JP7373964B2 - Films, security cards, passports, and film manufacturing methods - Google Patents

Description

The present invention relates to films, security cards, passports, and methods of manufacturing films. In particular, it relates to identification films and the like.

Conventionally, cards containing resin films and laminates thereof have begun to be used in ID cards, e-passports, non-contact IC cards, and the like. For the purpose of preventing counterfeiting, an encrypted code such as a QR code (registered trademark) or a photograph of the owner is pasted on the surface of a resin film. However, with this, there remains a possibility that QR codes and the like may be forged due to processes such as copying the entire print or removing and replacing photographs.
On the other hand, Patent Document 1 discloses a counterfeit prevention sheet in which two or more types of fluorescent fibers made of synthetic fibers are incorporated, and the fluorescent fibers are two or more types of fluorescent fibers with different lengths, An anti-counterfeit sheet is proposed, characterized in that the type and blending ratio of the fluorescent fibers are recorded by the manufacturer as unique information of the anti-counterfeit sheet, and authenticity can be determined by comparing with the unique information. has been done.
Patent Document 2 proposes an anti-counterfeit paper comprising a fibrous liquid crystal polymer that emits fluorescence when irradiated with ultraviolet rays.

Japanese Patent Application Publication No. 2009-000829 Japanese Patent Application Publication No. 2016-060997

As mentioned above, the use of films and the like containing fibrous molded bodies for identification purposes such as prevention of forgery and determination of authenticity is being considered. However, when such a fibrous molded body is composed of a thermoplastic resin, when the fibrous molded body is added to the thermoplastic resin, melt-kneaded, and formed into a film, the fibrous molded body is It has been found that the fibrous molded product itself may melt and the identification function of the fibrous molded product may not be fully exhibited.
The present invention aims to solve such problems, and provides a film containing a thermoplastic resin and a fibrous molded body, in which the fibrous molded body sufficiently exhibits an identification function. The present invention also aims to provide a method for manufacturing security cards, passports, and films.

As a result of the inventor's studies based on the above-mentioned problems, the above-mentioned problems were solved by the following means.
<1> (A) includes a thermoplastic resin and (B) a fibrous molded article, the (B) fibrous molded article includes a thermoplastic resin (b), and the thermoplastic resin (b) has a differential When measured with a scanning calorimeter, it exhibits at least one of the glass transition temperature T ² [°C] and the melting point T ³ [°C], and (A) the thermoplastic resin has a melt viscosity at a shear rate of 1,216 [1/s]. When the temperature at which the temperature becomes 500 [Pa·s] is T ¹ [°C], the temperature T ¹ [°C], the glass transition temperature T ² [°C] and the melting point T ³ [°C] are expressed by the following formula (1) and ( A film that satisfies at least one of 2).
(1) T ² > T ¹ - 30
(2) T ³ > T ¹ + 50
<2> The film according to <1>, wherein the content of the fibrous molded article (B) is 0.01 to 10.0 parts by mass based on 100 parts by mass of the thermoplastic resin (A).
<3> The film according to <1>, wherein the content of the fibrous molded article (B) is less than 2.0 parts by mass based on 100 parts by mass of the thermoplastic resin (A).
<4> The film according to any one of <1> to <3>, wherein the thermoplastic resin (b) has a glass transition temperature T ² [° C.] of 150≦T ² ≦300.
<5> The film according to any one of <1> to <3>, wherein the thermoplastic resin (b) has a melting point T ³ [° C.] of 230≦T ³ ≦380.
<6> The film according to any one of <1> to <5>, wherein the fibrous molded article (B) has a number average diameter of 200 μm or less.
<7> The film according to any one of <1> to <6>, wherein the fibrous molded article (B) has a number average fiber length of 500 μm or more.
<8> The film according to any one of <1> to <7>, wherein the thermoplastic resin (A) contains at least one selected from the group consisting of polycarbonate and polyester.
<9> The film according to any one of <1> to <8>, wherein the fibrous molded article (B) contains at least one selected from the group consisting of polyarylate and polyetheretherketone.
<10> The film according to any one of <1> to <9>, wherein the fibrous molded article (B) contains a phosphor.
<11> The film according to any one of <1> to <10>, having a thickness of 800 μm or less.
<12> The film according to any one of <1> to <11>, which is for a security card or a passport.
<13> A security card comprising the film according to any one of <1> to <12>.
<14> A passport containing the film described in any one of <1> to <13>.
<15> A resin composition including (A) a thermoplastic resin and (B) a fibrous molded article, wherein the (B) fibrous molded article includes a thermoplastic resin (b), and the thermoplastic resin (b) shows at least one of the glass transition temperature T ² [°C] and the melting point T ³ [°C] when measured with a differential scanning calorimeter, and (A) the shear rate of the thermoplastic resin is 1,216 [°C]. When the temperature at which the melt viscosity at 1/s is 500 [Pa·s] is T ¹ [°C], the temperature T ¹ [°C], the glass transition temperature T ² [°C], and the melting point T ³ [°C] A method for producing a film, which comprises extruding a resin composition that satisfies at least one of the following formulas (1) and (2).
(1) T ² > T ¹ - 30
(2) T ³ > T ¹ + 50

The present invention provides a film containing a thermoplastic resin and a fibrous molded body, in which the fibrous molded body sufficiently exhibits an identification function, a security card, a passport, and a method for producing the film. Now available.

FIG. 1 is a schematic diagram showing an example of the film of the present invention. FIG. 1 is a schematic diagram showing an example of the film of the present invention, where 1 indicates the film and 2 indicates a fibrous molded product.

The content of the present invention will be explained in detail below. In addition, in this specification, "~" is used to include the numerical values described before and after it as a lower limit value and an upper limit value.

[film]
The film of the present invention includes (A) a thermoplastic resin and (B) a fibrous molded article, the (B) fibrous molded article includes a thermoplastic resin (b), and the thermoplastic resin (b) indicates at least one of the glass transition temperature T ² [°C] and the melting point T ³ [°C] when measured with a differential scanning calorimeter, and the shear rate of the thermoplastic resin (A) is 1,216 [1/s] When ^{the temperature} at which the ^{melt viscosity} in It is characterized by satisfying at least one of (1) and (2).
(1) T ² > T ¹ - 30
(2) T ³ > T ¹ + 50
With such a configuration, a film including (A) a thermoplastic resin and (B) a fibrous molded body, in which the identification function is sufficiently exhibited by the (B) fibrous molded body, can be obtained. becomes available.
That is, in the present invention, by adjusting the various temperature relationships between (A) the thermoplastic resin, which is the main material of the film, and (B) the fibrous molded product, the fibrous molded product (B) becomes the molten state of (A). ) Even if it exists in a thermoplastic resin, it becomes possible to maintain a high percentage of its fibrous shape. More specifically, even when the fibrous molded article (B) used in the present invention is extruded into a film shape together with the thermoplastic resin (A), it is dispersed in the resulting film while maintaining its shape. can exist. More specifically, as shown in FIG. 1, the (B) fibrous molded bodies 2 are dispersed in the film 1 while maintaining their shape, and present in a unique pattern. Therefore, it can be distinguished from other films made of the same or similar materials by the difference in the dispersion state of the (B) fibrous molded product.
Specifically, in the present invention, the thermoplastic resin (b) constituting the fibrous molded article (B) has a glass transition temperature T ² [°C] and a melting point T ³ [°C] when measured with a differential scanning calorimeter. ], and when the temperature at which the melt viscosity of the thermoplastic resin (A) at a shear rate of 1,216 [1/s] is 500 [Pa・s] is T ¹ [°C], the temperature T ¹ [°C], glass transition temperature T ² [°C], and melting point T ³ [°C] satisfy at least one of the following formulas (1) and (2).
(1) T ² > T ¹ - 30
(2) T ³ > T ¹ + 50

In the present invention, at least one of the following formulas (1) and (2) may be satisfied. One of the preferred embodiments of the present invention is an aspect that satisfies formula (1) but does not satisfy formula (2). Another preferred embodiment of the present invention is an aspect that satisfies formula (2) but does not satisfy formula (1).
Formula (1) allows the fibrous molded article (B) to maintain its shape for the following reason.
The temperature T ¹ [°C] indicates the temperature level ^at which the (A) thermoplastic resin, which is the main material of the film, is molded into a film shape. In order to maintain the shape, it is necessary to satisfy at least one of formula (1) and formula (2). That is, the fibrous molded article (B) can maintain its fibrous form without being melted and dispersed when extrusion molded into a film together with the thermoplastic resin (A). In addition, when (B) the fibrous molded product is made of an amorphous resin, one of the criteria is usually the glass transition point T ² [°C] shown by a differential scanning calorimeter, and when it is made of a crystalline resin, usually One of the criteria is the melting point T ³ [° C.] as measured by a differential scanning calorimeter.
In formula (1), T ¹ −T ² is preferably 25 [° C.] or less. Further, it is preferable that the lower limit value of T ¹ -T ² is -30 [°C] or more.
In formula (2), T ³ -T ¹ is preferably 60 [°C] or more, more preferably 70 [°C] or more, and even more preferably 80 [°C] or more. Further, the upper limit value of T ³ -T ¹ is preferably 110 [°C] or less, and more preferably 100 [°C] or less.
The temperature T ¹ at which the melt viscosity at a shear rate of 1,216 [1/s] is 500 [Pa·s] is preferably 200 [°C] or higher, and preferably 220 [°C] or higher. Further, the temperature is preferably 290 [°C] or less, more preferably 270 [°C] or less.
In the present invention, when two or more types of (A) thermoplastic resins are included, T ¹ [°C] is T ¹ [°C] of the mixture. Also, when the thermoplastic resin (b) constituting the fibrous molded article (B) is composed of two or more types, the T ² [°C] and T ³ [°C] of the mixture are the T ² of the thermoplastic resin (b). [°C] and T ³ [°C].

Although the thickness of the film of the present invention is not particularly limited, it is preferably 800 μm or less, more preferably 300 μm or less, and even more preferably 200 μm or less. Moreover, the lower limit of the thickness of the film of the present invention is practically 50 μm or more.

<(A) Thermoplastic resin>
The present invention includes (A) a thermoplastic resin.
(A) The type of thermoplastic resin is not particularly limited, and includes polyolefins such as polyethylene and polypropylene, polyesters such as polyamide, polyethylene terephthalate, and polybutylene terephthalate, polycarbonate, polyoxymethylene, polyether ketone, polyether ether ketone, and polyester. Polyetherketones such as etherketoneketone and polyetheretherketoneketone, thermoplastic polyimide resins such as polyethersulfone, polyethersulfide, thermoplastic polyetherimide, thermoplastic polyamideimide, fully aromatic polyimide, and semiaromatic polyimide. It is preferable to include at least one selected from the group consisting of polycarbonate and polyester.

<<Polycarbonate>>
Polycarbonates include -[O-R-OCO]- units containing carbonate ester bonds in the molecular main chain (R contains an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group, and It is not particularly limited as long as it contains a straight chain structure or a branched structure. However, from the point of view of impact resistance and heat resistance, stability as an aromatic dihydroxy compound, and the fact that it contains a small amount of impurities but is easily available, aromatic polycarbonate is more preferred. It will be done. Examples of aromatic polycarbonates include those having a bisphenol A skeleton.

Although there are no specific restrictions on the specific type of polycarbonate, examples thereof include polycarbonate obtained by reacting a dihydroxy compound and a carbonate precursor. At this time, in addition to the dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. Alternatively, a method in which carbon dioxide is used as a carbonate precursor and is reacted with a cyclic ether may also be used. Moreover, the polycarbonate may be a monopolymer consisting of one type of repeating unit, or a copolymer having two or more types of repeating units. At this time, the copolymer can be selected from various copolymerization forms such as a random copolymer and a block copolymer.

The method for producing polycarbonate is not particularly limited, and any method can be adopted. Examples include interfacial polymerization, melt transesterification, pyridine method, ring-opening polymerization of cyclic carbonate compounds, and solid phase transesterification of prepolymers.

The molecular weight of the polycarbonate is preferably 10,000 to 35,000, more preferably 10,500 or more, as a viscosity average molecular weight calculated from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent. More preferably, it is 11,000 or more, even more preferably 11,500 or more, even more preferably 12,000 or more. Further, it is preferably 32,000 or less, more preferably 29,000 or less. By setting the viscosity average molecular weight at or above the lower limit of the above range, the mechanical strength of the film of the present invention can be further improved, and by setting the viscosity average molecular weight at or below the upper limit of the above range, the fluidity of the resin can be improved. This can be improved by suppressing the decrease, and molding processability tends to improve.
Note that two or more types of polycarbonates having different viscosity average molecular weights may be mixed and used, and in this case, polycarbonates having a viscosity average molecular weight outside the above-mentioned preferred range may be mixed.
Here, the viscosity average molecular weight [Mv] is calculated by calculating the intrinsic viscosity [η] (unit: dL/g) at a temperature of 25°C using an Ubbelohde viscometer using methylene chloride as a solvent, and using Schnell's viscosity formula, That is, it means the value calculated from η=1.23×10 ⁻⁴ Mv ^0.83 . Moreover, the intrinsic viscosity [η] is a value calculated by measuring the specific viscosity [η _sp ] at each solution concentration [C] (g/dL) and using the following formula.

<<Polyester>>
As the polyester resin, for example, PET (polyethylene terephthalate), PETG, PCTG (polyethylene terephthalate glycol-modified with cyclohexanedimethanol), etc. are used, and PETG and PCTG are preferable.

The film of the present invention preferably contains (A) thermoplastic resin in an amount of 90% by mass or more of the film, more preferably 95% by mass or more, and still more preferably 97% by mass or more. (A) The upper limit of the content of the thermoplastic resin is, for example, 99.999% by mass.
Moreover, one embodiment of the film of the present invention is a form in which the film contains polycarbonate in an amount of 90% by mass or more, preferably 95% by mass or more, and more preferably 97% by mass or more. The upper limit of the polycarbonate content is, for example, 99.999% by mass.
In another embodiment of the film of the present invention, the film contains polyester in an amount of 90% by mass or more, preferably 95% by mass or more, and more preferably 97% by mass or more. The upper limit of the polyester content is, for example, 99.999% by mass.

The film of the present invention may contain only one type of (A) thermoplastic resin, or may contain two or more types of thermoplastic resin. When two or more types are included, it is preferable that the total amount falls within the above range.

<(B) Fibrous molded body>
The film of the present invention includes the above-mentioned (B) fibrous molded product. Fibrous means a shape that is sufficiently long in length relative to its cross section. More specifically, it is preferable that the number average diameter and number average fiber length, which will be described later, be satisfied. In the present invention, when the (B) fibrous molded product is extruded together with the (A) thermoplastic resin, it generally exists dispersed in the (A) thermoplastic resin film. The film in which (B) the fibrous molded body used in the present invention is present is different from other films made of the same type of material in the dispersion state of the (B) fibrous molded body, and is suitable for identification. Can be used.

(B) The number average diameter of the fibrous molded product is preferably at most 200 μm, more preferably at most 160 μm, even more preferably at most 120 μm, and the obtained film is It is possible to more effectively reduce the unevenness of the film, and to make it difficult for the fibrous molded product to fall out of the film. Further, the lower limit of the number average diameter is preferably 10 μm or more, more preferably 50 μm or more, and even more preferably 80 μm or more. By setting the value to be equal to or higher than the lower limit value, visual observation tends to become easier during identification.
Moreover, the cross section of the fibrous molded article (B) may be circular or non-circular. (B) When the cross section of the fibrous molded body is non-circular, the number average diameter is the diameter of a circle corresponding to the area of the cross section.
(B) The number average fiber length of the fibrous molded product is preferably 500 μm or more, more preferably 900 μm or more, even more preferably 1300 μm or more, and even more preferably 1700 μm or more. Visibility tends to be further improved by making it equal to or more than the lower limit value. Further, the upper limit of the number average fiber length is preferably 5 mm or less, more preferably 4 mm or less, even more preferably 3 mm or less, even more preferably 2600 μm or less, and 2200 μm or less. It is even more preferable that there be. By setting it below the above-mentioned upper limit, agglomeration during extrusion molding of the film can be more effectively suppressed.

<<Thermoplastic resin (b)>>
The fibrous molded article (B) used in the present invention is composed of a thermoplastic resin (b). That is, the thermoplastic substance (b) is usually present in the thermoplastic resin (A) as a fibrous molded article (B), dispersed in the form of fibers. The thermoplastic resin (A) and the thermoplastic resin (b) have a relationship that satisfies at least one of the above formula (1) and formula (2). (B) The fibrous molded product has a thermoplastic resin (b) as its main component, and may contain other components without departing from the spirit of the present invention.
In the present invention, the glass transition temperature T ² [°C] of the thermoplastic resin (b) is preferably 150≦T ² ≦300, more preferably 170≦T ² ≦300, and 190≦T ² More preferably, it is ≦300. By setting it to the above lower limit or more, it will have a certain heat resistance, and the fibrous molded article (B) tends to easily maintain its fibrous form during film molding. Moreover, by setting it below the said upper limit, the molding processability at the time of molding thermoplastic resin (b) into a fibrous shape is excellent.

In the present invention, the melting point T ³ [°C] of the thermoplastic resin (b) is preferably 230≦T ³ ≦380, more preferably 250≦T ³ ≦380, and 270≦T ³ ≦360. It is more preferable that By setting it to the above lower limit or more, it will have a certain heat resistance, and the fibrous molded article (B) tends to easily maintain its fibrous form during film molding. Moreover, by setting it below the said upper limit, the molding processability at the time of molding thermoplastic resin (b) into a fibrous shape is excellent.

In the present invention, the fibrous molded article (B) preferably contains at least one selected from the group consisting of polyarylate, polyether ether ketone, liquid crystal polymer, polyester, and polyamide, and polyarylate and polyether It is more preferable that at least one selected from the group consisting of ether ketones is included. In particular, by using a resin with a high glass transition temperature or melting point, such as polyarylate and polyetheretherketone, as the main component of (B) the fibrous molded product, it is possible to blend it into the molten resin that is the main component of the film, etc. , it becomes possible to better maintain its fibrous form.

(B) The fibrous molded article preferably contains the thermoplastic resin (b) in a total amount of 90% by mass or more, more preferably 93% by mass or more, and even more preferably 95% by mass or more. Further, the upper limit of the total amount is preferably 99.99% by mass or less, more preferably 99.9% by mass or less.

The polyarylate used in the present invention preferably has a glass transition temperature of 180°C or higher, more preferably 185°C or higher, even more preferably 190°C or higher, and even more preferably 195°C or higher, as measured by a differential scanning calorimeter. More preferably, the temperature is above 200°C, or 210°C or above. By setting the amount to be equal to or more than the lower limit, the fibrous morphology tends to be more effectively maintained during extrusion molding of the film. Further, the upper limit of the glass transition temperature of the polyarylate is preferably 300°C or lower, more preferably 280°C or lower. By setting the temperature to below the upper limit, the temperature tends to move away from the decomposition temperature of the resin, so that deterioration due to a decrease in molecular weight during molding can be more effectively suppressed.

The polyarylate used in the present invention is preferably an aromatic polyester composed of repeating units derived from an aromatic dicarboxylic acid and repeating units derived from bisphenol.
Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, benzophenone dicarboxylic acid, and 4,4'-diphenyl dicarboxylic acid. , 3,3'-diphenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, and the like.
Examples of bisphenols include 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3, 5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide , 4,4'-dihydroxydiphenylketone, 4,4'-dihydroxydiphenylmethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1, Examples include 1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane. These compounds may be used alone or in combination of two or more.

The method for producing polyarylate is not particularly limited, and those obtained by known methods can be used. Polyarylates obtained by interfacial polymerization and melt polymerization can be suitably used.

The polyetheretherketone (PEEK) used in the present invention preferably has a melting point of 320°C or higher, more preferably 325°C or higher, as measured by a differential scanning calorimeter. By setting the amount to be equal to or more than the lower limit, the fibrous morphology tends to be more effectively maintained during extrusion molding of the film. Further, the upper limit of the melting point of the polyetheretherketone is preferably 380°C or lower, more preferably 350°C or lower. By setting the temperature to below the upper limit, the temperature tends to move away from the decomposition temperature of the resin, so that deterioration due to a decrease in molecular weight during molding can be more effectively suppressed.
Further, the glass transition temperature of polyetheretherketone measured with a differential scanning calorimeter is preferably 120°C or higher, more preferably 130°C or higher. By setting the amount to be equal to or more than the lower limit, the fibrous morphology tends to be more effectively maintained during extrusion molding of the film. Further, the upper limit of the glass transition temperature of the polyetheretherketone is preferably 170°C or lower, more preferably 160°C or lower. By setting the temperature to below the upper limit, the temperature tends to move away from the decomposition temperature of the resin, so that deterioration due to a decrease in molecular weight during molding can be more effectively suppressed.

Polyetheretherketone is a polymer containing repeating units represented by the following formula.
-Ar-C(=O)-Ar-O-Ar'-O-
(In the formula, Ar and Ar' each independently represent an arylene group.)
For details of the polyetheretherketone, the descriptions in paragraphs 0036 to 0038 of JP 2017-003722A can be referred to, and the contents thereof are incorporated herein.

Commercially available PEEK products include, for example, the "Victrex PEEK" series manufactured by Victrex, such as PEEK 450G, 381G, 151G, and 90G (trade name) manufactured by Victrex. Further examples include VESTAKEEP (trade name) manufactured by Daicel Degussa. It is also marketed by Solvay.

The liquid crystal polymer used in the present invention has, for example, a structure based on parahydroxybenzoic acid. More specifically, a liquid crystal polyester obtained by polymerizing parahydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and other monomers is exemplified.
Examples of commercially available liquid crystal polymers include UENO LCP manufactured by Ueno Pharmaceutical Co., Ltd., Sumika Super LCP manufactured by Sumitomo Chemical, and Liquid Crystal Polymer manufactured by KDA.

As the polyester, polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, polybutylene terephthalate, etc. can be used. An example of the melting point of polyester is 250 to 270°C.

As the polyamide, polyamide 6, polyamide 66, polyamide 6T, polyamide 6I/6T, xylylene diamine polyamide (MXD6, etc.), etc. can be used. An example of the melting point of polyamide is 250 to 350°C.

The film of the present invention preferably contains the fibrous molded article (B) in a proportion of 0.01 parts by mass or more, and preferably 0.02 parts by mass or more, based on 100 parts by mass of the (A) thermoplastic resin. is more preferable. Further, it is preferable that the fibrous molded article (B) is contained in a proportion of 10.0 parts by mass or less, more preferably 7.0 parts by mass or less, based on 100 parts by mass of (A) thermoplastic resin. It is more preferably 5.0 parts by mass or less, even more preferably less than 2.0 parts by mass, even more preferably 1.0 parts by mass or less, even if it is 0.5 parts by mass or less. The amount may be 0.3 parts by mass or less, or 0.1 parts by mass or less.
The film of the present invention may contain only one kind of the above-mentioned (B) fibrous molded product, or may contain two or more kinds. When two or more types are included, it is preferable that the total falls within the above range.

＜＜Fluorescent material＞＞
The fibrous molded article (B) used in the present invention preferably contains a phosphor. By including the phosphor, identification by irradiation with light becomes easier.
The phosphor is not particularly limited as long as it emits light when irradiated with light (for example, at least one type selected from ultraviolet light and infrared light), and preferably it emits visible light or infrared light when irradiated with ultraviolet light or the like. Those that emit light are preferred. The phosphor may be an inorganic phosphor or an organic phosphor.
(B) The fibrous molded product used in the present invention is prepared by adding a phosphor (especially in the case of an inorganic phosphor) to 100 parts by mass of the thermoplastic resin (b) constituting the fibrous molded product. It is preferable to contain 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, and even more preferably 1.0 parts by mass or more. Furthermore, the fibrous molded article (B) used in the present invention preferably contains 5 parts by mass or less, and preferably 3 parts by mass or less of a phosphor, based on 100 parts by mass of the total amount of polyarylate and polyetheretherketone. More preferably, it is contained in an amount of 2.5 parts by mass or less.
In particular, when the phosphor is an organic phosphor (particularly a dye), it is preferably contained at 0.01 parts by mass or more, more preferably at least 0.02 parts by mass, even more preferably at least 0.03 parts by mass. . Further, the fibrous molded article (B) used in the present invention preferably contains 1.0 parts by mass or less, and 0.5 parts by mass of an organic dye, based on 100 parts by mass of the total amount of polyarylate and polyetheretherketone. It is more preferable to contain 0.3 parts by mass or less, and even more preferably 0.3 parts by mass or less.
(B) The fibrous molded product may contain only one type of phosphor, or may contain two or more types of phosphor. When two or more types are included, it is preferable that the total amount falls within the above range.

<<<Inorganic phosphor>>>
Inorganic phosphors include B, F, Mg, Al, Si, P, S, Cl, Ca, V, Mn, Cu, Zn, Ge, Sr, Y, Ba, La, Ce, Pr, Nd, Pm, Sm , Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. Examples of compounds constituting the phosphor include composite oxides of these elements and oxygen atoms.

As the phosphor, it is preferable to use a phosphor that emits light in infrared light or ultraviolet light, and it is more preferable to use a phosphor that emits light in ultraviolet light. Examples of phosphors that emit light with ultraviolet light include those that are excited by ultraviolet light and have emitted spectrum peaks in wavelength ranges such as blue, green, and red. Specifically, trace amounts of metals (copper, silver, manganese, bismuth, lead, etc.) are added as activators to high-purity phosphors such as zinc sulfide and alkaline earth metal sulfides to make them emit stronger. Examples include those obtained by high-temperature firing. Phosphors that emit light with ultraviolet light can have their hue, brightness, and degree of color attenuation adjusted by combining host crystals and activators.

The inorganic phosphor preferably has an average particle diameter (D ₅₀ ) of 0.01 μm or more. Further, the upper limit of the average particle diameter (D ₅₀ ) is preferably 50 μm or less, preferably 10 μm or less, and more preferably 5 μm or less. By setting it below the above-mentioned upper limit, it is possible to further reduce the possibility that molding defects such as thread breakage will occur when processing into fibers.

Examples of the compound that can be used as an inorganic phosphor in the present invention include the descriptions in paragraphs 0019, 0090 to 0097 of JP-A No. 2015-168728, paragraphs 0033, 0034, 0069 of JP-A-10-129107, etc. , the descriptions of which are incorporated herein.

<<<Organic phosphor>>>
The compound used as the organic phosphor is usually a pigment or a dye, with dyes being preferred.
Examples of the compound used as an organic phosphor include the following.
Red light emitting phosphor: Rare earth complex compounds such as Eu complex compounds, Sm complex compounds, Pr complex compounds, dicyanomethylene compounds, benzopyran derivatives, rhodamine derivatives, benzothioxanthene derivatives, polyalkylthiophene derivatives Yellow light emitting phosphors: Rubrene compounds , perimidone derivatives Blue-emitting phosphor: coumarin-based compounds, perylene-based compounds, pyrene-based compounds, anthracene-based compounds, naphthalene-based compounds, distyryl derivatives, polydialkylfluorene derivatives, polyparaphenylene derivatives, benzoxazole derivatives Green-emitting phosphors: coumarin type compounds, rare earth complex compounds such as Tb complex compounds, quinacridone compounds, quinoline compounds

As such an organic phosphor, commercially available products can be used. For example, as a blue-emitting phosphor, "Lumisys/B-800" and "Lumisys/B-1400" manufactured by Central Techno Co., Ltd., and Showa Kagaku Kogyo Co., Ltd. "Hakkol PSR" manufactured by Clariant Japan, "Hostalux KS" manufactured by Clariant Japan, "Lumisys/G-900" and "Lumisys/G-3300" manufactured by Central Techno as green-emitting phosphors, and "Lumisis/G-3300" manufactured by Central Techno as red-emitting phosphors, Central "Lumisis/E-400" manufactured by Techno Co., Ltd. can be used.

<Other ingredients>
In addition to the above-mentioned components, the components constituting the film may contain additives such as antioxidants, heat stabilizers, flame retardants, flame retardant aids, and mold release agents. Alternatively, additives such as ultraviolet light absorbers, antistatic agents, optical brighteners, antifogging agents, fluidity improvers, plasticizers, dispersants, antibacterial agents, etc. may be contained as long as they do not impair the effects of the present invention. Good too. The content of the additives as described above is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, based on the mass of the entire thermoplastic resin (A), and 0.0% by mass or less, more preferably 0.5% by mass or less, It is more preferable that the amount is .1% by mass or less.

<Film manufacturing method>
The method for producing the film of the present invention is not particularly limited, but an example is to blend (B) a fibrous molded article into a molten thermoplastic resin (A), knead it, and extrude it.
Another example is to blend the (B) fibrous molded article into the (A) thermoplastic resin in the form of pellets, then melt the (A) thermoplastic resin, knead the two, and perform extrusion molding.
In the present invention, (A) thermoplastic resin in a molten state is blended with (B) fibrous molded product, or (A) thermoplastic resin is blended with (B) fibrous molded product, and then (A) Even when the thermoplastic resin is melted, it can maintain its fibrous shape.
More specifically, the method for producing a film of the present invention provides a resin composition containing (A) a thermoplastic resin and (B) a fibrous molded article, wherein the (B) fibrous molded article is heated The thermoplastic resin (b) exhibits at least one of a glass transition temperature T ² [°C] and a melting point T ³ [°C] when measured with a differential scanning calorimeter, and ( A) When the temperature at which the melt viscosity of the thermoplastic resin at a shear rate of 1,216 [1/s] is 500 [Pa·s] is T ¹ [°C], the temperature T ¹ [°C], the glass transition temperature The method includes extrusion molding a resin composition whose T ² [°C] and melting point T ³ [°C] satisfy at least one of the following formulas (1) and (2).
(1) T ² > T ¹ - 30
(2) T ³ > T ¹ + 50

Moreover, it may be a multilayer body containing the film of the present invention, and in this case, the thermoplastic resin (A) constituting each layer can be coextruded.

[Applications of film]
The film of the present invention is preferably used for authenticity determination. In particular, it is preferably used for determining authenticity by irradiating light.
The film of the present invention can further be used in combination with other layers.
The film of the present invention can also be used in security cards or passports. More specifically, it is suitably used as an ID card, e-passport, non-contact IC card, etc. However, its uses are not limited, and it can be widely used in fields where prevention of counterfeiting is desired, such as product tags, distribution information, personal data management, and crime prevention systems.
Also disclosed herein are security cards comprising the films of the invention and passports comprising the films of the invention.

In addition, without departing from the spirit of the present invention, reference may be made to the descriptions in Japanese Patent Publication No. 2010-514950, the descriptions in Japanese Patent Application Publication No. 2006-504883, and the descriptions in Japanese Patent Application Laid-open No. 2009-228172, and their contents are incorporated herein by reference. Incorporated into the specification.

The present invention will be explained in more detail with reference to Examples below. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[(B) Production of fibrous molded body]
<(B) Thermoplastic resin (b) constituting the fibrous molded body>
VICTREX PEEK 450G: manufactured by Victrex, polyetheretherketone resin (PEEK), glass transition temperature (T ² ) 146°C, melting point (T ³ ) 331°C
U polymer D type: Manufactured by Unitika, polyarylate resin (PAR), glass transition temperature (T ² ) 198°C, U polymer that did not show a melting point (T ³ ) when measured by DSC T-240AF: Manufactured by Unitika, polyarylate resin (PAR) Arylate resin (PAR), glass transition temperature (T ² ) 218°C, U polymer that showed no melting point (T ³ ) when measured by DSC T-200: manufactured by Unitika, polyarylate resin (PAR), glass transition temperature ( Torelina A-900: manufactured by Toray Industries, polyphenylene sulfide resin (PPS), glass transition temperature (T ² ) 92°C, melting point (T ³ ) did not show melting point (T ³ ) when measured by DSC at T 2 ⁾ 260°C. 273℃

<phosphor>
Green phosphor D1164: Inorganic phosphor, manufactured by Nemoto Tokushu Kagaku Co., Ltd., composition BaMg ₂ Al ₁₆ O ₂₇ :Eu, Mn), average particle diameter (D ₅₀ ) 1 to 3 μm
Red phosphor D1124: Inorganic phosphor, manufactured by Nemoto Tokushu Kagaku Co., Ltd., composition Y ₂ O ₂ S: Eu, average particle size 1 to 3 μm
Phosphor G-300FF: Inorganic phosphor, manufactured by Nemoto Tokushu Kagaku Co., Ltd., "N Luminous G Series", (composition SrAl ₂ O ₄ : Eu, Dy), average particle diameter (D ₅₀ ) 3 μm
Infrared excited phosphor VIR-009-AA: Inorganic phosphor, manufactured by Nemoto Tokushu Kagaku Co., Ltd., average particle diameter (D ₅₀ ) 1 μm
Hakkol PSR: Organic phosphor, manufactured by Showa Kagaku Kogyo Co., Ltd., the following compound

[Manufacture example 1]
<Manufacture of resin pellets>
The thermoplastic resin and phosphor shown in Table 1 were blended as shown in Table 1 (the unit of each component is parts by mass), and each component was blended in a tumbler. Next, the mixture was melt-kneaded using a twin-screw melt extruder ("Laboplast Mill" manufactured by Toyo Seiki Seisakusho Co., Ltd.) at a cylinder temperature of 340 to 370°C and a screw rotation speed of 25 rpm, and pellets were obtained by strand cutting.
<Manufacture of fibrous molded body>
The obtained resin pellets were processed into fibers with a diameter of 100 μm using Capillograph 1D (manufactured by Toyo Seiki Seisakusho Co., Ltd.) at a cylinder temperature of 320 to 370°C. The obtained fibrous resin molded body was cut into a length of 2 mm to obtain a fibrous molded body having a number average diameter of 100 μm and a number average fiber length of 2 mm.

[Production Examples 2 to 9]
In Production Example 1, the type of thermoplastic resin and the type of phosphor were changed as shown in Table 1, and the other procedures were carried out in the same manner to obtain a fibrous molded body. The obtained fibrous molded bodies each had a number average diameter of 100 μm and a number average fiber length of 2 mm.

<Measurement of glass transition temperature Tg (T ² ) and melting point Tm (T ³ )>
Glass transition temperature and/or melting point were measured as follows.
Two cycles of heating and cooling were performed under the following DSC measurement conditions, and the glass transition temperature and/or melting point during the second cycle of heating was measured.
The starting glass transition temperature is the intersection of the straight line extending the low-temperature side baseline to the high-temperature side and the tangent to the inflection point, and the intersection of the straight line extending the high-temperature side baseline to the low-temperature side and the tangent to the inflection point is the starting glass transition temperature. The end glass transition temperature was defined as the end glass transition temperature, and the start glass transition temperature was defined as the glass transition temperature (Tg). Furthermore, the temperature at which the endothermic peak reached the top was defined as the melting point. Measurement start temperature: 30°C, temperature increase rate: 10°C/min, final temperature: 400°C, temperature fall rate: 20°C/min.
The measuring device used was a differential scanning calorimeter (DSC, "DSC7020" manufactured by Hitachi High-Tech Science Co., Ltd.).
In Tables 2 to 4, which will be described later, the glass transition temperature and melting point marked with "-" mean that they could not be measured using this measurement method.

<Temperature T ¹ [°C] at which the melt viscosity is 500 [Pa·s] at a shear rate of 1,216 [1/s]>
The temperature T ¹ [° C.] at which the melt viscosity at a shear rate of 1,216 [1/s] was 500 [Pa·s] was measured as follows.
Using Capillograph 1D (manufactured by Toyo Seiki Seisakusho Co., Ltd.), nozzle length 10.0 mm, nozzle diameter 1.0 mm, shear rate 1,216 [1/S], cylinder temperature in the range of 200 to 320 °C, melting every 20 °C. The viscosity was measured. The melt viscosity obtained by the measurement is plotted on the Y axis and the temperature is plotted on the X axis, and the points showing the highest melt viscosity when the melt viscosity is less than 500 [Pa s] and the points where the melt viscosity is 500 [Pa s] or more are plotted. The temperature at which the melt viscosity was 500 [Pa·s] was determined from the straight line connecting the two points showing the lowest melt viscosity.

[Manufacture of film]
<(A) Thermoplastic resin>
E-2000F: PC, polycarbonate, viscosity average molecular weight Mv28,000, manufactured by Mitsubishi Engineering Plastics H-4000F: PC, polycarbonate, viscosity average molecular weight Mv16,000, manufactured by Mitsubishi Engineering Plastics S2008: PETG, high strength polyethylene terephthalate Resin, manufactured by SK Chemical Co., Ltd.

<(B) Fibrous molded body>
Fibrous molded polyamide (PA) fibers obtained in Production Examples 1 to 9 above: Security Fiber, manufactured by PETREL, melting point (T ² ) 250°C, number average diameter 100 μm, number average fiber length 2 mm, glass transition temperature ( T ³ ) could not be measured by the above DSC method.

Examples 1 to 8, Comparative Examples 1 to 5
<Production of film>
Films were produced as follows using the thermoplastic resin (A) and the fibrous molded product (B) shown in Tables 2 to 4 (the units of each component are parts by mass). As shown in Table 2 (the unit of each component is parts by mass), each component was blended in a tumbler. Next, using a vented twin-screw extruder with a screw diameter of 26 mm ("TEM26" manufactured by Toshiba Machine Co., Ltd.), melt-kneading was performed at the molding temperature shown in Tables 2 to 4 and a screw rotation speed of 100 rpm, and pellets were obtained by strand cutting. .
Using the obtained resin pellets, the molding temperature shown in Tables 2 to 4, roll temperature 110°C, discharge rate 5 kg/h, and screw rotation speed were performed using a single-screw extruder with a T-die (PSV-30 manufactured by Praenji Co., Ltd.). A film with a width of 25 cm and a thickness of 150 μm was obtained under the conditions of 30 rpm.

<Fluorescence performance>
The fluorescence performance of the obtained film was evaluated as follows. The evaluation was performed by five people, and the evaluation category with the largest number of evaluations was used as the evaluation in this example.
A: It was confirmed visually and/or with an infrared camera that the fibrous molded body part emitted light due to ultraviolet irradiation.
B: Other than A above. For example, when a fibrous molded article melts and is irradiated with ultraviolet or infrared rays, the entire surface of the film emits light.

<Fibrous form maintenance performance>
The obtained film was visually confirmed and evaluated as follows. The evaluation was performed by five people, and the evaluation category with the largest number of evaluations was used as the evaluation in this example.
A: It was confirmed that the fibrous molded article could maintain its fibrous shape in the film.
B: Other than A above. For example, the fibrous molded body had melted.

<Distinction (form)>
The obtained film was visually confirmed and evaluated as follows. The evaluation was performed by five people, and the evaluation category with the largest number of evaluations was used as the evaluation in this example.
A: The fibrous form was maintained, and it was possible to distinguish it from other films from the form of the fibrous molded product.
B: Other than A above.

<Distinction (luminescence)>
The obtained film was visually confirmed and evaluated as follows. The evaluation was performed by five people, and the evaluation category with the largest number of evaluations was used as the evaluation in this example.
A: It maintained a fibrous form, and could be distinguished from other films by the fact that the fibrous molded body part emitted light when irradiated with ultraviolet rays.
B: Other than A above.

1 Film 2 Fibrous molded product

Claims (15)

(A) a thermoplastic resin and (B) a fibrous molded body,
The fibrous molded article (B) contains a thermoplastic resin (b), and the thermoplastic resin (b) has a glass transition temperature T ² [°C] and a melting point T ³ [°C] when measured with a differential scanning calorimeter. °C];
(A) When the temperature at which the melt viscosity of the thermoplastic resin at a shear rate of 1,216 [1/s] is 500 [Pa・s] is T ¹ [°C], the temperature T ¹ [°C], the glass transition Temperature T ² [°C] and melting point T ³ [°C] satisfy at least one of the following formulas (1) and (2),
(A) The thermoplastic resin is at least one of polyolefin, polyamide, polyester, polycarbonate, polyoxymethylene, polyether ketone, polyether sulfone, polyether sulfide, thermoplastic polyetherimide, thermoplastic polyamideimide, and thermoplastic polyimide resin. A film containing seeds, wherein the thermoplastic resin (b) contains at least one selected from the group consisting of polyarylate, polyetheretherketone, liquid crystal polymer, polyester, and polyamide.
(1) T ² > T ¹ - 30
(2) T ³ > T ¹ + 50 The film according to claim 1, wherein the content of the fibrous molded article (B) is 0.01 to 10.0 parts by mass based on 100 parts by mass of the thermoplastic resin (A). The film according to claim 1, wherein the content of the fibrous molded article (B) is less than 2.0 parts by mass based on 100 parts by mass of the thermoplastic resin (A). The film according to any one of claims 1 to 3, wherein the thermoplastic resin (b) has a glass transition temperature T ² [° C.] of 150≦T ² ≦300. The film according to any one of claims 1 to 3, wherein the thermoplastic resin (b) has a melting point T ³ [°C] of 230≦T ³ ≦380. The film according to any one of claims 1 to 5, wherein the fibrous molded article (B) has a number average diameter of 200 μm or less. The film according to any one of claims 1 to 6, wherein the number average fiber length of the fibrous molded product (B) is 500 μm or more. The film according to any one of claims 1 to 7, wherein the thermoplastic resin (A) contains at least one selected from the group consisting of polycarbonate and polyester. The film according to any one of claims 1 to 8, wherein the fibrous molded product (B) contains at least one member selected from the group consisting of polyarylate and polyetheretherketone. The film according to any one of claims 1 to 9, wherein the fibrous molded product (B) contains a phosphor. The film according to any one of claims 1 to 10, having a thickness of 800 μm or less. Film according to any one of claims 1 to 11, which is for security cards or passports. A security card comprising the film according to any one of claims 1 to 12. A passport comprising the film according to any one of claims 1 to 12 . A resin composition comprising (A) a thermoplastic resin and (B) a fibrous molded article,
The fibrous molded article (B) contains a thermoplastic resin (b),
The thermoplastic resin (b) exhibits at least one of a glass transition temperature T ² [°C] and a melting point T ³ [°C] when measured with a differential scanning calorimeter, and
(A) When the temperature at which the melt viscosity of the thermoplastic resin at a shear rate of 1,216 [1/s] is 500 [Pa・s] is T ¹ [°C], the temperature T ¹ [°C], the glass transition including extrusion molding a resin composition whose temperature T ² [°C] and melting point T ³ [°C] satisfy at least one of the following formulas (1) and (2) ,
(A) The thermoplastic resin is at least one of polyolefin, polyamide, polyester, polycarbonate, polyoxymethylene, polyether ketone, polyether sulfone, polyether sulfide, thermoplastic polyetherimide, thermoplastic polyamideimide, and thermoplastic polyimide resin. A method for producing a film, wherein the thermoplastic resin (b) contains at least one selected from the group consisting of polyarylate, polyetheretherketone, liquid crystal polymer, polyester, and polyamide.
(1) T ² > T ¹ - 30
(2) T ³ > T ¹ + 50