JP4431650B2 - Fluorescent whitening enhancer - Google Patents

Description

The present invention relates to a fluorescent whitening enhancer. More specifically, the present invention relates to a fluorescent whitening enhancer that is suitable as a fluorescent whitening enhancer that is used in a paint for coated paper together with a fluorescent whitening agent.

In order to improve the fluorescent whiteness and whiteness of coated paper and other papers, it is known to further enhance the fluorescent whitening effect by using a fluorescent whitening enhancer together with the fluorescent whitening agent. .
Examples of such fluorescent whitening enhancers include polyvinyl alcohol, water-soluble cellulose derivatives, starch derivatives, casein, melamine / formaldehyde resins, urea / formaldehyde resins, polyglycols, polyvinylpyrrolidone and polyhydroxy compounds (Patent Document 1) Polyacrylamide (Patent Document 2) and the like are known.
Japanese translation of PCT publication No. 2002-543306 JP 2001-81692 A

Conventional fluorescent whitening enhancers have a problem that it is difficult to obtain higher fluorescent whiteness and whiteness even if the amount of fluorescent whitening agent or fluorescent whitening enhancer is increased. That is, an object of the present invention is to provide a fluorescent whitening enhancer capable of remarkably improving the fluorescent whiteness and whiteness when used together with the fluorescent whitening agent.

  The inventor of the present invention has reached the present invention as a result of intensive studies to solve the above problems. That is, the fluorescent whitening enhancer of the present invention is characterized in that in the fluorescent whitening enhancer used together with the fluorescent whitening agent, a sulfonated aromatic vinyl polymer, a sulfonated aromatic urethane polymer and / or a sulfonated aromatic ester polymer. The point which contains is made into a summary.

When the fluorescent whitening enhancer of the present invention is used together with a fluorescent whitening agent, the fluorescent whitening and whiteness of paper can be remarkably improved. Further, even when used for coating paper, there is almost no change in the viscosity of the coating. Therefore, it is suitably used for coated paper used for pigment coated paper, clear coated paper, and the like.

A sulfonated aromatic vinyl polymer is a structure produced by sulfonation (introducing a sulfo group) after obtaining an aromatic vinyl polymer, or (co) polymerization using a sulfo group-containing aromatic vinyl monomer as an essential constituent monomer. It has a structure manufactured. Of these, the former structure is preferable from the viewpoint of ease of production. In addition, although the structure by these manufacturing methods may differ strictly, in the effect of this invention, there is no difference by a manufacturing method and it is not limited to these manufacturing methods.
In the case of sulfonating an aromatic vinyl polymer, an aromatic vinyl polymer produced by (co) polymerizing an aromatic vinyl monomer as an essential constituent monomer can be used.

As the aromatic vinyl monomer, any compound having an aromatic ring and a vinyl group can be used without limitation, but a vinyl monomer having 8 to 12 carbon atoms is preferably used, and styrene, α-methylstyrene, vinylnaphthalene, vinyltoluene. , Methoxystyrene, chlorostyrene, hydroxystyrene, p-methylstyrene, and the like. Of these, styrene, α-methylstyrene, vinylnaphthalene and vinyltoluene are preferable from the viewpoint of fluorescent whiteness and whiteness, more preferably styrene, α-methylstyrene and vinyltoluene, particularly preferably styrene and α. Methyl styrene, most preferably styrene.

The aromatic vinyl polymer can contain a copolymerized vinyl monomer as a constituent monomer in addition to the aromatic vinyl monomer. The copolymerized vinyl monomer is not particularly limited as long as it can be copolymerized with an aromatic vinyl monomer, and unsaturated carboxylic acid ester, fatty acid vinyl ester, unsaturated carboxylic acid (salt), olefin, and other monomers can be used. . In addition, unsaturated carboxylic acid (salt) means unsaturated carboxylic acid or unsaturated carboxylate. In addition, as the salt, alkali metal (sodium, potassium, lithium, etc.) salt, alkaline earth metal (magnesium, calcium, etc.) salt, ammonium salt, alkanolamine (monoethanolamine, diethanolamine, triethanolamine etc.) salt, amine (Methylamine, trimethylamine, triethylamine, methylethylamine, methyldiethylamine and the like) salts and quaternary ammonium (tetramethylammonium, tetraethylammonium, methyltriethylammonium and dimethyldiethylammonium) salts and the like. Of these, alkali metal salts are preferable, potassium salts and sodium salts are more preferable, and sodium salts are particularly preferable.

As the unsaturated carboxylic acid ester, a monomer having 4 to 20 carbon atoms can be used, such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, ethylhexyl (meth) acrylate, (meth ) Stearyl acrylate, methyl crotonate, dimethyl maleate, hexyl maleate, butyl itaconate and the like.

As the fatty acid vinyl ester, a monomer having 4 to 20 carbon atoms can be used, and examples thereof include vinyl acetate, vinyl palmitate, vinyl laurate, and vinyl stearate.
As unsaturated carboxylic acid (salt), a C3-C6 monomer etc. can be used, (meth) acrylic acid (salt), crotonic acid (salt), maleic acid (salt), itaconic acid (salt), etc. In addition, acid anhydrides (such as maleic anhydride and itaconic anhydride) can also be used.
As the olefin, a monomer having 2 to 20 carbon atoms can be used, and α-olefin (ethylene, propylene, butylene, hexylene, octylene, undecylene, tetradecylene, nonadecylene, etc.), diisobutylene, butadiene, piperylene, chloroprene, pinene, Examples include limonene, indene, cyclopentadiene, bicyclopentadiene, and ethylidene norbornene.

As other monomers, monomers such as nitrile, amide or ether can be used.
As the nitrile, a monomer having 3 to 5 carbon atoms or the like is used, and (meth) acrylonitrile, cyanopropene, cyanopentene, and the like can be given.
As the amide, a monomer having 2 to 8 carbon atoms can be used, and (meth) acrylamide, N-methyl (meth) acrylamide, N-2-hydroxymethyl (meth) acrylamide, N- (2-aminoethyl) (meth) ) Acrylamide and N- (2-dimethylaminoethyl) (meth) acrylamide.
As the ether, a monomer having 5 to 60 carbon atoms can be used, and methoxypolyethylene glycol (25 mol addition) (meth) acrylate, methoxypolyethylene glycol (5 mol addition) (meth) acrylate, polyethylene glycol (20 mol addition) mono Examples include (meth) acrylate and polyethylene glycol (10 mol addition) mono (meth) acrylate.
Of these copolymerizable monomers, unsaturated carboxylic acid esters, fatty acid vinyl esters, unsaturated carboxylic acids (salts) and olefins are preferred from the viewpoint of productivity, and more preferably unsaturated carboxylic acid esters, fatty acid vinyl esters and An unsaturated carboxylic acid (salt), particularly preferably an unsaturated carboxylic acid ester and an unsaturated carboxylic acid (salt), most preferably an unsaturated carboxylic acid ester.

When a copolymerized vinyl monomer is used, the content (% by weight) is preferably 2 to 80, more preferably 5 to 70, particularly preferably 8 based on the weight of the aromatic vinyl monomer and the copolymerized vinyl monomer. ~ 65, most preferably 10-60. Within this range, the fluorescent whiteness and whiteness can be further improved.

The weight average molecular weight (Mw) of the aromatic vinyl polymer is preferably 1,000 to 400,000, more preferably 1500 to 350,000, particularly preferably 2000 to 300,000, and most preferably 3,000 to 200,000. Within this range, there is little increase in viscosity during sulfonation, and sulfonation is easy.
The molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn) is preferably 1.2 to 5, more preferably 1.3 to 4.8, and particularly preferably 1.4 to 4.5.
In the present invention, the Mw, Mn, and molecular weight distribution of a non-sulfonated polymer are measured by gel permeation chromatography (GPC) using standard polystyrene as a reference substance.

As a method of (co) polymerizing an aromatic vinyl monomer and, if necessary, a copolymerized vinyl monomer, polymerization can be carried out by a usual polymerization method of vinyl monomers, suspension polymerization, bulk polymerization, solution polymerization, etc. can be applied, and fluorescent whitening degree From the viewpoint of brightness and whiteness, solution polymerization is preferable.
A polymerization catalyst can be used for the polymerization. As the polymerization catalyst, an ordinary polymerization catalyst or the like is used, and an azo catalyst, a persulfate, an inorganic peroxide, a redox catalyst, an organic peroxide, and the like are included.
Examples of the azo catalyst include 2,2′-azobisisobutyronitrile, 4,4′-azobis-4-cyanovaleric acid, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile, 2 , 2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-albonitrile), 2,2′-azobis (2,4,4-trimethylpentane), dimethyl 2,2 Examples include '-azobis (2-methylpropionate), 2,2'-azobis [2- (hydroxymethyl) propionitrile] and 1,1'-azobis (1-acetoxy-1-phenylethane).
Examples of the persulfate include ammonium persulfate, potassium persulfate, and sodium persulfate.
Examples of inorganic peroxides include perborate and hydrogen peroxide.
Examples of the redox catalyst include ascorbic acid-hydrogen peroxide.
Examples of the organic peroxide include benzoyl peroxide.
When a polymerization catalyst is used, the amount used (% by weight) is preferably 0.001 to 10, more preferably 0.003 to 9, particularly preferably 0.005, based on the total weight of the monomers used. 7, most preferably 0.08-5.

In the case of solution polymerization and suspension polymerization, water, alcohol solvents (such as methanol, ethanol and isopropyl alcohol) and / or aromatic solvents (such as toluene and xylene) can be used as the solvent.
The reaction temperature is preferably about 40 to 130 ° C., and the reaction time is preferably about 1 to 15 hours.
The amount (% by weight) of the solvent used is preferably 50 to 900, more preferably 60 to 800, particularly preferably 80 to 700, and most preferably 100 to 600, based on the total weight of the monomers used.
In addition, you may superpose | polymerize, dripping the whole quantity or one part of a monomer. Moreover, you may superpose | polymerize, dripping the whole quantity or one part of a polymerization catalyst. Moreover, you may superpose | polymerize, dripping the whole quantity or one part of a solvent with a monomer or a polymerization catalyst. On the other hand, the whole amount of the solvent may be charged into the polymerization tank and polymerization may be performed while removing the solvent. Among these, from the viewpoint of productivity and the like, the method of dropping the total amount of the monomer and the polymerization catalyst and the method of dropping a part of the solvent together with the monomer or the polymerization catalyst are preferable, and the total amount of the monomer and the polymerization catalyst is more preferable. It is the method of dripping together with a part of solvent.

A reaction solvent can be used for sulfonation of the aromatic vinyl polymer. The reaction solvent is not particularly limited as long as it is inert to the sulfonating agent, and examples thereof include aliphatic halogenated hydrocarbons having 1 to 2 carbon atoms and nitrated hydrocarbons having 1 to 3 carbon atoms. Can be used.
Examples of the halogenated hydrocarbon include 1,2-dichloroethane, methylene dichloride, ethyl chloride, carbon tetrachloride, 1,1-dichloroethane, 1,1,2,2, -tetrachloroethane, chloroform and ethylene dibromide. .
Examples of the nitro hydrocarbon include nitromethane, nitroethane, 1-nitropropane and 2-nitropropane.
These reaction solvents may be used alone or in a mixture.
Of these reaction solvents, aliphatic halogenated hydrocarbons having 1 to 2 carbon atoms are preferable from the viewpoint of solubility of the sulfonating agent in the reaction solvent, and more preferably 1,2-dichloroethane and methylene dichloride. 1,2-dichloroethane is preferred.
When using a reaction solvent, the amount used (% by weight) is preferably from 100 to 10,000, more preferably from 130 to 8,000, particularly preferably from 150 to 10,000, based on the weight of the sulfonated aromatic vinyl polymer. 5,000, most preferably 200 to 2,000. Within this range, the sulfonation reaction efficiency is further improved.

The sulfonating agent is not particularly limited as long as it can be sulfonated (introducing a sulfo group), and examples thereof include sulfuric anhydride, fuming sulfuric acid and concentrated sulfuric acid. Of these, anhydrous sulfuric acid is preferred. These may be used alone or in combination.
The use amount (mol) of the sulfonating agent is preferably 0.5 to 2, more preferably 0.6 to 1.9, based on the number of moles of the aromatic vinyl monomer used in the production of the aromatic vinyl polymer. Particularly preferred is 0.8 to 1.7, and most preferred is 1.0 to 1.5. Within this range, the sulfonation reaction efficiency is further improved.

In sulfonation, a Lewis base can be used together with a sulfonating agent (particularly sulfuric anhydride). When a Lewis base is used, a complex is formed from a sulfonating agent (particularly sulfuric anhydride) and a Lewis base, the crosslinking reaction is suppressed (the content of water-insoluble crosslinked polymer is reduced), and the sulfonation efficiency is further improved. .
As the Lewis base, trialkyl phosphate, fatty acid alkyl ester, ether, thioether and the like can be used.
As the trialkyl phosphate, a phosphate having an alkyl group having 1 to 3 carbon atoms can be used, and examples thereof include triethyl phosphate and trimethyl phosphate.
As the fatty acid alkyl ester, a fatty acid ester having 1 to 20 carbon atoms can be used, and examples thereof include ethyl acetate and ethyl palmitate.
As ether, C2-C5 ether etc. can be used and a dioxane, diethyl ether, etc. are mentioned.
Examples of thioethers include thioxan and diethyl thioether.
Of these, trialkyl phosphates and fatty acid alkyl esters are preferred, more preferred are trialkyl phosphates, and particularly preferred is triethyl phosphate. These may be used alone or in combination.

When a Lewis base is used, the added weight (mole) is preferably 0.2 to 2, more preferably 0.4 to 1.8, particularly preferably 0.5, based on the number of moles of the sulfonating agent. ~ 1.5. Within this range, the sulfonation reaction efficiency is further improved.

The temperature (° C.) of the sulfonation reaction is preferably 0 to 100, more preferably 10 to 70, particularly preferably 15 to 60, and most preferably 20 to 50. The time for the sulfonation reaction is preferably about 10 minutes to 10 hours.

When a reaction solvent is used, a sulfonated reaction product (sulfonated aromatic vinyl polymer) is precipitated as a solvent insoluble matter with the progress of the aromatic vinyl polymer and the sulfonating agent.
The resulting sulfonated aromatic vinyl polymer may be neutralized with a neutralizing agent in order to improve water solubility.
Neutralization may be performed after the solvent is removed or before the removal. When the solvent is not used, neutralization may be performed after further adding a solvent or water. When adding water, the addition amount (% by weight) of water is preferably 0.5 to 20, more preferably 1 to 18, particularly preferably 3 to 15, based on the weight of the sulfonated aromatic vinyl polymer. Most preferably, it is 5-10. The neutralization may be complete neutralization or partial neutralization, but complete neutralization is preferable from the viewpoint of quality stability (ease of repeated production of the same quality). A normal method can be applied to the end point of neutralization.
Examples of neutralizers include hydroxides or carbonates of alkali metals (sodium, potassium, lithium, etc.) or alkaline earth metals (magnesium, calcium, etc.), ammonia, alkanolamines (monoethanolamine, diethanolamine, triethanolamine, etc.) ), Amines (methylamine, trimethylamine, triethylamine, methylethylamine, methyldiethylamine, etc.) and aqueous solutions thereof (concentration is about 1 to 50% by weight). Of these, alkali metal hydroxides are preferable, potassium hydroxide and sodium hydroxide are more preferable, and sodium hydroxide is particularly preferable.
When removing the reaction solvent, atmospheric pressure and reduced pressure distillation methods can be applied. Further, after adding water, the solvent may be removed. In this case, the sulfonated aromatic vinyl polymer is obtained as an aqueous solution.
The unreacted sulfonating agent may be removed by filtration or the like after forming a neutralized salt with the neutralizing agent.
Among these sulfonation methods, from the viewpoint of ease of production and quality stability, a method using a reaction solvent, a method using a Lewis base, a method of neutralizing with a neutralizing agent (after adding water) And a method of removing the reaction solvent is preferred, more preferably a method using a reaction solvent and a Lewis base, a method of adding water and then neutralizing with a neutralizing agent, and a method of removing the reaction solvent, particularly preferred Is a method using a reaction solvent and a Lewis base, and a method of removing the reaction solvent after neutralizing with a neutralizing agent after adding water, most preferably reacting with a sulfonating agent using a reaction solvent and a Lewis base, In this method, the reaction solvent is removed after neutralizing with a neutralizing agent after adding water.

As the sulfo group-containing aromatic vinyl monomer, a monomer having 8 to 12 carbon atoms can be used, and styrene sulfonic acid, α-methyl styrene sulfonic acid, vinyl naphthalene sulfonic acid, vinyl toluene sulfonic acid, methoxy styrene sulfonic acid, chlorostyrene. Examples include sulfonic acid, hydroxystyrene sulfonic acid, and p-methylstyrene sulfonic acid.
Of these, styrene sulfonic acid, α-methyl styrene sulfonic acid, vinyl naphthalene sulfonic acid and vinyl toluene sulfonic acid are preferable from the viewpoint of fluorescent whiteness and whiteness, and more preferably styrene sulfonic acid and α-methyl styrene. Sulfonic acid and vinyltoluenesulfonic acid, particularly preferably styrenesulfonic acid and α-methylstyrenesulfonic acid, most preferably styrenesulfonic acid.

The sulfonated aromatic vinyl polymer can contain a copolymerized vinyl monomer as a constituent monomer in addition to the sulfo group-containing aromatic vinyl monomer. The copolymerized vinyl monomer is not particularly limited as long as it can be copolymerized with a sulfo group-containing aromatic vinyl monomer, and the above-mentioned copolymerized vinyl monomers can be used. Of these, unsaturated carboxylic acid esters, fatty acid vinyl esters, unsaturated carboxylic acids (salts) and olefins are preferred from the viewpoint of productivity, etc., more preferably unsaturated carboxylic acid esters, fatty acid vinyl esters and unsaturated carboxylic acids. (Salts), particularly preferably unsaturated carboxylic acid esters and unsaturated carboxylic acids (salts), most preferably unsaturated carboxylic acid esters.

When a copolymerized vinyl monomer is used, the content (% by weight) is preferably 2 to 80, more preferably 5 to 70, particularly based on the weight of the sulfo group-containing aromatic vinyl monomer and the copolymerized vinyl monomer. Preferably it is 8-60, Most preferably, it is 10-50. Within this range, the fluorescent whiteness and whiteness can be further improved.

The same method as described above can be applied to the method of (co) polymerizing the sulfo group-containing aromatic vinyl monomer and, if necessary, the copolymerized vinyl monomer. Among these methods, from the viewpoint of productivity, etc., solution polymerization is preferable, more preferably a method in which the whole amount of the monomer and the polymerization catalyst is dropped, and a method in which a part of the solvent is dropped together with the monomer or the polymerization catalyst, particularly preferably. In this method, the entire amount of the monomer and the polymerization catalyst is dropped together with a part of the solvent.

The sulfonated aromatic urethane polymer has a structure produced by obtaining an aromatic urethane polymer and then sulfonating (introducing a sulfo group). The production method is not limited.
Examples of the aromatic urethane polymer include those produced by (co) polymerizing aromatic diisocyanate, aromatic dialcohol and / or dihydric phenol as essential constituent monomers.

As the aromatic diisocyanate, aromatic diisocyanates having 8 to 20 carbon atoms and the like are used. Metaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, xylylene diisocyanate, 2,6-tolylene diisocyanate, dimethylbenzene Diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, biphenyl diisocyanate, tolidine diisocyanate, 3,3′-dimethoxybiphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,2′-dimethyldiphenylmethane-4,4 '-Diisocyanate, 3,3'-dimethoxydiphenylmethane-4,4'-diisocyanate, 4,4'-dimeth Xylphenylmethane-3,3′-diisocyanate, 4,4′-diethoxydiphenylmethane-3,3′-diisocyanate, 2,2′-dimethyl-5,5′-dimethoxydiphenylmethane-4,4′-diisocyanate, etc. Can be mentioned.
Of these, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, and tolidine diisocyanate are preferable from the viewpoint of fluorescent whitening and whiteness. Preferably 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate and 4,4′-diphenylmethane diisocyanate, particularly preferably 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and xylylene Diisocyanate, most preferably xylylene diisocyanate.

As the aromatic dialcohol, an aromatic dialcohol having 6 to 20 carbon atoms is used, and an alkylene oxide adduct such as hydroquinone, catechol, bisphenol A, bisphenol S, tetramethylbisphenol A or tetramethylbisphenol S, di ( Hydroxyethyl) benzene, di (hydroxymethyl) benzene, di (hydroxypropyl) benzene or di (hydroxyhexyl) benzene and their alkylene oxide adducts.

As the alkylene oxide, an alkylene oxide having 2 to 4 carbon atoms is used, and examples thereof include ethylene oxide, propylene oxide, and butylene oxide. Among these, from the viewpoint of fluorescent whiteness and whiteness, ethylene oxide, propylene oxide and a mixture of ethylene oxide and propylene oxide or butylene oxide are preferable, and ethylene oxide and a mixture of ethylene oxide and propylene oxide or butylene oxide are more preferable. Preference is given to ethylene oxide and a mixture of ethylene oxide and propylene oxide, most preferably ethylene oxide. The number of added moles is preferably 5 to 650, more preferably 10 to 600, particularly preferably 13 to 570, and most preferably 10 to 550 per hydroxyl group. When a plurality of alkylene oxides are used, the addition form may be any of a block form, a random form, and a mixture thereof, but a block form and a mixture are preferable, and a block form is more preferable.
Among these, from the viewpoint of fluorescent whitening and whiteness, alkylene oxide adducts of bisphenol A, bisphenol S, tetramethylbisphenol A or tetramethylbisphenol S are preferred, and bisphenol A, bisphenol S and tetramethyl are more preferred. An alkylene oxide adduct of bisphenol A, particularly preferably an alkylene oxide adduct of bisphenol A and bisphenol S, most preferably an alkylene oxide adduct of bisphenol A.

As the divalent phenol, bisphenol having 6 to 20 carbon atoms is used, and examples thereof include hydroquinone, catechol, bisphenol A, bisphenol S, tetramethylbisphenol A, and tetramethylbisphenol S.
Of these, bisphenol A, bisphenol S, tetramethyl bisphenol A and tetramethyl bisphenol S are preferable from the viewpoint of fluorescent whitening and whiteness, and more preferably bisphenol A, bisphenol S and tetramethyl bisphenol A, and particularly preferable. Is bisphenol A and bisphenol S, most preferably bisphenol A.

The aromatic urethane polymer can contain a (co) polymerization monomer as a constituent monomer in addition to the aromatic diisocyanate, aromatic dialcohol and / or dihydric phenol. The (co) polymerization monomer is not particularly limited as long as it can be (co) polymerized with aromatic diisocyanate, aromatic dialcohol and / or dihydric phenol, and isocyanate, alcohol, amine and other monomers can be used.

Examples of the isocyanate include aliphatic isocyanate, aromatic monoisocyanate, and alicyclic isocyanate.
As the aliphatic isocyanate, aliphatic monoisocyanate and aliphatic diisocyanate can be used.
Examples of the aliphatic monoisocyanate include ethyl isocyanate, butyl isocyanate, hexyl isocyanate, 2-ethylhexyl isocyanate, nonyl isocyanate, isododecyl isocyanate, hexadecyl isocyanate and octadecyl isocyanate.
Aliphatic diisocyanates include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, dipropyl ether diisocyanate. 1,4-butane diisocyanate, 2,2′-dimethylpentane-1,5-diisocyanate, 3-methoxyhexane diisocyanate, 2,2,4-trimethylpentane-1,5-diisocyanate, 3-butoxyhexane diisocyanate, , 4-Butylene glycol dipropyl ether diisocyanate, metaxylylene Examples include diisocyanate, paraxylylene diisocyanate, and tetramethylxylylene diisocyanate.

  Examples of the aromatic monoisocyanate include phenyl isocyanate, methylphenyl isocyanate, biphenyl isocyanate, and naphthalene isocyanate.

As the alicyclic isocyanate, alicyclic monoisocyanate and alicyclic diisocyanate can be used.
Examples of the alicyclic monoisocyanate include cyclohexyl isocyanate and dicyclohexyl isocyanate.
Examples of the alicyclic diisocyanate include cyclohexyl diisocyanate, hydrogenated TDI, hydrogenated XDI, hydrogenated MDI, isophorone diisocyanate (IPDI), and dicyclohexylmethane-4,4′-diisocyanate.

In addition to these, polyisocyanate can also be used, and examples thereof include HDI-trimethylolpropane adduct, HDI-biuret, HDI isocyanurate, polymeric MDI, TDI-trimethylolpropane adduct and TDI isocyanurate.

Of these isocyanates, aliphatic isocyanates and alicyclic isocyanates are preferred from the viewpoint of fluorescent whitening and whiteness, more preferably aliphatic isocyanates, particularly preferably aliphatic monoisocyanates and aliphatic diisocyanates, most preferably. Is an aliphatic diisocyanate.

Examples of the alcohol include aliphatic alcohols, alicyclic alcohols, and aromatic monoalcohols.
As the aliphatic alcohol, alkyl monoalcohols, alkenyl monoalcohols, aliphatic polyhydric alcohols, and alkylene oxide adducts thereof can be used.
Examples of the alkyl monoalcohol include monoalcohol having 1 to 20 carbon atoms, such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, Examples include dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecyl alcohol, and aralkyl alcohol.
Examples of the alkenyl monoalcohol include monoalcohol having 3 to 20 carbon atoms, such as propenyl alcohol, hexenyl alcohol, hexadienyl alcohol, heptenyl alcohol, octenyl alcohol, nonenyl alcohol, decenyl alcohol, and undecenyl. Examples include alcohol, dodecenyl alcohol, tetradecenyl alcohol, and oleyl alcohol.
As the aliphatic polyhydric alcohol, a polyhydric alcohol having 2 to 20 carbon atoms or the like is used, and ethylene glycol, propanediol, butanediol, pentadiol, hexanediol, decanediol, pinacol, glycerin, butanetriol, hexanetriol, Examples include trimethylolpropane, pentaerythritol, sorbitol, erythritol, pentitol, sucrose, hexit and the like. In addition, polyvinyl alcohol having a weight average molecular weight of 5,000 to 100,000 can also be used.
These alkylene oxide adducts have the same alkylene oxide type, number of added moles, addition form, and preferred ranges thereof as described above.

As the alicyclic alcohol, cycloalkyl monoalcohol, cycloalkenyl monoalcohol, alicyclic polyhydric alcohol, and alkylene oxide adducts thereof can be used.
Examples of the cycloalkyl monoalcohol include alkanols having 5 to 7 carbon atoms, and examples thereof include cyclopentyl alcohol, cyclohexyl alcohol, cycloheptyl alcohol, methylcyclopentyl alcohol, methylcyclohexyl alcohol, and methylcycloheptyl alcohol.
As the cycloalkenyl monoalcohol, an alkenol having 5 to 7 carbon atoms is used, and cyclopentene alcohol, 2,4-cyclohexadienyl alcohol, cyclohexenyl alcohol, cycloheptenyl alcohol, methylcyclopentenyl alcohol, methylcyclohexenyl alcohol and Examples include methylcycloheptenyl alcohol.
As the alicyclic polyhydric alcohol, a polyhydric alcohol having 5 to 7 carbon atoms or the like is used, and examples thereof include cyclopentanediol, cyclohexanediol, and cycloheptanediol.
These alkylene oxide adducts have the same alkylene oxide type, number of added moles, addition form, and preferred ranges thereof as described above.

As the aromatic monoalcohol, a monoalcohol having 7 to 15 carbon atoms and an alkylene oxide adduct thereof can be used.
Examples of the monoalcohol include benzyl alcohol. In addition, monophenol (phenol, ethylphenol, isobutylphenol, pentylphenol, octylphenol, etc.) is also included.
The kind of alkylene oxide of this alkylene oxide adduct, the number of addition moles, addition form, and these preferable ranges are the same as the above.

Among these alcohols, from the viewpoint of fluorescent whiteness and whiteness, an alkylene oxide adduct of an aliphatic alcohol or an alicyclic alcohol is preferred, an alkylene oxide adduct of an aliphatic alcohol is more preferred, and a fatty acid is particularly preferred. An alkylene oxide adduct of an aliphatic polyalcohol, most preferably an alkylene oxide adduct of an aliphatic dialcohol.

Examples of amines include primary amines, secondary amines, alkanolamines, and alkylene oxide adducts thereof.
As the primary amine, primary amines having 1 to 20 carbon atoms are used, and methylamine, ethylamine, propylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecyl. Examples include amine, tridecylamine, tetradecylamine, pentadecylamine, cetylamine, heptadecylamine, octadecylamine, nonadecylamine, aralkylamine, arylamine, aniline, toluidine, ethylenediamine and propylenediamine.
As the secondary amine, a secondary amine having 2 to 40 carbon atoms is used, and examples thereof include dimethylamine, diethylamine, dipropylamine, dibutylamine, didodecylamine and dioctadecylamine. In addition to these, polyamines such as diethylenetriamine and triethylenetetramine can also be used.
As the alkanolamine, alkanolamine having 2 to 10 carbon atoms is used, and examples thereof include monoethanolamine, diethanolamine, triethanolamine, and aminomethylpropanol.
These alkylene oxide adducts have the same alkylene oxide type, number of added moles, addition form, and preferred ranges thereof as described above.
Among these amines, primary amine alkylene oxide adducts are preferred from the viewpoint of fluorescent whiteness and whiteness, more preferably methylamine, ethylamine, propylamine or butylamine alkylene oxide adducts, particularly preferably. An alkylene oxide adduct of methylamine, ethylamine or propylamine, most preferably an alkylene oxide adduct of methylamine or ethylamine.

As other monomers, amides and the like can be used, and amides having 1 to 20 carbon atoms are used. Formamide, acetamide, propionic acid amide, butyric acid amide, valeric acid amide, caproic acid amide, oleic acid amide, stearic acid amide Succinic acid amide, malonic acid amide, glutaric acid amide and the like.

Of these copolymerized monomers, aliphatic monoisocyanates, aliphatic diisocyanates, alkylene oxide adducts of aliphatic polyhydric alcohols and alkylene oxide adducts of primary amines are preferred from the viewpoint of fluorescent whiteness and whiteness. More preferably, aliphatic diisocyanates, alkylene oxide adducts of aliphatic polyhydric alcohols and alkylene oxide adducts of primary amines, particularly preferably alkylene oxide adducts of aliphatic polyhydric alcohols and alkylene oxide adducts of primary amines. Most preferred is an alkylene oxide adduct of an aliphatic polyhydric alcohol.

When a (co) polymerization monomer is used, this content (% by weight) is preferably 2 to 80, based on the weight of the aromatic diisocyanate, aromatic dialcohol, dihydric phenol and (co) polymerization monomer, Preferably it is 5-70, Most preferably, it is 8-60, Most preferably, it is 10-50. Within this range, the fluorescent whiteness and whiteness can be further improved.

The weight average molecular weight (Mw), molecular weight distribution (Mw / Mn) and measuring method of the aromatic urethane polymer are the same as Mw, Mw / Mn and measuring method of the aromatic vinyl polymer.

The aromatic urethane polymer has a structure that can be produced by polymerizing an aromatic diisocyanate, an aromatic dialcohol and / or a dihydric phenol as an essential constituent monomer. However, the diisocyanate component {aromatic diisocyanate, aliphatic diisocyanate and / or Or alicyclic diisocyanate} and diol component {aromatic dialcohol, dihydric phenol, aliphatic polyvalent (divalent) alcohol, alicyclic polyvalent (divalent) alcohol, primary amine and / or alkylene oxide thereof And the like produced by reaction with an adduct}.
Diisocyanate component {aromatic diisocyanate, aliphatic diisocyanate and / or alicyclic diisocyanate} and diol component {aromatic dialcohol, dihydric phenol, aliphatic polyvalent (divalent) alcohol, alicyclic polyvalent (divalent) The amount ratio of alcohol, primary amine and / or these alkylene oxide adducts is (1.0-2) as the equivalent ratio (OH / NCO) of hydroxyl group (OH) to isocyanate group (NCO). 0.0) / 1 is preferred, more preferably (1.05 to 1.95) / 1, particularly preferably (1.1 to 1.90) / 1, most preferably (1.15 to 1). .85) / 1.
Moreover, the usage amount (% by weight) of the monoisocyanate component {aliphatic monoisocyanate, aromatic monoisocyanate and / or alicyclic monoisocyanate} is preferably 1 to 50, more preferably based on the weight of the diisocyanate component. It is 2-45, Most preferably, it is 3-40, Most preferably, it is 5-35.
When using a monool component {alkyl monoalcohol, alkenyl monoalcohol, cycloalkyl monoalcohol, cycloalkenyl monoalcohol, aromatic monoalcohol, monophenol, secondary amine and / or alkylene oxide adduct thereof} The amount used (% by weight) is preferably from 1 to 50, more preferably from 2 to 45, particularly preferably from 3 to 40, and most preferably from 5 to 35, based on the weight of the diol component.
In addition, when a polyol {trivalent or higher, alkanolamine, polyamine and / or alkylene oxide adduct thereof} is used, the amount used (% by weight) is 0.1 to 50 based on the weight of the diol component. More preferably, it is 0.5-45, Most preferably, it is 0.8-35, Most preferably, it is 1-35.

As the polymerization method of the diisocyanate component, diol component, and if necessary, the monoisocyanate component, monool component and / or polyol component, polymerization can be carried out by the usual polymerization method of isocyanate and active hydrogen compound, suspension polymerization, bulk polymerization and solution polymerization. From the viewpoint of productivity, solution polymerization is preferable.
A polymerization catalyst can be used for the polymerization. As the polymerization catalyst, an ordinary polymerization catalyst or the like is used, and an amine {triethylamine, triethylenediamine, heptamethyldiethylenetriamine, N-methylmorpholine, benzyltriethylammonium hydroxide, etc.} and a metal-containing compound {stannous chloride, chloride chloride) 2 tin, tin octylate, lead octylate, dibutyltin dilaurate, cobalt naphthenate, lead naphthenate, potassium naphthenate, antimony trichloride, etc.).
When a polymerization catalyst is used, the amount (% by weight) used is preferably from 0.001 to 1, more preferably from 0.005 to 0.9, and particularly preferably from 0.001 to 0.9, based on the total weight of the monomers used. 01 to 0.85, most preferably 0.05 to 0.8.

In the case of solution polymerization and suspension polymerization, any solvent can be used as long as it does not have (1) active hydrogen and (2) dissolves the diisocyanate component, diol component, and aromatic urethane polymer. Such solvents include aromatic solvents (such as toluene and xylene), aliphatic solvents (such as petroleum ether and n-hexane), alicyclic solvents (such as cyclohexane, cyclohexanone, and decalin), and halogen-containing solvents (such as chloroform). Carbon tetrachloride, ethylene dichloride, chlorobenzene, etc.), ester solvents (ethyl acetate, butyl acetate, pentyl acetate, etc.) and ketone solvents (methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, etc.).
When a solvent is used, the amount (% by weight) used is preferably 20 to 800, more preferably 30 to 750, particularly preferably 40 to 700, and most preferably 50, based on the total weight of the diisocyanate component and the diol component. ~ 650.
When a solvent is used, the solvent may be removed after the reaction. As a method for removing the solvent, a vacuum distillation method or the like can be applied. As conditions for distilling off under reduced pressure, conditions such as distillation at 100 to 130 ° C. under a reduced pressure of 26.6 to 0.7 MPa can be applied.

The reaction temperature (° C.) is preferably 40 to 130, more preferably 50 to 120, particularly preferably 60 to 110, and most preferably 65 to 105. The reaction atmosphere is preferably a dry inert gas (nitrogen gas, carbon dioxide gas, argon gas, etc.) atmosphere. The end point of the reaction can be confirmed by determining when the isocyanate group content is 0.01% by weight or less in the isocyanate group content measurement method using a dioxane solution of di-n-butylamine. The reaction time is preferably about 2 to 10 hours.
In addition, you may superpose | polymerize, dripping the whole quantity or one part of a monomer. Moreover, you may superpose | polymerize, dripping the whole quantity or one part of a polymerization catalyst. Moreover, you may superpose | polymerize, dripping the whole quantity or one part of a solvent with a monomer or a polymerization catalyst. On the other hand, the whole amount of the solvent may be charged into the polymerization tank and polymerization may be performed while removing the solvent. Among these, from the viewpoint of productivity and the like, the method of dropping the total amount of the monomer and the polymerization catalyst and the method of dropping a part of the solvent together with the monomer or the polymerization catalyst are preferable, and the total amount of the monomer and the polymerization catalyst is more preferable. It is the method of dripping together with a part of solvent.

As a method for sulfonation of the aromatic urethane polymer, a method similar to that for the sulfonated aromatic vinyl polymer can be applied.

The sulfonated aromatic ester polymer has a structure produced by obtaining an aromatic ester polymer and then sulfonating (introducing a sulfo group). The production method is not limited.
Examples of the aromatic ester polymer include those produced by (co) polymerizing aromatic dicarboxylic acid, aromatic dialcohol and / or dihydric phenol as essential constituent monomers.

Examples of the aromatic dicarboxylic acid include dicarboxylic acids having 8 to 12 carbon atoms, and examples thereof include phthalic acid, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid.
Of these, phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid are preferred from the viewpoint of fluorescent whitening and whiteness, more preferably phthalic acid, terephthalic acid and isophthalic acid, particularly preferably terephthalic acid and isophthalic acid. Acid, most preferably terephthalic acid.

As the aromatic dialcohol, an alkylene oxide adduct such as hydroquinone, catechol, bisphenol A, bisphenol S, tetramethylbisphenol A, or tetramethylbisphenol S can be used. These alkylene oxide adducts have the same alkylene oxide type, number of added moles, addition form, and preferred ranges thereof as described above.
Among these, from the viewpoints of fluorescent whiteness and whiteness, alkylene oxide adducts of bisphenol A, bisphenol S, tetramethylbisphenol A or tetramethylbisphenol S are preferred, and bisphenol A, bisphenol S or tetramethyl are more preferred. An alkylene oxide adduct of bisphenol A, particularly preferably an alkylene oxide adduct of bisphenol or bisphenol S, most preferably an alkylene oxide adduct of bisphenol A.

Examples of the divalent phenol include hydroquinone, catechol, bisphenol A, bisphenol S, tetramethylbisphenol A, and tetramethylbisphenol S.
Of these, bisphenol A, bisphenol S, tetramethyl bisphenol A and tetramethyl bisphenol S are preferable from the viewpoint of fluorescent whitening and whiteness, and more preferably bisphenol A, bisphenol S and tetramethyl bisphenol A, and particularly preferable. Is bisphenol A and bisphenol S, most preferably bisphenol A.

  The aromatic ester polymer can contain a (co) polymerization monomer as a constituent monomer in addition to the aromatic dicarboxylic acid, aromatic dialcohol and / or dihydric phenol. The (co) polymerization monomer is not particularly limited as long as it can be (co) polymerized with aromatic dicarboxylic acid, aromatic dialcohol and / or dihydric phenol, and carboxylic acid, alcohol and other monomers can be used.

Carboxylic acids include aliphatic monocarboxylic acids, aliphatic dicarboxylic acids, aliphatic polycarboxylic acids, alicyclic monocarboxylic acids, alicyclic dicarboxylic acids, alicyclic polycarboxylic acids, aromatic monocarboxylic acids and aromatic Polycarboxylic acids and the like are included.
Examples of the aliphatic monocarboxylic acid include monocarboxylic acids having 2 to 20 carbon atoms such as acetic acid, propionic acid, butyric acid, caproic acid, capric acid, tridecanoic acid, and nonadecanoic acid.
Examples of the aliphatic dicarboxylic acid include dicarboxylic acids having 2 to 25 carbon atoms, maleic acid, fumaric acid, succinic acid, adipic acid, sebacic acid, malonic acid, azelaic acid, mesaconic acid, citraconic acid, glutaconic acid, Examples thereof include isododecenyl succinic acid and n-dodecenyl succinic acid.
As the aliphatic polycarboxylic acid, a polycarboxylic acid having 6 to 15 carbon atoms (3- to 4-valent) is used, and 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1, Examples include 3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, and 1,2,7,8-octanetetracarboxylic acid.
Examples of the alicyclic monocarboxylic acid include monocarboxylic acids having 5 to 10 carbon atoms such as 1,2-cyclopentanedicarboxylic acid and 1,2-cyclohexanedicarboxylic acid.
As the alicyclic dicarboxylic acid, dicarboxylic acid having 3 to 10 carbon atoms is used, and examples thereof include cyclohexanedicarboxylic acid and methylmedicic acid.
As alicyclic polycarboxylic acid, C5-C10 polycarboxylic acid (3-4 valence) etc. are used, and 1,2, 4- cyclohexane tricarboxylic acid etc. are mentioned.
As aromatic monocarboxylic acid, C7-9 monocarboxylic acid etc. are used, and benzoic acid etc. are mentioned.
As the aromatic polycarboxylic acid, a polycarboxylic acid having 5 to 15 carbon atoms (3- to 4-valent) is used, and 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2, Examples include 5,7-naphthalene tricarboxylic acid, 1,2,4-naphthalene tricarboxylic acid, pyromellitic acid, and benzophenone tetracarboxylic acid.
Of these carboxylic acids, from the viewpoints of fluorescent whiteness and whiteness, aliphatic monocarboxylic acids, aliphatic dicarboxylic acids, aliphatic polycarboxylic acids, aromatic monocarboxylic acids and aromatic polycarboxylic acids are preferred, More preferably aliphatic monocarboxylic acids, aliphatic dicarboxylic acids, aromatic monocarboxylic acids and aromatic polycarboxylic acids, particularly preferably aliphatic dicarboxylic acids, aromatic monocarboxylic acids and aromatic polycarboxylic acids, most preferably aromatic Monocarboxylic acids and aromatic polycarboxylic acids.

  The same alcohol and dihydric phenol as above can be used, and the preferred range is also the same.

When using a (co) polymerization monomer, this content (% by weight) is preferably 2 to 80, based on the weight of the aromatic dicarboxylic acid, aromatic dialcohol, dihydric phenol and (co) polymerization monomer, More preferably, it is 5-70, Most preferably, it is 8-60, Most preferably, it is 10-50. Within this range, the fluorescent whiteness and whiteness can be further improved.

The weight average molecular weight (Mw), molecular weight distribution (Mw / Mn) and measurement method of the aromatic ester polymer are the same as Mw, Mw / Mn and measurement method of the aromatic vinyl polymer.

The aromatic ester polymer has a structure produced by polymerizing an aromatic dicarboxylic acid, an aromatic dialcohol and / or a divalent phenol as an essential constituent monomer, but is dicarboxylic acid {aromatic dicarboxylic acid, aliphatic Dicarboxylic acid and / or alicyclic dicarboxylic acid} and those produced by the reaction of the diol component are included.
The amount of dicarboxylic acid component and diol component used is such that the equivalent ratio (OH / COOH) of hydroxyl group (OH) to carboxyl group (COOH) is (0.6 to 1.4) / 1. It is preferably (0.7 to 1.3) / 1, more preferably (0.8 to 1.2) / 1, and most preferably (0.9 to 1.1) / 1.
Moreover, the usage-amount (weight%) of the monocarboxylic acid component {aliphatic monocarboxylic acid, aromatic monocarboxylic acid and / or alicyclic monocarboxylic acid} is 1 to 50 based on the weight of the dicarboxylic acid component. More preferably, it is 2-45, Most preferably, it is 3-40, Most preferably, it is 5-35.
Moreover, the usage-amount (weight%) of polycarboxylic acid component {3-4 valent aliphatic polycarboxylic acid, aromatic polycarboxylic acid, and / or alicyclic polycarboxylic acid} is based on the weight of the dicarboxylic acid component. 0.1-50, more preferably 0.5-45, particularly preferably 0.8-35, most preferably 1-35.
When using a monool component {alkyl monoalcohol, alkenyl monoalcohol, cycloalkyl monoalcohol, cycloalkenyl monoalcohol, aromatic monoalcohol, monophenol, secondary amine and / or alkylene oxide adduct thereof} The amount used (% by weight) is preferably from 1 to 50, more preferably from 2 to 45, particularly preferably from 3 to 40, and most preferably from 5 to 35, based on the weight of the diol component.
In addition, when a polyol {trivalent or higher, alkanolamine, polyamine and / or alkylene oxide adduct thereof} is used, the amount used (% by weight) is 0.1 to 50 based on the weight of the diol component. More preferably, it is 0.5-45, Most preferably, it is 0.8-35, Most preferably, it is 1-35.

As a polymerization method of a dicarboxylic acid component, a diol component, and if necessary a monocarboxylic acid component, a polycarboxylic acid component, a monool component and / or a polyol component, polymerization can be performed by a normal polymerization method of a carboxylic acid and an active hydrogen compound, Suspension polymerization, bulk polymerization, solution polymerization, and the like can be applied, and solution polymerization is preferable from the viewpoint of productivity.
A polymerization catalyst can be used for the polymerization. As a polymerization catalyst, a normal polymerization catalyst or the like is used, and metals (tin, titanium, antimony, manganese, nickel, zinc, lead, iron, magnesium, calcium, germanium, etc.) and metal compounds (dibutyltin oxide, orthodibutyl titanate, Tetrabutyl titanate, zinc acetate, lead acetate, cobalt acetate, sodium acetate, antimony trioxide, etc.).
When a polymerization catalyst is used, the amount (% by weight) used is preferably from 0.001 to 1, more preferably from 0.005 to 0.9, and particularly preferably from 0.001 to 0.9, based on the total weight of the monomers used. 01 to 0.85, most preferably 0.05 to 0.8.

In the case of solution polymerization and suspension polymerization, any solvent can be used as long as it does not have (1) active hydrogen and (2) dissolves the dicarboxylic acid component, diol component, and aromatic ester polymer. As such a solvent, the same solvent etc. as the case of an aromatic urethane polymer can be used.
When using a solvent, the amount used (% by weight) is preferably 20 to 800, more preferably 30 to 750, particularly preferably 40 to 700, most preferably based on the total weight of the dicarboxylic acid component and the diol component. 50-650.
When a solvent is used, the solvent may be removed after the reaction. As a method for removing the solvent, a vacuum distillation method or the like can be applied. As conditions for distilling off under reduced pressure, conditions such as distillation at 100 to 130 ° C. under a reduced pressure of 26.6 to 0.7 MPa can be applied.

The reaction temperature (° C.) is preferably from 150 to 300, more preferably from 170 to 280, particularly preferably from 180 to 250. The reaction atmosphere is preferably a dry inert gas (nitrogen gas, carbon dioxide gas, argon gas, etc.) atmosphere. The reaction can be carried out under atmospheric pressure, under reduced pressure or under pressure, but from the viewpoint of reaction efficiency, it is preferably under reduced pressure, and more preferably reacted at a pressure of about 26.6 to 0.7 MPa or less. .

The end point of the esterification reaction is confirmed according to JIS K6751-2: 1999, appendix, acid value measurement, and the end point of the reaction can be the time when the acid value becomes 5 or less. The reaction time is preferably about 1 to 20 hours.
In addition, you may superpose | polymerize, dripping the whole quantity or one part of a monomer. Moreover, you may superpose | polymerize, dripping the whole quantity or one part of a polymerization catalyst. Moreover, you may superpose | polymerize, dripping the whole quantity or one part of a solvent with a monomer or a polymerization catalyst. On the other hand, the whole amount of the solvent may be charged into the polymerization tank and polymerization may be performed while removing the solvent. Among these, from the viewpoint of productivity and the like, the method of dropping the total amount of the monomer and the polymerization catalyst and the method of dropping a part of the solvent together with the monomer or the polymerization catalyst are preferable, and the total amount of the monomer and the polymerization catalyst is more preferable. It is the method of dripping together with a part of solvent.

As a method for sulfonation of the sulfonated aromatic ester polymer, a method similar to that for the sulfonated aromatic vinyl polymer can be applied.

Of the sulfonated aromatic vinyl polymer, sulfonated aromatic urethane polymer, and sulfonated aromatic ester polymer, sulfonated aromatic vinyl polymer and sulfonated aromatic polyester polymer are preferred from the viewpoint of fluorescent whiteness and whiteness. More preferably, it is a sulfonated aromatic vinyl polymer.

Inclusion of sulfo (—SO ₃ H) group and sulfonate (—SO ₃ M: M is counter ion of neutralized salt) group in sulfonated aromatic vinyl polymer, sulfonated aromatic urethane polymer or sulfonated aromatic ester polymer The amount (% by weight, hereinafter abbreviated as the content of the sulfo group) is 5 to 45 based on the weight of these polymers from the viewpoints of solubility in water, fluorescent whitening and whiteness improving effects, and the like. More preferably, it is 10-42, Most preferably, it is 15-41, Most preferably, it is 30-40.

The content (% by weight) of the sulfo group in the sulfonated aromatic vinyl polymer, sulfonated aromatic urethane polymer or sulfonated aromatic ester polymer is determined by ICP (inductively coupled high frequency plasma method, plasma temperature 3000 ° C., for example, Shimadzu The content (% by weight) of sulfur in the polymer is measured by ICPS-8000 (manufactured by Seisakusho Co., Ltd.), and is calculated by converting it to the content of “SO ₃ H”.

The weight average molecular weight (Mw) of the sulfonated aromatic vinyl polymer, the sulfonated aromatic urethane polymer, and the sulfonated aromatic ester polymer is preferably 2,000 to 500,000, more preferably 3,000 to 400,000. Is 3500-350,000, most preferably 4,000-300,000. Within this range, the fluorescent whiteness and whiteness are further improved.
The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably from 1.2 to 5, more preferably from 1.3 to 4.8, particularly preferably from 1.4 to 4.5, most preferably 1.5 to 4.3. Within this range, the fluorescent whiteness and whiteness are further improved.
In the present invention, Mw, Mn and Mw / Mn of a polymer after sulfonation (including a polymer obtained by polymerizing a sulfo group-containing vinyl monomer) are polyethylene glycol {for example, PEO-15, PEO -8 (manufactured by Sumitomo Seika Co., Ltd.), TSK standard POLY (ETHYLENEOXIDE) SE-150, SE-30, SE-8 (manufactured by Tosoh Corp.)} are measured by gel permeation chromatography.

Preferable examples of the sulfonated aromatic vinyl polymer, the sulfonated aromatic urethane polymer, and the sulfonated aromatic ester polymer include the following copolymers. The numerical value following = represents the weight ratio of the monomers.

(1) Sulfonated polystyrene Mw 31,000 Mw / Mn 2.3 Sulfo group content 36% by weight
(2) Sulphonated product of styrene / α-methylstyrene = 90/10 copolymer Mw 3,5000 Mw / Mn 2.4 Sulfo group content 36% by weight
(3) Sulfonate of styrene / ethyl methacrylate = 90/10 copolymer Mw 29,000 Mw / Mn 3.1 Sulfo group content 32% by weight
(4) Polyethylene terephthalate Mw20,000 Mw / Mn3.6 Sulfo group content 25% by weight
(5) Sulfonate of styrene / ethyl methacrylate = 90/10 copolymer Mw28,000 Mw / Mn3.1 Sulfo group content 36% by weight
(6) Sulfonated product of styrene / ethyl methacrylate = 85/15 copolymer Mw27,000 Mw / Mn3.1 Sulfo group content 31% by weight
(7) Sulfonate of styrene / ethyl methacrylate = 50/50 copolymer Mw27,000 Mw / Mn3.1 Sulfo group content 18% by weight
(8) Sulfonate of styrene / ethyl methacrylate = 55/45 copolymer Mw 27,000 Mw / Mn 3.1 Sulfo group content 20% by weight
(9) Sulfonated product of polystyrene Mw4,200 Mw / Mn2.0 Sulfo group content 36% by weight
(10) Sulfonated product of polystyrene Mw4,500 Mw / Mn2.0 Sulfo group content 36% by weight
(11) Sulfonated product of polystyrene Mw280,000 Mw / Mn2.7 Sulfo group content 36% by weight
(12) Sulfonated product of polystyrene Mw250,000 Mw / Mn2.6 Sulfo group content 36% by weight
(13) Polysulfonated product Mw3,700 Mw / Mn2.0 Sulfo group content 36% by weight
(14) Sulfonated product of polystyrene Mw3,200 Mw / Mn2.0 Sulfo group content 36% by weight
(15) Sulfonated polystyrene Mw 330,000 Mw / Mn 2.8 Sulfo group content 36% by weight
(16) Sulfonated product of polystyrene Mw 360,000 Mw / Mn 2.9 Sulfo group content 36% by weight
(17) Sulfonated product of polystyrene Mw28,000 Mw / Mn2.3 Sulfo group content 32% by weight
(18) Sulfonated product of polystyrene Mw29,000 Mw / Mn2.3 Sulfo group content 33% by weight
(19) Sulfonated product of polystyrene Mw33,000 Mw / Mn2.3 Sulfo group content 39% by weight
(20) Sulfonated polystyrene Mw 31,000 Mw / Mn 2.3 Sulfo group content 37% by weight
(21) Sulfonated product of polystyrene Mw28,000 Mw / Mn2.3 Sulfo group content 29% by weight
(22) Polysulfonated polystyrene Mw28,000 Mw / Mn2.3 Sulfo group content 28% by weight
(23) Sodium styrene sulfonate / acrylic acid = 90/10 copolymer Mw 3,5000 Mw / Mn 2.4 Sulfo group content 41 wt%

Of these, (1), (2), (3), (5), (6), (9), (10), (11), (12), (17), (18), (19 ), (20) and (23), more preferably (1), (2), (3), (5), (6), (12), (19), (20) and (23). It is.

Further, the fluorescent whitening enhancer of the present invention includes, for example, a solvent, a dispersant, a lubricant, an antifoaming agent, a water retention agent, a thickening agent, a water-resistant agent, a wetting agent, a surface sizing agent, an antiseptic / antifungal agent, an anti-fouling agent. Known additives such as odorants, fragrances, dyes, ultraviolet absorbers, antioxidants, fillers, slime control agents and / or pitch control agents used in the production of paper can be added. When the additive agent is added, the amount used (% by weight) is 0.01 to 50 based on the weight of the sulfonated aromatic vinyl polymer, sulfonated aromatic urethane polymer and / or sulfonated aromatic ester polymer. More preferably 0.05 to 40, particularly preferably 0.08 to 30, and most preferably 0.1 to 20.
The fluorescent whitening enhancer of the present invention can contain water. When water is contained, the content (% by weight) is determined from the viewpoint of handling of the fluorescent whitening enhancer (viscosity, etc.), etc., sulfonated aromatic vinyl polymer, sulfonated aromatic urethane polymer and / or sulfonated. Based on the weight of the aromatic ester polymer, it is preferably 1 to 500, more preferably 5 to 400, particularly preferably 10 to 300, and most preferably 15 to 200.

The fluorescent whitening enhancer of the present invention is used together with the fluorescent brightening agent, and the fluorescent whitening degree and the whiteness can be remarkably improved as compared with the case where the fluorescent whitening enhancer of the present invention is not blended.
As the fluorescent whitening agent used together with the fluorescent whitening enhancer of the present invention, those used at the time of paper production and the like can be used without limitation, diaminostilbene, coumarin, pyrazoline, imidazole, triazole, oxazole And naphthalimide-based optical brighteners, etc. {Paper and Processing Chemical Dictionary, page 65, Tech Times Co., Ltd., issued on February 25, 1991} are preferred, but diaminostilbene-based optical brighteners are preferred. .

The use amount (% by weight) of the fluorescent whitening enhancer of the present invention is preferably 0.2 to 50000, more preferably 1 to 9000, particularly preferably 2 to 5000 based on the weight of the fluorescent whitening agent. Preferably it is 2.9-3500. That is, the lower limit of the amount (% by weight) of the fluorescent whitening enhancer of the present invention is preferably 0.2, more preferably 1, particularly preferably 2, and most preferably based on the weight of the fluorescent whitening agent. Similarly, the upper limit is preferably 50000, more preferably 9000, particularly preferably 5000, and most preferably 3500.

The fluorescent whitening enhancer of the present invention is blended in a coating paper coating mainly composed of pigment and latex together with the fluorescent whitening agent, and is blended in a coating paper coating containing no pigment. And coated with pigment coated paper or clear coated paper.
In addition, the fluorescent whitening enhancer of the present invention is internally added to a pulp slurry or the like together with the fluorescent whitening agent in a papermaking (making) process to finish various papers.

As pigments, inorganic pigments such as clay, calcium carbonate, titanium oxide, satin white, barium sulfate, talc, zinc oxide, gypsum, silica and ferrite, and organic pigments such as polystyrene pigment are used alone or in combination. The
Latex includes styrene butadiene latex, carboxyl modified styrene butadiene latex, acrylic resin emulsion, vinyl acetate resin emulsion, vinyl chloride resin emulsion, acrylic styrene resin emulsion, silicone resin emulsion, urethane resin emulsion, epoxy resin emulsion, fluororesin emulsion, ABS Synthetic binders such as latex, NBR latex and CR latex can be mentioned.
In addition, for coated paper coatings, if necessary, dispersants, lubricants, antifoaming agents, water retention agents, thickeners, water resistance agents, wetting agents, antiseptic / antifungal agents, deodorants, fragrances, Dyes, ultraviolet absorbers, antioxidants and / or surface sizing agents can be added.
Moreover, a sizing agent, a filler, a dye, an antifoaming agent, a slime control agent, and / or a pitch control agent can be added to the pulp slurry as necessary.

When the fluorescent whitening enhancer of the present invention is added to a paint for coated paper for pigment coated paper, the amount used (wt%) of the fluorescent whitening enhancer is based on the weight of the pigment in the paper coated paint. 0.01-5, more preferably 0.05-4.5, particularly preferably 0.08-4, most preferably 0.1-3.5. That is, in this case, the lower limit of the amount (% by weight) of the fluorescent whitening enhancer used is preferably 0.01, more preferably 0.05, particularly preferably based on the weight of the pigment in the paper coating material. The upper limit is 0.08, most preferably 0.1, and the upper limit is preferably 5, more preferably 4.5, particularly preferably 4, and most preferably 3.5.

Further, in this case, the use amount (% by weight) of the optical brightener is preferably 0.01 to 5, more preferably 0.05 to 4.5, based on the weight of the pigment in the coating material for coated paper. Particularly preferred is 0.08 to 4, most preferably 0.1 to 3.5. That is, in this case, the lower limit of the use amount (% by weight) of the optical brightener is preferably 0.01, more preferably 0.05, particularly preferably based on the weight of the pigment in the coating material for coated paper. 0.08, most preferably 0.1, and similarly the upper limit is preferably 5, more preferably 4.5, particularly preferably 4, most preferably 3.5.

When the fluorescent whitening enhancer of the present invention is added to a coated paper paint for clear coat paper, the amount (wt%) of the fluorescent whitening enhancer is 0 based on the weight of the coated paper paint. 0.01 to 5 is preferable, 0.05 to 4.5 is more preferable, 0.08 to 4 is particularly preferable, and 0.1 to 3.5 is most preferable. That is, in this case, the lower limit of the use amount (% by weight) of the fluorescent whitening enhancer is preferably 0.01, more preferably 0.05, particularly preferably 0. 0 based on the weight of the coating paper coating material. 08, most preferably 0.1, and similarly the upper limit is preferably 5, more preferably 4.5, particularly preferably 4, and most preferably 3.5.

When the fluorescent whitening enhancer of the present invention is added to a coated paper coating for clear coat paper, the amount (% by weight) of the fluorescent whitening agent is set to 0. 0 based on the weight of the coated paper coating. 01-5 are preferable, More preferably, it is 0.05-4.5, Most preferably, it is 0.08-4, Most preferably, it is 0.1-3.5. That is, in this case, the lower limit of the use amount (% by weight) of the optical brightener is preferably 0.01, more preferably 0.05, particularly preferably 0.08, based on the weight of the coating material for coated paper. Most preferably, the upper limit is 0.1, and similarly, the upper limit is preferably 5, more preferably 4.5, particularly preferably 4, and most preferably 3.5.

When the fluorescent whitening enhancer of the present invention is internally added to the pulp slurry, the used amount (% by weight) of the fluorescent whitening enhancer is preferably 0.01 to 5, more preferably 0, based on the weight of the pulp. 0.05 to 4.5, particularly preferably 0.08 to 4, and most preferably 0.1 to 3.5. That is, in this case, the lower limit of the use amount (% by weight) of the fluorescent whitening enhancer is preferably 0.01, more preferably 0.05, particularly preferably 0.08, most preferably based on the weight of the pulp. Is 0.1, and the upper limit is preferably 5, more preferably 4.5, particularly preferably 4, and most preferably 3.5.

When the fluorescent whitening enhancer of the present invention is internally added to the pulp slurry, the amount (% by weight) of the fluorescent whitening agent used is preferably from 0.01 to 5, more preferably from 0.005 based on the weight of the pulp. It is 05 to 4.5, particularly preferably 0.08 to 4, most preferably 0.1 to 3.5. That is, in this case, the lower limit of the use amount (% by weight) of the optical brightener is preferably 0.01, more preferably 0.05, particularly preferably 0.08, most preferably based on the weight of the pulp. Similarly, the upper limit is preferably 5, more preferably 4.5, particularly preferably 4, and most preferably 3.5.

The coating material for coated paper is coated on paper by a known method using an air knife coater, blade coater, roll coater, rod coater, spray coater, curtain flow coater, size press or the like. After coating, it is dried and subjected to calendering finishing such as super calendering or soft nip calendering as necessary to produce coated paper. The coating temperature is usually 10 to 60 ° C., the drying temperature is usually 70 to 150 ° C., and the calendering finish temperature is usually 30 to 160 ° C.

The pulp slurry containing the fluorescent whitening enhancer of the present invention used together with the fluorescent whitening agent is made by a known method using a long paper machine or a round paper machine and then dried to produce a paper. Is done.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. Unless otherwise specified, “part” means “part by weight” and “%” means “% by weight”.
<Example 1>
100 parts of polystyrene having a weight average molecular weight of 16,000 (Mw / Mn2.1) was dissolved in 400 parts of 1,2-dichloroethane, and 10 parts of triethyl phosphate was further added to prepare a raw material solution. This raw material solution and 84.8 parts of anhydrous sulfuric acid (sulfuric anhydride / molar ratio of aromatic ring in polymer 1.10) were continuously supplied to a reaction vessel equipped with a stirrer over 3 hours, and sulfonated at 30 ° C. Reaction was performed.
The produced dispersion slurry of sulfonated polystyrene was added to 200 parts of water at a temperature of 30 ° C. with stirring, and then neutralized to a pH of 7 using a 30% aqueous sodium hydroxide solution. 1,2-Dichloroethane was distilled from the neutralized mixture at normal pressure (83.5 ° C.) to obtain an aqueous sodium polystyrene sulfonate solution. Next, after finely adjusting the pH to 8 using a 10% aqueous sodium hydroxide solution, water was added to obtain a 10% sodium polystyrene sulfonate aqueous solution. This polymer aqueous solution was directly used as the fluorescent whitening enhancer (A1) of the present invention. The weight average molecular weight of the obtained polymer was 31,000, Mw / Mn was 2.3, and the sulfo group content was 36%.

<Example 2>
A polystyrene is a styrene / α-methylstyrene (90 parts / 10 parts) copolymer having a weight average molecular weight of 15,000 (Mw / Mn2.2), and 84.8 parts of anhydrous sulfuric acid is 83.7 parts of anhydrous sulfuric acid (anhydrous sulfuric acid). / Mole ratio of aromatic ring in polymer 1.10) A styrene / α-methylstyrene (90/10) copolymer sodium sulfonate aqueous solution having a concentration of 10% was obtained in the same manner as in Example 1 except that the molar ratio was changed to 1.10). It was. And this polymer aqueous solution was made into the fluorescent whitening enhancer (A2) of this invention as it was. The weight average molecular weight of the obtained polymer was 35,000, Mw / Mn was 2.4, and the sulfo group content was 36%.

<Example 3>
A polystyrene is a styrene / ethyl methacrylate (90 parts / 10 parts) copolymer having a weight average molecular weight of 14,000 (Mw / Mn 2.7), 84.8 parts of anhydrous sulfuric acid is 76.22 parts of anhydrous sulfuric acid (anhydrous sulfuric acid / A 10% concentration aqueous sodium styrenesulfonate / ethyl methacrylate (90/10) copolymer solution was obtained in the same manner as in Example 1 except that the molar ratio of the aromatic rings in the polymer was changed to 1.10). And this polymer aqueous solution was made into the fluorescent whitening enhancer (A3) of this invention as it was. The weight average molecular weight of the obtained polymer was 29,000, Mw / Mn was 3.1, and the content of sulfo group was 32%.

<Example 4>
A polystyrene is a styrene / ethyl methacrylate (90 parts / 10 parts) copolymer having a weight average molecular weight of 13,000 (Mw / Mn 2.7), and 84.8 parts of anhydrous sulfuric acid is 79.1 parts of anhydrous sulfuric acid (anhydrous sulfuric acid / A 10% concentration sodium styrenesulfonate / ethyl methacrylate (90/10) copolymer aqueous solution was obtained in the same manner as in Example 1 except that the molar ratio of the aromatic rings in the polymer was changed to 1.14). And this polymer aqueous solution was made into the fluorescent whitening enhancer (A4) of this invention as it was. The weight average molecular weight of the obtained polymer was 27,000, Mw / Mn was 3.1, and the sulfo group content was 36%.

<Example 5>
A polystyrene is a styrene / ethyl methacrylate (85 parts / 15 parts) copolymer having a weight average molecular weight of 13,000 (Mw / Mn 2.7), and 84.8 parts of anhydrous sulfuric acid is 72.1 parts of anhydrous sulfuric acid (anhydrous sulfuric acid / A 10% concentration sodium styrenesulfonate / ethyl methacrylate (85/15) copolymer aqueous solution was obtained in the same manner as in Example 1 except that the molar ratio of aromatic rings in the polymer was changed to 1.10). And this polymer aqueous solution was made into the fluorescent whitening enhancer (A5) of this invention as it was. The weight average molecular weight of the obtained polymer was 27,000, Mw / Mn was 3.1, and the sulfo group content was 31%.

<Example 6>
A polystyrene having a weight average molecular weight of 16,000 (Mw / Mn2.1) is converted to a polystyrene having a weight average molecular weight of 130,000 (Mw / Mn2.4), 84.8 parts of anhydrous sulfuric acid is 86.1 parts of anhydrous sulfuric acid (anhydrous sulfuric acid / A polystyrene sodium sulfonate aqueous solution having a concentration of 10% was obtained in the same manner as in Example 1 except that the molar ratio of aromatic rings in the polymer was changed to 1.12). And this polymer aqueous solution was made into the fluorescent whitening enhancer (A6) of this invention as it was. The weight average molecular weight of the obtained polymer was 250,000, Mw / Mn was 2.6, and the sulfo group content was 36%.

<Example 7>
Sodium polystyrene sulfonate having a concentration of 10% in the same manner as in Example 1 except that 84.8 parts of sulfuric anhydride was changed to 87.7 parts of anhydrous sulfuric acid (molar ratio of sulfuric acid anhydride / aromatic ring in polymer 1.14). An aqueous solution was obtained. And this polymer aqueous solution was made into the fluorescent whitening enhancer (A7) of this invention as it was. The weight average molecular weight of the obtained polymer was 33,000, Mw / Mn was 2.3, and the sulfo group content was 39%.

<Example 8>
Sodium polystyrene sulfonate having a concentration of 10% in the same manner as in Example 1 except that 84.8 parts of sulfuric anhydride was changed to 86.1 parts of anhydrous sulfuric acid (sulfuric anhydride / molar ratio of aromatic ring in polymer 1.12). An aqueous solution was obtained. And this polymer aqueous solution was made into the fluorescent whitening enhancer (A8) of this invention as it was. The weight average molecular weight of the obtained polymer was 31,000, Mw / Mn was 2.3, and the sulfo group content was 37%.

<Example 9>
Into a reaction vessel equipped with a dripping device, a reflux condenser, a nitrogen introducing tube, a stirring device and a thermometer, 650 parts of water was added, and after replacing with nitrogen under stirring, 6 parts of sodium persulfate was dissolved at 95-98 ° C. 50 parts of the aqueous solution and a mixed monomer of 270 parts of sodium styrenesulfonate and 30 parts of acrylic acid were continuously dropped from two dropping devices for 2 hours, respectively, and kept at the same temperature for 2 hours after the completion of dropping. Thereafter, the mixture was cooled to 40 ° C. to obtain a sodium styrenesulfonate / acrylic acid copolymer aqueous solution having a concentration of 30%. This polymer was directly used as the fluorescent whitening enhancer (A9) of the present invention. The weight average molecular weight of the obtained polymer was 35,000, Mw / Mn was 2.4, and the sulfo group content was 41%.

<Example 10>
A polystyrene is a styrene / ethyl methacrylate (50 parts / 50 parts) copolymer having a weight average molecular weight of 13,000 (Mw / Mn 2.9), and 84.8 parts of anhydrous sulfuric acid is 42.4 parts of anhydrous sulfuric acid / A 10% concentration aqueous sodium styrenesulfonate / ethyl methacrylate (50/50) copolymer solution was obtained in the same manner as in Example 1 except that the molar ratio of the aromatic rings in the polymer was changed to 1.10). And this polymer aqueous solution was made into the fluorescent whitening enhancer (A10) of this invention as it was. The weight average molecular weight of the obtained polymer was 27,000, Mw / Mn was 3.1, and the sulfo group content was 18%.

<Example 11>
A polystyrene having a weight average molecular weight of 16,000 (Mw / Mn2.1) is converted to a polystyrene having a weight average molecular weight of 2,000 (Mw / Mn1.6), 84.8 parts of anhydrous sulfuric acid is 84.8 parts of anhydrous sulfuric acid (anhydrous sulfuric acid / A polystyrene polystyrene sulfonate aqueous solution having a concentration of 10% was obtained in the same manner as in Example 1 except that the molar ratio of aromatic rings in the polymer was changed to 1.10). And this polymer aqueous solution was made into the fluorescent whitening enhancer (A11) of this invention as it was. The weight average molecular weight of the obtained polymer was 4,200, Mw / Mn was 2.0, and the sulfo group content was 36%.

<Example 12>
A polystyrene having a weight average molecular weight of 16,000 (Mw / Mn2.1) is converted to a polystyrene having a weight average molecular weight of 140,000 (Mw / Mn2.5), 84.8 parts of anhydrous sulfuric acid is 86.3 parts of anhydrous sulfuric acid (anhydrous sulfuric acid / A polystyrene sodium sulfonate aqueous solution having a concentration of 10% was obtained in the same manner as in Example 1 except that the molar ratio of aromatic rings in the polymer was changed to 1.12). And this polymer aqueous solution was made into the fluorescent whitening enhancer (A12) of this invention as it was. The weight average molecular weight of the obtained polymer was 280,000, Mw / Mn was 2.7, and the sulfo group content was 36%.

<Comparative Example 1>
In a reaction vessel equipped with a dropping device, a reflux condenser, a nitrogen inlet tube, a stirring device, and a thermometer, charge water (59.9%), 50% acrylamide aqueous solution (392.2 parts) and methallylic acid (1.8 parts). Substitution was carried out and the temperature was raised to 50 to 55 ° C., and then 6.3 parts of 5% aqueous ammonium persulfate solution and 3.3 parts of 2% aqueous sodium metabisulfite solution were added. After 30 minutes, the temperature in the reaction system rose to 85 ° C., and further reacted at a temperature of 85 ° C. for 2 hours. Thereafter, 20.8 parts of water was added to obtain a polyacrylamide aqueous solution having a concentration of 21.1%. This polymer aqueous solution was directly used as a fluorescent whitening enhancer (B1) for comparison. The weight average molecular weight of the obtained polymer was 200,000, and Mw / Mn was 3.9.

<Comparative example 2>
A 10% aqueous solution of polyvinyl alcohol (PVA-105 manufactured by Kuraray Co., Ltd., weight average molecular weight 22000, saponification degree 98 to 99 mol%) was prepared and used as a fluorescent whitening enhancer (B2) for comparison.

<Comparative Example 3>
A 10% aqueous solution of carboxymethyl cellulose (FINFIX 5 (4% aqueous solution viscosity, 25 ° C., 40 mPa · s) manufactured by NOVIANT) was prepared and used as a fluorescent whitening enhancer (B3) for comparison.

<Comparative example 4>
A 10% aqueous solution of hydroxyethyl cellulose (NATROLSOL 250LR (5% aqueous solution viscosity, 25 ° C., 140 mPa · s) manufactured by HERCULES INC.) Was prepared and used as a fluorescent whitening enhancer (B4) for comparison.

<Comparative Example 5>
A 10% aqueous solution of polyethylene glycol (manufactured by Sanyo Chemical Industries, Ltd., PEG-400, average molecular weight 400, hydroxyl value 281) was prepared and used as a fluorescent whitening enhancer (B5) for comparison.

<Comparative Example 6>
A 10% aqueous solution of polyvinylpyrrolidone (manufactured by Nippon Shokubai Co., Ltd., K-90, K value = 90) was prepared as a comparative fluorescent whitening enhancer (B6).

In addition, each characteristic etc. were calculated | required as follows.
(1) Weight average molecular weight, molecular weight distribution (Mw / Mn)
Apparatus: HLC-8020 manufactured by Tosoh Corporation, column: TSKgel G6000 PW XL manufactured by Tosoh Corporation, detector: differential refractometer detector built in the apparatus main body, eluent: 0.2 M phosphate buffer, flow rate: 0 .6 ml / min, column temperature: 40 ° C., measurement sample concentration: 0.1 wt% eluent solution, injection volume: 50 μl, standard materials: PEO-15, PEO-8, Tosoh (manufactured by Sumitomo Seika Co., Ltd.) TSK standard POLY (ETHYLENEOXIDE) SE-150, SE-30, SE-8

(2) Content of sulfo group in polymer The content (%) of sulfo group of sulfonated aromatic vinyl polymer, sulfonated aromatic urethane polymer or sulfonated aromatic ester polymer is ICPS-8000 manufactured by Shimadzu Corporation. Then, the content (%) of sulfur in the polymer was measured by the inductively coupled high-frequency plasma method (plasma temperature 3000 ° C.), and this was converted to the content of “SO ₃ H”. As a measurement sample, 20 ml of a 10% concentration polymer aqueous solution was used.

(3) Amount of use of sulfonating agent (anhydrous sulfuric acid) The amount of sulfonating agent (anhydrous sulfuric acid) used is such that the molar ratio of sulfonating agent (anhydrous sulfuric acid) / aromatic ring in the polymer is 1.10, 1.12 or It was determined to be 1.14.
The number of moles of the aromatic ring in the polymer is the number of moles of the aromatic monomer contained in the polymer (100 parts) {in the case of polystyrene, a value obtained by dividing 100 by the molecular weight of the styrene monomer; styrene / α- In the case of a methylstyrene (90/10) copolymer, the sum of 90 divided by the molecular weight of the styrene monomer and 10 divided by α-methylstyrene; styrene / ethyl methacrylate (90/10) copolymer In the case of coalescence, a value obtained by dividing 90 by the molecular weight of the styrene monomer; in the case of a styrene / ethyl methacrylate (85/15) copolymer, a value obtained by dividing 85 by the molecular weight of the styrene monomer}.

Using the fluorescent whitening enhancers (A1 to A12 and B1 to B6) of Examples 1 to 12 and Comparative Examples 1 to 6, pigment coated paper coating paints 1-2 and clear coated paper coating paints were prepared. And coated on high-quality paper to produce pigment-coated papers 1 and 2 and clear-coated paper, respectively.
Further, using the above-mentioned fluorescent whitening enhancer and kraft pulp, paper was made to produce an internal paper having a basis weight of 63 g / m ² .
The performances of the pigment coated paper coating paints 1-2 and clear coated paper coating paints, pigment coated papers 1-2, clear coated paper, and internal papers were evaluated by the following methods, and the results are shown in Table 1. Shown in ~ 4.

(1) Pigment coated paper coating paint 1:
50 parts of second grade clay (HT clay manufactured by ENGELHARD MINERAL & CHEMICALS), 50 parts of heavy calcium carbonate (FMT-90 manufactured by FMT), 0.2 part of dispersant (San Nopco, SN Dispersant 5040), hydroxylated 0.2 parts of sodium, 10 parts of SBR latex [JSR0629 manufactured by JSR Corporation], 0.4 parts of thickener [manufactured by San Nopco Co., Ltd., SN thickener 920], fluorescent whitening agent [Nippon Kayaku Co., Ltd. A paper coating material having a pH of 9 and a coating concentration of 62% by weight was prepared with 2.0 parts of Kyaphor NV liquid] and 0.5 parts of fluorescent whitening enhancer.

(2) Pigment coated paper coating paint 2:
50 parts of second grade clay (HT clay manufactured by ENGELHARD MINERAL & CHEMICALS), 50 parts of heavy calcium carbonate (FMT-90 manufactured by FMT), 0.2 part of dispersant (San Nopco, SN Dispersant 5040), hydroxylated 0.2 parts of sodium, 10 parts of SBR latex [JSR0629 manufactured by JSR Co., Ltd.], 5 parts of oxidized starch [manufactured by Nippon Shokuhin Kako Co., Ltd., MS-3600], fluorescent whitening agent [Nippon Kayaku Co., Ltd. A paper coating composition having a pH of 9 and a coating concentration of 62% by weight was prepared with a composition of 2.0 parts of Kyaphor PAS liquid] and 0.5 parts of fluorescent whitening enhancer.

(3) Clear coat paper coating paint fluorescent whitening agent [Nippon Kayaku Co., Ltd., Kyaphor NV liquid] 0.9 part and fluorescent whitening enhancer 0.5 part diluted with water, paper coating 100 parts of the paint were prepared.

(4) Pigment coated paper 1-2
The coating speed for pigment coated paper coating 1 or 2 is 20 m / m so that the coating amount is about 12 g / m ² on one side of commercially available high-quality paper (basis weight 68 g / m ² , whiteness 73.5%). Each coated paper was obtained by performing blade coating at min and then drying with hot air at 135 ° C. for 20 seconds. The obtained coated paper was subjected to a super calendar process to obtain pigment-coated paper 1 or 2. In addition, MLC [made by Osugi Co., Ltd.] was used for the coating apparatus. Supercalender treatment conditions were a temperature of 40 ° C., a linear pressure of 70 kg / cm, and paper passing twice.

(5) Clear-coated paper Clear-coated paper coating is applied on one side of commercially available high-quality paper (basis weight 68 g / m ² , whiteness 73.5%) at a coating speed of 20 m / min. I got paper. The obtained coated paper was dried with a drum dryer to obtain clear coated paper. In addition, MLC [made by Osugi Co., Ltd.] was used for the coating apparatus. The drying conditions were 80 ° C. and 60 seconds.

(6) A pulp composed of 30 parts by weight of internally-fitted softwood bleached kraft pulp (NBKP) and 70 parts of hardwood bleached kraft pulp (LBKP) (dry mass part, hereinafter the same) is beaten with a refiner, and Canadian Standard Freeness (JIS) P8121-1995, 4. Canadian Standard Freeness Test Method) was 400 ml CSF. This pulp was made into 1% pulp slurry, and 10 parts of light calcium carbonate (TP121S manufactured by Okutama Kogyo Co., Ltd.) and diaminostilbene fluorescent brightening agent (100 parts of pulp) in a pulp disaggregator. Nippon Kayaku Co., Ltd. (Kyaphor NV liquid) 0.5 part, fluorescent whitening enhancer 0.5 part, and a commercial cation yield improver 0.03 part were added. Then, using a handbrushing device, paper was made (made) according to JIS P8209-1994 to produce an internal paper having a basis weight of 63 g / m ² .

<Pigment coated paper paint properties>
(1) Low shear viscosity (mPa · s): Measured using a BM viscometer (60 rpm, 25 ° C.) manufactured by Tokyo Keiki Co., Ltd. In addition, it is preferable that the low shear viscosity does not change as compared with no addition.
(2) High shear viscosity (mPa · s): Measured using a high shear viscometer PM-9001HV (8800 rpm, 25 ° C.) manufactured by SMT Co., Ltd. It is preferable that the high shear viscosity does not change.

<Fluorescent whitening>
Pigment coated paper 1-2, clear coated paper and internal paper are left in a constant temperature and humidity chamber at 25 ° C and 50RH% (relative humidity) for 48 hours, and then light in the visible / ultraviolet region (using a pulsed xenon lamp) The whiteness (W1) (wavelength: measured from 400 to 700 nm) was measured, and the whiteness (W2) (wavelength: measured from 400 to 700 nm) was measured with light (light in the visible region) passed through an ultraviolet filter. . Next, the difference (W1−W2) between the whiteness (W1) and the whiteness (W2) was defined as the fluorescent whitening degree. In addition, whiteness (%) was measured about the coating surface based on JIS P8148-1993, characteristic B) using Nippon Denshoku Industries Co., Ltd. PF-10. The fluorescent whitening degree (%) is preferably as the numerical value is large.

As described in Tables 1 to 4, those using the fluorescent whitening enhancers (A1) to (A12) of the present invention are those using the fluorescent whitening enhancers (B1) to (B6) for comparison. In comparison, it can be seen that the fluorescent whiteness and whiteness are remarkably high. It is also clear that the fluorescence-enhanced brightener of the present invention has almost no change in the viscosity of the paint even when used in a paint for coated paper.

The fluorescent whitening enhancer of the present invention is used together with the fluorescent brightening agent, and can significantly improve the fluorescent whiteness and whiteness compared to the case where the fluorescent whitening enhancer of the present invention is not blended. Therefore, it can be used without limitation as long as the fluorescent whitening agent is used. Among various fields, the fluorescent whitening enhancer of the present invention is a paint for coated paper mainly composed of pigment and latex (finished to pigment-coated paper), and a paint for coated paper containing no pigment (for clear-coated paper). It can be suitably used together with a fluorescent whitening agent used for pulp slurry and the like in the papermaking (making) process.

Claims (7)

A fluorescent whitening enhancer for use with a fluorescent whitening agent, comprising a sulfonated aromatic vinyl polymer, a sulfonated aromatic urethane polymer and / or a sulfonated aromatic ester polymer. Agent. The fluorescent whitening enhancer according to claim 1, comprising a sulfonated aromatic vinyl polymer, wherein the vinyl polymer comprises styrene sulfonic acid as an essential constituent unit. The fluorescent whitening according to claim 1 or 2, comprising a sulfonated aromatic urethane polymer, wherein the urethane polymer comprises aromatic diisocyanate, aromatic dialcohol and / or dihydric phenol as essential constituent units. Enhancer. The fluorescence according to any one of claims 1 to 3, comprising a sulfonated aromatic ester polymer, wherein the ester polymer comprises an aromatic dicarboxylic acid, an aromatic dialcohol and / or a dihydric phenol as an essential constituent unit. Whitening enhancer. A paint for coated paper comprising the fluorescent whitening enhancer according to any one of claims 1 to 4. Coated paper obtained by coating the paint for coated paper according to claim 5. A paper formed by internally adding the fluorescent whitening enhancer according to any one of claims 1 to 4.