CN104005264B - Surface sizing agent for paper making and be coated with the paper that this sizing agent obtains - Google Patents
Surface sizing agent for paper making and be coated with the paper that this sizing agent obtains Download PDFInfo
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- CN104005264B CN104005264B CN201410035991.7A CN201410035991A CN104005264B CN 104005264 B CN104005264 B CN 104005264B CN 201410035991 A CN201410035991 A CN 201410035991A CN 104005264 B CN104005264 B CN 104005264B
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Abstract
It is an object of the invention 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 high shear force, bubbling when being coated less, meanwhile, sizing efficiency is excellent.Containing aqueous polymer emulsion in described surface sizing agent for paper making, described aqueous polymer emulsion uses specific starch, the unsaturated monomer mixture of specific composition and specific polymerization initiator and uses the described starch of specific consumption to obtain through emulsion 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, it is known to starch, olefinic unsaturation list containing carboxyl can be used
The water-soluble graft polymers (with reference to patent documentation 1) of body.Additionally, as paper surface conditioning agent, it is known that can use by
Phenylethylene and the monomer mixture of the composition of the ethylenically unsaturated monomer containing carboxyl and be made up of water dispersible polysaccharides class
Water-soluble graft polymers (with reference to patent documentation 2).Owing to these polymer are water-soluble polymer, therefore, for institute
State surface sizing agent for paper making or paper surface conditioning agent that polymer is main constituent, generally when processing high-viscosity products,
Particularly poor by operability during pump transfer product.Additionally, in terms of improving paper sizing effect, described surface sizing agent for paper making
With the space that paper surface conditioning agent still has improvement.
In view of the above problems, have studied that (polymer divides with Emulgating polymers (polymer emulsion) or aqueous polymer dispersion
A prose style free from parallelism) it is the surface sizing agent for paper making of main constituent.Such as, patent documentation 3 has been recorded a kind of in the presence of starch, by olefinic
The paper sizing microparticle polymer dispersion liquid that unsaturated monomer emulsion polymerization obtains.In described polymer dispersion liquid, starch
Usage amount is that all solids composition of described dispersion liquid is designated as 100 weight % by 10～40 weight %().In recent years, along with paper machine
High speed, the requirement for the mechanical stability of surface sizing agent for paper making improves constantly, but above-mentioned polymer dispersion liquid
Mechanical stability is the most inadequate.
As it has been described above, from guaranteeing the mechanical stability to high speed machines, further, from ring to chemical material in recent years
Border considers to require and the angle of low price purpose is set out, and improving that the use ratio of cheap natural material starch becomes to have very much must
Want.
Patent documentation
Patent documentation 1: examined patent publication 61-56359 publication
Patent documentation 2: Unexamined Patent 10-158993 publication
Patent documentation 3: specially permit No. 4202600 publication
Summary of the invention
It is an object of the invention to provide a kind of surface sizing agent for paper making, described surface sizing agent for paper making is for being suitable for
Coating process (by door roller or size press etc.) in the high shear force of high speed machines has good mechanical stability, carries out
Bubbling during coating less, the process operability of product is good, and meanwhile, the sizing efficiency of the one-tenth paper obtained is excellent.
In view of above-mentioned various characteristics, present inventor is conceived to use the kind of starch, the use ratio of starch, unsaturated list
The compositions of body etc. conduct in-depth research, it was found that by using the aqueous polymer emulsion obtained under rated condition to prepare
Surface sizing agent for paper making can solve the problems referred to above, complete the present invention based on this discovery.
That is, the present invention relates to a kind of surface sizing agent for paper making, it is characterised in that described surface sizing agent for paper making contains
Aqueous polymer emulsion, described aqueous polymer emulsion is in the presence of starch, polymerization initiator and chain-transferring agent, makes insatiable hunger
Obtaining with monomer emulsion polymerization, wherein, described starch is to use inorganic peroxide that intrinsic viscosity is adjusted to 0.1～0.9
Starch (A)；Described unsaturated monomer is to be in terms of 100 weight % by 3～30 weight %(by the total amount of unsaturated monomer mixture (B))
Phenylethylene and 70～97 weight % (methyl) esters of acrylic acid composition unsaturated monomer mixture (B)；Described polymerization is drawn
Sending out agent is the polymerization initiator (C) being made up of hydrogen peroxide and heavy metallic salt；Further, relative to described unsaturated monomer mixture
(B) total amount 100 weight portion, uses the described starch (A) of 80～200 weight portions to carry out emulsion polymerization and obtains described polymerizable aqueous
Thing emulsion.Additionally, the present invention relates to a kind of be coated with the paper that described surface sizing agent for paper making obtains on body paper.
Pass through the present invention, it is possible to provide a kind of surface sizing agent for paper making, described surface sizing agent for paper making is for high shear
The coating process (by door roller or size press etc.) of power has good mechanical stability, bubbles less when being coated, and produces
The process operability of product is good, and meanwhile, sizing efficiency is excellent.Additionally, due to the use ratio of starch is high, examine from environment in recent years
Considering and require that the angle with low price purpose is set out, the present invention is well suited for.
Detailed description of the invention
The surface sizing agent for paper making of the present invention is characterised by containing specific aqueous polymer emulsion.Described aqueous is gathered
Compound emulsion, while meeting following each important document, obtains through fully emulsified polymerization: (1) uses inorganic peroxide by intrinsic
Viscosity is adjusted to the starch (A) (hereinafter referred to as important document (1)) of 0.1～0.9；(2) it is 100 weights with the total amount of unsaturated monomer (B)
Amount % meter, uses the unsaturated list being made up of the phenylethylene of 3～30 weight % and (methyl) esters of acrylic acid of 70～97 weight %
Body mixture (B) (hereinafter referred to as important document (2))；(3) polymerization initiator (C) being made up of hydrogen peroxide and heavy metallic salt is used
(hereinafter referred to as important document (3))；And (4) are 100 weight portions relative to the total amount of unsaturated monomer mixture (B), starch (A)
Use ratio be 80～200 weight portions (hereinafter referred to as important document (4)).
In the present invention, as important document (1), it is necessary to the reason using described starch (A) is as follows: during emulsion polymerization, system is cohesion
Conjunction has good stability, and obtains the water that viscosity mechanical stability low, product operation (when particularly shifting) is good with pump simultaneously
Property polymer emulsion.As the intrinsic viscosity of starch (A), preferably 0.1～0.6.
As preparing the raw starch that starch (A) uses, can be without using various known raw starch with limiting especially,
Such as, the various shallow lakes obtained by Semen Maydis, Rhizoma Solani tuber osi, Maninot esculenta crantz., Semen Tritici aestivi, rice, sago Petiolus Trachycarpi (sago palm), Glutinous Semen Maydis can be enumerated
Powder, additionally, also can enumerate cationic starch, Oxytarch, phosphoric acid modification starch, carboxymethylated starch, hydroxyethyl starch,
The starch derivatives etc. such as carbamoylethyl starch, dialdehyde starch, acetic acid modified starch.
In order to above-mentioned raw starch modulation starch (A), make inorganic peroxide act on raw starch, to reach
Such mode in the range of stating intrinsic viscosity, reduces with making molecular weight.As described inorganic peroxide, without especially
Limit, such as can use hypochlorite, peroxydisulfate (Ammonium persulfate., potassium peroxydisulfate, sodium peroxydisulfate etc.), hydrogen peroxide or it
The inorganic peroxide such as combination, it is possible to further by least one water solublity huge sum of money in iron sulfate and copper sulfate
Belong to salt and hydrogen peroxide is applied in combination.Wherein it is possible at least appointing in Ammonium persulfate., potassium peroxydisulfate and sodium peroxydisulfate, is preferably used
Anticipate a kind.As starch (A), it is possible to use commercially available product, the trade name that such as can produce purchased from prince's Application ス タ チ (strain)
For " prince エ ス A " etc..Additionally, the starch obtained after the ferment treatment such as amylase with described raw starch, due to obtain
Bu Shi (Brookfield) viscosity of aqueous polymer emulsion uprises, thus is not suitable as the starch of important document (1).
As important document (2), it is necessary to the reason using unsaturated monomer mixture (B) is to obtain the aqueous that sizing efficiency is good
Polymer emulsion.But, reason that sizing efficiency is good is the most uncertain, thus it is speculated that its reason is, by unsaturated monomer mixture (B)
The copolymer hydrophobicity constituted is strong, and then after being coated with described Cypres, in drying machine is dried, this copolymer easily dissolves
Launch.
As the phenylethylene of the compositing monomer of unsaturated monomer mixture (B), styrene, Alpha-Methyl benzene second can be enumerated
Alkene, vinyltoluene, but consider from price angle, styrene is preferably used.Additionally, as unsaturated monomer mixture (B)
(methyl) esters of acrylic acid of compositing monomer, can be without using various known material with limiting especially.As above-mentioned esters, example
As, (methyl) alkyl acrylate etc. that carbon number is 1～18 of alkyl can be used, from the aqueous polymer emulsion obtained
(methyl) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) acrylic acid from the point of view of sizing efficiency, are preferably used
The tert-butyl ester, (methyl) 2-EHA, wherein, most preferably (methyl) Isobutyl 2-propenoate.
Within the scope without prejudice to the object of the present invention, the copolymer of the present invention can will constitute the unsaturation of described copolymer
Monomer mixture (B) merges use with other copolymerizable any unsaturated monomers.As above the most unsaturated single
Body, acrylonitrile can be enumerated, vinylacetate, acrylamide, carbon number be 6～22 alpha-olefin, vinyl pyrrolidone etc..
Additionally, in described copolymer, the use ratio of above-mentioned unsaturated monomer is usually less than 20 weight %, preferably shorter than 10 weights
Amount %.
Additionally, the compositing monomer of the unsaturated monomer mixture (B) as the present invention, ion-type unsaturated monomer is got rid of
Outside.Such as, be not suitable for using following ion-type unsaturated monomer: (methyl) acrylic acid .beta.-methylacrylic acid, maleic acid, fumaric acid, clothing
The anionic unsaturated monomers such as health acid；(methyl) acrylic acid N, N-dialkyl aminoalkyl ester, (methyl) acrylic acid N, N-bis-
The cationic insatiable hungers such as the quaternary ammonium salt (utilizing the modifier that the quaternizing agents such as Methoxybenzyl chloride obtain) of alkylaminoalkyl
And monomer.Its reason is, the hydrophobicity of copolymer reduces, and sizing efficiency reduces.
In important document (2), the kind of the compositing monomer of the most described unsaturated monomer mixture (B) in the range of specific,
And their use ratio is also in the range of specific.That is, using the total amount of unsaturated monomer mixture (B) as 100 weights
Amount %, the use ratio of phenylethylene is 3～30 weight %, more preferably 3～10 weight %, additionally, (methyl) esters of acrylic acid
Use ratio is 70～97 weight %, more preferably 90～97 weight %.If beyond above-mentioned use ratio, the polymerizable aqueous obtained
The sizing efficiency of thing emulsion is unable to reach desired level.
As important document (3), it is necessary to use the reason of the polymerization initiator (C) being made up of hydrogen peroxide and heavy metallic salt to exist
With low cost in, products obtained therefrom, sizing efficiency and dispersion stabilization are good simultaneously.But, polymerization initiator (C) makes described
The reason of various function admirables is the most uncertain, thus it is speculated that be likely to be due to make being swift in response of unsaturated monomer mixture (B) carry out,
While shortening manufacturing time, the amount of unreacted unsaturated monomer in aqueous polymer emulsion is made to reduce.
As described heavy metallic salt, the sulfate etc. of cerium, manganese, ferrum, copper etc. can be enumerated.Polymerization initiator (C) is made
Consumption, is not particularly limited, and the monomer composition in visual unsaturated monomer mixture (B) suitably determines, generally, with unsaturated monomer
The total amount of mixture (B) is 100 weight portions, and polymerization initiator (C) uses about 0.1～10 weight portions.In polymerization initiator (C)
The use ratio of hydrogen peroxide is usually about 95～99 weight %.
In the present invention, when carrying out described polymerization, in the degree not damaging the object of the invention, can be by known to other
Polymerization initiator and polymerization initiator (C) merge use.Additionally, in post polymerization step, it is possible to use poly-known to other
Close initiator.As polymerization initiator known to other, the inorganic peroxide such as Ammonium persulfate., potassium peroxydisulfate can be enumerated；Peroxide
Change the organic peroxides such as benzoyl, cumyl peroxide, lauroyl peroxide；2,2'-azodiisobutyronitrile, 2,2 '-idol
Nitrogen two isopropylformic acid. dimethyl ester etc..Additionally, when using radical polymerization initiator, it is possible to incite somebody to action and with sodium sulfite, sulfur for sulfur
The system of the reducing agents such as acid sodium is as redox system.
In the present invention, reach desired viscosity to regulate the degree of polymerization when carrying out emulsion polymerization, it is necessary to use chain to turn
Move agent.As chain-transferring agent, can be without using with limiting especially known chain-transferring agent, such as, 2 can be enumerated, 4-diphenyl-4-
Methyl-1-pentene；Tertiary lauryl mercaptan, n-dodecyl mercaptan, n octylmercaptan, mercaptopropionic acid dodecyl ester；Isopropyl
Benzene；Carbon tetrachloride；Terpinolene etc.；Mercaptoethanol；TGA and its salt；The alcohols such as amylalcohol；Polyethylene Glycol, poly-the third two
The polyethers such as the copolymer of alcohol, polyoxytetramethylene glycol, polyglycereol, oxirane and expoxy propane.In above-mentioned chain-transferring agent,
From the angle of the dispersion stabilization of aqueous polymer emulsion, suitably use 2,4-diphenyl-4-methyl-1-pentene.As
The usage amount of chain-transferring agent, relative to the total amount 100 parts of unsaturated monomer (B), generally uses about 0.01～3 weight portions.
As important document (4), relative to total amount 100 weight portion of unsaturated monomer mixture (B), the use ratio of starch (A)
Example is 80～200 weight portions, and reason is, so can obtain controlling product cost and carrying capacity of environment is low, mechanically stable simultaneously
The aqueous polymer emulsion that property is excellent.Relative to total amount 100 weight portion of unsaturated monomer mixture (B), when making of starch (A)
During by ratio less than 80 weight portion, the mechanical stability of the aqueous polymer emulsion obtained is not enough；Additionally, when use ratio exceedes
During 200 weight portion, sizing efficiency reduces.
The aqueous polymer emulsion of the present invention can use various known method manufacture.Such as, add to equipped with suitable
In the reaction vessel of thermal and agitator, after adding starch (A), add unsaturated monomer mixture (B), polymerization initiator
(C), water, chain-transferring agent, add emulsifying agent described later if desired, the most under agitation carry out 2～12 in about 40～150 DEG C little
Polyreaction time about, thus can manufacture aqueous polymer emulsion.Additionally, the Adding Way of described monomer mixture (B), can
To use any one methods such as disposable addition, step by step instillation, in addition it is also possible to use and polymerization initiator (C), chain tra nsfer
The method that agent instills together.
During additionally, carry out emulsion polymerization, within the scope without prejudice to the object of the present invention, may be used alone or in combination
Various known nonionics, anionic or cationic surface active agent and/or reactive emulsifier.Mix relative to monomer
The total amount of compound (B), the consumption of described surfactant is usually below 10 weight %, below more preferably 5 weight %.When described
When consumption is more than 10 weight %, the foaming characteristic of the emulsion obtained becomes strong, can cause problem because bubbling as during coating fluid.As non-
Ionic surfactant, can enumerate Polyethylene Glycol, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene benzene
Vinyl phenyl ether, polyoxyethylene sorbitan fatty acid ester etc..As anionic surfactant, alkyl sulfide can be enumerated
Hydrochlorate, alkylbenzenesulfonate, polyoxyethylene alkyl ether sulfate salt, polyoxyethylene alkylphenyl ether sulfate salt, 2-Sulfosuccinic acid two
Alkyl ester salt, alkylsulfonate, polyoxyethylene alkyl ether sulfosuccinate, polyoxyethylene styrene phenyl ether 2-Sulfosuccinic acid
Salt, polyoxyethylene alkyl ether phosphate ester, alpha-alkene sulfonate, naphthalene sulfonic acid-formaldehyde condensation product, polyoxyethylene alkyl phenyl ether sulphuric acid
Ester salt etc..As cationic surface active agent, alkyl trimethyl ammonium chloride, such as, trimethyl chlorination can be enumerated
Ammonium, hexadecyltrimethylammonium chloride, stearyl trimethyl ammonium chloride, VARISOFT TA100, docosyl three
Ammonio methacrylate (behenyl base trimethyl ammonium chloride), VARISOFT TA100, cetyl trimethylammonium bromide, 18
Alkyl trimethyl ammonium bromide；Lanoline cocamidopropyl ethyl dimethyl disulfide acetoacetic ester ammonium；Octadecyl trimethyl Saccharin Ammonium salt
(stearyl trimethyl ammonium saccharin)；Cetyl trimethyl Saccharin Ammonium salt；Methacryloxy second
Base trimethyl ammonium chloride；Docosanol trimethyl sulfate methyl ammonium and quaternary ammonium salt-91.Additionally, as reactive emulsifier,
Such as, the intramolecular described in JP 2003-293288 publication can be enumerated and there is the compound of polymerizable functional group.
The aqueous polymer emulsion obtained as mentioned above presents micro white emulsion outward appearance, when concentration is 25 weight %, has
PH is 1～8, and brookfield viscosity (25 DEG C of mensuration) is 3～100mPa s, and particle diameter is the character of 40～100nm.In view of balancing machine
Tool stability, low foaming characteristic, sizing efficiency etc., described particle diameter is more preferably 40～80nm.Additionally, " particle diameter " is described emulsion
The average primary particle diameter of particle, for example, it is possible to pass through dynamic light scattering determination.Additionally, as described particle size determination instrument
It is not particularly limited, it is, for example possible to use light scattering particle size analyser (trade name " ELSZ-2 ", big son (strain) manufactures).
As required, the surface sizing agent for paper making of the present invention can add various adding in described aqueous polymer emulsion
Add agent to prepare.As described additive, such as, defoamer, preservative, chelating agen, water soluble aluminum compound can be enumerated
Deng.
By adding water soluble aluminum compound, sizing efficiency can be improved further.As this water soluble aluminum compound, nothing
It is particularly limited to, known water soluble aluminum compound can be used.For example, it is preferable to use selected from by aluminum sulfate, aluminum chloride, alkalescence sulfur
The group that the polymer of acid aluminum, basic aluminium chloride, silicic acid aluminum sulfate (sulphuric acid acid ア Le ミ ニ ウ system) and above-claimed cpd is formed
In at least one.In above-claimed cpd, from a cost perspective, particularly preferred aluminum sulfate.
As the ratio (each in terms of the ratio of solid constituent) of surface sizing agent for paper making Yu water soluble aluminum compound, nothing
It is particularly limited to, from the point of view of sizing efficiency, preferably 5:95～95:5.Add additionally, water soluble aluminum compound can mix
It is added in surface sizing agent for paper making, it is also possible to be added separately in the coating fluid containing surface sizing agent for paper making.
As the coating fluid of the surface sizing agent for paper making containing the present invention, can directly use described paper grade (stock) surface
Sizing agent, or by it dilution after use, as required, it is possible to various additives with the use of.As described interpolation
Agent, such as, can enumerate the starch such as Oxytarch, organic phosphate starch, autologous modified starch, cationic starch, amphoteric starch
Class；The cellulose families such as carboxymethyl cellulose；Polyvinyl alcohol；Polyacrylamide；The paper of the water soluble polymers etc. such as sodium alginate
Open reinforcing agent；And it is antilubricant, preservative, antirust agent, pH adjusting agent, defoamer, thickening agent, filler, antioxidant, water-fast
Agent, coalescents, pigment, dyestuff etc..
Time actually used, as the solid component concentration in coating fluid, the surface sizing agent for paper making of the present invention is usually
About 0.001～2 weight %, the scope of preferably 0.05～0.5 weight %.
The paper of the present invention is the coating fluid using the surface sizing agent for paper making containing the present invention, utilizes various known
Means, obtain described coating solution on body paper.
As described body paper, it is not particularly limited, generally can use not the carrying out with lignocellulose fiber as raw material
The paper of coating and cardboard.Additionally, described body paper is prepared by paper grade pulp, as described paper grade pulp, can enumerate
The chemical pulps such as LBKP, NBKP, the mechanical pulp such as GP, TMP, secondary stock etc..Additionally, fill out for interpolation in described body paper
The various additives such as material, sizing agent, dry strength agent, are not particularly limited.
As the kind of paper that the Cypres of the above-mentioned body paper coating present invention is obtained, can enumerate list paper using,
The paper used for recording such as PPC paper using, heat sensitive recording chart；The coating paper such as art paper, cast-coated paper, high-quality coating paper；Kraft paper, white volume
The package papers such as paper；Other specifiable paper have: the various paper such as writing folio, books paper using, printing, paper for newspapers
Open (machine-made paper)；Paper-made vessel cardboard and lining paper, the Concha Arcaes such as Manila board, white board, chipboard (chip board)
The cardboards such as core.
Additionally, use the surface sizing agent for paper making of the present invention that the method for described various body paper coating be there is no particularly
Limit, be suitable for known method, such as infusion process, size press method, door roller method, scrape rod coating (bar coater) method,
Calender (calender) method, spraying process etc..Owing to the surface sizing agent for paper making of the present invention has above-mentioned good machinery surely
Qualitative, can be perfectly suitable for high speed machines this kind of there is high shear force coating method (rod metering size press rubbing method,
The transfer printing type Machine coating methods such as door roller rubbing method).
Embodiment
Manufacture example, embodiment and comparative example are set forth below and are further elaborated with the present invention, but the present invention does not limit
In these embodiments.Additionally, unless otherwise specified, " part " and " % " in each example is all weight standard.
Additionally, in each example, brookfield viscosity refers to sample regulation to the solution after 25 DEG C, utilize Brookfield viscometer (
(strain) manufactures) value that measures；Intrinsic viscosity refers to the value utilizing capillary viscosimeter (Ubbelohde) to measure；Particle diameter is
Refer to the value utilizing light scattering particle size analyser (trade name " ELSZ-2 ", big son (strain) manufactures) to measure.
The synthesis of synthesis example 1(amidin (A))
In the reaction vessel with agitator, condensing tube, nitrogen ingress pipe and thermometer, add ion exchange water 400
Part, the cationic starch of 88% (trade name " HI-CAT260 ", Japan's NSC(strain) manufactures) 114 parts, Ammonium persulfate. 10 parts,
Under nitrogen protection, carry out while stirring being incubated 1 hour in 80～85 DEG C.Then, the water regulation solid constituent adding ormal weight is dense
Degree is 20%, obtains amidin (A1).The gained amidin (A1) brookfield viscosity, intrinsic viscosity and pH when 25 DEG C
As shown in table 1.
Synthesis example 2～5
Except the kind of inorganic peroxide and consumption as viscosity reducers in synthesis example 1 is become as shown in table 1
Outside, other are identical with synthesis example 1 reacts, obtain various amidins (A2) that solid component concentration is 20%～
(A5).Brookfield viscosity, intrinsic viscosity and the pH when 25 DEG C is as shown in table 1 for these amidins.Additionally, the Fe table in table 1
Show green vitriol.
Table 1
Manufacture the synthesis of example 1(aqueous polymer emulsion (surface sizing agent for paper making))
In the reaction vessel with agitator, condensing tube, nitrogen ingress pipe, thermometer and Dropping funnel, add starch
Aqueous solution (A1) 500 parts, ion exchange water 80 parts, green vitriol 0.08 part, be sufficiently displaced from reaction vessel with nitrogen
Oxygen after, in making system while stirring, temperature rises to 80 DEG C.Then, in system, unsaturated monomer was dripped with about 2 hours
Mixture and polymerization initiator aqueous solution, wherein said unsaturated monomer mixture is by styrene 20 parts, isobutyl
Ester 80 parts mixes, and described polymerization initiator aqueous solution is (relative to institute by aqueous hydrogen peroxide solution 10 parts that concentration is 35%
State unsaturated monomer, be 3.5 weight portions) it is dissolved in 100 parts of water and obtains.Dripping and finish, insulation reaction makes reaction complete in 2 hours.
It follows that add the sodium hydrate aqueous solution 14 parts of 32% after Leng Que, dilute with water obtains surface sizing agent for paper making.Thus
To the concentration of surface sizing agent for paper making be 25%, at 25 DEG C, brookfield viscosity is 5mPa s, and pH is 3.3, and particle diameter is 75nm.
Manufacture example 2～11 and compare manufacture example 1～10
Except according to the kind of the amidin shown in table 2 and usage amount and/or the kind of unsaturated monomer and use
Outside the kind of amount and/or initiator, example 1 is identical operates with manufacture for other, obtains 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 arrived is as shown in table 2.
Manufacture example 12
In the beaker of 1L, the aluminum sulfate solution of the surface sizing agent for paper making 100 parts that obtains and 50% will be manufactured in example 1
After 50 parts (solid constituent ratio=50/50 of surface sizing agent for paper making/aluminum sulfate) mixing, add quantitative water dilution, obtain
Surface sizing agent for paper making, the aqueous polymer emulsion of described surface sizing agent for paper making and the total solid constituent concentration of aluminum sulfate
Be the brookfield viscosity of 25%, 25 DEG C be 5mPa s, pH is 2.2, and particle diameter is 78nm.
In table 2, AMSD represents 2, and 4-diphenyl-4-methyl-1-pentene, NDM represent that n-dodecyl mercaptan, St represent benzene
Ethylene, IBMA represent that isobutyl methacrylate, BA represent that butyl acrylate, 2-EHA represent 2-EHA, AN table
Show that acrylonitrile, DM represent that dimethylaminoethyl methacrylate, AA represent that acrylic acid, APS represent that Ammonium persulfate., Fe represent seven water
Close ferrous sulfate, sulphuric acid Al represents 16 hydrazine aluminum sulfates.
<preparation of coating fluid>
Oxytarch (prince's U Application ス タ チ (strain) manufactures, trade name " prince エ ス A ") is become according to solid
Point concentration 15% carries out gelatinizing, and using the preparation of described Oxytarch is 5% Oxytarch, 0.2% paper grade (stock) containing solid component concentration
The various coating fluids of Cypres.
<preparation of test paper using>
Utilize door roll coater ((strain) エ ス エ system テ manufacture) respectively by matter on described coating solution to neutrality
Paper (basic weight 60g/m2, 1 μ L water droplet degree of sizing 5 seconds) on.Then, various coating paper is made to be dried by rotary roller drying machine
(105 DEG C, 1 minute), obtain testing paper using.
<mensuration of infiltration colloidality>
Paper using is respectively tested for what profit obtained with the aforedescribed process, the method specified based on Japan TAPPI No.33,
Drip 1 μ L water on test paper using surface, measures paper and absorbs the time of water droplet, measures water droplet degree of sizing (second).Numeral is the biggest, represents
Its sizing efficiency is the best.Result is as shown in table 3.
<test of foaming characteristic>
Described coating fluid is heated to 50 DEG C, processes 2 minutes with home-use agitator, measure liquid level after process immediately high
Degree (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 regulated to 30 ° of dH, is heated to 50 DEG C, keep while this temperature with the experiment of two rollers
Room size press circulates 1 hour, according to following standard, the generation of agglutinator and the pollution of two rollers is carried out visual assessment.Result is such as
Shown in table 3.
◎: mechanical stability fabulous (not can confirm that agglutinator, roller is pollution-free)
Zero: good mechanical stability (not can confirm that agglutinator, roller has light contamination)
△: mechanical stability poor (can confirm that a small amount of agglutinator, roller has pollution)
×: mechanical stability poor (having can confirm that substantial amounts of agglutinator, roller has substantially pollution)
Table 3
From table 3 it can be seen that the surface sizing agent for paper making of the present invention with compare with compared with surface sizing agent for paper making, right
Good in the mechanical stability of the coating process (by door roller or size press etc.) of high shear force, bubble during coating few, simultaneously
Sizing efficiency is excellent.
Claims (9)
1. a surface sizing agent for paper making, it is characterised in that described surface sizing agent for paper making contains aqueous polymer emulsion,
Described aqueous polymer emulsion is in the presence of starch, polymerization initiator and chain-transferring agent, makes unsaturated monomer emulsion polymerization
Obtaining, wherein, described starch is the starch (A) using inorganic peroxide that intrinsic viscosity is adjusted to 0.1～0.9；Described not
Saturated monomer be by the total amount of unsaturated monomer mixture (B) be in terms of 100 weight %, by the phenylethylene of 3～30 weight % and
The unsaturated monomer mixture (B) of (methyl) esters of acrylic acid composition of 70～97 weight %；Described polymerization initiator is by mistake
The polymerization initiator (C) that hydrogen oxide and heavy metallic salt are made；Further, relative to the total amount of described unsaturated monomer mixture (B)
100 weight portions, use the described starch (A) of 80～200 weight portions to carry out emulsion polymerization and obtain described aqueous polymer emulsion.
2. surface sizing agent for paper making as claimed in claim 1, wherein, described inorganic peroxide is for selected from by persulfuric acid
At least one in the group of ammonium, potassium peroxydisulfate and sodium peroxydisulfate composition.
3. surface sizing agent for paper making as claimed in claim 1 or 2, wherein, described chain-transferring agent is 2,4-diphenyl-4-first
Base-1-amylene.
4. surface sizing agent for paper making as claimed in claim 1 or 2, wherein, described polymerization initiator (C) is iron sulfate and sulfur
At least one water solublity heavy metallic salt in acid copper is made with hydrogen peroxide, and meanwhile, the use ratio of hydrogen peroxide is 95～99
Weight %.
5. surface sizing agent for paper making as claimed in claim 1 or 2, wherein, the particle diameter of described aqueous polymer emulsion is 40
～100nm.
6. surface sizing agent for paper making as claimed in claim 1 or 2, wherein, described (methyl) esters of acrylic acid is for being selected from
In by (methyl) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) tert-butyl acrylate, (methyl) acrylic acid 2-second
At least one in the group of base own ester composition.
7. surface sizing agent for paper making as claimed in claim 1 or 2, wherein, the Bu Shi of described surface sizing agent for paper making
Viscosity is 3～100mPa s, and described brookfield viscosity measures under conditions of solid component concentration is 25 weight %, temperature 25 DEG C.
8. surface sizing agent for paper making as claimed in claim 1 or 2, wherein, described surface sizing agent for paper making contains water-soluble
Property aluminium compound, and, each in terms of the ratio of solid constituent, described surface sizing agent for paper making and described water-soluble aluminum chemical combination
The ratio of thing is 5:95～95:5.
9. one kind uses in claim 1～8 surface sizing agent for paper making described in any one to be coated on body paper
The paper arrived.
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| 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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| CN104005264B true CN104005264B (en) | 2016-08-17 |
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| JP (1) | JP6090657B2 (en) |
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| JP6566204B2 (en) * | 2014-09-30 | 2019-08-28 | 荒川化学工業株式会社 | Paper additive and 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 |
| CN104497721B (en) * | 2014-12-02 | 2017-02-22 | 周宏亮 | Release agent as well as release paper and release film of release agent |
| CN105038488B (en) * | 2015-08-04 | 2017-07-14 | 上海维凯光电新材料有限公司 | Possess offset printing transfer coatings of high anti-scratch performance and preparation method thereof |
| JP7188113B2 (en) * | 2018-01-22 | 2022-12-13 | 荒川化学工業株式会社 | Surface emulsion sizing agent for papermaking, method for producing surface emulsion sizing agent for papermaking, and coated paper |
| 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 |
| 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 |
| 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 |
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| US4855343A (en) * | 1986-08-14 | 1989-08-08 | Basf Aktiengesellschaft | Paper size based on finely divided aqueous dispersions |
| CN101851877A (en) * | 2009-03-31 | 2010-10-06 | 荒川化学工业株式会社 | Surface coating liquid for papermaking and paper |
| CN102656192A (en) * | 2009-10-02 | 2012-09-05 | 巴斯夫欧洲公司 | Finely divided starch-containing polymer dispersions, method for the production thereof and use thereof as sizing agent in paper manufacturing |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19806745A1 (en) * | 1998-02-18 | 1999-08-19 | Bayer Ag | Aqueous polymer dispersion useful as surface sizing agent for paper, cardboard etc. |
| US6114417A (en) * | 1998-10-16 | 2000-09-05 | Cytec Technology Corp. | Paper sizing agents and methods |
| JP5136862B2 (en) * | 2009-01-27 | 2013-02-06 | 荒川化学工業株式会社 | Paper-making surface sizing agent, coating liquid containing paper-making surface sizing agent, and paper obtained using these |
| JP5879041B2 (en) * | 2011-03-29 | 2016-03-08 | ハリマ化成株式会社 | Method for producing cationic surface sizing agent and sizing agent obtained by the method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4855343A (en) * | 1986-08-14 | 1989-08-08 | Basf Aktiengesellschaft | Paper size based on finely divided aqueous dispersions |
| CN101851877A (en) * | 2009-03-31 | 2010-10-06 | 荒川化学工业株式会社 | Surface coating liquid for papermaking and paper |
| CN102656192A (en) * | 2009-10-02 | 2012-09-05 | 巴斯夫欧洲公司 | Finely divided starch-containing polymer dispersions, method for the production thereof and use thereof as sizing agent in paper manufacturing |
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| CN104005264A (en) | 2014-08-27 |
| JP6090657B2 (en) | 2017-03-08 |
| TW201441448A (en) | 2014-11-01 |
| TWI585268B (en) | 2017-06-01 |
| JP2014163002A (en) | 2014-09-08 |
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