DE1944159A1 - Process for increasing the rate of absorption and moisture-stabilizing effectiveness of polyoxyalkylene glycols in cellulosic materials - Google Patents

Description

Process for increasing the rate of absorption and moisture stabilizing effectiveness of polyoxyalkylene glycols in cellulosic materials

The present invention relates to moisture stabilizers Preparations for cellulosic film materials and a method for Stabilizing cellulosic film materials against changes in physical dimensions with changes in air humidity, in particular to a moisture stabilizing preparation made from a polyoxyalkylene glycol moisture stabilizer and a polyoxyethylene oxypropylene glycol copolymer to improve the rate of adsorption of the preparation and to a method of improving the moisture stability of more cellulosic !! Foil material · by applying such a preparation.

Changes in humidity result in severe coating problems and treating cellulosic »! Foil or sheet material in one automatic device. Due to the changes in the air humidity changes in the moisture content of the material that cause shrinkage and lead sources of the same. Different parts of the material will shrink and do not always swell to the same extent, causing wrinkling and blistering and curling, and thereby the material does not lie flat.

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The through the crowd! Problems with moisture stability are particularly evident in the case of paper which has to be fed from a stack into a high-speed machine, for example an offset printing device. If such a paper is not completely flash, it can jam in the machine or form folds, which can lead to errors in the process and possibly to paper jamming and shutdown of the device.

A particularly serious problem arises in the case of layout paper, the ) must lie absolutely flat in order to satisfy the user. These

Papers can be attached to various surfaces by means of elastic adhesives are applied, and those to change the moisture content in the paper Leading changes in humidity can cause the adhesive layer to loosen and cause it to peel off from the paper due to wrinkling, blistering, or curling of the paper.

Changes in the moisture content of photograph! sshem paper, ozalid paper, Xerox paper and copier paper for the Therroofax process produce defective Copies, misaligned images, and possibly device shutdown ■ due to a paper block.

To reduce or overcome these problems, paper and other cellulosic film material treated with moisture stabilizing agents ; delt. It is known that low molecular weight polyalcohols such as ethylene glycol inhibit and glycerin, changes in moisture content of cellulosic

I - ■ .- ■■ '■ ". ■■ ■■■"■'". ^: ■ '■ -." ■■■

Foil material. These polyols become relatively quickly in large quantities in a short period of time

However, the difficulty is that these polyols

'' are rather volatile and will soon be lost to the paper through evaporation, on which of course there is no further moisture stability «*

High molecular weight polyols, such as the Polyoxyalkyleng3ykole _t are less volatile · These materials are due to their high molecular weight, however, is slow in cellulosic "! Foil material is absorbed and therefore not

very satisfactory if not on the long before processing Paper have been applied. When processing paper in a high-speed Machine there is just no time the polyoxyalkylene glycol or apply another, high molecular weight material and wait for it to until it is absorbed by the paper in sufficient quantity to produce the desired To impart level of moisture stability · A low molecular weight Polyol mixed with a high molecular weight polyol (cf. US patent 3 301 680} improves the absorption rate, but still < the mixture is absorbed into paper too slowly to be used in a size press where, for example, the moisture content of the cellulosic Foil material is quite low, i.e. around 5-15 $ and the processing speed in the device is quite high.

According to the invention, a moisture-stabilizing preparation is now created, This is due to a high absorption rate in the cellulosic fiber material and is characterized by low volatility. This material can therefore be applied to the cellulosic film material in a high-speed machine should be applied ensuring that it is absorbed quickly enough and in sufficient quantity to be used for subsequent processing to give the film the desired level of moisture stability. The cellulosic fiber material can also be used in film form before processing, as s.B. to cellulosic pulp, to cellulosic fibers

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iffi Dutch or paper entry ("fjxrriish") or for each hand- ·

can be added before or during the R ^ ea production. 3h'this The case has the Polyethylene Ethylene Glycol Block MisohpoliTOerisat the Function, the moisture-stabilizing effectiveness of Po3yo3 £ yalkylen ~ ". Glycols to improve · Furthermore, the strength of the treated paper greater than the temperature when the preparation is added to the cellulosic material in film form ·. "" "■ -." ':,

Thus, the preparation of Polyoxyalkyienglykol · Feuohtigkeitsstabilisator undVotyi ^ ^ ethylene xypropylenglykol ^ Blockmischpoly · is ira erfindüngsgejnäßen method - \ Bierisat incorporated into the cell.ulostsche Fasematerial, causing the block

copolymer dia absorption speed of the

and also improves its moisture-stabilizing effectiveness «Afterwards

See ΐή JOlien material shows good moisture stability.

The preparations according to the invention, based on a feußhtägkeitsstabilisierendßn Polyosyalkylenglykol as f euchtigkeitsstabilisierendes means and eineiB ^^ Po3yoxyatfeyl # ß = Oagrpropyl gsig3ykol-Blookiais0hpolya © risat to verbessertea "EiadringiangsgeseterMigkeit of Polyoi ^ alkylengljrkols in the ceUulosissfa® ^ film material and in. Some cases to improve * of - The effectiveness of which is "i * sid®2" effective. The polyalkylene glycol metal sheet is itself "also a polyosylgaglylsoil, * j © doda .in * its structure si @ n- <>'- .. borrowed-different and has a very different and synergistic © "" ■■ -.- effectiveness · "** -_. ■" - ■. **

The Po ^^ äthylmHDjqrpro ^ lmglykol-Blockpoly ^ has a central

Core made from a polyo ^ ypropi ^ lengljkolpoljmerisat, on whose ain or two terminal Hydroaylgraigpen Po ^ o3 ^ äthylm-Blocl ^ lyES © risateiiÄeiten _e di © even terminal H ^ dro3? Yigruppenhab®i » gebunäm sissd · These

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are known and are described in U.S. Patent 2,6-4,619 · You can -be represented by the following general formula: ■

• HO / TC ^ O) ^ (Q ₃ H ₅ O) _n ^ (C ₂ H ₄ O) ^ J _{11 H}

the values of rn ^ and jju are such that the oxyethylene groups are 20-90 wt. of the connection and either m or nu can be 0; η is a whole Number corresponding to the number of CJL-O units; and the value of η is that the molecular weight of the compound excluding the oxyethylene units is at least 900 (as determined by the hydroxyl number); ρ is a integer with a value of 1 or more.

“These block polymers are made by condensing ethylene oxide with a polyoxyproylene glycol having a molecular weight of at least 900. Other details of the preparation and properties of these compounds can be found in US Pat. No. 2,661,619.

3h of the preferred copolymers of the present invention is the Sum of hl and nu between 2 and 20; η is a number with a value of 1 up to 25; ρ is a number with a value from 1 to 5ί and the average Molecular weight of the block polymer is about 1000-5000

Block polymers of this type are available commercially as "Fluronics" and "Berol". The "Pluronics" are identified by the letters L, P or F and a number. You letters identify the physical form, L for liquids ( "liquids"), P for pastes ( "pastes") and S for solid forms ( "solid form's ^11), which are hard enough to flakes. Identify the first one site or sites dfts typical molecular weight of the polyoxypropylene base

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materials and the last ones digit indicates the approximate percentage Ethylene Oxide in the Entire Molecule · The commercially available ones in the inventions Preparations that can be used are "Pluronics" and their properties

shown in the following table 1; ·,

Table 1

MoI.- ia polyoxyethylene 20th 30th in total molecular 50 60 70 80 ^ weight 10 ~~ ·. ««. HO L35 - F38 950 L31 L42 IA3 - ■ - - __. 1200 ■ ~ - -. IN THE - - 1450 - L62 L63 - P65 - - - F78 1750 L61- L72 - Lo ^. P75 - F77 ~ - 2050 -. _- - P85 - F87 F88 2250 . L81 L92 - P84 - ■ —i. - F98 ■ 2750 ~ P103 P94 PI05 - F108 ■ 3250 LlOl ,. ■ · -. - PlO ^ _ ■ '__ " ■ - ■ .. " - 3625 - -. L122 P123 - nw. . . ■ _ - «b * u FI27 ΊΟ00 L121 __

The polyoxyalkylene glycols used as moisture stabilizers correspond to the general formula?

"h / ÖCHCCHo) 1 OH

... ■■? '■■' ■■■ ■■■■■■ '''.':' ■ '■

In this formula, R stands for hydrogen or methyl; n ^ has a value of

1 to etti & 3V ¹ UJ ^ n 'such between about 5 to about 350 · The Polyoxyalkjlengljkol should be water soluble and has a molecular weight between about I5O-Ioooo have _e.

Such polyoxyalkylene glycols are, for example, polyoxyethylene glycol and polyoxy-1,2-perylene glycols Polycacy-1, S-butylene glycol, polyoxy-1,4-ethylene glycol, polyoxy-1,4-butylene glycol and

1 * f t

The relative proportions of the polyoxyalkylene glycol and the polyoxyalkylene glycol block polymer are not critical. However, there is no reason to use more block polymer than is necessary to sufficiently improve the rate of penetration of the polyoxyalkylene glycol into the cellulosic material to the desired extent. In general, a considerably improved rate of absorption is found with a block polymeric breath amount of only 1.0% by weight of the poly (alkylene glycol). The effectiveness increases with an increased amount, and reaches a practical maximum at about 2.5-20 wt .- ^ of the polyo ^ alkylene glycol. Although larger amounts can be used, the increase in the absorption rate does not correspond to the additional amount of polyoxyalkylene glycol block polymer added; however, if appropriate, they can be used in order to take advantage of other properties of the polyoxyalkylene glycol block polymer.

The present invention is applicable to cellulosic sheet materials of all kinds. It is particularly suitable for paper, cardboard, corrugated cardboard, kraft paper, kraft Auslegekarton ( "linerboard") νιιά cardboard "The type of material celliilosischen- kana strong variidreB _p and there were excellent results- found duesh Verasndung of Fapi © ran high irtBipengehalt and papers that completely consisted of cellulosic Palpe · Cellulosisehes Folienraaterial of jader Pulps kana improved T? _t srden including pulp from spruce "spruce, birch, beech and other 381 se" ¹ ". , .The material can be bleached © or possibly unbleached.

Bas öE € "iad ^ Geg'-3HäSe PrSpa? © * tesm ans - an" aqueous solution "can be easily sprayed onto the filler-dissolving film material. The concentration of the solution is chosen so that the desired polyoxyalkylene glycol builds up after the treatment dga paper yields. The preparation can be dipped

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or soaking, by spraying or brushing on or other, customary, methods known to those skilled in the art can be applied. When immersed or,;, The cellulosic sheet material can be soaked to reduce the absorbed Amount of solution to be squeezed out to the desired hatred of absorption Optionally, the cellulosic material can then be stored at room temperature or dried in an oven.

The moisture stabilizing preparations according to the invention can the cellulosic material from the pulp to any other process stage to the film, e.g. in the pulp slurry or paper entry, the cellulosic fibers after film formation, during or after dewatering * and laying or Fourdrinier sieves,

before, during or after the drying of the film and before, during or after the pressing. You can also connect with others

Treatments - e.g. during sizing, pigmentation, coating,

("seasoning")
Humidifying or air drying / or wet strength treatment. Thus, the preparations are very versatile in their use. Their unusually high absorption rate is only determined when they are incorporated into the ceHulosic fiber material in foil or bulk form and not when applied or used with aqueous suspensions or paper entry ("furnish").

It is possible to add small amounts of the polyoxylakylene glycol block polyacrylate use to increase the rate of absorption of the polyoxyalkylene glycol through the cellulosic film material by 1.5 to 2 times or more heights. Therefore, the cellulosic sheet material can be in dry or wet Condition to be treated. Smaller amounts of polyoxyalkylene glycol can also be used to achieve the desired level of moisture stability

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ti · · ♦

are used than when using preparations that ^{do not} contain any polyoxyalkylene glycol block polymer, and of course the treatment time can be shortened considerably.

The effect of the polyoxyalkylene glycol block polymers according to the invention is obviously unique and not used by any other wetting agent or detergent shown. These materials in combination with polyoxyalkylene glycols. cause undesirable hygroscopicity and renewed wetting power in the more cellulosic! Foil material and still do not give the noticeable Increase in the rate of absorption of the polyoxyalkylene glycol by the Foil material. ·

The following examples illustrate the present invention without restricting it.
Example 1 to 3

Using unbleached "Dynapac Extrensible Clupac Paper" paper, numerous polyoxyethylene glycol moisture stabilizer preparations were tested a roller press was removed. The foils were placed in an oven at 10.degree. C. for Zk hours. left to dry. The films were exposed to air and weighed before and after treatment and the weights compared. The difference in weight is given in Table 2 as the amount of absorbed polyethylene glycol, expressed in weight percent of the dried paper.

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Table 2

Example no. water 35 Ethylene ^ Parts by weight • 1500 4000 ■ absorption . - ' glycol Block potym. , - - 9.1 33 - Berol TVM 370 - - 11 ₈ 2 Control A 35 35 Polyethylene glycol 1n.M0l.5ew. - - 18.2 Control B - - ■■ ' Λ00 65 - 8.6 1 33 2.. · ■ '■'. 65 65 - 11.4 Control C 35 35 , .-- 65 65 - 19.6 Control D '■ - ·. ^: ■ • ta . . . - '■ "' ■ ' 65 65 10.2 2 33 ; Z ■, ■ '. ■ .. .. ■ te 13.3 Control E 35 ■ -. ; ■ ^:. 53 19.6 Control F mm mm - 3 ^'2: ·: __ -

+ = Polyoxyethylene-oxypropylene glycol, molecular weight 1 ^ 00 with 21 moles of propylene oxide and 5 moles of ethylene oxide.

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From the above data it can be seen that the addition of the polyoxyethylene-oxypropylene glycol block polymer in Example 1 doubles the rate of absorption of the polyoxyethylene glycol 400 compared to control A, since twice the amount was absorbed in the same time. In contrast, ethylene glycol in control B increased the rate of absorption of polyoxyethylene glycol only very slightly. Similar results are shown in Example 2 for polyoxyethylene glycol 1500 in comparison with controls C and D and in Example 3 for polyoacyethylene glycol 4000 in comparison with controls E and F. The advantages of the polyoxyethylene-oxypropylene glycol block polymerizate are thus clearly evident from the above data .
B is ρ i <e 1 4- to 6

A similar series of experiments was carried out, measuring the time it took was necessary so that the paper sheet with the aqueous treatment solution was completely saturated by absorption from the surface of the solution. Writing paper of a writing quality with surface sizing was used tested; the treatment solutions were 20% by weight aqueous solutions of the Polyoxyethylene glycol preparations mentioned in Table 3. The ones to be tested Sheets of paper were placed on the surface of the solution, which turned into a clear container. A light source in the form of a strong fluorescent tube was attached under the container, which is located behind a Frosted glass was located. Then the time was determined by observation from above which was necessary in order for the paper to complete with the treatment solution was saturated. The untreated paper immediately after it was placed Significantly more light passes through the surface of the solution than it does completely saturated paper foil · So was the time from placing the foil on the Solution surface measured up to the point in time when the light is no longer

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-in the - same measure ^: §i <ekfcbai "was md .none ■ -more variation of the intensity ' _: , * more untaiag .-. Var the paper not -completely saturated ^ ' _$ after 120 seconds. so the test "was aborted, and the ^ results were fixed as close to 120 seconds- *

Di © Bat @ rL sand-la 'ä @ t the following table "-3 is listed ·

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Tabel Example no.

Parts by weight

Water ethylene block polymer. Polyethylene glycol m «Mol.gew. glycol Berol TVM 370 4 € 0 1500 4000

Control G control H

° control J

^ Control K

*** control L co

⁰⁰ Control M Time to Abscrp-tion in see

35

32

35

33 35

33

35

35

35

65 65 65

65 65 65

> 120> 120

> 120> 120

> 120> 120

% ■ «r

From the above data it can be seen that each control preparation required more than 120 seconds for the paper to be completely saturated with the test solution. Jm contrast, was the absorption time for 3 to 5 seconds when the Poljoxyäthylen-O ^ propylene glycol block polymer was present in the preparation · ν example? until 20

Writing paper of the ^r ^ in Example "6 \ erwendeten species was after the procedures defined therein with different proportions of polyoxyethylene Oxypropylenglykcl-block polymer tested · The data are given in the following table" · '

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Beiepel Kr. Parts by weight Block polym. Table 4 Polyethylene « Berol TVM 370 » glycol; Mole, wt.
400 0 Time to invade Ouroh Control N 100.0 0 * 5 sec 7th 99.5, 1.0 > 1800 8th 99.0 1.5 > 1800 9 98.5 2.0 600 98.0 2.5 • 150 ' O
O 11th 97.5 3.0 10.7 to
co 12th 97.0 3 "5 «Α 13th 96.5 4.0 4.1 K>
* «■>» 14th 96.0 4.5 3, o ~ -i
.P " 15th 95.5 5 * 0 2.2 co
CD 16 95.0 5ö 1.8 ■ 1? 94.5 6.0 1.4 18th 94.0 1.1 19th 93b5 ? »0 · 0.9 20th 93.0 0 _s 7 0 ₈ 6

As can be seen, with proportions of more than 1% by weight of Pplyo.KiräthyjLenglykol the Polyoxjräthylen-Cxypropyleneglykol-Blockpolynierisate give a noticeable reduction in the time necessary to penetrate the film, optimal results are achieved at 2.5-7 wt .- $ of the block polymer, where the difference in time is so small that it is almost impossible to detect · Obviously, if the amount of k # is increased, the reduction in the time necessary for penetration is quite small and can, except in very unusual cases, do not justify the use of the large amount of block potentizate (almost double, ie 7-Ji in Example 20).
Example 21 '

To the uses of the polyalkylene glycol preparation in different To show stages of paper making, the following comparative tests were performed on the paper machine * That actually paper produced was of the MG type. .

At the same time, using water instead of the polyalkylene glycol preparation controls A and B made.

1. In the press part of the paper device, after drying the paper to a content of about 30 % (second press), a 20- ^ water solution of the polyalkylene glycol preparation from 97 $ polyethylene glycol with a molecular weight ναι 400 ("PEG 400") and 3 <$ > Berol TVM 370. This solution was sprayed onto the upper press roller by means of a sprinkler pipe that was fed by a metering pump.

. 2. In the size press of the paper machine where the paper has a dry solids content of about 95 "$, this was treated with a 5 ^ water solution of the above Polyalkylenglykolpräparates..

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The physical properties of the papers were examined and separated listed in Table 5.

The practical properties, i.e. the moisture stabilization of the Paper were tested as follows:

A certain amount of an elastic adhesive was applied to one side of the dry test films of the papers, and the paper was then attached to a flat cardboard plate *. The test pieces were exposed to relative humidity of -6 $ $ »for 24 hours. Films 1 and 2 were in no way affected by the humid conditions after the test. In contrast, the Kon-checks showed A ^- and B blisters and bumps on their entire

-Surfaces.

Table 5 .

Basic thickness mass bursting polyalkylene glycol weight mm _em 3 / _ factor preparation; # ■ g / m ^ ^{/ g} ;

Test in the press section

Control A 77.4 0.092 .1.19 27.3 0

1 7 &, 5 0.092 1.20 29.5 '-1.2

Experiment in the size press,

Control 8 82.9 0.081 0.977 33.2 0

2 '80.9 0.0? 8 0.964 24.1 1.1

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Claims (1)

Ϊ9.4-Α159 Claims -: - _S in methods for increasing the Absorptionsgesnhwindigkeit and moisture stabilizing effectiveness of polyoxyalkylene glycols in cellulosic fiber materials characterized ^ characterized in that a product from a Polyoxyalkylenglykolfeuchtigksits- in the csllulosische fiber material - - 1 · incorporated stabilizer and a polyoxyethylene-oxypropylene glycol-Blockpol ^ msrisat, wherein the block polymer both the The rate of absorption of the polyoxyalkylene glycol is increased and its moisture-stabilizing effect is improved. 2, - Method according to claim 1, characterized in that the preparation on cellulosic film material is applied, ■ 3 · - Method according to spoke 1 and Z _9, characterized in that the preparation is applied to paper by immersing it in an aqueous solution of the preparation. · 4-9 method according to claim I _9, characterized in that the preparation is applied to cellulosic pulp. 5 · - Method according to claim 1 to ^ f-, characterized in that the preparation is applied with other chemicals during paper production _c 6 · - Process according to Claims 1 _e 2 and 5 »characterized« in that the preparation is applied * to paper in a paper machine, for example during film production, dewatering or couching; ? · - Method according to claim 6 “characterized in that the preparation is applied in the press part of the 4-way paper machine” 003812/1498 8.- The method according to claim 6, characterized in that the preparation is applied to the paper in the drying part of a paper machine. 9.- The method according to claim 6, characterized in that the preparation on Paper in connection with surface sizing, pigmenting or coating processes is applied in the paper machine. 10.- The method according to claim 6, characterized in that the preparation on Paper in connection with a surface treatment in a paper machine is applied. 11 · - method according to claim 6, characterized in that the preparation on Paper in connection with its moistening or storage ("seasoning") is applied. 12.- The method according to claim 6, characterized in that the preparation on paper in connection with and by means of surface sizing and pigmentation codes The coating process is applied in separate operations outside of the paper machine 13 * -Cellulosic fiber material with good moisture stability, containing a polyoxyalkylene glycol moisture stabilizer and a polyoxyethylene-hydroxypropylene glycol block polymer to improve the moisture-stabilizing effectiveness of the polyoxyalkylene glycol. 1 ^ .- moisture stabilizing preparation for cellulose fiber material, consisting of or containing a polyoxyalkylene glycol as a moisture stabilizer and a polyethylene-oxypropylene glycol block polymer for Increase in the rate of penetration of the polycykylene glycol into the cellulosic fiber material and increasing its moisture-stabilizing properties Effectiveness. . 009812 / U98 ■ - .; ":, ■■■ '19Ü159 15 · preparation according to claim 14, characterized in that the block polymer has the following formula: HO f (C ₂ V) _rai . <C ₃ H ₆ O) _n (W ^ Jp H in which m. and nu are whole numbers, the sum of which is 2 to about 20, where m or rru can also be 0; η is an integer from 1 to about 25; ρ is an integer from 1 to about 5, and the average molecular weight of the block polymer is between about 1000-5000. " 16.- preparation according to claim 15, characterized in that m, + nu = 3 to 18, η has a value of 1? to 23 and ρ = 1, and the average The molecular weight of the block polymer is between 1100-2200. 17 · - preparation according to claim 14 to 16, characterized in that the amount of block polymer between about 1.0-20 wt .- # of the polyalkylene glycol im Preparation lies. 18.- preparation according to claim 14 to 17, characterized in that it is 0.5-35 Parts by weight of a polyalkylene glycol or a mixture thereof with a molecular weight of about 200-6000, 0.25-7 parts by weight of block polymer and 65-99 parts by weight of a solvent for the polyalkylene glycol and the Contains block polymer. 19 · - preparation according to claim 14 to 18, characterized in that the polyalkylene glycol is a polyethylene glycol with a molecular weight of 400 or a mixture of polyethylene glycols with a molecular weight of 200-600 "". "■■ - ■ '" · ■. ""-■" - ^: ■■ '". ":: 09812/1498 20- preparation according to claim I ^, characterized in that the polyoxyalkylene glycol has the general formula h £ oGH (CH,) J OH £ ■ * ⁿ l ⁿ 2. in which R is hydrogen or methyl, n has a value from 1 to about 3 and n _{o has} a value between about 5 to about 350. The patent attorney: 009812/149 8