CN102472019A - Sizing agent composition - Google Patents

Sizing agent composition Download PDF

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Publication number
CN102472019A
CN102472019A CN2010800357911A CN201080035791A CN102472019A CN 102472019 A CN102472019 A CN 102472019A CN 2010800357911 A CN2010800357911 A CN 2010800357911A CN 201080035791 A CN201080035791 A CN 201080035791A CN 102472019 A CN102472019 A CN 102472019A
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China
Prior art keywords
acid
latex
oxetanone compound
alkenyl succinic
quality
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CN2010800357911A
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Chinese (zh)
Inventor
藤原康史
白石诚
冲永俊治
伊藤贤一
稻田幸督
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Nippon Pmc K K
Seiko PMC Corp
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Nippon Pmc K K
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Publication of CN102472019A publication Critical patent/CN102472019A/en
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    • 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
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/14—Carboxylic acids; Derivatives thereof
    • D21H17/15—Polycarboxylic acids, e.g. maleic acid
    • D21H17/16—Addition products thereof with hydrocarbons
    • 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
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/17—Ketenes, e.g. ketene dimers

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Abstract

Provided is an alkenyl succinic anhydride sizing agent composition with superior water resistance and emulsion stability that does not soil easily during use, said alkenyl succinic anhydride sizing agent composition being an emulsion obtained by emulsifying a mixture comprising 60-95 wt.% of an alkenyl succinic anhydride that is liquid at 25 DEG C and 5-40 wt.% of a 2-oxetanone compound that is liquid at 25 DEG C, the 2-oxetanone compound preferably fulfilling (1) and (2) below: (1) a 2-oxetanone compound obtained from a fatty acid mixture comprising a C8-10 fatty acid at 8-20 wt.% and a C12-18 fatty acid at 92-80 wt.% (2) a 2-oxetanone compound obtained from a fatty acid mixture as described in (1), which comprises an unsaturated fatty acid at 2 wt.% or less.

Description

The sizing agent constituent
Technical field
The present invention relates to the sizing agent constituent, being specifically related to the alkenyl succinic anhydrides is the sizing agent constituent of main component.
Background technology
Alkenyl succinic anhydrides (Alkenyl Succinic Anhydride, below abbreviate ASA sometimes as) is given the sizing agent of resistance to water as paper feeding and is being widely used in field of papermaking.Equally, the 2-oxetanone compound (2-oxetanone) with alkyl ketene dimer (alkyl ketene dimer) representative is also being used as sizing agent.But, compare with the 2-oxetanone, ASA have copy paper after dryer sizing degree more excellent, to the also more excellent characteristic of the sizing efficiency of old paper paper pulp or mechanical pulp.In actual paper technology, the latex that ASA is scattered in as emulsification in the aqueous medium uses.Because ASA is oily mater under normal temperature or warm-up mode, so can carry out emulsification (for example referring to patent documentation 1) through the existing emulsification method that has adopted emulsifying dispersant and homogenizer.
As the emulsifying dispersant that is used for emulsification ASA, the someone has proposed for example: use the method (for example referring to patent documentation 1 and 2) of cationic starch paste liquid, the method (for example referring to patent documentation 3 and 4) of using the cation property copolymer of ethene system or (methyl) acrylamide, the method (for example referring to patent documentation 5) of using the grafting cationic starch that the monomer class glycerol polymerization that will contain (methyl) acrylamide forms in cationic starch and the method (such as referring to patent documentation 6 and 7) of use both sexes acrylamide polymer.
Yet, even used above-mentioned emulsifying dispersant, ASA still cause easily with contact with moisture due to hydrolysis; Cause that the sizing agent effect to paper reduces; Moreover, the ASA hydrolysate also constitutes the dirty reason of paper technology easily, still also is not can gratifying material.
As the emulsified dispersed liquid quality is carried out improved additive method, the someone has proposed to use the method (for example referring to patent documentation 8) of the ASA with particular chemical structure, the method (for example referring to patent documentation 9) that mixing is dissolved in the lyophobic dust of ASA mutually or the method (for example referring to patent documentation 10) of using the applying glue dispersion liquid that contains ASA and 2-oxetanone compound etc.In the above-mentioned patent documentation 10; Record " it is thus clear that the part of hydrophobicity sizing agent also is fit to be used in this paper wadding: be not only AKD and (annotate: other sizing agents that alkyl ketene dimer) also are added with the sort of suitable raising hydrophobicity of alkenyl succinic anhydrides (ASA).Yet ... Owing in paper technology, need add the ASA filler effectively, mark problem occur polluting.Therefore, as if this glue applying method is not by preferably." (the 7th page referring to patent documentation 10 several 21 is walked to 15 row down).It is thus clear that the sizing agent that contains the ASA of high rate can not understood by preferred this understanding.That is, insufficient to the sizing efficiency of paper, hydrolysate causes is not dirtyly fully solved.
Also have, in patent documentation 11, disclose a kind of paper gluing agents (referring to claim 1 in claims of patent documentation 11) that contains certain cationic property starch, liquid 2-oxetanone compound, ASA and water.Cationic starch in the paper gluing agents that patent documentation 11 is put down in writing is effectively (referring to the 12nd page of patent documentation 11) as emulsifying agent with keeping accessory agent.In addition, the sizing agent that patent documentation 12 is put down in writing, relating to 2-oxetanone compound is the improvement technology of the sizing agent of main body, does not solve the problem that above-mentioned ASA has fully.
The prior art document
Patent documentation
Patent documentation 1: No. 3821069 communiques of United States Patent (USP) (it is corresponding with it that the spy opens clear 49-94907 communique)
Patent documentation 2: special public clear 39-002305 communique
Patent documentation 3: the spy opens clear 60-246893 communique
Patent documentation 3: special public clear 39-002305 communique
Patent documentation 4: special fair 6-33597 communique
Patent documentation 5: the spy opens flat 9-111692 communique
Patent documentation 6: special fair 3-4247 communique
Patent documentation 7: the spy opens clear 58-45731 communique
Patent documentation 8: the spy opens flat 6-248596 communique (speciallyying permit No. 2915241 communique)
Patent documentation 9: No. 6576049 communiques of United States Patent (USP)
Patent documentation 10: specially permit communique No. 3834699
Patent documentation 11: special table 2000-506941 communique
Patent documentation 12: special table 2002-517638 communique
Summary of the invention
Problem to be solved by this invention
The object of the invention just is to provide that a kind of resistance to water is excellent, stability of emulsion is excellent, be difficult for producing dirty sizing agent constituent when using.
The means of dealing with problems
Result through constantly studying with keen determination such as the inventor; Find out: the 2-oxetanone compound through synthesizing the aliphatic acid by specific composition is mixed in alkenyl succinic anhydrides with specific ratios; Just can access resistance to water excellence, the excellent sizing agent constituent of stability of emulsion, accomplish the present invention therefrom.
That is the means that, address the above problem are following:
< 1>a kind of sizing agent constituent; It is characterized in that, be that the mixture that contains under 25 ℃ of 60～95 quality % under 25 ℃ for the alkenyl succinic anhydrides of liquid state and 5～40 quality % for the 2-oxetanone compound of liquid state is carried out the emulsion that emulsification obtains.
< 2>according to the sizing agent constituent of above-mentioned < 1 >; It is characterized in that 2-oxetanone compound is that raw material obtains with the fatty acid mixt, in this fatty acid mixt; The aliphatic acid of carbon number 8～10 is 8～20 quality %, and the aliphatic acid of carbon number 12～18 is 92～80 quality %.
According to the sizing agent constituent of above-mentioned < 1>or < 2 >, it is characterized in that < 3>2-oxetanone compound is that fatty acid mixt below the 2 quality % is that raw material obtains with unsaturated fatty acid content.
< 4>according to any sizing agent constituent in above-mentioned < 1>to < 3 >, wherein, alkenyl succinic anhydrides is: the addition reaction product of the carbon number that contains inner the isomerizing olefins alkene below 24 and maleic anhydride more than 16.
< 5>according to any sizing agent constituent in above-mentioned < 1>to < 4 >, it is characterized in that, is a kind of emulsion of mixture; This mixture contains: 25 ℃ is the surfactant of 0.1～5 parts by mass for liquid 2-oxetanone compound and total 100 parts by mass of above-mentioned relatively alkenyl succinic anhydrides and above-mentioned 2-oxetanone compound down for liquid alkenyl succinic anhydrides, 25 ℃ down.
< 6>according to any sizing agent constituent in above-mentioned < 1>to < 5 >, wherein, the average grain diameter of decentralized photo is below the above 1.5 μ m of 0.5 μ m in the above-mentioned emulsion.
The effect of invention
The present invention can provide that a kind of resistance to water is excellent, stability of emulsion is excellent.Be difficult for producing dirty sizing agent constituent during use.
As above-mentioned alkenyl succinic anhydrides, so long as 25 ℃ be down liquid getting final product, but the addition reaction product of the carbon number that preferably contains inner the isomerizing olefins alkene below 24 and maleic anhydride more than 16.At this, inner isomerizing olefins is meant through two keys someway and more leans on the inner chain hydrocarbon that exists of carbochain than alpha-position, rather than alpha-olefin (position of double bond is in the alkene on 1 of connection alkene and 2 bit positions).Also have, in the present invention, inner isomerizing olefins, as long as its pair key is not formed on the α position, the carbon location that has two keys to form does not constitute any problem for realization the object of the invention.
Specifically can give an example out inner isomerization 16 allyl succinic anhydrides (hexadecenyl Succinic Anhydride), inner isomerization 18 allyl succinic anhydrides (octadecenyl Succinic Anhydride), inner isomerization 20 allyl succinic anhydrides (icosenyl Succinic Anhydride), inner isomerization 22 allyl succinic anhydrides (docosenyl Succinic Anhydride), inner isomerization 24 allyl succinic anhydrides (tetracosenyl Succinic Anhydride) etc.; These can use separately also and can a plurality of mixing use.Also have, the formed mixture that contains multiple inner isomerizing olefins base succinyl oxide of multiple alpha-olefin and succinyl oxide reaction also can use as suitable inside isomerizing olefins base succinyl oxide.
The carbon number of above-mentioned alkene is more than 16 24 when following, and the sizing agent component is given the effect excellence to the applying glue of paper, so preferred.Also have, when alkenyl succinic anhydrides is that ASA is difficult to hydrolysis when containing the addition reaction product of alkene and maleic anhydride of inner isomerizing olefins, the sizing agent constituent is given effect to the applying glue of paper and is reduced and alleviate, so preferably.
About inner isomerizing olefins, two keys are than more inner of the alpha-position (position that connects 1 carbon and 2 carbon) of alkene and there is a thing, at alkene 1During H-NMR analyzes, can be through near 5.4ppm, occurring obtaining affirmation because of the peak value that inner isomerizing olefins produces.Otherwise, when containing alpha-olefin, alkene 1During H-NMR analyzes, occur obtaining confirming near the 5.0ppm with near the 5.8ppm because of the peak value that alpha-olefin produces.Also have,, can also obtain the ratio of alpha-olefin and inner isomerizing olefins according to the integrated value of above-mentioned peak value.
Inner isomerizing olefins can make through common methodology of organic synthesis is synthetic, for example can obtain through utilizing the silica alumina series catalysts that alpha-olefin is carried out inner isomerization.Though through common methodology of organic synthesis alpha-olefin being carried out inside isomerizing olefins that inner isomerization obtains is the mixture that position of double bond is formed at the inside isomerizing olefins that all places such as 2 of carbochain and 3 obtain; In the present invention, about the mixture of the inside alkene that forms through isomerization reaction, promptly inner isomerizing olefins; The concrete position of double bond of its inner alkene can be specific, also has, so long as the mixture of inner alkene; Each internal chain also can be specific; And, so long as do not hinder realization the object of the invention, also can contain alpha-olefin.About containing the inside isomerizing olefins of various inner alkene, the alpha-olefin content of allowing is below the 10 quality %.
As above-mentioned maleic anhydride is added the method that is formed in above-mentioned alkene and obtains alkenyl succinic anhydrides, can be suitable for common methodology of organic synthesis.For example, under nitrogen environment, little by little add maleic anhydride, stir and to obtain alkenyl succinic anhydrides in 6～10 hours toward the alkene that has been heated to 210 ℃.
The 2-oxetanone compound that the present invention is used, normal pressure and 25 ℃ of following getting final product for liquid state.Do not become liquid 2-oxetanone compound under normal pressure and 25 ℃, can't realize the object of the invention owing to some problems can occur.These problems comprise: need carry out the heated and stirred operation when mixing with ASA for a long time; Cause in 25 ℃ of keepings that 2-oxetanone compound separates out as solid even if evenly mix also easily under normal pressure with ASA; Unstable easily with the emulsion of the mixture of ASA and cause cohesion and separate etc.At least a, the preferably two or more mixture of preferred 2-oxetanone compound in the middle of one group of aliphatic acid, selecting; And be that the normal pressure that produces from these aliphatic acid and 25 ℃ are liquid 2-oxetanone compound down, the normal pressure that preferably produces from the mixture of aliphatic acid and 25 ℃ are liquid 2-oxetanone compound mixture down.Above-mentioned one group of aliphatic acid comprises: the unsaturated dicarboxylic of the unsaturated monocarboxylic acid of the saturated monocarboxylic acid of carbon number 8～30, carbon number 8～30, the saturated dicarboxylic acid of carbon number 6～44 and carbon number 6～44.More preferably such 2-oxetanone compound: the alkyl ketene dimer of contain alkyl ketene dimer, making by the aliphatic acid that contains branching aliphatic acid such as isostearic acid and utilize the alkyl ketene dimer of making as the aliphatic acid of fatty acid mixt from the aliphatic acid manufacturing that contains unrighted acids such as oleic acid or linoleic acid, and normal pressure and 25 ℃ are liquid 2-oxetanone compound down.In the above-mentioned fatty acid mixt, the aliphatic acid of the aliphatic acid of carbon number 8 and carbon number 10 accounts for 8～20 quality %, and the aliphatic acid of carbon number 12～18 accounts for 92～80 quality %, and unrighted acid accounts for more than the 2 quality %.
These are preferred, because have following advantage: just become uniform admixture easily through slow stirring of short time when mixing with ASA; Mixture also has, even also can be kept uniform state 25 ℃ of down long-time keepings; Further and the latex excellent storage stability of the mixture of ASA.
As above-mentioned concrete raw material, the crowd that saturated monocarboxylic acid can be given an example out and be made up of caproic acid, caprylic acid, capric acid, n-nonanoic acid, stearic acid, isostearic acid, myristic acid, palmitic acid, pentadecanoic acid, hendecanoic acid, dodecylic acid, tridecanoic acid, nonadecylic acid, arachic acid, behenic acid and this a few mixture; Unsaturated monocarboxylic acid can give an example out oleic acid, linoleic acid, dodecenoic acid, tetradecenoic acid, gaidic acid, octadecadienoic acid, octatecatrienoic acid, eicosenoic acid, eicosatetraenoic acid, docosenoic acid, clupanodonic acid and this a few mixture; As raw material, the aliphatic acid that the aliphatic acid of preferred carbon number 8 and carbon number 10 accounts for 8～20 quality %, carbon number 12～18 accounts for the fatty acid mixt of 92～80 quality %, because of its 25 ℃ down for liquid, and sizability is excellent.Also preferred aliphatic acid by the caprylic acid that resembles carbon number 8～18 (carbon number 8), capric acid (carbon number 10), dodecylic acid (carbon number 12), myristic acid (carbon number 14), palmitic acid (carbon number 16), stearic acid (carbon number 18), oleic acid (carbon number 18), linoleic acid (carbon number 18) constitutes in the middle of these; Preferred dodecylic acid and content of myristic acid are at 50～80 quality % of raw material.Also more preferably the aliphatic acid of carbon number 8 and carbon number 10 is 8～20 quality %; And the aliphatic acid of carbon number 8 is that the aliphatic acid of 3～10 quality %, carbon number 10 is 3～12 quality %; The aliphatic acid of carbon number 12 and carbon number 14 is 54～78 quality %, and the aliphatic acid of carbon number 16 and carbon number 18 is 6～37 quality %.Further, be raw material more preferably also:, converted the alkenyl of fatty acid distribution of coconut oil to through hydrogenation reaction the aliphatic acid of alkyl for satisfying above-mentioned condition with such aliphatic acid.
The above-mentioned hydrogenation reaction that contains the unsaturated carboxylic acid raw material is the general reduction reaction of making reductant with hydrogen; Usually mainly be with metal superfine powder such as nickel, cupric oxide chromium, ruthenium, palladium, rhodium, platinum, or the thing that is adsorbed onto these powder behind the indissolubility carriers such as activated carbon, aluminium oxide, diatomite be catalyst, can enough general methods carry out.
Above-mentioned 2-oxetanone compound can be synthetic through common methodology of organic synthesis with above-mentioned raw materials, can also easily from the market sale product, obtain.For example octadecyl ketene dimer (stearyl ketene dimer) obtains through method in this way: make chlorination reactions such as stearic acid and phosgene, phosphorus trichloride, thionyl chloride; Form 18 phosgenes (Stearic acid chloride); After then carrying out desalination acid, remove triethylamine hydrochloride and get final product with triethylamine.
In addition, the preferred 2-oxetanone of the present invention compound is as above-mentioned, owing to the fatty acid mixt reaction is obtained, so be the mixture of multiple 2-oxetanone compound.
The ratio of unrighted acid is in the 2 quality % in the middle of the aliphatic acid that preferred 2-oxetanone compound uses, because this can prevent two key oxidations, helps storage stability, dispersion stabilization and the sizability of sizing agent constituent.
Among the present invention; Through with above-mentioned alkenyl succinic anhydrides with have the 2-oxetanone compound that above-mentioned mixing forms and use by the emulsifying mixture that special ratios mixes, can obtain to improve sizing efficiency, the raising aqueous liquid dispersion is stable and reduce dirty effect.The mixed proportion of alkenyl succinic anhydrides and 2-oxetanone compound with above-mentioned mixing composition; Must be in alkenyl succinic anhydrides: have the scope of mixing the 2-oxetanone compound formed=60: 40～95: 5, be preferably 70: 30～90: 10.If 2-oxetanone compound surpasses above-mentioned scope, also poor when then the sizing efficiency ratio uses alkenyl succinic separately, this is worthless.And if 2-oxetanone compound is lower than above-mentioned scope, then can't see sizing efficiency, stability and reduce dirty effect, also be worthless.
Among the present invention, 2-oxetanone compound and alkenyl succinic anhydrides compatibility are excellent, and both can mix under any temperature conditions so long as liquid, but preferably in the mixing of heating below 100 ℃.If reach the high temperature more than 100 ℃, then because of heat goes bad, variable color may appear, as the effect reduction of sizing agent etc.Also have, when the mixing, in stirring, divide hydrolysis or modification, preferably under moisture free environment such as dry air, nitrogen, argon gas, mix because of water in air in order to prevent alkenyl succinic anhydrides and 2-oxetanone compound.
Sizing agent constituent of the present invention compared with using alkenyl succinic anhydrides and 2-oxetanone compound respectively individually, has been seen the excellent effect of sizability.This is considered to owing to except the effect of above-mentioned inhibition alkenyl succinic hydrolysis, produced again because of both sides' molecular mixing and the directed cause that has improved this effect of hydrophobicity.
Sizing agent constituent of the present invention is liquid at normal temperatures, also is dissolvable in water behind the toluene equal solvent as the varnish coating so can directly be coated with.But see from operation property, preferably use as aqueous liquid dispersion.Aqueous liquid dispersion can adopt surfactant or various macromolecule water dispersant, carries out emulsification through known emulsification method and disperses to modulate.In addition, the modulation of aqueous liquid dispersion is reduced to minimum this purpose from the performance that causes because of hydrolysis that makes alkenyl succinic anhydrides, preferably before using, just disperses, and perhaps sends into emulsifier unit modulation aqueous liquid dispersion continuously, uses continuously with pump.
In the present invention, preferably further mixed surfactant mixtures again in the mixture to alkenyl succinic anhydrides and 2-oxetanone compound and carried out emulsification,, and copied the paper apparatus and be difficult to adhere to dirt because this can improve emulsibility.The use amount of the surfactant that the mixture of above-mentioned the sort of alkenyl succinic anhydrides and 2-oxetanone compound adds (following abbreviate as sometimes to mix use surfactant) is preferred: total 100 parts by mass of relative alkenyl succinic anhydrides and 2-oxetanone compound are 0.01～10 parts by mass; 0.1～5 parts by mass more preferably.If the amount with surfactant of mixing is too much; Then when chain of custody alkenyl succinic anhydride, 2-oxetanone compound and surfactant mixtures; Mixture absorbs airborne moisture easily; Promote the alkenyl succinic anhydrides hydrolysis sometimes, can cause as the alkenyl succinic pollution of hydrolysate and copy paper apparatus reduction sizability.The amount with surfactant of mixing the situation that can not be given full play to by the above-mentioned advantage that mixing brings then possibly occur as if very few.
Mix and to use known in the past cationic surfactant, amphoteric surfactant, anionic surfactant or nonionic surfactant with surfactant.These can use more than a kind or 2 kinds.
Above-mentioned cationic surfactant for example can be enumerated: chain alkyl amine salt, modification amine salt, tetraalkyl ammonium salt, trialkyl benzene quaternary ammonium salt (trialkyl benzil salt), Fixanol, alkyl quinoline salt (alkyl quinolinium salt), alkyl sulfonium salt (alkyl sulfonium salt) etc.It is surfactant that above-mentioned amphoteric surfactant for example can be enumerated various betaines.
Above-mentioned anionic surfactant for example can enumerate: alkylsulfonate; Alkyl sulfate salt; Alkyl phosphate salt; Polyoxyalkylene alkyl sulfate salt (polyoxyalkylene alkyl sulfate); Polyoxyalkylene alkyl aryl sulfate salt (polyoxyalkylene alkyl aryl sulfate); Polyoxyalkylene aralkyl aromatic yl acid ester salt (polyoxyalkylene aralkyl aryl sulfate); Alkylaryl sulfonates (alkyl aryl sulfonate); Polyoxyalkylene alkyl phosphate salt and various sulfosuccinate are surfactant etc.
Above-mentioned nonionic surfactant can be enumerated: sorbitan fatty acid ester and gather the alkyl epoxy additives; Fatty acid polyglycol diethyl alcohol ester; Various alkyl epoxy type nonionic surfactant (the PEO fatty acid esters that gather; The PEO fatty acid amide; The PEO fatty acid amine; PEO aliphatic mercaptan; Gather the oxireme alkyl aryl ether; Oxirane propylene oxide block polymer; Gather the oxireme alkyl aryl ether; Polyoxyethylene distyrene phenolic ether phosphate etc.).
Also preferred anionic surfacant, nonionic surfactant in the middle of these, particularly, preferred dialkyl sodium sulfosuccinate salt or gather the oxireme alkyl ether phosphate.
Mixing both can mix when combination chain alkenyl succinic anhydride and the 2-oxetanone compound with surfactant simultaneously; Also can before emulsification, be mixed in the mixture of alkenyl succinic anhydrides and 2-oxetanone compound continuously, but preferably be pre-mixed in the mixture of alkenyl succinic anhydrides and 2-oxetanone compound.
As emulsifier unit; Not special restriction; As long as can be from the used alkenyl succinic anhydrides of the present invention, 2-oxetanone compound, as required and the dispersion liquid that the surfactant that uses or various aqueous high molecular dispersant and water etc. are modulated into the sizing agent constituent, static(al) blender, jet mixer, mixer (blender), homogeneous blender, high-voltage high-speed spray that homogenizer, ultrasonic emulsification machine, high cut-off type rotate various mulsers such as mulser and emulsifier unit all can use.
When making the sizing agent constituent through emulsification among the present invention,, preferably use the aqueous high molecular dispersant from the excellent viewpoint of dispersion stabilization as the sizing agent constituent of emulsion.
Can enumerate water miscible various synthetic high polymer, natural polymer as the aqueous high molecular dispersant, can enumerate particularly, starch based, acrylamide polymer class, starch graft acrylamide based polymer, polyvinyl alcohol, carboxyethyl cellulose class, rubber-like, casein etc.Go back preferred starch class, acrylamide polymer, starch graft acrylamide based polymer, carboxyethyl cellulose class, polyvinyl alcohol in the middle of these.
The weight average molecular weight of aqueous high molecular dispersant is preferably more than 10,000 10,000, below 000.Weight average molecular weight was less than 10,000 o'clock, and emulsibility and dispersion stabilization may reduce.And work as weight average molecular weight greater than 10,000,000 o'clock, then the viscosity of aqueous high molecular dispersant can increase, and possibly become to be difficult to handle.
Above-mentioned starch based for example can enumerate contain primary in lifes starch such as corn, wheat, potato, rice, cassava and these starch again, the second month in a season, uncle is amino and the quaternary ammonium basic group in the cationic starch of at least a basic nitrogen selected.Can also use the two ionic starch that mixed anionic property base (for example phosphate-based etc.) at above-mentioned cationic starch.Other can also enumerate oxidized starch, dialdehyde stareh, alkyl etherification starch, starch phosphate, urea starch phosphate, hydrophobically modified starch etc.In addition, among the present invention, even do not contain the purpose that liquid cation property starch also can reach the present invention.
Can enumerate acrylamide and/or Methacrylamide as aforesaid propylene acid amides based polymer class, that is, contain above (methyl) acrylamide of 50 moles of % and also can have the water-soluble polymer of cationic base and/or anionic property base.Making this acrylamide polymer, for example can to adopt through making (methyl) acrylamide be the method for modifying that the water-soluble polymer modification of main component imports ionic base; Perhaps adopt and to contain (methyl) acrylamide and the copolymerization process of the monomer mixture that also can contain cationic monomer, anionic property monomer and other polyethylene-based monomer as required, also or adopt method that these two kinds of methods make up etc. with existing known method polymerization.
When adopting above-mentioned method of modifying, the importing of cationic base can be adopted Huffman conversion reaction, Mannich reaction and utilize the acid amides conversion reaction of polyamine; The importing of anionic property base then can be adopted hydrolysis etc.
Can enumerate as above-mentioned cationic monomer: monomer or dimeric alkylamine alkyl acrylate, monomer or dimeric alkylamine alkylmethacrylate, monomer or dimeric alkylamine alkyl methyl acrylamide, vinylpyridine, vinyl imidazole, monomer or dimeric allylamine and these mixture even also have these quaternary ammonium salt etc.
Can enumerate as above-mentioned anionic property monomer: α such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, beta-unsaturated carboxylic acid class or known various polymerizable monomer classes in addition with sulfonic group or phosphate.
As above-mentioned other vinyl monomer, also can and with can with nonionic vinyl monomers such as bridging property vinyl monomer, (methyl) acrylic acid ester, styrene, vinyl acetate such as the N hydroxymethyl acrylamide of polymerizations such as (methyl) acrylamide, methylene (two) acrylamide, 2 group monomer, 3 group monomer, 4 group monomer.
The preparation method of the acrylamide polymer class that the present invention is used can adopt existing known the whole bag of tricks.For example, to the tube equipped with a stirrer and a nitrogen inlet was put into a reaction vessel and water components of the vinyl monomer as a polymerization initiator, the hydrogen peroxide, ammonium persulfate, potassium persulfate, ammonium and hydrogen peroxide over oxide, or a peroxide and a reducing agent such as sodium bisulfite, an arbitrary combination of redox initiators, as well as further 2-2 'azobis (aminopropane) hydrochloride type water-soluble azo initiators that and the like, the reaction temperature is 40 ~ 80 ℃ the reaction was 1 to 5 hours, to obtain the acrylamide polymer.
The starch graft acrylamide based polymer that the present invention is used is to obtain having to let in the presence of the starch based can form the monomer class glycerol polymerization of aforesaid propylene acid amides based polymer class and modulate.
For example, in the cationic amidin, will contain monomer, (b) that (a) contain the cationic base and contain the monomer of anionic property base and carry out copolymerization with (c) monomer mixture of (methyl) acrylamide and can obtain.
As the concrete example of above-mentioned cationic monomer (a), can give an example: monomer or dimeric alkylamine alkyl acrylate, monomer or dimeric alkylamine alkylmethacrylate, monomer or dimeric alkylamine alkyl acrylamide, monomer or dimeric alkylamine alkyl methyl acrylamide, vinylpyridine, vinyl imidazole, monomer or dimeric allylamine and these mixture even also have these quaternary ammonium salt etc.Then can use the α of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid etc. as above-mentioned anionic property monomer (b), the beta-unsaturated carboxylic acid class has the known various polymerizable monomer classes of sulfonic group or phosphate in addition in addition.Above-mentioned modification or copolyreaction are by the known reactions operation, so can select appropriate reaction conditions arbitrarily.
As other water-soluble polymer, can use carboxyethyl cellulose class, polyvinyl alcohol, dextrin class, shitosan etc.
The not special restriction of the concentration of aqueous high molecular dispersant, addition can change addition and concentration according to purposes.But the preferred sizing agent constituent relatively of the present invention is pressed solid content than adding 0.1～4 times.
Also have, obtain the sizing agent constituent through emulsification when, preferred and with surfactant (following abbreviate emulsification sometimes as use surfactant), because can further improve emulsibility and stability.
Use surfactant as emulsification, can use above-mentioned existing known cationic surfactant, anionic surfactant, amphoteric surfactant or nonionic surfactant.These can use more than a kind or 2 kinds.
In the middle of the above-mentioned surfactant, as emulsification of the present invention with preferred nonionic surfactant of surfactant and anionic surfactant.
Above-mentioned emulsification can change addition, concentration according to purposes with the not special restriction of surfactant concentrations, addition.But the preferred sizing agent constituent relatively of the present invention is pressed solid content than using 0.3～3 quality %, because can further improve the stability of emulsibility and resulting latex like this.
Emulsification both can be pre-mixed when the aqueous high molecular dispersant also can be in emulsification with surfactant and be mixed in the aqueous high molecular dispersant continuously, but preferably was pre-mixed in the aqueous high molecular dispersant.
The specific embodiment
Embodiment
Below give an example and make example and embodiment specifies effect of the present invention.But the present invention is not limited only to these examples.
(alkenyl succinic anhydrides)
The manufacturing of (making example 1) alkenyl succinic anhydrides (A1)
With the silica alumina series catalysts with the isomerization of 1-vaccenic acid.Inside isomerization vaccenic acid mixture to gained carries out 1H-NMR analyzes, and has confirmed not contain alpha-olefin.Let inner isomerization vaccenic acid mixture 200g and maleic anhydride 86g in autoclave, react 8 hours under 215 ℃ under the nitrogen environment.From reactant liquor, remove maleic anhydride and the alkene that does not have reaction through decompression distillation, obtained normal pressure and be liquid and inside isomerization vaccenic acid succinyl oxide (A1) 235g that be mixture down for following 25 ℃.Table 1 show this isomerization vaccenic acid succinyl oxide carbon number and 25 ℃ of following states, supply the content of contained alpha-olefin in the alkene of isomerization reaction.
The manufacturing of (making example 2) alkenyl succinic anhydrides (A2)
Replace to make that the 1-vaccenic acid uses cetene in the example 1, carry out with making the same inside isomerization reaction of example 1, obtained by 1H-NMR analyzes and knows the inside isomerization hexadecene mixture that does not contain alpha-olefin.Further, adopt except maleic anhydride is 96g all the other all with making the same mode of example 1, having obtained normal pressure is down liquid state and inside isomerization vaccenic acid succinyl oxide (A2) 243g that be mixture for following 25 ℃.Table 1 show this isomerization hexadecene succinyl oxide carbon number and 25 ℃ of following states, supply the content of contained alpha-olefin in the alkene of isomerization reaction.
The manufacturing of (making example 3) alkenyl succinic anhydrides (A3)
Replace to make the alpha-olefin mixture that 1-vaccenic acid in the example 1 uses 1-20 carbene/1-22 carbene/1-24 carbene=70/20/10 (mass ratio), carry out with making the same inside isomerization reaction of example 1, obtained by 1H-NMR analyzes and knows the inside isomerizing olefins mixture that does not contain alpha-olefin.Further, adopt except maleic anhydride is 75g all the other all with making the same mode of example 1, having obtained normal pressure is down liquid state and inside isomerizing olefins base succinyl oxide (A3) 231g that be mixture for following 25 ℃.Table 1 show this isomerization alkenyl succinic anhydrides carbon number and 25 ℃ of following states, supply the content of contained alpha-olefin in the alkene of isomerization reaction.
The manufacturing of (making example 4) alkenyl succinic anhydrides (A4)
Replace to make that the 1-vaccenic acid uses the 1-12 carbene in the example 1, carry out with making the same inside isomerization reaction of example 1, obtained by 1H-NMR analyzes and knows the inside isomerization 12 carbene mixtures that do not contain alpha-olefin.Further, adopt except maleic anhydride is 128g all the other all with making the same mode of example 1, having obtained normal pressure is down liquid state and isomerization 12 carbene base succinyl oxide (A4) 259g in inside that be mixture for following 25 ℃.Table 1 show these isomerization 12 carbene base succinyl oxides carbon number and 25 ℃ of following states, supply the content of contained alpha-olefin in the alkene of isomerization reaction.
The manufacturing of (making example 5) alkenyl succinic anhydrides (A5)
Let polypropylene tetramer (by 1The H-NMR analysis confirmation alpha-olefin be 7%) 200g and maleic anhydride 128g 215 ℃ of reactions 8 hours down under the nitrogen environment in autoclave.From reactant liquor, remove maleic anhydride and the alkene that does not have reaction through decompression distillation, obtained normal pressure and be liquid and branched dodecenyl succinic anhydride (A5) 230g that contain inner isomerizing olefins down for following 25 ℃.Table 1 show this branched dodecenyl succinic anhydride carbon number and 25 ℃ of following states, supply the content of contained alpha-olefin in the alkene of isomerization reaction.
The manufacturing of (making example 6) alkenyl succinic anhydrides (A6)
Let the 1-vaccenic acid (by 1The H-NMR analysis confirmation alpha-olefin be 100%) 200g and maleic anhydride 86g 215 ℃ of reactions 8 hours down under the nitrogen environment in autoclave.From reactant liquor, remove maleic anhydride and the 1-vaccenic acid that does not have reaction through decompression distillation, obtained the following 25 ℃ of solids of normal pressure not by the isomerized vaccenic acid succinyl oxide in inside (A6) 239g.Table 1 show this not by the carbon number of the isomerized vaccenic acid succinyl oxide in inside and 25 ℃ of following states, supply the content of contained alpha-olefin in the alkene of isomerization reaction.
The manufacturing of (making example 1) 2-oxetanone compound (B1)
Drop into thionyl chloride 200g toward four-hole boiling flask, temperature is made as 80 ℃ (thionyl chloride counterflow conditions).Be that hydrogenation fatty acid distribution of coconut oil (a1) 205.8g of caprylic acid/capric acid/dodecylic acid/myristic acid/palmitic acid/stearic acid/oleic acid=7/7/51/18/9/8/0 (not containing unrighted acid) spends 2 hours dropping liquids to move pipe then with the quality constituent ratio.At 80 ℃ down continue stir 1 hour thereafter; Further thionyl chloride is removed in distillation under 80 ℃ of normal pressures, obtains caprylic acid chloride, capric acid chloride, dodecylic acid chloride, myristic acid chloride, palmitic acid chloride and the muriatic mixture of stearic acid, is aliphatic acid chlorination thing 212.7g.Then drop into above-mentioned aliphatic acid chlorination thing 200g and toluene 200ml toward four-hole boiling flask again, be cooled to 20 ℃, remain in and spend 3 hours under 20 ℃ triethylamine 108.4g dropping liquid is moved pipe.Dropping liquid is warmed up to 30 ℃ after moving the duct ligation bundle, continues reaction 3 hours again.Add 3% diluted hydrochloric acid aqueous solution 200ml then; Stir after 10 minutes, left standstill 1 hour, after the aqueous phase separation with lower floor; Toluene is removed in decompression down distillation, obtain the different 2-oxetanone of carbon number mixture, be 2-oxetanone compound (B1) 141.5g.The 2-oxetanone compound (B1) that obtains is liquid state under 25 ℃ under normal pressure.In addition, table 2 shows kind and the proportioning of making the used raw fatty acid of 2-oxetanone compound.
The manufacturing of (making example 2) 2-oxetanone compound (B2)
Hydrogenation fatty acid distribution of coconut oil (a1) in the manufacturing example 1 is become hydrogenation fatty acid distribution of coconut oil (a2) 205.8g of caprylic acid/capric acid/dodecylic acid/myristic acid/palmitic acid/stearic acid/oleic acid=7/7/51/18/9/7/1 (unrighted acid 1 quality %); Carry out same reaction, obtain aliphatic acid chlorination thing 210.4g.Then carry out the reaction the same, obtain 2-oxetanone compound (B2) 144.7g with manufacturing routine 1 with resulting aliphatic acid chlorination thing 200g and triethylamine 208.4g.The 2-oxetanone compound (B2) that obtains is liquid state under 25 ℃ under normal pressure.In addition, table 2 shows kind and the proportioning of making the used raw fatty acid of 2-oxetanone compound.
The manufacturing of (making example 3) 2-oxetanone compound (B3)
The hydrogenation fatty acid distribution of coconut oil of making in the example 1 (a1) is become hydrogenation fatty acid distribution of coconut oil (a3) 205.8g that the quality ratio of components is caprylic acid/capric acid/dodecylic acid/myristic acid/palmitic acid/stearic acid/oleic acid=7/7/51/18/9/6/2 (unrighted acid 2 quality %); Carry out same reaction, obtain aliphatic acid chlorination thing 211.5g.Then carry out the reaction the same, obtain 2-oxetanone compound (B3) 142.3g with manufacturing routine 1 with resulting aliphatic acid chlorination thing 200g and triethylamine 108.4g.The 2-oxetanone compound (B3) that obtains is liquid state under 25 ℃ under normal pressure.In addition, table 2 shows kind and the proportioning of making the used raw fatty acid of 2-oxetanone compound.
The manufacturing of (making example 4) 2-oxetanone compound (B4)
Hydrogenation fatty acid distribution of coconut oil (a1) in the manufacturing example 1 is become hydrogenation fatty acid distribution of coconut oil (a4) 205.8g of caprylic acid/capric acid/dodecylic acid/myristic acid/palmitic acid/stearic acid/oleic acid=7/7/51/18/9/1/7 (unrighted acid 7 quality %); Carry out same reaction, obtain aliphatic acid chlorination thing 210.6g.Then carry out the reaction the same, obtain 2-oxetanone compound (B4) 140.3g with manufacturing routine 1 with resulting aliphatic acid chlorination thing 200g and triethylamine 108.4g.The 2-oxetanone compound (B4) that obtains is liquid state under 25 ℃ under normal pressure.In addition, table 2 shows kind and the proportioning of making the used raw fatty acid of 2-oxetanone compound.
The manufacturing of (making example 5) 2-oxetanone compound (B5)
Hydrogenation fatty acid distribution of coconut oil (a1) in the manufacturing example 1 is become hydrogenation fatty acid distribution of coconut oil (a5) 200.3g of caprylic acid/capric acid/dodecylic acid/myristic acid/palmitic acid/stearic acid/oleic acid=11/11/47/14/9/8/0 (unrighted acid 0 quality %); Carry out same reaction, obtain aliphatic acid chlorination thing 204.8g.Then carry out the reaction the same, obtain 2-oxetanone compound (B5) 142.1g with manufacturing routine 1 with resulting aliphatic acid chlorination thing 200g and triethylamine 111.2g.The 2-oxetanone compound (B5) that obtains is liquid state under 25 ℃ under normal pressure.In addition, table 2 shows kind and the proportioning of making the used raw fatty acid of 2-oxetanone compound.
The manufacturing of (making example 6) 2-oxetanone compound (B6)
The hydrogenation fatty acid distribution of coconut oil of making in the example 1 (a1) is become (a6) 282.5g of oleic acid (unrighted acid 100 quality %), carry out same reaction, obtain aliphatic acid chlorination thing 279.1g.Then carry out the reaction the same, obtain 2-oxetanone compound (B6) 149.6g with manufacturing routine 1 with resulting aliphatic acid chlorination thing 200g and triethylamine 80.8g.The 2-oxetanone compound (B6) that obtains is liquid state under 25 ℃ under normal pressure.In addition, table 2 shows kind and the proportioning of making the used raw fatty acid of 2-oxetanone compound.
The manufacturing of (making example 7) 2-oxetanone compound (B7)
The hydrogenation fatty acid distribution of coconut oil of making in the example 1 (a1) is become isostearic acid (a7) 280.3g, carry out same reaction, obtain aliphatic acid chlorination thing 277.7g.Then carry out the reaction the same, obtain 2-oxetanone compound (B4) 146.8g with manufacturing routine 1 with resulting aliphatic acid chlorination thing 200g and triethylamine 81.3g.The 2-oxetanone compound (B7) that obtains is liquid state under 25 ℃ under normal pressure.In addition, table 2 shows kind and the proportioning of making the used raw fatty acid of 2-oxetanone compound.
The manufacturing of (making example 8) 2-oxetanone compound (B8)
The hydrogenation fatty acid distribution of coconut oil of making in the example 1 (a1) is become fatty acid mixt (a8) 267.0g that mass ratio is palmitic acid/stearic acid=60/40 (unrighted acid 0 quality %); Carry out dropping liquid and move and carry out same reaction the pipe except being warmed to 80 ℃, obtain aliphatic acid chlorination thing 274.2g.Then carry out the reaction the same, obtain 2-oxetanone compound (B8) 152.5g with manufacturing routine 1 with resulting aliphatic acid chlorination thing 200g and triethylamine 85.1g.The 2-oxetanone compound (B8) that obtains is paraffin shape solid under 25 ℃ under normal pressure.In addition, table 2 shows kind and the proportioning of making the used raw fatty acid of 2-oxetanone compound.
The manufacturing of (making example 9) comparative example 3 usefulness 2-oxetanone compounds (B9)
The hydrogenation fatty acid distribution of coconut oil of making in the example 1 (a1) is become fatty acid mixt (a9) 229.9g that mass ratio is dodecylic acid/palmitic acid/stearic acid=50/25/25 (unrighted acid 0 quality %); Carry out dropping liquid and move and carry out same reaction the pipe except being warmed to 80 ℃, obtain aliphatic acid chlorination thing 228.3g.Then carry out the reaction the same, obtain 2-oxetanone compound (B9) 147.7g with manufacturing routine 1 with resulting aliphatic acid chlorination thing 200g and triethylamine 97.9g.The 2-oxetanone compound (B5) that obtains is paraffin shape solid under 25 ℃ under normal pressure.In addition, table 2 shows kind and the proportioning of making the used raw fatty acid of 2-oxetanone compound.
(surfactant)
As surfactant, used nonionic surfactant polyoxyethylene distyrene phenolic ether (Di-ichi Kogyo Seiyaku Co., Ltd. system NoigenEA-167) (D1), anionic surfactant's dioctyl sodium sulphosuccinate salt (D2), phosphoric acid be nonionic surfactant polyoxyethylene distyrene phenolic ether phosphate (the system Ply Surf AL of Di-ichi Kogyo Seiyaku Co., Ltd.) (D3), phosphoric acid is that nonionic surfactant gathers oxireme alkyl ether phosphate (the system Ply Surf A208N of Di-ichi Kogyo Seiyaku Co., Ltd.) (D4).
(aqueous high molecular dispersant)
Modulation example 1 < the acrylamide polymer class aqueous solution >
In the four-hole boiling flask that possesses mixer, thermometer, reflux condenser and nitrogen ingress pipe, drop into 335.7 parts of 50% acrylamide aqueous solutions, N; N acrylamide propyl-dimethyl amine (N; N-Dimethylaminopropylacrylamide) 16.2 parts, 80 11.2 parts of quality % metering system aqueous acids and 4.1 parts of SMASs (sodium methallylsulfonate), 2.6 parts of standard dodecyl mercaptans (normal-Dodecyl Mercaptan), 215.6 parts of ion exchange waters, 199.8 parts of isopropyl alcohols adjust to 4.5 with 20% sulfuric acid with pH.Under nitrogen environment, be warmed up to 60 ℃ while stirring this mixed liquor.Add 14.8 parts of 2% ammonium persulfate aqueous solutions as polymerization initiator, be warmed up to 80 ℃, kept 3 hours.Then, isopropyl alcohol is removed in distillation, adds ion exchange water, cool to room temperature, and obtaining concentration is that 20 quality %, viscosity are the macromolecule dispersing agent aqueous solution (C1) of 190mPas, pH4.2.Table 3 shows the corresponding relation of the macromolecule dispersing agent aqueous solution and modulation example.
Modulation example 2 < the acrylamide polymer class aqueous solution >
In 25 parts of both sexes acrylamide paper power agent DS4388 (Nippon PMC K. K.'s system), add 75 parts of ion exchange waters,, obtain the acrylamide polymer class aqueous solution (C2) of solid content 5.0 quality % through stirring, diluting.Table 3 shows the corresponding relation of the macromolecule dispersing agent aqueous solution and modulation example.
Modulation example 3 < the starch graft acrylamide based polymer aqueous solution >
Toward 33.3 parts of starch graft acrylamides is to add 66.7 parts of ion exchange waters among the paper power agent DG4204 (Nippon PMC K. K.'s system), and through stirring, diluting, obtaining solid content is the starch graft acrylamide based polymer aqueous solution (C3) of 5.0 quality %.Table 3 shows the corresponding relation of the macromolecule dispersing agent aqueous solution and modulation example.
Modulation example 4 < starch based paste liquid >
In the reaction vessel that has mixer, thermometer, reflux condensing tube, drop into cationic starch Cato304 (Japanese Niigata Seimitsu Co., Ltd. system, moisture rate measured value 13%) 57 parts, then drop into 943 parts in water, begin to stir, make dispersion.Then be warmed up to 95 ℃, continue stirring and be cooled to 40 ℃ after 20 minutes, obtaining solid content is the cationic starch class paste liquid (C4) of 5.0 quality %.Table 3 shows the corresponding relation of the macromolecule dispersing agent aqueous solution and modulation example.
Modulation example 5 < polyvinyl alcohol >
In the reaction vessel that has mixer, thermometer, reflux condensing tube, drop into 20 parts of polyvinyl alcohol " PVA-117 " (Kuraray Co., Ltd.'s system), then drop into 980 parts in water, begin to stir, make dispersion.Then be warmed up to 95 ℃, continue stir after 20 minutes and be cooled to 40 ℃, obtain solid content and be 2.0 quality %, viscosity and be 1000 parts of the polyvinyl alcohol water solutions (C5) of 10mPas, pH6.1.Table 3 shows the corresponding relation of the macromolecule dispersing agent aqueous solution and modulation example.
Modulation example 6 < water-soluble cellulose classes >
In the reaction vessel that has mixer, thermometer, reflux condensing tube, drop into 20 parts of carboxyethyl celluloses " Serogen 5A " (the first industrial pharmacy system), then drop into 980 parts in water, begin to stir, make dispersion.Then be warmed up to 95 ℃, continue stir after 20 minutes, be cooled to 40 ℃, obtain solid content and be 2.0 quality %, viscosity and be 1000 parts of the carboxyethyl cellulose aqueous solution (C6) of 10mPas, pH6.1.Table 3 shows the corresponding relation of the macromolecule dispersing agent aqueous solution and modulation example.
In addition, particle size determination, stability test and Water Resistance Test have also been carried out, as following.
< particle size determination >
For the latex that obtains through emulsification, measured weight average particle diameter with laser scattering type particles distribution instrument LA-910 (Horiba Seisakusho K.k.'s system).
< Water Resistance Test 1 >
With the thinned water of conductance 35mS/m dilution bleached kraft pulp (coniferous tree is 1: 9 mixed pulp to broad leaf tree paper pulp ratio), make pulp density reach 2.5 quality %, with the beater Canadian Standard Freeness 430 of pulling an oar.Then; 1.2L takes by weighing the disassociation machine with the gained pulp; Be incubated in 40 ℃; Under agitation add the precipitated calcium carbonate that relative paper pulp is 5 quality % (Okutama Kogyo Co., Ltd. system TP121), add aluminum sulfate that relative paper pulp is 0.5 quality %, paper pulp is that afterwards, having added relative paper pulp again is the sizing agent constituent of 0.1 quality % for the cationic starch (the Japanese system Cato304 of Niigata Seimitsu Co., Ltd.) of 0.7 quality % relatively.Thereafter; It is 0.8 quality % that the dilution water of use pH8, conductance 35mS/m is diluted to concentration with resulting pulp; Add relative paper pulp again successively and be the above-mentioned precipitated calcium carbonate of 15 quality %, paper pulp is that the cationic of 0.01 quality % and stayed agent (HYMO Co., Ltd. system and stayed agent NR12MLS) relatively; Carry out write by hand with The Noble & Wood corporate system paper machine, make to reach grammes per square metre 65g/m 2, with after moisture rate adjusts to 55% in the l Water Paper, following dry 80 seconds at 100 ℃ with drum dryer with servo roller press (labor roller press).The damping in 23 ℃, the thermostatic constant wet chamber of 50%R.H. of resulting paper was gone up the degree of beating according to JIS P-8122 standard test Stockigt after 24 hours, the resistance to water performance is estimated.This measured value means that more greatly resistance to water gives more excellent.In addition, the paper slip spare of copying here is suitable for vellum.
< Water Resistance Test 2 >
To stay before the agent and keep down 1 hour in 40 ℃ of states under the agitating pulp slurry except adding cationic, carry out with the same test of Water Resistance Test 1.In this test, the time ratio Water Resistance Test 1 that the sizing agent latex is scattered in the pulp moisture is long, and the sizing agent hydrolysis is carried out, so under the condition of the easier instabilityization of latex particle, estimate.
< Water Resistance Test 3 >
Thinned water with conductance 100mS/m dilutes old corrugated paper, and making pulp density is 2.5 quality %, with the beater Canadian Standard Freeness 330 of pulling an oar.Then, 1.2L takes by weighing the disassociation machine with the gained pulp, is incubated in 40 ℃, under agitation add relative paper pulp and be the dry paper power agent (the system DS4416 of Nippon PMC K. K.) of 0.3 quality % after, adding relative paper pulp is the sizing agent constituent of 0.14 quality %.Thereafter; It is 0.8 quality % that the dilution water of use pH7.5, conductance 100mS/m is diluted to concentration with resulting pulp; Adding relative paper pulp is the dry paper power agent (the system DH4160 of Nippon PMC K. K.) of 0.05 quality %; Carry out write by hand with The Noble&Wood corporate system paper machine, make to reach grammes per square metre 80g/m 2, with after moisture rate adjusts to 58% in the l Water Paper, following dry 80 seconds at 100 ℃ with drum dryer with servo roller press.The damping in 23 ℃, the thermostatic constant wet chamber of 50%R.H. of resulting paper according to JIS P-8140 standard test CoBB absorption of water (120 seconds), has been estimated water resistance after 24 hours in view of the above.The more for a short time resistance to water that means of this measured value is given more excellent.In addition, the paper slip spare of copying here is suitable for paperboards such as liner sheet.
< Water Resistance Test 4 >
Keep down 1 hour in 40 ℃ of states under the agitating pulp slurry except adding before the dry paper power agent DH4160, carry out with the same test of Water Resistance Test 3.In this test, the time ratio Water Resistance Test 3 that the sizing agent latex is scattered in the pulp moisture is long, and the sizing agent hydrolysis is carried out, so under the condition of the easier instabilityization of latex particle, estimate.
< dirty test 1 >
The same with Water Resistance Test 1 medicine is made an addition to bleached kraft pulp, do not carry out the write by hand test, filter slurry, let the filtration residue be clouded in corrosion resistant plate, with 4.2kgf/cm but replace with 60 order stainless steel sifts 2Pressure pressed 2 minutes, it is dirty to observe adhering to of corrosion resistant plate after peeling off, divides 4 grades to estimate.Latex instabilityization, to the tack of paper pulp fiber poor more just more increased ease of implantation thereof to corrosion resistant plate; The alkenyl succinic hydrolysis is carried out just can increasing adherence more, transplanting to corrosion resistant plate more easily more.During this is estimated, dirty many more, just can become more and under actual service conditions, also cause same dirty reason.Evaluation criterion is following:
It is dirty that ◎ does not have discovery to adhere to.
Zero only finds a bit to adhere to.
△ finds to adhere on a small quantity.
* find to adhere in a large number.
< dirty test 2 >
Pulp modulation is the same with Water Resistance Test 2, also has, and except stay agent to remain in that all the other all make an experiment with dirty test 11 hour the state of 40 ℃ of stirrings before adding the samely, divides 4 grades and estimates.
Embodiment 1
Drop into alkenyl succinic anhydrides (A1) 70g toward the closed container that has mixer, thermometer and nitrogen ingress pipe; Then drop into 2-oxetanone compound (B1) 30g; 25 ℃ continue down to stir 1 hour under nitrogen environment, obtain the mixture 100g of the ratio of A2/B1=70/30.Then,, amount to 30g, stirred 2 minutes with 15000rpm, obtain latex with rotary-type homogeneous blender (the smart mechanism of Co., Ltd. Japan is done made) acrylamide polymer (C1) 15g of resulting mixture 15g and solid content 20 quality %.This latex stably was maintained at the latex state more than 6 hours.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.
Embodiment 2
All the same except having become the alkenyl succinic anhydrides among the embodiment 1 (A1) the alkenyl succinic anhydrides (A2) all the other with embodiment 1, obtained latex.This latex stably was maintained at the latex state more than 6 hours.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.
Embodiment 3
All the same except having become the alkenyl succinic anhydrides among the embodiment 1 (A1) the alkenyl succinic anhydrides (A3) all the other with embodiment 1, obtained latex.This latex stably was maintained at the latex state more than 6 hours.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.
Embodiment 4
All the same except having become the alkenyl succinic anhydrides among the embodiment 1 (A1) the alkenyl succinic anhydrides (A4) all the other with embodiment 1, obtained latex.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.
Embodiment 5
All the same except having become the alkenyl succinic anhydrides among the embodiment 1 (A1) the alkenyl succinic anhydrides (A5) all the other with embodiment 1, obtained latex.This latex stably was maintained at the latex state more than 6 hours.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.
Embodiment 6
All the same except having become the 2-oxetanone compound (B1) among the embodiment 1 the 2-oxetanone compound (B2) all the other with embodiment 1, obtained latex.This latex stably was maintained at the latex state more than 6 hours.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.
Embodiment 7
All the same except having become the 2-oxetanone compound (B1) among the embodiment 1 the 2-oxetanone compound (B3) all the other with embodiment 1, obtained latex.This latex stably was maintained at the latex state more than 6 hours.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.
Embodiment 8
All the same except having become the 2-oxetanone compound (B1) among the embodiment 1 the 2-oxetanone compound (B4) all the other with embodiment 1, obtained latex.This latex stably was maintained at the latex state more than 6 hours.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.
Embodiment 9
All the same except having become the 2-oxetanone compound (B1) among the embodiment 1 the 2-oxetanone compound (B5) all the other with embodiment 1, obtained latex.This latex stably was maintained at the latex state more than 6 hours.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.
Embodiment 10
All the same except having become the 2-oxetanone compound (B1) among the embodiment 1 the 2-oxetanone compound (B6) all the other with embodiment 1, obtained latex.This latex stably was maintained at the latex state more than 6 hours.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.
Embodiment 11
All the same except having become the 2-oxetanone compound (B1) among the embodiment 1 the 2-oxetanone compound (B7) all the other with embodiment 1, obtained latex.This latex stably was maintained at the latex state more than 6 hours.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.
Embodiment 12
All the same except having become the alkenyl succinic anhydrides among the embodiment 1 (A1) 70g, 2-oxetanone compound (B 1) 30g respectively alkenyl succinic anhydrides (A1) 85g, 2-oxetanone compound (B1) 15g all the other with embodiment 1, obtained latex.This latex stably was maintained at the latex state more than 6 hours.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.
Embodiment 13
All the same except having become the alkenyl succinic anhydrides among the embodiment 1 (A1) 70g, 2-oxetanone compound (B 1) 30g respectively alkenyl succinic anhydrides (A1) 95g, 2-oxetanone compound (B1) 5g all the other with embodiment 1, obtained latex.This latex stably was maintained at the latex state more than 6 hours.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.
Embodiment 14
Stir 1 minute with 10000rpm with rotary-type homogeneous blender (Co., Ltd. Japan smart mechanism do made) in embodiment 1 that all the other are all the same with embodiment 1, obtained latex.This latex stably was maintained at the latex state more than 6 hours.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.
Embodiment 15
Stir 3 minutes with 15000rpm with rotary-type homogeneous blender (Co., Ltd. Japan smart mechanism do made) in embodiment 1 that all the other are all the same with embodiment 1, obtained latex.This latex stably was maintained at the latex state more than 6 hours.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.
Comparative example 1
Except becoming 2-oxetanone compound (B8) to 2-oxetanone compound (B1) among the embodiment 1, the temperature during stirring becomes outside 50 ℃ from 25 ℃ that all the other are all the same with embodiment 1, is modulated into latex.But resulting dispersion liquid has paraffin shape 2-oxetanone compound (B8) to separate out, separate after 10 minutes warps, so fail to carry out particle size determination and Water Resistance Test.Because the latex state just has been destroyed in the latex short time that this comparative example is modulated, so exceeded the scope of the invention.
Comparative example 2
All the same except having become the 2-oxetanone compound (B1) among the embodiment 1 the 2-oxetanone compound (B9) all the other with embodiment 1, obtained latex.But leave standstill 1 hour latex separation later, do not obtain stable latex.Therefore fail to carry out particle size determination and Water Resistance Test.
Comparative example 3
All the same except alkenyl succinic anhydrides (A1) 70g, 2-oxetanone compound (B1) 30g among the embodiment 1 being become alkenyl succinic anhydrides (A1) 50g, 2-oxetanone compound (B1) 50g all the other respectively with embodiment 1, obtained latex.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.
Comparative example 4
All the same except becoming alkenyl succinic anhydrides (A1) 70g, 2-oxetanone compound (B1) 30g among the embodiment 1 respectively alkenyl succinic anhydrides (A1) 98g, 2-oxetanone compound (B1) 2g all the other with embodiment 1, obtained latex.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.
Comparative example 5
All the same except becoming alkenyl succinic anhydrides (A1) among the embodiment 1 alkenyl succinic anhydrides (A6) all the other with embodiment 1, obtained latex.But leave standstill 20 minutes latex separation later, do not obtain stable latex.Therefore fail to carry out particle size determination and Water Resistance Test.
Comparative example 6
Acrylamide polymer (C1) 15g with alkenyl succinic anhydrides (A1) 15g and solid content 20 quality %; Amount to 30g; Stirred 2 minutes with 15000rpm with rotary-type homogeneous blender (the smart mechanism of Co., Ltd. Japan is done made), obtained alkenyl succinic anhydrides (A1) latex.To this dispersion liquid; In all < Water Resistance Test 1 >, < Water Resistance Tests 2 >, < dirty test 1>and < dirty test 2 >; Not that the relative paper pulp of interpolation is the dispersion liquid of the sizing agent constituent of 0.1 quality %; To add relative paper pulp be after alkenyl succinic anhydrides (A1) latex of 0.1 quality % but replace, each test of carrying out.Performance evaluation result sees table 6.
Comparative example 7
Acrylamide polymer (C1) 15g with alkenyl succinic anhydrides (A1) 15g and solid content 20 quality %; Amount to 30g; Stirred 2 minutes with 15000rpm with rotary-type homogeneous blender (the smart mechanism of Co., Ltd. Japan is done made), obtained alkenyl succinic anhydrides (A1) latex.Also in addition with acrylamide polymer (C1) 15g of 2-oxetanone compound (B1) 15g and solid content 20%; Amount to 30g; Stirred 2 minutes with 15000rpm with rotary-type homogeneous blender (the smart mechanism of Co., Ltd. Japan is done made), obtained 2-oxetanone compound (B1) latex.Alkenyl succinic anhydrides (A1) latex 21g and 2-oxetanone compound (B1) latex 9g are promptly mixed, and the ratio that has obtained alkenyl succinic anhydrides (A1) and 2-oxetanone compound (B1) is the latex mixture of 70 to 30 mass ratioes.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.
This comparative example; Owing to not being " mixture to containing under 25 ℃ of 60～95 quality % under 25 ℃ for the alkenyl succinic anhydrides of liquid state and 5～40 quality % for the 2-oxetanone compound of liquid state carries out the emulsion that emulsification obtains ", so not within the scope of the present invention.
Comparative example 8
Acrylamide polymer (C1) 15g with alkenyl succinic anhydrides (A1) 15g and solid content 20 quality %; Amount to 30g; Stirred 2 minutes with 15000rpm with rotary-type homogeneous blender (the smart mechanism of Co., Ltd. Japan is done made), obtained alkenyl succinic anhydrides (A1) latex.Also in addition with acrylamide polymer (C1) 15g of 2-oxetanone compound (B1) 15g and solid content 20%; Amount to 30g; Stirred 2 minutes with 15000rpm with rotary-type homogeneous blender (the smart mechanism of Co., Ltd. Japan is done made), obtained 2-oxetanone compound (B1) latex.To these 2 kinds of dispersion liquids; In all < Water Resistance Test 1 >, < Water Resistance Tests 2 >, < dirty test 1>and < dirty test 2 >; Not that the relative paper pulp of interpolation is the dispersion liquid of the sizing agent constituent of 0.1 quality %; To add the alkenyl succinic anhydrides that relative paper pulp is 0.07 quality % (A1) latex and relative paper pulp respectively be after 2-oxetanone compound (B1) latex of 0.03 quality % but replace, each test of carrying out.Performance evaluation result sees table 6.
Embodiment 16
Drop into alkenyl succinic anhydrides (A1) 70g toward the closed container that has mixer, thermometer and nitrogen ingress pipe; Then drop into 2-oxetanone compound (B1) 30g, anionic surfactant (D2) 0.5g; 60 ℃ continue down to stir after 1 hour to be cooled to 25 ℃ under nitrogen environment, have obtained containing the mixture 100.5g of the A1/B1=70/30 of 0.5 quality % surfactant.Then,, amount to 30g, stirred 2 minutes with 15000rpm, obtain latex with rotary-type homogeneous blender (the smart mechanism of Co., Ltd. Japan is done made) acrylamide polymer (C1) 15g of resulting mixture 15g and solid content 20 quality %.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.In addition, table 4 shows the mark of representing surfactant and the corresponding relation of kinds of surfactants.
Embodiment 17
On embodiment 16 bases, except alkenyl succinic anhydrides (A1) is added alkenyl succinic anhydrides (A2), outside input table surface-active agent (D2) 1.1g, all the other are all the same with embodiment 16, have obtained latex again.This latex stably was maintained at the latex state more than 6 hours.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.In addition, table 4 shows the mark of representing surfactant and the corresponding relation of kinds of surfactants.
Embodiment 18
On embodiment 16 bases, except alkenyl succinic anhydrides (A1) is added alkenyl succinic anhydrides (A3), outside input table surface-active agent (D2) 6.4g, all the other are all the same with embodiment 16, have obtained latex again.This latex stably was maintained at the latex state more than 6 hours.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.In addition, table 4 shows the mark of representing surfactant and the corresponding relation of kinds of surfactants.
Embodiment 19
On embodiment 16 bases, all the other are all the same with embodiment 16 except input table surface-active agent (D2) 5.3g, have obtained latex.This latex stably was maintained at the latex state more than 6 hours.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.
Embodiment 20
Drop into alkenyl succinic anhydrides (A1) 70g toward the closed container that has mixer, thermometer and nitrogen ingress pipe; Then drop into 2-oxetanone compound (B1) 30g, surfactant (D2) 1.1g; 60 ℃ continue down to stir after 1 hour to be cooled to 25 ℃ under nitrogen environment, have obtained containing the mixture 101.1g of the A1/B1=70/30 of 1.0 quality % surfactants.Then, solid content is diluted to acrylamide polymer (C2) 20g of 5 quality % to resulting mixture 10g and water, amounts to 30g, with 15000rpm stirring 2 minutes, obtain latex with rotary-type homogeneous blender (the smart mechanism of Co., Ltd. Japan is done made).This latex stably was maintained at the latex state more than 6 hours.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.In addition, table 4 shows the mark of representing surfactant and the corresponding relation of kinds of surfactants.
Embodiment 21
On embodiment 20 bases; Mixture 2g and starch-grafted polymer (C3) 40g that solid content is 5 quality % of A1/B1=70/30 that will contain the surfactant of 1.0 quality %; Add up to 42g; Stirred 2 minutes with 15000rpm with rotary-type homogeneous blender (the smart mechanism of Co., Ltd. Japan is done made), obtain latex.This latex stably was maintained at the latex state more than 6 hours.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.In addition, table 4 shows the mark of representing surfactant and the corresponding relation of kinds of surfactants.
Embodiment 22
On embodiment 20 bases; Mixture 2g and starch paste liquid (C4) 40g that solid content is 5 quality % of A1/B1=70/30 that will contain the surfactant of 1.0 quality %; Add up to 42g; Stirred 3 minutes with 15000rpm with rotary-type homogeneous blender (the smart mechanism of Co., Ltd. Japan is done made), obtain latex.This latex stably was maintained at the latex state more than 6 hours.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.In addition, table 4 shows the mark of representing surfactant and the corresponding relation of kinds of surfactants.
Embodiment 23
On embodiment 20 bases; Mixture 2g and polyvinyl alcohol water solution (C5) 40g that solid content is 5 quality % of A1/B1=70/30 that will contain the surfactant of 1.0 quality %; Add up to 42g; Stirred 3 minutes with 15000rpm with rotary-type homogeneous blender (the smart mechanism of Co., Ltd. Japan is done made), obtain latex.This latex stably was maintained at the latex state more than 6 hours.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.In addition, table 4 shows the mark of representing surfactant and the corresponding relation of kinds of surfactants.
Embodiment 24
On embodiment 20 bases; Mixture 2g and the carboxyethyl cellulose aqueous solution (C6) 40g that solid content is 5 quality % of A1/B1=70/30 that will contain the surfactant of 1.0 quality %; Add up to 42g, stirred 3 minutes with 15000rpm with rotary-type homogeneous blender (the smart mechanism of Co., Ltd. Japan is done made).This latex stably was maintained at the latex state more than 6 hours.Obtained latex.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.In addition, table 4 shows the mark of representing surfactant and the corresponding relation of kinds of surfactants.
Embodiment 25
On embodiment 20 bases; 2-oxetanone compound (B1) is become 2-oxetanone compound (B2); Acrylamide polymer (C2) is become acrylamide polymer (C1); Surfactant (D2) is become surfactant (D1), and in addition all the other are all the same with embodiment 20, have obtained latex.This latex stably was maintained at the latex state more than 6 hours.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.In addition, table 4 shows the mark of representing surfactant and the corresponding relation of kinds of surfactants.
Embodiment 26
On embodiment 20 bases; 2-oxetanone compound (B1) is become 2-oxetanone compound (B3); Acrylamide polymer (C2) is become acrylamide polymer (C1); Surfactant (D2) is become surfactant (D3), and in addition all the other are all the same with embodiment 20, have obtained latex.This latex stably was maintained at the latex state more than 6 hours.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.In addition, table 4 shows the mark of representing surfactant and the corresponding relation of kinds of surfactants.
Embodiment 27
On embodiment 20 bases; 2-oxetanone compound (B1) is become 2-oxetanone compound (B3); Acrylamide polymer (C2) is become acrylamide polymer (C1); Surfactant (D2) is become surfactant (D4), and in addition all the other are all the same with embodiment 20, have obtained latex.This latex stably was maintained at the latex state more than 6 hours.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.In addition, table 4 shows the mark of representing surfactant and the corresponding relation of kinds of surfactants.
Embodiment 28
Drop into alkenyl succinic anhydrides (A1) 70g toward the closed container that has mixer, thermometer and nitrogen ingress pipe; Then drop into 2-oxetanone compound (B1) 30g, surfactant (D1) 1.1g; 60 ℃ continue down to stir after 1 hour to be cooled to 25 ℃ under nitrogen environment, have obtained containing the mixture 101.1g of the A1/B1=70/30 of 1.0 quality % surfactants.Drop into acrylamide polymer (C1) 195g, surfactant (D2) 1g, the water 604g of solid content 20% in addition; 25 ℃ were stirred 1 hour down, and the solid content mass ratio that has obtained acrylamide polymer (C1)/surfactant (D2) is the aqueous solution of the solid content 5% of 97.5/2.5.Then,, amount to 30g, stirred 2 minutes with 10000rpm, obtain latex with rotary-type homogeneous blender (the smart mechanism of Co., Ltd. Japan is done made) resulting mixture 10g and aqueous solution 20g.This latex stably was maintained at the latex state more than 6 hours.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.In addition, table 4 shows the mark of representing surfactant and the corresponding relation of kinds of surfactants.
Embodiment 29
Drop into alkenyl succinic anhydrides (A1) 70g toward the closed container that has mixer, thermometer and nitrogen ingress pipe; Then drop into 2-oxetanone compound (B1) 30g; 25 ℃ continue down to stir 1 hour under nitrogen environment, have obtained the mixture 100g of A1/B1=70/30.Drop into acrylamide polymer (C1) 195g, surfactant (D2) 1g, the water 604g of solid content 20% in addition; Normal temperature stirred 1 hour down, and the solid content mass ratio that has obtained acrylamide polymer (C1)/surfactant (D2) is the aqueous solution of the solid content 5% of 97.5/2.5.Then,, amount to 30g, stirred 2 minutes with 1200rpm, obtain latex with rotary-type homogeneous blender (the smart mechanism of Co., Ltd. Japan is done made) resulting mixture 10g and aqueous solution 20g.This latex stably was maintained at the latex state more than 6 hours.Resulting dispersion particle size is as shown in table 5, and performance evaluation result sees table 6.In addition, table 4 shows the mark of representing surfactant and the corresponding relation of kinds of surfactants.
[table 1]
Carbon number Alpha-olefin proportion in the raw material olefin 25 ℃ of following states
A1 C18 0 Liquid
A2 C16 0 Liquid
A3 C20/C22/C24＝70/20/10 0 Liquid
A4 C12 0 Liquid
A5 C12 (polypropylene tetramer) 7 Liquid
A6 C18 100 Solid
Symbol description in the table 1
C18: carbon number is 18
C16: carbon number is 16
C22/C22/C24=70/20/10: it is 70,20,10 that carbon number 20,22,24 occupies ratio
C12: carbon number is 12
[table 2]
Figure BDA0000135293300000271
[table 3]
Water-soluble polymer
C1 Modulation example 1
C2 Modulation example 2
C3 Modulation example 3
C4 Modulation example 4
C5 Modulation example 5
C6 Modulation example 6
[table 4]
Kinds of surfactants
D1 Nonionic
D2 Anion
D3 Phosphoric acid system
D4 Phosphoric acid system
[table 5]
Figure BDA0000135293300000281
Symbol description in the table 5
Annotate 1:A1 latex and B1 latex and process the back mixing respectively.
Annotate 2: the particle diameter that mixes the back latex
Annotate 3:A1 latex and B1 latex and process respectively, add respectively.
[table 6]
Figure BDA0000135293300000301

Claims (6)

1. a sizing agent constituent is characterized in that, is the mixture that contains under 25 ℃ of 60～95 quality % under 25 ℃ for the alkenyl succinic anhydrides of liquid state and 5～40 quality % for the 2-oxetanone compound of liquid state is carried out the emulsion that emulsification obtains.
2. sizing agent constituent according to claim 1; It is characterized in that 2-oxetanone compound is that raw material obtains with the fatty acid mixt, in this fatty acid mixt; The aliphatic acid of carbon number 8～10 is 8～20 quality %, and the aliphatic acid of carbon number 12～18 is 92～80 quality %.
3. sizing agent constituent according to claim 1 and 2 is characterized in that, 2-oxetanone compound is that fatty acid mixt below the 2 quality % is that raw material obtains with unrighted acid.
4. according to each described sizing agent constituent in the claim 1 to 3, it is characterized in that alkenyl succinic anhydrides is: the addition reaction product of the carbon number that contains inner the isomerizing olefins alkene below 24 and maleic anhydride more than 16.
5. according to each described sizing agent constituent in the claim 1 to 4, it is characterized in that, is a kind of emulsion of mixture; This mixture contains: 25 ℃ is the surfactant of 0.1～5 parts by mass for liquid 2-oxetanone compound and total 100 parts by mass of above-mentioned relatively alkenyl succinic anhydrides and above-mentioned 2-oxetanone compound down for liquid alkenyl succinic anhydrides, 25 ℃ down.
6. according to each described sizing agent constituent in the claim 1 to 5, it is characterized in that the average grain diameter of decentralized photo is below the above 1.5 μ m of 0.5 μ m in the above-mentioned emulsion.
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