JP2018045163A - Electrophotographic recording sheet, and recorded matters using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic recording sheet that improves much durability and weatherability, as maintaining a recording quality of the electrophotographic recording sheet, and various physical properties such as water-resistance, consecutive printability, or the like.SOLUTION: An electrophotographic recording sheet includes a laminate that has adhesive layer (B), a surface film layer (C), and a surface coat layer (D) lamented on one surface of a white resin film layer (A) in foregoing order, and has an adhesive layer (E), and a rear surface film layer (F) laminated on other surface of the white resin film layer (A) in foregoing order. The white resin film layer (A) has a layer that contains thermoplastic resin (X) with a melting point equal to or higher than 200°C at 50 to 97 mass%, and at least one of an organic filler and an inorganic filler at 3 to 50 mass%, and density of the electrophotographic recording sheet is 1.01 to 1.60 g/cm.SELECTED DRAWING: Figure 1

Description

  The electrophotographic recording paper of the present invention can be suitably used for color recording by an electrophotographic recording system such as a copying machine or a laser printer, has excellent recording quality such as density, color tone, gradation, etc., and has fixability, water resistance, Electrophotographic recording paper with excellent durability, especially when the recorded material is posted outdoors and used for a long time, the recorded material is less deformed and the adherend is less likely to be contaminated due to deterioration. In addition, the present invention relates to an electrophotographic recording sheet capable of producing a recorded matter that can be posted and used for a long period of time.

  Recent advances in copiers and printers are remarkable, and not only in terms of price, but also in terms of performance such as recording quality and recording speed, they are dramatically improving. For this reason, printed materials such as posters, catalogs, brochures, etc. that were conventionally created by printing machines can now be created more easily and quickly while maintaining conventional recording quality using copiers and printers. became. Such recording by a copying machine or a printer can be used particularly suitably when a variety of printed materials are produced quickly.

Among various copying machines and printers, copying machines and printers employing an electrophotographic method, in particular, copying machines and laser printers using a semiconductor laser are excellent in that they can perform high-resolution and high-speed recording. Although there are problems with electrophotographic colorization, the size of the apparatus is increased because a plurality of developing devices are required, and the color tone is slightly inferior because a pigment is used as a toner color material. The problems are being solved by downsizing the apparatus and improving the materials such as toner and recording paper.
Regarding the improvement of recording paper, a thick film for printing (Patent Document 1) in which an antistatic agent is applied to a polyester biaxially stretched film having high heat resistance and water resistance has been proposed and put into practical use.

However, this thick film for printing has the drawback that when used outdoors for a long period of time, the filler used to form fine cavities easily flows out and contaminates the adherend. It was.
On the other hand, in an electrophotographic recording paper (Patent Document 2) in which a synthetic resin film having a coating layer is laminated on at least one surface of a base material layer made of water-resistant paper material, the electrophotographic recording paper made of conventional pulp paper An electrophotographic recording paper having better recording quality, fixing properties, water resistance and durability than recording paper has been devised and put into practical use. Further, in an electrophotographic recording paper (Patent Document 3) in which a toner receiving layer containing a fat-soluble polymer antistatic agent is provided on at least one surface of a water-resistant support, recording of density, color tone, gradation, and the like. An electrophotographic recording paper that is excellent in quality and excellent in fixability, water resistance, and durability, and has no sticking due to charging even after continuous printing has been proposed and put into practical use.

However, although the recorded matter using the conventional electrophotographic recording paper as described above has sufficient water resistance and durability for a short period, it is used when posted outdoors for a long time. It has been found that there is a defect that the recorded material is deformed.
Specifically, since the electrophotographic recording paper of Example 1 of Patent Document 2 uses a photographic paper base paper as a core material, when this is used outdoors as a posting material for a long time, from the end face of the posting material. Water entered and swelled on the posting due to moisture absorption. In addition, the electrophotographic recording paper of Example 3 of Patent Document 2 is an inorganic fine material used as a core material when pasted on an adherend such as a metal plate that is likely to rise in temperature and used outdoors for a long time. Swelling occurred in the posting due to the difference between the linear expansion coefficient and the thermal contraction ratio of the powder-containing polyolefin film and the polyester film used for the recording layer.

JP 2004-08389 A JP 2002-091049 A JP 2008-299017 A

  In the present invention, there is provided an electrophotographic recording paper having improved durability and weather resistance while maintaining the recording quality of the conventional electrophotographic recording paper and various physical properties such as water resistance and continuous printability. Objective.

As a result of diligent investigations to solve these problems, the present inventor has improved the durability of a base material layer made of a paper material having a conventional water resistance, and has a melting point of 200 ° C. or higher. It has been found that by using a white resin film layer mainly containing a resin, an electrophotographic recording paper having the desired characteristics can be provided, and the present invention has been completed.
That is, in the present invention, the adhesive layer (B), the surface film layer (C), and the surface coat layer (D) are laminated in this order on one side of the white resin film layer (A), and the white resin film layer (A) An electrophotographic recording paper comprising a laminate in which an adhesive layer (E) and a back film layer (F) are laminated in this order on the other side of the white resin film layer (A) having a melting point of 200 ° C. or higher Thermoplastic resin (X) of 50 to 97% by mass and at least one of organic filler and inorganic filler of 3 to 50% by mass, and the density of the white resin film layer (A) is 1.01 to 1.60 g / cm. ³ is an electrophotographic recording sheet.

In the present invention, the adhesive layer (B), the surface film layer (C), and the surface coat layer (D) are laminated in this order on one side of the white resin film layer (A), and the white resin film layer (A) An electrophotographic recording paper comprising a laminate in which an adhesive layer (E), a back film layer (F), and a back coat layer (G) are laminated in this order on the other side of the white resin film layer (A) contains 50 to 97% by mass of a thermoplastic resin (X) having a melting point of 200 ° C. or higher, and 3 to 50% by mass of at least one of an organic filler and an inorganic filler, and the density of the white resin film layer (A) is 1. The present invention relates to an electrophotographic recording paper having a density of .01 to 1.60 g / cm ³ .
The surface film layer (C) and the back film layer (F) are substantially free of pigments and have a high durability, a thermoplastic resin (Y) having a melting point of 200 ° C. or higher, as in the case of the base material layer, of 99 to 100 mass. % Is preferably included.

The thermoplastic resin (X) is preferably a polyester resin, and the thermoplastic resin (Y) is preferably a polyester resin.
The present invention also relates to a recorded matter obtained by performing electrophotographic printing on the above-described electrophotographic recording paper, having excellent recording quality, and further improving durability and weather resistance.

  The electrophotographic recording paper of the present invention has superior recording quality and various physical properties such as water resistance and continuous printability, and has durability and weather resistance superior to those of conventional electrophotographic recording paper. ing.

FIG. 3 is a partially enlarged cross-sectional view of a uniform state of the electrophotographic recording paper of the present invention. FIG. 6 is a partially enlarged cross-sectional view of another aspect of the electrophotographic recording paper of the present invention. In the figure, 1 is an electrophotographic recording paper, 2 is a white resin film layer (A), 3 is an adhesive layer (B), 4 is a surface film layer (C), 5 is a surface coat layer (D), 6 is An adhesive layer (E), 7 is a back film layer (F), and 8 is a back coat layer (G).

  The electrophotographic recording paper and recorded matter of the present invention will be described in detail below. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

《Electrophotographic recording paper》
[Features and layer structure]
In the electrophotographic recording paper of the present invention, an adhesive layer (B), a surface film layer (C), and a surface coat layer (D) are laminated in this order on one side of the white resin film layer (A) to obtain a white resin A laminate in which an adhesive layer (E) and a back film layer (F) are laminated in this order on the other surface of the film layer (A) is included.
The white resin film layer (A) contains 50 to 97% by mass of a thermoplastic resin (X) having a melting point of 200 ° C. or higher, and 3 to 50% by mass of at least one of an organic filler and an inorganic filler, and has a density of 1.01. ˜1.60 g / cm ³ .
As shown in FIGS. 1 and 2, the electrophotographic recording paper can have a structure in which a synthetic resin film layer is laminated on both sides of a white resin film layer via an adhesive layer. The coat layer that becomes a toner-receiving layer during electrophotographic printing can be at least one outermost layer in the same structure.
Hereinafter, each layer constituting the electrophotographic recording paper of the present invention will be described, and physical properties of the electrophotographic recording paper will be referred to.

[White resin film layer (A)]
The white resin film layer (A) constituting the electrophotographic recording paper of the present invention serves as a support or base material for the electrophotographic recording paper. The white resin film layer (A) imparts physical strength such as bending elasticity and tensile elasticity to electrophotographic recording paper, whiteness and opacity as recording paper, and further imparts water resistance. In particular, in the present invention, more excellent durability and weather resistance are imparted.
The white resin film layer (A) has a whiteness of preferably 80% or more, and more preferably 85% or more. By setting the whiteness of the white resin film layer (A) to 80% or more, the contents printed and recorded on the electrophotographic recording paper of the present invention can be more easily distinguished. The “whiteness” in the present specification means whiteness measured in accordance with the method described in JIS-L1015.

  The white resin film layer (A) may have a single layer structure or a multilayer structure. In the case of a single layer structure, the film may be non-stretched, uniaxially stretched, or biaxially stretched. In the case of a multilayer structure, it may have a two-layer structure or a structure having three or more layers. In the case of a two-layer structure, any structure of non-stretching / uniaxial stretching, non-stretching / biaxial stretching, monoaxial stretching / uniaxial stretching, monoaxial stretching / biaxial stretching, biaxial stretching / biaxial stretching, It doesn't matter. In the case of a structure of three or more layers, the single layer structure and the two layer structure may be combined, and any combination may be used. Among these, those including at least one biaxially stretched layer are preferable, and those including a three-layer structure in which a biaxially stretched layer is used as a core layer and thin skin layers are laminated on the front and back surfaces are more preferable. Such a configuration is suitable as a support for an electrophotographic recording sheet because the thickness is uniform in the surface direction and the thickness can be reduced.

The white resin film layer (A) has a layer containing 50 to 97% by mass of a thermoplastic resin (X) having a melting point of 200 ° C. or higher and 3 to 50% by mass of at least one of an organic filler and an inorganic filler. The white resin film layer (A) preferably has a layer containing 70 to 96% by mass of the thermoplastic resin and 4 to 30% by mass of the filler, and 80 to 95% by mass of the thermoplastic resin and the filler. It is more preferable to have a layer containing 5 to 20% by mass. If the blending ratio of the filler is within the above range, the white resin film layer can be easily whitened, opaqued, reduced in weight, or softened.
The thickness of the white resin film layer (A) is preferably 20 to 500 μm, more preferably 30 to 400 μm, and still more preferably 40 to 300 μm. By setting the thickness of the white resin film layer (A) to 20 μm or more, the mechanical strength of the electrophotographic recording paper of the present invention can be improved, and as a result, a large area recorded matter such as a poster can be produced. It becomes possible. On the other hand, by setting the thickness of the white resin film layer (A) to 500 μm or less, it is possible to prevent the entire electrophotographic recording paper of the present invention from becoming too strong, and to reduce its own weight during electrophotographic printing. It is possible to improve the paper supply / discharge performance.

  Examples of the thermoplastic resin (X) having a melting point of 200 ° C. or higher include polyethylene terephthalate (melting point approximately 260 ° C.), polybutylene terephthalate (melting point approximately 225 ° C.), polyethylene naphthalate (melting point approximately 270 ° C.), polycarbonate (melting point 220 to 250 ° C. ), Poly (4-methylpent-1-ene) (melting point: about 230 ° C.), isotactic polystyrene (melting point: about 240 ° C.), syndiotactic polystyrene (melting point: about 270 ° C.), nylon-6 (melting point: about 225 ° C.) , Nylon-6,6 (melting point: 265 ° C) and the like. Among these, the thermoplastic resin (X) is preferably a polyester-based resin such as polyethylene terephthalate or polybutylene terephthalate, and more preferably polyethylene terephthalate. A polyester-based resin can be easily obtained as a film having a uniform thickness and can be easily processed, and it is easy to impart an appropriate capacitance to an electrophotographic recording paper using the polyester resin.

  As the organic filler, the thermoplastic resin (X) is an incompatible thermoplastic resin, and when the thermoplastic resin (X) serving as the matrix resin of the white resin film layer (A) is melt-kneaded, It is preferable that the resin is finely dispersed in an island shape in the thermoplastic resin (X). Specifically, as the organic filler when the thermoplastic resin (X) is polyethylene terephthalate, polystyrene resin, polypropylene resin, polymethylpentene resin, polyphenylene ether resin, poly (meth) acrylic resin, Examples thereof include polycarbonate resin, polysulfone resin, cellulose resin, polyphenylene sulfide resin, cyclic olefin ring-opening polymer resin, and cyclic olefin-ethylene copolymer resin. Among these, a polystyrene resin and a polypropylene resin are preferable, and it is more preferable to use a polystyrene resin and a polypropylene resin in combination.

The inorganic filler can be dispersed in the thermoplastic resin (X) described above, and whitens or opacifies the white resin film layer (A), or serves as a pore nucleating agent, and the white resin film layer (A). It is preferable to reduce the weight and soften. Specifically, examples of the inorganic filler when the thermoplastic resin (X) is polyethylene terephthalate include calcium carbonate, titanium oxide, zinc oxide, silica, barium sulfate, kaolinite, talc, zeolite, and alumina. Said organic filler and inorganic filler can also be used together.
As a method for producing the white resin film layer (A), a conventionally known method can be applied. For example, a resin composition in which the above raw materials are mixed is melt-kneaded at a temperature equal to or higher than the melting point of the thermoplastic resin (X) and extruded. A method of forming the sheet into a non-stretched sheet using a machine or the like and then stretching the unstretched sheet can be used.

Examples of the stretching method for the unstretched sheet include longitudinal stretching using a difference in peripheral speed of a group of rolls, rolling using a number of rolls, transverse stretching using a tenter, and sequential biaxial combination of the longitudinal stretching and the transverse stretching. Examples thereof include stretching, simultaneous biaxial stretching using a tenter and a linear motor, simultaneous biaxial stretching using a pantograph type stretching machine, and simultaneous biaxial stretching using a tubular method.
For example, when the thermoplastic resin (X) is polyethylene terephthalate and the white resin film layer (A) is desired to be lighter and more flexible, an unstretched sheet containing at least one of an organic filler and an inorganic filler is used as a stretching temperature. Is stretched 2 to 5 times in the machine direction at a temperature 10 ° C. or more lower than the melting point of polyethylene terephthalate, and then stretched 2 to 5 times in the transverse direction at a temperature lower than the glass transition temperature of polyethylene terephthalate + 50 ° C. Thus, a lightweight and flexible white resin film layer (A) having a large number of fine pores formed therein can be obtained.
The white resin film layer (A) made of the biaxially stretched polyethylene terephthalate film thus obtained is subjected to heat treatment within a temperature range from a temperature 50 ° C. lower than the melting point of polyethylene terephthalate to the melting point of polyethylene terephthalate as necessary ( It is preferable to improve the dimensional stability by performing an annealing treatment.

[Surface film layer (C), Back film layer (F)]
The front film layer (C) and the back film layer (F) constituting the electrophotographic recording paper of the present invention characterize the electrophotographic recording paper in terms of heat resistance, durability, and suitable capacitance. There is a surface film layer (C) on one surface of the white resin film layer (A) via an adhesive layer (B), and an adhesive layer on the other surface of the white resin film layer (A). The back film layer (F) is laminated via (E).

  The thickness of each of the surface film layer (C) and the back film layer (F) is preferably 10 to 250 μm, more preferably 12 to 125 μm, and still more preferably 12 to 50 μm. Moreover, it is preferable that the thickness of each of the surface film layer (C) and the back film layer (F) is thinner than the thickness of the white resin film layer (A), and the surface film layer (C) and the back film layer ( It is more preferable that the total thickness of F) is thinner than the thickness of the white resin film layer (A). If the thickness of the front film layer (C) and the back film layer (F) is within the same range, the filler in the white resin film layer (A) is exposed to the outside in the electrophotographic recording paper of the present invention. It is easy to prevent contamination of the kimono and to have a suitable capacitance.

  As the component resin for the front film layer (C) and the back film layer (F), the white resin film layer (A) contains a thermoplastic resin (Y) having a melting point of 200 ° C. or higher, and has water resistance and insulation properties. It is preferable to apply a thermoplastic resin having the same. By using a thermoplastic resin (Y) having a melting point of 200 ° C. or higher for the film layer, the thermoplastic resin (Y) is not easily deformed or melted by heat in the toner fixing process of electrophotographic recording paper. It is easy to prevent the recording paper itself from being greatly deformed, sticking to a toner fixing device (such as a heat fusing roll), or damaging the recording device.

As such a thermoplastic resin (Y), like the thermoplastic resin (X), polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, poly (4-methylpent-1-ene), isotactic Examples include polystyrene, syndiotactic polystyrene, nylon-6, nylon-6,6, and the like. The thermoplastic resin (Y) may be the same as or different from the thermoplastic resin (X). The thermoplastic resin (Y) is also preferably a polyester-based resin such as polyethylene terephthalate or polybutylene terephthalate, and more preferably polyethylene terephthalate, like the thermoplastic resin (X).
The front film layer (C) and the back film layer (F) preferably contain 99 to 100% by mass of a thermoplastic resin (Y) having a melting point of 200 ° C. or higher, and substantially does not contain the filler as described above. It is more preferable. Examples of the minor component include resin additives such as antioxidants, light stabilizers, and antistatic agents.

By forming the surface film layer mainly containing a thermoplastic resin (Y) having a melting point of 200 ° C. or higher, substantially containing no filler, the filler in the white resin film layer (A) is exposed to the outside and covered. Less contamination of the kimono.
The front film layer (C) and the back film layer (F) can be produced by applying the same method as the production method of the white resin film layer (A).
An electrophotographic recording paper obtained by constituting the white resin film layer (A), the front film layer (C) and the back film layer (F) with a water-resistant thermoplastic resin having a melting point of 200 ° C. or higher. The water resistance can be greatly improved, and the durability and weather resistance can be further improved.

[Coat layer (D), coat layer (G)]
The coat layer (D) constituting the electrophotographic recording paper of the present invention and the coat layer (G) capable of constituting the electrophotographic recording paper of the present invention are a front film layer (C) or a back film layer (F). Laminated on top of each other and constitutes the outermost layer of electrophotographic recording paper. It is a layer that accepts and fixes toner during electrophotographic recording (copying and laser printing), and is particularly resistant to water and durability. The present invention realizes an electrophotographic recording sheet that is excellent and prevents post-printing charging so that the sheets do not stick to each other.

The thickness of the coat layer (D) and the coat layer (G) is preferably from 0.1 to 20 μm, more preferably from 0.5 to 8 μm, still more preferably from 1 to 4 μm. By setting the thickness of the coat layer to 0.1 μm or more, it becomes easy to obtain toner receiving performance and antistatic performance that are uniform in the surface direction. On the other hand, when the thickness of the coat layer is 20 μm or less, stable antistatic performance and water resistance can be easily obtained regardless of the environment.
The coating layer (D) and the coating layer (G) have a surface resistivity of 1 × 10 ^{7 to} 9 × 10 ¹² at a temperature of 25 ° C. and a relative humidity of 20%, as in the toner receiving layer described in Patent Document 2. It is preferable to contain a polymer antistatic agent so as to be in the range of Ω.

(Polymer antistatic agent)
The polymer antistatic agent must have both antistatic performance and water resistance performance, and should have a small influence on the antistatic effect even after a heating process using an electrophotographic toner fixing device. is there. That is, for the polymer antistatic agent, the surface specific resistance value of the coating layer which is a toner receiving layer at a temperature of 25 ° C. and a relative humidity of 20% can be in the range of 1 × 10 ^{7 to} 9 × 10 ¹² Ω. It is preferable to use a polymer antistatic agent. If it is fat-soluble, it can be used in combination with a binder resin having higher water resistance. In the present invention, the fat-soluble means that it dissolves in an organic solvent to be described later at a solid concentration of 5% by weight or more under normal temperature and pressure and does not generate a precipitate. The polymer antistatic agent used in the present invention is preferably a copolymer of a monomer exhibiting antistatic performance and a hydrophobic (lipophilic) monomer. By copolymerizing a hydrophobic monomer, the solubility in various organic solvents can be enhanced. Examples of such hydrophobic monomers include esters of acrylic acid or methacrylic acid with various alcohols.

  The polymer antistatic agent has an alkylene oxide group and / or a hydroxyl group in the molecule, and an alkali metal ion having a relatively small ion diameter such as lithium ion, sodium ion or potassium ion as a counter ion of the hydroxyl group. It is more preferable that it is an ion conductive antistatic agent. For example, an antistatic agent having a copolymer structure represented by the following general formula (1) contributes to water resistance and a unit having an alkylene oxide group that exhibits antistatic performance (improves lipophilicity). Since it has a structure composed of units having a lipophilic group, it is possible to obtain an antistatic agent with excellent water resistance, which is a preferred form. The specific gravity and degree of polymerization of each unit can be determined from the antistatic performance and water resistance performance to be obtained.

In the general formula (1), R ¹ and R ² each independently represents a hydrogen atom or a methyl group. When m is 2 or more, m R ^{1 s} may be the same or different. When n is 2 or more, n R ^{2 s} may be the same or different. Therefore, for example, R ¹ and R ² can all be methyl groups.
In the general formula (1), R ⁴ represents an alkyl group having 1 to 30 carbon atoms. The number of carbon atoms of the alkyl group may be selected from the range of, for example, 1 to 25, further 2 to 23, further 3 to 20, and further 4 to 18. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, dodecyl group, tridecyl group, stearyl group and the like. These may be linear or branched. When m is 2 or more, m R ^{4 s} may be the same or different. For example, an alkyl group having less than 10 carbon atoms and an alkyl group having 10 or more carbon atoms may be mixed, and further, an alkyl group having 1 to 6 carbon atoms and an alkyl group having 15 to 20 carbon atoms may be mixed. Also good.

In the general formula (1), A is one type of linking group selected from the following <Group 1> or one or more types of linking groups selected from the following <Group 1> and <Group 2> below. It represents a linking group in which one or more selected linking groups are alternately bonded, or a single bond.
<Group 1> An alkylene group having 1 to 6 carbon atoms which may have a substituent,
An arylene group having 6 to 20 carbon atoms which may have a substituent,
<Group 2> —CONH—, —NHCO—, —OCONH—, —NHCOO—,
-NH-, -COO-, -OCO-, -O-,

Examples of the C1-C6 alkylene group of <Group 1> include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group, and these may be linear or branched. Although it may be, it is preferably linear. Examples of the substituent include a hydroxyl group and an aryl group. Examples of the arylene group having 6 to 20 carbon atoms include a phenylene group, a naphthylene group, and an anthrylene group. Examples of the substituent include a hydroxyl group and an alkyl group. Examples of the arylene group substituted with an alkyl group include a tolylene group and a xylylene group. Moreover, as a coupling group selected from <Group 2>, a urethane group and an ester group can be preferably selected. As the linking group in which one or more linking groups selected from <Group 1> and one or more linking groups selected from <Group 2> are alternately bonded,
A linking group represented by ((linking group selected from group 1)-(linking group selected from group 2) "or" (linking group selected from group 1)-(linkage selected from group 2) Group)-(a linking group selected from group 1)-(a linking group selected from group 2) ". In the latter case, the two types (the linking group selected from the first group) may be the same as or different from each other, and the two types (the linking group selected from the second group) are the same as each other. It may or may not be.

In the general formula (1), R ³ represents a hydrogen atom, a chlorine atom or a methyl group, preferably a hydrogen atom or a methyl group. When p is 2 or more, p R ^{3 s} may be the same or different, but are preferably the same. Although p represents the integer of 1-100, 2-50 are preferable and 3-50 are more preferable. For example, when R ³ is a hydrogen atom, p is selected from the range of 10 to 35, more preferably 15 to 30, and further 20 to 25, or when R ³ is a methyl group, p is 1 to 20, May be selected from the range of 3 to 16, or 5 to 14.

In general formula (1), when n is 2 or more, all of A, R ³ and p of n side chains bonded to n repeating units may be the same or different. Also good. For example, all of R ³ may be a hydrogen atom or a methyl group, or a hydrogen atom and a methyl group may be mixed. If hydrogen atom and methyl group are mixed, it is preferable that all the p number of R ³ constituting one of the side chains is either hydrogen atom or a methyl group.
In the general formula (1), M is an alkali metal, and can include Li, Na, K, and the like, and Li having a small ionic radius is preferably used from the viewpoint of conductivity. When n is 2 or more, n Ms may be the same or different. Preferred is the same case.

In general formula (1), m represents an integer of 0 to 300, n represents an integer of 1 to 300, and p represents an integer of 1 to 100. Preferably, m represents an integer of 0 to 200, n represents an integer of 10 to 200, and p represents an integer of 3 to 50.
The m repeating units and the n repeating units may be bonded so as to be a block copolymer, or may be bonded so as to be a random copolymer.
The production method of the antistatic agent having the structure represented by the general formula (1) is not particularly limited, and can be appropriately synthesized by combining known synthesis methods. Typically, it can be prepared by copolymerizing having R ¹ and R ⁴ (meth) acrylate monomers, and having R ² and alkylene oxide group-containing (meth) acrylate monomer. Specifically, it can be carried out by dissolving these monomers in an inert organic solvent and adding a polymerization initiator, followed by heating to 65 to 150 ° C. with stirring. The polymerization time is usually set to 1 to 24 hours.

Specific examples of (meth) acrylate monomers having R ¹ and R ⁴ are methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, cyclohexyl Examples thereof include alkyl (meth) acrylates such as (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, and stearyl (meth) acrylate.

The (meth) acrylate monomer having R ² and an alkylene oxide group can be produced by introducing an alkali metal into the alkylene oxide monomer. Examples of alkylene oxide monomers that can be suitably used in the present invention include, for example, (poly) ethylene glycol (meth) acrylate, (poly) propylene glycol (meth) acrylate, (poly) chloroethylene glycol (meth) acrylate, (poly And (poly) alkylene oxide (meth) acrylates such as tetramethylene glycol (meth) acrylate, methoxy (poly) ethylene glycol (meth) acrylate, and methoxy (poly) propylene glycol (meth) acrylate. Moreover, in these specific examples, the alkylene oxide monomer which has further connecting groups other than a single bond in the location corresponding to A of General formula (1) is also mentioned. For example, as a compound having a urethane bond in A, a compound described in JP-A No. 09-113704 can be used. The method for introducing an alkali metal corresponding to M is not particularly limited, but it is usually possible to impart ion conductivity by alkali metal ions by ionizing hydroxyl terminal by reacting an alkali metal salt with an alkylene oxide monomer. Examples of alkali metal salts that can be suitably used in the present invention include lithium, sodium or potassium perchlorates, or inorganic salts thereof such as chlorides, bromides, iodides, thiocyanides, and the like.

  The polymerization initiator used for copolymerization is preferably oil-soluble, and examples of suitable polymerization initiators include organic peroxides and azonitriles. Organic peroxides include alkyl peroxides (dialkyl peroxides), aryl peroxides (diaryl peroxides), acyl peroxides (diacyl peroxides), aroyl peroxides (diaroyl peroxides), ketone peroxides, peroxides Carbonates (peroxydicarbonates), peroxycarboxylates, hydroperoxides, peroxyketals, peroxyesters and the like are included. Examples of the alkyl peroxide include diisopropyl peroxide, ditertiary butyl peroxide, and tertiary butyl hydroperoxide. Examples of the aryl peroxide include dicumyl peroxide and cumyl hydroperoxide. Examples of the acyl peroxide include dilauroyl peroxide. Examples of aroyl peroxide include dibenzoyl peroxide. Examples of the ketone peroxide include methyl ethyl ketone peroxide and cyclohexanone peroxide. Examples of the azonitrile include azobisisobutylnitrile and azobisisopropionitrile.

  The molecular weight of the polymer antistatic agent is preferably in the range of 10,000 to 1,000,000, as measured by gel permeation chromatography (GPC). If the molecular weight is 10,000 or more, the antistatic agent is difficult to exude from the formed coating layer, so that sufficient water resistance tends to be easily obtained. If the molecular weight is 1,000,000 or less, since it is easy to mix with the binder component, coating defects are less likely to occur, and a uniform antistatic effect tends to be obtained.

  In the coating layer (D) and the coating layer (G), the alkali metal ion concentration is preferably 0.01 to 1% by weight, more preferably 0.01 to 0.7% by weight, still more preferably 0.01 to 0. 0%. It is desirable to add a polymer antistatic agent so as to be 5% by weight. If the alkali metal ion concentration is 0.01% by weight or more, an antistatic effect is easily obtained, and sticking between discharged papers tends to be prevented when continuously printed by an electrophotographic printer. On the other hand, if the amount is 1% by weight or less, there is no excessive increase in hydrophilicity due to an increase in metal ions, so that the water-resistant adhesion of the toner tends to be easily maintained. These alkali metal ion concentrations are described as values to be set at the time of preparation, but can also be obtained by analysis using a technique such as ICP emission spectroscopic analysis after dry ashing.

  The amount of the polymer antistatic agent added to the coat layer (D) and the coat layer (G) is appropriately determined depending on the amount of alkali metal ions contained, but is preferably 1 to 50% by weight, more preferably 2 to 2%. It is 45 weight%, More preferably, it is the range of 3-40 weight%. If it is 1% by weight or more, it tends to be uniformly dispersed in the coating layer and a sufficient polymer antistatic effect tends to be obtained. On the other hand, if the amount is 50% by weight or less, there is a tendency that poor fixing of the toner hardly occurs because the balance with the amount of the binder resin and pigment particles added is good.

(Binder resin)
The coat layer (D) and the coat layer (G) desirably contain a binder resin in order to impart toner fixability and stronger water resistance. The binder resin is used to fix the polymer antistatic agent on the film layer and to improve the acceptability of the toner at the time of electrophotographic printing, and constitutes the coat layer (D) and the coat layer (G). As a component to be used, it is preferable to use it together with the polymer antistatic agent.

  The binder resin is preferably a water-insoluble binder. A coating layer having excellent water resistance can be obtained by using a water-insoluble binder. Examples of water-insoluble binders include urethane resins, terpene resins, petroleum resins, ethylene-vinyl acetate copolymer resins, vinyl chloride resins, vinyl chloride-vinyl acetate copolymer resins, vinylidene chloride resins, vinyl chloride-vinylidene chloride copolymers. Copolymer resin, acrylate copolymer resin, methacrylate ester copolymer resin, chlorinated ethylene resin, chlorinated propylene resin, butyral resin, silicone resin, polyester resin, nitrocellulose resin, styrene-acrylic copolymer resin, styrene -A butadiene copolymer resin, an acid-modified olefin resin, a hydroxyl group-modified olefin resin, etc. can be mentioned. Any one of these binder resins may be used alone, or two or more kinds thereof may be mixed and used. Among these, urethane resins such as polyether urethane, polyester polyurethane, and acrylic urethane or acrylic ester copolymer resins have good compatibility (compatibility) with the above-described antistatic agent composed of an alkylene oxide compound, and are mixed. The coating layer is preferable because it is stable and easy to apply, and the coating layer obtained has good adhesion to the toner. The binder resin content in the coat layer is preferably in the range of 10 to 99% by weight, more preferably 15 to 98% by weight, and still more preferably 20 to 97% by weight. If it is 10% by weight or more, the coat layer can have a sufficient cohesive force, so that there is a tendency that peeling is unlikely to occur in an image formed by an electrophotographic method. If it is 99% by weight or less, the antistatic effect tends to be easily obtained.

(Organic solvent)
When the organic solvent is laminated on the front film layer (C) and the back film layer (F), respectively, the above-mentioned polymer antistatic agent is a constituent component of the coat layer (D) and the coat layer (G). It is used for dissolving and mixing an agent and a binder resin into a paint.
Examples of the organic solvent include general organic solvents and are not particularly limited. The solubility parameter (hereinafter abbreviated as SP value) is preferably 6 to 12, more preferably 7 to 11. Here, the solubility parameter (SP value) is synonymous with a solubility parameter (Solubility Parameter), and is a characteristic value of a liquid that serves as a measure of the miscibility between liquids. When the SP value is δ, the molecular cohesive energy of the liquid is E, and the molecular volume is V, the SP value δ is expressed by δ = (E / V) ^1/2 .

Specific examples of the solvent having an SP value of 6 to 12 include n-hexane (SP value: 7.3), n-butanol (SP value: 11.4), 2-propanol (SP value: 11.5). , Toluene (SP value: 8.9), xylene (SP value: 8.8), methyl ethyl ketone (SP value: 9)
. 3), acetone (SP value: 10), methyl isobutyl ketone (SP value: 8.4), cyclohexanone (SP value: 9.9), ethyl acetate (SP value: 9.1), isopropyl acetate (SP value: 8.4), butyl acetate (SP value: 8.5), tetrahydrofuran (SP value: 9.5), ethyl cellosolve (SP value: 9.9), butyl cellosolve (SP value: 8.9) and the like. . If the SP value is 12 or less, the solubility of the binder resin tends to be improved, and when a cross-linking agent is used, the cross-linking reaction is prevented from starting in the solution, and the stability of the paint tends to be improved. If the SP value is 6 or more, the volatility is not excessively high and the handling tends to be easy.

(Pigment particles)
The coat layer (D) and the coat layer (G) may contain pigment particles as necessary. The coating layer can contain pigment particles in the range of 0 to 70% by weight. That is, it may or may not contain 70% by weight or less of pigment particles.
Pigment particles improve toner fixing properties due to their oil absorption, improve surface texture and gloss as extender pigments, improve whiteness as white pigments, improve anti-blocking performance by imparting surface irregularities, improve light resistance and weather resistance as UV reflectors , Etc. can be appropriately selected and used for the purpose of imparting performance. Organic and inorganic fine powders are used as pigment particles. Specific examples include silicon oxide, calcium carbonate, calcined clay, titanium oxide, zinc oxide, barium sulfate, diatomaceous earth, acrylic particles, styrene particles, polyethylene particles, polypropylene. Particles and the like. The particle diameter of the pigment particles is preferably 20 μm or less, more preferably 15 μm or less. If the particle diameter of the pigment particles is 20 μm or less, the pigment particles are unlikely to fall off from the formed coating layer, so that there is a tendency that the powder blowing phenomenon does not easily occur. The pigment particle content in the coat layer is preferably in the range of 0 to 70% by weight, more preferably 0 to 60% by weight, and still more preferably 0 to 45% by weight. If the content of the pigment particles is 70% by weight or less, there is a tendency that it is easy to suppress peeling of an image formed by the electrophotographic method by giving the coat layer sufficient cohesive force.

(Coating)
The coat layer (D) and the coat layer (G) can be formed by forming a coating film on a support with a known coating apparatus and then drying. Specific examples of the coating apparatus include a die coater, a bar coater, a comma coater, a lip coater, a roll coater, a curtain coater, a gravure coater, a spray coater, a blade coater, a reverse coater, and an air knife coater.
The coating amount of the coating layer is preferably 0.1 to 20 g / m ² , more preferably 0.5 to 10 g / m ² in terms of solid content after drying per layer. If the coating amount is 0.1 g / m ² or more, uniform antistatic performance tends to be easily obtained. If it is 20 g / m ² or less, the polymer antistatic agent is less likely to have a distribution in the thickness direction depending on the coating conditions and the coating environment, so that stable antistatic performance and water resistance tend to be easily obtained.

[Adhesive layer (B), adhesive layer (E)]
In order to bond and bond the white resin film layer (A) used for the electrophotographic recording paper of the present invention to the front film layer (C) or the back film layer (F), an adhesive layer is used.
For the bonding of both, an adhesive such as a solvent-based adhesive or a hot-melt adhesive is provided on the white resin film layer (A) as an adhesive layer by a technique such as coating, spraying, melt extrusion laminating, etc. It can carry out by the method of carrying out dry lamination of a surface film layer (C) or a back film layer (F) via. Moreover, both bonding can be performed by techniques, such as a melt lamination, arrange | positioning a heat-fusible film and a melt-extrusion film on a white resin film layer (A), making this into an adhesive layer.

Examples of the solvent-based adhesive include resin components composed of acrylic resins, urethane resins, ether resins, ester resins, epoxy resins, rubber resins, silicone resins, ABS resins, etc. Typical examples are liquid adhesives in the form of a solution type or an emulsion type, which can be dissolved, dispersed, emulsion-dispersed and diluted in the phase by using a liquid and can be applied.
These adhesives are applied by die coater, bar coater, comma coater, lip coater, roll coater, rod coater, curtain coater, gravure coater, spray coater, blade coater, reverse coater, air knife coater, slide hopper, etc. Is called. Thereafter, smoothing is performed as necessary, and an adhesive layer is formed through a drying step.

These adhesives are generally applied such that the basis weight is 0.5 to 25 g / m ² and an adhesive layer is provided.
When using an adhesive, apply the adhesive on the surface of the white resin film layer (A), and then overlay the surface film layer (C) or back film layer (F), which is a synthetic resin film, and press Apply pressure-sensitive adhesive with a roll, or apply the adhesive on one side of the surface film layer (C) or the back film layer (F) which is a synthetic resin film, and then overlay the white resin film layer (A), What is necessary is just to press-bond with a press roll.

Hot melt adhesives include polyolefin resins such as low density polyethylene, ethylene / vinyl acetate copolymers, metal salts of ethylene / (meth) acrylic acid copolymers (so-called Surlyn), chlorinated polyethylene, chlorinated polypropylene, etc. And polyamide resins, polybutyral resins, urethane resins and the like.
When using a hot-melt type adhesive, it is applied to the surface of the white resin film layer (A) by a method such as beet coating, curtain coating, slot coating, or the surface of the white resin film layer (A). Then, it is extruded into a molten film from a die and laminated, and then a surface film layer (C) or a back film layer (F), which is a synthetic resin film, is stacked and pressure bonded with a pressure roll.

The kind of adhesive used for the adhesive layer (B) and the adhesive layer (E), the coating method, and the coating amount (basis weight, thickness) may be the same or different.
These adhesive layer (B) and adhesive layer (E) may contain a known ultraviolet absorber that absorbs any wavelength of 280 to 400 nm for the purpose of improving weather resistance. . By containing the ultraviolet absorber, it is possible to form an adhesive layer that also serves as an ultraviolet blocking layer.

[Lamination]
For example, when the above-mentioned solvent-based adhesive is used for the adhesive layer, an adhesive is applied to both sides of the white resin film layer (A). Then, the surface film layer (C) is superposed on the front surface, and the surface film layer (F) is superposed on the back surface and pressure bonded with a pressure roll, or an adhesive is applied to one surface of the white resin film layer (A). The layer (B) is applied, the surface film layer (C) is overlaid and pressure-bonded with a pressure roll, and the adhesive layer (E) is then applied to the other surface of the white resin film layer (A). And then apply the adhesive layer (B) on one side of the surface film layer (C), which is a synthetic resin film, by overlapping the back film layer (F) and pressurizing with a pressure roll, Stack the white resin film layer (A) and pressurize with a pressure roll Then, the adhesive layer (E) is applied to one side of the back film layer (F), which is a synthetic resin film, and then the other side of the white resin film layer (A) is overlaid and applied with a pressure roll. The method of pressure bonding is mentioned.
Lamination of the coat layer (D) on the surface film layer (C) may be performed before or after the white resin film layer (A) and the surface film layer (C) are laminated. Similarly, the coating layer (G) may be laminated on the surface film layer (F) before or after the white resin film layer (A) and the back film layer (F). .

[Physical properties of electrophotographic recording paper]
The electrophotographic recording paper of the present invention is characterized in that its density is 1.01-1.60 g / cm ³ . The density is preferably 1.05~1.50g / cm ^3, more preferably 1.10~1.40g / cm ^3. If the density of the electrophotographic recording paper is within the above range, the transfer energy for transferring the toner is easily transmitted when an image is formed by the electrophotographic recording apparatus, and it is easy to obtain an image quality excellent in density, color tone and gradation. . Further, if the density of the electrophotographic recording paper is within the above range, it is easy to have the waist and flexibility necessary for printing with the electrophotographic recording apparatus, and the transportability in paper feeding and discharging can be obtained. It is excellent in workability when handling recorded material as posted material.

[Recording device]
The electrophotographic recording paper of the present invention can be favorably color-recorded by an electrophotographic recording apparatus such as a copying machine or a laser printer. In the electrophotographic color recording method, (1) an intermediate transfer method in which an intermediate transfer is performed for each color, a plurality of colors are transferred to an intermediate transfer member, and then transferred and developed on a sheet. (2) two or more photosensitive members are used, A tandem method that transfers and develops multiple colors on paper one by one, and (3) a tandem + transfer method that uses two or more photoconductors, transfers multiple colors one by one to an intermediate transfer body, and then transfers and develops them on paper. There are three types. In the present invention, in particular, (2) and (3) are collectively referred to as a tandem system. The electrophotographic recording paper of the present invention can be used in the intermediate transfer system of (1), but is preferably used in the tandem system of (2) and (3). In the method (1), in the case of a small-sized electrophotographic copying machine or the like, the electrophotographic recording paper may be squeezed while being transported in the apparatus and may be difficult to use. The tandem methods (2) and (3) are compatible with high speed, and are preferable because of the structure of the apparatus because the electrophotographic recording paper is not crushed during conveyance.

  The electrophotographic recording paper of the present invention may be subjected to ordinary printing such as oil-based offset printing, UV offset printing, gravure printing, flexographic printing and the like before recording using the recording apparatus. If necessary, a management bar code may be printed by such printing, thermal transfer method, or electrophotographic method. The electrophotographic recording paper of the present invention has an entire surface before lamination with the base material layer on the back surface of the synthetic resin film (the surface opposite to the coat layer as the toner receiving layer) in order to promote sales and visibility. Printing or partial printing may be performed. Similarly, full surface printing or partial printing may be performed on the surface of the paper material on which the synthetic resin film is laminated before the synthetic resin film is laminated. These printings are preferably performed so as to be regular information when viewed through a synthetic resin film.

[Recordings]
The recorded material using the electrophotographic recording paper of the present invention includes a POP card (poster, sticker, display, etc.), store information (pamphlet, company information, product writing, menu, etc.), underlay (lunch mat, table mat, stationery) Supplies), manuals (various manuals for duties, operations, operations, etc., process charts, timetables, etc.), charts (nautical charts, weather charts, charts, ruled line charts, etc.), catalogs, cards (price cards, point cards, members cards) , Various membership cards, student ID cards, licenses, employee ID cards, entrance / exit certificates, association IDs, ID cards, student attendance cards, book cards, examination cards, management cards, parking licenses, ski tickets, CD, MD titles Card, CD, MD index card, photo card, etc.), panel, plate (alternative to metal plate), bromide, preservation document (Word processing documents, various lists, appraisals, certificates, important documents, certificates, etc.), pictorial books, drawings (architectural drawings, civil engineering site screens, etc.), maps (nautical charts, route maps, outdoor maps, etc.), commuter pass, shop front Price list, mountain climbing guide, business card, lost child tag, cooking recipe, information board (sales guidance, direction / destination guidance, sweets / food, etc.), gardening POP (hanging label, feed label, etc.), schedule table, road・ Signs (funerals / housing exhibition places, etc.), circular boards, room name tags, school records, display boards (forbidden to enter, forest road work, etc.), division piles, nameplates, calendars (with images), simple whiteboards, postcards, Greeting cards, flyers, picture books, picture-story shows, portable timetables, album picture diaries, paperwork (paper craft), copy manuscripts, round fans, megaphones, mouse pads, bookmarks, pet toilets, packaging materials Wrapping paper, boxes, bags, etc.), coasters, flower pots, printed materials that do not require lamination, label lighter replacement printed materials, adhesive labels, tags (air tags, IC tags, triage tags), etc. It is. In particular, it can be suitably used for applications based on outdoor use.

[Examples and Comparative Examples]
Hereinafter, the present invention will be described more specifically with reference to adjustment examples, production examples, examples and comparative examples. In addition, the material, usage-amount, ratio, processing content, and processing procedure shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[Adjustment Examples 1 to 3]
(Polymer antistatic agent adjustment example 1)
100 parts by mass of polyethylene glycol monomethacrylate (trade name: Blemmer PE-350, manufactured by NOF Corporation), 20 parts by mass of lithium perchlorate (manufactured by Wako Pure Chemical Industries, Ltd., reagent), hydroquinone (Wako Pure Chemical Industries, Ltd.) (Reagents), 1 part by mass, and 400 parts by mass of methyl ethyl ketone were introduced into a four-necked flask equipped with a stirrer, condenser, nitrogen inlet tube and thermometer, and the system was purged with nitrogen. Reacted for hours. Stearyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd., reagent) 20 parts by mass, n-butyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd., reagent) 20 parts by mass, azobisisobutyronitrile (Wako Pure Chemicals) (Made by Kogyo Co., Ltd., reagent) 1 part by mass was added and polymerized at 80 ° C. for 3 hours, then methyl ethyl ketone was added to adjust the solid content to 20% by mass, and the mass average molecular weight was about 300,000. A solution of a polymer antistatic agent having a lithium concentration of 0.8 wt% was obtained.
(Example 2 of preparation of (meth) acrylic resin polymer binder)

2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd., reagent) 15 parts by mass, methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd., reagent) 50 parts by mass, ethyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.) , Reagent) and 100 parts by mass of toluene were charged into a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer. After purging with nitrogen, 2,2′-azobisisobutyronitrile (sum) 0.6 parts by mass of Reagent, manufactured by Kojun Pharmaceutical Co., Ltd. was added as an initiator, and the mixture was polymerized at 80 ° C. for 4 hours. The obtained solution was a 50 mass% toluene solution of a hydroxyl group-containing (meth) acrylic acid ester copolymer resin having a hydroxyl value of 65. Next, 40 parts by mass of a 20% by mass methyl ethyl ketone solution of vinyl chloride-vinyl acetate copolymer (trade name: ZEST C150ML, manufactured by Shin Daiichi PVC Co., Ltd.) and hexamethylene diisocyanate (trade name: 20 parts by mass of HDI (manufactured by Tosoh Corporation) was added, and a solvent in which toluene and methyl ethyl ketone were mixed 1: 1 was added to the mixture to adjust the solid content to 20% by mass. Obtained.
(Example 3 of preparation of polyester resin polymer binder)
10 parts by mass of amorphous polyester resin (trade name: Byron GK130, manufactured by Toyobo Co., Ltd.), 10 parts by mass of amorphous polyester resin (trade name: Byron 240, manufactured by Toyobo Co., Ltd.), 40 parts by mass of ethyl methyl ketone And 40 parts by mass of toluene were mixed with a stirrer, and the polyester resin was dissolved in an organic solvent to obtain a polymer binder solution having a solid content of 20% by mass.

[Production Examples 1 to 12]
(Production Example 1 of white resin film layer (A))
Polyethylene terephthalate (trade name: Novapex G5, manufactured by Mitsubishi Chemical Corporation) 88 mass%, styrene homopolymer (trade name: PSJ-polystyrene SGP10, manufactured by PS Japan) 10 mass%, and titanium dioxide fine powder (trade name: TA) -300, manufactured by Fuji Titanium Co., Ltd.) 2% by mass of resin composition C, and polyethylene terephthalate (trade name: Novapex G5, manufactured by Mitsubishi Chemical Corporation) 95% by mass, and titanium dioxide fine powder (trade name: TA-300, (Made by Fuji Titanium Co., Ltd.) Resin composition B consisting of 5% by mass was melt-kneaded at 280 ° C. using three kneading extruders, and then supplied to a coextrusion die set at 280 ° C. and laminated in the die. Then, it was extruded into a sheet shape and rapidly cooled to 30 ° C. with a cooling roll to obtain a three-layer unstretched sheet (B / C / B). The obtained unstretched sheet was heated to 85 ° C. using a longitudinal stretching machine composed of a plurality of roll groups and stretched in the longitudinal direction (MD direction) at a magnification of 3.4 times to obtain a longitudinally stretched sheet. Next, the obtained longitudinally stretched sheet was heated again to 130 ° C. using a tenter, then cooled with cold air, stretched at a magnification of 3.7 times in the transverse direction (TD direction) at 12 ° C., and 85 ° C. Then, the sheet ear portion was slit to obtain a white resin film layer (A) of Production Example 1 composed of a multilayer stretched resin sheet.

The obtained white resin film layer (A) has a total thickness of 50 μm (each layer thickness: B / C / B = 5 μm / 40 μm / 5 μm) and a porosity of 16.7% as measured by the method described later. there were.
(Production Example 2 of white resin film layer (A))
Polyethylene terephthalate (trade name: Novapex G5, manufactured by Mitsubishi Chemical Corporation) 85% by mass, styrene homopolymer (trade name: PSJ-polystyrene SGP10, manufactured by PS Japan) 2% by mass, and propylene homopolymer (trade name: Novatec) PP FY6, manufactured by Nippon Polypro Co., Ltd.) 13% by mass of resin composition D, polyethylene terephthalate (trade name: Novapex G5, manufactured by Mitsubishi Chemical) 98% by mass, and titanium dioxide fine powder (trade name: TA-300, (Made by Fuji Titanium Co., Ltd.) Resin composition A consisting of 2% by mass was melt-kneaded at 280 ° C. using three kneading extruders, and then supplied to a coextrusion die set at 280 ° C. and laminated in the die. Then, it was extruded into a sheet shape and rapidly cooled to 30 ° C. with a cooling roll to obtain a three-layer unstretched sheet (A / D / A). The obtained unstretched sheet was heated to 85 ° C. using a longitudinal stretching machine composed of a plurality of roll groups and stretched in the longitudinal direction (MD direction) at a magnification of 3.4 times to obtain a longitudinally stretched sheet. Next, the obtained longitudinally stretched sheet was heated again to 130 ° C. using a tenter, then cooled with cold air, stretched at a magnification of 3.7 times in the transverse direction (TD direction) at 12 ° C., and 85 ° C. Then, the sheet ear portion was slit to obtain a white resin film layer (A) of Production Example 2 consisting of a multilayer resin stretched sheet.

The obtained white resin film layer (A) had a total thickness of 50 μm (each layer thickness: A / D / A = 4 μm / 42 μm / 4 μm) and a porosity of 28.5% as measured by the method described later. there were.
(Production Example 3 of White Resin Film Layer (A))
In Production Example 1 of the white resin film layer (A), a production example consisting of a multi-layered resin stretched sheet was performed in the same manner as in Production Example 1 except that the discharge amount of each extruder was changed and the thickness of each layer was changed. 3 white resin film layer (A) was obtained.
The obtained white resin film layer (A) has a total thickness of 100 μm (each layer thickness: B / C / B = 10 μm / 80 μm / 10 μm) and a porosity of 16.7% as measured by the method described later. there were. (Production Example 4 of white resin film layer (A))
In Production Example 2 of the white resin film layer (A), a production example consisting of a multi-layered resin stretched sheet is the same as Production Example 2 except that the discharge amount of each extruder is changed and the thickness of each layer is changed. 4 white resin film layer (A) was obtained.

The obtained white resin film layer (A) had a total thickness of 100 μm (each layer thickness: A / D / A = 5 μm / 90 μm / 5 μm) and a porosity of 30.6% as measured by the method described later. there were.
(Production Example 5 of white resin film layer (A))
A resin composition E composed of 85% by mass of polyethylene terephthalate (trade name: Novapex G5, manufactured by Mitsubishi Chemical Corporation) and 15% by mass of titanium dioxide fine powder (trade name: TA-300, manufactured by Fuji Titanium Co., Ltd.) After being melt-kneaded at 280 ° C., the mixture was supplied to an extrusion die set at 280 ° C., extruded into a sheet shape, and rapidly cooled to 30 ° C. with a cooling roll to obtain an unstretched sheet having a single layer structure. The obtained unstretched sheet was heated to 85 ° C. using a longitudinal stretching machine composed of a plurality of roll groups and stretched in the longitudinal direction (MD direction) at a magnification of 3.4 times to obtain a longitudinally stretched sheet. Next, the obtained longitudinally stretched sheet was heated again to 130 ° C. using a tenter, then cooled with cold air, stretched at a magnification of 3.7 times in the transverse direction (TD direction) at 12 ° C., and 85 ° C. Then, the sheet ear portion was slit to obtain a white resin film layer (A) of Production Example 5 comprising a single-layer stretched resin sheet.

The obtained white resin film layer (A) had a total thickness of 100 μm and a porosity of 0% as measured by the method described later.
(Production Example 6 of white resin film layer (A))
In Production Example 1 of the white resin film layer (A), a production example consisting of a multi-layered resin stretched sheet was performed in the same manner as in Production Example 1 except that the discharge amount of each extruder was changed and the thickness of each layer was changed. 6 white resin film layer (A) was obtained.
The obtained white resin film layer (A) has a total thickness of 200 μm (each layer thickness: B / C / B = 10 μm / 180 μm / 10 μm) and a porosity of 18.8% as measured by the method described later. there were.
(Production Example 7 of white resin film layer (A))
An OTP base paper for printing paper having a thickness of 170 μm (manufactured by Oji Paper Co., Ltd., basis weight 175 g / m ² , Cobb method water absorption 24.8 g / m ² ) was used as the white resin film layer (A) of Production Example 7.

(Manufacture example 8 of a surface film layer (C) and a back film layer (F))
A stretched polyethylene terephthalate film (trade name: Diafoil T100, manufactured by Mitsubishi Plastics, Inc.) having a thickness of 25 μm was used as the front film layer (C) and the back film layer (F) of Production Example 8.
(Production Example 9 for the front film layer (C) and the back film layer (F))
A stretched polyethylene terephthalate film (trade name: Toyobo Ester Film E5200, manufactured by Toyobo Co., Ltd.) having a thickness of 12 μm was used as the surface film layer (C) and the back film layer (F) of Production Example 9.
(Production Example 10 for Front Film Layer (C) and Back Film Layer (F))
A stretched polyethylene terephthalate film (trade name: Espet Film T6140, manufactured by Toyobo Co., Ltd.) having a thickness of 12 μm was used as the front film layer (C) and the back film layer (F) of Production Example 10.

(Manufacture example 11 of a coating agent)
While gently stirring 8 kg of methyl ethyl ketone with a Cowles mixer, 1 kg of precipitated silica (trade name: Mizukasil P-527, manufactured by Mizusawa Chemical Co., Ltd.) with an average particle diameter of 1.6 μm and an oil absorption of 180 cc / 100 g and average particles After weighing 1 kg each of barium sulfate (trade name: Variace B-32, manufactured by Sakai Chemical Industry Co., Ltd.) with a diameter of 0.3 μm and adjusting the solid content concentration to 20% by mass, Cowles The rotation speed of the mixer was increased and the mixture was stirred for 30 minutes to obtain a pigment dispersion.

Next, the number of rotations of the cowless mixer was reduced, and 11.8 kg of the solution of the (meth) acrylic resin-based polymer binder obtained in Preparation Example 2 was added to the pigment dispersion, and the polymer obtained in Preparation Example 1 above. 2.5 kg of an antistatic agent solution and 0.8 kg of a polyisocyanate for coating (trade name: Coronate HL, manufactured by Tosoh Corporation) previously diluted with ethyl acetate to a solid content of 20% by mass were added in this order, and 20 The mixture was stirred for minutes and mixed, and then the coarse particle size was removed through a 100-mesh filter to obtain the coating agent of Production Example 11.
(Manufacture example 12 of a coating agent)
While gently stirring a mixed solvent of 1 kg of methyl ethyl ketone and 1 kg of toluene with a Cowles mixer, 0.5 kg of cross-linked acrylic resin particles having an average particle diameter of 4.0 μm (trade name: Ganzpearl GM-0401S, manufactured by Aika Industries Co., Ltd.) After adding little by little and adjusting so that solid content concentration might be 20 mass%, the rotation speed of the cowless mixer was raised and it stirred for 30 minutes, and obtained the pigment dispersion liquid.

Subsequently, the rotation speed of the cowless mixer was reduced, and 20 kg of the polyester resin polymer binder solution obtained in Preparation Example 3 and the polymer antistatic agent obtained in Preparation Example 1 were added to the pigment dispersion. 2.5 kg of the solution was added in this order, and the mixture was stirred as it was for 20 minutes, and then the coarse particle size was removed through a 100-mesh filter to obtain the coating agent of Production Example 12.

[Example 1]
The stretched polyethylene terephthalate film (trade name: Diafoil T100, manufactured by Mitsubishi Plastics, melting point: 258 ° C.) obtained in Production Example 8 was used as the surface film layer (C), and a polyether urethane adhesive (Toyo Morton Co., Ltd.) was used. ) Product name: TM-317) 60 parts by weight,
Adhesive paint consisting of 40 parts by weight of a polyisocyanate curing agent (trade name: CAT-11B, manufactured by Toyo Morton Co., Ltd.) (indicated as “DL” in Table 5) has a dry solid content of 2 g / m ^2. And then dried at 60 ° C. for 1 minute to provide an adhesive layer (B). This was overlaid on one side of the white resin film layer (A) obtained in Production Example 1 so that the adhesive layer (B) was opposed, and pressure-bonded via a pressure-bonding roll, and then obtained in Production Example 8 A polyethylene terephthalate film (trade name: Diafoil T100, manufactured by Mitsubishi Plastics Co., Ltd., melting point: 258 ° C.) was used as a surface film layer (F), and a polyether urethane adhesive (manufactured by Toyo Morton Co., Ltd., trade name: TM). -317) Dry solid content of an adhesive paint (indicated as “DL” in Table 5) consisting of 60 parts by weight and 40 parts by weight of a polyisocyanate-based curing agent (trade name: CAT-11B, manufactured by Toyo Morton Co., Ltd.) Was 2 g / m ² and dried at 60 ° C. for 1 minute to provide an adhesive layer (E). This is overlaid on the other surface of the white resin film layer (A) so that the adhesive layer (E) faces, and is pressure-bonded via a pressure-bonding roll to form a five-layer structure (surface film layer ( C) / Adhesive layer (B) / White resin film layer (A) / Adhesive layer (E) / Back film layer (F)) was obtained.

On the both sides of the laminate, the coating agent obtained in Production Example 11 was applied using a bar coater so that the dry solid content per side was 10 g / m ^2, and the dryer set at 70 ° C. The electrophotographic recording paper of Example 1 was obtained by drying for 1 minute to form a front coat layer (D) and a back coat layer (G), respectively. Table 5 summarizes the physical properties and evaluation results of the obtained electrophotographic recording paper.

[Examples 2 to 6, Comparative Example 4]
Using the white resin film layer (A), surface film layer (C), back film layer (F), surface coat layer (D), and back coat layer (G) described in Table 5, Examples 3 to 6 and The electrophotographic recordings of Examples 2 to 6 and Comparative Example 4 were performed in the same manner as in Example 1 except that the coating agent was applied so that the dry solid content per side was 2 g / m ^{2 in} Comparative Example 4. Got the paper. Table 5 summarizes the physical properties and evaluation results of the obtained electrophotographic recording paper.

[Example 7]
The white resin film layer (A) obtained in Production Example 3, the surface film layer (C) obtained in Production Example 9, the back film layer (F) obtained in Production Example 10, and the coating agent obtained in Production Example 12 The surface coating layer (D) was used and the coating was not performed on the back film layer (F) side, and the back coating layer (G) was not formed. The electrophotographic recording paper of Example 7 was obtained. This is an example of an electrophotographic recording sheet having no back coat layer (G). Table 5 summarizes the physical properties and evaluation results of the obtained electrophotographic recording paper.

[Comparative Example 1]
The white resin film layer (A) obtained in Production Example 5 was used as the electrophotographic recording paper of Comparative Example 1 as it was. Table 5 summarizes the physical properties and evaluation results of the obtained electrophotographic recording paper.
[Comparative Example 2]
The coating agent obtained in Production Example 12 is applied to both sides of the white resin film layer (A) obtained in Production Example 5 using a bar coater so that the dry solid content per side is 2 g / m ^2. The electrophotographic recording paper of Comparative Example 2 was used as a front coat layer (D) and a back coat layer (G) that were dried for 1 minute in a drier set at 70 ° C., respectively. Table 5 summarizes the physical properties and evaluation results of the obtained electrophotographic recording paper.

[Comparative Example 3]
The stretched polyethylene terephthalate film (trade name: Espet Film T6140, manufactured by Toyobo Co., Ltd., melting point: 257 ° C.) obtained in Production Example 10 was used as the surface film layer (C), and a polyether urethane adhesive (Toyo Morton Co., Ltd.) was used. ) Product name: TM-317) 60
An adhesive paint consisting of 40 parts by weight of polyisocyanate curing agent (product name: CAT-11B, manufactured by Toyo Morton Co., Ltd.) was applied so that the dry solid content was 2 g / m ^2, and 60 ° C. And dried for 1 minute to provide an adhesive layer (B). This was overlaid on one side of the white resin film layer (A) obtained in Production Example 3 so that the adhesive layer (B) was opposed, and pressure-bonded via a pressure-bonding roll, and then obtained in Production Example 10 A polyethylene terephthalate film (trade name: Espet film T6140, manufactured by Toyobo Co., Ltd., melting point: 257 ° C.) is used as a surface film layer (F), and a polyether urethane adhesive (manufactured by Toyo Morton Co., Ltd.), trade name: TM -317) 60 parts by weight of polyisocyanate-based curing agent (trade name: CAT-11B, manufactured by Toyo Morton Co., Ltd.) 40 parts by weight of the adhesive coating was applied so that the dry solid content was 2 g / m ^2. And dried at 60 ° C. for 1 minute to provide an adhesive layer (E). This is overlaid on the other surface of the white resin film layer (A) so that the adhesive layer (E) faces, and is pressure-bonded via a pressure-bonding roll to form a five-layer structure (surface film layer ( C) / Adhesive layer (B) / White resin film layer (A) / Adhesive layer (E) / Back film layer (F)) was obtained. The obtained laminate was used as an electrophotographic recording paper of Comparative Example 3 as it was. Table 5 summarizes the physical properties and evaluation results of the obtained electrophotographic recording paper.

[Evaluation example]
[Thickness]
The thickness of each of the electrophotographic recording paper and the white resin film layer (A), the front film layer (C), and the back film layer (F) constituting the recording paper is measured according to the method described in JIS P8118. It measured using the apparatus (made by a hybrid company).
In addition, the thickness of each layer when the white resin film layer (A) has a multilayer structure is measured by observing the cross section using an electron microscope during the following porosity observation, and determining the interface between the layers based on the appearance. The ratio was calculated and calculated from the thickness measured above and the thickness ratio of each layer.
[Basis weight]
The basis weight of each of the electrophotographic recording paper and the white resin film layer (A) constituting the recording paper was measured with an electronic balance according to the method described in JIS P8124, and this was measured with an electronic balance. Converted to per weight.
[density]
The densities of the electrophotographic recording paper and the white resin film layer (A) constituting the recording paper were calculated by applying the thickness and basis weight obtained above to the following formula.

[Formula 1]

Density (g / m ³ ) = Basis weight (g / m ² ) / Thickness (m) (1)

[Porosity]
The porosity in the white resin film layer (A) is obtained by observing a cross section of the white resin film layer (A) with a scanning electron microscope, capturing an observation image in an image analyzer, and analyzing the image of the observation region. This is a value obtained by calculating the area ratio of the holes on the cross section. Specifically, a sample for cross-sectional observation is prepared from the white resin film layer (A) using a technique such as a gallium focused ion beam so that vacancies are not crushed, and the obtained sample is a scanning electron microscope ( Using a product name: JSM-6490 (manufactured by JEOL Ltd.), etc., perform cross-sectional observation at an appropriate magnification, and use an image analyzer (product name: LUZEX AP, manufactured by Nireco) from the obtained cross-sectional photograph. Then, the ratio (area ratio) of the area occupied by the pores or the like in the sheet cross section can be calculated and used as the porosity. The porosity is an average value of the porosity when observed in the entire thickness direction of the white resin film layer (A).

[Surface resistivity]
The surface resistivity of the electrophotographic recording paper was measured using a double ring electrode in accordance with JIS K6911: 2006 under conditions of 23 ° C. and 50% relative humidity.
[Printing test]
The electrophotographic recording papers obtained in Examples 1 to 7 and Comparative Examples 1 to 4 were each cut to A3 size to produce evaluation papers, and commercially available laser printers (trade name: Speedia GE5000, manufactured by Casio) ) Is used to feed the evaluation paper from the cassette 1 of the same machine, and N7RGB. 50 continuous TIF images were printed to evaluate the following paper feeding / discharging properties, and from the obtained recorded materials, the following toner adhesion, image quality, and weather resistance were evaluated.

[Feeding / discharging properties]
The paper feeding and discharging properties during printing of electrophotographic recording paper were evaluated according to the following criteria.
○: Both paper feeding and paper ejection are smooth and no problem.
Δ: The paper is not well aligned when paper is ejected.
X: There is a problem that paper clogging occurs during paper feeding or paper ejection.
[Toner adhesion of printed matter]
The recorded matter printed on the electrophotographic recording paper is immersed so that it does not float in the water (ion exchange water) filled in the pad, and after being immersed in water for 24 hours, the recorded image is strongly rubbed with a coin, and the toner adhesion Was visually judged according to the following criteria.
○: No change in recorded image.
X: Peeling occurs in the recorded image.

[Image quality of printed matter]
The recording quality of the recorded matter printed on the electrophotographic recording paper, such as image density, color tone, gradation, etc., was visually judged according to the following criteria.
○: Good in density, color tone and gradation.
Δ: The concentration is slightly low, but it can be used.
X: Density, color tone, or gradation is inferior and cannot be used.
[Weather resistance test]
The recorded matter printed on the recording sheets for electrophotography obtained from Examples 1 to 7 and Comparative Examples 1 to 4 is larger than the A3 size and is coated on a black painted aluminum plate with a double-sided tape. The sample was placed vertically in a sunny place, exposed to direct sunlight and wind and rain for half a year including summer, and after half a year, the contamination of the adherend and the deformation of the recorded material were evaluated.

[Contamination of adherend]
The state of contamination of the aluminum plate around the recorded matter was visually evaluated according to the following criteria.
○: The aluminum plate is free from contamination due to recorded matter.
X: The trace of the component which flowed out from the recorded matter has adhered to the aluminum plate.
[Deformation of recorded material]
The state of deformation of the recorded matter itself was visually evaluated according to the following criteria.
○: The recorded material is not deformed.
X: Wrinkles are generated in the recorded matter.

The thickness of the coat layer (D) and the coat layer (G) is preferably from 0.1 to 20 μm, more preferably from 0.5 to 8 μm, still more preferably from 1 to 4 μm. By setting the thickness of the coat layer to 0.1 μm or more, it becomes easy to obtain toner receiving performance and antistatic performance that are uniform in the surface direction. On the other hand, when the thickness of the coat layer is 20 μm or less, stable antistatic performance and water resistance can be easily obtained regardless of the environment.
Coating layer (D) and coating layer (G), as well as the toner-receiving layer described in Patent Document 2, the temperature 25 ° C., Table Men抵 anti index at a relative humidity of 20% 1 × ¹⁰ 7 ~9 × ¹⁰ It is preferable to contain a polymer antistatic agent so as to be in the range of ¹² Ω.

(Polymer antistatic agent)
The polymer antistatic agent must have both antistatic performance and water resistance performance, and should have a small influence on the antistatic effect even after a heating process using an electrophotographic toner fixing device. is there. That is, a polymer antistatic agent, may be in the range of Table Men抵 anti rate ^{1 × 10 7 ~9 × 10 12} Ω of the coating layer is a toner-receiving layer at a temperature 25 ° C., a relative humidity of 20% fat It is preferable to use a soluble polymer antistatic agent. If it is fat-soluble, it can be used in combination with a binder resin having higher water resistance. In the present invention, the fat-soluble means that it dissolves in an organic solvent to be described later at a solid concentration of 5% by weight or more under normal temperature and pressure and does not generate a precipitate. The polymer antistatic agent used in the present invention is preferably a copolymer of a monomer exhibiting antistatic performance and a hydrophobic (lipophilic) monomer. By copolymerizing a hydrophobic monomer, the solubility in various organic solvents can be enhanced. Examples of such hydrophobic monomers include esters of acrylic acid or methacrylic acid with various alcohols.

[Surface resistivity]
The surface resistivity of the electrophotographic recording paper was measured using a double ring electrode in accordance with JIS K6911: 2006 under the conditions of 25 ° C. and 20 % relative humidity.
[Printing test]
The electrophotographic recording papers obtained in Examples 1 to 7 and Comparative Examples 1 to 4 were each cut to A3 size to produce evaluation papers, and commercially available laser printers (trade name: Speedia GE5000, manufactured by Casio) ) Is used to feed the evaluation paper from the cassette 1 of the same machine, and N7RGB. 50 continuous TIF images were printed to evaluate the following paper feeding / discharging properties, and from the obtained recorded materials, the following toner adhesion, image quality, and weather resistance were evaluated.

Claims (6)

On one side of the white resin film layer (A), the adhesive layer (B), the surface film layer (C), and the surface coat layer (D) are laminated in this order,
An electrophotographic recording paper comprising a laminate in which an adhesive layer (E) and a back film layer (F) are laminated in this order on the other surface of the white resin film layer (A),
The white resin film layer (A) has a layer containing 50 to 97% by mass of a thermoplastic resin (X) having a melting point of 200 ° C. or higher, and 3 to 50% by mass of at least one of an organic filler and an inorganic filler,
The density of the electrophotographic recording paper is 1.01-1.60 g / cm ³ ;
Recording paper for electrophotography. On one side of the white resin film layer (A), the adhesive layer (B), the surface film layer (C), and the surface coat layer (D) are laminated in this order,
2. The laminate according to claim 1, comprising a laminate in which an adhesive layer (E), a back film layer (F), and a back coat layer (G) are laminated in this order on the other surface of the white resin film layer (A). Recording paper for electrophotography.   The recording sheet for electrophotography according to claim 1 or 2, wherein the front film layer (C) and the back film layer (F) contain 99 to 100% by mass of a thermoplastic resin (Y) having a melting point of 200 ° C or higher.   The electrophotographic recording paper according to any one of claims 1 to 3, wherein the thermoplastic resin (X) is a polyester resin.   The recording paper for electrophotography according to claim 3 or 4, wherein the thermoplastic resin (Y) is a polyester resin.   A recorded matter obtained by performing electrophotographic printing on the electrophotographic recording paper according to any one of claims 1 to 5.

Images