CN103937434B - A kind of preparation method of double gummed paper wetting ability adhesive bookbinding sizing agent - Google Patents

Abstract

The invention discloses a preparation method of a hydrophilic bookbinding adhesive for double offset paper, which is used to solve the problem that the existing adhesive for double offset paper affects paper quality or even paper forming during paper recycling. The preparation method of the hydrophilic bookbinding adhesive for double offset paper of the present invention adopts the introduction of sulfo group on the alkyd polycondensation monomer, which greatly increases the hydrophilicity of the polycondensation product. Compared with the commonly used adhesives in the prior art, the present invention has significantly improved bonding strength, and the demand for dissolved and colloidal substances (DCS) and cationic charges in the process of paper recycling is significantly reduced, and the waste paper is easy to be shredded and reused. The difficulty and cost are greatly reduced, and the efficiency of the wet end of the paper machine is significantly improved.

Description

A kind of preparation method of hydrophilic bookbinding adhesive for offset paper

technical field

The invention relates to the technical field of bookbinding adhesives, in particular to a preparation method of a hydrophilic bookbinding adhesive for offset paper.

Background technique

Hot-melt adhesive for double-adhesive paper book wireless binding is one of the earliest hot-melt adhesive varieties developed in China. Its main features are high flatness when the book is opened; The amount of glue is small, cold-resistant, heat-resistant, once cured, it will not soften, and can be used in a wide temperature range. Polyether polyol is used as the basic raw material, supplemented with various additives and polyisocyanate to polymerize to obtain reactive polyurethane hot melt adhesive. However, due to the limitation of the price of books (especially textbooks for primary and secondary school students), there are many problems in the quality of glue used in this field, such as low bonding strength, brittleness at low temperature, short life, etc. Mainly. At present, the hot-melt adhesives used for the wireless binding of double-adhesive paper books in China are all EVA type, and polyurethane hot-melt adhesives have been widely used in the wireless binding of double-adhesive paper books abroad.

The invention patent with the authorized announcement number "CN1021811259B" discloses a polyurethane hot melt adhesive for bookbinding and its preparation method, which belongs to the technical field of polyurethane preparation. In the present invention, polyester polyol and additives are placed in a reaction kettle to be heated, vacuum dehydrated under stirring, and then lowered in temperature; hexamethylene diisocyanate and diphenylmethane diisocyanate are obtained

Waste paper recycling is an important measure to achieve sustainable development of my country's paper forestry industry, and it has significant energy saving, consumption reduction, pollution reduction and efficiency increase. The use of hot melt adhesive has an important impact on the recycling characteristics of offset paper printed matter. On the one hand, the hot melt adhesive is closely combined with the paper, and it is difficult to separate the paper during the recycling process, resulting in spots, transparency, etc. of the hot melt adhesive in the residual pulp. Paper disease affects the sensory and quality of recycled paper; on the other hand, hot melt adhesives are hydrophobic and difficult to disperse in water, and stickies are produced during the recycling process. Hot melt adhesives dispersed in water are used to reduce cationic Auxiliary performance, affecting paper forming and reducing fiber bonding performance. Therefore, the development of highly hydrophilic hot-melt adhesives is of great significance for the efficient utilization of offset paper prints.

Contents of the invention

The purpose of the present invention is to provide a method for preparing a hydrophilic bookbinding adhesive for double offset paper, which is used to solve the problem that the existing adhesive for double offset paper affects paper quality or even paper forming in paper recycling. question.

In order to solve the problems referred to above, the technical scheme that the present invention takes is:

A preparation method of a hydrophilic bookbinding adhesive for offset paper, comprising the following steps:

1) According to parts by weight, mix 50-150 parts of succinic acid and 1-5 parts of octadecanoic acid, stir, feed inert gas, heat up to 188-194 ° C, and keep mechanical stirring;

2) Add 50-60 parts by weight of potassium 1-hydroxymethyl-2-hydroxy-ethanesulfonate dropwise, and raise the temperature to 196-206°C after the addition is complete;

3) adding 1 to 3 parts by weight of a polycondensation catalyst;

4) Add 120-180 parts by weight of pentanediol dropwise. After the dropwise addition, raise the temperature to 208-216°C and continue the reaction for 15-20 minutes;

5) Cool down to 188-194°C, add 1-3 parts by weight of paraffin, 3-15 parts by weight of binder, 2-6 parts by weight of filler, 0.1-1 part by weight of antioxidant, mix and stir evenly, and cool.

Among them, the inert gas plays a protective role and can be nitrogen or helium; octadecanoic acid is used as an external acid catalyst; the polycondensation catalyst can be tetrabutyl titanate, potassium fluorotitanate and antimony glycol; 1-hydroxy Potassium methyl-2-hydroxy-ethanesulfonate is used to introduce a strong hydrophilic group sulfo group on the polycondensation reaction product.

Preferably, the polycondensation reaction catalyst is ethylene glycol antimony.

Preferably, the potassium 1-hydroxymethyl-2-hydroxy-ethanesulfonate is uniformly added dropwise, and the dropwise addition is completed within 20-25 minutes. Uniform and slow dropwise addition makes the potassium 1-hydroxymethyl-2-hydroxy-ethanesulfonate evenly distributed in the reaction system, which is conducive to the uniformity of the subsequent reaction.

Preferably, the pentylene glycol is evenly added dropwise, and the dropwise addition is completed within 30-45 minutes. Evenly and slowly adding pentylene glycol dropwise can increase the yield of polycondensation products to a certain extent.

Preferably, the binder includes 2-10 parts by weight of carboxylated nitrile rubber, and 1-5 parts by weight of water-based tackifying resin. The use of the water-based tackifying resin further increases the hydrophilicity of the bookbinding adhesive for offset paper prepared by the method of the present invention.

Preferably, the filler is talcum powder. The filler can be at least one of talcum powder, titanium dioxide, and calcium carbonate, preferably talcum powder.

Preferably, the antioxidant is propyl gallate.

Preferably, the inert gas is nitrogen. Nitrogen is low cost and does not cause air pollution.

The beneficial effects of the present invention are:

Compared with the commonly used adhesives in the prior art, the present invention has significantly improved cohesive strength, and because the adhesive contains more hydrophilic groups (sulfonic acid groups), the paper recycle process dissolves and colloidal substances (DCS) The demand for and cationic charge is significantly reduced, the waste paper is easy to shred, the difficulty and cost of recycling are greatly reduced, and the efficiency of the wet end of the paper machine is significantly improved. During the paper recycling process of the books and periodicals bound with the adhesive, the adhesive is soluble in water, and the paper recycling does not affect the quality of the paper, nor does it affect the forming of the paper.

Detailed ways

The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some of the embodiments of the present invention, but not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.

Example 1

Add 100 grams of succinic acid and 2 grams of octadecanoic acid, pass in nitrogen, mix well by mechanical stirring, heat up to 188 ° C, keep mechanical stirring, and evenly add 60 grams of 1-hydroxymethyl-2- Potassium hydroxy-ethanesulfonate, then heat up to 198°C, add 1.5 grams of ethylene glycol antimony, and evenly add 150 grams of pentanediol dropwise within 40 minutes. When the temperature reaches 194°C, add 5 grams of carboxylated nitrile rubber, 3 grams of water-based tackifying resin, 2 grams of paraffin wax, 4 grams of talcum powder, and 0.5 grams of propyl gallate, mix and stir for 10 minutes to cool, and package.

The prepared adhesive has a bonding strength of 5.62MPa, a melt viscosity of 3.15Pa s, a softening point of 87.1°C, a brittleness temperature of -3.2°C, and a hardness of 82.7; the solubility of aqueous solution at room temperature is 99.1% (<3h), and the printing paper reuse process dissolves and colloidal substances (DCS) 0.042%, cationic charge demand 1.75μeq/g; elongation at break 395%, elastic recovery times 12000 times.

Example 2

Add 100 grams of succinic acid and 2 grams of octadecanoic acid, pass through nitrogen, mix well by mechanical stirring, heat up to 194 ° C, keep mechanical stirring, and evenly add 50 grams of 1-hydroxymethyl-2 within 25 minutes -Potassium hydroxy-ethanesulfonate, then heat up to 200°C, add 1.5 grams of antimony ethylene glycol, and evenly add 140 grams of pentanediol dropwise within 40 minutes, and then raise the temperature to 208°C to continue the reaction for 15 minutes. Lower the temperature to 194°C, add 7 grams of carboxylated nitrile rubber, 4 grams of water-based tackifying resin, 1 gram of paraffin wax, 3 grams of talcum powder, and 0.8 grams of propyl gallate, mix and stir for 10 minutes to cool, and package.

The prepared adhesive has a bonding strength of 5.54MPa, a melt viscosity of 3.42Pa s, a softening point of 89.5°C, a brittleness temperature of -3.8°C, a hardness of 86.1, and a solubility of 99.0% (<3h) in aqueous solution at room temperature. DCS) 0.036%, cationic charge requirement 1.65μeq/g; elongation at break 420%, elastic recovery times 13500 times.

Example 3

Add 80 grams of succinic acid and 2 grams of octadecanoic acid, pass in nitrogen, mix evenly by mechanical stirring, heat up to 190 ° C, keep mechanical stirring, and evenly add 55 grams of 1-hydroxymethyl-2 within 20 minutes -Potassium hydroxy-ethanesulfonate, then raise the temperature to 201°C, add 1.5 grams of ethylene glycol antimony, add 125 grams of pentylene glycol dropwise evenly in 40 minutes, raise the temperature to 208°C to continue the reaction for 18 minutes after the dropwise addition of pentylene glycol, and reduce When the temperature reaches 194°C, add 8 grams of carboxylated nitrile rubber, 4 grams of water-based tackifying resin, 3 grams of paraffin wax, 6 grams of talcum powder, and 0.8 grams of propyl gallate, mix and stir for 10 minutes to cool, and package.

The prepared adhesive has a bonding strength of 5.39MPa, a melt viscosity of 4.16Pa s, a softening point of 91.3°C, a brittleness temperature of -4.2°C, and a hardness of 84.6; the solubility of the aqueous solution at room temperature is 99.2% (<3h), and the printing paper reuse process dissolves and colloidal substances (DCS) 0.046%, cationic charge requirement 1.54μeq/g; elongation at break 415%, elastic recovery times 13700 times.

Example 4

Add 130 grams of succinic acid and 4 grams of octadecanoic acid, blow in nitrogen, mix well by mechanical stirring, raise the temperature to 194 ° C, keep mechanical stirring, and evenly add 55 grams of 1-hydroxymethyl-2- Potassium hydroxy-ethanesulfonate, then heat up to 200°C, add 1.5 grams of ethylene glycol antimony, add 175 grams of pentanediol dropwise evenly in 40 minutes, raise the temperature to 208°C after the dropwise addition of pentanediol and continue the reaction for 18 minutes, lower the temperature To 190°C, add 4 grams of carboxylated nitrile rubber, 5 grams of water-based tackifying resin, 2 grams of paraffin wax, 4 grams of talcum powder, and 1 gram of propyl gallate, mix and stir for 10 minutes to cool, and package.

The prepared adhesive has a bonding strength of 5.53MPa, a melt viscosity of 4.56Pa s, a softening point of 88.7°C, a brittleness temperature of -4.0°C, and a hardness of 83.2; the solubility of aqueous solution at room temperature is 99.4% (<3h), and the printing paper reuse process dissolves and colloidal substances (DCS) 0.041%, cationic charge demand 1.53μeq/g; elongation at break 392%, elastic recovery times 12800 times.

Example 5

Add 90 grams of succinic acid and 3 grams of octadecanoic acid, pass in nitrogen, mix uniformly by mechanical stirring, heat up to 192 ° C, keep mechanical stirring, and evenly add 56 grams of 1-hydroxymethyl-2- Potassium hydroxy-ethanesulfonate, then raise the temperature to 202°C, add 1.5 grams of ethylene glycol antimony, add 135 grams of pentanediol evenly in 40 minutes, raise the temperature to 208°C after the dropwise addition of pentanediol and continue the reaction for 17 minutes, lower the temperature To 192°C, add 5 grams of carboxylated nitrile rubber, 4 grams of water-based tackifying resin, 2 grams of paraffin wax, 4 grams of talcum powder, and 0.3 grams of propyl gallate, mix and stir for 10 minutes to cool, and package.

The prepared adhesive has a bonding strength of 5.61MPa, a melt viscosity of 3.94Pa s, a softening point of 94.2°C, a brittleness temperature of -4.3°C, and a hardness of 84.2; the solubility of the aqueous solution at room temperature is 99.3% (<3h), and the printing paper reuse process dissolves and colloidal substances (DCS) 0.051%, cationic charge requirement 1.26μeq/g; elongation at break 408%, elastic recovery times 14100 times.

Example 6

Add 130 grams of succinic acid and 4 grams of octadecanoic acid, pass through helium, mix uniformly by mechanical stirring, heat up to 194 ° C, keep mechanical stirring, and evenly add 55 grams of 1-hydroxymethyl-2 in 20 minutes -Potassium hydroxy-ethanesulfonate, then heat up to 200°C, add 1.5 grams of tetrabutyl titanate, add 175 grams of pentylene glycol dropwise evenly in 40 minutes, raise the temperature to 208°C after the dropwise addition of pentanediol and continue the reaction for 18 minutes, Lower the temperature to 190°C, add 4 grams of carboxylated nitrile rubber, 5 grams of water-based tackifying resin, 2 grams of paraffin wax, 4 grams of talcum powder, and 1 gram of propyl gallate, mix and stir for 10 minutes to cool, and package.

The prepared adhesive has a bonding strength of 5.51MPa, a melt viscosity of 4.52Pa s, a softening point of 88.6°C, a brittle temperature of -3.9°C, and a hardness of 83.1; the solubility of the aqueous solution at room temperature is 99.2% (<3h), and the printing paper reuse process dissolves and colloidal substances (DCS) 0.043%, cationic charge requirement 1.55μeq/g; elongation at break 390%, elastic recovery times 12800 times.

Example 7

Add 90 grams of succinic acid and 3 grams of octadecanoic acid, pass in nitrogen, mix uniformly by mechanical stirring, heat up to 192 ° C, keep mechanical stirring, and evenly add 56 grams of 1-hydroxymethyl-2- Potassium hydroxy-ethanesulfonate, then heat up to 202°C, add 1.5 grams of potassium fluotitanate, add 135 grams of pentylene glycol dropwise evenly in 40 minutes, raise the temperature to 208°C after the dropwise addition of pentylene glycol, continue the reaction for 17 minutes, lower the temperature To 192°C, add 5 grams of carboxylated nitrile rubber, 4 grams of water-based tackifying resin, 2 grams of paraffin wax, 4 grams of talcum powder, and 0.3 grams of propyl gallate, mix and stir for 10 minutes to cool, and package.

The prepared adhesive has a bonding strength of 5.56MPa, a melt viscosity of 3.91Pa s, a softening point of 94.1°C, a brittleness temperature of -4.1°C, and a hardness of 84.0; the solubility of the aqueous solution at room temperature is 99.1% (<3h), and the printing paper reuse process dissolves and colloidal substances (DCS) 0.053%, cationic charge requirement 1.28μeq/g; elongation at break 405%, elastic recovery times 14100 times.

At present, the typical EVA hot melt adhesive used for double offset paper binding has a bonding strength of 4.67MPa, a melt viscosity of 3.08Pa s, a softening point of 78.4°C, a brittle temperature of 2.1°C, and a hardness of 78.5; The dissolved and colloidal substance (DCS) in the reuse process is 3.21%, the cationic charge demand is 6.54μeq/g; the elongation at break is 185%, and the number of elastic recovery times is 7800 times. Compared with it, the present invention has significantly improved bond strength , and the demand for dissolved and colloidal substances (DCS) and strong ionic charges in the paper recycling process is significantly reduced, the waste paper is easy to shred, the difficulty and cost of recycling are greatly reduced, and the efficiency of the wet end of the paper machine is significantly improved.

Claims (7)

1. a double gummed paper preparation method for wetting ability adhesive bookbinding sizing agent, is characterized in that: comprise the following steps:

1) according to weight parts, by 50 ~ 150 parts of succinic acid and 1 ~ 5 part of octadecanoic acid mixing, stir, pass into rare gas element, be warming up to 188 ~ 194 DEG C, keep mechanical stirring;

2) drip 50 ~ 60 weight part 1-methylol-2-hydroxy-ethane potassium sulfonates, after dropwising, be warming up to 196 ~ 206 DEG C; The described 1-methylol of even dropping-2-hydroxy-ethane potassium sulfonate, and dropwise in 20 ~ 25min;

3) 1 ~ 3 weight part polycondensation catalyst is added;

4) drip 120 ~ 180 weight part pentanediols, after dropwising, be warming up to 208 ~ 216 DEG C, continue reaction 15 ~ 20min;

5) be cooled to 188 ~ 194 DEG C, add 1 ~ 3 weight part paraffin, 3 ~ 15 parts by weight binder, 2 ~ 6 parts by weight of filler, 0.1 ~ 1 weight part antioxidant, mix and stir, cooling.

2. the double gummed paper preparation method of wetting ability adhesive bookbinding sizing agent as claimed in claim 1, is characterized in that: described polycondensation catalyst is antimony glycol.

3. the double gummed paper preparation method of wetting ability adhesive bookbinding sizing agent as claimed in claim 1, is characterized in that: evenly drip described pentanediol, and dropwise in 30 ~ 45min.

4. the double gummed paper preparation method of wetting ability adhesive bookbinding sizing agent as claimed in claim 1, is characterized in that: described binding agent comprises 2 ~ 10 weight part carboxy nitrile rubbers, 1 ~ 5 weight part water-based tackifying resin.

5. the double gummed paper preparation method of wetting ability adhesive bookbinding sizing agent as claimed in claim 1, is characterized in that: described weighting agent is talcum powder.

6. the double gummed paper preparation method of wetting ability adhesive bookbinding sizing agent as claimed in claim 1, is characterized in that: described antioxidant is Tenox PG.

7. the double gummed paper preparation method of wetting ability adhesive bookbinding sizing agent as claimed in claim 1, is characterized in that: described rare gas element is nitrogen.