Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/14—Protective coatings, e.g. hard coatings

Definitions

• the present invention relates to an ionizing radiation-curable composition, a hard coat film, and a method for producing a hard coat film.
• the display surface of a flat panel display such as a liquid crystal display (LCD) is required to be scratch-resistant so that it will not be scratched during handling and visibility will not deteriorate. Therefore, it is common practice to provide scratch resistance by using a hard coat film in which a hard coat layer is provided on a base film.
• a hard coat film in which a hard coat layer is provided on a base film.
• polyethylene terephthalate film, polyethylene naphthalate film, and cycloolefin film which are excellent in transparency, heat resistance, dimensional stability, and low moisture absorption, are expected to be used for optical members as base films.
• cycloolefin films with excellent optical isotropy are particularly expected.
• a hard coat layer is provided on such a base film in order to further impart hard properties.
• such a base film, especially a cycloolefin film has a problem of poor adhesion between the base film and the hard coat layer due to the small number of polar groups on the film surface.
• Patent Documents 1 and 2, etc. have conventionally disclosed methods for imparting easy adhesion to a hard coat layer to a cycloolefin film.
• Patent Document 1 discloses coating an anchor coating agent made of an olefin-based resin on the cycloolefin film.
• This anchor coat treatment improves the adhesion between the cycloolefin film and the hard coat layer to some extent.
• cracks film breakage, cracks, etc.
• Patent Document 2 As a method of adhering a hard coat layer to a cycloolefin film without performing an anchor coat treatment, in Patent Document 2, a polymerizable hindered amine-based photostabilizer is added to a curable composition containing an active energy ray-curable compound.
• a method of using an agent and a silane coupling agent as separate agents has been proposed.
• the adhesion initial adhesion
• the adhesion immediately after the formation of the hard coat layer and the adhesion when exposed to strong light after the formation of the hard coat layer can be obtained to some extent.
• the adhesion to light was not sufficient, such as the adhesion being extremely degraded.
• the present invention provides a hard coat layer for a base film such as a cycloolefin film, which has few polar groups and poor adhesion to the hard coat layer, without requiring surface treatment of the base film or an anchor coat layer.
• An object of the present invention is to provide a hard coat film having excellent adhesion to a layer (initial adhesion and light resistance adhesion) and a method for producing the same.
• Another object of the present invention is to provide an ionizing radiation-curable composition suitable for forming a hard coat layer having excellent adhesion (initial adhesion and light-resistant adhesion) to such a base film.
• the inventors of the present invention conducted intensive studies to solve the above problems, and found that a silane coupling agent having a hindered amine-based photostabilizing group is used in an ionizing radiation-curable composition for forming a hard coat layer. found that it is possible to improve the adhesion (especially the initial adhesion and light resistance adhesion) to the hard coat layer even for substrate films such as cycloolefin films that have few polar groups and have poor adhesion to the hard coat layer. , have completed the present invention.
• the first invention comprises at least an ionizing radiation-curable resin (component A) containing an acrylic resin having a (meth)acryloyl group and a silane coupling agent (component B) having a hindered amine photostabilizing group. and the content ratio of the silane coupling agent (component B) having the hindered amine photostabilizing group is 0.5% by mass to 2.8% by mass based on the solid content.
• a second invention is characterized in that the silane coupling agent having a hindered amine-based photostabilizing group (component B) does not contain a silane coupling agent having a fluorine group in its structure. 2.
• component B the silane coupling agent having a hindered amine-based photostabilizing group
• the ionizing radiation-curable composition further contains inorganic oxide fine particles (component C), and the inorganic oxide fine particles (component C) have an average particle size of 5 nm to 200 nm,
• the ionizing radiation-curable composition according to the first or second invention is provided, wherein the content ratio of the inorganic oxide fine particles (component C) is 1% by mass to 75% by mass relative to the solid content. .
• the ionizing radiation curable composition contains a diluent (component D), and when the diluent (component D) contains an aromatic hydrocarbon solvent, the solvent ratio after dilution 3, there is provided the ionizing radiation-curable composition according to any one of the first to third inventions, wherein the aromatic hydrocarbon solvent is less than 30% by mass.
• a fifth invention is characterized in that a hard coat layer comprising a cured coating film of the ionizing radiation-curable composition according to any one of the first to fourth inventions is provided on at least one surface of the base film.
• a sixth invention provides the hard coat film according to the fifth invention, wherein the base film is a cycloolefin film.
• a seventh invention is the fifth or sixth invention, wherein the base film is a cycloolefin film that has not been pretreated for the purpose of making the hard coat layer easier to adhere.
• a hard coat film as described is provided.
• An eighth invention is a method for producing a hard coat film having a hard coat layer comprising a cured coating film of an ionizing radiation-curable composition on at least one surface of a base film, wherein the base film comprises a cyclo It is an olefin film, and the ionizing radiation curable composition according to any one of the first to fourth inventions is applied to at least one surface of the base film, and the base temperature at the last stage of the drying process after coating
• a method for producing a hard coat film characterized in that the coating film is dried under conditions where the temperature is 50°C to 100°C.
• a hard coat can be obtained without the need for surface treatment of the base film or an anchor coat layer. It is possible to provide a hard coat film having excellent adhesion to a layer (initial adhesion and light resistance adhesion) and a method for producing the same. Further, according to the present invention, there is provided an ionizing radiation-curable composition suitably used for forming a hard coat layer having excellent adhesion (initial adhesion and light resistance adhesion) to such a base film. can be done.
• the ionizing radiation-curable composition of the present invention has an ionizing radiation-curable resin (component A) containing an acrylic resin having a (meth)acryloyl group and a hindered amine-based photostabilizing group.
• the content ratio of the silane coupling agent (component B) containing at least a silane coupling agent (component B) and having the hindered amine-based photostabilizing group (component B) is 0.5% by mass to 2.8% by mass relative to the solid content. It is characterized by
• the ionizing radiation-curable composition of the present invention comprises at least an ionizing radiation-curable resin containing an acrylic resin having a (meth)acryloyl group as component A, and a silane having a hindered amine-based photostabilizing group as component B. It contains a coupling agent.
• the resin component (component A) contained in the ionizing radiation-curable composition includes the surface hardness of the hard coat layer ( scratch resistance, pencil hardness), and it is possible to adjust the degree of cross-linking by adjusting the exposure dose of ultraviolet rays or electron beams, making it possible to adjust the surface hardness of the hard coat layer. It is preferred to use a mold resin.
• the ionizing radiation curable resin used in the present invention is a transparent resin that is cured by irradiation with ultraviolet rays (hereinafter abbreviated as "UV”) or electron beams (hereinafter abbreviated as “EB”).
• UV ultraviolet rays
• EB electron beams
• acrylic resin by using an acrylic resin in particular, the transparency and scratch resistance of the surface of the cured coating film can be made suitable.
• the acrylic resin contained as component A is an acrylic resin having a (meth)acryloyl group, such as (meth)acrylate.
• a (meth)acryloyl group refers to one or both of an acryloyl group and a methacryloyl group
• a (meth)acrylate refers to one or both of an acrylate and a methacrylate.
• the acrylic resin having a (meth)acryloyl group used in the present invention has three or more (meth)acryloyl groups in one molecule to form a three-dimensional crosslinked structure.
• a curable polyfunctional (meth)acrylate is preferred.
• Specific examples of UV- or EB-curable polyfunctional (meth)acrylates having 3 or more (meth)acryloyl groups in the molecule include trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate.
• pentaerythritol tetra(meth)acrylate dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane ethoxytri Acrylate, glycerin propoxy triacrylate, ditrimethylolpropane tetraacrylate and the like can be mentioned.
• polyfunctional (meth)acrylate may not only be used individually but may be used in mixture of 2 or more types.
• the ionizing radiation-curable resin used in the present invention preferably uses a polymer having a weight average molecular weight (Mw) within the range of 700 to 3600, more preferably having a weight average molecular weight within the range of 700 to 3000.
• Mw weight average molecular weight
• a weight average molecular weight of 700 to 2400 is more preferred.
• the weight-average molecular weight is less than 700, curing shrinkage when cured by UV or EB irradiation is large, and the phenomenon (curling) in which the hard coat film is warped toward the hard coat layer side becomes large. Defects occur and processing aptitude is poor.
• the weight average molecular weight exceeds 3600, the flexibility of the hard coat layer is increased, but the hardness is insufficient, which is not suitable.
• thermoplastic resins such as polyethylene, polypropylene, polystyrene, polycarbonate, polyester, styrene-acryl, cellulose, etc.
• resin components contained in the ionizing radiation-curable composition include , phenolic resins, urea resins, unsaturated polyesters, epoxy resins, silicon resins, and other thermosetting resins may be blended within a range that does not impair the effects of the present invention.
• the ionizing radiation-curable composition of the present invention contains, as Component B, a silane coupling agent having a hindered amine-based photostabilizing group.
• a silane coupling agent having a hindered amine-based light-stabilizing group contained as component B for example, a silane coupling agent represented by the following general formula is preferably mentioned.
• R 1 represents an alkyl group having 1 to 3 carbon atoms.
• R 2 represents an alkylene group or alkyleneoxy group (-O-alkylene group) having 2 to 5 carbon atoms.
• X represents either a hydrogen atom, a methyl group, an ethyl group, or an alkoxyl group having 1 to 3 carbon atoms.
• Specific compounds of the silane coupling agent having a hindered amine photostabilizing group used in the present invention include, for example, 3-(2,2,6,6-tetramethylpiperid-4-yloxypropyl)triethoxy silane, 3-(1,2,2,6,6-pentamethylpiperid-4-yloxypropyl)triethoxysilane, and the like.
• the ionizing radiation-curable composition of the present invention uses a silane coupling agent having a hindered amine-based light-stabilizing group as component B to obtain a hard coat layer comprising a cured coating film of the ionizing radiation-curable composition of the present invention. is formed, it is possible to obtain initial adhesion with the hard coat layer and excellent light resistance adhesion even for substrate films with few polar groups such as cycloolefin films and poor adhesion with the hard coat layer. It becomes possible.
• the initial adhesion is the covalent bond between the silane coupling agent and the substrate surface that is formed at the substrate surface interface (that is, the silane coupling agent and the hydroxy
• the excellent light resistance adhesion is due to the fact that the silane coupling agent is unevenly distributed near the substrate interface and the hindered amine photostabilizing group of the silane coupling agent is fixed. be.
• the surface treatment of the base film and the anchor coat layer are not required.
• a hard coat film having excellent adhesion to the hard coat layer initial adhesion and light-resistant adhesion
• the ionizing radiation-curable composition of the present invention has excellent adhesion to such a substrate film ( It is suitable for forming a hard coat layer having excellent initial adhesion and light resistance adhesion.
• the content ratio of the silane coupling agent (component B) having a hindered amine-based photostabilizing group is in the range of 0.5% by mass to 2.8% by mass based on the solid content. It is particularly preferably in the range of 1.0% by mass to 2.6% by mass based on the solid content.
• silane coupling agent (component B) having the hindered amine-based light-stabilizing group within the above range, it is possible to obtain a base film such as a cycloolefin film having few polar groups and poor adhesion to the hard coat layer. Also, it is possible to obtain initial adhesion to the hard coat layer and excellent light resistance adhesion.
• the amount of the silane coupling agent (component B) having a hindered amine photostabilizing group is less than the above range (less than 0.5% by mass relative to the solid content), the effect of the present invention cannot be obtained sufficiently. In particular, light resistance adhesion becomes insufficient. Further, when the silane coupling agent (component B) having the hindered amine-based photostabilizing group is blended in an amount larger than the above range (exceeding 2.8% by mass relative to the solid content), radicals generated by irradiation with ionizing radiation are Since the component B is absorbed, the initial adhesion is particularly insufficient.
• the silane coupling agent having a hindered amine photostabilizing group may be used alone or in combination of two or more.
• a general silane coupling agent such as methyltrimethoxysilane may be used in combination within a range that does not impair the effects of the present invention.
• the silane coupling agent having the hindered amine photostabilizing group desirably does not have a fluorine group. That is, it is desirable not to contain a silane coupling agent having a fluorine group in its structure.
• the silane coupling agent having the hindered amine photostabilizing group is unevenly distributed at the interface between the cured coating film of the ionizing radiation-curable composition and the substrate film, and the hindered amine photostabilizing group of the silane coupling agent is fixed. This contributes to the improvement of light resistance adhesion.
• the silane coupling agent such as a silane coupling agent having a fluorine group in its structure in addition to the hindered amine photostabilizing group, is introduced to the interface between the air layer and the cured coating film,
• a compound having a structure that has the effect of lowering the concentration of the silane coupling agent unevenly distributed at the interface between the cured coating film and the substrate film cannot be preferably used.
• the ionizing radiation-curable composition of the present invention can further contain inorganic oxide fine particles as Component C.
• inorganic oxide fine particles include silicon oxide (silica), aluminum oxide (alumina), titanium oxide, and zirconia.
• inorganic oxide fine particles particularly by blending silica fine particles, it is possible to improve the surface hardness (pencil hardness, scratch resistance) of the cured coating film of the ionizing radiation-curable composition of the present invention and to suppress curling.
• adhesion to the base film can be further improved.
• the inorganic oxide fine particles are desirably nano-order sized particles, and the average particle diameter is from 5 nm to 5 nm.
• a range of 200 nm is preferred, a range of 5 nm to 50 nm is more preferred, and a range of 10 nm to 20 nm is even more preferred.
• the average particle size is less than 5 nm, it is difficult to obtain sufficient surface hardness.
• the average particle size exceeds 200 nm, the transparency and gloss of the cured coating film are likely to be reduced, and the flexibility may also be reduced.
• the content ratio of the inorganic oxide fine particles can further improve the pencil hardness of the surface of the cured coating film of the ionizing radiation-curable composition of the present invention, and can further improve the adhesion to the substrate film. % to 75% by mass, more preferably 10% to 50% by mass based on the solid content. If the content ratio of the inorganic oxide fine particles is less than 1% by mass, it is difficult to obtain the effect of improving the surface hardness (pencil hardness). On the other hand, if the content exceeds 75% by mass, the haze increases, which is not preferable.
• the ionizing radiation-curable composition of the present invention can contain a diluent (component D).
• the diluent can be used to adjust the solution (coating) viscosity when applying the ionizing radiation curable composition of the present invention.
• the diluent can be appropriately selected depending on the solubility of the ionizing radiation curable type to be blended, and at least the solid content (resin, silane coupling agent, other additives (leveling agent, photoinitiator, etc.), etc.) Any solvent can be used as long as it can dissolve or disperse uniformly.
• Solvents that can be used here include ethers such as diethyl ether and propylene glycol monomethyl ether, alcohols such as methanol, ethanol, isopropanol, and t-butanol, and ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and the like.
• ethers such as diethyl ether and propylene glycol monomethyl ether
• alcohols such as methanol, ethanol, isopropanol, and t-butanol
• ethyl acetate butyl acetate
• propylene glycol monomethyl ether acetate and the like.
• Examples include esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. These solvents can be used singly or in combination of two or more.
• the solvent may be propylene glycol monomethyl ether or the like in order to prevent aggregation and sedimentation of the inorganic oxide fine particles.
• Ethers and ketones such as methyl ethyl ketone are preferably used.
• the solvent ratio after dilution (the final solvent ratio in the ionizing radiation-curable composition) is The content of the hydrocarbon solvent is preferably less than 30% by mass, more preferably 15% by mass or less, still more preferably 10% by mass or less, and most preferably 5% by mass or less. If 30% by mass or more of the aromatic hydrocarbon solvent is used as the diluent, it is not preferable because it corrodes the substrate and causes chemical cracks in the hard coat film.
• the ionizing radiation-curable composition of the present invention uses an ionizing radiation-curable resin as a resin component, it can contain a photopolymerization initiator.
• photopolymerization initiators include commercially available acetophenones such as Omnirad 651 and Omnirad 184 (both trade names: manufactured by IGM Resins), and benzophenones such as Omnirad 500 (trade name: manufactured by IGM Resins). can be used.
• the ionizing radiation curable composition of the present invention contains, in addition to the above components A, B, C and D, the above photopolymerization initiator, and if necessary, a leveling agent, a light stabilizer, Additives such as polymerization inhibitors, ultraviolet absorbers, organic pigments, inorganic pigments, pigment dispersants, and organic beads can be added. These formulations can be used singly or in combination of two or more.
• a leveling agent for the purpose of improving coatability.
• a leveling agent can be used.
• the compounding amount can be in the range of 0.03 to 3.0 parts by weight per 100 parts by weight of the solid content of the resin in the composition.
• OCR optically transparent adhesive
• OCR optically transparent adhesive
• the hard coat film of the present invention has a hard coat layer comprising a cured coating film of the above-described ionizing radiation-curable composition of the present invention on at least one surface of a base film. It is characterized by
• examples of the base film of the hard coat film include polyethylene terephthalate film, polyethylene naphthalate, and cycloolefin film (cycloolefin polymer film).
• the ionizing radiation-curable composition of the present invention can obtain excellent transparency, scratch resistance, initial adhesion and light-resistant adhesion using any of these substrates, but in particular, cycloolefin film substrates can be used. It can be used preferably.
• a cycloolefin film is excellent in transparency, heat resistance, dimensional stability, low hygroscopicity, low birefringence, optical isotropy, etc., but is inferior in adhesion to a hard coat layer.
• the ionizing radiation curable composition of the present invention By using the ionizing radiation curable composition of the present invention, even for a substrate film such as a cycloolefin film having few polar groups and poor adhesion to the hard coat layer, the surface treatment of the substrate film and the anchor coat layer It is possible to obtain a hard coat film excellent in adhesion (initial adhesion and light resistance adhesion) to the hard coat layer without the need for
• cycloolefin film base material a homopolymer or a copolymer can be used without limitation as long as the cycloolefin is polymerized.
• cycloolefin units are alternately or randomly polymerized in the polymer skeleton and have an alicyclic structure in the molecular structure, and are norbornene compounds, monocyclic cyclic olefins, cyclic conjugated dienes and vinyl alicyclic compounds.
• thermogravimetry (TG) method and differential scanning calorimetry (DSC) method that measure the thermal change when the sample is subjected to a temperature change. It is preferable to use a film having a glass transition temperature of about 120° C. to 170° C. as measured by the above method.
• the thickness of the base film is appropriately selected depending on the application, but it is preferably in the range of 10 ⁇ m to 300 ⁇ m from the viewpoint of mechanical strength, handleability, thinning of the display device, etc. and more preferably in the range of 20 ⁇ m to 200 ⁇ m.
• a hard coat layer is formed on one side of the base film, for example, a cycloolefin film
• the back side of the cycloolefin film on which the hard coat layer is not formed is provided to prevent crimping of the base film winding.
• polyethylene resin, polypropylene resin, or polyester resin which has excellent releasability from the cycloolefin film by co-extrusion, is used as a protective layer during cycloolefin film formation. It is good also as a film laminated as.
• cycloolefin film examples include commercially available Zeonor (trade name: manufactured by Nippon Zeon Co., Ltd.), Optica (trade name: manufactured by Mitsui Chemicals, Inc.), ARTON (trade name: manufactured by JSR Corporation), and Kozek (trade name: manufactured by JSR Corporation).
• Zeonor trade name: manufactured by Nippon Zeon Co., Ltd.
• Optica trade name: manufactured by Mitsui Chemicals, Inc.
• ARTON trade name: manufactured by JSR Corporation
• Kozek trade name: manufactured by JSR Corporation.
• Product name manufactured by Kurashiki Boseki Co., Ltd.
• a cycloolefin film when used as the base film of the hard coat film, a cycloolefin film that has not been pretreated for the purpose of making the hard coat layer easier to adhere can be preferably used.
• the hard coat layer composed of the cured coating film of the ionizing radiation-curable composition of the present invention can obtain sufficient adhesion to the substrate film without pretreatment of the substrate film for the purpose of hardening. .
• the hard coat layer of the hard coat film of the present invention comprises a cured coating film of the ionizing radiation-curable composition of the present invention. Description is omitted.
• the present invention also provides a method for producing a hard coat film having the configuration described above. That is, as in the eighth invention, the method for producing a hard coat film of the present invention includes a hard coat layer comprising a cured coating film of an ionizing radiation-curable composition on at least one surface of a base film.
• the production of the hard coat film of the present invention includes a step of applying the ionizing radiation-curable composition to the base film, a drying step of the coating film of the ionizing radiation-curable composition, and curing the coating film using ultraviolet rays or the like.
• a process is required at least. That is, on the substrate film, the ionizing radiation-curable composition (hard coat paint) of the present invention whose solution viscosity is appropriately adjusted with the above-mentioned diluent is applied, dried to form a coating film, and then coated.
• the hard coat film of the present invention is produced by irradiating the film with ionizing radiation to form a cured coating film (hard coat layer) of the ionizing radiation curable composition.
• the method of applying the ionizing radiation curable composition is not particularly limited, but gravure coating, micro gravure coating, wire bar coating, fountain bar coating, slide die coating, slot die coating.
• a known coating method such as a coating method, a screen printing method, or a spray coating method can be applied.
• the coating thickness of the coating film of the hard coat layer is not particularly limited, but is preferably in the range of, for example, 0.5 ⁇ m to 5.0 ⁇ m, more preferably 1.0 ⁇ m to 3.5 ⁇ m. range. If the coating thickness is less than 0.5 ⁇ m, the necessary scratch resistance and pencil hardness are lowered, which is not preferable. On the other hand, if the coating thickness exceeds 5.0 ⁇ m, the curling tends to occur strongly, and the handleability in the manufacturing process is deteriorated, which is not preferable.
• the coating thickness of the hard coat layer can be measured by actual measurement with a micrometer.
• the coating film in the step of drying the coating film after application of the ionizing radiation-curable composition, is dried under the condition that the substrate temperature in the last stage of the drying step is 50°C to 100°C. is preferred.
• the substrate temperature as used herein is the temperature of the substrate film or the ionizing radiation-curable composition coating film.
• the substrate temperature is the temperature measured directly on the substrate. That is, in order to remove volatile components contained in the ionizing radiation-curable composition and keep the temperature of the ionizing radiation-curable composition sufficiently high in the subsequent curing step, the substrate temperature in the final stage of the drying process should be 50° C. or higher. is preferred, and 55°C or higher is more preferred.
• the substrate temperature is preferably 100° C. or lower, more preferably 85° C. or lower.
• the heat drying time can be appropriately set.
• the wind speed can be appropriately set.
• the last stage of the drying process is, for example, when the drying process is performed using a dryer having a single drying area, the single drying area is the last stage. Further, when the drying process is carried out by passing through a dryer having a plurality of drying zones (for example, three stages of drying zones, front stage, middle stage, and rear stage), the rear stage zone is the final stage.
• the irradiation amount of ionizing radiation (UV, EB, etc.) to the coating film after drying may be any irradiation amount necessary for imparting sufficient hardness to the hard coat layer. It can be set as appropriate according to, for example.
• the surface treatment of the base film and the anchor coat layer can be applied. It is possible to provide a hard coat film excellent in adhesion (initial adhesion and light resistance adhesion) to the hard coat layer without requiring Further, according to the present invention, there is provided an ionizing radiation-curable composition suitably used for forming a hard coat layer having excellent adhesion (initial adhesion and light resistance adhesion) to such a base film. can be done.
• Example 1 Contains 30% silica fine particles (average particle diameter about 15 nm) in the resin and 3% photopolymerization initiator in the resin, acrylic ester containing (meth) acryloyl group (manufactured by Arakawa Chemical Industries, Ltd. "CHCI-102", 52% propylene glycol monomethyl ether (PGME) solution, hereinafter sometimes referred to as "CHCI-102".) 188.4 parts, 3-(2,2,6,6-tetramethylpiperidi-4-yloxy Propyl) triethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.
• TMPS-E solid content 100%, hereinafter sometimes referred to as "TMPS-E"
• PGME solvent propylene glycol monomethyl ether
• Ftergent 602A a leveling agent manufactured by Neos Co., Ltd., 50% ethyl acetate solution, hereinafter sometimes referred to as "FT602A”
• Example 2 The amount of the silane coupling agent (TMPS-E) in Example 1 was changed from 2.0 parts to 1.0 parts, and the amount of each of the acrylic ester (CHCI-102) and the solvent propylene glycol monomethyl ether (PGME) was changed to An ionizing radiation-curable composition (2) was prepared in the same manner as in Example 1 except that the composition was changed as shown in Table 1 below.
• Example 3 The compounded amount of the silane coupling agent (TMPS-E) in Example 1 was changed from 2.0 parts to 2.6 parts, and the compounded amount of each of the acrylic ester (CHCI-102) and the solvent propylene glycol monomethyl ether (PGME) was changed to An ionizing radiation-curable composition (3) was prepared in the same manner as in Example 1 except that the composition was changed as shown in Table 1 below.
• Example 4 Instead of the silane coupling agent (TMPS-E) in Example 1, a silane coupling agent containing a fluorine group ("X-12-1310A" manufactured by Shin-Etsu Chemical Co., Ltd., solid content 100%, hereinafter "X-12 -1310A") was used in the same manner as in Example 1 to prepare an ionizing radiation-curable composition (4).
• TMPS-E silane coupling agent
• FT602A leveling agent
• An ionizing radiation curable composition (6) was prepared in the same manner as in 1.
• the solid content ratio is the same as in Example 1 above.
• Example 7 In the same manner as in Example 1 except that the acrylic ester (CHCI-102) not containing silica particles was used instead of the acrylic ester (CHCI-102) in Example 1, an ionizing radiation curable composition (7 ) was prepared.
• the solid content ratio is the same as in Example 1 above.
• Example 8 Same as Example 1 except that instead of the acrylic ester (CHCI-102) in Example 1, an acrylic ester (CHCI-102) with increased silica fine particles (50% silica fine particles in the resin) was used. to prepare an ionizing radiation curable composition (8).
• the solid content ratio is the same as in Example 1 above.
• Example 1 The silane coupling agent (TMPS-E) of Example 1 was not used, and the amounts of acrylic ester (CHCI-102) and solvent propylene glycol monomethyl ether (PGME) were changed as shown in Table 2 below.
• An ionizing radiation-curable composition (9) was prepared in the same manner as in Example 1 except that the above was performed.
• Example 2 The amount of the silane coupling agent (TMPS-E) of Example 1 was changed from 2.0 parts to 3.0 parts, and the amount of each of the acrylic ester (CHCI-102) and the solvent propylene glycol monomethyl ether (PGME) was changed to An ionizing radiation-curable composition (10) was prepared in the same manner as in Example 1, except that the composition was changed as shown in Table 2 below.
• Example 3 methyltrimethoxysilane ("KBM-13" manufactured by Shin-Etsu Chemical Co., Ltd., solid content 100%, hereinafter "KBM-13") was used as a silane coupling agent.
• Ionizing radiation curable composition (11) was prepared in the same manner as in Example 1, except that 2.0 parts of the composition was used.
• Example 4 Vinyltriethoxysilane ("KBE-1003" manufactured by Shin-Etsu Chemical Co., Ltd., solid content 100%, hereinafter "KBE-1003") was used as a silane coupling agent.
• Ionizing radiation curable composition (12) was prepared in the same manner as in Example 1, except that 2.0 parts of " was used.
• Example 5 Comparative Example 5
• An ionizing radiation-curable composition (13) was prepared in the same manner as in Example 1, except that 1.0 part of a solid content of 100% (hereinafter sometimes referred to as "TN292") was also used.
• Example 1 [Preparation of hard coat film] (Examples 1 to 8, Comparative Examples 1 to 6)
• the ionizing radiation-curable composition (1) of Example 1 prepared as described above was applied to one surface of a cycloolefin film (“ZEONOR film” manufactured by Nippon Zeon Co., Ltd., thickness 22 ⁇ m, with a polyethylene terephthalate protective film). It was evenly applied on (the side to which the protective film is not applied) using a cast or wire bar.
• this film with a coating film is provided with three stages of drying areas, the first stage, the middle stage, and the last stage, and the temperature in the drying area of the first stage to the middle stage is 50 ° C., and the temperature in the final drying area is 100 ° C.
• the coating film was dried by heating under conditions such that the substrate temperature in the final stage of the drying process was 75°C. Next, using an ultraviolet irradiation device, this is irradiated with ultraviolet rays at an irradiation light amount of 80 mJ/cm 2 to cure the coating film, forming a hard coat layer having a thickness of 1 ⁇ m, and the hard coat film of Example 1 ( 1) was produced.
• the above cycloolefin film is not subjected to any pretreatment for easy adhesion such as surface roughening treatment, electrical treatment, ozone/ultraviolet/electron beam irradiation treatment, flame treatment, hot air treatment, oxidation treatment, etc. .
• Example 9 The procedure was carried out in the same manner as above, except that the ionizing radiation-curable composition (1) of Example 1 was used and the coating film was heated and dried under conditions such that the substrate temperature in the final stage of the drying step was 65°C. , a hard coat film (9) of Example 9 was produced.
• Adhesion was evaluated by a cross-cut peeling test according to JIS-K5600-5-6. Specifically, for each hard coat film produced in Examples and Comparative Examples, a cutter knife was applied to the hard coat layer formation surface under a normal environment, that is, under a constant temperature and humidity environment (25 ° C., 50% RH). 11 vertical and 11 horizontal incisions were made in a grid pattern at intervals of 1 mm to cut a total of 100 squares, and adhesive tape No. 252 manufactured by Sekisui Chemical Co., Ltd. was pasted thereon.
• evaluation criteria are as follows, and regarding the initial adhesion, ⁇ and ⁇ evaluation products were judged to be acceptable. Evaluation criteria ⁇ : 100 pieces ⁇ : 99 to 95 pieces ⁇ : 94 to 50 pieces ⁇ : 49 to 0 pieces
• the hard coat films of Examples of the present invention using the ionizing radiation-curable composition of the present invention are excellent in both initial adhesion and light resistance adhesion, and can be used for 150 hours.
• the light resistance adhesion after 300 hours was evaluated as " ⁇ " or " ⁇ ".
• a hard coat layer having excellent adhesion is formed even on a substrate film such as a cycloolefin film that has few polar groups and poor adhesion to the hard coat layer. It is possible to provide an ionizing radiation curable composition suitable for Furthermore, the hard coat films of the examples of the present invention also gave good results in surface texture evaluation.
• Comparative Example 1 which does not contain the silane coupling agent having a hindered amine photostabilizing group of the present invention in the ionizing radiation curable composition, and the silane cup having a hindered amine photostabilizing group in the ionizing radiation curable composition.
• Comparative Example 2 in which the compounding amount of the ring agent is larger than the range of the present invention.
• Comparative Example 4 and Comparative Examples 5 and 6 in which the hindered amine light stabilizer and the silane coupling agent were used as separate agents in the ionizing radiation curable composition, initial adhesion and/or light resistance However, it is inferior (“ ⁇ ” evaluation), and practical improvement is desired.

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• 2022
  • 2022-03-18 JP JP2023509142A patent/JPWO2022202699A1/ja active Pending
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