CN102167781A - Copolymer latex, producing method thereof and composition for paper coating - Google Patents

Copolymer latex, producing method thereof and composition for paper coating Download PDF

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Publication number
CN102167781A
CN102167781A CN2011100504141A CN201110050414A CN102167781A CN 102167781 A CN102167781 A CN 102167781A CN 2011100504141 A CN2011100504141 A CN 2011100504141A CN 201110050414 A CN201110050414 A CN 201110050414A CN 102167781 A CN102167781 A CN 102167781A
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weight
monomer
copolymer emulsion
section
monomers
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CN102167781B (en
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细谷隆史
中森弘
木户正树
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Nippon A&L Inc
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Nippon A&L Inc
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Priority claimed from JP2010041206A external-priority patent/JP5466044B2/en
Priority claimed from JP2010061674A external-priority patent/JP2011195972A/en
Priority claimed from JP2010061677A external-priority patent/JP5302251B2/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paper (AREA)

Abstract

The invention provides a copolymer latex which is obtained by the polymerization of at least two sections of polymerization processes and is composed by different monomer components. The copolymer latex is obtained by the polymerization of monomer compositions composed by monomer components of the first and the second sections in a regulated range. The velocity slope dependence of an E type viscosity when the solid constituent is adjusted to 50% and the liquid temperature is adjusted to 25 DEG meets a formula (1) that is B/A=0.50-1.1. In the formula (1), A represents the E type viscosity of a velocity slope 2sec-1, and B represents the E type viscosity of a velocity slope 10sec-1.

Description

Copolymer emulsion, its manufacture method and paper coating composition
Technical field
The present invention relates to copolymer emulsion, its manufacture method and paper coating composition.
The generation that is specifically related to agglutinator in the manufacturing process or dirt settling is few, and viscosity of latex is low, good copolymer emulsion and paper coating compositions such as transportation property, keeping and storage stability.
Also relating to paper is coated with copolymer emulsion and paper coating composition, the coating of this paper is the copolymer emulsion that is used as tackiness agent in the paper coating composition with copolymer emulsion, the paper coating composition that will contain this latex coat paper and blank sheet of paper gloss, the print gloss of White Board and the good strength when printing.
Also relate to paper coating with copolymer emulsion, its manufacture method and contain the paper coating composition of this copolymer emulsion, this paper coating is the copolymer emulsion that is used as tackiness agent in the paper coating composition with copolymer emulsion, coating operation in White Board manufacturing process is good, and good strength during the printing of White Board.
Background technology
As everyone knows, to be widely used as the back starching etc. with paper conversion field or carpet be the various tackiness agents of representative to carboxy-modified butadiene-based copolymer emulsion.Corresponding each purposes is varied to the desired performance of tackiness agent, for corresponding with it, tries every possible means to change the composition and the structure of copolymer emulsion, so that can bring into play performances such as the improvement of bonding strength and adhering reduction.On the other hand, owing to be tackiness agent, that is, so-called " caking agent " therefore also can cause the bad problem in the manufacturing process.Agglutinator increase in the time of can exemplifying attachment issue in each equipment for example or transportation, the curing in pipe arrangement etc.
Particularly in the paper conversion field, in the manufacturing of White Board, also carry out cost degradation in recent years, copolymer emulsion for higher price in coating compound, owing to improve the performance of latex, the fusion umber is correspondingly reduced, help to significantly reduce manufacturing cost, the influence that latex such as intensity raising brings the manufacturing cost of White Board quality and White Board when therefore making the printing of latex more and more is much accounted of.In addition, the intensity in the time of generally will improving printing importantly increases bonding surface area by the particle diameter that reduces latex, or guarantees the stability of coating by increasing amount of functional groups, gives full play to the effect of caking agent.But another side, viscosity of latex rises, cause in the blending process of manufacturing stage of copolymer emulsion or transportation operation, keeping operation and paper coating composition, the unworkable example of copolymer emulsion constantly increases, thereby just becomes problem keeping how reducing viscosity of latex in high-quality.
In order to solve above-mentioned problem, for example introduced following technology in Japanese patent laid-open 3-182504 communique: the fine coagulative generation by the latex that in the presence of the seed latex of specific composition and α-Jia Jibenyixierjuwu specific composition monomer composition polymeric manufacture method made is few, excellent in stability.Also have, in Japanese patent laid-open 11-117189 communique, disclosed following technology: use the polymerization residue of copolymer emulsion few by the paper coating of in polymerization process, separately using 2 kinds of different emulsifying agents to get, can stablize and manufacturing effectively, use the White Board rerum natura of this latex good.
But the operability of intensity and copolymer emulsion when these various improving technologies still are not enough to get both the desired good printing of White Board just becomes big problem in the viscosity that keeps how reducing latex under the more high-quality state.
In addition, in recent years, owing to reasons such as its printing effect are good, White Board is used to very many prints.In periodicals such as quarterly, monthly magazine, all use the situation of White Board also to increase greatly at all pages.Particularly, Direct Mail advertisement in the mail order business or goods catalogue etc. basically all pages or leaves all use White Board.
Generally, the paper coating composition be by white pigments such as carclazyte or lime carbonate are scattered in water dispersible pigment dispersion, be used for pigment is adhesively fixed to each other and with the pigment water-borne coatings that tackiness agent on body paper and other additives constitute that is adhesively fixed.Use with styrene butadiene based copolymer latex as the synthetic emulsion tackiness agent of representative or with starch, casein natural glue as tackiness agent as representative.Wherein, the degree of freedom of the quality design of styrene butadiene based copolymer latex is big, be widely used as being suitable for most the tackiness agent of paper coating composition at present, qualities such as the print gloss of operation the when performance of the performance impact paper coating composition of known styrene butadiene based copolymer latex and White Board are made or final White Board goods, surface strength.
Especially the outward appearance of end article being had the blank sheet of paper gloss of considerable influence and print gloss in the quality of White Board is very important project.The gloss of White Board represented by the normal reflection rate of the light on White Board surface and printing ink epithelium surface, if therefore White Board surface and printing ink epithelium surface smoothing then gloss uprise.This just illustrates that the employed pigment of coating layer plays important effect.Generally, because tackiness agents such as copolymer emulsion are the essential factors that hinders the orientation of pigment, therefore add the visible White Board surface roughen in back, the tendency that has blank sheet of paper gloss to reduce.On the other hand, for print gloss, absorb printing ink epithelium drying and must form more level and smooth printing ink epithelium surface owing to the vehicle in the printing ink (vehicle) is difficult to applied paper surface more with regard to slow more, print gloss is improved in the space that tackiness agents such as therefore general increase copolymer emulsion reduce White Board.So blank sheet of paper gloss and print gloss are opposite rerum natura, be difficult to improve simultaneously.Along with the high speed of printing, the intensity when also requiring to improve the White Board printing in order to solve these problems, has proposed various technical schemes in addition.
For example, open the Japanese Patent spy and introduced the technology of improving the blank sheet of paper gloss, print gloss, bonding strength etc. of White Board by the copolymer emulsion that uses the specific composition scope among the 2001-31727.For example, the Japanese Patent spy open disclosed among the 2005-139577 utilize that pH is 2～6, alkali metal content obtains to be coated with the good and blank sheet of paper gloss of operation, print gloss, surface smoothing, White Board that surface strength is good for the copolymer emulsion of the specific composition below the specified quantitative technology.Also have, open to have introduced in the 2007-204513 communique the Japanese Patent spy and be controlled at 200ppm to obtain down that foul smell is suppressed and the technology of blank sheet of paper gloss, print gloss, ink setting, copolymer emulsion that surface strength is good by the trimerical amount of styrene dimer body, vinylbenzene in the volatile component that latex is contained.
On the other hand, in the manufacture method of White Board,, blank sheet of paper gloss is improved by in general mineral dye, also using hollow plastic pigment.But, if add the hollow plastic raw material then ink setting accelerates, so have the tendency be difficult to manifest print gloss, therefore open to have disclosed in the 2006-37312 communique and contain the technology that hollow plastic pigment and water-ground limestone obtain the good coating layer of blank sheet of paper gloss and print gloss in the paper coating composition of using by the undercoat in 2 layers of coating the Japanese Patent spy.
But, these improving technologies do not reach the level of the performance that fully satisfies desired blank sheet of paper gloss of White Board and print gloss as yet, and because though hollow plastic pigment is to blank sheet of paper glossy influence big but coating cost significantly raises, need very urgently therefore that this does bigger improvement on the one hand from copolymer emulsion.
Also have, the technology that the paper coating composition that uses the copolymer emulsion of specified particle diameter scope in the paper coating composition of the water-ground limestone by containing the specified particle diameter scope more than the 30 weight % obtains the good and basic matt uneven high-quality coated paper for printing of the high-speed coating of blade coating has for example been introduced in the improvement of the operation when making about White Board in Japanese patent laid-open 11-50390 communique.
About the quality improving of the surface strength of White Board goods etc., for example open and introduced in the 2006-152484 communique by using the hud typed copolymer emulsion that get by multi-stage polymeric below the median size 150mm to obtain print gloss well and the technology of printing ink setting (イ Application Network セ ッ ト), delustring White Board that ink setting is good the Japanese Patent spy.In Japanese patent laid-open 9-31894 communique, disclosed by use after the initial feeding section of polymeric will contain the monomer mixture polymerization of whole consumptions of unsaturated dicarboxylic acid and methacrylic acid, the technology of offset printing usefulness White Board that surface strength, water tolerance, even China ink (イ Application Network meat), anti-whipability when the paper coating composition of the 2nd section copolymer emulsion that get with post polymerization obtains to print is good.Also have, surface strength, print gloss, printing ink when the Japanese Patent spy opens the film introduced in the 2008-248446 communique by the regulation copolymer emulsion and can provide printing to the contact angle of soybean oil such as is provided with at the technology of the good White Board of printing adaptability, obtain this copolymer emulsion, preferably adopt multi-stage polymeric.
But these various improving technologies still are unrealized can the corresponding desired coating operation of paper coating composition and the White Board rerum natura of the coating apparatus of high speed day by day, particularly needs to do from the latex aspect further improvement very urgently.
Summary of the invention
The purpose of this invention is to provide in the manufacturing process adhere to or agglutinator produces less, the excellent in stability of particle and make the copolymer emulsion that production efficiency improves and viscosity of latex is low, transportation property is good by this.
In addition, the purpose of this invention is to provide can obtain blank sheet of paper gloss, print gloss is good and the paper coating of the good White Board of when printing intensity with copolymer emulsion and paper coating composition.
In addition, copolymer emulsion, its manufacture method and the paper coating composition of the good White Board of intensity when the redispersibility of adhesivity that the purpose of this invention is to provide latex film good (that is, be difficult for adhere to) and paper coating composition well can access the good and printing of coating operation by this.
Promptly, the present invention forms the copolymer emulsion that the polymerization of at least 2 sections polymerization process that constitute gets by having by different monomers, at the 1st section is aliphatics conjugated diene monomer 1.5～24 weight %, acrylic monomer 5.1～25 weight %, ethene is unsaturated carboxylic acid monomer 3.1～20 weight % and monomeric 13～32 weight % (all monomers add up to 100 weight %) that add up to that can constitute with other monomers 0～22.3 weight % of their copolymerization, at the 2nd section is later on aliphatics conjugated diene monomer 10～60 weight %, acrylic monomer 5～30 weight %, ethene is unsaturated carboxylic acid monomer 0～13 weight % and can adds up to 68～87 weight % (all monomers add up to 100 weight %) with the monomer that other monomers 0～72 weight % of their copolymerization constitutes, it is characterized in that the solids component of this copolymer emulsion is adjusted into 50%, the velocity slope dependency of the E type viscosity when the liquid temperature is adjusted into 25 ℃ satisfies following formula (1):
B/A＝0.50～1.1 ……(1)
Wherein, A represents velocity slope 2sec -1E type viscosity, B represents velocity slope 10sec -1E type viscosity.
The present invention relates to paper is coated with copolymer emulsion and paper coating composition.Be specifically related to form the copolymer emulsion that the polymerization of at least 2 sections polymerization process that constitute gets by having by different monomers, at the 1st section is aliphatics conjugated diene monomer 1.5～24 weight %, acrylic monomer 5.1～25 weight %, ethene is unsaturated carboxylic acid monomer 3.1～20 weight % and monomeric 13～32 weight % (all monomers add up to 100 weight %) that add up to that can constitute with other monomers 0～22.3 weight % of their copolymerization, at the 2nd section is later on aliphatics conjugated diene monomer 10～60 weight %, acrylic monomer 5～30 weight %, ethene is unsaturated carboxylic acid monomer 0～13 weight % and can adds up to 68～87 weight % (all monomers add up to 100 weight %) with the monomer that other monomers 0～72 weight % of their copolymerization constitutes, it is characterized in that, this copolymer emulsion is coated the transparent substrate after drying and film (glue spread is counted 13g/m with dry weight 2± 1g/m 2) the haze value of measuring by JIS K7136 and the difference of the haze value of transparent substrate self be 0～1.0%.
In addition, copolymer emulsion of the present invention is the copolymer emulsion that is used as tackiness agent in the paper coating composition, and be with aliphatics conjugated diene monomer, the acrylic monomer, ethene be unsaturated carboxylic acid monomer and can be with other monomers (monomer adds up to 100 weight %) letex polymerization of their copolymerization copolymer emulsion, it is characterized in that, have by different monomers and form at least 3 sections polymerization process that constitute, at the 1st section is with aliphatics conjugated diene monomer 1.5～24 weight %, acrylic monomer 5.1～25 weight %, ethene is unsaturated carboxylic acid monomer 4.1～20 weight % and can adds up to 13～34 weight % polymerizations with the monomer that other monomers 0～23.3 weight % of their copolymerization constitutes, again after the 2nd section with aliphatics conjugated diene monomer 10～60 weight %, acrylic monomer 5～30 weight %, ethene is unsaturated carboxylic acid monomer 0～13 weight % and can adds up to 66～87 weight % polymerizations with the monomer that other monomers 0～72 weight % of their copolymerization constitutes.
Also have, the manufacture method of copolymer emulsion of the present invention is with aliphatics conjugated diene monomer, the acrylic monomer, ethene be unsaturated carboxylic acid monomer and can be with other monomers (monomer adds up to 100 weight %) letex polymerization of their copolymerization the manufacture method of copolymer emulsion, this copolymer emulsion is used as tackiness agent in the paper coating composition, it is characterized in that, have by different monomers and form at least 3 sections polymerization process that constitute, be included in the 1st section with aliphatics conjugated diene monomer 1.5～24 weight %, acrylic monomer 5.1～25 weight %, ethene is unsaturated carboxylic acid monomer 4.1～20 weight % and can adds up to 13～34 weight % polymeric operations with the monomer that other monomers 0～23.3 weight % of their copolymerization constitutes, and after the 2nd section with aliphatics conjugated diene monomer 10～60 weight %, acrylic monomer 5～30 weight %, ethene is unsaturated carboxylic acid monomer 0～13 weight % and can adds up to 66～87 weight % polymeric operations with the monomer that other monomers 0～72 weight % of their copolymerization constitutes.
By the present invention, can obtain in manufacturing process adhere to and agglutinator produces less and the low copolymer emulsion of viscosity.
By copolymer emulsion of the present invention and paper coating composition, can obtain blank sheet of paper gloss, print gloss is good and the good White Board of when printing intensity.
Coating operation when in addition, the conduct of copolymer emulsion of the present invention is made White Board brings the redispersibility of the adhesivity of latex film of principal element of influence and paper coating composition good.Also have, be coated with this paper coating composition and the printing of White Board the time good strength.
Copolymer emulsion of the present invention is by being unsaturated carboxylic acid monomer with aliphatics conjugated diene monomer, acrylic monomer, ethene and can getting with other monomer emulsion polymerizations of their copolymerization.
As aliphatics conjugated diene monomer, can exemplify 1,3-butadiene, 2-methyl isophthalic acid, 3-divinyl, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-divinyl, substituted straight chain conjugation pentadiene class, replacement and side chain conjugation hexadiene class etc., these monomers can use more than a kind or 2 kinds.Especially preferably use 1,3-butadiene.
As the acrylic monomer, can exemplify vinyl cyanide, methacrylonitrile, α-Lv Bingxijing, α-ethyl acrylonitrile etc., these monomers can use more than a kind or 2 kinds.Especially preferably use vinyl cyanide or methacrylonitrile.
As ethene is unsaturated carboxylic acid monomer, but monoprotic acid or diprotic acid (acid anhydride) such as exemplified by acrylic, methacrylic acid, Ba Dousuan, toxilic acid, fumaric acid, methylene-succinic acid, and these monomers can use more than a kind or 2 kinds.
As being other monomers of unsaturated carboxylic acid monomer copolymerization, can exemplify alkenyl aromatic monomer, unsaturated carboxylic acid alkyl ester monomer, the unsaturated monomer that contains hydroxyalkyl, unsaturated carboxylic acid amide monomer etc. with above-mentioned aliphatics conjugated diene monomer, acrylic monomer and ethene.
As the alkenyl aromatic monomer, can exemplify vinylbenzene, α-vinylbenzene, methyl α-vinylbenzene, Vinyl toluene and Vinylstyrene etc., these monomers can use more than a kind or 2 kinds.Especially preferably use vinylbenzene.
As the unsaturated carboxylic acid alkyl ester monomer, but exemplified by acrylic methyl esters, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, butyl acrylate, glycidyl methacrylate, dimethyl fumarate, DEF, dimethyl maleate, ethyl maleate, dimethyl itaconate, monomethyl fumarate, monomethyl ester, 2-EHA etc., these monomers can use more than a kind or 2 kinds.Especially preferably use methyl methacrylate.
As the unsaturated monomer that contains hydroxyalkyl, but exemplified by acrylic beta-hydroxy ethyl ester, Jia Jibingxisuanβ-Qiang Yizhi, Propylene glycol monoacrylate, Rocryl 410, vinylformic acid hydroxy butyl ester, methacrylic acid hydroxy butyl ester, methacrylic acid 3-chloro-2-hydroxypropyl acrylate, toxilic acid two-(ethylene glycol) ester, methylene-succinic acid two-(ethylene glycol) ester, toxilic acid 2-hydroxyl ethyl ester, two (2-hydroxyethyl) esters of toxilic acid, toxilic acid 2-hydroxyethyl methyl esters etc., these monomers can use more than a kind or 2 kinds.Especially preferably use propenoic acid beta-hydroxy ethyl ester.
As the unsaturated carboxylic acid amide monomer, can exemplify acrylamide, Methacrylamide, N hydroxymethyl acrylamide, N-methylol methacrylamide, N,N-DMAA etc., these monomers can use more than a kind or 2 kinds.Especially preferably use acrylamide or Methacrylamide.
Also have, except above-mentioned monomer, the monomer that ethene, propylene, vinyl-acetic ester, propionate, vinylchlorid, vinylidene chloride etc. are generally used for letex polymerization all can use.
Copolymer emulsion of the present invention with solids component be adjusted to 50%, the liquid temperature be adjusted to 25 ℃ and change that velocity slope is measured E type viscosity and numerical value must satisfy following formula (1).
B/A＝0.50～1.1 ·······(1)
In the following formula, A represents velocity slope 2sec -1E type viscosity, B represents velocity slope 10sec -1E type viscosity.
If the numerical value of this B/A is not in 0.50～1.1 scope, then the generation of dirt settling in the manufacturing process or agglutinator increases, and viscosity of latex uprises.
Also have, when for example copolymer emulsion being used as the tackiness agent of paper coating composition, sometimes intensity and reduce latex particle size or increase the consumption of functional group's (for example ethene unsaturated carboxylic acid monomer etc.) when improving the printing of White Board, in these cases, if the velocity slope dependency of latex also satisfies following formula (1), then viscosity of latex is difficult for rising, and is more satisfactory.
Transparency height behind the copolymer emulsion drying and forming-film of the present invention, at painting layer surface and the inner reflection of light that suppresses of coating layer, normal reflection rate by this is improved, and blank sheet of paper gloss and print gloss are improved.Be specifically with copolymer emulsion coat transparent substrate and dry and latex film (glue spread is counted 13g/m with dry weight 2± 1g/m 2) the difference based on the mist degree of the mist degree measured value of JIS K7136 and transparent substrate self be 0～1.0%.Here, general haze value is meant by departing from the percentage of the transmitted light of incident light direction more than 2.5 ° in the transmitted light of test film because of scattering forwards, defines with " diffused transmission rate with the ratio of light transmittance (parallel transmissivity+diffused transmission rate) " entirely.Therefore, the little then transparency of haze value height.If the difference of the haze value of above-mentioned latex and transparent substrate surpasses 1.0%, then poor in the transparency of the latex part of painting layer surface and the inner membranization of coating layer, diffuse-reflectance increases, and causes blank sheet of paper gloss and print gloss to reduce.
Copolymer emulsion of the present invention has different monomers and forms at least 2 sections polymerization process that constitute, and monomer whose is formed must be in following ranges.That is must be that aliphatics conjugated diene monomer 1.5～24 weight %, acrylic monomer 5.1～25 weight %, ethene are unsaturated carboxylic acid monomer 3.1～20 weight % and can add up to 13～32 weight % with the monomer that other monomers 0～22.3 weight % of their copolymerization constitutes, at the 1st section.Must be after the 2nd section be that unsaturated carboxylic acid monomer 0～13 weight % and the monomer that can constitute with other monomers 0～72 weight % of their copolymerization add up to 68～87 weight % polymerizations with aliphatics conjugated diene monomer 10～60 weight %, acrylic monomer 5～30 weight %, ethene.
If outside the scope of shown in above the 1st section and the 2nd section later monomer compositing range and monomer total amount, then the velocity slope dependency of copolymer emulsion can't satisfy following formula (1), the agglutinator in the manufacturing process of latex or the generation of dirt settling are many, and viscosity of latex can not reduce yet, and causes operability deteriorations such as transportation property.In addition, the difference of the haze value of copolymer emulsion film and coated substrate can be below 1.0%, blank sheet of paper gloss and print gloss deterioration.
Ethene the 1st section interpolation is that unsaturated carboxylic acid monomer is preferably more than the 3.6 weight % because like this during the printing of White Board intensity manifest better.Further more preferably more than the 4.1 weight %.
Ethene is that unsaturated carboxylic acid monomer better is that 60 weight % of total amount are above and add in the 1st section polymerization process, if less than 60 weight % then the agglutinator that has in the manufacturing process produces many tendencies, intensity during the printing of White Board manifests the tendency of deterioration, and is therefore undesirable.
Be more preferably to have and form the different polymerization process more than 3 sections by monomer, at the 1st section with aliphatics conjugated diene monomer 1.5～24 weight %, acrylic monomer 5.1～25 weight %, ethene is unsaturated carboxylic acid monomer 4.1～20 weight % and can adds up to 13～32 weight % polymerizations with the monomer that other monomers 0～21.3 weight % of their copolymerization constitutes, again after the 2nd section with aliphatics conjugated diene monomer 10～60 weight %, acrylic monomer 5～30 weight %, ethene is unsaturated carboxylic acid monomer 0～13 weight % and can adds up to 68～87 weight % polymerizations with the monomer that other monomers 0～72 weight % of their copolymerization constitutes.By this, the manifesting property of intensity is better during the printing of White Board.
When having the polymerization process more than 3 sections, when the 2nd section monomeric total amount of using later on of acrylic is made as 100 weight %, the acrylic amount of monomer of adding in final polymerization process better is less than 45 weight %, viscosity of latex easily descends like this, the intensity exhibit excellent the during adhesivity of latex film and printing simultaneously.
In addition,, then have the trend that the generation of the agglutinator in the manufacturing process reduces, and the intensity the during printing of White Board manifests better, therefore preferably if the 2nd section monomer adds up to 10～66 weight %, the 3rd section later monomer adds up to 2～62 weight %.
The polymerization of copolymer emulsion of the present invention can be used known emulsifying agent (tensio-active agent).Can exemplify the sulfuric acid, alkylbenzene sulfonate, alkyl diphenyl base ether stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, aliphatic sulfonate, aliphatic carboxylate, westvaco rosin hydrochlorate, the formaldehyde condensation products of naphthene sulfonic acid, the anionic surfactants such as sulfuric acid of nonionic surfactant of higher alcohols for example, nonionic surfactants such as the alkyl ester type of polyoxyethylene glycol, alkyl phenyl ether type, alkyl ether type, these emulsifying agents can use more than a kind or 2 kinds.
The polymerization of copolymer emulsion of the present invention can be used known chain-transfer agent (molecular weight regulator) in indefinite ground.Can exemplify for example n-hexyl mercaptan, n-octyl mercaptan, tert octyl mercaptan, n-dodecyl mercaptan, uncle's lauryl mercaptan, alkyl sulfhydryls such as Octadecane base mercaptan, curing xanthogenic acid dimethyl ester, xanthate compounds such as diisopropyl xanthate disulfide, tetramethyl-thiuram disulfide, tetraethylthiuram disulfide, thiuram based compounds such as tetramethylthiuram monosulfide, 2, the 6-di-tert-butyl-4-methy phenol, phenol based compounds such as styrenated phenol, allylic cpds such as vinyl carbinol, methylene dichloride, methylene bromide, halogenated hydrocarbon compounds such as carbon tetrabromide, α-benzyloxy vinylbenzene, α-benzyloxy vinyl cyanide, α-vinyl ether such as benzyloxy acrylamide, triphenylethane, pentaphenylethane, propenal, Methylacrylaldehyde, Thiovanic acid, mercaptosuccinic acid, 2-ethylhexyl mercaptoacetate, terpinolene, α-Jia Jibenyixierjuwu etc., these chain-transfer agents can use more than a kind or 2 kinds.
In the polymerization of copolymer emulsion of the present invention, as known polymerization starter, can suitably use water-soluble polymerization initiators such as persulfuric acid lithium, Potassium Persulphate, Sodium Persulfate, ammonium persulphate, cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, hydrogen peroxide diisopropyl benzene, hydrogen peroxide 1,1,3, oil-soluble polymerization initiators such as 3-tetramethyl butyl.Especially preferably use Potassium Persulphate, Sodium Persulfate, cumene hydroperoxide, t-butyl hydroperoxide.
The concrete example of the reductive agent that preferably uses as the present invention, can exemplify sulphite, hydrosulphite, pyrosulfite, hyposulfite, dithionate, thiosulphate, formaldehyde sulfonate, phenyl aldehyde sulfonate, and carboxylic-acid and salt thereof such as L-xitix, saccharosonic acid, tartrate, citric acid, and recuding sugars such as glucose, sucrose, and amine such as xylidine, trolamine.Preferred especially L-xitix, saccharosonic acid.
In the polymerization of copolymer emulsion of the present invention, can use stable hydrocarbon such as pentane, hexane, heptane, octane, hexanaphthene, suberane as required, unsaturated hydrocarbons such as amylene, hexene, heptene, cyclopentenes, tetrahydrobenzene, suberene, 4-tetrahydrotoluene, 1-tetrahydrotoluene, hydrocarbon compounds such as aromatic hydrocarbon such as benzene,toluene,xylene.Though it is different with purpose of the present invention by tetrahydrobenzene or toluene that recovery such as wet distillation also utilize again easily that particularly the boiling point appropriateness is low, polymerization finishes the back, proper from the angle of environmental problem.
There is no particular limitation for the particle diameter of copolymer emulsion of the present invention, preferred 50～200nm.If number average bead diameter is less than 50nm then the stability degradation of particle, blank sheet of paper gloss deterioration, if surpass 200nm then the population of per unit weight tails off, bond area reduces, thereby is difficult to manifest bonding strength, and is therefore undesirable.In addition, and if surpassed 150nm during the printing of White Board intensity be difficult to manifest, therefore be more preferably 50～150nm.
To the gel content of copolymer emulsion of the present invention without any qualification, but preferred 60～100 weight % of gel content.If gel content is less than 60 weight %, then the film toughness of latex reduces, and the bonding strength of various caking agents descends.The trend that also has the strength degradation of White Board.Preferred especially 65～95 weight %.
In the polymerization of copolymer emulsion of the present invention, can use known additives such as oxygen trapping agent, sequestrant, dispersion agent as required, all there is no particular limitation for their kind, consumption, can use in right amount.Can also use known additives such as defoamer, protective agent, sanitas, antiseptic-germicide, fire retardant, UV light absorber, all there is no particular limitation for their kind, consumption, can use in right amount.In addition, copolymer emulsion of the present invention also can be according to its application target other latex of fusion in right amount.
During the manufacturing of copolymer emulsion of the present invention, there is no particular limitation to the addition means of monomer and other compositions, can adopt portion-wise addition method, continuous any one in addition means, the automatic feeding method, but among the present invention, polymerization process must carry out the multi-stage polymeric more than 2 sections.
In addition, paper coating composition of the present invention can be used alone or as a mixture known pigment respectively, for example, and mineral dyes such as kaolin, carclazyte, lime carbonate, talcum, barium sulfate, titanium oxide, aluminium hydroxide, zinc oxide, stain white; Perhaps pigment dyestuff such as polystyrene latex.
Also have, the content of the copolymer emulsion of the present invention in the paper coating composition better is to be 2～15 weight parts (solids components) with respect to 100 weight parts (solids component) pigment.The content of copolymer emulsion 2 weight parts with next can't bonding fully pigment, undesirable, if surpass 15 weight parts then the manufacturing cost of the copolymer emulsion that causes comprising in the coating rises.Be more preferably 2.5～12 parts of weight parts (solids component).
Can also use treated starches such as starch, Sumstar 190, esterification starch as required, natural glues such as soybean protein, casein, perhaps water-soluble composite adhesives such as polyvinyl alcohol, carboxymethyl cellulose etc.Can also be with synthetic latexes such as poly latex, acrylic acid series latex etc. with copolymer emulsion of the present invention and use.
When modulating paper coating composition of the present invention, can also add other auxiliary agents as required, dispersion agent (trisodium phosphate, sodium polyacrylate, Sodium hexametaphosphate 99 etc.) for example, defoamer (polyoxyethylene glycol, fatty acid ester, phosphoric acid ester, silicone oil etc.), levelling agent (turkey red oil, Dyhard RU 100, urea etc.), sanitas, releasing agent (calcium stearate, paraffin wax emulsion etc.), fluorescence dye, color water-retentivity rising agent (sodium alginate etc.).
The paper coating composition is coated coating can use technique known with the method for paper, for example airblade coating, curtain coating, blade coating, roller coat, rod such as are coated with at coating machine arbitrarily.After the coating, desiccated surface is with precision work such as calenderings.
The angle of copolymer emulsion of the present invention intensity etc. when improving coating operation and printing, must have by different monomers and form at least 3 sections polymerization process that constitute, at the 1st section polymeric monomer composition is aliphatics conjugated diene monomer 1.5～24 weight %, acrylic monomer 5.1～25 weight %, ethene be unsaturated carboxylic acid monomer 4.1～20 weight % and can with other monomers 0～22.3 weight % of their copolymerization (monomer adds up to 13～34 weight %), adding and carry out the polymeric monomer composition later at the 2nd section is aliphatics conjugated diene monomer 10～60 weight %, acrylic monomer 5～30 weight %, ethene be unsaturated carboxylic acid monomer 0～13 weight % and can with other monomers 0～72 weight % of their copolymerization (monomer adds up to 68～87 weight %).
If the 1st section aliphatics conjugated diene monomer is less than 1.5 weight % then the strength deterioration the during printing of White Board, if surpass 24 weight % then the adhesivity deterioration of latex, coating operation when particularly White Board being made brings detrimentally affect, as easily being attached to back flow roll etc.
If the 1st section acrylic monomer is less than 5.1 weight %, then the manifesting property of intensity the during printing of White Board and print gloss is poor, in addition, if surpass 25 weight % then intensity during the printing of White Board reduces.
If the 1st section ethene is unsaturated carboxylic acid monomer intensity difference less than 4.1 weight % then during the printing of the redispersibility of paper coating composition and White Board, if surpass 20 weight % then the viscosity of latex self is too high, cause the operability deteriorations such as latex delivery deterioration of liquid-feeding pump.
The redispersibility of paper coating composition is poor if the 1st section monomer adds up to less than 13 weight %, in addition, if surpass 34 weight % then intensity during the printing of White Board reduces.
If the 2nd section later aliphatics conjugated diene monomer is less than 10 weight % then the intensity difference the during printing of White Board, in addition, if surpass 60 weight % then the poor adhesion of latex film, the coating operation when particularly White Board being made brings detrimentally affect, as easily being attached to back flow roll etc.
If the 2nd section later acrylic monomer be less than 5 weight %, the manifesting property deterioration of intensity and print gloss during the printing of White Board then, in addition, if surpass 30 weight % then strength degradation during the printing of White Board.
The viscosity of latex self is too high if the 2nd section later ethene is that unsaturated carboxylic acid monomer surpasses 13 weight %, causes the operability deteriorations such as latex delivery deterioration of liquid-feeding pump.
Be made of the polymerization process that constitutes different monomers below 2 sections the time, the adhesivity of latex film descends.
Add and in the polymerization process of terminal section, do not add the good strength of the White Board when then printing if ethene is the above polymerization process at the 1st section of 60 weight % of whole consumptions of unsaturated carboxylic acid monomer.Also have, if when the 2nd section monomeric total amount of using later on of acrylic be made as 100 weight %, the acrylic amount of monomer of adding in final polymerization process is less than 45 weight %, and then the adhesivity of latex is good.
In having at least 3 sections the polymerization of copolymer emulsion of polymerization process, can use known emulsifying agent (tensio-active agent).For example, can exemplify above-mentioned emulsifying agent (tensio-active agent), these emulsifying agents can use more than a kind or 2 kinds.
In having at least 3 sections the polymerization of copolymer emulsion of polymerization process, can use known chain-transfer agent (molecular weight regulator) in indefinite ground.Can exemplify for example above-mentioned chain-transfer agent (molecular weight regulator), these chain-transfer agents can use more than a kind or 2 kinds.
In having at least 3 sections the polymerization of copolymer emulsion of polymerization process,, except above-mentioned polymerization starter, can also suitably use the reducto oxydative system polymerization starter as known polymerization starter.Especially preferably use Potassium Persulphate, Sodium Persulfate, cumene hydroperoxide, t-butyl hydroperoxide.There is no particular limitation to the amount of polymerization starter, can consider that monomer is formed, the pH of polyreaction system, do suitable adjustment with the combination of other additives etc.
In having at least 3 sections the polymerization of copolymer emulsion of polymerization process, can use above-mentioned hydrocarbon compound.Though it is different with purpose of the present invention by tetrahydrobenzene or toluene that wet distillation etc. reclaims, utilizes easily that particularly low, the polymerization of boiling point appropriateness finishes the back, proper from the angle of environmental problem.
There is no particular limitation for the particle diameter of De copolymer emulsion therefrom, preferred 50～150nm.If number average bead diameter is less than 50nm then blank sheet of paper gloss deterioration, if surpass 150nm then the trend of strength degradation when having the printing of White Board.The particle diameter of copolymer emulsion can be by suitably changing the various emulsifying agents that use, polymerization starter in the polymerization of copolymer emulsion the kind and the usage ratio of consumption or addition means, polywater thereof wait to be adjusted.
To the gel content of copolymer emulsion without any qualification, preferred 60～100 weight % of gel content.If the trend of strength degradation was undesirable when, then there was the printing of White Board less than 60 weight % in gel content.Preferred especially 65～98 weight %.
In having at least 3 sections the polymerization of copolymer emulsion of polymerization process, can use known additives such as oxygen trapping agent, sequestrant, dispersion agent as required, all there is no particular limitation for their kind, consumption, can use in right amount.Can also use known additives such as defoamer, protective agent, sanitas, antiseptic-germicide, fire retardant, UV light absorber, all there is no particular limitation for their kind, consumption, can use in right amount.
In addition, therefrom copolymer emulsion also can be according to its application target other latex of fusion in right amount.
During the manufacturing of this copolymer emulsion, addition means to monomer and other compositions, there is no particular limitation except having forming at least 3 sections polymerization process this point that constitute by different monomers, and monomeric addition means can adopt portion-wise addition method, any one in the addition means continuously.
The polymer latex that paper coating composition of the present invention contains pigment and got by above-mentioned operation.Pigment can be used alone or as a mixture known pigment respectively, for example above-mentioned pigment.
Also have, the content of the copolymer emulsion in the paper coating composition better is to be 2～20 weight parts (solids components) with respect to 100 weight parts (solids component) pigment.The content of copolymer emulsion then can't bonding fully pigment less than 2 weight parts, and is undesirable, if surpass 20 weight parts then opaqueness and blank sheet of paper gloss descend, and the cost of paper coating composition rises.
Can also use treated starches such as starch, Sumstar 190, esterification starch as required, natural glues such as soybean protein, casein, perhaps water-soluble composite adhesives such as polyvinyl alcohol, carboxymethyl cellulose etc.Can also be with synthetic latexes such as poly latex, acrylic acid series latex etc. with copolymer emulsion of the present invention and use.
When modulating paper coating composition of the present invention, can also add other auxiliary agents as required, dispersion agent (trisodium phosphate, sodium polyacrylate, Sodium hexametaphosphate 99 etc.) for example, defoamer (polyoxyethylene glycol, fatty acid ester, phosphoric acid ester, silicone oil etc.), levelling agent (turkey red oil, Dyhard RU 100, urea etc.), sanitas, releasing agent (calcium stearate, paraffin wax emulsion etc.), fluorescence dye, color water-retentivity rising agent (carboxymethyl cellulose, sodium alginate etc.).
The paper coating composition is coated coating can use technique known with the method for paper, for example above-mentioned any coating machine.After the coating, desiccated surface is with precision work such as calenderings.
Embodiment
Below, exemplifying embodiment the present invention is carried out more specific description, the present invention is only otherwise exceed the qualification that its technology main idea is not subjected to these embodiment.In addition, the part and the short of special explanation of % of expression ratio all refer to weight basis among the embodiment.Also have, the evaluation of the various rerum naturas among the embodiment is carried out according to following method.
＜latex 1～21 〉
The mensuration of the number average bead diameter of copolymer emulsion
The number average bead diameter of copolymer emulsion is passed through dynamic light scattering determination.Use FPAR-1000 (Otsuka Electronics Co., Ltd. system during mensuration).
The E type viscosity of copolymer emulsion
The solids component of copolymer emulsion is adjusted to 50% measures E type viscosity.In addition, survey periodic liquid temperature and use Water Tank with Temp.-controlled to keep constant 25 ℃, use 3 ° of circular cones to measure.Determining instrument uses the E type viscometer of Tokyo gauge corporate system.
The evaluation of dirt settling
To each copolymer emulsion, detect by an unaided eye and in polymerization, be attached to the dirt of reactor, estimate by following 3 grades.
A: dirt settling is considerably less
B: hardly staining metal
C: dirt settling is many
The mensuration of agglutinator production rate and evaluation
Gather the 1kg sample of the copolymer emulsion after polymerization finishes, with 300 order metal mesh filters.Will be after agglutinator drying residual on the wire netting gravimetry, obtain the ratio (agglutinator production rate) with sample (solids component conversion), estimate with following 3 grades.
A: less than 0.05% (lacking)
B: more than or equal to 0.05 but less than 0.10% (many slightly)
C:0.10% above (quite a lot of)
The viscosimetric analysis of latex and evaluation
Measuring method according to JIS K7117-1 is measured the viscosity that the solids component of copolymer emulsion is adjusted into 50% o'clock latex.Viscosity to gained is pressed following grade evaluation.
Below the A:300mPas
B：301～800mPa·s
C：801～2000mPa·s
More than the D:2001mPas
The mensuration of the gel content of copolymer emulsion
In the atmosphere of 40 ℃ of temperature, humidity 85%, make latex film.Thereafter, the latex film of the about 1g of weighing is as Xg.Put it in the toluene of 400ml the swelling dissolving 48 hours.Thereafter, with 300 order wire nettings of weighing it is filtered, then make the toluene evaporates drying, weight deducts screen cloth weight after the drying, and the dry back weight of weighing sample is as Yg.
Gel content (%)=Y/X * 100
The evaluation of the dried fluffing of White Board (De ラ イ ピ ッ Network) intensity
Judge nappy degree when printing each White Board sample simultaneously by naked eyes with the RI printing press, relatively visual valuation from 5 grades (excellent) to 1 grade (bad).
The blank sheet of paper glossy of White Board is estimated
The glossiness of each White Board sample is measured according to JIS P8142.The big more blank sheet of paper gloss of numerical value is good more.
The evaluation of the print gloss of White Board
(process ink 0.5g) places diel after printing each White Board sample, by the reflecting feel of visual judgement printing surface with colored ink by the RI printing press.
(excellent) A＞B＞C＞D (bad)
The measuring method of the haze value of copolymer emulsion film
Use No. 12 wire-wound rods (ワ イ ヤ one バ one) after transparent base material (the thick 100 μ m haze values 2.2% of the system polyester film DIA FOIL S100-100 of Mitsubishi Plastics Inc) is gone up the coating copolymer emulsion, drying is 1 minute in 120 ℃ of heated air circulation type stoves, make latex film, the affirmation glue spread is counted 13g/m with solids component 2± 1g/m 2To the latex film of gained, use color technical institute system spectrophotometric Meter CMS35SP in the village, measure according to the measuring method of asking method (2000) of the haze value of plastics-transparent material of JIS K7136.
Haze value (%)=(the only transmitted light of scattering composition)/(full light transmitted light) * 100
Obtain the haze value of the latex film of coating transparent substrate by the aforementioned calculation formula, calculate poor with the haze value of transparent substrate self.The mist degree value difference of this latex film and transparent substrate is more little transparent more, is the few latex film of diffuse-reflectance of light.
Synthesizing of copolymer emulsion (1)
Each monomer and other compounds that in withstand voltage system polymerization reactor, add the 1st section record shown in 160 parts of polywaters and the table 1,70 ℃ of beginning polymerizations, at polymerisation conversion above 80% o'clock, each monomer and other compounds that add the 2nd section, carry out polymerization at 70 ℃, surpass at 96% o'clock at final polymerisation conversion and finish polymerization.
Then, use sodium hydroxide that the pH of the copolymer emulsion of gained is adjusted into 7, remove unreacted monomer and other low-boiling compounds, obtain copolymer emulsion 1 by wet distillation.
Synthesizing of copolymer emulsion (2,11～14)
The monomer of each section is formed the content that changes table 1 and table 2 record into, similarly carry out polymerization, obtain latex 2 and 11～14 with latex 1.
Synthesizing of copolymer emulsion (3)
Each monomer and other compounds that in withstand voltage system polymerization reactor, add the 1st section record shown in 140 parts of polywaters and the table 1,70 ℃ of beginning polymerizations, at polymerisation conversion above 80% o'clock, each monomer and other compounds that add the 2nd section, carry out polymerization at 70 ℃, surpass at 96% o'clock at final polymerisation conversion and finish polymerization.
Then, use sodium hydroxide that the pH of the copolymer emulsion of gained is adjusted into 7, remove unreacted monomer and other low-boiling compounds, obtain copolymer emulsion 3 by wet distillation.
Synthesizing of copolymer emulsion (4,15～18)
The monomer of each section is formed the content that changes table 1 and table 2 record into, similarly carry out polymerization, obtain latex 4 and 15～18 with latex 3.
Synthesizing of copolymer emulsion (5～7,19～21)
Each monomer and other compounds that in withstand voltage system polymerization reactor, add the 1st section record shown in 140 parts of polywaters and table 1 and the table 2,70 ℃ of beginning polymerizations, surpass at 50% o'clock at polymerisation conversion, add the 2nd section each monomer and other compounds, carry out polymerization at 70 ℃.After adding the 2nd section, surpass each monomer and other compounds that added the 3rd section at 80% o'clock, surpass at 96% o'clock at final polymerisation conversion and finish polymerization at polymerisation conversion.
Then, use sodium hydroxide that the pH of the copolymer emulsion of gained is adjusted into 7, remove unreacted monomer and other low-boiling compounds, obtain copolymer emulsion 5～7,19～21 by wet distillation.
Synthesizing of copolymer emulsion (8)
Each monomer and other compounds that in withstand voltage system polymerization reactor, add the 1st section record shown in 180 parts of polywaters and the table 1,70 ℃ of beginning polymerizations, surpass at 50% o'clock at polymerisation conversion, add the 2nd section each monomer and other compounds, carry out polymerization at 70 ℃.After adding the 2nd section monomer, surpass each monomer and other compounds that added the 3rd section at 80% o'clock, surpass each monomer and other compounds that added the 4th section at 85% o'clock, surpass at 96% o'clock at final polymerisation conversion and finish polymerization at polymerisation conversion at polymerisation conversion.
Then, use sodium hydroxide that the pH of the copolymer emulsion of gained is adjusted into 7, remove unreacted monomer and other low-boiling compounds, obtain copolymer emulsion 8 by wet distillation.
Synthesizing of copolymer emulsion (9)
Each monomer and other compounds that add the 1st section record shown in 140 parts of polywaters and the table 1 in withstand voltage system polymerization reactor 70 ℃ of beginning polymerizations, surpass each monomer and other compounds that added the 2nd section at 50% o'clock at polymerisation conversion, carry out polymerization at 70 ℃.After adding the 2nd section monomer, surpass each monomer and other compounds that added the 3rd section at 80% o'clock, surpass each monomer and other compounds that added the 4th section at 85% o'clock, surpass at 96% o'clock at final polymerisation conversion and finish polymerization at polymerisation conversion at polymerisation conversion.
Then, use sodium hydroxide that the pH of the copolymer emulsion of gained is adjusted into 7, remove unreacted monomer and other low-boiling compounds, obtain copolymer emulsion 9 by wet distillation.
Synthesizing of copolymer emulsion (10)
Each monomer and other compounds that add the 1st section record shown in 140 parts of polywaters and the table 2 in withstand voltage system polymerization reactor 70 ℃ of beginning polymerizations, surpass at 96% o'clock at polymerisation conversion and finish polymerization.
Then, use sodium hydroxide that the pH of the copolymer emulsion of gained is adjusted into 7, remove unreacted monomer and other low-boiling compounds, obtain copolymer emulsion 10 by wet distillation.
Figure BSA00000442858300191
Figure BSA00000442858300201
As shown in table 1, the velocity slope dependency of the E type viscosity of the latex of copolymer emulsion 1～9 of the present invention all satisfies following formula (1), and the dirt settling in the manufacturing process and the generation of agglutinator are few, and the viscosity of the latex of gained is also low.
Press shown in the table 2, polymerization process has only 1 section in the comparative example 1, and the velocity slope dependency of E type viscosity is outside specialized range, and the generation of agglutinator and dirt settling is many slightly, the viscosity of latex height.
In the comparative example 2, at the acrylic monomer of the 1st section interpolation and ethene unsaturated carboxylic acid monomer outside the scope of claim 1 record, in the comparative example 3, on the basis of comparative example 2, also has aliphatics conjugated diene monomer the 1st section interpolation also outside the scope of claim 1 record, therefore the velocity slope dependency of E type viscosity is outside scope, and the generation of agglutinator and dirt settling is many, latex viscosity height.
Comparative example 4 surpasses 32 weight % because the 1st section monomer adds up to, in addition, comparative example 5 is because the 2nd section acrylic monomer that adds later on surpasses 30 weight %, and the velocity slope dependency of E type viscosity is outside scope, the generation of agglutinator and dirt settling is many, latex viscosity height.
Comparative example 10 is because the ethene unsaturated carboxylic acid monomer of the 1st section interpolation surpasses 20 weight %, and the velocity slope dependency of E type viscosity is outside scope, and the generation of agglutinator and dirt settling is many, latex viscosity height.
Comparative example 11 is because the 2nd section aliphatics conjugated diene monomer that uses later on surpasses 60 weight %, comparative example 12 since the acrylic monomer that adds in the 2nd section later operation less than 5 weight %, the velocity slope dependency of E type viscosity is outside scope, the generation of agglutinator and dirt settling is many, latex viscosity height.
The manufacturing of paper coating composition and evaluation
Use copolymer emulsion 3～7,9,10,15～21 according to the prescription shown in following, pH is adjusted into 9.5, make the paper coating composition with sodium hydroxide.
(prescription of paper coating composition)
Prescription
40 parts of particulate kaolin
60 parts of water-ground limestones
2 parts of treated starches
7 parts of copolymer emulsions
·······················
Solid component concentration 67%
The manufacturing of White Board and evaluation
At bodystock paper (unit surface amount 55g/m 2) on, with every to be coated with by amount be 10g/m 2Use wire-wound rod to be coated with above-mentioned paper coating composition, after the drying, roll processing, obtain White Board with the condition of 50 ℃ of line pressure 60kg/cm, temperature.The White Board of gained is used for respectively testing estimating, and it the results are shown in table 1 and table 2.
Shown in table 1, table 2, intensity is all fine during the printing of the White Board of copolymer emulsion 3～7,9 of the present invention, and blank sheet of paper gloss number, print gloss value height.
Polymerization process has only 1 section in the comparative example 1, and the mist degree difference of latex film and base material surpasses 1.0%, blank sheet of paper gloss print gloss deterioration.
In the comparative example 6 at the acrylic monomer of the 1st section interpolation and ethene unsaturated carboxylic acid monomer outside the scope of claim 1 record, the mist degree difference of latex film and base material surpasses 1.0%, blank sheet of paper gloss print gloss deterioration.
In the comparative example 7 at aliphatics conjugated diene monomer, acrylic monomer and the ethene unsaturated carboxylic acid monomer of the 1st section interpolation outside the scope of claim 1 record, the mist degree difference of latex film and base material surpasses 1.0%, blank sheet of paper gloss print gloss deterioration, and do the fluffing strength deterioration.
Comparative example 8 surpasses 32 weight % because the 1st section monomer adds up to, and the mist degree difference of latex film and base material surpasses 1.0%, blank sheet of paper gloss print gloss deterioration.
Comparative example 9 surpasses 30 weight % at the 2nd section acrylic monomer that adds later on, and the mist degree difference of latex film and base material surpasses 1.0%, blank sheet of paper gloss print gloss deterioration.
Comparative example 10 surpasses 20 weight % at the ethene unsaturated carboxylic acid monomer of the 1st section interpolation, and the mist degree difference of latex film and base material surpasses 1.0%, blank sheet of paper gloss deterioration, and print gloss is deterioration also.
Comparative example 11 is owing to surpass 60 weight % at the 2nd section aliphatics conjugated diene monomer that uses later on, and the mist degree difference of latex film and base material surpasses 1.0%, and blank sheet of paper gloss print gloss deterioration is done the fluffing strength deterioration.
The acrylic monomer that comparative example 12 adds in the 2nd section later operation is done the fluffing strength deterioration less than 5 weight %, and the mist degree difference of latex film and base material surpasses 1.0%, blank sheet of paper gloss print gloss deterioration.
＜latex 22～31 〉
The mensuration of the number average bead diameter of copolymer emulsion
The number average bead diameter of copolymer emulsion is passed through dynamic light scattering determination.Use FPAR-1000 (Otsuka Electronics Co., Ltd. system during mensuration).
The mensuration of the gel content of copolymer emulsion
Make latex film in room temperature atmosphere.Thereafter, the latex film of the about 1g of weighing is as Xg.Put it into and make its swelling dissolving 48 hours in the toluene of 400ml.Thereafter, with 300 order wire nettings of weighing it is filtered, then make the toluene evaporates drying, weight deducts screen cloth weight after the drying, and the dry back weight of weighing sample is as Yg.Calculate gel content with following formula.
Gel content (%)=Y/X * 100
The adhesiveness test of copolymer emulsion film
The standard of the difficulty of adhering to back flow roll etc. as latex is tested with regard to the adhesivity of copolymer emulsion film.On polyester film with glue spread 12g/m 2Be coated with each copolymer emulsion, in 120 ℃ baking oven, after dry 1 minute, be cut into the wide rectangular shape of 1cm.On black platform paper, attach the rectangular parallelepiped of the whole multipolymers of synthetic side by side.
Stacked thereon filter paper is with the crimping of RI printing press.Thereafter, after filter paper peeled off, visual judgement filter paper fibre was at the lip-deep attachment state of each latex film, relatively the adhesivity of each latex film.Fiber is adhered to few, fiber is adhered to many D as poor adhesion, relatively estimate by following grade as the good A of adhesivity.
(excellent) A＞B＞C＞D (bad)
The evaluation of the redispersibility of paper coating composition
Be coated with each composition sample abreast with the #6 wire-wound rod on NBR black rubber plate, after dry 3 minutes, cleaned 1 minute with 30 ℃ flowing water in 60 ℃ of heated air circulation type stoves, visual observation remains in the epithelium of the composition on the NBR black rubber plate.With the less residue of epithelium as the good A of redispersibility, the E as the redispersibility difference that the residual quantity of epithelium is many relatively estimates by following grade by visual.
(excellent) A＞B＞C＞D＞E (bad)
The evaluation of the dried fluffing intensity of White Board
Nappy degree when printing each White Board sample by the naked eyes judgement simultaneously with the RI printing press, from 5 grades (excellent) to 1 grade (bad) carry out visual valuation relatively.
The evaluation of the wet raising intensity of White Board
Use the RI printing press to pass through glue clearer (モ Le ト Application ロ one Le) simultaneously at each White Board sample humidification, give print each White Board sample simultaneously with ink roller immediately after the water after, with the naked eye judge the nappy degree of this moment, from 5 grades (excellent) to 1 grade (bad) carry out visual valuation relatively.
Synthesizing of copolymer emulsion (22～24,28～31)
Add 1 part of 150 parts of polywaters and Potassium Persulphate in withstand voltage system polymerization reactor, after fully stirring, each monomer and other compounds shown in the 1st section of adding table 3 and table 4 is warming up to 70 ℃ of beginning polymerizations.Polymerization for the 2nd section, surpass each monomer and other compounds that added the 2nd section at 50% o'clock at the 1st section polymerisation conversion and carry out polymerization, polymerization for the 3rd section, surpass each monomer and other compounds that added the 3rd section at 80% o'clock at the 2nd section polymerisation conversion, surpass at 95% o'clock at final polymerisation conversion and finish polymerization.
Then, use sodium hydroxide and potassium hydroxide that the pH of the copolymer emulsion of gained is adjusted into 7, remove unreacted monomer and other low-boiling compounds, obtain copolymer emulsion 22～24,28～31 by wet distillation.
Synthesizing of copolymer emulsion (25～27)
Add 1 part of 150 parts of polywaters and Potassium Persulphate in withstand voltage system polymerization reactor, after fully stirring, each monomer and other compounds shown in the 1st section of adding table 3 is warming up to 70 ℃ of beginning polymerizations.Polymerization for the 2nd section, surpass each monomer and other compounds that added the 2nd section at 50% o'clock at the 1st section polymerisation conversion and carry out polymerization, polymerization for the 3rd section, surpass each monomer and other compounds that added the 3rd section at 80% o'clock at the 2nd section polymerisation conversion and carry out polymerization, polymerization for the 4th section, surpass each monomer and other compounds that added the 4th section at 85% o'clock at the 3rd section polymerisation conversion and carry out polymerization, surpass at 95% o'clock at final polymerisation conversion and finish polymerization.
Then, use sodium hydroxide and potassium hydroxide that the pH of the copolymer emulsion of gained is adjusted into 7, remove unreacted monomer and other low-boiling compounds, obtain copolymer emulsion 25～27 by wet distillation.
Figure BSA00000442858300261
The manufacturing of paper coating composition and evaluation
Use by the above-mentioned copolymer emulsion that is synthesized into 22～31 according to the prescription shown in following, pH is adjusted into 9.5, make the paper coating composition with sodium hydroxide.
(prescription of paper coating composition)
Prescription
40 parts of kaolin
60 parts of water-ground limestones
2 parts of treated starches
7 parts of copolymer emulsions
·······················
Solid component concentration 67%
The manufacturing of White Board and evaluation
At bodystock paper (unit surface amount 55g/m 2) on, with every to be coated with by amount be 10g/m 2Use wire-wound rod to be coated with above-mentioned paper coating composition, after the drying, roll processing, obtain White Board with the condition of 50 ℃ of line pressure 60kg/cm, temperature.The White Board of gained is used for respectively testing and estimating, and it the results are shown in table 3 and table 4.
Shown in table 3,4, the adhesivity of the latex film of copolymer emulsion 22～27 of the present invention is all fine, and uses the redispersibility of paper coating composition of these copolymer emulsions also all fine, and the dried fluffing intensity and the wet raising intensity of the White Board of gained are good.
The 1st section acrylic monomer in the comparative example 13 is less than 5.1 weight %, and ethene unsaturated carboxylic acid monomer amount is less than 4.1 weight %, the dried fluffing intensity difference of the redispersibility of composition and White Board.
The 1st section acrylic monomer in the comparative example 14 is less than 5.1 weight %, the dried fluffing intensity difference of White Board.
The 1st section aliphatics conjugated diene monomer in the comparative example 15 is less than 1.5 weight %, the ethene unsaturated carboxylic acid monomer is less than 4.1 weight %, the 1st section monomer adds up to less than 13 weight %, and the dried fluffing intensity of the redispersibility of paper coating composition and White Board is deterioration significantly.
The 1st section monomer in the comparative example 16 adds up to and surpasses 34 weight %, the dried fluffing intensity difference of White Board.
Foregoing invention provides as illustrative embodiment of the present invention, but this only is an illustration, does not constitute determinate explanation.The variation tangible of the present invention of being made by the practitioner of this technical field is also contained in the scope of claim described later.
As mentioned above, dirt settling and the generation of agglutinator of copolymer emulsion of the present invention in manufacturing process is few, and production efficiency is good, and viscosity of latex is low, therefore in manufacturing stage of copolymer emulsion and transportation operation, keeping operation etc., have good operability, exceedingly useful.
When copolymer emulsion of the present invention is used as the tackiness agent of paper coating composition, can when the printing that improves White Board, keep lower viscosity of latex in the intensity, therefore particularly useful.
As mentioned above, use copolymer emulsion of the present invention and paper coating composition, the White Board of good strength in the time of can obtaining the good and printing of blank sheet of paper gloss, print gloss.
As mentioned above, the adhesivity of the latex film of copolymer emulsion of the present invention is good, use the redispersibility of paper coating composition of the present invention of this copolymer emulsion good, the coating operation when White Board is made by this is good, also can tackle the high speed of coating apparatus.In addition, the coating said composition and the printing of White Board the time good strength, therefore very useful with tackiness agent and composition as the paper coating composition.

Claims (11)

1. copolymer emulsion, it is to form the copolymer emulsion that the polymerization of at least 2 sections polymerization process that constitute gets by having by different monomers, and at the 1st section is aliphatics conjugated diene monomer 1.5～24 weight %, acrylic monomer 5.1～25 weight %, ethene is unsaturated carboxylic acid monomer 3.1～20 weight % and can adds up to 13～32 weight % with the monomer that other monomers 0～22.3 weight % of their copolymerization constitutes, all monomer adds up to 100 weight %, at the 2nd section is later on aliphatics conjugated diene monomer 10～60 weight %, acrylic monomer 5～30 weight %, ethene is unsaturated carboxylic acid monomer 0～13 weight % and can adds up to 68～87 weight % with the monomer that other monomers 0～72 weight % of their copolymerization constitutes, all monomer adds up to 100 weight %, it is characterized in that the solids component of this copolymer emulsion is adjusted into 50%, the velocity slope dependency of the E type viscosity when the liquid temperature is adjusted into 25 ℃ satisfies following formula (1):
B/A＝0.50～1.1 ……(1)
In the formula, A represents velocity slope 2sec -1E type viscosity, B represents velocity slope 10sec -1E type viscosity.
2. copolymer emulsion as claimed in claim 1, it is characterized in that, have by different monomers and form at least 3 sections polymerization process that constitute, at the 1st section with aliphatics conjugated diene monomer 1.5～24 weight %, acrylic monomer 5.1～25 weight %, ethene is unsaturated carboxylic acid monomer 4.1～20 weight % and can adds up to 13～32 weight % polymerizations with the monomer that other monomers 0～21.3 weight % of their copolymerization constitutes, after the 2nd section with aliphatics conjugated diene monomer 10～60 weight %, acrylic monomer 5～30 weight %, ethene is unsaturated carboxylic acid monomer 0～13 weight % and can adds up to 68～87 weight % polymerizations with the monomer that other monomers 0～72 weight % of their copolymerization constitutes.
3. copolymer emulsion as claimed in claim 1 is characterized in that, ethene is that the above polymerization process at the 1st section of 60 weight % of whole consumptions of unsaturated carboxylic acid monomer adds, and does not add in the polymerization process of terminal section.
4. copolymer emulsion as claimed in claim 1 is characterized in that, is used as paper coating copolymer emulsion.
5. copolymer emulsion as claimed in claim 4 is characterized in that, counts 13g/m with dry weight 2± 1g/m 2Glue spread this copolymer emulsion is coated the transparent substrate after drying and the haze value of measuring by JIS K7136 of film and the difference of the haze value of transparent substrate self be 0～1.0%.
6. the paper coating composition is characterized in that, contains the described copolymer emulsion of claim 5.
7. copolymer emulsion, it is the aliphatics conjugated diene monomer that monomer is added up to 100 weight %, the acrylic monomer, ethene is unsaturated carboxylic acid monomer and can carries out letex polymerization with other monomers of their copolymerization and must be used as the copolymer emulsion of tackiness agent in the paper coating composition, it is characterized in that, have by different monomers and form at least 3 sections polymerization process that constitute, at the 1st section with aliphatics conjugated diene monomer 1.5～24 weight %, acrylic monomer 5.1～25 weight %, ethene is unsaturated carboxylic acid monomer 4.1～20 weight % and can adds up to 13～34 weight % polymerizations with the monomer that other monomers 0～23.3 weight % of their copolymerization constitutes, after the 2nd section with aliphatics conjugated diene monomer 10～60 weight %, acrylic monomer 5～30 weight %, ethene is unsaturated carboxylic acid monomer 0～13 weight % and can adds up to 66～87 weight % polymerizations with the monomer that other monomers 0～72 weight % of their copolymerization constitutes.
8. copolymer emulsion as claimed in claim 7 is characterized in that, ethene is that the above polymerization process at the 1st section of 60 weight % of whole consumptions of unsaturated carboxylic acid monomer adds, and does not add in the polymerization process of terminal section.
9. copolymer emulsion as claimed in claim 7 is characterized in that, when the 2nd section monomeric total amount of using later on of acrylic was made as 100 weight %, the acrylic amount of monomer of adding in final polymerization process was less than 45 weight %.
10. the paper coating composition is characterized in that, contains the described copolymer emulsion of claim 7.
11. the manufacture method of copolymer emulsion, it is the aliphatics conjugated diene monomer that monomer is added up to 100 weight %, the acrylic monomer, ethene be unsaturated carboxylic acid monomer and can carry out letex polymerization with other monomers of their copolymerization and the manufacture method that in the paper coating composition, is used as the copolymer emulsion of tackiness agent, it is characterized in that, have by different monomers and form at least 3 sections polymerization process that constitute, be included in the 1st section with aliphatics conjugated diene monomer 1.5～24 weight %, acrylic monomer 5.1～25 weight %, ethene is unsaturated carboxylic acid monomer 4.1～20 weight % and can adds up to 13～34 weight % polymeric operations with the monomer that other monomers 0～23.3 weight % of their copolymerization constitutes, and after the 2nd section with aliphatics conjugated diene monomer 10～60 weight %, acrylic monomer 5～30 weight %, ethene is unsaturated carboxylic acid monomer 0～13 weight % and can adds up to 66～87 weight % polymeric operations with the monomer that other monomers 0～72 weight % of their copolymerization constitutes.
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