DE1812416A1 - Process for gluing paper and its product - Google Patents

Description

Process for gluing. Paper and its product

The invention relates to a method for sizing paper and its product.

The invention is based on the object of improved glues which, when used in the manufacture of paper, result in a paper which has reduced water and ink absorption and is also resistant to aqueous acidic and alkaline solutions. Glues should also be used that are suitable for All types of paper fibers can be used throughout the pH range that is normally used during various processes Papermaking occurs.

Under "paper" and "cardboard", sheet-like masses and Shaped articles are understood to be those made from fibrous cellulosic materials are made, which can be natural as well as synthetic Ur Sprungs's. This also includes leaf-like Bulk and molded articles made from combinations of cellulosic and non-cellulosic materials made from plastics such as polyamide, polyester and polyacrylic resin fibers as well as mineral fibers such as asbestos and glass.

Paper and cardboard are often glued with different materials in order to ensure their resistance to water and other aqueous materials Solutions to increase. These materials are called sizes, and they can be added during the actual papermaking process what is known as internal moisturizing or machine gluing. On the other hand, the glues can also be used on top of the finished Web or finished sheet, known as outer or surface gluing.

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Various water-repellent or hydrophobic materials "" are used as glue. These include rosin, fortified rosin, mixtures of rosin with waxes, wax emulsions, Ketene dimer emulsions, fluorocarbons, fatty acid complexes of chromium or aluminum chloride, long-chain thermoplastic copolymers as well as some thermosetting condensation resins. Although these materials can be used under certain conditions, their use is subject to one or more restrictions.

For example, rosin, although relatively cheap and readily available, has poor resistance to alkaline solutions and cannot be used for sizing neutral or alkaline pulp. It cannot therefore be for the latter can be used as it must normally be used in conjunction with alum or an acidic aluminum ion donor that is present is to the metal rosinate, i.e. the rosin soap precipitate and harden the fibers. However, the use of alum for this purpose is for neutral or alkaline pulp locked out. This is a serious disadvantage because paper is made from neutral or alkaline pulp has higher strength, greater stability and better aging properties than paper made from acid pulp. The indoor use of alkaline dyes such as calcium carbonate is also excluded. The same limitation also applies the use of most wax emulsions too, which cannot be used for alkaline pulp as they normally do with small amounts of alum used to break up the emulsions. On the other hand, certain glues don't allow strong acidic conditions. Furthermore, certain glues may not be sufficient are retained in the sheet during sheet formation, which is why they are only suitable for external or surface application.

In addition to the pH restrictions just noted, water resistance, or water resistance, is common with many of the Glues used up to now are inadequate for many purposes where the paper or cardboard is exceptionally water-resistant must be. On the other hand, some glues lead to complete water repellency in contrast to the desired water resistance. Many of these glues are also incompatible with dyes, fillers, or other additives that are often the

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Paper can be added. Another disadvantage of some sizes is that they require a considerable degree of heat curing is to develop the full effect. Therefore, when using these sizes, the full effect and the full size value cannot be achieved immediately after the formation and drying of the paper web can be achieved. Furthermore, high concentrations of some sizes lead to an undesirably low coefficient of friction for the paper.

The invention specifies the use of certain substances as sizes for paper and cardboard, which are used for the production of Paper and cardboard products that have an unusually high Show water resistance with simultaneous resistance to acidic and alkaline solutions. Of particular importance is that Fact that the successful use of these new glues is not is limited to any particular pH range so that its use in the treatment of neutral and alkaline pulp just as is possible from acid pulp. Another advantage of these glues is that they can be used together with others Gluing can be used to achieve additional gluing effects. Another advantage of these glues is that they don't affect the strength of the paper and, when used with certain additives, even increase the strength of the finished sheets. An additional advantage of the glue according to the invention is expressed in that only mild drying and curing conditions are required to develop the full glue value.

The glues according to the invention have the formula

CH Y '

N-CH-CH

Z-CH X Y,

where X is a radical which is hydrogen, a cyano or a substituted one Carboxyl radical with the formula

Il

-C-OR

where R is an alkyl group having 8-22 carbon atoms;

*) (usually cyano)

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Y is a radical which is a cyano radical, a substituted one Keto, i.e. Carbonyl-RaditeL with the formula

-CR
or a substituted carboxy radical with the formula

0
dd

-C -OR

where R for each of the last two radicals is an alkyl group with 8-22 carbon atoms;

Y ^{1 is} a radical which is a hydrogen radical, a cyano radical, a substituted keto, - ie carbonyl, radical with the formula

0
ti

- C -'r

or a substituted carboxyl radical having the formula

I!

-C-OR

where R for each of the last two radicals is an alkyl group having 8-22 carbon atoms; and Z is a radical that is a hydrogen radical or an alkyl radical having 1-2 carbon atoms.

The processes for making the above-identified N-substituted Aziridine compounds are already known. In general, these manufacturing processes involve the reaction of a Alkylenimines with a carbonyl-substituted alpha-beta-ethylenic unsaturated compound such as an alkyl acrylate ester, a Dialkyl maleate ester or a vinyl ketone. To the applicable Alkylenimines, which can be used for the latter reaction, include ethyleneimine, propyleneimine, and butyleneimine. Suitable ethylenically unsaturated compounds containing carbonyl are alkyl esters of acrylic acid and dialkyl esters of maleic acid, the alkyl groups of the last two types of esters being 8-22 carbon · Contain atoms, as well as vinyl ketones. Examples of the latter substances are: lauryl, stearyl and dodecyl acrylate; Dilauryl, Dipalmityl and distearyl maleates as well as mixtures of the latter maleates; and stearyl vinyl ketone. Details about this

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For example, response operations can be found in an article by Rosenthal et al in the Journal of Organic Chemistry, 30, 3689 (1965).

The actual use of the sizes according to the invention in papermaking can be carried out in the most varied of ways and the modes of application can again be according to the practical needs can be modified. It should be noted, however, that in all of these procedures it is very important is to achieve a uniform dispersion of the glue in the pulp. A uniform dispersion can be achieved by adding the glue in fully dispersed form such as an emulsion or by adding Adding chemical dispersants to the glue or pulp can be achieved.

Another point, if you want when using the glue according to the invention has to be considered relates to their use together with a material which is either more cationic Nature or otherwise capable of ionizing or dissociating in such a way that one or more cations or other positive ones Charge carriers are generated. These cationic agents, as they are to be mentioned below, are useful in making the glues to hold according to the invention and to bring them into close proximity to the pulp fibers. As the cationic agent, the following can be used Substances used are: long-chain fatty amines; Polyamines; Polyacrylamide; Polyethyleneimine and its derivatives; Copolymers of ethyleneimine with various monomers such as diethylaminoethyl methacrylate; Chromium sulfate; Sodium aluminate, animal glue; cationic thermosetting resins such as the reaction products of two basic carboxylic acids, polyalethylene polyamines and epihalohydrins; as well as polyamide polymers and copolymers. Various cationic starch derivatives are of particular interest as a cationic agent including primary, secondary, tertiary or quaternary amine starch derivatives and other cationic nitrogen substituted Starch derivatives such as cationic sulfonium and phosphonium starch derivatives. The production of such cationic starches is described in particular in US Patents 2,813,093, 2 989 520 and 3 077 i * 69. Such derivatives can be made from all types of starch including maize, tapioca, potato, waxy maize, Wheat and rice are produced. They can also be used in

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their original granular form or in pre-gelatinized, cold water soluble products be converted »

One of the above cationic agents can be added to the core, i.e. the pulp, either before, during or after the addition of the glue can be added. However, to ensure the best possible distribution To achieve this, the cationic agent should be added either immediately after or directly with the glue. That actual addition to the core of the cationic agent or size can occur at any time during papermaking before the final conversion of the wet pulp to a dry sheet or sheet. Hence can E.g. the glues according to the invention are added to the pulp, while the pulp is in the upper box, in the chopper, in the water pulping device or in the Bütteneinrichtung.

To enable good gluing, it is desirable to that the sizes according to the invention are uniformly dispersed in the pulp with the smallest possible particle size. A procedure making such uniform dispersions consists in emulsifying the glue prior to using it to add it to the core either mechanical devices such as high-speed agitators, mechanical homogenizers or ultrasonic homogenizers or by adding a suitable emulsifying agent. The latter emulsification can if desired by using the cationic agent "can be used as an emulsifier, which is particularly effective when cationic starch derivatives are used. which can be used as emulsifying agents for the sizes according to the invention include hydrocolloids such as common starches, non-cationic Starch derivatives, dextrins, carboxylmethyl cellulose, hydroxyethyl cellulose, Gum arabic, gelatin and polyvinyl alcohol as well as various surfactants. If such non-cationic emulsifiers are used, a katior Chemical agent can also be added to the paper pulp. In the Production of these emulsions with the help of an emulsifying agent must first disperse this in water, after which the glue under vigorous Stirring is added. .

A further improvement in the water resistance of the paper, that is produced by the glues according to the invention

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can be achieved by drying the finished webs, sheets or molded products. This drying comprises heating the paper to temperatures of 80-15O ⁰ C for 1-60 minutes. It should be pointed out, however, that subsequent drying is not necessary for the gluing to be carried out successfully.

The glues according to the invention can be used successfully for gluing paper made from all types of cellulose and combinations of cellulose with non-cellulose fibers is. Cellulose fibers that can be used include bleached and unbleached sulfate (KrafiJ-, bleached and unbleached sulfite, bleached and unbleached soda, neutral sulfite, semi-chemical, chemically ground wood, ground wood and any combination of these fibers. These names refer to wood pulp fibers produced by various processes which are known in pulp and paper technology can be produced. Synthetic fibers made from viscose rayon can also be used or regenerated cellulose as well as of the chemically synthetically produced kind.

All kinds of dyes and fillers can be used in the paper be added to be sized by the sizes according to the invention. These include clay, talc, titanium dioxide, calcium carbonate and diatomaceous earths. Other sizes can also be used together with the sizes according to the invention.

Regarding the proportion, it should be noted that the sizes according to the invention in amounts of about 0.05 to about 5.0% of the Dry weight of the pulp in the finished sheet or web can be used. Within this range depends the exact amount to be used will depend, in large part, on the type of pulp being used and the particular process conditions as well as the intended use of the paper. For example, if paper has good water resistance or should be ink-fast, must have a higher concentration ::, The glue can be used as for paper used for purposes where only a small amount of glue is required. These considerations apply to the amount of the cationic agent as well valid, which can be used together with the glues according to the invention. Therefore these substances can be used in practice in any concentration may be used, which prove to be applicable to the speci-

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express procedural conditions. However, under normal conditions, it should be in the range of about 0.5-2.0 parts by weight of the cationic agent per 1.0 part of the glue will usually be sufficient. Therefore, the cationic agent can be used in an amount be present which is at least 0.025% by dry weight of the pulp in the paper.

It can also be seen that the sizes according to the invention either in the form of an aqueous emulsion or in an organic solvent loosened, applied externally to the paper by any conventional surface sizing process, e.g. by Butten, calender or size press glues. These surface glue systems may also include any of the cationic and non-cationic agents mentioned above, as well as other common ones Paper additives.

In any case, the use of the substances according to the invention for the manufacture of paper and cardboard products gives them a water resistance comparable to the results that have been obtained with other glues so far, or even surpasses these results. Furthermore, the glue according to the invention has a resistance to acids and Leaches are given that can hardly be achieved with other glues.

The invention is based on the following exemplary embodiments explained. In these exemplary embodiments, all parts given are parts by weight, unless otherwise stated.

Embodiment I.

This example explains the use of a typical Glue according to the invention in the form of an aqueous solution in which a cationic agent is used as the only emulsifying agent. This exemplary embodiment also indicates the improved properties of the paper that is produced with the sizes according to FIG Invention has been glued.

An aqueous emulsion of the glue, which was the reaction product of ethylene imine and distearyl maleate _s was prepared "by first 7.5 parts of Beta-Diäthylaminoäthylchloridhydrochloridäthers of corn starch, the preparation of the US patent is 2,813,039 described in Embodiment Example I, in 85 parts of Water was boiled, which was heated in a boiling water bath '. After boiling for 20 min, the dispersion of the cationic

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The starch derivative is cooled to room temperature and then transported into a high-speed stirrer, with 7.5 parts of the above glue was slowly added to the stirred dispersion. The stirring lasted 5 minutes, and the resulting The emulsion was then diluted by adding a further 900 parts of water. A final 10-fold dilution was made and the emulsion was then added to an aqueous slurry of bleached softwood kraft. Sheets were accordingly molded and dried to the TAPPI standards, the latter Sheets related to 1% of both the glue and the cationic agent based on the weight of the thick pulp. The same procedure made another number more comparable Sheets made each containing different amounts of glue.

The water resistance of the resulting sheets was then determined by the uranium stain test and the ink penetration test. The uranium stain test consists of applying a small amount of Üranin dye powder on top of a strip of test paper, which is then placed floating on distilled water. if the water is absorbed by the paper, the dye becomes humidified and therefore sensitive to ultraviolet light. The time in see for this ultraviolet sensitivity to occur is therefore directly related to the water resistance of the paper, since the larger the The water resistance of the paper is, the more the wetting of the dye that is on the top of the paper is delayed has been applied.

The ink penetration test involves floating a strip of the treated paper in an ink container. The time it takes for the ink to penetrate the paper so that it is visible on more than 50% of the area of the top of the paper strip is called the ink penetration time. The greater the ink permeability, the greater the water resistance of that part of the paper sample.

■ The following table shows the results after examination of the various paper sheets were obtained by the latter test method.

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Ί812ΑΊ6

glue catxonic Uranium dye Ink flow £% based on Mean [% related test urgent test Weight of on weight of the [secj jsecj dry fiber dry PspLer- porridge sj breisj 0.25 0.25 76 2000+ 0.50 0.50 91 2000+ 0.75 0.75 101 2000+ 1.00 1.00 108 2000+ 3.00 3.00 186 2000+ 0.00 (control) o, 00 0 0

The results summarized above clearly show the very good water resistance of the paper sheets treated with the sizes according to the invention.

Embodiment I I

This embodiment explains the use of additional Glues according to the invention in the form of aqueous emulsions in which a cationic agent is the only emulsifying agent was used. It also illustrates the improved properties exhibited by sheets of paper which have been sized with the sizes according to the invention.

Aqueous emulsions of the sizes used in this embodiment were prepared according to the emulsification method of embodiment I. The cationic agent in all cases was beta-diethylaminoethyl chloride hydrochloride ether of corn starch. Sheets of paper that were internally sized with the appropriate emulsions were subsequently made accordingly manufactured and dried according to TAPPI standards; The water resistance of the resulting leaves was then assessed by the uranium staining test determined by embodiment I.

The proportion of the different glue systems also xvie the The degrees of water resistance exhibited by the paper sheets produced thereby are given in the following table ben:

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glue

Glue [% based on the weight of the dry paper · tereisj cationic agent [% based on weight of dry pulp]

Uranium dye test [see]

control

Reaction 0.50 product of ethyleneimine and stearyl acrylate fdto 1.00 0.50

1.00

0 58

91

Reaction product of ethyleneimine and di-n-octyl maleate 0.50

62

dto.

1.00

Reaction 0.50 product of propyleneimine and an equal molar Mixture of distearyl and dipalmityl maleate

ditto 1.00

Reaction product of butylene imine and didoeicosyl maleate ditto 1.00 1.00 0.50

1.00 0.50

98 90

105

1.00

110 *

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Reaction 0.25 0.50 0.25 product of 1.00 Ethylene imine 0.50 and stearyl beta cyane___acrylate dto. 0.50 dto. 1.00 Reaction 1.00 0.50 product of 0.50 Ethylene imine and tue-n- dodecyl maleate dto. 1.00 Reaction 1.00 0.50 product of 0.50 Ethylene imine and Di-n-tetra- decyl maleate dto. 1.00 Reaction , 00 0.50 product of , 50 Ethylene imine and Hexadecylacry- lat dto. 1 1.00 Reaction 0 , 00 0.50 product of Ethylene imine and Stearyl vinyl ketone dto. i 1.00

43

105 108

70

100 80

104 60

95 50

90

The results given underline the extraordinarily good water resistance of the paper sheets with the glue were sized according to the invention.

909827713 50

Embodiment III

This embodiment explains the use of the sizes according to the invention in the form of aqueous emulsions, which with a non-cationic emulsifiers are made, as are the properties of the paper sheets made with these emulsion products have been glued.

The same emulsification method as in Embodiment I was used to make that described in this embodiment Produce core emulsion with the exception that slightly anionic, unmodified shark starch as an emulsifier for the ethyleneimine distearyl maleate glue instead of the cationic starch ether was used. The resulting emulsion was then either alone or together with the alum or together with the cationic Beta ethylaminoethyl chloride hydrochloride ether of corn starch used to glue the inside of sheets of paper made according to TAPPI standards. The alum and the cationic Starch ethers were added independently at the same time in papermaking that the size emulsion was added. The water resistance of the resulting paper sheets was then determined by the uranium dye test, which has already been explained for exemplary embodiment I. was measured.

The results obtained are shown in the following table:

% Based on glue more cationic. cationxian Uranium staining on weight of the additive Additional% related Test see dry paper on weight of the porridge dry paper porridge 0.25 without - 65 0.50 without - 88 0.25 alum 1.0 90 0.50
0.10 alum
more cationic
Starch ether 1.0
0.5 100
38 0.25
0.50 more cationic
Starch ether
more cationic 0.5
0.5 81
104

Starch ether

The results given show the good water resistance

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speed imparted to the paper by the use of the sizes according to the invention, regardless of the shape, in of which they were used, and the special additives that are also used may exist in the system.

The glue emulsion with the ethylene imine distearyl maleate product " and the corn starch emulsifier was also used for surface sizing used. The latter glue was applied from the outside by conventional size press gluing on a sheet of paper made of bleached Softwood kraft pulp made according to TAPPI standards had been. After drying, the resulting paper sheet showed that on the surface with 0.9% glue, based on the The dry weight of the paper pulp that had been sized had very good water resistance.

Claims

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Claims (1)

-15- 28.11.1968 EH / Kü My file: N-2292 Claims 1 Q 1? / 1 R 1. Method of sizing paper, in which in the wet pulp before the final conversion of the pulp into a dry web a glue is well dispersed, thereby marked that the glue has the formula Tk> ' Z-CH XY has, where X is a radical which is hydrogen, a cyano or a substituted carboxyl radical with. the formula If - C-OR where R is an alkyl group having 8-22 carbon atoms; whereby Y is a radical that is a cyano radical], a substituted one Keto radical with the formula Il - C-R or a substituted carboxyl radical having the formula ti - C - OR where R for the last two radicals is an alkyl group having 8-22 carbon atoms; whereby Y ^{1 is} a radical which is a hydrogen radical, a cyano radical, a substituted keto radical having the formula Il - C - R or a substituted carboxyl radical having the formula Il C - OR where R for the last two radicals is an alkyl group having 8-22 carbon atoms; and where 9 0 9 8 2 7/1350 is a radical that is a hydrogen radical or a
Alky! Radical with 1-2 carbon atoms. 2. The method according to claim!, Characterized in that the concentration of the glue in the
wet pulp is about 0.05-5.0% of the dry weight of the pulp. 3. The method according to claim 1 or 2, characterized in that that the glue is in the form of an aqueous emulsion. 4.- The method according to any one of the preceding claims, characterized in that prior to the final conversion of the paper pulp into a dry web, a cationic one
Agent with the glue is dispersed in the wet pulp. 5. The method according to claim! +, Characterized in chn e t that the concentration of the cationic agent is at least about 0.025% based on the dry weight of the pulp , amounts to. 6. The method according to claim 4 or 5, characterized in that that the glue is in the form of an aqueous emulsion in which the cationic agent is the primary emulsifier is. . Method according to claim ¹ ! , characterized by shows that the glue is in the form of an aqueous emulsion, in which a non-cationic agent is the primary
Is emulsifier. 8. Paper, made by a method according to any one of the preceding claims, with a well dispersed glue, characterized in that the glue.
the formula 909827/13 50 Γ ¹ ; "N-CH-CH Z-CH X has, where X is a radical which is hydrogen, a cyano or a substituted carboxyl radical having the formula Il - C - OR where R is an alkyl group with 8-22 carbon atoms is; whereby Y is a radical which is a cyano radical, a substituted keto radical having the formula I » - C - R or a substituted carboxy radical of the formula Il - C - OR where R for the last two radicals is an alkyl group having 8-22 carbon atoms; whereby Y 'is a radical that is a hydrogen radical, a cyano radical, a substituted keto radical having the formula Il - C - R or a substituted carboxyl radical having the formula Il - C - OR where R is the last two radicals of an alkyl group is of 8-22 carbon atoms; where Z is a radical which is a hydrogen radical or a Is an alkyl radical of 1-2 carbon atoms. 9. Paper according to claim 8, characterized in that the glue is present in a concentration of about O ₃ Ö5 - 5.0% of the dry weight of the paper pulp in the paper. 909827V1350 10. Paper according to claim 8 or 9, d a d. u r c h marked, that the paper also contains a well dispersed cationic agent. 11. Paper according to claim 9 or 10, characterized geken n- shows that the cationic agent is in a consensus approximately
Tration of at least / 0.025% based on the dry weight of the pulp in which the paper is present. 12. A method for gluing according to claim 1 of a previously prepared Paper web in which the glue is applied to at least one side of the paper web, characterized in that that the glue has the formula CH ₉ Y ^T N - CH - CH Z-CH XY, where X is a radical, hydrogen, cyano or substituted carboxyl radical with the formula Il - ■ C - OR where R is an alkyl group having 8-2 2 carbon atoms is j where "'. Y is a radical which is a cyan radical, a substituted keto radical having the formula o - ■■ - 11th C - R or a substituted carboxy radical of the formula It - - C - OR is, where R is for the last two radicals, one. Alkyl group is of 8-22 carbon atoms; whereby Y 'is a radical that is a hydrogen radical, a cyano radical a substituted keto radical having the formula. ■ 3 9098 27/13 50 Il - C - R or a substituted carboxyl radical having the formula ti - C - OR where R is an alkyl group for the last two radicals having 8-2 2 carbon atoms; whereby Z is a radical that is a hydrogen radical or an alkyl radical having 1-2 carbon atoms, and that then the paper web treated in this way is dried. 13. The method according to claim 12, characterized in that that the glue is in the form of an aqueous emulsion. 14. The method according to claim 12, d a d u r c h characterized, that the glue is in the form of a solution in an organic solvent. 15. The method according to any one of claims 12-14, characterized It is known that a cationic agent is applied with the glue on at least one side of the paper web will. 16. The method according to claim 15, characterized in that that the glue and the cationic agent are combined in the form of an aqueous emulsion. 17. The method according to claim 15, characterized in that that the glue and the cationic agent are in the form of a solution in an organic solvent be combined. 18. Paper with glue applied to at least one side has been characterized 909827 / .1350 that the glue has the formula CH ■ \ Z -CH N - CH - y « CH has, where X is a radical which is hydrogen, a cyano or a substituted carboxy! radical with the formula 0 ti -C-OR where R is an alkyl group with 8-22 carbon atoms is, where Y is a radical which is a cyano radical, a substituted one Keto radical with the formula Sl - C - R or · a substituted carboxyl radical with the oil Q κ -C- OR where R is an alkyl group for the last two radicals is of 8-22 carbon atoms; whereby Y ^! a radical is a hydrogen radical, a cyano radical Ke to kai, a substituted radical with the formula -C-R or · a substituted carboxyl radical with. the formula ti - C - OR where R is an alkyl group for the last two radicals is of 8-22 carbon atoms; and where Z is a radical that is a hydrogen radical or a Alky! Radical with 1-2 carbon atoms. 9827/13