DE1917053C3 - Paper or paper product - Google Patents

Description

Hydroxyethyl acrylate, N-isopropyl acrylamide, N-ethyl or paper product, which the above-described after-

methacrylamide, diammonium itaconate, maleic acid no longer has 40 parts, d. H. that with a material

monobutyl ester or N-methacrylylpropionic acid is coated, which is good oil, fat, solvent

amide, can be replaced. medium and water vapor barrier resistance of the

Surprisingly, it has been found that the layered paper ensures.

Paper or paper product according to the invention. Surprisingly, it has been found that the improved resistance to the paper or paper product according to the invention penetration of liquids, water vapor and gases has desired properties, d. H. through aufweis? .. a good oil, grease, solvent and steam paper is known to be widely recognized for barrier resistance.

Used for packaging purposes. However, it has one of the characteristics of the improved Spexre properties

The paper or paper product according to the invention has a relatively low resistance to one another

above the penetration of water vapor, gas, oils, through good oil, grease and solvent resistance

Solvents and fats. To improve this.

For this resistance, paper was used with the mixed polymer latex used as a coating

various substances coated. Mostly used, generally contains 5 to 70%

the paper coated with wax. 55 ethylene, 30 to 95% vinyl chloride and 0.1 to 10%

Wax-coated paper has good cons- acrylamide.

Resistance to water vapor as long as the acrylamide can be wholly or partially through a

it is smooth or unfolded, its resistance further copolymerizable, polar monomer

however, it is slight when the paper is creased. be replaced. Such monomers are, for example

Obviously the brittleness of the wax is so great that 60 sodium acrylate, sodium methacrylate, _ hydroxyethyl-

that the wax through the buckling to crack formation acrylate, N-isopropyl acrylamide, N-ethyl methacrylate

and is caused to break, whereby many places amide, diammonium itaconate, maleic acid monobutyl

created by the water vapor with ester or N-methacrylylpropionamide. the

can penetrate with little or no resistance. Acrylamide content should generally be at least

In addition, the wax coated paper does not constitute 55–50 percent by weight of the third polar monomer

hard and wear-resistant surface. make up in the copolymer and preferably

Attempts have also been made to make paper with asphalt at least 80% of the polar monomer.

to be coated in order to increase the resistance.

3 4

position at least terpolymers. You can use acrylamide either alone or mixed with others

also quaternary or higher polymers, monomers in smaller portions in a suitable one

which - in addition to ethylene, vinyl chloride and acrylamide - diluents, such as water, in the under pressure

one or more of the above-exemplified held polymerization mixtures of ethylene and

Additional polar monomers introduced in small amounts 5 vinyl chloride.

contain. In general, such additional The following examples explain the preparation of monomers in the copolymer not present in amounts of the polymers used in this invention which exceed 2 percent by weight. latices. In the examples the polymerization is preferably the copolymer contains 5 to a 3820 ml pressure vessel at 30 ⁰ C and at a 70% ethylene, 30 to 95% vinyl chloride and 1 to 5% ίο stirring speed of 600 rpm performed.

A particular example is a terpolymer, the example

19 to 23% ethylene, 74 to 78% vinyl chloride and 2 to This example illustrates the preparation of one containing 4% acrylamide. 21/76/3-ethylene-vinyl chloride-acrylamide-terpolymeri-albeit the copolymers used in the implementation of this invention latex and its stabilization with an emulsion generally greasing agent. are not modified, modified copolymers can also be used. The initial charge of the polymerisation vessel is particularly suitable for hydrolytic 110 g K SO modification using small amounts of> ₁₅ ' ₀ ° N _a HCO ₃ , a strongly alkaline material such as an alkali ₀ ' _{8 g} p _e (NO _s ) ₃ ' · 9 H, O, metallhydroxyds or a quaternary ammonium _{5 Tetranatriumäthy'lendiamintetraacetat, hydroxide, such as tetramethylammonium hydroxide, or _{2 sodium lauryl sulfate, a strong acid, such as hydrochloric, sulfuric, phosphoric _{H 'o au} fg _e fills 1700 ml, or nitric acid, are suitable. The _{base or acid used, preferably 5450 g of} vinyl chloride, has a dissociation conjugation of ethylene which is greater than 10% at 25 ° C. ^B.

The hydrolytic treatment with an acid or base does not always have to be carried out to the same extent with stirring and with the formation of a reaction. The polymer latex of ethylene, 30 tion pressure heated from 59.8 kg / cm in ^a 30 ⁰ C. The vinyl chloride and acrylamide is generally initiated with polymerization by treating an aqueous solution of a base or acid in a mixture of a 1 m sodium formaldehyde sulfoxylate / amount containing 100% of the amide content in the 1.5 m ammonium hydroxide solution a GeMischpolymerisat is equivalent. The ethylene-vinyl speed of 5.2 ml / hour and at the same time chloride-acrylamide copolymers can thus 35 at a rate of 18 ml / hour, a are / 25 manufactured _cent, by first zusetzte ethylene and sodium lauryl sulfate solution and - as far as vinyl chloride in an aqueous medium in the presence of this was necessary - kept the pressure constant by adding a suitable anionic or nonionic pure vinyl chloride. After expiry of emulsifying agent and an initiator for 3 hours, a 50 ° / _o solution of sodium formation of free radicals at the selected acrylamide in 40 water at a speed of reaction temperature and the chosen reaction was 40 ml / hour was added. The polymerization was pressure capable of mixing. The acrylamide is then interrupted after 5.5 hours. Preferably in aqueous solution - - either vinyl chloride, 95 ml of 50 ° / ₀ sodium acrylamide, 27 ml <alone or mixed with suitable amounts of other 1 m-sodium-L5 m- N Η, ϋΗ-nolarer monomers gradually during Then, 1330 g of of poly-45 solution and 92 ml of 25 ° / _o strength Natnumlaurylsulfat-solution polymerization the polymerizing ethylene-vinyl added. The polymer latex obtained was added from the chloride mixture. Because acrylamide is very drained bottom of the autoclave. If it became a reactive one, it cannot be added in full immediately when the total amount of polymer is about 3500 g of ethylene vinyl chloride. Preferential acrylamide polymer latex is obtained, the added acrylamide is added until 50 substance content of 47 and 1.5% sodium lauryl sulfate, about 40 to 50% of the ethylene and the vinyl chloride based on the weight of the polymer, have polymerized because when using the latex the product obtained had a pH of /, /. the surface of the polymer particles is where the ethylene-vinyl chloride-acrylamide terpolymer is adhered. In this way a latex is produced, in had an approximate composition of ZlJ ιψ. which the polar monomer is concentrated in the outer layers 55 after adding 1.5% sodium dodecylbenzenesulfo. Of course, the latex can be used directly as a barrier coating

The ethylene vinyl chloride described above can be used.

Acrylamide copolymers can be prepared according to B e i s ρ i e 1 2 known processes. You become preferential

wisely prepared by combining ethylene and vinyl 60 This example explains the preparation of the base

chloride in the presence of an alkaline buffered modified ethylene vinyl chloride acrylamide ter-

Redox catalyst system, water and 1 to 8 polymers. . .

Weight percent based on the monomer charge. The reaction vessel of Example 1 and

or 4 to 7%, based on the polymer, anio- the constituents specified in Example 1 "; .. m, <. c" Her nir-htirmkr-hps fixing agents were used at 65 with the exception that IU g Κ, ί> ₂ υ _{8 a}

"! -,.", "Ο" the n ^ hti "nisches emulsion agent used at 65 with the A, g, ₂

dn ^ TemperaiüV and a pressure polymerized, 0.5 g of sodium lauryl sulfate as _f ^Anfan £ ^ * J _o ^u _x ⁿ _v ^g which or which is sufficient to the polymerization of were used. The sodium formaldehyde sulfoxy ethylene and vinyl chloride bring about. Then lat-NH-OH solution was added at one rate

of 4 ml / hour and the sodium lauryl sulfate solution was added at a rate of 8 ml / hour.

The polymerization was interrupted after 5.75 hours. At this point in time 1340 g of vinyl chloride, 100 ml of acrylamide _{solution, 23 ml of sodium formaldehyde sulfoxyate / NH 4} OH solution and 43 ml of 25% sodium lauryl sulfate were added. The terpolymer latex obtained was stabilized by adding a further 17 ml of 25% sodium lauryl sulfate. The stabilized latex was then drained from the bottom of the reaction vessel. 3460 g of latex with a solids content of 49 and 1% sodium lauryl sulfate were obtained. The terpolymer had essentially the same composition as that of Example 1. The particle size of this polymer latex was, however, somewhat larger than that of the latex of Example 1.

This stabilized ethylene Vinyxhlorid-acrylamide TerpolymerisatJatex was 4 to 16 hours at 50 ⁰ C after the addition of 0.4 to 2.0 g of sodium hydroxide (added in the form of a 10 ^o / ₀ sodium hydroxide solution) per kg of latex, is heated.

Example 3

A polymer latex from four monomers was prepared as follows:

A pressure reaction vessel was initially charged with

9.0 g
12.0 g

K ₁ S ₂ O ₈ ,
NaHCO ₃

0.8 g Fe (NO ₃ ) 9 H ₁ O,
1.5 g tetrasodium ethylenediamine tetraacetate,
0.5 g sodium lauryl sulfate,
H ₂ O, made up to 1700 ml,
575 g ethylene,
47Og vinyl chloride.

Amount of sodium methacrylate was used. An ethylene-vinyl chloride-acrylamide-sodium methacrylate polymer was obtained with essentially the same composition.

Copolymers were prepared analogously to Example 1 using the following. table specified components.

Table I.

at
game vinyl
chloride
(%) Ethylene
(%) acrylic
amide Solid
gchalt des
Polymer
latex
(%) Sodium-
lauryl
sulfate
(%) 4th
5
6th 70.5
74.0
72.2 27
25th
27 2.36
1.48
0.65 45.7
48.1
47.7 1.79
1.40
2.06

The copolymers prepared in Examples 4 to 6 were treated with sodium hydroxide Formation of hydrolyzed polymer latices modified:

example example
of table I. Solid content of the
Polymer latex
% 7th
8th 4th
5 44.2
46.9

The reaction vessel was sealed and heated until a pressure of 110 kg / cm ^{2 was} obtained. The polymerization was initiated by pumping a 1 M sodium formaldehyde sulfoxylate / 1.5 M NH ₄ OH solution into the reaction vessel at a rate of 4 ml / hour.

At the same time, 10 ml / hour of 25% sodium lauryl sulfate were added admitted. «5

During the polymerization, vinyl chloride was metered in to such an extent that the pressure remained constant. After 3 hours of polymerization, an aqueous solution of 40% acrylamide and 10% sodium acrylate was introduced into the reaction vessel at a rate of 24 ml / hour. The polymerization was interrupted after 6 hours. At this point in time 591 g of vinyl chloride, 52 ml of 25% sodium lauryl sulfate, 27 ml of sodium formaldehyde sulfoxylate / NH ₄ OH solution and 72 ml of acrylamide-acrylate solution were added. Unreacted ethylene and vinyl chloride were vented from the reaction vessel to reduce the pressure to about 18.6 kg / cm ^2. The latex was then vented from the bottom of the reaction vessel. 3060 g of latex with a solids content of 43 and 1.1% sodium lauryl sulfate were obtained. The ethylene vinyl chloride acrylamide sodium acrylate polymer had a composition of 21/76 / 2.3 / 0.7.

The polymer was suitable for direct use as a coating for paper or cardboard. The The procedure was repeated with the modification that instead of the sodium acrylic a corresponding one Examples 9-14

The procedure is analogous to Example 3, with the modification that instead of sodium acrylate, an equivalent Amount of the components listed below is used. In this way, polymer latices are obtained which have essentially the same composition as the product of Example 3.

9. Component
Polymer

10. Component
Polymer

11. Component
Polymer

12th component
Polymer

13. Component
Polymer

14. Component
Polymer

■ hydroxyethyl acrylate,

■ Ethylene / vinyl chloride / acrylamide / hydroxyethyl acrylate.
N-isopropyl acrylamide,
Ethylene / vinyl chloride / acrylamide / N-isopropyl acrylamide.
N-ethyl methacrylamide,
Ethylene / vinyl chloride / acrylamide / N-ethyl methacrylamide.

A diammonium salt of Ita-

consic acid,

Ethylene / vinyl chloride / acrylamide /

Diammonium itaconate.

Monobutylic acid maleate,

Ethylene / vinyl chloride / acrylamide /

Monobutylic acid maleate.

N-methacrylylpropionamide,

Ethylene / vinyl chloride / acrylamide /

N-methacrylyl propionamide.

According to the invention, paper is coated with an ethylene-vinyl chloride-acrylamide copolymer latex to form a product with improved barrier properties, namely about 0.027 to 40.8 kg of polymer latex per 279 m ^{2 of} paper with one-sided coating applied to the paper. Generally, however, be 0.5 to 9.0 kg per 279 m ^a paper, which are 1.8 to 32.5 g per m ⁴ paper, is applied. Preferably 0.5 to 1.8 kg per 279 m ^{2 of} paper, that is 1.8 to 6.5 g per m ²

brings. Paper to which the polymer latices can be applied includes all types of paper, such as glued writing paper, fibrous cardboard paper, cardboard, etc. The coated papers can be used as Wallpaper, paper can be used to line drawers and cupboards. Also suitable the papers coated according to the invention for book covers. The procedures for applying the Misrhpolymerisatlatex on the paper are the expert known. This process includes spraying, roller coating, slot nozzle application, the paint coating and the like.

The advantages and unexpected properties of the papers of the present invention are demonstrated by the following Examples.

The ethylene-vinyl chloride-acrylamide copolymer latices are applied as barrier coatings to paper using the following process.

The ethylene vinyl chloride acrylamide latex is on the matted side of the fibrous paper is applied with the help of a wire-wound rod. There were No. 6, 18 and 28 coating rods used to apply the latex. The rod number 6 has a smaller wire diameter and more turns for a given rod length, during the Rod No. 28 has a larger wire diameter and fewer turns per cm.

The fibrous paper is placed on a flat glass surface. The wire-wound rod is then fitted into the downward-moving rod attached to the top of the plate. The latex is then poured across the paper just in front of the downward moving bar and the moving down bar is pushed over the paper at a steady rate, leaving a uniform latex film on the surface of the paper. The coated samples are then ^{heated to 120 °} C. for 2 minutes and then calendered. The coated papers are then tested for resistance to oil. The test procedure is described below. The results are summarized in Table II. The samples are conditioned according to TAPPI T 402 m-49 before the test. The paper material used in the test described below is a 22.7 kg bleached Kraft paper.

oil resistance or oil resistance

»O A 15.2 χ 15.2 cm one side coated die cut Sample is folded diagonally from corner to corner, each fold being made with a pressure of 2.3 kg will. The sample is also folded about an inch from each corner and then folded into one 10.1 χ 10.1 cm box so that all kinks, except those of the side walls, converge as a star in the center of the box bottom.

Then 50 ml of SAE oil No. 10 was poured into the box and the time taken to penetrate was determined of the kinked surfaces is required.

I. Coating *) Solids
salary Coating
Weight test
sample time Kind of Braches 709 650 / eC 0.454 kg / Oil barrier properties of ethylene-vinyl chloride mixed polymers 7, 92.9 m (Min.) Table 1 Polyvinylidene chloride .. 60 4.35 13th 11 penetrations along the folds, 20 penetrations in unfolded Surfaces Example 4 latex. 47.5 3.44 - 180 1 penetration after 70 minutes a corner. The rest of the sample was up unchanged after 3 hours Example 5 latex. 48.1 3.64 - 180 1 penetration after 74 minutes, on one Corner. The rest of the sample was un changed after 3 hours Example 6 latex. 47.7 3.52 - 180 1 penetration after 72 minutes on one Gusset. The rest of the sample was up unchanged after 3 hours Polyvinylidene chloride .. 60 5.8 1
2 15th
17th 9 penetrations in the fold
25 penetrations into the unfolded Surfaces 13 penetrations into the fold 20 penetrations into the unfolded Surfaces Example 7 latex. 44.2 3.5 1
2 11th
12th 2 penetrations in the fold
6 penetrations in the ground 1 penetration in the fold 6 penetrations in the ground Example 8 latex. 46.9 4.2 1 38 No break in the fold,
3 penetrations in the ground 2 39 No break in the fold, 3 penetrations in the ground • \ A 11 *. Tl. Ii nil iri1il..nn.n times Shih number 6.

9 10

If the latex of Example 4 is replaced by latices. The coated papers can easily be heated

of Examples 9-14, essentially that will be welded. They are also suitable for manufacturing

get same result. Cardboard paper, such as cardboard, from paper drinking cups and the like,

has the excellent properties as they The films have better oil drainage properties s

in Table II were obtained when using the 5 and are not moistened by oil, as is the 1

Latices of Examples 4 to 8 are coated. the use of polyvinylidene chloride coating

The coated papers can be the case in particular.
Food wrapping can be used.

as

Claims (1)

to improve the paper. But after folding it has Claim: _{also e} j _{n s0} ) _c hes paper only one proportionately Paper or paper product that has at least a low resistance to water vapor, a surface by applying an aqueous addition, asphalt e.n black is also still Coated copolymer latex and the toxic material. Its application for the purpose of is characterized in that the paper coating is thereby a priori Coating from a stabilized and / or restricted. Asphalt coatings have about it optionally modified with acid or base also have the disadvantage that they Copolymers with gene change the flow properties. j ίο paper has also been made with a polyethylene film a) 5 to H) / _o ethylene, coated The polyäthylenül!> educated paper shows b) 30 to 95 Λ; Vinyl chloride and _{but little} resistance to it c) 0.1 to _10/0 acrylamide steam as a wax-coated paper, if there is, in which the whole or acrylamide, the coating under conditions unfolded part by another copolymerizable, i is ₅ tested. Polyethylene-coated paper is polar Mouoiaeres, like sodium acrylate, more sodium-resistant than wax-coated paper, if methacrylate, hydroxyethyl acrylate, N-isopropyl-it is folded. In order to improve the resistance to acrylamide, N-ethyl methacrylamide, diammonics, oils, solvents and fats, umitakonate, maleic acid monobutyl ester or paper has also been replaced with a polyvinylidene-N-methacrylylpropionic acid amide, its ao chloride coating. The polyvinylidene can. brittleness peculiar to chloride leads to cracking formation or breakage of such coatings, when they are folded. Try this disadvantage The invention relates to a paper or paper to be eliminated by adding plasticizers to the polyvinylidene chloride product on at least one surface, but led to a reduced effectiveness of the water and steam layers, which increases the effectiveness of the water and steam layers is. The paper or barrier properties according to the invention. The relatively low paper product is characterized by the fact that the impact resistance of the polyvinylidene chloride further results in a stabilized coating and / or the formation of cracks and breakage of the film in the case of acid or base modified copoly- 30 rapid scratches and wrinkles,
merisat with Plasticized polyvinyl “x _{s hi} _ _7n o / Ä _thv i. _n Chloride polymers for coating paper b 30 hU 95 ° / VinSorid and used. With paper coated in this way, c Ο, ίΐ s θ! Ac ^y ry.am d * ^'a * _A ^{Verlui of} resistance _£ egenüber ν, w, i UiS iu / _D / -ivijiannu ^ water, oils, fats and solvents is as a result in which the acrylamide all or part of the extraction and the exudation of the softener by another copolymerizable, polar maker. Monomers such as sodium acrylate, sodium methacrylate, There is therefore a need for a paper