CN102167781B - Copolymer emulsion, its manufacture method and paper coating composition - Google Patents

Copolymer emulsion, its manufacture method and paper coating composition Download PDF

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Publication number
CN102167781B
CN102167781B CN201110050414.1A CN201110050414A CN102167781B CN 102167781 B CN102167781 B CN 102167781B CN 201110050414 A CN201110050414 A CN 201110050414A CN 102167781 B CN102167781 B CN 102167781B
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monomer
copolymer emulsion
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unsaturated carboxylic
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CN102167781A (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 and form the polymerization of at least 2 sections of polymerization process formed and the copolymer emulsion obtained by having by different monomers, and this copolymer emulsion is undertaken being polymerized by the monomer monomer composition formed in specialized range of the 1st section and the 2nd section and is obtained, it is characterized in that, solids component is adjusted to 50%, the velocity slope dependency of the E type viscosity of liquid temperature when being adjusted to 25 DEG C meets formula (1): in B/A=0.50 ~ 1.1 (1) formula, A represents velocity slope 2sec -1e type viscosity, B represents velocity slope 10sec -1e type viscosity.

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 being specifically related to agglutinator or dirt settling in manufacturing process is few, and viscosity of latex is low, transportability, keeping and good copolymer emulsion and the paper coating composition such as storage stability.
Also relate to paper coating copolymer emulsion and paper coating composition, this paper coating copolymer emulsion is the copolymer emulsion being used as tackiness agent in paper coating composition, the blank sheet of paper gloss of the White Board obtain coating paper containing the paper coating composition of this latex, print gloss and good strength when printing.
Also relate to paper coating copolymer emulsion, its manufacture method and the paper coating composition containing this copolymer emulsion, this paper coating copolymer emulsion is the copolymer emulsion being used as tackiness agent in paper coating composition, coating operations in White Board manufacturing process is excellent, and good strength during the printing of White Board.
Background technology
As everyone knows, the various tackiness agents that it is representative that carboxy-modified butadiene-based copolymer emulsion is widely used as with back starching of paper conversion field or carpet etc.Corresponding each purposes is varied to the performance required by tackiness agent, in order to correspond, tries every possible means to change composition and the structure of copolymer emulsion, can play the performances such as the improvement of bonding strength and adhering reduction.On the other hand, owing to being tackiness agent, that is, so-called " caking agent ", therefore also can cause the bad problem in manufacturing process.Agglutinator increase when can exemplify the attachment issue such as in each equipment or transport, the solidification etc. in pipe arrangement.
Particularly in paper conversion field, also cost degradation is carried out in recent years in the manufacture of White Board, for the copolymer emulsion of higher price in coating compound, owing to improving the performance of latex, fusion number is correspondingly reduced, contribute to greatly reducing manufacturing cost, the impact that when therefore making the printing of latex, the manufacturing cost of the latex such as intensity raising on White Board quality and White Board is brought more and more is taken seriously.In addition, intensity when generally will improve printing importantly increases bonding surface area by the particle diameter reducing 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 manufacturing stage of copolymer emulsion or the blending process of transport operation, keeping operation and paper coating composition, the unworkable example of copolymer emulsion constantly increases, and thus while maintenance high-quality, how to reduce viscosity of latex and just becomes problem.
In order to solve above-mentioned problem, such as in Japanese Patent Laid-Open 3-182504 publication, describe following technology: the fine coagulative generation of obtained latex is few by the manufacture method of being polymerized by specific composition monomer composition under the seed latex of specific composition and the existence of α-methylstyrenedimer, excellent in stability.Also have, following technology is disclosed: the polymerization residue of the paper coating copolymer emulsion obtained by separately using 2 kinds of different emulsifying agents in polymerization process is few in Japanese Patent Laid-Open 11-117189 publication, can stablize and effectively manufacture, using the White Board physical property of this latex excellent.
But the operability of intensity and copolymer emulsion during the good printing that these various improving technologies are still not enough to get both required by White Board, the viscosity how reducing latex under the state keeping more high-quality just becomes large problem.
In addition, in recent years, due to reasons such as its printing effect are good, White Board is used to very many prints.In the periodical such as quarterly, monthly magazine, the situation of White Board is all used also greatly to increase at all pages.Particularly, the Direct Mail advertisement in mail order business or goods catalogue etc. substantially all pages all use White Board.
Generally, paper coating composition is by the dispersible pigment dispersion obtained in water by the White Pigment Dispersion such as carclazyte or calcium carbonate, the water-borne coatings that forms for the tackiness agent that is adhesively fixed to each other by pigment and be bonded and fixed to by pigment on body paper and other additives.Use as tackiness agent with the styrene butadiene based copolymer latex synthesis emulsion tackiness agent that is representative or the natural glue that is representative with starch, casein.Wherein, the degree of freedom of the Quality Design of styrene butadiene based copolymer latex is large, be widely used as the tackiness agent being best suited for paper coating composition at present, the workability when performance of the performance impact paper coating composition of known styrene butadiene based copolymer latex and White Board manufacture or the quality such as print gloss, surface strength of final White Board goods.
Especially the blank sheet of paper gloss of considerable influence and print gloss is had to be very important projects to the outward appearance of end article in the quality of White Board.The gloss of White Board is represented by the normal reflection rate of the light of White Board surface and ink epithelial surfaces, if therefore White Board surface and ink epithelial surfaces level and smooth, gloss uprises.This pigment used with regard to explanation coating layer plays very important effect.Generally, because the tackiness agents such as copolymer emulsion are the essential factors of the orientation hindering pigment, after therefore adding, visible White Board surface roughen, has the tendency that blank sheet of paper gloss reduces.On the other hand, for print gloss, due to the vehicle (vehicle) in ink is more difficult to that applied paper Surface absorption ink epithelium is dry must be slower and form more level and smooth ink epithelial surfaces, therefore generally increase the space that the tackiness agents such as copolymer emulsion reduce White Board, improve print gloss.So blank sheet of paper gloss and print gloss are contrary physical property, be difficult to improve simultaneously.In addition along with the high speed of printing, also requiring intensity when improving White Board printing, in order to solve these problems, proposing various technical scheme.
Such as, in Japanese Patent Laid-Open 2001-31727, describe the technology by using the copolymer emulsion of specific composition scope to improve the blank sheet of paper gloss, print gloss, bonding strength etc. of White Board.Such as, disclose in Japanese Patent Laid-Open 2005-139577 and utilize pH is 2 ~ 6, alkali metal content is the specific composition below specified quantitative copolymer emulsion to obtain the excellent and technology of the White Board that blank sheet of paper gloss, print gloss, surface smoothness, surface strength are excellent of coating operations.Further, describe in Japanese Patent Laid-Open 2007-204513 publication by the amount of the styrene dimer in the volatile component contained by latex, styrene trimer being controlled obtain the suppressed and technology of the copolymer emulsion that blank sheet of paper gloss, print gloss, ink setting, surface strength are excellent of foul smell at below 200ppm.
On the other hand, in the manufacture method of White Board, by also using hollow plastic pigments in general mineral dye, blank sheet of paper gloss can be made to improve.But, if add hollow plastic raw material, ink setting accelerates, be difficult to so exist the tendency manifesting print gloss, in Japanese Patent Laid-Open 2006-37312 publication, therefore disclose in the paper coating composition by the undercoat in 2 layers of coating the technology obtaining blank sheet of paper gloss and the good coating layer of print gloss containing hollow plastic pigments and water-ground limestone.
But, these improving technologies not yet reach the level of the performance fully meeting blank sheet of paper gloss required by White Board and print gloss, and due to hollow plastic pigments, although on the impact of blank sheet of paper gloss, large but coating cost significantly raises, and therefore needs from copolymer emulsion that this does larger improvement on the one hand very urgently.
Also have, the improvement of workability when manufacturing about White Board, such as describe in Japanese Patent Laid-Open 11-50390 publication by containing more than 30 % by weight specified particle diameter scope water-ground limestone paper coating composition in use the paper coating composition of the copolymer emulsion of specified particle diameter scope to obtain the excellent and technology of basic matt uneven high-quality coated paper for printing of the high speed coatability of blade coating.
About the quality improving of the surface strength etc. of White Board goods, such as, in Japanese Patent Laid-Open 2006-152484 publication, describe the technology by using the core-shell type latex obtain by multi-stage polymeric of below median size 150mm to obtain good and ink setting (イ Application Network セ ッ ト) of print gloss, delustring White Board that ink setting is good.Disclose in Japanese Patent Laid-Open 9-31894 publication initial feeding section by being used in polymerization by after the polymerize monomer mixtures of the whole consumptions containing unsaturated dicarboxylic acid and methacrylic acid, the 2nd section of copolymer emulsion obtained with post polymerization paper coating composition and obtain printing time surface strength, water tolerance, even ink (イ Application Network meat), offset printing White Board that resistance to whipability is excellent technology.Also have, in Japanese Patent Laid-Open 2008-248446 publication, describe surface strength when can provide printing by the film of regulation copolymer emulsion to the contact angle of soybean oil, the technology of White Board that the printing adaptability such as print gloss, ink are arranged is excellent, obtain this copolymer emulsion, preferably adopt multi-stage polymeric.
But these various improving technologies not yet realize can the coating operations required by paper coating composition of the corresponding coating apparatus of high speed day by day and White Board physical property, particularly needs very urgently to do further improvement from latex aspect.
Summary of the invention
The object of this invention is to provide attachment in manufacturing process or agglutinator produces less, the excellent in stability of particle and production efficiency is by this improved and low, the transportability excellent copolymer emulsion of viscosity of latex.
In addition, the object of this invention is to provide paper coating copolymer emulsion and the paper coating composition of the White Board that intensity is good when can obtain the excellent and printing of blank sheet of paper gloss, print gloss.
In addition, the adhesivity that the object of this invention is to provide latex film excellent (that is, not easily adhering to) and the redispersibility of paper coating composition good by this and can obtain coating operations excellent and printing time the copolymer emulsion of intensity good White Board, its manufacture method and paper coating composition.
Namely, the present invention forms the polymerization of at least 2 sections of polymerization process formed and the copolymer emulsion obtained by having by different monomers, aliphatic conjugated diene system monomer 1.5 ~ 24 % by weight at the 1st section, acrylic monomer 5.1 ~ 25 % by weight, ethene system unsaturated carboxylic acid monomer 3.1 ~ 20 % by weight and the monomer that can form with other monomers 0 ~ 22.3 % by weight of their copolymerization added up to for 13 ~ 32 % by weight (whole monomer adds up to 100 % by weight), aliphatic conjugated diene system monomer 10 ~ 60 % by weight at the 2nd section later, acrylic monomer 5 ~ 30 % by weight, ethene system unsaturated carboxylic acid monomer 0 ~ 13 % by weight and the monomer that can form with other monomers 0 ~ 72 % by weight of their copolymerization added up to for 68 ~ 87 % by weight (whole monomer adds up to 100 % by weight), it is characterized in that, the solids component of this copolymer emulsion is adjusted to 50%, the velocity slope dependency of E type viscosity when liquid temperature is adjusted to 25 DEG C meets 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 coating copolymer emulsion and paper coating composition.Be specifically related to form the polymerization of at least 2 sections of polymerization process formed and the copolymer emulsion obtained by having by different monomers, aliphatic conjugated diene system monomer 1.5 ~ 24 % by weight at the 1st section, acrylic monomer 5.1 ~ 25 % by weight, ethene system unsaturated carboxylic acid monomer 3.1 ~ 20 % by weight and the monomer that can form with other monomers 0 ~ 22.3 % by weight of their copolymerization added up to for 13 ~ 32 % by weight (whole monomer adds up to 100 % by weight), aliphatic conjugated diene system monomer 10 ~ 60 % by weight at the 2nd section later, acrylic monomer 5 ~ 30 % by weight, ethene system unsaturated carboxylic acid monomer 0 ~ 13 % by weight and the monomer that can form with other monomers 0 ~ 72 % by weight of their copolymerization added up to for 68 ~ 87 % by weight (whole monomer adds up to 100 % by weight), it is characterized in that, after this copolymer emulsion is coated transparent substrate, (glue spread counts 13g/m with dry weight for the dry and film that obtains 2± 1g/m 2) the haze value measured by JIS K7136 and the difference of haze value of transparent substrate self be 0 ~ 1.0%.
In addition, copolymer emulsion of the present invention is the copolymer emulsion being used as tackiness agent in paper coating composition, and be by aliphatic conjugated diene system monomer, acrylic monomer, ethene system unsaturated carboxylic acid monomer and the copolymer emulsion that can obtain with other monomers of their copolymerization (monomer adds up to 100 % by weight) letex polymerization, it is characterized in that, have and form by different monomers at least 3 sections of polymerization process formed, by aliphatic conjugated diene system monomer 1.5 ~ 24 % by weight at the 1st section, acrylic monomer 5.1 ~ 25 % by weight, ethene system unsaturated carboxylic acid monomer 4.1 ~ 20 % by weight and the monomer that can form with other monomers 0 ~ 23.3 % by weight of their copolymerization add up to 13 ~ 34 % by weight to be polymerized, later by aliphatic conjugated diene system monomer 10 ~ 60 % by weight at the 2nd section again, acrylic monomer 5 ~ 30 % by weight, ethene system unsaturated carboxylic acid monomer 0 ~ 13 % by weight and the monomer that can form with other monomers 0 ~ 72 % by weight of their copolymerization add up to 66 ~ 87 % by weight to be polymerized.
Also have, the manufacture method of copolymer emulsion of the present invention is by aliphatic conjugated diene system monomer, acrylic monomer, ethene system unsaturated carboxylic acid monomer and the manufacture method of copolymer emulsion that can obtain with other monomers of their copolymerization (monomer adds up to 100 % by weight) letex polymerization, this copolymer emulsion is used as tackiness agent in paper coating composition, it is characterized in that, have and form by different monomers at least 3 sections of polymerization process formed, be included in the 1st section by aliphatic conjugated diene system monomer 1.5 ~ 24 % by weight, acrylic monomer 5.1 ~ 25 % by weight, ethene system unsaturated carboxylic acid monomer 4.1 ~ 20 % by weight and the monomer that can form with other monomers 0 ~ 23.3 % by weight of their copolymerization add up to 13 ~ 34 % by weight operations of being polymerized, and by aliphatic conjugated diene system monomer 10 ~ 60 % by weight after the 2nd section, acrylic monomer 5 ~ 30 % by weight, ethene system unsaturated carboxylic acid monomer 0 ~ 13 % by weight and the monomer that can form with other monomers 0 ~ 72 % by weight of their copolymerization add up to 66 ~ 87 % by weight operations of being polymerized.
By the present invention, attachment in manufacturing process and agglutinator can be obtained and produce less and the low copolymer emulsion of viscosity.
By copolymer emulsion of the present invention and paper coating composition, the White Board that when can obtain the excellent and printing of blank sheet of paper gloss, print gloss, intensity is good.
In addition, copolymer emulsion of the present invention bring the redispersibility of the adhesivity of the latex film of the principal element of impact and paper coating composition excellent as coating operations when manufacturing White Board.Further, be coated with this paper coating composition and the printing of the White Board obtained time good strength.
Copolymer emulsion of the present invention by by aliphatic conjugated diene system monomer, acrylic monomer, ethene system unsaturated carboxylic acid monomer and can with other monomer emulsion polymerization of their copolymerization and obtaining.
As aliphatic conjugated diene system monomer, 1,3-butadiene, 2-methyl isophthalic acid can be exemplified, 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 one kind or two or more.Particularly preferably use 1,3-butadiene.
As acrylic monomer, can exemplify vinyl cyanide, methacrylonitrile, α-chloro-acrylonitrile, α-ethyl acrylonitrile etc., these monomers can use one kind or two or more.Particularly preferably use vinyl cyanide or methacrylonitrile.
As ethene system unsaturated carboxylic acid monomer, can monoprotic acid or the diprotic acid (acid anhydride) such as exemplified by acrylic, methacrylic acid, β-crotonic acid, toxilic acid, fumaric acid, methylene-succinic acid, these monomers can use one kind or two or more.
As can with other monomers of above-mentioned aliphatic conjugated diene system monomer, acrylic monomer and the unsaturated carboxylic acid monomer copolymerization of ethene system, alkenyl aromatic monomers, unsaturated carboxylic acid alkyl ester monomer, unsaturated monomer, unsaturated carboxylic acid amide monomer etc. containing hydroxyalkyl can be exemplified.
As alkenyl aromatic monomers, can exemplify vinylbenzene, α-vinylbenzene, methyl α-vinylbenzene, Vinyl toluene and Vinylstyrene etc., these monomers can use one kind or two or more.Particularly preferably use vinylbenzene.
As unsaturated carboxylic acid alkyl ester monomer, can exemplified by acrylic methyl esters, methyl methacrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, butyl acrylate, glycidyl methacrylate, dimethyl fumarate, DEF, dimethyl maleate, ethyl maleate, dimethyl itaconate, monomethyl fumarate, monomethyl ester, 2-EHA etc., these monomers can use one kind or two or more.Particularly preferably use methyl methacrylate.
As the unsaturated monomer containing hydroxyalkyl, can exemplified by acrylic beta-hydroxy ethyl ester, β-hydroxyethyl methacrylate, Propylene glycol monoacrylate, Rocryl 410, hy-droxybutyl, methacrylate, the chloro-2-hydroxypropyl acrylate of methacrylic acid 3-, toxilic acid two-(ethylene glycol) ester, methylene-succinic acid two-(ethylene glycol) ester, toxilic acid 2-hydroxyl ethyl ester, toxilic acid two (2-hydroxyethyl) ester, toxilic acid 2-hydroxyethyl methyl esters etc., these monomers can use one kind or two or more.Particularly preferably use propenoic acid beta-hydroxy ethyl ester.
As unsaturated carboxylic acid amide monomer, can exemplify acrylamide, Methacrylamide, N hydroxymethyl acrylamide, N-methylol methacrylamide, N,N-DMAA etc., these monomers can use one kind or two or more.Particularly preferably use acrylamide or Methacrylamide.
Further, 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.
Solids component is adjusted to 50% by copolymer emulsion of the present invention, liquid temperature is adjusted to 25 DEG C and change the numerical value that velocity slope obtains to measure E type viscosity and must meet following formula (1).
B/A＝0.50～1.1 ·······(1)
In above 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 the scope of 0.50 ~ 1.1, then the dirt settling in manufacturing process or the generation of agglutinator increase, and viscosity of latex uprises.
Also have, such as, when copolymer emulsion being used as the tackiness agent of paper coating composition, sometimes reduce latex particle size in order to intensity when improving the printing of White Board or increase the consumption of functional group's (such as ethene unsaturated carboxylic acid monomer etc.), in these cases, if the velocity slope dependency of latex also meets above formula (1), then viscosity of latex not easily rises, more satisfactory.
After copolymer emulsion drying and forming-film of the present invention, transparency is high, and suppress the reflection of light at painting layer surface and coating layer inside, normal reflection rate is by this improved, and blank sheet of paper gloss and print gloss are improved.Specifically copolymer emulsion is coated transparent substrate and the dry and latex film that obtains (glue spread counts 13g/m with dry weight 2± 1g/m 2) the difference based on the mist degree measured value of JIS K7136 and the mist degree of transparent substrate self be 0 ~ 1.0%.Here, general haze value refers to the percentage departing from the transmitted light in more than 2.5 °, incident light direction in the transmitted light by test film because of forwards scattering, defines with " ratio of diffused transmission rate and full light transmittance (parallel transmission+diffused transmission rate) ".Therefore, the little then transparency of haze value is high.If the difference of the haze value of above-mentioned latex and transparent substrate is more than 1.0%, then poor in the transparency of the latex part of painting layer surface and coating layer inner membranization, diffuse-reflectance increases, and causes blank sheet of paper gloss and print gloss reduction.
Copolymer emulsion of the present invention has at least 2 sections of polymerization process that different monomer compositions is formed, and monomer whose composition must in following ranges.That is, must the 1st section be aliphatic conjugated diene system monomer 1.5 ~ 24 % by weight, acrylic monomer 5.1 ~ 25 % by weight, ethene system unsaturated carboxylic acid monomer 3.1 ~ 20 % by weight and the monomer that can form with other monomers 0 ~ 22.3 % by weight of their copolymerization add up to 13 ~ 32 % by weight.Must 68 ~ 87 % by weight be added up to be polymerized aliphatic conjugated diene system monomer 10 ~ 60 % by weight, acrylic monomer 5 ~ 30 % by weight, ethene system unsaturated carboxylic acid monomer 0 ~ 13 % by weight and the monomer that can form with other monomers 0 ~ 72 % by weight of their copolymerization after the 2nd section.
If outside the scope of the 1st section shown in above and the 2nd section of later monomer compositing range and monomer total amount, then the velocity slope dependency of copolymer emulsion cannot meet above formula (1), agglutinator in the manufacturing process of latex or the generation of dirt settling many, and viscosity of latex also can not reduce, cause the operability deteriorations such as transportability.In addition, the difference of the haze value of copolymer emulsion film and coated substrate can not below 1.0%, blank sheet of paper gloss and print gloss deterioration.
At the 1st section of ethene system unsaturated carboxylic acid monomer added preferably more than 3.6 % by weight because during the printing of White Board like this intensity manifest better.Further more preferably more than 4.1 % by weight.
Ethene system unsaturated carboxylic acid monomer is better more than 60 % by weight of total amount and adds in the polymerization process of the 1st section, if be less than 60 % by weight, the agglutinator had in manufacturing process produces many tendencies, the intensity during printing of White Board manifests the tendency of deterioration, therefore undesirable.
Be more preferably to have and form the different polymerization process of more than 3 sections by monomer, at the 1st section by aliphatic conjugated diene system monomer 1.5 ~ 24 % by weight, acrylic monomer 5.1 ~ 25 % by weight, ethene system unsaturated carboxylic acid monomer 4.1 ~ 20 % by weight and the monomer that can form with other monomers 0 ~ 21.3 % by weight of their copolymerization add up to 13 ~ 32 % by weight to be polymerized, later by aliphatic conjugated diene system monomer 10 ~ 60 % by weight at the 2nd section again, acrylic monomer 5 ~ 30 % by weight, ethene system unsaturated carboxylic acid monomer 0 ~ 13 % by weight and the monomer that can form with other monomers 0 ~ 72 % by weight of their copolymerization add up to 68 ~ 87 % by weight to be polymerized.By this, during the printing of White Board, the manifesting property of intensity is better.
When there is the polymerization process of more than 3 sections, when the total amount of the 2nd section of acrylic monomer later used is set to 100 % by weight, the acrylic amount of monomer of adding in final polymerization process is better be less than 45 % by weight, such viscosity of latex easily declines, and the adhesivity of latex film and intensity when printing manifest excellent simultaneously.
In addition, if the monomer of the 2nd section adds up to 10 ~ 66 % by weight, the 3rd sections of later monomers add up to 2 ~ 62 % by weight, then the trend that the generation with the agglutinator in manufacturing process reduces, and the intensity during printing of White Board manifests better, therefore preferably.
The polymerization of copolymer emulsion of the present invention can use known emulsifying agent (tensio-active agent).The anionic surfactants such as the sulfuric acid of such as higher alcohols, 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 sulfuric acid of nonionic surfactant can be exemplified, the nonionic surfactant such as alkyl ester, alkyl phenyl ether type, alkyl ether type of polyoxyethylene glycol, these emulsifying agents can use one kind or two or more.
The polymerization of copolymer emulsion of the present invention can use known chain-transfer agent (molecular weight regulator) in indefinite ground.Such as n-hexyl mercaptan can be exemplified, n octylmercaptan, tert octyl mercaptan, n-dodecyl mercaptan, tertiary lauryl mercaptan, the alkyl sulfhydryls such as Octadecane base mercaptan, curing xanthogenic acid dimethyl ester, the xanthate compounds such as diisopropyl xanthate disulfide, tetramethyl-thiuram disulfide, tetraethylthiuram disulfide, the thiuram based compounds such as tetramethylthiuram monosulfide, 2, 6-di-tert-butyl-4-methy phenol, the phenol based compounds such as styrenated phenol, the allylic cpds such as vinyl carbinol, methylene dichloride, methylene bromide, the halogenated hydrocarbon compounds such as carbon tetrabromide, α-benzyloxy vinylbenzene, α-benzyloxy vinyl cyanide, the vinyl ether such as α-benzyloxy acrylamide, triphenylethane, pentaphenylethane, propenal, Methylacrylaldehyde, Thiovanic acid, mercaptosuccinic acid, 2-ethylhexyl mercaptoacetate, terpinolene, α-methylstyrenedimer etc., these chain-transfer agents can use one kind or two or more.
In the polymerization of copolymer emulsion of the present invention, as known polymerization starter, can suitably use the 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, the oil-soluble polymerization initiators such as 3,3-tetramethyl butyl.Particularly preferably use Potassium Persulphate, Sodium Persulfate, cumene hydroperoxide, t-butyl hydroperoxide.
As the concrete example of the reductive agent that the present invention preferably uses, sulphite can be exemplified, hydrosulphite, pyrosulfite, hyposulfite, dithionate, thiosulphate, formaldehyde sulfonate, phenyl aldehyde sulfonate, and carboxylic-acid and the salt thereof such as L-AA, saccharosonic acid, tartrate, citric acid, and the recuding sugars such as glucose, sucrose, and the amine such as xylidine, trolamine.Particularly preferably L-AA, saccharosonic acid.
In the polymerization of copolymer emulsion of the present invention, the stable hydrocarbon such as pentane, hexane, heptane, octane, hexanaphthene, suberane can be used as required, the unsaturated hydrocarbons such as amylene, hexene, heptene, cyclopentenes, tetrahydrobenzene, suberene, 4-tetrahydrotoluene, 1-tetrahydrotoluene, the hydrocarbon compounds such as aromatic hydrocarbon such as benzene,toluene,xylene.Although particularly low, the polymerization of boiling point appropriateness terminate rear easily reclaimed by wet distillation etc. and the tetrahydrobenzene recycled or toluene different from object of the present invention, proper from the angle of environmental problem.
There is no particular limitation for the particle diameter of copolymer emulsion of the present invention, preferably 50 ~ 200nm.If number average bead diameter is less than 50nm, the stability degradation of particle, the deterioration of blank sheet of paper gloss, if more than 200nm, the population of per unit weight tails off, and bond area reduces, thus is difficult to manifest bonding strength, therefore undesirable.In addition, if more than 150nm, during the printing of White Board, intensity is difficult to manifest, and is therefore more preferably 50 ~ 150nm.
To the gel content of copolymer emulsion of the present invention without any restriction, but gel content preferably 60 ~ 100 % by weight.If gel content is less than 60 % by weight, then the film toughness of latex reduces, and the bonding strength of various caking agent declines.Also there is the trend of the strength degradation of White Board.Particularly preferably 65 ~ 95 % by weight.
In the polymerization of copolymer emulsion of the present invention, can use the 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 the 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 according to its application target other latex of fusion in appropriate amount.
During the manufacture of copolymer emulsion of the present invention, to the addition means of monomer and other compositions, there is no particular limitation, can adopt in portion-wise addition method, continuously addition means, automatic feeding method any one, but in the present invention, polymerization process must carry out the multi-stage polymeric of more than 2 sections.
In addition, paper coating composition of the present invention can individually or known pigment used in combination, such as, and the mineral dyes such as kaolin, carclazyte, calcium carbonate, talcum, barium sulfate, titanium oxide, aluminium hydroxide, zinc oxide, stain white; Or the pigment dyestuffs such as polystyrene latex.
Further, the content of the copolymer emulsion of the present invention in paper coating composition is better be 2 ~ 15 weight parts (solids components) relative to 100 weight parts (solids component) pigment.The content of copolymer emulsion then cannot bond pigment fully below 2 weight parts, undesirable, if more than 15 weight parts, causes the manufacturing cost of the copolymer emulsion comprised in coating to rise.Be more preferably 2.5 ~ 12 parts of weight parts (solids component).
The treated starches such as starch, Sumstar 190, esterification starch can also be used as required, the natural glue such as soybean protein, casein, or the water-soluble composite adhesives such as polyvinyl alcohol, carboxymethyl cellulose etc.Synthetic latexes such as poly latex, acrylic acid series latex etc. can also be used with copolymer emulsion of the present invention.
When modulating paper coating composition of the present invention, other auxiliary agents can also be added as required, such as dispersion agent (trisodium phosphate, sodium polyacrylate, Sodium hexametaphosphate 99 etc.), 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.).
Method paper coating composition being coated coating paper using can use known technology, the arbitrary coating machines such as such as airblade coating, curtain coating, blade coating, roller coat, rod painting.After coating, desiccated surface, with precision work such as calenderings.
Copolymer emulsion of the present invention is from the angle of intensity when improving coating operations and print etc., must have and form by different monomers at least 3 sections of polymerization process formed, the 1st section polymerization monomer composition be aliphatic conjugated diene system monomer 1.5 ~ 24 % by weight, acrylic monomer 5.1 ~ 25 % by weight, ethene system unsaturated carboxylic acid monomer 4.1 ~ 20 % by weight and can with other monomers 0 ~ 22.3 % by weight (monomer adds up to 13 ~ 34 % by weight) of their copolymerization, to add and the monomer composition carrying out being polymerized is aliphatic conjugated diene system monomer 10 ~ 60 % by weight at the 2nd section later, acrylic monomer 5 ~ 30 % by weight, ethene system unsaturated carboxylic acid monomer 0 ~ 13 % by weight and can with other monomers 0 ~ 72 % by weight (monomer adds up to 68 ~ 87 % by weight) of their copolymerization.
If the aliphatic conjugated diene system monomer of the 1st section is less than 1.5 % by weight, the strength deterioration during printing of White Board, if more than 24 % by weight, the adhesivity deterioration of latex, coating operations when particularly manufacturing White Board brings detrimentally affect, as being easily attached to back flow roll etc.
If the acrylic monomer of the 1st section is less than 5.1 % by weight, then the intensity during printing of White Board and the manifesting property difference of print gloss, in addition, if more than 25 % by weight, the intensity during printing of White Board reduces.
If the ethene system unsaturated carboxylic acid monomer of the 1st section is less than 4.1 % by weight, the intensity difference during printing of the redispersibility of paper coating composition and White Board, if more than 20 % by weight, the viscosity of latex self is too high, causes the operability deteriorations such as the latex delivery deterioration of liquid-feeding pump.
If the monomer of the 1st section adds up to and is less than 13 % by weight, the redispersibility of paper coating composition is poor, in addition, if more than 34 % by weight, and the intensity reduction during printing of White Board.
If the 2nd section of later aliphatic conjugated diene system monomer is less than 10 % by weight, the intensity difference during printing of White Board, in addition, if more than 60 % by weight, the poor adhesion of latex film, coating operations when particularly manufacturing White Board brings detrimentally affect, as being easily attached to back flow roll etc.
If the 2nd section of later acrylic monomer is less than 5 % by weight, then the manifesting property deterioration of intensity and print gloss during the printing of White Board, in addition, if more than 30 % by weight, the strength degradation during printing of White Board.
If the 2nd section of later ethene system unsaturated carboxylic acid monomer is more than 13 % by weight, the viscosity of latex self is too high, causes the operability deteriorations such as the latex delivery deterioration of liquid-feeding pump.
Be made up of different monomers the polymerization process that forms below 2 sections time, the adhesivity of latex film declines.
If more than 60 % by weight of whole consumptions of ethene system unsaturated carboxylic acid monomer add at the polymerization process of the 1st section and do not add in polymerization process in final stage, then the good strength of White Board when printing.Further, if when the total amount of the 2nd section of acrylic monomer used is set to 100 % by weight, the acrylic amount of monomer of adding in final polymerization process is less than 45 % by weight, then the adhesivity of latex is excellent later.
Have at least 3 sections polymerization process copolymer emulsion polymerization in can use known emulsifying agent (tensio-active agent).Such as, can exemplify above-mentioned emulsifying agent (tensio-active agent), these emulsifying agents can use one kind or two or more.
Have at least 3 sections polymerization process copolymer emulsion polymerization in, can indefinite ground use known chain-transfer agent (molecular weight regulator).Can exemplify chain-transfer agent as escribed above (molecular weight regulator), these chain-transfer agents can use one kind or two or more.
Have at least 3 sections polymerization process copolymer emulsion polymerization in, as known polymerization starter, except above-mentioned polymerization starter, can also suitably use reducto oxydative system polymerization starter.Particularly preferably use Potassium Persulphate, Sodium Persulfate, cumene hydroperoxide, t-butyl hydroperoxide.To the amount of polymerization starter, there is no particular limitation, can consider monomer composition, polyreaction system pH, do suitable adjustment with the combination of other additives etc.
Have at least 3 sections polymerization process copolymer emulsion polymerization in, above-mentioned hydrocarbon compound can be used.Although particularly low, the polymerization of boiling point appropriateness terminate easily to be reclaimed by wet distillation etc. afterwards, the tetrahydrobenzene that recycles or toluene different from object of the present invention, proper from the angle of environmental problem.
There is no particular limitation for the particle diameter of the copolymer emulsion obtained therefrom, preferably 50 ~ 150nm.If number average bead diameter is less than 50nm, if more than 150nm, there is the trend of strength degradation during the printing of White Board in the deterioration of blank sheet of paper gloss.The particle diameter of copolymer emulsion can by suitably changing the various emulsifying agents, the kind of polymerization starter and the consumption thereof that use in the polymerization of copolymer emulsion or addition means, the usage ratio etc. of polywater adjusts.
To the gel content of copolymer emulsion without any restriction, gel content preferably 60 ~ 100 % by weight.If gel content is less than 60 % by weight, then there is the trend of strength degradation during the printing of White Board, undesirable.Particularly preferably 65 ~ 98 % by weight.
Have at least 3 sections polymerization process copolymer emulsion polymerization in, can use the 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 the 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, the copolymer emulsion obtained therefrom also can according to its application target other latex of fusion in appropriate amount.
During the manufacture of this copolymer emulsion, to the addition means of monomer and other compositions, to be made up of except at least 3 sections of polymerization process this point forming different monomers that there is no particular limitation except having, the addition means of monomer can adopt in portion-wise addition method, continuously addition means any one.
The polymer latex that paper coating composition of the present invention contains pigment and obtained by above-mentioned operation.Pigment can individually or known pigment used in combination, such as above-mentioned pigment.
Further, the content of the copolymer emulsion in paper coating composition is better be 2 ~ 20 weight parts (solids components) relative to 100 weight parts (solids component) pigment.The content of copolymer emulsion is less than 2 weight parts and then cannot bonds pigment fully, undesirable, if more than 20 weight parts, opaqueness and blank sheet of paper gloss decline, and the cost increase of paper coating composition.
The treated starches such as starch, Sumstar 190, esterification starch can also be used as required, the natural glue such as soybean protein, casein, or the water-soluble composite adhesives such as polyvinyl alcohol, carboxymethyl cellulose etc.Synthetic latexes such as poly latex, acrylic acid series latex etc. can also be used with copolymer emulsion of the present invention.
When modulating paper coating composition of the present invention, other auxiliary agents can also be added as required, such as dispersion agent (trisodium phosphate, sodium polyacrylate, Sodium hexametaphosphate 99 etc.), 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.).
Method paper coating composition being coated coating paper using can use known technology, such as any one coating machine above-mentioned.After coating, desiccated surface, with precision work such as calenderings.
Embodiment
Below, exemplify embodiment and carry out more specific description to the present invention, the present invention only otherwise exceed its technology main idea by the restriction of these embodiments.In addition, represent in embodiment that part of ratio and % are as long as no special explanation, all refer to weight basis.Further, the evaluation of the various physical property in 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 passes through dynamic light scattering determination.FPAR-1000 (Otsuka Electronics Co., Ltd. system is used) during mensuration.
The E type viscosity of copolymer emulsion
The solids component of copolymer emulsion is adjusted to 50% to measure E type viscosity.In addition, liquid temperature during mensuration uses Water Tank with Temp.-controlled to keep constant 25 DEG C, uses 3 ° of circular cones to measure.Determining instrument uses the E type viscometer of Tokyo gauge Inc..
The evaluation of dirt settling
To each copolymer emulsion, detect by an unaided eye in polymerization, be attached to the dirt of reactor, evaluate 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 being polymerized the copolymer emulsion after terminating, with 300 order metal mesh filters.By gravimetry after agglutinator drying residual on wire netting, obtain and the ratio of sample (solids component converts) (agglutinator production rate), evaluate with following 3 grades.
A: be less than for 0.05% (lacking)
B: be more than or equal to 0.05 but be less than 0.10% (slightly many)
More than C:0.10% (quite a lot of)
The viscosimetric analysis of latex and evaluation
The viscosity of the latex when solids component of copolymer emulsion being adjusted to 50% is measured according to the measuring method of JIS K7117-1.Following grade evaluation is pressed to the viscosity of gained.
Below A:300mPas
B：301～800mPa·s
C：801～2000mPa·s
More than D:2001mPas
The mensuration of the gel content of copolymer emulsion
Latex film is made in the atmosphere of temperature 40 DEG C, humidity 85%.Thereafter, the latex film of about 1g is weighed as Xg.Put it into swelling in the toluene of 400ml and dissolve 48 hours.Thereafter, filtered with 300 weighed order wire nettings, then make toluene evaporates dry, after drying, weight deducts screen cloth weight, and weight after the drying of weighing sample, as Yg.
Gel content (%)=Y/X × 100
The evaluation of dry fluffing (the De ラ イ ピ ッ Network) intensity of White Board
The degree of fluffing when simultaneously printing each White Board sample by naked eyes judgement RI printing press, relatively visual valuation is from 5 grades (excellent) to 1 grade (bad).
The evaluation of the blank sheet of paper gloss of White Board
The glossiness of each White Board sample measures according to JIS P8142.The larger blank sheet of paper gloss of numerical value is better.
The evaluation of the print gloss of White Board
Diel is placed, by the reflecting feel of visual judgement printing surface after printing each White Board sample by RI printing press with colored ink (process ink, 0.5g).
(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 mono-バ mono-) after transparent base material (the thick 100 μm of haze values 2.2% of Mitsubishi Plastics Inc polyester film DIA FOIL S100-100) upper coating copolymer emulsion, drying 1 minute in 120 DEG C of heated air circulation type stoves, obtained latex film, confirms that glue spread counts 13g/m with solids component 2± 1g/m 2.To the latex film of gained, use color technical institute spectrophotometric Meter CMS35SP in village, measure according to the measuring method of method (2000) of asking of the haze value of the plastics-transparent material of JIS K7136.
Haze value (%)=(only the transmitted light of scattering composition)/(full ght transmission light) × 100
Obtained the haze value of the latex film coating transparent substrate by above-mentioned calculating formula, calculate the difference with the haze value of transparent substrate self.The mist degree value difference of this latex film and transparent substrate is more little more transparent, is the latex film that the diffuse-reflectance of light is few.
The synthesis of copolymer emulsion (1)
The 1st shown in polywater 160 parts He table 1 section each monomer recorded and other compounds is added in the polymerization reactor of resistance to compacting, polymerization is started at 70 DEG C, when polymerisation conversion is more than 80%, add each monomer and other compounds of the 2nd section, be polymerized at 70 DEG C, terminate polymerization when final polymerisation conversion is more than 96%.
Then, use sodium hydroxide that the pH of the copolymer emulsion of gained is adjusted to 7, by wet distillation removing unreacted monomer and other low-boiling compounds, obtain copolymer emulsion 1.
The synthesis of copolymer emulsion (2,11 ~ 14)
The monomer of each section composition is changed into the content that table 1 and table 2 are recorded, be polymerized in the same manner as latex 1, obtain latex 2 and 11 ~ 14.
The synthesis of copolymer emulsion (3)
The 1st shown in polywater 140 parts He table 1 section each monomer recorded and other compounds is added in the polymerization reactor of resistance to compacting, polymerization is started at 70 DEG C, when polymerisation conversion is more than 80%, add each monomer and other compounds of the 2nd section, be polymerized at 70 DEG C, terminate polymerization when final polymerisation conversion is more than 96%.
Then, use sodium hydroxide that the pH of the copolymer emulsion of gained is adjusted to 7, by wet distillation removing unreacted monomer and other low-boiling compounds, obtain copolymer emulsion 3.
The synthesis of copolymer emulsion (4,15 ~ 18)
The monomer of each section composition is changed into the content that table 1 and table 2 are recorded, be polymerized in the same manner as latex 3, obtain latex 4 and 15 ~ 18.
The synthesis of copolymer emulsion (5 ~ 7,19 ~ 21)
Each monomer and other compounds of polywater 140 parts and table 1 and section record of the 1st shown in table 2 is added in the polymerization reactor of resistance to compacting, polymerization is started at 70 DEG C, when polymerisation conversion is more than 50%, adds each monomer and other compounds of the 2nd section, be polymerized at 70 DEG C.After adding the 2nd section, add each monomer and other compounds of the 3rd section when polymerisation conversion is more than 80%, terminate polymerization when final polymerisation conversion is more than 96%.
Then, use sodium hydroxide that the pH of the copolymer emulsion of gained is adjusted to 7, by wet distillation removing unreacted monomer and other low-boiling compounds, obtain copolymer emulsion 5 ~ 7,19 ~ 21.
The synthesis of copolymer emulsion (8)
The 1st shown in polywater 180 parts He table 1 section each monomer recorded and other compounds is added in the polymerization reactor of resistance to compacting, polymerization is started at 70 DEG C, when polymerisation conversion is more than 50%, adds each monomer and other compounds of the 2nd section, be polymerized at 70 DEG C.After adding the monomer of the 2nd section, add each monomer and other compounds of the 3rd section when polymerisation conversion is more than 80%, add each monomer and other compounds of the 4th section when polymerisation conversion is more than 85%, terminate polymerization when final polymerisation conversion is more than 96%.
Then, use sodium hydroxide that the pH of the copolymer emulsion of gained is adjusted to 7, by wet distillation removing unreacted monomer and other low-boiling compounds, obtain copolymer emulsion 8.
The synthesis of copolymer emulsion (9)
In the polymerization reactor of resistance to compacting, add the 1st shown in polywater 140 parts He table 1 section each monomer recorded and other compounds, start polymerization at 70 DEG C, add each monomer and other compounds of the 2nd section when polymerisation conversion is more than 50%, be polymerized at 70 DEG C.After adding the monomer of the 2nd section, add each monomer and other compounds of the 3rd section when polymerisation conversion is more than 80%, add each monomer and other compounds of the 4th section when polymerisation conversion is more than 85%, terminate polymerization when final polymerisation conversion is more than 96%.
Then, use sodium hydroxide that the pH of the copolymer emulsion of gained is adjusted to 7, by wet distillation removing unreacted monomer and other low-boiling compounds, obtain copolymer emulsion 9.
The synthesis of copolymer emulsion (10)
In the polymerization reactor of resistance to compacting, add the 1st shown in polywater 140 parts He table 2 section each monomer recorded and other compounds, start polymerization at 70 DEG C, terminate polymerization when polymerisation conversion is more than 96%.
Then, use sodium hydroxide that the pH of the copolymer emulsion of gained is adjusted to 7, by wet distillation removing unreacted monomer and other low-boiling compounds, obtain copolymer emulsion 10.
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 meets above formula (1), the dirt settling in manufacturing process and the generation of agglutinator few, the viscosity of the latex of gained is also low.
By shown in table 2, in comparative example 1, polymerization process only has 1 section, and the velocity slope dependency of E type viscosity is outside specialized range, and the generation of agglutinator and dirt settling is slightly many, and viscosity of latex is high.
In comparative example 2, outside the scope that the 1st section of acrylic monomer and ethene unsaturated carboxylic acid monomer added is recorded in claim 1, in comparative example 3, on the basis of comparative example 2, also has the aliphatic conjugated diene system monomer added at the 1st section 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, and latex viscosity is high.
Comparative example 4 is because the monomer total of the 1st section is more than 32 % by weight, in addition, comparative example 5 due to the 2nd section of acrylic monomer later added more than the velocity slope dependency of 30 % by weight, E type viscosity outside scope, the generation of agglutinator and dirt settling is many, and latex viscosity is high.
Comparative example 10 due to the 1st section of ethene unsaturated carboxylic acid monomer added more than the velocity slope dependency of 20 % by weight, E type viscosity outside scope, the generation of agglutinator and dirt settling is many, and latex viscosity is high.
Comparative example 11 is because the 2nd section of aliphatic conjugated diene system monomer used is more than 60 % by weight later, comparative example 12 is less than 5 % by weight due to the acrylic monomer added in the 2nd section of later operation, the velocity slope dependency of E type viscosity is outside scope, the generation of agglutinator and dirt settling is many, and latex viscosity is high.
The manufacture of paper coating composition and evaluation
Use copolymer emulsion 3 ~ 7,9,10,15 ~ 21 according to the formula shown in following, with sodium hydroxide, pH is adjusted to 9.5, makes paper coating composition.
(formula of paper coating composition)
Formula
Particulate kaolin 40 parts
Water-ground limestone 60 parts
Treated starch 2 parts
Copolymer emulsion 7 parts
·······················
Solid component concentration 67%
The manufacture of White Board and evaluation
At bodystock paper (unit plane accumulated amount 55g/m 2) on, measured as 10g/m with the painting in every face 2use wire-wound rod to be coated with above-mentioned paper coating composition, after drying, carry out calendering process with the condition of line pressure 60kg/cm, temperature 50 C, obtain White Board.The White Board of gained is used for each test evaluate, the results are shown in table 1 and table 2.
As shown in table 1, table 2, during the printing of the White Board of copolymer emulsion 3 ~ 7,9 of the present invention, intensity is all fine, and blank sheet of paper gloss number, print gloss value are high.
In comparative example 1, polymerization process only has 1 section, and the mist degree difference of latex film and base material is more than 1.0%, and blank sheet of paper gloss printing gloss is deteriorated.
Outside the scope that the acrylic monomer and ethene unsaturated carboxylic acid monomer that add at the 1st section in comparative example 6 are recorded in claim 1, the mist degree difference of latex film and base material is more than 1.0%, and blank sheet of paper gloss printing gloss is deteriorated.
Outside the scope recorded in claim 1 at the 1st section of aliphatic conjugated diene system monomer added, acrylic monomer and ethene unsaturated carboxylic acid monomer in comparative example 7, the mist degree difference of latex film and base material is more than 1.0%, the deterioration of blank sheet of paper gloss printing gloss, and dry fluffing strength deterioration.
Comparative example 8 is because the monomer total of the 1st section is more than 32 % by weight, and the mist degree difference of latex film and base material is more than 1.0%, and blank sheet of paper gloss printing gloss is deteriorated.
Comparative example 9 is at the 2nd section of acrylic monomer added later more than 30 % by weight, and the mist degree difference of latex film and base material is more than 1.0%, and blank sheet of paper gloss printing gloss is deteriorated.
Comparative example 10 is at the 1st section of ethene unsaturated carboxylic acid monomer added more than 20 % by weight, and the mist degree difference of latex film and base material is more than 1.0%, and the deterioration of blank sheet of paper gloss, print gloss is also deteriorated.
Comparative example 11 is because the aliphatic conjugated diene system monomer used at the 2nd section is more than 60 % by weight later, and the mist degree difference of latex film and base material is more than 1.0%, and the deterioration of blank sheet of paper gloss printing gloss, does fluffing strength deterioration.
The acrylic monomer that comparative example 12 adds in the 2nd section of later operation is less than 5 % by weight, and dry fluffing strength deterioration, the mist degree difference of latex film and base material is more than 1.0%, and blank sheet of paper gloss printing gloss is deteriorated.
< latex 22 ~ 31>
The mensuration of the number average bead diameter of copolymer emulsion
The number average bead diameter of copolymer emulsion passes through dynamic light scattering determination.FPAR-1000 (Otsuka Electronics Co., Ltd. system is used) during mensuration.
The mensuration of the gel content of copolymer emulsion
Latex film is manufactured in room temperature atmosphere.Thereafter, the latex film of about 1g is weighed as Xg.Put it in the toluene of 400ml and make its swelling dissolve 48 hours.Thereafter, filtered with 300 weighed order wire nettings, then make toluene evaporates dry, after drying, weight deducts screen cloth weight, and after weighing the drying of sample, weight is as Yg.Gel content is calculated with following formula.
Gel content (%)=Y/X × 100
The adhesiveness test of copolymer emulsion film
As the standard of the difficulty that latex adheres to back flow roll etc., the adhesivity with regard to copolymer emulsion film is tested.With glue spread 12g/m on polyester film 2be coated with each copolymer emulsion, in the baking oven of 120 DEG C after dry 1 minute, be cut into the rectangular shape that 1cm is wide.Black platform paper attaches the rectangular parallelepiped of whole multipolymers of synthesis side by side.
Stacked filter paper thereon, crimps with RI printing press.Thereafter, after filter paper is peeled off, the attachment state of visual judgement filter paper fibre on each latex film surface, the adhesivity of more each latex film.Fiber is adhered to few A excellent as adhesivity, using the D as poor adhesion many for fiber attachment, relatively evaluate by following grade.
(excellent) A > B > C > D (bad)
The evaluation of the redispersibility of paper coating composition
NBR black rubber plate is coated with each composition sample abreast with #6 wire-wound rod, and in 60 DEG C of heated air circulation type stoves after dry 3 minutes, clean 1 minute with the flowing water of 30 DEG C, visual observation remains in the epithelium of the composition on NBR black rubber plate.Using the A excellent as redispersibility of the less residue of epithelium, using the E as redispersibility difference many for the residual quantity of epithelium, relatively evaluated by following grade by visual.
(excellent) A > B > C > D > E (bad)
The evaluation of the dry fluffing intensity of White Board
The degree of fluffing when simultaneously printing each White Board sample by naked eyes judgement RI printing press, carries out relatively visual valuation from 5 grades (excellent) to 1 grade (bad).
The evaluation of the wet raising intensity of White Board
Use RI printing press by glue clearer (モ Le ト Application ロ mono-Le) simultaneously at each White Board sample humidification, after printing each White Board sample with ink roller immediately after giving water simultaneously, with the naked eye judge the degree of fluffing now, carry out relatively visual valuation from 5 grades (excellent) to 1 grade (bad).
The synthesis of copolymer emulsion (22 ~ 24,28 ~ 31)
In the polymerization reactor of resistance to compacting, add polywater 150 parts and Potassium Persulphate 1 part, after fully stirring, add each monomer shown in the 1st section and other compounds of table 3 and table 4, be warming up to 70 DEG C and start polymerization.For the polymerization of the 2nd section, the each monomer and other compounds that add the 2nd section when the polymerisation conversion of the 1st section is more than 50% are polymerized, for the polymerization of the 3rd section, add each monomer and other compounds of the 3rd section when the polymerisation conversion of the 2nd section is more than 80%, terminate polymerization when final polymerisation conversion is more than 95%.
Then, use sodium hydroxide and potassium hydroxide that the pH of the copolymer emulsion of gained is adjusted to 7, by wet distillation removing unreacted monomer and other low-boiling compounds, obtain copolymer emulsion 22 ~ 24,28 ~ 31.
The synthesis of copolymer emulsion (25 ~ 27)
In the polymerization reactor of resistance to compacting, add polywater 150 parts and Potassium Persulphate 1 part, after fully stirring, add each monomer shown in the 1st section and other compounds of table 3, be warming up to 70 DEG C and start polymerization.For the polymerization of the 2nd section, the each monomer and other compounds that add the 2nd section when the polymerisation conversion of the 1st section is more than 50% are polymerized, for the polymerization of the 3rd section, the each monomer and other compounds that add the 3rd section when the polymerisation conversion of the 2nd section is more than 80% are polymerized, for the polymerization of the 4th section, the each monomer and other compounds that add the 4th section when the polymerisation conversion of the 3rd section is more than 85% are polymerized, and terminate polymerization when final polymerisation conversion is more than 95%.
Then, use sodium hydroxide and potassium hydroxide that the pH of the copolymer emulsion of gained is adjusted to 7, by wet distillation removing unreacted monomer and other low-boiling compounds, obtain copolymer emulsion 25 ~ 27.
The manufacture of paper coating composition and evaluation
Use by the above-mentioned copolymer emulsion 22 ~ 31 be synthesized into according to the formula shown in following, with sodium hydroxide, pH is adjusted to 9.5, makes paper coating composition.
(formula of paper coating composition)
Formula
Kaolin 40 parts
Water-ground limestone 60 parts
Treated starch 2 parts
Copolymer emulsion 7 parts
·······················
Solid component concentration 67%
The manufacture of White Board and evaluation
At bodystock paper (unit plane accumulated amount 55g/m 2) on, measured as 10g/m with the painting in every face 2use wire-wound rod to be coated with above-mentioned paper coating composition, after drying, carry out calendering process with the condition of line pressure 60kg/cm, temperature 50 C, obtain White Board.The White Board of gained be used for each test and evaluate, the results are shown in table 3 and table 4.
As 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 the paper coating composition of these copolymer emulsions also all fine, and dry fluffing intensity and the wet raising intensity of the White Board of gained are good.
The acrylic monomer of the 1st section in comparative example 13 is less than 5.1 % by weight, and ethene unsaturated carboxylic acid monomer amount is less than 4.1 % by weight, the redispersibility of composition and the dry fluffing intensity difference of White Board.
The acrylic monomer of the 1st section in comparative example 14 is less than 5.1 % by weight, the dry fluffing intensity difference of White Board.
The aliphatic conjugated diene system monomer of the 1st section in comparative example 15 is less than 1.5 % by weight, ethene unsaturated carboxylic acid monomer is less than 4.1 % by weight, the monomer of the 1st section adds up to and is less than 13 % by weight, the redispersibility of paper coating composition and the dry fluffing intensity of White Board significantly deteriorated.
The monomer of the 1st section in comparative example 16 adds up to more than 34 % by weight, the dry fluffing intensity difference of White Board.
Foregoing invention provides as illustrative embodiment of the present invention, but this is only illustrate, and does not form determinate explanation.The variation obvious 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, the generation of the dirt settling of copolymer emulsion of the present invention in manufacturing process and agglutinator is few, and production efficiency is excellent, and viscosity of latex is low, therefore in the manufacturing stage and transport operation, keeping operation etc. of copolymer emulsion, there is good operability, exceedingly useful.
When copolymer emulsion of the present invention is used as the tackiness agent of paper coating composition, lower viscosity of latex can be kept when the printing improving White Board while intensity, therefore particularly useful.
As mentioned above, use copolymer emulsion of the present invention and paper coating composition, the White Board of good strength during the good and printing of blank sheet of paper gloss, print gloss can be obtained.
As mentioned above, the adhesivity of the latex film of copolymer emulsion of the present invention is excellent, use the redispersibility of the paper coating composition of the present invention of this copolymer emulsion good, coating operations when White Board manufactures by this is excellent, also can tackle the high speed of coating apparatus.In addition, the good strength during printing of coating said composition and the White Board that obtains, therefore as paper coating composition tackiness agent and composition very useful.

Claims (11)

1. copolymer emulsion, it forms the polymerization of at least 2 sections of polymerization process formed and the copolymer emulsion obtained by having by different monomers,
The 1st section be aliphatic conjugated diene system monomer 1.5 ~ 24 % by weight, acrylic monomer 5.1 ~ 25 % by weight, ethene system unsaturated carboxylic acid monomer 3.1 ~ 20 % by weight and the monomer that can form with other monomers 0 ~ 22.3 % by weight of their copolymerization add up to 13 ~ 32 % by weight, whole monomer adds up to 100 % by weight
The 2nd section be aliphatic conjugated diene system monomer 10 ~ 60 % by weight later, acrylic monomer 5 ~ 30 % by weight, ethene system unsaturated carboxylic acid monomer 0 ~ 13 % by weight and the monomer that can form with other monomers 0 ~ 72 % by weight of their copolymerization add up to 68 ~ 87 % by weight, whole monomer adds up to 100 % by weight
It is characterized in that, described aliphatic conjugated diene system monomer for being selected from 1,3-butadiene, 2-methyl isophthalic acid, at least one of 3-divinyl, 2,3-dimethyl-1,3-butadiene, chlorbutadiene,
Described ethene system unsaturated carboxylic acid monomer is at least one being selected from vinylformic acid, methacrylic acid, β-crotonic acid, toxilic acid, fumaric acid, methylene-succinic acid,
The velocity slope dependency of the E type viscosity when solids component of this copolymer emulsion is adjusted to 50%, liquid temperature is adjusted to 25 DEG C meets following formula (1):
B/A＝0.50～1.1……(1)
In 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, is characterized in that,
Have and form by different monomers at least 3 sections of polymerization process formed,
13 ~ 32 % by weight are added up to be polymerized aliphatic conjugated diene system monomer 1.5 ~ 24 % by weight, acrylic monomer 5.1 ~ 25 % by weight, ethene system unsaturated carboxylic acid monomer 4.1 ~ 20 % by weight and the monomer that can form with other monomers 0 ~ 21.3 % by weight of their copolymerization at the 1st section
68 ~ 87 % by weight are added up to be polymerized aliphatic conjugated diene system monomer 10 ~ 60 % by weight, acrylic monomer 5 ~ 30 % by weight, ethene system unsaturated carboxylic acid monomer 0 ~ 13 % by weight and the monomer that can form with other monomers 0 ~ 72 % by weight of their copolymerization after the 2nd section.
3. copolymer emulsion as claimed in claim 1, is characterized in that, more than 60 % by weight of whole consumptions of ethene system unsaturated carboxylic acid monomer add at the polymerization process of the 1st section, and do not add in the polymerization process of final stage.
4. copolymer emulsion as claimed in claim 1, is characterized in that, be used as paper coating copolymer emulsion.
5. copolymer emulsion as claimed in claim 4, is characterized in that, count 13g/m with dry weight 2± 1g/m 2glue spread this copolymer emulsion is coated transparent substrate after the dry and film that obtain be 0 ~ 1.0% by the difference of the haze value of JIS K7136 mensuration and the haze value of transparent substrate self.
6. paper coating composition, is characterized in that, containing copolymer emulsion according to claim 5.
7. copolymer emulsion, it monomer is added up to aliphatic conjugated diene system monomer, acrylic monomer, the ethene system unsaturated carboxylic acid monomer of 100 % by weight and can carry out letex polymerization with other monomers of their copolymerization and must be used as the copolymer emulsion of tackiness agent in paper coating composition, it is characterized in that
Have and form by different monomers at least 3 sections of polymerization process formed, at the 1st section by aliphatic conjugated diene system monomer 1.5 ~ 24 % by weight, acrylic monomer 5.1 ~ 25 % by weight, ethene system unsaturated carboxylic acid monomer 4.1 ~ 20 % by weight and the monomer that can form with other monomers 0 ~ 23.3 % by weight of their copolymerization add up to 13 ~ 34 % by weight to be polymerized, by aliphatic conjugated diene system monomer 10 ~ 60 % by weight after the 2nd section, acrylic monomer 5 ~ 30 % by weight, ethene system unsaturated carboxylic acid monomer 0 ~ 13 % by weight and the monomer that can form with other monomers 0 ~ 72 % by weight of their copolymerization add up to 66 ~ 87 % by weight to be polymerized,
Described aliphatic conjugated diene system monomer for being selected from 1,3-butadiene, 2-methyl isophthalic acid, at least one of 3-divinyl, 2,3-dimethyl-1,3-butadiene, chlorbutadiene,
Described ethene system unsaturated carboxylic acid monomer is at least one being selected from vinylformic acid, methacrylic acid, β-crotonic acid, toxilic acid, fumaric acid, methylene-succinic acid.
8. copolymer emulsion as claimed in claim 7, is characterized in that, more than 60 % by weight of whole consumptions of ethene system unsaturated carboxylic acid monomer add at the polymerization process of the 1st section, and do not add in the polymerization process of final stage.
9. copolymer emulsion as claimed in claim 7, is characterized in that, when the total amount of the 2nd section of acrylic monomer later used is set to 100 % by weight, the acrylic amount of monomer of adding in final polymerization process is less than 45 % by weight.
10. paper coating composition, is characterized in that, containing copolymer emulsion according to claim 7.
The manufacture method of 11. copolymer emulsions, it is the manufacture method being used as the copolymer emulsion of tackiness agent in paper coating composition that monomer is added up to the aliphatic conjugated diene system monomer of 100 % by weight, acrylic monomer, ethene system unsaturated carboxylic acid monomer and can carry out letex polymerization with other monomers of their copolymerization and obtain, it is characterized in that
Have and form by different monomers at least 3 sections of polymerization process formed, be included in the 1st section by aliphatic conjugated diene system monomer 1.5 ~ 24 % by weight, acrylic monomer 5.1 ~ 25 % by weight, ethene system unsaturated carboxylic acid monomer 4.1 ~ 20 % by weight and the monomer that can form with other monomers 0 ~ 23.3 % by weight of their copolymerization add up to 13 ~ 34 % by weight operations of being polymerized, and by aliphatic conjugated diene system monomer 10 ~ 60 % by weight after the 2nd section, acrylic monomer 5 ~ 30 % by weight, ethene system unsaturated carboxylic acid monomer 0 ~ 13 % by weight and the monomer that can form with other monomers 0 ~ 72 % by weight of their copolymerization add up to 66 ~ 87 % by weight operations of being polymerized,
Described aliphatic conjugated diene system monomer for being selected from 1,3-butadiene, 2-methyl isophthalic acid, at least one of 3-divinyl, 2,3-dimethyl-1,3-butadiene, chlorbutadiene,
Described ethene system unsaturated carboxylic acid monomer is at least one being selected from vinylformic acid, methacrylic acid, β-crotonic acid, toxilic acid, fumaric acid, methylene-succinic acid.
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