JP2006206844A - Releasable resin composition, releasable sheet, releasable film and adhesive sheet or adhesive film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a releasable resin composition that is subjected to extrusion lamination molding, has excellent mold release characteristics, heat resistance, solvent resistance and substrate adhesivity. <P>SOLUTION: The releasable resin composition comprises 99.99-70 wt.% of a polyolefin resin (A) and 0.01-30 wt.% of a block copolymer (B) having a polydialkylsiloxane block and a polyolefin block with ≥1,000 molecular weight. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  TECHNICAL FIELD The present invention relates to a releasable resin composition, and more specifically, a releasable resin composition that can be extrusion-laminated, is excellent in releasability, and has good substrate adhesion, and a sheet or film using the same. The present invention relates to a releasable sheet or a releasable film, and a pressure-sensitive adhesive sheet or pressure-sensitive adhesive film.

  As a method for forming a release layer (release layer) of a separator such as release paper and a back treatment layer of an adhesive tape, a release agent (release agent) has been conventionally applied to a substrate such as a film or paper. A method is adopted in which a solution is applied and then dried to form a release layer. In addition, when a release agent solution is applied directly to a paper base material, it will be soaked in. Therefore, when producing release paper, polyethylene is laminated on the paper base material, and a release agent is applied on the laminate. I was working.

  However, in recent years, the solvent-free release layer forming process has been studied from the viewpoint of environmental considerations and cost. For example, a releasable resin or a method of extruding a releasable resin containing a releasable compound such as a silicone compound or a long-chain alkyl compound and laminating it on a substrate (extrusion lamination) Has been proposed. As such a releasable resin, a polyolefin resin having a good balance of physical and chemical properties and excellent film formability is suitable, and among these, polyethylene and ethylene-α-olefin copolymers are preferably used. It is done. It is particularly suitable for acrylic adhesive materials. Furthermore, an example in which a modified silicone compound is blended with polyethylene or an ethylene-α-olefin copolymer has been proposed (Patent Documents 1 to 3).

  However, since an ethylene-α-olefin copolymer is usually difficult to extrusion laminate by itself, it is necessary to use it in combination with polyethylene. In general, since the molding temperature is 300 ° C. or higher, the resin tends to be oxidized and deteriorated easily. Furthermore, when the adhesive layer is formed, when the solvent or water-based acrylic adhesive is applied and dried on the release layer, heat of about 100 ° C. to 120 ° C. is applied, so that the release layer has heat resistance and solvent resistance. If it is insufficient, there is a problem such as variation in peeling force. In order to solve these problems, it has been proposed to add an antioxidant within a specific range (Patent Document 3). However, there is a desire to obtain a release layer with better release properties.

In addition, as the silicone compound to be mixed with the releasable resin, those having a structure considered to be compatible with the base resin such as polyethylene and ethylene-α-olefin copolymer, that is, silicone having a similar structure to the base resin Compounds are mainly used. However, since the substrates that can react with the silicone compound in a bonded form having heat resistance and solvent resistance are limited, the design of the silicone compound is limited. For this reason, there has been a desire to obtain a release layer that can be designed with a higher degree of freedom.
JP-A 63-003076 Japanese Patent Laid-Open No. 04-085022 Japanese Patent No. 2991348

  An object of the present invention is to provide a releasable resin composition that is capable of extrusion laminate molding, has excellent releasability, and is excellent in heat resistance, solvent resistance, and substrate adhesion.

As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by mixing a small amount of a block copolymer of polydialkylsiloxane and polyolefin with a polyolefin resin, and have completed the present invention.
That is, the gist of the present invention is that the polyolefin resin (A) is 99.99 to 70% by weight, and the block copolymer (B) having a polydialkylsiloxane block and a polyolefin block having a molecular weight of 1000 or more is 0.01 to 30% by weight. %, In the releasable resin composition. The releasable resin composition may contain an arbitrary addition amount of an arbitrary compound without departing from the object of the present invention.

  The molecular weight of the polyolefin block is preferably 15000 or less. The molecular weight of the polydialkylsiloxane is preferably 3000 or more, and preferably 30000 or less. The block copolymer (B) preferably contains 50% by weight or more of polydialkylsiloxane. However, it is preferably 98% by weight or less. Moreover, it is preferable that a block copolymer (B) is a triblock or more.

The releasable resin composition preferably comprises 99.9 to 85% by weight of the polyolefin resin (A) and 0.1% to 15% by weight of the block copolymer (B).
Another gist of the present invention resides in a sheet or film characterized by being obtained by extruding this releasable resin composition.
Still another subject matter of the present invention lies in a releasable sheet or a releasable film, which is obtained by extruding the releasable resin composition and laminating it on a substrate. The base material that can be used is not particularly limited, such as paper, cloth, and resin. However, since the releasable resin composition of the present invention is extrusion molded and laminated on the base material, a conventional release agent solution such as paper or cloth is used. This is particularly effective for a base material that could not be directly coated due to infiltration. In addition, when paper is used as a base material, it may be called release paper or release paper.

Still another subject matter of the present invention is a pressure-sensitive adhesive sheet or pressure-sensitive adhesive film including at least a resin base material, a release layer, and a pressure-sensitive adhesive layer, and the release layer extrudes the release resin composition and base material. The present invention resides in a pressure-sensitive adhesive sheet or a pressure-sensitive adhesive film, characterized by being laminated. In addition, what is called an adhesive tape is included in an adhesive sheet or an adhesive film.
Alternatively, it is also preferable to obtain a releasable sheet or a releasable film as a resin base material and a release layer by co-extrusion of the resin to be the base material and the releasable resin composition of the present invention. Moreover, you may obtain an adhesive sheet or an adhesive film by co-extruding 3 layers with the adhesive resin composition which should become an adhesion layer.

  The releasable resin composition of the present invention is capable of extrusion molding, extrusion laminate molding, and can provide a releasable sheet, a releasable film, a pressure-sensitive adhesive sheet, and a pressure-sensitive adhesive film without using a solvent. It is environmentally preferable, and waste solvent treatment is unnecessary and costs can be reduced. Moreover, the release sheet, release film, pressure-sensitive adhesive sheet and pressure-sensitive adhesive film of the present invention are excellent in releasability such as peeling force and residual adhesive force, and excellent in substrate adhesion.

  According to the present invention, it is possible to provide a cyan-based recording liquid that hardly undergoes bronzing due to little discoloration due to natural exposure after printing on glossy paper and exposure to ozone gas. In addition, according to the present invention, when recording on plain paper or ink jet dedicated paper by a method such as ink jet recording, the print quality is good and the density, saturation and color tone of the recorded image are excellent, especially light resistance and ozone resistance. A recorded image with good properties can be formed. In the present invention, it is not always essential to exhibit all the effects, and it is only necessary to have one or more of the effects described above.

Hereinafter, the present invention will be described in more detail.
In the releasable resin composition of the present invention, the polyolefin resin (A) is 99.99 to 70% by weight, and the block copolymer (B) having a polydialkylsiloxane block and a polyolefin block having a molecular weight of 1000 or more is 0.00. 01 to 30% by weight. In addition, arbitrary addition amount may be included in the range which does not deviate from the objective of this invention.

(1) Polyolefin resin (A)
The polyolefin resin (A) is not particularly limited, and a polymer obtained by polymerizing an α-olefin alone or a polymer copolymerized with other reactive monomers using olefin as a main component can be widely used. Examples thereof include homopolymers of α-olefins such as ethylene, propylene, butene, hexene, and octene, and copolymers thereof. A copolymer of α-olefin such as ethylene and ethylidene norbornene or norbornene can also be used. Furthermore, diene rubbers obtained by living polymerization represented by polyisoprene, polymers obtained by hydrogenating them, polymers obtained by ring-opening polymerization of cyclic olefins, and hydrogenated products thereof can also 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, a polyolefin obtained by hydrogenation such as a nuclear hydrogenated product of styrene / butadiene copolymer or a nuclear hydrogenated product of styrene / isoprene copolymer can be used. These plural types of resins can also be mixed and used.

When laminate molding or coextrusion molding is performed, it is preferable to use a polymer mainly composed of ethylene because of excellent moldability. The main component means containing 50% by weight or more.
As the polymerization method of the polyolefin resin (A), any known method can be used. For example, it can be obtained by radical polymerization at high temperature and high pressure (high pressure method), polymerization by Ziegler-Natta catalyst, metallocene catalyst, or the like. It is preferable to use the obtained polyolefin. In particular, when laminate molding is performed, it is preferable to use a high pressure method in order to improve adhesion to the release layer.

  The melt flow index (MFR) at 180 ° C. of the polyolefin resin (A) is preferably 100 g / 10 min or less. The MFR has a correlation with the average molecular weight, and usually the smaller the average molecular weight, the larger the MFR. In order to obtain a sufficient film strength when the release layer is formed, the MFR is preferably 100 g / 10 min or less. More preferably, the MFR is 50 g / 10 min or less, and further preferably 20 g / 10 min or less. However, in order to improve moldability, the MFR is usually 1 g / 10 min or more.

  The polyolefin resin (A) used in the present invention may have a functional group to such an extent that the release characteristics as the release material of the present invention are not excessively lowered. For example, (meth) acrylate group, vinyl group, halogen atom, ester group, hydroxyl group and the like can be mentioned. Examples of the polyolefin resin having such a functional group include ethylene- (meth) acrylate copolymer, polybutadiene, polyvinyl chloride, polyvinyl acetate, and ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyethylene-vinyl. An alcohol copolymer is mentioned. These may be mixed with the aforementioned polyolefin resin. Here, the (meth) acrylate group refers to an acrylate group and a methacrylate group, and the (meth) acrylic acid refers to acrylic acid and methacrylic acid.

(2) Block copolymer (B)
The block copolymer (B) having a polydialkylsiloxane block and a polyolefin block used in the present invention usually has a polydialkylsiloxane having two or more reactive groups and one functional group capable of reacting with the reactive group. Or it can obtain by making the polyolefin compound which has two or more react. Moreover, you may make the non-siloxane compound which has the same functional group as the said siloxane compound react as needed.

  The alkyl group in the polydialkylsiloxane is preferably a chain, branched or branched alkyl group having 1 to 10 carbon atoms. The alkyl group may be substituted with an aryl group, but in this case, it is preferable to have 1 to 10 carbon atoms as a whole. For example, examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a hexyl group, a cyclohexyl group, an octyl group, a decyl group, and a benzyl group. A chain, branched or cyclic alkyl group having 1 to 10 carbon atoms is preferred, and a chain or branched alkyl group having 1 to 10 carbon atoms is more preferred. In particular, a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, and a hexyl group are preferable, and a methyl group is most preferable.

  The functional group possessed by the polydialkylsiloxane is preferably an amino group, a hydroxyl group, an epoxy group, a thiol group, a (meth) acryl group, a carboxyl group, or a hydride group. In view of the stability of the bond with the silicon atom, it is desirable that an alkylene group having about 2 to 5 carbon atoms be interposed between the siloxane and the siloxane other than the hydride group. These functional groups are preferably those having one end or both ends, particularly preferably a compound possessed at both ends.

  The molecular weight of the polydialkylsiloxane used in these reactions is preferably 3000 or more, more preferably 4000 or more, in order to suppress the adhesiveness of the release layer. However, it is preferably 30000 or less, more preferably 25000 or less. In order to obtain sufficient releasability, the weight of the siloxane compound in the block copolymer (B) is preferably 50% to 98%.

Moreover, it is preferable that these block copolymers are more than a triblock. In particular, in order to avoid the formation of free silicone when the block chain is cleaved by heat or the like, it is preferable that both ends of the molecular chain of the block copolymer (B) are polyolefin blocks.
The polyolefin block is not particularly limited as long as it is a functional group capable of reacting with the functional group of the polydialkylsiloxane, but preferred functional groups are a hydroxyl group, an amino group, an epoxy group, and a carboxyl group. The polyolefin preferably has a functional group at one or both ends. As the polyolefin forming the polyolefin block, linear polyethylene and ethylene-α-olefin copolymers are preferable. The polyolefin having a functional group at one or both ends is not particularly limited, and the terminal can be functionalized after directly polymerizing a monomer such as ethylene, or butadiene and isoprene can be anionically polymerized to form a terminal. It can also be produced by hydrogenating the double bond after functionalizing the.

The molecular weight of the polyolefin block is 1000 or more. Here, the molecular weight is a value including a functional group. If it is less than 1000, the compatibility with the base resin becomes insufficient. However, in order to obtain an appropriate peeling force, the molecular weight is preferably 15000 or less.
Although the manufacturing method of the block copolymer (B) of this invention is not specifically limited, For example, it can manufacture by the following method. By reacting α, ω-bis (carboxyl) polydimethylsiloxane (carboxylic acid at both ends) and α, ω-dihydroxypolyolefin in the presence of an acid catalyst or in the presence of a dehydrating agent such as dicyclohexylcarbodiimide, a multi-block polymer ( The block copolymer (B) of the present invention is obtained.

Conversely, both ends of the polyolefin may be carboxylic acid, and the polydialkylsiloxane may have a hydroxyl group. Alternatively, an amino group may be used in place of the hydroxyl group.
Further, α, ω-bis (hydrido) polydimethylsiloxane and α, ω-divinyl polyolefin may be added in the presence of a platinum catalyst to form a block copolymer (B).

In addition, the number of blocks and the molecular weight of the block copolymer (B) can be adjusted by, for example, adjusting the amount of a compound having a functional group at one end only.
Moreover, you may coexist amines, carboxylic acids, and alcohol as a 3rd component at the time of reaction. Preferred amines are aliphatic and aromatic diamines. For example, ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexamethylenediamine, 1,8-octamethylenediamine, 1,10-decamethylenediamine, 1,12-dodecamethylenediamine, 1 , 4-cyclohexanediamine and other low molecular weight diamines, polyethylene glycol diamine, high molecular amines such as polypropylene glycol diamine; trimethylolpropane and glycerin polyaminoethylene glycol, polyaminopropylene glycol adducts, p-phenylenediamine, 3, 3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, bis (3-aminophen Le) sulfone, bis (4-aminophenyl) sulfone. Of these, two or more diamines may be used in combination.

  Preferred carboxylic acids are dicarboxylic acids. For example, aliphatic polyvalents such as oxalic acid, propanedioic acid (malonic acid), butanedioic acid (succinic acid), adipic acid, octanedioic acid, dodecanedioic acid, octadecanedioic acid, pimelic acid, suberic acid, tricarballylic acid Examples include polycarboxylic acid polymers containing a carboxyl group-containing monomer such as carboxylic acid and (meth) acrylic acid as structural units. Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid. And positional isomers thereof.

  Preferred alcohols are diols, and aliphatic and aromatic diols can be used. For example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, cyclohexanediol and stereoisomers and positional isomers thereof Low molecular weight diols such as cyclohexanedimethanol and its stereoisomers and positional isomers, various polyether diols such as polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, ethylene oxide-propylene oxide copolymer, and aliphatic polyesters Diol, polybutadiene diol, hydrogenated polybutadiene diol, aliphatic polycarbonate diol, polycaprolactone diol, and aromatic diol include hydroquinone and its positional isomers Bisphenol A, bisphenol F, octamethyl bisphenol A or the bisphenol F, 2,6,2 ', 6'-tetramethyl-4,4'-bisphenol A, or the like the bisphenol F and the like.

  Moreover, a branched structure can be produced | generated by adding a trifunctional or more functional monomer, and the primary structure of a block copolymer (B) can also be made into a branched structure or a star-shaped structure. Examples of the trifunctional or higher functional monomer include triamine and tetraamine polyamines, trifunctional or higher polycarboxylic acids or derivatives thereof, glycerol, polyglycidol, hydroxyethyl (meth) acrylate-various (meth) acrylate copolymers, and the like. Examples include polymers having the above hydroxyl group-containing monomers as constitutional units, modified polyvinyl alcohols with an appropriate amount of hydroxyl groups remaining, hydrogenated polybutadiene polyols, polycaprolactone polyols, and the like.

Alternatively, the molecular weight of the block copolymer (B) can be adjusted by adding a monofunctional amine, carboxylic acid, or alcohol.
Two or more of the above monomers and polymers may be used simultaneously. Moreover, it can also manufacture while dehydrochlorinating using said acid chloride, and can also manufacture using the ester- amide exchange method using alkylesters, such as methyl ester, and phenyl ester.

The reaction method and reaction conditions for these block copolymers are not particularly limited as long as they are known methods. For example, no solvent or various organic solvents can be used, and the direct method is carried out while distilling off the water produced under heating and reduced pressure. In the case of using an acid chloride, it can be carried out while capturing the generated hydrogen chloride as a hydrochloride with pyridine or triethylamine. In the ester-amide exchange, the produced alcohols are removed under reduced pressure. On the other hand, in the reaction of a terminal olefin compound with hydride, there is an activity of adding a Si—H compound such as chloroplatinic acid or rhodium compound to an olefin under a solvent such as toluene, xylene, cyclohexane, or a solvent-free condition. A catalyst system can be used.
In addition, all the raw material compounds may be added simultaneously, or after adding bifunctional siloxane and excess functionalized polyolefin to react first, the adjustment compound may be added, or in the reverse order. And may be reacted.

(3) Releasable Resin Composition The releasable resin composition of the present invention is a block having a polyolefin resin (A) of 99.99 to 70% by weight and a polydialkylsiloxane block and a polyolefin block having a molecular weight of 1000 or more. A copolymer (B) consists of 0.01-30 weight%. In addition, arbitrary addition amount may be included in the range which does not deviate from the objective of this invention.

  As the amount of the polyolefin resin (A) increases, the moldability tends to be good. Preferably, the polyolefin resin (A) is 80% by weight or more, more preferably 85% by weight or more. On the other hand, the more the block copolymer (B), the better the releasability. Preferably, the polyolefin resin (A) is 99.9% by weight or less, more preferably 99% by weight or less.

  The method for preparing the composition is not particularly limited. For example, both are dissolved in a solvent in which both (A) and (B) are dissolved, cooled after heating and mixed, or poured into a poor solvent in which both are not dissolved, and the mixture is precipitated. The composition can be obtained by collecting and drying. Alternatively, it can also be obtained by a direct melt mixing method. It is preferable to knead in a molten state and directly melt and mix. A uniaxial or biaxial melt kneader is used as a kneading machine for melt kneading. The mixing temperature is preferably a temperature at which both resins are in a molten state. In particular, since the melting temperature of the silicone compound varies depending on the compound, the mixing temperature is preferably equal to or higher than the melting temperature of the silicone compound. Preferably it is 150 degreeC or more, More preferably, it is 200 degreeC or more. However, the temperature is such that the resin does not decompose and is usually 400 ° C. or lower. The composition thus kneaded is pelletized.

The (A) and (B) may be mixed according to the weight ratio of in the object composition (A) and (B), were mixed in advance either in larger amount, it may be diluted. In this case, usually, (B) may be diluted with (A) after being mixed in a larger amount than in the target composition.
Since the composition of the present invention has high heat resistance of the peelable compound, it can withstand kneading at a high temperature, and a releasable resin composition having a low releasability and a high residual adhesive strength can be obtained.

(4) Sheet and film A mold release sheet and a mold release film can be obtained by extrusion molding the mold release resin composition of the present invention. Conventionally known methods and conditions for extrusion molding can be used. Since the releasable resin composition of the present invention can be processed into a sheet or film by extrusion molding, it is not necessary to perform coating using a solvent, and a single layer sheet / film can be obtained more easily than in the past. In addition, it is environmentally preferable and waste solvent treatment is unnecessary, and the cost can be reduced.

When a releasable sheet or a releasable film is obtained with a single layer, the film thickness is sufficient if it has rigidity strength according to the purpose of use, and is usually 0.1 μm or more, preferably 0.5 μm or more. On the other hand, if it is too thick, the peel force may increase, and the cost also increases. Therefore, the thickness is usually 5 mm or less, preferably 2 mm or less.
Moreover, a release sheet or a release film can also be obtained by extruding the release resin composition of the present invention and laminating the substrate. Or the resin which should become a base material and a mold release resin composition can be coextruded, and a mold release sheet or a mold release film can also be obtained as a resin base material and a mold release layer. Conventionally known methods and conditions for extrusion molding, laminate molding, and co-extrusion can be used. Since the releasable resin composition of the present invention can be extruded, a release layer can be formed on the substrate without using a solvent, which is environmentally preferable, waste solvent treatment is unnecessary, and cost can be reduced.

The base material used for the releasable film or the releasable sheet used in the present invention is not particularly limited as long as it has rigidity and strength according to the purpose of use, and various materials such as resin, paper, and cloth can be used.
Resin is preferable in terms of high rigidity and strength. For example, the resin may have been subjected to corona treatment, plasma treatment, flame plasma treatment, or the like. Specific examples include stretched products such as polyethylene and polypropylene, stretched products of polyester resins such as polyethylene terephthalate and polybutylene terephthalate, films of polyimide, polycarbonate, polystyrene, cellophane, and sheets thereof.

The releasable resin composition of the present invention is particularly effective for substrates such as paper and cloth, which could not be applied directly because of the conventional release agent solution. Paper is preferable in terms of cost and ease of handling. Here, the paper includes synthetic paper, paper surface-treated with polyethylene and polyvinyl alcohol for surface smoothing, glassine paper, and the like.
The release layer can be formed by laminating the composition on the above-described substrate, or by coextrusion molding of the composition and the other resin layer. When performing laminate molding, it is preferable to mold at 260 ° C. to 330 ° C. in order to ensure adhesion to the substrate. In the case of coextrusion molding, the resin temperature of each layer may be the same or different.

When the release layer is formed on the substrate, the thickness of the release layer is usually 0.01 μm or more and preferably 0.05 μm or more in order to sufficiently reduce the peeling force. On the other hand, even if it is too thick, the peel force may increase, so it is usually 30 μm or less, preferably 20 μm or less.
The releasable sheet / film of the present invention can be used for various applications and can also be used for an adhesive surface. The kind of adhesive surface to which the releasable film of the present invention is applied is not particularly limited. For example, it can be applied to an adhesive surface made of various adhesives such as an acrylic adhesive, a rubber adhesive, and a polyurethane adhesive.

Moreover, it is good also as an adhesive sheet / film by providing an adhesive layer in the time of preparation of said release sheet / film or after preparation. For example, the adhesive layer may be laminated at the same time as the release layer is laminated on the substrate. Alternatively, the adhesive layer may be laminated after the release layer is formed.
Alternatively, the adhesive layer may be laminate-molded after two layers of the resin to be the base material and the release resin composition are coextruded to form the resin base material and the release layer. Or it is good also as an adhesive sheet / film provided with the adhesion layer, the resin base material, and the mold release layer by co-extruding 3 layers of adhesive resin composition, resin used as a base material, and mold release resin composition. As the adhesive resin composition, various known ones such as acrylic, rubber, and polyurethane can be used.

The features of the present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.
<Production Example 1> (Synthesis of silicone-polyolefin multi-block copolymer)
In a 4-neck separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a reflux condenser equipped with a dry nitrogen gas inlet tube, a silicone dicarboxylic acid (X-22-162C manufactured by Shin-Etsu Chemical Co., Ltd .; average molecular weight) 4600) 46 g (10 mmol) was dissolved in 400 g of toluene, and 5.1 g (25 mmol) of dicyclohexylcarbodiimide was gradually added thereto with stirring.

  After reacting at room temperature (25 ° C.) for 5 hours, 40.5 g (15 mmol) of Polytail H (molecular weight 2700, average functional group number 2.3) manufactured by Mitsubishi Chemical Corporation was added and reacted at 100 ° C. for 6 hours. The reaction solution was cooled to room temperature and then poured into 2000 g of ethanol to produce a precipitate. This was filtered to collect only the solid content, and then dried at 100 ° C. for 8 hours under reduced pressure in a vacuum dryer. Furthermore, this dry powder was put into 1500 g of n-hexane, stirred for 30 minutes with a magnetic stirrer, and filtered to recover a solid (n-hexane washing operation). This n-hexane washing operation was repeated three times and then dried again under reduced pressure in a vacuum dryer at 100 ° C. for 8 hours to obtain a reaction product (peelable polymer compound). Yield was 85.2 g.

<Production Example 2> (Synthesis of silicone graft PMMA)
In a 500 ml flask, 40 g of one-end methacryl-modified silicone compound (FM-0725 manufactured by Chisso Corporation) and 40 g of MMA monomer are dissolved in 150 g of MEK, and 80 mg of AIBN (azobisisobutyronitrile) is added to the flask at 70 ° C. Time heating and polymerization were performed. After cooling, it was washed with n-hexane to remove the unreacted silicone compound, then redissolved in 300 ml of THF, poured into 1.5 L of methanol, and the polymer was recovered and dried under reduced pressure to obtain silicone grafted PMMA. The yield was 37.1 g, and the block derived from the silicone compound was 75% by weight.

<Production Example 3> (Synthesis of silicone-low molecular weight polyolefin multi-block copolymer)
In a 300 ml flask, 40 g of hydride-sealed polydimethylsiloxane (manufactured by Aldrich, molecular weight 17500) and 2.5 g of Mitsubishi Chemical Dialene 30 (iodine number 44, average molecular weight 580) were dissolved in 50 g of toluene, 0.1 mg of chloroplatinic acid was heated at 90 ° C. for 12 hours for polymerization. After confirming that the absorption of Si-H disappeared in the infrared absorption spectrum, it was cooled, redissolved in 300 ml of THF, poured into 1.5 L of methanol, recovered, dried under reduced pressure, and a waxy triblock. A polymer was obtained. The yield was 39.9 g, and the block derived from the silicone compound was 94% by weight.

<Example 1>
To 95 parts of low density polyethylene (density 0.919 g / cm ³ , MFR = 8.2 g / 10 min), 5 parts of the peelable polymer compound produced in Production Example 1 was added, and Laboplast Mill (Toyo Seiki Co., Ltd.). (Manufactured by Seisakusho Co., Ltd.) was melt kneaded at a temperature of 300 ° C., a rotation speed of 100 rpm, and a kneading time of 3 minutes to obtain a polyethylene resin composition. The resin composition was pressed with a press molding machine at 200 ° C. to a thickness of 200 μm, and then cooled to obtain a release sheet.

  About the obtained release sheet, peeling force and residual adhesive force were measured in the following manner. The releasable sheet is cut into a width of 30 mm and a length of 150 mm, and a commercially available adhesive tape (Nitto Denko Corporation, Nitto Tape No. 502) is applied to this by reciprocating a rubber roller weighing 2 kg from above. This was used as a test piece. Thereafter, the test piece was fixed to a tensile tester, the adhesive tape was peeled 180 ° at a rate of 300 mm / min at 23 ° C., and the force (peeling force) required for the peeling was measured.

Subsequently, the pressure-sensitive adhesive tape peeled from the release sheet was reciprocated once by a Teflon (registered trademark) sheet (thickness: 200 μm) with the rubber roller. After leaving at 23 ° C. for 1 hour, 180 ° peeling was performed, and the peeling force (F ₁ ) was measured.
The pressure-sensitive adhesive tape that is not attached to the release sheet was measured peel force (F ₀₎ by the same method. The residual adhesive strength was defined by the following formula.

Residual adhesive strength (%) = (F ₁ / F ₀ ) × 100

The release sheet prepared in the above examples was peeled and evaluated by the method described above. The results are shown in Table-1. The peel strength was low and the residual adhesive strength was 92%, showing almost no decrease and good.

<Comparative Example 1>
A release sheet was prepared in the same manner as in Example 1 except that the compound obtained in Production Example 2 was used as the peelable polymer compound, and peel evaluation was performed. The results are shown in Table-1. The residual adhesive rate was low, probably because of free silicone that was thought to have decomposed out of the peelable compound.

<Comparative example 2>
A release sheet was prepared in the same manner as in Example 1 except that the compound obtained in Production Example 3 was used as the peelable polymer compound, and peel evaluation was performed. The results are shown in Table-1. The releasable polymer compound was waxy and the cohesive force was low, so the residual adhesion rate was low.

<Comparative Example 3>
A releasable sheet was prepared in the same manner as in Example 1 except that the peelable polymer compound was not used, and peel evaluation was performed. The results are shown in Table-1. A very high peel force was required.

  As described above, the releasable resin composition of the present invention is capable of extrusion molding and extrusion laminate molding, and provides a releasable sheet, a releasable film, a pressure-sensitive adhesive sheet, and a pressure-sensitive adhesive film without using a solvent. It is possible to reduce the cost because it is environmentally preferable and the waste solvent treatment is unnecessary. The release sheet, release film, pressure-sensitive adhesive sheet and pressure-sensitive adhesive film of the present invention are excellent in releasability such as peeling force and residual adhesive force and excellent in substrate adhesion, and can be used industrially. The nature is extremely high.

Claims (11)

The polyolefin resin (A) is composed of 99.99 to 70% by weight, and the block copolymer (B) having a polydialkylsiloxane block and a polyolefin block having a molecular weight of 1000 or more is composed of 0.01 to 30% by weight. A releasable resin composition. The mold release resin composition of Claim 1 whose molecular weight of the said polydialkylsiloxane is 5000 or more. The releasable resin composition according to claim 1 or 2, wherein the block copolymer (B) is a triblock or more. The releasable resin composition according to any one of claims 1 to 3, wherein the block copolymer (B) contains 60% by weight or more of the polydialkylsiloxane. A sheet or film obtained by extrusion-molding the releasable resin composition according to any one of claims 1 to 4. A releasable sheet or a releasable film comprising a base material and a release layer comprising the releasable resin composition according to any one of claims 1 to 4. A pressure-sensitive adhesive sheet or pressure-sensitive adhesive film comprising a base material, a pressure-sensitive adhesive layer, and a release layer composed of the releasable resin composition according to any one of claims 1 to 4. A releasable sheet or a releasable film, wherein the releasable resin composition according to any one of claims 1 to 4 is extruded and laminated on a substrate. 5. A releasability characterized in that a resin to be a base material and a releasable resin composition according to any one of claims 1 to 4 are coextruded to form a resin base material and a release layer. Sheet or releasable film. It is an adhesive sheet or adhesive film containing at least a resin base material, a release layer, and an adhesive layer, and the release layer extrudes the release resin composition according to any one of claims 1 to 4. A pressure-sensitive adhesive sheet or a pressure-sensitive adhesive film, which is molded and laminated on a substrate. The adhesive resin composition, the resin to be the base material, and the release resin composition according to any one of claims 1 to 4 are coextruded to form an adhesive layer, a resin base material, and a release layer. A releasable sheet or a releasable film, characterized in that