WO2006033321A1

WO2006033321A1 - Fluorescent whitening potentiator

Info

Publication number: WO2006033321A1
Application number: PCT/JP2005/017278
Authority: WO
Inventors: Akira Kodani; Hirofumi Ohi
Original assignee: San Nopco Ltd.
Priority date: 2004-09-22
Filing date: 2005-09-20
Publication date: 2006-03-30
Also published as: JP4787926B2; JPWO2006033321A1

Abstract

A fluorescent whitening potentiator which can remarkably enhance fluorescent brightness and whiteness when used together with a fluorescent brightening agent. Namely, a fluorescent whitening potentiator which is to be used together with a fluorescent brightening agent and contains as the essential component a polyoxyalkylene compound represented by the general formula (1): {B-(OA)n-O-}t Q (1) wherein Q is an organic group of 1 to 90 carbon atoms (particularly preferably, methyl, propenyl, propane-1,2,3-triyl, hexane -1,2,3,4,5,6-hexayl, or a residue derived from a polyglycerol having a polycondensation degree (m) of 3 to 10 by the removal of (m+2) hydroxyl groups); OA is oxyalkylene of 2 to 4 carbon atoms (preferably, oxyethylene or oxypropylene); B is alkyl of 1 to 3 carbon atoms, alkenyl, or hydrogen; t is an integer of 1 to 32; n is an integer of 0 to 500; and (n × t) is an integer of 1 to 9600.

Description

Fluorescent whitening enhancer

Technical field

[0001] The present invention relates to a fluorescent whitening enhancer. More specifically, the present invention relates to a fluorescent whitening enhancer that is used in combination with a fluorescent whitening agent.

Background art

[0002] In order to improve the whiteness of coated paper and other papers, for example, in the case of coated paper, together with a fluorescent brightening agent, polybutyl alcohol or carboxymethylcellulose as an auxiliary binder for coating paper Are known to be used (Patent Document 1). Also, together with the fluorescent brightening agent, ethylene glycol, propylene glycol or the like (Patent Document 2) is used as a solvent, and as the fluorescent brightening enhancer, a nonionic polysaccharide derivative (hydroxyethinoresenorelose, hydroxypropylene) is used. Noresenorelose, methinoresenorelose, methinoreoxy, chelinoresenorelose, methinorehydroxypropenoresenorelose, ethinorehydroxyethinorenorose, hydroxyethinoremethinoresenorelose, hydroxypropinoremethenolesenorose, Hydroxy shetilder, hydroxypropyl guay, hydroxyethyl starch and hydroxypropyl starch, etc.) (Patent Document 3), polyacrylamide (Patent Document 4), etc. are known to be used.

[0003] Patent Document 1: Japanese Patent Application Laid-Open No. 61-174269 (corresponding US Patent: No. 4717502)

Patent Document 2: Japanese Patent Laid-Open No. 6-322697 (corresponding US Patent: No. 5622749) Patent Document 3: Special Table 2002-543306 (Compatible PCT Application: WO00Z66834 Nonfret)

Patent Document 4: Japanese Patent Laid-Open No. 2001-81692

Disclosure of the invention

Problems to be solved by the invention

[0004] With conventional auxiliary binders, solvents, and fluorescent whitening enhancers, high whitening and whiteness can be obtained even if the amount of fluorescent whitening agent, fluorescent whitening enhancer, etc. is increased. There is a problem that it is difficult. For this reason, the object of the present invention is to use a fluorescent whitening agent together with An object of the present invention is to provide a fluorescent whitening enhancer capable of remarkably improving light whiteness and whiteness.

Means for solving the problem

[0005] The present inventor has reached the present invention as a result of intensive studies to solve the above problems. The feature of the fluorescent whitening enhancer of the present invention is the fluorescent whitening enhancer used together with the fluorescent whitening agent, which comprises the polyoxyalkylene compound represented by the general formula (1) as an essential component. The point is the gist.

(General formula)

{B- (OA) n-0-} t Q (1)

However, in the general formula (1), Q is an organic group having 1 to 90 carbon atoms, OA is an oxyalkylene group having 2 to 4 carbon atoms, B is an alkyl group having 1 to 3 carbon atoms, an alkyl group, or hydrogen. Atom, t is an integer of 1 to 32, n is an integer of 0 to 500, and (nX t) is an integer of 1 to 9600.

The invention's effect

[0006] When the fluorescent whitening enhancer of the present invention is used together with a fluorescent brightening agent, the fluorescent whiteness and whiteness can be remarkably improved. In addition, there is almost no change in paint viscosity when used in paints for coated paper and paints for inkjet paper. Therefore, it is suitably used for coated paper (pigment coated paper or tara coat paper), ink jet paper, and the like.

BEST MODE FOR CARRYING OUT THE INVENTION

[0007] General formula (1) will be described.

As the organic group (Q) having 1 to 90 carbon atoms, 1 to 90 valent aliphatic hydrocarbons and the like are used, such as methyl, ethyl, propyl, butyl, pentyl, ethylene, propenyl (1 or 2-propyl). Lopenyl), butylene, pentylene, propane 1, 2, 3 tolyl, butane 1, 2, 3, 4—tetrayl, pentane— 1, 2, 3, 4, 5 pentile, hexane—1, 2, 3, 4, 5, 6-hexayl, a residue obtained by removing three hydroxyl groups from trimethylolpropane, a pentaerythritol force removing a residue of 4 hydroxyl groups, a sorbitan force removing a residue of 4 hydroxyl groups, Dipentaerythritol removed 6 hydroxyl groups, 8 hydroxyl groups removed from saccharose, and (m + 2) residues from polyglycerol with a degree of condensation (m) of 2-30. Residues other than hydroxyl groups are included. [0008] Of these, from the viewpoints of fluorescent whiteness and whiteness improvement, methyl, ethyl, propyl, butyl, ethylene, propenyl, propane 1, 2, 3 triyl, butane 1, 2, 3, 4—Tetrayl, pentane— 1, 2, 3, 4, 5 Pentile, hexane— 1, 2, 3, 4, 5, 6 —Hexayl and trimethylolpropane power also removes the hydroxyl group and the residue and degree of condensation ( m) (m + 2) hydroxyl groups are removed from polyglycerin with a force of ~ 30, preferably a residue, more preferably methyl, ethyl, propyl, ethylene, probe, propane 1, 2, 3—Triyl, butane— 1, 2, 3, 4—tetrayl, pentane— 1, 2, 3, 4, 5 Pentile, hexane— 1, 2, 3, 4, 5, 6 Hexayl and degree of condensation (m ) Is a residue obtained by removing (m + 2) hydroxyl groups from polyglycerin having 3-20, particularly preferably methyl, probe, or propan-1, 2 , 3 卜 liyl, hexane— 1, 2, 3, 4, 5, 6 Hexayl and polyglycerin with a degree of condensation (m) of 3 to 10 (m + 2) hydroxyl groups are removed! It is.

[0009] The oxyalkylene group (OA) having 2 to 4 carbon atoms includes oxyethylene, oxypropylene and oxybutylene. Of these, oxyethylene and oxypropylene are preferred, and oxyshethylene is more preferred from the viewpoint of fluorescent whitening and whiteness improvement.

[0010] The plurality of OA may be the same or different, and t (OA) n may be the same or different.

When OA contains multiple types of oxyalkylene groups, there is no limitation on the bonding order (block, random and combinations thereof) and content of these oxyalkylene groups. It is preferable to include a combination with a random state. In this case, the content (weight%) of oxyethylene, which preferably contains oxyethylene, is preferably 20 to 99, more preferably 25 to 99, based on the total weight of the oxyalkylene group. Particularly preferred is 30 to 99, most preferred 35 to 99.

(OA) n is preferably a mixture with oxyethylene and oxypropylene! /.

[0011] Among the alkyl group having 1 to 3 carbon atoms, the alkyl group or the hydrogen atom (B), the alkyl group having 1 to 3 carbon atoms includes methyl, ethyl, propyl and the like. The alkenyl group includes bur, 1 probe, and 2 probe.

Of these, from the viewpoints of fluorescent whiteness and whiteness improvement, hydrogen atoms, methyl, ethyl More preferred are hydrogen, methyl, ethyl and vinyl, particularly preferred are hydrogen and methyl, and most preferred is a hydrogen atom. When a plurality of B are contained, they may be the same or different.

[0012] t is an integer of 1 to 32, preferably an integer of 1 to 27, more preferably an integer of 1 to 22, particularly preferably an integer of 1 to 17, and most preferably an integer of 1 to 12. . Within this range, the fluorescent whitening and whiteness improving effects are further improved.

[0013] n is an integer of 0 to 500, preferably an integer of 1 to 460, more preferably an integer of 1 to 350, particularly preferably an integer of 1 to 300, and most preferably an integer of 1 to 250. . Within this range, the fluorescent whitening and whiteness improving effects are further improved.

When there are a plurality of n (when t is 2 or more), the plurality of n may be the same value or different values.

[0014] (n X t) is 1 to 9600, preferably 2 to 9500, more preferably 2 to 9400, and particularly preferably 2 to 9300.

(N X t) is preferably 1 to 460, more preferably 10 to 350, particularly preferably 20 to 300, and most preferably 30 to 250 when t = l. Further, when t = 2, 2 to 600 force S is preferable, more preferably 2 to 500, particularly preferably 2 to 400, and most preferably 2 to 300. Further, when t = 3, the force is preferably 3 to 900, more preferably 3 to 890, particularly preferably 3 to 880, and most preferably 3 to 870. Further, when t = 4 to 32, 4 to (460 X t) is preferable, more preferably 4 to (350 X t), particularly preferably 4 to (300 X t), and most preferably 4 to ( 250 X t).

[0015] Among the polyoxyalkylene compounds represented by the general formula (1), preferable examples include compounds represented by the following chemical formulas. H is a hydrogen atom, po is an oxypropylene group, eo is an oxyethylene group, Q ¹ is a methyl group, Q ² is an ethyl group, Q ³ is a 1, 2, 3 tolyl group, Q ⁴ is butane 1, 2, 3, 4—tetrayl group, Q ⁵ is pentane—1, 2, 3, 4, 5 pentile group, Q ⁶ is hexane—1, 2, 3, 4, 5 , 6 hexyl group, Q ⁷ is a 1-probe group, Q ⁸ is a residue obtained by removing 12 hydroxyl groups from decaglycerin, and Q ⁹ is a group obtained by removing 6 hydroxyl groups from tetraglycerin. Residues.

[0016] (Chemical formula) H- (eo)--Q ¹ (1)

40

H- (eo)-Q ¹ (2)

250

CH-(eo) Q (3)

3 40

H- (po)-(eo) Q ¹ (4)

2 40

H- (eo)--Q ² (5)

70

H- (eo)-"(po) Q ² (6)

40 1

{H- (eo)--} Q ³ (7)

40 3

{H- (eo) —} Q ^: (8)

270 3

{H- (eo)--} Q ⁴ (9)

40 4

{H- (eo)--} Q ⁵ (10)

40 5

{H- (eo) ―} Q ⁶ (11)

4 6

{H- (eo)--} Q ⁶ (12)

40 6

{H- (eo) —} Q * (13)

120 6

H- (eo)--Q ⁷ (14)

30

CH-(eo) -Q ⁷ (15)

3 30

{H- (eo) ―} Q ⁸ (16)

4 12

{H- (eo)--} Q ⁹ (17)

10 6

{H- (eo)--} Q ⁹ (18)

40 6

[0017] Of these, equations (1), (2), (4), (5), (6), (7), (8), (9), (10), (11), (12 ),

The polyoxyalkylene compound represented by (13), (14), (16), (17) or (18) is preferred, more preferably the formula (1), (2), (7), It is a polyoxyalkylene compound represented by (8), (9), (10), (11), (12), (13), (14), (16) or (17).

[0018] The polyoxyalkylene compound represented by the general formula (1) includes a chemical reaction of an alcohol (al) having 1 to 90 carbon atoms and an alkylene oxide (a2) having 2 to 4 carbon atoms. Those having a structure that can be manufactured by the method are included. That is, a polyoxyalkylene compound having a structure that can be produced by such a chemical reaction may cause a distribution in the oxyalkylene group. In this case, strictly speaking, a plurality of types of polyoxyalkylene compounds are used. This mixture includes a polyoxyalkylene compound represented by the general formula (1). It is. Even in this case, the manufacturing method is not limited.

[0019] The amount (mole part) of the alkylene oxide (a2) used is preferably 1 to 9600 force S relative to an al = 3 monolole (al) 1 monolole having 1 to 90 carbon atoms, more preferably ί 2-9500, particularly preferably 2-9400, most preferably 2-9300. Within this range, the fluorescent whitening and whiteness improving effects are further improved.

[0020] As the alcohol (al) having 1 to 90 carbon atoms, those constituting the reaction residue (Q) in the general formula (1) (1 to 90-valent alcohol, etc.) are used, and methanol, ethanol, Propanol, butanol, pentanol, ethylene glycol, 1- or 2-propyl alcohol, butylene glycol, pentylene glycol, glycerin, butane 1, 2, 3, 4-tetraol, pentane 1, 2, 3 , 4, 5 Pentaol, sorbitol, trimethylolpropane, pentaerythritol, sorbitan, dipentaerythritol, saccharose and polyglycerin having a degree of condensation (m) of 2 to 30 are included. Of these, methanol, ethanol, propanol, butanol, ethylene glycol, 1 or 2-propal alcohol, glycerin, butane—1, 2, 3, 4-tetraol, pentane—1, 2, 3, 4 , 5 Pentaol, sorbitol, trimethylolpropane and polyglycerin having a degree of condensation (m) of 2 to 30 are preferred, more preferably methanol, ethanol, propanol, ethylene glycol, 1 or 2-propenyl alcohol, Glycerin, butane-1, 2, 3, 4-tetraol, pentane 1, 2, 3, 4, 5 pentaol, sorbitol and polyglycerin having a degree of condensation (m) of 3 to 20, particularly preferably methanol, 1- or 2 Propylene alcohol, glycerin, sorbitol and polyglycerin having a condensation degree (m) of 3-10.

Polyglycerin can be synthesized by a known method (US Pat. No. 3637774) in which glycerin is subjected to dehydration condensation under a small amount of alkaline catalyst.

[0021] Examples of polyglycerin include diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, heptaglycerin, otatagglycerin, nonaglycerin, decaglycerin, pentadecaglycerin, eicosaglycerin, and triacontagglycerin. Etc. Of these, diglycerin, triglycerin, tetraglycerin, pentaglycerin , Hexaglycerin, heptaglycerin, otatag glycerin, nonaglycerin, decaglycerin, pentadecaglycerin and eicosaglycerin are preferred, more preferred are diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, heptaglycerin. In particular, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, heptaglycerin, otatagglycerin, nonaglycerin and decaglycerin. is there.

Polyglycerin may be used as it is as a mixture having a different degree of condensation, or it may be refined to have a narrow degree of condensation, and it may be used as a force (even if it is dipentaerythritol).

[0022] Examples of the alkylene oxide (a2) having 2 to 4 carbon atoms include ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO), and mixtures thereof. Of these, EO, PO, and a mixture of EO and PO are preferred from the viewpoint of fluorescent whiteness and whiteness improvement, and more preferred are EO and a mixture of EO and PO, most preferred. Preferably EO.

When multiple types of alkylene oxide are used, the order of reaction (block, random, and combinations thereof) and the ratio of use are preferably limited, but preferably include block or a combination of block and random . In this case, the proportion of it is good Mashigu EO containing EO (weight ^_0/0), based on the total weight of alkylene O dimethylsulfoxide, 20-99 force transducer preferred, more preferably 25 to 99 Particularly preferred is 30 to 99, most preferred 35 to 99.

[0023] A reaction catalyst can be used for the reaction of the alcohol (al) having 1 to 90 carbon atoms with the alkylene oxide (a2). Note that when an amide described below is used as a reaction solvent, it is not necessary to use a reaction catalyst.

As the reaction catalyst, a conventionally used alkylene oxide addition reaction catalyst or the like can be used. Alkali metal or alkaline earth metal hydroxides (hydroxy potassium hydroxide, rubidium hydroxide and hydroxide hydroxide) can be used. Cesium, etc.), alkali metal alcoholates (potassium methylate and cesium ethylate, etc.), alkali metal or alkaline earth metal carbonates (such as potassium carbonate, cesium carbonate, and barium carbonate), carbon number 3-24 Tertiary amines such as trimethylamine, trioctylamine, triethylenediamine and tetramethylethylenediamine, and Lewis acids (such as salt 匕 stannic and boron trifluoride) are used. Of these, alkali metal hydroxides and tertiary amine compounds are preferred, and potassium hydroxide, cesium hydroxide and trimethylamine are more preferred.

[0024] When a reaction catalyst is used, the amount used (% by weight) is preferably 0.05 to 2 force S, more preferably 0.1 to 1 based on the total weight of (al) and (a2). Particularly preferred is 0.2 to 0.6.

When using a reaction catalyst, it is preferable to remove the reaction catalyst from the reaction product. For example, an alkali adsorbent such as a synthetic aluminosilicate (eg, trade name: Kiyo Ward 700, Kyowa Chemical Industry Co., Ltd.) ) Manufactured by Komatsu (Japanese Patent Laid-Open No. 53-123499), washing with water such as xylene or toluene (Japanese Patent Publication No. 49-14359), ion exchange resin And a method of filtering a carbonate produced by neutralizing an alkaline catalyst with carbon dioxide (Japanese Patent Publication No. 52-33000) and the like.

As the end point of removal of the reaction catalyst, it is preferable that the CPR (Controlled Polymerization Rate) value described in JIS K1557- 1970 is 20 or less, more preferably 10 or less, particularly preferably 5 or less, and most preferably 2 It is as follows.

[0025] As the reaction vessel, it is preferable to use a pressure-resistant reaction vessel capable of heating, cooling and stirring. The reaction atmosphere is preferably an atmosphere of an inert gas (such as argon, nitrogen and carbon dioxide) in which the inside of the reaction apparatus is vacuumed or dried before introducing the alkylene oxide (a2) into the reaction system. The reaction temperature (° C) is preferably 80 to 150, more preferably 90 to 130. The reaction pressure (gauge pressure: MPa) is preferably 0.8 or less, more preferably 0.5 or less.

The end point of the reaction can be confirmed by the following method. In other words, if the reaction temperature is kept constant for 15 minutes and the decrease in reaction pressure (gauge pressure) falls below 0.0OOlMPa, the reaction end point is reached.

[0026] In the reaction step of the alcohol (al) having 1 to 90 carbon atoms and the alkylene oxide (a2), a reaction solvent may be used as necessary. The reaction solvent includes (1) no active hydrogen, (2) reaction product of alcohol (al) with 1 to 90 carbon atoms, alkylene oxide (a2), (al) and (a2). Any material that dissolves the composition {polyoxyalkylene compound} can be used.

As such a reaction solvent, an alkylamide having 3 to 8 carbon atoms and a bicyclic amide having 5 to 7 carbon atoms can be used. Examples of alkyl amides include N, N dimethylformamide (DMF), N, N dimethylacetamide, N, N dimethylacetamide, N-methyl N propylacetamide, and 2-dimethylaminoacetaldehyde dimethyl acetal. Can be mentioned. Examples of the heterocyclic amide include N-methylpyrrolidone, N-methyl-ε-caplatatatam, and Ν, Ν dimethyl bilolcarboxylic acid amide.

Of these, alkylamides and メチル methylpyrrolidone are preferred, more preferably DMF, N, N dimethylacetamide and N-methylpyrrolidone, particularly preferably DMF and N-methylpyrrolidone, most preferably DMF. .

When a reaction solvent is used, the amount used (% by weight) is preferably 20 to 200, more preferably 40 to 180, and most preferably 60 to 60, based on the total weight of (al) and (a2). 150.

[0027] When a reaction solvent is used, it is preferable to remove the reaction solvent after the reaction.

As a method for removing the reaction solvent, vacuum distillation, adsorption removal and the like can be applied, and it is preferable to further remove by adsorption after vacuum distillation.

Conditions for distilling off under reduced pressure include conditions of distillation at 100 to 150 ° C. under reduced pressure of 26.6 to 0.7 MPa.

Further, when removing by adsorption, a treatment method using an alkali adsorbent such as synthetic aluminosilicate {for example, trade name: Kiyo Ward 700, manufactured by Kyowa Chemical Industry Co., Ltd.} can be applied. For example, when using Kiyo one word 700, the addition amount of the alkali sorbent (wt ^_0/0), 1 to 10 about 0.1 based on the weight of the polyoxyalkylene compound, the treatment temperature is sixty to twelve 0 ° C approximately The processing time is about 0.5 to 5 hours. Subsequently, the residual amount of the reaction solvent can be further reduced by removing the alkali adsorbent by filtering with filter paper or filter cloth.

[0028] Further, the fluorescent whitening enhancer of the present invention includes 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-foaming agent. Odorants, fragrances, dyes, ultraviolet absorbers, antioxidants, fillers, slime control agents, Z or pitch control agents, etc. Known additive agents used for paper production and the like can be used. When using additive chemicals, the amount used (% by weight) is preferably 0.01 to 50, more preferably 0.05 to 40, based on the weight of the polyoxyalkylene compound. Particularly preferred is 0.08 to 30, most preferably 0.1 to 20.

[0029] The fluorescent whitening enhancer of the present invention is used together with the fluorescent brightening agent, 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, and diaminostilbene, coumarin, pyrazoline, imidazole, triazole, Oxazole-based or naphthalimide-based optical brighteners, etc. {The chemical dictionary of paper and paper, page 65, Tech Times Co., Ltd., published on February 25, 1991} are widely used in the market. Preferred diaminostilbene fluorescent brightener

[0030] The use amount (% by weight) of the fluorescent whitening enhancer of the present invention is preferably 20 to 2000 S based on the weight of the optical brightener, more preferably 21 to 1900, and particularly preferably 22 to ί. -1800, most preferably 23-1700.

[0031] The fluorescent whitening enhancer of the present invention is blended together with the fluorescent whitening agent in a paper coating mainly composed of pigments and soot or fillers and binders, and paper containing no pigments and soot or fillers. It is blended into paints for coating, coated in the coating process, and finished into coated paper (pigment paper and tarry coat paper) and inkjet 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 the papermaking (making) process to finish various papers.

[0032] Examples of pigments and / or fillers include inorganic pigments such as clay, light calcium carbonate, heavy calcium carbonate, titanium oxide, satin white, barium sulfate, talc, zinc oxide, gypsum, silica, synthetic silica, and ferrite. Organic pigments such as polystyrene pigments are used, either alone or in combination.

Examples of binders include styrene butadiene latex, carboxyl-modified styrene butadiene latex, acrylic resin emulsion, acetate acetate resin emulsion, vinyl chloride emulsion, acrylic styrene resin emulsion, and silicone resin emulsion. Synthetic binders such as urethane resin emulsion, epoxy resin emulsion, fluorine resin emulsion, ABS latex, NBR latex, CR latex, and polybulu alcohol.

In addition, for paper paints, dispersants, lubricants, antifoaming agents, water retention agents, thickeners, water resistance agents, wetting agents, antiseptic / antifungal agents, deodorants, fragrances, dyes, UV absorbers, antioxidants and Z 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.

[0033] When the fluorescent whitening enhancer of the present invention is added to a coating paper coating for pigment paper, the amount (% by weight) of the fluorescent whitening enhancing agent used is the pigment in the paper coating paint and / or Based on the weight of the filler, it is preferably 0.01 to 10 force, more preferably 0.05 to 9, particularly preferably 0.08 to 8, and most preferably 0.1 to 7.

Further, in this case, the amount (% by weight) of the optical brightener used is preferably 0.01 to 5 and more preferably 0.05 based on the weight of the pigment and / or filler in the coating material for coated paper. −4.5, particularly preferably 0.08 to 4, most preferably 0.1 to 3.5.

[0034] 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 based on the weight of the coated paper paint. On the basis of 0.01 to: L0 is more preferred, more preferably 0.05 to 9, particularly preferably 0.08 to 8, most preferably 0.1 to 7.

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 agent is based on the weight of the coated paper paint. 01 to 5 are preferred, more preferably 0.05 to 4.5, particularly preferably 0.08 to 4, and most preferably 0.1 to 3.5.

[0035] When the fluorescent whitening enhancer of the present invention is added to an ink jet paper paint for ink jet paper, the amount used (% by weight) of the fluorescent whitening enhancer is based on the weight of the coated paper paint. 0.01-20 is preferred, more preferably 0.05-19, particularly preferably 0.08-18, and most preferably 0.1-17.

The fluorescent whitening enhancer of the present invention is added to inkjet paper paints for inkjet paper In this case, the use amount (% by weight) of the optical brightener is preferably from 0 to 1 to 5, more preferably from 0.05 to 4.5, particularly preferably based on the weight of the coating paper coating material. Is 0.08-4, most preferably 0.1-3.5.

[0036] When the fluorescent whitening enhancer of the present invention is internally added to the pulp slurry, the use amount (wt%) of the fluorescent brightening enhancer is preferably 0.01 to 10 based on the weight of the pulp. More preferably, it is 0.05 to 9, particularly preferably 0.08 to 8, and most preferably 0.1 to 7.

When the fluorescent whitening enhancer of the present invention is internally added to the pulp slurry, the used amount (% by weight) of the fluorescent brightening agent is 0.01 to 5 or more, more preferably, 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.

[0037] 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, curtain flow coater, spray coater, size press or the like. After coating, it is dried and, if necessary, calendering finish such as super calendering or soft-up calendering is performed to produce coated paper. The coating temperature is usually 10-60 ° C, the drying temperature is usually 70-150 ° C, and the calendering temperature is usually 30-160 ° C.

[0038] The ink-jet paper coating material is applied to paper by a known method using an air knife coater, blade coater, Rohno coater, rod coater, curtain flow coater, spray coater, size press or the like. After coating, it is dried, and calendering finish such as calendering or soft-up calendering is performed as necessary to produce inkjet paper. The coating temperature is usually 10-50 ° C, the drying temperature is usually 70-150 ° C, and the calendering finish temperature is usually 30-150 ° C.

[0039] The pulp slurry internally added with the fluorescent whitening enhancer of the present invention used together with the optical brightener is made (paper) by a known method using a long net paper machine or a round net paper machine, and then dried. Paper is produced.

Example 1

[0040] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. Unless otherwise specified, “part” means “part by weight” and “%” means “% by weight”.

[0041] <Example 1> Operation of heating, stirring, cooling, dripping, pressurizing and depressurizing using nitrogen gas to increase pressure to 0.4MPa with gauge pressure and discharging to 0.02MPa (replacement with pressurized nitrogen) ) Was repeated three times. Thereafter, 32 parts (1 mol part) of methanol {special reagent grade, manufactured by Wako Pure Chemical Industries, Ltd., the same applies below} and 2 parts of potassium hydroxide hydroxide were added. Then, the temperature was raised to 100 ° C while stirring, and then 1760 parts (40 mole parts) of EO was added dropwise at the same temperature over 12 hours, followed by stirring for 1 hour at the same temperature to react with the remaining EO. It was. Then, after adding 20 parts of ion-exchanged water at 90 ° C, 100 parts of Kiyo Ward 700 (manufactured by Kyowa Chemical Industry Co., Ltd., the same shall apply hereinafter) was added and stirred at the same temperature for 1 hour. Next, filter using No. 2 filter paper (manufactured by Toyo Filter Paper Co., Ltd., the same applies below) at the same temperature to remove Kiyoword 700, and further 2.7 to 0. IMP a under reduced pressure at 120 ° C. After dehydration for 1 hour, 40 mol of ZEO methanol was obtained. This adduct was directly used as the fluorescent whitening enhancer (A1) of the present invention.

A reaction vessel similar to that in Example 1 was purged with nitrogen in the same manner as in Example 1. 32 parts (1 mole part) of methanol and 22 parts of potassium hydroxide were added. Then, the temperature was raised to 100 ° C with stirring, and then 1000 parts of EOl (250 mole parts) was added dropwise at the same temperature over 36 hours, followed by stirring at the same temperature for 1 hour to react with the remaining EO. I let you. Thereafter, Kiyo Ward treatment was carried out in the same manner as in Example 1 to obtain a methanol ZEO 250 mol adduct. This adduct was directly used as the fluorescent whitening enhancer (A2) of the present invention.

In the same reaction vessel as in Example 1, glycerin {special reagent grade, manufactured by Wako Pure Chemical Industries, Ltd., the same shall apply hereinafter} Nitrogen was replaced in the same manner as in Example 1. Then, the temperature was raised to 100 ° C while stirring, and then 1760 parts (40 mole parts) of EO was dropped over 12 hours at the same temperature, and then the remaining EO was reacted by continuing stirring at the same temperature for 1 hour. . Thereafter, Kiyo Ward treatment was performed in the same manner as in Example 1 to obtain a 40 mol glycerin Z EO adduct. This adduct was directly used as the fluorescent whitening enhancer (A3) of the present invention.

[0044] Example 4>

In a reaction vessel similar to Example 1, 92 parts (1 mole part) of glycerin and 24.5 parts of potassium hydroxide hydroxide were added. After the addition, nitrogen substitution was performed in the same manner as in Example 1. Then, the temperature was raised to 100 ° C while stirring, and then 4840 parts (110 mole parts) of EO was added dropwise at the same temperature over 36 hours, followed by stirring for 1 hour at the same temperature to react with the remaining EO. . Thereafter, Kiyo Ward treatment was carried out in the same manner as in Example 1 to obtain a 110 mol glycerin ZEO adduct. This adduct was directly used as the fluorescent whitening enhancer (A4) of the present invention.

Into a reaction vessel similar to Example 1, sorbitol {reagent grade 1, manufactured by Wako Pure Chemical Industries, Ltd., the same shall apply hereinafter} 182 parts (1 mol part) and potassium hydroxide 3 parts were added, and then Example 1 Nitrogen substitution was performed in the same manner as described above. Then, the temperature was raised to 100 ° C while stirring, and then 1056 parts (24 mole parts) of EO was added dropwise at the same temperature over 6 hours, and then stirring was continued for 1 hour at the same temperature to react with the remaining EO. . Thereafter, Kiyo Ward treatment was carried out in the same manner as in Example 1 to obtain an adsorbate of sorbitol ZE024 mol. This adduct was directly used as the fluorescent whitening enhancer (A5) of the present invention.

Into a reaction vessel similar to that in Example 1, 182 parts (1 mole part) of sorbitol and 13 parts of potassium hydroxide hydroxide were added, and then purged with nitrogen in the same manner as in Example 1. Then, the temperature was raised to 100 ° C while stirring, and then 4400 parts (100 mole parts) of EO was added dropwise at the same temperature over 36 hours, and then stirring was continued for 1 hour at the same temperature to remove the remaining EO. Reacted. Thereafter, the Kiyo Ward treatment was performed in the same manner as in Example 1 to obtain a 100 mol sorbitol ZEO adduct. This adduct was directly used as the fluorescent whitening enhancer (A6) of the present invention.

Into the same reaction vessel as in Example 1, 58 parts (1 mole part) of allylic alcohol {special reagent grade, manufactured by Wako Pure Chemical Industries, Ltd.} and 7 parts of potassium hydroxide hydroxide were added up to 70 ° C. The temperature was raised, and nitrogen substitution was carried out in the same manner as in Example 1. Then, the temperature was raised to 100 ° C while stirring, and then EO1320 parts (30 mole parts) was added dropwise at the same temperature over 12 hours, and then stirring was continued for 1 hour at the same temperature to react with the remaining EO. . Thereafter, Kiyo Ward treatment was carried out in the same manner as in Example 1 to obtain a force product with 30 mol of aryl alcohol ZEO. This adhesive cake was directly used as the fluorescent whitening enhancer (A7) of the present invention. <Example 8>

In the same reaction vessel as in Example 1, polyglycerin mixture {polyglycerin # 750 manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., average value of degree of condensation (m): 10} 76 parts (0.1 mole part) and potassium hydroxide 6 After dehydrating at 120 ° C under reduced pressure of IM. IMPa for 1 hour, the temperature was raised to 70 ° C and nitrogen substitution was performed in the same manner as in Example 1. Then, the temperature was raised to 100 ° C while stirring, and then E02112 parts (48 mole parts) were added dropwise at the same temperature over 12 hours, followed by stirring at the same temperature for 1 hour to react with the remaining EO. It was. Thereafter, Kiyo Ward treatment was carried out in the same manner as in Example 1 to obtain a polyglycerin ZE048 mol adduct. This adduct was directly used as the fluorescent whitening enhancer (A8) of the present invention.

Polyglycerin mixture {Polyglycerin # 310, Sakamoto Yakuhin Kogyo Co., Ltd., average degree of condensation (m): 4} 31 parts (0.1 mole part), potassium hydroxide 7 After dehydration at 120 ° C under reduced pressure of IM. Pa for 1 hour, the temperature was raised to 70 ° C and the atmosphere was replaced with nitrogen in the same manner as in Example 1. Then, the temperature was raised to 100 ° C while stirring, and then 2640 parts (60 mole parts) of EO was added dropwise over 12 hours at the same temperature, and then the remaining EO was reacted by continuing stirring at the same temperature for 1 hour. It was. Thereafter, Kiyo Ward treatment was carried out in the same manner as in Example 1 to obtain a polyglycerin / EO 60 mol adduct. This adduct was directly used as the fluorescent whitening enhancer (A9) of the present invention.

[0050] <Comparative Example 1>

A 10% aqueous solution of polyvinyl alcohol {PVA-105 manufactured by Kuraray Co., Ltd., number average molecular weight 22000, saponification degree 98-99 mol%} was prepared and used as a fluorescent whitening enhancer (B1) for comparison.

[0051] <Comparative Example 2>

Carboxymethylcellulose {NOVIANT FINFIX5, 4% aqueous solution viscosity (25 ° C) 40mPa's} 10% aqueous solution was prepared as a comparative fluorescent whitening enhancer (B2).

[0052] <Comparative Example 3>

Polyethylene glycol {PEG-400 manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight 400, hydroxyl value 281} was used as a fluorescent whitening enhancer (B3) for comparison.

<Comparative Example 4> Hydroxyethyl cellulose {NACUSOL250LR, manufactured by HERCULES INC., 10% aqueous solution with 5% aqueous solution viscosity (25 ° C) 140mPa's} was prepared as a comparative fluorescent whitening enhancer (B4).

[0054] <Comparative Example 5>

Into a dropping apparatus, reflux condenser, nitrogen inlet tube, stirring apparatus and reaction apparatus equipped with a thermometer, were charged 5699.9 parts of water, 392.2 parts of 50% aqueous acrylamide and 1.8 parts of methacrylic acid. Nitrogen substitution was performed, and the temperature was raised to 50 to 55 ° C. Next, 6.3 parts of 5% ammonium persulfate aqueous 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 the reaction was further continued at 85 ° C for 2 hours. Thereafter, 20.8 parts of water was added to obtain a polyacrylamide aqueous solution having a solid concentration of 21.1%. This aqueous polymer solution was directly used as a fluorescent whitening enhancer (B5) for comparison. The polymer obtained had a weight average molecular weight of 200,000 and MwZMn of 3.9.

[0055] <Comparative Example 6>

Lauryl alcohol {Reagent grade 1, manufactured by Wako Pure Chemical Industries, Ltd.} 186 parts (1 mole part) and potassium hydroxide 7 parts were charged into the same reaction vessel as in Example 1, and then the same as in Example 1. Nitrogen substitution was performed by the method described above. Then, the temperature was raised to 100 ° C while stirring, and then 1320 parts (30 mole parts) of EO was added dropwise at the same temperature over 12 hours, and then stirring was continued for 1 hour at the same temperature to react with the remaining EO. . Thereafter, Kiyo Ward treatment was carried out in the same manner as in Example 1 to obtain a lauryl alcohol ZEO 30 mol adduct. This adduct was directly used as a fluorescent whitening enhancer (B6) for comparison.

[0056] Using the fluorescent whitening enhancers (A1 to A9, B1 to B6) of Examples 1 to 9 and Comparative Examples 1 to 6, pigment coated paper coating paints (1 and 2), for tarry coat paper Coating paints and inkjet paper paints were prepared and coated on fine paper to produce pigment coated paper (1 and 2), tarier coated paper and inkjet paper, respectively.

Further, by using the above-described fluorescent whitening enhancer and kraft pulp, paper was made to produce an internally added paper having a basis weight of 63 g / m ² .

Pigment coated paper coating paint (1 and 2), Tariya coated paper coating paint, Inkjet paper paint, Pigment coated paper (1 and 2), Clear coat paper, Inkjet paper and internal additives The performance of the paper was evaluated by the following method, and these results are shown in Tables 1-5.

[0057] (1. 1) Coating paint for pigment coated paper (1)

Second grade clay (HT clay manufactured by ENGELHARD MINERAL & CHEMICALS) 50 parts, calcium carbonate 50 parts FMT-90 manufactured by FMT Co., Ltd. Part, 0.2 parts of sodium hydroxide, 10 parts of SBR latex (Diesal Co., Ltd. Hen SR0629), thickener (manufactured by Sannopco, SN Thickener 920), 0.4 parts, fluorescent whitening agent (Nipponization) Yaku Colors Co., Ltd., Kayaphor NV liquid] and 0.5 part of fluorescent whitening enhancer were uniformly mixed with stirring to prepare pH 9 pigment coated paper coating paint (1).

[0058] (1. 2) Coating paint for pigment coated paper (2)

Second grade clay (HT clay manufactured by ENGELHARD MINERAL & CHEMICALS) 50 parts, calcium carbonate 50 parts FMT-90 manufactured by FMT Co., Ltd. Part, 0.2 parts of sodium hydroxide, SBR latex (Diesal Co., Ltd. ¾ [SR0629], 10 parts, oxidized starch (manufactured by Nippon Food Chemical Co., Ltd., MS-3600), 5 parts, fluorescent whitening agent (Japan) Kayaphor PAS liquid], 0.5 parts made by Gyaku Colors Co., Ltd., and 0.5 part of fluorescent whitening enhancer were mixed with stirring to create a pH 9 pigment coated paper coating paint (2) did.

[0059] (2) Clear coated paper coating

1 part of fluorescent whitening agent [Kayaphor NV liquid] (manufactured by Nippon Kayaku Colors Co., Ltd.) and 1 part of fluorescent whitening enhancer were diluted with 98 parts of water to prepare 100 parts of clear coat paper coating paint.

[0060] (3) Inkjet paper paint

Synthetic silica (manufactured by Tokuyama Co., Ltd., Fine Seal X-38) 100 parts, acetic acid 0.2 parts, wetting agent (manufactured by San Nopco, SN wet 366) 1.0 part, polybulu alcohol [Kuraray Co., Ltd. ), PVA-117] 4C ^, dye fixing agent [Senriki Co., Ltd., Papiogen P-105] 10 parts, fluorescent brightener [Nippon Kayaku Co., Ltd., Kayaphor PAS liquid] 1 0 part and fluorescent whitening enhancer 1. 0 part was uniformly stirred and mixed to prepare a pH 7 ink jet paper coating material.

[0061] (4) Pigment coated paper (1 or 2)

Pigment coated paper coating paint or 2) commercial high-quality paper (basis weight 68gZm ² , whiteness 73 5%) was coated with a blade at a coating speed of 20 mZmin so that the coating amount was about 12 gZm ² , and then dried with hot air at 135 ° C. for 20 seconds to obtain a coated paper. The obtained coated paper was subjected to a super calendar process to obtain pigment coated paper (1 or 2). The coating device used was MLC (manufactured by Osugi Co., Ltd.). The super calender processing condition is temperature 40. C, linear pressure 70KgZcm, two passes.

[0062] (5) Clear coated paper

Commercially available coating paint clear coat paper quality paper (basis weight 68GZm ^2, whiteness 73.5%) wire bar at a coated rate 20mZmin on one side of the [RDS Webster Inc., RDS12] was applied, the coated paper Obtained. The obtained coated paper was dried with a drum dryer to obtain each taliacoat paper. The coating device used was MLC (manufactured by Osugi Co., Ltd.). The drying was performed at 80 ° C for 60 seconds.

[0063] (6) Inkjet paper

Inkjet paper paint is blade coated at a coating speed of 20 mZmin so that the coating amount is about 12 gZm ² on one side of high-quality commercial paper (basis weight 68 gZm ² , whiteness 73.5%), then 13 5 ° C. Inkjet paper was obtained by drying with hot air for 20 seconds. The obtained ink jet paper was subjected to a super calendar process to obtain an ink jet paper. The coating device used was MLC [manufactured by Ausugi Co., Ltd.]. The supercalendering conditions were a temperature of 40 ° C, a linear pressure of 40 kg Zcm, and a single paper pass.

[0064] (7) Internal paper

A pulp consisting of 30 parts by weight of softwood bleached kraft pulp (NBKP) and 70 parts of hardwood bleached kraft pulp (LBKP) (dry weight part, the same shall apply hereinafter) is beaten with a refiner, and Canadian Standard Freeness (JIS P8121-1995. 4. Canada Standard Freeness Test Method) was 400ml CSF. This pulp was made into 1% pulp slurry, and 10 parts of light calcium carbonate (TP1 21S manufactured by Okutama Kogyo Co., Ltd.) and diaminostilbene fluorescent whitening agent (100 parts of pulp) in a pulp disintegrator. 0.5 parts of Kayap hor NV liquid (manufactured by Nippon Gyaku Colors Co., Ltd.), 0.5 parts of fluorescent whitening enhancer, and 0.03 parts of a commercial cation yield improver were added. Using a handbrushing device, paper was made according to JIS P8209-1994, and an internal paper having a basis weight of 63 g / m ² was produced. [0065] <Physical properties of pigments for pigment coated paper>

(1) Low shear viscosity (mPa's): Measured using a BM type 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-9900HV (88 OOrpm, 25 ° C) manufactured by SMT Co., Ltd. In addition, it is preferable that the high shear viscosity is low.

[0066] <Physical Properties of Inkjet Paper Coating>

[0067] <Fluorescent whitening>

Pigment coated paper (1 or 2), clear coated paper, inkjet paper, and internal paper are left in a constant temperature and humidity chamber at 25 ° C, 5 01¾ %% humidity for 48 hours, and then in the visible and ultraviolet region. Measure whiteness (W1) (wavelength: 400 to 700 nm measured) with light (using a pulsed xenon lamp), and then whiteness (W2) (wavelength: 400-70 Onm was measured). Next, the difference between the whiteness (W1) and the whiteness (W2) (W1-W2) was defined as the fluorescent whitening degree. The whiteness (%) was measured on the coated surface using PF-10 manufactured by Nippon Denshoku Industries Co., Ltd. according to J IS P8148-1993, characteristic B) (corresponding ISO: ISO2470-1999). did. Further, the higher the value of the fluorescent whitening degree (%), the better.

[0068] [Table 1]

Pigment coated paper paint (1) Pigmented paper (1) Low shear viscosity High shear viscosity White color Fluorescence increased whiteness Wl> W2> <W1-W2> Actual 1 1 390 1 8. 0 80. 5 75. 3 5. 2

2 1400 1 8. 3 80. 6 75 .3 5. 3 Out 3 1 390 1 8. 1 80. 8 75 .4 5. 4

4 1420 1 8. 3 80. 5 75. 3 5. 2 Example 5 1 390 1 8. 0 80. 7 75. 4 5. 3

6 1420 1 8. 3 80. 3 75. 2 5. 1

7 14 1 0 1 8. 2 80. 5 75. 3 5. 2

8 14 1 0 1 8. 2 80. 5 75 .3 5. 2

9 1400 1 8. 1 80. 4 75. 2 5. 2 Ratio 1 1420 1 9. 7 79. 0 75. 0 4.0

2 1 900 1 9. 8 78. 8 74 .9 3. 9 Comparison 3 1 390 1 7. 4 78. 8 74 .9 3. 9

4 2700 22. 7 78. 7 75 .0 3. 7 Example 5 1490 1 8. 1 78. 5 74. 9 3. 6

6 14 1 0 1 8. 6 77. 3 74. 4 2. 9 No addition Note 1400 1 8. 3 76. 3 73. 8 2. 3 Note) No addition: Do not add fluorescent whitening enhancer Pigment-coated paper paint 1 was prepared and evaluated in the same manner as the others, except that ヽ.

[Table 2] Paint for pigment coated paper (2) Pigment coated paper (2) Low shear viscosity High shear viscosity White color Fluorescence increased whiteness

<W1> <W2> <W1-W2> Actual 1 1 240 1 9. 2 8 2. 7 76. 0 6. 7

2 1 240 1 9. 2 8 2. 6 76. 0 6. 6 Out 3 1 240 1 9. 2 8 2. 7 76. 1 6. 6

4 1 250 1 9. 4 8 2. 5 76. 0 6. 5 Example 5 1 240 1 9. 3 8 2. 7 75. 9 6. 8

6 1 260 1 9. 5 8 2. 6 75 .9 6. 7

7 1 240 1 9. 3 8 2. 5 75 .9 6. 6

8 1 240 1 9. 3 8 2. 5 75 .9 6. 6

9 1 250 1 9. 3 8 2. 6 75 .9 6. 7 Ratio 1 1 290 2 1. 1 8 1. 0 75 .3 5. 7

2 1 770 2 1. 7 80. 9 75 .3 5. 6 Comparison 3 1 220 1 9. 2 80. 8 75 .3 5. 5

4 2600 22. 9 80. 8 75. 3 5. 5 Example 5 1 370 1 9. 9 80. 7 75. 3 5. 4

6 1 260 1 9. 7 80. 8 75. 3 5. 5 No additive Note 1 250 1 9. 5 8 0. 0 74. 8 5. 2 Note) Uncoated ink: Pigment coated paper paint 2 was prepared and evaluated in the same manner as above except that no fluorescent whitening enhancer was added.

[0070] [Table 3] Clear paper

White color Fluorescence whitening

Real 1 9 1. 2 81. 1 10. 1

2 8 1. 2 81. 1 10. 1

Out 3 9 1. 3 81. 1 10. 2

4 9 1. 2 81. 1 10. 1

Example 5 9 1. 3 81. 1 10. 2

6 9 1. 2 81. 1 10. 1

7 9 1. 3 81. 1 10. 2

8 9 1. 3 81. 1 10. 2

9 9 1. 2 81. 1 10. 1

Ratio 1 8 8. 6 80. 2 8. 4

2 8 8. 6 80. 3 8. 3

3 8 8. 4 80. 3 8. 1

4 8 8. 5 80. 3 8. 2

Example 5 8 8. 5 80. 3 8. 2

6 8 8. 0 80. 3 8. 0

Additive-free Note 8 0. 2 72. 3 7. 9 Note) Additive potato: Thaliaco was prepared and evaluated in the same manner as the above except that no fluorescent whitening enhancer was added.

[0071] [Table 4]

Inkjet paper paint f ink paper

Low shear viscosity White color Fluorescence increase whiteness

<W1> <W2> <W1-W2> Actual 1 44 86. 9 79. 2 7. 7

2 44 86. 9 79. 2 7. 7 Out 3 45 87. 1 79. 3 7. 8

4 47 87. 0 79. 3 7. 7 Example 5 47 87. 3 79. 4 7. 9

6 48 87. 0 79. 3 7. 7

7 47 87. 1 79. 3 7. 8

8 46 87. 2 79. 2 7. 8

9 48 86. 9 79. 2 7. 7 Ratio 1 1 52 84. 9 78. 3 6. 6

2 220 84. 8 78. 3 6. 5 Comparison 3 42 84. 4 78. 2 6. 2

4 1 74 84. 5 78. 2 6. 3 Example 5 60 84. 6 78. 3 6. 3

6 47 84. 6 78. 3 6. 3 No addition Note 50 84. 2 78. 0 6. 2 Note) No addition: Ink gel is the same as the others except that no fluorescent whitening enhancer is added. A paint was prepared and evaluated.

[Table 5]

Internal paper

White color Fluorescence whitening

Real 1 8 2. 0 79. 3 2. 7

2 8 2. 0 79. 3 2. 7

Out 3 8 2. 2 79. 4 2. 8

4 8 2. 0 79. 3 2. 7

Example 5 8 2. 2 79. 4 2. 8

6 8 2. 0 79. 3 2. 7

7 8 2. 2 79. 4 2. 8

8 8 2. 1 79. 4 2. 7

9 8 2. 0 79. 3 2. 7

Ratio 1 8 0. 7 79. 1 1. 6

2 8 0. 5 79. 0 1. 5

3 8 0. 5 79. 0 1. 5

4 8 0. 5 79. 0 1. 5

Example 5 8 0. 3 79. 0 1. 3

6 8 0. 2 79. 0 1. 2

No addition Note 79. 9 78. 9 1. 0 Note) No additive: Internal paper was prepared and evaluated in the same manner as above except that no fluorescent whitening enhancer was added.

[0073] As shown in Tables 1 to 5, those using the fluorescent enhancing brighteners (A1) to (A9) of the present invention use comparative fluorescent enhancing brighteners (B1) to (B6). Compared with those with and without additives, the fluorescent whitening degree was remarkably high. Further, even when the fluorescence-enhanced brightener of the present invention was used in a paper coating, the viscosity of the paint was almost completely changed.

Industrial applicability

[0074] 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 as compared with the case where the fluorescent whitening enhancer of the present invention is not blended. it can. Therefore, it is 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 coating paper coating material (finished as pigment paper) mainly composed of pigment, Z filler and binder, and coated paper containing no pigment and Z filler. Suitable for paint for inkjet paper (finished in clear coat paper), pigment and Z filler and binder, and fluorescent whitening agent used for pulp slurry etc. Can be used for In addition, fluorescent inks (dyes and pigments System) can also be used suitably.

Claims

The scope of the claims

[I] A fluorescent whitening enhancer that is used together with a fluorescent whitening agent, and which comprises a polyoxyalkylene compound represented by the general formula (1) as an essential component.

(General formula)

{B- (OA) n-0-} t Q (1)

[2] The fluorescent whitening enhancer according to claim 1, wherein the oxyalkylene group (OA) is oxyethylene and / or oxypropylene.

[3] Organic group (Q) is methyl, ethyl, propyl, butyl, pentyl, ethylene, probe, butylene, propane 1, 2, 3 tolyl, butane 1, 2, 3, 4-tetrayl, pentane 1, 2 , 3, 4, 5 Pentile, hexane— 1, 2, 3, 4, 5, 6 Hexayl, trimethylolpropane with 3 hydroxyl groups removed, residue, pentaerythritol with 4 hydroxyl groups removed Group, sorbitan force is also a residue excluding 4 hydroxyl groups, 6 hydroxyl groups are removed from dipentaerythritol, 8 residues are removed from saccharose, residue and Z or degree of condensation (m) 2. The fluorescent whitening enhancer according to claim 1, which is a residue obtained by removing (m + 2) hydroxyl groups from polyglycerin having 2 to 30.

[4] The fluorescent whitening enhancer according to claim 1, wherein the polyoxyalkylene compound can be produced by a reaction between an alcohol (al) having 1 to 90 carbon atoms and an alkylene oxide (a2) having 2 to 4 carbon atoms.

[5] A fluorescent whitening composition comprising the fluorescent whitening agent and the fluorescent whitening enhancer according to claim 1.

[6] A coated paper paint comprising the fluorescent whitening enhancer according to claim 1.

[7] A paint for inkjet paper, comprising the fluorescent whitening enhancer according to claim 1.

[8] An ink composition comprising the fluorescent whitening enhancer according to claim 1.

[9] A coated paper obtained by coating the coated paper paint according to claim 6.

[10] An inkjet paper obtained by coating the inkjet paper paint according to [7].

[II] Paper obtained by internally adding the fluorescent whitening enhancer according to claim 1.