DE3125006C2 - Process for the production of an oil-proof paper - Google Patents

Description

The invention relates to a method for producing an oil-resistant paper, in which paper with a liquid that is coated or impregnated Contains at least one fluorine-containing oil-resistant agent.

Water-soluble, fluorine-containing, oil-resistant agents have been used to make oil-resistant paper, but used alone they are too expensive and, more importantly, when used with ordinary cardboard or wood-free paper that has wood glue or aluminum sulfate incorporated into it, the oil-tightness takes off due to the harmful influence of the incorporated chemicals. With the conventional process in particular, it is impossible to make paper sufficiently oil-resistant that the oil resistance extends to the middle of the paper's interior; and when such methods are applied to paper cups and the like, oil can penetrate through the exposed cut edges in the bonded areas or through the ϊίύκ in the paper material, making it impossible to provide a sufficiently oil-resistant product.

Fs is also known that even when water

soluble fluorine-containing, oil-resistant Agents are used for ordinary paper containing resin or petroleum resin sizing agents, insufficient resistance to oil expected

s can be. It is therefore in those cases where the Surface treatment of paper with the aqueous solution of a water-soluble fluorine-containing versus oil resistant agent, sufficient wetting cannot be achieved, alternative attempts have been made

to add isopropanol or the like. In this method, however, a larger amount is necessary Isopropanol, about 20 to 30 "of the coating composition, should be used. In addition, the composition has an unpleasant odor and

Flash point which makes the process dangerous.

In order to achieve improved oil stability and homogeneity Attempts have been made to combine fluorine-containing oil-resistant agents with film-binding materials such as polyvinyl alcohol, oxidized starch, carboxy- methyl cellulose and polyacrylic resin emulsions or with chelating agents such as ethylenediamine tetraacetic acid (EDTA) and Natilum Tri-Polyphosphate together to use. However, because of the problem of wetting, such methods are limited to unsized paper and cannot be used on ordinary sized paper.

The invention is therefore based on the object To provide a method for making a new and usable oil-proof paper. With the procedure is intended all paper, including resin-sized paper, can be given better resistance to oil. Water-soluble fluorine-containing oil-resistant agents are said to be used in ordinary sized Paper to be practical.

The solution to the problem is in the above Main claim, advantageous embodiments are In specified in the subclaims.

The oil-proof paper is made by coating or impregnating paper with a liquid, a oil-resistant composition. This liquid or composition contains at least an oil-resistant agent containing fluorine and, according to the invention, additionally at least one Compound selected from the group consisting of Non-ionic surfactants with a cloud point of 35 up to 99 ° C, and ethers of the following general formula

HO- (X-O -) "R in the mean

X -CH ₂ CH ₁ -, -CH ₁ CH ₁ CH; - or

-CH (CHj) CH ₃ -,

η is an integer from 1 to 3 and R is an alkyl radical with 1 to 5 carbon atoms.

The oil-containing composition can also contain at least one additive, such as paraffin wax.

The non-ionogenic surfactants according to the invention are used, are preferably water-soluble, the are able to. Penetrate into paper and get the solution of the water-soluble fluorine-containing oil-resistant agents. The surfactants include ordinary ones non-ionic surfactants. Ethylene oxide condensate products. Propylene oxide condensate products and ethy- lenoxide-propyleneoxide condensation products. Typical examples are Polyoxläthylen-Alkyläther, Polyoxlalkyl-Aryläther, Polyäthylen-Polypropylen-Ether and Polyoxyethylene alkyl ester. Are particularly preferred

3 4

Polyoxyethylene-alkyl ether and polyoxyethylene-polyoxy wax emulsions, for the oil-resistant composition

propylene ether. These compounds can be nitrogenized according to the invention is especially used for production

Containing or phosphorus-containing condensation components are made of oil-proof paper, which is both water repellent

or compounds whose terminal stability and oil resistance is better are preferred. the

that hydroxyl groups are modified. 5 Wax emulsion can be used together with other water-

Since it is necessary, as described above, to use repellent agents,

that they have an ability to penetrate or penetrate, and furthermore, the oil-resistant composition can according to

Have solvency, it is necessary that the invention inorganic and organic metal ion

Cloud point of the non-ionogenic surfactants In the area of chelating agents, such as ethylendlamine tetraacetic acid (EDTA)

from 35 to 99 "C Hegt. 10 and sodium tri-polyphosphate. The additive

The cloud point is related to the phenomenon in of metal ion chelating agents is preferred as it Compound after which the tensld in a diluted not only the use of hard water is possible aqueous solution with increasing the temperature of the make, but also the Ölfestlgkelt and the lei solution fails. This phenomenon increases the degree of non-ionization and accelerates the homogenization Tenslden together. The cloud point will be 15.

using a transparent aqueous solution. In the method according to the invention, with

determined (calculated on a solids basis). Resin glue and petroleum resin helmets sized papers or

The other surfactants, such as Natrlum-Dodecylbenzolsul- other types of paper are used. Preferred case

Fonat and the like are in the process according to the games are papers containing alkyl ketone dtmer, cationic

Invention not effective. 20 sizing agents and paraffin wax glue incorporated

The ethers which are general through-h those brought above. There is no reason the pulp or pulp

rneinc form !! are reproduced are also preprints that are used for the production of these papers

preferably water-soluble, which are able. In paper will be, to restrict. So could a multitude of

to penetrate and the solution of water-soluble fluorine pulps are called, including the various

containing oil-resisting agents to increase. 25 wood pulp, hemp pulp, cotton liner, bagasse

The monoalkyl ethers with pulp and synthetic pulps from rayon, vinylon,

Alkyl groups selected from the group of methyl, acrylonitrile fibers and polyolefin pulps. Furthermore

Ethyl, η-butyl, isobutyl and tert-butyl. the pulp can also contain anganic fibers such as asbestos

The ratio of non-ionic surfactant or fibers, ceramic fibers and glass fibers contain or

Ether to fluorine-containing oil-resistant agent is 30 consist of it.

not particularly critical, but is preferably in the The oil-resistant composition is inventively

Range from 300: 1 to 0.1: 1, in particular from 5: 1 to in accordance with Applied in the form of an aqueous solution, with

60: 1 on a dry weight basis. which the paper by means of an impregnation device, such as

The water-soluble, fluorine-containing oil-resistant properties are impregnated using a Kallbrler press or a calender

the means that can be inserted according to the invention or by means of a loading device, such as a

include: an aqueous solution is coated with an Amlnsal squeegee or a Gravler coating,

zes of perfluoroalkylphosphoric acid ester (solids content The optimal amount of oil-solid composition that

15%); an aqueous solution of an ammonium salt to be applied to paper varies with the quality of the

Perfluoroalkylphosphoric acid ester (solids content 33 *); Paper and the desired oil content. So is the

Aqueous dispersions of fluorine-containing resins (solid amount of water-soluble fluorine-containing

substance content 10 to 30%). against oil-resistant agents, based on

The oil-resistant compositions, which are used dry weight, 0.1 to 5 g / m ² for cardboard in the process according to the invention, 300 g / m ² with a degree of sizing of 400 seconds, contain at least one and 0.5 to 2 as indispensable components g / m ² for wood-free paper of 60 g / m ^{] of} the specified non-ionogenic surfactants and / or a degree of sizing of 20 seconds. This shows that ether with at least one water-soluble fluorine-containing agent is very economical in comparison with the daily oil-resistant agent, such as the method commonly used above.
described. Corrugated paper according to the invention to increase the oil, however, you can additionally use ordinary additives strength with a liquid, which include a special surfactant, such as pigments, starches and anti-foam 50 or a special ether in addition to a water sealer. Furthermore, they can also make other resins containing soluble fluorine-containing oils resistant to oil, such as acrylic latex, styrene-butadlene latex (SBR latex) containing the agent as described above, treated and carboxylates SBR. The addition of surface texture can be applied to all types of paper, uniformity agents such as oxidized starch, polyvinyl alcohol, through the paper material, an essentially polyacrylamide, sodium polyacrylate, methyl cellulose, 55 improved oil strength.
Carboxymethyl cellulose, sodium alginate, vinyl acetate- Since the oil-resistant sized paper, which is possible according to the process of malelic acid copolymer and vegetable oil, has been obtained according to the invention, which is excellent, however, the addition of petroleum resin sizing agents with properties such as oil-setting and the degree of sizing is inexpedient. The compositions may also have, as described below, may include anti-water repellants such as wax emulsions in a wide variety of fields for a wide variety of uses, e.g. B. Para-wax emulsions, petroleum resins or purposes in which synthetic resin-modified wax emulsions and mixtures are made use of these properties. Examples of such see of these, ethylene urea derivatives, e.g. B. Alkyläthy- uses are wrapping paper for food. len urea. Methylolamine derivatives, e.g. B. Methylol feed and fertilizers. Gauze sacks. Paraffin paper. stearyl amd, stearyl amd, Pyridlnlum-Verhlnclungen, fc ¹ »iron sheeillnated paper, ζ. B. Methylpyridlumchlorld. Silicon compounds. Release paper. Carbon paper. Electron photographer-Papler. Alkylkcten-Dlmer and the like. electrostatic recording paper, light-sensitive

The addition of water repellants, especially paper. Image transfer paper (Image transfer

paper) 'SOLUTION RESISTANT'; Paper and other papers for industrial purposes.

The advantages provided by the invention are achieved by using a small amount of a particular surfactant or ether with a water-soluble fluorine-containing oil-resistant agent. The required amount is about V ₅ compared to isopropanol. The composition obtained according to the invention is therefore economical and the problems associated with the flash point of a coating composition are eliminated.

Preferred embodiments of the invention are discussed in detail below. The examples serve to illustrate the invention, but are not intended to be a limitation thereof. If not otherwise indicated, parts and percentages mean parts by weight and% by weight.

example 1

Various oil-resistant compositions, as indicated in Tab. 1, were applied by means of a wire bundle No. 10 to the surfaces of commercially available cardboard whose weight was 316 g / m ² hurug and whose degree of sizing was 15 g / m ² Cobb. Then the boards were dried in an oven at 90 ° C for one minute. The products obtained were tested for their physical properties. The test results are shown in Table 1.

Example 2

Example 1 was repeated using it of the surfactants listed below together with a fluorine-containing oil-resistant one Middle.

A) Adduct of isodecanol with 8 mol of ethylene oxide (solids content 100%, cloud point 71 ° C),

B) Adduct of lauryl alcohol with 2 moles of propylene and 10 mol of ethylene oxide (solids content 100%, cloud point 66 °),

C) Adduct of nonylphenol with 17 mol of ethylene oxide (solids content 100%, cloud point 94 to 99 ° C),

D) adduct of lauryl alcohol with 6 mol of ethylene oxide (solids content 100%, cloud point 3O ⁰ C), and

E) Sodium dodecylbenzenesulfonate (solids content 50%).

The physical properties of the resulting Products were tested and the results are listed in Tab.

Pure white machine glazed paper with a weight of 50 gZm ¹ and a Stöcklgt-Lelmungsgrad of 8 see. applied by means of a horizontal long press with a degree of compression of 50%. The resulting materials were dried with a drum dryer at 100 ° C for 5 seconds. dried. The products have been tested for their physical properties. The test results are shown in Table 4.

Example 5

Various oil-resistant compositions, as shown in Table 5, were applied to samples of commercially available Clupak paper having a weight of 60 g / m ² and a Stöckigt level of 16 seconds. would have. For this purpose, a horizontal Lelmungspres.se with a degree of compression of about 50% was used. The samples were then placed in a drum dryer at 100 ° C for 10 seconds. dried. The test results are shown in Tab. 5.

Example 6

The following composition of freeness of 580 ml csf was placed in a long-life paper machine to produce a base paper of 75 g / m ² .

NUKP * "100 parts,

Resin glue 0.2 parts based on dry weight,

aluminum sulfate 2.0 parts based on dry weight,

based on dry weight.

Various aqueous oil-resistant compositions, as indicated in Tab. 6, the base paper was applied with a size press. The resulting Paper was dried in a dryer at 100 ° C. The products were based on their physical properties tested out. The test results are shown in Table 6.

Example 7

There were 100 parts of an aqueous, oil-resistant composition, which contained the following components:

30th

35

50

Example 3

Various oil-resistant compositions, as shown in Table 3, were applied to wood-free paper with a weight of 50 g / m ² _> 5 and an Lc / mungsgrad of 9 seconds. applied by means of a bottle fluidization technology and then the resulting material 30 see. at 100 to 110 ° C by passing through a drum dryer with a gap pressure of 20 kg / cm ² and a papler swirl of 10 m / ml. dried. The products have been tested for their physical properties. The results are shown in Table 3. AG-550 · '

Mixture of non-ionogenic T'insld
of a cloud point
from 45 to 48 ° C
and ethylene glycol monobutyl ether im
1: 1 ratio
Paraffin wax emulsion
(Solids content 40%)

0.3 parts on a dry weight basis 1.5 parts on a dry weight basis based

3.0 parts on a dry weight basis

Example 4

Various oil resistant compositions. The oil-resistant composition was applied to base paper made from various cell slurries or pulps as shown in Table 7, using a size press. The resultant paper was dried in an m-Troclper at 11O ⁰ C. Your products have been tested for their physical properties. The test results are shown in Table 7.

Table I.

Sample Ölhestiindigc / usamnienset / ii! en (I hurry > M No.

ACi- Isopro- fIhylen- Dietliylcn- Propylen- Diprn-530 * 1 panol glycol- glycol- glycol- pylene-

miinii- mono- mono- glwol-

butyl

ciher

huivl- bin vl-

Dior. On

letra- Physical see I l.imm- hyil ro- l-'igensch il'ten the riinkl animal l'u ran Products ö'S-.esiiin- Di- (H- kero- (leagues / u- nieltn1- li .-> lig- > ene s.imnicn- siiHnxid wedge degree lesl '2 ■> et / ungcn

elher

elher

niDiiobuivlcthcr (KiI No.
Ί I

1 15

2 15

3 15

4 15

5 15

7 15

8 15

9 15

10 15

12 15

13 15

14 15

15 15

IO

10

10

10

10

10

O O

10-11 C

X
X
X

(JIS
K-253 '.)) M

while boiling

ι 111 ' W \ J I .J IN-

2274) * 5

at Siedon (JIS K-2274) * 5

when boiling (JIS K-

2274) * 5

when boiling (JIS K-

2274) * 5

at Siedsn (JIS K-

2274) * 5

when boiling (JIS K-

2274) * 5

when boiling (JIS K-

2274) * 5

when boiling (JIS K-

2274) * 5

Table 2

Sample Oi Resistant Compositions (parts) * 3

AG- isosurfactants 530 * 1 propanol

Physical Properties
of the products

Oil resistance grade (Kit No.)
»11

Kerosene test * 2

Flash point of

oil-resistant

Compositions

1 15

2 15

3 15

XX
X
X

28 ° C (JIS K-2539)

still table 2

l'rohe (!! stable compositions (parts) * .1 No.

Λ (ί-! So- surfactants
> 3 () "I prnpa-

niil

15th

8th 13th '■■ I 15th IO 1 Γ Il Ι 5

30th

10

IO

Physical 1 ". igenschal'len flash point of of the products remove oil Oil resistance Kerosene- Compositions grai! (Kit No.) test * 2 ♦ II 10 O X while boiling (JIS K-2274) * 5 10 O while boiling (JIS K-2274) * 5 7th X while boiling (JIS K-2274) * 5 IO O while boiling (JIS K-2274) * 5 10 O 2 XX 2 XX

Table 3

l'robe (!! permanent composition Physical properties of the products No. (Parts)

Aü-530 * 1 Ethylcnglycol oil strength grade Stöckigt sizing grade

monobutyl ether (Kit No.) ♦! I (sec I (>

2 3 10 3 5 10 4th 7th 10 5 2 10 6th 3 5 7th 5 5 8th 5

5 7

8-9 10 4 6 7 6.0 8.0 8.7 9.0 9.3 8.0 9.0 10.0

Table 4

sample
No.

Oil-resistant composition (%)

Solid amount physical. Properties of the products

AG-

550 * 7

PVA * 8 Propyienglycol- propylene glycol ^vo "Contrast ölfestigkeits- Stöckigt

" ¹ ^ degree degree of sizing

(KitNo.) * Ll (sec.) * 6

monobutyl ether mon-i-octyl ether (g / m-)

3.7 2.2 2.2

1.5

1.5
1.5
1.5

10

3.0

0.22 1 23 0.22 i0 28 0.22 7th 25th

12th

Table 5 ("» Stable composition ("*) oil quantity of
... r. . .... detached Λ (ί-55 (Ι
ACi surfactants 10,. ,,
"" .-, lg / '"" »
- ^{M) 7} ABCI) V. Table 6 0.75 0.75 0.75 Mixture of
non-iom-: n
Surfactant one,
Cloudy
point of
45-48 ° C and
Ethylene
glycol-mono-
butyl ether im
Ratio 1: I. Petrox
P-200 * 0.20 lot Physical highlights
Oil resistance level
(Kit No.) Ml 11th e F-: keeping the products
Slöckigt glueing
Degree
(sec.I "f> Slockigi-
l. degree of acceptance
I <ec.) * H sample
No. 3.7 test 1.50 1.50 1.50 1.5 3.0 0.20 Γ 22.0 52 ι * ⁴ 2.2 No. 2.5 3.0 0.22 8th 37.2 50 2 2.2 1 2.5 3.0 0.18 10- 32.8 48 3 2.2 2 2.5 2.1 0.21 6th 2 ¹ U 45 4th 2.2 3 2.5 2.1 0.18 11th 30.2 51 5 2.2 4th Oil-resistant composition C - - 0.20 7th 33.5 49 (l 2.2 5 AG-
550 * 7 1.5 _ 0.75 0.19 11th 35.2 50 7th 2.2 6th 0.3 1.50 0.20 Γ 21.6 8th 2.2 7th 0.6 I .M) U, 2U 2 Physically 22.3 9 2.2 0.9 i Know
astonishment
(No.) M5 ~ 20.0 10 0.6 Ό on a dry basis) 10 0.6 Meikaset PoIy-
12 P-801 '13 marron
365 * 14 away- 10 0.3 sorbed
(!! more consistent
Together
settlement
g / m- ' 10 0.3 - 21.0 8th - 23.0 10 - 23.5 0 0.8 0.1 22.0 4th - 22.5 18.0 21.5 Ownership of the product Oil stick
keitsgr.id
(Kit No.)
MI (l 8th q 8th 7th Γ 7th

Table 7

Test Pulp composition (parts on dry basis) Cell Weight Amount Physical properties

No.

Pulp Tbrci

NUKP M6

NBKP

M7

LBKP M8

Resin glue

Alumi means
nium to sulphate increase
the wet strength
speed

stoli grind (ml)

of the absorbed beer

of the products

Water- Ölfestia- Stöckigtpap, ers olbestan- _ab . _ness sgrad LEI

g / m- d.ger _{influx (Kjl No) mungs} .

together- _(No) * - _{15M] d} ~

Settlement

g / m ²

(sec.) * 6

100 100 100

30th

50

50

100

0.2 0.3

0.2 0.3 0.3

2.0
2.0
1.5
2.0
2.0
2.0

1.5
1.0

580 570 580 570 500 540

75 21.0 75 20.5 75 24.8 80 19.0 170 * 20 15.2 64 22.3

10

10

10

52 65 45 80 50 48

13 14

'i Fluorhalilges across from ()! pestilizing agent (a wallrlgc solution of an amine ^{salt 1} ; of Perfiuoroalkylpho'nhor-

s.turcester: solids content IS ¹ M.
"2 kerosene test

About :; 0.2 ml of kerosene was taken on each sample and then each sample; Observed for 10 minutes at room temperature. Oils

Rehearsals where there. Oil not penetrated to the back. ha; .. ··, ilcp test found and were rated (o)
"3 A lot of sizing is 20 g / m '.
• 4 JIS K-2539

This test method is intended for petroleum products with a flash point below 80 "C.

The sample is placed in a teaspoon and this is sealed airtight with a lid. Fine flame predetermined GrOBe is introduced into the test cup after each rise in temperature by 0.5 C. The lowest temperature at which the

If fumes of the sample are ignited, it is determined
• 5 JIS K-2274

Fine Sample Is Put In An Oil Spot And It Is In Predetermined! Measure gradually increases when the temperature is near the flash point l-i. a test flame is passed over the sample after a temperature increase of 2 ° C. Fs will be the Determines the temperature at which the sample's vapors catch fire.

• d Stocl'.igt-l.clmungsgrad

Fr is determined in accordance with JIS P 8122

For example, sample sheets of 50 mm 'are produced and every four portions of each sheet are bent upwards. The resulting test sheets are placed on a 2% ammonium rhodanld solution of 20-IC in a dish and at the same time Add a drop of Mger Ferrlk's chlorine solution at the same temperature to the solution using a pipette. Then the Tent is in place. until three red spots appear on the surface of the sample sheets.

* ⁷ fluoride protection agents against oil (an aqueous dispersion of a fluorine-containing resin: solids content 30%. * 8 polyvinyl alcohol (degree of polymerisation 1700).
• 4 applied pressure approx. 30 »

"10 The surfactants are the same as those used in Example 2.
• II Determined according to the kit test, described in TAPPI RC 338.
'12 Pearly wax emulsions (solids content 40'v).
M ι Aerylharzemulslon (solids content 45 * 1

"M Oherflächebelmungsmlttel (styrene-malelic anhydride copolymer; solids content 10%).
"15 Water repellency

It was determined according to JiJ P 8137.

A drop of distilled water at 20 ± Γ C is placed on a test sheet at an angle of 45 ^r and with a vertical distance from the sheet of more than 1 cm. The trail of drops on the test sheet is observed. The results are rated in steps from 0 to 10

0 means: the track has a width of that of the drop (or is even wider) and a length of more than 30 cm.

10 means: the drop has fallen completely and no trace can be seen on the test sheet.
"16 Welchholz unbleached kraft pulp.
T / Bleached kraft pulp from Welchholz.
"18 Bleached Kraft Pulp from Hardwood.
"19 Decolorized paper.
* 20 This base paper is cardboard.

Claims (5)

Patent claims: 1. Process for the production of an oil-proof paper, in which paper is coated with a liquid or is impregnated which contains at least one fluorine-containing oil-resistant agent, characterized in that the coating or impregnation is carried out with a liquid which is at least a compound selected from the group consisting of non-ionic surfactants which have a cloud point in the Range from 35 to 99 ° C, and ethers that fall under the general formula I. HCHX-O -) »R in the mean X -CH ₂ CH ₂ ^ -CH ₂ CH ₂ CH ₂ -OdCr-CH (CH ₁ ) CH ₂ -, η is an integer from 1 to 3 and R is an alkyl radical with 1 to 5 carbon atoms, is added. 2. The method according to claim!, Characterized in that coating is carried out with a liquid or impregnated. In which the connection and that fluorine-containing oily agents in a weight ratio of 300: 1 to 0.1: 1, on dry weight related, are available. 3. The method according to claim 1 or 2, characterized in that one with a liquid coated or impregnated, the surfactant is a compound from the group of polyoxyethylene-alkyl-ethers, polyoxyalkyl-aryl-ethers, polyethylene-polyoxypropylene-ethers and polyoxyethylene-alkyl-esters contains. 4. The method according to claim I, characterized in that coating is carried out with a liquid or impregnated, which contains a compound of the formula as ether. In which R is methyl, ethyl, n-butyl, Means isobutyl or tert-butyl. 5. The method according to claim 1, characterized in that the liquid is a wax emulsion includes.