Laminate

Abstract

To provide a laminate which has an ant-static layer on at least one surface of a polycarbonate resin base material, and imparts such characteristics as to prevent adhesion a foreign matter such as dust even when being bent and stretched.SOLUTION: A laminate has an anti-static layer on at least one surface of a polycarbonate resin base material, wherein a surface resistance value after the laminate is stretched by 10% is 1×1013 Ω or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a laminate having an antistatic layer on at least one surface of a polycarbonate resin substrate. [Background technology]

[0002] Plastic materials such as polycarbonate, polyester, polymethyl methacrylate, triacetylcellulose, polystyrene, and polyvinyl chloride are used in a wide variety of applications, including display components, electrical and electronic components, automotive parts, building materials, lenses, containers, and packaging materials. Among these, polycarbonate, for example, is one of the resins with excellent impact resistance and heat resistance, making it suitable for a wide range of applications.

[0003] Polycarbonates using isosorbide have been proposed (Patent Document 1). Although there have been proposals to add antistatic agents to polycarbonate substrates, specific material systems and amounts of additives have not been disclosed. Furthermore, when added to the substrate, it is difficult to segregate the antistatic agent to the surface, making it difficult to achieve sufficient antistatic properties. In addition, the conductive network is easily damaged by stretching processes such as bending, folding, and stretching, making it difficult to achieve antistatic properties. Therefore, there are concerns about the adhesion of foreign matter such as dust and deterioration of handling due to the substrate sticking together. Moreover, if antistatic properties are achieved by using a large amount of antistatic agent, the polycarbonate substrate itself becomes brittle, which may make it unsuitable depending on the application. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2016-150990 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] The present invention relates to a laminate having an antistatic layer on at least one surface of a polycarbonate resin substrate, wherein the surface resistance value of the laminate after being stretched by 10% is 1 × 10⁻⁶ 13 The objective is to provide a laminate that has properties such as preventing the adhesion of foreign matter like dust even when the laminate is bent or stretched, by making the laminate less than or equal to Ω. [Means for solving the problem]

[0006] The present invention has the following aspects. In other words, the above objectives of the present invention can be achieved by the following means [1] to [9]. [1] A laminate having an antistatic layer on at least one surface of a polycarbonate resin substrate, wherein the surface resistance value of the laminate after being stretched by 10% is 1 × 10 13 A laminate with an Omega value of less than Ω. [2] The laminate according to [1], wherein the polycarbonate resin constituting the base material contains a heterobicyclo ring structure. [3] The laminate according to [2], wherein the polycarbonate resin constituting the base material is a copolymerized polycarbonate resin. [4] The laminate according to [3], wherein the glass transition temperature of the polycarbonate resin constituting the substrate is 40 to 180°C. [5] The laminate according to [1], wherein the antistatic layer contains an antistatic agent, and the antistatic agent is a polymer type antistatic agent. [6] The laminate according to [5], wherein the polymer type antistatic agent is a compound having an ammonium group or a conductive organic polymer. [7] The laminate according to [6], wherein the antistatic layer is a hardened layer. [8] The laminated film according to [4] or [6], wherein the substrate is a film. [9] A method for manufacturing a laminate, comprising applying a coating solution containing an antistatic agent to at least one surface of a polycarbonate resin substrate to form an antistatic layer, and then stretching the laminate in at least one direction. [Effects of the Invention]

[0007] The laminate of the present invention has the property of preventing the adhesion of foreign substances such as dust even when bent or stretched.

Mode for Carrying Out the Invention

[0008] <Base material> Any polycarbonate resin can be used as long as the base material is composed of a material that can be bent or stretched. Among them, it is preferable to contain a compound having a bicyclic structure as a constituent element, and among the heterocycles, a bicyclic structure containing oxygen (a bicyclic structure having a cyclic ether) is preferable from the viewpoint of weather resistance. Among them, in particular, by containing the structure represented by the following formula (1), optical properties such as birefringence, weather resistance, and scratch resistance can be improved compared to general polycarbonate resins.

[0009]

Chemical formula

[0010] Examples of the dihydroxy compound represented by formula (1) include isosorbide, isomannide, and isoidide, which are in a stereoisomeric relationship. Among these stereoisomers, as a plant-derived compound, it can be easily produced by hydrogenating D-glucose obtained from starch and then dehydrating it, and isosorbide is more preferable because it is easily available as a resource. Especially in recent years, there is a concern that it may lead to the depletion of petroleum resources, so there is a demand for providing plastic products using plant-derived raw materials. Also, global warming due to an increase in carbon dioxide emissions is also an issue. Therefore, from the perspective of carbon neutrality, it is required to use plant-derived raw materials, so it is ideal to use isosorbide.

[0011] In addition, by using isosorbide as the dihydroxy component of the polycarbonate resin, many isosorbide structures can be incorporated into the polycarbonate resin, so the amount of plant origin can be increased, which is a preferable form.

[0012] When using a polycarbonate resin with isosorbide as the dihydroxy component as the base material, conventionally known materials can be used as the diester carbonate used as the raw material for the polycarbonate resin. Examples include phenyl carbonates such as diphenyl carbonate and dityl carbonate, and alkyl carbonates such as dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate. Among these, phenyl carbonates are preferred, and diphenyl carbonate is particularly preferred. These diester carbonates may be used individually or in combination of two or more types.

[0013] Furthermore, it is also preferable to use compounds other than isosorbide as the dihydroxy component in combination with isosorbide. In other words, it is preferable to use a copolymer polycarbonate resin as a copolymer component with isosorbide. Preferred dihydroxy components include, for example, aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, aromatic bisphenol compounds, or ether group-containing dihydroxy compounds other than isosorbide. By introducing a molecular structure that is more flexible than the isosorbide structure, the toughness of the polycarbonate resin can be adjusted. In addition, from the viewpoint of further improving impact resistance, it is preferable to use aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, or aromatic bisphenol compounds. Furthermore, from the viewpoint of improving weather resistance, it is more preferable to use compounds that do not have an aromatic ring structure in their molecular structure, i.e., aliphatic dihydroxy compounds or alicyclic dihydroxy compounds. Furthermore, considering the improvement of heat resistance, alicyclic dihydroxy compounds are even more preferable. These dihydroxy components may be used individually or in combination of two or more. In addition, compounds having three or more hydroxyl groups, such as trihydroxy and tetrahydroxy, can also be used, not limited to dihydroxy structures.

[0014] Examples of alicyclic dihydroxy compounds include 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, pentacyclopentadecanedimethanol, 2,6-decalingimethanol, 1,5-decalingimethanol, 2,3-decalingimethanol, 2,3-norbornanedimethanol, 2,5-norbornanedimethanol, 1,3-adamantanedimethanol, and limonene. Among these, 1,4-cyclohexanedimethanol or tricyclodecanedimethanol are more preferred when considering the balance of impact resistance and flexibility, as well as ease of manufacture. In particular, 1,4-cyclohexanedimethanol is even more preferred in applications where flexibility and high bendability and elongation are important.

[0015] Aliphatic dihydroxy compounds may be linear aliphatic or branched aliphatic. Specific examples of aliphatic dihydroxy compounds include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-heptanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol.

[0016] Aromatic bisphenol compounds include 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxy-(3,5-diphenyl)phenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxyphenyl)pentane, 2,4'-dihydroxy-diphenylmethane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-5-nitrophenyl)methane, and 1,1-bis Examples include (4-hydroxyphenyl)ethane, 3,3-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenylsulfone, bis(4-hydroxyphenyl)sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, 9,9-bis(4-(2-hydroxyethoxy-2-methyl)phenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-2-methylphenyl)fluorene. Among these, bisphenol A is more preferred when considering the balance of performance.

[0017] Examples of ether group-containing dihydroxy compounds include diethylene glycol, triethylene glycol, polyethylene glycol, poly-1,3-propylene glycol, and polytetramethylene glycol. For polyethylene glycol, those with a molecular weight of, for example, 150 to 2,000 can be used.

[0018] When using copolymer polycarbonate resin having an isosorbide structure as the base material, the proportion of isosorbide-derived structural units in 100 mol% of total dihydroxy compound-derived structural units is preferably in the range of 1 mol% or more, more preferably 10 mol% or more, even more preferably 30 mol% or more, particularly preferably 45 mol% or more, and most preferably 55 mol% or more. There is no particular upper limit, and all structural units may be isosorbide-derived, but it is preferably in the range of 99 mol% or less, more preferably 95 mol% or less, even more preferably 90 mol% or less, and particularly preferably 85 mol% or less. Using the above range makes it easier to adjust properties that balance heat resistance, rigidity, moldability, and mechanical strength.

[0019] The copolymerized polycarbonate resin may contain structural units other than the dihydroxy compounds mentioned above. For example, dihydroxy compounds of aromatic hydrocarbons can be used, but compounds containing aromatic rings often absorb ultraviolet rays and undergo structural degradation when exposed to sunlight or ultraviolet rays, resulting in defects such as yellowing. Therefore, when using dihydroxy compounds of aromatic hydrocarbons, it is desirable to use them in a way that does not impair the required product characteristics such as moldability, weather resistance, and surface properties.

[0020] The glass transition temperature of polycarbonate resin is preferably in the range of 40 to 180°C, more preferably 60 to 160°C, even more preferably 80 to 150°C, and particularly preferably 90 to 140°C, considering heat resistance and toughness. Furthermore, when molding, it is necessary to take into consideration the molding temperature, and it is preferable that the glass transition temperature is below the molding temperature.

[0021] Polycarbonate resins can be synthesized by polycondensation via a transesterification reaction between the aforementioned dihydroxy compounds and the aforementioned diester carbonates. More specifically, the polycondensation reaction can be carried out by removing by-products such as monohydroxy compounds from the transesterification reaction. The transesterification reaction is promoted in the presence of a transesterification catalyst. As the catalyst, metal compounds of Group 1 or Group 2 in the long-period periodic table, as well as basic compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds can be used, and it is preferable to use at least one of a Group 1 metal compound or a Group 2 metal compound. The amount of catalyst used is preferably 0.1 to 300 μmole, more preferably 0.5 to 100 μmole, and particularly 1 to 50 μmole per mole of total dihydroxy compounds subjected to the reaction.

[0022] The molar ratio of dihydroxy compound to diester carbonate is preferably in the range of 0.90 to 1.20. In this case, the increase in the amount of hydroxyl groups at the ends of the polycarbonate resin can be suppressed, thereby improving the thermal stability of the resin. As a result, discoloration during molding can be reduced. Furthermore, the decrease in the rate of the transesterification reaction can be suppressed, enabling more reliable production of copolymers with the desired molecular weight. In addition, in this case, discoloration of the polycarbonate resin can be reduced from the viewpoint of suppressing the increase in the thermal history during the reaction. Moreover, in this case, the amount of residual diester carbonate in the polycarbonate resin can be reduced, further reducing discoloration of the resin. Furthermore, the generation of odor can be avoided or mitigated. From the viewpoint of further enhancing these effects, the molar ratio of dihydroxy compound to diester carbonate is particularly preferably in the range of 0.95 to 1.10.

[0023] Examples of polymerization reaction methods include batch, continuous, or combinations thereof. Among these, the continuous reaction, carried out in multiple stages using multiple reactors in the presence of the catalyst, is preferred from the viewpoint of productivity and ease of thermal history management.

[0024] Furthermore, the polycarbonate resin used as the base material can also contain various additives. Examples of additives include ultraviolet absorbers, antioxidants, light stabilizers, catalyst deactivators, dyes and pigments, flame retardants, flame retardant aids, fillers, impact modifiers, hydrolysis inhibitors, nucleating agents, and plasticizers.

[0025] Polycarbonate resin can be processed as a base material by various conventionally known methods. While not limited to the methods described below, examples include introducing the resin into an extruder, continuously supplying additives while kneading, removing by-product gases and low-molecular-weight volatile components via a vacuum device, and then extruding the molten material in strand form from the extruder tip, allowing it to cool and solidify while being cut into pellets. A twin-screw extruder equipped with a vacuum device at the vent port is preferred to ensure sufficient devolatilization capacity and uniform dispersion of additives.

[0026] For extruder operating conditions, a lower resin melt viscosity is preferable to improve devolatilization efficiency, and a higher melt-mixing temperature within the extruder system is preferable. However, if the temperature is too high, discoloration and thermal decomposition may occur, so it is necessary to process at the highest possible and appropriate temperature. The appropriate melt temperature depends on the type of resin, the glass transition temperature of the resin, molecular weight, melt viscosity, etc., but considering the temperature at which thermal decomposition begins rapidly, 200°C to 320°C is preferable. In this case, the plasticizing load on the extruder is reduced, productivity can be improved, and thermal decomposition of the resin can be suppressed, further preventing discoloration, reduction in mechanical strength due to molecular weight decrease, and generation of thermal decomposition gases. From the viewpoint of further enhancing this effect, a melt temperature of 210°C to 300°C is more preferable, and 220°C to 290°C is particularly preferable.

[0027] The resin, melted in an extruder and preferably passed through a gear pump and filtered as needed, is extruded, for example, in the form of strands from a die head, and after cooling and solidification, is cut into pellets using a rotary cutter or the like. The strands are usually cooled by air or water. When using air cooling, it is preferable to use clean air filtered for foreign matter using a HEPA filter or the like to prevent contamination from the air. When using water cooling, it is preferable to use clean water from which metal components have been removed using an ion exchange resin or the like, and then for which foreign matter has been removed using a water filter.

[0028] The resulting pelletized resin can be further processed by conventionally known methods. Examples include processing into a film or molding using a mold. While not limited to the following methods, for example, when making a film, a common manufacturing method involves melting the resin, forming it into a sheet, and stretching it as needed to increase its strength.

[0029] For example, the above-mentioned resin is melted and extruded from a die using an extruder, and the molten film is cooled and solidified with a cooling roll to obtain an unstretched film. In this case, in order to improve the flatness of the film, it is preferable to increase the adhesion between the molten sheet and the cooling roll, and electrostatic application adhesion or liquid coating adhesion methods can be used. If the film is to be used as is as an unstretched film, the thickness variation can be reduced by adjusting the roll temperature and extrusion speed. It is also possible to stretch the obtained unstretched film to improve production efficiency, reduce thickness variation and roughness. For example, stretching in the longitudinal direction of the film can be achieved by utilizing the difference in peripheral speed of the rolls, and stretching in the transverse direction of the film can be achieved with a tenter-type stretcher, etc. It is also possible to combine both to produce a biaxially oriented film. It is also possible to use a simultaneous biaxial stretching method. The stretching temperature and stretching ratio vary depending on the type of resin, but are preferably in the range of 70 to 200°C, more preferably 80 to 160°C, and the stretching ratio is in the range of 7 times or less, more preferably 5 times or less in one direction. There is no particular lower limit, but it is 1 time. Subsequently, a stretched film can be obtained by applying appropriate heat treatment or other methods depending on the type of resin.

[0030] It is also possible to use various additives at any stage of the resin processing described above. For example, it is preferable to add them before or during melt extrusion, such as when making pellets or films, because this improves dispersion efficiency. Examples of additives include catalyst deactivators, heat stabilizers, neutralizing agents, UV absorbers, light stabilizers, particles, mold release agents, dyes, pigments, lubricants, plasticizers, compatibilizers, and flame retardants used in resin manufacturing.

[0031] Any form of substrate can be used, such as film, sheet, plate, or molded body. The thickness is also arbitrary, but for example, for film, from the viewpoint of handling, productivity, and processability, it is in the range of 1 to 500 μm, preferably 10 to 300 μm, and more preferably 20 to 250 μm. For molded bodies, from the viewpoint of lightweight, it is in the range of 0.05 to 10 mm, preferably 0.1 to 6 mm, and more preferably 0.2 to 4 mm.

[0032] <Antistatic layer> On a polycarbonate resin substrate, the surface resistance value after 10% stretching is 1 × 10⁻⁶. 13 It has an antistatic layer with a resistance of Ω or less. Even after 10% stretching, the surface resistance value is low, meaning it retains antistatic properties, allowing it to exhibit antistatic properties even after stretching (bending, folding, stretching, etc.), thus broadening its range of applications. Generally, antistatic properties are imparted to prevent foreign matter such as dust from adhering to the material before processing, or to improve the handling of materials such as films. However, it has been found that it is difficult to ensure antistatic properties after processing, especially after bending, folding, and stretching, because the conductive network breaks down. This invention overcomes these problems and maintains antistatic properties even after bending, folding, stretching, etc.

[0033] The antistatic layer contains an antistatic agent to reduce surface resistance. Conventional known materials can be used as antistatic agents, including polymer-type antistatic agents, surfactant-based low-molecular-weight antistatic agents, carbon-based antistatic agents, and metal-based antistatic agents. Among these, from the viewpoint of durability, low-molecular-weight antistatic agents are prone to loss of antistatic properties due to bleed-out, deterioration of appearance, and difficulty in maintaining long-term antistatic properties from a durability standpoint. Furthermore, considering heat resistance and heat and humidity resistance, the applications of low-molecular-weight types are limited, so polymer-type antistatic agents, carbon-based antistatic agents, and metal-based antistatic agents are preferred. Moreover, from the viewpoint of exhibiting antistatic properties even after high stretching, polymer-type antistatic agents or carbon-based antistatic agents are preferred, and if transparency is also important, polymer-type antistatic agents are even more preferred. Note that polymer-type refers to compounds with a number average molecular weight of 1,000 or more.

[0034] Examples of polymer-type antistatic agents include compounds having ammonium groups, conductive organic polymers, polyether compounds, compounds having sulfonic acid groups, and betaine compounds. Among these, compounds having ammonium groups and conductive organic polymers are more preferred from the viewpoint of compatibility with other compounds used in combination in the antistatic layer and antistatic performance. Furthermore, compounds having ammonium groups are more preferred from the viewpoint of transparency, and conductive organic polymers are more preferred in applications requiring higher antistatic performance.

[0035] Compounds containing an ammonium group are compounds that have an ammonium group in their molecule, and examples include ammonium compounds of aliphatic amines, alicyclic amines, and aromatic amines. In polymer-type compounds containing an ammonium group, it is preferable that the ammonium group is incorporated into the main chain or side chains of the polymer rather than as a counterion. Examples of such compounds include those obtained by polymerizing an addition-polymerizable monomer having an ammonium group or a precursor group of an ammonium group, such as an amine, and, if necessary, converting the precursor group of the ammonium group into an ammonium group to obtain a polymer compound containing an ammonium group. Addition-polymerizable monomers containing an ammonium group or a precursor group of an ammonium group may be polymerized individually, copolymerized with two or more types, or copolymerized with other monomers.

[0036] Compounds containing an ammonium group are also preferred because they exhibit excellent antistatic properties and heat stability, particularly those containing a pyrrolidinium ring. The two substituents bonded to the nitrogen atom of a compound containing a pyrrolidinium ring are independently alkyl groups, phenyl groups, etc., and these alkyl and phenyl groups may be substituted with the following groups. Substitutable groups include, for example, hydroxyl groups, amide groups, ester groups, alkoxy groups, phenoxy groups, naphthoxy groups, thioalkoxy groups, thiophenoxy groups, cycloalkyl groups, trialkylammonium alkyl groups, cyano groups, and halogens. Furthermore, the two substituents bonded to the nitrogen atom may be chemically bonded, and an example of a group formed by the chemical bonding of two substituents is -(CH2)m Examples include -(m=an integer from 2 to 5), -CH(CH3)CH(CH3)-, -CH=CH-CH=CH-, -CH=CH-CH=N-, -CH=CH-N=C-, -CH2OCH2-, -(CH2)2O(CH2)2-, etc.

[0037] Polymers having a pyrrolidinium ring can be obtained, for example, by cyclopolymerizing a diallylamine derivative using a radical polymerization catalyst. A compound having a polymerizable carbon-carbon unsaturated bond with the diallylamine derivative may also be used as a copolymer component. Polymerization can be carried out by known methods using a polymerization initiator such as hydrogen peroxide, benzoyl peroxide, or tertiary butyl peroxide in a polar solvent (water, methanol, ethanol, isopropanol, formamide, dimethylformamide, dioxane, acetonitrile, etc.), but is not limited to these methods.

[0038] Examples of anions that act as counterions to the ammonium group in the aforementioned compounds containing an ammonium group include halogen ions, sulfonates, phosphates, nitrates, alkyl sulfonates, and carboxylates.

[0039] The number-average molecular weight of the compound having an ammonium group is preferably 1,000 to 500,000, more preferably 2,000 to 350,000, and even more preferably 5,000 to 200,000. If the number-average molecular weight is 1,000 or more, the strength and heat resistance stability of the coating film are better. If the number-average molecular weight is 500,000 or less, the viscosity of the coating liquid for forming the antistatic layer is low, resulting in good handling and application properties.

[0040] As conductive organic polymers, known materials can be used, such as polythiophene-based, polyaniline-based, polypyrrole-based, polyacetylene-based, and polyphenylene sulfide-based polymers. Among these, polythiophene-based polymers (polythiophene or polythiophene derivatives) are preferred because they offer both high transparency and high conductivity, are less prone to discoloration, and exhibit good performance through coating. Among polythiophene-based polymers, compounds obtained by combining poly(3,4-ethylenedioxythiophene) with polystyrene sulfonic acid are particularly preferred from the viewpoint of conductive performance. Conductive organic polymers are preferred because they exhibit high conductivity, have low humidity dependence, and are expected to have a wide range of applications.

[0041] Examples of polyether compounds include polyethylene oxide, polyether ester amide, and acrylic resins having polyethylene glycol as a side chain.

[0042] In compounds having a sulfonic acid group, the sulfonic acid group may be neutralized with a neutralizing agent to form a salt. Preferred compounds having a sulfonic acid group include polystyrene sulfonic acid and its salts, which have multiple sulfonic acid groups in their molecule.

[0043] Examples of low-molecular-weight surfactant-based antistatic agents include anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants. Among these, anionic surfactants and nonionic surfactants are preferred from the viewpoint of providing good antistatic properties and compatibility with various resins used in combination in the antistatic layer, with anionic surfactants being particularly preferred.

[0044] Examples of anionic surfactants include sulfonic acid types such as alkyl sulfonates, alkylaryl sulfonates, and ester sulfonates; phosphate types such as alkyl phosphate esters or their salts, polyoxyalkylene alkyl ether phosphate esters or their salts; sulfate ester types such as alkyl sulfate salts and alkyl ether sulfate salts; and carboxylate types such as alkyl fatty acid salts. Among these, sulfonic acid types are preferred from the viewpoint of excellent antistatic properties.

[0045] Examples of sulfonic acid-type anionic surfactants include alkyl sulfonates such as decyl sulfonate, dodecyl sulfonate, tetradecyl sulfonate, hexadecyl sulfonate, and octadecyl sulfonate; alkylaryl sulfonates such as butylbenzene sulfonate, hexylbenzene sulfonate, octylbenzene sulfonate, decylbenzene sulfonate, dodecylbenzene sulfonate, tetradecylbenzene sulfonate, hexadecylbenzene sulfonate, octadecylbenzene sulfonate, dibutylnaphthalene sulfonate, and triisopropylnaphthalene sulfonate; and ester sulfonates such as dibutyl sulfosuccinate SL salt, dioctyl sulfosuccinate ester salt, dodecyl sulfoacetate ester salt, and nonylphenoxypolyethylene glycol sulfoacetate ester salt. Among these, from the viewpoint of excellent antistatic properties, the alkyl group has 8 or more carbon atoms, preferably 10 to 22, and more preferably 12 to 18. Furthermore, metal salts are preferred as the salt, alkali metal salts such as lithium, sodium, and potassium are more preferred, and sodium salts are even more preferred. From the viewpoint of antistatic properties, alkyl sulfonates are preferred.

[0046] Examples of phosphate-type anionic surfactants include alkyl phosphates or their salts such as butyl phosphate, butyl phosphate salt, hexyl phosphate, hexyl phosphate salt, octyl phosphate, octyl phosphate salt, decyl phosphate, decyl phosphate salt, lauryl phosphate, lauryl phosphate salt, tetradecyl phosphate, tetradecyl phosphate salt, hexadecyl phosphate, hexadecyl phosphate salt, stearyl phosphate, stearyl phosphate salt, polyoxyethylene butyl ether phosphate, polyoxyethylene butyl ether phosphate salt, polyoxyethylene hexyl ether phosphate, polyoxyethylene hexyl ether phosphate salt, polyoxyethylene octyl ether phosphate, polyoxyethylene octyl ether phosphate salt, polyoxyethylene decyl ether phosphate, polyoxyethylene Examples include polyoxyalkylene alkyl ether phosphates or their salts, such as ethylenedecyl ether phosphate salts, polyoxyethylene lauryl ether phosphate salts, polyoxyethylene lauryl ether phosphate salts, polyoxyethylene tetradecyl ether phosphate salts, polyoxyethylene tetradecyl ether phosphate salts, polyoxyethylene hexadecyl ether phosphate salts, polyoxyethylene hexadecyl ether phosphate salts, polyoxyethylene stearyl ether phosphate salts, polyoxyethylene stearyl ether phosphate salts, polyoxypropylene octyl ether phosphate salts, polyoxypropylene octyl ether phosphate salts, polyoxypropylene decyl ether phosphate salts, polyoxypropylene lauryl ether phosphate salts, and polyoxypropylene lauryl ether phosphate salts.

[0047] Among these, alkyl phosphate salts and polyoxyalkylene alkyl ether phosphate salts or their salts are preferred from the viewpoint of their performance as surfactants and antistatic properties.

[0048] Furthermore, with respect to alkyl phosphate ester salts, the number of carbon atoms in the alkyl group is 4 or more, preferably in the range of 4 to 22, and more preferably in the range of 6 to 12. With respect to polyoxyalkylene alkyl ether phosphate esters or salts thereof, the number of carbon atoms in the alkyl group is 4 or more, preferably in the range of 6 to 22, and more preferably in the range of 8 to 18. As for the salts, metal salts and amine salts are preferred, with alkali metal salts such as lithium, sodium, and potassium, alkylamine salts, and alcoholamine salts being more preferred, and sodium salts and monoethanolamine salts being even more preferred.

[0049] Examples of cationic surfactants include quaternary ammonium salts such as alkylammonium salts and alkylbenzylammonium salts, and amine salts such as N-methylbishydroxyethylamine fatty acid ester hydrochloride. Among these, quaternary ammonium salts are preferred from the viewpoint of excellent antistatic properties.

[0050] Examples of quaternary ammonium salt type cationic surfactants include alkylammonium salts such as octyltrimethylammonium salt, decyltrimethylammonium salt, lauryltrimethylammonium salt, tetradecyltrimethylammonium salt, hexadecyltrimethylammonium salt, stearyltrimethylammonium salt, octyldimethylethylammonium salt, decyldimethylethylammonium salt, lauryldimethylethylammonium salt, tetradecyldimethylethylammonium salt, hexadecyldimethylethylammonium salt, octyltriethylammonium salt, lauryltriethylammonium salt, hexadecyltriethylammonium salt, didecyldimethylammonium salt, etc., and alkylbenzylammonium salts such as octyldimethylbenzylammonium salt, decyldimethylbenzylammonium salt, lauryldimethylbenzylammonium salt, tetradecyldimethylbenzylammonium salt, hexadecyldimethylbenzylammonium salt, stearyldimethylbenzylammonium salt, tributylbenzylammonium salt, trihexylbenzylammonium salt, etc.

[0051] Among these, alkylammonium salts are preferred from the viewpoint of their performance as surfactants and antistatic properties.

[0052] Furthermore, the longest number of carbon atoms in the alkyl group is usually 4 or more, preferably 6 to 22, and more preferably 8 to 18. Examples of counterions for the ammonium group include halogen ions, sulfonates, sulfates, phosphates, nitrates, and carboxylates. Among these, chlorides, sulfonates, and sulfates are preferred from the viewpoint of good antistatic properties.

[0053] Examples of amphoteric surfactants include betaine-type surfactants such as alkylbetaine, amino acid-type surfactants such as alkylamino fatty acid salts, and amine oxide-type surfactants such as alkylamine oxides. Among these, betaine-type surfactants are preferred from the viewpoint of having excellent antistatic properties.

[0054] Examples of betaine-type amphoteric surfactants include octyldimethylaminoacetic acid betaine, decyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, tetradecyldimethylaminoacetic acid betaine, hexadecyldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid betaine, octanoic acid amidopropyl betaine, decanoic acid amidopropyl betaine, lauryl acid amidopropyl betaine, tetradecanoic acid amidopropyl betaine, hexadecanoic acid amidopropyl betaine, and stearic acid amidopropyl betaine.

[0055] Examples of nonionic surfactants include ester-type surfactants in which polyhydric alcohols such as glycerin and sugars are ester-bonded to fatty acids; ether-type surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene alkylphenyl ethers; ester-ether-type surfactants in which alkylene oxide is added to fatty acids or polyhydric alcohol fatty acid esters; and amide-type surfactants such as fatty acid alkanolamides in which hydrophobic and hydrophilic groups are connected by amide bonds. Among these, ester-type, ether-type, and ester-ether-type surfactants are preferred when considering heat resistance, and ether-type surfactants are preferred when considering antistatic performance.

[0056] Examples of ester-type and ester / ether-type nonionic surfactants include glycerol fatty acid esters such as glycerol mono(di)laurate, glycerol mono(di)stearate, glycerol, glycerol mono(di)oleate, diglycerol mono(di)stearate, triglycerol mono(di)stearate, polyoxyethylene glycerol fatty acid esters such as polyoxyethylene glycerol mono(di)laurate, polyoxyethylene glycerol mono(di)stearate, polyoxypropylene glycerol mono(di)laurate, polyoxypropylene glycerol mono(di)stearate, polyoxybutylene glycerol mono(di)laurate, polyoxybutylene glycerol mono(di)stearate, polyoxyethylene mono(di)laurate, and polyoxyethylene mono(di)stearate. Examples include polyoxyalkylene fatty acid esters such as polyoxyethylene mono(di)oleate, polyoxypropylene mono(di)laurate, and polyoxypropylene mono(di)stearate; sorbitan fatty acid esters such as sorbitan mono(di)laurate, sorbitan mono(di)palmitate, sorbitan mono(di)stearate, and sorbitan mono(di)oleate; and polyoxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxypropylene sorbitan monolaurate, and polyoxypropylene sorbitan monostearate.

[0057] Among these, glycerin fatty acid esters, polyoxyalkylene glycerin fatty acid esters, and polyoxyalkylene fatty acid esters are preferred from the viewpoint of compatibility with various resins used in combination in the antistatic layer and antistatic properties, and glycerin fatty acid esters and polyoxyalkylene glycerin fatty acid esters, which are fatty acid esters having a glycerin skeleton, are more preferred.

[0058] Furthermore, among these, those with superior antistatic properties and compatibility are those in which the number of carbon atoms in the alkyl group is 8 or more, preferably 10 to 22, and more preferably 12 to 18.

[0059] Examples of ether-type nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene isodecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyldodecyl ether, polyoxypropylene lauryl ether, polyoxypropylene cetyl ether, polyoxypropylene stearyl ether, polyoxypropylene oleyl ether, polyoxybutylene lauryl ether, polyoxybutylene cetyl ether, polyoxybutylene stearyl ether, polyoxybutylene oleyl ether, and other polyoxyalkylene alkyl ethers, as well as polyoxyethylene triphenylphenyl ether, polyoxyethylene tripenzylphenyl ether, polyoxyethylene disstyrenephenyl ether, and other polyoxyalkylene phenyl ethers.

[0060] Among these, polyoxyalkylene alkyl ethers are preferred from the viewpoint of antistatic properties. Furthermore, from the viewpoint of excellent antistatic properties and compatibility, the number of carbon atoms in the alkyl group is 8 or more, preferably in the range of 10 to 22, and more preferably in the range of 12 to 18.

[0061] The low-molecular-weight surfactant-based antistatic agents mentioned above may be used alone or in combination of two or more types. A preferred combination of two types is, for example, an anionic surfactant and a nonionic surfactant, but two types of anionic surfactants may also be used.

[0062] Conventional known materials can be used as carbon-based antistatic agents, such as carbon nanotubes, graphite, and carbon black. Among these, carbon nanotubes are preferred because they easily maintain transparency, and either single-walled or multi-walled carbon nanotubes are acceptable. Single-walled carbon nanotubes are more preferred from the viewpoint of high conductivity.

[0063] Conventional known materials can be used as metal-based antistatic agents, including metal powders and fibers such as silver, copper, and nickel, and metal oxides such as tin oxide, zinc oxide, indium oxide, indium tin oxide, and antimony tin oxide. Among these, metal oxides are preferred when forming an antistatic layer by coating, from the viewpoint of ease of application to paints.

[0064] In addition to the antistatic agent, various conventionally known resins can be used in the antistatic layer to impart properties such as retention of the antistatic agent. Specific examples of resins include acrylic resin, urethane resin, polyester resin, and polyvinyl resin (polyvinyl alcohol, vinyl chloride-vinyl acetate copolymer, etc.). Among these, acrylic resin and polyvinyl resin are preferred when considering compatibility with the antistatic agent. Furthermore, polyester resin, acrylic resin, and urethane resin are preferred when considering adhesion to the substrate.

[0065] Acrylic resin is a polymer of polymerizable monomers, including (meth)acrylic monomers. Examples of acrylic resins include homopolymers and copolymers of (meth)acrylic monomers, and copolymers of (meth)acrylic monomers and polymerizable monomers other than (meth)acrylic monomers. Acrylic resins may be copolymers of these polymers with other polymers (e.g., polyester, polyurethane, etc.). Such copolymers are, for example, block copolymers and graft copolymers. Alternatively, polymers (and possibly mixtures of polymers) obtained by polymerizing polymerizable monomers in a solution or dispersion of polyester are also included. Similarly, polymers (and possibly mixtures of polymers) obtained by polymerizing polymerizable monomers in a solution or dispersion of polyurethane are also included. Similarly, polymers (and possibly mixtures of polymers) obtained by polymerizing polymerizable monomers in a solution or dispersion of other polymers are also included. In this invention, "(meth)acrylic" means "acrylic" and "methacrylic," and "(meth)acrylate" means "acrylate" and "methacrylate," or both.

[0066] The polymerizable monomers mentioned above are not particularly limited, but some representative compounds include, for example, carboxyl group-containing monomers and their salts such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and citraconic acid; hydroxyl group-containing monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, monobutyl hydroxyl fumarate, and monobutyl hydroxyitaconate; methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethyl Examples include alkyl(meth)acrylates such as hexyl(meth)acrylate and lauryl(meth)acrylate; nitrogen-containing monomers such as (meth)acrylamide, diacetone acrylamide, N-methylolacrylamide, and (meth)acrylonitrile; styrene compounds such as styrene, α-methylstyrene, divinylbenzene, and vinyltoluene; vinyl esters such as vinyl propionate and vinyl acetate; silicon-containing monomers such as γ-methacryloxypropyltrimethoxysilane and vinyltrimethoxysilane; phosphorus-containing vinyl monomers; vinyl halides such as vinyl chloride and pyridene chloride; and conjugated dienes such as butadiene.

[0067] Urethane resins are polymer compounds that contain urethane bonds within their molecules, and are typically synthesized by the reaction of polyols and polyisocyanate compounds. Chain extenders may be used when synthesizing urethane resins. Examples of polyols used to obtain urethane resin include polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, and acrylic polyols. These compounds may be used individually or in combination of two or more.

[0068] Polycarbonate polyols are obtained by the reaction (de-alcoholization reaction) of a polyhydric alcohol with a carbonate compound. Examples of polyhydric alcohols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 3,3-dimethylolheptane. Examples of carbonate compounds include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and ethylene carbonate. Specific examples of polycarbonate polyols include poly(1,6-hexylene) carbonate and poly(3-methyl-1,5-pentylene) carbonate.

[0069] Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene ether glycol, and polyhexamethylene ether glycol.

[0070] Polyester polyols include those obtained by the reaction of a polycarboxylic acid or its acid anhydride with a polyhydric alcohol, and those having derivative units of lactone compounds such as polycaprolactone. Examples of polycarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, isophthalic acid, etc. Examples of polyhydric alcohols include 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 Examples include ,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-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, alkyldialkanolamines, lactonediols, etc.

[0071] Considering adhesion performance, polyester polyols and polycarbonate polyols are preferred as polyols.

[0072] Examples of polyisocyanate compounds used to obtain urethane resins include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylenediphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and tolidine diisocyanate; aliphatic diisocyanates having aromatic rings such as α,α,α',α'-tetramethylxylylene diisocyanate; aliphatic diisocyanates such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, and hexamethylene diisocyanate; and alicyclic diisocyanates such as cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and isopropylidene dicyclohexyl diisocyanate. These may be used individually or in combination of two or more.

[0073] Polyester resins include those whose main components are polycarboxylic acids and polyhydroxy compounds. Examples of polycarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 4,4'-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, 5-sodium sulfisoisophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid, succinic acid, trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, phthalic anhydride, monopotassium salt of trimellitic acid, and their ester-forming derivatives. Examples of polyvalent hydroxy compounds include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,5-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, p-xylylene glycol, bisphenol A-ethylene glycol adduct, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetramethylene oxide glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, sodium dimethylolethylsulfonate, potassium dimethylolpropionate, and the like. From these compounds, one or more can be appropriately selected, and polyester resins can be synthesized by conventional polycondensation reactions.

[0074] Examples of polyvinyl resins include polyvinyl alcohol, which has a polyvinyl alcohol moiety. Conventional known polyvinyl alcohols can be used, including modified compounds that have been partially acetalized or butyralized. The degree of polymerization of the polyvinyl alcohol is not particularly limited, but is usually 100 or higher, preferably in the range of 300 to 40,000. If the degree of polymerization is less than 100, the water resistance of the antistatic layer may decrease. The degree of saponification of the polyvinyl alcohol is not particularly limited, but is a polyvinyl acetate saponified product with a degree of 70 mol% or higher, preferably in the range of 70 to 99.9 mol%.

[0075] To strengthen the antistatic layer, it is possible to include compounds derived from crosslinking agents. Known materials can be used as crosslinking agents, including, for example, melamine compounds, oxazoline compounds, isocyanate compounds, epoxy compounds, carbodiimide compounds, silane coupling compounds, hydrazide compounds, and aziridine compounds. Among these, melamine compounds, isocyanate compounds, epoxy compounds, oxazoline compounds, carbodiimide compounds, and silane coupling compounds are preferred, and from the viewpoint of further improving durability, melamine compounds, oxazoline compounds, isocyanate compounds, and epoxy compounds are more preferred. These crosslinking agents may be used individually or in combination of two or more. Using two or more in combination may further improve substrate adhesion and durability.

[0076] The antistatic layer may further contain particles for blocking or improving slipperiness. Furthermore, to the extent that it does not impair the spirit of the present invention, it may optionally contain additives such as defoaming agents, coating properties improvers, thickeners, organic lubricants, ultraviolet absorbers, antioxidants, foaming agents, dyes, and pigments.

[0077] Furthermore, the antistatic layer may not only be a resin-based layer as described above, but may also be a hardened layer, such as a hard coat layer, in order to improve scratch resistance and expand its use to various applications. The antistatic agent described above can also be used in a hard coat layer.

[0078] The hard coat layer can be formed using conventionally known methods such as active energy ray curing or thermal curing. A hard coat layer formed by active energy ray curing is preferred because it can be cured in a short time and causes little damage to the substrate.

[0079] As the active energy ray curable compound, conventionally known materials can be used, but (meth)acrylate is a preferred material, for example. The (meth)acrylate is not particularly limited and may be monofunctional (meth)acrylate, difunctional (meth)acrylate, or polyfunctional (meth)acrylate with three or more functions. (Meth)acrylate that is commercially available as a curable resin material can also be used. The (meth)acrylate may contain other components as long as it does not impair the purpose of the present invention. Among these, difunctional or polyfunctional (meth)acrylate with three or more functions is preferred because it has excellent abrasion resistance, and trifunctional (meth)acrylate with three or more functions is particularly preferred. In addition, as the (meth)acrylate, (meth)acrylic (meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate, silicone (meth)acrylate, etc. can also be used. (Meth)acrylic (meth)acrylate is particularly preferred when considering moldability and elongation.

[0080] Examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, morpholyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and diethyl Examples include mono(meth)acrylates such as aminoethyl (meth)acrylate, tricyclodecane (meth)acrylate, polyethylene glycol mono(meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, allyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and phenyl (meth)acrylate, as well as mono(meth)acrylate compounds such as adducts of phthalic anhydride and 2-hydroxyethyl (meth)acrylate.

[0081] Examples of difunctional and polyfunctional (meth)acrylates include alkane diol di(meth)acrylates such as 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and tricyclodecanedimethylol di(meth)acrylate; bisphenol-modified di(meth)acrylates such as bisphenol A ethylene oxide-modified di(meth)acrylate and bisphenol F ethylene oxide-modified di(meth)acrylate; polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, urethane di(meth)acrylate, and epoxy di(meth)acrylate.

[0082] Examples of polyfunctional (meth)acrylates with three or more functions include dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, and ethylene oxide-modified penta(meth)acrylate. Examples include ethylene oxide-modified (meth)acrylates such as lithritol tetra(meth)acrylate, isocyanuric acid-modified tri(meth)acrylates such as ethylene oxide-modified isocyanurate, isocyanuric acid-modified tri(meth)acrylates such as ε-caprolactone-modified tris(acrooxyethyl)isocyanurate, urethane (meth)acrylates such as pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, and dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer. Among these, (meth)acrylates with four or more functions are preferred due to their excellent wear resistance, and (meth)acrylates with six or more functions are even more preferred. Furthermore, considering compatibility with elongation during molding, polyfunctional (meth)acrylates with extended alkyl chains are preferred, particularly (meth)acrylates with four or more functions with extended alkyl chains, and (meth)acrylates with six or more functions with extended alkyl chains are even more preferred. For example, caprolactone-modified dipentaerythritol hexa(meth)acrylate is an optimal material. In particular, if there are two or more caprolactone modifications per molecule of (meth)acrylate, it is preferable for elongation, and for applications where elongation is particularly important, it is even preferable to have six or more modifications.

[0083] Photopolymerization initiators can also be used to accelerate the curing of active energy ray-curable compounds. Specific examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin phenyl ether, benzyl diphenyl disulfide, dibenzyl, diacetyl, anthraquinone, naphthoquinone, 3,3'-dimethyl-4-methoxybenzophenone, benzophenone, p,p'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, pivaloin ethyl ether, benzyl dimethyl ketal, 1,1-dichloroacetophenone, pt-butyldichloroacetophenone, and 1-hydroxy Examples include cyclohexylphenyl ketone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-dichloro-4-phenoxyacetophenone, phenylglyoxylate, α-hydroxyisobutylphenone, dibenzosparone, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, tribromophenylsulfone, and tribromomethylphenylsulfone. These photopolymerization initiators may be used individually or in combination of two or more.

[0084] Furthermore, various compounds having active energy ray curable functional groups other than (meth)acrylate can be used, and various additives such as UV absorbers, light stabilizers, leveling agents, antioxidants, anti-yellowing agents, bluing agents, pigments, dyes, defoamers, thickeners, anti-settling agents, and anti-fogging agents may also be used as needed.

[0085] Furthermore, when forming an antistatic layer, if the method involves coating it onto the substrate, Various solvents can be used as needed. Examples of solvents include water, aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, and phenethole; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; amide solvents such as dimethylformamide, diethylformamide, and N-methylpyrrolidone; cellosolve solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol; and halogen solvents such as dichloromethane and chloroform. These solvents may be used individually or in combination of two or more. Of these solvents, water is preferred from an environmental perspective, and ester-based solvents, ether-based solvents, alcohol-based solvents, and ketone-based solvents are preferred because they easily improve workability during application.

[0086] The content of non-volatile components (solids) in the composition forming the antistatic layer cannot be stated definitively as it depends on the material system used, but it is generally in the range of 0.1 to 100% by mass. Non-volatile content refers to the total mass of components other than the solvent, such as solvents. The non-volatile content of a composition that forms an antistatic layer can be measured by conventionally known methods. For example, it can be measured by the change in weight when 1 g of the composition is spread out and heated at 100°C for 1 hour to evaporate the solvent.

[0087] Conventional methods can be used to form the antistatic layer, such as coating and transfer. Coating is preferred because it involves fewer steps and can be applied easily. Known coating methods such as gravure coating, reverse roll coating, die coating, air doctor coating, blade coating, rod coating, bar coating, curtain coating, knife coating, transfer roll coating, squeeze coating, impregnation coating, kiss coating, spray coating, calender coating, extrusion coating, dip coating, and spin coating can be used as coating methods when forming the antistatic layer.

[0088] Furthermore, the substrate can be subjected to corona treatment or plasma treatment to improve adhesion with the antistatic layer and enhance coating properties.

[0089] While there are no particular limitations on the drying and curing conditions when forming the antistatic layer, the drying temperature of the medium, such as water or organic solvent used in the coating solution, is typically in the range of 30 to 200°C, preferably 50 to 150°C, and more preferably 70 to 120°C. The drying time is preferably 0.01 to 30 minutes, and more preferably 0.1 to 10 minutes. In the case of an antistatic layer formed by heat curing, drying and heat curing can be performed simultaneously or consecutively.

[0090] Examples of active energy rays used in curing with active energy rays include ultraviolet rays, electron beams, visible light, infrared rays, and X-rays. Among these, ultraviolet rays and electron beams are preferred from the viewpoint of curing properties and prevention of resin degradation, with ultraviolet rays being more preferred. The irradiation dose of the active energy rays can be appropriately selected depending on the active energy rays being irradiated.

[0091] For example, when using ultraviolet light, the integrated light intensity of the irradiation is 20 to 5000 mJ / cm². 2 Preferably, 100-3000 mJ / cm² 2 More preferably, 200-2000 mJ / cm² 2 This is even more preferable. Furthermore, the illuminance should be 50-600 mW / cm². 2is preferable, 75 to 450 mW / cm 2 is more preferable, 100 to 300 mW / cm 2 is even more preferable. As the light source, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, an electrodeless lamp, a metal halide lamp, or an electron beam such as an electron beam by a scanning type or curtain type electron beam accelerator, an ultra-high-pressure mercury lamp, etc., a low-pressure mercury lamp, etc. can be used.

[0092] Also, when curing by electron beam irradiation, various electron beam irradiation devices can be used. The irradiation dose (Mrad) of the electron beam is preferably 0.5 to 20 Mrad, and more preferably 1 to 15 Mrad from the viewpoints of the curability of the active energy ray curable composition of the present invention, the flexibility of the cured product, and the prevention of damage to the substrate.

[0093] The ratio of the antistatic agent in 100% by mass of the antistatic layer depends on the type of the antistatic agent and is not absolute. For example, it is in the range of 0.1% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more, and the upper limit is 100% by mass without particular limitation. When improving the adhesion to the substrate or when further providing a functional layer on the antistatic layer, etc., the ratio of other materials used in combination can also be increased. In that case, it is preferably in the range of 0.1 to 90% by mass, more preferably 1 to 80% by mass, and even more preferably 3 to 70% by mass. If the ratio of the antistatic agent is within the above range, it is easy to impart a sufficient antistatic function to the antistatic layer and the durability is also good.

[0094] The thickness of the antistatic layer is preferably in the range of 0.01 to 20 μm, more preferably 0.05 to 10 μm, and even more preferably 0.1 to 7 μm. If the thickness of the antistatic layer is within the above range, it is easy to realize the desired antistatic characteristics. The thickness of the antistatic layer is determined by cross-sectional observation using an electron microscope or the like.

[0095] As the surface resistance value of the antistatic layer, usually 1×10 13 Ω or less, preferably 1×10 12 Ω or less, more preferably 1×10 11 Ω or less, even more preferably 1×1010 Ω or less, particularly preferably 5 × 10 9 The resistance should be within the range of Ω or less. While there is no specific lower limit, it should be 100Ω or higher. Keeping it within this range helps to suppress the adhesion of foreign matter such as dust.

[0096] The surface resistance of the laminate after 10% stretching is 1 × 10⁻⁶ 13 It is less than or equal to Ω, preferably 1 × 10⁻¹⁶ 12 Ω or less, more preferably 1 × 10⁻¹⁰ 11 Ω or less, more preferably 5 × 10 10 Ω or less, particularly preferably 1 × 10⁻⁶ 10 The resistance is within the range of Ω or less. There is no specific lower limit, but it should be 100Ω or more. By keeping it within this range, the adhesion of foreign matter such as dust can be suppressed even after stretching (bending, folding, stretching).

[0097] The surface resistance of the laminate after 20% stretching is 1 × 10⁻⁶ 13 It is less than or equal to Ω, preferably 1 × 10⁻¹⁶ 12 Ω or less, more preferably 5 × 10 11 Ω or less, more preferably 2 × 10⁻¹⁰ 11 Ω or less, particularly preferably 5 × 10 10 The resistance is within the range of Ω or less. There is no specific lower limit, but it should be 100Ω or more. By keeping it within this range, the adhesion of foreign matter such as dust can be suppressed even after stretching (bending, folding, stretching).

[0098] For applications requiring higher processability, it is preferable that the material retains antistatic properties even after 50% stretching, and the surface resistance value after 50% stretching is preferably 1 × 10⁻⁶. 13 Ω or less, more preferably 1 × 10⁻¹⁰ 12 Ω or less, more preferably 1 × 10⁻¹⁰ 11 Ω or less, particularly preferably 1 × 10⁻⁶ 10 The range is less than or equal to Ω. There is no specific lower limit, but it is 100Ω or more.

[0099] Furthermore, for applications requiring higher processability, the surface resistance value should be 1 × 10 13The stretching range in which the resistance is less than or equal to Ω is preferably 100% stretch (2x stretch) or less, more preferably 150% stretch or less, and even more preferably 200% stretch or less. A preferred surface resistance value is 1 × 10⁻⁶. 13 There is no upper limit on the stretched region that can maintain a value of Ω or less, but for example, it can be stretched to 2000%.

[0100] The components in the substrate and antistatic layer can be analyzed by methods such as TOF-SIMS (time-of-flight secondary ion mass spectrometry), ESCA (X-ray photoelectric spectroscopy), X-ray fluorescence, and IR (infrared spectroscopy).

[0101] Furthermore, it is possible to provide a functional layer on top of the antistatic layer of the present invention. Examples of conventionally known functional layers include anti-reflective layers, low-reflective layers, high-reflective layers, anti-glare layers, anti-blocking layers, anti-fouling layers, anti-fogging layers, and adhesive layers. It is also possible to provide various functional layers on the side of the substrate opposite to the side with the antistatic layer. It is also possible to provide the antistatic layer on both sides of the substrate.

[0102] The laminate of the present invention is particularly suitable for use in display components and electrical / electronic components due to its excellent optical properties, such as birefringence, among various applications. It is also suitable for use in automotive parts and various lenses due to its superior scratch resistance compared to general polycarbonate resins. Similarly, it is suitable for various film applications, such as display components and decorative applications, due to its superior processability compared to general polycarbonate resins. In particular, it is ideal for flexible display applications, bending applications for housings of various components, and decorative applications, as it exhibits excellent antistatic properties even after bending, folding, and stretching. [Examples]

[0103] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the essence of the invention. The measurement and evaluation methods used in this invention are as follows.

[0104] (1) Measurement of weight-average molecular weight (Mw) and number-average molecular weight Equipment: Tosoh Corporation's "HLC-8120GPC" Column: "TSKgel Super H1000+H2000+H3000" manufactured by Tosoh Corporation. Detector: Differential refractive index detector (RI detector / built-in), Solvent: Tetrahydrofuran, Temperature: 40℃, Flow rate: 0.5mL / min, Injection volume: 10μL, Concentration: 0.2% by mass, Calibration sample: Monodisperse polystyrene, Calibration method: Polystyrene equivalent.

[0105] (2) Measurement of glass transition temperature A viscoelastic spectrometer DVA-200 (manufactured by IT Measurement Control Co., Ltd.) was used to perform dynamic viscoelastic temperature dispersion measurements (dynamic viscoelastic measurement according to JIS K7198A method) at a strain of 0.1%, a frequency of 10 Hz, and a heating rate of 3 °C / min. The temperature at which the peak of the main dispersion of the loss tangent (tanδ) was observed was defined as the glass transition temperature.

[0106] (3) Measurement of surface resistance Using a high-resistivity meter, the MCP-HP450, manufactured by Mitsubishi Chemical Analytec Corporation, the sample was conditioned for 30 minutes under an applied overvoltage of 100V, 23°C, and 50%RH, and then the surface resistance value was measured. If the surface resistance value shows "OVER," it indicates that the surface resistance is too high to be measured by a high resistivity meter. If the surface resistance value is UNDER, it means the surface resistance is too low to be measured with a high resistivity meter, so the value measured using the method described below was used as the surface resistance value. A low resistivity meter, Loresta GP MCP-T610, manufactured by Mitsubishi Chemical Analytec Corporation, was used with a four-probe ESP probe (probe spacing: 5 mm, probe tip shape: 2 mm diameter cylinder, probe pressure: 240 g / probe, RCF value kept constant at 4.235). The sample was conditioned for 30 minutes in a measurement atmosphere of 23°C and 50% RH, and then the surface resistance value was measured.

[0107] (4) Measurement of surface resistance after stretching The obtained film was stretched at various magnifications using a Tensilon tensile testing machine (MX2-500N, manufactured by Imada Corporation) in a uniaxial direction under the conditions of a temperature of 140°C, a tensile speed of 40 mm / min, and a chuck distance of 40 mm. The surface resistance value was measured in the same manner as in measurement (3). Note that 10% stretching refers to 1.1 times stretching.

[0108] (5) Method for evaluating the scratch resistance of the coated layer The antistatic layer was strongly rubbed using a nonwoven fabric (Bencot® M-3II, manufactured by Asahi Kasei Corporation). If no scratches or marks were observed (good scratch resistance), the result was rated as A; if scratches or marks were observed, the result was rated as B.

[0109] The materials used in the examples and comparative examples are as follows:

[0110] (base material) ISB: Isosorbide • CHDM: 1,4-Cyclohexanedimethanol TCDDM: Tricyclodecanedimethanol DPC: Diphenyl carbonate Irganox1010: Pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (manufactured by BASF, heat stabilizer) AS2112: Tris(2,4-di-tert-butylphenyl) phosphite (manufactured by ADEKA Corporation, heat stabilizer) • E-275: Ethylene glycol distearate (manufactured by NOF Corporation, mold release agent)

[0111] (Examples of compounds for antistatic layers) • Polymer-type antistatic agents containing ammonium groups: (A1) A polymer with a number-average molecular weight of 30,000, composed of the following monomer composition, each having a pyrrolidinium ring in the main chain. Monomer composition: diallyldimethylammonium chloride / dimethylacrylamide / N-methylolacrylamide = 90 / 5 / 5 (mol%). • Polymer-type antistatic agents containing ammonium groups: (A2) A polymer with a number-average molecular weight of 100,000, manufactured by the method described below. In a reactor equipped with a stirrer, reflux condenser, and thermometer, 66 parts by mass of N,N-dimethylaminoethyl methacrylate quaternary, 20 parts by mass of N,N-dimethylaminoethyl methacrylate, 30 parts by mass of 2-ethylhexyl methacrylate, 1 part by mass of azobisisobutyronitrile, 200 parts by mass of isopropyl alcohol, and 100 parts by mass of methyl ethyl ketone were charged. After stirring was started, the system was purged with nitrogen, the temperature was raised to 80°C, and the reaction was carried out for 8 hours to obtain a copolymer solution. • A conductive organic polymer compound having a number-average molecular weight of 1,000 or more, obtained by compounding poly(3,4-ethylenedioxythiophene) with polystyrene sulfonic acid: (A3).

[0112] • Acrylic resin: (B1) Acrylic resin having the following composition Ethyl acrylate / n-butyl methacrylate / acrylic acid = 25 / 73 / 2 (mass%) • Polyvinyl alcohol: (B2) Polyvinyl alcohol with a saponification degree of 88 mol% and a degree of polymerization of 500.

[0113] • (Meth)acrylate: (C1) Dipentaerythritol hexaacrylate (hexafunctional) (manufactured by Nippon Kayaku Co., Ltd., Kayarad® DPHA) • (Meth)acrylic (meth)acrylate: (C2) (Meth)acrylic resin manufactured by the method shown below In a flask equipped with a thermometer, stirrer, and reflux condenser, 178 parts by mass of propylene glycol monomethyl ether, 20 parts by mass of glycidyl methacrylate, 79 parts by mass of methyl methacrylate, 1.0 part by mass of ethyl acrylate, and 0.6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) were added and reacted at 65°C for 3 hours. Then, 0.3 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was added and reacted for another 3 hours, after which 48 parts by mass of propylene glycol monomethyl ether and 0.5 parts by mass of p-methoxyphenol were added and heated to 100°C. Next, acrylic acid (10 parts by mass) and triphenylphosphine (1.6 parts by mass) were added and the mixture was reacted at 110°C for 6 hours to obtain (meth)acrylic resin (A-1) with a radical polymerizable double bond content (acryloyl group concentration (amount of acryloyl groups introduced)) of 615 g / mmol. The weight-average molecular weight was 48800. The hydroxyl value was 91 mgKOH / mg.

[0114] • Photopolymerization initiator: (D) 1-Hydroxycyclohexylphenyl ketone (Omnirad 184, manufactured by IGM Resins BV)

[0115] [Example 1] Polycarbonate resin polymerization was carried out using a continuous polymerization system consisting of three vertical agitated reactors, one horizontal agitated reactor, and a twin-screw extruder with a vacuum vent, connected in that order. ISB, CHDM, and DPC were melted in separate raw material preparation tanks and continuously supplied to the first vertical agitated reactor in a molar ratio of ISB / CHDM / DPC = 70 / 30 / 101. In addition, an aqueous solution of calcium acetate monohydrate was supplied to the first vertical agitated reactor as a polymerization catalyst at a ratio of 1.5 μmol per mole of total hydroxyl compounds. The temperature, pressure, and residence time for each reactor were approximately as follows: First vertical reactor: 190°C, 25kPa, 90 minutes; Second vertical reactor: 195°C, 10kPa, 45 minutes; Third vertical reactor: 210°C, 3kPa, 45 minutes; Fourth horizontal reactor: 225°C, 0.5kPa, 90 minutes. The fourth horizontal stirring reactor was operated while adjusting the internal pressure so that the reduced viscosity of the resulting polycarbonate resin was approximately 0.38 to 0.39 dL / g.

[0116] The polymerization reaction product was extracted from the fourth horizontal agitator at a flow rate of approximately 60 kg / hour and supplied in its molten state to a twin-screw extruder with a vacuum vent (TEX30α, L / D=42, manufactured by Japan Steel Works). This extruder was equipped with three vacuum vents. Before the second vent, water was continuously injected into the molten resin at a ratio of approximately 2000 ppm by mass to perform so-called water defoliation. Next, before the third vent, heat stabilizers such as Irganox 1010, AS2112, and E-275 were continuously supplied in ratios of 0.1 parts by mass, 0.05 parts by mass, and 0.3 parts by mass to melt and knead the resin. The molten resin that passed through the extruder was filtered for impurities through a candle-type filter with a mesh size of 10 μm, discharged from the die in strand form, solidified by water cooling, and pelletized with a rotary cutter to obtain a copolymer polycarbonate resin with a glass transition temperature of 120°C.

[0117] Copolymerized polycarbonate resin was supplied to an extruder, melted at 240°C, and then cooled and solidified on a cooling roll set to 120°C using a T-die to obtain a film with a thickness of 50 μm (substrate S1).

[0118] The obtained film was coated with the coating solution F1 shown in Table 1 below, dried at 80°C for 1 minute to form an antistatic layer with a thickness of 0.1 μm, and a laminate was obtained.

[0119] The resulting laminate had low surface resistance values ​​both before and after stretching, preventing the adhesion of foreign matter such as dust. The characteristics of this laminate are shown in Table 2 below.

[0120] [Examples 2-5] In Example 1, the laminate was manufactured in the same manner as in Example 1, except that the coating liquid composition of the antistatic layer was changed to the coating agent composition shown in Table 1, or the film thickness of the antistatic layer was changed. The properties of the obtained laminate are shown in Table 2 below.

[0121] [Example 6] In Example 1, the antistatic layer coating solution composition was changed to coating solution F4 shown in Table 1, dried at 80°C for 1 minute, and then subjected to a high-pressure mercury lamp treatment of 300 mJ / cm². 2 The laminate was manufactured in the same manner as in Example 1, except that a 5 μm thick antistatic layer was formed by irradiating the coating with 200 mW of light and curing it. The characteristics of the obtained laminate are shown in Table 2 below, and it had good surface resistance.

[0122] [Example 7] In Example 1, the laminate was manufactured in the same manner as in Example 1, except that the resin raw material of the base material was changed from CHDM to TCDDM (base material S2). The properties of the obtained laminate were as shown in Table 2 below, and it had a good surface resistance value. The glass transition temperature of the copolymerized polycarbonate resin in Example 7 was 130°C.

[0123] [Comparative Example 1] In Example 1, the film was manufactured in the same manner as in Example 1, except that an antistatic layer was not provided. As shown in Table 2, the obtained film had poor surface resistance. The surface resistance was measured using the same method as the surface resistance of the antistatic layer.

[0124] [Comparative Example 2] In Example 1, the coating liquid composition was changed to the coating liquid shown in Table 1, and a laminate was obtained in the same manner as in Example 1, except that a coating layer without an antistatic agent was formed. As shown in Table 2, the obtained laminate had poor surface resistance.

[0125] [Table 1]

[0126] [Table 2]

Claims

1. A laminate having an antistatic layer on at least one surface of a copolymer polycarbonate resin substrate comprising structural units derived from isosorbide and structural units derived from 1,4-cyclohexanedimethanol or tricyclodecanedimethanol, wherein the surface resistance of the laminate after being stretched by 10% is 1 × 10 １３ A laminate with an Omega value of less than Ω.

2. The laminate according to claim 1, wherein the glass transition temperature of the copolymerized polycarbonate resin constituting the substrate is 40 to 180°C.

3. The laminate according to claim 1, wherein the antistatic layer contains an antistatic agent, and the antistatic agent is a polymer-type antistatic agent.

4. The laminate according to claim 3, wherein the polymer-type antistatic agent is a compound having an ammonium group or a conductive organic polymer.

5. The laminate according to claim 4, wherein the antistatic layer is a cured layer.

6. The laminated film according to claim 2 or 4, wherein the substrate is a film.

7. A method for producing a laminate, comprising forming an antistatic layer by applying a coating solution containing an antistatic agent to at least one surface of a copolymer polycarbonate resin substrate containing structural units derived from isosorbide and structural units derived from 1,4-cyclohexanedimethanol or tricyclodecanedimethanol, and then stretching the laminate in at least one direction.

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