IMAGE RECEIVING MATERIAL FOR OFFSET PRINTING

[DESCRIPTION]

FIELD OF THE INVENTION

The present invention relates to an image receiving material for offset printing, in particular to a synthetic paper that can be used for offset printing.

BACKGROUND OF THE INVENTION

Offset printing on paper is a widely used printing process. Instead of conventional cellulose paper supports, optionally provided with one or more additional layers, so called plastic or synthetic papers are also available. An advantage of such plastic or synthetic papers is their outdoor usability due to their improved resistance towards moisture .

Synthetic papers may be classified into two different types: one with a fibrous structure comprising synthetic fibers made from for example polyamides, polyester, or polyolefins; and one in which a film is directly extruded from a thermoplastic polymer.

Extruded films typially have a smooth surface. There are no cavities with capillary activity such as between the fibers of cellulose paper or synthetic fiber webs. The combination of a smooth surface, low absorbing power and a non-polar structure often makes it difficult to print on such polymer films: drying times are long, and the adhesion of the printing ink is poor.

Extruded films are typically made from polyethylene, polypropylene or polyester. By the incorporation of "voids" and/or opacifying pigments in for example the polyester film, an opaque plastic paper can be obtained, such as for example disclosed in WO2008040670 , WO2008040701, WO2008116869 and WO2008116797. To improve the printability, dedicated ink receiving layers have been provided on plastic supports. See for example EP-A 1743976, US20060257593 , US20040146699 , WO2003033577 , US6300393 and

JP 11-107194, US5397637 and GB2177413.

An example of a synthetic paper for offset printing is disclosed in EP-A 2103736. It comprises an optionally subbed support and a single layer, the single layer having a layer thickness of at least

3 μτη, a pore volume of at least 1.2 ml/m and comprising at least one porous pigment, at least one latex and at least one water soluble binder. The water soluble binder is a polyvinyl alcohol- polyvinyl acetate copolymer.

It has been observed that while or after printing on synthetic paper, the blanket roller may be contaminated with "dust", the dust originating from the ink receiving layer. Such a contamination of the blanket roller with dust may result in printing artefacts. Such a contamination of the blanket roller worsen as more prints are made on synthetic paper without cleaning the blanket roller.

As synthetic paper is often used outdours, the coating has to be as resistant as possible to moisture. Even under moist conditions, the scratch resistance of the ink reveiving layer must be sufficient to avoid damage of the printed image upon contact .

SUMMARY OF THE INVENTION

It is an object of the present invention to provide an image receiving material for offset printing which has an improved water resistance and which has been improved with respect to contamination of the blanket roller.

The object of the present invention has been realized by an image receiving material for offset printing comprising a support and an image receiving layer, the image receiving layer comprising a porous pigment and an aqueous dispersion of a polymer particle characterized in that the image receiving layer further comprises a copolymer comprising alkylene and vinyl alcohol units.

DETAILED DESCRIPTION OF THE INVENTION

The image receiving material for offset printing according to the present invention comprises a support and an image receiving layer, the image receiving layer comprising a porous pigment and an aqueous dispersion of a polymer particle characterized in that the image receiving layer further comprises a copolymer comprising alkylene and vinyl alcohol units.

Copolymer comprising alkylene and vinyl alcohol units.

The image receiving layer comprises a copolymer comprising alkylene and vinyl alcohol units. The alkylene units are preferably ethylene units .

The copolymer is preferably prepared by hydrolysis of a copolymer comprising vinyl ester units and alkylene units wherein the vinyl ester units are partly or totally converted by hydrolysis to vinyl alcohol units. The vinyl ester units are preferably vinyl acetate.

The amount of vinyl ester units converted to vinyl alcohol units is typically defined by the degree of hydrolysis (in mol %) . The degree of hydrolysis is preferably at least 85 mol %, more preferably at least 90 mol %.

A particularly preferred copolymer is a copolymer comprising vinyl alcohol units, vinyl acetate units and ethylene units.

The copolymer comprising vinyl alcohol and alkylene units is preferably water soluble. Preferably, the copolymer has a solubility in water at room temperature up to 2 wt.%, more preferably up to 4 wt.%; most preferably up to 5 wt.%. To improve the solubility, minor amounts of an organic solvent, for example fenoxyethanol , may be added. When organic solvent is used, the amount is preferably less than 5 wt.%, preferably less than 2.5 wt . %

To prepare stable solutions, it may be necessary to heat the solution up to 90 - 95°C while stirring, to keep it at that

temperature while stirring for 1 or 2 hours and then cooling it down to room temperature .

The amount of ethylene units in the copolymer is preferably between 0.1 and 20 wt.%, more preferably between 0.25 and 15 wt.%, most preferably between 0.50 and 10 wt.%.

When considering the amount of ethylene units in the copolymer in mol%, the amount is preferably between 0.25 and 25 mol%, more preferably between 0.50 and 20 mol%, most preferably between 1.0 and 15 mol %.

Examples of commercially available copolymers (all from KURARAY) comprising vinyl alcohol and ethylene units are given in Table 1, together with the degree of hydrolysis and the amount of ethylene units (based on commercial information from KURARAY) . Regarding the ethylene content, the numbers 1 to 4 reflect the amount in that a higher number means a higher amount of ethylene .

Table 1

Product name Degree of hydrolysis Ethylene

(mol%) content

Exceval AQ-4104 98.0-99.0 4

Exceval HR-3010 99.0-99.4 3

Exceval RS-2117 97.5-99.0 2

Exceval RS-1717 92.0-94.0 1

Exceval RS-1713 92.0-94.0 1

Exceval RS-4105 9 .5-99.0 4 Exceval RS-2713 92.0-94.0 2

Exceval RS-2817 95.5-97.5 2

A quantitative analysis by means of element analysis, corrected for the water content of the samples and neglecting the vinyl acetate content, indicated that the tested copolymers have an ethylene content up to approximately 10 wt . % (or approximately 15 mol %) Two or more different copolymers comprising vinyl alcohol and ethylene units may be used in the image receiving layer.

The image receiving layer may also comprise, in addition to the copolymer comprising vinyl alcohol and ethylene units, other types of, preferably water soluble, copolymers such as polyvinyl - polyvinylacetate copolymers, carboxy-modified polyvinyl alcohol, carboxymethyl-cellulose, hydroxyethylcellulose , cellulose sulfate, polyethylene oxides, gelatin, cationic starch, casein, sodium polyacrylate , styrene-maleic anhydride copolymer sodium salt, sodium polystyrene sulfonate. Among these, vinyl alcohol-vinyl acetate copolymers such as disclosed in EP2103736, paragraph [79] - [82] are preferred .

The total amount of the copolymer comprising vinyl alcohol and ethylene units in the image receiving layer is preferably between

2 2

0.05 and 1.0 g/m , more preferably between 0.10 and 0.75 mg/m , most

2

preferably between 0.15 and 0.45 mg/m .

The ratio of the amount of the copolymer comprising vinyl alcohol and ethylene units to the amount of porous pigment, both present in the image receiving layer, is preferably between 0.05 and 0.50, more preferably between 0.10 and 0.25. Aqueous dispersion of polymer particles

The image receiving layer comprises an aqueous dispersion of polymer particles, often referred to as a latex.

A preferred latex is an acrylic latex, a polyester latex or a polyurethane latex. Particularly preferred, an anionic acrylic or polyurethane latex is used. The polyurethane latex is preferably an aliphatic polyurethane latex.

Suitable latexes are given in Table 2.

Table 2

Product name Producer comonomers

Polysol Showa

vinyl acetate ethylene EVA550 Denko K.K.

The latex may be a self -crosslinking latex.

Suitable self-crosslinking resins are given in Table 3.

Table 3

Product name Producer Type

Acronal LR 8977 BASF acrylic

Acronal S 760 BASF acrylic

Joncryl 1580 BASF acrylic

Joncryl 8380 BASF acrylic

Joncryl 8383 BASF acrylic

Joncryl 8384 BASF acrylic

Joncryl 8385 BASF acrylic

Joncryl 8386 BASF acrylic

Joncryl 8300 BASF acrylic

Joncryl 8311 BASF acrylic

Luhydran S 937 T BASF acrylic

NeoCryl XK-98 DSM Neo-Resins acrylate

NeoPac R-9029 DSM Neo-Resins aliphatic

urethane Porous pigment

The i gage receiving layer comprises a porous pigment. The porous pigment may be an inorganic pigment and/or a polymeric pigment . Suitable pigments are those of which the primary particles have an internal porosity. However, suitable pigments are also those of which the primary particles do not have an internal porosity but which form secundary particles as a result of an aggregation of the primary particles.

Preferred pigments are inorganic pigments having a specific surface

2 2

of at least 100 m /g and a porosity of at least 1.2 ml/m .

The average particle diameter of the pigments is preferably between 1 and 10 μιτι, more preferably between 2 and 7.5 μπ\.

Suitable porous inorganic pigments are given in Table 4.

Table 4

Product name Producer Chemical

composition

Sunsphere H53 Asahi Glass Si0 ₂ 5

Sunsphere H33 Asahi Glass Si0 ₂ 3

Sunsphere H52 Asahi Glass Si0 ₂ 5

Sunsphere H32 Asahi Glass Si0 ₂ 3

Sunsphere H52 Asahi Glass Si0 ₂ 5

Sunsphere H32 Asahi Glass Si0 ₂ 3

Sunsphere H51 Asahi Glass Si0 ₂ 5

Sunsphere H31 Asahi Glass Si0 ₂ 3

Sunsil 130H-SC Sunj in Si0 ₂ 7

Sunsil 130SH Sunj in Si0 ₂ 7

Sunsil 130XH Sunj in Si0 ₂ 7

A preferred porous pigment is silica having an average particle siz preferably between 1 and 10 μτη, more preferably between 2 and 7.5 and a pore volume preferably between 0.05 and 5 ml/g, more

preferably between 0.75 and 2.5 ml/g.

The total amount of porous pigment in the image receiving layer is preferably between 0.25 and 5 g/m , more preferably between 0.5 and

2 2

4.0 g/m , most preferably between 1.0 and 3.0 g/m . Other ingredients

The image receiving layer may in addition to the porous pigment, the aqueous dispersion of a polymer particle and the copolymer

comprising alkylene and vinyl alcohol units comprise other

ingredients such as matting agents, preservatives, surfactants, colorants and antistatic components.

Preferred matting agents are disclosed in EP-A 2103736, paragraphs [91] and [92] . A preferred preservative is the sodium salt of 1,2- benzisothiazolin-3-one, commercially available under the trade name Proxel and Bronidox K.

The image receiving layer may also comprise insolubilization agents such as disclosed in EP-A 2103736, paragraph [0087] - [0090] .

The total dry weight of the image receiving layer is preferably between 1.0 and 10.0 g/m , more preferably between 2.0 and 8.0 g/m2 , most preferably between 3.0 and 6.0 g/m .

Support

The support of the image receiving material for offset printing may be transparant or opaque .

The supports that can be used in the present invention include resin-coated cellulosic paper, webs having a fibrous structure formed with synthetic fibers and webs in which a film is directly extruded from a thermoplastic polymer. The resin-coating of resin- coated cellulosic paper can be rendered non-transparent by the inclusion of opacifying pigments therein. Webs having a fibrous structure formed with synthetic fibers and webs in which a film is directly extruded from a thermoplastic polymer can be rendered non- transparent by the inclusion of opacifying pigments. Furthermore, webs in which a film is directly extruded from a thermoplastic polymer can be also rendered non-transparent by axial stretching- induced microvoid formation resulting from the presence of poorly compatible dispersions of amorphous high polymers with a higher glass transition temperature than the glass transition temperature or melting point of the matrix polymer and/or the crystalline high polymers which melt at a higher temperature than the glass transition temperature or melting point of the matrix polymer and axially stretching the extruded film. Widely used matrix polymers include polyethylene, polypropylene, polystyrene, polyamide and polyester .

The support is preferably a synthetic paper made from polyester, polyolefin or polyvinylchloride .

The support is preferably a web in which a film is directly extruded from a thermoplastic polymer. The thermoplastic polymer is

preferably a polyester. Preferably the support comprises at least 50 wt . % of a linear polyester.

According to a particularly preferred embodiment, the support is a non-transparent microvoided axially stretched directly extruded thermoplastic polymer comprising dispersed therein at least one amorphous high polymer with a higher glass transition temperature than the glass transition temperature of the thermoplastic polymer and/or at least one crystalline high polymer having a melting point which is higher than the glass transition of the thermoplastic polymer .

The thermoplastic polymer is preferably a linear polyester.

The crystalline polymer is preferably selected from the group consisting of polyethylene, preferably high density polyethylene, polypropylene, preferably isotactic polypropylene, and isotactic poly (4 -methyl-1-pentene) .

The amorphous polymer is preferably selected from the group

consisting of polystyrene, styrene copolymers, styrene-acrylonitrile (SAN) -copolymers , polyacrylates , acrylate-copolymers , poly- methacrylates and methacrylate-copolymers .

According to a particularly preferred embodiment, the support is a non-transparent microvoided axially stretched directly extruded linear polyester having dispersed therein 5 to 20 wt . % of a styrene- acrylonitrile-block copolymer.

The support preferably also comprises an opacifying pigment, the opacifying pigment being preferably selected from the group

consisting of silica, zinc oxide, zinc sulphide, barium sulphate, calcium carbonate, titanium dioxide, aluminium phosphate and clays. Preferred opacifying pigments are Ti0 ₂ pigments. Ti0 ₂ particles may be of the anatase or the rutile type. Preferably Ti0 ₂ particles of the rutile type are used due to their higher covering power. Because Ti0 ₂ is UV- sensitive , radicals may be formed upon exposure to UV radiation, Ti0 ₂ particles are typically coated with Al , Si, Zn or g oxides. Preferably such Ti0 ₂ particles having an A1 ₂ C>3 or Al ₂ 03/Si0 ₂ coating are used in the present invention. Other preferred Ti0 ₂ particles are disclosed in US6849325.

The support may further comprise one or more ingredients selected from the group consisting of of whitening agents or optical

brighteners, UV-absorbers, light stabilizers, antioxidants, flame retardants and colorants.

A particularly preferred support is disclosed in WO2008040670 and comprises a continuous phase linear polyester matrix having

dispersed therein a non-crosslinked random SAN-polymer and dispersed or dissolved therein at least one ingredient from the group of ingredients consisting of inorganic opacifying pigments, whitening agents, colorants, UV-absorbers, light stabilizers, antioxidants and flame retardants, wherein the film is white, microvoided, non- transparent and axially stretched; the linear polyester matrix has monomer units consisting essentially of at least one aromatic dicarboxylic acid, at least one aliphatic diol and optionally at least one aliphatic dicarboxylic acid; the weight ratio of the linear polyester to the non-crosslinked SAN-polymer is in the range of 2.0:1 to 19.0:1; and one of said at least one aromatic

dicarboxyate monomer units is isophthalate and said isophthalate is present in said polyester matrix in a concentration of 10 mole % or less of all the dicarboxylate monomer units in said linear polyester matrix .

A preferred process to prepare the support is disclosed in

O2008040699.

Subbing layers

To improve the adhesion of the image receiving layer to the support, one or more subbing layers may be provided between the image receiving layer and the support. Preferably, the subbing layer comprises a vinylidene chloride containing copolymer, such as for example a vinylidene chloride - methacrylic - itaconic acid

copolymer .

To optimize the antistatic properties of the image receiving material, the subbing layers preferably comprise an antistatic agent. Preferred antistatic agents are PEDOT/PSS dispersions as disclosed in the EP-As 564911, 570795 and 686662.

Process for producing the image recording material

Aspects of the present invention are also realized by a method for preparing an image receiving material for offset printing comprising the steps of :

(i) providing a support having two sides,

(ii) optionally applying a subbing layer on one or both sides of the support , and

(iii) applying the image receiving layer as described above on one or both sides of the optionally subbed support,

Preferably a subbing layer and an image receiving layer are applied on both sides of the support. Even more preferred, the subbing layers and image receiving layers on both sides of the support are identical .

As the support is typically produced by an extrusion process wherein first a thick film is formed, followed by longitudinal and then transversal stretching of the thick film, the subbing layers are preferably provided after the longitudinal stretching step while the image recording layer is preferably applied after the transversal stretching step. EXAMPLES

Materials

All materials used in the examples were readily available from standard sources such as Aldrich Chemical Co. (Belgium) and Acros (Belgium) unless otherwise specified.

• Si0 ₂ , a 20 wt.% dispersion in water of Syloid 244 from Grace GMBH.

• Joncryl FLX 5010, a 45 wt.% dispersion in water of styrene- acrylic polymer from BASF.

• PVA-1, a 3.81 wt.% aqueous solution of a fully hydrolysed (97.5 - 99.5 mol.%) polyvinylalcohol from ACETEX.

• surfactant, a 5 wt.% solution of Zonyl FSO100 from Dupont in

isopropanol .

• matting agent, a methacrylate/styreneacrylate matting agent

having an average particle diameter of 7-8 μτη.

• Exceval AQ-4104, Exceval HR-3010, Exceval RS-2117, Exceval RS- 1717, Exceval RS-1713, Exceval RS-4105, Exceval RS-2713, Exceval RS-2817, 4 wt.% solution in DW/fenoxyethanol (947 g/10 g) of a vinylalcohol - vinylacetate - ethylene copolymer, all from

KURARAY.

• S-LEC KW-1, a 20 wt.% aqeuous solution of a vinylalcohol - vinylacetate-vinylbutyral copolymer from SEKISUI .

• Polyviol LL603, a 20 wt.% aqueous solution of a vinylalcohol- vinylacetate-isopropylenealcohol-isopropyleneacetate from WACKER CHEMIE .

• Polyviol LL620, a 20 wt.% aqueous solution of a vinylalcohol - vinylacetate-vinylversatate copolymer from WACKER CHEMIE.

• MP103, a 4 wt.% solution in DW/fenoxyethanol (950/10) of

vinylalochol - vinyacetate copolymer modified with hydrophilic and hydrophobic groups from KURARAY. S-LEC KW-3, a 20 wt . % aqueous solution of a vinylalcohol - vinylacetate-vinylbutyral copolymer from SEKISUI.

Poval KL118, a 4 wt . % solution in DW/fenoxyethanol (950/10) of a carboxylated vinylalcohol - vinylacetate copolymer from KURARAY.

ichem EM39235, a 35 wt . % high density polyethylene wax from

MICHELMAN.

Chemguard S-550, a 5 wt . % solution in isopropanol of a

perfluoroalkyl polyether surfactant from CHEMGUARD.

Mersolat H, a surfactant from Lanxess.

Kieselsol 100F, a colloidal silica from HC STARCK.

PEDOT/PSS, poly (ethylene dioxythiophene) /poly (styrene sulfonic acid) sodium salt .

Dust deposition test on a AB-D360 printing press

125 sheets (size A4) of testmaterial were run 4 times through a AB D360 printing machine. So the testmaterial made contact with the blanket for 500 times.

The deposition of dust on the blanket was evaluated qualitatively. In each examples, all samples were evaluated (+ better, - worse) against a reference (O) .

Waterresistance test

An image was printed on the test samples on a Heidelberg GT046 printing press, using Novavit K+E800 printing ink.

After drying for at least 24 hr, part of the printed samples was put in a cup, filled with tapwater for 24 hours.

Subsequently, the wet sample was scratched three times with a fingernail. The damage on the printed image was evaluated

qualitatively. In each examples, all samples were evaluated (+ better, - worse) against a reference (O) . EXAMPLE 1

Preparation of the support

A subbing layer with a composition of Table 5 was provided on both sides of the support. The support has been prepared as disclosed in EP-A 2103736 (example 1 and example l/LSl/BSl; page 19, Tables 1 and 2) .

Table 5

EXAMPLE 2

The coating solutions with a composition as given in Table 6 were applied on the support described in EXAMPLE 1 at a thickness of 33 m at a coating temperature of 45°C.

Table 6

Ingredients (g) COMP-01 INV-01 INV-02 INV-03 I V-04

DW 873.5 899.5 899.5 899.5 899.5

Si0 ₂ 1050.0 1050.0 1050.0 1050.0 1050.0

Joncryl FLX 5010 466.0 466.0 466.0 466.0 466.0

PVA-1 550.5 - - - - Exceval RS4104 - 524.5 - - -

Exceval HR3010 - - 524.5 - -

Exceval RS2117 - - - 524.5 -

Exceval RS1717 - - - - 524.5 surfactant 15.0 15.0 15.0 15.0 15.0 matting agent 45.0 45.0 45.0 45.0 45.0

The pH of the coating solutions was adjusted to 8.1 with an 25 wt . % aqueous NH ₃ solution.

The dry coating weight of the ingredients are given in Table 7.

Table 7

2

Dry weight (g/m ) COMP-01 INV-01 INV-02 INV-03 I V-04

Joncryl FLX 5010 2.31 2.31 2.31 2.31 2.31

PVA-1 0.23 - - - -

Exceval RS4104 - 0.23 - - -

Exceval HR3010 - - 0.23 - - Exceval RS2117 - - - 0.23 -

Exceval RS1717 - - - - 0.23

Si0 ₂ 2.31 2.31 2.31 2.31 2.31

Matting agent 0.10 0.10 0.10 0.10 0.10

Surf ctant 0.094 0.094 0.093 0.093 0.093

Total 4.96 4.96 4.96 4.96 4.96

All samples were subjected to both the dust test and the water resistance test. The results are shown in Table 8.

Table 8

Water

Hydrolysis H ₂ 0 soluble ethylene Dust

(mol.%) resistance binder

COMP-01 PVA-1 97.5 - 99.5 0 0 0

Exceval

INV-01 98.0-99.0 4 + +++

AQ-4104

Exceval

I V-02 99.0-99.4 3 + 0

HR-3010

Exceval

INV-03 97.5-99.0 2 0/+ +

RS-2117 Exceval

I V-04 92.0-94.0 1 0 / + 0

RS-1717

Exceval

INV-05 1 + 0

RS-1713

Exceval

INV-06 97.5-99.0 4 + ++

RS-4105

Exceval

INV-07 92.0-94.0 2 +

RS-2713

Exceval

I V-08 95.5-97.5 2 + +

RS-2817

It is clear from the results of Table 8 that all samples with a vinylalcohol - vinylacetate - ethylene copolymer have improved properties compared with the comparative example having a

vinylalcohol - vinylacetate copolymer. The best results are obtaine with those copolymers having the highest ethylene content (I V-01 and INV-06) .

EXAMPLE 3

In example 3, a variety of copolymers were tested.

The coating solutions with a composition as given in Table 9 were applied on the support described in EXAMPLE 1 at a thickness of 33 μτη at a coating temperature of 45 °C.

Table 9

Ingredients (g) COMP-02 COMP-03 INV-09 COMP-04 COMP-05

DW 873.5 899.5 899.5 1319.0 1319.0

Si0 ₂ 1050.0 1050.0 1050.0 1050.0 1050.0

Joncryl FLX 5010 466.0 466.0 466.0 466.0 466.0 PVA-1 550.5 - - - -

Poval 103 - 524.5 - - -

Exceval RS4104 - - 524.5 - -

S LEC KW-1 - - - 105.0 -

Polyviol LL603 - - - - 105.0 surfactant 15.0 15.0 15.0 15.0 15.0 matting agent 45.0 45.0 45.0 45.0 45.0

The pH of the coating solutions was adjusted to 8.1 with an 25 wt . % aqueous NH ₃ solution.

The dry coating weight of the ingredients are given in Table 10. Table 10

2

Dry weight (g/m ) COMP-02 COMP-03 INV-09 COMP-04 COMP-05

Joncryl FLX 5010 2.31 2.31 2.31 2.31 2.31

PVA-1 0.23 - - - - Poval 103 - 0.23 - - -

Exceval S4104 - - 0.23 - -

S LEC KW-1 - - - 0.23 -

Polyviol LL603 - - - - 0.23

Si0 ₂ 2.31 2.31 2.31 2.31 2.31

Matting agent 0.10 0.10 0.10 0.10 0.10

Surfactant 0.094 0.094 0.093 0.093 0.093

Total 4.96 4.96 4.96 4.96 4.96

All samples were subjected to both the dust test and the water resistance test. The results are shown in Table 11.

Table 11

H ₂ 0

Dust

resistance

COMP-02 PVA-1 0 0

COMP-03 Poval 103 ++ Exceval

INV-09 ++ ++

RS4104

COMP-04 S LEC KW-1 0 -

Polyviol

COMP-05 + 0

LL603

Polyviol

COMP-06 ++ -- LL620

COMP-07 P103 + --

CO P-08 S LEC KW-3 0

Exceval

INV-10 ++ o / - RS4105

CO P-09 Poval KL118 + 0

It is clear form the results of Table 11 that the best results with respect to dust formation and water resistance are obtained with those samples comprising a vinyl alcohol - vinylacetate - ethylene copolymer .

EXAMPLE 4

The coating solutions with a composition as given in Table 12 were applied on the support described in EXAMPLE 1 at a thickness of

33 m at a coating temperature of 45°C.

Table 12

Ingredients (g) INV-11 INV-12 INV-13 INV-14 INV-15

DW 1292.0 953.0 966.0 979.0 613.0

Si0 ₂ 819.0 819.0 819.0 819.0 819.0

Joncryl FLX 5010 464.0 464.0 464.0 464.0 464.0

Michem EM39235 26.0 26.0 13.0 - 26.0 Exceval RS4104 339.0 678.0 678.0 678.0 1018.0

Chemguard S550 15.0 15.0 15.0 15.0 15.0

Matting agent 45.0 45.0 45.0 45.0 45.0

The pH of the coating solutions was adjusted to 8.1 with an 25 wt . % aqueous NH ₃ solution.

The dry coating weight of the ingredients are given in Table 13.

Table 13

2

Dry weight (g/m ) I V-11 INV-12 I V-13 INV-14 I V-15

Si0 ₂ 1.80 1.80 1.80 1.80 1.80 Joncryl FLX 5010 2.30 2.30 2.30 2.30 2.30

Michem EM39235 0.1 0.1 0.05 - 0.1

Exceval RS4104 0.15 0.30 0.30 0.30 0.45

Chemguard S550 0.0083 0.0083 0.0083 0.0083 0.0083

Matting agent 0.10 0.10 0.10 0.10 0.10

The results of the water resistance test are given in Table 14.

Table 14

Water

resistance

I V-11 0

INV-12 0/+ I V-13 +

INV-14 +

INV-15 +

INV-16 0

I V-17 +

INV-18 + +

INV-19 + +

INV-20 + +

INV-21 0

I V-22 +

INV-23 + +

I V-24 + +

INV-25 + +

The best results are obtained with those samples having the highest concentration of vinylalcohol - vinylacetate - ethylene copolymer.

EXAMPLE 5

The coating solutions with a composition as given in Table 15 were applied on the support described in EXAMPLE 1 at a thickne 33 m at a coating temperature of 45 °C.

Table 15

Ingredients (g) INV-26 I V-27 I V-28 INV-29 INV-30

D 1292.0 1383.0 1775.0 1565.0 1656.0 sio ₂ 819.0 728.0 636.0 546.0 455.0

Joncryl FLX 5010 464.0 464.0 464.0 464.0 464.0

Michem EM39235 26.0 26.0 13.0 - 26.0 Exceval RS4104 339.0 339.0 339.0 339.0 339.0

Chemguard S550 15.0 15.0 15.0 15.0 15.0

Matting agent 45.0 45.0 45.0 45.0 45.0

Ingredients (g) INV-31 I V-32 INV-33 COMP-10 I V-34

D 0 953.0 1461.0 1631.0 1318.0 sio ₂ 819.0 819.0 819.0 819.0 819.0

Joncryl FLX 5010 464.0 464.0 464.0 464.0 464.0

Michem EM39235 26.0 26.0 13.0 - 26.0

Exceval RS4104 1631.0 678.0 170.0 - 339.0

Chemguard S550 15.0 15.0 15.0 15.0 15.0

Matting agent 45.0 45.0 45.0 45.0 45.0

The pH of the coating solutions was adjusted to 8.1 with an 25 wt . aqueous NH ₃ solution.

The dry coating weight of the ingredients are given in Table 16.

Table 16

Dry weight (g/m ² ) INV-26 INV-27 INV-28 INV-29 INV-30

Si0 ₂ 1.80 1.60 1.40 1.20 1.00 Joncryl FLX 5010 2.30 2.30 2.30 2.30 2.30

Michem EM39235 0.10 0.10 0.10 0.10 0.10

Exceval RS4104 0.15 0.15 0.15 0.15 0.15

Chemguard S550 0.0083 0.0083 0.0083 0.0083 0.0083

Matting agent 0.10 0.10 0.10 0.10 0.10

All samples were subjected to both the dust test and the water resistance test. The results are shown in Table 17.

Table 17

Water

dust

resistance

I V-26 0 0

INV-27 0 0 INV-28 0 0

INV-29 0 0

INV-30 0 0

INV-31 - + + +

I V-32 + + + + +

I V-33 0 0

COMP-10 - 0

I V-34 + 0

INV-35 + 0

INV-36 + + 0

I V-37 + + 0

It is clear from the results of Table 17 that all inventive samples comprising a vinylalcohol - vinylacetate - ethylene copolymer have better dust and water resistance properties compared to the sample having no such copolymer. The best water resistance is obtained with those samples having the highest concentration of the water soluble or dispersible copolymer (INV-31 and INV-32) . A higher amount of wax also improves the dust deposition (INV-36 and INV-37) .