JP2011038013A - Vinyl modified polyester polyol, two-component curable coating composition and cured object - Google Patents
Vinyl modified polyester polyol, two-component curable coating composition and cured object Download PDFInfo
- Publication number
- JP2011038013A JP2011038013A JP2009187509A JP2009187509A JP2011038013A JP 2011038013 A JP2011038013 A JP 2011038013A JP 2009187509 A JP2009187509 A JP 2009187509A JP 2009187509 A JP2009187509 A JP 2009187509A JP 2011038013 A JP2011038013 A JP 2011038013A
- Authority
- JP
- Japan
- Prior art keywords
- polyester polyol
- vinyl
- vegetable oil
- modified polyester
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 57
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title abstract description 13
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 62
- 239000008158 vegetable oil Substances 0.000 claims abstract description 62
- 239000002994 raw material Substances 0.000 claims abstract description 56
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 43
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Landscapes
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
本発明は、いわゆるカーボンニュートラルな材料である植物油由来原料を利用したビニル変性ポリエステルポリオールと、これを用いた二液硬化型塗料組成物および硬化物（硬化塗膜）とに関する。 The present invention relates to a vinyl-modified polyester polyol using a vegetable oil-derived raw material, which is a so-called carbon neutral material, and a two-component curable coating composition and a cured product (cured coating film) using the same.
現在、塗料の多くは、主に石油などの化石資源由来の原材料を使用して製造されている。そして、このような塗料の製造時や廃棄時には、地球温暖化の原因となる二酸化炭素が発生し、大気中の二酸化炭素量を増加させることになる。
一方、植物由来の原料は、植物が大気中の二酸化炭素を取り込み光合成反応によって生成したものであるので、例えば焼却等によりこれから二酸化炭素が発生しても、発生した二酸化炭素は元々大気中にあった二酸化炭素に相当し、収支はプラスマイナスゼロとなるため、大気中の二酸化炭素の総量を増加させない。このように大気中の二酸化炭素の総量を増加させない材料は、カーボンニュートラルな材料と称され、近年、地球温暖化の防止が重要視されるなか、注目されている。例えば、日本バイオプラスチック協会は、２５重量％以上の植物由来原料から構成されるプラスチックをバイオプラスチック識別認定するといった制度を設けており、塗料の分野においても、乾燥塗膜全体中２５重量％以上がカーボンニュートラルな植物由来原料で構成される塗料が望まれている。
Currently, many paints are manufactured using raw materials mainly derived from fossil resources such as petroleum. And at the time of manufacture and disposal of such a paint, carbon dioxide causing global warming is generated, and the amount of carbon dioxide in the atmosphere is increased.
On the other hand, since plant-derived raw materials are produced by a photosynthesis reaction by a plant taking in carbon dioxide from the atmosphere, for example, even if carbon dioxide is generated by incineration or the like, the generated carbon dioxide is originally in the atmosphere. It is equivalent to carbon dioxide, and the balance is plus or minus zero, so it does not increase the total amount of carbon dioxide in the atmosphere. Such a material that does not increase the total amount of carbon dioxide in the atmosphere is called a carbon-neutral material, and has been attracting attention in recent years, while prevention of global warming is regarded as important. For example, the Japan Bioplastics Association has established a system for bioplastic identification and recognition of plastics made from plant-derived raw materials of 25% by weight or more. A paint composed of carbon-neutral plant-derived materials is desired.
植物由来原料を利用した塗料としては、これまでに、植物油で変性されたポリエステルポリオールをポリイソシアネートで硬化させる塗料（特許文献１）、（半）乾性油や（半）乾性油脂肪酸を含有するアルキド樹脂でビニル系樹脂を変性したアルキド変性ビニル系重合体を塗料樹脂成分とした塗料（特許文献２）、トウモロコシ等から得られる糖質を原料として製造されるポリ乳酸を樹脂成分とした被覆材（特許文献３）、キシロースやアラビトースから構成される多糖類を水酸基と反応する官能基を有する硬化剤で硬化させる塗料（特許文献４）、澱粉、変性澱粉またはそのビニル変性物、もしくはこれらにイソシアネート化合物を反応させて得られる樹脂をバインダーとする塗料(特許文献５、６)などが知られている。 As paints using plant-derived raw materials, paints for curing polyester polyols modified with vegetable oils with polyisocyanate (Patent Document 1), alkyds containing (semi) dry oils and (semi) dry oil fatty acids. A coating material (Patent Document 2) using an alkyd-modified vinyl polymer obtained by modifying a vinyl resin with a resin as a coating resin component (Patent Document 2), a coating material using polylactic acid produced from a saccharide obtained from corn or the like as a raw material (resin component) Patent Document 3), a paint for curing a polysaccharide composed of xylose or arabitose with a curing agent having a functional group that reacts with a hydroxyl group (Patent Document 4), starch, modified starch or vinyl modified product thereof, or isocyanate compounds thereof There are known paints (Patent Documents 5 and 6) using a resin obtained by reacting as a binder.
しかしながら、特許文献１に記載の植物油変性ポリエステルポリオール（アルキド樹脂）は、その脂肪酸骨格によって、得られる塗膜の耐摩耗性、硬度および耐候性を低下させるとともに、エステル結合を有することによって、塗膜の耐水性を低下させる、といった問題があった。また、特許文献２に記載のアルキド変性ビニル系重合体では、アルキド樹脂に起因する欠点がビニル系樹脂のビニル構造によって改善されるものの、植物油（（半）乾性油や（半）乾性油脂肪酸）の含有量を多くすると、それに応じて耐摩耗性等の塗膜物性が低下する、といった問題があった。さらに、特許文献３に記載のポリ乳酸は、硬脆い特性があるため、塗膜の耐摩耗性の低下を招くことになり、特許文献４に記載の多糖類や、特許文献５、６に記載の澱粉やその各種変性物等も、同様に塗膜の耐摩耗性を損なうことになる。 However, the vegetable oil-modified polyester polyol (alkyd resin) described in Patent Document 1 reduces the abrasion resistance, hardness, and weather resistance of the resulting coating film by its fatty acid skeleton, and has an ester bond, thereby providing a coating film. There was a problem that the water resistance of the resin was lowered. In addition, in the alkyd-modified vinyl polymer described in Patent Document 2, although the defects caused by the alkyd resin are improved by the vinyl structure of the vinyl resin, vegetable oil ((semi) dry oil or (semi) dry oil fatty acid) When the content of is increased, there has been a problem that the physical properties of the coating such as wear resistance are lowered accordingly. Furthermore, since the polylactic acid described in Patent Document 3 has hard and brittle characteristics, it causes a decrease in the wear resistance of the coating film. The polysaccharide described in Patent Document 4 and Patent Documents 5 and 6 are described. Similarly, the starch and various modified products thereof also impair the abrasion resistance of the coating film.
このように、カーボンニュートラルな材料である植物油由来原料を用いた従来の塗料では、充分に満足しうる塗膜物性を得ることができず、とりわけ塗膜の耐摩耗性については、植物油由来原料を用いる場合（特に多量に用いる場合）、その低下は避けられない、という問題があった。 Thus, with a conventional paint using a vegetable neutral raw material that is a carbon neutral material, it is not possible to obtain a sufficiently satisfactory coating film physical property. When used (especially when used in large amounts), there is a problem that the reduction is inevitable.
本発明は、上記問題点に鑑みなされたものであって、その目的は、カーボンニュートラルな材料である植物油由来原料を用いながら、耐摩耗性、硬度、耐候性などの塗膜物性を損なうことのない塗料の樹脂成分として有用なビニル変性ポリエステルポリオールと、これを用いた二液硬化型塗料組成物および硬化物（硬化塗膜）とを提供することにある。 The present invention has been made in view of the above problems, and its purpose is to impair coating film properties such as wear resistance, hardness, and weather resistance while using a vegetable oil-derived raw material that is a carbon neutral material. Another object of the present invention is to provide a vinyl-modified polyester polyol useful as a resin component of a coating material, a two-component curable coating composition using the same, and a cured product (cured coating film).
本発明者らは、上記課題を解決すべく鋭意検討を行なった。その結果、植物油由来原料を用いて得られた特定のポリエステルポリオール（Ａ）に対して、特定のビニル重合体部（Ｂ）を特定の構成比率で結合させることにより変性したビニル変性ポリエステルポリオールであれば、イソシアネート化合物と組合せて二液硬化型塗料としたときに、良好な塗膜物性を発現しうることを見出し、本発明を完成した。 The present inventors have intensively studied to solve the above problems. As a result, a vinyl-modified polyester polyol modified by bonding a specific vinyl polymer part (B) at a specific composition ratio to a specific polyester polyol (A) obtained using a vegetable oil-derived raw material. For example, it was found that when a two-component curable coating was combined with an isocyanate compound, good physical properties of the coating film could be expressed, and the present invention was completed.
すなわち、本発明は以下の構成を有する。
（１）植物油由来原料を用いて得られたポリエステルポリオール（Ａ）に、ビニル重合体部（Ｂ）を結合させたビニル変性ポリエステルポリオールであって、
（ｉ）ポリエステルポリオール（Ａ）とビニル重合体部（Ｂ）との構成比率が、重量比で、（Ａ）：（Ｂ）＝２０：８０〜８０：２０であり、
（ｉｉ）ビニル変性ポリエステルポリオールに含まれる植物油由来原料が、該ビニル変性ポリエステルポリオール中の不揮発分に対して２０〜８０重量％であり、
（ｉｉｉ）ポリエステルポリオール（Ａ）の水酸基価が４０〜３００であり、
（ｉｖ）ビニル重合体部（Ｂ）の水酸基価が１０〜３００であり、
（ｖ）ビニル重合体部（Ｂ）のガラス転移点が２０〜１５０℃である、
ことを特徴とするビニル変性ポリエステルポリオール。
（２）ポリエステルポリオール（Ａ）中に占める植物油由来原料の含有割合が３０〜１００重量％であり、かつ、この植物油由来原料が、植物油またはその脂肪酸、植物油を原料として製造されるカルボン酸、および、植物油由来の水酸基を有する原料からなる群より選ばれる１種以上である、前記（１）に記載のビニル変性ポリエステルポリオール。
（３）ビニル重合体部（Ｂ）は、２個以上の環からなる飽和脂環基を有する(メタ)アクリル酸エステル（ｂ１）が５〜８０重量％、水酸基含有モノマー（ｂ２）が２〜８０重量％、前記（ｂ１）または前記（ｂ２）とラジカル重合可能なその他のモノマー（ｂ３）が０〜９３重量％からなる単量体成分で構成されている、前記（１）または（２）に記載のビニル変性ポリエステルポリオール。
（４）前記（１）〜（３）に記載のビニル変性ポリエステルポリオールを含むポリオール成分と、イソシアネート化合物を含むポリイソシアネート成分とからなることを特徴とする二液硬化型塗料組成物。
（５）前記（１）〜（３）に記載のビニル変性ポリエステルポリオールをイソシアネート化合物で硬化させてなる、ことを特徴とする硬化物。
That is, the present invention has the following configuration.
(1) A vinyl-modified polyester polyol obtained by binding a vinyl polymer part (B) to a polyester polyol (A) obtained using a vegetable oil-derived raw material,
(I) The composition ratio of the polyester polyol (A) and the vinyl polymer part (B) is (A) :( B) = 20: 80 to 80:20 by weight ratio,
(Ii) The vegetable oil-derived raw material contained in the vinyl-modified polyester polyol is 20 to 80% by weight based on the nonvolatile content in the vinyl-modified polyester polyol,
(Iii) The polyester polyol (A) has a hydroxyl value of 40 to 300,
(Iv) The hydroxyl value of the vinyl polymer part (B) is 10 to 300,
(V) The glass transition point of the vinyl polymer part (B) is 20 to 150 ° C.
A vinyl-modified polyester polyol characterized by that.
(2) The content ratio of the vegetable oil-derived raw material in the polyester polyol (A) is 30 to 100% by weight, and the vegetable oil-derived raw material is a vegetable oil or a fatty acid thereof, a carboxylic acid produced using the vegetable oil as a raw material, and The vinyl-modified polyester polyol according to (1), which is at least one selected from the group consisting of raw materials having a hydroxyl group derived from vegetable oil.
(3) The vinyl polymer part (B) has 5 to 80% by weight of the (meth) acrylic acid ester (b1) having a saturated alicyclic group composed of two or more rings, and 2 to 2 hydroxyl group-containing monomers (b2). 80% by weight, (b1) or (b2) and another monomer (b3) capable of radical polymerization being composed of monomer components consisting of 0 to 93% by weight, (1) or (2) The vinyl-modified polyester polyol described in 1.
(4) A two-component curable coating composition comprising a polyol component containing the vinyl-modified polyester polyol according to (1) to (3) and a polyisocyanate component containing an isocyanate compound.
(5) A cured product obtained by curing the vinyl-modified polyester polyol according to (1) to (3) with an isocyanate compound.
本発明によれば、カーボンニュートラルな材料である植物油由来原料を用いながら、耐摩耗性、硬度、耐候性などの塗膜物性が良好である硬化塗膜を形成することができる、という効果が得られる。このようにカーボンニュートラルな材料を用いて形成された硬化塗膜は、廃棄時等にも大気中の二酸化炭素の総量を増加させることがないので、地球温暖化の防止に有効である。したがって、このような硬化塗膜を形成する塗料は、例えば携帯電話やノートパソコン等のモバイル製品、自動車の内装、外装部品等のように、多くの衝撃が加わり、耐摩耗性が要求される用途における塗装に好適である。 According to the present invention, it is possible to form a cured coating film having good coating properties such as abrasion resistance, hardness, and weather resistance while using a vegetable oil-derived raw material that is a carbon neutral material. It is done. The cured coating film formed using a carbon neutral material in this way is effective in preventing global warming because it does not increase the total amount of carbon dioxide in the atmosphere even when discarded. Therefore, paints that form such a cured coating film are used for applications that require a lot of impact and wear resistance, such as mobile products such as mobile phones and laptop computers, automobile interiors, and exterior parts. It is suitable for painting.
本発明のビニル変性ポリエステルポリオールは、植物油由来原料を用いて得られたポリエステルポリオール（Ａ）に、ビニル重合体部（Ｂ）を結合させたものである。 The vinyl-modified polyester polyol of the present invention is obtained by bonding a vinyl polymer part (B) to a polyester polyol (A) obtained using a vegetable oil-derived raw material.
前記植物油由来原料は、植物油またはその脂肪酸、植物油を原料として製造されるカルボン酸、および、植物油由来の水酸基を有する原料からなる群より選ばれる１種以上であることが好ましい。
植物油または植物油脂肪酸としては、例えば、支那桐油（脂肪酸）、亜麻仁油（脂肪酸）、脱水ひまし油（脂肪酸）、トール油脂肪酸、綿実油（脂肪酸）、大豆油（脂肪酸）、オリーブ油（脂肪酸）、サフラワー油（脂肪酸）、ひまし油（脂肪酸）米糠油（脂肪酸）、水添やし油（脂肪酸）、やし油（脂肪酸）、パーム油（脂肪酸）等が挙げられる。
The vegetable oil-derived raw material is preferably at least one selected from the group consisting of vegetable oil or fatty acids thereof, carboxylic acids produced using vegetable oil as a raw material, and raw materials having a hydroxyl group derived from vegetable oil.
Examples of vegetable oil or vegetable oil fatty acid include Chinese tung oil (fatty acid), flaxseed oil (fatty acid), dehydrated castor oil (fatty acid), tall oil fatty acid, cottonseed oil (fatty acid), soybean oil (fatty acid), olive oil (fatty acid), safflower oil (Fatty acid), castor oil (fatty acid) rice bran oil (fatty acid), hydrogenated coconut oil (fatty acid), coconut oil (fatty acid), palm oil (fatty acid) and the like.
植物油を原料として製造されるカルボン酸としては、例えば、ひまし油から製造される１２−ヒドロキシステアリン酸、ヘプチル酸、ウンデシレン酸、セバシン酸；松ヤニより精製されるロジン、その水素化物である水添ロジン、およびその重合体である重合ロジン；トール油脂肪酸等の乾性植物油脂肪酸から製造されるダイマー酸、およびその水素化物である水添ダイマー酸；ダイマー酸製造時に副生されるイソステアリン酸；等が挙げられる。
植物油由来の水酸基を有する原料としては、例えば、ひまし油から製造されるヘプタナール、オクタノール、１，１０−デカンジオール；各植物油から精製されるグリセリン；等が挙げられる。
Examples of the carboxylic acid produced from vegetable oil include 12-hydroxystearic acid, heptyl acid, undecylenic acid, sebacic acid produced from castor oil; rosin purified from pine ani, and hydrogenated rosin that is a hydride thereof. And a polymerized rosin that is a polymer thereof; a dimer acid produced from a dry vegetable oil fatty acid such as tall oil fatty acid, and a hydrogenated dimer acid that is a hydride thereof; isostearic acid produced as a by-product during the production of dimer acid; It is done.
Examples of the raw material having a hydroxyl group derived from vegetable oil include heptanal, octanol, 1,10-decanediol produced from castor oil; glycerin purified from each vegetable oil; and the like.
前記ポリエステルポリオール（Ａ）は、上述した植物油由来原料を用いて得られたものであればよく、その製造方法は特に制限されないが、例えば、前記植物油由来原料と、必要に応じて、エステル化反応に一般に使用される酸成分および／またはアルコール成分とを、エステル化反応させることにより、得ることができる。 The polyester polyol (A) is not particularly limited as long as it is obtained using the above-described vegetable oil-derived raw material. For example, the vegetable oil-derived raw material and, if necessary, an esterification reaction It is possible to obtain an acid component and / or an alcohol component that are generally used in the above by esterification.
前記ポリエステルポリオール（Ａ）を得る際に用いることのできる酸成分としては、例えば、安息香酸、ｐ−ｔｅｒｔ−ブチル安息香酸、イソフタル酸、無水フタル酸、テレフタル酸、オルソフタル酸、２，６−ナフタレンジカルボン酸、アゼライン酸、セバシン酸、イソセバシン酸、シュウ酸、トリメリット酸、（無水）コハク酸、（無水）マレイン酸、フマル酸、（無水）イタコン酸、ドデカンオン酸、テトラヒドロ（無水）フタル酸、ヘキサヒイドロ（無水）フタル酸、ヘキサハイドロイソフタル酸、ヘキサハイドロテレフタル酸、テトラクロロ（無水）フタル酸、ヘキサクロロ（無水）フタル酸、テトラブロモ（無水）フタル酸、グルタール酸、アジピン酸、ピメリン酸、ユベリン酸、水添フタル酸、１，４−シクロヘキサンジカルボン酸等が挙げられる。なお、酸成分は、１種のみであってもよいし、２種以上であってもよい。 Examples of the acid component that can be used for obtaining the polyester polyol (A) include benzoic acid, p-tert-butylbenzoic acid, isophthalic acid, phthalic anhydride, terephthalic acid, orthophthalic acid, and 2,6-naphthalene. Dicarboxylic acid, azelaic acid, sebacic acid, isosebacic acid, oxalic acid, trimellitic acid, (anhydrous) succinic acid, (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, dodecanoic acid, tetrahydro (anhydride) phthalic acid, Hexahydro (anhydride) phthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, tetrachloro (anhydride) phthalic acid, hexachloro (anhydride) phthalic acid, tetrabromo (anhydride) phthalic acid, glutaric acid, adipic acid, pimelic acid, uberic acid , Hydrogenated phthalic acid, 1,4-cyclohexanedicar Such as phosphate and the like. In addition, only 1 type may be sufficient as an acid component, and 2 or more types may be sufficient as it.
前記ポリエステルポリオール（Ａ）を得る際に用いることのできるアルコール成分としては、例えば、エチレングリコール、ネオペンチルグリコール、ジエチレングリコール、テトラメチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、２，３，４−トリメチル−１，３−ペンタンジオール、３−メチルペンテン−１，５−ジオール、１，４−シクロヘキサンジメタノール、ビスフェノールＡまたは水素化ビスフェノールＡのエチレンオキシドもしくはプロピレノキシド、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール、ポリブチレングリコール、２，２−ジエチル−１，３−プロパンジオール、２−ｎ−ブチル−エチル−１，３−プロパンジオール、トリシクロデカンジメタノール、シクロヘキサンジカルボン酸、シクロヘキサンジメタノール、シクロヘキサンジオールなどの２価アルコール成分；合成グリセリン（植物油由来ではない）、トリメチロールプロパン、トリメチロールエタンなどの３価アルコール成分；ペンタエリスリトールなどの４価アルコール；等が挙げられる。なお、アルコール成分は、１種のみであってもよいし、２種以上であってもよい。 Examples of the alcohol component that can be used in obtaining the polyester polyol (A) include ethylene glycol, neopentyl glycol, diethylene glycol, tetramethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 2,3,4. -Trimethyl-1,3-pentanediol, 3-methylpentene-1,5-diol, 1,4-cyclohexanedimethanol, ethylene oxide or propylene oxide of bisphenol A or hydrogenated bisphenol A, polyethylene glycol, polypropylene glycol, polytetramethylene Glycol, polybutylene glycol, 2,2-diethyl-1,3-propanediol, 2-n-butyl-ethyl-1,3-propanediol, Dihydric alcohol components such as licyclodecane dimethanol, cyclohexanedicarboxylic acid, cyclohexanedimethanol, cyclohexanediol; trihydric alcohol components such as synthetic glycerin (not derived from vegetable oil), trimethylolpropane, trimethylolethane; pentaerythritol, etc. Tetrahydric alcohol; and the like. In addition, only 1 type may be sufficient as an alcohol component, and 2 or more types may be sufficient as it.
前記ポリエステルポリオール（Ａ）を得るにあたり、植物油由来原料の使用量は、得られるポリエステルポリオール（Ａ）中に占める植物油由来原料の含有割合が３０〜１００重量％となるように設定することが好ましい。ポリエステルポリオール（Ａ）中に占める植物油由来原料の含有割合が３０重量％未満であると、カーボンニュートラルな材料を利用することにより得られる地球温暖化防止効果が小さくなる傾向がある。
なお、前記ポリエステルポリオール（Ａ）を得る際のエステル化反応は、従来公知のエステル化方法や条件等を適宜採用して行えばよい。
When obtaining the said polyester polyol (A), it is preferable to set the usage-amount of a vegetable oil origin raw material so that the content rate of the vegetable oil origin raw material which occupies in the obtained polyester polyol (A) may be 30-100 weight%. When the content ratio of the vegetable oil-derived raw material in the polyester polyol (A) is less than 30% by weight, the effect of preventing global warming obtained by using a carbon neutral material tends to be small.
In addition, what is necessary is just to employ | adopt conventionally well-known esterification method, conditions, etc. for the esterification reaction at the time of obtaining the said polyester polyol (A) suitably.
本発明において、前記ポリエステルポリオール（Ａ）の水酸基価は４０〜３００であることが重要である。ポリエステルポリオール（Ａ）の水酸基価が４０未満であると、得られるビニル変性ポリエステルポリオールを二液硬化型塗料組成物として硬化塗膜を形成したときに、塗膜の架橋密度が低くなり、結果として、耐摩耗性、耐候性、耐水性、耐溶剤性、耐薬品性が不充分になる。一方、ポリエステルポリオール（Ａ）の水酸基価が３００を超えると、やはり、硬化塗膜を形成したときに、塗膜の耐候性、耐水性、耐溶剤性、耐薬品性が低下する。 In the present invention, it is important that the polyester polyol (A) has a hydroxyl value of 40 to 300. When the hydroxyl value of the polyester polyol (A) is less than 40, when a cured coating film is formed using the resulting vinyl-modified polyester polyol as a two-component curable coating composition, the crosslinking density of the coating film becomes low, and as a result Insufficient wear resistance, weather resistance, water resistance, solvent resistance, and chemical resistance. On the other hand, when the hydroxyl value of the polyester polyol (A) exceeds 300, the weather resistance, water resistance, solvent resistance, and chemical resistance of the coating film are lowered when a cured coating film is formed.
前記ポリエステルポリオール（Ａ）に結合させるビニル重合体部（Ｂ）は、２個以上の環からなる飽和脂環基を有する(メタ)アクリル酸エステル（ｂ１）と、水酸基含有モノマー（ｂ２）と、必要に応じて、前記（ｂ１）または前記（ｂ２）とラジカル重合可能なその他のモノマー（ｂ３）とからなる単量体成分で構成されていることが好ましい。 The vinyl polymer part (B) to be bonded to the polyester polyol (A) is a (meth) acrylic acid ester (b1) having a saturated alicyclic group composed of two or more rings, a hydroxyl group-containing monomer (b2), As needed, it is preferable to be comprised with the monomer component which consists of said (b1) or said (b2) and the other monomer (b3) which can be radically polymerized.
２個以上の環からなる飽和脂環基を有する(メタ)アクリル酸エステル（ｂ１）としては、多環式、架橋環式、スピロ環式などの各種環状構造、例えば、ビシクロ基、トリシクロ基、テトラシクロ基などを有する(メタ)アクリル酸エステルが挙げられ、特に、ビシクロ基を含有する（メタ）アクリレートが好ましい。ビシクロ基を含有する（メタ）アクリレートとしては、例えば、イソボルニル（メタ）アクリレート、ボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、アダマンチル（メタ）アクリレート、ジメチルアダマンチル（メタ）アクリレート等が挙げられ、これらの中でも、イソボルニル（メタ）アクリレートがより好ましい。なお、(メタ)アクリル酸エステル（ｂ１）は１種のみであってもよいし、２種以上であってもよい。 As the (meth) acrylic acid ester (b1) having a saturated alicyclic group composed of two or more rings, various cyclic structures such as polycyclic, bridged cyclic and spirocyclic, for example, bicyclo group, tricyclo group, Examples include (meth) acrylic acid esters having a tetracyclo group and the like, and (meth) acrylates containing a bicyclo group are particularly preferable. Examples of the (meth) acrylate containing a bicyclo group include isobornyl (meth) acrylate, bornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, and dimethyl. Examples thereof include adamantyl (meth) acrylate, and among these, isobornyl (meth) acrylate is more preferable. In addition, only 1 type may be sufficient as (meth) acrylic acid ester (b1), and 2 or more types may be sufficient as it.
水酸基含有モノマー（ｂ２）としては、例えば、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２，３−ジヒドロキシブチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレートなどの多価アルコールと（メタ）アクリル酸とのモノエステル化物や、当該モノエステル化物にε−カプロラプトンを開環重合させた化合物等が挙げられる。なお、水酸基含有モノマー（ｂ２）は１種のみであってもよいし、２種以上であってもよい。 Examples of the hydroxyl group-containing monomer (b2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and polyethylene. Examples include monoesterified products of polyhydric alcohols such as glycol mono (meth) acrylate and (meth) acrylic acid, and compounds obtained by subjecting the monoesterified product to ring-opening polymerization of ε-caprolapton. In addition, only 1 type may be sufficient as a hydroxyl-containing monomer (b2), and 2 or more types may be sufficient as it.
その他のモノマー（ｂ３）としては、前記（ｂ１）または前記（ｂ２）とラジカル重合可能なものであれば、特に制限はなく、例えば、以下のような種々のモノマー類が挙げられる。その他のモノマー（ｂ３）は１種のみであってもよいし、２種以上であってもよい。
その他のモノマー（ｂ３）の具体例としては、例えば、アクリル酸、メタクリル酸、イタコン酸、フマル酸、マレイン酸のようなα，β−不飽和カルボン酸などのカルボン酸含有モノマー；
Other monomers (b3) are not particularly limited as long as they can be radically polymerized with (b1) or (b2), and examples thereof include the following various monomers. One other monomer (b3) may be used, or two or more monomers may be used.
Specific examples of the other monomer (b3) include carboxylic acid-containing monomers such as α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid;
Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリレート、Ｎ，Ｎ−ジ−ｔ−ブチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノブチル（メタ）アクリレートのようなＮ，Ｎ−ジアルキルアミノアルキル（メタ）アクリレートや、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミドのようなＮ，Ｎ−ジアルキルアミノアルキル（メタ）アクリルアミドなどのアミノ基含有モノマー；
メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレートなどのＣ１〜Ｃ３５の直鎖状、分岐状または環状アルキルの（メタ）アクリレートモノマー；
N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-di-t-butylaminoethyl (meth) acrylate N, N-dialkylaminoalkyl (meth) acrylate such as N, N-dimethylaminobutyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide Amino group-containing monomers such as N, N-dialkylaminoalkyl (meth) acrylamide such as N, N-dimethylaminopropyl (meth) acrylamide;
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2- C1-C35 linear, branched or cyclic alkyl (meth) acrylate monomers such as ethylhexyl (meth) acrylate, n-octyl (meth) acrylate;
グリシジル（メタ）アクリレート、３，４−エポキシシクロヘキシルメチル（メタ）アクリレートなどのエポキシ基含有（メタ）アクリル酸モノマー；
スチレン、α−メチルスチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレン、ビニルトルエンなどの芳香族エチレン性不飽和モノマー；
イタコン酸ベンジルのようなイタコン酸エステル、マレイン酸ジメチルのようなマレイン酸エステル、フマル酸ジメチルのようなフマル酸エステルなどの不飽和カルボン酸エステルモノマー；
アクリロニトリル、メタクリロニトリル、酢酸ビニルなどの重合性モノマー；
Epoxy group-containing (meth) acrylic acid monomers such as glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate;
Aromatic ethylenically unsaturated monomers such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-tert-butylstyrene, vinyltoluene;
Unsaturated carboxylic acid ester monomers such as itaconic acid esters such as benzyl itaconic acid, maleic acid esters such as dimethyl maleate, and fumaric acid esters such as dimethyl fumarate;
Polymerizable monomers such as acrylonitrile, methacrylonitrile, vinyl acetate;
パーフルオロシクロヘキシル（メタ）アクリレート、ジ−パーフルオロシクロヘキシルフマレート、Ｎ−イソプロピルパーフルオロオクタンスルホンアミドエチル（メタ）アクリレートのような（パー）フルオロアルキル基を含有するビニルエステル類、ビニルエーテル類、（メタ）アクリレート類、不飽和ポリカルボン酸エステル類などの含フッ素重合性モノマー；
ビニルエトキシシラン、γ−（メタ）アクリロキシプロピルトリメトキシシラン、γ−（メタ）アクリロキシプロピルトリエトキシシラン、γ−（メタ）アクリロキシプロピルトリプロポキシシラン、γ−（メタ）アクリロキシプロピルメトキシジメトキシシラン、γ−（メタ）アクリロキシプロピルメトキシジエトキシシラン、γ−（メタ）アクリロキシプロピルメトキシジプロポキシシラン、γ−（メタ）アクリロキシブチルフェニルジメトキシシラン、γ−（メタ）アクリロキシブチルフェニルジエトキシシラン、γ−（メタ）アクリロキシブチルフェニルジプロポキシシラン、γ−（メタ）アクリロキシプロピルジメチルメトキシシラン、γ−（メタ）アクリロキシプロピルジメチルエトキシシラン、γ−（メタ）アクリロキシプロピルジメチルエトキシシランなどのシラン系モノマー；
ポリジメチルシロキシプロピル（メタ）アクリレートなどのポリオルガノシロキサン含有ビニルモノマー；等が挙げられる。
また、ビニル重合体部（Ｂ）を構成する単量体成分として、例えば、植物油脂肪酸と、水酸基含有（メタ）アクリル酸モノマーもしくはエポキシ基含有（メタ）アクリル酸モノマーとをエステル化させて得られる脂肪酸（メタ）アクリル酸エステルモノマーなどを用いると、得られるビニル変性ポリエステルポリオール中の植物油由来原料の含有量を増加させることができるので、好ましい。
Vinyl esters, vinyl ethers containing (per) fluoroalkyl groups, such as perfluorocyclohexyl (meth) acrylate, di-perfluorocyclohexyl fumarate, N-isopropylperfluorooctanesulfonamidoethyl (meth) acrylate, (meta ) Fluorine-containing polymerizable monomers such as acrylates and unsaturated polycarboxylic acid esters;
Vinylethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltripropoxysilane, γ- (meth) acryloxypropylmethoxydimethoxy Silane, γ- (meth) acryloxypropylmethoxydiethoxysilane, γ- (meth) acryloxypropylmethoxydipropoxysilane, γ- (meth) acryloxybutylphenyldimethoxysilane, γ- (meth) acryloxybutylphenyldi Ethoxysilane, γ- (meth) acryloxybutylphenyl dipropoxysilane, γ- (meth) acryloxypropyldimethylmethoxysilane, γ- (meth) acryloxypropyldimethylethoxysilane, γ- (meth) acryloxypropyl dimethyl Silane monomers, such as Le ethoxysilane;
And polyorganosiloxane-containing vinyl monomers such as polydimethylsiloxypropyl (meth) acrylate.
Moreover, as a monomer component which comprises a vinyl polymer part (B), it is obtained by esterifying a vegetable oil fatty acid and a hydroxyl-containing (meth) acrylic acid monomer or an epoxy group-containing (meth) acrylic acid monomer, for example. Use of a fatty acid (meth) acrylic acid ester monomer or the like is preferable because the content of the vegetable oil-derived raw material in the obtained vinyl-modified polyester polyol can be increased.
前記ビニル重合体部（Ｂ）を構成する単量体成分（ビニル重合体部構成単量体成分）における各モノマー（前記（ｂ１）、前記（ｂ２）および前記（ｂ３））の含有割合は、特に制限されないが、好ましくは、前記 (メタ)アクリル酸エステル（ｂ１）は５〜８０重量％、前記水酸基含有モノマー（ｂ２）は２〜８０重量％、前記その他のモノマー（ｂ３）は０〜９３重量％であるのがよい。特に、前記 (メタ)アクリル酸エステル（ｂ１）が５重量％未満であると、得られるビニル変性ポリエステルポリオールを二液硬化型塗料組成物として硬化塗膜を形成したとき、塗膜の耐摩耗性が不充分となるおそれがあり、一方、８０重量％を超えても、二液硬化型塗料組成物として硬化塗膜を形成したときに塗膜が硬脆くなり、結果として耐摩耗性が不充分になる傾向がある。 The content ratio of each monomer (the (b1), the (b2) and the (b3)) in the monomer component (vinyl polymer part constituting monomer component) constituting the vinyl polymer part (B) is as follows: Although not particularly limited, preferably, the (meth) acrylic acid ester (b1) is 5 to 80% by weight, the hydroxyl group-containing monomer (b2) is 2 to 80% by weight, and the other monomer (b3) is 0 to 93%. It should be weight percent. In particular, when the (meth) acrylic acid ester (b1) is less than 5% by weight, when a cured coating film is formed using the resulting vinyl-modified polyester polyol as a two-component curable coating composition, the abrasion resistance of the coating film On the other hand, even if it exceeds 80% by weight, when a cured coating film is formed as a two-component curable coating composition, the coating film becomes hard and brittle, resulting in insufficient wear resistance. Tend to be.
前記ポリエステルポリオール（Ａ）に前記ビニル重合体部（Ｂ）を結合させるには、例えば、該ビニル重合体部（Ｂ）を構成する上述した単量体成分を、ポリエステルポリオール（Ａ）の存在下で、従来公知のラジカル重合触媒（アゾ系化合物、パーオキサイド系化合物、スルフィド類、スルフィン類、スルフィン酸類、ジアゾ化合物、レドックス系化合物など）を用いて従来公知のブロック重合法やグラフト重合法等により重合させればよい。 In order to bond the vinyl polymer part (B) to the polyester polyol (A), for example, the above-described monomer component constituting the vinyl polymer part (B) is added in the presence of the polyester polyol (A). With a conventionally known radical polymerization catalyst (azo compound, peroxide compound, sulfide, sulfin, sulfinic acid, diazo compound, redox compound, etc.) by a conventionally known block polymerization method or graft polymerization method, etc. What is necessary is just to superpose | polymerize.
本発明において、前記ビニル重合体部（Ｂ）の水酸基価は１０〜３００であることが重要である。ビニル重合体部（Ｂ）の水酸基価が１０未満であると、得られるビニル変性ポリエステルポリオールを二液硬化型塗料組成物として硬化塗膜を形成したときに、塗膜の架橋密度が低くなり、結果として、耐摩耗性、耐候性、耐水性、耐溶剤性、耐薬品性が不充分になる。一方、ビニル重合体部（Ｂ）の水酸基価が３００を超えると、硬化塗膜を形成したときに、硬化架橋による塗膜収縮が大きくなるため、基材等に対する付着性（密着性）を損なうことがある。
なお、本発明において、ビニル重合体部（Ｂ）の水酸基価は、当該ビニル重合体部（Ｂ）を構成する単量体成分（ビニル重合体部構成単量体成分）の組成に基づき算出される理論計算値である。具体的には、ビニル重合体部（Ｂ）を形成する際に用いるビニル重合体部構成単量体成分の合計重量をＷ（ｇ）とし、該ビニル重合体部構成単量体成分に含まれる水酸基含有モノマー（ｂ２）のモル数をＸとして、式：ビニル重合体部（Ｂ）の水酸基価（ｍｇＫＯＨ／ｇ）＝〔（Ｘ×５６．１（ＫＯＨの分子量））/Ｗ〕×１０００、に基づき算出すればよい。
In the present invention, it is important that the hydroxyl value of the vinyl polymer part (B) is 10 to 300. When the hydroxyl value of the vinyl polymer part (B) is less than 10, when a cured coating film is formed using the resulting vinyl-modified polyester polyol as a two-component curable coating composition, the crosslinking density of the coating film becomes low, As a result, wear resistance, weather resistance, water resistance, solvent resistance, and chemical resistance become insufficient. On the other hand, when the hydroxyl value of the vinyl polymer part (B) exceeds 300, when a cured coating film is formed, the shrinkage of the coating film due to curing crosslinking is increased, so that the adhesion (adhesion) to the substrate or the like is impaired. Sometimes.
In the present invention, the hydroxyl value of the vinyl polymer part (B) is calculated based on the composition of the monomer component (vinyl polymer part constituting monomer component) constituting the vinyl polymer part (B). It is a theoretical calculation value. Specifically, the total weight of the vinyl polymer part constituting monomer component used when forming the vinyl polymer part (B) is W (g), and is included in the vinyl polymer part constituting monomer component. When the number of moles of the hydroxyl group-containing monomer (b2) is X, the formula: hydroxyl value of the vinyl polymer part (B) (mgKOH / g) = [(X × 56.1 (KOH molecular weight)) / W] × 1000, It may be calculated based on
本発明において、前記ビニル重合体部（Ｂ）のガラス転移点（Ｔｇ）が２０〜１５０℃であることが重要である。ビニル重合体部（Ｂ）のガラス転移点が２０℃未満であると、塗膜が柔らかくなり、耐摩耗性が悪くなる。一方、ビニル重合体部（Ｂ）のガラス転移点が１５０℃を超えると、塗膜が硬くなりすぎる結果、硬脆くなり、耐摩耗性が悪くなる。
なお、本発明において、ビニル重合体部（Ｂ）のガラス転移点（Ｔｇ）は、該ビニル重合体部（Ｂ）を構成する各単量体（モノマー）を単独で重合させたときのホモポリマーのＴｇを用いて、下記Ｆｏｘの計算式により算出することができる。
In this invention, it is important that the glass transition point (Tg) of the said vinyl polymer part (B) is 20-150 degreeC. When the glass transition point of the vinyl polymer part (B) is less than 20 ° C., the coating film becomes soft and wear resistance deteriorates. On the other hand, if the glass transition point of the vinyl polymer part (B) exceeds 150 ° C., the coating film becomes too hard, resulting in hard and brittleness and poor wear resistance.
In the present invention, the glass transition point (Tg) of the vinyl polymer part (B) is a homopolymer obtained by polymerizing each monomer (monomer) constituting the vinyl polymer part (B) alone. Can be calculated by the following Fox calculation formula.
Ｔｇｉ：ビニル重合体部を構成する各単量体のホモポリマーのＴｇ（Ｋ）
Ｗｉ ：ビニル重合体部を構成する各単量体の重量分率
Tgi: Tg (K) of homopolymer of each monomer constituting the vinyl polymer part
Wi: Weight fraction of each monomer constituting the vinyl polymer part
本発明のビニル変性ポリエステルポリオールにおいて、前記ポリエステルポリオール（Ａ）と前記ビニル重合体部（Ｂ）との構成比率は、重量比で、（Ａ）：（Ｂ）＝２０：８０〜８０：２０であることが重要であり、４０：６０〜６０：４０であることがより好ましい。ポリエステルポリオール（Ａ）の比率が前記範囲よりも少ない場合、カーボンニュートラルな材料を利用することにより得られる地球温暖化防止効果が小さくなる。一方、ポリエステルポリオール（Ａ）の比率が前記範囲よりも多い場合には、得られるビニル変性ポリエステルポリオールを二液硬化型塗料組成物として硬化塗膜を形成したときに、塗膜の耐摩耗性、耐候性、耐水性、耐溶剤性、耐薬品性が不充分になる。 In the vinyl-modified polyester polyol of the present invention, the composition ratio between the polyester polyol (A) and the vinyl polymer part (B) is a weight ratio of (A) :( B) = 20: 80 to 80:20. It is important that it is 40:60 to 60:40. When the ratio of the polyester polyol (A) is less than the above range, the effect of preventing global warming obtained by using a carbon neutral material is reduced. On the other hand, when the ratio of the polyester polyol (A) is larger than the above range, when a cured coating film is formed using the resulting vinyl-modified polyester polyol as a two-component curable coating composition, the abrasion resistance of the coating film, The weather resistance, water resistance, solvent resistance, and chemical resistance are insufficient.
本発明のビニル変性ポリエステルポリオールにおいて、このビニル変性ポリエステルポリオールに含まれる植物油由来原料の含有量は、ビニル変性ポリエステルポリオール中の不揮発分に対して２０〜８０重量％であることが好ましい。植物油由来原料の含有量が、前記範囲よりも少ないと、カーボンニュートラルな材料としての有用性が低くなり、一方、前記範囲よりも多いと、耐候性や耐摩耗性が悪くなる傾向がある。 In the vinyl-modified polyester polyol of the present invention, the content of the vegetable oil-derived raw material contained in the vinyl-modified polyester polyol is preferably 20 to 80% by weight based on the nonvolatile content in the vinyl-modified polyester polyol. When the content of the vegetable oil-derived raw material is less than the above range, the usefulness as a carbon neutral material is lowered. On the other hand, when the content is more than the above range, weather resistance and wear resistance tend to be deteriorated.
本発明のビニル変性ポリエステルポリオールの水酸基価は３０〜３００であることが好ましい。ビニル変性ポリエステルポリオールの水酸基価が３０未満であると、二液硬化型塗料組成物として硬化塗膜を形成したときに、塗膜の架橋密度が低くなり、結果として、耐摩耗性、耐候性、耐水性、耐溶剤性、耐薬品性が不充分になるおそれがある。一方、ビニル変性ポリエステルポリオールの水酸基価が３００を超えると、硬化塗膜を形成したときに、硬化架橋による塗膜収縮が大きくなるため、基材等に対する付着性（密着性）を損なうおそれがある。 The hydroxyl value of the vinyl-modified polyester polyol of the present invention is preferably 30 to 300. When the hydroxyl value of the vinyl-modified polyester polyol is less than 30, when a cured coating film is formed as a two-component curable coating composition, the crosslinking density of the coating film is lowered, resulting in wear resistance, weather resistance, Water resistance, solvent resistance, and chemical resistance may be insufficient. On the other hand, when the hydroxyl value of the vinyl-modified polyester polyol exceeds 300, when a cured coating film is formed, the coating film shrinkage due to curing cross-linking increases, which may impair the adhesion (adhesiveness) to the substrate or the like. .
本発明のビニル変性ポリエステルポリオールの重量平均分子量は５，０００〜５００，０００であることが好ましい。ビニル変性ポリエステルポリオールの重量平均分子量が５，０００未満であると、二液硬化型塗料組成物として硬化塗膜を形成したときに、塗膜の耐摩耗性、耐候性、耐水性、耐溶剤性、耐薬品性が不充分になるおそれがある。一方、ビニル変性ポリエステルポリオールの重量平均分子量が５００，０００を超えると、粘度が高くなり、塗料として用いる際の扱いが困難になる傾向がある。 The weight average molecular weight of the vinyl-modified polyester polyol of the present invention is preferably 5,000 to 500,000. When the weight average molecular weight of the vinyl-modified polyester polyol is less than 5,000, when a cured coating film is formed as a two-component curable coating composition, the abrasion resistance, weather resistance, water resistance, and solvent resistance of the coating film are increased. The chemical resistance may be insufficient. On the other hand, when the weight average molecular weight of the vinyl-modified polyester polyol exceeds 500,000, the viscosity tends to be high and the handling when used as a paint tends to be difficult.
本発明の二液硬化型塗料組成物（以下、単に「塗料組成物」と称することもある）は、上述した本発明のビニル変性ポリエステルポリオールを含むポリオール成分と、イソシアネート化合物を含むポリイソシアネート成分とからなる。これらポリオール成分とポリイソシアネート成分とは、使用時（硬化物形成時）には混合して用いられるが、通常、使用直前までは混合せずに別々に保管される。 The two-component curable coating composition of the present invention (hereinafter sometimes simply referred to as “coating composition”) includes a polyol component containing the above-described vinyl-modified polyester polyol of the present invention, a polyisocyanate component containing an isocyanate compound, and Consists of. These polyol component and polyisocyanate component are mixed and used at the time of use (at the time of forming a cured product), but are usually stored separately without being mixed until just before use.
ポリイソシアネート成分に含まれるイソシアネート化合物としては、例えば、芳香族系ポリイソシアネート、脂肪族系ポリイソシアネート、環式脂肪族系ポリイソシアネート、脂環式ポリイソシアネート、またはこれらポリイソシアネートとポリオールとの反応生成物等が挙げられる。これらの中でも、トリレンジイソシアネート（ＴＤＩ）、ジフェニルメタンジイソシアネート（ＭＤＩ）、ポリフェニルメタンポリイソシアネート（クルードＭＤＩ）、変性ジフェニルメタンジイソシアネート（変性ＭＤＩ）、キシリレンジイソシアネート（ＸＤＩ）、ヘキサメチレンジイソシアネート（ＨＭＤＩ）などの芳香族系ポリイソシアネートあるいはこれらポリイソシアネートの三量体化合物や、これらポリイソシアネートとポリオールとの反応生成物等が好ましい。ポリイソシアネート成分は、１種のみであってもよいし、２種以上であってもよい。 Examples of the isocyanate compound contained in the polyisocyanate component include aromatic polyisocyanates, aliphatic polyisocyanates, cycloaliphatic polyisocyanates, alicyclic polyisocyanates, or reaction products of these polyisocyanates and polyols. Etc. Among these, such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polyphenylmethane polyisocyanate (crude MDI), modified diphenylmethane diisocyanate (modified MDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), etc. Aromatic polyisocyanates or trimer compounds of these polyisocyanates, reaction products of these polyisocyanates and polyols, and the like are preferable. Only one type of polyisocyanate component may be used, or two or more types may be used.
ポリオール成分とポリイソシアネート成分との配合割合は、ポリオール成分中の水酸基当量数とポリイソシアネート成分中のイソシアネート当量数の比（ポリオール成分の水酸基当量数：ポリイソシアネート成分のイソシアネート当量数）が１００：５０〜１００：２００の範囲になるように設定するのが好ましく、より好ましくは、１００：８０〜１００：１８０の範囲になるように設定するのがよい。ポリオール成分中の水酸基当量数を１００としたときに、ポリイソシアネート成分中のイソシアネートの当量数が５０未満であると、ポリオール成分とポリイソシネート成分との架橋反応が不充分となって、塗膜の速硬化性が低下したり、耐摩耗性、硬度、耐候性、耐水性、耐溶剤性、耐薬品性等の塗膜物性が低下したりするおそれがある。一方、ポリオール成分中の水酸基当量数を１００としたときに、ポリイソシアネート成分中のイソシアネートの当量数が２００を超えると、余剰のポリイソシアネートが存在することにより物性が低下するおそれがある。 The mixing ratio of the polyol component and the polyisocyanate component is such that the ratio of the number of hydroxyl equivalents in the polyol component to the number of isocyanate equivalents in the polyisocyanate component (number of hydroxyl equivalents in the polyol component: number of isocyanate equivalents in the polyisocyanate component) is 100: 50. It is preferable to set to be in a range of ˜100: 200, and more preferably to be in a range of 100: 80 to 100: 180. When the number of hydroxyl equivalents in the polyol component is 100 and the number of equivalents of isocyanate in the polyisocyanate component is less than 50, the crosslinking reaction between the polyol component and the polyisocyanate component is insufficient, and the coating speed is increased. There is a possibility that the curability is lowered and the physical properties of the coating film such as wear resistance, hardness, weather resistance, water resistance, solvent resistance, chemical resistance and the like are lowered. On the other hand, when the number of hydroxyl equivalents in the polyol component is 100 and the number of equivalents of isocyanate in the polyisocyanate component exceeds 200, the physical properties may be deteriorated due to the presence of excess polyisocyanate.
本発明の塗料組成物（ポリオール成分および／またはポリイソシアネート成分）は、それぞれ、前記ビニル変性ポリエステルポリオールや前記イソシアネート化合物を溶解もしくは分散させるための溶剤を適宜含有していてもよい。溶剤は、ポリオール成分とポリイソシアネート成分のいずれか一方に含有させてもよいし、両方に含有させてもよい。また、溶剤を、ポリオール成分とポリイソシアネート成分とを混合した後に適当な粘度になるよう希釈する目的で用いることもできる。
溶剤としては、例えば、トルエン、キシレン、ソルベントナフサ、メチルシクロヘキサン、エチルシクロヘキサンなどの炭化水素系溶剤；酢酸エチル、酢酸ブチル、酢酸エチレングリコールモノメチルエーテルなどのエステル系溶剤；アセトン、メチルエチルケトン、メチルイソブチルケトン、ジイソブチルケトンなどのケトン系溶剤；等が挙げられる。溶剤は、１種のみであってもよいし、２種以上であってもよい。また、ポリオール成分に用いる溶剤とポリイソシアネート成分に用いる溶剤は、同じであってもよいし、異なっていてもよい。
The coating composition (polyol component and / or polyisocyanate component) of the present invention may appropriately contain a solvent for dissolving or dispersing the vinyl-modified polyester polyol and the isocyanate compound, respectively. The solvent may be contained in one or both of the polyol component and the polyisocyanate component. Moreover, a solvent can also be used in order to dilute so that it may become a suitable viscosity after mixing a polyol component and a polyisocyanate component.
Examples of the solvent include hydrocarbon solvents such as toluene, xylene, solvent naphtha, methylcyclohexane, and ethylcyclohexane; ester solvents such as ethyl acetate, butyl acetate, and ethylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, And ketone solvents such as diisobutyl ketone. One type of solvent may be sufficient and 2 or more types may be sufficient as it. Moreover, the solvent used for a polyol component and the solvent used for a polyisocyanate component may be the same, and may differ.
本発明の塗料組成物には、必要に応じて、天然色素、有機合成色素、顔料、無機顔料または光輝材（塗膜にキラキラとした光輝感または光干渉性を付与するりん片状顔料）等の着色成分を含有させることができる。これら着色成分は、ポリオール成分とポリイソシアネート成分のどちらに含有させてもよいが、ポリオール成分に含有させるのが好ましい。着色成分は、１種のみであってもよいし、２種以上であってもよい。なお、本発明の塗料組成物は、着色成分を含有しないクリヤー塗料であってもよいことは言うまでもない。 In the coating composition of the present invention, natural pigments, organic synthetic pigments, pigments, inorganic pigments or glittering materials (flaky pigments that impart a glittering sensation or optical interference to the coating film), etc., as necessary The coloring component can be contained. These coloring components may be contained in either the polyol component or the polyisocyanate component, but are preferably contained in the polyol component. Only one color component may be used, or two or more color components may be used. Needless to say, the coating composition of the present invention may be a clear coating containing no coloring component.
天然色素としては、例えば、カロチン、カロチナール、カプサンチン、リコピン、ビキシン、クロシン、カンタキサンチン、アナトーなどのカロチノイド系色素；シソニン、ラファニン、エノシアニンのようなアントシアニジン類、サフロールイエロー、ベニバナのようなカルコン類、ルチン、クエルセチンのようなフラボノール類、カカオ色素のようなフラボン類などのフラボノイド系色素；、リボフラビンなどのフラビン系色素；ラッカイン酸、カルミン酸（コチニール）、ケルメス酸、アリザリンのようなアントラキノン類、シコニン、アルカニン、エキノクロームのようなナフトキノン類などのキノン系色素；クロロフィル、血色素などのポリフィリン系色素；クルクミン（ターメリック）などのジケトン系色素；ベタニンなどのベタシアニジン系色素；等が挙げられる。 Examples of natural pigments include carotenoid pigments such as carotene, carotenal, capsanthin, lycopene, bixin, crocin, canthaxanthin and anato; anthocyanidins such as shisonin, raphanin and enocyanin, chalcones such as safrole yellow and safflower, Flavonols such as rutin and quercetin, flavonoids such as flavones such as cacao pigments, flavin pigments such as riboflavin; anthraquinones such as lacaic acid, carminic acid (cochineal), kermesic acid, alizarin, shikonin Quinone dyes such as naphthoquinones such as alkanin and echinochrome; polyphyrin dyes such as chlorophyll and hemoglobin; diketone dyes such as curcumin (turmeric); Cyanidin-based pigments; and the like.
有機合成色素または顔料としては、厚生省令第３０号で定められているものが挙げられる。例えば、赤色２０２号（リソールルビンＢＣＡ）、赤色２０３号（レーキレッドＣ）、赤色２０４号（レーキレッドＣＢＡ）、赤色２０５号（リソールレッド）、赤色２０６号（リソールレッドＣＡ）、赤色２０７号（リソールレッドＢＡ）、赤色２０８号（リソールレッドＳＲ）、赤色２１９号（ブリリアントレーキレッドＲ）、赤色２２０号（ディープマルーン）、赤色２２１号（トルイジンレッド）、赤色２２８号（パーマトンレッド）、だいだい色２０３号（パーマネントオレンジ）、だいだい色２０４号（ベンチジンオレンジＧ）、黄色２０５（ベンチジンエローＧ）、赤色４０４号（ブリリアントファストスカーレット）、赤色４０５号（パーマネントレッドＦ５Ｒ）、だいだい色４０１号（ハンザオレンジ）、黄色４０１号（ハンザエロー）、青色４０４号（フタロシアニンブルー）等が挙げられる。 Examples of the organic synthetic dye or pigment include those defined in Ordinance No. 30 of the Ministry of Health and Welfare. For example, Red 202 (Risor Rubin BCA), Red 203 (Rake Red C), Red 204 (Rake Red CBA), Red 205 (Risor Red), Red 206 (Risor Red CA), Red 207 (Risole) Red BA), Red 208 (Risor Red SR), Red 219 (Brilliant Lake Red R), Red 220 (Deep Maroon), Red 221 (Toluidine Red), Red 228 (Parmaton Red), orange No. 203 (Permanent Orange), Orange No. 204 (Bench Gin Orange G), Yellow 205 (Bench Gin Yellow G), Red No. 404 (Brilliant Fast Scarlet), Red No. 405 (Permanent Red F5R), Orange No. 401 ( Hansa Orange), Yellow No. 401 ( Nzaero), Blue No. 404 (phthalocyanine blue), and the like.
無機顔料としては、例えば、無水ケイ酸、ケイ酸マグネシウム、タルク、カオリン、ベントナイト、酸化ジルコニウム、酸化マグネシウム、酸化亜鉛、酸化チタン、軽質炭酸カルシウム、重質炭酸カルシウム、軽質炭酸マグネシウム、重質炭酸マグネシウム、硫酸バリウム、黄酸化鉄、ベンガラ、黒酸化鉄、グンジョウ、酸化クロム、水酸化クロム、カーボンブラック、カラミン等が挙げられる。
光輝材としては、例えば、りん片状のアルミニウム、蒸着アルミニウム、酸化アルミニウム、塩化オキシビスマス、雲母、酸化チタン被覆雲母、酸化鉄被覆雲母、雲母状酸化鉄、酸化チタン被覆シリカ、酸化チタン被覆アルミナ、酸化鉄被覆シリカ、酸化鉄被覆アルミナ、ガラスフレーク、着色ガラスフレーク、蒸着ガラスフレーク、ホログラムフィルム等が挙げられる。これら光輝材の大きさは、特に制限されないが、長手方向が１〜３０μｍ、厚さが０．００１〜１μｍであるのが好ましい。
Examples of inorganic pigments include silicic anhydride, magnesium silicate, talc, kaolin, bentonite, zirconium oxide, magnesium oxide, zinc oxide, titanium oxide, light calcium carbonate, heavy calcium carbonate, light magnesium carbonate, and heavy magnesium carbonate. , Barium sulfate, yellow iron oxide, bengara, black iron oxide, gunjou, chromium oxide, chromium hydroxide, carbon black, calamine and the like.
Examples of the bright material include flaky aluminum, vapor-deposited aluminum, aluminum oxide, oxybismuth chloride, mica, titanium oxide-coated mica, iron oxide-coated mica, mica-like iron oxide, titanium oxide-coated silica, and titanium oxide-coated alumina. Examples thereof include iron oxide-coated silica, iron oxide-coated alumina, glass flakes, colored glass flakes, vapor-deposited glass flakes, and hologram films. The size of these glitter materials is not particularly limited, but it is preferable that the longitudinal direction is 1 to 30 μm and the thickness is 0.001 to 1 μm.
本発明の塗料組成物には、本発明の効果を損なわない範囲で、必要に応じて、その他の天然物由来樹脂が含有されていてもよい。その場合、その他の天然物由来樹脂は、ポリオール成分とポリイソシアネート成分のどちらに含有させてもよいが、ポリオール成分に含有させるのが好ましい。その他の天然物由来樹脂は、１種のみであってもよいし、２種以上であってもよい。 The coating composition of the present invention may contain other natural product-derived resins as necessary within the range not impairing the effects of the present invention. In that case, the other natural product-derived resin may be contained in either the polyol component or the polyisocyanate component, but is preferably contained in the polyol component. One type of other natural product-derived resins may be used, or two or more types may be used.
その他の天然物由来樹脂としては、特に制限されないが、例えば、植物性繊維、セルロース樹脂、ポリ乳酸に代表されるポリヒドロキシカルボン酸、ポリカプロラクタム、変性ポリビニルアルコールなどのほか、ポリカプロラクトンに代表される生分解性脂肪族ポリエステル等が挙げられる。その他の天然物由来樹脂としては、特に、上述した溶剤に可溶であるものが好ましく、なかでもセルロース由来の樹脂が好適である。例えば、セロース、ニトロセルロース、およびセルロースアセテートブチレートから選ばれる１種以上を少量含有させることにより、得られる硬化塗膜の表面硬度等の物性をより向上させることができる。その他の天然物由来樹脂として用いることのできる好ましい市販品としては、ニトロセルロースでは、仏国ベルジュラックＮＣ社製の工業用硝化綿「ＢＮＣ−ＨＩＧ−２」、韓国ＣＮＣ社製の工業用硝化綿「ＲＳ１−４」、（株）協鮮洋行製の「スワンセルＨＭ１−４」、旭化成ケミカルズ（株）製の「セルノバＢＴＨ１−４」）等が挙げられ、セルロースアセテートブチレートでは、米国イーストマンケミカルプロダクツ社製の「ＣＡＢ３８１−０．１」、「ＣＡＢ３８１−０．５」、「ＣＡＢ３８１−２」、「ＣＡＢ５３１−１」、「ＣＡＢ５５１−０．０１」、「ＣＡＢ５５１−０．２」等が挙げられる。 Other natural product-derived resins are not particularly limited, but include, for example, plant fibers, cellulose resins, polyhydroxycarboxylic acids typified by polylactic acid, polycaprolactam, modified polyvinyl alcohol, and the like, as well as typified by polycaprolactone. Examples include biodegradable aliphatic polyester. As other natural product-derived resins, those that are soluble in the above-mentioned solvents are particularly preferable, and cellulose-derived resins are particularly preferable. For example, physical properties such as surface hardness of the obtained cured coating film can be further improved by containing a small amount of one or more selected from cellulose, nitrocellulose, and cellulose acetate butyrate. Examples of other commercially available products that can be used as other natural product-derived resins include nitrocellulose, industrial nitrified cotton “BNC-HIG-2” manufactured by Bergerac NC, France, and industrial nitrified cotton manufactured by Korea CNC. “RS1-4”, “Swancell HM1-4” manufactured by Kyosei Yoko Co., Ltd., “Sellnova BTH1-4” manufactured by Asahi Kasei Chemicals Co., Ltd.) and the like. “CAB381-0.1”, “CAB381-0.5”, “CAB381-2”, “CAB531-1”, “CAB551-0.01”, “CAB551-0.2”, etc., manufactured by Products It is done.
本発明の塗料組成物には、本発明の効果を損なわない範囲で、必要に応じて、従来公知の表面調整剤（ワックス、ハジキ防止剤、消泡剤など）、可塑剤、紫外線安定剤、酸化防止剤、流動性調整剤、垂れ止め剤、つや消し剤、艶出し剤、防腐剤等の各種添加物を適宜含有させることができる。これら添加物は、ポリオール成分とポリイソシアネート成分のどちらに含有させてもよいが、ポリオール成分に含有させるのが好ましい。 In the coating composition of the present invention, as long as the effects of the present invention are not impaired, a conventionally known surface conditioner (wax, repellency inhibitor, antifoaming agent, etc.), plasticizer, UV stabilizer, Various additives such as an antioxidant, a fluidity modifier, a sag-preventing agent, a matting agent, a polishing agent, and a preservative can be appropriately contained. These additives may be contained in either the polyol component or the polyisocyanate component, but are preferably contained in the polyol component.
本発明の硬化物は、上述したビニル変性ポリエステルポリオールをイソシアネート化合物で硬化させてなるものであり、このような硬化物は、例えば、上述した本発明の塗料組成物（ポリオール成分およびポリイソシアネート成分）を混合し、基材に塗装することにより作製することができる。
本発明の塗料組成物を塗装（印刷も含む）する際には、従来公知の方法を採用すればよく、例えば、ハケ、スプレー、ロールコーター、浸漬、スクリーン印刷などの手段を用いて、塗布量が乾燥膜厚で平均１〜２００μｍ、好ましくは２〜１００μｍの範囲内になるように塗装することができる。また、本発明の塗料組成物を塗装（印刷も含む）する基材としては、特に制限はないが、例えば、木材、プラスチック、コンクリート、ガラス、金属などが挙げられる。
The cured product of the present invention is obtained by curing the above-mentioned vinyl-modified polyester polyol with an isocyanate compound. Such a cured product is, for example, the above-described coating composition of the present invention (polyol component and polyisocyanate component). It can be produced by mixing and coating on a substrate.
When applying (including printing) the coating composition of the present invention, a conventionally known method may be employed. For example, using a means such as brush, spray, roll coater, dipping, or screen printing, the coating amount Can be applied so that the average thickness is 1 to 200 μm, preferably 2 to 100 μm. In addition, the substrate on which the coating composition of the present invention is applied (including printing) is not particularly limited, and examples thereof include wood, plastic, concrete, glass, and metal.
以下、実施例により本発明をより詳細に説明するが、本発明は、かかる実施例により限定されるものではない。
なお、実施例および比較例における各種物性の測定は、以下の方法で行なった。
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by this Example.
The various physical properties in Examples and Comparative Examples were measured by the following methods.
＜粘度＞
ガードナー気泡粘度計を用いて、ＪＩＳ−Ｋ５６００に準じて測定した。
＜酸価（ｍｇＫＯＨ／ｇ）＞
ＪＩＳ−Ｋ５６０１に準じて測定した。
＜水酸基価（ｍｇＫＯＨ／ｇ）＞
ＪＩＳ−Ｋ００７０に準じて測定した。ただし、ビニル重合体部（Ｂ）の水酸基価については、当該ビニル重合体部（Ｂ）を構成する単量体成分（ビニル重合体部構成単量体成分）の組成に基づき算出した。
＜色数（ヘリーゲ）＞
ヘリーゲ比色計を用いて測定した。
＜重量平均分子量＞
ゲルパーミエーションクロマトグラフィーにて測定した。
＜不揮発分（％）＞
ＪＩＳ−Ｋ５６０１に準じて測定した。
<Viscosity>
It measured according to JIS-K5600 using a Gardner bubble viscometer.
<Acid value (mgKOH / g)>
It measured according to JIS-K5601.
<Hydroxyl value (mgKOH / g)>
It measured according to JIS-K0070. However, the hydroxyl value of the vinyl polymer part (B) was calculated based on the composition of the monomer component (vinyl polymer part constituting monomer component) constituting the vinyl polymer part (B).
<Number of colors (Heligue)>
Measured using a Helige colorimeter.
<Weight average molecular weight>
Measured by gel permeation chromatography.
<Non-volatile content (%)>
It measured according to JIS-K5601.
（製造例１−植物油由来原料使用ポリエステルポリオール（Ａ）の合成）
反応器中に、ひまし油脂肪酸（植物油由来原料）７００重量部と、安息香酸２３重量部と、無水フタル酸６２重量部と、セバシン酸（植物油由来原料）８０重量部と、ペンタエリスリトール１３５重量部と、還流溶剤としてキシレン３０重量部とを仕込み、２４０℃まで昇温し、酸価が５以下になった時点で減圧を開始してキシレンを留去させ、その後、冷却することによって、ポリエステルポリオール（Ａ−１）を得た。このポリエステルポリオールの各種物性（粘度、酸価、水酸基価、色数（ヘリーゲ））は表１に示す通りであった。
(Production Example 1-Synthesis of polyester polyol (A) using raw material derived from vegetable oil)
In the reactor, 700 parts by weight of castor oil fatty acid (raw material derived from vegetable oil), 23 parts by weight of benzoic acid, 62 parts by weight of phthalic anhydride, 80 parts by weight of sebacic acid (raw material from vegetable oil), 135 parts by weight of pentaerythritol, Then, 30 parts by weight of xylene was charged as a refluxing solvent, the temperature was raised to 240 ° C., and when the acid value became 5 or less, pressure reduction was started to distill off xylene, and then the polyester polyol ( A-1) was obtained. Various physical properties (viscosity, acid value, hydroxyl value, number of colors (helige)) of this polyester polyol were as shown in Table 1.
（製造例２−植物油由来原料使用ポリエステルポリオール（Ａ）の合成）
反応器中に、ひまし油脂肪酸（植物油由来原料）５００重量部と、セバシン酸（植物油由来原料）２８９重量部と、１，１０−デカンジオール（植物油由来原料）１２１重量部と、グリセリン（植物油由来原料）９０重量部と、還流溶剤としてキシレン３０重量部とを仕込み、２４０℃まで昇温し、酸価が５以下になった時点で減圧を開始してキシレンを留去させ、その後、冷却することによって、ポリエステルポリオール（Ａ−２）を得た。このポリエステルポリオールの各種物性（粘度、酸価、水酸基価、色数（ヘリーゲ））は表１に示す通りであった。
(Production Example 2-Synthesis of Polyester Polyol (A) Using Vegetable Oil-derived Raw Material)
In the reactor, castor oil fatty acid (vegetable oil-derived raw material) 500 parts by weight, sebacic acid (vegetable oil-derived raw material) 289 parts by weight, 1,10-decanediol (vegetable oil-derived raw material) 121 parts by weight, and glycerin (vegetable oil-derived raw material) ) Charge 90 parts by weight and 30 parts by weight of xylene as a refluxing solvent, raise the temperature to 240 ° C., start depressurization when the acid value becomes 5 or less, distill off xylene, and then cool. To obtain a polyester polyol (A-2). Various physical properties (viscosity, acid value, hydroxyl value, number of colors (helige)) of this polyester polyol were as shown in Table 1.
（製造例３−植物油由来原料使用ポリエステルポリオール（Ａ）の合成）
反応器中に、トール油脂肪酸（植物油由来原料）７００重量部と、安息香酸１２重量部と、無水フタル酸２２重量部と、セバシン酸（植物油由来原料）８０重量部と、ペンタエリスリトール１８６重量部と、還流溶剤としてキシレン３０重量部とを仕込み、２４０℃まで昇温し、酸価が５以下になった時点で減圧を開始してキシレンを留去させ、その後、冷却することによって、ポリエステルポリオール（Ａ−３）を得た。このポリエステルポリオールの各種物性（粘度、酸価、水酸基価、色数（ヘリーゲ））は表１に示す通りであった。
(Production Example 3-Synthesis of Polyester Polyol (A) Using Vegetable Oil Derived Raw Material)
In the reactor, 700 parts by weight of tall oil fatty acid (vegetable oil-derived raw material), 12 parts by weight of benzoic acid, 22 parts by weight of phthalic anhydride, 80 parts by weight of sebacic acid (raw material of vegetable oil), and 186 parts by weight of pentaerythritol And 30 parts by weight of xylene as a refluxing solvent, heated to 240 ° C., when the acid value became 5 or less, pressure reduction was started to distill off xylene, and then the polyester polyol was cooled. (A-3) was obtained. Various physical properties (viscosity, acid value, hydroxyl value, number of colors (helige)) of this polyester polyol were as shown in Table 1.
（製造例４−植物油由来原料使用ポリエステルポリオール（Ａ）の合成）
反応器中に、トール油脂肪酸（植物油由来原料）７００重量部と、安息香酸２０重量部と、無水フタル酸４１重量部と、セバシン酸（植物油由来原料）８０重量部と、ペンタエリスリトール１５９重量部と、還流溶剤としてキシレン３０重量部とを仕込み、２４０℃まで昇温し、酸価が５以下になった時点で減圧を開始してキシレンを留去させ、その後、冷却することによって、ポリエステルポリオール（Ａ−４）を得た。このポリエステルポリオールの各種物性（粘度、酸価、水酸基価、色数（ヘリーゲ））は表１に示す通りであった。
(Production Example 4-Synthesis of Polyester Polyol (A) Using Vegetable Oil-derived Raw Material)
In the reactor, 700 parts by weight of tall oil fatty acid (raw material derived from vegetable oil), 20 parts by weight of benzoic acid, 41 parts by weight of phthalic anhydride, 80 parts by weight of sebacic acid (raw material from vegetable oil), and 159 parts by weight of pentaerythritol And 30 parts by weight of xylene as a refluxing solvent, heated to 240 ° C., when the acid value became 5 or less, pressure reduction was started to distill off xylene, and then the polyester polyol was cooled. (A-4) was obtained. Various physical properties (viscosity, acid value, hydroxyl value, number of colors (helige)) of this polyester polyol were as shown in Table 1.
（製造例５−植物油由来原料使用ポリエステルポリオール（Ａ）の合成）
反応器中に、トール油脂肪酸（植物油由来原料）６７０重量部と、無水フタル酸９６重量部と、グリセリン（植物油由来原料）１１０重量部と、ペンタエリスリトール１２４重量部と、還流溶剤としてキシレン３０重量部とを仕込み、２４０℃まで昇温し、酸価が５以下になった時点で減圧を開始してキシレンを留去させ、その後、冷却することによって、ポリエステルポリオール（Ａ−５）を得た。このポリエステルポリオールの各種物性（粘度、酸価、水酸基価、色数（ヘリーゲ））は表１に示す通りであった。
(Production Example 5-Synthesis of Polyester Polyol (A) Using Raw Material Derived from Vegetable Oil)
In the reactor, tall oil fatty acid (vegetable oil-derived raw material) 670 parts by weight, phthalic anhydride 96 parts by weight, glycerin (vegetable oil-derived raw material) 110 parts by weight, pentaerythritol 124 parts by weight, and xylene as a refluxing solvent 30 parts by weight The polyester polyol (A-5) was obtained by heating up to 240 ° C. and starting pressure reduction when the acid value became 5 or less to distill off xylene and then cooling. . Various physical properties (viscosity, acid value, hydroxyl value, number of colors (helige)) of this polyester polyol were as shown in Table 1.
（実施例１〜５および比較例１〜５）
反応器中に、上記各製造例で得られた植物油由来原料使用ポリエステルポリオール（Ａ−１）〜（Ａ−５）のうち表２または表３に示すものと、酢酸ブチルとを仕込み、１２０℃まで昇温した。この反応器の中に、イソボルニルメタクリレート、２−ヒドロキシエチルアクリレート、ノルマルブチルアクリレートおよびメチルメタクリレートが各々表２または表３に示す比率で混合されてなるビニル重合体部（Ｂ）構成単量体成分とｔ−ブチルパーオキシベンゾエートとを予め混合した混合物を、３時間かけて均一に滴下し、その後、さらに３時間重合反応を行うことによって、ビニル変性ポリエステルポリオールを得た。
なお、各成分の使用量は、ポリエステルポリオール（Ａ）とビニル重合体部（Ｂ）構成単量体成分との合計量を６００重量部とし、これを両者の比率（すなわち、ポリエステルポリオール（Ａ）／ビニル重合体部（Ｂ）の構成比率）が表２または表３に示す割合になるように使用するとともに、酢酸ブチルは４００重量部、ｔ−ブチルパーオキシベンゾエートは３．６重量部とした。
得られたビニル変性ポリエステルポリオールの各種物性（粘度、酸価、水酸基価、色数（ヘリーゲ）、重量平均分子量）は表２および表３に示す通りであった。なお、得られたビニル変性ポリエステルポリオールの不揮発分は、いずれも６０重量％であった。
(Examples 1-5 and Comparative Examples 1-5)
In the reactor, among the plant oil-derived raw material-use polyester polyols (A-1) to (A-5) obtained in the above production examples, those shown in Table 2 or Table 3 and butyl acetate were charged, and 120 ° C. The temperature was raised to. Monomer polymer part (B) constituent monomer in which isobornyl methacrylate, 2-hydroxyethyl acrylate, normal butyl acrylate and methyl methacrylate are mixed in this reactor in the ratios shown in Table 2 or Table 3, respectively. A mixture in which the component and t-butyl peroxybenzoate were mixed in advance was dropped uniformly over 3 hours, and then a polymerization reaction was further performed for 3 hours to obtain a vinyl-modified polyester polyol.
In addition, the usage-amount of each component makes 600 weight part the total amount of polyester polyol (A) and a vinyl polymer part (B) constituent monomer component, and makes this ratio (namely, polyester polyol (A)). / Constitution ratio of vinyl polymer part (B)) is used so that the ratio is as shown in Table 2 or Table 3, 400 parts by weight of butyl acetate and 3.6 parts by weight of t-butyl peroxybenzoate. .
Various physical properties (viscosity, acid value, hydroxyl value, color number (Heligue), weight average molecular weight) of the obtained vinyl-modified polyester polyol were as shown in Tables 2 and 3. The nonvolatile content of the obtained vinyl-modified polyester polyol was 60% by weight.
次に、各実施例および比較例で得られたビニル変性ポリエステルポリオールをそれぞれ用い、二液硬化型塗料組成物を作製した。
すなわち、ビニル変性ポリエステルポリオール（不揮発分６０重量％）が７０重量％、顔料（チタン白）が１８重量％、酢酸ブチルが１２重量％となるように配合し、サンドミルで分散させて、不揮発分が６０重量％、ＰＷＣ（全固形分に対する顔料の比率）が３０重量％のポリオール成分を得た。このポリオール成分に対し、ポリイソシアネート成分としてヘキサメチレンジイソシアネートポリイソシアヌレート系硬化剤（旭化成工業（株）製「デュラネートＴＰＡ−１００」）を、ポリオール成分の水酸基当量数：ポリイソシアネート成分のイソシアネート当量数＝１００：１００となるように組合わせて、二液硬化型塗料組成物とした。
Next, a two-component curable coating composition was prepared using each of the vinyl-modified polyester polyols obtained in each Example and Comparative Example.
That is, a vinyl-modified polyester polyol (non-volatile content 60% by weight) is 70% by weight, a pigment (titanium white) is 18% by weight, and butyl acetate is 12% by weight. A polyol component having 60% by weight and 30% by weight of PWC (ratio of pigment to the total solid content) was obtained. For this polyol component, hexamethylene diisocyanate polyisocyanurate curing agent (“Duranate TPA-100” manufactured by Asahi Kasei Kogyo Co., Ltd.) as the polyisocyanate component, the number of hydroxyl equivalents of the polyol component: the number of isocyanate equivalents of the polyisocyanate component = A two-component curable coating composition was obtained by combining the components so as to be 100: 100.
上記で得られた二液硬化型塗料組成物を用いて硬化塗膜を作製し、その性能を以下の各試験により評価した。硬化塗膜は、二液硬化型塗料組成物の２液（ポリオール成分およびポリイソシアネート成分）を混合し、酢酸ブチルにてスプレー塗装可能な粘度に調整して、ポリカーボネート基材に乾燥塗膜が２０μｍになるように塗布した後、８０℃で１時間乾燥することにより、作製した。各評価結果は表２および表３に示す。
なお、対照として、植物油由来原料を含まない市販の二液硬化型アクリル／ウレタン系塗料（武蔵塗料（株）製「ハイウレックスＰ」；主剤：アクリルポリオール樹脂、硬化剤：イソシアネート化合物）を用い、上記と同様にして乾燥塗膜２０μｍの硬化塗膜を作製して、その性能を上記と同様に評価した。対照の評価結果については表２に示す。
A cured coating film was prepared using the two-component curable coating composition obtained above, and its performance was evaluated by the following tests. The cured coating is prepared by mixing two liquids (polyol component and polyisocyanate component) of a two-component curable coating composition and adjusting the viscosity to spray coating with butyl acetate. Then, it was produced by drying at 80 ° C. for 1 hour. Each evaluation result is shown in Table 2 and Table 3.
In addition, as a control, a commercially available two-component curable acrylic / urethane-based paint containing no vegetable oil-derived raw material ("Hi-Ulex P" manufactured by Musashi Paint Co., Ltd .; main agent: acrylic polyol resin, hardener: isocyanate compound) is used. A cured coating film having a dry coating film thickness of 20 μm was prepared in the same manner as described above, and its performance was evaluated in the same manner as described above. The control evaluation results are shown in Table 2.
＜耐摩耗性＞
硬化塗膜上で砂消しゴムを１ｋｇ加重にて１０００回往復させた後、硬化塗膜の表面を目視にて観察し、下記の基準で判定した。
◎：全く傷がついていない
○：ほとんど傷がついていない
△：うすくスリ傷が認められる
×：深いスリ傷が認められる
<Abrasion resistance>
After the sand eraser was reciprocated 1000 times with a 1 kg load on the cured coating film, the surface of the cured coating film was visually observed and judged according to the following criteria.
◎: No scratch at all ○: Slightly scratched △: Slight scratches are observed ×: Deep scratches are observed
＜鉛筆硬度＞
ＪＩＳ−Ｋ５６００−５−４（１９９９）に準じ、硬化塗膜面に対して約４５°の角度で鉛筆の芯を当て、芯が折れない程度に強く硬化塗膜面に押し付けながら前方に均一な速さで約１０ｍｍ動かした。鉛筆の芯を当てる箇所を変えてこの操作を５回繰り返し、５回とも塗膜が破れなかった場合のもっとも硬い鉛筆の硬度記号を鉛筆硬度とした。
<Pencil hardness>
According to JIS-K5600-5-4 (1999), a pencil lead is applied at an angle of about 45 ° with respect to the cured coating surface, and evenly pressed forward against the cured coating surface so as not to break the core. Moved about 10 mm at speed. This operation was repeated 5 times by changing the location where the pencil core was applied, and the hardness symbol of the hardest pencil when the coating film was not torn was used 5 times.
＜耐候性＞
ＪＩＳ−Ｈ８６０２−５．１２（１９９２）に準じ、カーボンアーク灯式促進耐候性試験機（サンシャインウェザオメーター）を用いて硬化塗膜の光沢を測定しながら、水スプレー時間を１２分間とし、ブラックパネル温度を６０℃として暴露試験を行い、暴露試験前の光沢に対する光沢保持率が８０％を割る時間を測定し、下記の基準で判定した。
◎：光沢保持率が８０％を割る時間が３００時間以上
○：光沢保持率が８０％を割る時間が２００時間以上かつ３００時間未満
△：光沢保持率が８０％を割る時間が１００時間以上かつ２００時間未満
×：光沢保持率が８０％を割る時間が１００時間未満
<Weather resistance>
In accordance with JIS-H8602-5.12 (1992), while measuring the gloss of the cured coating film using a carbon arc lamp type accelerated weathering tester (sunshine weatherometer), the water spray time was 12 minutes, and the black An exposure test was conducted at a panel temperature of 60 ° C., and the time during which the gloss retention ratio with respect to the gloss before the exposure test was divided by 80% was measured and judged according to the following criteria.
A: Time for gloss retention to break 80% is 300 hours or more ○: Time for gloss retention to break 80% is 200 hours or more and less than 300 hours Δ: Time for gloss retention to break 80% is 100 hours or more Less than 200 hours x: less than 100 hours when gloss retention is less than 80%
＜付着性＞
ＪＩＳ−Ｋ５６００−５−６（１９９０）に準じ、硬化塗膜に１ｍｍ×１ｍｍの碁盤目１００個を作成した後、硬化塗膜表面に粘着テープを貼着し、急激に剥した後に、塗面に残存している碁盤目（塗膜）の個数を計測し、下記の基準で判定した。
◎：残存個数／全体個数＝１００個／１００個
○：残存個数／全体個数＝９９個／１００個
△：残存個数／全体個数＝９０個〜９８個／１００個
×：残存個数／全体個数＝８９個以下／１００個
<Adhesiveness>
In accordance with JIS-K5600-5-6 (1990), after creating 100 grids of 1 mm × 1 mm on the cured coating film, an adhesive tape was applied to the surface of the cured coating film, and the coating surface was peeled off rapidly. The number of cross-cuts (coating film) remaining on the surface was measured and judged according to the following criteria.
◎: remaining number / total number = 100/100 ○: remaining number / total number = 99/100 Δ: remaining number / total number = 90 to 98/100 ×: remaining number / total number = 89 or less / 100
＜耐湿付着性＞
硬化塗膜を温度６５℃、相対湿度９５％の雰囲気下に４８時間放置した後、ＪＩＳ−Ｋ５６００−５−６（１９９０）に準じ、硬化塗膜に１ｍｍ×１ｍｍの碁盤目１００個を作成した後、硬化塗膜表面に粘着テープを貼着し、急激に剥した後に、塗面に残存している碁盤目（塗膜）の個数を計測し、下記の基準で判定した。
◎：残存個数／全体個数＝１００個／１００個
○：残存個数／全体個数＝９９個／１００個
△：残存個数／全体個数＝９０個〜９８個／１００個
×：残存個数／全体個数＝８９個以下／１００個
<Moisture resistance>
After leaving the cured coating film in an atmosphere of 65 ° C. and 95% relative humidity for 48 hours, 100 grids of 1 mm × 1 mm grids were prepared on the cured coating film according to JIS-K5600-5-6 (1990). Then, after sticking an adhesive tape on the surface of the cured coating film and removing it rapidly, the number of grids (coating film) remaining on the coating surface was measured and judged according to the following criteria.
◎: remaining number / total number = 100/100 ○: remaining number / total number = 99/100 Δ: remaining number / total number = 90 to 98/100 ×: remaining number / total number = 89 or less / 100
＜耐アルカリ性＞
硬化塗膜の表面に１％水酸化ナトリウム水溶液を０．５ｍＬ滴下して、温度２０℃、相対湿度６５％の雰囲気下に２４時間放置した後、塗膜表面をガーゼで拭き取り、目視にて観察し、下記の基準で判定した。
◎：変色（白化）などの異常が全くない
○：わずかに変色が認められるが実用レベルである
△：変色（白化）が認められる
×：変色（白化）が著しい
<Alkali resistance>
0.5 mL of 1% sodium hydroxide aqueous solution is dropped on the surface of the cured coating film and left for 24 hours in an atmosphere at a temperature of 20 ° C. and a relative humidity of 65%. Then, the coating film surface is wiped with gauze and visually observed. The determination was made according to the following criteria.
◎: No abnormality such as discoloration (whitening) ○: Slight discoloration is observed but at a practical level △: Discoloration (whitening) is recognized ×: Discoloration (whitening) is remarkable
＜耐薬品性＞
硬化塗膜上にろ紙２枚を並べて置き、各ろ紙上に、ひまし油と人工汗とをそれぞれ滴下して、ろ紙を湿らし、温度２０℃、相対湿度６５％の雰囲気下で２時間放置した後、ろ紙を取り除き、硬化塗膜の表面を目視にて観察し、下記の基準で判定した。
◎：フクレやハガレなどの異常が全くない
○：フクレやハガレなどの異常が殆どなく、ろ紙を置いた部分の見分けがつかない
△：軽度なフクレやハガレなどの異常が認められる
×：フクレやハガレが顕著であり、塗膜の一部が溶けてしまっている
<Chemical resistance>
Two filter papers are placed side by side on the cured coating film, castor oil and artificial sweat are dropped on each filter paper to moisten the filter paper, and left for 2 hours in an atmosphere at a temperature of 20 ° C. and a relative humidity of 65%. The filter paper was removed, and the surface of the cured coating film was visually observed and judged according to the following criteria.
◎: No abnormalities such as bulges and peelings ○: Little abnormalities such as bulges and peelings are found, and the part where the filter paper is placed cannot be distinguished △: Abnormalities such as mild bulges or peelings are observed ×: The peeling is prominent and part of the coating has melted
＜耐温水性＞
硬化塗膜を６０℃の温水中に４時間浸漬した後、硬化塗膜の表面を目視にて観察し、下記の基準で判定した。
◎：艶引け、白化、フクレなどの異常が全く認められず、良好な塗膜状態を維持している
○：わずかに艶引けが認められるが、実用レベルである
△：艶引け、白化、フクレが認められる
×：著しくフクレが認められるか、もしくは塗膜が軟化している
<Hot water resistance>
After immersing the cured coating film in warm water at 60 ° C. for 4 hours, the surface of the cured coating film was visually observed and judged according to the following criteria.
◎: No abnormalities such as gloss, whitening, and swelling are observed, and a good coating state is maintained. ○: Slight glossiness is observed, but at a practical level. Δ: Gloss, whitening, swelling. X: Remarkable blistering is observed, or the coating is soft
Claims (5)
（ｉ）ポリエステルポリオール（Ａ）とビニル重合体部（Ｂ）との構成比率が、重量比で、（Ａ）：（Ｂ）＝２０：８０〜８０：２０であり、
（ｉｉ）ビニル変性ポリエステルポリオールに含まれる植物油由来原料が、該ビニル変性ポリエステルポリオール中の不揮発分に対して２０〜８０重量％であり、
（ｉｉｉ）ポリエステルポリオール（Ａ）の水酸基価が４０〜３００であり、
（ｉｖ）ビニル重合体部（Ｂ）の水酸基価が１０〜３００であり、
（ｖ）ビニル重合体部（Ｂ）のガラス転移点が２０〜１５０℃である、
ことを特徴とするビニル変性ポリエステルポリオール。 A vinyl-modified polyester polyol obtained by binding a vinyl polymer part (B) to a polyester polyol (A) obtained using a vegetable oil-derived raw material,
(I) The composition ratio of the polyester polyol (A) and the vinyl polymer part (B) is (A) :( B) = 20: 80 to 80:20 by weight ratio,
(Ii) The vegetable oil-derived raw material contained in the vinyl-modified polyester polyol is 20 to 80% by weight based on the nonvolatile content in the vinyl-modified polyester polyol,
(Iii) The polyester polyol (A) has a hydroxyl value of 40 to 300,
(Iv) The hydroxyl value of the vinyl polymer part (B) is 10 to 300,
(V) The glass transition point of the vinyl polymer part (B) is 20 to 150 ° C.
A vinyl-modified polyester polyol characterized by that.
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| JP2009187509A JP5291569B2 (en) | 2009-08-12 | 2009-08-12 | Vinyl-modified polyester polyol, two-component curable coating composition and cured product |
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Cited By (6)
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| JP2011225863A (en) * | 2010-04-02 | 2011-11-10 | Dainichiseika Color & Chem Mfg Co Ltd | Biopolyurethane resin |
| JP2012229408A (en) * | 2011-04-25 | 2012-11-22 | Dow Global Technologies Llc | Two-component moisture-curable coating composition |
| JP2016534181A (en) * | 2013-07-22 | 2016-11-04 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Coating system |
| JP2019196455A (en) * | 2018-05-11 | 2019-11-14 | 株式会社トウペ | Vinyl-modified polyester polyol copolymer composition and two-pack curable coating composition |
| WO2022259740A1 (en) * | 2021-06-08 | 2022-12-15 | Dic株式会社 | Curable resin composition, coating material, and article |
| JP2023080375A (en) * | 2021-10-18 | 2023-06-08 | 株式会社イノアックコーポレーション | polyurethane foam |
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| CN112920693B (en) * | 2021-01-22 | 2022-04-19 | 湖南松井新材料股份有限公司 | High-wear-resistance vacuum coating hydroxyl acrylic coating and preparation method and application thereof |
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| JP2011225863A (en) * | 2010-04-02 | 2011-11-10 | Dainichiseika Color & Chem Mfg Co Ltd | Biopolyurethane resin |
| JP2012229408A (en) * | 2011-04-25 | 2012-11-22 | Dow Global Technologies Llc | Two-component moisture-curable coating composition |
| US8722815B2 (en) | 2011-04-25 | 2014-05-13 | Dow Global Technologies Llc | Two-component moisture curable coating compositions |
| JP2016534181A (en) * | 2013-07-22 | 2016-11-04 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Coating system |
| US10808140B2 (en) | 2013-07-22 | 2020-10-20 | Basf Se | Coating system |
| JP2019196455A (en) * | 2018-05-11 | 2019-11-14 | 株式会社トウペ | Vinyl-modified polyester polyol copolymer composition and two-pack curable coating composition |
| WO2022259740A1 (en) * | 2021-06-08 | 2022-12-15 | Dic株式会社 | Curable resin composition, coating material, and article |
| JP2023080375A (en) * | 2021-10-18 | 2023-06-08 | 株式会社イノアックコーポレーション | polyurethane foam |
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| CN101993531B (en) | 2014-07-16 |
| CN101993531A (en) | 2011-03-30 |
| JP5291569B2 (en) | 2013-09-18 |
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