EP0296971B1 - Continuous process for producing a printing/writing paper and perfumed product obtained - Google Patents

Abstract

The invention relates to a scented paper. This paper consists of at least one fibrous sheet and at least one surfacing coat comprising: - at least one sizing agent, - at least one binder, - at least one aromatic composition, - and optionally at least one additive. Application as paper for printing and/or writing.

Description

The present invention relates to a continuous process for manufacturing printing-writing paper in order to obtain a perfumed product bonded to inks, which allows very good printability.

Up to now, the manufacture of perfumed papers has been limited by the fact that the perfume compositions are essentially composed of oils which destroy the bonding to the inks of the paper and therefore make it very difficult to use for printing-writing.

• ― soit en incorporant le parfum dans les encres d'impression (document GB-A-1176262),
• ― soit en incorporant le parfum dans des microcapsules plastiques introduites dans le papier (document JP-A-50-06113).

The difficulty was therefore circumvented by isolating these oils from the paper:

• - either by incorporating the perfume into the printing inks (document GB-A-1176262),
• - or by incorporating the perfume into plastic microcapsules introduced into the paper (document JP-A-50-06113).

The technique of printing paper with inks containing perfume therefore requires an additional operation after the paper is made, outside the machine, and the incorporation, necessarily very superficial, of the perfume does not allow a high permanence of the fragrance.

Besides a relatively high cost, the microcapsule technique also requires an additional operation, since the microcapsules are generally introduced by coating. Finally, to develop its fragrance, the paper must be subjected to friction or a rise in temperature, necessary to burst the microcapsules.

In other paper applications, perfuming can be done by spraying on the paper sheet after manufacture. In addition to the fact that this technique involves a slow unwinding of the paper reel, the vaporized oils give an unpleasant feeling of greasy paper and considerably reduce the printability properties of the support.

• ― en lubrifiant les lames de la coupeuse avec des huiles essentielles,
• ― lors de l'emballage, en vaporisant le parfum sur le support en carton des rouleaux de papier ou sur quelques feuilles seulement par unité d'emballage. Ces papiers très poreux assurent une diffusion du parfum dans toute l'unité d'emballage au bout de quelques semaines.

For very absorbent papers, such as toilet papers, where good printability properties are not sought, perfuming can be done:

• - by lubricating the cutter blades with essential oils,
• - during packaging, by spraying the perfume on the cardboard support of the paper rolls or on only a few sheets per packaging unit. These very porous papers ensure diffusion of the perfume throughout the packaging unit after a few weeks.

For more pronounced odoriferous effects, the absorbent paper can be impregnated or saturated with aqueous solutions, containing for example propylene glycol, glycerin and a perfume (document JP-A-53-11059).

Document FR-A-1023954 describes a paper for packaging citrus fruits.

A layer consisting of diphenyl, lemon oil and / or bergamot oil and a wax is deposited on this paper. The object described in this document is completely different from the invention. This is to mask the odor of diphenyl. However, it is specified that only lemon and bergamot oils can provide this technical effect.

Document GB-A-1319951 describes a process for impregnating a paper with a composition which inhibits volatile corrosion. The purpose described in this document is to obtain a protective paper for metallic parts.

This document only describes a composition containing a sizing agent and a corrosion inhibiting agent.

However, this agent can also be deposited in the pulper or vaporized or impregnated.

The object of the invention is to obtain a perfumed printing-writing paper which retains all of its properties of good printability, and which can be manufactured by a process which is integrated into the conventional stages of manufacturing paper on a machine, namely in particular the stages of placing an aqueous suspension on canvas, draining and drying.

• ― une rémanence du parfum,
• ― un papier non gras en surface,
• ― une surface permettant l'impression et/ou l'écriture.

The object of the invention is therefore to obtain a paper capable of receiving printing and / or writing, this paper being scented. The qualities required of this paper are therefore:

• - a persistence of the perfume,
• - non-greasy paper on the surface,
• - a surface allowing printing and / or writing.

However, the problem posed by the production of such paper is that the perfume is composed of essential oils which destroy the bonding of the paper. As a result, when the paper receives printing or writing, the ink, instead of remaining in a determined sector, spreads and lines which are not sharp are obtained.

The object of the invention is to obtain a scented paper which has a good degree of bonding-writing, preferably equal to 5 (NFQ 03015).

To this end, the invention relates to a continuous process for the manufacture of a scented paper, with a high degree of adhesive bonding, consisting in forming a fibrous sheet and in depositing thereon, during manufacture, an aqueous surfacing composition. containing at least one aromatic composition, at least one sizing agent, at least one binder, optionally at least one additive. The aqueous surfacing composition can be deposited on the fibrous sheet which is still wet, that is to say, having a dryness lower than the desired final dryness of the paper.

The fibrous sheet can be produced from an aqueous suspension containing at least natural and / or synthetic fibers, binders, fillers and other additives such as charge retention agents, dyes, pigments, boards, etc. This suspension is deposited on a canvas and it is drained to obtain a wet fibrous sheet. The fibrous sheet is moved at a certain speed to drying devices. The speed can for example be several hundred meters per minute.

The surfacing composition is deposited on the fibrous sheet without substantially modifying the speed of the latter. The surfacing layer is deposited during the manufacture of the paper, preferably in a size press or by coating. The process is thus simplified by limiting to one surfacing operation, bonding and perfuming without harming the printability characteristics of the finished product.

The fibrous sheet thus coated is then dried.

The invention is remarkable in that the paper covered with the surfacing composition is dried at a relatively high temperature. Surprisingly, there is still enough perfume for it to perform its function.

In fact, the drying is rapid due to the speed of the sheet and a large part of the perfume does not have time to volatilize.

In addition, an advantage of the invention is that the paper obtained does not have a greasy feel, unlike the paper obtained by spraying perfume.

Another advantage of the invention is that the process is rapid and does not require subsequent treatment. Everything is done at the speed of the paper machine, for example several hundred meters per minute. However, a subsequent spraying treatment requires unwinding and then rewinding because the spraying does not allow a high speed. Thus the reel unwinding speed is ten times slower than the papermaking speed.

According to the invention, it is essential that the composition of the three agents be deposited on the surface to obtain the expected technical results.

The surfacing composition can be a true solution but also be a homogeneous emulsion, the essential oils of the aromatic composition being little or not soluble in water.

The sizing agent is taken from the group of conventional sizing agents for paper. Bonding agents are chemicals of natural or synthetic origin which, when introduced into paper, improve the bonding of paper, by reducing its Cobb value (NFQ 03-014) and / or by improving its resistance to writing. in ink (NFQ 03-015).

These products come in various forms (dispersion, aqueous or alcoholic emulsion, soaps ...) and are of great chemical diversity. Rosin derivatives, alkyl derivatives can be used according to the invention dimer ketene, wax derivatives, paraffin derivatives, protein derivatives, derivatives of hydrocarbon, organochlorine polymers, often rich in carboxyl function, of Baysinthol ^R AL2 of BAYER ^R consisting mainly of maleic anhydride with styrene copolymers- acrylic.

Mixtures of these products can be used.

The aromatic composition is composed of natural or synthetic essential oils with low saturation vapor pressure and heat stable. To avoid loss of paper sticking, solubilizers should be kept to a bare minimum. The term aromatic composition covers not only the field of perfumes for cosmetics, but also extends to natural or synthetic perfumes (fruit, food, drinks, leather, etc.). According to the invention, most of the possible perfumes can be used, including other aromatic compounds.

The binder is taken from the group of the following compounds: starch, polyvinyl alcohol, carboxymethylcellulose, alginates, latex or any other surface binder used in stationery.

• ― agent de collage: 0,05% à 2% en poids sec,
• ― liant: 0,5 à 10% en poids sec,
• ― parfum: 0,05 à 5%,

éventuellement jusqu'à 10% en poids sec d'un additif le reste étant de l'eau.The composition can include:

• - bonding agent: 0.05% to 2% by dry weight,
• - binder: 0.5 to 10% by dry weight,
• - fragrance: 0.05 to 5%,

possibly up to 10% by dry weight of an additive, the rest being water.

In a preferred embodiment, the aqueous surfacing composition comprises at least one dye or a mixture of dyes, the surfactants incorporated in these products contributing to better "solubilization" of the perfume.

The drying temperature is preferably between 80 ° and 140 ° C. The drying time can be between 30s and 5 min.

The surfacing composition may also comprise one or more additives taken from the group of the following additives: defoamer, sequestering agents, wetting agents, fillers, optical brighteners, finishing aids, dyeing aid.

The invention also relates to the perfumed paper obtained by the process below, intended for the printing-writing application and which preferably has a writing collage of 5 defined in standard AFNOR NFQ 03-015.

The technique of the invention also has the advantage of incorporating essential oils inside the paper: the cellulose thus acts as a diffuser. It allows a certain stability and durability of the fragrance (3 to 12 months in the open air depending on the doses used and external conditions, almost permanent in storage in sealed packaging).

The invention will be better understood on reading the description of the exemplary embodiments which will follow.

COMPARATIVE EXAMPLE I

A print-write paper medium bonded en masse and / or on the surface by a size press is then surfaced with a perfume solution by spraying or on another size press. The paper thus obtained is well scented. However, while the support was well bonded with No. 5 inks before the scented treatment, the final product gives a feeling of oily feel and is no longer even bonded to inks 1 or 2. This product is therefore rendered unsuitable for writing and printing.

It can therefore be seen that the vaporization of the perfume on a paper stuck with a composition containing a sizing agent and a binder no longer allows printing and / or writing.

COMPARATIVE EXAMPLE II

If one surfaces a paper support on a size press, with a sauce containing only perfume and the sizing agent in aqueous solution, it can be noted that the solution has a much greater tendency to decant. In addition, the printability properties of the support without surfacing with binder are seriously affected: dusting, tearing of fibers.

It can therefore be seen that the composition of perfume and sizing agent is not suitable for obtaining a scented paper.

EXAMPLE 1

• ― 200 g d'amidon
• ― 0,5 g d'antimousse
• ― 6 ml de Baysynthol ^R A12 (agent de collage de BAYER ^R)
• ― 25 ml de mimosa 1034 (composition parfumée mimosa de Synarome ^R)
• ― eau quantité suffisante pour un litre.

On a paper support is deposited on the surface, by a conventional papermaking technique (size press), the coating composition comprising per liter of liquid:

• - 200 g starch
• - 0.5 g of antifoam
• - 6 ml of Baysynthol ^R A12 (BAYER ^R sizing agent)
• - 25 ml of mimosa 1034 (mimosa scented composition from Synarome ^R )
• - water sufficient for one liter.

The paper after drying gives off a pleasant smell of mimosa which persists for several months in the open air and more than a year in sealed packaging. Paper has very good printability and writing characteristics.

EXAMPLE 2

• ― 200 g d'amidon
• ― 0,5 g d'antimousse
• ― 5 g Trilon ^R B (agent sequestrant de BASF ^R)
• ― 6 ml de Baysynthol ^R A12
• ― 5 g jaune Levacell ^R 5G (de BAYER ^R)
• ― 50 ml de base Citron 976 (de PARFLOR ^R)
• ― eau quantité suffisante pour un litre.

On a paper support colored in mass in yellow, is deposited on the surface, by a conventional papermaking technique (size press), the coating composition comprising per liter of liquid:

• - 200 g starch
• - 0.5 g of antifoam
• - 5 g Trilon ^R B (sequestering agent from BASF ^R )
• - 6 ml of Baysynthol ^R A12
• - 5 g Levacell ^R 5G yellow (from BAYER ^R )
• - 50 ml of Lemon 976 base (from PARFLOR ^R )
• - water sufficient for one liter.

The paper after drying gives off a pleasant lemon scent which matches the color of the paper. This paper has the same qualities of permanence of fragrance and printability as that of the previous example.

EXAMPLE 3

• ― 400 g de kaolin mis en dispersion
• ― 100 g de latex DOW ^R 615 (latex styrène-butadiène de DOW CHEMICAL ^R)
• ― 10 g d'alcool polyvinylique
• ― 30 g de Masquodor ^R FRD 485 (composition aromatique mandarine de J et E SOZIO ^R
• ― eau qsp 1 litre

A paper support is coated by conventional papermaking methods (air knife, drag blade, etc.), the coating sauce comprising for one kilogram of mixture:

• - 400 g of kaolin dispersed
• - 100 g of DOW ^R 615 latex (DOW CHEMICAL ^R styrene-butadiene latex)
• - 10 g of polyvinyl alcohol
• - 30 g of Masquodor ^R FRD 485 (mandarin aromatic composition of J and E SOZIO ^R
• - water qs 1 liter

The coated paper obtained is well scented with tangerine and retains very good printability characteristics. In this type of application, the latex acts as a bonding agent.

EXAMPLE 4

• ― 100 g d'amidon,
• ― 20 g d'alcool polyvinylique,
• ― 0,5 g d'antimousse,
• ― 8 ml de Baysynthol ^R 36053 (agent de collage de BAYER ^R),
• ― 40 ml d'arome artificiel N.I. de fruits de la passion (référence LC 15048 commercialisée par la société MERO ROUSSELOT SATIA)
• ― eau qsp 1 litre.

On a paper support is deposited on the surface, by a conventional paper method, the coating solution comprising, per liter of sauce:

• - 100 g of starch,
• - 20 g of polyvinyl alcohol,
• - 0.5 g of antifoam,
• - 8 ml of Baysynthol ^R 36053 (fining agent of BAYER ^R ),
• - 40 ml artificial aroma NI passion fruit (reference LC 15048 sold by the company MERO ROUSSELOT SATIA)
• - water qs 1 liter.

The paper after drying gives off a pleasant smell of passion fruit. Paper has the same characteristics of printability and permanence of the fragrance.

Claims (10)

1. Perfumed paper destined to printing-writing, characterized in that it is composed of at least one fibrous sheet and at least one surface-sizing layer comprising:

― at least one sizing agent,

― and least one binder,

― at least one aromatic composition, and

― optionally at least one additive.

2. Perfumed paper according to claim 1, characterized by the fact that it has a degree of sizing towards writing of 5.

3. Perfumed paper according to one of claims 1 and 2, characterized by the fact that the sizing agent is selected from the group formed by the derivatives of rosin, of alkyl ketene dimers, of waxes, of paraffins, of proteins, of polymers, of hydrocarbons, of organochlorine polymers, of styreneacrylic copolymers and mixtures thereof.

4. Perfumed paper according to one of claims 1 to 3, characterized by the fact that the binder is selected from the group formed by starch, polyvinyl alcohol, carboxymethyl cellulose, alginates, latex and mixtures thereof.

5. Perfumed paper according to one of claims 1 to 4, characterized by the fact that the aromatic composition is selected from the group of natural or synthetic essential oils.

6. Continuous process for producing a perfumed paper destined for printing-writing, consisting in placing an aqueous suspension containing at least fibers, on a web in order to form a sheet, and in draining and drying, characterized in that an aqueous surface-sizing composition is applied on at least one face of the sheet, said composition containing:

― at least one sizing agent,

― at least one binder,

― at least one aromatic composition,

― optionally, at least one additive, and the resultingly coated sheet is dried.

7. Continuous process according to claim 6, characterized in that the aqueous surface-sizing composition is applied on the partly dried sheet.

8. Process according to one of claims 6 and 7, characterized in that the coated sheet is dried at a temperature varying between 80 and 140°C to obtain the final dry content.

9. Process according to one of claims 6 to 8, characterized in that the coated sheet is dried for a period varying between 30 secs. and 5 mins.

10. Process according to one of claims 6 to 9, characterized in that the aqueous surface-sizing composition comprises:

― between 0.05% and 2% of at least one sizing agent by dry weight,

― between 0.5% and 10% of at least one binder, by dry weight,

― between 0.05% and 5% of at least an aromatic composition,

― optionally up to 10% by dry weight of an additive, the remainder being water.