JP2001089689A - Matting agent for printing ink, printing ink composition comprising the same and its use - Google Patents

Matting agent for printing ink, printing ink composition comprising the same and its use

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Publication number
JP2001089689A
JP2001089689A JP2000039763A JP2000039763A JP2001089689A JP 2001089689 A JP2001089689 A JP 2001089689A JP 2000039763 A JP2000039763 A JP 2000039763A JP 2000039763 A JP2000039763 A JP 2000039763A JP 2001089689 A JP2001089689 A JP 2001089689A
Authority
JP
Japan
Prior art keywords
chloride resin
printing ink
polyvinyl chloride
weight
particle size
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.)
Pending
Application number
JP2000039763A
Other languages
Japanese (ja)
Inventor
Koji Inage
康二 稲毛
Hitoshi Narabe
仁 奈良部
Satoshi Nakamura
中村　　聡
Yasushi Hori
靖史 堀
Yoji Matsumoto
洋二 松本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tosoh Corp
Original Assignee
Tosoh Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tosoh Corp filed Critical Tosoh Corp
Priority to JP2000039763A priority Critical patent/JP2001089689A/en
Publication of JP2001089689A publication Critical patent/JP2001089689A/en
Pending legal-status Critical Current

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Abstract

PROBLEM TO BE SOLVED: To provide a matting agent for a printing ink capable of exhibiting a matte feeling equal or superior to a matting agent using silica or the like while maintaining excellency in ink flowability and dispersibility. SOLUTION: The matting agent for a printing ink comprises polyvinyl chloride resin particles having a particle size ranging from 0.01 to 50 μm and an average particle size of 0.1-40 μm, and 100 pts.wt. of a dried powder of the particles are admixed with 60 pts.wt. of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate and kneaded by a dissolver type mixer at 800 rpm at 25 deg.C for 3 min to give an average resin particle size of 0.1-70 μm and a maximum particle size of less than 150 μm. The subject printing ink composition comprises 3-60 pts.wt. of the matting agent.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、印刷インキ用艶消
し剤に関するものであり、更に詳しくは印刷効果を高め
るためのマットインキ（艶消しインキ）の分野におい
て、流動性に優れ、良好な艶消し効果を有する印刷イン
キを得るための艶消し剤、及びそれよりなる印刷インキ
組成物、並びにその用途に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a matting agent for printing inks, and more particularly to a matting ink (matting ink) for enhancing a printing effect, which has excellent fluidity and good gloss. The present invention relates to a matting agent for obtaining a printing ink having a matting effect, a printing ink composition comprising the same, and uses thereof.

【０００２】[0002]

【従来の技術】一般にカレンダー、ポスター等の印刷物
では、目が疲れにくく、広角度から印刷物を見ることが
できる様にマットインキ（艶消しインキ）が使用されて
いる。2. Description of the Related Art In general, in printed materials such as calendars and posters, mat ink (matte ink) is used so that eyes are hardly tired and the printed materials can be viewed from a wide angle.

【０００３】このマットインキは、インキの乾燥後にイ
ンキ表面に微細な凹凸をつくる必要があり、そのためシ
リカ等の無機物が艶消し剤として用いられてきた。[0003] In this matte ink, it is necessary to form fine irregularities on the surface of the ink after the ink is dried. Therefore, inorganic substances such as silica have been used as matting agents.

【０００４】一方、ポリ塩化ビニル樹脂を使用した艶消
し方法についても種々の提案がなされているものの、い
ずれもがポリ塩化ビニル樹脂成形品の艶消しに関するも
のであり、印刷用インキの艶消し剤としての検討は行わ
れてこなかった。[0004] On the other hand, various proposals have been made on matting methods using polyvinyl chloride resin, but all of them are related to matting of polyvinyl chloride resin molded articles, and are used as matting agents for printing inks. The study has not been carried out.

【０００５】例えば、特開昭５４−１１７５５０号は、
テトラヒドロフランに不溶のゲル分が１〜９０重量%の
ポリ塩化ビニル樹脂１００重量部と可塑剤２５〜２００
重量部からなるポリ塩化ビニル系組成物を用いること
で、成形品の艶消しに効果のあることを開示している。For example, Japanese Patent Application Laid-Open No. Sho 54-117550 discloses that
100 parts by weight of a polyvinyl chloride resin having a gel content insoluble in tetrahydrofuran of 1 to 90% by weight and a plasticizer of 25 to 200%
It discloses that the use of a polyvinyl chloride-based composition consisting of parts by weight is effective in matting a molded article.

【０００６】また、特開昭５４−１６３９３９号は、塩
化ビニルモノマーと架橋モノマーの共重合体を1成分と
するポリ塩化ビニル系組成物を用いることで成形品の圧
縮歪が少なく、成形品表面の艶消しに効果があることを
開示している。Japanese Patent Application Laid-Open No. Sho 54-163939 discloses that a polyvinyl chloride composition containing a copolymer of a vinyl chloride monomer and a cross-linking monomer as one component is used to reduce the compression strain of the molded product and reduce the surface of the molded product. Discloses that it is effective for matting.

【０００７】さらに、塗料関係では、特開平１０−２７
９８７８号は、平均粒径が５μ未満の架橋型ポリ塩化ビ
ニル樹脂２５〜４０重量部と非架橋型ポリ塩化ビニル樹
脂の合計１００重量部に対して可塑剤３０〜１００重量
部からなるポリ塩化ビニル系の塗料を用いることで金属
塗装板の艶消しに効果があることを開示している。Further, regarding paints, Japanese Patent Application Laid-Open No. H10-27
No. 9878 discloses polyvinyl chloride comprising 25 to 40 parts by weight of a crosslinked polyvinyl chloride resin having an average particle size of less than 5 μm and a plasticizer of 30 to 100 parts by weight based on a total of 100 parts by weight of a non-crosslinked polyvinyl resin. It is disclosed that the use of a system paint is effective in matting a metal coated plate.

【０００８】ところで、上記公知文献の技術は、いわゆ
るポリ塩化ビニル樹脂と可塑剤の組合せをベースとする
プラスチゾル加工、或いはポリ塩化ビニル自体を成形加
工する場合に限られた技術範囲に留まっており、いわゆ
る印刷用インキへの技術検討はなされていなかった。[0008] The techniques disclosed in the above-mentioned known documents are limited to a plastisol process based on a combination of a so-called polyvinyl chloride resin and a plasticizer, or a technology range limited to the case of forming and processing polyvinyl chloride itself. Technical studies on so-called printing inks have not been made.

【０００９】そのため、数μm〜数１０μmの塗布を行う
印刷用インキでは従来艶消し剤としてはシリカ等の無機
物が用いられ、数１００μ〜数mmの塗布を行うポリ塩化
ビニルゾル系塗料とは技術分野が異なっていた。For this reason, in a printing ink for applying a coating of several μm to several tens of μm, an inorganic substance such as silica is conventionally used as a matting agent, and a polyvinyl chloride sol-based coating for applying a coating of several hundred μm to several mm is a technical field. Was different.

【００１０】[0010]

【発明が解決しようとする課題】印刷物の艶消し感の要
求は広がってきているものの、上記に示した様にシリカ
等を艶消し剤に使用した場合、マットインキのコストが
高くなる。また、シリカ等の無機物をインキ中に含有さ
せる場合、インキ中への分散に大きな労力が必要なうえ
に、インキ自体の粘度が高くなり流動性を調整するため
に粘稠度調整剤等を添加しなければならなかった。[0005] Although the demand for a matte feeling of printed matter has been widened, when silica or the like is used as a matting agent as described above, the cost of matte ink increases. In addition, when inorganic substances such as silica are contained in the ink, a great effort is required for dispersing in the ink, and the viscosity of the ink itself becomes high, and a viscosity modifier is added to adjust the fluidity. I had to.

【００１１】そこで本発明では従来のマットインキが持
つ艶消し感は保持したまま、インキ中への分散が容易
で、且つインキ自体の流動性に優れた印刷インキを与え
る印刷インキ用艶消し剤、及びそれを用いた印刷インキ
組成物、並びにその用途を提供することにある。Therefore, in the present invention, a matting agent for a printing ink which provides a printing ink which is easily dispersed in the ink and has excellent fluidity of the ink itself, while maintaining the matte feeling of the conventional mat ink, And a printing ink composition using the same, and an application thereof.

【００１２】[0012]

【課題を解決するための手段】本発明者らは、上記課題
について鋭意検討した結果、特定の粒子径分布を有する
ポリ塩化ビニル樹脂を印刷用インキに含有させることに
より、艶消し感は保持したまま、粘稠度調整剤等の助剤
の添加をしなくとも良好な流動性が保持できることを見
出し本発明を完成させるに至った。Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have maintained a matte feeling by including a polyvinyl chloride resin having a specific particle size distribution in a printing ink. It has been found that good fluidity can be maintained without adding an auxiliary agent such as a viscosity modifier as it is, and the present invention has been completed.

【００１３】即ち、本発明は、粒子径が０．０１〜５０
μm、かつ、平均粒径が０．１〜４０μmであるポリ塩化
ビニル樹脂粒子であって、このポリ塩化ビニル樹脂粒子
の乾燥粉末１００重量部と２，２，４−トリメチル１，
３−ペンタンジオールジイソブチレート６０重量部とを
配合しデイゾルバー式ミキサーを用い２５℃、８００ｒ
ｐｍで３分間混錬したときの配合物中のポリ塩化ビニル
樹脂の平均粒子径が０．１〜７０μｍでその最大粒子径
が１５０μｍ未満となるポリ塩化ビニル樹脂粒子からな
る印刷インキ用艶消し剤、及びそれを用いた印刷インキ
組成物、並びにその用途に関するものである。That is, according to the present invention, the particle diameter is from 0.01 to 50.
μm, and polyvinyl chloride resin particles having an average particle size of 0.1 to 40 μm, wherein 100 parts by weight of dry powder of the polyvinyl chloride resin particles and 2,2,4-trimethyl 1,2
60 parts by weight of 3-pentanediol diisobutyrate were mixed with a dissolver type mixer at 25 ° C. and 800 r.
Matting agent for printing ink consisting of polyvinyl chloride resin particles having an average particle size of 0.1 to 70 μm and a maximum particle size of less than 150 μm when kneaded at pm for 3 minutes. And a printing ink composition using the same, and uses thereof.

【００１４】以下に本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.

【００１５】本発明の印刷インキ用艶消し剤は、粒子径
が０．０１〜５０μm、かつ、平均粒径が０．１〜４０
μmであるポリ塩化ビニル樹脂粒子であって、このポリ
塩化ビニル樹脂粒子の乾燥粉末１００重量部と２，２，
４−トリメチル１，３−ペンタンジオールジイソブチレ
ート６０重量部とを配合しデイゾルバー式ミキサーを用
い２５℃、８００ｒｐｍで３分間混錬したときの配合物
（Ａ）中のポリ塩化ビニル樹脂の平均粒子径が０．１〜
７０μｍでその最大粒子径が１５０μｍ未満となるポリ
塩化ビニル樹脂粒子からなるものである。The matting agent for printing ink of the present invention has a particle size of 0.01 to 50 μm and an average particle size of 0.1 to 40.
μm polyvinyl chloride resin particles, wherein 100 parts by weight of dry powder of the polyvinyl chloride resin particles are
Average particles of polyvinyl chloride resin in blend (A) when blended with 60 parts by weight of 4-trimethyl 1,3-pentanediol diisobutyrate and kneaded with a dissolver mixer at 25 ° C. and 800 rpm for 3 minutes Diameter 0.1 ~
It is made of polyvinyl chloride resin particles having a maximum particle size of less than 150 μm at 70 μm.

【００１６】ポリ塩化ビニル樹脂粒子の粒径範囲として
は、０．０１〜５０μｍ、好ましくは０．０５〜４５μ
ｍ、更に好ましくは０．０５〜４０μｍであり、ポリ塩
化ビニル樹脂粒子の平均粒径としては、０．１〜４０μ
ｍ、好ましくは０．１５〜２０μｍ、更に好ましくは
０．５〜１０μｍである。The particle size range of the polyvinyl chloride resin particles is 0.01 to 50 μm, preferably 0.05 to 45 μm.
m, more preferably 0.05 to 40 μm, and the average particle size of the polyvinyl chloride resin particles is 0.1 to 40 μm.
m, preferably 0.15 to 20 μm, more preferably 0.5 to 10 μm.

【００１７】一方、配合物（Ａ）中のポリ塩化ビニル樹
脂の平均粒径としては、０．１〜７０μｍ、好ましくは
１〜３０μｍ、更に好ましくは、１．５〜２５μｍであ
り、その最大粒径は１５０μｍ未満、好ましくは１００
μｍ未満である。On the other hand, the average particle size of the polyvinyl chloride resin in the compound (A) is 0.1 to 70 μm, preferably 1 to 30 μm, and more preferably 1.5 to 25 μm. The diameter is less than 150 μm, preferably 100
It is less than μm.

【００１８】本発明の印刷インキ用艶消し剤のポリ塩化
ビニル樹脂粒子の粒子径が０．０１μｍ未満、もしくは
平均粒子径が０．１μｍ未満である場合、または配合物
（Ａ）中のポリ塩化ビニル樹脂の平均粒径が０．１μｍ
未満である場合は、得られる印刷インキの流動性の悪化
や、艶消し効果が十分でない等の問題が生じるおそれが
ある。When the polyvinyl chloride resin particles of the matting agent for printing ink of the present invention have a particle size of less than 0.01 μm or an average particle size of less than 0.1 μm, or the polyvinyl chloride in the formulation (A) Average particle size of vinyl resin is 0.1μm
If it is less than 1, there is a possibility that problems such as deterioration of the fluidity of the obtained printing ink and insufficient matting effect may occur.

【００１９】一方、ポリ塩化ビニル樹脂粒子の粒子径が
５０μｍを越える場合、もしくは平均粒子径が４０μｍ
を超える場合、または配合物（Ａ）中のポリ塩化ビニル
樹脂の平均粒径が７０μｍを超える場合、もしくは最大
粒子径が１５０μｍ以上の場合には、印刷塗布物表面の
凹凸が悪化する問題等が生じるおそれがある。On the other hand, when the particle size of the polyvinyl chloride resin particles exceeds 50 μm, or when the average particle size is 40 μm
When the average particle diameter of the polyvinyl chloride resin in the composition (A) exceeds 70 μm, or when the maximum particle diameter is 150 μm or more, the unevenness of the surface of the printed coating material may be deteriorated. May occur.

【００２０】ここでいうポリ塩化ビニル樹脂の粒径と
は、ポリ塩化ビニル樹脂の1次粒子径を意味し、一般に
乾燥後の粒径は、ポリ塩化ビニル樹脂がインク内で分散
可能な乾燥凝集力であれば特に限定はなく、顆粒状、微
粉状での使用が可能である。The particle size of the polyvinyl chloride resin as referred to herein means the primary particle size of the polyvinyl chloride resin. Generally, the particle size after drying is determined by the dry agglomeration in which the polyvinyl chloride resin can be dispersed in the ink. There is no particular limitation as long as it is a force, and it can be used in the form of granules or fine powder.

【００２１】上述のようなポリ塩化ビニル樹脂粒子の粒
度分布の一例として、粒子径０．０１μｍ以上０．４５
μｍ未満の粒子が３〜５０重量％（好ましくは、３〜２
０重量％、更に好ましくは５〜１５重量％）、０．４５
μｍ以上１．８μｍ未満の粒子が３０〜９５重量％（好
ましくは、５０〜８５重量％、更に好ましくは６０〜８
５重量％）、１．８μｍ以上５０μｍの粒子が２〜４０
重量％（好ましくは、５〜４０重量％）のような例を挙
げることができるが、この粒度分布の例に限定されるも
のではない。As an example of the particle size distribution of the polyvinyl chloride resin particles as described above, a particle size of 0.01 μm or more and 0.45
3 to 50% by weight (preferably 3 to 2%)
0% by weight, more preferably 5 to 15% by weight), 0.45%
30 to 95% by weight (preferably 50 to 85% by weight, more preferably 60 to 8% by weight)
5% by weight) 2 to 40 particles of 1.8 μm to 50 μm
Examples such as% by weight (preferably 5 to 40% by weight) can be given, but are not limited to this example of particle size distribution.

【００２２】本発明の印刷インキ用艶消し剤を、溶剤系
印刷インキ（非水系印刷用インキ）塗布後の印刷物の艶
消しに用いる場合には、良好な艶消し感を得るために、
ポリ塩化ビニル樹脂粒子中のテトラヒドロフランに不溶
のゲル分が３０重量％以上であることが好ましく、更に
好ましくはゲル分が５０重量％以上、特に好ましくはゲ
ル分が８５重量％以上あるものがよい。一方、ポリ塩化
ビニル樹脂と親和性の低い配合剤で構成されているオフ
セットインキ等の艶消しに用いる場合には、ゲル分が３
０重量％以下であってもよい。When the matting agent for printing ink of the present invention is used for matting printed matter after applying a solvent-based printing ink (non-aqueous printing ink), in order to obtain a good matte feeling,
It is preferable that the gel component insoluble in tetrahydrofuran in the polyvinyl chloride resin particles is 30% by weight or more, more preferably 50% by weight or more, particularly preferably 85% by weight or more. On the other hand, when used for matting an offset ink or the like composed of a compound having a low affinity for a polyvinyl chloride resin, the gel content is 3%.
It may be 0% by weight or less.

【００２３】また、上記の溶剤としては、例えば、ソル
ビリテイパラメーターが３〜２０（ｃａｌ／ｃｍ3）0.5
の範囲にある溶剤であり、具体的には、例えば、ヘキサ
ン、メチルイシブチルケトン、トルエン、酢酸エチル、
メチルエチルケトン、アセトン、ブチルアルコール、イ
ソプロピルアルコール、エチルアルコール等を挙げるこ
とができる。Further, as the solvent, for example, sorbitan kink Tay parameter 3~20 (cal / cm 3) 0.5
Solvents, specifically, for example, hexane, methyl isibutyl ketone, toluene, ethyl acetate,
Examples thereof include methyl ethyl ketone, acetone, butyl alcohol, isopropyl alcohol, and ethyl alcohol.

【００２４】また、本発明の印刷インキ用艶消し剤の印
刷インキ組成物中における含有量としては、印刷インキ
組成物の３〜６０重量部が好ましい。艶消し剤の含有量
が３重量部未満の場合、艶消し効果が少ない等の問題が
生じるおそれがあり、また、艶消し剤の含有量が６０重
量部を超える場合にはインキの流動性が低下し、印刷適
性が悪化する等の問題が発生するおそれがある。The content of the matting agent for printing ink of the present invention in the printing ink composition is preferably 3 to 60 parts by weight of the printing ink composition. When the content of the matting agent is less than 3 parts by weight, problems such as a low matting effect may occur, and when the content of the matting agent exceeds 60 parts by weight, the fluidity of the ink may be reduced. This may cause problems such as deterioration in printability and deterioration of printability.

【００２５】そして、印刷インキ組成物中の含有量とし
ては、特に艶消し効果と流動性とのバランスに優れるこ
とから５〜５０重量％が好ましく、さらに６〜３０重量
％が好ましい。The content in the printing ink composition is preferably from 5 to 50% by weight, and more preferably from 6 to 30% by weight, since the balance between the matting effect and the fluidity is particularly excellent.

【００２６】本発明の印刷インキ用艶消し剤を印刷イン
キに使用する場合、適度な粘着性が必要なインキに関し
ては増粘剤を本発明の艶消し剤１００重量部に対して２
〜５０重量部、好ましくは５〜３０重量部、更に好まし
くは７〜２０重量部となるような割合で配合することが
好ましい。When the matting agent for a printing ink of the present invention is used for a printing ink, a thickening agent is added to 100 parts by weight of the matting agent of the present invention for an ink requiring an appropriate tackiness.
It is preferable to mix them in such a ratio as to be 50 to 50 parts by weight, preferably 5 to 30 parts by weight, more preferably 7 to 20 parts by weight.

【００２７】増粘剤とは、例えばシリカ、炭酸カルシウ
ム、ベントナイト、合成雲母、セラミックス、炭酸マグ
ネシウム、ガラス、ステアリン酸アルミニウム、ステア
リン酸亜鉛、ケイ酸マグネシウム、パルミチン酸金属塩
等が挙げられ、特に０．１〜１０μmのシリカを用いる
ことが好ましく、さらに有機表面処理シリカ、疎水性シ
リカが好ましい。Examples of the thickener include silica, calcium carbonate, bentonite, synthetic mica, ceramics, magnesium carbonate, glass, aluminum stearate, zinc stearate, magnesium silicate, and metal palmitate. It is preferable to use silica having a thickness of 0.1 to 10 μm, and more preferable is an organic surface-treated silica and hydrophobic silica.

【００２８】本発明の印刷インク用艶消し剤は、界面活
性剤及び重合開始剤の存在下、塩化ビニル単量体、また
は塩化ビニル単量体およびエチレン性二重結合を分子内
に２個以上有する多官能単量体を重合して得られた、特
定の物性をもつポリ塩化ビニル樹脂を用いるものであ
り、その重合方法としては、塩化ビニル単量体または塩
化ビニルを主体とする単量体混合物（以下、塩化ビニル
系単量体という。）を乳化重合法、微細懸濁重合法、シ
ード乳化重合、シード微細懸濁重合等の播種重合で重合
することが好ましく、特に播種乳化重合法で、さらにシ
ード微細懸濁重合が好ましい。この際、いずれの重合方
法においても３０〜８０℃の温度範囲で重合することが
好ましい。The matting agent for printing ink of the present invention comprises a vinyl chloride monomer or a vinyl chloride monomer and two or more ethylenic double bonds in the molecule in the presence of a surfactant and a polymerization initiator. Polyvinyl chloride resin having specific physical properties obtained by polymerizing a polyfunctional monomer having a vinyl chloride monomer or a vinyl chloride-based monomer The mixture (hereinafter, referred to as a vinyl chloride monomer) is preferably polymerized by seed polymerization such as emulsion polymerization, fine suspension polymerization, seed emulsion polymerization, and seed fine suspension polymerization. , Furthermore, seed fine suspension polymerization is preferred. In this case, it is preferable to carry out the polymerization in a temperature range of 30 to 80 ° C. in any of the polymerization methods.

【００２９】重合される塩化ビニル系単量体は、塩化ビ
ニル単量体又は塩化ビニル単量体と塩化ビニル単量体と
の共重合可能なビニル単量体との混合物であり、塩化ビ
ニル単量体と共重合し得るビニル単量体としては、例え
ば酢酸ビニル、プロピオン酸ビニル、ミリスチン酸ビニ
ル、安息香酸ビニル等のビニルエステル類；アクリル
酸、メタクリル酸、マレイン酸、フマル酸等の不飽和カ
ルボン酸又はその無水物；アクリル酸メチル、アクリル
酸エチル、アクリル酸ブチル等のアクリル酸エステル
類、メタクリル酸エチル、メタクリル酸エチル、メタク
リル酸ブチル等のメタクリル酸エステル類；マレイン酸
エステル、フマル酸エステル、桂皮酸エステル等の不飽
和カルボン酸エステル類、ビニルメチルエーテル、ビニ
ルアミルエーテル、ビニルフェニルエーテル等のビニル
エーテル類、エチレン、プロピレン、ブテン、ペンテン
等のモノオレフィン類；塩化ビニリデン、スチレン及び
その誘導体、アクリロニトリル、メタクリロニトリル等
を挙げることができ、これらビニル単量体は１種以上で
用いることが可能である。The vinyl chloride monomer to be polymerized is a mixture of a vinyl chloride monomer or a vinyl monomer copolymerizable with a vinyl chloride monomer and a vinyl chloride monomer. Examples of the vinyl monomer copolymerizable with the monomer include vinyl esters such as vinyl acetate, vinyl propionate, vinyl myristate, and vinyl benzoate; and unsaturated esters such as acrylic acid, methacrylic acid, maleic acid, and fumaric acid. Carboxylic acid or anhydride thereof; acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, etc .; methacrylates such as ethyl methacrylate, ethyl methacrylate, butyl methacrylate; maleic ester, fumaric ester Carboxylic esters such as cinnamate, cinnamic acid ester, vinyl methyl ether, vinyl amyl ether, Vinyl ethers such as phenyl ether; monoolefins such as ethylene, propylene, butene and pentene; vinylidene chloride, styrene and derivatives thereof, acrylonitrile, methacrylonitrile and the like. It is possible to use in.

【００３０】上記重合の際にはエチレン性二重結合を分
子内に２個以上有する多官能単量体をポリ塩化ビニル樹
脂の重合前、重合中に添加し重合することが好ましく、
エチレン性二重結合を分子内に2個以上有する多官能単
量体としては、トリアリルイソシアヌレート、トリアリ
ルシアヌレート、及びジアリルフタレートの１種以上を
用いることが好ましい。In the above polymerization, it is preferable to add and polymerize a polyfunctional monomer having two or more ethylenic double bonds in the molecule before and during the polymerization of the polyvinyl chloride resin.
As the polyfunctional monomer having two or more ethylenic double bonds in the molecule, it is preferable to use one or more of triallyl isocyanurate, triallyl cyanurate, and diallyl phthalate.

【００３１】エチレン性二重結合を分子内に2個以上有
する多官能単量体の添加量としては、塩化ビニル単量体
に対し０．０５重量％以上１０重量％以下の範囲が好ま
しく、特に０．１〜５重量％で、さらに０．３〜３重量
％の範囲が好ましい。The amount of the polyfunctional monomer having two or more ethylenic double bonds in the molecule is preferably in the range of 0.05% by weight to 10% by weight based on the vinyl chloride monomer. It is preferably 0.1 to 5% by weight, more preferably 0.3 to 3% by weight.

【００３２】トリアリルイソシアヌレート、トリアリル
シアヌレート、及びジアリルフタレートと他の多官能性
単量体を１種以上併用して用いることも可能である。It is also possible to use triallyl isocyanurate, triallyl cyanurate, and diallyl phthalate together with one or more other polyfunctional monomers.

【００３３】本発明の印刷インク用艶消し剤を重合する
場合、適宜エチレン性二重結合を分子内に２個以上有す
る多官能単量体をポリ塩化ビニル樹脂の重合前、重合中
に添加するに際して連鎖移動剤と併用して重合すること
が好ましい。When polymerizing the matting agent for printing ink of the present invention, a polyfunctional monomer having two or more ethylenic double bonds in a molecule is appropriately added before and during polymerization of the polyvinyl chloride resin. In this case, the polymerization is preferably carried out in combination with a chain transfer agent.

【００３４】ここで併用される連鎖移動剤としては、例
えば塩化ブチル、塩化イソブチル、ｎ−ブタノール、二
硫化炭素、テトラヒドロフラン、酢酸ブチル、メタノー
ル、シクロヘキサン、四臭化炭素、エチレンクロリド、
ジオキサン、メチルエチルケトン、ドデシルメルカプタ
ン、メルカプトエタノール、メルカプトプロピオン酸オ
クチル、メルカプトプロピオン酸ドデシル、高級アルコ
ール等が挙げられる。Examples of the chain transfer agent used here include butyl chloride, isobutyl chloride, n-butanol, carbon disulfide, tetrahydrofuran, butyl acetate, methanol, cyclohexane, carbon tetrabromide, ethylene chloride,
Examples include dioxane, methyl ethyl ketone, dodecyl mercaptan, mercaptoethanol, octyl mercaptopropionate, dodecyl mercaptopropionate, and higher alcohols.

【００３５】エチレン性二重結合を分子内に２個以上有
する多官能単量体と連鎖移動剤と併用して重合する際の
添加比率としては連鎖移動剤／エチレン性二重結合を分
子内に２個以上有する多官能単量体＝１／１〜１／７０
（重量比）が好ましく、特に１／５〜１／５０（重量
比）、さらに１／１０〜１／３０が好ましい。When the polymerization is carried out in combination with a polyfunctional monomer having two or more ethylenic double bonds in the molecule and a chain transfer agent, the addition ratio of the chain transfer agent / ethylenic double bond in the molecule may be as follows. Polyfunctional monomer having two or more = 1/1 to 1/70
(Weight ratio), preferably 1/5 to 1/50 (weight ratio), more preferably 1/10 to 1/30.

【００３６】重合に使用する界面活性剤としては、ジア
ルキルスルホコハク酸塩、アルキルベンゼンスルホン酸
塩、アルキル硫酸塩、及びエチレン性二重結合を分子内
に有する界面活性剤が好ましい。As the surfactant used for the polymerization, a dialkyl sulfosuccinate, an alkylbenzene sulfonate, an alkyl sulfate, and a surfactant having an ethylenic double bond in a molecule are preferable.

【００３７】エチレン性二重結合を分子内に有する界面
活性剤としては、例えばノニルプロペニルフェノールエ
チレンオキシド１０モル付加体硫酸エステル塩、ノニル
プロペニルフェノールエチレンオキシド２０モル付加体
硫酸エステル塩、オクチルジプロペニルフェノールエチ
レンオキシド１０モル付加体硫酸エステル塩、オクチル
ジプロペニルフェノールエチレンオキシド１００モル付
加体硫酸エステル塩、ドデシルプロペニルフェノールブ
チレンオキシド４モル、エチレンオキシド３０モルブロ
ック付加体硫酸エステル塩等が挙げられる。Examples of the surfactant having an ethylenic double bond in the molecule include sulfates of nonylpropenylphenol ethylene oxide 10 mol adduct, sulfates of nonylpropenylphenol ethylene oxide 20 mol adduct, octyl dipropenylphenol ethylene oxide 10 mol Sulfuric acid ester of a molar adduct, 100 mol of octyl dipropenylphenol ethylene oxide adduct, 4 mol of dodecylpropenylphenol butylene oxide, 30 mol of ethylene oxide block adduct and the like.

【００３８】界面活性剤の使用量としては、塩化ビニル
単量体１００重量部に対し、０．０５重量部以上１．５
重量部以下が好ましく、特に０．５〜１．２重量部、さ
らに０．６〜１．０重量部を重合前、重合中に添加する
ことが好ましい。The surfactant is used in an amount of 0.05 to 1.5 parts by weight based on 100 parts by weight of the vinyl chloride monomer.
It is preferably added in an amount of 0.5 to 1.2 parts by weight, more preferably 0.6 to 1.0 part by weight, before and during the polymerization.

【００３９】また、添加時期における界面活性剤の添加
量としては、重合前添加／重合中添加（重量比）＝１／
５〜１／２０が好ましく、特に１／６〜１／１７、さら
に好ましくは１／９〜１／１５である。The addition amount of the surfactant at the time of the addition was as follows: addition before polymerization / addition during polymerization (weight ratio) = 1 /
It is preferably from 5 to 1/20, particularly preferably from 1/6 to 1/17, more preferably from 1/9 to 1/15.

【００４０】重合開始剤としては、例えば過硫酸カリウ
ム、過硫酸アンモニウム、過酸化水素等の水溶性開始
剤；ベンゾイルパーオキサイド、ｐ−クロロベンゾイル
パーオキサイド等の芳香族ジアシルパーオキサイド、カ
プロイルパーオキサイド、ラウロイルパーオキサイド等
の脂肪族ジアシルパーオキサイド、アゾビスイソブチロ
ニトロリル、アゾビスイソバレロニトリル等のアゾ化合
物、ｔ−ブチルパーオキシピバレート等の有機酸のパー
オキシジエステル、ジイソプロピルパーオキシジカーボ
ネート、ジオクチルパーオキシジカーボネート等のパー
オキシジカーボネート、アセチルシクロヘキシルスルホ
ニルパーオキサイド等の油溶性開始剤が挙げられる。そ
して、これらは単独又は2種類以上の組合わせで用いる
ことが可能である。Examples of the polymerization initiator include water-soluble initiators such as potassium persulfate, ammonium persulfate and hydrogen peroxide; aromatic diacyl peroxides such as benzoyl peroxide and p-chlorobenzoyl peroxide; caproyl peroxide; Aliphatic diacyl peroxides such as lauroyl peroxide, azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile, peroxydiesters of organic acids such as t-butylperoxypivalate, diisopropylperoxydicarbonate And peroxydicarbonates such as dioctyl peroxydicarbonate, and oil-soluble initiators such as acetylcyclohexylsulfonyl peroxide. These can be used alone or in combination of two or more.

【００４１】また重合温度が、重合開始剤の１０時間半
減期温度よりも低い場合は、重合温度をコントロールす
る目的で、例えばチオ硫酸ナトリウム、アスコルビン酸
などの還元剤を単独で重合時に添加するか、硫酸鉄−ア
スコルビン酸、硫酸銅−アスコルビン酸のようなレドッ
クス系開始剤との併用でもよい。When the polymerization temperature is lower than the 10-hour half-life temperature of the polymerization initiator, for the purpose of controlling the polymerization temperature, a reducing agent such as sodium thiosulfate or ascorbic acid may be added alone during the polymerization. And a redox initiator such as iron sulfate-ascorbic acid or copper sulfate-ascorbic acid.

【００４２】更に、重合時に分散剤を添加してもよい。
使用可能な分散剤としては、鹸化度７０％以上、重合度
３０００以下のポリビニルアルコールが好ましく、特に
鹸化度８０％以上、重合度１５００以下が好ましく、さ
らに鹸化度９０％以上、重合度１０００以下が好まし
い。Further, a dispersant may be added during the polymerization.
As a dispersant that can be used, a polyvinyl alcohol having a saponification degree of 70% or more and a polymerization degree of 3000 or less is preferable, and a saponification degree of 80% or more and a polymerization degree of 1500 or less are particularly preferable, and a saponification degree of 90% or more and a polymerization degree of 1000 or less are more preferable. preferable.

【００４３】分散剤の使用量としては、塩化ビニル単量
体１００重量部に対し、０．０１重量部以上５重量部以
下が好ましく、特に１．５〜４重量部、更に２〜３．５
重量部を重合前に一括添加して使用することが好まし
い。The amount of the dispersant used is preferably 0.01 to 5 parts by weight, particularly 1.5 to 4 parts by weight, more preferably 2 to 3.5 parts by weight, based on 100 parts by weight of the vinyl chloride monomer.
It is preferable to add parts by weight before polymerization before use.

【００４４】この際に乳化、分散を補助する目的で、適
宜他の界面活性剤、分散補助剤を併用して用いることも
可能であるが、上記の界面活性剤、分散剤を１種以上使
用することが好ましい。At this time, for the purpose of assisting emulsification and dispersion, other surfactants and dispersing agents may be used in combination as appropriate, but one or more of the above surfactants and dispersing agents may be used. Is preferred.

【００４５】ポリ塩化ビニル樹脂の重合において、前記
した界面活性剤と鹸化度７０％以上、重合度３０００以
下のポリビルアルコールを併用する場合、界面活性剤の
使用量は、塩化ビニル単量体に対し０．０５重量％以上
０．３重量％の範囲が好ましく、特に０．１〜０．３重
量％、更に好ましくは０．１５〜０．３重量％の範囲
で、且つポリビルアルコールの使用量は、塩化ビニル単
量体に対し０．０１重量％以上０．５重量％が好まし
く、特に０．０２〜０．２重量％、更に好ましくは０．
０３〜０．１重量％の範囲がよい。In the polymerization of polyvinyl chloride resin, when the above-mentioned surfactant is used in combination with polyvinyl alcohol having a saponification degree of 70% or more and a polymerization degree of 3000 or less, the amount of the surfactant used is On the other hand, it is preferably in the range of 0.05% by weight to 0.3% by weight, particularly in the range of 0.1 to 0.3% by weight, more preferably in the range of 0.15 to 0.3% by weight, and use of polyvinyl alcohol. The amount is preferably 0.01% by weight or more and 0.5% by weight with respect to the vinyl chloride monomer, particularly preferably 0.02 to 0.2% by weight, more preferably 0.1% by weight.
The range of from 03 to 0.1% by weight is good.

【００４６】本発明の印刷インキ用艶消し剤の形態には
特に制限はなく、重合して得られた水性分散液の状態、
及び乾燥粉末の状態で使用が可能である。The form of the matting agent for a printing ink of the present invention is not particularly limited, and the state of an aqueous dispersion obtained by polymerization may be used.
And it can be used in the form of dry powder.

【００４７】重合で得られた樹脂の乾燥方法の種類は特
に制限はないが、乾燥時の熱劣化が緩和できることか
ら、噴霧乾燥による方法が好ましい。この際の乾燥機の
種類には制限がなく、一般に使用されているものでよ
く、例えば「SPRAY DAYING HANDBOOK」(K.Ｍａｓｔｅｒ
著、３版、１９７９年、Ｇｅｏｒｇｅ ｇｏｄｗｉｎ
Ｌｉｍｉｔｅｄより出版)の１２１頁第４．１０図に記
載されている各種のスプレー乾燥機が挙げられ、一般に
は乾燥出口温度４０〜９０℃の範囲で運転され、好まし
くは４０〜７０℃、特に好ましくは４０〜６５℃で乾燥
される。The type of drying method of the resin obtained by polymerization is not particularly limited, but spray drying is preferred because thermal degradation during drying can be reduced. The type of dryer at this time is not limited, and may be a commonly used dryer, for example, “SPRAY DAYING HANDBOOK” (K. Master)
Author, 3rd edition, 1979, George Godwin
(Published by Limited), page 121, FIG. 4.10, and various spray dryers, which are generally operated at a drying outlet temperature of 40 to 90 ° C., preferably 40 to 70 ° C., and particularly preferably. Is dried at 40-65 ° C.

【００４８】本発明の印刷インク用艶消し剤の特定の粒
子径分布、分散性を有するポリ塩化ビニル樹脂を製造す
る場合、前記の乳化重合法、微細懸濁重合法、播種重合
法で得られたポリ塩化ビニル樹脂粒子１種以上をブレン
ドして特定の粒子径分布を得ることも可能である。ま
た、重合して得られたポリ塩化ビニル樹脂粒子に対して
遠心分離、膜分離等を行うことにより、特定の粒子径分
布を得ることも可能である。When a polyvinyl chloride resin having a specific particle size distribution and dispersibility of the matting agent for printing ink of the present invention is produced, it can be obtained by the above-mentioned emulsion polymerization method, fine suspension polymerization method and seeding polymerization method. It is also possible to obtain a specific particle size distribution by blending one or more types of polyvinyl chloride resin particles. Further, a specific particle size distribution can be obtained by subjecting the polyvinyl chloride resin particles obtained by polymerization to centrifugal separation, membrane separation, and the like.

【００４９】これら重合方法で得られるポリ塩化ビニル
樹脂は、オフセット印刷、或いはグラビア印刷で一般的
に用いられる溶剤系インキへの分散性はもちろん、最近
環境問題の高まりから要求が高まっている水性インキ中
へも良好な分散性を示すため、本発明の印刷インキは溶
剤系、水性インキの両タイプに使用が可能である。The polyvinyl chloride resin obtained by these polymerization methods can be used not only for dispersibility in solvent-based inks generally used in offset printing or gravure printing, but also for aqueous inks, which have recently been required due to environmental problems. Since it shows good dispersibility in the printing ink, the printing ink of the present invention can be used in both solvent-based and water-based inks.

【００５０】本発明の印刷インキを調整する際に、併用
することが可能なものとしては特に印刷インキとして使
用される配合剤であれば限定はないが、例えば、ボイル
油、油ワニス、アルキド系樹脂、フェノール系樹脂、ア
ミノアルキド系樹脂、エポキシ系樹脂、アクリル系樹
脂、ポリエステル系樹脂、ポリウレタン系樹脂、ケイ素
系樹脂、ロジン変性樹脂、アマニ油、石油系溶剤、エス
テル類、ケトン類、アルコール類、水、各種界面活性
剤、鉱物油系消泡剤、シリコン系消泡剤等が挙げられ
る。特に、油ワニス、アルキド系樹脂、アクリル系樹
脂、ロジン変性樹脂、アマニ油、エステル類、ケトン類
等が好ましい。In preparing the printing ink of the present invention, there is no particular limitation on the compounding agent that can be used in combination as long as it is a compounding agent particularly used as a printing ink. For example, boiling oil, oil varnish, alkyd-based Resins, phenolic resins, aminoalkyd resins, epoxy resins, acrylic resins, polyester resins, polyurethane resins, silicon resins, rosin-modified resins, linseed oil, petroleum solvents, esters, ketones, alcohols , Water, various surfactants, mineral oil-based antifoaming agents, and silicon-based antifoaming agents. Particularly, oil varnish, alkyd resin, acrylic resin, rosin modified resin, linseed oil, esters, ketones and the like are preferable.

【００５１】また、本発明の印刷インキには用途に応じ
て適当な顔料を添加しても良く、好ましい顔料として
は、チタンホワイト、カーボンブラック、フタロシアニ
ン系、酸化亜鉛、赤色酸化鉄等の無機顔料、或いは各種
の有機顔料が挙げられる。特に、チタンホワイト、フタ
ロシアニン系顔料が多くの場合に使用される。Further, an appropriate pigment may be added to the printing ink of the present invention according to the intended use. Preferred pigments include inorganic pigments such as titanium white, carbon black, phthalocyanine, zinc oxide and red iron oxide. Or various organic pigments. In particular, titanium white and phthalocyanine pigments are used in many cases.

【００５２】更に、本発明においては、艶消し剤として
従来用いられている無機物を適宜併用してもよい。Further, in the present invention, an inorganic substance conventionally used as a matting agent may be appropriately used in combination.

【００５３】本発明の印刷インキ用艶消し剤は、従来用
いられてきた各種印刷用インキにそのまま添加分散する
ことで艶消し効果が得られることから、艶消し感の要求
が強いポスター、或いは雑誌中の写真等の印刷に用いら
れるオフセット印刷、グラビア印刷、凸版印刷、スクリ
ーン印刷用等のインキやプラスチックインキの艶消し剤
として効果がある。The matting agent for printing inks of the present invention can provide a matting effect by directly adding and dispersing it to various printing inks conventionally used, so that posters or magazines that require a strong matte feeling can be obtained. It is effective as a matting agent for inks such as offset printing, gravure printing, letterpress printing, screen printing, and plastic inks used for printing inside photographs and the like.

【００５４】本発明の印刷インキ用艶消し剤は、特定の
粒子径分布、分散性を有するポリ塩化ビニル樹脂を、特
定量配合することにより、従来のシリカ等の無機物を添
加した場合に比較し、良好なインキの流動性でありなが
ら、しかも容易に同等以上の艶消し感をだすことが可能
であり、特に、溶剤系、水性インキの両方に使用するこ
とができ、マットインキの製造工程簡素化に有用である
とともに、省コストが可能となる。The matting agent for a printing ink of the present invention is prepared by adding a specific amount of a polyvinyl chloride resin having a specific particle size distribution and dispersibility, and comparing with a case where a conventional inorganic substance such as silica is added. Despite good fluidity of ink, it can easily give the same or more matte feeling. Especially, it can be used for both solvent-based and water-based inks, simplifying the process of producing matte ink. This is useful for cost reduction and can save costs.

【００５５】また、従来用いられている無機系艶消し剤
は、その比重の大きさから同量配合した場合には、本発
明に使用されるポリ塩化ビニル樹脂に比較し２〜３倍の
重量となり、これら無機系艶消し剤を用いた印刷用イン
キは重量が重くなり、ハンドリング性、輸送コスト等に
問題があるが、本発明の艶消し剤の場合は、これらの問
題点についても優れた効果が得られる。When the same amount of the conventional inorganic matting agent is blended due to its specific gravity, the weight of the matting agent is 2-3 times that of the polyvinyl chloride resin used in the present invention. And printing inks using these inorganic matting agents are heavy in weight, and have problems in handling properties, transportation costs, etc., but in the case of the matting agent of the present invention, these problems are also excellent. The effect is obtained.

【００５６】さらに、従来一般的に使用されているシリ
カは、基本粒子が数十ｎｍで構成される凝集粒子として
数μｍの粒子となっていることから、配合混練時の混練
条件により凝集体が崩壊し、混練条件により得られるマ
ット感にバラツキが発生する問題があるが、本発明の艶
消し剤の場合は、基本粒子が数〜数十μｍとしているた
めこれらの問題についても優れた効果が得られる。Furthermore, silica that has been generally used in the past is a few μm particles as agglomerated particles whose basic particles are composed of several tens of nanometers. Disintegrate, there is a problem that the matte feeling obtained by kneading conditions varies, but in the case of the matting agent of the present invention, since the basic particles are several to several tens of μm, an excellent effect on these problems is also obtained. can get.

【００５７】[0057]

【実施例】実施例により、本発明をより詳細に説明する
が、本発明はこれらによってなんら限定されるものでは
ない。EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

【００５８】合成例１ ２．５Ｌオートクレーブ中に重合開始前に脱イオン水５
００ｇ、塩化ビニル単量体８００ｇ、トリアリルイソシ
アヌレート２．８ｇ、ラウロイルパーオキサイドを２重
量％含有させたシード粒子を１１０ｇ、乳化重合により
得られたシード粒子を７０ｇ、０．１重量％硫酸第一鉄
水溶液８ｇ、界面活性剤０．８ｇを仕込み、反応混合物
の温度を４２℃に上げると共に、０．１重量％アスコル
ビン酸水溶液１６０ｇを重合終了まで連続的に添加し
た。Synthesis Example 1 In a 2.5 L autoclave, deionized water 5
00 g, 800 g of vinyl chloride monomer, 2.8 g of triallyl isocyanurate, 110 g of seed particles containing 2 wt% of lauroyl peroxide, 70 g of seed particles obtained by emulsion polymerization, 0.1 wt% of sulfuric acid 8 g of an aqueous solution of ferrous iron and 0.8 g of a surfactant were charged, the temperature of the reaction mixture was raised to 42 ° C., and 160 g of an aqueous solution of 0.1% by weight ascorbic acid were continuously added until the completion of the polymerization.

【００５９】更に重合開始から１０時間後まで界面活性
剤８ｇを連続的に添加した。Further, 8 g of a surfactant was continuously added until 10 hours after the start of the polymerization.

【００６０】重合前、重合中の界面活性剤はジアルキル
スルホコハク酸ソーダを使用した。Before the polymerization, a sodium dialkyl sulfosuccinate was used as a surfactant during the polymerization.

【００６１】重合温度が４２℃における塩化ビニル飽和
蒸気圧から２．１ｋｇ／ｃｍ2降下した時に重合を停止
し、重合終了後に未反応の塩化ビニル単量体を回収し、
塩化ビニル重合体ラテックスを得た。When the polymerization temperature dropped 2.1 kg / cm 2 from the vinyl chloride saturated vapor pressure at 42 ° C., the polymerization was stopped, and after the polymerization was completed, unreacted vinyl chloride monomer was recovered.
A vinyl chloride polymer latex was obtained.

【００６２】得られた塩化ビニル重合体ラテックス中の
ポリ塩化ビニル樹脂粒子の粒子径、平均粒子径を表１に
示す。Table 1 shows the particle size and average particle size of the polyvinyl chloride resin particles in the obtained vinyl chloride polymer latex.

【００６３】次いで、このラテックスを回転円盤式噴霧
乾燥機により乾燥機入口温度１４０℃、乾燥機出口温度
５０℃乾燥し、粉砕機を通して艶消し剤となる塩化ビニ
ル樹脂を得た。Next, this latex was dried by a rotary disk type spray dryer at a dryer inlet temperature of 140 ° C. and a dryer outlet temperature of 50 ° C., and passed through a pulverizer to obtain a vinyl chloride resin as a matting agent.

【００６４】なお、得られた塩化ビニル樹脂粉末１００
重量部と２，２，４−トリメチル１，３−ペンタンジオ
ールジイソブチレート６０重量部を配合しデイゾルバー
式ミキサーデイゾルバー式ミキサー（ＴＯＫＵＳＹＵ
ＫＩＫＡ ＫＯＧＹＯ（製）、商品名「Ｔ．Ｋ．ＨＯＭ
Ｏ ＤＩＳＰＥＲ ＭＯＤＥＬ７Ｃ」）を用い２５℃、
８００ｒｐｍで３分間混錬し配合物（Ａ）を得た。塩化
ビニル樹脂粉末のゲル分、配合物（Ａ）の粒子径を表１
に示す。The obtained vinyl chloride resin powder 100
Parts by weight and 60 parts by weight of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, and a dissolver-type mixer dissolver-type mixer (TOKUSYU)
KIKA KOGYO (product name), trade name "TK HOM
O DISPER MODEL7C ") at 25 ° C,
The mixture was kneaded at 800 rpm for 3 minutes to obtain a blend (A). Table 1 shows the gel content of the vinyl chloride resin powder and the particle size of the compound (A).
Shown in

【００６５】合成例２ ジアルキルスルホコハク酸ソーダの替りにアルキルベン
ゼンスルホン酸ソーダを重合前に０．７ｇ、重合開始後
に９ｇ添加した以外は、合成例１と同様にして塩化ビニ
ル重合体、塩化ビニル樹脂の乾燥粉末、配合物（Ａ）を
得た。Synthesis Example 2 A vinyl chloride polymer and a vinyl chloride resin were prepared in the same manner as in Synthesis Example 1 except that 0.7 g of sodium alkylbenzenesulfonate was added before the polymerization and 9 g after the start of the polymerization in place of the sodium dialkylsulfosuccinate. A dry powder, formulation (A) was obtained.

【００６６】得られた塩化ビニル樹脂粒子の粒子径、平
均粒子径、塩化ビニル樹脂粒子のゲル分、配合物（Ａ）
の粒子径を表１に示す。The particle size and average particle size of the obtained vinyl chloride resin particles, the gel content of the vinyl chloride resin particles, and the composition (A)
Are shown in Table 1.

【００６７】合成例３ ジアルキルスルホコハク酸ソーダの替りにノニルプロペ
ニルフェノールエチレンオキシド１０モル付加体硫酸ソ
ーダ／アルキルベンゼンスルホン酸ソーダ＝１／５（重
量比）に混合した界面活性剤を重合前に０．２ｇ、重合
開始後に２．６ｇを添加した以外は、合成例１と同様に
して塩化ビニル重合体、塩化ビニル樹脂の乾燥粉末、配
合物（Ａ）を得た。Synthesis Example 3 Instead of sodium dialkyl sulfosuccinate, 0.2 g of a surfactant mixed with nonylpropenyl phenol ethylene oxide 10 mol adduct sodium sulfate / alkyl benzene sulfonate = 1/5 (weight ratio) before polymerization was used. A vinyl chloride polymer, a dry powder of a vinyl chloride resin, and a blend (A) were obtained in the same manner as in Synthesis Example 1 except that 2.6 g was added after the start of the polymerization.

【００６８】得られた塩化ビニル樹脂粒子の粒子径、平
均粒子径、塩化ビニル樹脂粒子のゲル分、配合物（Ａ）
の粒子径を表１に示す。The particle size and average particle size of the obtained vinyl chloride resin particles, the gel content of the vinyl chloride resin particles, and the composition (A)
Are shown in Table 1.

【００６９】合成例４ ジアルキルスルホコハク酸ソーダの替りにアルキル硫酸
ソーダを添加した以外は、合成例１と同様にして塩化ビ
ニル重合体、塩化ビニル樹脂の乾燥粉末、配合物（Ａ）
を得た。Synthesis Example 4 The same procedure as in Synthesis Example 1 was repeated except that sodium alkylsulfate was added instead of sodium dialkylsulfosuccinate, and a dry powder of a vinyl chloride polymer and a vinyl chloride resin, formulation (A)
I got

【００７０】得られた塩化ビニル樹脂粒子の粒子径、平
均粒子径、塩化ビニル樹脂粒子のゲル分、配合物（Ａ）
の粒子径を表１に示す。The particle size and average particle size of the obtained vinyl chloride resin particles, the gel content of the vinyl chloride resin particles, and the composition (A)
Are shown in Table 1.

【００７１】合成例５ ジアルキルスルホコハク酸ソーダを重合前に２．４ｇ、
重合開始後に連続的に７．２ｇを添加した以外は、合成
例１と同様にして塩化ビニル重合体、塩化ビニル樹脂の
乾燥粉末、配合物（Ａ）を得た。Synthesis Example 5 2.4 g of sodium dialkylsulfosuccinate was added before polymerization.
A vinyl chloride polymer, a dry powder of a vinyl chloride resin, and a blend (A) were obtained in the same manner as in Synthesis Example 1 except that 7.2 g was continuously added after the start of the polymerization.

【００７２】得られた塩化ビニル樹脂粒子の粒子径、平
均粒子径、塩化ビニル樹脂粒子のゲル分、配合物（Ａ）
の粒子径を表１に示す。The particle size and average particle size of the obtained vinyl chloride resin particles, the gel content of the vinyl chloride resin particles, and the composition (A)
Are shown in Table 1.

【００７３】合成例６ ジアルキルスルホコハク酸ソーダを重合前に０．２４
ｇ、重合開始後に連続的に１．９ｇを添加した以外は、
合成例１と同様にして塩化ビニル重合体、塩化ビニル樹
脂の乾燥粉末、配合物（Ａ）を得た。Synthesis Example 6 Sodium dialkyl sulfosuccinate was added at 0.24 before polymerization.
g, except that 1.9 g was continuously added after the polymerization was started.
In the same manner as in Synthesis Example 1, a dry powder of a vinyl chloride polymer and a vinyl chloride resin, and a blend (A) were obtained.

【００７４】得られた塩化ビニル樹脂粒子の粒子径、平
均粒子径、塩化ビニル樹脂粒子のゲル分、配合物（Ａ）
の粒子径を表１に示す。The particle size and average particle size of the obtained vinyl chloride resin particles, the gel content of the vinyl chloride resin particles, and the composition (A)
Are shown in Table 1.

【００７５】合成例７ ジアルキルスルホコハク酸ソーダを重合前に２．４ｇ、
重合開始後に連続的に１３．６ｇを添加した以外は、合
成例１と同様にして塩化ビニル重合体、塩化ビニル樹脂
の乾燥粉末、配合物（Ａ）を得た。Synthesis Example 7 2.4 g of sodium dialkyl sulfosuccinate was added before polymerization.
A vinyl chloride polymer, a dry powder of a vinyl chloride resin, and a blend (A) were obtained in the same manner as in Synthesis Example 1 except that 13.6 g was continuously added after the initiation of the polymerization.

【００７６】得られた塩化ビニル樹脂粒子の粒子径、平
均粒子径、塩化ビニル樹脂粒子のゲル分、配合物（Ａ）
の粒子径を表１に示す。The particle size and average particle size of the obtained vinyl chloride resin particles, the gel content of the vinyl chloride resin particles, and the composition (A)
Are shown in Table 1.

【００７７】合成例８ 合成例１と同様にして塩化ビニル重合体を得た。次い
で、このラテックスを回転円盤式噴霧乾燥機により乾燥
機入口温度１６０℃、乾燥機出口温度７３℃乾燥し、粉
砕機を通して塩化ビニル樹脂を得た。Synthesis Example 8 A vinyl chloride polymer was obtained in the same manner as in Synthesis Example 1. Next, this latex was dried by a rotating disk type spray dryer at a dryer inlet temperature of 160 ° C. and a dryer outlet temperature of 73 ° C., and a vinyl chloride resin was obtained through a pulverizer.

【００７８】次いで得られた塩化ビニル樹脂粉末１００
重量部と２，２，４−トリメチル１，３−ペンタンジオ
ールジイソブチレート６０重量部を配合しデイゾルバー
式ミキサーデイゾルバー式ミキサー（ＴＯＫＵＳＹＵ
ＫＩＫＡ ＫＯＧＹＯ（製）、商品名「Ｔ．Ｋ．ＨＯＭ
Ｏ ＤＩＳＰＥＲ ＭＯＤＥＬ７Ｃ」）を用い２５℃、
８００ｒｐｍで３分間混錬し配合物（Ａ）を得た。Next, the obtained vinyl chloride resin powder 100
Parts by weight and 60 parts by weight of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, and a dissolver-type mixer dissolver-type mixer (TOKUSYU)
KIKA KOGYO (product name), trade name "TK HOM
O DISPER MODEL7C ") at 25 ° C,
The mixture was kneaded at 800 rpm for 3 minutes to obtain a blend (A).

【００７９】得られた塩化ビニル樹脂粒子の粒子径、平
均粒子径、塩化ビニル樹脂粒子のゲル分、配合物（Ａ）
の粒子径を表１に示す。The particle size and average particle size of the obtained vinyl chloride resin particles, the gel content of the vinyl chloride resin particles, and the composition (A)
Are shown in Table 1.

【００８０】合成例９ ２．５Ｌオートクレーブ中に重合開始前に脱イオン水８
００ｇ、塩化ビニル単量体５００ｇ、ラウロイルパーオ
キサイド０．５ｇ、鹸化度９１〜９４、重合度６００の
ポリビニルアルコール１５ｇ、トリアリルイソシアヌレ
ート３ｇを仕込み、５０００ｒｐｍで均質化処理を行な
った。その後、反応混合物の温度を規程温度に昇温し
た。Synthesis Example 9 Deionized water 8 in a 2.5 L autoclave prior to initiation of polymerization
00 g, 500 g of vinyl chloride monomer, 0.5 g of lauroyl peroxide, 15 g of polyvinyl alcohol having a saponification degree of 91 to 94 and a polymerization degree of 600, and 3 g of triallyl isocyanurate were charged and homogenized at 5000 rpm. Thereafter, the temperature of the reaction mixture was raised to the prescribed temperature.

【００８１】オートクレーブ内の圧力が規定温度の塩化
ビニル飽和蒸気圧から２ｋｇ／ｃｍ２降下した時に重合
を停止し、重合終了後に未反応の塩化ビニル単量体を回
収し、塩化ビニル重合体、塩化ビニル樹脂の乾燥粉末を
得た。When the pressure in the autoclave drops by 2 kg / cm 2 from the saturated vapor pressure of vinyl chloride at the specified temperature, the polymerization is stopped, and after the polymerization is completed, unreacted vinyl chloride monomer is recovered. A dry powder of the resin was obtained.

【００８２】なお、得られた塩化ビニル樹脂粉末１００
重量部と２，２，４−トリメチル１，３−ペンタンジオ
ールジイソブチレート６０重量部を配合しデイゾルバー
式ミキサーデイゾルバー式ミキサー（ＴＯＫＵＳＹＵ
ＫＩＫＡ ＫＯＧＹＯ（製）、商品名「Ｔ．Ｋ．ＨＯＭ
Ｏ ＤＩＳＰＥＲ ＭＯＤＥＬ７Ｃ」）を用い２５℃、
８００ｒｐｍで３分間混錬し配合物（Ａ）を得た。The obtained vinyl chloride resin powder 100
Parts by weight and 60 parts by weight of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, and a dissolver-type mixer dissolver-type mixer (TOKUSYU)
KIKA KOGYO (product name), trade name "TK HOM
O DISPER MODEL7C ") at 25 ° C,
The mixture was kneaded at 800 rpm for 3 minutes to obtain a blend (A).

【００８３】得られた塩化ビニル樹脂粒子の粒子径、平
均粒子径、塩化ビニル樹脂粒子のゲル分、配合物（Ａ）
の粒子径を表１に示す。The particle size and average particle size of the obtained vinyl chloride resin particles, the gel content of the vinyl chloride resin particles, and the composition (A)
Are shown in Table 1.

【００８４】合成例１０ ポリビニルアルコールを２ｇ添加した以外は、合成例９
と同様にして塩化ビニル重合体、塩化ビニル樹脂の乾燥
粉末、配合物（Ａ）を得た。Synthesis Example 10 Synthesis Example 9 except that 2 g of polyvinyl alcohol was added.
In the same manner as in the above, a dry powder of a vinyl chloride polymer and a vinyl chloride resin, and a blend (A) were obtained.

【００８５】得られた塩化ビニル樹脂粒子の粒子径、平
均粒子径、塩化ビニル樹脂粒子のゲル分、配合物（Ａ）
の粒子径を表１に示す。The particle size and average particle size of the obtained vinyl chloride resin particles, the gel content of the vinyl chloride resin particles, and the composition (A)
Are shown in Table 1.

【００８６】合成例１１ ジアルキルスルホコハク酸ソーダを重合前に０．７５
ｇ、鹸化度９１〜９４、重合度６００のポリビニルアル
コールを０．５g添加した以外は、合成例９と同様にし
て塩化ビニル重合体、塩化ビニル樹脂の乾燥粉末、配合
物（Ａ）を得た。得られた塩化ビニル樹脂粒子の粒子
径、平均粒子径、塩化ビニル樹脂粒子のゲル分、配合物
（Ａ）の粒子径を表１に示す。Synthesis Example 11 Sodium dialkyl sulfosuccinate was added at 0.75 before polymerization.
g, a dry powder of a vinyl chloride polymer and a vinyl chloride resin, and a blend (A) were obtained in the same manner as in Synthesis Example 9 except that 0.5 g of polyvinyl alcohol having a saponification degree of 91 to 94 and a polymerization degree of 600 was added. . Table 1 shows the particle size, average particle size, gel content of the vinyl chloride resin particles, and the particle size of the compound (A) of the obtained vinyl chloride resin particles.

【００８７】合成例１２ ジアルキルスルホコハク酸ソーダを重合前に２ｇ、鹸化
度９１〜９４、重合度６００のポリビニルアルコールを
０．５g添加した以外は、合成例９と同様にして塩化ビ
ニル重合体、塩化ビニル樹脂の乾燥粉末、配合物（Ａ）
を得た。得られた塩化ビニル樹脂粒子の粒子径、平均粒
子径、塩化ビニル樹脂粒子のゲル分、配合物（Ａ）の粒
子径を表１に示す。Synthesis Example 12 The same procedure as in Synthesis Example 9 was repeated except that 2 g of sodium dialkylsulfosuccinate and 0.5 g of polyvinyl alcohol having a saponification degree of 91 to 94 and a polymerization degree of 600 were added before polymerization. Dry powder of vinyl resin, compound (A)
I got Table 1 shows the particle size, average particle size, gel content of the vinyl chloride resin particles, and the particle size of the compound (A) of the obtained vinyl chloride resin particles.

【００８８】合成例１３ トリアリルイソシアヌレートを０．８g添加した以外
は、合成例１と同様にして塩化ビニル重合体、塩化ビニ
ル樹脂の乾燥粉末、配合物（Ａ）を得た。Synthesis Example 13 A vinyl chloride polymer, a dry powder of a vinyl chloride resin, and a blend (A) were obtained in the same manner as in Synthesis Example 1 except that 0.8 g of triallylisocyanurate was added.

【００８９】得られた塩化ビニル樹脂粒子の粒子径、平
均粒子径、塩化ビニル樹脂粒子のゲル分、配合物（Ａ）
の粒子径を表１に示す。The particle size and average particle size of the obtained vinyl chloride resin particles, the gel content of the vinyl chloride resin particles, and the composition (A)
Are shown in Table 1.

【００９０】合成例１４ トリアリルイソシアヌレートを添加しなかったこと以外
は、合成例１と同様にして塩化ビニル重合体、塩化ビニ
ル樹脂の乾燥粉末、配合物（Ａ）を得た。Synthesis Example 14 A vinyl chloride polymer, a dry powder of a vinyl chloride resin, and a blend (A) were obtained in the same manner as in Synthesis Example 1 except that triallyl isocyanurate was not added.

【００９１】得られた塩化ビニル樹脂粒子の粒子径、平
均粒子径、塩化ビニル樹脂粒子のゲル分、配合物（Ａ）
の粒子径を表１に示す。The particle size and average particle size of the obtained vinyl chloride resin particles, the gel content of the vinyl chloride resin particles, and the composition (A)
Are shown in Table 1.

【００９２】合成例１５ トリアリルイソシアヌレートの替りにトリアリルシアヌ
レートを添加した以外は、合成例１と同様にして塩化ビ
ニル重合体、塩化ビニル樹脂の乾燥粉末、配合物（Ａ）
を得た。Synthesis Example 15 A vinyl chloride polymer, a dry powder of a vinyl chloride resin, and compound (A) were prepared in the same manner as in Synthesis Example 1 except that triallyl cyanurate was added instead of triallyl isocyanurate.
I got

【００９３】得られた塩化ビニル樹脂粒子の粒子径、平
均粒子径、塩化ビニル樹脂粒子のゲル分、配合物（Ａ）
の粒子径を表１に示す。The particle size and average particle size of the obtained vinyl chloride resin particles, the gel content of the vinyl chloride resin particles, and the composition (A)
Are shown in Table 1.

【００９４】合成例１６ トリアリルイソシアヌレートの替りにジアリルフタレー
トを添加した以外は、合成例１と同様にして塩化ビニル
重合体、塩化ビニル樹脂の乾燥粉末、配合物（Ａ）を得
た。Synthesis Example 16 A vinyl chloride polymer, a dry powder of a vinyl chloride resin, and a blend (A) were obtained in the same manner as in Synthesis Example 1 except that diallyl phthalate was added instead of triallyl isocyanurate.

【００９５】得られた塩化ビニル樹脂粒子の粒子径、平
均粒子径、塩化ビニル樹脂粒子のゲル分、配合物（Ａ）
の粒子径を表１に示す。The particle size and average particle size of the obtained vinyl chloride resin particles, the gel content of the vinyl chloride resin particles, and the composition (A)
Are shown in Table 1.

【００９６】合成例１７ トリアリルイソシアヌレートの替りにトリメチロールプ
ロペントリメタクリレートを添加した以外は、合成例１
と同様にして塩化ビニル重合体、塩化ビニル樹脂の乾燥
粉末、配合物（Ａ）を得た。Synthesis Example 17 Synthesis Example 1 except that trimethylolpropene trimethacrylate was added instead of triallyl isocyanurate.
In the same manner as in Example 1, a dry powder of a vinyl chloride polymer and a vinyl chloride resin, and a blend (A) were obtained.

【００９７】得られた塩化ビニル樹脂粒子の粒子径、平
均粒子径、塩化ビニル樹脂粒子のゲル分、配合物（Ａ）
の粒子径を表１に示す。The particle size and average particle size of the obtained vinyl chloride resin particles, the gel content of the vinyl chloride resin particles, and the composition (A)
Are shown in Table 1.

【００９８】合成例１８ 連鎖移動溶剤としてメルカプトエタノールを０．２g添
加した以外は、合成例１と同様にして塩化ビニル重合
体、塩化ビニル樹脂の乾燥粉末、配合物（Ａ）を得た。Synthesis Example 18 A vinyl chloride polymer, a dry powder of a vinyl chloride resin, and a blend (A) were obtained in the same manner as in Synthesis Example 1 except that 0.2 g of mercaptoethanol was added as a chain transfer solvent.

【００９９】得られた塩化ビニル樹脂粒子の粒子径、平
均粒子径、塩化ビニル樹脂粒子のゲル分、配合物（Ａ）
の粒子径を表１に示す。The particle size and average particle size of the obtained vinyl chloride resin particles, the gel content of the vinyl chloride resin particles, and the composition (A)
Are shown in Table 1.

【０１００】合成例１９ 連鎖移動溶剤としてメルカプトエタノールを０．０４g
添加した以外は、合成例１と同様にして塩化ビニル重合
体、塩化ビニル樹脂の乾燥粉末、配合物（Ａ）を得た。Synthesis Example 19 0.04 g of mercaptoethanol as a chain transfer solvent
Except for the addition, a dry powder of a vinyl chloride polymer and a vinyl chloride resin, and a blend (A) were obtained in the same manner as in Synthesis Example 1.

【０１０１】得られた塩化ビニル樹脂粒子の粒子径、平
均粒子径、塩化ビニル樹脂粒子のゲル分、配合物（Ａ）
の粒子径を表１に示す。The particle size and average particle size of the obtained vinyl chloride resin particles, the gel content of the vinyl chloride resin particles, and the composition (A)
Are shown in Table 1.

【０１０２】合成例２０ トリアリルイソシアヌレートを添加しなかったこと以外
は、合成例９と同様にして塩化ビニル重合体、塩化ビニ
ル樹脂粉末、配合物（Ａ）を得た。Synthesis Example 20 A vinyl chloride polymer, a vinyl chloride resin powder, and a blend (A) were obtained in the same manner as in Synthesis Example 9 except that triallyl isocyanurate was not added.

【０１０３】得られた塩化ビニル樹脂粒子の粒子径、平
均粒子径、塩化ビニル樹脂粒子のゲル分、配合物（Ａ）
の粒子径を表１に示す。The particle size and average particle size of the obtained vinyl chloride resin particles, the gel content of the vinyl chloride resin particles, and the composition (A)
Are shown in Table 1.

【０１０４】尚、実施例中の各物性値は以下の方法によ
り測定した。The physical properties in the examples were measured by the following methods.

【０１０５】〜平均粒径〜 装置はレーザー回析／散乱式粒径測定装置（堀場製作所
（株）製、商品名「ＬＡ−７００」）を用いた。測定に
際しては、測定サンプルのレーザー透過率が７５〜８５
％になるように濃度調整を行なった。Average Particle Size A laser diffraction / scattering type particle size measuring device (trade name “LA-700”, manufactured by Horiba, Ltd.) was used. When measuring, the laser transmittance of the measurement sample is 75 to 85
% Was adjusted.

【０１０６】〜ゲル分の測定〜 ポリ塩化ビニル樹脂１ｇにテトラヒドロフラン５０ｃｃ
を加え、６０℃にて２４時間攪拌し、その後、遠心沈降
機（日立０５−Ｐ２１）で４０００ｒｐｍ×６０分処理
することにより、不溶分を沈降分離し、上澄み液を除去
後、不溶分を回収した。この不溶分を真空乾燥後、重量
を測定し、測定試料量に対する割合としてゲル分を算出
した。-Measurement of gel content- 50 g of tetrahydrofuran per 1 g of polyvinyl chloride resin
, And stirred at 60 ° C. for 24 hours, and then subjected to centrifugal sedimentation (Hitachi 05-P21) at 4,000 rpm × 60 minutes to precipitate and separate insoluble components, remove supernatant, and collect insoluble components. did. After vacuum drying the insoluble matter, the weight was measured, and the gel content was calculated as a ratio to the amount of the measurement sample.

【０１０７】〜インキの流動性〜 インキを１５０ｃｃデイスポカップに入れて、６０°に
傾けた際の流動性を調べた。評価の判定基準は下記の通
りである。-Fluidity of Ink-The fluidity when the ink was placed in a 150 cc disposable cup and tilted at 60 ° was examined. The evaluation criteria are as follows.

【０１０８】○；流動性に問題なし △；流動性に多少問題あり。インキが多少流れずらい。；: No problem in fluidity Δ: Some problem in fluidity Ink is hard to flow.

【０１０９】×；流動性に問題あり。インキが流れな
い。X: There is a problem in fluidity. Ink does not run.

【０１１０】〜印刷物の艶消し性〜 グロスメーター（日本電色工業（株）製、商品名「ＶＧ
Ｓ−３００Ａ」）を用いて、印刷シートに入射角６０℃
で照射された光の反射率を測定した。反射率が小さいほ
ど艶消しの度合いが大きい。-Matting property of printed matter-Gloss meter (trade name "VG" manufactured by Nippon Denshoku Industries Co., Ltd.)
S-300A ") to the printed sheet at an incident angle of 60 ° C.
The reflectance of the light irradiated in was measured. The lower the reflectance, the greater the degree of matting.

【０１１１】〜印刷物の表面凹凸性〜 印刷塗布面の凸物を目視判定により評価を行なった。-Surface Irregularity of Printed Material-The convexity of the print-coated surface was evaluated by visual judgment.

【０１１２】○；平滑性に問題なし △；平滑性に多少問題あり ×；平滑性に問題あり 実施例１ 樹脂ワニスと合成例１で得られたポリ塩化ビニル樹脂と
をポリ塩化ビニル樹脂含有量が１５重量％となるように
配合し、デイゾルバー式ミキサー（ＴＯＫＵＳＹＵ Ｋ
ＩＫＡ ＫＯＧＹＯ（株）製、商品名「Ｔ．Ｋ．ＨＯＭ
Ｏ ＤＩＳＰＥＲ ＭＯＤＥＬ７Ｃ」）を用い、５００
ｒｐｍ×２０分間混練し、マットインキを得た。；: No problem in smoothness Δ: some problem in smoothness ×: problem in smoothness Example 1 Resin varnish and polyvinyl chloride resin obtained in Synthesis Example 1 were used for the content of polyvinyl chloride resin And a dissolver mixer (TOKYUSUK).
Product name "TK HOM" manufactured by IKA KOGYO Co., Ltd.
O DISPER MODEL7C ") and 500
The mixture was kneaded at rpm × 20 minutes to obtain a mat ink.

【０１１３】得られたマットインクを離型紙上に卓上印
刷機で塗布後、４０℃のギアオーブンで１時間乾燥させ
印刷塗布物を得た。マットインキ、及び印刷塗布物の評
価結果を表２に示す。The obtained mat ink was applied on release paper by a desktop printer, and then dried in a gear oven at 40 ° C. for 1 hour to obtain a printed coating. Table 2 shows the evaluation results of the mat ink and the printed coating.

【０１１４】実施例２ 合成例１で得られたポリ塩化ビニル樹脂の代りに、合成
例２で得られたポリ塩化ビニル樹脂を用いた以外は、実
施例１と同様の方法で評価をおこなった。Example 2 Evaluation was conducted in the same manner as in Example 1 except that the polyvinyl chloride resin obtained in Synthesis Example 2 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1. .

【０１１５】マットインキ、及び印刷塗布物の評価結果
を表２に示す。Table 2 shows the evaluation results of the mat ink and the printed coating.

【０１１６】実施例３ 合成例１で得られたポリ塩化ビニル樹脂の代りに、合成
例３で得られたポリ塩化ビニル樹脂を用いた以外は、実
施例１と同様の方法で評価をおこなった。マットイン
キ、及び印刷塗布物の評価結果を表２に示す。Example 3 Evaluation was performed in the same manner as in Example 1 except that the polyvinyl chloride resin obtained in Synthesis Example 3 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1. . Table 2 shows the evaluation results of the mat ink and the printed coating.

【０１１７】実施例４ 合成例１で得られたポリ塩化ビニル樹脂の代りに、合成
例４で得られたポリ塩化ビニル樹脂を用いた以外は、実
施例１と同様の方法で評価をおこなった。マットイン
キ、及び印刷塗布物の評価結果を表２に示す。Example 4 Evaluation was performed in the same manner as in Example 1 except that the polyvinyl chloride resin obtained in Synthesis Example 4 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1. . Table 2 shows the evaluation results of the mat ink and the printed coating.

【０１１８】実施例５ 合成例１で得られたポリ塩化ビニル樹脂の代りに、合成
例９で得られたポリ塩化ビニル樹脂を用いた以外は、実
施例１と同様の方法で評価をおこなった。マットイン
キ、及び印刷塗布物の評価結果を表２に示す。Example 5 Evaluation was performed in the same manner as in Example 1 except that the polyvinyl chloride resin obtained in Synthesis Example 9 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1. . Table 2 shows the evaluation results of the mat ink and the printed coating.

【０１１９】実施例６ 合成例１で得られたポリ塩化ビニル樹脂の代りに、合成
例１１で得られたポリ塩化ビニル樹脂を用いた以外は、
実施例１と同様の方法で評価をおこなった。マットイン
キ、及び印刷塗布物の評価結果を表２に示す。Example 6 The procedure of Example 1 was repeated, except that the polyvinyl chloride resin obtained in Synthesis Example 11 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1.
Evaluation was performed in the same manner as in Example 1. Table 2 shows the evaluation results of the mat ink and the printed coating.

【０１２０】実施例７ 合成例１で得られたポリ塩化ビニル樹脂の代りに、合成
例１３で得られたポリ塩化ビニル樹脂を用いた以外は、
実施例１と同様の方法で評価をおこなった。マットイン
キ、及び印刷塗布物の評価結果を表２に示す。Example 7 [0120] Except that the polyvinyl chloride resin obtained in Synthesis Example 13 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1,
Evaluation was performed in the same manner as in Example 1. Table 2 shows the evaluation results of the mat ink and the printed coating.

【０１２１】実施例８ 合成例１で得られたポリ塩化ビニル樹脂の代りに、合成
例１５で得られたポリ塩化ビニル樹脂を用いた以外は、
実施例１と同様の方法で評価をおこなった。マットイン
キ、及び印刷塗布物の評価結果を表２に示す。Example 8 The procedure of Example 15 was repeated, except that the polyvinyl chloride resin obtained in Synthesis Example 15 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1.
Evaluation was performed in the same manner as in Example 1. Table 2 shows the evaluation results of the mat ink and the printed coating.

【０１２２】実施例９ 合成例１で得られたポリ塩化ビニル樹脂の代りに、合成
例１６で得られたポリ塩化ビニル樹脂を用いた以外は、
実施例１と同様の方法で評価をおこなった。マットイン
キ、及び印刷塗布物の評価結果を表２に示す。Example 9 The procedure of Example 16 was repeated, except that the polyvinyl chloride resin obtained in Synthesis Example 16 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1.
Evaluation was performed in the same manner as in Example 1. Table 2 shows the evaluation results of the mat ink and the printed coating.

【０１２３】実施例１０ 合成例１で得られたポリ塩化ビニル樹脂の代りに、合成
例１８で得られたポリ塩化ビニル樹脂を用いた以外は、
実施例１と同様の方法で評価をおこなった。マットイン
キ、及び印刷塗布物の評価結果を表２に示す。Example 10 The procedure of Example 18 was repeated, except that the polyvinyl chloride resin obtained in Synthesis Example 18 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1.
Evaluation was performed in the same manner as in Example 1. Table 2 shows the evaluation results of the mat ink and the printed coating.

【０１２４】実施例１１ 合成例１で得られたポリ塩化ビニル樹脂の代りに、合成
例１９で得られたポリ塩化ビニル樹脂を用いた以外は、
実施例１と同様の方法で評価をおこなった。マットイン
キ、及び印刷塗布物の評価結果を表２に示す。Example 11 The polyvinyl chloride resin obtained in Synthesis Example 19 was used in place of the polyvinyl chloride resin obtained in Synthesis Example 1 except that
Evaluation was performed in the same manner as in Example 1. Table 2 shows the evaluation results of the mat ink and the printed coating.

【０１２５】実施例１２ 合成例１で得られたポリ塩化ビニル樹脂の代りに、合成
例５で得られたポリ塩化ビニル樹脂を用いた以外は、実
施例１と同様の方法で評価をおこなった。マットイン
キ、及び印刷塗布物の評価結果を表２に示す。Example 12 Evaluation was conducted in the same manner as in Example 1 except that the polyvinyl chloride resin obtained in Synthesis Example 5 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1. . Table 2 shows the evaluation results of the mat ink and the printed coating.

【０１２６】実施例１３ 合成例１で得られたポリ塩化ビニル樹脂の代りに、合成
例６で得られたポリ塩化ビニル樹脂を用いた以外は、実
施例１と同様の方法で評価をおこなった。マットイン
キ、及び印刷塗布物の評価結果を表２に示す。Example 13 Evaluation was performed in the same manner as in Example 1 except that the polyvinyl chloride resin obtained in Synthesis Example 6 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1. . Table 2 shows the evaluation results of the mat ink and the printed coating.

【０１２７】実施例１４ 合成例１で得られたポリ塩化ビニル樹脂の代りに、合成
例７で得られたポリ塩化ビニル樹脂を用いた以外は、実
施例１と同様の方法で評価をおこなった。マットイン
キ、及び印刷塗布物の評価結果を表２に示す。Example 14 Evaluation was performed in the same manner as in Example 1 except that the polyvinyl chloride resin obtained in Synthesis Example 7 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1. . Table 2 shows the evaluation results of the mat ink and the printed coating.

【０１２８】実施例１５ 合成例１で得られたポリ塩化ビニル樹脂の代りに、合成
例１４で得られたポリ塩化ビニル樹脂を用いた以外は、
実施例１と同様の方法で評価をおこなった。マットイン
キ、及び印刷塗布物の評価結果を表２に示す。Example 15 The procedure of Example 14 was repeated, except that the polyvinyl chloride resin obtained in Synthesis Example 14 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1.
Evaluation was performed in the same manner as in Example 1. Table 2 shows the evaluation results of the mat ink and the printed coating.

【０１２９】実施例１６ 合成例１で得られたポリ塩化ビニル樹脂の代りに、合成
例１７で得られたポリ塩化ビニル樹脂を用いた以外は、
実施例１と同様の方法で評価をおこなった。マットイン
キ、及び印刷塗布物の評価結果を表２に示す。Example 16 The procedure was repeated except that the polyvinyl chloride resin obtained in Synthesis Example 17 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1.
Evaluation was performed in the same manner as in Example 1. Table 2 shows the evaluation results of the mat ink and the printed coating.

【０１３０】実施例１７ 合成例１で得られたポリ塩化ビニル樹脂の代りに、合成
例２０で得られたポリ塩化ビニル樹脂を用いた以外は、
実施例１と同様の方法で評価をおこなった。マットイン
キ、及び印刷塗布物の評価結果を表２に示す。Example 17 The procedure of Example 20 was repeated, except that the polyvinyl chloride resin obtained in Synthesis Example 20 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1.
Evaluation was performed in the same manner as in Example 1. Table 2 shows the evaluation results of the mat ink and the printed coating.

【０１３１】実施例１８ 合成例１で得られたポリ塩化ビニル樹脂の含有量を、１
０重量％とした以外は、実施例１と同様の方法で評価を
行なった。マットインキ、及び印刷塗布物の評価結果を
表２に示す。Example 18 The content of the polyvinyl chloride resin obtained in Synthesis Example 1 was adjusted to 1
Evaluation was performed in the same manner as in Example 1 except that the amount was set to 0% by weight. Table 2 shows the evaluation results of the mat ink and the printed coating.

【０１３２】実施例１９ 合成例１で得られたポリ塩化ビニル樹脂の含有量を、３
０重量％とした以外は、実施例１と同様の方法で評価を
行なった。マットインキ、及び印刷塗布物の評価結果を
表２に示す。Example 19 The content of the polyvinyl chloride resin obtained in Synthesis Example 1 was adjusted to 3
Evaluation was performed in the same manner as in Example 1 except that the amount was set to 0% by weight. Table 2 shows the evaluation results of the mat ink and the printed coating.

【０１３３】実施例２０ 合成例１で得られたポリ塩化ビニル樹脂の含有量を、５
０重量％とした以外は、実施例１と同様の方法で評価を
行なった。マットインキ、及び印刷塗布物の評価結果を
表２に示す。Example 20 The content of the polyvinyl chloride resin obtained in Synthesis Example 1 was adjusted to 5
Evaluation was performed in the same manner as in Example 1 except that the amount was set to 0% by weight. Table 2 shows the evaluation results of the mat ink and the printed coating.

【０１３４】実施例２１ メチルエチルケトン５０ｗｔ％、トルエン４０ｗｔ％、
メチルイソブチルケトン１０ｗｔ％からなる混合溶媒８
０重量部、ポリメチルメタクリレート２０重量部と合成
例１で得られたポリ塩化ビニル樹脂とを、ポリ塩化ビニ
ル樹脂含有量が１０重量％となるように配合し、デイゾ
ルバー式ミキサー（ＴＯＫＵＳＹＵ ＫＩＫＡ ＫＯＧ
ＹＯ（株）製、商品名「Ｔ．Ｋ．ＨＯＭＯ ＤＩＳＰＥ
Ｒ ＭＯＤＥＬ７Ｃ」）を用い、２０００ｒｐｍ×３０
分間混練し、マットインキを得た。Example 21 50% by weight of methyl ethyl ketone, 40% by weight of toluene,
Mixed solvent 8 consisting of 10 wt% methyl isobutyl ketone
0 parts by weight, 20 parts by weight of polymethyl methacrylate, and the polyvinyl chloride resin obtained in Synthesis Example 1 were blended so that the content of the polyvinyl chloride resin was 10% by weight, and a dissolver-type mixer (TOKYUSU KIKA KOG) was used.
Product name "TK HOMO DISPE" manufactured by YO Corporation
R MODEL7C ") and 2000 rpm x 30
After kneading for minutes, a matte ink was obtained.

【０１３５】得られたマットインキを離型紙上に卓上印
刷機で塗布後、８０℃のギアオーブンで１Ｈｒ間乾燥さ
せ印刷塗布物を得た。マットインキ、及び印刷塗布物の
評価結果を表２に示す。The obtained matte ink was applied on a release paper using a desktop printer, and then dried in a gear oven at 80 ° C. for 1 hour to obtain a print coating. Table 2 shows the evaluation results of the mat ink and the printed coating.

【０１３６】実施例２２ 樹脂ワニスと合成例１で得られたポリ塩化ビニル樹脂、
平均粒径２μmのシリカとを、ポリ塩化ビニル樹脂含有
量が１５重量％、シリカ含有量が１重量％となるように
配合し、デイゾルバー式ミキサー（ＴＯＫＵＳＹＵ Ｋ
ＩＫＡ ＫＯＧＹＯ（株）製、商品名「Ｔ．Ｋ．ＨＯＭ
Ｏ ＤＩＳＰＥＲ ＭＯＤＥＬ７Ｃ」）を用い、５００
ｒｐｍ×２０分間混練し、マットインキを得た。Example 22 A resin varnish and the polyvinyl chloride resin obtained in Synthesis Example 1,
Silica having an average particle diameter of 2 μm is blended so that the polyvinyl chloride resin content is 15% by weight and the silica content is 1% by weight, and a dissolver mixer (TOKUSYUK) is used.
Product name "TK HOM" manufactured by IKA KOGYO Co., Ltd.
O DISPER MODEL7C ") and 500
The mixture was kneaded at rpm × 20 minutes to obtain a mat ink.

【０１３７】得られたマットインクを離型紙上に卓上印
刷機で塗布後、４０℃のギアオーブンで１Ｈｒ間乾燥さ
せ印刷塗布物を得た。マットインキ、及び印刷塗布物の
評価結果を表２に示す。The obtained matte ink was applied on release paper by a desktop printer, and dried in a gear oven at 40 ° C. for 1 hour to obtain a print coating. Table 2 shows the evaluation results of the mat ink and the printed coating.

【０１３８】比較例１ 合成例１で得られたポリ塩化ビニル樹脂を添加しなかっ
た以外は実施例１と同様の方法で評価を行なった。マッ
トインキ、及び印刷塗布物の評価結果を表１に示す。Comparative Example 1 Evaluation was performed in the same manner as in Example 1 except that the polyvinyl chloride resin obtained in Synthesis Example 1 was not added. Table 1 shows the evaluation results of the mat ink and the printed coating.

【０１３９】比較例２ 合成例１で得られたポリ塩化ビニル樹脂の代りに、粒径
２．５μｍのシリカを用いた以外は実施例１と同様の方
法で評価を行なった。マットインキ、及び印刷塗布物の
評価結果を表２に示す。Comparative Example 2 Evaluation was performed in the same manner as in Example 1 except that silica having a particle size of 2.5 μm was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1. Table 2 shows the evaluation results of the mat ink and the printed coating.

【０１４０】比較例３ 合成例１で得られたポリ塩化ビニル樹脂の代りに、合成
例８で得られたポリ塩化ビニル樹脂を用いた以外は、実
施例１と同様の方法で評価をおこなった。マットイン
キ、及び印刷塗布物の評価結果を表２に示す。Comparative Example 3 Evaluation was performed in the same manner as in Example 1 except that the polyvinyl chloride resin obtained in Synthesis Example 8 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1. . Table 2 shows the evaluation results of the mat ink and the printed coating.

【０１４１】比較例４ 合成例１で得られたポリ塩化ビニル樹脂の代りに、合成
例１０で得られたポリ塩化ビニル樹脂を用いた以外は、
実施例１と同様の方法で評価をおこなった。マットイン
キ、及び印刷塗布物の評価結果を表２に示す。Comparative Example 4 The procedure was repeated except that the polyvinyl chloride resin obtained in Synthesis Example 10 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1.
Evaluation was performed in the same manner as in Example 1. Table 2 shows the evaluation results of the mat ink and the printed coating.

【０１４２】比較例５ 合成例１で得られたポリ塩化ビニル樹脂の代りに、合成
例１２で得られたポリ塩化ビニル樹脂を用いた以外は、
実施例１と同様の方法で評価をおこなった。マットイン
キ、及び印刷塗布物の評価結果を表２に示す。Comparative Example 5 A polyvinyl chloride resin obtained in Synthesis Example 12 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1, except that
Evaluation was performed in the same manner as in Example 1. Table 2 shows the evaluation results of the mat ink and the printed coating.

【０１４３】比較例６ 合成例１で得られたポリ塩化ビニル樹脂の代りに、粒径
８５μｍの汎用塩ビを用いた以外は実施例１と同様の方
法で評価を行なった。マットインキ、及び印刷塗布物の
評価結果を表２に示す。Comparative Example 6 Evaluation was carried out in the same manner as in Example 1 except that general-purpose polyvinyl chloride having a particle size of 85 μm was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1. Table 2 shows the evaluation results of the mat ink and the printed coating.

【０１４４】比較例７ 合成例１で得られたポリ塩化ビニル樹脂の代りに、粒径
２．５μｍのシリカを用いた以外は実施例２１と同様の
方法で評価を行なった。マットインキ、及び印刷塗布物
の評価結果を表２に示す。Comparative Example 7 Evaluation was performed in the same manner as in Example 21 except that silica having a particle size of 2.5 μm was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1. Table 2 shows the evaluation results of the mat ink and the printed coating.

【０１４５】比較例８ 合成例１で得られたポリ塩化ビニル樹脂の含有量を、７
０重量％とした以外は、実施例１と同様の方法で評価を
行なった。マットインキ、及び印刷塗布物の評価結果を
表２に示す。Comparative Example 8 The content of the polyvinyl chloride resin obtained in Synthesis Example 1 was changed to 7
Evaluation was performed in the same manner as in Example 1 except that the amount was set to 0% by weight. Table 2 shows the evaluation results of the mat ink and the printed coating.

【０１４６】[0146]

【表１】 [Table 1]

【０１４７】[0147]

【表２】 [Table 2]

【０１４８】合成例２１ ２．５Ｌオートクレーブ中に重合開始前に脱イオン水５
００ｇ、塩化ビニル単量体８００ｇ、トリアリルイソシ
アヌレート２．８ｇ、ラウロイルパーオキサイドを２重
量％含有させたシード粒子を１１０ｇ、乳化重合により
得られたシード粒子を７０ｇ、０．１重量％硫酸第一鉄
水溶液８ｇ、界面活性剤を仕込み、反応混合物の温度を
４２℃に上げると共に、０．１重量％アスコルビン酸水
溶液１６０ｇを重合終了まで連続的に添加した。Synthesis Example 21 In a 2.5 L autoclave, deionized water 5
00g, vinyl chloride monomer 800g, triallyl isocyanurate 2.8g, 110g of seed particles containing 2% by weight of lauroyl peroxide, 70g of seed particles obtained by emulsion polymerization, 0.1% by weight of sulfuric acid 8 g of an aqueous solution of ferrous iron and a surfactant were charged, the temperature of the reaction mixture was raised to 42 ° C., and 160 g of an aqueous solution of ascorbic acid of 0.1% by weight were continuously added until the polymerization was completed.

【０１４９】更に重合開始から１０時間後まで界面活性
剤を連続的に添加した。重合前、重合中の界面活性剤は
スルホコハク酸エステル塩類を使用した。Further, a surfactant was continuously added until 10 hours after the start of the polymerization. Before the polymerization, sulfosuccinate salts were used as the surfactant during the polymerization.

【０１５０】重合温度が４２℃における塩化ビニル飽和
蒸気圧から２．１ｋｇ／ｃｍ2降下した時に重合を停止
し、重合終了後に未反応の塩化ビニル単量体を回収し、
塩化ビニル重合体ラテックスを得た。得られた塩化ビニ
ル重合体は平均粒径１．０５μｍであった。When the polymerization temperature dropped 2.1 kg / cm 2 from the saturated vapor pressure of vinyl chloride at 42 ° C., the polymerization was stopped, and after the polymerization was completed, unreacted vinyl chloride monomer was recovered.
A vinyl chloride polymer latex was obtained. The obtained vinyl chloride polymer had an average particle size of 1.05 μm.

【０１５１】このラテックスを回転円盤式噴霧乾燥機に
より乾燥し、粉砕機を通して塩化ビニル樹脂を得た。得
られた塩化ビニル樹脂のゲル分は８５重量％であった。This latex was dried by a rotating disk type spray drier, and a vinyl chloride resin was obtained through a pulverizer. The gel content of the obtained vinyl chloride resin was 85% by weight.

【０１５２】合成例２２ トリアリルイソシアヌレートを０．８ｇ添加した以外
は、合成例１と同様にして塩化ビニル重合体を得た。得
られた塩化ビニル重合体は平均粒径０．９６μｍであっ
た。Synthesis Example 22 A vinyl chloride polymer was obtained in the same manner as in Synthesis Example 1 except that 0.8 g of triallylisocyanurate was added. The obtained vinyl chloride polymer had an average particle size of 0.96 μm.

【０１５３】このラテックスを回転円盤式噴霧乾燥機に
より乾燥し、粉砕機を通して塩化ビニル樹脂を得た。得
られた塩化ビニル樹脂のゲル分は４５重量％であった。This latex was dried by a rotating disk type spray drier, and a vinyl chloride resin was obtained through a pulverizer. The gel content of the obtained vinyl chloride resin was 45% by weight.

【０１５４】合成例２３ ２．５Ｌオートクレーブ中に重合開始前に脱イオン水８
００ｇ、塩化ビニル単量体５００ｇ、ラウロイルパーオ
キサイド０．５ｇ、ポリビニルアルコール１５ｇ、トリ
アリルイソシアヌレート３ｇを仕込み、５０００ｒｐｍ
で均質化処理を行なった。その後、反応混合物の温度を
規程温度に昇温した。Synthesis Example 23 Deionized water 8 in a 2.5 L autoclave before polymerization was started
00 g, vinyl chloride monomer 500 g, lauroyl peroxide 0.5 g, polyvinyl alcohol 15 g, triallyl isocyanurate 3 g, and 5000 rpm
For homogenization. Thereafter, the temperature of the reaction mixture was raised to the prescribed temperature.

【０１５５】オートクレーブ内の圧力が規定温度の塩化
ビニル飽和蒸気圧から２ｋｇ／ｃｍ2降下した時に重合
を停止し、重合終了後に未反応の塩化ビニル単量体を回
収し、塩化ビニル重合体ラテックスを得た。得られた塩
化ビニル重合体は平均粒径９．０μｍであった。When the pressure in the autoclave drops by 2 kg / cm 2 from the saturated vapor pressure of vinyl chloride at the specified temperature, the polymerization is stopped. After the polymerization is completed, unreacted vinyl chloride monomer is recovered, and the vinyl chloride polymer latex is recovered. Obtained. The obtained vinyl chloride polymer had an average particle size of 9.0 μm.

【０１５６】このスラリーを遠心脱水後流動乾燥により
乾燥し、塩化ビニル樹脂を得た。得られた塩化ビニル樹
脂のゲル分は８６重量％であった。This slurry was centrifugally dehydrated and dried by fluidized drying to obtain a vinyl chloride resin. The gel content of the obtained vinyl chloride resin was 86% by weight.

【０１５７】尚、以下の実施例中の各物性値は、「イン
クの流動性」の項目を除き、前記と同様な方法により測
定した。The physical properties in the following examples were measured in the same manner as described above, except for the item of “ink fluidity”.

【０１５８】〜インクの流動性〜 インクを１５０ｃｃデイスポカップに入れて、３０°に
傾けた際の流動性を調べた。評価の判定基準は下記の通
りである。-Fluidity of Ink-The fluidity when the ink was placed in a 150 cc disposable cup and tilted at 30 ° was examined. The evaluation criteria are as follows.

【０１５９】○；流動性に問題なし △；流動性に多少問題あり。インクが多少流れずらい。；: No problem in fluidity Δ: Some problem in fluidity Ink flows slightly.

【０１６０】×；流動性に問題あり。インクが流れな
い。X: There is a problem in fluidity. Ink does not flow.

【０１６１】実施例２３ 油ワニスと合成例２１で得られたポリ塩化ビニル樹脂と
を、ポリ塩化ビニル樹脂含有量が１０重量％となるよう
に配合し、デイゾルバー式ミキサー（商品名「Ｔ．Ｋ．
ＨＯＭＯ ＤＩＳＰＥＲ ＭＯＤＥＬ７Ｃ」；ＴＯＫＵ
ＳＹＵ ＫＩＫＡ ＫＯＧＹＯ（株）製）を用い、１０
００ｒｐｍ×１０分間混練し、マットインクを得た。Example 23 An oil varnish and the polyvinyl chloride resin obtained in Synthesis Example 21 were blended so that the content of the polyvinyl chloride resin was 10% by weight, and a dissolver mixer (trade name “TK”) was used. .
HOMO DISPER MODEL7C "; TOKU
SYU KIKA KOGYO Co., Ltd.)
The mixture was kneaded at 00 rpm for 10 minutes to obtain a mat ink.

【０１６２】得られたマットインクを離型紙上にクリア
ランス３μｍのアプリケーターを用いて塗布後、１００
℃のギアオーブンで乾燥させ印刷塗布物を得た。マット
インク、及び印刷塗布物の評価結果を表3に示す。After the obtained mat ink was applied on release paper using an applicator having a clearance of 3 μm,
The coating was dried in a gear oven at ℃ to obtain a printed coating. Table 3 shows the evaluation results of the matte ink and the printed material.

【０１６３】実施例２４ 合成例２１で得られたポリ塩化ビニル樹脂の含有量を、
３０重量％とした以外は、実施例２３と同様の方法で評
価を行なった。マットインク、及び印刷塗布物の評価結
果を表3に示す。Example 24 The content of the polyvinyl chloride resin obtained in Synthesis Example 21 was
Evaluation was performed in the same manner as in Example 23 except that the content was 30% by weight. Table 3 shows the evaluation results of the matte ink and the printed material.

【０１６４】実施例２５ 合成例２１で得られたポリ塩化ビニル樹脂の含有量を、
５０重量％とした以外は、実施例２３と同様の方法で評
価を行なった。マットインク、及び印刷塗布物の評価結
果を表3に示す。Example 25 The content of the polyvinyl chloride resin obtained in Synthesis Example 21 was
Evaluation was performed in the same manner as in Example 23 except that the amount was 50% by weight. Table 3 shows the evaluation results of the matte ink and the printed material.

【０１６５】実施例２６ 合成例２１で得られたポリ塩化ビニル樹脂の代りに、合
成例２２で得られたポリ塩化ビニル樹脂を用いた以外
は、実施例２と同様の方法で評価を行った。マットイン
ク、及び印刷塗布物の評価結果を表3に示す。Example 26 Evaluation was performed in the same manner as in Example 2 except that the polyvinyl chloride resin obtained in Synthesis Example 22 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 21. . Table 3 shows the evaluation results of the matte ink and the printed material.

【０１６６】実施例２７ 合成例２１で得られたポリ塩化ビニル樹脂の代りに、合
成例２３で得られたポリ塩化ビニル樹脂を用いた以外
は、実施例２と同様の方法で評価を行った。マットイン
ク、及び印刷塗布物の評価結果を表3に示す。Example 27 Evaluation was performed in the same manner as in Example 2 except that the polyvinyl chloride resin obtained in Synthesis Example 23 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 21. . Table 3 shows the evaluation results of the matte ink and the printed material.

【０１６７】[0167]

【表３】 [Table 3]

【０１６８】実施例２８ 油ワニスと合成例１で得られたポリ塩化ビニル樹脂と
を、ポリ塩化ビニル樹脂含有量が３０重量％となるよう
に配合し、デイゾルバー式ミキサー（ＴＯＫＵＳＹＵ
ＫＩＫＡ ＫＯＧＹＯ（株）製、商品名「Ｔ．Ｋ．ＨＯ
ＭＯ ＤＩＳＰＥＲ ＭＯＤＥＬ７Ｃ」）を用い、１０
００ｒｐｍ×１０分間混練し、マットインクを得た。Example 28 An oil varnish and the polyvinyl chloride resin obtained in Synthesis Example 1 were blended so that the content of the polyvinyl chloride resin was 30% by weight, and a dissolver type mixer (TOKUSYU) was used.
KIKA KOGYO Co., Ltd., trade name "TKHO"
MO DISPER MODEL7C ”)
The mixture was kneaded at 00 rpm for 10 minutes to obtain a mat ink.

【０１６９】得られたマットインクを離型紙上にクリア
ランス３μｍのアプリケーターを用いて塗布後、１００
℃のギアオーブンで乾燥させ印刷塗布物を得た。マット
インク、及び印刷塗布物の評価結果を表4に示す。After the obtained mat ink was applied on release paper using an applicator having a clearance of 3 μm,
The coating was dried in a gear oven at ℃ to obtain a printed coating. Table 4 shows the evaluation results of the matte ink and the printed coating.

【０１７０】実施例２９ 合成例１で得られたポリ塩化ビニル樹脂の代わりに合成
例２で得られたポリ塩化ビニル樹脂を用いた以外は、実
施例２８と同様の方法で評価を行なった。マットイン
ク、及び印刷塗布物の評価結果を表4に示す。Example 29 Evaluation was conducted in the same manner as in Example 28 except that the polyvinyl chloride resin obtained in Synthesis Example 2 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1. Table 4 shows the evaluation results of the matte ink and the printed coating.

【０１７１】実施例３０ 合成例１で得られたポリ塩化ビニル樹脂の代わりに合成
例３で得られたポリ塩化ビニル樹脂を用いた以外は、実
施例２８と同様の方法で評価を行なった。マットイン
ク、及び印刷塗布物の評価結果を表4に示す。Example 30 Evaluation was performed in the same manner as in Example 28 except that the polyvinyl chloride resin obtained in Synthesis Example 3 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1. Table 4 shows the evaluation results of the matte ink and the printed coating.

【０１７２】実施例３１ 合成例１で得られたポリ塩化ビニル樹脂の代わりに合成
例４で得られたポリ塩化ビニル樹脂を用いた以外は、実
施例２８と同様の方法で評価を行なった。マットイン
ク、及び印刷塗布物の評価結果を表4に示す。Example 31 Evaluation was conducted in the same manner as in Example 28 except that the polyvinyl chloride resin obtained in Synthesis Example 4 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1. Table 4 shows the evaluation results of the matte ink and the printed coating.

【０１７３】実施例３２ 合成例１で得られたポリ塩化ビニル樹脂の代わりに合成
例９で得られたポリ塩化ビニル樹脂を用いた以外は、実
施例２８と同様の方法で評価を行なった。マットイン
ク、及び印刷塗布物の評価結果を表4に示す。Example 32 Evaluation was performed in the same manner as in Example 28 except that the polyvinyl chloride resin obtained in Synthesis Example 9 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1. Table 4 shows the evaluation results of the matte ink and the printed coating.

【０１７４】実施例３３ 合成例１で得られたポリ塩化ビニル樹脂の代わりに合成
例１１で得られたポリ塩化ビニル樹脂を用いた以外は、
実施例２８と同様の方法で評価を行なった。マットイン
ク、及び印刷塗布物の評価結果を表4に示す。Example 33 The procedure was repeated except that the polyvinyl chloride resin obtained in Synthesis Example 11 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1.
Evaluation was performed in the same manner as in Example 28. Table 4 shows the evaluation results of the matte ink and the printed coating.

【０１７５】実施例３４ 合成例１で得られたポリ塩化ビニル樹脂の代わりに合成
例１３で得られたポリ塩化ビニル樹脂を用いた以外は、
実施例２８と同様の方法で評価を行なった。マットイン
ク、及び印刷塗布物の評価結果を表4に示す。Example 34 The procedure was repeated except that the polyvinyl chloride resin obtained in Synthesis Example 13 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1.
Evaluation was performed in the same manner as in Example 28. Table 4 shows the evaluation results of the matte ink and the printed coating.

【０１７６】実施例３５ 合成例１で得られたポリ塩化ビニル樹脂の代わりに合成
例１５で得られたポリ塩化ビニル樹脂を用いた以外は、
実施例２８と同様の方法で評価を行なった。マットイン
ク、及び印刷塗布物の評価結果を表4に示す。Example 35 A polyvinyl chloride resin obtained in Synthesis Example 15 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1, except that
Evaluation was performed in the same manner as in Example 28. Table 4 shows the evaluation results of the matte ink and the printed coating.

【０１７７】実施例３６ 合成例１で得られたポリ塩化ビニル樹脂の代わりに合成
例１６で得られたポリ塩化ビニル樹脂を用いた以外は、
実施例２８と同様の方法で評価を行なった。マットイン
ク、及び印刷塗布物の評価結果を表4に示す。Example 36 The procedure was repeated except that the polyvinyl chloride resin obtained in Synthesis Example 16 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1.
Evaluation was performed in the same manner as in Example 28. Table 4 shows the evaluation results of the matte ink and the printed coating.

【０１７８】実施例３７ 合成例１で得られたポリ塩化ビニル樹脂の代わりに合成
例１８で得られたポリ塩化ビニル樹脂を用いた以外は、
実施例２８と同様の方法で評価を行なった。マットイン
ク、及び印刷塗布物の評価結果を表4に示す。Example 37 The procedure was repeated except that the polyvinyl chloride resin obtained in Synthesis Example 18 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1.
Evaluation was performed in the same manner as in Example 28. Table 4 shows the evaluation results of the matte ink and the printed coating.

【０１７９】実施例３８ 合成例１で得られたポリ塩化ビニル樹脂の代わりに合成
例１９で得られたポリ塩化ビニル樹脂を用いた以外は、
実施例２８と同様の方法で評価を行なった。マットイン
ク、及び印刷塗布物の評価結果を表4に示す。Example 38: Except that the polyvinyl chloride resin obtained in Synthesis Example 19 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1,
Evaluation was performed in the same manner as in Example 28. Table 4 shows the evaluation results of the matte ink and the printed coating.

【０１８０】実施例３９ 合成例１で得られたポリ塩化ビニル樹脂の代わりに合成
例５で得られたポリ塩化ビニル樹脂を用いた以外は、実
施例２８と同様の方法で評価を行なった。マットイン
ク、及び印刷塗布物の評価結果を表4に示す。Example 39 Evaluation was performed in the same manner as in Example 28 except that the polyvinyl chloride resin obtained in Synthesis Example 5 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1. Table 4 shows the evaluation results of the matte ink and the printed coating.

【０１８１】実施例４０ 合成例１で得られたポリ塩化ビニル樹脂の代わりに合成
例６で得られたポリ塩化ビニル樹脂を用いた以外は、実
施例２８と同様の方法で評価を行なった。マットイン
ク、及び印刷塗布物の評価結果を表4に示す。Example 40 Evaluation was conducted in the same manner as in Example 28 except that the polyvinyl chloride resin obtained in Synthesis Example 6 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1. Table 4 shows the evaluation results of the matte ink and the printed coating.

【０１８２】実施例４１ 合成例１で得られたポリ塩化ビニル樹脂の代わりに合成
例７で得られたポリ塩化ビニル樹脂を用いた以外は、実
施例２８と同様の方法で評価を行なった。マットイン
ク、及び印刷塗布物の評価結果を表4に示す。Example 41 Evaluation was conducted in the same manner as in Example 28 except that the polyvinyl chloride resin obtained in Synthesis Example 7 was used instead of the polyvinyl chloride resin obtained in Synthesis Example 1. Table 4 shows the evaluation results of the matte ink and the printed coating.

【０１８３】実施例４２ 合成例１で得られたポリ塩化ビニル樹脂の代わりに合成
例１４で得られたポリ塩化ビニル樹脂を用いた以外は、
実施例２８と同様の方法で評価を行なった。マットイン
ク、及び印刷塗布物の評価結果を表4に示す。Example 42 A polyvinyl chloride resin obtained in Synthesis Example 14 was used in place of the polyvinyl chloride resin obtained in Synthesis Example 1, except that
Evaluation was performed in the same manner as in Example 28. Table 4 shows the evaluation results of the matte ink and the printed coating.

【０１８４】実施例４３ 合成例１で得られたポリ塩化ビニル樹脂の代わりに合成
例１７で得られたポリ塩化ビニル樹脂を用いた以外は、
実施例２８と同様の方法で評価を行なった。マットイン
ク、及び印刷塗布物の評価結果を表4に示す。Example 43 A polyvinyl chloride resin obtained in Synthesis Example 17 was used in place of the polyvinyl chloride resin obtained in Synthesis Example 1, except that
Evaluation was performed in the same manner as in Example 28. Table 4 shows the evaluation results of the matte ink and the printed coating.

【０１８５】[0185]

【表４】 [Table 4]

【０１８６】[0186]

【発明の効果】本発明の印刷インク用艶消し剤は、艶消
し性優れるだけでなく、インク中への分散性、流動性に
優れたものであり、その工業的価値は非常に高いもので
あり、特にオフセット印刷、グラビア印刷、凸版印刷、
スクリーン印刷等の印刷インク用途に優れたものであ
る。The matting agent for printing inks of the present invention is not only excellent in matting properties but also excellent in dispersibility and fluidity in inks, and its industrial value is very high. Yes, especially offset printing, gravure printing, letterpress printing,
It is excellent for printing ink applications such as screen printing.

───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4J039 AD05 BA16 BA21 BA22 BA23 BA26 BA30 BA31 BA32 BC02 BC03 BC07 BC08 BC16 BC19 BC20 BE12 BE20 BE23 CA07 EA33 GA01 GA02 GA03 GA10 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J039 AD05 BA16 BA21 BA22 BA23 BA26 BA30 BA31 BA32 BC02 BC03 BC07 BC08 BC16 BC19 BC20 BE12 BE20 BE23 CA07 EA33 GA01 GA02 GA03 GA10

Claims (13)

【特許請求の範囲】[Claims] 【請求項１】 粒子径が０．０１〜５０μm、かつ、平
均粒径が０．１〜４０μmであるポリ塩化ビニル樹脂粒
子であって、このポリ塩化ビニル樹脂粒子の乾燥粉末１
００重量部と２，２，４−トリメチル１，３−ペンタン
ジオールジイソブチレート６０重量部とを配合しデイゾ
ルバー式ミキサーを用い２５℃、８００ｒｐｍで３分間
混錬したときの配合物中のポリ塩化ビニル樹脂の平均粒
子径が０．１〜７０μｍでその最大粒子径が１５０μｍ
未満となるポリ塩化ビニル樹脂粒子からなる印刷インキ
用艶消し剤。1. Polyvinyl chloride resin particles having a particle size of 0.01 to 50 μm and an average particle size of 0.1 to 40 μm, wherein the dry powder 1 of the polyvinyl chloride resin particles
00 parts by weight and 60 parts by weight of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate were mixed and kneaded with a dissolver mixer at 25 ° C. and 800 rpm for 3 minutes. The average particle size of the vinyl resin is 0.1 to 70 μm and the maximum particle size is 150 μm
Matting agent for printing ink consisting of polyvinyl chloride resin particles less than. 【請求項２】 ポリ塩化ビニル樹脂粒子が、テトラヒド
ロフランに不溶のゲル分を３０重量％以上含んでなる請
求項１記載の印刷インキ用艶消し剤。2. The matting agent for a printing ink according to claim 1, wherein the polyvinyl chloride resin particles contain at least 30% by weight of a gel component insoluble in tetrahydrofuran. 【請求項３】 ポリ塩化ビニル樹脂粒子を３〜６０重量
部含有してなる印刷用インキ組成物。3. A printing ink composition comprising 3 to 60 parts by weight of polyvinyl chloride resin particles. 【請求項４】 ポリ塩化ビニル樹脂粒子が、テトラヒド
ロフランに不溶のゲル分を３０重量％以上含んでなる請
求項３記載の印刷用インキ組成物。4. The printing ink composition according to claim 3, wherein the polyvinyl chloride resin particles contain at least 30% by weight of a gel component insoluble in tetrahydrofuran. 【請求項５】 請求項１記載の印刷インキ用艶消し剤を
３〜６０重量部含有してなる印刷用インキ組成物。5. A printing ink composition comprising 3 to 60 parts by weight of the matting agent for printing ink according to claim 1. 【請求項６】 請求項２記載の印刷インキ用艶消し剤を
３〜６０重量部含有してなる印刷用インキ組成物。6. A printing ink composition comprising 3 to 60 parts by weight of the matting agent for printing ink according to claim 2. 【請求項７】 印刷インキとして、ソルビリテイパラメ
ーターが３〜２０（ｃａｌ／ｃｍ3）0.5の範囲にある溶
剤を含む非水系印刷用インキを用いる、請求項３〜６の
いずれか１項記載の印刷用インキ組成物。7. The printing ink according to claim 3 , wherein a non-aqueous printing ink containing a solvent having a solubility parameter in the range of 3 to 20 (cal / cm 3 ) 0.5 is used. Printing ink composition. 【請求項８】 印刷インキ用艶消し剤１００重量部に対
して、増粘剤を２〜５０重量部配合してなる請求項３〜
７のいずれか１項記載の印刷インキ組成物。8. The method according to claim 3, wherein 2 to 50 parts by weight of a thickener is mixed with 100 parts by weight of the matting agent for printing ink.
8. The printing ink composition according to any one of items 7 to 7. 【請求項９】 増粘剤が平均粒子径０．１〜１０μmの
シリカである請求項８記載の印刷インキ組成物。9. The printing ink composition according to claim 8, wherein the thickener is silica having an average particle diameter of 0.1 to 10 μm. 【請求項１０】 請求項３〜９のいずれか１項記載の印
刷インキ組成物を含むオフセット印刷用インキ。10. An offset printing ink comprising the printing ink composition according to claim 3. Description: 【請求項１１】 請求項３〜９のいずれか１項記載の印
刷インキ組成物を含むグラビア印刷用インキ。A gravure printing ink comprising the printing ink composition according to any one of claims 3 to 9. 【請求項１２】 請求項３〜９のいずれか１項記載の印
刷インキ組成物を含む凸版印刷用インキ。A letterpress printing ink comprising the printing ink composition according to any one of claims 3 to 9. 【請求項１３】 請求項３〜９のいずれか１項記載の印
刷インキ組成物を含むスクリーン印刷用インキ。13. A screen printing ink comprising the printing ink composition according to claim 3. Description:
JP2000039763A 1999-02-15 2000-02-14 Matting agent for printing ink, printing ink composition comprising the same and its use Pending JP2001089689A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2000039763A JP2001089689A (en) 1999-02-15 2000-02-14 Matting agent for printing ink, printing ink composition comprising the same and its use

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
JP3570799 1999-02-15
JP4841599 1999-02-25
JP11-35707 1999-07-19
JP11-48415 1999-07-19
JP20518899 1999-07-19
JP11-205188 1999-07-19
JP2000039763A JP2001089689A (en) 1999-02-15 2000-02-14 Matting agent for printing ink, printing ink composition comprising the same and its use

Publications (1)

Publication Number Publication Date
JP2001089689A true JP2001089689A (en) 2001-04-03

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Country Link
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006070236A (en) * 2004-08-06 2006-03-16 Sakura Color Prod Corp Aqueous ink composition
JP2008163293A (en) * 2006-12-08 2008-07-17 Toyo Ink Mfg Co Ltd Active energy ray-curable overprint varnish composition, printed sheet and printed sheet molded article
JP2013006973A (en) * 2011-06-24 2013-01-10 Cbj Scratch:Kk White ink for scratch printing
US10368374B2 (en) 2013-01-30 2019-07-30 Qualcomm Incorporated PRACH-based proximity detection
WO2020203970A1 (en) * 2019-03-29 2020-10-08 株式会社Ｄｎｐファインケミカル Matting ink composition, layered body manufactured by using same, and method for manufacturing layered body

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6295366A (en) * 1985-10-15 1987-05-01 ゼロツクス　コ−ポレ−シヨン Preparation of inkject composition
JPH02283746A (en) * 1989-04-25 1990-11-21 Achilles Corp Delustering composition
JPH06179283A (en) * 1992-12-14 1994-06-28 Dainippon Printing Co Ltd Transfer film improved in film cutting properties of transfer layer
JPH10279878A (en) * 1997-03-31 1998-10-20 Nippon Paint Co Ltd Matte polyvinyl chloride sol coating composition and matte coated metal sheet

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6295366A (en) * 1985-10-15 1987-05-01 ゼロツクス　コ−ポレ−シヨン Preparation of inkject composition
JPH02283746A (en) * 1989-04-25 1990-11-21 Achilles Corp Delustering composition
JPH06179283A (en) * 1992-12-14 1994-06-28 Dainippon Printing Co Ltd Transfer film improved in film cutting properties of transfer layer
JPH10279878A (en) * 1997-03-31 1998-10-20 Nippon Paint Co Ltd Matte polyvinyl chloride sol coating composition and matte coated metal sheet

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006070236A (en) * 2004-08-06 2006-03-16 Sakura Color Prod Corp Aqueous ink composition
US8080098B2 (en) 2004-08-06 2011-12-20 Sakura Color Products Corporation Water-based ink composition
JP2008163293A (en) * 2006-12-08 2008-07-17 Toyo Ink Mfg Co Ltd Active energy ray-curable overprint varnish composition, printed sheet and printed sheet molded article
JP2013006973A (en) * 2011-06-24 2013-01-10 Cbj Scratch:Kk White ink for scratch printing
US10368374B2 (en) 2013-01-30 2019-07-30 Qualcomm Incorporated PRACH-based proximity detection
WO2020203970A1 (en) * 2019-03-29 2020-10-08 株式会社Ｄｎｐファインケミカル Matting ink composition, layered body manufactured by using same, and method for manufacturing layered body
JPWO2020203970A1 (en) * 2019-03-29 2021-04-30 株式会社Ｄｎｐファインケミカル Matte ink composition, laminates produced using it, and methods for producing laminates

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