JP2006249590A - Printing coated paper using composite pigment, and paperboard - Google Patents
Printing coated paper using composite pigment, and paperboard Download PDFInfo
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Abstract
Description
本発明は、顔料と接着剤とを含む塗料が塗布された塗工紙又は塗工板紙、及びこれらの塗工層形成のための塗料組成物に関する。特に、印刷用塗工紙、及びその塗工層形成のために用いられる塗料組成物に関する。 The present invention relates to a coated paper or coated paperboard to which a paint containing a pigment and an adhesive is applied, and a paint composition for forming these coating layers. In particular, the present invention relates to a coated paper for printing and a coating composition used for forming the coated layer.
近年、印刷物のカラー化、高級化に伴い、印刷用紙の高白色度が求められている。特に、板紙分野では古紙の配合割合が増加し、古紙パルプの再利用回数が増えることによって、パルプ繊維が短くなり、脱墨工程においてパルプが漂白しきれず白色度が低下する問題があり、塗工層に高い白色度・不透明度が要求されている。 In recent years, high whiteness of printing paper has been demanded along with the colorization and upgrading of printed matter. In particular, in the paperboard field, the proportion of wastepaper increases, and the number of reuses of wastepaper pulp increases, resulting in shortening of pulp fibers, resulting in the problem that the pulp cannot be completely bleached in the deinking process and the whiteness is lowered. High whiteness and opacity are required for the layer.
これに対応するため、塗工紙用塗料組成物には、通常、白色度・不透明度の高い高白色カオリンクレー、デラミネートクレー、微細立方体軽質炭酸カルシウム、二酸化チタンなどの顔料が含まれている。 In order to cope with this, the coating composition for coated paper usually contains pigments such as high white kaolin clay, delaminated clay, fine cubic light calcium carbonate, and titanium dioxide with high whiteness and opacity. .
これらの顔料のうち、炭酸カルシウムは製造コストが安く、高い白色度とインキ受理性を有しているが、微細な粒子の配合割合を増加すると表面強度が低下する。また、カオリン系顔料を配合すると白紙光沢・不透明度は得られるが、白色度やインキ受理性が十分ではない。二酸化チタンについては、その高い屈折率によって、高い不透明度を付与することができるが、他の顔料よりも特に高価であるため、多量に配合すると製造コストが高くなる。 Among these pigments, calcium carbonate is low in production cost and has high whiteness and ink acceptability. However, increasing the blending ratio of fine particles decreases the surface strength. Further, when a kaolin pigment is added, white paper gloss and opacity can be obtained, but whiteness and ink acceptability are not sufficient. Titanium dioxide can impart high opacity due to its high refractive index, but is particularly expensive than other pigments, and its production cost increases when blended in large amounts.
紙・板紙市場においては、塗工紙の軽量化に代表されるようにユーザーのコストダウン指向が明瞭になっており、高白色度・不透明度で且つ低コストであることが重要になってきている。しかしながら、近年の古紙パルプの品質低下から、二酸化チタンを含めた白色顔料の配合割合を増加せざるを得ない状況である。 In the paper and paperboard market, the trend toward cost reduction for users has become clear, as typified by the reduction in weight of coated paper, and high whiteness, opacity and low cost are becoming important. Yes. However, due to the recent decline in the quality of waste paper pulp, the proportion of white pigments including titanium dioxide must be increased.
本発明は、白色度・不透明度およびインキ受理性の高い塗工層を形成することができる塗工紙又は塗工板紙用塗料組成物、及びこのような塗工層を有する塗工紙又は塗工板紙を提供することを目的とする。 The present invention relates to a coating composition for coated paper or coated paperboard that can form a coating layer having high whiteness, opacity, and ink acceptability, and a coated paper or coating having such a coating layer. The purpose is to provide paperboard.
本発明者らは、前記目的を達成するために研究を重ね、以下の知見を得た。
(i) 二酸化チタン粒子表面に炭酸カルシウム粒子を定着させた二酸化チタン／炭酸カルシウム複合粒子を無機顔料として含む塗料組成物を塗布してなる塗工紙は、高い白色度と不透明度を有する。これは、炭酸カルシウム粒子がスペーサーの役割をして二酸化チタン粒子間の距離を大きくすることにより、酸化チタンが有する光散乱力を最大限に発揮することによると考えられる。
(ii) また塗工層の上にインキを用いて印刷したときに、複合粒子の特殊な形状及びその大きさによって、高いインキ受理性が得られる。即ち、印刷インキの塗工層への吸収量が多く、かつ塗工表面にミクロな粗面が形成されるため、インキ受理量が多く、印刷濃度が高くなる。
The inventors of the present invention have made extensive studies in order to achieve the above object, and have obtained the following knowledge.
(i) A coated paper obtained by applying a coating composition containing titanium dioxide / calcium carbonate composite particles having calcium carbonate particles fixed on the surface of titanium dioxide particles as an inorganic pigment has high whiteness and opacity. This is considered to be due to the fact that the calcium carbonate particles act as spacers and increase the distance between the titanium dioxide particles to maximize the light scattering force of titanium oxide.
(ii) Further, when ink is printed on the coating layer, high ink acceptability is obtained due to the special shape and size of the composite particles. That is, the amount of printing ink absorbed into the coating layer is large, and a micro rough surface is formed on the coating surface, so that the amount of ink received is large and the printing density is high.
本発明は、上記知見に基づき完成されたものであり、以下の塗工紙又は塗工板紙用塗料組成物、塗工紙又は塗工板紙を提供する。 The present invention has been completed based on the above findings, and provides the following coated paper or coated paperboard coating composition, coated paper or coated paperboard.
項１． 基紙上に、二酸化チタン粒子表面に炭酸カルシウム粒子を定着させた二酸化チタン／炭酸カルシウム複合粒子と接着剤とを含む塗料組成物を塗布してなる塗工紙又は塗工板紙。 Item 1. A coated paper or a coated paperboard obtained by applying a coating composition containing titanium dioxide / calcium carbonate composite particles in which calcium carbonate particles are fixed on the surface of titanium dioxide particles and an adhesive on a base paper.
項２． 二酸化チタン／炭酸カルシウム複合粒子における二酸化チタンと炭酸カルシウムとの重量比が、１：９９〜５０：５０である項１に記載の塗工紙又は塗工板紙。 Item 2. Item 2. The coated paper or coated paperboard according to Item 1, wherein the weight ratio of titanium dioxide to calcium carbonate in the titanium dioxide / calcium carbonate composite particles is 1:99 to 50:50.
項３． 接着剤が親水性ポリマーである項１又は２に記載の塗工紙又は塗工板紙。 Item 3. Item 3. The coated paper or coated paperboard according to Item 1 or 2, wherein the adhesive is a hydrophilic polymer.
項４． 複合顔料の塗布量が５〜３０ｇ／ｍ2である項１〜３のいずれかに記載の塗工紙又は塗工板紙。 Item 4. Item 4. The coated paper or coated paperboard according to any one of Items 1 to 3, wherein the amount of the composite pigment applied is 5 to 30 g / m 2 .
項５． 二酸化チタン粒子表面に炭酸カルシウム粒子を定着させた二酸化チタン／炭酸カルシウム複合粒子と、接着剤とを含む塗工紙又は塗工板紙用塗料組成物。 Item 5. A coating composition for coated paper or coated paperboard, comprising titanium dioxide / calcium carbonate composite particles having calcium carbonate particles fixed on the surface of titanium dioxide particles, and an adhesive.
項６． 二酸化チタン／炭酸カルシウム複合粒子における二酸化チタンと炭酸カルシウムとの重量比が、１：９９〜５０：５０である項５に記載の塗工紙又は塗工板紙用塗料組成物。 Item 6. Item 6. The coated paper or coated paperboard coating composition according to Item 5, wherein the weight ratio of titanium dioxide to calcium carbonate in the titanium dioxide / calcium carbonate composite particles is 1:99 to 50:50.
項７． 水性組成物である項５又は６に記載の塗工紙又は塗工板紙用塗料組成物。 Item 7. Item 7. The coated paper or coated paperboard coating composition according to Item 5 or 6, which is an aqueous composition.
本発明の塗料組成物は、二酸化チタン粒子の表面に炭酸カルシウム粒子を定着させた特殊な顔料を含むことにより、白色度、不透明度が高く、しかも、インキ受理性の高い印刷用塗工紙又は板紙を製造することができる。また、高い隠蔽性が得られるため、高価な二酸化チタンの使用量を少なくすることができ、コストが抑えられる。 The coating composition of the present invention includes a special pigment in which calcium carbonate particles are fixed on the surface of titanium dioxide particles, so that the whiteness and opacity are high, and the printing paper having high ink acceptability or Paperboard can be manufactured. Moreover, since high concealability is obtained, the amount of expensive titanium dioxide used can be reduced, and the cost can be reduced.
詳述すれば、本発明の複合顔料は、二酸化チタン粒子表面に炭酸カルシウム粒子が付着したものであり、炭酸カルシウム粒子がスペーサーの役割をして二酸化チタン粒子間の距離を大きくし、二酸化チタンが有する光散乱力を最大限に発揮させる。その結果白色度・不透明度に優れた塗工紙又は塗工板紙が得られると考えられる。 More specifically, the composite pigment of the present invention has calcium carbonate particles attached to the surface of the titanium dioxide particles. The calcium carbonate particles act as a spacer to increase the distance between the titanium dioxide particles. Make the most of the light scattering power you have. As a result, it is considered that coated paper or coated paperboard having excellent whiteness and opacity can be obtained.
また、本発明の複合顔料は、粒度が比較的大きく、塗工層中の分散性が極めて良好である。さらにこの複合粒子の形状、及び大きさから、インキを塗工層に吸収しやすく、かつ複合粒子によって塗工表面にミクロな粗面が形成されるため、表面にインキがのりやすくなる。そのため高いインキ受理性を付与できる。 In addition, the composite pigment of the present invention has a relatively large particle size and extremely good dispersibility in the coating layer. Furthermore, because of the shape and size of the composite particles, the ink is easily absorbed by the coating layer, and a micro rough surface is formed on the coated surface by the composite particles, so that the ink is easily applied on the surface. Therefore, high ink acceptability can be imparted.
以下、本発明を詳細に説明する。
（Ｉ）塗工紙又は塗工板紙用塗料組成物
本発明の塗工紙又は塗工板紙用塗料組成物は、二酸化チタン粒子表面に炭酸カルシウム粒子を定着させた二酸化チタン／炭酸カルシウム複合粒子と接着剤とを含む組成物である。
二酸化チタン／炭酸カルシウム複合粒子
本発明の塗料組成物中には、無機顔料として、二酸化チタン粒子表面に炭酸カルシウム粒子を定着させた二酸化チタン／炭酸カルシウムの複合粒子が含まれる。本発明において二酸化チタン粒子表面に炭酸カルシウム粒子が「定着」している状態には、二酸化チタン粒子と炭酸カルシウム粒子とがファンデアワールス力により互いに吸着している状態が含まれる。
Hereinafter, the present invention will be described in detail.
(I) Coated paper or coated paperboard coating composition The coated paper or coated paperboard coating composition of the present invention comprises titanium dioxide / calcium carbonate composite particles in which calcium carbonate particles are fixed on the surface of titanium dioxide particles. It is a composition containing an adhesive agent.
Titanium dioxide / calcium carbonate composite particles The coating composition of the present invention contains titanium dioxide / calcium carbonate composite particles in which calcium carbonate particles are fixed on the surface of titanium dioxide particles as an inorganic pigment. In the present invention, the state in which the calcium carbonate particles are “fixed” on the surface of the titanium dioxide particles includes a state in which the titanium dioxide particles and the calcium carbonate particles are adsorbed to each other by van der Waals force.
二酸化チタンと炭酸カルシウムの重量比は、通常１：９９〜５０：５０程度、好ましくは５：９５〜４０：６０程度、より好ましくは１５：８５〜３０：７０程度である。上記範囲であれば、二酸化チタン粒子間の凝集が防止され、また、二酸化チタン量が相対的に十分であるため、実用上十分な白色度、及び不透明度が得られる。 The weight ratio of titanium dioxide to calcium carbonate is usually about 1:99 to 50:50, preferably about 5:95 to 40:60, more preferably about 15:85 to 30:70. If it is the said range, since aggregation between titanium dioxide particles is prevented and the amount of titanium dioxide is relatively sufficient, practically sufficient whiteness and opacity can be obtained.
二酸化チタン／炭酸カルシウムの複合粒子の比表面積は、通常５〜３０ｍ2／ｇ程度、好ましくは８〜１５ｍ2／ｇ程度である。本発明において、比表面積は、BET法において、比表面積測定装置（商品名：フローソーブII２３００、島津製作所社製）を用い、窒素ガス吸着法により測定した値である。 The specific surface area of the composite particles of titanium dioxide / calcium carbonate is usually about 5 to 30 m 2 / g, preferably about 8 to 15 m 2 / g. In the present invention, the specific surface area is a value measured by a nitrogen gas adsorption method using a specific surface area measuring device (trade name: Flowsorb II2300, manufactured by Shimadzu Corporation) in the BET method.
二酸化チタン粒子の結晶型は、特に限定されないが、例えばアナターゼ型またはルチル型のものを用いることができる。二酸化チタン粒子の粒度は通常５０〜５００ｎｍ程度であり、好ましくは１００〜３００ｎｍ程度である。上記範囲であれば、高い白色度・不透明度を有する塗工紙を与える塗料が得られる。また、上記粒度範囲であれば、高いインキ受理性を持つ塗工層が得られる。 The crystal form of the titanium dioxide particles is not particularly limited. For example, an anatase type or rutile type can be used. The particle size of the titanium dioxide particles is usually about 50 to 500 nm, preferably about 100 to 300 nm. If it is the said range, the coating material which gives the coated paper which has high whiteness and opacity will be obtained. Moreover, if it is the said particle size range, the coating layer with high ink acceptability will be obtained.
炭酸カルシウムは、天然カルシウム及び合成カルシウム（沈降性炭酸カルシウム）のいずれも用いることができるが、沈降性炭酸カルシウムを用いることが好ましい。天然炭酸カルシウムは石灰石を機械的に粉砕、分級することにより生産するため粒度分布が比較的広く、粒子形も不均一になりがちである。これに対して、沈降性炭酸カルシウムは粒度分布が狭く、粒子形が比較的均一である。これにより、沈降性炭酸カルシウムでは、粒子どうしが最密充填し難く、粒子間に空間ができるために複合粒子の光散乱力が向上し、その結果白色度・不透明度が高い塗工紙を与える塗料が得られる。 As the calcium carbonate, both natural calcium and synthetic calcium (precipitated calcium carbonate) can be used, but it is preferable to use precipitated calcium carbonate. Since natural calcium carbonate is produced by mechanically grinding and classifying limestone, the particle size distribution is relatively wide and the particle shape tends to be non-uniform. In contrast, precipitated calcium carbonate has a narrow particle size distribution and a relatively uniform particle shape. As a result, precipitated calcium carbonate makes it difficult for the particles to be closely packed, and a space is formed between the particles, so that the light scattering power of the composite particles is improved, resulting in a coated paper with high whiteness and opacity. A paint is obtained.
炭酸カルシウム粒子の粒度は、通常５０〜４００ｎｍ程度、特に７０〜１５０ｎｍ程度であることが好ましい。上記の炭酸カルシウム粒子の粒度範囲であれば、二酸化チタン粒子間の距離が十分になって十分な白色度・不透明度が得られるとともに、二酸化チタン粒子表面に付着し易く、二酸化チタン粒子から離れて存在する炭酸カルシウム粒子の比率が抑えられて、良好な白色度・不透明度が得られる。また、上記粒度範囲であれば、十分なインキの吸収性が得られる。 The particle size of the calcium carbonate particles is preferably about 50 to 400 nm, particularly about 70 to 150 nm. If the above-mentioned particle size range of the calcium carbonate particles, the distance between the titanium dioxide particles is sufficient to obtain sufficient whiteness and opacity, and easily adhere to the surface of the titanium dioxide particles, away from the titanium dioxide particles. The ratio of the calcium carbonate particles present is suppressed, and good whiteness and opacity can be obtained. Moreover, if it is the said particle size range, sufficient absorptivity of ink will be obtained.
上記の粒度の二酸化チタン粒子及び炭酸カルシウム粒子を用いることにより、複合粒子の粒度は、通常０．１〜２μm程度、好ましくは０．５〜１μｍ程度となる。この範囲であれば、高いインキ受理性が得られる。 By using the titanium dioxide particles and calcium carbonate particles having the above particle sizes, the composite particles usually have a particle size of about 0.1 to 2 μm, preferably about 0.5 to 1 μm. Within this range, high ink acceptability can be obtained.
本発明において、粒度はＸ線回折法又は走査型電子顕微鏡観察により測定した値であり、粒度の範囲は、少なくとも８０％以上の粒子がその範囲内に入る場合を指す。 In the present invention, the particle size is a value measured by X-ray diffraction or observation with a scanning electron microscope, and the particle size range refers to a case where at least 80% or more of the particles fall within the range.
炭酸カルシウムの粒子形状は特に制限されず、球形又はｎ面体（ｎは自然数）等のどのような形状であってもよい。いずれの場合も、長軸と短軸との長さの比が、通常０．８〜１程度、特に０．９〜１程度、さらに特に１程度であることが好ましい。特に、球形又は立方体であることが好ましい。また、粒子形状はできるだけ均一であることが好ましい。沈降性炭酸カルシウムである場合には、水酸化カルシウム懸濁液中に炭酸ガスを吹き込むことにより、このような炭酸カルシウム粒子を作製することができる。 The particle shape of calcium carbonate is not particularly limited, and may be any shape such as a sphere or an n-hedron (n is a natural number). In any case, it is preferable that the ratio of the length between the major axis and the minor axis is usually about 0.8 to 1, particularly about 0.9 to 1, and more particularly about 1. In particular, a spherical shape or a cubic shape is preferable. The particle shape is preferably as uniform as possible. In the case of precipitated calcium carbonate, such calcium carbonate particles can be produced by blowing carbon dioxide into a calcium hydroxide suspension.
二酸化チタン／炭酸カルシウム複合粒子は、それには限定されないが、例えば、二酸化チタン粒子と炭酸カルシウム粒子とを水相中で混合する方法で作製することができる。 The titanium dioxide / calcium carbonate composite particles are not limited thereto, but can be produced by, for example, a method of mixing titanium dioxide particles and calcium carbonate particles in an aqueous phase.
ここで、液体中の粒子間の斥力はゼータ電位に関係する。ゼータ電位は、液体中に固体が存在し、固体と液体とが相対運動をするとき、固体に密着して動く液体層の最も外側の面（滑り面）と液体内部との電位差である。ここでは、二酸化チタン粒子のゼータ電位と炭酸カルシウム粒子のゼータ電位との和が最小となるか又は両者のゼータ電位が反対符号となるように、分散媒である水相のｐＨを調整する。例えば、二酸化チタン粒子と沈降性炭酸カルシウム粒子との組み合わせの場合には、ｐＨ６〜１１程度の水相中に両粒子を分散させ、混合すればよい。 Here, the repulsive force between particles in the liquid is related to the zeta potential. The zeta potential is a potential difference between the outermost surface (sliding surface) of the liquid layer that moves in close contact with the solid and the inside of the liquid when the solid is present in the liquid and the solid and the liquid move relative to each other. Here, the pH of the aqueous phase that is the dispersion medium is adjusted so that the sum of the zeta potential of the titanium dioxide particles and the zeta potential of the calcium carbonate particles is minimized, or the zeta potentials of both are opposite signs. For example, in the case of a combination of titanium dioxide particles and precipitated calcium carbonate particles, both particles may be dispersed and mixed in an aqueous phase having a pH of about 6-11.
また、水相中に分散させる二酸化チタン粒子と炭酸カルシウム粒子との重量比は、１：９９〜５０：５０程度とすればよい。
その他の無機顔料
本発明の塗料組成物には、上記説明した複合顔料の他に、本発明の効果を妨げない範囲で、塗工紙用塗料組成物に通常含まれる無機顔料が１種以上含まれていてもよい。このような無機顔料として、例えば、重質炭酸カルシウム、軽質炭酸カルシウム、カオリン、クレー、タルク、サチンホワイト、プラスチックピグメント、二酸化チタン等が挙げられる。
バインダー
本発明の塗料組成物に含まれる接着剤の種類は特に限定されず、塗工紙用塗料組成物の接着剤として公知のものを制限なく使用できる。塗工紙用塗料組成物の接着剤としては、通常、親水性の接着剤が用いられる。このような公知の親水性バインダーとしては、代表的には、スチレン・ブタジエン系共重合体が挙げられる。スチレン・ブタジエン系共重合体としては、スチレン・ブタジエン共重合体の他、さらに、アクリル酸、メチル（メタ）アクリレート、フマル酸、アクリロニトリルのようなビニルモノマーが共重合されたものが挙げられる。また、アクリル酸エステル重合体、エチレン・酢酸ビニル共重合体等も使用できる。
The weight ratio of titanium dioxide particles and calcium carbonate particles dispersed in the aqueous phase may be about 1:99 to 50:50.
Other Inorganic Pigments In addition to the composite pigments described above, the coating composition of the present invention contains one or more inorganic pigments that are usually contained in a coating composition for coated papers, as long as the effects of the present invention are not impaired. It may be. Examples of such inorganic pigments include heavy calcium carbonate, light calcium carbonate, kaolin, clay, talc, satin white, plastic pigment, titanium dioxide and the like.
Binder The type of adhesive contained in the coating composition of the present invention is not particularly limited, and any known adhesive as a coating composition for coated paper can be used without limitation. As the adhesive for the coating composition for coated paper, a hydrophilic adhesive is usually used. A typical example of such a known hydrophilic binder is a styrene-butadiene copolymer. Examples of the styrene / butadiene copolymer include those obtained by copolymerizing vinyl monomers such as acrylic acid, methyl (meth) acrylate, fumaric acid, and acrylonitrile in addition to the styrene / butadiene copolymer. In addition, acrylic acid ester polymers, ethylene / vinyl acetate copolymers, and the like can also be used.
上記のバインダーに加えて、塗料組成物の保水性を維持し、原紙の内部結合強度を高めるために、酸化澱粉、エステル化又はエーテル化デンプン、酵素変性デンプン、それらをフラッシュドライして得られる冷水可溶性デンプン、カゼイン、大豆タンパク質のような天然系接着剤、ポリビニルアルコールのような合成系接着剤を併用しても良い。 In addition to the above binder, in order to maintain the water retention of the coating composition and increase the internal bond strength of the base paper, oxidized starch, esterified or etherified starch, enzyme-modified starch, cold water obtained by flash drying them Natural adhesives such as soluble starch, casein, and soy protein, and synthetic adhesives such as polyvinyl alcohol may be used in combination.
バインダーの使用量は、顔料に対して８〜３０重量％程度が好ましい。本発明の塗料組成物は水性組成物であり、無機顔料、バインダーなどが水に相溶している。
その他の成分
本発明の塗料組成物には、この他、分散剤、増粘剤、保水剤、消泡剤、耐水化剤、着色剤等通常の塗工紙用塗料組成物に配合される各種助剤が含まれていてよい。
（ＩＩ）塗工紙又は塗工板紙
本発明の塗工紙は、基材となる紙又は板紙上に、本発明の塗料組成物が塗布されてなるものである。
The amount of the binder used is preferably about 8 to 30% by weight with respect to the pigment. The coating composition of the present invention is an aqueous composition, and an inorganic pigment, a binder and the like are compatible with water.
Other components In addition to the above, the coating composition of the present invention includes a dispersant, a thickener, a water retention agent, an antifoaming agent, a water resistance agent, a colorant, and the like, which are variously incorporated into a normal coating paper coating composition. Auxiliaries may be included.
(II) Coated paper or coated paperboard The coated paper of the present invention is obtained by applying the coating composition of the present invention on a paper or paperboard serving as a substrate.
基紙の種類は特に限定されず、一般の印刷用塗工紙および塗工板紙に用いられる原紙を使用する。紙と板紙は区別されているが、その定義は必ずしも明確ではない。一般に板紙とは目方が重く、厚みや硬さもあり多層に抄き合わされている紙のことを呼ぶ。印刷用塗工紙の場合、基紙の坪量は、３０〜２００ｇ／ｍ2程度が好ましく、必要に応じて上質紙、中質紙を選択して使用する。板紙の場合、坪量が２００ｇ／ｍ2以上、好ましくは１０００ｇ／ｍ2程度のものを使用すればよい。 The type of base paper is not particularly limited, and base paper used for general printing coated paper and coated paperboard is used. Paper and paperboard are distinguished, but their definition is not always clear. In general, a paperboard is a paper that is heavier and has a thickness and hardness, and is laminated in multiple layers. In the case of coated paper for printing, the basis weight of the base paper is preferably about 30 to 200 g / m 2 , and high-quality paper or medium-quality paper is selected and used as necessary. In the case of paperboard, a basis weight of 200 g / m 2 or more, preferably about 1000 g / m 2 may be used.
塗工紙を製造するに当たっては、塗工紙製造に一般に用いられているブレードコータ、エアナイフコータ、ロールコータ、バーコータ、スプレーコータ等の塗工装置を設けたオンマシンあるいはオフマシンコータによって原紙上に単層あるいは多層塗布すればよい。 When producing coated paper, on-machine or off-machine coaters equipped with coating devices such as blade coaters, air knife coaters, roll coaters, bar coaters, spray coaters and the like that are commonly used in coated paper production are used on the base paper. Single layer or multilayer coating may be applied.
塗布時の塗料組成物中の固形分濃度は４０〜６８％程度に調整することが好ましい。また、塗布量は、固形分の塗布量が７〜２０ｇ／ｍ2程度になるようにするのが好ましい。そのうち複合顔料の含有比率は０．５〜５０％程度とすれば良い。このような塗布量にすることにより、複合顔料の塗布量が５〜３０ｇ／ｍ2程度になる。 The solid content concentration in the coating composition at the time of application is preferably adjusted to about 40 to 68%. The coating amount is preferably such that the solid coating amount is about 7 to 20 g / m 2 . Of these, the content ratio of the composite pigment may be about 0.5 to 50%. By setting it as such an application quantity, the application quantity of a composite pigment will be about 5-30 g / m < 2 >.
さらに、白紙光沢度、平滑度を上げるためにスーパーカレンダ、ソフトカレンダなどの仕上げ装置で処理をすればよい。
実施例
以下、実施例及び試験例を示して本発明を説明するが、本発明はこれらに限定されるものではない。実施例中「部」とあるのは特に断りのない限り、「重量部」を意味する。
実施例1
＜複合粒子の調製＞
平均粒径２００ｎｍのアナターゼ型二酸化チタンと平均粒径１００ｎｍの立方体形状の沈降性炭酸カルシウムとを、２０：８０の割合で混合した後、水を加え２０重量％スラリーに調整した。この混合スラリーに二酸化炭素を吹き込むことにより、そのｐＨを７．８に調節した。ｐＨが安定化したスラリーをコロイドミルに通した。コロイドミルのロータとステータとの間隙は100μmに設定した。また、コロイドミル内での滞留時間は０．１秒未満にした。混合物の温度は２０℃であった。生成した１００ｎｍの沈降性炭酸カルシウム粒子がファンデルワールス力によって二酸化チタンの表面に付着した。得られた複合粒子は、二酸化チタン:炭酸カルシウムの重量比が２０：８０であり、その比表面積は１０ｍ2／ｇであった。
＜塗料組成物の調製＞
次いで、該スラリーをフィルタープレス等で脱水し、得られた濾過ケーキに二酸化チタン／炭酸カルシウム複合粒子１００部に対してポリアクリル酸ソーダ系分散剤を０．５部添加して、ディスパー分散機によって分散し、濃度６０％のスラリーを調製した。
Furthermore, in order to increase the glossiness and smoothness of the blank paper, the processing may be performed by a finishing device such as a super calendar or a soft calendar.
EXAMPLES Hereinafter, the present invention will be described with reference to examples and test examples, but the present invention is not limited thereto. In the examples, “parts” means “parts by weight” unless otherwise specified.
Example 1
<Preparation of composite particles>
Anatase-type titanium dioxide having an average particle diameter of 200 nm and cubic precipitated calcium carbonate having an average particle diameter of 100 nm were mixed at a ratio of 20:80, and water was added to prepare a 20 wt% slurry. The pH was adjusted to 7.8 by blowing carbon dioxide into the mixed slurry. The pH stabilized slurry was passed through a colloid mill. The gap between the rotor and stator of the colloid mill was set to 100 μm. Also, the residence time in the colloid mill was less than 0.1 seconds. The temperature of the mixture was 20 ° C. The produced 100 nm precipitated calcium carbonate particles adhered to the surface of titanium dioxide by van der Waals force. The obtained composite particles had a titanium dioxide: calcium carbonate weight ratio of 20:80 and a specific surface area of 10 m 2 / g.
<Preparation of coating composition>
Next, the slurry is dehydrated with a filter press or the like, and 0.5 part of a polyacrylic acid soda-based dispersant is added to 100 parts of titanium dioxide / calcium carbonate composite particles to the obtained filter cake. Dispersed to prepare a slurry with a concentration of 60%.
さらに、この複合顔料１００部に対して、接着剤として尿素リン酸エステル化でんぷん（日本食品化工製、ＭＳ＃４６００）３部及びスチレン−ブタジエン共重合ラテックス（日本エイアンドエル製、ＳＮ−３０７）１３部を添加して、固形分濃度で５６％の塗料を調製した。
＜塗工紙の製造＞
かくして調製された塗料を坪量８０ｇ／ｍ2の上質原紙にコーティングロッドで塗工量片面あたり１０ｇ／ｍ2になるように手塗りした。さらにスーパーカレンダで処理温度６０℃、処理線圧５８．８ｋＮ／ｍ、通紙速度 ２０ｍ／ｍｉｎ，通紙回数 3回の条件で表面処理して印刷用塗工紙を得た。
比較例１
実施例１において、複合顔料に代えて、市販の二酸化チタン（Ａ−２２０：石原産業(株)製）を顔料として用い、その他は同様にして、印刷用塗工紙を得た。
比較例２
実施例１において、複合顔料に代えて、市販の沈降性炭酸カルシウム（Ｂｒｉｌｌｉａｎｔ−１５：白石工業(株)製）を顔料として用い、その他は同様にして、印刷用塗工紙を得た。
比較例３
実施例１において、複合顔料に代えて、No.1高白色クレー（Ｋａｏｇｌｏｓｓ
−９０：Ｔｈｉｅｌｅ Ｋａｏｌｉｎ社製）を顔料として用い、その他は同様にして、印刷用塗工紙を得た。
比較例４
実施例１において、複合顔料に代えて、市販の二酸化チタン（Ａ−２２０：石原産業(株)製）と市販の沈降性炭酸カルシウム（Ｂｒｉｌｌｉａｎｔ−１５：白石工業(株)製）とを、２０：８０の重量比で混合した顔料を用い、その他は同様にして、印刷用塗工紙を得た。
比較例５
実施例１において、複合顔料に代えて、市販の二酸化チタン（Ａ−２２０：石原産業(株)製）と市販の沈降性炭酸カルシウム（Ｂｒｉｌｌｉａｎｔ−１５：白石工業(株)製）とを、４０：６０の重量比で混合した顔料を用い、その他は同様にして、印刷用塗工紙を得た。
白色度・不透明度の評価
実施例及び比較例１〜６により得られた各印刷用塗工紙の白色度・不透明度を、テクニブライトマイクロＴＢ−１Ｃ型(カルテックサイエンス社製)を用いて、ＪＩＳ Ｐ−８１４８に準じてＩＳＯ白色度・不透明度を測定することにより評価した。
Furthermore, with respect to 100 parts of this composite pigment, 3 parts of urea phosphated starch (manufactured by Nippon Shokuhin Kako, MS # 4600) and 13 parts of styrene-butadiene copolymer latex (manufactured by Nippon A & L, SN-307) as adhesives Was added to prepare a paint having a solid content concentration of 56%.
<Manufacture of coated paper>
The coating material thus prepared was hand-coated on a high-quality base paper having a basis weight of 80 g / m 2 with a coating rod so that the coating amount was 10 g / m 2 per side. Further, a surface treatment was performed with a super calender at a processing temperature of 60 ° C., a processing linear pressure of 58.8 kN / m, a paper passing speed of 20 m / min, and a paper passing rate of 3 times to obtain a coated paper for printing.
Comparative Example 1
In Example 1, instead of the composite pigment, commercially available titanium dioxide (A-220: manufactured by Ishihara Sangyo Co., Ltd.) was used as a pigment, and the others were similarly obtained to obtain a coated paper for printing.
Comparative Example 2
In Example 1, instead of the composite pigment, commercially available precipitated calcium carbonate (Brilliant-15: manufactured by Shiroishi Kogyo Co., Ltd.) was used as the pigment, and the others were similarly used to obtain a coated paper for printing.
Comparative Example 3
In Example 1, instead of the composite pigment, No. 1 high white clay (Kaogloss)
-90: manufactured by Thiele Kaolin) was used as a pigment, and the others were similarly obtained to obtain a coated paper for printing.
Comparative Example 4
In Example 1, instead of the composite pigment, commercially available titanium dioxide (A-220: manufactured by Ishihara Sangyo Co., Ltd.) and commercially available precipitated calcium carbonate (Brilliant-15: manufactured by Shiroishi Kogyo Co., Ltd.) A coated paper for printing was obtained in the same manner except that the pigment mixed at a weight ratio of 80 was used.
Comparative Example 5
In Example 1, instead of the composite pigment, commercially available titanium dioxide (A-220: manufactured by Ishihara Sangyo Co., Ltd.) and commercially available precipitated calcium carbonate (Brilliant-15: manufactured by Shiroishi Kogyo Co., Ltd.) A coated paper for printing was obtained in the same manner using the pigment mixed at a weight ratio of 60:60.
The whiteness and opacity of each coated paper for printing obtained in the evaluation examples of whiteness and opacity and Comparative Examples 1 to 6, using Technibright Micro TB-1C type (manufactured by Caltech Science), It evaluated by measuring ISO whiteness and opacity according to JIS P-8148.
また、光散乱係数を以下のクベルカ−ムンクの式に従い算出した。
R0：黒色標準版を裏当てした場合の白色度
R∞：白色度
R0/R∞：不透明度
X：坪量（ｇ／ｍ2）
インキ受理性の評価
実施例及び比較例１〜６により得られた各印刷用塗工紙のインキ受理性を、これらの塗工紙の上に、K&Nテストインキを3milのアプリケーターによって均一な厚さに塗布し、2分後の白色度の変化率を測定することにより評価した。白色度の測定方法は前出した通りである。
R 0 : Whiteness when backed by black standard version
R∞: Whiteness
R 0 / R∞: Opacity
X: Basis weight (g / m 2 )
Evaluation of Ink Acceptability Ink acceptability of each printing coated paper obtained in Examples and Comparative Examples 1 to 6 was measured with a uniform thickness of K & N test ink on these coated papers using a 3 mil applicator. It was evaluated by measuring the rate of change in whiteness after 2 minutes. The measuring method of whiteness is as described above.
結果を以下の表１に示す。 The results are shown in Table 1 below.
表１から明らかなように、本発明の複合顔料を使用した実施例１は、白色度、不透明度が共に良好で、さらに良好なインキ受理性を示した。 As can be seen from Table 1, Example 1 using the composite pigment of the present invention had good whiteness and opacity, and also showed good ink acceptability.
これに対して、顔料として二酸化チタンのみ用いた比較例１では、不透明度は優れていたが、白色度が低かった。また、二酸化チタン及び炭酸カルシウムを複合粒子とせずに含有する比較例４では、不透明度は優れているが白色度が悪かった。 On the other hand, in Comparative Example 1 using only titanium dioxide as the pigment, the opacity was excellent, but the whiteness was low. Further, in Comparative Example 4 containing titanium dioxide and calcium carbonate without using composite particles, the opacity was excellent but the whiteness was poor.
比較例５は、白色度、不透明度ともに良好であった。このことは、白色度・不透明度を勘案した光散乱係数にも現れている。比較例５の光散乱係数は実施例１と略同様である。即ち、実施例１は高価な二酸化チタンを２０％しか配合していないにもかかわらず、複合粒子の形態をとるため、二酸化チタンを単独で４０％配合した比較例５と同等の白色度・不透明度を示す。 In Comparative Example 5, both whiteness and opacity were good. This also appears in the light scattering coefficient considering whiteness and opacity. The light scattering coefficient of Comparative Example 5 is substantially the same as that of Example 1. That is, although Example 1 contains only 20% of expensive titanium dioxide, it takes the form of composite particles. Indicates transparency.
また、炭酸カルシウムのみ含む比較例２、カオリンのみ含む比較例４では、白色度及び不透明度の双方が悪かった。 In Comparative Example 2 containing only calcium carbonate and Comparative Example 4 containing only kaolin, both whiteness and opacity were poor.
さらに、全ての比較例で、インキ受理性が悪かった。
Furthermore, in all comparative examples, the ink acceptability was poor.
Claims (7)
The coating composition for coated paper or coated paperboard according to claim 5 or 6, which is an aqueous composition.
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| JP2014058427A (en) * | 2012-09-19 | 2014-04-03 | Shiraishi Kogyo Kaisha Ltd | White resin composition |
| JP2016166806A (en) * | 2015-03-10 | 2016-09-15 | 国立大学法人埼玉大学 | Three-dimensional measurement method |
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| JP2016166806A (en) * | 2015-03-10 | 2016-09-15 | 国立大学法人埼玉大学 | Three-dimensional measurement method |
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