JP3049830B2 - Coating laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating laminate, and more particularly to a coating laminate applied to various printing sheets such as ink jet printing, offset printing, flexographic printing and the like.

[0002]

2. Description of the Related Art As a coating laminate conventionally applied to a printing sheet, there is known a coating laminate in which a water-based coating agent composed of inorganic particles and an aqueous binder emulsion is applied to the surface of high quality paper, synthetic paper, plastic film or the like. Have been.

[0003]

However, the coating laminate of the above-mentioned production method has insufficient adhesion to a substrate and water resistance, and the above coating agent uses an aqueous binder emulsion. Various problems such as foaming at the time occur.

[0004]

According to the present invention, in order to solve the above-mentioned problems, a coating layer containing inorganic and / or organic particles and a polymer binder is provided on a support. Wherein the polymer binder is mainly composed of a graft copolymerized acrylic resin having a main chain composed of a hydrophobic monomer and a branched chain composed of a hydrophilic monomer, and a cationic polymer. The gist of the present invention is a coating laminate.

[0005] As the support in the present invention, paper (high quality paper), coated paper, Japanese paper, nonwoven fabric and plastic film can be used.

[0006] As the paper, "JIS P3 for printing paper"
101 to P3105 "and" Print Magazine 1988 (vol.
71)) can be used.
(High quality paper) is preferred.

As the non-woven fabric, those described in "Non-woven Fabrics" (published by Kobunshi Kanko, Yoshito Miura, published in 1973) are preferable.

[0008] Plastic films include polyester, polyolefin, polyamide, polyesteramide, polyether, polyimide, polyamideimide, polystyrene, polycarbonate, poly-P-phenylene sulfide, polyetherester, polyvinyl chloride,
Poly (meth) acrylate is preferred. Furthermore, these copolymers, blends, and further crosslinked products can also be used.

Among the above supports, a plastic film is particularly preferred, and among them, polyester, preferably polyethylene terephthalate, is preferred in terms of mechanical properties, workability and the like.

[0010] More preferably, a polyester having a cushioning property by adding an incompatible polymer or a low specific gravity agent to a polyester is particularly preferable. That is, the heat shrinkage at 150 ° C. is preferably less than 2% and the specific gravity is preferably 1.2 or less. If it is larger than 1.2, the film does not have softness and cushioning properties.

In the present invention, the heat shrinkage of the polyester film suitable for the support is preferably less than 2% at 150 ° C. in both the longitudinal and transverse directions, and preferably less than 1%.

The polyester film referred to in the present invention is:
A polymer obtained by condensation polymerization from a diol and a dicarboxylic acid.Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, adipic acid, and sebacic acid. Is 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 carboxylate and the like can be mentioned. In the case of the present invention, polyethylene terephthalate and polyethylene naphthalate are particularly preferred. 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 necessary, various known additives such as antioxidants and antistatic agents may be added to the polyester as long as the properties are not impaired.

The polyester film used in the present invention comprises:
Inside the film is contained fine bubbles, it is preferred to use those is whitened by scattered light in the bubbles. The formation of the fine bubbles is formed by finely dispersing an incompatible polymer in a film base material, for example, polyester, and stretching it uniaxially or biaxially. At the time of stretching, voids (bubbles) are formed around the incompatible polymer lupus, which exhibit white light scattering action, thereby obtaining a high reflectance.

The immiscible polymer refers to a polymer that does not dissolve in polyester, and includes poly-3-methylbutene-1, poly-4-methylpentene-1, polypropylene, polyvinyl-t-butane, 1,4-trans -Poly-2,3-dimethylbutadiene, cellulose triacetate, cellulose tripropionate, polychlorotrifluoroethylene and the like. Among them, polyolefin, particularly polymethylpentene is preferred. The reason is that voids are easily formed 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 immiscible polymer is preferably 2% by weight or more and 25% by weight or less. 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 has a low specific gravity because it contains fine bubbles. The specific gravity is preferably in the range of 0.5 to 1.2.
More preferably, it is 0.7 or more and 1.0 or less. If the specific gravity is less than 0.5, the film strength becomes too low. If it exceeds 1.2, sufficient whitening cannot be achieved.

The whiteness of the film obtained as described above is preferably at least 70%. It is more preferably at least 80%.

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 that is added as an auxiliary agent together with the incompatible polymer, promotes generation of voids at the interface between the polyester and the incompatible polymer, and has the effect of reducing the specific gravity. Only the compound exhibits its effect. For example, for polyesters, polyalkylene glycols such as polyethylene glycol, methoxypolyethylene glycol, polytetramethylene glycol, and polypropylene glycol and derivatives thereof, ethylene oxide / propylene oxide copolymers, sodium dodecylbenzenesulfonate, and alkyl sulfonates Sodium salt, glycerin monostearate, tetrabutylphosphonium paraaminobenzenesulfonate and the like. In the case of the present invention, polyethylene glycol is particularly preferred. The specific gravity of the polyester film can be reduced by 0.1 g / cc or more by adding a low specific gravity agent. Furthermore, the addition of the low specific gravity agent has the effects of improving the whiteness of the polyester film, smoothing the surface, improving the cleavage resistance, and greatly improving the stretchability of the polyester. The amount of the low specific gravity agent is preferably 0.1 to 5% by weight. If the amount is less than 0.1% by weight, the effect of the addition is weakened, and if it exceeds 5% by weight, the properties of the film base material may be impaired.

Next, it is preferable that the immiscible polymer has a nearly spherical shape in the polyester film, that is, the shape factor is in the range of 1-4. Significant differences occur in the properties of the obtained film, particularly the correlation between the specific gravity of the film and the cushion rate, the thermal dimensional stability, the surface roughness, the whiteness, etc., depending on the properties of the incompatible polymer in the polyester film. That is, when the shape of the immiscible polymer is close to spherical, not only can the specific gravity be reduced compared to the case where the incompatible polymer is dispersed in a layer, but also a whiteness, a cushion ratio and a film having good thermal dimensional properties can be obtained. . Dispersing a polymer in a shape close to a spherical shape strongly depends on the viscosity, the compatibility parameter, the melting point of the incompatible polymer to be added to the polyester, the kind of the low specific gravity agent, the amount added, and the like. 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 from 1 to 4, preferably from 1 to 2.

The cushion rate of the polyester film suitable as the support of the present invention is preferably at least 10%, more preferably at least 15%. Cushion rate is 10
%, The feeling when touched by hand is inferior.

The optical density of the polyester film suitable as the support of the present invention is preferably from 0.7 to 1.6, more preferably from 0.8 to 1.6. When the optical density is less than 0.7, the concealing property of the film is insufficient and the back side is transparent, which is not preferable. If the optical density exceeds 1.6, a large amount of fine bubbles must be contained.
The film strength becomes weak, which is not preferable.

Further, in the present invention, a polyester film 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 may be used. The amount of these additives is preferably 0.0005 to 25 parts by weight based on 100 parts by weight of the polyester composition. In addition to the fine particles, fine particles precipitated by the reaction between the catalyst residue and the phosphorus compound in the polyester polymerization reaction system can be used in combination. Examples of the precipitated 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 based on 100 parts by weight of the polyester.

In the present invention, a laminated film may be used if necessary. For example, it has a two-layer configuration of A / B or a three-layer configuration 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 is 1
It is preferably from 0 μm to 250 μm. More preferably, the thickness is 15 μm to 150 μm, which is excellent in practical handling as a substrate base.

If necessary, the plastic film may be subjected to a known surface treatment, for example, a corona discharge treatment, a plasma discharge treatment, an anchor coat, etc., in order to improve the adhesiveness.

In the present invention, the inorganic particles include amorphous silica, anhydrous silica, aluminum silicate, magnesium silicate, zinc silicate, calcium silicate, hydrotalcite, zeolite, satin white, titanium oxide, and aluminum oxide. , Magnesium oxide, calcium carbonate, calcium sulfate, barium sulfate, diatomaceous earth, kaolin, talc, acid clay, activated clay, bentonite and the like.

Among them, a porous material having pores on the particle surface is preferable, and a porous or non-hollow porous material capable of freely enclosing and releasing a liquid, solid or gas inside has a high ink absorbing property. Is preferred. The method for producing the porous particles is not particularly limited, but typical examples of the production method include JP-A-62-292476, JP-B-54-6251, and JP-B-57-55.
No. 454 and Japanese Examined Patent Publication No. 55-43404 describe a method of preparing an inorganic powder by "interfacial reactivity", that is, an aqueous solution precipitation reaction. In the preparation process, a water-in-oil type (W / O (Type) It can be produced by adjusting hollow, spherical, or porous inorganic powder particles by using an emulsion.

Specific examples of the wall material of the inorganic material constituting the porous particles include, for example, alkaline earth metal carbonates such as calcium carbonate, barium carbonate and magnesium carbonate;
Alkaline earth metal silicates such as calcium silicate, barium silicate and magnesium silicate, alkaline earth metal phosphates such as calcium phosphate, barium phosphate and magnesium phosphate, calcium sulfate, barium sulfate,
Alkaline earth metal sulfates such as magnesium sulfate, silicic anhydride, aluminum oxide, zinc oxide, iron oxide, titanium oxide, cobalt oxide, nickel oxide, metal oxides such as manganese oxide, antimony oxide, tin oxide, and iron hydroxide ,
Metal hydroxides such as nickel hydroxide, aluminum hydroxide, calcium hydroxide, and chromium hydroxide; metal silicates such as zinc silicate, aluminum silicate, and copper silicate; zinc carbonate, aluminum carbonate, cobalt carbonate, and carbonic acid Representative examples thereof include metal carbonates such as nickel and basic copper carbonate. Among them, in the present invention, those composed of silicic anhydride are particularly preferable in terms of the properties of the coating laminate.

The organic particles in the present invention include ion exchange resin powder, urea resin powder, polyethylene resin powder, polystyrene resin powder, urea formalin resin powder, acrylic resin powder, styrene-acryl resin powder and the like. Above all, specific shaped particles of acrylic resin powder and styrene-acrylic resin powder are preferable. Among them, donut-shaped flat particles, fine particle aggregated particles, core-shell structured particles, hollow porous particles, and the like are preferable. By using these peculiar particles, the ink absorbency can be increased.

The average particle size of the inorganic and / or organic particles is from 0.1 μm to 25 μm, preferably from 0.5 μm to 1 μm.
5 μm, more preferably 0.5 μm to 10 μm is preferable from the viewpoint of handleability, coating property, printability and the like.

The content of the inorganic and / or organic particles in the coating layer is 1 to 100% by weight, preferably 5 to 7%.
It is preferably 0% by weight. If the content is less than 1% by weight, the ink settability becomes insufficient, and if it exceeds 100% by weight, the adhesion between the coating layer and the film support tends to be reduced.

In the present invention, the polymer binder is mainly composed of a graft copolymerized acrylic resin, and different types of monomers are selected for the backbone and the branch, and the function of the backbone and the function of the backbone are selected. It is a function-separated polymer that combines functions. Above all, by using a hydrophobic polymer for the backbone and a hydrophilic polymer for the branches, a coated film having hydrophilicity and water resistance can be obtained after coating. The graft copolymerized acrylic resin as the main component in the present invention means 50% by weight or more, preferably 60% by weight in the polymer binder.
This refers to the above, and other substances may be added as needed as long as the properties are not impaired. In the polymer binder used in the present invention, examples of the monomer unit for introducing a hydrophobic polymer include styrene, styrene derivatives, vinylnaphthalene, vinylnaphthalene derivatives, and (meth) acrylates. The monomer unit for introducing the hydrophilic polymer has a hydrophilic structural portion such as a carboxylic acid group, a sulfonic acid group, a sulfate ester group, a phosphoric acid group, a hydroxyl group, an amino group, and an amide group. In addition to the above monomer units, acrylonitrile, acrylamide, methacrylamide, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate, N-methylol acrylamide, N-butoxymethyl acrylamide and the like can be used. Among them, methyl methacrylate in the backbone, hydroxyethyl methacrylate in the branch,
And / or those obtained by copolymerizing N-methylolacrylamide.

To adjust the electric resistance of the surface of the coating layer, a polymer electrolyte or a conductive powder is usually added. In the present invention, as the polymer electrolyte, a cationic polymer such as a quaternary ammonium salt is preferably used from the viewpoint of the conductivity and the compatibility with the polymer binder.
Among them, a cationic acrylic polymer is more preferably used. Examples of the cationic acrylic polymer include salts of butyl methacrylate and dimethylaminoethyl methacrylate, and specifically, Eleconde PQ-10, PQ-50B, B-149 and the like manufactured by Soken Chemical can be effectively used. In the present invention, the addition of the conductive powder is not particularly limited, but tin oxide, indium oxide, zinc oxide, tantalum oxide, and a combination thereof are preferable.

The coating layer constituting the coating laminate of the present invention has a smoothness of 2 to 5000 seconds, preferably 10 to 3 seconds.
2,000 seconds, more preferably in the range of 20 to 2500 seconds. If the smoothness is smaller than the present invention, the ink permeation rate is too high and the recording becomes lighter, which is not preferable. On the other hand, when the recording surface is larger than the present invention, the ink permeation rate is too low, so that the ink tends to remain on the surface of the coating layer.

The thickness of the coating layer constituting the coating laminate of the present invention is not particularly limited, but is preferably 0.5 μm to 50 μm, and more preferably 1.0 μm to 20 μm.
Those having a range of m are desirable in terms of uniformity of formation of the coating layer, adhesion and the like. If necessary, the coating layer may contain known additives such as a coating improver, a thickener, an antioxidant, an ultraviolet absorber, and a dye in an amount that does not impair the present invention.

[0038] The coating laminate of the present invention is provided with a coating layer comprising the above-mentioned composition on at least one surface of a support. As a method of providing a coating layer, when the support is a plastic film, a film support serving as a substrate is stretched in advance in a film forming step, and then a liquid adjusted to a predetermined amount is applied, and then dried. Method A method of providing a coating-drying step after winding as a base film single film is preferably applicable.

The solution of the composition to be applied is used in the form of an organic solvent solution in order to solve various problems such as the water resistance of the coating film and the foamability of the paint. The organic solvent is not particularly limited, but preferably, toluene, methyl ethyl ketone, methyl cellosolve, isopropyl alcohol and the like are applied.

The coating method is not particularly limited, but a gravure coating method, a reverse coating method, a reverse gravure coating method, a kiss coating method, a die coating method, a metaling bar coating method, etc., because a thin film can be coated at a high speed. Known methods can be applied. In addition, application speed,
The conditions for drying the coating film are not particularly limited, but the drying conditions for the coating film are desirably in a range that does not adversely affect the properties of the coating layer and the support.

[0041]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS First, a method for measuring various characteristics according to the present invention will be described.

(1) Smoothness Asahi Seiko Co., Ltd. Oken type smoothness tester (Model KB-15)
Was measured. It was shown as an average of n = 5.

(2) Surface Roughness According to JIS B0601-1967, a cut-off of 0.
25 mm, measurement length 4 mm, center line average roughness Ra (μm)
And the maximum roughness Rt (μm).

(3) Average equivalent sphere diameter of voids A cross section cut in the machine direction or its vertical direction in the film forming process is photographed with a scanning electron microscope at a magnification of 1,000 to 5,000 times, and the designated thickness range is specified. Is subjected to an image analyzer to obtain a distribution of diameters of circles corresponding to void areas.
The volume average diameter of this distribution is defined as the average sphere equivalent diameter of the voids.

(4) Specific Gravity: 25% by a carbon tetrachloride-n-heptane system density gradient tube.
Use the value at ° C.

(5) Heat Shrinkage The film has a width of 10 mm and a length of 300 in the longitudinal or width direction.
After cutting into mm, marking at intervals of 200 mm and fixing to a support plate under constant tension (5 g), the original length a (mm) of the marking interval is measured. Next, a load is applied by using a 3 g clip, and processing 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 original length measurement. The heat shrinkage is determined by the following equation, and the average value of five pieces is used. Heat shrinkage (%) = (ab) / a

(6) Optical Density The 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). The thickness of the film and the optical density are plotted to determine the optical density corresponding to a thickness of 150 μm.

(7) Whiteness According to JIS-L-1015, U-manufactured by Shimadzu Corporation
When the reflectance at wavelengths of 450 nm and 550 nm is B% and G% using V-260, whiteness (%) = 4B-3G.

(8) Stretchability When a film is continuously formed for 24 hours, a film having no film tear is defined as “good”, and a film having two or more breaks is determined as “breakable”.

(9) Cushion rate Dial gauge No. 2109-10
The standard gauge head 900030 is used for the dial gauge stand no. It is obtained from the respective film thicknesses d ₅₀ and d ₅₀₀ when a load of 50 g and a load of 500 g are applied to the dial gauge holding portion using 7001DGS-M according to the following formula. Cushion factor _{= (d 50 -d 500) /} d 50

(10) Shape Factor In the same manner as when determining the average diameter of voids, the shape of the incompatible polymer in the cross section of the film is subjected to an image analyzer and expressed as a ratio of 100 average major axis / minor axis.

(11) Adhesiveness of coating layer The adhesiveness of the coating layer / support was measured by inserting a cross cut (100 pcs / cm ² ) on the coating layer and 45 ° to the cross cut surface. 24 (Nichiban Co., Ltd.)
And apply 10kg with a load of about 5kg using a hand roller.
The cellophane tape was forcibly peeled off in a 180 ° direction, and the degree of peeling of the coating layer was observed and evaluated. Judgment criteria: ：: very good (no peeling), ○: good (less than 5% peeling), Δ: slightly poor (5% or more less than 20% peeling), ×: bad (20% or more peeling) And

(12) Water Resistance of Coating Layer Water was applied to a cotton swab and the coating layer was slightly rubbed for evaluation. Judgment criteria: ◎: very good (no dissolution at all), ：: good (dissolve after 10 to 15 rubs), Δ: slightly poor (dissolve after 5 to 10 rubs), ×: poor (5 rubs) (13) Thickness of coating layer The thickness was determined by measuring with a micrometer or a dial gauge.

(14) Recordability Inkjet Personal computer “98no” manufactured by NEC Corporation
te ”is connected to a bubble jet printer“ BJ-10V ”manufactured by Canon Inc., and a character pattern is printed.
The print quality and ink absorbability were evaluated, and the recordability was determined as follows. The print quality was evaluated by visual observation with a magnifying glass.
It was rubbed and evaluated based on the degree of contamination of the receiving layer with the ink. ：: Printing quality and ink absorption are very good ○: Printing quality and ink absorption are good △: Printing quality and ink absorption are slightly poor ×: Printing quality and ink absorption are poor

Offset Printing TK Mark Five Red (manufactured by Toyo Ink Co., Ltd.), which is an ink for offset printing, was printed using a printability tester RI-2 type (manufactured by Akira Seisakusho Co., Ltd.). The judgment was made based on the standard. The ink volume was 0.3 cc, and the absorptivity was evaluated using OK coated paper (Oji Paper Co., Ltd.)
Then, a metal roll having a line thickness of 353 g / cm was run from the top of the coated surfaces, and the time until ink was no longer transferred to the OK coated paper was visually determined. ◎: Good (No transfer in 15 minutes or less) ○: Good (No transfer in 15 to 30 minutes) △: Slightly poor (No transfer in 30 to 60 minutes) ×: Bad (After 60 minutes or more) Also transcribe)

Next, the present invention will be described more specifically with reference to examples.

Example 1 A polyethylene terephthalate chip and a master chip to which polyethylene glycol having a molecular weight of 4000 was added at the time of polymerization of polyethylene terephthalate were used.
After vacuum drying at ℃, polyethylene terephthalate 89% by weight, polyethylene glycol 1% by weight, and polymethylpentene 10% by weight were mixed and mixed.
Feed to extruder B heated to 300 ° C. The polyethylene terephthalate containing 10% by weight of calcium carbonate having an average particle diameter of 1.0 μm is dried as described above and then supplied to the extruder A. The polymers extruded from the extruders A and B were laminated so as to have a three-layer configuration of A / B / A, and formed into a sheet from a T die. Further, the unstretched film cooled and solidified by a cooling drum having a surface temperature of 25 ° C. was led to a group of rolls heated to 85 to 95 ° C., stretched 3.4 times in the longitudinal direction, and cooled by a group of rolls of 25 ° C. Subsequently, the longitudinally stretched film was guided to a tenter while gripping both ends of the film with clips, and was horizontally stretched 3.6 times in a direction perpendicular to the longitudinal direction in an atmosphere heated to 130 ° C. Thereafter, the film was thermally solidified at 230 ° C. in a tenter, cooled slowly to room temperature, and wound up to obtain a film having a thickness of 100 μm. The laminated configuration was 5/90/5 μm. A coating agent having the following composition was applied on the polyester film obtained by the above method using a gravure coater. Table 1 shows the properties of the film.

[0058]

[Table 1]

[Coating composition] 70 parts by weight (solids weight ratio) of a graft copolymerized acrylic resin (Soken Chemical Co., Ltd. L-40) and a cationic acrylic polymer (Soken Chemical Co., Ltd.)
30 parts by weight (solid content weight ratio), an average particle diameter of 3.5 μm as inorganic particles, and a specific surface area of 350 m ² /
g of amorphous silica (Mizukasil P- manufactured by Mizusawa Chemical Co., Ltd.)
78A) 50 parts by weight (solid content weight ratio) were diluted with a toluene / methyl ethyl ketone mixed solvent (weight ratio = 1/1) to obtain a 20% by weight coating composition.

As is clear from Table 2, this coating laminate exhibited excellent properties in all of the coating film strength, recording properties and water resistance.

Examples 2 to 3 Coating laminates were obtained in the same manner as in Example 1, except that the amount of the inorganic particles was changed. As is clear from Table 2, this coating laminate has excellent coating strength, recordability, and water resistance.

Example 4 In the coating composition of Example 1, the type of the inorganic particles was changed (average particle diameter: 1.5 to ² μm, specific surface area: 220 to 260 m ² /
g A coating laminate was obtained by the same method except that Fine Seal K-40 manufactured by Tokuyama Soda Co., Ltd. was used. As is clear from Table 2, this coating laminate showed excellent properties in all of the coating film strength, recording properties and water resistance.

Examples 5 to 6 Coating laminates were obtained in the same manner as in Example 4, except that the amount of inorganic particles was changed. Table 2
As shown in Table 2, the coating film strength, recording properties and water resistance were excellent.

Example 7 In the coating composition of Example 1, the inorganic particles were changed to organic particles. A coating laminate was obtained by the same method except that styrene-acrylic resin powder (Muticle 110C manufactured by Mitsui Toatsu Chemicals, Inc.) was used as the particles. As is clear from Table 2, this coating laminate has excellent coating strength, recordability, and water resistance.

Example 8 In the coating composition of Example 7, styrene resin powder (Muticle 240 manufactured by Mitsui Toatsu Chemicals, Inc.) was used as organic particles.
A coating laminate was obtained by the same method except that D) was used. As is clear from Table 2, this coating laminate has excellent coating strength, recordability, and water resistance.

Comparative Example 1 A coating laminate was obtained in the same manner as in Example 1, except that the particles were omitted. As shown in Table 2, the coating laminate thus obtained had a drawback of poor recording properties.

Comparative Example 2 50 parts by weight (solid content ratio) of an acrylic polymer emulsion having an average particle size of 0.2 μm and the inorganic particles 5 of Example 1
0 parts by weight (solid content weight ratio) was diluted with water to make a coating composition of 20% by weight, and coated by the same method as in Example 1. However, at the time of coating, the coating composition foamed, and the obtained coating laminate was coated. The appearance of the film was poor, and as shown in Table 2, the printability was good in offset printing, but the ink jet had ink absorption speed and ink bleeding.

Example 9 A polyethylene terephthalate homopolymer chip manufactured by a conventional method (intrinsic viscosity: 0.62, melting point: 25)
(9 ° C.) to obtain a 75 μm biaxially stretched polyester film by a conventional method. A coating laminate was obtained on the polyester film thus obtained by the same method as in Example 1. The coating laminate thus obtained was excellent in all of the coating strength, recording properties and water resistance as shown in Table 2.

Example 10 A commercially available high-quality paper was coated on one side with a bar coater so that the coating amount after drying was 10 g / m ² to obtain a coating laminate. As shown in Table 2, this coating laminate had excellent coating strength, recording properties, and water resistance.

[0070]

[Table 2]

[0071]

The coating laminate of the present invention has water resistance,
It has excellent adhesion to the substrate, printing quality, and ink absorbency.

The coating laminate manufactured as described above can be preferably used in applications such as ink jet printing, offset printing, and flexographic printing.

Further, the coating laminate of the present invention utilizes the excellent ink absorbency and adhesion to the substrate to make use of other sublimation-type heat-sensitive ink receivers, electrophotographic toner receivers, fabric ink receivers and the like. It can also be applied as an ink or toner receptor.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) B32B 1/00-35/00 B41J 15/00-15/24 B41M 5/00-5/26 C08J 7 / 04

Claims (1)

(57) [Claims] 1. A coating laminate comprising a support and a coating layer comprising inorganic and / or organic particles and a polymer binder, wherein the polymer binder has a backbone that is hydrophobic. A coating laminate comprising, as main components, a graft copolymerized acrylic resin composed of a monomer and having a branched chain composed of a hydrophilic monomer, and a cationic polymer.