JPS5893764A - Aqueous adhesive mixture and manufacture - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new aqueous adhesive mixture based on starch derivatives for mechanical labeling, in particular for the labeling of glass bottles in automatic machines operating at high speeds, and to a process for their production.

It is known to use starch, dextrin and casein adhesives for labeling glass containers. Starch adhesives make simple adhesive systems and provide bonds with good drip strength in general.

For mechanical labeling, the adjustment of a large number of combinations of properties is of course an unavoidable prerequisite, both at the initial working stage and in the final labeled product.
There are many requirements for adhesives, in order to be able to l&ring on machines with rapidly rotating equipment parts, the adhesive must have sufficient Kl dynamicity and at the same time have sufficient 1kHz adhesion strength to label the objects to be applied. It must have a high initial adhesive strength to prevent slipping on the top. Next K.

The adhesive strength of dried labels is exposed to numerous loads under the influence of moisture during use of labeled bottles, and the adhesion must be maintained accordingly.

K for mechanical labeling, generally approximately 20.
It is necessary to adjust the viscosity to a certain range of 000 to 20 Q, OOOmPL-. 10Q, 000mPa
, in the range of sl, preferably from about 20,000 to 7 o
A range of o o mpa, - may be particularly suitable.

In order not to exceed such a viscosity range with starch adhesives, a solids content of at most 30% by weight is usually considered. Due to the resulting high water content, this starch adhesive does not have the necessary high initial adhesion strength.

In comparison to starch adhesives, dex)9 adhesives are generally thicker and therefore have less adhesive strength, so that they can be used for labeling in high speed automatic machines.

However, its disadvantages are that it has a relatively low water resistance due to its relatively low molecular weight and a high brittleness after drying, which tends to cause cracking of the label. It is generally not used for surface heat treatment and labeling of nine bottles.

Casein adhesives, which are often used for labeling, do not have the nine drawbacks mentioned above, but compared to starch adhesives and dextrin adhesives, casein adhesives are expensive to produce.2. This is due to the price of raw materials. Furthermore, casein exhibits some shrinkage, which is characteristic of animal substances, and therefore casein can be adjusted, at least in part, to other adhesion substances with reproducible properties (furthermore, this is better than casein). It should be cheap.）Yo1
There will be a need to replace it.

Starting from this problem, the present invention proposes the use of certain selected starch derivatives as the main adhesive component, which are mixed with certain other selected adhesive ingredients to form an aqueous adhesive mixture. ), a new adhesive mixture is proposed which is particularly suitable for use in mechanical lining in high-speed automatic machines.

The object of the present invention is therefore, as one aspect, an aqueous adhesive suitable for mechanical labeling, in particular for labeling glass containers, based on starch derivatives, containing a viscosity regulating side and optionally further customary additives. In the adhesive mixture (&) hydroxyalkyl ether of oxidatively decomposed starch with an average degree of substitution @S) < O, 2, and (1))
Water-borne cellulose conductors, synthetic water-soluble polymers,
The mixture is characterized in that it contains at least one polymeric compound selected from the group consisting of water-soluble starch derivatives different from casein and -), which is dissolved in an aqueous phase by KfII.

Therefore, the important features characterizing the present invention are the use of a starch adhesive component according to (-), i.e., the use of certain hydroxyalkyl ethers of oxidatively decomposed starch as the main adhesive component.

This starch ether is characterized by very little substitution by hydroxyalkyl ether groups.

It is preferably MS<0.1. The MS of this starch ether is particularly preferably in the range 0.01 to 0.1.
It is in. %% as hydroxyalkyl ether residue
Hydroxyethyl and hydroxypropyl groups come into consideration, especially those substituted by oxypropyl ether groups, and oxidatively decomposed starches may be of interest.

The four most important starch ethers of this group (&J are approximately 0.05
It has an MS in the range ~0.1.

The starch component (IL) is further preferably characterized by its viscosity. Drage Rheomat 15 (Drags-Rh
Approximately 40-20011P measured with @Omat 15)
Starch tool chills with a viscosity in the range of IL , - are preferred; starch ethers of the above-mentioned type with a dragee viscosity in the range of about sO to 140 mPa, - under the conditions described above are particularly preferred.
FftL is ugly and □Uru.

In this case, only one type of selected 9-hydroxyalkyl starch derivatives of the type mentioned above can be used as adhesive component (1).

An important aspect of the invention is, of course, that a plurality of oxidatively decomposed human tetraxyalkyl ether derivatives of nine starches are prepared in one place - by the product used - by adjusting their individual properties and their mutual quantitative ratios. It can also be used in a range that provides an aqueous solution within a given drag range. Therefore, it is preferable in the present invention to use, for example, a mixture of hydroxyalkyl ethers of oxidized starch having the following characteristic values as the adhesive component (a).
It can be particularly advantageous: (al)M8=0.08.
Drage viscosity of about 60111P&, - at 65°C and 25K solids content, and IIc (a2) M8 = 0.
Approximately 150 mPa at 08.65°C and 25K solids content,
- a Dragee viscosity of
) may be a preferred adhesive component in 41 in the sense of the definition according to the present invention for K).

An aqueous solution of such an adhesive component (-) alone is, of course, not sufficient to solve the problem of the invention; it is particularly unsuitable for use in high-speed automatic labeling machines. For solid volume high enough,
much higher than the intended use requires. Therefore, the present invention further presupposes the use of the above-mentioned component (b) in combination. In other words, the ingredients (the ingredients are selected from the details below)
or multiple O compounds: water-soluble cellulose derivatives, synthetic water droplet polymers, casein and/or water-soluble starch derivatives different from (1). Another important aspect of the invention is the 9th K and the present WA, which collectively obtain the controllability of adhesive properties in the sense of 11 problems according to the 11 iK of the present invention.
For the production of KN adhesive mixtures, one absolutely constant operating method is required. II. Before dissolving most of the adhesive component (&), it is necessary to dissolve the soluble polymer component (1) in the aqueous phase according to the definition and definition. Best of all, within the scope of the present invention, this particular order, ie first (b) and then (a)
Poly! - It has been found that component (1)) has a very specific structural improvement effect on the sK of component (1). If the above-mentioned order of dissolution according to the invention is followed, an aqueous solution of component (1) without the addition of (b) will generally act to lower the viscosity and/or ) will cause a storm in the retention of KR properties during the subsequent dissolution. Hydroxyalkyl ether substituted nine components (1
) is further alleviated by the addition of polymeric viscosity reducers (It). Interestingly, the addition of (1)) at the same time also leads to an increase in the adhesion and is therefore quite desirable in the sense of the task according to the invention, due to the combination of (- and The desired high solids content in the adhesive mixture can be prepared without risk of reducing the usability of the rounded adhesive mixture.

Component ((conversion)) or the corresponding mixture of component (a) is preferably present in the finished adhesive in an amount of about 15 to 50% by weight, with a range of about 25 to 40% by weight being preferred. On the other hand, the adhesive component (b
), component (a) is also advantageously used in small amounts.

Approximately 0.1 to 10% based on the weight of the finished round wire adhesive mixture
A proportion of (b) in the range from 0.5 to 6% by weight is preferred. Of course, in special cases, it is very expensive (1
)), for example up to 20% or 25% by weight
The adhesive component (b) can be divided into various sub-concepts. In the O subconcept, water-soluble starch derivatives that are chemically different from the starch ethers of evaluation (1) are used. For example, such starch derivatives of (b) are carboxyalkyl precipitates, starch conductors containing cationic groups and/or dextrins, which are usually reformed and have water-tactic properties. As such starch inducers, furthermore, the reaction products of starch with afi/acetic acid or epoxycoupa/sulfonic acids and the reaction products of alkylene oxides with alkylene oxides, such as ethylene oxides or poupylene oxides, may also be considered. In this case, it is possible to start from natural or decomposed starches, for example oxidatively decomposed starches. Starch ethers or starch mixed ethers consisting of nine starch ethers are suitable. If a hydroxyalkyl ether is considered as a starch derivative, it must be significantly different in its chemical structure and therefore in its properties from the starch hydroxyalkyl ethers of the (&) group, as dextrins, commercially available A medium-sized, medium-sized or thick dextrin paste is used, which is obtained by the decomposition of starch in an omniscient manner. where aqueous cotetraid (t)) O
The weight ratio of aqueous colloid (SL) to K is, for example, 1
:50 to 1:2, especially between 1:1S and 1:20.

In another sub-concept of polymer viscosity reducers (b), according to the invention water-soluble synthetic poly! - is used. Zuko ζ
Homopolymers and/or copolymers containing a vinyl alcohol group and/or a vinylpyrrolidone group and/or an acrylic ado group and/or a substituted nine acryl ado group are mentioned. However, homopolymers and/or copolymers of acrylic acid or methacrylic acid or water-soluble salts of these acids are also suitable.Individually, synthetic water-soluble polymers such as those with a saponification degree of about 70 to 98 and 2-100 m for 4% aqueous solution
Polyvinyl alcohol, polyvinylpyrrolide/, vinylbisilide/, vinyl acetate and vinyl lafricate O copolymer, polyacrylamide, acrylic and methacryl acetate, preferably having a viscosity of 4 to 1 Pa, s%. N-Methylolathalylamide, Natsu-ethylacrylamide, Iris-propylacrylamide, Natsu-butylacrylamide, dimethacrylic acid, methacrylic acid, acrylonitrile, acrylic acid methyl ester, acrylic acid ethyl ester, ( copolymers with metaphacrylic acid methyl ester, polyacrylic acid, acrylic acid and acrylonitrile,
Copolymers of acrylic acid methyl- and ethyl esters or their alkali metal and ammonium salts and other commercially available water-soluble polys ff + .

The weight ratio of water-soluble synthetic polymer a according to (t)) K to starch ester according to (IL) K is 1 usually 1:2 to 1:50.
A stone in the range of. Alternatively, smaller amounts of water-soluble synthetic polymers can be used. That is, for example, it is conceivable that the corresponding weight ratio is less than 1:200.

Finally, the sub-concept Ks of polymer viscosity reducer 0)
PVh, its aqueous adhesive solution (IL)
Water-soluble cellulose derivatives are used which provide controllable improvements in properties. Suitable water-soluble cellulose conductors are mixed ethers of 41-carxymethylcellulose, hydroxyalkylcellulose and/or the above-mentioned cellulose conductors, as well as their water-soluble salts.

Specifically, the above-mentioned carboxymethyl cellulose and its water-soluble salts, hydroxyethylcellulose and/or hydroxyethylcellulose, methylcellulose, hydroxyethylcellulose, methylhydrochloride, etc. dipropyl cellulose and/or carboxymethyl methyl cellulose ethers and water-soluble salts thereof.

Even in F-ζ, the weight ratio of Cb) K-compliant aqueous:X roid to (a) K-compliant aqueous;
In the range of 50. However, even with ζζ゛ it is also possible to use smaller amounts of aqueous colloid.

For example, a mixing ratio of up to 1:600 is used, preferably 11, <
is used in an amount not less than 1:200.

Cellulose derivatives of groups related to ζζ are usually 0
．． It can be a cellulose ether with a degree of substitution ranging from 1 to S. The viscosity of the 2-weight sacrificial fluid is 200~ at room temperature.
翫000鳳あa,-, 40υ or more, preferably 8
A cellulose derivative having a condensation temperature of 0°C or higher and 0°C is preferred.

In another embodiment of the invention, the polymer viscosity reducer (b)
Casein can be used as 0 normal casein/! Unlike I adhesives, the adhesive mixtures of the invention are characterized by a comparatively very low case/content. Here again, it is appropriate that the weight ratio of casei according to (b) to (IL) K 41a adhesive main component is in the range of about 1=15 to 1:2. Again, the casein content of the adhesive mixture is in the range of about 0.1 to 10% by weight, for example 0.5 to 6% by weight, based on the finished adhesive mixture. It is appropriate to take care to ensure that there is XK.

Another O1! In embodiments, the present invention provides an aqueous starch adhesive (D
It takes advantage of the fact that flL dynamics can be significantly adjusted by the addition of water-soluble low molecular weight viscosity reducing agents. In particular, it is known to add urea, thiourea and/or dicyancyamide to starch adhesives, but only inorganic or organic salts, such as halides, nitrates, sulfates, acetates,
Rienate or tartrate 4Has viscosity adjusting effect.

This end is [Watts, 1isif@n, mn
atriOhmitt@IJio6s, Fang 845-84
Page 7, by H. Harllert, [V@ran4@
rung dar F11*ssfahigkeit
vonK1@M16sungan uM klsbst
sffhaltigon! 1ind@m1ttelnJ
and l'-Han4buch (16r day tark
*J Fang IIIk, R, xahxer, 8t; rk
eklebstoffs, published by Paul Par@y,
1971, pages 55-57. The addition of such low molecular weight viscosity reducers to starch adhesives causes viscosity reduction, and also other O Rheology 41I+! It is known that it can also have a desirable effect. At the same time, the undesirable aging tendency of starch adhesives is also reduced.

In fact, the adhesive mixtures of the present invention comprising components (&) and K(b) and additionally known per se low molecular weight viscosity reducers of the above-mentioned type can be used even at high solids contents of up to about 60% by weight. The mixture has good fluidity, the aging tendency of the starch derivative is strongly suppressed, the viscosity is relatively low and can be controlled to a predetermined value of nine, but at the same time the adhesive strength of this mixture is high. Here too, an optimal combination of adhesive properties exists in Scope II of the invention.

The low molecular weight substances known for controlling the flow properties, such as inorganic salts, urea, thiourea and/or dicyancyamide, are advantageously used in amounts of about 2 to 411%, based on the finished adhesive mixture.
It is used in an amount of 20% by weight, preferably 5-12% by weight. From the point of view of the side building method which is compatible with the present invention, the following is valid: Similar to the polymeric viscosity reducing agent (b), a small portion of the low molecular weight viscosity reducing agent is added to the adhesive main component (a). The aqueous phase must be dissolved before dissolution can take place.

According to the invention, other customary auxiliaries can be present in the adhesive mixture. Examples include wetting agents, antifoaming agents and preservatives, fillers, and the like. Particular mention may be made here of natural starches and of starch derivatives which do not fall within the definition already given.

Such conventional additives may be present, for example, in an amount of about 0.3 to 20% by weight, based on the finished adhesive mixture.

The total solids content of the adhesive mixture of the present invention is preferably in the range of about 50-60% by weight.

Finished product: The viscosity of the adhesive is usually about 20,000 to 20 Q, 00 mPa, s, especially about 20,000 to IQ Q at 25°C. , OOOmPa,a.

In the process according to the invention for the production of this new adhesive mixture, the above-mentioned auxiliaries can be added both in the first stage (pre-melting) and in the third stage (dissolving component (a)). .

To obtain an adhesive that is suitable for rolling viscosity for mechanical labeling and at the same time has sufficient adhesive strength, it is important to carry out the two-step melting process described above. If all the components of the adhesive were subjected to simultaneous KWI digestion in one step, a product with a very high viscosity, i.e. non-uniform or difficult to flow, would be obtained, which is not suitable for mechanical labeling.

Of course, here the aqueous colloidal component (a) according to the invention
It is contemplated that various aqueous colloids may be used with (b) and (b). Often one aqueous cotetraid i.e. (b)
quickly dissipates. 4I Alternatively, it is also possible to use a mixture of K (a) and (1)) for the production of the adhesive according to the invention, since (b) dissolves very quickly and thus a state of pre-dissolution is achieved. followed by aqueous colloid)
is possible as long as it dissolves or swells.

The well-known fact that the fII1wIfi rate of water-soluble starch derivatives can be altered by slight cross-linking in both tables makes a difference here. This crosslinking is primarily considered to prevent the material from agglomerating when placed in water. However, in this case, the dissolution rate of component (&) is such that the polymer substance (b) introduced at the same time is +lI after the starch derivative (a) has swelled.
Before dissolution, the K can be lowered to virtually complete dissolution.

In Section 11 of the invention, heating the adhesive mixture to a temperature of from 70 to about 90° C. and thereby dissolves another starch derivative, natural starch or only slightly decomposed starch (optionally placed in the tip). This results in an adhesive charge having particularly favorable flow behavior together with very good storage stability.

The adhesive mixture according to the invention has properties that were hitherto only achievable from casein-based adhesives. Thus, the present invention makes it possible to completely or at least significantly eliminate the use of casein while still achieving the unique and necessary properties of conventional Q casein label adhesives.

EXAMPLES The adhesive described in detail below can be heated in a water bath, optionally cooled, and equipped with a stirring device.
made using a capacitive beaker. The water used in the examples has a Ho (German hardness) of % 16°.

Example 1 50p urea and 40I in 100j water under continuous stirring
Distribution of the cationic starch ether of I (reaction product of 3-Cool-2-Hytroxybuvyl-trimethylammonium chloride, DB = 0.05) and 111C) commercially available antifoam agent (based on silicone oil) Let's make it easy b60
Heat to ℃ to dissolve. After this material has become shiny, it is cooled, evaporated and refilled with logs, and an additional 100 g of water is added.

Next, the starting material was 140.9 oxidized potato starch human tetraxypropyl ether (Me: 0.08.65°C, 2
Drage viscosity at 0%** = 50 mPa, s, 65°C,
25 wt % solution Φ corresponding viscosity = 58 mPa, mass) and! After adding 611 noise starch [heat to 70°C. After stirring at this temperature for 15 minutes, it was cooled to 40 °C and after the addition of the 61 ethylene glycol 0
．． Add 5g01,2-pe/diisothiazol/-3-one solution.

The product so obtained has a temperature of 5 o, oo at 30°C.

It has a Brookfield viscosity of - mPa. This adhesive is used to affix the labels to the pinots of the internal quarters at a temperature of 6-9° C. in a high-speed automatic machine (5 & QOO bit hours). The device is equipped with a glue pump and a glue heater.

Adhesive temperature is 27-28°C. No cracking or falling off of the label occurred.

Example 2 79j water (16°LH) Ks? , 21DJii!
*and 1? , 4j'C) Disperse casei/. Ojj
1゜2-benzisothiasilyl/-5-o/and 11O
After adding antifoaming agents (mainly fatty alcohols).

1. Heat to 80°C under stirring in a water bath. Add ojO borax and heat at 80℃ for 10 minutes to completely remove casein.
Gently stir until dissolved.

The contents are cooled to 40°C and vaporized to replenish the logs.

Then in another step after addition of 100 p of water 1 (20 p
Noise starch, 30I cationic starch (see Example 1), and 150II human mixipropyl ether of oxidized potato starch (see Example 1) are added and stirred. The suspension is heated to 75° C. in a water bath under continuous stirring. Leave at this temperature for 10 minutes, then cool to 40℃ and add 1N of sucrose. Next, add water to the finished round wire adhesive solution.
Adjust to a solids content of 7.5 - (measured with a bending needle).

The product has a Brookfield viscosity of 6 QOOOmPm, - at 25°C.

45. Using this adhesive. When 0 bits are produced, a moderately efficient labeling machine can be used to produce beer beer at a temperature of 6 degrees Celsius (
Attach the label to the ws-a tsubaho).

At that time, apply labels to the center and top. Adhesive supply is performed by a pump, and the adhesive temperature is set to 1) 2 ft+ by an adjacent heating section. There is virtually no label cracking and no subsequent cracking is observed.

Example 5 ? 54.94 J' of urea in 2.5 J of water with stirring.

1.15j borax and 22. ? Add 6II casei/. Furthermore antifoaming agents based on fatty alcohols 1.159
and o, add 5 g of 1,2-pe/diisothiazol/-5-one. After heating to 80°C and leaving at ζO humidity temperature for 20 minutes after death.

After cooling to 40℃, evaporate and supplement the log (114N),
Add 0jj noise starch and 115IIo oxidized nine potato starch human tetraxypropyl ether (see Example 1) and stir. After stirring this charge at 70° C. for 16 minutes, an additional 85 I of water is added.

The resulting adhesive had a temperature of 8 ao O (llPa,
sO has a Pruttafield viscosity. A 15° C. moist bottle is used for mechanical labeling.

The adhesive is at 32° C. after the heating section.

Comparative Example The same materials as in Example 5 are used in the same amounts. However, the maize starch, urea, borax, oxidized hydroxypropyl ether of nine-potato starch, casein, antifoam agent, and Kffl-containing agent are added to the water with stirring. Stir at 80° C. for 50 minutes and cool for 94 IkK. *Viscous at temperature, 25℃
A proboscis with a Przterfield viscosity of more than 000 mPa is obtained. This product is difficult to use as an adhesive because of its viscosity, and its use in labeling machines is not possible. If a viscosity suitable for application on a paper machine is adjusted by dilution with water, the adhesion is insufficient.

1IIIA Example 4 Nakate Potato Yellow Dextri Inori (25°C, 60wt - Brookfield viscosity of solution: &gOgmPa,
5011 at room temperature in Boll water fII solution 1201 of s)
Add O urea together with 100 I of water and stir. Then lsqg cation/delay & (see Example 1) 176
I Hydroxypropyl ether of oxidized potato starch (see Example 1) 11 Antifoam based on mineral oil 0.29 Benzisothiazolin-3-one 106 g
Add water and 12 g sucrose as above and dissolve at 75° C. while stirring.

15 G at 25°C after 7 days of storage, OOOm
An adhesive with a Brookfield viscosity of Pa,s is obtained. Tests in the hinterlands have shown that the adhesive is suitable for labeling nine bottles in a high-speed labeling machine without an adhesive pump and heated to 70 degrees Celsius.

Comparative Example B Mix the following in the following order (stir at 75°C): 10
0g water, 50g urea, 59#O cationic starch, 1
Hydroxypropyl ether of oxidized potato starch as in Example 1 of 74II, 1 g antifoam based on mineral oil, 0.
2IiID Benzisothiazolin-3-one, 1041
1c) Sugar in water and 121101.

After cooling to 40°C, add 12 (1/2) of a 50% weight aqueous solution of potato and yellow dextrin laver in the same middle hand.The resulting product gels strongly after 7 days of storage and after being stirred vigorously at 25°C. 50 o, oo.

Otori Pa, - indicates Brookfield viscosity.

Due to its high viscosity, this product is not suitable for mechanical labeling.

Example 5 Reaction formation of 504F urea and 45.90% thionic starch derivative (5-cool-2-human tetraxyglobiltrimethelammonium trichloride) in 1011 water under continuous stirring. D8=O,OS) and KIN's commercially available O antifoaming agent (based on silicone oil) were distributed and slowly heated to 60°C to dissolve. K after death when the material becomes uniform.

Cool the evaporated water and add more IQOII□ water.

Next, this material was added with 951i oxidized potato starch hydro-oxypropyl ether (Ma: = 0.08.Draghe strength of 2 s weight solution at 65°C #about 60 mPa, s)
, 45 pO oxidized potato starch hydroxypropyl ether (Ma = θ, OII, Doge viscosity of a 25 wt% solution at 45°C = approx. 12 Q111P&0m and 5611
Add maize starch and heat to 70°C. ζO humidity temperature 1
After stirring for 5 minutes, cool to 40° C. and add 12:10 crude sucrose and o, s g of 1,2-benzisothiazolin-3-one after death to make up for the evaporated water.

The product so obtained has a temperature of 46% at 50°C. (100
It has a Brookfield viscosity of mpa, -.

This object is a high speed automatic machine with adhesive pump and adhesive heating section, suitable for applying labels to cold and hot bottles.

Example 6 Place the following into 1009 cold water under stirring: S
Q, Q fl 40 weight solution of polyvinyl alcohol (degree of saponification = about 88 mol%, viscosity of 4% solution according to ptechN5!$015 at 20 ° C = 4 mPa, s), 2
2. ? J maize starch, 4.51 cationic potato starch ether (S-chloro-2-hydroxypurvyl-
Reaction product with trimethylammonium chloride I:+2ide, D8:=: 0. Os ), 25I urea, 81pQ
Antifoam agent based on human tetraxypropyl ether of oxidized potato starch and human tIO mineral oil according to Example 1. dHeat at 9@KBO℃ for 15 minutes until uniform, and after cooling to 50℃, 0.
Add 17 of 1,2-benzisothiazolin-5-one.

The product thus obtained was approximately 40.0OO at 25t.
It has a viscosity of 7 (-L) in Pa, s() and is suitable for labeling cold and hot bottles in high-speed machines.

No product separation (phase separation) occurred during the one month observation period9.

For comparison, starch was dissolved as described above without using polyvinyl alcohol, and after cooling to 50°C, polyvinyl alcohol and the solution were added and stirred. The resulting nine solution (8Q,
GOOnPa,s) undergoes phase separation after 5 days.

Example 7 16% by weight solution of polyacrylamide in water with stirring 48p, 50I urea, 59I cationic potato starch, 174Ii hydroxypropyl ether of oxidized potato starch (see Example 6) and 211 silicon-based commercially available O antifoaming agent and added 80 t to the homogenized Ovk.
Heat to. After stirring for 10 minutes, cooled to 40tK and 0.5
J01.2-benzisothiazolin-3-one and 3
Add 0JIO natural potato starch. The resulting product has a viscosity of about 70.000 mPm at 25 DEG C. and is suitable for labeling hot bottles in machines with adhesive pumps and heating sections.

Comparison rounding K, first dissolve the starch by K as above, 4
After cooling to 0°C, add the polyacrylate solution. The solution so obtained has a viscosity of 18,000 mPa, - although the chemical composition is exactly the same, and has a high threading viscosity - which makes it well suited for use in labeling machines. Not 〇.

Example Dipropyl cellulose in methylhydro (degree of substitution = 1?~24% by weight O) in 155.5 sg of water under continuous stirring
Methoxy groups and 4 to 12% by weight of hydroxypropyl groups, 2% by weight aqueous solution Nopuru 7 Field R Tema viscosity (2
0rp)=h1000 mPa, s) is dissolved in cold water. 22. After the death, when the ingredients are uniform, the preparation is done in one phase.22.
9 N maize starch, 4. SjQ cationic starch (S-
Reaction product with chlor-2-human xypropyltrimethylammonium chloride, Dliil==0. O
i), oxidized potato starch O hydroxypropyl ether and KII according to Example 1 of 25JJO urea, say
Add the silicone-based commercial defoamer of I and stir to evenly distribute. Stir for 15 minutes after heating to 70-80'C, followed by cooling to about 4o-so'c and 0.1 j
Add ro 1,2-benzisothiazolin-3-one and the amount of water to make a positive #500 IIK.

The product so obtained is JIJ4Q in 50t
, Goo Pa, has a Brookfield viscosity of s.

It is suitable for labeling cold and hot bottles with high speed machines with adhesive pump and heating section.

Example 9 Carboxymethyl methyl cellulose (degree of substitution = 27-29 wt. methoxy groups, 2-5 wt. (
2o C, 20 rpm) = approx. 2,000 mPa, s
), 45.8 IC) noise starch, 1sI cationic starch ether (see Example 1), 176 g oxidized potato starch hydroxypropyl ether (see Example 1)
A commercially available antifoaming agent was added to the mineral oil No. 211, and the mixture was stirred in a well until the carboxymethylmethyl cellulose was completely dissolved. At this time, the other substances mentioned above are suspended 11 0-order 401i urea and 1゜IiO
Add sodium nitrate. These are dissolved under constant stirring.

After heating to 80°C and stirring for 20 minutes, cooled to 40°C, 0.21i of 1,2-benzisothiazoline-3-
On and net 400! ! Add amount of water until.

The product obtained has a temperature of 80°C at 20°C. It has a Brookfield viscosity of OOOmPa,s and is characterized by high storage stability. It is suitable for mechanically labeling cold to warm bottles in high speed machines with an adhesive pump and no heating section.

For comparison purposes, first, starch was dissolved as described above, and after cooling to 50°C, carboxymethyl methyl cellulose was added and stirred.

A product is obtained which invariably becomes viscous within a few days, which becomes uneven within a week.

Example 10 599 cationic potato starch according to Example 1, 50 g of polyvinyl bitetraridone (
Hydroxylp-tetrabyl ether of oxidized potato starch according to Example 1 (molecular weight approximately 40,000), 176 gos is distributed in the cold and stirred slowly until the polyvinylpyrrolidone is dissolved. The other ingredients are homogeneously dispersed but not dissolved but suspended. Commercial defoamers based on mineral oil 2
After addition of 1, heat at 9G to 95°C for 20 minutes. Approximately 50
Cooling to ℃ 1c, 409 urea, 10j sucrose and 0
．． Add 61 portions of 1,2-benzisothiazolin-3-one in batches.

After cooling the product so obtained to 50°C, 2
Addition of 0% urea solution to a solids content of 46.5% (according to the bending needle) produces approximately 55,00 o at 20°C.
mpa, go Fultsk 7 (- has a viscosity, it is
It is particularly suitable for the rapid labeling of moderately cold (15-20 DEG C.) and warm bottles in automatic machines having an adhesive pump but without additional heating means.

Continuation of page 1 Priority claim @February 13, 1982 ■West Germany (DE
)■P3205211.1 ゛■February 1, 1982
3rd ■ West Germany (DE) ■ P3205210.3 0 Inventor Reinel Hasenkampf Federal Republic of Germany Erklade 2 Alte Körner Strasse 8 0 Inventor Heinrich Merkeldeutsche Federal Republic of Erklade Stahlhausener Strasse 30

Claims (1)

[Claims] In aqueous adhesive mixtures based on starch derivatives containing t viscosity modifiers and optionally other customary additives, (IL) the average degree of substitution (hereinafter referred to as Ml, ) is 0
．． (b) a water-soluble cellulose anchor conductor, a synthetic water-soluble poly! -, casein, and aqueous starch derivatives different from (SL);
An adhesive mixture comprising at least one of -y- compounds. 2 M8 with starch adhesive component (&) smaller than 0.1
An adhesive mixture according to claim 1 having the following properties: - Measured with Rheomart 15 Shiso 40 ~ 20011P&, -
The adhesive mixture according to claim 1 or t2, having a dragee viscosity in the range 110. 4. Multiple types of human-xyalkyl starch as starch ether (a)! An adhesive mixture according to claim 1, 2 or 0S, comprising a mixture of derivatives. (v) Claims 1 to 3 which contain an oxybupyl starch derivative having an M8 of 0.05 to 0.1 as the component (&)
Adhesive mixture according to any one of clause 4. 4 Component (a) is added to the finished pressure adhesive mixture in an amount of 1
Adhesive mixture according to any one of claims 1 to 5, in an amount of 5 to 50% by weight. 2. The adhesive mixture according to any one of claims S-1 to E-6, wherein component (b) can be molded in a smaller amount than component (a). a. As component (1)), carboxyalkyl starch, cationic group-containing starch conductor and/or dextrino, vinyl alcohol, vinylpyrrolidone, optionally substituted acrylamide, acrylic acid and/or methacrylic acid polyester! -and/or copoly! - or water-soluble salts thereof, carboxymethyl heptylcellulose or mixed ethers thereof, water SaW, hydroxyalkyl cellulose and/or mixed ethers thereof. An adhesive mixture according to any one of the above. 9. Any of claims 1 to 0S, which contains a known low molecular weight compound for rounding to adjust the ease of rolling, in an amount of 2 to 20% by weight based on the finished round wire adhesive mixture. The adhesive mixture described in . 1α Adhesive mixture according to any one of claims 1 to 9, which contains natural starch, agents, antifoaming agents and/or preservatives as customary additives. 1t, the total solenoid content is about 30-60% by weight, and the Brookfield viscosity is about 20,000-2'OQ,
Adhesive mixture according to any one of claims 1 to 9, which is OOOmPa, s. An aqueous adhesive mixture based on (a) an average degree of substitution (hereinafter referred to as M8) of 0.
(b) water-soluble cellulose derivatives, synthetic water-soluble polyesters;
In a method of making an adhesive mixture comprising at least four selected polymeric compounds selected from the group consisting of casein and a waterborne sludge aS conductor different from (-), the sludge adhesive component A manufacturing method characterized by dissolving (a) in an aqueous solution of a polymer compound (-), optionally with heating.