JP4367082B2 - Release agent and release sheet - Google Patents

Description

  The present invention relates to a release agent and a release sheet. In the present invention, the term “sheet” used for a release sheet is used as a concept including a film.

  The release film has a release layer on at least one of the substrates, and is widely used to protect the adhesive surface or the adhesive surface. And as a mold release agent which forms a mold release layer, it divides roughly into a silicone type release agent and a non-silicone type release agent.

  Silicone mold release agents are excellent in releasability, but in the field of electronic equipment and electrical equipment, there is a problem of failure (corrosion, contact trouble, etc.) due to a small amount of siloxane-based gas.

The non-silicone release agent includes a release agent whose surface energy is reduced by a halogen compound such as fluoride, and a polyvinyl carbamate (reaction product of PVA and C ₁₈ H ₃₇ NCO) which is a long chain alkyl group-containing polymer. Release agent, release agent comprising a reaction product of polyethyleneimine and C ₁₈ H ₃₇ NCO, release agent comprising a copolymer based on perfluoroalkyl vinyl, release agent comprising a polyethylene resin composition Etc. have been proposed.

  Non-silicone mold release agents do not have the problem of generation of siloxane gas, do not require the use of special catalysts or heat treatment, and can be released just by drying after application, resulting in pot life. There are advantages such as long. However, in general, a non-silicone release agent requires a greater release force than a silicone release agent, or has a poor heat resistance, and the release force increases when stored in a state pasted with an adhesive under heating. There's a problem. Further, the non-silicone release agent has inherent problems depending on the material system to be used as follows.

  For example, a release agent whose surface energy has been reduced by a halogen compound such as fluoride does not meet the current trend where dehalogenation is required to reduce the environmental burden in waste treatment. A mold release agent composed of a copolymer containing perfluoroalkyl vinyl as a main component has excellent mold release properties, but is generally insoluble in organic solvents and only soluble in special and expensive solvents such as FR thinner. Applications are greatly limited.

In addition, the release agent composed of the polyethylene resin composition includes a release agent mainly composed of a low density polyethylene resin (see, for example, Patent Documents 1 and 2) and a release agent mainly composed of a high density polyethylene resin. There is a mold agent (see, for example, Patent Documents 3 and 4), and a release agent mainly composed of a low-density polyethylene resin requires a large peeling force. When used as a pressure-sensitive adhesive layer protective film, There is a problem that a part of the adhesive layer is transferred to the surface of the release layer, or that the surface of the adhesive layer after peeling has a pulse shape and causes peeling called stick-slip. A mold release agent mainly composed of a high-density polyethylene-based resin has a problem that it is inferior in adhesion to a base material when a polar polymer is used as a base material and has a large peeling force.
Japanese Patent Publication No.51-20205 Japanese National Patent Publication No. 11-508958 JP 2000-239624 A JP 2000-119411 A

  The present invention has been made in view of the above circumstances, and its purpose is not to include a silicone-based gas component, and has a good releasability with respect to various pressure-sensitive adhesives, and has a small variation in peeling force. And it aims at providing the mold release agent and mold release sheet which can hold | maintain a low peeling force even after sticking with an adhesive and putting it under heating.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors easily achieved the above object by using a release agent mainly composed of a low-density olefin elastomer and a high-density ethylene-α-olefin polymer. As a result, the present invention has been completed.

  That is, the first gist of the present invention is that the component (A): an olefin elastomer having a density of 0.855 g / cc or more and less than 0.868 g / cc and the component (B): a density of 0.868 g / cc or more and 0. A release agent mainly composed of an ethylene-α-olefin copolymer of 970 g / cc or less, wherein the difference between the average density of component (A) and the average density of component (B) is 0.005 g / It is cc or more and exists in the mold release agent characterized by the compounding ratio (weight ratio) of a component (A): component (B) being 90: 10-10: 90. In a preferred embodiment of the present invention, the component (A) is a copolymer of at least one selected from the group of propylene, butene and hexene and ethylene, and the component (A) and / or the component (B) ) Has a functional group, and the component (A) and the component (B) have an endothermic peak of 1 J / g or more as measured with a differential scanning calorimeter in a temperature range of 0 to 200 ° C.

  The second gist of the present invention resides in a release sheet characterized by having a release layer composed of the above release agent on at least one side of a substrate. And in a preferable aspect, a mold release layer consists of a mold release agent obtained by the crosslinking reaction with the reactive compound which can react with the functional group which component (A) or component (B) has.

  The mold release agent of the present invention does not contain contaminating silicone, has no problem of workability such as coating, has heat resistance, and has excellent mold release performance on the adhesive surface. It fully satisfies the required characteristics.

  First, the release agent of the present invention will be described. The component (A): olefin elastomer used in the present invention is an olefin elastomer having a density density of 0.855 g / cc or more and less than 0.868 g / cc. When the density of the component (A) is too small, the release force of the obtained release agent is increased, and sufficient release properties cannot be obtained. If the density of the component (A) is too large, depending on the balance with the component (B): ethylene-α-olefin copolymer described later, the release force of the obtained release agent tends to increase, and sufficient Releasability cannot be obtained.

  The component (B): ethylene-α-olefin copolymer used in the present invention is an ethylene-α-olefin copolymer having a density of 0.868 g / cc to 0.970 g / cc. If the density of the component (B) is too small, the heat resistance and coating strength of the obtained release agent will be insufficient. Moreover, when the density of a component (B) is too large, depending on balance with a component (A), it will become the tendency for the peeling force of the mold release agent to become large, and sufficient mold release property will not be acquired.

  By the way, in general, the density of a polymer depends on crystallinity. The density of the crystallized part of the polymer is high. And the crystallinity of a polymer can be evaluated by the size of an endothermic peak of a differential scanning calorimeter (DSC) in the following manner.

  Using “DSC7” manufactured by Perkin Elmer as a measuring device, in accordance with JIS K 7122-1987 “Method of measuring the transition heat of plastic” 3 (2) “When measuring heat of fusion after a certain heat treatment” taking measurement. The measurement conditions are as shown in Table 1 below.

  The measurement device is adjusted as follows. In other words, prepare two empty aluminum pans with approximately the same mass, place them on two sample holders, measure them under the same conditions as in the actual case, and adjust the measuring device so that the baseline is a straight line. I do.

  The sample is prepared as follows. That is, a sample is sandwiched between Teflon sheets, formed into a film having a thickness of 250 μm with a compression molding machine heated to 200 ° C., and then cooled and solidified with a press molding machine maintained at 25 ° C. Is left to stand at 25 ° C. for 1 day and subjected to DSC measurement. By such an operation, a sample having a constant thermal history after polymerization can be obtained.

  The method of drawing the baseline for the endothermic peak is performed as shown in FIGS. 1A to 1C according to the shape of the endothermic peak. FIG. 1 is an explanatory diagram of how to draw a baseline with respect to an endothermic peak obtained by DSC measurement.

  (A) is a case where the end point of the endothermic peak exists on the same base and the base line is a straight line. In this case, a linear base line connecting the start point and the end point is drawn, the peak area is obtained, and the heat absorption amount is obtained.

  (B) is the case where the start point and end point of the endothermic peak do not exist on the same base, and the straight line extrapolated from the start point side in the peak direction intersects with the straight line extrapolated from the end point to the peak direction. is there. In this field, a curved base line that can overlap the starting point side line and the ending point side line to the maximum is drawn, the peak area is obtained, and the endothermic amount is obtained.

  (C) is the case where the start point and end point of the endothermic peak do not exist on the same base, and the straight line extrapolated from the start point side in the peak direction and the straight line extrapolated from the end point to the peak direction do not intersect. is there. In this case, a linear base line connecting the start point and the end point is drawn, the peak area is obtained, and the heat absorption amount is obtained. The endothermic amount when the end point of the endothermic peak is 0 ° C. or less and the end point exceeds 0 ° C. is the amount expressed from 0 ° C. to the end point (the region below 0 ° C. is cut).

  In a preferred embodiment of the present invention, from the viewpoint of heat resistance, a crystalline polymer exhibiting an endothermic peak of 1 J / g or more is used in a temperature range of 0 to 200 ° C. by DSC.

  The lower limit (about 0.855 g / cc) of the density of the component (A) is particularly when the component (A) is a copolymer of ethylene and one or more selected from the group of propylene, butene and hexene. The lower limit of the density of the component (A) is about 0.860 g / cc from the viewpoint of crystallinity. The component (B) is much richer in crystallinity than the component (A).

  The mold release agent of the present invention comprising the components (A) and (B) having the crystallinity as described above as a main component has increased cohesive force due to the presence of an agglomerated phase based on the crystallized portion, and has heat resistance. In addition, it has excellent scratch resistance. The endothermic peak of the component (A) in the DSC measurement is preferably 1 to 50 J / g, more preferably 3 to 30 J / g. When the endothermic peak of component (A) exceeds 30 J / g, the crystallinity is too high and the release agent tends to be hard. On the other hand, the endothermic peak of the component (B) in the DSC measurement is preferably 30 to 250 J / g, more preferably 35 to 200 J / g. When the endothermic peak of component (B) is less than 30 J / g, there is a tendency that a thermally stable release agent cannot be obtained. When the endothermic peak of component (B) exceeds 250 J / g, there is too much difference in relative crystallinity with component (A), and component (B) crystallizes first in the melting crystallization process and component (B) There is a tendency to separate from A), and a release agent having excellent heat resistance cannot be obtained.

  Component (A): The olefin-based elastomer has a small peeling force and excellent releasability, but is inferior in heat resistance and coating strength. On the other hand, the component (B): ethylene-α-olefin copolymer has a large peeling force and is inferior in releasability, but is excellent in heat resistance and film strength. In order to develop both the releasability of component (A) and the heat resistance of component (B), the difference (Δρ) between the average density of component (A) and the average density of component (B) is set to 0. 0.005 g / cc or more, preferably 0.01 g / cc or more. When the average density difference (Δρ) is too small, the release agent composed mainly of the component (A) and the component (B) cannot maintain a balance between the release property and the heat resistance.

  In the present invention, the blending ratio (weight ratio) of component (A): component (B) needs to be 90:10 to 10:90. That is, as described above, the mold release agent of the present invention increases the heat resistance by using a component having crystallinity, and by selecting the density of component (A): component (B) in an appropriate range, Maintains a balance between heat resistance and releasability, but further improves the balance between heat resistance and releasability by defining the compounding ratio of component (A): component (B) as described above. It is a thing. That is, when the blending ratio of the component (A) exceeds 90 weight ratio, the heat resistance is lowered because the component (A) which is a low density component, that is, a low melting point component is too much, and the blending ratio of the component (B) When the ratio exceeds 90 weight ratio, the component (B), which is a high-density component, is too much, so that it becomes hard and causes a problem in terms of cohesion. The compounding ratio (weight ratio) of component (A): component (B) is preferably 80:20 to 40:60.

  As a method of adjusting the peeling force by the olefin-based elastomer, not only a method of adjusting the compounding ratio but also various methods can be adopted. As such a method, (1) a method of adjusting the crystallinity and the glass transition temperature by appropriately controlling the stereoregularity of the olefin elastomer and the ethylene-α-olefin copolymer, and (2) carrying out the copolymerization. And a method for controlling the crystallinity and the glass transition temperature.

  When the glass transition temperature and elastic modulus of the release layer are excessively increased, the film strength of the release layer is improved, but the peeling force is increased and the flexibility (secondary workability) of the release layer is lowered. When the glass transition temperature and the elastic modulus of the release layer are excessively lowered, the peeling force is reduced and the release property is improved, but the film strength of the release layer is lowered.

  As said olefin type elastomer, the polymer copolymerized with the other reactive monomer by using an olefin as a main component other than the olefin homopolymer can be used. Specific examples of the olefin elastomer include homopolymers and copolymers of α-olefins such as ethylene, propylene, butene, hexene and octene. Moreover, the copolymer of alpha-olefins, such as ethylidene norbornene and norbornene, and ethylene, is also mentioned.

  Also, hydrocarbon elastomers such as diene rubber obtained by living polymerization represented by polyisoprene, hydrogenated products thereof, and elastomers obtained by ring-opening polymerization of cyclic olefins can be used. Examples of the olefin polymer obtained by ring-opening polymerization of a cyclic olefin include ring-opening polymers of alicyclic olefins such as cyclopentene, cyclooctene and norbornene. Furthermore, polyolefin obtained by hydrogenation such as a nuclear hydrogenated product of a styrene / diene copolymer or a nuclear hydrogenated product of a styrene isoprene copolymer can be used. A composition comprising a plurality of olefinic elastomers may be used.

  In the present invention, it is preferable to use an olefin elastomer obtained by polymerization using a metallocene catalyst and a vanadium catalyst. If polymerization is performed using a metallocene catalyst, an olefin-based elastomer having a narrow molecular weight distribution and few low molecular weight components can be obtained. In addition, if a catalyst such as that described above is used, uniform copolymerization is possible, and generation of low molecular weight components whose comonomer content is significantly different from the average composition can be suppressed. For this reason, the stickiness of the release layer can be suppressed, and the gelation can be efficiently performed in the crosslinking reaction for imparting chemical resistance to the release layer, and the release layer has high chemical resistance. A layer is obtained.

  On the other hand, the ethylene α-olefin copolymer is not particularly limited as long as it has a density higher than that of the olefin elastomer and contains the ethylene α-olefin copolymer as a main component. A copolymer and multi-component copolymer of ethylene and one or more α-olefins selected from the group of propylene, butene, and hexene may be used as long as they have units of ethylene and α-olefin in the molecular structure. Coalescence is preferred. In addition, a copolymer of ethylidene norbornene, norbornene or the like and an α-olefin such as ethylene is also included within the range in which the releasability is not impaired. The amount of ethylene contained in the ethylene α-olefin copolymer is usually 30 mol% or more, preferably 50 to 95 mol%.

  In the present invention, the ethylene α-olefin copolymer may be a polymer obtained using any catalyst such as a metallocene catalyst, a Ziegler-Natta catalyst, or a vanadium catalyst, but is obtained by using a metallocene catalyst. Multi-component copolymers with ethylene are preferred. If polymerization is performed using a metallocene catalyst, an olefin-based elastomer having a narrow molecular weight distribution and few low molecular weight components can be obtained. Moreover, if a metallocene catalyst is used, uniform copolymerization is possible and the production | generation of the low molecular-weight component from which a comonomer content is remarkably different from an average composition can be suppressed. For this reason, the stickiness of the release layer can be suppressed, and efficient gelation is possible in the crosslinking reaction for imparting chemical resistance to the coating film, and the heat resistance and coating film strength are high. A release agent is obtained.

  Moreover, the manufacturing method of an olefin-type elastomer and an ethylene alpha-olefin copolymer is not specifically limited, You may use solution polymerization, vapor phase polymerization, slurry polymerization, high pressure polymerization, block polymerization (bulk), etc. Regardless of whether the monomer type is gas or liquid, the polymerization method may be such that the monomer is enclosed in advance in the polymerization system, and the monomer is fed at a constant rate during the polymerization, or the pressure in the polymerization system is kept constant. The monomer may be fed so as to maintain the temperature.

  Specific examples of the metallocene catalyst include rac-isopropylidenebis (1-indenyl) zirconium dichloride, rac-dimethylsilylbis-1- (2-methylindenyl) zirconium dichloride, rac-dimethylsilylbis-1- (2- Methyl-4-phenylindenyl) zirconium dichloride, rac-dimethylsilylbis-1- (2-methyl-4.5-benzoindenyl) zirconium dichloride, isopropylidene-9-fluorenylcyclopentadienylzirconium dichloride, etc. Can be mentioned.

  Specific examples of Ziegler-Natta catalysts include titanium trichloride and magnesium chloride-supported titanium tetrachloride, which are currently used industrially. Specific examples of vanadium catalysts include vanadium oxytrichloride and alkoxy. Examples thereof include (monoethoxy) oxyvanadium dichloride and (diethoxy) oxyvanadium chloride having a group. The co-catalyst components used in combination with these are trialkylaluminum such as trimethylaluminum, triethylaluminum and triisobutylaluminum, dialkylmonohaloaluminum such as diethylaluminum chloride, monoalkyldihaloaluminum such as ethylaluminum dichloride, ethyl Examples thereof include sesquialuminum compounds such as aluminum sesquihalide.

  In the present invention, a blend of component (A): olefin elastomer and component (B): ethylene α-olefin copolymer can be used directly as a release agent. Moreover, the mold release agent excellent in base-material adhesiveness can be obtained by providing a functional group to one or both of the above. Furthermore, by partially cross-linking the release agent component, it is possible to sufficiently suppress the transfer to the adhesive surface of the release agent layer, as well as excellent heat resistance, chemical resistance, and film strength in addition to substrate adhesion. A mold release agent can be realized.

  The modified olefin elastomer having a functional group has a structure in which a functional group is introduced into the olefin elastomer. The modified olefin elastomer may be used alone or in combination with the olefin elastomer. Examples of the functional group herein include a functional group having reactivity such as an epoxy group, a succinic anhydride group, a carboxyl group, a hydroxyl group, an amine group, an isocyanate group, and a hydroxyphenyl group, as well as a vinyl group and an isopropenyl group. , Groups having an unsaturated bond such as (meth) acrylate group and allyl group. The modified olefin elastomer can be obtained by a method of adding a reactive monomer having a functional group to the olefin elastomer.

  On the other hand, the modified ethylene α-olefin copolymer having a functional group has a structure in which a functional group is introduced into the ethylene α-olefin copolymer described above. The modified ethylene α-olefin copolymer may be used alone or in combination with a modified ethylene α-olefin copolymer or ethylene α-olefin copolymer having different functional groups. Examples of the functional group herein include the same groups as in the case of the modified olefin elastomer. The modified ethylene α-olefin copolymer can be obtained by a method in which a reactive monomer having a functional group is added to the ethylene α-olefin copolymer in the presence of peroxide.

  When crosslinking is performed using a functional group, the maximum content of the functional group contained in the composition is usually 5% by weight, preferably 1% by weight. When the amount of the functional group is more than 5% by weight, the low releasability that is produced by the olefin elastomer and the ethylene α-olefin copolymer may be impaired. The minimum content of functional groups contained in the composition is usually 0.001% by weight, preferably 0.01% by weight.

  The release agent of the present invention may contain a crosslinking agent. In this invention, it is preferable to use the crosslinking agent and organic peroxide which have a functional group.

  Examples of the crosslinking agent having a functional group include a compound having at least two functional groups capable of reacting with a modified olefin elastomer having a functional group and / or an ethylene α-olefin copolymer. Such a compound may be a low molecular compound or a modified olefin elastomer and / or a modified ethylene α-olefin copolymer having a functional group capable of crosslinking reaction. The addition amount of the crosslinking agent is usually 0.1 to 10, preferably 0.5 to 2, as a molar ratio (elastomer / crosslinking agent) between the functional group of the elastomer and the functional group of the crosslinking agent that reacts with the functional group. is there. When the ratio of the functional groups is out of the range of 0.1 to 10, many unreacted functional groups may remain and cause an increase in peeling force.

  As the organic peroxide, general peroxides such as ketone peroxide, hydroperoxide, and diacyl peroxide can be used. When crosslinking is performed using a peroxide, it is preferable to use an olefin-based elastomer containing a reactive double bond or ethylene. The amount of peroxide added is usually 0.01 to 3 parts by weight, preferably 0.1 to 1 part by weight, based on 100 parts by weight of the release agent composition.

  In the present invention, any additive may be added as long as it does not impair the release agent characteristics. For example, peeling aids typified by paraffin wax, process oils that are plasticizers, anti-blocking agents, antioxidants, UV absorbers, antistatic agents, lubricants, dispersants, nucleating agents, colorants, corrosion inhibitors Etc. can be appropriately added depending on the purpose. Furthermore, a copolymer of an α-olefin and a compound having a functional group may be added as necessary for the purpose of improving the adhesion of the substrate and the crosslinking efficiency.

  The release agent of the present invention may be formed as a release layer on the substrate by dissolving it in a solvent and then applying to the substrate surface and drying, or laminating the substrate in a molten state, A release sheet can be obtained by using a method of co-extrusion with a substrate.

  Next, the release sheet of the present invention will be described. The release sheet of the present invention is characterized by having a release layer composed of the above release agent on at least one surface of a substrate.

  The base material is not limited as long as it is a material having a function of supporting the release layer. For example, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyolefins such as polypropylene and polymethylpentene, plastic films such as polycarbonate, aluminum And metal foils such as stainless steel, glassine paper, fine paper, coated paper, impregnated paper, paper such as synthetic paper, and non-woven fabric.

  Among the above, a plastic film is preferable. Further, so-called dust-free paper (see, for example, Japanese Patent Publication No. 6-11959) with less dust generation is also preferable. When the substrate is made of a plastic film or dust-free paper, dust and the like are hardly generated during processing and use, and it is difficult to adversely affect electronic devices such as a hard disk device. Further, when the substrate is made of a plastic film or dust-free paper, cutting or punching during processing becomes easy. Moreover, when using a plastic film for a base material, the material has a preferable polyethylene terephthalate. The polyethylene terephthalate film has the advantages that it generates less dust and generates less gas during heating.

  Although the thickness of a base material is not specifically limited, Usually, 10-200 micrometers, Preferably it is 25-50 micrometers. The substrate used in the present invention may be subjected to corona treatment, plasma treatment, flame plasma treatment, and the like. Moreover, in order to obtain adhesiveness with the release layer, a multilayer structure may be provided by providing a primer layer, an anchor coat layer, or the like.

  The thickness of the release layer is usually 0.01 to 5 μm, preferably 0.1 to 5 μm, when a release layer is provided by applying a solution on a substrate. If the thickness is less than 0.1 μm, the peeling force increases due to the influence of the substrate, and if it exceeds 5 μm, the coating tends to be peeled off from the substrate. Moreover, the thickness of a mold release layer in the case of providing a mold release layer on a base material using a molten liquid is 0.1-100 micrometers normally, Preferably it is 0.1-50 micrometers. However, although it depends on the molding apparatus, in general, when the thickness is less than 0.1 mμ, problems such as increased film thickness non-uniformity occur. Therefore, in the present invention, the film may be thinned by a process of laminating a release layer on a substrate, or a method of stretching and rolling uniaxially or multiaxially after lamination. According to such a method, a release layer having a thickness of less than 0.1 μm can be formed.

  The release sheet of the present invention can be used for various applications and can also be used for an adhesive surface. In particular, the release sheet of the present invention is preferably used for a semiconductor or ceramic green sheet manufacturing process, an adhesive tape, a surface protective film, a laminated container, and the like.

  The kind of adhesive surface to which the release sheet of the present invention is applied is not particularly limited. Examples of the surface of the material to which the release agent of the present invention exhibits releasability include an adhesive surface composed of the following adhesives. For example, rubber adhesives, acrylic adhesives, urethane adhesives, silicone adhesives, vinyl adhesives, and other various adhesives that are generally known. One-component, two-component, and emulsion-type adhesives Any pressure-sensitive adhesive may be used (for example, see “Encyclopedia of Adhesion / Tackiness” (supervised by Shozaburo Yamaguchi, published by Asakura Shoten, p 118-169, 1993))

  Since an adhesive tape for electronic equipment is required to have low outgassing properties and reliability of adhesion, it is preferable to use an acrylic adhesive.

  The acrylic pressure-sensitive adhesive is mainly composed of an acrylic polymer obtained by a conventional polymerization method such as a solution polymerization method, an emulsion polymerization method, an ultraviolet polymerization method, and a crosslinking agent, a tackifier, a softening agent, and an aging agent as necessary. It can be prepared by adding various additives such as inhibitors and fillers.

  Examples of the acrylic pressure-sensitive adhesive include ethyl (meth) acrylate, butyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and isooctyl (meth) acrylate. , Alkyl (meth) acrylates such as isononyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate (preferably an alkyl (meth) having about 2 to 12 carbon atoms (particularly about 4 to 10 carbon atoms) ) Acrylate) as a main component, and a monomer for modification which can be copolymerized therewith if necessary (for example, a hydroxyl group-containing monomer such as hydroxyalkyl (meth) acrylate; a cyano group-containing monomer such as acrylonitrile; acrylamide; Substituted acrylamide, etc. Amide group-containing monomer, vinyl esters such as vinyl acetate; a copolymer of an aromatic vinyl compound such as styrene, etc.) a monomer mixture was added is used.

  For example, the release sheet of the present invention is a release film for an adhesive sheet such as an adhesive sheet for surface protection or an adhesive sheet for dicing used when processing a silicon wafer used for a semiconductor integrated circuit (IC) or the like. Can be used. Moreover, the release sheet of this invention can also be used as a release film for semiconductor resin sealing. That is, the release sheet of the present invention can be used between the sealed surface of the semiconductor chip and the mold.

  When manufacturing a ceramic green sheet, a ceramic slurry can be applied on the release layer of the release sheet of the present invention. Thus, the green sheet formed on the release sheet of the present invention can be provided with an electrode made of palladium, silver, nickel or the like, for example, by screen printing. Moreover, after performing such processing, a multilayer structure can be formed by repeating the process of coating the ceramic slurry again on the ceramic green sheet and providing an electrode. After performing these steps as appropriate, the release sheet is peeled off from the green sheet, laminated and cut into chips as appropriate, and then fired and processed to produce capacitors, multilayer inductor elements, piezoelectric components, thermistors, varistors, etc. Ceramic electronic parts can be obtained.

  The release sheet of the present invention is used, for example, as an adhesive sheet or an adhesive tape mount, or as a surface protective film for protecting a coated steel sheet of automobiles, building materials, etc. I can do it.

  By forming a laminated sheet containing the release sheet of the present invention on at least one surface, a container in which various pressure-sensitive adhesive display labels can be easily applied and removed can be obtained. As a preferable production method of the laminated container, there are a method of laminating in a molten or semi-molten state such as a sheet thermoforming method, a blow molding method, a multi-layer injection molding method by two-color molding or sandwich molding.

  Further, a predetermined film or sheet having the release agent of the present invention on the surface layer is separately prepared and thermally laminated, that is, inserted into a mold at the time of molding and thermally fused to the surface. The method of using a laminated container is mentioned. For example, in a thermoformed container by sheet molding, there is a method including a step of forming a surface layer and an inner layer in contact with the sheet by melt extrusion from a die into a sheet. The method for laminating each layer may be any method as long as the resin material for forming each layer is laminated in a molten state before being extruded from a die. In general, a multi-manifold system in which each material is melt-kneaded by each extruder and then stacked in a die, or a feed block system (combining adapter system) in which the material is stacked before flowing into the die may be used. Examples of the shape of the container include various cups, trays, dishes, bowls and the like.

  Here, thermoforming is a method in which a sheet or the like is heated and softened and then formed into a mold shape. As a forming method, use vacuum or compressed air, and if necessary, use a plug together to form into a mold shape (straight method, drape method, air slip method, snapback method, plug assist method, etc.) And a press molding method. Conditions such as temperature at the time of thermoforming, degree of vacuum, compressed air pressure, and forming speed are appropriately set depending on the shape of the plug, the shape of the mold or the raw material sheet.

  Containers obtained by thermoforming are used for the contents of milk drinks and various food containers, as well as various dairy products specified in the “Ministerial Ordinance on Milk and Dairy Product Component Standards” (Ministerial Ordinance on Milk, etc.). On the other hand, it has very little effect on odor and taste, and has excellent rigidity, heat resistance, and impact characteristics.

  Moreover, according to the blow molding method, the polymer described above is obtained by blow molding using at least the container surface layer. The molding can be performed by a known method, and is molded by a direct blow method, an injection blow method, a hot stretch blow method, a cold stretch blow method, or the like. In the direct blow method, each layer material is extruded simultaneously from a plurality of extruders, the multilayer parison is injected using a multilayer die, and the parison is closed and shaped by a mold, while the injection blow is performed. In the method, the hot stretch blow method and the cold stretch blow method, it is obtained by heating and shaping using a multilayer preform.

  Specific examples include containers such as milk containers, fermented milk containers, lactic acid beverage containers, milk drinks, and similar products. Beverage containers include mineral water containers, tea containers, juice containers, cola containers, and food containers include salad oil containers, ketchup containers, mayonnaise containers, lemon juice containers, sauce containers, soy sauce containers, and the like. .

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example, unless the summary is exceeded.

Production Example 1:
700L of SUS pressurized polymerization kettle replaced with nitrogen was charged with 700L of degassed and dehydrated n-hexane, and dried ethylene gas, propylene gas and hydrogen gas were fed at a volume ratio of 6/4/1 and stirred. The solution was dissolved for 60 minutes at room temperature. Next, 5 mol of ethylaluminum sesquichloride (Al ₂ Et ₃ Cl ₃ ) and 0.5 mol of VOCl ₃ were charged into this, and polymerization was performed at 35 ° C. for 1 hour while maintaining the mixed gas at 0.5 MPa. Thereafter, the catalyst was deactivated with isopropyl alcohol to terminate the polymerization.

  After the solvent 400L was distilled off and concentrated from the obtained copolymer solution under reduced pressure, it was transferred to a kneader and introduced into an extruder while the solvent was distilled off under heating and reduced pressure. , Sometimes referred to as “olefinic elastomer (1)”). The composition molar ratio of the product determined by H-NMR is ethylene / propylene = 80/20, the weight average molecular weight of the product determined by GPC is 131,000, the molecular weight distribution is 2.5, and the density is 0.860 g / cc. Met. The density is a value measured using a density gradient tube in a water-ethanol liquid system according to JIS K7112 D method (hereinafter the same). Moreover, the heat of fusion in the range of 0-200 degreeC measured by DSC was 8 J / g. DSC measurement was performed according to the method described in the text of the specification (hereinafter the same).

Production Example 2:
In Production Example 1, except that the ratio of ethylene, propylene, and hydrogen gas was changed to 6/4/2, the same operation as in Production Example 1 was performed to obtain an ethylene-propylene copolymer (hereinafter referred to as “olefin elastomer (2)”. 39kg) was obtained. The composition molar ratio of the product determined by H-NMR is ethylene / propylene = 81/19, the weight average molecular weight of the product determined by GPC is 100,000, the molecular weight distribution is 2.5, and the density is 0.860 g / cc. Met. The heat of fusion in the range of 0 to 200 ° C. measured by DSC was 11 J / g.

Production Example 3:
A 1000 L pressure polymerization kettle made of SUS was replaced with a mixed gas of ethylene and propylene (partial pressure ratio 85/15), and 750 L of deaerated and dried toluene was added. The system was charged with 100 mol of a methylalumoxane toluene solution manufactured by Witco as an Al component and stirred at 70 ° C. for 30 minutes, and then 0.1 mol of a metallocene catalyst (dimethylsilylene biscyclopentadienylzirconium dichloride) was added, and the above ethylene and propylene were added. The mixture was pressurized to 0.7 MPa with a mixed gas of and polymerized for 2 hours. Thereafter, the polymerization was stopped with isopropyl alcohol.

  400 L of solvent was distilled off from the obtained copolymer solution under reduced pressure and concentrated, and then transferred to a kneader and introduced into an extruder while distilling off the solvent under heating and reduced pressure. 33 kg of coalescence (hereinafter also referred to as “olefin elastomer (3)”) was obtained. The composition molar ratio of the product determined by H-NMR is ethylene / propylene = 89/11, the weight average molecular weight of the product determined by GPC is 101,000, the molecular weight distribution is 2.3, and the density is 0.867 g / cc. Met. The heat of fusion in the range of 0 to 200 ° C. measured by DSC was 20 J / g.

Production Example 4:
A 1000 L pressure polymerization kettle made of SUS was replaced with a mixed gas of ethylene and 1-butene (partial pressure ratio 65/35), and 650 L of deaerated and dried toluene was added. The system was charged with 100 mol of a methylalumoxane toluene solution manufactured by Witco as an Al component and stirred at 70 ° C. for 30 minutes, and then 0.1 mol of a metallocene catalyst (dimethylsilylenebis (1-indenyl) zirconium dichloride) was added, and the above ethylene and Pressurized and maintained at 0.8 MPa with a mixed gas of 1-butene and polymerized for 2 hours. Thereafter, the polymerization was stopped with isopropyl alcohol.

  400 L of solvent was distilled off from the obtained copolymer solution under reduced pressure and concentrated, and then transferred to a kneader and introduced into an extruder while distilling off the solvent under heating and reduced pressure. 36 kg of coalescence (hereinafter also referred to as “olefin elastomer (4)”) was obtained. The compositional molar ratio of the product determined by H-NMR is ethylene / butene = 80/20, the weight average molecular weight of the product determined by GPC is 78,900, the molecular weight distribution is 2.4, and the density is 0.861 g / cc. Met. The heat of fusion in the range of 0 to 200 ° C. measured by DSC was 12 J / g.

Production Example 5:
The 1 L autoclave was replaced with a mixed gas of ethylene and propylene (partial pressure ratio 25/75), and 450 mL of deaerated and dried toluene was added. The system was charged with 100 mmol of a methylalumoxane toluene solution manufactured by Witco as Al content and stirred at 75 ° C. for 10 minutes, and then 0.1 mmol of a metallocene catalyst (dimethylsilylenebis (1-indenyl) zirconium dichloride) was added, and the above ethylene and Pressurized and maintained at 0.95 MPa with a mixed gas of propylene and polymerized for 2 hours.

  Thereafter, the polymerization is stopped with isopropyl alcohol, reprecipitated in methanol, filtered, dried under reduced pressure at 70 ° C., and 24 g of an ethylene-propylene random copolymer (hereinafter sometimes referred to as “olefin elastomer (5)”). Got. The composition molar ratio of the product determined by H-NMR is ethylene / propylene = 41/59, the weight average molecular weight of the product determined by GPC is 212,500, the molecular weight distribution is 3.3, and the density is 0.863 g / cc. Met. The heat of fusion in the range of 0 to 200 ° C. measured by DSC was 7 J / g. In this heat measurement, two endothermic peaks represented by a heterogeneous polymer are obtained, and the heat of fusion 7 J / g is the sum of the values of the two peaks.

Production Example 6:
40 g of the ethylene propylene random copolymer obtained in Production Example 1, 1.2 g of 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA), and 2,5-dimethyl-2,5-di-t-butylperoxy as a radical initiator After dry blending 0.06 g of hexane, a lab plast mill kneader (manufactured by Toyo Seiki Seisakusho) is used and kneaded for 3 minutes at a reaction temperature of 180 ° C. and at a rotation speed of 100 rpm. A coalescence (hereinafter sometimes referred to as “HEMA-modified olefin elastomer (1)”) was obtained. This polymer was press-molded into a film, and quantified using a calibration curve prepared by the characteristic absorption of a carbonyl group of 1724 cm ⁻¹ separately with an FT-IR spectrum. The HEMA content was 0.9% by weight (ie, The hydroxyl group content was 0.12% by weight). The density was 0.861 g / cc and the molecular weight was 150,000. The heat of fusion in the range of 0 to 200 ° C. measured by DSC was 10 J / g.

Production Example 7:
The 1 L autoclave was replaced with an ethylene / butene-1 / propylene mixed gas (partial pressure ratio 65/25/10), and 450 mL of deaerated and dried toluene was added. The system was charged with 100 mmol of a methylalumoxane toluene solution manufactured by Witco as Al content and stirred at 75 ° C. for 10 minutes, and then 0.1 mmol of a metallocene catalyst (dimethylsilylenebis (1-indenyl) zirconium dichloride) was added, and the above ethylene and The mixture was maintained under pressure at 0.95 MPa with a mixed gas of Ten-1 and propylene and polymerized for 2 hours.

  Thereafter, the polymerization is stopped with isopropyl alcohol, reprecipitated in methanol, filtered, dried under reduced pressure at 70 ° C., and referred to as an ethylene / butene-1 / propylene random copolymer (hereinafter referred to as “olefin elastomer (6)”). 24g was obtained. The composition molar ratio of the product determined by H-NMR is ethylene / butene-1 / propylene = 64/22/14, the weight average molecular weight of the product determined by GPC is 340,000, the molecular weight distribution is 1.9, and the density Was 0.860 g / cc. There was no heat of fusion peak in the range of 0-200 ° C as measured by DSC.

Production Example 8:
A 1000 L pressure polymerization kettle made of SUS was replaced with ethylene gas, and 650 L of deaerated and dried toluene, and 30 kg of 1-hexene that was also deaerated and dried were charged. The system was charged with 150 mol of a methylalumoxane toluene solution manufactured by Witco as an Al component, stirred at 70 ° C. for 30 minutes, 0.1 mol of a metallocene catalyst (dimethylsilylene biscyclopentadienylzirconium dichloride) was added, and ethylene gas was charged with 0. Pressurized to 5 MPa and polymerized for 3 hours. Thereafter, the polymerization was stopped with isopropyl alcohol.

  After removing 450 L of the solvent from the resulting copolymer solution under reduced pressure and concentrating, it was transferred to a kneader and introduced into the extruder while distilling off the solvent under heating and reduced pressure. 38 kg of a combination (hereinafter sometimes referred to as “ethylene-α-olefin copolymer (1)”) was obtained. The compositional molar ratio of the product determined by H-NMR is ethylene / hexene = 90/10, the weight average molecular weight of the product determined by GPC is 70,100, the molecular weight distribution is 2.3, and the density is 0.880 g / cc. Met. The heat of fusion in the range of 0 to 200 ° C. measured by DSC was 40 J / g.

Production Example 9:
In Production Example 8, the procedure was the same as in Production Example 8, except that the amount of 1-hexene was 25 kg, the reaction temperature was 85 ° C., the ethylene pressure was 0.85 MPa, and the polymerization time was 2.5 hours. 34 kg of a copolymer (hereinafter sometimes referred to as “ethylene-α-olefin copolymer (2)”) was obtained. The composition molar ratio of the product determined by H-NMR is ethylene / hexene = 93/7, the weight average molecular weight of the product determined by GPC is 51,300, the molecular weight distribution is 2.4, and the density is 0.898 g / cc. Met. The heat of fusion in the range of 0 to 200 ° C. measured by DSC was 78 J / g.

Production Example 10:
A 1000 L SUS pressure polymerization kettle was replaced with propylene gas, and 650 L of deaerated and dried toluene was added. The system was charged with 200 mol of a methylalumoxane toluene solution manufactured by Witco as an Al component and stirred at 75 ° C. for 45 minutes, then 0.15 mol of a metallocene catalyst (dimethylsilylenebis (1-indenyl) hafnium dichloride) was added, and propylene 1. Polymerization was carried out for 2 hours by feeding at a constant rate of 5 kg / hour and ethylene of 20 kg / hour. Thereafter, the polymerization was stopped with isopropyl alcohol.

  After removing 450 L of the solvent from the copolymerized solution under reduced pressure and concentrating, the mixture was transferred to a kneader and introduced into the extruder while distilling off the solvent under heating and reduced pressure. 39 kg of coalescence (hereinafter sometimes referred to as “ethylene-α-olefin copolymer (3)”) was obtained. The composition molar ratio of the product determined by H-NMR is ethylene / propylene = 97/3, the weight average molecular weight of the product determined by GPC is 102,500, the molecular weight distribution is 2.2, and the density is 0.900 g / cc. Met. The heat of fusion in the range of 0 to 200 ° C. measured by DSC was 150 J / g.

Production Example 11:
The 1 L autoclave was replaced with propylene gas, and 450 mL of deaerated and dried toluene was added. The system was charged with 200 mmol of a methylalumoxane toluene solution manufactured by Witco as an Al component and stirred at 75 ° C. for 15 minutes, and then 0.15 mmol of a metallocene catalyst (dimethylsilylenebis (1-indenyl) zirconium dichloride) was added, and 1 g of propylene was added. The polymer was polymerized for 2 hours by feeding at a constant speed of 40 g / hour of ethylene.

  Thereafter, the polymerization is stopped with isopropyl alcohol, reprecipitated in methanol, filtered, dried under reduced pressure at 70 ° C., and 24 g of an ethylene-propylene random copolymer (hereinafter sometimes referred to as “olefin elastomer (4)”). Got. The composition molar ratio of the product determined by H-NMR is ethylene / propylene = 99/1, the weight average molecular weight of the product determined by GPC is 70,500, the molecular weight distribution is 2.2, and the density is 0.910 g / cc. Met. The heat of fusion in the range of 0 to 200 ° C. measured by DSC was 165 J / g.

Example 1:
The olefin elastomer (1) and the ethylene-α-olefin copolymer (1) were weighed in the proportions shown in Table 2, and heated and dissolved in toluene to obtain a toluene solution containing a 2 wt% release agent. A release agent solution is applied to one side of a polyethylene terephthalate (PET) film so that the thickness after drying is 0.1 μm, and is dried in a safe bend dryer heated to 150 ° C. for 3 minutes. A mold sheet was obtained. The PET film used is a product “Diafoil T100-38” (thickness: 38 μm) manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.

Example 2:
Using a multilayer extrusion molding machine, molding temperature 220 ° C., die width 70 cm, take-off speed 21 m / min, chill roll temperature 30 ° C., release agent discharge rate 1.1 kg / hr, substrate discharge rate 25.5 kg / hr Under these conditions, a multilayer film having a release layer thickness of 1 μm and a substrate thickness of 25 μm was obtained by a T-die coextrusion method.

  The olefin elastomer and ethylene-α-olefin copolymer composition used for the release layer are shown in Table 2. These were used after weighing a predetermined amount, adding 0.1 part by weight of “Irganox 1010” as an antioxidant to 100 parts by weight of the olefin elastomer, and homogenizing with a mixer. As the base material, polypropylene (PP) (“NOVATEC FW3E” manufactured by Nippon Polychem) (melting point: 140 ° C.) was used as it was. The film thickness of each layer was calculated | required from the optical microscope observation result and film thickness of a multilayer film cross section.

Example 3:
In Example 1, except that the olefin-based elastomer (1) and the ethylene-α-olefin copolymer (1) were used and the composition shown in Table 2 was used as a release agent, the same as in Example 1. A release sheet was obtained.

Example 4:
In Example 1, except that the olefin-based elastomer (4) and the ethylene-α-olefin copolymer (1) were used and the composition shown in Table 2 was used as a release agent, the same as in Example 1. A release sheet was obtained.

Example 5:
In Example 1, the olefin elastomer (3) and the ethylene-α-olefin copolymer (1) were used, the composition shown in Table 2 was used as a release agent, and the release layer thickness was 0.2 μm. A release sheet was obtained in the same manner as in Example 1 except for changing to.

Example 6:
In Example 1, the olefin elastomer (5) and the ethylene-α-olefin copolymer (1) were used, the composition shown in Table 3 was used as a release agent, and the release layer thickness was 0.2 μm. A release sheet was obtained in the same manner as in Example 1 except for changing to.

Example 7:
In Example 1, HEMA-modified olefin elastomer (1) and olefin elastomer (2) were used as the olefin elastomer, and ethylene-α-olefin copolymer (2) was used as the ethylene α-olefin copolymer. A release sheet was obtained in the same manner as in Example 1 except that the composition shown in Table 3 was used as a mold and the release layer thickness was changed to 0.2 μm.

Example 8:
As the release agent used in Example 7, as a polyfunctional isocyanate compound, “NY718A” (76% by weight butyl acetate solution of an aliphatic diisocyanate / triol adduct (trifunctional isocyanate)) manufactured by Mitsubishi Chemical Corporation was used as a modified olefin elastomer. A release sheet having a release layer thickness of 0.2 μm was added to a PET film and dried in the same manner as in Example 1 so that the isocyanate group was 1.1 equivalents relative to the number of moles of HEMA contained. Got.

Example 9:
On the rough surface of the peeling support substrate made of one-sided bleached kraft paper (weight per unit: 80 g / m ² : manufactured by Daio Paper Co., Ltd.), a low density of 0.920 g / cc and a melt index of 7.0 g / 10 min. A primer layer having a thickness of 30 μm was formed as a melt extruded laminate of density polyethylene at 325 ° C. On the surface of this primer layer, a release agent similar to that used in Example 2 was melt-extruded laminate at 240 ° C. so as to have a thickness of 30 μm, and the layer structure consisting of substrate / primer layer / release layer was formed. A release sheet was obtained (see Table 3).

Example 10:
The same primer layer as that used in Example 9 was formed from the release agent obtained by weighing the olefin elastomer (2) and the ethylene-α-olefin copolymer (1) in the proportions shown in Table 3. A release sheet having a layer structure of substrate / primer layer / release layer was obtained by melt extrusion lamination at 240 ° C. so that the thickness of the primer layer of kraft paper was 30 μm.

Comparative Example 1:
In Example 1, the olefin-based elastomer (1) is changed to the olefin-based elastomer (2), and only the olefin-based elastomer (2) is used as a release agent, and no ethylene-α-olefin copolymer is used. A release sheet was obtained in the same manner as in Example 1 except that the release layer thickness was changed to 0.2 μm (see Table 4).

Comparative Example 2:
In Example 1, as a release agent, ethylene-α-olefin copolymer: ethylene octene copolymer having a density of 0.868 g / cc (“Deng Pont Dow Elastomers“ engage 8150 ”, measured by DSC at 0 to 200 ° C.) The mold release sheet was obtained in the same manner as in Example 1 except that the heat of fusion in the range of 27 J / g) was used, no olefin elastomer was used, and the release layer thickness was changed to 0.2 μm. (See Table 4).

Comparative Example 3:
In Example 1, as a release agent, ethylene-α-olefin copolymer: ethylenebutene copolymer having a density of 0.890 g / cc (“A20090M” manufactured by Mitsui Chemicals, in the range of 0 to 200 ° C. measured by DSC) A release sheet was obtained in the same manner as in Example 1 except that the heat of fusion was 73 J / g), no olefin elastomer was used, and the release layer thickness was changed to 0.2 μm (Table 1). 4).

Comparative Example 4:
In Example 2, as a mold release agent, an ethylene-α-olefin copolymer: “Engage 8200” manufactured by DuPont Dow elastomers, density 0.870 g / cc, heat of fusion in the range of 0 to 200 ° C. measured by DSC is 27 J / g), the olefin-based elastomer was not used, the release agent discharge rate was changed to 2.3 kg / hr, and the release layer thickness was changed to 2 μm. A mold sheet was obtained (see Table 4).

Comparative Example 5:
In Example 2, an elastomer (3) and an ethylene-α-olefin copolymer: “Engage 8200” manufactured by DuPont Dow elastomers) were used as a release agent, and the discharge rate of the release agent was 2.2 kg / hr. A release sheet was obtained in the same manner as in Example 2 except that the release layer thickness was changed to 2 μm (see Table 4).

Comparative Example 6:
In Example 2, only the ethylene-α-olefin copolymer (1) was used as the release agent, no olefin elastomer was used, the release amount of the release agent was 2.3 kg / hr, and the release layer. A release sheet was obtained in the same manner as in Example 2 except that the thickness was changed to 2 μm (see Table 4).

Comparative Example 7:
In Example 1, a release sheet was obtained in the same manner as in Example 1 except that only the olefin elastomer (6) was used as a release agent and the release layer thickness was changed to 0.2 μm ( (See Table 4).

Comparative Example 8:
The olefin elastomer (2) and the ethylene-α-olefin copolymer (2) were weighed in the proportions shown in Table 4, and heated and dissolved in toluene to give a toluene solution containing 2 wt% release agent. A release agent solution was applied to one side of the same PET film as in Example 1 in the same manner as in Example 1 and dried to obtain a release sheet.

Comparative Example 9:
The olefin elastomer (2) and the ethylene-α-olefin copolymer (4) were weighed in the proportions shown in Table 4, and heated and dissolved in toluene to obtain a toluene solution containing a 2 wt% release agent. A release agent solution was applied to one side of the same PET film as in Example 1 in the same manner as in Example 1 and dried to obtain a release sheet.

(1) Peel test:
The release sheets obtained in the above examples and comparative examples were cut into a width of 30 mm and a length of 150 mm, and a commercial double-sided adhesive tape with a width of 25 mm (“Nitto Tape No. 500” manufactured by Nitto Denko Corporation) was used. The rubber roller having a weight of 2 kg was reciprocated once and pressed. Thereafter, the adhesive tape is fixed to a stainless steel plate (SUS304), and the release agent layer and the adhesive layer are peeled 180 ° at a speed of 300 mm / min at 23 ° C., and the force required for the peeling (average value of five samples) ) Was measured using a tensile tester. The results are shown in Table 5.

(2) Heat peeling test heat (measurement of the ratio of peel strength between heat-treated product and room temperature product):
The release sheets obtained in the above examples and comparative examples were cut into a width of 30 mm and a length of 150 mm, and then a commercially available double-sided adhesive tape having a width of 25 mm (“Nitto Tape No. 502” manufactured by Nitto Denko Corporation). The rubber roller having a weight of 2 kg was reciprocated once and pressed. Half of the 10 samples were subjected to heat treatment for 1 hour under a load of 20 g / cm ² in a safe ben dryer (manufactured by Satake Safe Ben Dryer) heated to 100 ° C and stabilized, Cooled down. The remaining five samples were kept at room temperature (23 ° C.).

  Thereafter, the adhesive tape is fixed to a stainless steel plate (SUS304), and the release agent and the adhesive interface are peeled at 180 ° at a speed of 300 mm / min at 23 ° C. using a tensile tester, and the force required for the peeling is obtained. It was measured. The results of 5 points were averaged for each of the heat treated product and the room temperature product, and the ratio (peel strength of the heat treated product / peel strength of the product kept at room temperature) was evaluated as heat resistance. The closer this ratio is to 1, the better the heat resistance. The results are shown in Table 5.

Illustration of how to draw a baseline for the endothermic peak obtained by DSC measurement

Claims (6)

  Component (A): Olefin elastomer having a density of 0.855 g / cc or more and less than 0.868 g / cc and Component (B): Ethylene-α- having a density of 0.868 g / cc or more and 0.970 g / cc or less A release agent mainly composed of an olefin copolymer, wherein the difference between the average density of component (A) and the average density of component (B) is 0.005 g / cc or more, and component (A): component A release agent, wherein the blending ratio (weight ratio) of (B) is 90:10 to 10:90.   The mold release agent according to claim 1, wherein the component (A) is a copolymer of at least one selected from the group consisting of propylene, butene and hexene and ethylene.   The mold release agent of Claim 1 or 2 in which a component (A) and / or a component (B) have a functional group.   The mold release agent according to any one of claims 1 to 3, wherein the component (A) and the component (B) have an endothermic peak of 1 J / g or more as measured with a differential scanning calorimeter in a temperature range of 0 to 200 ° C.   A release sheet comprising a release layer comprising the release agent according to any one of claims 1 to 4 on at least one surface of a sheet-like substrate.   6. The release sheet according to claim 5, wherein the release layer comprises a release agent obtained by a crosslinking reaction with a reactive compound capable of reacting with the functional group of component (A) or component (B).

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