JP6760411B2 - Laminate - Google Patents

Description

The present invention relates to a laminate and a method for producing the same. For example, the present invention has a shaping layer such as a prism sheet or a microlens sheet used for a backlight unit of a liquid crystal display, and has an adhesive layer on the back surface side. The present invention relates to a laminate obtained by laminating the adhesive layer and a shaping layer of another film, and a method for producing the same.

Conventionally, a liquid crystal display has been widely used as a display device for televisions, personal computers, mobile phones, and the like. Since the liquid crystal display unit does not have a light emitting function by itself, a backlight is used to irradiate the light from the back side, but the brightness is improved in order to improve the optical efficiency of the backlight. It is necessary to make it, and prism sheets and microlens sheets are used.

For example, as an example for improving brightness and viewing angle as an improvement in optical efficiency, a prism sheet and a microlens have been proposed around a backlight (Patent Documents 1 to 3). Further, in order to improve performance such as improvement of brightness, it has been proposed to manufacture a backlight unit by superimposing a plurality of prism sheets (Patent Documents 4 and 5).

However, although these sheets are used in layers with some members inside the backlight unit, they may be easily displaced due to their high slipperiness, resulting in poor workability. In addition, since the members rub against each other due to slipping, defects such as scratches and breakage of the shape of the shaping layer such as a prism are likely to occur. In order to improve these problems, there has been a demand for a member that can easily fix the members to each other without slipping and can increase the brightness.

Japanese Unexamined Patent Publication No. 8-304608 JP-A-2002-98816 Japanese Unexamined Patent Publication No. 10-39769 JP-A-2002-6317 JP-A-2004-110025

The present invention has been made in view of the above circumstances, and the problem to be solved is that defects are less likely to occur when various members are laminated, for example, improvement of optical efficiency in a backlight unit, and a manufacturing process is simplified. The purpose is to provide a laminated body that is standardized and cost-competitive.

As a result of diligent studies in view of the above circumstances, the present inventors have found that the above-mentioned problems can be easily solved by using a laminate having a specific structure, and have completed the present invention.

That is, the gist of the present invention is a film (A) having a shaping layer on one surface of the film and an adhesive layer containing a resin having a glass transition point of 0 ° C. or lower on the other surface. The film (B) having a shape layer is laminated so that the adhesive layer of the film (A) and the shaping layer of the film (B) are in contact with each other, and the resin having a glass transition point of 0 ° C. or lower is functional. acid as groups, sulfonate, polyester resins der containing carboxylic acid or carboxylic acid salt, is, shaping layer and a film shaping layer (B) of the film (a) is a prism layer, a microlens layer and lies in the laminate, wherein 1 Tanedea Rukoto selected from moth eye layer.

According to the laminate of the present invention, it is possible to provide a laminate that is less likely to cause defects when various members are laminated, such as improvement of optical efficiency, simplifies the manufacturing process, and has cost competitiveness. The industrial value is high.

By superimposing films having a conventional shaping layer into a film having an adhesive layer as in the present invention and laminating the films, defects such as scratches caused by slipping between the films and destruction of the shaping layer It was found that it can be reduced. In addition, since it is possible to work and store the laminated body from the work and storage of each sheet, the number of punching of the sheet is reduced, the number of assembly processes of the backlight unit is reduced, and the product is used as a shaped sheet. It was also found that it would be possible to reduce inventory space. Furthermore, it was found that the strength of the laminated body (strength of stiffness) is also improved as compared with the conventional superposition without an adhesive layer.

As the film base material of the laminate, conventionally known ones can be used, and polyester film, polycarbonate film, fluororesin film, polyimide film, triacetyl cellulose film, polyacrylate film, polystyrene film, polyvinyl chloride film, etc. Examples thereof include polyvinyl alcohol film and nylon film. In particular, in order to develop into various applications, it is preferable to have transparency and heat resistance, and polyester film, polycarbonate film, fluororesin film, polyimide film, and triacetyl cellulose film are preferably used, and polyester film and polycarbonate film. Is more preferable, and a polyester film is more preferably used in consideration of high transparency, moldability, and versatility.

The film constituting the laminated body may have a single-layer structure or a multi-layer structure, and may have a multi-layer structure of four layers or more as long as the gist of the present invention is not exceeded in addition to the two-layer and three-layer structure. It is also good and is not particularly limited. It is preferable to have a multi-layer structure of two or more layers, and to give each layer a characteristic to make it multifunctional.

As a polyester film that can be used as a film, the polyester may be a homopolyester or a copolymerized polyester. When it is made of homopolyester, it is preferably obtained by polycondensing an aromatic dicarboxylic acid and an aliphatic glycol. Examples of the aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid, and examples of the aliphatic glycol include ethylene glycol, diethylene glycol and 1,4-cyclohexanedimethanol. Examples of typical polyesters include polyethylene terephthalate and the like. On the other hand, examples of the dicarboxylic acid component of the copolymerized polyester include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, and oxycarboxylic acid (for example, p-oxybenzoic acid). One or more of them may be mentioned, and examples of the glycol component include one or more of ethylene glycol, diethylene glycol, propylene glycol, butanediol, 4-cyclohexanedimethanol, neopentyl glycol and the like.

From the viewpoint of producing a film that can withstand various processing conditions, it is preferable that the film has high mechanical strength and heat resistance (dimensional stability due to heating), and for that purpose, it may be preferable that the amount of the copolymerized polyester component is small. Specifically, the proportion of the monomer forming the copolymerized polyester in the polyester film is usually in the range of 10 mol% or less, preferably 5 mol% or less, and more preferably produced as a by-product during homopolyester polymerization. It contains 3 mol% or less of a diether component, which is a degree of storage. A more preferable form of polyester is, in consideration of mechanical strength and heat resistance, a film formed from polyethylene terephthalate or polyethylene naphthalate, which is polymerized from terephthalic acid and ethylene glycol, more preferably among the above compounds. A film formed from polyethylene terephthalate is more preferable in consideration of ease of use and handleability as a surface protective film.

The polyester polymerization catalyst is not particularly limited, and conventionally known compounds can be used. Examples thereof include antimony compounds, titanium compounds, germanium compounds, manganese compounds, aluminum compounds, magnesium compounds and calcium compounds. Among these, antimony compounds are preferable because they are inexpensive, and titanium compounds and germanium compounds have high catalytic activity, can be polymerized in a small amount, and the amount of metal remaining in the film is small. It is preferable because the transparency of the film is increased. Further, since the germanium compound is expensive, it is more preferable to use a titanium compound.

In the case of polyester using a titanium compound, the titanium element content is usually in the range of 50 ppm or less, preferably 1 to 20 ppm, and more preferably 2 to 10 ppm. If the content of the titanium compound is too high, the deterioration of the polyester may be accelerated in the process of melt extrusion of the polyester, resulting in a film with a strong yellow tint. If the content is too low, the polymerization efficiency is poor and the cost is high. It may not be possible to obtain a film that is up or has sufficient strength. When a polyester made of a titanium compound is used, it is preferable to use a phosphorus compound in order to reduce the activity of the titanium compound for the purpose of suppressing deterioration in the melt extrusion process. As the phosphorus compound, orthophosphoric acid is preferable in consideration of polyester productivity and thermal stability. The phosphorus element content is usually in the range of 1 to 300 ppm, preferably 3 to 200 ppm, and more preferably 5 to 100 ppm with respect to the amount of polyester to be melt-extruded. If the content of the phosphorus compound is too high, it may cause gelation or foreign matter, and if the content is too low, the activity of the titanium compound cannot be sufficiently reduced, resulting in a yellowish color. It may be a film.

As the polycarbonate film that can be used as a film, conventionally known polycarbonate can be used, but a type containing a cyclic structure is preferable, and a type containing a bisphenol A structure is particularly preferable.

Particles can also be blended into the film for the purpose of imparting slipperiness, preventing scratches in each process, and improving blocking resistance. When the particles are blended, the type of the particles to be blended is not particularly limited as long as it is a particle capable of imparting slipperiness, and specific examples thereof include silica, calcium carbonate, magnesium carbonate, barium carbonate, and sulfuric acid. Examples thereof include inorganic particles such as calcium, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, zirconium oxide and titanium oxide, and organic particles such as acrylic resin, styrene resin, urea resin, phenol resin, epoxy resin and benzoguanamine resin. Further, during the polyester production process, precipitated particles in which a part of a metal compound such as a catalyst is precipitated and finely dispersed can also be used. Among these, silica particles and calcium carbonate particles are particularly preferable in that a small amount is likely to produce an effect.

The average particle size of the particles is usually 10 μm or less, preferably 0.01 to 5 μm, and more preferably 0.01 to 3 μm. If the average particle size exceeds 10 μm, there may be a concern about defects due to a decrease in the transparency of the film.

Further, the particle content in the film cannot be unconditionally determined because it has a balance with the average particle size of the particles, but is usually 5% by weight or less, preferably in the range of 0.0003 to 3% by weight, more preferably 0. It is in the range of 0005 to 1% by weight. If the particle content exceeds 5% by weight, there may be concerns about problems such as falling of particles and deterioration of transparency of the film. When there are no or few particles, the transparency is excellent, but the slipperiness may be insufficient. Therefore, the slipperiness is improved by putting particles in the adhesive layer or the functional layer described later. It may be necessary to devise such as.

The shape of the particles to be used is not particularly limited, and any of spherical, lumpy, rod-shaped, flat-shaped and the like may be used. Further, the hardness, specific gravity, color and the like are not particularly limited.
Two or more kinds of these series of particles may be used in combination, if necessary.

The method of adding the particles to the film is not particularly limited, and a conventionally known method can be adopted. For example, it can be added at any stage in which the resin constituting each layer is produced, but it is preferably added after the resin formation reaction is completed.

In addition to the above-mentioned particles, conventionally known ultraviolet absorbers, antioxidants, antistatic agents, heat stabilizers, lubricants, dyes, pigments and the like can be added to the film, if necessary.

The thickness of the film is not particularly limited as long as it can be formed as a film, but is usually in the range of 2 to 350 μm, preferably 5 to 250 μm, and more preferably 10 to 200 μm.

A production example of the film will be specifically described, but the present invention is not limited to the following production examples, and a generally known film-forming method can be adopted. Generally, the resin is melted, made into a sheet, and stretched for the purpose of increasing the strength to prepare a film. For example, in the case of producing a biaxially stretched polyester film, first, a polyester raw material is melt-extruded from a die using an extruder, and the melted sheet is cooled and solidified with a cooling roll to obtain an unstretched sheet. In this case, in order to improve the flatness of the sheet, it is preferable to improve the adhesion between the sheet and the rotary cooling drum, and the electrostatic application adhesion method and the liquid coating adhesion method are preferably adopted. Next, the obtained unstretched sheet is stretched in one direction by a roll or tenter type stretching machine. The stretching temperature is usually 70 to 120 ° C., preferably 80 to 110 ° C., and the stretching ratio is usually 2.5 to 7 times, preferably 3.0 to 6 times. Then, in the direction orthogonal to the stretching direction of the first stage, stretching is usually performed at 70 to 170 ° C. and a stretching ratio is usually 2.5 to 7 times, preferably 3.0 to 6 times. A method of subsequently performing heat treatment at a temperature of 180 to 270 ° C. under tension or relaxation within 30% to obtain a biaxially oriented film can be mentioned. In the above stretching, a method of stretching in one direction in two or more steps can also be adopted. In that case, it is preferable to finally set the stretching ratios in the two directions within the above ranges.

Further, the simultaneous biaxial stretching method can be adopted for film production. The simultaneous biaxial stretching method is a method of simultaneously stretching and orienting the unstretched sheet in the mechanical direction and the width direction while the temperature is controlled at 70 to 120 ° C., preferably 80 to 110 ° C., and the stretching ratio is Is 4 to 50 times, preferably 7 to 35 times, and more preferably 10 to 25 times in area magnification. Then, the heat treatment is subsequently performed at a temperature of 180 to 270 ° C. under tension or relaxation within 30% to obtain a stretch-oriented film. As for the simultaneous biaxial stretching device that employs the above-mentioned stretching method, a conventionally known stretching method such as a screw method, a pantograph method, and a linear drive method can be adopted.

Next, the formation of the adhesive layer will be described. Examples of the method for forming the adhesive layer include methods such as coating, transfer, and laminating. Considering the ease of forming the adhesive layer, it is preferably formed by coating.

As a coating method, it may be provided by in-line coating, which is performed in the process of film production, or may be provided by offline coating, which coats the once produced film outside the system. More preferably, it is formed by in-line coating.

Specifically, the in-line coating is a method in which the resin forming the film is melt-extruded, stretched, heat-fixed, and wound up at any stage. Usually, it is coated on any of an unstretched sheet obtained by melting and quenching, a stretched uniaxially stretched film, a biaxially stretched film before heat fixing, and a film after heat fixing and before winding. Although not limited to the following, for example, in sequential biaxial stretching, a method of coating a uniaxially stretched film stretched in the longitudinal direction (longitudinal direction) and then stretching in the lateral direction is particularly excellent. According to such a method, since the film formation and the adhesive layer formation can be performed at the same time, there is an advantage in manufacturing cost, and the thickness of the adhesive layer can be changed by the stretching ratio in order to perform stretching after coating. , Thin film coating can be performed more easily than offline coating.

Further, by providing the adhesive layer on the film before stretching, the adhesive layer can be stretched together with the base film, whereby the adhesive layer can be firmly adhered to the base film. Further, in the production of a biaxially stretched polyester film, the film can be restrained in the vertical and horizontal directions by stretching while gripping the end of the film with a clip or the like, and in the heat fixing step, a flat surface without wrinkles or the like. High temperature can be applied while maintaining the sex.

Therefore, since the heat treatment applied after coating can be at a high temperature that cannot be achieved by other methods, the film-forming property of the adhesive layer is improved, and the adhesive layer and the base film can be more firmly adhered to each other. Furthermore, it can be a strong adhesive layer. In particular, it is very effective for reacting a cross-linking agent.

According to the above-mentioned in-line coating process, the film size does not change significantly depending on the presence or absence of the adhesive layer, and the risk of scratches and foreign matter adhesion does not change significantly depending on the presence or absence of the adhesive layer. This is a great advantage over the one extra offline coating. Furthermore, as a result of various studies, it has been found that the in-line coating has an advantage that the adhesive residue, which is the transfer of the components of the adhesive layer when the film of the present invention is attached to the adherend, can be reduced. It was. This is considered to be the result of the adhesive layer and the base film being more firmly adhered to each other because the heat treatment can be performed at a high temperature which cannot be obtained by the offline coating.

Further, in the total area coating by the above method, the formed adhesive layer has an increased contact area with the shaping layer, so that even if the adhesive force per area is weak, the adhesive force with the shaping layer is maintained. Easy to secure. In addition, when peeling off due to re-sticking work or the like, a relatively weak adhesive force works advantageously. That is, by making the area wide (adhesive over the entire area) with a weak adhesive force, it is possible to secure an appropriate adhesive force and reworkability with the shaping layer. Furthermore, the coating of the entire area of the adhesive layer makes it possible to obtain uniform brightness in the surface direction, which is a preferable form for use in a backlight unit.

In the present invention, it is essential that the film (A) having the shaping layer and the adhesive layer containing the resin having the glass transition point of 0 ° C. or lower and the film (B) having the shaping layer are constituent elements. It is a requirement of.

As the resin having a glass transition point of 0 ° C. or lower, a conventionally known resin can be used. Specific examples of the resin include polyester resin, acrylic resin, urethane resin, polyvinyl resin (polyvinyl alcohol, vinyl chloride vinyl acetate copolymer, etc.), and among them, polyester resin is particularly considered in terms of adhesive properties and coating properties. , Acrylic resin and urethane resin are preferable, polyester resin and acrylic resin are more preferable because of their strong adhesive properties, and polyester resin is further preferable because they have high adhesive strength to various adherends. When considering the reusability of the film, polyester resin or acrylic resin is preferable, and when the base material is a polyester film, polyester resin is used when considering the adhesion to the base material, and the change with time is small. Acrylic resin is most preferable when considering. Furthermore, when considering the transferability of the components of the adhesive layer to the adherend, it was also found that the acrylic resin has less transferability and is preferable to the polyester resin.

Examples of the polyester resin include those composed of the following polyvalent carboxylic acids and polyvalent hydroxy compounds as main constituents. That is, as the polyvalent carboxylic acid, terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 4,4'-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid and 2,6 -Naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, 5-sodium sulfoisophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutaru Acids, succinic acid, trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, phthalic anhydride, p-hydroxybenzoic acid, monopotassium trimellitic acid and ester-forming derivatives thereof can be used. As polyvalent hydroxy compounds, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanedioyl, 2 -Methyl-1,5-pentandiol, neopentylglycol, 1,4-cyclohexanedimethanol, p-xylyleneglycol, bisphenylene A-ethyleneglycol adduct, diethyleneglycol, triethyleneglycol , Polyethylene glycol, Polypropylene glycol, Polytetramethylene glycol, Polytetramethylene oxide glycol, Dimethylolpropionic acid, Glycerin, Trimethylolpropane, Sodium dimethylolethylsulfonate, Dimethylpropion Potassium acid or the like can be used. One or more of each of these compounds may be appropriately selected, and a polyester resin may be synthesized by a conventional polycondensation reaction.

Among the above, it is preferable to contain an aliphatic polyvalent carboxylic acid or an aliphatic polyvalent hydroxy compound as a constituent component in order to lower the glass transition point to 0 ° C. or lower. In general, polyester resins are composed of aromatic polyvalent carboxylic acids and polyvalent hydroxy compounds including aliphatics. Therefore, in order to lower the glass transition point compared to general polyester resins, aliphatic polyvalents are used. It is effective to contain a carboxylic acid. From the viewpoint of lowering the glass transition point, it is preferable that the aliphatic polyvalent carboxylic acid has a long carbon number, and usually has 6 or more carbon atoms (adipic acid), preferably 8 or more carbon atoms, and more preferably 10 or more carbon atoms. The upper limit of the preferable range is 20.

From the viewpoint of improving the adhesive properties, the content of the aliphatic polyvalent carboxylic acid in the acid component in the polyester resin is usually 2 mol% or more, preferably 4 mol% or more, more preferably 6 mol% or more. More preferably, it is 10 mol% or more, and the upper limit of the preferable range is 50 mol%.

In the aliphatic polyvalent hydroxy compound, in order to lower the glass transition point, the number of carbon atoms is preferably 4 or more (butanediol), and the content of the hydroxy component in the polyester resin is preferably 10 mol. % Or more, more preferably 30 mol% or more.

Considering the suitability for in-line coating, it is preferable to use an aqueous system, and therefore, it is preferable that the polyester resin contains hydrophilic functional groups such as sulfonic acid, sulfonate, carboxylic acid, and carboxylic acid salt. Sulfonic acid and sulfonate are preferable, and sulfonate is particularly preferable, in that dispersibility in water is particularly good. Among the sulfonates, sulfonic acid metal salts are more preferable.

When the above-mentioned sulfonic acid, sulfonic acid salt, carboxylic acid, and carboxylic acid salt are used, the content in the acid component in the polyester resin is usually 0.1 to 10 mol%, preferably 0.2 to 8 mol%. Is the range of. By using it in the above range, the dispersibility in water becomes good.

In addition, considering the coating appearance in in-line coating, adhesion and blocking to the film, and reduction of transfer (glue residue) to the adherend when used as a surface protective film, it is used as an acid component in the polyester resin. It preferably contains a certain amount of aromatic polyvalent carboxylic acid. As a ratio in the acid component in the polyester resin, the aromatic polyvalent carboxylic acid is usually in the range of 30 mol% or more, preferably 50 mol% or more, more preferably 60 mol% or more, and the upper limit of the preferable range is 98. It is mol%. Further, among aromatic polyvalent carboxylic acids, a benzene ring structure such as terephthalic acid or isophthalic acid is preferable to a naphthalene ring structure from the viewpoint of adhesive properties. Further, in order to further improve the adhesive properties, it is more preferable to use two or more kinds of aromatic polyvalent carboxylic acids in combination.

The glass transition point of the polyester resin for improving the adhesive properties is indispensable to be 0 ° C. or lower, preferably -10 ° C. or lower, more preferably -20 ° C. or lower, and the lower limit of the preferable range is −. It is 60 ° C. By using it in the above range, it becomes easy to obtain a film having optimum adhesive properties.

The acrylic resin is a polymer composed of a polymerizable monomer containing acrylic and methacrylic monomers (hereinafter, acrylic and methacrylic may be collectively abbreviated as (meth) acrylic). These may be homopolymers or copolymers, and may be copolymers with polymerizable monomers other than acrylic and methacrylic monomers.

Also included are copolymers of these polymers with other polymers (eg polyester, polyurethane, etc.). For example, block copolymers and graft copolymers. Alternatively, a polymer (possibly a mixture of polymers) obtained by polymerizing a polymerizable monomer in a polyester solution or a polyester dispersion is also included. Similarly, a polymer (in some cases, a mixture of polymers) obtained by polymerizing a polymerizable monomer in a polyurethane solution or a polyurethane dispersion is also included. Similarly, a polymer (in some cases, a polymer mixture) obtained by polymerizing a polymerizable monomer in another polymer solution or dispersion is also included. However, considering the adhesive properties and the adhesive residue on the adherend, it should not contain other polymers such as polyester and polyurethane (polymerizable monomers containing carbon-carbon double bonds (either homopolymers or copolymers). A (meth) acrylic resin) composed of only (possible) is preferable.

The polymerizable monomer is not particularly limited, but typical compounds include, for example, various carboxyl groups such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and citraconic acid. Monomers and salts thereof; such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monobutylhydroquilfumarate, monobutylhydroxyitaconate. Various hydroxyl group-containing monomers; various types such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and lauryl (meth) acrylate. (Meta) acrylic acid esters; various nitrogen-containing compounds such as (meth) acrylamide, diacetone acrylamide, N-methylol acrylamide or (meth) acrylonitrile; of styrene, α-methylstyrene, divinylbenzene, vinyl toluene, etc. Various styrene derivatives such as, various vinyl esters such as vinyl propionate, vinyl acetate; various silicon-containing polymerizable monomers such as γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, etc .; phosphorus-containing vinyl Monomers; various vinyl halides such as vinyl chloride and billidene chloride; various conjugated dienes such as butadiene.

In order to lower the glass transition point to 0 ° C or lower, it is necessary to use a (meth) acrylic system in which the glass transition point of the homopolymer is 0 ° C or lower, for example, ethyl acrylate (glass transition point: -22 ° C), n-propyl acrylate (glass transition point: -37 ° C), isopropyl acrylate (glass transition point: -5 ° C), normal butyl acrylate (glass transition point: -55 ° C), normal hexyl acrylate (glass transition point: -57) ℃), 2-ethylhexyl acrylate (glass transition point: -70 ° C), normal octyl acrylate (glass transition point: -65 ° C), isooctyl acrylate (glass transition point: -83 ° C), normal nonyl acrylate (glass) Transition point: -63 ° C), normal nonyl methacrylate (glass transition point: -35 ° C), isononyl acrylate (glass transition point: -82 ° C), normal decyl acrylate (glass transition point: -70 ° C), normal decyl methacrylate (Glass transition point: -45 ° C), Isodecyl acrylate (Glass transition point: -55 ° C), Isodecyl methacrylate (Glass transition point: -41 ° C), Lauryl acrylate (Glass transition point: -30 ° C), Lauryl meta Acrylate (glass transition point: -65 ° C), tridecyl acrylate (glass transition point: -75 ° C), tridecyl methacrylate (glass transition point: -46 ° C), isomistyryl acrylate (glass transition point: -56 ° C), Examples thereof include 2-hydroxyethyl acrylate (glass transition point: −15 ° C.).

Among the above, in order to improve the adhesive properties, the number of carbon atoms of the alkyl group is usually in the range of 4 or more, preferably in the range of 4 to 30, more preferably in the range of 4 to 20, and further preferably in the range of 4 to 14. Alkyl (meth) acrylate is adopted. Since it is mass-produced industrially, a (meth) acrylic resin containing normal butyl acrylate and 2-ethylhexyl acrylate is most suitable from the viewpoint of handleability and supply stability.

The content of the (meth) acrylate unit having an alkyl group having 4 or more carbon atoms at the ester terminal in the (meth) acrylic resin is usually 20% by weight or more, preferably 35 to 99% by weight, and more preferably 50 to 98% by weight. It is in the range of% by weight, more preferably 65 to 95% by weight, and particularly preferably 75 to 90% by weight. The higher the content of the (meth) acrylate unit having an alkyl group having 4 or more carbon atoms at the ester terminal, the stronger the adhesive property. On the contrary, if the content is too small, the adhesive strength may not be sufficient.

In the above (meth) acrylic resin, the content of the (meth) acrylate unit having the glass transition point of the homopolymer at 0 ° C. or lower and having an alkyl group having less than 4 carbon atoms at the ester terminal is usually 50% by weight or less. It is preferably in the range of 40% by weight or less, more preferably 30% by weight or less. Good adhesive properties can be obtained by using in the above range.

Further, from the viewpoint of reducing the transfer of the adhesive component to the adherend, among the above, a compound having 2 or less carbon atoms at the ester terminal or a compound having a cyclic structure is preferable, and further preferable. Is a compound having 1 carbon atom or an aromatic compound.
Specific examples include methyl methacrylate, acrylonitrile, styrene, and cyclohexyl acrylate as preferred compounds.

The content of the compound unit having 2 or less carbon atoms at the ester terminal in the (meth) acrylic resin is usually 50% by weight or less, preferably 1 to 40% by weight, and more preferably 3 to 30% by weight. %, More preferably in the range of 5 to 20% by weight. It is possible to impart an appropriate range of adhesive properties to the adherend when the content of the unit is low, without significantly degrading the adhesive properties, and conversely, when the content is high, the adhesive properties are applied to the adherend. It is possible to reduce the transfer of adhesive components. Therefore, within the above range, it becomes easy to achieve the two objectives of adhesive properties and migration reduction.

The content of the compound unit having a cyclic structure in the (meth) acrylic resin is usually in the range of 50% by weight or less, preferably 1 to 45% by weight, and more preferably 5 to 40% by weight. It is possible to impart an appropriate range of adhesive properties to the adherend when the content of the unit is low, without significantly degrading the adhesive properties, and conversely, when the content is high, the adhesive properties are applied to the adherend. It is possible to reduce the transfer of adhesive components. Therefore, within the above range, it becomes easy to achieve the two objectives of adhesive properties and migration reduction.

From the viewpoint of adhesive properties, the content of the monomer having a glass transition point of homopolymer of 0 ° C. or lower as a monomer constituting the (meth) acrylic resin is usually 30% by weight or more as a ratio to the whole (meth) acrylic resin. It is preferably in the range of 45% by weight or more, more preferably 60% by weight or more, and further preferably 70% by weight or more. The upper limit of the preferable range is 99% by weight. Good adhesive properties can be easily obtained by using in the above range.

The glass transition point of the monomer having a glass transition point of the homopolymer having a glass transition point of 0 ° C. or lower, which improves the adhesive properties, is usually −20 ° C. or lower, preferably −30 ° C. or lower, more preferably −40 ° C. or lower, and further. It is preferably −50 ° C. or lower, and the lower limit of the preferable range is −100 ° C. By using it in this range, it becomes easy to obtain a film having appropriate adhesive properties.

As a more optimal (meth) acrylic resin form for improving the adhesive properties, the total content of normal butyl acrylate and 2-ethylhexyl acrylate in the (meth) acrylic resin is usually 30% by weight or more. The range is preferably 40% by weight or more, more preferably 50% by weight or more, further preferably 60% by weight or more, particularly preferably 70% by weight or more, and the upper limit of the preferable range is 99% by weight. It depends on the composition of the (meth) acrylic resin used and the composition of the adhesive layer, but in particular, when it is desired to eliminate the transfer of the adhesive component to the adherend with a small amount of the cross-linking agent, 2-ethylhexyl The content of the acrylate is usually in the range of 90% by weight or less, preferably 80% by weight or less.

Further, in consideration of application to in-line coating and the like, it is possible to introduce various hydrophilic functional groups in order to obtain a (meth) acrylic resin that can be used in an aqueous system. Preferred examples of the hydrophilic functional group are carboxylic acid group, carboxylic acid base, sulfonic acid group, sulfonic acid base and hydroxyl group, and among them, carboxylic acid group, carboxylic acid base and hydroxyl group are preferable from the viewpoint of water resistance.

Examples of the introduction of the carboxylic acid include copolymerization of various carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and citraconic acid. Among the above, acrylic acid and methacrylic acid are preferable because effective water dispersion is possible.

As the introduction of hydroxyl groups, various types such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monobutylhydroquilfumarate, and monobutylhydroxyitaconate are used. Copolymerization of hydroxyl group-containing monomers can be mentioned. Among the above, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable in consideration of industrial ease of handling.

Further, as the cross-linking reactive group, it is also possible to contain a copolymer of an amino group-containing monomer such as dimethylaminoethyl (meth) acrylate and a copolymer of an epoxy group-containing monomer such as glycidyl (meth) acrylate. is there. However, if the content is too large, it affects the adhesive properties, so it is necessary to set the content to an appropriate level.

The proportion of the hydrophilic functional group-containing monomer in the (meth) acrylic resin is usually in the range of 30% by weight or less, preferably 1 to 20% by weight, more preferably 2 to 15% by weight, still more preferably 3 to 10% by weight. Is. By using it in the above range, it becomes easier to develop the water system.

The glass transition point of the (meth) acrylic resin for improving the adhesive properties is indispensable to be 0 ° C. or lower, preferably -10 ° C. or lower, more preferably -20 ° C. or lower, and further preferably -20 ° C. or lower. The range is −30 ° C. or lower, particularly preferably −35 ° C. or lower, most preferably −45 ° C. or lower, and the lower limit of the preferable range is −80 ° C. By using it in the above range, it becomes easy to obtain a film having optimum adhesive properties. Further, when it is necessary to consider the reduction of the transfer of the adhesive component to the adherend, the temperature is preferably −70 ° C. or higher, more preferably −60 ° C. or higher.

The urethane resin is a polymer compound having a urethane bond in the molecule, and is usually produced by a reaction between a polyol and an isocyanate. Examples of the polyol include polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, and acrylic polyols, and these compounds may be used alone or in a plurality of types.

Polycarbonate polyols are obtained from polyhydric alcohols and carbonate compounds by a dealcohol reaction. Examples of polyhydric alcohols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentane. Diol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decane Examples thereof include diols, neopentyl glycol, 3-methyl-1,5-pentanediol, and 3,3-dimethylol heptane. Examples of the carbonate compound include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate and the like, and examples of the polycarbonate-based polyols obtained from these reactions include poly (1,6-hexylene) carbonate and poly (3-). Methyl-1,5-pentylene) carbonate and the like can be mentioned.

From the viewpoint of improving the adhesive properties, the chain alkyl chain is a polycarbonate polyol composed of a diol component usually in the range of 4 to 30, preferably 4 to 20, more preferably 6 to 12, and is industrial. From the viewpoint of good handleability and supply stability, 1,6-hexanediol, or 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are available. Optimal is a copolymerized polycarbonate polyol containing at least two selected diols.

Examples of the polyether polyols include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol and the like.

From the viewpoint of improving the adhesive properties, the monomer forming the polyether has an aliphatic diol usually in the range of 2 to 30, preferably 3 to 20, more preferably 4 to 12, and particularly a linear aliphatic diol. It is a polyether polyol containing.

Polypolypolyols include polyvalent carboxylic acids (malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, suberic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, isophthalic acid, etc.) or their acid anhydrides. Products and polyhydric alcohols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-Methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol , 2-Methyl-2-propyl-1,3-propanediol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2 , 5-Diol-2,5-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-butyl-2 -Hexyl-1,3-propanediol, cyclohexanediol, bishydroxymethylcyclohexane, dimethanolbenzene, bishydroxyethoxybenzene, alkyldialkanolamine, lactonediol, etc.), lactone compounds such as polycaprolactone Examples thereof include those having a derivative unit.

Considering the adhesive properties, polycarbonate polyols and polyether polyols are more preferably used among the above-mentioned polyols, and polycarbonate polyols are particularly preferable.

Examples of the polyisocyanate compound used to obtain a urethane resin include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylenedi isocyanate, naphthalene diisocyanate, and trizine diisocyanate, α, α, α', and α'. − Arophilic diisocyanates such as tetramethylxylylene diisocyanate, methylene diisocyanates, propylene diisocyanates, lysine diisocyanates, trimethylhexamethylene diisocyanates, aliphatic diisocyanates such as hexamethylene diisocyanates, cyclohexane diisocyanates, methylcyclohexane diisocyanates, isophorone diisocyanates, dicyclohexyl Examples thereof include alicyclic diisocyanates such as methane diisocyanate and isopropyridene dicyclohexyl diisocyanate. These may be used alone or in combination of two or more.

A chain extender may be used when synthesizing the urethane resin, and the chain extender is not particularly limited as long as it has two or more active groups that react with the isocyanate group, and is generally a hydroxyl group. Alternatively, a chain extender having two amino groups can be mainly used.

Examples of the chain extender having two hydroxyl groups include aliphatic glycols such as ethylene glycol, propylene glycol and butanediol, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, and esters such as neopentyl glycol hydroxypivalate. Examples of glycols such as glycols can be mentioned. Examples of the chain extender having two amino groups include aromatic diamines such as tolylene diamine, xylylene diamine, and diphenylmethanediamine, ethylenediamine, propylenediamine, hexanediamine, 2,2-dimethyl-1,3-. Propanediamine, 2-methyl-1,5-pentanediamine, trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10- Aliphatic diamines such as decanediamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethanediamine, isopropylidenecyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, 1, Examples thereof include alicyclic diamines such as 3-bisaminomethylcyclohexane.

The urethane resin may use a solvent as a medium, but is preferably water as a medium. In order to disperse or dissolve the urethane resin in water, there are a forced emulsification type using an emulsifier, a self-emulsification type in which a hydrophilic group is introduced into the urethane resin, a water-soluble type, and the like. In particular, the self-emulsifying type in which an ionic group is introduced into the structure of the urethane resin to form an ionomer is preferable because it is excellent in storage stability of the liquid, water resistance of the obtained adhesive layer, and transparency.

Examples of the ionic group to be introduced include various types such as a carboxyl group, a sulfonic acid, a phosphoric acid, a phosphonic acid, and a quaternary ammonium salt, and a carboxyl group is preferable. As a method for introducing a carboxyl group into the urethane resin, various methods can be taken in each stage of the polymerization reaction. For example, at the time of prepolymer synthesis, there are a method of using a resin having a carboxyl group as a copolymerization component and a method of using a component having a carboxyl group as one component of a polyol, a polyisocyanate, a chain extender and the like. In particular, a method of using a carboxyl group-containing diol and introducing a desired amount of carboxyl groups according to the amount of this component charged is preferable.

For example, copolymerizing dimethylolpropionic acid, dimethylolbutanoic acid, bis- (2-hydroxyethyl) propionic acid, bis- (2-hydroxyethyl) butanoic acid, etc. with the diol used for polymerizing the urethane resin. Can be done. Further, this carboxyl group is preferably in the form of a salt neutralized with ammonia, amines, alkali metals, inorganic alkalis and the like. Particularly preferred are ammonia, trimethylamine and triethylamine.
In such a urethane resin, the carboxyl group from which the neutralizing agent has been removed in the drying step after coating can be used as a cross-linking reaction point by another cross-linking agent. As a result, the stability of the liquid before coating is excellent, and the durability, solvent resistance, water resistance, blocking resistance and the like of the obtained adhesive layer can be further improved.

The glass transition point of the urethane resin for improving the adhesive properties is indispensable to be 0 ° C. or lower, preferably −10 ° C. or lower, more preferably −20 ° C. or lower, and further preferably −30 ° C. The range is as follows, and the lower limit of the preferable range is −80 ° C. By using it in the above range, it becomes easy to obtain a film having optimum adhesive properties.

As the above-mentioned resin having a glass transition point of 0 ° C. or lower, only one type may be used, or two or more types may be used in combination. Preferred forms when two or more types are used in combination include polyester resin and urethane resin, polyester resin and acrylic resin, and urethane resin and acrylic resin.

It is also preferable to use a cross-linking agent in combination from the viewpoint of the strength of the adhesive layer. We have mainly studied the adhesive layer using a resin with a glass transition point of 0 ° C. or lower, but it has become clear in the study that the adhesive component is transferred to the adherend under severe conditions. Therefore, as a result of various studies, it was also found that the transfer of the adhesive layer to the adherend can be improved by using a cross-linking agent in combination.

As the cross-linking agent, conventionally known materials can be used, and examples thereof include melamine compounds, isocyanate compounds, epoxy compounds, oxazoline compounds, carbodiimide compounds, silane coupling compounds, hydrazide compounds, and aziridine compounds. Among them, melamine compounds, isocyanate compounds, epoxy compounds, oxazoline compounds, carbodiimide compounds, and silane coupling compounds are preferable, and further, melamine compounds and isocyanate compounds can be easily adjusted from the viewpoint of maintaining appropriate adhesive strength and being easy to adjust. Compounds and epoxy compounds are more preferable, and isocyanate compounds and epoxy compounds are particularly preferable because the decrease in adhesive strength due to the combined use can be suppressed. Further, a melamine compound or an isocyanate compound is preferable, and a melamine compound is particularly preferable, particularly from the viewpoint of reducing the transfer to the adherend. Further, the melamine compound is particularly preferable from the viewpoint of the strength of the adhesive layer. Further, these cross-linking agents may be used alone or in combination of two or more.

Depending on the structure of the pressure-sensitive adhesive layer and the type of cross-linking agent, if the content of the cross-linking agent in the pressure-sensitive adhesive layer becomes too large, the pressure-sensitive adhesive properties may deteriorate too much. Therefore, it is preferable to pay attention to the content in the adhesive layer.

A melamine compound is a compound having a melamine skeleton in the compound, for example, an alkylolated melamine derivative, a compound obtained by reacting an alcoholylated melamine derivative with an alcohol to partially or completely etherify, and these. A mixture can be used. As the alcohol used for etherification, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol and the like are preferably used. Further, the melamine compound may be either a monomer or a multimer of a dimer or more, or a mixture thereof may be used. Considering the reactivity with various compounds, it is preferable that the melamine compound contains a hydroxyl group. Further, a copolymer of urea or the like in a part of melamine can be used, or a catalyst can be used to increase the reactivity of the melamine compound.

The isocyanate-based compound is a compound having an isocyanate derivative structure typified by isocyanate or blocked isocyanate. Examples of the isocyanate include aromatic isocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylenedi isocyanate and naphthalene diisocyanate, and aromatic rings such as α, α, α'and α'-tetramethylxylylene diisocyanate. Aliphatic isocyanates such as aliphatic isocyanates, methylene diisocyanates, propylene diisocyanates, lysine diisocyanates, trimethylhexamethylene diisocyanates, hexamethylene diisocyanates, cyclohexanediisocyanates, methylcyclohexanediisocyanates, isophorone diisocyanates, methylenebis (4-cyclohexylisocyanates), isopropyridene dicyclohexyldiisocyanates and the like. The alicyclic isocyanate of the above is exemplified. In addition, polymers and derivatives such as burettes, isocyanurates, uretdiones, and carbodiimides of these isocyanates can also be mentioned. These may be used alone or in combination of two or more. Among the above isocyanates, aliphatic isocyanates or alicyclic isocyanates are more preferable than aromatic isocyanates in order to avoid yellowing due to ultraviolet rays.

When used in the state of blocked isocyanate, the blocking agent includes, for example, phenolic compounds such as heavy sulfites, phenol, cresol and ethylphenol, and alcoholic compounds such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol and ethanol. Compounds, active methylene compounds such as dimethyl malonate, diethyl malonate, methyl isobutanoyl acetate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, mercaptan compounds such as butyl mercaptan and dodecyl mercaptan, ε-caprolactam, δ-valerolactam, etc. Examples include lactam compounds, amine compounds such as diphenylaniline, aniline, and ethyleneimine, acid amide compounds of acetanilide and acetate amide, and oxime compounds such as formaldehyde, acetoaldoxime, acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime. These may be used alone or in combination of two or more. Among the above, an isocyanate compound blocked by an active methylene compound is preferable from the viewpoint of being particularly effective in reducing the transferability of the adhesive layer to the adherend.

Further, the isocyanate compound may be used alone, or may be used as a mixture or a bond with various polymers. In terms of improving the dispersibility and crosslinkability of the isocyanate compound, it is preferable to use a mixture or a bond with a polyester resin or a urethane resin.

The epoxy compound is a compound having an epoxy group in the molecule, and examples thereof include a condensate of epichlorohydrin and an ethylene glycol, polyethylene glycol, glycerin, polyglycerin, bisphenol A, or the like with a hydroxyl group or an amino group. There are polyepoxy compounds, diepoxy compounds, monoepoxy compounds, glycidylamine compounds and the like. Examples of the polyepoxy compound include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyltris (2-hydroxyethyl) isocyanate, glycerol polyglycidyl ether, and trimethylolpropane. Examples of the polyglycidyl ether and the diepoxy compound include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcin diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and propylene glycol diglycidyl ether. , Polypropylene glycol diglycidyl ether, Polytetramethylene glycol diglycidyl ether, Monoepoxy compounds include, for example, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenylglycidyl ether, glycidylamine compounds N, N, N', N ′ -Tetraglycidyl-m-xylylene diamine, 1,3-bis (N, N-diglycidylamino) cyclohexane and the like can be mentioned.

Among the above, a polyether epoxy compound is preferable from the viewpoint of good adhesive properties and good adhesion to various shaping layers in the formation of the functional layer described later. The amount of epoxy group is preferably a polyepoxy compound having trifunctional or higher functionalities rather than bifunctionality.

The oxazoline compound is a compound having an oxazoline group in the molecule, and a polymer containing an oxazoline group is particularly preferable, and it can be prepared by polymerization of an addition-polymerizable oxazoline group-containing monomer alone or with another monomer. The addition polymerizable oxazoline group-containing monomer is 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, Examples thereof include 2-isopropenyl-4-methyl-2-oxazoline and 2-isopropenyl-5-ethyl-2-oxazoline, and one or a mixture of two or more thereof can be used. Of these, 2-isopropenyl-2-oxazoline is industrially readily available and suitable. The other monomer is not limited as long as it is a monomer copolymerizable with the addition polymerizable oxazoline group-containing monomer, and is, for example, an alkyl (meth) acrylate (the alkyl group is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, (Meta) acrylic acid esters such as n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group); acrylic acid, methacrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene Unsaturated carboxylic acids such as sulfonic acid and salts thereof (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); unsaturated nitriles such as acrylonitrile and methacrylonitrile; (meth) acrylamide, N-alkyl ( Meta) acrylamide, N, N-dialkyl (meth) acrylamide, (alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl Unsaturated amides such as groups (groups, cyclohexyl groups, etc.); vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; α-olefins such as ethylene and propylene; vinyl chloride and vinylidene chloride , Halogen-containing α, β-unsaturated monomers such as vinyl fluoride; α, β-unsaturated aromatic monomers such as styrene, α-methylstyrene, etc., and one or more of these. Monomer can be used.

The amount of the oxazoline group of the oxazoline compound is preferably in the range of 0.5 to 10 mmol / g, more preferably 1 to 9 mmol / g, still more preferably 3 to 8 mmol / g, and particularly preferably 4 to 6 mmol / g. By using it in the above range, the durability is improved and the adhesive characteristics can be easily adjusted. Further, in the formation of the functional layer described later, the adhesion to various shaping layers is improved, which is preferable.

The carbodiimide-based compound is a compound having one or more carbodiimide or a carbodiimide derivative structure in the molecule. A polycarbodiimide-based compound having two or more in the molecule is more preferable for better adhesive layer strength and the like.

The carbodiimide-based compound can be synthesized by a conventionally known technique, and a condensation reaction of a diisocyanate compound is generally used. The diisocyanate compound is not particularly limited, and any aromatic type or aliphatic type can be used. Specifically, tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, phenylenedi isocyanate, naphthalenedi isocyanate, hexa Examples thereof include methylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyldiisocyanate and dicyclohexylmethane diisocyanate.

Further, in order to improve the water solubility and water dispersibility of the polycarbodiimide compound within the range where the effect of the present invention is not lost, a surfactant may be added, or a quaternary ammonium salt of a polyalkylene oxide or a dialkylamino alcohol may be added. , Hydrophilic monomers such as hydroxyalkyl sulfonates may be added and used.

The content of the carbodiimide group contained in the carbodiimide-based compound is a carbodiimide equivalent (weight [g] of the carbodiimide compound for giving 1 mol of the carbodiimide group), and is usually 100 to 1000, preferably 250 to 800, and more preferably 300. It is in the range of ~ 700, more preferably 350 ~ 650. Use within the above range is preferable because the adhesion to various shaping layers is improved in the formation of the adhesive layer and the functional layer described later.

The silane coupling compound is an organosilicon compound having an organic functional group and a hydrolyzing group such as an alkoxy group in one molecule. For example, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-) (Propylcyclohexyl) Epyl group-containing compounds such as ethyltrimethoxysilane, vinyl group-containing compounds such as vinyltrimethoxysilane and vinyltriethoxysilane, styryl group-containing compounds such as p-styryltrimethoxysilane and p-styryltriethoxysilane, 3- (Meta) Acryloxypropyltrimethoxysilane, 3- (Meta) Acryloxypropyltriethoxysilane, 3- (Meta) Acryloxypropylmethyldimethoxysilane, 3- (Meta) Acryloxypropylmethyldiethoxysilane, etc. (Meta) Acrylic group-containing compound, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl)- 3-Aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-triethoxysilyl-N Amino group-containing compounds such as-(1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, tris (trimethoxysilylpropyl) Isocyanurate group-containing compounds such as isocyanurate and tris (triethoxysilylpropyl) isocyanurate, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldi Examples thereof include mercapto group-containing compounds such as ethoxysilane.

Among the above compounds, from the viewpoint of maintaining the strength and adhesive strength of the adhesive layer, an epoxy group-containing silane coupling compound, a double bond-containing silane coupling compound such as a vinyl group or a (meth) acrylic group, and an amino group-containing silane coupling compound. Compounds are more preferred.

These cross-linking agents are used in a design to improve the performance of the adhesive layer by reacting them in the drying process and the film forming process. It can be inferred that unreacted products of these cross-linking agents, compounds after the reaction, or mixtures thereof (compounds derived from cross-linking agents) are present in the completed adhesive layer.

In addition, the glass transition point is 0 ° C. from the viewpoints of appearance of the adhesive layer, adjustment of adhesive strength, strengthening of the adhesive layer, adhesion to the base film, blocking resistance, and prevention of transfer of the adhesive component to the adherend. It is also possible to use a resin exceeding the above. Conventionally known materials can be used as the resin having a glass transition point exceeding 0 ° C. Among them, polyester resin, acrylic resin, urethane resin and polyvinyl (polyvinyl alcohol, vinyl chloride vinyl acetate copolymer, etc.) are preferable, and considering the influence on the appearance and adhesive strength of the adhesive layer, polyester resin, acrylic resin and urethane A resin selected from the resins is preferable. However, depending on the method of use, there is a concern that the adhesive strength may be significantly reduced, so caution is required.

Resins with a glass transition point exceeding 0 ° C. are used for the appearance of the adhesive layer, adjustment of adhesive strength, strengthening of the adhesive layer, adhesion to the base film, improvement of blocking resistance, etc., but depending on the method of use, Care must be taken because there is a concern that the adhesive strength will be significantly reduced.

As the polyester resin as a resin having a glass transition point exceeding 0 ° C., a polyester resin containing an aromatic compound is preferable. Further, as the aromatic compound, an aromatic polyvalent carboxylic acid is preferable to an aromatic polyvalent hydroxy compound from the viewpoint of adjusting the adhesive strength and the like. Further, as a ratio in the acid component in the polyester resin, the content of the aromatic polyvalent carboxylic acid is usually 50% by weight or more, preferably 70% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight. It is preferably in the range of% and does not contain an aliphatic polyvalent carboxylic acid, particularly an aliphatic polyvalent carboxylic acid having 6 or more carbon atoms, from the viewpoint of adjusting the adhesive strength and blocking resistance.

Various urethanes can be used as the urethane resin as a resin having a glass transition point exceeding 0 ° C. Among them, urethane made of polyester polyols from the viewpoint of adjusting adhesive strength, slipperiness, and blocking resistance. Resin is more preferable. Further, the polyester polyols preferably contain an aromatic compound, and an aromatic polyvalent carboxylic acid is preferable to an aromatic polyvalent hydroxy compound from the viewpoint of adjusting the adhesive strength and the like. The content of the aromatic polyvalent carboxylic acid in the urethane resin is usually in the range of 5 to 80% by weight, preferably 15 to 65% by weight, and more preferably 20 to 50% by weight. By using it in this range, it becomes easy to adjust the adhesive strength and improve the performance of blocking resistance.

The glass transition point of the resin having a glass transition point exceeding 0 ° C. is usually in the range of 10 ° C. or higher, preferably 20 ° C. or higher, more preferably 30 ° C. or higher, and the upper limit of the preferable range is 150 ° C. Within the above range, the adhesive strength can be adjusted without excessively reduced, and it becomes easy to improve the performance such as slipperiness and blocking resistance.

Further, in the formation of the adhesive layer, particles can be used in combination for blocking, improvement of slipperiness, and adjustment of adhesive properties. However, care must be taken because the adhesive strength may decrease depending on the type of particles used. In order not to reduce the adhesive strength so much, the average particle size of the particles used is preferably 3 times or less, more preferably 1.5 times or less, still more preferably 1.0 times or less the film thickness of the adhesive layer. , Especially preferably in the range of 0.8 times or less. In particular, when it is desired to exhibit the adhesive performance of the resin of the adhesive layer as it is, it may be preferable that the adhesive layer does not contain particles.

It has a shaping layer on the film surface opposite to the adhesive layer. The shaping layer is used for improving the functions of various members, and is not particularly limited. Examples thereof include a prism layer, a microlens layer, and a moth-eye layer. In particular, as an improvement in optical efficiency, A prism layer or a microlens layer for improving brightness and viewing angle is preferable, and a prism layer is particularly preferable.

Various shapes have been proposed for the prism layer in order to efficiently improve the brightness, but in general, prism rows having a triangular cross section are arranged in parallel. For example, a prism having a thickness of 10 to 500 μm, a prism row pitch of 10 to 500 μm, and an apex angle of 40 ° to 100 ° can be mentioned.

Various shapes have been proposed for the microlens layer as well, but in general, a large number of hemispherical convex lenses are provided on the film. For example, a hemispherical shape having a thickness of 10 to 500 μm and a diameter of 10 to 500 μm can be mentioned, but it may be shaped like a cone or a polygonal weight.

The material for forming the shaping layer is not particularly limited, and examples thereof include cured products of reactive silicon compounds such as monofunctional (meth) acrylate, polyfunctional (meth) acrylate, and tetraethoxysilane. Of these, from the viewpoint of achieving both productivity and hardness, a polymerized cured product of a composition containing an active energy ray-curable (meth) acrylate is particularly preferable.
The shaping layer is generally formed of a solvent-free active energy ray-curable compound having a solvent content of 5% by weight or less, preferably 3% by weight or less, and more preferably no solvent. To.

The composition containing the active energy ray-curable (meth) acrylate is not particularly limited. For example, a mixture of one or more known active energy ray-curable monofunctional (meth) acrylates, bifunctional (meth) acrylates, and polyfunctional (meth) acrylates is commercially available as an active energy ray-curable resin material. In addition to these, those to which other components are further added can be used as long as the object of the present embodiment is not impaired.

The active energy ray-curable monofunctional (meth) acrylate is not particularly limited, but is, for example, methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and lauryl (meth). ) Acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, alkyl (meth) acrylate such as isobornyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and the like hydroxy Alkoxyalkyl (meth) acrylates such as alkyl (meth) acrylates, methoxyethyl (meth) acrylates, ethoxyethyl (meth) acrylates, methoxypropyl (meth) acrylates, and ethoxypropyl (meth) acrylates, benzyl (meth) acrylates, and phenoxyethyl. Aromatic (meth) acrylates such as (meth) acrylates, diaminoethyl (meth) acrylates, amino group-containing (meth) acrylates such as diethylaminoethyl (meth) acrylates, methoxyethylene glycol (meth) acrylates, phenoxypolyethylene grill (meth) ) Acrylate, ethylene oxide-modified (meth) acrylate such as phenylphenol ethylene oxide-modified (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) acrylic acid and the like.

The active energy ray-curable bifunctional (meth) acrylate is not particularly limited, but for example, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6- Alcandiol di (meth) acrylates such as hexanediol di (meth) acrylates, 1,9-nonanediol di (meth) acrylates and tricyclodecanedimethylol di (meth) acrylates, bisphenol A ethylene oxide-modified di (meth) acrylates. , Bisphenol F ethylene oxide modified di (meth) acrylate and other bisphenol modified di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, urethane di (meth) acrylate, epoxy di (meth) acrylate and the like. Can be mentioned.

The active energy ray-curable polyfunctional (meth) acrylate is not particularly limited, but for example, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, and ditrimethylolpropantetra (meth) acrylate. , Pentaerythritol tri (meth) acrylate, trimethylolpropantri (meth) acrylate, isocyanuric acid ethylene oxide-modified tri (meth) acrylate, ε-caprolactone-modified tris (acroxyethyl) isocyanurate-modified tri (meth) Examples thereof include acrylate, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer and the like.

Other components contained in the composition containing the active energy ray-curable (meth) acrylate are not particularly limited. Examples thereof include inorganic or organic fine particles, polymerization initiators, polymerization inhibitors, antioxidants, antistatic agents, dispersants, surfactants, light stabilizers and leveling agents. Further, in the case of drying after forming a film in the wet coating method, an arbitrary amount of solvent can be added.

The refractive index of the shaping layer is preferably 1.57 or more when high brightness is particularly required. In general, the higher the refractive index, the better the brightness tends to be. In particular, when a polyester film is selected as the base film, the refractive index of the polyester film is around 1.65, and therefore the range of the refractive index of the shaping layer is preferably 1.57 to 1.65, more preferably. Is in the range of 1.58 to 1.64, more preferably 1.59 to 1.63. By setting the above range, the brightness can be effectively increased.

In order to bring the refractive index into the above range, in addition to the above-mentioned general compounds, a method using a compound having many aromatic structures, a sulfur atom, a halogen atom, and a metal compound can be mentioned. Among them, in particular, a method using a compound or a sulfur atom having a large amount of aromatic structure is preferable from the viewpoint of the environment where the refractive index of the shaping layer can be made uniform.

Examples of the compound having many aromatic structures include condensed polycyclic aromatic structures such as naphthalene, anthracene, phenanthrene, naphthalene, benzo [a] anthracene, benzo [a] phenanthrene, pyrene, benzo [c] phenanthrene, and perylene. Examples thereof include a compound having a biphenyl structure, a compound having a fluorene structure, and the like.

Various substituents may be introduced into the fused polycyclic aromatic structure, biphenyl structure, and fluorene structure. In particular, those having a benzene ring-containing substituent such as a phenyl group have a higher refractive index. It is preferable because it can be increased. It is also possible to introduce an atom having a high refractive index, such as a sulfur atom or a halogen atom. Further, in order to improve the adhesion with the base film, it is possible to introduce various functional groups such as an ester group, an amide group, a hydroxyl group, an amino group and an ether group.

When used for higher brightness applications, the sum of fused polycyclic aromatic structures, biphenyl structures, fluorene structures and aromatic compounds that replace those structures can be contained in the shaping layer with other structural types. Although it cannot be said unconditionally because it depends on the amount or the curing condition, it is usually in the range of 20 to 80% by weight, preferably 25 to 70% by weight, and more preferably 30 to 60% by weight based on the entire shaping layer. Is. By using it in the above range, it is possible to form a functional layer having high brightness.

When used for higher brightness applications, the proportion of compounds having a fused polycyclic aromatic structure, biphenyl structure, or fluorene structure that can be contained in the shaping layer is based on the total non-volatile components of the compound composition forming the shaping layer. The ratio is usually in the range of 10% by weight or more, preferably 20 to 90% by weight, and more preferably 25 to 80% by weight. By using it in the above range, it is possible to form a functional layer having high brightness.

The analysis of the components of the shaping layer can be performed by, for example, analysis of TOF-SIMS, ESCA, fluorescent X-ray, NMR and the like.

It is preferable to provide a functional layer in order to firmly adhere the shaping layer to the base film. The main purpose of the functional layer is to improve the adhesion with the shaping layer for giving various performances.

The functional layer can be provided by various conventionally known methods, coatings, transfers, laminates and the like. Among them, it is preferable to provide by coating from the viewpoint of ease of manufacture. It may be provided by in-line coating or by offline coating, but in-line coating is preferably used from the viewpoint of manufacturing cost, function and strength of the functional layer by in-line heat treatment, and improvement of adhesion to the base film. Be done.

As the resin contained in the functional layer, a conventionally known resin can be used, and the resin is not particularly limited as long as it can improve the adhesion to the shaping layer. Examples of resins used for the adhesive layer without being particular about the glass transition point include polyester resin, acrylic resin, urethane resin, polyvinyl resin (polyvinyl alcohol, vinyl chloride vinyl acetate copolymer, etc.) and the like. Among them, polyester resin, acrylic resin, and urethane resin are preferable from the viewpoint of particularly good adhesion, and polyester resin and acrylic resin are more preferable from the viewpoint of film reusability, and they are used with various shaping layers. Acrylic resin and urethane resin are more preferable in consideration of improvement of adhesion. When adhesion is particularly important, urethane resin is preferable, but among them, polyester-based urethane resin formed from polyester polyols and polycarbonate-based urethane resin formed from polycarbonate polyols are more preferable.

Furthermore, a compound containing a carbon-carbon double bond is preferable for improving the adhesion to the shaping layer.
The reason is that when a (meth) acrylate compound is used to form the shaping layer and it is cured by irradiating it with active energy rays, the carbon-carbon double bond in the functional layer and the (meth) acrylate compound This is because it is considered that the carbon-carbon double bond of the above reacts to form a covalent bond.

The functional layer formed from the compound containing a carbon-carbon double bond is a shaping layer formed from a solvent-free active energy ray-curable composition, which is generally difficult to secure adhesion. Ideal for improving adhesion with. For example, in the case of backlight units, there has been a trend toward lower power consumption in recent years, and it is necessary to improve the brightness of prism sheets and microlens sheets more than before. Therefore, materials used for prism layers and microlens layers are used. There is a tendency for the refractive index to increase. In order to increase the refractive index of these shaped layers, a method using a compound containing a large amount of aromatics is adopted. However, on the other hand, when the content of aromatics is large, there is a problem that the adhesion with the functional layer is lowered due to the small interaction thereof. Therefore, a film having a functional layer having a high aromatic content, a high refractive index, that is, a functional layer capable of ensuring sufficient adhesion even in a design having a high brightness is desired.

As the compound containing a carbon-carbon double bond, a polymer containing a carbon-carbon double bond or a (meth) acrylate compound can be used. Examples of the polymer containing a carbon-carbon double bond include urethane resin, acrylic resin and polyester resin. Further, from the viewpoint of introducing a stable carbon-carbon double bond, a urethane resin is more preferable, and among them, a polyester-based urethane resin formed from polyester polyols or a polycarbonate-based urethane resin formed from polycarbonate polyols. Is preferable.

A urethane resin containing a carbon-carbon double bond is a urethane resin having a carbon-carbon double bond, and is a carbon-carbon double bond contained in a compound forming a shaping layer or the like. Conventionally known materials can be used as long as they react. For example, it may be introduced into a urethane resin in the form of an acrylate group, a methacrylate group, a vinyl group, an allyl group or the like.

Various substituents can be introduced into the carbon-carbon double bond, for example, an alkyl group such as a methyl group or an ethyl group, a phenyl group, a halogen group, an ester group, an amide group or the like, or a conjugated double bond. It may have such a structure. The amount of the substituent is not particularly limited, and any of a mono-substituted product, a 2-substituted product, a 3-substituted product, or a 4-substituted product can be used. Considering the reactivity, the mono-substituted product or the 1-substituted product or the 4-substituted product can be used. A di-substituted product is preferable, and a mono-substituted product is more preferable.

Considering the ease of introduction into the urethane resin and the reactivity with the carbon-carbon double bond contained in the compound forming the shaping layer, an acrylate group or a methacrylate group is preferable, and an acrylate group or a methacrylate group having no substituent is preferable. Is more preferable, and an acrylate group having no substituent is particularly preferable.

Further, the ratio of the carbon-carbon double bond portion (C = C portion, molecular weight 24) to the entire urethane resin is preferably 0.5% by weight or more, more preferably 1.0% by weight or more, still more preferably 1. It is 5.5% by weight or more. When the ratio of the carbon-carbon double bond portion to the entire resin is 0.5% by weight or more, the adhesion to the shaping layer is effectively improved.

Further, in order to increase the strength of the functional layer, it is preferable to use a cross-linking agent in combination. As the cross-linking agent, it is possible to use a cross-linking agent similar to that used in the adhesive layer. Among them, oxazoline compounds, epoxy compounds, isocyanate compounds, carbodiimide compounds, melamine compounds, and silane coupling compounds are preferable from the viewpoint of easy to increase strength and ease of use, and oxazoline compounds are particularly preferable from the viewpoint of adhesion. Epoxy compounds, isocyanate compounds, carbodiimide compounds, particularly oxazoline compounds and isocyanate compounds are more preferable, and from the viewpoint of increasing the strength of the functional layer and having an aromatic structure, other cross-linking agents. A melamine compound is more preferable from the viewpoint of having a higher refractive index than that of the above.

Further, in order to further improve the adhesion to the shaping layer, it is also preferable to use two or more kinds of cross-linking agents in combination. From the viewpoint of good adhesion, a combination of an oxazoline compound and an epoxy compound, an oxazoline compound and an isocyanate compound, an oxazoline compound and a carbodiimide compound, and an isocyanate compound and a carbodiimide compound is preferable, and the adhesion is remarkably improved. Is possible.

As a result of various studies, it was found that when the above-mentioned adhesive layer is formed and the films are held in a stacked state, blocking may occur depending on the adhesive force. As a result of examining the solution, it was confirmed that blocking can be reduced by including particles in the functional layer. Furthermore, it was found that the larger the average particle size of the particles, the greater the improvement effect, and the larger the content of the particles in the functional layer, the greater the improvement effect. In other words, we have found a method that can be useful not only for the functional layer to adhere to the shaping layer but also to prevent blocking with the adhesive layer.

Considering that it is related to the volume of particles protruding from the functional layer, it was examined by multiplying the cube of the average particle size (nm) of the particles in the functional layer by the particle content (% by weight) in the functional layer. , A value calculated by dividing the film thickness (nm) of the functional layer (that is, (the cube of the average particle size) × (particle content) ÷ (thickness of the functional layer)). Correlates with the effect of improving blocking, and when it is 50,000 or more, it is found that it is effectively improved. When the value of the above formula is 50,000 or more, not only blocking but also slipperiness can be improved, and a film having good handleability can be obtained. In the following, the above calculation formula may be abbreviated as a particle volume calculation formula.

When it is necessary to improve blocking due to the properties of the adhesive layer and the functional layer, the value of the particle volume calculation formula is preferably 50,000 or more, more preferably 100,000 or more, still more preferably 500,000 or more, and particularly preferably 500,000 or more. It is 1 million or more, most preferably 5 million or more, and the upper limit of the preferable range is 100 million. If the value is too large, there is a concern that particles may fall off, so use within the above range is optimal.

As the above particles, various conventionally known particles can be used, for example, silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, zirconium oxide, titanium oxide. Inorganic particles such as acrylic resin, styrene resin, urea resin, phenol resin, epoxy resin, organic particles such as benzoguanamine resin and the like can be mentioned. Among them, inorganic particles are preferable in terms of imparting hardness, and silica particles are more preferable when they are formed by coating, considering the stability in the state of the coating liquid.

The average particle size of the particles used in the functional layer for improving blocking is preferably 10 to 2000 nm, more preferably 50 to 1000 nm, still more preferably 100 to 700 nm, and particularly preferably 200 to 500 nm. If the average particle size is too large, there is a concern that the particles will fall off. On the contrary, if the average particle size is too small, blocking cannot be reduced, and slipperiness may not be sufficient. By using the film in the above range, blocking with the adhesive layer can be reduced, and the slipperiness is improved to make the film easy to handle.

In addition, the functional layer may contain a release agent for improving blocking and slipperiness. However, if the content is too large, the adhesion to the shaping layer will decrease, so consideration must be given.

Further, as long as the gist of the present invention is not impaired, a defoaming agent, a coatability improving agent, a thickener, an organic lubricant, an antistatic agent, an ultraviolet absorber, etc. are formed as necessary for forming the adhesive layer and the functional layer. It is also possible to use an antioxidant, a foaming agent, a dye, a pigment and the like in combination.

Further, with respect to the film (B) having a shaping layer, from various materials used for forming the film (A) as described above, a shaping layer and further a shaping layer can be obtained as in the film (A). It is possible to provide a functional layer in order to improve the adhesion of the film.

As a ratio in the adhesive layer of the film (A) constituting the laminate, the resin having a glass transition point of 0 ° C. or lower is usually 5% by weight or more, preferably 10 to 99.5% by weight, more preferably 30 to 30 to It is in the range of 98% by weight, more preferably 45 to 96% by weight, particularly preferably 55 to 94% by weight, and most preferably 70 to 90% by weight. By using it in the above range, it is easy to obtain sufficient adhesive strength and it is easy to adjust the adhesive strength. If the content is too small, the adhesive strength may decrease, so it may be necessary to take measures such as increasing the film thickness of the adhesive layer.
However, in order to increase the film thickness, it is necessary to note that the degree and in some cases the line speed may be reduced, which may adversely affect the productivity.

As a ratio in the adhesive layer of the film (A) constituting the laminate, the cross-linking agent is usually 0.5 to 80% by weight, preferably 1 to 65% by weight, more preferably 3 to 50% by weight, still more preferably. It is in the range of 5 to 40% by weight, particularly preferably 8 to 25% by weight. By using it within the above range, the strength of the adhesive layer can be improved, the transfer of the adhesive layer to the adherend can be reduced, and the adhesive strength can be easily adjusted. If the content is too low, the transfer to the adherend will increase, and if the content is too high, the adhesive strength may decrease. Therefore, it is necessary to take measures such as increasing the film thickness of the adhesive layer. May become. However, in order to increase the film thickness, it is necessary to note that the degree and in some cases the line speed may be reduced, which may adversely affect the productivity.

As a ratio in the adhesive layer of the film (A) constituting the laminate, the particles are usually 70% by weight or less, preferably 0.1 to 50% by weight, more preferably 0.5 to 30% by weight, still more preferably. It is in the range of 1 to 20% by weight. By using it in the above range, sufficient adhesive properties, blocking resistance and slipperiness can be easily obtained.

As a ratio in the functional layer of the film constituting the laminate, the resin is usually 1% by weight or more, preferably 10 to 96% by weight, more preferably 15 to 85% by weight, still more preferably 25 to 80% by weight. Particularly preferably in the range of 40 to 75% by weight. By using it in the above range, the adhesion with the shaping layer becomes good.

As a ratio in the functional layer of the film constituting the laminate, the cross-linking agent is usually less than 80% by weight, preferably 5 to 70% by weight, more preferably 10 to 60% by weight, still more preferably 15 to 50% by weight. The range. By using it in the above range, a good appearance and a strong functional layer can be obtained, and a high-quality shaping layer can be formed. In particular, when it is desired to strengthen the functional layer, it is preferable to use a melamine compound in combination, and the preferable range is 3 to 30% by weight, more preferably 5 to 20% by weight.

The proportion of the particles in the functional layer of the film constituting the laminate is usually in the range of 1 to 60% by weight, preferably 2 to 50% by weight, and more preferably 3 to 40% by weight. By using it in the above range, the blocking property with the adhesive layer becomes sufficient while maintaining an appropriate adhesion with the shaping layer.

The analysis of the components in the adhesive layer and the functional layer can be performed by, for example, analysis of TOF-SIMS, ESCA, fluorescent X-ray, IR and the like.

Regarding the formation of the adhesive layer and the functional layer, the above series of compounds are used as a solution or a dispersion of a solvent, and a liquid having a solid content concentration of about 0.1 to 80% by weight is coated on the film. It is preferable to produce a film. In particular, when it is provided by in-line coating, it is more preferably an aqueous solution or an aqueous dispersion. A small amount of organic solvent may be contained in the coating liquid for the purpose of improving the dispersibility in water, improving the film-forming property, and the like. Further, only one type of organic solvent may be used, and two or more types may be used as appropriate.

The thickness of the adhesive layer cannot be unequivocally determined because it depends on the material used for the adhesive layer, but it is usually used for more suitable adjustment of adhesive force or improvement of blocking characteristics, appearance of the adhesive layer, etc. It is 10 μm or less, preferably 0.05 to 8 μm, more preferably 0.1 to 5 μm, still more preferably 0.3 to 3.0 μm, and particularly preferably 0.5 to 2.0 μm.

A general adhesive layer has a thick film thickness of several tens of μm, but in such a case, the adhesive squeezes out from the adhesive layer when it is bonded to an adherend and molded, or when it is cut. May occur noticeably.

However, by adjusting the film thickness within the above range, the protrusion can be minimized. This effect becomes better as the film thickness of the adhesive layer becomes thinner. Further, the thinner the film thickness of the adhesive layer, the smaller the absolute amount of the adhesive layer existing on the film, and it is also effective in reducing the adhesive residue due to the transfer of the components of the adhesive layer to the adherend. Furthermore, it was found that an appropriate adhesive strength that is not too strong can be achieved by setting the film thickness within the above range, and when it is used in applications where it is necessary to achieve both adhesive performance and peeling performance that peels off after bonding. The adhesive-peeling operation can be easily performed, and the optimum film can be obtained.

The thinner the film thickness, the more effective the blocking property, and when the adhesive layer is formed by in-line coating, it is preferable because it is easy to manufacture. On the contrary, when the film thickness is too thin, the adhesive property is deteriorated depending on the composition of the adhesive layer. Since it may disappear, it is preferable to use it in the above-mentioned suitable range depending on the application.

The film thickness of the functional layer is preferably in the range of 1 nm to 1 μm, more preferably 10 to 500 nm, and further preferably 20 to 200 nm. By using the film thickness of the functional layer within the above range, the adhesion to the shaping layer and the blocking prevention property are improved.

Examples of methods for forming the adhesive layer and the functional layer include gravure coat, reverse roll coat, die coat, air doctor coat, blade coat, rod coat, bar coat, curtain coat, knife coat, transfer roll coat, squeeze coat, and impregnation. Conventionally known coating methods such as a coat, a kiss coat, a spray coat, a calendar coat, and an extrusion coat can be used.

The drying and curing conditions for forming the adhesive layer on the film are not particularly limited, but in the case of the coating method, the drying of a solvent such as water used in the coating liquid is preferably 70. It is in the range of ~ 150 ° C., more preferably 80 to 130 ° C., and even more preferably 90 to 120 ° C. The drying time is, as a guide, in the range of 3 to 200 seconds, preferably 5 to 120 seconds. Further, in order to improve the strength of the adhesive layer, a heat treatment step in the range of preferably 180 to 270 ° C., more preferably 200 to 250 ° C., and further preferably 210 to 240 ° C. is performed in the film manufacturing process. The time of the heat treatment step is, as a guide, in the range of 3 to 200 seconds, preferably 5 to 120 seconds.

Further, if necessary, heat treatment and active energy ray irradiation such as ultraviolet irradiation may be used in combination. The film constituting the laminate in the present invention may be subjected to surface treatment such as corona treatment and plasma treatment in advance.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded. The measurement method and evaluation method used in the present invention are as follows.

(1) Method for measuring the ultimate viscosity of polyester 1 g of polyester from which other polymer components and pigments incompatible with polyester have been removed is precisely weighed, and 100 ml of a mixed solvent of phenol / tetrachloroethane = 50/50 (weight ratio) is added. And dissolved, and measured at 30 ° C.

(2) Measurement method of average particle size (d50: μm) 50% value of integration (weight basis) in equivalent spherical distribution measured using a centrifugal sedimentation type particle size distribution measuring device SA-CP3 manufactured by Shimadzu Corporation. Was taken as the average particle size.

(3) Method for measuring film thickness of adhesive layer and functional layer The surface of the adhesive layer or functional layer was dyed with RuO ₄ and embedded in an epoxy resin. Then, the section prepared by the ultrathin section method was stained with RuO ₄ , and the cross section of the adhesive layer was measured using TEM (H-7650 manufactured by Hitachi High-Technologies Corporation, accelerating voltage 100 kV).

(4) Glass transition point Using a differential scanning calorimetry device (DSC) 8500 manufactured by Perkin Elmer Japan Co., Ltd., the measurement was performed at -100 to 200 ° C. under a temperature rising condition of 10 ° C. per minute.

(5) Adhesive Strength Evaluation Method The two films (A) and the film (B) of the laminated body were peeled off by hand, and their resistance was evaluated. That is, A has resistance and is sticky, and has weak resistance but has adhesive strength, and has only the laminated film (B) (the film on which the adhesive layer is not formed). However, B was defined as the case where the film could not be peeled off, and C was defined as the case where the film had only enough adhesive force to peel off when only the laminated film (B) was held, or the case where the laminated body could not be formed due to no adhesive force. In the case of evaluation C, there is a concern that scratches may occur due to slippage between the films, or defects may occur due to destruction of the shaping layer.

(6) Evaluation Method of Transferability of Adhesive Layer to Shaped Layer After treating the laminate at 60 ° C. for 3 days, the film was peeled off and the surface of the shaped layer was observed.
A was defined as a case where there was no trace on the shaping layer (no migration of the adhesive layer was observed), B was when a thin trace was observed, and C was when a clear trace was observed on the entire surface. In applications where migration is a concern, C should be avoided, and especially in applications where low migration is required, levels A and B, particularly A level, are preferable.

(7) Method for evaluating the adhesion of the adhesive layer to the substrate The adhesive layer side of one A4 size film (A) and the A4 size film without the adhesive layer of Comparative Example 1 described later are overlapped and attached with a finger. After that, the film having the adhesive layer is peeled off, the surface of the film without the adhesive layer of Comparative Example 1 is observed, and when there is no adhesive residue (transfer trace of the adhesive layer) (adhesion between the adhesive layer and the original base material). The case where the property is good) is defined as A, and the case where there is adhesive residue (when the adhesion of the adhesive layer to the substrate is poor) is defined as B.

(8) Evaluation method of adhesion of shaping layer After treating the laminate for 24 hours in an environment of 60 ° C. and 90% RH, the shaping layer (prism layer) is cross-cut by 10 × 10 and the cross cut is performed. Attach a tape with a width of 18 mm (Cellotape (registered trademark) CT-18 manufactured by Nichiban Co., Ltd.) on top, observe the peeled surface after sharply peeling at a peeling angle of 180 degrees, and if the peeled area is less than 5% A was 5% or more and less than 20%, B was, 20% or more and less than 50% was C, and 50% or more was D.

(9) Luminance Evaluation Method A, when the luminance is measured using a luminance measuring device (BM-7 manufactured by Topcon Co., Ltd.) and the luminance is improved as compared with Comparative Example 13, is A, equivalent or less. Was B. In addition, the case where the brightness could not be measured due to the inability to form the shaping layer was set as "-".

The polyester used in Examples and Comparative Examples was prepared as follows.
<Manufacturing method of polyester (a)>
Ester 100 parts by weight of dimethyl terephthalate, 60 parts by weight of ethylene glycol, 30 ppm of ethyl acid phosphate for the produced polyester, and 100 ppm of magnesium acetate / tetrahydrate as a catalyst for the produced polyester in a nitrogen atmosphere at 260 ° C. A chemical reaction was allowed. Subsequently, 50 ppm of tetrabutyl titanate was added to the produced polyester, the temperature was raised to 280 ° C. over 2 hours and 30 minutes, the pressure was reduced to an absolute pressure of 0.3 kPa, and the mixture was further polycondensed for 80 minutes to obtain the ultimate viscosity. A polyester (a) having 0.63 and a diethylene glycol content of 2 mol% was obtained.

<Manufacturing method of polyester (b)>
100 parts by weight of dimethyl terephthalate, 60 parts by weight of ethylene glycol, and magnesium acetate tetrahydrate as a catalyst were subjected to an esterification reaction at 225 ° C. with 900 ppm in a nitrogen atmosphere. Subsequently, 3500 ppm of positive phosphoric acid was added to the produced polyester, and 70 ppm of germanium dioxide was added to the produced polyester, the temperature was raised to 280 ° C. over 2 hours and 30 minutes, and the pressure was reduced to an absolute pressure of 0.4 kPa. Polyester (b) having an ultimate viscosity of 0.64 and a diethylene glycol content of 2 mol% was obtained by melt polycondensation for 85 minutes.

<Manufacturing method of polyester (c)>
In the method for producing polyester (a), the polyester (c) is obtained by using the same method as the method for producing polyester (a) except that 0.3 parts by weight of silica particles having an average particle size of 2 μm are added before melt polymerization. It was.

Examples of compounds constituting the adhesive layer and the functional layer are as follows.
(Compound example)
-Polyester resin: (IA)
Aqueous dispersion of polyester resin (glass transition point: -20 ° C) having the following composition Monomer composition: (acid component) dodecanedicarboxylic acid / terephthalic acid / isophthalic acid / 5-sodium sulfoisophthalic acid // (diol component) ethylene Glycol / 1,4-butanediol = 20/38/38/4 // 40/60 (mol%)
-Polyester resin: (IB)
Aqueous dispersion of polyester resin (glass transition point: -30 ° C) having the following composition Monomer composition: (acid component) dodecanedicarboxylic acid / terephthalic acid / isophthalic acid / 5-sodium sulfoisophthalic acid // (diol component) ethylene Glycol / 1,4-butanediol = 30/33/33/4 // 40/60 (mol%)

・ Acrylic resin: (IC)
Acrylic resin (glass transition point: -50 ° C) aqueous dispersion having the following composition 2-ethylhexyl acrylate / methyl methacrylate / methacrylic acid = 85/12/3 (% by weight)
・ Acrylic resin: (ID)
Aqueous dispersion of acrylic resin (glass transition point: -40 ° C) having the following composition 2-ethylhexyl acrylate / normal butyl acrylate / methyl methacrylate / 2-hydroxyethyl methacrylate / acrylic acid = 58/20/15/5 / 2 (% by weight)

・ Acrylic resin: (IE)
Aqueous dispersion of acrylic resin (glass transition point: -40 ° C) having the following composition Normal butyl acrylate / 2-ethylhexyl acrylate / acrylonitrile / acrylic acid = 82/10/5/3 (% by weight)
・ Acrylic resin: (IF)
Aqueous dispersion of acrylic resin (glass transition point: -50 ° C) having the following composition 2-ethylhexyl acrylate / normal butyl acrylate / ethyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 50/27/15/5 / 3 (% by weight)

-Melamine compound: (IIA) Hexamethoxymethylol melamine-Isocyanate compound: (IIB)
1000 parts of hexamethylene diisocyanate was stirred at 60 ° C., and 0.1 part of tetramethylammonium caprilate was added as a catalyst. After 4 hours, 0.2 part of phosphoric acid was added to stop the reaction to obtain an isocyanurate-type polyisocyanate composition. 100 parts of the obtained isocyanurate-type polyisocyanate composition, 42.3 parts of methoxypolyethylene glycol having a number average molecular weight of 400, and 29.5 parts of propylene glycol monomethyl ether acetate were charged and held at 80 ° C. for 7 hours. Then, the reaction solution temperature was maintained at 60 ° C., 35.8 parts of methyl isobutanoyl acetate, 32.2 parts of diethyl malonate, and 0.88 parts of a 28% methanol solution of sodium methoxide were added and kept for 4 hours. Block polyisocyanate with active methylene obtained by adding 58.9 parts of n-butanol, holding at a reaction solution temperature of 80 ° C. for 2 hours, and then adding 0.86 parts of 2-ethylhexyl acid phosphate.

-Oxazoline compound: (IIC)
Acrylic polymer Epocross with oxazoline group and polyalkylene oxide chain (Oxazoline group amount = 4.5 mmol / g, manufactured by Nippon Shokubai Co., Ltd.)
-Epoxy compound: (IID) Polyglycerol polyglycidyl ether-carbodiimide compound, which is a polyfunctional polyepoxy compound: (IIE)
Polycarbodiimide compound Carbodilite (carbodiimide equivalent = 600, manufactured by Nisshinbo Holdings Inc.)

-Polyester resin: (IIIA)
Aqueous dispersion of polyester resin (glass transition point: 30 ° C) consisting of the following composition Monomer composition: (acid component) terephthalic acid / isophthalic acid / 5-sodium sulfoisophthalic acid // (diol component) ethylene glycol / 1,4 -Butandiol / diethylene glycol = 40/56/4 // 45/25/30 (mol%)
-Polyester resin: (IIIB)
Aqueous dispersion of polyester resin (glass transition point: 50 ° C.) having the following composition Monomer composition: (acid component) terephthalic acid / isophthalic acid / 5-sodiumsulfoisophthalic acid // (diol component) ethylene glycol / 1,4 -Butandiol / diethylene glycol = 50/46/4 // 70/20/10 (mol%)
・ Acrylic resin: (IIIC)
Acrylic resin (glass transition point: 10 ° C.) aqueous dispersion having the following composition Normal butyl acrylate / ethyl acrylate / methyl methacrylate / 2-hydroxyethyl methacrylate / acrylic acid = 10/52/30/5/3 (% by weight)

・ Acrylic resin: (IIID)
Acrylic resin (glass transition point: 40 ° C.) aqueous dispersion having the following composition Ethyl acrylate / methyl methacrylate / N-methylol acrylamide / acrylic acid = 48/45/4/3 (% by weight)

-Urethane resin with carbon-carbon double bond: (IIIE)
Hydroxyethyl acrylate: Dicyclohexylmethane diisocyanate: Hexamethylene diisocyanate trimeric: Caprolactone: Ethylene glycol: Dimethylolpropaneic acid = 18: 12: 22: 26: 18: 4 (mol%) carbon-carbon double bond Urethane resin with a weight of 2.0% by weight.
-Urethane resin with carbon-carbon double bond: (IIIF)
Hydroxyethyl acrylate: Dicyclohexylmethane diisocyanate: Hexamethylene diisocyanate trimeric: Caprolactone: Ethylene glycol: Dimethylolpropaneic acid = 6: 10: 20: 38: 22: 4 (mol%) carbon-carbon double bond Urethane resin with a weight of 0.7% by weight.

-Particles: (IVA) Silica particles with an average particle size of 45 nm-Particles: (IVB) Silica particles with an average particle size of 450 nm

Examples of compounds constituting the shaping layer are as follows.
(Compound example)
-UV curable compound: (ia)
2-biphenoxyethyl acrylate
-UV curable compound: (ib)
4,4'-(9-fluorenylidene) bis (2-phenoxyethyl acrylate)
-UV curable compound: (ic)
Ethylene glycol-modified bisphenol A acrylate (ethylene glycol chain = 8)
-UV curable compound: (id)
Ethylene glycol-modified bisphenol A acrylate (ethylene glycol chain = 10), UV curable compound: (ie)
Trimethylolpropane triacrylate / photopolymerization initiator: (ii)
Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide

Example 1:
A mixed raw material in which polyesters (a), (b) and (c) are mixed at a ratio of 91%, 3% and 6%, respectively, is used as a raw material for the outermost layer (surface layer), and polyesters (a) and (b) are 97, respectively. Using the mixed raw material mixed at a ratio of% and 3% as the raw material for the intermediate layer, each of them was supplied to two extruders, melted at 285 ° C., and then placed on a cooling roll set at 40 ° C. An unstretched sheet was obtained by co-extruding and cooling and solidifying with a layer structure of layers (surface layer / intermediate layer / surface layer = discharge amount of 3: 44: 3).
Next, after stretching 3.2 times in the longitudinal direction at a film temperature of 85 ° C. using the difference in roll peripheral speed, the coating liquid A1 shown in Table 1 below was applied to one side of the vertically stretched film to form a film thickness (drying) of the adhesive layer. The coating liquid B1 shown in Table 2 below is applied to the opposite surface so that the film thickness (after drying) of the functional layer is 90 nm, and the film is guided to a tenter to 95. After drying at ° C. for 10 seconds, the film was stretched 4.2 times at 120 ° C. in the lateral direction, heat-treated at 230 ° C. for 10 seconds, and then relaxed by 2% in the lateral direction to obtain a polyester film having a thickness of 50 μm. ..

In order to form a prism layer which is a shaping layer on the functional layer of the obtained polyester film, a large number of prism rows having a pitch of 50 μm and an apex angle of 65 ° are arranged in parallel on a mold member, which is a solvent-free system shown in Table 3 below. The composition P1 of the above is arranged, a polyester film is layered on the polyester film in a direction in which the functional layer of the film obtained above comes into contact with the composition, the composition is uniformly stretched by a roller, and ultraviolet rays are irradiated from the ultraviolet irradiation device. , Hardened. Next, the film was peeled off from the mold member to obtain a film (A) on which a prism layer (hereinafter, may be referred to as P1) was formed.

Further, a polyester film having a thickness of 50 μm having a functional layer by the coating liquid B1 was obtained in the same manner as described above except that the adhesive layer was not provided. The prism layer, which is a shaping layer, was formed on the functional layer in the same manner as described above to obtain a film (B) on which the prism layer formed by the composition P1 was formed.

A laminated body was obtained by laminating the adhesive layer of the obtained film (A) and the prism layer of the film (B) so as to be in contact with each other. When the obtained laminate was evaluated, it was good with adhesive strength and high brightness. The characteristics of this laminated body are shown in Table 5.

Examples 2-222:
In Example 1, a laminate was obtained in the same manner as in Example 1 except that the coating agent compositions were changed to the compositions shown in Tables 1 and 2 and the compound composition of the shaping layer was changed to the compositions shown in Table 3. As shown in Tables 4 to 15 below, the obtained laminates had good adhesive strength and high brightness.

Example 223:
A polyester film was obtained in the same manner as in Example 1 except that the adhesive layer was not provided in Example 1. On this polyester film without an adhesive layer, the coating liquid A3 shown in Table 1 below was applied so that the film thickness (after drying) of the adhesive layer was 2.5 μm, dried at 100 ° C. for 90 seconds, and then offline. A polyester film having a non-stretched adhesive layer formed by coating was obtained. A prism layer was formed in the same manner as in Example 1 to obtain a laminated body. As shown in Table 15, the obtained laminate had good adhesive strength and brightness. However, the adhesion of the adhesive layer to the base material and the transferability to the shaping layer were not good.

Example 224:
In Example 223, a laminate was obtained in the same manner as in Example 223 except that the composition of the adhesive layer was changed to the composition shown in Table 1. As shown in Table 15 below, the obtained laminate had good adhesive strength and brightness, but the adhesion of the adhesive layer to the substrate and the transferability to the shaping layer were not good.

Comparative Example 1:
A polyester film was obtained in the same manner as in Example 1 except that the adhesive layer and the functional layer were not provided in Example 1. Even when laminated, as shown in Table 17 below, there was no adhesive strength and the brightness was low.

Comparative Example 2:
A polyester film having no adhesive layer and no functional layer was obtained in the same manner as in Comparative Example 1. After that, an attempt was made to form a shaping layer in the same manner as in Example 1, but the adhesion between the film and the shaping layer was poor, and the shaping layer could not be formed well.

Comparative Examples 3 to 12:
In Example 1, a laminate was obtained in the same manner as in Example 1 except that the coating agent composition was changed to the coating agent composition shown in Tables 1 and 2. As shown in Table 17, the obtained laminate was a film having no adhesive strength.

Comparative Examples 13 and 14:
A laminate was obtained in the same manner as in Example 3 except that the shaping layer of the film (A) or the film (B) was not provided in Example 3. As shown in Table 17, the obtained laminate had low brightness.

Comparative Example 15:
On the polyester film without the adhesive layer and the functional layer obtained in Comparative Example 1, the coating liquid A3 shown in Table 1 below was applied at 100 ° C. for 3 minutes so that the film thickness (after drying) of the adhesive layer was 20 μm. Drying was performed to obtain a polyester film on which an unstretched adhesive layer was formed by an offline coating. When the adhesive layer side was bonded to the polyester film and then cut, a protrusion of the adhesive layer component, which was not seen in the examples, was observed, and there was a concern about contamination by the adhesive component. Other characteristics are as shown in Table 17.

The film of the present invention is used for applications that require a laminated body that is less likely to cause defects when various members are laminated, simplifies the manufacturing process, and has cost competitiveness, such as improvement of optical efficiency in a backlight unit. It can be preferably used.

Claims (8)

A film (A) having a shaping layer on one surface of the film and an adhesive layer containing a resin having a glass transition point of 0 ° C. or lower on the other surface, and a film (B) having a shaping layer. And are laminated so that the adhesive layer of the film (A) and the shaping layer of the film (B) are in contact with each other, and the resin having a glass transition point of 0 ° C. or lower is a sulfonic acid or sulfonate as a functional group. , A carboxylic acid, or a carboxylic acid salt, and a polyester resin having an aliphatic polyvalent carboxylic acid having 10 or more carbon atoms as a constituent component , and the shaping layer of the film (A) and the shaping of the film (B). A laminate characterized in that the layer is one selected from a prism layer, a microlens layer, and a moth-eye layer. A film (A) having a shaping layer on one surface of the film and an adhesive layer containing a resin having a glass transition point of 0 ° C. or lower on the other surface, and a film (B) having a shaping layer. And are laminated so that the adhesive layer of the film (A) and the shaping layer of the film (B) are in contact with each other.
The resin having a glass transition point of 0 ° C. or lower contains an alkyl (meth) acrylate having an alkyl group having 4 or more and 8 or less carbon atoms as a constituent monomer , and the ester terminal contains 2 or less carbon atoms. An acrylic resin containing a certain ester compound or a compound having a cyclic structure .
Among the monomers constituting the acrylic resin, the content of the monomer having a glass transition point of 0 ° C. or lower in the case of homopolymer is 30% by weight or more as a ratio to the entire acrylic resin.
The acrylic resin has a hydrophilic functional group
The film shaping layer and a film shaping layer (B) of (A) is a prism layer, a laminate which is a one selected from the microlens layer and the moth-eye layer. The laminate according to claim 1 or 2 , wherein the pressure-sensitive adhesive layer of the film (A) has a film thickness of 10 μm or less. The laminate according to any one of claims 1 to 3 , wherein the adhesive layer is a layer formed of a coating liquid containing a cross-linking agent. The laminate according to any one of claims 1 to 4 , wherein the adhesive layer contains particles. The laminate according to claim 5 , wherein the average particle size of the particles is three times or less the film thickness of the adhesive layer. The laminate according to any one of claims 1 to 6 , wherein the excipient layer is a polymerized cured product of a composition containing an active energy ray-curable (meth) acrylate. The laminate according to any one of claims 1 to 7 , wherein the film (A) has a functional layer for improving adhesion between the shaping layer and the film.