JPH071822A - Receiving sheet for printing - Google Patents

Abstract

PURPOSE:To improve printability, ink setting properties and ink drying properties by providing a coating layer containing a specific prolyolefinic resin and porous particles on the surface of a plastic film. CONSTITUTION:A coating layer containing a linearly irregularly arranged polyolefinic resin with a wt. average mol. wt. of 1000-50000 consisting of 65-99 mol% of an ethylene structural unit represented by formula I, 0-15mol% of an acrylate structural unit represented by formula II (wherein R1 is a 1-4C alkyl group) and 1-35mol% of an acrylamide structural unit represesnted by formula III (wherein R3 and R4are a 1-4C alkyl group, R2 is a 2-8C alkylene group, R5 is a 1-12C alkyl group, an arylalkyl group or an alicyclic alkyl group and X is a halogen atom, CH3OSO3 or C2H5OSO3) and porous particles with oil absorption of 200-400ml/100g is provided on at least the single surface of a plastic film. By this constitution, excellent printability, ink setting properties, ink drying properties, ink adhesion and water resistance are obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printing receiving sheet and is applied to various printing sheets such as offset printing. More particularly, it relates to a printing receiving sheet having excellent printability, ink setting property, ink drying property, ink adhesion property and water resistance.

[0002]

2. Description of the Related Art In a printing receiving sheet, a paper support has been dominant in the past, but in recent years, a plastic film has begun to be used as a support. Among plastic films, polyester films having excellent properties such as mechanical properties and transparency are becoming popular. However, in general, the polyester film surface has high cohesiveness and poor adhesiveness, and therefore, when performing various printing treatments on the surface, it has excellent affinity with ink in order to make the ink adhesiveness strong. The formation of the coating layer is actively practiced. As such a printing receiving sheet, a printing receiving sheet in which a coating layer made of an aqueous polymer resin containing a white pigment is provided on the surface of a polyester film, for example, JP-A-57-82085 is known. There is.

Recently, there has been known a printing receiving sheet provided with a coating layer containing a polymer binder such as an acrylic resin and inorganic or organic particles.

[0004]

However, when an aqueous polymer resin is used, such a receiving sheet for printing is
Since the water resistance and hot water resistance of the coating layer are poor, deformation such as dissolution and expansion of the coating layer may occur under high temperature or high humidity atmosphere, or the adhesive strength of the coating layer may decrease significantly when subjected to hot water treatment. Become.

Further, the one provided with a coating layer containing a polymer binder such as an acrylic resin and inorganic or organic particles,
Since the ink absorption amount of the coating layer is relatively low, the printability such as ink setting property and ink drying property is poor, and the appearance of the coating layer is improved by using a polymer binder having a poor affinity with inorganic or organic particles. It will be extremely bad.

Therefore, it is an object of the present invention to provide a printing receiving sheet which is excellent in water resistance, adhesion to a support, printability, ink setting property, ink drying property and ink adhesion property.

[0007]

The present invention SUMMARY OF THE INVENTION To achieve the above object, on at least one side of a plastic film, wherein _{(1) - [- CH 2} -CH 2 -] - represented by (1) Ethylene structural unit of 65-99 mol% represented by the formula (2)

[Chemical 3] (In the formula, R ₁ represents an alkyl group having 1 to 4 carbon atoms) 0 to 15 mol% of an acrylate structural unit represented by the formula (3)

[Chemical 4] (In the formula, R ₂ is an alkylene group having 2 to 8 carbon atoms, R ₃ and R ₄ are respectively alkyl groups having 1 to 4 carbon atoms, R ₅ is an alkyl group having 1 to 12 carbon atoms, and 1 to 12 carbon atoms. An arylalkyl group or an alicyclic alkyl group having 1 to 12 carbon atoms, X
Is a halogen atom, CH ₃ OSO ₃ or C ₂ H ₅ OSO
Acrylamide structural units 1 to 3 represented by ₃ are shown)
A coating layer containing 5 mol% of a polyolefin resin having a weight average molecular weight of 1,000 to 50,000 randomly arranged in a linear pattern and porous particles having an oil absorption of 200 to 400 ml / 100 g. The present invention is directed to a printing receiving sheet for printing.

The plastic film referred to in the present invention is
Polyester, polyolefin, polyamide, polyester amide, polyether, polyimide, polyamide imide, polystyrene, poly-P-phenylene sulfide, polyether ester, polyvinyl chloride, poly (meth) acrylic acid ester and the like are preferable. Furthermore, these copolymers, blends, and further crosslinked products can be used. Among these plastic films, polyester film is preferable.

The polyester film referred to in the present invention is
It is a polymer obtained by polycondensation from a diol and a dicarboxylic acid, and the dicarboxylic acid is represented by terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, adipic acid, sebacic acid, etc. Are represented by ethylene glycol, trimethylene glycol, tetramethylene glycol, and cyclohexanedimethanol. Specifically, for example, polyethylene terephthalate, polyethylene-P-oxybenzoate, poly-1,4-cyclohexylene dimethylene terephthalate, polyethylene-
2,6-naphthalene dicarboxylate and the like can be mentioned. In the case of the present invention, polyethylene terephthalate and polyethylene naphthalate are particularly preferable. The polyethylene terephthalate film has excellent water resistance, durability and chemical resistance.

Of course, these polyesters may be homopolyesters or copolyesters. Examples of the copolymerization component include diol components such as diethylene glycol and polyalkylene glycol, and dicarboxylic acid components such as adipic acid, sebacic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid and 5-sodium sulfoisophthalic acid.

If desired, various known additives such as antioxidants and antistatic agents may be added to the polyester as long as the characteristics are not impaired.

As the polyester film used in the present invention, it is possible to use a film in which fine bubbles are contained in the film, and the bubbles are whitened by scattering light. The formation of the fine bubbles is formed by finely dispersing an incompatible polymer in a film base material such as polyester and stretching it uniaxially or biaxially. During stretching, voids (air bubbles) are formed around the incompatible polymer particles, and these exhibit white light scattering effect.

The incompatible polymer means a polymer which is incompatible with polyester, such as poly-3-methylbutene-1, poly-4-methylpentene-1, polypropylene, polyvinyl-t-butane and 1,4-trans. -Poly-2,3-dimethylbutadiene, cellulose triacetate, cellulose tripropionate, polychlorotrifluoroethylene and the like. Among them, polyolefin, particularly polymethylpentene is preferable. The reason is that voids are easily generated when stretched, and the polymer has high transparency, so that light absorption is small and light scattered by the voids is not absorbed.

The amount of the incompatible polymer added is preferably 2 parts by weight or more and 25 parts by weight or less. This is because if the amount is less than this, sufficient whitening cannot be achieved, and if it is more than this, the film strength becomes too low.

The film obtained as described above contains fine bubbles and thus has a low specific gravity. The range of this specific gravity is preferably 0.5 or more and 1.2 or less.
More preferably, it is 0.7 or more and 1.0 or less. This is because if the specific gravity is less than 0.5, the film strength becomes too low, and if it exceeds 1.2, sufficient whitening cannot be achieved.

The whiteness of the film obtained as described above is preferably 70% or more. More preferably, it is 80% or more.

Further, the incompatible polymer is uniformly dispersed,
In addition, it is preferable to add a low specific gravity agent in order to sufficiently generate fine bubbles. The low specific gravity agent is a compound which is added together with the incompatible polymer as an auxiliary agent, promotes the formation of voids at the interface between the polyester and the incompatible polymer, and has a specific gravity reducing effect. Only the compound has the effect. For example, for polyester, polyalkylene glycols such as polyethylene glycol, methoxy polyethylene glycol, polytetramethylene glycol, polypropylene glycol and their derivatives, ethylene oxide / propylene oxide copolymers, and further sodium dodecylbenzene sulfonate, alkyl sulfonates. It is represented by sodium salt, glycerin monostearate, tetrabutylphosphonium para-aminobenzene sulfonate and the like. In the case of the present invention, polyethylene glycol is particularly preferable. By adding the low specific gravity agent, the specific gravity of the polyester film can be reduced by 0.1 or more. Furthermore, the addition of this low specific gravity agent not only improves the whiteness of the polyester film and smoothes the surface, but also improves the cleavage resistance and further greatly improves the stretchability of the polyester. The addition amount of the low specific gravity agent is preferably 0.1 to 5 parts by weight. If the addition amount is less than 0.1 part by weight, the effect of the addition is weakened and 5
If it exceeds the weight part, the characteristics of the film base material may be impaired.

Next, it is preferable that the incompatible polymer has a shape close to a sphere in the polyester film, that is, the shape factor is in the range of 1 to 4. Large differences occur in the film properties obtained by the shape of the incompatible polymer in the polyester film, particularly in the correlation between the specific gravity of the film and the cushion rate, thermal dimensional stability, surface roughness, whiteness and the like. That is, to disperse the incompatible polymer in a shape close to spherical means that the shape of the polymer is the viscosity of the incompatible polymer added to the polyester, the incompatibility parameter, the melting point, the type of the low specific gravity agent, and the addition amount. Strongly depends on. The shape close to a sphere means that the shape factor of the incompatible polymer dispersed in the film, that is, the ratio of the major axis to the minor axis is 1 to 4, preferably 1 to 2.

The cushion rate of the polyester film obtained as described above is preferably 10% or more, more preferably 15% or more. If the cushion rate is less than 10%, the feel to the touch will be poor.

Further, in the present invention, a polyester film may be used in which fine particles such as calcium carbonate, amorphous zeolite particles, anatase type titanium dioxide, calcium phosphate, silica, kaolin, talc and clay are used in combination. The addition amount of these is preferably 0.0005 to 25 parts by weight with respect to 100 parts by weight of the polyester composition. In addition to such fine particles, fine particles deposited by the reaction of the catalyst residue and the phosphorus compound in the polyester polymerization reaction system may be used in combination. Examples of the deposited fine particles include those composed of calcium, lithium and phosphorus compounds. The content of these particles in the polyester is preferably 0.05 to 1.0 part by weight with respect to 100 parts by weight of the polyester.

In the present invention, a laminated film may be used if necessary. For example, A / B
Or a three-layer structure of A / B / A. In this case, the layer B is a layer containing fine bubbles, and the layer A may contain an inorganic additive such as titanium dioxide, silicon dioxide or calcium carbonate.

The thickness of the plastic film used in the present invention is preferably 10 μm to 300 μm. More preferably, the thickness is 15 μm to 150 μm, which is excellent in practical handling as a base material.

The plastic film used in the present invention is
If necessary, known surface treatments such as corona discharge treatment, plasma discharge treatment, and anchor coating may be performed to improve the adhesiveness.

The polyolefin resin of the present invention means an ethylene structural unit represented by the formula (1)-[-CH2-CH2-]-(1) in the range of 65 to 99 mol% and the formula (2).

[Chemical 5] (In the formula, R ₁ represents an alkyl group having 1 to 4 carbon atoms) 0 to 15 mol% of an acrylate structural unit represented by the formula (3)

[Chemical 6] (In the formula, R ₂ is an alkylene group having 2 to 8 carbon atoms, R ₃ and R ₄ are respectively alkyl groups having 1 to 4 carbon atoms, R ₅ is an alkyl group having 1 to 12 carbon atoms, and 1 to 12 carbon atoms. An arylalkyl group or an alicyclic alkyl group having 1 to 12 carbon atoms, X
Is a halogen atom, CH ₃ OSO ₃ or C ₂ H ₅ OSO
Acrylamide structural units 1 to 3 represented by ₃ are shown)
It is a polyolefin resin having a weight average molecular weight of 1000 to 50000, which is 5 mol% and is arranged randomly in a linear manner.

The proportion of the ethylene structural unit represented by the formula (1)-[CH ₂ -CH ₂ -]-(1) in the polyolefin resin is 65 to 99 mol%. When the proportion of the ethylene structural unit is less than 65 mol%, the softening point of the polyolefin resin becomes low, and tack or stickiness occurs, and 99 mol%
If it exceeds, the antistatic property is deteriorated. In the present invention, the ratio of the ethylene structural unit is 85 to 97.
It is particularly preferable that the content is mol%.

Formula (2) in the polyolefin resin

[Chemical 7] The ratio of the acrylate structural unit represented by the formula (wherein R ₁ is the same as above) is 0 to 15 mol%. When the proportion of the acrylate structural unit exceeds 15 mol%, the softening point of the polyolefin resin becomes low and tack or stickiness occurs. In the present invention, when the acrylate structural unit is contained, toughness and impact resistance are imparted, which is preferable. In the present invention, the proportion of the acrylate structural unit is particularly preferably 1 to 15 mol%, further preferably 3 to 7 mol%.

In the acrylate structural unit, R ₁
Is an alkyl group having 1 to 4 carbon atoms. Specific examples of R ₁ include methyl group, ethyl group, n-propyl group, n
-Butyl group and i-butyl group are mentioned, and these groups are 1
It may be mixed in the molecule. Among these groups, the methyl group and the ethyl group are preferable for maintaining the softening point of the polyolefin resin.

Formula (3) of the polyolefin resin

[Chemical 8] The ratio of the acrylamide structural unit represented by the formula (wherein R ₂ , R ₃ , R ₄ and R ₅ are the same as above) is 1 to 35 mol%. When the proportion of the acrylamide structural unit is less than 1 mol%, the antistatic property is deteriorated. Again 3
When it exceeds 5 mol%, the polyolefin resin becomes hygroscopic. In the present invention,
The ratio of the acrylamide structural unit is particularly preferably 3 to 15 mol%.

In the acrylamide structural unit, R
₂ is an alkylene group having 2 to 8 carbon atoms. Specific examples of such R ₂ include, for example, ethylene group, propylene group, hexamethylene group, neopentylene group and the like, and these groups may be mixed in one molecule. Among these groups, an ethylene group and a propylene group are preferable, and a propylene group is particularly preferable, from the viewpoint of easy production and economy.

R ₃ and R ₄ each have 1 to 1 carbon atoms.
4 is an alkyl group. Specific examples of R ₃ and R ₄ include a methyl group, an ethyl group, a propyl group, and a butyl group, and these groups may be mixed in one molecule. Among these groups, a methyl group and an ethyl group are preferable from the viewpoint of antistatic property.

R ₅ is an alkyl group having 1 to 12 carbon atoms,
C1-C12 arylalkyl group or C1-C1
12 is an alicyclic alkyl group. Specific examples of R ₅ include, for example, methyl group, ethyl group, n-propyl group, i
-Propyl group, n-butyl group, sec-butyl group, n-
Examples include alkyl groups such as octyl group and n-lauryl group, arylalkyl groups such as benzyl group and 4-methylbenzyl group, alicyclic alkyl groups such as cyclohexyl group and methylcyclohexyl group, and these groups are included in one molecule. It may be mixed. As R ₅ , a linear alkyl group and an arylalkyl group are preferable from the viewpoint of heat resistance, and a lower alkyl group is preferable from the viewpoint of antistatic properties. Particularly preferred R ₅ includes a methyl group and an ethyl group.

The X is, for example, a halogen atom such as Cl, Br or I, CH ₃ OSO ₃ or C ₂ H ₅ OSO ₃ , and these may be mixed in one molecule. Among these, Cl, CH ₃ OSO are used from the viewpoint of antistatic property.
₃ and C ₂ H ₅ OSO ₃ are preferred.

The weight average molecular weight of the polyolefin resin is 1,000 to 50,000. When the weight average molecular weight is less than 1000, the molecular weight becomes too small and volatilizes when heated, and when it exceeds 50,000, the viscosity becomes too large and workability deteriorates. A preferred weight average molecular weight is 3,000 to 30,000.

The weight average molecular weight in the present invention means
It refers to a monodisperse polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

Since the polyolefin resin used in the present invention is hardly soluble in a normal gel permeation eluent such as tetrahydrofuran (THF) or xylene, its weight average molecular weight cannot be easily measured. GPC (Kinukawa, Journal of Polymer Science, Vol. 44, No. 2, 13
9 to 141 (1987)).

An ethylene structural unit represented by the formula (1) — [— CH ₂ —CH ₂ —] — (1), which is an intermediate of the polyolefin resin, and the formula (2)

[Chemical 9] (Wherein R ₁ is the same as above) and an acrylate structural unit represented by the formula (4)

[Chemical 10] (Wherein R ₂ , R ₃ , and R ₄ are the same as above), the olefinic copolymer having a weight average molecular weight of 1,000 to 50,000 linearly and irregularly arranged and composed of an acrylamide structural unit is, for example, It is obtained by the method of.

First, the raw material of the olefin-based copolymer is not particularly limited, but more preferably ethylene (C
A (partial) hydrolyzate of a copolymer composed of ₂ H ₄ ) and CH ₂ CHCOOR ₁ (wherein R ₁ is the same as above) is used. Such a copolymer is
It can be easily obtained by copolymerizing ethylene and the acrylate by a high pressure polymerization method.

The ratio of the ethylene structural unit derived from the ethylene to the acrylate structural unit derived from the acrylate is determined by determining the ratio of the ethylene structural unit, the acrylate structural unit and the acrylamide structural unit of the obtained olefinic copolymer. become.

Since the above-mentioned copolymer usually has a high molecular weight of about 5 to 300 as a melt index, it has a low molecular weight by a degradation method in which hydrolysis is carried out at the same time as hydrolysis at high temperature and high pressure in the presence of water. Preferably. At this time, the formula (2) derived from the acrylate

[Chemical 11] (Wherein R ₁ is the same as the above), all or part of the acrylate structural unit represented by the formula (5)

[Chemical 12] It becomes an acrylic acid structural unit represented by.

In order to prepare a copolymer having a weight average molecular weight of 1,000 to 50,000 by lowering the molecular weight by thermally decomposing the copolymer, the copolymer is reacted in the presence of water at a reaction temperature of 150 to 500. ℃, pressure 3-500kg / c
The molecule may be cut by heating at m ² .

Further, in the present invention, the ratio of the acrylic acid structural unit can be appropriately adjusted by adjusting the charged amount of water, the reaction temperature, the pressure and the reaction time.

Specific examples of the degradation method are, for example, JP-A-53-57295 and JP-A-53-65389.
JP, JP-A-60-79008, JP-A-60-
The method described in Japanese Patent Publication No. 79015 can be used.

Since the polyolefin resin used in the present invention may impair its commercial value when colored, the raw material used in the present invention is exemplified in, for example, JP-A-60-79008. Preference is given to using the products of the processes mentioned.

The polyolefin resin used in the present invention can be obtained by using the polyolefin resin intermediate thus obtained.

The method for producing the polyolefin resin used in the present invention from the above intermediate is not particularly limited. An example thereof will be described below.

Examples of the intermediate include benzene, toluene,
It is dissolved in an inert solvent such as an aromatic or aliphatic hydrocarbon such as xylene, cyclohexanone, decane, cumene or cymene, and 1 is added to the carboxyl group of the intermediate.
Add a dialkylamine-based monomer such as dialkylaminoalkylamine in an amount of 0 to 150 mol%,
After reacting at 220 ° C. to convert the carboxyl group contained in the acrylic acid structural unit into a dialkylaminoalkylamide group to form an intermediate, for example, an alkyl halide,
The polyolefin resin, which is a linear random copolymer used in the present invention, can be obtained by cation modification with a known quaternizing agent such as dialkyl sulfate.

Further, in the present invention, since the acrylamide structural unit does not exhibit volatility even at high temperature and is chemically incorporated into the polyolefin resin used in the present invention, it is volatilized during processing. Therefore, it is considered that blocking does not occur even after processing.

If necessary, other polymeric binder may be added to the coating layer of the present invention as long as the desired properties of the present invention are not impaired. Other polymer binders include, for example, polyvinyl acetate, ethylene-vinyl acetate copolymer,
Saponified ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-
(Meth) acrylic acid-maleic anhydride terpolymer, ethylene- (meth) acrylic acid ester-maleic anhydride terpolymer, polyester, polyamide, polyesteramide, polyvinyl acetal, poly (meth) acrylic acid ester And so on.

The porous particle in the present invention is a porous particle having pores on the surface of the particle, and can be freely filled and released with a liquid, a solid or a gas inside as a hollow porous or non-hollow porous form. Those are preferable from the viewpoint of ink absorbency.

The constituents of the porous particles include amorphous silica, anhydrous silica, aluminum silicate, magnesium silicate, zinc silicate, calcium silicate, hydrotalcite, zeolite, satin white, titanium oxide, and oxide. Aluminum, magnesium oxide, calcium carbonate, calcium sulfate, barium sulfate, diatomaceous earth, kaolin, talc, acid clay, activated clay, bentonite, ion exchange resin powder, urea resin powder, polyethylene resin powder, urea formalin resin powder, acrylic resin Powder, styrene-acrylic resin powder, etc. are mentioned. The oil absorption of these porous particles is 200 to 400 ml / 10.
It needs to be 0 g. Preferably 250-3
50 ml / 100 g. Oil absorption is 200 ml / 10
If it is less than 0 g, the ink absorbency of the obtained printing sheet will be poor, and sufficient ink setting property and ink drying property will not be obtained, and if it exceeds 400 ml / 100 g, the obtained printed product will become light and become a so-called sunken printed product. Cheap.

The average particle diameter of the porous particles used in the present invention is preferably from 0.1 to 25 μm, and more preferably from 0.5 to 10 μm from the viewpoints of handleability, coatability, printability and the like.

The content of the porous particles in the coating layer is preferably 20 to 100 parts by weight, more preferably 30 to 70 parts by weight, based on 100 parts by weight of the olefin resin / polymer binder. Is. If the content is less than 20 parts by weight, the ink setting property and the ink drying property become insufficient, and 10
If it exceeds 0 parts by weight, the adhesiveness between the coating layer and the film support tends to deteriorate.

The smoothness of the coating layer constituting the printing receiving sheet of the present invention is preferably 2 to 5000 seconds, more preferably 10 to 3000 seconds. When the smoothness is smaller than the range of the present invention, the ink permeation rate is too high and the printed matter becomes pale, which is not preferable. Further, when it is larger than the range of the present invention, the ink permeation rate is too low and the ink is likely to remain on the coating layer surface, and when the printing surface is rubbed,
It is not preferable because the printed surface is easily stained with residual ink.

Furthermore, the thickness of the coating layer constituting the printing receiving sheet of the present invention is not particularly limited,
The thickness is preferably 0.5 to 50 μm, and is preferably in the range of 1.0 to 20 μm from the viewpoint of uniform forming property of the coating layer and adhesion. Further, the coating layer may optionally contain known additives within a range that does not impair the characteristics of the present invention, for example, a coating property improver, a thickener, an antioxidant, an ultraviolet absorber, a dye and the like. Good.

The setting time of the oil-based offset ink for the printing receiving sheet of the present invention is preferably within 30 minutes, more preferably within 20 minutes. Ink set time is 30
If it is more than a minute, not only will the ink drying time be delayed,
Problems such as set-off occur during printing. Here, the set time of the oil-based offset ink is a value obtained based on the following measuring method. That is, a printability tester RI-2 type (manufactured by Akira MFG.
Set 4-division rolls of m and width of 4.7 cm, apply 0.3 cc of oil-based offset printing ink "TK Mark Five New" Beni (Toyo Ink Co., Ltd.) to each roll with an ink pipettor, and print solidly. Do. Next, OK coated paper (Oji Paper Co., Ltd.)
Product) and the line pressure of 353 g /
This is to observe the time required for running a metal roll of cm to stop the transfer to the OK coated paper.

In the present invention, as a method for providing a coating layer, a film support as a base material is previously stretched in a film forming step, then a liquid adjusted to a predetermined amount is applied, and then dried. The method of applying a step of coating and drying after winding as a base film single film is preferably applied.

The coating method is not particularly limited, but it is known in the art such as gravure coating method, reverse coating method, reverse gravure coating method, kiss coating method, die coating method and bar coating method because it is possible to perform thin film coating at high speed. The method can be applied. Although the coating speed and the coating film drying conditions are not particularly limited, it is desirable that the coating film drying conditions be within a range that does not adversely affect various properties of the coating layer and the support.

[0058]

[Characteristic Measuring Method] First, various characteristic measuring methods in the present invention will be described.

(1) Smoothness Oken type smoothness tester (model KB-15) manufactured by Asahi Seiko Co., Ltd.
It was measured at. The average is shown as n = 5.

(2) Surface Roughness Cutoff of 0.
Center line average roughness Ra (μ
m) and the maximum roughness Rt (μm).

(3) Specific gravity 25 using a density gradient tube of carbon tetrachloride-n-heptane system
Values in ° C are used.

(4) Heat shrinkage rate The film has a width of 10 mm and a length of 3 in the longitudinal or width direction.
It is cut into 00 mm, marked at intervals of 200 mm, fixed on a support plate under constant tension (5 g), and then the original length a (mm) of the marking intervals is measured. Next, a load is applied by using a clip of 3 g and the treatment is performed for 30 minutes while rotating in a hot air oven at 150 ° C., and the marking interval b (mm) is measured in the same manner as the measurement of the original length. The heat shrinkage rate is calculated by the following formula, and the average value of 5 is used.

Thermal shrinkage (%) = (ab) / a

(5) Optical Density Films are stacked so as to have a thickness of about 150 μm, and the transmission density is measured using an optical densitometer (TR927, manufactured by Macbeth Co.). The thickness of the film and the optical density are plotted to determine the optical density corresponding to a thickness of 150 μm.

(6) Whiteness U manufactured by Shimadzu Corporation according to JIS-L-1015
When V-260 is used and reflectances at wavelengths of 450 nm and 550 nm are B% and G%, respectively, whiteness (%) = 4B-3G.

(7) Stretchability When a film is continuously formed for 24 hours, the film having no breakage is defined as “good”, and the film having two or more breaks is defined as “broken”.

(8) Cushion ratio Dial gauge No. manufactured by Mitoyo Seisakusho Co., Ltd. 2109-1
No. 0 standard probe 900030, and dial gauge stand No. It is calculated from the respective film thicknesses d ₅₀ and d ₅₀₀ when a load of 50 g and 500 g is applied to the dial gauge pressing portion using 7001DGS-M by the following formula.

Cushion rate = (d ₅₀ −d ₅₀₀ ) / d ₅₀

(9) Oil Absorption of Porous Particles The oil absorption was measured according to JIS-K-5101 to obtain an oil absorption (ml / 100 g) corresponding to 100 g of particles.

(10) Adhesiveness of coating layer The adhesiveness of the coating layer / support was determined by putting a crosscut (100 pieces / cm ² ) on the coating layer and serotape: CT- at 45 ° to the crosscut surface. 24 (manufactured by Nichiban Co., Ltd.)
Affix, and use a hand roller to apply a load of about 5 kg to 10
The cellophane tape was forcibly peeled in the direction of 180 ° by pressing back and forth twice, and the degree of peeling of the coating layer was observed and evaluated. The criteria for evaluation are: ⊚: very good (no peeling) ○: good (peeling area less than 5%) Δ: somewhat inferior (peeling area 5 or more and less than 10%) x: poor (peeling area 10% or more)

(11) Water resistance of the coating layer A cotton swab was dipped in water and the coating layer was slightly rubbed for evaluation. The criterion is ◎: very good (no peeling at all) ○: good (peeling after rubbing 10 to less than 15 times) Δ: somewhat inferior (peeling after rubbing 5 to less than 10 times) ×: poor (peeling after less than 5 times) And

(12) Coating layer thickness It was determined by measuring with a micrometer or a dial gauge.

(13) Ink setting property The ink composition was evaluated according to the following evaluation criteria by the evaluation method described above.

◎: Less than 30 minutes ○: 30 or more and less than 45 minutes △: 45 or more and less than 60 minutes ×: 60 minutes or more

(14) Ink drying time Printing was carried out in the same manner as the ink setting property measurement, and O was printed on the printing surface.
The coated surfaces of the K-coated paper were overlaid, allowed to stand for 24 hours in that state, and the printed surface was rubbed with a light nail to evaluate. The criteria for evaluation are: ◯: Not peeled off Δ: Peeled off after repeated rubbing ×: Peeled off easily

(15) Electrophotographic copying recording property Canon full color electrostatic copying machine PIXEL D
A full color test pattern was printed using io, the print quality and runnability were evaluated, and the printability was judged. The criteria for judgment are ⊚: very good ∘: good Δ: slightly inferior x: poor

[0077]

EXAMPLES Next, the present invention will be specifically described by way of examples. In addition, all compounding parts in the examples are parts by weight.

Example 1 Polyethylene terephthalate homopolymer chips produced by a conventional method (intrinsic viscosity: 0.62, melting point: 259)
C.) was used to obtain a 75 μm biaxially stretched polyester film by a conventional method. On the thus obtained biaxially stretched polyester film, a coating layer having the following composition was coated by a gravure coater (the coating amount of the coating layer after drying was 5 μm).

Coating layer Ethylene-acrylic acid copolymer (acrylic acid concentration 20% by weight): 60 parts Formula:-[-CH ₂ -CH ₂ -]-ethylene structural unit represented by 85 mol%, formula:

[Chemical 13] An acrylate structural unit represented by 5 mol% and a formula:

[Chemical 14] Polyolefin resin having a weight average molecular weight of 31300 and linearly irregularly arranged consisting of 10 mol% of acrylamide structural unit represented by: 40 parts Porous particles (Fineseal: Tokuyama Soda Co., Ltd. average particle diameter 3.5 μm, oil absorption Amount 260 ml / 100 g): 40 parts Water / methanol = 4/1 adjusted to 20%. The printing receiving sheet thus obtained has water resistance, adhesiveness, ink setting properties, ink drying properties, and electrophotography as shown in Table 1. It was excellent in copy recording property and coating film appearance.

Example 2 In Example 1, the type of the porous particles was changed (nip seal E: manufactured by Nippon Silica Industry Co., Ltd., average particle size 2.0 μm).
m, oil absorption of 255 ml / 100 g), and a receiving sheet for printing was obtained in the same manner. The printing receiving sheet thus obtained was excellent in water resistance, adhesiveness, ink setting property, ink drying property, electrophotographic copy recording property and coating film appearance as shown in Table 1.

Comparative Example 1 A receiving sheet for printing was obtained in the same manner as in Example 1 except that the porous particles were removed. The printing receiving sheet thus obtained was inferior in ink setting property, ink drying property and electrophotographic copy recording property as shown in Table 1.

Comparative Example 2 In Example 1, the porous particle oil absorption was 45 ml / 10.
A receiving sheet for printing was obtained in the same manner except that 0 g of calcium carbonate was used. The printing receiving sheet thus obtained was inferior in ink setting property and ink drying property as shown in Table 1.

Example 3 In Example 1, as the polyolefin resin, the acrylamide structural unit has the formula:

[Chemical 15] A receiving sheet for printing was obtained in the same manner except that the one represented by The printing receiving sheet thus obtained was excellent in water resistance, adhesiveness, ink setting property, ink drying property, electrophotographic copy recording property and coating film appearance as shown in Table 1.

Example 4 Polyethylene terephthalate (intrinsic viscosity [η] = 0.6
5) 94% by weight, poly-4-methylpentene-1 (Mitsui Petrochemical Co., Ltd. TPX-D820) 5% by weight, and a raw material obtained by mixing 1% by weight of polyethylene glycol having a molecular weight of 4000 to the extruder A, It was melted at 285 ° C. by a conventional method and introduced into the central layer of the T-die three-layer composite die.

On the other hand, the above polyethylene terephthalate 9
0% by weight of calcium carbonate (average particle size 0.8 μm) 1
The raw material added with 0 wt% was supplied to an extruder B, melted at 285 ° C. by a conventional method and laminated on both surface layers of a T-die three-layer composite spinneret, and the melt sheet was kept at a surface temperature of 25 ° C. The solid was cooled and solidified on the cooling drum by the electrostatic charge method. Then, the cast sheet was stretched 3.5 times by a roll group heated to 98 ° C in the longitudinal direction according to a conventional method, and cooled to 25 ° C. Further, the drawn film is guided to a tenter 1
The film was stretched 3.2 times in the width direction in an atmosphere heated to 25 ° C. and heat-set at 225 ° C. to obtain a film having a thickness of 100 μm. The thickness of each film layer was 5 μm on the surface layer and 90 μm on the central layer. The characteristics of the film are shown in Table 2. In order to improve the adhesiveness of the surface of the thus obtained biaxially stretched polyester film, corona discharge treatment was performed, and a printing receiving sheet was obtained in the same manner as in Example 1. The printing receiving sheet thus obtained was excellent in water resistance, adhesiveness, ink setting property, ink drying property, electrophotographic copy recording property and coating film appearance as shown in Table 1.

[0086]

[Table 1]

[Table 2]

[0087]

The printing receiving sheet of the present invention has a water resistance,
It is characterized by excellent adhesion to the support, printability, ink setting properties, ink drying properties, and ink adhesion properties. The printing receiving sheet produced as described above can be preferably used in applications such as offset printing, flexographic printing and electrophotographic copying recording. Further, the printing receiving sheet of the present invention is a thermal ink receptor containing a sublimation type,
It can also be applied as other inks and toner receivers such as wet electrophotographic toner receivers and fabric ink receivers.

Claims (1)

[Claims] 1. An ethylene structural unit represented by the formula (1)-[— CH ₂ —CH ₂ —]-(1) in an amount of 65 to 99 mol% on at least one surface of a plastic film, and a compound represented by the formula (2): (Wherein R ₁ represents an alkyl group having 1 to 4 carbon atoms), the acrylate structural unit is represented by 0 to 15 mol%, and the compound represented by formula (3) (In the formula, R ₂ is an alkylene group having 2 to 8 carbon atoms, R ₃ and R ₄ are respectively alkyl groups having 1 to 4 carbon atoms, R ₅ is an alkyl group having 1 to 12 carbon atoms, and 1 to 12 carbon atoms. An arylalkyl group or an alicyclic alkyl group having 1 to 12 carbon atoms, X
Is a halogen atom, CH ₃ OSO ₃ or C ₂ H ₅ OSO
Acrylamide structural units 1 to 3 represented by ₃ are shown)
A coating layer containing 5 mol% of a polyolefin resin having a weight average molecular weight of 1,000 to 50,000 randomly arranged in a linear pattern and porous particles having an oil absorption of 200 to 400 ml / 100 g. Receiving sheet for printing.