JPH0660477B2 - Lubricant for paper coating and manufacturing method thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a paper coating lubricant. More specifically, it relates to a lubricant used for a paper coating mainly composed of a pigment and a binder.

Conventionally, higher fatty acid metal salt, higher fatty acid amide, wax emulsion, polyethylene glycol, polyethylene glycol ester, liquid hydrocarbon oil emulsion, polyethylene dispersion and aliphatic sulfated oil have been used as lubricants for paper coating. . However, these lubricants have the drawbacks that the releasing effect and the dusting preventing effect in the calendering process of offset paper, gravure paper, etc. are weak and stains occur on the surface of the calender roll. Particularly in the production of coated paper using a binder having a low strength or coated paper having a low binder level, for example, gravure paper, these lubricants are completely ineffective in preventing dusting in the super calendering process, resulting in significant dusting on the super calender. It has the disadvantage that it often occurs and the calender must be stopped to clean the calender roll surface. The amount of dusting generated can be reduced to some extent by increasing the amount of lubricant added, but on the other hand, the friction coefficient of the coated paper is reduced. However, addition of a large amount of lubricant is limited. Further, these lubricants have a drawback that the effect of improving the printing gloss of the coated paper is hardly recognized.

In recent years, sucrose higher fatty acid ester (JP-A-52-55707) and aqueous emulsion of dimer of higher fatty acid (JP-A-56-6507)
Higher fatty acid esters such as 4) have been reported as anti-blocking agents or anti-dusting agents, but similar to the above-mentioned lubricants, the releasing effect, the anti-dusting effect, and the printing gloss improving effect are all insufficient, so that the conventional It does not solve the drawbacks of the above lubricants. Further, in gravure printing, there is a drawback that the dot loss rate increases.

The inventors of the present invention are superior to the conventional lubricants in the releasing effect and the dustproofing effect in the calendering process, exhibit the effect at a lower addition amount than the conventional lubricants, and have the effect of improving the printing gloss. The present invention has been achieved as a result of repeated research for developing agents.

The present invention has the general formula (Wherein R represents an alkyl group or an alkenyl group having 11 to 21 carbon atoms, and R'represents an alkyl group or an alkenyl group having 12 to 22 carbon atoms). It is an agent.

In the general formula [I], when R which is an alkyl group or an alkenyl group has less than 11 carbon atoms and R ′ which is an alkyl group or an alkenyl group has less than 12 carbon atoms, the lubrication effect is insufficient and a sufficient releasing effect is obtained. However, the effect of preventing dusting is not obtained, which is not preferable.

R is usually a residue of a saturated or unsaturated carboxylic acid having 11 or more carbon atoms, and examples thereof include the following carboxylic acids.

Lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid,
Saturated fatty acids such as cerotic acid and montanic acid, butenoic acid, pentenoic acid, hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, undecenoic acid, dodecenoic acid,
Unsaturated fatty acids such as tridecenoic acid, tetradecenoic acid, pentadecenoic acid, hexadecenoic acid, octadecenoic acid, gadrenic acid and erucic acid, linoleic acid, linolenic acid, stearolic acid, and the above saturated or unsaturated fatty acids such as isostearic acid, oleic acid, and elaidic acid. It is a structural isomer fatty acid of unsaturated fatty acid.

Among these fatty acids, preferred ones have 12 to 22 carbon atoms.
Straight chain saturated fatty acids such as lauric acid, myristic acid,
Palmitic acid, stearic acid and behenic acid. R may be a residue of a carboxylic acid anhydride or a carboxylic acid halide, for example, saturated or unsaturated fatty acid anhydride such as stearic anhydride or oleic anhydride, or palmitic acid bromide, stearic acid chloride or oleic acid chloride. Examples of saturated and unsaturated fatty acid halides are:

These carboxylic acids, carboxylic acid anhydrides and carboxylic acid halides can be used alone or in a mixture of two or more kinds.

In addition to the above-mentioned carboxylic acids, carboxylic acids having an aromatic group such as benzoic acid and ω-phenylcapric acid, and halogenated fatty acids such as chlorinated stearic acid may be used together.

R'is usually a residue of a saturated or unsaturated alcohol having 12 or more carbon atoms, and examples thereof include the following alcohols.

Lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, eicosyl alcohol and behenyl alcohol,
2-undecyl tetradecyl alcohol and other saturated aliphatic alcohols, dodecenol, fiseteryl alcohol, somalyl alcohol, oleyl alcohol, gadreyl alcohol and 11-docosenol and other unsaturated alcohols, and isotridecyl alcohol, sec-
Tridecyl alcohol, isostearyl alcohol, 2
-Structural isomer alcohols of the above saturated and unsaturated aliphatic alcohols such as octadecenyl alcohol.

Among these aliphatic alcohols, preferred are saturated aliphatic alcohols having 12 to 22 carbon atoms, such as lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol and behenyl alcohol.

The emulsifying dispersant used for emulsifying and dispersing the ester compound is at least one nonionic surfactant selected from polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether or polyoxyethylene alkyl ester, and sulfonic acid. At least one anionic surfactant selected from salt type or sulfate ester type anionic surfactants, or a salt of a copolymer of αβ-unsaturated dibasic acid or its monoester and styrene as an essential component It is a necessary condition for obtaining a highly concentrated, low-viscosity and stable emulsion dispersion.

The polyoxyethylene alkylphenyl ether has usually 6 to 12 carbon atoms, preferably 7 to 10 carbon atoms, more preferably 8 to 9 ethylene oxide of alkyl group-substituted phenol, 4 to 70 moles, preferably 4 to 50 moles, and further preferably Examples include 5 to 25 mol adducts.

The polyoxyethylene alkyl ether has usually 8 to 20 carbon atoms, preferably 12 to 20 carbon atoms, more preferably 16 to 18 carbon atoms.
Addition products of the higher alcohols of 5 to 70 mol, preferably 13 to 50 mol, and more preferably 22 to 45 mol of ethylene oxide.

The polyoxyethylene alkyl ester has usually 8 to 20 carbon atoms, preferably 12 to 20 carbon atoms, more preferably 16 to 18 carbon atoms.
Higher fatty acid and ethylene oxide mole number is usually 5-7
Examples thereof include mono- and diesters of 0, preferably 13 to 50, and more preferably 22 to 45 polyethylene glycol. As the polyoxyethylene alkyl ester, a monoester having a small thickening effect is more preferable.

Examples of the sulfonate type anionic surfactant include alkyl benzene sulfonates such as tetrapropylene benzene sulfonate, linear dodecyl benzene sulfonate and eicosyl benzene sulfonate, and α-sulfonate such as 1-hexadecene sulfonate. -Dialkyl sulfosuccinates such as olefin sulfonate, N-methyl-N-oleyl taurine, sulfosuccinic acid di-2-ethylhexyl ester salt, alkyls such as tetradecyl sulfonate, hexadecyl sulfonate and petroleum sulfonate Α such as sulfonate and α-sulfopalmitate
-Sulfofatty acid salts, α-sulfolauric acid ethyl ester salts and ester-bonded sulfonates such as dioctyl sulfosuccinate, polyoxyethylene styrenated phenyl ether sulfonates and naphthalene sulfonate formalin condensation with a condensation degree of 2-12 Things can be given.

Examples of the sulfate ester type anionic surfactant include alkyl sulfates such as stearyl sulfate, sulfated oil and fat salts such as sulfated castor oil, other polyoxyethylene alkyl ether sulfates, polyoxyethylene styrenated phenyl ether sulfates, and the like. Aliphatic sulfates such as stearyl alcohol sulfate are included.

Ammonium as the salt of sulfonate and sulfate,
Examples include amines such as sodium, potassium, calcium, magnesium, and diethanolamine. Preferred among these anionic surfactants are alkylbenzene sulfonates such as linear dodecylbenzene sulfonate, tetradecyl sulfonate, hexadecyl sulfonate and alkyl sulfonates such as petroleum sulfonate, condensed 2-10 naphthalene sulfonate formalin condensates and stearyl sulphates. Ammonium, sodium and potassium salts are preferred as salts.

Examples of the salt of a copolymer of α, β-unsaturated dibasic acid or its monoester and styrene include maleic acid,
Examples thereof include fumaric acid, maleic acid monomethyl ester, maleic acid monoisopropyl ester, maleic acid monobutyl ester, and a salt of a copolymer of styrene and a monoester of maleic acid with ethylene glycol monobutyl ether. Alkali metal or ammonium salts are usually preferred as the salt.

The proportion of the emulsifying dispersant used is usually 3 to 40 parts by weight with respect to 100 parts by weight of the ester compound [I],
It is preferably 5 to 20 parts by weight, and the anionic surfactant is usually 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, more preferably 0.3 to 2 parts by weight. In the case of a salt of a copolymer of α, β unsaturated dibasic acid or its monoester and styrene, the amount is usually 2 to 30 parts by weight, preferably 3 to 20 parts by weight.

For producing the aqueous dispersion of the ester compound [I], is the ester compound [I] heated and dissolved at 60 to 150 ° C. and added to water at 60 to 100 ° C. in which a necessary amount of an emulsifying dispersant is dissolved? ,
Alternatively, an emulsifying dispersant is previously mixed and dissolved in the ester compound [I] heated and dissolved at 60 to 150 ° C.
It can be obtained by pouring the mixture into water and then emulsifying and dispersing with a high-speed stirring emulsifying machine at a liquid temperature of 60 to 100 ° C. at a speed of 500 to 10,000 rpm or a piston type high pressure emulsifying machine at a pressure of 50 to 500 kg / cm and then cooling.
The ester compound [I] can be synthesized by a usual method. For example, in the case of a fatty acid or a fatty acid halide and an aliphatic monohydric alcohol, usually in a molar ratio of 1: 1, and in the case of a fatty acid anhydride and an aliphatic monohydric alcohol, usually in a molar ratio of 1: 2, under a nitrogen atmosphere. The dehydration or dehydrochlorination reaction may be carried out at 70 to 200 ° C. until an arbitrary esterification rate is reached. To accelerate the esterification reaction, a catalyst such as hydrogen chloride, sulfuric acid, P-toluenesulfonic acid or boron trifluoride etherate may be used in combination, and dehydration or dehydrochlorination may be carried out under reduced pressure. Azeotropic dehydration may be performed using a solvent such as.

The paper coating lubricant of the present invention comprises an antioxidant, an ultraviolet absorber,
Water resistance agent, antiseptic and fungicide, insecticidal fungicide, dispersant, defoamer,
A fragrance, a bulking agent, a dye, a pigment or other lubricant may be contained or mixed and used.

The lubricant for paper coating of the present invention is used by adding it to a paper coating paint mainly containing a pigment and a binder. Examples of the pigment include inorganic pigments such as clay, calcium carbonate, titanium oxide, satin white, barium sulfate, talc and zinc oxide; organic pigments such as plastic pigments (Japanese Patent Publication No. 46-65).
24) and combinations thereof. As the binder, a natural binder, a synthetic binder or a mixture thereof can be used. Natural binders include starch, modified starch, soy protein,
Casein is mentioned. Styrene butadiene latex as synthetic binder; acrylic resin emulsion,
Aqueous suspensions of polymers containing especially small amounts of copolymerized ethylenically unsaturated carboxylic acids; butadiene and acrylonitrile, vinyl acetate and acrylate, butadiene and methyl methacrylate, vinyl chloride and vinylidene chloride copolymers, butadiene and methyl. Mention may be made of homopolymers of methacrylates, vinyl acetate, chlorobrene, vinyl chloride and butyl methacrylate, as well as latexes of polymerizable materials which are at least partially soluble in aqueous media such as polyvinyl alcohol.

The amount of the lubricant for paper coating of the present invention (in terms of solid content) is a pigment.
It is usually 0.1 to 20 parts, preferably 0.2 to 10 parts, and more preferably 0.3 to 5 parts per 100 parts (parts by weight, the same hereinafter). When it is less than 0.1 part, the releasing effect and dustproofing effect and printing gloss improving effect are insufficient, and when it is more than 20 parts, the coated paper is too slippery, which is not preferable.

The paper coating paint using the lubricant for paper coating of the present invention is usually used in the form of an aqueous dispersion, and if necessary, other additives,
For example, dispersant (sodium pyrophosphate, sodium hexametaphosphate, sodium polyacrylate, etc.), defoaming agent (paraffin, phosphate ester, polyglycol, silicon compound, etc.) Leveling agent (urea, dicyandiamide, etc.), water retention agent, fluidity Improvement agents (carboxymethyl cellulose, sodium alginate, hydroxyethyl cellulose, etc.), water resistance agents (urea resin, melamine resin, glyoxal, etc.), preservatives (formalin, etc.), fluorescent dyes, etc. are added.

The paper coating can be applied to the paper substrate by known techniques, such as air knife coaters, trailing blade coaters, inverted blade coaters, roll coaters, applicators. After coating, dry and apply calendering or super calendering as needed. The coating temperature is usually 10 to 60 ℃, and the drying temperature is usually
90 ~ 130 ℃, the temperature of calender ring, super calender ring is 40 ~ 100 ℃.

The paper coating lubricant of the present invention is extremely excellent in the releasing effect in the calendering process and the dusting preventing effect, and the addition amount is 1/2 to 1/3 that of the conventional lubricant as compared with the conventional lubricants such as calcium stearate. In addition, the effect of preventing release and dusting far superior to that of the conventional lubricant such as calcium stearate can be exhibited. Also, due to the drastic reduction of this addition amount, there is an unavoidable side effect problem when adding a large amount as a countermeasure against dusting in conventional lubricants, that is, paper winding due to excessive slipping of paper and sheet ejection work at the time of sheet printing. It has become possible to eliminate problems such as deterioration of printing suitability such as defectiveness, ink receptivity of coated paper, and reduction of wet strength, suitability for lapping coated white paperboard, and suitability for blister pack.

In addition, it has an effect that cannot be obtained with conventional lubricants and can improve the printing gloss of coated paper that has not been obtained. Further, since the dusting does not occur, the smoothness of the coated paper is improved, and it also has effects such as reduction of missing dots in gravure printing and improvement of white paper gloss.

The paper coating lubricant of the present invention can also be used as a sizing agent, and its addition amount can be variously changed, but it is usually 0.01 to 5% by weight (in terms of solid content) of the pulp, preferably 0.05 to 2% by weight, and further preferably Is 0.1 to 1% by weight. The size of paper is not particularly limited and can be applied to a wide range of base papers,
Can be used with or without paper strengthening agents
It can be applied to paper made in the H region. How to use
The sizing agent and the fixing agent may be added to and mixed with the dispersion liquid of the beating and dispersed pulp and the filler such as clay and calcium charcoal, and the papermaking may be performed.

The lubricant of the present invention can also be used as a waterproofing agent for cement, gypsum board and the like.

The present invention will be described below with reference to examples, but the present invention is not limited thereto.

Example 1-5 (Lubricant A) 1190 gr of water, 90 gr of ethylene oxide 7 mol adduct of stearyl alcohol were added to an emulsifier equipped with a piston type high pressure emulsifier.
Ethylene oxide 14 mol adduct of lauryl alcohol 80
gr, sulfosuccinic acid dihexyl ester sodium 15g
Add r, and 5 gr of sodium lauryl sulfonate 70
After heating to 0 ° C. to uniformly dissolve, 1000 gr of behenyl behenate heated to 120 ° C. was added under stirring, emulsification was performed with a piston type high pressure emulsifier at a pressure of 300 kg / cm ² , and immediately cooled to 28 ° C. Emulsion dispersion with 50% concentration and 150 cps viscosity (Lubricant A)
Got

Lubricant [B] In the same emulsifying device as in the example of the lubricant [A], water 1138 gr, stearyl alcohol ethylene oxide 14 mol adduct 85 g
25 g of a monoester of r, lauric acid and polyethylene glycol consisting of 18 mol of ethylene oxide, 20 gr of ethylene oxide 20 mol adduct of nonylphenol, 4 gr of sodium formalin naphthalenesulfonate condensate with an average degree of condensation of 3 and 4 gr of sodium dodecylbenzenesulfonate. Put in, heat to 80 ℃, dissolve evenly, add 1000 gr of stearyl stearate heated to 120 ℃, stir and stir, and then emulsify with a piston type high pressure emulsifier at a pressure of 250 kg / cm ² and immediately cool to 25 ℃ and concentration 50% A white emulsion dispersion (lubricant B) having a viscosity of 120 cps was obtained.

Lubricant [C] Oleyl oleate 1000 gr, ethylene oxide 14 mol adduct 60 gr, stearyl alcohol ethylene oxide 23 mol adduct 25 gr, stearic acid / polyethylene glycol monoester 40 gr 40 mol, myristin Monoester of acid and polyethylene glycol consisting of 23 mol of ethylene oxide 25gr, sodium petroleum sulfonate 10
Add gr and potassium hydroxide 0.15gr and mix evenly at 80 ℃, then add 1160gr of water at 80 ℃ little by little at 3000rpm.
After high-speed stirring at 27 ° C, cool to 27 ° C and concentrate at a concentration of 50% and a viscosity of 25 ° C.
A pale yellowish white emulsion dispersion of cps (Lubricant C) was obtained.

Lubricant [D] By replacing stearyl stearate with lauryl stearate under the same conditions as in the example of lubricant [B], a white emulsion dispersion (lubricant D) having a lauryl stearate concentration of 50% and a viscosity of 105 cps was obtained. Obtained.

Lubricant [E] 1,500 gr of water and 75 gr of ammonium salt of a copolymer of maleic acid monobutyl ester and styrene were put in an emulsifier equipped with a piston type high pressure emulsifier, and heated to 80 ° C to uniformly dissolve them.
1425 gr of lauryl stearate heated to 90 ° C. was added under stirring, and emulsification was performed at a pressure of 300 kg / cm ² by a piston type high pressure emulsifying machine and cooled to 30 ° C. A white emulsion dispersion [E] having a concentration of 50% and a viscosity of 60 cps was obtained.

Comparative Examples (1 to 6) Lubricants [F] to [K] Lubricants [F] to [J] were obtained under the same conditions as the examples of the lubricant [B]. The concentration is 50% in each case. Methyl stearate with a viscosity of 210 cps is a lubricant [F], and lauralyl acetate with a viscosity of 130 cps is a lubricant.
[G] and an emulsion dispersion of butylcaprylate having a viscosity of 75 cps are lubricants [H].

Lubricant [I] In the same emulsifying apparatus as in the example of the lubricant [A], 1130 gr of water and 120 gr of ethylene oxide 9.5 mol adduct of nonylphenol.
And, add 10gr sodium naphthalenesulfonate formalin condensate with an average degree of condensation of 3 and heat it to 70 ℃ to dissolve it homogeneously, then add 1000gr ethylene glycol distearate heated to 120 ℃ and stir it to emulsify it under a high pressure of 300kg / cm ^2. Immediately after that, the mixture was cooled to 25 ° C. to obtain a pale yellowish white emulsion dispersion (lubricant I) having a concentration of 50% and a viscosity of 200 cps.

Lubricant [J] A commercially available commercial dispersion of calcium stearate at a concentration of 50% was used as a lubricant [J].

Lubricant [K] In the production of the emulsion dispersion of lauryl stearate, only the sodium naphthalenesulfonate formalin condensate having a degree of condensation of 3 and the anionic surfactant of sodium dodecylbenzenesulfonate in the example of the lubricant [D] are used. Emulsification was carried out in the same manner as in the example of the lubricant [D] without adding any additives. The finished emulsion had a concentration of 50% and a viscosity of 15000c.
It was abnormally high at ps and solidified after 1 day and could not be used.

The above-mentioned lubricants [A] to [E] of the present invention and, as comparative examples, lubricants [F] to [J] and blank (no addition) were added to the coating color to obtain coated paper in the super calendering step. The preventive properties and the physical properties of the coated paper were evaluated, and the results are shown in Tables 1 and 2. The dust-proof property was evaluated by using a gravure paper prepared by a coating color prescription for gravure and an offset paper prepared by a coating color prescription for offset. The physical properties of the coated paper were evaluated using offset paper. The gravure coating color is No.
1 pre-dispersed clay (EMC, UW-90) 45 parts, N
o.2 Pre-dispersed clay (EMC, HT clay) 55
Parts, polyacrylic acid sodium dispersant (San Nopco
Co., Ltd., SN Dispersant 5040) 0.2 parts, sodium hydroxide 0.3 parts, carboxymethyl cellulose (Daiichi Kogyo Seiyaku Co., Ltd., Serogen PR) 0.3 parts, carboxyl modified styrene-butadiene copolymer latex (Nippon Synthetic Rubber, JS
R 0628) is a dispersion liquid for paper coating of solid content 62%, color PH 9.0 consisting of 8 parts, lubricant 0 to 1 part.

Offset coating color is No. 1 pre-dispersed clay (same as above) 70 parts, light calcium carbonate (Okutama Industry Co., Ltd., Tamapearl TP-222H) 15 parts, heavy calcium carbonate (Sankyo Seiko Kako Co., Ltd.) ), Escalon ^# 1500)
15 parts, sodium polyacrylate dispersant (same as above)
0.2 parts, oxidized starch (Japan Food Processing Co., Ltd., MS-3800) 5
Part, 12 parts carboxy-modified styrene-butadiene copolymer latex (JSR-0692, Japan Synthetic Rubber Co., Ltd.), 62% solid content, 0 to 1 part lubricant, color PH 9.0 dispersion for paper coating Is.

All the blending amounts in the coating color are parts by weight in terms of solid content.

The dispersion for paper coating was applied to a medium quality paper having a basis weight of 65 gr / m ² for a gravure paper and a high quality paper for an offset paper by using a heli coater. The coating amount is 12 gr with gravure paper
/ M ² , and 16 gr / m ² for offset paper.

The coated paper obtained was evaluated at a temperature of 70 ° C.
The state of occurrence of dusting on the chilled roll surface was visually evaluated by passing through a super calendar at a linear pressure of 150 kg / cm and expressed by a 10-point method. In the 10-point method, 10 is the best and 1 is the worst.

The coated paper for measuring the physical properties of coated paper was subjected to a supercalendering test at a temperature of 50 ° C and a linear pressure of 80 kg / cm for the test.

As is clear from the results shown in Table 1, the lubricant for paper coating of the present invention has an extremely excellent dusting-preventing effect with a small amount of addition, and also has an excellent effect of improving white paper gloss, especially printing gloss.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C10N 40:00 Z 8217-4H F 8217-4H 50:02

Claims (4)

[Claims] 1. A general formula (Wherein R represents an alkyl group or an alkenyl group having 11 to 21 carbon atoms, and R'represents an alkyl group or an alkenyl group having 12 to 22 carbon atoms). Agent. 2. At least one nonionic surfactant selected from polyoxyethylene alkyl ether, polyoxyethylene alkyl ester or polyoxyethylene alkylphenyl ether, and a sulfonate type or sulfate ester type anionic interface. The lubricant according to claim 1, which is emulsified and dispersed with at least one anionic surfactant selected from activators. 3. The lubricant according to claim 1, which is emulsified and dispersed by a salt of a copolymer of α, β-unsaturated dibasic acid or its monoester and styrene. 4. A general formula (In the formula, R represents an alkyl group or alkenyl group having 11 to 21 carbon atoms, and R'represents an alkyl group or alkenyl group having 12 to 22 carbon atoms.) An ester compound represented by Using a surfactant in combination with a surfactant, or a salt of a copolymer of α, β-unsaturated dibasic acid or its monoester and styrene, and water in the presence of a high-speed stirring emulsifier or a piston-type high-pressure emulsifier. A method for producing a paper coating lubricant comprising an aqueous dispersion, which is characterized in that it is emulsified and dispersed.