JP6831290B2 - Self-adhesive synthetic paper - Google Patents

Description

The present invention can be attached to various objects to be attached as stickers, labels, signs, posters, advertisements, etc., can be used for display for a long period of time, and can be easily peeled off after use. It also relates to self-adhesive synthetic paper with little adhesive residue after peeling.

Conventionally, adhesives, adhesive tapes, etc. have been used to attach posters, advertisements, etc. created by printing to hard objects such as walls, glass surfaces, pillars, bulletin boards, lockers, and bookcases. However, those using adhesives or double-sided tape are not easy to peel off, and the adhesives and adhesives remain on the adherend, so-called "glue residue" occurs, or the paint on the surface of the adherend is peeled off. There was a problem.

As a method of posting posters and advertisements without using an adhesive or adhesive tape, a film that adheres to a smooth adherend is disclosed. For example, Patent Document 1 describes self-adhesion consisting of 50 to 80% by mass of a hydrogenated styrene-based elastomer (C) and 50 to 20% by mass of a propylene / α-olefin random copolymer (D) having a melting point of 135 ° C. or lower. A transparent film having a layer and an intermediate layer and a non-adhesive layer is disclosed. Further, Patent Document 2 discloses a biaxially stretched polypropylene film having a two-layer structure in which a resin composition layer A containing polypropylene and a polypropylene-based elastomer is used as an adhesive layer and a polypropylene resin layer B is used as a core layer. .. These are useful as protective films for electronic, electrical, optical components, etc.

However, since these films are used as protective films, they are required to have flexibility to flexibly follow the shape of the surface of the base material, and when these films are used for posters, etc., they are vertical to walls and the like. When it is attached to the body to be attached, it bends due to gravity and workability is significantly impaired. Further, since it is preferably transparent because it is used as a protective film, an opaque film is not disclosed. When printed on an opaque film and attached to an object to be attached to form a bulletin board, the printing tends to be unclear, and the printability of the surface is not taken into consideration.

Further, since these films do not have voids inside, the density is 0.8 or more. Even if a white inorganic pigment is added to these films so that the printing does not become unclear, or if the film is underwritten with white ink during printing, the density of the film is high, so even if it is attached to the object to be attached, its own weight. Tends to fall easily.
In addition, when the force generated by the curl of the film is stronger than the adsorption force with the adherend, it is expected that the film will be lifted from the adherend by the curl of the film during long-term use. As described above, the current situation is that a film having various conditions required for these self-adhesive synthetic papers has not yet been developed.

Japanese Unexamined Patent Publication No. 2008-006815 Japanese Unexamined Patent Publication No. 2014-20095

In view of the above-mentioned drawbacks of the prior art, the present invention can directly attach and display a printed matter as a poster, an advertisement, etc. on an object to be attached, has a high adsorption force when used for display, and has a sufficient sustainability of the adsorption force for a long period of time. It can be used for display and can be easily peeled off after use, there is no adhesive residue after peeling off, it is possible to wind a long film into a roll shape, and there is no roll type blocking. It is an object of the present invention to provide a self-adhesive synthetic paper that can be pulled out and has excellent ink adhesion, and thus can be used in various printing methods.

As a result of diligent studies to solve these problems, the present inventor has a specific value for the isotactic crystallinity or polyethylene crystallinity of one surface of the film, and the other surface of the film. Has found that it is possible to provide a self-adhesive synthetic paper having desired characteristics by adopting a structure having printability, and has completed the present invention.
That is, the present invention is as follows.

(1) A self-adhesive synthetic paper having at least three layers of a self-adhesive layer (A), a resin film layer (B), and a surface layer (C) in this order, under the following conditions (1) or (2). Meet self-adhesive synthetic paper.
(1) The self-adhesive layer (A) contains a propylene resin and contains
The isotactic crystallinity obtained by measuring the surface of the self-adhesive layer (A) by ATR infrared spectroscopy is 20 to 65%.
(2) The self-adhesive layer (A) contains an ethylene resin and contains
The polyethylene crystallinity obtained by measuring the surface of the self-adhesive layer (A) by ATR infrared spectroscopy is 60 to 75%.
(2) The propylene-based resin is characterized by containing a propylene-based resin having an endothermic peak by the differential scanning calorimetry at 120 to 180 ° C. and a resin having no endothermic peak by the differential scanning calorimetry at 0 to 200 ° C. The self-adhesive synthetic paper according to (1).

(3) The resin having no heat absorption peak by the differential scanning calorimetry method at 0 to 200 ° C. is a copolymer of propylene and ethylene or α-olefin, or a copolymer of ethylene and α-olefin. The self-adhesive synthetic paper according to (2), which is a feature.
(4) The self-adhesive synthetic paper according to (2), wherein the resin having no endothermic peak by the differential scanning calorimetry method at 0 to 200 ° C. contains a hydrogenated styrene resin.
(5) The arithmetic mean roughness (Ra) of the surface of the self-adhesive synthetic paper on the self-adhesive layer (A) side according to JIS B0601: 2003 is 0.2 to 0.7 μm (1). The self-adhesive synthetic paper according to any one of (4).

(6) The self-adhesive synthetic paper according to any one of (1) to (5), wherein the resin film layer (B) is a stretched film layer.
(7) The surface resistivity of the surface layer (C) measured in accordance with JIS K6911: 2006 is 1 × 10 ^{-1 to} 9 × 10 ¹² Ω (1) to (6). The self-adhesive synthetic paper described in any of.
(8) The surface layer (C) contains an antistatic polymer and a polymer binder, and contains
The antistatic polymer comprises an alkali metal salt containing polymer or a quaternary ammonium salt type copolymer.
The self-adhesive synthetic paper according to (7), wherein the polymer binder contains a (meth) acrylic resin or a polyethyleneimine-based resin.

(9) Any of (1) to (8), wherein the self-adhesive synthetic paper has a rigidity of 0.05 to 10 mN according to the bending repulsion A method (Gale method) according to JIS L1096: 2010. Self-adhesive synthetic paper described in Crab.
(10) The self-adhesive synthetic paper according to any one of (1) to (9), wherein the self-adhesive synthetic paper has an opacity of 50 to 100% according to JIS P8149: 2000.
(11) The coefficient of static friction between the surface of the self-adhesive layer (A) side of the self-adhesive synthetic paper according to JIS K7125: 1999 and the glass plate is 0.7 to 1.1 (1) to 1. The self-adhesive synthetic paper according to any one of (10).
(12) The self-adhesive layer (A) of the self-adhesive synthetic paper is moistened with water, attached to an acrylic plate, stored at 25 ° C. for 24 hours, and then the self-adhesive synthetic paper is peeled off. The self-adhesive synthetic paper according to any one of (1) to (11), wherein there is no visible mark on the surface.
(13) A bulletin board characterized in that the self-adhesive synthetic paper according to any one of (1) to (12) is attached to an object to be attached.

According to the present invention, it is possible to provide a self-adhesive synthetic paper capable of displaying a printed matter as it is as a poster, an advertisement or the like on a sticking body.
The self-adhesive synthetic paper has a high adsorptive power and has sufficient long-term adsorption power sustainability, and at the same time, it can be easily peeled off after use, and adhesive residue may occur after the peeling off. Absent.
In addition, it is possible to wind a long film formed into a roll shape, and even when it is made into a roll shape, it can be pulled out without blocking and has excellent ink adhesion. .. Due to these characteristics, the self-adhesive synthetic paper of the present invention can be used for various printing methods.

It is the schematic of the adhesion measuring apparatus used in an Example.

The self-adhesive synthetic paper of the present invention is a self-adhesive synthetic paper having at least three layers of a self-adhesive layer (A), a resin film layer (B) and a surface layer (C) in this order, and is a base of the synthetic paper. It has a structure in which a self-adhesive layer (A) is laminated on one surface of a resin film layer (B) as a material, and a surface layer (C) having printability is laminated on the other surface.
Hereinafter, each layer of the self-adhesive layer (A), the resin film layer (B), and the surface layer (C) will be described in sequence.

[Self-adhesive layer (A)]
(1) The self-adhesive layer (A) contains a propylene resin and contains
The self-adhesive layer (A) has an isotactic crystallinity of 20 to 65% obtained by measuring the surface by ATR infrared spectroscopy, or (2) the self-adhesive layer (A) contains an ethylene resin. ,
The polyethylene crystallinity obtained by measuring the surface of the self-adhesive layer (A) by ATR infrared spectroscopy is 60 to 75%.
More preferably, (A) mainly contains a propylene-based resin.
Regarding which of the conditions (1) and (2) is adopted, the maximum value of the absorbance at 720.0 ± 1 cm ^-1 when the surface of the self-adhesive layer (A) is measured by ATR infrared spectroscopy ( a ₇₂₀₎ and the ratio _a 720 _{/ a 974} of maximum absorbance and _{(a 974)} in 974.0 ± ^{1 cm -1} _is applied condition (1) when less than _{1.0, a} 720 _/ a ₉₇₄ 1 When it is 0.0 or more, the condition (2) is applied.
As the ATR infrared spectrophotometry, a Fourier transform infrared spectrophotometer (FTIR) is used, and the degree of crystallization of the surface of the measurement sample can be measured by measuring by the attenuation total reflection method. Here, the FTIR method uses a germanium prism, and the number of integrations is preferably 32 to 128 times. The maximum value of absorbance is the distance between the apex of the absorbance peak and the baseline. (Satoshi Tanaka, Shin Takeuchi, Kenji Takemoto, Fumio Nakamura: Central Customs Analysis Bulletin, 46, 65 (2007).)

(Isotactic crystallinity)
The isotropic crystallinity of the surface of the self-adhesive layer (A) is preferably in the range of 20 to 65%. If the isotactic crystallinity value is less than 20%, problems may occur in terms of suppression of take-up blocking, and if it exceeds 65%, problems may occur in terms of adhesion. There is.
Therefore, the isotactic crystallinity of the surface of the self-adhesive layer (A) is preferably in the above range, more preferably in the range of 35 to 62%, and further preferably in the range of 40 to 60%.
Here, the degree of isotactic crystallinity on the surface of the self-adhesive layer (A) means the ratio of the crystal region of the isotactic to the surface of the self-adhesive layer (A) composed of a polypropylene resin containing isotactic. To do.

When the self-adhesive layer (A) mixes a propylene resin having an endothermic peak at 120 to 180 ° C. and a resin having no endothermic peak at 0 to 200 ° C. by the differential scanning calorimetry method, the differential scanning calorimetry is performed. The endothermic peak at 120-180 ° C. according to the method is a peak derived from the melting of the crystalline portion in the polymer. Therefore, the inclusion of a propylene resin having an endothermic peak at 120 to 180 ° C. according to the differential scanning calorimetry has the effect of increasing the isotactic crystallinity of the self-adhesive layer (A), and the self-adhesive synthetic paper It has the effect of improving the molding processability in manufacturing and suppressing the self-adhesive layer (A) from sticking (blocking) when a plurality of self-adhesive synthetic papers are stacked. Further, the resin having no endothermic peak at 0 to 200 ° C. has an effect of lowering the isotactic crystallinity of the self-adhesive layer (A), improving the adhesive force of the self-adhesive layer (A), and the coefficient of static friction with respect to glass. It has the effect of improving the adhesion to the adherend and improving the adhesion to the adherend.

(Polyethylene crystallinity)
In order for the self-adhesive layer (A) to have sufficient adhesive strength, the self-adhesive layer (A) has a polyethylene crystallinity of 60 to 75% determined by ATR infrared spectroscopy. If the polyethylene crystallinity value is less than 60%, problems may occur in terms of suppression of take-up blocking, and if it exceeds 75%, problems may occur in terms of adhesion. .. 62-70% is preferable, and 65-68% is more preferable.

(Propene resin)
The self-adhesive layer (A) may have an isotactic crystallinity of 20 to 65%, preferably 35 to 62%, more preferably 40 to 60%, as determined by ATR infrared spectroscopy.
In order for the isotactic crystallinity of the self-adhesive layer (A) to be within the above range, a homopropylene in which the self-adhesive layer (A) exhibits isotactic crystallinity and an amorphous resin are mixed. This may reduce the isotactic crystallinity, or the isotactic crystallinity may be lowered by including another monomer copolymerizable with propylene as a copolymer component. The self-adhesive layer (A) preferably contains 5 to 60% by mass, more preferably 10 to 50% by mass of the propylene component. It is more preferable that the self-adhesive layer (A) is a mixture of a propylene resin having an endothermic peak at 120 to 180 ° C. and a resin having no endothermic peak at 0 to 200 ° C. according to the differential scanning calorimetry method.

When the isotactic crystallinity is lowered by mixing homopropylene and an amorphous resin, a mixture of a propylene resin and an α-olefin ternary copolymer having 4 to 20 carbon atoms of propylene-ethylene-. , A mixture of a propylene resin and polyethylene, or a mixture of a propylene resin and a hydrogenated styrene resin can be preferably used. In this case, the composition ratio of both is 50 to 90% by mass of the ternary copolymer with respect to 50 to 10% by mass of the propylene resin, and preferably the ternary common weight with respect to 40 to 20% by mass of the propylene resin. 60 to 80% by mass of coalescence, 50 to 10% by mass of polyethylene with respect to 50 to 90% by mass of propylene resin, preferably 60 to 80% by mass of polyethylene with respect to 40 to 20% by mass of propylene resin, 20 to 20% by mass of propylene resin A composition of 50 to 80% by mass of the hydrogenated styrene resin with respect to 50% by mass, preferably 60 to 70% by mass of the hydrogenated styrene resin with respect to 40 to 30% by mass of the propylene resin (improvement of the static friction coefficient). It is also suitable in terms of (adhesion to the object to be attached) and (prevention of blocking).

When a propylene resin having a heat absorption peak at 120 to 180 ° C. and a resin having no heat absorption peak at 0 to 200 ° C. are mixed according to the differential scanning calorimetry method, the propylene resin having a heat absorption peak at 120 to 180 ° C. is used. Can be used as a homopolymer of propylene or a polymer containing propylene as a main component and copolymerized with ethylene or α-olefin as a component other than propylene. When the propylene component of this copolymer is 95 mol% or more and less than 100 mol%, an endothermic peak of 120 ° C. or higher appears. Specific examples of the α-olefin include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene and the like. ..
Specific examples of those copolymerized with ethylene or α-olefin as components other than propylene include propylene / ethylene copolymer, propylene / ethylene / 1-butene copolymer, and propylene / ethylene / 1-pentene copolymer. , Propylene / ethylene / 1-hexene copolymer, propylene / ethylene / 4-methyl-1-pentene copolymer, propylene / ethylene / 1-heptene copolymer, propylene / ethylene / 1-octene copolymer, propylene -Examples include ternary copolymers such as ethylene / 1-nonene copolymer and propylene / ethylene / 1-decene copolymer. These polymers can be used alone or in admixture of two or more.

On the other hand, the resin having no heat absorption peak at 0 to 200 ° C. is a copolymer of propylene and ethylene or the above-mentioned α-olefin, a copolymer of ethylene and α-olefin, or hydrogenated styrene-butadiene. Is preferable. In the case of a copolymer of propylene and ethylene or the above-mentioned α-olefin, the endothermic peak does not appear when the propylene component of the copolymer is less than 95 mol%.
The method for producing the polypropylene-based resin composition is not particularly limited, and any production method may be used as long as the above characteristics are satisfied. For example, a polypropylene-based resin composition can be produced by continuously polymerizing polypropylene and a copolymer by multi-stage polymerization. Specifically, a method of polymerizing polypropylene in the first stage and then polymerizing ethylene or α-olefin in the presence of polypropylene in the second stage to polymerize a polypropylene-based resin composition using a plurality of polymerizers. Can be mentioned. Further, a polypropylene-based resin composition may be produced by mixing polypropylene obtained by individually polymerizing and an ethylene-α-olefin copolymer by melt-kneading or the like. Specifically, a method of melt-kneading an ethylene-α-olefin copolymer polymerized using a Ziegler-Natta catalyst such as a titanium-supporting catalyst can be mentioned.
As a propylene-based resin containing a propylene-based resin having an endothermic peak at 120 to 180 ° C. and a resin having no endothermic peak at 0 to 200 ° C., a commercially available product can be used. Examples thereof include Toughmer PN-2060 manufactured by Mitsui Chemicals, Inc. and Zelas MC717R4 manufactured by Mitsui Chemicals, Inc. The production method of Zelas MC717R4 is a propylene-based elastomer produced by a continuous polymerization method in which crystalline polypropylene is polymerized in the first stage and ethylene is polymerized in the second stage, and ethylene polymerized in the second stage. It is presumed that there is no heat absorption peak of the component, and only the heat absorption peak of the polypropylene polymerized in the first stage is observed.

Examples of the hydrogenated styrene-based resin that can be used as a resin having no heat absorption peak at 0 to 200 ° C. include hydrogenated styrene-butadiene copolymer (HSBR), styrene-ethylene / butylene-ethylene copolymer (SEBC), and styrene. Examples thereof include -ethylene-butylene-styrene copolymer (SEBS), and among them, hydrogenated styrene-butadiene copolymer (HSBR) is preferable. In order for the self-adhesive layer (A) to have sufficient adhesive strength, the styrene content of the hydrogenated styrene resin is preferably 30% by mass or less, and more preferably 20% by mass or less. When the styrene content exceeds 30% by mass, the flexibility of the adhesive layer is inferior and the adhesive strength tends to decrease.
As such a hydrogenated styrene resin, a commercially available product can be used, and specific examples thereof include Dynaron 1320P manufactured by JSR Corporation.

On the other hand, when the isotactic crystallinity is lowered by containing another monomer copolymerizable with propylene as a copolymer component, the copolymerized polymer has a propylene unit of 95 to 99, based on the mass of the copolymer. A propylene-ethylene random copolymer containing in the range of 9% by mass, preferably 98 to 99.9% by mass is preferable. When the propylene unit is much less than 95% by mass, the self-adhesive synthetic paper tends to be excessively flexible and the blocking tends to be deteriorated.

(Polyethylene resin)
The self-adhesive layer (A) may have a polyethylene crystallinity of 60 to 75%, preferably 63 to 72%, more preferably 65 to 70%, as determined by ATR infrared spectroscopy. As the polyethylene-based resin that can be used in the present invention, low-density polyethylene polymerized by a high-pressure method, linear low-density polyethylene, or a copolymer of ethylene and α-olefin is preferable. Specific examples of the copolymers include ethylene / propylene copolymers, ethylene / 1-butene copolymers, ethylene / 1-pentene copolymers, ethylene / 1-hexene copolymers, and ethylene / 4-methyl. Examples thereof include -1-pentene copolymer, ethylene / 1-heptene copolymer, ethylene / 1-octene copolymer, ethylene / 1-nonene copolymer, and ethylene / 1-decene copolymer. These can be used alone or in admixture of two or more. At this time, the α-olefin is preferably 0.5 to 15% by mass, more preferably 1.0 to 10% by mass, based on the mass of the copolymer.
As such a polyethylene-based resin, a commercially available product can be used. Specifically, as an example of the high-pressure method polyethylene, Novatec LD LC602A manufactured by Nippon Polyethylene Co., Ltd. can be mentioned, and ethylene / α-olefin can be mentioned. As an example of the copolymer, Evolu SP1071C manufactured by Prime Polymer Co., Ltd. can be mentioned.

The thickness of the self-adhesive layer (A) is preferably 2 to 10 μm, more preferably 2 to 5 μm. When the thickness of the self-adhesive layer (A) is less than 2 μm, the adhesion to the object to be attached tends to be inferior, and when it exceeds 10 μm, the self-adhesive synthetic paper tends to curl.

(Arithmetic Mean Roughness (Ra))
The self-adhesive layer (A) of the present invention has an arithmetic average roughness (Ra) of 0.2 to 0.7 μm measured according to JIS-B-0601: 1994 from the viewpoint of adhesiveness. The surface roughness is more preferably 0.3 to 0.6 μm. If the surface roughness is less than 0.2 μm, the adhesion of the self-adhesive layer (A) becomes too high and peeling occurs. After that, the degree of contamination may be inferior, while if the surface roughness exceeds 0.7 μm, the adsorption surface of the self-adhesive layer (A) will be affected by the undulations and will not be able to maintain smoothness, and will be attached. The adhesion to an object may decrease. In order to obtain the desired value of the surface roughness of the self-adhesive layer (A), the material itself should be selected within the above range, or the above-mentioned embossing or embossing or embossing may be performed. It is preferable to add undulations in the above range to the surface by processing.
A specific method for measuring the arithmetic mean roughness (Ra) on the surface of the self-adhesive layer (A) will be described in Examples.

[Resin film layer (B)]
The resin film layer (B) is a layer that serves as a core portion of the self-adhesive synthetic paper, and a stretched film can be preferably used. As this stretched film, either a single-phase film or a laminated film can be used. The resin material used in the resin film layer (B) may be the same as the polypropylene-based resin used as one component of the self-adhesive layer (A). A self-adhesive layer (A) or a surface layer (C) is laminated on each surface of the resin film layer (B), and it is also effective to perform a corona discharge treatment to improve the adhesiveness with those layers. is there.

(Inorganic powder and organic filler)
In the present invention, the resin film layer (B) is preferably opaque in order to conceal the print information printed on the surface layer (C) described later. The opacity of the resin film layer (B) is preferably 50% or more, more preferably 70% or more, and even more preferably 80% or more.
The volume average particle size of the inorganic powder or organic filler that can be added to the resin film layer (B) is usually 0.01 μm or more, preferably 0., from the viewpoint of achieving whitening and opacity of the base layer (A). It is 1 μm or more. On the other hand, it is usually 10 μm or less, preferably 5 μm or less, from the viewpoint of flow characteristics during film forming and the difficulty of breaking the film. In the present invention, the volume average particle size is measured by using a particle size distribution meter by laser diffraction.

The types of inorganic powder used for the resin film layer (B) include calcium carbonate, calcined clay, silica, diatomaceous earth, white clay, talc, titanium oxide, barium sulfate, alumina, zeolite, mica, sericite, bentonite, sepiolite, etc. Examples include vermiculite, zeolite, wallastonite, and glass fiber. Of these, calcium carbonate, talc, and titanium oxide are preferable, and calcium carbonate and titanium oxide are even more preferable, from the viewpoints of whitening, opacity, and resin moldability.
When the resin film layer (B) contains an inorganic powder, the resin film layer (B) contains 1% by mass or more of the inorganic powder from the viewpoint of increasing the opacity and whiteness of the resin film layer (B). It is preferable, and it is more preferable to contain 5% by mass or more. On the other hand, from the viewpoint of stretching stability during the production of the resin film layer (B) described later, the resin film layer (B) preferably contains 70% by mass or less of the inorganic powder, and preferably contains 60% by mass or less. Is more preferable, 50% by mass or less is further preferable, and 30% by mass or less is most preferable.

When the resin film layer (B) contains an organic filler, it is preferably contained in an amount of 0.01% by mass or more from the viewpoint of exhibiting the function of the organic filler. On the other hand, from the viewpoint of improving the appearance after printing, the content is preferably 20% by mass or less, and more preferably 10% by mass or less. As the organic filler, it is preferable to select a resin of a type different from the thermoplastic resin which is the main component of the resin film layer (B). Above all, it is more preferable to select a resin exhibiting a higher melting point or glass transition point than the thermoplastic resin which is the main component of the resin film layer (B). For example, when the thermoplastic resin which is the main component of the resin film layer (B) is a polyolefin resin (melting point is 80 to 160 ° C.), the melting point of the organic filler is preferably 170 to 300 ° C., and the organic filler The glass transition point is preferably 170 to 280 ° C. Examples of the organic filler exhibiting such a melting point or glass transition point include polyethylene terephthalate, polybutylene terephthalate, poly-4-methylpentene-1, polycarbonate, nylon-6, nylon-6,6, and the like, and a resin film layer. It is more preferable to select a resin that is incompatible with the thermoplastic resin that is the main component of (B).
When the thermoplastic resin which is the main component of the resin film layer (B) is a polyolefin resin, examples of the organic filler include polystyrene, polymethylmethacrylate and the like in addition to the resins listed above, and the resin film layer (B) When the thermoplastic resin which is the main component of the above is a propylene resin, examples of the organic filler include high-density polyethylene, low-density polyethylene, cyclic polyolefin, and the like in addition to the resins listed above.

(Stretched film)
The resin film layer (B) is preferably a stretched film, and the stretched film may be either a uniaxially stretched film or a biaxially stretched film. Further, in the case of a laminated film, a combination of a uniaxially stretched film and a biaxially stretched film may be used. The thickness of the resin film layer (B) is preferably 40 to 200 μm, more preferably 50 to 150 μm. If the thickness of the resin film layer (B) is less than 40 μm, the Gale rigidity and softness will be low, and the workability when the resin film layer (B) will be attached to the object to be attached tends to be inferior. Or it becomes difficult to wind.

(Stretching)
The resin film layer (B) preferably includes a stretched resin film layer stretched in at least one axial direction. The stretching of the resin film layer can be carried out by any of various commonly used methods.
The stretching temperature may be a temperature range equal to or higher than the glass transition temperature of the thermoplastic resin mainly used for the resin film layer (B) and lower than the melting point of the crystal portion, and a known temperature range suitable for the thermoplastic resin. it can. Specifically, when the thermoplastic resin of the resin film layer (B) is a propylene homopolymer (melting point 155 to 167 ° C.), it is 100 to 166 ° C., and when it is high density polyethylene (melting point 121 to 136 ° C.), it is 70 to 70 to It is 135 ° C., which is 1 to 70 ° C. lower than the melting point. Also,
The stretching speed is preferably 20 to 350 m / min.

As the stretching method, longitudinal stretching using the difference in peripheral speed of the roll group, transverse stretching using a tenter oven, sequential biaxial stretching combining longitudinal stretching and transverse stretching, rolling, and simultaneous 2 by combining a tenter oven and a linear motor. Axial stretching, simultaneous biaxial stretching by a combination of a tenter oven and a pantograph, and the like can be mentioned. Further, as a method for stretching the inflation film, simultaneous biaxial stretching by the tubular method can be mentioned.
The draw ratio is not particularly limited, and is appropriately determined in consideration of the characteristics of the thermoplastic resin used for the resin film layer (B). For example, when a propylene homopolymer or a copolymer thereof is used as the thermoplastic resin and it is stretched in one direction, it is about 1.2 to 12 times, preferably 2 to 10 times, and is biaxially stretched. In some cases, the area magnification is 1.5 to 60 times, preferably 4 to 50 times. When other thermoplastic resins are used and stretched in one direction, the ratio is 1.2 to 10 times, preferably 2 to 5 times, and in the case of biaxial stretching, the area magnification is 1.5 to 5. It is 20 times, preferably 4 to 12 times.

The resin film layer (B) thus obtained has a large number of pores inside the film, and the pore ratio calculated by the following formula (1) is preferably 5 to 60%. More preferably, it is ~ 45%. Due to the presence of the pores, the light diffusivity is improved and the resin film layer (B) having high opacity can be obtained.

[Surface layer (C)]
The surface layer (C) in the present invention imparts antistatic performance to the self-adhesive synthetic paper to make it less likely to cause troubles in the printing process and improve handleability, and the surface layer (C) and the printing ink. It improves the adhesion with and improves the printability.
As a result, the self-adhesive synthetic paper of the present invention can be applied to various printing methods.
Since the surface layer (C) has an antistatic performance, the surface layer (C) has a low electrostatic adsorption force even when the self-adhesive synthetic paper has an electric charge inside. In the printing process, troubles such as sticking to rolls and blocking between sheets are unlikely to occur.

(Surface resistivity)
The surface resistivity of the surface layer (C) is preferably 1 × 10 ^{-1 to} 9 × 10 ¹² Ω, more preferably 1 × 10 ^{-7, as} measured in accordance with JIS K6911: 2006.
~ 9 × 10 ¹¹ Ω.
If the surface resistivity of the surface layer (C) exceeds 9 × 10 ¹² Ω, troubles such as sticking of self-adhesive synthetic paper to rolls and blocking between sheets are likely to occur in the printing process. In some cases. On the other hand, it is technically difficult to form the surface layer (C) having high conductivity such that the surface resistivity of the surface layer (C) is less than 1 × 10 ^-1 Ω, or even if it can be formed. , It is not realistic because it will be expensive.

(Composition of surface layer (C))
The surface layer (C) preferably contains 0.1 to 100% by mass of the antistatic agent, 0 to 99.9% by mass of the polymer binder, and 0 to 70% by mass of the pigment particles, and 0.5 to 70% by mass of the antistatic agent. More preferably, it contains 1 to 50% by mass of the antistatic agent, 50 to 99% by mass of the polymer binder, and the pigment particles, and more preferably contains 30 to 99.5% by mass of the polymer binder and 0 to 69.5% by mass of the pigment particles. It is more preferable to contain 0 to 49% by mass.
The surface layer (C) is provided as a coating layer containing these components by direct coating on the resin film layer (B), or a surface layer (C) is previously formed on another film to form the surface layer (C). It is preferably formed by laminating on the resin film layer (A).

(Antistatic polymer)
The antistatic agent is added to impart antistatic performance to the surface layer (C), and is so-called electron conductivity that exhibits conductivity by pi electrons in the molecular chain such as polythiophene, polypyrrole, and polyaniline. Polymers, nonionic polymer-based antistatic agents such as polyethylene glycol and polyoxyethylenediamine, quaternary ammonium salt-type copolymers such as polyvinylbenzyltrimethylammonium chloride and polydimethylaminoethylmethacrylate quaternized products, and alkylene oxide groups. And / or a polymer having an antistatic function typified by an alkali metal salt-containing polymer such as an alkali metal ion additive to a hydroxyl group-containing polymer can be mentioned. Electroconductive polymers are generally colored black, green, or bluish gray due to the coloring derived from the conjugated system, and although excellent antistatic effect can be obtained by using this, it becomes a dull color label for printing. There are drawbacks such as not being suitable as a base paper. A polymer having an antistatic function is preferable as an antistatic agent used in the present invention because it has little effect on the adhesion and transferability of ink and has almost no coloring.

Among these, alkali metal salt-containing polymers such as alkali metal ion additives to alkylene oxide group and / or hydroxyl group-containing polymers, and quaternary ammonium salt types such as polyvinylbenzyltrimethylammonium chloride and polydimethylaminoethylmethacrylate quaternary products. Since the copolymer has good antistatic performance and the influence of environmental humidity on the antistatic performance is small, it is more preferable as the antistatic agent used in the present invention.

(Polymer containing alkali metal salt)
Another example of the polymer having an antistatic function that can be used as the antistatic agent of the present invention is an alkali metal salt-containing polymer. The alkali metal salt-containing polymer is a polyalkylene oxide compound monomer structural unit (a) represented by the following general formula (Chemical formula 1) and a hydrophobic monomer structural unit represented by the following general formula (Chemical formula 2). (B) and the structural unit (c) composed of a monomer copolymerizable with these are contained, and the mass ratio of these structural units is determined by (a) :( b) :( c) = 1 to 99: 0. It is an alkali metal salt-containing polymer obtained by copolymerizing these in the range of ~ 99: 0 to 40 (wt%).

The mass ratio of each structural unit (a), (b) and (c) is preferably 20 to 70:30 to 80: 0 to 20 (wt%), particularly preferably 30 to 60:40 to 70: 0 to 0. It is 10 (wt%). Next, the structural units (a), (b), and (c) will be described.
(A) Polyalkylene Oxide Compound Monomer Unit The polyalkylene oxide compound monomer forming the structural unit (a) is an ester of acrylic acid to methacrylic acid represented by the following general formula (Chemical Formula 1). The unit is a component that contributes to the antistatic function of the surface layer (C) by anions and alkali metal ions in the structure. If the amount of the same component in the surface layer (C) is less than 1% by mass, a sufficient antistatic effect cannot be given. If it exceeds 99% by mass, it becomes excessively water-soluble and causes stickiness under high humidity conditions.

In the above formula, R ¹⁰ is a hydrogen atom or a methyl group, R ¹¹ is a hydrogen atom, a chlorine atom or a methyl group, A is one kind of linking group selected from the following <1 group>, or the following <1 group. > Represents a linking group in which one or more linking groups selected from> and one or more linking groups selected from the following <2 groups> are alternately bonded, or a single bond, where M is an alkali metal ion. n represents an integer of 1 to 100.
<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 alkylene group having 1 to 6 carbon atoms in <Group 1> include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group and a hexylene group, and these groups are linear or branched. It may be, but 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, an anthrylene group and the like. Examples of the substituent include a hydroxyl group and an alkyl group. Examples of the arylene group substituted with the alkyl group include a trilene group and a kyrylylene group.

Further, as the linking group selected from <Group 2>, a urethane group or an ester group can be preferably selected.
As a linking group in which one or more linking groups selected from <1 group> and one or more linking groups selected from <2 group> are alternately bonded, "(linking group selected from 1 group) )-(Linking group selected from 2 groups) "or" (Linking group selected from 1 group)-(Linking group selected from 2 groups)-(Selected from 1 group Linking groups)-(Linking groups selected from the two groups) ”. In the latter case, the two types (linking groups selected from the first group) may be the same or different from each other, and the two types (linking groups selected from the two groups) are the same as each other. It may or may not be different.

In the above general formula (Chemical formula 1), when n is 2 or more, n R ^11s may be the same or different, but it is preferable that they are the same. Although n represents an integer of 1 to 100, 2 to 50 is preferable, and 3 to 50 is more preferable. For example, when R ¹¹ is a hydrogen atom, n can be selected from the range of 10 to 35, further 15 to 30, and even 20 to 25, and when R ¹¹ is a methyl group, n can be selected from 1 to 20, and further. May be selected from the range of 3 to 16, and further 5 to 14.

In the above general formula (Chemical formula 1), M is an alkali metal, and Li, Na, K and the like can be mentioned, and it is preferable to use Li having a small ionic radius from the viewpoint of conductivity.
Examples of the polyalkylene oxide compound monomer preferably used in the present invention include (poly) ethylene glycol (meth) acrylate, (poly) propylene glycol (meth) acrylate, and (poly) chloroethylene glycol (meth). Examples thereof include ( poly) alkylene oxide (meth) acrylates such as acrylates, (poly) tetramethylene glycol (meth) acrylates, methoxy (poly) ethylene glycol (meth) acrylates, and methoxy (poly) propylene glycol (meth) acrylates.

Further, in these specific examples, an alkylene oxide monomer having a linking group other than a single bond at a position corresponding to A in the general formula (Chemical formula 1) can also be mentioned. For example, as the compound having a urethane bond in A, the compound described in JP-A-09-113704 can be used.
The method for introducing the alkali metal corresponding to M is not particularly limited, but usually, the alkylene oxide monomer is reacted with an alkali metal salt to ionize the hydroxyl end end, whereby ionic conductivity due to the alkali metal ion can be imparted. .. Examples of alkali metal salts that can be preferably used in the present invention include perchlorates of lithium, sodium or potassium, or inorganic salts such as chlorides, bromides, iodides and thiocyanates thereof. By adding these inorganic salts to the polyalkylene oxide compound monomer and alkoxide it, ionic conductivity due to alkali metal ions can be obtained. Further, Japanese Patent Application Laid-Open No. 09-113704 proposes an alkyd compound having a urethane bond in A of formula 1.

As the alkali metal ion that can be used in the present invention, the above-mentioned lithium, sodium, and potassium can be used, and among them, lithium having a small ionic radius is most suitable. The coating layer of the present invention has an alkali metal ion concentration of preferably 0.01 to 1.00% by mass, more preferably 0.01 to 0.70% by mass, and further preferably 0.01 to 0.50% by mass. It is desirable to add a polymer having an antistatic function so that, if the alkali metal ion concentration is less than 0.01% by mass, a sufficient antistatic effect cannot be obtained, and if it exceeds 1.00% by mass, antistatic is prevented. Although the effect can be obtained, the adhesion with the printing ink is lowered due to the increase of metal ions.

(B) Hydrophobic Monomer Unit The hydrophobic monomer forming the structural unit (b) is an ester of acrylic acid to methacrylic acid represented by the following general formula (Chemical Formula 2). The unit imparts lipophilicity to the copolymer and is a component that contributes to water resistance and printing ink transferability. Copolymerization with a hydrophobic monomer is required to achieve both printability and antistatic properties. If the same component in the polymer is less than 30% by mass, the above effect is reduced. Further, if it exceeds 70% by mass, the antistatic effect is relatively lowered.

In the above formula, R ⁸ represents a hydrogen atom or a methyl group, R ⁹ represents an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 22 carbon atoms, or a cycloalkyl group having 5 to 22 carbon atoms.
Examples of the monomer forming the structural unit represented by the general formula (Chemical Formula 2) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and tertiary butyl (). Examples thereof include alkyl (meth) acrylates such as meta) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, and stearyl (meth) acrylate.

(C) Other monomer units copolymerizable In addition, other simple monomers copolymerizable with the above-mentioned monomer (a) component and monomer (b) component, which are used for copolymerization as needed. As the metric unit, hydrophobic monomers such as styrene, vinyltoluene and vinylacetate represented by the following general formulas (Chemicals 3) to (Chemical formula 7) and hydrophilic singles such as vinylpyrrolidone and (meth) acrylamide are used. The monomer can be mentioned. These monomers can be suitably incorporated as the structural unit (c) in the quaternary ammonium salt type copolymer. The unit facilitates the copolymerization of the copolymer and adjusts the solubility in a solvent when adjusting the coating solution.

(Copolymerization)
The alkali metal salt-containing polymer that can be used in the present invention includes a polyalkylene oxide compound monomer structural unit (a) represented by the above general formula (Chemical Formula 1), a hydrophobic monomer structural unit (b), and these. It can be produced by copolymerizing with the monomeric structural unit (c) that can be copolymerized with.
The method for producing this alkali metal salt-containing polymer is not particularly limited, and known polymerization methods can be appropriately used alone or in combination. However, known polymerization methods such as bulk polymerization, solution polymerization, and emulsion polymerization using a radical initiator are used. It is preferable to adopt the polymerization method of.

The molecular weight of the alkali metal salt-containing polymer that can be used in the present invention is preferably in the range of 10,000 to 1,000,000 in terms of mass average molecular weight measured by gel permeation chromatography (GPC). When the molecular weight is 10,000 or more, it is difficult for the polymer to exude from the formed coating layer, so that sufficient water resistance tends to be easily obtained. When the molecular weight is 1 million or less, it tends to be easily miscible with the binder component, so that coating defects are less likely to occur and a uniform antistatic effect tends to be obtained.

(Quaternary ammonium salt type copolymer)
Another example of the polymer having an antistatic function that can be used in the present invention is a multication type water-soluble polymer composed of a quaternary ammonium salt type copolymer. The copolymer is a quaternary ammonium salt-type monomer structural unit (d) represented by the following general formula (Chemical formula 8) and a hydrophobic monomer structural unit represented by the general formula 2 (Chemical formula 2). (B) and the structural unit (c) composed of a monomer copolymerizable with these are contained, and the mass ratio of these structural units is determined by (d) :( b) :( c) = 30 to 70:30. It is a quaternary ammonium salt type copolymer obtained by copolymerizing these in the range of ~ 70: 0 to 40 (wt%).
The mass ratio of each structural unit (d), (b) and (c) is preferably 35 to 65: 35 to 65: 0 to 20 (wt%), particularly preferably 40 to 60:40 to 60: 0 to 0. It is 10 (wt%).

(D) Quaternary Ammonium Salt Monomer Unit The quaternary ammonium salt monomer forming the structural unit (d) is an ester of acrylic acid to methacrylic acid represented by the following general formula (Chemical Formula 8). To amide. The unit is a component that contributes to the antistatic function of the copolymer by two or more cations in the structure. If the content of the same component in the copolymer is less than 30% by mass, a sufficient antistatic effect cannot be provided. If it exceeds 70% by mass, it becomes excessively water-soluble and causes stickiness under high humidity conditions.

In the above formula, A is an oxo group (-O-) or a secondary amine group (-NH-), R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 2 to 4 carbon atoms or the following general formula. The 2-hydroxypropylene group represented by (Chemical Formula 9), R ³ , R ⁴ , R ⁵ and R ⁶ are alkyl groups having 1 to 3 carbon atoms, and R ⁷ is an alkyl group having 1 to 10 carbon atoms. Alternatively, an aralkyl group having 7 to 10 carbon atoms, X represents a chlorine atom, a bromine atom, or an iodine atom, and m represents an integer of 1 to 3. R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different.

The quaternary ammonium salt-type monomer forming the structural unit (d) represented by the general formula (Chemical formula 8) is a dimethylaminoethyl (meth) acrylate or diethylamino represented by the following general formula (Chemical formula 10). Amine-containing monomers such as ethyl (meth) acrylate and dimethylaminopropyl (meth) acrylamide are modified with a modifier such as 3-chloro-2-hydroxypropyltrimethylammonium chloride represented by the following general formula (Chemical Formula 12). , Can be obtained by modification before or after polymerization.

In the above formula, A is an oxo group (-O-) or a secondary amine group (-NH-), R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 2 to 4 carbon atoms or the following general formula. It is a 2-hydroxypropylene group represented by (Chemical formula 11), and R ³ and R ⁴ represent an alkyl group having 1 to 3 carbon atoms. R ³ and R ⁴ may be the same or different.

In the above formula (Chemical formula 12), R ⁵ and R ⁶ are alkyl groups having 1 to 3 carbon atoms, and R ⁷ has 1 to 1 carbon atoms.
An alkyl group of 10 or an aralkyl group having 7 to 10 carbon atoms, X represents a chlorine atom, a bromine atom, or an iodine atom, and m represents an integer of 1 to 3. R ⁵ and R ⁶ may be the same or different.
(B) Hydrophobic Monomer Unit The hydrophobic monomer forming the structural unit (b) is an ester of acrylic acid to methacrylic acid represented by the following general formula (Chemical Formula 2). The unit imparts lipophilicity to the copolymer and is a component that contributes to water resistance and printing ink transferability. Copolymerization with a hydrophobic monomer is required to achieve both printability and antistatic properties. If the same component in the polymer is less than 30% by mass, the above effect is reduced. Further, if it exceeds 70% by mass, the antistatic effect is relatively lowered.

In the above formula, R ⁸ represents a hydrogen atom or a methyl group, R ⁹ represents an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 22 carbon atoms, or a cycloalkyl group having 5 to 22 carbon atoms.
Examples of the monomer forming the structural unit represented by the general formula (Chemical Formula 2) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and tertiary butyl (). Examples thereof include alkyl (meth) acrylates such as meta) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, and stearyl (meth) acrylate.

(C) Other monomer units copolymerizable In addition, other simple monomers copolymerizable with the above-mentioned monomer (d) component and monomer (b) component, which are used for copolymerization as needed. As the metric unit, hydrophobic monomers such as styrene, vinyltoluene and vinylacetate represented by the following general formulas (Chemicals 3) to (Chemical formula 7) and hydrophilic singles such as vinylpyrrolidone and (meth) acrylamide are used. The monomer can be mentioned. These monomers can be suitably incorporated as the structural unit (c) in the quaternary ammonium salt type copolymer. The unit facilitates the copolymerization of the copolymer and adjusts the solubility in a solvent when adjusting the coating solution.

[Copolymerization]
As a copolymerization method for obtaining the above-mentioned copolymer, a known polymerization method such as bulk polymerization, solution polymerization, or emulsion polymerization using a radical initiator can be adopted. Of these, the preferred polymerization method is the solution polymerization method, which is carried out by dissolving each monomer in a solvent, adding a radical polymerization initiator to the solvent, and heating and stirring under a nitrogen stream. To. The solvent is preferably water, or alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and cellosolob, and these solvents may be mixed and used. As the polymerization initiator, peroxides such as benzoyl peroxide and lauroyl peroxide, and azo compounds such as azobisisobutyronitrile and azobisvaleronitrile are preferably used. The monomer solid content concentration at the time of polymerization is usually 10 to 60% by mass, and the concentration of the polymerization initiator is usually 0.1 to 10% by mass with respect to the monomer. The molecular weight of the quaternary ammonium salt-type copolymer can be set to any level depending on the polymerization conditions such as the polymerization temperature, the polymerization time, the type and amount of the polymerization initiator, the amount of the solvent used, and the chain transfer agent.
The molecular weight of the quaternary ammonium salt-type copolymer that can be used in the present invention is generally such that the mass average molecular weight measured by gel permeation chromatography (GPC) is in the range of 10 to 1,000,000. However, the range of 1,000 to 500,000 is preferable.

(Polymer binder)
The surface layer (C) of the present invention may contain a polymer binder, if necessary. The polymer binder is appropriately used for the purpose of having adhesion to the resin film layer (B) provided with the surface layer (C) and improving the adhesion to the printing ink.
Specific examples of the polymer binder include acrylic acid ester copolymer, methacrylic acid ester copolymer, acrylic acid amide-acrylic acid ester copolymer, acrylic acid amide-acrylic acid ester-methacrylic acid ester copolymer, and polyacrylamide. (Meta) acrylic polymers such as oxazoline group-containing acrylic acid ester-based polymers, polyethyleneimine, alkyl-modified polyethyleneimine having 1 to 12 carbon atoms, poly (ethyleneimine-urea), poly (ethyleneimine-). Polyethyleneimine-based polymers such as ethyleneimine adduct of urea), polyamine polyamide, ethyleneimine adduct of polyamine polyamide, and epichlorohydrin adduct of polyamine polyamide, polyvinylpyrrolidone, polyethylene glycol, etc., as well as acid-modified polyolefin resin and hydroxyl group. Modified polyolefin resin, vinyl acetate resin, urethane resin, polyether resin, polyester resin, urea resin, terpene resin, petroleum resin, ethylene-vinyl acetate copolymer resin, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, Vinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer resin, chlorinated ethylene resin, chlorinated propylene resin, butyral resin, silicone resin, nitrocellulose resin, styrene-acrylic copolymer resin, styrene-butadiene copolymer resin, Acrylic nitrile-butadiene copolymer resin and the like can be mentioned.

Any one of these polymer binders may be used alone, or two or more thereof may be mixed and used. These polymer binders can be used in a form diluted or dispersed in an organic solvent or water. Among these, the (meth) acrylic polymer or the polyethyleneimine-based polymer has good compatibility (compatibility) with the above-mentioned ionic polymer-based polymer having an antistatic function, and is mixed to form a coating material. It is stable, easy to apply, and preferable.

(Inorganic pigment)
The surface layer (C) of the present invention may contain pigment particles, if necessary. The surface layer (C) can contain pigment particles in the range of 0 to 70% by mass. That is, it may or may not contain pigment particles of 70% by mass or less. The content of the pigment particles is preferably 0 to 69.5% by mass, more preferably 0 to 49% by mass.
Pigment particles improve the fixability of printing inks due to their oil absorption, improve the texture and glossiness of the surface as an extender pigment, improve the whiteness as a white pigment, improve the blocking prevention performance by imparting surface irregularities, and light resistance and weather resistance as an ultraviolet reflective material. It can be selected and used as appropriate in consideration of performance enhancement such as performance improvement.

Organic and inorganic powders are used as pigment particles, and specific examples include silicon oxide, calcium carbonate, calcined clay, titanium oxide, zinc oxide, barium sulfate, diatomaceous earth, acrylic particles, styrene particles, polyethylene particles, and polypropylene. Particles and the like can be used. The particle size of the pigment particles is preferably 20 μm or less, and more preferably 15 μm or less. When the particle size of the pigment particles exceeds 20 μm, the pigment particles are likely to fall off from the formed coating layer, and a powder blowing phenomenon occurs. The pigment particle content in the surface layer (C) is preferably in the range of 0 to 70% by mass, more preferably 0 to 60% by mass, and further preferably 0 to 45% by mass. When the content of the pigment particles exceeds 70% by mass, the binder resin is relatively insufficient, the cohesive force of the surface layer (C) is insufficient, and the printing ink tends to be easily peeled off.
The surface layer (C) can be provided as a coating layer by preparing a coating liquid containing the above components, coating the surface layer (C) on the resin film layer (B) or the like, and drying and solidifying the coating liquid. Conventionally known methods and devices can be used for coating.

The surface layer (C) can also be provided on the resin film layer (B) by laminating. In this case, another film provided with the surface layer (C) in advance may be prepared, and this may be laminated on the resin film layer (B). The laminating process can be performed by a method such as ordinary dry laminating or hot laminating.
The surface layer (C) of the present invention has antistatic performance. The surface resistivity of the surface of the surface layer (C) is 1 × 10 ^{-1 to} 9 × 10 ¹² Ω, preferably 1 × 10 ^{3 to} 9 × 10 ¹¹ Ω, and more preferably 1 × 10 ^{6 to} 9 × 10 ¹⁰ Ω. It is adjusted within the range of.

The film thickness of the surface layer (C) is preferably 0.01 to 50 μm, more preferably 0.05 to 30 μm, further preferably 0.1 to 10 μm, and 0.3. It is particularly preferably ~ 8 μm. If the film thickness is less than 0.01 μm, it is difficult to maintain the uniformity of the surface layer (C), and the adhesion of the printing ink may decrease. On the other hand, if it exceeds 50 μm, the surface layer (C) becomes heavy and the self-adhesive layer (A) cannot support its own weight and easily peels off, so that the desired performance of the present invention can be achieved. Hard to achieve.

[Physical characteristics of self-adhesive synthetic paper]
The self-adhesive synthetic paper of the present invention is required to have desirable properties in terms of opacity, friction coefficient, adhesion, stain degree, thickness, curl, blocking, printability, etc., depending on the application. In some cases, describe them.
(Rigidity and softness by the Gale method)

The self-adhesive synthetic paper of the present invention is also suitable for use in posters and other notices, and in the case of that use, it is preferable that the self-adhesive synthetic paper has a certain degree of rigidity from the viewpoint of ease of handling at the time of sticking. The preferred rigidity is 0.05 to 10 mN, more preferably 0.1 to 7 mN, and even more preferably 0.3 to 4 mN. If the rigidity and softness is 0.05 mN or more, the self-adhesive synthetic paper itself is stiff and easy to handle, the work of sticking to the object to be attached can be performed efficiently, and wrinkles are formed when pasting. Hateful. On the other hand, if the rigidity and softness is 10 mN or less, even if a small curl is generated before the application, the material is not easily peeled off from the object to be attached and can be attached neatly.
The rigidity and softness in the present invention are based on the bending repulsion A method (Gale method) according to JIS L1096: 2010.
A specific measurement method will be described in Examples.

(Opacity)
When the self-adhesive synthetic paper of the present invention is used for posters and other notices, it may be preferable to print on the surface layer of the self-adhesive synthetic paper itself, and the self-adhesive synthetic paper itself to avoid the influence of the underlying material to be attached. May be required to be opaque. Further, when the material to be attached is transparent, the back surface of the front surface printing layer may be visible from the side to be attached through the self-adhesive layer and the resin film layer of the self-adhesive synthetic paper, in order to avoid such a situation. Opacity may be required for the self-adhesive synthetic paper itself. The self-adhesive synthetic paper of the present invention preferably has an opacity of 50 to 100%, more preferably 60 to 100%, and even more preferably 70 to 100%. When the opacity is 50 to 100%, a self-adhesive synthetic paper having excellent decorativeness can be obtained because the coloring and the pattern of the object to be attached are not transparent when used as a bulletin board.
The opacity in the present invention is based on JIS P8149: 2000.
A specific measurement method will be described in Examples.

(Coefficient of friction)
The coefficient of static friction between the self-adhesive layer (A) surface of the self-adhesive synthetic paper of the present invention and the glass plate is 0.7 to 1.1, more preferably 0.8 to 1.0. The coefficient of friction is also affected by the arithmetic mean roughness of the self-adhesive layer (A), and as the arithmetic mean roughness increases, the coefficient of static friction tends to decrease and the adhesion to the glass plate tends to decrease. When the coefficient of static friction is in the range of 0.7 to 1.1, it shows good adhesion to the glass plate.
The coefficient of static friction in the present invention is based on JIS K7125: 1999.
A specific measurement method will be described in Examples.

(Adhesion, pollution degree)
The self-adhesive synthetic paper of the present invention has the characteristics that it does not easily peel off after sticking, can be easily peeled off as needed, and has no adhesive residue. Therefore, it has an appropriate adhesive force. Peeling characteristics are also required. Specifically, 70~700gf / cm ² with respect to the acrylic plate, and more preferably preferably it has the adhesion 140~450gf / cm ^2. As for the degree of contamination, it is preferable that there is no visible trace of glue on the acrylic plate after peeling.
A specific measurement method will be described in Examples.

(Thickness, curl, blocking, printability)
The self-adhesive synthetic paper of the present invention includes at least a self-adhesive layer (A), a resin film layer (B), and a surface layer (C), and the total thickness thereof is preferably 40 to 200. Further, since the self-adhesive synthetic paper of the present invention is a laminated film containing layers having different physical properties from each other and contains a stretched film layer, the self-adhesive synthetic paper may curl. The smaller the curl, the more preferable it is, but if it is about 1 to 50 mm, it does not hinder the normal use of self-adhesive synthetic paper.
Since the self-adhesive synthetic paper of the present invention is wound and stored in a roll shape, it does not cause blocking during storage, and it can be pulled out smoothly without causing blocking when it is pulled out from the roll. Required.

The self-adhesive synthetic paper of the present invention can be printed on the surface layer (C), so that it can be used in various fields. As will be described later, it can be used for various purposes, and it is required that the printing ink and the surface layer (C) are sufficiently adhered to each other, and the adhesion strength of the ink is preferably 1.4 kg · cm or more. ..
Specific measurement methods for thickness, curl property, blocking property, and printability will be described in Examples.

[Use of self-adhesive synthetic paper]
The self-adhesive synthetic paper of the present invention can be printed on the surface layer (C), and the printed matter is used for POP cards (posters, stickers, displays, etc.) and store guides (pamphlets, companies). Information, items, menus, etc.), underlays (lunch mats, table mats, stationery supplies, etc.), manuals (various manuals for duties, work, operations, etc., process charts, time schedules, etc.), charts (sea charts, weather charts, charts, etc.) Ruled line table, etc.), catalog, map (sea map, route map, outdoor map, etc.), store price list, mountain climbing guide, business card, lost card, cooking recipe, information board (sales floor information, direction / destination information, etc.), schedule Table, road sign (funeral / house exhibition place, etc.), room name tag, school record table, display board (no entry, forest road work, etc.), section pile, name tag, calendar (with image), simple white board, mouse pad , Packaging materials (wrapping paper, boxes, bags, etc.), coasters, etc. can be exemplified, and all of them can be used.

The present invention will be described in more detail below with reference to test methods, production examples, preparation examples, examples and comparative examples. The materials, amounts used, proportions, operations, etc. shown below can be appropriately changed as long as they do not deviate from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, the mass part described below is based on the mass of solid content, and% is mass% unless otherwise specified.

[Test method]
(Isotactic crystallinity)
The isotactic crystallinity of the surface of the laminated resin film on the self-adhesive layer (A) side was determined by using a Fourier transform infrared spectrophotometer (manufactured by JASCO Corporation, trade name: FT-IR / 2R-410). The surface on the self-adhesive layer (A) side was measured by the attenuation total reflection method, and the maximum values of absorbance in the range of 998 ± 1 cm ^-1 , 974 ± 1 cm ^-1 and 920 ± 1 cm ^-1 were A ₉₉₈ and A ₉₇₄ , respectively. , A ₉₂₀ . Next, "Material Analysis by Infrared Method-Basics and Applications-" (Kodansha Scientific,
In August 1986, in accordance with the first 214-215 pages) ", it was determined isotactic crystallinity _{X PP} using the following equation.
X _PP (%) = 109 × (A _998- A ₉₂₀ ) / (A _974- A ₉₂₀ ) -31.4

(Polyethylene crystallinity)
The degree of polyethylene crystallinity on the surface of the laminated resin film on the self-adhesive layer (A) side was attenuated by using a Fourier transform infrared spectrophotometer (manufactured by JASCO Corporation, trade name: FT-IR / 2R-410). The surface on the self-adhesive layer (A) side was measured by the reflection method, and the maximum values of absorbance in the range of 731 ± 1 cm ^-1 and 720 ± 1 cm ^-1 were set to A ₇₃₁ and A ₇₂₀ , respectively. Next, the polyethylene crystallinity X _PE was determined using the following formula.
X _PE (%) = 100 x (A ₇₃₁ / A ₇₂₀ )

(Endothermic peak by differential scanning calorimetry)
The endothermic peak by the differential scanning calorimetry was determined by the following measurement.
Using a differential scanning calorimeter (Seiko Instruments Inc., trade name: DSC6200), the sample (about 5 mg) is melted at 230 ° C. for 5 minutes, then cooled to 30 ° C. at a rate of 10 ° C./min, and 30 ° C. After holding at ° C. for 3 minutes, the temperature was raised to 230 ° C. at a rate of 10 ° C./min to obtain a calorific value curve. If a valley of the calorific value curve exists within the measurement temperature range, it is determined to have an endothermic peak.
(Measurement of melting point Tm)
A calorie curve was obtained in the same manner as the measurement of the endothermic peak by the differential scanning calorimetry method.
The endothermic peak top temperature of the calorific value curve was defined as the melting point Tm.
(Arithmetic Mean Roughness Ra)
The arithmetic mean roughness Ra (μm) of the surface on the self-adhesive layer (A) side of the laminated resin film conforms to JIS B0601: 2003, and is a three-dimensional roughness measuring device (manufactured by Kosaka Laboratory Co., Ltd., trade name: SE). -3AK) and an analyzer (manufactured by Kosaka Laboratory Co., Ltd., trade name: SPA-11) were used for the measurement.

(Thickness)
The thickness (total thickness) of the laminated resin film was measured using a constant pressure thickness measuring instrument (manufactured by Teclock Co., Ltd., trade name: PG-01J) in accordance with JIS K7130: 1999. The thickness of each layer in the laminated resin film is determined by cooling the sample to be measured with liquid nitrogen to a temperature of -60 ° C or lower and placing it on a glass plate with a razor blade (manufactured by Chic Japan Co., Ltd.). (Product name: Proline blade) is applied at a right angle to cut to prepare a sample for cross-sectional observation, and the obtained sample is used with a scanning electron microscope (manufactured by JEOL Ltd., product name: JSM-6490). The cross section was observed, the boundary line for each thermoplastic resin composition was discriminated from the appearance of the composition, and the total thickness of the laminated resin film was multiplied by the observed thickness ratio of each layer to obtain the value.

(Surface resistivity)
The surface resistivity of the laminated resin film is 23 ° C. and the relative humidity is 50%. When the surface resistivity is 1 × 10 ⁷ Ω or more, the electrode of the double ring method is used in accordance with JIS K6911: 2006. Was measured. If the surface resistivity is less than 1 × 10 ⁷ Ω, JIS K7194: 19
Based on 94, the resistance (R) obtained by measuring with the 4-deep needle method was multiplied by the correction coefficient F to obtain the surface resistivity.

(Gare stiffness and softness)
The Gale stiffness of the laminated resin film conforms to JIS L1096: 2010, and in an environment of temperature 23 ° C and humidity 50% RH, Gale stiffness tester (Daei Kagaku Seiki Seisakusho) in each of the MD and TD directions. It was measured using a product manufactured by GAS-100 Co., Ltd., trade name: GAS-100).
(Opacity)
The opacity of the laminated resin film was determined in accordance with JIS P8149: 2000 by applying black and white standard plates to the back surface of the measurement and determining the ratio of light reflectance (black plate / white plate) as a percentage value. ..
(Static friction coefficient and dynamic friction coefficient)
The coefficient of static friction and the coefficient of dynamic friction of the laminated resin film with respect to the glass plate were measured using a friction coefficient tester (manufactured by Toyo Seiki Co., Ltd., trade name: TR-2) in accordance with JIS K7125: 1999.

(Adhesion)
For the adhesion of the self-adhesive synthetic paper to the acrylic plate, cut the self-adhesive synthetic paper into a size of 700 mm × 250 mm, moisten the self-adhesive layer (A) of the self-adhesive synthetic paper with water, and attach it to the acrylic plate. After wearing and storing at 25 ° C. for 24 hours, the adsorption area becomes 500 mm × 200 mm on the glass plate of the adhesion measuring device shown in FIG. 1 in an atmosphere of relative humidity of 50%, and the lower end width of the measurement sample is 20 mm. Stick the weight so that it sticks out, attach the clip to the lower end of the measurement sample, combine the weights of 10, 50, 200, and 500 g with the thread attached and attach it to the clip, and the weight of the weight when the measurement sample slides down. The adhesion was calculated by converting it to per square meter.

(Degree of pollution)
In the adhesion test of self-adhesive synthetic paper, the degree of contamination was evaluated by the following method for the acrylic plate after peeling.
◯: No visible traces △: No traces when wiped lightly with a cloth ×: No traces can be removed without using water or solvent (curl)
When the self-adhesive synthetic paper is left on a flat table at a temperature of 50 ° C. and a relative humidity of 50%, placed in a direction in which the curls at the four corners are lifted upward one day later, and lifted toward the self-adhesive layer (A) side. Was negative, and the time when it was lifted to the surface layer (C) side was positive, and the average value of the heights of the four corners was measured, and the curl was determined by the following method.
⊚: Average height of 4 corners is less than ± 3 mm 〇: Average height of 4 corners is ± 3 mm or more and less than ± 5 mm △: Average height of 4 corners is ± 5 mm or more and less than ± 10 mm ×: The average height of the four corners is ± 10 mm or more.

(Rewind blocking)
Is it possible to wind the self-adhesive synthetic paper into a roll and store it in an atmosphere of a temperature of 40 ° C. and a relative humidity of 50% for 1 day, and then pull it out smoothly without causing blocking when it is pulled out from the roll? , Wind-up blocking was evaluated by the following method.
◯: There is no peeling sound and it can be pulled out smoothly △: There is peeling sound, but the appearance of the surface layer (C) after picking up is not spoiled ×: There is a loud peeling sound and the surface layer (C) after picking up Spoiling the appearance of

(Printability)
The self-adhesive synthetic paper was stored for one day in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%, and then printed on the surface layer (C) of the self-adhesive synthetic paper, manufactured by Akira Seisakusho Co., Ltd. , Product name: RI-III type printability tester), and evenly apply printing ink (manufactured by T & K TOKA Co., Ltd., product name: Best Cure 161 ink) to a thickness of 1.5 g / m ^2. After printing, the printing ink was dried and solidified by UV irradiation under a metal halide lamp (manufactured by Eye Graphic Co., Ltd., output: 80 W / cm) so that the UV irradiation intensity was 0.04 W / cm ² .
After storing this self-adhesive synthetic paper again in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50% for one day, cellophane tape (manufactured by Nichiban Co., Ltd., trade name: CT-18) was attached to the printed surface. JAPAN TAPPI No. Using an internal bond tester (manufactured by Kumagai Riki Kogyo Co., Ltd., trade name) according to 18-2 (internal bond strength test method), measure the peel strength of the ink and average the results of the two measurements. The value was taken as the adhesion strength. Based on the results, pass / fail evaluation was made based on the following criteria.
◯: Passed adhesion strength is 1.4 kg ・ cm or more ×: Failed Adhesion strength is less than 1.4 kg ・ cm

[Manufacturing example of laminated resin film]
Table 1 shows the blending ratio (parts by mass) of the thermoplastic resin composition. The laminated resin films of Production Examples 1 to 19 were produced according to the following procedure.
“MFR” described in Table 1 refers to the melt flow rate measured by JIS K7210: 1999 (“Test method for melt mass flow rate (MFR) and melt volume flow rate (MVR) of plastic-thermoplastic plastic”). Point to.

Production example of film 1 (Production example 1)
The thermoplastic resin composition j shown in Table 1 is melt-kneaded in an extruder set at 230 ° C., then supplied to an extrusion die set at 250 ° C., extruded into a sheet, and cooled to 60 ° C. by a cooling device. A non-stretched sheet was obtained. This unstretched sheet was heated to 135 ° C. and stretched 5 times in the longitudinal direction by utilizing the difference in peripheral speed of the roll group. Next, the plastic resin composition a is melt-kneaded in one extruder set at 250 ° C., then extruded into a sheet and laminated on the first surface of the 5-fold stretched sheet, and at the same time, the thermoplastic resin composition j is 230. After melt-kneading with one extruder set at ° C., it was extruded into a sheet and laminated on the second surface of the 5-fold stretched sheet to obtain a three-layer laminated sheet. Next, the three-layer laminated sheet was cooled to 60 ° C. Next, the three-layer laminated sheet was heated to about 150 ° C. using a tenter oven to be stretched 8.5 times in the lateral direction, and then further heated to 160 ° C. for heat treatment. Next, the mixture was cooled to 60 ° C., the ears were slit, and the uniaxially stretched layer of the thermoplastic resin composition a was the self-adhesive layer (A), the wall thickness was 80 μm, and the resin composition (a / j /) of each layer. j), a laminated resin film having each layer thickness (10 μm / 60 μm / 10 μm) and each layer stretching axis number (1 axis / 2 axis / 1 axis ) was obtained.

(Manufacturing Examples 2, 3, 7, 8, 10-13, 20-27)
In Production Example 1 of the laminated resin film, instead of the thermoplastic resin composition a, the thermoplastic resin compositions (a, c, d , k to r ) for the self-adhesive layer (A) shown in Table 3 or 4 are used. used. Further, assuming that the thickness of the uniaxially stretched layer of the resin film layer (B) is the same as the thickness of the self-adhesive layer (A), the thickness of the biaxially stretched layer of the resin film layer (B) is 80 μm. Was adjusted.
(Manufacturing Example 4)
The thermoplastic resin composition e, the thermoplastic resin composition g, and the thermoplastic resin composition f shown in Table 1 are melt-kneaded by three extruders set at 230 ° C., and then extruded at 250 ° C. It was supplied to a die, laminated in the die, extruded into a sheet, and cooled to 60 ° C. by a cooling device to obtain a non-stretched three-layer laminated sheet. This three-layer laminated sheet was heated to 135 ° C. and stretched 5 times in the vertical direction by utilizing the difference in peripheral speed of the roll group. The laminated sheet was then cooled to 60 ° C. Then, it was heated again to about 150 ° C. using a tenter oven and stretched 8.5 times in the lateral direction, and then further heated to 160 ° C. for heat treatment.
Next, the mixture was cooled to 60 ° C., the ears were slit, and the biaxially stretched layer of the thermoplastic resin composition e was the self-adhesive layer (A), the wall thickness was 30 μm, and the resin composition (e / g /) of each layer. f), a laminated resin film having each layer thickness (2 μm / 26 μm / 2 μm) and each layer stretching axis number (2 axes / 2 axes / 2 axes) was obtained.

(Manufacturing Example 5)
Except that in Production Example 4 of the laminated resin film, the thermoplastic resin composition i was used instead of the thermoplastic resin composition e of the self-adhesive layer (A), and the thickness of each layer was set to (3 μm / 24 μm / 3 μm). A laminated resin film was obtained in the same manner as in Production Example 4.

(Manufacturing Example 6)
In Production Example 1 of the laminated resin film, the uniaxially stretched layer of the thermoplastic resin composition a is a self-adhesive layer (A) in the same manner as in Production Example 1 except that the thickness of each layer is (3 μm / 14 μm / 3 μm). A laminated resin film having a wall thickness of 20 μm was obtained.
(Manufacturing Example 9)
The thermoplastic resin composition a and the thermoplastic resin composition j are melt-kneaded in two extruders set at 230 ° C., then supplied to an extrusion die set at 250 ° C. and laminated in the die to form a sheet. The non-stretched layer of the thermoplastic resin composition a is the self-adhesive layer (A), the thickness is 80 μm, and the resin of each layer is extruded into a shape, cooled to 60 ° C. by a cooling device, and the ears are slit. An unstretched laminated resin film having a composition (a / j / j) and a thickness of each layer (4 μm / 72 μm / 4 μm) was obtained.

(Manufacturing Examples 14 to 16)
Laminated resin in the same manner as in Production Example 1 except that the thermoplastic resin composition of the self-adhesive layer (A) shown in Table 3 was used instead of the thermoplastic resin composition a in Production Example 1 of the laminated resin film. I got a film. The uniaxially stretched layer of the thermoplastic resin composition b, d, h or g corresponds to the self-adhesive layer (A).
(Manufacturing Example 17)
Except that in Production Example 4 of the laminated resin film, the thermoplastic resin composition g was used instead of the thermoplastic resin composition e of the self-adhesive layer (A), and the thickness of each layer was set to (5 μm / 24 μm / 6 μm). A laminated resin film was obtained in the same manner as in Production Example 4.

Production Example of Film 2 (Production Example 18)
Except that in Production Example 1 of the laminated resin film, the thermoplastic resin composition j was used instead of the thermoplastic resin composition a of the self-adhesive layer (A), and the thickness of each layer was set to (5 μm / 50 μm / 5 μm). A laminated resin film was obtained in the same manner as in Production Example 1.

[Preparation example of polymer having antistatic function]
(Adjustment example P-1)
Polyethylene glycol monomethacrylate (manufactured by Nippon Oil & Fats Co., Ltd., trade name: Blemmer PE-350) 100 parts by mass, lithium perchlorate (manufactured by Wako Pure Chemical Industries, Ltd., reagent) 20 parts by mass, hydroquinone (Wako Pure Chemical Industries, Ltd.) 1 part by mass of reagent) manufactured by Wako Pure Chemical Industries, Ltd. and 400 parts by mass of propylene glycol monoethyl ether (reagent manufactured by Wako Pure Chemical Industries, Ltd.), a stirrer, a reflux condenser, a thermometer, and a dropping funnel. It was introduced into the mounted four-necked flask, the inside of the system was replaced with nitrogen, and the reaction was carried out at 60 ° C. for 40 hours. To this, 5 parts by mass of stearyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd., reagent), 5 parts by mass of n-butyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd., reagent), azobisisobutyronitrile (Wako Pure Chemical Industries, Ltd.) 1 part by mass of (Reagent) manufactured by Kogyo Co., Ltd. was added, and after a polymerization reaction at 80 ° C. for 3 hours, propylene glycol monoethyl ether was added to adjust the solid content to 20% by mass, and the mass average molecular weight was about 300,000. , A solution containing an alkali metal salt-containing polymer having a lithium concentration of 0.6% by mass in the solid content was obtained.

(Adjustment example P-2)
35 parts by mass of N, N-dimethylaminoethyl methacrylate (manufactured by Mitsubishi Gas Chemical Industries, Ltd.), 20 parts by mass of ethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd., reagent), cyclohexyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) , Reagent) 20 parts by mass, Stearyl Methacrylate (manufactured by Wako Pure Chemical Industries, Ltd., reagent) 25 parts by mass, ethyl alcohol 150 parts by mass, and azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd., reagent) 1 part by mass was introduced into a four-necked flask equipped with a stirrer, a reflux cooling tube (condenser), a thermometer, and a dropping funnel, the inside of the system was replaced with nitrogen, and 6 at a temperature of 80 ° C. under a nitrogen stream. A time polymerization reaction was carried out. Next, 85 parts by mass (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) of a 50% by mass aqueous solution of 3-chloro-2-hydroxypropyltrimethylammonium chloride was added, and the mixture was further reacted at a temperature of 80 ° C. for 15 hours, and then water was added. Ethyl alcohol was distilled off while dropping to obtain a solution of a quaternary ammonium salt type copolymer having a final solid content of 20% by mass.

[Example of adjusting polymer binder]
(Adjustment example P-3)
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) 35 parts by mass and toluene (manufactured by Wako Pure Chemical Industries, Ltd., reagent) 100 parts by mass in a four-necked flask equipped with a stirrer, recirculation cooling tube, thermometer, and dropping funnel, and after nitrogen replacement. , 2,2'-azobis (isobutyronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., reagent) was introduced as an initiator and polymerized at 80 ° C. for 4 hours. The obtained solution was a 50% toluene solution of a hydroxyl group-containing methacrylic acid ester-based polymer having a hydroxyl value of 65. Next, 30 parts by mass of a 20% methyl ethyl ketone solution of a vinyl chloride-vinyl acetate copolymer (manufactured by Shin Daiichi PVC Co., Ltd., trade name: ZESTC150ML) was added to 100 parts by mass of this solution, and methyl ethyl ketone (Wako Pure Chemical Industries, Ltd.) was added. ), The solid content was adjusted to 20% by mass, and a polymer binder solution was obtained.

(Adjustment example P-4)
In a four-necked flask equipped with a stirrer, recirculation cooler, thermometer and nitrogen gas inlet, 100 parts by mass of 25% by mass aqueous solution of polyethylene imine (manufactured by Nippon Catalyst Co., Ltd., trade name: Epomin P-1000), 1- 10 parts by mass of chlorobutane (manufactured by Wako Pure Chemical Industries, Ltd., reagent) and 10 parts by mass of propylene glycol monomethyl ether (manufactured by Wako Pure Chemical Industries, Ltd., reagent) were introduced and stirred under a nitrogen stream at 80 ° C. The modification reaction was carried out at temperature for 20 hours, and then water was added to this solution to adjust the solid content to 20% by mass to obtain a polymer binder solution.
[Example of adjusting the coating composition for the surface layer (C)]
Table 2 shows the blending ratio (parts by mass) of the coating composition for the surface layer (C).

(Adjustment example 1: For surface layer (C))
While gently stirring the methyl ethyl ketone with a cowless mixer, 30 parts by mass of the precipitated silica and 15 parts by mass of the surface-treated barium sulfate shown in Table 2 were added little by little to adjust the solid content concentration to 20% by mass. After that, the rotation speed of the cowless mixer was increased and the mixture was stirred for 30 minutes to prepare a pigment dispersion. Next, the number of rotations of the cowless mixer was reduced, and in this pigment dispersion, 42 parts by mass of the polymer binder solution of P-3, 10 parts by mass of the polymer solution having an antistatic function of P-1, and hexa as a curing agent. 3 parts by mass of a solution of methylene diisocyanate (diluted with ethyl acetate to a solid content of 20% by mass) was added in this order, and the mixture was stirred and mixed for 20 minutes as it was. Next, the coarse particle size was removed through a 100-mesh filter and diluted with methyl ethyl ketone so that the solid content concentration was 20% by mass to obtain a coating composition (Preparation Example 1) for the surface layer (C). ..

(Adjustment example 2: For surface layer (C))
40 parts by mass of the polymer binder solution of P-4 shown in Table 2, 20 parts by mass of the polymer solution having an antistatic function of P-2, and polyamide / epichlorohydrin of P-5 in a container equipped with a stirrer. 40 parts by mass of the resin solution is added in this order, then diluted with water so as to have a solid content concentration of 20% by mass, and the mixture is stirred and mixed for 20 minutes as it is to prepare a coating composition for the surface layer (C) (Preparation Example 2). Got
(Adjustment example 3: For surface layer (C))
In the coating composition for the surface layer (C) (Preparation Example 1), the surface layer was the same as in the adjustment example except that the polymer solution having the antistatic function of P-1 was not used and the amount of P-3 was increased. A coating composition for (C) (Preparation Example 3) was obtained.

[Examples and Comparative Examples]
(Example 1)
The resin film layer (B) surface (the surface on the j side of the thermoplastic resin composition j ) of the laminated resin film 1 obtained in Production Example 1 is subjected to surface treatment by corona discharge, and then corona is applied with a bar coater to which Mayer bar # 6 is attached. The surface of the discharge-treated surface is coated with the coating composition (Preparation Example 1) for the surface layer (C), dried in an oven at 70 ° C. for 30 seconds, and further cured at 40 ° C. for 8 hours. A self-adhesive synthetic paper was obtained.
(Examples 10 and 19)
In Example 1, self-adhesive synthetic paper was used in the same manner as in Example 1 except that the laminated resin film 1 obtained in Production Example 7 and Production Example 16 were used instead of the laminated resin film 1 obtained in Production Example 1, respectively. Got

(Examples 2, 3 , 7-9, 11-18, 20-24, Comparative Examples 3-5)
In Example 1, the laminated resin film 1 shown in Table 3 or 4 was used instead of the laminated resin film 1 obtained in Production Example 1, and the coating composition for the surface layer (C) was prepared in Preparation Example 2. A self-adhesive synthetic paper was obtained in the same manner as in Example 1 except that the coating composition was changed.
(Example 4)
Both sides of the laminated resin film 2 obtained in Production Example 18 are surface-treated by corona discharge, and then a coating composition for the surface layer (C) is applied to one side with a bar coater to which Mayer bar # 6 is attached (Preparation Example 2). ), And dried in an oven at 70 ° C. for 30 seconds. On the other hand, both surfaces of the laminated resin film 1 obtained in Production Example 4 were subjected to surface treatment by corona discharge, and then the surface opposite to the self-adhesive layer (A) (the surface on the thermoplastic resin composition ( f ) side) was formed. Apply an adhesive (manufactured by Toyo Morton Co., Ltd., trade name: TM-329 and trade name: CAT-18B equal amount mixture) so that the solid content is 3 g / m ^2, and apply at 40 ° C for 1 minute. After drying, the side of the laminated resin film 2 not provided with the surface layer (C) was continuously bonded and further cured at 40 ° C. for 8 hours to obtain the self-adhesive synthetic paper of Example 4.

(Example 5, Comparative Example 1)
A self-adhesive synthetic paper was obtained in the same manner as in Example 4 except that the laminated resin film 1 shown in Table 3 was used instead of the laminated resin film 1 obtained in Production Example 8.
(Example 6)
A self-adhesive synthetic paper was obtained in the same manner as in Example 1 except that the laminated resin film 1 obtained in Production Example 3 was used instead of the laminated resin film 1 obtained in Production Example 1. ..

As can be seen from Tables 3-1 to 4-2, the self-adhesive synthetic papers obtained in Examples 1 to 19 having an isotactic crystallinity on the surface of the self-adhesive layer (A) of 20 to 65%, and The self-adhesive synthetic paper obtained in Examples 20 to 24 having a polyethylene crystallinity on the surface of the self-adhesive layer (A) of 60 to 75% can enhance the adhesive force to the glass plate and leave marks on the acrylic plate. No residue was found, or the marks could be wiped off by wiping with a cloth, and blocking did not occur or was slight when wound up, showing good properties.

On the other hand, in Comparative Example 1 in which the isotactic crystallinity on the surface of the self-adhesive layer (A) is higher than 65%, and Comparative Examples 3 and 4 in which the polyethylene crystallinity on the surface of the self-adhesive layer (A) is higher than 75%, The adhesion to the glass plate was as low as 20 or less. Further, the residue on the acrylic plate instead of the self-adhesive layer (A) was so bad that the residue did not come off unless water or a solvent was used.
Comparing Example 6 and Example 3, when the surface layer (C) contains an alkali metal salt-containing polymer or a quaternary ammonium salt type copolymer as an antistatic polymer, antistatic property is imparted, which is caused by antistatic property. It is shown that the take-up blocking property is suppressed.

Comparing Example 7 and Example 2, it is shown that the rigidity by the Gale method can be controlled within the range of 0.05 to 10 mN by adjusting the thickness of the self-adhesive synthetic paper. Further, comparing Examples 8 and 9 with Examples 4 and 5, it was found that the thickness of the self-adhesive synthetic paper can be adjusted by laminating the laminated resin films, and the rigidity and softness can be within the above range. Shown. If the rigidity is within the above range, it is easy to wind and wind up a long self-synthetic paper, and when the self-adhesive synthetic paper is attached to the object to be attached, the self-synthetic paper is self-weight. Easy to handle without bending.

Examples 10 to 12 show that as the arithmetic mean roughness increases, the coefficient of static friction tends to decrease, and the adhesion to the glass plate tends to decrease. Further, Examples 13 and 14 show that the adhesion to the glass plate tends to increase as the coefficient of static friction increases.
Example 13 (14) shows that when the degree of isotactic crystallinity on the surface of the self-adhesive layer (A) is low, the adhesion to the glass plate is increased and the degree of contamination to the acrylic plate tends to be low.

The self-adhesive synthetic paper of the present invention can be rolled into a roll-shaped roll, and the surface layer (C) can be printed. If the self-adhesive synthetic paper is pulled out from the roll and cut, It is possible to paste the self-adhesive synthetic paper as it is on the material to be attached, and since the self-adhesive synthetic paper is opaque, the texture of the material to be attached cannot be seen through and the print can be clearly seen. It is possible, and it is very useful as a bulletin board such as a sticker, a label, a sign, a poster, and an advertisement.

11 Self-adhesive synthetic paper 51 Evaluation sample 52 Acrylic plate 61 Adhesion measuring device 62 Strut 63 Strut 64 Glass plate 65 Adhesive tape for fixing 66 Clip 67 Thread 68 Weight

Claims (13)

A self-adhesive synthetic paper having at least three layers of a self-adhesive layer (A), a resin film layer (B), and a surface layer (C) in this order, and self-adhesive satisfying the following conditions (1) or (2). Gender synthetic paper.
(1) The self-adhesive layer (A) contains a propylene resin and contains
Self-adhesive layer (A) surface ATR infrared spectrum isotactic crystallinity obtained by measuring by method X _PP is 20 to 65%. Here, X _PP is, 998 ± 1 cm ^-1, 974 the maximum value of absorbance at a range of ± 1 cm ^-1 and 920 ± 1 cm ^-1 when set to A _998, A _974, A _920, respectively, the following formula Demanded by.
_{X PP (%) = 109 ×} (A 998 -A 920) / (A 974 -A 920) -31.4
(2) The self-adhesive layer (A) contains an ethylene resin and contains
Self-adhesive layer (A) polyethylene crystallinity X _PE obtained by measuring by ATR infrared spectrum method surface is 60 to 75%. Here, _XPE is calculated by the following formula, where the maximum values of absorbance in the range of 731 ± 1 cm ^-1 and 720 ± 1 cm ^-1 are A ₇₃₁ and A ₇₂₀ , respectively .
X _PE (%) = 100 x (A ₇₃₁ / A ₇₂₀ )
Then, the condition (1) is applied when A ₇₂₀ / A ₉₇₄ is less than 1.0, and the condition (2) is applied when A ₇₂₀ / A ₉₇₄ is 1.0 or more. The propylene resin comprises a propylene resin having an endothermic peak by the differential scanning calorimetry at 120 to 180 ° C. and a resin having no endothermic peak by the differential scanning calorimetry at 0 to 200 ° C. Item 2. The self-adhesive synthetic paper according to Item 1. The resin having no heat absorption peak according to the differential scanning calorimetry at 0 to 200 ° C. is a copolymer of propylene and ethylene or α-olefin, or a copolymer of ethylene and α-olefin. The self-adhesive synthetic paper according to claim 2. The self-adhesive synthetic paper according to claim 2, wherein the resin having no endothermic peak according to the differential scanning calorimetry at 0 to 200 ° C. contains a hydrogenated styrene resin. Claims 1 to 4, wherein the arithmetic mean roughness (Ra) of the surface of the self-adhesive synthetic paper on the self-adhesive layer (A) side according to JIS B0601: 2003 is 0.2 to 0.7 μm. The self-adhesive synthetic paper according to any one item. The self-adhesive synthetic paper according to any one of claims 1 to 5, wherein the resin film layer (B) is a stretched film layer. Any one of claims 1 to 6, wherein the surface resistivity of the surface layer (C) measured in accordance with JIS K6911: 2006 is 1 × 10 ^{-1 to} 9 × 10 ¹² Ω. Self-adhesive synthetic paper described in. The surface layer (C) contains an antistatic polymer and a polymer binder, and contains
The antistatic polymer comprises an alkali metal salt containing polymer or a quaternary ammonium salt type copolymer.
The self-adhesive synthetic paper according to claim 7, wherein the polymer binder contains a (meth) acrylic resin or a polyethyleneimine-based resin. The invention according to any one of claims 1 to 8, wherein the self-adhesive synthetic paper has a rigidity of 0.05 to 10 mN according to the bending repulsion A method (Gale method) according to JIS L1096: 2010. Self-adhesive synthetic paper. The self-adhesive synthetic paper according to any one of claims 1 to 9, wherein the self-adhesive synthetic paper has an opacity of 50 to 100% according to JIS P8149: 2000. Any of claims 1 to 10, wherein the static friction coefficient between the surface of the self-adhesive layer (A) side of the self-adhesive synthetic paper and the glass plate according to JIS K7125: 1999 is 0.7 to 1.1. The self-adhesive synthetic paper according to item 1. The self-adhesive layer (A) of the self-adhesive synthetic paper is moistened with water, attached to an acrylic plate, stored at 25 ° C. for 24 hours, and then visually recognized on the surface of the acrylic plate after the self-adhesive synthetic paper is peeled off. The self-adhesive synthetic paper according to any one of claims 1 to 11, characterized in that there are no traces formed. A bulletin board characterized in that the self-adhesive synthetic paper according to any one of claims 1 to 12 is attached to an object to be attached.

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