JPWO2008053756A1 - Coated polyester film for rubber lamination, rubber / polyester film laminate, method for producing the same, and composite - Google Patents

Abstract

[PROBLEMS] To provide a rubber / polyester film laminate having high adhesion between a polyester film and a rubber layer, excellent durability, and excellent moldability, and excellent durability using the laminate. Provide plastic moldings. A polyester film having a degree of plane orientation of 0.005 to 0.15 has a cross-linked polymer film having a thickness of 0.003 to 5 μm on at least one side and is stretched 10% in the longitudinal direction and the width direction of the film. A coated polyester film for rubber lamination having a stress (25 ° C.) of 20 to 200 MPa. Also, a rubber / polyester film laminate obtained by laminating the above-mentioned polyester film for rubber lamination and a rubber layer. Also, a plastic molded body using the rubber / polyester film laminate as a constituent material. [Selection figure] None

Description

TECHNICAL FIELD OF THE INVENTION

The present invention relates to a laminated polyester film for rubber lamination and a laminated body of the laminated polyester film for rubber lamination and rubber. More specifically, the present invention relates to a polyester film and rubber using an adhesive or a pressure-sensitive adhesive. Can be directly integrated, the adhesion between the polyester film and rubber of the integrated rubber / polyester film laminate is strong, the durability of the adhesion is good, and the moldability is excellent It is related with the laminated polyester film for rubber lamination which can obtain the laminated body with the rubber | gum, and the laminated body of the coated polyester film for rubber lamination, and rubber | gum.
The present invention also relates to a method for producing the rubber / polyester film laminate, and more specifically, the invention relates to an economical method for producing a rubber / polyester film laminate.
Furthermore, the present invention relates to a plastic molded body using the rubber / polyester film laminate, and more specifically, a fiber reinforced that has excellent surface smoothness and surface decoration and generates less molding distortion during molding. The present invention relates to a plastic molded body using a composite material as one of constituent materials.

Conventional technology

Since rubber has excellent cushioning properties, it is used for sealing materials and cushioning materials in a wide range of industrial fields. However, since a film made only of rubber is too flexible, it is inferior in workability when incorporated in an apparatus or a part. On the other hand, a polyester film is harder than rubber, has good dimensional stability, is excellent in workability when incorporated in an apparatus or a part, and has good slipperiness, and is therefore used in a wide range of fields. However, polyester films are unsuitable as sealing materials and cushioning materials because of their low elasticity and sealing properties.
As a method for solving the above problems, a rubber / film laminate in which various films such as a polyester film and a film made of rubber are directly bonded without using an adhesive and a manufacturing method thereof are disclosed (for example, Patent Documents). 1-7).
JP 10-53659 A Japanese Patent Laid-Open No. 10-58605 JP-A-10-86282 Japanese Patent Laid-Open No. 10-95071 Japanese Patent Laid-Open No. 10-119394 Japanese Patent Laid-Open No. 10-226022 Japanese Patent Laid-Open No. 11-157010

  The polyester film is excellent in heat resistance, dimensional stability, and the like, and is excellent in economic efficiency, and is suitable as a base film for a laminate with the rubber. The laminated body using this as a base film is disclosed. However, since the laminate disclosed in the patent document uses a general-purpose polyester film, the obtained rubber laminate has a problem that it is inferior in moldability.

  One of the uses of the rubber laminate is sometimes used as a component of a molded body as a member of various molded bodies. By using a rubber laminate as the member, distortion generated in the molding of the molded body can be relaxed by utilizing the elasticity of rubber. For example, the surface state of the molded body can be improved, and the The external force applied to the molded body in the use of the molded body can be relaxed by the elasticity of the rubber. For example, effects such as improving the durability of the molded body can be provided.

  In the method of use as described above, the rubber laminate requires high moldability, adhesiveness between the rubber and the polyester film in the rubber laminate, or high adhesiveness with the material of the molding.

  Further, as one of the above usage methods, there is a case where a rubber laminate is used in combination with the surface of the above molded body, and in one of the usage methods, the polyester film side is incorporated into the molded body as the outermost layer, and the polyester is used. There are cases where printing, painting, or laminating metal thin films or metal foils on the surface of the film by vapor deposition or laminating methods. By the correspondence, the effect of reducing the gas permeability of the surface of the molded body and oxygen gas, water vapor and the like can be exhibited. In this method of use, the adhesiveness between the rubber and the polyester film is lowered by the solvent used in printing, painting, laminating and the like. In addition, the molded body may be used under harsh conditions such as outdoor use, and even under such harsh conditions, it is required to maintain the adhesion between rubber and a polyester film, and therefore requires excellent adhesion durability. is there. Further, strong adhesive force and durability of the adhesive force are also required between the printing ink or paint and the polyester film.

  In addition, although the adhesive force between the rubber and the polyester film of the rubber laminate obtained by the method disclosed in the above patent document is high in a normal state, for example, a state where a solvent exists, a high temperature, a high humidity, etc. It has the subject that the durability of the adhesive force in an environment is inferior.

On the other hand, a polyester film for a laminate of a highly moldable polyester film and rubber and a laminate using the film are disclosed (see Patent Documents 8 and 9).
JP 2001-322167 A JP 2001-330881 A

  The laminate in the method disclosed in the above-mentioned patent document satisfies a part of the above requirements in that the moldability is excellent. However, the method of the patent document has a problem that the polyester film and the rubber are laminated using an adhesive, which is disadvantageous in terms of economy. In addition, there may be a problem in adhesion and adhesion durability. Furthermore, depending on the type of adhesive, the moldability may be inferior.

  From the above background, for rubber lamination, a highly cost-effective method for producing a laminate with high moldability and high adhesion between the polyester film and rubber, excellent durability, and excellent moldability. The development of a polyester film and a laminate with rubber is strongly desired.

Plastic moldings have been used in a wide range of fields. In particular, molded products using fiber reinforced composite materials are thin, lightweight, high-rigidity, excellent in productivity, economical efficiency, electrical / electronic equipment parts, automotive equipment parts, personal computers, OA equipment, AV equipment, mobile phones, telephones. It is frequently used in parts and casings of electrical and electronic equipment such as facsimiles, home appliances, and toy supplies, and is expected to grow rapidly.
For example, in a molded body using a fiber reinforced composite material, a fiber reinforced resin sheet for thermoforming is molded into molded bodies of various shapes by press molding, drawing molding, vacuum molding, or the like.
As a method for producing the above-mentioned fiber reinforced resin sheet for thermoforming, there is known a method in which thermoplastic resin sheets are laminated on the upper and lower sides of a fiber reinforced mat, and the fiber reinforced mat is impregnated with a resin by heating and pressing it. When a molded product is molded using the thermoformed fiber reinforced resin sheet obtained by such a method, the reinforcing fibers float on the surface of the molded product, resulting in poor appearance. In addition, when reinforcing fibers emerge on the surface of the molded product, it also becomes an obstacle when the surface is painted or plated. Therefore, it is required to have a smooth surface for displaying a map.
Further, a method is known in which a fiber reinforced mat is impregnated with an uncured thermosetting resin, and the thermosetting resin is cured simultaneously with molding by a press molding machine or the like. This method also has the same problems as described above.

As a method for solving such a problem, for example, a method of forming a thermoplastic resin skin layer having a melting point higher than that of the matric resin of the sheet on the surface of a fiber reinforced thermoplastic resin sheet (see Patent Document 10), a thermoplastic resin and A method of laminating a thermoplastic resin layer not containing a fiber mat on the surface layer of a fiber reinforced thermoplastic resin sheet made of a fiber mat (see Patent Document 11), a crosslinking agent on at least one side of a core layer made of a fiber reinforced thermoplastic resin sheet A method of laminating a surface layer made of a thermoplastic resin sheet and heating and pressurizing the surface layer to heat-seal the core layer and the surface layer, and cross-linking the surface thermoplastic resin layer with a cross-linking agent (see Patent Document 12) ), At least one side of the core layer made of a fiber reinforced thermoplastic resin sheet, such as ethylene-propylene rubber or acrylonitrile-butadiene rubber. Tensile elasticity through a method of laminating a surface layer composed of a laster sheet by thermal fusion (see Patent Document 13) and a low elastic modulus layer having a tensile elastic modulus of 0.1 to 500 MPa on at least one surface of a fiber reinforced plastic layer A method of disposing a high elastic modulus layer having a rate of 1000 to 30000 MPa (see Patent Document 14) and the like are disclosed.
JP 58-188649 A JP 63-214444 A JP-A-5-84737 Japanese Patent Laid-Open No. 5-154922 Japanese Patent Laid-Open No. 2006-51813

Although the surface smoothness is improved by the method disclosed in the above patent document and the market demand can be satisfied in some applications, the market demand is required in applications where a high level smooth surface for displaying a mapping is required. There are cases where it cannot be satisfied.
In addition, in the methods disclosed in Patent Documents 10 to 12, there is no layer that relieves strain that occurs when molding into a molded body because the constituent layer of the molded body does not include a low elastic modulus layer. Therefore, the dimensional accuracy and dimensional stability of the molded body may be a problem.
Moreover, since the method of patent document 13 and 14 has arrange | positioned the low elastic modulus layer in the structure layer of a molded object, the said subject is improved, However, In these methods, the low elastic modulus with a bad handleability is improved. Since the method of incorporating the layers into the molded body independently is employed, when the molded body is manufactured, the operability may be inferior or the occurrence frequency of defective products may increase.
Furthermore, none of the methods disclosed in the above-mentioned patent documents give consideration to decorating the surface of the molded body and disposing a functional layer on the surface.
As described above, each of the conventional methods has problems.

  The present invention relates to a coated polyester film for rubber composites and a rubber for obtaining a rubber / polyester film laminate having high adhesion between a polyester film and rubber, excellent durability of the adhesion, and excellent moldability. -It is providing the manufacturing method of a polyester film laminated body. It is another object of the present invention to provide a plastic molded body having a smooth surface and a composite of the rubber / polyester film laminate.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, this invention consists of the following structures.
1. A polyester film having a plane orientation degree of 0.005 to 0.15 has a crosslinked polymer film having a thickness of 5 μm or less on at least one side, and a 10% elongation stress (25 ° C.) in the longitudinal and width directions of the film is 20 A coated polyester film for rubber lamination, characterized in that it is -200 MPa.
2. 2. The coated polyester film for rubber lamination according to 1 above, wherein the crosslinked polymer film comprises at least one resin selected from polyester, polyurethane and acrylic polymer.
3. 3. The coated polyester film for rubber lamination as described in 2 above, wherein the crosslinked polymer film is crosslinked with a crosslinking agent.
4). The crosslinking agent is a melamine crosslinking agent, an oxazoline crosslinking agent, an isocyanate crosslinking agent, an aziridine crosslinking agent, an epoxy crosslinking agent, a methylolated or alkylolized urea, acrylamide, polyamide resin, amide epoxy compound, 4. The coated polyester film for rubber lamination as described in 3 above, which is at least one selected from a silane coupling agent and a titanate coupling agent.
5). 5. The coated polyester film for rubber lamination according to 3 or 4 above, wherein the ratio of the resin constituting the crosslinked polymer film to the crosslinking agent is 0.5 or more in terms of the weight ratio of the crosslinking agent / resin.
6). Any one of 2 to 5 above, wherein the crosslinked polymer film includes one or more self-crosslinked polymers selected from the group consisting of self-crosslinked polyester, polyurethane and acrylic polymers. The coated polyester film for rubber lamination as described.
7). 7. The coated polyester film for rubber lamination according to any one of 1 to 6 above, wherein the crosslinked polymer film is formed on both sides of the polyester film.
8). A rubber / polyester film laminate obtained by laminating a rubber-coated polyester film according to any one of 1 to 6 above and a rubber.
9. 9. The rubber / polyester film laminate according to 8 above, wherein the coated polyester film and the rubber layer are directly laminated without using an adhesive.
10. The rubber / polyester film laminate according to claim 8 or 9, wherein the adhesive strength between the coated polyester film and the rubber layer is 9 N / 20 mm or more.
11. 11. The rubber / polyester film laminate according to any one of 8 to 10 above, wherein the adhesive strength between the polyester film and the rubber layer after immersion in toluene (25 ° C., 72 hours) is 8 N / 20 mm or more.
12 The rubber / polyester film laminate according to any one of 8 to 11 above, wherein the adhesive strength between the polyester film and the rubber layer after the water-resistant durability treatment by the method defined in the specification is 8 N / 20 mm or more.
13. 10% elongation stress (25 ° C.) in the longitudinal and width directions of the film having a cross-linked polymer film having a thickness of 5 μm or less on at least one surface of a polyester film having a degree of plane orientation of 0.005 to 0.15 is 20 to 13. The method for producing a rubber / polyester film laminate according to the above 8 to 12, wherein an uncrosslinked rubber layer is laminated on the surface of the crosslinked polymer film of a polyester film of 200 MPa, and then the uncrosslinked rubber layer is crosslinked.
14 14. The method for producing a rubber / polyester film laminate as described in 13 above, wherein an adhesion improver is blended in the uncrosslinked rubber layer.
15. A composite of the rubber / polyester film laminate according to any one of 8 to 12 above and a plastic molding.
16. 16. The composite according to 15 above, wherein a polyester film is disposed on the outermost surface.
17. 17. The composite according to 16 above, wherein a decorative layer made of at least one selected from printing ink, metal thin film, inorganic thin film and paint is provided on the surface of the polyester film.
18. 16. The composite according to 15 above, wherein the rubber / polyester film laminate is used as an intermediate layer of a plastic molding.
19. 19. The composite according to any one of 15 to 18 above, wherein the plastic molding is a sheet.
20. 20. The composite according to 19 above, wherein the plastic molded body has a curved portion.

Since the coated polyester film for rubber lamination of the present invention can directly bond a highly moldable polyester film and a rubber layer without using an adhesive, a laminate of a polyester film and a rubber layer having excellent moldability. Can be obtained economically. Further, the coated polyester film for rubber lamination of the present invention is a cross-linked polymer film layer having a thin layer thickness, which improves the adhesion between the polyester film and the rubber layer, and eliminates the adhesive layer, so that the thick adhesive layer is adhered. A decrease in moldability caused by the agent layer can be avoided. On top of that, a laminate having high adhesion between the polyester film and the rubber layer and excellent durability can be obtained.
Moreover, since the rubber / polyester film laminate of the present invention has excellent moldability, for example, when used as a member for a plastic molded body, the moldability of the plastic molded body is not lowered. Furthermore, since the rubber / polyester film laminate of the present invention has a rubber layer laminated thereon, for example, in the case of a composite used as a member of the plastic molded product, the distortion that occurs during the molding of the plastic molded product. Can be relaxed by utilizing the elasticity of the rubber layer, for example, the surface state of the plastic molded body can be improved, and the elastic force of the rubber layer can be applied to the molded body when the plastic molded body is used. For example, it is possible to impart effects such as improving the appearance and durability of the plastic molded body. Moreover, since the polyester film is laminated | stacked, the rubber | gum and polyester film laminated body of this invention is excellent in the handleability compared with the rubber layer single-piece | unit product.

In addition, the rubber / polyester film laminate of the present invention is excellent in the durability of the adhesiveness and adhesiveness between the rubber layer and the polyester film. For example, when used as a member for a plastic molded body, the durability of the plastic molded body Improve.
In addition, the rubber / polyester film laminate of the present invention includes a form in which a crosslinked polymer film layer is formed on both sides of the coated polyester film. Even on the surface opposite to the surface on which the layers are laminated, there is an advantage that, for example, adhesion to printing ink and adhesion durability can be improved. Therefore, when decorating the surface of the polyester film of the rubber / polyester film laminate of the present invention by printing, painting, metal deposition, etc., the adhesion and adhesion between the printing ink, paint, metal thin film, etc. and the polyester film It has the advantage that durability is improved. In addition, when pasting other materials such as film, woven fabric, nonwoven fabric or molded body on the surface opposite to the surface on which the rubber layer is laminated, the advantage of improving the adhesion and adhesion durability between the material and the polyester film Also has.
The method for producing a rubber / polyester film laminate of the present invention can produce a rubber / polyester film laminate having the above-mentioned properties economically and stably.

The plastic molded body of the present invention has the following characteristics because the rubber / polyester film laminate is used as a component of the plastic molded body.
(1) Since the strain generated in the molding of a plastic molded body can be relaxed by utilizing the elasticity of the rubber layer, for example, the surface state of the plastic molded body can be improved and the strain generated during molding can be improved. In addition, the external force applied to the molded body in the use of the plastic molded body can be relaxed by the elasticity of the rubber layer. For example, the durability of the plastic molded body can be improved.
(2) Since the rubber / polyester film laminate is laminated with a polyester film, the rubber / polyester film laminate exhibits a reinforcing effect to increase the strength of the plastic molded article.
(3) Since the polyester film is laminated on the rubber / polyester film laminate, the barrier properties such as gas barrier properties of the plastic molded article may be improved.
(4) Polyester film surface smoothness and rubber when the polyester film surface of the rubber / polyester film laminate is laminated so that the polyester film surface side of the rubber / polyester film laminate is a surface layer. It has the advantage that extremely high surface smoothness can be obtained by the print-through effect of the layer. Therefore, high-quality surface decoration is possible when the surface of the plastic molded body is decorated.
(5) Since the rubber / polyester film laminate having the above characteristics is used, the adhesive strength between the coated polyester film and the rubber layer is high, and the durability of the adhesive strength is excellent. It can be suitably used as a constituent member of a molded body requiring durability such as a plate.

  The coated polyester film for rubber lamination of the present invention has a crosslinked polymer film having a thickness of 0.003 to 5 μm on at least one surface of a polyester film having a degree of plane orientation of 0.005 to 0.15, and the longitudinal direction of the film and The 10% elongation stress (25 ° C.) in the width direction is 20 to 200 MPa.

The plane orientation degree of the polyester film in the present invention is 0.005 to 0.15. The upper limit of the degree of plane orientation is 0.15, and 0.14 is more preferable. When high moldability is required, 0.13 or less is more preferable. The degree of plane orientation is a physical property related to moldability. The higher the degree of plane orientation, the more the molecular chains are arranged in the plane direction and the moldability is lowered. Accordingly, the smaller the degree of plane orientation, the better the moldability. On the other hand, from the viewpoint of ensuring flatness such as strength and thickness unevenness of the film, or from the viewpoint of ensuring solvent resistance, the lower limit of the degree of plane orientation is more preferably 0.01 and even more preferably 0.04.
Here, the degree of plane orientation of the polyester film is the following according to the longitudinal refractive index (Nx), the lateral refractive index (Ny), and the refractive index (Nz) of the film measured using an Abbe refractometer ( 1) A value calculated from the equation.
Plane orientation degree = (Nx + Ny) / 2−Nz (1)
In the coated polyester film for rubber lamination of the present invention, when the thickness of the crosslinked polymer layer is 0.5 μm or less, the influence of the crosslinked polymer layer on the refractive index of the polyester base film is small. By measuring the refractive index of the polyester film, the refractive index of the polyester base film can be measured, and the degree of plane orientation can be calculated.

A method for bringing the degree of plane orientation to the above range is not limited, but a biaxially stretched polyester is preferably used. Such a biaxial stretching method may be either simultaneous biaxial stretching or sequential biaxial stretching.
The production method of the above-described biaxially stretched polyester film is not particularly limited. For example, after drying the polyester as necessary, the polyester is supplied to a known melt extruder, extruded from a slit-shaped die into a sheet, and electrostatically The unstretched sheet is stretched after being brought into close contact with the casting drum by a method such as application, solidified by cooling, and an unstretched sheet is obtained. Such a stretching method may be either simultaneous biaxial stretching or sequential biaxial stretching. In short, the unstretched sheet is stretched and heat-treated in the longitudinal direction and the width direction of the film to obtain a film having a desired degree of plane orientation. The method is adopted.

  The method for bringing the degree of plane orientation in the above-mentioned biaxially stretched polyester film is not limited, but for example, by optimizing the stretch ratio and heat setting temperature using a homopolyester resin such as polyethylene terephthalate or polyethylene naphthalate as a raw material. Examples of the method and polyester resin include a copolyester resin, a method of reducing the degree of plane orientation using a compounded resin in which the copolyester resin and the homopolyester resin are blended, and a method combining the above methods. It is done.

  For example, in order to reduce the degree of plane orientation under the stretching conditions, the stretching ratio of biaxial stretching is preferably 1.6 to 4.2 times in each direction, and more preferably 1.7 to 4. 0 times. Most preferably, it is 1.8 to 3.2 times. In this case, either of the stretching ratios in the longitudinal direction and the width direction may be increased or the same. The stretching speed is desirably 1000% / min to 200000% / min, and the stretching temperature can be any temperature as long as it is not less than the glass transition temperature of the polyester and not less than the glass transition temperature + 100 ° C., preferably It is good to extend | stretch in the range of 80-170 degreeC. Further, the film is heat-treated after biaxial stretching, and this heat treatment can be performed by any conventionally known method such as in an oven or on a heated roll. The heat treatment temperature can be any temperature between 120 ° C. and 245 ° C., preferably 150 to 220 ° C. Moreover, although the heat processing time can be made arbitrary, Preferably it is good to carry out for 1 to 60 seconds. In addition, you may perform this heat processing, relaxing a film to the longitudinal direction and / or the width direction. Furthermore, re-stretching may be performed once or more in each direction, and then heat treatment may be performed. Here, the heat treatment temperature can be confirmed by the peak temperature of the crystal melting sub-peak caused by the heat treatment observed by DSC.

In the present invention, when developing to applications where high moldability is required, it is preferable to cope with the method exemplified below.
In the present invention, it is important that the 10% elongation stress (25 ° C.) in the longitudinal direction and the width direction of the polyester film is 20 to 200 MPa. The stress at 10% elongation (25 ° C.) is more preferably 20 to 180 MPa, and further preferably 20 to 160 MPa. If the stress at 10% elongation (25 ° C.) is 20 MPa or more, the film can be prevented from being stretched or broken when the roll film is pulled and unwound. On the other hand, if the stress at 10% elongation (25 ° C.) is 200 MPa or less, moldability can be secured. In particular, when using a mold with irregularities and depressions, the film before molding may be followed by lightly following the mold in advance, and in such cases, the film has good moldability. , Product design is improved.

  In the polyester film, the thermal shrinkage in the longitudinal direction and the width direction at 150 ° C. is preferably 0.01 to 5.0%. The lower limit value of the heat shrinkage rate at 150 ° C. is more preferably 0.1%, still more preferably 0.5%. On the other hand, the upper limit value of the thermal shrinkage rate at 150 ° C. is more preferably 4.5%, further preferably 4.1%, and particularly preferably 3.2%. If the thermal shrinkage of the film in the longitudinal direction and the width direction at 150 ° C. is 0.01% or more, productivity can be ensured. On the other hand, if the heat shrinkage ratio of the film in the longitudinal direction and the width direction at 150 ° C. is 5.0% or less, the appearance of the film after the post-processing without causing deformation of the film even in the post-processing step where heat is applied. And design properties are improved.

  The haze of the polyester film is preferably 0.1 to 3.0%. The lower limit of haze is more preferably 0.3%, still more preferably 0.5%. On the other hand, the upper limit of haze is more preferably 2.5%, still more preferably 2.0%. If the haze is 0.1% or more, the film can be produced on an industrial scale with high normal productivity. On the other hand, if the haze of the film is 3.0% or less, when the vapor deposition or sputtering surface of a metal or the like, or the printed surface is viewed from the back surface of the film, the metal or the printed surface becomes clear and a good design property is ensured. be able to. In addition, it is difficult to obtain a film having a haze of 2.0% or less by a method for forming irregularities on the film surface by incorporating particles in the film, which is generally performed for improving handling properties in the film. . This characteristic is an important characteristic in the application to the application where the coated polyester film for rubber lamination of the present invention is used as the outermost layer of the molded body and is decorated.

  When the rubber / polyester film laminate of the present invention is used as the outermost layer of the molded product, the surface roughness (Ra) of at least one film is preferably 0.005 to 0.030 μm. The lower limit value of Ra is more preferably 0.006 μm, still more preferably 0.007 μm. On the other hand, the upper limit of Ra is more preferably 0.025 μm, and still more preferably 0.015 μm. If Ra of the film on at least one side is 0.005 μm or more, blocking or tearing of the film does not occur when winding the film or unwinding the film once wound into a roll. Moreover, if Ra is 0.03 micrometer or less, defects, such as a protrusion, will not generate | occur | produce in post-processing processes, such as vapor deposition, sputtering, or printing, and design property will be ensured.

Although the manufacturing method of the polyester film which has the said characteristic is not limited, Implementing with the method illustrated below is a preferable embodiment.
As a raw material of the polyester film, it is preferable to use a copolymerized polyester containing 5 to 50 mol% of a copolymer component as a raw material. A polyester film obtained by using a copolymer polyester containing 5 to 50 mol% of a copolymer component as a raw material has a lower crystallization rate and lower crystallinity than a polyethylene terephthalate film or the like. In addition, in order to reduce the degree of plane orientation and the thermal shrinkage at 150 ° C., when a method of heat treatment at a temperature higher than usual is used, the heat treatment is rapidly performed at a high temperature after the end of stretching, The mobility of the molecules that make up the lower material is increased. Therefore, the surface protrusions formed by the bulging of the particles (particles in the biaxially oriented film or particles in the coating layer) in the stretching process are buried again in the heat treatment zone, so that the surface roughness is sufficient. Can't get. Therefore, avoiding the problem of haze reduction when the amount of added particles is increased more than necessary in order to prevent blocking and tearing when winding the film neatly and unwinding the film wound into a roll. can do.

In order to solve the above-mentioned problem, it is preferable that the heat treatment zone has two stages (or more) and the first stage heat treatment temperature TS1 and the second stage heat treatment temperature TS2 are controlled within a specific range.
As a result, in the first heat treatment zone, the crystallization of the film is promoted to some extent before the particles are buried in the film, and the temperature is further increased in the second heat treatment zone. The mobility of the molecules is sufficiently lowered, and the film having a low thermal shrinkage rate can be obtained by further promoting the crystallinity while forming the protrusions on the surface. Moreover, it is not necessary to contain particles more than necessary from the viewpoint of transparency.

  The copolymer polyester used for the polyester film for molding includes (a) a copolymer polyester composed of an aromatic dicarboxylic acid component, ethylene glycol, and a glycol component containing a branched aliphatic glycol or alicyclic glycol, or (B) Copolyesters composed of an aromatic dicarboxylic acid component containing terephthalic acid and isophthalic acid and a glycol component containing ethylene glycol are preferred. Moreover, it is preferable from the point which further improves the moldability that the polyester which comprises a biaxially-oriented polyester film contains a 1, 3- propanediol unit or a 1, 4- butanediol unit as a glycol component further.

In the present invention, as a raw material for the polyester film, (a) when only the copolymerized polyester is used alone, (b) when two or more types of copolymerized polyester are used in a blend, (c) one or more types are used. In the case of blending the copolymerized polyester and one or more homopolyesters, any method is possible. Among these, the blending method is preferable from the viewpoint of suppressing the lowering of the melting point.
As the above-mentioned copolymer polyester, when using a copolymer polyester composed of an aromatic dicarboxylic acid component, ethylene glycol, and a glycol component containing a branched aliphatic glycol or alicyclic glycol, as the aromatic dicarboxylic acid component, Terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid or ester-forming derivatives thereof are suitable, and the amount of terephthalic acid and / or naphthalenedicarboxylic acid component relative to the total dicarboxylic acid component is 70 mol% or more, preferably 85 mol% or more, Especially preferably, it is 95 mol% or more, Most preferably, it is 100 mol%.

Examples of branched aliphatic glycols include neopentyl glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, and the like. Examples of the alicyclic glycol include 1,4-cyclohexanedimethanol and tricyclodecane dimethylol.
Among these, neopentyl glycol and 1,4-cyclohexanedimethanol are particularly preferable. Furthermore, it is a more preferable embodiment that 1,3-propanediol or 1,4-butanediol is used as a copolymerization component in addition to the glycol component. Use of these glycols as a copolymerization component is suitable for imparting the above-mentioned properties, and is also excellent in transparency and heat resistance, from the viewpoint of improving the adhesion with the adhesion modified layer. Is also preferable.

  Further, when a copolymer polyester composed of an aromatic dicarboxylic acid component containing terephthalic acid and isophthalic acid and a glycol component containing ethylene glycol is used as the copolymer polyester, the amount of ethylene glycol is 70 with respect to the total glycol component. It is at least mol%, preferably at least 85 mol%, particularly preferably at least 95 mol%, particularly preferably at least 100 mol%. As the glycol component other than ethylene glycol, the above-mentioned branched aliphatic glycol, alicyclic glycol, or diethylene glycol is suitable.

Examples of the catalyst used in producing the copolymer polyester include alkaline earth metal compounds, manganese compounds, cobalt compounds, aluminum compounds, antimony compounds, titanium compounds, titanium / silicon composite oxides, and germanium compounds. . Of these, titanium compounds, antimony compounds, germanium compounds, and aluminum compounds are preferred from the viewpoint of catalytic activity.
When manufacturing the said copolyester, it is preferable to add a phosphorus compound as a heat stabilizer. As said phosphorus compound, phosphoric acid, phosphorous acid, etc. are preferable, for example.
The above copolyester preferably has an intrinsic viscosity of 0.50 dl / g or more, more preferably 0.55 dl / g or more, and particularly preferably from the viewpoint of moldability, adhesion, and film-forming stability. 60 dl / g or more. If the intrinsic viscosity is less than 0.50 dl / g, the moldability tends to decrease. In addition, when a filter for removing foreign substances is provided in the melt line, the upper limit of the intrinsic viscosity is preferably 1.0 dl / g from the viewpoint of ejection stability during extrusion of the molten resin.

By using one or more homopolyesters or copolymerized polyesters as the polyester raw material and blending them to form a film, transparency is maintained while maintaining the same flexibility as when only the copolymerized polyester is used. And a high melting point (heat resistance) can be realized. In addition, when only a high melting point homopolyester (for example, polyethylene terephthalate) is used, it is possible to realize a melting point (heat resistance) having no flexibility and practical problem while maintaining high transparency.
In addition, it is more preferable from the viewpoint of moldability to blend the copolymerized polyester and at least one homopolyester other than polyethylene terephthalate (for example, polytetramethylene terephthalate or polybutylene terephthalate) as a raw material. .

  The melting point of the polyester film having the above characteristics is preferably 200 to 245 ° C. from the viewpoint of heat resistance and moldability. By controlling the type and composition of the polymer to be used and the film forming conditions within the range of the melting point, a balance between moldability and finish can be achieved, and a high-quality molded product can be produced economically. Here, the melting point is an endothermic peak temperature at the time of melting, which is detected at the time of primary temperature rise in so-called differential scanning calorimetry (DSC). The melting point was determined by measuring using a differential scanning calorimeter (manufactured by Mac Science, DSC3100S) at a heating rate of 20 ° C./min. The lower limit of the melting point is more preferably 210 ° C, particularly preferably 230 ° C. When the melting point is 200 ° C. or higher, the heat resistance is not deteriorated. Further, even when the rubber layer is crosslinked by thermal crosslinking, the problem that distortion occurs in the polyester film laminate does not occur.

The polyester film preferably has a light transmittance at a wavelength of 370 nm of 50% or less, more preferably 40% or less, and particularly preferably 30% or less. By controlling the light transmittance of the polyester film at a wavelength of 370 nm to 50% or less, particularly when the rubber / polyester film laminate of the present invention is used as the outermost layer of the molded body, the weather resistance of the molded body is improved. Can do.
As a method of controlling the light transmittance at a wavelength of 370 nm to 50% or less, a method of blending an ultraviolet absorber in any of the constituent layers of the polyester film is used. The ultraviolet absorber may be either inorganic or organic as long as it can impart the above characteristics. Examples of organic ultraviolet absorbers include benzotoazole, benzophenone, cyclic imino ester, and combinations thereof. From the viewpoint of heat resistance, benzotoazole and cyclic imino ester are preferred. When two or more kinds of ultraviolet absorbers are used in combination, ultraviolet rays having different wavelengths can be absorbed simultaneously, so that the ultraviolet absorption effect can be further improved.
Examples of inorganic ultraviolet absorbers include ultrafine particles of metal oxides such as cerium oxide, zinc oxide, and titanium oxide.

  Examples of the benzotriazole ultraviolet absorber include 2- [2′-hydroxy-5 ′-(methacryloyloxymethyl) phenyl] -2H-benzotriazole and 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl). ) Phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxypropyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxyhexyl) phenyl ] -2H-benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-tert -Butyl-3 '-(methacryloyloxyethyl) phenyl] -2 -Benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxyethyl) phenyl] -5-methoxy-2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-cyano-2H-benzotriazole, 2- [2'-hydroxy-5'-( Methacryloyloxyethyl) phenyl] -5-tert-butyl-2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -5-nitro-2H-benzotriazole, and the like. However, it is not particularly limited to these.

  Examples of the cyclic imino ester UV absorber include 2,2 ′-(1,4-phenylene) bis (4H-3,1-benzoxazin-4-one), 2-methyl-3,1-benzoxazine. -4-one, 2-butyl-3,1-benzoxazin-4-one, 2-phenyl-3,1-benzoxazin-4-one, 2- (1- or 2-naphthyl) -3,1- Benzoxazin-4-one, 2- (4-biphenyl) -3,1-benzoxazin-4-one, 2-p-nitrophenyl-3,1-benzoxazin-4-one, 2-m-nitrophenyl -3,1-benzoxazin-4-one, 2-p-benzoylphenyl-3,1-benzoxazin-4-one, 2-p-methoxyphenyl-3,1-benzoxazin-4-one, 2- o-methoxy Enyl-3,1-benzoxazin-4-one, 2-cyclohexyl-3,1-benzoxazin-4-one, 2-p- (or m-) phthalimidophenyl-3,1-benzoxazin-4-one 2,2 ′-(1,4-phenylene) bis (4H-3,1-benzoxazinon-4-one) 2,2′-bis (3,1-benzoxazin-4-one), 2, 2′-ethylenebis (3,1-benzoxazin-4-one), 2,2′-tetramethylenebis (3,1-benzoxazin-4-one), 2,2′-decamethylenebis (3 1-benzoxazin-4-one), 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2′-m-phenylenebis (3,1-benzoxazine-4) -On), 2,2 '-(4,4 -Diphenylene) bis (3,1-benzoxazin-4-one), 2,2 '-(2,6- or 1,5-naphthalene) bis (3,1-benzoxazin-4-one), 2, 2 '-(2-methyl-p-phenylene) bis (3,1-benzoxazin-4-one), 2,2'-(2-nitro-p-phenylene) bis (3,1-benzoxazine-4 -One), 2,2 '-(2-chloro-p-phenylene) bis (3,1-benzoxazin-4-one), 2,2'-(1,4-cyclohexylene) bis (3,1 -Benzoxazin-4-one) 1,3,5-tri (3,1-benzoxazin-4-one-2-yl) benzene, 1,3,5-tri (3,1-benzoxazine-4- On-2-yl) naphthalene and 2,4,6-tri (3,1-benzo) Oxazin-4-on-2-yl) naphthalene, 2,8-dimethyl-4H, 6H-benzo (1,2-d; 5,4-d ′) bis- (1,3) -oxazine-4,6 -Dione, 2,7-dimethyl-4H, 9H-benzo (1,2-d; 5,4-d ') bis- (1,3) -oxazine-4,9-dione, 2,8-diphenyl- 4H, 8H-benzo (1,2-d; 5,4-d ′) bis- (1,3) -oxazine-4,6-dione, 2,7-diphenyl-4H, 9H-benzo (1,2 -D; 5,4-d ') bis- (1,3) -oxazine-4,6-dione, 6,6'-bis (2-methyl-4H, 3,1-benzoxazin-4-one) 6,6′-bis (2-ethyl-4H, 3,1-benzoxazin-4-one), 6,6′-bis (2-phenyl-4H) 3,1-benzoxazin-4-one), 6,6′-methylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6′-methylenebis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6,6′-ethylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6′-ethylenebis (2-phenyl-) 4H, 3,1-benzoxazin-4-one), 6,6′-butylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6′-butylenebis (2-phenyl-) 4H, 3,1-benzoxazin-4-one), 6,6′-oxybis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6′-oxybis (2-phenyl-) 4H, 3,1-benzoxa 4-one), 6,6′-sulfonylbis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6′-sulfonylbis (2-phenyl-4H, 3,1) -Benzoxazin-4-one), 6,6'-carbonylbis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6'-carbonylbis (2-phenyl-4H, 3 , 1-benzoxazin-4-one), 7,7′-methylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 7,7′-methylenebis (2-phenyl-4H, 3 , 1-benzoxazin-4-one), 7,7′-bis (2-methyl-4H, 3,1-benzoxazin-4-one), 7,7′-ethylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 7, 7′-oxybis (2-methyl-4H, 3,1-benzoxazin-4-one), 7,7′-sulfonylbis (2-methyl-4H, 3,1-benzoxazin-4-one), 7 , 7′-carbonylbis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,7′-bis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,7′-bis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6,7′-methylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), And 6,7′-methylenebis (2-phenyl-4H, 3,1-benzoxazin-4-one) and the like.

When blending the above-mentioned organic UV absorbers with polyester films, they are exposed to high temperatures in the extrusion process. Therefore, UV absorbers that use a UV absorber with a decomposition start temperature of 290 ° C. or higher use process contamination during film formation. This is preferable for reducing the amount of the ink. If an ultraviolet absorber having a decomposition start temperature of 290 ° C. or higher is used, the decomposed product of the ultraviolet absorber adheres to the roll group of the manufacturing apparatus during film formation, and may be reattached to the film or scratched. The situation that becomes an optical defect can be prevented.
The upper limit of the melting point is preferably higher from the viewpoint of heat resistance, but when the polyethylene terephthalate unit is the main component, if the melting point is 250 ° C. or less, the moldability and transparency of the film can be ensured. Therefore, in order to obtain high moldability and transparency, it is preferable to control the upper limit of the melting point to 245 ° C.

Moreover, in order to improve handling properties, such as slipperiness and winding property of a polyester film, it is preferable to form unevenness on the film surface. As a method for forming irregularities on the film surface, a method of incorporating particles in the film is generally used.
As said particle | grains, external particles, such as an internal precipitation particle | grain with an average particle diameter of 0.01-10 micrometers, an inorganic particle, and / or an organic particle, are mentioned. If an average particle diameter is 10 micrometers or less, the defect of a film, the designability, and the deterioration of transparency will not be caused. On the other hand, when the average particle diameter is 0.01 μm or more, it is possible to prevent the handling properties such as the slipping property and the winding property of the film from being lowered. The lower limit of the average particle diameter of the particles is more preferably 0.10 μm, particularly preferably 0.50 μm, from the viewpoint of handling properties such as slipping property and winding property. On the other hand, when the upper limit is preferably 5 μm, it is possible to reduce film defects due to good transparency and coarse protrusions. Particularly preferably, it is 2 μm.
The average particle size of the particles was taken by taking a plurality of photographs of at least 200 particles by electron microscopy, tracing the outline of the particles on an OHP film, and converting the trace image into an equivalent circle diameter with an image analyzer. To calculate.

Examples of the external particles include wet and dry silica, colloidal silica, aluminum silicate, titanium oxide, calcium carbonate, calcium phosphate, barium sulfate, alumina, mica, kaolin, clay, hydroxyapatite and the like, and styrene, silicone, acrylic Organic particles or the like containing acids as constituent components can be used. Among these, inorganic particles such as dry, wet and dry colloidal silica and alumina, and organic particles containing styrene, silicone, acrylic acid, methacrylic acid, polyester, divinylbenzene and the like as constituent components are preferably used. Two or more of these internal particles, inorganic particles and / or organic particles may be used in combination as long as the characteristics defined in the present invention are not impaired.
Furthermore, the content of the particles in the film is preferably in the range of 0.001 to 10% by mass. If it is 0.001 mass% or more, deterioration of handling property, such as deterioration of the slidability of a film and difficulty in winding, will not be caused. On the other hand, if it is 10 mass% or less, formation of a coarse protrusion, deterioration of film forming property, transparency, etc. can be prevented.

Moreover, since the particle | grains contained in a film generally differ in refractive index from polyester, it becomes a factor which reduces the transparency of a film.
In many cases, the molded product is printed on the surface of the film before the film is molded in order to improve the design. Since such a printing layer is often applied to the back side of a molding film, it is desired that the transparency of the film is high from the viewpoint of printing clarity.
Therefore, in order to obtain a high degree of transparency while maintaining the handleability of the film, the particles are not substantially contained in the base film of the main layer, and the particles are only in the surface layer having a thickness of 0.01 to 5 μm. It is effective to use a laminated film having a laminated structure containing. The upper limit of the thickness of the surface layer is preferably 3 μm, particularly preferably 1 μm. In this case, the particles exemplified above can be used.

In order to make haze of the above-mentioned polyester film 0.1 to 3.0%, in order to make it especially 2.0 or less, particle | grains are not included substantially in said film, and thickness is 0.01- A laminated structure in which particles are contained only in a surface layer of 5 μm is preferable. In addition, it is difficult to obtain a film having a haze of 3.0% or less only by incorporating particles in the film while maintaining handling properties.
In order to obtain a film having a low haze and a high design property, it is preferable that particles are not substantially contained in the above-mentioned film. Note that “substantially no particles are contained in the base film” as used above means, for example, in the case of inorganic particles, the content that is below the detection limit when inorganic elements are quantified by fluorescent X-ray analysis. means. This is because contaminants derived from foreign substances may be mixed without intentionally adding particles to the base film.

  The thin surface layer can be formed by a coating method or a coextrusion method. Especially, in the case of the coating method, since the adhesiveness with a printing layer can also be improved by using the composition which consists of adhesiveness modification resin containing particle | grains as an application layer, it is a preferable method. As said adhesive property modification resin, resin which consists of at least 1 sort (s) chosen from polyester, a polyurethane, an acrylic polymer, and / or those copolymers is preferable.

As the particles to be contained in the surface layer, the same particles as those described above can be used. Among the particles, silica particles, glass fillers, and silica-alumina composite oxide particles are particularly suitable from the viewpoint of transparency because the refractive index is relatively close to that of polyester.
Furthermore, the particle content in the surface layer is preferably in the range of 0.01 to 25% by mass. When the content is less than 0.01% by mass, handling properties are likely to deteriorate, for example, the slipperiness of the film deteriorates or winding becomes difficult. On the other hand, when it exceeds 25 mass%, transparency and applicability are likely to deteriorate.

  In order to impart other functions, the polyester film can have a laminated structure by a known method using different types of polyester. The form of the laminated film is not particularly limited. For example, the laminated film has an A / B type 2 layer configuration, a B / A / B type 2 type 3 layer configuration, and a C / A / B type 3 layer 3 configuration. The form is mentioned

It is important that the polyester film is a biaxially stretched film. By molecular orientation by biaxial stretching, the thermal deformation rate of the film under a micro tension (initial load 49 mN) can be controlled within a preferable range, and solvent resistance and dimensional stability, which are disadvantages of the unstretched sheet. Is improved. The correspondence can improve the solvent resistance and heat resistance, which are disadvantages of the unstretched sheet, while maintaining the good formability of the unstretched sheet.
The method for producing the polyester film is not particularly limited. For example, after drying the polyester resin as necessary, the polyester film is supplied to a known melt extruder, extruded into a sheet from a slit die, and applied by a method such as electrostatic application. An example is a method in which the unstretched sheet is biaxially stretched after being brought into close contact with the casting drum and cooled and solidified to obtain the unstretched sheet.

As the biaxial stretching method, a method is employed in which an unstretched sheet is stretched in the longitudinal direction (MD) and the width direction (TD) of the film and heat treated to obtain a biaxially stretched film having a desired in-plane orientation degree. . Among these methods, in terms of film quality, the MD / TD method in which the film is stretched in the longitudinal direction and then stretched in the width direction, or the TD / MD method in which the film is stretched in the width direction and then stretched in the longitudinal direction. An axial stretching method and a simultaneous biaxial stretching method in which the longitudinal direction and the width direction are stretched almost simultaneously are desirable. In the case of the simultaneous biaxial stretching method, a tenter driven by a linear motor may be used. Furthermore, if necessary, a multistage stretching method in which stretching in the same direction is performed in multiple stages may be used.
The film stretching ratio when biaxially stretching is preferably 1.6 to 4.2 times in the longitudinal direction and the width direction, particularly preferably 1.7 to 4.0 times. In this case, the stretching ratio in the longitudinal direction and the width direction may be either larger or the same ratio. More preferably, the stretching ratio in the longitudinal direction is 2.8 to 4.0 times, and the stretching ratio in the width direction is 3.0 to 4.5 times.

It is preferable to select, for example, the following conditions as stretching conditions for producing the polyester film.
In the longitudinal stretching, it is more preferable that the stretching temperature is 50 to 110 ° C. and the stretching ratio is 1.6 to 4.0 times so that the subsequent lateral stretching can be performed smoothly.
Usually, when stretching the polyethylene terephthalate, if the stretching temperature is lower than the appropriate conditions, the yield stress increases abruptly at the beginning of the lateral stretching, and therefore stretching cannot be performed. Moreover, even if it can be stretched, it is not preferable because the thickness and stretch ratio are likely to be non-uniform.
In addition, when the stretching temperature is higher than appropriate conditions, the initial stress is low, but the stress does not increase even when the stretch ratio is high. Therefore, the film has a small stress at 10% elongation at 25 ° C. Therefore, by taking the optimum stretching temperature, a highly oriented film can be obtained while ensuring stretchability.
However, when the copolymerized polyester contains 1 to 40 mol% of a copolymer component, the stretching stress rapidly decreases as the stretching temperature is increased so as to eliminate the yield stress. In particular, since the stress does not increase even in the latter half of the stretching, the orientation does not increase, and the stress at 10% elongation at 25 ° C. decreases.
Such a phenomenon is likely to occur when the thickness of the film is 60 to 500 μm, and is particularly noticeable in a film having a thickness of 100 to 300 μm. Therefore, in the case of a film using the copolymerized polyester of the present invention, the stretching temperature in the transverse direction is preferably set as follows.

  First, the preheating temperature is in the range of +10 to + 50 ° C. of the glass transition temperature when the mixture (raw material) after extruding the film material with an extruder is measured by DSC. Next, in the first half of the transverse stretching, the stretching temperature is preferably −20 to + 15 ° C. with respect to the preheating temperature. In the latter half of the transverse stretching, the stretching temperature is preferably 0 to −30 ° C. with respect to the stretching temperature of the first half, and particularly preferably in the range of −10 to −20 ° C. with respect to the stretching temperature of the first half. By adopting such conditions, the first half of the transverse stretching is easy to stretch because the yield stress is small, and the second half is easily oriented. In addition, it is preferable that the draw ratio of a horizontal direction shall be 2.5 to 5.0 times. As a result, it is possible to obtain a film satisfying the 10% elongation stress at 25 ° C. defined in the present invention.

  Furthermore, the film is subjected to heat treatment (heat setting treatment) after biaxial stretching. This heat treatment condition is an important condition for achieving both haze and surface roughness, that is, slipperiness of the film. The stretched film is subsequently heat-treated in the tenter. In this case, it is important to perform the heat treatment in two or more stages. The first stage heat treatment temperature (TS1) is −5 to −30 ° C. of the second stage heat treatment temperature (TS2), the lower limit is preferably TS2-10 ° C., and the upper limit is preferably TS2-25 ° C. The heat treatment temperature (TS2) of the second stage is performed in the range of −5 to −35 ° C. of the melting point when the mixture (raw material) after extruding the film material with an extruder is measured by DSC described later. The lower limit value of TS2 is preferably a melting point of −10 ° C., and the upper limit value of TS2 is preferably a melting point of −30 ° C. An intermediate heat treatment zone can be provided between TS1 and TS2, and a heat treatment zone can be provided after TS2. In these cases, TS2 shows the highest heat treatment temperature. By taking such conditions, a film having a low haze and good sliding properties can be obtained.

  The reason is considered as follows. A polyester film containing about 5 to 50 mol% of a copolymer component as in the present invention has a lower crystallization speed and lower crystallinity than a polyethylene terephthalate film. Therefore, when heat treatment is performed rapidly at a high temperature after the end of stretching, the mobility of molecules constituting the material having low crystallinity is increased in the heat treatment zone. Therefore, the surface protrusion formed by the bulging of the particles (particles in the film and / or particles of the coating layer) in the stretching process is buried again in the heat treatment zone, so that sufficient surface roughness is obtained. I can't. Therefore, in order to wind up the film neatly, the content of the particles is increased more than necessary, which causes a decrease in haze. On the other hand, if the temperature of TS2 is lower than a predetermined temperature, a film having a sufficiently low thermal shrinkage at 150 ° C. cannot be obtained.

  Therefore, the method of the present invention in which the heat treatment zone has two stages (or more) is that the crystallization of the film is promoted to some extent before the particles are buried in the TS1 and the TS2 zone is sufficient. Even when the temperature is increased, the molecular mobility is sufficiently lowered as compared with the state of the previous paragraph, and the film is further promoted in crystallinity with the surface protrusions formed, and a film having a low thermal shrinkage rate can be obtained. Moreover, the addition of more than necessary particles can be prevented.

  In general, as a means for lowering the degree of plane orientation, a method of lowering the draw ratio and a method of increasing the blending amount of the copolymer component are known, but the former method deteriorates the thickness unevenness of the film. This is not preferable because the melting point is lowered and the heat resistance is deteriorated. In the present invention, in order to reduce the plane orientation degree of the biaxially oriented polyester film and the thermal shrinkage at 150 ° C., heat setting is performed at a higher temperature than usual. The heat setting is preferably performed in the above-described heat treatment, particularly the second heat treatment.

  Moreover, since it is preferable to use a copolyester for the polyester film, since the melting point is lower than that of a uniform polymer, if the heat setting temperature is increased, the film is difficult to peel off to the clip that holds the film in the transverse stretching step. Become. Therefore, it is important to sufficiently cool the vicinity of the clip when the clip releases the film at the tenter outlet. Specifically, in order to make it easy to peel the film and the clip, (1) a method of providing a heat shielding wall on the clip portion so that the clip is hardly heated, and (2) a method of adding a clip cooling mechanism to the tenter. (3) A method in which the cooling section after heat setting is set long in order to enhance the cooling capacity, and the entire film is sufficiently cooled. (4) The cooling efficiency is increased by increasing the length of the cooling section and the number of sections. It is preferable to employ a method of increasing the clip, and (5) a method of enhancing the cooling of the clip by using a type in which the return portion of the clip travels outside the furnace.

  It is important that the coated polyester film for rubber lamination of the present invention is formed by coating a crosslinked polymer layer having a thickness of 0.003 to 5 μm on at least one surface of the polyester film. When the thickness of the crosslinked polymer layer is 0.003 μm or more, an effect of improving the adhesion between the polyester film and the rubber layer can be obtained. Moreover, if it is 5 micrometers or less, it can fully exhibit the adhesive improvement effect on the industrial production of a polyester film and a rubber layer, Furthermore, the stress at the time of 10% elongation in the longitudinal direction and the width direction of the below-mentioned film (25 C)) can be lowered, and the possibility of lowering the moldability and durability of the adhesive strength between the rubber layer and the polyester film can be prevented. The thickness of the crosslinked polymer layer is more preferably 3 μm or less, further preferably 1 μm or less, and particularly preferably 0.5 μm or less. By setting the thickness to 0.5 μm or less, the adhesion durability between the polyester film and the rubber layer may be improved.

  The polymer compound constituting the crosslinked polymer layer is not limited, but is preferably at least one resin selected from polyester, polyurethane, and acrylic acid polymer. As the polymer compound, the above resins may be used alone, or two or three different types may be used in combination.

The polyester resin has an ester bond in the main chain or side chain, and is obtained by polycondensation of dicarboxylic acid and diol.
As the carboxylic acid component constituting the polyester resin, aromatic, aliphatic, and alicyclic dicarboxylic acids and trivalent or higher polyvalent carboxylic acids can be used.
As aromatic dicarboxylic acids, terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 2,5-dimethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2 -Bisphenoxyethane-p, p'-dicarboxylic acid, phenylindanedicarboxylic acid, etc. can be used. From the viewpoint of the strength and heat resistance of the coating film, these aromatic dicarboxylic acids preferably account for 30 mol% or more, more preferably 35 mol% or more, most preferably 40 mol% or more of the total dicarboxylic acid component. Is preferably used.
Examples of the aliphatic and alicyclic dicarboxylic acids include succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, dimer acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like, and ester-forming derivatives thereof can be used.

  As the glycol component of the polyester resin, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2,4-dimethyl-2-ethylhexane-1,3- Diol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2 , 4-Trimethyl-1,6-hexanediol, 1,2-si Rhohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 4,4'-thiodiphenol, bisphenol A 4,4′-methylenediphenol, 4,4 ′-(2-norbornylidene) diphenol, 4,4′-dihydroxybiphenol, o-, m-, and p-dihydroxybenzene, 4,4′-isopropylidene Phenol, 4,4′-isopropylidene bin diol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol and the like can be used.

In addition, when a polyester resin is used as a coating liquid in an aqueous solution, a compound containing a sulfonate group, a compound containing a phosphonate group, and a carboxylate base are used to facilitate water-solubilization or water-dispersion of the polyester resin. It is preferable to copolymerize a compound containing
Examples of the compound containing a carboxylate group include trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, 4-methylcyclohexene-1,2,3-tricarboxylic acid, trimesic acid, 1,2, 3,4-butanetetracarboxylic acid, 1,2,3,4-pentanetetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 5- (2,5-dioxotetrahydrofurfuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid, 5- (2,5-dioxotetrahydrofurfuryl) -3-cyclohexene-1,2-dicarboxylic acid, cyclopentanetetracarboxylic acid, 2,3 , 6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, ethylene glycol bistrimellitate, , 2 ′, 3,3′-diphenyltetracarboxylic acid, thiophene-2,3,4,5-tetracarboxylic acid, ethylenetetracarboxylic acid, etc., or alkali metal salts, alkaline earth metal salts, ammonium salts, etc. thereof However, it is not limited to these.

  Examples of the compound containing a sulfonate group include sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, sulfo-p-xylylene glycol, 2-sulfo -1,4-bis (hydroxyethoxy) benzene or the like, or alkali metal salts, alkaline earth metal salts, and ammonium salts thereof can be used, but are not limited thereto.

  Examples of the compound containing a phosphonate group include phosphoterephthalic acid, 5-phosphosophthalic acid, 4-phosphoisophthalic acid, 4-phosphonaphthalene-2,7-dicarboxylic acid, phospho-p-xylylene glycol, 2-phospho- 1,4-bis (hydroxyethoxy) benzene or the like, or an alkali metal salt, alkaline earth metal salt, or ammonium salt thereof can be used, but is not limited thereto.

  In the present invention, for example, a modified polyester copolymer such as a block copolymer or a graft copolymer modified with acrylic, urethane, epoxy, or the like can be used.

  Preferred polyesters include terephthalic acid, isophthalic acid, sebacic acid, 5-sodium sulfoisophthalic acid as the acid component, and a copolymer selected from ethylene glycol, diethylene glycol, 1,4-butanediol, and neopentyl glycol as the glycol component. Can be mentioned. When water resistance is required, a copolymer having trimellitic acid as its copolymer component can be suitably used instead of 5-sodium sulfoisophthalic acid.

The polyester resin can be produced by the following production method. For example, a polyester resin composed of terephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid as a dicarboxylic acid component, and ethylene glycol and neopentyl glycol as a glycol component will be described as follows: terephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid A first stage in which ethylene glycol or neopentyl glycol is directly esterified, or terephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid and ethylene glycol or neopentyl glycol are transesterified, and It can be produced by a method of producing the reaction product by a second stage in which a polycondensation reaction is performed.
At this time, as the reaction catalyst, for example, alkali metal, alkaline earth metal, manganese, cobalt, zinc, antimony, germanium, titanium compound, or the like can be used.

Further, as a method for obtaining a polyester resin having a large amount of carboxylic acid at the terminal and / or side chain, JP-A-54-46294, JP-A-60-209073, JP-A-62-240318, JP-A-53-26828, JP-A-53-26829, JP-A-53-98336, JP-A-56-116718, JP-A-61-124684, JP-A-62-240318 Although it can be produced from a resin obtained by copolymerization of a trivalent or higher polyvalent carboxylic acid described in Japanese Patent Publication No. Gazette, etc., other methods may be used.
Further, as the water-dispersed polyester resin, for example, a commercially available “Vaironal (registered trademark)” series (manufactured by Toyobo Co., Ltd.) can also be used.
Further, as the solvent or the required polyester resin, for example, a commercially available “Byron (registered trademark)” series (manufactured by Toyobo Co., Ltd.) can be used.

  The intrinsic viscosity of the polyester resin is not particularly limited, but is preferably 0.3 dl / g or more, more preferably 0.35 dl / g or more, and most preferably 0.4 dl / g in terms of adhesiveness. That is all. The glass transition point (hereinafter sometimes abbreviated as Tg) of the polyester resin is preferably 0 to 130 ° C, more preferably 10 to 85 ° C. When Tg is less than 0 ° C, for example, heat-resistant adhesiveness is inferior, or a blocking phenomenon occurs in which the coating films adhere to each other. On the contrary, when it exceeds 130 ° C, the stability and water dispersibility of the polyester resin are inferior This is not preferable.

The polyurethane urethane resin is not particularly limited as long as it has a urethane bond, and the main component is obtained by polymerizing a polyol compound and a polyisocyanate compound.
As the polyurethane resin, a urethane resin whose affinity for water is increased by introducing a carboxylate group, a sulfonate group, or a sulfuric acid half ester base can be used. The content of a carboxylate group, a sulfonate group, or a sulfuric acid half ester base is preferably 0.5 to 15% by mass.
Examples of the polyol compound include polyethylene glycol, polypropylene glycol, polyethylene / propylene glycol, polytetramethylene glycol, hexamethylene glycol, hexamethylene glycol, tetramethylene glycol, 1,5-pentanediol, diethylene glycol, triethylene glycol, polycaprolactone. Polyhexamethylene adipate, polytetramethylene adipate, trimethylolpropane, trimethylolethane, glycerin, acrylic polyol, and the like can be used.
Examples of the polyisocyanate compound include tolylene diisocyanate, hexamethylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, an adduct of tolylene diisocyanate and trimethylolpropane, an adduct of hexamethylene diisocyanate and trimethylolethane, and the like. it can.
Here, the main structural components of the urethane resin may contain a chain extender, a crosslinking agent and the like in addition to the polyol compound and the polyisocyanate compound.
As the chain extender or crosslinking agent, ethylene glycol, propylene glycol, butanediol, diethylene glycol, ethylenediamine, diethylenetriamine, or the like can be used.

The polyurethane resin having an anionic group is, for example, a method of using a compound having an anionic group for polyol, polyisocyanate, chain extender, etc. Can be produced using a method of reacting a specific compound with a group having active hydrogen of polyurethane or a specific compound, but is not particularly limited.
The anionic group in the polyurethane resin is preferably used as a sulfonic acid group, a carboxylic acid group and an ammonium salt, lithium salt, sodium salt, potassium salt or magnesium salt thereof, and particularly preferably a sulfonic acid group.
The amount of the anionic group in the polyurethane resin is preferably 0.05% by mass to 8% by mass. If it is less than 0.05% by mass, the water dispersibility of the polyurethane resin tends to be poor, and if it exceeds 8% by mass, the water resistance and blocking resistance tend to be inferior.
For example, as an aqueous dispersion of a polyurethane resin, “Hydran (registered trademark)” series (manufactured by Dainippon Ink & Chemicals, Inc.) can be used.

  Examples of the monomer component constituting the acrylic polymer resin include alkyl acrylate and alkyl methacrylate (alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl. Group, 2-ethylhexyl group, lauryl group, stearyl group, cyclohexyl group, phenyl group, benzyl group, phenylethyl group), 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl Hydroxyl group-containing monomers such as methacrylate, acrylamide, methacrylamide, N-methyl acrylamide, N-methyl methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N, -Amide group-containing monomers such as dimethylolacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-phenylacrylamide, etc., and amino group-containing monomers such as N, N-diethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate , Epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate, monomers containing a carboxyl group such as acrylic acid, methacrylic acid and salts thereof (lithium salt, sodium salt, potassium salt, etc.) or salts thereof can be used. These are copolymerized using 1 type, or 2 or more types. Furthermore, these can be used in combination with other types of monomers.

  Examples of other types of monomers include epoxy group-containing monomers such as allyl glycidyl ether, sulfonic acids such as styrene sulfonic acid, vinyl sulfonic acid, and salts thereof (lithium salt, sodium salt, potassium salt, ammonium salt, and the like). A monomer containing a group or a salt thereof, a monomer containing a carboxyl group or a salt thereof such as crotonic acid, itaconic acid, maleic acid, fumaric acid and salts thereof (lithium salt, sodium salt, potassium salt, ammonium salt, etc.), Monomers containing acid anhydrides such as maleic anhydride and itaconic anhydride, vinyl isocyanate, allyl isocyanate, styrene, vinyl methyl ether, vinyl ethyl ether, vinyl trisalkoxysilane, alkyl maleic acid monoester, alkyl fumaric acid mono Ester, acrylonitrile, methacrylonitrile, alkyl itaconic acid monoester, vinylidene chloride, vinyl acetate, etc. can be used vinyl chloride.

Moreover, as said acrylic polymer resin, a modified acrylic polymer resin, for example, a block copolymer modified with polyester, urethane, epoxy, etc., a graft copolymer, etc. can be used.
Although Tg of the said acrylic polymer resin is not specifically limited, Preferably it is -10-90 degreeC, More preferably, it is 0-50 degreeC, Most preferably, it is 10-40 degreeC. When an acrylic resin having a low Tg is used, the heat resistant adhesiveness tends to be inferior and blocking tends to occur. On the other hand, when the acrylic resin is too high, the adhesiveness may deteriorate and the film forming property may be inferior. The molecular weight of the acrylic polymer is preferably 50,000 or more, more preferably 300,000 or more from the viewpoint of adhesiveness.
Examples of the acrylic polymer resin include copolymers selected from methyl methacrylate, ethyl acrylate, n-butyl acrylate, 2-hydroxyethyl acrylate, acrylamide, N-methylol acrylamide, and acrylic acid.

The acrylic polymer resin is preferably dissolved, emulsified or suspended in water and used as an aqueous liquid from the viewpoint of environmental pollution and explosion-proof properties during application. Such water-based acrylic polymer resins are copolymerized with monomers having a hydrophilic group (such as acrylic acid, methacrylic acid, acrylamide, vinyl sulfonic acid and salts thereof), and emulsion polymerization using reactive emulsifiers and surfactants. , Suspension polymerization, soap-free polymerization and the like.
Commercially available acrylic emulsions may also be used, for example, “Jonkrill (registered trademark)” series (manufactured by BASF Japan).

  Moreover, in this invention, the modified body which introduce | transduced frame | skeleton of rubber components, such as nitrile butadiene, for example to the resin which consists of said polyester, a polyurethane, and an acryl-type polymer may be sufficient. Since the modified body may be able to further improve the adhesion to the rubber layer and the adhesion durability, this is a preferred embodiment. In this case, the structure of the rubber component to be introduced preferably has the same structure as the rubber component to be combined, but is not necessarily limited. Introducing rubber components having different structures may also be effective. Inferred not only by the effect of introducing rubber components but also by the effect caused by the improvement of adhesion durability due to the flexibility improvement effect of the crosslinked polymer film as well as the compatibility with the composite rubber layer is doing.

  The method for preparing the modified product is not limited. For example, a rubber component having a carboxyl group, a hydroxyl group or an amino group introduced therein may be added during the preparation of the polymer and introduced into the polymer using, for example, a condensation reaction or an addition reaction. Alternatively, it may be introduced by grafting or block polymerization using a rubber component having a vinyl group or an acrylic group introduced at the terminal.

In the present invention, the resin composed of the polyester, polyurethane, and acrylic polymer is preferably crosslinked.
The crosslinking method is not limited, and examples thereof include a method of crosslinking a resin made of the above polymer using a crosslinking agent.
The crosslinking agent in the method of crosslinking using the above-mentioned crosslinking agent is not particularly limited, but functional groups present in the above-described polymer, such as carboxyl group, hydroxyl group, methylol group, amide group, etc. Any melamine-based crosslinking agent, oxazoline-based crosslinking agent, isocyanate-based crosslinking agent, aziridine-based crosslinking agent, epoxy-based crosslinking agent, methylolated or alkylolized urea-based, acrylamide-based Polyamide resins, amide epoxy compounds, various silane coupling agents, various titanate coupling agents, and the like can be used. Among these, an isocyanate-based crosslinking agent, a melamine-based crosslinking agent, and an oxazoline-based crosslinking agent can be suitably used from the viewpoint of compatibility with the resin, adhesiveness, and the like. In particular, the use of an isocyanate-based crosslinking agent is preferable from the viewpoint of adhesion durability.

  For example, the melamine-based crosslinking agent is not particularly limited, but a melamine, a methylolated melamine derivative obtained by condensing melamine and formaldehyde, a compound partially or completely etherified by reacting a methylolated melamine with a lower alcohol, or These mixtures can be used. As the melamine-based crosslinking agent, a monomer, a condensate composed of a dimer or higher polymer, a mixture thereof, or the like can be used. As the lower alcohol used for etherification, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol and the like can be used. The functional group has an imino group, a methylol group, or an alkoxymethyl group such as a methoxymethyl group or a butoxymethyl group in one molecule, and an imino group type methylated melamine resin, a methylol group type melamine resin, or a methylol group type. Examples include methylated melamine resins and fully alkyl type methylated melamine resins. Among these, an imino group type melamine resin and a methylolated melamine resin are preferable, and an imino group type melamine resin is most preferable. Furthermore, an acidic catalyst such as p-toluenesulfonic acid may be used in order to promote thermal curing of the melamine-based crosslinking agent.

The oxazoline-based crosslinking agent is not particularly limited as long as it has an oxazoline group as a functional group in the compound, but includes at least one monomer containing an oxazoline group, and at least one kind What consists of an oxazoline group containing copolymer obtained by copolymerizing other monomers is preferable.
Monomers containing an oxazoline group include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, and the like can be used, and one or a mixture of two or more thereof can also be used. Of these, 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially.

In the oxazoline-based cross-linking agent, the at least one other monomer used for the monomer containing the oxazoline group is not particularly limited as long as it is a monomer copolymerizable with the monomer containing the oxazoline group. Acrylates or methacrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, acrylate-2-ethylhexyl, methacrylate-2-ethylhexyl, etc. Unsaturated carboxylic acids such as acid, methacrylic acid, itaconic acid and maleic acid, unsaturated nitriles such as acrylonitrile and methacrylonitrile, acrylamide, methacrylamide, N-methylolacrylamide, N-methylol methacrylate Contains unsaturated amides such as amides, vinyl esters such as vinyl acetate and vinyl propionate, vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, olefins such as ethylene and propylene, vinyl chloride, vinylidene chloride, and vinyl fluoride. Halogen-α, β-unsaturated monomers, α, β-unsaturated aromatic monomers such as styrene and α-methylstyrene can be used, and these should be used alone or in a mixture of two or more. You can also.
As the oxazoline group-containing crosslinking agent, for example, “Epocross (registered trademark)” series (manufactured by Nippon Shokubai Co., Ltd.) is available.

The isocyanate-based crosslinking agent is not particularly limited as long as it has an isocyanate group as a functional group in the compound, but use of a polyfunctional isocyanate compound containing two or more isocyanate groups in one molecule. Is preferred.
As the polyfunctional isocyanate compound, a low-molecular or high-molecular aromatic or aliphatic diisocyanate, or a trivalent or higher polyisocyanate can be used. Polyisocyanates include tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and trimers of these isocyanate compounds. Further, an excess amount of these isocyanate compounds and low molecular active hydrogen compounds such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, or polyester polyols, poly The terminal isocyanate group containing compound obtained by making it react with polymer active hydrogen compounds, such as ether polyols and polyamides, can be mentioned.
As the isocyanate-based crosslinking agent, for example, “Coronate (registered trademark)” series (manufactured by Polyurethane Industry Co., Ltd.) and “Millionate (registered trademark)” series (manufactured by Polyurethane Industry Co., Ltd.) are available. In particular, the use of the Millionate series is preferable from the viewpoint of adhesive durability.

In addition, when using an isocyanate compound as a crosslinking agent, it is also possible to use a block type isocyanate compound.
The blocked isocyanate can be prepared by subjecting the above isocyanate compound and blocking agent to an addition reaction by a conventionally known appropriate method. Examples of the isocyanate blocking agent include phenols such as phenol, cresol, xylenol, resorcinol, nitrophenol, and chlorophenol; thiophenols such as thiophenol and methylthiophenol; oximes such as acetoxime, methyl etiketooxime, and cyclohexanone oxime. Alcohols such as methanol, ethanol, propanol and butanol; halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol; tertiary alcohols such as t-butanol and t-pentanol ; Lactams such as ε-caprolactam, δ-valerolactam, ν-butyrolactam, β-propyllactam; aromatic amines; imides; acetylacetone, acetoacetate Active methylene compounds such as malonic acid ethyl ester; mercaptans; imines; ureas; diaryl compounds; and sodium bisulfite and the like.

Epoxy-based crosslinking agent The epoxy-based crosslinking agent is not particularly limited as long as it has an epoxy group as a functional group. However, it is preferable to use a polyfunctional epoxy compound containing two or more epoxy groups in one molecule.
Examples of the polyfunctional epoxy compound include diglycidyl ether of bisphenol A and oligomer thereof, diglycidyl ether of hydrogenated bisphenol A and oligomer thereof, orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, p-oxybenzoic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene Glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether and poly Lukylene glycol diglycidyl ether, trimellitic acid triglycidyl ester, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol triglycidyl Examples thereof include triglycidyl ethers of ethers and glycerol alkylene oxide adducts.

Examples of the cross-linking agent include phenol formaldehyde resins of condensates with formaldehyde such as alkylated phenols and cresols; adducts of urea, melamine, benzoguanamine and the like with formaldehyde, and the adducts having 1 to 6 carbon atoms. Amino resins such as alkyl ether compounds made of alcohol can also be used.
Examples of the phenol formaldehyde resin include alkylated (methyl, ethyl, propyl, isopropyl or butyl) phenol, p-tert-amylphenol, 4,4′-sec-butylidenephenol, p-tert-butylphenol, o-, m-, p-cresol, p-cyclohexylphenol, 4,4'-isopropylidenephenol, p-nonylphenol, p-octylphenol, 3-pentadecylphenol, phenol, phenyl o-cresol, p-phenylphenol, xylenol, etc. Mention may be made of condensates of phenols and formaldehyde.

  Examples of amino resins include methoxylated methylol urea, methoxylated methylol N, N-ethyleneurea, methoxylated methylol dicyandiamide, methoxylated methylol melamine, methoxylated methylol benzoguanamine, butoxylated methylol melamine, butoxylated methylol benzoguanamine, and the like. Are preferably methoxylated methylol melamine, butoxylated methylol melamine, methylolated benzoguanamine, and the like.

  The resin and the cross-linking agent can be mixed and used at an arbitrary ratio, but the cross-linking agent is added in a solid content mass ratio of 2 parts by mass or more and less than 50 parts by mass with respect to 100 parts by mass of the resin generally used. Even if the effect is exhibited, it is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, and still more preferably 90 parts by mass or more when imparting adhesion durability. Is preferred. When the addition amount of the crosslinking agent is less than 2 parts by mass, the addition effect is small. Although an upper limit is not limited, it is 500 mass parts.

  In the present invention, in addition to the above method, for example, a crosslinked polymer layer may be formed using a self-crosslinking resin in which a crosslinkable functional group is introduced into the above-described polymer. The crosslinking method in the case of using a self-crosslinking resin may be, for example, thermal crosslinking, or may be crosslinking with high energy active rays such as ultraviolet rays, electron beams and γ rays.

Hereinafter, a specific method is illustrated for the case of polyester as the self-crosslinking resin.
The self-crosslinking type polyester resin preferably used in the present invention is a polyester-based graft copolymer resin obtained by grafting at least one compound having a radical polymerizable double bond to a hydrophobic copolymer polyester resin. . The “grafting” of the polyester-based graft copolymer resin in the present invention is to introduce a branched polymer composed of a polymer different from the main chain into the main polymer as the main chain. Graft polymerization is usually carried out by reacting at least one radical polymerizable monomer using a radical initiator in a state where a hydrophobic copolyester resin is dissolved in an organic solvent. Hydrophobic copolyester resins are essentially water-insoluble polyester resins that do not inherently dissolve in water, so compared to using polyester resins that are soluble in water as the backbone polymer for graft polymerization. Excellent in heat-resistant water adhesion.

  The hydrophobic copolyester resin is composed of 60 to 99.5 mol% aromatic dicarboxylic acid, 0 to 39.5 mol% aliphatic dicarboxylic acid and / or alicyclic dicarboxylic acid in 100 mol% dicarboxylic acid component, It is preferable that the dicarboxylic acid containing a radically polymerizable double bond is 0.5 to 10 mol%. More preferably, the aromatic dicarboxylic acid is 68 to 98 mol%, the aliphatic dicarboxylic acid and / or the alicyclic dicarboxylic acid is 0 to 30 mol%, and the dicarboxylic acid containing a polymerizable unsaturated double bond is 2 to 7 Mol%.

When the aromatic dicarboxylic acid is 60 mol% or more and the aliphatic dicarboxylic acid and / or alicyclic dicarboxylic acid is 39.5 mol% or less, the heat resistant water adhesion is good. Moreover, the grafting of the radically polymerizable monomer with respect to the polyester resin can be efficiently performed by using 0.5 mol% or more of the dicarboxylic acid containing a radically polymerizable double bond. On the other hand, the content of 10 mol% or less is preferable because the viscosity of the reaction solution can be prevented from significantly increasing in the later stage of the grafting reaction, and the reaction can proceed uniformly.
As the aromatic dicarboxylic acid, aliphatic and / or alicyclic dicarboxylic acid, any of the exemplified compounds can be used. Examples of the dicarboxylic acid containing a radical polymerizable double bond include fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, and other α, β-unsaturated dicarboxylic acids; 2,5-norbornene dicarboxylic acid anhydride And alicyclic dicarboxylic acids containing unsaturated double bonds such as tetrahydrophthalic anhydride. Of these dicarboxylic acids containing a polymerizable unsaturated double bond, fumaric acid, maleic acid, and 2,5-norbornene dicarboxylic acid are preferred from the viewpoint of polymerizability.
As the glycol component, any of the compounds exemplified above can be used. Two or more glycol components may be used in combination. Especially, C2-C10 aliphatic glycol, C6-C12 alicyclic glycol, etc. are preferable.

The hydrophobic copolymerized polyester resin can be copolymerized with 0 to 5 mol% of a trifunctional or higher polycarboxylic acid and / or polyol. The tri- or higher functional polycarboxylic acid includes (anhydrous) trimellitic acid, (anhydrous) pyromellitic acid, (anhydrous) benzophenone tetracarboxylic acid, trimesic acid, ethylene glycol bis (anhydrotrimellitate), glycerol tris (anne) Hydrotrimellitate) and the like. As the trifunctional or higher functional polyol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, or the like is used.
The tri- or higher functional polycarboxylic acid and / or polyol is copolymerized in the range of 0 to 5 mol%, preferably 0 to 3 mol% with respect to the total acid component or the total glycol component. Gelation can be suppressed.
The lower limit of the weight average molecular weight of the hydrophobic copolyester resin is preferably 5,000 from the viewpoint of adhesiveness. Moreover, it is preferable that an upper limit is 50,000 at points, such as gelatinization at the time of superposition | polymerization.

  After synthesizing the hydrophobic copolyester resin, graft polymerization is performed. Graft polymerization is carried out by reacting at least one radical polymerizable monomer using a radical initiator in a state where the hydrophobic copolyester resin is dissolved in an organic solvent. The reaction product after completion of the grafting reaction includes a graft copolymer of a desired hydrophobic copolymerized polyester resin and a radically polymerizable monomer, as well as a hydrophobic copolymerized polyester and a hydrophobic copolymer that have not undergone grafting. It also contains a (co) polymer obtained from a radical polymerizable monomer that has not been grafted to the polymerized polyester resin. The polyester-based graft copolymer in the present invention is not only the above-mentioned polyester-based graft copolymer, but in addition to this, a hydrophobic copolymerized polyester resin that has not undergone grafting, and a radically polymerizable monomer that has not been grafted. Also included are reaction mixtures that also contain (co) polymers and monomers (residual monomers) obtained from

In the present invention, the acid value of a reaction product obtained by graft-polymerizing a radically polymerizable monomer to a hydrophobic copolymerized polyester resin is preferably 600 eq / 10 ⁶ g or more from the viewpoint of heat-resistant water adhesion. More preferably, the acid value of the reactant is 1200 eq / 10 ⁶ g or more. When the acid value of the reaction product is less than 600 eq / 10 ⁶ g, the hot water adhesion may be lowered.
The mass ratio of the desired hydrophobic copolyester and radical polymerizable monomer suitable for the purpose of the present invention is desirably in the range of polyester / radical polymerizable monomer = 40/60 to 95/5, more preferably 55/45. ~ 93/7, most preferably in the range of 60/40 to 90/10.
By setting the mass ratio of the hydrophobic copolymerized polyester resin to 40% by mass or more, the excellent adhesiveness of the polyester can be exhibited. On the other hand, when the mass ratio of the hydrophobic copolyester is 95% by mass or less, the blocking resistance can be improved and the acid value of the reaction product can be adjusted to the above range.

  The graft polymerization reaction product is in the form of an organic solvent solution or dispersion or an aqueous solvent solution or dispersion. In particular, a dispersion of an aqueous solvent, that is, a form of an aqueous dispersion is preferable in terms of working environment and applicability. Therefore, as the radical polymerizable monomer to be grafted, it is preferable to use a radical polymerizable monomer that essentially contains a hydrophilic radical polymerizable monomer. Then, after graft polymerization in an organic solvent, an aqueous dispersion can be obtained by adding water and distilling off the organic solvent.

  The hydrophilic radical polymerizable monomer means a radical polymerizable monomer having a hydrophilic group or a group that can be changed to a hydrophilic group later. Examples of the radical polymerizable monomer having a hydrophilic group include a radical polymerizable monomer containing a carboxyl group, hydroxyl group, phosphoric acid group, phosphorous acid group, sulfonic acid group, amide group, quaternary ammonium base and the like. . On the other hand, examples of the radical polymerizable monomer having a group that can be changed into a hydrophilic group include radical polymerizable monomers containing an acid anhydride group, a glycidyl group, a chloro group, and the like. Among these, from the viewpoint of water dispersibility, a carboxyl group is preferable, and a radical polymerizable monomer having a carboxyl group or a group capable of generating a carboxyl group is preferable.

In order to make the acid value of the graft reaction product within the above preferred range, it is preferable that a radical polymerizable monomer containing a carboxyl group or a group capable of generating a carboxyl group is contained. Such monomers include fumaric acid, monoethyl fumarate; maleic acid and its anhydride, monoethyl maleate; itaconic acid and its anhydride, monoester of itaconic acid; acrylic acid, methacrylic acid; and salts thereof (sodium Salt, potassium salt, ammonium salt) and the like. Maleic anhydride is preferable. The said monomer can be copolymerized using 1 type, or 2 or more types.
The radically polymerizable monomer to be grafted may contain other types of monomers as long as the acid value is within the above-mentioned preferable range. As other types of monomers, monomers that can be used when synthesizing the acrylic polymer described above can be used as they are.
Examples of the graft polymerization initiator include organic peroxides and organic azo compounds known to those skilled in the art. Examples of the organic peroxide include benzoyl peroxide, t-butyl peroxypivalate, and examples of the organic azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2, 4-dimethylvaleronitrile). The amount of the polymerization initiator used for the graft polymerization is at least 0.2% by mass, preferably 0.5% by mass or more, based on the radical polymerizable monomer.
In addition to the polymerization initiator, a chain transfer agent for adjusting the chain length of the branched polymer, for example, octyl mercaptan, mercaptoethanol, 3-t-butyl-4-hydroxyanisole may be used as necessary. In this case, it is desirable to add in the range of 0 to 5% by mass with respect to the polymerizable monomer.

The grafting reaction product is preferably neutralized with a basic compound, and can be easily dispersed in water by neutralization. As the basic compound, a compound that volatilizes at the time of coating film formation is desirable, and ammonia, organic amines, and the like are preferable. Desirable compounds include, for example, triethylamine, N, N-diethylethanolamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine , 3-ethoxypropylamine, 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, dimethylaminopropylamine, methyliminobispropylamine, 3-methoxypropylamine, monoethanolamine, diethanolamine, triethanol An amine etc. can be mentioned.
The basic compound has a pH value of the aqueous dispersion in the range of 5.0 to 9.0 by at least partial neutralization or complete neutralization depending on the carboxyl group content contained in the grafting reaction product. It is desirable to use it. If a basic compound with a boiling point of 100 ° C. or less is used, there are few residual basic compounds in the coating film after drying, and for example, improved hot water adhesion in harsh environments such as high temperature and humidity To do.

In the grafting reaction product, the weight average molecular weight of the polymer of the radical polymerizable monomer is preferably 500 to 50,000. It is generally difficult to control the weight average molecular weight of the polymer of the radical polymerizable monomer to be less than 500, the graft efficiency is lowered, and there is a tendency that hydrophilic groups are not sufficiently imparted to the copolymer polyester. In addition, the graft polymer of the radical polymerizable monomer forms a hydrated layer of dispersed particles. To obtain a stable aqueous dispersion with a sufficient thickness of the hydrated layer, the graft polymer of the radical polymerizable monomer is used. The weight average molecular weight of is desirably 500 or more.
The upper limit of the weight average molecular weight of the graft polymer of the radical polymerizable monomer is preferably 50,000 from the viewpoint of polymerizability in solution polymerization. In order to set the weight average molecular weight of the graft polymer of the radical polymerizable monomer within the range of 500 to 50,000, the initiator amount, the monomer dropping time, the polymerization time, the reaction solvent, the monomer composition, or a chain as necessary. It is preferable to carry out by appropriately combining a transfer agent and a polymerization inhibitor.
The glass transition temperature of the graft copolymer is not particularly limited, but is preferably 20 ° C. or higher, more preferably 40 ° C. or higher in consideration of heat resistant water adhesion.

In the present invention, a reaction product obtained by graft polymerization of a radically polymerizable monomer to a hydrophobic copolymerized polyester resin has a self-crosslinking property because a hydroxyl group in the polyester and a carboxyl group present in the graft portion react. Moreover, although it does not bridge | crosslink at normal temperature, it carries out intermolecular reaction, such as a hydrogen abstraction reaction by a thermal radical, with the heat at the time of drying at the time of coating film formation, and bridge | crosslinks without a crosslinking agent. As a result, a high degree of heat resistant water adhesion is exhibited. The degree of crosslinking of the coating film can be evaluated by various methods, and examples thereof include a method of measuring the insoluble fraction in a chloroform solvent or the like that dissolves both the hydrophobic copolymerized polyester and the grafted polymer.
The insoluble fraction of the coating film obtained by drying at about 80 ° C. and heat-treating at 120 ° C. for 5 minutes is preferably 50% by mass or more, more preferably 70% by mass, from the viewpoints of heat resistant water adhesion and blocking resistance. That's it.
As the self-crosslinking polyester resin aqueous dispersion, for example, a commercially available product such as “Vylonal (registered trademark) AGN702” (manufactured by Toyobo Co., Ltd.) can be used.
In addition, a grafted polyurethane can be prepared by a method similar to the above.

Further, various additives such as an antioxidant, a heat stabilizer, a weather stabilizer, an ultraviolet absorber, an organic lubricant, and the like within the range in which the effects of the present invention are not impaired in the crosslinked polymer layer, Pigments, dyes, organic or inorganic fine particles, fillers, antistatic agents, nucleating agents and the like may be blended.
In particular, a material obtained by adding inorganic particles to the crosslinked polymer layer is more preferable because the slipperiness and blocking resistance are improved. In this case, silica, colloidal silica, alumina, alumina sol, kaolin, talc, mica, calcium carbonate, or the like can be used as the inorganic particles to be added. The average particle size used is preferably 0.005 to 5 μm, more preferably 0.01 to 3 μm, and most preferably 0.05 to 2 μm, and the mixing ratio with respect to the resin in the coating film is not particularly limited. However, 0.05-10 mass parts is preferable by solid content mass ratio, More preferably, it is 0.1-5 mass parts.

  A method of coating the crosslinked polymer layer is not limited and is arbitrary, but a method of performing by a coating method is preferable. As the step of applying the coating solution in this method, a method of coating on an unstretched film and then stretching in at least one direction, a method of coating after longitudinal stretching, a method of coating on the film surface after the orientation treatment, etc. Either method is possible. In particular, when producing a polyester base film, a so-called in-line coating method is applied in which the film is applied before the crystal orientation of the film is completed, and then stretched in at least one direction and then the crystal orientation of the polyester film is completed. This is a preferable method that can exhibit the effect of the above.

There are various coating methods such as reverse coating, gravure coating, rod coating, bar coating, Mayer bar coating, die coating, and spray coating. The method etc. can be used.
In the present invention, as described above, it is essential that the crosslinked polymer layer is coated on at least one surface of the polyester film, but a form in which the crosslinked polymer layer is coated on both surfaces of the polyester film is a more preferable embodiment. . The effect of this embodiment will be described later.

  The reason why the rubber / polyester film laminate of the present invention can maintain the moldability and improve the adhesive strength between the rubber layer and the polyester and the durability of the adhesive strength is unknown, but the rubber layer of the present invention In the case of lamination, the stress difference at the time of elongation between the rubber layer and the polyester film in a very small deformation region is reduced, so that the occurrence of strain at the interface between the rubber layer and the polyester film during molding is reduced and the above characteristics are improved. Estimated. In the present invention, since a crosslinked polymer layer exists between the polyester rubber layers, the above-mentioned interface means an interface between the rubber layer and the crosslinked polymer layer.

Although the method for imparting the above properties is not limited, it is a preferred embodiment that the plane orientation degree and the cross-linked polymer layer thickness of the polyester film are within the above ranges.
The rubber / polyester film laminate of the present invention is preferably formed by laminating a rubber layer directly on the surface of the crosslinked polymer layer of the coated polyester film for rubber lamination obtained by the above method without using an adhesive.
The use of an adhesive for bonding the polyester film and the rubber layer and the bonding step can be omitted by the above measures, which is economically advantageous. Moreover, the adhesive layer can suppress a decrease in moldability.

In the rubber / polyester film laminate of the present invention, the adhesive strength between the rubber layer and the coated polyester film is preferably 9 N / 20 mm or more. 10 N / 20 mm or more is more preferable, and 11 N / 20 mm or more is more preferable. It is most preferable that the interface cannot be formed even if a cut is made between the rubber layer and the coated polyester film with a knife. Hereinafter, in order to distinguish from the adhesive strength after various durability tests, the adhesive strength before the durability test is also referred to as initial adhesive strength.
When the initial adhesive strength is less than 9 N / 20 mm, for example, when a rubber / polyester laminate is used as a member of a molded body, the rubber layer is peeled off from the coated polyester film for rubber lamination when a molding process or molded body is used. May occur, which is not preferable.
In the present invention, since a cross-linked polymer layer exists between the polyester film and the rubber layer, the adhesive strength in the present invention is the peel strength between the rubber layer and the cross-linked polymer layer or the cross-linked high strength with the polyester film. It means the delamination strength of either of the delamination strength with the molecular layer.

  The rubber / polyester film laminate of the present invention preferably has an adhesive strength of 8 N / 20 mm or more between the polyester film and the rubber layer after immersion in toluene (at 25 ° C. for 72 hours). 9N / 20mm or more is more preferable, and 10N / 20mm or more is more preferable. Hereinafter, the adhesive strength is also referred to as solvent-resistant adhesive strength. Moreover, the said characteristic is also called solvent-resistant adhesion durability. When the solvent-resistant adhesive strength is less than 8 N / 20 mm, for example, when printing or coating is applied to the surface of the rubber / polyester film laminate, the polyester film and the organic film contained in the printing ink or paint Peeling from the rubber layer occurs or the durability of the adhesive force between the polyester film and the rubber layer is lowered, and the durability of the molded body using the rubber / polyester film laminate and the reliability to the durability Is unfavorable because it decreases.

  In the rubber / polyester film laminate of the present invention, the adhesive strength between the polyester film and the rubber layer after the water-resistant durability treatment evaluated by the following method is more preferably 8 N / 20 mm or more. 9N / 20mm or more is more preferable, and 10N / 20mm or more is particularly preferable. Hereinafter, the adhesive strength is also referred to as water-resistant adhesive strength. The above characteristics are also referred to as water-resistant adhesion durability. When the water-resistant adhesive strength is less than 8 N / 20 mm, for example, when used as a constituent member of a molded body requiring durability such as an automobile outer plate, the polyester film and the rubber layer between the rubber and polyester film laminates are used. May cause peeling, or the durability of the adhesive force between the polyester film and the rubber layer may be reduced, and the durability of the molded body using the rubber / polyester film laminate and the reliability of the durability may be reduced. Therefore, it is not preferable.

(Water-resistant adhesive durability)
A measurement sample obtained by cutting a rubber / polyester film laminate into 50 mm × 50 mm is placed in a 500 cc lidded cylindrical glass container containing 400 cc of distilled water so that the rubber layer of the sample is on the lower side. Cap the container with the entire sample immersed in water. When the sample is not immersed in water by its own weight, for example, a polyester film of 60 mm × 60 mm and a thickness of 188 μm may be placed on the sample and weighted. The size and material of the weight are not particularly limited, and the entire sample may be immersed in water. The container containing the sample is placed in a gear oven set at 90 ° C. and allowed to stand for 14 days. After the heat treatment, take out the container from the oven, quickly take out the sample, put a knife at the interface between the rubber layer and the polyester film of the rubber / polyester film laminate, apply stress to the part with your fingers, and generate interface peeling, The peel strength is measured by a T-type peel method according to JIS K6854.

In the present invention, the rubber component constituting the rubber layer is not limited. For example, natural rubber (NR), silicone rubber (Q), ethylene propylene diene rubber (EPDM), acrylonitrile butadiene rubber (NBR), chloroprene rubber (CR), acrylic rubber (ACM), fluorine rubber (FKM), etc. Rubber or a mixture thereof may be mentioned.
The rubber component is appropriately selected depending on the required characteristics according to the purpose of use.

In the present invention, the method for imparting the various adhesive strengths described above is not limited, but it is preferable to blend an adhesion improver with the rubber layer.
As the adhesion improver, it is preferable to use a compound containing a reactive group active against radical reaction. Examples of this compound include acrylic acid derivatives, methacrylic acid derivatives, and allyl derivatives. Among them, derivatives having 2 or more, particularly 3 or more unsaturated bonds are preferable. These compounds are widely used as rubber co-crosslinking agents, and examples thereof include acrylic acid esters and methacrylic acid esters of polyhydric alcohols, allyl esters of polycarboxylic acids, triallyl isocyanurate, triallyl cyanurate, and the like. .

The polyhydric alcohol acrylic acid ester or methacrylic acid ester is an ester compound obtained by esterifying two or more alcoholic hydroxyl groups of a polyhydric alcohol having two or more alcoholic hydroxyl groups with acrylic acid or methacrylic acid. Glycol diacrylate, ethylene glycol dimethacrylate, 1,3 butanediol diacrylate, 1,3 butanediol dimethacrylate, 1,4 butanediol acrylate, 1,4 butanediol methacrylate, 1,6 hexanediol diacrylate, 1,6 Hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 2,2′bis (4-acryloxydiethoxyphenyl) propane, 2,2′bis (4-methacrylic) Xydiethoxyphenyl) prone, glycerin dimethacrylate, glycerin triacrylate, glycerin trimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, Pentaerythritol tetramethacrylate, tetramethylol methane diacrylate, tetramethylol methane dimethacrylate, tetramethylol methane triacrylate, tetramethylol methane trimethacrylate, tetramethylol tetraacrylate, tetramethylol tetramethacrylate, dimer diol diacrylate, dimer -Diol dimethacrylate etc. are mentioned, The compound containing 3 or more allylic acid ester or methacrylic acid ester is especially preferable. In addition, although said compound illustrated each single ester compound of acrylic acid and phthalacrylic acid, the form of mixed ester of acrylic acid and methacrylic acid may be sufficient.
Examples of the allyl ester of polyvalent carboxylic acid include phthalic acid diarylate, trimellitic acid diarylate, and pyromellitic acid tetraarylate.
Any one of the above-mentioned adhesive property improving agents may be used alone, or two or more thereof may be used in combination. Further, the adhesion improver used in the present invention is not limited to the above exemplary compounds.

The compounding amount of the adhesive property improving agent is 0.2 to 20 parts by mass, preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the total rubber component. On the contrary, when the amount exceeds 20 parts by mass, the effect of improving the adhesive strength reaches saturation, and the physical properties of the rubber decrease.
Moreover, in order to accelerate | stimulate the expression of the adhesive improvement effect by an above described adhesive improvement agent, it is a preferable embodiment to mix | blend a peroxide compound with respect to a rubber layer. The correspondence further improves the delamination strength between the rubber and the polyester film for rubber lamination.

The peroxide compound may be either acyl-based or alkyl-based, and may be benzoyl peroxide, monochlorobenzoyl peroxide, 2,4 dichlorobenzoyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5. Bis (t-butylperoxy) hexane, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-bis-t-butylperoxy-3,3,5-trimethyl Examples include cyclohexane, di-t-butyl peroxide, t-butyl cumyl peroxide and the like.
The compounding amount of the peroxide compound is preferably 0.05 to 10 parts by mass, particularly 1 to 8 parts by mass with respect to 100 parts by mass of the rubber component. By making this compounding amount 0.05 parts by mass or more, the adhesiveness is improved, and if it is 10 parts by mass or less, the above-mentioned promoting effect is maintained and the physical properties of the rubber and the film are not lowered.

When rubber other than silicone rubber is used, it is preferable to blend uncrosslinked silicone rubber in the rubber layer. The uncrosslinked silicone rubber is an organopolysiloxane represented by an average unit formula: RaSiO _{(4-a) / 2} . In the above formula, R is a substituted or unsubstituted monovalent hydrocarbon group, for example, an alkyl group such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, vinyl group, allyl group, butenyl. Group, alkenyl group such as pentenyl group and hexenyl group, aryl group such as phenyl group, tolyl group, xylyl group and naphthyl group, cycloalkyl group such as cyclopentyl group and cyclohexyl group, aralkyl group such as benzyl group and phenethyl group, 3 -Halogenated alkyl groups such as chloropropyl group and 3,3,3-trifluoropropyl group, etc. are mentioned, and preferred are methyl group, vinyl group, phenyl group and 3,3,3-trifluoropropyl group. In the above formula, a is a number in the range of 1.9 to 2.1. The silicone rubber component is represented by the above average unit formula. Specific siloxane units constituting the silicone rubber component are, for example, R ₃ SiO _1/2 units, R ₂ (HO) SiO _1/2 units, R ₂ SiO _2/2 units, RSiO _3/2 units and SiO _4/2 units.

The main component of the silicone rubber component is a linear polymer essentially comprising R ₂ iO _2/2 units and R ₃ SiO _1/2 units or R ₂ (HO) SiO _1/2 units, and in some cases a small amount The RSiO _3/2 unit and / or the R ₃ SiO _1/2 unit can be partially branched. In addition, a resinous polymer composed of R ₃ SiO _1/2 units and SiO _4/2 units can be blended as a part of the silicone rubber component. As described above, the silicone rubber component may be a mixture of two or more polymers.

In addition, the molecular structure of the uncrosslinked silicone rubber component is not particularly limited, and examples thereof include a straight chain, a partially branched linear chain, a branched chain, and a resin. A linear polymer or a mixture containing a linear polymer as a main component. Examples of the silicone rubber component include, for example, molecular chain both ends trimethylsiloxy group-capped dimethylpolysiloxane, molecular chain both ends trimethylsiloxy group-capped methylvinylpolysiloxane, molecular chain both ends trimethylsiloxy group-capped methylphenylpolysiloxane, molecule Trimethylsiloxy group-capped dimethylsiloxane / methylvinylsiloxane copolymer, both ends of the chain trimethylsiloxy group-capped dimethylsiloxane / methylphenylsiloxane copolymer, trimethylsiloxy group-capped dimethylsiloxane / methyl (3,3) 3,3-trifluoropropyl) siloxane copolymer, trimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, both ends of molecular chain dimethyl Nylsiloxy group-blocked dimethylpolysiloxane, molecular chain both ends dimethylvinylsiloxy group-blocked methylvinylpolysiloxane, molecular chain both ends dimethylvinylsiloxy group-blocked methylphenylpolysiloxane, molecular chain both ends dimethylvinylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane Copolymer, dimethylvinylsiloxy group-capped dimethylvinylsiloxy group-blocked dimethylvinylsiloxy group, dimethylvinylsiloxy group-capped dimethylsiloxane-methyl (3,3,3-trifluoropropyl) siloxane copolymer Dimethylvinylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, silanol group-blocked dimethylpolysiloxane, molecular chain Silanol group-blocked methylvinylpolysiloxane, molecular chain both-end silanol-blocked methylphenylpolysiloxane, molecular chain both-end silanol-blocked dimethylsiloxane / methylvinylsiloxane copolymer, molecular chain both-end silanol-blocked dimethylsiloxane / methylphenyl Siloxane copolymer, silanol group-blocked dimethylsiloxane / methyl (3,3,3-trifluoropropyl) siloxane copolymer, both ends of molecular chain silanol group-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane Polymer, molecular chain both ends trimethoxysiloxy-blocked dimethylpolysiloxane, molecular chain both ends trimethoxysiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, molecular chain both ends trimethoxysiloxane Si-group-blocked dimethylsiloxane / methylphenylsiloxane copolymer, trimethoxysiloxy-group-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, R ₃ SiO _1/2 unit and SiO _4/2 unit Organopolysiloxane copolymer, R ₂ SiO _2/2 unit and RSiO _3/2 unit organopolysiloxane copolymer, R ₃ SiO _1/2 unit, R ₂ SiO _2/2 unit and RSiO _3/2 Examples thereof include an organopolysiloxane copolymer composed of units, and a mixture of two or more of these. The viscosity of the silicone rubber component at 25 ° C. is not particularly limited, but is practically preferably 100 centistokes or more, particularly 1,000 centistokes or more.

  The blending amount of the uncrosslinked silicone rubber is preferably 5 to 100 parts by mass, particularly 10 to 70 parts by mass with respect to 100 parts by mass of the ethylene propylene rubber. If the said compounding quantity is 5 mass parts or more, the improvement of an adhesive improvement effect will be accelerated | stimulated, and if it is 100 mass parts or less on the contrary, said promotion effect can be maintained economically. In addition, the heat resistance of rubber | gum may improve by mix | blending silicone rubber.

Also, instead of blending uncrosslinked silicone rubber in the rubber layer, an uncrosslinked silicone rubber composition layer in which an adhesion improver is blended as an intermediate layer between the polyester and rubber layer for rubber lamination is interposed. Thus, the adhesive strength between the rubber lamination covering polyester and the rubber layer may be improved. In this case, the uncrosslinked silicone rubber can be the same as described above, and the adhesion improver can be the same as that blended in the rubber layer. And the compounding quantity of the adhesive improvement agent with respect to a silicone rubber is 0.5-30 mass parts with respect to 100 mass parts of silicone rubbers in the case of the said methacrylic acid ester, Especially 1-20 mass parts is preferable. If it is 0.5 mass part or more, the adhesive strength with a base film will be favorable, and if it is 30 mass parts or less, intensity | strength can be maintained economically.
The thickness of the uncrosslinked silicone rubber layer is preferably 0.0005 to 0.05 mm.
If necessary, reinforcing fillers, pigments, dyes, antioxidants, antioxidants, mold release agents, flame retardants, thixotropic agents, filler dispersants, and the like can be blended. Moreover, a peroxide can be mix | blended as an adhesive improvement promoter for promoting the adhesive improvement effect by said adhesive improvement agent.

  The method of blending the above compounding agent with rubber is not particularly limited. For example, when preparing a rubber compound, it may be performed using a rubber kneader such as a two-roll, Banbury mixer, or dough mixer (kneader). When the rubber is dissolved in a solvent and formed into a film by the casting method, the rubber compound may be dissolved in the solvent to prepare a solution, or may be added and blended either after forming the solution.

In the present invention, the method for producing the rubber / polyester film laminate is not limited. For example, it is preferable to produce by laminating an uncrosslinked rubber layer on the surface of the crosslinked polymer layer of the coated polyester film for rubber lamination, and subsequently crosslinking the rubber layer. In the method, it is a more preferable embodiment that the rubber layer is blended with the above-mentioned adhesion improver.
By the above measures, a rubber / polyester film laminate having the characteristics as described above can be produced economically and stably.
The method of laminating the rubber layer on the rubber lamination-coated polyester is arbitrary. For example, a solution obtained by dissolving the rubber composition in a solvent is applied to the crosslinked polymer layer surface of the rubber lamination-coated polyester film and dried to form the rubber layer. Examples thereof include a forming method, a method of forming a rubber layer by extruding a rubber composition onto the surface of a crosslinked polymer layer of a coated polyester film for rubber lamination under high pressure, and a calendering method. When liquid rubber such as liquid silicone rubber is used, it can be applied without dilution with a solvent.

  The crosslinking method in the said manufacturing method is not specifically limited. For example, thermal crosslinking may be used, and crosslinking using high-energy active rays such as electron beams and γ rays may be used. In particular, the method using actinic radiation does not require the addition of additives for radical generation such as peroxides, there is no deterioration in rubber properties due to residues of these additives, and it can be crosslinked efficiently and productivity. Is preferable.

  Depending on the intended use of the rubber / polyester film laminate of the present invention, the surface roughness of the rubber layer may be variously changed. As a means for controlling the surface roughness of the rubber layer for such a purpose, a cover sheet made of a film or fabric having a different surface roughness is overlapped on the surface of the uncrosslinked rubber layer so that the surface form of the cover sheet is changed to the rubber layer surface. It is known to transcribe. For example, as a means for imparting fine irregularities on the surface of a general rubber sheet, a fabric weight that uses a matte or embossed polyethylene film or vinyl chloride film, or a filament fabric such as nylon taffeta or polyester taffeta as a cover sheet Is widely practiced. The method can also be applied to the present invention.

The above cover sheet is overlapped on the surface of the rubber layer when it is crosslinked and peeled after the crosslinking is completed. As described above, an adhesion improver for improving the adhesive strength between the rubber layer and the polyester film, etc. When the cover sheet is blended, even if an attempt is made to peel the cover sheet after cross-linking, the peel strength between the rubber layer and the cover sheet is also improved, so that it may be difficult to peel the cover sheet. On the other hand, if the cover sheet is peeled before the crosslinking treatment, there is a problem that rubber is chipped and adheres to the cover sheet.
Therefore, it is preferable to perform a surface treatment for improving the peelability of the cover sheet. Moreover, you may use the film | membrane which consists of a raw material with low adhesive force with respect to a rubber layer, for example, a poly-4-methylpentene-1 or an ethylene methylmethacrylate copolymer, as a cover sheet. In addition, the rubber layer can be multilayered, and the amount of the adhesion improver in the rubber layer on the side opposite to the polyester film can be reduced on the cover sheet side than the rubber layer on the polyester film side. Moreover, when performing bridge | crosslinking by electron beam irradiation, it is also one method to perform the irradiation from the polyester film side, and this case is preferable at the point which the adhesive force of a rubber layer and a polyester film improves.

Although the usage method of the rubber polyester film laminated body of this invention is not limited, It is one preferable aspect to use as a member of a plastic molding. The composite of the rubber / polyester film laminate and the plastic molding obtained by the use can make use of various effects described in [Effects of the Invention].
Resin used for the said plastic molding is suitably selected by market demand etc., for example, both the thermoplastic resin and the hardened | cured material of a thermosetting resin can be used.

What is necessary is just to select suitably as a thermoplastic resin according to a market request | requirement or the kind of resin used for a base material for a plastic molding. Examples of the thermoplastic resin include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polypropylene terephthalate, polyethylene naphthalate and polybutylene terephthalate, polyamide, polyamideimide, polycarbonate, polysulfone, polyacetal, polyphenylene ether, polyphenylene sulfide, poly Examples include arylate, polyetherimide, polyethersulfone and polyetherketone, and blends and alloy compositions thereof.
Specific examples of the thermosetting resin include, but are not limited to, unsaturated polyester resins, vinyl ester resins, epoxy resins, and phenol resins.
Among these, since the balance between heat resistance and mechanical properties is excellent, it is preferable to use a cured product of a thermosetting resin. Especially, the balance between heat resistance and mechanical properties is particularly excellent, and the cure shrinkage is small. It is more preferable to use an epoxy resin because of its characteristics.

  In the present invention, it is preferable that the base material of the plastic molding is a fiber reinforced plastic in which a resin selected from the above resins and a fiber are combined. The fiber-reinforced plastic can increase the strength and elastic modulus of the molded body due to the reinforcing effect of the fibers, and can lead to weight reduction.

Specific examples of the reinforcing fiber include glass fiber, carbon fiber, aramid fiber, alumina fiber, and boron fiber. Among these, carbon fibers are preferably used because they have excellent characteristics of high strength and high elastic modulus while being lightweight.
As the reinforcing fibers, both short fibers and long fibers can be used. When emphasizing mechanical properties, it is preferable to use a reinforcing fiber having a length of 10 cm or more because a fiber-reinforced plastic having excellent properties of high strength and high elastic modulus can be obtained while being lightweight. . When emphasizing moldability, it is preferable to use reinforcing fibers having a length of 10 cm or less.
Specific examples of the reinforcing fiber array structure include a single direction, two directions, and a random direction. Specific examples of the form of the reinforcing fiber include a mat, a woven fabric, and a knitted fabric. Among them, it is preferable to use a single-directional array structure because a fiber-reinforced plastic molded body having excellent properties of high strength and high elastic modulus while being lightweight can be obtained. Moreover, since it is excellent in handleability, it is preferable to use the thing of the form of a textile fabric or a knitting.

  The plastic molded body is preferably in the form of a sheet. Moreover, it is preferable that the said plastic molding has a curved part. By taking advantage of the features of being capable of handling complex shapes and being lightweight, this aspect makes it possible to use electrical and electronic equipment parts, automobile equipment parts, personal computers, OA equipment, AV equipment, mobile phones, telephones, facsimiles, home appliances, toy supplies. It can be suitably used in various applications such as parts and casings of electrical / electronic devices.

The molding method of the plastic molded body of the present invention may be appropriately selected depending on the constituent material of the molded body, the shape of the molded body, and the like, and examples thereof include press molding, draw molding, and vacuum molding.
As a method of forming a composite of a rubber / polyester film laminate and a plastic molded body according to the present invention, for example, a rubber / polyester film laminate and a plastic molded body may be combined and integrally molded. After molding separately, both may be bonded with an adhesive or a pressure-sensitive adhesive. When the former method is used and a thermosetting resin is used as the plastic molded body, the thermosetting resin may be cured in the molding process, or pre- or post-curing treatment may be performed before and after molding.

  The rubber / polyester film laminate described above is laminated on the surface of the molded body so that the polyester film side of the rubber / polyester film laminate is the outermost surface in one of the forms of a composite used as a constituent material of the plastic molded body. There is a method to use. When used in this form, since the polyester film becomes the outermost layer, the occurrence of poor appearance due to the deterioration of the smoothness of the surface of the molded body is suppressed. Further, since the rubber / polyester film laminate of the present invention is laminated with a rubber layer, the rubber layer can relieve the distortion of the molded product generated at the time of molding, so that the molding accuracy and surface of the molded product can be reduced. Can be improved. Furthermore, since the external force applied to the molded body in use of the molded body can be relaxed by the elasticity of the rubber, the durability of the molded body can be improved. Further, since the rubber / polyester film laminate of the present invention is excellent in moldability as described above, it can follow molding of a complicated shape having a curved portion when used as a constituent material of a plastic molded body.

  Furthermore, in the above-mentioned usage pattern, it is preferable that at least one decorative layer selected from printing ink, metal thin film, inorganic thin film and paint is provided on the polyester film surface of the rubber / polyester film laminate. It is. For example, a molded body can be decorated by laminating printing ink, a metal thin film, and a paint, and the design of the molded body can be improved. Further, the lamination of the metal thin film or the inorganic thin film suppresses the permeation of oxygen gas, water vapor or the like to the molded body base layer, so that the durability of the molded body can be improved.

In the present invention, as described above, the cross-linked polymer layer is a more preferable embodiment in which both sides of the polyester film are coated. By this structure, when laminating a decoration layer on the opposite surface of the rubber layer of the above-mentioned polyester film for rubber lamination, the adhesion and adhesion durability between the decoration layer and the polyester film can be improved.
Lamination of the decorative layer may be performed after being combined with the molded body, or may be molded and combined after the decorative layer is previously stacked on the rubber / polyester film laminate.

  As described above, by using the rubber / polyester film laminate of the present invention, it was difficult to mold with a conventional biaxially oriented polyester film, and the molding pressure at the time of molding was 10 atm or less. Also in the molding methods such as vacuum molding and pressure molding, it is possible to obtain a molded product with good finish. In addition, these molding methods are advantageous in terms of economy in the production of molded products because the molding costs are low. Therefore, the effects of the rubber / polyester film laminate of the present invention can be exhibited most effectively by applying to these molding methods.

The formation method of said decoration layer is not limited. Various known methods can be applied. For example, as a printing method for forming the decorative layer, a known printing method such as gravure printing, flat printing, flexographic printing, dry offset printing, pad printing, or screen printing is used according to the product shape or printing application. be able to. In particular, offset printing and gravure printing are suitable for multicolor printing and gradation expression.
Further, the decorative layer may be not only a printed layer but also a metal or metal oxide thin film layer, and may further comprise a combination of a printed layer and a metal or metal oxide thin film layer. Examples of a method for forming a metal or metal oxide thin film layer include vapor deposition, thermal spraying, and plating. As the vapor deposition method, either a physical vapor deposition method or a chemical vapor deposition method can be used. Examples of physical vapor deposition include vacuum vapor deposition, sputtering, and ion plating. Examples of the chemical vapor deposition (CVD) method include a thermal CVD method, a plasma CVD method, and a photo CVD method.

Examples of the thermal spraying method include an atmospheric pressure plasma spraying method and a low pressure plasma spraying method. Examples of the plating method include an electroless plating (chemical plating) method, a hot dipping method, and an electroplating method. In the electroplating method, a laser plating method can be used. Among these, the vapor deposition method and the plating method are preferable for forming the metal layer, and the vapor deposition method is preferable for forming the metal oxide layer. The vapor deposition method and the plating method can be used in combination.
As the metal for the vapor deposition method, aluminum, chromium, silver, gold, and a combination thereof are used. Since it may be molded into a complicated shape, it is preferable that the metal forming the metal layer is excellent in spreadability. For example, in the case of aluminum metal, a compound containing a metal such as indium is preferable.

  In addition, in the case of using a decoration method for partially forming a metal or metal oxide thin film layer, after forming a solvent-soluble resin layer in a portion that does not require the thin film layer, the thin film layer is formed on the entire surface thereof. There is a method of removing the unnecessary metal thin film together with the solvent-soluble resin layer by forming a film and performing solvent cleaning. The solvent often used in this case is water or an aqueous solution. Further, as another decoration method, a method of forming such a thin film on the entire surface, then forming a resist layer on a portion where the thin film is to be left, etching with acid or alkali, and removing the resist layer Is mentioned.

The spreadability is a characteristic required even when the printing ink is used. Therefore, it is preferable to use a flexible resin such as a polyurethane resin as a main component as the binder resin constituting the printing ink.
You may perform formation of said decoration layer, after producing a plastic molding.
One of the forms in which the rubber / polyester film laminate is used as a constituent material of the plastic molded body is a method of using the rubber / polyester film laminated body as an intermediate layer of the plastic molded body. When used in this form, other than the effect of providing a decorative layer, which is one of the effects when used to become the outermost layer of the above plastic molded body, it should be expressed in the same manner as the above use. Can do.

  The rubber / polyester film laminate of the present invention can be suitably used as a member of a plastic molding as described above, but is not limited thereto. For example, the rubber / polyester film laminate itself can be used in combination with other materials. Taking advantage of the cushioning properties, cushioning properties, and gripping properties of the rubber layer of the rubber / polyester film laminate, it can be suitably used as a sealing material, cushioning material, and skin material for various devices and apparatuses. In particular, as described above, the rubber / polyester film laminate of the present invention is excellent in adhesion and durability of the polyester film and the rubber layer. Can be used particularly preferably.

  In the present invention, when used as a constituent material of a plastic molding as described above, in order to improve the adhesion between the rubber layer of the rubber / polyester film laminate and the base plastic material of the plastic molding, You may surface-treat the rubber | gum surface of a film laminated body with active rays, such as a plasma and a corona. An uncrosslinked rubber layer may be laminated on the rubber layer surface.

Hereinafter, the present invention will be described more specifically with reference to examples. These are all included in the technical scope of the present invention.
The measurement and evaluation methods employed in this specification are as follows.

(1) Film thickness Using a millitron, 5 points per sheet, a total of 15 points were measured, and the average value was obtained.
(2) Degree of plane orientation (ΔP)
A polyester film is obtained by using a sodium D line (wavelength 589 nm) as a light source, and using an Abbe refractometer, the refractive index in the longitudinal direction (Nz), the refractive index in the width direction (Ny), and the refractive index in the thickness direction (Nz). The surface orientation degree (ΔP) was calculated from the following equation.
ΔP = ((Nx + Ny) / 2) −Nz

(3) Stress at 10% elongation A sample was cut with a single-blade razor into strips having a length of 180 mm and a width of 10 mm, respectively, in the longitudinal direction and the width direction of the polyester film having a crosslinked polymer layer. Next, the strip sample was pulled using a tensile tester (manufactured by Toyo Seiki Co., Ltd.), and the stress at 10% elongation (MPa) and the elongation at break (%) in each direction were determined from the obtained load-strain curve. .
The measurement was performed in an atmosphere of 25 ° C. under the conditions of an initial length of 40 mm, a distance between chucks of 100 mm, a crosshead speed of 100 mm / min, a recorder chart speed of 200 mm / min, and a load cell of 25 kgf. In addition, this measurement was performed 10 times and the average value was used.

(4) Initial adhesive strength A knife is inserted into the interface between the rubber layer and the polyester film of the rubber / polyester film laminate, and stress is applied to the part with a finger to generate interface peeling. By T-type peeling method according to JIS K6854 The peel strength was measured.
(5) Solvent resistance adhesion strength The measurement sample obtained by cutting the rubber / polyester film laminate into 50 mm × 50 mm was placed in a 500 cc cylindrical glass container with a lid containing 400 cc of toluene, and the rubber layer of the sample was The container is covered with the sample soaked in toluene so that the entire sample is immersed in toluene. In the case where the sample does not immerse itself in toluene only by its own weight, for example, a polyester film of 60 mm × 60 mm and a thickness of 188 μm may be placed on the sample and weighted. The size and material of the weight are not particularly limited, and the entire sample may be immersed in toluene. The container containing the sample is allowed to stand at 25 ° C. for 72 hours. After standing still, the sample was quickly taken out from the container, toluene was wiped off, and the delamination strength was measured by the above method.

(6) Water-resistant adhesive strength A measurement sample obtained by cutting a rubber / polyester film laminate into 50 mm × 50 mm is placed in a cylindrical glass container with a lid of 400 cc containing distilled water and the rubber layer of the sample is The container was covered with water so that the entire sample was immersed in water. When the sample is not immersed in water by its own weight, for example, a polyester film of 60 mm × 60 mm and a thickness of 188 μm may be placed on the sample and weighted. The size and material of the weight are not particularly limited, and the entire sample may be immersed in water. The container containing the sample is placed in a gear oven set at 90 ° C. and allowed to stand for 14 days. After the heat treatment, take out the container from the oven, quickly take out the sample, put a knife at the interface between the rubber layer and the polyester film of the rubber / polyester film laminate, apply stress to the part with your fingers, and generate interface peeling, The peel strength was measured by a T-type peel method according to JIS K6854.

(7) Moldability (a) Mold moldability After printing on the rubber / polyester film laminate, contact heating with a hot plate heated to 100-140 ° C for 4 seconds, then mold temperature 30-70 ° C is maintained. Press molding was performed at a pressure time of 5 seconds. In addition, the heating conditions selected the optimal conditions within the said range with respect to each film. The shape of the mold is a cup shape, the opening has a diameter of 50 mm, the bottom has a diameter of 40 mm, a depth of 30 mm, and all corners are curved with a diameter of 0.5 mm. .
The moldability and finish of the five molded products molded under optimal conditions were evaluated and ranked according to the following criteria. In addition, (double-circle) and (circle) were set as the pass, and x was set as the disqualification.
A: (i) The molded product is not torn,
(Ii) the radius of curvature of the corner is 1 mm or less and the printing deviation is 0.1 mm or less,
(Iii) Further, there is no appearance defect corresponding to ×: (i) The molded product is not torn,
(Ii) The radius of curvature of the corner exceeds 1 mm and is 1.5 mm or less, or the printing deviation is 0.1
greater than 0.2 mm and less than 0.2 mm,
(Iii) Further, there is no appearance defect corresponding to ×, and there is no problem in practical use. ×: The molded product is broken, or even if it is not broken, it falls under any of the following items (i) to (iv) (I) A corner with a radius of curvature exceeding 1.5 mm (ii) A large crease and a poor appearance (iii) A film whitened and reduced in transparency (iv) A printing deviation of 0.2 mm More than

(B) Vacuum moldability After 5 mm square printing is performed on the rubber / polyester film laminate, the film is heated with an infrared heater heated to 500 ° C. for 10 to 15 seconds, and then at a mold temperature of 30 to 100 ° C. Vacuum forming was performed. In addition, the heating conditions selected the optimal conditions within the said range with respect to each film. The shape of the mold was a cup shape, the opening had a diameter of 50 mm, the bottom part had a diameter of 40 mm, the depth was 50 mm, and all corners were curved with a diameter of 0.5 mm. .
Five molded products that were vacuum-molded under the optimum conditions were evaluated for moldability and finish, and ranked according to the following criteria. In addition, (double-circle) and (circle) were set as the pass, and x was set as the disqualification.
A: (i) The molded product is not torn,
(Ii) the radius of curvature of the corner is 1 mm or less and the printing deviation is 0.1 mm or less,
(Iii) Further, there is no appearance defect corresponding to ×: (i) The molded product is not torn,
(Ii) The radius of curvature of the corner exceeds 1 mm and is 1.5 mm or less, or the printing deviation is 0.1
greater than 0.2 mm and less than 0.2 mm,
(Iii) Further, there is no appearance defect corresponding to ×, and there is no problem in practical use. ×: The molded product is broken, or even if it is not broken, it falls under any of the following items (i) to (iv) (I) A corner with a radius of curvature exceeding 1.5 mm (ii) A large crease and a poor appearance (iii) A film whitened and reduced in transparency (iv) A printing deviation of 0.2 mm More than

(8) Solvent resistance The sample was immersed in toluene adjusted to 25 ° C. for 30 minutes, and the appearance change before and after immersion was determined according to the following criteria. The haze value was measured by the method described above.
○: Little change in appearance, change in haze value is less than 1% ×: Change in appearance is observed, or change in haze value is 1% or more

(9) Ink adhesion The ink adhesion on the surface of the polyester film of the rubber / polyester film laminate was evaluated in accordance with the cross-cut evaluation method described in 8.5.1 of JIS-K5400. Specifically, after printing the following ink on the polyester film surface of the rubber / polyester film laminate, 100 cross-cut guides were used to create 100 1 mm squares with a cutter blade on the printing surface, and then an adhesive tape (manufactured by Nichiban Co., Ltd.). , Product name cellophane tape) was affixed to the printed surface and adhered completely so that no air remained. Next, after the adhesive tape was peeled off vertically, the remaining number of squares on the printed surface was evaluated as adhesion (remaining number / 100), and 80/100 or more was evaluated as ○, and less than that was determined as ×. .
Using UV curable ink (manufactured by Toka Dye Co., Ltd., Best Cure 161), the polyester film surface of the rubber / polyester film laminate was irradiated with 100 mJ of UV after printing with an RI tester, and evaluated according to the above method.

Example 1
[Coated polyester film for rubber lamination]
Polyethylene terephthalate (inherent viscosity: 0.65 dl / g) pellets containing 0.04% by mass of amorphous silica having an average particle size (SEM method) of 1.5 μm are sufficiently dried in vacuum and then heated at 280 ° C. for extrusion. It was supplied to a machine, extruded into a sheet form from a T-shaped base, wound around a mirror casting drum having a surface temperature of 30 ° C. using an electrostatic application casting method, and cooled and solidified. The unstretched film was stretched 3.0 times in the longitudinal direction while passing through a heating roll group at 105 ° C. to obtain a uniaxially oriented film. Both sides of this film were subjected to corona discharge treatment, and the following coating solutions were applied to both treatment surfaces. The coated uniaxially stretched film is guided to the preheating zone while being gripped with a clip, dried at 110 ° C., continuously stretched 3.2 times in the width direction in a heating zone of 125 ° C., and further at 195 ° C. 6% relaxation in the direction and heat treatment for 6 seconds were performed to obtain a coated polyester film for rubber lamination having a thickness of 100 μm in which a cross-linked polymer layer of 0.15 μm was coated on both sides.

[Coating solution]
The acid component is terephthalic acid / isophthalic acid / trimellitic acid / sebacic acid = 28 mol% / 9 mol% / 10 mol% / 3 mol%, and the glycol component is ethylene glycol / neopentyl glycol / 1,4- Methylolated melamine resin “Cymel (registered trademark) 303” (Mitsui Cytec Co., Ltd.) with respect to 100 parts by mass of ammonium salt type aqueous dispersion of polyester resin comprising butanediol = 15 mol% / 18 mol% / 17 mol% 5 parts by solid content and 0.025 part of “Catalyst 600” (Mitsui Cytec Co., Ltd.) as a catalyst was added and mixed to obtain a coating solution.

[Rubber / polyester film laminate]
EPDM (manufactured by Nippon Synthetic Rubber, EP21; ethylene content: 34% by mass) as rubber, and zinc salt of 2-mercaptobenzimidazole (manufactured by Ouchi Shinsei Chemical Co., Ltd., Nocrack MBZ) as aging inhibitor A As the inhibitor B, 4,4- (α, α-dimethylbenzyl) diphenylamine (manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., Nocrack CD) was used, respectively, and kneaded in a conventional manner at the following blending ratio.
(Composition composition)
(A) EPDM: 100.0 parts by mass (b) Polyethylene glycol (molecular weight 4000): 2.5 parts by mass (c) Stearic acid: 0.5 parts by mass (d) Anti-aging agent A: 1.5 parts by mass ( e) Anti-aging agent B: 0.7 parts by mass (f) Phenol formaldehyde resin: 2.0 parts by mass (g) MAF carbon: 30.0 parts by mass (h) FT carbon: 40.0 parts by mass (i) Polybutene : 15.0 parts by mass (j) N, N'-m phenylenedimaleimide: 1.5 parts by mass (k) 2,5-dimethyl-2,5-di (t-butylperoxy) hexane: 5.0 Parts by mass

  The kneaded rubber was formed into a sheet having a thickness of 3 mm. This unvulcanized rubber sheet is cut into 1 cm square pieces, and these pieces are weighed so that the ratio to toluene is 30% by mass and put into a stirrer with a vacuum deaerator together with toluene. Under stirring for 15 hours, the strip was dissolved in toluene. Subsequently, pentaerythritol tetraacrylate was added to this solution so that it might become 8 mass parts with respect to 100 mass parts of EPDM rubber | gum, and was stirred uniformly. Further, the vacuum deaerator was driven, and the mixture was further stirred for 20 minutes under vacuum with a gauge pressure of 750 mmHg for defoaming.

  Next, the EPDM rubber solution obtained by the above-described dissolution and defoaming was supplied to a roll coater, and applied to the coated polyester film for rubber lamination so that the thickness after drying was 0.15 mm. Then, it introduce | transduced into oven and dried at 80 degreeC. The surface of the EPDM rubber is made of a copolymer of poly-4-methylpentene-1 and has a thickness of 0.035 mm mat processing film (Mitsui Petrochemical Co., Ltd., Opulan X-60YMT4). The layers were stacked so as to face the surface, and continuously stacked using a pressure-bonding roll while pressing at a pressure of 5 kgf / cm. The obtained laminate was further continuously introduced into an electron beam irradiation apparatus, and pre-crosslinking was performed by irradiating an electron beam with an energy of 200 KV and 3 Mrad from the polyester film side. Subsequently, the cover sheet was peeled off to obtain a laminate composed of an EPDM rubber layer and a polyester film. Then, this laminate was further introduced into an electron beam irradiation apparatus, post-crosslinking was performed by 200 KV, 30 Mrad electron beam irradiation from the EPDM rubber layer side, and the obtained rubber / polyester film laminate was wound into a roll.

The properties of the obtained rubber / polyester film laminate are shown in Table 1.
The rubber / polyester film laminate obtained in this example was excellent in initial adhesive strength and solvent-resistant adhesive strength. Moreover, it was excellent also in mold moldability and ink adhesion, and could be suitably used as a member of a molded body.

(Comparative Example 1)
In the method of Example 1, a polyester film was obtained in the same manner as in Example 1 except that the application of the coating solution was stopped in the polyester film production process. A rubber / polyester film laminate was obtained in the same manner as in Example 1 using the obtained polyester film. The results are shown in Table 1. The rubber / polyester film laminate obtained in this comparative example was inferior in initial adhesive strength and solvent-resistant adhesive strength and was of low quality.

(Comparative Example 2)
In the method of Example 1, a polyester film was obtained in the same manner as in Example 1 except that the blending of the methylolated melamine resin, which is a crosslinking agent into the coating solution used in the polyester film production process, was stopped. A rubber / polyester film laminate was obtained in the same manner as in Example 1 using the obtained polyester film. The results are shown in Table 1. The rubber / polyester film laminate obtained in this Comparative Example was poor in solvent-resistant adhesive strength and low quality. Ink adhesion was also poor.

(Comparative Example 3)
In the method of Example 1, a rubber / polyester film laminate was obtained in the same manner as in Example 1 except that an unstretched polyester film was used instead of the polyester film. The results are shown in Table 1. Since the rubber / polyester film laminate obtained in this comparative example was not provided with a crosslinked polymer layer, the initial adhesive strength, solvent-resistant adhesive strength, and ink adhesion were inferior and low quality.

(Comparative Example 4)
In the method of Example 1, the coated polyester film for rubber lamination was the same as Example 1 except that the longitudinal stretching temperature was 95 ° C., the longitudinal and lateral stretching ratios were changed to 3.5 times, and the heat treatment temperature was changed to 225 ° C. Got. A rubber / polyester film laminate was obtained in the same manner as in Example 1 using the obtained polyester film for rubber lamination. The results are shown in Table 1. The coated polyester film for rubber lamination obtained in this comparative example had poor moldability and low quality.

(Example 2)
[Coated polyester film for rubber lamination]
Copolymer polyester chip having an intrinsic viscosity of 0.69 dl / g, comprising 100 mol% of terephthalic acid units as aromatic dicarboxylic acid components, 40 mol% of ethylene glycol units and 60 mol% of neopentyl glycol units as diol components. (A), 0.04% by mass of amorphous silica having an intrinsic viscosity of 0.69 dl / g and an average particle diameter (SEM method) of 1.5 μm, and a benzotriazole-based ultraviolet absorber (N) (Ciba -Chips (B) made of polyethylene terephthalate containing 0.67% by mass of Tinuvin 326) manufactured by Specialty Chemicals Co., Ltd. were dried. Furthermore, the chip (A) and the chip (B) were mixed so as to have a mass ratio of 25:75. Subsequently, these chip mixtures were melt-extruded from the slit of the T die at 270 ° C. with an extruder, rapidly cooled and solidified on a chill roll having a surface temperature of 40 ° C., and at the same time, the amorphous mixture was adhered to the chill roll using an electrostatic application method. A stretched sheet was obtained.

  The obtained unstretched sheet was stretched 3.3 times at 90 ° C. in the longitudinal direction between the heating roll and the cooling roll. Next, the coating solution used in Example 1 was applied to both sides of the uniaxially stretched film. The coated uniaxially stretched film is guided to a preheating zone while being gripped with a clip, dried at 110 ° C., guided to a tenter, preheated to 120 ° C. for 10 seconds, and the first half of transverse stretching is 110 ° C. and the latter half is 100 ° C. The film was stretched 3.9 times. Furthermore, heat setting treatment was performed at 235 ° C. while the first heat treatment (TS1) was 220 ° C. and the second heat treatment (TS2) was subjected to a 7% relaxation treatment in the lateral direction. A coated polyester film for rubber lamination having a thickness of 100 μm and coated with a polymer layer was obtained.

In the heat setting treatment zone, a 2m intermediate section is provided between the stretching section, a far infrared heater is installed in the heating section of the heat setting zone, and the limit position where the shielding plate in each section does not contact the film Expanded and installed. Also in the cooling section after heating, section shielding is strengthened, an external return method is used as a clip return method, a clip cooling device is installed, and forced cooling is performed with cold air of 20 ° C., and the clip temperature at the tenter outlet is set to 40. Measures were taken to prevent clip fusion to below ℃
A rubber / polyester film laminate was obtained in the same manner as in Example 1 using the obtained polyester film for rubber lamination. The results are shown in Table 1. Compared to the rubber / polyester film laminate obtained in Example 1, the rubber / polyester film laminate obtained in this example has improved moldability, is capable of vacuum molding, and has a higher quality. there were.

(Example 3)
In the method of Example 1, a polyester film was obtained in the same manner as in Example 1 except that the application of the coating solution was stopped in the polyester film production process. Both sides of the obtained polyester film are subjected to corona treatment, and further, a coater is used with a coating solution blended so that the solid content ratio of Byron 30SS and Coronate HX is 100: 30 (parts by mass) on both sides of the corona treatment. Then, the thickness after drying was applied to be 1 μm, and a crosslinked polymer layer was provided. A rubber / polyester film laminate was obtained in the same manner as in Example 1 using the obtained polyester film for rubber lamination. The results are shown in Table 1. The rubber / polyester film laminate obtained in this example had the same properties as the rubber / polyester film laminate obtained in Example 1 and was of high quality.

Example 4
In the method of Example 1, a coated polyester film for rubber lamination was obtained in the same manner as in Example 1 except that an acrylonitrile butadiene rubber (NBR) composition was used as the rubber composition. A rubber / polyester film laminate was obtained in the same manner as in Example 1 using the coated polyester film for rubber lamination obtained in this example. The results are shown in Table 1. The rubber / polyester film laminate obtained in this example had the same properties as the rubber / polyester film laminate obtained in Example 1 and was of high quality.

(Comparative Example 5)
In the method of Example 4, a polyester film was obtained in the same manner as in Example 4 except that the application of the coating solution was stopped in the polyester film manufacturing process. A rubber / polyester film laminate was obtained in the same manner as in Example 4, using the obtained polyester film. The results are shown in Table 2. The rubber / polyester film laminate obtained in this comparative example was inferior in initial adhesive strength and solvent-resistant adhesive strength and was of low quality.

(Comparative Example 6)
In the method of Example 4, the coated polyester film for rubber lamination was prepared in the same manner as in Example 4 except that the coating amount of the coating liquid was increased in the polyester film manufacturing process and the thickness after drying was changed to 15 μm. Obtained. A rubber / polyester film laminate was obtained in the same manner as in Example 4 using the polyester film obtained in this comparative example. The results are shown in Table 2. The rubber / polyester film laminate obtained in this comparative example had poor moldability and low quality. Further, the initial adhesive strength and solvent-resistant adhesive strength were also deteriorated as compared with the rubber / polyester film laminate obtained in Example 4.

(Example 5)
In the method of Example 2, a rubber / polyester film was obtained in the same manner as in Example 2 except that an acrylonitrile butadiene rubber (NBR) composition was used as the rubber composition. The results are shown in Table 2. The rubber / polyester film laminate obtained in this example had the same properties as the rubber / polyester film laminate obtained in Example 2 and was of high quality.

(Example 6)
In the method of Example 5, a coated polyester film for rubber lamination was obtained in the same manner as in Example 5 except that the application of the coating liquid in the polyester production process was changed to be applied to one side. Using the coated polyester film for rubber lamination obtained in this example, a rubber layer was laminated on the surface of the coating layer (crosslinked polymer layer), and a rubber / polyester film laminate was obtained in the same manner as in Example 5. It was. The results are shown in Table 2. The rubber / polyester film laminate obtained in this example was of high quality as in Example 5, but the cross-linked polymer layer was not formed on the surface opposite to the rubber layer, so the ink adhesion was poor. It was.

(Examples 7 to 9)
In the method of Example 2, a coated polyester film for rubber lamination was obtained in the same manner as in Example 2 except that the coating liquid used in the process for producing a coated polyester film for rubber lamination was changed to the following composition. A rubber / polyester film laminate was obtained in the same manner as in Example 2, using the coated polyester film for rubber lamination obtained in these examples. The results are shown in Table 2. The rubber / polyester film laminates obtained in these examples had the same or better properties as those of Example 2 and were of high quality.
[Coating liquid of Example 7]
(A) Acrylic resin copolymer emulsion [methyl methacrylate (60 mass%), ethyl acrylate (35 mass%), acrylic acid (2 mass%), N-methylolacrylamide (2 mass%), acrylonitrile (1 mass%) ), (B) melamine-based crosslinking agent (made of methylolated melamine), and (c) oxazoline-based crosslinking agent [methyl methacrylate (50 mass%), ethyl acrylate (25 mass%), styrene (5 (Mass%) and 2-isopropenyl-2-oxazoline (20 mass%) copolymerized] are 5 parts by mass of melamine crosslinking agent and 5 parts by mass of oxazoline crosslinking agent with respect to 100 parts by mass of acrylic resin. An aqueous coating solution formulated as described above was prepared.

[Coating liquid of Example 8]
192 parts by weight of polyether containing sodium sulfonate obtained by sulfonation of polyether of ethylene oxide (sulfonic acid group content: 8% by weight), 1013 parts by weight of polytetramethylene adipate, and 248 parts by weight of polypropylene oxide polyether were mixed and reduced in pressure. After dehydration at 100 ° C., the mixture was brought to 70 ° C., a mixture of 178 parts by mass of isophorone diisocyanate and 244 parts by mass of hexamethylene-1,6-diisocyanate was added, and the product mixture was further added with an isocyanate content of 5.6. The mixture was stirred in the range of 80 to 90 ° C. until the mass was reached. The obtained prepolymer was cooled to 60 ° C., and 56 parts by mass of biuret polyisocyanate obtained from 3 mol of hexamethylene diisocyanate and 1 mol of water, and 173 parts by mass of bisketimine obtained from isophoronediamine and acetone were sequentially added. Next, a 50 ° C. aqueous solution in which 15 parts by mass of hydrazine hydrate was dissolved was added to this mixture with stirring to obtain an aqueous polyurethane resin dispersion. An aqueous coating solution was prepared by adding 3 parts by mass of the oxazoline-based crosslinking agent used in Example 7 to 100 parts by mass of the polyurethane resin in the polyurethane resin aqueous dispersion.

[Coating liquid of Example 9]
A reaction vessel was charged with 95 parts by weight of dimethyl terephthalate, 95 parts by weight of dimethyl isophthalate, 35 parts by weight of ethylene glycol, 145 parts by weight of neopentyl glycol, 0.1 part by weight of zinc acetate and 0.1 part by weight of antimony trioxide. The transesterification was carried out over 3 hours. Next, 6.0 parts by mass of 5-sodium sulfoisophthalic acid was added, and esterification was performed at 240 ° C. over 1 hour, and then at 250 ° C. under reduced pressure (10 to 0.2 mmHg) over 2 hours. A polycondensation reaction was performed to obtain a copolyester resin having a number average molecular weight of 19,500 and a softening point of 60 ° C.
7.5% by mass of a 30% by mass aqueous dispersion of the obtained copolyester resin (A) and a 20% by mass aqueous solution of a self-crosslinking polyurethane resin (B) containing an isocyanate group blocked with sodium bisulfite. 11.3 parts by mass (Eastron H-3 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 0.3 parts by mass of a catalyst for Elastron (Cat 64 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 39.8 parts by mass of water and isopropyl alcohol 37.4 parts by mass were mixed.
Furthermore, colloidal silica (manufactured by NISSAN CHEMICAL INDUSTRY CO., LTD., Snowtex OL) as 0.6 parts by mass of a 10% by mass aqueous solution of a fluorine-based nonionic surfactant (manufactured by Dainippon Ink & Chemicals, Inc., MegaFac F142D); 2.3 parts by mass of a 20% by mass aqueous dispersion having an average particle size of 40 nm) and 3.5 masses of dry-process silica (produced by Nippon Aerosil Co., Ltd., Aerosil OX50; average particle size of 200 nm, average primary particle size of 40 nm) as particles B 0.5 parts by mass of% aqueous dispersion was added. Next, the pH of the coating solution is adjusted to 6.2 with a 5% by weight aqueous sodium bicarbonate solution, and the solution is precisely filtered through a felt type polypropylene filter having a filtration particle size (initial filtration efficiency: 95%) of 10 μm. Obtained.

(Example 10)
In the method of Example 2, a rubber / polyester film laminate was obtained in the same manner as in Example 2 except that the chloroprene rubber (CR) composition was used as the rubber composition. The results are shown in Table 2. The rubber / polyester film laminate obtained in this example had the same properties as the rubber / polyester film laminate obtained in Example 2 and was of high quality.

(Example 11)
In the method of Example 2, using a rubber component as a silicone rubber compound, a commercially available high-strength silicone rubber compound (manufactured by Shin-Etsu Chemical Co., Ltd., “KE555-U”) and a commercially available silicone rubber compound for general molding (Shin-Etsu Chemical Co., Ltd.) Manufactured by “KE958-U”) at a mass ratio of 60:40, and the amount of pentaerythritol tetraacrylate is changed to 3 parts by mass with respect to 100 parts by mass of the total amount of the silicone rubber compound. A rubber / polyester film laminate was obtained in the same manner as in Example 2 except that. The results are shown in Table 2. The rubber / polyester film laminate obtained in this example had the same properties as the rubber / polyester film laminate obtained in Example 2 and was of high quality. In particular, the rubber / polyester film laminate obtained in this example was excellent in properties related to adhesive strength.

(Example 12)
In Example 1, the same as Example 1 except that a self-crosslinking polyester resin made of a graft-modified polyester resin prepared by the following method was used as the coating liquid used in the process for producing a rubber-laminated coated polyester film. Thus, a coated polyester film for rubber lamination was obtained. Next, a rubber / polyester film laminate was obtained in the same manner as in Example 1 using the coated polyester film for rubber lamination. The properties of the obtained rubber / polyester film laminate are shown in Table 3.
The rubber / polyester film laminate obtained in Example 12 had higher properties than the rubber / polyester film laminate obtained in Example 1, and was of high quality.
[Coating fluid]
(Preparation of copolymer polyester resin)
40 parts of a self-crosslinking polyester resin aqueous dispersion “Vylonal (registered trademark) AGN702” (manufactured by Toyobo Co., Ltd.), 24 parts of water and 36 parts of isopropyl alcohol are mixed, and a 10% aqueous solution of an anionic surfactant 0.6 Part, propionate 1 part, colloidal silica particles (“Snowtex (registered trademark) OL”; average particle size 40 nm; manufactured by Nissan Chemical Industries Ltd.) 1.8% 20% aqueous dispersion, dry process silica particles (“ Aerosil OX50 "; average particle size 200 nm; average primary particle size 40 nm; manufactured by Nippon Aerosil Co., Ltd.

(Example 13)
In the method of Example 5, the coating solution used in the process for producing a rubber-laminated coated polyester film has the following composition, and the thickness of the crosslinked polymer layer is 0.08 μm on both sides as the thickness on the final rubber-laminated polyester film. A coated polyester film for rubber lamination was obtained in the same manner as in Example 5 except that the change was made. A rubber / polyester film laminate was obtained in the same manner as in Example 5 using the coated polyester film for rubber lamination obtained in this example. The results are shown in Table 3. The rubber / polyester film laminate obtained in this example was superior to the rubber / polyester film laminate obtained in Example 5 in solvent-resistant adhesive strength and water-resistant adhesive strength, and was of higher quality. In particular, the water-resistant adhesive strength was remarkably improved.

[Coating solution]
1. Production method of NBR-modified polyurethane (1) Synthesis of polyester polyol Stirrer, thermometer, 2L 4-neck flask equipped with Liebig condenser, 194 parts dimethylterephthalic acid, 194 parts dimethylisophthalic acid, 146 parts neopentyl glycol, ethylene 161 parts of glycol and 0.2 part of titanium monomer as a catalyst were charged and stirred at 190 ° C., 210 ° C. and 230 ° C. for 1 hour at each temperature, and the transesterification reaction was completed while distilling off the produced methanol. . Next, the temperature was raised to 250 ° C., and polymerization was performed under reduced pressure for 20 minutes to complete the reaction. The characteristics of the obtained polyester polyol were as follows.
Number average molecular weight 2000
Acid value is 5 eq / ton
Composition Acid component
Terephthalic acid 50 mol%
Isophthalic acid 50 mol%
Glycol component
Neopentyl glycol 50 mol%
Ethylene glycol 50 mol%

(2) Synthesis of NBR polyol oligomer 121 parts of liquid synthetic rubber CTBN 1300X13 (manufactured by Ube Industries) and 54 parts of toluene were uniformly dissolved in a 0.5 L four-necked flask equipped with a stirrer, a thermometer, and a condenser. Subsequently, 5.5 parts of glycidol and 02 parts of triphenylphosphine as a reaction catalyst were added and reacted at 105 ° C. for 6 hours to obtain a 70% toluene solution of NBR polyol oligomer. The acid values of the solid resin before and after the reaction were as follows.
Acid value of liquid synthetic rubber before reaction: 630 eq / ton
Acid value after reaction (generated NBR polyol oligomer): 90 eq / ton

(3) Synthesis of NBR-modified polyurethane 100 parts of the above polyester polyol, 2,2-dimethyl-3-hydroxypropyl-2 ′, 2′-dimethyl-3-hydroxy were added to a 1 L four-necked flask equipped with a stirrer, a thermometer and a condenser. 30 parts of propanate and 80 parts of toluene were charged and dissolved uniformly. Subsequently, 54 parts of 4,4′-diphenylmethane diisocyanate was added and reacted at 70 ° C. for 3 hours, and then diluted with 280 parts of cyclohexanone. Next, 115 parts of a 70% toluene solution of the NBR polyol oligomer was added, reacted at 70 ° C. for 3 hours, and diluted with 223 parts of methyl ethyl ketone to obtain a 30% solution of NBR-modified polyurethane.
In the above synthesis method, “part” means part by weight, and the acid value of resin, molecular weight, and composition analysis of polyester polyol were each carried out by the following methods.
-Number average molecular weight Gel permeation chromatography (GPC) 150C manufactured by Waters, Inc. was used, and measurement was performed at a flow rate of 1 ml / min using tetrahydrofuran as a carrier solvent. Three columns, Shodex KF-802, KF-804, and KF-806, manufactured by Showa Denko K.K., were connected as columns, and the column temperature was set to 30 ° C. As a molecular weight standard sample, polystyrene standard was used. Acid value 0.2 g of solid resin or 0.2 g of resin solution in solid content was dissolved in 20 ml of chloroform, and then phenolphthalein was used as an indicator with 0.1 N NaOH NaOH solution. And the measured value was shown as equivalent in 1 ton of resin solid content.
Polyester polyol composition A resin was dissolved in chloroform-d, and a resin composition ratio was determined by ¹ H-NMR using a nuclear magnetic resonance analyzer (NMR) “Gemini-200” manufactured by Varian.
(4) Coating solution A solution prepared by mixing NBR-modified polyurethane prepared by the above method and Millionate (registered trademark) MR (manufactured by Nippon Polyurethane Co., Ltd.), which is an isocyanate crosslinking agent, at a solid content mass ratio of 100: 150 is used. It was.

(Example 14)
By the method of Example 13, the thickness of the cross-linked polymer layer of the rubber lamination coating film was set to 0.2 μm on both sides to obtain a rubber lamination coating film. A rubber / polyester film laminate in which EPDM rubber was laminated in the same manner as in Example 1 was obtained using the obtained polyester film for rubber lamination. The results are shown in Table 3. The rubber / polyester film laminate obtained in this example is superior to the rubber / polyester film laminate obtained in Example 1 in terms of initial adhesive strength, solvent-resistant adhesive strength, and water-resistant adhesive strength. Met. In particular, the water-resistant adhesive strength was remarkably improved.

(Example 15)
In the method of Example 1, a polyester film was obtained in the same manner as in Example 1 except that the application of the coating solution was stopped in the polyester film production process. Both sides of the obtained polyester film were subjected to corona treatment, and further, the coating solution used in Example 13 was coated on the both surfaces subjected to the corona treatment using a coater so that the thickness after drying was 0.11 μm on both sides. Thus, a coated polyester film for rubber lamination was obtained. A rubber / polyester film laminate was obtained in the same manner as in Example 5 using the coated polyester film for rubber lamination obtained in this example. The results are shown in Table 3. The rubber / polyester film laminate obtained in this example was superior to the rubber / polyester film laminate obtained in Example 5 in solvent-resistant adhesive strength and water-resistant adhesive strength, and was of higher quality. In particular, the water-resistant adhesive strength was remarkably improved.

(Example 16)
In the method of Example 15, the composition ratio of the coating solution NBR-modified polyurethane and the isocyanate cross-linking agent Millionate (registered trademark) MR (manufactured by Nippon Polyurethane Co., Ltd.) is changed to a solid content mass ratio of 100: 10. Except for the above, a rubber-laminated coating film and a rubber / polyester film laminate were obtained in the same manner as in Example 15. The results are shown in Table 3. The rubber / polyester film laminate obtained in this example is inferior in adhesive properties to the rubber / polyester film laminate obtained in Example 15, but has the same characteristics as Example 5 and is of high quality. there were.

(Example 17)
In the method of Example 15, the composition ratio of the coating solution NBR-modified polyurethane and the isocyanate cross-linking agent Millionate (registered trademark) MR (manufactured by Nippon Polyurethane Co., Ltd.) is changed to a solid content mass ratio of 100: 100. Except for the above, a rubber laminated coating film and a rubber / polyester film laminate were obtained in the same manner as in Example 15. The results are shown in Table 3. The rubber / polyester film laminate obtained in this example had characteristics equivalent to those of the rubber / polyester film laminate obtained in Example 15, and was extremely high quality.

(Example 18)
In the method of Example 15, the isocyanate crosslinking agent in the coating solution was changed so that the composition ratio of Coronate (registered trademark) L (manufactured by Nippon Polyurethane Co., Ltd.) was 100: 250 in terms of the solid content mass ratio, and the crosslinked polymer A rubber laminated coating film and a rubber / polyester film laminate were obtained in the same manner as in Example 15 except that the layer thickness was changed to 0.02 μm as the thickness after drying. The results are shown in Table 3. The rubber / polyester film laminate obtained in this example had characteristics equivalent to those of the rubber / polyester film laminate obtained in Example 15, and was extremely high quality.

(Example 19)
As a core layer made of a fiber-reinforced thermoplastic resin sheet, a glass fiber-reinforced polypropylene resin sheet (thickness: 3.3) obtained by melt-impregnating a continuous glass fiber mat (a swirl roving mat subjected to needle punching) with a polypropylene resin. 7 mm, fiber content: 40 mass%) was used. The EPDM rubber solution used in Example 1 on the surface of the rubber / polyester film laminate obtained by laminating the EPDM rubber layer obtained by the method of Example 1 on the surface opposite to the rubber layer by printing. The rubber / polyester film laminate laminated to a thickness of 3 μm after drying is laminated on both sides of the core layer so that the rubber layer side of the rubber / polyester film laminate is the core layer side. The core layer and the surface layer were thermally fused by inserting into a mold and heating and pressurizing at a temperature of 200 ° C. and a pressure of 10 kg / cm ² by hot pressing. Next, cooling was performed to obtain a plastic molded body having a curved surface structure (hereinafter, simply referred to as a molded body). The surface of the obtained plastic molding had a highly smooth surface on which a mapping was projected, and the printing appearance was extremely excellent. Further, the dimensional accuracy of the molded body was good, and there was no distortion of the shape.

(Comparative Example 7)
In the method of Example 19, a plastic molding was obtained in the same manner as in Example 19 without laminating the rubber / polyester film laminate. The obtained plastic molding had surface irregularities such as glass fiber embossing and the surface condition was not good. Accordingly, although the same printing as that applied to the rubber / polyester film laminate used in Example 19 was performed on the surface of the molding, it did not look good.

(Comparative Example 8)
In the method of Example 19, instead of the rubber / polyester film laminate, an EPDM rubber sheet having a thickness of 250 μm was laminated, and a composite with a plastic molding was obtained in the same manner as in Example 19. Although the surface state of the composite with the obtained molded body was better than that of the molded body obtained in Comparative Example 7, there were surface irregularities such as partially raised glass fibers, which were obtained in Example 19. Compared with composites with plastic moldings, the surface condition was not good. Moreover, in this comparative example, since the EPDM rubber sheet was thin and the polyester film was not integrated, it was difficult to handle and the operability at the time of manufacturing the plastic molding was inferior.

(Comparative Example 9)
In the method of Example 19, a composite with a plastic molded body was obtained in the same manner as in Example 19 by using a single layer film having only a polyester layer in which the lamination of the rubber layer was stopped instead of the rubber / polyester film laminate. It was. Although the surface state of the composite with the obtained plastic molding was good, the dimensional accuracy and shape distortion of the plastic molding were inferior to those of the plastic molding obtained in Example 19.

(Example 20)
A carbon fiber fabric 4ply cut so that each side is a square with a side of 300 mm parallel to either warp or weft was laminated in a mold, and a peel ply and a resin distribution medium were laminated thereon. Next, after bagging with a nylon film and reducing the pressure to [atmospheric pressure-0.1] (MPa) using a vacuum pump, the mold was held at 90 ° C., and “Epicoat (registered trademark)” 828 ( “Cureazole (registered trademark)” 2E4MZ (part number, 2-ethyl-4-methylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd.) 3% by mass was added to 100% by mass of Japan Epoxy Resin Co., Ltd. (bisphenol A type epoxy resin).
Next, a liquid epoxy resin composition RTM resin composition was injected. The injection is finished 5 minutes after the RTM resin composition has flowed into the mold, and demolding is started 40 minutes after the RTM resin composition has flowed into the mold. A layer was obtained. The rubber layer side of the rubber / polyester film laminate obtained by laminating the NBR rubber layer obtained in Example 5 or the like on both sides of the obtained core layer (the NBR rubber layer surface was plasma-treated immediately before use) becomes the core layer side. This is inserted into a curved mold, heated and pressed at a temperature of 170 ° C. and a pressure of 10 kg / cm ² for 2 hours by hot press, molded and cured, and then cooled to form a plastic with a curved structure A molded body was obtained. The surface of the obtained plastic molding had a highly smooth surface for displaying a map. Further, the dimensional accuracy of the molded body was good, and there was no distortion of the shape.
The surface of the plastic molded body obtained by the above method was washed with isopropyl alcohol, and a melamine-based baking paint was applied so that the thickness of the coating film was 35 μm after drying. Then, it was left to stand at room temperature for 30 minutes, and further dried and baked in an oven at 140 ° C. for 30 minutes. The appearance of the coating film was very good. Moreover, the adhesiveness and adhesion durability of the coating film were also good.

(Comparative Example 10)
In the method of Example 20, a plastic molded body was obtained in the same manner as in Example 20 without laminating the rubber / polyester film laminate. The obtained plastic molding had surface irregularities such as carbon fiber embossing and the surface condition was not good. Therefore, the same printing as in Example 20 was performed on the surface of the plastic molded body, but the appearance was not good.

(Comparative Example 11)
In the method of Example 20, instead of the rubber / polyester film laminate, an NBR rubber sheet having a thickness of 250 μm was laminated, and a plastic molded article was obtained in the same manner as in Example 20. Although the surface state of the obtained plastic molding was better than that of the plastic molding obtained in Comparative Example 10, the molding obtained in Example 20 had surface irregularities such as carbon fiber partly raised. The surface condition was not good compared to the body. Moreover, like the comparative example 8, since the NBR rubber sheet was thin and the polyester film was not integrated, it was difficult to handle and the operativity at the time of plastic molding manufacture was inferior.

(Comparative Example 12)
In the method of Example 20, a composite with a plastic molded body was obtained in the same manner as in Example 20 using a polyester-only single-layer film in which the lamination of the rubber layer was stopped instead of the rubber / polyester film laminate. . Although the surface state of the composite with the obtained plastic molded body was good, the dimensional accuracy and shape distortion of the molded body were inferior to those of the plastic molded body obtained in Example 20. Moreover, the distortion of the plastic molding increased in the painting process.

(Example 21)
In the method of Example 20, a core layer made of a fiber reinforced plastic member was laminated on both sides of a rubber / polyester film laminate in which an NBR rubber layer was laminated. -A plastic molded body having a curved surface structure in which the polyester film laminate was an intermediate layer was obtained. The smoothness of the surface of the obtained plastic molded body was slightly inferior to the molded body obtained in Example 20, but was much better than the plastic molded body obtained in Comparative Example 10.

Industrial applicability

The coated polyester film for rubber lamination of the present invention is a cross-linked polymer film layer with a thin layer thickness, which improves the adhesion between the polyester film and the rubber layer, and eliminates the adhesive layer, so that the thick adhesive layer It is possible to avoid the deterioration of moldability caused by the above. In addition, a rubber / polyester film laminate having high adhesion between the polyester film and the rubber layer and excellent adhesion durability can be obtained.
Moreover, since the rubber / polyester film laminate of the present invention has excellent moldability, for example, when used as a member for a plastic molded body, the moldability of the plastic molded body is not lowered. Further, since the rubber / polyester film laminate of the present invention has a rubber layer laminated thereon, for example, when used as a member of the plastic molded product, the strain generated in the folding of the molded plastic product is reduced. Since it can be relaxed using elasticity, for example, the surface state of the plastic molded body can be improved, and the external force applied to the molded body in use of the plastic molded body can be relaxed by the elasticity of the rubber layer. For example, effects such as the appearance and durability of a plastic molded body being improved can be imparted. Moreover, since the polyester film is laminated | stacked, the rubber | gum and polyester film laminated body of this invention is excellent in the handleability compared with the rubber layer single-piece | unit product.
In addition, since the rubber / polyester film laminate of the present invention has excellent adhesion and adhesion durability between rubber and polyester film, for example, when used as a member for plastic molding, the durability of the plastic molding Will improve.
In addition, the rubber / polyester film laminate of the present invention includes a form in which a cross-linked polymer film layer is formed on both sides of the base polyester film, so that not only the adhesion to the rubber layer and the durability of adhesion, but also the rubber Also on the surface opposite to the surface on which the layers are laminated, for example, there is an advantage that the adhesiveness with the printing ink and the adhesive durability can be improved. Therefore, when decorating the surface of the polyester film of the rubber / polyester film laminate of the present invention by printing, painting, metal deposition, etc., the adhesion and adhesion between the printing ink, paint, metal thin film, etc. and the polyester film It has the advantage that durability is improved. In addition, when pasting other materials such as film, woven fabric, nonwoven fabric or molded body on the surface opposite to the surface on which the rubber layer is laminated, the advantage of improving the adhesion and adhesion durability between the material and the polyester film Also has.

The plastic molded body of the present invention has the following characteristics because the rubber / polyester film laminate is used as a component of the plastic molded body.
(1) Since the strain generated in the molding of a plastic molded body can be relaxed by utilizing the elasticity of the rubber layer, for example, the surface state of the plastic molded body can be improved and the strain generated during molding can be improved. In addition, the external force applied to the molded body in the use of the plastic molded body can be relaxed by the elasticity of the rubber layer. For example, the durability of the plastic molded body can be improved.
(2) Since the rubber / polyester film laminate is laminated with a polyester film, the rubber / polyester film laminate exhibits a reinforcing effect to increase the strength of the plastic molded article.
(3) Since the polyester film is laminated on the rubber / polyester film laminate, the barrier properties such as gas barrier properties of the plastic molded article may be improved.
(4) Polyester film surface smoothness and rubber when the polyester film surface of the rubber / polyester film laminate is laminated so that the polyester film surface side of the rubber / polyester film laminate is a surface layer. It has the advantage that extremely high surface smoothness can be obtained by the print-through effect of the layer. Therefore, high-quality surface decoration is possible when the surface of the plastic molded body is decorated.
(5) Since the rubber / polyester film laminate having the above characteristics is used, the adhesive strength between the coated polyester film and the rubber layer is high, and the durability of the adhesive strength is excellent. It can be suitably used as a constituent member of a molded body requiring durability such as a plate.

  Also, for example, in the form laminated with a rubber / polyester film laminate single film or other materials, utilizing the cushioning, buffering and gripping properties of the rubber layer of the rubber / polyester film composite, It can also be suitably used as a sealing material, cushioning material, skin material and the like. In particular, as described above, the rubber / polyester film laminate of the present invention is excellent in adhesion and durability of the polyester film and the rubber layer. Can be used particularly preferably. Therefore, it is important to contribute to the industry.

Claims (20)

  A polyester film having a degree of plane orientation of 0.005 to 0.15 has a crosslinked polymer film having a thickness of 0.003 to 5 μm on at least one surface, and 10% elongation stress (25 ° C. in the longitudinal direction and width direction of the film). ) Is 20 to 200 MPa, a coated polyester film for rubber lamination.   2. The coated polyester film for rubber lamination according to claim 1, wherein the crosslinked polymer film comprises at least one resin selected from polyester, polyurethane and acrylic polymer.   The coated polyester film for rubber lamination according to claim 1 or 2, wherein the crosslinked polymer film is crosslinked with a crosslinking agent.   The crosslinking agent is a melamine-based crosslinking agent, an oxazoline-based crosslinking agent, an isocyanate-based crosslinking agent, an aziridine-based crosslinking agent, an epoxy-based crosslinking agent, a methylolated or alkylolized urea-based, acrylamide-based, polyamide-based resin, an amide epoxy compound The coated polyester film for rubber lamination according to claim 3, which is at least one selected from a silane coupling agent and a titanate coupling agent.   The coated polyester film for rubber lamination according to claim 3 or 4, wherein the ratio of the resin constituting the crosslinked polymer film to the crosslinking agent is 0.5 or more in terms of the weight ratio of the crosslinking agent / resin.   6. The cross-linked polymer film according to claim 2, wherein the one or more self-crosslinkable polymers selected from the group consisting of self-crosslinkable polyesters, polyurethanes, and acrylic polymers include self-crosslinked polymers. A coated polyester film for rubber lamination as described in 1.   The coated polyester film for rubber lamination according to any one of claims 1 to 6, wherein the crosslinked polymer film is formed on both sides of the polyester film.   A rubber / polyester film laminate formed by laminating a rubber-coated polyester film according to any one of claims 1 to 6 and rubber.   The rubber / polyester film laminate according to claim 8, wherein the coated polyester film and the rubber layer are directly laminated without using an adhesive.   The rubber / polyester film laminate according to claim 8 or 9, wherein the adhesive strength between the coated polyester film and the rubber layer is 9 N / 20 mm or more.   The rubber / polyester film laminate according to any one of claims 8 to 10, wherein the adhesive strength between the coated polyester film and the rubber layer after immersion in toluene (25 ° C, 72 hours) is 8 N / 20 mm or more.   The rubber / polyester film laminate according to any one of claims 8 to 11, wherein the adhesive strength between the coated polyester film and the rubber layer after the water-resistant durability treatment by the method defined in the specification is 8 N / 20 mm or more.   10% elongation stress (25 ° C.) in the longitudinal direction and width direction of the film having a cross-linked polymer film having a thickness of 0.003 to 5 μm on at least one side of a polyester film having a degree of plane orientation of 0.005 to 0.15. The rubber / polyester film laminate according to claim 8, wherein an uncrosslinked rubber layer is laminated on the surface of the crosslinked polymer film of a polyester film having a thickness of 20 to 200 MPa, and then the uncrosslinked rubber layer is crosslinked. Production method.   The method for producing a rubber / polyester film laminate according to claim 13, wherein an adhesion improver is blended in the uncrosslinked rubber layer.   A composite of the rubber / polyester film laminate according to any one of claims 8 to 12 and a plastic molding.   The composite according to claim 15, wherein a polyester film is disposed on the outermost surface.   The composite according to claim 16, wherein a decorative layer comprising at least one selected from printing ink, metal thin film, inorganic thin film and paint is provided on the surface of the polyester film.   The composite according to claim 15, wherein the rubber / polyester film laminate is used as an intermediate layer of a plastic molding.   The composite according to any one of claims 15 to 18, wherein the plastic molding is a sheet.   The composite according to claim 19, wherein the plastic molded body has a curved portion.