JPS58126395A - Paper coating composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a coating composition for paper, and in particular a coating composition that has excellent water resistance and ink transfer properties, is free from coloration, generates extremely little formaldehyde, and has excellent blister resistance. The present invention relates to a paper coating composition that can provide textured paper.

It has long been known to produce coated paper with excellent printability by coating paper with a paper coating composition that mainly consists of pigments and a water-based binder, and also contains auxiliary agents such as water control agents. It is being

In recent years, there has been significant progress in coated paper manufacturing technology. For example, in order to increase productivity, the solid concentration in the coating composition is increased and coating is performed at high speed with a blade coater. It is required that there is no increase in viscosity and that coating properties are good.

Furthermore, as printing becomes more sophisticated and faster, and rotary offset printing becomes more widespread, improvements in the water resistance, ink transferability, and blister resistance of the coated layer are required.

In order to improve these performances, many proposals have been made in the past, including modification of the aqueous binder component and improvement of the auxiliary component.

For example, water resistance can be improved by increasing the amount of aqueous binder relative to the pigment, but on the other hand, ink transferability during printing decreases, so a method is generally used in which a water resistance agent is added as an auxiliary component.

A typical water-resistant agent in this case is a water-based binder water-resistant agent, but while all of the previously used or proposed water-resistant agents are effective, they also have serious drawbacks. , which was not practically satisfactory.

For example, the melamine-formaldehyde initial condensate has insufficient ink transfer properties to coated paper, and the pH of the coating composition
When this is high, there are problems such as insufficient water resistance and a large amount of free formaldehyde generated from the coated paper. In addition, the reaction product of polyamide polyurea and formaldehyde has an excellent effect on improving the ink transfer property of coated paper.
Although it has the advantage of good water resistance and little generation of free formaldehyde from coated paper, it is still a step inferior in water resistance and ink transfer improvement effect.Dialdehydes such as glyoxal are It is not preferable to use polyvalent metal salts such as zirconium because they cause significant thickening of the coating solution.

In order to improve these drawbacks, the present inventors have repeatedly investigated the amount of iron, and as a result, the present inventors have developed a coating composition for paper containing a thermosetting resin produced by a specific method as a water-resistant agent. The inventors have discovered that the product satisfies the purpose and has extremely excellent effects, and have completed the present invention.

That is, the present invention provides a paper material which is mainly composed of a pigment and an aqueous binder, and further contains a mixture of a polyamide polyurea, a reaction product with formaldehyde and epihalohydrin, and a polyalkylene polyamine, or a reaction product thereof. In the present invention, which may be a coating composition, polyamide polyurea refers to a product obtained by subjecting urea and polyalkylene polyamine to a deammoniation reaction, followed by dehydration condensation with a dibasic carboxylic acid, and further deammoniation reaction with urea [hereinafter Polyamide polyurea (A)
[hereinafter referred to as polyamide polyurea (B)], which is obtained by dehydration condensation of a polyalkylene polyamine and a dibasic carboxylic acid, and then subjected to a deammonia reaction with urea.

In the present invention, polyalkylene polyamines are those having two primary amine groups and at least one secondary amino group in the molecule, such as diethylene triamine, triethylene tetramine, tetraethylene pentamine, imino Bispropylamine, 3-asahexane-1,6-diamine, 4,7-diasadecane-1.10
-Diamines, etc. These polyalkylene polyamines may be used alone or in combination of two or more.

Dibasic carboxylic acids used in the present invention include aliphatic carboxylic acids such as succinic acid, glitaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, aromatic carboxylic acids such as isophthalic acid and terephthalic acid, and A mixture of

In the present invention, the general manufacturing method conditions for polyamide polyurea are as follows.

0 Production method of polyamide polyurea (A) The molar ratio of urea and polyalkylene polyamine is approximately 1.
: It is preferable to carry out the reaction at around 2, and the reaction temperature is 100
The temperature is preferably 120 to 170°C, preferably 5) to 200°C, and the reaction is allowed to proceed for 2 to 8 hours while removing the generated ammonia from the system. Next, 0.3 to 0.0% per 21 moles of polyalkylene polyamide
Dehydration condensation with 7 mol of dibasic carboxylic acid is carried out at a reaction temperature of 120 to 250° C., preferably 140 to 200° C., and the reaction is carried out for 2 to 10 hours while removing the water produced from the system. The synthetic reaction product thus obtained is further reacted with urea. The amount of urea is 0.2 to 1.0 per mole of secondary amino group in the raw material polyalkylene polyamine.
5 mol, preferably 0.5 to 1.1 mol.

The reaction temperature is 100-180℃, preferably 120-150℃
℃, and the reaction is carried out at this temperature for 1 to 5 hours while removing generated ammonia from the system. In this way, polyamide polyurea (A) is obtained.

The reaction between the polyalkylene polyamine and the dibasic carboxylic acid is preferably carried out in an amount of 1.4 to 3.0 mol of the polyalkylene polyamine per 1 mol/G) mol of the dibasic carboxylic acid. The reaction is carried out at 1.8 to 2.5 moles at 120 to 250° C., preferably at 140 to 200° C., for 2 to 10 hours while removing the produced water in series. The dehydration condensation reaction product thus obtained is then reacted with urea.

The amount of urea used is 0.2 to 1.0 mol, preferably 0.4 to 1.0 mol, per 1 mol of amino groups in the raw material polyalkylene polyamine.
It is 0.8 mol. The reaction temperature is 100-180°C, preferably 120-150°C. At this temperature 1~
The reaction is carried out for 5 hours while removing the generated ammonia from the system. As a method of charging urea, it is possible to charge the required amount all at once and react, or to charge a portion of the required amount and complete the deammonification reaction, then charge the remaining urea and perform the deammonification reaction again. be. In this way, a polyamide polyurea (, B) is obtained.

The polyamide polyurea obtained as described above is dissolved in water and further reacted with formaldehyde. The reaction is carried out using an aqueous solution of polyamide polyurea with a concentration of 20 to 70% by weight, preferably 80 to 60% by weight, and 0.2 to 1 mole of total urea used to synthesize the polyamide polyurea.
．． The reaction is carried out using 0 mol, preferably 0.8 to 0.7 mol, of formaldehyde at 40 to 80°C for 0.5 to 10 hours under acidic or alkaline conditions. Furthermore, it is preferable to carry out the reaction under acidic conditions.

The reaction product of the obtained polyamide polyurea and formaldehyde is further reacted with epihalohydrin. Examples of the epihalohydrin used in the present invention include Teha, epichlorohydrin, and epichlorohydrin.

The appropriate amount of epihalohydrin to be used is 0.1 to 4 mol, preferably 0.5 to 3 mol, per 1 mol of the dibasic carboxylic acid used to synthesize the polyamide polyurea. The reaction is carried out at a temperature ranging from 30°C to reflux for 0.5 to 15 hours.

The reaction product of the polyamide polyurea, formaldehyde, and epihalohydrin obtained as described above is used by further mixing or reacting with a polyalkylene polyamine. When mixing, the reaction product of polyamide polyurea, formaldehyde, epihalohydrin, and polyalkylene polyamine may be mixed separately into the paper coating composition, or the reaction product of polyamide polyurea, formaldehyde, epihalohydrin, and polyalkylene may be mixed in advance. The polyamine may be mixed and added to the paper coating composition. The amount of polyalkylene polyamine used here is 0.1 to 3 mol per mol of dibasic carboxylic acid used to synthesize polyamide polyurea.
．． 0 mol, preferably 0.2 to 1.5 mol.

When the reaction product of polyamide polyurea, formaldehyde, and epihalohydrin is reacted with polyalkylene polyamine, the reaction is carried out at a temperature of 80 to 100° C. for 0.5 to 10 hours.

The paper coating composition of the present invention is prepared in the same manner as the conventional method, but in order to fully exhibit the seedlings, a mixture of a reaction product of polyamide polyurea, formaldehyde, and epihalohydrin and a polyalkylene polyamine, or a mixture thereof is used. The reaction product is usually 0.05 to 5% by weight based on the weight of the pigment.
, preferably in the range of 0.01 to 2% N.The water resistance agent specified in the present invention alone is sufficiently effective, but in some cases, a part of it may be replaced with other water resistance agents. It is also possible.

As the aqueous binder and pigment used in preparing the paper coating composition of the present invention, conventionally known ones or those used as they are may be used. Examples of water-based binders include starch, oxidized starch, modified A
,, AT, polyvinyl alcohol, carlein, gelatin, (10) carboxyl methyl cellulose, hydroxyethyl cellulose, water-soluble binder with soy protein, styrene-butadiene resin, vinyl acetate resin, ethylene-vinyl acetate resin, methyl methacrylate resin, etc. Examples include water emulsion and dispersion binders.

Examples of pigments include inorganic pigments such as kaolin clay, talc, titanium dioxide, aluminum hydroxide, calcium carbonate, satin white, and barium sulfate, and organic pigments whose main components are styrene, urea, etc. These may be used alone or in combination of two or more in any proportion.

In addition, the paper coating composition of the present invention includes, as other components, a dispersant, a thickener, a thinner, an antifoaming agent, a foam suppressor, a preservative,
Antifungal agents, fluidity regulators, release agents, dyes, coloring agents such as colored pigments, special performance imparting agents such as conductive agents, etc. may be added as necessary, but this will hinder the effects of the present invention. It's not a thing.

Further, the concentration and other adjustment conditions of the coating composition of the present invention can be adjusted by conventional methods in exactly the same manner as conventional methods.

The paper coating composition of the present invention can be coated on a paper substrate by a conventionally known method, such as a blade coater, an air knife coater, a roll coater, a size press coater, or a cast coater. Coated paper can be produced by coating the song on a paper, drying it as necessary using a conventional method, and subjecting the song to a super calender, machine calender, or other treatment as required.

The paper coating composition of the present invention obtained in this manner does not cause color shock (such as significant thickening of the composition and scattering of pigments).
The coating liquid has excellent stability, and it can be used on paper substrates.
The coated paper obtained by coating has excellent deicing properties, generates very little formaldehyde, has excellent ink transfer properties, and shows no discoloration. It has various excellent features that are effective in improving blister resistance in rotary offset printing.

The present invention will be explained below with reference to Examples.

Reference Example 1 (]) Synthesis of resin [A] Triethylenetetramine 292y- (2 mol) and urea 6 were placed in a four-eye flask equipped with a thermometer, reflux condenser, and stirring bar.
0? - (1 mol) was charged, and the reaction was carried out at 145 to 150°C for 4 hours while removing the generated ammonia from the system. Then, 14 fl (1 mol) of adipic acid was added, and 1 mol of adipic acid was added.
The feeding reaction was carried out at 50-155°C for 5 hours. 120℃
Add 240P (4 mol) of urine after cooling to 125 ~
Deammonification reaction was carried out at 180°C for 2 hours. Thereafter, water 18501 was gradually added to obtain an aqueous solution of polyurea polyamide.

Next, 87% formalin 202.51i' (2.5 mol) was added, the pI was adjusted to 5 with concentrated hydrochloric acid, and then 65°C
The mixture was stirred for 4 hours while keeping it warm for 4 hours, and then (1B) was cooled to 25°C to obtain a thermosetting resin [A] with a solid content of 80% by weight.

(2) Synthesis of resin [IB] Resin (A) was obtained in exactly the same manner as in (1), and then epichlorohydrin 98y (1 mol) and water 217y! Add -,
The mixture was stirred for 2 hours at 60°C. The mixture was cooled to 25° C. to obtain a thermosetting resin [B] with a solid content of 80% by weight.

(3) Synthesis of resin [C] Resin CB) was obtained in the same manner as in (2), and then triethylenetetramine 7B ¥-(0.5 mol) and water 170F
was added, stirred at 60°C for 3 hours, and then cooled to 25°C to obtain a thermosetting resin [C] with a solid content of 80% by weight.

(4) Diethylenetriamine 2065'
(2 mol) and urea 605' (1 mol), 140
Ammonia removal reaction was carried out at ~1115°C for 5 hours, then 146g of adipic acid (1 mol) was added,
Dehydration condensation was carried out at 70° C. for 2/lj) hours. After cooling to 120"c, add urine accumulation 1209 (2 mol), ]3c) ~ 1401",
], the deammonia reaction was carried out for 5 hours. Then water 9
0 (151) was gradually added to obtain a saturated aqueous solution of polyurea polyamide.

Next, 37% formalin 145.8P (1.8 mol) was added, and 20. Adjust the pH to 4.5 with N-sulfuric acid and heat at 60°C.
The mixture was stirred and kept warm for 3 hours. Then epichlorohydrin 1
Add 85P (2 mol) and water 2772 and mix at 60"c.
The mixture was kept warm and stirred for an hour. Thereafter, it was cooled to 25 ° C. to obtain a pA curable resin [D] with a solid content of 40%. Synthesis of t = 7 (5) resin (,E) (resin CD) was obtained in the same manner as in 4, >. Then 1.46 P (1 mol) of diethylenetriamine and 219 p of water
was added to obtain a thermally nitrifiable resin [E] with a solid content of 40%.

Diameter example 2 (]) Preparation of coating composition for paper Pigment slurry using kaolin clay, calcium carbonate, and aluminum hydroxide as pigments, adding a sodium polyacrylate-based dispersant, and dispersing them in water. Add an aqueous oxidized starch solution and a styrene-butadiene latex that have been gelatinized in advance, and then add an appropriate amount of a waterproofing agent and mix well with stirring.Finally, the pH of the composition is adjusted to 9.5 with an aqueous caustic soda solution. So, the solid content concentration is 55
i, :! :%, and the coating composition for negative use was adjusted. The basic blending ratios of components other than the water resistant agent in the composition are shown in Table 1.

(2) Preparation of coated paper The composition obtained by the above method was coated on both sides of coated base paper with a weight of 8,517 m using a coach ink rod so that the dry solid content was approximately 15 P/m on one side. Coating,
Hot air drying was performed at 120°C for 30 seconds. This coated paper was then subjected to a super calender (roll temperature 60°C,
Roll linear pressure 60Kg/(to), 2 passes), 20℃, 6
Test samples were prepared in a 5% RH environment and subjected to various tests.

(3) Various test methods (A) Physical properties of coating liquid 1) pFI of coating liquid Using glass electrode pH meter, measurement temperature 20"C■ Viscosity of coating liquid Using B-type viscometer, rotation speed (iQrpm, measurement temperature 20℃ (B) Coating properties ■Water resistance of coating film (A) Wet, Rub method Approximately 0.1 drop of ion-exchanged water was placed on the coated paper surface, rubbed 7 times with a fingertip, and the elution amount was measured on black paper. The amount of elution was determined visually.

The criterion amount was determined as follows.

Water resistance (poor) 1-5 (excellent) (o) Wet Pick method RI tester (
(manufactured by Mei Seisakusho), the coated surface was moistened with a water supply roll and then printed (17), and the peeling off and damage on the coated surface were observed and judged with the naked eye.

f(I constant standard is the same as the Wet Rub method.

(Formaldehyde standard JISL-1 from 0 coating roughness
041 Liquid phase extraction method (2) Based on the acetylacetone method The amount of formaldehyde was measured by sealing it in a polyethylene bag to prevent it from migrating or escaping.

(2) Ink transferability of coated paper Printing was performed using the R1 test method using the submerging method, and the ink transferability was visually observed and judged.

The evaluation criteria were 5 (excellent) to 1 (poor).

(b)　　　　A　Method Water was dropped onto the ink that was being mixed in. Print later.

(b) Method B After moistening the surface to be coated with a water supply roll to print.

(c) C method (18) By a combination of methods A and B above, Print.

(iil? The white skin of paper and heat-resistant white skin The B value of the Hunter reflectance meter is measured in accordance with JISP-8128 for the white skin of the coated boat before and after heat treatment in a hot air dryer at 150°C for 80 minutes. It was tested by

The thicker the number, the better the white box.

■ Blister resistance Using an R1 tester, print on both sides of double-sided coated paper using off-circle ink, and after adjusting the humidity, immerse it in a heated silicone oil bath to determine the lowest temperature at which blisters occur. show.

Examples 1 to 6 Using the resin obtained in Reference Example 1, evaluation was performed by the method shown in Reference Example 2. The resin used and the compounding recipe are as follows.
The performance test results are shown in Table 2. Comparative Examples 1 to 2 A coating liquid was prepared in the same manner as in the example except that resin CB) to [El and polyalkylene polyamine were not used as a water resistant agent. We then conducted a performance evaluation. Combination formulation, performance (Test results are shown in Table 2.

Comparative Examples 8 to 6 Coating liquids were prepared in the same manner as in the examples except that resin CA] or resin [■3] was used as a water-strengthening agent, and performance evaluation was performed. The formulation and performance test results are shown in Table 2.

Table 1 Procedural Amendment W (Voluntary) 1. Indication of matter A'1 Patent Application No. 7255 of 1982 2. Title of invention Coating composition for paper: 3. Relationship with the person making the amendment: Patent applicant: 5-15 Kita-1, Higashi-ku, Osaka (2 (19)) Representative Takeshi Kamigata, Sumitomo Chemical Co., Ltd. 9 Agent: 5-15 Kitahama, Higashi-ku, Osaka Address 5, Detailed explanation of the invention column of the specification subject to amendment (1) Contents of amendment (1) In the third line of page 7 of the specification, the text "r 250" was corrected to "r 2511 tej" do.

(2) From page 12, page 1ζ'', line 2-1, ``Not allowed. Offset rotary printing'' is corrected to ``Not allowed, offset rotary printing.'' 1F.

(C3) In the 5th line from the bottom of page 13, correct the statement ``polyurea polyamide'' (also ``polyamide polyurea'').

(/L) On page 15, lines 4-5, the phrase "polyurea polyurea/mide" is corrected to "polyamide polyurea".

(5) rWe L, Ru l on page 17, line 11
) Law' should be corrected to read 'rWe t RtJ b9left'.

(15) On page 18, line 11 of the same page, the phrase ``rRI test method'' is corrected to ``R1 test machine.''

From J- Written amendment (voluntary) 1.Display of the incident 1981 Patent Application No. 7255 2. Name of the invention Coating composition for paper 3. Person who makes corrections Relationship to the case Patent applicant 5-15 Kitahama, Higashi-ku, Osaka (209) Sumitomo Chemical Co., Ltd. Representative Takeshi Tsuchikata 4. Agent 5-15 Kitahama, Higashi-ku, Osaka 5. Subject of correction Detailed description of the invention in the specification <1)　　　　　　　　　　.

6. Contents of amendment (1) On page 10, lines 3-4 of the specification, there is a statement that says, ``The paper coating composition of the present invention exhibits 139111.''
Correct as shown below.

The paper coating composition of the present invention can be prepared in the same manner as conventional methods, and there are no restrictions on the method of preparation. Specifically, a coating composition may be prepared by adding a water-resistant agent to a mixture of a pigment and an aqueous binder, or the necessary amount of a water-resistant agent may be added to a binder component such as latex or starch or a slurry of a pigment in advance. They may be blended in advance and used to prepare a coating composition, or they may be prepared in any other order. In order to fully demonstrate the effects of the present invention,

Claims (1)

[Claims] 1. A paper coating composition which mainly contains a pigment and an aqueous binder, and further contains a mixture of a polyamide polyurea, a reaction product with formaldehyde and epihalohydrin, and a polyalkylene polyamine, or a reaction product thereof.