DE2037455A1 - - Google Patents

Description

Dr. F. Zumstein Sr. - Dr. E. Assmann
Dr. R. Koenigsberger - Dipl. Phys. R. Holzhauer

Dr. F. Zumstein jun.
Godparents la π W ä I t β
8 Munich 2, BräuhouMtraße 4 / III

SC 3581

RHONE-POULENC S.A., Paris, France

Method of gluing paper

The present invention relates to a new method of gluing paper by means of a molten adhesive.

In French patent 1 Oj56 600 are in the heat meltable adhesives for bonding described. These compositions contain 1 part of a vinyl acetate-crotonic acid copolymer and 1/2 to 2 parts of a plasticizing plasticizing agent such as a chlorinated diphenyl.

These compositions are dispersible in alkalis, which enables remove any trace of glue from scrap paper resulting from trimming, binding operations is made, and as a result to reuse this waste, especially for the production of new paper.

A new method for gluing paper has now been found, which is characterized in that a melted paper is applied to the paper Applies adhesive containing a terpolymer resulting from the copolymerization of (based on the total weight of monomers):

109809/2008

a) 40 to 90 % of a vinyl ester of a saturated aliphatic monocarboxylic acid with 1 to 4 carbon atoms,

b) 2 to 20 % of an ethylenically unsaturated mono- or polycarboxylic acid with 3 to 6 carbon atoms and

c) 5 to 58 # of a vinyl ester of a saturated aliphatic. Monocarboxylic acid with 8 to JO carbon atoms or a mixture of such esters

originates

The first component of the terpolymer can be vinyl formate, vinyl acetate, vinyl propionate or vinyl butyrate. .

The proportion by weight of this ester in the terpolymer is preferably between 60 and 85 %.

As examples of ethylenically unsaturated mono- or polycarboxylic acids one can name acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and aconltsic acid.

The proportion by weight of the unsaturated acid in the terpolymer is preferably between 5 and 10 %.

The monocarboxylic acid with 8 to 50 carbon atoms, which is also called higher alkanoic acid in the following and from which the third constituent of the terpolymer is derived, can be linear or branched. It can be an acid with a well-defined formula, such as caprylic acid, pelargonic acid, capric acid, lauric acid, stearic acid and cerotic acid, or mixtures of acids, such as "Versatio 91!" Acids (trade name), the mixtures of tertiary monocarboxylic acids (about 90 #) and secondary monocarboxylic acids (about 10 %) having 9 to 11 carbon atoms per molecule. The production of such sauces is described in Chemical Products and Aerosol News (March 1962, pages 119-120, 132). ;

109809/2006

ORiGiNAL INSPECTED

The manufacture of vinyl esters of the various above Acids are known. What the special pail of vinyl esters of branched acids ("Versatic 911"), these according to the in French patents 1,250,158 (example 1) and 1 330 746 (Example 2) given method or by Reaction of the branched acids with vinyl acetate in the presence of a mercury salt (French patent 1 350 937) getting produced.

The proportion by weight of the vinyl esters of the higher alkanoic acids is preferably between 10 and 30 #.

The terpolymers can be prepared by the customary techniques for polymerizing vinyl monomers. '' *

A bulk polymerization is preferably carried out using a peroxidic initiator and a chain-limiting agent, such as acetaldehyde.

It should be noted that although the terpolymer is used alone as an adhesive can be used, but it is also possible to mix this with different products that have certain properties of the adhesive, such as, for example, the mechanical properties or the impermeability to water, or also its May reduce melt viscosity.

An additive should be evident with the melted Polymers be compatible and its good adhesion to paper and does not change its dispersibility in alkalis.

Examples of additives are the liquefying plasticizers, such as the chlorinated diphenyls, the plasticizers, such as the alkyl phthalates, the paraffins, the fillers and pigments and the resins that are called "reinforcing resins ¹¹ and their use in the compositions described in molten state are applied, is known example, one can up to 30 wt -..% of chlorinated diphenyl, based on the terpolymers used.

10980972006

"Paraffin" refers to straight-chain hydrocarbons with 22 to ^ O carbon atoms, which come from the distillation of petroleum that has already been refined by chemical treatment. Its melting point is generally between 34 and 7O ⁰ C.

For reasons of compatibility with the polymer, the proportion is of paraffin generally not more than 50 wt .- ^ des Polymers.

As examples of reinforcing resins, the melting point of which is generally below 100 ^° C., the following can be mentioned; the ester resins, such as, for example, the glycerol esters of hydrogenated rosin, the glycerol esters of polymerized rosin, the ρ-toluenesulfonamide-formaldehyde resins, the phenol-formaldehyde resins, the indene-coumarone resins, the phenolic resins or also the terpene resins. A plasticizer or plasticizer can themselves be added to these resins. The proportion of reinforcing resin can be 95 wt .- # of the mixture of polymers! plus resin.

The method according to the invention can be carried out using the customary techniques coating, enrobing or gluing by means of compositions applied in the molten state will. In general, the apparatus comprises a heated vessel in which the adhesive is kept in the melt System based on the application of a certain amount of this glue allows on the carrier.

Those produced with the aid of adhesives according to the invention Bondings are of excellent quality and are also dispersible in an alkaline medium. There is no need to use primers with these adhesives.

To measure the strength of the with the inventively used, ten adhesives, the following test is carried out:

109809/2006

20374SS

One stacks 50 sheets of paper with a thickness of 0.25 now and with Dimensions of 25 χ 50 mm on top of each other. These arches are firmly clamped between two wooden panels with dimensions of 25 χ 45 mm. Use a fine arrow to edit the cut of the sheet stack exactly.

The mixture is poured onto the brought to 19O ⁰ C to the adhesive section. Then you press a wooden plate (P) of the same thickness as that of the stack of sheets against the glued cut and then place it in a drying cabinet for 2 minutes. Then leave the whole thing for 1 week in an atmosphere of 23 ° C with a humidity level of 60. ■

Then you tear off the sheets of paper. To do this, you attach the plate (P) in one of the grips of a dynamometer one after the other each of the paper sheets in a different clamping clamp and increases the distance between the clamping clamps (displacement speed 15 mm / min) until the adhesive point tears.

The strength of the bond at break is measured. Hereinafter is the value of this strength calculated from the mean of 30 Sheet of paper, indicated.

The following examples illustrate the invention without restricting it. I.

Example 1 ,

In this example the terpolymer originates from the copolymerization of vinyl acetate, crotonic acid and one commercially available under the Trade name "Versatate VEOVA 911" available product that is a Mixture of vinyl esters of branched monocarboxylic acids with Cq to C-- is * This product has the following characteristics:

Average molecular weight ι 197 Viscosity at 20 ⁰ C: · 2.2

ΤΛ

Refractive index η « ₀ : 1

10 9809/2006

Acid number: 1

Bromine number: 78-80

Boiling range (100 mm Hg) ϊ 129 - 180 ° C

The polymer is made in the following way:

In a 2 l reaction vessel, which is equipped with a stirrer, a thermometer, a condenser, a dropping funnel, and a system allowing sampling to be carried out are brought as follows Components a:

Vinyl acetate: 41 # solution
»
• 825 G Crotonic acid: with 15.5 % 20th G 120 G 41 G "Versatate VEOVA 911" i 5 * 7 g Acetaldehyde in
in vinyl acetate: Benzoyl peroxide
Humidity:

The following ingredients are placed in the dropping funnel:

Vinyl acetate: 195 g

Crotonic acid: 40 g

Acetaldehyde: 27 g of the above

th solution

Benzoyl peroxide: 2.55 g

The water introduced into the reaction vessel mixture is stirred (80 r / min) and by means of a temperature-controlled bath for 30 minutes to heated to boiling (68-72 ⁰ C).

One then begins with the inflow, which is continuous within of 6 hours and 20 minutes is made.

After completion of the addition, the temperature of the bath for 1 hour, raised to 90-92 ⁰ C and reducing the stirring speed (22 rev / min).

109809/2006

18th cnr / g O .5 % 5 .9 % O .8 % 71 ⁰ C

'2037458

Priority 380 cnr ⁵ acetone under cooling the mass to 60 ° C.

After removing the acetone by heating under reduced By printing a product is obtained that has the following properties:

Viscosity number: Free crotonic acid:

Total acidity expressed as crotonic acid:

Unsaturation, expressed as "Versatate VEOVA 911":

Kraemer-Sarnow point: (

The composition by weight of the terpolymer obtained is im essential the following:

Vinyl acetate: 85

Crotonic acid: 5

"Versatate VEOVA 911": 10

It is found that 10 g of the terpolymer obtained in this way, while stirring, in 90 g of an aqueous solution with a content of 1.04 g of ammonia of 22 ^° Be * and in 90 g of an aqueous solution at room temperature within 11/2 hours dissolve a content of 0.8 g of sodium carbonate. I.

The terpolymer is subjected to the adhesive test described above:

The mean value for the tensile strength of the bond is 25 kg / cm ² .

For comparison purposes, it should be noted that the value for the tensile strength of a of a vinyl acetate-crotonic acid copolymers with a content of 95 weight under the conditions described above using -.% Vinyl acetate adhesive bond prepared is near.

109809/2006

Example 2

Compositions are prepared containing 100 parts of the terpolymer of Examples 1 and 5> Contain 10 or 15 parts of a chlorinated diphenyl (with 54 wt .- ^ chlorine).

With the help of these compositions, sheets of paper are glued according to the procedure described above »

The test of the adhesive strength provides the following results:

with 5 % chlorinated diphenyl, based on the _2nd

Terpolymers: 42.5 kg / cm

with 10 % chlorinated diphenyl, based on the ^ ₂ terpolymer:> 73 kg / cm

with 15 % chlorinated diphenyl, based on the terpolymer: 120 kg / cm

For comparison purposes, it should be noted that compositions containing 100 parts of the vinyl acetate-crotonic acid copolymer described in Example 1 and 5, 10 or 15 parts of chlorinated diphenyl result in bonds whose strength is J, 15 and 23 kg / cm ² , respectively.

Example 3

According to the procedure described in Example 1, “is set Terpolymer that has the following properties:

Weight composition: vinyl acetate: 65

Crotonic acid: 5

"Versatate VEOVA 911": 30

Viscosity number: 26 onrVg Free crotonic acid: 0.2 %
Total acidity: 5.6 %
Unsaturation: 0.5 %

Kraemer-Sarnow point: 69 ⁰ C

109809/2006

20374S5

This terpolymer has the same properties with respect to Dispersibility in an alkaline medium like the terpolymer of Example 1 on.

One leads with the terpolymer and with compositions that Parts of this terpolymer and 5 and 10 parts, respectively, contain chlorinated diphenyl, the gluing of paper sheets through and takes the measurement the strength of this bond according to the procedure described above.

The following results are found:

with the polymer alone: strength 8 kg / cm

with the polymer plus 5 % ' 2

chlorinated diphenyl: 15 kg / cm

with the polymer plus 10 % ο

chlorinated diphenyl: 40 kg / cm

Example 4

The procedure described in Example 1 is used Terpolymer made from vinyl acetate ($ 65), crotonic acid (5 #), and vinyl stearate (j50 #) that has the following properties:

Viscosity number: 29 cm- egg - Free crotonic acid: 0 , 25 % Overall acidity: 5 , 5 Unsaturation, expressed as vinyl acetate: 0 , 2 Kraemer-Sarnow point: 59 ⁰ C

This terpolymer has the same properties with respect to Dispersibility in an alkaline medium like the terpolymers of Examples 1 and 3 on. One with this terpolymer to the top Bonding carried out in the manner described results in a tear strength from 32 kg / cm.

109809/2 00 6

Example 5

The procedure described in Example 1 is used to prepare a terpolymer from vinyl acetate (65 %) , crotonic acid (5 %) and vinyl laurate (30 %) , which has the following properties:

Viscosity number: 35 cm ⁵ / g Free crotonic acid: 0.3 % Overall acidity: 5.2 % Unsaturation (based on Vinyl laurate): 0.6 % Kraemer-Sarnow point: 61 ⁰ C

This terpolymer has the same properties in terms of dispersibility in an alkaline medium and adhesive strength on paper like the terpolymers of the previous examples.

109809/20 OB

Claims (2)

Claims 1. Method for gluing paper, characterized * that a molten adhesive is applied to the paper containing a terpolymer obtained from the polymerization of ( on the total weight of the monomers): a) 40 to 90 % of a vinyl ester of a saturated aliphatic monocarboxylic acid with 1 to 4 carbon atoms, b) 2 to 20 % of an ethylenically unsaturated mono- or polycarboxylic acid with 3 to 6 carbon atoms and " c) 5 to 58 % of a vinyl ester or a mixture of vinyl esters of saturated aliphatic monocarboxylic acids having 8 to 30 carbon atoms originates » 2. The method according to claim 1, characterized in that the Adhesive in addition to the polymer, an additive from the group of paraffin, fillers, pigments, reinforcing resins and contains chlorinated diphenylene. >. Method according to claim 1 or 2, characterized in that " that the terpolymer from the polymerization of (based on the total weight of the monomers): a) 60 to 85 % of a vinyl ester of a saturated aliphatic monocarboxylic acid with 1 to 4 carbon atoms, b) 5 to 10 % of an ethylenically unsaturated mono- or polycarboxylic acid with 2 to 6 carbon atoms and c) 10 to JO % of a vinyl ester or a mixture of vinyl esters of saturated aliphatic monocarboxylic acids with 8 to 30 carbon atoms " originates * 109809/20 06.