WO2010061630A1 - Processing assistant for expansion molding, vinyl chloride resin composition for expansion molding, and expansion molded body - Google Patents
Processing assistant for expansion molding, vinyl chloride resin composition for expansion molding, and expansion molded body Download PDFInfo
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- WO2010061630A1 WO2010061630A1 PCT/JP2009/006436 JP2009006436W WO2010061630A1 WO 2010061630 A1 WO2010061630 A1 WO 2010061630A1 JP 2009006436 W JP2009006436 W JP 2009006436W WO 2010061630 A1 WO2010061630 A1 WO 2010061630A1
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- vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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- Engineering & Computer Science (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Disclosed is a vinyl chloride resin expansion molded body having fine and uniform foam cells and excellent appearance. Also disclosed are a processing assistant for expansion molding, which is useful for production of the vinyl chloride resin expansion molded body, and a vinyl chloride resin composition for expansion molding. The processing assistant for expansion molding comprises a polymer (A) which is obtained by polymerizing a monomer component (a) containing not less than 65% by mass of isobutyl methacrylate, and the polymer (A) has a reduced viscosity (ηsp/c) of not less than 4, when measured at 25˚C by dissolving 0.1 g of the polymer (A) into 100 ml of chloroform.
Description
本発明は、発泡成形用加工助剤、前記加工助剤を含む発泡成形用塩化ビニル系樹脂組成物及び前記樹脂組成物を成形して得られる発泡成形体に関する。
本願は、２００８年１１月２８日に日本に出願された特願２００８－３０５１５７号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a foam molding processing aid, a vinyl chloride resin composition for foam molding containing the processing aid, and a foam molded article obtained by molding the resin composition.
This application claims priority based on Japanese Patent Application No. 2008-305157 for which it applied to Japan on November 28, 2008, and uses the content here.
本願は、２００８年１１月２８日に日本に出願された特願２００８－３０５１５７号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a foam molding processing aid, a vinyl chloride resin composition for foam molding containing the processing aid, and a foam molded article obtained by molding the resin composition.
This application claims priority based on Japanese Patent Application No. 2008-305157 for which it applied to Japan on November 28, 2008, and uses the content here.
塩化ビニル系樹脂は、耐薬品性、耐衝撃性、耐候性等に優れた性質を有し、かつ、安価であることから、利用価値の高い汎用樹脂材料として広く用いられている。発泡成形は、好適な用途の一つであり、例えば合成木材等を指向した建材として発泡成形体の製造が試みられている。
しかしながら、塩化ビニル系樹脂からそのまま発泡成形体を製造する場合は、塩化ビニル系樹脂の通常の成形加工温度下では、伸び特性、溶融強度が不足するので、不均質な発泡セル構造となり、また、任意の高発泡倍率とすることができず、満足な発泡成形体を得ることは困難である。更に、塩化ビニル系樹脂は、許容成形条件幅が狭いので、成形加工条件の変更だけによって満足な発泡成形体を得ることも困難である。
また、塩化ビニル系樹脂の発泡成形の普及、拡大と相俟って、近年、発泡成形体に対して、より優れた成形外観が要求されている。
塩化ビニル系樹脂の発泡成形性及び発泡成形体の成形外観を改善する方法としては、例えば、特許文献１には、炭素数３～５のアルキル基を有するメタクリル酸アルキルエステルを２０～５０質量％含む単量体成分を共重合して得られる共重合体からなる発泡成形用加工助剤が開示されている。また、特許文献２には、数平均分子量が１０万以下のポリメタクリル酸イソブチルを含む発泡成形用塩化ビニル系樹脂組成物が開示されている。 Vinyl chloride-based resins are widely used as general-purpose resin materials with high utility value because they have excellent properties such as chemical resistance, impact resistance, and weather resistance, and are inexpensive. Foam molding is one of the preferred applications, and for example, attempts are being made to produce foam molded articles as building materials oriented toward synthetic wood and the like.
However, in the case of producing a foamed molded product as it is from a vinyl chloride resin, under the normal molding temperature of the vinyl chloride resin, the elongation characteristics and the melt strength are insufficient, resulting in a heterogeneous foam cell structure, Arbitrary high expansion ratios cannot be achieved, and it is difficult to obtain satisfactory foamed molded articles. Further, since the allowable molding condition width of the vinyl chloride resin is narrow, it is difficult to obtain a satisfactory foamed molded article only by changing the molding processing conditions.
In addition, in conjunction with the popularization and expansion of vinyl chloride resin foam molding, in recent years, a more excellent molded appearance has been demanded for foam molded articles.
As a method for improving the foaming moldability of a vinyl chloride resin and the molded appearance of a foamed molded article, for example, Patent Document 1 discloses that 20 to 50% by mass of an alkyl methacrylate having an alkyl group having 3 to 5 carbon atoms. There is disclosed a processing aid for foam molding comprising a copolymer obtained by copolymerizing a monomer component to be contained. Patent Document 2 discloses a vinyl chloride resin composition for foam molding containing polyisobutyl methacrylate having a number average molecular weight of 100,000 or less.
しかしながら、塩化ビニル系樹脂からそのまま発泡成形体を製造する場合は、塩化ビニル系樹脂の通常の成形加工温度下では、伸び特性、溶融強度が不足するので、不均質な発泡セル構造となり、また、任意の高発泡倍率とすることができず、満足な発泡成形体を得ることは困難である。更に、塩化ビニル系樹脂は、許容成形条件幅が狭いので、成形加工条件の変更だけによって満足な発泡成形体を得ることも困難である。
また、塩化ビニル系樹脂の発泡成形の普及、拡大と相俟って、近年、発泡成形体に対して、より優れた成形外観が要求されている。
塩化ビニル系樹脂の発泡成形性及び発泡成形体の成形外観を改善する方法としては、例えば、特許文献１には、炭素数３～５のアルキル基を有するメタクリル酸アルキルエステルを２０～５０質量％含む単量体成分を共重合して得られる共重合体からなる発泡成形用加工助剤が開示されている。また、特許文献２には、数平均分子量が１０万以下のポリメタクリル酸イソブチルを含む発泡成形用塩化ビニル系樹脂組成物が開示されている。 Vinyl chloride-based resins are widely used as general-purpose resin materials with high utility value because they have excellent properties such as chemical resistance, impact resistance, and weather resistance, and are inexpensive. Foam molding is one of the preferred applications, and for example, attempts are being made to produce foam molded articles as building materials oriented toward synthetic wood and the like.
However, in the case of producing a foamed molded product as it is from a vinyl chloride resin, under the normal molding temperature of the vinyl chloride resin, the elongation characteristics and the melt strength are insufficient, resulting in a heterogeneous foam cell structure, Arbitrary high expansion ratios cannot be achieved, and it is difficult to obtain satisfactory foamed molded articles. Further, since the allowable molding condition width of the vinyl chloride resin is narrow, it is difficult to obtain a satisfactory foamed molded article only by changing the molding processing conditions.
In addition, in conjunction with the popularization and expansion of vinyl chloride resin foam molding, in recent years, a more excellent molded appearance has been demanded for foam molded articles.
As a method for improving the foaming moldability of a vinyl chloride resin and the molded appearance of a foamed molded article, for example, Patent Document 1 discloses that 20 to 50% by mass of an alkyl methacrylate having an alkyl group having 3 to 5 carbon atoms. There is disclosed a processing aid for foam molding comprising a copolymer obtained by copolymerizing a monomer component to be contained. Patent Document 2 discloses a vinyl chloride resin composition for foam molding containing polyisobutyl methacrylate having a number average molecular weight of 100,000 or less.
しかしながら、特許文献１及び特許文献２で提案されている方法では、塩化ビニル系樹脂の発泡成形性及び発泡成形体の成形外観の向上効果は、必ずしも充分ではなかった。
However, with the methods proposed in Patent Document 1 and Patent Document 2, the effect of improving the foaming moldability of the vinyl chloride resin and the molding appearance of the foamed molded product is not always sufficient.
本発明の目的は、微細で均一な発泡セルを有し、かつ、優れた成形外観を有する発泡成形体を得るための発泡成形用加工助剤を提供することにある。
An object of the present invention is to provide a processing aid for foam molding for obtaining a foam molded article having fine and uniform foam cells and having an excellent molded appearance.
すなわち、本発明は、メタクリル酸イソブチルを６５質量％以上含有する単量体成分（ａ）を重合して得られる重合体（Ａ）からなる発泡成形用加工助剤であって、重合体（Ａ）が、１００ｍｌのクロロホルムに０．１ｇを溶解して２５℃で測定した還元粘度（ηｓｐ／ｃ）が４以上である、発泡成形用加工助剤である。
また、本発明は、塩化ビニル系樹脂１００質量部に対して、前記発泡成形用加工助剤１～２５質量部を含有する発泡成形用塩化ビニル系樹脂組成物である。
更に、本発明は、前記発泡成形用塩化ビニル系樹脂組成物を成形して得られる発泡成形体である。 That is, the present invention is a processing aid for foam molding comprising a polymer (A) obtained by polymerizing a monomer component (a) containing 65% by mass or more of isobutyl methacrylate, wherein the polymer (A ) Is a processing aid for foam molding in which 0.1 g is dissolved in 100 ml of chloroform and the reduced viscosity (η sp / c) measured at 25 ° C. is 4 or more.
The present invention also relates to a vinyl chloride resin composition for foam molding, comprising 1 to 25 parts by mass of the foam molding processing aid per 100 parts by mass of the vinyl chloride resin.
Furthermore, the present invention is a foam molded product obtained by molding the vinyl chloride resin composition for foam molding.
また、本発明は、塩化ビニル系樹脂１００質量部に対して、前記発泡成形用加工助剤１～２５質量部を含有する発泡成形用塩化ビニル系樹脂組成物である。
更に、本発明は、前記発泡成形用塩化ビニル系樹脂組成物を成形して得られる発泡成形体である。 That is, the present invention is a processing aid for foam molding comprising a polymer (A) obtained by polymerizing a monomer component (a) containing 65% by mass or more of isobutyl methacrylate, wherein the polymer (A ) Is a processing aid for foam molding in which 0.1 g is dissolved in 100 ml of chloroform and the reduced viscosity (η sp / c) measured at 25 ° C. is 4 or more.
The present invention also relates to a vinyl chloride resin composition for foam molding, comprising 1 to 25 parts by mass of the foam molding processing aid per 100 parts by mass of the vinyl chloride resin.
Furthermore, the present invention is a foam molded product obtained by molding the vinyl chloride resin composition for foam molding.
本発明の発泡成形用加工助剤を配合することにより、塩化ビニル系樹脂組成物の溶融及び混練を効率良く行い、かつ溶融強度を高めることができる。これにより、塩化ビニル系樹脂組成物を用いた発泡成形において、微細で均一な発泡セルを有し、更には優れた成形外観を有する発泡成形体を得ることができる。
By blending the processing aid for foam molding of the present invention, the vinyl chloride resin composition can be efficiently melted and kneaded and the melt strength can be increased. Thereby, in the foam molding using the vinyl chloride resin composition, it is possible to obtain a foam molded article having fine and uniform foam cells and having an excellent molded appearance.
本発明の発泡成形用加工助剤は、メタクリル酸イソブチルを含有する単量体成分（ａ）を重合して得られる重合体（Ａ）を含有する。
単量体成分（ａ）（１００質量％）中のメタクリル酸イソブチルの含有率は、６５質量％以上、好ましくは７０質量％以上、より好ましくは７６質量％以上である。他方、単量体成分（ａ）（１００質量％）中のメタクリル酸イソブチルの含有率は、１００質量％以下、好ましくは９９質量％以下、より好ましくは９８質量％以下である。単量体成分（ａ）中のメタクリル酸イソブチルの含有率が６５質量％以上であれば、発泡成形用塩化ビニル系樹脂組成物の溶融及び混練を効率良く行うことができ、微細で均一な発泡セル構造と高発泡倍率の達成が容易となる。
単量体成分（ａ）は、必要に応じて、他の単量体を含有してもよい。
他の単量体としては、例えば、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ｎ－ブチル、メタクリル酸ｔ－ブチル、メタクリル酸ペンチル、メタクリル酸２－エチルヘキシル等のメタクリル酸エステル；アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ－ブチル、アクリル酸イソブチル、アクリル酸ｔ－ブチル、アクリル酸２－エチルヘキシル、アクリル酸ベンジル、アクリル酸フェニル等のアクリル酸エステル；スチレン、α－メチルスチレン、ビニルトルエン等の芳香族ビニル単量体；アクリロニトリル、メタクリロニトリル等のシアン化ビニル単量体；酢酸ビニル等のビニルエステル；無水マレイン酸等の酸無水物が挙げられる。他の単量体は、目的に応じて１種を単独で用いてもよく２種以上を併用してもよい。
単量体成分（ａ）（１００質量％）中の、他の単量体の含有率は、３５質量％以下、好ましくは３０質量％以下、より好ましくは２４質量％以下である。他方、単量体成分（ａ）（１００質量％）中の、他の単量体の含有率は、０質量％以上、好ましくは１質量％以上、より好ましくは２質量％以上である。これらは、発泡成形用塩化ビニル系樹脂組成物の溶融及び混練、更には得られる発泡成形体の成形外観を損なわない範囲で任意に設定できる。また、塩化ビニル系樹脂とのブレンド時におけるコンパウンドの嵩比の低下をさせず、発泡成形用加工助剤を粉体として回収する工程での回収性を損なわず、粉体のブロッキングを損なわない範囲で任意に設定できる。
また、上述の各単量体以外に、ジビニルベンゼン、アリルメタクリレート、１，３－ブタンジオールジメタクリレート、トリアリルシアヌレート等の多官能性単量体を含有してもよい。単量体成分（ａ）（１００質量％）中の多官能性単量体の含有率は、好ましくは０．０１～２．０質量％、より好ましくは０．１～２．０質量％である。多官能性単量体を０．０１質量％以上使用することにより、見掛けの分子量を高くして、発泡成形性を向上することができる。他方、２．０質量％以下とすることで発泡倍率の低下や成形外観の悪化を招くことがない。 The processing aid for foam molding of the present invention contains a polymer (A) obtained by polymerizing a monomer component (a) containing isobutyl methacrylate.
The content of isobutyl methacrylate in the monomer component (a) (100% by mass) is 65% by mass or more, preferably 70% by mass or more, and more preferably 76% by mass or more. On the other hand, the content of isobutyl methacrylate in the monomer component (a) (100% by mass) is 100% by mass or less, preferably 99% by mass or less, more preferably 98% by mass or less. If the content of isobutyl methacrylate in the monomer component (a) is 65% by mass or more, the vinyl chloride resin composition for foam molding can be efficiently melted and kneaded, resulting in fine and uniform foaming. The cell structure and high foaming ratio can be easily achieved.
The monomer component (a) may contain other monomers as necessary.
Examples of other monomers include methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, pentyl methacrylate, 2-ethylhexyl methacrylate; Acrylic acid esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, phenyl acrylate; styrene, α-methylstyrene, vinyl Examples thereof include aromatic vinyl monomers such as toluene; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; vinyl esters such as vinyl acetate; and acid anhydrides such as maleic anhydride. Other monomers may be used alone or in combination of two or more depending on the purpose.
The content of other monomers in the monomer component (a) (100% by mass) is 35% by mass or less, preferably 30% by mass or less, more preferably 24% by mass or less. On the other hand, the content of other monomers in the monomer component (a) (100% by mass) is 0% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more. These can be arbitrarily set as long as the vinyl chloride resin composition for foam molding is melted and kneaded, and further the molded appearance of the resulting foam molded article is not impaired. In addition, the volume ratio of the compound at the time of blending with the vinyl chloride resin is not reduced, the recoverability in the process of recovering the foaming processing aid as a powder is not impaired, and the powder blocking is not impaired. Can be set arbitrarily.
In addition to the above-mentioned monomers, polyfunctional monomers such as divinylbenzene, allyl methacrylate, 1,3-butanediol dimethacrylate, triallyl cyanurate may be contained. The content of the polyfunctional monomer in the monomer component (a) (100% by mass) is preferably 0.01 to 2.0% by mass, more preferably 0.1 to 2.0% by mass. is there. By using 0.01% by mass or more of the polyfunctional monomer, the apparent molecular weight can be increased and the foam moldability can be improved. On the other hand, when the content is 2.0% by mass or less, the foaming ratio is not reduced and the molded appearance is not deteriorated.
単量体成分（ａ）（１００質量％）中のメタクリル酸イソブチルの含有率は、６５質量％以上、好ましくは７０質量％以上、より好ましくは７６質量％以上である。他方、単量体成分（ａ）（１００質量％）中のメタクリル酸イソブチルの含有率は、１００質量％以下、好ましくは９９質量％以下、より好ましくは９８質量％以下である。単量体成分（ａ）中のメタクリル酸イソブチルの含有率が６５質量％以上であれば、発泡成形用塩化ビニル系樹脂組成物の溶融及び混練を効率良く行うことができ、微細で均一な発泡セル構造と高発泡倍率の達成が容易となる。
単量体成分（ａ）は、必要に応じて、他の単量体を含有してもよい。
他の単量体としては、例えば、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ｎ－ブチル、メタクリル酸ｔ－ブチル、メタクリル酸ペンチル、メタクリル酸２－エチルヘキシル等のメタクリル酸エステル；アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ－ブチル、アクリル酸イソブチル、アクリル酸ｔ－ブチル、アクリル酸２－エチルヘキシル、アクリル酸ベンジル、アクリル酸フェニル等のアクリル酸エステル；スチレン、α－メチルスチレン、ビニルトルエン等の芳香族ビニル単量体；アクリロニトリル、メタクリロニトリル等のシアン化ビニル単量体；酢酸ビニル等のビニルエステル；無水マレイン酸等の酸無水物が挙げられる。他の単量体は、目的に応じて１種を単独で用いてもよく２種以上を併用してもよい。
単量体成分（ａ）（１００質量％）中の、他の単量体の含有率は、３５質量％以下、好ましくは３０質量％以下、より好ましくは２４質量％以下である。他方、単量体成分（ａ）（１００質量％）中の、他の単量体の含有率は、０質量％以上、好ましくは１質量％以上、より好ましくは２質量％以上である。これらは、発泡成形用塩化ビニル系樹脂組成物の溶融及び混練、更には得られる発泡成形体の成形外観を損なわない範囲で任意に設定できる。また、塩化ビニル系樹脂とのブレンド時におけるコンパウンドの嵩比の低下をさせず、発泡成形用加工助剤を粉体として回収する工程での回収性を損なわず、粉体のブロッキングを損なわない範囲で任意に設定できる。
また、上述の各単量体以外に、ジビニルベンゼン、アリルメタクリレート、１，３－ブタンジオールジメタクリレート、トリアリルシアヌレート等の多官能性単量体を含有してもよい。単量体成分（ａ）（１００質量％）中の多官能性単量体の含有率は、好ましくは０．０１～２．０質量％、より好ましくは０．１～２．０質量％である。多官能性単量体を０．０１質量％以上使用することにより、見掛けの分子量を高くして、発泡成形性を向上することができる。他方、２．０質量％以下とすることで発泡倍率の低下や成形外観の悪化を招くことがない。 The processing aid for foam molding of the present invention contains a polymer (A) obtained by polymerizing a monomer component (a) containing isobutyl methacrylate.
The content of isobutyl methacrylate in the monomer component (a) (100% by mass) is 65% by mass or more, preferably 70% by mass or more, and more preferably 76% by mass or more. On the other hand, the content of isobutyl methacrylate in the monomer component (a) (100% by mass) is 100% by mass or less, preferably 99% by mass or less, more preferably 98% by mass or less. If the content of isobutyl methacrylate in the monomer component (a) is 65% by mass or more, the vinyl chloride resin composition for foam molding can be efficiently melted and kneaded, resulting in fine and uniform foaming. The cell structure and high foaming ratio can be easily achieved.
The monomer component (a) may contain other monomers as necessary.
Examples of other monomers include methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, pentyl methacrylate, 2-ethylhexyl methacrylate; Acrylic acid esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, phenyl acrylate; styrene, α-methylstyrene, vinyl Examples thereof include aromatic vinyl monomers such as toluene; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; vinyl esters such as vinyl acetate; and acid anhydrides such as maleic anhydride. Other monomers may be used alone or in combination of two or more depending on the purpose.
The content of other monomers in the monomer component (a) (100% by mass) is 35% by mass or less, preferably 30% by mass or less, more preferably 24% by mass or less. On the other hand, the content of other monomers in the monomer component (a) (100% by mass) is 0% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more. These can be arbitrarily set as long as the vinyl chloride resin composition for foam molding is melted and kneaded, and further the molded appearance of the resulting foam molded article is not impaired. In addition, the volume ratio of the compound at the time of blending with the vinyl chloride resin is not reduced, the recoverability in the process of recovering the foaming processing aid as a powder is not impaired, and the powder blocking is not impaired. Can be set arbitrarily.
In addition to the above-mentioned monomers, polyfunctional monomers such as divinylbenzene, allyl methacrylate, 1,3-butanediol dimethacrylate, triallyl cyanurate may be contained. The content of the polyfunctional monomer in the monomer component (a) (100% by mass) is preferably 0.01 to 2.0% by mass, more preferably 0.1 to 2.0% by mass. is there. By using 0.01% by mass or more of the polyfunctional monomer, the apparent molecular weight can be increased and the foam moldability can be improved. On the other hand, when the content is 2.0% by mass or less, the foaming ratio is not reduced and the molded appearance is not deteriorated.
本発明において、発泡成形用加工助剤を構成する重合体（Ａ）の還元粘度（ηｓｐ／ｃ）は、４以上、好ましくは５以上である。他方、発泡成形用加工助剤を構成する重合体（Ａ）の還元粘度（ηｓｐ／ｃ）は、好ましくは２０以下、より好ましくは１５以下である。還元粘度（ηｓｐ／ｃ）を４以上とすることにより、溶融強度付与効果が高められ、充分な発泡倍率の成形体を得られ易くなる。他方、還元粘度（ηｓｐ／ｃ）を２０以下とすることにより、過剰な溶融強度を付与することなく、成形外観が良好な発泡成形体が得られ易くなる。
この還元粘度（ηｓｐ／ｃ）は、重合体（Ａ）０．１ｇを１００ｍｌのクロロホルムに溶解し、２５℃で測定した値である。
重合体（Ａ）の還元粘度（ηｓｐ／ｃ）をこの範囲に調節する方法としては、例えば、重合時の連鎖移動剤や開始剤の使用量の調節、重合温度の調節等の方法が挙げられる。表面外観の良好な発泡成形体を得るには連鎖移動剤を使用して調節する方法が好ましい。 In the present invention, the reduced viscosity (η sp / c) of the polymer (A) constituting the processing aid for foam molding is 4 or more, preferably 5 or more. On the other hand, the reduced viscosity (η sp / c) of the polymer (A) constituting the processing aid for foam molding is preferably 20 or less, more preferably 15 or less. By setting the reduced viscosity (η sp / c) to 4 or more, the effect of imparting melt strength is enhanced, and it becomes easy to obtain a molded article having a sufficient expansion ratio. On the other hand, when the reduced viscosity (η sp / c) is 20 or less, a foamed molded article having a good molded appearance can be easily obtained without imparting excessive melt strength.
This reduced viscosity (η sp / c) is a value measured at 25 ° C. by dissolving 0.1 g of the polymer (A) in 100 ml of chloroform.
Examples of the method for adjusting the reduced viscosity (η sp / c) of the polymer (A) within this range include methods such as adjustment of the amount of chain transfer agent and initiator used during polymerization and adjustment of the polymerization temperature. It is done. In order to obtain a foamed molded article having a good surface appearance, a method of adjusting using a chain transfer agent is preferred.
この還元粘度（ηｓｐ／ｃ）は、重合体（Ａ）０．１ｇを１００ｍｌのクロロホルムに溶解し、２５℃で測定した値である。
重合体（Ａ）の還元粘度（ηｓｐ／ｃ）をこの範囲に調節する方法としては、例えば、重合時の連鎖移動剤や開始剤の使用量の調節、重合温度の調節等の方法が挙げられる。表面外観の良好な発泡成形体を得るには連鎖移動剤を使用して調節する方法が好ましい。 In the present invention, the reduced viscosity (η sp / c) of the polymer (A) constituting the processing aid for foam molding is 4 or more, preferably 5 or more. On the other hand, the reduced viscosity (η sp / c) of the polymer (A) constituting the processing aid for foam molding is preferably 20 or less, more preferably 15 or less. By setting the reduced viscosity (η sp / c) to 4 or more, the effect of imparting melt strength is enhanced, and it becomes easy to obtain a molded article having a sufficient expansion ratio. On the other hand, when the reduced viscosity (η sp / c) is 20 or less, a foamed molded article having a good molded appearance can be easily obtained without imparting excessive melt strength.
This reduced viscosity (η sp / c) is a value measured at 25 ° C. by dissolving 0.1 g of the polymer (A) in 100 ml of chloroform.
Examples of the method for adjusting the reduced viscosity (η sp / c) of the polymer (A) within this range include methods such as adjustment of the amount of chain transfer agent and initiator used during polymerization and adjustment of the polymerization temperature. It is done. In order to obtain a foamed molded article having a good surface appearance, a method of adjusting using a chain transfer agent is preferred.
重合体（Ａ）を得る際の重合法としては、公知の各種方法を用いることができ、例えば、乳化重合法、懸濁重合法、溶液重合法が挙げられる。重合時の単量体の添加方法は、一括添加、滴下、分割添加の何れでもよい。共重合体は、ランダム共重合体、ブロック共重合の何れでもよいが、単量体の一括添加により得られるランダム共重合体が好ましい。
乳化重合法において用いる乳化剤としては、例えば、脂肪酸塩、アルキル硫酸エステル塩、アルキルベンゼンスルホン酸塩、アルキルリン酸エステル塩、ジアルキルスルホコハク酸塩等のアニオン性界面活性剤；ポリオキシエチレンアルキルエーテル、ポリオキシエチレン脂肪酸エステル、ソルビタン酸脂肪エステル、グリセリン脂肪酸エステル等のノニオン性界面活性剤；アルキルアミン塩等のカチオン性界面活性剤が挙げられる。これら乳化剤は、１種を単独で用いてもよく２種以上を併用してもよい。
乳化剤の種類により重合系のｐＨがアルカリ側になるときは、メタクリル酸アルキルエステルの加水分解を防止するために適当なｐＨ調節剤を用いることもできる。ｐＨ調節剤としては、例えば、ホウ酸－塩化カリウム－水酸化カリウム、リン酸二水素カリウム－リン酸水素二ナトリウム、ホウ酸－塩化カリウム－炭酸カリウム、クエン酸－クエン酸水素カリウム、リン酸二水素カリウム－ホウ砂、リン酸水素二ナトリウム－クエン酸が挙げられる。 Various known methods can be used as the polymerization method for obtaining the polymer (A), and examples thereof include an emulsion polymerization method, a suspension polymerization method, and a solution polymerization method. The addition method of the monomer at the time of superposition | polymerization may be any of lump addition, dripping, and divided addition. The copolymer may be either a random copolymer or a block copolymer, but a random copolymer obtained by batch addition of monomers is preferred.
Examples of the emulsifier used in the emulsion polymerization method include anionic surfactants such as fatty acid salt, alkyl sulfate ester salt, alkylbenzene sulfonate salt, alkyl phosphate ester salt, dialkyl sulfosuccinate salt; polyoxyethylene alkyl ether, polyoxy Nonionic surfactants such as ethylene fatty acid esters, sorbitan acid fatty esters, and glycerin fatty acid esters; and cationic surfactants such as alkylamine salts. These emulsifiers may be used individually by 1 type, and may use 2 or more types together.
When the pH of the polymerization system is on the alkali side depending on the type of emulsifier, an appropriate pH adjusting agent can be used to prevent hydrolysis of the alkyl methacrylate. Examples of pH regulators include boric acid-potassium chloride-potassium hydroxide, potassium dihydrogen phosphate-disodium hydrogen phosphate, boric acid-potassium chloride-potassium carbonate, citric acid-potassium hydrogen citrate, diphosphate Examples include potassium hydrogen-borax and disodium hydrogen phosphate-citric acid.
乳化重合法において用いる乳化剤としては、例えば、脂肪酸塩、アルキル硫酸エステル塩、アルキルベンゼンスルホン酸塩、アルキルリン酸エステル塩、ジアルキルスルホコハク酸塩等のアニオン性界面活性剤；ポリオキシエチレンアルキルエーテル、ポリオキシエチレン脂肪酸エステル、ソルビタン酸脂肪エステル、グリセリン脂肪酸エステル等のノニオン性界面活性剤；アルキルアミン塩等のカチオン性界面活性剤が挙げられる。これら乳化剤は、１種を単独で用いてもよく２種以上を併用してもよい。
乳化剤の種類により重合系のｐＨがアルカリ側になるときは、メタクリル酸アルキルエステルの加水分解を防止するために適当なｐＨ調節剤を用いることもできる。ｐＨ調節剤としては、例えば、ホウ酸－塩化カリウム－水酸化カリウム、リン酸二水素カリウム－リン酸水素二ナトリウム、ホウ酸－塩化カリウム－炭酸カリウム、クエン酸－クエン酸水素カリウム、リン酸二水素カリウム－ホウ砂、リン酸水素二ナトリウム－クエン酸が挙げられる。 Various known methods can be used as the polymerization method for obtaining the polymer (A), and examples thereof include an emulsion polymerization method, a suspension polymerization method, and a solution polymerization method. The addition method of the monomer at the time of superposition | polymerization may be any of lump addition, dripping, and divided addition. The copolymer may be either a random copolymer or a block copolymer, but a random copolymer obtained by batch addition of monomers is preferred.
Examples of the emulsifier used in the emulsion polymerization method include anionic surfactants such as fatty acid salt, alkyl sulfate ester salt, alkylbenzene sulfonate salt, alkyl phosphate ester salt, dialkyl sulfosuccinate salt; polyoxyethylene alkyl ether, polyoxy Nonionic surfactants such as ethylene fatty acid esters, sorbitan acid fatty esters, and glycerin fatty acid esters; and cationic surfactants such as alkylamine salts. These emulsifiers may be used individually by 1 type, and may use 2 or more types together.
When the pH of the polymerization system is on the alkali side depending on the type of emulsifier, an appropriate pH adjusting agent can be used to prevent hydrolysis of the alkyl methacrylate. Examples of pH regulators include boric acid-potassium chloride-potassium hydroxide, potassium dihydrogen phosphate-disodium hydrogen phosphate, boric acid-potassium chloride-potassium carbonate, citric acid-potassium hydrogen citrate, diphosphate Examples include potassium hydrogen-borax and disodium hydrogen phosphate-citric acid.
重合の際には、通常は重合開始剤を使用する。重合開始剤としては、例えば、過硫酸カリウム等の過硫酸塩；ｔ－ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、過酸化ベンゾイル、過酸化ラウロイル等の有機過酸化物；アゾビスイソブチロニトリル等のアゾ化合物；上記の過硫酸塩とナトリウムホルムアルデヒドスルホキシレート等の還元剤を組合せたレドックス系開始剤；上記の有機過酸化物と還元剤を組合せたレドックス系開始剤が挙げられる。
In the polymerization, a polymerization initiator is usually used. Examples of the polymerization initiator include persulfates such as potassium persulfate; organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide; azobisisobutyronitrile, etc. A redox initiator comprising a combination of the above persulfate and a reducing agent such as sodium formaldehyde sulfoxylate; a redox initiator comprising a combination of the above organic peroxide and a reducing agent.
本発明の重合体（Ａ）の回収方法は、例えば乳化重合法により製造する場合には、得られた重合体（Ａ）ラテックスを冷却し、しかる後に、硫酸、塩酸、リン酸等の酸、又は塩化アルミニウム、塩化カルシウム、硫酸マグネシウム、硫酸アルミニウム、酢酸カルシウム等の塩等の電解質により、酸凝固もしくは塩析させて重合体（Ａ）を沈澱せしめた後、更に濾過、洗浄、乾燥して得ることができる。また、噴霧乾燥、凍結乾燥等の種々の方法により回収することもできる。
発泡成形用塩化ビニル系樹脂組成物における微細で均一な発泡セルの形成の促進及び良好な成形外観を得るためには、噴霧乾燥によることが好ましい。噴霧乾燥の条件に特に制限はないが、生成した粒子が下記の条件を満たしたものであることが好ましく、このような粒子が生成する任意の条件で噴霧乾燥することができる。
即ち、好ましいのは噴霧乾燥により形成された粉体のうち、その粒子内部が融着して均質な状態になった粉体の含有率が５０質量％未満、より好ましくは２５質量％未満のものである。５０質量％未満にすることで、本発明の目的である均質な発泡セル構造と高発泡倍率の達成可能な成形加工範囲が拡がる傾向にあり、更に塩化ビニル樹脂とのブレンド時におけるコンパウンドの嵩比の低下等を抑制できる。 In the method for recovering the polymer (A) of the present invention, for example, when it is produced by an emulsion polymerization method, the obtained polymer (A) latex is cooled, and then an acid such as sulfuric acid, hydrochloric acid, phosphoric acid, Alternatively, the polymer (A) is precipitated by acid coagulation or salting out with an electrolyte such as a salt of aluminum chloride, calcium chloride, magnesium sulfate, aluminum sulfate, calcium acetate or the like, followed by further filtration, washing and drying. be able to. It can also be recovered by various methods such as spray drying and freeze drying.
In order to promote the formation of fine and uniform foam cells in the vinyl chloride resin composition for foam molding and to obtain a good molded appearance, it is preferable to use spray drying. Although there is no particular limitation on the spray drying conditions, it is preferable that the generated particles satisfy the following conditions, and spray drying can be performed under any conditions for generating such particles.
That is, among the powders formed by spray drying, it is preferable that the content of the powder in which the inside of the particles are fused and become homogeneous is less than 50% by mass, more preferably less than 25% by mass. It is. By making it less than 50% by mass, the homogeneous foamed cell structure and high foaming ratio, which are the object of the present invention, tend to be expanded, and the bulk ratio of the compound when blended with a vinyl chloride resin is further increased. Can be suppressed.
発泡成形用塩化ビニル系樹脂組成物における微細で均一な発泡セルの形成の促進及び良好な成形外観を得るためには、噴霧乾燥によることが好ましい。噴霧乾燥の条件に特に制限はないが、生成した粒子が下記の条件を満たしたものであることが好ましく、このような粒子が生成する任意の条件で噴霧乾燥することができる。
即ち、好ましいのは噴霧乾燥により形成された粉体のうち、その粒子内部が融着して均質な状態になった粉体の含有率が５０質量％未満、より好ましくは２５質量％未満のものである。５０質量％未満にすることで、本発明の目的である均質な発泡セル構造と高発泡倍率の達成可能な成形加工範囲が拡がる傾向にあり、更に塩化ビニル樹脂とのブレンド時におけるコンパウンドの嵩比の低下等を抑制できる。 In the method for recovering the polymer (A) of the present invention, for example, when it is produced by an emulsion polymerization method, the obtained polymer (A) latex is cooled, and then an acid such as sulfuric acid, hydrochloric acid, phosphoric acid, Alternatively, the polymer (A) is precipitated by acid coagulation or salting out with an electrolyte such as a salt of aluminum chloride, calcium chloride, magnesium sulfate, aluminum sulfate, calcium acetate or the like, followed by further filtration, washing and drying. be able to. It can also be recovered by various methods such as spray drying and freeze drying.
In order to promote the formation of fine and uniform foam cells in the vinyl chloride resin composition for foam molding and to obtain a good molded appearance, it is preferable to use spray drying. Although there is no particular limitation on the spray drying conditions, it is preferable that the generated particles satisfy the following conditions, and spray drying can be performed under any conditions for generating such particles.
That is, among the powders formed by spray drying, it is preferable that the content of the powder in which the inside of the particles are fused and become homogeneous is less than 50% by mass, more preferably less than 25% by mass. It is. By making it less than 50% by mass, the homogeneous foamed cell structure and high foaming ratio, which are the object of the present invention, tend to be expanded, and the bulk ratio of the compound when blended with a vinyl chloride resin is further increased. Can be suppressed.
本発明の発泡成形用加工助剤は、本発明の重合体（Ａ）以外にも、必要に応じて、添加剤を含有してもよく、例えば、アエロジル、無機塩等の粉体流動性改質剤が挙げられる。
The processing aid for foam molding of the present invention may contain additives as necessary in addition to the polymer (A) of the present invention. For example, powder flow properties such as aerosil and inorganic salts may be modified. And a quality agent.
本発明の発泡成形用塩化ビニル系樹脂組成物は、塩化ビニル系樹脂１００質量部に対し、発泡成形用加工助剤を１～２５質量部、好ましくは５～１５質量部配合してなるものである。発泡成形用加工助剤の配合割合を１質量部以上とすることで、溶融強度付与効果が高められ、微細で均一な発泡セルを有した高発泡倍率で、かつ良好な成形外観を有した発泡成形体が得られ易くなる。また、２５質量部以下とすることで、発泡成形体の成形外観の低下を防ぐことができる。
The vinyl chloride resin composition for foam molding of the present invention comprises 1 to 25 parts by mass, preferably 5 to 15 parts by mass of a processing aid for foam molding per 100 parts by mass of the vinyl chloride resin. is there. By making the blending ratio of the processing aid for foam molding to be 1 part by mass or more, the effect of imparting melt strength is enhanced, the foam has a high foaming ratio with fine and uniform foam cells, and has a good molding appearance. A molded body is easily obtained. Moreover, the fall of the shaping | molding external appearance of a foaming molding can be prevented by setting it as 25 mass parts or less.
本発明の塩化ビニル系樹脂は特に制限されず、例えば、塩化ビニルの単独重合体、後塩素化塩化ビニル重合体、部分架橋塩化ビニル重合体、塩化ビニルと他のビニル単量体とを共重合してなる塩化ビニル系共重合体が挙げられる。これら塩化ビニル系樹脂は、１種を単独で用いてもよく２種以上を併用してもよい。
この内、塩化ビニル系共重合体については、塩化ビニル系樹脂の本来の特徴を維持する点から、他のビニル単量体の使用割合は３０質量％以下であることが好ましい。塩化ビニルと共重合させる他のビニル単量体としては、例えば、酢酸ビニル、プロピオン酸ビニル等の脂肪酸ビニルエステル；メタクリル酸メチル、メタクリル酸エチル等のメタクリル酸アルキルエステル；エチレン、プロピレン等のオレフィン；スチレン等の芳香族ビニル単量体；ビニルメチルエーテル、ビニルブチルエーテル等のアルキルビニルエーテル；アクリル酸、メタクリル酸、無水マレイン酸等の不飽和カルボン酸又はその酸無水物が挙げられる。これらは１種を単独で用いてもよく２種以上を併用してもよい。
塩化ビニル系樹脂の平均重合度は、３００～５０００の範囲内が好ましく、５００～３０００の範囲内がより好ましい。塩化ビニル系樹脂の平均重合度が３００以上であれば、発泡倍率や発泡成形体の機械物性の低下を抑制できる傾向にあり、５０００以下であれば、加工性の低下を抑制できる傾向にある。
塩化ビニル系樹脂の製造方法は、特に制限されず、例えば、乳化重合法、懸濁重合法、塊状重合法が挙げられる。 The vinyl chloride resin of the present invention is not particularly limited. For example, a vinyl chloride homopolymer, a post-chlorinated vinyl chloride polymer, a partially crosslinked vinyl chloride polymer, a copolymer of vinyl chloride and another vinyl monomer. And a vinyl chloride copolymer. These vinyl chloride resins may be used alone or in combination of two or more.
Among these, with respect to the vinyl chloride copolymer, the proportion of other vinyl monomers used is preferably 30% by mass or less from the viewpoint of maintaining the original characteristics of the vinyl chloride resin. Examples of other vinyl monomers copolymerized with vinyl chloride include fatty acid vinyl esters such as vinyl acetate and vinyl propionate; alkyl methacrylates such as methyl methacrylate and ethyl methacrylate; olefins such as ethylene and propylene; Examples thereof include aromatic vinyl monomers such as styrene; alkyl vinyl ethers such as vinyl methyl ether and vinyl butyl ether; unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic anhydride, or acid anhydrides thereof. These may be used alone or in combination of two or more.
The average degree of polymerization of the vinyl chloride resin is preferably within the range of 300 to 5000, and more preferably within the range of 500 to 3000. If the average degree of polymerization of the vinyl chloride resin is 300 or more, it tends to suppress the reduction of the foaming ratio and the mechanical properties of the foam molded article, and if it is 5000 or less, it tends to be able to suppress the deterioration of workability.
The production method of the vinyl chloride resin is not particularly limited, and examples thereof include an emulsion polymerization method, a suspension polymerization method, and a bulk polymerization method.
この内、塩化ビニル系共重合体については、塩化ビニル系樹脂の本来の特徴を維持する点から、他のビニル単量体の使用割合は３０質量％以下であることが好ましい。塩化ビニルと共重合させる他のビニル単量体としては、例えば、酢酸ビニル、プロピオン酸ビニル等の脂肪酸ビニルエステル；メタクリル酸メチル、メタクリル酸エチル等のメタクリル酸アルキルエステル；エチレン、プロピレン等のオレフィン；スチレン等の芳香族ビニル単量体；ビニルメチルエーテル、ビニルブチルエーテル等のアルキルビニルエーテル；アクリル酸、メタクリル酸、無水マレイン酸等の不飽和カルボン酸又はその酸無水物が挙げられる。これらは１種を単独で用いてもよく２種以上を併用してもよい。
塩化ビニル系樹脂の平均重合度は、３００～５０００の範囲内が好ましく、５００～３０００の範囲内がより好ましい。塩化ビニル系樹脂の平均重合度が３００以上であれば、発泡倍率や発泡成形体の機械物性の低下を抑制できる傾向にあり、５０００以下であれば、加工性の低下を抑制できる傾向にある。
塩化ビニル系樹脂の製造方法は、特に制限されず、例えば、乳化重合法、懸濁重合法、塊状重合法が挙げられる。 The vinyl chloride resin of the present invention is not particularly limited. For example, a vinyl chloride homopolymer, a post-chlorinated vinyl chloride polymer, a partially crosslinked vinyl chloride polymer, a copolymer of vinyl chloride and another vinyl monomer. And a vinyl chloride copolymer. These vinyl chloride resins may be used alone or in combination of two or more.
Among these, with respect to the vinyl chloride copolymer, the proportion of other vinyl monomers used is preferably 30% by mass or less from the viewpoint of maintaining the original characteristics of the vinyl chloride resin. Examples of other vinyl monomers copolymerized with vinyl chloride include fatty acid vinyl esters such as vinyl acetate and vinyl propionate; alkyl methacrylates such as methyl methacrylate and ethyl methacrylate; olefins such as ethylene and propylene; Examples thereof include aromatic vinyl monomers such as styrene; alkyl vinyl ethers such as vinyl methyl ether and vinyl butyl ether; unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic anhydride, or acid anhydrides thereof. These may be used alone or in combination of two or more.
The average degree of polymerization of the vinyl chloride resin is preferably within the range of 300 to 5000, and more preferably within the range of 500 to 3000. If the average degree of polymerization of the vinyl chloride resin is 300 or more, it tends to suppress the reduction of the foaming ratio and the mechanical properties of the foam molded article, and if it is 5000 or less, it tends to be able to suppress the deterioration of workability.
The production method of the vinyl chloride resin is not particularly limited, and examples thereof include an emulsion polymerization method, a suspension polymerization method, and a bulk polymerization method.
本発明の発泡成形用塩化ビニル系樹脂組成物を得る方法は特に制限されるものではなく、公知の溶融混練方法を用いることができ、例えば、所定量の塩化ビニル系樹脂と発泡成形用加工助剤をヘンシェルミキサ、バンバリーミキサ、Ｖ型ミキサ、リボンブレンダ等で混合したものを、単軸押出機、二軸押出機等の混練押出機により発泡成形用塩化ビニル系樹脂組成物を得ることができ、各種の所望の形状に成形されて製造される。また、フリー発泡成形、セルカ発泡成形等のいずれの発泡成形方法にも、本発明の発泡成形用塩化ビニル系樹脂組成物を適用することができる。
The method for obtaining the vinyl chloride resin composition for foam molding of the present invention is not particularly limited, and a known melt-kneading method can be used. For example, a predetermined amount of vinyl chloride resin and processing aid for foam molding can be used. A vinyl chloride resin composition for foam molding can be obtained by kneading extruders such as single-screw extruders and twin-screw extruders that are mixed with Henschel mixers, Banbury mixers, V-type mixers, ribbon blenders, etc. These are manufactured by being molded into various desired shapes. Moreover, the vinyl chloride resin composition for foam molding of the present invention can be applied to any foam molding method such as free foam molding and Selka foam molding.
なお、塩化ビニル系樹脂及び発泡成形用加工助剤を配合して本発明の発泡成形用塩化ビニル系樹脂組成物を得る場合には、本発明の効果を損なわない限りにおいて、その目的に応じて、発泡剤の他、慣用の安定剤、滑剤、充填剤、耐衝撃性改質剤、顔料等の各種添加剤を必要に応じて添加することができる。
発泡剤としては、例えば、アゾビスイソブチロニトリル、アゾジカルボンアミド等のアゾ系発泡剤；Ｎ，Ｎ’－ジニトロソペンタメチレンテトラミン、Ｎ，Ｎ’－ジメチル－Ｎ，Ｎ’－ジニトロソテレフタルアミド等のニトロソ系発泡剤；炭酸水素ナトリウム等の無機系発泡剤等が使用でき、これらは１種を単独で用いてもよく２種以上を併用してもよい。
安定剤としては、例えば、三塩基性硫酸鉛、二塩基性亜リン酸鉛、塩基性亜硫酸鉛、ケイ酸鉛等の鉛系安定剤、カリウム、マグネシウム、バリウム、亜鉛、カドミウム、鉛等の金属と２－エチルヘキサン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、イソステアリン酸、ヒドロキシステアリン酸、オレイン酸、リシノール酸、リノール酸、ベヘニン酸等の脂肪酸から誘導される金属石けん系安定剤；アルキル基、エステル基、脂肪酸基、マレイン酸基、含硫化物基等を有してなる有機スズ系安定剤；Ｂａ－Ｚｎ系、Ｃａ－Ｚｎ系、Ｂａ－Ｃａ－Ｓｎ系、Ｃａ－Ｍｇ－Ｓｎ系、Ｃａ－Ｚｎ－Ｓｎ系、Ｐｂ－Ｓｎ系、Ｐｂ－Ｂａ－Ｃａ系等の複合金属石けん系安定剤；バリウム、亜鉛等の金属基と２－エチルヘキサン酸、イソデカン酸、トリアルキル酢酸等の分岐脂肪酸、オレイン酸、リシノール酸、リノール酸等の不飽和脂肪酸、ナフテン酸等の脂環族酸、石炭酸、安息香酸、サリチル酸、それらの置換誘導体等の芳香族酸といった有機酸の通常二種以上から誘導される金属塩系安定剤；これら安定剤を石油系炭化水素、アルコール、グリセリン誘導体等の有機溶剤に溶解し、更に亜リン酸エステル、エポキシ化合物、発色防止剤、透明性改良剤、光安定剤、酸化防止剤、ブリードアウト防止剤、滑剤等の安定化助剤を配合してなる金属塩液状安定剤等の金属系安定剤のほか、エポキシ樹脂、エポキシ化大豆油、エポキシ化植物油、エポキシ化脂肪酸アルキルエステル等のエポキシ化合物、有機亜リン酸エステル等の非金属系安定剤が挙げられる。これらは、１種を単独で用いてもよく２種以上を併用してもよい。
また、滑剤としては、例えば、流動パラフィン、天然パラフィン、マイクロワックス、合成パラフィン、低分子量ポリエチレン等の純炭化水素系滑剤、ハロゲン化炭化水素系滑剤、高級脂肪酸、オキシ脂肪酸等の脂肪酸系滑剤、脂肪酸アミド、ビス脂肪酸アミド等の脂肪酸アミド系滑剤、脂肪酸の低級アルコールエステル、グリセリド等の脂肪酸の多価アルコールエステル、脂肪酸のポリグリコールエステル、脂肪酸の脂肪アルコールエステル（エステルワックス）等のエステル系滑剤のほか、金属石けん、脂肪アルコール、多価アルコール、ポリグリコール、ポリグリセロール、脂肪酸と多価アルコールの部分エステル、脂肪酸とポリグリコール、ポリグリセロールの部分エステルが挙げられる。これらは、１種を単独で用いてもよく２種以上を併用してもよい。
充填剤としては、例えば、重質炭酸カルシウム、沈降性炭酸カルシウム、膠質炭酸カルシウム等の炭酸塩、水酸化アルミニウム、水酸化マグネシウム、酸化チタン、クレー、マイカ、タルク、ウォラストナイト、ゼオライト、シリカ、酸化亜鉛、酸化マグネシウム、カーボンブラック、グラファイト、ガラスビーズ、ガラス繊維、炭素繊維、金属繊維等の無機質系のほか、ポリアミド等のような有機繊維が挙げられる。これらは、１種を単独で用いてもよく２種以上を併用してもよい。
耐衝撃性改質剤としては、例えば、ポリブタジエン、ポリイソプレン、ポリクロロプレン、フッ素ゴム、スチレン－ブタジエン共重合体ゴム、アクリロニトリル－スチレン－ブタジエン共重合体ゴム、スチレン－ブタジエン－スチレンブロック共重合体ゴム、スチレン－イソプレン－スチレンブロック共重合体ゴム、スチレン－エチレン－ブチレン－スチレンブロック共重合体ゴム、エチレン－プロピレン共重合体ゴム、エチレン－プロピレン－ジエン共重合体ゴム（ＥＰＤＭ）が挙げられる。ＥＰＤＭのジエンとしては、１，４－ヘキサジエン、ジシクロペンタジエン、メチレンノルボルネン、エチリデンノルボルネン、プロペニルノルボルネン等が使用できる。これらの耐衝撃性改質剤は、１種を単独で用いてもよく２種以上を併用してもよい。
更に、顔料としては、公知の有機顔料、無機顔料を用いることができ、例えば、アゾ系、ニトロソ系、ニトロ系、ペリノン系、フタロシアニン系、キナクリドン系等の有機顔料、酸化チタン系、酸化亜鉛系、酸化鉄系、硫化物系、カーボンブラック系、炭酸塩系、金属粉系、クロム酸塩系、フェロシアン化物系、硫酸塩系、ケイ酸塩系、リン酸塩系等の無機顔料が挙げられる。これらの顔料は、１種を単独で用いてもよく２種以上を併用してもよい。
その他、塩素化パラフィン、水酸化アルミニウム、三酸化アンチモン、ハロゲン化合物等の難燃剤、離型剤、流動性改良剤、着色剤、帯電防止剤、界面活性剤、防曇剤、抗菌剤等も、本発明の効果を損なわない限りにおいて、目的に応じて任意に配合することができる。 In the case where the vinyl chloride resin and the foaming molding processing aid are blended to obtain the vinyl chloride resin composition for foam molding of the present invention, depending on the purpose, the effects of the present invention are not impaired. In addition to foaming agents, various additives such as conventional stabilizers, lubricants, fillers, impact modifiers, and pigments can be added as necessary.
Examples of the foaming agent include azo foaming agents such as azobisisobutyronitrile and azodicarbonamide; N, N′-dinitrosopentamethylenetetramine, N, N′-dimethyl-N, N′-dinitrosotephthale Nitroso-based foaming agents such as amides; inorganic foaming agents such as sodium bicarbonate can be used, and these may be used alone or in combination of two or more.
Examples of stabilizers include lead stabilizers such as tribasic lead sulfate, dibasic lead phosphite, basic lead sulfite, and lead silicate, and metals such as potassium, magnesium, barium, zinc, cadmium, and lead. And a metal soap stabilizer derived from a fatty acid such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, ricinoleic acid, linoleic acid, behenic acid; Organotin stabilizers having an alkyl group, an ester group, a fatty acid group, a maleic acid group, a sulfide-containing group, etc .; Ba—Zn series, Ca—Zn series, Ba—Ca—Sn series, Ca—Mg— Composite metal soap-based stabilizers such as Sn-based, Ca-Zn-Sn-based, Pb-Sn-based, Pb-Ba-Ca-based; metal groups such as barium and zinc; 2-ethylhexanoic acid, isode Acids, branched fatty acids such as trialkylacetic acid, unsaturated fatty acids such as oleic acid, ricinoleic acid, linoleic acid, alicyclic acids such as naphthenic acid, aromatic acids such as carboxylic acid, benzoic acid, salicylic acid, and substituted derivatives thereof Metal salt stabilizers usually derived from two or more organic acids such as: These stabilizers are dissolved in organic solvents such as petroleum hydrocarbons, alcohols, glycerin derivatives, etc., and phosphites, epoxy compounds, coloring prevention In addition to metal stabilizers such as metal salt liquid stabilizers that contain stabilizers, transparency improvers, light stabilizers, antioxidants, bleed-out inhibitors, and lubricants, epoxy resin, epoxy Non-metallic stabilizers such as epoxy compounds such as epoxidized soybean oil, epoxidized vegetable oil, and epoxidized fatty acid alkyl esters, and organic phosphites. These may be used alone or in combination of two or more.
Examples of the lubricant include liquid hydrocarbons, natural paraffins, micro waxes, synthetic paraffins, pure hydrocarbon lubricants such as low molecular weight polyethylene, halogenated hydrocarbon lubricants, fatty acid lubricants such as higher fatty acids and oxy fatty acids, fatty acids In addition to fatty acid amide lubricants such as amides and bisfatty acid amides, lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids such as glycerides, polyglycol esters of fatty acids, fatty alcohol esters of fatty acids (ester waxes) and the like Metal soap, fatty alcohol, polyhydric alcohol, polyglycol, polyglycerol, fatty acid and polyhydric alcohol partial ester, fatty acid and polyglycol, polyglycerol partial ester. These may be used alone or in combination of two or more.
Examples of the filler include carbonates such as heavy calcium carbonate, precipitated calcium carbonate, and colloidal calcium carbonate, aluminum hydroxide, magnesium hydroxide, titanium oxide, clay, mica, talc, wollastonite, zeolite, silica, In addition to inorganic systems such as zinc oxide, magnesium oxide, carbon black, graphite, glass beads, glass fibers, carbon fibers, and metal fibers, organic fibers such as polyamide can be used. These may be used alone or in combination of two or more.
Examples of impact modifiers include polybutadiene, polyisoprene, polychloroprene, fluororubber, styrene-butadiene copolymer rubber, acrylonitrile-styrene-butadiene copolymer rubber, and styrene-butadiene-styrene block copolymer rubber. Styrene-isoprene-styrene block copolymer rubber, styrene-ethylene-butylene-styrene block copolymer rubber, ethylene-propylene copolymer rubber, and ethylene-propylene-diene copolymer rubber (EPDM). As the diene of EPDM, 1,4-hexadiene, dicyclopentadiene, methylene norbornene, ethylidene norbornene, propenyl norbornene and the like can be used. These impact modifiers may be used alone or in combination of two or more.
Furthermore, as the pigment, known organic pigments and inorganic pigments can be used, for example, organic pigments such as azo, nitroso, nitro, perinone, phthalocyanine, quinacridone, titanium oxide, and zinc oxide. Inorganic pigments such as iron oxide, sulfide, carbon black, carbonate, metal powder, chromate, ferrocyanide, sulfate, silicate, and phosphate It is done. These pigments may be used alone or in combination of two or more.
In addition, flame retardants such as chlorinated paraffin, aluminum hydroxide, antimony trioxide, halogen compounds, mold release agents, fluidity improvers, colorants, antistatic agents, surfactants, antifogging agents, antibacterial agents, etc. As long as the effect of the present invention is not impaired, it can be arbitrarily blended depending on the purpose.
発泡剤としては、例えば、アゾビスイソブチロニトリル、アゾジカルボンアミド等のアゾ系発泡剤；Ｎ，Ｎ’－ジニトロソペンタメチレンテトラミン、Ｎ，Ｎ’－ジメチル－Ｎ，Ｎ’－ジニトロソテレフタルアミド等のニトロソ系発泡剤；炭酸水素ナトリウム等の無機系発泡剤等が使用でき、これらは１種を単独で用いてもよく２種以上を併用してもよい。
安定剤としては、例えば、三塩基性硫酸鉛、二塩基性亜リン酸鉛、塩基性亜硫酸鉛、ケイ酸鉛等の鉛系安定剤、カリウム、マグネシウム、バリウム、亜鉛、カドミウム、鉛等の金属と２－エチルヘキサン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、イソステアリン酸、ヒドロキシステアリン酸、オレイン酸、リシノール酸、リノール酸、ベヘニン酸等の脂肪酸から誘導される金属石けん系安定剤；アルキル基、エステル基、脂肪酸基、マレイン酸基、含硫化物基等を有してなる有機スズ系安定剤；Ｂａ－Ｚｎ系、Ｃａ－Ｚｎ系、Ｂａ－Ｃａ－Ｓｎ系、Ｃａ－Ｍｇ－Ｓｎ系、Ｃａ－Ｚｎ－Ｓｎ系、Ｐｂ－Ｓｎ系、Ｐｂ－Ｂａ－Ｃａ系等の複合金属石けん系安定剤；バリウム、亜鉛等の金属基と２－エチルヘキサン酸、イソデカン酸、トリアルキル酢酸等の分岐脂肪酸、オレイン酸、リシノール酸、リノール酸等の不飽和脂肪酸、ナフテン酸等の脂環族酸、石炭酸、安息香酸、サリチル酸、それらの置換誘導体等の芳香族酸といった有機酸の通常二種以上から誘導される金属塩系安定剤；これら安定剤を石油系炭化水素、アルコール、グリセリン誘導体等の有機溶剤に溶解し、更に亜リン酸エステル、エポキシ化合物、発色防止剤、透明性改良剤、光安定剤、酸化防止剤、ブリードアウト防止剤、滑剤等の安定化助剤を配合してなる金属塩液状安定剤等の金属系安定剤のほか、エポキシ樹脂、エポキシ化大豆油、エポキシ化植物油、エポキシ化脂肪酸アルキルエステル等のエポキシ化合物、有機亜リン酸エステル等の非金属系安定剤が挙げられる。これらは、１種を単独で用いてもよく２種以上を併用してもよい。
また、滑剤としては、例えば、流動パラフィン、天然パラフィン、マイクロワックス、合成パラフィン、低分子量ポリエチレン等の純炭化水素系滑剤、ハロゲン化炭化水素系滑剤、高級脂肪酸、オキシ脂肪酸等の脂肪酸系滑剤、脂肪酸アミド、ビス脂肪酸アミド等の脂肪酸アミド系滑剤、脂肪酸の低級アルコールエステル、グリセリド等の脂肪酸の多価アルコールエステル、脂肪酸のポリグリコールエステル、脂肪酸の脂肪アルコールエステル（エステルワックス）等のエステル系滑剤のほか、金属石けん、脂肪アルコール、多価アルコール、ポリグリコール、ポリグリセロール、脂肪酸と多価アルコールの部分エステル、脂肪酸とポリグリコール、ポリグリセロールの部分エステルが挙げられる。これらは、１種を単独で用いてもよく２種以上を併用してもよい。
充填剤としては、例えば、重質炭酸カルシウム、沈降性炭酸カルシウム、膠質炭酸カルシウム等の炭酸塩、水酸化アルミニウム、水酸化マグネシウム、酸化チタン、クレー、マイカ、タルク、ウォラストナイト、ゼオライト、シリカ、酸化亜鉛、酸化マグネシウム、カーボンブラック、グラファイト、ガラスビーズ、ガラス繊維、炭素繊維、金属繊維等の無機質系のほか、ポリアミド等のような有機繊維が挙げられる。これらは、１種を単独で用いてもよく２種以上を併用してもよい。
耐衝撃性改質剤としては、例えば、ポリブタジエン、ポリイソプレン、ポリクロロプレン、フッ素ゴム、スチレン－ブタジエン共重合体ゴム、アクリロニトリル－スチレン－ブタジエン共重合体ゴム、スチレン－ブタジエン－スチレンブロック共重合体ゴム、スチレン－イソプレン－スチレンブロック共重合体ゴム、スチレン－エチレン－ブチレン－スチレンブロック共重合体ゴム、エチレン－プロピレン共重合体ゴム、エチレン－プロピレン－ジエン共重合体ゴム（ＥＰＤＭ）が挙げられる。ＥＰＤＭのジエンとしては、１，４－ヘキサジエン、ジシクロペンタジエン、メチレンノルボルネン、エチリデンノルボルネン、プロペニルノルボルネン等が使用できる。これらの耐衝撃性改質剤は、１種を単独で用いてもよく２種以上を併用してもよい。
更に、顔料としては、公知の有機顔料、無機顔料を用いることができ、例えば、アゾ系、ニトロソ系、ニトロ系、ペリノン系、フタロシアニン系、キナクリドン系等の有機顔料、酸化チタン系、酸化亜鉛系、酸化鉄系、硫化物系、カーボンブラック系、炭酸塩系、金属粉系、クロム酸塩系、フェロシアン化物系、硫酸塩系、ケイ酸塩系、リン酸塩系等の無機顔料が挙げられる。これらの顔料は、１種を単独で用いてもよく２種以上を併用してもよい。
その他、塩素化パラフィン、水酸化アルミニウム、三酸化アンチモン、ハロゲン化合物等の難燃剤、離型剤、流動性改良剤、着色剤、帯電防止剤、界面活性剤、防曇剤、抗菌剤等も、本発明の効果を損なわない限りにおいて、目的に応じて任意に配合することができる。 In the case where the vinyl chloride resin and the foaming molding processing aid are blended to obtain the vinyl chloride resin composition for foam molding of the present invention, depending on the purpose, the effects of the present invention are not impaired. In addition to foaming agents, various additives such as conventional stabilizers, lubricants, fillers, impact modifiers, and pigments can be added as necessary.
Examples of the foaming agent include azo foaming agents such as azobisisobutyronitrile and azodicarbonamide; N, N′-dinitrosopentamethylenetetramine, N, N′-dimethyl-N, N′-dinitrosotephthale Nitroso-based foaming agents such as amides; inorganic foaming agents such as sodium bicarbonate can be used, and these may be used alone or in combination of two or more.
Examples of stabilizers include lead stabilizers such as tribasic lead sulfate, dibasic lead phosphite, basic lead sulfite, and lead silicate, and metals such as potassium, magnesium, barium, zinc, cadmium, and lead. And a metal soap stabilizer derived from a fatty acid such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, ricinoleic acid, linoleic acid, behenic acid; Organotin stabilizers having an alkyl group, an ester group, a fatty acid group, a maleic acid group, a sulfide-containing group, etc .; Ba—Zn series, Ca—Zn series, Ba—Ca—Sn series, Ca—Mg— Composite metal soap-based stabilizers such as Sn-based, Ca-Zn-Sn-based, Pb-Sn-based, Pb-Ba-Ca-based; metal groups such as barium and zinc; 2-ethylhexanoic acid, isode Acids, branched fatty acids such as trialkylacetic acid, unsaturated fatty acids such as oleic acid, ricinoleic acid, linoleic acid, alicyclic acids such as naphthenic acid, aromatic acids such as carboxylic acid, benzoic acid, salicylic acid, and substituted derivatives thereof Metal salt stabilizers usually derived from two or more organic acids such as: These stabilizers are dissolved in organic solvents such as petroleum hydrocarbons, alcohols, glycerin derivatives, etc., and phosphites, epoxy compounds, coloring prevention In addition to metal stabilizers such as metal salt liquid stabilizers that contain stabilizers, transparency improvers, light stabilizers, antioxidants, bleed-out inhibitors, and lubricants, epoxy resin, epoxy Non-metallic stabilizers such as epoxy compounds such as epoxidized soybean oil, epoxidized vegetable oil, and epoxidized fatty acid alkyl esters, and organic phosphites. These may be used alone or in combination of two or more.
Examples of the lubricant include liquid hydrocarbons, natural paraffins, micro waxes, synthetic paraffins, pure hydrocarbon lubricants such as low molecular weight polyethylene, halogenated hydrocarbon lubricants, fatty acid lubricants such as higher fatty acids and oxy fatty acids, fatty acids In addition to fatty acid amide lubricants such as amides and bisfatty acid amides, lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids such as glycerides, polyglycol esters of fatty acids, fatty alcohol esters of fatty acids (ester waxes) and the like Metal soap, fatty alcohol, polyhydric alcohol, polyglycol, polyglycerol, fatty acid and polyhydric alcohol partial ester, fatty acid and polyglycol, polyglycerol partial ester. These may be used alone or in combination of two or more.
Examples of the filler include carbonates such as heavy calcium carbonate, precipitated calcium carbonate, and colloidal calcium carbonate, aluminum hydroxide, magnesium hydroxide, titanium oxide, clay, mica, talc, wollastonite, zeolite, silica, In addition to inorganic systems such as zinc oxide, magnesium oxide, carbon black, graphite, glass beads, glass fibers, carbon fibers, and metal fibers, organic fibers such as polyamide can be used. These may be used alone or in combination of two or more.
Examples of impact modifiers include polybutadiene, polyisoprene, polychloroprene, fluororubber, styrene-butadiene copolymer rubber, acrylonitrile-styrene-butadiene copolymer rubber, and styrene-butadiene-styrene block copolymer rubber. Styrene-isoprene-styrene block copolymer rubber, styrene-ethylene-butylene-styrene block copolymer rubber, ethylene-propylene copolymer rubber, and ethylene-propylene-diene copolymer rubber (EPDM). As the diene of EPDM, 1,4-hexadiene, dicyclopentadiene, methylene norbornene, ethylidene norbornene, propenyl norbornene and the like can be used. These impact modifiers may be used alone or in combination of two or more.
Furthermore, as the pigment, known organic pigments and inorganic pigments can be used, for example, organic pigments such as azo, nitroso, nitro, perinone, phthalocyanine, quinacridone, titanium oxide, and zinc oxide. Inorganic pigments such as iron oxide, sulfide, carbon black, carbonate, metal powder, chromate, ferrocyanide, sulfate, silicate, and phosphate It is done. These pigments may be used alone or in combination of two or more.
In addition, flame retardants such as chlorinated paraffin, aluminum hydroxide, antimony trioxide, halogen compounds, mold release agents, fluidity improvers, colorants, antistatic agents, surfactants, antifogging agents, antibacterial agents, etc. As long as the effect of the present invention is not impaired, it can be arbitrarily blended depending on the purpose.
得られた発泡成形用塩化ビニル系樹脂組成物は、発泡押出成形の他、通常の公知の成形方法、例えば、射出成形、中空成形、押出成形等にも適用して各種成形体を得ることができる。
また、各種成形方法により、板状発泡成形体、筒状発泡成形体、異形発泡成形体が得られ、広汎な建材用途、合成木材等を指向した部材；ディスプレー用部材、収納ケース等を指向した発泡ボード、断熱性や保温性が必要とされる工業用部材に利用することができる。 The obtained vinyl chloride resin composition for foam molding can be applied to ordinary known molding methods such as injection molding, hollow molding, extrusion molding and the like in addition to foam extrusion molding to obtain various molded products. it can.
In addition, by various molding methods, a plate-like foam molded body, a cylindrical foam molded body, and an irregular-shaped foam molded body are obtained, and members for a wide range of building materials, synthetic wood, etc .; for display members, storage cases, etc. It can be used for foamed boards, industrial members that require heat insulation and heat retention.
また、各種成形方法により、板状発泡成形体、筒状発泡成形体、異形発泡成形体が得られ、広汎な建材用途、合成木材等を指向した部材；ディスプレー用部材、収納ケース等を指向した発泡ボード、断熱性や保温性が必要とされる工業用部材に利用することができる。 The obtained vinyl chloride resin composition for foam molding can be applied to ordinary known molding methods such as injection molding, hollow molding, extrusion molding and the like in addition to foam extrusion molding to obtain various molded products. it can.
In addition, by various molding methods, a plate-like foam molded body, a cylindrical foam molded body, and an irregular-shaped foam molded body are obtained, and members for a wide range of building materials, synthetic wood, etc .; for display members, storage cases, etc. It can be used for foamed boards, industrial members that require heat insulation and heat retention.
本発明の発泡成形用加工助剤によれば、発泡成形用塩化ビニル系樹脂組成物の混練を効率良く行い、かつ溶融強度をも高めることができ、その結果、微細で均一な発泡セルを形成し、高発泡倍率で、更には優れた成形外観を呈する発泡成形体を得ることができる。
According to the processing aid for foam molding of the present invention, the vinyl chloride resin composition for foam molding can be efficiently kneaded and the melt strength can be increased, resulting in the formation of fine and uniform foam cells. In addition, it is possible to obtain a foamed molded article having a high foaming ratio and an excellent molded appearance.
以下、実施例により本発明を具体的に説明するが、本発明はかかる実施例のみに限定されるものではない。なお、各実施例、比較例中「部」とあるのは「質量部」を示す。
尚、還元粘度（ηｓｐ／ｃ）は、重合体０．１ｇを１００ｍｌのクロロホルムに溶解し、２５℃でウベローデ型粘度計を使用して測定した。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited only to this Example. In each example and comparative example, “part” means “part by mass”.
The reduced viscosity (η sp / c) was measured by dissolving 0.1 g of the polymer in 100 ml of chloroform and using an Ubbelohde viscometer at 25 ° C.
尚、還元粘度（ηｓｐ／ｃ）は、重合体０．１ｇを１００ｍｌのクロロホルムに溶解し、２５℃でウベローデ型粘度計を使用して測定した。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited only to this Example. In each example and comparative example, “part” means “part by mass”.
The reduced viscosity (η sp / c) was measured by dissolving 0.1 g of the polymer in 100 ml of chloroform and using an Ubbelohde viscometer at 25 ° C.
［実施例１］
攪拌装置及び環流冷却器付き反応容器に、脱イオン水２３０部を仕込み、更にジオクチルスルホコハク酸ナトリウム１．５部を加えて、容器内を窒素ガスで置換した。その後、過硫酸カリウム０．１５部、メタクリル酸イソブチル１００部を仕込み、攪拌しながら反応容器の外温を６５℃に昇温し、２時間加熱攪拌して重合を終了し、ラテックスを得た。
このラテックスを冷却し、乾燥用ガスの入口温度１６０℃及び乾燥用ガスの出口温度７０℃の条件で噴霧乾燥を行い、重合体の粉体を得た。重合体の還元粘度（ηｓｐ／ｃ）は９．７であった。得られた重合体（Ａ）の粉体を、発泡成形用加工助剤（Ｂ－１）とした。
得られた発泡成形用加工助剤（Ｂ－１）１５部を、下記配合にて混合し、内温９０℃にてブレンドを終了し、発泡成形用塩化ビニル系樹脂組成物を得た。
発泡成形用加工助剤 １５部
塩化ビニル樹脂 平均重合度：７００（ＴＫ７００：信越化学（株）製） １００部
メチル錫メルカプチド（ＴＭ－７０１：勝田化工（株）製） ２部
ステアリン酸カルシウム（ＳＡＫ－ＣＳ－Ｇ：品川化工（株）製） １部
脂肪酸アルコール二塩基酸エステル（ＬＯＸＩＯＬ Ｇ６０：コグニス（株）製） ０．８部
酸化ポリエチレンワックス（ＨＩ－ＷＡＸ４２０２Ｅ：三井化学（株）製） ０．７部
ポリエチレンワックス（ＰＥ５２０：三井化学（株）製） ０．１部
複合ワックス（Ｌ－４２０：勝田化工（株）製） ２部
滑剤 （メタブレンＬ１０００：三菱レイヨン（株）製） ０．５部
タルク（ＭＳ：日本タルク（株）製） １０部
発泡剤（アゾジカルボンアミド：永和化成（株）製） １部
発泡剤（重曹：ＳＣ－Ｐ永和化成（株）製） ０．７部
顔料（ＤＡ ＥＰ４８２０ ブラウン：大日精化（株）製） ０．０５部
得られた発泡成形用塩化ビニル系樹脂組成物を、３０ｍｍ単軸押出機（ＧＭ ＥＮＧ社製）を用いて、Ｃ１：１５０℃，Ｃ２：１７０℃，Ｃ３：１８０℃，ＡＤ：１９０℃，Ｄ：１９０℃の温度条件で、直径５ｍｍのダイ形状から押出し、発泡成形体を製造した。
得られた発泡成形体について、以下の（１）～（３）の評価を行った。
（１）比重
得られた発泡成形体を切断し、自動比重計（ＡＮＤ－ＤＭＡ－２２０：（株）安藤計器製工所製）にて測定した。
（２）発泡成形性
得られた発泡成形体を１０箇所で切断し、その切断面を観察した。各切断面での、長径１ｍｍを超える発泡セルを数え、以下の基準により評価した。
Ａ：長径１ｍｍを超える発泡セルが、確認されなかった
Ｂ：長径１ｍｍを超える発泡セルが、１～２箇所の切断面で確認された
Ｃ：長径１ｍｍを超える発泡セルが、３箇所以上の切断面で確認された
（３）顔料分散性
得られた発泡成形体の表面を観察して、顔料の分散性を以下の基準により評価した。
Ａ：顔料が均一に分散している
Ｂ：部分的に、顔料が不均一に分散している
Ｃ：全体的に、顔料が不均一に分散している
Ｄ：顔料の筋が明白に確認される [Example 1]
In a reaction vessel equipped with a stirrer and a reflux condenser, 230 parts of deionized water was charged, 1.5 parts of sodium dioctyl sulfosuccinate was further added, and the inside of the vessel was replaced with nitrogen gas. Thereafter, 0.15 part of potassium persulfate and 100 parts of isobutyl methacrylate were charged, the external temperature of the reaction vessel was raised to 65 ° C. while stirring, and the mixture was heated and stirred for 2 hours to complete the polymerization, thereby obtaining a latex.
The latex was cooled and spray-dried under the conditions of a drying gas inlet temperature of 160 ° C. and a drying gas outlet temperature of 70 ° C. to obtain a polymer powder. The reduced viscosity (η sp / c) of the polymer was 9.7. The obtained polymer (A) powder was used as a foaming processing aid (B-1).
15 parts of the resulting foam molding processing aid (B-1) was mixed in the following composition, blending was completed at an internal temperature of 90 ° C., and a vinyl chloride resin composition for foam molding was obtained.
Processing aid for foam molding 15 parts Vinyl chloride resin Average polymerization degree: 700 (TK700: manufactured by Shin-Etsu Chemical Co., Ltd.) 100 parts Methyl tin mercaptide (TM-701: manufactured by Katsuta Chemical Co., Ltd.) 2 parts Calcium stearate (SAK- CS-G: manufactured by Shinagawa Chemical Co., Ltd.) 1 part fatty acid alcohol dibasic acid ester (LOXIOL G60: manufactured by Cognis Co., Ltd.) 0.8 part Oxidized polyethylene wax (HI-WAX4202E: manufactured by Mitsui Chemicals, Inc.) 0. 7 parts Polyethylene wax (PE520: manufactured by Mitsui Chemicals) 0.1 part Composite wax (L-420: manufactured by Katsuta Chemical Co., Ltd.) 2 parts Lubricant (Metabrene L1000: manufactured by Mitsubishi Rayon Co., Ltd.) 0.5 part Talc (MS: Nihon Talc Co., Ltd.) 10 parts Foaming agent (Azodicarbonamide: Eiwa Kasei Co., Ltd.) 1 part Foaming agent (heavy : SC-P Eiwa Kasei Co., Ltd.) 0.7 part Pigment (DA EP4820 Brown: manufactured by Dainichi Seika Co., Ltd.) 0.05 part The obtained vinyl chloride resin composition for foam molding is 30 mm uniaxial. Using an extruder (manufactured by GM ENG), extrusion was performed from a die shape having a diameter of 5 mm under a temperature condition of C1: 150 ° C, C2: 170 ° C, C3: 180 ° C, AD: 190 ° C, D: 190 ° C, and foamed. A molded body was produced.
The obtained foamed molded article was evaluated in the following (1) to (3).
(1) Specific gravity The obtained foamed molded article was cut and measured with an automatic specific gravity meter (AND-DMA-220: manufactured by Ando Keiki Seisakusho Co., Ltd.).
(2) Foam moldability The obtained foam molded article was cut at 10 locations, and the cut surface was observed. Foamed cells with a major axis exceeding 1 mm on each cut surface were counted and evaluated according to the following criteria.
A: No foam cell exceeding 1 mm of major axis was confirmed B: Foam cell exceeding 1 mm of major axis was confirmed at one or two cut surfaces C: Three or more foam cells exceeding 1 mm of major axis were cut (3) Pigment dispersibility confirmed on the surface The surface of the obtained foamed molded article was observed, and the dispersibility of the pigment was evaluated according to the following criteria.
A: The pigment is uniformly dispersed. B: The pigment is partially dispersed unevenly. C: The pigment is dispersed unevenly. D: The pigment streaks are clearly confirmed. Ru
攪拌装置及び環流冷却器付き反応容器に、脱イオン水２３０部を仕込み、更にジオクチルスルホコハク酸ナトリウム１．５部を加えて、容器内を窒素ガスで置換した。その後、過硫酸カリウム０．１５部、メタクリル酸イソブチル１００部を仕込み、攪拌しながら反応容器の外温を６５℃に昇温し、２時間加熱攪拌して重合を終了し、ラテックスを得た。
このラテックスを冷却し、乾燥用ガスの入口温度１６０℃及び乾燥用ガスの出口温度７０℃の条件で噴霧乾燥を行い、重合体の粉体を得た。重合体の還元粘度（ηｓｐ／ｃ）は９．７であった。得られた重合体（Ａ）の粉体を、発泡成形用加工助剤（Ｂ－１）とした。
得られた発泡成形用加工助剤（Ｂ－１）１５部を、下記配合にて混合し、内温９０℃にてブレンドを終了し、発泡成形用塩化ビニル系樹脂組成物を得た。
発泡成形用加工助剤 １５部
塩化ビニル樹脂 平均重合度：７００（ＴＫ７００：信越化学（株）製） １００部
メチル錫メルカプチド（ＴＭ－７０１：勝田化工（株）製） ２部
ステアリン酸カルシウム（ＳＡＫ－ＣＳ－Ｇ：品川化工（株）製） １部
脂肪酸アルコール二塩基酸エステル（ＬＯＸＩＯＬ Ｇ６０：コグニス（株）製） ０．８部
酸化ポリエチレンワックス（ＨＩ－ＷＡＸ４２０２Ｅ：三井化学（株）製） ０．７部
ポリエチレンワックス（ＰＥ５２０：三井化学（株）製） ０．１部
複合ワックス（Ｌ－４２０：勝田化工（株）製） ２部
滑剤 （メタブレンＬ１０００：三菱レイヨン（株）製） ０．５部
タルク（ＭＳ：日本タルク（株）製） １０部
発泡剤（アゾジカルボンアミド：永和化成（株）製） １部
発泡剤（重曹：ＳＣ－Ｐ永和化成（株）製） ０．７部
顔料（ＤＡ ＥＰ４８２０ ブラウン：大日精化（株）製） ０．０５部
得られた発泡成形用塩化ビニル系樹脂組成物を、３０ｍｍ単軸押出機（ＧＭ ＥＮＧ社製）を用いて、Ｃ１：１５０℃，Ｃ２：１７０℃，Ｃ３：１８０℃，ＡＤ：１９０℃，Ｄ：１９０℃の温度条件で、直径５ｍｍのダイ形状から押出し、発泡成形体を製造した。
得られた発泡成形体について、以下の（１）～（３）の評価を行った。
（１）比重
得られた発泡成形体を切断し、自動比重計（ＡＮＤ－ＤＭＡ－２２０：（株）安藤計器製工所製）にて測定した。
（２）発泡成形性
得られた発泡成形体を１０箇所で切断し、その切断面を観察した。各切断面での、長径１ｍｍを超える発泡セルを数え、以下の基準により評価した。
Ａ：長径１ｍｍを超える発泡セルが、確認されなかった
Ｂ：長径１ｍｍを超える発泡セルが、１～２箇所の切断面で確認された
Ｃ：長径１ｍｍを超える発泡セルが、３箇所以上の切断面で確認された
（３）顔料分散性
得られた発泡成形体の表面を観察して、顔料の分散性を以下の基準により評価した。
Ａ：顔料が均一に分散している
Ｂ：部分的に、顔料が不均一に分散している
Ｃ：全体的に、顔料が不均一に分散している
Ｄ：顔料の筋が明白に確認される [Example 1]
In a reaction vessel equipped with a stirrer and a reflux condenser, 230 parts of deionized water was charged, 1.5 parts of sodium dioctyl sulfosuccinate was further added, and the inside of the vessel was replaced with nitrogen gas. Thereafter, 0.15 part of potassium persulfate and 100 parts of isobutyl methacrylate were charged, the external temperature of the reaction vessel was raised to 65 ° C. while stirring, and the mixture was heated and stirred for 2 hours to complete the polymerization, thereby obtaining a latex.
The latex was cooled and spray-dried under the conditions of a drying gas inlet temperature of 160 ° C. and a drying gas outlet temperature of 70 ° C. to obtain a polymer powder. The reduced viscosity (η sp / c) of the polymer was 9.7. The obtained polymer (A) powder was used as a foaming processing aid (B-1).
15 parts of the resulting foam molding processing aid (B-1) was mixed in the following composition, blending was completed at an internal temperature of 90 ° C., and a vinyl chloride resin composition for foam molding was obtained.
Processing aid for foam molding 15 parts Vinyl chloride resin Average polymerization degree: 700 (TK700: manufactured by Shin-Etsu Chemical Co., Ltd.) 100 parts Methyl tin mercaptide (TM-701: manufactured by Katsuta Chemical Co., Ltd.) 2 parts Calcium stearate (SAK- CS-G: manufactured by Shinagawa Chemical Co., Ltd.) 1 part fatty acid alcohol dibasic acid ester (LOXIOL G60: manufactured by Cognis Co., Ltd.) 0.8 part Oxidized polyethylene wax (HI-WAX4202E: manufactured by Mitsui Chemicals, Inc.) 0. 7 parts Polyethylene wax (PE520: manufactured by Mitsui Chemicals) 0.1 part Composite wax (L-420: manufactured by Katsuta Chemical Co., Ltd.) 2 parts Lubricant (Metabrene L1000: manufactured by Mitsubishi Rayon Co., Ltd.) 0.5 part Talc (MS: Nihon Talc Co., Ltd.) 10 parts Foaming agent (Azodicarbonamide: Eiwa Kasei Co., Ltd.) 1 part Foaming agent (heavy : SC-P Eiwa Kasei Co., Ltd.) 0.7 part Pigment (DA EP4820 Brown: manufactured by Dainichi Seika Co., Ltd.) 0.05 part The obtained vinyl chloride resin composition for foam molding is 30 mm uniaxial. Using an extruder (manufactured by GM ENG), extrusion was performed from a die shape having a diameter of 5 mm under a temperature condition of C1: 150 ° C, C2: 170 ° C, C3: 180 ° C, AD: 190 ° C, D: 190 ° C, and foamed. A molded body was produced.
The obtained foamed molded article was evaluated in the following (1) to (3).
(1) Specific gravity The obtained foamed molded article was cut and measured with an automatic specific gravity meter (AND-DMA-220: manufactured by Ando Keiki Seisakusho Co., Ltd.).
(2) Foam moldability The obtained foam molded article was cut at 10 locations, and the cut surface was observed. Foamed cells with a major axis exceeding 1 mm on each cut surface were counted and evaluated according to the following criteria.
A: No foam cell exceeding 1 mm of major axis was confirmed B: Foam cell exceeding 1 mm of major axis was confirmed at one or two cut surfaces C: Three or more foam cells exceeding 1 mm of major axis were cut (3) Pigment dispersibility confirmed on the surface The surface of the obtained foamed molded article was observed, and the dispersibility of the pigment was evaluated according to the following criteria.
A: The pigment is uniformly dispersed. B: The pigment is partially dispersed unevenly. C: The pigment is dispersed unevenly. D: The pigment streaks are clearly confirmed. Ru
［実施例２～３、比較例１～８］
単量体成分の組成を、表１に示した比率に変更した以外は、実施例１と同様にして重合及び噴霧乾燥を行い、重合体の粉体、発泡成形用塩化ビニル系樹脂組成物、発泡成形体を得た。 [Examples 2 to 3, Comparative Examples 1 to 8]
Except that the composition of the monomer component was changed to the ratio shown in Table 1, polymerization and spray drying were performed in the same manner as in Example 1 to obtain a polymer powder, a vinyl chloride resin composition for foam molding, A foamed molded product was obtained.
単量体成分の組成を、表１に示した比率に変更した以外は、実施例１と同様にして重合及び噴霧乾燥を行い、重合体の粉体、発泡成形用塩化ビニル系樹脂組成物、発泡成形体を得た。 [Examples 2 to 3, Comparative Examples 1 to 8]
Except that the composition of the monomer component was changed to the ratio shown in Table 1, polymerization and spray drying were performed in the same manner as in Example 1 to obtain a polymer powder, a vinyl chloride resin composition for foam molding, A foamed molded product was obtained.
実施例１～３、比較例１～８で得られた発泡成形体の各評価結果を、表１に示す。
Table 1 shows the evaluation results of the foam molded articles obtained in Examples 1 to 3 and Comparative Examples 1 to 8.
表中の略号は、以下の通りである。
ｉ－ＢＭＡ：メタクリル酸イソブチル
ｎ－ＢＭＡ：メタクリル酸ｎ－ブチル
ｔ－ＢＭＡ：メタクリル酸ｔ－ブチル
ＭＭＡ：メタクリル酸メチル
ｎ－ＢＡ：アクリル酸ブチル
ｎ－ＯＭ：ｎ－オクチルメルカプタン Abbreviations in the table are as follows.
i-BMA: Isobutyl methacrylate n-BMA: n-butyl methacrylate t-BMA: t-butyl methacrylate MMA: methyl methacrylate n-BA: butyl acrylate n-OM: n-octyl mercaptan
ｉ－ＢＭＡ：メタクリル酸イソブチル
ｎ－ＢＭＡ：メタクリル酸ｎ－ブチル
ｔ－ＢＭＡ：メタクリル酸ｔ－ブチル
ＭＭＡ：メタクリル酸メチル
ｎ－ＢＡ：アクリル酸ブチル
ｎ－ＯＭ：ｎ－オクチルメルカプタン Abbreviations in the table are as follows.
i-BMA: Isobutyl methacrylate n-BMA: n-butyl methacrylate t-BMA: t-butyl methacrylate MMA: methyl methacrylate n-BA: butyl acrylate n-OM: n-octyl mercaptan
表１の結果からも明らかなように、メタクリル酸イソブチル６５質量％以上含有する単量体成分（ａ）を重合して得られた重合体（Ａ）を含有する発泡成形用加工助剤を用いて発泡成形することによって、優れた顔料分散性及び発泡性の成形体を得ることができた。特に、ｉ－ＢＭＡを用いることによってｎ－ＢＭＡやｔ－ＢＭＡに比して顕著な効果が発揮されること、また、重合体（Ａ）の還元粘度（ηｓｐ／ｃ）を４以上とすることで顕著な効果が発揮されることは特筆すべきである。
As is clear from the results of Table 1, a foaming processing aid containing a polymer (A) obtained by polymerizing a monomer component (a) containing 65% by mass or more of isobutyl methacrylate was used. By performing foam molding, a molded article having excellent pigment dispersibility and foamability could be obtained. In particular, by using i-BMA, a remarkable effect is exhibited compared to n-BMA and t-BMA, and the reduced viscosity (η sp / c) of the polymer (A) is 4 or more. It should be noted that a remarkable effect is exhibited.
本発明の発泡成形用加工助剤によれば、微細で均一な発泡セルを形成し、高発泡倍率で、更には優れた成形外観を呈する発泡成形体を得ることができる。
これらの発泡成形体は、各種成形方法により、板状発泡成形体、筒状発泡成形体、異形発泡成形体が得られ、広汎な建材用途、合成木材等を指向した部材；ディスプレー用部材、収納ケース等を指向した発泡ボード、断熱性や保温性が必要とされる工業用部材に利用することができる。 According to the processing aid for foam molding of the present invention, it is possible to obtain a foam molded article that forms fine and uniform foamed cells, has a high foaming ratio, and further exhibits an excellent molded appearance.
These foam moldings can be obtained by various molding methods to obtain plate-like foam moldings, cylindrical foam moldings, and irregular-shaped foam moldings, and members for a wide range of building materials, synthetic wood, etc .; display members, storage It can be used for foam boards oriented to cases and the like, and industrial members that require heat insulation and heat retention.
これらの発泡成形体は、各種成形方法により、板状発泡成形体、筒状発泡成形体、異形発泡成形体が得られ、広汎な建材用途、合成木材等を指向した部材；ディスプレー用部材、収納ケース等を指向した発泡ボード、断熱性や保温性が必要とされる工業用部材に利用することができる。 According to the processing aid for foam molding of the present invention, it is possible to obtain a foam molded article that forms fine and uniform foamed cells, has a high foaming ratio, and further exhibits an excellent molded appearance.
These foam moldings can be obtained by various molding methods to obtain plate-like foam moldings, cylindrical foam moldings, and irregular-shaped foam moldings, and members for a wide range of building materials, synthetic wood, etc .; display members, storage It can be used for foam boards oriented to cases and the like, and industrial members that require heat insulation and heat retention.
Claims (5)
- メタクリル酸イソブチルを６５質量％以上含有する単量体成分（ａ）を重合して得られる重合体（Ａ）からなる発泡成形用加工助剤であって、
１００ｍｌのクロロホルムに０．１ｇを溶解して２５℃で測定した重合体（Ａ）の還元粘度（ηｓｐ／ｃ）が４以上である、発泡成形用加工助剤。 A processing aid for foam molding comprising a polymer (A) obtained by polymerizing a monomer component (a) containing 65% by mass or more of isobutyl methacrylate,
A processing aid for foam molding in which 0.1 g is dissolved in 100 ml of chloroform and the reduced viscosity (η sp / c) of the polymer (A) measured at 25 ° C. is 4 or more. - 単量体成分（ａ）が、メタクリル酸イソブチルを７６質量％以上含有する、請求項１記載の発泡成形用加工助剤。 The processing aid for foam molding according to claim 1, wherein the monomer component (a) contains 76% by mass or more of isobutyl methacrylate.
- １００ｍｌのクロロホルムに０．１ｇを溶解して２５℃で測定した重合体（Ａ）の還元粘度（ηｓｐ／ｃ）が２０以下である、請求項１または２記載の発泡成形用加工助剤。 The processing aid for foam molding according to claim 1 or 2, wherein the reduced viscosity (η sp / c) of the polymer (A) measured at 25 ° C by dissolving 0.1 g in 100 ml of chloroform is 20 or less.
- 塩化ビニル系樹脂１００質量部に対して、請求項１～３何れか１項に記載の発泡成形用加工助剤１～２５質量部を含有する発泡成形用塩化ビニル系樹脂組成物。 A vinyl chloride resin composition for foam molding, comprising 1 to 25 parts by mass of a processing aid for foam molding according to any one of claims 1 to 3 with respect to 100 parts by mass of the vinyl chloride resin.
- 請求項４記載の発泡成形用塩化ビニル系樹脂組成物を成形して得られる発泡成形体。 A foam molded article obtained by molding the vinyl chloride resin composition for foam molding according to claim 4.
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| JP2009553862A JP5636673B2 (en) | 2008-11-28 | 2009-11-27 | Vinyl chloride resin composition for foam molding and foam molded article |
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| US11685827B2 (en) | 2017-10-16 | 2023-06-27 | Kaneka Corporation | Vinyl chloride resin composition for powder molding, vinyl chloride resin molded body and laminate |
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| JP5636673B2 (en) | 2014-12-10 |
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