DE2710325A1 - SOLID PASTE - Google Patents

Description

Various solid / pastes are known that can be used under normal conditions have a waxy or gel-like consistency. You can, for example, by mixing a water-soluble Adhesives »such as starch, starch or cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone, Vinyl methyl ether-maleic anhydride or vinyl alcohol-crotonic acid copolymers with Water, a water-soluble organic solvent and a gelling agent such as a salt of a fatty acid or benzylidene sorbitol, and then allowing the resulting mixture to solidify will.

The known solid pastes, however, have the disadvantage that they do not give a satisfactory uniform layer

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let it apply, soften too much in the heat, stick badly to heavily sized paper and the painting after Drying easily cracks and deforms.

The invention is based on the object of providing a solid paste based on an adhesive, water or a water-miscible paste organic solvent as well as a gelling agent that spreads on a carrier to form a uniform Layer can be easily applied, which does not soften too much in the heat, also sticks well to heavily sized paper and none after application to a support and drying

does not crack or crack and deform / deform. This task .

is achieved by the invention.

The invention thus relates to the subject matter characterized in the claims.

Pullulan is a polymer of oc-1,6-linked maltotriose, a trimer of glucose. It has the following structural formula:

CH ₂ OH CH ₂ OH CH ₂ OH

oT-CH, CH ₂ OH CH ₂ OH

0- ^r

O CH ₂ CH ₂ OH CH ₂ OH

η is an integer that has a value from 20 to 10,000

can.

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Pullulan is known as a water-soluble, slimy product. For example, from JA-AS 33 824/75 and JA-OS 99 341/74 and the corresponding US-PS 3,873,333 known that pullulan and pullulan derivatives as a paste for Textile fabrics or paper have good adhesiveness.

The present invention is based on the finding that when using pullulan and / or a pullulan derivative as Adhesive component for the production of a solid paste, especially the strength of which can be significantly improved.

In contrast to the known pastes, the paste of the invention can be applied very easily and in a uniformly thin layer. wear. The paste shows practically no toughness. Furthermore, it is firm and can still be applied easily. The known pastes do not have such properties. Adhesives based on polyvinyl alcohol have excellent strength, but this limits them application. Pastes made of, for example, starch or Polyvi Nylpyrrolidon have insufficient strength, so that they cannot meet the requirements for strength and breadth of application at the same time.

In the preparation of the paste of the invention, the cooling time required for solidification can be determined by suitable ones Choice of the degree of polymerization of the pullulan used and control its amount. For example, if you have a 90 ⁰ C

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If hot liquid paste with polyvinylpyrrolidone as an adhesive is allowed to cool to room temperature, it loses its flowability within 10 minutes and it solidifies. Under the same conditions, a pullulan with a molecular weight of 280,000 as an adhesive-containing paste solidifies within 4 minutes. This property offers advantages in terms of production and processing.

The known solid pastes made from water-soluble substances, such as starch or polyvinyl alcohol, are affected by the ambient temperature strongly influenced. During the summer months they lose their toughness and they have to be used in too large quantities will. During the cold season, their hardness increases, which makes them difficult to process. The paste of the invention with a pullulan or pullulan derivative does not have these disadvantages and their hardness is determined by the ambient temperature influenced to a lesser extent. Furthermore, the solid pastes of the invention are, to a lesser extent, time dependent Increase in hardness, as in the case of polyvinyl alcohol as pastes containing adhesive is the case. Their properties are over a much longer period of time stable than with pastes containing polyvinyl alcohol.

The pullulan used in the present invention can be prepared, for example, by the process described in US Pat. No. 3,827,937. A pullulan-producing strain of Pullularia pullulans is grown for 5 days at 24 ⁰ C in a nutrient medium that contains 10 % partially saponified starch, 0.5 % K ₂ HPO ₄ , 0.1 Si cooking

l_ salt, 0.02 % MgSO ₄ .7H ₂ O, 0.06 % ammonium sulfate and 0.04 # _l

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Contains yeast extract. The nutrient medium contains glucose as a carbon source. Pullulan is excreted as a sticky substance from the cells into the culture broth. The culture broth is freed from the cells by centrifugation and the supernatant is poured into methanol. The resulting precipitate is purified several times by dissolving it in water and precipitating it with methanol. After washing with methanol and drying, pullulan is obtained in a yield of 60 to 70 %, based on the Saccharic! Used. The molecular weight of the pullulan used according to the invention can be in a relatively wide range. It is preferably at least 10,000 to 5,000,000, in particular 50,000 to 1,000,000.

As pullulan derivatives come for the purposes of the invention in particular Pullulan ester and pullulan ether in question. Their production is in the JA-OS 83 779/1974 and 112 954/1974 described. The pullulan ester can by reacting pullulan with an acid anhydride or an organic halide or inorganic acid or an ester of these acids. Examples of pullulan esters that can be used are the esters with lower fatty acids, such as pullulan formate, acetate and butyrate, as well as the esters of higher fatty acids such as pullulan laurate and palmitate. examples for Inorganic acid esters are pullulan sulfate and pullulan phosphate. The pullulanethers can be achieved by implementing Pullulan can be made with an epoxy or halide. Specific examples are pullulan ethyl ether, pullulan hydro-

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xyethyl ether, pullulan hydroxypropyl ether, pullulan carboxymethyl ether and pullulan diethylaminoethyl ether. The solubility of the pullulan derivatives in solvents depends on the degree of substitution. According to the invention, any pullulander can vat can be used so long as it is soluble in the solvent used for preparing the solid paste of the invention is.

The pullulan and / or pullulan derivative can be used either in part or alone as an adhesive in the solid pastes of the invention be used. Examples of additionally usable adhesives are starch, cellulose derivatives, polyvinyl alcohol, Polyvinylpyrrolidone, salts of polyacrylic acid, vinyl methyl ether-maleic anhydride copolymers and ethylene-acrylic acid copolymers.

A mixture of water and a water-miscible organic solvent is used as the solvent for producing the paste. Examples of the organic ones that can be used Solvents are alcohols such as methanol, ethanol and isopropanol, polyhydric alcohols such as ethylene glycol, propylene glycol and glycerol, ethers such as ethylene glycol monomethyl ether and monoethyl ether, and dioxane, dimethylformamide and

Dimethyl sulfoxide. 25th

For the preparation of the paste of the invention, any substance can be used as a gelling agent provided it is in the presence of the mixture of the components listed above

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Forms gel which melts at elevated temperature and which gives strength to the paste at the application temperature. Specific examples of usable gelling agents are benzylidene sorbitol and benzylidene xylitol obtained by reacting sorbitol

⁵ or xylitol can be obtained with benzaldehyde, as well as salts of higher aliphatic carboxylic acids, such as stearic acid or palmitic acid. Dibenzylidene sorbitol and dibenzylidene xylitol are particularly preferred.

To produce the solid paste of the invention, at least the four ingredients listed in claim 1 must be mixed with one another, namely the adhesive including pullulan or pullulan derivative, water, water-miscible organic solvent and gelling agent.

These four ingredients can be mixed together in a relatively wide range of blends. That The proportion depends on the type of adhesive and the gelling agent as well as the intended use of the solid paste away. In general, the four components are as follows

²⁰ quantity ratio before:

(1) Adhesive 10 parts by weight

(2) water 5 to 40 parts by weight

(3) organic solvent 5 to 60 parts by weight

(4) Gelling agent 0.2 to 20 parts by weight.

To produce the paste of the invention, the constituents can be mixed with one another in a conventional manner. Usually, the mixture is at temperatures of 70 to 100 ⁰ C in a screw kneader or paddle mixer to a liquid

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mixed, which is then filled into containers and allowed to solidify. The molten liquid can also be extruded through a nozzle. The extrudate is allowed to solidify. During the mixing of the four ingredients, further ingredients can be added, for example dyes, fragrances, fillers and customary auxiliaries.

The examples illustrate the invention. Parts relate

based on weight, unless otherwise stated. 10

example 1

A mixture of 30 parts of dimethyl sulfoxide, 25 parts v / ater, 10 parts of pullulan of a molecular weight 143 000 and 2 parts of dibenzylidenexylitol was heated for 1 hour at 90 ⁰ C and stirred. The homogeneous solution obtained is filled into cylindrical vessels similar to a lipstick container. These vessels have a diameter of 14 mm and a height of 50 mm. The contents are allowed to cool to room temperature. Solidification begins within about 3 minutes.

The solidified paste is applied to Kraft paper by pressing lightly. The paste can be easily applied without pulling, forming an evenly thin layer. The initial bond strength is very satisfactory. The paste retains its firm consistency over a relatively wide temperature range and changes its hardness only slightly.

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1 example 2

Aue 20 parts of dimethyl sulfoxide, 7 parts of ethanol, 20 parts Water, 5 parts polyvinyl alcohol (degree of saponification 87 #, Degree of polymerization 1400), 8 parts of polyvinylpyrrolidone from Molecular weight 360,000, 8 parts of pullulan with a molecular weight of 280,000 and 2 parts of dibenzylidene xylitol are used as described in Example 1 to produce a solid paste. This paste united inherently excellent strength and application properties and shows good initial adhesive strength. 10

Example 3

According to Example 1, 20 parts of dimethyl sulfoxide, 10 parts of ethylene glycol monomethyl ether, 25 parts of water, 10 parts of pullulan with a molecular weight of 10,000, 5 parts of polyvinyl alcohol ( degree of saponification 87%, degree of polymerization 1400), 5 parts of polyvinylpyrrolidone with a molecular weight of 360,000 and 2 parts of dibenzylidene sorbitol become a solid Glue paste made.

20 Example4

According to example 3, a solid adhesive paste is produced, However, a pullulan with a molecular weight of 143,000 is used.

25 example?

A solid adhesive paste is produced according to Example 3, but a pullulan with a molecular weight of 280,000 used.

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1 examples

A solid adhesive paste is produced according to Example 3. However, a pullulan with a molecular weight of

600,000 used.
5

Example 7

A solid adhesive paste is produced according to Example 1, but the pullulan is produced by an acetylated pullulan Molecular weight 100,000 and a degree of substitution of 0.5 used.

Example 8

A solid adhesive paste is produced as in Example 1, but instead of pullulan, a hydroxyethylpullulan is used with a molecular weight of 100,000 and a degree of substitution of 0.2 were used.

All solid pastes prepared according to Examples 3 to 8 combined excellent strength and application properties. With increasing molecular weight took place faster solidification of the melt on cooling. This characteristic property of pullulan allows one easy control of the solidification time of the melt.

^25th Comparative example A.

A solid paste is produced according to Example 1, but 10 parts of dextrin are used instead of 10 parts of pullulan. When applying the solid paste to kraft paper

l_ followed crack formation. There was an even application of the paste

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not possible. It was also difficult to apply the adhesive paste to small areas of the paper. The initial adhesive strength of the paste was insufficient. The paste showed a marked change in strength with temperature. At ⁰ ° C scraps education and granule formation occurred while occurred at 40 ⁰ C complete soften and lose their original form.

Comparative example B

A solid paste is produced as in Example 1, but instead of 10 parts of pullulan, 10 parts of polyvinyl alcohol (degree of saponification 87 #, degree of polymerization 1700) are used. When applying the solid adhesive paste to Kraft paper, it could not be applied evenly due to its excessive hardness and rubber-like elasticity. Furthermore, their initial adhesive strength was insufficient. At 0 ^° C. it had too great a hardness, so that a uniform layer could not be obtained when applied to Kraft paper. At 40 ^° C. it exhibited elasticity similar to rubber, so that the adhesive layer as a whole could easily be deformed.

Comparative Example C

According to Example 2, a solid paste is produced, however no pullulan is used. The solid paste deforms into granules when it is applied and shows neither uniform applicability nor good strength. Their initial adhesive strength is poor.

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1 Table Ϊ summarizes the properties of the adhesive pastes produced in the above manner.

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Table I.

at • Initial HaJ 40
sec 50
sec rtfesi iiekeit ^ ¹ ' 120
sec Hardness £ ²⁾ Temperature- To whom Strength ^ t mistake game 20th
sec 30th
sec Δ ο 60
sec 90
sec O dyn / cm (dvn / cm / de «) dungs
proper /, N
stocks ^ ' Mushrooms 4O ⁰ O 1 X X O ο 0 O O 4.8 χ 10 ⁶ 0.7 χ 10 ⁵ O O ⁰ C O 2 X Δ Δ O O O O 5.5 0.6 ® O O 3 X χ O O O 0 O 3.7 0.7 O O O σ
( rt 4th X Δ O O O 0 O 4.7 0.6 ® O O OO
co 5 X Δ Δ O O C. O 4.9 0.6 © O O -J 6th X X Δ O O O O 5.4 0.6 O O O CD
CO 7th X X Δ O O O O 5.0 0.6 ® O O K) 8th X X χ X O O O 4.9 0.6 O O O A. X X χ X Δ O O 3.0 1.1 X O 86 B. X X χ Δ Δ. O O 7.2 1.0 X 1? 74 C. X X O O 4.3 1.1 Δ 21 19th 8th

(1) The initial bond strength is determined as follows:

A certain amount of the adhesive paste is applied to Kraft paper at 25 ° C and a relative humidity of 60 # and a load of 30 kg applied. The bond is then quickly peeled off. The characters X, Δ and 0 means peeling off the paste layer, beginning peeling off of the paper layer and complete peeling off the paper layer.

(2) To determine the hardness, a sample with a diameter of 14 mm and a height of 45 mm is used at 25 ^° C. and 60 % relative humidity determined by means of a needle with a diameter of 1.5 mm in a rheometer of the RUD-J type.

(3) The application properties are determined as follows:

A stick of the solid paste is laid on using Kraft paper applied to a load of 800 g. The paper is then pulled off at a speed of 5 mm / sec. The appearance of cracks or cracks is observed. The characters ©, O »Δ and X mean very good,

good, moderate and bad behavior. 25th

(4) The strength is determined as follows:

100 containers for glue sticks, which are filled with the solid adhesive composition can be, for 7 days at O ⁰ C and 40 ⁰ C L 709837/0942 J

ditched. Then the part of the glue stick which has the screw, each rotated 10 times with a motor. The number of defects is measured, including shredding, cracking and poor filling properties. This number is printed out in percentages.

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Claims (1)

SUMITOMO CHEMICAL COMPANY, LIMITED Osaka, Japan and 10 HAYASHIBARA BIOCHEMICAL LABORATORIES, INC. Okayama, Japan "Solid paste" Priority: March 11, 1976, Japan, No. 26 680/76 Claims 1. Solid paste based on an adhesive, water, a water-miscible organic solvent and a gelling agent and optionally with a content of a dye, such as fragrance, filler and customary auxiliaries, characterized in that the adhesive is either partially or solely pullulan or a pullulan derivative. 2. Solid paste according to claim 1, characterized in that the pullulan has a molecular weight of at least 10,000. 709837/0942 _j ORIGINAL INSPECTED 3 · Solid paste according to claim 1, characterized in that the pullulan derivative is a pullulan ester or ether. 4. Solid paste according to claim 1, characterized in that the additional adhesive starch, a cellulose derivative, polyvinyl alcohol, polyvinylpyrrolidone, a salt of polyacrylic acid, a vinyl methyl ether-maleic acid copolymer or is an ethylene-acrylic acid copolymer. 5. Solid paste according to claim 1, characterized in that the water-miscible organic solvent is methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol, Ethylene glycol monomethyl ether or monoä thy lather, Oioxan, Dimethylformamide or Dlmethylsulfoxid or a mixture of 15 is at least two of these solvents. 6. Solid paste according to claim 1, characterized in that the gelling agent benzylidene sorbitol, benzylidene xylitol or a Is the salt of stearic or palmitic acid. 7. Solid paste according to claim 1, characterized by a Content of 10 parts by weight of adhesive, 5 to 40 parts by weight of water, 5 to 60 parts by weight of organic solvent and 0.2 to 20 parts by weight of gelling agent. 709837/0942