JP2013155313A - Adhesive sheet for optical base material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive sheet for an optical base material, which has functions of high transparency, scattering prevention and the like in the case of being used in optical applications, and is suitable, for example, for manufacture of liquid crystal constituting members such as touch panels, liquid crystal polarizing sheets and retardation sheets, for manufacture of various types of display constituting members such as PDP constituting member manufacture and organic EL constituting member manufacture, and additionally for various types of optical applications.SOLUTION: An adhesive sheet for an optical base material has an adhesive sheet layer on each of both surfaces of a film base material, wherein the haze of the adhesive sheet when a float glass of 1 mm in thickness is pasted on each of the adhesive sheet layers is ≤1.2%; and a releasing layer is provided on each of both the surfaces of the adhesive sheet layers.

Description

  Since the present invention has functions such as high transparency and scattering prevention when the pressure-sensitive adhesive sheet for an optical substrate is used for optical applications, for example, for producing liquid crystal components such as a touch panel, a liquid crystal polarizing plate, a retardation plate, The present invention relates to an adhesive sheet for an optical substrate suitable for various optical applications and the like, as well as for the production of various display components such as for the production of PDP components and for the production of organic EL components.

  Conventionally, various pressure-sensitive adhesive sheets for surface bonding between objects are known, and a base-less double-sided pressure-sensitive adhesive sheet is known as one of pressure-sensitive adhesive sheets.

  The substrate-less double-sided pressure-sensitive adhesive sheet is configured by laminating a light release sheet having a relatively low peeling force and a heavy release sheet having a relatively high peeling force on both sides of the pressure-sensitive adhesive layer, and removing the double-sided release sheet. The latter is a double-sided pressure-sensitive adhesive sheet that only has a pressure-sensitive adhesive layer that does not have a supporting substrate.

  The baseless double-sided PSA sheet is first peeled off from the light release release film, and one side of the exposed PSA layer is bonded to the object surface. Then, the other surface of the exposed pressure-sensitive adhesive layer is bonded to a different object surface, whereby the objects are surface-bonded. In the process of bonding to this separate object, it is important to balance the release forces of the release films on the light release side and the heavy release side.

  In recent years, the base-less double-sided pressure-sensitive adhesive sheet is being used for various optical applications and the like. For example, when the electronic base material and the glass on the surface of the touch panel are bonded to each other as a touch panel member, defects such as a foreign substance of an adhesive remaining as a base material are more important than ever.

  By applying the technology of the baseless double-sided pressure-sensitive adhesive sheet shown above and sandwiching it between highly transparent film base materials, the thickness and amount of pressure-sensitive adhesive can be reduced, and the cost-effective pressure-sensitive adhesive sheet for optical substrates Development is required.

  In the case of using glass on the outer surface of some touch panels, TVs, and the like, such an adhesive sheet for an optical substrate has a scattering prevention function. Moreover, in the case of the use which uses glass for outer surfaces, such as a touch panel and TV, such an adhesive sheet for optical base materials has an impact absorption function. Further, in applications where the pressure-sensitive adhesive has multiple functions, such as high transparency for the first pressure-sensitive adhesive, high refraction for the second pressure-sensitive adhesive, etc., it can be used as a variety-rich additional function pressure-sensitive adhesive.

  The technical barrier of the pressure-sensitive adhesive sheet for optical substrates of the above uses is in the optical properties of the film used as the film substrate (the role of the core), and compared with the sheet of pressure-sensitive adhesive alone, the light transmittance, haze and It is required that there is no significant optical loss or change in appearance due to the refractive index.

JP 2009-220296 A JP 2009-214360 A JP 2006-305915 A

  The present invention has been made in view of the above circumstances, and the problem to be solved is that when the pressure-sensitive adhesive sheet for an optical substrate is used for optical applications, it has functions such as high transparency and scattering prevention, for example, a touch panel. For manufacturing various liquid crystal components such as liquid crystal polarizing plates and retardation plates, for manufacturing PDP components, for manufacturing organic EL components, etc. For optical substrates suitable for various optical applications, etc. It is to provide an adhesive sheet.

  As a result of intensive studies in view of the above circumstances, the present inventors have found that the above problem can be easily solved by a polyester film having a specific configuration, and have completed the present invention.

  That is, the gist of the present invention is a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive sheet layer on both surfaces of a film substrate, and the haze of the pressure-sensitive adhesive sheet when a 1 mm thick float plate glass is bonded to each surface of the pressure-sensitive adhesive sheet layer. The pressure-sensitive adhesive sheet for optical substrates is 1.2% or less and has release layers on both sides of the pressure-sensitive adhesive sheet layer.

  According to the present invention, by sandwiching a polyester film, it is usually possible to ensure low cost and necessary transparency as compared with a pressure-sensitive adhesive having the same thickness. The pressure-sensitive adhesive sheet for an optical substrate can be provided, and the industrial value of the present invention is high.

Typical sectional drawing which shows the adhesive sheet for optical base materials which concerns on embodiment of this invention Typical sectional drawing which shows the precursor of the 1st and 2nd base material less double-sided adhesive sheet layer which comprises the adhesive sheet 10 for optical base materials

  As shown in FIG. 1, the pressure-sensitive adhesive sheet 10 for an optical substrate is configured by laminating the first and second substrate-less double-sided pressure-sensitive adhesive sheets on both surfaces of a film substrate 11. . The first release film 31 of the first substrate-less double-sided pressure-sensitive adhesive sheet 41 bonded to the film substrate 11 is a so-called light release sheet, and is a release film substrate 13 made of a polyester film, a coating layer 14, a first release film 31. The release agent layer 15 is laminated, and the first release agent layer 15 is temporarily attached to the pressure-sensitive adhesive layer 12 so as to be peeled off. Further, the second release film 32 of the second substrate-less double-sided pressure-sensitive adhesive sheet 42 bonded to the film substrate 11 is a so-called heavy release sheet, which is a release film substrate 23 made of a polyester film, a coating layer 24, The 2nd mold release agent layer 25 is laminated | stacked, and the 2nd mold release agent layer 25 is temporarily attached to the adhesive layer 22 so that peeling is possible.

  As shown in FIG. 2, the first baseless double-sided pressure-sensitive adhesive sheet precursor 41 ′ is configured by laminating first and first ′ release films on both sides of the pressure-sensitive adhesive layer 12. The first release film 31 bonded to the pressure-sensitive adhesive layer 12 is a so-called heavy release sheet as compared with the first 'release film 31', and is a first release film substrate 13 made of a polyester film, and a first application. The layer 14 and the 1st mold release agent layer 15 are laminated | stacked, and the 1st mold release agent layer 15 is temporarily attached to the adhesive layer 12 so that peeling is possible. Further, the first 'release film 31' bonded to the pressure-sensitive adhesive layer 12 is a so-called light release sheet as compared with the first release film 31, and is a first 'release film substrate 13' made of a polyester film. The first 'coating layer 14' and the first 'release agent layer 15' are laminated, and the first 'release agent layer 15' is temporarily attached to the pressure-sensitive adhesive layer 12 in a peelable manner.

  Further, as shown in FIG. 2, the second base-less double-sided pressure-sensitive adhesive sheet precursor 42 ′ is configured by laminating a second and second ′ release film on both surfaces of the pressure-sensitive adhesive layer 22. The second release film 32 bonded to the pressure-sensitive adhesive layer 22 is a so-called heavy release sheet as compared with the second 'release film 32', and is a second release film substrate 23 made of a polyester film, a second application. The layer 24 and the 2nd mold release agent layer 25 are laminated | stacked, and the 2nd mold release agent layer 25 is temporarily attached to the adhesive layer 22 so that peeling is possible. Further, the second 'release film 32' bonded to the pressure-sensitive adhesive layer 22 is a so-called light release sheet as compared with the second release film 32, and is a second 'release film substrate 23' made of a polyester film. The second ′ coating layer 24 ′ and the second ′ release agent layer 25 ′ are laminated, and the second ′ release agent layer 25 ′ is temporarily attached to the pressure-sensitive adhesive layer 22 so as to be peeled off.

  The film substrate in the present invention may be a polymer film characterized by high transparency and low haze as optical characteristics. In particular, in the present invention, it is particularly preferable to use a polyester excellent in the above characteristics, inexpensive and excellent in workability.

  The polyester film referred to in the present invention is a film which is melt-extruded from an extrusion die, and is subjected to stretching and heat treatment as necessary after cooling a molten polyester sheet extruded by a so-called extrusion method.

  The base material used for the release films 31, 31 ′ and 32, 32 ′ and the polyester forming the film base material 11 are obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic glycol. Examples of the aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid, and examples of the aliphatic glycol include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol. Representative polyesters include polyethylene terephthalate (PET), polyethylene-2,6-naphthalenedicarboxylate (PEN), and the like. The polyester used may be a homopolyester or a copolyester. In the case of a copolyester, it may be a copolymer containing 30 mol% or less of the third component. Examples of the dicarboxylic acid component of such a copolyester include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, and oxycarboxylic acid (eg, P-oxybenzoic acid). 1 type or 2 types or more chosen from are mentioned. One glycol component includes one or more selected from ethylene glycol, diethylene glycol, propylene glycol, butanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, and the like.

  In the polyester obtained by the present invention, a weathering agent, a light-proofing agent, an antistatic agent, a lubricant, a light-shielding agent, an antioxidant, a fluorescent whitening agent, a matting agent, and a heat-stabilizing agent as long as the gist of the present invention is not impaired. You may mix | blend an agent and coloring agents, such as dye and a pigment.

  Examples of the particles to be blended in the film include silicon oxide, alumina, calcium carbonate, kaolin, titanium oxide, and crosslinked polymer fine powder as described in JP-B-59-5216. These particles may be used alone or in combination of two or more components. The blending amount of these particles is usually 1% by weight or less, preferably 0.01 to 1% by weight, more preferably 0.02 to 0.6% by weight, based on the polyester constituting the film. When the content of the particles is small, the film surface cannot be appropriately roughened, and in the film production process, there is a tendency that the surface is easily scratched or the winding properties are inferior. Further, when the content of the particles exceeds 1% by weight, the degree of roughening of the film surface becomes too large, and the transparency may be impaired.

  Although it does not specifically limit as an average particle diameter of the particle | grains mix | blended in the polyester film used for release film 31, 31 'and 32, 32', Usually 0.02 micrometer-5 micrometers, Preferably it is 0.02 micrometer-. It is in the range of 3.5 μm, more preferably 0.02 μm to 3.2 μm. When particles having an average particle size of less than 0.02 μm are used, sufficient slipperiness cannot be imparted, so that the winding characteristics in the film production process tend to be inferior. On the other hand, when the average particle diameter exceeds 5 μm, the degree of roughening of the film surface becomes too large, and the cloudiness of the film may increase.

  On the other hand, in order to improve the transparency of the film, when a laminated film of two or more layers is used, a method of blending particles only in the surface layer is also preferably employed. The surface layer in this case is at least one of the front and back layers, and of course, particles can be blended in both the front and back layers. The blending amount of the particles in the case of such a laminated film is preferably 0.01 to 1% by weight, more preferably 0.02 to 0.6% by weight, based on the polyester constituting the surface layer.

  In addition, a sharp particle size distribution is preferably used. Specifically, those having a particle size distribution value of 1.0 to 2.0, which is an index representing the sharpness of the particle size distribution, are preferable. Here, the particle size distribution value is the particle size distribution value d25 / d75 (d25 and d75 are calculated by calculating the accumulated accumulation of the particle group from the large particle side, and the particle size (μm corresponding to 25% and 75% of the total volume, respectively) Is a value defined by When the particle size distribution value exceeds 2.0, transparency may be insufficient.

  Although it does not specifically limit as an average particle diameter of the particle | grains mix | blended in the polyester film used for the film base material 11, Usually, 0.02 micrometer-3 micrometers, Preferably it is 0.02 micrometer-2.5 micrometers, More preferably, it is 0. The range is 0.02 μm to 2 μm. When particles having an average particle size of less than 0.02 μm are used, sufficient slipperiness cannot be imparted, so that the winding characteristics in the film production process tend to be inferior. On the other hand, when the average particle diameter exceeds 3 μm, the degree of roughening of the film surface becomes too large and the film may become hazy.

  On the other hand, the content of particles in the polyester layer used for the film substrate 11 is usually 0.0005 to 0.5% by weight, preferably 0.001 to 0.3% by weight. When the particle content is less than 0.0005% by weight, the slipperiness of the film may be insufficient, resulting in poor appearance such as scratches during film processing. On the other hand, when adding over 0.5 weight%, the transparency of a film may be inadequate.

  In the present invention, the method of blending the particles with the polyester is not particularly limited, and a known method can be adopted. For example, it can be added at any stage for producing the polyester, but it is preferably added as a slurry dispersed in ethylene glycol or the like at the stage of esterification or before the start of the polycondensation reaction after completion of the transesterification reaction. The condensation reaction may proceed. Also, a method of blending a slurry of particles dispersed in ethylene glycol or water with a vented kneading extruder and a polyester raw material, or a method of blending dried particles and a polyester raw material using a kneading extruder Etc.

  The polyester may be converted into chips after melt polymerization, and further subjected to solid phase polymerization as necessary under heating under reduced pressure or in an inert gas stream such as nitrogen. The intrinsic viscosity of the obtained polyester is preferably 0.40 dL / g or more, and more preferably 0.40 to 0.90 dL / g.

  Next, although the manufacturing method of the film of this invention is demonstrated concretely, as long as the summary of this invention is satisfied, it is not specifically limited to the following illustrations.

  First, the preferable example of the manufacturing method of polyester used by this invention is demonstrated. Here, an example in which polyethylene terephthalate is used as the polyester is shown, but the production conditions differ depending on the polyester used. According to a conventional method, esterification from terephthalic acid and ethylene glycol, or transesterification of dimethyl terephthalate and ethylene glycol, the product is transferred to a polymerization tank, the temperature is increased while reducing the pressure, and finally vacuum is applied. Under heating to 280 ° C., the polymerization reaction proceeds to obtain polyethylene terephthalate.

  Next, for example, the polyester chip obtained as described above and dried by a known method is supplied to a melt-extrusion apparatus and heated to a temperature equal to or higher than the melting point of each polymer and melted. Next, the molten polymer is extruded from the die, and rapidly cooled and solidified on the rotary cooling drum so as to have a temperature equal to or lower than the glass transition temperature to obtain a substantially amorphous unoriented sheet. In this case, in order to improve the flatness of the sheet, it is preferable to improve the adhesion between the sheet and the rotary cooling drum. In the present invention, an electrostatic application adhesion method and / or a liquid application adhesion method is preferably employed. In the present invention, the sheet thus obtained is stretched biaxially to form a film.

  Specifically describing the stretching conditions, the unstretched sheet is preferably stretched 2 to 6 times at 70 to 145 ° C. in the longitudinal direction to form a longitudinal uniaxially stretched film, and then 2 to 90 to 160 ° C. in the lateral direction. It is preferable to perform ~ 6 times stretching and heat treatment at 150 to 240 ° C for 1 to 600 seconds. Further, at this time, a method of relaxing 0.1 to 20% in the longitudinal direction and / or the transverse direction in the maximum temperature zone of the heat treatment and / or the cooling zone at the heat treatment outlet is preferable. Further, it is possible to add re-longitudinal stretching and re-lateral stretching as necessary. Furthermore, it is also possible to perform simultaneous biaxial stretching of the unstretched sheet so that the area magnification is 10 to 40 times.

  The thickness of the release film of the present invention is not particularly limited as long as it can be formed as a film and can be processed as a release film, but is usually 10 to 300 μm, preferably 30. It is -188 micrometers, More preferably, it is the range of 50-75 micrometers. If the film thickness is less than 10 μm, the film is not stiff, foreign matter in the process may be transferred, and trouble may occur in the process of peeling the release film. When the film thickness exceeds 300 μm, the productivity becomes worse at the time of film formation or processing, and the production cost increases.

  In the present invention, it is preferable to use release films having different thicknesses on both sides of the substrate-less double-sided pressure-sensitive adhesive sheet. Specifically, the thickness of the second release film is the thickness of the first release film. 1.2 times or more, preferably 1.4 times or more. By reducing the film thickness of the first release film on the light release side, it is possible to prevent the floating that occurs at the interface between the second release film and the adhesive layer when the first release film is peeled off. The above phenomenon of floating refers to a phenomenon in which the peeling force is weak at the time of peeling, and part of the pressure-sensitive adhesive layer peels off, bites air or the like, and the appearance deteriorates.

  In addition, when the adhesive is applied on the release surface of the release film, it is more susceptible to unevenness and foreign matter when manufacturing costs are taken into account to eliminate the influence of foreign matter and unevenness in the process. It is preferable to increase the film thickness of the second release film.

  The ratio of the thickness of the release film on the light release side and the thickness of the release film on the heavy release side is preferably larger than 1.2 times, and if it is less than 1.2 times, the cost contribution tends to be less. is there.

  The internal haze of the film substrate 11 of the present invention refers to a value measured by filling a quartz cell with ethanol and putting one produced film therein. The internal haze of the film substrate 11 of the present invention is preferably 0.6% or less, and is widely used for optical applications because of its excellent transparency. When the internal haze exceeds 0.6%, the transparency as an optical display member is impaired due to poor transparency.

  In order to make the internal haze of the film substrate 11 within the above range, it is possible to cause the phenomenon of pressure-sensitive adhesive particles or agglomerates by filtering, but the device of the film substrate also greatly affects. For example, various kinds of particles used for the film substrate, such as particle size, addition amount, filter reinforcement in the production line, film production conditions (film stretching temperature, draw ratio), smoothing of rolls used in the film production line, etc. This can be achieved by appropriately combining the conditions.

  The thickness of the film substrate 11 of the present invention is usually in the range of 12 to 75 μm. When the total film thickness is less than 12 μm, there are problems that wrinkles may occur at the time of bonding with the substrate-less pressure-sensitive adhesive sheet, or the effect of preventing scattering when using glass is impaired. On the other hand, when it is thicker than 75 μm, when it is used as a member near the surface of the touch panel, the writing effect due to the cushioning effect of the pressure-sensitive adhesive is lowered, and the transparency as an optical application pressure-sensitive adhesive sheet is impaired.

  In the present invention, an oligomer (hereinafter sometimes abbreviated as OL) is defined as a cyclic trimer among low molecular weight substances that crystallize and precipitate on the film surface after heat treatment.

  In the present invention, a film having a structure in which a polyester having a low OL content is coextruded and laminated on at least one surface of a layer composed of a polyester having a normal OL content may be used. In the polyester film for release film obtained by the invention, the effect of preventing the bright spot due to the precipitated OL is obtained, which is particularly preferable.

  The method for forming the coating layers 14 and 14 'or the coating layers 24 and 24' for preventing OL is not particularly limited, but a method of coating the coating solution in the process of producing the polyester film is preferably employed. . Specifically, a method of applying and drying a coating solution on the surface of an unstretched sheet, a method of applying and drying a coating solution on the surface of a uniaxially stretched film, and a method of applying and drying a coating solution on the surface of a biaxially stretched film Etc. Among these, it is economical to apply a coating solution on the surface of an unstretched film or a uniaxially stretched film, and then simultaneously dry and cure the coating layer in the process of heat-treating the film. Moreover, as a method for forming the coating layer, a method in which some of the above-described coating methods are used in combination can be adopted as necessary. Specifically, a method of applying a first layer on the surface of an unstretched sheet and drying, then stretching in a uniaxial direction, and then applying and drying a second layer can be used. Use the reverse roll coater, gravure coater, rod coater, air doctor coater, etc. shown in “Coating Method” by Yuji Harasaki, Tsuji Shoten, published in 1979, as a method of applying the coating solution to the surface of the polyester film. Can do.

  The coating solution used in the present invention is usually preferably adjusted with water as the main medium from the viewpoint of safety and hygiene. As long as water is the main medium, a small amount of an organic solvent may be contained for the purpose of improving the dispersion in water or improving the film forming performance. The organic solvent is preferably used as long as it is dissolved in water when mixed with water, which is the main medium. However, if it is a stable emulsion (emulsion) that does not separate after standing for a long time, Alternatively, it may be used in a state where it does not dissolve in water. The organic solvent may be used alone or in combination of two or more as necessary.

  The in-line coating is not limited to the following, but for example, in the sequential biaxial stretching, the coating treatment can be performed particularly before the lateral stretching after the longitudinal stretching is finished. When a coating layer is provided on a polyester film by in-line coating, coating can be performed simultaneously with film formation, and the coating layer can be processed at a high temperature, and a film suitable as a polyester film can be produced.

  In the present invention, a binder polymer is usually used for the coating layers 14 and 14 'or the coating layers 24 and 24'. The binder polymer is a polymer compound safety evaluation flow scheme (November 1985). The number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is defined as a high molecular compound having a film forming property of 1000 or more, according to the Chemical Substance Council).

  Analysis of the components in the coating layer can be performed by surface analysis such as TOF-SIMS.

  When providing a coating layer by in-line coating, the above-mentioned series of compounds is applied as an aqueous solution or dispersion, and the coating solution adjusted to a solid content concentration of about 0.1 to 50% by weight as a guide is applied onto the polyester film. It is preferable to produce a laminated polyester film. Moreover, in the range which does not impair the main point of this invention, a small amount of organic solvents may be contained in the coating liquid for the purpose of improving dispersibility in water, improving film-forming properties, and the like. Only one type of organic solvent may be used, or two or more types may be used as appropriate.

  In order to achieve the above object, in the present invention, an OL precipitation preventing layer is formed on the film surface by coating, and the layer comprises 10 to 100% by weight of polyvinyl alcohol, preferably 20 to 90% by weight, more preferably 30 to 30%. It shall contain 90% by weight. If the content of polyvinyl alcohol is less than 10% by weight, the oligomer sealing effect is insufficient, which is not preferable.

  The polyvinyl alcohol used in the present invention can be synthesized by a normal polymerization reaction and is preferably water-soluble. The degree of polymerization of polyvinyl alcohol is not particularly limited, but is usually 100 or more, preferably 300 to 40,000. When the degree of polymerization is 100 or less, the water resistance of the coating layer tends to decrease. The degree of saponification of the polyvinyl alcohol used in the present invention is not particularly limited, but a polyvinyl acetate saponified product that is usually 70 mol% or more, preferably 80 mol% or more and 99.9 mol% or less is practically used. It is done.

  A water-soluble or water-dispersible binder resin other than the above-mentioned polyvinyl alcohol may be used in combination with the coating layers 14 and 14 ′ or the coating layers 24 and 24 ′ in the present invention, if necessary. Examples of the binder resin include polyester, polyurethane, acrylic resin, vinyl resin, epoxy resin, amide resin, acrylate resin, and the like. In these, each skeleton structure may have a composite structure substantially by copolymerization or the like. Examples of the binder resin having a composite structure include acrylic resin graft polyester, acrylic resin graft polyurethane, vinyl resin graft polyester, vinyl resin graft polyurethane, and acrylate resin graft polyethylene glycol. The blending amount of the binder component is preferably 50 parts by weight or less, and more preferably 30 parts by weight or less in terms of parts by weight with respect to the coating layer. Furthermore, the coating layer of the film of the present invention may contain a crosslinking reactive compound as required.

  Cross-linking reactive compounds include methylolated or alkylolized urea, melamine, guanamine, acrylamide, polyamide and other compounds, polyamines, epoxy compounds, oxazoline compounds, aziridine compounds, blocked isocyanate compounds, silane cups Polyfunctional low molecular weight compounds such as ring agents, titanium coupling agents, zirco-aluminate coupling agents, metal chelates, organic acid anhydrides, organic peroxides, thermally or photoreactive vinyl compounds and photosensitive resins, and It is selected from polymer compounds.

  Crosslinkable compounds improve the cohesiveness, surface hardness, scratch resistance, solvent resistance, and water resistance of the easy-adhesive resin layer mainly by cross-linking reaction with the functional groups of the resin contained in the easy-adhesive resin layer. can do. For example, when the functional group of the easily adhesive resin is a hydroxyl group, the crosslinking reactive compound is preferably a melamine compound, a blocked isocyanate compound, an organic acid anhydride, or the like, and the functional group of the easily adhesive polyester is an organic acid or an anhydride thereof. In this case, epoxy-based compounds, melamine-based compounds, oxazoline-based compounds, metal chelates and the like are preferable as the cross-linking reactive compound. When the functional group of the easy-adhesion resin is an amine, an epoxy-based compound is preferable as the cross-linking reactive compound. It is preferable to select and use a functional group contained in the easily adhesive resin and one having a high crosslinking reaction efficiency. Examples of the melamine compound in the present invention include methoxymethylated melamine and butoxymethylated melamine which are alkylol or alkoxyalkylolated melamine compounds, and those obtained by co-condensing urea or the like with a part of melamine can also be used. .

The cross-linking reactive compound may be either a low molecular weight compound or a high molecular polymer having a reactive functional group as long as the reactive functional group is always contained in two or more functional groups in one molecule. The compounding amount of the crosslinking reactive compound is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, and particularly preferably 15 parts by weight or less in terms of parts by weight with respect to the easily adhesive resin layer.
Furthermore, the easily adhesive resin layer of the present invention may contain inert particles for improving the slipperiness of the coating layer, if necessary.

Examples of the inert particles include inorganic inert particles and organic inert particles. Examples of the inorganic inert particles include silica sol, alumina sol, calcium carbonate, and titanium oxide.
Examples of the organic inert particles include fine particles containing a single or copolymer of polystyrene resin, polyacrylic resin, and polyvinyl resin, or organic particles represented by crosslinked particles in which these and a crosslinking component are combined. These inert particles preferably have a softening temperature or decomposition temperature of about 200 ° C. or higher, more preferably 250 ° C. or higher, particularly 300 ° C. or higher. The average particle diameter (d) of the inert particles is 1/3 ≦ d / L ≦ 3, and further 1/2 ≦ d / L ≦ 2, when the average film thickness of the easily adhesive resin layer is (L). It is preferable to select so as to satisfy the relationship.

  The coating layers 14 and 14 ′ or the coating layers 24 and 24 ′ of the present invention may include a surfactant, an antifoaming agent, a coating property improving agent, a thickening agent, a low molecular antistatic agent, and an organic lubricant as necessary. , Antioxidants, ultraviolet absorbers, foaming agents, dyes, pigments and other additives may be included in small amounts. These additives may be used alone or in combination of two or more as necessary. The coating layer of the film of the present invention may be formed only on one side of the polyester film or on both sides. In the case of forming only on one side, another type of coating layer can be formed on the opposite side if necessary, and further characteristics can be imparted. In addition, in order to improve the applicability | paintability and adhesiveness to the film of a coating liquid, you may give a chemical process, an electrical discharge process, etc. to the film before application | coating.

Respect polyester film of the present invention, the thickness of the coating layer provided on the polyester film is usually 0.002~1.0g / ^{m 2,} more preferably 0.005 to 0.5 / ^{m 2,} more preferably 0 The range is from 0.01 to 0.2 g / m ² . If the film thickness is less than 0.002 g / m ^2, sufficient adhesion may not be obtained, and if it exceeds 1.0 g / m ² , the appearance, transparency, and film blocking properties may be deteriorated. There is sex.

  In the present invention, the drying and curing conditions for forming the coating layer 14 or the coating layer 24 on the polyester film are not particularly limited. For example, when the coating layer is provided by offline coating, Heat treatment may be performed at 80 to 200 ° C. for 3 to 40 seconds, preferably 100 to 180 ° C. for 3 to 40 seconds.

  On the other hand, when the coating layer is provided by in-line coating, heat treatment is usually performed at 70 to 280 ° C. for 3 to 200 seconds as a guide.

  Further, irrespective of off-line coating or in-line coating, heat treatment and active energy ray irradiation such as ultraviolet irradiation may be used in combination as required. The polyester film constituting the laminated polyester film in the present invention may be subjected to surface treatment such as corona treatment or plasma treatment in advance.

  The coating layers 14 and 14 'or the coating layers 24 and 24' of the polyester film of the present invention are preferably formed by blending a binder resin and a cross-linking agent in an arbitrary ratio. Since the barrier layer is formed, OL can be suppressed. For this reason, there is an effect that OL from the polyester film is not attached to the adhesive as much as possible and is not produced in the previous processing step. Therefore, the layer structure of the coating layer 14 or the coating layer 24 of the polyester film of the present invention is preferably double-sided, and it is necessary to apply to at least one side according to the application.

  The release film used for the pressure-sensitive adhesive sheet for an optical substrate of the present invention is formed by providing at least a biaxially oriented polyester film (release film substrate) and a release agent layer in this order. In order to prevent production process contamination, it is preferable to provide a coating layer which is an OL sealing layer. In that case, the biaxially oriented polyester film 13, the coating layer 14, and the release agent layer 15 are provided in this order.

  When the coating layer is not provided, OL is likely to occur in the production process of the release film and the double-sided pressure-sensitive adhesive sheet, and in the process of bonding the pressure-sensitive adhesive sheet for optical substrates to other members. It is not preferable.

  In the substrate-less double-sided pressure-sensitive adhesive sheet used in the pressure-sensitive adhesive sheet for optical substrates of the present invention, for example, after the pressure-sensitive adhesive is coated on the release layer of the release film, the pressure-sensitive adhesive layer is formed by drying. Next, a release film having a different peeling force is laminated on the release layer, but when the coating layer is not provided, other process contamination is caused by OL generated in the manufacturing process. In addition, when the pressure-sensitive adhesive layer is bonded to the electronic base material, a problem may occur in the electronic component due to the influence of OL.

In the present invention, when the release film has a coating layer, after heat-treating those release films (180 ° C., 10 minutes), the amount of OL extracted from the release layer surface with the coating layer by dimethylformamide is: It is preferably 1.0 mg / m ² or less. When OL exceeds 1.0 mg / m ² , there is a process contamination, and when the adhesive is bonded, a foreign matter may be generated, resulting in a problem such as a decrease in product yield.

  In addition, in the release film of the pressure-sensitive adhesive sheet for optical substrates of the present invention, in order to have a further surface function, the coating layer to be formed is an easy adhesion layer, an antistatic layer, or an antistatic easy adhesion layer. It is preferable to have.

  The coating layer in the present invention, or the release coating layers 15 and 15 ′ provided on the film or the coating layers 25 and 25 ′ are particularly limited as long as they contain a releasable material. It is not a thing. Among them, the one containing a curable silicone resin is preferable because the releasability is improved. A type having a curable silicone resin as a main component may be used, or a modified silicone type by graft polymerization with an organic resin such as a urethane resin, an epoxy resin, or an alkyd resin may be used.

  As the type of the curable silicone resin, any of the curing reaction types such as an addition type, a condensation type, an ultraviolet ray curable type, an electron beam curable type, and a solventless type can be used.

  The silicone used in the film 31 on the light release side used in the present invention is based on the concept of light release due to the migration component of the silicone, and the realization of dependence on a low release rate.

  In the present invention, the migratory component is a low molecular weight silicone compound mainly having a molecular weight of 1000 or less, and indicates a silicone resin having an alkenyl group and an alkyl group as functional groups. Examples thereof are as follows. Is mentioned. That is, first, the curable silicone resin containing an alkenyl group is a diorganopolysiloxane having a trimethylsiloxy group-blocked dimethylsiloxane / methylhexenylsiloxane copolymer (96 mol% of dimethylsiloxane units, methylhexenylsiloxane units 4). Mol%, dimethylvinylsiloxy group-blocked dimethylsiloxane / methylhexenylsiloxane copolymer (97 mol% dimethylsiloxane unit, 3 mol% methylhexenylsiloxane unit), dimethylsiloxane with dimethylhexylsiloxy group blocked at both ends of molecular chain And methyl hexenyl siloxane copolymer (95 mol% of dimethyl siloxane units, 5 mol% of methyl hexenyl siloxane units). As the nohydrogenpolysiloxane, molecular chain both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane, molecular chain both ends trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, molecular chain both ends dimethylhydrogensiloxy group-blocked Examples include methyl hydrogen polysiloxane, dimethyl hydrogen siloxy group-blocked dimethyl siloxane / methyl hydrogen siloxane copolymer, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, etc. In addition to the former low-molecular-weight cyclic siloxane, a trimethylsiloxy group-blocked dimethylsiloxane oligomer at both ends of the molecular chain; The Shishirokishi group-blocked dimethylsiloxane oligomers may be mixed as necessary.

  Further, in the present invention, silicone oil may be added in addition to the above compound in order to impart migration. The silicone oil is a silicone oil called a straight silicone oil or a modified silicone oil, and examples thereof include the following. Examples of the straight silicone include dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, and the like. Further, as modified silicone oil, side chain type polyether modified, aralkyl modified, fluoroalkyl modified, long chain alkyl modified, higher fatty acid ester modified, higher fatty acid amide modified, polyether / long chain alkyl modified / aralkyl modified, Examples include phenyl modification, polyether modification at both ends, and polyether / methoxy modification.

  These silicone oils are preferably contained in the silicone resin in an amount of 0.1 to 5.0% by weight as a migration component. Both straight silicone oil and modified silicone oil are non-reactive, non-functional oils.

  The migration component contained in the silicone resin used in the present invention is in the range of 5 to 20% by weight, preferably 10 to 13% by weight. If the content of the transition component is lower than 5%, the speed dependency becomes high, and if it exceeds 20% by weight, the curability is remarkably lowered and the adhesion is also deteriorated.

  Specific examples of the curable silicone resin include KS-774, KS-775, KS-778, KS-779H, KS-847H, KS-856, X-62-2242, X-manufactured by Shin-Etsu Chemical Co., Ltd. 62-2461, DKQ3-202, DKQ3-203, DKQ3-204, DKQ3-205, DKQ3-210 manufactured by Dow Corning Asia Co., Ltd. YSR-3022, TPR-6700, TPR-6720 manufactured by Toshiba Silicone Co., Ltd. , TPR-6721, SD 7220, SD 7226, SD 7229 manufactured by Toray Dow Corning Co., Ltd., and the like. Further, a release control agent may be used in combination to adjust the release property of the release layer. Further, as described above, a silane compound having an amino group may be added to the release layer.

In the present invention, as a method for providing the release coating layers 15 and 15 'or the coating layers 25 and 25' on the polyester film, a conventionally known coating such as reverse roll coating, gravure coating, bar coating, doctor blade coating, etc. A scheme can be used. The application amount of the release layer in the present invention is usually in the range of 0.01 to 1 g / m ² .

  In the present invention, coating layers such as an adhesive layer, an antistatic layer and an oligomer precipitation preventing layer may be provided on the surface where the release coating layers 15 and 15 'or the coating layers 25 and 25' are not provided. Further, the polyester film may be subjected to surface treatment such as corona treatment or plasma treatment.

  Also, drying and / or curing (thermal curing, ionizing radiation curing, etc.) of the pressure-sensitive adhesive layer or the release layer coating can be performed individually or simultaneously. When performing simultaneously, it is preferable to carry out at the temperature of 80 degreeC or more. The drying and curing conditions are preferably 80 ° C. or higher and 10 seconds or longer. If the drying temperature is less than 80 ° C. or the curing time is less than 10 seconds, the coating film is incompletely cured and the coating film tends to fall off.

In order to make the coated layer of the polyester film of the present invention clean and strong, a transition metal catalyst that promotes an addition-type reaction is used. In the present invention, the transition metal catalyst in the coating layer is preferably a catalyst using platinum. In addition to platinum, transition metals used as a catalyst include titanium, zirconium, chromium, nickel, copper, cobalt, iron, Manganese, molybdenum, palladium, ruthenium, rhodium, silver, gold, iridium and the like are preferably used.
The platinum catalyst used in the present invention includes chloroplatinic acid, an alcohol solution of chloroplatinic acid, a platinum compound such as a complex of chloroplatinic acid and an olefin, a complex of chloroplatinic acid and an alkenylsiloxane, platinum black And platinum-supported silica and platinum-supported activated carbon. The platinum-based catalyst content in the release layer is in the range of 0.5 to 5.0% by weight, preferably 1.5 to 4.0% by weight. When the content of the transition metal catalyst in the coating layer is lower than 0.5% by weight, there may be a problem such as deterioration of the surface condition due to insufficient peeling force or insufficient curing reaction in the coating layer. On the other hand, if the content of the transition metal catalyst in the coating layer exceeds 5.0% by weight, the cost is increased, the reactivity is increased, and process defects such as generation of gel foreign matter are caused. End up.

  In addition, since the addition-type reaction is very reactive, acetylene alcohol may be added as an unreactive inhibitor in some cases. The component is an organic compound having a carbon-carbon triple bond and a hydroxyl group, and preferably 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol and phenylbuty It is a compound selected from the group consisting of nor.

  In the present invention, the release force of the polyester film having the release coating layers 15 and 15 'or the application layers 25 and 25' is a double-sided adhesive tape ("No. 502" manufactured by Nitto Denko) attached to the release layer surface. It is indicated by a value measured with a tensile tester when the tape was peeled from the base film at a peeling angle of 180 ° and an arbitrary tensile speed after standing at room temperature for 1 hour. In the present invention, a method for adjusting a specific peeling force can be achieved by selecting a composition in the release layer, but other means can also be adopted, mainly of a release agent for the silicone release layer. It is preferable to change the type according to the desired peeling force. Furthermore, since the peeling force largely depends on the application amount of the release agent to be used, a method of adjusting the application amount of the release agent is more preferable.

  In the pressure-sensitive adhesive sheet 10 for optical substrates of the present invention, the first substrate-less double-sided pressure-sensitive adhesive sheet 41 having the first release film 31 that is a light release sheet, that is, the first substrate-less double-sided pressure-sensitive adhesive sheet precursor 41 ′. No. of the first release film 31. The 180 ° peeling force in a 502 tape, 300 mm / min speed range is usually 20 to 40 mN / cm, preferably 25 to 35 mN / cm. When the peeling force of the first release film 31 is less than 20 mN / cm, since the peeling force is close when peeling the first release film 31 ′, zipping may occur. Moreover, when the peeling force of the 1st release film 31 exceeds 40 mN / cm, the peeling force with the 2nd release film 32 is the process which produces the optical base material sheet 10 and bonds it to another member. However, there is a tendency that zipping occurs or the peel force of the second release film 32 has to be increased, and the possibility of causing cohesive failure of the adhesive 22 is increased.

  In the present invention, No. 1 of the first release film 31 of the first substrate-less double-sided pressure-sensitive adhesive sheet precursor 41 ′. The 180 ° peeling force in a 502 tape, 300 mm / min speed range is usually 20 to 40 mN / cm, preferably 25 to 35 mN / cm. When the peeling force of the first release film 31 is less than 20 mN / cm, since the peeling force is close when peeling the first 'release film 31', zipping may occur. Moreover, when the peeling force of the 1st release film 31 exceeds 40 mN / cm, the peeling force with the 2nd release film 32 is the process which produces the optical base material sheet 10 and bonds it to another member. However, there is a tendency that zipping occurs or the peel force of the second release film 32 has to be increased, and the possibility of causing cohesive failure of the adhesive 22 is increased.

  In the present invention, No. 1 of the first 'release film 31' of the first substrate-less double-sided pressure-sensitive adhesive sheet precursor 41 'is used. The 180 ° peeling force in a 502 tape, 300 mm / min speed region is usually 3 to 50 mN / cm, preferably 5 to 25 mN / cm, and more preferably 10 to 20 mN / cm. If the release force of the first release film is less than 3 mN / cm, the release film is easily peeled off, and the release film may be peeled off with a slight external force generated in the manufacturing process. Moreover, when the peeling force of the first release film exceeds 50 mN / cm, a gap is formed between the second release film and the adhesive layer to bite bubbles due to peeling in the step of peeling the first release film. May end up.

  In the first 'substrate-less double-sided pressure-sensitive adhesive sheet precursor 41' of the present invention, the No. The 180 ° peeling force in a 502 tape, 300 mm / min speed region is usually 10 to 20 mN / cm, preferably 12 to 18 mN / cm. When the peeling force of the first 'release film 31' is less than 10 mN / cm, since the peeling force is low, there may be a problem such as peeling off without permission. Further, when the peeling force of the first 'release film 31' exceeds 20 mN / cm, the first 'release film 31' is peeled off from the pressure-sensitive adhesive when the optical substrate sheet 10 is produced. The difference in peeling force with the 1 release film 31 is small, and there may be a problem that peeling is impossible.

  In the first 'substrate-less double-sided pressure-sensitive adhesive sheet precursor 41' of the present invention, the No. of the first release film 31 and the first 'release film 31'. The ratio of 180 ° peeling force in the 502 tape, 300 mm / min speed region is preferably 2.0 times or more on the heavy peeling side / light peeling side. When it is smaller than 2.0 times, the above-mentioned peeling abnormality may occur.

  In the pressure-sensitive adhesive sheet 10 for optical substrates of the present invention, the second substrate-less double-sided pressure-sensitive adhesive sheet 42 having the second release film 32 that is a heavy release sheet, that is, the second substrate-less double-sided pressure-sensitive adhesive sheet precursor 42 ′. The release force of the second release film 32 is that a double-sided adhesive tape (Nitto Denko “No. 502”) is attached to the release layer surface and left at room temperature for 1 hour, and then the substrate film and release angle are 180 °. The value measured with a tensile tester when the tape was peeled off at an arbitrary tensile speed. The method for adjusting the specific peeling force in the present invention can be achieved by selecting the composition in the release layer, but other means can also be adopted, mainly the type of release agent for the silicone release layer. Is preferably changed according to the desired peeling force, and furthermore, since the peeling force largely depends on the application amount of the release agent to be used, a method of adjusting the application amount of the release agent is more preferable.

  In the present invention, the No. 2 of the second release film 32 of the second substrate-less double-sided pressure-sensitive adhesive sheet precursor 42 ′. The peel force for 502 is 300 mm / min, preferably 20 to 100 mN / cm, and more preferably 40 to 80 mN / cm. If the peel strength of the second release film is less than 20 mN / cm, the peel strength of the second 'release film 32' must be lowered to the limit. In this case, the second 'release film 32' is arbitrarily used. In the process of producing the pressure-sensitive adhesive sheet 10 for an optical substrate and bonding it to another substrate, there is a problem that the difference in peeling force with the first release film 31 is small and a peeling abnormality is caused. May occur. Moreover, when the peeling force of the 2nd mold release film 32 exceeds 100 mN / cm, the bonding process to a polyester film, the optical base material sheet 10 is produced, and the bonding process to another member WHEREIN: When the release film 32 is peeled off, problems such as cohesive failure of the pressure-sensitive adhesive may occur because the peel force is too heavy.

  In the 2 ′ substrate-less double-sided pressure-sensitive adhesive sheet precursor 42 ′ of the present invention, the No. The 180 ° peeling force in a 502 tape, 300 mm / min speed range is usually 20 to 40 mN / cm, preferably 25 to 35 mN / cm. When the peeling force of the second 'release film 32' exceeds 40 mN / cm, the peeling force of the second release film 32 increases, and therefore, when the optical substrate sheet 10 is bonded to another member. In addition, when the second release film 32 is peeled from the pressure-sensitive adhesive, the pressure-sensitive adhesive may cause cohesive failure, or may cause a peeling abnormality such as the film not being peeled from the pressure-sensitive adhesive.

  In the 2 'substrate-less double-sided pressure-sensitive adhesive sheet precursor 42' of the present invention, the second release film 32 and the second 'release film 32' No. The ratio of 180 ° peeling force in the 502 tape, 300 mm / min speed region is preferably 2.0 times or more on the heavy peeling side / light peeling side. When it is smaller than 2.0 times, the above-mentioned peeling abnormality may occur.

  In the pressure-sensitive adhesive sheet for optical substrates of the present invention, the peeling force of the second release film 32 provided on the second substrate-less double-sided pressure-sensitive adhesive sheet precursor 42 and the first substrate-less double-sided pressure-sensitive adhesive sheet precursor 41 are provided. No. of the second release film 31 formed. The ratio of 180 ° peeling force in the 502 tape, 300 mm / min speed region is preferably 2.0 times or more on the heavy peeling side / light peeling side. When it is smaller than 2.0 times, the release film may not be peeled off well when bonded to another member.

  As the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer 11, an acrylic pressure-sensitive adhesive is usually used. The acrylic pressure-sensitive adhesive is composed mainly of an acrylic copolymer obtained by copolymerizing a functional group-containing monomer and another monomer such as an acrylic ester or methacrylic ester, and if necessary, a solvent , A crosslinking agent, a tackifier, a filler, a colorant, an antioxidant, an antistatic agent, an ultraviolet absorber and the like may be further contained.

  Examples of the functional group-containing monomer include carboxyl group-containing monomers such as acrylic acid and methacrylic acid. The functional group-containing monomer preferably includes 0.3 to 5.0% by mass as a monomer unit based on the whole monomer constituting the acrylic copolymer (100% by mass).

  By containing functional groups, acrylic copolymers can adjust the cohesive force by reaction with the crosslinking agent, and prevent the adhesive from sticking out from the base material and improve the adhesive strength and heat resistance. Can be made. There is no restriction | limiting in particular as a crosslinking agent used for an adhesive, It uses suitably selecting from what was conventionally used in the acrylic adhesive conventionally, for example, a polyisocyanate compound, an epoxy resin, a melamine resin, a urea resin , Dialdehydes, methylol polymers, aziridine compounds, metal chelate compounds, metal alkoxides, metal salts and the like, preferably polyisocyanate compounds are used.

  In the pressure-sensitive adhesive sheet 10 for an optical substrate of the present invention, the haze means that the first release film 31 is peeled off, bonded to a 1 mm thick float plate glass, and the second release film 32 on the opposite surface is peeled off, It refers to the haze value of the pressure-sensitive adhesive sheet itself, which is obtained by subtracting the haze value of the float plate glass from the total haze value measured when bonded to a 1 mm thick float plate glass. The haze is preferably 1.5% or less. When the haze is larger than 1.5%, the visibility of the final product is lowered, which is not preferable.

  In order to set the haze of the above-mentioned pressure-sensitive adhesive sheet for optical substrates to the above range, it is possible to cause the phenomenon of pressure-sensitive adhesive particles and aggregates by filtering, but the device of the film substrate also greatly affects. For example, various kinds of particles used for the film substrate, such as particle size, addition amount, filter reinforcement in the production line, film production conditions (film stretching temperature, draw ratio), smoothing of rolls used in the film production line, etc. This can be achieved by appropriately combining the conditions.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded. The measurement method and evaluation method used in the present invention are as follows.

(1) Measurement of intrinsic viscosity of polyester 1 g of polyester from which other polymer components and pigments incompatible with polyester have been removed are precisely weighed, and 100 ml of a mixed solvent of phenol / tetrachloroethane = 50/50 (weight ratio) is added. It was dissolved and measured at 30 ° C.

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

(3) Measurement of amount of catalyst in coating layer Using SAICAS, the sample film was obliquely cut to expose the cross section. after that,
The amount of catalyst containing platinum contained in the polyester film coating layer was determined using TOF-SIMS (time-of-flight mass spectrometry mass spectrum).

(4) Measurement of amount of migrating component in release layer composition Add 0.04% by weight of platinum catalyst to 15g of silicone resin (silicone of release layer composition) diluted with toluene to a solid content concentration of 4% by weight. After stirring, the mixture is placed in a box made of a sheet made of Teflon (registered trademark) and thermally cured at 150 ° C. for 1 hour (Sample 1). When adding a migration component (corresponding to Comparative Example 2 described later), 30% by weight is added to the solid content of the silicone resin. Sample 1 is immersed in toluene for 1 day, and the sample taken out is dried at 120 ° C. for 30 minutes and allowed to cool to room temperature (sample 2). The migration component amount was calculated from the following formula.
Migration component amount (% by weight) = (weight of sample 1−weight of sample 2) ÷ weight of sample 1 × 100

(5) No. of release film. Evaluation of peeling force with 502 tape After applying one side of double-sided adhesive tape (“No. 502” and “No. 31B” manufactured by Nitto Denko) to the surface of the release layer of the sample film, the size is 50 mm × 300 mm. After cutting, the peel strength after standing for 1 hour at room temperature is measured. For the peeling force, a tensile tester (“Intesco model 2001 type” manufactured by Intesco Co., Ltd.) was used, and 180 ° peeling was performed under the condition of a tensile speed of 300 mm / min. Judgment is based on the following criteria.

(6) Measurement of OL extracted from anchor layer surface In advance, an unheated release film is heated in air at 180 ° C. for 10 minutes. After that, the heat-treated film is brought into close contact with the inner surface of a box having a top and width of 10 cm and a height of 3 cm, and the box shape is obtained. When the coating layer is provided, the coating layer surface is set to the inside. Next, 4 ml of DMF (dimethylformamide) is placed in the box prepared by the above method and left for 3 minutes, and then DMF is recovered. The recovered DMF was supplied to liquid chromatography (manufactured by Shimadzu Corporation: LC-7A) to determine the amount of OL in DMF, and this value was divided by the area of the film in contact with DMF to obtain the amount of film surface OL (mg / M ² ).

  The amount of oligomer in DMF was determined from the peak area ratio between the standard sample peak area and the measured sample peak area (absolute calibration curve method). The standard sample was prepared by accurately weighing OL (cyclic trimer) collected in advance and dissolving it in DMF accurately weighed. The concentration of the standard sample is preferably in the range of 0.001 to 0.01 mg / ml. The conditions for the liquid chromatograph were as follows.

Mobile phase A: Acetonitrile Mobile phase B: 2% acetic acid aqueous solution Column: “MCI GEL ODS 1HU” manufactured by Mitsubishi Chemical Corporation
Column temperature: 40 ° C
Flow rate: 1 ml / min Detection wavelength: 254 nm

(7) Measurement of internal haze of film substrate Internal haze was measured according to JIS K7136 using a haze meter (HZ-2) manufactured by Suga Test Instruments. Ethanol was used as the solvent.

(8) Measurement of haze of pressure-sensitive adhesive sheet for optical substrate The first release film 31 of the first substrate-less double-sided pressure-sensitive adhesive sheet 41 is peeled off, and a float plate glass having a thickness of 5 cm × 5 cm × 1 mm (manufactured by Sekiya Rika Co., Ltd.) In addition, the second release film 32 was peeled off and similarly laminated on a 1 mm-thick float plate glass to prepare a sample. The produced sample was measured for turbidity by an integrating sphere turbidimeter NDH manufactured by Nippon Denshoku Industries Co., Ltd. according to 10 JIS K 7136. At this time, the haze of the pressure-sensitive adhesive sheet for an optical substrate was determined by the following formula using the haze value of the float plate glass measured in advance.
Haze (%) = {(haze (%) of prepared sample) − (haze of float plate glass (%)) × 2}

(9) Practical properties <Releasability 1 of the release film of the base material-less double-sided pressure-sensitive adhesive sheet and the pressure-sensitive adhesive sheet for optical substrates>
No. above. The ratio of peel force with 502 tape was compared and evaluated.
○: 2.0 times or more: No abnormality is observed at the interface between the second release layer and the adhesive, or the release film floats at the interface between the second release layer and the adhesive, and the adhesive has a pattern. Occurred but practically acceptable level Δ: 1.2 to 2.0 times: level at which no abnormality is observed at the interface between the second release layer and the pressure-sensitive adhesive, but slightly caught ×: smaller than 1.2 times: When the release film floats at the interface between the second release layer and the pressure-sensitive adhesive, a clear pattern is generated on the pressure-sensitive adhesive.

<Releasability 2 of Release Film of Substrate-less Double-Sided Adhesive Sheet and Optical Adhesive Sheet for Optical Substrate> At the stage of forming a sheet, the adhesive and the release film were peeled and evaluated.
○: Neither catching nor zipping occurs, and the surface is clean
×: Causes catching and zipping, resulting in rough surface or cohesive failure

<Occurrence of zipping at the time of peeling of the release film of the double-sided pressure-sensitive adhesive sheet and the pressure-sensitive adhesive sheet for optical substrates>
When measuring the peeling force, the peeling state of the pressure-sensitive adhesive and the release film was observed, and the occurrence of zipping was evaluated in three stages.
○: Peeling extremely smoothly, no peeling stripes, no peeling noise △: Slight peeling stripes are observed, peeling noise is slightly generated, and slight zipping occurs ×: Peeling stripes are observed , Peeling sound is generated, and zipping occurs. The grades of ○ and Δ are at a level that does not cause a problem in actual use.

(10) Comprehensive evaluation An evaluation that takes all of film forming property, workability, functionality, etc. into consideration is performed. Judgment is based on the following criteria.
○: Even if it is produced, it can be sufficiently supplied as a product.
Δ: Productivity is good and the frequency of defects in optical inspection is low. ×: Productivity is poor. There are many problems with optical inspection.

The polyester used in the examples and comparative examples was prepared as follows.
<Method for producing polyester (a)>
Using 100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol as starting materials, adding tetrabutoxy titanate as a catalyst to the reactor, setting the reaction start temperature to 150 ° C., and gradually increasing the reaction temperature as methanol is distilled off. It was 230 degreeC after 3 hours. After 4 hours, the transesterification reaction was substantially completed, and then a polycondensation reaction was performed for 4 hours.
That is, the temperature was gradually raised from 230 ° C. to 280 ° C. On the other hand, the pressure was gradually reduced from normal pressure, and finally 0.3 mmHg. After the start of the reaction, the reaction was stopped at a time corresponding to an intrinsic viscosity of 0.61 due to a change in the stirring power of the reaction vessel, and the polymer was discharged under nitrogen pressure to obtain a polyester (a) having an intrinsic viscosity of 0.61.

<Method for producing polyester (b)>
In the method for producing polyester (a), after adding ethyl acid phosphate, an ethylene glycol slurry of synthetic calcium carbonate particles having an average particle diameter of 0.8 μm was added so that the content of the particles with respect to polyester was 1% by weight. Obtained polyester (b) using the method similar to the manufacturing method of polyester (a). The obtained polyester (b) had an intrinsic viscosity of 0.60.

<Production of polyester (c)>
Starting from 100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol, magnesium acetate tetrahydrate is added as a catalyst to the reactor, the reaction start temperature is 150 ° C., and the reaction temperature is gradually increased as methanol is distilled off. The temperature was raised to 230 ° C. after 3 hours.
After 4 hours, the transesterification reaction was substantially terminated. Ethyl acid phosphate was added to the reaction mixture, which was then transferred to a polycondensation tank, and 0.04 part of antimony trioxide was added to carry out a polycondensation reaction for 4 hours. That is, the temperature was gradually raised from 230 ° C. to 280 ° C.
On the other hand, the pressure was gradually reduced from normal pressure, and finally 0.3 mmHg. After the start of the reaction, the reaction was stopped at a time corresponding to an intrinsic viscosity of 0.45 due to a change in stirring power of the reaction tank, and the polymer was discharged under nitrogen pressure to obtain a polyester chip (c). The intrinsic viscosity of this polyester was 0.45.

<Manufacture of polyester (d)>
The intrinsic viscosity of this polyester chip was increased by a solid phase polycondensation method. After treatment in a preliminary crystallization tank at 170 ° C. in a nitrogen atmosphere for 0.5 hours, the moisture content becomes 0.005% at a temperature of 200 ° C. using a tower dryer that flows an inert gas. Until dried. Thereafter, it was sent to a solid phase polymerization tank and subjected to solid phase polymerization at 240 ° C. for 3 hours to obtain a polyester (d) having an intrinsic viscosity of 0.70.

<Manufacture of polyester (e)>
When producing the polyester (d), solid phase polymerization was performed in a solid phase polymerization tank for 5 hours to obtain a polyester (e) having an intrinsic viscosity of 0.80.

Example 1:
<Manufacture of polyester film>
As a raw material for the surface layer, 70% by weight of polyester (e) and 30% by weight of polyester (b) are mixed. As a raw material for the intermediate layer, 84% by weight of polyester (a) and 16% by weight of polyester (b) are mixed. Each was supplied to an extruder with a vent and melt-extruded at 290 ° C., and then cooled and solidified on a cooling roll having a surface temperature set to 40 ° C. using an electrostatic application adhesion method to obtain an unstretched sheet. Next, the film was stretched 3.0 times in the longitudinal direction at 100 ° C., and then the following coating agent was coated on one side of the longitudinally stretched film so that the coating amount (after drying) was 0.03 g / m ² . Then, after guiding to the tenter, through the preheating process in the tenter, the film was stretched 4.3 times at 120 ° C, then heat-treated at 220 ° C for 10 seconds, and then relaxed by 4% in the width direction at 180 ° C. Was added to obtain a master roll having a width of 4000 mm. A slit was made from a position of 1400 mm from the end of the master roll, and the core roll was wound up 1000 m to obtain a polyester film. The total thickness of the obtained film was 50 μm (layer structure: surface layer 2.5 μm / intermediate layer 45 μm / surface layer 2.5 μm). However, in the case of the present invention, only when a coating layer (corresponding to 14, 14 ', 24, 24' in the figure) aiming at OL sealing ability is provided, coating processing is performed after stretching in the longitudinal direction as necessary. However, stretching in the transverse direction shall be performed.

<Coating layer>
Examples of the compounds constituting the coating layers 14, 14 ′, 24, 24 ′ are as follows.
(Example compounds)
-Polyvinyl alcohol binder polymer having a saponification degree of 88 mol% and a polymerization degree of 350: A
Emulsion polymer of methyl methacrylate / ethyl acrylate / acrylonitrile / N-methylol methacrylamide = 45/45/5/5 (molar ratio) (emulsifier: anionic surfactant) Binder polymer: B
・ Crosslinking agent Hexamethoxymelamine crosslinking agent: C
・ Particulate colloidal silica (average particle diameter: 70 nm): D
Solid content ratio: A / B / C / D = 30/24/42/4

  In the release films 31, 31 ', 32, and 32', the stretching prescription and the thickness of the film were variously changed (see Table 1).

Reverse gravure coating method so that the coating amount (after drying) of the release agent shown below is 0.1 g / m ² on the polyester films for the obtained release films 31, 31 ′, 32 and 32 ′. Then, a roll-like release polyester film was obtained under the conditions of a dryer temperature of 120 ° C. and a line speed of 30 m / min (see Table 1).

<Release layer>
A biaxially oriented polyester film obtained by the production of a polyester film is provided with a paint having a release layer composition shown below so that the coating amount is 0.1 g / m ² (after drying). Obtained (see Table 1).

-Release layer composition-1
Curable silicone resin (LTC303E: manufactured by Toray Dow Corning) 20 parts Addition type platinum catalyst (SRX212: manufactured by Toray Dow Corning) 0.2 parts MEK / toluene / n-heptane mixed solvent (mixing ratio is 1: 1: 1) )
Migrating amount of release agent composition-1: 15% by weight

・ Releasing layer composition-2
Curable silicone resin (KS-847H: manufactured by Shin-Etsu Chemical Co., Ltd.) 17 parts Peeling control agent (KS-3800: manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts Addition type platinum catalyst (PL-50T: manufactured by Shin-Etsu Chemical Co., Ltd.) 0.2 parts MEK / toluene / N-heptane mixed solvent (mixing ratio is 1: 1: 1)

・ Release layer composition-3
Curable silicone resin (X-62-5039: manufactured by Shin-Etsu Chemical Co., Ltd.) 14 parts Peeling control agent (KS-3800: manufactured by Shin-Etsu Chemical Co., Ltd.) 6 parts Cross-linking agent (X-92-185: manufactured by Shin-Etsu Chemical Co., Ltd.) 0.4 Part catalyst (PL-5000: manufactured by Shin-Etsu Chemical Co., Ltd.) 1.0 part MEK / toluene / n-heptane mixed solvent (mixing ratio is 1: 1: 1)

-Release layer composition-4
Curable silicone resin (X-62-5039: manufactured by Shin-Etsu Chemical Co., Ltd.) 12 parts Peeling control agent (KS-3800: manufactured by Shin-Etsu Chemical Co., Ltd.) 8 parts Cross-linking agent (X-92-185: manufactured by Shin-Etsu Chemical Co., Ltd.) 0.4 Part catalyst (PL-5000: manufactured by Shin-Etsu Chemical Co., Ltd.) 1.0 part MEK / toluene / n-heptane mixed solvent (mixing ratio is 1: 1: 1)

(II) Production of film substrate 11 <Production of polyester (f)>
Using 100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol as starting materials, 0.09 parts by weight of magnesium acetate tetrahydrate as a catalyst is placed in the reactor, the reaction start temperature is set to 150 ° C., and the methanol is distilled off gradually. The reaction temperature was raised to 230 ° C. after 3 hours. After 4 hours, the transesterification reaction was substantially terminated. After adding 0.04 part of ethyl acid phosphate to this reaction mixture, 0.04 part of antimony trioxide was added, and a polycondensation reaction was carried out for 4 hours. That is, the temperature was gradually raised from 230 ° C. to 280 ° C. On the other hand, the pressure was gradually reduced from normal pressure, and finally 0.3 mmHg. After the start of the reaction, the reaction was stopped at a time corresponding to an intrinsic viscosity of 0.63 due to a change in stirring power of the reaction tank, and the polymer was discharged under nitrogen pressure. The obtained polyester (f) had an intrinsic viscosity of 0.63 and an oligomer (cyclic trimer) content of 0.83% by weight.

<Manufacture of polyester (g)>
In the method for producing polyester (f), after adding 0.04 part of ethyl acid phosphate, 0.2 part of silica particles dispersed in ethylene glycol having an average particle diameter of 1.6 μm and 0.04 part of antimony trioxide are added. In addition, polyester (g) was obtained using the same method as the production method of polyester (f) except that the polycondensation reaction was stopped at the time corresponding to the intrinsic viscosity of 0.65. The obtained polyester (g) had an intrinsic viscosity of 0.65 and an oligomer (cyclic trimer) content of 0.82% by weight.

<Manufacture of polyester film>
A mixture raw material in which the polyesters (f) and (g) are mixed at a ratio of 85% and 15%, respectively, is used as a raw material for the I layer, and a raw material of 100% polyester (f) is used as a raw material for the II layer. Each was supplied to the machine and melted at 285 ° C., and then the I layer was the outermost layer (surface layer), the II layer was the intermediate layer, and two types of 3 layers (I / II / In I), a non-oriented sheet was obtained by coextrusion and cooling and solidification so that the thickness composition ratio was I: II: I = 2: 19: 2. Next, the film was stretched 3.4 times in the machine direction at a film temperature of 82 ° C. using the roll peripheral speed difference, led to a tenter, stretched 4.0 times at 120 ° C. in the transverse direction, and heat-treated at 230 ° C. Thereafter, the film was wound on a roll to obtain a laminated polyester film having a thickness of 25 μm and a film haze of 0.5%. The surface of the obtained film had almost no scratches visible under a three-wavelength fluorescent lamp.

(III) Production of Substrate-less Double-Sided Adhesive Sheet Precursors 41 ′ and 42 ′ <Manufacture of Substrate-less Double-Sided Adhesive Sheet Precursor>
On the release agent layer of the obtained 1 ′ release film, the acrylic pressure-sensitive adhesive solution was coated using an applicator so that the film thickness after drying was 25 μm, and then the coating film Was dried at 120 ° C. for 1 minute to form an adhesive layer. The acrylic pressure-sensitive adhesive solution was prepared by adding polyisocyanate-based crosslinking to 100 parts by mass of a copolymer solution (solvent: toluene, solid content concentration: 40% by mass) having a monomer-based mass ratio of butyl acrylate and acrylic acid of 99: 1. It was obtained by adding 1 part by weight of an agent (manufactured by Toyo Ink Manufacturing Co., Ltd., trade name “BHS8515”, solid content concentration 37.5% by mass). Subsequently, the release agent layer and adhesive layer of the 1st release film were bonded together, and the base material-less double-sided adhesive sheet precursor of Example 1 was obtained (refer Table 1).

(IV) Production of optical substrate pressure-sensitive adhesive sheet 10 <Production of optical substrate pressure-sensitive adhesive sheet>
The first 'release film 31', which is a light release sheet of the obtained first substrate-less double-sided PSA sheet precursor 41 ', was peeled off, and the exposed adhesive layer and one side of the film substrate were bonded together. Next, the second release film 32 ′, which is a light release sheet of the second substrate-less double-sided pressure-sensitive adhesive sheet precursor 42 ′, was peeled off, and the exposed adhesive layer and the above prepared (first substrate-less double-sided pressure-sensitive adhesive sheet 31). / The other side of the film substrate 11 (of the polyester film 11) was bonded to obtain the target optical substrate pressure-sensitive adhesive sheet 10. The haze of the pressure-sensitive adhesive sheet when the release films 31 and 32 of the obtained pressure-sensitive adhesive sheet 10 for an optical substrate were peeled and bonded to glass having a thickness of 1 mm was 0.9% (Table 1).

Examples 2-3:
Example 1 except that the release film of Example 1 changes the presence or absence of a coating film at the time of production of the polyester film, and the silicone composition is changed when the silicone layer is processed on the polyester film, and the coat thickness is changed. To produce a polyester film. Subsequently, in the film base material 11 of Example 1, it manufactured like Example 1 except changing the compounding quantity and layer structure of polyester, and changing film thickness, and obtained the polyester film. Finally, the obtained member was bonded to obtain a target optical pressure-sensitive adhesive sheet. The characteristic results of the obtained sheet are summarized in Table 1 below.

Comparative Examples 1-2:
Example 1 except that the release film of Example 1 changes the presence or absence of a coating film at the time of production of the polyester film, and the silicone composition is changed when the silicone layer is processed on the polyester film, and the coat thickness is changed. To produce a polyester film. Subsequently, in the film base material 11 of Example 1, it manufactured like Example 1 except changing the compounding quantity and layer structure of polyester, and changing film thickness, and obtained the polyester film. Finally, the obtained member was bonded to obtain a target optical pressure-sensitive adhesive sheet. The characteristic results of the obtained sheet are summarized in Table 1 below.

  The sheet of the present invention is generally inexpensive and can secure the required transparency as compared with a pressure-sensitive adhesive having the same thickness. Further, in a configuration using a glass substrate, the pressure-sensitive adhesive for optical substrates has an anti-scattering effect. Since it can be suitably used as a sheet, it is useful.

DESCRIPTION OF SYMBOLS 10 Adhesive sheet for optical base materials 11 Film base material 12 1st adhesive layer 13 1st release film base material 13 '1' release film base material 14 1st application layer 14 '1' application layer 15 1st Release agent layer 15 ′ First ′ release agent layer 22 Second pressure-sensitive adhesive layer 23 Second release film substrate 23 ′ Second ′ release film substrate 24 Second coating layer 24 ′ Second ′ coating layer 25 Second release agent layer 25 'Second' release agent layer 31 First release film (light release sheet; release force: 32> 31)
31 '1' release film (light release sheet; release force: 31> 31 ')
32 Second release film (heavy release sheet; release force: 32> 31)
32 ′ 2 ′ release film (light release sheet; release force: 32> 32 ′)
41 1st base material-less double-sided adhesive sheet 42 2nd base material-less double-sided adhesive sheet 41 '1st base material-less double-sided adhesive sheet precursor 42' 2nd base material-less double-sided adhesive sheet precursor

Claims (1)

It is a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive sheet layer on both sides of the film substrate, and the haze of the pressure-sensitive adhesive sheet when a 1 mm thick float plate glass is bonded to each surface of the pressure-sensitive adhesive sheet layer is 1.2% or less, An adhesive sheet for an optical substrate, comprising release layers on both sides of the adhesive sheet layer.

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