TW201033323A - Surface protection film for prism sheet, and process for production thereof, and prism sheet with the film put thereon - Google Patents

Abstract

Provided is a surface protection film for a prism sheet, which can be spread from a roll with a small force, and the tacky adherence force of which is not easily lowered by the release layer adhering to the pressure-sensitive adhesive layer. The surface protection film is a laminated film composed of (A) a release layer which consists mainly of a saturated fatty acid bisamide and has a thickness of 1 to 100nm, (B) a substrate layer consisting of a polyolefin resin, and (C) a pressure-sensitive adhesive layer consisting of a styrene-based elastomer, said laminated film being produced by co-extruding a molding material (A) which comprises the saturated fatty acid bisamide and the polyolefin resin and another molding material (B) which comprises the styrene-based elastomer.

Description

201033323 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a surface protective film for a cymbal sheet, a method for producing the same, and a ruthenium sheet attached thereto. [Prior Art] The shuttle lens has a triangular prismatic prism as a plurality of lens faces on one side, which can improve the brightness of the liquid crystal display. In order to avoid damage to the crucible, a surface protective film is attached to the crucible formed on the surface of the crucible to protect it. The enamel sheet to which the surface protective film is attached is exposed to a high temperature during handling and storage. Therefore, the adhesive used in the surface protective film is a rubber having a small degree of increase in adhesion due to heating or passage of time. Adhesive. On the other hand, the surface protective film is used in the form of a wound. The rubber-based adhesive generally has a large force (expansion force) required when the wound material is wound up, and has a problem that the developing force gradually increases after long-term storage in the form of a wound.表面 s large surface protection m, since the surface protective film is unwound from the winding in a state of tension, when the surface protective film is attached to the prism sheet, the surface protective film is followed from the cymbal The part that floats on the surface (also known as the "floating" part) is the problem. Therefore, it began to require the development of a surface protective film with a small force (known as "light expansion"). On the right, the release layer is provided on the surface protective film, and although the development force can be reduced, the adhesion of the surface protective film is lowered when the release agent is peeled off from the substrate layer and transferred to the adhesive layer. When the surface protective film is applied to the lens surface of the 3 201033323 of the cymbal sheet, since the contact area between the concave and convex portions of the mirror surface and the surface protective film is small, the release agent is transferred to the adhesive layer. The adhesive layer and the lens surface are concave, and the convex contact area is reduced, so that the adhesion of the surface protective film is greatly reduced. Especially in Patent Document 1, it is proposed that the release layer is not easily transferred to the surface of the adhesive layer. (4) Membrane. OBJECTS OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION However, the release layer of the surface protective film described in Patent Document 1 applies a release agent to a substrate. Formed by. If an organic solvent is used to coat the release agent, the load on the environment is large. Further, if the moisture of the release agent is applied to the dispersion, a drying step is required. When a UV-curable resin liquid of a release agent is applied, an ultraviolet irradiation device is required. SUMMARY OF THE INVENTION An object of the present invention is to provide a surface protective film for a prism sheet which has a small developing force from a wound material and which is less likely to be lowered even if the release layer adheres to the adhesive layer. Further, another object of the present invention is to provide a method for producing a surface protective film for a sheet of the present invention. Means for Solving the Problems The present invention provides the surface protective film of the following [1] to [6], the method for producing the surface protective film of the following [7], and the surface protective film attached to the following [8] The film. 201033323 - A surface protective film for ruthenium sheet is produced by co-extruding a molding material A containing a saturated fatty acid diamine and a polyolefin resin, and a molding material B containing a styrene-based elastomer, and (8) a release layer consisting mainly of a saturated fatty acid melamine, a thick 纟i~ trace m; (B) a polyolefin-based resin layer as a substrate layer; and (C) a styrene-based elasticity as an adhesive layer Body layer. [2] As shown in the above [1], the sputum sheet ^ ^ ^ You Tian your dura mater, wherein the forming raw material A is seriously injured with respect to the polyolefin resin 1 含有 heavy saturated diamine 1-4 Parts by weight. [3] A surface protective film for a ruthenium sheet according to the above [1] or [2], wherein the saturated fatty acid diamine is ethylene stearate stearic acid, methylene distearate decylamine or hexa Indole bisamine succinate. [4] A surface protective film for a ruthenium sheet according to the above (1) or [2], wherein (iv) a fatty acid diamine-based saturated fatty acid aromatic diamine. [5] The surface protective film for a ruthenium according to any of the above [!] to [4], wherein an intermediate layer is formed between the base material layer and the adhesive layer. [6] The surface protective film for a ruthenium sheet according to the above [5], wherein the intermediate layer contains a mixture of a polyolefin-based resin and a styrene-based elastomer containing a saturated fatty acid diamine. [7] A method for producing a surface protective film for a ruthenium, which is used for producing a release layer composed of (A) mainly composed of a saturated fatty acid diamine; 201033323 (B) as a substrate layer An olefin-based resin layer; and (C) a surface protective film for a prism sheet obtained by laminating a stupid vinyl-based elastomer layer as an adhesive layer in this order; and containing a saturated fatty acid dioxime relative to 100 parts by weight of the polyolefin-based resin The molding raw material a of 1 to 4 parts by weight of the amine and the molding raw material B containing the styrene-based elastomer are coextruded. [8] - a ruthenium sheet with a surface protective film attached thereto, comprising: a prism sheet having a plurality of triangular columnar ridges on a lens surface, and (A) mainly composed of a saturated fatty acid tyranamine attached to the lens surface The release layer having a thickness of 1 to 100 nm, (B) a polyolefin-based resin layer as a base material layer, and (C) a styrene-based elastomer layer as an adhesive layer are laminated. Surface protection film; the entangled film has a depth of 〇.3 or more in the adhesive layer. EFFECTS OF THE INVENTION According to the present invention, it is possible to provide a surface protective film for a prism sheet which has a small developing force from the wound material and which is less likely to be lowered even if the release layer adheres to the adhesive layer. Further, 'in accordance with the present invention' can provide a manufacturing method for producing a surface protection crucible for a gusset formed with a very thin release layer. [Embodiment] The surface protective film for a sheet of the present invention (A) is mainly composed of a saturated fatty acid diamine, a release layer having a thickness of i 〜1 〇〇 nm; 1 (B) as a substrate layer An olefin-based resin layer; and 201033323 (c) A styrene-based elastomer layer as an adhesive layer is laminated in this order. The thickness of the surface protective film for a enamel sheet of the present invention is not particularly limited, and the lower limit thereof is usually 12 μm, preferably 20; czm, and the upper limit is usually 100/z 坩, more preferably 60 #m, and particularly preferably 50" m, especially good for 45 ren m. (A) Release layer The release layer is mainly composed of a saturated fatty acid diamine. The term "mainly composed of" as used herein means that the release layer is formed by a saturated fatty acid diamine which is bleed out from the olefin-based resin layer. More specifically, it means that the content of the saturated fatty acid diamine is 9% by weight or more based on the entire release layer. The saturated fatty acid diamine is, for example, a saturated fatty acid such as ethylene bisamine stearate, decyl methylene distearate, and decylamine hexamethylene distearate; and isophthalic acid; A saturated fatty acid aromatic diamine such as methyl bis stearate, N_N, or bis-indolyl phthalic acid phthalic acid is preferred. Among the saturated and fatty acid aliphatic diamines, the ethylene stearate captanamine is furthermore. Further, the saturated sulphuric acid aromatic quinone diamine is preferably isodecyl distearate decylamine. These saturated fatty acid diamines may be used singly or in combination. In addition, other release agents may also be used in combination. > The thickness of the release agent is 1 to 10 nm. The lower limit of a thickness is preferably 5 nm, more preferably 7 (10). The thickness and the upper limit are preferably 80 nm, more preferably 60 nm, and particularly preferably 40 nm. 201033323 When the surface protective film for enamel sheet of the present invention is in the form of a wound, even if the release layer is brought into contact with the adhesive layer and transferred onto the surface of the adhesive layer, since the thickness of the release layer is controlled to be less than 100 nm, The ridge line on the surface of the prism sheet penetrates the release layer and the depth of the adhesive is more than 〇3, so that floating and the like can be avoided, and the adhesion without practical problems can be ensured. By controlling the thickness of the release layer to be less than 1 ιηηη, when attached to the prism sheet, the ridge line of the triangular columnar ridge of the cymbal is used to adhere the surface protection film when it is wound back from the winding (that is, Transfer) The release layer of the adhesive layer is pierced so that the crepe is in contact with the adhesive layer. Thereby, a practically sufficient adhesive force can be obtained. On the other hand, by setting the thickness of the release layer to 1 nm or more, the developing force of the self-winding material can be sufficiently reduced. The thickness of the release layer was determined by the following method. The surface protective film of the present invention is dyed with ruthenium tetroxide, and the dyeing is distinguished by the difference in dyeing workability between the release layer and the substrate layer. The resin sample sealed with the surface protective film was subjected to ultrathin microtome (ultramicr〇t〇me, manufactured by Leica, REICHERT ULTRAeuT y, and thinly cut to produce a plurality of thin film sheets. A thin film for observation in which a cross section of the release layer and the substrate layer was observed was selected from a plurality of film sheets by a transmission electron microscope. The observation film sheet was observed by a transmission electron microscope '& The thickness of the layer is determined by the value of the measured value as the thickness of the release layer. (B) Base material layer 201033323 The base material layer is composed of a polyolefin resin. The release layer of the surface protective film for a sheet of the present invention, The release agent is formed by exudation from the base material layer. The saturated fatty acid diamine which is added to the polyolefin resin to form the release layer remains in the base material layer. The polyolefin resin may be a low density poly Ethylene resin, medium density polyethylene resin, high density polyethylene resin, linear low density polyethylene resin, ethylene-α-dilute copolymer resin, ethylene-ethyl acrylate copolymer resin, - B Ethyl acetate copolymer resin, acetonitrile-acrylic acid decyl ester copolymer resin, ethylene-n-butyl acrylate copolymer resin, polypropylene resin, a mixture of the same. The resin may also contain an additive usually added to the resin. The additive may, for example, be an antioxidant, an ultraviolet absorber, an anti-aging agent, etc. The amount of the additive is usually 5% by weight or less, preferably 3% by weight or less based on the total amount of the resin. The thickness of the substrate layer may be based on the raw material of the ruthenium sheet. The shape of the crucible is suitably adjusted. The general setting is 4 to 80; tzm, preferably 20 to 50/zm. φ (C) The adhesive layer of the adhesive layer contains a styrene elastomer. The adhesive layer mainly contains benzene. The vinyl elastomer further preferably contains an adhesive riding agent. The term "main body" as used herein means that the entire component of the adhesive layer is the most: the weight is preferably 'containing 5% by weight or more. The styrene-based elastomer to be used is preferably a polymer (〇, the following polymer (ii) or a mixture thereof.

"Polymer (i)" contains the following polymer block A and the following polymer block B, and has the formula [AB]n (wherein A represents polymer block A, B 201033323 represents polymer inlay) The copolymer (1) having the structure represented by the segment B, n represents an integer of 1 to 3) or a hydrogenated product thereof. Since n represents an integer of Bu 3, it is apparent that the "structure represented by the general formula [Α-Β] η" is, for example, a structure represented by AB, Α-Β-Α-Β, and α_Β_α·β_α_β. . Among the block copolymers, the incorporation and the 3 may be the same or different in the repetition. "Polymer (ii)" contains the following polymer block oxime and the following polymer block B, having the formula [A_B_A]n (wherein the symbol is synonymous with the above) or the formula (AB)xY ( In the formula, x represents an integer of 2 or more, γ represents a coupling agent residue, and the copolymer (π) having a structure represented by the above-mentioned synonym (symbol) is preferably a polymer (1) and a hydrogenated material of the styrene-based elastomer. a mixture of the polymer (ii) and a weight ratio of the total amount of the polymer block A contained in the polymer (1) to the polymer (i) and the total amount of the polymer block B is 5:95~ In the range of the singularity, the polymer block of the I-stage A" system and the eucalyptus compound unit is mainly composed of the aromatic olefin compound unit. The "polymer block B" is a conjugated diene compound. The unit and the aromatic olefin compound unit are randomly contained in the aromatic olefin/co-battery copolymer. The "aromatic olefin compound unit" is derived from the repeating unit of the aromatic compound compound. Examples of the compound include styrene, tetrabutyl styrene, α-methyl styrene, p_. Styrene, ethyl stupid, diethyl stupid 'u. diphenylethylene, ethyl ethene 蒽 N, N ethyl _p_aminoethyl styrene and B Examples of the "complex diene compound" include 1,3·butadiene, isoprene 201033323 olefin, 2,3-dimethylbutadiene, 13 pentadiene, and 2 methyl group. _ΐ3·octadiene, 1,3-hexadiene, 13_cyclohexadiene, 4,5 diethylene_ι 3·octadiene, 3 butyl-1,3-octadiene, geranene The thickness of the adhesive layer is not particularly limited and is 2 to 20 " m, preferably 3 to 15 m. The adhesive layer of the present invention usually contains an adhesion-imparting agent. A petroleum-based tree, an aromatic-based copolymer, or an alicyclic copolymer, such as an aliphatic copolymer, an aromatic aromatic copolymer, or an alicyclic copolymer, a dandroke-oxime resin, an anthraquinone resin, a phenol resin, and polymerization The rosin-based scent-based resin, (alkyl) resin, xylene-based resin, or the like, which are generally used for the adhesive, are used without particular limitation. The softening temperature of the adhesive-imparting agent is 9 〇 14 (The rc is more preferable. These adhesion-imparting agents may be used singly or in combination of two or more. In addition, in order to improve peeling, and the weather resistance, etc., it is more preferable to use a hydrogenated resin as an adhesion-imparting agent. An adhesive imparting agent commercially available in the form of a mixture with an olefin resin may be used. The adhesive imparting agent is a polymer block B phase with respect to a unit having a conjugated diene compound having a total of a diene compound unit or hydrogenation. The adhesion-imparting agent is used to prevent the amount of the residual paste when the surface protective film is peeled off from the adherend. For example, the mixing ratio of the adhesion-imparting agent is 100 parts by weight relative to the present ethylene-based elastomer. 5 to 5 parts by weight is preferably 2 to 40 parts by weight. The blending ratio differs depending on the kind of the adhesive-imparting agent'. For example, when an adhesive-imparting agent having a softening temperature of 9 〇 to 14 μc is used, it is 15 to 4 Torr with respect to 1 part by weight of the styrene-based elastomer. The weight of 201033323 is better, and it is better to take 20~30% of the inflammation. As long as the amount of the adhesion-imparting agent is within this range, even if the surface protective film is attached to the prism sheet for a long period of time, the adhesion is not easily lowered, and the surface protective film bonded to the prism sheet is less likely to float. The adhesive layer may be blended with, for example, a softener, an antioxidant, and an additive to prevent the yarn, depending on the purpose of controlling the adhesion.

Examples of the softening agent include a low molecular weight diuretic polymer, a polyisobutylene hydrogenated polyisoprene, a hydrogenated polybutadiene, a paraffin-based process oil agent (10), a naphthalene-based process oil, and an aromatic operation. The oil agent is sesame oil tall oil, natural oil, liquid polyisobutylene resin, polybutylene, or the like. These softeners may be used alone or in combination of two or more. The antioxidant is not particularly limited, and examples thereof include an antioxidant (for example, a single antioxidant, a (four) antioxidant, a polymer antioxidant, a sulfur antioxidant, a phosphorus antioxidant, and the like). Next, the preventive agent may be a fatty acid guanamine 'polyethyleneimine, long chain burned graft 4, soybean oil modified alkyd resin (manufactured by Arakawa Chemical Co., Ltd.

Named Ajid 25 1"), Tall oil-modified alkyd resin (manufactured by Arakawa Chemical Co., Ltd., trade name "Aragid 63"). (D) Intermediate layer The surface protective film for a sheet of the present invention further comprises an intermediate layer between the base material layer and the adhesive layer. The release layer is formed by the surface of the substrate layer which is melted immediately after the completion of the co-extrusion (the opposite side of the adhesive layer) from the contact with the cooling roll and solidification to the surface. At this time, the surface of the base material opposite to the release layer also has a saturated fatty acid diamine leakage. When the saturated fatty acid bismuthamine layer is in contact with the adhesive layer 12 201033323, the bonding force between the substrate layer and the adhesive layer sometimes decreases. The intermediate layer has a function of preventing the reduction of the bonding force. The intermediate layer may be a resin which can be bonded to the base layer and the adhesive layer, and a layer composed of a polyolefin resin is preferred. Preferably, the polyolefin resin of the intermediate layer contains a saturated fatty acid diamine and a styrene elastomer. This intermediate layer can also be produced using the sapwood of the surface protective film for enamel sheets. <Production Method> © The surface protective film for enamel sheet of the present invention is obtained by co-extruding a molding material A containing a saturated fatty acid diamine and a polyolefin resin, and a molding material B containing a styrene elastomer. Manufacturer. Further, the saturated fatty acid diamine is usually synthesized by subjecting a diamine to a dehydration condensation reaction with a saturated fatty acid. Therefore, the saturated fatty acid diamine may sometimes contain a diamine which is an impurity and a saturated fatty acid. According to the review by the present inventors, it has been found that the above-mentioned diamine and saturated fatty acid are used for surface protection of the ruthenium sheet of the present invention in association with the feature of the method for producing a surface protective film for a ruthenium sheet of the present invention by osmosis to form a release layer. The film can contaminate the manufacturing device. Therefore, the content of the diamine of the saturated fatty acid diamine and the saturated fatty acid used in the present invention is preferably low. The molding material A and the molding material B can be prepared by mixing the components in a known manner. For example, in the case of molding the raw material A, the polyolefin-based resin containing the saturated fatty acid diamine is prepared by granulation by a biaxial extruder. By adjusting the amount of the saturated fatty acid diamine contained in the molding material A, 13 201033323 can be adjusted to the thickness of the release layer formed on the surface of the substrate layer. In order to form the release layer by bleed, the lower limit of the amount of the saturated fatty acid dimethylamine contained in the molding material A is preferably 1 part by weight, more preferably 1.5 parts by weight, based on 100 parts by weight of the polyolefin resin. On the other hand, based on the viewpoint of obtaining a sufficient adhesive force with the release sheet by forming a release layer of a suitable thickness, and suppressing the release of the release layer from the release roll, the saturated raw material A of the molding material A is contained. The upper limit of the amount of the decylamine is preferably 4 parts by weight, more preferably 2 to 3 parts by weight, per part by weight of the polyolefin resin. The molding raw material A comprising a polyolefin resin containing a saturated fatty acid diamine and the molding raw material b containing a styrene elastomer are coextruded by, for example, two or more multi-layer extruders using a T-die method. Thereafter, the resin side of the extruded raw material A was quenched by a cooling roll. Thereby a multilayer film was obtained. The extrusion temperature is preferably from 160 to 230 °C. The substrate layer and the adhesive layer are first formed by coextrusion. Next, the substrate layer immediately after the completion of the co-extrusion is brought into contact with the cooling, so that the saturated fatty acid diamine contained in the molding material A exudes on the surface of the substrate layer by itself to form a release layer. When the polyolefin resin contains 1 to 4 parts by weight of the saturated fatty acid dimethylamine, a release layer of 1 to 100 nm can be formed on the surface of the base material layer. The surface protective film of the present invention formed in this manner is usually cooled by casting, and taken up by a take-up roll, and stored in the form of a wound. The temperature of the casting rolls was set at 20 to 90 °C. The release layer of the present invention is a layer formed on the surface of the substrate layer on the side opposite to the adhesive layer. <Surface Protective Film> 201033323 As described above, the surface protective film for enamel sheet of the present invention is usually stored in a state of being wound into a wound material. At this time, the release layer is in contact with the adhesive surface of the attached adhesive layer. When the winding is unfolded and attached to the crepe, a portion of the release layer is transferred to the surface of the adhesive surface. In general, the adhesion of the surface protective film is greatly lowered by the transfer of the release layer, but in the surface protective film of the present invention, the ridge line of the crepe sheet penetrates the transferred release layer. Thereby, even if the release layer is transferred, the adhesion of the adhesive layer can be exerted. © (Into the depth) The surface protective film of the present invention is preferably a depth of 0.3 μm or more in the adhesive layer. This can be used to exert proper adhesion. The upper limit of the trap depth is not particularly limited, and is usually 2 private m or less. The depth of penetration is at a room temperature of 23 C and a relative humidity of 50%, and is attached by a 2 kg crimping rubber knee roll at a speed of 300 mm/min. After being left in this state for 30 minutes, a surface protective film is attached. The prism sheet was frozen and cut by a beam slicer. The cut section was observed using a scanning electron microscope® mirror, and the measured value was the depth of penetration. The depth of penetration can be adjusted by adjusting the shear modulus and thickness of the adhesive layer of the surface protective film of the present invention in accordance with the ridge line size of the gusset of the enamel of the surface protective film of the present invention. From this point of view, the shear modulus (23 ° C) of the adhesive layer is preferably 5 χ 10 δ or less. However, the shear elastic modulus is preferably 5 χ 104 or more from the viewpoint of preventing the occurrence of residual paste. Further, from this point of view, the thickness of the adhesive layer is preferably 4 # m or more. 15 201033323 Among them, from the viewpoint of cost, the thickness is preferably 15#m or less. (Expansion force) The wound of the surface protective film of the present invention can be easily rewinded. The developing force of the winding of 50 mm width at a speed of 20 m/min is preferably 3 5 N or less, more preferably 2 N or less. By using this expansion force, even if the width of the wound material exceeds 10 mm, for example, the sound emitted at the time of expansion can be reduced, and the occurrence of floating after sticking to the cymbal can be prevented. (Adhesive adhesion with time) The surface protective film of the present invention preferably has an adhesion at 23 C as measured by the following conditions: 〇 5 〇 5 〇 N / 25 mm. [Condition] A surface protective film of 25 mm width was attached to cover the mirror surface of the cymbal within 3 days from the production of the surface protective film. A crucible composed of an acrylic resin having a thickness of 13 〇 Mm and having a pitch of 5 〇 #m and a height of 25 Å was used. At room temperature 23. (: and a surface with a relative humidity of 50%, a 2 kg pressure-bonded rubber roller, 30 〇mm/min.). The surface protection film is placed at room temperature of 23 ° C and a relative humidity of 50% for 2 weeks. Thereafter, the surface protective film was peeled off at a speed of 3 〇〇mm/min in accordance with JIS Z0237', and the 180-degree peeling strength was measured. The peeling direction of the surface protective film was set to the ridge line direction of the 稜鏡. The measured 180-degree peeling strength was used as a bonding adhesive force at 23 ° C. <Bladding sheet with surface protective film> The prism sheet of the present invention was attached to the lens surface of the prism sheet by a surface protective medium. A prism sheet to which a surface protection film for a enamel sheet of the present invention is attached, that is, a ruthenium sheet having a plurality of triangular columnar ridges on a lens surface, and a affixed to the lens surface (A) a release layer having a thickness of 1 to 100 nm mainly composed of a saturated fatty acid diamine, (B) a polyolefin resin layer as a substrate layer, and (C) a styrene system as an adhesive layer Surface protection of the prism sheet by laminating the elastomer layer And the ruthenium of the enamel sheet having a depth of 〇.3//m in the adhesive layer is also one aspect of the invention. The surface protective film for the enamel sheet of the present invention is bonded. For example, the number of the triangular prisms whose apex angle of the apex angle is about 90. The distance between the apexes of the adjacent ridges is about 10 to 1000 angstroms. The relevant surface protection is attached. The cymbal of the film includes: a cymbal having a plurality of triangular prism prisms on a lens surface; and a cymbal according to any one of the above [1] to [6] attached to a lens surface of the cymbal, and The prism sheet has a depth of penetration of the adhesive layer of 〇. 3 or more, and a ruthenium sheet to which a surface protection Å film is attached. [Examples] Hereinafter, the surface protective film of the present invention is made according to Examples and Comparative Examples. In addition, the present invention is not limited to the following examples. (Example 1) A polyglycoside is saturated with a fatty acid by a polyacrylonitrile "Y9〇〇GV (manufactured by Prime Polymer Co., Ltd.)" Ethyl stearate stearic amine "ALFLOW H50F" Manufactured in a mixture of 1 part by weight of the original material 17 201033323, material A, made of styrene-based elastomer "Dyna丨onl32〇p (100 parts by weight of JSR company, adhesion-promoting agent "alcon P100 (made by Arakawa Chemical Co., Ltd.) 20 parts by weight and a mixture of 1 part by weight of an antioxidant "Irganox 1010 (manufactured by Kabart Chemical Co., Ltd.)" was used as a molding material B, and these mixtures were co-extruded by a T-die method under the following conditions. A surface protective film was produced, and the base layer thickness of the surface protective film was 34/zm, and the thickness of the adhesive layer was ° fi m. The release layer of the surface protective film has a thickness of 6 nm. <Condition> ❹ Extrusion temperature: 2 〇〇 ° C Casting roll temperature: 25 ° C <Measurement method of release layer thickness > The release layer thickness was calculated by the following method. The enamel sheet was dyed with a surface protective film by using four enamel enamels, and the difference between the release layer and the substrate layer in dyeing difficulty was used for the dyeing. The resin sample sealed with the surface protective film was repeatedly subjected to thin-cutting to form a plurality of film sheets in an ultramicrotome (REICHERT ULTRACUT S manufactured by Leica) having a sheet thickness of 70 nm. A film for observation in which a cross section of the release layer and the substrate layer was observed was selected from a plurality of film sheets by a transmission electron microscope (JE-2100, manufactured by JEOL Co., Ltd.). The film sheet for observation was observed by a transmission electron microscope (JE-2100, manufactured by JEOL Co., Ltd.), and the thickness of the release layer was measured from three places. The average value of the measured values is taken as the thickness of the release layer. (Example 2) A surface protective film was produced in the same manner as in Example 1 except that the amount of the decyl ethylene distearate was changed to 1.5 parts by weight to 18 201033323. The base layer of the surface protective film had a thickness of 34 Am, the thickness of the adhesive layer was 6 μm, and the thickness of the release layer was 9 nm. (Example 3) A surface protective film was produced in the same manner as in Example 1 except that the amount of the decyl ethylene distearate was changed to 3 parts by weight. The thickness of the substrate layer of the surface protective film was 34 #m, the thickness of the adhesive layer was 6#m, and the thickness of the release layer was 80 nm.

❹ (Example 4) The sapwood produced when the both ends of the surface protective film of the present invention were formed as a whole was formed into pellets by a twin-screw extruder. 1 part by weight of polypropylene "Y9〇〇GV (manufactured by Prime Polymer Co., Ltd.)" and an ethylene bis stearate amide "alfl〇w H5〇F (made by Nippon Oil Co., Ltd.)" 1 The mixture of the parts by weight is used as the forming material A, and a mixture of 7 parts by weight of polypropylene ("Y900GV (manufactured by Prime Polymer)" and 3 parts by weight of the above particles is used as a raw material for forming an intermediate layer to be used for the benzene. 1 part by weight of the ethylene-based elastomer "Dynal 〇nl32〇p (manufactured by JSR)", the adhesion-imparting agent "alcon ρι〇〇 (made by Arakawa Chemical Co., Ltd.)", 2 parts by weight, and the antioxidant "Irganox 1〇1" A mixture of 1 part by weight of 〇 (manufactured by Kabart Chemical Co., Ltd.) was used as a molding material B, and these mixtures were extruded by a tau mold method under the same conditions as in Example , to prepare a surface protective film. The thickness of the base layer of the surface protective film is 28 μm, the thickness of the intermediate layer is 6 m, and the thickness of the adhesive layer is 6/zm. Further, the release layer of the surface protective film is 65 nm at a degree of 65 nm. (Example 5) A surface protective film was produced in the same manner as in Example 1 except that 3 parts by weight of decylamine bis-stearate bisamine (manufactured by Nippon Kasei Co., Ltd.) was used as the saturated fat decylamine. The thickness of the base layer of the surface protective film was 34/zm, and the thickness of the adhesive layer was 6/m. Further, the release layer of the surface protective film had a thickness of 40 nm. (Example 6) The same as Example 1 except that 2.5 parts by weight of hexamethylene distearate amide "Surripax ZHS (manufactured by Nippon Chemical Co., Ltd.)" was used as the saturated fatty acid diamine. The same method is used to make a surface protective film. The base layer of the surface protective film had a thickness of 34 / zm and the thickness of the adhesive layer was 6 μm. Further, the release layer of the surface protective film had a thickness of 15 nm. (Example 7) The same procedure as in Example 1 was carried out, except that 2.5 parts by weight of m-xylylene distearate bismuth succinimide "Seripolix pxs (manufactured by Nippon Kasei Co., Ltd.)" was used as the saturated fatty acid diamine. To make a surface protective film. The thickness of the substrate layer of the protective film is 34/zm, the thickness of the adhesive layer is further, and the thickness of the release layer of the surface protective film is 30 ηηη. (Comparative Example 1) A surface protective film was produced in the same manner as in Example i except that the saturated fatty acid diamine was not used. (Comparative Example 2) A surface protective film was produced in the same manner as in Example 1 except that the amount of the decyl ethylene distearate was changed to 0.5 part by weight to 20 201033323. Although the thickness of the release layer was to be determined, no release agent layer was observed. (Comparative Example 3) A surface protective film was produced in the same manner as in Example 1 except that the amount of the decyl ethylene distearate was changed to 0.5 part by weight. The release layer of the surface protective film had a thickness of 200 nm. (Comparative Example 4) A surface protective film was produced in the same manner as in Example 1 except that 3 parts by weight of stearic acid amine "ALFLOW S-10 (manufactured by NOF)" was used as the saturated fatty acid decylamine. . Although the thickness of the release layer was to be determined, the release agent layer was not observed. (Comparative Example 5) In addition to the substitution of the phthalic acid amide of the saturated fatty acid diamine, the oleic acid decyl amide of the unsaturated fatty acid guanamine "ALFLOW E-10 (manufactured by Nippon Oil Co., Ltd.)" 3 weight A surface protective film was produced in the same manner as in Example 1 except for the portions. Although the thickness of the release layer was to be determined, the release agent layer was not observed. (Comparative Example 6) In addition to the substitution of the decylamine ethylene stearate which is a saturated fatty acid diamine, the cis-pentadienoyl decylamine which is an unsaturated fatty acid decylamine "ALFLOW Pl〇 (manufactured by Nippon Oil Co., Ltd.) A surface protective film was produced in the same manner as in Example 1 except for 3 parts by weight. Although the thickness of the release layer was to be determined, no release agent layer was observed. (Comparative Example 7) 21 201033323 In addition to replacing the decylamine ethylene stearate, which is a present amine which is a saturated fatty acid diamine, is the dianion of the unsaturated fatty acid diamine?铋-, mountain & slave r

The oleic acid amide amine "ALFLOW AD-281 (manufactured by Nippon Oil Co., Ltd.)" was used to produce a surface protective film in the same manner as in Example 1 except that it was more severely burned.矣 Only the surface protective film has a release layer thickness of 20 nm. (Evaluation) Surface protection from 1 to 7

Films The following items were evaluated for the obtained Examples 1 to 7 and Comparative Examples. The results are shown in Table 1. (1) Developing force The surface protective film was wound around a paper core having an inner diameter of 3 inches to produce a wound having a width of 5 mm. According to JIS z〇237, the surface protective film was wound back from the winding at a rewinding speed of 2 〇m/min, and the high-speed rewinding force was measured. The measured value obtained is the developing power.

When the developing power was 2 N/50 mm or less, it was evaluated as excellent (?), and when it was more than 2 N/50 mm and 3.5 N/50 mm or less, it was evaluated as good (〇), and when the developing power exceeded 3.5 N/50 mm, it was evaluated as poor (X). ). (Evaluation of the stability of the expansion force) After the coiling property was evaluated as excellent or good, the wound material was aged in a thermostat at 40 ° C for 1 week, and the developing force was measured, and the developing force was evaluated on the same basis. Comparative Example 3, in which the initial adhesion was poor, was not evaluated. (2) Whether there is floating, initial adhesion, and depth of penetration toward the adhesive layer for a slab composed of an acrylic resin having a thickness of ΠΟ/zm, a prism pitch of 22 201033323 50# m, and a height of 25 _ A test piece was produced by attaching a surface protective film having a width of 25 mm to the lens surface of the cymbal. Further, to 23 C and a relative humidity of 50%, a 2 kg pressure-bonding rubber roller was used to attach the surface protective film to the cymbal at a catch rate of 300 mm/min. After the test piece was left in this state for 3 minutes, the presence or absence of floating was evaluated. The person who did not float was evaluated as good (〇), and the person who had floated was evaluated as bad (the father was the next, and the initial test force was measured for the test piece that did not float. According to JIS Z0237, the surface protective film was 3 mm. The peeling strength of the surface protective film is set to the ridge line direction of the 稜鏡. The obtained 180-degree peel strength is used as the initial adhesion force. In addition, the scanning electron microscope is used. (SEM) Observed that the apex of the ridge line of the enamel sheet was deeper toward the adhesive, and the depth of penetration into the adhesive was 0.6 m. The peel strength (initial adhesion) was evaluated as 〇5 N/25 mm or less. (〇)' The case of exceeding 0.5N/25mm was evaluated as poor (X). (3) The surface protective film with a width of 25 mm was attached in such a manner as to cover the lens surface of the cymbal with a thickness of 130/. A crucible composed of an acrylic resin of zm and having a pitch of 50 μm and a height of 25 μm. Under a temperature of 23 ° C and a relative humidity of 50%, a 2 kg pressure-bonded rubber roller is used, which is attached at a speed of 300 mm/min. Surface warranty The film was allowed to stand at room temperature of 23 ° C and a relative humidity of 50% for 2 weeks, and then the surface protective film was peeled off at a rate of 300 mm/min according to JIS Z0237, and the 180-degree peel strength "surface protective film was measured. The peeling direction is set to the ridge line direction of the 稜鏡. In this way, the measurement of 23 201033323 determines the 180 degree peel strength as 23t). When the peel strength was 0.7 N/25 mm or less, it was evaluated as good (〇), and when it exceeded 0.7 N/25 mm, it was evaluated as poor (X). [Results] [Table 1]

Olein amide type l A 2 3 Example 4 5 6 7 1 2 3 — A ~~5~ Comparative Example 4 5 6 7 AAABCDA Mn melamine tl 1.5 3 3 3 2.5 2.5 a 0.5 HFGH surface ionization Wide thickness Nltl 6 9 80 65 40 15 30 One - 200 X 〇〇〇i 20 〇 Initial initial adhesion N/25mm o 0.22 〇0.21 〇0.09 〇0.16 〇0.18 〇0.20 〇0.19 〇0.25 〇0.23 Attachment time Adhesion 4% N/25mm 〇0.50 〇0.43 〇0.20 〇0.41 〇0.43 〇0,43 〇0.40 〇0.60 〇0.53 -X_ 0.16 , 〇0.18 〇0.15 〇0.20 〇0.40 0.44 0.48 0.49 〇〇υ 〇〇〇〇〇〇 V 〇〇π 〇W Λ period iN/5Umrn 3.4 2.5 1.5 2.1 1.9 1.8 1.8 4.5 3.8 1.0 3.6 3.5 3.5 3 0 o 〇 ◎ ◎ ◎ ◎ XX ◎ VVV 〇 时 M M M M M M M M M M M M M M M M M M M M M M M M M M M M M A 3.6 〇◦ 〇 ◎ ◎ —————— ———— — X

Note: The fatty acid guanamine types are as follows. A: decylamine ethylene stearate B: decyl methylene distearate C: decyl hexamethylene distearate D: m-xylylene metastearate

E: decylamine stearate F ··oleic acid decylamine G: cis-dodecenoic acid decylamine H: ethylene diol oleate amide (Example 8) by polypropylene "Y900GV (Prime Polymer) (manufacturing) 100 parts by weight of a mixture of 3 parts by weight of ethylene bis stearate allysamine "ALFLOW H50F (manufactured by Nippon Oil Co., Ltd.)" as a raw material A, and a styrene-based elastomer. "Dynalonl320P (manufactured by JSR)" 24 201033323 100 parts by weight and adhesion-imparting agent "alcon P100 (manufactured by Arakawa Chemical Co., Ltd.) 15 parts by weight and 1 part by weight of antioxidant "Irganox 101" (manufactured by Kabate Chemical Co., Ltd.) The mixture was used as the forming material B, and the mixture was coextruded by the tau mold method under the following conditions to prepare a surface protective film. The thickness of the surface protective film was 40/zm, the thickness of the substrate layer was 34 " m, and the thickness of the adhesive layer was 6/zm. Further, the release layer thickness of the surface protective film was 49 nm. <conditions>

Extrusion temperature: 200 ° C, casting roll temperature: 25 ° C (Example 9), except that the adhesion imparting agent "alc〇n ρι〇〇 (manufactured by Arakawa Chemical Co., Ltd.)" was adjusted to 20 parts by weight. The surface protective film was obtained in the same manner as in Example 8. The release layer thickness of the outer surface protective film is 5 Onm. (Example 1) A surface protective film was obtained in the same manner as in Example 8 except that the amount of the adhesion-imparting agent "alcon P100 (manufactured by Arakawa Chemical Co., Ltd.) was adjusted to 25 parts by weight. Further, the release layer thickness of the surface protective film was 48 nm. (Example 1 1) A surface protective film was obtained in the same manner as in Example 8 except that the amount of the agent "alcon P100 (manufactured by Arakawa Chemical Co., Ltd.)" was adjusted to i i i and 30 parts by weight. 25 201033323 In addition, the release layer thickness of the surface protective film is 53 nm. (Example 12) The surface protective film β was obtained in the same manner as in Example 8 except that the amount of the adhesion-imparting agent "alcon P1 〇〇 (manufactured by Arakawa Chemical Co., Ltd.) was adjusted to 35 parts by weight. The thickness of the release layer of the surface protective film was 55 nm. (Example 13) In addition to the dispensing agent "alcon Pl〇〇 (manufactured by Arakawa Chemical Co., Ltd.)

A surface protective film was obtained in the same manner as in Example 8 except that the amount was adjusted to 40 parts by weight. Further, the release layer thickness of the surface protective film was 48 nm. (Example 14) A surface protective film was obtained in the same manner as in Example 8 except that the amount of the adhesion-imparting agent "alc〇n P 1 (manufactured by Arakawa Chemical Co., Ltd.) was adjusted to 45 parts by weight.

Further, the release layer thickness of the surface protective film was 52 nm. (Comparative Example 8) A surface protective film was obtained in the same manner as in Example 8 except that the saturated fatty acid diamine was not used. (Comparative Example 9) The same procedure as in Example 8 except that the saturated fatty acid diamine was not used and the amount of the adhesion-imparting agent "alcon P1 〇〇 (manufactured by Arakawa Chemical Co., Ltd.) was adjusted to 3 parts by weight. To get a surface protective film. (Evaluation) 26 201033323 The following items were evaluated for the surface protective films of Examples 8 to 14 and Comparative Examples 8 to 9 thus obtained. The specific results are shown in Table 2. (1) Deployment force The surface protective film was wound around the #3胄忖 paper core to make a winding of 5 mm width. According to JIS z〇237, the surface protective film was wound back from the winding at a rewinding speed of 2 〇m/min, and the high-speed rewinding force was measured. The measured value obtained is the developing power. ^ When the expansion force is 2N/50mm or less, it is evaluated as excellent (?), and when it is more than 2N/50mm and 3.5N/5〇mm or less, it is evaluated as good (〇), and when the expansion force exceeds 3.5N/50mm, it is evaluated as Bad (X). (2) Initial adhesion The surface protection film was attached to cover the mirror surface of the enamel within 3 days from the production of the surface protective film. The ruthenium film is made of an acrylic resin having a thickness of l3 〇 Wm, a pitch of 5 〇em, and a height of 25//m. The attachment conditions were as follows: a room temperature of 23 〇c and a relative humidity of 〇%, and a 2k crimping rubber roller at a speed of 3 〇〇mm/min, and placed in this state for 30 minutes. JIS z〇237, a 180 degree peel strength of 25 mm wide was measured at a speed of 300 mm/min. The peeling direction at this time is the ridge line direction of the 稜鏡. The peel strength measured in this manner was taken as the initial adhesion force. (3) Adhesive adhesion at 23 ° C, except after attaching the surface protective film, at 23. (: Outside the environment for one week) The adhesion measured by the same method as the initial adhesion was used as the adhesive adhesion of 2 3 C. 27 201033323 [Table 2] Comparative Example 8 9 10 11 12 13 14 8 9 Adhesive-imparting agent 4 Θ*15 15 25 30 35 40 45 15 30 Deployment force|Initial N/50mm 1.2 1.0 1.3 1.0 U 1.2 1.2 4.8 5.3 1 ◎ ◎ ◎ ◎ ◎ ◎ ◎ χ χ Initial adhesion Force N/25mm 0.09 0.14 0.21 0.26 0.37 0.45 0.60 0.10 0.29 23 °C Adhesive adhesion time N/25mm 0.02 0.05 0.05 0.14 0.28 0.37 0.52 0.08 0.22 It is apparent from Table 2 'Unsaturated fatty acid diamine Although the surface protective film 'has a moderate adhesive strength', even if the amount of the adhesive-imparting agent to be inhibited is not good, the developing power is not good. In contrast, the use of the saturated fatty acid diamine as the ethylene bis-stearate amide is used. Inventive surface protective film can obtain moderate spreading force and moderate initial adhesion. ® (Example 15) 1"

A mixture of the weight loss and the amount of the ethylene bis-stearate amine, r alfl〇W H50F (manufactured by Nippon Oil Co., Ltd.), j3 parts by weight, as a forming material A', from styrene 100 parts by weight of an elastomer r dynalonl 320P (manufactured by JSR), 20 parts by weight of an adhesion-imparting agent r alc〇n Pioo (manufactured by Arakawa Chemical Co., Ltd.), and an antioxidant "irganox 1〇1〇 (manufactured by Kabate Chemical Co., Ltd.)" One part by weight of the mixture was used as the forming material B, and the mixture was coextruded by the T-die method under the following conditions to prepare a surface protective film. The thickness of the surface protective film is 40, and the thickness of the substrate layer is . v Jy m, the thickness of the adhesive layer is 6 / / m. Further, the release layer of the surface protective film has a thickness of 5 Å. <conditions>

Extrusion temperature: 200 ° C Casting roll temperature: 25 ° C 28 201033323 (Comparative Example) A wound of a surface protective film was obtained in the same manner as in Example 15 except that the saturated fatty acid diamine was not used. (Evaluation) The following items were evaluated for each of the surface protective films obtained in the above manner. These results are shown in Table 3. (1) Dispersing force For each of the surface protective films of the examples and the comparative examples, a winding of 50 mm width was used to measure the high-speed rewinding force as a developing force in accordance with JIS Z0237 at a rewinding speed of 20 m/min. When the developing power was 2 N/50 mm or less, it was evaluated as excellent (?), and when it was more than 2 N/50 mm and 3.5 N/50 mm or less, it was evaluated as good (〇), and when the developing power exceeded 3.5 N/50 mm, it was evaluated as poor (X). ). (2) Adhesion (normal temperature) The surface protective film to be wound was produced at 23. (: The thermostat was aged for 1 week, and the result was attached to the lens surface of the cymbal sheet and the acrylic plate. The attachment condition was ® at a room temperature of 23 ° C and a relative humidity of 50%, with a 2 kg pressure-bonded rubber roller, The film was attached at a speed of 300 mm/min, and placed in an environment of 23 ° C for 1 day, and the obtained product was measured at a speed of 300 mm/min in accordance with JIS Z0237 at a peeling strength of 180 degrees in width of 25 mm. Adhesive force is used as the rate of mirror adhesion (normal temperature) and plane adhesion (normal temperature). (3) Adhesion (4〇t) In addition to setting the curing condition of the surface protective film winding to 4 〇, Adhesive force (normal temperature) The adhesion measured by the same method is 29, 201033323 lens surface adhesion (40 ° C), plane adhesion (40 ° C). (4) temperature stability, lens surface, plane Adhesion (4 〇. (:) divided by the adhesion (normal temperature) value as the reduction ratio of adhesion. When the reduction ratio is 7〇% or more, it is evaluated as good (〇)' will be less than 70% The situation was evaluated as poor stability (X). [Results] Example 15 - Exhibition The rib force is adhered to the surface of the lens surface - a transparent φ ιυ plane evaluation result JN/DUmm 1.0 〇-- 5 1 adhesion normal temperature N/25mm 0.123 5.8 ~0Λ56~2\ $__ 4〇t N/25nim 0.096 2.4 0.128 8.4 Reduction ratio 78% 41% 82% _ 7.7 Stability 〇X ~~·~ο-- 92% Overall evaluation r 〇----~~Δ--- It is obvious from Table 3 that saturation is not used The surface protective film of the fatty acid diamine has excellent adhesion stability, but has poor developing power. In contrast, the surface protective film of the present invention which is a saturated fatty acid diamine of ethylene distearate decylamine is used. When it is applied to the lens surface of the prism sheet, it is excellent in both temperature stability and development force in the adhesive force. INDUSTRIAL APPLICABILITY The surface protective film of the present invention can be used for the protection of the lens surface of the cymbal sheet. Simple description of the schema] No [Main component symbol description] None

Claims (1)

201033323 VII. Patent application scope: 1. A surface protective film for enamel film, which is obtained by co-extruding a forming material A containing a saturated fatty acid diamine and a polyolefin resin, and a forming raw material B containing a styrene-based elastomer. Manufactured, laminated (A) a release layer composed mainly of a saturated fatty acid diamine, a thickness; (B) a polyolefin resin layer as a substrate layer; and (C) benzene as an adhesive layer A vinyl elastomer layer. The surface protective film for a prism sheet according to the first aspect of the invention, wherein the molding material A contains 1 to 4 parts by weight of the saturated fatty acid diamine with respect to 1 part by weight of the polyolefin resin. 3. The surface protective film for ruthenium according to claim 1 or 2, wherein the saturated fatty acid diamine is ethyleneamine distearate, decyl methylene distearate or hexamidine Decylamine bisamine stearate. 4. The surface protective film for ruthenium according to claim 1 or 2, wherein the 'saturated fatty acid diamine is a saturated fatty acid aromatic diamine. The surface protective film for a ruthenium according to any one of claims 1 to 4, wherein an intermediate layer is formed between the base material layer and the adhesive layer. 6. The surface protective film for a prism sheet according to claim 5, wherein the intermediate layer comprises a mixture of a polybasic resin and a styrene elastomer containing a saturated fatty acid diamine. 7. A method for producing a surface protective film for a ruthenium, which is used for producing a release layer composed of (A) mainly composed of a saturated fatty acid diamine; 31 201033323 (B) as a substrate layer An olefin-based resin layer; and (C) a surface protective film for a ruthenium sheet obtained by laminating the ethylenic elastomer layer as an adhesive layer in this order; and containing a saturated fatty acid in 100 parts by weight with respect to the polyene-based resin The molding material A of 1 to 4 parts by weight of the diamine is co-extruded with the molding material B containing the styrene elastomer. 8. A prism sheet to which a surface protective film is attached, comprising: a ruthenium having a plurality of triangular columnar ridges on a lens surface, and (A) mainly composed of a saturated fatty acid dimethylamine on the lens surface a prism having a thickness of 1 to 10 nm, a (B) polyolefin resin layer as a base layer, and (C) a styrene elastomer layer as an adhesive layer The surface protective film for the sheet; the enamel:: ash 1! 'The depth of the agent layer is 〇.3" m or more. Eight, schema · no 32