JP2009068024A - Process for production of vinyl chloride resin for paste - Google Patents
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本発明は、発泡性に優れるペースト用塩化ビニル樹脂及びその製造方法に関するものであり、更に詳しくは、ペースト用塩化ビニル樹脂を発泡加工する際、配合時の可塑剤の種類、量、充填剤量に関わらず、発泡体の表面平滑性に優れ、緻密なセル構造を有し、凹凸模様を施す際の発泡体の再加熱において発泡体の厚み減少が少なく、ボリューム感のある発泡成形体を提供するペースト用塩化ビニル樹脂、その製造方法及びそれよりなるペースト用塩化ビニル樹脂組成物に関するものである。 The present invention relates to a vinyl chloride resin for paste excellent in foamability and a method for producing the same, and more specifically, when foaming a vinyl chloride resin for paste, the type, amount, and amount of filler at the time of blending Regardless of the foam surface, it has excellent surface smoothness, has a dense cell structure, and provides a foamed molded product with a sense of volume with little reduction in the thickness of the foam during reheating of the foam when applying an uneven pattern. The present invention relates to a vinyl chloride resin for paste, a method for producing the same, and a vinyl chloride resin composition for paste comprising the same.
ペースト用塩化ビニル樹脂は、可塑剤、安定剤、発泡剤等の配合剤と混練することにより、ペースト用塩ビゾルとして加工に供され種々の加工法により様々な成形品が得られる。その中で、壁紙、床材のような建築資材はペースト用塩化ビニル樹脂の主な用途の一つである。通常、壁紙、床材は、ペースト塩ビ用ゾルを難燃紙などの裏打ち材料にコーティング後、加熱し、発泡体とした後、さらにエンボスロールにより凹凸模様をつけることで製造される。その際、発泡体は、エンボスロールの模様を再現良く転写可能でエンボスロール通過後の発泡体の極端な厚み減少を起こさないような、表面が平滑で緻密なセル構造を有するものが望まれている。 The vinyl chloride resin for paste is kneaded with compounding agents such as a plasticizer, a stabilizer, and a foaming agent, so that it is subjected to processing as a vinyl chloride sol for paste, and various molded products can be obtained by various processing methods. Among them, building materials such as wallpaper and flooring are one of the main uses of vinyl chloride resin for paste. Usually, wallpaper and flooring materials are manufactured by coating paste PVC sol on a backing material such as flame retardant paper, heating to form a foam, and then applying an uneven pattern with an embossing roll. At that time, it is desirable that the foam has a smooth and dense cell structure that can transfer the pattern of the embossing roll with good reproducibility and does not cause an extreme reduction in the thickness of the foam after passing through the embossing roll. Yes.
最近、壁紙、床材のような内装用建築資材においては、屋内環境問題への配慮から、高沸点の可塑剤を使用したり、充填剤を増量するなど配合の変更が活発に行われている。このような、配合の変化により、同一加工条件において発泡体表面の平滑性が損なわれたり、セルが肥大化するなどの問題が起こった。 In recent years, interior building materials such as wallpaper and flooring have been undergoing active changes in formulation, such as using high-boiling plasticizers or increasing the amount of fillers, in consideration of indoor environmental issues. . Due to such a change in the composition, problems such as deterioration of the smoothness of the foam surface under the same processing conditions and enlargement of the cells occurred.
これら、問題を解決する方法として、配合時にセル調整剤といわれるアクリル系ポリマーを添加する方法、ペースト用塩化ビニル樹脂の粒子径の分布を制御することによって発泡性を向上する方法等、が提案されている。 As methods for solving these problems, a method of adding an acrylic polymer called a cell regulator at the time of blending, a method of improving foamability by controlling the particle size distribution of the vinyl chloride resin for paste, and the like have been proposed. ing.
しかし、セル調整剤といわれるアクリル系ポリマーを添加する方法においては、配合費用のコストアップ、再加熱時の発泡体の厚み減少を抑制することが困難である等の問題を有している。また、ペースト用塩化ビニル樹脂の粒子径の分布を制御することによって発泡性を向上する方法においては、粒子径の分布を制御するだけでは良好な発泡体を得るためには限界を有するともに、粒子径分布の制御によってペースト用塩ビゾルの粘度上昇を伴うためにコーティングしづらくなるなど問題があった。 However, the method of adding an acrylic polymer called a cell modifier has problems such as an increase in the cost of blending and difficulty in suppressing a decrease in the thickness of the foam during reheating. In addition, in the method of improving foamability by controlling the particle size distribution of the vinyl chloride resin for paste, there is a limit to obtain a good foam only by controlling the particle size distribution. There is a problem that it becomes difficult to coat because the viscosity of the vinyl chloride sol for paste is increased by controlling the diameter distribution.
そこで、本発明はペースト用塩化ビニル樹脂を発泡加工する際、配合時の可塑剤の種類、量、充填剤量に関わらず、発泡体の表面平滑性に優れ、緻密なセル構造を有し、凹凸模様を施す際の発泡体の再加熱において発泡体の厚み減少が少なく、ボリューム感のある発泡成形体を提供するペースト用塩化ビニル樹脂、その製造方法及びそれよりなるペースト用塩化ビニル樹脂組成物を提供することを課題とするものである。 Therefore, when foaming vinyl chloride resin for paste, the present invention is excellent in surface smoothness of the foam regardless of the type and amount of the plasticizer at the time of blending, the amount of filler, and has a dense cell structure, A vinyl chloride resin for paste that provides a foamed molded article with a small volume reduction in reheating of the foam during the application of a concavo-convex pattern and a volume feeling, a method for producing the same, and a vinyl chloride resin composition for paste comprising the same It is a problem to provide.
本発明者らは、上記課題に関し鋭意検討した結果、特定のペースト用塩化ビニル樹脂を使用することにより、発泡体の表面平滑性に優れ、セル構造が緻密でかつ再加熱による厚み減少率が少ない発泡体が得られるとの知見に至り本発明を完成させるに至った。 As a result of intensive studies on the above problems, the present inventors have achieved excellent surface smoothness of the foam by using a specific vinyl chloride resin for paste, a dense cell structure, and a small thickness reduction rate due to reheating. It came to the knowledge that a foam was obtained and came to complete this invention.
即ち、本発明は、ペースト用塩化ビニル樹脂１００重量部に対し、可塑剤としてジ−２−エチルヘキシルフタレート６０重量部、充填剤として炭酸カルシウム７５重量部、バリウム−亜鉛系安定剤３重量部、発泡剤としてアゾジカーボンアミド４重量部、顔料として酸化チタン１５重量部をディスパーミキサーにより混練してペースト塩ビゾルとし、該ペースト塩ビゾルを難燃紙上に０．２５ｍｍの厚みでコーティングしセミゲル状のシートを作製し、該シートを室温まで冷却した後、２３０℃で４０秒加熱することにより得られた発泡体の表面が平滑で緻密なセル構造を成形するペースト用塩化ビニル樹脂であって、該発泡体を室温まで冷却した後、更に、該発泡体を２３０℃で１０秒再加熱した際、下記式（１）で示される発泡体の厚み減少率が１０％以下となることを特徴とするペースト用塩化ビニル樹脂、及びその製造方法に関するものである。 That is, the present invention relates to 100 parts by weight of vinyl chloride resin for paste, 60 parts by weight of di-2-ethylhexyl phthalate as a plasticizer, 75 parts by weight of calcium carbonate as a filler, 3 parts by weight of a barium-zinc stabilizer, foaming 4 parts by weight of azodicarbonamide as an agent and 15 parts by weight of titanium oxide as a pigment are kneaded with a disper mixer to form a paste vinyl chloride sol, and the paste vinyl chloride sol is coated on a flame retardant paper to a thickness of 0.25 mm. The sheet is cooled to room temperature, and then heated at 230 ° C. for 40 seconds to obtain a foamed vinyl chloride resin for molding a cell structure having a smooth and dense cell structure. After cooling the body to room temperature, when the foam is reheated at 230 ° C. for 10 seconds, the thickness of the foam represented by the following formula (1) Paste vinyl chloride resin low rate is characterized by comprising 10% or less, and a manufacturing method thereof.
厚み減少率（％）＝（２３０℃で１０秒の再加熱前の発泡体厚み（ｍｍ）−２３０℃で１０秒再加熱後の発泡体厚み（ｍｍ））／２３０℃で１０秒再加熱前の発泡体厚み（ｍｍ）×１００ （１）
以下に、本発明をより詳細に説明する。
Thickness reduction rate (%) = (foam thickness before reheating at 230 ° C. for 10 seconds (mm) −foam thickness after reheating at 230 ° C. for 10 seconds) / before reheating at 230 ° C. for 10 seconds Foam thickness (mm) × 100 (1)
Hereinafter, the present invention will be described in more detail.
本発明のペースト用塩化ビニル樹脂は、ペースト用塩化ビニル樹脂１００重量部に対し、可塑剤としてジ−２−エチルヘキシルフタレート６０重量部、充填剤として炭酸カルシウム７５重量部、バリウム−亜鉛系安定剤３重量部、発泡剤としてアゾジカーボンアミド４重量部、顔料として酸化チタン１５重量部をディスパーミキサーにより混練してペースト塩ビゾルとし、該ペースト塩ビゾルを難燃紙上に０．２５ｍｍの厚みでコーティングしセミゲル状のシートを作製し、該シートを室温まで冷却した後、２３０℃で４０秒加熱することにより得られる発泡体の表面が平滑で緻密なセル構造を形成するペースト用塩化ビニル樹脂であって、該発泡体を室温まで冷却した後、更に、該発泡体を２３０℃で１０秒再加熱した際、上記式（１）で示される発泡体の厚み減少率が１０％以下となるものである。そして、上記式（１）で示される発泡体の厚み減少率が１０％を超える場合、そのようなペースト用塩化ビニル樹脂より得られる発泡体は、ボリューム感を損なうものである。また、２３０℃で４０秒加熱することにより得られる発泡体の表面が平滑でない場合、又は、緻密なセル構造を形成しない場合、そのようなペースト用塩化ビニル樹脂より得られた発泡体は、意匠性が劣るものとなり好ましくない。 The vinyl chloride resin for paste of the present invention comprises 60 parts by weight of di-2-ethylhexyl phthalate as a plasticizer, 75 parts by weight of calcium carbonate as a filler, and barium-zinc stabilizer 3 with respect to 100 parts by weight of the vinyl chloride resin for paste. Part by weight, 4 parts by weight of azodicarbonamide as a foaming agent, and 15 parts by weight of titanium oxide as a pigment are kneaded with a disper mixer to form a paste vinyl chloride sol, and the paste vinyl chloride sol is coated on a flame retardant paper to a thickness of 0.25 mm. A vinyl chloride resin for paste that forms a semi-gel sheet, cools the sheet to room temperature, and heats at 230 ° C. for 40 seconds to form a smooth and dense cell structure on the surface of the foam. After cooling the foam to room temperature, when the foam is reheated at 230 ° C. for 10 seconds, the above formula (1) The foam thickness reduction rate of which is is made 10% or less. And when the thickness decreasing rate of the foam shown by said Formula (1) exceeds 10%, the foam obtained from such a vinyl chloride resin for pastes impairs a volume feeling. In addition, when the surface of the foam obtained by heating at 230 ° C. for 40 seconds is not smooth, or when a dense cell structure is not formed, the foam obtained from such a vinyl chloride resin for paste is a design. It becomes inferior in property and is not preferable.
本発明のペースト用塩化ビニル樹脂は、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（以下、塩化ビニル系単量体という。）よりなる塩化ビニル単独重合体または塩化ビニル系ランダム共重合体、塩化ビニル系ブロック共重合体、塩化ビニル系グラフト共重合体等の塩化ビニル系共重合体よりなるものである。 The vinyl chloride resin for paste of the present invention is a vinyl chloride monomer, or a mixture of vinyl chloride monomer and vinyl monomer copolymerizable with vinyl chloride monomer (hereinafter referred to as vinyl chloride monomer). A vinyl chloride homopolymer or a vinyl chloride random copolymer, a vinyl chloride block copolymer, a vinyl chloride graft copolymer, or the like.
ここで、塩化ビニル単量体と共重合可能なビニル単量体の具体例としては、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またはその無水物類；アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ブチル、マレイン酸エステル、フマル酸エステル、桂皮酸エステル類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る。また、本発明のペースト用塩化ビニル樹脂を共重合体とする場合、上記単量体を１種類以上で用いることが可能である。 Here, specific examples of the vinyl monomer copolymerizable with the vinyl chloride monomer include, for example, vinyl esters such as vinyl acetate, vinyl propionate, vinyl myristate, vinyl benzoate; acrylic acid, methacrylic acid , Unsaturated carboxylic acids such as maleic acid and fumaric acid or their anhydrides; methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, maleic acid ester, fumaric acid ester, Unsaturated carboxylic esters such as cinnamic acid esters; vinyl methyl ether, vinyl amyl ether, vinyl phenyl ethers; monoolefins such as ethylene, propylene, butene, pentene; vinylidene chloride, styrene and its derivatives, acrylonitrile, methacrylate List nitrile etc. Door can be. Moreover, when making the vinyl chloride resin for pastes of this invention into a copolymer, it is possible to use the said monomer by 1 or more types.
本発明でいう発泡体表面が平滑とは、発泡体表面に凹凸が少ないものであり、セル構造が緻密とは、セル径が小さく均一ということである。 The term “smooth foam surface” as used in the present invention means that the foam surface has few irregularities, and the dense cell structure means that the cell diameter is small and uniform.
本発明のペースト用塩化ビニル樹脂は、いかなる製造方法により製造してもよく、その中でも特に品質に優れたペースト用塩化ビニル樹脂を製造することが可能となることからシードミクロ懸濁重合法により製造することが好ましい。ここで、シードミクロ懸濁重合法とは、塩化ビニル単量体又は塩化ビニル系単量体を脱イオン水、乳化剤、必要に応じて高級アルコール等の乳化補助剤、油溶性重合開始剤をホモジナイザー等で混合分散した後、緩やかな攪拌下で重合を行うミクロ懸濁重合法によって得られた平均粒子径０．３〜０．７μｍの塩化ビニル系重合体粒子であるシード粒子を得る第一段階、該シード粒子と塩化ビニル単量体又は塩化ビニル系単量体を脱イオン水、乳化剤、必要に応じて高級アルコール等の乳化補助剤を緩やかな攪拌下で重合を行いシードを肥大化させる第二段階からなる重合方法である。該シードミクロ懸濁重合方法によって得られるペースト用塩化ビニル樹脂の平均粒子径は１〜２μｍであることが好ましい。 The vinyl chloride resin for paste of the present invention may be produced by any production method, and among them, it is possible to produce a vinyl chloride resin for paste having particularly excellent quality, and produced by a seed micro suspension polymerization method. It is preferable to do. Here, the seed micro-suspension polymerization method means that the vinyl chloride monomer or vinyl chloride monomer is deionized water, an emulsifier, an emulsification aid such as higher alcohol if necessary, and an oil-soluble polymerization initiator is a homogenizer. First step of obtaining seed particles, which are vinyl chloride polymer particles having an average particle size of 0.3 to 0.7 μm, obtained by a microsuspension polymerization method in which polymerization is performed with gentle stirring after mixing and dispersion The seed particles and vinyl chloride monomer or vinyl chloride monomer are polymerized with deionized water, an emulsifier, and, if necessary, an emulsification aid such as higher alcohol under gentle stirring to enlarge the seed. This is a two-stage polymerization method. The average particle size of the vinyl chloride resin for paste obtained by the seed microsuspension polymerization method is preferably 1 to 2 μm.
ここで、該シード粒子を得る第一段階での重合温度は、シード粒子内部に油溶性重合開始剤を効率的に残存できるように４０〜５５℃、特に４５〜５０℃であることが好ましく、第二段階の重合温度は、高い重合生産性を得るために６０〜７０℃、特に６２〜６８℃であることが好ましい。また、第二段階の重合時に、あらかじめ乳化重合において調整した粒子を該シード粒子とともに添加して重合を行っても差し支えない。更には、重合時に水溶性重合開始剤を併用しても良い。 Here, the polymerization temperature in the first stage to obtain the seed particles is preferably 40 to 55 ° C., particularly 45 to 50 ° C. so that the oil-soluble polymerization initiator can be efficiently left inside the seed particles. The polymerization temperature in the second stage is preferably 60 to 70 ° C., particularly 62 to 68 ° C. in order to obtain high polymerization productivity. In addition, during the second stage polymerization, it is possible to carry out the polymerization by adding particles prepared in advance in the emulsion polymerization together with the seed particles. Furthermore, you may use a water-soluble polymerization initiator together at the time of superposition | polymerization.
また、本発明のペースト用塩化ビニル樹脂を製造する際には、本発明のペースト用塩化ビニル樹脂が生産効率よく製造できることから下記一般式（２）で示される３−メルカプトプロピオン酸エステルを用いることが好ましい。 Moreover, when producing the vinyl chloride resin for pastes of the present invention, the 3-mercaptopropionic acid ester represented by the following general formula (2) should be used because the vinyl chloride resin for pastes of the present invention can be produced with high production efficiency. Is preferred.
このような３−メルカプトプロピオン酸エステルの添加量としては、特に生産効率よく発泡体としたときの色相に優れるペースト用塩化ビニル樹脂が製造できることから塩化ビニル単量体または塩化ビニル系単量体１００重量部に対し、０．００５〜０．２重量部が好ましく、特に０．０２５〜０．１重量部が好ましい。また、３−メルカプトプロピオン酸エステルの添加時期としては、シードミクロ懸濁重合法を採用した際には第二段階の重合の際に添加することが好ましく、その添加方法はいずれでもよいが、塩化ビニル単量体または塩化ビニル系単量体を仕込む前に、脱イオン水、乳化剤、必要に応じて使用される高級アルコール等の乳化補助剤と同時に、全量を一括で仕込むことが好ましい。なお、３−メルカプトプロピオン酸エステルは、少なくとも１種類用いればよいが、２種類以上を混合して使用しても差し支えない。 As the addition amount of such 3-mercaptopropionic acid ester, a vinyl chloride monomer for a paste or a vinyl chloride monomer 100 can be produced because a vinyl chloride resin for paste having excellent hue when producing a foam with particularly high production efficiency can be produced. 0.005-0.2 weight part is preferable with respect to weight part, and 0.025-0.1 weight part is especially preferable. Further, as the addition time of 3-mercaptopropionic acid ester, when the seed micro suspension polymerization method is adopted, it is preferably added during the second stage polymerization, and any addition method may be used. Prior to charging the vinyl monomer or vinyl chloride monomer, it is preferable to charge the whole amount together with an emulsification aid such as deionized water, an emulsifier, and a higher alcohol used if necessary. In addition, at least one kind of 3-mercaptopropionic acid ester may be used, but two or more kinds may be mixed and used.
ここでいう乳化剤とは、ペースト用塩化ビニル樹脂を製造する際に用いられる乳化剤でよく、例えばラウリル硫酸エステルナトリウム、ミリスチル硫酸エステルの如きアルキル硫酸エステル塩類；ドデシルベンゼンスルホン酸ナトリウム、ドデシルベンゼンスルホン酸カリウムの如きアルキルアリールスルホン酸塩類；ジオクチルスルホコハク酸ナトリウム、ジヘキシルスルホコハク酸ナトリウムの如きスルホコハク酸塩類；ラウリン酸アンモニウム、ステアリン酸カリウムの如き脂肪酸塩類；ポリオキシエチレンアルキル硫酸エステル塩類、ポリオキシエチレンアルキルアリール硫酸エステル塩類などのアニオン系乳化剤；ソルビタンモノオレート、ポリオキシエチレンソルビタンモノステアレートの如きソルビタンエステル類；ポリオキシエチレンアルキルフェニルエーテル類、ポリオキシエチレンアルキルエステル類などのノニオン系乳化剤などを１種類または２種類以上用いることができる。 The emulsifier here may be an emulsifier used in producing a vinyl chloride resin for pastes, for example, alkyl sulfate esters such as sodium lauryl sulfate and myristyl sulfate; sodium dodecylbenzenesulfonate, potassium dodecylbenzenesulfonate. Alkyl sulfonates such as sodium dioctyl sulfosuccinate, sulfosuccinates such as sodium dihexyl sulfosuccinate; fatty acid salts such as ammonium laurate and potassium stearate; polyoxyethylene alkyl sulfates, polyoxyethylene alkyl aryl sulfates Anionic emulsifiers such as salts; sorbitan esters such as sorbitan monooleate and polyoxyethylene sorbitan monostearate; polyoxy Alkylphenyl ethers, nonionic emulsifiers such as polyoxyethylene alkyl esters can be used one or two or more.
また、必要に応じて使用される乳化補助剤としては、例えばセチルアルコールおよびラウリルアルコール等の高級アルコール；ラウリン酸、パルミチン酸およびステアリン酸等の高級脂肪酸又はそのエステル；芳香族炭化水素、高級脂肪酸炭化水素、塩素化パラフィンのようなハロゲン化炭化水素等が挙げられる。 Examples of the emulsification aid used as necessary include higher alcohols such as cetyl alcohol and lauryl alcohol; higher fatty acids such as lauric acid, palmitic acid and stearic acid or esters thereof; aromatic hydrocarbons and higher fatty acid carbonization. Examples thereof include hydrogen and halogenated hydrocarbons such as chlorinated paraffin.
本発明のペースト用塩化ビニル樹脂は、表面平滑性に優れ、緻密なセル構造を有し、凹凸模様を施す際の発泡体の再加熱において発泡体の厚み減少が少なく、ボリューム感のある発泡成形体が得られることから、該ペースト塩化ビニル樹脂１００重量部に対し、可塑剤３０〜２００重量部、充填剤３００重量部以下、安定剤１〜１０重量部、発泡剤２〜２０重量部からなるペースト用塩化ビニル樹脂組成物とすることが好ましい。 The vinyl chloride resin for paste of the present invention has excellent surface smoothness, has a dense cell structure, has little foam thickness reduction during reheating of the foam when applying uneven patterns, and has a volumetric foam molding Since a body is obtained, it is composed of 30 to 200 parts by weight of a plasticizer, 300 parts by weight or less of a filler, 1 to 10 parts by weight of a stabilizer, and 2 to 20 parts by weight of a foaming agent with respect to 100 parts by weight of the paste vinyl chloride resin. It is preferable to use a vinyl chloride resin composition for paste.
この際の可塑剤としては、例えばジ−２−エチルヘキシルフタレート、ジイソノニルフタレート、ジブチルフタレート、ブチルベンジルフタレート、ジヘキシルフタレート、ジイソデシルフタレート等のフタル酸エステル系可塑剤；トリオクチルトリメリテート、ジオクチルアジペート、エポキシ化大豆油、エポキシ化脂肪酸エステル、塩素化脂肪酸エステル、リン酸トリス−β−クロルエチル、塩素化パラフィン等の可塑剤が挙げられ、これらの可塑剤は２種以上を混合して用いることもできる。 Examples of the plasticizer used here include phthalic acid ester plasticizers such as di-2-ethylhexyl phthalate, diisononyl phthalate, dibutyl phthalate, butyl benzyl phthalate, dihexyl phthalate, and diisodecyl phthalate; trioctyl trimellitate, dioctyl adipate, epoxy Plasticizers such as hydrogenated soybean oil, epoxidized fatty acid ester, chlorinated fatty acid ester, tris-β-chloroethyl phosphate, and chlorinated paraffin can be used, and these plasticizers can be used in combination of two or more.
また、安定剤としては、例えばエポキシ系安定剤、バリウム系安定剤、カルシウム系安定剤、スズ系安定剤、亜鉛系安定剤等が挙げられ、これらは１種類以上を併用することもできる。また、市販のカルシウム−亜鉛系（Ｃａ−Ｚｎ系）、バリウム−亜鉛系（Ｂａ−Ｚｎ系）等の複合安定剤を使用することもできる。そして、これら安定剤も添加量としては、ペースト用塩化ビニル樹脂１００重量部に対して、１〜１０重量部であることが好ましい。 Examples of the stabilizer include epoxy stabilizers, barium stabilizers, calcium stabilizers, tin stabilizers, zinc stabilizers, and the like, and one or more of these may be used in combination. Moreover, commercially available composite stabilizers such as calcium-zinc (Ca-Zn) and barium-zinc (Ba-Zn) can also be used. And it is preferable that these stabilizers also add 1-10 weight part with respect to 100 weight part of vinyl chloride resins for pastes.
発泡剤としては、例えば重炭酸ナトリウム、炭酸アンモニウム、重炭酸アンモニウム、亜硝酸アンモニウム、アミド化合物、ホウ水素化ナトリウム等の無機系発泡剤；イソシアネート化合物、アゾジカーボンアミド、アゾビスイソブチロニトリル、バリウムアゾジカルボキシレートらのアゾ化合物；ｐ，ｐ’−オキシビスベンゼンスルホニルヒドラジド、ｐ−トルエンスルホニルヒドラジドらのヒドラジン誘導体；セミカルバジド化合物；アジ化合物；ジニトロソペンタメチレンテトラミンらのニトロソ化合物；トリアゾール化合物等の有機系発泡剤が挙げられ、これらの各種発泡剤を２種以上組み合わせて使用することもできる。また、必要に応じて上記発泡体と亜鉛華（酸化亜鉛）等の分解促進剤を併用することも可能である。 Examples of the foaming agent include inorganic foaming agents such as sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, ammonium nitrite, amide compounds, sodium borohydride; isocyanate compounds, azodicarbonamide, azobisisobutyronitrile, barium Azo compounds such as azodicarboxylate; hydrazine derivatives such as p, p′-oxybisbenzenesulfonyl hydrazide and p-toluenesulfonyl hydrazide; semicarbazide compounds; azides; nitroso compounds such as dinitrosopentamethylenetetramine; An organic foaming agent is mentioned, These various foaming agents can also be used in combination of 2 or more types. Moreover, it is also possible to use together the said foam and decomposition accelerators, such as zinc white (zinc oxide), as needed.
さらに、充填剤としては、例えば炭酸カルシウム、ケイソウ土、炭酸マグネシウム、酸化チタン等が挙げられる。 Furthermore, examples of the filler include calcium carbonate, diatomaceous earth, magnesium carbonate, and titanium oxide.
本発明の製造方法で得られたペースト用塩化ビニル樹脂は、発泡加工する際、配合時の可塑剤の種類、量、充填剤量に関わらず、発泡体の表面平滑性に優れ、緻密なセル構造を有し、凹凸模様を施す際の発泡体の再加熱において発泡体の厚み減少が少なく、ボリューム感のある発泡成形体を提供することができることから、その工業的価値は非常に高いものである。 The vinyl chloride resin for paste obtained by the production method of the present invention is excellent in the surface smoothness of the foam and is a dense cell regardless of the kind, amount and filler amount of the plasticizer at the time of blending. It has a very high industrial value because it has a structure and can provide a foamed molded article with a volume feeling with little reduction in the thickness of the foam during reheating of the foam when applying uneven patterns. is there.
以下に、本発明を実施例により詳細に説明するが、本発明はこれら実施例に制限されるものではない。 EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
実施例及び比較例により得られたペースト用塩化ビニル樹脂は以下の方法により評価を行った。 The vinyl chloride resin for pastes obtained in Examples and Comparative Examples was evaluated by the following method.
〜ペースト用塩化ビニル樹脂の重合度〜
ＪＩＳ Ｋ ６７２１に準拠して測定した。
~ Degree of polymerization of vinyl chloride resin for paste ~
It measured based on JISK6721.
〜発泡体表面平滑性〜
ペースト用塩化ビニル樹脂を下記に示す、（配合１）または（配合２）の配合において、Ｔ．Ｋ．ホモディスパー（特殊機化工業製）を用い３０００ｒｐｍで２分間混練し、ペースト塩ビゾルを調整した。得られたペースト塩ビゾルを難燃紙上に、０．２５ｍｍの厚みでコーティングし、１９０℃に加熱されたオーブン中で８秒加熱することにより、半ゲル状のシートを作製し、該シートを室温まで冷却した後、２３０℃に加熱したオーブン中で４０秒加熱することにより発泡し、得られた発泡体の表面を観察することにより平滑性を評価した。
-Foam surface smoothness-
In the compounding of (Formulation 1) or (Formulation 2) shown below for the vinyl chloride resin for paste, K. Using a homodisper (manufactured by Koki Kogyo Kogyo Co., Ltd.), kneading was performed at 3000 rpm for 2 minutes to prepare a paste vinyl chloride sol. The obtained paste vinyl chloride sol was coated on a flame-retardant paper with a thickness of 0.25 mm, and heated in an oven heated to 190 ° C. for 8 seconds to produce a semi-gel sheet, Then, the foam was heated for 40 seconds in an oven heated to 230 ° C., and the smoothness was evaluated by observing the surface of the obtained foam.
発泡表面平滑性の評価基準を以下に示す。 Evaluation criteria for foam surface smoothness are shown below.
○：表面が平滑 ×：表面が粗い
（配合１）
ペースト用塩化ビニル樹脂 １００重量部
ジ−２−エチルヘキシルフタレート ６０重量部
炭酸カルシウム ７５重量部
Ｂａ−Ｚｎ系安定剤 ３重量部
顔料（ＴｉＯ２） １５重量部
発泡剤（アゾジカーボンアミド） ４重量部
（配合２）
ペースト用塩化ビニル樹脂 １００重量部
ジ−２−エチルヘキシルフタレート ６０重量部
炭酸カルシウム １５０重量部
Ｂａ−Ｚｎ系安定剤 ３重量部
顔料（ＴｉＯ２） １５重量部
発泡剤（アゾジカーボンアミド） ６重量部
希釈剤 １５重量部
〜発泡セル構造〜
発泡体表面平滑性の評価と同様の方法で発泡体を作製し、得られた発泡体の発泡セル構造を光学顕微鏡により観察することにより評価した。
○: Surface is smooth ×: Surface is rough (Formulation 1)
Vinyl chloride resin for paste 100 parts by weight Di-2-ethylhexyl phthalate 60 parts by weight Calcium carbonate 75 parts by weight Ba-Zn stabilizer 3 parts by weight Pigment (TiO 2 ) 15 parts by weight Foaming agent (azodicarbonamide) 4 parts by weight (Formulation 2)
Vinyl chloride resin for paste 100 parts by weight Di-2-ethylhexyl phthalate 60 parts by weight Calcium carbonate 150 parts by weight Ba-Zn stabilizer 3 parts by weight Pigment (TiO 2 ) 15 parts by weight Foaming agent (azodicarbonamide) 6 parts by weight Diluent 15 parts by weight-foamed cell structure-
A foam was prepared by the same method as the evaluation of the foam surface smoothness, and the foamed cell structure of the obtained foam was evaluated by observing it with an optical microscope.
発泡セル構造の評価基準を以下に示す。 The evaluation criteria for the foam cell structure are shown below.
○：セルが緻密 ×：セルが粗い
〜合成例１（油溶性重合開始剤含有シード粒子１の製造例）〜
１ｍ３オートクレーブ中に脱イオン水３６０Ｋｇ、塩化ビニル単量体３００Ｋｇ、過酸化ラウロイル５．７Ｋｇ及び１５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液３０Ｋｇを仕込み、該重合液をホモジナイザーにより３時間循環し、均質化処理後、温度を４５℃に上げて重合反応を開始した。
○: Cell is dense ×: Cell is rough ~ Synthesis Example 1 (Production Example of Oil-Soluble Polymerization Initiator-Containing Seed Particle 1) ~
A 1 m 3 autoclave was charged with 360 kg of deionized water, 300 kg of vinyl chloride monomer, 5.7 kg of lauroyl peroxide and 30 kg of 15 wt% sodium dodecylbenzenesulfonate aqueous solution, and the polymerization solution was circulated for 3 hours with a homogenizer. After the treatment, the temperature was raised to 45 ° C. to initiate the polymerization reaction.
そして、重合反応系の圧力が低下した後、未反応塩化ビニル単量体を回収し、固形分含有率３５％、粒子が０．５５μｍの平均粒子径を有し、かつポリマーを幹として２重量％の過酸化ラウロイルを含有する水性分散液（以下、シード粒子１という。）を得た。 Then, after the pressure of the polymerization reaction system is lowered, the unreacted vinyl chloride monomer is recovered, the solid content is 35%, the particles have an average particle diameter of 0.55 μm, and 2 wt. An aqueous dispersion (hereinafter referred to as seed particles 1) containing 1% lauroyl peroxide was obtained.
〜合成例２（乳化重合による粒子２の製造例）〜
１ｍ３オートクレーブ中に脱イオン水４００Ｋｇ、塩化ビニル単量体３５０Ｋｇ、１６重量％ラウリン酸カリウム水溶液２Ｋｇ及び１６重量％ドデシルベンゼンスルホン酸ナトリウム水溶液５Ｋｇを仕込み、温度を５４℃に上げて重合反応を開始した。
-Synthesis Example 2 (Production Example of Particle 2 by Emulsion Polymerization)-
A 1 m 3 autoclave was charged with 400 kg of deionized water, 350 kg of vinyl chloride monomer, 2 kg of 16 wt% potassium laurate aqueous solution and 5 kg of 16 wt% sodium dodecylbenzenesulfonate aqueous solution, and the temperature was raised to 54 ° C. to initiate the polymerization reaction. did.
そして、重合反応系の圧力が低下した後、未反応塩化ビニル単量体を回収し、固形分含有率４０重量％、粒子が０．１５μｍの平均粒子を有する水性分散液（以下、粒子２という。）を得た。 And after the pressure of a polymerization reaction system falls, an unreacted vinyl chloride monomer is collect | recovered, the solid content rate is 40 weight%, and the aqueous dispersion liquid (henceforth particle | grain 2) which has an average particle | grain whose particle | grain is 0.15 micrometer. .)
実施例１
１ｍ３オートクレーブ中に脱イオン水３５０Ｋｇ、塩化ビニル単量体４００Ｋｇ、２０重量％ドデシルベンゼンスルホン酸ナトリウム２Ｋｇ、合成例１により得られたシード粒子１を４４Ｋｇ、合成例２により得られた粒子２を４０Ｋｇ、３−メルカプトプロピオン酸オクチルを塩化ビニル単量体１００重量部に対し、０．０５重量部仕込み、この重合反応系の温度を６６℃に上げて重合反応を開始した。そして、重合反応開始から重合反応終了までの間、塩化ビニル単量体１００重量部に対して２０重量％ドデシルベンゼンスルホン酸ナトリウム０．７重量部を連続的に添加した。
Example 1
In a 1 m 3 autoclave, 350 kg of deionized water, 400 kg of vinyl chloride monomer, 2 kg of 20 wt% sodium dodecylbenzenesulfonate, 44 kg of seed particles 1 obtained in Synthesis Example 1, and particles 2 obtained in Synthesis Example 2 0.05 kg by weight of 40 kg of octyl 3-mercaptopropionate with respect to 100 parts by weight of the vinyl chloride monomer was added, and the temperature of this polymerization reaction system was raised to 66 ° C. to initiate the polymerization reaction. Then, 0.7 parts by weight of 20% by weight sodium dodecylbenzenesulfonate was continuously added to 100 parts by weight of the vinyl chloride monomer from the start of the polymerization reaction to the end of the polymerization reaction.
重合反応系の重合圧が６６℃における塩化ビニル単量体の飽和蒸気圧から０．６ＭＰａ降下した時に重合反応を停止し、未反応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 pressure of the polymerization reaction system dropped 0.6 MPa from the saturated vapor pressure of the vinyl chloride monomer at 66 ° C., the polymerization reaction was stopped and the unreacted vinyl chloride monomer was recovered to obtain a vinyl chloride polymer latex. .
得られたラテックスは、スプレードライヤーにて、熱風温度１９０℃、出口温度６３℃の条件で噴霧乾燥した後、粉砕して、ペースト用塩化ビニル樹脂とした。 The obtained latex was spray-dried with a spray dryer under conditions of a hot air temperature of 190 ° C. and an outlet temperature of 63 ° C., and then pulverized to obtain a vinyl chloride resin for paste.
得られたペースト用塩化ビニル樹脂１００重量部に対し、ジ−２−エチルヘキシルフタレート６０重量部、炭酸カルシウム７５重量部、Ｂａ−Ｚｎ系安定剤３重量部、アゾジカーボンアミド４重量部、酸化チタン１５重量部をディスパーミキサーにより混練してペースト塩ビゾルとし、該ペースト塩ビゾルを難燃紙上に０．２５ｍｍの厚みでコーティングしセミゲル状のシートを作製し、該シートを室温まで冷却した後、２３０℃で４０秒加熱することにより表面が平滑で緻密なセル構造を有する発泡体を形成し室温まで冷却した後、更に、該発泡体を２３０℃で１０秒再加熱した際、下記式で示される発泡体の厚み減少率は６％であった。 For 100 parts by weight of the obtained vinyl chloride resin for paste, 60 parts by weight of di-2-ethylhexyl phthalate, 75 parts by weight of calcium carbonate, 3 parts by weight of a Ba-Zn stabilizer, 4 parts by weight of azodicarbonamide, titanium oxide 15 parts by weight is kneaded with a disper mixer to obtain a paste vinyl chloride sol, and the paste vinyl chloride sol is coated on a flame retardant paper to a thickness of 0.25 mm to prepare a semi-gel sheet. After cooling the sheet to room temperature, 230 When a foam having a smooth and dense cell structure is formed by heating at 40 ° C. for 40 seconds and cooled to room temperature, when the foam is reheated at 230 ° C. for 10 seconds, it is represented by the following formula: The thickness reduction rate of the foam was 6%.
厚み減少率（％）＝（２３０℃で１０秒の再加熱前の発泡体厚み（ｍｍ）−２３０℃で１０秒再加熱後の発泡体厚み（ｍｍ））／２３０℃で１０秒再加熱前の発泡体厚み（ｍｍ）×１００得られたペースト用塩化ビニル樹脂を評価した結果を表１に示す。 Thickness reduction rate (%) = (foam thickness before reheating at 230 ° C. for 10 seconds (mm) −foam thickness after reheating at 230 ° C. for 10 seconds) / before reheating at 230 ° C. for 10 seconds Table 1 shows the evaluation results of the obtained vinyl chloride resin for paste.
図１に配合１により得られた発泡体断面の光学顕微鏡写真を示す。また、図３に配合２により得られた発泡体断面の光学顕微鏡写真を示す。 FIG. 1 shows an optical micrograph of a cross section of the foam obtained by Formulation 1. Moreover, the optical microscope photograph of the foam cross section obtained by the mixing | blending 2 in FIG. 3 is shown.
得られたペースト用塩化ビニル樹脂は、表面平滑性とセル構造が良好で、再加熱後の厚み減少率も低い値を示す発泡体を提供するものであった。 The obtained vinyl chloride resin for paste provided a foam having good surface smoothness and cell structure, and a low thickness reduction rate after reheating.
実施例２
３−メルカプトプロピオン酸オクチルを塩化ビニル単量体１００重量部に対し、０．０５重量部の代わりに、３−メルカプトプロピオン酸オクチルを塩化ビニル単量体１００重量部に対し、０．１重量部仕込んだ以外は、実施例１と同様の方法でペースト用塩化ビニル樹脂を得た。
Example 2
Instead of 0.05 part by weight of octyl 3-mercaptopropionate per 100 parts by weight of vinyl chloride monomer, 0.1 part by weight of octyl 3-mercaptopropionate per 100 parts by weight of vinyl chloride monomer A vinyl chloride resin for paste was obtained in the same manner as in Example 1 except that it was charged.
得られたペースト用塩化ビニル樹脂の厚み減少率を実施例１と同様の方法により評価した結果、７％であった。 As a result of evaluating the thickness reduction rate of the obtained vinyl chloride resin for paste by the same method as in Example 1, it was 7%.
得られたペースト用塩化ビニル樹脂の評価結果を表１に示す。 The evaluation results of the obtained vinyl chloride resin for paste are shown in Table 1.
得られたペースト用塩化ビニル樹脂は、表面平滑性とセル構造が良好で、再加熱後の厚み減少率も低い値を示す発泡体を提供するものであった。 The obtained vinyl chloride resin for paste provided a foam having good surface smoothness and cell structure, and a low thickness reduction rate after reheating.
実施例３
３−メルカプトプロピオン酸オクチルを塩化ビニル単量体１００重量部に対し、０．０５重量部の代わりに、３−メルカプトプロピオン酸ドデシルを塩化ビニル単量体１００重量部に対し、０．１８重量部仕込んだ以外は、実施例１と同様の方法によりペースト用塩化ビニル樹脂を得た。
Example 3
Instead of 0.05 parts by weight of octyl 3-mercaptopropionate per 100 parts by weight of vinyl chloride monomer, 0.18 parts by weight of dodecyl 3-mercaptopropionate per 100 parts by weight of vinyl chloride monomer A vinyl chloride resin for paste was obtained in the same manner as in Example 1 except that it was charged.
得られたペースト用塩化ビニル樹脂の厚み減少率を実施例１と同様の方法により評価した結果、６％であった。 The thickness reduction rate of the obtained vinyl chloride resin for paste was evaluated by the same method as in Example 1. As a result, it was 6%.
得られたペースト用塩化ビニル樹脂の評価結果を表１に示す。 The evaluation results of the obtained vinyl chloride resin for paste are shown in Table 1.
得られたペースト用塩化ビニル樹脂は、表面平滑性とセル構造が良好で、再加熱後の厚み減少率も低い値を示す発泡体を提供するものであった。 The obtained vinyl chloride resin for paste provided a foam having good surface smoothness and cell structure, and a low thickness reduction rate after reheating.
比較例１
３−メルカプトプロピオン酸オクチルを添加しない以外は、実施例１と同様の方法でペースト用塩化ビニル樹脂を得た。
Comparative Example 1
A vinyl chloride resin for paste was obtained in the same manner as in Example 1 except that octyl 3-mercaptopropionate was not added.
得られたペースト用塩化ビニル樹脂を用いた発泡体の表面平滑性及びセル構造を評価したところ、表面平滑性及びセル構造はわるいものであった。ちなみにその状態で得られたペースト用塩化ビニル樹脂の厚み減少率を実施例１と同様の方法により評価した結果、９％であった。 When the surface smoothness and cell structure of the foam using the vinyl chloride resin for paste obtained were evaluated, the surface smoothness and cell structure were poor. By the way, the thickness reduction rate of the vinyl chloride resin for paste obtained in that state was evaluated by the same method as in Example 1, and as a result, it was 9%.
得られたペースト用塩化ビニル樹脂の評価結果を表１に示す。 The evaluation results of the obtained vinyl chloride resin for paste are shown in Table 1.
図２に配合１により得られた発泡体断面の光学顕微鏡写真を示す。 FIG. 2 shows an optical micrograph of the cross section of the foam obtained by Formulation 1.
得られたペースト用塩化ビニル樹脂は、表面平滑性とセル構造が悪い発泡体を提供するものであった。 The obtained vinyl chloride resin for paste provided a foam having poor surface smoothness and cell structure.
比較例２
３−メルカプトプロピオン酸オクチルを塩化ビニル単量体１００重量部に対し、０．０５重量部の代わりに、塩化ビニル単量体１００重量部に対し、メルカプトエタノール０．０５重量部を仕込んだ以外は、実施例１と同様の方法で重合を行った。重合途中で重合反応が失速したため、目的とするペースト用塩化ビニル樹脂を得ることができなかった。
Comparative Example 2
Except for adding 0.05 parts by weight of mercaptoethanol to 100 parts by weight of vinyl chloride monomer instead of 0.05 parts by weight of octyl 3-mercaptopropionate to 100 parts by weight of vinyl chloride monomer Polymerization was carried out in the same manner as in Example 1. Since the polymerization reaction was stalled during the polymerization, the intended vinyl chloride resin for paste could not be obtained.
比較例３
３−メルカプトプロピオン酸オクチルを塩化ビニル単量体１００重量部に対し、０．０５重量部の代わりに、塩化ビニル単量体１００重量部に対し、３−メルカプトプロピオン酸オクチル０．３重量部を仕込んだ以外は、実施例１と同様の方法で重合を行った。重合途中で重合反応が失速したため、目的とするペースト用塩化ビニル樹脂を得ることができなかった。
Comparative Example 3
Instead of 0.05 parts by weight of octyl 3-mercaptopropionate per 100 parts by weight of vinyl chloride monomer, 0.3 parts by weight of octyl 3-mercaptopropionate per 100 parts by weight of vinyl chloride monomer Polymerization was carried out in the same manner as in Example 1 except for charging. Since the polymerization reaction was stalled during the polymerization, the intended vinyl chloride resin for paste could not be obtained.
比較例４
１ｍ３オートクレーブ中に脱イオン水５００Ｋｇ、塩化ビニル単量体３００Ｋｇ、過酸化ラウロイル０．２４Ｋｇ、３−メルカプトプロピオン酸オクチルを塩化ビニル単量体１００重量部に対し０．０５重量部及び１５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液２０Ｋｇを仕込み、該重合液をホモジナイザーにて１．５時間循環し、均質化処理後、温度を６６℃に上げて重合反応を開始した。重合圧が６６℃における塩化ビニル単量体の飽和蒸気圧から０．６ＭＰａ降下した時に重合反応を停止し、未反応塩化ビニル単量体を回収し、固形分含有率３０％、粒子が１．０１μｍの平均粒子径を有する塩化ビニル重合ラテックスを得た。得られたラテックスは、スプレードライヤーにて、熱風温度１９０℃、出口温度６３℃で噴霧乾燥した後、粉砕して、ペースト用塩化ビニル樹脂を得た。
Comparative Example 4
In 1 m 3 autoclave, 500 kg of deionized water, 300 kg of vinyl chloride monomer, 0.24 kg of lauroyl peroxide and octyl 3-mercaptopropionate are added in an amount of 0.05 parts by weight and 15% by weight with respect to 100 parts by weight of the vinyl chloride monomer. 20 kg of sodium dodecylbenzenesulfonate aqueous solution was charged, and the polymerization solution was circulated for 1.5 hours in a homogenizer. After homogenization, the temperature was raised to 66 ° C. to initiate the polymerization reaction. The polymerization reaction was stopped when the polymerization pressure dropped from the saturated vapor pressure of the vinyl chloride monomer at 66 ° C. by 0.6 MPa, the unreacted vinyl chloride monomer was recovered, the solid content was 30%, and the particles were 1. A vinyl chloride polymerized latex having an average particle size of 01 μm was obtained. The obtained latex was spray-dried with a spray dryer at a hot air temperature of 190 ° C. and an outlet temperature of 63 ° C., and then pulverized to obtain a vinyl chloride resin for paste.
得られたペースト用塩化ビニル樹脂の厚み減少率を実施例１と同様の方法により評価した結果、４８％であった。 The thickness reduction rate of the obtained vinyl chloride resin for paste was evaluated by the same method as in Example 1. As a result, it was 48%.
得られたペースト用塩化ビニル樹脂の評価結果を表１に示す。また、図４に配合２により得られた発泡体断面の光学顕微鏡写真を示す。 The evaluation results of the obtained vinyl chloride resin for paste are shown in Table 1. Moreover, the optical microscope photograph of the foam cross section obtained by the mixing | blending 2 in FIG. 4 is shown.
得られたペースト用塩化ビニル樹脂より得られた発泡体は、配合１においては発泡表面平滑性及び発泡セルは良好であったが、厚み減少率は劣るものであった。そして、配合２においては、表面平滑性とセル構造ともに悪いものであった。 The foam obtained from the obtained vinyl chloride resin for paste had good foam surface smoothness and foam cells in Formulation 1, but the thickness reduction rate was inferior. In Formula 2, both surface smoothness and cell structure were poor.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102952224A (en) * | 2011-08-26 | 2013-03-06 | 沈阳化工股份有限公司 | Low-polymerization-degree polyvinyl chloride pasty resin preparation method |
| JP2014521823A (en) * | 2011-09-02 | 2014-08-28 | エルジー・ケム・リミテッド | High-functional polymerization additive and method for producing vinyl chloride seed using the same |
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| JP2014521823A (en) * | 2011-09-02 | 2014-08-28 | エルジー・ケム・リミテッド | High-functional polymerization additive and method for producing vinyl chloride seed using the same |
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