JP2009297973A - Laminated film for screen board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated film for screen board which includes excellent writable property, erasability, and anti-glare quality, and, at the same time, can be manufactured economically by decreasing the amount of fluororesin used, and can be manufactured with sufficient workability by lessening the laminating work using the adhesive bond. <P>SOLUTION: In a laminated film for metal surface coating 100A to manufacture screen board by coating on the metal surface, a substrate resin layer 10, a stratum 20 whereupon the embossing can be given, an adhesive polymer composition stratum 30 which consists of denaturation polyester-based elastomer, a stratum 40 which consists of ethylene-vinyl alcohol copolymer resin, and a stratum 50 which consists of adhesive fluororesin are stacked in this order. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a laminated film-covered metal plate for a screen board that has both a function as a marker board and a function as a screen for OHP and the like, and a laminated film for a screen board used therefor.

  Conventional screen boards include those obtained by laminating a fluorine film on the surface of a white base material. In this screen board, the surface of the fluorine film is written with a dedicated marker, and the written material can be erased.

  Moreover, in order to use it for screens, such as OHP, it is required to have anti-glare property. In order to impart this antiglare property, it is necessary to impart irregularities to the fluorine film on the surface. As a method for imparting irregularities, there has been performed a method in which silica particles or the like are contained in a fluorine film, or an irregular shape is formed on the surface of the film by an embossing roll immediately after film formation.

Patent Document 1 describes a method for producing a whiteboard sheet in which embossing is transferred by pressing an embossed surface of an embossed plate against the surface of a laminate film that is a laminate of a fluorine film and a white substrate. ing.
Japanese Patent Application Laid-Open No. 11-254885

  In order to impart antiglare properties to the screen board, the unevenness imparted to the surface of the fluorine film needs to have a constant height and pitch. If these are not constant, ink clogging occurs in a portion where the pitch of the unevenness is narrow, and there is a problem of erasability that written characters are difficult to wipe cleanly.

  However, among the above-described method for providing unevenness, when silica particles or the like are included, the unevenness is determined by the position of the particles, so it is difficult to adjust the unevenness position to a constant level. It could not be made constant. In addition, when forming an uneven shape on the surface of the film with an embossing roll immediately after film formation, the fluorine film shrinks due to a rapid temperature difference after film formation. I couldn't.

  In addition, the clogging of the ink can be prevented by increasing the pitch of the unevenness, but in this case, the antiglare treatment is insufficient and the antiglare property cannot be imparted to the surface of the fluorine film. In addition, when the surface of the fluorine film is not uneven, the marker ink is repelled and cannot be written on the surface of the fluorine film. Therefore, a certain degree of unevenness is also required from the point of writability.

  The manufacturing method described in Patent Document 1 aims to solve the above problems. However, in the manufacturing method described in Patent Document 1, since the fluorine film and the white base material are bonded together using an adhesive, the film has a certain amount of elasticity from the viewpoint of workability when the films are bonded together. And the fluorine film must have a certain thickness.

  Here, since the fluororesin is generally expensive, it is required to reduce the amount of the fluororesin by making the fluorofilm as thin as possible. However, the method described in Patent Document 1 has a problem that due to the above reasons, the amount of fluororesin used is reduced and the screen board cannot be manufactured economically. In addition, there is a problem that workability is poor because there is a process of bonding films.

  Therefore, the present invention has both writing property, erasability and anti-glare property, and can be produced economically by reducing the amount of fluororesin used, and the laminating operation using an adhesive is also possible. It is an object of the present invention to provide a laminated film for a screen board and a laminated film-coated metal plate for a screen board, which can be manufactured with a reduced amount, can be manufactured with good workability, and have an excellent interlayer adhesion.

  The present invention will be described below. In order to facilitate understanding of the present invention, reference numerals in the accompanying drawings are appended in parentheses, but the present invention is not limited to the illustrated embodiments.

  A first aspect of the present invention is a metallized laminated film for coating a metal surface to form a screen board, comprising a base resin layer (10), an embossable layer (20), and a polyalkylene ether glycol segment. An adhesive polymer comprising a modified polyester elastomer obtained by modifying a saturated polyester thermoplastic elastomer having a content of 58 to 73% by weight with an unsaturated carboxylic acid or a derivative thereof in the presence of a radical generator. A laminated film (100) for a screen board in which a composition layer (30), a layer (40) made of an ethylene-vinyl alcohol copolymer resin, and a layer (50) made of an adhesive fluororesin are laminated in this order. .

The second aspect of the present invention is a laminated film for metal coating for coating a metal surface to form a screen board, which is a base resin layer (11), an embossable layer (21), and an elastic modulus at an embossing temperature. There ¹⁰ 7 Pa or less, the layer elastic modulus of the film temperature during steel lamination made of resin is ¹⁰ 8 Pa or more (25), the content of the polyalkylene ether glycol segment is saturated polyester is 58 to 73 wt% Adhesive polymer composition layer (31) comprising a modified polyester elastomer obtained by modifying a thermoplastic elastomer with an unsaturated carboxylic acid or derivative thereof in the presence of a radical generator, ethylene-vinyl alcohol copolymer A screen board in which a layer (41) made of a combined resin and a layer (51) made of an adhesive fluororesin are laminated in this order. A laminated film (101).

In the second aspect of the present invention, the resin having an elastic modulus of 10 ⁷ Pa or less at the embossing temperature and a modulus of elasticity of 10 ⁸ Pa or more at the film temperature when laminating steel plates is preferably a polycarbonate resin.

  In the above-mentioned laminated film for screen board (100, 101), the surface on which the layer (40, 41) made of an ethylene-vinyl alcohol copolymer resin in the layer (50, 51) made of an adhesive fluororesin is laminated Layers (60, 61) made of a fluororesin may be further laminated on the opposite surface.

  In the laminated film for screen board (100, 101), the embossable layer (20, 21) is substantially free from a clear crystal melting peak at the time of temperature rise as measured by a differential scanning calorimeter (DSC). It is preferable that the amorphous polyester-based resin is a layer containing 50% by mass or more with respect to 100% by mass of the entire embossable layer.

  In the laminated film for a screen board (100, 101), the base resin layer (10, 11) has a clear crystal melting peak observed when the temperature rises in the measurement with a differential scanning calorimeter (DSC). The crystalline polyester resin is a layer containing 50% by mass or more, based on the total mass of the base resin layer as 100% by mass, and the crystal melting peak temperature (Tm) of the substantially crystalline polyester resin. ) And the glass transition temperature (Tg) are preferably Tm (° C.)> (Tg + 30) (° C.).

  In the laminated film for screen board (100, 101), the weight average molecular weight in terms of styrene by gel permeation chromatography (GPC) at the time of forming the embossable layer (20, 21) is 65,000 to 140000. It is preferable to be in the range.

  In the above-mentioned laminated film for screen board (100, 101), the embossable layer (20, 21) contains crystalline polybutylene terephthalate resin and has a clear crystal at the time of temperature rise by a differential scanning calorimeter (DSC). The melting peak temperature (Tm) is indicated, and the heat of crystal melting (ΔHm (J / g)) is preferably 10-60.

  In the laminated film (100, 101) for the screen board, the adhesive fluororesin preferably contains a carbonate group and / or a maleic acid group.

  In the laminated film for a screen board (100, 101), an adhesive polymer composition layer (30, 31) made of a modified polyester elastomer, a layer (40, 41) made of an ethylene-vinyl alcohol copolymer resin, And the total thickness of each layer of the layers (50, 51) made of adhesive fluororesin is preferably 10 μm or less.

  In the above-mentioned laminated film for screen board (100, 101), each layer is preferably formed into a laminated film by coextrusion, and the layer (50, 51) side made of adhesive fluororesin or the layer (60 made of fluororesin) (60) , 61), it is preferable that unevenness is formed by an embossing roll.

  The roughness of the surface on which the unevenness is formed by the embossing roll is such that Ra (center line average roughness) is 0.7 μm or more and 5 μm or less, Rmax (maximum height) is 4 μm or more and 40 μm or less, and Rz (ten-point average roughness). Is 3 μm or more and 30 μm or less, Rp (average depth) is 1.5 μm or more and 20 μm or less, Pc (number of peaks) is 7 or more and 50 or less / 8 mm, and gloss is preferably 50 or less.

  Here, “glossiness” refers to the glossiness measured according to JIS K7105.

  3rd this invention consists of a metal plate (90, 91) which affixed the base film resin layer (10, 11) side in said laminated film (100, 101) and this laminated film, It is a laminated film covering metal plate (200, 201) for screen boards.

  4th this invention is a screen board provided with said laminated film covering metal plate (200, 201) for screen boards.

  The laminated film for a screen board of the present invention has a writing property, an erasability, and an antiglare property, and can be produced economically by reducing the amount of fluororesin used. The laminated film-coated metal plate for boards can be manufactured with good workability by reducing the laminating operation using an adhesive. Furthermore, according to the laminated film for a screen board of the present invention, it is possible to suppress the occurrence of emboss return that becomes a problem during processing.

  Hereinafter, the present invention will be described based on embodiments shown in the drawings.

1. Screen Board Laminated Film FIGS. 1A and 2A schematically show the layer structure of the screen board laminated film 100 according to the first aspect of the present invention. A laminated film 100A for a screen board shown in FIG. 1A includes a base resin layer 10, an embossable layer 20, an adhesive polymer composition layer 30 made of a modified polyester elastomer, and an ethylene-vinyl alcohol copolymer. The resin layer 40 and the adhesive fluororesin layer 50 are laminated in this order. Further, as shown in FIG. 2 (a), in another embodiment of the laminated film 100B for a screen board according to the first aspect of the present invention, from the ethylene-vinyl alcohol copolymer resin in the layer 50 made of an adhesive fluororesin. A layer 60 made of a fluororesin is further laminated on the surface opposite to the surface on which the layer 40 is laminated.

FIG. 1B and FIG. 2B schematically show the layer structure of the laminated film 101 for a screen board according to the second invention. The laminated film 101A for a screen board shown in FIG. 1 (b) has a base resin layer 11, an embossable layer 21, an elastic modulus of 10 ⁷ Pa or less at the embossing temperature, and an elastic modulus at the film temperature when the steel plates are laminated. A layer made of a resin having a viscosity of 10 ⁸ Pa or more (hereinafter referred to as “emboss return prevention layer 25”), an adhesive polymer composition layer 31 made of a modified polyester elastomer, and an ethylene-vinyl alcohol copolymer resin. The layer 41 and the layer 51 made of an adhesive fluororesin are stacked in this order. Further, as shown in FIG. 2B, in another embodiment of the laminated film 101B for a screen board according to the second aspect of the present invention, from the ethylene-vinyl alcohol copolymer resin in the layer 51 made of an adhesive fluororesin. A layer 61 made of a fluororesin is further laminated on the surface opposite to the surface on which the layer 41 is laminated.

  Hereinafter, each layer constituting the laminated film 100 or 101 for the screen board of each form according to the first and second aspects of the present invention will be described in detail. In the following, for one word or phrase, a reference code without parentheses and a reference code with parentheses may be written together. In this case, the reference code in parentheses is according to the second invention. This means that the reference numerals without parentheses described before are those according to the first aspect of the present invention.

1.1. Base resin layer The base resin layer 10 (11) is an unstretched layer containing a polyester resin as a main component. Here, “non-stretching” means that a stretching operation is not intentionally applied, and does not mean, for example, that there is no orientation generated by pulling with a casting roll during extrusion film formation. . Further, “as the main component” means that the layer containing itself is 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more based on the whole layer (100% by mass) ( The same applies hereinafter). The base resin layer 10 has a role of giving stiffness to the laminated film 100 and adhering to the metal plate 90.

  It does not specifically limit as a polyester-type resin, A various thing can be used. Typical examples include one or more alcohol components selected from ethylene glycol, propylene glycol, butanediol, cyclohexanedimethanol, and the like, and one or more acid components selected from terephthalic acid, isophthalic acid, adipic acid, and the like. Or a blend of these polymers can be used.

  The base resin layer 10 (11) is a substantially crystalline polyester resin in which a clear crystal melting peak is observed when the temperature is raised in the measurement with a differential scanning calorimeter (DSC). , 11 is 100% by mass, preferably 50% by mass or more, more preferably 50% by mass or more and 80% by mass or less. The relationship between the crystal melting peak temperature (Tm) and the glass transition temperature (Tg) of the substantially crystalline polyester resin is preferably Tm (° C.)> (Tg + 30) (° C.). By making the base resin layer 10 such a layer, in order to give emboss, when the laminated film 100 (101) for screen board of the present invention is heated and passed through an emboss roll, the base resin layer 10 (11) and a metal roll do not show adhesiveness, and an embossing provision process can be performed smoothly.

  As such a substantially crystalline polyester-based resin, a crystalline polybutylene terephthalate-based resin (hereinafter sometimes abbreviated as “PBT”) can be used. As the crystalline polybutylene terephthalate resin, so-called homo-polybutylene terephthalate using only terephthalic acid as the acid component and 1,4-butanediol as the alcohol component can be preferably used. In addition, polybutylene terephthalate in which a part of the acid component is substituted with isophthalic acid so that the surface temperature of the metal plate 90 (91) can be lowered during the lamination with the metal plate 90 (91). Can also be used.

1.2. Embossable layer The embossable layer 20 (21) is an unstretched layer containing a polyester-based resin as a main component. The non-stretched layer containing a polyester resin as a main component is the same as that in the base resin layer 10 (11).

  The embossable layer 20 (21) is formed from a substantially amorphous polyester-based resin in which a clear crystal melting peak is not observed at the time of temperature rise as measured by a differential scanning calorimeter (DSC). (21) The total mass is 100% by mass, preferably 50% by mass or more.

  As the substantially amorphous polyester resin, an amorphous or low-crystalline polyester resin can be used. Specifically, it is preferable to use “Easter 6663” manufactured by Eastman Chemical Co., Ltd., which has been reduced in cost because of a stable supply of raw materials and a large amount of production, and a similar resin. However, the present invention is not limited to this, and neopentyl glycol copolymerized PET does not exhibit crystallinity, or exhibits a melting point under special cooling conditions, but can generally be handled as an amorphous resin. “PCTG 5445” manufactured by Eastman Chemical Co. may be used.

  The polyester resin forming the embossable layer 20 (21) preferably has a weight average molecular weight in terms of styrene by gel permeation chromatography (GPC) at the time of film formation in the range of 65,000 to 140000, and 75000. More preferably, it is in the range of ˜120,000.

  If the molecular weight is too low, the durability of the laminated film-coated metal plate will be inferior. When the molecular weight is too high, the durability improving effect is saturated at the time when the film is formed on the sheet, and more energy is required for film formation.

  The embossable layer 20 (21) includes a crystalline polybutylene terephthalate-based resin, and is clear at the time of the primary temperature rise measured at a heating temperature of 10 ° C./min according to JIS K7121 by differential scanning calorimetry. An endothermic peak due to crystal melting is shown, and the heat of crystal melting (ΔHm (J / g)) is preferably 10 to 60.

  Specifically, the differential scanning calorimetry is performed using a DSC-7 manufactured by PerkinElmer, Inc., and 10 mg of a sample according to JIS K7121 “Method for measuring transition temperature of plastic / determining melting temperature” at a heating rate of 10 ° C. / Measured in minutes to determine the heat of crystal melting at the time of primary temperature rise.

  Here, that the endothermic peak due to crystal melting is “clear” means that this peak is due to crystal melting of 10 J / g or more.

1.3. Adhesive polymer composition layer comprising a modified polyester elastomer The adhesive polymer composition layer 30 (31) comprising a modified polyester elastomer is a saturated polymer having a polyalkylene ether glycol segment content of 58 to 73% by weight. A layer containing as a main component an adhesive polymer composition obtained by modifying a polyester thermoplastic elastomer with an unsaturated carboxylic acid or a derivative thereof in the presence of a radical generator. By using such an adhesive polymer composition, it is possible to firmly and stably bond a polyester resin, a polyamide resin, an ethylene vinyl alcohol copolymer resin, and the like, which has been difficult in the past. Here, “modification” refers to graft modification of a saturated polyester thermoplastic elastomer containing a polyalkylene ether glycol segment with an unsaturated carboxylic acid or a derivative thereof, terminal modification and modification by transesterification, modification by decomposition reaction, and the like. . Specifically, as the site to which the unsaturated carboxylic acid or derivative thereof is bonded, a terminal functional group or an alkyl chain moiety is conceivable, particularly for the ether bond of the terminal carboxylic acid, terminal hydroxyl group and polyalkylene ether glycol segment. Examples include α-position and β-position carbon. In particular, it is presumed that the polyalkylene ether glycol segment has many bonds at the α position with respect to the ether bond.

  The adhesive polymer composition of the present invention has a JIS-D hardness (in accordance with JIS K 6253, a durometer type D hardness) of 10 to 80, preferably 15 to 70, particularly preferably 20 to 60. Those are preferred. When the JIS-D hardness is within the above range, the heat resistance, rubber elasticity, and adhesion tend to be good. Furthermore, MFR (JIS K7210 conformity, 230 degreeC, 2.16 kg) of this adhesive polymer composition is 40-300 (g / 10min), Preferably it is 42-150 (g / 10min), More preferably 45 to 100 (g / 10 min).

The amount of modification by the infrared absorption spectrum method of the modified polyester elastomer is as follows:
A ₁₇₈₆ / (Ast × r)
[However, A ₁₇₈₆ is a peak intensity of 1786 cm ⁻¹ measured for a film of a modified polyester elastomer having a thickness of 20 μm, and As is a standard sample (content of polyalkylene ether glycol segment is 65% by weight). Is a peak intensity of a standard wave number measured for a film having a thickness of 20 μm, and r is the molar fraction of the polyester segment in the modified polyester elastomer and the polyester segment in the standard sample. It is the value divided by the mole fraction. ]
It is desirable that the value obtained from the formula is 0.01 to 15, preferably 0.03 to 2.5, more preferably 0.1 to 2.0, and particularly preferably 0.2-1.8. The method for obtaining the value of the modification amount of the modified polyester elastomer by the infrared absorption spectrum method is as follows. That is, a film sample having a thickness of 20 μm is dried under reduced pressure at 100 ° C. for 15 hours to remove unreacted substances, and an infrared absorption spectrum is measured. From the obtained spectrum, the tangent line connecting the both sides of the foot of the mountain of the absorption band the baseline in the range of the absorption peak (1750~1820cm ^-1 by stretching vibration of the carbonyl group derived from an acid anhydride appears at 1786 cm ^-1 ) Is calculated as “peak intensity A ₁₇₈₆ ”. On the other hand, an infrared absorption spectrum is measured in the same manner for a 20 μm thick film of a standard sample (saturated polyester elastomer having a polyalkylene ether glycol segment content of 65% by weight). From the obtained spectrum, the peak of the reference wave number, for example in the case of an aromatic polyester elastomer having a benzene ring, the absorption peak due to out-of-plane deformation of the C-H in benzene ring appearing at 872cm ^-1 (850~900cm ^-1 The peak height of the tangent line connecting the mountain hems on both sides of the absorption band in the range of (the base line is used) is calculated as “peak intensity As”. The peak of the reference wave number may be selected from those that are not affected by denaturation and do not have an absorption peak that overlaps in the vicinity thereof. From these two peak intensities, the amount of modification by the infrared absorption spectrum method is calculated according to the above formula. At that time, as r, a value obtained by dividing the mole fraction of the polyester segment in the modified polyester elastomer for which the amount of modification is to be obtained is divided by the mole fraction of the polyester segment in the standard sample. Moreover, the molar fraction mr of the polyester segment of each sample is the weight fraction (w ₁ and w ₂ ) of the polyester segment and the polyalkylene ether glycol segment and the molecular weight of the monomer units constituting both segments (e ₁ and e _{From 2} ), the following equation is used.
mr = (w ₁ / e ₁ ) / [(w ₁ / e ₁ ) + (w ₂ / e ₂ )]

1.3.1. Component (A): Saturated polyester thermoplastic elastomer The saturated polyester thermoplastic elastomer is a block copolymer composed of a soft segment containing a polyalkylene ether glycol segment and a hard segment containing an aromatic polyester. It is important that the soft segment is a polyalkylene ether glycol segment or a segment containing the same in view of physical properties of the adhesive polymer composition, in particular, adhesiveness.
In addition, the content of the polyalkylene ether glycol segment in the saturated polyester thermoplastic elastomer needs to be 58 to 73% by weight, preferably 60 to 70% by weight in the polyester elastomer.

Examples of the polyalkylene ether glycol constituting the soft segment include polyethylene glycol, poly (1,2 and 1,3-propylene ether) glycol, poly (tetramethylene ether) glycol, poly (hexamethylene ether) glycol, and the like. Can be mentioned. Particularly preferred is poly (tetramethylene ether) glycol. In the present invention, as the polyalkylene ether glycol, those having a number average molecular weight of 400 to 6,000 are usually used, but those having a number average molecular weight of 600 to 4,000 are preferred, and those having 1,000 to 3,000 are particularly preferred. Is preferred.
The “number average molecular weight” here is measured by gel permeation chromatography (GPC). For calibration of GPC, a POLYTETRAHYDROFURAN calibration kit manufactured by POLYMERLABORATORIES, UK may be used.

  The saturated polyester-based thermoplastic elastomer includes i) an aliphatic and / or alicyclic diol having 2 to 12 carbon atoms, ii) an aromatic dicarboxylic acid and / or alicyclic dicarboxylic acid or an alkyl ester thereof, and iii) A polyalkylene ether glycol having a number average molecular weight of 400 to 6,000 is used as a raw material, and an oligomer obtained by an esterification reaction or a transesterification reaction can be polycondensed.

  As the aliphatic and / or alicyclic diol having 2 to 12 carbon atoms, those usually used as a raw material for polyester, particularly as a raw material for a polyester-based thermoplastic elastomer, can be used. For example, ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like are mentioned, among which 1,4-butanediol and ethylene glycol are preferable. In particular, 1,4-butanediol is preferred. These diols can be used singly or as a mixture of two or more.

  As the aromatic dicarboxylic acid and / or alicyclic dicarboxylic acid, those generally used as raw materials for polyesters, particularly polyester-based thermoplastic elastomers, can be used, such as terephthalic acid, isophthalic acid, phthalic acid, Examples include 2,6-naphthalenedicarboxylic acid and cyclohexanedicarboxylic acid. Among these, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferable, and terephthalic acid is particularly preferable. Two or more of these dicarboxylic acids may be used in combination. When using an aromatic dicarboxylic acid and / or an alkyl ester of an alicyclic dicarboxylic acid, the dimethyl ester or diethyl ester of the above-mentioned dicarboxylic acid is used. Preference is given to dimethyl terephthalate and 2,6-dimethyl naphthalate.

  In addition to the above components, trifunctional triols, tricarboxylic acids or esters thereof may be copolymerized in a small amount, and aliphatic dicarboxylic acids such as adipic acid or dialkyl esters thereof can also be used as a copolymerization component. As a kind and suitable molecular weight range of polyalkylene ether glycol, the thing similar to what was demonstrated by said clause can be used. Examples of commercially available polyester thermoplastic elastomers include “Primalloy” manufactured by Mitsubishi Chemical Corporation, “Perprene” manufactured by Toyobo Co., Ltd., “Hytrel” manufactured by Toray DuPont Co., Ltd., and the like.

1.3.2. Component (B): unsaturated carboxylic acid or derivative thereof As unsaturated carboxylic acid or derivative thereof, for example, acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, etc. Unsaturated carboxylic acid; 2-octen-1-yl succinic anhydride, 2-dodecen-1-yl succinic anhydride, 2-octadecene-1-yl succinic anhydride, maleic anhydride, 2,3- Dimethylmaleic anhydride, bromomaleic anhydride, dichloromaleic anhydride, citraconic anhydride, itaconic anhydride, 1-butene-3,4-dicarboxylic anhydride, 1-cyclopentene-1,2-dicarboxylic acid Acid anhydride, 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, exo-3,6-epoxy -1,2,3,6-tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, endo-bicyclo [2.2 .2] Unsaturated carboxylic acids such as oct-5-ene-2,3-dicarboxylic acid anhydride and bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid anhydride Acid anhydride; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylic 2-ethylhexyl acid, lauryl (meth) acrylate, stearyl (meth) acrylate, glycidyl methacrylate, dimethyl maleate, maleic acid (2-ethylhexyl) And unsaturated carboxylic acid esters such as 2-hydroxyethyl methacrylate. Of these, unsaturated carboxylic acid anhydrides are preferred. These compounds having an unsaturated bond may be appropriately selected according to the copolymer containing the polyalkylene ether glycol segment to be modified and the modification conditions, or two or more of them may be used in combination. The compound having an unsaturated bond can be added after being dissolved in an organic solvent or the like.

1.3.3. Component (C): Radical generator As the radical generator used for performing a radical reaction in the modification treatment, for example, t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5 -Dihydroperoxide, 2,5-dimethyl-2,5-bis (tertiarybutyloxy) hexane, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxybenzoate, benzoyl peroxide, dicumyl Peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene, dibutyl peroxide, methyl ethyl ketone peroxide, potassium peroxide, hydrogen peroxide and other organic and inorganic peroxides, 2,2′-azobisiso Butyronitrile, 2,2'-azobis (isobutyramide Dihalide, 2,2'-azobis [2-methyl-N-(2-hydroxyethyl) propionamide], azo compounds such as azodi -t- butane, and carbon radical generators such as dicumyl can be exemplified. These radical generators may be appropriately selected according to the type of the saturated polyester thermoplastic elastomer containing the polyalkylene ether glycol segment used for the modification treatment, the type of the unsaturated carboxylic acid or its derivative, and the modification conditions. Moreover, you may use 2 or more types together. The radical generator can also be added after being dissolved in an organic solvent or the like. In order to further improve the adhesiveness, not only the component (C) but also a compound having an unsaturated bond (component (D)) can be used in combination as a modification aid.

1.3.4. Component (D): Compound having an unsaturated bond The compound having an unsaturated bond refers to a compound having a carbon-carbon multiple bond other than the component (B), specifically, styrene, methylstyrene, Examples thereof include vinyl aromatic monomers such as ethyl styrene, isopropyl styrene, phenyl styrene, o-methyl styrene, 2,4-dimethyl styrene, o-chloro styrene, and o-chloromethyl styrene. Improvement of the modification efficiency can be expected by these blends.

1.3.5. Optional component In addition to the above-mentioned components (A) to (D), the adhesive polymer composition layer of the present invention is blended with optional components according to the purpose within a range not impairing the purpose and effect of the present invention. can do. Specifically, resin component, rubber component, talc, calcium carbonate, mica, glass fiber filler, plasticizer such as paraffin oil, antioxidant, heat stabilizer, light stabilizer, ultraviolet absorber, neutralizer Add various additives such as lubricants, anti-fogging agents, anti-blocking agents, slip agents, cross-linking agents, cross-linking aids, colorants, flame retardants, dispersants, antistatic agents, antibacterial agents, fluorescent whitening agents, etc. be able to. Among them, it is preferable to add at least one of various antioxidants such as phenol, phosphite, thioether, and aromatic amine.

1.3.6. Mixing ratio The mixing ratio of each component constituting the adhesive polymer composition is such that the component (B) unsaturated carboxylic acid or its derivative is 0.01 with respect to 100 parts by weight of the component (A) saturated polyester thermoplastic elastomer. To 30 parts by weight, preferably 0.05 to 5 parts by weight, more preferably 0.1 to 2 parts by weight, and particularly preferably 0.1 to 1 part by weight. C) The radical generator is 0.001 to 3 parts by weight, preferably 0.005 to 0.5 parts by weight, more preferably 0.01 to 0.2 parts by weight, and particularly preferably 0.01 to 0 parts by weight. The blending ratio is 1 part by weight. By using such a blending ratio, there is no possibility that the modification will be insufficient, express good adhesiveness, and there is a possibility that the melt viscosity of the thermoplastic elastomer to be produced is lowered and the moldability is deteriorated. Absent.

1.3.7. Blending method Blending method for obtaining a thermoplastic elastomer composition using blending components such as component (A), component (B) and component (C), and component (D) added as necessary There are a melting method, a solution method, a suspension dispersion method and the like, and there is no particular limitation. Practically, the melt kneading method is preferable. Specific methods for melt-kneading include powdery or granular component (A), component (B) and component (C), and, if necessary, component (D), the additional compounding material ( Other ingredients listed as optional components) are uniformly mixed using a Henschel mixer, ribbon blender, V-type blender, etc. at a prescribed blending ratio, and then Banbury mixer, kneader, roll, uniaxial or biaxial Examples thereof include a kneading method using a normal kneader such as a multi-screw kneading extruder. The temperature of melt kneading of each component is in the range of 100 ° C to 300 ° C, preferably in the range of 120 ° C to 280 ° C, and particularly preferably in the range of 150 ° C to 250 ° C. Furthermore, the kneading order and method of each component are not particularly limited, and the component (A), the component (B) and the component (C), and additional compounding materials such as the component (D) are collectively included. A method of kneading, or a method of kneading a part of components (A) to (D) and then kneading the remaining components including additional compounding materials may be used. However, when mix | blending a component (C), it is preferable from the point of an adhesive improvement to add this simultaneously with a component (B) and a component (D).

  In the screen board laminated films 100A and 100B of the present embodiment, the embossable layer 20 and the layer 40 made of an ethylene-vinyl alcohol copolymer resin are formed by the adhesive polymer composition layer 30 made of a modified polyester elastomer. And are adhered.

  Specific examples of the adhesive polymer composition comprising a modified polyester elastomer include “Primalloy-AP” and “Primalloy-IF203” manufactured by Mitsubishi Chemical Corporation.

1.4. Embossed return prevention layer In the laminated films 100A and 100B for the screen board in the present invention, an embossed return prevention layer 25 is optionally provided with an embossable layer 20 and an adhesive polymer composition layer 30 comprising a modified polyester elastomer. It can arrange | position between and can be set as the laminated film 101A for screen boards, and 101B. By disposing the emboss return prevention layer 25 between the embossable layer 21 and the adhesive polymer composition layer 31 made of a modified polyester elastomer, the emboss return prevention of the screen board laminated films 100A and 100B is achieved. More enhanced laminated films 101A and 101B for screen boards can be obtained.

  The resin constituting the emboss return preventing layer 25 is preferably a resin mainly composed of a polycarbonate resin.

1.5. Layer made of ethylene-vinyl alcohol copolymer resin Layer 40 (41) made of ethylene-vinyl alcohol copolymer resin refers to a layer containing an ethylene-vinyl alcohol copolymer as a main component. Here, the ethylene-vinyl alcohol copolymer is obtained by hydrolyzing a resin obtained by copolymerizing ethylene and vinyl acetate. The ethylene-vinyl alcohol copolymer used in the present invention preferably has an ethylene content of 20 to 65 mol%, more preferably 25 to 60 mol%. Further, the saponification degree of the vinyl ester component is preferably 90 mol% or more, and more preferably 95 mol% or more.

  The melt flow rate (MFR) measured according to JIS K7210 of the ethylene-vinyl alcohol copolymer is preferably 8-15, and more preferably 10-14.

  A layer 40 (41) made of an ethylene-vinyl alcohol copolymer resin is placed between an adhesive polymer composition layer 30 (31) made of a modified polyester elastomer and a layer 50 (51) made of an adhesive fluororesin. By arranging, adhesion between the respective layers becomes possible.

1.6. Layer composed of adhesive fluororesin The layer 50 (51) composed of adhesive fluororesin refers to a layer containing an adhesive fluororesin as a main component. The adhesive fluororesin in the present invention has a melting point of 150 ° C. to 250 ° C., and 4 × 10 ^{5 to} 5 × of Lexpearl RA3150 (manufactured by Nippon Polyethylene), which is a kind of modified polyolefin resin, and fluororesin. A sample was pressed at 240 ° C. for 10 minutes at a sample pressure of 10 ⁵ Pa to produce a laminated sheet, and a sample taken by cutting to a width of 2.5 cm and a length of 25 cm was obtained by a method according to JIS Z0237. It means a fluororesin having a 180 degree peel strength of 4 N / cm or more when a 180 degree peel strength is measured at a peel rate of 5 mm / min and a temperature of 23 ° C.

Further, IR spectrum of the adhesive fluorocarbon resin in the present invention ^has an absorption peak between 1780cm ^-1 ~1880cm -1. Preferably, IR spectrum of the adhesive ^fluororesin, 1790 cm -1 during and between ^{1845cm -1 ~1855cm} -1 of ～1800Cm ^-1, has an absorption peak due to anhydride such as maleic anhydride groups, ^{Alternatively,} it has an absorption peak due to end carbonate groups between 1800cm ^-1 ~1815cm -1, ^or 1790 cm between ^-1 ~1800cm ^-1, and between 1800 cm ^-1 ~ of 1845cm ^-1 ~1855cm -1 Between 1815 cm ⁻¹ , it has an absorption peak due to a mixture of anhydrides such as maleic anhydride groups and terminal carbonate groups.

Among this, IR spectrum of the adhesive ^fluororesin, 1790 cm -1 during and between ^{1845cm -1 ~1855cm} -1 of ～1800Cm ^-1, has an absorption peak due to anhydride such as maleic anhydride groups, ^{Alternatively,} preferably one having an absorption peak due to end carbonate groups between 1800cm ^-1 ~1815cm -1.

Further, the main chain due to the CH ₂ groups of the absorption peak near 2881cm ^-1 to the height of the absorption peaks between ^{1790cm -1 ~1800cm} -1 attributed to anhydride such as maleic anhydride groups of height The ratio is 0.5 to 1.5, preferably 0.7 to 1.2, and more preferably 0.8 to 1.0.

Moreover, the ratio of the height of the absorption peak between 1800 cm ⁻¹ to 1815 cm ⁻¹ due to the terminal carbonate group to the height of the absorption peak near 2881 cm ⁻¹ due to the CH ₂ group of the main chain is 1. It is 0-2.0, Preferably it is 1.2-1.8, More preferably, it is 1.5-1.7.

  As such a fluororesin having adhesive strength, for example, a homopolymer or copolymer having a tetrafluoroethylene unit, such as a carbonate group, a carboxylic acid halide group, a hydroxyl group, a carboxyl group, or an epoxy group at the terminal or side chain A resin having a functional group of A plurality of resins may be mixed as long as the melting point and the adhesive strength are expressed. Examples of commercially available fluororesins having adhesive strength as described above include Neoflon EFEP (manufactured by Daikin Industries) and Fullon LM-ETFE AH2000 (manufactured by Asahi Glass Co., Ltd.).

  By placing the layer 40 (41) made of a fluororesin on the upper side of the layer 30 (31) made of an ethylene-vinyl alcohol copolymer resin, the adhesion is good and the erasability characteristic of the fluororesin is provided on the surface. Can be granted.

1.7. Layer made of fluororesin The layer 60 (61) made of fluororesin refers to a layer containing a fluororesin as a main component. The fluororesin is not particularly limited, and various types can be used. Typical examples include ethylene-tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride-polyvinylidene fluoroethylene copolymer (PVdF), fluorinated ethylene propylene-tetrafluoroethylene-hexafluoropropylene copolymer (FEP). ), Tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (THV), etc., and these copolymers and mixtures can be used. Among these, ethylene-tetrafluoroethylene copolymer (ETFE) is preferable from the viewpoints of antifouling property, mechanical properties, workability, and the like. An ethylene-tetrafluoroethylene copolymer (ETFE) can be easily obtained as a commercial product, and for example, Aflon COP (manufactured by Asahi Glass Co., Ltd.), Tefzel (manufactured by DuPont Co., Ltd.), NEOFLON ETFE (manufactured by Daikin Industries, Ltd.), etc. are obtained. be able to.

  By disposing the layer 60 (61) made of the fluororesin in the outermost layer, the adhesion is good and the erasability characteristic of the fluororesin can be imparted to the surface.

  The above-mentioned adhesive polymer composition layer 30 (31) made of a modified polyester elastomer, layer 40 (41) made of an ethylene-vinyl alcohol copolymer resin, and layer 50 (51) made of an adhesive fluororesin. The total thickness is preferably 10 μm or less, and more preferably 5 μm or less. By adjusting the total thickness, the embossing imparted to the embossable layer 20 (21) clearly appears on the surface of the laminated film 100 (101). Further, the material cost can be reduced. In addition, also when laminating | stacking the layer 60 (61) which consists of fluororesins on the layer 50 (51) which consists of adhesive fluororesins, for the same reason, 10 micrometers or less are preferable. Also, an adhesive polymer composition layer 30 (31) made of a modified polyester elastomer, a layer 40 (41) made of an ethylene-vinyl alcohol copolymer resin, a layer 50 (51) made of an adhesive fluororesin, and fluorine The total thickness of the resin layer 60 (61) is preferably 10 μm or less.

2. Manufacturing method of laminated film Base resin layer 10 (11), embossable layer 20 (21), emboss return preventing layer 25, adhesive polymer composition layer 30 (31) composed of a modified polyester elastomer, ethylene-vinyl The layer 40 (41) made of an alcohol copolymer resin and the layer 50 (51) made of an adhesive fluororesin are coextruded to form a laminated film 100A (101A). In this co-extrusion molding, five or six kinds of resin materials corresponding to each resin layer are guided to an extrusion die formed by combining them together using five or six extruders. The laminated film 100A (101A), which is a single extruded product, is brought into contact at the die opening. In addition, when laminating | stacking the layer 60 (61) which consists of fluororesin, six types or seven types of resin materials are similarly coextruded using six or seven extruders, and laminated film 100B (101B).

3. Giving an embossed pattern An embossed pattern is imparted to the laminated film 100 (101) for a screen board of the present invention. Hereinafter, the screen board laminated film 100 will be described as an example. As a method for applying the embossed pattern, for example, there is a method for applying the embossed pattern by the embossing machine 300 shown in FIG. In the embossing machine 300, the laminated film 100A is subjected to a predetermined treatment by the infrared heater 3 through the heating roll 1 and the take-off roll 2 so that the layer 50 made of an adhesive fluororesin is in contact with the embossing roll 5, Further, it is sent to the nip roll 4, the embossing roll 5, and the cooling roll 6. Moreover, when laminating | stacking the layer 60 which consists of fluororesins and it is set as the laminated | multilayer film 100B, the process similar to the above is made so that the layer 60 which consists of fluororesin may contact the embossing roll 5. FIG.

  As for the roughness of the surface of the laminated film 100 for a screen board of the present invention to which an emboss pattern is given, Ra (center line average roughness) is preferably 0.7 μm or more and 5 μm or less, and Rmax (maximum height) is set. It is preferably 4 μm or more and 40 μm or less, Rz (ten-point average roughness) is preferably 3 μm or more and 30 μm or less, Rp (average depth) is preferably 1.5 μm or more and 20 μm or less, and Pc ( The number of peaks is preferably 7 or more and 50 or less / 8 mm, and the glossiness is preferably 50 or less. Here, Ra (center line average roughness), Rmax (maximum height), Rz (ten-point average roughness), Rp (average depth), and Pc (number of peaks) are JIS B0601 (geometric characteristics of the product). (GPS) -Surface property: Contour curve method-Terminology, definition and surface property parameter), for example, using a SE-3FK tester manufactured by Kosaka Laboratory Co., Ltd., using a 2 μmR diamond needle Can be measured. Moreover, glossiness shall be measured according to JISZ8741-1997 (mirror glossiness-measuring method), for example, can be measured using the UGV-5DP tester by Suga Test Instruments Co., Ltd. Note that the incident angle of the light source in the gloss measurement is set to 60 °.

4). Laminated Film Coated Metal Plate FIG. 4 schematically shows the layer structure of the laminated film coated metal plate 200 for a screen board of the present invention. As shown in FIG. 4 (a), the laminated film-covered metal plate for screen board 200 of the present invention is manufactured by attaching the base resin layer 10 side to the metal plate 90 in the laminated film for screen board 100B. Can do. Moreover, as shown in FIG.4 (b), the laminated film covering metal plate 201 for screen boards of this invention is produced by affixing the base resin layer 11 side in the laminated film 101B for screen boards to the metal plate 90. As shown in FIG. can do. Examples of the attaching method include heat fusion or dry lamination. It does not specifically limit as an adhesive agent used for dry lamination, Various things can be used. Typical examples include polyester-based, epoxy-based, acrylic-based and urethane-based adhesives. As a specific example, as polyester-based thermosetting adhesive, 100 parts by mass of Takelac A310 and 5 parts by mass of Takenate A3 (both manufactured by Mitsui Takeda Chemical Co., Ltd.) can be mentioned. In the case of dry laminating, the surface to be dry laminated can be subjected to surface treatment or undercoating treatment.

5. Screen Board The screen board of the present invention can be produced, for example, by cutting the above-mentioned laminated film-coated metal plate for a screen board into a rectangle of 600 mm × 900 mm and attaching a plastic frame to the peripheral portion. The screen board can be attached with a hook for hanging on the wall and a moving means such as a caster.

(Example 1)
Using the following resins, co-extrusion was performed with a five-layer multi-manifold die at a die temperature of 260 ° C. to obtain a laminated film having the following layers. The total thickness of the first layer to the third layer is 5 μm.
First layer: Adhesive fluororesin NEOFLON EFEP RP4020 (manufactured by Daikin Industries)
Second layer: ethylene-vinyl alcohol copolymer resin EVOH (Eval F101 manufactured by Kuraray Co., Ltd.)
Third layer: Adhesive polymer composition layer made of modified polyester elastomer (Primalloy-IF203, manufactured by Mitsubishi Chemical Corporation)
Fourth layer: Embossable layer (PC Novalex 7027PU, manufactured by Mitsubishi Engineering Plastics Co., Ltd .; 50 μm)
Fifth layer: base resin layer (Novaduran 5020S manufactured by Mitsubishi Engineering Plastics; 100 μm)

  The embossing apparatus 300 shown in FIG. 3 is used to emboss the laminated film produced at a speed of 10 m / min between a pair of rolls having a film heating temperature of 180 ° C. and a roll linear pressure of 1.8 MPa. A was performed. Here, “embossing A” is an embossing process in which Ra is 2.3 μm, Rmax is 13.2 μm, Rz is 11.0 μm, Rp is 5.8 μm, Pc is 18, and gloss is 30% or less. is there.

  Next, a polyester adhesive (SC611 (manufactured by Sony Chemical)) is applied to the galvanized steel sheet (thickness 0.45 mm) so that the adhesive film thickness after drying is about 2 to 4 μm. The coated surface was dried and heated by a hot air drying furnace and an infrared heater so that the surface temperature was 235 ° C. Then, using a roll laminator, the coated surface of the adhesive on the steel sheet is coated on the base resin layer side of the laminated film of the present invention, and is naturally air-cooled for screen board coated with the laminated film of the present invention. A laminated film-coated metal plate was obtained.

(Example 2)
In Example 1, except that the total thickness of the first layer to the third layer was 8 μm, a laminated film for screen board and a laminated film-coated metal plate for screen board were obtained in the same manner as in Example 1.

(Example 3)
In Example 1, except that a layer made of polycarbonate resin was provided between the third layer (adhesive polymer composition layer made of modified polyester elastomer) and the fourth layer (embossable layer). In the same manner as in Example 1, a laminated film for screen board and a laminated film-coated metal plate for screen board were obtained.

(Example 4)
In Example 2, except that a layer made of polycarbonate resin was provided between the third layer (adhesive polymer composition layer made of modified polyester elastomer) and the fourth layer (embossable layer). In the same manner as in Example 1, a laminated film for screen board and a laminated film-coated metal plate for screen board were obtained.

(Example 5)
In Example 1, the total thickness of the first layer to the third layer was set to 12 μm, and the embossing B was performed in the same manner as in Example 1 except that the laminated film for screen board and the laminated film-coated metal plate for screen board were used. Got. Here, “embossing B” is embossing in which Ra is 0.2, Rmax is 3.5, Rz is 1.7, Rp is 0.8, Pc is 11, and gloss is 50% or more. is there.

(Example 6)
In Example 1, except having performed the embossing B, it carried out similarly to Example 1, and obtained the laminated film for screen boards, and the laminated film covering metal plate for screen boards.

(Comparative Example 1)
A laminated film was obtained by laminating a mat-treated ethylene-tetrafluoroethylene film (Fullon ETFE C-88AXP, manufactured by Asahi Glass Co., Ltd., 25 μm) on a white film (50 μm) made of polyethylene terephthalate. For the laminate, a polyester thermosetting adhesive as an adhesive was obtained by blending Takelac A310; 100 parts by mass with Takenate A3; 5 parts by mass (both manufactured by Mitsui Takeda Chemical Co., Ltd.). Then, it carried out similarly to Example 1, and affixed on the galvanized steel plate, and obtained the laminated film coating metal plate.

(Comparative Example 2)
Co-extrusion molding was performed with a two-layer multi-manifold die at a die temperature of 260 ° C. to obtain a two-layer laminated film composed of an embossable layer and a base resin layer used in Example 1. And embossing A was given. Then, it carried out similarly to Example 1, and affixed on the galvanized steel plate, and obtained the laminated film coating metal plate.

(Evaluation methods)
The laminated film and laminated film-coated metal plate obtained above were evaluated according to the following criteria.

(Embossability)
The embossed sheet is visually observed, and “○” indicates that the embossed pattern is clearly transferred. “△” indicates that the transfer is slightly shallower than this. Indicated by “−”.

  The surface of the sheet immediately after being laminated on the galvanized steel sheet is visually observed. “○” indicates that there is no emboss return, “△” indicates that there is a slight emboss return, and “−” indicates that there is no embossing and is not subject to evaluation. Was recorded.

(Erasability)
Letters were written on the surface with an oil-based felt pen and judged from the following criteria based on the remaining amount of ink when the surface was wiped with a towel 60 seconds later.
○: Can be wiped clean.
X: There is a part where ink remains even in part.

(Anti-glare)
When a 40 W halogen lamp was incident on the surface at an angle of 45 to 30 cm, the surface of the laminated film-coated metal plate was visually observed and evaluated according to the following criteria.
○: There is no reflection of light, and the surface can be visually recognized.
(Triangle | delta): Although there is some reflection of light, the surface can be visually recognized.
X: The light is reflected and the surface cannot be visually recognized.

(Pencil hardness)
Regarding the laminated film-coated metal plate, according to JIS K5600-5-4: 1999 (Paint General Test Method-Part 5: Mechanical Properties of Coating Film-Section 4: Scratch Hardness (Pencil Method)) Using a 431 test machine, the test was performed at a load of 9.807 N (1000 gf). Using a jig capable of drawing in a state where a load of 9.8 N is applied while maintaining a 45 ° angle with respect to the resin sheet surface of the laminated film-coated metal plate cut out to 80 mm × 60 mm in a constant temperature room at 23 ° C. Draw a line. The surface state of the laminated film of the part was visually judged according to the following criteria.
○: The 2B pencil was not scratched at all.
Δ: Scratches occurred at 2B, but scratches did not occur at all with the 3B pencil.
X: The 3B pencil was also scratched.

(Economic)
The cost when producing a laminated film and a laminated film-coated metal plate was evaluated.
○: The cost is relatively low.
X: The cost is relatively high.

(Evaluation results)
The results obtained from the above evaluation are shown in Table 1.

  The laminated film for screen board and the laminated film-coated metal plate for screen board (particularly Examples 1 to 5) of the present invention showed good results in any evaluation item. Among them, in particular, the laminated film-coated metal plates for screen boards of Examples 1 to 4 subjected to the embossing A are excellent in embossing property, erasability and anti-glare property, especially the third layer (modified polyester elastomer). Example 3 and Example 4 in which a layer made of a polycarbonate resin is provided between the adhesive polymer composition layer made of (a) and the fourth layer (an embossable layer) are also excellent in embossing returnability. It was recognized that In Example 5, since the total thickness of the first layer to the third layer was too thick, the embossability was slightly inferior. Moreover, in Example 5 and 6, embossing remove | deviated from the preferable range of this invention, and it was recognized that it is somewhat inferior by the point of anti-glare property. Moreover, in Example 6, since the embossing was shallow and the surface layer was thin and the influence of the PC layer was large, the pencil hardness was slightly inferior.

  In Comparative Example 1, since the matted fluororesin layer is used, the erasability is inferior, the fluororesin layer is thick, and a laminated film is produced. Since the laminating work is required, the economy is inferior. In Comparative Example 2, since the surface layer did not have a layer made of a fluororesin, the erasability was inferior.

  As described above, the screen board laminated film and the screen board laminated film-coated metal plate of the present invention satisfy all of the erasability, antiglare property, and writing property. Since the laminated film for screen board and the laminated film-coated metal plate for screen board according to the present invention have an embossed transfer surface by pressing an embossed plate, the pitch between the convex portions (that is, the width of the concave portions) and the height of the convex portions. (That is, the depth of the concave portion) becomes constant. In addition, since the unevenness formed on the surface of the laminated film for screenboard and the laminated film-covered metal plate for screenboard of the present invention is due to the pressing of the embossed plate, the unevenness can be formed at a relatively low temperature compared to the conventional method, Since the cooling effect of the white base material stuck to the fluorine film can be expected, the temperature difference between the film forming and after film forming is less than the conventional method, the surface irregularities of the fluorine film are crushed and finer It is hard to become. Accordingly, the laminated film for screen board and the laminated film-coated metal plate for screen board of the present invention are excellent in erasability because ink clogging hardly occurs. Moreover, since the laminated film for screen board and the laminated film-coated metal plate for screen board of the present invention use an embossed plate for forming irregularities, the pitch between the convex parts is increased or the height of the convex parts is reduced. Needless to say, ink clogging hardly occurs. Therefore, the laminated film for screen board and the laminated film-coated metal plate for screen board according to the present invention are less likely to be glossy on the surface of the fluorine film, and thus have excellent antiglare properties and can be used in meetings and the like. As a result, the laminated film for screen board and the laminated film-coated metal plate for screen board of the present invention can be used for a reflective screen for projection equipment such as a video projector (VP) and an overhead projector (OHP). .

  While the present invention has been described in connection with embodiments that are presently the most practical and preferred, the present invention is not limited to the embodiments disclosed herein. However, the invention can be changed as appropriate without departing from the spirit or concept of the invention that can be read from the claims and the entire specification, and the laminated film for screen board and the laminated film-coated metal plate for screen board accompanied by such a change are also included. It should be understood as being included within the scope of the present invention.

It is the schematic diagram which showed the layer structure of the laminated film for screen boards of this invention. It is the schematic diagram which showed the other layer structure of the laminated film for screen boards of this invention. It is explanatory drawing which shows the outline | summary of an embossing machine. It is the figure which showed typically the laminated constitution of the laminated film coating metal plate for screen boards of this invention.

Explanation of symbols

100A, 100B, 101A, 101B Screen board laminated film 200, 201 Screen board laminated film coated metal plate 10 Base resin layer 20 Embossable layer 25 Emboss return prevention layer 30 Adhesive polymer composition comprising modified polyester elastomer Physical layer 40 Layer made of ethylene-vinyl alcohol copolymer resin 50 Layer made of adhesive fluororesin 60 Layer made of fluororesin 90 Metal plate

Claims (15)

A laminated film for metal coating for coating a metal surface to form a screen board,
Base resin layer,
Embossable layer,
A modified polyester elastomer obtained by modifying a saturated polyester thermoplastic elastomer having a polyalkylene ether glycol segment content of 58 to 73% by weight with an unsaturated carboxylic acid or a derivative thereof in the presence of a radical generator. An adhesive polymer composition layer comprising:
A layer of an ethylene-vinyl alcohol copolymer resin, and
A layer made of adhesive fluororesin,
Laminated films for screen boards, laminated in this order. A laminated film for metal coating for coating a metal surface to form a screen board,
Base resin layer,
Embossable layer,
A layer made of a resin having an elastic modulus of 10 ⁷ Pa or less at the embossing temperature, and an elastic modulus of 10 ⁸ Pa or more at the film temperature when laminating steel plates
A modified polyester elastomer obtained by modifying a saturated polyester thermoplastic elastomer having a polyalkylene ether glycol segment content of 58 to 73% by weight with an unsaturated carboxylic acid or a derivative thereof in the presence of a radical generator. An adhesive polymer composition layer comprising:
A layer of an ethylene-vinyl alcohol copolymer resin, and
A layer made of adhesive fluororesin,
Laminated films for screen boards, laminated in this order. 3. The laminated film for a screen board according to claim 2, wherein the resin having an elastic modulus of 10 ⁷ Pa or less at the embossing temperature and an elastic modulus of 10 ⁸ Pa or more at the film temperature when laminating steel plates is a polycarbonate resin.   The layer which consists of a fluororesin is further laminated | stacked on the surface opposite to the surface where the layer which consists of the said ethylene-vinyl alcohol copolymer resin in the layer which consists of the said adhesive fluororesin was laminated | stacked. A laminated film for a screen board according to any one of the above.   When the embossable layer is measured by a differential scanning calorimeter (DSC), a substantially amorphous polyester-based resin in which no clear crystal melting peak is observed at the time of temperature rise, the mass of the entire embossable layer can be determined. The laminated film for a screen board according to any one of claims 1 to 4, which is a layer containing 50% by mass or more as 100% by mass.   When the base resin layer is measured by a differential scanning calorimeter (DSC), a substantially crystalline polyester resin, in which a clear crystal melting peak is observed at the time of temperature rise, is the mass of the whole base resin layer. Is a layer containing 50% by mass or more with respect to 100% by mass, and the relationship between the crystal melting peak temperature (Tm) and the glass transition temperature (Tg) of the substantially crystalline polyester resin is Tm (° C.)> The laminated film for screen boards according to claim 1, which is (Tg + 30) (° C.).   The screen board according to any one of claims 1 to 6, wherein the weight average molecular weight in terms of styrene by gel permeation chromatography (GPC) at the time of forming the embossable layer is in the range of 65,000 to 140000. Laminated film.   The embossable layer contains a crystalline polybutylene terephthalate-based resin and exhibits a clear crystal melting peak temperature (Tm) when the temperature is raised by a differential scanning calorimeter (DSC), and the heat of crystal melting (ΔHm (J The laminated film for screen boards according to any one of claims 1 to 7, wherein / g)) is 10 to 60.   The laminated film for screen boards according to any one of claims 1 to 8, wherein the adhesive fluororesin contains a carbonate group.   The laminated film for screen boards according to any one of claims 1 to 9, wherein the adhesive fluororesin contains a maleic acid group.   The total thickness of each layer of the adhesive polymer composition layer composed of the modified polyester elastomer, the layer composed of the ethylene-vinyl alcohol copolymer resin, and the layer composed of the adhesive fluororesin is 10 μm or less. The laminated film for screen boards in any one of 1-10.   The laminated film for a screen board according to any one of claims 1 to 11, wherein a laminated film is formed by coextrusion, and irregularities are formed by an embossing roll on a layer side made of an adhesive fluororesin or a layer side made of a fluororesin. The roughness of the surface with the unevenness formed by the embossing roll
Ra (centerline average roughness): 0.7 to 5 μm,
Rmax (maximum height): 4 to 40 μm,
Rz (10-point average roughness): 3 to 30 μm,
Rp (average depth): 1.5 to 20 μm,
Pc (number of peaks): 7 to 50/8 mm
The laminated film for a screen board according to claim 12, wherein the glossiness is 50 or less.   A laminated film-covered metal plate for a screen board, comprising the laminated film for a screen board according to any one of claims 1 to 13 and a metal plate to which the base resin layer side of the laminated film is attached.   A screen board comprising the laminated film-coated metal plate for a screen board according to claim 14.

Images