JP2016030780A - Latex containing copolymer, composition for paper coating, coated paper and method for producing thereof - Google Patents
Latex containing copolymer, composition for paper coating, coated paper and method for producing thereof Download PDFInfo
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- JP2016030780A JP2016030780A JP2014153093A JP2014153093A JP2016030780A JP 2016030780 A JP2016030780 A JP 2016030780A JP 2014153093 A JP2014153093 A JP 2014153093A JP 2014153093 A JP2014153093 A JP 2014153093A JP 2016030780 A JP2016030780 A JP 2016030780A
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- Prior art keywords
- polymerization
- added
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- mass
- monomer
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- 239000004816 latex Substances 0.000 title claims abstract description 106
- 229920000126 latex Polymers 0.000 title claims abstract description 106
- 229920001577 copolymer Polymers 0.000 title claims abstract description 76
- 239000000203 mixture Substances 0.000 title claims abstract description 69
- 238000000576 coating method Methods 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 239000011248 coating agent Substances 0.000 title claims description 23
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 224
- 239000000178 monomer Substances 0.000 claims abstract description 143
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 48
- 150000001993 dienes Chemical class 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 22
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- 239000008199 coating composition Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000003247 decreasing effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000012986 chain transfer agent Substances 0.000 description 19
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- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
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- 239000005977 Ethylene Substances 0.000 description 2
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- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical class CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical class CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
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- 239000000344 soap Substances 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- GYHZLNKMZPYTFB-UHFFFAOYSA-N 2-(oxiran-2-yl)acetamide Chemical compound NC(=O)CC1CO1 GYHZLNKMZPYTFB-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical class CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
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- OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 description 1
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- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 description 1
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- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical class CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000005385 peroxodisulfate group Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical class CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 239000013053 water resistant agent Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Abstract
Description
本発明は、共重合体を含むラテックス、紙塗工用組成物、塗工紙、及びラテックスの製造方法に関する。 The present invention relates to a latex containing a copolymer, a composition for paper coating, a coated paper, and a method for producing the latex.
共重合体を含むラテックスは、紙塗工における顔料バインダー、カーペットバッキング剤、各種接着剤及び粘着剤、繊維結合剤並びに塗料等といった広範な用途に用いられている。これらの用途に用いられる共重合体を含むラテックスには、基材や配合される顔料等に対する優れた接着力が要求される。 Latex containing a copolymer is used in a wide range of applications such as pigment binders in paper coating, carpet backing agents, various adhesives and pressure-sensitive adhesives, fiber binders and paints. Latex containing a copolymer used for these applications is required to have excellent adhesion to a substrate, a pigment to be blended, and the like.
塗工紙は、抄造された紙の表面の平滑性を高め、光沢や印刷適性を向上させる目的で、カオリンクレー、炭酸カルシウム、サチンホワイト、タルク、酸化チタン等の無機顔料やプラスチック顔料等の有機顔料を原紙に塗布したものが汎用されている。これらの顔料のバインダーとしては、ジエン系共重合体を含むラテックスが一般的に用いられている。顔料バインダーとして用いられる共重合体を含むラテックスの性質は、これを利用した塗工紙の表面強度や印刷品質、塗工紙の生産操業性等に影響を及ぼす。 Coated paper is made of organic pigments such as kaolin clay, calcium carbonate, satin white, talc, titanium oxide, and other organic pigments for the purpose of enhancing the smoothness of the surface of the paper and improving the gloss and printability. A material in which a pigment is applied to a base paper is widely used. As a binder for these pigments, a latex containing a diene copolymer is generally used. The nature of the latex containing a copolymer used as a pigment binder affects the surface strength and print quality of coated paper using this, and the production operability of the coated paper.
近年、印刷の高速化や高度化が進み、塗工紙に要求される性能が厳しくなってきている。特に、インクのタックによる紙表面の破壊に対する抵抗性（いわゆるピック強度）の向上が以前にも増して要求されている。さらには、塗工紙の生産コストを抑制する目的で、高コスト原材料であるラテックスの使用割合を減らす観点でも、ラテックスのピック強度の向上が望まれている。 In recent years, the speed and sophistication of printing have progressed, and the performance required for coated paper has become severe. In particular, an improvement in resistance (so-called pick strength) to the destruction of the paper surface due to ink tack is required more than ever before. Furthermore, in order to reduce the production cost of coated paper, an improvement in the pick strength of the latex is also desired from the viewpoint of reducing the usage rate of latex, which is a high-cost raw material.
一方、塗工紙の生産においても、生産能力及び生産性の向上のために、塗工速度の高速化が進んでいる。これに伴って塗工操業性の改良、特に主な障害であるバッキングロール汚れに対する諸特性、すなわち塗工層の耐湿潤ベタツキ性の向上も強く要求されている。 On the other hand, in the production of coated paper, the coating speed is increasing in order to improve production capacity and productivity. Along with this, improvement in coating operability, in particular, various properties against the backing roll stain, which is the main obstacle, that is, improvement in the wet stickiness resistance of the coating layer is also strongly demanded.
上述した様な共重合体を含むラテックスに関する技術として、例えば、特定の単量体組成で二段又は二段以上の多段で重合を行う共重合体を含むラテックスに関する技術が提案されている（特許文献１、２）。また、特定の単量体混合物を比較的低温で重合を開始し、特定の重合転化率になるまで特定の割合で重合温度を昇温する方法で得られる共重合体を含むラテックスに関する技術が提案されている（特許文献３）。さらには、特定の単量体混合物を比較的高温で重合し、特定の重合転化率になるまで特定の割合で重合温度を降温する方法で得られる共重合体を含むラテックスに関する技術が提案されている（特許文献４）。 As a technique relating to a latex containing a copolymer as described above, for example, a technique relating to a latex containing a copolymer that performs polymerization in a specific monomer composition in two or more stages is proposed (patent) References 1, 2). Also proposed is a technology related to latex containing a copolymer obtained by starting polymerization of a specific monomer mixture at a relatively low temperature and raising the polymerization temperature at a specific rate until a specific polymerization conversion rate is reached. (Patent Document 3). Furthermore, a technology relating to a latex containing a copolymer obtained by polymerizing a specific monomer mixture at a relatively high temperature and lowering the polymerization temperature at a specific rate until a specific polymerization conversion rate is obtained has been proposed. (Patent Document 4).
上述したように、塗工紙の品質や生産に関する問題を踏まえて、共重合体を含むラテックスについても種々検討されているが、未だ不十分である。例えば、ピック強度を改良するために共役ジエン系単量体の組成比率を上げて共重合体のガラス転移温度を低くする方法等も検討されているが、この方法では白紙光沢の低下や耐膨潤ベタツキ性の低下が起こるといった問題がある。 As described above, various types of latex containing a copolymer have been studied in view of problems relating to the quality and production of coated paper, but it is still insufficient. For example, in order to improve the pick strength, a method of increasing the composition ratio of the conjugated diene monomer and lowering the glass transition temperature of the copolymer has been studied. There is a problem that the stickiness decreases.
また、ラテックスのピック強度と、塗工操業性に関連する特性である耐膨潤ベタツキ性やバッキングロール汚れの抑制効果は、相反する特性であり、一方が向上しても他方が低下するといった関係に陥りやすく、これらを高いレベルで両立させることは困難であるといった問題もある。 In addition, the picking property of latex and the anti-swelling property, which is a property related to coating operability, and the effect of suppressing backing roll soiling are contradictory properties, and there is a relationship in which the other decreases even if one improves. There is also a problem that it is easy to fall and it is difficult to make them compatible at a high level.
そして、特許文献１及び２の技術では、塗工紙の接着強度の向上とバッキングロール汚れ特性の向上を両立させる手段としていずれも不十分なものである。特許文献３及び４の技術では、得られる共重合体を含むラテックスの耐湿潤ベタツキ性は不十分であり、これらの共重合体を含むラテックスを用いた塗工紙のピック強度も、近年の高い要求を満足するものではない。 The techniques of Patent Documents 1 and 2 are insufficient as means for achieving both improvement in adhesive strength of coated paper and improvement in backing roll dirt characteristics. In the techniques of Patent Documents 3 and 4, the wet stickiness resistance of the latex containing the obtained copolymer is insufficient, and the pick strength of coated paper using the latex containing these copolymers is also high in recent years. It does not satisfy the requirements.
本発明は、上記事情に鑑みなされたものであり、塗工紙とした際のピック強度に優れ、かつ耐湿潤ベタツキ性に優れ、バッキングロール汚れの抑制効果も有する、ラテックスを提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a latex that has excellent pick strength when used as coated paper, has excellent wet stickiness resistance, and also has an effect of suppressing backing roll dirt. And
本発明者らは、鋭意研究した結果、（ａ）共役ジエン系単量体と（ｂ）その他共重合可能な単量体を特定の割合で乳化重合して得られる共重合体を含むラテックスであり、乳化重合が第一重合工程と第二重合工程とを含み、第一重合工程において添加される単量体総量に対する、第一重合工程において添加される（ａ）成分の割合が、第二重合工程において添加される単量体総量に対する、第二重合工程において添加される（ａ）成分の割合よりも小さく、第一重合工程で添加される単量体混合物（Ａ）から得られる共重合体（Ａ）の溶解性パラメータと、第二重合工程で添加される単量体混合物から得られる共重合体（Ｂ）の溶解性パラメータが特定の関係を満たし、かつ、乳化重合の間に重合温度を降温させることを行うことで、上記課題を解決できることを見出し、本発明を完成させるに至った。 As a result of diligent research, the present inventors have found that a latex containing a copolymer obtained by emulsion polymerization of (a) a conjugated diene monomer and (b) other copolymerizable monomer at a specific ratio. Yes, the emulsion polymerization includes a first polymerization step and a second polymerization step, and the ratio of the component (a) added in the first polymerization step to the total amount of monomers added in the first polymerization step is Copolymer obtained from the monomer mixture (A) added in the first polymerization step, which is smaller than the ratio of the component (a) added in the second polymerization step to the total amount of monomers added in the polymerization step. The solubility parameter of the coalescence (A) and the solubility parameter of the copolymer (B) obtained from the monomer mixture added in the second polymerization step satisfy a specific relationship, and polymerization is performed during emulsion polymerization. By lowering the temperature, the above section It can be solved and have completed the present invention.
すなわち、本発明は、以下のとおりである。
〔１〕
（ａ）共役ジエン系単量体２５〜６５質量％、及び（ｂ）その他共重合可能な単量体３５〜７５質量％（但し、（ａ）＋（ｂ）＝１００質量％）を含む混合物を乳化重合して得られる共重合体を含むラテックスであり、
前記乳化重合が、第一重合工程と第二重合工程とを含み、
前記第一重合工程において添加される単量体総量に対する、前記第一重合工程において添加される前記（ａ）成分の割合が、前記第二重合工程において添加される単量体総量に対する、前記第二重合工程において添加される前記（ａ）成分の割合よりも小さく、
前記第一重合工程で添加される単量体混合物（Ａ）から得られる共重合体（Ａ）の溶解性パラメータ（ＳＰＡ）と、前記第二重合工程で添加される単量体混合物（Ｂ）から得られる共重合体（Ｂ）の溶解性パラメータ（ＳＰＢ）とが、下記式（１）で表される関係を満たし、
前記乳化重合の間に、重合温度を降温させる、
共重合体を含むラテックス。
０．１＜（ＳＰＡ）−（ＳＰＢ）＜１．５ （１）
（溶解性パラメータ（ＳＰＡ）及び（ＳＰＢ）は、Ｒｏｂｅｒｔ Ｆ．Ｆｅｄｏｒｓが規定する方法に基づく値である。）
〔２〕
前記乳化重合は、前記第一重合工程の前に、単量体として前記（ｂ）成分のみを単独重合させる初期工程を、更に含み、
前記初期工程で添加される前記（ｂ）成分の添加量は、前記乳化重合において添加される単量体の総量１００質量％に対して５〜５０質量％であり、
前記初期工程は、重合転化率が２０〜６５質量％に達するまで重合させる、
〔１〕に記載のラテックス。
〔３〕
前記乳化重合の各重合工程は、α−メチルスチレンダイマーを少なくとも用いて行われ、
前記第一重合工程において添加される前記単量体総量に対する、前記第一重合工程において添加されるα−メチルスチレンダイマーの割合が、前記第二重合工程以降の各重合工程で添加される単量体の総量に対する、前記第二重合工程以降の各工程で添加されるα−メチルスチレンダイマーの総量の割合よりも大きい、
〔１〕又は〔２〕記載のラテックス。
〔４〕
〔１〕〜〔３〕のいずれか一項に記載のラテックスを含む紙塗工用組成物。
〔５〕
〔４〕に記載の紙塗工用組成物を用いて塗工した塗工紙。
〔６〕
（ａ）共役ジエン系単量体２５〜６５質量％、及び（ｂ）その他共重合可能な単量体３５〜７５質量％（但し、（ａ）＋（ｂ）＝１００質量％）を含む混合物を乳化重合する共重合体を含むラテックスの製造方法であって、
前記乳化重合が、第一重合工程と第二重合工程とを含み、
前記第一重合工程において添加される単量体総量に対する、前記第一重合工程において添加される前記（ａ）成分の割合が、前記第二重合工程において添加される単量体総量に対する、前記第二重合工程において添加される前記（ａ）成分の割合よりも小さく、
前記第一重合工程で添加される単量体混合物（Ａ）から得られる共重合体（Ａ）の溶解性パラメータ（ＳＰＡ）と、前記第二重合工程で添加される単量体混合物（Ｂ）から得られる共重合体（Ｂ）の溶解性パラメータ（ＳＰＢ）とが、下記式（１）で表される関係を満たし、
前記乳化重合の間に、重合温度を降温させる、
共重合体を含むラテックスの製造方法。
０．１＜（ＳＰＡ）−（ＳＰＢ）＜１．５ （１）
（溶解性パラメータ（ＳＰＡ）及び（ＳＰＢ）は、Ｒｏｂｅｒｔ Ｆ．Ｆｅｄｏｒｓが規定する方法に基づく値である。）
〔７〕
前記乳化重合は、前記第一重合工程の前に、単量体として前記（ｂ）成分のみを単独重合させる初期工程を、更に含み、
前記初期工程で添加される前記（ｂ）成分の添加量は、前記乳化重合において添加される単量体の総量１００質量％に対して５〜５０質量％であり、
前記初期工程は、重合転化率が２０〜６５質量％に達するまで重合させる、〔６〕に記載のラテックスの製造方法。
〔８〕
前記乳化重合の各重合工程は、α−メチルスチレンダイマーを少なくとも用いて行われ、
前記第一重合工程において添加される前記単量体総量に対する、前記第一重合工程において添加されるα−メチルスチレンダイマーの割合が、前記第二重合工程以降の各重合工程で添加される単量体の総量に対する、前記第二重合工程以降の各工程で添加されるα−メチルスチレンダイマーの総量の割合よりも大きい、
〔６〕又は〔７〕記載のラテックスの製造方法。
That is, the present invention is as follows.
[1]
A mixture containing (a) 25 to 65% by mass of a conjugated diene monomer and (b) 35 to 75% by mass of another copolymerizable monomer (provided that (a) + (b) = 100% by mass). Is a latex containing a copolymer obtained by emulsion polymerization,
The emulsion polymerization includes a first polymerization step and a second polymerization step,
The ratio of the component (a) added in the first polymerization step with respect to the total amount of monomers added in the first polymerization step is based on the total amount of monomers added in the second polymerization step. Smaller than the proportion of the component (a) added in the bipolymerization step,
The solubility parameter (SPA) of the copolymer (A) obtained from the monomer mixture (A) added in the first polymerization step, and the monomer mixture (B) added in the second polymerization step The solubility parameter (SPB) of the copolymer (B) obtained from the above satisfies the relationship represented by the following formula (1),
During the emulsion polymerization, the polymerization temperature is lowered.
Latex containing a copolymer.
0.1 <(SPA)-(SPB) <1.5 (1)
(The solubility parameters (SPA) and (SPB) are values based on the method prescribed by Robert F. Fedors).
[2]
The emulsion polymerization further includes an initial step of homopolymerizing only the component (b) as a monomer before the first polymerization step,
The addition amount of the component (b) added in the initial step is 5 to 50% by mass with respect to 100% by mass of the total amount of monomers added in the emulsion polymerization,
In the initial step, the polymerization is performed until the polymerization conversion rate reaches 20 to 65% by mass.
The latex according to [1].
[3]
Each polymerization step of the emulsion polymerization is performed using at least α-methylstyrene dimer,
The ratio of α-methylstyrene dimer added in the first polymerization step to the total amount of the monomer added in the first polymerization step is a single amount added in each polymerization step after the second polymerization step. Greater than the ratio of the total amount of α-methylstyrene dimer added in each step after the second polymerization step to the total amount of the body,
The latex according to [1] or [2].
[4]
The composition for paper coating containing the latex as described in any one of [1]-[3].
[5]
Coated paper coated using the paper coating composition described in [4].
[6]
A mixture containing (a) 25 to 65% by mass of a conjugated diene monomer and (b) 35 to 75% by mass of another copolymerizable monomer (provided that (a) + (b) = 100% by mass). A process for producing a latex comprising a copolymer for emulsion polymerization of
The emulsion polymerization includes a first polymerization step and a second polymerization step,
The ratio of the component (a) added in the first polymerization step with respect to the total amount of monomers added in the first polymerization step is based on the total amount of monomers added in the second polymerization step. Smaller than the proportion of the component (a) added in the bipolymerization step,
The solubility parameter (SPA) of the copolymer (A) obtained from the monomer mixture (A) added in the first polymerization step, and the monomer mixture (B) added in the second polymerization step The solubility parameter (SPB) of the copolymer (B) obtained from the above satisfies the relationship represented by the following formula (1),
During the emulsion polymerization, the polymerization temperature is lowered.
A method for producing a latex containing a copolymer.
0.1 <(SPA)-(SPB) <1.5 (1)
(The solubility parameters (SPA) and (SPB) are values based on the method prescribed by Robert F. Fedors).
[7]
The emulsion polymerization further includes an initial step of homopolymerizing only the component (b) as a monomer before the first polymerization step,
The addition amount of the component (b) added in the initial step is 5 to 50% by mass with respect to 100% by mass of the total amount of monomers added in the emulsion polymerization,
The said initial process is a manufacturing method of the latex as described in [6] superposed | polymerized until a polymerization conversion rate reaches 20-65 mass%.
[8]
Each polymerization step of the emulsion polymerization is performed using at least α-methylstyrene dimer,
The ratio of α-methylstyrene dimer added in the first polymerization step to the total amount of the monomer added in the first polymerization step is a single amount added in each polymerization step after the second polymerization step. Greater than the ratio of the total amount of α-methylstyrene dimer added in each step after the second polymerization step to the total amount of the body,
[6] or the method for producing a latex according to [7].
本発明によれば、塗工紙とした際のピック強度に優れ、かつ耐湿潤ベタツキ性に優れ、バッキングロールの汚れの抑制効果も有する、ラテックスを提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the latex which is excellent in the pick strength at the time of using coated paper, is excellent in wet-sticking resistance, and has the inhibitory effect of the stain | pollution | contamination of a backing roll can be provided.
以下、本発明を実施するための形態（以下、単に「本実施形態」という。）について詳細に説明する。以下の本実施形態は、本発明を説明するための例示であり、本発明を以下の内容に限定する趣旨ではない。本発明は、その要旨の範囲内で適宜に変形して実施できる。 Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist.
本実施形態に係る共重合体を含むラテックスは、
（ａ）共役ジエン系単量体２５〜６５質量％、及び（ｂ）その他共重合可能な単量体３５〜７５質量％（但し、（ａ）＋（ｂ）＝１００質量％）を含む混合物を乳化重合して得られる共重合体を含むラテックスであり、
乳化重合が、第一重合工程と第二重合工程とを含み、
第一重合工程において添加される単量体総量に対する、第一重合工程において添加される（ａ）成分の割合が、第二重合工程において添加される単量体総量に対する、第二重合工程において添加される（ａ）成分の割合よりも小さく、
第一重合工程で添加される単量体混合物（Ａ）から得られる共重合体（Ａ）の溶解性パラメータ（ＳＰＡ）と、第二重合工程で添加される単量体混合物（Ｂ）から得られる共重合体（Ｂ）の溶解性パラメータ（ＳＰＢ）とが、下記式（１）で表される関係を満たし、
乳化重合の間に、重合温度を降温させる、
共重合体を含むラテックスである、
０．１＜（ＳＰＡ）−（ＳＰＢ）＜１．５ （１）
（溶解性パラメータ（ＳＰＡ）及び（ＳＰＢ）は、Ｒｏｂｅｒｔ Ｆ．Ｆｅｄｏｒｓが規定する方法に基づく値である。）
Latex containing the copolymer according to this embodiment,
A mixture containing (a) 25 to 65% by mass of a conjugated diene monomer and (b) 35 to 75% by mass of another copolymerizable monomer (provided that (a) + (b) = 100% by mass). Is a latex containing a copolymer obtained by emulsion polymerization,
The emulsion polymerization includes a first polymerization step and a second polymerization step,
The ratio of the component (a) added in the first polymerization step to the total monomer amount added in the first polymerization step is added in the second polymerization step with respect to the total monomer amount added in the second polymerization step. Smaller than the proportion of component (a)
Obtained from the solubility parameter (SPA) of the copolymer (A) obtained from the monomer mixture (A) added in the first polymerization step and the monomer mixture (B) added in the second polymerization step. The solubility parameter (SPB) of the copolymer (B) to be satisfied the relationship represented by the following formula (1),
During the emulsion polymerization, the polymerization temperature is lowered.
A latex containing a copolymer,
0.1 <(SPA)-(SPB) <1.5 (1)
(The solubility parameters (SPA) and (SPB) are values based on the method prescribed by Robert F. Fedors).
また、上記したラテックスの製造方法の好適例としては、例えば、以下の方法が挙げられる。
（ａ）共役ジエン系単量体２５〜６５質量％、及び（ｂ）その他共重合可能な単量体３５〜７５質量％（但し、（ａ）＋（ｂ）＝１００質量％）を含む混合物を乳化重合する共重合体を含むラテックスの製造方法であって、
乳化重合が、第一重合工程と第二重合工程とを含み、
第一重合工程において添加される単量体総量に対する、第一重合工程において添加される（ａ）成分の割合が、第二重合工程において添加される単量体総量に対する、第二重合工程において添加される（ａ）成分の割合よりも小さく、
第一重合工程で添加される単量体混合物（Ａ）から得られる共重合体（Ａ）の溶解性パラメータ（ＳＰＡ）と、第二重合工程で添加される単量体混合物（Ｂ）から得られる共重合体（Ｂ）の溶解性パラメータ（ＳＰＢ）とが、下記式（１）で表される関係を満たし、
乳化重合の間に、重合温度を降温させる、
共重合体を含むラテックスの製造方法。
０．１＜（ＳＰＡ）−（ＳＰＢ）＜１．５ （１）
（溶解性パラメータ（ＳＰＡ）及び（ＳＰＢ）は、Ｒｏｂｅｒｔ Ｆ．Ｆｅｄｏｒｓが規定する方法に基づく値である。）
Moreover, as a suitable example of the manufacturing method of an above-described latex, the following method is mentioned, for example.
A mixture containing (a) 25 to 65% by mass of a conjugated diene monomer and (b) 35 to 75% by mass of another copolymerizable monomer (provided that (a) + (b) = 100% by mass). A process for producing a latex comprising a copolymer for emulsion polymerization of
The emulsion polymerization includes a first polymerization step and a second polymerization step,
The ratio of the component (a) added in the first polymerization step to the total monomer amount added in the first polymerization step is added in the second polymerization step with respect to the total monomer amount added in the second polymerization step. Smaller than the proportion of component (a)
Obtained from the solubility parameter (SPA) of the copolymer (A) obtained from the monomer mixture (A) added in the first polymerization step and the monomer mixture (B) added in the second polymerization step. The solubility parameter (SPB) of the copolymer (B) to be satisfied the relationship represented by the following formula (1),
During the emulsion polymerization, the polymerization temperature is lowered.
A method for producing a latex containing a copolymer.
0.1 <(SPA)-(SPB) <1.5 (1)
(The solubility parameters (SPA) and (SPB) are values based on the method prescribed by Robert F. Fedors).
以下、これらについて順次説明する。 Hereinafter, these will be sequentially described.
（ａ）共役ジエン系単量体を含むことにより、共重合体に柔軟性を与えるとともに、ピック強度、衝撃吸収性を与えることができる。（ａ）成分の好ましい具体例としては、例えば、１，３−ブタジエン、イソプレン、２−クロロ−１，３−ブタジエン等が挙げられる。これらを用いることで、ピック強度を一層向上させることができる。これらは１種単独で用いてもよいし、２種以上を併用してもよい。 (A) By including a conjugated diene monomer, the copolymer can be given flexibility, and pick strength and impact absorption can be given. Preferable specific examples of the component (a) include 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene and the like. By using these, the pick strength can be further improved. These may be used alone or in combination of two or more.
共重合体を構成する単量体の総量を１００質量％とした場合、（ａ）成分の割合は２５〜６５質量％であり、好ましくは２７〜６３質量％であり、より好ましくは３０〜６０質量％である。（ａ）成分の割合を上記範囲とすることで、共重合体に適度の柔軟性と弾性を付与し、ピック強度を向上させることができる。さらには、耐湿潤ベタツキ性を向上させることができる。 When the total amount of monomers constituting the copolymer is 100% by mass, the proportion of component (a) is 25 to 65% by mass, preferably 27 to 63% by mass, more preferably 30 to 60%. % By mass. (A) By making the ratio of a component into the said range, moderate softness | flexibility and elasticity can be provided to a copolymer, and pick strength can be improved. Furthermore, the wet stickiness resistance can be improved.
（ａ）単量体と共重合可能な他の単量体（ｂ）を用いることで、ラテックスにさまざまな特性を付与できる。（ｂ）成分としては、例えば、スチレン、α−メチルスチレン、ビニルトルエン、ｐ−メチルスチレン等の芳香族ビニル単量体、アクリル酸、メタクリル酸、イタコン酸、マレイン酸、フマール酸等のエチレン系不飽和カルボン酸単量体；アクリロニトリル、メタクリロニトリル、α−クロルアクリロニトリル等のシアン化ビニル系単量体；アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸２−エチルヘキシル等のアクリル酸アルキルエステル類；メタクリル酸メチル、メタクリル酸ブチル等のメタクリル酸アルキルエステル類；アクリル酸２−ヒドロキシエチル、メタクリル酸２−ヒドロキシエチル等のヒドロキシアルキルエステル類；アクリル酸アミノエチル、アクリル酸ジメチルアミノエチル、アクリル酸ジエチルアミノエチル等のアミノアルキルエステル類；２−ビニルピリジン、４−ビニルピリジン等のピリジン類；アクリル酸グリシジル、メタクリル酸グリシジル等のグリシジルエステル類；アクリルアミド、メタクリルアミド、Ｎ−メチロールアクリルアミド、Ｎ−メチルアクリルアミド、Ｎ−メチルメタクリルアミド、グリシジルメタクリルアミド、Ｎ，Ｎ−ブトキシメチルアクリルアミド等のアミド類；酢酸ビニル等のカルボン酸ビニルエステル類；塩化ビニル等のハロゲン化ビニル類；ｐ−スチレンスルホン酸及びそのナトリウム塩等が挙げられる。これを用いることで、ピック強度を一層向上させることができる。これらは１種単独で用いてもよいし、２種以上を併用してもよい。 (A) By using the other monomer (b) copolymerizable with the monomer, various properties can be imparted to the latex. Examples of the component (b) include aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, and p-methylstyrene, and ethylene-based materials such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid. Unsaturated carboxylic acid monomers; vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile; alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate Esters; alkyl methacrylates such as methyl methacrylate and butyl methacrylate; hydroxyalkyl esters such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate; aminoethyl acrylate, dimethylaminoethyl acrylate, acrylic Diethyl acid Aminoalkyl esters such as aminoethyl; pyridines such as 2-vinylpyridine and 4-vinylpyridine; glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; acrylamide, methacrylamide, N-methylolacrylamide, N-methylacrylamide Amides such as N-methylmethacrylamide, glycidylmethacrylamide, N, N-butoxymethylacrylamide; vinyl carboxylic acid esters such as vinyl acetate; vinyl halides such as vinyl chloride; p-styrene sulfonic acid and its sodium Examples include salts. By using this, the pick strength can be further improved. These may be used alone or in combination of two or more.
共重合体を構成する単量体の総量を１００質量％とした場合、（ｂ）成分の総量は３５〜７５質量％であり、好ましくは３７〜７３質量％であり、より好ましくは４０〜７０質量％である。（ｂ）成分の割合を上記範囲とすることで、ピック強度を向上させることができる。 When the total amount of monomers constituting the copolymer is 100% by mass, the total amount of component (b) is 35 to 75% by mass, preferably 37 to 73% by mass, and more preferably 40 to 70%. % By mass. (B) Pick strength can be improved by making the ratio of a component into the said range.
ラテックスの製造法は、従来用いられている乳化重合法の装置を使用して行うことができるが、第一重合工程と第二重合工程を少なくとも行う多段重合法を採用する。第一重合工程と第二重合工程は、少なくとも（ａ）成分を含む単量体を乳化重合させるものである。多段重合法とは、例えば、特開２００２−２２６５２４号公報等に開示されている如く、組成の異なる複数の単量体混合物を準備し、重合反応の進行に伴って系内に添加する単量体混合物の組成を、重合反応の途中で変化させる重合法である。 The method for producing the latex can be performed using a conventionally used emulsion polymerization apparatus, but a multistage polymerization method in which at least the first polymerization step and the second polymerization step are performed is employed. In the first polymerization step and the second polymerization step, a monomer containing at least the component (a) is emulsion-polymerized. The multistage polymerization method is, for example, as disclosed in JP-A No. 2002-226524 and the like, and a plurality of monomer mixtures having different compositions are prepared and added to the system as the polymerization reaction proceeds This is a polymerization method in which the composition of the body mixture is changed during the polymerization reaction.
少なくとも（ａ）成分を含む単量体を、少なくとも二段の多段重合法を用いて乳化重合するにあたり、最初の重合工程を第一重合工程、次の重合工程を第二重合工程、更にこれに続く重合工程を第三重合工程、第四重合工程等という。 In emulsion polymerization of a monomer containing at least component (a) using at least a two-stage multi-stage polymerization method, the first polymerization process is the first polymerization process, the next polymerization process is the second polymerization process, and The subsequent polymerization process is referred to as a third polymerization process, a fourth polymerization process, or the like.
乳化重合において、第一重合工程において添加される単量体総量に対する、第一重合工程において添加される（ａ）成分の割合が、第二重合工程において添加される単量体総量に対する、第二重合工程において添加される（ａ）成分の割合よりも小さい。このような割合とすることで、良好な耐湿潤ベタツキ性とピック強度が発現する。 In the emulsion polymerization, the ratio of the component (a) added in the first polymerization step to the total amount of monomer added in the first polymerization step is the second to the total amount of monomer added in the second polymerization step. It is smaller than the proportion of the component (a) added in the polymerization step. By setting such a ratio, good wet-sticking resistance and pick strength are developed.
また、第一重合工程と第二重合工程に限らず、先の重合工程において添加される単量体に占める（ａ）成分の割合が、直後の重合工程において添加される単量体中に占める（ａ）成分の割合よりも小さいことがより好ましい。例えば、第一〜第三重合工程を行う場合、第一重合工程の（ａ）成分の割合と第二重合工程の（ａ）成分の割合が上記した関係を満たすとともに、第二重合工程において添加される単量体総量に占める（ａ）成分の割合が、第三重合工程において添加される単量体総量に占める（ａ）成分の割合よりも小さい関係にあることが、より好ましい。 Further, not only in the first polymerization step and the second polymerization step, the proportion of the component (a) in the monomer added in the previous polymerization step accounts for in the monomer added in the immediately subsequent polymerization step. (A) It is more preferable that it is smaller than the ratio of a component. For example, when the first to third polymerization steps are performed, the proportion of the component (a) in the first polymerization step and the proportion of the component (a) in the second polymerization step satisfy the relationship described above, and in the second polymerization step, More preferably, the proportion of the component (a) in the total amount of added monomers is smaller than the proportion of the component (a) in the total amount of monomers added in the third polymerization step.
さらに、先の重合工程において添加される原料単量体の総量に対する当該重合工程において添加される（ａ）成分の割合（ａ−１）と、当該重合工程の直後の重合工程において添加される原料単量体の総量に対する直後の重合工程において添加される（ａ）成分の割合（ａ−２）の関係が、（ａ−１）／（ａ−２）＜１．０となることが好ましい。（ａ）成分を上記割合で添加することによって、耐湿潤ベタツキ性及びピック強度が一層向上する。 Furthermore, the ratio (a-1) of the component (a) added in the polymerization step to the total amount of raw material monomers added in the previous polymerization step, and the raw material added in the polymerization step immediately after the polymerization step It is preferable that the relationship of the ratio (a-2) of the component (a) added in the polymerization step immediately after the total amount of monomers is (a-1) / (a-2) <1.0. By adding the component (a) in the above ratio, the wet stickiness resistance and pick strength are further improved.
本実施形態では、第一重合工程で添加される単量体混合物（Ａ）から得られる共重合体（Ａ）の溶解性パラメータ（ＳＰＡ）と、第二重合工程で添加される単量体混合物（Ｂ）から得られる共重合体（Ｂ）の溶解性パラメータ（ＳＰＢ）とが、下記式（１）で表される関係を満たす。
０．１＜（ＳＰＡ）−（ＳＰＢ）＜１．５ （１）
（溶解性パラメータ（ＳＰＡ）及び（ＳＰＢ）は、Ｒｏｂｅｒｔ Ｆ．Ｆｅｄｏｒｓが規定する方法に基づく値である。）
In this embodiment, the solubility parameter (SPA) of the copolymer (A) obtained from the monomer mixture (A) added in the first polymerization step and the monomer mixture added in the second polymerization step The solubility parameter (SPB) of the copolymer (B) obtained from (B) satisfies the relationship represented by the following formula (1).
0.1 <(SPA)-(SPB) <1.5 (1)
(The solubility parameters (SPA) and (SPB) are values based on the method prescribed by Robert F. Fedors).
溶解性パラメータ（ＳＰＡ）と（ＳＰＢ）は、０．３＜（ＳＰＡ）−（ＳＰＢ）＜１．４の関係を満たすことが好ましく、０．５＜（ＳＰＡ）−（ＳＰＢ）＜１．３の関係を満たすことがより好ましい。 It is preferable that the solubility parameters (SPA) and (SPB) satisfy the relationship of 0.3 <(SPA) − (SPB) <1.4, and 0.5 <(SPA) − (SPB) <1.3. It is more preferable to satisfy the relationship.
溶解性パラメータ（ＳＰ値；Ｓｏｌｕｂｉｌｉｔｙ Ｐａｒａｍｅｔｅｒ）は、Ｒｏｂｅｒｔ Ｆ．Ｆｅｄｏｒｓが規定する方法に基づく値である。例えば、ポリマーのＳＰ値（σｐ）は、そのポリマーを構成するモノマーの蒸発エネルギー（Δｅｉ）及びモル体積（Δｖｉ）をモノマー毎に求め、モノマーのポリマーにおけるモル比（ｊ）との積をそれぞれ算出し、モノマーの蒸発エネルギーの総和をモル体積の総和で割ることによって求め、下記式から算出する。蒸発エネルギー（Δｅｉ（ｃａｌ／ｍｏｌ））及びモル体積（Δｖｉ（ｃｍ3／ｍｏｌ））は、ＰＯＬＹＭＥＲ ＥＮＧＩＮＮＥＥＲＩＮＧ ＡＮＤ ＳＣＩＥＮＣＥ，１９７４，Ｖｏｌ．１４，Ｎｏ．２，１４７−１５４に記載されている値を用いることができる。
σｐ＝｛（Σｊ×ΣΔｅｉ）／（Σｊ×ΣΔｖｉ）｝1/2
Solubility parameter (SP value; Solubility Parameter) was measured by Robert F. It is a value based on the method prescribed by Fedors. For example, for the SP value (σp) of a polymer, the evaporation energy (Δei) and molar volume (Δvi) of the monomer constituting the polymer are obtained for each monomer, and the product of the monomer-molar ratio (j) in the polymer is calculated. Then, the sum of the evaporation energies of the monomers is divided by the sum of the molar volumes, and is calculated from the following formula. Evaporation energy (Δei (cal / mol)) and molar volume (Δvi (cm 3 / mol)) were measured in POLYMER ENGINNEERING AND SCIENCE, 1974, Vol. 14, no. 2, 147-154 can be used.
σp = {(Σj × ΣΔei) / (Σj × ΣΔvi)} 1/2
また、各重合工程において用いられる単量体混合物から得られる共重合体の溶解性パラメータ（ＳＰ値）に関して、ある重合工程（但し、初期工程を除く）で用いられる単量体混合物から得られる共重合体のＳＰ値と、その重合工程の直後の重合工程で用いられる単量体混合物から得られる共重合体のＳＰ値との差分（以下、ΔＳＰ値という。）が０．１を超えて１．５未満の範囲に入るように、各重合工程の単量体混合物が調整されることが好ましい。つまり、隣接する重合工程の各ＳＰ値がこの差を有していることが好ましい。このΔＳＰ値が０．１を超えて１．５未満の範囲に入ることによって、耐湿潤ベタツキ性とピック強度の双方が一層優れるラテックスが得られる。ΔＳＰ値のより好ましい範囲は、０．１を超えて１．２未満である。各重合工程のＳＰ値は、単量体の種類や含有量を適宜調節することで制御できる。 Further, regarding the solubility parameter (SP value) of the copolymer obtained from the monomer mixture used in each polymerization step, the copolymer obtained from the monomer mixture used in a certain polymerization step (excluding the initial step). The difference between the SP value of the polymer and the SP value of the copolymer obtained from the monomer mixture used in the polymerization step immediately after the polymerization step (hereinafter referred to as ΔSP value) exceeds 0.1 and is 1 It is preferable that the monomer mixture of each polymerization step is adjusted so as to fall within the range of less than .5. That is, it is preferable that each SP value of an adjacent polymerization process has this difference. When this ΔSP value is in the range of more than 0.1 and less than 1.5, a latex having both excellent wet stickiness resistance and pick strength can be obtained. A more preferable range of ΔSP value is more than 0.1 and less than 1.2. The SP value of each polymerization step can be controlled by appropriately adjusting the type and content of the monomer.
本実施形態では、乳化重合の間に重合温度を降温させる。降温は、必ずしも乳化重合を行っている全期間にわたって行われる必要はなく、乳化重合を行っている一部期間において行われていればよい。降温は、降温開始時の重合温度と降温終了時の重合温度の差が４℃以上となるよう降温することが好ましい。また、乳化重合が行われる間の任意の２０分間において重合温度が０．１℃以上降下することが好ましい。降温速度は、１〜１０℃／ｈｒであることが好ましく、２〜５℃／ｈｒであることがより好ましく、２．５〜４℃／ｈｒであることが更に好ましい。重合温度の降下速度を上記範囲とすることにより、ピック強度、耐湿潤ベタツキ性が一層向上するとともに、量産を考慮した大型実機設備等においても温度制御が容易にできる。 In this embodiment, the polymerization temperature is lowered during emulsion polymerization. The temperature lowering is not necessarily performed over the entire period during which the emulsion polymerization is performed, but may be performed during a part of the period during which the emulsion polymerization is performed. It is preferable to lower the temperature so that the difference between the polymerization temperature at the start of temperature decrease and the polymerization temperature at the end of temperature decrease is 4 ° C. or more. Further, it is preferable that the polymerization temperature falls by 0.1 ° C. or more in any 20 minutes during the emulsion polymerization. The temperature lowering rate is preferably 1 to 10 ° C./hr, more preferably 2 to 5 ° C./hr, and further preferably 2.5 to 4 ° C./hr. By setting the rate of decrease in the polymerization temperature within the above range, pick strength and wet stickiness resistance are further improved, and temperature control can be easily performed even in large-scale actual equipment that takes mass production into consideration.
重合温度の降温は、間欠的、段階的、又は連続的に重合温度を降温させることができるが、得られるラテックスのピック強度と耐湿潤ベタツキ性、及び量産大型設備での温度コントロールのし易さ等の観点から、連続的に降温させることが好ましく、一定の降温速度で降温させることがより好ましい。 The polymerization temperature can be lowered intermittently, stepwise, or continuously, but the latex pick strength and wet stickiness resistance of the resulting latex, and the ease of temperature control in mass production facilities From such a viewpoint, it is preferable to continuously lower the temperature, and it is more preferable to lower the temperature at a constant rate.
また、本実施形態のラテックスは、降温終了時の重合温度で重合反応を継続した後は、重合温度を上昇させて最終の重合転化率を引き上げる工程（いわゆるクッキング工程）を更に含むことが好ましい。このクッキング工程の重合温度は、８０〜１００℃であることが好ましい。クッキング工程の重合温度を上記範囲とすることでが、ピック強度及びラテックスの生産性の観点から好ましい。 Moreover, it is preferable that the latex of this embodiment further includes a step of raising the final polymerization conversion rate (so-called cooking step) by raising the polymerization temperature after continuing the polymerization reaction at the polymerization temperature at the end of the temperature drop. The polymerization temperature in this cooking step is preferably 80 to 100 ° C. It is preferable from the viewpoint of pick strength and latex productivity that the polymerization temperature in the cooking step be in the above range.
本実施形態のラテックスは、前述の単量体混合物を乳化重合法により重合することで得られる。乳化重合を行うに当たり、単量体の添加方法は特に限定されない。すなわち、重合の開始時から終了時にかけて単量体を連続的に重合系内に添加する方法、重合開始前に単量体混合物の全量を重合系内に添加しておき、その後反応を開始する方法、重合開始前に単量体混合物の一部を重合系内に添加した後に重合反応を開始し、その後残りの単量体を重合系内に連続又は間欠的に添加する方法等が挙げられる。 The latex of this embodiment can be obtained by polymerizing the above monomer mixture by an emulsion polymerization method. In carrying out the emulsion polymerization, the method for adding the monomer is not particularly limited. That is, a method of continuously adding monomers into the polymerization system from the start to the end of the polymerization, adding the entire amount of the monomer mixture into the polymerization system before starting the polymerization, and then starting the reaction Examples thereof include a method in which a part of the monomer mixture is added to the polymerization system before the polymerization is started and then the polymerization reaction is started, and then the remaining monomer is continuously or intermittently added to the polymerization system. .
単量体混合物の成分組成についても、重合を時系列的に複数の工程に分け、各工程での単量体組成を任意に変えることにより均一組成ではないラテックスとすることも可能である。しかしながら、得られるラテックスのピック強度を一層向上させる観点から、単量体混合物はその７０質量％以上は連続又は間欠的に重合の系内に添加されることが好ましい。 Regarding the component composition of the monomer mixture, it is also possible to divide the polymerization into a plurality of steps in a time series and arbitrarily change the monomer composition in each step to obtain a non-uniform latex. However, from the viewpoint of further improving the pick strength of the resulting latex, it is preferable that 70% by mass or more of the monomer mixture is continuously or intermittently added to the polymerization system.
乳化重合は、第一重合工程の前に、単量体として（ｂ）成分のみを単独重合させる初期工程を更に含むことが好ましい。初期工程を有することにより、ピック強度や耐湿潤ベタツキ性が一層優れるラテックスが得られる。 The emulsion polymerization preferably further includes an initial step of homopolymerizing only the component (b) as a monomer before the first polymerization step. By having an initial step, a latex with even better pick strength and wet stickiness resistance can be obtained.
初期工程で添加される（ｂ）成分の添加量は、乳化重合において添加される単量体の総量１００質量％に対して、５〜５０質量％であることが好ましく、５〜３０質量％であることがより好ましく、５〜１５質量％であることが更に好ましい。初期工程の（ｂ）成分の添加量を上記範囲とすることで、ピック強度や耐湿潤ベタツキ性が一層優れるラテックスが得られる。 The amount of the component (b) added in the initial step is preferably 5 to 50% by mass, and 5 to 30% by mass with respect to 100% by mass of the total amount of monomers added in the emulsion polymerization. More preferably, it is more preferably 5 to 15% by mass. By setting the addition amount of the component (b) in the initial step within the above range, a latex having further excellent pick strength and wet stickiness resistance can be obtained.
初期工程は、単量体の重合転化率が２０〜６５質量％に達するまで重合させることが好ましく、２５〜５５質量％であることがより好ましく、３０〜５０質量％であることが更に好ましい。重合転化率を上記下限値以上とすることで、紙塗工における耐バッキングロール汚れ特性が一層向上する。重合転化率を上記下限値以下とすることで、ピック強度の一層向上する。重合転化率は、後述する実施例に記載の方法に準じて測定することができる。 In the initial step, the polymerization is preferably performed until the polymerization conversion rate of the monomer reaches 20 to 65% by mass, more preferably 25 to 55% by mass, and further preferably 30 to 50% by mass. By setting the polymerization conversion rate to be equal to or more than the above lower limit value, the anti-backing roll stain property in paper coating is further improved. By setting the polymerization conversion rate to be equal to or lower than the above lower limit, the pick strength is further improved. The polymerization conversion rate can be measured according to the method described in Examples described later.
本実施形態のラテックスを製造するに当たっては、上述した特定の方法以外については特に限定されず、例えば、水性媒体中で界面活性剤の存在下、ラジカル開始剤により重合を行う等の方法を用いることができる。 In producing the latex of this embodiment, there is no particular limitation except for the specific method described above. For example, a method of performing polymerization with a radical initiator in the presence of a surfactant in an aqueous medium is used. Can do.
本実施形態において使用できる乳化剤は、特に限定されず、従来公知のアニオン性界面活性剤、カチオン性界面活性剤、両性界面活性剤、非イオン性界面活性剤等を用いることができる。好ましい界面活性剤の具体例としては、脂肪族セッケン、ロジン酸セッケン、アルキルスルホン酸塩、アルキルスルホコハク酸塩、ポリオキシエチレンアルキル硫酸塩等のアニオン性界面活性剤；ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルアリルエーテル、ポリオキシエチレンオキシプロピレンブロックコポリマー等のノニオン性界面活性剤等が挙げられる。これらは１種単独で用いてもよいし、２種以上を併用してもよい。 The emulsifier that can be used in the present embodiment is not particularly limited, and conventionally known anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, and the like can be used. Specific examples of preferable surfactants include anionic surfactants such as aliphatic soaps, rosin acid soaps, alkyl sulfonates, alkyl sulfosuccinates, polyoxyethylene alkyl sulfates; polyoxyethylene alkyl ethers, polyoxy Nonionic surfactants such as ethylene alkyl allyl ether and polyoxyethylene oxypropylene block copolymer are listed. These may be used alone or in combination of two or more.
乳化剤の使用量は、単量体１００質量部に対して、０．１〜２．０質量部であることが好ましく、０．２〜０．８質量部であることがより好ましく、０．２〜０．６質量部であることが更に好ましい。乳化剤の使用量を上記範囲とすることで、より優れたピック強度を達成するラテックスが得られる。 The amount of the emulsifier used is preferably 0.1 to 2.0 parts by mass, more preferably 0.2 to 0.8 parts by mass with respect to 100 parts by mass of the monomer, and 0.2 More preferably, it is -0.6 mass part. By setting the amount of the emulsifier to be in the above range, a latex that achieves better pick strength can be obtained.
ラジカル開始剤は、熱又は還元剤の存在下でラジカル分解して単量体の付加重合を開始させるものであればよく特に限定されない。ラジカル開始剤としては、無機系開始剤、有機系開始剤のいずれも使用することができる。ラジカル開始剤としては、ペルオキソ二硫酸塩、過酸化物、アゾビス化合物等が好ましく、具体的にはペルオキソ二硫酸カリウム、ペルオキソ二硫酸ナトリウム、ペルオキソ二硫酸アンモニウム、過酸化水素、ｔ−ブチルヒドロペルオキシド、過酸化ベンゾイル、２，２−アゾビスブチロニトリル及びクメンハイドロパーオキサイド等が挙げられる。これらは１種単独で用いてもよいし、２種以上を併用してもよい。また、酸性亜硫酸ナトリウム、アスコルビン酸やその塩、エリソルビン酸やその塩及びロンガリット等の還元剤を重合開始剤と組み合わせて用いる、いわゆるレドックス重合法を用いることもできる。 The radical initiator is not particularly limited as long as it is capable of radically decomposing in the presence of heat or a reducing agent to initiate monomer addition polymerization. As the radical initiator, either an inorganic initiator or an organic initiator can be used. As the radical initiator, peroxodisulfate, peroxide, azobis compound and the like are preferable. Specifically, potassium peroxodisulfate, sodium peroxodisulfate, ammonium peroxodisulfate, hydrogen peroxide, t-butyl hydroperoxide, peroxide Examples include benzoyl oxide, 2,2-azobisbutyronitrile, cumene hydroperoxide, and the like. These may be used alone or in combination of two or more. In addition, a so-called redox polymerization method in which a reducing agent such as acidic sodium sulfite, ascorbic acid or a salt thereof, erythorbic acid or a salt thereof, or Rongalite is used in combination with a polymerization initiator can also be used.
ラテックスを製造する際には、ラジカル重合で通常用いられる公知の連鎖移動剤を必要に応じて用いることができる。連鎖移動剤の好ましい具体例としては、核置換α−メチルスチレンの二量体であるα−メチルスチレンダイマー；ｎ−ブチルメルカプタン、ｔ−ブチルメルカプタン、ｎ−オクチルメルカプタン、ｎ−ラウリルメルカプタン、ｔ−ドデシルメルカプタン等のメルカプタン類；テトラメチルチウラジウムジスルフィド、テトラエチルチウラジウムジスルフィド等のジスルフィド類；四塩化炭素、四臭化炭素等のハロゲン化誘導体；２−エチルヘキシルチオグリコレート等が挙げられる。これらは１種単独で用いてもよいし、２種以上を併用してもよい。特に、α−メチルスチレンダイマーとｔ−ドデシルメルカプタンとを併用することが好ましい。 In producing the latex, a known chain transfer agent usually used in radical polymerization can be used as necessary. Preferred examples of the chain transfer agent include α-methylstyrene dimer which is a dimer of nucleus-substituted α-methylstyrene; n-butyl mercaptan, t-butyl mercaptan, n-octyl mercaptan, n-lauryl mercaptan, t- And mercaptans such as dodecyl mercaptan; disulfides such as tetramethylthiudium disulfide and tetraethylthuradium disulfide; halogenated derivatives such as carbon tetrachloride and carbon tetrabromide; and 2-ethylhexylthioglycolate. These may be used alone or in combination of two or more. In particular, α-methylstyrene dimer and t-dodecyl mercaptan are preferably used in combination.
乳化重合の各重合工程は、α−メチルスチレンダイマーを少なくとも用いて行われ、第一重合工程において添加される単量体総量に対する、第一重合工程において添加されるα−メチルスチレンダイマーの割合が、第二重合工程以降の各重合工程で添加される単量体の総量に対する、第二重合工程以降の各工程で添加されるα−メチルスチレンダイマーの総量の割合よりも大きいことが好ましい。単量体としてα−メチルスチレンダイマーを使用する場合、α−メチルスチレンダイマーを上記割合で使用することによって、ピック強度が一層向上する。 Each polymerization step of emulsion polymerization is performed using at least α-methylstyrene dimer, and the ratio of α-methylstyrene dimer added in the first polymerization step to the total amount of monomers added in the first polymerization step is The ratio of the total amount of α-methylstyrene dimer added in each step after the second polymerization step to the total amount of monomers added in each polymerization step after the second polymerization step is preferably larger. When α-methylstyrene dimer is used as a monomer, pick strength is further improved by using α-methylstyrene dimer in the above ratio.
ラテックスを製造する場合の重合温度は、前述の様に重合の途中で温度降下を行う点以外は特に限定されず、通常４０〜１００℃の範囲であるが、生産効率と、得られるラテックスを使用した塗工紙のピック強度等の品質の観点から、重合開始時の重合温度は、５０〜８５℃であることが好ましく、５５〜８０℃であることがより好ましく、６０〜８０℃であることが更に好ましい。 The polymerization temperature for producing the latex is not particularly limited except that the temperature is lowered during the polymerization as described above, and is usually in the range of 40 to 100 ° C., but the production efficiency and the obtained latex are used. The polymerization temperature at the start of polymerization is preferably 50 to 85 ° C, more preferably 55 to 80 ° C, and 60 to 80 ° C from the viewpoint of quality such as pick strength of the coated paper. Is more preferable.
ラテックスを製造する場合の重合固形分濃度は、生産効率と、乳化重合時の粒子径制御の観点から、好ましくは３０〜６０質量％であり、より好ましくは３５〜５０質量％である。ここでいう固形分濃度とは、乾燥前のラテックスの質量に対する、ラテックスを乾燥することにより得られる固形分の質量の割合をいう。 The polymerization solid content concentration in the case of producing latex is preferably 30 to 60% by mass, more preferably 35 to 50% by mass, from the viewpoint of production efficiency and particle size control during emulsion polymerization. The solid content concentration here refers to the ratio of the mass of the solid content obtained by drying the latex to the mass of the latex before drying.
ラテックスの製造に際しては、粒子径の調整のため公知のシード重合法を用いることもでき、シードを作製後同一反応系内で共重合体を含むラテックスの重合を行うインターナルシード法、別途作製したシードを用いるエクスターナルシード法等の方法を適宜選択することができる。 In the production of latex, a known seed polymerization method can be used to adjust the particle size. An internal seed method in which a latex containing a copolymer is polymerized in the same reaction system after the seed is prepared, and a separately prepared seed. A method such as an external seed method using can be selected as appropriate.
本実施形態のラテックスのトルエン不溶分の含有量は、８０〜９７質量％であることが好ましく、８５〜９６質量％であることがより好ましく、８９〜９５質量％であることが更に好ましい。トルエン不溶分の含有量を上記範囲とすることで、ラテックスの耐湿潤ベタツキ性が一層向上し、バッキングロール汚れ等のロール汚れトラブルを回避することや、優れたピック強度をより顕著に達成すること等が可能となる。ラテックスのトルエン不溶分の調整は、重合反応中に使用する連鎖移動剤の使用量を調整すること等により可能である。連鎖移動剤の重合系内への添加方法としては、一括添加、回分的添加、連続的添加のいずれでもよく、これらを組み合わせてもよい。なお、ここでいうトルエン不溶分の含有量は、後述する実施例に記載の方法に準じて測定することができる。 The content of the toluene insoluble matter in the latex of the present embodiment is preferably 80 to 97% by mass, more preferably 85 to 96% by mass, and still more preferably 89 to 95% by mass. By making the content of insoluble toluene in the above range, the wet stickiness resistance of the latex is further improved, and roll dirt troubles such as backing roll dirt are avoided, and excellent pick strength is achieved more remarkably. Etc. are possible. The toluene-insoluble matter in the latex can be adjusted by adjusting the amount of chain transfer agent used during the polymerization reaction. As a method for adding the chain transfer agent into the polymerization system, any of batch addition, batch addition and continuous addition may be used, or these may be combined. In addition, content of a toluene insoluble part here can be measured according to the method as described in the Example mentioned later.
本実施形態のラテックスの粒子径は、６０〜１３０ｎｍであることが好ましく、７０〜１２０ｎｍであることがより好ましく、８０〜１１０ｎｍであることが更に好ましい。ラテックスの粒子径を上記範囲とすることで、ラテックスの粘度を好適な範囲に調整することができ、作業性の低下を一層効率よく防ぐことができる。さらには、一層優れたピック強度、耐湿潤ベタツキ性を達成することができる。なお、ここでいう粒子径とは、平均粒子径であり、動的光散乱法により測定される体積平均粒径である。 The particle size of the latex of the present embodiment is preferably 60 to 130 nm, more preferably 70 to 120 nm, and still more preferably 80 to 110 nm. By setting the particle diameter of the latex within the above range, the viscosity of the latex can be adjusted to a suitable range, and deterioration of workability can be prevented more efficiently. Furthermore, it is possible to achieve further excellent pick strength and wet stickiness resistance. In addition, a particle diameter here is an average particle diameter, and is a volume average particle diameter measured by the dynamic light scattering method.
本実施形態のラテックスには、必要に応じて公知の各種重合調整剤を配合することができる。このような各種重合調整剤としては、例えば、ｐＨ調整剤、キレート剤等が挙げられる。ｐＨ調整剤の好ましい具体例としては、水酸化ナトリウム、水酸化カリウム、水酸化アンモニウム、炭酸水素ナトリウム、リン酸水素二ナトリウム等が挙げられる。キレート剤の好ましい具体例としては、エチレンジアミン四酢酸ナトリウム等が挙げられる。これらは１種単独で用いてもよいし、２種以上を併用してもよい。 Various known polymerization regulators can be blended in the latex of the present embodiment as necessary. Examples of such various polymerization regulators include pH regulators and chelating agents. Preferable specific examples of the pH adjuster include sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium hydrogen carbonate, disodium hydrogen phosphate and the like. Preferable specific examples of the chelating agent include sodium ethylenediaminetetraacetate. These may be used alone or in combination of two or more.
本実施形態のラテックスには、その効果を損ねない限り、必要に応じて各種添加剤を添加することができる。さらには、他のラテックスを混合して用いることもできる。各種添加剤としては、例えば、分散剤、消泡剤、老化防止剤、耐水化剤、殺菌剤、印刷適性向上剤、滑剤、アルカリ感応型ラテックス、有機顔料等が挙げられる。 Various additives can be added to the latex of the present embodiment as needed as long as the effect is not impaired. Furthermore, other latexes can be mixed and used. Examples of the various additives include dispersants, antifoaming agents, anti-aging agents, water resistance agents, bactericides, printability improvers, lubricants, alkali-sensitive latexes, and organic pigments.
次に、本実施形態のラテックスを用いる方法について説明する。
まず、本実施形態のラテックスを塗工紙用のバインダーとして使用する場合の一例を説明する。まず、紙塗工用組成物を調製する。該紙塗工用組成物は、通常行われている方法によって製造することができる。例えば、分散剤を溶解させた水中に、カオリンクレー、炭酸カルシウム、二酸化チタン、水酸化アルミニウム、サチンホワイト及びタルク等の無機顔料、プラスチックピグメントやバインダーピグメントとして知られる有機顔料、澱粉、カゼイン、ポリビニルアルコール、カルボキシメチルセルロース等の水溶性高分子、増粘剤、染料、消泡剤、防腐剤、耐水化剤、滑剤、印刷適性向上剤、ｐＨ調整剤、保水剤等の各種添加剤とともに、共重合体を含むラテックスを添加して混合し、均一な分散液（紙塗工用組成物）とする。
Next, a method using the latex of this embodiment will be described.
First, an example in the case of using the latex of this embodiment as a binder for coated paper is demonstrated. First, a composition for paper coating is prepared. The paper coating composition can be produced by a conventional method. For example, in water in which a dispersant is dissolved, inorganic pigments such as kaolin clay, calcium carbonate, titanium dioxide, aluminum hydroxide, satin white and talc, organic pigments known as plastic pigments and binder pigments, starch, casein, polyvinyl alcohol Copolymers with various additives such as water-soluble polymers such as carboxymethylcellulose, thickeners, dyes, antifoaming agents, preservatives, water-resistant agents, lubricants, printability improvers, pH adjusters, water retention agents, etc. Is added and mixed to obtain a uniform dispersion (composition for paper coating).
本実施形態のラテックスと顔料との使用割合は、紙塗工用組成物の使用目的によって適宜決定することができるが、顔料１００質量部に対する本実施形態のラテックスの含有量は、３〜３０質量部であることが好ましい。 The use ratio of the latex and the pigment of the present embodiment can be appropriately determined according to the purpose of use of the paper coating composition, but the content of the latex of the present embodiment with respect to 100 parts by mass of the pigment is 3 to 30 masses. Part.
そして、この紙塗工用組成物は、各種ブレードコーター、ロールコーター、エアーナイフコーター及びバーコーター等を用いる通常の方法によって原紙に塗工することができるところ、かかる塗工においてはブレードコーターを用いることが好ましい。塗工形態としては、原紙に対し片面に塗工してもよいし、原紙の両面に塗工してもよい。また、片面当たりの塗工回数についても、１回であるシングル塗工でもよいし、２回の塗工工程を行ういわゆるダブル塗工であってもよいし、２回以上塗工してもよい。この場合、本実施形態のラテックスは、その下塗り用紙塗工用組成物、及び上塗り用紙塗工用組成物のいずれにも用いることができる。 The paper coating composition can be applied to the base paper by a usual method using various blade coaters, roll coaters, air knife coaters, bar coaters, and the like. In such coating, a blade coater is used. It is preferable. As a coating form, you may apply to one side with respect to a base paper, and may apply to both surfaces of a base paper. Also, the number of coatings per side may be one single coating, or so-called double coating in which two coating processes are performed, or two or more coatings may be performed. . In this case, the latex of this embodiment can be used for both the undercoat paper coating composition and the overcoat paper coating composition.
前述の紙塗工用組成物を塗工原紙の少なくとも一方の表面に塗工処理して、印刷用塗工紙を得ることができる。この印刷用塗工紙は、オフセット枚葉式印刷用紙、オフセット輪転式印刷用紙、グラビア式印刷用紙、フレキソ印刷用紙及び凸版式印刷用紙等の各種印刷用紙に好適に用いられる。 A coating paper for printing can be obtained by coating the above-mentioned composition for paper coating on at least one surface of the base paper for coating. This printing coated paper is suitably used for various printing papers such as offset sheet-fed printing paper, offset rotary printing paper, gravure printing paper, flexographic printing paper, and relief printing paper.
また、本実施形態のラテックスは、紙のコーティング剤、カーペットバッキング剤の他、接着剤及び各種塗料にも用いることができる。 Moreover, the latex of this embodiment can be used for adhesives and various paints in addition to paper coating agents and carpet backing agents.
以下、本発明を実施例及び比較例を用いてより具体的に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated more concretely using an Example and a comparative example, this invention is not limited to a following example.
［各物性の評価方法］
（１）ピック強度：
ＲＩ印刷試験機（明製作所社製）を用いて、印刷インク（東洋インキ製造社製 ＰＲＩＮＴＩＮＧ ＩＮＫ；タック１５）（商品名）０．４ｃｃを１回刷りし、ゴムロールに現れたピッキング状態を別の台紙に裏取りし、その状態を目視で観察した。評価は相対的な１０点評価法とし、ピッキング現象の少ないもの（白化した領域の面積が小さいもの）ほど高得点とした。
[Evaluation method of each physical property]
(1) Pick strength:
Using an RI printing tester (manufactured by Meisei Seisakusho Co., Ltd.), printing ink (Printing Ink, manufactured by Toyo Ink Manufacturing Co., Ltd .; tack 15) (product name) 0.4 cc was printed once, and the picking state that appeared on the rubber roll was changed to another The backing was backed and the state was observed visually. Evaluation was based on a relative 10-point evaluation method, and the higher the score, the lower the picking phenomenon (the smaller the area of the whitened region).
（２）共重合体を含むラテックスの耐湿潤ベタツキ性：
共重合体を含むラテックスを、Ｎｏ．１０のワイヤーバーでＰＥＴフィルムに塗布して１３０℃で３０秒乾燥した。そして、フィルムを３０℃の水中に５秒間浸漬させた後、黒ラシャ紙と重ね合わせ、温度６０℃、線圧１９６００Ｎ／ｍのスーパーカレンダーを通過させた後、黒ラシャ紙を剥離した。黒ラシャ紙を剥離した後の、フィルム表目上への黒ラシャ紙の繊維の転移状態を目視観察することで、耐湿潤ベタツキ性を評価した。評価は１０点評価法で行ない、転移の少ないものほど高得点とした。
(2) Wet stickiness resistance of latex containing copolymer:
A latex containing a copolymer is designated No. The film was applied to a PET film with 10 wire bars and dried at 130 ° C. for 30 seconds. Then, the film was immersed in water at 30 ° C. for 5 seconds, overlapped with black lasha paper, passed through a super calendar having a temperature of 60 ° C. and a linear pressure of 19600 N / m, and then the black lasha paper was peeled off. The wet stickiness resistance was evaluated by visually observing the transition state of the fibers of the black lasha paper onto the film surface after the black lasha paper was peeled off. The evaluation was performed by a 10-point evaluation method, and the smaller the transition, the higher the score.
（３）共重合体を含むラテックスの粒子径：
共重合体を含むラテックスの粒子径については、マイクロトラック超微粒子粒度分析計（Ｗ）ＵＰＡ−１５０（日機装社製）を用いて、動的光散乱法によって体積平均粒径を測定することにより求めた。
(3) Particle size of latex containing copolymer:
The particle size of the latex containing the copolymer is determined by measuring the volume average particle size by a dynamic light scattering method using a Microtrac Ultrafine Particle Size Analyzer (W) UPA-150 (manufactured by Nikkiso Co., Ltd.). It was.
（４）共重合体を含むラテックスのトルエン不溶分の測定：
水酸ナトリウムと水酸化カリウムを添加することによって、共重合体を含むラテックスのｐＨを８に調整した後、１３０℃で３０分乾燥させて成膜させてフィルムとした。このフィルム０．５ｇをトルエン３０ｃｃに浸漬し、３時間振とう後、目開き４５μｍの金属網にてろ過して不溶分を採取した。採取した不溶分を１３０℃で１時間乾燥させて、質量を測定した。そして、次式に基づきトルエン不溶分（質量％）を求めた。
トルエン不溶分（質量％）＝（乾燥後のトルエン不溶分の質量／浸漬前に採取したフィルムの質量）×１００
(4) Measurement of toluene-insoluble content of latex containing copolymer:
The pH of the latex containing the copolymer was adjusted to 8 by adding sodium hydroxide and potassium hydroxide, and then dried at 130 ° C. for 30 minutes to form a film. 0.5 g of this film was immersed in 30 cc of toluene, shaken for 3 hours, and then filtered through a metal net having an opening of 45 μm to collect insoluble matter. The collected insoluble matter was dried at 130 ° C. for 1 hour, and the mass was measured. And toluene insoluble content (mass%) was calculated | required based on following Formula.
Toluene insoluble matter (mass%) = (mass of insoluble toluene content after drying / mass of film collected before immersion) × 100
（５）重合転化率の測定：
重合途中でサンプリングしたラテックスを２ｇ精秤後、１３０℃で３０分間乾燥し、乾燥前後の質量を測定して固形分（質量％）を求めた。次に、以下の式に基づき全単量体に対する重合転化率（質量％）を算出した。
重合転化率（質量％）＝（固形分（質量％）−不揮発分（質量％））／全仕込み原料中の単量体分（質量％）×１００
(5) Measurement of polymerization conversion:
After precisely weighing 2 g of the latex sampled during the polymerization, it was dried at 130 ° C. for 30 minutes, and the mass before and after drying was measured to obtain the solid content (% by mass). Next, the polymerization conversion ratio (% by mass) relative to all monomers was calculated based on the following formula.
Polymerization conversion rate (mass%) = (solid content (mass%) − nonvolatile content (mass%)) / monomer content in all charged raw materials (mass%) × 100
ここでいう不揮発分とは、サンプリングしたラテックス中に含まれる、乳化剤や開始剤等の不揮発分である。全仕込み原料中の単量体分とは、水、単量体、開始剤、乳化剤等といった全ての仕込み原料の総量に対する、単量体の総量の割合（質量％）である。 The non-volatile content here refers to non-volatile content such as emulsifier and initiator contained in the sampled latex. The monomer content in all the charged raw materials is the ratio (mass%) of the total amount of monomers with respect to the total amount of all the charged raw materials such as water, monomer, initiator and emulsifier.
（６）各重合段における単量体混合物から得られる共重合体のＳＰ値：
Ｒｏｂｅｒｔ Ｆ．Ｆｅｄｏｒｓが規定する方法に基づき、各々の単量体化合物構造と単量体組成から算出した。すなわち、ポリマーのＳＰ値（σｐ）は、そのポリマーを構成するモノマーの蒸発エネルギー（Δｅｉ）及びモル体積（Δｖｉ）をモノマー毎に求め、モノマーのポリマーにおけるモル比（ｊ）との積をそれぞれ算出し、モノマーの蒸発エネルギーの総和をモル体積の総和で割ることによって求め、下記式から算出した。
例えば、モノマーがスチレンである場合、重合によって二重結合が開裂した状態の分子構造を単量体として計算した。蒸発エネルギー（Δｅｉ（ｃａｌ／ｍｏｌ））及びモル体積（Δｖｉ（ｃｍ3／ｍｏｌ））は、ＰＯＬＹＭＥＲ ＥＮＧＩＮＮＥＥＲＩＮＧ ＡＮＤ ＳＣＩＥＮＣＥ，１９７４，Ｖｏｌ．１４，Ｎｏ．２，１４７−１５４に記載されている値を用いた。
σｐ＝｛（Σｊ×ΣΔｅｉ）／（Σｊ×ΣΔｖｉ）｝1/2
(6) SP value of the copolymer obtained from the monomer mixture in each polymerization stage:
Robert F. Based on the method prescribed by Fedors, each monomer compound structure and monomer composition were calculated. That is, the SP value (σp) of a polymer is obtained by calculating the evaporation energy (Δei) and molar volume (Δvi) of the monomer constituting the polymer for each monomer and calculating the product of the monomer-molar ratio (j) in the polymer. The sum of the evaporation energies of the monomers was divided by the sum of the molar volumes, and was calculated from the following formula.
For example, when the monomer is styrene, the molecular structure in which the double bond is cleaved by polymerization was calculated as the monomer. Evaporation energy (Δei (cal / mol)) and molar volume (Δvi (cm 3 / mol)) were measured in POLYMER ENGINNEERING AND SCIENCE, 1974, Vol. 14, no. 2, 147-154 were used.
σp = {(Σj × ΣΔei) / (Σj × ΣΔvi)} 1/2
［実施例１］
（共重合体を含むラテックス（イ）の作製）
攪拌機と内部温度調整用の温水ジャケット、及び各種原材料の定量添加設備を備えた耐圧反応器に、水７８質量部、ドデシルベンゼンスルホン酸ナトリウム０．１質量部、ドデシルジフェニルエーテルジスルホン酸ナトリウム０．１質量部、α−メチルスチレンダイマー０．４質量部、表１に示す第一重合工程用単量体の内のイタコン酸とフマール酸を仕込み、内温を７８℃に維持して充分に撹拌した。
[Example 1]
(Preparation of latex containing copolymer)
A pressure-resistant reactor equipped with a stirrer, a hot water jacket for adjusting the internal temperature, and equipment for quantitative addition of various raw materials, 78 parts by mass of water, 0.1 parts by mass of sodium dodecylbenzenesulfonate, 0.1 parts by mass of sodium dodecyldiphenyl ether disulfonate Part, α-methylstyrene dimer 0.4 parts by mass, and itaconic acid and fumaric acid among the monomers for the first polymerization step shown in Table 1 were charged, and the internal temperature was maintained at 78 ° C. and sufficiently stirred.
次いで、表１に示す第一重合工程用単量体の内のイタコン酸とフマール酸を除く単量体と連鎖移動剤からなる混合物の内の１０質量％を、この耐圧反応容器内に一括して仕込み、撹拌混合後、ペルオキソ二硫酸ナトリウム０．４質量部を耐圧反応器内に５分間かけて添加して重合反応を開始させた。 Next, 10% by mass of the mixture consisting of the monomer for the first polymerization step shown in Table 1 and the chain transfer agent, excluding itaconic acid and fumaric acid, is put together in this pressure resistant reactor. After stirring and mixing, 0.4 part by mass of sodium peroxodisulfate was added to the pressure resistant reactor over 5 minutes to initiate the polymerization reaction.
ペルオキソ二硫酸ナトリウム水溶液の添加終了時点から９０分後、残りの第一重合工程用の単量体及び連鎖移動剤の混合物をこの耐圧容器内に添加し始め、５時間２０分かけて連続的に添加した。この残りの第一重合工程用の単量体及び連鎖移動剤の混合物の添加と同時に、水１７質量部、水酸化ナトリウム０．１質量部、ドデシルジフェニルエーテルジスルホン酸ナトリウム０．４質量部、及びペルオキソ二硫酸ナトリウム０．６質量部からなる水系混合物の添加を始め、３時間１０分かけて連続的に添加し、重合反応を加速させた。更に同時に、重合温度即ち耐圧反応器の内温を、降温速度３．０℃／ｈｒで降温させ始め、重合温度が７０℃になった時点で降温を終了した。その後は降温終了後の温度で反応を継続させた。 After 90 minutes from the end of the addition of the aqueous sodium peroxodisulfate solution, the mixture of the remaining monomer and chain transfer agent for the first polymerization step was started to be added to the pressure vessel, and continuously for 5 hours and 20 minutes. Added. Simultaneously with the addition of the remaining monomer and chain transfer agent mixture for the first polymerization step, 17 parts by weight of water, 0.1 parts by weight of sodium hydroxide, 0.4 parts by weight of sodium dodecyl diphenyl ether disulfonate, and peroxo The addition of an aqueous mixture composed of 0.6 parts by mass of sodium disulfate was started continuously over 3 hours and 10 minutes to accelerate the polymerization reaction. At the same time, the polymerization temperature, that is, the internal temperature of the pressure-resistant reactor, was started to decrease at a temperature decrease rate of 3.0 ° C./hr, and the temperature decrease was terminated when the polymerization temperature reached 70 ° C. Thereafter, the reaction was continued at the temperature after completion of the temperature decrease.
第一重合工程用の単量体及び連鎖移動剤混合物の添加が終了した時点で、直ちに表１に示す第二重合工程用単量体と連鎖移動剤からなる混合物を４時間かけて連続的にこの耐圧容器内に添加し、重合反応を継続させた。 Immediately after the addition of the monomer for the first polymerization step and the chain transfer agent mixture, the mixture consisting of the monomer for the second polymerization step and the chain transfer agent shown in Table 1 was continuously added over 4 hours. It added in this pressure-resistant container, and the polymerization reaction was continued.
第二重合工程用の単量体及び連鎖移動剤の混合物の添加終了後、６０分間かけて耐圧容器内の温度を９５℃に昇温し、最終的な重合転化率を引き上げ、共重合体を含むラテックスを得た。この共重合体を含むラテックスには、水酸化カリウム及び水酸化ナトリウムを添加してｐＨを６．０以上に調整し、スチームストリッピング法で未反応の単量体を除去した後、水酸化ナトリウムを用いてｐＨを８．０に調整し、固形分濃度を５０質量％に調整して、共重合体を含むラテックス（イ）を得た。 After completing the addition of the monomer and chain transfer agent mixture for the second polymerization step, the temperature in the pressure vessel is raised to 95 ° C. over 60 minutes, raising the final polymerization conversion rate, A latex containing was obtained. To the latex containing this copolymer, potassium hydroxide and sodium hydroxide are added to adjust the pH to 6.0 or more, and unreacted monomers are removed by a steam stripping method. Was used to adjust the pH to 8.0 and the solid content concentration was adjusted to 50% by mass to obtain a latex (a) containing a copolymer.
このようにして得られた共重合体を含むラテックス（イ）について、耐湿潤ベタツキ性の評価を行った。その結果を表２に示す。 The latex (a) containing the copolymer thus obtained was evaluated for wet stickiness resistance. The results are shown in Table 2.
（紙塗工用組成物の調製と塗工紙の調製）
次に、得られた共重合体を含むラテックスと以下の材料を均一に混合して、紙塗工用組成物を調製した。なお、以下の配合（質量部）は、特に断りがない限り、水を除いて、全て固形分に換算した値である。
(Preparation of composition for paper coating and preparation of coated paper)
Next, the latex containing the obtained copolymer and the following materials were uniformly mixed to prepare a paper coating composition. In addition, the following mixing | blending (mass part) is the value converted into solid content altogether except water, unless there is particular notice.
カオリンクレー ３５質量部
重質炭酸カルシウム ６５質量部
ポリアクリル酸ナトリウム ０．０５質量部
水酸化ナトリウム ０．０６質量部
酸化でんぷん ３．０質量部
共重合体ラテックス（イ） ８質量部
水（塗工液の全固形分濃度が６６質量％となるように添加）
Kaolin clay 35 parts by weight Heavy calcium carbonate 65 parts by weight Sodium polyacrylate 0.05 parts by weight Sodium hydroxide 0.06 parts by weight Oxidized starch 3.0 parts by weight Copolymer latex (ii) 8 parts by weight Water (Coating Add so that the total solid concentration of the liquid is 66% by mass)
カオリンクレー：「アマゾンプラス」（カダム社製；粒子径２μｍ以下の割合＝９７質量％以上）
重質炭酸カルシウム：「カービタル９０」（イメリス社製；粒子径２μｍ以下の割合＝９０質量％以上）（商品名）
ポリアクリル酸ナトリウム：「アロンＴ−５０」（東亞合成社製）
酸化でんぷん：「王子コーンスターチＢ」（王子コーンスターチ社製）
Kaolin clay: “Amazon Plus” (manufactured by Kadam; ratio of particle size of 2 μm or less = 97 mass% or more)
Heavy calcium carbonate: “Carbital 90” (manufactured by Imeris; ratio of particle size of 2 μm or less = 90% by mass or more) (trade name)
Sodium polyacrylate: “Aron T-50” (manufactured by Toagosei Co., Ltd.)
Oxidized starch: “Oji Corn Starch B” (manufactured by Oji Corn Starch)
次に、得られた紙塗工用塗料組成物を、塗工量が片面８ｇ／ｍ2になるように坪量７４ｇ／ｍ2の塗工原紙にブレードコーターで塗工し、乾燥した後、ロール温度５０℃、線圧１４７，０００Ｎ／ｍでスーパーカレンダー処理を行い、塗工紙を得た。得られた塗工紙を印刷試験で評価した。この塗工紙のピック強度を測定し、結果を表２に記載した。いずれにおいても優れた結果が得られた。 Next, the obtained paper coating composition was applied to a base paper having a basis weight of 74 g / m 2 with a blade coater so that the coating amount was 8 g / m 2 on one side, and dried. Super calendering was performed at a roll temperature of 50 ° C. and a linear pressure of 147,000 N / m to obtain coated paper. The obtained coated paper was evaluated by a printing test. The pick strength of this coated paper was measured, and the results are shown in Table 2. In any case, excellent results were obtained.
［実施例２、３］
表１に示した条件に変更した点以外は実施例１と同様にして、共重合体を含むラテックス（ロ）、（ハ）を作製し、物性を評価した。評価結果を表２に示す。
[Examples 2 and 3]
Except for the point changed to the conditions shown in Table 1, latex (b) and (c) containing a copolymer were produced in the same manner as in Example 1, and the physical properties were evaluated. The evaluation results are shown in Table 2.
［実施例４］
（共重合体ラテックス（ニ）の作製）
実施例１で用いたものと同様の耐圧反応容器に、水７８質量部、ドデシルベンゼンスルホン酸ナトリウム０．１質量部、ドデシルジフェニルエーテルジスルホン酸ナトリウム０．１質量部、α−メチルスチレンダイマー０．４質量部、表１に示す初期工程用単量体の内のイタコン酸とフマール酸（質量部）を仕込み、内温を７８℃に維持して充分に撹拌した。
[Example 4]
(Production of copolymer latex (d))
In a pressure-resistant reaction vessel similar to that used in Example 1, 78 parts by mass of water, 0.1 part by mass of sodium dodecylbenzenesulfonate, 0.1 part by mass of sodium dodecyldiphenyl ether disulfonate, and α-methylstyrene dimer 0.4 Itaconic acid and fumaric acid (mass part) among the monomers for initial process shown in Table 1 were charged, and the internal temperature was maintained at 78 ° C. and sufficiently stirred.
次いで、表１に示す初期工程用単量体の内のイタコン酸とフマール酸を除く単量体と連鎖移動剤からなる、初期工程用の単量体及び連鎖移動剤の混合物を、この耐圧反応容器内に一括して仕込み、撹拌混合した後、ペルオキソ二硫酸ナトリウム０．４質量部を、耐圧反応器内に５分間かけて添加して重合反応を開始させた。 Next, a mixture of the monomer for the initial step and the chain transfer agent, which is composed of a monomer excluding itaconic acid and fumaric acid in the initial step monomer shown in Table 1 and a chain transfer agent, is subjected to this pressure reaction. After charging all in a container and stirring and mixing, 0.4 part by mass of sodium peroxodisulfate was added to the pressure resistant reactor over 5 minutes to initiate the polymerization reaction.
ペルオキソ二硫酸ナトリウム水溶液の添加終了から９０分後、表１に示す第一重合工程用単量体と連鎖移動剤からなる、第一重合工程用の単量体及び連鎖移動剤の混合物を５時間２０分かけて連続的にこの耐圧容器内に添加し、重合反応を継続させた。この第一重合工程用の単量体及び連鎖移動剤混合物の添加と同時に、水１７質量部、水酸化ナトリウム０．１質量部、ドデシルジフェニルエーテルジスルホン酸ナトリウム０．４質量部、及びペルオキソ二硫酸ナトリウム０．６質量部からなる水系混合物を添加し始め、３時間１０分かけて連続的に添加し、重合反応を加速させた。更に同時に、重合温度即ち耐圧反応器の内温を降温速度３．０℃／ｈｒで降温させ始め、重合温度が７０℃になった時点で降温を終了した。その後は降温終了後の温度で反応を継続させた。 90 minutes after completion of the addition of the aqueous sodium peroxodisulfate solution, a mixture of the monomer for the first polymerization step and the chain transfer agent, which is composed of the monomer for the first polymerization step shown in Table 1 and the chain transfer agent, was added for 5 hours. It added continuously in this pressure-resistant container over 20 minutes, and the polymerization reaction was continued. Simultaneously with the addition of the monomer and chain transfer agent mixture for this first polymerization step, 17 parts by weight of water, 0.1 parts by weight of sodium hydroxide, 0.4 parts by weight of sodium dodecyl diphenyl ether disulfonate, and sodium peroxodisulfate The addition of an aqueous mixture consisting of 0.6 parts by mass was started continuously over 3 hours and 10 minutes to accelerate the polymerization reaction. At the same time, the polymerization temperature, that is, the internal temperature of the pressure-resistant reactor, was started to decrease at a temperature decrease rate of 3.0 ° C./hr. Thereafter, the reaction was continued at the temperature after completion of the temperature decrease.
第一重合工程用の単量体及び連鎖移動剤混合物の添加が終了した時点で、直ちに表１に示す第二重合工程用単量体と連鎖移動剤からなる、第二重合工程用の単量体及び連鎖移動剤の混合物を４時間かけて連続的にこの耐圧容器内に添加し、重合反応を継続させた。
第二重合工程用の単量体及び連鎖移動剤の混合物の添加終了後、６０分間かけて耐圧容器内の温度を９５℃に昇温し、最終的な重合転化率を引き上げ、共重合体を含むラテックスを得た。
この共重合体を含むラテックスには、水酸化カリウム及び水酸化ナトリウムを添加してｐＨを６．０以上に調整し、スチームストリッピング法で未反応の単量体を除去した後、水酸化ナトリウムを用いてｐＨを８．０に調整し、固形分濃度を５０質量％に調整して、共重合体を含むラテックス（ニ）を得た。
When the addition of the monomer for the first polymerization step and the chain transfer agent mixture is completed, the monomer for the second polymerization step immediately comprising the monomer for the second polymerization step and the chain transfer agent shown in Table 1 The mixture of the body and the chain transfer agent was continuously added into the pressure vessel over 4 hours, and the polymerization reaction was continued.
After completing the addition of the monomer and chain transfer agent mixture for the second polymerization step, the temperature in the pressure vessel is raised to 95 ° C. over 60 minutes, raising the final polymerization conversion rate, A latex containing was obtained.
To the latex containing this copolymer, potassium hydroxide and sodium hydroxide are added to adjust the pH to 6.0 or more, and unreacted monomers are removed by a steam stripping method. Was used to adjust the pH to 8.0 and the solid content concentration was adjusted to 50% by mass to obtain a latex (d) containing a copolymer.
このようにして得られた共重合体を含むラテックス（ニ）について、実施例１と同様に、ピック強度、耐湿潤ベタツキ性を評価した。評価結果を表２に示す。 The latex (d) containing the copolymer thus obtained was evaluated for pick strength and wet stickiness resistance in the same manner as in Example 1. The evaluation results are shown in Table 2.
［比較例１〜４］
表１に示した条件に変更した点以外は実施例１と同様にして、共重合体を含むラテックス（ホ）〜（チ）を作製し、物性を評価した。評価結果を表２に示す。
[Comparative Examples 1-4]
Except for the points changed to the conditions shown in Table 1, latexes (e) to (h) containing a copolymer were produced in the same manner as in Example 1, and the physical properties were evaluated. The evaluation results are shown in Table 2.
下記表に、各実施例及び各比較例の製造条件及び評価結果を示す。なお、表中、特に断りが無い限り、各成分の含有量は質量％基準に基づくものである。 The following table shows the production conditions and evaluation results of each example and each comparative example. In the table, unless otherwise specified, the content of each component is based on the mass% standard.
上記表から明らかなように、各実施例のラテックス組成物に関して、ピック強度と耐湿潤ベタツキ性のいずれもが優れていることが少なくとも確認された。 As is clear from the above table, it was at least confirmed that the latex composition of each example was excellent in both pick strength and wet stickiness resistance.
本発明によれば、塗工紙のピック強度を向上させ、かつ共重合体を含むラテックスの耐湿潤ベタツキ性に優れてバッキングロール汚れ適性に優れる共重合体を含むラテックスを提供することができ、特に、塗工紙製造業及び関連産業の分野での産業上の利用可能性を少なくとも有する。 According to the present invention, it is possible to provide a latex containing a copolymer that improves the pick strength of the coated paper and is excellent in wet stickiness resistance of the latex containing the copolymer and excellent in backing roll soilability. In particular, it has at least industrial applicability in the field of coated paper manufacturing and related industries.
Claims (8)
前記乳化重合が、第一重合工程と第二重合工程とを含み、
前記第一重合工程において添加される単量体総量に対する、前記第一重合工程において添加される前記（ａ）成分の割合が、前記第二重合工程において添加される単量体総量に対する、前記第二重合工程において添加される前記（ａ）成分の割合よりも小さく、
前記第一重合工程で添加される単量体混合物（Ａ）から得られる共重合体（Ａ）の溶解性パラメータ（ＳＰＡ）と、前記第二重合工程で添加される単量体混合物（Ｂ）から得られる共重合体（Ｂ）の溶解性パラメータ（ＳＰＢ）とが、下記式（１）で表される関係を満たし、
前記乳化重合の間に、重合温度を降温させる、
共重合体を含むラテックス。
０．１＜（ＳＰＡ）−（ＳＰＢ）＜１．５ （１）
（溶解性パラメータ（ＳＰＡ）及び（ＳＰＢ）は、Ｒｏｂｅｒｔ Ｆ．Ｆｅｄｏｒｓが規定する方法に基づく値である。） A mixture containing (a) 25 to 65% by mass of a conjugated diene monomer and (b) 35 to 75% by mass of another copolymerizable monomer (provided that (a) + (b) = 100% by mass). Is a latex containing a copolymer obtained by emulsion polymerization,
The emulsion polymerization includes a first polymerization step and a second polymerization step,
The ratio of the component (a) added in the first polymerization step with respect to the total amount of monomers added in the first polymerization step is based on the total amount of monomers added in the second polymerization step. Smaller than the proportion of the component (a) added in the bipolymerization step,
The solubility parameter (SPA) of the copolymer (A) obtained from the monomer mixture (A) added in the first polymerization step, and the monomer mixture (B) added in the second polymerization step The solubility parameter (SPB) of the copolymer (B) obtained from the above satisfies the relationship represented by the following formula (1),
During the emulsion polymerization, the polymerization temperature is lowered.
Latex containing a copolymer.
0.1 <(SPA)-(SPB) <1.5 (1)
(The solubility parameters (SPA) and (SPB) are values based on the method prescribed by Robert F. Fedors).
前記初期工程で添加される前記（ｂ）成分の添加量は、前記乳化重合において添加される単量体の総量１００質量％に対して５〜５０質量％であり、
前記初期工程は、重合転化率が２０〜６５質量％に達するまで重合させる、
請求項１に記載のラテックス。 The emulsion polymerization further includes an initial step of homopolymerizing only the component (b) as a monomer before the first polymerization step,
The addition amount of the component (b) added in the initial step is 5 to 50% by mass with respect to 100% by mass of the total amount of monomers added in the emulsion polymerization,
In the initial step, the polymerization is performed until the polymerization conversion rate reaches 20 to 65% by mass.
The latex according to claim 1.
前記第一重合工程において添加される前記単量体総量に対する、前記第一重合工程において添加されるα−メチルスチレンダイマーの割合が、前記第二重合工程以降の各重合工程で添加される単量体の総量に対する、前記第二重合工程以降の各工程で添加されるα−メチルスチレンダイマーの総量の割合よりも大きい、
請求項１又は２記載のラテックス。 Each polymerization step of the emulsion polymerization is performed using at least α-methylstyrene dimer,
The ratio of α-methylstyrene dimer added in the first polymerization step to the total amount of the monomer added in the first polymerization step is a single amount added in each polymerization step after the second polymerization step. Greater than the ratio of the total amount of α-methylstyrene dimer added in each step after the second polymerization step to the total amount of the body,
The latex according to claim 1 or 2.
前記乳化重合が、第一重合工程と第二重合工程とを含み、
前記第一重合工程において添加される単量体総量に対する、前記第一重合工程において添加される前記（ａ）成分の割合が、前記第二重合工程において添加される単量体総量に対する、前記第二重合工程において添加される前記（ａ）成分の割合よりも小さく、
前記第一重合工程で添加される単量体混合物（Ａ）から得られる共重合体（Ａ）の溶解性パラメータ（ＳＰＡ）と、前記第二重合工程で添加される単量体混合物（Ｂ）から得られる共重合体（Ｂ）の溶解性パラメータ（ＳＰＢ）とが、下記式（１）で表される関係を満たし、
前記乳化重合の間に、重合温度を降温させる、
共重合体を含むラテックスの製造方法。
０．１＜（ＳＰＡ）−（ＳＰＢ）＜１．５ （１）
（溶解性パラメータ（ＳＰＡ）及び（ＳＰＢ）は、Ｒｏｂｅｒｔ Ｆ．Ｆｅｄｏｒｓが規定する方法に基づく値である。） A mixture containing (a) 25 to 65% by mass of a conjugated diene monomer and (b) 35 to 75% by mass of another copolymerizable monomer (provided that (a) + (b) = 100% by mass). A process for producing a latex comprising a copolymer for emulsion polymerization of
The emulsion polymerization includes a first polymerization step and a second polymerization step,
The ratio of the component (a) added in the first polymerization step with respect to the total amount of monomers added in the first polymerization step is based on the total amount of monomers added in the second polymerization step. Smaller than the proportion of the component (a) added in the bipolymerization step,
The solubility parameter (SPA) of the copolymer (A) obtained from the monomer mixture (A) added in the first polymerization step, and the monomer mixture (B) added in the second polymerization step The solubility parameter (SPB) of the copolymer (B) obtained from the above satisfies the relationship represented by the following formula (1),
During the emulsion polymerization, the polymerization temperature is lowered.
A method for producing a latex containing a copolymer.
0.1 <(SPA)-(SPB) <1.5 (1)
(The solubility parameters (SPA) and (SPB) are values based on the method prescribed by Robert F. Fedors).
前記初期工程で添加される前記（ｂ）成分の添加量は、前記乳化重合において添加される単量体の総量１００質量％に対して５〜５０質量％であり、
前記初期工程は、重合転化率が２０〜６５質量％に達するまで重合させる、
請求項６に記載のラテックスの製造方法。 The emulsion polymerization further includes an initial step of homopolymerizing only the component (b) as a monomer before the first polymerization step,
The addition amount of the component (b) added in the initial step is 5 to 50% by mass with respect to 100% by mass of the total amount of monomers added in the emulsion polymerization,
In the initial step, the polymerization is performed until the polymerization conversion rate reaches 20 to 65% by mass.
The method for producing a latex according to claim 6.
前記第一重合工程において添加される前記単量体総量に対する、前記第一重合工程において添加されるα−メチルスチレンダイマーの割合が、前記第二重合工程以降の各重合工程で添加される単量体の総量に対する、前記第二重合工程以降の各工程で添加されるα−メチルスチレンダイマーの総量の割合よりも大きい、
請求項６又は７記載のラテックスの製造方法。 Each polymerization step of the emulsion polymerization is performed using at least α-methylstyrene dimer,
The ratio of α-methylstyrene dimer added in the first polymerization step to the total amount of the monomer added in the first polymerization step is a single amount added in each polymerization step after the second polymerization step. Greater than the ratio of the total amount of α-methylstyrene dimer added in each step after the second polymerization step to the total amount of the body,
The method for producing a latex according to claim 6 or 7.
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