WO2001094485A1 - Coating material - Google Patents

Coating material Download PDF

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Publication number
WO2001094485A1
WO2001094485A1 PCT/JP2000/003739 JP0003739W WO0194485A1 WO 2001094485 A1 WO2001094485 A1 WO 2001094485A1 JP 0003739 W JP0003739 W JP 0003739W WO 0194485 A1 WO0194485 A1 WO 0194485A1
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WIPO (PCT)
Prior art keywords
weight
coating agent
parts
agent according
points
Prior art date
Application number
PCT/JP2000/003739
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French (fr)
Japanese (ja)
Inventor
Minoru Asano
Naramitsu Nakagawa
Masayuki Ogawa
Toshihiro Yasuda
Original Assignee
Mitsubishi Chemical Functional Products, Inc.
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Priority to PCT/JP2000/003739 priority Critical patent/WO2001094485A1/en
Publication of WO2001094485A1 publication Critical patent/WO2001094485A1/en

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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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
    • C08J3/095—Oxygen containing compounds
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • 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
    • C08J2333/00—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
    • C08J2333/04—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—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 esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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

Definitions

  • the present invention relates to a coating agent, particularly a coating agent suitable for use in polyvinyl chloride.
  • a coating agent containing a large amount of a curable polyurethane / curable epoxy-based organic solvent is usually applied to a polyvinyl chloride vinyl sheet used for a waterproof sheet or the like.
  • a coating agent is accompanied by a flammable odor when forming a coating film, and an organic solvent is released into the atmosphere, which is environmentally unfavorable.
  • the coating film itself has a problem with weather resistance over a long length of m.
  • a coating agent in which rosin, petroleum resin, or the like is added to an acrylic resin emulsion containing a large amount of an aqueous solvent as a component for improving the adhesion to polyvinyl chloride.
  • coating agents containing rosin, petroleum resin, etc. have poor weather resistance and are prone to yellowing, and the acrylic resin coating film has insufficient weather resistance. Disclosure of the invention
  • the present invention solves the above-mentioned problem, and relates to a coating agent comprising an acryl resin emulsion containing an aromatic alcohol.
  • This coating agent is composed of a mixed solution mainly composed of 7-acryl resin, an aromatic alcohol, a surfactant and water.
  • the acrylic resin is a homopolymer of acrylic ester or a copolymer of acrylic ester and other vinyl compound monomers.
  • the acrylyl ester as a monomer raw material used in the present invention is acrylate and methacrylate (hereinafter, the rain may be collectively referred to as “(meth) acrylate”). ) o Specific examples of acrylyl esters include methyl (meth) acrylate and ethyl.
  • Examples include (meth) acrylate, dimethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylate.
  • vinyl monomers that can be copolymerized with the acrylic ester include acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, atropoic acid, and citraconic acid.
  • the coating agent of the present invention is in the form of an emulsion
  • the monomer material is dispersed in water in the presence of a surfactant and emulsion polymerization is carried out.
  • a method in which the resin emulsion is used as it is is suitably used.
  • the surfactant used for the emulsion polymerization is preferably an anionic surfactant or a nonionic surfactant. Two on-surfactant at a force s, or a cationic surfactant.
  • anionic surfactant include dialkyl lfosuccinate, higher alcohol sulfate (Na salt or amine salt), alkylaryl sulfonate (Na salt or amine salt), and alkyl naphthene sulfonate ( Na salt or amine salt), anoalkyl naphthalene sulfonate condensate, alkyl phosphate, rosin stone, and fatty acid salt (Na salt or amine salt).
  • nonionic surfactant examples include ether, polyoxyethylene alkylster, polyoxyethylene alkylamine, polyoxyethylene alkylmonoamine, and polyoxyethylene alkyl ester.
  • examples of the above-mentioned cationic surfactant include trimethylaminoethylalkylamitobarogenide, alkylridinium sulfate, and alkyltrimethylammonium barogenide.
  • the amount of water used in the emulsion polymerization is usually 20 to 100 parts by weight, preferably 20 to 100 parts by weight, based on the acrylic resin obtained by the polymerization (usually calculated as the total amount of the monomer raw material). It is 40 to 300 parts by weight.
  • the amount of the surfactant to be used is generally 1 to 10 parts by weight, preferably 2 to 4 parts by weight, based on 100 parts by weight of the acrylic resin.
  • Emulsion polymerization is carried out by adding a polymerization initiator to the reaction system and heating and stirring usually at about 30 to 90 ° C.
  • the reaction system should be in an inert gas atmosphere such as nitrogen if necessary.
  • the pH may be adjusted by adding an alkali such as sodium hydroxide, potassium hydroxide, or ammonia.
  • the polymerization initiator includes water-soluble inorganic polymerization such as ammonium persulfate, potassium sulfate, sodium persulfate, and sodium persulfate, and 2,2′-asobis (2-methylpropionamidine) dihydrochloride.
  • Water-soluble organic polymerization initiators such as dihadrochlorite, inorganic or organic polymerization initiators and sodium sulfite, sodium bisulfite, sodium hyposulfite, ascorpin
  • a redox polymerization initiator system using a reducing agent such as an acid in combination is exemplified.
  • the amount of the polymerization initiator to be used is usually 1 to 0.5 part by weight based on 100 parts by weight of the monomer raw material.o
  • the coating agent of the present invention can be obtained by mixing a predetermined amount of an aromatic alcohol with the acrylic resin emulsion produced as described above.
  • aromatic alcohol examples include benzene methanol (benzyl alcohol), benzene ethanol, diphenyl methanol, 2-naphthalene methanol, and 1,2-benzene dimethanol, and benzyl alcohol is particularly preferable.
  • Aromatic alcohol slightly swells the surface of a coating object typified by a polychlorinated vinyl sheet, and enhances adhesion to a coating film.
  • the amount of the aromatic alcohol to be used is usually 5 to 50 parts by weight, preferably 10 to 40 parts by weight, per 100 parts by weight of the acryl resin.
  • the concentration and composition can be adjusted by adding water or a surfactant to the acryl resin emulsion later according to the object or purpose of coating.
  • the coating agent of the present invention comprising an anionic or nonionic acrylic resin emulsion
  • sodium, potassium and lithium salts of dialkyl sulfosuccinates are used.
  • an alkali metal salt such as an ammonium salt, particularly a sodium salt of dialkyl sulfosuccinate.
  • the alkyl group portion of dialkyl sulfosuccinate Usually, it consists of a single or mixed alkyl group having about 6 to 16 carbon atoms.
  • the amount of the alkali metal salt of dialkyl sulfosuccinate is usually 1 to 10 parts by weight, preferably 2 to 5 parts by weight, based on 100 parts by weight of the acrylic resin. If the amount of the dialkyl sulfosuccinate metal salt is less than the above range, the effect of improving the wettability is not sufficient, and if it is more than the above range, the water resistance of the coating film tends to decrease. .
  • the coating agent of the present invention can be applied to polyvinyl chloride, polyester sheet, FRP, concrete panel, mortar, etc., and is particularly preferably used for molded articles made of polyvinyl chloride.
  • the target polychlorinated vinyl (PVC) is not particularly limited, but typical examples include octyl phthalate, dibutyl phthalate, and tricle phthalate. Examples include ordinary semi-rigid or soft PVC sheets to which a plasticizer such as zyl phosphate is usually added in an amount of 50 to 100% by weight.
  • the coating agent of the present invention is coated on a sheet using a knife coater, a flow coater, a spray or the like so as to have a predetermined film thickness.
  • the surface of the sheet may be coated with the coating agent of the present invention as an undercoat, and then a top coat agent may be applied thereon.
  • a top coat agent include an asphalt emulsifier, a silicone resin emulsion, a fluororesin emulsion, and a mixture of these with an acrylic resin emulsion.
  • the mixture was maintained at 80 ° C for 1 hour, cooled, and neutralized with aqueous ammonia to obtain an ataryl polymer emulsion having a pH of 8, a solid content of 50 parts by weight, and a viscosity of 200 cps. .
  • a mixture of 70 parts by weight of benzyl alcohol, 3 parts by weight of dialkylsulfosuccinate sodium salt and 350 parts by weight of water was added to 400 parts by weight of the acryl resin emulsion, and the mixture was stirred.
  • a coating agent for pills was prepared.
  • PVC sheet (1) A new PVC sheet irradiated by a sunshine carbon arc accelerated weathering tester for 100 hours
  • PVC sheet (2) PVC sheet constructed 10 years ago
  • PVC sheet (3) New PVC sheet
  • the above waterproof sheet was subjected to a weather resistance test, and the adhesion before and after the weathering was measured.
  • a weather resistance test a sunshine carbon arc type accelerated weather resistance test was performed in accordance with JIS K540 "General Paint Test Method 9.8 Accelerated Weather Resistance Test", and irradiation was performed for 100 hours using a testing machine.
  • the test for the adhesion of Goban eyes was performed by JIS K540
  • the test was performed according to K 5400 "General paint test method 8.5.2 Adhesive grid tape method".
  • the slit width was set to 2 mm, and the evaluation was made according to JISK 5408.5.5.1 (5), and expressed as a score.
  • Cellophane adhesive tape (width 18 mm, adhesive strength 300 gf / 10 mm or more) specified in JIS Z1522 was used as the adhesive tape. Table 1 shows the results.
  • the sheet has extremely good adhesion to the VC sheet.
  • a B C invention A B C invention
  • PVC sheet (1) 10 points 10 points 8 points 10 points 6 points 6 points 4 points 10 points
  • PVC sheet (2) 10 points 10 points 8 points 10 points 6 points 6 points 4 ⁇ , 10 points
  • the surface of the PVC sheet slightly swells due to the contained aromatic alcohol, whereby the coating of the acrylic resin emulsion is excellent on the TPVC sheet surface.
  • Adhere to Therefore unlike the conventional method, it is not necessary to add an adhesion improver having poor weather resistance such as rosin or petroleum resin, so that extremely excellent weather resistance and durability can be imparted to the surface of the PVC sheet. O Can be used, greatly reducing the amount of PVC sheet waste o

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

A coating material which comprises an acrylic resin emulsion containing an aromatic alcohol. It is suitable especially for preventing a polyvinyl chloride sheet from deteriorating.

Description

明 細 書 コーティング剤 技術分野  Description Coating agent Technical field
本発明は、 コーティング剤、 特にポリ塩ィ匕ビニル用途に適したコーティング剤 に関する。 背景技術  The present invention relates to a coating agent, particularly a coating agent suitable for use in polyvinyl chloride. Background art
従来、 防水シート等に使用されるポリ塩ィ匕ビニルシートには、 通常、 硬化型ゥ レタン系ゃ硬化型エポキシ系の有機溶剤を多く含むのコーティング剤が塗布され ている。 斯かるコーティング剤は、 塗膜形成の際に引火性のある臭気を伴い、 有 機溶剤が大気中に放出され、 環境上好ましくない。 また、 その塗膜そのものも長 mに渡る耐候性に問題がある。  2. Description of the Related Art Conventionally, a coating agent containing a large amount of a curable polyurethane / curable epoxy-based organic solvent is usually applied to a polyvinyl chloride vinyl sheet used for a waterproof sheet or the like. Such a coating agent is accompanied by a flammable odor when forming a coating film, and an organic solvent is released into the atmosphere, which is environmentally unfavorable. Also, the coating film itself has a problem with weather resistance over a long length of m.
そこで、 水系溶媒を多く含むアクリル樹脂ェマルジヨンに、 ポリ塩化ビニルと の密着性を向上させるための成分として、 ロジン、 石油樹脂などを添加したコー ティング剤が知られている。 しかしながら、 ロジン、 石油樹脂などを含むコーテ イング剤は、 耐候性が悪くて黄変し易く、 しかも、 アクリル樹脂塗膜の耐候性が 不十分である。 発明の開示  Therefore, a coating agent is known in which rosin, petroleum resin, or the like is added to an acrylic resin emulsion containing a large amount of an aqueous solvent as a component for improving the adhesion to polyvinyl chloride. However, coating agents containing rosin, petroleum resin, etc. have poor weather resistance and are prone to yellowing, and the acrylic resin coating film has insufficient weather resistance. Disclosure of the invention
本発明は、 上記課題を解決するものであり、 芳香族アルコールを含むァクリル 樹脂ェマルジヨンより成ることを特徴とするコーティング剤に関する。 このコー ティング剤は、 7クリル樹脂、 芳香族アルコール、 界面活性剤および水を主成分 とした混合液から成る。  The present invention solves the above-mentioned problem, and relates to a coating agent comprising an acryl resin emulsion containing an aromatic alcohol. This coating agent is composed of a mixed solution mainly composed of 7-acryl resin, an aromatic alcohol, a surfactant and water.
ここで、 アクリル樹脂とは、 アクリルエステルの単独重合体またはアクリルェ ステルとその他のビニル化合物モノマーとの共重合体である。 本発明で使用され るモノマー原料としてのァクリルエステルは、 ァクリレート及ぴメタクリレート である （以下、 雨者をまとめて 「 （メタ） ァクリレート」 として示すことがある ) o ァクリルエステルの具体例としては、 メチル （メタ） ァクリレート、 ェチルHere, the acrylic resin is a homopolymer of acrylic ester or a copolymer of acrylic ester and other vinyl compound monomers. The acrylyl ester as a monomer raw material used in the present invention is acrylate and methacrylate (hereinafter, the rain may be collectively referred to as “(meth) acrylate”). ) o Specific examples of acrylyl esters include methyl (meth) acrylate and ethyl.
(メタ） ァクリレート、 n—プロピル （メタ） アタリレート、 n—ブチル （メタ） ァクリレート、 iso—プロピル （メタ一） ァクリレート、 iso—プチル （メタ） ァク リレート、 t一ブチル （メタ） ァクリレート、 シクロへキシル （メタ） ァクリレ ート、 テトラヒ ドロフルフリル （メタ） ァクリレート、 2—ェチルへキシル （メ タ） ァクリレート、 2—ヒドロキシェチル （メタ） ァクリレート、 2—ヒドロキ シプロピル （メタ） アタリレート、 ステアリル （メタ） ァクリレート、 ラウリル(Meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-propyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclo Hexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meta) Acrylate, Lauryl
(メタ） ァクリレート、 ジメチルアミノエチル （メタ） ァクリレート、 ジメチル ァミノプロピル （メタ） ァクリレート等がある。 Examples include (meth) acrylate, dimethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylate.
また、 上記アクリルエステルと共重合可能な他のビニル単量体としては、 ァク リル酸、 メタクリル酸、 イタコン酸、 マレイン酸、 クロトン酸、 ァトロパ酸、 シ トラコン酸などの《， /?—不飽和カルボン酸、 スチレン、 α—メチルスチレン、 メチルビニルエーテル、 ェチルビニルエーテル、 η—プロピルビニルエーテル、 η —ブチルビニルエーテル、 iso—ブチルビニルエーテル、 アクリロニトリル、 メタ タリロニトリル、 酢酸ビニル、 プロピオン酸ビニル、 塩化ビニル、 塩ィ匕ビニリデ ン、 ァリルアルコール、 （メタ） アクリルアミ ド、 ジアセトンアクリルアミ ド、 グリシジル （メタ） ァクリレート、 グリシジルァリルエーテル、 ビニルピロリ ド ン、 ビニルピリジン、 ビニルカルバゾール等がある。  Other vinyl monomers that can be copolymerized with the acrylic ester include acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, atropoic acid, and citraconic acid. Saturated carboxylic acid, styrene, α-methylstyrene, methyl vinyl ether, ethyl vinyl ether, η-propyl vinyl ether, η-butyl vinyl ether, iso-butyl vinyl ether, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, vinyl chloride, vinyl chloride There are dani vinylidene, aryl alcohol, (meth) acrylamide, diacetone acrylamide, glycidyl (meth) acrylate, glycidylaryl ether, vinylpyrrolidone, vinylpyridine, vinylcarbazole and the like.
以上のモノマー原料の処方には種々の組み合わせがあり、 本発明においては任 意の処方を採用し得る。 しかしなが、ら、 特に、 プチルァクリレート及び/又は 2 一ェチルへキシルァクリレート 5〜 5 0重量％、 スチレン 2 0〜 6 0重量％、 a , β一不飽和カルボン酸 0〜 5重量％の割合から成るモノマー原料を重合して得ら れるアタリル樹脂を使用したコーティング剤は、 特に優れた効果を発現する。 アタリル樹脂は以上の様なモノマー原料を重合することにより製造される。 ァ クリル樹脂の製造方法は特に限定されないが、 本発明のコーティング剤がエマル ジョンの形態であるため、 界面活性剤の存在下、 水にモノマー原料を分散して乳 化重合し、 得られたアクリル樹脂ェマルジヨンをそのまま使用する方法が好適に 採用される。  There are various combinations of the above formulas of the monomer raw materials, and any formula can be adopted in the present invention. However, in particular, butyl acrylate and / or 2-ethylhexyl acrylate 5 to 50% by weight, styrene 20 to 60% by weight, a, β-unsaturated carboxylic acid 0 to 5% A coating agent using an atalyl resin obtained by polymerizing a monomer raw material having a percentage by weight exhibits particularly excellent effects. Ataryl resin is produced by polymerizing the above-mentioned monomer raw materials. The method for producing the acrylic resin is not particularly limited. However, since the coating agent of the present invention is in the form of an emulsion, the monomer material is dispersed in water in the presence of a surfactant and emulsion polymerization is carried out. A method in which the resin emulsion is used as it is is suitably used.
乳化重合に使用する界面活性剤は、 好ましくはァニオン性界面活性剤またはノ 二オン性界面活性剤である力 s、 カチオン性界面活性剤でもよい。 上記のァニオン 性界面活性剤としては、 ジアルキルルフォサクシネート、 高級アルコールサルフ ェト （Na塩またはァミン塩） 、 アルキルァリルスルフォン酸塩 （Na塩またはアミ ン塩） 、 アルキルナフ夕レンスルフォン酸塩 （Na塩またはアミン塩） 、 ァノキル ナフタレンスルフォン酸塩縮合物、 アルキルフォスフヱート、 ロジン石鹼、 脂肪 酸塩 （Na塩またはアミン塩） 等がある。 上記のノニォン性界面活性剤としては、 エーテル、 ポリォキシエチレンアルキルステル、 ポリォキシエチレンアルキルァ ミン、 ポリォキシエチレンアルキロ一ノアミン、 ポリォキシエチレンアルキルァ エステル等がある。 上記のカチオン性界活性剤としては、 トリメチルァミノェチ ルアルキルアミ トバロゲニド、 アルキルリジニゥム硫酸塩、 アルキルトリメチル アンモニゥムバロゲニド等がある。 The surfactant used for the emulsion polymerization is preferably an anionic surfactant or a nonionic surfactant. Two on-surfactant at a force s, or a cationic surfactant. Examples of the above-mentioned anionic surfactant include dialkyl lfosuccinate, higher alcohol sulfate (Na salt or amine salt), alkylaryl sulfonate (Na salt or amine salt), and alkyl naphthene sulfonate ( Na salt or amine salt), anoalkyl naphthalene sulfonate condensate, alkyl phosphate, rosin stone, and fatty acid salt (Na salt or amine salt). Examples of the nonionic surfactant include ether, polyoxyethylene alkylster, polyoxyethylene alkylamine, polyoxyethylene alkylmonoamine, and polyoxyethylene alkyl ester. Examples of the above-mentioned cationic surfactant include trimethylaminoethylalkylamitobarogenide, alkylridinium sulfate, and alkyltrimethylammonium barogenide.
乳化重合の際に使用する水の量は、 重合して得られるアクリル樹脂 （通常、 モ ノマー原料全体量として計算できる） に对し、 通常 2 0〜： 1 0 0 0重量部、 好ま しくは 4 0〜3 0 0重量部である。 また、 界面活性剤の使用量は、 アクリル樹脂 1 0 0重量部に対し、 通常 1〜 1 0重量部、 好ましくは 2〜4重量部である。 乳化重合は、 反応系に重合開始剤を加え、 通常 3 0〜9 0 °C程度の加温攪拌下 で行う。 反応系は、 必要に応じ、 窒素などの不活性ガス雰囲気とする。 また、 重 合後は、 所望により、 水酸ィ匕ナトリウム、 水酸化カリウム、 アンモニア等のアル カリを添加して pHを調節してもよい。 ここで、 重合開始剤としては、 過硫酸アン モニゥム、 硫酸力リウム、 過硫酸ナトリウム、 過棚酸ナトリウム等の水溶性無機 重合開始、 2 , 2 ' ーァソビス （2—メチルプロピオンアミジン） ジハイ ドロク 口ライ、 2， 2 ' —ァソビス （2—メチルー N—フエニルプロピオンアミジン） ジハドロクロライト等の水溶性有機重合開始剤、 上記無機または有機重合開始剤 と亜硫酸ナトリウム、 重亜硫酸ナトリウム、 次亜硫酸ナトリウム、 ァスコルピン 酸などの還元剤とを併用したレドックス重合開始剤系が例示される。 重合開始剤 の使用量は、 モノマー原料 1 0 0重量部に対し、 通常 1〜0 . 5重量部であ る o 本発明のコーティング剤は、 以上の様に製造して得られたアクリル樹脂エマル ジョンに所定量の芳香族アルコールを混合して得られる。 この芳香族アルコール としては、 ベンゼンメタノール (ベンジルアルコール) 、 ベンゼンエタノール、 ジフエニルメタノール、 2—ナフタレンメタノール、 1 , 2—ベンゼンジメタノ ール等があり、 特にべンジルアルコールが好ましい。 芳香族アルコールは、 ポリ 塩ィ匕ビ二ルシートに代表されるコ一ティング対象の表面を若干膨潤せしめてコー ティング被膜との密着性を高める。 芳香族アルコールの使用量は、 ァクリル樹脂 1 0 0重量部に対し、 通常 5〜 5 0重量部、 好ましく 1 0〜4 0重量部である。 ポリ塩ィヒビ二ルシートにコ一ティングする場合、 芳香族アルコールの添加量が 5 重量部未満であると皮膜密着性が低下し、 5 0重量部を超えるとポリ塩ィヒビニル の表面が過度に膨潤して被膜にポリ塩ィヒビニルに含まれる可塑剤が、転移する。 本発明のコーティング剤においては、 コーティングの対象や目的に応じ、 水や 界面活性剤をァクリル樹脂ェマルジョンに後から添加して濃度や組成を調整する ことが出来る。 The amount of water used in the emulsion polymerization is usually 20 to 100 parts by weight, preferably 20 to 100 parts by weight, based on the acrylic resin obtained by the polymerization (usually calculated as the total amount of the monomer raw material). It is 40 to 300 parts by weight. The amount of the surfactant to be used is generally 1 to 10 parts by weight, preferably 2 to 4 parts by weight, based on 100 parts by weight of the acrylic resin. Emulsion polymerization is carried out by adding a polymerization initiator to the reaction system and heating and stirring usually at about 30 to 90 ° C. The reaction system should be in an inert gas atmosphere such as nitrogen if necessary. After the polymerization, if necessary, the pH may be adjusted by adding an alkali such as sodium hydroxide, potassium hydroxide, or ammonia. Here, the polymerization initiator includes water-soluble inorganic polymerization such as ammonium persulfate, potassium sulfate, sodium persulfate, and sodium persulfate, and 2,2′-asobis (2-methylpropionamidine) dihydrochloride. , 2, 2'-Asobis (2-methyl-N-phenylpropionamidine) Water-soluble organic polymerization initiators such as dihadrochlorite, inorganic or organic polymerization initiators and sodium sulfite, sodium bisulfite, sodium hyposulfite, ascorpin A redox polymerization initiator system using a reducing agent such as an acid in combination is exemplified. The amount of the polymerization initiator to be used is usually 1 to 0.5 part by weight based on 100 parts by weight of the monomer raw material.o The coating agent of the present invention can be obtained by mixing a predetermined amount of an aromatic alcohol with the acrylic resin emulsion produced as described above. Examples of the aromatic alcohol include benzene methanol (benzyl alcohol), benzene ethanol, diphenyl methanol, 2-naphthalene methanol, and 1,2-benzene dimethanol, and benzyl alcohol is particularly preferable. Aromatic alcohol slightly swells the surface of a coating object typified by a polychlorinated vinyl sheet, and enhances adhesion to a coating film. The amount of the aromatic alcohol to be used is usually 5 to 50 parts by weight, preferably 10 to 40 parts by weight, per 100 parts by weight of the acryl resin. When coating on polyvinyl chloride sheet, if the amount of aromatic alcohol added is less than 5 parts by weight, the film adhesion will decrease, and if it exceeds 50 parts by weight, the surface of polyvinyl chloride will swell excessively. The plasticizer contained in the polyvinyl chloride is transferred to the coating. In the coating agent of the present invention, the concentration and composition can be adjusted by adding water or a surfactant to the acryl resin emulsion later according to the object or purpose of coating.
更に、 ァニオン性またはノニオン性のアクリル樹脂エマルジョンょり成る本発 明のコーティング剤においては、 コーティング剤としての濡れ性改良の観点から 、 ジアルキルスルフォサクシネートのナトリウム塩、 カリウム塩、 'リチウム塩、 アンモニゥム塩等のアル力リ金属塩、 特にジアルキルスルフォサクシネートのナ トリウム塩を添加することが好ましい。 なお、 ジアルキルスルフォサクシネート のアルキル基部分は、 特に制限はな
Figure imgf000005_0001
通常、 炭素数 6〜 1 6程度のアルキル 基の単独または混合種より成る。 ジアルキルスルフォサクシネートのアルカリ金 属塩の添加量は、 アクリル樹脂 1 0 0重量部に対し、 通常 1〜 1 0重量部、 好ま しくは 2〜 5重量部である。 ジアルキルスルフォサクシネートのアル力リ金属塩 の添加量が上記の範囲より少ない場合は濡れ性改良の効果が十分ではなく、 上記 の範囲より多い場合は塗膜の耐水性が低下する傾向がある。 Furthermore, in the coating agent of the present invention comprising an anionic or nonionic acrylic resin emulsion, from the viewpoint of improving the wettability as a coating agent, sodium, potassium and lithium salts of dialkyl sulfosuccinates are used. It is preferable to add an alkali metal salt such as an ammonium salt, particularly a sodium salt of dialkyl sulfosuccinate. There are no particular restrictions on the alkyl group portion of dialkyl sulfosuccinate.
Figure imgf000005_0001
Usually, it consists of a single or mixed alkyl group having about 6 to 16 carbon atoms. The amount of the alkali metal salt of dialkyl sulfosuccinate is usually 1 to 10 parts by weight, preferably 2 to 5 parts by weight, based on 100 parts by weight of the acrylic resin. If the amount of the dialkyl sulfosuccinate metal salt is less than the above range, the effect of improving the wettability is not sufficient, and if it is more than the above range, the water resistance of the coating film tends to decrease. .
本発明のコーティング剤は、 ポリ塩ィ匕ビニル、 ポリエステルシート、 FRP、 コ ンクリートパネル、 モルタル等に適用できるが、 特にポリ塩化ビニルから成る成 形体に好適に使用される。 対象とするポリ塩ィヒビニル （PVC) は、 特に制限はな いが、 代表例としては、 ジォクチルフタレート、 ジブチルフタレート、 トリクレ ジルホスフヱ一ト等の可塑剤を通常 5 0〜 1 0 0重量％添加した通常の半硬質ま たは軟質の PVCシートが挙げられる。 本発明のコーティング剤は、 ナイフコータ 一、 フローコーター、 スプレー等を使用し、 所定の膜厚となる様にシートにコー ティングされる。 更に、 特に防水シートとして使用する場合は、 シートの表面に アンダーコートとして本発明のコーティング剤をコーティングした後、 その上に トップコート剤を塗布するとよい。 トップコート剤としては、 例えば、 ァスファ ルト乳化剤、 シリコン樹脂ェマルジョン、 弗素樹脂ェマルジヨン、 これらとァク リル樹脂ェマルジヨンとの混合物などがある。 The coating agent of the present invention can be applied to polyvinyl chloride, polyester sheet, FRP, concrete panel, mortar, etc., and is particularly preferably used for molded articles made of polyvinyl chloride. The target polychlorinated vinyl (PVC) is not particularly limited, but typical examples include octyl phthalate, dibutyl phthalate, and tricle phthalate. Examples include ordinary semi-rigid or soft PVC sheets to which a plasticizer such as zyl phosphate is usually added in an amount of 50 to 100% by weight. The coating agent of the present invention is coated on a sheet using a knife coater, a flow coater, a spray or the like so as to have a predetermined film thickness. Further, particularly when used as a waterproof sheet, the surface of the sheet may be coated with the coating agent of the present invention as an undercoat, and then a top coat agent may be applied thereon. Examples of the topcoat agent include an asphalt emulsifier, a silicone resin emulsion, a fluororesin emulsion, and a mixture of these with an acrylic resin emulsion.
発明を実施するための最良の形態 BEST MODE FOR CARRYING OUT THE INVENTION
以下、 本発明について実施例により具体的に説明する。  Hereinafter, the present invention will be described specifically with reference to examples.
実施例 1  Example 1
還流器、 温度計、 不活性ガス導入管、 温度計などを備えたフラスコ中に、 水 2 0 0重量部、 ジアルキルスルフォサクシネートナトリゥム塩 1 2重量部、 過硫酸 アンモニゥム 0 . 8重量部を仕込み、 温度 7 0 °Cに加熱しつつ、 スチレン 3 0重 量0 /0、 ブチルアタリレート 1 8重量0 /0、 アクリル酸 1 . 5重量0 /0のモノマー混合 物 2 0 0重量部を略 6時間かけて連続滴下した。 滴下終了後、 8 0 °Cで 1時間維 持した後に冷却し、 アンモニア水で中和し、 p H 8、 固形分濃度 5 0重量部、 粘 度 2 0 0 c p sのアタリル樹脂ェマルジヨンを得た。 In a flask equipped with a reflux condenser, thermometer, inert gas inlet tube, thermometer, etc., 200 parts by weight of water, 12 parts by weight of dialkyl sulfosuccinate sodium salt, 0.8 parts by weight of ammonium persulfate g of parts, while heating to a temperature 7 0 ° C, styrene 3 0 by weight 0/0, butyl Atari rate 1 8 wt 0/0, 1 acrylate. 5 wt 0/0 monomer mixture 2 0 0 weight Was continuously dropped over approximately 6 hours. After completion of the dropwise addition, the mixture was maintained at 80 ° C for 1 hour, cooled, and neutralized with aqueous ammonia to obtain an ataryl polymer emulsion having a pH of 8, a solid content of 50 parts by weight, and a viscosity of 200 cps. .
上記ァクリル樹脂エマルジョン 4 0 0重量部に、 ベンジルアルコール 7 0重量 部、 ジアルキルスルフォサクシネートナトリウム塩 3重量部および水 5 3 0重量 部とから成る混合液を添加して攪拌し、 ポリ塩ィヒビ二ル用コ一ティング剤を調製 した。  A mixture of 70 parts by weight of benzyl alcohol, 3 parts by weight of dialkylsulfosuccinate sodium salt and 350 parts by weight of water was added to 400 parts by weight of the acryl resin emulsion, and the mixture was stirred. A coating agent for pills was prepared.
次いで、 上記のコーティング剤を下記 3種類の PVCシ一ト表面に刷毛で塗工量 0 . 2 K g /m2で均一に塗布し、 気温 2 0 °C、 湿度 6 0 %で 3日間乾燥させ、 防 水シートを得た。 Then, 3 days drying the coating agent at the following three types of PVC sheet one preparative surface coating amount with a brush 0. Was uniformly coated with 2 K g / m 2, temperature 2 0 ° C, Humidity 6 0% Then, a waterproof sheet was obtained.
PVCシート （1 ) ：新品の PVCシートをサンシャインカーボンアーク促進耐候 性試験機により 1 0 0 0時間照射したもの  PVC sheet (1): A new PVC sheet irradiated by a sunshine carbon arc accelerated weathering tester for 100 hours
PVCシート （2 ) ： 1 0年前に施工された PVCシート PVCシート （ 3 ) ：新品の PVCシ一ト PVC sheet (2): PVC sheet constructed 10 years ago PVC sheet (3): New PVC sheet
上記の防水シートに対して耐侯性試験を施し、 その前後のゴバン目付着性を測 定した。 耐候性試,験としては、 J I S K 5 4 0 0 「塗料一般試験方法 9 . 8 促進耐候性試験」 に準ずるサンシャインカーボンアーク式促進耐候性試験を行い 、 試験機により 1 0 0 0時間照射した。 また、 ゴバン目付着性の試験は、 J I S The above waterproof sheet was subjected to a weather resistance test, and the adhesion before and after the weathering was measured. As the weather resistance test, a sunshine carbon arc type accelerated weather resistance test was performed in accordance with JIS K540 "General Paint Test Method 9.8 Accelerated Weather Resistance Test", and irradiation was performed for 100 hours using a testing machine. In addition, the test for the adhesion of Goban eyes was performed by JIS
K 5 4 0 0 「塗料一般試験方法 8 . 5 . 2 付着性の碁盤目テープ法」 に準じ て行った。 スリッ ト幅は 2 mmとし、 J I S K 5 4 0 0 8 . 5 . 1 ( 5 ) に 準じて評価し、 点数で表した。 粘着テープとしては、 J I S Z 1 5 2 2に規 定されるセロファン粘着テープ （幅 1 8 mm、 粘着力 3 0 0 g f / 1 0 mm以上の もの） を使用した。 結果を表 1に示す。 The test was performed according to K 5400 "General paint test method 8.5.2 Adhesive grid tape method". The slit width was set to 2 mm, and the evaluation was made according to JISK 5408.5.5.1 (5), and expressed as a score. Cellophane adhesive tape (width 18 mm, adhesive strength 300 gf / 10 mm or more) specified in JIS Z1522 was used as the adhesive tape. Table 1 shows the results.
また、 比較として、 PVCシート表面に下記 2種類のプライマーを上記と同様に 塗布して得た防水シートについて上記と同様の試験を行った。 結果を表 1に示す  As a comparison, the same test as above was performed on a waterproof sheet obtained by applying the following two types of primers to the surface of a PVC sheet in the same manner as above. Table 1 shows the results
A . 市販 2液硬ィヒ型水性ェポキシ樹脂系プライマー A. Commercially available two-component hard water-based epoxy resin primer
B . 市販 1液湿気硬化型ウレタン系プライマー  B. One-pack moisture-curable urethane primer on the market
C . 上記ァクリル樹脂ェマルジョン (但し、 ベンジルアルコールを含有せず) 表 1より、 本発明のコーティング剤が、 従来からコーティング剤と比較して、 p C. The above acryl resin emulsion (but not containing benzyl alcohol) From Table 1, it is clear that the coating agent of the present invention has p
VCシートに対して極めて良好な付着力を有していることが分かる。 It can be seen that the sheet has extremely good adhesion to the VC sheet.
耐候性試験前 耐候性試験後 Before weathering test After weathering test
. A B C 発明品 A B C 発明品 A B C invention A B C invention
PVCシート （1 ) 10点 10点 8点 10点 6点 6点 4点 10点  PVC sheet (1) 10 points 10 points 8 points 10 points 6 points 6 points 4 points 10 points
PVCシート （2 ) 10点 10点 8点 10点 6点 6点 4丄ハ占、、 10点 PVC sheet (2) 10 points 10 points 8 points 10 points 6 points 6 points 4 丄, 10 points
PVCシート （3 ) 8点 8点 6点 10点 6点 6点 4点 10点 注） 1 0点：切り傷 1本毎が細く雨側が滑らかで、 切り傷との交点と正方形の一 目一目に剥がれがない。 PVC sheet (3) 8 points 8 points 6 points 10 points 6 points 6 points 4 points 10 points Note) 10 points: Each cut is thin and the rain side is smooth, and the intersection with the cut and the square are not peeled at every glance.
8点：切り傷の交点にわずかな剥がれがあって、 正方形の一目一目に剥が れがなく、欠損部の面積は全正方形面積の 5 %以内である。  8 points: There is slight peeling at the intersection of the cuts, and there is no peeling at a glance of the square, and the area of the defect is within 5% of the total square area.
6点：切り傷の両側と交点とには剥がれがあつて、 欠損部の面積は全正方 形面積の 5〜：！ 5 %である。  6 points: Both sides of the cut and the intersection are peeled off, and the area of the defect is 5 ~ of the total square area! 5%.
4点：切り傷による剥がれの巾力 ¾ く、 欠損不の面積は全正方形面積の 1 5〜3 5 %である。 産業上の利用可能性  4 points: The width of peeling due to cuts is large, and the area of no defect is 15 to 35% of the total square area. Industrial applicability
本発明のァクリル樹脂エマルジョンは、 特に PVCシートに塗布した場合、 含有 する芳香族アルコールによつて PVCシ一ト表面が若干膨潤し、 それによつてァク リル樹脂ェマルジヨンの被膜が TPVCシート表面に良好に密着する。 従って、 従来 法の様にロジンや石油樹脂などの耐候性の悪い密着改良剤を添加する必要がない ため、 PVCシート表面に極めて優れた耐候性と耐久性を与えることが出来、 PVC シートの長期使用が可能になり、 PVCシートの廃棄物量を大巾に減少することが 出来 o  In particular, when the acryl resin emulsion of the present invention is applied to a PVC sheet, the surface of the PVC sheet slightly swells due to the contained aromatic alcohol, whereby the coating of the acrylic resin emulsion is excellent on the TPVC sheet surface. Adhere to Therefore, unlike the conventional method, it is not necessary to add an adhesion improver having poor weather resistance such as rosin or petroleum resin, so that extremely excellent weather resistance and durability can be imparted to the surface of the PVC sheet. O Can be used, greatly reducing the amount of PVC sheet waste o

Claims

請 求 の 範 囲 The scope of the claims
1 . 芳香族アルコールを含むアクリル樹脂ェマルジヨンより成ることを特徴とす るコーティング剤。 1. A coating agent comprising an acrylic resin emulsion containing an aromatic alcohol.
2 . アタリル樹脂エマルジョンが、 アタリル樹脂、 芳香族ァルコール、 界面活性 剤及び水の混合液である請求項 1に記載のコーティング剤。  2. The coating agent according to claim 1, wherein the ataryl resin emulsion is a mixture of an ataryl resin, an aromatic alcohol, a surfactant and water.
3 . アタリル樹脂 1 0 0重量部に対して、 芳香族アルコール 5〜 5 0重量部から 成る混合液である請求項 2に記載のコーティング剤。  3. The coating agent according to claim 2, which is a mixed solution comprising 5 to 50 parts by weight of an aromatic alcohol with respect to 100 parts by weight of an ataryl resin.
4 . アタリル樹脂 1 0 0重量部に対して、 界面活性剤 1〜 1 0重量部から成る混 合液である請求項 2又は 3に記載のコーティング剤。  4. The coating agent according to claim 2 or 3, which is a mixed solution comprising 1 to 10 parts by weight of a surfactant with respect to 100 parts by weight of an ataryl resin.
5 . アタリル樹脂 1 0 0重量部に対して、 水 2 0〜 1 0 0 0重量部から成る混合 液である請求項 2〜 4の何れかに 載のコ一ティング剤。  5. The coating agent according to any one of claims 2 to 4, wherein the coating agent is a mixed solution comprising 20 to 100 parts by weight of water with respect to 100 parts by weight of the ataryl resin.
6 . ァクリル樹脂が、 プチルァクリレート及ぴ Z又は 2—ェチルへキシルアタリ レート 5〜5 0重量0 /0、 スチレン 2 0〜6 0重量0 /0、 a , /3—不飽和カルボン酸 0〜 5重量％の割合から成るモノマー原料を重合して得られる請求項 2〜 5の何 れかに言己載のコーティング剤。 6. Akuriru resin, Petit Rua chestnut rate及Pi Z or Kishiruatari rate 5-5 0 weight 0/0 to 2 Echiru, styrene 2 0-6 0 weight 0/0, a, / 3- unsaturated carboxylic acid 0 The coating agent according to any one of claims 2 to 5, which is obtained by polymerizing a monomer material having a ratio of 5 to 5% by weight.
7 . 芳香族アルコ一ルがべンジルアルコールである請求項 1〜 6の何れかに記載 のコーティング剤。  7. The coating agent according to any one of claims 1 to 6, wherein the aromatic alcohol is benzyl alcohol.
8 . 界面活性剤がジアルキルスルホサクシネートアルカリ金属塩である請求項 2 〜 7の何れかに記載のコーティング剤。  8. The coating agent according to any one of claims 2 to 7, wherein the surfactant is an alkali metal salt of dialkyl sulfosuccinate.
9 . ポリ塩ィ匕ビニル用である請求項 1〜 8の何れかに記載のコーティング剤。  9. The coating agent according to any one of claims 1 to 8, which is used for polyvinyl chloride vinyl.
PCT/JP2000/003739 2000-06-09 2000-06-09 Coating material WO2001094485A1 (en)

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Application Number Priority Date Filing Date Title
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Application Number Priority Date Filing Date Title
PCT/JP2000/003739 WO2001094485A1 (en) 2000-06-09 2000-06-09 Coating material

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5991158A (en) * 1982-11-15 1984-05-25 Mitsui Toatsu Chem Inc Water-dispersed coating composition
JPS6372764A (en) * 1986-09-16 1988-04-02 Asahi Chem Ind Co Ltd Thickened latex composition for coating
JPH10152634A (en) * 1996-11-25 1998-06-09 Showa Electric Wire & Cable Co Ltd Release agent for fire spread preventive coating
EP0846736A1 (en) * 1996-12-06 1998-06-10 Elf Atochem S.A. Paint stripper for removing coatings and lacquers
JPH11137084A (en) * 1997-11-12 1999-05-25 Dainichiseika Color & Chem Mfg Co Ltd Colorant for vegetational grass and coloring of vegetational grass

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5991158A (en) * 1982-11-15 1984-05-25 Mitsui Toatsu Chem Inc Water-dispersed coating composition
JPS6372764A (en) * 1986-09-16 1988-04-02 Asahi Chem Ind Co Ltd Thickened latex composition for coating
JPH10152634A (en) * 1996-11-25 1998-06-09 Showa Electric Wire & Cable Co Ltd Release agent for fire spread preventive coating
EP0846736A1 (en) * 1996-12-06 1998-06-10 Elf Atochem S.A. Paint stripper for removing coatings and lacquers
JPH11137084A (en) * 1997-11-12 1999-05-25 Dainichiseika Color & Chem Mfg Co Ltd Colorant for vegetational grass and coloring of vegetational grass

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