JP3203726B2 - Vinyl chloride resin for granular paste - Google Patents
Vinyl chloride resin for granular pasteInfo
- Publication number
- JP3203726B2 JP3203726B2 JP684292A JP684292A JP3203726B2 JP 3203726 B2 JP3203726 B2 JP 3203726B2 JP 684292 A JP684292 A JP 684292A JP 684292 A JP684292 A JP 684292A JP 3203726 B2 JP3203726 B2 JP 3203726B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- particles
- chloride resin
- particle size
- paste
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は粉立ちが少なく、粉体流
動性が良く、しかも低粘度でかつ高剪断領域でも流動性
の良好なペーストゾルを調製することのできる顆粒状ペ
ースト用塩化ビニル系樹脂に係る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride for a granular paste capable of preparing a paste sol having little powderiness, good powder fluidity, low viscosity and good fluidity even in a high shear range. Related to resin.
【０００２】[0002]
【従来の技術】ペースト用塩化ビニル樹脂の粉立ち防
止、自動計量の目的で近年ペースト用塩化ビニル樹脂そ
のものを顆粒状にする試みがなされている。例えば、特
開平２−１３３４０９号公報にはペースト加工用塩化ビ
ニル樹脂の水性分散液を回転円盤式のアトマイザーを有
するスプレー乾燥機を用いて乾燥し、乾燥の際に回転円
盤の回転数と乾燥空気の温度及び湿度を調整して顆粒状
レジンを製造している。しかしながら、該方法では顆粒
の粒子径を大きくするために回転円盤の回転数を小さく
すると高温での乾燥が必要となり、得られる顆粒レジン
は固くなり、可塑剤中で容易に分散せず、ペーストゾル
は形成されない。一方、乾燥温度を低くすると乾燥が不
充分となり再度別の乾燥工程が必要になるという欠点が
ある。2. Description of the Related Art In recent years, attempts have been made to granulate a vinyl chloride resin for pastes in order to prevent powdering of the vinyl chloride resin for pastes and to automatically measure them. For example, Japanese Patent Application Laid-Open No. 2-133409 discloses that an aqueous dispersion of a vinyl chloride resin for paste processing is dried using a spray dryer having a rotary disk type atomizer. Temperature and humidity are adjusted to produce granular resin. However, in this method, when the rotation speed of the rotating disk is reduced to increase the particle diameter of the granules, drying at a high temperature is required, and the obtained granular resin becomes hard and does not easily disperse in a plasticizer, and the paste sol Is not formed. On the other hand, when the drying temperature is lowered, there is a disadvantage that the drying becomes insufficient and another drying step is required again.
【０００３】また、得られた顆粒レジンが可塑剤中で従
来のペースト加工用塩化ビニル樹脂粉末から得られるよ
うなペーストゾルになったとしても、該ゾルは粘度が高
く、粘度の経時的安定性も劣り、高剪断領域での流動性
が劣ったものとなる。また、微粉状ペースト加工用塩化
ビニル樹脂に液状凝集剤を混合した後に押出造粒機を通
して造粒し、得られた造粒物を流動乾燥機で乾燥する粒
状塩化ビニル樹脂の製造方法が特公昭４８−２３１８０
号公報に開示されている。Further, even if the obtained granular resin is converted into a paste sol as obtained from a conventional vinyl chloride resin powder for paste processing in a plasticizer, the sol has a high viscosity and the stability of the viscosity over time. And the fluidity in the high shear region is poor. In addition, a method for producing a granular vinyl chloride resin is disclosed in which a liquid coagulant is mixed with a vinyl chloride resin for fine powder paste processing, the mixture is granulated through an extrusion granulator, and the obtained granules are dried with a fluidized drier. 48-23180
No. 6,086,045.
【０００４】この方法では、新たな乾燥工程が必要にな
るとともに、製造される粒状塩化ビニル樹脂が塩化ビニ
ル樹脂微粒子のみを固めているので乾燥温度によっては
ペースト加工用に供することはできず、仮に可塑剤を混
合してペーストゾルになったとしても、その流動性は必
ずしも良いものではなく、また、経時的粘度安定性にも
問題が残った。これらペーストゾルでは、高速コーティ
ング、ロータリースクリーン印刷、スプレー塗布、ディ
ッピング等の用途に供することは難しく、改めて粘度、
流動性等の調整を必要としていた。[0004] In this method, a new drying step is required, and since the granular vinyl chloride resin to be produced solidifies only the fine particles of the vinyl chloride resin, it cannot be used for paste processing depending on the drying temperature. Even if a plasticizer is mixed to form a paste sol, its fluidity is not always good, and the viscosity stability with time remains a problem. It is difficult to use these paste sols for applications such as high-speed coating, rotary screen printing, spray coating, and dipping.
Adjustment of liquidity was required.
【０００５】[0005]
【発明が解決しようとする課題】本発明者らは、ペース
トゾル調製時に粉立ちが少なく、粉体流動性にすぐれて
自動計量が可能で、可塑剤中に分散したとき容易に低粘
度でかつ高剪断領域でも流動性の良好なペーストゾルを
与え、高速コーティング、ロータリースクリーン印刷、
スプレー塗布等の用途に適したペースト加工用塩化ビニ
ル系樹脂を得るべく鋭意検討した結果、乳化重合または
微細懸濁重合した後の水性分散液を噴霧乾燥して得られ
た塩化ビニル系樹脂そのものまたはある程度の大きさに
粉砕したものと、別途この樹脂を微粉砕したものとを特
定の割合で混合した後に顆粒状に固めたものが、上述の
目的を達成するのに最適であることを見い出し、本発明
を完成するに到った。DISCLOSURE OF THE INVENTION The present inventors have found that there is little powder at the time of preparation of a paste sol, powder flowability is excellent, and automatic weighing is possible. Gives paste sol with good fluidity even in high shear area, high speed coating, rotary screen printing,
As a result of intensive studies to obtain a vinyl chloride resin for paste processing suitable for applications such as spray coating, the vinyl chloride resin itself obtained by spray drying an aqueous dispersion after emulsion polymerization or fine suspension polymerization or What was pulverized to a certain size, and what was separately pulverized this resin was mixed at a specific ratio and then solidified into granules, was found to be optimal to achieve the above-mentioned object, The present invention has been completed.
【０００６】すなわち、本発明の目的は、ペーストゾル
に調製時に粉塵の発生が少なく、粉体流動性が良好でか
つ自動計量が可能であり、また可塑剤に容易に分散して
低粘度のかつ、高剪断領域においてでさえ良好な流動性
を有するペーストゾルを得ることのできる顆粒状ペース
ト用塩化ビニル系樹脂を提供するにある。That is, an object of the present invention is to produce a paste sol with less dust at the time of preparation, good powder flowability and automatic weighing, and easily dispersed in a plasticizer to have a low viscosity. Another object of the present invention is to provide a vinyl chloride resin for a granular paste capable of obtaining a paste sol having good fluidity even in a high shear region.
【０００７】[0007]
【課題を解決するための手段】しかして、本発明の要旨
は、次の塩化ビニル系樹脂粒子（Ａ）、（Ｂ）及び
（Ｃ）を主成分とする混合物が粒径５０〜３００μの球
形に、または直径３００〜３０００μの円柱状に固めら
れた顆粒状ペースト用塩化ビニル系樹脂に存する。 （Ａ）粒径５〜６５μの範囲の粒子（以下粒子（Ａ）という）１０〜９０重量％ （Ｂ）粒径３μ以下の微粒子（以下微粒子（Ｂ）という） ９０〜１０重量％ （Ｃ）（Ａ）及び（Ｂ）以外の粒径の粒子 ０〜１０重量％The gist of the present invention is that a mixture mainly composed of the following vinyl chloride resin particles (A), (B) and (C) has a spherical shape having a particle size of 50 to 300 μm. Or a vinyl chloride resin for a granular paste which is solidified into a columnar shape having a diameter of 300 to 3000 μm. (A) Particles having a particle size of 5 to 65 μm (hereinafter referred to as particles (A)) 10 to 90% by weight (B) Fine particles having a particle size of 3 μm or less (hereinafter referred to as fine particles (B)) 90 to 10% by weight (C) Particles having a particle size other than (A) and (B) 0 to 10% by weight
【０００８】本発明を詳細に説明する。本発明の顆粒状
ペースト用塩化ビニル系樹脂の一成分である粒子（Ａ）
は粒径が５〜３５μの範囲にあることが必要である。こ
のような粒子（Ａ）を製造するには、例えば乳化重合法
または微細懸濁重合法によって製造された塩化ビニル樹
脂または塩化ビニル共重合体の微粒子を含む塩化ビニル
系樹脂ラテックス（水性分散液）を噴霧乾燥することに
よって得られる。この粒子（Ａ）は、乾燥過程でラテッ
クス中に存在する塩化ビニル系樹脂の微細粒子同士がそ
の表面で融着し、噴霧粒子の表面張力と相俟って乾燥粒
子形状が通常球形となったものである。The present invention will be described in detail. Particles (A) which are one component of the vinyl chloride resin for granular paste of the present invention
Needs to have a particle size in the range of 5 to 35 μm. To produce such particles (A), for example, a vinyl chloride resin latex (aqueous dispersion) containing fine particles of a vinyl chloride resin or a vinyl chloride copolymer produced by an emulsion polymerization method or a fine suspension polymerization method By spray drying. In the particles (A), the fine particles of the vinyl chloride resin present in the latex in the drying process are fused together at the surface thereof, and the dry particle shape is usually spherical in combination with the surface tension of the spray particles. Things.
【０００９】噴霧乾燥に用いる噴霧機構は、回転円盤、
加圧ノズル、二流体ノズル等いかなるものでもよく、通
常回転円盤または二流体ノズルが用いられる。得られる
粒子（Ａ）の粒径は回転円盤の回転数、二流体ノズルの
口径、ラテックスの供給流量、乾燥風量及び温度によっ
て適宜所望の大きさに調節する。噴霧直後の粒子は、微
細粒子または大粒径粒子が含まれていることが多く、粒
径５μ未満及び６５μより大きい粒子を分級除去して用
いるのが、例えば顆粒状ペースト用塩化ビニル系樹脂製
造工程における、他の成分との混合割合を明確にできる
ので望ましい。また、噴霧直後の粒子を所望の粒径に揃
えるために粉砕することもあり、この場合は粉砕後に分
級操作が施される。The spray mechanism used for spray drying includes a rotating disk,
Any type of pressurizing nozzle, two-fluid nozzle, etc. may be used, and a rotating disk or a two-fluid nozzle is usually used. The particle size of the obtained particles (A) is appropriately adjusted to a desired size depending on the number of revolutions of the rotating disk, the diameter of the two-fluid nozzle, the supply flow rate of latex, the amount of drying air and the temperature. Particles immediately after spraying often contain fine particles or large-diameter particles, and it is preferable to classify and remove particles having a particle size of less than 5 μm and larger than 65 μm, for example, for producing a vinyl chloride resin for a granular paste. This is desirable because the mixing ratio with other components in the process can be clarified. In addition, the particles immediately after spraying may be pulverized in order to make the particles have a desired particle size. In this case, a classification operation is performed after the pulverization.
【００１０】噴霧乾燥の乾燥温度は、噴霧乾燥装置の出
口の気流温度で５０℃以上にするのが望ましく、上限は
８０℃迄が適当である。この乾燥温度条件は、顆粒状ペ
ースト用塩化ビニル系樹脂に可塑剤を混合してプラスチ
ゾルにしたとき、粒子（Ａ）の７０％以上を粒径５〜６
５μの大きさで残すためにも重要であり、高剪断領域で
の流動性を良好に保つ上からも望ましい乾燥条件であ
る。この乾燥温度で乾燥した粒子（Ａ）の圧裂強度は１
ｇ／mm2 以上、好ましくは５ｇ／mm2 以上の範囲にある
のが望ましい。圧裂強度が１ｇ／mm2 より小さい場合、
顆粒状ペースト用塩化ビニル系樹脂をプラスチゾルにし
た時高粘度となり易い。The drying temperature of the spray drying is desirably 50 ° C. or higher as the air flow temperature at the outlet of the spray drying apparatus, and the upper limit is suitably up to 80 ° C. The drying temperature conditions are such that when a plasticizer is mixed with a vinyl chloride resin for a granular paste to form a plastisol, 70% or more of the particles (A) have a particle size of 5 to 6;
It is also important to leave a size of 5 μm, which is a desirable drying condition from the viewpoint of maintaining good fluidity in a high shear region. The tear strength of the particles (A) dried at this drying temperature is 1
g / mm 2 or more, preferably 5 g / mm 2 or more. If the tear strength is less than 1 g / mm 2 ,
When a vinyl chloride resin for granular paste is used as a plastisol, it tends to have a high viscosity.
【００１１】また、粒子（Ａ）としてペースト混和用レ
ジンと称される塩化ビニル系樹脂粒子を使用することも
できる。ペースト混和用レジンは、通常塩化ビニルまた
はそれと共重合可能なコモノマーとの混合物を懸濁剤及
び乳化剤並びに油溶性重合触媒の存在下に重合して得ら
れ、個々の粒子は、多数の微粒子が互いに融着したもの
ではなく、単一の球形粒子である。この粒子は普通５〜
１００μの範囲のほぼ均一な粒径で得られるものであ
り、重合操作により６５μまでの粒子を製造して使用す
る。この粒子の圧裂強度は、少なくとも１０００ｇ／mm
2 以上を示す。ペースト混和用レジンを用いることによ
り、プラスチゾルでの粒子（Ａ）のほぐれという現象は
おこらず、プラスチゾルは低粘度であるとともに高剪断
領域での流動性も安定する。Further, as the particles (A), vinyl chloride resin particles called a resin for mixing a paste can be used. Paste admixture resins are usually obtained by polymerizing a mixture of vinyl chloride or a copolymerizable comonomer in the presence of a suspending agent, an emulsifier and an oil-soluble polymerization catalyst. It is not fused but a single spherical particle. These particles are usually
It is obtained with a substantially uniform particle size in the range of 100μ. Particles of up to 65μ are produced and used by a polymerization operation. The breaking strength of the particles is at least 1000 g / mm
Indicates 2 or more. By using the resin for paste mixing, the phenomenon of loosening of the particles (A) in the plastisol does not occur, and the plastisol has low viscosity and stable fluidity in the high shear region.
【００１２】顆粒状ペースト用塩化ビニル系樹脂の成
分、微粒子（Ｂ）は、３μよりも小さい粒径をもつもの
であり、通常乳化重合法または微細懸濁重合法によって
製造された塩化ビニル系樹脂ラテックスを噴霧乾燥し、
得られた塩化ビニル系樹脂を粉砕機、例えばマイクロア
トマイザーで微粉砕し、粒径３μよりも大きい粒子を分
級除去して用いられる。また、微粒子（Ｂ）は、塩化ビ
ニル系ラテックスを噴霧乾燥することなく、該ラテック
スと上述の粒子（Ａ）とを混合し、粒子（Ａ）にラテッ
クス中の微細塩化ビニル系樹脂を吸着または合体した状
態で乾燥し、すなわち粒子（Ａ）に付着した状態で形成
してもよい。The fine particles (B), a component of the vinyl chloride resin for a granular paste, have a particle size smaller than 3 μm, and are usually produced by an emulsion polymerization method or a fine suspension polymerization method. Spray dry latex,
The obtained vinyl chloride resin is finely pulverized with a pulverizer, for example, a micro atomizer, and the particles having a particle size larger than 3 μm are classified and removed. The fine particles (B) are obtained by mixing the latex and the above-mentioned particles (A) without spray-drying the vinyl chloride-based latex, and adsorbing or combining the fine vinyl chloride-based resin in the latex with the particles (A). It may be formed in a dried state, that is, in a state of being attached to the particles (A).
【００１３】顆粒状ペースト用塩化ビニル系樹脂の成
分、粒子（Ｃ）は、粒子（Ａ）及び微粒子（Ｂ）と異な
る粒径の粒子を有するものであり、粒子（Ａ）及び微粒
子（Ｂ）を製造する工程で両粒子で規定する粒子径以外
の粒子（Ｃ）を完全に除去できず、それぞれの粒子に若
干の規定外の粒径のものを含む場合、または顆粒状ペー
スト用塩化ビニル系樹脂の製造工程で新たに両粒子の粒
径以外のものが生ずる可能性がある。この粒子を粒子
（Ｃ）と称する。The component, particles (C), of the vinyl chloride resin for a granular paste has particles having different particle diameters from the particles (A) and the fine particles (B), and the particles (A) and the fine particles (B) When the particles (C) having a particle size other than those defined by both particles cannot be completely removed in the step of producing, and each of the particles contains a particle having a slightly out-of-specification size, or a vinyl chloride system for a granular paste. There is a possibility that something other than the particle size of both particles may newly occur in the resin manufacturing process. These particles are referred to as particles (C).
【００１４】しかして、顆粒状ペースト用塩化ビニル系
樹脂のそれぞれ粒子の含有割合は、全塩化ビニル系樹脂
中、粒子（Ａ）が１０〜９０重量％、微粒子（Ｂ）が９
０〜１０重量％及び粒子（Ｃ）が０〜１０重量％の範囲
にあることが必要で、好ましくは粒子（Ａ）が２２〜７
８重量％、特に２５〜６０重量％、及び微粒子（Ｂ）が
７８〜２２重量％特に７５〜４０重量％の範囲であるこ
とが望ましく、プラスチゾルにしたとき明瞭な二山粒径
分布になるのが望ましい。顆粒状ペースト用塩化ビニル
系樹脂は、必要に応じ他の添加剤、例えば耐熱安定剤、
酸化防止剤、紫外線吸収剤、充填剤、着色剤、可塑剤等
が含有されていてもよい。Thus, the content ratio of each particle of the vinyl chloride resin for the granular paste is 10 to 90% by weight of the particles (A) and 9% of the fine particles (B) in the whole vinyl chloride resin.
The content of the particles (C) must be in the range of 0 to 10% by weight and the content of the particles (A) is preferably 22 to 7%.
It is desirable that the content of the fine particles (B) is in the range of 78 to 22% by weight, especially 75 to 40% by weight, and a clear bimodal particle size distribution is obtained when the plastisol is formed. Is desirable. Vinyl chloride resin for granular paste, if necessary, other additives, such as heat stabilizers,
An antioxidant, an ultraviolet absorber, a filler, a colorant, a plasticizer, and the like may be contained.
【００１５】本発明の顆粒状ペースト用塩化ビニル系樹
脂は、例えば次のようにして製造される。 （１）ラテックスを噴霧乾燥して得られた粒子（Ａ）を
乳化重合または微細懸濁重合の微細塩化ビニル系樹脂粒
子を含むラテックスに所定量混合した分散液とし、これ
を粒径５０〜３００μの範囲になるように噴霧乾燥す
る。乾燥温度は、噴霧乾燥装置出口付近で４５〜５５℃
程度が適当であり、得られる顆粒状ペースト用塩化ビニ
ル系樹脂は球形を呈する。 （２）ペースト混和用レジンを粒子（Ａ）とし、これを
上述（１）と同様にして噴霧乾燥して球形の顆粒状ペー
スト用塩化ビニル系樹脂とする。The vinyl chloride resin for a granular paste of the present invention is produced, for example, as follows. (1) A dispersion in which a predetermined amount of particles (A) obtained by spray-drying a latex is mixed with a latex containing fine vinyl chloride resin particles of emulsion polymerization or fine suspension polymerization to obtain a dispersion having a particle size of 50 to 300 μm. Spray-dry so that it falls within the range. Drying temperature is 45-55 ° C near the outlet of the spray dryer.
The degree is appropriate, and the obtained vinyl chloride resin for granular paste has a spherical shape. (2) The resin for paste mixing is made into particles (A), which are spray-dried in the same manner as in the above (1) to obtain spherical vinyl chloride resin for granular paste.
【００１６】（３）噴霧乾燥した粒子（Ａ）またはペー
スト混和用レジンをラテックスに混合して固形分濃度７
０％以上のウェットケーキまたはウェットパウダーと
し、これを押出機を用いて５０℃以下の温度で直径３０
０〜３０００μの円柱に押出し、一定寸法に切断した後
棚段式または流動式等の乾燥機を用いて５０℃以下の温
度で乾燥する。真空乾燥を採用してもよい。 （４）粒子（Ａ）及び微粒子（Ｂ）それぞれを所定割合
で配合し、必要に応じて水、アルコール、可塑剤、界面
活性剤等の湿潤剤を均一に混合してウェットケーキ、ウ
ェットパウダーとし、上述（３）と同様にして押出し、
顆粒状ペースト用塩化ビニル系樹脂とする。 （５）上述（３）または（４）のウェットケーキまたは
ウェットパウダーを粒径５０μ以上の大きさに転動造粒
し、得られた造粒物を乾燥する。(3) Spray-dried particles (A) or a resin for mixing a paste are mixed with latex to obtain a solid content of 7%.
0% or more of a wet cake or wet powder, and this is extruded at a temperature of 50 ° C. or less using an extruder at a diameter of 30% or less.
It is extruded into a cylinder of 0 to 3000 μm, cut into a certain size, and then dried at a temperature of 50 ° C. or less using a dryer of a tray type or a flow type. Vacuum drying may be employed. (4) Each of the particles (A) and the fine particles (B) is blended in a predetermined ratio, and if necessary, a wetting agent such as water, alcohol, plasticizer, and surfactant is uniformly mixed to obtain a wet cake or wet powder. Extruded in the same manner as in (3) above,
Vinyl chloride resin for granular paste. (5) The wet cake or wet powder of the above (3) or (4) is tumbled and granulated to a particle size of 50 μm or more, and the obtained granules are dried.
【００１７】このようにして製造された顆粒状ペースト
用塩化ビニル系樹脂は、その圧裂強度１０〜６０ｇ／mm
2 、好ましくは２０〜５０ｇ／mm2 の範囲にあるのが好
ましい。圧裂強度が１０ｇ／mm2 であれば顆粒が移送、
輸送中に壊れ易く、包装時及び開袋時に粉立ちが多い。
逆に６０ｇ／mm2 よりも大きければ、粉体流動性は良好
であるが、プラスチゾル調製時、可塑剤と混合しても顆
粒が崩壊せず、プラスチゾルを形成しないかまたは良好
なプラスチゾルとはならない。The vinyl chloride resin for granular paste thus produced has a tear strength of 10 to 60 g / mm.
2 and preferably in the range of 20 to 50 g / mm 2 . If the crushing strength is 10 g / mm 2 , the granules are transferred,
It is fragile during transportation and has a lot of dust at the time of packaging and opening of bags.
Conversely, if it is larger than 60 g / mm 2 , the powder fluidity is good, but the granules do not disintegrate even if mixed with a plasticizer during plastisol preparation, do not form a plastisol or do not become a good plastisol .
【００１８】[0018]
【実施例】次に本発明を実施例にて詳述するが、本発明
は、その要旨を超えない限り、以下の実施例に限定され
るものではない。なお、顆粒状ペースト用塩化ビニル系
樹脂、粒子（Ａ）、粒子形状、圧裂強度、粉体流動性、
粉立ち性、プラスチゾルの粘度等は次のように測定し
た。Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. In addition, vinyl chloride resin for granular paste, particles (A), particle shape, tear strength, powder fluidity,
The powdering property, the viscosity of plastisol, etc. were measured as follows.
【００１９】１ 粒径の測定 ａ）ラテックス中の粒径 遠心沈降式粒径測定機 ＣＰＳＭ（ＴＥＣＨＮＩＤＹＮ
Ｅ社製）により測定 ｂ）乾燥品の粒径 レーザー回折式粒径測定装置（堀場製作所製ＬＡ−５０
０）を用いて測定 ｃ）顆粒レジンの粒径 上記ｂ）と同じ。但し、粒径２００μを超える場合タイ
ラー篩を使用 ２ 粒子形状 走査型電子顕微鏡（ＳＥＭ）を用いて観察1) Measurement of particle size a) Particle size in latex Centrifugal sedimentation type particle size analyzer CPSM (TECHNIDYN)
B) Particle size of dried product Laser diffraction particle size analyzer (LA-50 manufactured by Horiba, Ltd.)
Measured using 0) c) Particle size of granular resin Same as b) above. However, if the particle size exceeds 200μ, use a Tyler sieve. 2 Particle shape Observed using a scanning electron microscope (SEM)
【００２０】３ 圧裂強度 微小圧縮試験機（島津製作所製、ＭＣＴＭ−５００）を
用い、塩化ビニル樹脂の凝集粒子１個をゆっくり荷重を
かけて圧縮し、急激な変化を起す荷重値を求める。急激
な荷重変化で粒子の圧裂が分る。粒子段面積当りの荷重
値（ｇ／mm2 ）を粒子１０個の平均でもって圧裂強度を
示した。 ４ 粉体流動性 パウダーテスター（細川粉体研究所製）を用い、安息角
を測定。 ５ 粉立ち性 １ｍ高さのメスシリンダーの上から１００ｇの顆粒レジ
ンを一度に落下させ、落下直後の粉煙の高さで評価し
た。 ◎印： 粉煙 ０cm ○印： 粉煙 ５０cm未満 △印： 粉煙 ５０〜１００cm ×印： 粉煙 １００cm超3 Compression strength Using a microcompression tester (MCTM-500, manufactured by Shimadzu Corporation), a single agglomerated particle of a vinyl chloride resin is slowly applied with a load to compress it, and a load value that causes a sudden change is determined. A sudden change in load reveals cracking of the particles. The load value (g / mm 2 ) per particle stage area was taken as the average of 10 particles to show the tear strength. 4 Powder flowability The angle of repose was measured using a powder tester (manufactured by Hosokawa Powder Research Laboratory). 5 Powdering property 100 g of granular resin was dropped at once from the top of a 1-meter-high measuring cylinder, and evaluated by the height of powder smoke immediately after falling. ◎ mark: powder dust 0 cm ○ mark: powder dust less than 50 cm △ mark: powder dust 50-100 cm × mark: powder dust more than 100 cm
【００２１】６ プラスチゾルの粘度 （ａ）初期粘度： 塩化ビニル樹脂／可塑剤＝１００／
６０（重量部）をプラネタリーミキサ（Ｎ−５０型）で
♯１スピード（６１rpm)×５分及び♯２スピード（１２
５rpm)×１５分混合して調製したプラスチゾルのブルッ
クフィールド型粘度計（Ｂ型粘度計）５０rpm 時の２３
℃での数値 （ｂ）経時粘度： 上述ゾルを２３℃で２４時間保持し
た後に（ａ）と同様に測定した数値 （ｃ）高剪断時の粘度： シーバース型粘度計（Ｓ型粘
度計）を用い、上述ゾルの９０psi 加圧下における１０
０秒間あたりの流出量（単位：ｇ）6 Viscosity of plastisol (a) Initial viscosity: vinyl chloride resin / plasticizer = 100 /
60 (parts by weight) using a planetary mixer (N-50 type) at # 1 speed (61 rpm) x 5 minutes and at # 2 speed (12
5 rpm) × 23 minutes of plastisol prepared by mixing for 15 minutes, Brookfield viscometer (B-type viscometer) at 50 rpm
Numerical value at ° C. (b) Viscosity over time: Numerical value measured in the same manner as (a) after holding the above sol at 23 ° C. for 24 hours. (C) Viscosity at high shear: A Seaverse type viscometer (S type viscometer) Of the above sol under pressure of 90 psi.
Outflow rate per 0 second (unit: g)
【００２２】実施例 塩化ビニル系樹脂粒子（Ａ）の製造法： ＜粒子（Ａ）−１〜３＞ （種子重合体ラテックスの調製）攪拌機を備えた容積２
００ｌの重合槽に９０kgの温度５４℃の脱イオン水、１
０ｇの過硫酸カリウム及び５０ｇのピロ亜硫酸ナトリウ
ムを入れ、約２０分攪拌して溶解させた後、重合槽内を
−６１０mmＨｇまで減圧し、５５℃で５０分間保持し
た。Example Production method of vinyl chloride resin particles (A): <Particles (A) -1 to 3> (Preparation of seed polymer latex) Volume 2 equipped with a stirrer
90 kg of deionized water at a temperature of 54 ° C.
After adding 0 g of potassium persulfate and 50 g of sodium pyrosulfite and stirring and dissolving for about 20 minutes, the pressure in the polymerization vessel was reduced to -610 mmHg and kept at 55 ° C. for 50 minutes.
【００２３】次いで、重合槽に６０kgの塩化ビニルを仕
込み、槽内温度を５０℃に昇温した。塩化ビニル仕込後
１５分経過してから、予め溶解しておいた０．２％過硫
酸カリウム水溶液を約１０ｍｌ／分の割合で徐々に添加
し、以後一定の重合速度を保つように、過硫酸カリウム
溶液の添加速度を制御しながら反応させ、重合率が約１
５％に達したときに、別途溶解しておいたラウリル硫酸
ナトリウム水溶液の添加を開始し、同水溶液を８０ｍｌ
／１０分前後の速度で全ラウリル硫酸ナトリウム添加量
が３６０ｇになるまで添加した。槽内圧力が５０℃での
塩化ビニルの飽和圧から２．０kg／cm2 降下したときに
反応を停止し、未反応塩化ビニルを回収して平均粒径が
０．５μの種子重合体粒子を含むラテックスを得た。Next, 60 kg of vinyl chloride was charged into the polymerization tank, and the temperature in the tank was raised to 50 ° C. 15 minutes after charging vinyl chloride, a 0.2% aqueous potassium persulfate solution previously dissolved was gradually added at a rate of about 10 ml / min. The reaction is performed while controlling the addition rate of the potassium solution, and the polymerization rate is about 1
When the amount reaches 5%, the addition of the separately dissolved aqueous sodium lauryl sulfate solution is started, and the aqueous solution is added to 80 ml.
/ 10 minutes until the total amount of sodium lauryl sulfate added reached 360 g. The reaction was stopped when the pressure in the tank dropped 2.0 kg / cm 2 from the saturation pressure of vinyl chloride at 50 ° C., unreacted vinyl chloride was recovered, and seed polymer particles having an average particle size of 0.5 μm were collected. A latex containing latex was obtained.
【００２４】（重合体ラテックスの調製）攪拌機を備え
た容量２００ｌの重合槽に、脱イオン水８０kg、重合体
種子として前記のように調製した平均粒径０．５μの重
合体粒子を含むラテックスを固形分換算量で４．５kg仕
込んだ後に脱気して塩化ビニル２５．５kgを加えた。次
いで温度を５７℃に昇温させた後、全量で０．０５％
（対塩化ビニル）の過酸化水素−ホルムアルデヒドナト
リウムスルホキシレートのレドックス系重合開始剤を、
一定の反応速度が保たれるように連続的に添加した。(Preparation of Polymer Latex) In a 200-liter polymerization tank equipped with a stirrer, 80 kg of deionized water and a latex containing polymer particles having an average particle diameter of 0.5 μm and prepared as a polymer seed as described above were placed. After charging 4.5 kg in terms of solid content, the mixture was degassed and 25.5 kg of vinyl chloride was added. Then, after raising the temperature to 57 ° C., the total amount was 0.05%.
A redox polymerization initiator of hydrogen peroxide-formaldehyde sodium sulfoxylate (vs. vinyl chloride)
It was added continuously so as to maintain a constant reaction rate.
【００２５】さらに重合率が重合体種子と塩化ビニルの
合計量の１０％に達した時点から重合完了までの間、重
合用乳化剤としてラウリル硫酸ナトリウムの８％水溶液
を塩化ビニルに対して純分換算で毎時０．１％の割合で
連続的に添加した。また反応率が１５％に達した時点か
ら全量で７０kgの塩化ビニルを１２kg／２０分の割合で
添加した。重合圧が５７℃における塩化ビニルの飽和圧
力から１kg／cm2 降下した時に開始剤の添加を停止して
重合を停止させ、未反応塩化ビニルを回収した。得られ
たラテックスは、平均粒径０．９μの重合体粒子を含
み、固形分濃度３９．６重量％であった。このラテック
スを限外濾過により固形分濃度４３．６重量％まで濃縮
した。Further, from the time when the polymerization rate reaches 10% of the total amount of the polymer seed and the vinyl chloride to the completion of the polymerization, an 8% aqueous solution of sodium lauryl sulfate as a polymerization emulsifier is converted to a pure content of vinyl chloride. At a rate of 0.1% per hour. When the conversion reached 15%, a total of 70 kg of vinyl chloride was added at a rate of 12 kg / 20 minutes. When the polymerization pressure dropped 1 kg / cm 2 from the saturation pressure of vinyl chloride at 57 ° C., the addition of the initiator was stopped to stop the polymerization, and unreacted vinyl chloride was recovered. The resulting latex contained polymer particles having an average particle size of 0.9 μm and had a solid content concentration of 39.6% by weight. This latex was concentrated by ultrafiltration to a solid concentration of 43.6% by weight.
【００２６】この濃縮ラテックスを噴霧乾燥装置、回転
円盤（出口温度５５℃）及び二流体ノズル（出口温度６
０℃）を用いて噴霧乾燥を行ない、それぞれ平均粒径６
０μ及び３０μの粒子（Ａ）−１及び粒子（Ａ）−２を
得た。また、粒子（Ａ）−１をマイクロアトマイザーで
粉砕し、極力微粒子を除去し、平均粒径５μの粒子
（Ａ）−３を得た。これら粒子（Ａ）のそれぞれの圧裂
強度及び見掛け密度を表１に示した。 ＜粒子（Ａ）−４＞また、市販の平均粒径３５μのペー
スト混和用レジン（三菱化成ビニル社製；ビニカ７５Ｂ
Ｘ）を（Ａ）−４として表１に併記した。The concentrated latex is spray-dried, a rotating disk (outlet temperature 55 ° C.) and a two-fluid nozzle (outlet temperature 6 ° C.).
0 ° C.) and spray dried using an average particle size of 6
Particles (A) -1 and (A) -2 of 0 μ and 30 μ were obtained. Further, the particles (A) -1 were pulverized with a micro atomizer to remove the fine particles as much as possible, thereby obtaining particles (A) -3 having an average particle diameter of 5 µm. Table 1 shows the crushing strength and apparent density of each of these particles (A). <Particle (A) -4> A commercially available paste mixing resin having an average particle diameter of 35 μm (manufactured by Mitsubishi Kasei Vinyl Co .; Binica 75B)
X) is also shown in Table 1 as (A) -4.
【００２７】[0027]
【表１】 [Table 1]
【００２８】顆粒レジンの製造法：上述重合ラテックス
の調製で製造された０．９μの微粒子を含む固形分４
３．６重量％の濃縮ラテックスを微粒子（Ｂ）として用
い、表２に示す配合割合で粒子（Ａ）及び微粒子（Ｂ）
を配合し、得られた分散液またはウェットケーキをそれ
ぞれ噴霧乾燥（出口温度５０℃）及び押出造粒（小径造
粒機ファインディスクペレッター、不二パウダル製）を
行った。押出造粒を行ったものは４５℃の温度で静置乾
燥を行った。得られた顆粒レジンの諸物性を表２に示し
た。Production method of granular resin: solid content 4 containing 0.9 μ fine particles produced in the preparation of the polymerized latex described above
Using the concentrated latex of 3.6% by weight as the fine particles (B), the particles (A) and the fine particles (B) were mixed at the compounding ratio shown in Table 2.
Was spray-dried (outlet temperature: 50 ° C.) and extruded (by a small-diameter granulator, Fine Disc Pelletter, manufactured by Fuji Paudal Co., Ltd.). The extruded granules were dried at 45 ° C. Table 2 shows the physical properties of the obtained granular resin.
【００２９】[0029]
【表２】 [Table 2]
【００３０】得られた顆粒状ペースト用塩化ビニル樹脂
のプラスチゾルでの粘度を測定し表３に示した。The viscosity of the obtained vinyl chloride resin for granular paste in a plastisol was measured and is shown in Table 3.
【００３１】[0031]
【表３】 [Table 3]
【００３２】[0032]
【発明の効果】本発明の顆粒状ペースト用塩化ビニル系
樹脂は、径５０μ以上の大きさを有する球状または円柱
状の顆粒であるので、粉体流動性が良好で、包装及びペ
ースト調製時に自動計量が可能になり、その際粉塵の発
生も従来のペーストレジンに比較して著しく少なくなっ
た。また該顆粒状樹脂は、大粒子及び微細粒子が一緒に
固められているので、該顆粒状樹脂を単に可塑剤中で攪
拌するだけで容易に微細粒子中に大粒子が均一に分散し
た状態のペーストゾルとなり、得られたゾルは低粘度で
あり、経時的粘度安定性が良好でかつ高剪断領域でのゾ
ル流動性にも優れている。したがって、従来のようにペ
ーストゾル調製時に行う粘度調整、ゾル流動性の調整等
の操作は不要になる。そして、このようにして調製され
たペーストゾルは、高速コーティングを可能にし、また
ロータリースクリーン印刷に用いた場合にはゾルの糸引
きがなく、シャープな模様印刷が可能である。Industrial Applicability The vinyl chloride resin for granular paste of the present invention is a spherical or cylindrical granule having a diameter of 50 μ or more, so that it has good powder fluidity and can be used automatically during packaging and paste preparation. Weighing became possible, and the generation of dust was significantly reduced as compared with the conventional paste resin. In addition, since the granular resin has large particles and fine particles solidified together, it is easy to simply stir the granular resin in a plasticizer to easily disperse the large particles in the fine particles. It becomes a paste sol, and the obtained sol has low viscosity, good viscosity stability over time, and excellent sol fluidity in a high shear region. Therefore, it is not necessary to perform operations such as viscosity adjustment and sol fluidity adjustment at the time of preparing the paste sol as in the related art. The paste sol thus prepared enables high-speed coating, and when used for rotary screen printing, has no stringiness of the sol and enables sharp pattern printing.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) B29B 9/00 - 9/16 C08J 3/12 - 3/16 ──────────────────────────────────────────────────続 き Continuation of front page (58) Field surveyed (Int. Cl. 7 , DB name) B29B 9/00-9/16 C08J 3/12-3/16
Claims (6)
（Ｂ）及び（Ｃ）を主成分とする混合物が粒径５０〜３
００μの球状に、または直径３００〜３０００μの円柱
状に固められた顆粒状ペースト用塩化ビニル系樹脂。 （Ａ）粒径５〜６５μの範囲の粒子（以下粒子（Ａ）という）１０〜９０重量％ （Ｂ）粒径３μ以下の微粒子（以下微粒子（Ｂ）という） ９０〜１０重量％ （Ｃ）（Ａ）及び（Ｂ）以外の粒径の粒子 ０〜１０重量％1. The following vinyl chloride resin particles (A):
The mixture containing (B) and (C) as main components has a particle size of 50 to 3
A vinyl chloride resin for a granular paste, which is solidified into a spherical shape of 00 μm or a columnar shape having a diameter of 300 to 3000 μm. (A) Particles having a particle size of 5 to 65 μm (hereinafter referred to as particles (A)) 10 to 90% by weight (B) Fine particles having a particle size of 3 μm or less (hereinafter referred to as fine particles (B)) 90 to 10% by weight (C) Particles having a particle size other than (A) and (B) 0 to 10% by weight
求項１記載の顆粒状ペースト用塩化ビニル系樹脂。2. The vinyl chloride resin for a granular paste according to claim 1, which has a tear strength of 10 to 60 g / mm 2 .
０重量部及び可塑剤６０重量部からプラスチゾルを調製
する際、プラネタリーミキサ（Ｎ−５０型）で♯１スピ
ード（６１rpm)×５分、♯２スピード（１２５rpm)×１
５分混合したとき、当該ゾル中に粒径１００μ以上の未
分散粒子を含まない請求項１または請求項２記載の顆粒
状ペースト用塩化ビニル系樹脂。3. A vinyl chloride resin 10 for a granular paste.
When preparing a plastisol from 0 parts by weight and 60 parts by weight of a plasticizer, a planetary mixer (N-50 type) was used at a speed of 1 rpm (61 rpm) for 5 minutes and a speed of 2 rpm (125 rpm) for 1 minute.
The vinyl chloride resin for a granular paste according to claim 1 or 2, wherein the sol does not contain undispersed particles having a particle size of 100 µ or more when mixed for 5 minutes.
５〜６５μの範囲で７０重量％以上残る請求項３記載の
顆粒状ペースト用塩化ビニル系樹脂。4. The vinyl chloride resin for a granular paste according to claim 3, wherein at least 70% by weight of the component (A) remains in the plastisol in a range of 5 to 65 μm in particle size.
である請求項１記載の顆粒状ペースト用塩化ビニル系樹
脂。5. The vinyl chloride resin for a granular paste according to claim 1, wherein the component (A) is a resin for mixing a paste.
（Ｂ）と同一である請求項１記載の顆粒状ペースト用塩
化ビニル系樹脂。6. The vinyl chloride resin for a granular paste according to claim 1, wherein the chemical composition of the component (A) is the same as that of the fine particles (B).
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP684292A JP3203726B2 (en) | 1992-01-17 | 1992-01-17 | Vinyl chloride resin for granular paste |
| ES93100485T ES2132144T3 (en) | 1992-01-17 | 1993-01-14 | VINYL CHLORIDE GRANULAR RESIN. |
| DE69324510T DE69324510T2 (en) | 1992-01-17 | 1993-01-14 | Granular vinyl chloride resin |
| EP93100485A EP0553653B1 (en) | 1992-01-17 | 1993-01-14 | Granular vinyl chloride resin |
| US08/221,456 US5554707A (en) | 1992-01-17 | 1994-04-01 | Granular vinyl chloride resin and process for its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP684292A JP3203726B2 (en) | 1992-01-17 | 1992-01-17 | Vinyl chloride resin for granular paste |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05194752A JPH05194752A (en) | 1993-08-03 |
| JP3203726B2 true JP3203726B2 (en) | 2001-08-27 |
Family
ID=11649501
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP684292A Expired - Fee Related JP3203726B2 (en) | 1992-01-17 | 1992-01-17 | Vinyl chloride resin for granular paste |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3203726B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4526843B2 (en) * | 2004-03-19 | 2010-08-18 | 新第一塩ビ株式会社 | Vinyl chloride resin particles for paste and composition thereof |
-
1992
- 1992-01-17 JP JP684292A patent/JP3203726B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05194752A (en) | 1993-08-03 |
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