JP2691690B2 - Paper coating resin and paper coating composition containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a paper coating resin which provides a coated paper having excellent printability and printing effect, and a paper coating composition using the same.

[0002]

2. Description of the Related Art Generally, coated paper is manufactured by coating a pigment such as clay or calcium carbonate with a binder such as latex or starch. This coated paper is required to have higher printability as printing speed, precision, and multicolor have increased in recent years. To improve these printability, for example, JP-B-44-11667 and JP-B-59-
A polyamide polyurea-formaldehyde resin such as 32597 and a polyamide polyurea-epihalohydrin-formaldehyde resin of JP-B-61-42931 have been proposed.

[0003]

However, when the above formaldehyde resin is used, there is a problem of formaldehyde generation, and when the ink acceptability is increased,
The pick strength tends to decrease, the printing gloss decreases, and the paint thickens significantly. On the other hand, increasing the pick strength,
When the viscosity of the paint is suppressed, contradictory unfavorable properties such as a decrease in ink acceptability tend to appear, and the degree of the effect is insufficient for the recent high demand for coated paper quality. .

Therefore, the present invention is particularly excellent in ink acceptability in recent years due to high quality requirements for coated paper, has little change in viscosity characteristics of the coating composition, and does not generate formalin. The purpose is to provide a coating composition.

[0005]

The present inventors have found that a specific condensation product obtained by reacting a polyalkylene polyamine with a specific aliphatic monocarboxylic acid, or a polyalkylene polyamine and a dibasic carboxylic acid compound. addition condensation from a particular specified condensation product obtained from the reaction of fat <br/> aliphatic-based monocarboxylic acid, or alkylenediamine and / or polyalkylenepolyamine and acrylic acid esters and / or methacrylic acid esters and When a condensation product obtained by reacting a specific aliphatic monocarboxylic acid with the product is used as a resin for paper coating, no formalin is generated, the ink acceptability is improved, and the viscosity of the coating composition is improved. We found that it can be a paper coating composition with little change in properties,
The present invention has been completed. That is, the present invention is a reaction condensation product of (I) a polyalkylene polyamine and an aliphatic monocarboxylic acid having 1 to 12 carbon atoms and having an amine value of 100 to 50.
0 , (II) polyalkylene polyamine, dibasic carboxylic acid compound and reaction condensation product with an aliphatic monocarboxylic acid having 1 to 12 carbon atoms and having an amine value of 100 to
Aliphatic monocarboxylic acid having 1 to 12 carbon atoms in addition-condensation product of amines selected from the group consisting of 500 and (III) alkylenediamines or polyalkylenepolyamines with esters selected from acrylic acid esters or methacrylic acid esters The resin for paper coating is characterized in that one or more of the condensation products obtained by reacting the above are used as essential components .

Examples of the polyalkylene polyamine used in the condensation product (I) include polyethylene polyamine, polypropylene polyamine and polybutylene polyamine. Among them, polyethylene polyamine is preferable, and triethylene tetramine and tetraethylene pentamine are more preferable. Minnes, pentaethylenehexamine, etc. may be mentioned, and these polyalkylene polyamines may be used alone or in combination of two or more.

The aliphatic monocarboxylic acid to be reacted with the polyalkylenepolyamine is preferably a monocarboxylic acid having 1 to 12 carbon atoms, and monocarboxylic acids such as acetic acid, propionic acid, octylic acid, nonanoic acid and decanoic acid. Can be mentioned. The reason for this is that if formic acid is used as the monocarboxylic acid, the heat generated during mixing with the polyamine is large and the reaction control is difficult, which is not preferable. Further, it is not preferable to use a monocarboxylic acid having 13 or more carbon atoms because the hydrophobicity becomes too strong and the water solubility decreases. These monocarboxylic acids may be used alone or in combination of two or more kinds. Particularly, when two or more kinds such as a mixture of a relatively lower acid and a relatively higher acid are used in combination, it is preferable to use the aliphatic monocarboxylic acid mixture so that the molar average carbon number is 2 to 6 and the ink acceptability is high. It is suitable for the balance of the viscosity of the paper coating composition.

The reaction between the polyalkylene polyamine and the aliphatic monocarboxylic acid is 0.1 to 0.9 (mol / mol) with respect to the polyalkylene polyamine and the amino group of the polyamine.
mol) aliphatic monocarboxylic acid is mixed and heated,
It can be obtained by heating to about 200 ° C. while dehydrating. In actual use, the condensation-produced resin can be cooled, added with water, neutralized and diluted with water to a predetermined concentration.

The condensation product resin (I) preferably has an amine value of 100 to 500. Amine value is 1
When the value is 00 or less, the effect of improving the ink acceptability is low, and when the value is 500 or more, when the composition is mixed with a pigment and an aqueous binder to form a paper coating composition, the viscosity is excessively increased due to aggregation of the pigment and the coating property is deteriorated. is there.

Further, in producing the condensation product (II) obtained by the reaction of the polyalkylene polyamine, the dibasic carboxylic acid compound and the aliphatic monocarboxylic acid, the polyalkylene polyamine and the aliphatic compound are used. A monocarboxylic acid can be used, and examples of the dibasic carboxylic acid compound include a dibasic carboxylic acid, a dibasic carboxylic acid monoester, and a dibasic carboxylic acid diester. Examples include succinic acid, glutaric acid and adipic acid, dibasic carboxylic acid monoesters such as monomethyl adipate, and dibasic carboxylic acid diesters such as diethyl succinate and diethyl adipate. These dibasic carboxylic acid compounds may be used alone or in combination of two or more. The dibasic carboxylic acid is used in an amount equal to or less than the equimolar amount of the polyalkylene polyamine, and the aliphatic monocarboxylic acid is used in an amount of 0.1 to 0.9 (mol / mol) of the residual amino group.

The amine value of this resin (II) is 10
0-500 is suitable. The amine value is 10 as in the above.
When it is 0 or less, the effect of improving the ink acceptability is low, and when it is 500 or more, when the composition is mixed with a pigment and an aqueous binder to prepare a paper coating composition, the viscosity of the pigment excessively increases due to aggregation of the pigment and the coating property deteriorates. is there.

In the reaction method of the present invention, polyalkylenepolyamine is gradually added to and mixed with the dibasic carboxylic acid compound, and the mixture is heated to about 200 ° C. to distill off by-produced water or alcohol. After cooling once, an aliphatic monocarboxylic acid is further added, and then slowly heated to about 200 ° C. to distill off water as a by-product. In actual use, the condensation-produced resin can be cooled, added with water, neutralized and diluted with water to a predetermined concentration.

The above-mentioned paper coating resin (III) is obtained by reacting the above-mentioned aliphatic monocarboxylic acid with the addition condensation product of alkylenediamine or the above-mentioned polyalkylenepolyamine and acrylic acid ester or methacrylic acid ester. , Ethylenediamine as the alkylenediamine,
Propylenediamine, butylenediamine and the like, and polyalkylenepolyamines include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and the like. From the viewpoints of reactivity and viscosity of the reaction product, ethylenediamine is preferable as the alkylenediamine, and diethylenetriamine and triethylenetetramine are preferable as the polyalkylenepolyamine.

As the acrylic ester or methacrylic ester that reacts with the amines, methyl acrylate in which the alkyl group in the ester portion has 1 to 3 carbon atoms,
Ethyl acrylate, propyl acrylate, methyl methacrylate, ethyl methacrylate and propyl methacrylate are preferred. When the alkyl group in the ester portion has more than 3 carbon atoms, the reaction rate is slow, and the boiling point of the by-product alcohol after the condensation reaction is high, so that the by-product alcohol cannot be sufficiently distilled off from the reaction system. In this respect, methyl acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate are particularly preferable.

The same aliphatic monocarboxylic acid as above can be used. These monocarboxylic acids may be used alone or in combination of two or more kinds. In particular, it is preferable to use two or more kinds such as a mixture of a relatively lower acid and a relatively higher acid so that the aliphatic monocarboxylic acid mixture has a molar average carbon number of 1 to 5 and high ink acceptability. It is suitable for the balance of the viscosity of the paper coating composition.

The addition condensation reaction of alkylenediamine or polyalkylenepolyamine with acrylic acid ester or methacrylic acid ester can utilize the Michael addition reaction which is an addition reaction to active double bonds of amines. That is, first, an acrylic acid ester or a methacrylic acid ester (hereinafter referred to as an acrylic acid ester or the like) is added to alkylenediamine or polyalkylenepolyamine, and an addition reaction is performed at 40 to 90 ° C. At this time, the molar ratio of the amines to the acrylic ester is 1 to 2 times the molar amount of the primary amino group contained in the amine, and the equimolar amount of the secondary amino group is added. Subsequently, the same molar amount of amines as the added acrylic acid ester or the like is added, and the mixture is gradually heated to about 130 to 160 ° C. to distill off by-produced alcohol by condensation. At this time, the addition reaction of the first step and the condensation reaction of the first step can be simultaneously mixed and continuously reacted. Again, an acrylic acid ester or the like is added in an amount according to the number of moles of the residual amine (1 to 2 times the molar amount of the primary amino group and the equimolar amount of the secondary amino group),
Addition reaction again at ~ 90 ° C. By repeating addition and condensation in this manner, an addition condensation product having a desired molecular weight can be obtained. In order to obtain the addition condensate for this purpose, the condensation reaction is carried out by 1-2
A molecular weight of about one time is preferable from the viewpoint of viscosity and performance. To the addition condensate of the desired molecular weight at the terminal amino group obtained above,
The resin of claim 3 can be obtained by adding an aliphatic monocarboxylic acid, heating it, and heating it to about 200 ° C. while dehydrating. In actual use, the condensation-produced resin can be cooled, added with water, neutralized and diluted with water to a predetermined concentration.

The coating resins (I), (I
I) and (III) are mixed with a pigment and an aqueous binder and used as a coating composition. Examples of the pigment include inorganic pigments such as calcium carbonate, kaolin, talc, satin white, aluminum hydroxide and titanium oxide, and organic pigments such as polystyrene resin and urea-formaldehyde resin. As the aqueous binder, water-soluble binders such as oxidized starch, phosphoric esterified starch, casein, polyvinyl alcohol, and carboxymethyl cellulose, carboxyl group-containing styrene-butadiene copolymer, vinyl acetate resin, ethylene-vinyl acetate resin, acrylic resin Emulsion binders such as resins can be used alone or in combination, and other dispersing agents, lubricants, defoaming agents, preservatives, etc. are added and mixed with the paper coating resin of the present invention to prepare a paper coating composition. And can be used for paper coating.

The composition ratio of the paper coating composition of the present invention is 5 to 30 parts by weight of an aqueous binder based on 100 parts by weight of the pigment.
Resin (I), (II) or (III) for paper coating
0.05 to 1.0 parts by weight is preferable. It is also possible to mix the resin for paper coating of the present invention with an aqueous binder in advance and prepare a composition for paper coating using the aqueous binder containing the resin for paper coating of the present invention.

The paper coating composition of the present invention is coated on a paper substrate by a conventionally known method, dried by a conventional method, and then dried.
Coated paper can be obtained by subjecting it to supercalendering, etc., if necessary.

[0020]

The coated paper using the resin for paper coating of the present invention is excellent in ink acceptability, especially in the flesh of a swimsuit, and has a thickening property of the paper coating composition which is apt to occur with conventional resins. It also has excellent viscosity stability at high shear.

[0021]

EXAMPLES The present invention will now be described with reference to examples, but the present invention is not limited to the following examples. All the following parts and% mean parts by weight and% by weight.

(Synthesis Example of Resin for Paper Coating) (Resin A) 81 parts (0.3 mol) of pentaethylenehexamine are charged and stirred in a reaction vessel equipped with a stir bar, a thermometer, a drainer, and a cooler. Nonanoic acid 77.4 parts (0.45 mol)
And 36 parts (0.6 mol) of acetic acid are gradually added so that the temperature does not exceed 100 ° C. When the addition is complete, the mixture is heated and the dehydration reaction by amidation proceeds at a temperature of 150 to 160 ° C., and the produced water is distilled out of the system. 200 to 2 from the time when 90% of the theoretical amount of water was distilled
After holding at 10 ° C. for 2 hours, the reaction was completed. This resin had an amine number of 256. After cooling, add water and adjust the pH with 30% sulfuric acid. Add water to obtain a solid content of 50.
%, PH 7.0, viscosity 60 cps of yellow resin aqueous solution was obtained.

(Resin B) 107.9 parts (0.4 mol) of pentaethylenehexamine are charged into a reaction vessel. 90 parts of acetic acid (1.5mo
The acid mixture obtained by mixing 1) and 55.8 parts (0.3 mol) of octylic acid is gradually added so that the reaction temperature does not exceed 100 ° C. When addition is complete, heat to 150-160
The dehydration reaction by amidation proceeds at ℃, the water produced is distilled out of the system. After 90% of the theoretical amount of water had been distilled off, the reaction was terminated after holding at 200 to 210 ° C. for 2 hours. This resin had an amine number of 173. After cooling, water was added, pH was further adjusted with 30% sulfuric acid, and finally water was added to obtain a brown resin aqueous solution having a solid content of 60%, a pH of 7.0, and a viscosity of 70 cps.

(Resin C) 57.6 parts of triethylenetetramine (0.4
(mol) is charged. Then, 29.3 parts of adipic acid (0.
2 mol) is gradually added. After adding, heat to 150
Although the dehydration reaction by amidation proceeds at ~ 160 ° C, it is 20
Heat to 0 ° C. The generated water is distilled out of the system. When 90% of the theoretical amount of water has distilled off, the mixture is cooled to 100 ° C. or lower. To this, an acid mixture of 40 parts (0.6 mol) of acetic acid and 19.5 parts (0.13 mol) of octylic acid is added and heated again to carry out the same dehydration reaction. 90% of theory
After the water was distilled off, the temperature was maintained at 200 to 210 ° C. for 2 hours, and then the reaction was completed. This resin had an amine number of 180. After cooling, water was added and further neutralized with 30% sulfuric acid to obtain a yellow resin aqueous solution having a solid content of 50%, pH of 7, and a viscosity of 155 cps.

(Resin D) 115.2 parts of triethylenetetramine (0.
8 mol) is charged. Adipic acid 87.6 parts (0.6 m
ol) is gradually added and heated when the addition is completed. 150-1
The dehydration reaction by amidation proceeds at 60 ° C, but 200 ° C
Heat until The generated water is distilled out of the system. When 90% of the theoretical amount of water was distilled off, the mixture was cooled to give octyl acid 14
6 parts (1.0 mol) are added and the temperature is raised again to carry out a dehydration reaction. 200 from the time when 90% of the total theoretical amount was distilled
The reaction was complete after holding at ~ 210 degrees for 2 hours. This resin had an amine number of 181. After cooling, add water and neutralize with 30% sulfuric acid to obtain solid content 50%, pH 7, viscosity 2
A yellow resin aqueous solution of 00 cps was obtained.

(Comparative Resin E) 81 parts of pentaethylenehexamine (0.3 m
ol). Add oleic acid 80.4 parts (0.3
mol) and 43.2 parts (0.72 mol) of acetic acid are gradually added, and when the addition is complete, the mixture is heated. 150 temperature
The dehydration reaction by the amidation of amine and acid proceeds at ˜160 ° C., and the produced water is distilled out of the system. 90% of theory
After the water was distilled off, the temperature was maintained at 200 to 210 ° C for 2 hours, and then the reaction was completed. This resin had an amine number of 250. After cooling, water was added, and the solution was further neutralized with 30% sulfuric acid to form an aqueous solution. However, the hydrophobicity was too strong to give an aqueous dispersion. Solid content 20%, pH 7, viscosity 1500
It was 0 cps.

(Comparative Resin F) 72 parts of triethylenetetramine (0.5 mo
l) is charged. To this, 45 parts (0.75 mol) of acetic acid was gradually added, and when the addition was completed, the mixture was heated. Temperature is 150-16
The dehydration reaction by amidation proceeds at 0 ° C. The generated water is distilled out of the system through a drain pipe. After 90% of the theoretical amount of water had been distilled off, the reaction was terminated after holding at 200 to 210 ° C. for 2 hours. This resin had an amine number of 678. After cooling, water was added, and the pH was adjusted with 30% sulfuric acid to obtain a yellow aqueous solution having a solid content of 60%, a pH of 7, and a viscosity of 200 cps.

[0028]

(Addition Condensation Resin H) 137.8 parts of methyl acrylate is charged into a reaction vessel. While stirring, 24 parts of ethylenediamine was added and maintained at 80 ° C. for 1 hour, then 96.2 parts of ethylenediamine was added and slowly heated to 140 ° C., and the temperature was maintained at 140 ° C. until the produced methanol was distilled, and the end group was an amino group. An addition condensation resin H was obtained.

(Resin I) 103.2 parts of addition condensation resin H was charged into a reaction vessel at 50 ° C.
Heat to 36 parts of acetic acid was slowly added to the reaction vessel while stirring so as not to exceed 100 ° C. The dehydration reaction started at about 150 ° C. by gradually heating, but the reaction was terminated after heating to 200 ° C. and distilling a predetermined amount of reaction water. This resin had an amine number of 262. Cool, add water,
Further, it was neutralized with 30% sulfuric acid to obtain a yellow resin aqueous solution having a solid content of 50%, a pH of 7, and a viscosity of 90 cps.

(Resin J) A reaction vessel was charged with 103.2 parts of an addition condensation resin H at 50 ° C.
Heat to 24 parts of acetic acid and 29.2 g of octylic acid are slowly added to the reaction vessel with stirring so as not to exceed 100 ° C. The dehydration reaction started at about 150 ° C. by gradually heating, but the reaction was terminated after heating to 200 ° C. and distilling a predetermined amount of reaction water. This resin had an amine number of 231. After cooling, water was added, and the mixture was further neutralized with 30% sulfuric acid to obtain a yellow resin aqueous solution having a solid content of 50%, a pH of 7, and a viscosity of 30 cps.

(Comparative Resin K) 103.2 parts of addition condensation resin H was charged into a reaction vessel at 50 ° C.
Heat to 40 parts of ethyl acrylate is gradually added to the reaction vessel, and then 44.4 parts of 40% aqueous acrylamide solution is added. After slowly heating and holding at 90 ° C. for 1 hour, the reaction was completed. This resin had an amine value of 443. After cooling, water was added and further neutralized with 30% sulfuric acid to obtain a pale yellow resin aqueous solution having a solid content of 50%, a pH of 7, and a viscosity of 35 cps.

(Examples 1 to 7) Resins A to D and resins I and J were blended according to the following paint blending compositions to prepare paper coating compositions. Using each of the paper coating compositions, coated paper was prepared by the following method, and a performance test was conducted.

Comparative Examples 1 to 3 Coated papers were prepared using comparative resins F and K in the same manner as in the examples, and the same tests were conducted. Further, a coated paper was prepared in the same manner as the composition for paper coating without using the comparative resin, and the test was conducted. The comparative resins G and E could not be coated because the viscosity of the paper coating composition was extremely high.

The composition of the paper coating composition is as follows. That is, Kaolin Cray (Ultra White 90):
70 parts, calcium carbonate (carbital 90): 30 parts,
Dispersant (Aron T-40): 0.2 part, sodium hydroxide: 0.1 part, starch (MS-4600): 5.0
Parts, SB latex: 9.8 parts, resin and comparative resin (as solid content): 0.2 part, water: appropriate amount added so that the solid content is 62%. SB latex composition (styrene / butadiene / methyl methacrylate / acrylamide / itaconic acid / acrylic acid) WT% = (25/49/15/8/2
/ 1).

The above-mentioned composition for paper coating was coated on a coated base paper by a rod coater so that the coating amount was 15 ± 0.5 g / m 2, and dried by a hot air dryer at 150 ° C. for 8 seconds. The coated paper obtained was treated at 20 ° C. and 65% R.C. H. After constant humidity control in a constant temperature and humidity room at 50 ° C, linear pressure 60 kg / cm, nip number 2
Was subjected to a super calender treatment and subjected to each test. The test methods are as follows. Paint viscosity: The solid content of the paint was 62%, and the viscosity immediately after dispersion at 25 ° C. was measured with a B-type viscometer using a rotor No. At 4, the measurement was carried out at 60 rpm. High shear viscosity: used with Hercules viscometer Bob A, rotation speed 4400
rpm, accelerator time 30 seconds (4000 for T4000
Torque value at rpm, unit is 10 ⁴ dyn · cm). White paper gloss: Measured (75 °) using a Murakami gloss meter. Printing gloss: An offset ink was printed with an RI printer and measured (60 °) using a Murakami gloss meter. Swimsuit Physical: RI
After kneading 0.40 ml of ink with a printing machine, water was flowed between rolls slightly separated to perform printing, and the print density was measured with a Macbeth densitometer. The higher the value, the higher the ink acceptability. Table 1 shows the test results.

[0037]

[Table 1]

Claims (3)

(57) [Claims] 1. (I) Polyalkylene polyamine and carbon
The reaction condensation products of aliphatic monocarboxylic acids having 1 to 12 and (II) a polyalkylene polyamine, formation reaction condensation of dibasic carboxylic acid compound and aliphatic monocarboxylic acids having 1 to 12 carbon atoms selected from those or Ranaru group,
One or more amines having an amine value of 100 to 500 as an essential component
A resin for paper coating that contains 2. (III) Alkylenediamine and poly
Amines selected from the group consisting of alkylene polyamines
And acrylic acid ester and methacrylic acid ester
Carbon in addition condensation products with esters selected from the group
Obtained by reacting an aliphatic monocarboxylic acid of the number 1 to 12
For coating paper containing the condensation product as an essential component
Fat. 3. An aqueous binder of 5 to 30 parts by weight per 100 parts by weight of the pigment, and 0.05 to 1.0 parts by weight of the paper coating resin according to claim 1 or 2 as essential components. A composition for paper coating, comprising: