FI57801C - FOERFARANDE FOER FRAMSTAELLNING AV KONSTFIBERPAPPER MED FOERBAETTRADE TRYCKNINGSEGENSKAPER FOER OFFSETTRYCK OCH ENLIGT FOERFARANDET TILLVERKAD PRODUKT - Google Patents

Description

R5F * 1 M (IDENTIFICATION)

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Patent-och refisterstyrelsan Ansökan uthgd oeh utl. * Kr1fUn puMicvrad 30.06.80 ___ (32) (33) (31) Requested «tuolka ·» -Begirt priority 2k. 03. 73

Japan-Japan (JP) 33696 (71) Kanzaki Paper Manufacturing Co., Ltd., 9 ~ Uonchome, Ginza, Chou-ku,

Tokyo, Japan i-Japan (JP) (72) Seigoro Fujita, Amagasaki, Hyogo, Tojiro Kitahori, Nishinomiya, Hyogo,

Japan-Japan (JP) (7 * 0 Antti Impola (5M Method for the production of man-made fiber paper with improved printability for transfer printing and the product produced according to the method) The present invention relates to an improved man-made fiber paper made of a fibrous material, at least a part of which consists of polyolefin fibers, and in particular to an man-made fiber paper having good printability for transfer printing, and to a method of making such an improved man-made fiber paper.

- An sheet material formed of a fibrous material consisting only of polyolefin fibers or a mixture of polyolefin fibers and natural cellulosic fibers has the advantage of having good - water resistance, chemical resistance and dimensional stability, but has the disadvantage of poor transferability, which is offset printing, made exclusively of cellulose fibers.

As is known, in the transfer printing method, it is impossible or very difficult to use the source solution and the printing ink separately. It is also known that the printing ink transfer error is often due to poor absorption of the source solution into the sheet to be printed.

In general, the pick resistance or fiber resistance of a sheet made of polyolefin fibers is not strong enough for the transfer weight because the internal bond between the polyolefin fibers in the sheet is not strong. One effective method for improving impact resistance is to treat the sheet in a known manner with an aqueous binder solution, for example glue, surface finish, 2,57801 coating, etc. However, the use of a binder solution in an amount sufficient to provide good release resistance prevents absorption of the source solution. the transition to the surface of the paper is incomplete. This phenomenon has been found to be most pronounced when the amount of polyolefin fibers in the sheet is high. Even in an sheet material containing polyolefin fibers, about 5% by weight of the weight of the cellulosic fibers is so-called snowflake-like on surfaces with polyolefin fibers.

The main object of the present invention is to provide an even better synthetic fiber paper which does not suffer from the above-mentioned drawbacks. It is a particular object of the invention to provide a man-made fiber paper made of a fibrous material, at least part of which consists of polyolefin fibers with improved "peel or liquid resistance" and "transfer pressure".

Another object of the present invention is to provide an economical and efficient method for treating printable man-made fiber paper made from a fibrous material at least a portion of which consists of polyolefin fibers to improve printability.

Other objects and advantages of the invention will become apparent from the following description.

According to the invention, a man-made fiber paper having improved printability for transfer printing is made by treating the surface of a sheet material made of a fibrous material at least a portion of which consists of polyolefin fibers with an aqueous mixture containing a water-soluble polymer and an aqueous polymer emulsion.

The sheet material can be made either exclusively from polyolefin fibers or a combination of these and natural cellulosic fibers. -

According to a preferred embodiment of the invention, the aqueous mixture further comprises at least one salt or oxide of a multivalent metal. The man-made fiber paper of the present invention is made of a fibrous material at least a portion of which consists of polyolefin fibers. That is, the synthetic fiber paper for the present invention is an sheet material which may be made exclusively of polyolefin fibers or a mixture thereof and natural cellulosic fibers and / or synthetic man-made fibers.

According to a preferred embodiment of the invention, the polyolefin fibers comprise at least 50% by weight of olefin fibers used for the production of a paper sheet. Polymers for polyolefin fibers may include homopolymers such as polyethylene and polypropylene, poly-1-butene, poly-4-methyl-1-pentene and polystyrene, binary or tertiary copolymers of olefins, for example poly (ethylene-propylene), bi - 3,57801 tertiary or tertiary copolymers, comprising an olefin and at least one other monomer copolymerizable with olefins, and graft copolymers and crosslinking polymers of the aforementioned polymers. These synthetic resins can be spun by any suitable rinsing spinning method, uniaxial spinning method and branching method, emulsion rinsing method, and centrifugal spinning method to obtain fibrous materials.

Mixtures of the above polymers and mixtures of these polymers with other polymers can also be used to effect spinning of fibrous materials.

It is very advantageous to use synthetic fibers of polyolefin with a hydrophilic component. The spinner for these man-made fibers comprises essentially olefin homopolymers, for example polypropylene, polyphenene and poly-4-methylpentene-1 or copolymer, made from a mixture of at least one olefin and a hydrophilic or water-soluble polymer component added to the spinner. and / or graft polymerizing the mixture. The hydrophilic or water-soluble polymer components to be added may include water-soluble polymers, for example polyvinyl alcohol, polyacrylamide, polyethylene oxide, polyethylene glycol and carboxymethylcellulose, and optionally hydrosylated or branched copolymers having a hydrophilic group or to which a hydrophilic group may be added. The hydrophilic polymer also includes copolymers of olefin and vinyl monomer in which the hydrophilic group or vinyl monomer is itself, to which the hydrophilic group can be introduced by proper post-treatment. Vinyl monomers having a hydrophilic group or which can take up the hydrophilic group by proper treatment may include vinyl acetate, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, acrylamide, allyl alcohol and butene tricarboxylic acid.

Monomers introduced into the polyolefin by graft polymerization include vinyl monomers having a hydroxyl and / or carboxyl group and vinyl monomers having a hydroxyl or carboxyl group by treatment such as hydrolysis. Examples which may be mentioned are vinyl acetate, acrylic acid, methacrylic acid, methacrylate, methyl methacrylate, allyl alcohol and butene tricarboxylic acid. The graft polymerization product may also include another monomer capable of graft polymerizing with the aforementioned vinyl monomers. Thus, for example, monomers such as acrylonitrile, vinyl chloride, methyl methacrylate and acrylamide can be used in amounts less than the amount of the above-mentioned vinyl monomer to obtain the copolymerization product.

The above polymers can be spun by various spinning methods to produce a fibrous material. Thus, for example, a compound obtained by adding a hydrophilic component to the above-mentioned olefin polymer or copolymer by mixing and / or graft polymerization is dissolved in a suitable solvent, for example hydrocarbons or chlorinated hydrocarbons. The solution thus prepared is then added to a non-solvent with a surfactant to form an emulsion. The fibrous material is thus prepared by the emulsion rinsing-spinning method, subjecting it, if necessary, to grinding and / or processing.

As mentioned above, the man-made fiber paper used for the purpose of the invention may be a sheet material made not only of the above-mentioned polyolefin fibers but also of polyolefin fibers and natural cellulose fibers and / or other man-made fibers. Of course, the sheet material may contain inorganic fillers, binders, deforming agents, dyes, adhesives, etc. as additives. The amount of natural cellulosic fibers to be mixed with the polyolefin fibers is not particularly limited. However, natural cellulosic fibers should not be blended in excess of an amount that degrades the beneficial properties of the polyolefin fibers. The amount of cellulosic fibers is preferably between 95 and 10% by weight. Thus, the amount of polyolefin fibers should be in the range of 5-90% by weight. The above-mentioned man-made fiber paper of the present invention is considered to be a "polyolefin fiber paper".

According to the present invention, the polyolefin fiber paper is treated with an aqueous mixture comprising mainly a water-soluble polymer and an aqueous polymer emulsion. The aqueous mixture is added to the polyolefin fibrous paper by any known method, for example - by dipping, surface finishing spraying, coating, etc. The addition of the aqueous mixture to the fiber mixture in the grinding step before forming the sheet does not produce the desired effect.

The water-soluble polymers of this invention include natural or synthetic water-soluble high molecular weight compounds, for example, protein, starch, cellulose ethers, alginates, polyvinyl alcohol, gum arabic acid, polyacrylamide, polyacrylamide, styrene-maleic acid anhydridic anhydride products. in terms of.

5,57801

Useful high molecular weight emulsions may be those emulsions prepared by emulsion or suspension polymerization of at least one monomer having an active double bond, for example vinyl acetate, acrylic ester, methacrylic ester, acrylonitrile, ethylene, ethylene, propylene, butylene, propylene, , vinylidene chloride, chloroprene, etc. The polymers in the emulsion may include partially carboxylated polymers together with monomers having a carboxyl group such as acrylic acid, methacrylic acid, etc. It is desirable that the above emulsions be selected from those which may form for drying paper, for example at a temperature of 80 to 150 ° C. These emulsions can also be used in the form of a mixture.

A suitable blend ratio of water-soluble polymer to aqueous polymer emulsion is 90:10 to 10:90% solids, preferably 75:25 to 20:80.

The exact reason why the water absorption of polyolefin fiber paper can be improved according to the invention is not yet known, but it is to be expected that the desired effect can be obtained by treating the surfaces of polyolefin fiber paper exclusively with either a water-soluble polymer or an aqueous polymer emulsion. It can be seen that a continuous or uniform film formed with a water-soluble polymer together with an aqueous polymer is porous enough to absorb enough of the source solution, due to the difference in film formation ability between the water-soluble polymer and the aqueous polymer emulsion.

The above-mentioned mixture may further contain at least one multivalent metal salt and / or a multivalent metal oxide, whereby the absorbency of the source solution may be better.

Useful metals for multivalent salts and oxides include, for example, magnesium, calcium, zinc, cadmium, barium, aluminum, zirconium, tin, lead, chromium, vanadium, manganese, iron, cobalt, nickel, and the like.

These multivalent metal salts and metal oxides can be used as mixtures thereof. Suitable examples are ZnO, Zn (OH) 2, ZnCl2, ZnSO4, Zr (NO3) 2, AlgOj, AlCOH) ^, AlOlj, NaAl (SO4) 2, ΑΐζσΗ ^ ΟΟΟ) ^, SnO2, Na2SnO5, SnCl2, Na2SnCl6, SnSO MgO, Mg (OH) 2, MgCl2, Mg (NO2) 2, Mg (CPO4) 2, Zr (CH5000) 2, Ca (OH) 2, CaCl2, CaSO4, Ca (CH5COO) 2 and CaCO3.

Of the multivalent metal salts and oxides useful in this invention, water-soluble salts and oxides are preferred, as efficacy can be achieved by using them in relatively small amounts. Multivalent metal salts and oxides should be added to at least 0.1% by weight of the solids of the water-soluble polymer and the aqueous polymer emulsion containing water. The most suitable amount of multivalent metal salts or oxides is 0.1 to 30% of the solids content of the water-soluble polymer and the aqueous polymer emulsion.

The effective amount of the aqueous mixture used for the polyolefin fiber paper is at least 0.3 g / m dry weight, with or without any of a multivalent metal salt or oxide. The upper limit is determined only by economy, as a result of which the most suitable - p treatment rate is 0.3 - 10 g / m dry weight.

The polyolefin fibrous paper according to the invention has an improved peel resistance and efficiently absorbs the source solution, making it best suited for transfer weight.

In addition, the surface of the polyolefin fibrous paper can be coated with a pigmented coating composition to provide an expanded pigmented paper. In pigment-coated paper, it is generally known that, in order to avoid the transfer of printing ink, due to poor absorption on the pigment-coated surface, the weight of such a dense pigment coating, if necessary, is at least 20 g / m by dry weight. However, if the polyolefin paper treated according to the invention is used as a backing sheet for a pigment-coated paper, the amount p of the pigment coating mixture to be used can be considerably less than 20 g / m by dry weight without deteriorating the water absorption.

This is a considerable advantage, as it is possible to produce a light pigment-coated polyolefin fiber paper which is fluffy and sufficiently transparent.

The following examples illustrate the invention without limiting it. Unless otherwise stated, parts are calculated on a dry weight basis.

Example 1 90 parts of isotactic polypropylene powder (= 1.8 dl / g) and 10 parts of polyvinyl alcohol powder (degree of polymerization 1400 and saponification number 99%) were mixed together in a mixer and the mixture was extruded at 230 ° C to obtain pills. 170 g of the obtained pills were introduced into the autoclave together with ί.25 liters of methylene chloride, 2 liters of water and 6 g of sodium dodecylbenzenesulfonate. The mixture was heated in an autoclave with stirring to form an emulsion. After the temperature of the emulsion had risen to 145 ° C, it was discharged through a nozzle with a diameter of 1.6 mm at the bottom of the autoclave to obtain a polyolefin dome mass.

The resulting mass was made into a 1% aqueous suspension which was ground in a Sprout Waldon plate refiner. To the pulp suspension containing 30 parts of NBKP (bleached softwood sulphate cellulose, CSP cm 2), 40 parts of LEKP (bleached hardwood cellulose, CSF 400 cm 2) and 30 parts of the above polyolefin pulp were then added 0.7 parts of resin glue and 2.5 parts of aluminum sulphate. A sheet of paper having a dry weight of 50 g / m 2 was prepared from the resulting pulp suspension in a Fourdrinier laboratory paper machine.

The surface of the obtained sheet was treated with various aqueous mixtures according to Table 1 in a surface sizing machine, and the paper sheet thus obtained was dried at a temperature of about 110 ° C and calendered. The treated paper sheet was tested for peel resistance and transferability.

The fiber peeling test was performed using a Pin STD T-499 »SN-64 type IGT printability tester (ink adhesive value 13 * 2, spring A, compression 35 kg). The transfer printability test was performed using two color transfer printing machines (Roland Rekord Type: RZKIIIB, manufactured in West Germany) to determine the receptivity of the ink.

The results obtained are shown in Table 1. The peel resistance of all treated sheet fibers was less than 80 cm / sec or less as measured by an IGT printability tester, whereby the separation of the fibers in the transfer printability test was performed on a Roland transfer printing machine.

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Example 2 80 parts of isotactic polypropylene powder C Tj = 23 dl / g), 20 parts of polyethylene powder (HI-ZEX 2100LP manufactured by Mitsui Petrochemical Inds., Ltd.), 12 parts of polyvinyl alcohol powder (Gosenol NM-14 manufactured by Nihon Synthetic Chemical Ind. Co. Ltd.) and 10 parts of calcium sulfate were mixed in a mixer, after which the mixture was extruded at 230 ° C to form pills. 170 g of the obtained pills were introduced into the autoclave together with 1.25 liters of methylene chloride, 2 liters of water and 6 g of sodium dodecylbenzene sulfonate. The mixture was heated in an autoclave with stirring to form an emulsion. After the temperature rose to 145 ° C, the emulsion was discharged from a nozzle with a diameter of 1.6 mm at the bottom of the autoclave to obtain a polyolefin mass.

The mass thus obtained was made into a 1% aqueous suspension, which was already obtained in a Sprout Waldron plate refiner. On the other hand, a cellulose pulp suspension was prepared containing 20 parts of NEKP (CSF 4-20 C cm -1) and 80 parts of LBKP (CSP 400 cm -1). The above-mentioned polyolefin pulp and natural cellulose pulp were mixed in different proportions as shown in Table 2, and paper pulps were prepared from the above-mentioned pulp blends.

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sheets weighing 50 g / m according to JISP-8290 (Japan Industrial Standard P-8290). The sheets thus obtained were treated in a surface treatment machine with various aqueous mixtures shown in Table 2. The sheets obtained were dried in a cylinder drier at 105 ° C and then calendered.

The peel resistance and transfer printability of the fibers of each sheet were tested. The test results are shown in Table 2.

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Commercial polyethylene pulp (SWP., Manufactured by Mitsui Zellebrach Co., Ltd.) was prepared as a 1% aqueous dispersion, which was then ground with a Sprout Valdron plate refiner. The cellulosic pulp of Example 2 and the above-mentioned polyethylene pulp were mixed together in various proportions shown in Table 3, and paper sheets were prepared from the pulp in the same manner as described in Example 2. The resulting sheets were treated with a various aqueous mixtures shown in Table 3. The peel resistance and transfer printability of the fibers of each treated sheet were tested as described in Example 1. The results are shown in Table 3 * 57801

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Example 4

Commercial polypropylene pulp (Dan. Pulp manufactured by ITbe-Nito Kasei Ind., Ltd.) was prepared as a 1% aqueous dispersion, which was then ground with a Sprout Valdron plate refiner. The cellulose pulp of Example 2 and the above-mentioned polypropylene pulp were mixed together in various proportions shown in Table 4, and sheets of paper were prepared as described in Example 2. The resulting sheets were treated with the various aqueous mixtures shown in Table 4 by a suitable coating method. The peel resistance and transfer printability of the fibers of each sheet were tested as described in Example 1. The results are shown in Table 4.

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Example 5

The pigment coating composition was prepared according to the following instructions:

Dry parts by weight

Quality No. 1 Kaolin 80

Calcium carbonate 20 T.B.P.Psta 0.4

Casein 7

Styrene-hutadiene latex (50% dry matter content) 15

The above pigment coating mixture was applied in an amount of ~

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10 g / m dry weight of the treated surface of the polyolefin fiber paper of Experiments No. 1-25 (Table 1) and the coated paper were supercalendered.

The fibers of the obtained pigment-coated paper sheet were tested for peel resistance and transfer printability as described in Example 1. The results are shown in Table 5 ·

In Table 5, test number 1 'indicates a coated paper obtained by applying the above-mentioned pigment coating mixture to the surface of the sheet obtained in Test No. 1. The others are presented in a similar way.

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Table 5 Exit resistance

Experience no IGT Print ink (cm / sec) susceptibility

Check 1 '<* 30 2' 16J x 3 '131 x 4' 154 x 5 '142 x 6' <30 7 '__ <30 __-_ 8' __ <30 __T __ <30

Example 10 '141 (o) 11' 145 (o) 12 '146 © 13' 150 ® 14 '104 © 15' 98 © 16 '108 (o) W 17' 108 © 18 '133 © 19' 128 © 20 ' 129 ©

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22 '126 © 23' 119 © 24 '122 © __25 | __129__ © _

Claims (11)

A method of fabricating synthetic paper with improved printing offset printing, wherein the sheet material made of fiber blank is coated, characterized in that (a) the fiber blank is made from the blanks selected from the group consisting of polyolefin fibers and a blend of polyolefin fibers and natural cellulose fibers, and (b) the coating is spread on the fiber substance in an amount of the dietary substance 0.3 g / m calculated in the dry weight where the coating is in aqueous solution, which consists essentially of a water-soluble polymer. an aqueous polymer emulsion which is coated by polymerization of at least one monomer with an active double bond and the ratio between the water-soluble polymer and the aqueous polymer emulsion is in the range of 90: 10, · .10: 90% by weight calculated by weight of solid. Process according to Claim 1, characterized in that said fibrous substance consists of a compound containing 90 ... 5% by weight polyolefin fibers and 10 ... 95% by weight natural cellulose fibers. 3. A process according to claim 1, characterized in that the water-soluble polymer is a substance selected from the group consisting of protein, starch, cellulose ether, alginate, polyvinyl alcohol, polyacrylamide, arabic, styrene-maleic anhydride anhydride products, of -ole-finmaleic acid anhydride copolymer and mixtures of the above. 4. A process according to claim 1, characterized in that said aqueous polymer emulsion is an aqueous emulsion of a polymer made by polymerization of at least one monomer selected from the group consisting of vinyl acetate, acrylic ester, methacrylic ester. , acrylonitrile, ethylene, propylene, butadiene, styrene, vinyl chloride, vinylidene chloride and chloroprene. Process according to claim 4, characterized in that said polymer is partially a carboxylated polymer. 6. A process according to claim 1, wherein the aqueous mixture comprises substantially 75 ·· * 20% by weight of water-soluble polymer and 25 to 80% by weight of aqueous polymeric emulsion.