film in a processing step involving heat treatment and has excellent adhesion to various hard coat agents.

  Thermoplastic resin films, especially biaxially stretched polyester films, have excellent properties such as mechanical properties, electrical properties, dimensional stability, transparency, and chemical resistance. Widely used as a substrate film in applications. In particular, in recent years, there has been an increasing demand for various optical films including antireflection materials for flat panel displays and display materials related to touch panels. In such applications, coating processes having various functions, and electrode materials and optical films are often bonded together.

  However, in the polyester film, the oligomer is precipitated from the polyester film due to the heat treatment performed in the coating process or the annealing process, and the polyester film may be whitened or the surface may be contaminated. Furthermore, when laminating various coating layers on a polyester film, or processing by laminating electrode materials and optical films, if the adhesion to the material to be laminated or laminated is poor, peeling or quality of the manufacturing process Decrease occurred and it could not be applied as a final product.

  For this reason, studies have been made for the purpose of imparting an easy adhesion function and an oligomer suppression function to a polyester film. For example, a method in which a binder resin, a polycarbodiimide compound or a melamine compound is reacted on the surface of a polyester film to form a layer having excellent blocking resistance, and adhesion to various topcoats (Patent Document 1), A method (Patent Documents 2 and 3) in which a coating film is formed using a thermosetting acrylic resin and a crosslinking agent by an in-line coating method in which coating is performed in the process of manufacturing a polyester film has been studied. Moreover, the method (patent document 4) which provides the coating film using an acrylic urethane copolymer resin and a some compound, and provides the adhesiveness after heat-and-moisture resistant adhesiveness and ultraviolet irradiation is proposed. Furthermore, studies have been made for the purpose of suppressing oligomer precipitation and imparting an easy adhesion function by sequentially laminating an oligomer precipitation preventing layer and an adhesive layer on a polyester film (Patent Document 5).

Japanese Patent No. 4637299 JP 2005-89622 A Special table 2011-11420 gazette JP 2011-94125 A JP 2012-92314 A

  However, the method of providing a resin layer by reacting a binder resin with a polycarbodiimide compound or a melamine compound on the surface of a polyester film as in Patent Document 1 is limited in the type of the compound, and thus has an adhesive property with various coatings. Inferior in general versatility. In addition, since the binder resin is not particularly limited, the reactivity between the binder resin and the compound is not constant, so that there is a disadvantage that the oligomer suppression is inferior. As in Patent Documents 2 and 3, the method of providing a resin layer using a general thermosetting acrylic resin and a cross-linking agent has a difference in surface energy between the oligomer precipitated from the polyester film and the acrylic resin. Although a certain oligomer precipitation inhibitory property is exhibited as compared with 1, the oligomer precipitation inhibitory property is inferior to a resin layer made of a general ultraviolet (UV) curable acrylic resin. Moreover, the method of providing a resin layer using an acrylic urethane resin and a plurality of compounds as in Patent Document 4 is superior in versatility in terms of adhesiveness to various coatings as compared to Patent Document 1. However, similarly to Patent Document 2 and Patent Document 3, there is a defect inferior in oligomer precipitation suppression. Furthermore, as in Patent Document 5, an oligomer precipitation preventing layer and an adhesive layer are sequentially laminated on a polyester film, and a method of providing a coating film for the purpose of suppressing oligomer precipitation and imparting an easy adhesion function is the method of forming an oligomer on a polyester film. Since the prevention layer and the adhesive layer are sequentially laminated, there are a plurality of manufacturing steps, which not only lowers the product yield but also increases the manufacturing cost. Moreover, since each process requires application | coating and heat processing, there existed a fault which the crack and dimensional change to a polyester film surface generate | occur | produce easily during manufacture.

  Accordingly, an object of the present invention is to provide a laminated film having a resin layer that eliminates the above-mentioned drawbacks, is excellent in adhesiveness with various hard coating agents, and is excellent in oligomer precipitation suppression from a polyester film. .

The present invention has the following configuration. That is,
Resin layer (X) comprising a resin (α) obtained from a resin composition containing at least one surface of a polyester film (A) having at least a hydroxyl group and an acryloyl group and a melamine compound (B) having a methylol group Is a laminated film in which the surface energy (x) of the resin layer (X) and the functional group index (y) satisfy the following formula (1).

y> −0.8x + 55 Formula (1)
However, 35 ≦ x ≦ 65 (unit: mN / m) and 10 ≦ y ≦ 35 (unit:%) are satisfied.
It is.

  The laminated film of the present invention has good transparency and excellent adhesion to various hard coat agents, and has the effect of suppressing the precipitation of oligomers from the polyester film, which is a base film that becomes a problem during heat treatment. .

  Hereinafter, the laminated film of the present invention will be described in detail.

  The present invention is a laminated film in which a resin layer (X) is laminated on at least one surface of a polyester film as a base film.

(1) Resin layer (X)
The resin layer (X) of the laminated film of the present invention needs to satisfy the following formula (1) in terms of surface energy (x) and functional group index (y).

y> −0.8x + 55 Formula (1)
However, the range satisfies 35 ≦ x ≦ 65 (unit: mN / m) and 10 ≦ y ≦ 35 (unit:%).

Although details of the calculation method of the surface energy (x) will be described later, the contact angles of four kinds of solutions of pure water, ethylene glycol, formamide, and diiodomethane are measured on the resin layer (X). The surface free energy (γ) is separated into three components of a dispersion force component (γ _S ^d ), a polar force component (γ _S ^p ), and a hydrogen bond force component (γ _S ^h ), and the Fowkes equation is expanded ( It is a value obtained as the sum of the dispersion force, the polar force, and the hydrogen bonding force by the geometric mean method based on the “Extended Fowkes equation)”.

  Although details of the calculation method of the functional group index (y) will be described later, the surface of the resin layer (X) is measured by X-ray photoelectron spectroscopy (XPS), and among the obtained element information, carbon element This is a value showing the total composition (%) of the C—N bond and C—O bond in the composition (%). That is, functional group index (y) = [carbon element composition (%)] × [total composition of C—N bond and C—O bond (%)]. Based on the functional group index (y), the amount of C—N bonds and C—O bonds existing on the surface of the resin layer (X) can be evaluated.

  When the laminated film of the present invention satisfies the formula (1), the resin layer (X) has various coatings such as a hard coating agent, ink, and pressure-sensitive adhesive, and has an adhesive property by approximation of surface energy and / or a resin layer ( Good adhesiveness can be expressed by the polar group having a C—O bond or a C—N bond contained in X) and the adhesion by hydrogen bond or intermolecular force.

  Formula (1) will be described in more detail. Conventionally, the adhesiveness between a resin layer and a layer to be overcoated (that is, a hard coat agent or the like) has been discussed based on the surface energy of the resin layer surface and the layer to be overcoated. However, as a result of intensive studies by the present inventors, it was found that the general-purpose adhesion between the resin layer and the overcoated layer cannot be sufficiently explained only by the surface energy of the resin layer surface and the overcoated layer. . Therefore, as a result of evaluating general-purpose adhesion between various resin layers and overcoated layers (such as various hard coat agents), the present inventors have determined that the surface of the resin layer (X) containing the resin (α). It was found that the resin layer (X) in which the energy (x) and the functional group index (y) of the resin layer (X) satisfy the formula (1) have good adhesiveness with various hard coating agents.

  First, as a condition satisfying general adhesiveness with various hard coating agents, the surface energy range of the resin layer (X) needs to be 35 mN / m or more and 65 mN / m or less. By setting the surface energy of the resin layer (X) to 35 mN / m or more, it is possible to suppress the release property from appearing in the resin layer (X). On the other hand, by setting the surface energy of the resin layer (X) to 65 mN / m or less, it is possible to prevent an extreme divergence of the surface energy from a hard coating agent generally composed of an acrylic resin or a urethane resin. In the range of the surface energy of the resin layer (X), the relationship of the formula (1) was found in the functional group index obtained from the amount of C—N bonds and C—O bonds of the resin layer (X). That is, in the range where the surface energy is small, by increasing the functional group index, the polarity of the surface of the resin layer (X) is increased, and general-purpose adhesiveness with various hard coat agents is exhibited. Moreover, in the range where the surface energy is large, even if the functional group index is small, the surface energy of the resin layer (X) is high, so that general-purpose adhesiveness with various hard coating agents is exhibited. On the other hand, when the value of the functional group index is generally small and is equal to or less than the formula (1), it is difficult to satisfy general-purpose adhesiveness with various hard coat agents.

  The resin layer (X) of the present invention comprises a resin (α) obtained by heating a resin composition comprising a resin (A) having a hydroxyl group and an acryloyl group and a melamine compound (B) having a methylol group. It is necessary to use it. A manufacturing method in particular is not ask | required if it is a laminated | multilayer film which satisfy | fills the conditions mentioned above. The laminated film having the resin layer (X) using the resin (α) is a polyester film (a resin composition using a resin (A) having a hydroxyl group and an acryloyl group and a melamine compound (B) having a methylol group. It can be manufactured by applying to at least one surface of a substrate film) and heating. Details of the resin (α) and the crosslinked structure contained in the resin (α) will be described later.

  The resin forming the resin layer (X) of the laminated film of the present invention has a total content of the resin (α), the resin (A) having a hydroxyl group and an acryloyl group, and the melamine compound (B) having a methylol group. It is preferable that it is 80 mass% or more with respect to the whole resin which forms a resin layer. By controlling the total content of the resin (α), the resin (A), and the melamine compound (B) in the resin forming the resin layer to be 80% by mass or more, oligomer precipitation suppression and surface energy (x ) And the formula (1) based on the functional group index (y), both excellent adhesiveness with various coatings can be achieved.

  The resin (α) is a resin obtained by heating a resin composition comprising a resin (A) having a hydroxyl group and an acryloyl group and a melamine compound (B) having a methylol group to 150 ° C. or higher. Is preferred. When a resin composition comprising the resin (A) and the melamine compound (B) is heated to 150 ° C. or higher, a crosslinked structure formed by crosslinking the acryloyl groups of the resin (A), or a hydroxyl group of the resin (A) And the methylol group of the melamine compound (B) are crosslinked to form a crosslinked structure (structure represented by the formula (2) described later) efficiently. At the same time, a crosslinked structure formed by crosslinking the methylol groups of the melamine compound (B) (structure represented by the formula (2) described later) can be efficiently formed. Since the cross-linking reaction between the acryloyl groups of the resin (A), the hydroxyl groups of the resin (A) and the methylol groups of the melamine compound (B), and the methylol groups of the melamine compound (B) is highly reactive, the resin (α) is It becomes a resin having many cross-linked structures. Increasing the number of hydroxyl groups and acryloyl groups in the resin (A) and the number of methylol groups in the melamine compound (B) makes it possible to obtain a resin (α) with a more dense cross-linked structure.

  That is, in the present invention, the resin forming the resin layer preferably has a cross-linked structure between acryloyl groups. Moreover, it is preferable that resin which forms a resin layer has a crosslinked structure (chemical structure) of the hydroxyl group and the methylol group couple | bonded with the amino group of a melamine compound shown by Formula (2). Moreover, it is preferable that resin which forms a resin layer has a crosslinked structure of methylol groups couple | bonded with the nitrogen atom of a melamine compound shown by Formula (3).

  Thus, since the resin or resin (α) forming the resin layer has a dense cross-linked structure, the hardness of the resin layer can be dramatically increased. In addition, it is possible to obtain a laminated film with less oligomer precipitation after heating and excellent transparency. In particular, even when the laminated film of the present invention is heat-treated at 150 ° C. for 1 hour, the haze change rate remains at 0.3% or less. Therefore, the laminated film of the present invention is suitably used for applications that are heated and require transparency. Specifically, it is suitably used for applications (for example, touch panel applications) in which a conductive layer such as a hard coat layer or indium tin oxide (hereinafter referred to as ITO) is provided on the laminated film of the present invention. This is because when a conductive layer such as a hard coat layer or ITO is laminated, high heat is applied to the laminated film, and high transparency is required even after these layers are laminated. .

  The resin layer (X) of the laminated film of the present invention preferably has a resin layer thickness of 80 nm or more and 500 nm or less. By setting the resin layer thickness to 80 nm or more, it becomes possible to impart oligomer precipitation inhibitory properties. By setting the resin layer thickness to 500 nm or less, the transparency and handling properties of the laminated film are improved.

  Furthermore, the laminated film of the present invention preferably has a haze value of 3.0% or less. By setting the haze value to 3.0% or less, for example, it can be suitably used for an optical film such as a display that requires transparency. For example, when the laminated film of the present invention is used as a display film, it becomes possible to suppress white turbidity of the display and suppress a decrease in resolution.

(2) Resin (α) and Crosslinked Structure As described above, the resin (α) used in the present invention is a resin composition comprising a resin (A) having a hydroxyl group and an acryloyl group and a melamine compound (B) having a methylol group. It is a resin obtained by heating an object. The resin (α) will be described in detail below.

  In the laminated film of the present invention, the resin (α) is preferably a resin having a glass transition temperature of 50 ° C. or higher. By setting the resin (α) to a resin having a glass transition temperature of 50 ° C. or higher, the hardness of the resin layer is increased, and not only the oligomer precipitation can be suppressed but also the scratch resistance and the penetration of organic solvents into the resin layer. And the effect of suppressing erosion can be provided. In order to set the glass transition temperature of the resin (α) to 50 ° C. or higher, the resin composition comprising the resin (A) having a glass transition temperature of 50 ° C. or higher and the melamine compound (B) is obtained by heating. Etc.

  Moreover, in order to improve the precipitation suppression property of the oligomer of a resin layer, it is preferable that resin and resin ((alpha)) which form a resin layer have the following structures.

  First, the resin (α) preferably has a structure obtained by crosslinking between acryloyl groups. That is, it is preferable that the resin forming the resin layer has a structure obtained by crosslinking between acryloyl groups. Such a crosslinked structure can be formed by heating the resin (A) having an acryloyl group.

  Next, the resin (α) preferably has a structure represented by the formula (2).

  The structure shown in Formula (2) is a structure obtained by crosslinking of a hydroxyl group and a methylol group bonded to the amino group of the melamine compound. That is, the resin forming the resin layer (X) preferably has a chemical structure of the formula (2) obtained by crosslinking of a hydroxyl group and a methylol group bonded to the amino group of the melamine compound. Such a crosslinked structure can be formed by heating the resin (A) having a hydroxyl group and the melamine compound (B) having a methylol group. When the resin or resin (α) forming the resin layer (X) has the structure represented by the formula (2), the resin layer can be provided with oligomer precipitation inhibitory property.

  Furthermore, the resin (α) preferably has a structure represented by the formula (3).

  The structure shown in Formula (3) is a structure obtained by cross-linking of methylol groups bonded to the amino group of the melamine compound. That is, it is preferable that the resin forming the resin layer (X) has a chemical structure represented by the formula (3) obtained by cross-linking of methylol groups bonded to the amino group of the melamine compound. Such a crosslinked structure can be formed by heating the melamine compound (B) having a methylol group. Resin and resin ((alpha)) which form resin layer (X) can give an oligomer precipitation inhibitory property to a resin layer by having the structure shown to Formula (3).

  In addition, the resin (α) preferably has a structure represented by the formula (4).

  The structure shown in Formula (4) is a urethane structure. That is, the resin forming the resin layer (X) preferably has a chemical structure of the formula (4). Such a structure can be introduced into the resin (α) by using, for example, a resin (A) having a urethane structure in addition to a hydroxyl group and an acryloyl group. The resin or resin (α) forming the resin layer (X) has the structure shown in the formula (4), so that the resin layer (X) can have elasticity and elasticity. That is, when the resin (α) is formed (when a crosslinked structure of acryloyl groups or a crosslinked structure represented by formulas (2) and (3) is formed), a crack occurs in the resin layer (X). The resin and the resin (α) forming the resin layer (X) may have the structure of the formula (4), thereby suppressing the generation of cracks and curls. it can.

  In the present invention, when the resin (α) is obtained using the resin (A) and the melamine compound (B), the resin composition (resin (A) and melamine compound (B) for forming the resin layer (X) is used. In the mixture), the mass ratio of the resin (A) to the melamine compound (B) is 10 parts by mass or more and 60 parts by mass or less when the mass of the resin (A) is 100 parts by mass. It is preferable that More preferably, the mass of the melamine compound (B) is 20 parts by mass or more and 50 parts by mass or less. By setting the mass of the melamine compound (B) to 10 parts by mass or more, the resin (α) can be sufficiently provided with the structure of the formula (3). As a result, the resin layer (X) can significantly suppress oligomer precipitation. Moreover, the adhesiveness between the resin layer (X) and various hard coat agents is enhanced, and further, flexibility, toughness, and solvent resistance are enhanced. On the other hand, the hardening shrinkage | contraction which generate | occur | produces when the structure of Formula (3) is formed can be suppressed because the mass of a melamine compound (B) shall be 60 mass parts or less. As a result, the occurrence of cracks in the resin layer (X) is suppressed, good oligomer precipitation suppression is maintained, and the transparency of the laminated film can be imparted.

(3) Resin (A) having hydroxyl group and acryloyl group
The resin (A) having a hydroxyl group and an acryloyl group used in the present invention is a resin having at least one hydroxyl group and one or more acryloyl groups. In the present invention, the acryloyl group includes a methacryloyl group.

  In the present invention, the resin (A) has a hydroxyl group and an acryloyl group as long as the resin (A) can be formed together with the melamine compound (B) by heating the resin (A) in any form. You may do it. For example, the resin (A) may be a resin having a polymer having a hydroxyl group and a polymer having an acryloyl group, or may be a resin having a polymer having a hydroxyl group and an acryloyl group as repeating units. Among them, the resin (A) includes an acrylic ester compound and / or a methacrylic ester compound (a), an ethylenically unsaturated compound (b) having a hydroxyl group, a chemical structure (urethane structure) represented by the formula (4), and A resin having a polymer obtained by using a compound (c) having a polyfunctional acryloyl group and polymerizing them is preferable. In terms of forming a dense cross-linked structure, it is more preferable to have a polymer in which (b) and (c) are randomly graft-polymerized on the hydrocarbon chain formed from (a). Resin (A) polymerized using these monomers ((a), (b) and (c)) can form the aforementioned resin (α) by heating with melamine compound (B). it can. Hereinafter, the compounds (a), (b) and (c) will be described.

Acrylic ester compound and / or methacrylic ester compound (a):
The compound (a) is a monomer that forms the main skeleton of the resin (A). Specific examples of the compound (a) include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, and acrylic acid. n-octyl, i-octyl acrylate, t-octyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, methacrylic acid C 1-18 alkyl of acrylic acid and / or methacrylic acid such as i-butyl, t-butyl methacrylate, n-octyl methacrylate, i-octyl methacrylate, t-octyl methacrylate, 2-ethylhexyl methacrylate Esters and other esters such as cyclohexyl acrylate Cycloalkyl esters of (b) 5 to 12 carbon atoms, and the like aralkyl ester of acrylic acid benzyl having 7 to 12 carbon atoms.

  When the resin (A) is polymerized using the compounds (a), (b) and (c), the mass of the compound (a) is 100 parts by mass of the total mass of the compounds (a) to (c). Is preferably 55 parts by mass or more and 98 parts by mass or less. The resin (A) can be efficiently polymerized by setting the mass (preparation amount) of the compound (a) within the above numerical range.

Ethylenically unsaturated compound (b) having a hydroxyl group:
The compound (b) needs to have a hydroxyl group. By using the compound (b) as a monomer, the resin (A) can have a hydroxyl group.

  Specific examples of the compound (b) include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, and 4-hydroxy acrylate. Butyl, 6-hydroxyhexyl acrylate, 2-hydroxyethyl allyl ether, 2-hydroxypropyl allyl ether, 2-hydroxybutyl allyl ether, allyl alcohol, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methacrylic acid 3 -Hydroxypropyl, 2-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl methacrylate, 2-hydroxyethyl methacrylate Le, 2-hydroxypropyl methallyl ether, unsaturated compounds containing one or more hydroxyl groups in the molecule such as 2-hydroxybutyl methallyl ether.

  Moreover, the compound (b) may have a carboxyl group.

  When polymerizing the resin (A) using the compounds (a), (b) and (c), the mass of the compound (b) is 100 parts by mass of the total mass of the compounds (a) to (c). When it is, it is preferable that it is 1 to 30 mass parts. By setting the mass (preparation amount) of the compound (b) to 1 part by mass or more, the resin (A) can have a sufficient amount of hydroxyl groups. Moreover, resin (A) can be efficiently polymerized because the mass of a compound (b) shall be 30 mass parts or less. When the mass of the compound (b) exceeds 30 parts by weight, the resin (A) dispersed in water or water-solubilized in the aqueous solvent (E) becomes a gel when preparing a coating liquid containing a resin composition by the method described later. It may become difficult to use suitably.

Compound (c) having chemical structure (urethane structure) represented by formula (4) and acryloyl group:
The compound (c) used in the present invention needs to have an acryloyl group. In addition, it is preferable that the acryloyl group of the compound (c) is polyfunctional because a dense cross-linked structure can be formed in the resin (α). The number of acryloyl groups possessed by the compound (c) is preferably 2 or more and 15 or less. In the present invention, the acryloyl group includes a methacryloyl group. By using the compound (c) as a monomer, the resin (A) can have an acryloyl group. In addition to the polyfunctional acryloyl group, the compound (c) preferably has a urethane structure in the molecule. By using such a compound (c) as a monomer, the resin (A) can have an acryloyl group and a urethane structure.

  Specifically, the compound (c) includes a compound obtained by reacting a polyhydric alcohol, an isocyanate monomer and / or an organic polyisocyanate, an acrylate monomer having a hydroxyl group and / or a methacrylate monomer having a hydroxyl group, A urethane acrylate compound obtained by reacting and synthesizing in a solvent-free or organic solvent is preferred.

  Examples of the polyhydric alcohol include acrylic polyols, polyester polyols, polycarbonate polyols, ethylene glycol, and propylene glycol. Isocyanate monomers include tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and organic polyisocyanates include adduct type, isocyanurate type and burette type polyisocyanates synthesized from isocyanate monomers. Can be mentioned. Examples of the acrylate monomer having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, isocyanuric acid ethylene oxide-modified diacrylate, pentaerythritol tri- and tetraacrylate, and dipentaerythritol pentaacrylate. Examples of the methacrylate monomer having a hydroxyl group include 2-hydroxyethyl methacrylate and hydroxypropyl methacrylate. The compound (c) may contain a methylol group.

  When the resin (A) is polymerized using the compounds (a), (b) and (c), the mass of the compound (c) is 100 parts by mass of the total mass of the compounds (a) to (c). It is preferable that it is 1 to 15 mass parts. By setting the mass of the compound (c) to 1 part by mass or more, the resin (A) can have a sufficient amount of acryloyl group or urethane structure.

  On the other hand, when the mass of the compound (c) exceeds 15 parts by mass, the following phenomenon may occur, which is not preferable. That is, when the mass of the compound (c) exceeds 15 parts by mass, since the resin (A) has an excessive amount of acryloyl groups, when the resin (A) is heated to obtain the resin (α), the acryloyl groups are The cross-linked structure is very much formed. As a result, significant curing shrinkage is caused, and cracks may occur in the resin layer.

(4) Production Method of Resin (A) Having Hydroxyl Group and Acrylyl Group The production method of the resin (A) used in the present invention is not particularly limited, and a known technique can be applied. It is preferable to use the compounds (a), (b) and (c). Furthermore, as a manufacturing method of resin (A), it is preferable to manufacture by emulsion polymerization in an aqueous solvent (E) using compounds (a), (b) and (c). By using the aqueous solvent (E), it becomes easy to adjust the coating liquid containing the resin composition using the aqueous solvent (E). Further, it is preferable to produce the resin (A) by emulsion polymerization because the mechanical dispersion stability of the resin (A) is excellent.

  The emulsifier used in the present invention is not particularly limited by any of an anionic emulsifier and a nonionic emulsifier, and may be used alone or in combination of two or more.

  Examples of the anionic emulsifier include higher fatty acid salts such as sodium oleate, alkylaryl sulfonates such as sodium dodecylbenzenesulfonate, and alkyl sulfate esters such as sodium lauryl sulfate. Examples of nonionic emulsifiers include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene octylphenyl ethers.

  In the emulsion polymerization, for example, persulfates such as sodium persulfate, potassium persulfate and ammonium persulfate, and organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide and p-menthane hydroperoxide are usually used. A polymerization initiator such as hydrogen peroxide is used. These polymerization initiators can also be used in any form of one kind or a combination of plural kinds.

  In emulsion polymerization, a reducing agent can be used in combination with a polymerization initiator as desired. Examples of such reducing agents include reducing organic compounds such as ascorbic acid, tartaric acid, citric acid, glucose, and formaldehyde sulfoxylate metal salts; sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium metabisulfite, A reducing inorganic compound such as ammonium sulfite can be used.

  Furthermore, a chain transfer agent can be used in the emulsion polymerization. Examples of such chain transfer agents include n-dodecyl mercaptan, t-dodecyl mercaptan, n-butyl mercaptan, 2-ethylhexyl thioglycolate, 2-mercaptoethanol, trichlorobromomethane, and the like. The polymerization temperature suitably employed in the emulsion polymerization of the resin (A) of the present invention is about 30 to 100 ° C.

(5) Melamine compound having a methylol group (B)
The melamine compound (B) that can be used in the present invention needs to have at least one triazine ring and one methylol group in one molecule. By using such a melamine compound (B), the resin (α) can have a cross-linked structure between methylol groups represented by the formula (2).

  Specifically, the melamine compound (B) is a compound obtained by dehydrating and condensing methyl alcohol melamine derivative obtained by condensing melamine and formaldehyde with methyl alcohol, ethyl alcohol, isopropyl alcohol or the like as a lower alcohol. Is preferred.

  Examples of methylolated melamine derivatives include monomethylol melamine, dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, and hexamethylol melamine.

  In the present invention, the mass ratio of the melamine compound (B) is preferably 10 parts by mass or more and 60 parts by mass or less as described above when the mass of the resin (A) is 100 parts by mass. More preferably, the mass of the melamine compound (B) is 20 parts by mass or more and 50 parts by mass or less.

(6) Compound (C) containing at least one selected from isocyanate compounds, carbodiimide compounds, and oxazoline compounds:
In the present invention, the resin forming the resin layer (X) includes at least one selected from an isocyanate compound, a carbodiimide compound, and an oxazoline compound in addition to the resin (α), the resin (A), and the melamine compound (B). A compound (C) can be contained.

  As compounds having an isocyanate group, 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 1,5-naphthylene diisocyanate, 4,4-diphenylmethane diisocyanate Aromatic polyisocyanate compounds such as 3,3-dimethyldiphenylmethane-4,4-diisocyanate, 1,3-xylylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2 , 4-trimethyl-1,6-hexamethylene diisocyanate, 1,8-octamethylene diisocyanate, 1,10-decamethylene diisocyanate and the like, or dimers or trimers of these isocyanates and their isocyanates When, for example, ethylene glycol, adduct of divalent or trivalent polyols such as trimethylolpropane and the like can be exemplified.

The compound having an oxazoline group is not particularly limited as long as it has at least one oxazoline group or oxazine group per molecule, but an addition polymerizable oxazoline group-containing monomer is preferable, and 2-vinyl-2-oxazoline, 2 -Vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl- Mention may be made of 5-ethyl-2-oxazoline.
The compound having a carbodiimide group is not particularly limited as long as it has at least one carbodiimide structure represented by the following formula (5) per molecule. Particularly preferred are polycarbodiimide compounds having two or more in them. In particular, when a polymer type isocyanate compound having a plurality of carbodiimide groups is used at the terminal or side chain of a polymer such as polyester resin or acrylic resin, the resin layer of the present invention is provided on the polyester film, In this case, not only the hardness of the resin layer is improved and the oligomer precipitation is suppressed, but also adhesion to various inks and hard coat agents, wet heat and heat resistance, flexibility, and toughness can be preferably used.
-N = C = N- (5)
A known technique can be applied to the production of the carbodiimide compound, and it is generally obtained by polycondensation of a diisocyanate compound in the presence of a catalyst. As the diisocyanate compound that is a starting material of the polycarbodiimide compound, aromatic, aliphatic, and alicyclic diisocyanates can be used. Specifically, tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate. , Isophorone diisocyanate, dicyclohexyl diisocyanate and the like can be used. Furthermore, in order to improve the water solubility and water dispersibility of the polycarbodiimide compound within the range not losing the effect of the present invention, a surfactant is added, polyalkylene oxide, quaternary ammonium salt of dialkylamino alcohol, hydroxy A hydrophilic monomer such as an alkyl sulfonate may be added or used.

  Other compounds such as aziridine compounds, amide epoxy compounds, titanate coupling agents such as titanium chelates, methylolated or alkylolated urea compounds, acrylamide compounds, and the like can be optionally used.

  In the present invention, the mass of the compound (C) containing at least one selected from an isocyanate compound, a carbodiimide compound, and an oxazoline compound is 40 parts by mass or more and 100 parts by mass when the mass of the resin (A) is 100 parts by mass. Part or less. More preferably, the mass of the compound (C) is 55 parts by mass or more and 85 parts by mass or less. By setting the compound (C) to 40 parts by mass or more, the resin layer (X) has a functional group index satisfying the formula (1), and can exhibit good adhesiveness with various hard coat agents. On the other hand, by setting the compound (C) to 100 parts by mass or less, the resin layer (X) maintains the good adhesiveness with various hard coat agents and expresses the oligomer inhibitory property of the resin (α). Can do.

(7) Polyester film In the laminated film of this invention, the polyester film used as a base film is demonstrated in detail. Polyester is a general term for polymers having an ester bond as a main bond chain, and includes ethylene terephthalate, propylene terephthalate, ethylene-2,6-naphthalate, butylene terephthalate, propylene-2,6-naphthalate, ethylene. Those having at least one component selected from -α, β-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylate as a main component can be preferably used. In the present invention, it is preferable to use polyethylene terephthalate as the polyester film. In addition, when heat or shrinkage stress acts on the polyester film, it is particularly preferable to use polyethylene-2,6-naphthalate having excellent heat resistance and rigidity as the polyester film.

  The polyester film is preferably biaxially oriented. A biaxially oriented polyester film is generally an unstretched polyester sheet or film that is stretched about 2.5 to 5 times in the longitudinal direction and in the width direction perpendicular to the longitudinal direction, and then subjected to heat treatment to produce crystals. The alignment is completed, and it indicates a biaxial alignment pattern by wide-angle X-ray diffraction. When the polyester film is not biaxially oriented, the thermal stability of the laminated film, particularly the dimensional stability and mechanical strength are insufficient, or the flatness is poor.

  In the polyester film, various additives such as antioxidants, heat stabilizers, weathering stabilizers, ultraviolet absorbers, organic lubricants, pigments, dyes, organic or inorganic fine particles, fillers, antistatic agents. An agent, a nucleating agent, etc. may be added to such an extent that the properties are not deteriorated.

  The thickness of the polyester film is not particularly limited and is appropriately selected depending on the application and type, but is preferably preferably 10 to 500 μm, more preferably 25 to 250 μm from the viewpoint of mechanical strength, handling properties, and the like. Most preferably, it is 50-150 micrometers. The polyester film may be a composite film obtained by coextrusion or a film obtained by bonding the obtained film by various methods.

(8) Method for forming resin layer In the present invention, a resin composition containing the resin (A), the melamine compound (B), and the compound (C) is provided on at least one surface of the polyester film, and then heated to obtain a polyester film. It is preferable to form a resin layer containing the resin (α) thereon. In particular, by setting the heating temperature to 150 ° C. or higher, it becomes possible to effectively form the resin layer (X) having the structures of the formulas (2) and (3). Thereby, it is possible to obtain a laminated film that is excellent in adhesiveness with various hard coat agents and is difficult to precipitate an oligomer.

  Moreover, in the said resin composition, it is preferable that the sum total of content of resin (A), a melamine compound (B), and a compound (C) is 80 mass% or more with respect to solid content in a resin composition. . By making the total content of the resin (A), the melamine compound (B) and the compound (C) 80% by mass or more, the structure of the formulas (2) and (3) can be efficiently formed when heated. It becomes possible to form the resin layer which has. On the other hand, other various additives other than the resin (A), the melamine compound (B), and the compound (C) may have a total content of less than 20% by weight based on the solid content in the resin composition. preferable. Formula (2) and Formula (3) obtained from the resin (A) and the melamine compound (B) described above by making the total content of the compound (C) and other various additives less than 20% by weight. The adhesiveness of the resin layer (X) to various hard coat agents can be improved without hindering the formation of the resin layer (X) having the following structure.

  When the resin composition containing the resin (A), the melamine compound (B), and the compound (C) is provided on the polyester film, a solvent may be used. That is, the resin (A), the melamine compound (B), and the compound (C) may be dissolved or dispersed in a solvent to form a coating solution, which may be applied to a polyester film. After the application, the solvent is dried and heated to obtain a film on which the resin (α) is laminated. In the present invention, it is preferable to use an aqueous solvent (E) as the solvent. By using an aqueous solvent, it is possible to suppress the solvent from rapidly evaporating in the heating step, and a uniform resin layer can be formed. Aqueous solvents are superior in terms of environmental burden compared to organic solvents.

  Here, the aqueous solvent (E) is water, water and alcohols such as methanol, ethanol, isopropyl alcohol and butanol, ketones such as acetone and methyl ethyl ketone, and glycols such as ethylene glycol, diethylene glycol and propylene glycol. Is an organic solvent that is soluble in a mixture at an arbitrary ratio.

  As a method for applying the resin composition to the polyester film, either an in-line coating method or an off-coating method can be used, but an in-line coating method is preferable. The in-line coating method is a method of applying in the process of manufacturing a polyester film. Specifically, it refers to a method of coating at any stage from melt extrusion of a polyester resin to biaxial stretching followed by heat treatment and winding up, and is generally substantially non-obtainable after melt extrusion and rapid cooling. An unstretched (unoriented) polyester film in a crystalline state (hereinafter sometimes referred to as A film), and then a uniaxially stretched (uniaxially oriented) polyester film (hereinafter sometimes referred to as B film) stretched in the longitudinal direction, or Further, it is applied to any one of biaxially stretched (biaxially oriented) polyester films (hereinafter sometimes referred to as C films) before heat treatment and stretched in the width direction.

  In the present invention, the resin composition is applied to any one of the A film and B film of the polyester film before crystal orientation is completed, the solvent is evaporated, and then the polyester film is uniaxially or biaxially. It is preferable to employ a method in which the resin film is provided while being stretched and heated to complete the crystal orientation of the polyester film. According to this method, the polyester film can be formed, the resin composition can be applied, the solvent can be dried, and the heating (that is, the resin layer can be formed) at the same time. Moreover, it is easy to make the thickness of the resin layer thinner in order to perform stretching after coating.

  Especially, the method of apply | coating a resin composition to the film (B film) uniaxially stretched in the longitudinal direction, drying a solvent, and extending | stretching in the width direction after that and heating is preferable. Compared with the method of biaxially stretching after applying to an unstretched film, the stretching process is less than once, so that the occurrence of defects and cracks in the resin layer due to stretching can be suppressed.

  On the other hand, the off-line coating method is different from the film-forming process on the film after the A film is stretched uniaxially or biaxially and subjected to heat treatment to complete the crystal orientation of the polyester film, or the A film. This is a method of applying a resin composition in the process. In this invention, it is preferable to provide by the in-line coating method from the various advantages mentioned above.

  Therefore, the best method for forming the resin layer in the present invention is to apply a resin composition using an aqueous solvent (E) on a polyester film using an in-line coating method, dry the aqueous solvent (E), and heat. It is the method of forming by doing.

(8) Adjustment method of coating liquid containing resin composition When preparing the coating liquid containing a resin composition, it is preferable to use an aqueous solvent (E) as a solvent. The coating liquid containing the resin composition is mixed and stirred in the desired weight ratio of the resin (A), the melamine compound (B), and the aqueous solvent (E), which are dispersed in water or water as necessary, in any order. Can be produced. Next, various additives such as a lubricant, inorganic particles, organic particles, a surfactant, an antioxidant, and a thermal initiator are arbitrarily selected as necessary so as not to deteriorate the properties of the resin layer formed by the resin composition. In this order, they can be mixed and stirred. The mixing and stirring methods can be performed by shaking the container by hand, using a magnetic stirrer or stirring blade, irradiating ultrasonic waves, vibrating and dispersing.

(9) Coating method As a coating method of the resin composition on the polyester film, a known coating method such as a bar coating method, a reverse coating method, a gravure coating method, a die coating method, or a blade coating method may be used. it can.

(10) Method for Producing Laminate Film The method for producing a laminate film of the present invention will be described with reference to an example using a polyethylene terephthalate (hereinafter referred to as PET) film as the polyester film. First, PET pellets are sufficiently vacuum-dried, then supplied to an extruder, melt extruded into a sheet at about 280 ° C., and cooled and solidified to produce an unstretched (unoriented) PET film (A film). This A film is stretched 2.5 to 5.0 times in the longitudinal direction with a roll heated to 80 to 120 ° C. to obtain a uniaxially oriented PET film (B film). A coating liquid having a resin composition containing a resin (A), a melamine compound (B), and a compound (C) prepared at a predetermined concentration is applied to one surface of the B film. At this time, surface treatment such as corona discharge treatment may be performed on the coated surface of the PET film before coating. By performing surface treatment such as corona discharge treatment, the coating property of the resin composition on the PET film is improved, so that the resin composition can be prevented from being repelled and a uniform coating thickness can be achieved.

  After coating, the edge of the PET film is held with a clip and guided to a preheating zone of 80 to 130 ° C., and the solvent of the coating solution is dried. After drying, the film is stretched 1.1 to 5.0 times in the width direction. Subsequently, the heat treatment is guided to a heat treatment zone of 150 to 250 ° C., and heat treatment is performed for 1 to 30 seconds to complete the crystal orientation and the formation of the resin layer containing the resin (α). In this heating step (heat treatment step), 3 to 15% relaxation treatment may be performed in the width direction or the longitudinal direction as necessary. The laminated film thus obtained has good transparency, suppresses the generation of scratches in the transport process and the processing process, and suppresses oligomer precipitation from the polyester film in the processing process involving heat treatment.

(Characteristic measurement method and effect evaluation method)
The characteristic measuring method and the effect evaluating method in the present invention are as follows.

(1) Measurement of total light transmittance and haze Three points (three) of square-shaped laminated film samples each having a side of 5 cm are prepared. The sample is then left for 40 hours at 23 ° C. and 50% relative humidity. Each sample was measured with a turbidimeter “NDH5000” manufactured by Nippon Denshoku Industries Co., Ltd., and the total light transmittance was measured according to JIS “Testing method of total light transmittance of plastic transparent material” (K7361-1, 1997 edition). ), Haze is measured by a method according to JIS “How to Obtain Haze of Transparent Materials” (K7136, 2000 edition). The total light transmittance and haze value of each of the three points (three) are averaged to obtain the total light transmittance and haze value of the laminated film.

(2) Measurement of resin layer thickness First, a laminated film, stained with RuO _4. Next, after freezing the laminated film, it is cut in the film thickness direction to obtain 10 (10) ultra-thin slice samples for observing the cross section of the resin layer. Each sample cross section is observed with a TEM (transmission electron microscope: H7100FA type manufactured by Hitachi, Ltd.) at a magnification of 10,000 to 1,000,000 to obtain a cross-sectional photograph. The measured values of the resin layer thickness of the 10 samples (10 pieces) are averaged to obtain the resin layer thickness of the laminated film.

(3) Structure confirmation of the formulas (2) to (4) in the resin forming the resin layer The method for confirming the structures of the formulas (2) to (4) in the resin forming the resin layer is a particularly specific method. Although not limited, the following methods can be illustrated. For example, the presence or absence of a weight peak derived from the structures of formulas (2) to (4) is confirmed by gas chromatograph mass spectrometry (GC-MS). Next, by Fourier transform infrared spectroscopy (FT-IR), the presence or absence of a peak derived from the bond between each atom of the structures of formulas (2) to (4) is confirmed. Further, in proton nuclear magnetic resonance spectroscopy (1H-NMR), the position of the chemical shift derived from the position of the hydrogen atom and the number of proton absorption lines derived from the number of hydrogen atoms in the structures of formulas (2) to (4) Confirm. A method of comprehensively confirming these results is preferable.

(4) Measurement of glass transition temperature (Tg) of resin (α) First, 5 mg of the laminated film is weighed. Next, the measured laminated film is measured with a temperature modulation differential scanning calorimeter (TMDSC) Q1000 (manufactured by TA Instruments). In a temperature-modulated differential scanning calorimeter, the entire DSC signal (total heat flow) is separated into a reversible thermal component that generates heat and endotherm, such as glass transition, and an irreversible thermal component, such as enthalpy relaxation, curing reaction, and solvent removal. it can. A signal derived from the glass transition point of the resin (α), which is a reversible component, is extracted from the entire differential scanning calorimetric signal obtained by the measurement, and used as the glass transition point of the resin (α). Here, the glass transition point of the polyester that forms the polyester film that is the base film of the laminated film is measured in advance to distinguish the polyester that forms the polyester film from the glass transition point of the resin (α). be able to.

(5) Calculation of surface energy (x) The surface energy (x) (unit: mN / m) of the resin layer (X) of the laminated film is calculated by the following method. The laminated film is allowed to stand for 24 hours in an atmosphere of room temperature 23 ° C. and relative humidity 65%. Thereafter, the contact angle of each of the four types of solutions of pure water, ethylene glycol, formamide, and diiodomethane with respect to the resin layer (X) under the same atmosphere was measured using a contact angle meter CA-D type (Kyowa Interface Science Co., Ltd.). ) And 5 points each. The average value of the three measured values excluding the maximum value and the minimum value of the five measured values is defined as the contact angle of each solution. In addition, the measurement of the interface side with the polyester film of the resin layer (X) is performed by once eluting the polyester film (P) with a solvent and exposing the interface with the polyester film of the resin layer (X).

Next, using the contact angles of the four types of solutions obtained, “the surface free energy (γ) of the solid, which is proposed by Hata et al., Is expressed as a dispersion force component (γ _S ^d ) and a polar force component (γ _S ^p ). , And the hydrogen bonding force component (γ _S ^h ), and the geometric mean method based on the formula (expanded Fowkes formula) obtained by extending the Fowkes formula, The surface energy that is the sum of the polar forces is calculated.

A specific calculation method is shown. The meaning of each symbol is described below. When γ _S ^L is the tension at the interface between the solid and the liquid, Equation (1) is established.

γ _S ^L : surface free energy of resin layer (X) and known solutions listed in Table 1 γ _S : surface free energy of resin layer (X) γ _L : surface free energy of known solutions listed in Table 1 γ _S ^d : Dispersion force component of surface free energy of resin layer (X) γ _S ^p : Polar force component of surface free energy of resin layer (X) γ _S ^h : Hydrogen bond strength of surface free energy of resin layer (X) Component γ _L ^d : Dispersion force component of the surface free energy of the known solution described in Table 1 γ _L ^p : Polar force component of the surface free energy of the known solution described in Table 1 γ _L ^h : As described in Table 1 Hydrogen bonding force component of the surface free energy of the known solution γ _S ^L = γ _S + γ _L -2 (γ _S ^d · γ _L ^d ) ^1/2 -2 (γ _S ^p · γ _L p) ^1/2 -2 (γ _S ^h · γ _L ^h ) ^1/2 Equation (5).

  The state when the smooth solid surface and the droplet are in contact with each other at the contact angle (θ) is expressed by the following equation (Young's equation).

γ _S = γ _S ^L + γ _L cos θ (6).

When these mathematical formulas (1) and (2) are combined, the following formula is obtained.
_{^{(γ S d · γ L d}} ) 1/2 + (γ S p · γ L p) 1/2 + (γ S h · γ L h) 1/2 = γ L (1 + cosθ) / 2 ··· formula (7).

Actually, the four components of water, ethylene glycol, formamide, and diiodomethane have contact angles (θ) and the components of the surface tension of known solutions listed in Table 1 (γ _L ^d , γ _L ^p , γ _L ^h ) is substituted into Equation (3) to solve the four simultaneous equations. As a result, the surface energy (γ) of the solid, that is, the surface energy of the surface of the resin layer (X) is calculated.

(6) Calculation of functional group index (y) First, an X-ray photoelectron spectroscopy (XPS) measuring device Quantera SXM (manufactured by PHI, excitation X-ray: monochoromatic AlKα _1.2 line is applied to the resin layer (X) surface of the laminated film. (1486.6 eV), X-ray diameter: 200 μm, photoelectron escape angle: 45 °), and the elemental composition and chemical state are examined. XPS analysis is a method in which the surface of the resin layer (X) placed in an ultra-high vacuum is irradiated with soft X-rays and photoelectrons emitted from the surface of the resin layer (X) are detected by an analyzer. Elemental information of the resin layer (X) can be obtained from the electron binding energy value, and information relating to quantification can be obtained from the energy shift of each peak and the valence, bonding state, and peak area ratio. Since the length (mean free path) that the photoelectron can travel through the substance is less than 10 nm, the detection depth in this analysis method is less than 10 nm. Composition ratio of carbon element composition (%) with respect to the total amount of elements obtained by XPS analysis and C—N bond and C—O bond in C1s peak obtained by dividing the peak related to carbon (carbon element) In the composition, the functional group index is obtained by multiplying the ratio of carbon to C—N bonds and C—O bonds. That is, the functional group index means that the total amount of elements detected by XPS is 100%, [Carbon element composition (%)] indicating the ratio of carbon, in which carbon is C- It is a value obtained by multiplying the ratio of N bonds and C—O bonds [the ratio of C—N bonds and C—O bonds to the carbon element composition]. Functional group index (y) (%) = [carbon element composition (%) with respect to the total amount of elements] × [proportion of being a C—N bond and a C—O bond with respect to the carbon element composition] By y), the amount of C—N bonds and C—O bonds existing on the surface of the resin layer (X) can be evaluated.

(7) Adhesive evaluation with hard coat agent In order to evaluate the adhesion of the laminated film to the hard coat agent in the present invention, an organic solvent paint-based ultraviolet curable hard coat agent (HC-A, HC-B), Solvent-free UV curable resin (HC-C) was used.

HC-A: (Adjusted with the following composition ratio)
Dipentaerythritol hexaacrylate: 70 parts by weight N-vinylpyrrolidone: 30 parts by weight 1-hydroxycyclohexyl phenyl ketone: 4 parts by weight

HC-B: “Opstar” (registered trademark) KZ6445A manufactured by JSR Corporation
HC-C: Solvent-free transparent ultraviolet curable resin (adjusted with the following composition ratio)
• Sanyo Chemical Co., Ltd. “Sunrad” (registered trademark) RC-610: 60 parts by weight • Mitsubishi Rayon Co., Ltd. “Diabeam” (registered trademark) UR-6530: 20 parts by weight • Nippon Kayaku Co., Ltd. DPHA (dipentaerythritol pentaacrylate / dipentaerythritol hexaacrylate mixture): 20 parts by weight.

Here, about hard coat A and hard coat B, it applied to the surface of resin layer (X) of a lamination film so that the film thickness after hardening may be set to 2 micrometers using a bar coater, and hot air made from ESPEC CORP. It was dried in an oven “HIGH-TEMP-OVEN PHH-200” at 100 ° C. for 1 minute, and then using an ultraviolet lamp with an irradiation intensity of 120 W / cm, an irradiation distance (distance between the lamp and the ink surface) of 12 cm, and a conveyor speed of 3 m / Minutes, the hard coat layer was cured by UV irradiation at an integrated intensity of about 350 mJ / cm ² . Adhesion evaluation was performed using the following cross-cut method.

About hard coat C, it apply | coats to the surface of resin layer (X) of a laminated film so that it may become a thickness of about 5 micrometers by the wire bar coating method, Then, an ultraviolet ray lamp with irradiation intensity 120W / cm is used, irradiation distance (lamp The distance between the ink and the ink surface) was 12 cm, UV irradiation was performed at a conveyor speed of 2 m / min, and an integrated intensity of about 550 mJ / cm ² to cure the solvent-free transparent ultraviolet curable resin. Adhesion evaluation was performed using the following cross-cut method.

<Cross cut method>
100 pcs of the cross cut of 1mm ² to the cured film of various hard coat, stuck Nichiban Co., Ltd. made "cellophane tape" (registered trademark) on it, using a rubber roller, 3 round-trip with a load of 19.6N And pressed, peeled in the direction of 90 degrees, and evaluated by the number of remaining cured films. The evaluation was carried out three times, and in the average value of the three measurements, the remaining number was 80 or more as good adhesion “◯”, and less than 80 as poor adhesion “x”.

(8) Heat treatment evaluation A laminated film sample having a side of 10 cm is fixed to a metal frame at four sides. Next, in the hot air oven “HIGH-TEMP-OVEN PHH-200” manufactured by ESPEC Co., Ltd., in which the laminated film sample fixed to the metal frame is set to 150 ° C. (air flow gauge “7”), the floor in the oven Stand and heat for 1 hour. Thereafter, the laminated film sample was allowed to stand for 1 hour by air cooling.

  Next, when the resin layer is formed only on one surface of the polyester film, the oligomer deposited from the polyester film surface opposite to the resin layer is removed by the following method. That is, the surface of the polyester film opposite to the resin layer was wiped off with a nonwoven fabric containing acetone (manufactured by Ozu Sangyo Co., Ltd., Hyze Gauze NT-4) and further rinsed with acetone at 23 ° C. and 50% relative humidity. Let dry for 40 hours. Thereafter, the haze is measured as in (1), and the difference from the haze before the heat treatment evaluation is evaluated as Δhaze.

  When the resin layer is formed on both sides of the polyester film, the haze of the sample that has been allowed to stand for 1 hour by air cooling is measured in the same manner as in (1), and the difference from the haze before the heat treatment evaluation is halved. The value (= ((haze value after evaluation of heat treatment) − (haze value before evaluation of heat treatment)) / 2) is evaluated as Δhaze. Δhaze is less than 0.3%.

  In both cases where the resin layer is formed only on one side of the polyester film and where the resin layer is formed on both sides of the polyester film, Δhaze is less than 0.3%. As a guide, if the Δhaze is less than 0.3%, the change in haze value is not visually recognized before and after the heat treatment. If it is 0.3% or more and less than 0.5%, there is an individual difference, but there is a possibility that a change in the haze value visually observed before and after the heat treatment. If it is 0.5% or more, a change in haze visually can be clearly seen before and after the heat treatment.

Example 1
Resin having a hydroxyl group and an acryloyl group (A):
In a stainless steel reaction vessel, methyl methacrylate (a), hydroxyethyl methacrylate (b), urethane acrylate oligomer (manufactured by Negami Kogyo Co., Ltd., Art Resin (registered trademark) UN-3320HA, the number of acryloyl groups is 6) (c ) Was added at a mass ratio in the table, and 2 parts by mass of sodium dodecylbenzenesulfonate as an emulsifier was added to a total of 100 parts by mass of (a) to (c) and stirred to prepare a mixed solution 1. Next, a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel was prepared. 60 parts by weight of the above mixed liquid 1, 200 parts by weight of isopropyl alcohol, and 5 parts by weight of potassium persulfate as a polymerization initiator were charged into a reactor, and heated to 60 ° C. to prepare a mixed liquid 2. The mixed liquid 2 was held for 20 minutes while being heated at 60 ° C. Next, a mixed solution 3 comprising 40 parts by weight of the mixed solution 1, 50 parts by weight of isopropyl alcohol, and 5 parts by weight of potassium persulfate was prepared. Subsequently, the mixed solution 3 was dropped into the mixed solution 2 using a dropping funnel over 2 hours to prepare the mixed solution 4. Thereafter, the mixed solution 4 was kept for 2 hours while being heated to 60 ° C. The obtained mixed liquid 4 was cooled to 50 ° C. or lower and then transferred to a container equipped with a stirrer and a decompression facility. Resin dispersed in pure water by adding 60 parts by weight of ammonia water having a concentration of 25% by weight and 900 parts by weight of pure water and recovering isopropyl alcohol and unreacted monomers under reduced pressure while heating to 60 ° C. (A) was obtained.
Melamine compound having a methylol group (B):
Methylolated melamine (manufactured by Sanwa Chemical Co., Ltd., Nicalac (registered trademark) MX-035) was used.
Compound (C) containing at least one selected from isocyanate compounds, carbodiimide compounds, and oxazoline compounds:
(C) -1: Oxazoline compound ("Epocross" WS-500 manufactured by Nippon Shokubai Co., Ltd.)
(C) -2: A carbodiimide compound (Nisshinbo Chemical Co., Ltd. “Carbodilite” V-04) was used.

-Resin composition and coating liquid containing resin composition:
Resin (A), melamine compound (B), and compound (C) in mass ratio, (A) / (B) / (C) ((C) -1 / (C) -2 = 37/40) = 100 / 10/77 was mixed. In order to impart easy slipping to the surface of the laminated film, silica particles having a number average particle size of 300 nm (Seahoster (registered trademark) KE-W30 manufactured by Nippon Shokubai Co., Ltd.) as resin particles (A) 100 are used. 2 parts by mass was added to parts by mass. Further, in order to improve the coating property of the resin composition on the polyester film, a fluorosurfactant (Plus Coat (registered trademark) RY-2 manufactured by Kyoyo Chemical Co., Ltd.) is added to the resin composition. It added so that content with respect to the coating liquid containing may be 0.03 mass part.

・ Polyester film:
PET pellets (intrinsic viscosity 0.63 dl / g) substantially free of particles were sufficiently vacuum-dried and then fed to an extruder and melted at 285 ° C. Next, the melted PET was extruded into a sheet form from a T-shaped die and wound around a mirror casting drum having a surface temperature of 25 ° C. by using an electrostatic application casting method to be cooled and solidified. This unstretched film was heated to 90 ° C. and stretched 3.4 times in the longitudinal direction to obtain a uniaxially stretched film (B film).

・ Laminated film:
The resin composition was applied to one side of the uniaxially stretched film with a coating thickness of about 8 μm using a bar coat. Subsequently, both end portions in the width direction of the uniaxially stretched film coated with the resin composition were held with clips and led to the preheating zone. The atmospheric temperature of the preheating zone was set to 90 ° C. to 100 ° C., and the solvent of the coating liquid containing the resin composition was dried. Subsequently, the film is continuously stretched 3.5 times in the width direction in a stretching zone at 110 ° C., and then heat treated for 20 seconds in a heat treatment zone at 235 ° C. to form a resin (α), thereby completing the crystal orientation of the polyester film. A laminated film was obtained. In the obtained laminated film, the thickness of the PET film was 100 μm, and the thickness of the resin layer (X) was 150 nm.

  About resin which forms resin layer (X) of a laminated | multilayer film, presence of the weight peak derived from the structure of Formula (2)-(4) was confirmed by gas chromatograph mass spectrometry (GC-MS). Next, the presence of peaks derived from the bonds between the atoms of the structures of formulas (2) to (4) was confirmed by Fourier transform infrared spectroscopy (FT-IR). Finally, in proton nuclear magnetic resonance spectroscopy (1H-NMR), the number of hydrogen atoms is calculated from the position of the chemical shift derived from the position of the hydrogen atom in the structures of formulas (2) to (4) and the proton absorption line area. confirmed. By combining these results, it was confirmed that the resin layer (X) had the structures of formulas (2) to (4).

  Table 2 shows the characteristics and the like of the obtained laminated film. The calculation result of the surface energy and functional group index satisfies the formula (1), is excellent in transparency such as total light transmittance and haze, and the evaluation of adhesiveness is “◯”, and change in haze after heat treatment at 150 ° C. for 1 hour. Was within 0.3%, which was a good result.

(Example 2)
Resin (A), melamine compound (B), and compound (C) in mass ratio, (A) / (B) / (C) ((C) -1 / (C) -2 = 35/35) = 100 A laminated film was obtained in the same manner as in Example 1 except that the mixture was mixed to be / 20/70. Table 2 shows the characteristics and the like of the obtained laminated film. Similar to Example 1, the calculation result of the surface energy and the functional group index satisfies the formula (1), is excellent in transparency such as total light transmittance and haze, and has an evaluation of adhesion of “◯” and 150 ° C. The haze change after the time heat treatment was a good result within 0.3%.

(Example 3)
Resin (A), melamine compound (B), and compound (C) in mass ratio, (A) / (B) / (C) ((C) -1 / (C) -2 = 35/48) = 100 A laminated film was obtained in the same manner as in Example 1 except that the mixture was mixed to be / 22/83. Table 2 shows the characteristics and the like of the obtained laminated film. Similar to Example 1, the calculation result of the surface energy and the functional group index satisfies the formula (1), is excellent in transparency such as total light transmittance and haze, and has an evaluation of adhesion of “◯” and 150 ° C. The haze change after the time heat treatment was a good result within 0.3%.

Example 4
Resin (A), melamine compound (B), and compound (C) in mass ratio, (A) / (B) / (C) ((C) -1 / (C) -2 = 23/23) = 100 A laminated film was obtained in the same manner as in Example 1 except that the mixture was mixed to be / 20/46. Table 2 shows the characteristics and the like of the obtained laminated film. Similar to Example 1, the calculation result of the surface energy and the functional group index satisfies the formula (1), is excellent in transparency such as total light transmittance and haze, and has an evaluation of adhesion of “◯” and 150 ° C. The haze change after the time heat treatment was a good result within 0.3%.

(Example 5)
Resin (A), melamine compound (B), and compound (C) in mass ratio, (A) / (B) / (C) ((C) -1 / (C) -2 = 46/46) = 100 A laminated film was obtained in the same manner as in Example 1 except for mixing so as to be / 20/92. Table 2 shows the characteristics and the like of the obtained laminated film. Similar to Example 1, the calculation result of the surface energy and the functional group index satisfies the formula (1), is excellent in transparency such as total light transmittance and haze, and has an evaluation of adhesion of “◯” and 150 ° C. The haze change after the time heat treatment was a good result within 0.3%.

(Example 6)
Resin (A), melamine compound (B), and compound (C) in mass ratio, (A) / (B) / (C) ((C) -1 / (C) -2 = 23/23) = 100 A laminated film was obtained in the same manner as in Example 1 except for mixing so as to be / 51/46. Table 2 shows the characteristics and the like of the obtained laminated film. Similar to Example 1, the calculation result of the surface energy and the functional group index satisfies the formula (1), is excellent in transparency such as total light transmittance and haze, and has an evaluation of adhesion of “◯” and 150 ° C. The haze change after the time heat treatment was a good result within 0.3%.

(Examples 7 and 8)
A laminated film was obtained in the same manner as in Example 2 except that the mass ratio of the resin (A) was changed to the mass ratio shown in Table 1. Table 2 shows the characteristics and the like of the obtained laminated film. Similar to Example 1, the calculation result of the surface energy and the functional group index satisfies the formula (1), is excellent in transparency such as total light transmittance and haze, and has an evaluation of adhesion of “◯” and 150 ° C. The haze change after the time heat treatment was a good result within 0.3%.

(Examples 9 and 10)
A laminated film was obtained in the same manner as in Example 2 except that the coating thickness of the resin composition on the polyester film was changed and the thickness of the resin layer (X) was changed to the thickness shown in Table 2. Table 2 shows the characteristics and the like of the obtained laminated film. As in Example 1, the formula (1) is satisfied from the calculation results of the surface energy and the functional group index, the adhesion evaluation is “◯”, and the haze change after heat treatment at 150 ° C. for 1 hour is within 0.3%. It was a good result.

(Example 11)
Compound (c) in resin (A) is converted into a urethane acrylate oligomer (manufactured by Toyo Chemicals Co., Ltd., Miramer (registered trademark) HR3200, the number of acryloyl groups is 4) (a compound having a urethane structure and a polyfunctional acryloyl group). A laminated film was obtained in the same manner as in Example 2 except for the change. Table 2 shows the characteristics and the like of the obtained laminated film. As in Example 1, the formula (1) is satisfied from the calculation results of the surface energy and the functional group index, the adhesion evaluation is “◯”, and the haze change after heat treatment at 150 ° C. for 1 hour is within 0.3%. It was a good result.

(Example 12)
Compound (c) in resin (A) is urethane acrylate oligomer (manufactured by Negami Kogyo Co., Ltd., Art Resin (registered trademark) UN-3320HS, number of acryloyl groups is 15) (having urethane structure and polyfunctional acryloyl group) A laminated film was obtained in the same manner as in Example 2 except that the compound was changed to (Compound). Table 2 shows the characteristics and the like of the obtained laminated film. As in Example 1, the formula (1) is satisfied from the calculation results of the surface energy and the functional group index, the adhesion evaluation is “◯”, and the haze change after heat treatment at 150 ° C. for 1 hour is within 0.3%. It was a good result.

(Example 13)
As compound (C), (C) -3: Isocyanate compound (“Burnock” DNW-500 manufactured by DIC Corporation) was used, and mass ratio of resin (A), melamine compound (B), and compound (C) (A) / (B) / (C) ((C) -1 / (C) -2 / (C) -3 = 30/30/10) = 100/20/70 A laminated film was obtained in the same manner as in Example 1 except for the above. Table 2 shows the characteristics and the like of the obtained laminated film. Similar to Example 1, the calculation result of the surface energy and the functional group index satisfies the formula (1), is excellent in transparency such as total light transmittance and haze, and has an evaluation of adhesion of “◯” and 150 ° C. The haze change after the time heat treatment was a good result within 0.3%.

(Example 14)
Resin (A), melamine compound (B), and compound (C) are mixed in a mass ratio such that (A) / (B) / (C) ((C) -1 = 100/20/70) Obtained a laminated film in the same manner as in Example 1. The characteristics and the like of the obtained laminated film are shown in Table 2. Similar to Example 1, from the calculation results of the surface energy and the functional group index, the formula (1 ), Excellent transparency such as total light transmittance, haze, etc., and the adhesive evaluation is “◯”, and the haze change after heat treatment at 150 ° C. for 1 hour is within 0.3%, which is a good result. .

(Comparative Example 1)
Resin (A), melamine compound (B), and compound (C) in mass ratio, (A) / (B) / (C) ((C) -1 / (C) -2 = 37/40) = 100 A laminated film was obtained in the same manner as in Example 1 except that the mixture was mixed to / 8/77. Table 2 shows the characteristics and the like of the obtained laminated film. Since the formula (1) was not satisfied from the calculation results of the surface energy and the functional group index, the adhesion evaluation was poor, and the content of the melamine compound (B) in the resin composition was small and the resin (α) was formed. Was insufficient, the haze change after the heat treatment at 150 ° C. for 1 hour was also greater than 0.3% and was poor.

(Comparative Example 2)
Resin (A), melamine compound (B), and compound (C) in mass ratio, (A) / (B) / (C) ((C) -1 / (C) -2 = 19/20) = 100 A laminated film was obtained in the same manner as in Example 1 except that the mixture was mixed to be / 20/39. Table 2 shows the characteristics and the like of the obtained laminated film. Since the calculation result of the surface energy and the functional group index did not satisfy the formula (1), the adhesion evaluation was poor.

(Comparative Example 3)
Resin (A), melamine compound (B), and compound (C) in mass ratio, (A) / (B) / (C) ((C) -1 / (C) -2 = 19/20) = 100 A laminated film was obtained in the same manner as in Example 1 except that the mixture was mixed to be / 15/15. Table 2 shows the characteristics and the like of the obtained laminated film. Since the calculation result of the surface energy and the functional group index did not satisfy the formula (1), the adhesion evaluation was poor.

(Comparative Example 4)
Resin (A), melamine compound (B), and compound (C) in mass ratio, (A) / (B) / (C) ((C) -1 / (C) -2 = 15/20) = 100 A laminated film was obtained in the same manner as in Example 1 except that the mixture was mixed to be / 15/35. Table 2 shows the characteristics and the like of the obtained laminated film. Since the calculation result of the surface energy and the functional group index did not satisfy the formula (1), the adhesion evaluation was poor.

(Comparative Example 5)
Example 1 except that the resin (A), the melamine compound (B), and the compound (C) were mixed in a mass ratio such that (A) / (B) / (C) = 100/50/0 In this way, a laminated film was obtained. Table 2 shows the characteristics and the like of the obtained laminated film. Although the change in haze after heat treatment at 150 ° C. for 1 hour was good, the evaluation of adhesion was poor because Expression (1) was not satisfied from the calculation results of the surface energy and the functional group index.

(Comparative Example 6)
A laminated film was obtained in the same manner as in Example 1 except that the mass ratio of the resin (A) was changed to the mass ratio shown in Table 1. In Comparative Example 6 in which the resin (A) did not contain an ethylenically unsaturated compound (b) having a hydroxyl group, the resin composition could not be dispersed in an aqueous solvent and could not be evaluated.

(Comparative Example 7)
A laminated film was obtained in the same manner as in Example 1 except that the mass ratio of the resin (A) was changed to the mass ratio shown in Table 1. Table 2 shows the characteristics and the like of the obtained laminated film. Table 2 shows the characteristics and the like of the obtained laminated film. Since the formula (1) was not satisfied from the calculation results of the surface energy and the functional group index, the adhesion evaluation was poor, and the chemical structure (urethane structure) represented by the formula (4) in the resin (A) and acryloyl Since there was no group-containing compound (c), cracks were generated in the resin layer (X), so that the transparency was lowered and the haze change after heat treatment at 150 ° C. for 1 hour was also poorer than 0.3%.

  The present invention relates to a laminated film having a resin layer that suppresses oligomers precipitated from a polyester film in a process involving film formation or heat treatment of the polyester film and has excellent adhesion to various hard coat agents. It can be used for optical films for touch panel applications and films that require various heating processes.

Claims (15)

Resin layer (X) comprising a resin (α) obtained from a resin composition containing at least one surface of a polyester film (A) having at least a hydroxyl group and an acryloyl group and a melamine compound (B) having a methylol group Is a laminated film in which the surface energy (x) of the resin layer (X) and the functional group index (y) satisfy the following formula (1).
y> −0.8x + 55 Formula (1)
However, the range satisfies 35 ≦ x ≦ 65 (unit: mN / m) and 10 ≦ y ≦ 35 (unit:%). The laminated film according to claim 1, wherein the resin (α) is a resin having a glass transition temperature of 50 ° C. or higher. The laminated film according to claim 1 or 2, wherein the resin (α) has a chemical structure represented by the formula (2).

The laminated film according to claim 1, wherein the resin (α) has a chemical structure represented by the formula (3).

Resin layer (X) comprising a resin (α) obtained from a resin composition containing at least one surface of a polyester film (A) having at least a hydroxyl group and an acryloyl group and a melamine compound (B) having a methylol group Is a laminated film provided with the following conditions (i) to (iii):
(I) A laminated film in which the surface energy (x) and the functional group index (y) of the resin layer (X) satisfy the following formula (1).
y> −0.8x + 55 Formula (1)
However, the range satisfies 35 ≦ x ≦ 65 (unit: mN / m) and 10 ≦ y ≦ 35 (unit:%).
(Ii) The resin (α) has a crosslinked structure of acryloyl groups, a chemical structure represented by the formula (2), and a chemical structure represented by the formula (3). (Iii) the resin (α) The resin must have a glass transition temperature of 50 ° C or higher.

The laminated film according to claim 1, wherein the resin (α) has a chemical structure represented by the formula (4).

Compound (C) in which the resin (α) includes at least one selected from a resin (A) having a hydroxyl group and an acryloyl group, a melamine compound (B) having a methylol group, an isocyanate compound, a carbodiimide compound, and an oxazoline compound. The laminated film according to any one of claims 1 to 6, obtained from a resin composition comprising A method for producing a laminated film satisfying the following conditions (i) to (ii), wherein a resin layer (X) is provided on at least one surface of a polyester film,
A resin composition containing a resin (A) having a hydroxyl group and an acryloyl group and a melamine compound (B) having a methylol group is applied to at least one surface of the polyester film and heated to form a resin layer (X). The manufacturing method of the laminated | multilayer film including a process.
(I) A laminated film in which the surface energy (x) and the functional group index (y) of the resin layer (X) satisfy the following formula (1).
y> −0.8x + 55 Formula (1)
However, the range satisfies 35 ≦ x ≦ 65 (unit: mN / m) and 10 ≦ y ≦ 35 (unit:%).
(Ii) The resin forming the resin layer (X) has a crosslinked structure of acryloyl groups, a chemical structure represented by the formula (2), and a chemical structure represented by the formula (3). The total content of the resin (A) having a hydroxyl group and an acryloyl group and the melamine compound (B) having a methylol group in the resin composition is 50% by mass or more based on the solid content in the resin composition. The manufacturing method of the laminated | multilayer film of Claim 8 which exists. In the resin composition, the mass ratio of the resin (A) and the compound (C) containing at least one selected from an isocyanate compound, a carbodiimide compound, and an oxazoline compound (content of resin (A) [parts by mass] ] The manufacturing method of the laminated | multilayer film of Claim 8 or 9 whose content [mass part] of a compound (C) is 100 / 40-100 / 100. In the resin composition, the mass ratio of the content of the resin (A) and the melamine compound (B) (content of resin (A) [parts by mass] / content of melamine compound (B) [parts by mass] The manufacturing method of the laminated | multilayer film in any one of Claims 8-10 which are 100 / 10-100 / 60. The method for producing a laminated film according to claim 8, wherein the resin (A) further has a chemical structure (urethane structure) represented by the formula (4).

The resin (A) is a resin obtained by polymerization using at least the following compounds (a) to (c), and the mass ratio of each compound used is as follows. The manufacturing method of the laminated film in any one.
-Acrylic ester compound and / or methacrylic ester compound (a): 55-98 parts by mass- Ethylenically unsaturated compound having a hydroxyl group (b): 1-30 parts by mass- Chemical structure represented by formula (4) ( (Urethane structure) and compound (c) having a polyfunctional acryloyl group: 1 to 15 parts by mass The total mass of (a) to (c) is 100 parts by mass.

The method for producing a laminated film according to claim 13, wherein the compound (c) further has a methylol group. The resin composition is applied to at least one surface of a polyester film, then stretched at least in a uniaxial direction, and then heated to 150 ° C or higher to form a resin layer (X). A method for producing a laminated film.