JP2020007388A - Vinyl chloride-vinyl acetate copolymer particles and automobile underbody coating agent containing the same - Google Patents
Vinyl chloride-vinyl acetate copolymer particles and automobile underbody coating agent containing the same Download PDFInfo
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Abstract
Description
本発明は、塩化ビニル−酢酸ビニル共重合体粒子及びその用途に関するものであり、さらに詳細には、コート剤、特に自動車アンダーボディコート用、自動車シーラント用として有用な塩化ビニル−酢酸ビニル共重合体粒子及びその用途に関するものである。 The present invention relates to vinyl chloride-vinyl acetate copolymer particles and uses thereof, and more particularly, to a vinyl chloride-vinyl acetate copolymer useful as a coating agent, particularly for an automobile underbody coat and an automobile sealant. It relates to particles and their uses.
ペースト加工用塩化ビニル系樹脂（以下、ペースト塩ビと略記する場合もある。）は、一般に可塑剤、充填剤、安定剤又はその他の配合剤などと共に混練することにより、ペースト塩ビゾルを調製し、該ペースト塩ビゾルを使用し種々の成形加工法により壁紙、タイルカーペット、手袋などの様々な成形加工品に用いられている。また、加工温度の低い用途用として、比較的低温でも機械的強度が得られるゲル化溶融性に優れた特性を持つペースト塩ビとして、塩化ビニルに酢酸ビニルを共重合させた塩化ビニル／酢酸ビニル共重合樹脂が知られている。 A vinyl chloride resin for paste processing (hereinafter sometimes abbreviated as paste PVC) is generally kneaded with a plasticizer, a filler, a stabilizer or other compounding agent to prepare a paste PVC sol, The paste salt visol is used for various molded products such as wallpaper, tile carpet, gloves, etc. by various molding methods. In addition, for use at low processing temperatures, as a paste PVC with excellent gelation and melting properties that provides mechanical strength even at relatively low temperatures, vinyl chloride / vinyl acetate copolymers obtained by copolymerizing vinyl acetate with vinyl acetate are used. Polymerized resins are known.
そして、塩化ビニル／酢酸ビニル共重合樹脂を自動車アンダーボディコート用、自動車シーラント用として好適に使用されているが、ペースト塩ビゾルの塗布時の垂れに課題を有しており、その対応が検討・提案されている（例えば特許文献１参照）。 And, vinyl chloride / vinyl acetate copolymer resin is suitably used for automobile underbody coats and automobile sealants, but it has a problem with sagging during application of paste vissol, and its countermeasures will be studied. It has been proposed (for example, see Patent Document 1).
しかし、特許文献１に提案の方法により得られる方法では、塩化ビニル系樹脂についてはなんら検討・提案されていないものであった。 However, in the method obtained by the method proposed in Patent Document 1, no study or proposal has been made on a vinyl chloride resin.
そこで、本発明は、ペースト塩ビゾル塗布時の垂れを抑制するため、ペースト塩ビゾルとした際の初期粘度が高く、経時変化が少ない、かつ低温加工による成形体であっても破断伸びに優れ、コート剤、特に自動車アンダーボディコート用、自動車用シーラント用として優れた特性を有する塩化ビニル−酢酸ビニル共重合体粒子及びそれを含む自動車アンダーボディコート剤を提供することを目的・効果とするものである。 Therefore, the present invention is to suppress the sagging during the application of the paste salt visol, the initial viscosity when the paste salt visol is high, little change over time, and excellent break elongation even in a molded body by low-temperature processing, It is an object and effect of the present invention to provide a coating agent, in particular, a vinyl chloride-vinyl acetate copolymer particle having excellent properties for use as an automobile underbody coat and an automotive sealant, and an automobile underbody coat agent containing the same. is there.
本発明者は、上記の課題について鋭意検討を重ねた結果、塩化ビニル−酢酸ビニル共重合体に特定量のアルキル硫酸エステル塩及びポリエーテルグリコールを含む塩化ビニル−酢酸ビニル共重合体粒子が上記課題を解決することを見出し、本発明を完成させるに至った。 The present inventors have conducted intensive studies on the above-mentioned problems, and as a result, vinyl chloride-vinyl acetate copolymer particles containing a specific amount of an alkyl sulfate salt and polyether glycol in a vinyl chloride-vinyl acetate copolymer have been described. And found that the present invention was completed.
即ち、本発明は、塩化ビニル−酢酸ビニル共重合体１００重量部に対して、アルキル硫酸エステル塩０．５〜２重量部、ポリエーテルグリコール２〜１５重量部を含有し、平均粒子径３〜３０μｍの範囲を有することを特徴とする塩化ビニル−酢酸ビニル共重合体粒子に関するものである。 That is, the present invention contains 0.5 to 2 parts by weight of an alkyl sulfate salt and 2 to 15 parts by weight of a polyether glycol based on 100 parts by weight of a vinyl chloride-vinyl acetate copolymer, and has an average particle size of 3 to 5 parts by weight. The present invention relates to vinyl chloride-vinyl acetate copolymer particles having a range of 30 μm.
以下、本発明に関し詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明の塩化ビニル−酢酸ビニル共重合体粒子は、塩化ビニル−酢酸ビニル共重合体１００重量部に対して、アルキル硫酸エステル塩０．５〜２重量部、ポリエーテルグリコール２〜１５重量部を含有し、平均粒子径３〜３０μｍの範囲を有する粒子形状を有するものである。そして、該塩化ビニル−酢酸ビニル共重合体粒子は、塩化ビニル−酢酸ビニル共重合体の一次粒子の集合体であり、該一次粒子が凝集した粒子形状を有するものであってもよい。該塩化ビニル−酢酸ビニル共重合体粒子は、可塑剤等を配合したペースト塩ビゾルとして成形加工を行うペースト塩ビと称される範疇に属するペースト加工用であるペースト塩化ビニル−酢酸ビニル共重合体粒子であることが好ましい。 The vinyl chloride-vinyl acetate copolymer particles of the present invention contain 0.5 to 2 parts by weight of an alkyl sulfate salt and 2 to 15 parts by weight of a polyether glycol based on 100 parts by weight of the vinyl chloride-vinyl acetate copolymer. It has a particle shape having an average particle diameter of 3 to 30 μm. The vinyl chloride-vinyl acetate copolymer particles are an aggregate of primary particles of the vinyl chloride-vinyl acetate copolymer, and may have a particle shape in which the primary particles are aggregated. The vinyl chloride-vinyl acetate copolymer particles are paste vinyl chloride-vinyl acetate copolymer particles for paste processing belonging to a category called paste vinyl chloride, which is molded and processed as a paste vinyl chloride sol containing a plasticizer or the like. It is preferred that
本発明の塩化ビニル−酢酸ビニル共重合体粒子を構成する塩化ビニル−酢酸ビニル共重合体は、塩化ビニル−酢酸ビニル共重合体と称される範疇に属するものであればよく、その中でも、可塑剤等を配合しペースト塩ビゾルとした際のゾルの粘度の経時変化の安定性、低温加工した際の成形品の特性に優れることから、平均酢酸ビニル残基単位含有量が５〜１５重量％（塩化ビニル−酢酸ビニル共重合体１００重量部中に酢酸ビニルが５重量部〜１５重量部共重合したものに相当。）が好ましく、特にペースト塩ビゾルの初期粘度が高く垂れ抑制に優れるものともなることから、当該平均酢酸ビニル残基単位含有量は５〜１２重量％であることが好ましく、さらに７〜１０重量％であることが好ましい。 The vinyl chloride-vinyl acetate copolymer constituting the vinyl chloride-vinyl acetate copolymer particles of the present invention may be any one belonging to a category referred to as a vinyl chloride-vinyl acetate copolymer. The average vinyl acetate residue unit content is 5 to 15% by weight because of the stability of the viscosity change of the sol over time when a paste salt visol is blended with an agent and the like, and the characteristics of the molded article when processed at low temperature are excellent. (Equivalent to a copolymer of 5 to 15 parts by weight of vinyl acetate in 100 parts by weight of a vinyl chloride-vinyl acetate copolymer) is preferred. Therefore, the average vinyl acetate residue unit content is preferably 5 to 12% by weight, and more preferably 7 to 10% by weight.
また、該塩化ビニル−酢酸ビニル共重合体の平均重合度は、例えばＪＩＳ−Ｋ６７２１に準拠した方法で求めることができ、成形品とした際の機械的強度に優れるものとなることから、平均重合度は１５００〜３０００のものであることが好ましく、特に自動車アンダーボディコート用、自動車用シーラント用として優れたものとなることから平均重合度１６００〜２８００であることが好ましく、さらに１８００〜２５００であることが好ましい。 The average degree of polymerization of the vinyl chloride-vinyl acetate copolymer can be determined, for example, by a method in accordance with JIS-K6721. The degree of polymerization is preferably from 1500 to 3000, particularly preferably from 16000 to 2800, and more preferably from 1800 to 2500, because the degree of polymerization is excellent for automotive underbody coats and automotive sealants. Is preferred.
該塩化ビニル−酢酸ビニル共重合体は、本発明の塩化ビニル−酢酸ビニル共重合体粒子を可塑剤等と配合しペースト塩ビゾルとした際のゾル粘度の経時変化安定性、成形体の力学特性に優れるものとなることから平均一次粒子径が１〜２μｍのものであることが好ましく、特に自動車アンダーボディコート剤、自動車用シーラント用として優れたものとなることから、１〜１．７μｍであることが好ましく。更に１．２〜１．６μｍであることが好ましい。なお、平均一次粒子径は、塩化ビニル−酢酸ビニル共重合体粒子とする前の塩化ビニル−酢酸ビニル共重体ラテックスにおける一次粒子の平均一次粒子径として測定することができる。また、その際には、例えばレーザー回折／散乱式粒子径測定装置によりメジアン径として測定する方法を挙げることができる。 The vinyl chloride-vinyl acetate copolymer is obtained by blending the vinyl chloride-vinyl acetate copolymer particles of the present invention with a plasticizer or the like to form a paste salt visol, with which the sol viscosity changes over time and the mechanical properties of the molded article. It is preferable that the average primary particle diameter is 1 to 2 μm in order to be excellent, and in particular, it is 1 to 1.7 μm in order to be excellent for an automobile underbody coating agent and an automobile sealant. It is preferable. Further, the thickness is preferably 1.2 to 1.6 μm. The average primary particle diameter can be measured as the average primary particle diameter of the primary particles in the vinyl chloride-vinyl acetate copolymer latex before being converted into the vinyl chloride-vinyl acetate copolymer particles. In this case, for example, a method of measuring the median diameter with a laser diffraction / scattering type particle diameter measuring device can be used.
本発明の塩化ビニル−酢酸ビニル共重合体粒子は、ペースト塩ビゾルとした際の粘度の経時変化が少なく、優れたものとなることからアルキル硫酸エステル塩を該塩化ビニル−酢酸ビニル共重合体１００重量部に対して０．５〜２重量部含有するものであり、特に低温加工での成形品の破断伸び、ペースト塩ビゾルとした際の粘度の経時変化が共に極めて優れたものとなり、特に自動車アンダーボディコート剤、自動車用シーラント用として優れたものとなることから、該アルキル硫酸エステル塩の含有量は塩化ビニル−酢酸ビニル共重合体１００重量部に対して０．８〜１．５重量部含有するものであることが好ましく、特に０．９〜１．２重量部であることが好ましい。ここで、アルキル硫酸エステル塩の含有量が０．２重量部未満である場合、ペースト塩ビゾルとした際の粘度の経時変化は大きなものとなる。一方、２重量部を越える場合、得られる成形体は機械特性に劣るものとなる。該アルキル硫酸エステル塩としてはその範疇に属するものであればよく、中でも、ペースト塩ビゾルとした際のゾル粘度の経時変化が特に少ないものとなることから、全炭素数が１０〜１４のアルキル硫酸エステル塩であることが好ましく、例えばラウリル硫酸リチウム、ラウリル硫酸カリウム、ラウリル硫酸ナトリウム、ラウリル硫酸アンモニウム、ラウリル硫酸トリエタノールアンモニウム等のラウリル硫酸塩；オレイル硫酸リチウム、オレイル硫酸カリウム、オレイル硫酸ナトリウム、オレイル硫酸アンモニウム、オレイル硫酸トリエタノールアンモニウム等のオレイル硫酸塩；ミリスチル硫酸リチウム、ミリスチル硫酸カリウム、ミリスチル硫酸ナトリウム、ミリスチル硫酸アンモニウム、ミリスチル硫酸トリエタノールアンモニウム等のミリスチル硫酸塩、等が挙げられ、特にラウリル硫酸リチウム、ラウリル硫酸カリウム、ラウリル硫酸ナトリウム、ラウリル硫酸アンモニウム、ラウリル硫酸トリエタノールアンモニウム等のラウリル硫酸エステル塩であることが好ましい。 The vinyl chloride-vinyl acetate copolymer particles of the present invention have little change over time in viscosity when formed into a paste salt visol and are excellent, so that the alkyl sulfate ester salt is converted to the vinyl chloride-vinyl acetate copolymer 100. It is contained in an amount of 0.5 to 2 parts by weight with respect to parts by weight. The content of the alkylsulfate is 0.8 to 1.5 parts by weight based on 100 parts by weight of the vinyl chloride-vinyl acetate copolymer because it is excellent as an underbody coating agent and an automotive sealant. Preferably, it is contained, and particularly preferably 0.9 to 1.2 parts by weight. Here, when the content of the alkyl sulfate salt is less than 0.2 parts by weight, the change with time of the viscosity of the paste salt visol becomes large. On the other hand, when the amount exceeds 2 parts by weight, the obtained molded article has poor mechanical properties. As the alkyl sulfate salt, any one belonging to the category may be used, and among them, since the change with time of the sol viscosity when formed into a paste salt visol is particularly small, the alkyl sulfate having a total carbon number of 10 to 14 is preferred. Preferred are ester salts, for example, lauryl sulfates such as lithium lauryl sulfate, potassium lauryl sulfate, sodium lauryl sulfate, ammonium lauryl sulfate, triethanolammonium lauryl sulfate; lithium oleyl sulfate, potassium oleyl sulfate, sodium oleyl sulfate, ammonium oleyl sulfate, Oleyl sulfates such as triethanol ammonium oleyl sulfate; lithium myristyl sulfate, potassium myristyl sulfate, sodium myristyl sulfate, ammonium myristyl sulfate, and triethanol ammonium myristyl sulfate Myristyl sulfate and the like, etc., and in particular lithium lauryl sulfate, potassium lauryl sulfate, sodium lauryl sulfate, ammonium lauryl sulfate, it is lauryl sulfate and lauryl triethanolammonium sulfate preferred.
本発明の塩化ビニル−酢酸ビニル共重合体粒子は、ポリエーテルグリコールを該塩化ビニル−酢酸ビニル共重合体１００重量部に対して２〜１５重量部含有する樹脂であり、特に低温加工での成形品の破断伸び、ペースト塩ビゾルとした際の初期粘度が高く極めて優れたものとなり、特に自動車アンダーボディコート剤、自動車用シーラント用として優れたものとなることから、２．５〜１２重量部であることが好ましく、更に５〜１０重量部であることが好ましい。ここで、ポリエーテルグリコールの配合量が２重量部未満である場合、ペースト塩ビゾルとした際の初期粘度、粘度の安定性に劣り、垂れ、成形不良が発生しやすいものとなる。一方、１５重量部を越える場合、成形体の力学特性に劣るものとなる。そして、ポリエーテルグリコールとしては、本発明の特性を損なわないものであれば、特に制限されることなく、中でも、ポリテトラメチレンエーテルグリコール（ＰＴＭＧ）、ポリトリメチレンエーテルグリコール等のポリアルキレンエーテルグリコール；１〜２０モル％の３−メチルテトラヒドロフランとテトラヒドロフランの共重合ポリエーテルポリオール（例えば、保土ヶ谷化学社製（商品名）ＰＴＧ−Ｌ１０００、ＰＴＧ−Ｌ２０００、ＰＴＧ−Ｌ３５００等）、ネオペンチルグリコールとテトラヒドロフランの共重合ポリエーテルグリコール、等が挙げられ、特にペースト塩ビゾルとした際の初期粘度、粘度の安定性に優れ、垂れ、成形不良の抑制に優れるものとなることからポリテトラメチレンエーテルグリコールが好ましい。また、ポリエーテルグリコールとしては、ペースト塩ビゾルとした際の初期粘度が極めて高くなることから、数平均分子量１０００〜３０００であるものが好ましく、特に１５００〜２５００であるものが好ましい。 The vinyl chloride-vinyl acetate copolymer particles of the present invention are resins containing polyether glycol in an amount of 2 to 15 parts by weight based on 100 parts by weight of the vinyl chloride-vinyl acetate copolymer. Elongation at break of the product, the initial viscosity when it is made into a paste salt visol is extremely high, and it is particularly excellent for an automobile underbody coating agent and an automotive sealant. Preferably, it is more preferably 5 to 10 parts by weight. Here, when the blending amount of the polyether glycol is less than 2 parts by weight, the initial viscosity and the viscosity stability when the paste salt visol is formed are inferior, and sagging and poor molding are likely to occur. On the other hand, when the amount exceeds 15 parts by weight, the mechanical properties of the molded body are inferior. The polyether glycol is not particularly limited as long as it does not impair the characteristics of the present invention. Among them, polyalkylene ether glycols such as polytetramethylene ether glycol (PTMG) and polytrimethylene ether glycol; 1 to 20 mol% of a copolymerized polyether polyol of 3-methyltetrahydrofuran and tetrahydrofuran (for example, PTG-L1000, PTG-L2000, PTG-L3500, etc., manufactured by Hodogaya Chemical Co., Ltd.), a copolymer of neopentyl glycol and tetrahydrofuran Polymerized polyether glycol, and the like, and particularly preferred is polytetramethylene ether glycol, which is particularly excellent in initial viscosity when formed into a paste salt visol, excellent in stability of viscosity, drooping, and excellent in suppressing poor molding.The polyether glycol preferably has a number average molecular weight of 1,000 to 3,000, and more preferably has a number average molecular weight of 1,000 to 2,500, since the initial viscosity of the paste salt visol becomes extremely high.
本発明の塩化ビニル−酢酸ビニル共重合体粒子は、塩化ビニル−酢酸ビニル共重合体１００重量部に対して、アルキル硫酸エステル塩０．５〜２重量部、ポリエーテルグリコール２〜１５重量部を含有し、平均粒子径３〜３０μｍの範囲を有する粒子形状を有するものである。ここで、平均粒子径が３μｍ未満である場合、紛体としての取り扱い性に劣るばかりか、ペースト塩ビゾルとした際の経時変化の安定性にも劣るものとなる。一方、３０μｍを越える場合、ペースト塩ビゾルとする際の可塑剤吸収性に劣り、成形加工性に劣るものとなる。なお、平均粒子径は、例えばレーザー回折／散乱式粒子径測定装置によりメジアン径として測定することができる
そして、本発明の塩化ビニル−酢酸ビニル共重合体粒子は、特にペースト塩ビゾルとした際の初期粘度が高いことから塗布時の垂れを抑制できるきわめて優れたものとなり、初期粘度が８００００ｍＰａ・ｓ以上となるものが好ましい。また、粘度の経時変化も極めて優れたものとなり、増粘率が９０％以下となるものが好ましく、さらに自動車アンダーボディコート剤、自動車用シーラント用として優れたものとなることから、増粘率が５０％未満となるものが好ましい。その際の増粘率の測定方法については後述する。
The vinyl chloride-vinyl acetate copolymer particles of the present invention contain 0.5 to 2 parts by weight of an alkyl sulfate salt and 2 to 15 parts by weight of a polyether glycol based on 100 parts by weight of the vinyl chloride-vinyl acetate copolymer. It has a particle shape having an average particle diameter of 3 to 30 μm. Here, when the average particle size is less than 3 μm, not only is the powder inferior in handleability, but also the stability over time when the paste salt visol is formed is poor. On the other hand, if it exceeds 30 μm, the plasticizer absorbability when forming a paste salt visol is inferior, and the moldability is inferior. The average particle diameter can be measured as a median diameter by, for example, a laser diffraction / scattering particle diameter measuring device. The vinyl chloride-vinyl acetate copolymer particles of the present invention are particularly suitable for use in a paste salt visol. Since the initial viscosity is high, dripping during coating is extremely excellent, and those having an initial viscosity of 80,000 mPa · s or more are preferable. Further, the change with time of the viscosity is also extremely excellent, and it is preferable that the viscosity increase rate is 90% or less. Further, since the viscosity increase rate is excellent for an automobile underbody coating agent and an automobile sealant, the viscosity increase rate is high. Those having less than 50% are preferred. The method of measuring the thickening rate at that time will be described later.
また、本発明の塩化ビニル−酢酸ビニル共重合体粒子は、特に低温加工での破断伸びに優れる成形体となり、特に自動車アンダーボディコート剤、自動車用シーラント用として優れたものとなることから、破断伸び３００％以上を示すものであることが好ましい。その際の破断伸びの測定方法としては、例えば、塩化ビニル−酢酸ビニル共重合体粒子１００重量部に対し、フタル酸ジイソノニル１００重量部、炭酸カルシウム７０重量部、ナフテン系炭化水素溶剤１５重量部を配合し、ペースト塩ビゾルを調製し、２ｍｍ厚に塗布したシートから、ＪＩＳ３号ダンベル試験片を用い、試験片の中央に２０ｍｍ間隔の標線を入れ、引張り試験装置に取り付け、５０ｍｍ／分の速度で引張り、破断時の荷重及び標線間の伸びを測定し、破断伸び及び引張強度を求めることができる。 Further, the vinyl chloride-vinyl acetate copolymer particles of the present invention are formed into a molded article having excellent breaking elongation particularly at low temperature processing, and are particularly excellent as an automobile underbody coating agent and an automotive sealant. It is preferable that it shows an elongation of 300% or more. As a method of measuring the elongation at break at that time, for example, 100 parts by weight of vinyl chloride-vinyl acetate copolymer particles, 100 parts by weight of diisononyl phthalate, 70 parts by weight of calcium carbonate, 15 parts by weight of a naphthenic hydrocarbon solvent. A JIS No. 3 dumbbell test piece was used to insert a mark line at intervals of 20 mm from the sheet coated with a 2 mm-thick sheet to prepare a paste-PVC sol. The tensile elongation, the load at break and the elongation between the marked lines are measured, and the elongation at break and tensile strength can be determined.
本発明のアルキル硫酸エステル塩及びポリエーテルグリコールを配合する塩化ビニル−酢酸ビニル共重合体粒子を製造する際の製造方法としては、該塩化ビニル−酢酸ビニル共重合体粒子の製造が可能であれば如何なる方法を用いてもよく、例えば塩化ビニル−酢酸ビニル共重合体の製造の際に、アルキル硫酸エステル塩、ポリエーテルグリコールを併用する方法、製造後の塩化ビニル−酢酸ビニル共重合体にアルキル硫酸エステル塩、ポリエーテルグリコールを添加する方法、アルキル硫酸エステル塩、ポリエーテルグリコールのそれぞれを独立して、重合時又は重合後に添加する方法、等を挙げることができる。 As a method for producing the vinyl chloride-vinyl acetate copolymer particles containing the alkyl sulfate ester salt and polyether glycol of the present invention, if it is possible to produce the vinyl chloride-vinyl acetate copolymer particles, Any method may be used, for example, in the production of a vinyl chloride-vinyl acetate copolymer, a method in which an alkyl sulfate ester salt and a polyether glycol are used in combination, and an alkyl sulfate is added to the vinyl chloride-vinyl acetate copolymer after the production. Examples thereof include a method of adding an ester salt and a polyether glycol, and a method of independently adding an alkyl sulfate salt and a polyether glycol during or after polymerization.
そして、塩化ビニル−酢酸ビニル共重合体を製造する際には、重合開始剤、連鎖移動剤、架橋剤、緩衝剤、水溶性開始剤、還元剤、高級アルコール等を適宜用いることができる。当該添加剤については、本発明の目的を奏する限りにおいて、本発明の塩化ビニル−酢酸ビニル共重合体粒子に含まれていてもよい。また、塩化ビニル−酢酸ビニル共重合体の製造方法としては、例えば、塩化ビニルモノマーと酢酸ビニルモノマーの混合液を、重合開始剤の存在下において水性媒体中で重合する製造方法を挙げることができる。 When producing the vinyl chloride-vinyl acetate copolymer, a polymerization initiator, a chain transfer agent, a crosslinking agent, a buffer, a water-soluble initiator, a reducing agent, a higher alcohol, and the like can be appropriately used. The additive may be contained in the vinyl chloride-vinyl acetate copolymer particles of the present invention as long as the object of the present invention is achieved. Examples of the method for producing the vinyl chloride-vinyl acetate copolymer include a production method in which a mixture of a vinyl chloride monomer and a vinyl acetate monomer is polymerized in an aqueous medium in the presence of a polymerization initiator. .
該製造方法においては、平均酢酸ビニル残基単位含有量を５〜１５重量％以下とする塩化ビニル−酢酸ビニル共重合体を効率的に製造することが可能となることから、塩化ビニルモノマー／酢酸ビニルモノマー＝９４／６〜８０／２０（重量／重量）よりなる混合単量体を用いてなることが好ましく、特に低温加工での破断伸び、ペースト塩ビゾルとした際の粘度の経時変化が共に極めて優れたものとなり、特に自動車アンダーボディコート剤、自動車用シーラント用として優れるものを効率的に製造することが可能となることから、塩化ビニルモノマー／酢酸ビニルモノマー＝９４／６〜８５／１５（重量／重量）よりなることが好ましい。 In the production method, it is possible to efficiently produce a vinyl chloride-vinyl acetate copolymer having an average vinyl acetate residue unit content of 5 to 15% by weight or less. It is preferable to use a mixed monomer consisting of vinyl monomer = 94/6 to 80/20 (weight / weight), and particularly, the elongation at break in low-temperature processing and the time-dependent change in viscosity when formed into a paste salt visol are both It is extremely excellent, and particularly, it is possible to efficiently produce an excellent product for an automobile underbody coating agent and an automotive sealant. Therefore, vinyl chloride monomer / vinyl acetate monomer = 94/6 to 85/15 ( (Weight / weight).
重合開始剤としては、重合開始剤の範疇に属するものであれば如何なるものであってもよく、例えば、過硫酸カリウム、過硫酸アンモニウム等の水溶性重合開始剤；アゾビスイソブチロニトリル等のアゾ化合物，ラウロイルパーオキサイド、ｔ−ブチルペルオキシピバレート、ジアシルパーオキサイド、パーオキシエステル、パーオキシジカーボネート等の過酸化物，等の油溶性重合開始剤等を挙げることができる。また、シードミクロ懸濁重合法の際には、油溶性開始剤を含む種粒子（シード）であってもよい。 The polymerization initiator may be any as long as it belongs to the category of the polymerization initiator. For example, water-soluble polymerization initiators such as potassium persulfate and ammonium persulfate; azo such as azobisisobutyronitrile Examples of the compound include oil-soluble polymerization initiators such as compounds, peroxides such as lauroyl peroxide, t-butyl peroxypivalate, diacyl peroxide, peroxyester, and peroxydicarbonate. In the case of the seed microsuspension polymerization method, seed particles (seed) containing an oil-soluble initiator may be used.
そして、該製造方法における重合法としては、例えば塩化ビニルモノマー、酢酸ビニルモノマー、界面活性剤、油溶性重合開始剤、必要に応じて脂肪族高級アルコール等の乳化補助剤を脱イオン水に添加し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；ミクロ懸濁重合法で得られた油溶性重合開始剤を含む種粒子（シード）を用いて行うシードミクロ懸濁重合法；塩化ビニル系単量体を脱イオン水、界面活性剤、水溶性重合開始剤とともに緩やかな攪拌下で重合を行う乳化重合法で得られた粒子をシードとして用いて乳化重合を行うシード乳化重合法等があげられ、その際に、例えば、重合温度は３０〜８０℃とし、塩化ビニル−酢酸ビニル共重合体ラテックスとして得ることができる。これらの重合により製造された塩化ビニル−酢酸ビニル共重合体ラテックスを噴霧乾燥し、必要に応じて粉砕することにより、塩化ビニル−酢酸ビニル共重合体の一次粒子が凝集した本発明の平均粒子径３〜３０μｍを有する塩化ビニル−酢酸ビニル共重合体粒子を得ることができる。 As a polymerization method in the production method, for example, an emulsifying aid such as a vinyl chloride monomer, a vinyl acetate monomer, a surfactant, an oil-soluble polymerization initiator, and, if necessary, an aliphatic higher alcohol is added to deionized water. A microsuspension polymerization method in which polymerization is performed under gentle stirring after mixing and dispersing with a homogenizer or the like; a seed microsuspension performed using seed particles (seed) containing an oil-soluble polymerization initiator obtained by the microsuspension polymerization method. Suspension polymerization method: Emulsion polymerization is performed using particles obtained by an emulsion polymerization method in which a vinyl chloride-based monomer is polymerized with deionized water, a surfactant, and a water-soluble polymerization initiator under gentle stirring, as a seed. A seed emulsion polymerization method and the like can be mentioned. In this case, for example, the polymerization temperature is 30 to 80 ° C., and a vinyl chloride-vinyl acetate copolymer latex can be obtained. The average particle diameter of the present invention in which the primary particles of the vinyl chloride-vinyl acetate copolymer are aggregated by spray drying the vinyl chloride-vinyl acetate copolymer latex produced by these polymerizations and pulverizing as necessary. Vinyl chloride-vinyl acetate copolymer particles having a size of 3 to 30 μm can be obtained.
塩化ビニル−酢酸ビニル共重合体粒子とする際に用いる乾燥機は一般的に使用されているものでよく、例えば、噴霧乾燥機等が挙げられる（具体例としては、「ＳＰＲＡＹ ＤＲＹＩＮＧ ＨＡＮＤＢＯＯＫ」（Ｋ．Ｍａｓｔｅｒｓ著、３版、１９７９年、ＧｅｏｒｇｅｇｏｄｗｉｎＬｉｍｉｔｅｄより出版）の１２１頁第４．１０図に記載されている各種の噴霧乾燥機）。乾燥用空気入口温度、乾燥用空気出口温度に特に制限はなく、乾燥用空気入口温度は８０〜２００℃、乾燥用空気出口温度は４５〜７５℃が一般的に用いられる。乾燥用空気入口温度は１００〜１７０℃、乾燥用空気出口温度は５０〜７０℃が更に好ましい。乾燥後に得られる塩化ビニル−酢酸ビニル共重合体粒子は、ラテックスを構成する一次粒子の集合体であり、場合によっては粉砕を経て５〜２０μｍの顆粒状とすることが好ましい。乾燥出口温度が５５℃を超える場合には、得られた顆粒状塩化ビニル−酢酸ビニル共重合体粒子を粉砕した方が可塑剤への分散の点から好ましく、乾燥出口温度が５５℃以下の場合には、顆粒状のままでも粉砕して使用してもどちらでも良い。 The dryer used for forming the vinyl chloride-vinyl acetate copolymer particles may be a commonly used dryer, and examples thereof include a spray dryer (specific examples include “SPRAY DRYING HANDBOOK” (K Masters, 3rd Edition, 1979, published by Georgegodwin Limited), page 121, Figure 4.10), various spray dryers). The drying air inlet temperature and the drying air outlet temperature are not particularly limited, and the drying air inlet temperature is generally 80 to 200 ° C, and the drying air outlet temperature is generally 45 to 75 ° C. More preferably, the drying air inlet temperature is 100 to 170 ° C, and the drying air outlet temperature is 50 to 70 ° C. The vinyl chloride-vinyl acetate copolymer particles obtained after drying are aggregates of primary particles constituting the latex, and in some cases, are preferably pulverized into granules of 5 to 20 μm. When the drying outlet temperature exceeds 55 ° C., it is preferable to pulverize the obtained granular vinyl chloride-vinyl acetate copolymer particles from the viewpoint of dispersion in a plasticizer, and when the drying outlet temperature is 55 ° C. or lower. The granules may be used either in the form of granules or by pulverization.
本発明の塩化ビニル−酢酸ビニル共重合体粒子は、フタル酸ジブチル、フタル酸ジヘキシル、フタル酸ジイソノニル、フタル酸ジオクチル等のフタル酸エステル類；トリクレジルホスフェート等のリン酸エステル類、等に代表される可塑剤等と配合することにより、ペースト加工に供することが可能となるペースト塩ビゾルとして、アンダーボディコート、シーラントに代表される各種用途に用いることができる。また、ペースト塩ビゾルとする際には、通常一般的に用いられるタルク、炭酸カルシウム等の充填剤；安定剤；プロセスオイル等の加工助剤、等の添加剤を併用することもできる。 The vinyl chloride-vinyl acetate copolymer particles of the present invention are represented by phthalic acid esters such as dibutyl phthalate, dihexyl phthalate, diisononyl phthalate and dioctyl phthalate; and phosphoric acid esters such as tricresyl phosphate. By being blended with a plasticizer or the like, it can be used as a paste salt visol that can be used for paste processing in various applications represented by underbody coats and sealants. Further, when the paste salt visol is used, additives such as generally used fillers such as talc and calcium carbonate; stabilizers; processing aids such as process oils and the like can be used in combination.
本発明の塩化ビニル−酢酸ビニル共重合体粒子は、可塑剤に分散させて調製したペースト塩ビゾルの初期粘度が高くかつ粘度の経時変化が少なく、低温加工時の機械的強度、破断伸びに優れ、コート剤、特に自動車アンダーボディコート剤、自動車用シーラント用として優れた特性を有するものである。 The vinyl chloride-vinyl acetate copolymer particles of the present invention have a high initial viscosity of paste salt visol prepared by dispersing in a plasticizer and a small change with time in viscosity, and have excellent mechanical strength and low elongation at low temperature processing. It has excellent properties as a coating agent, particularly as an underbody coating agent for automobiles and a sealant for automobiles.
以下に、本発明を実施例により、さらに詳細に説明するが本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
以下に実施例より得られた塩化ビニル−酢酸ビニル共重合体粒子の評価方法を示す。 The evaluation method of the vinyl chloride-vinyl acetate copolymer particles obtained from the examples will be described below.
＜初期粘度の測定方法＞
塩化ビニル−酢酸ビニル共重合体粒子１００重量部、フタル酸ジイソノニル１００重量部（株式会社ジェイプラス製）、脂肪酸塩表面処理炭酸カルシウム（（商品名）Ｖｉｓｃｏｌｉｔｅ−ＯＳ 白石工業株式会社製）７０重量部、及びナフテン系炭化水素溶剤（（商品名）Ｅｘｘｓｏｌ Ｄ４０ 東燃ゼネラル石油株式会社製）１５重量部を混練し、ペースト塩ビゾルを得た。得られたペースト塩ビゾルを２３℃にて２４時間保管した後、Ｂ８Ｈ型回転粘度計で２３℃、２０ｒｐｍ条件にて測定した粘度を初期粘度とした。
<Method of measuring initial viscosity>
100 parts by weight of vinyl chloride-vinyl acetate copolymer particles, 100 parts by weight of diisononyl phthalate (manufactured by J-PLUS Co., Ltd.), 70 parts by weight of fatty acid salt surface-treated calcium carbonate ((trade name) Viscolite-OS manufactured by Shiraishi Industry Co., Ltd.) , And 15 parts by weight of a naphthenic hydrocarbon solvent (trade name: Exxsol D40 manufactured by TonenGeneral Sekiyu KK) were kneaded to obtain a paste salt visol. After storing the obtained paste salt visol at 23 ° C. for 24 hours, the viscosity measured at 23 ° C. and 20 rpm with a B8H rotational viscometer was defined as the initial viscosity.
＜増粘率の測定方法＞
塩化ビニル−酢酸ビニル共重合体粒子１００重量部、フタル酸ジイソノニル１００重量部（株式会社ジェイプラス製）、脂肪酸塩表面処理炭酸カルシウム（（商品名）Ｖｉｓｃｏｌｉｔｅ−ＯＳ 白石工業株式会社製）７０重量部、及びナフテン系炭化水素溶剤（（商品名）Ｅｘｘｓｏｌ Ｄ４０ 東燃ゼネラル石油株式会社製）１５重量部を混練し、ペースト塩ビゾルを得た。得られたペースト塩ビゾルを２３℃にて２４時間保管した後、Ｂ８Ｈ型回転粘度計で２３℃、２０ｒｐｍ条件にて測定した粘度を粘度Ａとし、該ゾルを、更に２３℃にて７日間保管した後、Ｂ８Ｈ型回転粘度計で２３℃、２０ｒｐｍ条件にて測定した粘度を粘度Ｂとした。粘度Ａ及び粘度Ｂを下記式にて、得られたペースト塩ビゾルの増粘率を求めた。
<Measurement method of viscosity increase>
100 parts by weight of vinyl chloride-vinyl acetate copolymer particles, 100 parts by weight of diisononyl phthalate (manufactured by J-PLUS Co., Ltd.), 70 parts by weight of fatty acid salt surface-treated calcium carbonate ((trade name) Viscolite-OS manufactured by Shiraishi Industry Co., Ltd.) , And 15 parts by weight of a naphthenic hydrocarbon solvent (trade name: Exxsol D40 manufactured by TonenGeneral Sekiyu KK) were kneaded to obtain a paste salt visol. After the obtained paste salt visol is stored at 23 ° C. for 24 hours, the viscosity measured at 23 ° C. and 20 rpm with a B8H rotational viscometer is set as viscosity A, and the sol is further stored at 23 ° C. for 7 days. After that, the viscosity measured at 23 ° C. and 20 rpm with a B8H rotational viscometer was defined as viscosity B. The viscosity A and the viscosity B were determined by the following formula to determine the viscosity increase rate of the obtained paste salt visol.
増粘率（％）＝１００×（Ｂ−Ａ）／Ａ
＜破断伸びの測定方法＞
塩化ビニル−酢酸ビニル共重合体粒子１００重量部、フタル酸ジイソノニル１００重量部（株式会社ジェイプラス製）、脂肪酸塩表面処理炭酸カルシウム（（商品名）Ｖｉｓｃｏｌｉｔｅ−ＯＳ 白石工業株式会社製）７０重量部、及びナフテン系炭化水素溶剤（（商品名）Ｅｘｘｓｏｌ Ｄ４０ 東燃ゼネラル石油株式会社製）１５重量部を混練してペースト塩ビゾルを製造した。脱泡処理した前記ペースト塩ビゾルを離型紙で２ｍｍ厚に塗布し、１４０℃×３０ｍｉｎ分間加熱してペースト塩ビシートを作成した。得られたペースト塩ビシートからＪＩＳ３号ダンベルを用いて試験片を作成し、試験片の中央に２０ｍｍ間隔の標線を入れ、引張り試験装置に取り付け、２３℃で５０ｍｍ／分の速度で引張り、破断時の荷重及び標線間の伸びを測定し、破断伸び及び引張強度を求めた。
Thickening rate (%) = 100 × (BA) / A
<Method of measuring elongation at break>
100 parts by weight of vinyl chloride-vinyl acetate copolymer particles, 100 parts by weight of diisononyl phthalate (manufactured by J-PLUS Co., Ltd.), 70 parts by weight of fatty acid salt surface-treated calcium carbonate ((trade name) Viscolite-OS manufactured by Shiraishi Industry Co., Ltd.) And 15 parts by weight of a naphthenic hydrocarbon solvent ((trade name) Exxsol D40 manufactured by TonenGeneral Sekiyu KK) were kneaded to produce a paste salt visol. The defoamed paste PVC sol was applied with a release paper to a thickness of 2 mm and heated at 140 ° C. for 30 minutes to prepare a paste PVC sheet. A test piece was prepared from the obtained paste PVC sheet using a JIS No. 3 dumbbell, a mark line at intervals of 20 mm was placed at the center of the test piece, attached to a tensile tester, pulled at 23 ° C. at a speed of 50 mm / min, and broken. The load at the time and the elongation between the marked lines were measured, and the elongation at break and the tensile strength were determined.
＜平均重合度の測定＞
ＪＩＳ−Ｋ６７２１に準拠し求めた。
<Measurement of average polymerization degree>
It was determined based on JIS-K6721.
＜平均酢酸ビニル残基単位含有量の測定方法＞
塩化ビニル−酢酸ビニル共重合体中に含有する平均酢酸ビニル残基単位含有量（重量％）（ＶＡｃ含量と記す場合もある。）は、塩化ビニル−酢酸ビニル共重合体１００ｍｇと臭化カリウム１０ｍｇを混合し、すりつぶして成形した測定サンプルと、赤外分光光度計（島津社製、（商品名）ＦＴＩＲ−８１００Ａ）を用いて、下記式より算出した。
<Method of measuring average vinyl acetate residue unit content>
The average vinyl acetate residue unit content (weight%) (sometimes referred to as VAc content) contained in the vinyl chloride-vinyl acetate copolymer is 100 mg of the vinyl chloride-vinyl acetate copolymer and 10 mg of potassium bromide. Were mixed, ground and molded, and an infrared spectrophotometer (manufactured by Shimadzu Corporation, (trade name) FTIR-8100A) was used to calculate from the following equation.
ＶＡｃ含量＝（３．７３×Ｂ／Ａ＋０．０２４）×１．０４
Ａ：１４３０ｃｍ−１付近のＣ−Ｈ面内変角による吸収ピークトップのＡｂｓ．値。
Ｂ：１７４０ｃｍ−１付近のＣ＝Ｏ伸縮による吸収ピークトップのＡｂｓ．値。
VAc content = (3.73 × B / A + 0.024) × 1.04
A: Abs. Of absorption peak top due to CH in-plane bending around 1430 cm -1 . value.
B: Abs. At the top of the absorption peak due to C = O stretching near 1740 cm -1 . value.
＜平均粒子径の測定＞
塩化ビニル−酢酸ビニル共重合体粒子にレーザー透過率が８４〜８６％となるように水を添加して濃度調整を行った測定用試料を、レーザー回折／散乱式粒子径測定装置（（商品名）ＬＡ−９２０、堀場製作所（株）製）を用いて、メジアン径を測定し平均粒子径とした。
<Measurement of average particle size>
A measurement sample obtained by adding water to the vinyl chloride-vinyl acetate copolymer particles so as to have a laser transmittance of 84 to 86% and adjusting the concentration is used as a laser diffraction / scattering particle size analyzer ((trade name) ) The median diameter was measured using LA-920 (manufactured by Horiba, Ltd.) to obtain the average particle diameter.
＜一次平均粒子径の測定＞
塩化ビニル−酢酸ビニル共重合体ラテックスにレーザー透過率が８４〜８６％となるように水を添加して濃度調整を行った測定用試料を、レーザー回折／散乱式粒子径測定装置（（商品名）ＬＡ−９２０、堀場製作所（株）製）を用いて、メジアン径を測定し一次平均粒子径とした。
<Measurement of primary average particle size>
A measurement sample obtained by adding water to a vinyl chloride-vinyl acetate copolymer latex and adjusting the concentration by adding water so that the laser transmittance becomes 84 to 86% is applied to a laser diffraction / scattering type particle diameter measuring device ((trade name) ) The median diameter was measured using LA-920 (manufactured by Horiba, Ltd.) to obtain a primary average particle diameter.
合成例１（開始剤等含有シードの製造例）
１ｍ３オートクレーブ中に脱イオン水３６０ｋｇ、塩化ビニルモノマー３００ｋｇ、過酸化ラウロイル６ｋｇ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を用いて２時間循環し、均質化処理後、温度を４５℃に上げて、重合を進めた。４５℃における塩化ビニルモノマーの飽和蒸気圧より０．２ＭＰａ圧力が低下した後、未反応の塩化ビニルモノマーを回収した。得られた開始剤等含有シードラテックス（以下、シード１と略記する。）の平均粒子径は０．６０μｍ、固形分濃度は３２％であった。
Synthesis Example 1 (Example of producing seed containing initiator etc.)
In a 1 m 3 autoclave, 360 kg of deionized water, 300 kg of vinyl chloride monomer, 6 kg of lauroyl peroxide and 30 kg of a 15% by weight aqueous solution of sodium dodecylbenzenesulfonate are charged, and the polymerization solution is circulated using a homogenizer for 2 hours. The temperature was raised to 45 ° C. to proceed with the polymerization. After the pressure decreased by 0.2 MPa from the saturated vapor pressure of the vinyl chloride monomer at 45 ° C., unreacted vinyl chloride monomer was recovered. The resulting seed latex containing initiator and the like (hereinafter abbreviated as seed 1) had an average particle diameter of 0.60 μm and a solid content of 32%.
実施例１
２．５リットルオートクレーブ中に脱イオン水５００ｇ、１段目仕込み単量体として塩化ビニルモノマーを４９０ｇ（混合単量体の全仕込み量に対して６１重量％）と酢酸ビニルモノマーを９５ｇ（混合単量体の全仕込み量に対して１２重量％）、ポリテトラメチレンエーテルグリコールを２０ｇ、５％水溶液ラウリル硫酸ナトリウムを９ｇ、シード１を８５ｇ、０．１％水溶液硫酸銅を４ｇ仕込み、その後、この反応混合物の温度を３５℃に上げて１段目重合を開始するとともに、０．０５重量％アスコルビン酸水溶液を全重合時間を通じて、重合温度を維持するように連続的に添加した。重合転化率が５０％となったところで、２段目仕込み単量体として、塩化ビニルモノマー１４０ｇ（混合単量体の全仕込み量に対して１８重量％）を２．５リットルオートクレーブに仕込み、重合温度３５℃にて２段目重合を継続した。更に、１段目仕込み単量体と２段目仕込み単量体の合計に対して重合転化率が７５％となったところで、３段目仕込み単量体として、塩化ビニルモノマー７０ｇ（混合単量体の全仕込み量に対して９重量％）を２．５リットルオートクレーブに仕込み、重合温度３５℃にて３段目重合を継続し、混合単量体の合計に対して重合転化率が９０％となったところで重合を終了した。
Example 1
In a 2.5 liter autoclave, 500 g of deionized water, 490 g of vinyl chloride monomer as the first-stage charged monomer (61% by weight based on the total charged amount of the mixed monomer) and 95 g of vinyl acetate monomer (mixed monomer) 20% of polytetramethylene ether glycol, 9 g of 5% aqueous sodium lauryl sulfate, 85 g of seed 1 and 4 g of 0.1% aqueous copper sulfate. The temperature of the reaction mixture was raised to 35 ° C. to start the first-stage polymerization, and a 0.05% by weight aqueous solution of ascorbic acid was continuously added throughout the entire polymerization time so as to maintain the polymerization temperature. When the polymerization conversion reached 50%, as a second-stage monomer, 140 g of vinyl chloride monomer (18% by weight based on the total amount of the mixed monomer) was charged into a 2.5-liter autoclave, and polymerized. The second-stage polymerization was continued at a temperature of 35 ° C. Further, when the polymerization conversion rate was 75% of the total of the first-stage monomer and the second-stage monomer, 70 g of a vinyl chloride monomer (mixed monomer) was used as the third-stage monomer. (9% by weight based on the total amount of the mixture) was charged into a 2.5-liter autoclave, the third-stage polymerization was continued at a polymerization temperature of 35 ° C., and the polymerization conversion was 90% based on the total amount of the mixed monomers. When it became, the polymerization was terminated.
なお、重合開始してから重合終了までの間、５％水溶液ラウリル硫酸ナトリウム１２０ｇを連続的に添加した。 From the start of the polymerization to the end of the polymerization, 120 g of a 5% aqueous sodium lauryl sulfate was continuously added.
そして、未反応モノマーを回収してラテックスとし、スプレードライヤーにて、熱風入口温度１６０℃、出口温度５５℃で噴霧乾燥を行って、塩化ビニル−酢酸ビニル共重合体粒子を得た。得られた塩化ビニル−酢酸ビニル共重合体樹脂は、平均一次粒子径１．５μｍを有し、平均重合度１８３０、平均酢酸ビニル残基単位含有量９．０重量％の塩化ビニル−酢酸ビニル共重合体１００重量部に対し、ラウリル硫酸ナトリウム０．９重量部、ポリテトラメチレンエーテルグリコール２．５重量部を含み、平均粒子径１６μｍを有するものであった。また、得られた塩化ビニル−酢酸ビニル共重合体粒子を用いてペースト塩ビゾルを作製し、物性を評価した。その結果を表１に示す。 Then, the unreacted monomer was recovered to be a latex, which was spray-dried with a spray dryer at a hot air inlet temperature of 160 ° C. and an outlet temperature of 55 ° C. to obtain vinyl chloride-vinyl acetate copolymer particles. The obtained vinyl chloride-vinyl acetate copolymer resin has an average primary particle diameter of 1.5 μm, an average degree of polymerization of 1830, and an average vinyl acetate residue unit content of 9.0% by weight. It contained 0.9 parts by weight of sodium lauryl sulfate and 2.5 parts by weight of polytetramethylene ether glycol with respect to 100 parts by weight of the polymer, and had an average particle diameter of 16 μm. A paste salt visol was prepared using the obtained vinyl chloride-vinyl acetate copolymer particles, and the physical properties were evaluated. Table 1 shows the results.
実施例２
２．５リットルオートクレーブ中に脱イオン水５００ｇ、１段目仕込み単量体として塩化ビニルモノマーを４９０ｇ（混合単量体の全仕込み量に対して６１重量％）と酢酸ビニルモノマーを９５ｇ（混合単量体の全仕込み量に対して１２重量％）、ポリテトラメチレンエーテルグリコールを４０ｇ、５％水溶液ラウリル硫酸ナトリウムを９ｇ、シード１を８５ｇ、０．１％水溶液硫酸銅を４ｇ仕込み、その後、この反応混合物の温度を３５℃に上げて１段目重合を開始するとともに、０．０５重量％アスコルビン酸水溶液を全重合時間を通じて、重合温度を維持するように連続的に添加した。重合転化率が５０％となったところで、２段目仕込み単量体として、塩化ビニルモノマー１４０ｇ（混合単量体の全仕込み量に対して１８重量％）を２．５リットルオートクレーブに仕込み、重合温度３５℃にて２段目重合を継続した。更に、１段目仕込み単量体と２段目仕込み単量体の合計に対して重合転化率が７５％となったところで、３段目仕込み単量体として、塩化ビニルモノマー７０ｇ（混合単量体の全仕込み量に対して９重量％）を２．５リットルオートクレーブに仕込み、重合温度３５℃にて３段目重合を継続し、混合単量体の合計に対して重合転化率が９０％となったところで重合を終了した。
Example 2
In a 2.5 liter autoclave, 500 g of deionized water, 490 g of vinyl chloride monomer as the first-stage charged monomer (61% by weight based on the total charged amount of the mixed monomer) and 95 g of vinyl acetate monomer (mixed monomer) 40% of polytetramethylene ether glycol, 9 g of 5% aqueous sodium lauryl sulfate, 85 g of seed 1 and 4 g of 0.1% aqueous copper sulfate. The temperature of the reaction mixture was raised to 35 ° C. to start the first-stage polymerization, and a 0.05% by weight aqueous solution of ascorbic acid was continuously added throughout the entire polymerization time so as to maintain the polymerization temperature. When the polymerization conversion reached 50%, as a second-stage monomer, 140 g of vinyl chloride monomer (18% by weight based on the total amount of the mixed monomer) was charged into a 2.5-liter autoclave, and polymerized. The second-stage polymerization was continued at a temperature of 35 ° C. Further, when the polymerization conversion rate was 75% of the total of the first-stage monomer and the second-stage monomer, 70 g of a vinyl chloride monomer (mixed monomer) was used as the third-stage monomer. (9% by weight based on the total amount of the mixture) was charged into a 2.5-liter autoclave, the third-stage polymerization was continued at a polymerization temperature of 35 ° C., and the polymerization conversion was 90% based on the total amount of the mixed monomers. When it became, the polymerization was terminated.
なお、重合開始してから重合終了までの間、５％水溶液ラウリル硫酸ナトリウム１２０ｇを連続的に添加した。 From the start of the polymerization to the end of the polymerization, 120 g of a 5% aqueous sodium lauryl sulfate was continuously added.
そして、未反応モノマーを回収してラテックスとし、スプレードライヤーにて、熱風入口温度１６０℃、出口温度５５℃で噴霧乾燥を行って、塩化ビニル−酢酸ビニル共重合体粒子を得た。得られた塩化ビニル−酢酸ビニル共重合体粒子は、平均一次粒子径１．５μｍを有し、平均重合度１８２０、平均酢酸ビニル残基単位含有量９．２重量％の塩化ビニル−酢酸ビニル共重合体１００重量部に対し、ラウリル硫酸ナトリウム０．９重量部、ポリテトラメチレンエーテルグリコール５重量部を含み、平均粒子径１２μｍを有するものであった。また、得られた塩化ビニル−酢酸ビニル共重合体樹脂を用いてペースト塩ビゾルを作製し、物性を評価した。その結果を表１に示す。 Then, the unreacted monomer was recovered to be a latex, which was spray-dried with a spray dryer at a hot air inlet temperature of 160 ° C. and an outlet temperature of 55 ° C. to obtain vinyl chloride-vinyl acetate copolymer particles. The obtained vinyl chloride-vinyl acetate copolymer particles have an average primary particle size of 1.5 μm, an average degree of polymerization of 1820, and an average vinyl acetate residue unit content of 9.2% by weight. It contained 0.9 parts by weight of sodium lauryl sulfate and 5 parts by weight of polytetramethylene ether glycol based on 100 parts by weight of the polymer, and had an average particle diameter of 12 μm. A paste salt visol was prepared using the obtained vinyl chloride-vinyl acetate copolymer resin, and the physical properties were evaluated. Table 1 shows the results.
比較例１
２．５リットルオートクレーブ中に脱イオン水５００ｇ、１段目仕込み単量体として塩化ビニルモノマーを４９０ｇ（混合単量体の全仕込み量に対して６１重量％）と酢酸ビニルモノマーを９５ｇ（混合単量体の全仕込み量に対して１２重量％）、５％水溶液ラウリル硫酸ナトリウムを９ｇ、シード１を８５ｇ、０．１％水溶液硫酸銅を４ｇ仕込み、その後、この反応混合物の温度を３５℃に上げて１段目重合を開始するとともに、０．０５重量％アスコルビン酸水溶液を全重合時間を通じて、重合温度を維持するように連続的に添加した。重合転化率が５０％となったところで、２段目仕込み単量体として、塩化ビニルモノマー１４０ｇ（混合単量体の全仕込み量に対して１８重量％）を２．５リットルオートクレーブに仕込み、重合温度３５℃にて２段目重合を継続した。更に、１段目仕込み単量体と２段目仕込み単量体の合計に対して重合転化率が７５％となったところで、３段目仕込み単量体として、塩化ビニルモノマー７０ｇ（混合単量体の全仕込み量に対して９重量％）を２．５リットルオートクレーブに仕込み、重合温度３５℃にて３段目重合を継続し、混合単量体の合計に対して重合転化率が９０％となったところで重合を終了した。
Comparative Example 1
In a 2.5 liter autoclave, 500 g of deionized water, 490 g of vinyl chloride monomer as the first-stage charged monomer (61% by weight based on the total charged amount of the mixed monomer) and 95 g of vinyl acetate monomer (mixed monomer) 9% of a 5% aqueous sodium lauryl sulfate, 85 g of seed 1 and 4 g of a 0.1% aqueous copper sulfate, and then the temperature of the reaction mixture was reduced to 35 ° C. At the same time, the first stage polymerization was started, and a 0.05% by weight aqueous solution of ascorbic acid was continuously added throughout the entire polymerization time so as to maintain the polymerization temperature. When the polymerization conversion reached 50%, as a second-stage monomer, 140 g of vinyl chloride monomer (18% by weight based on the total amount of the mixed monomer) was charged into a 2.5-liter autoclave, and polymerized. The second-stage polymerization was continued at a temperature of 35 ° C. Further, when the polymerization conversion rate was 75% of the total of the first-stage monomer and the second-stage monomer, 70 g of a vinyl chloride monomer (mixed monomer) was used as the third-stage monomer. (9% by weight based on the total amount of the mixture) was charged into a 2.5-liter autoclave, the third-stage polymerization was continued at a polymerization temperature of 35 ° C., and the polymerization conversion was 90% based on the total amount of the mixed monomers. When it became, the polymerization was terminated.
なお、重合開始してから重合終了までの間、５％水溶液ラウリル硫酸ナトリウム１２０ｇを連続的に添加した。 From the start of the polymerization to the end of the polymerization, 120 g of a 5% aqueous sodium lauryl sulfate was continuously added.
そして、未反応モノマーを回収してラテックスとし、スプレードライヤーにて、熱風入口温度１６０℃、出口温度５５℃で噴霧乾燥を行って、塩化ビニル−酢酸ビニル共重合体樹脂を得た。得られた塩化ビニル−酢酸ビニル共重合体樹脂は、平均一次粒子径１．５μｍを有し、平均重合度１９１０、平均酢酸ビニル残基単位含有量９．１．重量％の塩化ビニル−酢酸ビニル共重合体１００重量部に対し、ラウリル硫酸ナトリウム０．９重量部を含むものであった。また、得られた塩化ビニル−酢酸ビニル共重合体樹脂を用いてペースト塩ビゾルを作製し、物性を評価した。その結果を表２に示す。 Then, the unreacted monomer was recovered to form a latex, which was spray-dried with a spray dryer at a hot air inlet temperature of 160 ° C. and an outlet temperature of 55 ° C. to obtain a vinyl chloride-vinyl acetate copolymer resin. The obtained vinyl chloride-vinyl acetate copolymer resin has an average primary particle diameter of 1.5 μm, an average degree of polymerization of 1910, and an average vinyl acetate residue unit content of 9.1. It contained 0.9 parts by weight of sodium lauryl sulfate based on 100 parts by weight of a vinyl chloride-vinyl acetate copolymer of 100% by weight. A paste salt visol was prepared using the obtained vinyl chloride-vinyl acetate copolymer resin, and the physical properties were evaluated. Table 2 shows the results.
比較例２
２．５リットルオートクレーブ中に脱イオン水５００ｇ、１段目仕込み単量体として塩化ビニルモノマーを４９０ｇ（混合単量体の全仕込み量に対して６１重量％）と酢酸ビニルモノマーを９５ｇ（混合単量体の全仕込み量に対して１２重量％）５％水溶液ラウリル硫酸ナトリウムを９ｇ、シード１を８５ｇ、０．１％水溶液硫酸銅を４ｇ仕込み、その後、この反応混合物の温度を３５℃に上げて１段目重合を開始するとともに、０．０５重量％アスコルビン酸水溶液を全重合時間を通じて、重合温度を維持するように連続的に添加した。重合転化率が５０％となったところで、２段目仕込み単量体として、塩化ビニルモノマー１４０ｇ（混合単量体の全仕込み量に対して１８重量％）を２．５リットルオートクレーブに仕込み、重合温度３５℃にて２段目重合を継続した。更に、１段目仕込み単量体と２段目仕込み単量体の合計に対して重合転化率が７５％となったところで、３段目仕込み単量体として、塩化ビニルモノマー７０ｇ（混合単量体の全仕込み量に対して９重量％）を２．５リットルオートクレーブに仕込み、重合温度３５℃にて３段目重合を継続し、混合単量体の合計に対して重合転化率が９０％となったところで重合を終了した。
Comparative Example 2
In a 2.5 liter autoclave, 500 g of deionized water, 490 g of vinyl chloride monomer as the first-stage charged monomer (61% by weight based on the total charged amount of the mixed monomer) and 95 g of vinyl acetate monomer (mixed monomer) 9% of a 5% aqueous sodium lauryl sulfate, 85 g of seed 1 and 4 g of a 0.1% aqueous copper sulfate, and then the temperature of the reaction mixture was raised to 35 ° C. In addition to the initiation of the first-stage polymerization, a 0.05% by weight aqueous solution of ascorbic acid was continuously added throughout the entire polymerization time so as to maintain the polymerization temperature. When the polymerization conversion reached 50%, as a second-stage monomer, 140 g of vinyl chloride monomer (18% by weight based on the total amount of the mixed monomer) was charged into a 2.5-liter autoclave, and polymerized. The second-stage polymerization was continued at a temperature of 35 ° C. Further, when the polymerization conversion rate was 75% of the total of the first-stage monomer and the second-stage monomer, 70 g of a vinyl chloride monomer (mixed monomer) was used as the third-stage monomer. (9% by weight based on the total amount of the mixture) was charged into a 2.5-liter autoclave, the third-stage polymerization was continued at a polymerization temperature of 35 ° C., and the polymerization conversion was 90% based on the total amount of the mixed monomers. When it became, the polymerization was terminated.
なお、重合開始してから重合終了までの間、５％水溶液ラウリル硫酸ナトリウム１２０ｇを連続的に添加した。 From the start of the polymerization to the end of the polymerization, 120 g of a 5% aqueous sodium lauryl sulfate was continuously added.
そして、未反応モノマーを回収してラテックスとした後、ポリテトラメチレンエーテルグリコールを５ｇ添加し、スプレードライヤーにて、熱風入口温度１６０℃、出口温度５５℃で噴霧乾燥を行って、塩化ビニル−酢酸ビニル共重合体樹脂を得た。得られた塩化ビニル−酢酸ビニル共重合体樹脂は、平均一次粒子径１．５μｍを有し、平均重合度１８２０、平均酢酸ビニル残基単位含有量９．２重量％の塩化ビニル−酢酸ビニル共重合体１００重量部に対し、ラウリル硫酸ナトリウム０．９重量部、ポリテトラメチレンエーテルグリコール０．５重量部を含むものであった。また、得られた塩化ビニル−酢酸ビニル共重合体樹脂を用いてペースト塩ビゾルを作製し、物性を評価した。その結果を表２に示す。 After collecting the unreacted monomer to form a latex, 5 g of polytetramethylene ether glycol was added, and spray drying was performed with a spray drier at a hot air inlet temperature of 160 ° C. and an outlet temperature of 55 ° C. to obtain vinyl chloride-acetic acid. A vinyl copolymer resin was obtained. The obtained vinyl chloride-vinyl acetate copolymer resin has an average primary particle size of 1.5 μm, an average degree of polymerization of 1820, and an average vinyl acetate residue unit content of 9.2% by weight. It contained 0.9 parts by weight of sodium lauryl sulfate and 0.5 parts by weight of polytetramethylene ether glycol based on 100 parts by weight of the polymer. A paste salt visol was prepared using the obtained vinyl chloride-vinyl acetate copolymer resin, and the physical properties were evaluated. Table 2 shows the results.
比較例３
２．５リットルオートクレーブ中に脱イオン水５００ｇ、１段目仕込み単量体として塩化ビニルモノマーを４９０ｇ（混合単量体の全仕込み量に対して６１重量％）と酢酸ビニルモノマーを９５ｇ（混合単量体の全仕込み量に対して１２重量％）、ポリオキシアルキレンラウリルエーテル（（商品名）ノイゲンＬＰ−１００、第一工業製薬製）４０ｇ、５％水溶液ラウリル硫酸ナトリウムを９ｇ、シード１を８５ｇ、０．１％水溶液硫酸銅を４ｇ仕込み、その後、この反応混合物の温度を３５℃に上げて１段目重合を開始するとともに、０．０５重量％アスコルビン酸水溶液を全重合時間を通じて、重合温度を維持するように連続的に添加した。重合転化率が５０％となったところで、２段目仕込み単量体として、塩化ビニルモノマー１４０ｇ（混合単量体の全仕込み量に対して１８重量％）を２．５リットルオートクレーブに仕込み、重合温度３５℃にて２段目重合を継続した。更に、１段目仕込み単量体と２段目仕込み単量体の合計に対して重合転化率が７５％となったところで、３段目仕込み単量体として、塩化ビニルモノマー７０ｇ（混合単量体の全仕込み量に対して９重量％）を２．５リットルオートクレーブに仕込み、重合温度３５℃にて３段目重合を継続し、混合単量体の合計に対して重合転化率が９０％となったところで重合を終了したが、凝集し、粒子を得ることができなかった。
Comparative Example 3
In a 2.5 liter autoclave, 500 g of deionized water, 490 g of vinyl chloride monomer as the first-stage charged monomer (61% by weight based on the total charged amount of the mixed monomer) and 95 g of vinyl acetate monomer (mixed monomer) 12% by weight based on the total charged amount of the monomer), 40 g of polyoxyalkylene lauryl ether (trade name: Neugen LP-100, manufactured by Daiichi Kogyo Seiyaku) 9 g of a 5% aqueous sodium lauryl sulfate, and 85 g of seed 1 , 4 g of a 0.1% aqueous copper sulfate solution, then raise the temperature of the reaction mixture to 35 ° C. to start the first-stage polymerization, and add a 0.05% by weight aqueous solution of ascorbic acid to the polymerization temperature throughout the polymerization time. Was added continuously to maintain When the polymerization conversion reached 50%, as a second-stage monomer, 140 g of vinyl chloride monomer (18% by weight based on the total amount of the mixed monomer) was charged into a 2.5-liter autoclave, and polymerized. The second-stage polymerization was continued at a temperature of 35 ° C. Further, when the polymerization conversion rate was 75% of the total of the first-stage monomer and the second-stage monomer, 70 g of a vinyl chloride monomer (mixed monomer) was used as the third-stage monomer. (9% by weight based on the total amount of the mixture) was charged into a 2.5-liter autoclave, the third-stage polymerization was continued at a polymerization temperature of 35 ° C., and the polymerization conversion was 90% based on the total amount of the mixed monomers. When it became, the polymerization was terminated, but aggregation occurred, and particles could not be obtained.
本発明の塩化ビニル−酢酸ビニル共重合体粒子は、ペースト塩ビゾルとした際の初期粘度が高く、低温加工した際の成形品の破断伸びに優れ、コート剤、特に自動車アンダーボディコート剤、自動車用シーラント用として優れた特性を有するものであり、その産業上の利用価値は高いものである。 The vinyl chloride-vinyl acetate copolymer particles of the present invention have a high initial viscosity when used as a paste salt visol, have excellent elongation at break of molded articles when processed at low temperature, and have excellent coating properties, especially underbody coating compositions for automobiles and automobiles. It has excellent properties for use as a sealant for applications, and its industrial utility value is high.
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