CN104005264A - Surface gluing agent for paper making and paper coated with the gluing agent - Google Patents
Surface gluing agent for paper making and paper coated with the gluing agent Download PDFInfo
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- CN104005264A CN104005264A CN201410035991.7A CN201410035991A CN104005264A CN 104005264 A CN104005264 A CN 104005264A CN 201410035991 A CN201410035991 A CN 201410035991A CN 104005264 A CN104005264 A CN 104005264A
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Abstract
The invention aims to provide a surface gluing agent for paper making. The surface gluing agent for paper making has excellent mechanical stability relative to a high-shear-force coating method (through gate rollers or gluing pressing, etc.) and has little foaming during a coating process. Meanwhile, the gluing effects are good. The surface gluing agent for paper making contains aqueous polymer emulsion which is acquired by using specific starch, unsaturated monomer compounds with specific compositions, specific polymerization initiators and using the starch with a certain amount for emulsification and polymerization.
Description
Technical field
The present invention relates to a kind of surface sizing agent for paper making and be coated with the paper that this sizing agent obtains.
Background technology
As existing surface sizing agent for paper making, the known water-soluble graft polymers (with reference to patent documentation 1) that has the ethylenically unsaturated monomer that can use starch, contain carboxyl.In addition,, as paper surface conditioning agent, knownly can use the monomer mixture being formed by phenylethylene and the ethylenically unsaturated monomer that contains carboxyl and the water-soluble graft polymers (with reference to patent documentation 2) being formed by water dispersible polysaccharide.Because these polymer are water-soluble polymer, therefore, for the surface sizing agent for paper making taking described polymer as principal component or paper surface conditioning agent, in the time processing high-viscosity products, while particularly shifting product with pump, operability is poor conventionally.In addition,, aspect raising paper sizing effect, described surface sizing agent for paper making and paper still have improved space with surface conditioning agent.
In view of the above problems, studied the surface sizing agent for paper making taking Emulgating polymers (polymer emulsion) or aqueous polymer dispersion (polymeric dispersions) as principal component.For example, in patent documentation 3, recorded one under starch exists, the paper sizing being obtained by ethylenically unsaturated monomer emulsion polymerization microparticle polymer dispersion liquid.In described polymer dispersion liquid, starch use amount is 10～40 % by weight (all solids composition of described dispersion liquid is designated as to 100 % by weight).In recent years, along with the high speed of paper machine, improve constantly for the requirement of the mechanical stability of surface sizing agent for paper making, but the mechanical stability of above-mentioned polymer dispersion liquid not.
As mentioned above, from guaranteeing the mechanical stability to high speed machines, further, from recent years the environmental consideration of chemical material being required and the angle of low price object, the usage ratio that improves cheap natural material starch becomes necessary.
Patent documentation
Patent documentation 1: examined patent publication 61-56359 communique
Patent documentation 2: Unexamined Patent 10-158993 communique
Patent documentation 3: specially permit No. 4202600 communique
Summary of the invention
The object of the present invention is to provide a kind of surface sizing agent for paper making, described surface sizing agent for paper making has good mechanical stability for the coating process (by door roller or size press etc.) of the high shear force that is applicable to high speed machines, while coating, bubble less, the processing operability of product is good, the sizing efficiency of the one-tenth paper meanwhile, obtaining is good.
In view of above-mentioned various characteristics, present inventor is conceived to use the kind of starch, usage ratio, the composition of unsaturated monomer etc. of starch to conduct in-depth research, found that, can address the above problem by the surface sizing agent for paper making that uses the aqueous polymer emulsion obtaining under rated condition to make, complete the present invention based on this discovery.
; the present invention relates to a kind of surface sizing agent for paper making; it is characterized in that; described surface sizing agent for paper making contains aqueous polymer emulsion; described aqueous polymer emulsion is under the existence of starch, polymerization initiator and chain-transferring agent; unsaturated monomer emulsion polymerization is obtained, and wherein, described starch is to use inorganic peroxide intrinsic viscosity to be adjusted into 0.1～0.9 starch (A); The unsaturated monomer mixture (B) that described unsaturated monomer is made up of the phenylethylene of 3～30 % by weight (taking the total amount of unsaturated monomer mixture (B) as 100 % by weight) and (methyl) esters of acrylic acid of 70～97 % by weight; Described polymerization initiator is the polymerization initiator (C) of being made up of hydrogen peroxide and heavy metallic salt; And with respect to total amount 100 weight portions of described unsaturated monomer mixture (B), the described starch (A) of use 80～200 weight portions carries out emulsion polymerization and obtains described aqueous polymer emulsion.In addition, the present invention relates to a kind of paper that described surface sizing agent for paper making obtains that is coated with on body paper.
By the present invention, a kind of surface sizing agent for paper making can be provided, described surface sizing agent for paper making has good mechanical stability for the coating process (by door roller or size press etc.) of high shear force, while coating, bubble less, the processing operability of product is good, meanwhile, sizing efficiency is good.In addition,, because the usage ratio of starch is high, from the angle of environment in recent years consideration requirement and low price object, the present invention is also well suited for.
Detailed description of the invention
Surface sizing agent for paper making of the present invention is characterised in that and contains specific aqueous polymer emulsion.Described aqueous polymer emulsion, in meeting following each important document, obtains through fully emulsified polymerization: (1) is used inorganic peroxide intrinsic viscosity to be adjusted into 0.1～0.9 starch (A) (following, to be called important document (1)); (2), taking the total amount of unsaturated monomer (B) as 100 % by weight, use the unsaturated monomer mixture (B) (below, being called important document (2)) form by the phenylethylene of 3～30 % by weight and (methyl) esters of acrylic acid of 70～97 % by weight; (3) use the polymerization initiator (C) (following, to be called important document (3)) of being made by hydrogen peroxide and heavy metallic salt; And (4) be 100 weight portions with respect to the total amount of unsaturated monomer mixture (B), the usage ratio of starch (A) is 80～200 weight portions (following, to be called important document (4)).
In the present invention, as important document (1), must use the reasons are as follows of described starch (A): when emulsion polymerization, polymerization stability is good in system, obtain that viscosity is low, the good aqueous polymer emulsion of mechanical stability of product operation (while particularly transfer with pump) simultaneously.As the intrinsic viscosity of starch (A), be preferably 0.1～0.6.
As the raw starch of preparing starch (A) use, can use without particular limitation various known raw starch, for example, can enumerate the various starch that obtained by corn, potato, cassava, wheat, rice, sago palm (sago palm), waxy corn, in addition, also can enumerate the starch derivatives such as cationic starch, oxidized starch, phosphoric acid modification starch, carboxymethylated starch, hydroxyethyl starch, carbamyl ethylated starch, dialdehyde starch, acetic acid modified starch etc.
For the raw starch modulation starch (A) with above-mentioned, make inorganic peroxide act on raw starch, to reach mode such within the scope of described intrinsic viscosity, make molecular weight oxidisability and reduce.As described inorganic peroxide, be not particularly limited, for example can use the inorganic peroxides such as hypochlorite, peroxydisulfate (ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate etc.), hydrogen peroxide or their combination, further, at least a kind of water-soluble heavy metallic salt and the hydrogen peroxide that are selected from ferric sulfate and copper sulphate can be used in combination.Wherein, can preferably use at least any a kind in ammonium persulfate, potassium peroxydisulfate and sodium peroxydisulfate.As starch (A), also can use commercially available product, the commodity " prince エ ー ス A " by name that for example can produce purchased from prince's Application ス タ ー チ (strain) etc.In addition, the starch obtaining after the enzyme such as amylase is processed with described raw starch, because Bu Shi (Brookfield) viscosity of the aqueous polymer emulsion obtaining uprises, thereby is not suitable as the starch of important document (1).
As important document (2), must use the reason of unsaturated monomer mixture (B) is to obtain the aqueous polymer emulsion that sizing efficiency is good.But the good reason of sizing efficiency is also uncertain, infer its former because, the copolymer hydrophobicity being made up of unsaturated monomer mixture (B) is strong, and then is coated with after described Cypres, in drying machine is dry, this copolymer easily dissolves expansion.
As the phenylethylene of the compositing monomer of unsaturated monomer mixture (B), can enumerate styrene, α-methyl styrene, vinyltoluene, but consider from price angle, preferably use styrene.In addition,, as (methyl) esters of acrylic acid of the compositing monomer of unsaturated monomer mixture (B), can use without particular limitation various known materials.As above-mentioned ester class, for example, (methyl) alkyl acrylate that the carbon number that can use alkyl is 1～18 etc., consider from the angle of the sizing efficiency of the aqueous polymer emulsion that obtains, preferably use (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, wherein, most preferably (methyl) isobutyl acrylate.
Not damaging in the scope of the object of the invention, copolymer of the present invention can merge with other any unsaturated monomers that can copolymerization the unsaturated monomer mixture (B) that forms described copolymer use.As any unsaturated monomer as above, alpha-olefin, vinyl pyrrolidone etc. that can to enumerate acrylonitrile, vinylacetate, acrylamide, carbon number be 6～22.In addition, in described copolymer, the usage ratio of above-mentioned unsaturated monomer is usually less than 20 % by weight, preferably lower than 10 % by weight.
In addition, as the compositing monomer of unsaturated monomer mixture of the present invention (B), ion-type unsaturated monomer is foreclosed.For example, be not suitable for using following ion-type unsaturated monomer: the anionic unsaturated monomers such as (methyl) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid; (methyl) acrylic acid N, N-dialkyl aminoalkyl ester, (methyl) acrylic acid N, the cationic unsaturated monomers such as the quaternary ammonium salt (modifier that utilizes the quaternizing agents such as benzyl chloride compound to obtain) of N-dialkyl aminoalkyl ester.Its reason is, the hydrophobicity reduction of copolymer, and sizing efficiency reduces.
In important document (2), not only the kind of the compositing monomer of described unsaturated monomer mixture (B) is in specific scope, and their usage ratio is also in specific scope.,, using the total amount of unsaturated monomer mixture (B) as 100 % by weight, the usage ratio of phenylethylene is 3～30 % by weight, more preferably 3～10 % by weight, in addition, the usage ratio of (methyl) esters of acrylic acid is 70～97 % by weight, more preferably 90～97 % by weight.If exceed above-mentioned usage ratio, the sizing efficiency of the aqueous polymer emulsion obtaining cannot reach the level of expectation.
As important document (3), must use the reason of the polymerization initiator (C) of being made by hydrogen peroxide and heavy metallic salt to be, products obtained therefrom with low cost, sizing efficiency and dispersion stabilization are good simultaneously.But, polymerization initiator (C) makes the reason of described various function admirables also uncertain, supposition may, due to being swift in response of unsaturated monomer mixture (B) carried out, in shortening manufacturing time, reduce the amount of unreacted unsaturated monomer in aqueous polymer emulsion.
As described heavy metallic salt, can enumerate the sulfate of cerium, manganese, iron, copper etc. etc.For the use amount of polymerization initiator (C), be not particularly limited, the monomer composition in visual unsaturated monomer mixture (B) suitably determines, common, taking the total amount of unsaturated monomer mixture (B) as 100 weight portions, polymerization initiator (C) uses 0.1～10 weight portion left and right.In polymerization initiator (C), the usage ratio of hydrogen peroxide is generally 95～99 % by weight left and right.
In the present invention, in the time carrying out described polymerization, do not damaging in the degree of the object of the invention, other known polymerization initiators and polymerization initiator (C) can merged to use.In addition,, in rear polymerization procedure, also can use other known polymerization initiators.As other known polymerization initiators, can enumerate the inorganic peroxide such as ammonium persulfate, potassium peroxydisulfate; The organic peroxides such as benzoyl peroxide, cumyl peroxide, lauroyl peroxide; 2,2'-azodiisobutyronitrile, 2,2 '-azo-bis-iso-dimethyl etc.In addition,, in the time using radical polymerization initiator, also can will also use the system of the reductants such as sodium hydrogensulfite, sodium thiosulfate as redox system.
In the present invention, in order to regulate the degree of polymerization to reach the viscosity of expectation, be necessary to use chain-transferring agent in the time carrying out emulsion polymerization.As chain-transferring agent, can use without particular limitation known chain-transferring agent, for example, can enumerate 2,4-diphenyl-4-methyl-1-pentene; Tertiary lauryl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan, mercaptopropionic acid dodecyl ester; Isopropylbenzene; Carbon tetrachloride; Terpinolene etc.; Mercaptoethanol; TGA and its salt; The alcohols such as amylalcohol; The polyethers such as the copolymer of polyethylene glycol, polypropylene glycol, polyoxy tetramethylene glycol, polyglycereol, oxirane and expoxy propane.In above-mentioned chain-transferring agent, from the angle of the dispersion stabilization of aqueous polymer emulsion, suitable use 2,4-diphenyl-4-methyl-1-pentene.As the use amount of chain-transferring agent, with respect to 100 parts of the total amounts of unsaturated monomer (B), conventionally use 0.01～3 weight portion left and right.
As important document (4), with respect to total amount 100 weight portions of unsaturated monomer mixture (B), the usage ratio of starch (A) is 80～200 weight portions, and reason is, like this can controlled product cost and carrying capacity of environment is low, the good aqueous polymer emulsion of mechanical stability simultaneously.With respect to total amount 100 weight portions of unsaturated monomer mixture (B), when the usage ratio of starch (A) is during lower than 80 weight portion, the mechanical stability deficiency of the aqueous polymer emulsion obtaining; In addition,, in the time that usage ratio exceedes 200 weight portion, sizing efficiency reduces.
Aqueous polymer emulsion of the present invention can adopt various known method manufactures.For example, to being equipped with in the reaction vessel of suitable heater and agitator, add after starch (A), add unsaturated monomer mixture (B), polymerization initiator (C), water, chain-transferring agent, add if desired emulsifying agent described later, conventionally under agitation carry out the polymerisation about 2～12 hours in 40～150 DEG C of left and right, can manufacture thus aqueous polymer emulsion.In addition, described monomer mixture (B) add method, can adopt and any one method such as disposablely add, substep splashes into, in addition, also can adopt the method splashing into together with polymerization initiator (C), chain-transferring agent.
In addition,, while carrying out emulsion polymerization, not damaging in the scope of the object of the invention, can use separately or mix use various known nonionics, anionic or cationic surface active agent and/or reactive emulsifier.With respect to the total amount of monomer mixture (B), the consumption of described surfactant is generally below 10 % by weight, more preferably below 5 % by weight.In the time that described consumption exceedes 10 % by weight, the foaming characteristic grow of the emulsion obtaining, can cause problem because bubbling during as coating fluid.As nonionic surface active agent, can enumerate polyethylene glycol, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitan fatty acid ester etc.As anionic surfactant, can enumerate alkyl sulfate, alkylbenzenesulfonate, polyoxyethylene alkyl ether sulfate salt, polyoxyethylene alkylphenyl ether sulfate salt, dialkyl sulfosuccinate salt, alkylsulfonate, polyoxyethylene alkyl ether sulfosuccinate, polyoxyethylene styrene phenyl ether sulfosuccinate, polyoxyethylene alkyl ether phosphate, alpha-alkene sulfonate, naphthalene sulfonic acid-formaldehyde condensation product, polyoxyethylene alkyl phenyl ether sulfuric acid etc.As cationic surface active agent, can enumerate alkyl trimethyl ammonium chloride, for example, Dodecyl trimethyl ammonium chloride, hexadecyltrimethylammonium chloride, stearyl trimethyl ammonium chloride, VARISOFT TA100, INCROQUAT TMC-80 (mountain Yu base trimethyl ammonium chloride), VARISOFT TA100, softex kw, Cetyltrimethylammonium bromide; Lanolin acylamino-propyl group ethyl dimethyl disulfide acetoacetic ester ammonium; Octadecyl trimethyl ammonium saccharin (stearyl trimethyl ammonium saccharin); Cetyl trimethyl ammonium saccharin; Methacryloxyethyl trimethyl ammonium chloride; Docosyl trimethyl sulfate methyl ammonium and quaternary ammonium salt-91.In addition,, as reactive emulsifier, for example, can enumerate the compound in the molecule of recording in JP 2003-293288 communique with polymerism functional group.
The aqueous polymer emulsion obtaining as mentioned above presents micro white emulsion outward appearance, and when concentration is 25 % by weight, having pH is 1～8, and brookfield viscosity (25 DEG C of mensuration) is 3～100mPas, the proterties that particle diameter is 40～100nm.Consider balancing machine stability, low foaming characteristic, sizing efficiency etc., more preferably 40～80nm of described particle diameter.In addition, the average primary particle diameter that " particle diameter " is described emulsion particle, for example, can pass through dynamic light scattering determination.In addition, be not particularly limited as described particle size determination instrument, for example, can use light scattering particle size analyzer (trade name " ELSZ-2 " ， great mound Electricity (strain) manufacture).
As required, surface sizing agent for paper making of the present invention can be prepared to adding various additives in described aqueous polymer emulsion.As described additive, for example, can enumerate defoamer, preservative agent, chelating agent, water soluble aluminum compound etc.
By adding water soluble aluminum compound, can further improve sizing efficiency.As this water soluble aluminum compound, be not particularly limited, can use known water soluble aluminum compound.For example, preferably use at least a kind that is selected from the group being formed by the polymer of aluminum sulfate, aluminium chloride, alkaline aluminum sulfate, basic aluminium chloride, silicic acid aluminum sulfate (sulfuric acid Gui acid ア Le ミ ニ ウ system) and above-claimed cpd.In above-claimed cpd, from cost angle, particularly preferably aluminum sulfate.
As the ratio of surface sizing agent for paper making and the water soluble aluminum compound ratio of solid constituent (separately in), be not particularly limited, consider from the angle of sizing efficiency, be preferably 5:95～95:5.In addition, water soluble aluminum compound can be mixed and added in surface sizing agent for paper making, also can add to separately in the coating fluid that contains surface sizing agent for paper making.
As the coating fluid that contains surface sizing agent for paper making of the present invention, can directly use described surface sizing agent for paper making, or by using after its dilution, as required, also can be used in conjunction with various additives.As described additive, for example, can enumerate the starch based such as oxidized starch, organic phosphate starch, autologous modified starch, cationic starch, amphoteric starch; The cellulose families such as carboxymethyl cellulose; Polyvinyl alcohol; Polyacrylamide; The paper strengthening agent of the water soluble polymers such as mosanom etc.; And antilubricant, preservative agent, rust inhibitor, pH adjusting agent, defoamer, thickener, filler, antioxidant, water-fast agent, coalescents, pigment, dyestuff etc.
When actual use, as the solid component concentration in coating fluid, surface sizing agent for paper making of the present invention is generally 0.001～2 % by weight left and right, is preferably the scope of 0.05～0.5 % by weight.
Paper of the present invention is to use the coating fluid that contains surface sizing agent for paper making of the present invention, utilizes various known means, and described coating fluid is coated on body paper and is obtained.
As described body paper, be not particularly limited, conventionally can use the paper being coated with and cardboard taking lignocellulose fiber as raw material.In addition, described body paper is made by paper grade pulp, as described paper grade pulp, can enumerate the chemical pulp such as LBKP, NBKP, the mechanical pulps such as GP, TMP, secondary stock etc.In addition, for various additives such as the filler adding in described body paper, sizing agent, dry strength agents, be not particularly limited.
As the kind that above-mentioned body paper is coated with to the paper that Cypres of the present invention obtains, can enumerate the paper used for recording such as list paper using, PPC paper using, electrothermal sensitive recording paper; The coated papers such as art paper, cast-coated paper, high-quality coated paper; The package paper such as brown paper, white coil paper; Other specifiable paper have: the various paper (machine-made paper) such as writing folio, books paper using, printing, newspaper paper using; The cardboards such as the paper-made vessel use cardboards such as Manila board, white board, chipboard (chip board) and lining paper, corrugated core.
In addition, use surface sizing agent for paper making of the present invention to there is no special restriction to the method for described various body paper coatings, be suitable for known method in the past, such as infusion process, size press method, door roller method, scraper coating (bar coater) method, calender (calender) method, spraying process etc.Because surface sizing agent for paper making of the present invention has above-mentioned good mechanical stability, can be applicable to well the coating method that this class of high speed machines has high shear force transfer printing type machine coating processes such as () excellent metering size press rubbing method, door roller rubbing methods.
Embodiment
Enumerate Production Example, embodiment and comparative example below and further illustrate the present invention, but the present invention is not limited to these embodiment.In addition, unless otherwise specified, " part " in each example and " % " are all weight standards.
In addition, in each example, brookfield viscosity refers to sample is adjusted to the solution after 25 DEG C, utilizes Brookfield viscometer (East Machine industry (strain) manufacture) value measured; Intrinsic viscosity refers to the value of utilizing capillary viscometer (Ubbelohde) to measure; Particle diameter refers to the value of utilizing light scattering particle size analyzer (trade name " ELSZ-2 " ， great mound Electricity (strain) manufacture) to measure.
Synthesizing of synthesis example 1(amidin (A))
In the reaction vessel with agitator, condenser pipe, nitrogen ingress pipe and thermometer; add 400 parts of ion exchange waters, 88% cationic starch (trade name " HI-CAT260 "; Japan's NSC(strain) manufacture) 10 parts of 114 parts, ammonium persulfate; under nitrogen protection, be incubated while stirring 1 hour in 80～85 DEG C.Then, adding the water adjusting solid component concentration of ormal weight is 20%, obtains amidin (A1).Brookfield viscosity, intrinsic viscosity and the pH in the time of 25 DEG C is as shown in table 1 for gained amidin (A1).
Synthesis example 2～5
Except using in synthesis example 1 as the kind of the inorganic peroxide of viscosity reducers and consumption become as shown in table 1, other react identical with synthesis example 1, obtain solid component concentration and are 20% various amidins (A2)～(A5).Brookfield viscosity, intrinsic viscosity and the pH in the time of 25 DEG C is as shown in table 1 for these amidins.In addition, the Fe in table 1 represents green vitriol.
Table 1
Synthesizing of Production Example 1(aqueous polymer emulsion (surface sizing agent for paper making))
In the reaction vessel with agitator, condenser pipe, nitrogen ingress pipe, thermometer and dropping funel, add 500 parts of amidins (A1), 80 parts of ion exchange waters, 0.08 part of green vitriol, with after the oxygen in the abundant displacement reaction container of nitrogen, when stirring, make temperature in system rise to 80 DEG C.Then, in system, dripped unsaturated monomer mixture and the polymerization initiator aqueous solution with approximately 2 hours, wherein said unsaturated monomer mixture is mixed by 80 parts of 20 parts of styrene, isobutyl methacrylate, the aqueous hydrogen peroxide solution 10 parts (with respect to described unsaturated monomer, being 3.5 weight portions) that the described polymerization initiator aqueous solution is is 35% by concentration is dissolved in 100 parts of water and obtains.Drip and finish, insulation reaction makes to react completely for 2 hours.Next, add 14 parts of 32% sodium hydrate aqueous solutions after cooling, dilute with water obtains surface sizing agent for paper making.The concentration of the surface sizing agent for paper making obtaining is thus that at 25%, 25 DEG C, brookfield viscosity is 5mPas, and pH is 3.3, and particle diameter is 75nm.
Production Example 2～11 and relatively Production Example 1～10
Except according to the kind of the kind of the kind of the amidin shown in table 2 and use amount and/or unsaturated monomer and use amount and/or initator, other operate identical with Production Example 1, obtain various surface sizing agent for paper making.The physical property (non-volatile component, viscosity, pH, particle diameter) of the various surface sizing agent for paper making that obtain is as shown in table 2.
Production Example 12
In the beaker of 1L, after 100 parts of the surface sizing agent for paper making obtaining in Production Example 1 are mixed with 50% aluminum sulfate solution 50 parts (solid constituent ratio=50/50 of surface sizing agent for paper making/aluminum sulfate), add quantitative water dilution, obtain surface sizing agent for paper making, the total solid constituent concentration of the aqueous polymer emulsion of described surface sizing agent for paper making and aluminum sulfate is 25%, the brookfield viscosity of 25 DEG C is 5mPas, pH is 2.2, and particle diameter is 78nm.
In table 2, AMSD represents that 2,4-diphenyl-4-methyl-1-pentene, NDM represent that n-dodecyl mercaptan, St represent that styrene, IBMA represent that isobutyl methacrylate, BA represent that butyl acrylate, 2-EHA represent that 2-EHA, AN represent that acrylonitrile, DM represent that dimethylaminoethyl methacrylate, AA represent that acrylic acid, APS represent that ammonium persulfate, Fe represent that green vitriol, sulfuric acid Al represent 16 hydrazine aluminum sulfates.
The preparation > of < coating fluid
By oxidized starch, (prince コ ー Application ス タ ー チ (strain) manufactures, trade name " prince エ ー ス A ") carry out gelatinization according to solid component concentration 15%, use described oxidized starch preparation to contain the various coating fluids that solid component concentration is 5% oxidized starch, 0.2% surface sizing agent for paper making.
The preparation > of < test paper using
Utilize door roll coater ((strain) エ ス エ ム テ ー manufacture) respectively described coating fluid to be applied to neutral upper matter paper (basic weight 60g/m
2, 1 μ L water droplet degree of sizing 5 seconds) on.Then, make various coated papers by rotary roller drying machine dry (105 DEG C, 1 minute), obtain testing paper using.
The mensuration > of < infiltration colloidality
For each test paper using of utilizing above-mentioned method to obtain, the method specifying based on Japan TAPPI No.33, the 1 μ L water that drips on test paper using surface, mensuration paper absorbs the time of water droplet, measures water droplet degree of sizing (second).Numeral is larger, represents that its sizing efficiency is better.Result is as shown in table 3.
The test > of < foaming characteristic
Described coating fluid is heated to 50 DEG C, processes 2 minutes with home-use agitator, after processing, measure immediately liquid level (liquid level at initial stage is 60mm).Result is as shown in table 3.
< mechanical stability test (hard water system) >
The hardness of described coating fluid is adjusted to 30 ° of dH, is heated to 50 DEG C, the laboratory size press with two rollers when keeping this temperature circulates 1 hour, and visual assessment is carried out in the pollution of the generation according to following standard to agglutinator and two rollers.Result is as shown in table 3.
◎: mechanical stability fabulous (can not confirm agglutinator, roller is pollution-free)
Zero: good mechanical stability (can not confirm agglutinator, roller has light contamination)
△: mechanical stability poor (can confirm has a small amount of agglutinator, and roller has pollution)
×: mechanical stability poor (can confirm to have a large amount of agglutinators, roller has obvious pollution)
Table 3
As can be seen from Table 3, surface sizing agent for paper making of the present invention with relatively with compared with surface sizing agent for paper making, mechanical stability for the coating process (by door roller or size press etc.) of high shear force is good, bubbles few when coating, and sizing efficiency is good simultaneously.
Claims (9)
1. a surface sizing agent for paper making, it is characterized in that, described surface sizing agent for paper making contains aqueous polymer emulsion, described aqueous polymer emulsion is under the existence of starch, polymerization initiator and chain-transferring agent, unsaturated monomer emulsion polymerization is obtained, wherein, described starch is to use inorganic peroxide intrinsic viscosity to be adjusted into 0.1～0.9 starch (A); Described unsaturated monomer be total amount taking unsaturated monomer mixture (B) as 100 % by weight, the unsaturated monomer mixture (B) being formed by the phenylethylene of 3～30 % by weight and (methyl) esters of acrylic acid of 70～97 % by weight; Described polymerization initiator is the polymerization initiator (C) of being made up of hydrogen peroxide and heavy metallic salt; And with respect to total amount 100 weight portions of described unsaturated monomer mixture (B), the described starch (A) of use 80～200 weight portions carries out emulsion polymerization and obtains described aqueous polymer emulsion.
2. surface sizing agent for paper making as claimed in claim 1, wherein, described inorganic peroxide is at least one being selected from the group being made up of ammonium persulfate, potassium peroxydisulfate and sodium peroxydisulfate.
3. surface sizing agent for paper making as claimed in claim 1 or 2, wherein, described chain-transferring agent is 2,4-diphenyl-4-methyl-1-pentene.
4. the surface sizing agent for paper making as described in any one in claim 1～3, wherein, described polymerization initiator (C) is made at least one water-soluble heavy metallic salt and hydrogen peroxide in ferric sulfate and copper sulphate, and meanwhile, the usage ratio of hydrogen peroxide is 95～99 % by weight.
5. the surface sizing agent for paper making as described in any one in claim 1～4, wherein, the particle diameter of described aqueous polymer emulsion is 40～100nm.
6. the surface sizing agent for paper making as described in any one in claim 1～5, wherein, described (methyl) esters of acrylic acid is for being selected from least one in the group being made up of (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA.
7. the surface sizing agent for paper making as described in any one in claim 1～6, wherein, the brookfield viscosity of described surface sizing agent for paper making is 3～100mPas, described brookfield viscosity is to measure under the condition of 25 DEG C of 25 % by weight, temperature at solid component concentration.
8. the surface sizing agent for paper making as described in any one in claim 1～7, wherein, described surface sizing agent for paper making contains water soluble aluminum compound, and, in the ratio of solid constituent, the ratio of described surface sizing agent for paper making and described water soluble aluminum compound is 5:95～95:5 separately.
One kind on body paper right to use require the surface sizing agent for paper making described in any one in 1～8 to be coated with the paper obtaining.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-032686 | 2013-02-22 | ||
| JP2013032686A JP6090657B2 (en) | 2013-02-22 | 2013-02-22 | Paper-making surface sizing agent and paper coated with the sizing agent |
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| CN104005264A true CN104005264A (en) | 2014-08-27 |
| CN104005264B CN104005264B (en) | 2016-08-17 |
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| CN201410035991.7A Active CN104005264B (en) | 2013-02-22 | 2014-01-24 | Surface sizing agent for paper making and be coated with the paper that this sizing agent obtains |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104452469A (en) * | 2014-11-13 | 2015-03-25 | 苏州誉之铖贸易有限责任公司 | Fragrant packaging material for packaging presents |
| CN105463935A (en) * | 2014-09-30 | 2016-04-06 | 荒川化学工业株式会社 | Papermaking additive and paper obtained by using same |
| CN110644283A (en) * | 2018-06-27 | 2020-01-03 | 玖龙纸业(重庆)有限公司 | Surface sizing agent for packaging paper and preparation method thereof |
| CN111851142A (en) * | 2020-07-24 | 2020-10-30 | 淄博圣泉纸业有限公司 | Surface treatment method for transfer printing paper |
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| CN104497721B (en) * | 2014-12-02 | 2017-02-22 | 周宏亮 | Release agent as well as release paper and release film of release agent |
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| JP6760344B2 (en) | 2018-09-18 | 2020-09-23 | 栗田工業株式会社 | Surface sizing agent for papermaking |
| JP7156089B2 (en) * | 2019-03-01 | 2022-10-19 | 荒川化学工業株式会社 | Surface sizing agent for paper manufacturing, coated paper |
| CN110541302B (en) * | 2019-09-06 | 2022-12-13 | 天津科技大学 | Method for modifying surface of paper-based material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105463935A (en) * | 2014-09-30 | 2016-04-06 | 荒川化学工业株式会社 | Papermaking additive and paper obtained by using same |
| CN105463935B (en) * | 2014-09-30 | 2018-07-10 | 荒川化学工业株式会社 | Additive for papermaking and the paper obtained using the additive |
| CN104452469A (en) * | 2014-11-13 | 2015-03-25 | 苏州誉之铖贸易有限责任公司 | Fragrant packaging material for packaging presents |
| CN110644283A (en) * | 2018-06-27 | 2020-01-03 | 玖龙纸业(重庆)有限公司 | Surface sizing agent for packaging paper and preparation method thereof |
| CN111851142A (en) * | 2020-07-24 | 2020-10-30 | 淄博圣泉纸业有限公司 | Surface treatment method for transfer printing paper |
| CN111851142B (en) * | 2020-07-24 | 2022-04-19 | 淄博圣泉纸业有限公司 | Surface treatment method for transfer printing paper |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2014163002A (en) | 2014-09-08 |
| CN104005264B (en) | 2016-08-17 |
| TWI585268B (en) | 2017-06-01 |
| TW201441448A (en) | 2014-11-01 |
| JP6090657B2 (en) | 2017-03-08 |
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