JP2013111941A - Laminate, release liner and adhesive tape substrate consisting of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate resulting in a less curled laminate-molded article while being good in heat resistance.SOLUTION: The laminate includes at least (A) layer, (B) layer, and (C) layer in this order. The (A) layer is a mold release agent layer. The (B) layer includes a layer comprising an ethylenic polymer composition comprising 50-80 wt.% of an ethylene/α-olefin copolymer (B-1) satisfying (a) 3-6C α-olefin, (b) the ratio of ≥6C long chain branches is 0.01-0.2 per 1,000 carbon atoms of a main chain, (c) the density is 920-935 kg/m, and (d) the MFR is 5-50 g/15 min; 3-30 wt.% of an ethylene/α-olefin copolymer (B-2) having a density of 860-910 kg/mand an MFR of 1-50 g/10 min; and 5-40 wt.% of high pressure method low density polyethylene (B-3) having a density of 915-930 kg/mand an MFR of 1-10 g/10 min; and the (C) layer comprises a substrate.

Description

  The present invention relates to a laminate that can be used for a release liner and a base material for an adhesive tape.

  As a release liner and a base material for an adhesive tape, a laminate obtained by laminating a polyethylene resin on a support such as paper and applying a release agent thereon is used. The polyethylene layer plays a role of a sealing agent for preventing the release agent from being absorbed by the support when the release agent and the support are in direct contact with each other, and is important in terms of configuration.

  In recent years, an extrusion laminator with a high processing speed has been developed, and the process of laminating a polyethylene layer to a support has also been performed at a high speed, but as the productivity increases, the adhesion to the support has increased. There was a problem of lowering.

  When the adhesiveness to the support is low, the product is peeled off from the other adherend when the adhesive tape and other products are peeled off. For liners and adhesive tape substrates, the adhesion between the support and the resin layer is important.

  It is effective to reduce the density of the resin layer in order to improve the adhesion to the support. However, in the case of low density polyethylene conventionally used for release liners and adhesive tape substrates, the melting point is lowered by lowering the density. Therefore, the drying time is reduced in the drying process after the release agent is applied. There is a problem that productivity is reduced.

  Further, when the release agent is a thermosetting type, there is a so-called curing process in which the release agent is cured at a high temperature after the release agent is applied. By heating at a high temperature, the resin layer contracts, and the laminate warps in one direction, so-called curling occurs. Curling of the laminate occurs because the resin volume shrinks when the molten resin is solidified, resulting in a size difference from the substrate. When the curl becomes large, the end of the laminate may come into contact with the processing machine during secondary processing, which may cause a problem. Since the size of the curl increases in proportion to the resin density, it is necessary to reduce the resin density in order to suppress the curl, but if the resin density is reduced, the occurrence of pinholes and a decrease in surface gloss will result. It is necessary to lower the heating temperature and extend the heating time, leading to a reduction in productivity. Therefore, there has been a demand for a resin with less curling due to heating even at the same density.

JP 2009-293014 A

  The present invention has been made to solve the above-mentioned problems of the prior art, and provides a laminate having good substrate adhesion at high speed processing and less curling of a laminate molded product. It is.

The present invention has been found as a result of intensive studies on the above-described object. That is, the present invention is a laminate having at least (A) layer / (B) layer / (C) layer in this order, wherein (A) layer is a release agent layer, and (B) layer has the following requirements: The ethylene / α-olefin copolymer (A) satisfying (a) to (d) is 50 to 80% by weight, the density is 860 kg / m ³ or more and 910 kg / m ³ or less, and the melt flow rate (hereinafter referred to as MFR) is 1 g / 10 min or more 50 g / 10 minutes or less ethylene · alpha-olefin copolymer (B) 3 to 30 wt% and a density 915 kg / ^{m 3} or more 930 kg / ^{m 3} or less, MFR is 1 g / 10 min or more 10 g / 10 A layer made of an ethylene polymer composition comprising 5 to 40% by weight of a high-pressure method low density polyethylene (C) of less than or equal to 5 minutes, and (C) a laminate comprising the layer comprising a substrate. is there.

(A) The α-olefin has 3 to 6 carbon atoms
(B) It has 0.01 to 0.2 long-chain branches having 6 or more carbon atoms per 1000 carbon atoms in the main chain. (C) Density is 920 kg / m ³ or more and 935 kg / m ³ or less (d) MFR is 5 g / 10 minutes or more and 50 g / 10 minutes or less Hereinafter, the present invention will be described in detail.

  The ethylene / α-olefin copolymer (A) constituting the layer (B) of the present invention is an ethylene / α-olefin composed of a repeating unit derived from ethylene and a repeating unit derived from an α-olefin having 3 to 6 carbon atoms. It is an olefin copolymer. Examples of the α-olefin having 3 to 6 carbon atoms include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 3-methyl-1-butene. You may use together at least 2 types of these C3-C6 alpha olefins.

The ethylene / α-olefin copolymer (A) constituting the layer (B) of the present invention has 0.01 to 0.2 long chain branches having a prime number of 6 or more per 1000 carbon atoms in the structure. is there. By having 0.01 to 0.2 long-chain branches per 1000 carbon atoms in the structure, the melt tension of the ethylene-α-olefin copolymer (A) is increased, and the resulting ethylene polymer composition Molding processability is improved. When the number of long chain branches is less than 0.01 per 1000 carbon atoms, the neck-in at the time of laminating the resulting ethylene polymer composition is undesirably increased. Further, when the number of long-chain branches is more than 0.2 per 1000 carbon atoms, the drawdown at the time of laminating the obtained ethylene polymer composition is not preferable. In addition, the number of long-chain branches is the number of branches of a hexyl group or more (carbon number of 6 or more) detected by ¹³ C-NMR measurement.

The ethylene / α-olefin copolymer (A) constituting the layer (B) of the present invention has a density measured by the method of JIS K6760 (1995) of 920 kg / m ³ or more and 935 kg / m ³ or less. Here, when the density is less than 920 kg / m ³ , the heat resistance of the ethylene polymer composition is inferior, which is not preferable. On the other hand, when it exceeds 935 kg / m ³ , the melting temperature of the ethylene / α-olefin copolymer is high, and the laminate is excellent in heat resistance and rigidity, but on the other hand, the curl is large, which is not preferable.

  The ethylene / α-olefin copolymer (A) constituting the layer (B) of the present invention has an MFR measured by the method of JIS K6760 (1995) of 5 g / 10 min to 50 g / 10 min, preferably 10 g / 10 min or more and 40 g / 10 min or less. An MFR of less than 5 g / 10 minutes is not preferable because the extrusion load increases and productivity decreases. On the other hand, when MFR exceeds 50 g / 10 min, the neck-in is large and the extrusion laminate formability is poor.

  The ethylene / α-olefin copolymer (A) constituting the layer (B) of the present invention is not limited in the production method, and is produced by a method using a Ziegler catalyst, a method using a Phillips catalyst, a method using a metallocene catalyst, or the like. Although possible, it is preferable to produce by a method using a metallocene catalyst.

  When producing an ethylene / α-olefin copolymer (A) using a metallocene catalyst, the metallocene catalyst used has a metallocene complex, an activation co-catalyst, and, if necessary, an organoaluminum compound as constituent components, A macromonomer is synthesized by a specific metallocene catalyst, and at the same time as the synthesis of the macromonomer, a specific metallocene catalyst is used to copolymerize the macromonomer with ethylene and a olefin having 3 to 6 carbon atoms, It is preferable to carry out copolymerization.

  The macromonomer is an olefin polymer having a vinyl group at the terminal, and is an ethylene copolymer having a vinyl group at the terminal obtained by copolymerizing ethylene and an olefin having 3 to 6 carbon atoms.

  The number average molecular weight (Mn) in terms of linear polyethylene of the macromonomer is preferably 2000 or more, more preferably 5000 or more, and most preferably 10,000 or more. The weight average molecular weight (Mw) in terms of linear polyethylene is preferably 4000 or more, more preferably 10,000 or more, and most preferably greater than 15,000. By increasing the molecular weight of the macromonomer, the length of the long chain branch introduced into the ethylene / α-olefin copolymer (A) is increased, and the melt tension is improved.

  The ethylene / α-olefin copolymer (A) constituting the layer (B) of the present invention preferably has a weight average molecular weight (Mw) to number average molecular weight ratio Mw / Mn in the range of 2 to 5. Mw / Mn can be calculated by measuring the weight average molecular weight (Mw) and the number average molecular weight (Mn), which are standard polyethylene equivalent values, by gel permeation chromatography (GPC). When Mw / Mn is in this range, the content ratio of the low molecular weight component in the resin is small, so roll contamination during lamination molding due to leaching of the low molecular weight component, stickiness of the surface of the laminate molded product, heat seal failure, etc. The adverse effect is suppressed, and at the same time, the extrusion load becomes higher than necessary, and the amount of extrusion during lamination is not limited.

  The ethylene / α-olefin copolymer (A) constituting the layer (B) of the present invention may be obtained by any method, for example, the production conditions per se of the present embodiment described later, or the condition factors. It is possible to make them arbitrarily by fine-tuning.

  Specific metallocene catalysts for synthesizing macromonomers include metallocene complexes, non-bridged bis (indenyl) zirconium complexes, non-bridged bis (cyclopentadienyl) zirconium complexes, bridged bis (cyclopentadienyl) zirconium complexes, Alternatively, a catalyst using a bridged (cyclopentadienyl) (indenyl) zirconium complex (hereinafter referred to as component (j)) is preferable.

  Specific examples of the component (j) include, for example, bis (indenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dichloride, 1,1,3,3-tetramethyldisiloxane-1,3-diyl-bis (cyclopenta). Dienyl) zirconium dichloride, 1,1-dimethyl-1-silaethane-1,2-diyl-bis (cyclopentadienyl) zirconium dichloride, propane-1,3-diyl-bis (cyclopentadienyl) zirconium dichloride, Dimethylsilanediyl (cyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2-methylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (4,7-dimethyl Ndenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride and the like, and dimethyl, diethyl, dihydro, diphenyl and dibenzyl of the above transition metal compounds However, it is not limited to these examples.

  In addition, specific metallocene catalysts that perform macromonomer copolymerization at the same time as the synthesis of the macromonomer include a metallocene complex, a bridged (cyclopentadienyl) (fluorenyl) zirconium complex or a bridged (indenyl) (fluorenyl) zirconium complex. A catalyst using (hereinafter referred to as component (k)) is preferred.

  Specific examples of component (k) include, for example, diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2-trimethylsilyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, Diphenylmethylene (1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium Dichloride, isopropylidene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenyl Randiyl (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, dimethylsilanediyl (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (1-indenyl) (9-fluorenyl) zirconium dichloride Diphenylmethylene (2-phenyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2-phenyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, etc. Examples thereof include dimethyl, diethyl, dihydro, diphenyl, and dibenzyl isomers of dichloride and the above transition metal compounds. Moreover, although the compound which substituted the zirconium atom of the said transition metal compound with the titanium atom or the hafnium atom can also be illustrated, it is not limited to these.

  There is no restriction | limiting in particular in the quantity of the component (k) with respect to a component (j), It is preferable that it is 0.0001-100 times mole, Most preferably, it is 0.001-10 times mole.

  The activation co-catalyst used as a component of the metallocene catalyst is a metallocene complex or a compound that plays a role in converting a reaction product of a metallocene complex and an organoaluminum compound into an active species capable of olefin polymerization. It is preferable that it is a compound which produces | generates a reactive compound, and the produced | generated cationic compound acts as a polymerization active seed | species which can superpose | polymerize an olefin. An activation co-catalyst is a compound that provides a compound that, after forming a polymerization active species, coordinates weakly or interacts with the generated cationic compound, but does not react directly with the active species.

  Specific examples of the activation promoter include alkylaluminoxanes such as methylaluminoxane, silica gel-supported alkylaluminoxanes, tris (fluorinated aryl) borons such as tris (pentafluoreophenyl) boron, N, N-dimethylammonium-tetrakis ( Examples thereof include boron compounds such as tetrakis (fluorinated aryl) boron salts such as pentafluorophenyl) boron, silica gel-supported materials thereof, clay minerals, clay minerals treated with organic compounds, and the like. Among these, it is preferable to use a clay mineral treated with an organic compound.

  When a clay mineral treated with an organic compound is used as the activation promoter, the clay mineral used is preferably a clay mineral belonging to the smectite group, and specific examples include montmorillonite, beidellite, saponite, hectorite and the like. It is also possible to use a mixture of a plurality of these clay minerals.

  The organic compound treatment means introducing an organic ion between clay mineral layers to form an ionic complex.

  Examples of the organic compound used in the organic compound treatment include N, N-dimethyl-n-octadecylamine hydrochloride, N, N-dimethyl-n-eicosylamine hydrochloride, N, N-dimethyl-n-docosylamine hydrochloride, N, N-dimethyloleylamine hydrochloride, N, N-dimethylbehenylamine hydrochloride, N-methyl-bis (n-octadecyl) amine hydrochloride, N-methyl-bis (n-eicosyl) amine hydrochloride, N-methyl -Alkylammonium salts such as dioleylamine hydrochloride, N-methyl-dibehenylamine hydrochloride, N, N-dimethylaniline hydrochloride can be exemplified.

  The metallocene catalyst is a method of reacting a mixture of component (j) and component (k) with an activation promoter, a method of reacting component (j) and the activation promoter, and then reacting component (k), Although it prepares by the method of making (j) and component (k) react separately, there is no restriction | limiting in particular in the preparation method of a metallocene catalyst.

  As the metallocene catalyst, an alkylaluminum such as triethylaluminum or triisobutylaluminum may be used as necessary for the activation of the metallocene complex and the removal of impurities in the solvent during the preparation of the catalyst.

  When producing the ethylene / α-olefin copolymer (A) constituting the layer of the present invention (B), it is preferable to carry out at a polymerization temperature of −100 to 120 ° C., particularly considering productivity, 20 to 120 ° C. It is preferable to carry out in the range of 60 to 120 ° C. The polymerization time is preferably in the range of 10 seconds to 20 hours, and the polymerization pressure is preferably in the range of normal pressure to 300 MPa. The polymerizable monomer is ethylene and an α-olefin having 3 to 6 carbon atoms, and the supply ratio of ethylene and the α-olefin having 3 to 6 carbon atoms is ethylene / α-olefin having 3 to 6 carbon atoms ( A feed ratio of 1 to 200, preferably 3 to 100, and more preferably 5 to 50 can be used. It is also possible to adjust the molecular weight using hydrogen during polymerization. The polymerization can be carried out by any of batch, semi-continuous and continuous methods, and can be carried out in two or more stages by changing the polymerization conditions. In addition, the ethylene copolymer can be obtained by separating and recovering from the polymerization solvent by a conventionally known method after the completion of the polymerization and drying.

  Polymerization can be carried out in a slurry state, a solution state, or a gas phase state. In particular, when the polymerization is performed in a slurry state, an ethylene-based copolymer having a powder particle shape is efficiently and stably produced. Can do.

  The number of long chain branches of the ethylene / α-olefin copolymer (A) constituting the layer (B) of the present invention can be increased by increasing the number of terminal vinyls of the macromonomer. The number of terminal vinyls of the macromonomer can be controlled by selecting a metallocene compound for synthesizing the macromonomer. For example, it can be increased by changing the non-bridged metallocene compound to a bridged metallocene compound.

  Mw / Mn of the ethylene / α-olefin copolymer (A) constituting the layer (B) of the present invention can be increased by decreasing Mn of the macromonomer. The Mn of the macromonomer can be controlled by selecting a metallocene compound for synthesizing the macromonomer. For example, it can be reduced by changing a non-bridged metallocene compound to a bridged metallocene compound.

The ethylene / α-olefin copolymer (B) constituting the layer (B) of the present invention has a density of 860 kg / m ³ or more and 910 kg / m ³ or less. When the density is less than 860 kg / m ³ , blocking of the laminate of the present invention is likely to occur, which is not preferable. Moreover, when a density exceeds 910 kg / m < ³ >, there exists a possibility that the adhesiveness of a laminated body may fall.

  The ethylene / α-olefin copolymer (B) constituting the layer (B) of the present invention has an MFR measured by the method of JIS K6760 (1995) of 1 g / 10 min to 50 g / 10 min, preferably 1 g / It is not less than 10 minutes and not more than 40 g / 10 minutes, more preferably not less than 1 g / 10 minutes and not more than 30 g / 10 minutes. When the MFR is less than 1 g / 10 minutes, the extrusion load at the time of laminating becomes large and the productivity is lowered, which is not preferable. On the other hand, if the MFR exceeds 50 g / 10 minutes, the neck-in at the time of lamination may increase.

  Commercially available products such as AFINITY EG8100G, EG8852G, PL1280G, and PL1845G (above, manufactured by Dow Chemical Co., Ltd.) may be used for the ethylene / α-olefin copolymer (B) constituting the layer (B) of the present invention. it can.

  The high-pressure method low-density polyethylene (C) constituting the layer (B) of the present invention can be obtained by a conventionally known high-pressure radical polymerization method, and is appropriately selected within the scope of the present invention.

High-pressure low-density polyethylene constituting the layer (B) of the present invention (C) has a density measured by the method of JIS K6760 (1995) is of 915 kg / ^{m 3} or more 930 kg / ^{m 3} or less. When it is in this range, film formation stability is obtained, which is preferable.

  The high-pressure low-density polyethylene (C) constituting the layer (B) of the present invention has an MFR measured by the method of JIS K6760 (1995) of 1 g / 10 min or more and 10 g / 10 min or less. When the MFR is less than 1 g / 10 minutes, the extrusion load at the time of laminating increases, and when it exceeds 10 g / 10 minutes, the neck-in at the time of laminating may increase.

  Commercially available products such as trade names Petrocene 360, Petrocene 205, Petrocene 203 (above, manufactured by Tosoh Corporation) can be used as the high-pressure method low density polyethylene (C) constituting the layer (B) of the present invention.

  Ethylene-based polymer composition for extrusion laminating blends of ethylene / α-olefin copolymer (A), ethylene / α-olefin copolymer (B), and high-pressure low-density polyethylene (C) satisfying the above requirements in specific amounts. Is excellent in heat resistance and curl balance when formed into a laminate by extrusion lamination. The ethylene-based polymer composition constituting the layer (B) of the present invention comprises an ethylene / α-olefin copolymer (A) of 50 to 80% by weight and an ethylene / α-olefin copolymer (B) of 3 to 30%. % And high pressure method low density polyethylene (C) 5 to 40% by weight. When the blending amount of the ethylene / α-olefin copolymer (A) is less than 50% by weight, there is a possibility that stable film forming property at the time of lamination processing cannot be obtained. On the other hand, when the blending amount exceeds 80% by weight, the density becomes high and the adhesion to the substrate may be lowered. If the blending amount of the ethylene / α-olefin copolymer (B) is less than 3% by weight, the effect of improving the substrate adhesion cannot be obtained. On the other hand, if the blending amount exceeds 30% by weight, the film is sticky. . Further, if the blending amount of the high-pressure method low density polyethylene (C) is less than 5% by weight, the melt tension of the ethylene polymer composition becomes small and the molding processability deteriorates, which is not preferable. On the other hand, the blending amount is 40% by weight. In the case of exceeding, it is not preferable because the melting point decreases.

  In the ethylene polymer composition constituting the layer (B) of the present invention, a stabilizer, a lubricant, a flame retardant, a dispersant, a filler, and a foaming agent are included in the range not departing from the gist of the present invention. , A foam nucleating agent, a crosslinking agent, an ultraviolet ray inhibitor, an antioxidant, a colorant and the like can be contained. Moreover, it can also be used by mixing with other thermoplastic resins.

  For the ethylene polymer composition constituting the layer (B) of the present invention, a method for forming a normal resin composition can be used. For example, as a melting / mixing method, a single screw extruder or a twin screw extruder is used. Known methods such as extrusion kneading and roll kneading can be used, and melt kneading can be performed by this method.

  Examples of the substrate constituting the layer (C) of the present invention include synthetic polymer films and sheets, woven fabrics, nonwoven fabrics, metal foils, papers, cellophane and the like. Examples thereof include films and sheets made of a synthetic polymer such as polyethylene terephthalate, polyamide, polyvinyl alcohol, polycarbonate, polyethylene, and polypropylene. Further, these polymer films and sheets may be further subjected to aluminum vapor deposition, alumina vapor deposition, or silicon dioxide vapor deposition. Further, these polymer films and sheets may be further printed using urethane-based ink or the like. Examples of the metal foil include aluminum foil and copper foil, and examples of paper include kraft paper, stretched paper, high-quality paper, and glassine paper.

  There is no restriction | limiting in particular as a mold release agent used for the mold release agent layer which comprises the (A) layer of this invention, As a silicone type mold release agent, a thermosetting silicone, an ultraviolet curable silicone, an electron beam curable silicone, etc. Can be illustrated. The organic mold release agent having a long chain alkyl group includes a long chain alkyl acrylate copolymer, a long chain alkyl vinyl ester copolymer, a long chain alkyl amide copolymer, and a copolymer of a long chain alkyl derivative of maleic acid. Examples thereof include copolymers and copolymers of long-chain alkyl allyl esters.

  The laminate of the present invention has at least (A) layer / (B) layer / (C) layer in this order, and consists of only three layers (A) layer, (B) layer, and (C) layer. It may include other layers as well as those.

  The laminate of the present invention can be produced by laminating the ethylene polymer composition constituting the (B) layer on the base material which is the (C) layer, and then applying a release agent to the (B) layer. .

  The ethylene polymer composition constituting the layer (B) is laminated on the base material which is the layer (C), but the method of laminating is not particularly limited, and in addition to the extrusion laminating method, a dry laminating method, The wet lamination molding method can be exemplified, but the extrusion lamination molding method is preferable from the viewpoint of production efficiency.

The extrusion laminate molding method may be any of single laminate, tandem laminate, coextrusion laminate, and sandwich laminate, and is not particularly limited. Moreover, when performing an extrusion laminating process, it is preferable to extrude from a die at a temperature of 250 to 350 ° C. in order to obtain a laminate having good adhesion between the substrate and the ethylene polymer composition layer. Further, at least the surface where the molten film of the ethylene polymer composition is in contact with the substrate may be oxidized with air or ozone gas. When the oxidation reaction with air proceeds, it is preferable to extrude from a die at a temperature of 270 ° C. or higher, and when the oxidation reaction with ozone gas proceeds, it is preferable to extrude at 250 ° C. or higher. In addition, it is preferable that the processing amount of ozone gas is 0.5 mg or more per 1 m ^{2 of} the film extruded from the die. Moreover, in order to improve adhesiveness with a base material, you may perform well-known surface treatments, such as an anchor-coat agent process, a corona discharge process, a flame process, and a plasma process, to the adhesion surface of a base material.

In producing the laminate of the present invention, a method usually used as a coating method of the release agent (B) layer, for example, gravure coater method, roll coater method, reverse coater method, doctor blade method, bar coater method , Comma coater method, die coater method, lip coater method, knife coater method and the like. The thickness of the release agent layer is not particularly limited, but is 0.1 to 1.5 g / m ² .

  The laminate of the present invention can be used for a release liner, a base material for an adhesive tape, and the like. As the release liner, the laminate of the present invention can be used as it is, and the adhesive sheet or adhesive tape can be re-applied by sticking an adhesive tape or adhesive seal to the surface of the layer (A) of the laminate of the present invention. It can be peeled and used without impairing the adhesiveness. The base material for adhesive tapes can be made into an adhesive tape by laminating an adhesive layer on the (C) layer side of the laminate of the present invention. That is, an adhesive tape can be manufactured by apply | coating an adhesive to the (C) layer surface of the laminated body of this invention, and drying to make a scroll.

  The laminate of the present invention has good adhesion to the substrate during high-speed processing, has little curl of the laminate molded product, and can be used as a release liner, a substrate for an adhesive tape, and the like.

  Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to these.

-Measurement of molecular weight and molecular weight distribution-
The weight average molecular weight (Mw), the number average molecular weight (Mn), and the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) of the macromonomer and the ethylene / α-olefin copolymer (A) are as follows. Measured by chromatography (GPC). Tosoh Co., Ltd. HLC-8121GPC / HT is used as the GPC apparatus, Tosoh Co., Ltd. TSKgel GMHhr-H (20) HT is used as the column, the column temperature is set to 140 ° C., and 1 is used as the eluent. Measurement was performed using 2,4-trichlorobenzene. A measurement sample was prepared at a concentration of 1.0 mg / ml, and 0.3 ml was injected and measured. The calibration curve of molecular weight is calibrated using a polystyrene sample having a known molecular weight. In addition, Mw and Mn were calculated | required as a value of linear polyethylene conversion.

~ Measurement of density ~
The density of the ethylene / α-olefin copolymer (A) and the ethylene polymer composition was measured by a density gradient tube method in accordance with JIS K6760 (1995).

~ Measurement of MFR ~
The MFR of the ethylene / α-olefin copolymer (A) and the ethylene polymer composition was measured with a melt indexer in accordance with JIS K6760 (1995).

-Measurement of the number of long chain branches-
The number of long chain branches of the ethylene / α-olefin copolymer (A) was measured by ¹³ C-NMR using a Varian VNMRS-400 nuclear magnetic resonance apparatus. The solvent is tetrachloroethane-d2. The number per 1,000 main chain methylene carbons was determined from the following formula (4) described in “Macromolecules” Vol. 31, No. 25, pages 8679-8683 (1998).

Number of long chain branches = IA _α / (3 × IA _tot ) (4)
[Wherein, IA _α is the integrated intensity of a long-chain branched α-carbon peak (chemical shift: 34.6 ppm) above the hexyl group, and IA _tot is the integrated intensity of the main chain methylene carbon peak (30.0 ppm). It is. ]
~ Neck-in ~
The ethylene polymer composition was supplied to an extruder of an extrusion laminator (manufactured by Musashinokikai Co., Ltd.) having a 90 mmφ screw, extruded from a T die having an air gap of 130 mm and a temperature of 315 ° C. and an opening width of 600 mm, T die opening width and ethylene polymer when extrusion lamination was performed on a glassine paper substrate having a grammage of 83 g / m ² and an ethylene polymer composition having a thickness of 20 μm at a take-up speed of 200 m / min. The difference from the coating width of the composition was defined as neck-in, and the value was measured.

~ Base material adhesion ~
The laminate produced in the neck-in measurement was cut to a width of 15 mm, and the peel strength between the surface of the paper substrate and the ethylene polymer composition was determined using a tensile tester (A & D Tensilon). Measurement was performed at 300 mm / min. The case where the adhesive strength was 2N / 15 mm width or more was judged as ◯, and the case where the adhesive strength was less than 2N / 15 mm width was judged as x.

-Production of release liner-
A silicone mold release agent (trade name: KM3950, manufactured by Shin-Etsu Chemical Co., Ltd.) containing an addition-type organopolysiloxane as a main component on the ethylene polymer composition layer side of the laminate produced in the neck-in measurement has a solid content of 1 It was applied using a gravure coater so as to be 5 g / m ² and dried and cured at 160 ° C. for 30 seconds to obtain a release liner.

~curl~
The release liner produced in the production of the release liner was placed on a flat surface with the release agent layer facing upward, and a 10 cm square was drawn on this. A cut was made in the diagonal line of the square, and after standing for 24 hours under conditions of an air temperature of 23 ° C. and a relative humidity of 50%, the height at which the cut portion was warped from the flat surface was measured. The case where the curl height was less than 5 mm was judged as ○ and the case where it was 5 mm or more and x.

Synthesis example 1
[Preparation of modified hectorite]
After adding 3 liters of ethanol and 100 ml of 37% concentrated hydrochloric acid to 3 liters of water, 585 g (1.1 mol) of N-methyl-dioleylamine was added to the resulting solution and heated to 60 ° C. to form the hydrochloride salt. A solution was prepared. 1 kg of hectorite was added to this solution. The suspension was stirred at 60 ° C. for 3 hours, the supernatant was removed, and then washed with 50 L of 60 ° C. water. Then, it dried at 60 degreeC and 10-3 torr for 24 hours, and the modified | denatured hectorite with an average particle diameter of 5.2 micrometers was obtained by grind | pulverizing with a jet mill.
[Preparation of production catalyst for polyethylene resin]
500 g of the modified hectorite was suspended in 1.7 liters of hexane, and 8.25 g (20.0 mmol) of dimethylsilanediyl (cyclopentadienyl) (2-methylindenyl) zirconium dichloride and a hexane solution of triisobutylaluminum ( 0.714M) Add 2.8 liters (2 mol) of mixture, stir at 60 ° C. for 3 hours, let stand and remove supernatant, add triisobutylaluminum in hexane (0.15M) Thus, a macromonomer synthesis catalyst (100 g / L) was obtained.

In the macromonomer synthesis catalyst prepared above, 10 mol% of isopropylidene (1-cyclopentadienyl) (2,7-di-) with respect to dimethylsilanediyl (cyclopentadienyl) (2-methylindenyl) zirconium dichloride is used. 1.21 g (2.22 mmol) of t-butyl-9-fluorenyl) zirconium dichloride was added and stirred at room temperature for 6 hours. The supernatant was removed by standing, and a hexane solution (0.15 M) of triisobutylaluminum was added to finally obtain a 100 g / L polyethylene resin production catalyst.
[Production of ethylene / α-olefin copolymer (A-1)]
In the polymerization vessel having an internal volume of 540 L, the above-described [ The catalyst slurry prepared in [Preparation of Production Catalyst for Polyethylene Resin] was continuously supplied, and the polymerization reaction was continuously carried out while maintaining the total pressure at 3,000 kPa and the polymerization vessel internal temperature at 60 ° C. The slurry was continuously extracted from the polymerization vessel to remove unreacted hydrogen, ethylene, and butene-1, and then separated and dried to obtain ethylene / α-olefin copolymer (A-1) powder. This was melt-kneaded using a 50 mm diameter single screw extruder set at 180 ° C. and pelletized to obtain ethylene / α-olefin copolymer (A-1) pellets. The density of the obtained ethylene / α-olefin copolymer (A-1) pellets was 925 kg / m ³ , MFR was 24.1 g / 10 min, the number of long-chain branches was 0.13 per 1000 carbon atoms, and the weight average The ratio Mw / Mn between the molecular weight (Mw) and the number average molecular weight (Mn) was 3.8.

  In this synthesis example, ethylene and 1-butene are polymerized simultaneously with the production of the macromonomer shown in Reference Example 1 below.

Reference example 1
[Synthesis of macromonomer]
In Synthesis Example 1 [Production of ethylene / α-olefin copolymer (A-1)], the macromonomer synthesis catalyst prepared in Synthesis Example 1 [Preparation of polyethylene resin production catalyst] was used instead of the polyethylene resin production catalyst. Except having used, it carried out similarly to the synthesis example 1, and obtained the macromonomer pellet. Mn of the obtained macromonomer pellet was 15,000, and Mw / Mn was 2.5. Further, when the terminal structure of the macromonomer pellet was analyzed, the number of terminal vinyls per 1,000 carbons was 0.07.

Synthesis example 2
[Preparation of polyethylene resin production catalyst]
500 g of modified hectorite prepared in Synthesis Example 1 [Preparation of modified hectorite] was suspended in 1.7 liters of hexane, and dimethylsilanediyl (cyclopentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride was suspended. Add a mixed solution of 8.81 g (20.0 mmol) and hexane solution (0.714 M) of triisobutylaluminum (2.814 M), stir at 60 ° C. for 3 hours, and leave to stand to remove the supernatant. After removal, a hexane solution (0.15 M) of triisobutylaluminum was added to obtain a macromonomer synthesis catalyst (100 g / L).

The macromonomer synthesis catalyst prepared above was mixed with 5 mol% of diphenylmethylene (1-cyclopentadienyl) (9- 9%) based on dimethylsilanediyl (cyclopentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride. Fluorenyl) zirconium dichloride (0.58 g, 1.05 mmol) was added and stirred at room temperature for 6 hours. The supernatant was removed by standing, and a hexane solution (0.15 M) of triisobutylaluminum was added to finally obtain a 100 g / L polyethylene resin production catalyst.
[Production of ethylene / α-olefin copolymer (A-2)]
In Synthesis Example 1 [Production of ethylene / α-olefin copolymer (A-1)], butene-1 was changed from 4.9 kg / hour to 5.3 kg / hour, and the hydrogen supply amount was changed from 20 NL / hour to 5 NL / hour. The ethylene / α-olefin copolymer (A-2) was prepared in the same manner as in Synthesis Example 1, except that the catalyst was changed to the polyethylene resin production catalyst prepared in [Preparation of polyethylene resin production catalyst]. Obtained. The density of the obtained ethylene / α-olefin copolymer (A-2) is 920 kg / m ³ , MFR is 12.7 g / 10 min, the number of long-chain branches is 0.10 per 1000 carbon atoms, and the weight average molecular weight The ratio Mw / Mn between (Mw) and the number average molecular weight (Mn) was 4.2.

Reference example 2
[Synthesis of macromonomer]
In Synthesis Example 2 [Production of ethylene / α-olefin copolymer (A-2)], the macromonomer synthesis catalyst prepared in Synthesis Example 2 [Preparation of polyethylene resin production catalyst] was used instead of the polyethylene resin production catalyst. A macromonomer pellet was obtained in the same manner as in Synthesis Example 2 except that it was used. Mn of the obtained macromonomer pellet was 20,000, and Mw / Mn was 2.8. Further, when the terminal structure of the macromonomer pellet was analyzed, the number of terminal vinyls per 1,000 carbons was 0.05.

Synthesis example 3
[Production of ethylene / α-olefin copolymer (A-3)]
In Synthesis Example 1 [Production of ethylene / α-olefin copolymer (A-1)], butene-1 was changed from 4.9 kg / hour to 5.3 kg / hour, and the hydrogen supply amount was changed from 20 NL / hour to 30 NL / hour. The ethylene / α-olefin copolymer (A-3) was prepared in the same manner as in Synthesis Example 1 except that the catalyst was changed to the polyethylene resin production catalyst prepared in Synthesis Example 2 [Preparation of Polyethylene Resin Production Catalyst]. ) The resulting ethylene / α-olefin copolymer (A-3) has a density of 920 kg / m ³ , an MFR of 39.2 g / 10 min, a long-chain branch number of 0.12 per 1000 carbon atoms, and a weight average molecular weight. The ratio Mw / Mn between (Mw) and the number average molecular weight (Mn) was 4.1.

Reference example 3
[Synthesis of macromonomer]
In Synthesis Example 3 [Production of ethylene / α-olefin copolymer (A-3)], the macromonomer synthesis catalyst prepared in Synthesis Example 2 [Preparation of polyethylene resin production catalyst] was used instead of the polyethylene resin production catalyst. A macromonomer pellet was obtained in the same manner as in Synthesis Example 3 except that it was used. Mn of the obtained macromonomer pellet was 10,000, and Mw / Mn was 3.0. Further, when the terminal structure of the macromonomer pellet was analyzed, the number of terminal vinyls per 1,000 carbons was 0.05.

  Table 1 shows the characteristics of the ethylene / α-olefin copolymers (A-1) to (A-3) in Synthesis Examples 1 to 3.

下記実施例および比較例で用いたエチレン・α−オレフィン共重合体および高圧法低密度ポリエチレンの特性を表２に示す。

Table 2 shows the characteristics of the ethylene / α-olefin copolymer and the high-pressure low-density polyethylene used in the following Examples and Comparative Examples.

実施例１
合成例１に示したエチレン・α−オレフィン共重合体（Ａ−１）７０重量％、エチレン・α−オレフィン共重合体（ダウ・ケミカル（株）製 商品名 ＡＦＦＩＮＩＴＹ ＥＧ８１００Ｇ；密度８７０ｋｇ／ｍ^３、ＭＦＲ１．０ｇ／１０分）（以下、（Ｂ−１）という。）１０重量％、高圧ラジカル重合法で得られた低密度ポリエチレン（東ソー（株）製 商品名ペトロセン ３６０；密度９１９ｋｇ／ｍ^３、ＭＦＲ１．６ｇ／１０分）（以下、（Ｃ−１）という。）２０重量％、をタンブラーミキサーにて予備混合した後、シリンダー温度１８０℃に調整した単軸押出機（（株）プラコー製、型式 ＰＤＡ−５０）で溶融混練、造粒し、エチレン系重合体組成物のペレットを得た。得られたペレットは、エチレン系重合体組成物の評価方法に示した方法によりラミネート成形した。 得られたエチレン系重合体組成物の密度、ＭＦＲを測定し、押出ラミネート成形時にネックインと基材接着性の評価を行った。また、離型ライナーの作製に示した方法で積層体を作成し、そのカールを測定した。これらの結果を表３に示す。

Example 1
70% by weight of ethylene / α-olefin copolymer (A-1) shown in Synthesis Example 1, ethylene / α-olefin copolymer (manufactured by Dow Chemical Co., Ltd., trade name: AFFINITY EG8100G; density: 870 kg / m ³ , MFR 1.0 g / 10 min) (hereinafter referred to as (B-1)) 10% by weight, low density polyethylene obtained by a high pressure radical polymerization method (trade name Petrocene 360 manufactured by Tosoh Corp .; density 919 kg / m ³ , MFR 1.6 g / 10 min) (hereinafter referred to as (C-1)) 20% by weight was premixed with a tumbler mixer, and then a single-screw extruder adjusted to a cylinder temperature of 180 ° C. (manufactured by Plako Corporation) The mixture was melt-kneaded and granulated with a model PDA-50) to obtain pellets of an ethylene-based polymer composition. The obtained pellets were laminated by the method shown in Evaluation method for ethylene polymer composition. The density and MFR of the obtained ethylene polymer composition were measured, and the neck-in and substrate adhesion were evaluated during extrusion lamination molding. Moreover, the laminated body was created with the method shown in preparation of a release liner, and the curl was measured. These results are shown in Table 3.

Example 2 to Example 9
Ethylene / α-olefin copolymers (A-1 to A-3) listed in Table 1, ethylene / α-olefin copolymers (B-1 to B-4) listed in Table 2, high pressure method low density Except having carried out with the mixing | blending of Table 3 using polyethylene (C-1 to C-3), it carried out similarly to Example 1, and obtained the pellet of the ethylene-type polymer composition. The density and MFR of the obtained ethylene polymer composition were measured, and the neck-in and substrate adhesion were evaluated during extrusion lamination molding. Moreover, the laminated body was created with the method shown in preparation of a release liner, and the curl was measured. These evaluation results are shown in Table 3.

比較例１
配合比率をＡ−１ ５０重量％、Ｂ−１ ３５重量％、Ｃ−１ １５重量％に変更した以外は実施例１と同様にしてエチレン系重合体組成物のペレットを得た。得られたエチレン系重合体組成物の密度、ＭＦＲを測定し、押出ラミネート成形時にネックインと基材接着性の評価を行った。また、離型ライナーの作製に示した方法で積層体を作成し、そのカールを測定した。結果を表４に示す。得られた積層体はべたつきがあった。

Comparative Example 1
Except having changed the mixture ratio into A-1 50 weight%, B-1 35 weight%, and C-1 15 weight%, it carried out similarly to Example 1, and obtained the pellet of the ethylene-type polymer composition. The density and MFR of the obtained ethylene polymer composition were measured, and the neck-in and substrate adhesion were evaluated during extrusion lamination molding. Moreover, the laminated body was created with the method shown in preparation of a release liner, and the curl was measured. The results are shown in Table 4. The obtained laminate was sticky.

比較例２
配合比率をＡ−２ ８０重量％、Ｃ−１ ２０重量％に変更した以外は実施例１と同様にしてエチレン系重合体組成物のペレットを得た。得られたエチレン系重合体組成物の密度、ＭＦＲを測定し、押出ラミネート成形時にネックインと基材接着性の評価を行った。また、離型ライナーの作製に示した方法で積層体を作成し、そのカールを測定した。結果を表４に示す。得られた積層体は、基材接着性に劣るものであった。

Comparative Example 2
Except having changed the mixture ratio into A-2 80 weight% and C-1 20 weight%, it carried out similarly to Example 1, and obtained the pellet of the ethylene-type polymer composition. The density and MFR of the obtained ethylene polymer composition were measured, and the neck-in and substrate adhesion were evaluated during extrusion lamination molding. Moreover, the laminated body was created with the method shown in preparation of a release liner, and the curl was measured. The results are shown in Table 4. The obtained laminate was inferior in substrate adhesion.

Comparative Example 3
Except having changed the mixture ratio into A-1 78 weight%, B-4 20 weight%, and C-1 2 weight%, it carried out similarly to Example 1, and obtained the pellet of the ethylene-type polymer composition. The density and MFR of the obtained ethylene polymer composition were measured. However, the film was cut during lamination, and a laminate was not obtained.

Comparative Example 4
Except having changed the mixture ratio into A-1 90 weight%, B-4 5 weight%, and C-3 5 weight%, it carried out similarly to Example 1, and obtained the pellet of the ethylene-type polymer composition. The density and MFR of the obtained ethylene polymer composition were measured, and the neck-in and substrate adhesion were evaluated during extrusion lamination molding. Moreover, the laminated body was created with the method shown in preparation of a release liner, and the curl was measured. The results are shown in Table 4. The obtained laminate was inferior in substrate adhesion and curl.

Comparative Example 5
Except having changed the mixture ratio into A-1 40 weight%, B-2 10 weight%, and C-1 50 weight%, it carried out similarly to Example 1, and obtained the pellet of the ethylene-type polymer composition. The density and MFR of the obtained ethylene polymer composition were measured. However, the film was cut during lamination, and a laminate was not obtained.

Comparative Example 6
Except having changed the mixture ratio into A-3 80 weight% and B-2 20 weight%, it carried out similarly to Example 1, and obtained the pellet of the ethylene-type polymer composition. The density and MFR of the obtained ethylene polymer composition were measured. However, the film was cut during lamination, and a laminate was not obtained.

Comparative Example 7
The density and MFR were measured in the same manner as in Example 1 with a blending ratio of C-2 of only 100% by weight, and the neck-in and substrate adhesion were evaluated during extrusion lamination molding. Moreover, the laminated body was created with the method shown in preparation of a release liner, and the curl was measured. The obtained laminate was inferior in substrate adhesion and curl.

Comparative Example 8
The density and MFR were measured in the same manner as in Example 1 except that the blending ratio was C-3 100% by weight, and the neck-in and substrate adhesion were evaluated during extrusion lamination molding. Moreover, the laminated body was created with the method shown in preparation of a release liner, and the curl was measured. The obtained laminate was inferior in substrate adhesion.

Claims (3)

A laminate having at least (A) layer / (B) layer / (C) layer in this order, wherein (A) layer is a release agent layer, and (B) layer has the following requirements (a) to (d) ) Ethylene / α-olefin copolymer (A) 50 to 80% by weight, density 860 kg / m ³ or more and 910 kg / m ³ or less, melt flow rate (hereinafter referred to as MFR) 1 g / 10 min or more 50 g / 10 minutes or less ethylene · alpha-olefin copolymer (B) 3 to 30 wt% and a density 915 kg / ^{m 3} or more 930 kg / ^{m 3} or less, MFR is 1 g / 10 min or more 10 g / 10 minutes or less high-pressure low A layered product comprising a layer made of an ethylene polymer composition comprising 5 to 40% by weight of density polyethylene (C), and the layered product (C) comprising a substrate.
(A) The α-olefin has 3 to 6 carbon atoms
(B) having 0.01 to 0.2 long chain branches having 6 or more carbon atoms per 1000 carbon atoms in the main chain (c) density is 920 kg / m ³ or more and 935 kg / m ³ or less (d) MFR is 5 g / 10 min. To 50 g / 15 min. A release liner comprising the laminate according to claim 1. The base material for adhesive tapes which consists of a laminated body of Claim 1.