Laminate

Abstract

To provide a laminate with properties such as scratch resistance and an antistatic property by creating a laminate having a functional layer and a hard coat layer in this order on at least one side of plane of a polycarbonate resin base material containing a heterocyclic bicyclo-ring structure.SOLUTION: There is provided a laminate having a functional layer and a hard coat layer in this order on at least one side of plane of a polycarbonate resin base material containing a heterocyclic bicyclo-ring structure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to at least one of a polycarbonate resin substrate containing a heterobicyclo ring structure. This invention relates to a laminate having a functional layer and a hard coat layer on its surface in that order. [Background technology]

[0002] Display components, electrical and electronic components, automotive parts, building materials, lenses, containers, packaging Polycarbonate, polyester, polymethyl methacrylate, and other materials are used in a variety of applications. Plastic materials such as acetylcellulose, polystyrene, and polyvinyl chloride are used. Among them, polycarbonate, for example, has excellent impact resistance and heat resistance and is applied to various applications. It is one of the resins with a wide range of applications.

[0003] A proposal has been made to directly laminate a hard coat layer onto polycarbonate using isosorbide. (Patent Document 1). Although the wear resistance is improved by laminating the hard coat layer, Depending on the type and form of the carbonate resin, as well as the type of hard coat layer, there is a concern that adhesion may be poor. Furthermore, it was difficult to impart other properties such as antistatic properties. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2016-68438 [Overview of the project] [Problems that the invention aims to solve]

[0005] The present invention relates to at least one of a polycarbonate resin substrate containing a heterobicyclo ring structure. By creating a laminate having a functional layer and a hard coat layer in that order on each surface, scratch resistance and banding can be achieved. The objective is to provide laminates with properties such as electrostatic discharge prevention. [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] On at least one surface of a polycarbonate resin substrate containing a heterobicyclo ring structure A laminate having a functional layer and a hard coat layer in that order. [2] The polycarbonate resin constituting the base material is a copolymerized polycarbonate resin. The laminate described in [1]. [3] The glass transition temperature of the polycarbonate resin constituting the substrate is 40 to 180°C. [2] The laminate described above. [4] The laminate according to [3], which contains a resin in the functional layer. [5] The laminate according to [4], comprising an antistatic agent in the functional layer. [6] The hard coat layer contains a compound derived from (meth)acrylate as described in [5]. A laminate of [something]. [7] Surface resistance value is 1 × 10 13 The laminate described in [6] is less than or equal to Ω. [8] The laminated film according to [3] or [6], wherein the substrate is a film. [9] On at least one surface of a polycarbonate resin substrate containing a heterobicyclo ring structure A functional layer is formed by applying a coating solution containing a resin or antistatic agent, and furthermore, A method for manufacturing a laminate in which a hard coat layer is formed on a functional layer by coating. [Effects of the Invention]

[0007] The laminate of the present invention has properties such as scratch resistance and antistatic performance.

BEST MODE FOR CARRYING OUT THE INVENTION

[0008] <Substrate> Any substrate can be used as long as it is a polycarbonate resin containing a bicyclic ring structure as a constituent element. Among heterocyclic rings, a bicyclic ring structure containing oxygen (bicyclic ring structure having a cyclic ether) is preferable from the viewpoint of weather resistance. Among them, in particular, by incorporating 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. Among heterocyclic rings, a bicyclic ring structure containing oxygen (bicyclic ring structure having a cyclic ether) is preferable from the viewpoint of weather resistance. Among them, in particular, by incorporating 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. Among them, in particular, by incorporating 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. By incorporating 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. By incorporating 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.

Chemical formula

[0009] 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. Also, isosorbide is more preferable because it is easily available as a resource. 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. Also, isosorbide is more preferable because it is easily available as a resource. Among these stereoisomers, as a plant-derived compound, it can be easily produced by hydrogenating D-glucose obtained from starch and then dehydrating it. Also, isosorbide is more preferable because it is easily available as a resource. Among these stereoisomers, as a plant-derived compound, it can be easily produced by hydrogenating D-glucose obtained from starch and then dehydrating it. Also, isosorbide is more preferable because it is easily available as a resource. Particularly in recent years, there is a concern that it may lead to the depletion of petroleum resources. Therefore, there is a demand for plastic products using plant-derived raw materials. Also, global warming due to an increase in carbon dioxide emissions is cited as an issue. Therefore, from the perspective of carbon neutrality, it is required to use plant-derived raw materials. Therefore, it is ideal to use isosorbide. Particularly in recent years, there is a concern that it may lead to the depletion of petroleum resources. Therefore, there is a demand for plastic products using plant-derived raw materials. Also, global warming due to an increase in carbon dioxide emissions is cited as an issue. Therefore, from the perspective of carbon neutrality, it is required to use plant-derived raw materials. Therefore, it is ideal to use isosorbide. Particularly in recent years, there is a concern that it may lead to the depletion of petroleum resources. Therefore, there is a demand for plastic products using plant-derived raw materials. Also, global warming due to an increase in carbon dioxide emissions is cited as an issue. Therefore, from the perspective of carbon neutrality, it is required to use plant-derived raw materials. Therefore, it is ideal to use isosorbide. Particularly in recent years, there is a concern that it may lead to the depletion of petroleum resources. Therefore, there is a demand for plastic products using plant-derived raw materials. Also, global warming due to an increase in carbon dioxide emissions is cited as an issue. Therefore, from the perspective of carbon neutrality, it is required to use plant-derived raw materials. Therefore, it is ideal to use isosorbide.

[0010] Also, by using isosorbide as the dihydroxy component of the polycarbonate resin, many isosorbide structures can be incorporated into the polycarbonate resin. Therefore, the amount of plant-derived components can be increased, which is a preferable form. Also, by using isosorbide as the dihydroxy component of the polycarbonate resin, many isosorbide structures can be incorporated into the polycarbonate resin. Therefore, the amount of plant-derived components can be increased, which is a preferable form. Also, by using isosorbide as the dihydroxy component of the polycarbonate resin, many isosorbide structures can be incorporated into the polycarbonate resin. Therefore, the amount of plant-derived components can be increased, which is a preferable form.

[0011] When using polycarbonate resin with isosorbide as the dihydroxy component as the base material In addition, diester carbonates used as raw materials for polycarbonate resins are conventionally known materials. This can be done. For example, phenyl carbonate such as diphenyl carbonate and ditril carbonate. Bonates, dimethyl carbonate, diethyl carbonate, di-t-butyl carbonate Examples include alkyl carbonates such as t. Among these, phenyl carbonates... These are preferred, and diphenyl carbonate is particularly preferred. These diester carbonates are used individually. You may use one type, or you may use two or more types in combination.

[0012] Furthermore, using compounds other than isosorbide as the dihydroxy component in combination with isosorbide is also possible. Both are desirable forms. That is, copolymers used as copolymer components with isosorbide A recarbonate resin is preferred. Examples of dihydroxy components include aliphatic resins. Dihydroxy compounds, alicyclic dihydroxy compounds, composites, bisphenol compounds, or Other ether-containing dihydroxy compounds besides isosorbide are listed as preferred compounds. By introducing a more flexible molecular structure than the isosorbide structure, polycarbonate resin The toughness can be adjusted. Also, from the perspective of further improving impact resistance, aliphatic Dihydroxy compounds, alicyclic dihydroxy compounds, or composites bisphenol compounds It is preferable to use it. Furthermore, from the viewpoint of improving weather resistance, it is desirable to have aromatic compounds in the molecular structure. Compounds that do not have a ring structure, i.e., aliphatic dihydroxy compounds or alicyclic dihydro It is more preferable that it be a xy compound, and if further consideration is given to improving heat resistance, an alicyclic dihydr Roxy compounds are even more preferred. These dihydroxy components may be one or two types. It is also possible to use the above in combination. Furthermore, it is not limited to dihydroxy structures, but also trihydroxy structures. Compounds with three or more hydroxyl groups, such as hydroxy and tetrahydroxy, are used. It is also possible to do so.

[0013] Examples of alicyclic dihydroxy compounds include 1,4-cyclohexanedimethanol and tricyclic dihydroxy compounds. Rodecanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol , 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, penta Cyclopentadecane dimethanol, 2,6-decalingimethanol, 1,5-decalingimethanol Methanol, 2,3-decalingimethanol, 2,3-norbornanedimethyl, 2, Examples include 5-norbornanedimethanol, 1,3-adamantanedimethanol, and limonene. This is possible. Among these, the balance between impact resistance and flexibility, as well as ease of manufacturing, should be considered. 1,4-cyclohexanedimethanol or tricyclodecanedimethanol is preferred. Furthermore, in applications where flexibility and high bendability / stretchability are particularly important, 1,4-cyclohexa Dimethanol is even more preferred.

[0014] The aliphatic dihydroxy compound may be a linear aliphatic or a branched aliphatic. Aliphatic dihydroxy compounds include, specifically, ethylene glycol and 1,3-propane. 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, 1,12-dodecanediol These are some examples.

[0015] Examples of aromatic bisphenol compounds include 2,2-bis(4-hydroxyphenyl)pro Pan(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-bi Su(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydro Xyphenyl)pentane, 2,4'-dihydroxy-diphenylmethane, bis(4-Hyd Roxyphenyl)methane, bis(4-hydroxy-5-nitrophenyl)methane, 1,1 -Bis(4-hydroxyphenyl)ethane, 3,3-bis(4-hydroxyphenyl)ethane 1,1-Bis(4-hydroxyphenyl)cyclohexane, Bis(4-hydroxy 2,4'-Dihydroxydiphenyl sulfone, bis(4-hydro Xyphenyl) sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-di Hydroxy-3,3'-dichlorodiphenyl ether, 9,9-bis(4-(2-hydro Xyethoxy-2-methyl)phenyl)fluorene, 9,9-bis(4-hydroxyphenyl Nyl fluorene, 9,9-bis(4-hydroxy-2-methylphenyl)fluorene These can be listed. Among these, bisphenol A is preferred when considering the balance of performance. stomach.

[0016] Examples of ether group-containing dihydroxy compounds include diethylene glycol and triethylene glycol. Recall, polyethylene glycol, poly-1,3-propylene glycol, polytetra Examples include methylene glycol. For polyethylene glycol, the molecular weight is, for example... For example, items ranging from 150 to 2,000 can be used.

[0017] When using copolymer polycarbonate resin having an isosorbide structure as the base material, Percentage of structural units derived from isosorbide in 100 mol% of structural units derived from dihydroxy compounds Preferably 1 mol% or more, more preferably 10 mol% or more, and even more preferably 30 mol The range is % or more, particularly preferably 45 mol% or more, and most preferably 55 mol% or more. Furthermore, there are no particular restrictions on the upper limit, and all structural units may be derived from isosorbide, but it is preferable Or 99 mol% or less, more preferably 95 mol% or less, even more preferably 90 mol% or less The range is preferably 85 mol% or less. Using it within the above range provides heat resistance and This improves rigidity and makes it easier to adjust the balance between formability and mechanical strength.

[0018] The copolymerized polycarbonate resin contains structural units other than the dihydroxy compounds mentioned above. It may have. For example, dihydroxy compounds of aromatic hydrocarbons can be cited, but the aroma Compounds containing rings undergo structural degradation when exposed to sunlight or ultraviolet light, due to their absorption of ultraviolet rays. This often results in problems such as yellowing. Therefore, dihydroxy compounds of aromatic hydrocarbons When using such materials, ensure that the required product characteristics, such as formability, weather resistance, and surface properties, are not compromised. It is desirable to use it within a limited range.

[0019] When considering heat resistance and toughness, the glass transition temperature of polycarbonate resin is preferable. The temperature range is 40-180°C, more preferably 60-160°C, and even more preferably 80-150°C. The temperature is preferably in the range of 90 to 140°C. The operating temperature must also be taken into consideration, and it is preferable that it be below the molding temperature. .

[0020] Polycarbonate resin is an ester of the aforementioned dihydroxy compound and the aforementioned diester carbonate. It can be synthesized by polycondensation via transesterification. More specifically, by transesterification The polycondensation reaction proceeds by removing the by-product monohydroxy compounds, etc., from the system. This is possible. The transesterification reaction is promoted in the presence of a transesterification catalyst. As catalysts, metal compounds of Group 1 or Group 2 in the long-period periodic table, and basic Boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds, etc. Basic compounds can be used, particularly Group 1 metal compounds or Group 2 metal compounds. It is preferable to use at least one of the following. The amount of catalyst used is the total dihydr subjected to the reaction. Preferably 0.1 to 300 μmol per mole of roxy compound, more preferably 0.5 to It is 100 μmoles, and especially 1 to 50 μmoles.

[0021] The molar ratio of dihydroxy compound to dicarbonate diester is preferably 0.90~ A range of 1.20 is good. In this case, the amount of hydroxyl groups at the end of the polycarbonate resin Because the increase can be suppressed, the thermal stability of the resin can be improved. This can reduce discoloration during the reaction. It also suppresses the decrease in the rate of the transesterification reaction. This allows for the more reliable production of copolymers with the desired molecular weight. Furthermore, in this case, From the perspective of being able to suppress the increase in thermal history during the reaction, polycarbonate resin The discoloration can be reduced. Furthermore, in this case, residual carbon in the polycarbonate resin The amount of acid diester can be reduced, and from this perspective, the discoloration of the resin can be reduced. It is possible. Furthermore, it is possible to avoid or mitigate the generation of odors. These effects can be further enhanced. From this perspective, the mixed molar ratio of dihydroxy compounds to diester carbonates is particularly favorable. The range is 0.95 to 1.10.

[0022] Examples of polymerization reaction methods include batch, continuous, or combinations thereof. In particular, a continuous process carried out in multiple stages using multiple reactors in the presence of the catalyst is possible. This is preferable in terms of productivity and ease of thermal history management.

[0023] Furthermore, the polycarbonate resin used as the base material can also contain various additives. It is possible. Examples of additives include UV absorbers, antioxidants, light stabilizers, catalyst deactivators, Examples include dyes and pigments, flame retardants, flame retardant additives, fillers, impact modifiers, hydrolysis inhibitors, nucleating agents, and plasticizers. It can be done.

[0024] Polycarbonate resin can be processed using various conventionally known methods as a base material. The following methods are not the only ones, but for example, the resin is introduced into the extruder and additives are added. The mixture is kneaded while being continuously supplied, and by-product gases and low molecular weight volatile components are removed via a vacuum system. The molten material is extruded in a strand-like manner from the tip of the extruder, and while it cools and solidifies, it is cut into pellets. One method is to reduce the extruder to obtain sufficient defoliation capacity and uniform dispersion of additives. A twin-screw extruder equipped with a pressure device at the vent port is preferred.

[0025] In terms of extruder operating conditions, a lower melt viscosity of the resin is preferable to increase devolatilization efficiency. Furthermore, a higher melt-mixing temperature within the extruder system is preferable. However, if the temperature is too high, discoloration may occur. Because thermal decomposition may occur, it is necessary to process the product at the highest possible and appropriate temperature. Yes, it exists. The appropriate melting temperature depends on the type of resin, the glass transition temperature of the resin, the molecular weight, the melt viscosity, etc. However, 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, which can improve productivity. Both methods can suppress the thermal decomposition of resin, preventing discoloration, a decrease in mechanical strength due to molecular weight reduction, and heat loss. This can further prevent the generation of decomposition gases, etc. From the perspective of further enhancing this effect, The melting temperature is more preferably 210°C to 300°C, and particularly preferably 220°C to 290°C.

[0026] It is melted in an extruder, preferably via a gear pump, and filtered as needed. The resin is extruded, for example, in strand form from a die head, and after cooling and solidification, it is processed using a rotary method. The strands are cut into pellets using a cutter or similar tool. Cooling of the strands is typically done by air or water. This is done in various ways, and in the case of air cooling, the air used is filtered to remove foreign matter from the air using a HEPA filter or the like. It is preferable to use clean air to prevent contamination from airborne contaminants. Also, when used in water cooling systems... The water is first treated to remove metal components using ion exchange resin, and then filtered to remove foreign matter from the water. It is preferable to use clean water from which impurities have been removed.

[0027] The resulting pelletized resin can be further processed by conventionally known methods. For example, Methods include processing the film and molding using molds. The following methods are limited to the following: Although it is not something that is done in this way, for example, when making a film, a common manufacturing method is to dissolve the resin. One method involves melting the material, forming it into a sheet, and then stretching it as needed to increase its strength or for other purposes. .

[0028] For example, the aforementioned resin is melt-extruded from a die using an extruder, and the molten film is cooled. The film is cooled and solidified on a roll to obtain an unstretched film. In this case, the flatness of the film is improved. Therefore, it is preferable to improve the adhesion between the molten sheet and the cooling roll, and methods such as electrostatic application adhesion and liquid A body coating and adhesion method can also be used. If the film is to be left as is and not stretched, the roll temperature and Thickness runout can be reduced by adjusting the extrusion speed, etc. Furthermore, production efficiency and thickness runout can be improved. Furthermore, it is also possible to stretch the unstretched film obtained for purposes such as reducing roughness. Stretching the film in the longitudinal direction can be achieved by utilizing the difference in peripheral speed of the rolls, and stretching the film in the transverse direction. This can be achieved using a tenter-type stretcher, etc., in the direction of the hand. It is also possible to produce a biaxially oriented film. Furthermore, a simultaneous biaxial stretching method is also possible. The stretching temperature and stretching ratio vary depending on the type of resin, but preferably 70°C The temperature is 200°C, more preferably in the range of 80 to 160°C, and the stretching ratio is 7 times in one direction. The following range is preferable, up to 5 times. There is no particular lower limit, but it is 1 time. After that, the tree Depending on the type of fat, it is possible to obtain a stretched film by applying appropriate heat treatment or other methods.

[0029] It is also possible to use various additives at any stage of the resin processing described above. For example, When added before or during melt extrusion, such as when creating a lett or film, It is preferable due to its good dispersion efficiency. Examples of additives include catalyst deactivators and heat stabilizers used in resin manufacturing. Neutralizing agents, UV absorbers, light stabilizers, particles, mold release agents, dyes, pigments, lubricants, plasticizers, and other similar substances. Examples include compatibilizers and flame retardants.

[0030] Any form of substrate can be used, for example, film, sheet Examples include sheets, plates, molded bodies, etc. The thickness is also arbitrary, but for example, if it is a film, handling From the viewpoint of ease of processing, productivity, and workability, the particle size should be 1 to 500 μm, preferably 10 to 300 μm, and more preferably 10 to 300 μm. The thickness is in the range of 20 to 250 μm. Also, if it is a molded product, from the standpoint of weight, 0 In the range of 0.05 to 10 mm, preferably 0.1 to 6 mm, more preferably 0.2 to 4 mm be.

[0031] <Functional Layer> On at least one surface of a polycarbonate resin substrate containing a heterobicyclo ring structure It has a functional layer. A functional layer is a layer that imparts a function to the constituent laminate, for example, a base material and An adhesion-enhancing layer to firmly bond the hard coat layer, and a band to provide antistatic properties. Examples include electrical insulation layers. During the investigation, a polycarbonate resin substrate containing a heterobicyclo ring structure was found to be used. In some cases, the adhesion to the hard coat layer may be inferior to that of a typical polycarbonate resin substrate. It was observed. Therefore, a method was proposed that can ensure adhesion even with various types of substrates and hard coat layers. It was determined that a plan was needed, and that a functional layer be laminated between the substrate and the hard coat layer. I thought about it. Furthermore, it's difficult to impart antistatic properties to the substrate or hard coat layer. For example, When an antistatic agent is added to a polycarbonate substrate to impart antistatic properties, It has the drawback of being difficult to segregate the agent on the surface, resulting in insufficient antistatic properties. If you try to achieve antistatic performance by using an antistatic agent, the polycarbonate substrate itself becomes brittle. However, depending on the application, it may not be suitable. On the other hand, the hard coat layer contains antistatic When adding an antistatic agent to impart antistatic properties, the interaction with the components constituting the hard coat layer is important. We found that we needed to consider the properties of the material, which narrowed the range of material choices. In addition, antistatic agents Inclusion of this substance in the hard coat layer may reduce the properties of the hard coat layer, such as scratch resistance. Furthermore, for applications requiring processability (bending, folding, stretching, etc.), Because the conductive network breaks down after construction, it is difficult to ensure antistatic properties. That's what I found out. In light of the above situation, an adhesion-enhancing layer or antistatic layer between the substrate and the hard coat layer may be used. We discovered that these problems could be solved by incorporating a functional layer, which led to the invention of this invention.

[0032] The functional layer (adhesion-improving layer) intended to provide adhesion is constructed using conventionally known resins. It is possible. Specific examples of resins include acrylic resin, polyester resin, and urethane. Resins, polyvinyl resins (polyvinyl alcohol, vinyl chloride-vinyl acetate copolymer, etc.), etc. These include acrylic resin and polyethylene, which are particularly good from the perspective of improving adhesion. Polyester resins and urethane resins are preferred, and acrylic resins and polyester resins are particularly preferred. These resins may be used individually or in combination of two or more types.

[0033] Acrylic resin is a polymer of polymerizable monomers, including (meth)acrylic monomers. Examples of acrylic resins include homopolymers and copolymers of (meth)acrylic monomers. Body, (meth)acrylic monomers and polymerizable monomers other than (meth)acrylic monomers Examples include copolymers of the same material. Acrylic resins are composed of these polymers and other polymers (e.g., polyester, polyurethane, etc.). ) may be a copolymer with ). Such copolymers may be, for example, block copolymers, globular copolymers. It is a raft copolymer. Alternatively, polymerizable monomers are polymerized in a polyester solution or dispersion. This also includes polymers (and sometimes mixtures of polymers) obtained by [processing]. Polymers obtained by polymerizing polymerizable monomers in a solution or dispersion of uretan (in some cases This also includes polymer mixtures. Similarly, polymerizable polymers in solutions or dispersions of other polymers. This also includes polymers (and sometimes polymer mixtures) obtained by polymerizing nomers. In this invention, "(meth)acrylic" refers to "acrylic" and "methacrylic," and "(Meth)acrylate" refers to either or both "acrylate" and "methacrylate". It means to include.

[0034] The polymerizable monomers mentioned above are not particularly limited, but some representative compounds include, for example, For example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, cyanoacrylate Carboxyl group-containing monomers such as traconic acid and their salts; 2-hydroxyethyl ( (T) Acrylate, 2-Hydroxypropyl (meth)acrylate, 4-Hydroxybutyl (meth)acrylate, monobutylhydrochloride, monobutylhydroxyyl acrylate Hydroxyl group-containing monomers such as conates; methyl (meth)acrylate, ethyl (meth)acrylate Rate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl Alkyl(meth)acrylates such as sil(meth)acrylate and lauryl(meth)acrylate Rates; (meth)acrylamide, diacetone acrylamide, N-methylol acrylic Nitrogen-containing monomers such as amides and (meth)acrylonitrile; styrene, α-methylstyrene Styrene compounds such as divinylbenzene and vinyltoluene, vinyl propionate, vinegar Vinyl esters such as vinyl acid; γ-methacryloxypropyltrimethoxysilane, vinyl Silicon-containing monomers such as trimethoxysilane; phosphorus-containing vinyl monomers; vinyl chloride, chloride Examples include vinyl halides such as pyridene and conjugated dienes such as butadiene.

[0035] Polyester resins primarily consist of polycarboxylic acids and polyhydroxy compounds. Examples include those consisting of the following. Polycarboxylic acids include terephthalic acid, isophthalic acid, and Luthophthalic acid, 4,4'-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-Naphthalenedicarboxylic acid, 2,6-Naphthalenedicarboxylic acid, and 2,7-Naph Tallendicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoteref Taric acid, 5-sodium sulfisophthalic acid, adipic acid, azelaic acid, sebaic acid, Decanedicarboxylic acid, glutaric acid, succinic acid, trimellitic acid, trimesic acid, pyromelitic acid phthalic acid, trimellitic anhydride, phthalic anhydride, monopotassium salt of trimellitic acid and related Examples include ester-forming derivatives of ethyleneglycanide. Examples of polyvalent hydroxy compounds include ethyleneglycanide. 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propylene Panediol, 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 Polyethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol Coal, polytetramethylene glycol, polytetramethylene oxide glycol, dimethyl Tyrolpropionic acid, glycerin, trimethylolpropane, dimethylolethylsulfate Examples include sodium phosphate and potassium dimethylolpropionate. From the above, select one or more as appropriate, and use a conventional polycondensation reaction to produce a polyester resin. You can combine them.

[0036] Urethane resin is a polymer compound that has urethane bonds within its molecule, and is a typical example. It is synthesized by the reaction of a polyol and a polyisocyanate compound. (Urethane resin) Chain extenders may be used when synthesizing the product. Polyols used to obtain urethane resin include polycarbonate polyols. Polyether polyol, polyester polyol, polyolefin polyol, Examples include acrylic polyols. Among these, polycarbonate polyols are considered to have good adhesion. Polyols and polyester polyols are preferred, and polycarbonate polyols are more preferred. These compounds may be used individually or in combination of two or more.

[0037] Polycarbonate polyols are formed by the reaction of polyhydric alcohols with carbonate compounds (de-algae formation). It is obtained by the glycol reaction. Examples of polyhydric alcohols include ethylene glycol and 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-cyclohexanedimethano 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol , 1,10-decanediol, neopentyl glycol, 3-methyl-1,5-pentane Examples include diols and 3,3-dimethylolheptane. Carbonate compounds include Dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate Examples include carbonates. A specific example of a polycarbonate polyol is poly(1,6-hexylene)carbonate. Examples include poly(3-methyl-1,5-pentylene) carbonate.

[0038] Examples of polyether polyols include polyethylene glycol and polypropylene glycol. Polyethylene propylene glycol, polytetramethylene ether glycol, poly Examples include hexamethylene ether glycol.

[0039] Polyester polyols include polycarboxylic acids or their acid anhydrides and polycarboxylic acids. The reaction with the compound, or a derivative unit of a lactone compound such as polycaprolactone. Examples include those containing t. Examples of polycarboxylic acids include malonic acid, succinic acid, glutaramine. uric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, tereic acid Examples include phthalic acid and isophthalic acid. Polyhydric alcohols include ethylene glycol. , diethylene glycol, triethylene glycol, propylene glycol, dipropyl Glycol, tripropylene glycol, butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol , 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2 -Methyl-2-propyl-1,3-propanediol, 1,8-octanediol, 2, 2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol L, 2,5-dimethyl-2,5-hexanediol, 1,9-nonanediol, 2-methyl Lu-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-Butyl-2-hexyl-1,3-propanediol, cyclohexanediol, bis Hydroxymethylcyclohexane, dimethanolbenzene, bishydroxyethoxybene Examples include zen, alkyldialkanolamines, and lactone diols.

[0040] Considering adhesion performance, polyester polyol and polycarbonate are suitable as polyols. Nat polyols are preferred.

[0041] Examples of polyisocyanate compounds used to obtain urethane resin include tolylene. Isocyanates, xylylene diisocyanate, methylenediphenyl diisocyanate, Phenylene diisocyanate, naphthalene diisocyanate, toridine diisocyanate Aromatic diisocyanates such as α,α,α',α'-tetramethylxylylene diisocyanate Aliphatic diisocyanates having aromatic rings such as nates; methylene diisocyanates, prophine Diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate Aliphatic diisocyanates such as phosphates and hexamethylene diisocyanates; cyclohexane Diisocyanates, methylcyclohexane diisocyanates, isophorone diisocyanates Dicyclohexylmethane diisocyanate, isopropylidene dicyclohexyl di Examples include alicyclic diisocyanates such as socianates. These can be used individually. You may also use two or more types in combination.

[0042] Examples of polyvinyl resins include polyvinyl alcohol. It has a coal portion, for example, partially acetate polyvinyl alcohol. This includes modified compounds such as polyvinyl alcohols and butyralized compounds, as well as conventionally known polyvinyl alcohols. It can be used. The degree of polymerization of polyvinyl alcohol is not particularly limited, Typically, a degree of polymerization of 100 or more, preferably in the range of 300 to 40,000, is used. If the value is less than 100, the water resistance of the antistatic layer may decrease. Also, polyvinyl alcohol The degree of saponification of the mol is not particularly limited, but is 70 mol% or more, preferably 70-9%. It is a polyvinyl acetate saponified product in the range of 9.9 mol%.

[0043] A functional layer (antistatic layer) intended to provide antistatic properties contains an antistatic agent. This reduces the surface resistance and prevents the adhesion of foreign matter such as dust. Conventional known materials can be used as antistatic agents. For example, polymer-type bands Antistatic agents, surfactant-based low molecular weight antistatic agents, carbon-based antistatic agents, metal-based bands Examples include antistatic agents. Among these, from the standpoint of durability, low molecular weight antistatic agents are... In the case of antistatic agents, this can lead to loss of antistatic properties due to bleed-out, deterioration of appearance, or deterioration of durability. From this perspective, it becomes difficult to maintain long-term antistatic properties, and considering heat resistance and moisture resistance, it becomes low. Because molecular types have limited applications, polymer-type antistatic agents and carbon-based antistatic agents are used. Antistatic agents, especially metal-based antistatic agents, are preferred. If adhesion is also to be considered, other resins may be used in combination. Due to compatibility with fats, high-molecular-weight antistatic agents are more preferable. Furthermore, after processing ( From the perspective of being able to exhibit antistatic properties even in bending, folding, stretching, etc., Molecular-type antistatic agents or carbon-based antistatic agents are preferred, and transparency is also important. If so, a polymer-type antistatic agent is more preferable. Note that polymer-type refers to a number average This refers to compounds with a molecular weight of 1,000 or more.

[0044] Examples of polymer-type antistatic agents include compounds having an ammonium group, and conductive compounds. Examples include organic polymers, polyether compounds, compounds containing sulfonic acid groups, and betaine compounds. This can be achieved. Among these, compatibility with other compounds used in combination in the antistatic layer and antistatic performance are important. From this viewpoint, compounds having an ammonium group or conductive organic polymers are more preferable. From the perspective of properties and the fact that the antistatic properties do not change easily even after a hard coat layer is applied, ammonia Compounds having a nium group are more preferred.

[0045] A compound containing an ammonium group is a compound that has an ammonium group in its molecule. Examples include aliphatic amines, alicyclic amines, and ammonium compounds of aromatic amines. In compounds having a type of ammonium group, the ammonium group is a counterion It is preferable that it is incorporated into the main chain or side chains of the polymer rather than as a separate entity. Examples of compounds include those containing an ammonium group or a precursor group of an ammonium group such as an amine. The addition polymerizable monomer is polymerized, and if necessary, the ammonium precursor group is added. Examples include polymer compounds that have been converted to ammonium groups. Addition polymerizable monomers containing a precursor group of a mononium group or an ammonium group are single-component monomers. Polymerization may be carried out in isolation, copolymerization of two or more monomers may be carried out, or copolymerization with other monomers may be carried out. stomach.

[0046] As a compound containing an ammonium group, it has excellent antistatic properties and heat stability. Compounds having a pyrrolidinium ring are also preferred. The two substituents bonded to the elementary atom are, independently, alkyl groups, phenyl groups, etc. Furthermore, these alkyl and phenyl groups may be substituted with the following groups: Substitutable Examples of such groups include hydroxyl groups, amide groups, ester groups, alkoxy groups, and phenoxy groups. naphthoxy group, thioalkoxy, thiophenoxy group, cycloalkyl group, trialkyl It is an ammonium alkyl group, a cyano group, and a halogen. Also, it is bonded to the nitrogen atom. The substituents may be chemically bonded, and a group in which two substituents are chemically bonded is For example, -(CH2) m -(m=an integer from 2 to 5), -CH(CH3)CH(CH3)- , -CH=CH-CH=CH-, -CH=CH-CH=N-, -CH=CH-N=C-, Examples include -CH2OCH2- and -(CH2)2O(CH2)2-.

[0047] Polymers having a pyrrolidinium ring include, for example, diallylamine derivatives, which are radicalized. It is obtained by cyclization polymerization using a catalyst. Diallylamine derivatives and polymerizable compounds Compounds having carbon-carbon unsaturated bonds may be used as copolymerization components. Polymerization is carried out in a polar solvent ( Water, methanol, ethanol, isopropanol, formamide, dimethylformamide Hydrogen peroxide, benzoyl peroxide, tertiary nitrile, etc. in dioxane, acetonitrile, etc. This can be carried out using polymerization initiators such as butyl peroxide and by known methods, but is not limited to this. It is not something that can be done.

[0048] The counterion of the ammonium group in the above-mentioned ammonium group compound. Examples of anions that become (n) include halogen ions, sulfonates, phosphates, and n Examples of ions include trate, alkyl sulfonate, and carboxylate.

[0049] The number-average molecular weight of compounds having an ammonium group is preferably 1,000 to 500. 00, more preferably 2,000 to 350,000, even more preferably 5,000 to 20 It is 0,000. If the number average molecular weight is 1,000 or more, the strength and heat stability of the coating film are Superior. If the number average molecular weight is 500,000 or less, for forming an antistatic layer. The coating solution has low viscosity, resulting in good handling and application properties.

[0050] As the conductive organic polymer, known materials can be used, for example, polythio Phenol-based, polyaniline-based, polypyrrole-based, polyacetylene-based, polyphenylene sulfur Examples include phosphates, etc. Among these, polythiophenes (polythiophene or polythio) are particularly noteworthy. Offen derivatives offer both high transparency and high conductivity, as well as resistance to discoloration and coating. It is preferable because it easily exhibits the desired performance. Among polythiophenes, poly(3,4-ethyl) A compound formed by combining rangeoxythiophene with polystyrene sulfonic acid exhibits conductive properties. From this perspective, it is particularly preferable. Conductive organic polymers exhibit high conductivity and low humidity dependence. Furthermore, it is desirable in that it can be expected to be used in a variety of applications.

[0051] Examples of polyether compounds include polyethylene oxide and polyether esters. Examples include amides and acrylic resins having polyethylene glycol as a side chain.

[0052] In compounds containing a sulfonic acid group, the sulfonic acid group is neutralized by a neutralizing agent to form a salt. It may be as follows. Compounds having a sulfonic acid group include polystyrene sulfonic acid and Compounds having multiple sulfonic acid groups in the molecule, such as bicarbonate salts, are preferred.

[0053] Examples of low-molecular-weight surfactant-based antistatic agents include anionic surfactants and cationic surfactants. Examples include ionic surfactants, amphoteric surfactants, and nonionic surfactants. In particular, from the perspective of improving antistatic properties, and compatibility with various resins used in combination within the antistatic layer, In terms of solubility, anionic surfactants and nonionic surfactants are preferred, in particular Anionic surfactants are preferred.

[0054] Examples of anionic surfactants include alkyl sulfonates and alkylaryls Sulfonic acid types such as sulfonates, ester sulfons, alkyl phosphates or so Phosphate-type salts, polyoxyalkylene alkyl ether phosphates or their salts, etc. , sulfate ester type such as alkyl sulfate salts, alkyl ether sulfate salts, Examples include carboxylate salts such as chloric acid fatty acid salts. Among these, those with excellent antistatic properties From this perspective, the sulfonic acid type is preferred.

[0055] Examples of sulfonic acid type anionic surfactants include decyl sulfonates and dodecyl Sulfonates, tetradecyl sulfonates, hexadecyl sulfonates, octadecyl Alkyl sulfonates such as ruhonates, butylbenzenesulfonates, hexylbenzene Sulfonates, octylbenzenesulfonates, decylbenzenesulfonates, dodecyl Benzenesulfonate, tetradecylbenzenesulfonate, hexadecylbenzenesulfonate honate, octadecylbenzenesulfonate, dibutylnaphthalenesulfonate, tri Alkylaryl sulfonates such as isopropylnaphthalene sulfonate, dibutylsulfonate SF6 fosuccinate, dioctyl sulfosuccinate, dodecyl sulfoacetate Esters such as ester salts, nonylphenoxypolyethylene glycol sulfoacetate salts A prime example is a sulfonate salt. Among these, in terms of its excellent antistatic properties, The number of carbon atoms in the kill group is 8 or more, preferably 10 to 22, and more preferably in the range of 12 to 18. Furthermore, metal salts are preferred as the salt, and lithium, sodium, and potassium are particularly preferred. Alkali metal salts such as the above are more preferred, and sodium salts are even more preferred. Types include bands. From the viewpoint of static electricity prevention, alkyl sulfonates are preferred.

[0056] Examples of phosphate-type anionic surfactants include butyl phosphate ester and butyl phosphorus. Acid ester salts, hexyl phosphate esters, hexyl phosphate ester salts, octyl phosphate Stel, octyl phosphate salt, decyl phosphate, decyl phosphate salt, Lauryl phosphate ester, lauryl phosphate salt, tetradecyl phosphate ester, tetradecyl phosphate Tradecyl phosphate salts, hexadecyl phosphates, hexadecyl phosphate esters Alkyl phosphates such as stearyl phosphate salts, stearyl phosphate esters, and stearyl phosphate ester salts Polyoxyethylene butyl ether or its salts, polyoxyethylene butyl ether phosphate, polyoxyethylene Polyethylene butyl ether phosphate salt, polyoxyethylene hexyl ether phosphate Polyoxyethylene hexyl ether phosphate salt, polyoxyethylene oxy Polyoxyethylene octyl ether phosphate salts, Polyoxyethylene decyl ether phosphate ester, polyoxyethylene decyl ether Phosphate ester salts, polyoxyethylene lauryl ether phosphate esters, polyoxyethylene Teylene lauryl ether phosphate salt, polyoxyethylene tetradecyl ether Polyoxyethylene tetradecyl ether phosphate salt, polyoxy Ethylene hexadecyl ether phosphate, polyoxyethylene hexadecyl ether Polyphosphate ester salt, polyoxyethylene stearyl ether phosphate, polyoxy ethylene stearyl ether phosphate salt, polyoxypropylene octyl ether Polyphosphate ester, polyoxypropylene octyl ether phosphate salt, polyoxypropylene Cypropylene decyl ether phosphate, polyoxypropylene decyl ether phosphate Acid ester salts, polyoxypropylene lauryl ether phosphate esters, polyoxypropylene Polyoxyalkylene alkyl ethers such as pyrene lauryl ether phosphate salts Examples include nitrate esters or their salts.

[0057] Among these, alkyl phosphate stands out from the perspective of its performance as a surfactant and its antistatic properties. Ester salts or polyoxyalkylene alkyl ether phosphate esters or their salts are preferred. It's nice.

[0058] Furthermore, with respect to alkyl phosphate salts, the number of carbon atoms in the alkyl group is preferably 4 or more. The range is 4 to 22, more preferably 6 to 12, and polyoxyalkylene With regard to kill ether phosphate esters or their salts, the alkyl group has 4 or more carbon atoms, preferably. The salt is in the range of 6 to 22, more preferably 8 to 18. Alkali metal salts and amine salts are preferred, and alkali metal salts such as lithium, sodium, and potassium are particularly preferred. Alkylamine salts and alcoholamine salts are more preferred, as are sodium salts and monoethanolamine salts. Amine salts are even more preferred.

[0059] Examples of cationic surfactants include alkylammonium salts and alkylbenzyl Quaternary ammonium salts such as ammonium salts, N-methylbishydroxyethylamine lipids Examples include amine salts such as fatty acid esters and hydrochlorides. Among these, those with superior antistatic properties are particularly noteworthy. From this viewpoint, the quaternary ammonium salt type is preferred.

[0060] Examples of quaternary ammonium salt type cationic surfactants include octyltrimethyl Ammonium salts, decyltrimethylammonium salts, lauryltrimethylammonium salts Tetradecyltrimethylammonium salt, hexadecyltrimethylammonium salt, Thearyltrimethylammonium salt, octyldimethylethylammonium salt, decyl Methylethylammonium salt, lauryldimethylethylammonium salt, tetradecyldi Methylethylammonium salt, hexadecyldimethylethylammonium salt, octyl ethylammonium salt, lauryltriethylammonium salt, hexadecyltriethyl Ammonium salts, alkylammonium salts such as didecyldimethylammonium salt, octyl Didimethylbenzylammonium salt, Decyldimethylbenzylammonium salt, Lauryl Dimethylbenzylammonium salt, tetradecyldimethylbenzylammonium salt, hex Sadecyldimethylbenzylammonium salt, stearyldimethylbenzylammonium salt Alkyl, tributylbenzylammonium salt, trihexylbenzylammonium salt, etc. Examples include rubenzylammonium salts.

[0061] Among these, alkylammol is considered to have the following properties from the perspective of its performance as a surfactant and its antistatic properties. A nium salt is preferred.

[0062] Furthermore, the longest number of carbon atoms in the alkyl group is usually 4 or more, preferably 6 to 22, Preferably in the range of 8 to 18. Also, the counterion of the ammonium group. Examples of (n) include halogen ions, sulfonates, sulfates, phosphates, Examples include nitrates and carboxylates, and among these, those with good antistatic properties. From this perspective, chlorides, sulfonates, and sulfates are preferred.

[0063] Examples of amphoteric surfactants include betaine-type surfactants such as alkyl betaines, and alkyl Examples include amino acid types such as ammonium fatty acid salts and amine oxide types such as alkylamine oxides. Among these, the betaine type is preferred in terms of its superior antistatic performance. It seems so.

[0064] Examples of betaine-type amphoteric surfactants include octyldimethylaminoacetic acid Betaine, Decyldimethylaminoacetic acid betaine, Lauryldimethylaminoacetic acid betaine, Tradecyldimethylaminoacetic acid betaine, hexadecyldimethylaminoacetic acid betaine, s Tearyldimethylaminoacetic acid betaine, octanoic acid amidopropyl betaine, decanoic acid Midopropyl betaine, lauryl amidopropyl betaine, tetradecanoate amide pro Pyrubbetaine, Hexadecanoamidepropyl betaine, Stearamidepropyl betaine Examples include Tine, etc.

[0065] Examples of nonionic surfactants include polyhydric alcohols such as glycerin and sugars and lipids. Polyoxyethylene alkyl ethers and polyoxyethylenes are ester-type ethers in which ester compounds are formed. Ether-type fatty acids such as ethylene alkylphenyl ethers, fatty acids, and polyhydric alcohol fatty acids Ester / ether type with alkylene oxide added to tel, hydrophobic group and hydrophilic group are amine Examples include amide types such as fatty acid alkanolamides, which are linked by a bond. In particular, considering heat resistance, ester type, ether type, and ester-ether type are Preferably, and considering antistatic performance, the ether type is preferred.

[0066] Examples of ester-type and ester / ether-type nonionic surfactants include glycero mono(di)laurate, glycerol mono(di)stearate, glycerol, glyc Cerol mono(di)oleate, diglycerol mono(di)stearate, triglycerol Glycerin fatty acid esters such as mono(di)stearate, polyoxyethylene glycerin Roll mono(di)laurate, polyoxyethylene glycerol mono(di)stearate , polyoxypropylene glycerol mono(di)laurate, polyoxypropylene Cerol mono(di)stearate, polyoxybutylene glycerol mono(di)laurate Polyoxyalkylene such as polyoxybutylene glycerol mono(di)stearate. Glycerin fatty acid ester, polyoxyethylene mono(di)laurate, polyoxyethylene Lenmono(di)stearate, polyoxyethylene mono(di)oleate, polyoxyprop Polypropylene mono(di)laurate, polyoxypropylene mono(di)stearate, etc. Xyalkylene fatty acid ester, sorbitan mono(di)laurate, sorbitan mono(di ) Palmitate, sorbitan mono(di)stearate, sorbitan mono(di)oleate, etc. Sorbitan fatty acid ester, polyoxyethylene sorbitan monolaurate, polyoxy Polyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate Polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan mo Noolate, polyoxyethylene sorbitan triolate, polyoxypropylene sorbate Polyoxypropylene monolaurate, polyoxypropylene sorbitan monostearate, etc. Examples include alkylene sorbitan fatty acid esters.

[0067] Among these, from the perspective of compatibility with various resins used in combination in the antistatic layer and antistatic properties , glycerin fatty acid ester, polyoxyalkylene glycerin fatty acid ester, polio Xyalkylene fatty acid esters are preferred, and are fatty acid esters having a glycerol skeleton. Glycerin fatty acid esters and polyoxyalkylene glycerin fatty acid esters are more preferable.

[0068] Furthermore, among these, alkyl groups are superior in terms of antistatic properties and compatibility. The carbon number is 8 or more, preferably in the range of 10 to 22, and more preferably in the range of 12 to 18. ru.

[0069] Examples of ether-type nonionic surfactants include polyoxyethylene lauryl ether. Polyoxyethylene isodecyl ether, polyoxyethylene cetyl ether, Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxy ethylene octyldodecyl ether, polyoxypropylene lauryl ether, polio Xypropylene cetyl ether, polyoxypropylene stearyl ether, polyoxy Propylene oleyl ether, polyoxybutylene lauryl ether, polyoxybutylene Cetyl ether, polyoxybutylene stearyl ether, polyoxybutylene oleate Polyoxyalkylene alkyl ethers such as ethers, polyoxyethylene triphenyl Polyoxyethylene tribenzylphenyl ether, polyoxyethylene Examples include polyoxyalkylene phenyl ethers such as ethylene distyrene phenyl ether. It is possible.

[0070] Among these, polyoxyalkylene alkyl ethers are preferred from the viewpoint of antistatic properties. Furthermore, in terms of excellent antistatic properties and compatibility, the number of carbon atoms in an alkyl group is 8. The above values ​​are preferably in the range of 10 to 22, and more preferably in the range of 12 to 18.

[0071] The aforementioned low-molecular-weight surfactant-based antistatic agents can be used alone or in combination of two or more types. They can be used in combination. For example, an anionic surfactant and a nonionic surfactant. While ionic surfactants are a preferred example, there are two types of anionic surfactants. You may use it.

[0072] Conventional known materials can be used as carbon-based antistatic agents, for example, Examples include carbon nanotubes, graphite, and carbon black. Carbon nanotubes are preferred because they easily maintain transparency, and single-walled carbon nanotubes Either a single layer or a multi-walled carbon nanotube would suffice. From the perspective of increasing conductivity, single layer Layered carbon nanotubes are more preferable.

[0073] Conventional known materials can be used as metal-based antistatic agents, for example, silver copper, nickel and other metal powders and metal fibers, tin oxide, zinc oxide, indium oxide, oxide Examples include metal oxides such as indium tin and antimony tin oxide. When forming an anti-static layer by coating, metal oxides are preferred from the viewpoint of ease of application to paint. .

[0074] Even when the functional layer is an antistatic layer, various resins used in the adhesion-enhancing layer are used in combination. This is also a desirable form. By using various resins in combination, the appearance can be improved, and the base material and hard coating can be improved. Improved adhesion to the layer can be obtained. Among the resins mentioned above, acrylic resin and polyester resin Fat and urethane resin are preferred, and acrylic resin or polyester resin is particularly preferred.

[0075] It is also possible to include compounds derived from crosslinking agents to strengthen the functional layer. For this purpose, known materials can be used, for example, melamine compounds, oxazophosphates Compounds, isocyanate compounds, epoxy compounds, carbodiimide compounds, silane compounds Examples include Pring compounds, hydrazide compounds, and aziridine compounds. Melamine compounds, isocyanate compounds, epoxy compounds, oxazoline compounds, Rubodiimide compounds and silane coupling compounds are preferred, and further improve durability. From this perspective, melamine compounds, oxazoline compounds, isocyanate compounds and epoxy A compound is more preferable. Also, from the viewpoint of improving adhesion, an oxazoline compound or epoxy Xyl compounds are more preferred. These crosslinking agents can be used individually or in combination of two or more. This is also good. Using two or more types together can further improve adhesion and durability, resulting in better performance. ru.

[0076] The functional layer contains particles to provide slipperiness, blockage prevention, and hardness. This is possible. Various conventionally known particles can be used as particles, for example, Silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate Calcium, magnesium phosphate, kaolin, aluminum oxide, zirconium oxide, oxide Inorganic particles such as titanium, acrylic resin, styrene resin, urea resin, phenolic resin, epoxy Examples include organic particles such as resins and benzoguanamine resins. Among these, those that impart hardness... In terms of being able to do so, inorganic particles are preferred, and when forming a functional layer by coating, the coating liquid Considering stability in the given state, silica particles are preferable. One type of particle is acceptable, but two types are also preferable. You may use more than one of the above types in combination.

[0077] The functional layer may further contain, as necessary, an antifoaming agent, to the extent that it does not impair the spirit of the present invention. Coatability modifiers, thickeners, organic lubricants, UV absorbers, antioxidants, foaming agents, dyes, pigments It may contain additives such as the following.

[0078] When the functional layer is an adhesion-enhancing layer, the proportion of resin in 100% by mass of the functional layer is used It depends on the type, so it's not a general rule, but for example, 1% by mass or more, preferably 10% by mass. More preferably, the amount is in the range of 20% by mass or more, and even more preferably 30% by mass or more. There is no particular upper limit, but it is 100% by mass. If it also serves as an antistatic layer, it is preferably 99% by mass. The following range is more preferably 90% by mass or less, and even more preferably 80% by mass or less. By using it within the above range, good adhesion between the substrate and the hard coat layer is achieved. The docote layer can be firmly maintained.

[0079] When the functional layer is an antistatic layer, the proportion of antistatic agent in 100% by mass of the functional layer is It depends on the type of antistatic agent, so it's not a general rule, but for example, 0.1% by mass or more is preferable. The range is 1% by mass or more, more preferably 3% by mass or more, with no particular upper limit. This is expressed in percent. Other materials used in combination to improve adhesion to the substrate or to improve the appearance of the functional layer. The proportion can also be increased, in which case it is preferably 0.1 to 90% by mass, more preferably More preferably 1 to 80% by mass, more preferably 3 to 70% by mass, and especially preferably 10 to 60% This is within the range of mass percent. If the proportion of antistatic agent is within the above range, the antistatic layer will be sufficiently charged. It is easy to add protective features, and it also has good durability.

[0080] The thickness of the functional layer is not particularly limited, but is preferably 0.01 to 20 μm, more preferably 0.05 to 5 μm, more preferably in the range of 0.1 to 3 μm, particularly preferably in the range of 0.1 to 0 The range is 0.8 μm. If the thickness of the functional layer is within the above range, the desired adhesion properties, or This makes it easier to achieve antistatic properties. The thickness of the functional layer is determined by cross-sectional observation using an electron microscope or similar device.

[0081] <Hard coat layer> Polycarbonate resin substrates containing heterobicyclo ring structures alone may not provide sufficient abrasion resistance depending on the application. In some cases, properties such as scratch resistance may be insufficient, so a hard coat layer is added to compensate for these shortcomings. The coat layer can be formed using conventionally known methods such as active energy ray curing or thermal curing. It is possible. Because it can be cured in a short time and causes little damage to the substrate, active energy is... A hard coat layer formed by Lugie wire curing is preferred.

[0082] Conventional known materials can be used as active energy ray curable compounds, For example, (meth)acrylate is a suitable material. There are no particular limitations; monofunctional (meth)acrylates, difunctional (meth)acrylates, trifunctional or more Any of the above polyfunctional (meth)acrylates may be used. (Meth)acrylates are hard Commercially available chemical resin materials can also be used. (Meth)acrylate is the subject of this invention. Other components may be included as long as they do not impair the target. Among these, particularly Due to its excellent abrasion resistance, it is a bifunctional or trifunctional (meth)acrylate. (Meth)acrylates are preferred, and trifunctional or more functional (meth)acrylates are particularly preferred. Examples of related materials include (meth)acrylic, (meth)acrylate, epoxy (meth)acrylate Uses such as urethane (meth)acrylate, silicone (meth)acrylate, etc. It is also possible to do so. Among these, (meth)acrylic (meth)acrylate and urethane (meth Acrylate is preferred because its hardness can be adjusted. In addition, it is particularly good in terms of moldability and elongation. When considering properties such as phosphate, (meth)acrylic (meth)acrylate is preferred.

[0083] Examples of monofunctional (meth)acrylates include methyl (meth)acrylate and ethyl (meth)acrylate. Acrylate, butyl (meth)acrylate, propyl (meth)acrylate, n-butyl i-butyl(meth)acrylate, i-butyl(meth)acrylate, t-butyl(meth)acrylate Rate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, Uryl (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, diethylaminoethyl (meth)acrylate (T) Acrylate, Tricyclodecane (meth)acrylate, Polyethylene Glycol Mo No(meth)acrylate, cyclohexyl(meth)acrylate, tetrahydrofurfurfur Dicyclopentanyl(meth)acrylate, dicyclopentanyl(meth)acrylate, dicyclopentenyl Isobornyl(meth)acrylate, allyl(meth)acrylate 2-Ethoxyethyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate Mono(meth)acrylates such as oxyethyl (meth)acrylate and phenyl (meth)acrylate Crilates, adducts of phthalic anhydride and 2-hydroxyethyl (meth)acrylate, etc. Examples include mono(meth)acrylate compounds.

[0084] Examples of difunctional and polyfunctional (meth)acrylates include 1,4-butanediol di( Meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexa 1,9-nonanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, Alkanediolic di(meth)acrylates such as tricyclodecane dimethylol di(meth)acrylate Acrylate, bisphenol A ethylene oxide modified di(meth)acrylate, bis Bisphenol-modified di(meth)acrylates such as phenol F ethylene oxide modified di (meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene Glycol di(meth)acrylate, urethane di(meth)acrylate, epoxy di( Examples include methacrylates.

[0085] Examples of polyfunctional (meth)acrylates with three or more functions include dipentaerythritol. Hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, ka Prolactone-modified dipentaerythritol hexa(meth)acrylate, pentaerythritol Tall tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, Ditrimethylolpropanetetra(meth)acrylate, pentaerythritol tri(meth)acrylate (T)Acrylate, Trimethylolpropane Tri(meth)acrylate, Ethylene Ox Iso-modified dipentaerythritol hexa(meth)acrylate, ethylene oxide modified Ethylene oxide-modified (meth) pentaerythritol tetra(meth)acrylate and other similar products Acrylate, isocyanurate ethylene oxide modified tri(meth)acrylate, ε- Isocyanuric acid modification such as caprolactone-modified tris(acrooxyethyl) isocyanurate Tri(meth)acrylate, pentaerythritol triacrylate hexamethylenedioxide Isocyanate urethane prepolymer, pentaerythritol triacrylate toluene Diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate Urethane (meth)acrylates such as xamethylene diisocyanate urethane prepolymer These are some examples. Among these, (meth)acrylate with four or more functions has particularly good abrasion resistance. A (meth)acrylate with six or more functional properties is preferred, and a (meth)acrylate with six or more functional properties is even more preferred. Considering the need to maintain elongation during processing, a polyfunctional (meth)acrylate with an extended alkyl chain is desirable. In particular, (meth)acrylates with four or more functional groups having extended alkyl chains are preferred, A more preferably extended (meth)acrylate with six or more functionalities is used. For example, Caprolact Modified dipentaerythritol hexa(meth)acrylate is an optimal material. In particular ( If there are two or more denaturations by caprolactone per molecule of meth)acrylate, it will extend. It is preferably 6 or more, and more preferably 6 or more for applications that particularly value elongation. Furthermore, it is also possible to use trifunctional or higher urethane (meth)acrylate. Particularly since it has good abrasion resistance, tetrafunctional or higher urethane (meth)acrylate is preferred , and hexafunctional or higher urethane (meth)acrylate is more preferred.

[0086] (Meth)acrylic (meth)acrylate is a (meth)acrylic resin having a (meth)acrylate group. The method of introducing a (meth)acrylate group into a (meth)acrylic resin includes reacting an acrylic resin having an epoxy group with a compound having a (meth)acrylate group and a carboxyl group (Method 1), reacting an acrylic resin having a carboxyl group with a compound having a (meth)acrylate group and an epoxy group (Method 2), reacting an acrylic resin having a hydroxyl group with a compound having a (meth)acrylate group and a carboxyl group (Method 3), reacting an acrylic resin having a carboxyl group with a (meth)acrylate group and a compound having a hydroxyl group (Method 4), reacting an acrylic resin having an isocyanate group with a compound having a (meth)acrylate group and a hydroxyl group (Method 5), reacting an acrylic resin having a hydroxyl group with a compound having a (meth)acrylate group and an isocyanate group (Method 6), etc. In addition, the above methods may be used in combination. In the following, a monomer having a (meth)acrylate group (radical polymerizable double bond) may be referred to as a vinyl monomer. In Method 1, the epoxy used to obtain an acrylic resin having an epoxy group group is as follows. In the following, a monomer having a (meth)acrylate group (radical polymerizable double bond) may be referred to as a vinyl monomer.

[0087] In the above Method 1, the epoxy used to obtain an acrylic resin having an epoxy group Examples of vinyl monomers having a 3, 4-Epoxycyclohexyl(meth)acrylate, 3,4-Epoxycyclohexylmeth Examples include chill (meth)acrylates. Among these, those with particularly good reactivity and material properties are also considered. Considering ease of use, glycidyl (meth)acrylate is preferred, and glycidyl Methacrylates are particularly preferred. These may be used individually or in combination of two or more. You may let them do it.

[0088] Furthermore, the compound having a (meth)acrylate group and a carboxyl group in Method 1 described above Examples include (meth)acrylic acid, carboxyethyl (meth)acrylate, and glyceryl acrylate. Sering (meth)acrylate and succinic anhydride adduct, pentaerythritol tri(meth)acrylate (T)Acrylate and succinic anhydride adduct, pentaerythritol tri(meth)acrylate Examples include adducts of phosphate and phthalic anhydride. Among these, (meth)acrylic acid, phosphate, etc. Adducts of erythritol tri(meth)acrylate and succinic anhydride are preferred, ( (T) Acrylic acid is more preferred, and acrylic acid is even more preferred. Note that (meth)acrylic acid A compound having a carboxyl group and a carboxyl group may be used alone, or two or more may be combined. It's okay to combine them.

[0089] In the above method 2, the carboxyl group used to obtain the acrylic resin having a carboxyl group Examples of vinyl monomers having a ruboxyl group include (meth)acrylic acid and carboxyl. Examples include ethyl (meth)acrylate and polybasic acid-modified (meth)acrylate. Among these, (meth)acrylic acid is preferred, and acrylic acid is more preferred. These are one type It may use only one kind, or may combine two or more kinds.

[0090] Also, in the said Method 2, a compound having a (meth) acrylate group and an epoxy group and as, for example, glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acry late glycidyl ether etc. are mentioned. Among these, glycidyl (meth) acry late is preferable. These may use only one kind, or may combine two or more kinds .

[0091] In the said Method 3, as the vinyl monomer having a hydroxyl group used for obtaining an acrylic resin having a hydroxyl group are, for example, 2-hydroxyethyl (meth) acrylate, 4 -hydroxybutyl (meth) acrylate, hydroxypropyl (meth) acrylate etc. are mentioned. These may use only one kind, or may combine two or more kinds.

[0092] Also, in the said Method 3, as the compound having a (meth) acrylate group and a carboxyl group the same ones as the compounds in the said Method 1 can be used.

[0093] In the said Method 4, as the acrylic resin having a carboxyl group, the same ones as in the said Method 2 can be used.

[0094] Also, in the said Method 4, as the compound having a (meth) acrylate group and a hydroxyl group are, for example, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth ) acrylate, hydroxypropyl (meth) acrylate etc. are mentioned. These are 1 kind may use only one kind, or may combine two or more kinds. s

[0095] In the above method 5, used to obtain an acrylic resin having an isocyanate group. Examples of vinyl monomers having an isocyanate group include isocyanate ethyl ( Examples include acrylates, etc.

[0096] Furthermore, in method 5 above, as a compound having a (meth)acrylate group and a hydroxyl group For example, compounds similar to those listed in Method 4 above can be used.

[0097] In the above method 6, the acrylic resin having a hydroxyl group is the compound in the above method 3. You can use something similar to the object.

[0098] Furthermore, in method 6, the chemical having a (meth)acrylate group and an isocyanate group Examples of compounds include isocyanate ethyl (meth)acrylate. These may be used individually or in combination of two or more types.

[0099] Among the above methods, Method 1 or Method 2 is preferred because it allows for the simultaneous introduction of hydroxyl groups. Furthermore, Method 1 is preferred because the reaction is easier to control. In Method 1, (meth)acrylic The rate group consists of the epoxy group of the acrylic resin having an epoxy group and the (meth)acrylate group. and ring-opening and addition reactions with carboxyl groups in compounds having carboxyl groups It will be introduced.

[0100] In the above method 1, the epoxy group-containing mono in the acrylic resin having epoxy groups Mer is preferably 2 of the total amount of monomers constituting the acrylic resin having epoxy groups. % by weight or more, more preferably 5% by weight or more, even more preferably 10% by weight or more, particularly preferred Or it is in the range of 15% by weight or more. There is no particular upper limit, but preferably 9% The range is 9.9% by weight or less. By using it within this range, the functional layer of the hard coat layer and Improved adhesion, scratch resistance, and hardness can be expected. However, this is not suitable for curved housing applications or decorative molding. When used for bending, folding, or stretching processes, etc. More preferably 80% by weight or less, even more preferably 70% by weight or less, and particularly preferably 5% by weight or less The range is 0% by weight or less. By using within this range, for example, the stress during decorative molding This allows for stretchability that prevents crack formation.

[0101] Furthermore, in Method 1, a compound having a (meth)acrylate group and a carboxyl group The substance is (meth)acrylate relative to the epoxy groups in an acrylic resin having epoxy groups. The proportion of compounds having a group and a carboxyl group is preferably 10 to 150 mol%. More preferably 30 to 130 mol%, even more preferably 50 to 120 mol%, particularly preferred The appropriate amount is 100-110 mol%, which is the amount that allows the reaction to proceed without excess or deficiency. By using this method, (meth)acrylate groups can be effectively introduced.

[0102] Furthermore, (meth)acrylic resins, such as the (meth)acrylic resin having the epoxy group mentioned above, The fat is a copolymer of (meth)acrylates and other vinyl monomers other than those mentioned above. It may also be the case that the polymerization reaction of these raw materials is usually radical polymerization, and conventionally known Polymerization can be carried out under these conditions.

[0103] Monomers that can be used in combination as raw materials include methyl (meth)acrylate and ester. Chil (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate Pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl ( Meth)acrylate, phenyl(meth)acrylate, methoxy(poly)ethylene glyco Methacrylate (meth)acrylate, methoxy(poly)propylene glycol (meth)acrylate T, Methoxy(poly)ethylene glycol (poly)propylene glycol (meth)acrylic Rate, octoxy(poly)ethylene glycol (meth)acrylate, octoxy(po Propylene glycol (meth)acrylate, octoxytetramethylene glycol (meth)acrylate, lauroxy(poly)ethylene glycol (meth)acrylate, (Meth)acrylates such as stearoxy(poly)ethylene glycol(meth)acrylate To; ethyl(meth)acrylamide, n-butyl(meth)acrylamide, i-butyl( meth)acrylamide, t-butyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide (T) Acrylamide, N-hydroxypropyl (meth)acrylamide, N,N-dihydro Acrylamides such as roxyethyl(meth)acrylamide; styrene, p-chlorostyrene Examples include styrene monomers such as p-bromostyrene. Only one type of these is used. You can have one, or you can combine two or more types.

[0104] (Meth)acrylic resin is produced by radical polymerization using the above-mentioned vinyl monomer raw material. It can be manufactured. Radical polymerization reactions occur in organic solvents in the presence of a radical polymerization initiator. It is preferable to carry it out in this way.

[0105] Examples of organic solvents used in radical polymerization include acetone and methyl ethyl ketone (M Ketone solvents such as EK; ethanol, methanol, isopropyl alcohol (IPA) , alcohol-based solvents such as isobutanol; ethylene glycol dimethyl ether, prop Ether-based solvents such as ethylene glycol monomethyl ether; ethyl acetate, propylene glycol Ester solvents such as 2-methyl monoether acetate and 2-ethoxyethyl acetate. Examples include aromatic hydrocarbon solvents such as toluene. Only one of these organic solvents should be used. However, you may also use two or more types in combination.

[0106] Examples of radical polymerization initiators used in radical polymerization include benzoyl peroxa. Organic peroxides such as di-t-butyl peroxide; 2,2'-azobisbutyronitrile , 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4- Examples include azo compounds such as methoxy-2,4-dimethylvaleronitrile. Dical polymerization initiators may be used individually or in combination of two or more. The polymerization initiator is used in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the total vinyl monomer raw materials. It is preferable to use it in an enclosure.

[0107] Furthermore, during radical polymerization, the weight-average molecular weight of the (meth)acrylic resin is controlled, etc. For this purpose, a chain transfer agent can be used. Examples of chain transfer agents include butanthio ol, octanthiol, decanethiol, dodecanethiol, hexadecanethiol, Octadecanethiol, cyclohexyl mercaptan, thiophenol, thioglycol Octyl mercaptopropionate, octyl 2-mercaptopropionate, octyl 3-mercaptopropionate 2-ethylhexyl mercaptopropionate, 2-ethyl thioglycolate Hexyl, butyl-3-mercaptopropionate, mercaptopropyltrimethoxysyl Lan, methyl-3-mercaptopropionate, 2,2-(ethylenedioxy)diethane Thiol, ethanethiol, 4-methylbenzenethiol, 2-mercaptoyl octanoate Tyl ester, 1,8-dimercapto-3,6-dioxaoctane, decantrichol , dodecyl mercaptan, diphenyl sulfoxide, dibenzyl sulfide, 2,3-di Methylcapto-1-propanol, mercaptoethanol, thiosalicylic acid, thioglycerides Roll, thioglycolic acid, 3-mercaptopropionic acid, thiomalic acid, mercaptovinegar Examples include acids, thiol compounds such as mercaptosuccal acid and 2-mercaptoethanesulfonic acid. These can be used individually or in combination of two or more types.

[0108] The amount of chain transfer agent used is 0.1 to 2 parts per 100 parts by weight of the total vinyl monomer raw materials. Preferably 5 parts by weight, more preferably 0.5 to 20 parts by weight, and even more preferably 1.0 to 15 parts by weight. preferable.

[0109] The reaction time for radical polymerization is preferably 1 to 20 hours, and more preferably 3 to 12 hours. Furthermore, the reaction temperature is preferably 40 to 120°C, and more preferably 50 to 100°C.

[0110] (meth)acrylic resin containing compounds having (meth)acrylate groups and carboxyl groups, etc. To react the (meth)acrylic resin obtained as described above, add (meth)acrylic By adding compounds having a rate group and a carboxyl group, triphenylphosphine, tetraphosphate, etc. Trabutylammonium bromide, tetramethylammonium chloride, triethyl In the presence of one or more catalysts such as amines, the mixture is typically heated at 90 to 140°C, preferably 100 to 1 The reaction should proceed at a temperature of 20°C for approximately 3 to 9 hours. Here, the catalyst is the (meth ) Acrylic acid ester polymers and chemical compounds having (meth)acrylate groups and carboxyl groups Use in a ratio of approximately 0.5 to 3 parts by weight per 100 parts by weight of the total amount of compound, such as a compound mixture. This is preferable. This reaction is carried out after producing (meth)acrylic resin by polymerization. Alternatively, after separating the (meth)acrylic resin from the reaction system, the (meth)acrylate group The process may also be carried out by adding compounds such as compounds having a carboxyl group.

[0111] The weight-average molecular weight of (meth)acrylic (meth)acrylate depends on the application of the curable composition. The appropriate range should be selected, but preferably 1,000 to 200,000, more preferably More preferably 5,000 to 100,000, more preferably 8,000 to 80,000, particularly preferred The range is approximately 10,000 to 60,000. Using it within this range provides wear resistance. Improved properties, enhanced adhesion with functional layers, and improved elongation during molding as required by application. This also allows for good results. Furthermore, the viscosity of the composition can be easily kept within an appropriate range, and the applicability is also good. It can be made into something excellent. Note that the weight-average molecular weight (Mw) of the resin is... Using geochromatography (GPC), the converted value based on the polystyrene standard is obtained. It can then be decided.

[0112] The content of (meth)acrylate-derived compounds in the hard coat layer depends on the application and required hard coat. It is difficult to say definitively as it varies depending on the characteristics of the coating layer, but preferably 10% by mass More preferably 20% by mass or more, even more preferably 30% by mass or more, and especially preferably The amount is in the range of 50% by mass or more, most preferably 70% by mass or more. There is no particular upper limit. It may be 100% by mass, and when other additives are added to impart performance, preferably The percentage is 99% by mass or less, more preferably 95% by mass or less. Use within the above range. This results in good scratch resistance and hardness.

[0113] Furthermore, within the hard coat layer, there are layers to improve or adjust wear resistance and hardness. It is also possible to use active energy ray curable compounds other than those described above. To improve adhesion with the functional layer, etc., conventionally known trees that do not have (meth)acrylate groups It is also possible to include fat.

[0114] The hard coat layer includes features such as improved scratch resistance, increased hardness, and anti-blocking properties. It is also possible to use particles for the purpose of [this purpose]. Conventionally known particles can be used, as described above. It is also possible to use particles that can be used in the functional layer. Among these particles, particularly resistant From the viewpoint of improving scratch resistance, silica particles and alumina particles are preferred, and silica particles The child is preferable.

[0115] The hard coat layer is designed to improve scratch resistance, or, in the case of being formed by coating, the coating liquid Leveling agents can be used as part of the composition. As leveling agents, acrylic-based Examples include leveling agents, silicone-based leveling agents, and fluorine-based leveling agents. Among these, one of the issues addressed in the present invention is that wear resistance can also be improved. Silicone-based leveling agents are more preferred, and furthermore, during various subsequent processing steps, etc. Furthermore, the perspective of preventing the bleed-out of the leveling agent after the hard coat layer is formed has also been added. Therefore, silicone-based leveling agents having radically polymerizable functional groups are particularly preferred. Silicone-based leveling agents impart slip properties to cured materials, enabling high wear resistance. Silicone-based leveling agents having radical polymerizable functional groups are curable by active energy rays. It is incorporated into the hardened material by reacting with other substances, providing long-term slip resistance, wear resistance, and It is extremely useful because it can achieve chemical resistance.

[0116] The content of the leveling agent-derived compound in the hard coat layer is preferably 20% by mass or less. More preferably 0.01 to 10% by mass, even more preferably 0.1 to 5% by mass, particularly preferred The amount is in the range of 0.2 to 4% by mass, most preferably 0.3 to 3% by mass. By using this method, not only is the appearance of the hard coat layer improved, but wear resistance is also enhanced. Cut.

[0117] To improve the weather resistance of the laminate, UV absorbers may be included in the hard coat layer. This is a preferred form. From the viewpoint of heat resistance, a molecular weight of 500 or more is preferred. UV absorption From the viewpoint of good solubility in the composition and improved weather resistance, the agents are triazine-based, benzo-based, etc. Phenone derivatives, benzotriazole derivatives, cyclic iminoester derivatives, salicylate derivatives, Alternatively, it is derived from cyanoacrylate compounds and has a maximum absorption wavelength of 24 UV absorbers in the range of 0 to 380 nm are preferred. Among these, UV absorbers are particularly preferred. In terms of good properties and superior appearance when used as a hard coat layer, triazine Benzotriazole-based compounds are more preferred, and triazine-based compounds are even more preferred.

[0118] Triazine-based UV absorbers are not limited to the following, but for example, 2- [4-([2-hydroxy-3-dodecyloxypropyl]oxy)-2-hydroxy [phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2- [4-([2-hydroxy-3-tridecyloxypropyl]oxy)-2-hydroxy Phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine(T inuvin(registered trademark)400 (manufactured by BASF), 2-[4,6-bis( 2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-[3-(dodecyl) [siloxy)-2-hydroxypropoxy]phenol), 2-(2,4-dihydroxy Phenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester reaction product (Tinuvin (registered trademark) )405, manufactured by BASF, 2,4-bis"2-hydroxy-4-butoxyphenyl" 6-(2,4-dibutoxyphenyl)-1,3-5-triazine (Tinuvin (Registered Trademark) 460, manufactured by BASF, 2-(4,6-diphenyl-1,3,5-triazine- 2-yl)-5-[(hexyl)oxy]-phenol (Tinuvin(registered trademark) 1 577, manufactured by BASF, 2-(4,6-diphenyl-1,3,5-triazine-2-) (ADK)-5-[2-(2-ethylhexanoyloxy)ethoxy]-phenol (ADK) STAB LA46 (manufactured by ADEKA), 2-(2-hydroxy-4-[1-octyl) Xycarbonylethoxy[phenyl]-4,6-bis(4-phenylphenyl)-1,3 Examples include 5-triazine (Tinuvin® 479, manufactured by BASF). .

[0119] Benzotriazole-based UV absorbers are not limited to the following, but for example... , 2-[2'-hydroxy-5'-(methacryloyloxymethyl)phenyl]-2H -benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl )phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacrylate [Royloxypropyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy C-5'-(methacryloyloxyhexyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-3'-tert-butyl-5'-(methacryloyloxyethyl [2H-benzotriazole, 2-[2'-hydroxy-5'-tert] -butyl-3'-(methacryloyloxyethyl)phenyl]-2H-benzotriazole Lu, 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5- Chloro-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyl Oxyethyl)phenyl]-5-methoxy-2H-benzotriazole, 2-[2'-H Droxy-5'-(methacryloyloxyethyl)phenyl]-5-cyano-2H-ben Zotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl) phen [Nyl]-5-tert-butyl-2H-benzotriazole, 2-[2'-hydroxy- 5'-(methacryloyloxyethyl)phenyl]-5-nitro-2H-benzotriazo Examples include [mention specific examples].

[0120] Examples of cyclic iminoester-based UV absorbers include, but are not limited to, the following: For example, 2-methyl-3,1-benzoxazine-4-one, 2-butyl-3,1-benzo Xazazine-4-one, 2-phenyl-3,1-benzoxazine-4-one, 2-(1- Or 2-naphthyl)-3,1-benzoxazine-4-one, 2-(4-biphenyl)- 3,1-Benzoxazine-4-one, 2-p-nitrophenyl-3,1-benzox Zin-4-one, 2-m-nitrophenyl-3,1-benzoxazin-4-one, 2- p-benzoylphenyl-3,1-benzoxazin-4-one, 2-p-methoxyphenyl Nyl-3,1-benzoxazine-4-one, 2-o-methoxyphenyl-3,1-ben Zooxazine-4-one, 2-cyclohexyl-3,1-benzoxazine-4-one, 2-p-(or m-)phthalimidophenyl-3,1-benzoxazin-4-one, N -phenyl-4-(3,1-benzoxazine-4-on-2-yl)phthalimide, N -benzoyl-4-(3,1-benzoxazine-4-on-2-yl)aniline, N- Benzoyl-N-methyl-4-(3,1-benzoxazine-4-on-2-yl)ani Phosphorus, 2-(p-(N-methylcarbonyl)phenyl)-3,1-benzoxazine-4 -one, 2,2'-bis(3,1-benzoxazine-4-one), 2,2'-ethylene Bis(3,1-benzoxazine-4-one), 2,2'-tetramethylenebis(3,1 -benzoxazine-4-one), 2,2'-decamethylenebis(3,1-benzox Zin-4-one, 2,2'-p-phenylenebis(3,1-benzoxazine-4-one) n), 2,2'-m-phenylenebis(3,1-benzoxazine-4-one), 2,2 '-(4,4)-diphenylene)bis(3,1-benzoxazine-4-one), 2,2 '-(2,6- or 1,5-naphthylene)bis(3,1-benzoxazine-4-one) ,2,2'-(2-methyl-p-phenylene)bis(3,1-benzoxazine-4-o n), 2,2'-(2-nitro-p-phenylene)bis(3,1-benzoxazine-4 -ON), 2,2'-(2-chloro-p-phenylene)bis(3,1-benzoxazine) -4-one), 2,2'-(1,4-cyclohexylene)bis(3,1-benzoxazine) (-4-one), 1,3,5-tri(3,1-benzoxazine-4-one-2-yl) Benzene, 1,3,5-tri(3,1-benzoxazine-4-on-2-yl)naphtha Len, 2,4,6-tri(3,1-benzoxazine-4-on-2-yl)naphthalene , 2,8-dimethyl-4H,6H-benzo(1,2-d;5,4-d')bis(1,3) -Oxazine-4,6-dione, 2,7-dimethyl-4H,9H-benzo(1,2-d; 4,5-d')bis(1,3)-oxazine-4,9-dione,2,8-diphenyl- 4H,8H-benzo(1,2-d;5,4-d')bis(1,3)-oxazine-4,6 -Zione, 2,7-diphenyl-4H,9H-benzo(1,2-d;4,5-d')bis (1,3)-Oxazine-4,6-dione, 6,6'-bis(2-methyl-4H,3,1 -Benzoxazine-4-one), 6,6'-bis(2-ethyl-4H,3,1-benzo Oxazine-4-one), 6,6'-bis(2-phenyl-4H,3,1-benzoxazine) Zin-4-one), 6,6'-methylenebis(2-methyl-4H,3,1-benzoxane) Zin-4-one), 6,6'-methylenebis(2-phenyl-4H,3,1-benzooxy (Sadin-4-one), 6,6'-ethylenebis(2-methyl-4H,3,1-benzooxy) (Sadin-4-one), 6,6'-ethylenebis(2-phenyl-4H,3,1-benzo) Xazazine-4-one), 6,6'-butylenebis(2-methyl-4H,3,1-benzo) Xazazine-4-one), 6,6'-butylenebis(2-phenyl-4H,3,1-benzo Oxazine-4-one), 6,6'-oxybis(2-methyl-4H,3,1-benzo Xazazine-4-one), 6,6'-oxybis(2-phenyl-4H,3,1-benzo) Xazazine-4-one), 6,6'-sulfonylbis(2-methyl-4H,3,1-benzo Oxazine-4-one), 6,6'-sulfonylbis(2-phenyl-4H,3,1-be (Nzooxazine-4-one), 6,6'-carbonylbis(2-methyl-4H,3,1- Benzoxazine-4-one), 6,6'-carbonylbis(2-phenyl-4H,3, 1-Benzoxazine-4-one), 7,7'-methylenebis(2-methyl-4H,3, 1-Benzoxazine-4-one), 7,7'-methylenebis(2-phenyl-4H,3 ,1-benzoxazine-4-one), 7,7'-bis(2-methyl-4H,3,1-be (Nzooxazine-4-one), 7,7'-ethylenebis(2-methyl-4H,3,1-be) (Xinooxazine-4-one), 7,7'-oxybis(2-methyl-4H,3,1-ben) Zooxazine-4-one), 7,7'-sulfonylbis(2-methyl-4H,3,1-be (Nzooxazine-4-one), 7,7'-carbonylbis(2-methyl-4H,3,1- Benzoxazine-4-one), 6,7'-bis(2-methyl-4H,3,1-benzo Xazazine-4-one), 6,7'-bis(2-phenyl-4H,3,1-benzoxazine) n-4-one, 6,7'-methylenebis(2-methyl-4H,3,1-benzooxadi 6,7'-methylenebis(2-phenyl-4H,3,1-benzoxane), 6,7'-methylenebis(2-phenyl-4H,3,1-benzoxane) Examples include din-4-one.

[0121] Benzophenone-based UV absorbers (benzophenone compounds), oxybenzophenone-based Examples of UV absorbers (oxybenzophenone compounds) include 2,4-dihydrox Cibenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4 -Methoxybenzophenone-5-sulfonic acid (anhydrous and trihydrate), 2-hydroxy-4- Octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2'-dihydroxy-4-methylbenzophenone Toxybenzophenone (product name "KEMISORB111", manufactured by Chemipro Chemical Co., Ltd.) , 2,2',4,4'-tetrahydroxybenzophenone (product name "SEESORB10") 6"), manufactured by Cipro Chemical Co., Ltd., 2,2'-dihydroxy-4,4-dimethoxybenzof Examples include Enon, among others.

[0122] Examples of salicylate ester-based UV absorbers (salicylate ester compounds) include, for example, , phenyl-2-acryloyloxybenzoate, phenyl-2-acryloyloxy -3-methylbenzoate, phenyl-2-acryloyloxy-4-methylbenzoate Phenyl-2-acryloyloxy-5-methylbenzoate, phenyl-2-acryloyloxy-5-methylbenzoate, phenyl-2-acryloyloxy-5-methylbenzoate Liloyloxy-3-methoxybenzoate, phenyl-2-hydroxybenzoate, Phenyl-2-hydroxy-3-methylbenzoate, phenyl-2-hydroxy-4methylbenzoate Tylbenzoate, phenyl-2-hydroxy-5-methylbenzoate, phenyl-2- Hydroxy-3-methoxybenzoate, 2,4-di-tert-butylphenyl-3, 5-di-tert-butyl-4-hydroxybenzoate (Tinuvin®) Examples include the 120 (manufactured by BASF).

[0123] Examples of cyanoacrylate-based UV absorbers (cyanoacrylate compounds) include, for example, , alkyl-2-cyanoacrylate, cycloalkyl-2-cyanoacrylate, aldehyde Coxyalkyl-2-cyanoacrylate, alkenyl-2-cyanoacrylate, al Examples include quinyl-2-cyanoacrylate. Furthermore, these compounds may be used individually or in combination of two or more.

[0124] The amount of UV absorber in the hard coat layer is preferably 20% by mass or less, more preferably More preferably 0.01 to 15% by mass, more preferably 0.1 to 10% by mass, and especially preferably 0 The range is 0.5 to 8% by mass, most preferably 1 to 5% by mass. This allows for the effective formation of a hard coat layer, improving the weather resistance of the laminate.

[0125] To further improve the weather resistance of the laminate, a light stabilizer is included in the hard coat layer. This is also a preferred form. The light stabilizer is not particularly limited as long as it is a hindered amine-based light stabilizer. No. A specific example of a light stabilizer is bis(2,2,6,6-tetramethyl-4-piperidi (L) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate T, Bis(1-methoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate , bis(1-ethoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, Bis(1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, Bis(1-butoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bi (1-pentyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, Bis(1-hexyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate Bis(1-heptyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebakey T, Bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidyl)sebakey T, Bis(1-nonyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebakey T, Bis(1-decaniloxy-2,2,6,6-tetramethyl-4-piperidyl)seba Bis(1-dodecyloxy-2,2,6,6-tetramethyl-4-piperidyl)seba Kate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(4-meth Xy-benzylidene) malonate, tetrakis(2,2,6,6-pentamethyl-4-p Peridyl) 1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2, 6,6-Pentamethyl-4-piperidyl)1,2,3,4-Butanetetracarboxylate Aminomethyl group-containing compounds such as , 1,2,3,4-butanetetracarboxylic acid and 1,2, 2,6,6-Pentamethyl-4-Piperidinol and β,β,β,β-Tetramethyl-3, 9-(2,4,8,10-tetraoxaspiro[5,5])undecane)diethanol and The condensate of 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-pentamethyl- 4-Piperidinol and β,β,β,β-tetramethyl-3,9-(2,4,8,10 Condensate with traoxaspiro[5,5])undecane)diethanol, decanedicarbon Diesterene of acid and 2,2,6,6-tetramethyl-1-octoxy-4-piperidinol Reaction product of a compound with 1,1-dimethylethyl hydroperoxide and octane (BA Made in SF, product name Chinuvin 123), bis(1,2,2,6,6-pentamethyl-4-pipe Lidinyl)-[[3,5-bis(1,1,dimethylethyl)-4-hydroxyphenyl] Examples of amino ether group-containing compounds include methyl (BASF, trade name Tinuvin 144). This can be achieved. Among these, amino ether group-containing compounds are preferred from the viewpoint of weather resistance of the cured product. In particular, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bi [(1,1,dimethylethyl)-4-hydroxyphenylmethyl] is particularly preferred. These compounds may be used individually or in combination of two or more.

[0126] The content of the light stabilizer in the hard coat layer is preferably 20% by mass or less, more preferably The amount is 0.01 to 15% by mass, more preferably 0.1 to 10% by mass, and especially preferably 0.5% by mass. The range is ~8% by mass, most preferably 1-5% by mass. Using it within this range will have an effect. This effectively forms a hard coat layer, improving the weather resistance of the laminate.

[0127] A photopolymerization initiator may be used to accelerate curing when forming the hard coat layer. The molecular weight of the polymerization initiator is preferably 1,000 or less. Specific examples include benzoin and benzo. Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Nzoin-n-butyl ether, benzoin phenyl ether, benzyl diphenyl disulfide Rufid, dibenzyl, diacetyl, anthraquinone, naphthoquinone, 3,3'-dimethicone ru-4-methoxybenzophenone, benzophenone, p,p'-bis(dimethylamino) Benzophenone, 4,4'-bis(diethylamino)benzophenone, pivaloin ethyl Ether, benzyldimethyl ketal, 1,1-dichloroacetophenone, pt-butyric acid Ludichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-chloro Thioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,2 -diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2, 2-Dichloro-4-phenoxyacetophenone, phenylglyoxylate, α-hydro Xyisobutylphenone, dibenzosparone, 1-(4-isopropylphenyl)-2- Hydroxy-2-methyl-1-propanone, 2-methyl-[4-(methylthio)phenyl ]-2-morpholino-1-propanone, tribromophenylsulfone, tribromomethicone Examples include phenylsulfone. These photopolymerization initiators can be used individually or in pairs. You may use the above methods in combination.

[0128] The content of the photopolymerization initiator-derived compound in the hard coat layer is preferably 20% by mass or less. More preferably 0.1 to 15% by mass, even more preferably 0.3 to 10% by mass, particularly preferred The amount is in the range of 0.5 to 8% by mass, most preferably 1 to 7% by mass. This effectively promotes the formation of the hard court layer.

[0129] The hard coat layer may also contain antioxidants, anti-yellowing agents, and bluing agents as needed. Various additives such as agents, pigments, dyes, defoamers, thickeners, anti-settling agents, antistatic agents, and anti-fogging agents. It may be added to the mixture.

[0130] Furthermore, when forming a functional layer or a hard coat layer, Depending on the application method, various solvents can be used as needed. Water, aromatic solvents such as toluene and xylene; methyl ethyl ketone, acetone, methyl ethyl ketone, etc. Ketone solvents such as butyl ketone and cyclohexanone; diethyl ether, isopropyl Ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ether Diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene Glycol diethyl ether, propylene glycol monomethyl ether, anisole Ether-based solvents such as phenetol; ethyl acetate, butyl acetate, isopropyl acetate, ethyl acetate Ester solvents such as ethylene glycol diacetate; dimethylformamide, diethylformamide Amide-based solvents such as muamide and N-methylpyrrolidone; methyl cellosolve, ethyl cellosol Cellosolve-based solvents such as butyl cellosolve; methanol, ethanol, propanol, Alcohol-based solvents such as isopropanol and butanol; dichloromethane, chloroform, etc. Examples include halogenated solvents; etc. These solvents may be used individually or in combination of two or more. The above may be used in combination. Of these solvents, water is preferred from an environmental perspective, and also for application. Ester-based solvents, ether-based solvents, and alcohol-based solvents are good choices because they make it easier to improve workability in this context. Solvents and ketone-based solvents are preferred.

[0131] The content of nonvolatile components (solids) in the composition that forms the functional layer or hard coat layer is determined by the use of the composition. It depends on the material system, so it's difficult to say definitively, but for example, in the range of 0.1 to 100 mass%, Preferably, the range is 1-80%. Note that non-volatile content refers to the total mass of components other than solvents, such as solvents. The non-volatile content of the composition forming the layer can be measured by conventionally known methods, for example, 1 The change in weight when the composition of g is spread out and heated at 100°C for 1 hour to evaporate the solvent. It is measured by chemical analysis.

[0132] Conventional known methods can be used for forming the functional layer and hard coat layer, for example. Examples include coating and transfer. From the perspective of having fewer steps and being able to apply easily... A coating method is preferred when forming a functional layer or a hard coat layer. Gravure Coat, Reverse Roll Coat, Dye Coat, Air Doctor Coat, Break Docoat, rodcoat, barcoat, curtaincoat, knifecoat, transfer coat Coating, squeeze coat, impregnation coat, kiss coat, spray coat, calendar coat Known coating methods such as extrusion coating, dip coating, and spin coating can be used. It is possible.

[0133] Furthermore, the substrate or functional layer improves its adhesion to the functional layer or hard coat layer, respectively. Furthermore, corona treatment or plasma treatment can be applied to improve coating properties, etc.

[0134] The drying and curing conditions when forming the functional layer or hard coat layer are particularly limited. Although it is not a matter of the coating solution itself, the drying of the water, organic solvents, and other media used in the coating solution is usually 3 In the range of 0 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 a hard coat layer formed by curing, drying and heat curing can be performed simultaneously or consecutively. be.

[0135] In the formation of a hard coat layer, the active energy rays used in curing Examples of harmful energy rays include ultraviolet rays, electron beams, visible light, infrared rays, and X-rays. Among these, ultraviolet light and electron beams are preferred from the viewpoint of curing properties and prevention of resin degradation, and ultraviolet light is more This is preferable. Furthermore, the irradiation dose of the active energy rays should be adjusted appropriately according to the active energy rays being irradiated. It can be selected.

[0136] For example, when using ultraviolet light, the integrated light intensity of the irradiation is 20 to 5000 mJ / cm². 2 that is preferable , 100-3000 mJ / cm² 2 More preferably, 200-2000 mJ / cm² 2 Gasa Furthermore, it is preferable. In addition, the illuminance should be 50-600 mW / cm². 2 Preferably, 75-45 0 mW / cm 2 More preferably, 100-300 mW / cm² 2 This is even more preferable. Light source and For example, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, electrodeless lamps, and metal halide lamps. , or electron beams such as scanning type or curtain type electron beam accelerating circuits, high-pressure mercury lamps, ultra-high-pressure mercury lamps, etc. Pressurized mercury lamps, etc., can be used.

[0137] 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 from the viewpoints of the curability of the active energy ray curable composition of the present invention, the flexibility of the cured product, and prevention of damage to the substrate, it is more preferably 1 to 15 Mrad.

[0138] The thickness of the hard coat layer is preferably 0.1 to 20 μm, more preferably 1 to 10 μm , and even more preferably in the range of 2 to 7 μm. If the thickness of the hard coat layer is within the above range, it is easy to realize desired properties such as abrasion resistance and hardness. The thickness of the hard coat layer is determined by cross-sectional observation using an electron microscope or the like.

[0139] When used in applications where antistatic performance is required, the surface resistance value of the laminate is usually 1×10 Ω or less, preferably 1×10 13 Ω or less, more preferably 5×10 12 Ω or less, even more preferably 1×10 Ω or less, particularly preferably 5×10 11 Ω or less, most 10 preferably in the range of not more than 1×10 Ω. The lower limit is not particularly limited but is 100 Ω or more 10 . By setting it within the above range, adhesion of foreign substances such as dust can be suppressed.

[0140] When the antistatic performance is also required for applications where the processability (such as bending, folding, or stretching) of the laminate is required, the surface resistance value of the laminate after 10% stretching is preferably 1 ×10 13 Ω or less, more preferably 1×10 12 Ω or less, even more preferably 5×1 0 11 Ω or less, particularly preferably 1×10 11It is within the range of Ω or less. Furthermore, there is no particular restriction on the lower limit. It is not present but is 100Ω or more. Processing (bending, folding, or stretching) is done within the above range. Even after processing, the adhesion of foreign matter such as dust is suppressed. If even greater processability is required, the surface resistance value of the laminate after 20% stretching is desirable. Mashiku is 1 x 10 13 It is less than or equal to Ω, and more preferably 1 × 10⁻⁶ 12 Omega or lower, even better kuha 5×10 11 The range is less than or equal to Ω. There is no specific lower limit, but it should be 100Ω or more. .

[0141] Analysis of components in the substrate, functional layer, and hard coat layer is performed, for example, by TOF-SIMS (Flight-to-Air Simulator). X-ray time-based secondary ion mass spectrometry, ESCA (X-ray photoelectric spectroscopy), X-ray fluorescence, IR (infrared spectroscopy) This can be done by methods such as spectroscopy.

[0142] Furthermore, it is possible to provide various characteristic layers on top of the hard coat layer of the present invention. Examples of characteristic layers include conventionally known ones, such as anti-reflective layers, low-reflection layers, high-reflection layers, and Examples include anti-glare layers, anti-blocking layers, anti-fouling layers, anti-fogging layers, and adhesive layers. Various functional layers and hard coat layers are located on the side of the substrate with the functional layer and hard coat layer, and on the opposite side. It is also possible to provide a characteristic layer. A functional layer and a hard coat layer are provided on both sides of the substrate. It is also possible to do so.

[0143] The laminate of the present invention is particularly excellent in optical properties such as birefringence among various applications. It can be suitably used for spray materials and electrical / electronic components, and is a general polycarbonate resin. Its superior scratch resistance compared to grease makes it suitable for use in automotive parts and various lenses. This is possible, and similarly, it has superior processability compared to general polycarbonate resin, so various It can be suitably used in film applications, such as display components and decorative applications. [Examples]

[0144] The present invention will be described in more detail below with reference to examples, but the present invention will not exceed its gist. The following examples are not limited to those described below. The measurement and evaluation methods used in this invention are as follows.

[0145] (1) Measurement of weight-average molecular weight (Mw) and number-average molecular weight Equipment: Tosoh Corporation's "HLC-8120GPC" Column: TSKgel Super H1000+H2000+H manufactured by Tosoh Corporation 3000, 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.

[0146] (2) Measurement of glass transition temperature Using a viscoelastic spectrometer DVA-200 (manufactured by IT Measurement Control Co., Ltd.), Dynamic viscoelasticity temperature dispersion measurement (JI) at strain 0.1%, frequency 10Hz, and heating rate 3℃ / min. Dynamic viscoelasticity measurements were performed using the S K7198A method. The principal variance of the loss tangent (tanδ) was determined by P. The temperature at which the glass transition temperature is indicated is defined as the glass transition temperature.

[0147] (3) Measurement of surface resistance High-resistivity meter: HighResta MCP-HP450, manufactured by Mitsubishi Chemical Analytec Corporation. Using this method, the sample was conditioned for 30 minutes in a measurement atmosphere of 100V overvoltage, 23°C, and 50%RH. Then, the surface resistance value of the hard coat layer was measured. If the surface resistance reading is OVER, it means the surface resistance is too high to be measured with a high resistivity meter. This indicates that. If the surface resistance value shows "UNDER," it means the surface resistance value is too low to be measured with a high resistivity meter. Since the value was low, the surface resistance was measured using the method described below. Low-resistivity meter: Loresta GP MCP-T610, manufactured by Mitsubishi Chemical Analytec Corporation. This is a four-pronged ESP probe (probe spacing: 5mm, probe tip shape: 2mm diameter cylinder, probe push Using a pressure of 240g / bottle and a constant RCF value of 4.235, at 23°C and 50%RH. The sample was conditioned in the specified measurement atmosphere for 30 minutes, and then the surface resistance value of the hard coat layer was measured. It was decided.

[0148] (4) Measurement of surface resistance after stretching The obtained film was subjected to a uniaxial tensile testing machine (IMADA Corporation "MX2- Using a 500N chuck, at a temperature of 140°C, a tensile speed of 40 mm / min, and a chuck distance of 40 mm. The stretching was performed at each magnification under the specified conditions, and the surface resistance value of the hard coat layer was measured in the same manner as in measurement (3). Yes. Note that a 10% extension means a 1.1x extension.

[0149] (5) Method for evaluating the scratch resistance of the hard coat layer Lightly rub the hard coat layer of the laminate with steel wool #0000 and if any scratches are visible... If no scratches are visible (good scratch resistance), classify as A; if light scratches are visible, classify as B (acceptable range); clearly Items with scratches or marks were rated as C.

[0150] (6) Method for evaluating the adhesion of the hard coat layer On the hard coat layer side of the laminate, in an environment of 23°C and 50% RH, a hard coat is applied with a cutter. Apply 18mm wide tape (Nichiban Co., Ltd. cellophane tape (registered trademark)) to the area where the layer has been scratched. After applying the (CT-18) label and rapidly peeling it off at a 180-degree peeling angle, observe the peeled surface. Case A was defined as having no delamination (good adhesion), and case B was defined as having delamination.

[0151] The materials used in the examples and comparative examples are as follows:

[0152] (base material) ISB: Isosorbide • CHDM: 1,4-Cyclohexanedimethanol TCDDM: Tricyclodecanedimethanol DPC: Diphenyl carbonate ·Irganox1010: Pentaerythritol-tetrakis[3-(3,5-di-t [ert-butyl-4-hydroxyphenyl)propionate] (manufactured by BASF Corporation) (Heat stabilizer) AS2112: Tris(2,4-di-tert-butylphenyl) phosphite (stock) (Manufactured by ADEKA Corporation, heat stabilizer) • E-275: Ethylene glycol distearate (manufactured by NOF Corporation, mold release agent)

[0153] (Examples of compounds in the functional layer) • Acrylic resin: (A1) Acrylic resin having the following composition Ethyl acrylate / n-butyl methacrylate / acrylic acid = 25 / 73 / 2 mass%) • Polyester resin: (A2) Polyester resin consisting of the following composition (Acid components) Terephthalic acid / Isophthalic acid / 5-sodium sulfisoisophthalic acid / / (Geo (Components) Ethylene glycol / 1,4-butanediol / diethylene glycol = 56 / 40 / 4 / / 70 / 20 / 10 (mol%)

[0154] • Polymer-type antistatic agent containing ammonium groups: (B1) Composed of the following monomer composition having a pyrrolidinium ring in the main chain, with a number average molecular weight of 30 ,000 polymers. Monomer composition: diallyldimethylammonium chloride / dimethylacrylamide / N-methylolacrylamide = 90 / 5 / 5 (mol%) • Poly(3,4-ethylenedioxythiophene) is compounded with polystyrene sulfonic acid. Conductive organic polymer compounds with a number-average molecular weight of 1,000 or more: (B2).

[0155] • Crosslinking agent: (C) Acrylic polymer having oxazoline groups and polyalkylene oxide chains (Nippon Co., Ltd.) This catalyst is manufactured using Epocross (registered trademark).

[0156] (Examples of compounds for hard coat layers) • (Meth)acrylate: (D1) Dipentaerythritol hexaacrylate (hexafunctional) (manufactured by Nippon Kayaku Co., Ltd.) Kayala (Registered Trademark DPHA) • Urethane (meth)acrylate: (D2) 10-function urethane (meth)acrylate (manufactured by Mitsubishi Chemical Corporation, Shiko (registered trademark)) (UV-1700B) • (Meta)acrylate: (D3) Dipentaerythritol hexa denatured with 12 caprolactone molecules per molecule Acrylate (hexafunctional) (manufactured by Nippon Kayaku Co., Ltd.) Kayarad (registered trademark) DPCA-12 0) • (Meta)acrylate: (D4) Pentaerythritol and acrylic acid condensate (mixture of trifunctional and tetrafunctional compounds) (Osaka Organic Chemical) (Manufactured by Gaku Kogyo Co., Ltd., Viscoat #300) • (Meth)acrylic (Meth)acrylate: (D5) (Meth)acrylic resin manufactured by the method shown below A flask equipped with a thermometer, stirrer, and reflux condenser contains propylene glycol monomethyl Ether (178 parts by mass), glycidyl methacrylate (20 parts by mass), methyl methacrylate Sulfate (79 parts by mass), ethyl acrylate (1.0 part by mass), and 2,2'-azobis Add (2,4-dimethylvaleronitrile) (0.6 parts by mass) and react at 65°C for 3 hours. Then, 2,2'-azobis(2,4-dimethylvaleronitrile) (0.3 After adding parts by mass and reacting for 3 hours, propylene glycol monomethyl ether (48 (parts by mass) and p-methoxyphenol (0.5 parts by mass) were added and the mixture was heated to 100°C. Next, add acrylic acid (10 parts by mass) and triphenylphosphine (1.6 parts by mass). Furthermore, by reacting at 110°C for 6 hours, the amount of radical polymerizable double bond (acryloyl (Meth)acrylic resin (A-) with a group concentration (amount of acryloyl group introduced) of 615 g / mmol 1) was obtained. The weight-average molecular weight was 48,800. The hydroxyl value was 91 mgKOH / mg That was the case.

[0157] • Silica particles: (E1) Organosilica sol (MEK-AC-2140Z, manufactured by Nissan Chemical Corporation) • Leveling agent: (E2) Silicone-based leveling agent with radical polymerizable functional groups (BYK-UV, manufactured by BYK Corporation) 3500) • UV absorber: (E3) 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)- 4,6-Bis(4-phenylphenyl)-1,3,5-triazine (BASF-manufactured Ti nuvin 479) • Light stabilizer: (E4) Bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis( 1,1-dimethylethyl)-4-hydroxyphenyl]methyl](BASF Tin uvin 144) • Photopolymerization initiator: (E5) 1-Hydroxycyclohexylphenyl ketone (manufactured by IGM Resins BV) Omnirad 184)

[0158] [Example 1] The reactor is connected in the following order: three vertical agitators, one horizontal agitator, and a twin-screw extruder with a vacuum vent. Polycarbonate resin polymerization was carried out using a continuous polymerization facility. ISB, CHDM, D The PCs are melted in separate raw material preparation tanks, and the mol% is ISB / CHDM / DPC = 70 / The mixture was continuously supplied to the first vertical stirring reactor at a ratio of 30 / 101. In addition, vinegar was used as a polymerization catalyst. The calcium hydroxyl monohydrate aqueous solution is added at a ratio of 1.5 μmol per 1 mole of total hydroxyl compounds. The sea urchin was supplied to the first vertical stirring reactor. The temperature, pressure, and residence time of each reactor are approximately as follows: First vertical reactor: 190°C, 25kPa , 90 minutes, second vertical type: 195℃, 10kPa, 45 minutes, third vertical type: 210℃, 3kPa, For the fourth horizontal type, the settings were 45 minutes, 225°C, 0.5kPa, and 90 minutes. The reduced viscosity of the resulting polycarbonate resin is approximately 0.38 to 0.39 dL / g. The fourth horizontal agitated reactor was operated while adjusting its internal pressure.

[0159] The polymerization reaction product is withdrawn from the fourth horizontal stirring reactor at a flow rate of approximately 60 kg / hour, and then in a molten state. In its current state, it is sent to a twin-screw extruder with a vacuum vent (TEX30α, L / D=42, manufactured by Japan Steel Works). It was supplied. This extruder is equipped with three vacuum vents, and before the second vent, the molten resin is subjected to Water was continuously injected at a ratio of approximately 2000 ppm by mass, performing what is known as water-induced defoliation. Before the third vent, heat stabilizers such as Irganox 1010, AS2112, and E-275 are added. The mixture was continuously supplied in the ratios of 0.1 parts by mass, 0.05 parts by mass, and 0.3 parts by mass, and then melted and kneaded. The molten resin that has passed through the dispensing machine is filtered for foreign matter through a candle-shaped filter with a mesh size of 10 μm. The material is then discharged from the die in strand form, solidified with water cooling, and pelletized using a rotary cutter. A copolymerized polycarbonate resin with a glass transition temperature of 120°C was obtained.

[0160] Copolymerized polycarbonate resin is supplied to the extruder, melted at 240°C, and then processed using a T-die. The material was then cooled and solidified on a cooling roll set to 120°C to obtain a film with a thickness of 50 μm. (Substrate S1).

[0161] Apply the coating solution F1 shown in Table 1 below to the obtained film and dry at 100°C for 1 minute. A functional layer with a thickness of 0.1 μm was formed.

[0162] The obtained functional layer is coated with coating solution H1 shown in Table 2 below, dried at 80°C for 1 minute, and then heated. 300 mJ / cm² with a pressurized mercury lamp 2 The coating is then cured by irradiating it with 200mW of light, resulting in a thickness of 3μm. A hard coat layer was formed to obtain a laminate. The properties of the obtained laminate are shown in Table 3 below. It exhibited good scratch resistance.

[0163] [Examples 2-23] In Example 1, the coating liquid composition of the functional layer was changed to the coating composition shown in Table 1, and the hard coat Change the coating liquid composition of the layer to the coating agent composition shown in Table 2, or change the film thickness of the functional layer to the composition shown in Table 1. The laminate was manufactured in the same manner as in Example 1, except for the changes made as described, and a laminate was obtained. The characteristics are shown in Table 3 below. In Example 9, the surface resistance value after 10% stretching is 9 × 10 10 Ω, after 20% stretch The surface resistance is 2 × 10 11 The surface resistance value remained good even after stretching.

[0164] [Example 24] In Example 1, the resin raw material of the base material is changed from CHDM to TCDDM (Base Material S2). The laminate was manufactured in the same manner as in Example 1, except for the exceptions. The properties of the obtained laminate are shown in Table 3 below. As shown, it exhibited good surface resistance, scratch resistance, and adhesion. Note the copolymerization in Example 7. The glass transition temperature of polycarbonate resin was 130°C.

[0165] [Examples 25-28] In Example 24, the coating liquid composition of the functional layer was changed to the coating composition shown in Table 1, and the hard coat Change the coating liquid composition of the T layer to the coating agent composition shown in Table 2, or change the film thickness of the functional layer to the composition shown in Table 1. The laminate was manufactured in the same manner as in Example 1, except for the changes as described above. The characteristics are shown in Table 3 below.

[0166] [Comparative Example 1] In Example 1, the functional layer and hard coat layer were not provided, except that they were the same as in Example 1. The same method was used to manufacture and obtain a film. The obtained film has the following properties, as shown in Table 3: scratch resistance and The surface resistance was poor. Note that the surface resistance and scratch resistance are related to the hard coat layer. Surface resistance and scratch resistance were measured and evaluated using the same methods.

[0167] [Comparative Example 2] The manufacturing process was the same as in Example 1, except that a hard coat layer was not provided. The process was carried out to obtain a laminate. As shown in Table 3, the obtained laminate exhibited scratch resistance and surface resistance values It was a bad product. Furthermore, the surface resistance and scratch resistance are based on the surface resistance of the hard coat layer. Scratch resistance was measured and evaluated using the same methods as above.

[0168] [Comparative Example 3] In Example 1, the manufacturing process was the same as in Example 3, except that a hard coat layer was not provided. The material was fabricated, and a laminate was obtained. As shown in Table 3, the obtained laminate had poor scratch resistance. Furthermore, the surface resistance and scratch resistance are the same as those of the hard coat layer. Measurement and evaluation were performed using the following method.

[0169] [Table 1]

[0170] [Table 2]

[0171] [Table 3]

Claims

1. A laminate having a functional layer and a hard coat layer in that order on at least one surface of a polycarbonate resin substrate containing a heterobicyclo ring structure. The hard coat layer contains a compound derived from (meth)acrylate, wherein the (meth)acrylate is a hexafunctional or more (meth)acrylate modified with six or more caprolactones per molecule of (meth)acrylate, or a mixture of a condensate of pentaerythritol and acrylic acid and a hexafunctional or more urethane (meth)acrylate. A laminate containing a polymer-type antistatic agent having ammonium groups in the functional layer.

2. The laminate according to claim 1, wherein the polycarbonate resin constituting the base material is a copolymerized polycarbonate resin.

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

4. The laminate according to claim 1, which contains a resin in the functional layer.

5. Surface resistance value is 1 × 10 １３ The laminate according to claim 1 or 2, wherein the Ω value is less than or equal to Ω.

6. A laminated film, wherein the substrate is a film, among the laminates described in claim 3.

7. A method for manufacturing a laminate, comprising forming a functional layer by applying a coating solution containing a resin or an antistatic agent to at least one surface of a polycarbonate resin substrate containing a heterobicyclo ring structure, and further forming a hard coat layer on the functional layer by coating. The hard coat layer contains a compound derived from (meth)acrylate, wherein the (meth)acrylate is a hexafunctional or more (meth)acrylate modified with six or more caprolactones per molecule of (meth)acrylate, or a mixture of a condensate of pentaerythritol and acrylic acid and a hexafunctional or more urethane (meth)acrylate. A method for producing a laminate containing a polymer-type antistatic agent having an ammonium group in the functional layer.

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