JP4675557B2 - Different layer latex for moisture-proof processing - Google Patents
Different layer latex for moisture-proof processing Download PDFInfo
- Publication number
- JP4675557B2 JP4675557B2 JP2003323261A JP2003323261A JP4675557B2 JP 4675557 B2 JP4675557 B2 JP 4675557B2 JP 2003323261 A JP2003323261 A JP 2003323261A JP 2003323261 A JP2003323261 A JP 2003323261A JP 4675557 B2 JP4675557 B2 JP 4675557B2
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- weight
- latex
- monomer
- moisture
- 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.)
- Expired - Fee Related
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- 238000002156 mixing Methods 0.000 claims description 10
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Images
Landscapes
- Paper (AREA)
- Graft Or Block Polymers (AREA)
Description
本発明は包装、容器などに用いられるリサイクル可能な防湿紙を製造する際の原紙表面に塗工するラテックス組成物に関する。特に、常態防湿性、折り曲げ防湿性及び耐ブロッキング性に優れる防湿紙用ラテックス組成物に関する。 The present invention relates to a latex composition that is applied to the surface of a base paper when manufacturing recyclable moisture-proof paper used for packaging, containers, and the like. In particular, the present invention relates to a latex composition for moisture-proof paper, which is excellent in normal moisture resistance, folding moisture resistance and blocking resistance.
従来より、防湿性を必要とする包装紙の分野においては、ターポリン紙やワックス紙などが知られている。また、加工の簡易性、安価性などからポリエチレン、ポリプロピレンなどの高分子化合物を塗工あるいは張り合わせなどを施し、防湿性を付与したポリオレフィンラミネート紙が一般的に使用されている。しかしながら、これらのラミネート紙は防湿性に関しては十分な機能を発揮し得るものであるが廃棄された場合のリサイクル性に乏しいという欠点を有している。つまり、防湿紙の製造工程で発生する損紙、トリミング屑及び成形加工時に発生する損紙、また製品になった後の回収品などは、水中離解性が極端に悪いため、パルプの再利用化が困難である。このため、これら廃棄物は古紙として回収することができない。これは、ラミネートに用いられている高分子フィルムが強固な連続皮膜を形成していて、かつ水不溶性であることに起因している。このため、省資源、環境問題の観点から再利用可能な新規な防湿紙の開発が進められてきている。 Conventionally, tarpaulin paper and wax paper are known in the field of wrapping paper requiring moisture resistance. In addition, polyolefin laminated paper to which moisture resistance is imparted by applying or pasting a polymer compound such as polyethylene or polypropylene is generally used because of its simplicity of processing and low cost. However, these laminated papers can exhibit a sufficient function with respect to moisture resistance, but have a drawback of poor recyclability when discarded. In other words, waste paper generated during the manufacturing process of moisture-proof paper, trimming waste, waste paper generated during molding processing, and recovered products after becoming a product are extremely poor in water disintegration. Is difficult. For this reason, these wastes cannot be recovered as waste paper. This is because the polymer film used for lamination forms a strong continuous film and is insoluble in water. For this reason, development of new moisture-proof paper that can be reused has been advanced from the viewpoint of resource saving and environmental problems.
これまでも、再利用可能な防湿加工による防湿紙の技術については、いくつか提案されている。例えば、ブタジエン系ラテックスにワックスを配合したものを塗工し、防湿紙を得る方法（例えば［特許文献１］）、アクリルラテックスを配合し塗工する方法（例えば［特許文献２］）、及びこの系で更にアクリルエマルジョンを架橋させたものを用いることにより離解性、ヒートシール性を向上させた防湿紙を得る方法（例えば［特許文献３］）などが提案されている。さらに近年では、架橋性ビニル単量体や金属架橋剤を用いることで離解性、耐ブロッキング性、折り曲げ性が良好な防湿用樹脂組成物が提案されている（例えば［特許文献４］、［特許文献５］）。 Until now, several techniques for moisture-proof paper by reusable moisture-proof processing have been proposed. For example, a method of coating a butadiene-based latex with a wax and obtaining moisture-proof paper (eg, [Patent Document 1]), a method of blending and coating an acrylic latex (eg, [Patent Document 2]), and this There has been proposed a method (for example, [Patent Document 3]) of obtaining moisture-proof paper with improved disaggregation and heat sealability by using a system obtained by further crosslinking an acrylic emulsion. In recent years, moisture-proof resin compositions having good disaggregation, blocking resistance, and bendability have been proposed by using a crosslinkable vinyl monomer or a metal crosslinking agent (for example, [Patent Document 4], [Patents] Reference 5]).
この様に、包装紙等の表面を加工する樹脂材料を親水性の樹脂エマルジョンにすることによって、その水中離解性を改良する技術は、従来より盛んに提案されているものである。
一方、防湿加工に樹脂ラテックスを用いた場合、その樹脂粒子の微細な形態構造に対する技術開発は、非常に重要である。すなわち、ラテックス等は、成膜してフィルムを形成した際に、フィルム樹脂構造中にラテックスの樹脂粒子の微細な形態構造に由来する微小な分散構造を形成する。これによって、均一の樹脂構造では実現できない特異な機能の発現が可能である。
As described above, a technique for improving the disintegration property in water by using a hydrophilic resin emulsion as a resin material for processing the surface of wrapping paper or the like has been actively proposed.
On the other hand, when resin latex is used for moisture-proof processing, technical development for the fine morphological structure of the resin particles is very important. That is, when latex or the like is formed into a film, a latex or the like forms a fine dispersion structure derived from the fine morphological structure of the latex resin particles in the film resin structure. As a result, it is possible to develop unique functions that cannot be realized with a uniform resin structure.
例えば、［特許文献６］には、高いガラス転移温度（Ｔｇ）（４０〜９０℃）のコア部及び低いガラス転移温度（Ｔｇ）（−４０〜２０℃）のシェル部からなるコア／シェル構造粒子を含有する共重合体ラテックスと合成ゼオライト並びにワックスエマルジョンを含有してなる防湿性組成物を原紙上に塗工することにより、離解性が非常に優れ、防湿性が高く、折り曲げ時の防湿性の低下もなく、ブロッキングを生じることのない防湿紙が得られることを開示している。
また、［特許文献７］では、低いガラス転移温度（Ｔｇ）（０℃以下）のコア部分と高いガラス転移温度（Ｔｇ）（−１０〜５０℃）のシェル部分からなるコア／シェル構造を有する変性スチレン・ブタジエン共重合体ラテックスを原紙上に塗工することにより、離解性が非常に優れ、防湿性が高い防湿紙が得られることを開示している。
For example, [Patent Document 6] describes a core / shell structure comprising a core portion having a high glass transition temperature (Tg) (40 to 90 ° C.) and a shell portion having a low glass transition temperature (Tg) (−40 to 20 ° C.). By coating the base paper with a moisture-proof composition comprising a copolymer latex containing particles, a synthetic zeolite, and a wax emulsion, it has excellent disaggregation, high moisture resistance, and moisture resistance when folded. It is disclosed that moisture-proof paper that does not cause blocking and does not cause blocking is obtained.
[Patent Document 7] has a core / shell structure composed of a core portion having a low glass transition temperature (Tg) (0 ° C. or less) and a shell portion having a high glass transition temperature (Tg) (−10 to 50 ° C.). It is disclosed that a moisture-proof paper having excellent disaggregation and high moisture resistance can be obtained by coating a modified styrene / butadiene copolymer latex on a base paper.
さらに、最近では、低いガラス転移温度（Ｔｇ）（−７０〜−５℃）のコア部及び高いガラス転移温度（Ｔｇ）（１０〜１００℃）のシェル部からなるコア／シェル構造を有する変性（メタ）アクリル酸エステル共重合体ラテックスからなる防湿紙塗工用ラテックスや、高いガラス転移温度（Ｔｇ）（６０〜９５℃）の変性（メタ）アクリル酸エステル共重合体からなるシェル部及び低いガラス転移温度（Ｔｇ）（−１５〜２０℃）の変性スチレン・ブタジエン共重合体からなるコア部によるコア／シェル構造を有するラテックスからなる防湿紙塗工用樹脂組成物なども、離解性が非常に優れ、防湿性が高く、折り曲げ時の防湿性の低下もなく、ブロッキングを生じることのない防湿紙を製造する技術として開示されている。 Furthermore, recently, a modified core / shell structure comprising a core portion having a low glass transition temperature (Tg) (−70 to −5 ° C.) and a shell portion having a high glass transition temperature (Tg) (10 to 100 ° C.) ( Latex for coating moisture-proof paper made of meth) acrylate ester latex, shell part made of modified (meth) acrylate ester copolymer having a high glass transition temperature (Tg) (60 to 95 ° C.) and low glass A moisture-proof paper coating resin composition made of latex having a core / shell structure with a core portion made of a modified styrene / butadiene copolymer having a transition temperature (Tg) (-15 to 20 ° C.) is also very disintegrating. It is disclosed as a technique for producing moisture-proof paper that is excellent, has high moisture-proof properties, does not deteriorate moisture-proof properties when bent, and does not cause blocking.
この様に、いわゆる異層構造を有する樹脂ラテックス、あるいは樹脂エマルジョンを防湿塗工用に用いる技術は盛んに提案されているが、ラテックスを構成する樹脂粒子の構造と最終的に構成される防湿紙の表面の樹脂塗膜の内部構造、または樹脂フィルムの物理性質との関係については十分明らかにされていない。これは、高温乾燥によって樹脂粒子の構造が破壊され、新たに構成される樹脂塗膜のモルフォロジーの生成過程を、予め予想するのが極めて困難なためである。
本出願人においても、近年、この分野において研究を重ね、低いガラス転移温度（Ｔｇ）（−７０〜１０℃）の変性スチレン・ブタジエン共重合体からなるコア部及び変性（メタ）アクリル酸エステル共重合体からなるシェル部によるコア／シェル構造を有するラテックスからなる防湿紙塗工用樹脂組成物を、離解性が非常に優れ、防湿性が高く、折り曲げ時の防湿性の低下もなく、ブロッキングを生じることのない防湿紙を製造する技術として開示している。
As described above, techniques for using a resin latex having a so-called different layer structure or a resin emulsion for moisture-proof coating have been actively proposed. However, the structure of the resin particles constituting the latex and the moisture-proof paper finally configured The relationship between the internal structure of the resin coating on the surface of the resin and the physical properties of the resin film has not been sufficiently clarified. This is because the structure of the resin particles is destroyed by high-temperature drying, and it is extremely difficult to predict in advance the formation process of the newly formed resin coating film morphology.
In recent years, the present applicant has also continued research in this field, and the core portion and the modified (meth) acrylic acid ester copolymer composed of a modified styrene-butadiene copolymer having a low glass transition temperature (Tg) (−70 to 10 ° C.). Resin composition for coating moisture-proof paper made of latex with a core / shell structure made of a polymer shell, has excellent disaggregation, high moisture resistance, and does not deteriorate moisture resistance when folded. It is disclosed as a technique for producing moisture-proof paper that does not occur .
このような微細な粒子の形態構造にまで踏み込んだ、ラテックス系コート剤の技術進歩により、古紙回収を容易とする良好な水離解性の防湿紙が得られるようになってきた。しかしながら、このような防湿紙は高温多湿の条件下に放置されると防湿紙の塗工面と包装内容物との間でブロッキングが生じる問題は充分に解決していない。ラテックス共重合体のガラス転移温度を上げることにより高温多湿下のブロッキングを防ぐことができるが、逆に重要な必要性能である折り曲げ防湿性（折り曲げた部分の防湿性）が著しく低下する問題が発生するためである。 Advances in the technology of latex-based coating agents that have advanced to such fine particle morphological structures have made it possible to obtain good water disintegrating moisture-proof paper that facilitates recovery of used paper. However, when such moisture-proof paper is left under high-temperature and high-humidity conditions, the problem of blocking between the coated surface of the moisture-proof paper and the package contents has not been sufficiently solved. By increasing the glass transition temperature of the latex copolymer, blocking under high temperature and high humidity can be prevented, but conversely, there is a problem that the bending moisture resistance (moisture resistance of the folded part), which is an important performance, is significantly reduced. It is to do.
本発明は従来のポリオレフィンラミネート紙に近似する常態防湿性を有するとともに高温多湿下での耐ブロッキング性と折り曲げ防湿性のバランスに特に優れる水離解性防湿紙のコート剤用ラテックス系組成物を提供することを目的とする。 The present invention provides a latex composition for a coating agent for water-disintegrating moisture-proof paper, which has a normal moisture-proof property similar to conventional polyolefin-laminated paper and is particularly excellent in the balance between blocking resistance and folding moisture-proof property under high temperature and high humidity. For the purpose.
本発明者等は、常態防湿性に優れるとともに高温多湿下での耐ブロッキング性と折り曲げ防湿性にも優れる水離解性防湿紙を与えるラテックス系塗工組成物を得るべく、ラテックス共重合体組成、ラテックス粒子層の構造などの面から検討を行った。この結果、特異な異層構造ラテックス［Ｉ］にワックスエマルジョン［ＩＩ］を配合したものが上記の目的とする性能を与えることを見いだし、本発明をなすにいたった。
すなわち、本発明は下記の通りである。
１．（１）ガラス転移温度（Ｔｇ）が−９０〜１０℃を有する共重合体（イ）からなるコア層と、（２）ガラス転移温度（Ｔｇ）が０〜１８０℃の範囲にあり、共重合体（イ）よりも高いガラス転移温度（Ｔｇ）の共重合体（ロ）からなる中間層と、（３）ガラス転移温度（Ｔｇ）が０〜５０℃の範囲にあり、共重合体（イ）よりも高く、共重合体（ロ）のガラス転移温度（Ｔｇ）より低くその差が４℃以上であるガラス転移温度（Ｔｇ）の共重合体（ハ）からなるシェル層とからなる異層構造ラテックスであって、該異層構造ラテックスを構成する共重合体の全重量に対して、中間層の共重合体（ロ)の重量比率が２〜５０重量％であり、共重合体（ハ）の重量比率が１２〜８０重量％であり、共重合体（イ）が単量体として、Ｔｇを低く調整する単量体であるブタジエンと、Ｔｇを高く調整する単量体であるスチレン及びメチルメタアクリレートから選ばれる少なくとも一種とを含み、共重合体（ロ）が単量体としてブタジエンを含まず、Ｔｇを低く調整する単量体である２−エチルヘキシルアクリレートと、Ｔｇを高く調整する単量体であるスチレン、メチルメタアクリレート及びアクリロニトリルから選ばれる少なくとも一種とを含み、共重合体（ハ）が単量体としてブタジエンを含まず、Ｔｇを低く調整する単量体である２−エチルヘキシルアクリレートと、Ｔｇを高く調整する単量体であるスチレン及びメチルメタアクリレートから選ばれる少なくとも一種とを含むことを特徴とする防湿加工用異層構造ラテックス［Ｉ］
In order to obtain a latex-based coating composition that gives a water-disintegrating moisture-proof paper that is excellent in normal moisture resistance and also excellent in blocking resistance and folding moisture resistance under high temperature and high humidity, a latex copolymer composition, The structure of the latex particle layer was examined. As a result, it has been found that a compound having a specific heterostructure latex [I] and a wax emulsion [II] gives the above-mentioned target performance, and the present invention has been made.
That is, the present invention is as follows.
1. (1) a core layer comprising a copolymer (I) having a glass transition temperature (Tg) of −90 to 10 ° C., and (2) a glass transition temperature (Tg) in the range of 0 to 180 ° C. An intermediate layer comprising a copolymer (b) having a glass transition temperature (Tg) higher than that of the blend (a), and (3) a glass transition temperature (Tg) in the range of 0 to 50 ° C. ), Lower than the glass transition temperature (Tg) of the copolymer (b), and the difference between them is 4 ° C. or more and the shell layer made of the copolymer (c) having the glass transition temperature (Tg). The weight ratio of the copolymer (b) in the intermediate layer is 2 to 50% by weight with respect to the total weight of the copolymer constituting the heterostructure latex, and the copolymer (c) ) Is 12 to 80% by weight, the copolymer (I) is used as a monomer, and Tg is adjusted to be low. Butadiene as a monomer and at least one selected from styrene and methyl methacrylate as a monomer for adjusting Tg high, and the copolymer (B) does not contain butadiene as a monomer. and 2-ethylhexyl acrylate is a monomer for adjusting the lower, a monomer higher adjust Tg styrene, saw including at least one selected from methyl methacrylate and acrylonitrile, a copolymer (c) is a single free of butadiene as dimer, and 2-ethylhexyl acrylate is a monomer for adjusting low Tg, the free Mukoto and at least one selected from styrene and methyl methacrylate is a monomer higher adjust Tg Distinctive structure latex for moisture-proof processing [I]
２．（１）コア層を形成する共重合体（イ)からなるラテックスの存在下で、（２）共重合体（ロ）を生成する単量体を乳化共重合させて中間層を形成し、（３）次いで、共重合体（ハ）を生成する単量体を乳化共重合させてシェル層を形成することによって製造する、上記１に記載の防湿加工用異層構造ラテックス［Ｉ］の製造方法。
３．上記１に記載の防湿加工用異層構造ラテックス［Ｉ］１００重量部（固形分換算）とワックスエマルジョン［ＩＩ］０．１〜２０重量部（固形分換算）の割合で配合してなる防湿紙用塗工組成物。
2. (1) In the presence of a latex composed of the copolymer (a) forming the core layer (2), an intermediate layer is formed by emulsion copolymerization of the monomer that forms the copolymer (b) ( 3) Next, the method for producing the moisture-proof heterogeneous structure latex [I] according to 1 above, wherein the shell layer is formed by emulsion copolymerization of the monomer that forms the copolymer (c) .
3. Moisture-proof paper formed by blending 100 parts by weight (in terms of solid content) of the different layer structure latex [I] for moisture-proof processing described in 1 above and 0.1 to 20 parts by weight (in terms of solid content) of wax emulsion [II] Coating composition.
本発明の特定の異層構造ラテックス［Ｉ］とワックスエマルジョン［ＩＩ］からなる組成物を紙に塗工して得られる塗工紙は優れた常態防湿性、折り曲げ防湿性及び耐ブロッキング性を有するとともに水中で容易に離解されるため、リサイクルできる機能をも有する。 The coated paper obtained by applying to the paper the composition comprising the specific heterostructure latex [I] and the wax emulsion [II] of the present invention has excellent normal moisture resistance, folding moisture resistance and blocking resistance. At the same time, since it is easily disaggregated in water, it also has a recyclable function.
本発明について、以下具体的に説明する。
本発明は乳化重合によって製造される、特異な異層構造ラテックス［Ｉ］からなる。ここで、ラテックスとは合成樹脂の水分散体の総称であり、乳化重合により、あるいは乳化分散工程により製造したエマルジョン等である。
また、本発明の異層構造ラテックス［Ｉ］とは、［図１］、［図２］に示す様に、コア層を構成する共重合体（イ）とシェル層を構成する共重合体（ハ）の中間に中間層を構成する共重合体（ロ）が存在する異層粒子構造を有するラテックスである。
本発明の異層構造ラテックス［Ｉ］を構成する共重合体（イ）〜（ハ）の合成には共重合可能なエチレン性不飽和単量体を共重合成分として用いることができる。
The present invention will be specifically described below.
The present invention comprises a unique heterostructure latex [I] produced by emulsion polymerization. Here, latex is a general term for an aqueous dispersion of a synthetic resin, such as an emulsion produced by emulsion polymerization or an emulsion dispersion process.
In addition, as shown in [FIG. 1] and [FIG. 2], the different layer structure latex [I] of the present invention includes a copolymer (A) constituting a core layer and a copolymer (A) constituting a shell layer ( C) Latex having a different layer particle structure in which a copolymer (b) constituting an intermediate layer exists in the middle.
A copolymerizable ethylenically unsaturated monomer can be used as a copolymerization component for the synthesis of the copolymers (a) to (c) constituting the heterostructure latex [I] of the present invention.
共重合可能な単量体としては共役ジエン系単量体、芳香族ビニル系単量体、（メタ）アクリル酸アルキルエステル単量体、エチレン系不飽和カルボン酸単量体、シアン化ビニル系単量体、（メタ）アクリルアミド系単量体、カルボン酸ビニルエステル系単量体、アミノ基含有エチレン性単量体類、ハロゲン化ビニル、スルホン酸基やリン酸基含有単量体、ラジカル重合性の二重結合を２個以上有しているビニル系単量体、重合後に架橋構造を与える官能基を有しているビニル系単量体、重合後に架橋構造を与えるシランカップリング剤などを挙げることができる。これらは単独で、又は２種類以上を組み合わせて使用できる。 Copolymerizable monomers include conjugated diene monomers, aromatic vinyl monomers, (meth) acrylic acid alkyl ester monomers, ethylenically unsaturated carboxylic acid monomers, and vinyl cyanide monomers. Monomer, (meth) acrylamide monomer, carboxylic acid vinyl ester monomer, amino group-containing ethylenic monomers, vinyl halide, sulfonic acid group or phosphate group-containing monomer, radical polymerizability A vinyl monomer having two or more double bonds, a vinyl monomer having a functional group that gives a crosslinked structure after polymerization, a silane coupling agent that gives a crosslinked structure after polymerization, etc. be able to. These can be used alone or in combination of two or more.
共役ジエン系単量体としては、例えば１，３−ブタジエン、イソプレン、２，３−ジメチル１，３−ブタジエン、２−エチル−１，３−ブタジエン、２−メチル−１，３−ブタジエン、１，３ペンタジエン、クロロプレン、２−クロロ−１，３ブタジエン、シクロブタジエンなどを挙げることができ、これらを単独で、又は２種以上組み合わせて使用できる。これらの中でも１，３ブタジエンが好適に使用できる。
共役ジエン系単量体は共重合体（イ）にのみ含まれ、コア層のみを構成する成分である場合、特に、高温多湿下での耐ブロッキング性と折り曲げ防湿性のバランスに特に優れる。
Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, 2,3-dimethyl 1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-butadiene, 1 , 3 pentadiene, chloroprene, 2-chloro-1,3 butadiene, cyclobutadiene and the like, and these can be used alone or in combination of two or more. Among these, 1,3 butadiene can be preferably used.
When the conjugated diene monomer is contained only in the copolymer (a) and is a component constituting only the core layer, it is particularly excellent in the balance between blocking resistance and bending moisture resistance under high temperature and high humidity.
芳香族ビニル系単量体としては、例えばスチレン、α−メチルスチレン、ビニルトルエン、ｐ−メチルスチレン，ｏ−メチルスチレン、ｍ−メチルスチレン、エチルスチレン、ヒドロキシメチルスチレン、ビニルキシレン、ブロモスチレン、ビニルベンジルクロリド、ｐ−ｔ−ブチルスチレン、クロロスチレン、アルキルスチレン、などを挙げることができ、これらを単独で、又は２種以上組み合わせて使用できる。これらの中でもスチレンが好適に使用できる。 Examples of aromatic vinyl monomers include styrene, α-methyl styrene, vinyl toluene, p-methyl styrene, o-methyl styrene, m-methyl styrene, ethyl styrene, hydroxymethyl styrene, vinyl xylene, bromostyrene, vinyl. Benzyl chloride, pt-butyl styrene, chlorostyrene, alkyl styrene, etc. can be mentioned, These can be used individually or in combination of 2 or more types. Among these, styrene can be preferably used.
（メタ）アクリル酸アルキルエステル単量体としては、例えばメチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｎ−アミル（メタ）アクリレート、イソアミルヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、ドデシル（メタ）アクリレート、オクタデシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、プロピレングリコール（メタ）アクリレート、ジエチレングリコールエトキシアクリレート、メトキシポリエチレングリコール（メタ）アクリレート、ステアリル（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、イソボルニル（メタ）アクリレートなどを挙げることができ、これらを単独に、又は２種以上を組み合わせて用いることができる。 Examples of the (meth) acrylic acid alkyl ester monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl ( (Meth) acrylate, n-amyl (meth) acrylate, isoamylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, cyclohexyl (Meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, propylene glycol (meth) Examples include acrylate, diethylene glycol ethoxy acrylate, methoxy polyethylene glycol (meth) acrylate, stearyl (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, and the like. Or two or more types can be used in combination.
エチレン系不飽和カルボン酸単量体としては、例えばアクリル酸、メタアクリル酸、イタコン酸、フマル酸、マレイン酸、クロトン酸、ブテントリカルボン酸、マレイン酸モノエチル、マレイン酸モノメチル、イタコン酸モノエチル、イタコン酸モノメチルなどを挙げることができ、これらを単独で、又は２種以上組み合わせて用いることができる。特に好ましい組み合わせはアクリル酸とメタアクリル酸を併用した場合が防湿性能の面から特に好ましい。また異層構造の上でも、共重合体（ロ）にアクリル酸を用いた場合に防湿性能、離解性能の面から特に好ましい。エチレン系不飽和カルボン酸は防湿性の点から、ラテックスを構成する全単量体の４重量％以下の使用が必須であり、特に好ましくは２．５重量％以下が好ましい。 Examples of the ethylenically unsaturated carboxylic acid monomer include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, crotonic acid, butenetricarboxylic acid, monoethyl maleate, monomethyl maleate, monoethyl itaconic acid, and itaconic acid. A monomethyl etc. can be mentioned, These can be used individually or in combination of 2 or more types. A particularly preferred combination is particularly preferred in terms of moisture-proof performance when acrylic acid and methacrylic acid are used in combination. Moreover, also on a different layer structure, when acrylic acid is used for a copolymer (b), it is especially preferable from the surface of moisture-proof performance and disaggregation performance. From the viewpoint of moisture resistance, the ethylenically unsaturated carboxylic acid must be used in an amount of 4% by weight or less, particularly preferably 2.5% by weight or less, based on the total monomers constituting the latex.
シアン化ビニル系単量体としては、例えばアクリロニトリル、メタクリロニトリル、α−クロルアクリロニトリルなどを挙げることができ、これらを単独に、又は２種以上組み合わせて用いることができる。
（メタ）アクリルアミド系単量体としては、例えば（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミドやＮ−メチル（メタ）アクリルアミドなどのＮ−モノアルキル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミドなどのＮ，Ｎジアルキル（メタ）アクリルアミド、グリシジルメタアクリルアミド、Ｎ−アルコキシ（メタ）アクリルアミド、２−アクリルアミド−２−メチルプロパンスルホン酸などをあげることができ、これらを単独又に、は２種以上組み合わせて用いることができる。
Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and the like, and these can be used alone or in combination of two or more.
Examples of (meth) acrylamide monomers include N-monoalkyl (meth) acrylamides such as (meth) acrylamide, N-methylol (meth) acrylamide and N-methyl (meth) acrylamide, N, N-dimethyl (meth) ) N, N dialkyl (meth) acrylamide such as acrylamide, glycidylmethacrylamide, N-alkoxy (meth) acrylamide, 2-acrylamido-2-methylpropane sulfonic acid and the like can be mentioned. It can be used in combination of more than one species.
他の単量体としては、例えばアミノエチル（メタ）アクリレートやジメチルアミノエチル（メタ）アクリレート及び２−ビニルピリジンなどのアミノ基含有エチレン性単量体、酢酸ビニルなどのカルボン酸ビニルエステル類、塩化ビニルや塩化ビニリデンなどのハロゲン化ビニル、スチレンスルホン酸塩や２−（メタ）アクリロイルオキシエチルスルホン酸及び（メタ）アリルスルホン酸塩などのスルホン酸基含有単量体、燐酸エチレン（メタ）アクリレートや燐酸プロピレン（メタ）アクリレート及び２−（メタ）アクリロイルオキシエチルアシッドホスフェートなどの燐酸基含有単量体などを挙げることができ、これらを単独に、又は２種以上を組み合わせて用いることができる。 Examples of other monomers include amino group-containing ethylenic monomers such as aminoethyl (meth) acrylate and dimethylaminoethyl (meth) acrylate and 2-vinylpyridine, vinyl ester carboxylates such as vinyl acetate, and chloride. Vinyl halides such as vinyl and vinylidene chloride, sulfonic acid group-containing monomers such as styrene sulfonate, 2- (meth) acryloyloxyethyl sulfonic acid and (meth) allyl sulfonate, ethylene (meth) acrylate, Examples thereof include phosphoric acid group-containing monomers such as propylene phosphate (meth) acrylate and 2- (meth) acryloyloxyethyl acid phosphate, and these can be used alone or in combination of two or more.
ラジカル重合性の二重結合を２個以上有しているビニル系単量体は例えば、ジビニルベンゼン、トリビニルベンゼン、ポリオキシエチレンジ（メタ）アクリレート、ポリオキシプロピレンジ（メタ）アクリレー ト、ネオペンチルグリコールジ（メタ）アクリレート、ブタンジオールジ（メタ）アクリレート、 トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレー ト、エチレングリコールジ（メタ）アクリレート、１−３−ブチレングリコールジ（メタ）アクリレート、１，４−ブチレングリコールジ（メタ）アクリレート、１，５−ペンタジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、テトラメチロールメタンテトラ（メタ）アクリレート、アリル（メタ）アクリレート２，２−ビス［４−（（メタ）アクリロキシエトキシ）フェニル］プロパン、２，２−ビス［４−（（メタ）アクリロキシ・ジエトキシ）フェニル］プロパン、２，２−ビス［４−（（メタ）アクリロキシ・ポリエトキシ）フェニル］プロパン、ビス（４−アクリロキシポリエトキシフェニル）プロパン等が挙げられる。 Examples of vinyl monomers having two or more radical polymerizable double bonds include divinylbenzene, trivinylbenzene, polyoxyethylene di (meth) acrylate, polyoxypropylene di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, butanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene glycol di (meth) acrylate, 1-3-butylene glycol di ( (Meth) acrylate, 1,4-butylene glycol di (meth) acrylate, 1,5-pentadiol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene Recall di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylol Propane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, allyl (meth) acrylate 2,2-bis [4-((meth) acryloxyethoxy) phenyl] propane, 2,2-bis [4- ( (Meth) acryloxy / diethoxy) phenyl] propane, 2,2-bis [4-((meth) acryloxy / polyethoxy) phenyl] propane, bis (4-acryloxypolyethoxyphenyl) propane, etc. And the like.
重合中、重合後に架橋構造を与える官能基を有しているビニル系単量体としては例えば、エポキシ基含有モノマー、例えばグリシジル（メタ）アクリレート、アリルグリシジルエーテル、メチルグリシジル（メタ）アクリレート、メチロール基含有モノマー、例えばＮ−メチロール（メタ）アクリルアミド、ジメチロール（メタ）アクリルアミド、アルコキシメチル基含有モノマー、例えばＮ−メトキシメチルアクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミド、Ｎ−ブトキシメチルメタクリルアミド等、ヒドロキシル基含有モノマー等が挙げられる。
重合後に架橋構造を与えるシランカップリング剤としてはビニルトリクロロシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、トリス−２−メトキシエトキシビニルシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルメチルジメト キシシラン等が挙げられる。
As a vinyl monomer having a functional group that gives a cross-linked structure after polymerization, for example, an epoxy group-containing monomer such as glycidyl (meth) acrylate, allyl glycidyl ether, methyl glycidyl (meth) acrylate, methylol group Containing monomers such as N-methylol (meth) acrylamide, dimethylol (meth) acrylamide, alkoxymethyl group-containing monomers such as N-methoxymethyl acrylamide, N-butoxymethyl (meth) acrylamide, N-butoxymethyl methacrylamide, etc. Examples thereof include monomers.
Examples of silane coupling agents that give a crosslinked structure after polymerization include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, tris-2-methoxyethoxyvinylsilane, γ-methacryloxypropyltrimethoxysilane, and γ-methacryloxypropylmethyldisilane. And methoxysilane.
本願発明の異層構造ラテックス［Ｉ］は水性媒体中で単量体、連鎖移動剤などを乳化剤、ラジカル重合開始剤、及び必要に応じてその他の添加剤成分を用いて重合する従来公知の乳化重合方法によって得られる。
連鎖移動剤としては、例えばα−メチルスチレンダイマーなどの核置換α−メチルスチレンの二量体、ｎ−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、ｎ−ドデシルメルカプタン及びｔ−ドデシ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ムジスルフィド及びテトラエチルチウラムジスルフィドなどのジスルフィド類、２−エチルヘキシルチオグリコレート、ターピノーレンなどの公知の全てのものを単独、又は２種以上組み合わせて用いることができる。
The different layer structure latex [I] of the present invention is a conventionally known emulsification in which a monomer, a chain transfer agent and the like are polymerized by using an emulsifier, a radical polymerization initiator, and other additive components as necessary. It is obtained by a polymerization method.
Examples of chain transfer agents include dimers of nucleus-substituted α-methylstyrene such as α-methylstyrene dimer, n-butyl mercaptan, n-octyl mercaptan, n-lauryl mercaptan, n-dodecyl mercaptan, and t-dodecyl mercaptan. All known compounds such as mercaptans, disulfides such as tetramethylthiuram disulfide and tetraethylthiuram disulfide, 2-ethylhexyl thioglycolate, and terpinolene can be used alone or in combination of two or more.
乳化剤としては、例えば脂肪族石鹸、ロジン酸石鹸、アルキルスルホン酸塩、ジアルキルアリールスルホン酸塩、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及びポリオキシエチレンアルキルアリール硫酸塩などのアニオン性乳化剤、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ールエーテル及び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乳化剤など公知のものを単独、あるいは２種以上組み合わせて用いることができる。又これらの他に親水基と親油基を有する界面活性剤の化学構造式の中にエチレン性二重結合を導入した反応性乳化剤も好適に使用でき、更に、ベタイン型などの両性乳化剤及びポリビニルアルコール、カルボキシメチルセルロース、メチルセルロース、ポリビニルピロリドンなどの水溶性高分子の保護コロイド乳化剤なども必要に応じて用いることができる。 Examples of the emulsifier include an anionic emulsifier such as an aliphatic soap, a rosin acid soap, an alkyl sulfonate, a dialkyl aryl sulfonate, an alkyl sulfo succinate, a polyoxyethylene alkyl sulfate, and a polyoxyethylene alkyl aryl sulfate. Known ones such as nonionic emulsifiers such as oxyethylene alkyl ether, polyoxyethylene alkyl aryl ether and polyoxyethylene oxypropylene block copolymer can be used alone or in combination of two or more. In addition to these, reactive emulsifiers in which an ethylenic double bond is introduced into the chemical structural formula of a surfactant having a hydrophilic group and a lipophilic group can also be suitably used. Further, amphoteric emulsifiers such as betaine type and polyvinyl Protective colloid emulsifiers of water-soluble polymers such as alcohol, carboxymethyl cellulose, methyl cellulose, and polyvinyl pyrrolidone can be used as necessary.
ラジカル重合開始剤は、熱又は還元性物質の存在下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、無機系開始剤及び有機系開始剤のいずれも使用できる。このようなものとしては、例えば水溶性及び油溶性のペルオキソ二硫酸塩、過酸化物、アゾビス化合物などで、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を挙げることができ、又他に、ＰＯＬＹＭＥＲ ＨＡＮＤＢＯＯＫ（３ｒｄ．ｅｄｉｔｉｏｎ）、Ｊ．Ｂｒａｎｄｒｕｐ及びＥ．Ｈ．Ｉｍｍｅｒｇｕｔ著、Ｊｏｈｎ Ｗｉｌｌｙ＆Ｓｏｎｓ刊（１９８９）に記載されている化合物も用いることができる。又、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に組み合わせて用いる、いわゆるレドックス重合法を採用することもできる。この重合開始剤の使用量は全単量体の重量に基づき、通常０．１〜５．０重量％、好ましくは０．２〜３．０重量％使用する。 The radical polymerization initiator is one that initiates addition polymerization of a monomer by radical decomposition in the presence of heat or a reducing substance, and any of inorganic initiators and organic initiators can be used. Examples of such compounds include water-soluble and oil-soluble peroxodisulfates, peroxides, azobis compounds, specifically potassium peroxodisulfate, sodium peroxodisulfate, ammonium peroxodisulfate, hydrogen peroxide, Mention may be made of t-butyl hydroperoxide, benzoyl peroxide, 2,2-azobisbutyronitrile, cumene hydroperoxide, and in addition, POLYMER HANDBOOK (3rd. edition), J. Am. Brandrup and E.I. H. The compounds described by Immersutt, published by John Willy & Sons (1989) can also be used. In addition, a so-called redox polymerization method in which a reducing agent such as acidic sodium sulfite, ascorbic acid or a salt thereof, erythorbic acid or a salt thereof or Rongalite is used in combination with a polymerization initiator may be employed. The amount of the polymerization initiator used is usually 0.1 to 5.0% by weight, preferably 0.2 to 3.0% by weight, based on the weight of all monomers.
本発明の異層構造ラテックス［Ｉ］を重合する際、重合中及び重合後に、必要に応じて各種調整剤を添加することができる。例えば、ｐＨ調整剤として水酸化カリウム、水酸化ナトリウム、水酸化アンモニウム、炭酸水素ナトリウム、炭酸ナトリウム、リン酸水素二ナトリウムなどを添加することができる。又、エチレンジアミン四酢酸ナトリウムなどの各種キレート剤なども重合調整剤として添加することができる。
本発明の異層構造ラテックス［Ｉ］を多段乳化重合で得る際の重合温度は通常５〜１２０℃であり、又各段での重合温度は同じでも異なっていても良い。
本発明の異層構造ラテックス［Ｉ］を構成する共重合体（イ）〜（ハ）の製造における単量体混合物の重合系への添加は一括添加法、連続的にあるいは断続的に添加する方法、これらの方法を組み合わせた方法（例えば、単量体混合物の一部添加した後に重合の進行に従って連続的もしくは断続的に添加する方法）などいずれでも良い。
When polymerizing the heterostructure latex [I] of the present invention, various regulators can be added as necessary during and after the polymerization. For example, potassium hydroxide, sodium hydroxide, ammonium hydroxide, sodium hydrogen carbonate, sodium carbonate, disodium hydrogen phosphate and the like can be added as a pH adjuster. Various chelating agents such as sodium ethylenediaminetetraacetate can also be added as a polymerization regulator.
The polymerization temperature for obtaining the heterostructure latex [I] of the present invention by multi-stage emulsion polymerization is usually 5 to 120 ° C., and the polymerization temperature in each stage may be the same or different.
The addition of the monomer mixture to the polymerization system in the production of the copolymers (a) to (c) constituting the heterogeneous latex [I] of the present invention is performed by a batch addition method, continuously or intermittently. Any method may be used, for example, a method combining these methods (for example, a method in which a monomer mixture is partially added and then added continuously or intermittently as the polymerization proceeds).
又、重合にあたってシード重合方法もとることができる。シード用ラテックスの組成は共重合体ラテックスの組成と同じであっても異なってもよく、シード用ラテックスも同一反応容器で製造したもの、異なる他の反応容器で製造したものを用いてもよい。
共重合体（イ）〜（ハ）の重合転化率は通常６０重量％以上、好ましくは８０重量％以上である。
本発明における共重合体（イ）のガラス転移温度（Ｔｇ）は−９０〜１０℃であり、好ましくは−５０〜０℃の範囲である。−９０℃以上の場合は常態防湿性及び耐ブロッキング性が良好であり、１０℃以下の場合は折り曲げ防湿性が顕著に良好である。
Further, a seed polymerization method can be used for the polymerization. The composition of the latex for seed may be the same as or different from the composition of the copolymer latex, and the seed latex produced in the same reaction vessel or a different reaction vessel may be used.
The polymerization conversion rate of the copolymers (a) to (c) is usually 60% by weight or more, preferably 80% by weight or more.
The glass transition temperature (Tg) of the copolymer (I) in the present invention is -90 to 10 ° C, preferably in the range of -50 to 0 ° C. When it is −90 ° C. or higher, normal moisture resistance and blocking resistance are good, and when it is 10 ° C. or lower, folding moisture resistance is remarkably good.
本発明の異層構造ラテックス［Ｉ］は、例えば共重合体（イ）の存在下で共重合体（ロ）、共重合体（ハ）を生成する単量体混合物を乳化共重合させることによって得られる。
生成する共重合体（ロ）のガラス転移温度（Ｔｇ）は０〜１８０℃の範囲であり、好ましくは１０〜８０℃である。ガラス転移温度（Ｔｇ）が０℃以上の場合、耐ブロッキング性が良好であり、１８０℃以下の場合は常態防湿性及び折り曲げ防湿性が顕著に良好であり好ましい。
生成する共重合体（ハ）のガラス転移温度（Ｔｇ）は０〜５０℃の範囲であり、好ましくは１０〜４５℃である。ガラス転移温度（Ｔｇ）が０℃以上の場合、耐ブロッキング性が良好であり、５０℃以下の場合は常態防湿性及び折り曲げ防湿性が顕著に良好であり好ましい。
The heterostructure latex [I] of the present invention is obtained by, for example, emulsion copolymerizing a monomer mixture that forms a copolymer (b) and a copolymer (c) in the presence of the copolymer (b). can get.
The glass transition temperature (Tg) of the produced copolymer (b) is in the range of 0 to 180 ° C, preferably 10 to 80 ° C. When the glass transition temperature (Tg) is 0 ° C. or higher, the blocking resistance is good, and when it is 180 ° C. or lower, the normal moisture resistance and the bending moisture resistance are remarkably good, which is preferable.
The glass transition temperature (Tg) of the produced copolymer (c) is in the range of 0 to 50 ° C, preferably 10 to 45 ° C. When the glass transition temperature (Tg) is 0 ° C. or higher, the blocking resistance is good, and when it is 50 ° C. or lower, the normal moisture resistance and the folding moisture resistance are remarkably good, which is preferable.
また、生成する共重合体（ロ）、（ハ）のガラス転移温度（Ｔｇ）は共重合体（イ）のそれよりも高いことが必要である。共重合体（ロ）、（ハ）のガラス転移温度（Ｔｇ）が共重合体（イ）のそれ以上の場合は耐ブロッキング性と折り曲げ防湿性とのバランスが良く好ましい。
共重合体（イ）〜（ハ）のガラス転移温度（Ｔｇ）は、用いるそれぞれの単量体について一般に示されているその単独重合体のＴｇと単量体の配合割合から概略推定することができる。例えば約１００℃のガラス転移温度（Ｔｇ）の重合体を与えるスチレン、メチルメタクリレート、及びアクリルニトリルなどの単量体を高比率で配合した共重合体は高いガラス転移温度（Ｔｇ）のものが得られ、例えば約−８０℃のガラス転移温度（Ｔｇ）の重合体を与えるブタジエンや約−５０℃のガラス転移温度（Ｔｇ）の重合体を与えるｎ−ブチルアクリレート及び２−エチルヘキシルアクリレートなどの単量体を高い比率で配合した共重合体は低いガラス転移温度（Ｔｇ）のものが得られる。
Further, the glass transition temperature (Tg) of the produced copolymers (b) and (c) needs to be higher than that of the copolymer (b). When the glass transition temperature (Tg) of the copolymers (b) and (c) is higher than that of the copolymer (b), a good balance between blocking resistance and bending moisture resistance is preferable.
The glass transition temperatures (Tg) of the copolymers (b) to (c) can be roughly estimated from the Tg of the homopolymer generally shown for each monomer used and the blending ratio of the monomers. it can. For example, a copolymer containing a high ratio of monomers such as styrene, methyl methacrylate, and acrylonitrile that gives a polymer having a glass transition temperature (Tg) of about 100 ° C. has a high glass transition temperature (Tg). For example, butadiene which gives a polymer with a glass transition temperature (Tg) of about -80 ° C, and n-butyl acrylate and 2-ethylhexyl acrylate which give a polymer with a glass transition temperature (Tg) of about -50 ° C. A copolymer with a high proportion of the body is obtained with a low glass transition temperature (Tg).
共重合体（イ）を合成するために用いる単量体としては共役ジエン系単量体、芳香族ビニル系、（メタ）アクリル酸アルキルエステル単量体を主体とするものが耐ブロッキング性の点で好ましい。
共重合体（ロ）、（ハ）を合成するために用いる単量体としては芳香族ビニル系、（メタ）アクリル酸アルキルエステル単量体を主体とするものが防湿性の点で好ましい。
本発明の異層構造ラテックス［Ｉ］を構成する共重合体（イ）〜（ハ）の重量割合（重量％）はそれぞれ、６〜８０：２〜５０：１２〜８０｛但し、（イ）＋（ロ）＋（ハ）＝１００｝の範囲が防湿性、耐ブロッキング性のバランス面で好ましい。共重合体（イ）の割合が６重量％以上で、折り曲げ防湿性が顕著に良好となり。共重合体（イ）の割合が８０重量％以下で、耐ブロッキング性が良好となる。
The monomers used for synthesizing the copolymer (I) are mainly composed of conjugated diene monomers, aromatic vinyl monomers, and (meth) acrylic acid alkyl ester monomers. Is preferable.
As monomers used for synthesizing the copolymers (b) and (c), those mainly composed of aromatic vinyl-based and (meth) acrylic acid alkyl ester monomers are preferred from the viewpoint of moisture resistance.
The weight ratios (% by weight) of the copolymers (b) to (c) constituting the heterogeneous structure latex [I] of the present invention are 6 to 80: 2 to 50:12 to 80, respectively. The range of + (b) + (c) = 100} is preferable in terms of the balance between moisture resistance and blocking resistance. When the proportion of the copolymer (a) is 6% by weight or more, the bending moisture resistance is remarkably improved. When the proportion of the copolymer (a) is 80% by weight or less, the blocking resistance is good.
また、本発明の異層構造ラテックス［Ｉ］は共重合体（ロ）成分の存在が必須である。すなわち、異層構造ラテックスが３層の異なるガラス転移温度（Ｔｇ）共重合体からなる場合に、防湿性、耐ブロッキング性のバランス面で良好である。共重合体（ロ）の割合が２重量％以上で、耐ブロッキング性が良好となり、共重合体（ロ）の割合が５０重量％以下で、折り曲げ防湿性が顕著に良好となる。
ここで、３層の共重合体はガラス転移温度（Ｔｇ）によって区別され、共重合体（ロ）成分のガラス転移温度（Ｔｇ）は共重合体（イ）成分のガラス転移温度（Ｔｇ）より高く、かつ、共重合体（ロ）成分のガラス転移温度（Ｔｇ）と共重合体（ハ）成分のガラス転移温度（Ｔｇ）の差が４℃以上であることが必須である。共重合体（ロ）成分のガラス転移温度（Ｔｇ）と共重合体（ハ）成分のガラス転移温度（Ｔｇ）の差が４℃以上である場合折り曲げ防湿性と耐ブロッキング性が良好となる。
さらに、共重合体（ハ）の割合が１２重量％以上で、耐ブロッキング性が良好となり、共重合体（ハ）の割合が８０重量％以下で、折り曲げ防湿性が顕著に良好となる。
In addition, in the heterostructure latex [I] of the present invention, the presence of a copolymer (b) component is essential. That is, when the heterostructure latex is composed of three layers of different glass transition temperature (Tg) copolymers, the balance between moisture resistance and blocking resistance is good. When the proportion of the copolymer (B) is 2% by weight or more, the blocking resistance is good, and when the proportion of the copolymer (B) is 50% by weight or less, the bending moisture resistance is remarkably improved.
Here, the three-layer copolymer is distinguished by the glass transition temperature (Tg), and the glass transition temperature (Tg) of the copolymer (b) component is more than the glass transition temperature (Tg) of the copolymer (b) component. It is essential that the difference between the glass transition temperature (Tg) of the copolymer (B) component and the glass transition temperature (Tg) of the copolymer (C) component is 4 ° C. or higher. When the difference between the glass transition temperature (Tg) of the copolymer (b) component and the glass transition temperature (Tg) of the copolymer (c) component is 4 ° C. or more, the bending moisture resistance and blocking resistance are improved.
Further, when the proportion of the copolymer (c) is 12% by weight or more, the blocking resistance is good, and when the proportion of the copolymer (c) is 80% by weight or less, the bending moisture resistance is remarkably improved.
本願発明の異層構造ラテックス［Ｉ］のみの皮膜では防湿紙で要求される防湿性能を十分満たすことはできず、ワックスエマルジョン［ＩＩ］の併用が必要である。ワックスとしては特に限定されないが、例えばパラフィンワックス及びこれにジルコニウム化合物を加えたもの、カルナバワックス、キャンデリアワックス、ライスワックス、セレシンワックス、ペトロラタム、フィッシャー・トリブッシュワックス、ポリエチレンワックス、モンタンワックス及びその誘導体、マイクロスタリンワックス及びその誘導体、硬化ひまし油、流動パラフィン、ステアリン酸アミドなどを挙げることができ、単独及び２種以上組み合わせて用いることができる。ワックスはエマルジョンの形態にして本発明の異層構造ラテックス［Ｉ］に配合されるが、ラテックス製造中に添加することもできる。ワックスエマルジョン［ＩＩ］は、例えばワックス、ロジンやロジンエステル及び石油樹脂などの樹脂類、多価アルコール及びそのエステルなどの流動化剤などを混合加熱して溶融し、これにアニオン、カチオン、ノニオン系乳化剤を、あるいは水酸化ナトリウムなどの塩基性化合物、並びに有機アミンなどを加えて乳化することにより得られる。ワックスは４０〜１００℃の融点を有するものが好ましい。 The film of only the different layer structure latex [I] of the present invention cannot sufficiently satisfy the moisture-proof performance required for moisture-proof paper, and it is necessary to use the wax emulsion [II] in combination. The wax is not particularly limited. For example, paraffin wax and a zirconium compound added thereto, carnauba wax, canderia wax, rice wax, ceresin wax, petrolatum, Fischer-Tribush wax, polyethylene wax, montan wax and derivatives thereof. , Microstarin wax and derivatives thereof, hardened castor oil, liquid paraffin, stearamide, and the like, and can be used alone or in combination of two or more. The wax is incorporated into the heterostructure latex [I] of the present invention in the form of an emulsion, but can also be added during the production of the latex. Wax emulsion [II] is, for example, mixed with wax, rosin, rosin ester and petroleum resin, fluidizing agent such as polyhydric alcohol and its ester, and melted, and anion, cation, nonionic It can be obtained by emulsifying by adding an emulsifier, a basic compound such as sodium hydroxide, and an organic amine. The wax preferably has a melting point of 40 to 100 ° C.
本発明においてワックスエマルジョン［ＩＩ］はラテックス１００重量部（固形分換算）に対して０．１〜２０重量部、好ましくは０．５〜２０重量部配合する。０．１重量部以上の配合で常態防湿性が顕著に良好であり、２０重量部を以下で水離解性が良好である。
本発明の異層構造ラテックス［Ｉ］とワックスエマルジョン［ＩＩ］からなる塗工組成物に生成塗膜の耐ブロッキング性の向上などを目的として顔料を必要に応じて配合することができる。顔料としては特に制約はなく、無機及び有機の顔料が使用できる。例えば、マグネシウム、亜鉛、バリウム、チタン、アルミニウム、アンチモン、鉛などの各種金属酸化物、水酸化物、硫化物、炭酸塩、硫酸塩又は珪酸塩化合物やポリスチレン、ポリエチレン、ポリ塩化ビニルなどの個体高分子微粉末などが挙げられる。具体的には、炭酸カルシウム、カオリン（クレー）、タルク、雲母、二酸化チタン、水酸化アルミニウム、シリカ、合成ゼオライト、バライト粉、アルミナホワイト、サチンホワイトなどである。配合する顔料の割合は常態防湿性が顕著に損なわれない程度に配合することが好ましく、ラテックス１００重量部（固形分）に対して１００重量部以下が一般的である。
In the present invention, the wax emulsion [II] is blended in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of latex (in terms of solid content). When the blending amount is 0.1 parts by weight or more, the normal moisture resistance is remarkably good, and when 20 parts by weight or less, the water disintegration property is good.
If necessary, a pigment can be blended in the coating composition comprising the heterostructure latex [I] and the wax emulsion [II] of the present invention for the purpose of improving the blocking resistance of the resulting coating film. The pigment is not particularly limited, and inorganic and organic pigments can be used. For example, individual metal oxides such as magnesium, zinc, barium, titanium, aluminum, antimony, lead, etc., hydroxides, sulfides, carbonates, sulfates or silicate compounds, polystyrene, polyethylene, polyvinyl chloride, etc. Examples thereof include molecular fine powders. Specific examples include calcium carbonate, kaolin (clay), talc, mica, titanium dioxide, aluminum hydroxide, silica, synthetic zeolite, barite powder, alumina white, and satin white. The ratio of the pigment to be blended is preferably blended to such an extent that the normal moisture resistance is not significantly impaired, and is generally 100 parts by weight or less with respect to 100 parts by weight (solid content) of the latex.
これに加えて更に必要に応じて、メチルセルロース、ヒドロキエチルセルロース、カルボキシメチルセルロースなどのセルロース誘導体、デキストリン、酸化処理澱粉、架橋澱粉、エステル澱粉、グラフトコポリマー澱粉などの澱粉誘導体、ポリビニルアルコール、ポリ（メタ）アクリル酸塩、ポリビニルピロリドンなどの各種水溶性高分子、並びに公知の消泡剤、濡れ剤、レベリング剤、成膜助剤、可塑剤、顔料分散剤、着色剤、耐水化剤、潤滑剤、防腐剤、防滑剤、撥水剤、離型剤、ブロッキング防止剤、架橋剤（例えば水溶性エポキシ化合物など）、水溶性金属及び各種溶剤なども加えることができる。
本発明の支持体として用いられる原紙は、例えば、広葉樹晒しクラフトパルプ、針葉樹晒クラフトパルプなどの化学パルプ、ＧＰ（砕木パルプ）、ＲＧＰ（リファイナーグラウンドパルプ）、などの機械パルプを原料として用い、長網多筒型抄紙機、長網ヤンキー型抄紙機及び丸網抄紙機で抄紙されてできる上質紙、中質紙、片艶紙及びクラフト紙などの酸性紙、中性紙を包含するものである。原紙中には紙力増強剤、サイズ剤、填料、歩留向上剤などの抄紙補助薬品が含まれていてもよい。通常、原紙の米坪は５０〜１５０ｇ／ｍ２程度のものが用いられる。
In addition to this, cellulose derivatives such as methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, dextrin, oxidized starch, crosslinked starch, ester starch, graft copolymer starch and other starch derivatives, polyvinyl alcohol, poly (meth) acrylic, as required Various water-soluble polymers such as acid salts and polyvinyl pyrrolidone, as well as known antifoaming agents, wetting agents, leveling agents, film forming aids, plasticizers, pigment dispersants, colorants, water resistance agents, lubricants, preservatives Further, an anti-slip agent, a water repellent, a release agent, an anti-blocking agent, a crosslinking agent (for example, a water-soluble epoxy compound), a water-soluble metal and various solvents can be added.
The base paper used as the support of the present invention is, for example, chemical pulp such as hardwood bleached kraft pulp, softwood bleached kraft pulp, GP (crushed wood pulp), mechanical pulp such as RGP (refiner ground pulp), etc. Includes high quality paper, medium quality paper, glossy paper, kraft paper, and other acidic paper and neutral paper that can be made with a multi-tubular paper machine, long-mesh Yankee paper machine, and round net paper machine. . The base paper may contain paper-making auxiliary chemicals such as a paper strength enhancer, a sizing agent, a filler, and a yield improver. Usually, the base weight of the base paper is about 50 to 150 g / m 2 .
原紙に塗工液を塗布する設備としてはサイズプレス、ゲートロールコーター、バーコーター、ロールコーター、エアナイフコーター及びブレードコーターなどから任意に選定することができる。塗工量は絶乾重量で２〜３０ｇ／ｍ２塗工されるよう調整するのが好ましい。塗工液を塗布後の乾燥条件も特に限定されないが、７０〜２００℃、５秒〜１０分程度の加熱乾燥が適している。本発明の塗工液の乾燥重量固形分も３５〜７０重量％程度が好ましい。
又、本発明の防湿性ラテックス系組成物は、原紙に２回以上の塗布操作により塗工することもできる。
The equipment for applying the coating liquid to the base paper can be arbitrarily selected from a size press, a gate roll coater, a bar coater, a roll coater, an air knife coater, a blade coater and the like. The coating amount is preferably adjusted so as to be 2 to 30 g / m 2 by dry weight. The drying conditions after applying the coating liquid are not particularly limited, but heat drying at 70 to 200 ° C. for 5 seconds to 10 minutes is suitable. The dry weight solid content of the coating liquid of the present invention is also preferably about 35 to 70% by weight.
Further, the moisture-proof latex composition of the present invention can be applied to a base paper by two or more coating operations.
次に、本発明について、実施例に基づいて説明する。なお、実施例及び比較例における塗布量、部数、混合割合などは全て固形分基準で示した。また「％」及び「部」は全て重量基準である。
共重合体ラテックスのガラス転移温度（Ｔｇ）、ラテックスとワックスを含む塗工紙及びその性能は以下の方法で作成、測定した。
（１）ガラス転移温度（Ｔｇ／℃）
共重合体ラテックスをガラス板上に流延し、９０℃、３０分で加熱乾燥して皮膜を形成させる。次いで得られた皮膜をＴｇ測定容器に入れ、蓋をし、示差走査熱量計（セイコー電子社製）にセットして昇温速度１０℃／分で測定した。
Next, the present invention will be described based on examples. In addition, the application amount, the number of parts, the mixing ratio, and the like in Examples and Comparative Examples are all shown on a solid basis. “%” And “parts” are all based on weight.
The glass transition temperature (Tg) of the copolymer latex, the coated paper containing latex and wax, and the performance thereof were prepared and measured by the following methods.
(1) Glass transition temperature (Tg / ° C)
The copolymer latex is cast on a glass plate and heated and dried at 90 ° C. for 30 minutes to form a film. Next, the obtained film was put in a Tg measuring container, covered, set on a differential scanning calorimeter (manufactured by Seiko Denshi), and measured at a heating rate of 10 ° C./min.
（２）トルエン不溶分率（重量％）
共重合体ラテックスをガラス板上に流延し、９０℃、３０分で加熱乾燥して皮膜を形成させる。次いで得られた皮膜０．５ｇをトルエン３０ｇ中に浸漬し、３時間しんとう後、３００メッシュのステンレスメッシュでろ過する。このときのメッシュに残った未溶解物を乾燥し、その重量を０．５で除してトルエン不溶分率とする。
（３）粒子径（ｎｍ）
日機装株式会社製、ＭＩＣＲＯＴＲＡＣ粒度分布径（型式：9230UPA）を用いて数平均粒子径を測定した。
(2) Toluene insoluble fraction (wt%)
The copolymer latex is cast on a glass plate and heated and dried at 90 ° C. for 30 minutes to form a film. Next, 0.5 g of the obtained film is immersed in 30 g of toluene, stirred for 3 hours, and then filtered through a 300 mesh stainless steel mesh. The undissolved matter remaining on the mesh at this time is dried, and the weight is divided by 0.5 to obtain the toluene insoluble fraction.
(3) Particle size (nm)
The number average particle size was measured using Nikkiso Co., Ltd. MICROTRAC particle size distribution size (model: 9230UPA).
（４）塗工紙の作成
ラテックスに所定量のワックスエマルジョンを配合した組成物について、約４５重量％の固形分濃度に調整した塗工液を作成する。次いで坪量約８０ｇ／ｍ２の未晒クラフト原紙に塗工液を約２０ｇ／ｍ２（固形分）の塗工量になるようワイヤーバーにて塗布し、熱風乾燥機で１０５℃、６０秒の条件で乾燥して、塗工紙を作成した。
（５）常態透湿度（ｇ／ｍ２・２４ＨＲ）
上記（４）で作成した塗工紙試料についてＪＩＳ Ｚ０２０８防湿包装材料の透湿度試験（高温高湿条件４０℃、９０重量％ＲＨ）に準じて透湿度を測定した。
（６）折り曲げ透湿度（ｇ／ｍ２・２４ＨＲ）
上記（４）で作製した試料を直径約７ｃｍの円形状に切断し、塗工面を内側にして２５の交差点ができるように１０回（重複なし）十字に折り曲げる。その後広げて、（５）と同様な方法で透湿度を測定する。
(4) Preparation of coated paper For a composition in which a predetermined amount of wax emulsion is blended with latex, a coating liquid adjusted to a solid content concentration of about 45% by weight is prepared. Next, the coating liquid is applied to an unbleached kraft base paper having a basis weight of about 80 g / m 2 with a wire bar so that the coating amount is about 20 g / m 2 (solid content), and is heated at 105 ° C. for 60 seconds with a hot air dryer. The coated paper was prepared by drying under the conditions described above.
(5) Normal moisture permeability (g / m 2 · 24HR)
The moisture permeability of the coated paper sample prepared in the above (4) was measured according to a moisture permeability test (high temperature and high humidity condition 40 ° C., 90 wt% RH) of JIS Z0208 moisture-proof packaging material.
(6) Bending moisture permeability (g / m 2 · 24HR)
The sample prepared in the above (4) is cut into a circular shape having a diameter of about 7 cm, and is bent 10 times (no overlap) into a cross so that there are 25 intersections with the coated surface on the inside. After that, the moisture permeability is measured by the same method as in (5).
（７）耐ブロッキング性
上記（４）で作製した試料を用い、ラテックス塗布面と未塗布面とを重ね合わせ、４０ｇ／ｃｍ２で加圧し、４０℃、９０重量％ＲＨの雰囲気下に２４時間放置する。次いで重ね合わせた部分をゆっくりと引き離し、付着の程度を観察する。
○：抵抗なく引き離すことができる。
△：少し抵抗があるが、引き離すことができる。
×：抵抗が大きく、紙が破れることがある。
(7) Blocking resistance Using the sample prepared in the above (4), the latex coated surface and the uncoated surface were overlapped, pressurized at 40 g / cm 2 , and 24 hours in an atmosphere of 40 ° C. and 90 wt% RH. put. Then, the overlapped portion is slowly pulled away and the degree of adhesion is observed.
○: Can be separated without resistance.
Δ: There is a little resistance, but it can be pulled apart.
X: Resistance is large and paper may be torn.
（８）水離解性
上記（２）で作製した試料５ｇを小片に切断し、２Ｌの水とともに家庭用ミキサーで１０分攪拌し、塗工紙の離解状態を観察した。
○：単繊維状となる
△：少し凝集物が見られる
×：凝集物が見られる
(8) Water disaggregation property 5 g of the sample prepared in the above (2) was cut into small pieces and stirred with 2 L of water for 10 minutes with a home mixer, and the disaggregation state of the coated paper was observed.
○: Becomes a single fiber Δ: Some aggregates are seen ×: Aggregates are seen
［製造例１］
（１段目／コア層共重合体（イ）の重合）
攪拌装置と温度調節用ジャケットを備えた耐圧反応容器に、窒素置換の後、イオン交換水７２重量部、約２０ｎｍの平均粒子径を有するシード粒子の水分散体（固形分）０．４５重量部、ラウリル硫酸ナトリウム０．３重量部を入れ、内温を８０℃に昇温し、真空脱気により酸素を除去したスチレン１２重量部、ブタジエン１８重量部、、ｔ−ドデシルメルカプタン０．２重量部及びα−メチルスチレンダイマー０．１重量部からなる単量体混合物を４時間かけて添加した。単量体混合物を添加し始めるとほぼ同時に、水２１重量部、ラウリル硫酸ナトリウム０．３重量部、水酸化ナトリウム０．１重量部、ペルオキソ二硫酸カリ０．７重量部を１４時間かけて、３段目の単量体混合物が添加を終了するまで連続して添加した。
[Production Example 1]
(Polymerization of the first stage / core layer copolymer (a))
In a pressure-resistant reaction vessel equipped with a stirrer and a temperature control jacket, after nitrogen substitution, 72 parts by weight of ion-exchanged water, 0.45 parts by weight of an aqueous dispersion of seed particles having an average particle diameter of about 20 nm (solid content) , 0.3 parts by weight of sodium lauryl sulfate was added, the internal temperature was raised to 80 ° C., oxygen was removed by vacuum degassing, 12 parts by weight of styrene, 18 parts by weight of butadiene, and 0.2 parts by weight of t-dodecyl mercaptan. And a monomer mixture consisting of 0.1 part by weight of α-methylstyrene dimer was added over 4 hours. Almost simultaneously with the start of addition of the monomer mixture, 21 parts by weight of water, 0.3 parts by weight of sodium lauryl sulfate, 0.1 parts by weight of sodium hydroxide, and 0.7 parts by weight of potassium peroxodisulfate were added over 14 hours. It was continuously added until the third stage monomer mixture was added.
（２段目／中間層共重合体（ロ）の重合）
１段目の単量体混合物の添加が終了した時から１時間後スチレン８重量部、２−エチルヘキシルアクリレート２重量部からなる単量体混合物を４時間かけて反応容器に追添し、重合した。
（３段目／シェル層共重合体（ハ）の重合）
２段目の単量体混合物の添加が終了した時から１時間後スチレン３６重量部、２−エチルヘキシルアクリレート２２重量部、アクリル酸２重量部からなる単量体混合物を４時間かけて反応容器に追添し、重合した。
重合終了後も反応系の温度を８０℃で約２時間維持した後、水酸化ナトリウムを加えて反応系のｐＨを約８．０に調整した。次いで、スチームストリッピングで残留単量体を除去し、冷却し、８０メッシュの濾布で濾過して、得られた異層構造共重合体ラテックス［Ｉ］の固形分（１３０℃、乾燥法）を４８重量％に調整した。粒子径は１２０ｎｍで、トルエン不溶分は９８重量％であった。
(Second stage / intermediate layer copolymer (b) polymerization)
One hour after the addition of the first stage monomer mixture was completed, a monomer mixture consisting of 8 parts by weight of styrene and 2 parts by weight of 2-ethylhexyl acrylate was added to the reaction vessel over 4 hours and polymerized. .
(Polymerization of the third stage / shell layer copolymer (c))
One hour after the addition of the second stage monomer mixture was completed, a monomer mixture consisting of 36 parts by weight of styrene, 22 parts by weight of 2-ethylhexyl acrylate, and 2 parts by weight of acrylic acid was added to the reaction vessel over 4 hours. Added and polymerized.
After completion of the polymerization, the temperature of the reaction system was maintained at 80 ° C. for about 2 hours, and then sodium hydroxide was added to adjust the pH of the reaction system to about 8.0. Next, the residual monomer is removed by steam stripping, cooled, and filtered through an 80-mesh filter cloth. The solid content of the resulting heterostructure copolymer latex [I] (130 ° C., drying method) Was adjusted to 48% by weight. The particle size was 120 nm and the toluene insoluble content was 98% by weight.
［製造例２］
（均一ラテックスの重合）
攪拌装置と温度調節用ジャケットを備えた耐圧反応容器に、窒素置換の後、イオン交換水７２重量部、約２０ｎｍの平均粒子径を有するシード粒子の水分散体（固形分）０．４５重量部、ラウリル硫酸ナトリウム０．３重量部を入れ、内温を８０℃に昇温し、真空脱気により酸素を除去したスチレン４０重量部、ブタジエン６０重量部、アクリル酸２重量部、ｔ−ドデシルメルカプタン０．２重量部及びα−メチルスチレンダイマー０．１重量部からなる単量体混合物を１２時間かけて添加した。単量体混合物を添加し始めるとほぼ同時に、水２１重量部、ラウリル硫酸ナトリウム０．３重量部、水酸化ナトリウム０．１重量部、ペルオキソ二硫酸カリ０．７重量部を１２時間かけて、単量体混合物が添加を終了するまで連続して添加した。
重合終了後も反応系の温度を８０℃で約２時間維持した後、水酸化ナトリウムを加えて反応系のｐＨを約８．０に調整した。次いで、スチームストリッピングで残留単量体を除去し、冷却し、８０メッシュの濾布で濾過して、得られた異層構造共重合体ラテックスの固形分（１３０℃、乾燥法）を４８重量％に調整した。粒子径は１２１ｎｍで、トルエン不溶分は９８重量％であった。
[Production Example 2]
(Uniform latex polymerization)
In a pressure-resistant reaction vessel equipped with a stirrer and a temperature control jacket, after nitrogen substitution, 72 parts by weight of ion-exchanged water, 0.45 parts by weight of an aqueous dispersion of seed particles having an average particle diameter of about 20 nm (solid content) , 0.3 parts by weight of sodium lauryl sulfate was added, the internal temperature was raised to 80 ° C., oxygen was removed by vacuum degassing, 40 parts by weight of styrene, 60 parts by weight of butadiene, 2 parts by weight of acrylic acid, t-dodecyl mercaptan A monomer mixture consisting of 0.2 parts by weight and 0.1 parts by weight of α-methylstyrene dimer was added over 12 hours. Almost simultaneously with the start of the monomer mixture addition, 21 parts by weight of water, 0.3 parts by weight of sodium lauryl sulfate, 0.1 parts by weight of sodium hydroxide and 0.7 parts by weight of potassium peroxodisulfate were added over 12 hours. It was added continuously until the monomer mixture was added.
After completion of the polymerization, the temperature of the reaction system was maintained at 80 ° C. for about 2 hours, and then sodium hydroxide was added to adjust the pH of the reaction system to about 8.0. Next, the residual monomer is removed by steam stripping, cooled, and filtered through an 80 mesh filter cloth. The solid content (130 ° C., drying method) of the obtained heterostructure copolymer latex is 48 wt. % Adjusted. The particle diameter was 121 nm and the toluene insoluble content was 98% by weight.
［製造例３］
（１段目／コア層の重合）
攪拌装置と温度調節用ジャケットを備えた耐圧反応容器に、窒素置換の後、イオン交換水７２重量部、約２０ｎｍの平均粒子径を有するシード粒子の水分散体（固形分）０．４５重量部、ラウリル硫酸ナトリウム０．３重量部を入れ、内温を８０℃に昇温し、真空脱気により酸素を除去したスチレン２６重量部、ブタジエン３重量部、アクリル酸１重量部、ｔ−ドデシルメルカプタン０．２重量部及びα−メチルスチレンダイマー０．１重量部からなる単量体混合物を６時間かけて添加した。単量体混合物を添加し始めるとほぼ同時に、水２１重量部、ラウリル硫酸ナトリウム０．３重量部、水酸化ナトリウム０．１重量部、ペルオキソ二硫酸カリ０．７重量部を１３時間かけて、２段目の単量体混合物が添加を終了するまで連続して添加した。
[Production Example 3]
(First stage / core layer polymerization)
In a pressure-resistant reaction vessel equipped with a stirrer and a temperature control jacket, after nitrogen substitution, 72 parts by weight of ion-exchanged water, 0.45 parts by weight of an aqueous dispersion of seed particles having an average particle diameter of about 20 nm (solid content) Then, 0.3 parts by weight of sodium lauryl sulfate was added, the internal temperature was raised to 80 ° C., 26 parts by weight of styrene from which oxygen was removed by vacuum degassing, 3 parts by weight of butadiene, 1 part by weight of acrylic acid, t-dodecyl mercaptan A monomer mixture consisting of 0.2 parts by weight and 0.1 parts by weight of α-methylstyrene dimer was added over 6 hours. Almost simultaneously with the start of addition of the monomer mixture, 21 parts by weight of water, 0.3 parts by weight of sodium lauryl sulfate, 0.1 parts by weight of sodium hydroxide, and 0.7 parts by weight of potassium peroxodisulfate were added over 13 hours. It was added continuously until the second stage monomer mixture was added.
（２段目／シェル層の重合）
２段目の単量体混合物の添加が終了した時から１時間後スチレン２７重量部、メチルメタアクリレート１０重量部、ブタジエン３２重量部、アクリル酸１重量部からなる単量体混合物を６時間かけて反応容器に追添し、重合した。
重合終了後も反応系の温度を８０℃で約２時間維持した後、水酸化ナトリウムを加えて反応系のｐＨを約８．０に調整した。次いで、スチームストリッピングで残留単量体を除去し、冷却し、８０メッシュの濾布で濾過して、得られた異層構造共重合体ラテックス［Ｉ］の固形分（１３０℃、乾燥法）を４８重量％に調整した。粒子径は１２５ｎｍで、トルエン不溶分は９５重量％であった。
(Second stage / shell layer polymerization)
One hour after the addition of the second stage monomer mixture was completed, a monomer mixture consisting of 27 parts by weight of styrene, 10 parts by weight of methyl methacrylate, 32 parts by weight of butadiene, and 1 part by weight of acrylic acid was taken over 6 hours. Was added to the reaction vessel and polymerized.
After completion of the polymerization, the temperature of the reaction system was maintained at 80 ° C. for about 2 hours, and then sodium hydroxide was added to adjust the pH of the reaction system to about 8.0. Next, the residual monomer is removed by steam stripping, cooled, and filtered through an 80-mesh filter cloth. The solid content of the resulting heterostructure copolymer latex [I] (130 ° C., drying method) Was adjusted to 48% by weight. The particle size was 125 nm and the toluene insoluble content was 95% by weight.
［実施例１〜４、６〜１３、１５および参考例１，２］
表１に示す配合割合の単量体及び連鎖移動剤を用いて製造例１と同様な重合方法でＡ〜Ｏの異層構造（三層構造）ラテックス［Ｉ］を作成し、ポリマー相のＴｇを測定した。得られた各異層構造共重合体ラテックス［Ｉ］にワックスエマルジョン［ＩＩ］（パラフィン系ワックス、中京油脂株式会社製セロゾールＨ−６２０、融点６８℃）をラテックス固形分１００重量部に対し６重量部（固形分）配合し、４５重量％固形分濃度の塗工液を作成した。次いで坪量約８０ｇ／ｍ２の未晒クラフト原紙に塗工液を約２０ｇ／ｍ２（固形分）の塗工量になるようワイヤーバーにて塗布し、熱風乾燥機で１０５℃、６０秒の条件で乾燥して、塗工紙を作成した。
得られた各塗工紙について前述の測定法に従って常態透湿度、折り曲げ透湿度、耐ブロッキング性及び水離解性を測定した。測定した結果を表３に示す。
なお、実施例５、１４は欠番である。
[Examples 1 to 4, 6 to 13, 15 and Reference Examples 1 and 2 ]
Using a monomer and a chain transfer agent in the blending ratio shown in Table 1, A to O different layer structure (three-layer structure) latex [I] was prepared by the same polymerization method as in Production Example 1, and Tg of the polymer phase Was measured. 6 weights of wax emulsion [II] (paraffin wax, Cerosol H-620 manufactured by Chukyo Yushi Co., Ltd., melting point 68 ° C.) is added to 100 parts by weight of the latex solid content in each of the different layer structure copolymer latex [I] thus obtained. Part (solid content) was blended to prepare a coating solution having a solid content concentration of 45% by weight. Next, the coating liquid is applied to an unbleached kraft base paper having a basis weight of about 80 g / m 2 with a wire bar so that the coating amount is about 20 g / m 2 (solid content), and heated at 105 ° C. for 60 seconds with a hot air dryer. The coated paper was prepared by drying under conditions.
With respect to each of the obtained coated papers, the normal moisture permeability, the bent moisture permeability, the blocking resistance and the water disintegration property were measured according to the above-described measurement methods. Table 3 shows the measurement results.
Examples 5 and 14 are missing numbers.
［実施例１６、１７］
実施例１に用いた異層構造（三層構造）ラテックス［Ｉ］（Ａ）にワックスエマルジョン［ＩＩ］（パラフィン系ワックス、中京油脂株式会社製セロゾール Ｈ−６２０、融点６８℃）をラテックス固形分１００重量部に対し０．１重量部および２０重量部（固形分）配合し、４５重量％固形分濃度の塗工液を作成した。次いで坪量約８０ｇ／ｍ２の未晒クラフト原紙に塗工液を約２０ｇ／ｍ２（固形分）の塗工量になるようワイヤーバーにて塗布し、熱風乾燥機で１０５℃、６０秒の条件で乾燥して、塗工紙を作成した。
得られた各塗工紙について前述の測定法に従って常態透湿度、折り曲げ透湿度、耐ブロッキング性及び水離解性を測定した。測定した結果を表３に示す。
[Examples 16 and 17]
The latex emulsion [II] (paraffinic wax, Cellosol H-620 manufactured by Chukyo Yushi Co., Ltd., melting point 68 ° C.) is added to the latex solid content of the different layer structure (three layer structure) latex [I] (A) used in Example 1. 0.1 parts by weight and 20 parts by weight (solid content) were blended with respect to 100 parts by weight to prepare a coating solution having a solid content concentration of 45% by weight. Next, the coating liquid is applied to an unbleached kraft base paper having a basis weight of about 80 g / m 2 with a wire bar so that the coating amount is about 20 g / m 2 (solid content), and is heated at 105 ° C. for 60 seconds with a hot air dryer. The coated paper was prepared by drying under the conditions described above.
With respect to each of the obtained coated papers, the normal moisture permeability, the bent moisture permeability, the blocking resistance and the water disintegration property were measured according to the above-described measurement methods. Table 3 shows the measurement results.
［比較例１〜６、９、１０、１７］
表２の配合割合の単量体及び連鎖移動剤を用いて製造例１の方法に従って重合及び後処理を行いａ〜ｊ、ｑの異層構造（三層構造）ラテックスを得た。次いでこれらの異層構造ラテックスに実施例１〜１５と同様にワックスエマルジョン［ＩＩ］（中京油脂株式会社製セロゾール Ｈ−６２０）を同量配合して塗工液を作成し、未晒クラフト原紙に塗工して塗工紙を得た。得られた塗工紙について実施例１〜１５と同様に各種物性を測定した。
結果を表４に示す。
なお、比較例７、８は欠番である。
[Comparative Examples 1 to 6, 9, 10 , 17]
Polymerization and post-treatment were carried out according to the method of Production Example 1 using the monomers and chain transfer agents in the blending ratios shown in Table 2 to obtain different layer structure (three-layer structure) latex of a to j and q. Next, the same amount of wax emulsion [II] (Cerosol H-620 manufactured by Chukyo Yushi Co., Ltd.) was blended in these different layer structure latexes in the same manner as in Examples 1 to 15 to prepare a coating solution. The coated paper was obtained by coating. Various physical properties of the obtained coated paper were measured in the same manner as in Examples 1-15.
The results are shown in Table 4.
Note that Comparative Examples 7 and 8 are missing numbers.
［比較例１１、１２］
表２の一段目の配合割合の単量体及び連鎖移動剤を用いて製造例２の方法に従って重合及び後処理を行いｋ、ｌの均一構造ラテックスを得た。次いでこれらの均一構造ラテックスに実施例１〜１５と同様にワックスエマルジョン［ＩＩ］（中京油脂株式会社製セロゾール Ｈ−６２０）を同量配合して塗工液を作成し、未晒クラフト原紙に塗工して塗工紙を得た。得られた塗工紙について実施例１〜１５と同様に各種物性を測定した。結果を表４に示す。
[Comparative Examples 11 and 12]
Polymerization and post-treatment were carried out according to the method of Production Example 2 using the monomer and chain transfer agent in the first stage of Table 2 to obtain a k and l uniform structure latex. Next, the same amount of wax emulsion [II] (Cerosol H-620, manufactured by Chukyo Yushi Co., Ltd.) was blended into these uniform latexes in the same manner as in Examples 1 to 15 to prepare a coating solution, which was applied to unbleached kraft base paper. To obtain coated paper. Various physical properties of the obtained coated paper were measured in the same manner as in Examples 1-15. The results are shown in Table 4.
［比較例１３〜１６］
表２の一段目と三段目の配合割合の単量体及び連鎖移動剤を用いて製造例３の方法に従って重合及び後処理を行いｍ〜ｐの異層（コア／シェル二層構造）構造ラテックスを得た。次いでこれらの異層（コア／シェル二層構造）構造ラテックスに実施例１〜１５と同様にワックスエマルジョン［ＩＩ］（中京油脂株式会社製セロゾール Ｈ−６２０）を同量配合して塗工液を作成し、未晒クラフト原紙に塗工して塗工紙を得た。得られた塗工紙について実施例１〜１５と同様に各種物性を測定した。結果を表４に示す。
[Comparative Examples 13 to 16]
Mp different layer (core / shell two-layer structure) by polymerization and post-treatment according to the method of Production Example 3 using monomers and chain transfer agents in the first and third stages of Table 2 Latex was obtained. Next, the same amount of wax emulsion [II] (Cerosol H-620 manufactured by Chukyo Yushi Co., Ltd.) is blended in these different layer (core / shell two-layer structure) structure latex in the same manner as in Examples 1 to 15. Prepared and coated on unbleached kraft paper to obtain coated paper. Various physical properties of the obtained coated paper were measured in the same manner as in Examples 1-15. The results are shown in Table 4.
［実施例１８、１９］
実施例１に用いた異層構造（三層構造）ラテックス［Ｉ］（Ａ）にワックスエマルジョン［ＩＩ］（パラフィン系ワックス、中京油脂株式会社製セロゾール Ｈ−６２０、融点６８℃）をラテックス固形分１００重量部に対し０．０５重量部および２５重量部（固形分）配合し、４５重量％固形分濃度の塗工液を作成した。次いで坪量約８０ｇ／ｍ２の未晒クラフト原紙に塗工液を約２０ｇ／ｍ２（固形分）の塗工量になるようワイヤーバーにて塗布し、熱風乾燥機で１０５℃、６０秒の条件で乾燥して、塗工紙を作成した。
得られた各塗工紙について前述の測定法に従って常態透湿度、折り曲げ透湿度、耐ブロッキング性及び水離解性を測定した。測定した結果を表３に示す。
[Examples 18 and 19]
The latex emulsion [II] (paraffinic wax, Cellosol H-620 manufactured by Chukyo Yushi Co., Ltd., melting point 68 ° C.) is added to the latex solid content of the different layer structure (three layer structure) latex [I] (A) used in Example 1. 0.05 parts by weight and 25 parts by weight (solid content) were blended with respect to 100 parts by weight to prepare a coating solution having a solid content concentration of 45% by weight. Next, the coating liquid is applied to an unbleached kraft base paper having a basis weight of about 80 g / m 2 with a wire bar so that the coating amount is about 20 g / m 2 (solid content), and is heated at 105 ° C. for 60 seconds with a hot air dryer. The coated paper was prepared by drying under the conditions described above.
With respect to each of the obtained coated papers, the normal moisture permeability, the bent moisture permeability, the blocking resistance and the water disintegration property were measured according to the above-described measurement methods. Table 3 shows the measurement results.
以下、実施例、比較例の物性測定結果に基づき、本発明の効果を説明する。
［実施例１〜４、１５と比較例１］
表３〜４の結果から、コア層共重合体（イ）のガラス転移温度（Ｔｇ）が１０℃以下で常態透湿度、折り曲げ透湿度が顕著に良好である。
［実施例１、６〜７、１５と比較例３］
表３〜４の結果から、中間層共重合体（ロ）のガラス転移温度（Ｔｇ）が０℃以上で耐ブロッキング性、水離解性が良好である。
Hereinafter, the effect of the present invention will be described based on the measurement results of physical properties of Examples and Comparative Examples.
[Examples 1 to 4, 15 and Comparative Example 1]
From the results of Tables 3 to 4, the core layer copolymer (A) has a glass transition temperature (Tg) of 10 ° C. or less, and the normal moisture permeability and the bent moisture permeability are remarkably good.
[Examples 1 , 6-7, 15 and Comparative Example 3]
From the result of Tables 3-4, the glass transition temperature (Tg) of an intermediate | middle layer copolymer (b) is 0 degreeC or more, and its blocking resistance and water disintegration property are favorable.
［実施例１、８、９、１５と比較例５、６］
表３〜４の結果から、シェル層共重合体（ハ）のガラス転移温度（Ｔｇ）が０℃以上で耐ブロッキング性、水離解性が良好である。また、シェル層共重合体（ハ）のガラス転移温度（Ｔｇ）が５０℃以下で常態透湿度、折り曲げ透湿度が顕著に良好である。
［実施例４と比較例２、４］
表３〜４の結果から、中間層共重合体（ロ）、シェル層共重合体（ハ）のガラス転移温度（Ｔｇ）がコア層共重合体（イ）のガラス転移温度（Ｔｇ）以上であるとき、耐ブロッキング性、水離解性が良好である。
[Examples 1, 8, 9 , 15 and Comparative Examples 5 and 6]
From the results of Tables 3 to 4, the glass transition temperature (Tg) of the shell layer copolymer (C) is 0 ° C. or higher, and the blocking resistance and water disintegration property are good. Further, the shell layer copolymer (C) has a glass transition temperature (Tg) of 50 ° C. or less, and the normal moisture permeability and the bent moisture permeability are remarkably good.
[Example 4 and Comparative Examples 2 and 4]
From the results of Tables 3 to 4, the glass transition temperature (Tg) of the intermediate layer copolymer (b) and the shell layer copolymer (c) is equal to or higher than the glass transition temperature (Tg) of the core layer copolymer (b). In some cases, blocking resistance and water disintegration are good.
［実施例１、１２〜１５と比較例９、１０］
表３〜４の結果から、中間層共重合体（ロ）の組成量が２重量％以上で耐ブロッキング
性、水離解性が良好である。また、中間層共重合体（ロ）の組成量が５０重量％以下で常
態透湿度、折り曲げ透湿度が顕著に良好である。
［実施例１、１２、１３、１５と比較例９、１０］
表３〜４の結果から、中間層共重合体（ロ）の組成量が２重量％以上で耐ブロッキング性、水離解性が良好である。また、中間層共重合体（ロ）の組成量が５０重量％以下で常態透湿度、折り曲げ透湿度が顕著に良好である。
[Examples 1, 12 to 15 and Comparative Examples 9 and 10]
From the results of Tables 3 to 4, the anti-blocking property and water disintegration property are good when the composition amount of the intermediate layer copolymer (b) is 2% by weight or more. In addition, the composition of the intermediate layer copolymer (b) is 50% by weight or less, and the normal moisture permeability and the bent moisture permeability are remarkably good.
[Examples 1 , 12 , 13, 15 and Comparative Examples 9, 10]
From the results of Tables 3 to 4, the anti-blocking property and water disintegration property are good when the composition amount of the intermediate layer copolymer (b) is 2% by weight or more. In addition, the composition of the intermediate layer copolymer (b) is 50% by weight or less, and the normal moisture permeability and the bent moisture permeability are remarkably good.
［実施例１〜４，６〜１３、１５と比較例１１、１２］
表３〜４の結果から、単一組成のラテックスに比べ、異層構造ラテックス［Ｉ］の方が、耐ブロッキング性、水離解性、常態透湿度、折り曲げ透湿度の各物性相互のバランスが良好である。
［実施例１〜４，６〜１３、１５と比較例１３〜１６］
表３〜４の結果から、コア／シェル構造（二層構造）を有するのラテックスに比べ、異層構造ラテックス［Ｉ］（三層構造）の方が、耐ブロッキング性、水離解性、常態透湿度、折り曲げ透湿度の各物性相互のバランスが良好である。
[Examples 1 to 4, 6 to 13, 15 and Comparative Examples 11 and 12]
From the results of Tables 3 to 4, the different structure latex [I] has a better balance between physical properties of blocking resistance, water disintegration, normal moisture permeability, and bent moisture permeability than the latex of a single composition. It is.
[Examples 1 to 4, 6 to 13, 15 and Comparative Examples 13 to 16]
From the results of Tables 3-4, the anti-blocking latex [I] (three-layer structure) is more resistant to blocking, water disintegration, and normal transparency than the latex having a core / shell structure (two-layer structure). Good balance between physical properties of humidity and bending moisture permeability.
［実施例１〜４、６〜１３、１５と比較例１３、１４、１６、１７］
表３〜４の結果から、中間層共重合体（ロ）、シェル層共重合体（ハ）に共役ジエン系単量体を有しない異層構造ラテックス［Ｉ］の方が、中間層共重合体（ロ）、シェル層共重合体（ハ）に共役ジエン系単量体を有する異層構造ラテックスに比較して耐ブロッキング性、水離解性、常態透湿度、折り曲げ透湿度の各物性相互のバランスが良好である。
［実施例１〜４、６〜１３、１５〜１７と比較例１８、１９］
表３〜４の結果から、ワックスエマルジョン［ＩＩ］の配合量が０．２重量％以上で常態透湿度、折り曲げ透湿度、耐ブロッキング性が良好であり、ワックスエマルジョン［ＩＩ］の配合量が２０重量％以下で常態透湿度、折り曲げ透湿度、水離解性が良好である。
以上の実施例及び比較例で示される結果から明らかなように、本願発明の特定の異層構造ラテックス［Ｉ］にワックスエマルジョン［ＩＩ］を配合した塗工液を塗工して得られる防湿塗工紙が常態防湿性、折り曲げ防湿性に優れるとともに耐ブロッキング性にも優れ、 又十分リサイクル可能な程度に容易に水中で離解され易い極めて有意な性能を有する。
[Examples 1 to 4, 6 to 13, 15 and Comparative Examples 13 , 14 , 16, and 17]
From the results of Tables 3 to 4, the intermediate layer copolymer (b) and the shell layer copolymer (c) have different layer structure latex [I] having no conjugated diene monomer. Compared to the heterostructure latex having a conjugated diene monomer in the coalescence (b) and shell layer copolymer (c), the properties of blocking properties, water disintegration, normal moisture permeability, bending moisture permeability Good balance.
[Examples 1 to 4, 6 to 13, 15 to 17 and Comparative Examples 18 and 19]
From the results of Tables 3 to 4, the blending amount of the wax emulsion [II] is 0.2% by weight or more, the normal moisture permeability, the bending moisture permeability, and the blocking resistance are good, and the blending amount of the wax emulsion [II] is 20 Normal moisture permeability, bent moisture permeability, and water disintegration are good at weight% or less.
As is clear from the results shown in the above Examples and Comparative Examples, the moisture-proof coating obtained by applying a coating liquid in which the wax emulsion [II] is blended with the specific heterostructure latex [I] of the present invention. The paper is excellent in normal moisture resistance and bending moisture resistance, as well as blocking resistance, and has extremely significant performance that is easily disintegrated in water to the extent that it can be sufficiently recycled.
本発明の異層構造ラテックス［Ｉ］は防湿性を必要とする包装紙の分野において好適に利用できる。 The lamellar latex [I] of the present invention can be suitably used in the field of wrapping paper requiring moisture resistance.
１ 共重合体（イ）からなるコア層
２ 共重合体（ロ）からなる中間層
３ 共重合体（ハ）からなるシェル層
４ 共重合体（イ）からなるコア層
５ 共重合体（ロ）からなる中間層
６ 共重合体（ハ）からなるシェル層
DESCRIPTION OF SYMBOLS 1 Core layer which consists of copolymer (b) 2 Intermediate layer which consists of copolymer (b) 3 Shell layer which consists of copolymer (c) 4 Core layer which consists of copolymer (b) 5 Copolymer (b) 6) Shell layer made of 6 copolymer (C)
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| JP4917268B2 (en) * | 2005-04-13 | 2012-04-18 | 旭化成ケミカルズ株式会社 | Thermal recording paper coating composition |
| JP4552744B2 (en) * | 2005-04-28 | 2010-09-29 | 王子製紙株式会社 | Release paper substrate and release paper using the release paper substrate |
| JP2007016332A (en) * | 2005-07-06 | 2007-01-25 | Asahi Kasei Chemicals Corp | Coating composition for moistureproof paper |
| US8674000B2 (en) * | 2006-10-24 | 2014-03-18 | Lg Chem, Ltd. | Multi-layered paper coating latex having high swelling and contraction property, method for preparing the same, and paper coating composition containing the same |
| WO2009016053A1 (en) | 2007-07-30 | 2009-02-05 | Basf Se | Core shell polymer |
| JP5468741B2 (en) * | 2008-02-18 | 2014-04-09 | 株式会社日本触媒 | Water-based resin composition and paint for building exterior topcoat containing the same |
| JP6116927B2 (en) * | 2012-02-17 | 2017-04-19 | 日本エイアンドエル株式会社 | Method for producing copolymer latex |
| JP5632954B1 (en) * | 2013-07-24 | 2014-11-26 | 日本エイアンドエル株式会社 | Copolymer latex |
| JP5632956B1 (en) * | 2013-07-24 | 2014-11-26 | 日本エイアンドエル株式会社 | Copolymer latex |
| JP5632955B1 (en) * | 2013-07-24 | 2014-11-26 | 日本エイアンドエル株式会社 | Copolymer latex |
| JP5632953B1 (en) * | 2013-07-24 | 2014-11-26 | 日本エイアンドエル株式会社 | Method for producing copolymer latex |
| JP5613316B1 (en) * | 2013-07-24 | 2014-10-22 | 日本エイアンドエル株式会社 | Copolymer latex |
| JP5613317B1 (en) * | 2013-07-24 | 2014-10-22 | 日本エイアンドエル株式会社 | Copolymer latex |
| JP5769841B2 (en) * | 2014-03-11 | 2015-08-26 | 株式会社スクウェア・エニックス | Portable game device with touch panel display |
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| JP2002194006A (en) * | 2000-12-27 | 2002-07-10 | Asahi Kasei Corp | Method for producing copolymer latex |
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| JPH0445169A (en) * | 1990-06-12 | 1992-02-14 | Kansai Paint Co Ltd | Paint composition of monolayer elastic emulsion |
| JPH0616736A (en) * | 1992-06-30 | 1994-01-25 | Sumitomo Dow Ltd | Production of copolymer latex |
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