JP2007154125A - Copolymer latex, composition comprising the copolymer latex for coating offset paper and coated paper - Google Patents
Copolymer latex, composition comprising the copolymer latex for coating offset paper and coated paper Download PDFInfo
- Publication number
- JP2007154125A JP2007154125A JP2005354718A JP2005354718A JP2007154125A JP 2007154125 A JP2007154125 A JP 2007154125A JP 2005354718 A JP2005354718 A JP 2005354718A JP 2005354718 A JP2005354718 A JP 2005354718A JP 2007154125 A JP2007154125 A JP 2007154125A
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- Prior art keywords
- copolymer latex
- monomer
- mass
- polymerization
- paper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 163
- 239000004816 latex Substances 0.000 title claims abstract description 156
- 229920000126 latex Polymers 0.000 title claims abstract description 156
- 239000000203 mixture Substances 0.000 title claims description 94
- 238000000576 coating method Methods 0.000 title description 27
- 239000011248 coating agent Substances 0.000 title description 25
- 239000000178 monomer Substances 0.000 claims abstract description 176
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 38
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000007787 solid Substances 0.000 claims abstract description 25
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 9
- 150000001993 dienes Chemical class 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 120
- 239000008199 coating composition Substances 0.000 claims description 38
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000000049 pigment Substances 0.000 claims description 20
- -1 acrylic acid hydroxyalkyl ester Chemical class 0.000 claims description 17
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- 239000005995 Aluminium silicate Substances 0.000 claims description 9
- 235000012211 aluminium silicate Nutrition 0.000 claims description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- 239000004927 clay Substances 0.000 claims description 8
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000007645 offset printing Methods 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 41
- 230000000694 effects Effects 0.000 abstract description 14
- 238000004140 cleaning Methods 0.000 abstract description 12
- 150000001735 carboxylic acids Chemical class 0.000 abstract 1
- 239000000123 paper Substances 0.000 description 110
- 238000000034 method Methods 0.000 description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 238000011156 evaluation Methods 0.000 description 22
- 239000012986 chain transfer agent Substances 0.000 description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- 238000007639 printing Methods 0.000 description 16
- 239000002994 raw material Substances 0.000 description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 14
- 230000006872 improvement Effects 0.000 description 12
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 12
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 8
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 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 5
- 239000000654 additive Substances 0.000 description 5
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- 239000003999 initiator Substances 0.000 description 5
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- 238000001035 drying Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- ZIWRUEGECALFST-UHFFFAOYSA-M sodium 4-(4-dodecoxysulfonylphenoxy)benzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCOS(=O)(=O)c1ccc(Oc2ccc(cc2)S([O-])(=O)=O)cc1 ZIWRUEGECALFST-UHFFFAOYSA-M 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
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- 239000004094 surface-active agent Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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- 229920001971 elastomer Polymers 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 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
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000006228 supernatant 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
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- UGIJCMNGQCUTPI-UHFFFAOYSA-N 2-aminoethyl prop-2-enoate Chemical compound NCCOC(=O)C=C UGIJCMNGQCUTPI-UHFFFAOYSA-N 0.000 description 1
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 description 1
- CLKLLOQFHJTTNV-UHFFFAOYSA-N 2-methyl-n-(oxiran-2-ylmethyl)prop-2-enamide Chemical class CC(=C)C(=O)NCC1CO1 CLKLLOQFHJTTNV-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、塗工紙における顔料バインダーに用いられる共重合体ラテックス、その共重合体ラテックスを使用した紙塗工組成物に関するものである。更に詳しくは、高い接着強度（ピック強度及び湿潤ピック強度）、と塗工操業性とを両立する共重合体ラテックス、オフセット紙塗工組成物、塗工紙に関する。 The present invention relates to a copolymer latex used as a pigment binder in coated paper, and a paper coating composition using the copolymer latex. More specifically, the present invention relates to a copolymer latex, an offset paper coating composition, and a coated paper that have both high adhesive strength (pick strength and wet pick strength) and coating operability.
共重合体ラテックスは、塗工紙における顔料バインダー、カーペットバッキング剤、各種接着剤および粘着剤、繊維結合剤ならびに塗料など広範な用途に用いられてきた。これらの用途に用いられる共重合体ラテックスには、基材や配合される顔料などに対する優れた接着力が要求される。 Copolymer latex has been used in a wide range of applications such as pigment binders in coated paper, carpet backing agents, various adhesives and tackifiers, fiber binders and paints. Copolymer latex used for these applications is required to have excellent adhesion to substrates and pigments to be blended.
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、原紙にカオリンクレー、炭酸カルシウム、サチンホワイト、タルク、酸化チタンなどの無機顔料およびプラスチック顔料などの有機顔料を塗布したものであり、これらの顔料のバインダーとしてジエン系共重合体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ラテックスの性質は、これを利用した塗工紙の表面強度に大きな影響を及ぼすことが知られている。 Coated paper is used to improve the smoothness of the surface of the paper and improve the gloss and printability. The base paper is composed of inorganic pigments such as kaolin clay, calcium carbonate, satin white, talc, titanium oxide, and plastic pigments. These organic pigments are applied, and diene copolymer latex is generally used as a binder for these pigments. It is known that the properties of the copolymer latex used as a pigment binder have a great influence on the surface strength of coated paper using this.
近年、カラー印刷された雑誌類やパンフレット、広告等の需要の増大に伴い、印刷速度の高速化が進められており、特にインクのタックによる紙の表面の破壊に対する抵抗性（いわゆるピック強度及び湿潤ピック強度）の改善が以前にも増して要求されるようになった。また、塗工紙を生産する製紙メーカーにとっては、製品のコストダウンが主要課題の１つでもあり、共重合体ラテックスの使用割合を減らす事が要求され、この観点でも共重合体ラテックスの持つ性能としての接着強度（ピック強度及び湿潤ピック強度）の改善が望まれている。更には最近の塗工紙品質へのニーズとして、白紙光沢の高いものが求められ、このニーズへの対応として紙塗工組成物には平均粒子径の小さい顔料が主体的に用いられる傾向がある。この作用は同時に塗工紙のピック強度や湿潤ピック強度を低下させる方向になる。この観点でも、共重合体ラテックスに対して高いピック強度や湿潤ピック強度の性能を付与する事が求められている。 In recent years, with the increasing demand for color-printed magazines, pamphlets, advertisements, etc., the printing speed has been increased, especially resistance to the destruction of the paper surface due to ink tack (so-called pick strength and wetness). Improvements in pick strength have become more demanding than ever before. In addition, reducing the cost of products is one of the main challenges for paper manufacturers that produce coated paper, and it is required to reduce the proportion of copolymer latex used. Improvement of adhesive strength (pick strength and wet pick strength) is desired. Furthermore, recent needs for coated paper quality require high glossy white paper, and in response to this need, paper coating compositions tend to mainly use pigments with a small average particle size. . This action simultaneously decreases the pick strength and wet pick strength of the coated paper. Also from this viewpoint, it is required to impart high pick strength and wet pick strength performance to the copolymer latex.
一方、塗工紙の生産においても、生産能力および生産性の向上のため塗工速度の高速化が進められ、ここでも塗工操業性に影響を与える共重合体ラテックスへの品質要求は高まっている。塗工紙の製造は、先に述べた共重合体ラテックスを主バインダーとする塗工液が、原紙にフラッデドニップロールやジェットファウンテン方式によってアプリケートされ、ブレード等によって余分な塗工液が掻き取られ、塗工液の所定量を塗布し、乾燥するのが一般的な方法である。塗工紙は表裏両面に印刷されることが多く、このため塗工紙の生産では、原紙の片面（おもて面）に塗布乾燥後、もう一方の面（裏面）に同様な方法で処理が行われる。 On the other hand, in the production of coated paper, the coating speed has been increased to improve the production capacity and productivity, and again, the quality requirements for copolymer latex, which affects the coating operability, are increasing. Yes. In the production of coated paper, the coating liquid containing the copolymer latex as the main binder described above is applied to the base paper by the flooded nip roll or jet fountain method, and the excess coating liquid is scraped off by a blade or the like. It is common practice to take, apply a predetermined amount of coating liquid and dry. Coated paper is often printed on both the front and back sides. For this reason, in coated paper production, after coating and drying on one side (front side) of the base paper, the other side (back side) is processed in the same way. Is done.
このブレードによる計量の際に塗工紙はブレードとバッキングロールとの間で高いシェアーと圧力を受け、特に裏面塗工時におもて面の塗工層表層部分がバッキングロールに転移する、いわゆるバッキングロール汚れを発生することがあり、汚れの発生が著しくなると原紙の紙切れや頻繁な研磨によるロール洗浄の必要が生じ、生産性が低下する。この塗工操業性の改良には、主として２種類の考え方がある。 When weighing with this blade, the coated paper receives a high shear and pressure between the blade and the backing roll, and the surface layer of the coating layer on the front surface is transferred to the backing roll, especially during backside coating. Roll stains may occur, and if the occurrence of stains becomes significant, it becomes necessary to perform roll cleaning by cutting out of the base paper or frequent polishing, and productivity is lowered. There are mainly two types of ideas for improving the coating operability.
まず第一に、ロールへの転移を少なくする事であり、その目的を果たす為には、更に２つの改良方向がある。改良方向の１点目は共重合体ラテックスの粘着性を低減させることであり、共重合体ラテックスのベタツキ性を低減させることが有効であるが、通常、バッキングロールにはフロークリン水と呼ばれる少量の洗浄水がロール上に連続的に流されている。従って、共重合体ラテックスの粘着性についても、水を介した状態でのベタツキ性、即ち、耐湿潤ベタツキ性の向上が特に有効である。ロールへの転移を少なくする改良方向の２点目は、塗工紙の表面強度を向上させる事であるが、前述のフロークリン水の存在を考慮し、水を介した状態での表面強度、即ち、耐湿潤強度の改良が有効である。塗工紙の耐湿潤強度は、塗工後より経時変化を伴う為、本課題に対する改良方向としては、塗工直後の耐湿潤強度、即ち初期耐水性を改良する事が特に有効である。 First of all, to reduce the transfer to the roll, there are two further directions for improvement in order to achieve that purpose. The first point in the improvement direction is to reduce the tackiness of the copolymer latex, and it is effective to reduce the stickiness of the copolymer latex, but usually a small amount called flow clean water is used for the backing roll. Of washing water is continuously flowing on the roll. Therefore, with respect to the tackiness of the copolymer latex, it is particularly effective to improve the stickiness in a state of passing through water, that is, the wet stickiness resistance. The second point in the improvement direction to reduce the transfer to the roll is to improve the surface strength of the coated paper, but considering the presence of the aforementioned flow clean water, the surface strength in the state through water, That is, improvement of the wet strength is effective. Since the wet strength of the coated paper is changed with time after coating, it is particularly effective to improve the wet strength immediately after coating, that is, the initial water resistance, as an improvement direction for this problem.
塗工操業性改良の考え方の第二は、ロール上に転移した共重合体ラテックスを含む異物（塗工層の一部）を、容易に洗浄・除去させる事である。通常、バッキングロールには付着した異物を掻きとって除去するドクターブレードが設置されている。この観点で必要な性能は、前述の様な共重合体ラテックスの耐湿潤ベタツキ性の向上に加え、ドクターブレードでの異物の掻き取り易さ、即ち洗浄性を改良する事が特に有効である。 The second idea of improving the coating operability is to easily wash and remove foreign matters (a part of the coating layer) containing the copolymer latex transferred onto the roll. Usually, a doctor blade that scrapes and removes adhering foreign matter is installed on the backing roll. In terms of the performance required from this point of view, it is particularly effective to improve the wettability and stickiness of the copolymer latex as described above, and to improve the ease of scraping of foreign matters with a doctor blade, that is, the cleaning property.
以上のような塗工紙の品質向上や塗工紙生産の操業上の問題解決を目的として、共重合体ラテックスについては様々な改良がなされてきた。例えば、ピック強度を改良する目的で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がある。しかし、この方法では白紙光沢の低下および耐湿潤ベタツキ性が低下する問題点が残る。 Various improvements have been made to the copolymer latex for the purpose of improving the quality of the coated paper and solving the operational problems in the production of the coated paper. For example, for the purpose of improving the pick strength, there is a method of increasing the composition ratio of the conjugated diene monomer to lower the glass transition temperature of the copolymer. However, this method still has a problem that the glossiness of the white paper is lowered and the wet stickiness resistance is lowered.
また、例えば、特定の単量体組成で二段もしくは多段で重合を行う共重合体ラテックスの改良が多数提案されている（特許文献１、特許文献２、特許文献３、特許文献４、特許文献５、特許文献６、特許文献７）。しかしながらこれらの発明では、塗工紙のピック強度、湿潤ピック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充分なものであった。 In addition, for example, many improvements of copolymer latexes in which polymerization is performed in a two-stage or multi-stage with a specific monomer composition have been proposed (Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4, and Patent Document). 5, Patent Document 6, Patent Document 7). However, these inventions are insufficient as means for achieving both improvement in pick strength and wet pick strength of coated paper and improvement in backing roll dirt characteristics.
更には、初期耐水性を改良させる方法として、ジルコニウムを含む特定組成の共重合体ラテックスを使用した紙塗工組成物（特許文献８）が開示されているが、この方法では初期耐水性改良の効果は未だ不充分である。また、水への洗浄性を改良する方法として特定組成の単量体を、特定組成を有する反応性乳化剤と共に共重合して製造する共重合体ラテックスの製造方法（特許文献９）が開示されているが、この発明では前述のようなドクターブレードでの掻き取り易さを考慮した洗浄性（以下、ドクターブレード洗浄性と言うことがある）を改良させる効果は不充分であり、従ってバッキングロール汚れの改良手段としては不充分なものであった。
本発明は、以上のような状況から、塗工紙のピック強度と湿潤ピック強度を向上させ、更に耐湿潤ベタツキ性、ドクターブレード洗浄性及び初期耐水性に優れてバッキングロール汚れの抑制効果をも有する共重合体ラテックスを提供することを課題とする。好ましくは、該共重合体ラテックスを使用した紙塗工組成物、印刷用塗工紙を提供する事を課題とする。 The present invention improves the pick strength and wet pick strength of coated paper from the above situation, and further has excellent wet stickiness resistance, doctor blade cleaning properties and initial water resistance, and also has an effect of suppressing backing roll stains. It is an object to provide a copolymer latex having the same. Preferably, it is an object to provide a paper coating composition and a coated paper for printing using the copolymer latex.
本発明者は、上述の問題点を解決するために鋭意検討した結果、共重合体ラテックスに関し、出発原料である単量体組成を特定範囲に限定すると共に、共重合体ラテックス中に含有した単量体の効果及び影響に着目し、特定のエチレン系不飽和カルボン酸単量体の含有量を調整する事によって顕著な効果を発現する事を見出し、鋭意検討した結果、本発明をなすに至った。即ち本発明は、下記の通りである。 As a result of intensive studies to solve the above-mentioned problems, the present inventor has limited the monomer composition as a starting material to a specific range with respect to the copolymer latex, and the monomer latex contained in the copolymer latex. Focusing on the effect and influence of the monomer, it has been found that a significant effect is manifested by adjusting the content of a specific ethylenically unsaturated carboxylic acid monomer, and as a result of intensive studies, the present invention has been made. It was. That is, the present invention is as follows.
［１］（ａ）共役ジエン系単量体２５〜６０質量％、（ｂ）エチレン系不飽和カルボン酸単量体１．５〜７質量％、（ｃ）シアン化ビニル単量体１０〜３０質量％、および（ｄ）その他共重合可能な単量体３〜６３．５質量％から成る単量体を乳化重合して得られる共重合体ラテックスであって、該共重合体ラテックス中に含有するアクリル酸単量体が、該共重合体ラテックスの固形分に対して１００〜５０００ｐｐｍである事を特徴とする共重合体ラテックス。 [1] (a) 25-60 mass% of conjugated diene monomer, (b) 1.5-7 mass% of ethylenically unsaturated carboxylic acid monomer, (c) vinyl cyanide monomer 10-30 And (d) a copolymer latex obtained by emulsion polymerization of a monomer comprising 3 to 63.5% by mass of another copolymerizable monomer, contained in the copolymer latex A copolymer latex characterized in that the acrylic acid monomer is 100 to 5000 ppm based on the solid content of the copolymer latex.
［２］前記の単量体混合物が、前記（ｂ）成分にアクリル酸を含有するか、または、前記（ｄ）成分にアクリル酸ヒドロキシアルキルエステル単量体を含有するかのいずれかであることを特徴とする前記［１］記載の共重合体ラテックス。 [2] The monomer mixture contains either acrylic acid in the component (b) or a hydroxyalkyl ester monomer of acrylic acid in the component (d). Copolymer latex as described in [1] above,
［３］前記の単量体混合物が、前記（ｂ）成分にアクリル酸を含有し、かつ前記（ｄ）成分にアクリル酸ヒドロキシアルキルエステル単量体を含有することを特徴とする前記［１］記載の共重合体ラテックス。 [3] The above-mentioned monomer mixture, wherein the monomer mixture contains acrylic acid in the component (b) and an acrylic acid hydroxyalkyl ester monomer in the component (d). The copolymer latex described.
［４］前記の単量体混合物が、前記（ｂ）成分に二塩基性エチレン系不飽和カルボン酸単量体を含有するものであり、前記の乳化重合は、少なくとも二段の重合工程を経ると共に、前記の二塩基性エチレン系不飽和カルボン酸の少なくとも６０質量％以上を、前記重合工程の第二重合段以降において系内の単量体の重合転化率が６５〜９５％の範囲内であるいずれかの時点から、添加を開始することを特徴とする前記［１］から［３］のいずれかに記載の共重合体ラテックス。 [4] The monomer mixture contains a dibasic ethylenically unsaturated carboxylic acid monomer in the component (b), and the emulsion polymerization undergoes at least a two-stage polymerization step. In addition, at least 60% by mass or more of the dibasic ethylenically unsaturated carboxylic acid is within the range of 65 to 95% of the polymerization conversion rate of the monomer in the system after the second polymerization stage of the polymerization process. The copolymer latex according to any one of [1] to [3], wherein the addition is started from a certain point in time.
［５］顔料と共重合体ラテックスとを含有するオフセット印刷紙用の紙塗工組成物であって、前記顔料は、粒子径が２μｍ以下のものが８０質量％以上であるカオリンクレーと、粒子径が２μｍ以下のものが８０質量％以上である重質炭酸カルシウムとから成るものであり、前記共重合体ラテックスは、前記［１］〜［４］のいずれかに記載の共重合体ラテックスであることを特徴とする紙塗工組成物。 [5] A paper coating composition for offset printing paper containing a pigment and a copolymer latex, wherein the pigment has a kaolin clay having a particle diameter of 2 μm or less and 80% by mass or more; The copolymer latex according to any one of [1] to [4], wherein the copolymer latex is composed of heavy calcium carbonate having a diameter of 2 μm or less and 80% by mass or more. A paper coating composition characterized by being.
［６］前記［５］に記載の紙塗工組成物が、表面に塗工処理されたオフセット印刷用塗工紙。 [6] A coated paper for offset printing, the surface of which is coated with the paper coating composition according to [5].
本発明の共重合体ラテックスによれば、塗工紙のピック強度及び湿潤ピック強度向上と共に、耐湿潤ベタツキ性、初期耐水性及びドクターブレード洗浄性の全てを向上させることができる。その結果、共重合体ラテックスを含む紙塗工組成物を用いた塗工工程での操業性、特にバッキングロール汚れトラブルを抑制でき、かつ印刷用塗工紙に極めて優れたピック強度と湿潤ピック強度を付与する事が可能になる。 According to the copolymer latex of the present invention, it is possible to improve all of wet stickiness resistance, initial water resistance and doctor blade cleanability as well as improved pick strength and wet pick strength of coated paper. As a result, the operability in the coating process using the paper coating composition containing the copolymer latex, especially the backing roll stain trouble can be suppressed, and the pick strength and wet pick strength that are extremely excellent for coated paper for printing Can be granted.
以下、本発明について、特にその好ましい実施の形態を中心に、具体的に説明する。共重合体ラテックスの原料の１つである（ａ）共役ジエン系単量体は、共重合体に柔軟性を与え、ピック強度、衝撃吸収性を与えるために必須の成分であり、該共重合体を構成する全単量体を１００質量％とした場合、２５〜６０質量％、好ましくは３０〜５５質量％、最も好ましくは３２〜５０質量％の割合で用いられる。この単量体の使用量を上記範囲に設定する事により、共重合体に適度の柔軟性と弾性を付与してピック強度を向上させ、更には耐湿潤ベタツキ性を向上させる事ができる。使用される共役ジエン系単量体の好ましい例としては、１，３−ブタジエン、イソプレン、２−クロロ−１，３−ブタジエンなどがあげられ、これらは１種または２種以上が組み合わせて用いられる。 Hereinafter, the present invention will be specifically described with a focus on preferred embodiments. (A) Conjugated diene monomer, which is one of the raw materials for the copolymer latex, is an essential component for imparting flexibility to the copolymer and providing pick strength and impact absorption. When the total monomer constituting the coalescence is 100% by mass, it is used in a proportion of 25 to 60% by mass, preferably 30 to 55% by mass, and most preferably 32 to 50% by mass. By setting the amount of the monomer used within the above range, the copolymer can be imparted with appropriate flexibility and elasticity to improve the pick strength and further improve the wet stickiness resistance. Preferable examples of the conjugated diene monomer used include 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene and the like, and these are used alone or in combination of two or more. .
また、原料の１つである（ｂ）エチレン系不飽和カルボン酸単量体は、共重合体ラテックスに必要な分散安定性を与え、ピック強度、湿潤ピック強度を高めるための必須成分であり、該共重合体を構成する全単量体を１００質量％とした場合、全単量体に対し１．５〜７質量％、好ましくは２〜６質量％、更に好ましくは２．５〜５質量％の割合で用いられる。この単量体の使用量を上記範囲に設定する事により、共重合体ラテックスの耐湿潤ベタツキ性を良好（べたつかない）に保つ事が可能になり、且つこの共重合体ラテックスを使用した紙塗工組成物のドクターブレード洗浄性を良好にすることが可能となり、塗工工程におけるさまざまな問題発生を回避する事が可能となる。また共重合体ラテックス組成物の粘度を取り扱いに支障をきたさない適度な範囲に調整する事が可能である。 In addition, (b) the ethylenically unsaturated carboxylic acid monomer which is one of the raw materials is an essential component for providing the dispersion stability necessary for the copolymer latex and for increasing the pick strength and the wet pick strength. When the total monomer constituting the copolymer is 100% by mass, it is 1.5 to 7% by mass, preferably 2 to 6% by mass, more preferably 2.5 to 5% by mass with respect to the total monomer. % Is used. By setting the amount of this monomer to be within the above range, it becomes possible to keep the wet-stickiness resistance of the copolymer latex good (not sticky), and paper coating using this copolymer latex. It becomes possible to improve the cleaning performance of the doctor blade of the work composition, and it is possible to avoid the occurrence of various problems in the coating process. It is also possible to adjust the viscosity of the copolymer latex composition to an appropriate range that does not hinder handling.
エチレン系不飽和カルボン酸単量体の好ましい例としては、アクリル酸、メタクリル酸等の一塩基性エチレン系不飽和カルボン酸単量体、イタコン酸、マレイン酸、フマル酸等の二塩基性エチレン系不飽和カルボン酸単量体などがあげられ、これらは１種または２種以上が組み合わせて用いられる。より好ましくは、二塩基性エチレン系不飽和カルボン酸単量体と、一塩基性エチレン系不飽和カルボン酸を併用して使用することであり、使用するエチレン系不飽和カルボン酸単量体の全質量に対し、少なくとも４０質量％以上９５質量％以下、好ましくは５０質量％以上９０質量％以下、最も好ましくは５５質量％以上８７質量％以下が二塩基性エチレン系不飽和カルボン酸単量体であることである。二塩基性エチレン系不飽和カルボン酸単量体の使用割合をこの範囲に定める事により、耐湿潤ベタツキ性をより良好なレベルに調整する事が可能になり、最も好ましくは、紙塗工組成物のドクターブレード洗浄性向上の観点から、イタコン酸とアクリル酸を併用して使用する事である。 Preferred examples of the ethylenically unsaturated carboxylic acid monomer include monobasic ethylene unsaturated carboxylic acid monomers such as acrylic acid and methacrylic acid, dibasic ethylene series such as itaconic acid, maleic acid, and fumaric acid. An unsaturated carboxylic acid monomer etc. are mention | raise | lifted and these are used 1 type or in combination of 2 or more types. More preferably, a dibasic ethylenically unsaturated carboxylic acid monomer and a monobasic ethylenically unsaturated carboxylic acid are used in combination. The dibasic ethylenically unsaturated carboxylic acid monomer is at least 40% by weight to 95% by weight, preferably 50% by weight to 90% by weight, and most preferably 55% by weight to 87% by weight, based on the weight. That is. By setting the use ratio of the dibasic ethylenically unsaturated carboxylic acid monomer within this range, it becomes possible to adjust the wet stickiness resistance to a better level, and most preferably a paper coating composition. From the viewpoint of improving the doctor blade cleaning properties, itaconic acid and acrylic acid are used in combination.
また、原料の１つである（ｃ）シアン化ビニル単量体は、耐湿潤ベタツキ性の向上に必須の成分であり、該共重合体を構成する全単量体を１００質量％とした場合、全単量体に対し１０〜３０質量％、好ましくは１３〜２８質量％、更に好ましくは１５〜２５質量％の割合で用いられる。この単量体の使用量を上記範囲に設定する事により、耐湿潤ベタツキ性を向上させる効果が得られ、かつ共重合体ラテックスの重合安定性を低下させる事がない。シアン化ビニル単量体の好ましい例としては、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などがあげられ、これらは１種または２種以上が組み合わせて用いられる。 In addition, (c) vinyl cyanide monomer, which is one of the raw materials, is an essential component for improving wet stickiness resistance, and when the total monomer constituting the copolymer is 100% by mass , 10 to 30% by mass, preferably 13 to 28% by mass, and more preferably 15 to 25% by mass, based on the total monomers. By setting the amount of the monomer used within the above range, the effect of improving the wet stickiness resistance is obtained, and the polymerization stability of the copolymer latex is not lowered. Preferable examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and the like, and these are used alone or in combination of two or more.
また、他の原料として（ｄ）上記単量体と共重合可能な他の単量体を含む。この共重合可能な他の単量体を適宜選択することにより、共重合体ラテックス及びその組成物にさまざまな特性を付与できる。共重合可能な他の単量体の好ましい例としては、スチレン、α−メチルスチレン、ビニルトルエン、ｐ−メチルスチレンなどの芳香族ビニル単量体、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、など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など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−ヒドロキシエチルなどのアクリル酸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などのアミノアルキルエステル類、２−ビニルピリジン、４−ビニルピリジンなどのピリジン類、アクリル酸グリシジル、メタクリル酸グリシジルなど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などのアミド類、酢酸ビニルなどのカルボン酸ビニルエステル類、塩化ビニルなどのハロゲン化ビニル類などがあげられ、これらは１種または２種以上が組み合わせて用いればよい。上記各種単量体の中でも、得られる共重合体ラテックスのピック強度及びドクターブレード洗浄性の観点から、スチレン、アクリル酸２−ヒドロキシエチル、メタクリル酸メチルを用いることが好ましい。 Further, as other raw materials, (d) other monomers copolymerizable with the above monomers are included. Various properties can be imparted to the copolymer latex and the composition thereof by appropriately selecting other copolymerizable monomers. Preferred examples of other copolymerizable monomers include aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, and p-methylstyrene, methyl acrylate, ethyl acrylate, butyl acrylate, Acrylic acid alkyl esters such as 2-ethylhexyl acrylate, alkyl methacrylates such as methyl methacrylate and butyl methacrylate, and hydroxyalkyl esters of acrylic acid such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate Aminoalkyl esters such as aminoethyl acrylate, dimethylaminoethyl acrylate and diethylaminoethyl acrylate, pyridines such as 2-vinylpyridine and 4-vinylpyridine, glycidyl acrylate and glycidyl methacrylate Sidyl esters, acrylamides, methacrylamides, N-methylol acrylamides, N-methyl acrylamides, N-methyl methacrylamides, glycidyl methacrylamides, N, N-butoxymethyl acrylamides and other carboxylic acid vinyl esters such as vinyl acetate And vinyl halides such as vinyl chloride. These may be used alone or in combination of two or more. Among the various monomers described above, styrene, 2-hydroxyethyl acrylate, and methyl methacrylate are preferably used from the viewpoint of the pick strength of the obtained copolymer latex and the doctor blade detergency.
この（ｄ）共重合可能な単量体は、共重合体ラテックスを構成する全単量体を１００質量％とした場合、全単量体に対し３〜６３．５質量％、好ましくは２３〜５０．５質量％の割合で用いられる。この単量体を上記範囲で使用する事で、好適なピック強度が発現する。 This (d) copolymerizable monomer is 3 to 63.5% by mass, preferably 23 to 30% by mass, based on 100% by mass of all monomers constituting the copolymer latex. It is used at a ratio of 50.5% by mass. By using this monomer in the above range, a suitable pick strength is exhibited.
本発明の共重合体ラテックスは、上記の単量体の混合物（ただし、（ａ）＋（ｂ）＋（ｃ）＋（ｄ）＝１００質量％）を乳化重合法により重合することで得られる。乳化重合後の共重合体ラテックス中に残存しているアクリル酸単量体の濃度は、該共重合体ラテックスの固形分に対して１００〜５０００ｐｐｍである事が必要である。ここで、共重合体ラテックスの固形分とは、共重合体ラテックスから水及びその他揮発成分を除去した残りの成分を言う。共重合体ラテックス中のアクリル酸単量体の濃度がこの範囲に入る事によって、共重合体ラテックスの耐湿潤ベタツキ性、塗工紙のピック強度、湿潤ピック強度及び初期耐水性、該共重合体ラテックスを用いた紙塗工組成物のドクターブレード洗浄性、以上の全ての物性を良好なレベルに引き上げる事が可能になる。これらの物性の観点から、好ましくは２００〜４０００ｐｐｍ、最も好ましくは３００〜３５００ｐｐｍの範囲に調整される事が望ましい。 The copolymer latex of the present invention is obtained by polymerizing a mixture of the above monomers (however, (a) + (b) + (c) + (d) = 100% by mass) by an emulsion polymerization method. . The concentration of the acrylic acid monomer remaining in the copolymer latex after the emulsion polymerization needs to be 100 to 5000 ppm with respect to the solid content of the copolymer latex. Here, the solid content of the copolymer latex refers to the remaining component obtained by removing water and other volatile components from the copolymer latex. When the concentration of the acrylic acid monomer in the copolymer latex falls within this range, the wet-stickiness resistance of the copolymer latex, the pick strength of the coated paper, the wet pick strength and the initial water resistance, the copolymer The doctor blade cleaning property of the paper coating composition using latex can be raised to a satisfactory level. From the viewpoint of these physical properties, it is preferably adjusted to a range of 200 to 4000 ppm, most preferably 300 to 3500 ppm.
共重合体ラテックス中のアクリル酸単量体の濃度は、幾つかの方法によって調整可能である。例えば原料としてアクリル酸を使用する場合には、他の原料単量体に対するその使用量割合、及び重合系内への添加時期及び／または添加速度を調整する事や、重合開始剤量、連鎖移動剤量、重合時間、重合温度を適正化する事で、アクリル酸単量体の重合転化率を調整し、最終製品としての共重合体ラテックス中のアクリル酸単量体濃度を適宜所望の範囲に調整する事が可能である。 The concentration of acrylic acid monomer in the copolymer latex can be adjusted by several methods. For example, when acrylic acid is used as a raw material, the ratio of the amount used relative to other raw material monomers, and the timing and / or rate of addition to the polymerization system, the amount of polymerization initiator, chain transfer By adjusting the amount of agent, polymerization time, and polymerization temperature, the polymerization conversion rate of acrylic acid monomer is adjusted, and the acrylic acid monomer concentration in the copolymer latex as the final product is appropriately adjusted to the desired range. It is possible to adjust.
また、原料としてアクリル酸を使用しない場合でも、最終製品としての共重合体ラテックス中にアクリル酸単量体を含有する事は事実上あり得る事であり、一例として（ｄ）の他の共重合可能な単量体として、特にアクリル酸アルキルエステル単量体またはアクリル酸ヒドロキシアルキルエステル単量体またはこれらの両者を用い、これらの加水分解率を調整すべく、重合温度や重合系内のｐＨを調整する事でやはり適宜所望の範囲に調整する事が可能である。更には共重合体ラテックスには、一般的に分散剤を代表とする各種の添加剤を添加する事が多いが、この際、使用する添加剤中に含まれるアクリル酸単量体濃度を適宜調整する事や、添加剤の添加量を調整する事、等も、本発明で必要な共重合体ラテックス中の単量体としてのアクリル酸濃度を所望の範囲に調整する手段の一つである。 Even when acrylic acid is not used as a raw material, it is practically possible that an acrylic acid monomer is contained in the copolymer latex as the final product. As a possible monomer, in particular, an acrylic acid alkyl ester monomer or an acrylic acid hydroxyalkyl ester monomer or both are used, and the polymerization temperature and the pH in the polymerization system are adjusted in order to adjust the hydrolysis rate thereof. By adjusting, it is possible to adjust to a desired range as appropriate. In addition, various additives such as dispersants are generally added to the copolymer latex. At this time, the concentration of the acrylic acid monomer contained in the additive used is appropriately adjusted. It is one of means for adjusting the concentration of acrylic acid as a monomer in the copolymer latex necessary in the present invention to a desired range.
共重合体ラテックスのガラス転移温度（Ｔｇ）は、特に限定されるものではないが、塗工紙用途におけるピック強度・湿潤ピック強度とラテックスの耐湿潤ベタツキ性を両立させる観点から、−２０℃〜＋４０℃の範囲内にあることが好ましく、より好ましくは−１５℃〜＋３５℃、さらに好ましくは−１０〜＋３０℃の範囲にあることである。なお、Ｔｇは、１種類の共重合体ラテックスにおいて１点だけに限定されず、複数のＴｇを有していても良い。 The glass transition temperature (Tg) of the copolymer latex is not particularly limited, but from the viewpoint of achieving both the pick strength / wet pick strength in coated paper applications and the wet stickiness resistance of the latex, from −20 ° C. It is preferably in the range of + 40 ° C, more preferably in the range of -15 ° C to + 35 ° C, and still more preferably in the range of -10 to + 30 ° C. Tg is not limited to one point in one type of copolymer latex, and may have a plurality of Tg.
共重合体ラテックスの粒子径は５０〜１５０ｎｍであることが好ましい。より好ましくは６０〜１１０ｎｍにあることが好適である。この範囲の粒子径に設定する事により、ラテックスの粘度を好適な範囲に調整する事が可能であり、作業性を低下せしめない。更には、ピック強度・湿潤ピック強度の低下や塗料粘度上昇発生を抑制させる事ができる。 The particle size of the copolymer latex is preferably 50 to 150 nm. More preferably, it is in the range of 60 to 110 nm. By setting the particle diameter within this range, the viscosity of the latex can be adjusted to a suitable range, and workability is not lowered. Furthermore, it is possible to suppress a decrease in pick strength / wet pick strength and an increase in paint viscosity.
共重合体ラテックスについては、共重合体中のゲル分率（トルエン不溶分）が７０〜９８質量％に有ることが好ましく、更に好ましくは８０〜９７質量％、最も好ましくは８８〜９４質量％の範囲にあることである。この範囲にゲル分率を調整する事によって、共重合体ラテックスの耐湿潤ベタツキ性と塗工紙のピック強度及び湿潤ピック強度を同時に向上させる事ができる。 About copolymer latex, it is preferable that the gel fraction (toluene insoluble content) in a copolymer exists in 70-98 mass%, More preferably, it is 80-97 mass%, Most preferably, it is 88-94 mass%. It is in range. By adjusting the gel fraction within this range, the wet stickiness resistance of the copolymer latex and the pick strength and wet pick strength of the coated paper can be simultaneously improved.
共重合体ラテックスの製造法は、従来商業的に用いられている乳化重合法の装置を使用して行われるものであるが、少なくとも二段の重合工程を含む多段重合法を取る事が好ましい。これにより目的の課題に対する効果がより大きくなる。多段重合法とは、例えば特開２００２−２２６５２４号公報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 copolymer latex is carried out using an emulsion polymerization method apparatus conventionally used commercially, but it is preferable to use a multi-stage polymerization method including at least a two-stage polymerization step. Thereby, the effect with respect to the target subject becomes larger. The multi-stage polymerization method is, for example, a monomer mixture prepared by preparing a plurality of monomer mixtures having different compositions and adding them to the system as the polymerization reaction proceeds, as disclosed in JP-A-2002-226524. Is a polymerization method in which the composition is changed during the polymerization reaction.
上記のような多段重合法を行う場合、本発明の共重合体ラテックスで目的とする効果を高める為には、各重合段の単量体混合物の組成が重要である。重合反応における時系列的な観点で整理した場合、最初の工程を第一重合段、これに続く工程を第二重合段、（更にこれに続く第三重合段以降が存在しても良い）と定義した場合に、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ガラス転移温度については、より後段の重合段ほど高いＴｇの得られる単量体混合物の組成にする事が望ましい。また第一重合段で用いる単量体混合物の量と、第二重合段以降の各重合段で用いられる単量体混合物合計量との質量比は、４０：６０〜８０：２０の範囲に入る事が好ましく、より好ましくは４５：５５〜６５：３５の範囲に入る事である。この範囲に入ることで共重合体ラテックスの耐湿潤ベタツキ性、及びこれを使用した塗工紙のピック強度・湿潤ピック強度と初期耐水性をより高める事ができる。最も好ましい範囲は、５５：４５〜６２：３８の範囲である。 When performing the multistage polymerization method as described above, the composition of the monomer mixture of each polymerization stage is important in order to enhance the intended effect of the copolymer latex of the present invention. When arranged from the viewpoint of time series in the polymerization reaction, the first process is the first polymerization stage, the subsequent process is the second polymerization stage, and the subsequent third polymerization stage may be present. As for the glass transition temperature of the copolymer obtained from the monomer mixture in each polymerization stage, it is desirable that the composition of the monomer mixture is such that a higher Tg is obtained in the subsequent polymerization stage. The mass ratio of the amount of the monomer mixture used in the first polymerization stage and the total amount of the monomer mixture used in each polymerization stage after the second polymerization stage falls within the range of 40:60 to 80:20. It is preferable that it falls within the range of 45:55 to 65:35. By entering this range, the wet stickiness resistance of the copolymer latex, and the pick strength / wet pick strength and initial water resistance of the coated paper using the copolymer latex can be further increased. The most preferred range is in the range of 55:45 to 62:38.
また、各重合段において用いられる単量体混合物（但し第二重合段以降で使用される二塩基性エチレン系不飽和カルボン酸単量体を除く）から得られる共重合体の溶解度パラメーター（ＳＰ値）に関して、ある重合段で用いられる単量体混合物組成から得られる共重合体のＳＰ値を基準として、その重合段の直後の重合段で用いられる単量体混合物組成から得られる共重合体のＳＰ値の増分（以下ΔＳＰ値と定義する。）が０．０１以上０．８以下の範囲に入る様、各重合重合段の単量体混合物組成が調整される事が好ましい。つまり、隣接する重合段の各ＳＰ値がこの差を有していることが好ましい。このΔＳＰ値が０．０１以上０．８以下の範囲に入る事によって、耐湿潤ベタツキ性とピック強度、湿潤ピック強度のいずれにも優れる共重合体ラテックスが得られる。ΔＳＰ値のより好ましい範囲は、０．１以上０．６以下、更に好ましい範囲は０．２以上０．５以下である。各重合段のＳＰ値の調整は、単量体混合物を構成する単量体の種類と量で実施可能であるが、特に、ＳＰ値が低い（ａ）共役ジエン系単量体と、ＳＰ値が高い（ｃ）シアン化ビニル単量体の使用量割合が重要な因子である。 The solubility parameter (SP value) of the copolymer obtained from the monomer mixture used in each polymerization stage (excluding the dibasic ethylenically unsaturated carboxylic acid monomer used in the second polymerization stage and thereafter) ) With respect to the SP value of the copolymer obtained from the monomer mixture composition used in a certain polymerization stage, the copolymer obtained from the monomer mixture composition used in the polymerization stage immediately after that polymerization stage. It is preferable that the monomer mixture composition of each polymerization polymerization stage is adjusted so that the SP value increment (hereinafter referred to as ΔSP value) falls within the range of 0.01 to 0.8. That is, it is preferable that the SP values of the adjacent polymerization stages have this difference. When this ΔSP value falls within the range of 0.01 or more and 0.8 or less, a copolymer latex excellent in all of wet stickiness resistance, pick strength, and wet pick strength can be obtained. A more preferable range of the ΔSP value is 0.1 or more and 0.6 or less, and a more preferable range is 0.2 or more and 0.5 or less. The SP value of each polymerization stage can be adjusted by the type and amount of monomers constituting the monomer mixture. In particular, (a) a conjugated diene monomer having a low SP value, and an SP value. (C) The amount of vinyl cyanide monomer used is a significant factor.
更に、カルボン酸の使用方法をある特定の条件下に限定することが好ましい。前述の様に、原料単量体として二塩基性エチレン系不飽和カルボン酸単量体と一塩基性エチレン系不飽和カルボン酸単量体とを併用して使用する事が好ましいが、この二塩基性エチレン系不飽和カルボン酸単量体については、重合開始時点で系内に存在する量と重合開始後に系内に後添加する量との比、および系内に後添加するタイミングが重要である。 Furthermore, it is preferable to limit the method of using the carboxylic acid under certain specific conditions. As described above, it is preferable to use a dibasic ethylenically unsaturated carboxylic acid monomer and a monobasic ethylenically unsaturated carboxylic acid monomer in combination as a raw material monomer. For the unsaturated ethylenically unsaturated carboxylic acid monomer, the ratio of the amount present in the system at the start of polymerization to the amount added after the start of polymerization into the system, and the timing of post-addition into the system are important. .
即ち、二塩基性エチレン系不飽和カルボン酸単量体量の少なくとも６０質量％以上は、第二重合段以降で、かつその時点までに系内に添加された単量体の重合転化率が６５〜９５質量％の範囲内にあるいずれかの時点から系内に後添加を開始する事が好ましく、この条件が満たされる事によって、得られる共重合体ラテックスはより良好な耐湿潤ベタツキ性を得ることが可能となり、この共重合体ラテックスを使用した紙塗工組成物はより良好な塗工操業性を有する。系内に後添加される二塩基性エチレン系不飽和カルボン酸単量体量割合のより好ましい範囲は８０質量％以上であり、最も好ましくは９０質量％以上である。この工程で使用される二塩基性エチレン系不飽和カルボン酸単量体の量は、使用する全単量体を１００質量部とした場合に、１．５〜３．５質量部に入る事が好ましい。系内に後添加する二塩基性エチレン系不飽和カルボン酸単量体の割合、及び量がこの範囲にはいる事で、共重合体ラテックスはより高い耐湿潤ベタツキ性を有することが可能となる。 That is, at least 60% by mass or more of the amount of the dibasic ethylenically unsaturated carboxylic acid monomer is such that the polymerization conversion rate of the monomer added to the system after the second polymerization stage and before that point is 65%. It is preferable to start post-addition into the system at any point in the range of ~ 95% by mass, and when this condition is satisfied, the copolymer latex obtained has better wet-sticking resistance. The paper coating composition using this copolymer latex has better coating operability. A more preferable range of the amount ratio of the dibasic ethylenically unsaturated carboxylic acid monomer added later in the system is 80% by mass or more, and most preferably 90% by mass or more. The amount of the dibasic ethylenically unsaturated carboxylic acid monomer used in this step may be in the range of 1.5 to 3.5 parts by mass when the total monomer used is 100 parts by mass. preferable. The ratio and amount of the dibasic ethylenically unsaturated carboxylic acid monomer added later in the system are within this range, so that the copolymer latex can have higher wet-sticking resistance. .
後添加される二塩基性エチレン系不飽和カルボン酸単量体の系内への後添加開始時期は、その時点までに系内に添加された他の単量体の重合転化率が７０〜９０質量％になったいずれかの時点から、系内に後添加開始される事がより好ましい。 The post-addition start timing of the post-added dibasic ethylenically unsaturated carboxylic acid monomer into the system is such that the polymerization conversion rate of other monomers added to the system up to that point is 70 to 90 It is more preferable to start the post-addition into the system from any point when the mass% is reached.
また、後添加される二塩基性エチレン系不飽和カルボン酸単量体の添加方法については、第二重合段以降の単量体混合物中に（必要なら予め乳化して）混合する方法、単量体混合物とは別途、単独で系内に添加する方法等があるが、得られる共重合体ラテックスの耐湿潤ベタツキ性を良好なレベルにする為に、或いは他の単量体の重合転化率が適切となる時点から添加を開始する為には、二塩基性エチレン系不飽和カルボン酸単量体を単独で水溶液化し、他の単量体混合物とは別途独立して系内に添加する事が好ましい。後添加する二塩基性エチレン系不飽和カルボン酸単量体の水溶液濃度は５〜３０質量％、好ましくは１０〜２０質量％の範囲にあることが、量産設備での効率を考慮すると好ましい。また系内に添加される前に二塩基性エチレン系不飽和カルボン酸単量体の変質や重合を抑制し、系内に添加された後の系内の温度を安定化させる為には、この水溶液の温度は、３０〜８０℃、好ましくは４０〜６５℃の範囲にある事が好ましい。 The addition method of the dibasic ethylenically unsaturated carboxylic acid monomer to be added later is a method of mixing in a monomer mixture after the second polymerization stage (emulsified in advance if necessary), single amount In addition to the body mixture, there is a method of adding it alone into the system, etc., but in order to make the resulting copolymer latex have a good level of wet stickiness resistance, or the polymerization conversion rate of other monomers In order to start the addition from the appropriate point of time, the dibasic ethylenically unsaturated carboxylic acid monomer can be made into an aqueous solution alone and added to the system separately from the other monomer mixture. preferable. The aqueous solution concentration of the dibasic ethylenically unsaturated carboxylic acid monomer to be added later is preferably in the range of 5 to 30% by mass, and preferably in the range of 10 to 20% by mass, considering the efficiency in mass production facilities. In order to suppress the alteration and polymerization of the dibasic ethylenically unsaturated carboxylic acid monomer before being added to the system, and to stabilize the temperature in the system after being added to the system, The temperature of the aqueous solution is preferably 30 to 80 ° C, preferably 40 to 65 ° C.
系内に後添加する二塩基性エチレン系不飽和カルボン酸単量体の添加に要する時間は、後添加開始から４５〜１２０分をかけて全量を系内に添加する事が好ましく、この範囲の時間で系内に後添加することにより、得られる共重合体ラテックスの耐湿潤ベタツキ性が優れる。 The time required for the addition of the dibasic ethylenically unsaturated carboxylic acid monomer to be added later to the system is preferably 45 to 120 minutes from the start of the post-addition, and the entire amount is preferably added to the system. By adding it to the system over time, the resulting copolymer latex is excellent in wet stickiness resistance.
共重合体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制限はなく、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などの方法を用いることができる。 In producing the copolymer latex, there is no particular limitation except for the specific method described above, and a method of performing polymerization with a radical initiator in the presence of a surfactant in an aqueous medium can be used.
使用する乳化剤についても特に制限はなく、従来公知のアニオン、カチオン、両性および非イオン性の界面活性剤を用いることができる。好ましい界面活性剤の例としては、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など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などのノニオン性界面活性剤があげられ、これらは単独または２種以上を組み合わせて用いられる。使用される界面活性剤の量は、単量体１００質量部当たり、０．３〜２．０質量部である事が好ましい。 There is no restriction | limiting in particular also about the emulsifier to use, A conventionally well-known anion, a cation, an amphoteric, and a nonionic surfactant can be used. Examples of preferred surfactants include anionic surfactants such as aliphatic soaps, rosin acid soaps, alkyl sulfonates, alkyl sulfosuccinates, polyoxyethylene alkyl sulfates, polyoxyethylene alkyl ethers, polyoxyethylenes Nonionic surfactants such as alkyl allyl ether and polyoxyethylene oxypropylene block copolymer are listed, and these are used alone or in combination of two or more. The amount of the surfactant used is preferably 0.3 to 2.0 parts by mass per 100 parts by mass of the monomer.
ラジカル開始剤は、熱また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り、無機系開始剤、有機系開始剤のいずれも使用することが可能である。好ましい例としてはペルオキソ二硫酸塩、過酸化物、アゾビス化合物などがあり、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、クメンハイドロパーオキサイドなどがあげられ、これらは単独または２種以上を組み合わせて用いることができる。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、ロンガリットなど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 initiates addition polymerization of the monomer by radical decomposition in the presence of heat or a reducing agent, and either an inorganic initiator or an organic initiator can be used. Preferable examples include peroxodisulfate, peroxide, azobis compound, etc., specifically potassium peroxodisulfate, sodium peroxodisulfate, ammonium peroxodisulfate, hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide 2,2-azobisbutyronitrile, cumene hydroperoxide and the like, and these can be used alone or in combination of two or more. Further, 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.
共重合体ラテックスを製造する場合、ラジカル重合において通常用いられる公知の連鎖移動剤を用いることが可能である。連鎖移動剤の好ましい例としては、核置換α−メチルスチレンの二量体のひとつである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などのメルカプタン類、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などのジスルフィド類、四塩化炭素、四臭化炭素など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などがあげられ、これらは単独または２種以上を組み合わせて用いることができる。連鎖移動剤の添加方法にも特に制限はなく、一括添加、回分添加、連続添加など公知の添加方法が用いられる。 When producing the copolymer latex, it is possible to use a known chain transfer agent usually used in radical polymerization. Preferred examples of the chain transfer agent include α-methylstyrene dimer, n-butyl mercaptan, t-butyl mercaptan, n-octyl mercaptan, n-lauryl mercaptan, which is one of dimers of nucleus-substituted α-methylstyrene. Examples include mercaptans, disulfides such as tetramethylthiudium disulfide and tetraethylthuradium disulfide, halogenated derivatives such as carbon tetrachloride and carbon tetrabromide, and 2-ethylhexyl thioglycolate. These may be used alone or in combination. Can be used in combination. The addition method of the chain transfer agent is not particularly limited, and known addition methods such as batch addition, batch addition, and continuous addition are used.
共重合体ラテックスを製造する場合の重合温度は、特に制約はなく、通常４０〜１００℃の範囲で行う事が一般的であるが、生産効率と、得られる共重合体ラテックス及びその組成物のピック強度等の品質の観点からは、重合開始時から単量体混合物の添加終了時までの期間においては、５５〜８５℃の範囲が好ましく、より好ましくは６０〜８０℃の範囲である。また全単量体を重合系内に添加終了後に、各単量体の重合転化率を引き上げる為に、重合温度を上げる方法（いわゆるクッキング工程）を設ける事も可能であり、この工程の重合温度は８０〜１００℃の範囲にある事が好ましい。 The polymerization temperature for producing the copolymer latex is not particularly limited, and it is generally performed in the range of 40 to 100 ° C., but the production efficiency and the obtained copolymer latex and the composition thereof are not limited. From the viewpoint of quality such as pick strength, the period from the start of polymerization to the end of addition of the monomer mixture is preferably in the range of 55 to 85 ° C, more preferably in the range of 60 to 80 ° C. It is also possible to provide a method of raising the polymerization temperature (so-called cooking process) in order to increase the polymerization conversion rate of each monomer after the addition of all the monomers in the polymerization system. Is preferably in the range of 80 to 100 ° C.
共重合体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、３５〜６０質量％、更に好ましくは４０〜５２質量％である。ここにいう固形分濃度とは、乾燥により得られた固形分質量の、元の共重合体ラテックス質量に対する割合を言う。 The polymerization solid content concentration in the case of producing the copolymer latex is 35 to 60% by mass, more preferably 40 to 52% by mass, from the viewpoint of production efficiency and particle diameter control during emulsion polymerization. The solid content concentration mentioned here refers to the ratio of the solid content mass obtained by drying to the original copolymer latex mass.
共重合体ラテックスを製造するにあたって、乳化重合の系内に（各重合段）の単量体混合物を添加する手段に関しては、上記で説明した方法以外には特に制約はない。単量体混合物の一部を一括して予め乳化重合系内に仕込み重合した後、残りの単量体混合物を連続的もしくは間欠的に仕込む方法、あるいは単量体混合物を各重合段の最初から連続的または間欠的に仕込む方法を採りうるものであり、これらの重合方法を組み合わせて重合してもよいが、商業生産ベースにおいて、発生する重合熱の除去の観点から、製品の生産性を考慮した場合に、全単量体混合物の８０質量％以上については、連続的に系内に添加する方法が好ましい。 In producing the copolymer latex, there are no particular restrictions on the means for adding the monomer mixture (each polymerization stage) to the emulsion polymerization system other than the method described above. A method in which a part of the monomer mixture is charged into the emulsion polymerization system in advance and polymerized, and then the remaining monomer mixture is charged continuously or intermittently, or the monomer mixture is added from the beginning of each polymerization stage. A method of charging continuously or intermittently may be adopted, and polymerization may be performed by combining these polymerization methods. However, in terms of removal of heat of polymerization generated on a commercial production basis, product productivity is considered. In such a case, a method of continuously adding 80% by mass or more of the total monomer mixture into the system is preferable.
共重合体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可能であり、シードを作製後同一反応系内で共重合体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などの方法を適宜選択して用いることができる。 In the production of the copolymer latex, it is also possible to use a known seed polymerization method for adjusting the particle size, and an internal seed method in which the copolymer latex is polymerized in the same reaction system after the seed is prepared. A method such as an external seed method using the produced seed can be appropriately selected and used.
共重合体ラテックスには、必要に応じて公知の各種重合調整剤を用いることができる。これらはたとえばｐＨ調整剤、キレート剤などであり、ｐＨ調整剤の好ましい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などがあげられ、キレート剤の好ましい例としてはエチレンジアミン四酢酸ナトリウムなどがあげられる。 Various known polymerization regulators can be used for the copolymer latex as required. These are, for example, pH adjusters, chelating agents, etc. Preferred examples of pH adjusting agents include sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium hydrogen carbonate, disodium hydrogen phosphate, and the like. Preferable examples include sodium ethylenediaminetetraacetate.
共重合体ラテックスの、最終製品としての固形分濃度についても特に制限はなく、通常固形分濃度は３０〜６０質量％の範囲に希釈もしくは濃縮して調製される。 There is no restriction | limiting in particular also about the solid content concentration as a final product of copolymer latex, Usually, solid content concentration is diluted or concentrated in the range of 30-60 mass%, and is prepared.
共重合体ラテックスには、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、あるいは他のラテックスを混合して用いることが可能であり、例えば分散剤、消泡剤、老化防止剤、耐水化剤、殺菌剤、印刷適性剤、滑剤などを添加すること、アルカリ感応型ラテックス、有機顔料などを混合して用いることもできる。但し上記の様に各種添加剤及び／又は他のラテックスが混合された状態においても、含有される単量体としてのアクリル酸は、共重合体ラテックスの固形分に対して１００〜５０００ｐｐｍの範囲に入る事が必要である。 Various additives can be added to the copolymer latex as needed, or other latex can be mixed and used as long as the effect is not impaired. For example, a dispersant, an antifoaming agent, aging, etc. Inhibitors, water-proofing agents, bactericides, printability agents, lubricants, and the like, alkali-sensitive latexes, organic pigments and the like can also be mixed and used. However, even when various additives and / or other latexes are mixed as described above, the acrylic acid as the monomer contained is in the range of 100 to 5000 ppm with respect to the solid content of the copolymer latex. It is necessary to enter.
次に、前述の共重合体ラテックスを紙塗工用塗料のバインダーとして用いることにより紙塗工組成物が得られる。これは、通常行われている実施態様で製造することができる。すなわち、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、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、保水剤等の各種添加剤とともに共重合体ラテックス組成物を添加して混合し、均一な分散液（紙塗工組成物）とする態様である。 Next, a paper coating composition is obtained by using the above-mentioned copolymer latex as a binder for a paper coating paint. This can be produced in the usual manner. That is, 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, and polyvinyl alcohol Add copolymer latex composition together with various additives such as water-soluble polymers such as carboxymethylcellulose, thickeners, dyes, antifoaming agents, preservatives, water resistance agents, lubricants, printability improvers, water retention agents, etc. And mixing to form a uniform dispersion (paper coating composition).
ここで、本発明の共重合体ラテックスは、紙塗工組成物を構成する顔料について、その平均粒子径が小さいものを主として用いた場合に使用する事が好ましく、この時に特に顕著なピック強度、湿潤ピック強度及び初期耐水性の改良効果を発現することが可能となる。即ち、カオリンクレーと重質炭酸カルシウムを必須成分とし、カオリンクレーについては粒子径が２μｍ以下のものが８０質量％以上であるもの、炭酸カルシウムについては粒子径が２μｍ以下のものが８０質量％以上であるものを、顔料として用いる場合にその効果がより顕著となる。即ち、本発明以外の共重合体ラテックスとの効果の差異が拡大するのである。その理由は定かではないが、本発明の共重合体ラテックスは最適な単量体組成を有し、最適量のアクリル酸単量体を含有している為に、顔料との吸着効果が促進され、特に良好な接着強度が発現するものと推定している。更には親水性の強いアクリル酸単量体の適正量を含むが故に、フロークリン水に対する再分散性が高まり、特に優れたドクターブレード洗浄性を発現するものと推定している。 Here, the copolymer latex of the present invention is preferably used when the pigment constituting the paper coating composition is mainly used when the average particle size is small. It is possible to develop an effect of improving wet pick strength and initial water resistance. That is, kaolin clay and heavy calcium carbonate are essential components, kaolin clay having a particle size of 2 μm or less is 80% by mass, and calcium carbonate having a particle size of 2 μm or less is 80% by mass or more. The effect becomes more prominent when the above is used as a pigment. That is, the difference in effect with the copolymer latex other than the present invention is expanded. The reason is not clear, but the copolymer latex of the present invention has an optimal monomer composition and contains an optimal amount of acrylic acid monomer, so that the adsorption effect with the pigment is promoted. It is estimated that particularly good adhesive strength is developed. Furthermore, since it contains an appropriate amount of acrylic acid monomer having a strong hydrophilic property, it is estimated that redispersibility with respect to flow clean water is enhanced, and particularly excellent doctor blade cleaning properties are exhibited.
顔料と共重合体ラテックス組成物との使用割合は、組成物の使用目的によって適宜決定することが出来るが、顔料１００質量部に対して共重合体ラテックス組成物３〜３０質量部を用いる事が好ましい。そして、この紙塗工組成物は、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、バーコーターなど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が、ブレードコーターを用いる事が好ましい。塗工形態も原紙に対し片面、又は表裏の両面に塗工されうるものであり、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の他、２回の塗工工程を行ういわゆるダブル塗工に供する事もできる。この場合、共重合体ラテックス組成物はその下塗り用顔料組成物、及び上塗り用顔料組成物のいずれにも用いる事ができる。 The use ratio of the pigment and the copolymer latex composition can be appropriately determined depending on the purpose of use of the composition, but 3 to 30 parts by mass of the copolymer latex composition may be used with respect to 100 parts by mass of the pigment. preferable. 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, but it is preferable to use a blade coater. The coating form can be applied to one side of the base paper, or both sides of the front and back sides, and the number of times of coating per side is one so that the coating process is performed twice, in addition to single coating. It can also be used for double coating. In this case, the copolymer latex composition can be used for both the undercoat pigment composition and the overcoat pigment composition.
次に、前述の紙塗工組成物を用いて、印刷用紙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、凸版式印刷用紙、フレキソ印刷用紙等の各種印刷用紙及び板紙、ダンボール用紙、包装紙等に好適に用いられるが、特にオフセット枚葉式印刷用紙及びオフセット輪転式印刷用紙に用いられる事が望ましい。 Next, using the above-mentioned paper coating composition, a coating paper for printing can be obtained by coating the surface of the printing paper. This coated paper is suitable for various types of printing paper such as offset sheet-fed printing paper, offset rotary printing paper, gravure printing paper, letterpress printing paper, flexographic printing paper, board, cardboard paper, wrapping paper, etc. In particular, it is desirable to use for offset sheet-fed printing paper and offset rotary printing paper.
更に、上述の共重合体ラテックス組成物は、紙のコーティング剤、カーペットバッキング剤、その他接着剤、各種塗料にも用いる事ができる。 Furthermore, the above-mentioned copolymer latex composition can also be used for paper coating agents, carpet backing agents, other adhesives, and various paints.
以下、本発明を実施例に基づいて説明するが、本発明はこれらの実施例の具体的態様に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to the specific aspect of these Examples.
［各物性の評価方法］
（１）ピック強度：
[Evaluation method of each physical property]
(1) Pick strength:
ＲＩ印刷試験機（明製作所製）を用いて、印刷インク（Ｔ＆Ｋ ＴＯＫＡ社製、商品名ＳＤスーパーデラックス５０紅Ｂ、タック１８）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、その状態を観察した。評価は１０点評価法とし、ピッキング現象の少ないものほど高得点とした。
（２）湿潤ピック強度：
Using an RI printing tester (Meiji Seisakusho), 0.4 cc of printing ink (trade name SD Super Deluxe 50 Red B, Tack 18) manufactured by T & K TOKA is printed once, and the picking state that appears on the rubber roll is separated. The backing was backed and the state was observed. The evaluation was based on a 10-point evaluation method, and the smaller the picking phenomenon, the higher the score.
(2) Wet pick strength:
ＲＩ印刷試験機（明製作所製）を用いてスリーブロールで塗工紙表面に給水し、その直後に印刷インク（Ｔ＆Ｋ ＴＯＫＡ社製ＳＤスーパーデラックス５０紅Ｂ；タック１５）０．４ｃｃ１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、その状態を観察した。評価は１０点評価法とし、ピッキング現象の少ないものほど高得点とした。
（３）紙塗工組成物のドクターブレード洗浄性：
Water was applied to the surface of the coated paper with a sleeve roll using an RI printing tester (manufactured by Meisei Seisakusho). Immediately after that, printing ink (SD Super Deluxe 50 Red B; Tack 15 manufactured by T & K TOKA) was printed 0.4 cc once. The picking state that appeared on the rubber roll was backed on another mount and the state was observed. The evaluation was based on a 10-point evaluation method, and the smaller the picking phenomenon, the higher the score.
(3) Doctor blade cleaning properties of paper coating composition:
枚葉式ブレードコーター（エスエムテイ株式会社製；ＰＭ−９０４０ＭＣＡ）を用いた。天然ゴム製のシートをこのコーターのステージ上にセットし、シート上に固形分換算で２ｇの紙塗工組成物を乗せ、Ｎｏ．１０のワイヤーバーでシート上に一定量を塗布し、１００℃で２０ｓｅｃ乾燥させる。次に紙塗工組成物の塗布面上に、Ｎｏ．１４のワイヤーバーを用いて２ｇの水を塗布し、直後にブレードで掻き取り操作を行う。ブレード圧力は０．２ＭＰａ、掻き取り速度は５０ｍ／分に固定した。ブレードで掻き取られた後の、シート上に残留した紙塗工組成物の量を目視で観察した。評価は１０点評価法とし、残留量の少ないものほど高得点とした。
（４）塗工紙の初期耐水性
A single-wafer blade coater (manufactured by SMT Corp .; PM-9040MCA) was used. A sheet made of natural rubber was set on the stage of this coater, and 2 g of a paper coating composition in terms of solid content was placed on the sheet. A fixed amount is applied onto the sheet with 10 wire bars and dried at 100 ° C. for 20 seconds. Next, on the coated surface of the paper coating composition, no. 2 g of water is applied using a 14 wire bar, and immediately after that, scraping operation is performed with a blade. The blade pressure was fixed at 0.2 MPa, and the scraping speed was fixed at 50 m / min. The amount of the paper coating composition remaining on the sheet after scraping with a blade was visually observed. Evaluation was based on a 10-point evaluation method, and the smaller the residual amount, the higher the score.
(4) Initial water resistance of coated paper
上記の枚葉式ブレードコーターを用い、同一原紙上にそれぞれの紙塗工組成物を一定量塗布し、（３）と同一の条件で乾燥させた。その直後に、３０℃の水中に５秒間浸漬させておいた黒ラシャ紙をこの塗工紙に重ね合わせ、温度８０℃、線圧１９６００Ｎ／ｍのスーパーカレンダーを通過させた後、黒ラシャ紙を剥離する。この黒ラシャ紙に転移した塗工層成分の転移状態を目視評価した。評価は１０点評価法で行い、転移の少ないものほど高得点とした。
（５）紙塗工組成物の耐湿潤ベタツキ性：
A fixed amount of each paper coating composition was applied on the same base paper using the above-described single-wafer blade coater, and dried under the same conditions as in (3). Immediately after that, the black lasha paper that had been immersed in 30 ° C water for 5 seconds was superimposed on this coated paper, passed through a super calendar at a temperature of 80 ° C and a linear pressure of 19600 N / m, and then the black lasha paper was Peel off. The transferred state of the coating layer component transferred to the black rush paper was visually evaluated. The evaluation was performed by a 10-point evaluation method, and the smaller the transition, the higher the score.
(5) Wet stickiness resistance of paper coating composition:
紙塗工組成物を、Ｎｏ．１２のワイヤーバーでマイラーフィルムに塗布して１３０℃で３０秒乾燥した。このフィルムを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、黒ラシャ紙を剥離する。この黒ラシャ紙繊維のラテックスフィルムのベタツキによる転移状態を目視評価した。評価は１０点評価法で行い、転移の少ないものほど高得点とした。
（６）共重合体ラテックス中に含有される単量体としてのアクリル酸濃度
The paper coating composition is designated No. It applied to the mylar film with 12 wire bars and dried at 130 ° C. for 30 seconds. This film is immersed in water at 30 ° C. for 5 seconds, then superimposed on black lasha paper, passed through a super calender having a temperature of 60 ° C. and a linear pressure of 19600 N / m, and then the black lasha paper is peeled off. The state of transition of the black lasha paper fiber latex film due to stickiness was visually evaluated. The evaluation was performed by a 10-point evaluation method, and the smaller the transition, the higher the score.
(6) Acrylic acid concentration as a monomer contained in the copolymer latex
固形分濃度が５０質量％に調整された共重合体ラテックス１．５ｇを採取し、純水４０ｇを添加して希釈する。次いでこの希釈された共重合体ラテックスに、硫酸バンド０．２ｇを添加・混合し、共重合体ラテックスの固形分を沈降させ、濾過して分離する。この操作で共重合体ラテックス中に含有されていた単量体としてのアクリル酸は、全て上澄み水溶液中に含まれる。液体クロマトグラフィー（島津製作所株式会社製ＬＣ−１０ＡＤ型）を使用し、得られた上澄み水溶液中のアクリル酸単量体の濃度を求める。この値と、前述の希釈操作後の共重合体ラテックスの固形分濃度から、共重合体ラテックスの固形分に対しての単量体としてのアクリル酸濃度（ｐｐｍ）を算出した。
（７）共重合体ラテックスの粒子径：
1.5 g of copolymer latex whose solid content concentration is adjusted to 50% by mass is collected, and diluted by adding 40 g of pure water. Next, 0.2 g of sulfuric acid band is added to and mixed with the diluted copolymer latex, and the solid content of the copolymer latex is allowed to settle, followed by filtration and separation. All acrylic acid as a monomer contained in the copolymer latex by this operation is contained in the supernatant aqueous solution. Using liquid chromatography (LC-10AD type, manufactured by Shimadzu Corporation), the concentration of the acrylic acid monomer in the obtained supernatant aqueous solution is determined. From this value and the solid content concentration of the copolymer latex after the dilution operation described above, the acrylic acid concentration (ppm) as a monomer relative to the solid content of the copolymer latex was calculated.
(7) Particle diameter of copolymer latex:
動的光散乱法により、光散乱光度計（シーエヌウッド社製、モデル６０００）を用いて、初期角度４５度−測定角度１３５度で測定した。
（８）共重合体ラテックスのゲル分率：
Measurement was performed by a dynamic light scattering method using a light scattering photometer (Model 6000, manufactured by CNN Wood) at an initial angle of 45 degrees and a measurement angle of 135 degrees.
(8) Gel fraction of copolymer latex:
２倍に希釈したラテックスを１３０℃で３０分間乾燥しラテックスフィルムを得る。このラテックスフィルムを０．５ｇとり秤量する。これをトルエン３０ｍｌと混合して３時間浸透したのち、目開き３２μｍの金属網にてろ過した場合の残留物の乾燥質量を秤量する。もとのラテックスフィルム質量に対する残留物の乾燥質量の割合をゲル分率（質量％）とする。
（９）系内に添加された単量体混合物の重合転化率：
The latex diluted twice is dried at 130 ° C. for 30 minutes to obtain a latex film. 0.5 g of this latex film is taken and weighed. This is mixed with 30 ml of toluene and infiltrated for 3 hours, and then the dry mass of the residue is weighed when filtered through a metal net having an opening of 32 μm. The ratio of the dry mass of the residue to the original latex film mass is defined as the gel fraction (% by mass).
(9) Polymerization conversion rate of monomer mixture added in the system:
反応の任意時間で重合槽（耐圧反応容器）から取り出したサンプルを熱風乾燥機中で１３０℃で１時間乾燥し、乾燥前重量と乾燥後重量から固形分濃度（％）を求める。次に、下記式（１）により重合転化率を求める。 A sample taken out from the polymerization tank (pressure-resistant reaction vessel) at an arbitrary time of reaction is dried in a hot air dryer at 130 ° C. for 1 hour, and the solid content concentration (%) is obtained from the weight before drying and the weight after drying. Next, the polymerization conversion rate is determined by the following formula (1).
重合転化率（％）＝１００×（固形分濃度−不揮発分濃度）／揮発分濃度・・（１）
（ここに、不揮発分濃度とは、サンプル採取時までに反応系内に添加した単量体混合物中の開始剤、乳化剤、カルボン酸などの揮発しない成分の質量割合（％）の合計値であり、揮発分濃度とは、サンプル採取時までに反応系内に添加した単量体混合物中のブタジエン、スチレンなどの揮発成分の質量割合（％）の合計値である。）
（１０）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：
Polymerization conversion rate (%) = 100 × (solid content concentration−nonvolatile content concentration) / volatile content concentration (1)
(Here, the non-volatile content concentration is a total value of mass ratios (%) of non-volatile components such as initiator, emulsifier, and carboxylic acid in the monomer mixture added to the reaction system by the time of sampling. The volatile concentration is the total value of the mass ratio (%) of volatile components such as butadiene and styrene in the monomer mixture added to the reaction system by the time of sampling.)
(10) SP value of the copolymer obtained from the monomer mixture in each polymerization stage:
Ｒｏｂｅｒｔ Ｆ．Ｆｅｄｏｒｓが規定する方法により、各々の単量体化合物構造と単量体組成から算出した。（ＰＯＬＹＭＥＲ ＥＮＧＩＮＮＥＥＲＩＮＧ ＡＮＤ ＳＣＩＥＮＣＥ，１９７４，Ｖｏｌ．１４，Ｎｏ．２，１４７−１５４ｐａｇｅ参照）
［実施例１］
○共重合体ラテックスの製造
Robert F. Each monomer compound structure and monomer composition were calculated by the method prescribed by Fedors. (Refer to POLYMER ENGINNEERING AND SCIENCE, 1974, Vol. 14, No. 2, 147-154 pages)
[Example 1]
○ Manufacture of copolymer latex
耐圧反応容器に、重合初期の原料として水１２０質量部、ドデシルベンゼンスルホン酸ナトリウム０．５質量部、イタコン酸１．５質量部、及びα−メチルスチレンダイマー０．５質量部を含む重合初期原料を一括して仕込み、６０℃にて十分に攪拌した。次いで、予め調整しておいたスチレン３５質量部、ブタジエン３４質量部、メタクリル酸メチル７質量部、アクリロニトリル１８質量部、２−ヒドロキシエチルアクリレート３質量部、アクリル酸１．５質量部、α−メチルスチレンダイマー０．５質量部、及びｔ−ドデシルメルカプタン０．０３質量部からなる単量体及び連鎖移動剤混合物を、耐圧容器内に連続的に添加開始し、７時間で全量を添加した。一方、上記単量体及び連鎖移動剤混合物の添加開始と同時に、水１２質量部、ペルオキソ二硫酸ナトリウム０．５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０．５質量部、及び水酸化ナトリウム０．２質量部からなる水系混合物の添加を開始し、３時間３０分かけて連続的に添加し、重合反応を開始させた。単量体及び連鎖移動剤混合物の添加終了後、耐圧容器内の温度を９５℃に昇温させ、２時間重合反応を継続させて各単量体の重合転化率を高めた。全単量体の最終的な重合転化率は９９．１質量％であった。 Polymerization initial raw material containing 120 parts by weight of water, 0.5 part by weight of sodium dodecylbenzenesulfonate, 1.5 parts by weight of itaconic acid, and 0.5 part by weight of α-methylstyrene dimer in the pressure resistant reactor Were charged together and stirred sufficiently at 60 ° C. Next, 35 parts by mass of styrene prepared in advance, 34 parts by mass of butadiene, 7 parts by mass of methyl methacrylate, 18 parts by mass of acrylonitrile, 3 parts by mass of 2-hydroxyethyl acrylate, 1.5 parts by mass of acrylic acid, α-methyl A monomer and chain transfer agent mixture consisting of 0.5 parts by mass of styrene dimer and 0.03 parts by mass of t-dodecyl mercaptan was continuously added into the pressure vessel, and the whole amount was added in 7 hours. Meanwhile, simultaneously with the start of addition of the monomer and chain transfer agent mixture, 12 parts by weight of water, 0.5 parts by weight of sodium peroxodisulfate, 0.5 parts by weight of sodium dodecyl diphenyl ether disulfonate, and 0.2% of sodium hydroxide The addition of an aqueous mixture consisting of parts by mass was started and continuously added over 3 hours and 30 minutes to start the polymerization reaction. After the addition of the monomer and chain transfer agent mixture, the temperature in the pressure vessel was raised to 95 ° C., and the polymerization reaction was continued for 2 hours to increase the polymerization conversion rate of each monomer. The final polymerization conversion of all monomers was 99.1% by mass.
この共重合体ラテックスには、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、分散剤としてポリアクリル酸ナトリウムを共重合体ラテックスの固形分１００質量部当たり１質量部添加し、水酸化ナトリウムを用いてｐＨを８．０に調整し、最後に固形分濃度を５０質量％に調整した。この共重合体ラテックスを３２５メッシュのフィルターを通過させて濾過し、各物性評価に用いた。この共重合体ラテックスをＡとする。共重合体ラテックスＡの各物性の評価結果を表１に記載した。優れた耐湿潤ベタツキ性が得られた。
○紙塗工組成物の調製
To this copolymer latex, potassium hydroxide and sodium hydroxide are added to adjust the pH to 6.0, and unreacted monomers are removed by a steam stripping method. Sodium was added in an amount of 1 part by mass per 100 parts by mass of the copolymer latex, the pH was adjusted to 8.0 using sodium hydroxide, and finally the solids concentration was adjusted to 50% by mass. The copolymer latex was filtered through a 325 mesh filter and used for evaluation of physical properties. Let this copolymer latex be A. The evaluation results of each physical property of the copolymer latex A are shown in Table 1. Excellent wet stickiness resistance was obtained.
○ Preparation of paper coating composition
次に、この共重合体ラテックスＡと以下の構成材料とを使用し、均一に混合して紙塗工組成物を調製した。尚、以下の配合（質量部）は、水を除いて、全て固形分に換算した値である。
カオリンクレー ５０質量部
重質炭酸カルシウム ４５質量部
酸化チタン ５質量部
ポリアクリル酸ナトリウム ０．１質量部
水酸化ナトリウム ０．１質量部
ヒドロキシエチルエーテル化酸化澱粉 ３質量部
共重合体ラテックスＡ １２質量部
水（塗工液の全固形分濃度が６４質量％となるように添加）
Next, the copolymer latex A and the following constituent materials were used and mixed uniformly to prepare a paper coating composition. In addition, the following mixing | blendings (mass part) are the values converted into solid content altogether except water.
Kaolin clay 50 parts by weight Heavy calcium carbonate 45 parts by weight Titanium oxide 5 parts by weight Sodium polyacrylate 0.1 part by weight Sodium hydroxide 0.1 part by weight Hydroxyethyl etherified oxidized starch 3 parts by weight Copolymer latex A 12 parts by weight Part Water (added so that the total solid concentration of the coating liquid is 64% by mass)
なお、カオリンクレーとしては、商品名カオファイン（ＴＨＩＥＬＥ ＫＡＯＬＩＮ社製；粒子径２μｍ以下の割合＝９５質量％以上）、重質炭酸カルシウムとしては、商品名カービタル９７（ＥＣＣ社製；粒子径２μｍ以下の割合＝９７質量％以上）、酸化チタンとしては商品名ＫＲＯＮＯＳ ＫＡ−１０（チタン工業社製）、ポリアクリル酸ナトリウムとしては商品名アロンＴ−４０（東亞合成社製）およびヒドロキシエチルエーテル化酸化澱粉としては商品名ペンフォードガム２８０（ペンフォード社製）をそれぞれ使用した。 In addition, as a kaolin clay, the brand name Kao Fine (manufactured by THIEL KAOLIN; ratio of particle diameter 2 μm or less = 95% by mass or more), as heavy calcium carbonate, a brand name Carbital 97 (manufactured by ECC; particle diameter 2 μm or less). Ratio = 97 mass% or more), trade name KRONOS KA-10 (manufactured by Titanium Industry Co., Ltd.) as titanium oxide, trade name Aron T-40 (manufactured by Toagosei Co., Ltd.) and hydroxyethyl etherified oxidation as sodium polyacrylate As the starch, trade name Penford Gum 280 (manufactured by Penford) was used.
次に、このようにして得られた紙塗工組成物を、塗工量が片面１１ｇ／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１５０ｋｇ／ｃｍ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に用いた。この塗工紙のピック強度、湿潤ピック強度を評価した。次いで前述の方法で、塗工紙の初期耐水性を評価した。また、前述の方法で紙塗工組成物のドクターブレード洗浄性を評価した。これらの評価結果を表１に記載した。優れたピック強度及び湿潤ピック強度、初期耐水性、ドクターブレード洗浄性を有していた。
［実施例２、３］
Next, the paper coating composition thus obtained 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 11 g / m 2 on one side and dried. Thereafter, a super calender treatment was performed at a roll temperature of 50 ° C. and a linear pressure of 150 kg / cm to obtain a coated paper. The obtained coated paper was used for a printing test. The coated paper was evaluated for pick strength and wet pick strength. Subsequently, the initial water resistance of the coated paper was evaluated by the method described above. Moreover, the doctor blade washability of the paper coating composition was evaluated by the method described above. These evaluation results are shown in Table 1. It had excellent pick strength and wet pick strength, initial water resistance, and doctor blade cleanability.
[Examples 2 and 3]
重合初期原料、重合温度、単量体組成及び連鎖移動剤組成を表１に記載した通りに変更した以外は、全て実施例１と同じ条件で共重合体ラテックスＢ、Ｃを得た。いずれも優れた耐湿潤ベタツキ性を有していた。続いて実施例１と全く同様の条件で紙塗工組成物を調製し、塗工紙を得た。いずれも優れたピック強度及び湿潤ピック強度、初期耐水性、ドクターブレード洗浄性を有していた。評価結果を表１に記載した。
［実施例４］
○共重合体ラテックスの製造
Copolymer latexes B and C were obtained under the same conditions as in Example 1, except that the initial polymerization raw material, polymerization temperature, monomer composition and chain transfer agent composition were changed as described in Table 1. All of them had excellent wet stickiness resistance. Subsequently, a paper coating composition was prepared under exactly the same conditions as in Example 1 to obtain a coated paper. All had excellent pick strength and wet pick strength, initial water resistance, and doctor blade cleaning properties. The evaluation results are shown in Table 1.
[Example 4]
○ Manufacture of copolymer latex
耐圧反応容器に重合初期の原料として水１２０質量部、ドデシルベンゼンスルホン酸ナトリウム０．５質量部、及びα−メチルスチレンダイマー０．５質量部を含む重合初期原料を一括して仕込み、６５℃にて十分に攪拌した。次いで、第一重合段用として調製しておいたスチレン２０．５質量部、ブタジエン２５質量部、メタクリル酸メチル２質量部、アクリロニトリル８質量部、２−ヒドロキシエチルアクリレート１質量部、アクリル酸１質量部、ｔ−ドデシルメルカプタン０．０３質量部、α−メチルスチレンダイマー１質量部から成る単量体混合物の内、１５質量％をこの耐圧反応容器内に一括して仕込み、攪拌混合後、ペルオキソ二硫酸ナトリウム０．５質量部を耐圧容器内に添加して重合反応を開始させた。この時点から１５分後、残りの第一重合段用の単量体混合物をこの耐圧容器内に添加開始し、３時間２０分で連続的に添加を行った。一方、この残りの第一重合段用の単量体混合物の添加と同時に、水１０質量部、水酸化ナトリウム０．２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０．５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開始し、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。 A pressure-resistant reaction vessel is charged with a polymerization initial raw material containing 120 parts by weight of water, 0.5 part by weight of sodium dodecylbenzenesulfonate, and 0.5 part by weight of α-methylstyrene dimer as a raw material for the initial polymerization. And stirred well. Next, 20.5 parts by mass of styrene prepared for the first polymerization stage, 25 parts by mass of butadiene, 2 parts by mass of methyl methacrylate, 8 parts by mass of acrylonitrile, 1 part by mass of 2-hydroxyethyl acrylate, 1 part by mass of acrylic acid 15% by mass of the monomer mixture consisting of 1 part by mass, 0.03 parts by mass of t-dodecyl mercaptan and 1 part by mass of α-methylstyrene dimer are charged all at once into this pressure-resistant reaction vessel, and after stirring and mixing, 0.5 parts by mass of sodium sulfate was added into the pressure vessel to initiate the polymerization reaction. Fifteen minutes after this point, the remaining monomer mixture for the first polymerization stage was started to be added into the pressure vessel, and added continuously for 3 hours and 20 minutes. On the other hand, simultaneously with the addition of the remaining monomer mixture for the first polymerization stage, 10 parts by weight of water, 0.2 parts by weight of sodium hydroxide, 0.5 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 and continuously added over 3 hours and 10 minutes to accelerate the polymerization reaction.
第一重合段用の単量体混合物の添加が終了した時点で、直ちに第二重合段用の単量体混合物の添加を開始した。この第二重合段用の単量体混合物は、スチレン１６質量部、ブタジエン１４質量部、メタクリル酸メチル１質量部、アクリロニトリル７質量部、２−ヒドロキシエチルアクリレート１質量部、アクリル酸１質量部、ｔ−ドデシルメルカプタン０．０４質量部、α−メチルスチレンダイマー０．８質量部から成るものであり、２時間２０分で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。 When the addition of the monomer mixture for the first polymerization stage was completed, the addition of the monomer mixture for the second polymerization stage was started immediately. The monomer mixture for the second polymerization stage is 16 parts by mass of styrene, 14 parts by mass of butadiene, 1 part by mass of methyl methacrylate, 7 parts by mass of acrylonitrile, 1 part by mass of 2-hydroxyethyl acrylate, 1 part by mass of acrylic acid, This was composed of 0.04 parts by mass of t-dodecyl mercaptan and 0.8 parts by mass of α-methylstyrene dimer, and was continuously added to the pressure vessel in 2 hours and 20 minutes to continue the polymerization reaction.
第二重合段の単量体混合物の添加開始時期から３０分後に、水１４質量部、イタコン酸２．５質量部からなる４５℃のイタコン酸水溶液について、この耐圧容器への添加を開始し、１時間かけて全量を添加した。イタコン酸水溶液の添加開始時点での、容器内の単量体混合物の重合転化率は、７４．２質量％であった。 30 minutes after the start of addition of the monomer mixture in the second polymerization stage, about 45 ° C. aqueous itaconic acid solution consisting of 14 parts by mass of water and 2.5 parts by mass of itaconic acid, The whole amount was added over 1 hour. The polymerization conversion rate of the monomer mixture in the container at the start of the addition of the itaconic acid aqueous solution was 74.2% by mass.
第二重合段の単量体混合物の添加終了後、耐圧容器内の温度を９５℃に昇温させ、２時間重合反応を継続させて各単量体の重合転化率を高めた。全単量体の最終的な重合転化率は９８．８質量％であった。 After the addition of the monomer mixture in the second polymerization stage, the temperature in the pressure vessel was raised to 95 ° C., and the polymerization reaction was continued for 2 hours to increase the polymerization conversion rate of each monomer. The final polymerization conversion of all monomers was 98.8% by mass.
この共重合体ラテックスには、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、分散剤としてポリアクリル酸ナトリウムを共重合体ラテックスの固形分１００質量部当たり１質量部添加し、水酸化ナトリウムを用いてｐＨを８．０に調整し、最後に固形分濃度を５０質量％に調整した。この共重合体ラテックスを３２５メッシュのフィルターを通過させて濾過し、各物性評価に用いた。この共重合体ラテックスをＤとする。共重合体ラテックスＤの各物性の評価結果を表２に記載した。優れた耐湿潤ベタツキ性が得られた。
○紙塗工組成物、塗工紙の調製
To this copolymer latex, potassium hydroxide and sodium hydroxide are added to adjust the pH to 6.0, and unreacted monomers are removed by a steam stripping method. Sodium was added in an amount of 1 part by mass per 100 parts by mass of the copolymer latex, the pH was adjusted to 8.0 using sodium hydroxide, and finally the solids concentration was adjusted to 50% by mass. The copolymer latex was filtered through a 325 mesh filter and used for evaluation of physical properties. This copolymer latex is designated D. The evaluation results of the physical properties of the copolymer latex D are shown in Table 2. Excellent wet stickiness resistance was obtained.
○ Preparation of paper coating composition and coated paper
次に、共重合体ラテックスＡに代えて上記で得られた共重合体ラテックスＤを用いた以外は、実施例１と同様にして紙塗工組成物と塗工紙を得た。評価結果を表２に記した。優れたピック強度及び湿潤ピック強度、初期耐水性、ドクターブレード洗浄性を有していた。
［実施例５］
Next, a paper coating composition and coated paper were obtained in the same manner as in Example 1 except that the copolymer latex D obtained above was used instead of the copolymer latex A. The evaluation results are shown in Table 2. It had excellent pick strength and wet pick strength, initial water resistance, and doctor blade cleanability.
[Example 5]
実施例１と同一の耐圧反応容器に、重合初期の原料として水１１０質量部、ドデシルベンゼンスルホン酸ナトリウム０．２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０．２質量部、及びα−メチルスチレンダイマー０．４質量部を含む重合初期原料を一括して仕込み、７０℃にて十分に攪拌した。次いで、第一重合段用として調製しておいたスチレン２０質量部、ブタジエン２３質量部、メタクリル酸メチル６質量部、アクリロニトリル８質量部、２−ヒドロキシエチルアクリレート０．５質量部、ｔ−ドデシルメルカプタン０．１質量部、α−メチルスチレンダイマー０．６質量部から成る単量体及び連鎖移動剤混合物の内、１７質量％をこの耐圧反応容器内に一括して仕込み、攪拌混合後、濃度３０質量％のペルオキソ二硫酸ナトリウム水溶液０．４５質量部（固形分換算）を耐圧容器内に５分間かけて添加して重合反応を開始させた。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１０分後、残りの第一重合段用の単量体及び連鎖移動剤混合物をこの耐圧容器内に添加開始し、３時間１０分で連続的に添加を行った。一方、この残りの第一重合段用の単量体及び連鎖移動剤混合物の添加開始時の１０分後より、水１５質量部、水酸化カリウム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０．７質量部、及びペルオキソ二硫酸ナトリウム１質量部からなる水系混合物の添加を開始し、４時間かけて連続的に添加し、重合反応を加速させた。 In the same pressure resistant reactor as in Example 1, 110 parts by weight of water, 0.2 parts by weight of sodium dodecylbenzenesulfonate, 0.2 parts by weight of sodium dodecyldiphenyl ether disulfonate, and α-methylstyrene dimer 0 as raw materials at the initial stage of polymerization were used. Polymerization initial raw materials containing 4 parts by mass were charged all at once and sufficiently stirred at 70 ° C. Next, 20 parts by mass of styrene prepared for the first polymerization stage, 23 parts by mass of butadiene, 6 parts by mass of methyl methacrylate, 8 parts by mass of acrylonitrile, 0.5 part by mass of 2-hydroxyethyl acrylate, t-dodecyl mercaptan Of the monomer and chain transfer agent mixture consisting of 0.1 parts by weight and 0.6 parts by weight of α-methylstyrene dimer, 17% by weight is charged all at once into this pressure-resistant reaction vessel, and after stirring and mixing, the concentration is 30. A polymerization reaction was initiated by adding 0.45 parts by mass (in terms of solid content) of a mass% aqueous sodium peroxodisulfate solution to the pressure vessel over 5 minutes. After 10 minutes from the end of the addition of the aqueous sodium peroxodisulfate solution, the remaining monomer for the first polymerization stage and the chain transfer agent mixture were started to be added into the pressure vessel, and continuously added in 3 hours and 10 minutes. went. On the other hand, from 10 minutes after the start of addition of the remaining monomer for the first polymerization stage and the chain transfer agent mixture, 15 parts by mass of water, 0.1 part by mass of potassium hydroxide, sodium dodecyl diphenyl ether disulfonate, 0. The addition of an aqueous mixture composed of 7 parts by mass and 1 part by mass of sodium peroxodisulfate was started and continuously added over 4 hours to accelerate the polymerization reaction.
第一重合段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から、１時間後に第二重合段用の単量体及び連鎖移動剤混合物の添加を開始した。この系においては、第一重合段と第二重合段との間に、系内に単量体及び連鎖移動剤を添加しないインターバル時間を設け、第一重合段の重合転化率を高めた。この第二重合段用の単量体及び連鎖移動剤混合物は、スチレン１３．５質量部、ブタジエン１３質量部、メタクリル酸メチル５質量部、アクリロニトリル７質量部、２−ヒドロキシエチルアクリレート１質量部、ｔ−ドデシルメルカプタン０．１質量部、α−メチルスチレンダイマー０．８質量部、アクリル酸０．５重量部から成るものであり、２時間で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。 The addition of the monomer and chain transfer agent mixture for the second polymerization stage was started 1 hour after the addition of the monomer and chain transfer agent mixture for the first polymerization stage was completed. In this system, an interval time during which no monomer or chain transfer agent was added was provided in the system between the first polymerization stage and the second polymerization stage to increase the polymerization conversion rate of the first polymerization stage. The monomer and chain transfer agent mixture for the second polymerization stage were 13.5 parts by mass of styrene, 13 parts by mass of butadiene, 5 parts by mass of methyl methacrylate, 7 parts by mass of acrylonitrile, 1 part by mass of 2-hydroxyethyl acrylate, It consists of 0.1 parts by weight of t-dodecyl mercaptan, 0.8 parts by weight of α-methylstyrene dimer, and 0.5 parts by weight of acrylic acid. Was continued.
一方、第二重合段の単量体及び連鎖移動剤混合物の添加開始時点と同時に、イタコン酸２．５質量部を含む固形分濃度１５質量％の、５０℃のイタコン酸水溶液について、この耐圧容器への添加を開始し、６０分かけて全量を添加した。添加開始時点での容器内の単量体混合物の重合転化率は、８２．７質量％であった。 On the other hand, at the same time as the start of addition of the monomer and chain transfer agent mixture in the second polymerization stage, this pressure-resistant container was used for an itaconic acid aqueous solution having a solid content concentration of 15% by mass containing 2.5 parts by mass of itaconic acid. The whole amount was added over 60 minutes. The polymerization conversion rate of the monomer mixture in the container at the start of the addition was 82.7% by mass.
第二重合段の単量体混合物の添加終了後、耐圧容器内の温度を、６０分かけて９５℃にまで昇温させ、更に３０分間重合反応を継続させて各単量体の重合転化率を高めた。全単量体の最終的な重合転化率は９８．８質量％であった。この共重合体ラテックスには、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、分散剤としてポリアクリル酸ナトリウムを共重合体ラテックスの固形分１００質量部当たり０．５質量部添加し、水酸化ナトリウムを用いてｐＨを８．０に調整し、前述の濾過装置及び条件でフィルターを通過させて濾過し、各物性評価に用いた。この共重合体ラテックスをＥとする。共重合体ラテックスＥの各物性の評価結果を表２に記載した。優れた耐湿潤ベタツキ性が得られた。 After the addition of the monomer mixture in the second polymerization stage, the temperature in the pressure vessel is raised to 95 ° C. over 60 minutes, and the polymerization reaction is continued for 30 minutes to obtain a polymerization conversion rate of each monomer. Increased. The final polymerization conversion of all monomers was 98.8% by mass. To this copolymer latex, potassium hydroxide and sodium hydroxide are added to adjust the pH to 6.0 or higher, and unreacted monomers are removed by a steam stripping method. Add 0.5 parts by weight of sodium oxide per 100 parts by weight of the solid content of the copolymer latex, adjust the pH to 8.0 using sodium hydroxide, and pass through the filter under the above-described filtration apparatus and conditions for filtration. And used for each physical property evaluation. This copolymer latex is designated E. Table 2 shows the evaluation results of the physical properties of the copolymer latex E. Excellent wet stickiness resistance was obtained.
次に、共重合体ラテックスＡに代えて上記で得られた共重合体ラテックスＥを用いた事以外は、実施例１と同様にして紙塗工組成物と塗工紙を得た。結果を表２に記載した。優れたピック強度及び湿潤ピック強度、初期耐水性及びドクターブレード洗浄性を有していた。
［実施例６］
Next, a paper coating composition and coated paper were obtained in the same manner as in Example 1 except that the copolymer latex E obtained above was used instead of the copolymer latex A. The results are shown in Table 2. It had excellent pick strength and wet pick strength, initial water resistance and doctor blade cleanability.
[Example 6]
重合初期原料、重合温度、各重合段の単量体組成及び連鎖移動剤組成、後添加する二塩基性エチレン系不飽和カルボン酸量について、表２に記載した通りに変更した事以外は、全て実施例５と同一の条件で共重合体ラテックスＦを製造した。優れた耐湿潤ベタツキ性が得られた。次いで共重合体ラテックスＡに代えて上記で得られた共重合体ラテックスＦを用いた事以外は、実施例１と同様にして紙塗工組成物と塗工紙を得た。結果を表２に記載した。優れたピック強度及び湿潤ピック強度、初期耐水性及びドクターブレード洗浄性を有していた。
［比較例１、２］
重合初期原料、重合温度、単量体組成及び連鎖移動剤組成を表１に記載した通りに変更した事以外は、全て実施例１と同じ条件で共重合体ラテックスＧ、Ｈを得た。いずれも耐湿潤ベタツキ性が劣る結果となった。続いて共重合体ラテックスＡに代えて上記で得られた共重合体ラテックスＧ又はＨを用いた事以外は、実施例１と全く同様の条件で紙塗工組成物を調製し、塗工紙を得た。ピック強度及び湿潤ピック強度、初期耐水性、ドクターブレード洗浄性はいずれも劣る結果となった。評価結果を表１に記載した。
［比較例３、４］
Initial polymerization raw material, polymerization temperature, monomer composition and chain transfer agent composition of each polymerization stage, and the amount of dibasic ethylenically unsaturated carboxylic acid to be added later, except for changes as described in Table 2, all A copolymer latex F was produced under the same conditions as in Example 5. Excellent wet stickiness resistance was obtained. Next, a paper coating composition and coated paper were obtained in the same manner as in Example 1 except that the copolymer latex F obtained above was used instead of the copolymer latex A. The results are shown in Table 2. It had excellent pick strength and wet pick strength, initial water resistance and doctor blade cleanability.
[Comparative Examples 1 and 2]
Copolymer latexes G and H were obtained under the same conditions as in Example 1 except that the initial polymerization raw material, polymerization temperature, monomer composition and chain transfer agent composition were changed as described in Table 1. In either case, the wet stickiness resistance was inferior. Subsequently, a paper coating composition was prepared under exactly the same conditions as in Example 1 except that the copolymer latex G or H obtained above was used instead of the copolymer latex A, and the coated paper was Obtained. The pick strength and wet pick strength, initial water resistance, and doctor blade washability all resulted in poor results. The evaluation results are shown in Table 1.
[Comparative Examples 3 and 4]
重合初期原料、各重合段の単量体組成及び連鎖移動剤組成、後添加する二塩基性エチレン系不飽和カルボン酸量について、表２に記載した通りに変更した事以外は、全て実施例５と同一の条件で共重合体ラテックスＩ、Ｊを製造した。いずれも耐湿潤ベタツキ性は劣る結果となった。次いで共重合体ラテックスＡに代えて上記で得られた共重合体ラテックスＩ又はＪを用いた事以外は、実施例１と同様にして紙塗工組成物と塗工紙を得た。結果を表２に記載した。ピック強度及び湿潤ピック強度、初期耐水性、ドクターブレード洗浄性はいずれも劣る結果となった。評価結果を表２に記載した。 Example 5 except that the initial polymerization material, the monomer composition and chain transfer agent composition of each polymerization stage, and the amount of dibasic ethylenically unsaturated carboxylic acid to be added later were changed as described in Table 2. Copolymer latexes I and J were produced under the same conditions as in Example 1. In all cases, the wet stickiness resistance was inferior. Next, a paper coating composition and coated paper were obtained in the same manner as in Example 1 except that the copolymer latex I or J obtained above was used in place of the copolymer latex A. The results are shown in Table 2. The pick strength and wet pick strength, initial water resistance, and doctor blade washability all resulted in poor results. The evaluation results are shown in Table 2.
Claims (6)
The coated paper for offset printing in which the paper coating composition of Claim 5 was coated on the surface.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008106276A (en) * | 2006-10-24 | 2008-05-08 | Lg Chem Ltd | Multilayered structure paper coating latex having high swelling and contraction property, method for manufacturing the same, and paper coating liquid containing the same |
| JP2011057854A (en) * | 2009-09-10 | 2011-03-24 | Asahi Kasei Chemicals Corp | Copolymer latex, paper coating composition and coated paper |
| JP2020139041A (en) * | 2019-02-28 | 2020-09-03 | 旭化成株式会社 | Water-based composition and coating film |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4834224A (en) * | 1971-09-06 | 1973-05-17 | ||
| JPH05272094A (en) * | 1992-03-18 | 1993-10-19 | Nippon Zeon Co Ltd | Paper-coating composition |
| JPH0616736A (en) * | 1992-06-30 | 1994-01-25 | Sumitomo Dow Ltd | Production of copolymer latex |
| JPH0718003A (en) * | 1993-07-02 | 1995-01-20 | Japan Synthetic Rubber Co Ltd | Production of latex |
| JPH07247327A (en) * | 1994-03-09 | 1995-09-26 | Nippon Zeon Co Ltd | Latex and composition for paper coating |
| JP2003277448A (en) * | 2002-03-27 | 2003-10-02 | Jsr Corp | Copolymer latex |
-
2005
- 2005-12-08 JP JP2005354718A patent/JP4863352B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4834224A (en) * | 1971-09-06 | 1973-05-17 | ||
| JPH05272094A (en) * | 1992-03-18 | 1993-10-19 | Nippon Zeon Co Ltd | Paper-coating composition |
| JPH0616736A (en) * | 1992-06-30 | 1994-01-25 | Sumitomo Dow Ltd | Production of copolymer latex |
| JPH0718003A (en) * | 1993-07-02 | 1995-01-20 | Japan Synthetic Rubber Co Ltd | Production of latex |
| JPH07247327A (en) * | 1994-03-09 | 1995-09-26 | Nippon Zeon Co Ltd | Latex and composition for paper coating |
| JP2003277448A (en) * | 2002-03-27 | 2003-10-02 | Jsr Corp | Copolymer latex |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008106276A (en) * | 2006-10-24 | 2008-05-08 | Lg Chem Ltd | Multilayered structure paper coating latex having high swelling and contraction property, method for manufacturing the same, and paper coating liquid containing the same |
| JP4703625B2 (en) * | 2006-10-24 | 2011-06-15 | エルジー・ケム・リミテッド | Highly swellable / shrinkable multilayer paper coating latex, method for producing the same, and paper coating solution containing the same |
| JP2011057854A (en) * | 2009-09-10 | 2011-03-24 | Asahi Kasei Chemicals Corp | Copolymer latex, paper coating composition and coated paper |
| JP2020139041A (en) * | 2019-02-28 | 2020-09-03 | 旭化成株式会社 | Water-based composition and coating film |
| JP7271228B2 (en) | 2019-02-28 | 2023-05-11 | 旭化成株式会社 | Water-based composition and coating film |
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