CN1402805A - Surface-sizing agent - Google Patents
Surface-sizing agent Download PDFInfo
- Publication number
- CN1402805A CN1402805A CN 00816596 CN00816596A CN1402805A CN 1402805 A CN1402805 A CN 1402805A CN 00816596 CN00816596 CN 00816596 CN 00816596 A CN00816596 A CN 00816596A CN 1402805 A CN1402805 A CN 1402805A
- Authority
- CN
- China
- Prior art keywords
- monomer
- cypres
- paper
- shellac
- alkali metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004513 sizing Methods 0.000 title abstract description 44
- 239000000178 monomer Substances 0.000 claims abstract description 135
- 229920001800 Shellac Polymers 0.000 claims abstract description 63
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 claims abstract description 63
- 239000004208 shellac Substances 0.000 claims abstract description 63
- 229940113147 shellac Drugs 0.000 claims abstract description 63
- 235000013874 shellac Nutrition 0.000 claims abstract description 63
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 49
- 239000002270 dispersing agent Substances 0.000 claims abstract description 37
- -1 alkali metal salt Chemical class 0.000 claims description 80
- 235000004258 Cordia alliodora Nutrition 0.000 claims description 76
- 244000085692 Cordia alliodora Species 0.000 claims description 76
- 229910052783 alkali metal Inorganic materials 0.000 claims description 42
- 125000000129 anionic group Chemical group 0.000 claims description 33
- 238000006116 polymerization reaction Methods 0.000 claims description 29
- 229920002521 macromolecule Polymers 0.000 claims description 28
- 229920001577 copolymer Polymers 0.000 claims description 24
- 239000002585 base Substances 0.000 claims description 22
- 239000004094 surface-active agent Substances 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 16
- 230000000694 effects Effects 0.000 claims description 16
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
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- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 3
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- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000002761 deinking Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical class CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 238000007648 laser printing Methods 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000010899 old newspaper Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000010010 raising Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- 210000000689 upper leg Anatomy 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
Abstract
A surface-sizing agent for papermaking which itself is excellent in mechanical stability and storage stability, and which is highly suitable for the sizing of acidic to neutral papers. When applied to papers for information, especially ink-jet printing papers, the sizing agent imparts excellent suitability for ink-jet printing. When the sizing agent is used to prepare a coating fluid, the coating fluid is significantly reduced in foaming. The sizing agent has excellent compatibility with other chemicals to be used in combination therewith. The surface-sizing agent is characterized by being obtained by polymerizing a nonionic hydrophilic monomer (b) with a hydrophobic monomer (d) in the presence of an alkali salt of shellac (a) and then mixing a polymeric dispersant (e) therewith.
Description
Technical field
The present invention relates to Cypres, more detailed ground carefully says, relate to mechanical stability, storage stability, for acidic paper to the sizability of neutralized paper, for information with the suitable property of paper, in the coating fluid low foaming, share the Cypres of the good paper grade (stock) of the intermiscibility of medicine with other.
Background technology
With regard to present surface sizing agent for paper making, the known aqueous solution that the alkali metal salt of phenylethylene-maleic oxalic acid series copolymer, styrene-(methyl) acrylic acid series copolymer, alpha-olefin-maleic acid based copolymer etc. is arranged.
Though the Cypres of phenylethylene-maleic oxalic acid series copolymer is copied paper for the acidity of using many alum, show good sizing efficiency, but copy paper, reach the paper that the few neutrality of alum use amount is copied paper for the neutrality of not using alum, then sizability is significantly abominable.
And when surface coated, because the foaming of sizing agent itself is many, so the use amount of defoamer is increased, its result causes repulsion on coated face, has problems such as making the sizing efficiency deterioration.
Styrene-(methyl) shows comparatively good STICKY HIT degree of sizing though the Cypres of acrylic acid series copolymer is copied the paper paper for above-mentioned neutrality, and to write degree of sizing poor because of pen, so there is problem such as literal seepage when record.And the coating fluid that uses this Cypres to modulate is not because significantly good for the stability of metal ion, so there is the problem that takes place more than condensation product (factory then is called ' dregs of rice ') and the foaming etc. in the operation.
Though the Cypres of alpha-olefin-maleic acid based copolymer demonstrates good pen and writes degree of sizing, then the fastness of toner is low with paper but if be used in PPC, then on the contact of ink, have problems if be used in printing, and then there is the problem in the foaming operations that wait in the coating fluid that uses this Cypres to modulate more.
And, the patent of the latex type Cypres by the emulsion polymerization manufactured, existing several are reported as the prior art type.
For example, open in the flat 8-246391 communique the spy, ' promptly containing in the aqueous solution of water solubility copolymer 100 weight portions that (1) contain carboxyl unsaturated monomer and (2) hydrophobicity unsaturated monomer, with the surface sizing agent for paper making that latex constituted of [A] hydrophobicity unsaturated monomer 10～500 weight portion emulsion polymerization gained containing [B] ' disclosed.
This corpuscular type Cypres is compared with present solution-type Cypres, though with other share medicine intermiscibility, and modulation deposit the stability of metal ion or the foaminess of this coating fluid is enhanced with respect to molten during coating fluid, its sizability is still not enough.
And, open in the clear 49-50209 communique the spy, disclose ' in the alkaline aqueous solution of shellac, but will be from styrene and styrene derivative selected at least a monomer or mix with other monomer of its copolymerization more as required, and add the Surface Machining agent that catalysts for radical polymerization carries out the obtained paper that aqueous liquid dispersion constituted of copolymerization therein '.
But, above-mentioned Surface Machining agent is in the ammonia spirit of shellac, makes styrene and styrene derivative carry out emulsion polymerization, though can improve the resistance to water and the glossiness of paper, but the problem in the manufacturing of the condensation product that mostly occurs when emulsion polymerization etc., and resistance to water is also insufficient.And the Surface Machining agent of gained is for the stability of metal ion, and mechanical stability extreme difference, so produce variety of issue on actual job.
And, recently not only for the ink-jet dedicated paper and for PPC paper, also the suitable property of ink-jet such as the printed desired lettering concentration of image quality, the paper degree of spreading and sinking in (feathering), the back side of ink-jetting style of monochrome or color inks is permeated, the border is oozed out are used in requirement, and expectation can obtain the sizing agent that satisfies this suitable property paper.
Summary of the invention
The object of the present invention is to provide a kind of Cypres of paper grade (stock), the mechanical stability and the storage stability of sizing agent itself are good, good for acidic paper to the sizability of neutralized paper, and has the suitable property of good ink-jet with paper, particularly ink-jet with paper for information, and when the modulation coating fluid, the foaminess of this coating fluid significantly diminishes, and good with other intermiscibility that share medicine.
In order to address the above problem, the inventor in depth studies repeatedly, its result, in the presence of the alkali metal salt of shellac at least, make hydrophobic monomer and nonionic hydrophilic monomer, or hydrophobic monomer, after the monomer that nonionic hydrophilic monomer and anionic property monomer are constituted carries out polymerization, mix macromolecule dispersing agent, perhaps, in the presence of the material except the alkali metal salt of shellac with surface-activity ability, make hydrophobic monomer and nonionic hydrophilic monomer, or hydrophobic monomer, after the monomer that nonionic hydrophilic monomer and anionic property monomer are constituted carries out polymerization, the alkali metal salt and the macromolecule dispersing agent that mix shellac are then made and are finished the surface sizing agent for paper making that can overcome the problems referred to above.
That is, the 1st mode of the present invention is:
In the presence of the alkali metal salt (a) of shellac, in the reactant liquor of nonionic hydrophilic monomer (b) and hydrophobic monomer (d) polymerization gained, mix the Cypres of macromolecule dispersing agent (e) gained,
The 2nd mode of the present invention is:
In the presence of the alkali metal salt (a) of shellac, in the reactant liquor of nonionic hydrophilic monomer (b), anionic property monomer (c) and hydrophobic monomer (d) polymerization gained, mix the Cypres of macromolecule dispersing agent (e) gained,
The 3rd mode of the present invention is:
In the presence of the material with surface-activity ability (f) except the alkali metal salt (a) of shellac, in the reactant liquor of nonionic hydrophilic monomer (b) and hydrophobic monomer (d) polymerization gained, mix the alkali metal salt (a) of shellac and the Cypres of macromolecule dispersing agent (e) gained
The 4th mode of the present invention is:
In the presence of the material with surface-activity ability (f) except the alkali metal salt (a) of shellac, in the reactant liquor of nonionic hydrophilic monomer (b), anionic property monomer (c) and hydrophobic monomer (d) polymerization gained, mix the alkali metal salt (a) of shellac and the Cypres of macromolecule dispersing agent (e) gained
Being characterized as of the Cypres of the 5th mode of the present invention:
Comprise: the alkali metal salt of shellac (a); Have with nonionic hydrophilic monomer (b) and hydrophobic monomer (d) as the polymer of repetitive or, have nonionic hydrophilic monomer (b), anionic property monomer (c) and hydrophobic monomer (d) polymer as repetitive; Macromolecule dispersing agent (e).
The 6th mode of the present invention is above-mentioned the 3rd or 4 described Cypres, wherein,
In the above-mentioned the 1st～the 5th in any one mode, the material with surface-activity ability (f) except the alkali metal salt (a) of shellac is for having the surfactant of polymerism base,
The 7th mode of the present invention is: in the above-mentioned the 1st～the 5th in any one mode,
Surfactant with polymerism base is for having methacryl and/or allylic reactive emulsifier,
The 8th mode of the present invention is: in the above-mentioned the 1st～the 5th in any one mode,
Above-mentioned nonionic hydrophilic monomer (b) is select from the group of being made up of (methyl) acrylamide, acrylonitrile and (methyl) hydroxyalkyl acrylate at least a,
The 9th mode of the present invention is: in the above-mentioned the 1st～the 5th in any one mode,
Above-mentioned hydrophobic monomer (d) is select from the group of being made up of styrene derivative and (methyl) alkyl acrylate at least a,
The 10th mode of the present invention is: in the above-mentioned the 1st～the 5th in any one mode,
Above-mentioned anionic property monomer (c) is the monomer with carboxylic acid group,
The 11st mode of the present invention is: in the above-mentioned the 1st～the 5th in any one mode,
Above-mentioned macromolecule dispersing agent (e) is salt and/or (methyl) acrylate based copolymer of styrene-propene acid based copolymer.
The specific embodiment
Cypres of the present invention is a latex type Cypres.This Cypres is by in the presence of the alkali metal salt (a) of shellac, at nonionic hydrophilic monomer (b) and hydrophobic monomer (d), or nonionic hydrophilic monomer (b), in the one stage polymer of anionic property monomer (c) and hydrophobic monomer (d) polymerization, mixing macromolecule dispersing agent (e) then can obtain, perhaps in the presence of the material with surface-activity ability (f) except the alkali metal salt (a) of shellac, at nonionic hydrophilic monomer (b) and hydrophobic monomer (d), or nonionic hydrophilic monomer (b), in the one stage polymer of anionic property monomer (c) and hydrophobic monomer (d) polymerization, mix the alkali metal salt (a) of shellac and then can obtain with macromolecule dispersing agent (e).
Shellac used in the present invention, be that the secreted resinoid of shellac shell worm that will parasitize the Nan Yang plant is made with extra care, being made of a plurality of resin acid mixtures, for example is to be carried out the soften resin of esterification or constituted in conjunction with several this kind soften resins by lac (acid of ァ レ ゥ リ チ Application), eleostearic acid (ジ ャ ラ-Le acid) or shelloic acid (ラ Network シ ジ ャ ラ-Le acid).
The alkali metal salt of the so-called shellac of the present invention (a) is meant shellac is neutralized with alkaline matter.For the employed alkaline matter of the alkali metal salt of obtaining shellac, if the water-soluble liquefaction of shellac is got final product, be not particularly limited, but preferred caustic alkali, caustic soda and ammonia.The use amount of above-mentioned alkaline matter is more than the acid value equivalent with respect to shellac, and is then preferable aspect stability when improving emulsion polymerization and gained Cypres stable.
In the present invention, if there is the alkali metal salt of shellac, then can makes to be polymerized to relax and carry out during polymerization, when emulsion polymerization, has the advantage that can obtain minuteness particle especially, the having good stability of the Emulgating polymers of gained, resistance to water improves, and has the tendency that reduces foaming.
The material with surface-activity ability (f) except the alkali metal salt of shellac used in the present invention, can use well-known emulsifying agent or dispersant, it can enumerate for example low-molecular-weight surfactant, surfactant with polymerism base, and can use from these groups, select at least a, wherein, owing to obtain the good Cypres of low foaming, so preferably have the surfactant of polymerism base.
Above-mentioned low-molecular-weight surfactant can use the material that is suitable for Emulgating polymers usually, can use the low-molecular-weight surfactant of nonionic, anionic property, both sexes and cationic, and can use from these groups, select at least a, wherein, according to the viewpoint of stability of emulsion, the low-molecular-weight surfactant of preferred nonionic and the low-molecular-weight surfactant of anionic property.
As the nonionic low-molecular-weight surfactant, can enumerate for example polyoxy alkene alkane phenyl ether, polyoxy olefin alkylation ether, polyoxy alkene fatty acid ester, polyoxyethylene polyoxypropylene glycol glycerol fatty acid ester, sorbitan fatty acid ester, cithrol, polyoxyethylene sorbitan fatty acid ester, sucrose fatty ester, pentaerythritol fatty ester, methyl glycol fatty acid ester, fatty diglycollic amide, polyoxyethylene polyoxypropylene ethylene glycol etc.In the present invention, can be used alone or share above-mentioned nonionic low-molecular-weight surfactant more than two kinds.
As the anionic surfactant, can enumerate the alkali metal salt of phosphate ester salt, sulfonate, succinate salt and the sulfosuccinate ester salt of polyoxy alkene alkane phenyl ether, polyoxy alkene list and diphenylethyllene phenyl ether, polyoxy olefin alkylation ether and polyoxy alkene fatty acid ester etc., the alkali metal salt that reaches alkylbenzenesulfonate, naphthalene sulfonic acid-formaldehyde condensation product, fat alkenyl succinate, rosin and the alkali metal salt of reinforcement rosin.In the present invention, can be used alone or share above-mentioned anionic property low-molecular-weight surfactant more than two kinds.
As cationic surfactant, but illustration chlorination tetra-allkylammonium, chlorination triakyl benzyl ammonium, alkylamine, list and polyoxyethylene alkyl amine etc.In the present invention, can use or share above-mentioned cationic low-molecular-weight surfactant more than two kinds separately.
Surfactant with above-mentioned polymerism base is commonly referred to as reactive emulsifier, has the compound of hydrophobic group, hydrophilic group and carbon-to-carbon double bond in molecule.So-called carbon-to-carbon double bond for example is meant the two keys in (methyl) allyl, 1-propenyl, 2-methyl isophthalic acid-propenyl, isopropenyl, vinyl and (methyl) acryloyl group etc.
As surfactant with these polymerism bases, can use the surfactant that is applicable to emulsion polymerization usually, be not particularly limited, but the polyoxy olefin alkylation ether that has above-mentioned functional group more than in its concrete example illustration molecule, polyoxy alkene aralkyl ether, polyoxy alkene phenylate, polyoxy alkene list and diphenylethyllene phenylate etc. and sulfonate thereof, sulfuric acid, phosphate ester salt and sulfosuccinate ester salt, the aliphatic series and the aromatic carboxylic acid salt that have polyoxy olefin alkylation ether or the polyoxy alkene phenyl ether of above-mentioned functional group more than in the molecule, acid phosphatase (methyl) acrylate based compound, rosin-(methyl) glycidyl acrylate based compound, and alkyl diphenyl base ether disulfonic acid based compound, for example hexyl diphenyl ether disulfonic acid, decyl diphenyl ether disulfonic acid, dodecyl diphenyl ether disulfonic acid, cetyl diphenyl ether disulfonic acid and sodium salt thereof, the alkali metal salt of sylvite etc. and ammonium salt etc.In the present invention, can be used alone or share above-mentioned surfactant more than two kinds with polymerism base.
Usually, when above-mentioned surfactant (f) uses separately at the alkali metal salt that does not use shellac, using with respect to hydrophobic monomer (d) 100 weight portions is the scope of 0.5～5 weight portion, when the alkali metal salt with shellac share, then the alkali metal 100 weight portions use with respect to shellac was the scope of 1～20 weight portion.
Above-mentioned macromolecule dispersing agent used in the present invention (e) can use synthetic high polymer with hydrophobicity base, nonionic base and/or ionic base or general natural polymer dispersant basically, if list the example of synthetic high polymer, but then (methyl) acrylate based copolymer of partially or completely corrective, anion or the cationic of illustration polyvinyl alcohol and modifier thereof, anionic property styrene-(methyl) acrylic acid series copolymer or the water-base resin of (methyl) acrylamide based copolymer, polyester, polyurethane, alkyd and polyamide etc.The natural polymer emulsifying agent can be enumerated for example cellulose derivative, starch and the producing starch etc. of casein, lecithin, hydroxyethylcellulose etc.In the present invention, can use or share above-mentioned macromolecule dispersing agent (e) more than two kinds separately.In the present invention,, can list the salt of styrene-(methyl) acrylic acid series copolymer, for example ammonium salt, and (methyl) acrylate based copolymer as the proper polymer dispersant.
Above-mentioned macromolecule dispersing agent (e) can share the alkali metal salt of its part with shellac before polymerization, but add after the preferred polymeric, this is because the mechanical stability of latex particle and the dilution stability when diluting with the water that contains metal ion are good.
The use amount of above-mentioned macromolecule dispersing agent (e) for hydrophobic monomer (d) 100 weight portions, is the scope of 5～100 weight portions, the scope of preferred 5～50 weight portions, even add more raisings of also not finding above-mentioned effect, and cause the reduction of sizability, so bad.
In the present invention, if with nonionic hydrophilic monomer (b) as the polymerization composition, the generation of the condensation product that side reaction generates in the time of then can suppressing emulsion polymerization especially, and have the advantage that can make easily, and have the storage stability of the Cypres of gained, with respect to the stability and the good advantage of mechanical stability of metal ion.
Nonionic hydrophilic monomer used in the present invention (b) is not possess cationic base and anionic property base and the polymerizable monomer that possesses the hydrophily base, for example can list (methyl) acrylamide, acrylonitrile, and (methyl) hydroxyalkyl acrylate etc.In the present invention, can be used alone or share nonionic hydrophilic monomer more than two kinds.The nonionic hydrophilic monomer (b) that the present invention is used is not if possess the cationic base and anionic property base and the polymerizable monomer that possesses the hydrophily base get final product, and contains the water-soluble monomer of nonionic.In above-mentioned nonionic hydrophilic monomer, preferred cheapness and the acrylamide that is easy to obtain.
In the present invention, as the polymerization composition, then can make the resistance to water of Cypres of gained good hydrophobic monomer (d).
The used hydrophobic monomer (d) of the present invention comprises the water-insoluble monomer.As this hydrophobic monomer, for example can list styrene, and the vinyl esters of styrene derivative, (methyl) alkyl acrylate, (methyl) acrylic acid cycloalkanes ester, maleic acid and the fumaric dialkyl group diester class of α-Jia Jibenyixi, vinyltoluene, divinylbenzene etc., tertiary carboxylic acid vinyl acetate that carbon number is 5～10 and propionate etc., N alkyl (methyl) acrylic amide, and ethylene methacrylic ether etc.These various hydrophobic monomers can be used alone, also can mix and use more than two kinds.When using (methyl) esters of acrylic acid and other hydrophobic monomer, as its match ratio, the deal of (methyl) alkyl acrylate class, for whole hydrophobic monomer amounts, being at least 25 weight %, being preferably 40～100 weight %, is good for sizability then.
In the present invention, if with anionic property monomer (c) as the polymerization composition, then have the advantage of the stability when improving emulsion polymerization more, and can improve the mechanical stability of the Cypres of gained more.
Anionic property monomer used in the present invention (c) is for having the monomer of anionic property base, for example can list (methyl) acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, butenoic acid etc. the monomer with carboxylic acid group, vinyl sulfonic acid, (methyl) propene sulfonic acid, 2-acrylamide-2-methyl propane sulfonic acid, sulfonated phenylethylene etc. the phosphate with sulfonic monomer, (methyl) hydroxyalkyl acrylate etc. have a phosphate-based monomer.These anionic property monomers can be used alone, also can mix and use more than two kinds.Wherein, owing to have the characteristic that the anionic property monomer of carboxyl is given the Cypres low foaming, so preferably have the anionic property monomer of carboxyl, wherein more preferably (methyl) acrylic acid and itaconic acid.
As the combination of above-mentioned monomer component, can list nonionic hydrophilic monomer (b) and the combination of hydrophobic monomer (d) and the combination of nonionic hydrophilic monomer (b) and anionic property monomer (c) and hydrophobic monomer (d).By adopting the combination of nonionic hydrophilic monomer (b) and hydrophobic monomer (d), the purpose of attainable cost invention then, and, if adopt nonionic hydrophilic monomer (b) and the combination of anionic property monomer (c), then can obtain the good Cypres that mechanical stability is improved more with hydrophobic monomer (d).
That is, Cypres of the present invention contain with nonionic hydrophilic monomer (b) and hydrophobic monomer (d) as the polymer of repetitive or, with nonionic hydrophilic monomer (b), anionic property monomer (c) and hydrophobic monomer (d) polymer as repetitive.
The alkali metal salt (a) of the shellac when Cypres of the present invention is made, material (f) with surface-activity ability, nonionic hydrophilic monomer (b), anionic property monomer (c), the use amount of hydrophobic monomer (d) and macromolecule dispersing agent (e), for hydrophobic monomer (d) 100 weight portions, the alkali metal salt (a) of preferred shellac is 1～20 weight portion, material (f) with surface-activity ability is 0.5～5 weight portion, nonionic hydrophilic monomer (b) is 1～20 weight portion, anionic property monomer (c) is that 0.1～10 weight portion and macromolecule dispersing agent (e) are 5～100 weight portions, this is for the stability of Cypres and sizability and Yan Weijia, and, for hydrophobic monomer (d) 100 weight portions, more preferably the alkali metal salt of shellac (a) is 5～15 weight portions, material (f) with surface-activity ability is 0.5～3 weight portion, nonionic hydrophilic monomer (b) is 5～15 weight portions, anionic property monomer (c) is that 0.5～5 weight portion and macromolecule dispersing agent (e) are 5～50 weight portions.And above-mentioned use amount with material (f) of surface-activity ability is not when share the alkali metal salt of shellac (a), use amount during for independent the use, when share the alkali metal salt of shellac (a), then for the alkali metal salt (a) of shellac, use the scope of 1～20 weight %.
When making Cypres of the present invention, currently known polymerization can be adopted, and solution polymerization process, mass polymerization, emulsion polymerization method etc. can be adopted, but for the easy degree of making, then preferred emulsion polymerization method.And at this moment, monomer in fact all polymerization generates homopolymers or copolymer, when having shellac before polymerization, thinks that then this shellac also participates in polymerization.
As the employed catalysts for radical polymerization of above-mentioned polymerization, for example can list peroxide, these persulfates or the peroxide of persulfate, tert-butyl hydroperoxide, hydrogen peroxide etc. of ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate etc. and the redox system polymerization catalyst or 2 of reductant combination, 2 '-azodiisobutyronitrile, 2,2 '-the azo series catalysts of azo two-2-methyl propanamide dihydrochloride (2,2 '-ァ ゾ PVC ス-2-メ チ Le プ ロ ピ ォ Na ミ ジ Application ジ ヒ De ロ Network ロ リ De) etc.And, also can share well-known chain as required and move agent.
Used paper pulp in the body paper that Cypres of the present invention was suitable for (base paper) can list the bleaching of kraft pulp or sulfite pulp etc. or not bleaching such as bleached chemical paper pulps, wood fragments paper pulp, mechanical pulp or thermomechanical pulp or do not bleach old paper paper pulp of high yield paper pulp, old newspaper, outdated magazine paper, the old paper of corrugated cardboard or the old paper of deinking etc. etc.
In order to obtain body paper, and show the desired rerum natura of various paper, also can to use filler, dyestuff, acidity to copy paper as required be that sizing agent, alkyl diketene system or alkenyl succinic anhydride system are neutral with rosin copies paper to copy paper with sizing agent, neutrality is the additive of the sizing agent of sizing agent etc., dry paper power reinforcing agent, moistening paper power reinforcing agent, productive rate improving agent, drainability improving agent, defoamer etc. with rosin.As filler, can list clay, talcum powder, titanium oxide, heavy or precipitated calcium carbonate etc.Can separately or merge and use.
For Cypres of the present invention is coated with used coating machine, can use applying glue to add press, film adds press, cast gate roller coat device, Lyceum gluing machine, knife type coater, calender, rod coater, scraper plate coating machine, Kohler coater, curtain formula coating machine etc.And, also can on the body paper surface, be coated with by Bracewell coater.
In coating during Cypres of the present invention, also the water soluble polymer of the cellulose family of the starch based of oxidized starch, organic phosphate starch, ferment modified starch, cationic starch etc., carboxymethyl cellulose etc., polyvinyl alcohol, polyacrylamide, mosanom etc. can be mixed in the coating fluid and use.And the additive such as Cypres, antilubricant, preservative agent, rust inhibitor, defoamer, viscosity modifier, dyestuff, pigment that share other is also passable.
For the sized paper of the Cypres of the present patent application being coated gained on the above-mentioned body paper, can be various paper and paperboard.For example can list package paper, photo that PPC changes the coated paper, brown paper, pure white roll web etc. of slurry coated paper etc. with paper, thermal sensitive recording with paper, hot transfer printing with the paper used for recording of paper etc., art paper, cast-coated paper, entirely with paper, ink-jet recording paper, used for laser printing paper, form with print paper, other notepaper, books with paperboard such as the paper device of the Western paper of paper, printing, newsprint etc., Manila paperboard, white board, thick paperboard etc. with paperboard, liner plate etc.
Top sizing agent concentration during the Cypres of coating the present patent application in the employed coating fluid is generally 0.1～5 weight %, is preferably 0.2～1 weight %.Less than 0.1 weight % then sizing efficiency is abundant inadequately sometimes, and surpasses 5 weight %, improves sizing efficiency hardly, and does not calculate economically, so bad.
And coating weight is counted 0.01～1g/m with solid content usually
2, be preferably 0.02～0.1g/m
2If above-mentioned scope then can be brought into play good sizing efficiency especially.
Below, enumerate embodiment and comparative example, further describe the present invention, but the present invention is not limited to these embodiment.
(synthesis example 1)
Open the reference example 2 of flat 8-246391 communique according to the spy, the aqueous solution of the ammonium salt (S-1) of the macromolecule dispersing agent styrene-propene acid copolymer as following among synthetic the present invention, i.e. macromolecule dispersing agent solution (S-1 solution).
In possessing 1 liter of four-hole boiling flask of agitator, thermometer, backflow cooling tube and nitrogen ingress pipe, add 100 parts of entry, 75 parts of 95% isopropyl alcohols, heat while stir, temperature is risen to till 80 ℃.Therein, after splashing into 3 hours full doses with the monomer mixed solution of 55 parts in 45 parts of benzene mixed ethene and acrylic acid, with potassium peroxydisulfate 5 parts of water-soluble polymerizations of 120 parts initiation solution, be incubated 2 hours and make to react and finish.Thereafter, steam and remove isopropyl alcohol, after cooling, add 46.4 parts of 28% ammonia spirits (with respect to 100 moles of % of acrylic acid), and dilute with water, being adjusted to and making copolymer concentration is 20%, obtain the aqueous solution of the ammonium salt (S-1) of water solubility copolymer styrene-propene acid copolymer, i.e. macromolecule dispersing agent solution (S-1 solution).
(synthesis example 2)
In possessing 1 liter of four-hole boiling flask of agitator, thermometer, backflow cooling tube and nitrogen ingress pipe, add 586 parts of entry, 80 parts of styrene, 39 parts of α-Jia Jibenyixi, 22 parts of methyl methacrylates, 75 parts of methacrylic acids, 3.3 parts of n-dodecyl mercaptans, 1 part of neopelex, add 33 parts of 30% ammonium persulfate aqueous solutions again, and be heated to 80 ℃, made reaction finish in 2 hours 80 ℃ of insulations., add 30% soda lye 121 part (with respect to methacrylic acid 95 mole %s), and kept 30 minutes in 80 ℃ thereafter.With the water dilution, being modulated into and making copolymer concentration is 25%, obtains the aqueous solution of the sodium salt (S-2) of water solubility copolymer styrene-methacrylic acid based copolymer, and promptly macromolecule disperses solution (S-2 solution).
(embodiment 1)
Possessing agitator, thermometer, in 1 liter of four-hole boiling flask of backflow cooling tube and nitrogen ingress pipe, add 535 parts of entry, 13.2 parts of shellac (the abundant SHELLAC of qi (strain) system N811) are (when hydrophobic monomer all is 100 weight portions, be 8 weight portions), 4.2 parts of ELEMINOL JS-2 (Sanyo's system of changing into) are (when hydrophobic monomer all is 100 weight portions, be 1 weight portion), 12.9 parts of acrylamides are (when hydrophobic monomer all is 100 weight portions, be 8 weight portions), 3.4 parts in 48% caustic alkali, and add 64.5 parts of styrene again (when hydrophobic monomer all is 100 weight portions, be 40 weight portions), 96.7 parts of n-butyl acrylates are (when hydrophobic monomer all is 100 weight portions, be 60 weight portions), reach 0.8 part of ammonium persulfate, stirring stumbles is warming up to 80 ℃ while mix under nitrogen current.Keep making in 2 hours the emulsion polymerization reaction to finish at 80 ℃, add macromolecule dispersing agent solution (S-1 solution) 161 parts (when hydrophobic monomer all was 100 weight portions, S-1 was 20 weight portions), obtain solid content concentration and be 25.3% latex type Cypres.
(implementing profit 2～9, comparative example 1～4)
The kind and deal change as shown in table 1 of the dispersant after the kind of the dispersant before making polymerization, nonionic hydrophilic monomer, anionic property monomer and deal, hydrophobic monomer kind and deal, the polymerization, handle with embodiment 1, obtain latex type Cypres.
(comparative example 5)
Comparative example 5 is Cypres SS315 (a Japanese PMC corporate system) for using commercially available styrene-propene acid.
(test example 1) is with the evaluation of matter paper on the acidity
(1) manufacturing of matter paper usefulness body paper on the acidity
Smash paper pulp to canadian standard freeness (Canadian Standard Freeness) (broad leaf tree to acerose paper pulp than the mixed pulp that is 9 pairs 1) to pieces with 380 milliliters and make 2.5% slurries, and add the talcum powder (TALC of Fuji industry system: ND TALC) therein with respect to paper pulp 15% (adiabatic drying weight basis).Therein, add successively alum with respect to paper pulp 2% (adiabatic drying weight basis), be sizing agent (Japanese PMC system with respect to the acidic paper of paper pulp 0.3% (adiabatic drying weight basis) with rosin; AL120) afterwards, the dilution water with PH4.5 is diluted to concentration 0.25% with this pulp slurry.Thereafter, interpolation is with respect to productive rate elevator (the HIMO corporate system of paper pulp 0.01%; NR12MLS), and with Noble ﹠amp; The Wood paper machine, amount 65g/m2 copies paper with the level ground.And the paper pH that copies of this moment is 4.5.The drying of l Water Paper is used heated drum, carries out with the condition in 100 ℃ of following 80 seconds.
(2) method of adjustment of coating fluid
Oxidized starch (MS3800 japanese food chemical company system) is diluted to concentration 10% with water, and carries out gelatinization, and in this dextrin, mix above-mentioned Cypres, be modulated into coating fluid at 95 ℃.At this moment, the solid content concentration with oxidized starch in the coating fluid and Cypres is adjusted to following value.Again this coating fluid is adjusted to pH8 with caustic soda or sulfuric acid, or is adjusted to pH6, then can modulate the coating fluid of pH8 and the coating fluid of pH6 with sulfuric acid.
The solid content concentration of the oxidized starch in the coating fluid: 6%
The solid content concentration of the Cypres in the coating fluid: 0.2%
(3) manufacturing of matter paper and evaluation on the acidity
On the body paper of being manufactured paper with pulp in above-mentioned (1), the coating fluid of above-mentioned (2) preparation is added press with applying glue be coated with, obtain the acid matter paper of going up.With the damping 24 hours under constant temperature and humidity (20 ℃, 65% relative humidity) environment of the ph test paper ph of gained, measure the mensuration (according to J TAPPI paper pulp test method No.12-76) of a STICKY HIT degree of sizing (according to JIS P8122) and a book degree of sizing.
Evaluation result is shown in table 2.And, STICKY HIT degree of sizing and the pen write degree of sizing all be worth high more then the expression good more.
(test example 2) is with the evaluation of matter paper on the neutrality
(1) manufacturing of matter usefulness body paper on the neutrality
Smash paper pulp to canadian standard freeness (broad leaf tree to acerose paper pulp than the mixed pulp that is 9 pairs 1) to pieces with 380 milliliters and make 2.5% slurries, and add calcium carbonate (Ao Duomo industrial group system therein with respect to paper pulp 2% (adiabatic drying weight basis); TP121S).Therein, add amphoteric starch (NationalStarch corporate system successively with respect to paper pulp 0.5% (adiabatic drying weight basis); Cato3210) the alkyl diketene that reaches with respect to paper pulp 0.08% (adiabatic drying weight basis) is a sizing agent (Japanese PMC system; AS263) afterwards, the dilution water with PH7.5 is diluted to concentration 0.25% with this pulp slurry.In the pulp slurry of dilution add calcium carbonate (Ao Duomo industrial group system with respect to paper pulp 8% (adiabatic drying weight basis) thereafter; TP121S), with respect to productive rate elevator (the HIMO corporate system of paper pulp 0.01%; NR12MLS), and with Noble ﹠amp; The Wood paper machine is with level ground amount 65g/m
2Copy paper.And the paper ph that copies of this moment is 7.5.The drying of l Water Paper is used heated drum, carries out with the condition in 100 ℃ of following 80 seconds.
(2) modulator approach of coating fluid
Oxidized starch (MS3800 japanese food chemical company system) is diluted to concentration 10% with water, and carries out gelatinization, and in this dextrin, mix above-mentioned Cypres, be modulated into coating fluid at 95 ℃.At this moment, the solid content concentration with oxidized starch in the coating fluid and Cypres is adjusted to following value.Again this coating fluid is modulated into PH8 with caustic soda or sulfuric acid, then can modulates the coating fluid of PH8.
The solid content concentration of the oxidized starch in the coating fluid: 6%
The solid content concentration of the Cypres in the coating fluid: 0.2%
(3) manufacturing of matter paper and evaluation on the neutrality
On the body paper of being manufactured paper with pulp in above-mentioned (1), the coating fluid of above-mentioned (2) configuration is added press with applying glue be coated with, obtain the neutral matter paper of going up.With the damping 24 hours under constant temperature and humidity (20 ℃, 65 ℃ relative humidity) environment of the ph test paper ph of gained, and, carry out the mensuration that STICKY HIT degree of sizing and pen are write degree of sizing with test example 1.The results are shown in table 2.
(test example 3) is with the evaluation of ink jet recording paper
Smash paper pulp to canadian standard freeness (broad leaf tree to acerose paper pulp than the mixed pulp that is 9 pairs 1) to pieces with 380 milliliters and make 2.5% slurries, and add calcium carbonate (Ao Duomo industrial group system therein with respect to paper pulp 1% (adiabatic drying weight basis); TP121S) and 5% talcum powder (TALC industrial group of Fuji system: ND TALC).Therein, add successively alum with respect to paper pulp 1.0% (adiabatic drying weight basis), with respect to amphoteric starch (the National Starch corporate system of paper pulp 0.5% (adiabatic drying weight basis); Cato3210) neutralized paper that reaches with respect to paper pulp 0.3% (adiabatic drying weight basis) is a sizing agent (Japanese PMC system with rosin; CC167) after, this pulp slurry is diluted to concentration 0.25% with the dilution water of PH7.5.In the pulp slurry of dilution add calcium carbonate (Ao Duomo industrial group system with respect to paper pulp 4% (adiabatic drying weight basis) thereafter; TP121S), with respect to productive rate elevator (the HIMO corporate system of paper pulp 0.01%; NR12MLS), and with Noble ﹠amp; The Wood paper machine, amount 65g/m2 copies paper with the level ground.And the paper pH that copies of this moment is 7.5.The drying of l Water Paper is used heated drum, carries out with the condition in 100 ℃ of following 80 seconds.
(2) modulator approach of coating fluid
Oxidized starch (MS3800 japanese food chemical company system) is diluted to concentration 10% with water, and carries out gelatinization, and in this dextrin, mix above-mentioned Cypres and salt, be modulated into coating fluid at 95 ℃.At this moment, the solid content concentration with the oxidized starch in the coating fluid, Cypres and salt is adjusted to following value.Again this coating fluid is modulated into PH8 with caustic soda or sulfuric acid, then can be modulated into the coating fluid of PH8.
The solid content concentration of the oxidized starch in the coating fluid: 8%
The solid content concentration of the Cypres in the coating fluid: 0.2%
The solid content concentration of the salt in the coating fluid: 0.5%
(3) manufacturing of record-paper
On the body paper of being manufactured paper with pulp in above-mentioned (1), the coating fluid of above-mentioned (2) preparation is added press with applying glue be coated with, obtain record-paper.With the damping 24 hours under constant temperature and humidity (20 ℃, 65% relative concentration) environment of the ph test paper ph of gained.
(4) evaluation of record-paper
With the damping 24 hours under constant temperature and humidity (20 ℃, 65% relative concentration) environment of the ph test paper ph of above-mentioned (3) gained, and carry out the suitable property test of following ink-jet.
(the property test method is fitted in ink-jet)
After being evaluated as ph test paper ph with above-mentioned sizing efficiency test gained and carrying out calender process of the suitable property of ink-jet, under constant temperature and humidity (20 ℃, 65% relative humidity) environment, carry out more than 24 hours after the damping, use Canon (thigh) to make Bubble Jet Printer BJ-220 JC II and carry out according to following method.The results are shown in table 3.
(a) lettering concentration test
On ph test paper ph, carry out the β printing, and the lettering concentration of deciding beat portion with MACBASE body instrumentation.The big more lettering concentration of then representing of numerical value is high more.
(b) spread and sink in paper test
On ph test paper ph that the live width of quadrature is certain straight line and literal carry out lettering, and with visual oozing out with 5 grades of straight line and literal outside line are estimated.The sample of the paper of not spreading and sinking in fully is made as 5, and ink oozes out and the sample that can't differentiate literal is made as 1.Can anti-normally used lettering quality be more than 4.
(c) back side permeability test
On ph test paper ph, carry out the β printing, ooze out degree with visual, 5 grades of inks of estimating the β lettering part back side.The back side is not had the sample that ink oozes out be made as 5, beat portion is made as 1 for the sample that is back side infiltration fully.Can anti-normally used lettering quality be more than 4.
(test example 4) foaminess test
(1) the foaminess evaluation modulation of experimental liquid
Oxidized starch (MS3800 japanese food chemical company system) is diluted to concentration 10% with water, carries out gelatinization, and in this dextrin, mix above-mentioned Cypres and salt, be modulated into coating fluid at 95 ℃.At this moment, the solid content concentration with the oxidized starch in the coating fluid, Cypres and salt is adjusted to following value.
The solid content concentration of the oxidized starch in the coating fluid: 5%
The solid content concentration of the Cypres in the coating fluid: 0.2%
The solid content concentration of the salt in the coating fluid: 0.5%
(2) the foaminess evaluation of coating fluid
With coating fluid 600 grams that above-mentioned (1) is cooperated, put into the brbble test pond of 50 centimeters of 7 centimeters of internal diameters and length, with following condition circulation, measure the height (mm) of foam.The results are shown in table 3.
60 ℃ of coating fluid temperature, 9 liters/minute of pump flows, 3 minutes circulation timei.
And in table 3, the height of foam is low more, then represents foaminess low more (gas release is few).
(test example 5) mechanical stability test
Coating fluid 50 grams that (1) of above-mentioned (test example 4) is adjusted are put into cup, carry out the stability test of 10 minutes Maron formulas with 60 ℃ of temperature, 20 kilograms of loads, rotation number 800rpm.The condensation product that the generates wire netting with 325 sieve apertures is filtered, measure the amount of separating out, and represent with percentage with respect to whole solid contents.The results are shown in table 3.
(test example 6) is for the stability test of metal ion
It is 0.2% that the dilution water of use 700ppm hardness (in CaCO3) is diluted to solid content with Cypres, is modulated into dispersion liquid.Observe the variation of this dispersion liquid state, the sample of not observing variation is made as zero, produce muddy sample a little and be made as △, produce sedimentary sample to be made as *.The results are shown in table 3.
By the evaluation result of matter paper on matter paper and the neutralized paper on the acidity of table 2 as can be known, the Cypres of embodiment is few for the PH variable effect of coating fluid, and STICKY HIT degree of sizing, that pen is write degree of sizing is more good than the Cypres of comparative example 1,3,4.
By the evaluation result of the ink-jet recording paper of table 3 as can be known, the evaluation of the lettering concentration of the Cypres of embodiment, the paper of spreading and sinking in test, back side infiltration is more good than the Cypres of comparative example 1,3,4.
By the evaluation result of table 3 as can be known, the Cypres of embodiment is lower than the foaminess of the Cypres of whole comparative examples, and mechanical stability is except comparative example 5, the Cypres of embodiment is more better than whole Cypres, for the stability of metal ion, the Cypres of embodiment is more better than the Cypres of whole comparative examples.
One of [table 1] ()
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | ||
| Dispersant before the polymerization | The kind weight portion | Shellac 8 | Shellac 12 | Shellac 5 | ????JS-2 ????2 | ????JS-2 ????2 | Shellac 12 | Shellac 7 |
| The kind weight portion | ????JS-2 ????1 | ????MS-60 ????1 | ||||||
| The nonionic hydrophilic monomer | The kind weight portion | ????AAm ????8 | ????AAm ????8 | ????AAm ????10 | ????AAm ????10 | ????AAm ????5 | ????AAm ????20 | ????AAm ????10 |
| The anionic property monomer | The kind weight portion | ????MAA ????2 | ????AA ????2 | ????MAA ????2 | ????MAA ????7 | |||
| Hydrophobic monomer | The kind weight portion | ????St ????40 | ????iBMA ????40 | ????nBMA ????60 | ????iBMA ????55 | ????St ????50 | ????iBMA ????40 | ????nBMA ????70 |
| The kind weight portion | ????n?BA ????60 | ????nBA ????60 | ????nBA ????40 | ????iBA ????45 | ????iBA ????50 | ????nBA ????60 | ????iBA ????30 | |
| Dispersant after the polymerization | The kind weight portion | ????S-1 ????20 | ????S-2 ????15 | ????S-2 ????20 | ????S-2 ????20 | ????S-2 ????20 | ????S-2 ????15 | ????S-1 ????30 |
| The kind weight portion | Shellac 5 | Shellac 7 | Shellac 5 | |||||
| Solid content (%) | ????25.3 | ????25.0 | ????25.2 | ????24.7 | ????24.8 | ????25.0 | ????23.5 | |
[table 1] (two)
| Embodiment 8 | Embodiment 9 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | ||
| Dispersant before the polymerization | The kind weight portion | Shellac 13 | Shellac 3 | Shellac 8 | Shellac 12 | ????JS-2 ????2 | ???S-1 ???50 |
| The kind weight portion | ????JS-2 ????1 | ||||||
| The nonionic hydrophilic monomer | The kind weight portion | ????AAm ????12 | ????AAm ????8 | ???AAm ???8 | |||
| The anionic property monomer | The kind weight portion | ????MAA ????2 | ???MAA ???2 | ????MAA ????2 | ???MAA ???2 | ||
| Hydrophobic monomer | The kind weight portion | ????nBMA ????60 | ????St ????40 | ????St ????40 | ???iBMA ???40 | ????St ????50 | ???St ???50 |
| The kind weight portion | ????nBA ????40 | ????nBA ????60 | ????nBA ????60 | ???nBA ???60 | ????iBA ????50 | ???iBA ???50 | |
| Dispersant after the polymerization | The kind weight portion | ????S-2 ????15 | ????S-2 ????15 | ????S-1 ????20 | |||
| Solid content (%) | ????25.1 | ????25.0 | ????23.5 | ???25.0 | ????25.2 | ???24.7 | |
And following material is represented in the abbreviation in the table.
AAm: acrylamide
MAA: methacrylic acid
AA: acrylic acid
St: styrene
IBMA: isobutyl methacrylate
NBMA: n-BMA
IBA: isobutyl acrylate
NBA: n-butyl acrylate
MS-60:ANTOX MS-60 (Japanese emulsifying agent corporate system) (reactive emulsifier with methacryl has following structural formula)
Wherein, in above-mentioned formula, R represents alkyl, and n represents integer, and X represents the alkali metal of sodium etc.
JS-2:ELEMINOL JS-2 (Sanyo's system of changing into) (have allylic reactive emulsifier, have following structural formula)
Shellac: N811 (the abundant Shellac of qi (strain) system), the shellac in the table all carries out 100% neutralization with KOH.
[table 2]
| Test example 1 | Test example 2 | |||||
| Coating fluid pH8 | Coating fluid pH6 | Coating fluid pH8 | ||||
| STICKY HIT degree of sizing | Pen is write degree of sizing | STICKY HIT degree of sizing | Pen is write degree of sizing | STICKY HIT degree of sizing | Pen is write degree of sizing | |
| Embodiment 1 | ????28 | ????6 | ????27 | ????6 | ????26 | ????5 |
| Embodiment 2 | ????29 | ????6 | ????26 | ????5 | ????26 | ????5 |
| Embodiment 3 | ????25 | ????5 | ????25 | ????5 | ????23 | ????5 |
| Embodiment 4 | ????22 | ????4 | ????20 | ????4 | ????19 | ????4 |
| Embodiment 5 | ????20 | ????4 | ????18 | ????4 | ????18 | ????4 |
| Embodiment 6 | ????19 | ????4 | ????17 | ????4 | ????18 | ????4 |
| Embodiment 7 | ????18 | ????4 | ????17 | ????4 | ????18 | ????4 |
| Embodiment 8 | ????18 | ????4 | ????17 | ????4 | ????17 | ????4 |
| Embodiment 9 | ????17 | ????4 | ????15 | ????4 | ????15 | ????4 |
| Comparative example 1 | ????12 | ????2 | ????6 | ????2 | ????9 | ????2 |
| Comparative example 2 | ????26 | ????5 | ????24 | ????5 | ????23 | ????5 |
| Comparative example 3 | ????8 | ????2 | ????7 | ????2 | ????5 | ????1 |
| Comparative example 4 | ????9 | ????2 | ????6 | ????2 | ????3 | ????1 |
| Comparative example 5 | ????24 | ????5 | ????16 | ????5 | ????21 | ????3 |
[table 3]
| Test example 3 | Test example 4 | Test example 5 | Test example 6 | |||
| Lettering concentration | The paper degree of spreading and sinking in | Back side infiltration | Foaminess | The stability of machinery | Metal ion stability | |
| Embodiment 1 | ????1.34 | ????6 | ????6 | ????19 | ????＜0.5％ | ????○ |
| Embodiment 2 | ????1.34 | ????6 | ????6 | ????14 | ????＜0.5％ | ????○ |
| Embodiment 3 | ????1.33 | ????6 | ????6 | ????21 | ????＜0.5％ | ????○ |
| Embodiment 4 | ????1.30 | ????5 | ????5 | ????25 | ????＜0.5％ | ????○ |
| Embodiment 5 | ????1.29 | ????5 | ????5 | ????40 | ????＜0.5％ | ????○ |
| Embodiment 6 | ????1.30 | ????5 | ????5 | ????36 | ????＜0.5％ | ????○ |
| Embodiment 7 | ????1.28 | ????5 | ????5 | ????30 | ????＜0.5％ | ????○ |
| Embodiment 8 | ????1.25 | ????5 | ????4 | ????53 | ????＜0.5％ | ????○ |
| Embodiment 9 | ????1.24 | ????4 | ????4 | ????49 | ????＜0.5％ | ????○ |
| Comparative example 1 | ????1.17 | ????2 | ????2 | ????74 | ????1.3％ | ????× |
| Comparative example 2 | ????1.32 | ????5 | ????5 | ????70 | ????0.9％ | ????△ |
| Comparative example 3 | ????1.17 | ????2 | ????2 | ????130 | ????3.5％ | ????× |
| Comparative example 4 | ????1.15 | ????2 | ????2 | ????90 | ????1.0％ | ????△ |
| Comparative example 5 | ????1.30 | ????5 | ????5 | ????150 | ????＜0.5％ | ????× |
Utilizability on the industry
The mechanical stability of Cypres of the present invention, low foaming and storage stability are all good, can improve acidic paper to the sizability of neutralized paper, and for the information paper using, particularly ink-jet paper using has good adaptive, and the low foaming of coating fluid, with other share medicine intermiscibility and for the molten excellent in stability of depositing metal ion.
Claims (11)
1. Cypres is characterized in that: in the presence of the alkali metal salt (a) of shellac, in the reactant liquor of nonionic hydrophilic monomer (b) and hydrophobic monomer (d) polymerization gained, mix macromolecule dispersing agent (e) and then can obtain.
2. Cypres, it is characterized in that: in the presence of the alkali metal salt (a) of shellac, in the reactant liquor of nonionic hydrophilic monomer (b), anionic property monomer (c) and hydrophobic monomer (d) polymerization gained, mix macromolecule dispersing agent (e) and then can obtain.
3. Cypres, it is characterized in that: in the presence of the material with surface-activity ability (f) except the alkali metal salt (a) of shellac, in the reactant liquor of nonionic hydrophilic monomer (b) and hydrophobic monomer (d) polymerization gained, mix the alkali metal salt (a) and the macromolecule dispersing agent (e) of shellac and then can obtain.
4. Cypres, it is characterized in that: in the presence of the material with surface-activity ability (f) except the alkali metal salt (a) of shellac, in the reactant liquor of nonionic hydrophilic monomer (b), anionic property monomer (c) and hydrophobic monomer (d) polymerization gained, mix the alkali metal salt (a) and the macromolecule dispersing agent (e) of shellac and then can obtain.
5. Cypres is characterized in that: comprise:
With alkali metal salt (a), nonionic hydrophilic monomer (b) and the hydrophobic monomer (d) of shellac as the polymer of repetitive or with nonionic hydrophilic monomer (b), anionic property monomer (c) and hydrophobic monomer (d) polymer as repetitive;
Macromolecule dispersing agent (e).
6. as claim 3 or 4 described Cypres, it is characterized in that: the material with surface-activity ability (f) except the alkali metal salt (a) of shellac is that to have the surface-activity of polymerism base neat.
7. Cypres as claimed in claim 6 is characterized in that: the surfactant with polymerism base is to have methacryl and/or allylic reactive emulsifier.
8. as any described Cypres in the claim 1～5, it is characterized in that: described nonionic hydrophilic monomer (b) is select from the group that (methyl) acrylamide, acrylonitrile and (methyl) hydroxyalkyl acrylate are formed at least a.
9. as any described Cypres in the claim 1～5, it is characterized in that: described hydrophobic monomer (d) is select from the group that styrene derivative and (methyl) alkyl acrylate are formed at least a.
10. as any described Cypres in the claim 2,4 and 5, it is characterized in that: described anionic property monomer (c) is the monomer with carboxylic acid group.
11. as any described Cypres in the claim 1～5, it is characterized in that: described macromolecule dispersing agent (e) is salt and/or (methyl) acrylate based copolymer of styrene-propene acid based copolymer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP37294399 | 1999-12-28 | ||
| JP372943/1999 | 1999-12-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1402805A true CN1402805A (en) | 2003-03-12 |
| CN1208517C CN1208517C (en) | 2005-06-29 |
Family
ID=18501304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00816596 Expired - Fee Related CN1208517C (en) | 1999-12-28 | 2000-12-27 | Surface-sizing agent |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP4730641B2 (en) |
| CN (1) | CN1208517C (en) |
| AU (1) | AU2227901A (en) |
| TW (1) | TW571013B (en) |
| WO (1) | WO2001048313A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100340717C (en) * | 2004-09-13 | 2007-10-03 | 上海东升新材料有限公司 | Nano emulsion type surface gluing agent |
| CN101487206B (en) * | 2008-01-16 | 2010-09-29 | 周静波 | Production method for surface sizing agent of colored ink-jet print paper |
| CN102517992A (en) * | 2011-12-14 | 2012-06-27 | 江南大学 | Compound surface reinforcing agent for packaging paperboard and method for preparing same |
| CN104411879A (en) * | 2012-06-29 | 2015-03-11 | 松本油脂制药株式会社 | Fiber sizing agent and use applications thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4560756B2 (en) * | 2001-01-24 | 2010-10-13 | 星光Ｐｍｃ株式会社 | Surface sizing agent and method for producing the same |
| CN103739788A (en) * | 2013-12-20 | 2014-04-23 | 天津商业大学 | Preparation method of surface sizing agent |
| CN106320076B (en) * | 2016-10-11 | 2018-03-16 | 宁波广博纸制品有限公司 | A kind of preparation method of glue used in paper-making |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5015883B2 (en) * | 1972-09-21 | 1975-06-09 | ||
| JPS4993430A (en) * | 1972-11-01 | 1974-09-05 | ||
| JPS55157611A (en) * | 1979-05-25 | 1980-12-08 | Sakata Shokai Ltd | Preparation of aqueous dispersion |
| JPS6037240B2 (en) * | 1979-12-17 | 1985-08-24 | 近代化学工業株式会社 | Strengthening treatment agent for cardboard base paper |
| JPS60170605A (en) * | 1984-02-16 | 1985-09-04 | Agency Of Ind Science & Technol | Preparation of ultrafine particulate already crosslinked polymer latex |
| JP3102958B2 (en) * | 1992-08-17 | 2000-10-23 | 日石三菱株式会社 | Papermaking sizing agent |
| JP3382006B2 (en) * | 1994-03-22 | 2003-03-04 | 近代化學工業株式会社 | Method for producing dispersant for sizing agent and aqueous emulsion sizing agent |
| JP3028308B1 (en) * | 1998-11-04 | 2000-04-04 | 日本ピー・エム・シー株式会社 | Surface sizing agent and method for producing the same |
| JP4395817B2 (en) * | 1999-01-27 | 2010-01-13 | 星光Ｐｍｃ株式会社 | Method for producing surface sizing agent and coated paper |
-
2000
- 2000-12-27 AU AU22279/01A patent/AU2227901A/en not_active Abandoned
- 2000-12-27 JP JP2001548809A patent/JP4730641B2/en not_active Expired - Fee Related
- 2000-12-27 CN CN 00816596 patent/CN1208517C/en not_active Expired - Fee Related
- 2000-12-27 WO PCT/JP2000/009317 patent/WO2001048313A1/en active Application Filing
- 2000-12-28 TW TW89128114A patent/TW571013B/en not_active IP Right Cessation
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100340717C (en) * | 2004-09-13 | 2007-10-03 | 上海东升新材料有限公司 | Nano emulsion type surface gluing agent |
| CN101487206B (en) * | 2008-01-16 | 2010-09-29 | 周静波 | Production method for surface sizing agent of colored ink-jet print paper |
| CN102517992A (en) * | 2011-12-14 | 2012-06-27 | 江南大学 | Compound surface reinforcing agent for packaging paperboard and method for preparing same |
| CN102517992B (en) * | 2011-12-14 | 2014-02-19 | 江南大学 | Compound surface reinforcing agent for packaging paperboard and method for preparing same |
| CN104411879A (en) * | 2012-06-29 | 2015-03-11 | 松本油脂制药株式会社 | Fiber sizing agent and use applications thereof |
| CN104411879B (en) * | 2012-06-29 | 2016-06-29 | 松本油脂制药株式会社 | Fiber paste and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4730641B2 (en) | 2011-07-20 |
| CN1208517C (en) | 2005-06-29 |
| AU2227901A (en) | 2001-07-09 |
| WO2001048313A1 (en) | 2001-07-05 |
| TW571013B (en) | 2004-01-11 |
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