TW201704011A - Mold release film - Google Patents

Abstract

Provided is a mold release film which has good releasability from an adhesive and is extremely suppressed in oligomer precipitation, while being suppressed in migration, and which is suitable for various adhesive layer protection applications for the production of a capacitive touch panel, the production of LCD constituent members such as a polarizing plate and a retardation film used for a liquid crystal display (LCD), the production of a plasma display panel constituent member, the production of an organic electroluminescent display constituent member, the production of various display constituent members, and the like. A mold release film that is characterized by having a silicone-based mold release layer, which is formed from a coating liquid containing a reactive silicone resin having a functional group, an unreactive silicone resin and a platinum-based catalyst, on one surface of a polyester film.

Description

Release film

The present invention relates to a release film, and is particularly suitable for use in various adhesive protection applications and requires light peeling, and the amount of oligomer precipitation is extremely small, for example, for the manufacture of a touch panel suitable for an electrostatic capacity type, etc. Various applications of the coating layer, and the use of a liquid crystal panel (hereinafter referred to as LCD), such as a polarizing plate or a phase difference plate, for the manufacture of an LCD component, and a plasma display panel (hereinafter referred to as PDP) for the manufacture of components, organic electro Light-emitting (hereinafter referred to as "organic EL") is a release film which is used for the manufacture of members and various types of display constituent members, and is used for various adhesive layer protection purposes.

In the past, a release film made of a polyester film as a base material can be used for various applications such as a touch panel manufacturing for electrostatic capacitance type, which is bonded through an adhesive layer, a polarizing plate for LCD, and a phase difference plate. The PDP is used for the production of a member, the production of an organic EL constituent member, the use of various display constituent members, various optical applications, and the like. In recent years, with the various display constituent members, particularly the polarizing plate for LCD, the peeling force of the release film and the thin polarizing plate is high, and the peeling force cannot be smoothly peeled off. Bad conditions can become a problem. If the release film is not peeled off smoothly from the thin polarizing plate, the yield is lowered and it becomes a problem. Further, after the application of the adhesive layer, the inspection property of the polarizing plate for LCD which is precipitated by the oligomer is lowered, and the deterioration of the visibility of the adhesive layer is a problem. Moreover, the foreign matter is caught by the charging of the release film, and the foreign matter is transferred to the adhesive layer, which is a problem.

In recent years, with the advancement of the IT (Information Technology) field, the quality of the release film used in the manufacture of display members such as LCD, PDP, and organic EL has been improved, and the use of the adhesive layer has been accompanied by self-protection. Various problems such as oligomerization of the polyester of the release film or peeling property of the adhesive and the release film are apparent.

It is not only the use of polarizing plates, but even in the application of adhering sheets between objects, there are still many reports indicating defects due to the peeling force of the release film. Adhesive sheets have been known to the art, and a two-sided adhesive sheet having no substrate is known. The non-substrate two-sided adhesive sheet is formed by a laminate of a lightly peeling film having a relatively low peeling force of the two layers of the adhesive layer and a heavy release film having a relatively high peeling force, and after removing the peeling film on both sides That is, it becomes an adhesive sheet which is formed by the adhesive layer without the support substrate and which is formed only by the adhesive layer.

In the method of using the two-sided adhesive sheet without the substrate, first, the light release film is peeled off, and the surface on one side of the exposed adhesive layer is next to the surface of the object to be bonded, and after that, the film is peeled off and peeled off again. The surface on the other side of the exposed adhesive layer is followed by a different object surface, thereby exemplifying the processing steps in which the objects are surface-to-face.

In recent years, the two-sided adhesive sheet having no substrate has been attracting attention because of its excellent workability, and it can be used not only for a wide range of applications but also for various optical applications such as mobile phones. In particular, the capacitive touch panel is a multi-touch operation using two fingers for screen operation, and the use as an information terminal is rapidly expanding. In the touch panel of the electrostatic capacitance type, the difference in the printing step tends to be thicker than that of the resistive film method, and there is a proposal to increase the thickness of the adhesive layer to cancel the printing step. When the adhesive layer is thickened, a part of the adhesive layer may be adhered to the release film at the time of peeling off the release film, or a problem may occur in which air bubbles are mixed in the adhesive layer transferred to the portion of the release film. Therefore, when the non-substrate two-sided adhesive sheet is used for optical use, it is not only a non-substrate adhesive sheet on both sides, but even in the combined release film, it must be more rigorous and higher quality than before. The condition of the film.

In the use of the non-substrate two-sided adhesive sheet, when the light release release film is peeled off from the adhesive layer, the peeling force of the light release release film is high, and the adhesive cannot be smoothly peeled off from the adhesive, resulting in a decrease in yield. problem.

In order to solve this problem, for example, as disclosed in Patent Document 1 and Patent Document 2, the peeling speed of the release layer is set to be a certain level or less. However, in recent years, in particular, when the adhesive layer itself is used in a form in which the adhesive layer is inferior in absorbability, even if the release film described above is used, it may not be satisfactory. Further, in the above method, since the polyfluorene resin containing the transition component is added, when the migration property is deteriorated and it is bonded to the adhesive, the transition component migrates to the adhesive. Side, and there may be problems that may contaminate the adhesive or contaminate the adhesive processing steps.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2012-25088

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2012-179888

The present invention has been made in view of the above circumstances, and a method for solving the problem is to provide a touch panel which is excellent in release property from a self-adhesive agent, has a small amount of oligomer deposition, and has less mobility, and is applicable to, for example, a capacitive touch panel. Manufacture of LCD components such as a polarizing plate or a phase difference plate used in a liquid crystal display (LCD), a plasma display panel constituting member, and an organic electroluminescence constituting member, and various display components are manufactured. In addition, it is also suitable for release films for various adhesive layer protection purposes.

The inventors of the present invention have found that the above problems can be easily solved by the polyester film having a specific constitution in view of the above-mentioned findings, and the present invention has been completed.

That is, the gist of the present invention is a release film characterized in that it has a reactive polyfluorene having a functional group on one side of the polyester film. A polyfluorene-based release layer formed of an oxygen resin, a non-reactive polyanthracene resin, and a platinum-based catalyst coating liquid.

According to the present invention, it is possible to provide a release polyester film which is excellent in release property from an adhesive, has a small amount of oligomer precipitation, and has low migration property, and has high industrial value.

1‧‧‧Two-sided adhesive sheet without substrate

2‧‧‧Adhesive layer

3‧‧‧1st release film substrate

4‧‧‧1st release layer

5‧‧‧Separate release film substrate

6‧‧‧Second release agent layer

7‧‧‧1st release film (light peeling side)

8‧‧‧Second release film (heavy peeling side)

Fig. 1 is a schematic cross-sectional view showing an example of a non-substrate double-sided adhesive sheet of the present invention.

[Formation of the Invention] <First embodiment>

The term "polyester film" as used in the present invention means a film obtained by stretching a sheet which is melted and extruded from a die by a pressing method.

The polyester constituting the above film means a polymer containing an ester group obtained by condensation condensation of a dicarboxylic acid with a diol or a hydroxycarboxylic acid. Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, adipic acid, sebacic acid, sebacic acid, 2,6-naphthalene dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and the like. As the diol, ethylene glycol, 1,4-butanediol, and the like can be exemplified. Ethylene glycol, triethylene glycol, neopentyl glycol, 1,4-cyclohexane dimethanol, polyethylene glycol, etc., and hydroxycarboxylic acid, p-hydroxybenzoic acid, 6-hydroxy-2- Naphthoic acid and the like. Representative examples of the polymer include polyethylene terephthalate or polyethylene-2,6-naphthalenedicarboxylate.

In the film of the present invention, it is preferred to blend the particles in order to impart slipperiness and prevent the occurrence of damage in each step. The type of the particles to be blended is not particularly limited as long as it imparts slipperiness, and specific examples thereof include cerium oxide, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, and phosphoric acid. Particles such as magnesium, kaolin, alumina, and titanium oxide. In addition, the heat-resistant organic particles described in Japanese Patent Publication No. 59-217755, and the like. Examples of the other heat-resistant organic particles include a thermosetting urea resin, a thermosetting phenol resin, a thermosetting epoxy resin, and a benzoguanamine resin. Further, in the polyester production step, precipitated particles in which a part of the metal compound such as a catalyst is precipitated or finely dispersed may be used.

Further, the shape of the particles to be used is not particularly limited, and any of a spherical shape, a block shape, a rod shape, and a flat shape may be used. Further, the hardness, specific gravity, color, and the like are not particularly limited. These series of particles may be used in combination of two or more types as needed.

Further, the particles to be used have an average particle diameter of usually from 0.01 to 3 μm, preferably from 0.1 to 2 μm. When the average particle diameter is less than 0.01 μm, the slipperiness may not be imparted. In addition, when it exceeds 3 μm, when the film is formed, the transparency of the particles is lowered due to the aggregation of the particles. The problem is also a problem on the productive side due to the possibility of breakage.

Further, the content of the particles in the polyester is usually in the range of 0.001 to 5% by weight, preferably 0.005 to 3% by weight. When the content of the particles is less than 0.001% by weight, the slipperiness of the film may be insufficient, and when the amount is more than 5% by weight, the transparency of the film may be insufficient.

The method of adding particles to the polyester layer is not particularly limited, and a conventionally known method can be employed. For example, it may be added at any stage in which the polyester constituting each layer is produced, but it is preferably added after the esterification or transesterification reaction is completed.

Further, it can also be carried out by a method of mixing a slurry of a particle of ethylene glycol or water with a polyester raw material by using a kneading extruder equipped with a vent hole, or by using a kneading pressure. A method of discharging and blending the dried particles with a polyester raw material, and the like.

Further, in the polyester film of the present invention, in addition to the above particles, a conventionally known antioxidant, an antistatic agent, a thermal stabilizer, a lubricant, a dye, a pigment, or the like may be added as needed.

The thickness of the polyester film in the present invention is not particularly limited as long as it can be formed into a film, and is usually in the range of 10 to 350 μm, preferably 15 to 100 μm.

In the release film of the present invention, after heating at 180 ° C for 10 minutes, the amount of oligomer (OL) on the surface of the release layer is 2.0 mg/m ² or less. The amount of the oligomer after heating is obtained by heating the release film at 180 ° C for 10 minutes, and then washing the surface with 4 ml of DMF (dimethylformamide) to obtain the DMF by liquid chromatography. The amount of oligomer, which was measured by dividing the film area of the DMF contact, was measured as the amount of film surface oligomer (mg/m ² ).

The method of reducing the OL after heating includes a method of reducing the amount of the oligomer in the polyester by solid phase polymerization of the polyester, or a method of providing a coating layer for preventing the precipitation of the oligomer. In particular, the present invention has a function of effectively preventing the oligomer from being deposited on the coating layer. Various methods can be employed in preventing the precipitation of oligomers. For example, there is a method of containing an organic compound containing aluminum in the coating layer, but it is not limited thereto.

Next, although the production example of the polyester film in the present invention is specifically described, it is not limited to the following production examples. That is, a method in which the molten sheet extruded from the extrusion nozzle is cooled and solidified by a cooling roll to obtain an unstretched sheet is preferably used. At this time, in order to improve the planarity of the sheet, it is preferable to improve the adhesion between the sheet and the rotary cooling drum, and it is preferable to use an electrostatic sealing method and/or a liquid coating adhesion method. The resulting unstretched sheet can then be extended in the biaxial direction. At this time, first, the unstretched sheet is stretched in a single direction in a roll or tenter type stretching machine. The stretching temperature is usually from 90 to 140 ° C, preferably from 95 to 120 ° C, and the stretching ratio is usually from 2.5 to 7 times, preferably from 3.0 to 6 times. Next, it extends in a direction perpendicular to the extending direction of the first stage, and at this time, the stretching temperature is usually 90 to 170 ° C, and the stretching ratio is usually 3.0 to 7 times, preferably 3.5 to 6 times. Then, heat treatment is continued at a temperature of 180 to 270 ° C under tension or within 30% to obtain a biaxial alignment film. The above extension can be carried out by extending the single direction in two or more stages. method. In this case, it is preferred that the stretching ratios in the final two directions are each in the above range.

Further, in the production of the polyester film of the present invention, a simultaneous biaxial stretching method can also be employed. At the same time, the biaxial stretching method is a method in which the unstretched sheet is simultaneously extended and aligned in the mechanical direction and the wide direction at a temperature of 90 to 140 ° C, preferably 80 to 110 ° C, and the stretching ratio is extended. In terms of area magnification, it is 4 to 50 times, preferably 7 to 35 times, more preferably 10 to 25 times. Then, heat treatment is continued at a temperature of 170 to 250 ° C under tension or within 30% to obtain an extended alignment film. Regarding the simultaneous biaxial stretching device using the above extension method, a conventionally known extension method such as a propeller method, a pantograph method, or a linear driving method can be employed.

The method of forming the coating layer on the surface of the polyester film is not particularly limited, but is preferably a method of applying a coating liquid in the step of producing a polyester film. Specifically, a method in which the coating liquid is applied to the surface of the unstretched sheet and dried, a method in which the coating liquid is applied to the surface of the one-axis stretched film and dried, and a coating liquid is applied to the surface of the biaxially stretched film to be dried. Method and so on. Among these, it is economical to dry and harden the coating layer while heat-treating the film after applying the coating liquid to the surface of the unstretched film or the one-axis stretching film. Further, in terms of the method of forming the coating layer, a method of using several of the above coating methods may be employed as needed. Specifically, a method in which the first layer is applied to the surface of the unstretched sheet and dried, and then the second layer is applied and dried after being stretched in the axial direction is used. For the method of applying the coating liquid on the surface of the polyester film, you can use Harahara, A reverse roll coater, a gravure coater, a bar coater, a pneumatic blade coater, and the like shown in "Coating Method" issued by the bookstore in 1979.

Next, the formation of the coating layer in the present invention will be described. The coating layer constituting the release film of the present invention contains an organic ruthenium compound in order to improve the deposition prevention property of the oligomer and to improve the adhesion of the release film and the polyester film over time. Preferably, the organic ruthenium compound represented by the following general formula (1) is more preferably used.

Si(X) _d (Y) _e (R ¹ ) _f ...(1)

In the above formula, X has at least one organic group selected from the group consisting of an epoxy group, a fluorenyl group, a (meth) acryl fluorenyl group, an alkenyl group, a haloalkyl group, and an amine group, and R1 is a monovalent hydrocarbon group and has a carbon number of 1 In the case of ~10, Y is a hydrolyzable group, d is an integer of 1 or 2, e is an integer of 2 or 3, f is an integer of 0 or 1, and d+e+f=4.

The organic ruthenium compound represented by the above general formula (1) may be a hydrolyzable group Y having two (D unit sources) or three (T unit sources) capable of forming a siloxane coupling by hydrolysis or condensation reaction. .

In the general formula (1), the monovalent hydrocarbon group R ^{1 has} a carbon number of from 1 to 10, particularly preferably a methyl group, an ethyl group or a propyl group.

In the general formula (1), a conventionally known one can be used as the hydrolyzable group Y, and the following can be exemplified. Methoxy, ethoxy, butoxy, isopropenyloxy, ethoxylated, butanone oxime and amine groups. These hydrolyzable groups may be used singly or in plural. When a methoxy group or an ethoxy group is used, the coating material can be imparted with good preservation stability and with appropriate water. It is especially good for solution.

In the present invention, as the organic ruthenium compound contained in the coating layer, specifically, vinyl trimethoxy decane, γ-glycidoxytrimethoxy decane, γ-glycidoxymethyl group can be exemplified. Diethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-mercaptopropyltrimethoxydecane, γ-methylpropoxypropyltrimethoxydecane, γ - propyleneoxypropyltrimethoxydecane, γ-aminopropyltriethoxydecane, 5-hexenyltrimethoxydecane, p-styryltrimethoxydecane, trifluoropropyltrimethoxy Decane, γ-glycidoxytriethoxydecane, γ-glycidoxymethyldiisopropenyloxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, etc. .

In the present invention, in order to improve the precipitation preventing property of the release film and to improve the coating film adhesion of the release film and the polyester film over time, the coating layer contains aluminum. Organic compounds are good.

An organic compound having an aluminum element, and specific examples thereof may be exemplified by aluminum ginseng (acetamidine pyruvate), aluminum monoethyl acetonate bis(acetate ethyl acetate), aluminum-di-n-butoxy-single Ethyl acetate, aluminum-di-iso-propoxy-monoethylammonium acetate, aluminum ginate (acetic acid ethyl acetate) and the like.

The amount of the aluminum compound contained in the coating layer is usually in the range of 0.001 to 70% by weight, preferably 5 to 35% by weight, more preferably 5 to 15% by weight. When the amount of the aluminum compound is 0.001% by weight or less, the hardening reaction of the coating layer cannot be rapidly performed, and the coating film adhesion property of the release surface after forming the release layer on the coating layer is deteriorated. Further, if the amount of the aluminum compound is 70% by weight or more, the hardening reaction of the coating layer and the residual aluminum in the coating layer are irrelevant. The compound hinders the hardening of the release layer, and the adhesion of the coating film on the release surface is deteriorated.

The coating layer may also contain an organic compound having a metal element other than aluminum. In particular, an organotin compound is preferred. Specific examples of the organotin compound include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctanoate, dibutyltin dioleate, diphenyltin diacetate, and dibutyltin oxidation. , dibutyltin dimethoxide, dibutyl bis(triethoxydecyloxy)tin, dibutyltinbenzyl maleate, dioctyltin diacetate, dioctyltin dilaurate Wait.

In addition, inorganic particles may be contained for the purpose of improving the fixing property and lubricity of the coating layer, and specific examples thereof include cerium oxide, aluminum oxide, kaolin, calcium carbonate, titanium oxide, and cerium salt.

Further, if necessary, an antifoaming agent, a coatability improver, a tackifier, an organic lubricant, an organic polymer particle, an antioxidant, an ultraviolet absorber, a foaming agent, a dye, or the like may be contained.

In the range which does not exceed the gist of the present invention, the organic solvent to be used may be used singly or in combination of two or more kinds.

The coating amount (after drying) of the coating layer provided on the polyester film constituting the release film of the present invention is usually in the range of 0.005 to 1 g/m ² , preferably 0.005 to 0.5 g/m ² . . When the coating amount (after drying) is less than 0.005 g/m ² , the uniformity of the coating thickness may be insufficient, and the amount of the oligomer precipitated from the surface of the coating layer may increase after the heat treatment. Further, when the coating amount exceeds 1 g/m ² , a problem such as a decrease in lubricity is caused.

In the present invention, the curing conditions in forming the coating layer on the polyester film are not particularly limited. For example, when the coating layer is provided by off-line coating, it is usually 60 to 200 ° C for 3 to 40 seconds. Preferably, the heat treatment is performed at 80 to 180 ° C for 3 to 40 seconds. Further, if necessary, it is also possible to use an active energy ray such as heat treatment or ultraviolet irradiation.

The type of the release layer-type polysulfonated resin which is formed on the one-side outermost layer of the polyester film obtained in the present invention includes addition molding, condensation type, ultraviolet curing type, electron beam curing type, solventless type, and the like. A hardening reaction form can be used.

Examples of the polyfluorene oxide resin having an alkenyl group and an alkyl group as a functional group used in the present invention include the following. First, an alkenyl group-containing hardening polyoxynoxy resin, in terms of diorganopolyoxyalkylene, a molecular chain having a terminal trimethyl methoxy group to block dimethyloxane ‧ methylhexenyl oxime Alkane copolymer (96 mole % of dimethyloxane, 4 mole % of methylhexenyl oxirane), dimethylvinyl methoxy group at the two ends of the molecular chain, dimethyl oxoxane ‧Methylhexenyl decane copolymer (methyl methoxide unit 97 mol%, methylhexenyl decane unit 3 mol%), molecular chain both ends dimethylhexenyl hydrazine The oxy group blocked the dimethyloxane ‧ methylhexenyl decane copolymer (dimethyloxane unit 95 mol%, methylhexenyl decane unit 5 mol%). Next, the alkyl-containing hardening polyfluorene oxide, in terms of the organic hydrogen polyoxyalkylene, may be exemplified by a molecular chain at both ends of a trimethyl methoxy group to block methyl hydrogen polyoxyalkylene, a molecular chain. The two-terminal trimethyl methoxy group blocks the dimethyl oxane ‧ methyl hydrazine copolymer, the two ends of the molecular chain dimethyl hydro hydroxy groups block the methyl hydrogen polyoxy siloxane, and the two ends of the molecular chain The methylhydroquinoneoxy group blocks the dimethyloxane ‧ methylhydroquinoxane copolymer.

The polyfluorene oxide resin having a hexenyl group and a phenyl group used in the present invention is preferably an organopolyoxane represented by the following general formula (I). Although the chemical structure is represented by the general formula (I), it may be a linear structure or a divergent structure. The introduction portion of each functional group may be any optional.

In the above formula, a and b each represent a positive integer.

The polyfluorene oxide resin having a vinyl group and a phenyl group used in the present invention is preferably an organopolyoxane represented by the following general formula (II). Although the chemical structure may be represented by the general formula (II), it may be a linear structure or a divergent structure. The introduction portion of each functional group may be any optional.

In the above formula, c and d each represent a positive integer.

The polyfluorene oxide having a hydrogenated alkylene group used in the present invention is preferably an organopolyoxane represented by the following general formula (III). Although the chemical structure may be represented by the general formula (III), it may be a linear structure or a divergent structure. The introduction portion of each functional group may be any optional.

In the above formula, e and f each represent a positive integer.

Although the polyhexyloxy resin having a hexenyl group and the polyoxyl resin having a vinyl polymer group are classified into the formulas (I) and (II), they may be contained in one organic polyoxane. Hexenyl and vinyl polymer groups.

Further, the phenyl group is not necessarily required to be contained in the polyfluorene oxide resin containing a hexenyl group and a vinyl group, and a phenyl group may be contained in one organic polysiloxane.

The ratio of the hexenyl group, the vinyl group, the phenyl group and the hydrazinyl group contained in the polyfluorene oxide resin used in the present invention is a hexenyl group of 35 to 65 and a vinyl group when the alkylene group is 100. It is preferably 5 to 35 and phenyl is 1 to 20. It is desirable to have a hexenyl group of 45 to 55, a vinyl group of 15 to 25, and a phenyl group of 2 to 10. If the hexenyl group does not reach 35, it is hard. The chemical reaction will be insufficient, and the peeling force at 30,000 mm/min will become high, and when the release film is peeled off at a high speed from the adhesive, there is a problem that the peeling film cannot be perfectly peeled off. When the amount of the hexenyl group exceeds 65, the degree of crosslinking is too large in the polyoxygen curing, and the peeling force at 300 mm/min is high, and when the release film is peeled off from the adhesive, there is a problem that the peeling film cannot be perfectly peeled off. occur. If the vinyl group is less than 15, the polyoxygen hardening reaction will be insufficient, and the peeling force at 30,000 mm/min will become high, and when the release film is peeled off at a high speed from the adhesive, there is a problem that the peeling film cannot be perfectly peeled off. When the vinyl group exceeds 35, in the case of polyoxygen curing, the crosslinking point is too large, and the peeling force at 300 mm/min is high, and when the release film is peeled off from the adhesive, the defective state may not be perfectly peeled off. . When the phenyl group is less than 1, the polyfluorene oxide film becomes soft, and the peeling force at 30,000 mm/min is increased. When the release film is peeled off at a high speed from the adhesive, a problem that the peeling film cannot be perfectly peeled off may occur. When the phenyl group exceeds 20, the polyfluorene oxide film becomes too hard, and the peeling force at 300 mm/min is high, and when the release film is peeled off from the adhesive, there is a problem that the peeling film cannot be perfectly peeled off.

The dimethyl fluorenyl group (general formula (I) a, general formula (II) c, general formula (III) f) contained in the polyfluorene oxide resin used in the present invention is 2,000 or more and 5,000 or less. It is better. More preferably, it is preferably 3000 or more and 4000 or less. If it is less than 2000, there will be a problem that the molecular weight is small and the unreacted polyoxygen will migrate to the adhesive layer. If it exceeds 5,000, the molecular weight is too large and the hardening reaction does not proceed smoothly, and the desired peeling characteristics may not be obtained.

In the present invention, in order to impart light peelability, it is necessary to add An unreactive polyxanthene resin having a mass average molecular weight of 50,000 or more and 100,000 or less.

The above-mentioned unreacted polyoxyphthalocene resin is preferably an organopolyoxane represented by the following general formula (IV).

In the above formula, g represents a positive integer.

The polyoxyphthalocene resin used in the present invention contains 1 to 10% by weight, preferably 1 to 5% by weight, of the unreacted polyoxyl resin. When the content of the unreacted polyoxyl resin is less than 1%, the peeling is not possible, and when it is more than 5% by weight, the curability is remarkably lowered, and the adhesion is also deteriorated.

In the present invention, in order to reduce the peeling force, polyoxygenated oil may be added. The polyoxygenated oil is a polyoxygenated oil called a straight-run polyoxyxene oil or a modified polyoxygenated oil, and the following may be mentioned. Examples of the straight-run polyoxyl oil include dimethylpolyphthalic acid oil, methylphenylpolyphosphoric acid oil, and methyl hydrogen polyoxygenated oil. Further, examples of the modified polyoxyxene oil include a polyether modification in a side chain type, an aralkyl modification, a fluoroalkyl modification, a long-chain alkyl modification, a higher fatty acid ester modification, and an advanced Fatty acid decylamine modification, polyether ‧ long-chain alkyl modification ‧ aralkyl modification, phenyl modification, two-terminal polyether modification, polyether ‧ Oxygen modification and the like.

The polyoxyxylene oil component contained in the polyoxyxylene resin used in the present invention is in the range of 1 to 10% by weight, preferably 1 to 5% by weight. When the content of the polyoxygenated oil component is less than 1%, the speed dependency becomes high, and if it exceeds 5% by weight, the transition property is high, and the roller is smeared or migrated to the adhesive surface during the processing of the adhesive to cause adhesion. The peeling force is lowered, and the like.

In the present invention, the residual adhesion ratio of the No. 31B tape manufactured by Nitto Denko Corporation is preferably 80% or more, more preferably 85% or more. When the residual adhesion ratio is less than 80%, the migration property is high, and the roller is smeared or moved to the adhesive surface during the processing of the adhesive, and the adhesive peeling force is lowered.

In the present invention, the No. 31B tape manufactured by Nitto Denko Corporation is preferably used at a peeling force of 300 mm/min of 10 to 20 mN/cm. When the peeling force of 300 mm/min is more than 20 mN/cm, when the release film is peeled off from the adhesive, there is a problem that the release film cannot be perfectly peeled off.

In the present invention, it is preferred that the No. 31B tape manufactured by Nitto Denko Co., Ltd. has a peeling force of less than 80 mN/cm at 30,000 mm/min. When the peeling force of 30,000 mm/min is more than 80 mN/cm, when the release film is peeled off at a high speed from the adhesive, a problem that the peeling film cannot be peeled off perfectly may occur.

As the type of the curable polyoxynoxy resin, any of the hardening reaction forms, such as addition molding, condensation type, ultraviolet curing type, electron beam curing type, and solventless type, can be used. For specific examples, KS-774, KS-775, KS-778, KS-779H, KS-847H, KS-856, X-62-2422, and X-62- can be exemplified by Shin-Etsu Chemical Co., Ltd. 2461, X- 62-1387, X-62-5039, X-62-5040, KNS-3051, X-62-1496, KNS320A, KNS316, X-62-1574A/B, X-62-7052, X-62-7028A/ B, X-62-7619, X-62-7213, X-62-2829, Momentive Performance Materials YSR-3022, TPR-6700, TPR-6720, TPR-6721, TPR6500, TPR6501, UV9300, UV9425, XS56- A2775, XS56-A2982, XS56-C6010, XS56-C4880, UV9430, TPR6600, TPR6604, TPR6605, Dow Corning Toray SRX357, SRX211, SD7220, SD7292, LTC750A, LTC760A, LTC303E, LTC300B, LTC856, SP7259, BY24 -468C, SP7248S, BY24-452, DKQ3-202, DKQ3-203, DKQ3-204, DKQ3-205, DKQ3-210, etc. Further, in order to adjust the peeling property of the release layer or the like, a release controlling agent may be used in combination.

In the present invention, a conventionally known coating method such as reverse roll coating, gravure coating, bar coating, or blade coating can be used for the method of providing the release layer of the polyester film. The coating 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, a coating layer such as an adhesive layer, an antistatic layer, an oligomer precipitation preventing layer or the like may be provided on the surface on which the release layer is not provided, and a corona treatment and a plasma may be applied to the polyester film. Surface treatment such as processing.

In the polyester film of the present invention, in order to make the release layer beautiful and strong, a platinum-based catalyst which promotes the reaction of the addition molding can be used. Examples of the component include platinum chloride acid, an alcohol solution of chloroplatinic acid, a complex of chloroplatinic acid and an olefin, and a platinum compound of a complex of a platinum chloride acid and an alkenyl siloxane. Platinum black, ruthenium oxide bearing platinum, and activated carbon holding platinum. The content of the platinum-based catalyst in the release layer is usually in the range of 0.3 to 3.0% by weight, preferably 0.5 to 2.0% by weight. When the content of the platinum-based catalyst in the release layer is lower than 0.3% by weight, the peeling force may be poor, or the hardening reaction in the coating layer may be insufficient, and the surface may be deteriorated, and the like may occur. When the content of the platinum-based catalyst in the release layer exceeds 3.0% by weight, the cost is high and the reactivity is high, and a step such as generation of colloidal foreign matter may occur.

Further, since the reaction of addition molding is extremely high in reactivity, acetylene alcohol may be added as a reaction inhibitor as the case may be. The composition is an organic compound having a carbon-carbon triple bond and a hydroxyl group, preferably 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol and A selected group of phenylbutynols.

The peeling force in the present invention means that the double-sided adhesive tape ("No. 31B" manufactured by Nitto Denko Corporation) is attached to the release layer, and after being left at room temperature for one hour, the peeling angle is 180° with the base film. When the tape was peeled off, the value was measured by a tensile tester. In the present invention, the method of adjusting the specific peeling force can be achieved by selecting the composition in the release layer, but other means can be used, mainly depending on the type of the release agent of the polyfluorinated release layer. The peeling force is preferably changed. Further, since the peeling force largely depends on the amount of the release agent to be used, it is more preferable to adjust the coating amount of the release agent.

The value of the peeling force of the polyester film of the present invention is usually in the range of 10 to 20 mN/cm at a low speed peeling force in a region of 300 mm/min. When the peeling force is less than 10 mN/cm, the peeling force is too light, and there will be originally In the case where it is not necessary to peel off, the defective condition which is easily peeled off occurs. When the peeling force exceeds 20 mN/cm, the difference in peeling force of the release film is small when the peeling force is heavy, and a problem occurs in the peeling step, and the peeling force is large, and the determined range of the release film is small.

Further, the high-speed peeling force in the region of the speed of 60,000 mm/min in consideration of workability is usually 90 mN/cm or less. When the peeling force is more than 90 mN/cm, the peeling force of the release film is small, and the peeling force difference is small, and the peeling step cannot be smoothly peeled off, and the entire adhesive is peeled off.

After the release film of the present invention is subjected to heat treatment (180 ° C, 10 minutes), the amount of the oligomer (OL) of the polyester extracted from the surface of the release layer by dimethylformamide is usually 2.0 mg/m. ² or less, preferably 1.0 mg/m ² or less. When the OL exceeds 2.0 mg/m ² , for example, when the liquid crystal constituent member is used for the purpose of protecting the adhesive layer, the transparency of the adhesive may be lowered, the adhesive force of the adhesive layer may be lowered, or the optical evaluation may be accompanied. In the inspection step, there are obstacles such as obstacles.

In the release film of the present invention, in order to make OL satisfy the above range, the amount of aluminum element contained in the coating layer is 0.2 kcps by a fluorescent X-ray measuring apparatus and measured by a FP (Fundamental Parameter Method) method. The above, more preferably 0.5 kcps or more, particularly preferably 0.8 kcps or more. When the amount of aluminum element is less than 0.2 kcps, the desired oligomer sealing performance may not be obtained.

The "oligomer" in the present invention is defined as a cyclic triad in a low molecular weight product of a polyester which is crystallized and precipitated on the surface of the film after heat treatment.

<Second embodiment>

In the present invention, the polyester film constituting the two release films (hereinafter referred to as the first release film having a small peeling force and the second release film having a large peeling force) may be a single layer structure or a laminated structure, for example, In addition to the two-layer and three-layer configuration, a layer of four or more layers may be used without exceeding the gist of the present invention, and is not particularly limited.

In the present invention, the polyester used in the polyester film may be a homopolyester or a copolyester. When it is made of a homopolyester, it is preferable to obtain a polycondensation of an aromatic dicarboxylic acid and an aliphatic diol.

Examples of the aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid, and examples of the aliphatic diol include ethylene glycol, diethylene glycol, and 1,4-cyclohexane. Dimethanol and the like.

As the polyester represented, polyethylene terephthalate (PET) or the like can be exemplified.

Further, examples of the dicarboxylic acid component of the copolyester include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, and oxycarboxylate. One or two or more kinds of the acid (for example, P-oxybenzoic acid), and examples of the diol component include ethylene glycol, diethylene glycol, propylene glycol, butanediol, and 1,4-ring. One or two or more kinds of hexane dimethanol or neopentyl glycol. In any case, the polyester in the present invention generally means a polyester such as polyethylene terephthalate having a content of 60 mol% or more, preferably 80 mol% or more. .

In the present invention, the polyester layer is mainly provided with imparting slipperiness. In terms of purpose, it is better to blend particles. The type of the particles to be blended is not particularly limited as long as it imparts slipperiness, and specific examples thereof include cerium oxide, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, and calcium phosphate. Particles such as magnesium phosphate, kaolin, alumina, and titanium oxide. Further, heat-resistant organic particles contained in JP-A-59-5216, JP-A-59-217755, and the like can be used. Examples of the other heat-resistant organic particles include a thermosetting urea resin, a thermosetting phenol resin, a thermosetting epoxy resin, and a benzoguanamine resin. Further, in the polyester production step, precipitated particles obtained by precipitating and finely dispersing a part of the metal compound such as a catalyst may be used.

Further, the shape of the particles to be used is not particularly limited, and any of a spherical shape, a block shape, a rod shape, and a flat shape may be used. Further, there is no particular limitation on the hardness, specific gravity, color, and the like. These series of particles can be used in combination of two or more types as needed.

Further, the average particle diameter of the particles to be used is usually in the range of 0.01 to 3 μm, preferably 0.01 to 1 μm. When the average particle diameter is less than 0.01 μm, the particles tend to aggregate and the dispersibility is insufficient. Further, when the thickness exceeds 3 μm, the surface roughness of the film becomes too thick, and in the subsequent step, the coating is provided with a release type. When there is a layer, there is a case where a bad condition occurs.

Further, the content of the particles in the polyester layer is usually in the range of 0.001 to 5% by weight, preferably 0.005 to 3% by weight. When the content of the particles is less than 0.001% by weight, the slipperiness of the film may be insufficient, and when it is added in an amount of more than 5% by weight, the transparency of the film may be insufficient.

There is no special way to add particles to the polyester layer. Restricted, a conventionally known method can be employed. For example, although it may be added at any stage of producing the polyester constituting each layer, it is preferred to carry out the polycondensation reaction after the stage of esterification or after the end of the transesterification reaction.

Further, the method may be carried out by using a kneading extruder equipped with a gas exchange device to blend a slurry of particles such as ethylene glycol or water with a polyester raw material, or using A method in which a kneading extruder is used to blend dried particles with a polyester raw material.

Further, in the polyester film of the present invention, in addition to the above-mentioned particles, conventionally known antioxidants, antistatic agents, thermal stabilizers, lubricants, dyes, pigments and the like may be added as needed.

The thickness of the polyester film constituting the first release film and the second release film of the present invention is not particularly limited as long as it can be formed into a film. The first release film is usually in the range of 25 to 75 μm, preferably 38 to 75 μm. Further, the second release film is usually in the range of 25 to 250 μm, preferably 38 to 188 μm, more preferably 50 to 125 μm.

Next, a production example of the polyester film in the present invention will be specifically described below, but is not limited to the production examples described below.

First, it is preferred to use a method in which the above-mentioned polyester raw material is used, and a molten sheet extruded from a nozzle is cooled and solidified by a cooling roll to obtain an unstretched sheet. At this time, in order to improve the planarity of the sheet, it is necessary to improve the adhesion between the sheet and the rotary cooling barrel, and it is preferable to employ an external electrostatic adhesion method and/or a liquid coating adhesion method. Next, the resulting unstretched sheet can be extended in the biaxial direction. At this time, the aforementioned unstretched sheet is first stretched in a single direction by a roll or tenter type stretching machine. The extension temperature is usually 70 ~120 ° C, preferably 80 ~ 110 ° C, the stretching ratio is usually 2.5 to 7 times, preferably 3.0 to 6 times. Then, the extension temperature perpendicular to the extending direction of the first stage is usually 70 to 170 ° C, and the stretching ratio is usually 3.0 to 7 times, preferably 3.5 to 6 times. Then, heat treatment is continued at a temperature of 180 to 270 ° C under tension or within 30% to obtain a biaxial alignment film. In the above extension, a method of performing the extension in a single direction in two or more stages may be employed. In this case, it is preferable that the stretching ratio in the two directions is individually set to the above range.

Further, in the production of the polyester film of the present invention, a simultaneous biaxial stretching method can also be employed. At the same time, the biaxial stretching method is a method in which the unstretched sheet is simultaneously extended and aligned in the mechanical direction and the wide direction in a temperature control state of usually 70 to 120 ° C, preferably 80 to 110 ° C, and the stretching ratio thereof is extended. In terms of area magnification, it is 4 to 50 times, preferably 7 to 35 times, more preferably 10 to 25 times. Then, heat treatment is continued at a temperature of 170 to 250 ° C under tension or within 30% to obtain an extended alignment film. Regarding the simultaneous biaxial stretching device using the above extension method, a conventionally known extension method such as a propeller method, a pantograph method, or a linear driving method can be employed.

Further, in the step of extending the polyester film, a coating stretching method (in-line coating) for treating the surface of the film can be carried out. When the coating layer is provided on the polyester film by the coating stretching method, the thickness of the coating layer can be thinned together with the stretching ratio when it is stretchable and simultaneously coated, and a film suitable as a polyester film can be produced. .

Next, it constitutes a coating layer of the release film in the present invention. Be explained.

The coating layer constituting the release film of the present invention contains the conductive compound (A) in order to enhance the antistatic property and the prevention of the precipitation of the oligomer. In the aspect of the conductive compound (A), a polymer obtained by separately or copolymerizing a thiophene or a thiophene derivative is preferred, and in particular, a compound obtained from a thiophene or a thiophene derivative is doped with another anionic compound. It is preferable to dope the compound with an anion group itself, since it exhibits excellent conductivity. In the case of the compound (A), those obtained by polymerizing a compound of the following formula (1) or (2) in the presence of a polyanion can be exemplified.

In the above formula (1), R ¹ and R ² each independently represent a hydrogen element, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group or an aromatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group or an isopropyl group. Base, butyl, cyclohexyl, phenyl, and the like.

In the above formula (2), n is an integer of 1 to 4.

In the release film of the present invention, it is preferred to use a polythiophene or a polythiophene derivative obtained by the structural formula shown by Chemical Formula 2, for example, in the case of 2, n=1 (methylene), n=2 ( Compounds having an ethyl group and n = 3 (extended propyl) are preferred. Among them, a compound of ethyl group having n = 2, that is, poly-3,4-extended ethyldioxythiophene is particularly preferable. As the polythiophene or polythiophene derivative, a compound having a functional group bonded at the 3-position and 4-position positions of the thiophene ring can be exemplified. As described above, a compound in which an oxygen atom is bonded to a carbon atom at the 3 position and the 4 position is preferred. The compound having a structure in which a carbon atom or a hydrogen atom is directly bonded to the carbon atom may be difficult to be aqueous.

Examples of the polyanion used in the polymerization include poly(meth)acrylic acid, polymaleic acid, polystyrenesulfonic acid, and the like. Again, these acids may be partially or completely neutralized.

Further, as a method of producing the polymer, for example, a method shown in Japanese Laid-Open Patent Publication No. Hei 7-90060 can be employed.

In the present invention, particularly preferred aspects are those in which the compound of the above formula (2) has n = 2 and polystyrene sulfonic acid is used as the polyanion.

The coating layer constituting the release film of the present invention is required to contain the above-mentioned conductive compound and binder polymer.

The binder polymer (B) constituting the coating layer in the present invention is defined as a flow chart for the safety evaluation of a polymer compound (mainly reminded by the Chemical Substance Review Meeting of the Showa 60, Japan), by colloidal permeation chromatography (GPC). A polymer compound having a number average molecular weight (Mn) of 1,000 or more and having a film-forming property.

The binder polymer (B) constituting the coating layer in the present invention may be a thermosetting resin or a thermoplastic resin if it is compatible with the thiophene or the thiophene derivative or may be mixed and dispersed. For example, polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.; polyimine, polyamidimide, etc. Polyimine; polyamido 6, polyamine 6,6, polyamide 12, polyamide amine, etc.; polyfluorinated vinylidene, polyfluorinated vinyl, polytetrafluoroethylene, ethylene a fluororesin such as a tetrafluoroethylene copolymer or a polychlorotrifluoroethylene; a vinyl resin such as polyvinyl alcohol, polyvinyl ether, polyvinyl butyral, polyvinyl acetate or polyvinyl chloride; Oxygen resin; propylene oxide resin; xylene resin; aromatic polyamide resin; polyimine polyoxyl; polyurethane; polyurea; melamine resin; phenol resin; polyether; And such copolymers and the like.

The blending ratio of the conductive compound (A) in the coating layer is from 10 to 90% by weight, preferably from 20 to 80% by weight. When it is less than 10% by weight, there is a case where the antistatic property and the oligomer precipitation preventing property are insufficient. In addition, if it exceeds 80% by weight, the antistatic property is already in a saturated state, that is, In the case of increments above this value, there are cases where it is difficult to obtain a significant effect.

These binder polymers (B) can also be dissolved in an organic solvent, and can impart an aqueous solution by imparting a functional group such as a sulfonic acid group or a carboxyl group. Further, in the binder polymer (B), a curing agent such as a crosslinking agent or a polymerization initiator, a polymerization accelerator, a solvent, a viscosity adjuster, or the like may be used in combination.

In the above-mentioned binder polymer (B), it is preferred to select one or more of the polyester resin, the acryl resin, and the polyurethane resin in order to facilitate the mixing of the coating liquid. In particular, a polyurethane resin is preferred.

The polyester resin used in the present invention is defined as a linear polyester having a dicarboxylic acid component and a diol component as constituent components. Examples of the dicarboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acid, 4,4-diphenyldicarboxylic acid, and 1,4-cyclohexane. Alkanedicarboxylic acid, adipic acid, sebacic acid, phenyldihydroindole dicarboxylic acid, dimer acid, and the like. These components can be used in two or more types. Further, an unsaturated polybasic acid such as maleic acid, fumaric acid, itaconic acid or the like or p-hydroxybenzoic acid, p-(β-hydroxyethoxy)benzoic acid may be used in a small proportion together with these components. The hydroxycarboxylic acid. The ratio of the unsaturated polybasic acid component or the hydroxycarboxylic acid component is 10 mol% or more, preferably 5 mol% or less.

Further, examples of the diol component include ethylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,6-hexanediol, and 1,4-ring. Hexane dimethanol, dimethyl phenyl diol, dimethylol propionic acid, glycerol, trimethylolpropane, poly(ethyleneoxy) diol, poly (tetramethyleneoxy) diol, an alkylene oxide adduct of bisphenol A, an alkylene oxide adduct of hydrogenated bisphenol A, and the like. These can be used in two or more types.

Among the polyol components, ethylene glycol, ethylene oxide adduct of bisphenol A or propylene oxide adduct, 1,4-butanediol is preferred, and ethylene glycol and bisphenol A are further included. The ethylene oxide adduct or the propylene oxide adduct is preferred. Further, in the polyester resin, in order to facilitate aqueous liquefaction, a certain amount of a compound having a sulfonate group or a compound having a carboxylate group may be copolymerized, and it is preferred. The compound having a sulfonate group is preferably, for example, 5-sodium sulfoisophthalic acid, 5-ammonium sulfoisophthalic acid, 4-sodium sulfoisophthalic acid, or 4- Methylammonium sulfoisophthalate, 2-sodium sulfoisophthalate, 5-potassium sulfoisophthalate, 4-potassium sulfoisophthalate, 2-potassium sulfonate An alkali metal sulfonate or a sulfonic acid amine salt compound such as isophthalic acid or sodium sulfosuccinate.

Examples of the compound having a carboxylate group include anhydrous trimellitic acid, trimellitic acid, anhydrous pyromellitic acid, pyromellitic acid, symmetrical trimellitic acid, cyclobutanetetracarboxylic acid, and dihydroxyl. Propionic acid, etc., or such monoalkali metal salts, and the like. Further, the free carboxyl group is subjected to copolymerization to cause an alkali metal compound or an amine compound to act as a carboxylate group. A polyester obtained by synthesizing one or more of these compounds in a suitable manner and synthesizing them by a conventional polycondensation reaction can be used.

The glass transition temperature (hereinafter abbreviated as Tg) of the polyester resin is usually 40 ° C or higher, preferably 60 ° C or higher. When the Tg is less than 40 ° C, in the case where the coating thickness of the coating layer is thick for the purpose of improving the adhesion, there is a problem that it is easy to seal the end.

The acryl-based resin is a polymer composed of a polymerizable monomer having a carbon-carbon double bond, as represented by an acrylic or methacrylic monomer. These may be individual polymers or copolymers. Also included are copolymers of such polymers with other polymers (e.g., polyesters, polyurethanes, etc.). For example, block copolymers, graft copolymers. Further, a polymer obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in a polyester solution or a polyester dispersion (which may optionally be a mixture of polymers) is also included. Similarly, a polymer obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in a polyurethane solution or a polyurethane dispersion (which may optionally be a mixture of polymers) is also included. . Similarly, a polymer obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond (which may optionally be a mixture of polymers) is also included in other polymer solutions or dispersions.

The polymerizable monomer having a carbon-carbon double bond is not particularly limited, but various compounds such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and citraconic acid are various. a carboxyl group-containing monomer and salts thereof; such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, single Various hydroxyl group-containing monomers of butyl hydroxy fumarate, monobutyl hydroxy itaconate; such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (a) Various (meth) acrylates of acrylate, butyl (meth) acrylate, lauryl (meth) acrylate; such as (meth) acrylamide, diacetone acrylamide, N-hydroxyl Various nitrogenous substances such as methacrylamide or (meth)acrylonitrile Vinyl monomer. Further, the polymerizable monomer as shown below can be copolymerized by using these in combination. That is, various styrene derivatives such as styrene, α-methylstyrene, divinylbenzene, and vinyltoluene; various vinyl esters such as vinyl acetate and vinyl propionate; Various fluorene-containing polymerizable monomers such as γ-methyl propylene methoxy propyl trimethoxy decane, vinyl trimethoxy decane, methacryl fluorenyl fluorene macromonomer; Monomers; such as vinyl chloride, vinyl chloride, fluorinated vinyl, vinylidene fluoride, chlorotrifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, various halogenated vinyls; Such as various conjugated dienes of butadiene.

In the acrylonitrile-based resin, the glass transition temperature (hereinafter abbreviated as Tg) is usually 40 ° C or higher, preferably 60 ° C or higher. When the Tg is less than 40 ° C, in the case where the coating thickness of the coating layer is thick for the purpose of improving the adhesion, there is a problem that it is easy to seal the end.

The term "polyurethane resin" as used in the present invention means a polymer compound having a urethane bond in a molecule. Among them, in view of suitability for in-line coating, a water-dispersible or water-soluble urethane resin is preferred. In order to impart water dispersibility or water solubility, a hydrophilic group such as a hydroxyl group, a carboxyl group, a sulfonic acid group, a sulfonyl group, a phosphoric acid group or an ether group may be introduced into the urethane resin. Among the above hydrophilic groups, a carboxylic acid group or a sulfonic acid group is preferably used from the viewpoint of improving the physical properties and adhesion of the coating film.

Specific examples of the production of the urethane resin include a method of using a reaction between a hydroxyl group and an isocyanate. In terms of the hydroxyl group used as the raw material, a polyol is preferably used, and for example, a polyether polyol, Polyester polyols, polycarbonate polyols, polyolefin polyols, and acryl-based polyols. These compounds may be used singly or in plural.

Examples of the polyether polyols include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene ether glycol, and polyhexamethylene ether glycol.

Examples of the polyester polyols include polycarboxylic acids (malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, and para-benzoic acid). Dicarboxylic acid, isophthalic acid, etc.) or the anhydrides and polyols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, 1,3-butyl) Alkanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1 ,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-methyl-2-propyl-1,3- Propanediol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5- Dimethyl-2,5-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3- Propane diol, 2-butyl-2-hexyl-1,3-propane diol, cyclohexane diol, bishydroxymethylcyclohexane, dimethanol benzene, bishydroxyethoxybenzene, alkyl dioxane The reaction of the reaction of an alcohol amine, a lactone diol, etc.).

Examples of the polycarbonate-based polyols include polycarbonate diols obtained by dealcoholization reaction of polyols with dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and ethylene carbonate. For example, poly(1,6-hexene) carbonate, poly(3-methyl-1,5-pentene) carbonate, etc. are mentioned.

Examples of the polyisocyanate compound used for obtaining the urethane resin include trichloroethylene diisocyanate, dimethylphenylene diisocyanate, methylene diphenyl diisocyanate, phenyl diisocyanate, and naphthalene diisocyanate. An aromatic diisocyanate such as tolidine diisocyanate or an aromatic diisocyanate having an aromatic ring such as α,α,α′,α′-tetramethyldimethylphenylene diisocyanate; methylene diisocyanate; Aliphatic diisocyanate such as propylene diisocyanate, leucine diisocyanate, trimethylhexamethylene diisocyanate or hexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophor An alicyclic diisocyanate such as keto diisocyanate, dicyclohexylmethane diisocyanate or isopropylidene dicyclohexyl diisocyanate. These may be used alone or in combination.

In the case of synthesizing a urethane resin, it is preferable to use a conventionally known chain extender, and a chain extender is not particularly limited as long as it has two or more active groups reactive with an isocyanate group, and can be used in general. A chain extender having two hydroxyl groups or an amine group is used.

The chain extender having two hydroxyl groups may, for example, be an aromatic diol such as ethylene glycol, propylene glycol or butanediol, or an aromatic group such as dimethyl phenyl diol or bishydroxy ethoxy benzene. Glycols such as diols, neopentyl glycol hydroxytrimethyl acetate, and the like are called ester diols. Further, examples of the chain extender having two amine groups include aromatic diamines such as trichloroethylene diamine, dimethyl phenyl diamine, and diphenylmethane diamine, ethylene diamine, and propylene diamine. Hexanediamine, 2,2-dimethyl-1,3-propanediamine, 2-methyl-1,5-pentanediamine, trimethylhexanediamine, 2-butyl-2 -ethyl-1,5-pentane II Aliphatic diamine, 1-amino-3-aminomethyl-3,5, such as amine, 1,8-octanediamine, 1,9-decanediamine, 1,10-decanediamine , 5-trimethylcyclohexane, dicyclohexylmethanediamine, isopropylcyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, 1,3-diamino An alicyclic diamine such as methylcyclohexane.

The blending ratio of the binder polymer (B) in the coating layer is in the range of 10 to 90%, more preferably 20 to 80%. When the range is less than 10%, the adhesion to the release layer may be lowered. Further, when it exceeds 80%, the performance is saturated, and even if there is an increase of the value or more, there is a case where a remarkable effect cannot be obtained.

In the present invention, in the coating layer constituting the release film, it is preferred to contain a polyurethane resin for the purpose of improving the adhesion to the release layer.

The coating liquid for coating layer of the present invention is provided, and the component (C) contains an alkylene oxide derived from glycerol (C1), polyglycerol (C2), p-glycerol or polyglycerol. It is preferred that one or more compounds selected from the group of the adducts (C3) or derivatives thereof are preferred. The average number of glycerol units in the molecule is preferably in the range of 2 to 20. Incidentally, when glycerin is used, the transparency of the coating layer may be slightly inferior.

Further, the alkylene oxide adduct of glycerol or polyglycerol has a structure in which a polymerized alkylene oxide or a derivative thereof is added to a hydroxyl group of glycerol or polyglycerol.

Here, the structure of the alkylene oxide or its derivative to be added on each of the hydroxyl groups of the glycerol or polyglycerol skeleton may be different. Moreover, at least one of the hydroxyl groups in the molecule is added, and does not need to be all An alkylene oxide or a derivative thereof is added to the hydroxyl group of the moiety.

In the case of an alkylene oxide or a derivative thereof, a structure containing an ethylene oxide or propylene oxide skeleton is preferred. When the alkyl chain in the alkylene oxide structure is too long, the hydrophobicity is enhanced, the uniform dispersibility in the coating liquid is deteriorated, and the antistatic property or transparency of the coating film tends to be deteriorated. Particularly preferred is ethylene oxide.

In the alkylene oxide adduct of the glycerol or polyglycerol, the copolymerization ratio of the alkylene oxide or its derivative to the glycerol or polyglycerol skeleton is not particularly limited, and the molecular weight ratio is When the triol or polyglycerol moiety is 1, the alkylene oxide moiety is preferably 20 or less, more preferably 10 or less. When the ratio of the alkylene oxide or the derivative thereof to the glycerin or polyglycerol skeleton is larger than this range, the properties at the time of using the polyalkylene oxide are usually close to each other, and the effect of the present invention may not be sufficiently obtained.

Regarding the compound (C) in the present invention, particularly preferred aspects of the aspect include polyglycerol (C2) and an alkylene oxide adduct (C3) of glycerol or polyglycerol. In the case of polyglycerol (C2), it is particularly preferable that n in the compound of the above formula (3) is 2 to 20. Further, in the case of the alkylene oxide adduct (C3) of glycerol or polyglycerol, the compound of the above formula (3) is particularly preferably a structure in which ethylene oxide and polyethylene oxide are added at n=2. Further, the number of additions is particularly preferably in the range of 300 to 2,000 as the weight average molecular weight of the final compound (C3).

The blending ratio of the component (C) in the coating layer is in the range of 10 to 90%, more preferably 20 to 80%. When the range is less than 10%, the coating property may be lowered. In addition, when it exceeds 90%, There is a case where the durability of the coating layer is insufficient.

In the coating layer constituting the release film, the weight of the coating agent component (A) in the coating layer is usually 0.5 mg/m ² or more, preferably 1 mg/m ² or more. When the amount of the coating agent component (A) is less than 0.5 mg/m ² , the antistatic property tends to be insufficient.

Further, in the present invention, the ratio of the coating agent component (A) to be contained in the coating layer constituting the release film is not limited, and the upper limit is preferably 90% by weight, more preferably 80% by weight, and most preferably It is 60%. When the ratio of the coating agent component (A) exceeds 90% by weight, the transparency of the coating film may be insufficient or the antistatic property may be insufficient. Further, the lower limit is preferably 1%, more preferably 2%. When the weight ratio of the coating agent component (A) is less than 1%, the antistatic property may be insufficient.

In the coating layer constituting the release film of the present invention, the ratio of the coating agent component (A) to the coating agent component (B) is preferably in the range of 90/10 to 1/99 by weight. More preferably, it is 70/30~1/99, and the best is 50/50~2/98. If it is not in this range, the antistatic property or the appearance of the coating film tends to be deteriorated. The coating liquid used in the present invention may contain a surfactant in order to improve the coatability to the polyester film. In terms of the surfactant, especially in the case where (poly)alkylene oxide or (poly)glycerol or a derivative thereof is used in the structure, the anti-charge property of the obtained coating layer is not hindered. good.

The coating liquid used in the present invention may further contain an antifoaming agent, a coating improver, a tackifier, an organic lubricant, a release agent, organic particles, inorganic particles, an antioxidant, an ultraviolet absorber, and a foaming agent. ,dye Additives such as materials and pigments. These additives may be used singly or in combination of two or more kinds as needed. Further, in the case of such an additive, if (poly)alkylene oxide or (poly)glycerol or a derivative thereof is used in the structure, it is preferred that the anti-charge property of the obtained coating layer is not inhibited. .

The coating liquid in the present invention is preferably used as an aqueous solution or an aqueous dispersion from the viewpoints of handling, work environment, and stability of the coating liquid composition, but is used as a water-based medium. An organic solvent may also be contained if it does not go beyond the gist of the present invention.

The coating layer in the present invention is preferably provided by coating a coating liquid containing a specific compound on a film, particularly in the present invention, by in-line coating by coating in a film forming film. The setting is good.

Next, the formation of the release layer in the present invention will be described.

The release layer constituting the first release film and the second release film in the present invention means a layer having a release property, specifically, a peeling force of the adhesive layer and the release layer is within a certain range The inventors were able to complete.

The first release film 31 needs to have a low-speed peeling force of 10 to 20 mN/cm at 0.3 m/min. When the peeling force of the first release film is less than 10 mN/cm, the release film is likely to be peeled off in the case where it is not necessary to peel off. Further, when the peeling force of the first release film exceeds 20 mN/cm, it is difficult to smoothly peel off when the first release film is peeled off.

Furthermore, in the present invention, it is necessary to peel off 60 m/min. The force is suppressed to 90 mN/cm or less, preferably 85 mN/cm or less. When the high-speed peeling force exceeds 90 mN/cm, it is difficult to peel off smoothly.

The present inventors, for example, generally, in a state before being attached to an electronic component, immediately when the first release film is peeled off from the adhesive sheet on both sides of the substrate, the small size of the electronic component can be cut in advance. It is in the form of flakes, and then the worker peels off by hand. In the peeling operation step, the cut piece was used, and the first release film was peeled off at a time, and then peeled off 180 degrees in the diagonal direction of the small piece.

In this case, unlike the case where the release film is peeled off at 180 degrees from a general self-adhesive tape, in order to peel off the release film in the diagonal direction, the peeling area tends to increase slowly as the peeling progresses. . The present inventors have focused on the peeling method and the phenomenon in which the peeling area is increased at a certain peeling speed, and the phenomenon of peeling off a larger area at the same time, that is, a peeling method in which the so-called peeling speed is faster. As in the present invention, in particular, when a soft adhesive layer in which the step difference absorbability is considered is used, it has been found that the high-speed peeling force of 60 m/min can be effectively suppressed to a certain peeling force, and the present invention has been completed.

Further, the peeling force of the second release film at 0.3 m/min is preferably 20 to 100 mN/cm, more preferably 40 to 80 mN/cm. When the peeling force of the second release film is less than 20 mN/cm, when the first release film is peeled off from the adhesive sheet on both sides without the substrate, a problem such as partial peeling of the second release film may occur. In addition, when the peeling force of the second release film exceeds 100 mN/cm, the second release film may have a problem such as a residue from the adhesive layer.

In the substrate-free double-sided adhesive sheet of the present invention, in addition to the adjustment of the peeling force, a peeling force difference between the first release film and the second release film is provided.

The peeling force of the second release film is usually 2.0 times or more, preferably 3.0 times or more, of the peeling force of the first release film. When the peeling force of the second release film is less than 2.0 times the peeling force of the first release film, when the first release film on the light release side is peeled off, the second release film floats from the adhesive layer. The phenomenon occurs, or a problem occurs in the second release film in which an adhesive layer component remains or zipping occurs.

The release layer constituting the release film of the present invention preferably contains a hardening type polyfluorene resin in order to improve the release property. It may be in the form of a hardened polyoxymethylene resin as a main component, and may be used by an organic resin such as a urethane resin, an epoxy resin or an alkyd resin, in the scope of the present invention without departing from the gist of the present invention. A modified polyfluorene form or the like formed by graft polymerization or the like.

In the present invention, it is necessary for the release film having a small peeling force to have a release layer which is based on a polyester film and which contains a reactive polyoxyl resin having an alkenyl group and an alkyl group as a functional group, and an average mass. A release layer of an unreacted polyanthracene resin having a molecular weight of 400,000 or more and a platinum-based catalyst.

Examples of the polyfluorene oxide resin having an alkenyl group and an alkyl group as a functional group used in the present invention include the following. First, an alkenyl group-containing hardening polyoxyl resin, in terms of diorganopolyoxyalkylene, may be cited Trimethyl methoxy group at both ends of the sub-chain blocks dimethyl oxane ‧ methyl hexenyl decane copolymer (dimethyl methoxy oxane unit 96 mol %, methyl hexenyl decane unit) 4 mol%), both ends of the molecular chain dimethylvinyl methoxy group blocked dimethyl oxa oxide ‧ methyl hexenyl decane copolymer (dimethyl methoxy oxane unit 97 mol%, A Hexenylalkenoxane unit 3 mole %), dimethyl hexenyl oxime oxy group at the two ends of the molecular chain, dimethyl oxane ‧ methyl hexenyl decane copolymer (dimethyl hydrazine) Oxysilane unit 95 mol%, methylhexenyl decane unit 5 mol%). Next, the alkyl-containing hardening polyfluorene oxide, in terms of the organohydrogen polyoxyalkylene, may be exemplified by a trimethyl methoxy group at both ends of the molecular chain, a methyl hydrogen polyoxyalkylene group, and a trimethyl group at both ends of the molecular chain. Oxyloxy blockade dimethyl methoxy oxane ‧ methylhydroquinone copolymer, molecular chain two-terminal dimethyl hydroquinone block methyl hydrogen polyoxyalkylene, molecular chain both ends dimethyl hydroquinone The base is blocked with a dimethyloxane ‧ methylhydroquinoxane copolymer.

In the present invention, in order to impart light peeling property without deteriorating the transition property, it is necessary to add an unreactive polyxanthene resin having a mass average molecular weight of 400,000 or more.

The above-mentioned unreacted polyoxyphthalocene resin is preferably an organopolyoxane represented by the following general formula (I).

R ³ SiO(R ² SiO) _m SiR ³ (I) (In the above formula, R is a monovalent hydrocarbon group of the same or different kind which does not have an aliphatic unsaturated bond, and m represents a positive integer).

Unreacted in the polyoxynoxy resin used in the present invention The polyoxyalkylene resin is in the range of 1 to 10% by weight, preferably 1 to 5% by weight. When the content of the unreacted polyoxyl resin is less than 1%, the speed dependency is high, and when it exceeds 5% by weight, the hardenability is remarkably lowered, and the adhesion is also deteriorated.

In the present invention, in order to reduce the peeling force in the high speed region, polyfluorene oxide oil may be added. The polyoxygenated oil is a polyoxygenated oil called a straight-run polyoxyxene oil or a modified polyoxygenated oil, and the following may be mentioned. Examples of the straight-run polyfluorinated oxygen include dimethylpolyphthalide oil, methylphenylpolyphosphonium oil, and methylhydrogenpolyoxygenated oil. Further, examples of the modified polyoxyxene oil include a polyether modification in a side chain type, an aralkyl modification, a fluoroalkyl modification, a long-chain alkyl modification, a higher fatty acid ester modification, and an advanced Fatty acid decylamine modification, polyether ‧ long-chain alkyl modification ‧ aralkyl modification, phenyl modification, two-terminal polyether modification, polyether ‧ methoxy modification, etc.

The polyoxyxylene oil component contained in the polyoxyxylene resin used in the present invention is usually in the range of 1 to 10% by weight, preferably 1 to 5% by weight. When the content of the polyoxygenated oil component is less than 1%, the speed dependency becomes high, and if it exceeds 5% by weight, the transition property is high, and the roller is smeared or migrated to the adhesive surface during the processing of the adhesive to cause adhesion. The peeling force is lowered, and the like.

In the present invention, the residual adhesion ratio of No. 31B tape manufactured by Nitto Denko Corporation is preferably 85% or more, more preferably 90% or more. If the residual adhesion ratio is lower than 80%, the migration property is high, and the roller is smeared or moved to the adhesive surface during the processing of the adhesive, and the adhesive peeling force is lowered.

For the type of hardened polyoxyl resin, the addition can be used. Type ‧ Condensation type ‧ UV curing type ‧ Electron line hardening type ‧ Solvent-free type, etc. For the specific examples, KS-774, KS-775, KS-778, KS-779H, KS-847H, KS-856, X-62-2422, and X-62-2461 can be exemplified by Shin-Etsu Chemical Co., Ltd. , X-62-1387, X-62-5039, X-62-5040, KNS-3051, X-62-1496, KNS320A, KNS316, X-62-1574A/B, X-62-7052, X-62 -7028A/B, X-62-7619, X-62-7213, YSR-3022, TPR-6700, TPR-6720, TPR-6721, TPR6500, TPR6501, UV9300, UV9425, XS56-A2775, XS56, manufactured by Momentive Performance Materials -A2982, XS56-C6010, XS56-C4880, UV9430, TPR6600, TPR6604, TPR6605, Dow Corning Toray SRX357, SRX211, SD7220, SD7292, LTC750A, LTC760A, LTC303E, LTC300B, LTC856, SP7259, BY24-468C, SP7248S, BY24-452, DKQ3-202, DKQ3-203, DKQ3-204, DKQ3-205, DKQ3-210, etc. Further, in order to adjust the peeling property of the release layer or the like, a release controlling agent may be used in combination.

In the present invention, the curing conditions for forming the release layer on the polyester film are not particularly limited, and when the release layer is provided by off-line coating, it is usually 120 to 200 ° C for 3 to 40 seconds. It is preferably 100 to 180 ° C and 3 to 40 seconds as a basis for heat treatment. Further, if necessary, it is also possible to use an active energy ray such as heat treatment or ultraviolet irradiation. Further, a conventionally known device or energy source can be used for the energy source which is hardened by irradiation with an active energy ray.

The coating amount of the release layer (after drying) is usually 0.005 to 1 g/m ² , preferably 0.005 to 0.5 g/m ² , more preferably 0.01 to 0.2 g/m from the viewpoint of coatability. ² range. When the coating amount (after drying) is less than 0.005 g/m ² , the coating property is insufficient in stability, and it may be difficult to obtain a uniform coating film. Further, when the coating is over 1 g/m ² thick, the coating film adhesion property and the curability of the release layer itself may be lowered.

In the composition of the two-sided adhesive sheet having no substrate in the present invention, it is necessary to apply a release film to both sides of the adhesive layer. Regarding the thickness ratio of each of the release films, the thickness of the second release film is preferably twice or more, more preferably three times or more, the thickness of the first release film in consideration of workability. For example, by thinning the film thickness of the first release film, when the first release film is peeled off, there is an advantage that floating of the second release film and the adhesive interface can be prevented. Further, when the adhesive layer is applied to the release surface of the second release film, in order to eliminate the influence of foreign matter or unevenness on the step, the second separation is easily affected by the unevenness or foreign matter in consideration of the production cost. It is preferred that the film thickness of the film is increased. When the thickness of the second release film is less than twice the thickness of the first release film, the difference in elasticity of the film substrate disappears, and when the first release film is peeled off from the adhesive sheet on both sides without the substrate, A case where a part of the second release film is peeled off or the like occurs.

In the first release film and the second release film of the present invention, an adhesive layer, an antistatic layer, and an oligomer can be provided on the film surface on which the release layer is not provided, without departing from the gist of the present invention. A coating layer such as a precipitation preventing layer is deposited.

In the polyester film of the present invention, in order to make the release layer of the release film of light peeling force beautiful and strong, platinum which promotes the reaction of addition molding is used. Catalyst. The present invention may, for example, be a platinum-based compound such as a platinum chloride acid, an alcohol solution of a platinum chloride acid, a complex of a platinum chloride acid and an olefin, a complex of a platinum chloride acid and an alkenyl alkane. , platinum black, ruthenium oxide holding platinum, active carbon holding platinum. The content of the platinum-based catalyst in the release layer is usually in the range of 0.3 to 3.0% by weight, preferably 0.5 to 2.0% by weight. When the content of the platinum-based catalyst in the release layer is lower than 0.3% by weight, the peeling force is not good, and the hardening reaction of the coating layer is insufficient, and a problem such as deterioration of the surface may occur, and the release layer may be formed. When the content of the platinum-based catalyst in the middle is more than 3.0% by weight, the cost is high, and the disadvantage of the step such as high reactivity and occurrence of colloidal foreign matter occurs.

Further, since the reaction reactivity due to addition molding is extremely high, acetylene alcohol may be added as a reaction inhibitor as the case may be. The component is an organic compound having a carbon-carbon triple bond and a hydroxyl group, preferably 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and A selected group of phenylbutynols.

Further, the polyester film constituting the first release film and the second release film may be subjected to surface treatment such as corona treatment or plasma treatment in advance.

In the present invention, when the release film is produced, after the coating layer is coated on the polyester film, the film may be rolled up at one end, and then the release layer may be provided on the coating layer, or may be coated on the polyester film. After the coating layer is dried, a release layer is continuously provided on the coating layer, and any method can be used in the present invention.

Next, the adhesive layer constituting the double-sided adhesive sheet having no substrate in the present invention will be described below. The adhesive layer in the present invention means A layer composed of an adhesive material can be used in a conventionally known material without departing from the gist of the present invention. One of the specific examples will be described below using an acrylic adhesive.

In the present invention, the acrylic adhesive means an adhesive layer containing an acrylic polymer formed of an acrylic monomer as an essential monomer (monomer) component as a base polymer. The acrylic polymer is obtained by using an alkyl (meth)acrylate having an alkyl group having a linear or branched chain and/or an alkoxyalkyl (meth)acrylate as an essential monomer component ( More preferably, it is an acrylic polymer formed as a main monomer component. Further, the acrylic polymer is an acrylic system formed by using an alkyl (meth) acrylate having an alkyl group having a linear or branched chain and an alkoxyalkyl acrylate as an essential monomer component. Polymer is good.

The adhesive layer of the present invention is an acrylic adhesive layer formed by using an alkyl (meth) acrylate having an alkyl group or a linear alkyl or alkyl acrylate as an essential monomer component. Good.

Further, in the monomer component forming the acrylic polymer as the base polymer in the adhesive layer of the present invention, a polar group-containing monomer, a polyfunctional monomer or another copolymerizable monomer may be further included as a copolymerization. Monomer component. In addition, the above-mentioned "(meth)acryloyl group" means "acryloyl group" and/or "methacryloyl group", and the others are the same. Further, the content of the acrylic polymer as the base polymer in the adhesive layer of the present invention is not particularly limited, but is preferably 60% by weight or more based on the total weight (100% by weight) of the adhesive layer. Preferably, it is 80% by weight or more.

In order to form a monomer component of the above acrylic polymer, it is preferred to use an alkyl (meth)acrylate having a linear or branched chain alkyl group (hereinafter simply referred to as "alkyl (meth)acrylate) "). Specific examples of the alkyl (meth)acrylate may, for example, be methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate or isopropyl (meth)acrylate. Base ester, butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate Base ester, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate , isooctyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, ( Undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, fifteen (meth) acrylate Alkyl ester, cetyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, pentadecyl (meth) acrylate, (a) Alkyl carbon such as decyl acrylate 1 to 20 of the (meth) acrylate and the like. Further, the alkyl (meth)acrylate may be used singly or in combination of two or more. Among them, an alkyl (meth)acrylate having an alkyl group having 2 to 14 carbon atoms is preferred, and an alkyl (meth)acrylate having an alkyl group having 2 to 10 carbon atoms is more preferred.

Examples of the above polar group-containing monomer include (meth)acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isobar. a carboxyl group-containing monomer such as stearic acid or an anhydride thereof (anhydrous maleic acid or the like); 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, or (meth)acrylic acid a hydroxyl group-containing monomer such as 4-hydroxybutyl ester or 6-hydroxyhexyl (meth)acrylate such as hydroxyalkyl (meth)acrylate, vinyl alcohol or allyl alcohol; (meth) propylene Indoleamine, N,N-dimethyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-butoxy Monomethylamine-containing monomer such as methyl (meth) acrylamide, N-hydroxyethyl acrylamide, etc.; aminoethyl (meth) acrylate, dimethylamino (meth) acrylate An amine group-containing monomer such as ethyl ester or t-butylaminoethyl (meth)acrylate; glycidyl (meth)acrylate; methyl glycidyl (meth)acrylate a monomer containing a glycidyl group; a cyano group-containing monomer such as acrylonitrile or methacrylonitrile; in addition to N-vinyl-2-pyrrolidone or (meth)propenylmorpholine, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-ethylene a heterocyclic-containing vinyl monomer such as piperazine, N-vinylpyrrole, N-vinylimidazole or N-vinyloxazole; a sulfonic acid group-containing monomer such as sodium vinylsulfonate; a phosphate group-containing monomer such as hydroxyethyl acryloyl phosphinate; a quinone-containing amino group-containing monomer such as cyclohexylmaleimide or isopropylmaleimide; 2-methylpropene oxime An isocyanate group-containing monomer or the like such as a methoxyethyl isocyanate. The above polar group-containing monomers may be used singly or in combination of two or more.

Examples of the polyfunctional monomer include hexanediol di(meth)acrylate, butanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, Polypropylene glycol di(a) Acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane Tris (meth) acrylate, tetramethylol methane tri (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, divinyl benzene, epoxy acrylate, Polyester acrylate, urethane acrylate, and the like. These polyfunctional monomers may be used singly or in combination of two or more.

The content of the polyfunctional monomer is preferably 0.5% by weight or less based on 100% by weight of the monomer component forming the acrylic polymer. When the content is more than 0.5% by weight, for example, the cohesive force of the adhesive layer may become too high, and the stress relaxation property may be lowered.

Further, examples of the copolymerizable monomer (other copolymerizable monomer) other than the polar group-containing monomer or the polyfunctional monomer include cyclopentyl (meth) acrylate and cyclohexyl (methyl). The above (meth) acrylate having an aromatic hydrocarbon group such as an alicyclic hydrocarbon group-containing (meth) acrylate or a phenyl (meth) acrylate such as an isodecyl (meth) acrylate or the like ( (meth)acrylic acid alkyl ester, (meth)acrylic acid alkoxyalkyl ester or polar group-containing monomer or polyfunctional monomer other than (meth) acrylate; vinyl acetate, propionic acid vinyl Vinyl esters such as esters; aromatic vinyl compounds such as styrene and vinyl toluene; olefins or dienes such as ethylene, butadiene, isoprene and isobutylene; and ethylene such as vinyl alkyl ether Ether ethers; vinyl chloride and the like.

The above acrylic polymer can be prepared by polymerizing the above monomer components by a conventionally known or conventional polymerization method. Propylene The polymerization method of the acid polymer may, for example, be a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, or a polymerization method (active energy ray polymerization method) by irradiation with an active energy ray. Among the above, a solution polymerization method or an active energy ray polymerization method is preferred in terms of transparency, water resistance, production cost, and the like.

The active energy ray to be irradiated during the active energy ray polymerization (photopolymerization) may, for example, be an ionizing radiation such as an α line, a β line, a γ line, a neutral line or an electron beam, or an ultraviolet ray. The use of the invention is preferred. Further, the irradiation energy of the active energy ray, the irradiation time, the irradiation method, and the like are not particularly limited as long as they do not impair the scope of the present invention.

Further, in the case of the above solution polymerization, various general solvents can be used. Specific examples thereof include esters of ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as toluene and benzene; aliphatic hydrocarbons such as n-hexane and n-heptane; and rings; An organic solvent such as an alicyclic hydrocarbon such as hexane or methylcyclohexane; or a ketone such as methyl ethyl ketone or methyl isobutyl ketone. The solvent may be used singly or in combination of two or more.

In the preparation of the above acrylic polymer, a polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator (photoinitiator) may be used depending on the type of the polymerization reaction. The polymerization initiators may be used singly or in combination of two or more.

The photopolymerization initiator is not particularly limited, and a benzoin ether photopolymerization initiator, an acetophenone photopolymerization initiator, an α-keto alcohol photopolymerization initiator, and an aromatic sulfonyl group can be used. Chloride photopolymerization Starting agent, photoactive oxime photopolymerization initiator, benzoin photopolymerization initiator, benzyl photopolymerization initiator, benzophenone photopolymerization initiator, ketal photopolymerization initiator, A thioxanthone photopolymerization initiator or the like. The amount of use of the photopolymerization initiator is not particularly limited as long as it does not impair the scope of the present invention. For example, it is 0.01 to 0.2 by weight based on 100 parts by weight of the total monomer component of the acrylic polymer. The range is best.

Specific examples of the benzoin ether photopolymerization initiator include, for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy Base-1,2-diphenylethane-1-one, methylphenyl ether methyl ether, and the like. Examples of the acetophenone-based photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 1-hydroxycyclohexylphenyl. Ketone, 4-phenoxydichloroacetophenone, 4-(t-butyl)dichloroacetophenone, and the like. The α-keto alcohol-based photopolymerization initiator may, for example, be 2-methyl-2-hydroxypropiophenone or 1-[4-(2-hydroxyethyl)phenyl]-2-methylpropane-1- Ketones, etc. Specific examples of the aromatic sulfonyl chloride-based photopolymerization initiator include 2-naphthalenesulfonyl chloride and the like. The photoactive oxime photopolymerization initiator may, for example, be 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-ruthenium or the like. The benzoin-based photopolymerization initiator may, for example, contain benzoin or the like. The benzyl photopolymerization initiator may, for example, contain a benzyl group or the like.

Specific examples of the benzophenone-based photopolymerization initiator include benzophenone, benzamidine benzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, and poly Vinyl benzophenone, α-hydroxycyclohexyl phenyl ketone Wait. Specific examples of the ketal-based photopolymerization initiator include benzyldimethylketal and the like. Specific examples of the thioxanthone photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, and isopropylthioxan Ketone, 2,4-diisopropylthioxanthone, dodecylthioxanthone, and the like.

Specific examples of the above thermal polymerization initiator are azo polymerization initiators (for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2 , 2'-azobis(2-methylpropionic acid) dimethyl, 4,4'-azobis-4-cyanoshikimic acid, azobisisopramonitrile, 2,2'-azo double (2-Methylpropanepropane) dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2' - azobis(2-methylpropionamidine) disulfate, 2,2'-azobis(N,N'-dimethylene isobutylphosphonium) dihydrochloride, etc., peroxide system A polymerization initiator (for example, benzoyl peroxide, tert-butyl permaleic acid, etc.), a redox polymerization initiator, or the like. The amount of the thermal polymerization initiator to be used is not particularly limited as long as it does not impair the scope of the present invention.

In the acrylic adhesive layer used as one form of the adhesive layer in the present invention, a crosslinking agent, a crosslinking accelerator, and an adhesion-imparting agent (for example, a rosin derivative) can be used as needed without impairing the characteristics of the present invention. Resin, polyterpene resin, petroleum resin, oil-soluble phenol resin, etc.), anti-aging agent, filler, colorant (pigment or dye, etc.), ultraviolet absorber, antioxidant, chain transfer agent, plasticizer, softener, A well-known additive such as a surfactant or an antistatic agent. Further, when an adhesive layer is formed, various general solvents can be used. The type of the solvent is not particularly limited, and examples thereof may be used as the solvent used in the solution polymerization described above. Wait.

The above crosslinking agent can control the colloid fraction of the adhesive layer by crosslinking the base polymer of the adhesive layer. In addition to the isocyanate crosslinking agent, the epoxy crosslinking agent, the melamine crosslinking agent, and the peroxide crosslinking agent, a urea crosslinking agent and a metal alkoxide crosslinking are mentioned. A crosslinking agent, a metal chelate crosslinking agent, a metal salt crosslinking agent, a carbodiimide crosslinking agent, an oxazoline crosslinking agent, an aziridine crosslinking agent, an amine crosslinking agent, etc. Preferably, an isocyanate crosslinking agent or an epoxy crosslinking agent can be used. The crosslinking agent may be used singly or in combination of two or more.

In the double-sided adhesive sheet having no substrate in the present invention, when an acrylic adhesive composition as the constituent unit is used in forming the adhesive layer, for example, it will be present in an optical member (for example, a surface protective layer or a touch panel). And the gap between the display surface of the image display unit and the like, which is replaced by a transparent adhesive sheet having a refractive index close to that of the optical member after being compared with the air, thereby improving the light transmittance, considering the brightness of the image display device or suppressing the contrast reduction. Next, it is better to design the adhesive layer itself to be soft.

The thickness of the adhesive layer (after drying) constituting the double-sided adhesive sheet having no substrate in the present invention is usually in the range of 25 μm to 200 μm, preferably 50 μm to 100 μm. When the thickness of the adhesive layer is less than 25 μm, for example, voids generated between the optical members may become excessively large, and it may be difficult to fill each corner with an adhesive layer. Further, when the thickness of the adhesive layer exceeds 200 μm, the thickness of the adhesive layer becomes too thick as compared with the void generated between the optical members, and there are cases where excessive adhesion of the adhesive layer component occurs between the optical members.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, which are not intended to be limited thereto. Further, the measurement method and evaluation method used in the present invention are as follows.

(1) Determination of average particle diameter (d50: μm):

A value of 50% of the total value (weight basis) in the equivalent spherical distribution measured by a centrifugal sedimentation type particle size distribution measuring apparatus (Model SA-CP3 manufactured by Shimadzu Corporation) was used as the average particle diameter.

(2) Peeling force of release film (I):

A single-sided adhesive tape ("No. 31B" manufactured by Nitto Denko Corporation) was attached to the surface of the release layer of the sample film, and then cut into a size of 50 mm × 300 mm, and then the peeling force after standing at room temperature for 1 hour was measured. The peeling force was 180° peeling at a tensile speed of 300 mm/min and 30,000 mm/min using a tensile tester ("INTESCO Model 2001" manufactured by INTESCO).

(3) Migration of the release film instead of evaluation (residual adhesion rate):

The sample film was cut into A4, and the adhesive tape (Nitto Denko Co., Ltd. "No. 31B" substrate thickness: 25 μm) was bonded to the measurement surface of the film using a rubber roller. After one hour, the adhesive tape was peeled off. Will Adhesive tape is attached to a stainless steel plate with a cleaned surface using a rubber roller. The adhesive tape was fixed on the upper side, and the stainless steel plate was fixed on the lower portion, peeled off at a speed of 300 mm/min in the 180° direction, and the adhesion force (1) was measured.

The adhesion force (2) was measured by the same procedure as above using an adhesive tape (Nitto Denko Co., Ltd. "No. 31B") which was not bonded to the sample. The residual adhesion ratio was determined by the following formula.

Residual adhesion rate (%) = subsequent force (1) ÷ adhesion force (2) × 100

(4) Release characteristics (practical replacement evaluation):

The acrylic pressure-sensitive adhesive composition having the following composition was applied onto the release film, and then heat-treated at 100 ° C for 5 minutes to obtain an adhesive layer having a thickness (after drying) of 20 μm. Then, the release film and the adhesive layer were heat-treated at 150 ° C for 90 minutes, and then the release film was peeled off, and the release property was evaluated from the state when the release film was peeled off from the adhesive layer.

A: The release film was perfectly peeled off, and no adhesion of the adhesive to the release layer was observed.

B: Although the release film can be peeled off, the adhesive adheres to the release layer when peeled off at a relatively high speed.

C: The adhesive adheres to the release film and cannot be peeled off perfectly.

(5) The amount of oligomer (OL) of the polyester extracted from the surface of the release layer of the release film:

The unheated release film was previously heated in air at 180 ° C for 10 minutes. Then, as far as possible, the heat-treated film was adhered to the inner surface of the box having a length of 10 cm and a height of 3 cm which was opened at the upper portion to have a box shape. When the coating layer is provided, the coating layer is made to be inside. Next, 4 ml of DMF (dimethylformamide) was added to the box prepared by the above method for 3 minutes, and then DMF was recovered. The recovered DMF was supplied to liquid chromatography (manufactured by Shimadzu Corporation: LC-7A), and the amount of oligomer in DMF was determined. This value was divided by the area of the film in which DMF was contacted, and the amount of the surface oligomer was (mg/m). ² ).

The amount of oligomer in DMF is determined by the ratio of the peak area of the standard sample to the peak area of the peak area of the sample (absolute gauge method). The preparation of the standard sample is carried out by accurately weighing the pre-separated oligomer (cyclic triad) and dissolving it in a properly weighed DMF. The concentration of the standard sample is preferably in the range of 0.001 to 0.01 mg/ml.

Further, the conditions of liquid chromatography are as follows.

Mobile phase A: acetonitrile

Mobile phase B: 2% aqueous acetic acid solution

Pipe column: MCI GEL ODS 1HU by Mitsubishi Chemical Corporation

Column temperature: 40 ° C

Flow rate: 1ml/min

Detection wavelength: 254nm

Then, the peeling condition is determined by the following criterion.

Judgment Benchmark

A: The amount of surface oligomer (OL) is 2.0 mg/m ² or less (the degree of practical use is not problematic)

B: The amount of surface oligomer (OL) exceeds 2.0 mg/m ² (the degree of practical problem)

(6) The amount of elements from the release side of the release film:

In the FD (Fundamental Parameter Method) method, the surface of the release layer provided with the sample sample is used in advance by the fluorescent X-ray measuring device (the product "Shimadzu Manufacturing Co., Ltd." "XRF-1500"). The amount of the elements was measured under the measurement conditions shown in Table 1.

(7) Initial evaluation of coating film adhesion of release film (applicability evaluation of practical characteristics):

Immediately after coating, the release surface of the sample film was wiped by a tentacle for 5 times, and the degree of detachment of the release layer was determined according to the following criteria.

Judgment Benchmark

A: No peeling of the coating film (a practical degree)

B: The coating film turns white but does not fall off (the degree of practicality)

C: The peeling of the coating film can be confirmed (the degree of difficulty in practical use)

(8) Evaluation of the adhesion of the coating film of the release film after the test (applicability evaluation of practical characteristics):

The sample film was placed in a constant temperature and humidity chamber, and placed in an atmosphere of 80 ° C and 90% RH for one week, and then the sample film was taken out. Then, the release surface of the sample film was wiped 100 times with a degreased cotton dyed with MEK (methyl ethyl ketone), and then wiped 5 times with a tentacle to determine the degree of detachment of the release layer according to the following criteria.

Judgment Benchmark

A: The coating film does not fall off at all, and there is no difference in the peeling force between the wiped portion and the unwiped portion (a practical degree)

B: The coating film is not peeled off, and the peeling force is slightly heavier than the unwiped portion (a practical degree)

C: Although the coating film turns white but does not fall off, the peeling force is slightly heavier than the unwiped portion (a practical degree)

D: The peeling of the coating film can be confirmed (the degree of difficulty in practical use)

(9) Foreign object inspection:

Observing the two sides of the optical substrate without the substrate provided with the release film on both sides A sheet is used to evaluate the checkability of foreign matter.

A: There is no surface oligomer, and the inspection property is good.

B: Although the surface oligomer was detected, it did not inhibit the degree of inspectability.

C: A large number of surface oligomers were detected and could not be checked smoothly.

(10) Intrinsic viscosity of polyester (dl/g):

The fine scale removes 1 g of the non-compatible other polymer component and the polyester of the pigment in the polyester, and dissolves it by adding 100 ml of a mixed solvent of phenol/tetrachloroethane = 50/50 (weight ratio) at 30 ° C. Determined below.

(11) Glass transition temperature (Tg) of polyester resin:

Using a DSC-II type measuring apparatus manufactured by PerkinElmer Co., Ltd., a sample weight of 10 mg was heated at a temperature increase rate of 10 ° C /min under a nitrogen gas flow so that the base deflection starting temperature was Tg.

(12) Peeling force of release film (II):

Adhesive tape ("No. 31B" manufactured by Nitto Denko Corporation) was attached to the surface of the release layer of the sample film, and then cut into a size of 50 mm × 300 mm, and the peeling force after standing at room temperature for 1 hour was measured. For the peeling force, a high-speed peeling tester (TESTER SANGYO high-speed peeling tester "TE-702 type") was used to fix the release film of the sample film so as to adhere to the opponent No. .31B Adhesive tape is peeled off, and stripped at 180° peeling speed of 0.3m/min and 60m/min. from.

(13) Coating film adhesion of release film (applicability evaluation of practical characteristics):

The sample film was placed in a constant temperature and humidity chamber, and allowed to stand in an atmosphere of 60 ° C and 80% RH for 4 weeks, and then the sample film was taken out. Then, the release surface of the sample film was wiped five times by a tentacle, and the degree of detachment of the release layer was determined according to the following criteria.

Judgment Benchmark

A: No peeling of the coating film (a practical degree)

B: Although the coating film turns white but does not fall off (the degree of practicality)

C: The peeling of the coating film can be confirmed (the degree of difficulty in practical use)

(14) Evaluation of peelability of the first release film and the second release film: (utility feature substitution evaluation)

When the first release film was peeled off, the state of the interface between the second release layer and the adhesive layer was evaluated by the following criteria.

Judgment Benchmark

A: No abnormality was observed at the interface between the second release layer and the adhesive layer (the extent of practical use).

B: At the interface between the second release layer and the adhesive layer, the floating is slightly seen (the extent of the problem in practical use).

C: at the interface between the second release layer and the adhesive layer, a clear floating can be seen (The extent of practical problems).

(15) Migration evaluation:

In the production of the double-sided adhesive sheet without the substrate, it was confirmed whether or not the roller was soiled, and the sensory evaluation was performed by the following criteria.

Judgment Benchmark

A: The roller is not dirty (the extent of practical use).

B: The roller is slightly dirty only due to the migration component (a practical degree of problem).

C: The roller is soiled by the moving component, causing transfer dirt (a practical problem).

(16) Surface specific resistance (R) of release film:

The surface specific resistance in the surface of the release layer of the sample film was measured based on the method (6-1) below. In the method of (6-1), since the surface specific resistance higher than 1 × 10 ⁸ Ω cannot be measured, the method of (6-1) which cannot be measured is used (6-2).

"test methods"

(6-1) Low resistivity meter manufactured by Mitsubishi Chemical Corporation: The surface specific resistance value was measured by measuring the atmosphere at 23 ° C and 50% RH using a Loresta-GP MCP-T600 for 30 minutes.

(6-2) High-resistance measuring device made by Hewlett-Packard Company, Japan: use HP4339B and measuring electrode: HP16008B, the sample was conditioned for 30 minutes at 23 ° C, 50% RH, and the surface specific resistance value was measured.

Judgment Benchmark

A: R (Ω) is 1 × 10 ⁸ or less (a practical degree, in particular, good)

B: R (Ω) is 1 × 10 ⁹ or less (a practical degree)

C: R (Ω) is 1 × 10 ¹⁰ or less (the degree of practical problems)

D: R (Ω) exceeds 1 × 10 ¹⁰ (the degree of difficulty is practical)

The polyesters used in the examples and comparative examples were prepared in the following manner.

<Manufacture of polyester> ‧Polyester (1)

100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol were used as starting materials, and 0.09 parts by weight of magnesium acetate ‧ tetrahydrate as a catalyst was placed in a reactor to set a reaction initiation temperature of 150. At ° C, the reaction temperature was slowly raised while distilling off methanol, and it was 230 ° C after 3 hours. The transesterification reaction was substantially completed after 4 hours. After 0.04 parts of the acid ethyl phosphate was added to the reaction mixture, 0.06 parts of cerium oxide particles and 0.04 parts of cerium oxide dispersed in ethylene glycol having an average particle diameter of 1.6 μm were added, and a polycondensation reaction was carried out for 4 hours. That is, the temperature was slowly raised from 230 ° C to 280 ° C. In addition, the pressure system is slowly reduced from normal pressure, and finally is 0.3 mmHg. After the reaction started, stop at the time of 4 hours. The polymer should be spit out under nitrogen pressure. The resulting polyester (1) had an ultimate viscosity of 0.53.

Example 1-1: <Manufacture of polyester film>

The polyester (1) is supplied as a raw material to an extruder equipped with a vent hole, and is melt-extruded at 290 ° C, and then cooled and solidified on a cooling roll having a surface temperature of 40 ° C by an external electrostatic chucking method. An amorphous film having a thickness of about 550 μm was obtained. This film was stretched 3.7 times in the longitudinal direction at 85 ° C, and extended 3.9 times in the width direction at 100 ° C, and heat-treated at 210 ° C to obtain a biaxially stretched polyester film having a thickness of 38 μm.

The obtained polyester film was coated by a reverse gravure coating method to form a release agent composition -A shown below by a coating amount (after drying) of 0.12 g/m ² . A release agent was obtained, and a roll-shaped release polyester film was obtained under the conditions of a dryer temperature of 150 ° C and a linear velocity of 30 m / min.

<release agent compound>

‧ a1: a hardened polyoxyxylene resin of the above general formula (I) having a ratio of methyl group to hexenyl group to phenyl group of 100:1:0.1 (molecular weight: 200,000)

‧ a2: a hardened polyxanthene resin of the above general formula (II) having a methyl to vinyl ratio of 100:0.2 (molecular weight: 200,000)

‧a3: the general formula of the ratio of methyl group to hydrogenated decyl group of 100:1.5 (III) hardened polyoxynoxy resin (molecular weight 200000)

‧ a4: a hardened polyxanthene resin of the above general formula (III) having a ratio of methyl group to hydrogenated decyl group of 100:0.4 (molecular weight: 200000)

‧b1: Unreacted polyoxyxylene resin of the above general formula (IV) (molecular weight: 80000)

‧c1: Addition of platinum catalyst (PL-50T: Shin-Etsu Chemical Co., Ltd.)

<release agent composition-A>

Hardened polyoxyl resin a1 20 parts

Unreacted polyoxyl resin b1 0.2 parts

Addition of platinum catalyst c1 0.2 parts

MEK/toluene mixed solvent (mixing ratio is 1:1)

Examples 1-2 to 1-5 and Comparative Examples 1-1 to 1-7:

In the same manner as in Example 1, except that the composition of the release agent was changed to the composition of the coating agent shown in Table 2 below, a release film was obtained. The results obtained by the finishing are shown in Table 3 below.

Example 2-1:

The same procedure as in Example 1-1 was carried out to obtain a biaxially stretched polyester film having a thickness of 38 μm.

Next, the following coating agent was applied by reverse gravure coating so that the coating amount (after drying) was 0.05 g/m ² , and then heat treatment was performed at 120 ° C for 30 seconds. The compound constituting the coating layer is, for example, the following.

(Compound example)

‧ Organic compounds with aluminum: (A1)

Aluminum ginseng (acetic acid ethyl acetate)

‧ Organic compounds with tin: (A2)

Dioctyldiethoxytin oxide

‧Organic compound: (B1)

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane

<Coating agent composition>

Organic compound with aluminum element (A1): 33% by weight

Organic germanium compound (B1): 67% by weight

The coating agent was diluted with a toluene/MEK mixed solvent (mixing ratio of 1:4) to be 4% by weight.

Then, the coating layer was applied by a reverse gravure coating method so that the coating amount (after drying) was 0.12 g/m ² to form a release agent composed of the release agent composition shown below. A roll-shaped release polyester film was obtained under the conditions of a dryer temperature of 150 ° C and a linear velocity of 30 m / min.

<release agent compound>

A1: a hardened polyxanthene resin of the above general formula (I) having a ratio of methyl group to hexenyl group to phenyl group of 100:1:0.1 (molecular weight: 200,000)

A2: the general formula (II) of the above ratio of methyl group to vinyl group of 100:0.2 Hardened polyoxynoxy resin (molecular weight 200000)

A3: a hardened polyxanthene resin of the above general formula (III) having a ratio of a methyl group to a hydrogenated decyl group of 100: 1.5 (molecular weight: 200,000)

A4: a hardened polyxanthene resin of the above general formula (III) having a ratio of a methyl group to a hydrazine alkyl group of 100:0.4 (molecular weight: 200,000)

B1: the unreacted polyanthracene resin of the above general formula (IV) (molecular weight: 80000)

C1: Addition of platinum catalyst (PL-50T: Shin-Etsu Chemical Co., Ltd.)

Examples 2-2 to 2-8 and Comparative Examples 2-1 to 2-9:

In the example 2-1, except that the coating agent composition was changed to the coating agent composition shown in the following Table 4, and the release agent composition was changed to the release agent composition shown in the following Table 5, In the same manner as in Example 2-1, a release film was obtained. The properties of the release films obtained in the above examples and comparative examples are shown in Table 6 below.

Example 3-1: (Manufacture of polyester film) ‧Polyester film-1 (50μm)

The polyester (1) is used as a raw material and is supplied to the vent hole. After melt-extrusion at 290 ° C, the film was cooled and solidified on a cooling roll having a surface temperature of 40 ° C by an external electrostatic adhesion method to obtain an amorphous film having a thickness of about 600 μm. This film was stretched 3.3 times in the longitudinal direction at 85 ° C, and stretched 3.6 times in the width direction at 100 ° C, and heat-treated at 210 ° C to obtain a biaxially stretched polyester film having a thickness of 50 μm.

‧Polyester film-2 (100μm)

The polyester (1) is supplied as a raw material to an extruder equipped with a vent hole, and is melt-extruded at 290 ° C, and then cooled and solidified on a cooling roll having a surface temperature of 40 ° C by an external electrostatic chucking method. Thus, an amorphous film having a thickness of about 1200 μm is obtained. This film was stretched 3.3 times in the longitudinal direction at 85 ° C, and stretched 3.6 times in the width direction at 100 ° C, and heat-treated at 210 ° C to obtain a biaxially stretched polyester film having a thickness of 100 μm.

<Manufacture of the first release film>

The release film composed of the following release agent composition A was applied to the polyester film-1 by a reverse gravure coating method so that the coating amount (after drying) became 0.1 g/m ² . After heat treatment at 150 ° C for 30 seconds, a first release film was obtained.

<release agent compound>

A1: Hardened polyoxyl resin (LTC310: Dow Corning Toray system)

A2: Hardened polyoxynoxy resin (LTC303E: Transition component content of Dow Corning Toray is 15%)

A3: Hardened polyoxyl resin (KS-847H: Shin-Etsu Chemical Co., Ltd.)

A4: Hardened polyoxyl resin (SD-7292: manufactured by Dow Corning Toray)

B1: unreactive polyxanthene resin having a mass average molecular weight of 400,000 or more

C1: Addition of platinum catalyst (SRX212: manufactured by Dow Corning Toray)

C2: Addition of platinum catalyst (PL-50T: Shin-Etsu Chemical Co., Ltd.)

<release agent composition-A>

Hardened polyoxyl resin a1 20 parts

Unreacted polyoxyl resin b1 0.2 parts

Addition of platinum catalyst c1 0.2 parts

MEK/toluene mixed solvent (mixing ratio is 1:1)

<Manufacture of second release film>

The release film composed of the following release agent composition B was applied to the polyester film-2 by a reverse gravure coating method so that the coating amount (after drying) was 0.1 g/m ² . After heat treatment at 150 ° C for 30 seconds, a second release film was obtained.

<release agent composition-B>

Hardened polyoxyl resin a3 19 parts

Hardened polyoxyl resin a4 1 part

Addition of platinum catalyst c1 0.2 parts

MEK/toluene mixed solvent (mixing ratio is 1:1)

<Manufacture of adhesive sheets on both sides without substrate>

The coating liquid composed of the following acrylic pressure-sensitive adhesive composition was applied onto the release layer of the obtained second release film, and then heat-treated at 100 ° C for 5 minutes to obtain a coating amount (after drying). 50 μm adhesive layer.

<Composition for forming an adhesive layer>

An acrylate copolymer obtained by randomly copolymerizing 75 parts by mass of 2-ethylhexyl acrylate, 20 parts by mass of vinyl acetate, and 5 parts by mass of acrylic acid (Mw=540000 Mn=67000 Mw/Mn = 8 theoretical Tg - 50 ° C) 1 kg, and 20 g of 4-phenylbenzophenone as a photopolymerization initiator was mixed to form an adhesive layer.

Next, the first release film was bonded to the exposed surface of the adhesive layer to obtain a two-sided adhesive sheet having no substrate.

Examples 3-2 to 3-4 and Comparative Examples 3-1 to 3-4:

In Example 3-1, except that the release agent composition and the thickness of the polyester film substrate were changed as shown in Tables 7 and 8 below, the other systems and examples were 3-1 was similarly manufactured, and the first release film and the second release film were obtained. Then, the two are adhered through the adhesive layer to obtain a two-sided adhesive sheet having no substrate. The characteristics of the release films obtained in the above examples and comparative examples are shown in Table 8.

Example 4-1 (Manufacture of polyester film) ‧Polyester film-1 (50μm)

The polyester (1) is supplied as a raw material to an extruder equipped with a vent hole, and is melt-extruded at 290 ° C, and then cooled and solidified on a cooling roll having a surface temperature of 40 ° C by an external electrostatic chucking method. Thus, an amorphous film having a thickness of about 600 μm is obtained. This film was stretched 3.3 times in the longitudinal direction at 85 ° C to apply a coating layer composed of the following coating agent so that the coating thickness (after drying) was 0.03 g/m ² . The film was stretched 3.6 times in the width direction at 100 ° C, and heat-treated at 210 ° C to obtain a biaxially stretched polyester film having a thickness of 50 μm.

‧Polyester film-2 (100μm)

The polyester (1) is supplied as a raw material to an extruder equipped with a vent hole, and is melt-extruded at 290 ° C, and then cooled and solidified on a cooling roll having a surface temperature of 40 ° C by an external electrostatic chucking method. Thus, an amorphous film having a thickness of about 1200 μm is obtained. This film was stretched 3.3 times in the longitudinal direction at 85 ° C to apply a coating layer composed of the following coating agent so that the coating thickness (after drying) was 0.03 g/m ² . The film was stretched 3.6 times in the width direction at 100 ° C, and heat-treated at 210 ° C to obtain a biaxially stretched polyester film having a thickness of 100 μm.

<Coating agent composition>

(A): Baytron PAG manufactured by Starck AG, which is made of polyethylene oxythiophene and polystyrene sulfonic acid

(B): Polyurethane resin

A polyester polyol obtained from 664 parts of terephthalic acid, 631 parts of isophthalic acid, 472 parts of 1,4-butanediol, and 447 parts of neopentyl glycol was obtained. Connect 321 parts of adipic acid and 268 parts of dimethylolpropionic acid were added to the obtained polyester polyol to obtain a polyester polyol having a short-chain carboxyl group. Further, 160 parts of hexamethylene diisocyanate was added to 1880 parts of the above polyester polyol to obtain a polyurethane coating resin aqueous coating material.

(C): glycerol with n=1 in the above formula (3)

A/B/C=40/40/20 (% by weight)

<Manufacture of the first release film>

A release agent composed of the following release agent composition A was applied to the polyester film-1 by a reverse gravure coating method so that the coating amount (after drying) became 0.1 g/m ² . After heat treatment at 150 ° C for 30 seconds, a first release film was obtained.

<release agent compound>

A1: Hardened polyoxyl resin (LTC310: manufactured by Dow Corning Toray)

A2: Hardened polyoxynoxy resin (LTC303E: manufactured by Dow Corning Toray, transition component content: 15%)

A3: Hardened polyoxyl resin (KS-847H: Shin-Etsu Chemical Co., Ltd.)

A4: Hardened polyoxyl resin (SD-7292: manufactured by Dow Corning Toray)

B1: unreactive polyxanthene resin having a mass average molecular weight of 400,000 or more

C1: Addition of platinum catalyst (SRX212: manufactured by Dow Corning Toray)

C2: Addition of platinum catalyst (PL-50T: Shin-Etsu Chemical Co., Ltd.)

<release agent composition-A>

Hardened polyoxyl resin a1 20 parts

Unreacted polyoxyl resin b1 0.2 parts

Addition of platinum catalyst c1 0.2 parts

MEK/toluene mixed solvent (mixing ratio is 1:1)

<Manufacture of second release film>

By using a reverse gravure coating method, a release agent composed of the following release agent composition B was applied to the polyester film-2 so that the coating amount (after drying) became 0.1 g/m ² . After heat treatment at 150 ° C for 30 seconds, a second release film was obtained.

<release agent composition-B>

Hardened polyoxyl resin a3 19 parts

Hardened polyoxyl resin a4 1 part

Addition of platinum catalyst c1 0.2 parts

MEK/toluene mixed solvent (mixing ratio is 1:1)

<Manufacture of adhesive sheets on both sides without substrate>

The coating liquid composed of the following acrylic pressure-sensitive adhesive composition was applied onto the release layer of the obtained second release film, and then heat-treated at 100 ° C for 5 minutes to obtain a coating amount (after drying) of 50 μm. Adhesive layer.

<Composition for forming an adhesive layer>

An acrylate copolymer obtained by randomly copolymerizing 75 parts by mass of 2-ethylhexyl acrylate, 20 parts by mass of vinyl acetate, and 5 parts by mass of acrylic acid (Mw=540000 Mn=67000 Mw/Mn = 8 theoretical Tg - 50 ° C) 1 kg, and 20 g of 4-phenylbenzophenone as a photopolymerization initiator was mixed to form an adhesive layer.

Next, the first release film was bonded to the exposed surface of the adhesive layer to obtain a two-sided adhesive sheet having no substrate.

Examples 4-2 to 4-5 and Comparative Examples 4-1 to 4-6:

In the same manner as in Example 4-1, except that the coating agent composition, the release agent composition, and the thickness of the polyester film substrate were changed as shown in Tables 9 and 10 below. A first release film and a second release film were obtained. Then, the two layers are bonded together through the adhesive layer to obtain a two-sided adhesive sheet having no substrate. The properties of the release films obtained in the above examples and comparative examples are shown in Tables 11 and 12 below.

[Industrial availability]

The release film of the present invention is excellent in release property from an adhesive and has little transition property, and is suitable for use in, for example, a touch panel manufacturing of a capacitance type, a polarizing plate used in a liquid crystal display (LCD), The manufacture of the LCD component such as the phase difference plate, the manufacture of the plasma display panel constituent member, the manufacture of the organic electroluminescence component, and the like are also applicable to various adhesive layer protection applications in addition to the manufacture of various display constituent members.

Claims (7)

A release film characterized by being formed on a single side of a polyester film by a coating liquid containing a reactive polyoxyxylene resin having a functional group, an unreactive polyoxyl resin, and a platinum-based catalyst. Polyoxygenated release layer. The release film of claim 1, wherein the polyfluorene-based release layer is formed of a coating liquid containing a hexenyl group, a vinyl group, a phenyl group, and a hydrazine alkyl group as a functional group. The reactive polyxanthene resin, the unreacted polyoxyl resin having a mass average molecular weight of 50,000 to 100,000, and a platinum-based catalyst. The release film according to claim 1 or 2, which is provided with a release film of a coating layer and the polyfluorinated oxygen release layer on one side of the polyester film, and the coating layer contains a casing compound. Further, the amount of the polyester oligomer on the surface of the polyfluorinated release layer after heating the release film at 180 ° C for 10 minutes was 2.0 mg/m ² or less. The release film of claim 3, wherein the coating layer contains an organic compound containing aluminum. The release film according to claim 1, wherein the polyfluorene-based release layer is formed of a coating liquid containing a component: a reactive polyoxyl resin having an alkenyl group and an alkyl group as a functional group, An unreacted polyxanthene resin having a mass average molecular weight of 400,000 or more and a platinum-based catalyst. A non-substrate two-sided adhesive sheet which is sequentially laminated with a release film (first release film) of claim 5, an adhesive layer, and a release film having a larger peeling force than the first release film (2nd) The release film is a non-substrate two-sided adhesive sheet, characterized in that the first release film and the adhesive layer have a low-speed peeling force of 0.3 m/min and a low-speed peeling force of 10 to 20 mN/cm, and a high speed of 60 m/min. The peeling force is 90 mN/cm or less. a non-substrate adhesive sheet according to claim 6, wherein a coating layer containing the conductive compound (A) and the binder polymer (B) is laminated on the polyester film of the first release film, and A release layer is laminated on the coating layer.