TWI568782B - Resin composition and release film - Google Patents

Description

Resin composition and release film

The present invention relates to a resin composition having a good release property and a release film. More particularly, the present invention relates to a release film suitable for surface protection of various members, and a resin composition suitable as a release layer of the release film.

The present invention relates to a release film for surface protection suitable for surface protection of building members, automobile members, display members, and the like, and a resin composition suitable as a release layer for the surface protection release film.

The present invention relates to a release film for surface protection suitable for surface protection of a resin, a metal, glass, or the like, and a resin composition suitable as a release layer for the release film for surface protection.

Generally, the release film is mostly used for a double-sided tape or a single-sided tape with a release film, a protective film for a product, and the like. Since such a release film has been applied to a surface of a substrate such as a resin film or paper by a release agent such as a polyfluorene-based compound, a long-chain alkyl compound or a polyvinyl alcohol urethane. The method. However, since such a release film of a type in which a release agent is applied to a substrate is difficult to uniformly apply, when it is difficult to control the release force, or when the release film is formed into a roll shape, The release agent is transferred to the opposite adhesive layer side to cause problems such as re-adhesiveness (adhesion of the adhesive layer after peeling off the release film).

As a method for solving such a problem, for example, there is disclosed a release film in which a release agent is formulated in a resin: a polyolefin tree crosslinked by polyoxyalkylene is used. A release film of a fat (refer to Patent Document 1), a release film containing a fatty amide-based compound in a polyethylene-based resin (see Patent Document 2), and a bismuth-based compound containing a fatty acid in a propylene-based polymer A release film (refer to Patent Document 3) or the like. In addition, an agricultural film containing a resin composition obtained by adding a fatty acid bis-amine compound to an ethylene-α-olefin copolymer is disclosed (see Patent Document 4).

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. Hei 10-44349

Patent Document 2: Japanese Patent Laid-Open No. 2006-219520

Patent Document 3: Japanese Patent Laid-Open Publication No. 2009-161482

Patent Document 4: Japanese Patent Laid-Open Publication No. 2002-128965

As a release film in the above-mentioned tape or protective film, it is important to protect the adhesive surface and have good release property to the adhesive, but it requires a higher level and uniformity to the recent release film. Type. For example, when manufacturing a tape, a plurality of narrow-width roll-shaped tapes are produced by cutting a slit having a wide width and forming a slit having a relatively narrow width, in order to eliminate the release property between the batches of the product. In all, it is necessary to make the release property of the sheet in the width direction uniform. In addition, in order to protect the automotive exterior components or large liquid crystal display components during the manufacturing process or shipment, a large area of protective film is required, and the requirements are Uniform adhesion and release.

On the other hand, the release film is usually produced by co-extrusion molding or extrusion lamination molding, but in the case of co-extrusion molding and winding into a roll, there are the following cases: the adhesive layer and the opposite side The release layer is firmly followed by the problem that the film cannot be continuously fed out from the roll during use (the roll-out property is poor).

However, with the above prior art, it is not possible to obtain a release film having uniform and moderate release property, good re-adhesiveness of the adhesive layer, and good roll-out property even by co-extrusion molding, and How to achieve it is not known.

An object of the present invention is to provide a release film and a resin composition which have good release properties. Specifically, an object of the present invention is to provide a release film which has uniform and moderate release property, good re-adhesiveness of an adhesive layer, and good roll-out property even by co-extrusion molding. A resin composition suitable as a release layer of the release film. In particular, it is an object of the present invention to provide a release film suitable for surface protection of various members and a resin composition suitable as a release layer of the release film.

An object of the present invention is to provide a release film for surface protection suitable for surface protection of a building member, an automobile member, a display member, and the like, and a resin composition suitable as a release layer for the surface protection release film.

Further, an object of the present invention is to provide a release film for surface protection suitable for surface protection of synthetic resins, metals, glass, and the like, and a resin composition suitable as a release layer for the release film for surface protection.

As a result of intensive studies in view of the above-described problems, the present inventors have found that the above problems can be solved by including a fatty acid bis-amine compound having a specific chemical structure in a polyolefin resin having a specific bending elastic modulus, and the present invention has been completed.

That is, the present invention is based on the following [1] to [15].

[1] A resin composition comprising a polyolefin resin (A) having a flexural modulus of elasticity of 800 MPa or less and a fatty acid bisamine compound (B) represented by the following formula (1); R-CONH-( CH ₂ ) _n -NHCO-R (1)

(wherein, n represents an integer of 1 to 6, and R each independently represents an aliphatic group having a carbon number of 19 or more).

[2] The resin composition according to [1] above, wherein the polyolefin resin (A) is a propylene-based polymer.

[3] The resin composition according to [1] above, wherein the polyolefin resin (A) is an ethylene-propylene copolymer.

[4] The resin composition according to the above [2] or [3], wherein the polyolefin resin (A) contains 4% by weight or more of a component other than propylene.

[5] A molded article obtained by molding the resin composition according to any one of the above [1] to [4].

[6] A release film comprising at least a release layer comprising a polyolefin resin (A) having a flexural modulus of elasticity of 800 MPa or less and a fatty acid bisamine compound (B) represented by the following formula (1); ; R-CONH-(CH ₂ ) _n -NHCO-R (1)

(wherein, n represents an integer of 1 to 6, and R each independently represents an aliphatic group having a carbon number of 19 or more).

[7] The release film according to the above [6], wherein the release layer contains 0.5 to 20 parts by weight of the fatty acid bis-amine compound (B).

[8] The release film according to the above [6] or [7] wherein the polyolefin resin (A) is a propylene-based polymer.

[9] The release film according to the above [6] or [7] wherein the above polyolefin resin (A) is an ethylene-propylene copolymer.

[10] The release film according to any one of [6] to [9] above which further comprises an adhesive layer.

[11] The release film according to [10] above, wherein the release layer forms a surface, and the adhesive layer forms the other surface.

[12] The release film according to any one of [6] to [11] above which is obtained by co-extrusion molding.

[13] The release film according to any one of [6] to [12] above which is for surface protection.

[14] The release film according to [13] above, which is used for surface protection of any one of a building member, an automobile member, and a display member.

[15] The release film according to [13] above, which is used for surface protection of any of a resin, a metal, and a glass.

According to the present invention, a release film and a tree having good release properties can be provided. Fat composition. According to the present invention, in particular, a release film suitable for surface protection of various members and a resin composition suitable as a release layer of the release film can be provided.

According to the present invention, it is possible to provide a release film which has uniform and moderate release property, good re-adhesiveness of an adhesive layer, and good roll-out property even by co-extrusion molding, and is suitable as the The resin composition of the release layer of the release film.

According to the present invention, it is possible to provide a release film for surface protection suitable for surface protection of a building member, an automobile member, a member for display, and the like, and a resin composition suitable as a release layer for the release film for surface protection.

Moreover, the present invention can provide a release film for surface protection suitable for surface protection of synthetic resins, metals, glass, and the like, and a resin composition suitable as a release layer for the release film for surface protection.

The present invention will be described in detail below, but the present invention is not limited thereto, and may be modified without departing from the spirit and scope of the invention. Further, in the present invention, the term "release" does not mean that it is released from a specific shape, and is synonymous with "peeling".

The resin composition of the present invention contains a polyolefin resin (A) and a fatty acid bis-amine compound (B). Further, the release film of the present invention has at least a release layer containing the resin composition.

First, the polyolefin resin (A) constituting the resin composition of the present invention and The fatty acid bis-amine compound (B) will be described.

<Polyolefin resin (A)>

The polyolefin resin used as the polyolefin resin (A) is not particularly limited, and examples thereof include a homopolymer such as ethylene, propylene, and 1-butene, a copolymer of the above homopolymers, or the above homopolymer and 3 -Methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, etc., other carbon atoms having a carbon number of 4 to 20 Various (meth) acrylates such as olefin, (meth)acrylic acid, methyl (meth) acrylate, polar monomers such as vinyl acetate, vinyl alcohol, maleic anhydride, styrene, styrene derivatives, etc. A styrene monomer or the like. Here, (meth)acrylic acid means acrylic acid or methacrylic acid, and the same is true about (meth)acrylate.

The polyolefin resin may be modified with an unsaturated carboxylic acid such as maleic anhydride, maleic acid or acrylic acid or a derivative thereof or an unsaturated decane compound. Further, it may have a crosslinked structure in part.

When the copolymer is used as the polyolefin resin, the chain form is not limited, and may be any one of a block copolymer, a random copolymer, a graft copolymer, and the like, and a polymerization method and a contact for polymerization. The media may also use well-known persons.

These polyolefin resins may be used alone or in combination of two or more.

The polyolefin resin (A) in the present invention is a polyolefin resin having a flexural modulus of 800 MPa or less. When the flexural modulus of the polyolefin resin exceeds the above upper limit value, the release property or uniformity thereof when the release film is formed is lowered. its The reason is not clear, and it is considered that the polyolefin resin having a low bending elastic modulus has a low crystallinity, and the crystallinity thereof is low to contribute to a good and uniform expression of the release property. In other words, it is considered that the reason is that since there is a certain amount or more of the amorphous region of the polyolefin resin, it has a good affinity with the fatty acid bis-amine compound (B) described below.

The polyolefin resin (A) in the present invention may be prepared and used as long as the polyolefin resin is appropriately selected and has a flexural modulus of 800 MPa or less.

Further, for the same reason as described above, the upper limit of the flexural modulus of the polyolefin resin is preferably 700 MPa or less, more preferably 650 MPa or less, still more preferably 600 MPa or less. In addition, the flexural modulus of the polyolefin resin is a value measured in accordance with JIS K7203 (1995) (the same in the following measurement).

The lower limit of the flexural modulus of the polyolefin resin is not limited, but is usually 5 MPa or more, preferably 10 MPa or more, and more preferably 15 MPa or more. When the flexural modulus of the polyolefin resin does not reach the above lower limit, the moldability tends to decrease or the mechanical properties of the release film tend to decrease.

[Propylene polymer]

As one aspect of the polyolefin resin (A) in the present invention, a propylene-based polymer having a flexural modulus of 800 MPa or less is preferable. Hereinafter, a case where a propylene-based polymer is used as the polyolefin resin (A) will be described.

The propylene-based polymer used as the polyolefin resin (A) is only required to have a propylene monomer The unit is not particularly limited as long as it is a component of propylene as a raw material monomer, and usually has 50% by weight or more, preferably 70% by weight or more, and more preferably 80% by weight of the propylene monomer unit. More than % of the polymer. When the propylene monomer unit constituting the propylene-based polymer is at least the above lower limit value, the release property of the release film obtained or the uniformity thereof is preferably optimized.

The upper limit of the propylene monomer unit constituting the propylene polymer is not limited, and may be a propylene homopolymer. Preferably, the propylene monomer unit preferably has 98% by weight or less, more preferably 95% by weight or less, and further preferably It is preferably a copolymer of 90% by weight or less. When the propylene monomer unit constituting the propylene-based polymer is at most the above upper limit value, it is easier to achieve the bending elastic modulus required for the polyolefin resin (A). Therefore, there is a tendency that the release property or the uniformity thereof when the release film is formed becomes good.

As described above, the propylene-based polymer used in the present invention may be a propylene homopolymer, but if it is an isotactic homopolypropylene or a syndiotactic polypropylene, it is difficult to achieve the flexural modulus defined by the present invention. Therefore, when a propylene homopolymer is used as the polyolefin resin (A), a person who lowers stereoregularity is generally used.

When a propylene-based polymer is used as the polyolefin resin (A), a copolymer of a propylene monomer and another monomer is preferred as compared with the propylene homopolymer. The monomer copolymerized with propylene is not particularly limited as long as it is a compound copolymerizable with propylene, and specific examples thereof include ethylene; 1-butene, 1-pentene, and 3-methyl-1-butene. , 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-ten Tetraene, 1-hexadecene, 1-(octadecene, 1-hexadecene, etc., α-olefin having a carbon number of about 4 to 20; (meth)acrylic acid; various (meth) acrylates such as methyl (meth) acrylate; vinyl acetate, A polar monomer such as vinyl alcohol or maleic anhydride; a styrene monomer such as styrene or a styrene derivative. Here, the term "(meth)acrylic acid" means acrylic acid or methacrylic acid, and the same applies to the above (meth)acrylate. These monomers may be used alone or in combination of two or more. Among them, as the monomer copolymerized with propylene, ethylene and an α-olefin having a carbon number of about 4 to 20 are preferable.

Such a copolymer is not limited, and specific examples thereof include a propylene-ethylene copolymer, a propylene-1-butene copolymer, a propylene-ethylene-1-butene copolymer, and a propylene-4-methyl-1-pentyl group. An alkene copolymer, a copolymer of propylene and another α-olefin, a copolymer of propylene and a polar monomer, and the like.

Each of the copolymers may be not only a random copolymer but also a block copolymer, a graft copolymer or the like.

The stereoregularity of each of the copolymers is not limited, and the propylene chain moiety may be any of isotactic, syndiotactic, irregular, and stereoblocks.

A catalyst and a polymerization method used for the polymerization of the propylene-based polymer can be suitably used.

Further, the propylene-based polymer in the present invention may be modified by using an unsaturated carboxylic acid or a derivative thereof, an unsaturated decane compound or the like. Further, it may have a crosslinked structure in part.

Among these, as the propylene-based polymer, propylene-ethylene copolymerization is preferred. , propylene-1-butene copolymer, propylene-ethylene-1-butene copolymer.

Further, the propylene-based polymer may be used in combination of two or more kinds of the above resins, and a propylene-based polymer or a polyolefin other than the propylene-based polymer may be used in combination.

The propylene-based polymer in the present invention has a flexural modulus of 800 MPa or less. When the flexural modulus of the propylene-based polymer exceeds the above upper limit value, the release property or uniformity thereof when the release film is formed is lowered. The reason for this is not clear, but it is considered that the propylene-based polymer having a low flexural modulus has a low crystallinity, and its low crystallinity contributes to a good and uniform expression of the release property. In other words, it is considered that the reason is that since there is a certain amount or more of the amorphous region of the propylene-based polymer, it has a good affinity with the fatty acid bis-amine compound (B) described below. Moreover, the upper limit of the flexural modulus of the propylene-based polymer is preferably 700 MPa or less, more preferably 650 MPa or less, and still more preferably 600 MPa or less, for the same reason as described above.

The lower limit of the flexural modulus of the propylene-based polymer is not limited, but is usually 5 MPa or more, preferably 10 MPa or more, and more preferably 15 MPa or more. When the flexural modulus of the propylene-based polymer does not reach the above lower limit, the moldability tends to decrease or the mechanical properties of the release film tend to decrease.

The melt flow rate (MFR, Melt Flow Rate) of the propylene-based polymer is not particularly limited, and is usually 0.5 to 50 g/10 minutes, preferably 1 to 2, at 230 ° C and a load of 2.16 kg (21.18 N). 30 g/10 points, more preferably 2 to 25 g/10 points. The release film of the present invention is produced in any of the cases where the MFR of the propylene-based polymer is less than the above lower limit value or exceeds the above upper limit value. The formability at the time is not sufficient.

[Propylene-ethylene block copolymer]

In the present invention, as the polyolefin resin (A), a block copolymer of one aspect of the propylene-based polymer is preferably used. Among them, it is preferred to use a block copolymer comprising a propylene block and at least one of ethylene and an α-olefin (hereinafter sometimes "containing at least one of a propylene block and an ethylene and an α-olefin. The block copolymer is referred to as "propylene-ethylene block copolymer").

Here, examples of the α-olefin include α-olefins having a carbon number of about 4 to 20. Furthermore, at least one of the ethylene and the α-olefin includes not only the individual polymer block of ethylene, the polymer block of the α-olefin, but also the copolymer block of ethylene and the α-olefin or A block of two or more different α-olefins, and also containing propylene as its constituent unit.

The propylene-ethylene block copolymer generally has a domain of a propylene copolymer block domain and at least one polymer block of ethylene and an alpha olefin. By using the block copolymer having different domains as the polyolefin resin (A), the release property or the uniformity thereof when the release film is formed using the resin composition of the present invention becomes good, and becomes resistant. The tendency of excellent impact and rigidity.

Preferred examples of the propylene-ethylene block copolymer include a block copolymer comprising a propylene homopolymerized portion (a) and an ethylene-propylene random copolymerized portion (b).

The content ratio of the propylene homopolymerization portion (a) to the ethylene-propylene random copolymerization portion (b) is not limited, and it is preferred that the propylene homopolymerization portion (a) is 20 to 50 parts by weight. %, the ethylene-propylene random copolymerization portion (b) is 80 to 50% by weight. When the content ratio of the propylene homopolymerized portion (a) is within the above range, the release property or uniformity thereof when the release resin film is formed using the resin composition of the present invention becomes good, and chemical resistance is obtained. Excellent in impact resistance and rigidity.

For the same reason as described above, the preferred ratio of the proportion of the propylene homopolymerized portion (a) to the ethylene-propylene random copolymerized portion (b) is: the propylene homopolymerized portion (a) is 30 to 45% by weight, ethylene. The propylene random copolymerization portion (b) is 70 to 55% by weight.

The ethylene content in the propylene-ethylene random copolymerization portion (b) is not limited, and may be composed only of an α-olefin containing propylene, but preferably has an ethylene content of 40 to 70% by weight. When the ethylene content is in the above range, the release property of the release film of the resin composition of the present invention or the uniformity thereof is improved, and the impact resistance and rigidity are excellent.

When a block copolymer comprising a propylene homopolymerized portion (a) and an ethylene-propylene random copolymerized portion (b) is used as the polyolefin resin (A), generally, the flexural elasticity of the propylene homopolymerized portion (a) is used. The modulus is higher than the flexural modulus of the ethylene-propylene random copolymerized portion (b).

As described above, the polyolefin resin (A) in the present invention has a flexural modulus of 800 MPa or less, and is used in block copolymerization using the propylene homopolymerized portion (a) and the ethylene-propylene random copolymerized portion (b). In the case of the blended polyolefin resin (A), the flexural modulus of the ethylene-propylene random copolymerized portion (b) may be 800 MPa or less.

In other words, as long as the flexural modulus of the ethylene-propylene random copolymerized portion (b) is 800 MPa or less, the flexural modulus of elasticity as a whole of the block copolymer is more than 800 MPa.

The reason for this is that, as described above, the propylene-ethylene block copolymer generally has a domain of a propylene polymer block domain and at least one polymer block of ethylene and an a-olefin, and the phases are independently present. Therefore, the effect of the present invention can be exhibited as long as the flexural modulus of the ethylene-propylene random copolymerized portion (b) is 800 MPa or less.

Further, for the same reason as described above, the flexural modulus of the ethylene-propylene random copolymerized portion (b) is preferably 700 MPa or less, more preferably 650 MPa or less, still more preferably 600 MPa or less.

The lower limit of the flexural modulus of the ethylene-propylene random copolymerization portion (b) is not limited, and is usually 5 MPa or more, preferably 10 MPa or more, and more preferably 15 MPa or more. When the flexural modulus of the ethylene-propylene random copolymerized portion (b) does not reach the above lower limit, the moldability tends to decrease or the mechanical properties of the release film tend to decrease.

In the block copolymer containing the propylene homopolymerized portion (a) and the ethylene-propylene random copolymerized portion (b), as a method for confirming the flexural modulus of the ethylene-propylene random copolymerized portion (b), A copolymer having a composition equivalent to only the ethylene-propylene random copolymerized portion (b) was produced and the flexural modulus was measured. Further, when the block copolymerized polymer is dissolved in a solvent and separated into a propylene homopolymerized portion (a) and an ethylene-propylene random copolymerized portion (b), The bending elastic modulus was measured by separating and recovering. As a condition at the time of the separation, for example, a method of extracting at 150 to 200 ° C using o-dichlorobenzene as a solvent can be mentioned.

The method for producing the propylene-ethylene block copolymer is not limited, and it can be usually produced by slurry polymerization, gas phase polymerization or liquid phase bulk polymerization using a high stereoregular catalyst, and as a polymerization method, batching can be employed. Any of the methods of polymerization and continuous polymerization.

In the production of the propylene-ethylene block copolymer, in terms of quality, it is preferred to first form a propylene homopolymerized portion (a) by homopolymerization of propylene, and then at least by ethylene and an α-olefin and propylene. One of the random copolymerizations forms an ethylene-propylene random copolymerized portion (b). For example, homopolymerization of propylene can be carried out by using a catalyst in which a solid component formed by contacting magnesium chloride with titanium tetrachloride, an organic acid halide, and an organic cerium compound and an organoaluminum compound component is used, followed by ethylene and propylene. Manufactured by random copolymerization.

The propylene-ethylene block copolymer may be a ternary system or more copolymer containing a vinyl ester such as vinyl acetate, or a mixture thereof, insofar as the effect of the present invention is not impaired.

As an example of such a propylene-ethylene block copolymer, "Zelas 7023" manufactured by Mitsubishi Chemical Corporation, "Novatec PP BC3H" manufactured by Japan Polypropylene Corporation, "Catalloy CA7320A" manufactured by SunAllomer Co., Ltd., " Catalloy Adflex C200F" and so on.

[Polyolefin resin (A) other than propylene-based polymer]

The polyolefin resin other than the propylene-based polymer which is used as the polyolefin resin (A) in the present invention, that is, the polyolefin resin other than the propylene-based polymer having a flexural modulus of 800 MPa or less, may be exemplified below.

Specifically, examples thereof include low-, medium-, high-density polyethylene (branched or linear) ethylene homopolymer, ethylene-propylene copolymer, ethylene-1-butene copolymer, and ethylene-4- Methyl-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-vinyl alcohol copolymer (including ethylene-vinyl acetate copolymer saponified product), ethylene-( An ethylene-based polymer such as a methyl methacrylate copolymer; a 1-butene polymer such as a 1-butene homopolymer, a 1-butene-ethylene copolymer, or a 1-butene-propylene copolymer; Open-ring metathesis polymer of alkenyl or A so-called cyclic polyolefin-based resin such as an olefin derivative or an ethylene copolymer.

Here, the ethylene-based polymer refers to a polymer containing ethylene as a main component as a raw material monomer, preferably containing 50% by weight or more, and the same is true for the 1-butene-based polymer.

The polyolefin resin other than the propylene-based polymer used as the polyolefin resin (A) may have a flexural modulus of 800 MPa or less, preferably 700 MPa or less, more preferably 650 MPa or less, in the resin exemplified above. Further, it is preferably a resin of 600 MPa or less. The lower limit of the flexural modulus is not limited, but is usually 5 MPa or more, preferably 10 MPa or more, and more preferably 15 MPa or more.

Used as a polyolefin resin other than the propylene-based polymer of the polyolefin resin (A) The melt flow rate (MFR) is not limited and is usually 0.5 to 50 g/10 minutes, preferably 1 to 30 g/10 minutes, more preferably 2 to 25 g/10 minutes. Here, when the polyolefin resin (A) is a propylene resin, as described above, MFR means a value at 230 ° C and a load of 21.2 N, but the polyolefin resin (A) is a vinyl system. In the case of a polymer, a 1-butene polymer or other polyolefin resin, it means a value at 190 ° C under a condition of 21.2 N load. When either the case where the MFR of the polyolefin resin (A) is less than the above lower limit value or exceeds the above upper limit value, the moldability when the release film of the present invention is produced may be insufficient.

In the present invention, it is preferred that the polyolefin resin (A) contains 4% by weight or more of a component other than propylene. The method for measuring the components other than propylene in the polyolefin resin (A) can be carried out by the following procedure.

‧ Method for extracting the release layer component from the film: a cross-sectional observation was carried out using a polarizing microscope, and the thickness of the release layer in the film was measured. The release layer is peeled off using a cutting tool or the like. In this case, the film may be immersed in a solvent such as ethanol or propanol, and swelled and peeled off.

‧ Components other than propylene (C3) were determined by NMR (Nuclear Magnetic Resonance). In particular, specific methods regarding the ethylene component are shown below.

1) Measurement by NMR other than propylene: The release layer from the film was completely utilized by protons and determined by the following conditions according to the following conditions. It can be obtained by analyzing a ¹³ C-NMR spectrum. As the model, for example, GSX-400 manufactured by JEOL Ltd. or an equivalent device (nuclear magnetic resonance frequency of 100 MHz or more) can be used, and the measurement conditions are as follows.

Solvent: o-dichlorobenzene: toluene = 4:1 (volume ratio)

Concentration: 100 mg/ml or more

Temperature: 130 ° C

Pulse angle: 90°

Pulse interval: 15 seconds

Cumulative number: 5000 times or more

2) Atlas: The attribution of the map can be carried out by referring to Macromolecules, 17, 1950 (1984). The maps determined according to the above conditions are shown in the following table. In the table, symbols such as "Sαα" are based on the representation of Carman et al. (Macromolecules, 10, 536 (1977)), P represents methyl carbon, S represents methylene carbon, and T represents methine carbon.

3) Calculation of ethylene content: When "P" is used as the propylene unit in the copolymer chain and "E" is the ethylene unit, PPP may be present in the chain. Six triads of PPE, EPE, PEP, PEE and EEE. As described in Macromololeoules, 15, 1150 (1982), etc., the concentration of these triplets and the peak intensity of the spectrum are related by the following relational expressions (a) to (f).

[PPP]=k×l(Tββ) (a)

[PPE]=k×l(Tβδ) (b)

[EPE]=k×l(Tδδ) (c)

[PEP]=k×l(Sββ) (d)

[PEE]=k×l(Sβδ) (e)

[EEE]=k×{l(Sδδ)/2+l(Sγδ)/4} (f)

Here, the braces "[]" indicate the fraction of the triads, for example, [PPP] is the fraction of the PPP triads in all triads. Therefore, [PPP]+[PPE]+[EPE]+[PEP]+[PEE]+[EEE]=1 (g).

Further, k represents a coefficient, and l represents a spectral intensity, for example, 1 (Tββ) means a peak intensity of 28.7 ppm attributed to Tββ.

The fraction of each triplet was obtained by using the above relational expressions (a) to (g), and the ethylene content was determined by the following formula.

Ethylene content (% by mole) = ([PEP] + [PEE] + [EEE]) × 100

Further, the conversion of the ethylene content from the mole % to the weight % was carried out using the following formula.

Ethylene content (% by weight) = (28 × X / 100) / {28 × X / 100 + 42 × (1-X / 100)} × 100

Here, X is the ethylene content in terms of mol%. The party described here The method is a method for determining the ethylene content, and the content of the components other than ethylene can be converted after each map is assigned.

<Fatty acid bis-amine compound (B)>

The fatty acid biguanide compound (B) in the present invention is a compound represented by the following formula (1). The aliphatic groups R at the two ends may be the same or different, but are preferably the same in terms of ease of manufacture.

R-CONH-(CH ₂ ) _n -NHCO-R (1)

(wherein, n represents an integer of 1 to 6, and R independently represents an aliphatic group having a carbon number of 19 or more.)

The chemical structure of the aliphatic group R represented by the formula (1) of the fatty acid bis-amine compound has an influence on the release property. Since the fatty acid biguanide compound (B) in the present invention is a fatty acid bis-indenamine compound having an aliphatic group having a carbon number of 19 or more at both terminals, a crystal structure having less confusion can be formed. Therefore, when the release layer containing the fatty acid biguanide compound (B) is brought into contact with the adhesive layer, molecular crosslinking between the two layers can be suppressed to exhibit good release properties.

Further, by forming a release layer containing the fatty acid bis-amine compound (B), even when an adhesive is applied to the release layer and dried to form an adhesive layer, when heated, or adhered to When the layer is placed in a state of being stored in a high-temperature environment, good release properties can be exhibited. This is because the fatty acid bis-amine compound (B) has a high melting temperature, so that the crystal structure can be maintained even at a high temperature, and molecular crosslinking with the adhesive substance can be suppressed. As a result, stable release characteristics can be exhibited even over time.

Further, the longer the two aliphatic groups (R in the above formula) constituting the fatty acid bis-indoleamine compound (B), the longer the chain, the better the release property, but it is easy to manufacture and easy to obtain. In view of the above, it is preferably selected from the group consisting of a fatty acid bis-indoleamine compound having an aliphatic group having a carbon number of 19 to 27, and more preferably a fatty acid biguanide selected from an aliphatic group having a carbon number of 19 to 23. The amine compound is further preferably a fatty acid bis-indenamine compound selected from the group consisting of aliphatic groups having a carbon number of 21 to 23. By the fatty acid bis-amine compound having the carbon number of the aliphatic group in the above range, sufficient release property can be obtained, and it is difficult to generate a hair when the resin composition or the release film of the polyolefin resin (A) is produced. It is better to have problems such as smoke and foaming.

The two aliphatic groups (R in the above formula) of the fatty acid bis-amine compound may each be a linear aliphatic group, or may have a branched aliphatic group, preferably a linear aliphatic group. If the aliphatic group in the fatty acid bis-amine compound is linear, the release property becomes good. The reason for this is not clear, but it is considered that the reason is that a fatty acid bis-amine compound having a linear aliphatic group having a carbon number of 19 or more can form a crystal structure with less confusion.

The two aliphatic groups (R in the above formula) of the fatty acid bis-amine compound may each be a saturated aliphatic group or an unsaturated aliphatic group, but are preferably a saturated aliphatic group. Examples of the aliphatic group include a nonyl group, an eicosyl group, a behenyl group, a behenyl group, and a behenyl group.

Among the above, an alkyl group having a carbon number of 21 to 23 is preferable, and specifically, a behenyl group and a behenyl group are particularly preferable.

The fatty acid bis-amine compound (B) has a divalent linking group (corresponding to the -(CH ₂ ) _n - moiety in the above formula) which connects two guanamine groups. The divalent linking group is not particularly limited, and examples thereof include a methylene group, an ethylidene group, a trimethylene group, a tetramethylene group, and a hexamethylene group, and a methylene group or an ethylidene group is preferred.

The fatty acid bis-indolamine compound (B) in the present invention may be a compound corresponding to the above formula (1), or two or more different compounds may be used in combination.

Further, in the present invention, a fatty acid bis-amine compound other than the above formula (1) may be used in combination. Specifically, in the above formula (1), R is a compound having a linear aliphatic group having a carbon number of 18 or less. Among them, it is preferred to contain a compound corresponding to the above formula (1) in an amount of 90 mol% or more of all fatty acid bisamine compounds.

The fatty acid bis-amine compound of the present invention can be produced by a usual method of hydrating a specific fatty acid with a specific alkylenediamine according to a conventional method. Further, the fatty acid bis-amine compound obtained by performing guanidation can also be purified by a usual method.

As a method for producing a normal fatty acid bis-amine compound, for example, it can be used at a temperature of 100 to 250 ° C under an atmospheric pressure of an inert gas atmosphere or under pressure, and if necessary, a borohydride alkali compound, phosphorous acid, hypophosphorous acid. Alternatively, it may be produced by reacting a fatty acid with an alkylenediamine in the presence of such an alkali metal salt or an alkaline earth metal salt or the like.

The fatty acid as a raw material is preferably a fatty acid having a carbon number of 20 or more, preferably a fatty acid having a carbon number of 20 to 28, more preferably a fat having a carbon number of 20 to 24 The acid is further preferably a fatty acid having 22 to 24 carbon atoms, and examples thereof include arachidic acid, behenic acid, and tetracosanoic acid. Preferred are behenic acid and tetrakisolic acid. Further, in the case where the carbon number of the fatty acid used as the raw material is dispersed, the molecular structure of the obtained fatty acid bis-guanamine can be obtained in various structures as long as it has the fatty acid bis-amine of the above formula (1). It may be a mixture of fatty acid bis-amines having different molecular configurations.

Examples of the alkylene diamines include alkylenediamines having a carbon number of 1 to 6, and examples thereof include methylene diamine, ethylene diamine, trimethylene diamine, and tetramethylene diamine. Amine, hexamethylenediamine, and the like. It is preferably methylene diamine or ethylene diamine, more preferably ethylene diamine.

<Other ingredients>

In the release layer of the release film of the present invention, a resin other than the polyolefin resin (A) or the fatty acid bis-amine compound (B) or an additive may be blended in the range which does not significantly impair the effects of the present invention (hereinafter Sometimes called "other ingredients"). The other components may be used alone or in combination of two or more kinds in any combination.

Specific examples of the resin other than the polyolefin resin (A) include polyolefins not included in the polyolefin resin (A); polyphenylene ether resins; and polyfluorenes such as nylon 6, nylon 66, and nylon 11; Amine resin; polycarbonate resin; polyester resin such as polyethylene terephthalate or polybutylene terephthalate; (meth)acrylic resin such as polymethyl methacrylate; polystyrene A thermoplastic resin such as a styrene resin or various thermoplastic elastomers.

The polyolefin which is not contained in the polyolefin resin (A) is a propylene homopolymer which is a propylene-based polymer having a bending elastic modulus of more than 800 MPa. As a preferable aspect of the resin composition of the present invention, a polyolefin resin (A) and a propylene-based polymer having a flexural modulus of more than 800 MPa are used in combination.

Further, examples of the additives include various heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, age resistors, nucleating agents, plasticizers, impact modifiers, phase solvents, defoamers, and tackifiers. Agents, cross-linking agents, surfactants, lubricants, anti-caking agents, processing aids, antistatic agents, flame retardants, flame retardant auxiliaries, fillers, colorants, inorganic crystal nucleating agents, and the like. Further, a release agent other than the fatty acid bis-amine compound may be contained.

These other resins or additives may be used singly or in combination of two or more kinds in any combination.

Examples of the heat stabilizer and the antioxidant include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, and halides of alkali metals.

The flame retardant can be roughly classified into a halogen-based flame retardant and a non-halogen flame retardant, but a non-halogen flame retardant is preferred in terms of environment. Examples of the non-halogen flame retardant include a phosphorus-based flame retardant, a hydrated metal compound (aluminum hydroxide, magnesium hydroxide) flame retardant, a nitrogen-containing compound (melamine-based or lanthanide-based) flame retardant, and an inorganic system. A compound (borate, molybdenum compound) flame retardant or the like.

Fillers can be broadly classified into organic fillers and inorganic fillers. Examples of the organic filler include starch, cellulose microparticles, wood flour, bean curd, rice husk, Wheat bran or the like is derived from a natural polymer or a modified product thereof. Further, examples of the inorganic filler include talc, calcium carbonate, zinc carbonate, ash stone, cerium oxide, aluminum oxide, magnesium oxide, calcium citrate, sodium aluminate, calcium aluminate, sodium aluminosilicate, and cesium. Magnesium silicate, glass balloon, carbon black, zinc oxide, antimony trioxide, zeolite, hydrotalcite, metal fiber, metal whisker, ceramic whisker, potassium titanate, boron nitride, graphite, carbon fiber, and the like.

Examples of the nucleating agent include a sorbitol compound and a metal salt thereof; a benzoic acid and a metal salt thereof; a phosphate metal salt; an ethylene bis decylamine, a methylene bis decyl decylamine, an ethylene bis acrylamide, and a hexa Methyl bis-9,10-dihydroxystearyl behenamide, p-xylylene bis-9,10-dihydroxystearamide, decane dibenzoic acid hydrazide, hexane dicarboxylic acid Dibenzoyl hydrazine, 1,4-cyclohexanedicarboxylic acid dicyclohexyl decylamine, 2,6-naphthalenediphthalamide, N,N',N"-tricyclohexylbenzene phthalamide , trimesic acid tris(t-butyldecylamine), 1,4-cyclohexanedimethylbenzidine, 2,6-naphthalene dicarboxylic acid dicyclohexyldecylamine, N,N'-dibenzidine 1,4-1,4-diaminocyclohexane, N,N'-dicyclohexanecarbonyl-1,5-diaminonaphthalene, ethylene bis-lipidamine, N,N'-ethylene bis-12- A guanamine compound such as hydroxystearylamine or octanedicarboxylate benzoate or the like. Further, examples of the inorganic crystal nucleating agent include talc, kaolin, and cerium oxide.

The content of the "other components" in the case of using the release layer in the present invention is not limited, and is preferably 0.01% by weight or more in the release layer or the resin composition described below. It is preferably 0.2% by weight or more, usually 10% by weight or less, and preferably 5% by weight or less. Furthermore, in advance, the release will be When the raw material used for the layer is a resin composition, when the other components are used as a master batch, it may be contained in a concentration of 2 to 50 times, preferably 3 to 30 times the above content.

<Resin composition and release layer>

The resin composition of the present invention contains a polyolefin resin (A), a fatty acid bis-amine compound (B), and a resin composition containing any other component.

Moreover, the release layer in the present invention contains a polyolefin resin (A), a fatty acid bis-amine compound (B), and a layer containing any other component.

The content ratio of the polyolefin resin (A) constituting the resin composition or the release layer to the fatty acid bis-amine compound (B) is not limited, and the fatty acid bis-amine compound is usually contained in 100 parts by weight of the polyolefin resin (A). (B) is 0.5 parts by weight or more, preferably 1 part by weight or more, more preferably 2 parts by weight or more, and on the other hand, it is usually contained in an amount of 20 parts by weight or less, preferably 15 parts by weight or less, based on the fatty acid bisammonium compound (B). More preferably, it is 10 parts by weight or less. When the content ratio of the fatty acid biguanide compound (B) is less than the above lower limit, the release property or the uniformity of the release film tends to be lowered. On the other hand, when the content ratio of the fatty acid biguanide compound (B) exceeds the above upper limit value, the excess fatty acid biguanide compound leaks from the release layer and is transferred to the adhesive layer side or away from the adhesive layer side. The mechanical strength of the film is reduced.

The content ratio of the fatty acid bis-amine compound (B) in the resin composition or the release layer is not limited, and is usually 0.5 parts by weight or more, preferably 1 part by weight or more, more preferably 2 parts by weight or more. On the one hand, usually contains It is 20 parts by weight or less, preferably 15 parts by weight or less, more preferably 10 parts by weight or less. When the content ratio of the fatty acid biguanide compound (B) is less than the above lower limit, the release property or the uniformity of the release film tends to be lowered. On the other hand, when the content ratio of the fatty acid biguanide compound (B) exceeds the above upper limit value, the excess fatty acid biguanide compound leaks from the release layer and is transferred to the adhesive layer side or away from the adhesive layer side. The mechanical strength of the film is reduced.

The release layer in the present invention may be obtained by blending the above-mentioned respective components as a raw material and directly forming the molded article, but it is preferred to prepare the resin composition of the present invention in advance and to manufacture the resin. The formed body obtained by molding the composition was set as a release layer.

The resin composition of the present invention can be obtained by mixing the above components in a specific ratio. The mixing method is not particularly limited as long as the raw material components can be uniformly dispersed and mixed. In other words, by mixing the above-mentioned respective raw material components or the like at the same time or in an arbitrary order, a composition in which the respective components are uniformly distributed can be obtained.

In order to carry out more uniform mixing and dispersion, it is preferred to melt and mix a specific amount of the above raw material components. Specifically, for example, each raw material component or the like of the resin composition may be mixed in an arbitrary order, and then heated, or all of the raw material components may be melted while being sequentially melted. Further, only one of the above components may be prepared as a resin composition in advance, and the resin composition and other components may be blended to form a release layer.

a mixing method or a mixing condition as long as the raw material components can be uniformly mixed There is no particular limitation, but in terms of productivity, it is preferred to mix raw materials using, for example, a drum mixer, a V-type agitator, a belt type agitator, a Henschel mixer, etc., and to use a single-axis extruder. Or a method such as a continuous kneading machine such as a twin-screw extruder and a batch kneading machine such as a roll mill, a Banbury mixer, and a pressure kneader to perform melt-kneading. The temperature at the time of melt mixing may be a temperature at which at least one of the raw material components is in a molten state, and a temperature at which all the components to be used are usually melted is generally carried out at 150 to 250 ° C in many cases.

The melt flow rate (MFR) of the resin composition of the present invention is not particularly limited, and is usually 0.5 to 200 g/10 minutes, preferably 1 to 50 at 230 ° C and a load of 2.16 kg (21.18 N). g/10 points, more preferably 2~25 g/10 points. When the MFR does not reach the above lower limit value, molding at a high speed may become difficult. Moreover, when the MFR exceeds the above upper limit value, the mechanical strength of the release layer obtained by molding the resin composition may be lowered.

<release film>

The release film of the present invention may be a single layer film obtained by molding only the release layer alone, or may have a layer other than the release layer (hereinafter sometimes referred to as another layer) as long as it contains the release layer. The layered body. Examples of the other layer include a base layer (support layer) such as another resin, metal, or glass, a protective layer, a coating layer, and the like, in addition to the adhesive layer described below. Since the release film of the present invention is excellent in release property, it can be clearly exerted as a laminate having a release layer and other layers. Furthermore, the layers of the laminate are randomly formed and may have the same species or different species. The plurality of layers may be used as other layers, and may have two or more release layers.

Further, the shape of the release film of the present invention is not limited, and it is usually a flat shape of a single piece or a roll shape obtained by winding a flat film, and may have a cylindrical shape or an indefinite shape.

The method for producing the release film of the present invention is not particularly limited, and is preferably melt extrusion molding. In the melt extrusion molding, a release film can be obtained by extrusion molding a raw material into a film shape or a sheet shape from an extruder. Expansion molding and blow molding are also included in the melt extrusion molding. Further, as a production method other than the melt extrusion molding, for example, a release film can be produced by a molding method such as injection molding or press molding. Further, the release film obtained by the molding methods may be subjected to stretching treatment such as uniaxial or biaxial. Further, secondary molding such as vacuum forming, pressure forming, and vacuum pressure forming may be performed.

In terms of production efficiency, it is preferred to produce a release film as a laminate by co-extrusion molding, extrusion lamination molding, extrusion coating, or the like.

In the case of producing a release film as a laminate by extrusion build-up or extrusion coating, at least one substrate layer can usually be used. That is, a method in which a base material layer which has been formed is rolled up, a molten resin or the like is laminated on the surface of the base material layer, or a solution is applied and dried to be coated.

In the release film of the present invention, the release layer may be used as the substrate layer, or the other layer may be used as the substrate layer.

In the case of co-extrusion molding, the raw material of the release layer of the present invention and the raw material resin constituting the other layer are extruded from different extruders, and are accumulated in the mold. Layered and formed. Since the release layer of the present invention is excellent in release property, a release film which is a good laminate can be obtained by co-extrusion molding by appropriately selecting a resin or the like which is used as another layer. Further, a laminate comprising three or more layers may be formed by co-extrusion molding.

In general, in the case of producing a release film of a laminate by co-extrusion molding, although it is advantageous in terms of production efficiency, the adhesion between the layers of the release film obtained tends to be strong. Therefore, in the case where the product value is produced by the release property between the release layer and the other layers, it becomes difficult to obtain a good product. However, since the release layer of the release film of the present invention is excellent in release property, the above problems are not caused.

The reason for this is not clear, but it is considered that the reason is that since the fatty acid bis-amine compound (B) has a specific aliphatic group, a stable crystal structure is formed, and since the polyolefin resin (A) has a specific bending elastic modulus, Therefore, it has a good affinity with the fatty acid biguanide compound (B). Therefore, it is considered that the transfer of the fatty acid bis-amine compound (B) to the other layer can be suppressed, whereby a release film having good release property can be obtained even by co-extrusion molding.

Specific examples of the release film of the present invention include a "single-layer release film" containing only a release layer, and a release film having a release layer on one side or both sides of the adhesive layer. "Double-sided tape", which is a single-sided tape that integrates the release layer and the adhesive layer by integrating the base layer with the adhesive layer and having a release layer on the adhesive layer side; "Wait.

As a function of the release layer, the adhesive layer is stored in a state where it is not used. The function of protecting the adhesive surface in a manner that does not adhere to other substances, the function of preventing the adhesive layer from sticking to each other, the function of preventing the adhesive component from leaking out, and the like, and can be easily peeled off from the adhesive layer, and the residue of the release agent must not be generated. The adhesion caused by the adhesive layer is reduced.

Since the release film of the present invention has a uniform release force due to the release layer, it can have the above characteristics at a higher level. Further, even when a release film having a wide width is formed, the release property in the width direction of the sheet can be made uniform. Therefore, even when a large-area release film is produced, uniform adhesion and release property can be exhibited. Further, even when a plurality of release films having a narrow width are formed in the slit-cutting film to form a plurality of release films (tapes) having a narrow width, the adhesion between the batches and the release property can be uniformly maintained.

The thickness of the release film of the present invention is not particularly limited, and the thickness of the release layer in the single-layer release film or laminate is usually 0.1 to 100 μm, preferably 0.5 to 100 μm. If the thickness is within the above range, the deterioration of the release property caused by the unevenness of the thickness does not occur, and it is also economically preferable.

The total thickness in the case where the release film of the present invention is a laminate is not particularly limited and is usually 0.5 μm to 5 mm, preferably 1 μm to 2 mm, more preferably 10 μm to 1 mm.

<adhesive layer>

The adhesive layer constituting the release film as the laminate is not limited, and may be any adhesive property to other materials. Further, in the present invention, not only the case of having an adhesive layer independently, for example, by coating or impregnating the adhesive component with the release type The case where the layer or the substrate layer functions as an adhesive layer is also included in the adhesive layer. Such a base material layer may be porous or may be a fibrous material such as a nonwoven fabric.

Examples of the material used for the adhesive layer in the present invention include amorphous or low crystallinity resins having a glass transition temperature of 23 ° C or lower, thermoplastic elastomers, and various oligomerizations having a number average molecular weight of 500 to 10,000. The body may also be a mixture of the above. Further, the crosslinked or uncrosslinked resin may be used by dissolving or swelling the solvent in a low volatility solvent.

Examples of the material of the specific adhesive layer include thermoplastic elastomers such as a styrene thermoplastic elastomer, an olefin thermoplastic elastomer, and a polyester thermoplastic elastomer, or an acrylic adhesive, a natural rubber adhesive, and a synthetic rubber. Adhesives, polyoxygenated adhesives, etc. Among them, a styrene-based thermoplastic elastomer or a polyoxyn-based adhesive is preferably used. These may be used singly or in combination of two or more.

The styrene-based thermoplastic elastomer may be a block copolymer having a polymer block mainly composed of a vinyl aromatic compound and a copolymer block which imparts flexibility. Specifically, a block copolymer having a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of butadiene and/or isoprene can be exemplified and/or embedded A hydrogenated block copolymer obtained by hydrogenating a segment copolymer. The vinyl aromatic compound is not limited, and a styrene derivative such as styrene or α-methylstyrene is preferred.

Examples of the olefin-based thermoplastic elastomer include ethylene, propylene, and carbon number. An α-olefin, a non-conjugated diene, a vinyl acetate or the like of about 4 to 10 is a copolymer of a monomer component. Specific examples thereof include a copolymer of ethylene and propylene, a copolymer of ethylene and an α-olefin having a carbon number of 4 to 10, a copolymer of propylene and an α-olefin having a carbon number of 4 to 10, and ethylene. A copolymer of a non-conjugated diene component, a copolymer of ethylene and an α-olefin having a carbon number of about 3 to 10 and a non-conjugated diene component, or a blend of an olefin resin such as polypropylene and an olefin rubber. These may be any of a block copolymer, a graft copolymer, and a random copolymer. Further, the olefin thermoplastic elastomer may be a crosslinked person.

Examples of the α-olefin include 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, and 1- Terpene and the like. Examples of the non-conjugated diene include 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, and 6-methyl-1,5-heptane. Chain-like non-conjugated dienes such as alkene, 7-methyl-1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroanthracene, 5-vinyl group Alkene, 5-ethylidene-2-nor Alkene, 5-methylene-2-nor Alkene, 5-isopropylidene-2-lower Alkene, 6-chloromethyl-5-isopropenyl-2-lower a cyclic non-conjugated diene or the like such as an alkene.

The polyester-based thermoplastic elastomer may, for example, be a block copolymer of a crystalline polyester and a polyalkylene ether or an aliphatic polyester. Examples of the crystalline polyester block include an aromatic polyester such as polybutylene terephthalate or an alicyclic polyester such as polyester obtained by condensing cyclohexane dicarboxylic acid with cyclohexane dimethanol. . Examples of the polyalkylene ether block include polytetramethylene ether glycol and polytrimethylene. Ether diol, poly(propylene ether diol), polyethyl ether diol, and the like. Examples of the aliphatic polyester include an aliphatic dicarboxylic acid having a carbon number of 2 to 10 such as adipic acid or sebacic acid, and a carbon number of 2 to 10 such as ethylene glycol or 1,4-butanediol. A polyester obtained by condensation of an aliphatic diol.

The above-mentioned other components which can be contained in the release layer can be similarly contained in the adhesive layer used in the present invention.

In particular, it is preferable to contain a softener for a hydrocarbon-based rubber in the adhesive layer. In particular, when a styrene-based thermoplastic elastomer is used, it is preferred to use a softener for a hydrocarbon-based rubber in combination. The softener for the hydrocarbon-based rubber is preferably a mineral oil-based or synthetic resin-based softener, and more preferably a mineral oil-based softener. The mineral oil softener is usually a mixture of an aromatic hydrocarbon, a naphthenic hydrocarbon, and a paraffinic hydrocarbon. Each of the total carbon atoms is said to be a paraffinic hydrocarbon, and the total carbon atom is called Those who are about 30 to 45% or more of naphthenic hydrocarbons are called naphthenic oils, and those in which more than 35% of the total carbon atoms are aromatic hydrocarbons are called carbon aromatic oils. Among these, an alkane-based oil is preferred in terms of good color tone. Further, examples of the synthetic resin-based softening agent include polybutene and low molecular weight polybutadiene. Further, the softener for the hydrocarbon-based rubber may be used alone or in combination of a plurality of the above-mentioned various softeners.

The dynamic viscosity of the hydrocarbon-based rubber softener at 40 ° C is preferably 20 psi or more, more preferably 50 psi or more, and preferably 800 psi or less. It is 600 cents or less.

The flash point of the softener for hydrocarbon rubber (COC (Cleveland Open Cup, gram) The open cup method is not limited, and is preferably 200 ° C or higher, and more preferably 250 ° C or higher.

In the adhesive layer used in the present invention, one or two or more of the following components may be appropriately selected and used as an adhesion-imparting agent, for example, an aliphatic-aromatic copolymerization system or a petroleum resin such as an alicyclic system, or a scented grass. An anthraquinone-based resin, a terpene-based resin, a nonylphenol-based resin, an alkylphenol-based resin, a rosin-based resin, a xylene-based resin, and the like, and the like. Further, in the adhesive layer used in the present invention, the adhesion-imparting agents themselves may be a main component.

<Separation film for surface protection>

The use of the release film of the present invention is not limited, and it can be preferably used as a release film (hereinafter sometimes referred to as a surface protective film) for protecting the surface of various products. The layer constitution in the case of use as a surface protective film is not limited, and in the aspect of the release film described above, a single-sided tape or a single-sided tape which is a release film is preferable.

In other words, the release layer can be peeled off from the "one-side tape of the release film" which is integrated with the adhesive layer and the release layer on the adhesive layer side, and can be attached to the object for surface protection. In the above, the adhesive layer of the "single-sided tape" which is formed by integrating the release layer and the adhesive layer may be attached to the object for surface protection.

The material of the object to be surface-protected is not limited, and examples thereof include resin, metal, glass, and other inorganic substances. Further, those who have been coated or the like on the surface or who have chemical or physical treatment may also be the object.

The use of the object to be surface-protected is not limited, and examples thereof include a building member, an automobile member, a display member, and a daily necessities. As a building component, an example Examples thereof include an external member, an internal member, a bathtub, a kitchen member, and the like. Examples of the automobile member include a cover, a door panel, a bumper, a baffle plate, a window, and a roof. Examples of the member for display include a polarizing plate, a phase difference plate, and an OA (Office Automation) equipment. External etc.

When the release film of the present invention is used as a surface protective film for the various articles, it is also possible to maintain good adhesion when the article is protected, and does not leave the release film or peel off when peeling off from the article. The type agent adheres to and remains on the product and is peeled off from the product with a stable release force. Further, even when the product of the release film of the present invention is adhered in a high temperature environment, good release properties and adhesion properties can be exhibited.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the examples below, without departing from the spirit thereof.

In the examples and comparative examples of the present invention, the following raw materials were used.

[raw material of release layer] <Propylene polymer>

‧A-1: Made by Japan Polypropylene Co., Ltd., Welnex PP, RFG4VA (MFR (230 ° C, 2.16 kg): 6 g/10 min, flexural modulus: 250 MPa, ethylene-propylene copolymer)

‧A-2: Made by Japan Polypropylene Co., Ltd., Novatec PP BC3H (MFR (230 ° C, 2.16 kg): 8.5 g/10 min, flexural modulus: 900 MPa, propylene-ethylene block copolymer)

There is a polypropylene block and a propylene-ethylene copolymer block, and the flexural modulus of the propylene-ethylene copolymer block portion corresponds to 20 MPa.

‧A-3: manufactured by SunAllomer Co., Ltd., Catalloy Adflex C200F (MFR (230 ° C, 2.16 kg): 6.0 g/10 min, flexural modulus: 200 MPa, propylene-ethylene block copolymer)

‧A-4: manufactured by Mitsui Chemicals Co., Ltd., Tafmer P0480 (MFR (230 ° C, 2.16 kg): 1.8 g/10 min, flexural modulus: 20 MPa, ethylene-propylene copolymer)

‧A-5: Made by Japan Polypropylene Co., Ltd., Novatec PP MA3 (MFR (230 ° C, 2.16 kg): 11 g/10 min, flexural modulus: 1500 MPa, propylene homopolymer)

‧A-6: Made by Japan Polypropylene Co., Ltd., Novatec PP FW4B (MFR (230 ° C, 2.16 kg): 6.5 g/10 min, flexural modulus: 850 MPa, propylene-1-butene-ethylene copolymer) )

‧A-7: Made by Japan Polypropylene Co., Ltd., Novatec PP EG7F (MFR (230 ° C, 2.16 kg): 1.3 g/10 min, flexural modulus: 1050 MPa, propylene-ethylene copolymer)

‧A-8: manufactured by Mitsui Chemicals Co., Ltd., Tafmer A4085S (MFR (230 ° C, 2.16 kg): 3.4 g/10 min, flexural modulus: 70 MPa, ethylene-butene copolymer)

<release agent>

‧B-1: Hawthorn

115.6 parts of behenic acid (C ₂₁ H ₄₃ COOH, manufactured by Tokyo Chemical Industry Co., Ltd., purity: 95% or more) was melted at 140 ° C under a nitrogen atmosphere, and ethylenediamine (manufactured by Wako Pure Chemical Industries, Ltd., purity 99%) was added thereto. Above) 10 copies. After the addition, the mixture was heated to 160 ° C and reacted for 6 hours. The moisture and the like formed in the reaction were separated and removed using a Dean-Stark tube. After the reaction, the mixture was cooled to room temperature, and then 1,320 parts of xylene was added thereto, and the mixture was heated to 160 ° C and stirred for 1 hour to be dissolved. Thereafter, the product was precipitated by cooling to room temperature, and the mixture was separated by filtration, dispersed in 1600 parts of acetone, and filtered again. The obtained product was dried under reduced pressure at 80 ° C for 12 hours to obtain 116.4 parts of a fatty acid bis-amine (B-1) containing behenamide as a main component.

‧B-2 (for comparison): manufactured by LION Co., Ltd., Armoslip E (mucilamine)

‧B-3 (for comparative use): manufactured by Nippon Oil Co., Ltd., Alflow AD-281F (ethylene bisamine)

‧B-4 (for comparative use): manufactured by Nippon Kasei Co., Ltd., Slipacks E (ethylene bis-stearate)

[Materials for Support Layer]

‧ Made by Japan Polypropylene Co., Ltd., Novatec PP FY4 (MFR (230 ° C, 2.16 kg): 5 g/10 min, propylene homopolymer)

[adhesive layer]

‧ Tape 1: Commercially available polyoxygenated adhesive tape with a width of 25 mm (manufactured by Nitto Denko Co., Ltd., No. 903UL)

‧ Tape 2: Each tape of acrylic adhesive tape cut into a width of 25 mm (manufactured by Nitto Denko Co., Ltd., No. 31B)

‧ Tape 3: Using three three-layer T-die film forming machines manufactured by Placo, at the forming temperature of 220 ° C and a pulling speed of 10 m / min, the outer layer/intermediate layer/adhesive is obtained from the side of the cooling roll. The layers are each a laminated body of a film thickness of 10 μm, 35 μm, and 5 μm. Further, the outer layer and the intermediate layer are the same resin and are regarded as a single layer having a thickness of 45 μm. A tape cutter having a width of 25 mm in the extrusion direction of the obtained laminate was set as a tape. The resin used for the outer layer/intermediate layer and the adhesive layer is as follows.

<Outer layer/intermediate layer> homopolypropylene: "Novatec PP FY4" manufactured by Nippon Polypropylene Co., Ltd. (MFR (230 ° C, load 21.2 N): 5.0 g/10 min)

<Adhesive layer> Styrene-isobutylene block copolymer: "Sibstar 062M-UN" manufactured by Kaneka Co., Ltd.

<Example 1>

6 parts by weight of B-1 was blended with respect to 100 parts by weight of A-1, and melt-kneading was carried out at 230 ° C using an extruder (manufactured by Nippon Steel Works Co., Ltd., TEX 30 twin-screw extruder) to obtain a resin composition. Particles.

The pellet of the resin composition was used for a release layer, and Novatec PP FY4 manufactured by Japan Polypropylene Co., Ltd. was used as a raw material of a support layer, and a multilayer T-die co-extrusion molding machine manufactured by Placo was used to have a thickness of 50. Μm (release layer: 10 μm, support layer: 40 μm), product with a width of 25 cm The layer body (release film) is formed. The following release property evaluation 1 was carried out using the obtained laminate (release film). The results are shown in Table-1.

<Evaluation 1>

The laminated body (release film) produced as described above is cut into a rectangular shape having a width of 30 mm in the extrusion direction (MD (Machine Direction)), and any of the above-mentioned tape 1, tape 2, and tape 3 is used. After the adhesive surface was superposed on the side of the release layer side, a rubber roller having a weight of 2 kg was reciprocated once and pressed to prepare a test piece for evaluation. After the test piece for evaluation was allowed to stand at room temperature for 1 hour, the force required to peel off the interface between the release layer and the adhesive layer in the direction of 180° at a tensile speed of 300 mm/min was measured (average of 5 samples) Value) and set it to "release force (N/cm)".

Further, the test piece cut into a width of 30 mm was selected from the one end of the laminated body (release film) having a width of 25 cm toward the other end at an equal position in the width direction, and was numbered as (1). )~(7), and the respective release forces are measured ((1) and (7) are the ends of the sheet, and (4) is the central portion of the sheet width). For the evaluation test pieces of (1) to (7), the average value was measured five times, and the maximum and minimum values of the release force on the test pieces of (1) to (7) were confirmed. Preferably, the value of the release force is small and the difference between the maximum value and the minimum value is smaller.

<Examples 2 to 9 and Comparative Examples 1 to 9>

The pellet of the resin composition was produced in the same manner as in Example 1 except that the type of the propylene-based polymer and the amount of the release agent were as shown in Table-1, and obtained in the same manner as in Example 1. Laminated body (release film). use The laminate (release film) obtained was evaluated for release property 1 in the same manner as in Example 1. The results are shown in Table-1.

According to the results of Table-1, in the examples, in any case where the amount of the release agent was changed, the release force was uniform, and the difference caused by the position of the sheet was not observed at all. On the other hand, in a comparative example in which a propylene-based polymer having a high flexural modulus is used as a raw material, a difference in release force occurs depending on the position of the laminate (release film). This performance becomes more apparent when the width of the laminate (release film) is wider.

<Examples 10 to 16, Comparative Examples 10 to 20>

A pellet of the resin composition was produced in the same manner as in Example 1 except that the kind and the amount of the release agent were as shown in Table-2, and the laminate was released in the same manner as in Example 1. Film) forming. The following release properties Evaluation 2 and Evaluation 3 were carried out using the obtained laminate (release film). The results of Evaluation 2 are shown in Table-2, and the results of Evaluation 3 are shown in Table-3. Further, the composition of the raw materials of Examples 10 to 16 was the same as that of Examples 1 to 6 and 8, respectively.

<Evaluation 2>

The central portion of the above-mentioned laminated body (release film) is cut into a rectangular shape having a width of 30 mm in the extrusion direction, and the adhesive surface of any of the above-mentioned tape 1, tape 2, and tape 3 is separated from the release layer thereof. After the side faces were overlapped, a rubber roller having a weight of 2 kg was crimped and reciprocated once to prepare a test piece for evaluation. After the test piece for evaluation was allowed to stand at room temperature for 1 hour, the force required to peel off the interface between the release layer and the adhesive layer in the direction of 180° at a tensile speed of 300 mm/min was measured (average of 5 samples) Value) and set it to "release force" (N/cm)". In addition, this value corresponds to the release force of the evaluation test piece of (4) in Evaluation 1. Preferably, the value is smaller.

Then, the adhesive layer side of the peeling evaluation test piece was attached to the upper surface of the stainless steel (SUS) plate (the adhesive surface of the tape was attached to the stainless steel plate), and the rubber roll having a weight of 2 kg was attached. Press once for a round trip. After standing at room temperature for 1 hour, the force required to peel off the interface between the stainless steel plate and the adhesive layer in the direction of 180° at a tensile speed of 300 mm/min (the average of 5 samples) was measured and Set to "adhesion (N/cm)". It is preferable that the value is larger.

<evaluation 3>

The central portion of the above-mentioned laminated body (release film) is cut into a rectangular shape having a width of 30 mm in the extrusion direction, so that the adhesive surface of either of the above-mentioned tape 1 or tape 2 and the release layer side thereof After the surface was superposed, a rubber roller having a weight of 2 kg was crimped one by one to prepare a test piece for evaluation, and then a load of 50 gf/cm ^{2 was} applied, and allowed to stand at 60 ° C for 3 days. Thereafter, it was allowed to stand at room temperature for 1 hour, and then the force required to peel off the interface between the release layer and the adhesive layer in the direction of 180° at a tensile speed of 300 mm/min was measured (average of 5 samples) And set it to "heating force (N/cm)". Preferably, the value is smaller.

Then, the adhesive layer side of the peeling evaluation test piece was attached to the upper surface of the stainless steel (SUS) plate (the adhesive surface of the tape was attached to the stainless steel plate), and the rubber roll having a weight of 2 kg was attached. Press once to reciprocate. After standing at room temperature for 1 hour, the tensile speed was measured at 300 mm / min at 180 ° The force required to peel the interface between the stainless steel plate and the tape (the average of 5 samples), and set it as "heating adhesion (N/cm)". It is preferable that the value is larger.

According to the results of Tables 2 and 3, in the examples, in any case where the amount of the release agent is changed, the release property is good, and the adhesive layer and the release layer are bonded together. In the case of storage in a high temperature environment, the change in peeling force is also small, and the adhesive property of the contact tape is also excellent.

On the other hand, in the comparative example in which the release agent was not used or the release agent different from the general formula (1) as a raw material, the release property was poor, and the adhesive layer and the release layer were bonded together. When the product was stored in a high temperature environment, it was confirmed that the peeling force was largely changed.

The present invention has been described in detail with reference to the preferred embodiments of the present invention. It is understood that various changes and modifications may be made without departing from the spirit and scope of the invention. The present application is based on a Japanese patent application filed on July 12, 2011 (Japanese Patent Application No. 2011-153804), and a Japanese patent application filed on March 27, 2012 (Japanese Patent Application No. 2012-072132) The contents are incorporated herein by reference.

Claims (14)

A resin composition comprising a polyolefin resin (A) having a flexural modulus of 800 MPa or less and a fatty acid bisamine compound (B) represented by the following formula (1); and the above polyolefin resin (A) is propylene A polymer; R-CONH-(CH ₂ ) _n -NHCO-R (1) (wherein, n represents an integer of 1 to 6, and R each independently represents an aliphatic group having a carbon number of 19 or more). The resin composition of the first aspect of the invention, wherein the propylene monomer unit constituting the propylene polymer is 50% by weight or more. The resin composition of claim 1, wherein the polyolefin resin (A) is an ethylene-propylene copolymer. The resin composition of the second or third aspect of the invention, wherein the polyolefin resin (A) contains 4% by weight or more of a component other than propylene. A release film having at least a release layer containing a polyolefin resin (A) having a flexural modulus of elasticity of 800 MPa or less and a fatty acid bis-amine compound (B) represented by the following formula (1) The above polyolefin resin (A) is a propylene-based polymer; R-CONH-(CH ₂ ) _n -NHCO-R (1) (wherein, n represents an integer of 1 to 6, and R independently represents a carbon number of 19 Above aliphatic base). The release film of claim 5, wherein the release layer contains 0.5 to 20 parts by weight of the fatty acid bis-amine compound (B). The release film of the fifth or sixth aspect of the invention, wherein the propylene monomer unit constituting the propylene polymer is 50% by weight or more. The release film of claim 5 or 6, wherein the polyolefin resin (A) is an ethylene-propylene copolymer. The release film of claim 5 or 6 further contains an adhesive layer. The release film of claim 9, wherein the release layer forms a surface and the adhesive layer forms another surface. A release film according to claim 5 or 6, which is obtained by co-extrusion molding. The release film of claim 5 or 6 is for surface protection. A release film according to claim 12, which is used for surface protection of any of a building member, an automobile member, and a display member. The release film of claim 12, which is used for surface protection of any of resin, metal and glass.