JP2019025764A - Laminate and display - Google Patents

Abstract

To provide a laminate having surface protection properties without occurrence of scratches and without trouble during winding up, while having antistatic properties.SOLUTION: A laminate has a resin base material and a surface protective layer. The surface protective layer comprises a coating composition comprising fine particles with an average particle size of 10-500 nm, a slip agent, and a conductive material. The surface protective layer has a dynamic friction coefficient of 1 or less, and peeling strength of 1.5 N/25 mm or more.SELECTED DRAWING: None

Description

The present invention relates to a laminate and a display.

Various optical films and optical filters used in flat panel displays or the like may require various characteristics in addition to excellent optical characteristics. For example, as in Patent Document 1, antistatic properties may be required to prevent dust adhesion, and by applying a coating composition containing a conductive material such as a surfactant or a conductive polymer to a film. Measures may be taken to provide an antistatic layer on the film. Further, in order to prevent scratches, surface protection (sliding property, scratch resistance) is often required, and a method for protecting the surface by adding a slip agent to impart slipping property has also been proposed.

On the other hand, in various optical films and optical filters, attempts have been made to greatly improve productivity by manufacturing by in-line coating in which coating is performed during a film forming process. However, when a slip agent is added, the slipping property may be excessive, it is difficult to control the movement of the film during winding, and bamboo shoot-like winding deviation may occur.

JP-A-2-73307

An object of the present invention is to provide a laminate having surface protection for an optical film or an optical filter that has antistatic properties, does not cause scratches, and does not cause defects during winding. To do.

As a result of intensive studies, the present inventors have surprisingly obtained new knowledge that the adhesion measured by the peel strength test affects the prevention of winding and based on the knowledge, the resin substrate and the surface The laminate composed of the protective layer is made of a coating composition containing fine particles having an average particle diameter of 10 to 500 nm, a slip agent, and a conductive material, has a dynamic friction coefficient of 1 or less, and a peel strength of 1 By using a surface protective layer of 5 N / 25 mm or more, while maintaining good antistatic properties, it achieves both moderate slipperiness and adhesion, does not cause scratches, and causes excessive slippage during winding. The present invention has been completed by finding out that no trouble occurs.

That is, the present invention relates to:
[1] A laminate comprising a resin base material and a surface protective layer,
The surface protective layer is composed of a coating composition containing fine particles having an average particle diameter of 10 to 500 nm, a slip agent, and a conductive material,
A laminated body, wherein the surface protective layer has a dynamic friction coefficient of 1 or less and a peel strength of 1.5 N / 25 mm or more;
[2] The laminate according to [1], wherein the coating composition contains 0.1 to 10% by weight of fine particles having an average particle diameter of 10 to 500 nm with respect to the total solid content;
[3] The laminate of [1] or [2], wherein the fine particles are inorganic fine particles and / or organic fine particles having a crosslinked structure;
[4] The laminate of [1] to [3], wherein the slip agent is a silicone resin and / or a fluorine resin;
[5] The laminate of [1] to [4], wherein the conductive material is at least one selected from the group consisting of a conductive polymer, a carbon nanomaterial, and a metal nanowire;
[6] The laminate according to [1] to [5], wherein the coating composition includes at least one thermoplastic resin selected from the group consisting of an acrylic resin, a urethane resin, an ester resin, and a polyether resin;
[7] The laminate of [1] to [6], wherein the surface protective layer is a stretched product;
[8] A laminate comprising [1] to [7], and further comprising a laminate of [9] [1] to [8], in which an acrylic pressure-sensitive adhesive layer and / or a urethane-based easy adhesion layer is further disposed. .

According to the present invention, by providing a surface protective layer having a specific dynamic friction coefficient and peel strength, the anti-slip property is maintained, but the slipping property and the adhesion property are appropriately maintained, so that scratches are generated. Therefore, it is possible to provide a laminate that does not cause a problem during winding. As a result, productivity is remarkably improved, which can contribute to improvement of productivity of general-purpose displays.

<< Laminate >>
First, the laminated body of this invention is demonstrated.
The laminate of the present invention comprises a resin base material and a surface protective layer, and the surface protective layer comprises a coating composition containing fine particles having an average particle size of 10 to 500 nm, a slip agent, and a conductive material. The surface protective layer has a dynamic friction coefficient of 1 or less and a laminate strength of 1.5 N / 25 mm or more.

<Resin substrate>
In the laminate of the present invention, the resin substrate is not particularly limited as long as it is a thermoplastic resin substrate. For example, amorphous polyethylene terephthalate (A-PET), polyester resins such as modified polyester, polyethylene ( PE) resin, polypropylene (PP) resin, polystyrene resin, polyolefin resin such as cyclic olefin resin, vinyl resin such as polyvinyl chloride and polyvinylidene chloride, polyether ether ketone (PEEK) resin, polysulfone (PSF) resin And base materials such as polyethersulfone (PES) resin, polycarbonate (PC) resin, polyamide resin, polyimide resin, acrylic resin, and triacetyl cellulose (TAC) resin. Amorphous polyethylene terephthalate (A-PET), polyolefin resin, acrylic resin, and triacetyl cellulose (TAC) resin are preferable from the viewpoints of flexibility, transparency, easy moldability, and the like. These resins may be used alone or in combination of two or more.

In the laminate of the present invention, the thickness of the resin base material is not particularly limited, but is preferably 40 to 900 μm, more preferably 80 to 800 μm, and further preferably 120 to 600 μm. . When the thickness of the resin base material is within the above range, it is possible to secure a high degree of transparency and mechanical strength that can withstand various processing processes when the processing is stretched 4 to 8 times while sufficiently maintaining the stretchability. It is.

<Surface protective layer>
The surface protective layer is made of a coating composition containing specific fine particles, a slip agent, and a conductive material, has a surface dynamic friction coefficient of 1 or less, and a peel strength of 1.5 N / 25 mm or more. By providing such a surface protective layer, it is possible to provide a laminate that has antistatic properties but does not cause scratches and does not cause problems during winding.

The fine particles have an average particle size of 10 to 500 nm, more preferably 20 to 200 nm. When the average particle size of the fine particles is within the above range, good slipperiness and adhesion can be obtained.

Examples of the fine particles include inorganic fine particles and / or organic fine particles having a crosslinked structure. These may be used in combination.
The inorganic fine particles are not particularly limited. For example, silica fine particles such as colloidal silica, hollow silica, and fumed silica, and metal oxide fine particles such as titania and zirconia, as well as thermoplastic or thermosetting. Core-shell type acrylic-silica composite particles with acrylic resin coated with silica, core-shell type melamine-silica composite particles with melamine resin coated with silica, core-shell type with silica particles coated with thermoplastic or thermosetting acrylic resin Organic inorganic such as acrylic-silica composite particles, core-shell type melamine-silica composite particles with silica particles coated with melamine resin, acrylic-silica composite particles with small silica particles supported by thermoplastic or thermosetting acrylic particles Examples include composite particles. These may be used alone or in combination of two or more.

The organic fine particles having a crosslinked structure are not particularly limited, and examples thereof include fluororesin fine particles, acrylic resin fine particles, melamine resin fine particles, and urethane rubber fine particles. These may be used alone or in combination of two or more.

The content of the fine particles is preferably 0.1 to 10% by weight, more preferably 0.5 to 10% by weight, further preferably 1 to 10% by weight based on the total solid content in the coating composition. %. When the blending amount of the fine particles is within the above range, sufficient and appropriate slipperiness can be obtained.

The slip agent is not particularly limited, and examples thereof include hydrocarbon resins, oxy fatty acids, aliphatic alcohols, silicone resins, fluorine resins, and the like. From the viewpoint of slipperiness, silicone resins and fluorine resins are preferable. These may be used alone or in combination of two or more.

Examples of the hydrocarbon resin include low molecular weight wax, paraffin wax, polyethylene wax, and chlorinated hydrocarbon.
Examples of the oxy fatty acid include higher fatty acids such as lauric acid, stearic acid, and behenic acid, and hydroxy stearic acid.
Examples of the aliphatic alcohol include stearyl alcohol, lauryl alcohol, and palmityl alcohol.

Examples of the silicone resin include polydimethylsiloxane, polyether-modified polydimethylsiloxane, and polymethylalkylsiloxane.
Fluorocarbon etc. are mentioned as a fluorine resin.

The content of the slip agent may be 1 to 20% by weight with respect to the total solid content in the coating composition, preferably 2 to 20% by weight, and more preferably 4 to 20% by weight. When the blending amount of the slip agent is within the above range, bleed out does not occur in the surface protective layer, and good slipperiness and transparency can be obtained.

Although it does not specifically limit as a conductive material, For example, a conductive polymer, a carbon nanomaterial, a metal nanowire etc. are mentioned. Conductive polymers and carbon nanomaterials are preferred because they are suitable for use in applications that require transparency, including displays. These may be used alone or in combination of two or more.

It does not specifically limit as a conductive polymer, A conventionally well-known conductive polymer can be used, For example, polythiophene, polypyrrole, polyaniline, polyacetylene, polyphenylene vinylene, polynaphthalene, derivatives thereof etc. are mentioned. These may be used alone or in combination of two or more. Among these, a conductive polymer including at least one thiophene ring in the molecule is preferable in that a molecule having high conductivity can be easily formed by including a thiophene ring in the molecule. The conductive polymer may form a complex with a dopant such as polyanion.

As the conductive polymer containing at least one thiophene ring in the molecule, poly (3,4-dialkoxythiophene) or poly (3,4-alkylenedioxythiophene) is particularly preferable. As poly (3,4-dialkoxythiophene) or poly (3,4-alkylenedioxythiophene), a cationic polythiophene composed of repeating structural units represented by the following formula (1) is preferable:

[Wherein, R ¹ and R ² independently represent a hydrogen atom or a C _1-4 alkyl group, or, when R ¹ and R ² are bonded, C _1-4 alkylene, Represents a group].

The C _1-4 alkyl group is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. .
In addition, when R ¹ and R ² are bonded, the C _1-4 alkylene group is not particularly limited, and examples thereof include a methylene group, a 1,2-ethylene group, a 1,3-propylene group, 1, 4-butylene group, 1-methyl-1,2-ethylene group, 1-ethyl-1,2-ethylene group, 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene group, etc. Can be mentioned. Among these, a methylene group, 1,2-ethylene group, and 1,3-propylene group are preferable, and a 1,2-ethylene group is more preferable. In the C _1-4 alkyl group and the C _1-4 alkylene group, a part of hydrogen may be substituted. As the polythiophene having a C _1-4 alkylene group, poly (3,4-ethylenedioxythiophene) is particularly preferable.

The weight average molecular weight of the conductive polymer is preferably 500 to 100,000, more preferably 1000 to 50000, and further preferably 1500 to 20000. When the weight average molecular weight of the conductive polymer is within the above range, the viscosity and conductivity required when used in various applications can be ensured.

The dopant is not particularly limited, but a polyanion is preferable. The poly anion forms a complex by forming an ion pair with polythiophene or a derivative thereof, and the polythiophene or the derivative thereof can be stably dispersed in water. Although it does not specifically limit as a poly anion, For example, carboxylic acid polymers (for example, polyacrylic acid, polymaleic acid, polymethacrylic acid, etc.), sulfonic acid polymers (for example, polystyrene sulfonic acid, polyvinyl sulfonic acid, polyisoprene) Sulfonic acid etc.). These carboxylic acid polymers and sulfonic acid polymers are also copolymers of vinyl carboxylic acids and vinyl sulfonic acids with other polymerizable monomers such as aromatic vinyl compounds such as acrylates, styrene, vinyl naphthalene, etc. It may be. Among these, polystyrene sulfonic acid is particularly preferable.

The polystyrene sulfonic acid preferably has a weight average molecular weight of 20,000 to 1,000,000, and more preferably 50,000 to 500,000. When the molecular weight of the polystyrene sulfonic acid is within the above range, the dispersion stability of the polythiophene conductive polymer in water is good.
The weight average molecular weight is a value measured by gel permeation chromatography (GPC).

The composite of the conductive polymer and the dopant is preferably a composite of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid because it is particularly excellent in conductivity.

The conductivity of the conductive polymer is not particularly limited, but is preferably 0.01 S / cm or more and 0.05 S / cm or more from the viewpoint of imparting sufficient conductivity to the surface protective layer. More preferred.

Examples of carbon nanomaterials include carbon nanotubes, carbon nanohorns, carbon nanowalls, and fullerenes. Among these, it is preferable to use carbon nanotubes. These may be used alone or in combination of two or more.
Carbon nanotubes generally have a hollow fiber shape and are carbon materials having a diameter of 0.5 nm to 5 μm and a length of about 10 nm to 1000 μm. Carbon nanotubes having a diameter of 0.5 nm to 1 μm and a length of 10 nm to 100 μm are used. It can be preferably used.

As metal nanowire, what consists of a metal simple substance or a metal containing compound is mentioned. Although it does not specifically limit as a metal simple substance, For example, silver, copper, silver, iron, cobalt, nickel, zinc, ruthenium, rhodium, palladium, cadmium, osmium, iridium, platinum etc. are mentioned, As a metal content compound, Although it does not specifically limit, For example, what contains these metals is mentioned. These may be used alone or in combination of two or more.

The content of the conductive material may be 30% by weight or less with respect to the total solid content in the coating composition, preferably 1 to 30% by weight, and more preferably 2 to 25% by weight. When the content of the conductive material is within the above range, the slipperiness is not impaired while exhibiting sufficient antistatic properties.

A thermoplastic resin may be added to the coating composition. As described above, it is preferable that the content of the slip agent is within a predetermined range from the viewpoint of obtaining appropriate slipperiness, but the addition of the thermoplastic resin is sufficient even if a small amount of slip agent is added. Appropriate slipperiness can be obtained. The reason why sufficient and moderate slipperiness can be obtained even if a small amount of slip agent is added is due to the high fluidity of the thermoplastic resin during film formation. This is because they tend to localize in the vicinity thereof. Moreover, it is preferable to add a thermoplastic resin also from the point which enables the application to the extending | stretching process mentioned later.

The thermoplastic resin that can be included in the coating composition is not particularly limited, and examples thereof include acrylic resins, urethane resins, ester resins, olefin resins, carboxyl group-containing resins, and polyether resins. These may be used alone or in combination of two or more. The same type of resin as the thermoplastic resin used in the resin substrate may be used, or a different thermoplastic resin may be used. Among these, an acrylic resin, a urethane resin, an ester resin, and a polyether resin are preferably used, and in particular, a combination of a polyether resin and one or more other thermoplastic resins is more preferably used. Furthermore, in order to facilitate the compatibility with the conductive material when using a solvent containing water, which will be described later, a thermoplastic resin that can be dissolved or dispersed in water is preferably used. The thermoplastic resin that can be dissolved or dispersed in water may be solubilized or dispersed as a result of imparting a hydrophilic functional group to the thermoplastic resin, or may be forcibly solubilized or emulsified by an emulsifier. It may be distributed.

The acrylic resin may be polymerized with a copolymerizable monomer as long as it contains a (meth) acrylic monomer as a main constituent monomer. When polymerized with a copolymerizable monomer, (meth) acrylic At least one should just have an acid group among a system monomer and a copolymerizable monomer. Examples of the acrylic resin include (meth) acrylic monomers having an acid group [(meth) acrylic acid, sulfoalkyl (meth) acrylate, sulfonic acid group-containing (meth) acrylamide, etc.] or copolymers thereof, acids (Meth) acrylic monomer which may have a group, and other polymerizable monomer having an acid group [other polymerizable carboxylic acid, polymerizable polycarboxylic acid or anhydride, vinyl aromatic sulfonic acid Etc.] and / or a copolymer with the above copolymerizable monomer [eg, (meth) acrylic acid alkyl ester, glycidyl (meth) acrylate, (meth) acrylonitrile, aromatic vinyl monomer, etc.], acid group (Meth) acrylic copolymerizable monomer [for example, (meth) acrylic acid alkyl ester, hydroxyalkyl (meth) acrylate, glycidyl ( Data) acrylate, copolymers of (meth) acrylonitrile, etc.], rosin-modified urethane acrylate, special modified acrylic resins, urethane acrylates, epoxy acrylates, and urethane acrylates emulsion and the like. Among these, (meth) acrylic acid- (meth) acrylic acid ester polymers (acrylic acid-methyl methacrylate copolymer, etc.), (meth) acrylic acid- (meth) acrylic acid ester-styrene copolymers ( Acrylic acid-methyl methacrylate-styrene copolymer, etc.) are preferred. These may be used alone or in combination of two or more.

The urethane resin is not particularly limited as long as it is a polymer compound obtained by copolymerizing a compound having an isocyanate group and a compound having a hydroxyl group. For example, an ester / ether polyurethane, an ether polyurethane, or a polyester Examples thereof include polyurethane, carbonate polyurethane, and acrylic polyurethane. These may be used alone or in combination of two or more.

The ester resin is not particularly limited as long as it is a polymer compound obtained by polycondensation of a compound having two or more carboxyl groups in the molecule and a compound having two or more hydroxyl groups. Examples include terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate. These may be used alone or in combination of two or more.

The olefin resin is not particularly limited, and examples thereof include chlorinated polypropylene, non-chlorinated polypropylene, chlorinated polyethylene, and non-chlorinated polyethylene. These may be used alone or in combination of two or more.

The carboxyl group-containing resin is not particularly limited. For example, a ring-opening, half-esterification, or half-amidation of an acid anhydride of a copolymer of a vinyl monomer such as styrene, ethylene, methyl vinyl ether and maleic anhydride. Resin and the like. These may be used alone or in combination of two or more.

The polyether resin is not particularly limited, and examples thereof include polyalkylene glycol, polyvinyl alcohol, polyether polyol, polyglycerin, pullulan, and derivatives thereof. These may be used alone or in combination of two or more.

When the coating composition contains a thermoplastic resin, the content of the thermoplastic resin may be 60 to 97.8% by weight, preferably 65 to 95% by weight, based on the total solid content in the coating composition. More preferably, it is 70 to 90% by weight. When the content of the thermoplastic resin is within the above range, it is possible to keep the content of the slip agent low while exhibiting the stretch followability necessary for the stretching process described later.

The coating composition may further contain a curable resin for the purpose of obtaining higher scratch resistance. Although it does not specifically limit as curable resin, For example, the compound, isocyanate resin, melamine resin, and silicate resin containing an epoxy group are mentioned. These may be used alone or in combination of two or more. A melamine resin is preferable from the viewpoint of maintaining good stretch processability while enhancing scratch resistance.
A curable resin that can be dissolved or dispersed in water is preferably used in order to facilitate compatibility with the conductive material when using a solvent containing water described later. The curable resin that can be dissolved or dispersed in water may be solubilized or dispersed as a result of imparting a hydrophilic functional group to the curable resin, or forcibly solubilized or dispersed by an emulsifier. It may be distributed.

Although it does not specifically limit as a melamine resin, For example, the melamine resin which consists of a monomer represented by the following General formula (2) is mentioned:
[Wherein X is —NR ¹ R ^{1 ′} ;
Y is —NR ² R ^{2 ′} ;
Z is —NR ³ R ^{3 ′} ;
R ¹ , R ^{1 ′} , R ² , R ^{2 ′} , R ³ and R ^{3 ′} are each independently a hydrogen atom, a C _1-5 alkyl group or a C _1-5 hydroxyalkyl group, And the C _1-5 alkyl group and the C _1-5 hydroxyalkyl group may each independently be interrupted by one or more oxygen atoms.

When the coating composition contains a curable resin, the content of the curable resin is preferably 0.1 to 5% by weight, and preferably 0.1 to 3% by weight with respect to the total solid content in the coating composition. % Is more preferable. When the blending amount of the curable resin is within the above range, the scratch resistance can be enhanced while maintaining the stretch followability necessary for the stretching process.

The coating composition may contain components such as an ultraviolet absorber, an antioxidant, an antiseptic, a release agent, an antifoaming agent, a leveling agent, a polymerization initiator, and a solvent as necessary.

In the process of producing the laminate of the present invention, the coating composition may contain a solvent in order to obtain good coating properties when applied on the resin substrate. Examples of the solvent include, but are not limited to, alcohols such as water, methanol, ethanol, 2-propanol, 1-propanol, and glycerin; ethylene such as ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol. Glycols; glycol ethers such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether, and diethylene glycol dimethyl ether; glycol ether acetates such as ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate; propylene Glycol, dipropylene glycol, Propylene glycols such as propylene glycol; propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl Propylene glycol ethers such as ether; propylene glycol ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate; Acetone, acetonitrile, isophorone, propylene carbonate, γ-butyrolactone, β-butyrolactone, 2-phenoxyethanol, dioxane, morpholine, 4-acryloylmorpholine, N-methylmorpholine N-oxide, 4-ethylmorpholine, 2-methoxyfuran; 1,3-dimethyl-2-imidazolidinone; N, N-dimethylacetamide; N-methylformamide; N, N-dimethylformamide; acetamide; N-ethylacetamide; N-phenyl-N-propylacetamide; Sulfoxide; β-thiodiglycol; triethylene glycol; tripropylene glycol; 1,4-butanediol; 1,5-pentanediol; 1,3-butanediol; 1,6-hexanediol Neopentyl glycol; catechol; cyclohexane diol; cyclohexane dimethanol; glycerin; erythritol; immitol; lactitol; maltitol; mannitol; sorbitol; xylitol; sucrose; N-methylpyrrolidone; β-lactam; epsilon caprolactam; laurolactam etc. are mentioned. These may be used alone or in combination of two or more. From the viewpoint of the coating property and storage stability of the resin composition, water and a mixture of water and another solvent miscible with water (mixed solvent) are preferable.

When the solvent is contained in the coating composition, the content of the solvent is not particularly limited, but is preferably 10% by weight or less, more preferably 7% by weight or less, based on the entire coating composition. More preferably 5% by weight or less. When the solid content of the coating composition is 10% or less, the coating property is good when forming the surface protective layer, and the storage stability is also excellent.

The pH of the coating composition is preferably 4 to 10, more preferably 5 to 9, and even more preferably 6 to 9. When the pH of the coating composition is within the above range, the storage stability is excellent, and corrosion of the coating equipment can be reduced.

The thickness of the surface protective layer is preferably 0.01 to 10 μm, more preferably 0.02 to 2 μm.

By adjusting the surface shape (uneven shape) of the surface protective layer, it is possible to impart desirable functions such as slipperiness, wettability, and adhesion to the surface protective layer depending on the application. In the surface protective layer, by adding fine particles having a particle size in the specific range described above, sufficient adhesion can be imparted while maintaining slipperiness. A fine concavo-convex structure is formed on the surface of the surface protective layer due to the shape of the fine particles.

The surface protective layer may be a stretch processed body after being subjected to a stretch processing. The stretching process may be performed together with the resin base material, and only the surface protective layer formed may be subjected to the stretching process. The stretching process is not particularly limited as long as it involves 2.5 to 9 times stretching, and may be, for example, stretching in one direction or two directions, or forming into a three-dimensional object. For example, the stretching ratio of the stretching process is preferably 3 to 7 times, and more preferably 4 to 6 times. When the draw ratio is within the above range, it is possible to process into a desired shape and develop high transparency while suppressing the decrease in conductivity and scratch resistance due to the stretching process.

The dynamic friction coefficient of the surface protective layer is 1 or less, preferably 0.8 or less, more preferably 0.4 or less. When the dynamic friction coefficient of the surface protective layer is 1 or less, sufficient slipperiness can be ensured.
In addition, the dynamic friction coefficient in this invention means what is measured by the method prescribed | regulated to JISK7125.

The peel strength of the surface protective layer is 1.5 N / 25 mm or more, preferably 2 or more, more preferably 3 or more. Sufficient adhesion can be secured when the peel strength is 1.5 N / 25 mm or more.
In addition, the peeling strength in this invention means 180 degree peeling strength measured according to JISK6854-2.

The surface resistivity of the surface protective layer is not particularly limited, but is preferably 1.0 × 10 ¹³ Ω / □ or less, more preferably 1.0 × 10 ¹⁰ Ω / □ or less, from the viewpoint of imparting antistatic properties. More preferably, it is 1.0 × 10 ⁸ Ω / □ or less. When the surface resistivity of the surface protective layer is 1.0 × 10 ¹³ Ω / □ or less, sufficient antistatic properties can be obtained.

The surface protective layer is preferably transparent. Specifically, the haze of the laminate of the resin base material and the surface protective layer is preferably 2.5% or less, more preferably 2.0% or less, and further preferably 1.0% or less. Since the haze is preferably as small as possible, the lower limit is not particularly limited, but is, for example, 0.1%.

The laminate of the present invention is a laminate in which a surface protective layer made of the above-described coating composition is disposed on a resin substrate.

In the laminate of the present invention, it is possible to attach to a liquid crystal cell, an OLED cell, a touch sensor, etc., and to facilitate device assembly, an acrylic adhesive layer and a urethane-based easy adhesion layer are further provided on the surface protective layer. A functional layer such as a layer or an ultraviolet curable adhesive layer may be disposed.

When the acrylic adhesive layer is disposed in the laminate of the present invention, the acrylic adhesive layer is not particularly limited. For example, in addition to the acrylic resin, a crosslinking agent, an ionic liquid, an organic solvent, or the like is used. May be formed.

Examples of acrylic resins include (meth) acrylate base polymers such as butyl (meth) acrylate, ethyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. A copolymer base polymer using two or more kinds of (meth) acrylic acid esters is preferably used. Further, polar monomers may be copolymerized with these base polymers. As polar monomers, (meth) acrylic acid, 2-hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, glycidyl (meth) Examples thereof include monomers having a carboxy group, a hydroxyl group, an amide group, an amino group, an epoxy group, and the like such as acrylate.
These acrylic resins can be used alone, but may contain a crosslinking agent. As the crosslinking agent, a divalent or polyvalent metal ion that forms a carboxylic acid metal salt with a carboxyl group, a polyamine compound that forms an amide bond with a carboxyl group, Examples thereof include polyepoxy compounds and polyols that form an ester bond with a carboxyl group, and polyisocyanate compounds that form an amide bond with a carboxyl group. Among them, polyisocyanate compounds are widely used as organic cross-linking agents, are excellent in transparency, weather resistance, heat resistance, maintain appropriate wettability and cohesive force, and exhibit an appropriate pressure-sensitive adhesive property. This is because the design is facilitated.

The urethane resin that can be used in the urethane-based easy-adhesion layer can be obtained, for example, by reacting a polyol, a polyisocyanate, and a chain extender having a free carboxyl group. The polyol is not particularly limited as long as it has two or more hydroxyl groups in the molecule, and any appropriate polyol can be used. For example, polyacryl polyol, polyester polyol, polyether polyol and the like can be mentioned. These can be used alone or in combination of two or more.

The polyisocyanate is not particularly limited as long as it has two or more isocyanate groups in the molecule, and any appropriate polyisocyanate can be used. For example, aliphatic isocyanate, aromatic isocyanate, etc. are mentioned. These can be used alone or in combination of two or more.

Examples of the chain extender having a free carboxyl group include dihydroxycarboxylic acid and dihydroxysuccinic acid. Examples of the dihydroxycarboxylic acid include dialkylolalkanoic acids such as dimethylolalkanoic acid (for example, dimethylolacetic acid, dimethylolbutanoic acid, dimethylolpropionic acid, dimethylolbutyric acid, dimethylolpentanoic acid). These can be used alone or in combination of two or more.

These urethane resins can be used alone, but may contain a crosslinking agent. As a crosslinking agent, the crosslinking agent which has an epoxy group is mentioned. The epoxy crosslinking agent is not particularly limited as long as it has at least one epoxy group in the molecule. Examples thereof include bisphenol type epoxy compounds, novolak type epoxy compounds, alicyclic epoxy compounds, aliphatic epoxy compounds, aromatic epoxy compounds, glycidylamine type epoxy compounds, halogenated epoxy compounds and the like.

These urethane resins and cross-linking agents include water-based ones and organic solvent-based ones, but water-based ones are preferable in consideration of stretch processability.

The UV curable adhesive layer is prepared by mixing a photocationic polymerization initiator with a compound having an epoxy group or an oxetane group, or by mixing a compound having a (meth) acrylic group with a photoradical polymerization initiator. Those used in combination are preferably used.

As a compound having an epoxy group or an oxetane group, for example, a polyfunctional alicyclic epoxy resin, a polyfunctional glycidyl ether resin, or a polyfunctional oxetane resin is used as a main agent, and a monofunctional alicyclic epoxy resin or a monofunctional is used for the purpose of reducing the viscosity. A fat glycidyl ether resin or a monofunctional fat oxetane resin may be used in combination.
As the cationic photopolymerization initiator, a phosphate compound, an antimonate compound, or an iodonium compound is preferably used. Usually, the cationic photopolymerization initiator is 0 with respect to 100 parts by weight of the compound having an epoxy group or an oxetane group. .1-10 parts by weight are mixed. Moreover, in order to improve the performance of the photocationic polymerization initiator, a thioxanthone photosensitizer or a benzophenone photosensitizer may be mixed.

In addition to ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, etc., polyfunctional urethane acrylates and polyfunctional epoxy acrylates are also included as compounds having (meth) acrylic groups. Preferably used.
Examples of the photo radical polymerization initiator include benzophenone series, thioxanthone series, acetophenone series, and acylphosphine series, and usually 0.1 to 10 parts by weight are mixed with 100 parts by weight of the compound having a (meth) acryl group. The

The laminate having such an ultraviolet curable adhesive layer is bonded to another functional film or device and the ultraviolet curable adhesive layer surface after the stretching process, and is subjected to i-line (365 nm), h-line (405 nm), g-line ( By irradiating ultraviolet rays including 436 nm) with an illuminance of 10 to 1200 mW / cm 2 and an irradiation light amount of 20 to 2500 mJ / cm 2, it can be easily adhered to other functional films and devices.

When the acrylic pressure-sensitive adhesive layer is disposed in the laminate of the present invention, the thickness of the acrylic pressure-sensitive adhesive layer is preferably 20 to 100 μm, more preferably 40 to 80 μm, and the urethane-based easy adhesion layer is disposed. In this case, the urethane-based easy-adhesion layer thickness is preferably 0.04 to 20 μm, more preferably 0.05 to 5 μm. When the UV-curable adhesive layer is disposed, the thickness of the UV-curable adhesive layer is It is preferable that it is 0.1-20 micrometers, More preferably, it is 0.5-5 micrometers. When the thickness of the acrylic pressure-sensitive adhesive layer, urethane-based easy-adhesive layer and UV-curable adhesive layer is within the above range, ensure the dimensional stability of the laminate while maintaining good stretch followability during the stretch processing. Can do.

In the laminated body of the present invention, other functional layers such as a polarizing layer, a retardation layer, and a viewing angle compensation layer can be further arranged as necessary in addition to the above-described resin base material, surface protective layer and functional layer. .

The laminate of the present invention can be produced by applying a coating composition containing fine particles, a slip agent, and a conductive material on a resin substrate.
The application method is not particularly limited, for example, roll coating method, bar coating method, dip coating method, spin coating method, casting method, die coating method, blade coating method, gravure coating method, curtain coating method, Examples thereof include a spray coating method, a doctor coating method, and a slit coating method.

Although it does not specifically limit as a method of drying the coating composition of this invention apply | coated on the resin base material, At 20-200 degreeC using ventilation drying equipment, reduced pressure drying equipment, IR drying equipment, a hotplate, etc. Examples include a method of drying for 0.1 to 30 minutes.

The coating composition can be applied on the resin substrate and simultaneously stretched. When performing a drawing process simultaneously with application | coating, it is preferable at the point which can perform drying and a drawing process simultaneously.

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The display according to the present invention includes the laminate according to the present invention.

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. “Parts” or “%” means “parts by weight” or “% by weight”, respectively, unless otherwise specified.

1-1. Conductive material / PEDOT: PSS (prepared in Production Example 1, solid content: 1.3% by weight)
・ Carbon nanotubes (prepared in CNT Production Example 2, solid content 1.1% by weight)
1-2. Thermoplastic resin / acrylic resin (manufactured by Toagosei Co., Ltd., Jurimer FC-80, solid content 30%, glass transition temperature 50 ° C.)
-Urethane resin (Daiichi Kogyo Seiyaku Co., Ltd., Superflex 830HS, solid content 35%, glass transition temperature 68 ° C)
Ester resin (Toagosei Co., Ltd., Aronmelt PES-2405A30, glass transition temperature 40 ° C., solid content 30% by weight)
Polyether resin (Daiichi Kogyo Seiyaku Co., Ltd., Evan U-103, number of hydroxyl groups per molecule: 2)
1-3. Slip agent / polyether-modified silicone (Toray Dow Corning Co., Ltd., 57 ADDITIVE, 100% solid content)
Fluorine group-containing oligomer (manufactured by DIC Corporation, MegaFuck F-477, solid content rate 100%)
1-4. Fine particles / silica fine particles (manufactured by CIK Nanotech Co., Ltd., SIRW15WT% -H27, solid content 15%, average particle size 20 nm)
Silica fine particles (Nippon Shokubai Co., Ltd., Seahoster KE-W10, solid content 15%, average particle size 100 nm)
Silica fine particles (Nippon Shokubai Co., Ltd., Seahoster KE-W50, solid content 20%, average particle size 500 nm)
・ Acrylic resin fine particles (Nippon Shokubai Co., Ltd., Epostor MX050W, solid content 10%, average particle size 70 nm)

(Production Example 1) Production of PEDOT: PSS aqueous dispersion Using a 2000 ml three-necked glass flask equipped with a cooling tube, 92.3 parts of polystyrenesulfonic acid aqueous solution (manufactured by Akzo Nobel, VERSA-TL72) and 3,4-ethylene 7.1 parts of dioxythiophene (EDOT) was added to 1000 parts of ion-exchanged water to obtain a mixed solution. While stirring this mixed solution, a solution prepared by dissolving 4.0 parts of ferric sulfate and 14.8 parts of ammonium peroxodisulfate in 100 parts of ion-exchanged water was added and stirred at 20 ° C. for 24 hours for oxidation polymerization. Went. Next, 15% by weight of a cation exchange resin (manufactured by Organo Corporation, Amberlite IR120B) and an anion exchange resin (manufactured by Organo Corporation, Amberlite IRA67) were added, and the mixture was further stirred for 18 hours. The obtained reaction mixture was filtered with a glass filter, then homogenized with a high pressure homogenizer 10 times at 100 MPa, and then 5% by weight of dimethyl sulfoxide was added to obtain a PEDOT: PSS aqueous dispersion. .

(Production Example 2) Production of aqueous dispersion of carbon nanotubes 1 part by weight of carbon nanotubes (Zeon Nanotechnology Co., Ltd., ZEONANO SG101) having an average length of 300 μm and a diameter of about 4 nm, sodium dodecylbenzenesulfonate (Wako Pure Chemical Industries, Ltd.) as a dispersant 10 parts by weight) and 989 parts by weight of pure water are placed in a glass beaker, dispersed with an ultrasonic homogenizer at 40 W for 30 minutes, and then undispersed carbon nanotubes are removed with a centrifuge 3500 rpm. Thus, a carbon nanotube dispersion having a solid content of 1.1% was obtained.

(Production Example 3) Production of acrylic resin film Acrylic resin (parapet HR-S, copolymer monomer weight ratio = methyl methacrylate / methyl acrylate = 99/1, manufactured by Kuraray Co., Ltd.) 90 parts by weight and acrylonitrile-styrene Pellets with 10 parts by weight of resin (Toyo AS AS20, manufactured by Toyo Styrene Co., Ltd.) were supplied to a biaxial extruder and melt extruded into a sheet at about 280 ° C. to obtain a film having a thickness of 160 μm.

2. Examples (Examples 1 to 8, Comparative Examples 1 and 2)
A conductive material, a thermoplastic resin slip agent, fine particles, water, and propylene glycol were mixed so that the solid content ratio shown in Table 1 was obtained to obtain a coating composition. Here, the amount of propylene glycol was added so as to be 2% by weight in the coating solution. About the obtained coating composition, the solid content rate was calculated | required with the following method.

In Examples 1, 3, 5-7, and Comparative Examples 1 and 2, the coating composition was applied onto the film (thermoplastic resin base material) produced in Production Example 3 using the bar coating method, and then air-dried. A laminate having a surface protective layer of 0.1 μm was produced by drying at 70 ° C. for 5 minutes using a machine.
In Examples 2, 4, and 8, the coating composition was applied on the thermoplastic resin base material produced in Production Example 3 using a wire bar, and 0.degree. A 1 μm surface protective layer was prepared. After cutting to 50 cm × 50 cm and fixing to a stage, the laminate was heated to 140 ° C. and stretched to 100 cm × 100 cm to perform a 4-fold stretching process, thereby producing a laminate subjected to a stretching process.
These laminates were cut into 10 cm × 100 cm, and peel strength, dynamic friction coefficient, surface resistivity, transparency, and winding shape were measured and evaluated. The evaluation results are shown in Table 1.

3. Evaluation method (solid content)
The weight of the coating composition obtained in each Example and Comparative Example and the weight after the coating composition was heated and dried at 120 ° C. for 2 hours in a blowing oven were weighed, and the solid content ratio was calculated based on the following formula: Calculated.
Solid content (%) = weight of coating composition after drying / weight of coating composition before drying

(Peel strength)
The laminate obtained by the above method was cut out to obtain a 25 × 150 mm test film, and a 180 ° peel strength was measured according to JIS K 6854-2 using a Toyo Seiki Co., Ltd. strograph tester. evaluated.
A: Peel strength is 3 N / 25 mm or more. O: Peel strength is 1.5 or more and less than 3 N / 25 mm. X: Peel strength is less than 1.5 N / 25 mm.

(Dynamic friction coefficient)
About the laminated body obtained by said method, based on the friction coefficient test method of JISK7125, it measured with the automatic horizontal type | mold servo stand (Nippon Measurement System Co., Ltd. make, JSH-H1000), and evaluated it with the following reference | standard.
At this time, a commercially available acrylic base material (manufactured by Sumitomo Chemical Co., Ltd., Technoloy S014G, 75 μm thickness) was attached to the bottom surface of the sliding piece using a double-sided tape having a thickness of 1 mm and pulled at a speed of 10 mm / min.
◎: Dynamic friction coefficient is 0.4 or less ○: Dynamic friction coefficient is larger than 0.4, 1 or less ×: Dynamic friction coefficient is larger than 1, or the sliding piece moves while causing obvious vibration

(Antistatic property)
About the antistatic property of a laminated body, surface resistivity was calculated | required by Loresta GP MCP-T600 by Mitsubishi Chemical Corporation, and the following reference | standard evaluated.
A: Surface resistivity is 1.0 × 10 ⁸ Ω / □ or less ○: Surface resistivity is greater than 1.0 × 10 ⁸ Ω / □, 1.0 × 10 ¹³ Ω / □ or less ×: Surface resistivity is Greater than 1.0 × 10 ¹³ Ω / □

(transparency)
The coating film was measured according to JIS K 7150 using a haze computer HGM-2B manufactured by Suga Test Instruments Co., Ltd. and evaluated according to the following criteria.
◎: 1.0% or less ○: greater than 1.0, 2.5% or less ×: greater than 2.5%

(Winding shape)
The laminate obtained by the above method was wound into a roll, the shape was visually observed, and evaluated according to the following criteria.
○: Taken up uniformly without winding deviation ×: Bamboo-like winding deviation or wrinkle occurs at the end in the film width direction

Claims (9)

A laminate comprising a resin substrate and a surface protective layer,
The surface protective layer is composed of a coating composition containing fine particles having an average particle diameter of 10 to 500 nm, a slip agent, and a conductive material,
A laminate comprising a surface protective layer having a dynamic friction coefficient of 1 or less and a peel strength of 1.5 N / 25 mm or more. The laminate according to claim 1, wherein the coating composition contains 0.1 to 10% by weight of fine particles having an average particle diameter of 10 to 500 nm with respect to the total solid content. The laminate according to claim 1 or 2, wherein the fine particles are inorganic fine particles and / or organic fine particles having a crosslinked structure. The laminate according to any one of claims 1 to 3, wherein the slip agent is a silicone resin and / or a fluorine resin. The laminate according to any one of claims 1 to 4, wherein the conductive material is at least one selected from the group consisting of a conductive polymer, a carbon nanomaterial, and a metal nanowire. The laminate according to any one of claims 1 to 5, wherein the coating composition comprises at least one thermoplastic resin selected from the group consisting of acrylic resin, urethane resin, ester resin and polyether resin. The laminate according to any one of claims 1 to 6, wherein the surface protective layer is a stretch-processed body. The laminate according to any one of claims 1 to 7, further comprising an acrylic pressure-sensitive adhesive layer and / or a urethane-based easy adhesion layer. The display provided with the laminated body of any one of Claims 1-8.