JP5382755B1 - Surface protection film - Google Patents

Abstract

[1] As the main component of the adhesive
(A) (I) which is a hydrogenated product of the copolymer (I ′) represented by the formula: [AB] n (n is 1 to 3), and (b) A at at least two ends. A combination of (II) which is a hydrogenated copolymer (II ′) having at least one B in its middle part, and [2] as a tackifier,
Containing a phenolic resin with a phenol component content of 5-45%,
The mass ratio of A and B contained in (I ′) and (II ′) is 5:95 to 25:75,
It has an adhesive layer in which the aromatic alkenyl compound unit content of (I ′) and (II ′) is 5 to 50% by mass, and the hydrogenation rate of (I) and (II) is 80% or more. Surface protective film.
A is a polymer block containing 80% by mass or more of an aromatic alkenyl compound unit.
The above B is a polymer block containing 50% by mass or more of conjugated diene compound units and having a vinyl bond content of 50% by mol or more derived from the conjugated diene compound.

Description

  The present invention relates to a surface protective film, particularly a surface protective film for a prism sheet.

The prism sheet is a sheet having a function of condensing light emitted from a backlight forward in a liquid crystal display, and is formed of a transparent resin. The surface of the prism sheet has irregularities in the shape of a triangular prism.
Since the above unevenness is extremely important for the performance of the prism sheet, even if the uneven shape of the prism sheet is deformed in an extremely fine area during the manufacture of a liquid crystal display or the like in recent years, the uneven shape Self-healing prism sheets that can recover elastically have been put into practical use.
In recent years, prism sheets are produced by a soft mold method using a resin mold for the purpose of reducing the cost of the prism sheets.
In order to prevent the unevenness of the prism sheet from being damaged during transportation or the like, a surface protective film that is used by being attached to the surface thereof is widely used. As such a surface protective film, the surface protective film currently disclosed by patent document 1 is mentioned, for example. Such a surface protective film can obtain an appropriate adhesive force with respect to the prism surface of the prism sheet by biting the concave-convex shape of the prism sheet into the adhesive layer. Can be suitably used.
By the way, such a surface protection film is industrially manufactured as a wound body obtained by winding a long film into a roll shape. It is known that the surface protection film as such a wound body has a high force (deployment force) necessary for unwinding the wound body, and the deployment force tends to increase with time. There is a strong demand for a small force, that is, the ability to easily rewind the wound body.

International Publication No. 2010/029773 Pamphlet

Even in the case of the self-recovering prism sheet as described above, self-healing is not performed when the concavo-convex shape is deformed so as to exceed an elastic recoverable range.
Therefore, a surface protective film is used even in the case of a self-healing prism sheet for the purpose of protecting the uneven shape from deformation caused by a relatively strong external force received during transportation and for the purpose of preventing adhesion of dust and the like. It is necessary to protect the surface.
However, since the concavo-convex shape is more easily deformed in a self-recovering prism sheet than in a normal prism sheet, when the surface protective film disclosed in Patent Document 1 is applied to the prism surface, the pressure at the time of application thereof As a result, the concavo-convex shape is deformed, and the top of the concavo-convex shape of the prism sheet cannot sufficiently penetrate into the pressure-sensitive adhesive layer, and an appropriate adhesive force to the prism surface of the prism sheet cannot be obtained. As a result, the surface protection sheet frequently peels off naturally from the prism surface against the user's intention, and the surface of the prism sheet (particularly, the prism surface) cannot be properly protected. There was a problem.
In addition, when a surface protection film for a normal prism sheet is attached to the prism surface of the prism sheet manufactured by the soft mold method as described above, the surface protection sheet can be used from the prism surface to the user's intention. On the other hand, it often happens that it naturally peels off, and there is a problem that the surface of the prism sheet (particularly the prism surface) cannot be properly protected. In the soft mold method, a release agent is blended in a resin mold for the purpose of facilitating peeling of the prism sheet from the resin mold (that is, for the purpose of improving mold release properties). The above-described peeling is presumed to be caused by the release agent blended in the mold being transferred to the prism surface of the prism sheet.
However, in order to deal with these problems, simply using a surface protective film with high adhesive strength, even if the aforementioned peeling problem is solved, the force required to unwind the wound body of the surface protective film (deployment) Therefore, the efficiency of the work of attaching the surface protective film to the prism sheet surface for protecting the surface of the prism sheet is reduced.
Therefore, the present invention provides a prism sheet (in particular, a prism sheet manufactured by a soft mold method and a self-recovering prism sheet) without reducing the efficiency of the work of attaching a surface protective film to the prism sheet surface. An object of the present invention is to provide a surface protective film that can appropriately protect (especially the prism surface).

  The present inventors have found that the above-mentioned object can be achieved by using a surface protective film having a specific pressure-sensitive adhesive and a pressure-sensitive adhesive layer containing a specific tackifier. It came to complete.

The present invention includes the following aspects.
Item 1.
[1] As the main component of the adhesive
(A) A structure represented by the formula: [AB] _n (A represents the following polymer block A, B represents the following polymer block B, and n represents an integer of 1 to 3). Copolymer (I), which is a hydrogenated product of copolymer (I ′), and (b) at least two terminals having the following polymer block A, and at least one of the following As a combination of copolymer (II), which is a hydrogenated product of copolymer (II ′) having combined block B, and [2] as a tackifier,
Containing a phenol resin whose phenol component content (molar ratio) is in the range of 5 to 45%;
The mass ratio (A: B) of the total amount of the polymer block A and the total amount of the polymer block B contained in the entire copolymer (I ′) and the copolymer (II ′) is from 5:95 to Within the range of 25:75,
The total aromatic alkenyl compound unit content (St (A + B)) of the copolymer (I ′) and the copolymer (II ′) is 5 to 50% by mass, and the copolymer (I ) And an adhesive layer having a total hydrogenation rate of the copolymer (II) of 80% or more, and a surface protective film having a base material layer.
[Polymer block A]: Polymer block containing an aromatic alkenyl compound unit at a content of 80% by mass or more [Polymer block B]: Containing a conjugated diene compound unit at a content of 50% by mass or more, and 1. Polymer block in which the content of vinyl bonds derived from a conjugated diene compound is 50 mol% or more.
Item 2. The surface protective film according to Item 1, which is used for a prism sheet.
Item 3.
Next way:
After the surface protection film is applied to the prism surface of the brightness enhancement film having a prism prism height h1 that is constant and 25 μm, punching is performed from the prism surface side, and then the surface protection film adhesive surface is cut in the cross section generated by the punching. Measuring the distance h2 from the straight line s connecting the two adjacent points where the vertexes of the prism crests are inserted to the apex p of the convex shape generated when the adhesive surface of the surface protective film is pushed into the prism valley. = 3
Calculate the arithmetic mean value of h2 / h1,
Define this as the adhesive surface deformation rate;
Item 3. The surface protective film according to Item 1 or 2, wherein the adhesive surface deformation rate obtained by the method is 50% or more.
Item 4.
When the hardness calculated by the measurement according to JIS R1639-5 of the prism mountain is 0.08 to 0.15 and is deformed to 20 gf according to JIS R1639-5, the weight is removed when the weight is removed. Item 4. The surface protective film according to any one of Items 1 to 3, which is used for a self-healing prism sheet in which deformation cannot be confirmed after 3 seconds from the removal.
Item 5.
Item 4. The surface protective film according to any one of Items 1 to 3, which is used for a prism sheet manufactured by a soft mold method.
Item 6.
The phenol resin is one selected from the group selected from terpene phenol resins, alkylphenol resins, rosin modified phenol resins, phenol modified coumarone indene resins, phenol modified formaldehyde resins, t-butylphenol resins, and t-butylphenol acetylene resins. Item 6. The surface protective film according to any one of Items 1 to 5, which is a phenol resin as described above.
Item 7.
Item 7. The surface protective film according to Item 6, wherein the phenol resin is a terpene phenol resin.

  According to the present invention, the surface of the prism sheet (particularly, the prism sheet manufactured by the soft mold method and the self-recovering prism sheet) without reducing the efficiency of the operation of attaching the surface protective film to the prism sheet surface. Protection can be properly protected.

It is sectional drawing explaining one aspect | mode of calculation of an adhesive surface deformation rate, and use of the surface protection film of this invention.

  1. Terms and symbols

  The symbol “˜” used to represent a numerical range in this specification is used with the intention that the numerical range includes the numerical values at both ends unless otherwise specified.

  In the present specification, the “content” of the repeating unit of the polymer used in the term “aromatic alkenyl compound unit content” or the like means the mass ratio in terms of the monomer from which the repeating unit is derived, that is, the polymer. The ratio (mass%) of the mass of the monomer from which the repeating unit is derived to the mass of all monomers to be formed, that is, the alkenyl aromatic compound content of the polymer. Here, the “mass of all monomers for forming the polymer” approximates the mass of the polymer. Similarly, in the present specification, the “content ratio” of the repeating unit of the polymer block is the mass ratio in terms of the monomer from which the repeating unit is derived, that is, the total monomer for forming the polymer block. It means the ratio (mass%) of the mass of the monomer from which the repeating unit is derived to the mass. Here, the “mass of all monomers for forming the polymer block” approximates the mass of the polymer block.

  In the present specification, the “vinyl bond content” means the total content of 1,2-vinyl bonds and 3,4-vinyl bonds calculated by the Morello method using an infrared absorption spectrum method.

2. Surface protective film The surface protective film of the present invention is
[1] As the main component of the adhesive
(A) A structure represented by the formula: [AB] _n (A represents the following polymer block A, B represents the following polymer block B, and n represents an integer of 1 to 3). Copolymer (I), which is a hydrogenated product of copolymer (I ′), and (b) at least two terminals having the following polymer block A, and at least one of the following As a combination of copolymer (II), which is a hydrogenated product of copolymer (II ′) having combined block B, and [2] as a tackifier,
Containing a phenol resin with a phenol component content (molar ratio) of 5 to 45%,
The mass ratio (A: B) of the total amount of the polymer block A and the total amount of the polymer block B contained in the entire copolymer (I ′) and the copolymer (II ′) is from 5:95 to Within the range of 25:75,
The total aromatic alkenyl compound unit content (St (A + B)) of the copolymer (I ′) and the copolymer (II ′) is 5 to 50% by mass, and the copolymer (I ) And the copolymer (II) have a pressure-sensitive adhesive layer having a total hydrogenation rate of 80% or more, and a base material layer.
[Polymer block A]: Polymer block containing an aromatic alkenyl compound unit at a content of 80% by mass or more [Polymer block B]: Containing a conjugated diene compound unit at a content of 50% by mass or more, and Polymer block having a vinyl bond content derived from a conjugated diene compound of 50 mol% or more

  The surface protective film of this invention has an adhesive layer and a base material layer at least. Preferably, the pressure-sensitive adhesive layer is laminated on one surface of the base material layer. In this specification, the pressure-sensitive adhesive surface of the surface protective film means the surface of the pressure-sensitive adhesive layer on the side opposite to the base material layer side.

3.1. Pressure-sensitive adhesive layer The pressure-sensitive adhesive layer contains a pressure-sensitive adhesive main component and a tackifier.

3.1.1. Main component of pressure-sensitive adhesive The pressure-sensitive adhesive layer contains copolymer (I) and copolymer (II) as the main component of pressure-sensitive adhesive.
In the present specification, the main component of the pressure-sensitive adhesive means a component that exists in the pressure-sensitive adhesive layer at the highest content (mass basis) and imparts pressure-sensitive adhesiveness to the pressure-sensitive adhesive layer.
Copolymer (I) is represented by the formula: [AB] n (A represents polymer block A described below, B represents polymer block B described below, and n is 1 to 3. It represents a hydrogenated product of copolymer (I ′) having a structure represented by:
The copolymer (II) is a hydrogenated product of the copolymer (II ′) having the polymer block A at at least two ends and having at least one polymer block B at an intermediate portion thereof. .

“Polymer block A” present in each of copolymer (I ′) and copolymer (II ′) is a polymer block containing an aromatic alkenyl compound unit at a content of 80% by mass or more.
The lower limit of the content is preferably 85% by mass, more preferably 90% by mass.

  In the present specification, the “aromatic alkenyl compound unit” is a repeating unit derived from an aromatic alkenyl compound. Examples of the “aromatic alkenyl compound” include styrene, tert-butylstyrene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, divinylbenzene, 1,1-diphenylethylene, vinylnaphthalene, vinylanthracene, N, N-diethyl-p-aminoethylstyrene, vinylpyridine and the like can be mentioned.

The polymer block A may have a repeating unit other than the aromatic alkenyl compound unit.
Examples of such a repeating unit include a conjugated diene compound unit.
In the present specification, the “conjugated diene compound unit” is a repeating unit derived from a conjugated diene compound. Examples of the “conjugated diene compound” include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-octadiene, 1,3. -Hexadiene, 1,3-cyclohexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, myrcene, chloroprene and the like.

  The “polymer block B” present in each of the copolymer (I ′) and the copolymer (II ′) contains a conjugated diene compound unit at a content of 50% by mass or more and is derived from the conjugated diene compound. The polymer block has a vinyl bond content of 50 mol% or more.

The polymer block B may have a repeating unit other than the conjugated diene compound unit.
Examples of such a repeating unit include an aromatic alkenyl compound unit.

<Copolymer (I ')>
The formula representing the copolymer (I ′): As is clear from the fact that “n” in [AB] n is an integer of 1 to 3, it is represented by the “formula [AB] n”. Examples of the “structure” include structures represented by A-B, A-B-A-B, and A-B-A-B-A-B. In these block copolymers, A and B may be the same or different in repetition.

  The copolymer (I ′) may be used alone or in combination of two or more.

<Copolymer (II ')>
The copolymer (II ′) has a polymer block A at at least two ends, for example, at both ends of the main chain, and at least one polymer block B at an intermediate portion thereof.
In the “copolymer (II ′)”, preferably, the copolymer (II ′) is represented by the formula: ABA (wherein the symbols are as defined above) or the formula: ( AB) x-Y (wherein x represents an integer of 1 or more, Y represents a coupling agent residue, and other symbols are as defined above). It is a polymer.

A structure represented by the formula: (AB) xY (wherein x represents an integer of 2 or more, Y represents a coupling agent residue, and other symbols are as defined above). In other words, the copolymer having has a structure in which the copolymer (I ′) is coupled by Y. Therefore, in the case of (AB) x-Y, a mixture of the copolymers (I ′) and (II ′) can be synthesized in the same reaction kettle. ) XY is preferred. When x is 3 or more, the copolymer is a so-called star polymer. x is preferably 2 to 4 from the viewpoint of suppressing side reactions during the production of the copolymer and controlling the physical properties of the copolymer.
It is preferable that the coupling agent residue Y does not affect the physical properties of the copolymer, and examples of the coupling agent that gives such a coupling agent residue Y include methyldichlorosilane.
When the effect of the coupling agent residue Y on the physical properties of the copolymer is small, (B) the portion represented by xY (eg, the portion represented by BYB) is substantially The same as block B.

  The copolymer (II ′) may be used alone or in combination of two or more.

  The total aromatic alkenyl compound unit content (St (A + B)) of the copolymer (I ′) and the copolymer (II ′) is 5 to 50% by mass, preferably 30 to 50% by mass. is there.

<Copolymer (I) and Copolymer (II)>
The copolymer (I) and the copolymer (II) are hydrogenated products of the copolymer (I ′) and the copolymer (II ′), respectively.
Accordingly, as those skilled in the art will readily understand, some of the matters described for the copolymer (I ′) and the copolymer (II ′) are partially related to the copolymer (I) and the copolymer (II). ).
The total hydrogenation rate of the copolymer (I) and the copolymer (II) is 80% or more, preferably 90%, more preferably 95%.
Moreover, the hydrogenation rate of each of the copolymer (I) and the copolymer (II) is 80% or more, preferably 90%, more preferably 95%.
In the present specification, the hydrogenation rate is the molar ratio (%) of the hydrogenated double bond to the double bond derived from the conjugated diene compound before the hydrogenation, Used as a solvent, means a hydrogenation rate calculated from 270 MHz, ¹ H-NMR spectrum.

  The mass ratio of the copolymer (I) and the copolymer (II) in the pressure-sensitive adhesive layer is preferably in the range of 5:95 to 40:60.

The copolymer (I) and the copolymer (II) can be produced using a known method.
For example, the copolymer (I) is a copolymer represented by A-B (the symbols in the formula are as defined above), and the copolymer (II) is A-B-Y-B--. In the case of a copolymer represented by A (the symbols in the formula are as defined above), these are:
(A) The block A raw material monomer is polymerized to synthesize block A, and the block B raw material monomer is added thereto to synthesize AB (copolymer (I ′)).
(B) using a coupling agent having Y, coupling AB, and synthesizing ABYYBA (copolymer (II ′));
(C) The copolymer (I ′) and the copolymer (II ′) may be synthesized by a method including hydrogenating the copolymer (I ′) and the copolymer (II ′) to obtain the copolymer (I) and the copolymer (II).

3.1.2. Tackifier The pressure-sensitive adhesive layer contains a phenol resin as a tackifier.
The tackifier is compatible with the copolymer (I) and the copolymer (II), which are the main components of the adhesive, and controls the adhesive force of the adhesive layer.
The phenol resin is preferably selected from the group selected from terpene phenol resins, alkylphenol resins, rosin-modified phenol resins, phenol-modified coumarone indene resins, phenol-modified formaldehyde resins, t-butylphenol resins, and t-butylphenol acetylene resins. One or more types of phenol resins, and particularly preferred are terpene phenol resins and hydrogenated products of terpene phenol resins.
The said phenol resin has content (molar ratio) of a phenol component in the range of 5-45 mol%. Here, the phenol component in the phenol resin means a structural unit derived from a monomer containing phenol.
The content (molar ratio) of the phenol component is obtained using a proton nuclear magnetic resonance apparatus ( ¹ H-NMR).

When the content (molar ratio) of the phenol component is within such a range, when the surface protective film of the present invention is attached to the prism surface, the adhesive surface can be deformed in accordance with the prism mountain shape. Therefore, the contact area between the surface protective film of the present invention and the prism surface can be increased, and as a result, a suitable adhesive force can be exerted on the prism sheet.
If it is 5% or less, the pressure-sensitive adhesive is deformed at the time of sticking, but since it is elastically recovered immediately, the deformation of the pressure-sensitive adhesive cannot be maintained and sufficient adhesive strength is not exhibited.
If it is 45% or more, the cohesive force of the pressure-sensitive adhesive becomes too high, the pressure-sensitive adhesive cannot be deformed at the time of application, and sufficient pressure-sensitive adhesive strength is not exhibited.

Such a phenol resin may be used independently and may be used in combination of 2 or more type.
The content of the tackifier in the pressure-sensitive adhesive layer is preferably 10 to 50 parts by mass with respect to 100 parts by mass as the total mass of the copolymer (I) and the copolymer (II).

3.1.3. Other components In addition to the main component of the adhesive and the tackifier, the adhesive layer further comprises a styrenic block phase reinforcing agent, a softening agent, an antioxidant, a light stabilizer, and an ultraviolet absorber. In addition, a known additive such as a filler, a pigment, an anti-adhesive agent, an olefin resin, a silicone polymer, a liquid acrylic copolymer, and a phosphate ester compound may be appropriately contained.

The “styrene block phase reinforcing agent” is used for suppressing the pressure-sensitive adhesive layer from progressing.
Examples of the styrene block phase reinforcing agent include, as monomer units, styrene and α-methylstyrene, p-methylstyrene, p-chlorostyrene, chloromethylstyrene, tert-butylstyrene, p-ethylstyrene, divinylbenzene, and the like. The styrene-type compound of this is mentioned. These can be used alone or in combination of two or more.
That is, the styrenic block phase reinforcing agent can be obtained by polymerizing these monomers. In the case of a copolymer composed of two or more types of monomers, it may be a block copolymer or a random copolymer. Among them, the styrenic block phase reinforcing agent preferably has a softening point of about 100 ° C. or higher, and more preferably 150 ° C. or higher. Specifically, trade names “ENDEX 155” (softening point 155 ° C.), “ENDEX 160” (softening point 160 ° C.) manufactured by Eastman Chemical Co., Ltd. are preferably used.

  The “softener” is usually effective for improving the adhesive strength. Examples of the softener include low molecular weight diene polymer, polyisobutylene, hydrogenated polyisoprene, hydrogenated polybutadiene, paraffinic process oil, naphthenic process oil, aromatic process oil, castor oil, tall oil, and natural oil. , Liquid polyisobutylene resin, polybutene, or hydrogenated products thereof.

The “antioxidant” is not particularly limited, and examples thereof include phenol-based (monophenol-based, bisphenol-based, polymer-type phenol-based), sulfur-based, phosphorus-based and the like.
Examples of the “light stabilizer” include hindered amine compounds.
The “ultraviolet absorber” is not particularly limited, and examples thereof include salicylic acid series, benzophenone series, benzotriazole series, and cyanoacrylate series.

Examples of the “filler” include calcium carbonate, magnesium carbonate, silica, zinc oxide, titanium oxide and the like.
Examples of the “adhesion progress inhibitor” include fatty acid amides, polyethyleneimine long-chain alkyl grafts, soybean oil-modified alkyd resins (eg, Arakawa Chemical Industries, trade name “Arachid 251”, etc.), tall oil-modified alkyd resins ( For example, Arakawa Chemical Industries, Ltd., trade name “Arachid 6300” and the like.

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

  Although the thickness in particular of an adhesive layer is not restrict | limited, For example, it is about 0.5-50 micrometers normally, Preferably it is 1-40 micrometers, More preferably, it is 2-30 micrometers.

3.2. Base Material Layer The base material layer is preferably a polyolefin base material layer.
Examples of the “polyolefin” include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ethylene-α-olefin copolymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer. Examples thereof include a copolymer, an ethylene-methyl acrylate copolymer, an ethylene-n-butyl acrylate copolymer, and polypropylene (homopolymer, random copolymer, block copolymer).
These can be used alone or in combination of two or more. The “polyolefin” may be a polyolefin having a substituent, and a resin other than the polyolefin may be added. Furthermore, the end material of the polyolefin base material layer and the end material of the surface protection film which were produced in the manufacturing process of the surface protection film may be added.

  The base material layer may be a single layer or a layer having two or more multilayer structures having different compositions.

  The thickness of the base material layer can be appropriately adjusted depending on the use of the surface protective film. Usually, it is suitable to set the thickness to about 10 to 100 μm.

3.3. Other Layers In addition to the base material layer and the adhesive layer, the surface protective film used in the present invention may further have other layers. Examples of such other layers include an intermediate layer formed from a polyolefin-based resin disposed between the base material layer and the adhesive layer.

The surface protective film of the present invention is obtained by the following method:
After sticking the surface protective film on the prism surface of a brightness enhancement film (BEF) having a prism mountain height h1 of 25 μm, punching is performed from the prism surface side;
In the cross section generated by punching, the surface protective film adhesive surface has a convex shape formed by pressing the surface protective film adhesive surface into the prism valley from the straight line s connecting the adjacent two points where the apex of the prism crests are respectively recessed. Measuring the distance h2 to the apex p with n = 3,
Calculate the arithmetic mean value of h2 / h1,
Define this as the adhesive surface deformation rate;
Is preferably 50% or more, more preferably 60% or more.
The measurement can be performed by observing with a microscope (magnification: 500 times).
Moreover, the said punching can be implemented using the following apparatus or its equivalent.
Product name: Toko hydraulic clicker Model number: TCM-3500
FIG. 1 is a sectional view for explaining the calculation of the adhesive surface deformation rate.
In FIG. 1, a convex shape having a height h2 is formed on the adhesive surface of the surface protective film 1 by sticking the surface protective film 1 to the prism surface of the brightness enhancement film 2 having a constant prism peak height h1. Yes. Here, the height h <b> 2 is generated by pressing the surface protective film adhesive surface into the prism valley from the straight line s connecting the two adjacent points where the apex of the prism crest of the surface protective film 1 is inserted. The distance to the apex p of the convex shape.
When the surface protective film of the present invention is attached to the prism surface, the adhesive surface can be deformed according to the shape of the prism peak, so that the contact area between the surface protective film of the present invention and the prism surface can be increased. As a result, it can have a suitable adhesive force to the prism sheet.

3.4. Production of Surface Protective Film The surface protective film used in the present invention contains, for example, the raw material A containing the copolymer (I) and the copolymer (II), and the main component of the adhesive and the tackifier. The raw material B to be manufactured can be manufactured by co-extrusion by a die method using a multilayer extruder.

  First, a base material layer and an adhesive layer are formed by coextrusion.

4. Protective object Suitable protective objects of the surface protective film of the present invention are a prism sheet, in particular, a prism sheet manufactured by a soft mold method, and a flexible prism sheet (preferably a self-recovering prism sheet).

The resin mold used in the soft mold method contains a release agent. The release agent can be transferred to the prism surface of the prism sheet.
In the present invention, the flexible prism sheet has a hardness calculated by measurement according to JIS R1639-5 of a prism mountain (convex portion) of 0.08 to 0.15. The flexible prism sheet is preferably a self-recovering prism sheet. The self-recovering prism sheet is a prism sheet in which deformation cannot be confirmed after 3 seconds from the removal of the weight when the weight is removed after the prism sheet is deformed until the weight is 20 gf according to JIS R1639-5. .
Specifically, the self-healing property is confirmed by applying a load with a flat indenter having a diameter of 50 μm to one of the crests (convex portions) of the prism using a micro compression tester MCT-510 and a flat indenter FLAT50. The load is increased at a constant speed (0.25 gf / second) until a load of 20 gf is reached. After reaching the maximum load, the load is decreased to the load 0 gf at the same speed (0.25 gf / second). By observing the prism from directly above at a magnification of 500 times.
The confirmation is performed by observation using an optical microscope with a magnification (eg, 500 times) at which the shape of the prism can be observed.

  The maximum unevenness height (maximum peak (projection) height) of the prism surface of the surface-protected prism sheet to which the surface protective film of the present invention is suitably applied is in the range of 10 to 70 μm. .

3.5. Surface protection method of the present invention The surface protection method of the prism sheet using the surface protection film of the present invention, if necessary,
The prism sheet contains the surface protective film of the present invention, that is, [1] copolymer (I) and copolymer (II) as the main component of the adhesive, and [2] phenol component as the tackifier. A surface protective film having a pressure-sensitive adhesive layer containing a phenol resin whose content (molar ratio) is in the range of 5 to 45%,
Affixing the pressure-sensitive adhesive layer in contact with the prism surface of the prism sheet.
The method can also be understood from FIG. The state where the surface protective film of the present invention is attached so as to be in contact with the prism surface of the prism sheet is shown in FIG. 1 where the deepest portion of the valley of the adhesive surface of the surface protective film 1 is in contact with the apex of the prism crest of the prism sheet 2. It is in the state.

4. Affixing In the surface protection method, the surface protection film is affixed to the prism sheet so that the adhesive layer of the surface protection film is in contact with the prism surface of the prism sheet.
At this time, it is possible to obtain a pressure-sensitive adhesive force suitable for the prism sheet by deforming and sticking the adhesive layer according to the triangular prism shape of the prism of the prism surface so that the adhesive layer has a high contact area. it can.

  Hereinafter, although the surface protection film of this invention is demonstrated in detail based on an Example, this invention is not limited to a following example.

(Production of copolymer composition)

(a) Polymerization of polymer block A A nitrogen-substituted reaction vessel was charged with 500 parts by mass of degassed and dehydrated cyclohexane, 9 parts by mass of styrene, and 5 parts by mass of tetrahydrofuran, and n- 0.13 parts by mass of butyllithium was added to perform temperature rising polymerization.

(b) Polymerization of polymer block B After the polymerization conversion rate of polymer block A reached approximately 100%, the reaction solution was cooled to 15 ° C., and then 91 parts by mass of 1,3-butadiene was added. Warm polymerization was performed.

(c) Coupling After reaching a polymerization conversion rate of almost 100%, 0.06 parts by mass of methyldichlorosilane was added as a coupling agent to carry out a coupling reaction. After the coupling reaction was completed, it was left for 10 minutes while supplying hydrogen gas at a pressure of 0.4 MPa-Gauge. A partially extracted polymer had a vinyl content of 64%, a mass average molecular weight of about 110,000, and a coupling rate of 60%.

Thereafter, 0.03 parts by mass of diethylaluminum chloride and 0.06 parts by mass of bis (cyclopentadienyl) titanium furfuryloxychloride were added to the reaction vessel and stirred. The hydrogenation reaction was started at a hydrogen gas supply pressure of 0.7 MPa-Gauge and a reaction temperature of 80 ° C., and when the absorption of hydrogen was completed, the reaction solution was returned to room temperature and normal pressure and extracted from the reaction vessel. A copolymer composition comprising the combination (I) and the copolymer (II) was obtained (Synthesis Example 1 in Table 1).
Hereinafter, the desired copolymer composition was obtained in the same manner (Synthesis Examples 1 to 3 in Table 1). The properties of these copolymer compositions are shown in Table 1.

In Table 1, “St (A + B)”, “St (B)”, “St (A)”, and “St (b)” represent numerical values defined as follows. In this definition, “total polymer” means the entire copolymer (I ′) and copolymer (II ′).
“St (A + B)” is the aromatic alkenyl compound unit content of the whole polymer, and means a numerical value represented by the following formula. This is equal to the sum of the following “St (B)” and the following “St (A)”.
formula:
St (A + B) = (aromatic alkenyl compound unit mass in all polymers) / (total monomer unit mass in all polymers) × 100 (mass%)

“St (B)” means a numerical value represented by the following equation.
formula:
St (B) = (aromatic alkenyl compound unit mass in all polymer blocks B) / (total monomer unit mass in all polymers) × 100 (mass%)

“St (A)” means a numerical value represented by the following formula.
formula:
St (A) = (aromatic alkenyl compound unit mass in all polymer blocks A) / (total monomer unit mass in all polymers) × 100 (mass%)

“St (b)” is the aromatic alkenyl compound unit content of the polymer block B, and means a numerical value represented by the following formula.
formula:
St (b) = (aromatic alkenyl compound unit mass in all polymer blocks B) / (total monomer unit mass in all polymer blocks B) × 100 (mass%)

  In Table 1, “A: B” represents a mass ratio between the total amount of the polymer block A and the total amount of the polymer block B.

  In Table 1, “(I) :( II)” represents a mass ratio of the copolymer (I) to the copolymer (II).

  In Table 1, “conjugated diene content (B)” represents the conjugated diene unit content of the polymer block B.

  In Table 1, “vinyl bond content (B)” represents the vinyl bond content of the polymer block B.

(Examples 1-5, Comparative Examples 1-5)
To 100 parts by mass of each copolymer composition (Table 1) obtained by each of the synthesis methods described above, as a tackifier, TH130 (terpene phenol resin, manufactured by Yasuhara Chemical Co., Ltd.), AP100 (alicyclic saturated hydrocarbon resin, Arakawa Chemical Co., Ltd.) or AP125 (alicyclic saturated hydrocarbon resin, Arakawa Chemical Co., Ltd.) was blended to obtain each adhesive composition. The composition is shown in Table 2 below.
Polypropylene (J715M manufactured by Prime Polymer Co., Ltd.) is used as the base material, and the base material and each pressure-sensitive adhesive composition are co-extruded by the T-die method, so that the base material layer having a thickness of 36 μm and the adhesive having a thickness of 4 μm are used. The surface protection films of Examples 1 to 5 and Comparative Examples 1 to 5 in which the agent layer was laminated and integrated were molded, and wound bodies wound on a paper core having an inner diameter of 3 inches were obtained.

(Examples 6 to 9)
YS Polystar UH115 (hydrogenated terpene phenol resin, manufactured by Yasuhara Chemical Co., Ltd.) as a tackifier is blended with 100 parts by mass of each copolymer composition (Table 1) obtained by each of the synthesis methods described above. An agent composition was obtained. The composition is shown in Table 3 below.
Polypropylene (J715M manufactured by Prime Polymer Co., Ltd.) is used as the base material, and the base material and each pressure-sensitive adhesive composition are coextruded by the T-die method, so that the base material layer having a thickness of 36 μm and the pressure-sensitive adhesive layer having a thickness of 4 μm are used. The surface protection films of Examples 6 to 9 were laminated and integrated to obtain a wound body wound around a paper core having an inner diameter of 3 inches.

(Examples 10-13 and Comparative Examples 6-7)
To 100 parts by mass of each copolymer composition (Table 1) obtained by the above synthesis methods, as a tackifier, YS Polystar S145 (terpene phenol resin, manufactured by Yashara Chemical Co., Ltd.), YS Polystar N125 (terpene phenol resin, Yasuhara Chemical Co., Ltd.) and Mighty Ace K125 (terpene phenol resin, Yasuhara Chemical Co., Ltd.) were blended to obtain each pressure-sensitive adhesive composition. The composition is shown in Table 4 below.
Polypropylene (J715M manufactured by Prime Polymer Co., Ltd.) is used as the base material, and the base material and each pressure-sensitive adhesive composition are coextruded by the T-die method, so that the base material layer having a thickness of 36 μm and the adhesive having a thickness of 4 μm The surface protection films of Examples 10 to 13 and Comparative Examples 6 to 7 in which the agent layer was laminated and integrated were molded, and wound bodies wound on a paper core having an inner diameter of 3 inches were obtained.

(Content of phenol component as tackifier)
Wherein as tackifier in the adhesive compositions of Examples and Comparative Examples, the content of the phenol component, using proton nuclear magnetic resonance apparatus ^{(1 H-NMR),} determined by the following measurement conditions and calculate It was. The results are shown in Table 5.
^<1 H-NMR measurement conditions, calculation formula>
(Peak attribution)
4.0-5.0 ppm: 14 hydrogen atoms adjacent to the terpene double bond 6.0-8.0 ppm: 3 hydrogen atoms adjacent to the OH group of phenol (weight fraction of phenol component (molar fraction) ) Calculation method)
Integrated value B of peak intensity of 4.0-5.0 ppm,
Calculate the integrated value C of the peak intensity of 6.0-8.0 ppm,
The following calculation was performed.
C ′ = C / 3 ÷ ((B / 14 + C / 3)) (weight ratio of phenol skeleton (molar fraction))

(Evaluation)
The following items were evaluated for each surface protective film obtained as described above.
The following two types of prism sheets were prepared as prism sheets that are non-protective bodies.
Prism sheet (A) (prism sheet manufactured by soft mold type):
A prism sheet made of an acrylic resin having a thickness of 130 μm and a prism pitch of 50 μm and a height of 25 μm, manufactured by a soft mold method.
Prism sheet (B) (self-healing prism sheet):
It is made of an acrylic resin having a thickness of 130 μm, the prism pitch is 50 μm, the height is 25 μm, the hardness calculated by measurement according to JIS R1639-5 is 0.11 ± 0.02, and According to JIS R1639-5, when the weight is removed after the prism sheet is deformed until the weight reaches 20 gf, the deformation cannot be confirmed by observation using an optical microscope (500 times magnification) 3 seconds after the weight is removed. Prism sheet.
Specifically, the measurement is performed by using a micro compression tester MCT-510 and a flat indenter FLAT50 to apply a load to one of the crests (convex portions) of the prism with a flat indenter having a diameter of 50 μm and to apply a load of 20 gf. The load is increased at a constant speed (0.25 gf / second) until reaching the maximum load, and then decreased until the load reaches 0 gf at the same speed (0.25 gf / second). ) By observing the prism from directly above.

  Tables 6 and 7 show the results for the prism sheet (A) (the prism sheet manufactured by the soft mold method), while Tables 8 and 9 show the results for the prism sheet (B) (self-recovering prism sheet). Shown in

(1) Film-forming property The external appearance of each surface protective film formed by coextrusion as described above was evaluated by visual observation.

(2) Initial adhesive strength Each surface protective film was affixed so that the prism surface (lens surface) of each prism sheet might be covered.
Affixing conditions were a room temperature of 23 ° C. and a relative humidity of 50%, each using a 2 kg pressure-bonded rubber roller, and affixed at a speed of 300 mm / min. About sheet | seat (B), after leaving to stand for 1 day, based on JISZ0237, 180 degree peel strength in 25 mm width was measured at the speed of 300 mm / min. The peeling direction at this time was the ridge line direction of the prism. The peel strength measured in this manner was taken as the initial adhesive strength.
(3) Adhesive force with time Each surface protective film was applied to the surface of the lens surface of the prism sheet produced by the soft mold type used in the initial adhesive strength evaluation of (2) under the environment of room temperature 23 ° C. and relative humidity 50%. Each was affixed at a speed of 300 mm / min using a 2 kg pressure-bonded rubber roller.
The prism sheet with the surface protective film attached was left at 60 ° C. for 72 hours. In accordance with JIS Z0237, the 180 degree peel strength at a width of 25 mm was measured at a speed of 300 mm / min.

(4) Unfolding force Rewinding force at a rewinding speed of 15 m / min, according to JIS Z0237, except that the rewinding speed of the wound body of 50 mm width of each surface protective film of Examples and Comparative Examples was changed. Was measured as the deployment force. The results are shown in Tables 4 and 5.
(5) Presence or absence of contamination Under an environment of room temperature of 60 ° C. and relative humidity of 50%, a 2 kg pressure-bonded rubber roller is applied to the surface of the lens surface of the prism sheet manufactured by the soft mold type used in the initial adhesive strength evaluation of (2). And pasted at a speed of 300 mm / min.
The prism sheet with the surface protective film attached was left at 60 ° C. for 168 hours. In accordance with JIS Z0237, a 25 mm wide test piece was prepared, and the surface protective film was peeled off from the prism sheet at a speed of 300 mm / min. The prism sheet surface was observed for the presence of contaminants using an electron microscope.
In addition, when the surface of the adherend was observed with an electron microscope in each of the surface protective films of Examples 6 to 9, no contaminants derived from the tackifier were observed on the surface of the adherend.
(6) Comprehensive evaluation In comprehensive evaluation, even if there is at least one “× (defect)” in each determination, it is determined that “× (defect)” is one, and there is no “× (defect)” Was determined to be “good”.

<Criteria>
Adhesive strength (initial), (aging)
○ (Good): 0.05 N / 25 mm or more × (Bad): Less than 0.05 N / 25 mm Deployment force ◎ (Excellent): Less than 2.0 N / 50 mm ○ (Good): 2.0 N / 50 mm or more 3.5 N / 50 mm or less x (defect): over 3.5 N / 50 mm

(6) Adhesive surface deformation rate The following method:
After the surface protection film is applied to the prism surface of the brightness enhancement film having a prism prism height h1 that is constant and 25 μm, punching is performed from the prism surface side, and then the surface protection film adhesive surface is cut in the cross section generated by the punching. Measuring the distance h2 from the straight line s connecting the two adjacent points where the vertexes of the prism crests are inserted to the apex p of the convex shape generated when the adhesive surface of the surface protective film is pushed into the prism valley. = 3
Calculate the arithmetic mean value of h2 / h1,
Define this as the adhesive surface deformation rate;
Thus, the adhesive surface deformation rate of the surface protective film was obtained.
The measurement was performed by observing with a microscope (magnification: 500 times).
The following apparatus was used for the punching.
Product name: Toko hydraulic clicker Model number: TCM-3500

Claims (7)

[1] As the main component of the adhesive
(A) A structure represented by the formula: [AB] _n (A represents the following polymer block A, B represents the following polymer block B, and n represents an integer of 1 to 3). Copolymer (I), which is a hydrogenated product of copolymer (I ′), and (b) at least two terminals having the following polymer block A, and at least one of the following As a combination of copolymer (II), which is a hydrogenated product of copolymer (II ′) having combined block B, and [2] as a tackifier,
Containing a phenol resin whose phenol component content (molar ratio) is in the range of 5 to 45%;
The mass ratio (A: B) of the total amount of the polymer block A and the total amount of the polymer block B contained in the entire copolymer (I ′) and the copolymer (II ′) is from 5:95 to Within the range of 25:75,
The total aromatic alkenyl compound unit content (St (A + B)) of the copolymer (I ′) and the copolymer (II ′) is 5 to 50% by mass, and the copolymer (I ) And an adhesive layer having a total hydrogenation rate of the copolymer (II) of 80% or more, and a surface protective film having a base material layer.
[Polymer block A]: Polymer block containing an aromatic alkenyl compound unit at a content of 80% by mass or more [Polymer block B]: Containing a conjugated diene compound unit at a content of 50% by mass or more, and Polymer block having a vinyl bond content derived from a conjugated diene compound of 50 mol% or more The surface protective film according to claim 1, which is for a prism sheet. Next way:
After the surface protection film is applied to the prism surface of the brightness enhancement film having a prism prism height h1 that is constant and 25 μm, punching is performed from the prism surface side, and then the surface protection film adhesive surface is cut in the cross section generated by the punching. Measuring the distance h2 from the straight line s connecting the two adjacent points where the vertexes of the prism crests are inserted to the apex p of the convex shape generated when the adhesive surface of the surface protective film is pushed into the prism valley. = 3
Calculate the arithmetic mean value of h2 / h1,
Define this as the adhesive surface deformation rate;
The surface protective film according to claim 1, wherein the deformation rate of the adhesive surface obtained by the step is 50% or more. When the hardness calculated by the measurement according to JIS R1639-5 of the prism mountain is 0.08 to 0.15 and is deformed to 20 gf according to JIS R1639-5, the weight is removed when the weight is removed. The surface protective film according to any one of claims 1 to 3, wherein the surface protective film is used for a self-recovering prism sheet in which deformation cannot be confirmed after 3 seconds from the removal of. The surface protective film according to claim 1, which is for a prism sheet manufactured by a soft mold method. The phenol resin is one selected from the group selected from terpene phenol resins, alkylphenol resins, rosin modified phenol resins, phenol modified coumarone indene resins, phenol modified formaldehyde resins, t-butylphenol resins, and t-butylphenol acetylene resins. It is the above phenol resin, The surface protection film of any one of Claims 1-5 characterized by the above-mentioned. The surface protection film according to claim 6, wherein the phenol resin is a terpene phenol resin.

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