JPH04364947A - Coating laminate - Google Patents

Abstract

PURPOSE:To provide a coating laminate with no foaming of a coating during coating process and excellent adhesiveness and water resistance. CONSTITUTION:In a coating laminate wherein a laminated layer contg. an inorg. and/or org. particle and a polymer adhesive is provided on a substrate, the polymer adhesive contains a graft-copolymerized acryllc resin wherein the trunk chains consist of a hydrophobia monomer and the branch chains consist of a hydrophilic monomer and a cationic acrylic polymer as main ingredients.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating laminate, which is applicable to various types of printing sheets such as inkjet printing, offset printing, and flexographic printing.

0002

[Prior Art] Conventionally, coating laminates applied to printing sheets include those in which a water-based coating agent consisting of inorganic particles and an aqueous binder emulsion is applied to the surface of high-quality paper, synthetic paper, plastic film, etc. It is being

0003

[Problems to be Solved by the Invention] However, the coating laminate produced by the above manufacturing method has insufficient adhesion to the base material and water resistance, and the coating agent uses a water-based binder emulsion, so the coating process is difficult. However, various problems such as foaming properties occurred during the process.

0004

[Means for Solving the Problems] In order to solve the above-mentioned problems, the present invention provides a coating layer containing inorganic and/or organic particles and a polymeric binder on a support. In the coating laminate, the polymer binder is mainly composed of a graft copolymerized acrylic resin whose main chain is made of a hydrophobic monomer and whose branch chains are made of a hydrophilic monomer, and a cationic polymer. The gist of the invention is a coating laminate having the following properties.

As the support in the present invention, paper (woodfree paper), coated paper, Japanese paper, nonwoven fabric, and plastic film can be used.

[0006] As for paper, ``JIS standard P3 for printing paper'' is used.
101-P3105” and “Print Magazine 1988 (vol.
71)" can be used, especially printing paper A.
(High quality paper) is preferred.

[0007] As the nonwoven fabric, those described in "Nonwoven Fabric Essentials" (Kobunshi Kankakai, written by Yoshito Miura, published in 1972) are preferred.

Plastic films include polyester, polyolefin, polyamide, polyester amide, polyether, polyimide, polyamideimide, polystyrene, polycarbonate, polyP-phenylene sulfide, polyether ester, polyvinyl chloride,
Poly(meth)acrylic acid ester and the like are preferred. Furthermore, copolymers, blends, and crosslinked products of these can also be used.

Among the above-mentioned supports, plastic films are particularly preferred, and polyesters, preferably polyethylene terephthalate, are particularly preferred from the viewpoint of mechanical properties, workability, and the like.

[0010] More preferably, polyester is provided with cushioning properties by adding an incompatible polymer or a specific gravity lowering agent. That is, it is preferable that the heat shrinkage rate at 150°C is less than 2% and the specific gravity is 1.2 or less. This is because if it is larger than 1.2, softness and cushioning properties will not be imparted to the film.

[0011] In the present invention, the polyester film suitable for the support preferably has a heat shrinkage rate of less than 2%, preferably less than 1%, at 150°C in both the longitudinal and transverse directions.

[0012] The polyester film referred to in the present invention is
It is a polymer obtained by condensation polymerization from diol and dicarboxylic acid. Dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid,
It is represented by adipic acid, sebacic acid, etc.
The diols are typified 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, etc. may be mentioned. In the case of the present invention, in particular polyethylene terephthalate,
Polyethylene naphthalate is preferred. Polyethylene terephthalate film has excellent water resistance, durability, and chemical resistance.

Of course, these polyesters may be homopolyesters or copolyesters. Examples of copolymerization components 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.

[0014] Furthermore, various known additives such as antioxidants and antistatic agents may be added to the polyester as necessary to the extent that the properties are not impaired.

[0015] The polyester film used in the present invention is
It is preferable to use a film that contains fine air bubbles inside the film and is whitened by preventing the air bubbles from scattering light. The formation of this fine bubble is caused by the film base material,
For example, it is formed by finely dispersing an incompatible polymer in polyester and stretching it uniaxially or biaxially. During stretching, voids (bubbles) are formed around the incompatible polymer particles, which exhibit a light scattering effect and become white, making it possible to obtain a high reflectance.

[0016] The incompatible polymer refers to a polymer that does not dissolve in polyester, such as poly-3-methylbutene-1, poly-4-methylpentene-1, polypropylene, polyvinyl-t-butane, 1,4-trans -Poly-
Examples include 2,3-dimethylbutadiene, cellulose triacetate, cellulose tripropionate, and polychlorotrifluoroethylene. Among these, polyolefins, particularly polymethylpentene, are preferred. This is because voids are easily generated when stretched, and because the polymer has high transparency, it absorbs little light and does not absorb light scattered by voids.

The amount of the incompatible polymer added is preferably 2% by weight or more and 25% by weight or less. If it is less than this, sufficient whitening will not be achieved, and if it is more than this, the film strength will become too low.

The film obtained as described above has a low specific gravity because it contains fine bubbles. 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. If the specific gravity is less than 0.5, the film strength will be too low, and if it exceeds 1.2, sufficient whitening will not be achieved.

[0019] Furthermore, the whiteness of the film obtained as described above is preferably 70% or more. More preferably, it is 80% or more.

[0020] Furthermore, by uniformly dispersing the incompatible polymer,
In addition, it is preferable to add a specific gravity lowering agent in order to sufficiently generate fine bubbles. A specific gravity lowering agent is a compound that is added as an auxiliary agent together with the above-mentioned incompatible polymer, and has the effect of promoting the creation of voids at the interface between the polyester and the incompatible polymer, thereby reducing the specific gravity. The effect is observed only for compounds. For example, for polyester, polyalkylene glycols and their derivatives such as polyethylene glycol, methoxypolyethylene glycol, polytetramethylene glycol, and polypropylene glycol, ethylene oxide/propylene oxide copolymers, and even sodium dodecylbenzene sulfonate and alkyl sulfonates are used. Representative examples include sodium salt, glycerin monostearate, and tetrabutylphosphonium para-aminobenzenesulfonate. In the case of the present invention, polyethylene glycol is particularly preferred. By adding a specific gravity lowering agent, the specific gravity of the polyester film can be reduced by 0.1 g/cc or more. Furthermore, the addition of this specific gravity lowering agent not only improves the whiteness of the polyester film and smoothes the surface, but also improves cleavage resistance and significantly improves the stretchability of the polyester. The amount of the specific gravity lowering agent added is preferably 0.1 to 5% by weight. If the amount added is less than 0.1% by weight, the effect of the addition will be diminished, and if it exceeds 5% by weight, the properties of the film base material may be impaired.

Next, it is preferable that the incompatible polymer has a nearly spherical shape in the polyester film, that is, the shape factor is in the range of 1 to 4. Significant differences arise in the film properties obtained depending on the properties of the incompatible polymer in the polyester film, particularly in the correlation between the film's specific gravity and cushioning ratio, thermal dimensional stability, surface roughness, whiteness, etc. In other words, when the shape of the incompatible polymer is close to spherical, it is possible not only to lower the specific gravity compared to when it is dispersed in layers, but also to obtain a film with high whiteness, high cushioning ratio, and good thermal dimensional properties. . Dispersing the polymer in a nearly spherical shape depends strongly on the viscosity, compatibility parameter, and melting point of the incompatible polymer added to the polyester, as well as the type and amount of the specific gravity lowering agent. A shape close to a spherical shape refers to a case where 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 cushioning ratio of the polyester film suitable as the support of the present invention is preferably 10% or more, more preferably 15% or more. Cushion rate is 10
If it is less than %, the feel when touching the hand will be poor.

The optical density of the polyester film suitable as the support of the present invention is preferably 0.7 or more and 1.6 or less, more preferably 0.8 or more and 1.6 or less. If the optical density is less than 0.7, the hiding power of the film will be insufficient and the back side will be transparent, which is not preferable. Furthermore, if the optical density exceeds 1.6, it must contain a large amount of microbubbles,
This is not preferable because the film strength becomes weak.

Furthermore, in the present invention, a polyester film containing fine particles of calcium carbonate, amorphous zeolite particles, anatase type titanium dioxide, calcium phosphate, silica, kaolin, talc, clay, etc. may be used. The amount of these additives added is preferably 0.0005 to 25 parts by weight per 100 parts by weight of the polyester composition. In addition to such fine particles, fine particles precipitated by a reaction between a catalyst residue and a phosphorus compound in a polyester polymerization reaction system can also be used in combination. Examples of the precipitated fine particles include those made of calcium, lithium, and phosphorus compounds. The content of these particles in the polyester is preferably 0.05 to 1.0 parts by weight per 100 parts by weight of the polyester.

Further, in the present invention, a laminated film structure may be used if necessary. For example, it has a two-layer structure of A/B or a three-layer structure of A/B/A. In this case, layer B is a layer containing microbubbles, and layer A may contain inorganic additives such as titanium dioxide, silicon dioxide, and calcium carbonate.

[0026] The thickness of the plastic film is 1
It is preferable that it is 0 micrometer - 250 micrometers. More preferably, the thickness is 15 μm to 150 μm, which is excellent in practical handling as a base material.

[0027] The plastic film may be subjected to known surface treatments such as corona discharge treatment, plasma discharge treatment, anchor coating, etc., to improve adhesion, if necessary.

Inorganic particles as used in the present invention 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 these, porous particles having pores on the particle surface are preferable, and particles having a hollow porous or non-hollow porous form that can freely enclose and release liquid, solid, or gas inside are preferable in terms of ink absorbency. preferred. The method for producing porous particles is not particularly limited, but typical production methods include those disclosed in JP-A No. 62-292476, Japanese Patent Publication No. 54-6251, and Japanese Patent Publication No. 57-55.
454 and Japanese Patent Publication No. 55-43404, etc., is a method of preparing inorganic powder by "interfacial reactivity", that is, aqueous precipitation reaction, but in the preparation process, water-in-oil (W/O type) can be manufactured by preparing hollow, spherical, and porous inorganic powder particles by using an emulsion.

[0030] Specific examples of the inorganic wall material constituting the porous particles include alkaline earth metal carbonates such as calcium carbonate, barium carbonate, and magnesium carbonate, calcium silicate, barium silicate, and magnesium silicate. Alkaline earth metal silicates, calcium phosphate, etc.
Alkaline earth metal phosphates such as barium phosphate and magnesium phosphate, alkaline earth metal sulfates such as calcium sulfate, barium sulfate, and magnesium sulfate, silicic anhydride, aluminum oxide, zinc oxide, iron oxide, titanium oxide, Metal oxides such as cobalt oxide, nickel oxide, manganese oxide, antimony oxide, tin oxide, iron hydroxide, nickel hydroxide, aluminum hydroxide, calcium hydroxide,
Metal hydroxides such as chromium hydroxide, metal silicates such as zinc silicate, aluminum silicate, copper silicate, metal carbonates such as zinc carbonate, aluminum carbonate, cobalt carbonate, nickel carbonate, basic copper carbonate, etc. Among them, those made of silicic anhydride are particularly suitable in the present invention in view of the characteristics of the coating laminate.

The organic particles referred to 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-acrylic resin powder, and the like. Among these, specifically shaped particles of acrylic resin powder and styrene-acrylic resin powder are preferred. Among these, doughnut-shaped flat particles, fine particle aggregate particles, core-shell structure particles, hollow porous particles, and the like are preferable. By using these uniquely shaped particles, ink absorbency can be increased.

The average particle size of the inorganic and/or organic particles is 0.1 μm to 25 μm, preferably 0.5 μm to 15 μm.
.mu.m, more preferably 0.5 .mu.m to 10 .mu.m from the viewpoint of ease of handling, coatability, printability, etc.

Further, the content of inorganic and/or organic particles in the coating layer is 1 to 100% by weight, preferably 5 to 7% by weight.
Preferably it is 0% by weight. If the content is less than 1% by weight, the ink setting properties will be insufficient, and if it exceeds 100% by weight, the adhesion between the coating layer and the film support will tend to decrease.

[0034] In the present invention, the polymer binder is one whose main component is a graft copolymerized acrylic resin, and different types of monomers are selected for the trunk chain and branch chains, and the functions of the trunk chain and the branch chains are differentiated. It is a functionally separated polymer with multiple functions. Among these, by using a hydrophobic polymer as the main chain and a hydrophilic polymer as the branch chain, the coating film after coating can be made hydrophilic and water resistant. In the present invention, the graft copolymerized acrylic resin as the main component refers to one in which it accounts for 50% by weight or more, preferably 60% by weight or more in the polymer binder, and if necessary, other materials may be used as long as the properties are not impaired. may be added. In the polymer binder used in the present invention, monomer units into which hydrophobic polymers are introduced include styrene, styrene derivatives, vinylnaphthalene, vinylnaphthalene derivatives, and (meth)
Examples include acrylic esters. The monomer unit into which the hydrophilic polymer is introduced is one having a hydrophilic structural moiety such as a carboxylic acid group, a sulfonic acid group, a sulfuric acid ester group, a phosphoric acid group, a hydroxyl group, an amino group, or an amide group. In addition to the above monomer units, acrylonitrile, acrylamide, methacrylamide, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate, N-methylolacrylamide, N-butoxymethylacrylamide, etc. can be used. Among these, those copolymerized with methyl methacrylate in the trunk chain, hydroxyethyl methacrylate in the branch chains, and/or N-methylolacrylamide are preferred.

[0035] A polymer electrolyte or conductive powder is usually added to the coating layer in order to adjust the electrical resistance of its surface. In the present invention, a cationic polymer such as a quaternary ammonium salt is preferably used as the polymer electrolyte from the viewpoint of conductivity and compatibility with the polymer binder. Among them, cationic acrylic polymers are more preferably used. Examples of cationic acrylic polymers include salts of butyl methacrylate and dimethylaminoethyl methacrylate, and specifically, Elecondo PQ-10, PQ-50B, B-149 manufactured by Soken Chemical Co., Ltd. can be effectively used. In the present invention, the conductive powder to be added is not particularly limited, but tin oxide, indium oxide, zinc oxide, tantalum oxide, and combinations thereof are preferred.

The coating layer constituting the coating laminate of the present invention has a smoothness of 2 to 5000 seconds, preferably 10 to 3 seconds.
000 seconds, preferably in the range of 20 to 2500 seconds. If the smoothness is lower than that of the present invention, the ink permeation rate will be too high and the recording will become pale, which is not preferable. If it is larger than the present invention, the ink permeation rate is too low, so ink tends to remain on the surface of the coating layer, and when the recording surface is rubbed, the recording surface is likely to be smeared with residual ink, which is not preferable.

Further, 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 preferably 1.0 μm to 20 μm.
It is preferable that the amount is within the range of m in terms of uniform formation of the coating layer, adhesion, etc. The coating layer may also contain known additives, such as coating properties improvers, thickeners, antioxidants, ultraviolet absorbers, and dyes, in amounts that do not impair the present invention, if necessary.

The coating laminate of the present invention has a coating layer made of the above-mentioned composition provided on at least one side of a support. When the support is a plastic film, the method for forming the coating layer is as follows: 1. In the film forming process, the base film support is stretched in advance, then a liquid adjusted to a predetermined amount is applied, and then dried. Method (2) A method in which the base film is rolled up as a single film and then a coating-drying process is provided is preferably applied.

The solution of the above-mentioned components 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 coating. The organic solvent is not particularly limited, but toluene, methyl ethyl ketone, methyl cellosolve, isopropyl alcohol, etc. are preferably used.

[0040] The coating method is not particularly limited, but gravure coating, reverse coating, reverse gravure coating, kiss coating, die coating, metaling bar coating, etc. can be used because it is possible to coat a thin film at high speed. Known methods can be applied. In addition, the coating speed,
The coating film drying conditions are not particularly limited, but it is desirable that the coating film drying conditions be within a range that does not adversely affect the properties of the coating layer or the support.

[0041]

[Example] First, methods for measuring various characteristics in the present invention will be explained.

(1) Smoothness Oken type smoothness tester manufactured by Asahi Seiko Co., Ltd. (model KB-15)
It was measured with Shown as the average of n=5.

(2) Surface roughness According to JIS B0601-1967, cutoff 0
．． 25 mm, measurement length 4 mm, center line average roughness Ra (μm
) and maximum roughness Rt (μm).

(3) Average spherical equivalent diameter of the void Take a photograph of a cross section taken in the machine direction or perpendicular direction of the film forming process, magnified 1,000 to 5,000 times with a scanning electron microscope, and measure the specified thickness range. At least 100 voids are subjected to an image analyzer to obtain the distribution of diameters of circles corresponding to the area of the voids. The volume average diameter of this distribution is defined as the average spherical equivalent diameter of the void.

(4) Specific gravity: 25% by carbon tetrachloride-n-heptane density gradient tube
Use the value in °C.

(5) Heat shrinkage rate The film has a width of 10 mm and a length of 300 mm in the longitudinal direction or width direction.
After cutting into pieces of mm, marking them at 200 mm intervals and fixing them to a support plate under constant tension (5 g), measure the original length a (mm) of the marking intervals. Next, a load is applied 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 rate is determined using the following formula, and the average value of the five samples is used. Heat shrinkage rate (%) = (a-b)/a

(6) Optical density The films were stacked to a thickness of about 150 μm, and the transmission density was 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, the whiteness (%) is expressed as 4B-3G.

(8) Stretchability When the film was continuously formed for 24 hours, a film with no tearing was evaluated as "good", and a film with two or more tears was evaluated as "broken".

(9) Cushion rate Mitoyo Seisakusho Co., Ltd. Dial Gauge No. 2109-10
Using standard probe 900030, dial gauge stand No. It is determined by the following formula from the film thicknesses d50 and d500 when a load of 50g and 500g is applied to the dial gauge holding part using 7001DGS-M. Cushion rate = (d50-d500)/d50

00
(10) Shape factor In the same way as when determining the average diameter of voids, the shape of the incompatible polymer in the cross section of the film is expressed by the ratio of 100 average major diameters to minor diameters using an image analyzer.

(11) Adhesion of the coating layer The adhesion of the coating layer/support is determined by cross-cutting (
100 pieces/cm2), and sellotape: CT-24 (manufactured by Nichiban Co., Ltd.) at 45 degrees to the cross-cut surface.
Paste it and use a hand roller to roll it for 10 minutes with a load of about 5 kg.
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 are: ◎: Very good (no peeling), ○: Good (peeling area less than 5%), △: Slightly poor (peeling area 5% or more and less than 20%), ×: Poor (peeling area 20% or more) And so.

(12) Water resistance of the coating layer A cotton swab was soaked in water and the coating layer was lightly rubbed for evaluation. The evaluation criteria are: ◎: Very good (does not dissolve at all), ○: Good (dissolves after rubbing 10 to 15 times), △: Slightly poor (
(Dissolves when rubbed 5 to 10 times), ×: Poor (Dissolves when rubbed less than 5 times.) (13) Coating layer thickness Determined by measuring with a micrometer or dial gauge.

(14) Recordability ■ Inkjet personal computer “98no” manufactured by NEC Corporation
Bubble jet printer manufactured by Canon Co., Ltd.
BJ-10V" were connected, a character pattern was printed, the print quality and ink absorption were evaluated, and the recording performance was determined as follows.The print quality was evaluated by visual observation using a magnifying glass, and the ink Immediately after printing, the absorbency was evaluated by rubbing the character pattern once with a finger and evaluating the degree of staining of the receiving layer by ink. ◎: Very good printing quality and ink absorption ○: Good printing quality and ink absorption △: Print quality and ink absorption are slightly inferior ×: Print quality,
Poor ink absorption

■ Offset printing Printing was carried out using TK Mark Five Beni (manufactured by Toyo Ink Co., Ltd.), an offset printing ink, using a printing aptitude tester RI-2 model (manufactured by Mei Seisakusho Co., Ltd.), and the following results were obtained. Judgment was made using evaluation criteria. The amount of ink applied was 0.3 cc, and the absorbency was evaluated by superimposing the coated surface of OK coated paper (manufactured by Oji Paper Co., Ltd.) on the printed surface with a line thickness of 353 g/cm.
A metal roll was run and the time until the ink stopped transferring to the OK coated paper was visually determined. ◎: Good (transfer stops within 15 minutes) ○:
Good (transfer stops after 15 to 30 minutes) △: Slightly poor (transfer stops after 30 to 60 minutes) ×: Poor (transfer occurs even after 60 minutes or more)

Next, the present invention will be explained in more detail with reference to Examples.

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

[0058]

[Table 1]

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

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

Examples 2 to 3 Coated laminates were obtained using the same method as in Example 1 except that the amount of inorganic particles added was changed. As is clear from Table 2, this coating laminate has excellent coating film strength, recording performance, and water resistance.

Example 4 In the coating material of Example 1, the type of inorganic particles was changed (average particle diameter 1.5 to 2 μm, specific surface area 220 to 260 m2).
/g Fine Seal K-40 manufactured by Tokuyama Soda Co., Ltd.
) A coated laminate was obtained by the same method except that. As is clear from Table 2, this coating laminate exhibited excellent properties in terms of coating film strength, recording performance, and water resistance.

Examples 5 to 6 Coated laminates were obtained using the same method as in Example 4 except that the amount of inorganic particles added was changed. Table 2
As shown in the figure, the film has excellent coating strength, recording performance, and water resistance.

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

Example 8 In the coating material of Example 7, styrene resin powder (Mitsui Toatsu Chemical Co., Ltd. Muticle 240) was used as the 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 film strength, recording performance, and water resistance.

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

Comparative Example 2 50 parts by weight (solid content weight ratio) of an acrylic polymer emulsion with an average particle diameter of 0.2 μm and 5 parts of the inorganic particles of Example 1
0 part by weight (solid content weight ratio) was diluted with water to make a 20% by weight coating and coated using the same method as in Example 1, but the coating foamed during coating and the resulting coating laminate was coated. The appearance of the film was poor, and as shown in Table 2, the recording performance was good in offset printing, but the ink absorption rate and ink bleeding were poor in inkjet printing.

Example 9 Homopolymer chips of polyethylene terephthalate (intrinsic viscosity: 0.62, melting point: 25
A 75 μm biaxially stretched polyester film was obtained using a conventional method. A coating laminate was obtained on the thus obtained polyester film by the same method as in Example 1. As shown in Table 2, the coating laminate thus obtained was excellent in coating strength, recording performance, and water resistance.

Example 10 The coating composition of Example 1 was coated on one side of a commercially available high-quality paper using a bar coater so that the coated amount after drying was 10 g/m 2 to obtain a coated laminate. As shown in Table 2, this coating laminate was excellent in coating strength, recording performance, and water resistance.

[0070]

[Table 2]

[0071]

[Effects of the invention] The coating laminate of the present invention has water resistance,
It has excellent adhesion to the substrate, print quality, and ink absorption.

The coating laminate produced as described above can be preferably used in applications such as inkjet printing, offset printing, and flexographic printing.

Furthermore, the coating laminate of the present invention can be used for other thermal ink receptors including sublimation type, electrophotographic toner receptors, fabric ink receptors, etc. by utilizing its excellent ink absorbency and adhesion with substrates. It can also be applied as an ink or toner receiver.

Claims (1)

[Claims] Claim 1: A coating laminate comprising a coating layer containing inorganic and/or organic particles and a polymeric binder on a support, wherein the polymeric binder has a hydrophobic backbone. A coating laminate characterized in that the main components are a graft copolymerized acrylic resin whose branch chains are composed of hydrophilic monomers, and a cationic polymer.