JP2019026655A - Dispersion stabilizer for lubricant and dispersion stability improvement method for lubricant - Google Patents
Dispersion stabilizer for lubricant and dispersion stability improvement method for lubricant Download PDFInfo
- Publication number
- JP2019026655A JP2019026655A JP2017143608A JP2017143608A JP2019026655A JP 2019026655 A JP2019026655 A JP 2019026655A JP 2017143608 A JP2017143608 A JP 2017143608A JP 2017143608 A JP2017143608 A JP 2017143608A JP 2019026655 A JP2019026655 A JP 2019026655A
- Authority
- JP
- Japan
- Prior art keywords
- copolymer latex
- lubricant
- dispersion stabilizer
- mass
- dispersion
- 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.)
- Granted
Links
- 239000006185 dispersion Substances 0.000 title claims abstract description 110
- 239000000314 lubricant Substances 0.000 title claims abstract description 92
- 239000003381 stabilizer Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims description 27
- 229920001577 copolymer Polymers 0.000 claims abstract description 150
- 239000004816 latex Substances 0.000 claims abstract description 150
- 229920000126 latex Polymers 0.000 claims abstract description 150
- 239000002270 dispersing agent Substances 0.000 claims abstract description 33
- 239000007787 solid Substances 0.000 claims abstract description 26
- 229920005646 polycarboxylate Polymers 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 10
- 230000006641 stabilisation Effects 0.000 abstract 1
- 238000011105 stabilization Methods 0.000 abstract 1
- 239000000178 monomer Substances 0.000 description 65
- 238000006243 chemical reaction Methods 0.000 description 45
- 238000006116 polymerization reaction Methods 0.000 description 39
- 238000004519 manufacturing process Methods 0.000 description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 18
- 239000003995 emulsifying agent Substances 0.000 description 18
- 239000003002 pH adjusting agent Substances 0.000 description 18
- 239000003505 polymerization initiator Substances 0.000 description 18
- -1 3-chloro-2-hydroxypropyl Chemical group 0.000 description 16
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 14
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 13
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- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
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- 238000002156 mixing Methods 0.000 description 10
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- 230000000052 comparative effect Effects 0.000 description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 8
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- 239000000654 additive Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 7
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 7
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- 229920002799 BoPET Polymers 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000008199 coating composition Substances 0.000 description 6
- 239000001530 fumaric acid Substances 0.000 description 6
- 239000011976 maleic acid Substances 0.000 description 6
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 239000012986 chain transfer agent Substances 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 4
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
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- 125000001931 aliphatic group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
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- 238000003786 synthesis reaction Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 2
- CTMHWPIWNRWQEG-UHFFFAOYSA-N 1-methylcyclohexene Chemical compound CC1=CCCCC1 CTMHWPIWNRWQEG-UHFFFAOYSA-N 0.000 description 2
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- FSWCCQWDVGZMRD-UHFFFAOYSA-N 4-methylcyclohexene Chemical compound CC1CCC=CC1 FSWCCQWDVGZMRD-UHFFFAOYSA-N 0.000 description 2
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- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-araboascorbic acid Natural products OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 2
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- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000002211 L-ascorbic acid Substances 0.000 description 2
- 235000000069 L-ascorbic acid Nutrition 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
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- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
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- 239000002253 acid Substances 0.000 description 2
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
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- 229960005070 ascorbic acid Drugs 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
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- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
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- 239000000661 sodium alginate Substances 0.000 description 1
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- 150000008163 sugars Chemical class 0.000 description 1
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- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
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- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Lubricants (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paper (AREA)
Abstract
Description
本発明は、潤滑剤の分散安定化剤及び潤滑剤の分散安定性向上方法に関する。 The present invention relates to a lubricant dispersion stabilizer and a method for improving the dispersion stability of a lubricant.
近年、塗工紙は、その印刷効果が高い等の理由から、非常に数多くの印刷物に利用されている。季刊、月刊紙等の定期刊行物の中にも、全ての頁に塗工紙が使用される場合もかなり増えている。特に、メールオーダービジネスにおけるダイレクトメールや商品カタログ等においては、そのほとんどが全ての頁に塗工紙を使用している。 In recent years, coated paper has been used in a large number of printed materials because of its high printing effect. Even in periodicals such as quarterly and monthly papers, the use of coated paper on all pages has increased considerably. In particular, most direct mails and product catalogs in the mail order business use coated paper for all pages.
一般に紙塗工用組成物は、クレーや炭酸カルシウムなどの白色顔料を水に分散した顔料分散液と、顔料同士および顔料と原紙とを接着固定するためのバインダーと、その他の添加剤とによって構成される水性塗料である。バインダーとしては、スチレン−ブタジエン系共重合体ラテックスに代表されるような合成エマルションバインダーや、デンプン、カゼインに代表されるような天然バインダーが使用される。その中でも、乳化重合により得られるスチレン−ブタジエン系共重合体ラテックスは、品質設計の自由度が大きく、紙塗工用組成物に最も適したバインダーとして広く使用されており、その特性が紙塗工用組成物の性能や塗工紙作成時の操業性あるいは最終的な塗工紙製品の表面強度、印刷光沢などの品質に影響することが知られている（例えば、下記特許文献１及び２を参照）。 Generally, a composition for paper coating is composed of a pigment dispersion in which a white pigment such as clay or calcium carbonate is dispersed in water, a binder for adhering and fixing the pigments to each other, and the pigment and the base paper, and other additives. It is a water-based paint. As the binder, a synthetic emulsion binder represented by styrene-butadiene copolymer latex, or a natural binder represented by starch or casein is used. Among them, styrene-butadiene copolymer latex obtained by emulsion polymerization has a high degree of freedom in quality design, and is widely used as the most suitable binder for paper coating compositions. It is known that it affects the performance of the composition for coating, the operability at the time of creating coated paper, or the quality of the final coated paper product, such as surface strength and printing gloss (for example, Patent Documents 1 and 2 below) reference).
また、塗工紙作成時の操業性を向上させるために、共重合体ラテックスを含む紙塗工用組成物に潤滑剤を添加することが知られている（例えば、下記特許文献３を参照）。 In addition, it is known to add a lubricant to a paper coating composition containing a copolymer latex in order to improve operability at the time of creating coated paper (see, for example, Patent Document 3 below). .
上述したような共重合体ラテックスには、必要に応じて低粘度化のために分散剤が添加されるが、分散剤が添加された共重合体ラテックスと、操業性を向上させるための潤滑剤と、顔料等とを混合して調製された紙塗工用組成物では、紙塗工用組成物中での潤滑剤の分散安定性が悪く、潤滑剤が凝集して凝集物を形成する場合がある。潤滑剤の凝集物が発生すると、例えば塗工紙作成時のバッキングロールやカレンダーロールの汚れの原因となり、操業性の低下や得られる塗工紙の外観不良が生じることとなる。 In the copolymer latex as described above, a dispersant is added to reduce the viscosity as necessary, but the copolymer latex to which the dispersant is added and a lubricant for improving the operability. And a paper coating composition prepared by mixing pigments and the like, the dispersion stability of the lubricant in the paper coating composition is poor, and the lubricant aggregates to form aggregates There is. When the aggregate of the lubricant is generated, for example, the backing roll and the calender roll at the time of preparation of the coated paper may be contaminated, and the operability is deteriorated and the appearance of the obtained coated paper is deteriorated.
本発明は、上記従来技術の有する課題に鑑みてなされたものであり、潤滑剤の分散安定性を良好にでき、潤滑剤の凝集物が発生することを抑制することができる、潤滑剤の分散安定化剤及び潤滑剤の分散安定性向上方法を提供することを目的とする。 The present invention has been made in view of the above-mentioned problems of the prior art, can improve the dispersion stability of the lubricant, and can suppress the occurrence of lubricant aggregates. It is an object to provide a method for improving the dispersion stability of a stabilizer and a lubricant.
本発明者らは、共重合体ラテックスと潤滑剤とを混合した際に潤滑剤が凝集する原因について鋭意研究を重ねた結果、潤滑剤の凝集に分散剤の存在が関与しており、分散剤がある一定量を超えて共重合体ラテックスに添加されている場合に、潤滑剤の凝集が生じやすいことを見出した。 As a result of intensive studies on the cause of the aggregation of the lubricant when the copolymer latex and the lubricant are mixed, the present inventors have found that the presence of the dispersant is involved in the aggregation of the lubricant. It has been found that when more than a certain amount is added to the copolymer latex, aggregation of the lubricant tends to occur.
そこで、本発明は、共重合体ラテックスを含有する、潤滑剤の分散安定化剤であって、分散剤の含有量が、上記共重合体ラテックスの固形分１００質量部に対して０．０１質量部以上１．８質量部以下である、分散安定化剤を提供する。かかる分散安定化剤によれば、分散剤の含有量を上記範囲内に制御することにより、当該分散安定化剤と潤滑剤とを混合した場合に、混合物中での潤滑剤の分散安定性が良好となり、潤滑剤の凝集物の発生を抑制することができる。そのため、この分散安定化剤を用いて紙塗工用組成物を調製した場合、塗工紙作成時のバッキングロールやカレンダーロールの汚れを防ぎ、操業性の低下及び得られる塗工紙の外観不良の発生を抑制することができる。 Therefore, the present invention is a dispersion stabilizer for a lubricant containing a copolymer latex, and the content of the dispersant is 0.01 mass relative to 100 mass parts of the solid content of the copolymer latex. Provided is a dispersion stabilizer that is at least 1 part and at most 1.8 parts by weight. According to such a dispersion stabilizer, by controlling the content of the dispersant within the above range, when the dispersion stabilizer and the lubricant are mixed, the dispersion stability of the lubricant in the mixture is improved. It becomes favorable and the generation | occurrence | production of the aggregate of a lubricant can be suppressed. Therefore, when a composition for paper coating is prepared using this dispersion stabilizer, it prevents dirt on the backing roll and calendar roll at the time of creating the coated paper, reduces operability and poor appearance of the resulting coated paper Can be suppressed.
上記分散安定化剤は、上記分散剤としてポリカルボン酸塩を含有していてもよい。分散安定化剤がポリカルボン酸塩を含有することで、潤滑剤の分散安定性を良好にしつつ、共重合体ラテックスの粘度を低減することができる。 The dispersion stabilizer may contain a polycarboxylate as the dispersant. When the dispersion stabilizer contains the polycarboxylate, the viscosity of the copolymer latex can be reduced while improving the dispersion stability of the lubricant.
ここで、上記ポリカルボン酸塩の重量平均分子量は１０００〜１０００００であってもよい。ポリカルボン酸塩の重量平均分子量を上記範囲内とすることで、上記範囲外である場合と比較して、潤滑剤の分散安定性を向上させることができる。 Here, the weight average molecular weight of the polycarboxylate may be 1000 to 100,000. By setting the weight average molecular weight of the polycarboxylic acid salt within the above range, it is possible to improve the dispersion stability of the lubricant as compared with the case where it is outside the above range.
上記分散安定化剤において、上記共重合体ラテックスのｐＨは６．０以上であってもよい。共重合体ラテックスのｐＨを上記範囲内とすることで、上記範囲外である場合と比較して、潤滑剤の分散安定性を向上させることができる。 In the dispersion stabilizer, the pH of the copolymer latex may be 6.0 or more. By setting the pH of the copolymer latex within the above range, the dispersion stability of the lubricant can be improved as compared with the case where the pH is outside the above range.
上記分散安定化剤において、上記共重合体ラテックスの平均粒子径は３０〜２５０ｎｍであってもよい。共重合体ラテックスの平均粒子径を上記範囲内とすることで、上記範囲外である場合と比較して、潤滑剤の分散安定性を向上させることができる。 In the dispersion stabilizer, the average particle size of the copolymer latex may be 30 to 250 nm. By setting the average particle diameter of the copolymer latex within the above range, it is possible to improve the dispersion stability of the lubricant as compared with the case where it is outside the above range.
本発明はまた、共重合体ラテックスを含有する分散安定化剤と潤滑剤とを混合した混合物における上記潤滑剤の分散安定性を向上させる方法であって、上記分散安定化剤における分散剤の含有量を、上記共重合体ラテックスの固形分１００質量部に対して０．０１質量部以上１．８質量部以下とする、潤滑剤の分散安定性向上方法を提供する。かかる方法によれば、潤滑剤と混合する分散安定化剤における分散剤の含有量を上記範囲内に制御することにより、当該分散安定化剤と潤滑剤とを混合した場合に、混合物中での潤滑剤の分散安定性を向上させることができる。 The present invention is also a method for improving the dispersion stability of the lubricant in a mixture in which a dispersion stabilizer containing a copolymer latex and a lubricant are mixed, and containing the dispersant in the dispersion stabilizer. Provided is a method for improving the dispersion stability of a lubricant, wherein the amount is 0.01 to 1.8 parts by mass with respect to 100 parts by mass of the solid content of the copolymer latex. According to this method, by controlling the content of the dispersant in the dispersion stabilizer mixed with the lubricant within the above range, when the dispersion stabilizer and the lubricant are mixed, The dispersion stability of the lubricant can be improved.
上記方法において、上記分散安定化剤は、上記分散剤としてポリカルボン酸塩を含有してもよい。分散安定化剤がポリカルボン酸塩を含有することで、潤滑剤の分散安定性を向上しつつ、共重合体ラテックスの粘度を低減することができる。 In the above method, the dispersion stabilizer may contain a polycarboxylate as the dispersant. When the dispersion stabilizer contains the polycarboxylate, the viscosity of the copolymer latex can be reduced while improving the dispersion stability of the lubricant.
本発明によれば、共重合体ラテックスと潤滑剤とを混合した場合に、潤滑剤の分散安定性を良好にでき、潤滑剤の凝集物が発生することを抑制することができる、潤滑剤の分散安定化剤及び潤滑剤の分散安定性向上方法を提供することができる。 According to the present invention, when the copolymer latex and the lubricant are mixed, the dispersion stability of the lubricant can be improved, and the occurrence of lubricant aggregates can be suppressed. A method for improving the dispersion stability of a dispersion stabilizer and a lubricant can be provided.
以下、本発明をその好適な実施形態に即して詳細に説明する。 Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.
本実施形態に係る潤滑剤の分散安定化剤は、少なくとも共重合体ラテックスを含有する。分散安定化剤は、分散剤の含有量が、上記共重合体ラテックスの固形分１００質量部に対して０．０１質量部以上１．８質量部以下である。潤滑剤の分散安定性を良好にする観点から、分散安定化剤における分散剤の含有量は、共重合体ラテックスの固形分１００質量部に対して、１．５質量部以下であることが好ましく、１．２質量部以下であることがより好ましく、１．０質量部以下であることが更に好ましい。一方、共重合体ラテックスの低粘度化の観点から、分散安定化剤における分散剤の含有量は、共重合体ラテックスの固形分１００質量部に対して、０．１質量部以上であってもよく、０．２質量部以上であってもよく、０．３質量部以上であってもよい。 The lubricant dispersion stabilizer according to this embodiment contains at least a copolymer latex. In the dispersion stabilizer, the content of the dispersant is 0.01 parts by mass or more and 1.8 parts by mass or less with respect to 100 parts by mass of the solid content of the copolymer latex. From the viewpoint of improving the dispersion stability of the lubricant, the content of the dispersant in the dispersion stabilizer is preferably 1.5 parts by mass or less with respect to 100 parts by mass of the solid content of the copolymer latex. 1.2 parts by mass or less, more preferably 1.0 parts by mass or less. On the other hand, from the viewpoint of lowering the viscosity of the copolymer latex, the content of the dispersant in the dispersion stabilizer may be 0.1 parts by mass or more with respect to 100 parts by mass of the solid content of the copolymer latex. It may be 0.2 parts by mass or more, or 0.3 parts by mass or more.
（共重合体ラテックス）
本実施形態の分散安定化剤に用いられる共重合体ラテックスは特に限定されず、乳化重合により得られる共重合体ラテックスを用いることができる。共重合体ラテックスは、分散剤の含有量を共重合体ラテックスの固形分１００質量部に対して０．０１質量部以上１．８質量部以下とした場合であっても低粘度化を図ることができると共に、潤滑剤の分散安定性をより良好にできることから、以下の共重合体ラテックスであることが好ましい。
(Copolymer latex)
The copolymer latex used for the dispersion stabilizer of the present embodiment is not particularly limited, and a copolymer latex obtained by emulsion polymerization can be used. The copolymer latex should have a low viscosity even when the content of the dispersant is 0.01 parts by mass or more and 1.8 parts by mass or less with respect to 100 parts by mass of the solid content of the copolymer latex. In addition, since the dispersion stability of the lubricant can be improved, the following copolymer latex is preferable.
すなわち、共重合体ラテックスは、乳化重合により得られる共重合体ラテックスであって、上記共重合体は、（ａ）脂肪族共役ジエン系単量体、必要に応じて用いられる（ｂ）エチレン系不飽和カルボン酸単量体、（ｃ）シアン化ビニル単量体、及び、必要に応じて用いられる（ｄ）これらと共重合可能な単量体、からなる単量体成分で構成されていることが好ましい。 That is, the copolymer latex is a copolymer latex obtained by emulsion polymerization, and the copolymer is (a) an aliphatic conjugated diene monomer, and is used as needed. It is composed of a monomer component comprising an unsaturated carboxylic acid monomer, (c) a vinyl cyanide monomer, and (d) a monomer copolymerizable therewith. It is preferable.
（ａ）脂肪族共役ジエン系単量体（以下、（ａ）成分という場合もある）としては、１，３−ブタジエン、２−メチル−１，３−ブタジエン、２，３−ジメチル−１，３−ブタジエン、２−クロル−１，３−ブタジエン、置換直鎖共役ペンタジエン類、並びに、置換および側鎖共役ヘキサジエン類などの単量体が挙げられる。これらは１種を単独でまたは２種以上を組み合わせて使用することができる。本実施形態においては、工業的に容易に製造され、入手の容易性及びコストの観点から、１，３−ブタジエンを用いることが好ましい。 As the (a) aliphatic conjugated diene monomer (hereinafter sometimes referred to as the component (a)), 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1, Examples include monomers such as 3-butadiene, 2-chloro-1,3-butadiene, substituted linear conjugated pentadienes, and substituted and side chain conjugated hexadienes. These can be used alone or in combination of two or more. In the present embodiment, it is preferable to use 1,3-butadiene from the viewpoint of easy production industrially and availability and cost.
（ｂ）エチレン系不飽和カルボン酸単量体（以下、（ｂ）成分という場合もある）としては、アクリル酸、メタクリル酸及びクロトン酸などのモノカルボン酸単量体、マレイン酸、フマル酸及びイタコン酸などのジカルボン酸単量体並びにこれらの無水物が挙げられる。これらの単量体は１種を単独でまたは２種以上を組み合わせて使用することができる。 (B) As the ethylenically unsaturated carboxylic acid monomer (hereinafter also referred to as component (b)), monocarboxylic acid monomers such as acrylic acid, methacrylic acid and crotonic acid, maleic acid, fumaric acid and Examples thereof include dicarboxylic acid monomers such as itaconic acid and anhydrides thereof. These monomers can be used alone or in combination of two or more.
（ｃ）シアン化ビニル単量体（以下、（ｃ）成分という場合もある）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、α−エチルアクリロニトリルなどが挙げられる。これらは１種を単独でまたは２種以上を組み合わせて使用することができる。本実施形態においては、工業的に容易に製造され、入手の容易性及びコストの観点から、アクリロニトリル又はメタクリロニトリルを用いることが好ましい。 Examples of (c) vinyl cyanide monomer (hereinafter sometimes referred to as component (c)) include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile and the like. These can be used alone or in combination of two or more. In the present embodiment, it is preferable to use acrylonitrile or methacrylonitrile from the viewpoint of easy production industrially and availability and cost.
（ｄ）上記（ａ）成分〜（ｃ）成分と共重合可能な単量体（以下、（ｄ）成分という場合もある）としては、アルケニル芳香族単量体、不飽和カルボン酸アルキルエステル単量体、ヒドロキシアルキル基を含有する不飽和単量体、不飽和カルボン酸アミド単量体などの単量体が挙げられる。 (D) Monomers copolymerizable with the above components (a) to (c) (hereinafter sometimes referred to as (d) component) include alkenyl aromatic monomers, unsaturated carboxylic acid alkyl ester monomers. And monomers such as a monomer, an unsaturated monomer containing a hydroxyalkyl group, and an unsaturated carboxylic acid amide monomer.
アルケニル芳香族単量体としては、スチレン、α−メチルスチレン、メチル−α−メチルスチレン、ビニルトルエン及びジビニルベンゼンなどが挙げられる。これらは１種を単独でまたは２種以上を組み合わせて使用することができる。本実施形態においては、工業的に容易に製造され、入手の容易性及びコストの観点から、スチレンを用いることが好ましい。 Examples of the alkenyl aromatic monomer include styrene, α-methylstyrene, methyl-α-methylstyrene, vinyl toluene and divinylbenzene. These can be used alone or in combination of two or more. In this embodiment, it is preferable to use styrene from the viewpoint of easy production industrially and availability and cost.
不飽和カルボン酸アルキルエステル単量体としては、メチルアクリレート、メチルメタクリレート、エチルアクリレート、エチルメタクリレート、ブチルアクリレート、グリシジルメタクリレート、ジメチルフマレート、ジエチルフマレート、ジメチルマレエート、ジエチルマレエート、ジメチルイタコネート、モノメチルフマレート、モノエチルフマレート及び２−エチルヘキシルアクリレートなどが挙げられる。これらは１種を単独でまたは２種以上を組み合わせて使用することができる。本実施形態においては、工業的に容易に製造され、入手の容易性及びコストの観点から、メチルメタクリレートを用いることが好ましい。 Examples of unsaturated carboxylic acid alkyl ester monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, glycidyl methacrylate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, dimethyl itaconate, Examples include monomethyl fumarate, monoethyl fumarate, and 2-ethylhexyl acrylate. These can be used alone or in combination of two or more. In the present embodiment, it is preferable to use methyl methacrylate from the viewpoint of easy production industrially and availability and cost.
ヒドロキシアルキル基を含有する不飽和単量体としては、β−ヒドロキシエチルアクリレート、β−ヒドロキシエチルメタクリレート、ヒドロキシプロピルアクリレート、ヒドロキシプロピルメタクリレート、ヒドロキシブチルアクリレート、ヒドロキシブチルメタクリレート、３−クロロ−２−ヒドロキシプロピルメタクリレート、ジ−（エチレングリコール）マレエート、ジ−（エチレングリコール）イタコネート、２−ヒドロキシエチルマレエート、ビス（２−ヒドロキシエチル）マレエート及び２−ヒドロキシエチルメチルフマレートなどが挙げられる。これらは１種を単独でまたは２種以上を組み合わせて使用することができる。 Examples of unsaturated monomers containing a hydroxyalkyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, and 3-chloro-2-hydroxypropyl. Examples include methacrylate, di- (ethylene glycol) maleate, di- (ethylene glycol) itaconate, 2-hydroxyethyl maleate, bis (2-hydroxyethyl) maleate, and 2-hydroxyethyl methyl fumarate. These can be used alone or in combination of two or more.
不飽和カルボン酸アミド単量体としては、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−メチロールメタクリルアミド及びＮ，Ｎ−ジメチルアクリルアミドなどが挙げられる。これらは１種を単独でまたは２種以上を組み合わせて使用することができる。 Examples of the unsaturated carboxylic acid amide monomer include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide and N, N-dimethylacrylamide. These can be used alone or in combination of two or more.
さらに、上記単量体の他に、エチレン、プロピレン、酢酸ビニル、プロピオン酸ビニル、塩化ビニル、塩化ビニリデン等、通常の乳化重合において使用される単量体を使用することができる。 Furthermore, in addition to the above monomers, monomers used in ordinary emulsion polymerization such as ethylene, propylene, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, and the like can be used.
（ａ）成分の含有量は、共重合体を構成する単量体成分全量に対し、２５〜６０質量％であることが好ましく、２７〜５６質量％であることがより好ましく、３０〜５２質量％であることが更に好ましい。（ａ）成分の含有量を上記範囲とすることにより、共重合体ラテックスの接着強度と塗工紙作成時の操業性とのバランスに優れた共重合体ラテックスを得ることができる。 The content of the component (a) is preferably 25 to 60% by mass, more preferably 27 to 56% by mass, and more preferably 30 to 52% by mass with respect to the total amount of monomer components constituting the copolymer. % Is more preferable. By making content of (a) component into the said range, the copolymer latex excellent in the balance of the adhesive strength of copolymer latex and the operativity at the time of coated paper preparation can be obtained.
（ｂ）成分の含有量は、共重合体を構成する単量体成分全量に対し、０〜２３質量％であり、１〜２０質量％であることが好ましく、２〜１５質量％であることがより好ましい。（ｂ）成分の含有量を上記範囲とすることにより、共重合体ラテックスの接着強度を十分に向上させることができる。 (B) Content of a component is 0-23 mass% with respect to the monomer component whole quantity which comprises a copolymer, it is preferable that it is 1-20 mass%, and it is 2-15 mass%. Is more preferable. By making content of (b) component into the said range, the adhesive strength of copolymer latex can fully be improved.
（ｃ）成分の含有量は、共重合体を構成する単量体成分全量に対し、１〜３０質量％であり、２〜２８質量％であることが好ましく、４〜２５質量％であることがより好ましい。（ｃ）成分の含有量を上記範囲とすることにより、耐溶剤性に優れる共重合体ラテックスを得ることができる。 (C) Content of a component is 1-30 mass% with respect to the monomer component whole quantity which comprises a copolymer, It is preferable that it is 2-28 mass%, and it is 4-25 mass%. Is more preferable. By making content of (c) component into the said range, the copolymer latex excellent in solvent resistance can be obtained.
（ｄ）成分の含有量は、共重合体を構成する単量体成分全量に対し、０〜６７．５質量％であり、２〜６５質量％であることが好ましく、８〜６０質量％であることがより好ましい。 (D) Content of component is 0-67.5 mass% with respect to the monomer component whole quantity which comprises a copolymer, It is preferable that it is 2-65 mass%, It is 8-60 mass%. More preferably.
本実施形態においては、共重合体ラテックスの硬さをコントロールすることを目的として、（ｄ）成分として、スチレンを、共重合体を構成する単量体成分全量に対し、１〜６５質量％含有させることが好ましい。 In this embodiment, for the purpose of controlling the hardness of the copolymer latex, styrene is contained as component (d) in an amount of 1 to 65% by mass based on the total amount of monomer components constituting the copolymer. It is preferable to make it.
次に、本実施形態に係る乳化重合について説明する。 Next, the emulsion polymerization according to this embodiment will be described.
本実施形態に係る乳化重合の反応系には、上記（ａ）〜（ｄ）成分以外に、乳化剤（界面活性剤）、重合開始剤、更に必要に応じて、連鎖移動剤、還元剤などを配合することができる。 In the emulsion polymerization reaction system according to the present embodiment, in addition to the components (a) to (d), an emulsifier (surfactant), a polymerization initiator, and, if necessary, a chain transfer agent, a reducing agent, and the like. Can be blended.
乳化剤としては、例えば、高級アルコールの硫酸エステル塩、アルキルベンゼンスルホン酸塩、アルキルジフェニルエーテルジスルホン酸塩、脂肪族スルホン酸塩、脂肪族カルボン酸塩、デヒドロアビエチン酸塩、ナフタレンスルホン酸のホルマリン縮合物、非イオン性界面活性剤の硫酸エステル塩等のアニオン性界面活性剤、ポリエチレングリコールのアルキルエステル型、アルキルフェニルエーテル型、及びアルキルエーテル型等のノニオン性界面活性剤などが挙げられる。これらは１種を単独でまたは２種以上を組み合わせて使用することができる。乳化剤の配合量は、他の添加剤などの組み合わせを考慮して適宜調整することができる。 Examples of the emulsifier include sulfate esters of higher alcohols, alkylbenzene sulfonates, alkyl diphenyl ether disulfonates, aliphatic sulfonates, aliphatic carboxylates, dehydroabietic acid salts, formalin condensates of naphthalene sulfonic acid, Anionic surfactants such as sulfate ester salts of ionic surfactants, and nonionic surfactants such as alkyl ester type, alkyl phenyl ether type, and alkyl ether type of polyethylene glycol. These can be used alone or in combination of two or more. The blending amount of the emulsifier can be appropriately adjusted in consideration of a combination of other additives.
重合開始剤としては、例えば、過硫酸リチウム、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等の水溶性重合開始剤、クメンハイドロパーオキサイド、過酸化ベンゾイル、ｔ−ブチルハイドロパーオキサイド、アセチルパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、及び１，１，３，３−テトラメチルブチルハイドロパーオキサイド等の油溶性重合開始剤が挙げられる。これらは１種を単独でまたは２種以上を組み合わせて使用することができる。これらのうち、過硫酸カリウム、過硫酸ナトリウム、クメンハイドロパーオキサイド、又はｔ−ブチルハイドロパーオキサイドを用いることが好ましい。重合開始剤の配合量は、単量体組成、重合反応系のｐＨ、他の添加剤などの組み合わせを考慮して適宜調整される。 Examples of the polymerization initiator include water-soluble polymerization initiators such as lithium persulfate, potassium persulfate, sodium persulfate, and ammonium persulfate, cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, Examples thereof include oil-soluble polymerization initiators such as diisopropylbenzene hydroperoxide and 1,1,3,3-tetramethylbutyl hydroperoxide. These can be used alone or in combination of two or more. Of these, potassium persulfate, sodium persulfate, cumene hydroperoxide, or t-butyl hydroperoxide is preferably used. The blending amount of the polymerization initiator is appropriately adjusted in consideration of the combination of the monomer composition, the pH of the polymerization reaction system, and other additives.
連鎖移動剤としては、例えば、ｎ−ヘキシルメルカプタン、ｎ−オクチルメルカプタン、ｔ−オクチルメルカプタン、ｎ−ドデシルメルカプタン、ｔ−ドデシルメルカプタン、ｎ−ステアリルメルカプタン等のアルキルメルカプタン；ジメチルキサントゲンジサルファイド、ジイソプロピルキサントゲンジサルファイド等のキサントゲン化合物；テトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、テトラメチルチウラムモノスルフィド等のチウラム系化合物；２，６−ジ−ｔ−ブチル−４−メチルフェノール、スチレン化フェノール等のフェノール系化合物；アリルアルコール等のアリル化合物；ジクロルメタン、ジブロモメタン、四臭化炭素等のハロゲン化炭化水素化合物；α−ベンジルオキシスチレン、α−ベンジルオキシアクリロニトリル、α−ベンジルオキシアクリルアミド等のビニルエーテル；トリフェニルエタン、ペンタフェニルエタン、アクロレイン、メタアクロレイン、チオグリコール酸、チオリンゴ酸、２−エチルヘキシルチオグリコレート、ターピノレン、α−メチルスチレンダイマーなどの連鎖移動剤が挙げられる。これらは１種を単独でまたは２種以上を組み合わせて使用することができる。連鎖移動剤の配合量は、他の添加剤などの組み合わせを考慮して適宜調整することができる。 Examples of the chain transfer agent include alkyl mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-stearyl mercaptan; dimethylxanthogen disulfide, diisopropylxanthogendi Xanthogen compounds such as sulfide; thiuram compounds such as tetramethylthiuram disulfide, tetraethylthiuram disulfide and tetramethylthiuram monosulfide; phenolic compounds such as 2,6-di-t-butyl-4-methylphenol and styrenated phenol; Allyl compounds such as allyl alcohol; halogenated hydrocarbon compounds such as dichloromethane, dibromomethane, carbon tetrabromide; α-benzyloxystyrene, α-benzine Vinyl ethers such as ruoxyacrylonitrile and α-benzyloxyacrylamide; Chain of triphenylethane, pentaphenylethane, acrolein, methacrolein, thioglycolic acid, thiomalic acid, 2-ethylhexyl thioglycolate, terpinolene, α-methylstyrene dimer A transfer agent is mentioned. These can be used alone or in combination of two or more. The blending amount of the chain transfer agent can be appropriately adjusted in consideration of combinations of other additives.
還元剤としては、例えば、亜硫酸塩、亜硫酸水素塩、ピロ亜硫酸塩、亜ニチオン酸塩、ニチオン酸塩、チオ硫酸塩、ホルムアルデヒドスルホン酸塩、ベンズアルデヒドスルホン酸塩；Ｌ−アスコルビン酸、エリソルビン酸、酒石酸、クエン酸などのカルボン酸類およびその塩；デキストロース、サッカロースなどの還元糖類；ジメチルアニリン、トリエタノールアミンなどのアミン類が挙げられる。これらは１種を単独でまたは２種以上を組み合わせて使用することができる。これらのうち、Ｌ−アスコルビン酸、エリソルビン酸が好ましい。還元剤の配合量は、他の添加剤などの組み合わせを考慮して適宜調整することができる。 Examples of the reducing agent include sulfite, bisulfite, pyrosulfite, nithionate, nithionate, thiosulfate, formaldehyde sulfonate, benzaldehyde sulfonate; L-ascorbic acid, erythorbic acid, tartaric acid. And carboxylic acids such as citric acid and salts thereof; reducing sugars such as dextrose and saccharose; and amines such as dimethylaniline and triethanolamine. These can be used alone or in combination of two or more. Of these, L-ascorbic acid and erythorbic acid are preferred. The blending amount of the reducing agent can be appropriately adjusted in consideration of a combination of other additives.
また、本実施形態に係る反応系には、共重合体の分子量及び架橋構造を制御する目的で、ペンタン、ヘキサン、ヘプタン、オクタン、シクロヘキサン、シクロヘプタン等の飽和炭化水素；ペンテン、ヘキセン、ヘプテン、シクロペンテン、シクロヘキセン、シクロヘプテン、４−メチルシクロヘキセン、１−メチルシクロヘキセン等の不飽和炭化水素；ベンゼン、トルエン、キシレン等の芳香族炭化水素などの炭化水素化合物を配合することができる。これらは１種を単独でまたは２種以上を組み合わせて使用することができる。これらのうち、シクロヘキセン、トルエンを用いることが好ましい。 In addition, the reaction system according to the present embodiment includes saturated hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, cycloheptane; pentene, hexene, heptene, Unsaturated hydrocarbons such as cyclopentene, cyclohexene, cycloheptene, 4-methylcyclohexene and 1-methylcyclohexene; hydrocarbon compounds such as aromatic hydrocarbons such as benzene, toluene and xylene can be blended. These can be used alone or in combination of two or more. Of these, cyclohexene and toluene are preferably used.
更に、本実施形態に係る反応系には、必要に応じて、電解質、酸素補足剤、キレート剤、消泡剤、老化防止剤、防腐剤、抗菌剤、難燃剤、紫外線吸収剤等の添加剤を配合してもよい。これらの添加剤は、種類及び使用量ともに適宜適量使用することができる。 Furthermore, the reaction system according to the present embodiment includes additives such as an electrolyte, an oxygen scavenger, a chelating agent, an antifoaming agent, an anti-aging agent, an antiseptic, an antibacterial agent, a flame retardant, and an ultraviolet absorber as necessary. May be blended. These additives can be used in appropriate amounts in both types and amounts.
本実施形態においては、重合開始剤投入開始時の反応系に（ａ）成分の一部、（ｂ）成分の一部、（ｃ）成分の一部、（ｄ）成分の一部、乳化剤、還元剤、連鎖移動剤を含有させることが好ましい。 In the present embodiment, a part of the component (a), part of the component (b), part of the component (c), part of the component (d), emulsifier, It is preferable to contain a reducing agent and a chain transfer agent.
重合開始剤投入開始時の反応系に（ａ）成分の一部を含有させる場合、（ａ）成分の全量の１〜２５質量％を含有させることが好ましく、３〜２０質量％を含有させることがより好ましい。 When a part of the component (a) is included in the reaction system at the start of charging the polymerization initiator, it is preferable to include 1 to 25% by mass, and 3 to 20% by mass of the total amount of the component (a). Is more preferable.
重合開始剤投入開始時の反応系に（ｂ）成分の一部を含有させる場合、（ｂ）成分の全量の０質量％超４０質量％以下を含有させることが好ましく、０．１〜３０質量％を含有させることがより好ましい。更に、（ｂ）成分は、反応系のポリマー転化率が１．０％に到達した到達時（以下、単に「到達時」という）から単量体成分の全量投入終了した終了時（以下、単に「終了時」という）までの時間、の５％の時点以降から、上記（ｂ）エチレン系不飽和カルボン酸単量体の残部の添加を開始して、上記到達時から終了時までの時間、の８０％の時点までに、上記（ｂ）エチレン系不飽和カルボン酸単量体の全量の９２％以上を投入することが好ましい。これらの条件を満たすように（ｂ）成分を添加することで、乾燥時及び湿潤時のいずれにおいても十分な接着強度を発現できる低粘度の共重合体ラテックスを得ることができる。さらに、上記到達時から終了時までの時間、の７０％の時点までに上記（ｂ）エチレン系不飽和カルボン酸単量体の全量の９５％以上を添加することが好ましく、最も好ましくは、６０％の時点までに上記（ｂ）エチレン系不飽和カルボン酸単量体の全量を添加することが好ましい。 When a part of the component (b) is included in the reaction system at the start of charging the polymerization initiator, it is preferable to include more than 0% by mass and 40% by mass or less of the total amount of the component (b). % Is more preferable. Furthermore, the component (b) is from the time when the polymer conversion rate of the reaction system reaches 1.0% (hereinafter simply referred to as “when reached”) to the time when the entire amount of the monomer component has been charged (hereinafter simply referred to as “only”). From the time point of 5% of the time to “end time”), the addition of the remainder of the (b) ethylenically unsaturated carboxylic acid monomer is started, and the time from the arrival time to the end time, It is preferable to add at least 92% of the total amount of the (b) ethylenically unsaturated carboxylic acid monomer by the time of 80%. By adding the component (b) so as to satisfy these conditions, it is possible to obtain a low-viscosity latex copolymer that can exhibit a sufficient adhesive strength both during drying and when wet. Further, it is preferable to add 95% or more of the total amount of the (b) ethylenically unsaturated carboxylic acid monomer by 70% of the time from the arrival time to the end time, most preferably 60%. % Of the total amount of the (b) ethylenically unsaturated carboxylic acid monomer is preferred.
上記到達時とは、反応系に添加した単量体のポリマー転化率が１．０％に到達した時点をいう。ポリマー転化率が１．０％に到達した時点は、単量体成分、開始剤及び水が共存開始した時点（０点）から３０分後に実測することから算出する。３０分後に測定したポリマー転化率が１％を超えていなかったら、さらに３０分経ってから測定し、ポリマー転化率が１％超えるまで３０分毎に測定する。ポリマー転化率が１％を超えたら、１％を超えたデータと０点とを結んでポリマー転化率が１．０％となる時点を「到達時」とする。 The term “arrival time” refers to the time when the polymer conversion rate of the monomer added to the reaction system reaches 1.0%. The time point when the polymer conversion rate reaches 1.0% is calculated from actual measurement 30 minutes after the time point (0 point) when the monomer component, the initiator and water coexist. If the polymer conversion rate measured after 30 minutes does not exceed 1%, it is measured after another 30 minutes, and is measured every 30 minutes until the polymer conversion rate exceeds 1%. When the polymer conversion rate exceeds 1%, the time when the polymer conversion rate reaches 1.0% by connecting the data exceeding 1% and 0 point is defined as “at the time of arrival”.
ポリマー転化率は、反応槽内より採取した反応液を秤量し、１５０℃で１時間乾燥後、再度秤量して固形分量Ｃを測定して、次式より算出することができる。
ポリマー転化率（％）＝［固形分量Ｃ（ｇ）−反応液に含まれる単量体以外の固形分量（ｇ）］／反応系に添加した単量体成分量（ｇ）×１００
なお、「到達時」は、予め求められたデータに基づき設定することができる。例えば、実施する乳化重合と同様の反応系を用意し、この反応系のポリマー転化率の推移に基づき予め到達時を求めておくことができる。
The polymer conversion rate can be calculated from the following equation by weighing the reaction solution collected from the reaction vessel, drying at 150 ° C. for 1 hour, weighing again, and measuring the solid content C.
Polymer conversion (%) = [Solid content C (g) −Solid content other than monomer contained in reaction solution (g)] / Amount of monomer component added to reaction system (g) × 100
Note that “at the time of arrival” can be set based on data obtained in advance. For example, a reaction system similar to the emulsion polymerization to be performed can be prepared, and the arrival time can be obtained in advance based on the transition of the polymer conversion rate of this reaction system.
重合開始剤投入開始時の反応系に（ｃ）成分の一部を含有させる場合、（ｃ）成分の全量の１０〜９０質量％を含有させることが好ましく、１５〜８０質量％を含有させることがより好ましい。また、（ｃ）成分は、到達時までに、（ｃ）成分の全量を投入せず、到達時から終了時までの時間、の６０％の時点までに、（ｃ）成分の全量の８０質量％以上を投入することが好ましい。 When a part of the component (c) is included in the reaction system at the start of charging the polymerization initiator, it is preferable to include 10 to 90% by mass of the total amount of the component (c), and 15 to 80% by mass. Is more preferable. In addition, the component (c) is not charged with the total amount of the component (c) by the time of arrival, and is 80% of the total amount of the component (c) by 60% of the time from the arrival to the end. % Or more is preferably added.
上記到達時までに、反応系に（ｃ）シアン化ビニル単量体の全量を投入せず、到達時から投入時までの時間の６０％の時点までに、（ｃ）シアン化ビニル単量体の全量の８０質量％以上を投入して乳化重合を行うことにより、得られる共重合体ラテックスは、乾燥時及び湿潤時のいずれにおいても十分な接着強度を発現できるとともに、塗工紙作成時の操業性も良好なものとなり、更に容易に低粘度化することが可能となる。上記到達時までに反応系に（ｃ）シアン化ビニル単量体の全量を投入した場合、共重合体ラテックスをフィルムにした際の耐溶剤性が劣り、接着強度が低下する傾向がある。また、上記到達時から単量体成分の全量投入終了時までの時間、の６０％の時点までに、（ｃ）シアン化ビニル単量体の全量の８０質量％以上を投入しなかった場合、ラテックス粘度の低減効果が著しく劣る傾向がある。 By the time of the above, (c) the vinyl cyanide monomer is not charged into the reaction system by the time 60% of the time from the time of arrival to the time of the introduction, without charging the total amount of the (c) vinyl cyanide monomer. By carrying out emulsion polymerization by adding 80% by mass or more of the total amount of the copolymer latex, the resulting copolymer latex can exhibit sufficient adhesive strength both when dry and when wet, and at the time of creating coated paper The operability is also good, and it is possible to easily lower the viscosity. When the total amount of (c) vinyl cyanide monomer is introduced into the reaction system by the time when the above is reached, the solvent resistance when the copolymer latex is made into a film is inferior, and the adhesive strength tends to decrease. Further, when 60% or more of the total amount of the vinyl cyanide monomer is not charged by 60% of the time from the above arrival to the end of the total amount of monomer components, There is a tendency that the latex viscosity reducing effect is remarkably inferior.
また、上記到達時から上記終了時までの時間、の６０％の時点までに投入する（ｃ）成分の量は、接着強度の向上及びラテックス粘度の低減の観点から、（ｃ）成分の全量を基準として８５質量％以上であることが好ましく、９０質量％以上であることがより好ましい。 In addition, the amount of the component (c) to be added up to 60% of the time from the time of arrival to the time of completion is the total amount of the component (c) from the viewpoint of improving the adhesive strength and reducing the latex viscosity. The reference is preferably 85% by mass or more, and more preferably 90% by mass or more.
重合開始剤投入開始時の反応系に（ｄ）成分の一部を含有させる場合、（ｄ）成分の全量の１〜４５質量％を含有させることが好ましく、２〜３０質量％を含有させることがより好ましい。 When a part of the component (d) is contained in the reaction system at the start of charging the polymerization initiator, it is preferable to contain 1 to 45% by mass, and 2 to 30% by mass of the total amount of the component (d). Is more preferable.
乳化剤及び重合開始剤は全量を重合開始剤投入開始時の反応系に含有させることが好ましい。 The total amount of the emulsifier and the polymerization initiator is preferably contained in the reaction system at the start of charging the polymerization initiator.
重合開始剤投入開始時の反応系は、例えば、耐圧性の重合反応容器に、純水、上述した各（ａ）〜（ｄ）成分、乳化剤、重合開始剤、連鎖移動剤、還元剤、その他の成分を所定量加え、例えば、傾斜翼、タービン翼及び、マックスブレンド翼などにより撹拌することにより調製できる。 The reaction system at the start of charging the polymerization initiator is, for example, a pressure-resistant polymerization reaction vessel, pure water, the components (a) to (d) described above, an emulsifier, a polymerization initiator, a chain transfer agent, a reducing agent, and the like. Can be prepared by adding a predetermined amount and stirring with, for example, an inclined blade, a turbine blade, and a Max blend blade.
本実施形態においては、安全性に配慮した槽内圧力および生産性の観点から、上記反応温度を３０〜１００℃の範囲に設定することが好ましく、４０〜８５℃の範囲に設定することがより好ましい。この場合、上記の反応温度の範囲に開始温度を有する重合開始剤が用いられる。 In the present embodiment, the reaction temperature is preferably set in the range of 30 to 100 ° C., more preferably set in the range of 40 to 85 ° C., from the viewpoint of safety in the tank and productivity in consideration of safety. preferable. In this case, a polymerization initiator having an initiation temperature in the above reaction temperature range is used.
反応系の温度は、例えば、外部加熱により０．２５〜１．０℃／分で昇温することができる。 The temperature of the reaction system can be raised at, for example, 0.25 to 1.0 ° C./min by external heating.
上記到達時以降の反応系に（ａ）〜（ｄ）成分を添加する方法としては、例えば、一括添加方法、分割添加方法、連続添加方法、パワーフィード方法を採用することができる。反応系内の単量体をある一定濃度以下に抑制して安全性を向上する観点からは、連続添加方法（以下、連添という場合もある）を採用することが好ましい。更に、連添を複数回行ってもよい。 As a method of adding the components (a) to (d) to the reaction system after the arrival, for example, a batch addition method, a divided addition method, a continuous addition method, and a power feed method can be employed. From the viewpoint of improving the safety by suppressing the monomer in the reaction system to a certain concentration or less, it is preferable to employ a continuous addition method (hereinafter sometimes referred to as continuous addition). Further, the attachment may be performed a plurality of times.
乳化重合の反応時間については、例えば、生産性の観点から、上記到達時から（ａ）〜（ｄ）成分の全量投入終了時までの時間を１〜１５時間とすることが好ましく、２〜１０時間とすることがより好ましい。また、乳化重合は、（ａ）〜（ｄ）成分のポリマー転化率が９５％以上となるまで行うことが好ましく、９７％以上となるまで行うことがより好ましい。 Regarding the reaction time of emulsion polymerization, for example, from the viewpoint of productivity, it is preferable that the time from the time of arrival to the end of charging all the components (a) to (d) is 1 to 15 hours. More preferably, it is time. The emulsion polymerization is preferably performed until the polymer conversion rate of the components (a) to (d) is 95% or more, and more preferably 97% or more.
また、本実施形態においては、ポリマー転化率が９５％を超えたことを確認して反応を終了させることが好ましい。ポリマー転化率は、固形分量から算出、又は重合槽を冷却した熱量から算出できる。こうして、共重体ラテックスが得られる。 Moreover, in this embodiment, it is preferable to complete | finish a reaction, confirming that the polymer conversion rate exceeded 95%. The polymer conversion rate can be calculated from the solid content or from the amount of heat obtained by cooling the polymerization tank. In this way, a copolymer latex is obtained.
共重合体ラテックスは、潤滑剤の分散安定性の観点から、アンモニア、水酸化カリウム、水酸化ナトリウムなどにより、ｐＨが６．０以上に調整されていることが好ましく、６．５以上に調整されていることがより好ましく、７．０以上に調整されていることが更に好ましい。ｐＨを比較的高くすることにより潤滑剤の分散安定性が向上する理由は定かではないが、（ｂ）成分の解離度が向上することにより、潤滑剤の分散安定性が向上するものと推察される。共重合体ラテックスのｐＨの上限値は特に限定されないが、ｐＨは９．０以下に調整されていることが好ましく、８．５以下に調整されていることがより好ましい。 From the viewpoint of the dispersion stability of the lubricant, the copolymer latex is preferably adjusted to a pH of 6.0 or higher with ammonia, potassium hydroxide, sodium hydroxide or the like, and is adjusted to 6.5 or higher. More preferably, it is more preferably adjusted to 7.0 or more. Although the reason why the dispersion stability of the lubricant is improved by increasing the pH is not clear, it is presumed that the dispersion stability of the lubricant is improved by improving the dissociation degree of the component (b). The Although the upper limit of pH of copolymer latex is not specifically limited, It is preferable that pH is adjusted to 9.0 or less, and it is more preferable that it is adjusted to 8.5 or less.
また、共重合体ラテックスは、加熱減圧蒸留などの方法により、未反応単量体及び他の低沸点化合物が除去されていることが好ましい。 The copolymer latex is preferably freed of unreacted monomers and other low-boiling compounds by a method such as heating under reduced pressure.
共重合体ラテックスの平均粒子径は、３０〜２５０ｎｍであることが好ましく、４０〜１８０ｎｍであることがより好ましく、５０〜１６０ｎｍであることが更に好ましく、６０〜１６０ｎｍであることが特に好ましい。共重合体ラテックスの平均粒子径が２５０ｎｍを超えると、共重合体ラテックスのバインダーとしての性能が低下する傾向があり、３０ｎｍ未満であると、共重合体ラテックスの分散安定性が低下する、または共重合体ラテックスの粘度が高くなる傾向がある。共重合体ラテックスの平均粒子径は、ＪＩＳ Ｚ８８２６に準拠し、光子相関法による平均粒子径を動的光散乱法により測定することができる。 The average particle size of the copolymer latex is preferably 30 to 250 nm, more preferably 40 to 180 nm, still more preferably 50 to 160 nm, and particularly preferably 60 to 160 nm. When the average particle size of the copolymer latex exceeds 250 nm, the performance of the copolymer latex as a binder tends to be reduced, and when it is less than 30 nm, the dispersion stability of the copolymer latex decreases or the copolymer latex decreases. The viscosity of the polymer latex tends to increase. The average particle diameter of the copolymer latex can be measured by a dynamic light scattering method based on JIS Z8826, and the average particle diameter by the photon correlation method can be measured.
（分散剤）
本実施形態の分散安定化剤には、分散剤を配合する。分散剤とは、一つの相に他の物質を微粒子状に安定に散在させる作用をする薬剤である。分散剤として具体的には、ポリカルボン酸塩、ピロリン酸塩、ヘキサメタリン酸塩、ナフタレンスルホン酸塩（ナフタレンスルホン酸ホルマリン縮合物塩等）などが挙げられる。これらの中でも、潤滑剤の分散安定性を良好にする観点から、ポリカルボン酸塩が好ましい。ポリカルボン酸塩としては、ポリアクリル酸塩が好ましい。分散剤を配合することにより、ラテックス粘度を低減することが可能である。しかし、分散剤を多量に配合した場合、分散安定化剤と潤滑剤とを混合した際の潤滑剤の分散安定性が低下し、潤滑剤の凝集物が発生する。そのため、分散安定化剤における分散剤の含有量は、共重合体ラテックスの固形分１００質量部に対して０．０１質量部以上１．８質量部以下にする必要がある。分散剤は、１種を単独で又は２種以上を組み合わせて用いることができる。
(Dispersant)
A dispersion agent is blended in the dispersion stabilizer of this embodiment. A dispersant is an agent that acts to stably disperse other substances in one phase in the form of fine particles. Specific examples of the dispersant include polycarboxylates, pyrophosphates, hexametaphosphates, naphthalenesulfonates (such as naphthalenesulfonate formalin condensate salts). Among these, a polycarboxylate is preferable from the viewpoint of improving the dispersion stability of the lubricant. As the polycarboxylate, polyacrylate is preferable. By blending a dispersant, the latex viscosity can be reduced. However, when a large amount of the dispersant is blended, the dispersion stability of the lubricant when the dispersion stabilizer and the lubricant are mixed decreases, and aggregates of the lubricant are generated. Therefore, the content of the dispersant in the dispersion stabilizer needs to be 0.01 parts by mass or more and 1.8 parts by mass or less with respect to 100 parts by mass of the solid content of the copolymer latex. A dispersing agent can be used individually by 1 type or in combination of 2 or more types.
分散剤としてポリカルボン酸塩を用いる場合、その重量平均分子量は１０００〜１０００００であることが好ましく、１５００〜８００００であることがより好ましく、２０００〜６００００であることが更に好ましく、２０００〜５００００であることが特に好ましく、２０００〜４００００であることが極めて好ましく、２０００〜２００００であることが最も好ましい。ポリカルボン酸塩の重量平均分子量が１０００未満であると、共重合体ラテックスへの減粘効果が小さい傾向があり、１０００００を超えると、共重合体ラテックスが増粘する傾向がある。ポリカルボン酸塩の重量平均分子量は、ゲル浸透クロマトグラフィーにより測定することができる。 When using a polycarboxylate as a dispersant, the weight average molecular weight is preferably 1000 to 100,000, more preferably 1500 to 80000, still more preferably 2000 to 60000, and 2000 to 50000. Particularly preferred is 2000 to 40000, most preferred is 2000 to 20000. When the weight average molecular weight of the polycarboxylic acid salt is less than 1000, the effect of reducing the viscosity to the copolymer latex tends to be small, and when it exceeds 100,000, the copolymer latex tends to increase in viscosity. The weight average molecular weight of the polycarboxylate can be measured by gel permeation chromatography.
ポリカルボン酸塩としては、例えば東亞合成株式会社製のアロン（登録商標）シリーズや、日本触媒株式会社製のアクアリック（登録商標）シリーズ、花王株式会社製のポイズ（登録商標）シリーズ等が挙げられる。 Examples of polycarboxylates include Aron (registered trademark) series manufactured by Toagosei Co., Ltd., Aquaric (registered trademark) series manufactured by Nippon Shokubai Co., Ltd., and Poise (registered trademark) series manufactured by Kao Corporation. It is done.
（その他の成分）
本実施形態の分散安定化剤には、必要に応じて、防腐剤、老化防止剤、印刷適性向上剤、界面活性剤などの機能性添加剤を配合してもよい。これらの添加剤は、種類及び使用量ともに適宜適量使用することができる。
(Other ingredients)
If necessary, the dispersion stabilizer of this embodiment may contain a functional additive such as a preservative, an anti-aging agent, a printability improver, and a surfactant. These additives can be used in appropriate amounts in both types and amounts.
本実施形態に係る分散安定化剤は、潤滑剤と混合した際の潤滑剤の分散安定性を向上させることができ、潤滑剤の凝集の発生を抑制することができる。そのため、この分散安定化剤を用いて紙塗工用組成物を調製することで、塗工紙作成時のバッキングロールやカレンダーロールの汚れを防ぎ、操業性の低下及び得られる塗工紙の外観不良の発生を抑制することができる。したがって、本実施形態に係る分散安定化剤は、特に塗工紙製品を製造するための紙塗工用組成物において、潤滑剤と混合して用いてその凝集を防ぐ、潤滑剤の分散安定化剤として有用である。 The dispersion stabilizer according to this embodiment can improve the dispersion stability of the lubricant when mixed with the lubricant, and can suppress the occurrence of aggregation of the lubricant. Therefore, by preparing a composition for paper coating using this dispersion stabilizer, dirt on the backing roll and calendar roll at the time of creating the coated paper is prevented, the operability is reduced, and the appearance of the resulting coated paper The occurrence of defects can be suppressed. Therefore, the dispersion stabilizer according to the present embodiment is used in the composition for paper coating particularly for producing coated paper products, and is used by mixing with the lubricant to prevent the aggregation thereof. Useful as an agent.
また、本実施形態に係る分散安定化剤は、紙塗工用以外にも、潤滑剤と混合して用いる用途に好適に用いることができ、不織布などの繊維結合用、カーペットのバッキング用、電池用（例えば電極、セパレータ、耐熱保護層など）、塗料用、粘接着剤用などに有用である。 Further, the dispersion stabilizer according to the present embodiment can be suitably used for applications used by mixing with a lubricant other than for paper coating, for bonding fibers such as nonwoven fabric, for backing a carpet, and for a battery. It is useful for applications (eg, electrodes, separators, heat-resistant protective layers, etc.), paints, and adhesives.
本実施形態に係る分散安定化剤と混合される潤滑剤としては特に限定されないが、例えば、ステアリン酸カルシウム等の脂肪酸金属塩の水系分散体、ポリエチレンワックス、モンタン酸ワックス等のワックスエマルションが挙げられる。潤滑剤は、１種を単独で又は２種以上を組み合わせて用いることができる。 The lubricant mixed with the dispersion stabilizer according to this embodiment is not particularly limited, and examples thereof include an aqueous dispersion of a fatty acid metal salt such as calcium stearate, and a wax emulsion such as polyethylene wax and montanic acid wax. One type of lubricant can be used alone, or two or more types can be used in combination.
紙塗工用組成物は、例えば、本実施形態に係る分散安定化剤と、潤滑剤と、必要に応じて、顔料、他のバインダー、助剤などとを含むものが挙げられる。 Examples of the paper coating composition include a dispersion stabilizer according to the present embodiment, a lubricant, and, if necessary, a pigment, another binder, an auxiliary agent, and the like.
顔料としては、カオリンクレー、炭酸カルシウム、タルク、硫酸バリウム、酸化チタン、水酸化アルミニウム、酸化亜鉛、サチンホワイトなどの無機顔料、ポリスチレンラテックスなどの有機顔料を用いることができる。これらは、１種を単独でまたは２種以上を組み合わせて使用することができる。 As the pigment, inorganic pigments such as kaolin clay, calcium carbonate, talc, barium sulfate, titanium oxide, aluminum hydroxide, zinc oxide, and satin white, and organic pigments such as polystyrene latex can be used. These can be used alone or in combination of two or more.
他のバインダーとしては、澱粉、酸化澱粉、エステル化澱粉等の変性澱粉、大豆蛋白、カゼインなどの天然バインダー、ポリビニルアルコール、カルボキシメチルセルロースなどの水溶性合成バインダー、ポリ酢酸ビニルラテックス、アクリル系ラテックスなどの合成ラテックスなどが挙げられる。これらは、１種を単独でまたは２種以上を組み合わせて使用することができる。 Other binders include starch, oxidized starch, modified starch such as esterified starch, natural binders such as soy protein and casein, water-soluble synthetic binders such as polyvinyl alcohol and carboxymethylcellulose, polyvinyl acetate latex, acrylic latex, etc. Examples include synthetic latex. These can be used alone or in combination of two or more.
助剤としては、消泡剤（ポリグリコール、脂肪酸エステル、リン酸エステル、シリコーンオイルなど）、レベリング剤（ロート油、ジシアンジアミド、尿素など）、防腐剤、蛍光染料、カラー保水性向上剤（アルギン酸ナトリウムなど）などが挙げられる。 Auxiliaries include antifoaming agents (polyglycols, fatty acid esters, phosphate esters, silicone oils, etc.), leveling agents (funnel oil, dicyandiamide, urea, etc.), preservatives, fluorescent dyes, color water retention agents (sodium alginate) Etc.).
紙塗工用組成物における共重合体ラテックスを含有する分散安定化剤の含有量は、顔料１００質量部に対して固形分の含有量が１〜２０質量部となることが好ましく、２〜１５質量部となることがより好ましい。 The content of the dispersion stabilizer containing the copolymer latex in the paper coating composition is preferably such that the solid content is 1 to 20 parts by mass with respect to 100 parts by mass of the pigment, and 2 to 15 It is more preferable to become a mass part.
紙塗工用組成物において、潤滑剤の固形分の含有量は、分散安定化剤の固形分１００質量部に対して、０．０５〜３００質量部であることが好ましく、０．１〜１００質量部であることがより好ましい。分散安定化剤に対する潤滑剤の含有量が上記範囲内であることで、潤滑剤の分散安定性の向上効果をより有効に得ることができる。 In the composition for paper coating, the solid content of the lubricant is preferably 0.05 to 300 parts by mass with respect to 100 parts by mass of the solid content of the dispersion stabilizer. More preferably, it is part by mass. When the content of the lubricant with respect to the dispersion stabilizer is within the above range, the effect of improving the dispersion stability of the lubricant can be obtained more effectively.
本発明の他の側面によれば、共重合体ラテックスを含有する分散安定化剤と潤滑剤とを混合した混合物における上記潤滑剤の分散安定性を向上させる方法であって、上記分散安定化剤における分散剤の含有量を、上記共重合体ラテックスの固形分１００質量部に対して０．０１質量部以上１．８質量部以下とする、潤滑剤の分散安定性向上方法が提供される。かかる方法では、上述した本実施形態の分散安定化剤を潤滑剤と混合することにより、潤滑剤の分散安定性を向上させることができる。 According to another aspect of the present invention, there is provided a method for improving the dispersion stability of the lubricant in a mixture obtained by mixing a dispersion stabilizer containing a copolymer latex and a lubricant, the dispersion stabilizer There is provided a method for improving the dispersion stability of a lubricant, wherein the content of the dispersing agent in is set to 0.01 to 1.8 parts by mass with respect to 100 parts by mass of the solid content of the copolymer latex. In such a method, the dispersion stability of the lubricant can be improved by mixing the dispersion stabilizer of the present embodiment described above with the lubricant.
以下、実施例により、本発明を更に具体的に説明する。ただし、本発明は以下の実施例に限定されるものではない。また、特段の断りが無い限り、％や部は質量を基準とする。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples. Unless otherwise specified,% and parts are based on mass.
＜共重合体ラテックスの製造＞
表１に示す材料を同表に示す配合量（単位：質量部）で配合して反応を行い、共重合体ラテックスＮｏ．１〜２３を合成した。各共重合体ラテックスの具体的な合成手順を以下に示す。また、表１中の各成分及び記号は下記の化合物を示す。なお、表１には示されていないが、場合により合成後に添加する乳化剤Ｅ−３〜Ｅ−５についても以下に示した。
<Manufacture of copolymer latex>
The materials shown in Table 1 were mixed in the amounts (unit: parts by mass) shown in the same table and reacted, and copolymer latex No. 1 was reacted. 1 to 23 were synthesized. The specific synthesis procedure for each copolymer latex is shown below. Moreover, each component and symbol in Table 1 indicate the following compounds. Although not shown in Table 1, emulsifiers E-3 to E-5 that are added after the synthesis in some cases are also shown below.
（ａ）成分：脂肪族共役ジエン系単量体
ＢＤＥ：１，３−ブタジエン
（ｂ）成分：エチレン系不飽和カルボン酸単量体
ＩＡ：イタコン酸
ＦＡ：フマル酸
ＡＡ：アクリル酸
ＭＡＡ：メタクリル酸
（ｃ）成分：シアン化ビニル単量体
ＡＣＮ：アクリロニトリル
（ｄ）成分：（ａ）〜（ｃ）成分と共重合可能な単量体
ＳＴＹ：スチレン
ＭＭＡ：メタクリル酸メチル
ＨＥＡ：ヒドロキシエチルアクリレート
（その他の成分）
ＣＨＸ：シクロヘキセン
α−ＭＳＤ：α−メチルスチレンダイマー
ＴＤＭ：ｔ−ドデシルメルカプタン
乳化剤
Ｅ−１：デモールＮＬ（β−ナフタレンスルホン酸ホルマリン縮合物ナトリウム塩、花王株式会社製）
Ｅ−２：サーフィノール１０４Ｅ（アセチレングリコール、日信化学工業株式会社製）
Ｅ−３：エマルゲンＡ６０（ポリオキシエチレンジスチレン化フェニルエーテル、花王株式会社製）
Ｅ−４：ニューコール７０７ＳＦ（ポリオキシアルキレン多環フェニルエーテルサルフェートアンモニウム塩、日本乳化剤株式会社製）
Ｅ−５：ネオペレックスＧＳ（ドデシルベンゼンスルホン酸ナトリウム、花王株式会社製）
ＫＰＳ：過硫酸カリウム（重合開始剤）
ＮａＨＣＯ３：炭酸水素ナトリウム（電解質）
重合水：純水
ｐＨ調整剤：ＮａＯＨ又はＫＯＨ
(A) Component: Aliphatic conjugated diene monomer BDE: 1,3-butadiene (b) Component: Ethylenically unsaturated carboxylic acid monomer IA: Itaconic acid FA: Fumaric acid AA: Acrylic acid MAA: Methacrylic acid (C) Component: Vinyl cyanide monomer ACN: Acrylonitrile (d) Component: Monomer copolymerizable with components (a) to (c) STY: Styrene MMA: Methyl methacrylate HEA: Hydroxyethyl acrylate (Others) Ingredients)
CHX: cyclohexene α-MSD: α-methylstyrene dimer TDM: t-dodecyl mercaptan emulsifier E-1: demole NL (β-naphthalenesulfonic acid formalin condensate sodium salt, manufactured by Kao Corporation)
E-2: Surfynol 104E (acetylene glycol, manufactured by Nissin Chemical Industry Co., Ltd.)
E-3: Emulgen A60 (polyoxyethylene distyrenated phenyl ether, manufactured by Kao Corporation)
E-4: New Coal 707SF (polyoxyalkylene polycyclic phenyl ether sulfate ammonium salt, manufactured by Nippon Emulsifier Co., Ltd.)
E-5: Neoperex GS (sodium dodecylbenzenesulfonate, manufactured by Kao Corporation)
KPS: potassium persulfate (polymerization initiator)
NaHCO 3 : Sodium bicarbonate (electrolyte)
Polymerized water: Pure water pH adjuster: NaOH or KOH
以下の各共重合体ラテックスの合成手順において、共重合体ラテックスの重合転化率は、反応器内より採取した反応液を秤量し、１５０℃で１時間乾燥後、再度秤量して固形分量を測定して、次式より算出することができる。
重合転化率（％）＝［（固形分量（ｇ）−反応液に含まれる単量体以外の固形分量（ｇ））／反応系に添加した単量体成分量（ｇ）］×１００
In the following copolymer latex synthesis procedures, the polymerization conversion rate of the copolymer latex is measured by weighing the reaction solution collected from the reactor, drying at 150 ° C. for 1 hour, and then weighing again to measure the solid content. And can be calculated from the following equation.
Polymerization conversion rate (%) = [(solid content (g) −solid content other than monomer contained in reaction solution (g)) / monomer component added to reaction system (g)] × 100
（共重合体ラテックスＮｏ．１、２、８の作製）
表１に示す乳化剤、重合開始剤、炭酸水素ナトリウム、重合水を耐圧性の重合反応器に仕込み、十分に攪拌した後、表１に示す１段目の各単量体及びその他の成分を加えて反応器内温度が７０℃となった時点から、表１に示す２段目の各単量体及びその他の成分を４００分かけて連続的に添加した。その後、重合反応器内を８０℃に昇温し、重合転化率が９５％を超えた時点で重合を終了した。次いで、得られた共重合体ラテックスについて、表１に示すｐＨ調整剤でｐＨを調整し、共重合体ラテックスＮｏ．１、２、８を得た。
(Production of copolymer latex No. 1, 2, 8)
The emulsifier, polymerization initiator, sodium hydrogen carbonate, and polymerization water shown in Table 1 were charged into a pressure-resistant polymerization reactor and stirred sufficiently, and then each monomer in the first stage shown in Table 1 and other components were added. From the time when the temperature in the reactor reached 70 ° C., the second-stage monomers shown in Table 1 and other components were continuously added over 400 minutes. Thereafter, the temperature in the polymerization reactor was raised to 80 ° C., and the polymerization was terminated when the polymerization conversion rate exceeded 95%. Subsequently, about the obtained copolymer latex, pH was adjusted with the pH adjuster shown in Table 1, and copolymer latex No. 1 was adjusted. 1, 2, 8 were obtained.
（共重合体ラテックスＮｏ．３、４、６、７の作製）
表１に示す乳化剤、重合開始剤、炭酸水素ナトリウム、重合水を耐圧性の重合反応器に仕込み、十分に攪拌した後、表１に示す１段目の各単量体及びその他の成分を加えて反応器内温度が７０℃となった時点から、表１に示す２段目の各単量体及びその他の成分を２００分かけて連続的に添加した。２段目の各単量体及びその他の成分の添加終了後、ただちに表１に示す３段目の各単量体及びその他の成分を１８０分かけて連続的に添加した。その後、重合反応器内を８０℃に昇温し、重合転化率が９５％を超えた時点で重合を終了した。次いで、得られた共重合体ラテックスについて、表１に示すｐＨ調整剤でｐＨを調整し、共重合体ラテックスＮｏ．３、４、６、７を得た。
(Production of copolymer latex No. 3, 4, 6, 7)
The emulsifier, polymerization initiator, sodium hydrogen carbonate, and polymerization water shown in Table 1 were charged into a pressure-resistant polymerization reactor and stirred sufficiently, and then each monomer in the first stage shown in Table 1 and other components were added. From the time when the temperature in the reactor reached 70 ° C., the second-stage monomers shown in Table 1 and other components were continuously added over 200 minutes. Immediately after the addition of each monomer and other components in the second stage, each monomer and other components in the third stage shown in Table 1 were continuously added over 180 minutes. Thereafter, the temperature in the polymerization reactor was raised to 80 ° C., and the polymerization was terminated when the polymerization conversion rate exceeded 95%. Subsequently, about the obtained copolymer latex, pH was adjusted with the pH adjuster shown in Table 1, and copolymer latex No. 1 was adjusted. 3, 4, 6, 7 were obtained.
（共重合体ラテックスＮｏ．５の作製）
表１に示す乳化剤、重合開始剤、炭酸水素ナトリウム、重合水を耐圧性の重合反応機に仕込み、十分に攪拌した後、表１に示す１段目の各単量体及びその他の成分を加えて反応器内温度が７０℃となった時点から、表１に示す２段目の各単量体及びその他の成分を２００分かけて連続的に添加した。２段目の各単量体及びその他の成分の添加終了後、ただちに表１に示す３段目の各単量体及びその他の成分を１８０分かけて連続的に添加した。３段目の各単量体及びその他の成分の添加終了後、ただちに表１に示す４段目の単量体を１５分かけて連続的に添加した。その後、重合反応器内を８０℃に昇温し、重合転化率が９５％を超えた時点で重合を終了した。次いで、得られた共重合体ラテックスについて、表１に示すｐＨ調整剤でｐＨを調整し、共重合体ラテックスＮｏ．５を得た。
(Production of copolymer latex No. 5)
The emulsifier, polymerization initiator, sodium hydrogen carbonate, and polymerization water shown in Table 1 were charged into a pressure-resistant polymerization reactor and stirred sufficiently, and then each monomer in the first stage shown in Table 1 and other components were added. From the time when the temperature in the reactor reached 70 ° C., the second-stage monomers shown in Table 1 and other components were continuously added over 200 minutes. Immediately after the addition of each monomer and other components in the second stage, each monomer and other components in the third stage shown in Table 1 were continuously added over 180 minutes. Immediately after the addition of each monomer in the third stage and other components, the fourth stage monomer shown in Table 1 was continuously added over 15 minutes. Thereafter, the temperature in the polymerization reactor was raised to 80 ° C., and the polymerization was terminated when the polymerization conversion rate exceeded 95%. Subsequently, about the obtained copolymer latex, pH was adjusted with the pH adjuster shown in Table 1, and copolymer latex No. 1 was adjusted. 5 was obtained.
（共重合体ラテックスＮｏ．９の作製）
１段目のイタコン酸を２部、１段目のフマル酸を０部とした以外は、共重合体ラテックスＮｏ．２と同様に重合を行い、共重合体ラテックスＮｏ．２と同様のｐＨ調整剤でｐＨを調整して、共重合体ラテックスＮｏ．９を得た。
(Production of copolymer latex No. 9)
The copolymer latex No. 1 was prepared except that the first stage itaconic acid was 2 parts and the first stage fumaric acid was 0 parts. Polymerization was carried out in the same manner as in Example 2, and copolymer latex No. The pH was adjusted with the same pH adjusting agent as in Example 2, and copolymer latex No. 9 was obtained.
（共重合体ラテックスＮｏ．１０の作製）
１段目のフマル酸を０部、１段目のアクリル酸を２部とした以外は、共重合体ラテックスＮｏ．２と同様に重合を行い、共重合体ラテックスＮｏ．２と同様のｐＨを調整して、共重合体ラテックスＮｏ．１０を得た。
(Production of copolymer latex No. 10)
Copolymer latex No. 1 except that the first stage fumaric acid was 0 parts and the first stage acrylic acid was 2 parts. Polymerization was carried out in the same manner as in Example 2, and copolymer latex No. The same pH as in Example 2 was adjusted, and copolymer latex no. 10 was obtained.
（共重合体ラテックスＮｏ．１１の作製）
乳化剤をＥ−２に変更し、Ｅ−２を１部とした以外は、共重合体ラテックスＮｏ．２と同様に重合を行い、共重合体ラテックスＮｏ．２と同様のｐＨ調整剤でｐＨを調整して、共重合体ラテックスＮｏ．１１を得た。
(Production of copolymer latex No. 11)
The copolymer latex No. was changed except that the emulsifier was changed to E-2 and 1 part of E-2 was used. Polymerization was carried out in the same manner as in Example 2, and copolymer latex No. The pH was adjusted with the same pH adjusting agent as in Example 2, and copolymer latex No. 11 was obtained.
（共重合体ラテックスＮｏ．１２の作製）
乳化剤Ｅ−１を０．８部、炭酸水素ナトリウムを０．２部、重合水を１３０部とした以外は、共重合体ラテックスＮｏ．３と同様に重合を行い、共重合体ラテックスＮｏ．３と同様のｐＨ調整剤でｐＨを調整して、共重合体ラテックスＮｏ．１２を得た。
(Production of copolymer latex No. 12)
Copolymer latex No. 1 except that the emulsifier E-1 was 0.8 part, the sodium bicarbonate was 0.2 part, and the polymerization water was 130 parts. Polymerization was carried out in the same manner as in Example 3, and copolymer latex No. The pH was adjusted with the same pH adjusting agent as in No. 3, and copolymer latex No. 12 was obtained.
（共重合体ラテックスＮｏ．１３の作製）
１段目のフマル酸を２部、３段目のスチレンを２２．３部とした以外は、共重合体ラテックスＮｏ．３と同様に重合を行い、共重合体ラテックスＮｏ．３と同様のｐＨ調整剤でｐＨを調整して、共重合体ラテックスＮｏ．１３を得た。
(Production of copolymer latex No. 13)
The copolymer latex No. 1 was changed except that the first stage fumaric acid was 2 parts and the third stage styrene was 22.3 parts. Polymerization was carried out in the same manner as in Example 3, and copolymer latex No. The pH was adjusted with the same pH adjusting agent as in No. 3, and copolymer latex No. 13 was obtained.
（共重合体ラテックスＮｏ．１４の作製）
１段目のアクリル酸を６部、３段目のスチレンを２２．３部とした以外は、共重合体ラテックスＮｏ．３と同様に重合を行い、共重合体ラテックスＮｏ．３と同様のｐＨ調整剤でｐＨを調整して、共重合体ラテックスＮｏ．１４を得た。
(Production of copolymer latex No. 14)
The copolymer latex No. 1 was changed except that the first-stage acrylic acid was 6 parts and the third-stage styrene was 22.3 parts. Polymerization was carried out in the same manner as in Example 3, and copolymer latex No. The pH was adjusted with the same pH adjusting agent as in No. 3, and copolymer latex No. 14 was obtained.
（共重合体ラテックスＮｏ．１５の作製）
乳化剤Ｅ−１を０．８部、炭酸水素ナトリウムを０．２部、重合水を１３０部とした以外は、共重合体ラテックスＮｏ．１４と同様に重合を行い、共重合体ラテックスＮｏ．１４と同様のｐＨ調整剤でｐＨを調整して、共重合体ラテックスＮｏ．１５を得た。
(Production of copolymer latex No. 15)
Copolymer latex No. 1 except that the emulsifier E-1 was 0.8 part, the sodium bicarbonate was 0.2 part, and the polymerization water was 130 parts. Polymerization was conducted in the same manner as in Example 14, and copolymer latex No. The pH was adjusted with the same pH adjusting agent as in No. 14, and the copolymer latex no. 15 was obtained.
（共重合体ラテックスＮｏ．１６の作製）
１段目のヒドロキシエチルアクリレートを１部、３段目のスチレンを２１．３部とした以外は、共重合体ラテックスＮｏ．１４と同様に重合を行い、共重合体ラテックスＮｏ．１４と同様のｐＨ調整剤でｐＨを調整して、共重合体ラテックスＮｏ．１６を得た。
(Production of copolymer latex No. 16)
Copolymer latex No. 1 was used except that 1 part of the first stage hydroxyethyl acrylate was changed to 1 part and 31.3 parts of styrene was changed to 21.3 parts. Polymerization was conducted in the same manner as in Example 14, and copolymer latex No. The pH was adjusted with the same pH adjusting agent as in No. 14, and the copolymer latex no. 16 was obtained.
（共重合体ラテックスＮｏ．１７の作製）
１段目のフマル酸を１部、３段目のスチレンを２１．３部とした以外は、共重合体ラテックスＮｏ．１４と同様に重合を行い、共重合体ラテックスＮｏ．１４と同様のｐＨ調整剤でｐＨを調整して、共重合体ラテックスＮｏ．１７を得た。
(Production of copolymer latex No. 17)
Copolymer latex No. 1 was used except that the first stage fumaric acid was 1 part and the third stage styrene was 21.3 parts. Polymerization was conducted in the same manner as in Example 14, and copolymer latex No. The pH was adjusted with the same pH adjusting agent as in No. 14, and the copolymer latex no. 17 was obtained.
（共重合体ラテックスＮｏ．１８の作製）
１段目と２段目のシクロヘキセンをそれぞれ５部とした以外は、共重合体ラテックスＮｏ．１４と同様に重合を行い、共重合体ラテックスＮｏ．１４と同様のｐＨ調整剤でｐＨを調整して、共重合体ラテックスＮｏ．１８を得た。
(Production of copolymer latex No. 18)
Copolymer latex No. 1 was used except that the first and second stages of cyclohexene were each 5 parts. Polymerization was conducted in the same manner as in Example 14, and copolymer latex No. The pH was adjusted with the same pH adjusting agent as in No. 14, and the copolymer latex no. 18 was obtained.
（共重合体ラテックスＮｏ．１９の作製）
共重合体ラテックスＮｏ．１４と同様に重合を行い、ｐＨ調整剤として水酸化カリウムを用いてｐＨを調整して、共重合体ラテックスＮｏ．１９を得た。
(Preparation of copolymer latex No. 19)
Copolymer latex no. Polymerization was conducted in the same manner as in Example 14, and the pH was adjusted using potassium hydroxide as a pH adjuster. 19 was obtained.
（共重合体ラテックスＮｏ．２０の作製）
１段目と２段目のシクロヘキセンをそれぞれ５部、１段目と２段目のα−メチルスチレンダイマーを０部、過硫酸カリウムを１．５部とした以外は、共重合体ラテックスＮｏ．４と同様に重合を行い、共重合体ラテックスＮｏ．４と同様のｐＨ調整剤でｐＨを調整して、共重合体ラテックスＮｏ．２０を得た。
(Production of copolymer latex No. 20)
Copolymer Latex No. 1 was prepared except that the first and second cyclohexenes were 5 parts, the first and second stages α-methylstyrene dimer were 0 parts, and potassium persulfate was 1.5 parts. Polymerization was carried out in the same manner as in Example 4, and copolymer latex No. The pH was adjusted with the same pH adjusting agent as in Example 4, and copolymer latex No. 4 was adjusted. 20 was obtained.
（共重合体ラテックスＮｏ．２１の作製）
乳化剤Ｅ−１を１．５部、過硫酸カリウムを１部、重合水を１７０部とした以外は、共重合体ラテックスＮｏ．２０と同様に重合を行い、共重合体ラテックスＮｏ．２０と同様のｐＨ調整剤でｐＨを調整して、共重合体ラテックスＮｏ．２１を得た。
(Production of copolymer latex No. 21)
Copolymer latex No. 1 except that the emulsifier E-1 was 1.5 parts, the potassium persulfate was 1 part, and the polymerization water was 170 parts. Polymerization was conducted in the same manner as in No. 20, and copolymer latex No. The pH was adjusted with the same pH adjusting agent as in No. 20, and copolymer latex No. 21 was obtained.
（共重合体ラテックスＮｏ．２２の作製）
乳化剤Ｅ−１を０．８部、炭酸水素ナトリウムを０．２部、過硫酸カリウムを１部、重合水を１３０部とした以外は、共重合体ラテックスＮｏ．２０と同様に重合を行い、共重合体ラテックスＮｏ．２０と同様のｐＨ調整剤でｐＨを調整して、共重合体ラテックスＮｏ．２２を得た。
(Production of copolymer latex No. 22)
Copolymer latex No. 1 was used except that the emulsifier E-1 was 0.8 part, the sodium bicarbonate was 0.2 part, the potassium persulfate was 1 part, and the polymerization water was 130 parts. Polymerization was conducted in the same manner as in No. 20, and copolymer latex No. The pH was adjusted with the same pH adjusting agent as in No. 20, and copolymer latex No. 22 was obtained.
（共重合体ラテックスＮｏ．２３の作製）
１段目のヒドロキシエチルアクリレートを１部、３段目のスチレンを１１部、過硫酸カリウムを１部とした以外は、共重合体ラテックスＮｏ．２０と同様に重合を行い、共重合体ラテックスＮｏ．２０と同様のｐＨ調整剤でｐＨを調整して、共重合体ラテックスＮｏ．２３を得た。
(Production of copolymer latex No. 23)
Copolymer Latex No. 1 was used except that 1 part of the first stage hydroxyethyl acrylate was 11 parts, 3 parts of styrene was 11 parts, and potassium persulfate was 1 part. Polymerization was conducted in the same manner as in No. 20, and copolymer latex No. The pH was adjusted with the same pH adjusting agent as in No. 20, and copolymer latex No. 23 was obtained.
［実施例１〜４０及び比較例１〜２８］
共重合体ラテックスに、場合により分散剤及び乳化剤を添加し、十分に攪拌することで、実施例１〜４０及び比較例１〜２８の分散安定化剤（固形分４５〜５５質量％）を得た。表２〜表５に、各実施例及び各比較例で使用した共重合体ラテックスの種類、そのｐＨ及び平均粒子径、分散剤の種類、その添加量（共重合体ラテックスの固形分１００質量部に対する量）及び分子量、並びに、乳化剤の種類及びその添加量（共重合体ラテックスの固形分１００質量部に対する量）を示した。
[Examples 1 to 40 and Comparative Examples 1 to 28]
In some cases, a dispersant and an emulsifier are added to the copolymer latex and sufficiently stirred to obtain dispersion stabilizers (solid content: 45 to 55% by mass) of Examples 1 to 40 and Comparative Examples 1 to 28. It was. In Tables 2 to 5, the type of copolymer latex used in each example and each comparative example, its pH and average particle size, the type of dispersant, the amount added (100 parts by mass of the solid content of the copolymer latex) ) And molecular weight, as well as the type of emulsifier and the amount added (amount based on 100 parts by mass of the solid content of the copolymer latex).
共重合体ラテックスの平均粒子径は、ＪＩＳ Ｚ８８２６に準拠し、光子相関法による平均粒子径を動的光散乱法により測定したものである。測定に際しては、ＦＰＡＲ−１０００（大塚電子製）を使用した。 The average particle diameter of the copolymer latex is based on JIS Z8826, and the average particle diameter by the photon correlation method is measured by the dynamic light scattering method. In the measurement, FPAR-1000 (manufactured by Otsuka Electronics) was used.
表２〜表５中の各分散剤は下記の化合物を示す。
Ａ−１：アロン Ｔ−５０（ポリアクリル酸ナトリウム、東亞合成株式会社製）
Ａ−２：分子量（Ｍｗ）６０００の特殊ポリカルボン酸塩、サンノプコ株式会社製
Ａ−３：分子量（Ｍｗ）３５００のポリアクリル酸ナトリウム、株式会社日本触媒製
Ａ−４：アクアリック ＴＬ３７（アクリル酸・マレイン酸コポリマーのナトリウム塩、株式会社日本触媒製）
Ａ−５：アクアリック ＴＬ２１３（アクリル酸・マレイン酸コポリマーのナトリウム塩、株式会社日本触媒製）
Ａ−６：アクアリック ＴＬ２００（アクリル酸・マレイン酸コポリマーのナトリウム塩、株式会社日本触媒製）
Ａ−７：アクアリック ＴＬ４００（アクリル酸・マレイン酸コポリマーのナトリウム塩、株式会社日本触媒製）
Ａ−８：ポイズ ５２１（アクリル酸・マレイン酸コポリマーのナトリウム塩、花王株式会社製）
Ａ−９：アクアリック ＤＬ−８００（ポリアクリル酸ナトリウム、株式会社日本触媒製）
Ａ−１０：アロン Ａ−２０ＵＮ（ポリアクリル酸ナトリウム、東亞合成株式会社製）
Ａ−１１：アロン Ａ−６３３０（ポリカルボン酸ナトリウム、東亞合成株式会社製）
Ａ−１２：アクアリック ＹＳ−１００（ポリアクリル酸ナトリウム、株式会社日本触媒製）
Ａ−１３：分子量（Ｍｗ）５５００のポリアクリル酸ナトリウム、株式会社日本触媒製
Ａ−１４：アロン Ａ−２１０（ポリアクリル酸ナトリウム、東亞合成株式会社製）
Each dispersant in Tables 2 to 5 represents the following compound.
A-1: Aron T-50 (sodium polyacrylate, manufactured by Toagosei Co., Ltd.)
A-2: Special polycarboxylate having a molecular weight (Mw) of 6000, Sannopco Co., Ltd. A-3: Sodium polyacrylate having a molecular weight (Mw) of 3500, Nippon Shokubai Co., Ltd. A-4: Aqualic TL37 (acrylic acid) -Sodium salt of maleic acid copolymer, manufactured by Nippon Shokubai Co., Ltd.
A-5: Aqualic TL213 (sodium salt of acrylic acid / maleic acid copolymer, manufactured by Nippon Shokubai Co., Ltd.)
A-6: Aqualic TL200 (sodium salt of acrylic acid / maleic acid copolymer, manufactured by Nippon Shokubai Co., Ltd.)
A-7: Aqualic TL400 (sodium salt of acrylic acid / maleic acid copolymer, manufactured by Nippon Shokubai Co., Ltd.)
A-8: Poise 521 (sodium salt of acrylic acid / maleic acid copolymer, manufactured by Kao Corporation)
A-9: Aqualic DL-800 (sodium polyacrylate, manufactured by Nippon Shokubai Co., Ltd.)
A-10: Aron A-20UN (sodium polyacrylate, manufactured by Toagosei Co., Ltd.)
A-11: Aron A-6330 (polycarboxylate sodium, manufactured by Toagosei Co., Ltd.)
A-12: Aquaric YS-100 (polyacrylic acid sodium, manufactured by Nippon Shokubai Co., Ltd.)
A-13: Sodium polyacrylate having a molecular weight (Mw) of 5500, Nippon Shokubai Co., Ltd. A-14: Aron A-210 (Sodium polyacrylate, manufactured by Toagosei Co., Ltd.)
＜潤滑剤添加安定性の評価＞
潤滑剤を添加した際の安定性を確認する試験として、実施例及び比較例で得られた分散安定化剤（固形分４８．３質量％）２０ｇに、潤滑剤として市販のステアリン酸カルシウムの水系分散体（固形分５４．２質量％）を０．８ｍＬ添加し、２分間静置させた後、スパチュラで１回／１秒の速さで６秒間かき混ぜた。その後、分散安定化剤と潤滑剤との混合溶液全量を黒ケント紙上に敷いたＰＥＴフィルム上に乗せ、凝集物の有無を観察した。この試験は、各実施例及び各比較例について、それぞれ３回繰り返して行った。
<Evaluation of lubricant addition stability>
As a test for confirming stability when a lubricant is added, an aqueous dispersion of commercially available calcium stearate as a lubricant is added to 20 g of the dispersion stabilizer (solid content: 48.3% by mass) obtained in Examples and Comparative Examples. 0.8 mL of the body (solid content 54.2% by mass) was added and allowed to stand for 2 minutes, and then stirred with a spatula at a speed of 1 time / second for 6 seconds. Thereafter, the entire mixed solution of the dispersion stabilizer and the lubricant was placed on a PET film laid on black Kent paper, and the presence or absence of aggregates was observed. This test was repeated three times for each example and each comparative example.
図１〜４は、分散安定化剤と潤滑剤との混合溶液全量を黒ケント紙上に敷いたＰＥＴフィルム上に乗せた状態を撮影した写真である。図１は、実施例２０の分散安定化剤を用いた場合の写真であり、凝集物が全く無く、潤滑剤の分散安定性が極めて良好な状態を示す。図２は、実施例２３の分散安定化剤を用いた場合の写真であり、凝集物Ａが少なく、潤滑剤の分散安定性が概ね良好である状態を示す。図３は、比較例１０の分散安定化剤を用いた場合の写真であり、凝集物Ａが多く、潤滑剤の分散安定性がやや劣る状態を示す。図４は、比較例１１の分散安定化剤を用いた場合の写真であり、凝集物Ａが多く且つ大きく、潤滑剤の分散安定性が劣る状態を示す。 1 to 4 are photographs of a state in which the entire amount of a mixed solution of a dispersion stabilizer and a lubricant is placed on a PET film laid on black Kent paper. FIG. 1 is a photograph of the case where the dispersion stabilizer of Example 20 was used, showing no state of aggregates and very good dispersion stability of the lubricant. FIG. 2 is a photograph when the dispersion stabilizer of Example 23 is used, and shows a state in which the aggregate A is small and the dispersion stability of the lubricant is generally good. FIG. 3 is a photograph when the dispersion stabilizer of Comparative Example 10 is used, and shows a state in which there are many aggregates A and the dispersion stability of the lubricant is slightly inferior. FIG. 4 is a photograph when the dispersion stabilizer of Comparative Example 11 is used, and shows a state where the aggregate A is large and large, and the dispersion stability of the lubricant is poor.
潤滑剤の分散状態が、図１に示した写真と同等の状態である場合を「Ａ」、図２に示した写真と同等の状態である場合を「Ｂ」、図３に示した写真と同等の状態である場合を「Ｃ」、図２に示した写真と同等の状態である場合を「Ｄ」とし、以下の評価基準により、潤滑剤添加安定性を評価した。その結果を表２〜表５に示す。
優良：３回の試験結果の全てが「Ａ」又は「Ｂ」であり、「Ｃ」及び「Ｄ」が１回も出なかったもの。
良：「Ａ」又は「Ｂ」が２回、「Ｃ」が１回出たもの。
不可：「Ｃ」及び「Ｄ」が合計で２回以上出たもの。
なお、「Ａ」又は「Ｂ」が２回、「Ｄ」が１回出たものについては、再度上記試験を３回繰り返し行って評価し直した。
When the dispersed state of the lubricant is the same as the photograph shown in FIG. 1, “A”, when the lubricant is the same as the photograph shown in FIG. 2, “B”, and the photograph shown in FIG. Lubricant addition stability was evaluated according to the following evaluation criteria, with “C” representing the equivalent state and “D” representing the state equivalent to the photograph shown in FIG. The results are shown in Tables 2-5.
Excellent: All three test results were “A” or “B”, and “C” and “D” were never generated.
Good: “A” or “B” appears twice and “C” appears once.
Impossible: “C” and “D” appear more than once in total.
In addition, about the thing which "A" or "B" appeared twice and "D" appeared once, the said test was repeated 3 times and evaluated again.
＊実施例６及び７の分散安定化剤では、潤滑剤の添加時に分散安定化剤と潤滑剤との混合溶液が増粘した。これは、分散剤の分子量が高いことに起因するものと考えられる。
＊＊実施例８の分散安定化剤では、潤滑剤の添加時に分散安定化剤と潤滑剤との混合溶液が増粘しなかったが、実施例１０の分散安定化剤では、潤滑剤の添加時に分散安定化剤と潤滑剤との混合溶液がやや増粘した。このことから、分散剤の分子量（Ｍｗ）２００００は、増粘するかしないかの境界線であると考えられる。そのため、増粘をより十分に抑制する観点では、分散剤の分子量（Ｍｗ）は２００００以下であることが好ましい。
* In the dispersion stabilizers of Examples 6 and 7, when the lubricant was added, the mixed solution of the dispersion stabilizer and the lubricant was thickened. This is considered due to the high molecular weight of the dispersant.
** In the dispersion stabilizer of Example 8, the mixed solution of the dispersion stabilizer and the lubricant did not thicken when the lubricant was added, but in the dispersion stabilizer of Example 10, the addition of the lubricant Occasionally, the mixed solution of dispersion stabilizer and lubricant was slightly thickened. From this, it is considered that the molecular weight (Mw) 20000 of the dispersant is a boundary line of whether or not to increase the viscosity. Therefore, from the viewpoint of sufficiently suppressing thickening, the molecular weight (Mw) of the dispersant is preferably 20000 or less.
表２〜表５に示した結果から明らかなように、本発明の分散安定化剤によれば、潤滑剤と混合した際に、混合物（混合溶液）中での潤滑剤の分散安定性を良好にできることが確認された。 As is apparent from the results shown in Tables 2 to 5, according to the dispersion stabilizer of the present invention, when mixed with the lubricant, the dispersion stability of the lubricant in the mixture (mixed solution) is good. It was confirmed that
Claims (7)
分散剤の含有量が、前記共重合体ラテックスの固形分１００質量部に対して０．０１質量部以上１．８質量部以下である、分散安定化剤。 A lubricant dispersion stabilizer containing a copolymer latex,
The dispersion stabilizer whose content of a dispersing agent is 0.01 mass part or more and 1.8 mass parts or less with respect to 100 mass parts of solid content of the said copolymer latex.
前記分散安定化剤における分散剤の含有量を、前記共重合体ラテックスの固形分１００質量部に対して０．０１質量部以上１．８質量部以下とする、潤滑剤の分散安定性向上方法。 A method for improving the dispersion stability of the lubricant in a mixture in which a dispersion stabilizer containing a copolymer latex and a lubricant are mixed,
A method for improving the dispersion stability of a lubricant, wherein the content of the dispersant in the dispersion stabilizer is 0.01 to 1.8 parts by mass with respect to 100 parts by mass of the solid content of the copolymer latex. .
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|---|---|---|---|---|
| JPH06248031A (en) * | 1993-02-25 | 1994-09-06 | Japan Synthetic Rubber Co Ltd | Copolymer latex |
| JPH0770988A (en) * | 1993-08-25 | 1995-03-14 | Mitsui Toatsu Chem Inc | Composition for paper coating |
| JPH08283544A (en) * | 1995-04-11 | 1996-10-29 | Teijin Ltd | Stretched polyester molding |
| JPH11350387A (en) * | 1998-06-02 | 1999-12-21 | Mitsui Chem Inc | Composition for coated paper |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06248031A (en) * | 1993-02-25 | 1994-09-06 | Japan Synthetic Rubber Co Ltd | Copolymer latex |
| JPH0770988A (en) * | 1993-08-25 | 1995-03-14 | Mitsui Toatsu Chem Inc | Composition for paper coating |
| JPH08283544A (en) * | 1995-04-11 | 1996-10-29 | Teijin Ltd | Stretched polyester molding |
| JPH11350387A (en) * | 1998-06-02 | 1999-12-21 | Mitsui Chem Inc | Composition for coated paper |
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