DE1696168A1 - Method for gluing paper - Google Patents

Description

BADISGIIB ANILIN- & S QDA-PABRIK AG _;

Our symbols: O.Z. 24 727 Mi / Bö Ludwigshafen / Khein, February 22nd, 1967

Method for gluing paper

The present invention relates to a process for Qberflä- λ chenleimung of paper using a new combination for the purpose of specific per se known means.

It is well known to make paper in bulk using rosin and related substances ("resin glue") and aluminum salts to glue *

It is also known to improve the strength properties the finished paper with carboxyl-containing copoly-, to impregnate merisates (see e.g. PP 931 044). A glue, thus an improvement associated with a certain degree of water repellency the water and unity resistance is here however not achieved.

Since the gluing achieved with the previously known means
are often insufficiently alkali-resistant and furthermore
often fill off rich papers with insufficient success in ratt
the mass, it was the task of the present invention

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finding to enrich technology with new means of leverage, which do not have the disadvantages mentioned.

It has been found that papers with excellent sizing effects are obtained if ^{paper containing Al +} or Fe ⁺ cations is impregnated on the surface with water-soluble salts of optionally partially esterified or amidated copolymers which are composed of

a) vinyl alkyl ethers and / or yinyl cyclohexyl ethers. and

b) maleic anhydride and / or maleic acid monoalkyl esters are constructed as characteristic comonomers.

The Al or Fe cations are primarily suitable for introducing them Aluminum sulphate ("alum") »Alumini urnace tat, basic aluminum chloride, basic aluminum acetate and ferric, Chloride. The aluminum salts are recommended for white papers, while with papers where a brownish-yellow tinge does not interfere, the iron (III) salts can be used in both Cases about 0.005 to 0.5, preferably 0.02 to 0.1 percent by weight of the cations, based on the amount of fiber. The salts are expediently added to the paper pulp; but you can also use the finished paper with a solution of the salts impregnate before treating it with the copolymer.

The vinyl alkyl ethers used to build up the copolymers (a) should preferably have 3 to 12, in particular 5 to 8, carbon atoms

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contain. The vinyl alkyl ethers have proven to be particularly suitable with branched CU- to Cg-alkyl radicals proved. The amount of these comonomers should be about 50 to 70, preferably 50 to 60, mol percent, based on the amount of the copolymer. ·

For the preparation of the copolymers by customary free radicals Copolymerization - expediently in organic solution or dispersion - takes place, maleic anhydride is preferred and then hydrolyzes the copolymer! sat. the Amido or alkyl groups are then introduced into the copolymer by subsequent ami dation or esterification, provided that one does not use the maleic acid monoalkyl esters as starting menu-mers (b) has used. The alkyl groups in the last-mentioned compounds should preferably contain 1 to 4 carbon atoms; this also applies to the alcohols with which the copolymers are subsequently esterified. Relevant for the middle one Amidation or degree of esterification is that the salts of the carb Copolymer! sates containing oxyl groups remain water-soluble. The average degree of amidation or esterification can therefore, generally up to 70% of all available carboxyl groups be.

As copolymers, those of about 50 to 60 mole percent vinyl butyl ether and 40 to 50 mole percent maleic anhydride have proven successful especially good. r:; . >

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Live the monomer (a) and (b), the copolymers can still be built up to about 20 mol percent of further polymerizable compounds (c), including, for example, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, the C | -C ₄ -Alkyl esters of acrylic acid and methacrylic acid, the vinyl esters of Cp- to C.-alkylcarboxylic acids, vinyl chloride and styrene. .

For the preparation of the water-soluble salts of the copolymers, which contain free carboxyl groups or anhydride groups do not need .all carboxyl groups to be neutralized, rather, a degree of neutralization of $ 60 is sufficient on the number of all carboxyl or anhydride groups in general already out.

The main cations are ammonium or mono-, di- or Trialkylammonium with a total of up to 6 carbon atoms and also, for example, sodium. These cations are introduced into the copolymers as usual, i.e. by reaction with, inter alia, * Ammonia and the free organic amines or caustic soda or sodium carbonate.

The amount of the copolymers required is approximately between 0.05 and 5, preferably 0.1 and 2, percent by weight, based on the amount of the fiber. The weight ratio of the amount of copolymer to the amount of ΑΓ ⁴ " ¹ "" ⁴ " or Pe ⁺⁺⁺ cations

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should "preferably be between about 1:10 to 1: 300.

. Lifting the salt copolymer combination to be used according to the invention for sizing Other non-ionic or anionic sizing agents, e.g. resin glue, can also be used will. The new means are very general with paper auxiliaries such as fillers, pigments, dyes, wet strength agents, Brighteners and other agents well tolerated. This applies to the manufacture of sized papers everyone Thickness and type, for example for paper and cardboard made of bleached and unbleached sulfite or sulfate cellulose and wood pulp.

The method of gluing with the new means is the same the rest of the conventional methods of surface sizing, so that there is no need for further explanations.

Papers are obtained in accordance with the object of the invention excellent sizing effects, with the alkali resistance and the good filler compatibility particularly highlighted be.

Unless otherwise stated, the following refer to percentages on weight.

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example 1

An approximately 0.5 $ wire suspension from ..- is processed. 100 tiger bleached sulphite pulp containing 0.5 # (based on the amount of fiber) contains aluminum sulphate, in the usual way for a paper with a basis weight of 80 g / m 2.

This paper is (fo salification 100) then impregnated with a 2.4 $ aqueous solution P of the ammonium salt of a copolymer of 50 mole percent Vinylisobuty lather 'and 50 mole percent maleic anhydride (based on the amount of the paper) to 1.2 fo would take on Peststoff and then dried.

In comparison, the same paper was glued in the mass with resin glue as usual, since this method allows the next comparable sizing effects achieved.

^ The degree of sizing was then determined according to the Cobb test (DIN standard 53/32 - 1 min) and after the ink swim test (test ink according to DIU 53 126) determined. The results are shown in the following overview:

Paper Cobb test ink swim test

after 1 min

according to the invention 20 no strike-through glued after 5 min

conventionally ge _ςη breakthrough

glues (mass) ° ^u 3 min

unsized HO penetration after

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Example 2

A fiber suspension of freeness 38 ⁰ SE _# from \ 30 fo., ^ Is processed.

/ Pulp and 70 $ bleached cellulose, the additives (based on the Kenge of the pulp) of 14 i ° kaolin and contains 1 $ aluminum sulfate, in a conventional manner to paper (80 g / m) and treating it with the above in Example 1 Sizing agents further.

The quality of the gluing is illustrated by the following values:

paper 'Cobb test
1 min 5 min 25th lint swim test according to the invention
glued . 17th 60 Breakthrough after
10 min conventional ge
glues (mass) 45 130 Breakthrough after
6 min unsized 120 Breakthrough after.
1 min

Example 3

A fiber suspension of bleached sulphite pulp (= 100 #), 12 % kaolin and 3% aluminum sulphate is processed as usual into paper with a basis weight of 80 g / m and it is then impregnated with an aqueous solution containing 1.5 % of the ammonium salt ( Degree of salinity 90 fo) of a copolymer of 50 mol percent yinyl butyl ether and 50 mol percent maleic acid

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anhydride and 2 io hot water soluble contains oxidatively degraded starch, to about $ 1.5 Feststoffaufnähme. . "-

In comparison, one puts a common in the mass with Harzieim glued "paper.. ■ ·

The evaluation of the degree of sizing would result in the following values:

Paper Cobb test Ink swim test - "-

1 min

according to the invention
glued 18th Breakthrough after
12 min conventional "ge
glues (mass) 60 Breakthrough after
6- min unsized 110 Breakthrough after
2-min '

• ■ ■ Example 4 ....

It processes a Paserstoffsuspension of bleached sulfite pulp (io = 100), 12 io kaolin, 5% aluminum sulfate and 1 io a commercially available anionic urea-formaldehyde wet strength resin in the usual manner to the paper the basis weight of 80 g / m. The paper is then impregnated with an aqueous solution of the methylammonium salt (degree of protection 100 io) of a copolymer of 55 mol percent vinylcyclohexyl ether and 45 mol percent maleic anhydride, which also contains 0.02 %

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of a commercially available anionic optical brightener. The solid on would take "was 1.8 <fo and in a Parallelyersuch 0.9 ^.

In comparison, the paper was glued in bulk as usual with resin glue. The test according to the Cobb test and for alkali resistance, at which the time was measured, the one! drop 10 $ caustic soda is required to soak into the paper, yielded the following values:

Paper Cobb test alkali resistance

5 min fminl

according to the invention
glued, $ 1.8 16 120 according to the invention
glued, $ 0.9 25th 80 conventional ge
glues (mass) 45 15th unsized 112 <5

Example 5

A fiber suspension of bleached sulphite pulp (= 100 fo) and 2 fo aluminum sulphate is processed in the usual way into paper with a basis weight of 80 g / m and this paper is then subjected to a surface sizing to 0.8% solids uptake with 0.5% each aqueous solution of the

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Ammonium salt (degree of salinity 100 $) of a copolymer from 50 mol percent maleic anhydride and 50 mol percent of a vinyl alkyl ether, which in the following table is designated xst4

Alkyl radical in the vinyl ether ink resistance Cobb test

(after 5 min)

-C (CH ₃ ), "Well 32 -OH ₂ -CH (CH, very good 28 - (0Hg) ₄ -CHl Well 36 -CH ₂ -GH (G ₂ I. Well 42 : oH ₃ ) ₂ I ₅ ) - (GH ₂ > ₃ -CH ₃

Example 6

A fiber suspension made of bleached sulphite pulp (= 100 <? ») , 1 $ aluminum sulfate and 0.5 $> aluminum aluminum is processed as usual into paper with a basis weight of 80 g / m 2 and then subjected to a surface size of 1.0 ^ Solids uptake with a 0.5 $ aqueous solution of the ammonium salt (degree of salinity 100 #) of a copolymer of 50 mol percent of maleic acid monobutyl ester and 50 mol percent of methyl vinyl ether or 50 mol percent of ethyl vinyl ether.

The results are shown in the following overview:

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Alkyl radical in vinyl ether

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Ink resistance

Cobb test (5 min)

-CH,

very good

40

very good

35

Example 7

A fiber suspension made of bleached suI-fitz-ellstoff (= 100 ^) and 5 ^c ß> aluminum sulphate is processed as usual into paper with a basis weight of 50 g / m and then glued to the surface. 1.4 fo pesticide uptake with a 0.5 $ aqueous solution of the ammonium salts ε (degree of salinity 100 fo) of a copolymer of 52 mole percent vinyl butyl ether and 48 mole percent of the maleic acid monobutyl ester. The sizing turned out to be excellent inkfast; the value for the Cobb test (5 min) was about 30. '■ -. -

Example 8.

It processes a Faserst off suspension of 30 fo groundwood and 70 io bleached cellulose containing 15 $ 3 $ kaolin and aluminum sulfate, as usual paper of basis weight 80 g / m. This paper is then glued to 1.2 $ Feststoffaufnähme with an aqueous solution superficial, 2 io hot water-soluble starch and 0.5 io the ammonium salt (degree of salt formation fo 100) of a copolymer! sates made from 50 mole percent vinyli? o-

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butyl ether and 50 mole percent maleic anhydride, its Anhydride groups were converted into mono amine groups after polymerization with ammonia.

The ink swimming time of the paper thus sized was about 10 Minutes, the values after the Cobb test were 17 (1 min) and 26 (5 min).

Example 9. .

It processes a fibrous suspension of bleached Sui fitzelleteff (= $ 100>) and the second%> Iron IlI chloride as usual au paper Fläcliengewichtes 80 g / m ~ and then glues it superficially to 0.8 <fo solid shot with a 2- ^ aqueous solution of the ammonium salt (degree of salification 100 fo) its copolymer from 55 .Kolprozent Yiiiyiicobutylather and 45 percent maleic anhydride. The yellow-brown paper thus sized had good ink fastness.

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Claims (5)

-13- O.Ζ »£ - ■ - 727 Pateiita fisprüche 1. A process for the sizing of paper, because it is marked by the fact that ^{paper containing Al +++} or Pe ⁺ cations is impregnated on the surface with water-soluble salts of optionally partially esterified or amidated Oopolymerisa-fcen, which from a) vinyl alkyl ethers and / or yinyl cyclohexyl ethers and b) maleic anhydride and / or maleic acid monoalkyl esters are constructed as characteristic coins » 2. The method according to claim 1, characterized in that the proportion of the conionomer (a) is 50 to 70 mole percent and that of the gomonomer (b) is 30 to 50 mole percent, 3. The method according to claims 1 and 2, characterized in that that the öopolymerioate are constructed not only from the Comonomereii (a) and A (b), but also up to 20 · I-Iolprozent from other monomers (o). '- ■ 4. Process according to Claims 1 to 3, characterized in that the water-soluble salts of the copolymers used are ammonium or sodium salts, ■ " 109847/0371 ⁴ ^ BATH -H- 0.3. 24 72? 5. The method according to claims 1 to 4, characterized, gekennζ ei without t , that one 0.005 to 0.5 Gev / ichtspr-ozent of Al ⁺ " ¹ "" ¹ " or J? E ⁺⁺⁺ - cations and 0, 05 to 5 percent by weight of the copolymer salts are used, based on the amount of oxygen. BAJ) ISGHE ΛίίΙΙΙίί- & 30DA-PABRIE AG 109347/0371 BAD OfWsHNAt