JPS6011535A - Primer composition for vinyl chloride resin molding - Google Patents
Primer composition for vinyl chloride resin moldingInfo
- Publication number
- JPS6011535A JPS6011535A JP11862183A JP11862183A JPS6011535A JP S6011535 A JPS6011535 A JP S6011535A JP 11862183 A JP11862183 A JP 11862183A JP 11862183 A JP11862183 A JP 11862183A JP S6011535 A JPS6011535 A JP S6011535A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- polyester resin
- chloride resin
- saturated polyester
- acid
- 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
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
塩化ビニル系樹脂成型物、特にシート、タイル、フィル
ム等はその安価さ及び化学特性、物理特性にすぐれてい
ることから住宅の内装材やテレビ、ステレオ等のキャビ
ネット等各種用途に多用されている。特（最近は美麗な
光沢や肉持ち感を与えるために不飽和ポリエステル樹脂
塗料等をその表面に塗布することが試みられその需要も
益々拡大しつつある。[Detailed Description of the Invention] Vinyl chloride resin molded products, especially sheets, tiles, films, etc., are inexpensive and have excellent chemical and physical properties, so they are used as interior materials for houses, cabinets for TVs, stereos, etc., etc. Used for many purposes. (Recently, attempts have been made to coat the surface with unsaturated polyester resin paint, etc. to give it a beautiful luster and texture, and the demand for this is increasing.
かかる塗布に当っては塩化ビニル系樹脂成型物と塗料と
の接着性を改善するため、通常フレタンシーラー等の下
塗シ塗料が塗布されるが、従来の下塗シ塗料はそれを塗
布して乾燥するまでにかなりの時間が必要とされるので
ある。充分な乾燥を行なわないまま上塗り塗料を塗布す
ると良好な密着性が得られないことから、かかる下塗り
塗料の乾燥時間を短縮化することは大量生産の場合の重
大な課題となるのである。一方、近時乾燥性の速い下塗
り塗料として不飽和ポリエステル樹脂とポリイソシアネ
ート系化合物とからなる組成物が提案されているが、該
組成物は塩化ビニル系樹脂成型物に対する接着力が充分
でない欠点がある。In order to improve the adhesion between the vinyl chloride resin molding and the paint, an undercoat paint such as a Frethane sealer is usually applied during such application, but with conventional undercoat paints, this is applied and then dried. It takes a considerable amount of time to do so. If the top coat is applied without sufficient drying, good adhesion cannot be obtained, so shortening the drying time of the undercoat is an important issue in mass production. On the other hand, compositions made of unsaturated polyester resins and polyisocyanate compounds have recently been proposed as fast-drying undercoating paints, but these compositions have the disadvantage of not having sufficient adhesion to vinyl chloride resin moldings. be.
しかるに本発明者等はかかる問題を解決するため鋭意研
究を重ねた結果、水酸基価３〜２５０ＫＯＨＷｑ／７の
飽和ポリエステル樹脂とポリイソシアネート化合物から
なる組成物が、塩化ビニル系樹脂成型物用の下地塗料と
して有用であることを見出し本発明を完成するに到った
。However, the inventors of the present invention have carried out intensive research to solve this problem, and as a result, a composition consisting of a saturated polyester resin with a hydroxyl value of 3 to 250 KOHWq/7 and a polyisocyanate compound has been developed as a base paint for vinyl chloride resin molded products. The present invention was completed based on the discovery that the method is useful as a method.
本発明の下地塗料組成物は塩化ビニル系樹脂成型物の表
面に塗布後、短時間で硬化してしまいかつ上塗シ塗料と
良好な接着力を有するので上塗り塗料の塗布が効率的に
実施出来、その工業的な有用性は極めて大である。The base coating composition of the present invention cures in a short time after being applied to the surface of a vinyl chloride resin molded article, and has good adhesion to the top coat, so the top coat can be applied efficiently. Its industrial utility is extremely large.
本発明における飽和ポリエステル樹脂は水酸基価が３〜
２５０ ＫＯＨη／ｙ好ましくは５〜５０ＫＯＨＴｎｇ
／ｙでなければならなイ。３ ＫＯＨ＋＋＋ｙ／７以下
では製造面から制約が多く、一方２５０ ＫＯＨ１’１
ｇ／ｙ以上ではエステル、ケトン等の汎用の溶剤に不溶
となり実用性に乏しくなる。The saturated polyester resin in the present invention has a hydroxyl value of 3 to
250 KOHη/y preferably 5 to 50 KOHTng
It must be /y. 3 KOH+++y/7 or less has many restrictions from a manufacturing perspective, while 250 KOH1'1
If it exceeds g/y, it becomes insoluble in general-purpose solvents such as esters and ketones, and becomes impractical.
本発明における飽和ポリエステル樹脂の酸成分としては
特に限定はされず通常飽和ポリエステル樹脂の製造に使
用されるカルボン酸、例えばイソフタル酸、テレフタル
酸、オルソフタル酸、マロン酸、コハク酸、アジピン酸
、アゼライン酸、セバシン酸、１，５−ナフタル酸、ｐ
−オキシ安息香酸ならびにこれらの低級アルキル部分エ
ステル、酸無水物などが挙げられる。The acid component of the saturated polyester resin in the present invention is not particularly limited, but includes carboxylic acids that are usually used in the production of saturated polyester resins, such as isophthalic acid, terephthalic acid, orthophthalic acid, malonic acid, succinic acid, adipic acid, and azelaic acid. , sebacic acid, 1,5-naphthalic acid, p
-oxybenzoic acid, lower alkyl partial esters thereof, acid anhydrides, and the like.
飽和ポリエステル樹脂を構成する多価アルコール成分と
してはエチレングリコール、ネオペンチルクリコール、
フロピレンゲリコール、１．５−７’ロバンジオール、
１．４−ブタンジオール、１，５−ベンタンジオール、
１，６−ヘキサンジオール、ジエチレンクリコール、ジ
プロピレンクリコール、トリエチレングリコール、シク
ロヘキサンジメタツール、ビスフェノールＡ１水添ビス
フエノールＡなどの２価のアルコールが最も一般的であ
るがトリメチロールエタン、トリメチロールプロパン、
グリセリン、ペンタエリスリトール等の６価以上の多価
ア？レコールもゲル化などが起らない範囲で適宜使用で
きる。The polyhydric alcohol components that make up the saturated polyester resin include ethylene glycol, neopentyl glycol,
Flopylene gelicol, 1.5-7'lovandiol,
1,4-butanediol, 1,5-bentanediol,
Dihydric alcohols such as 1,6-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, cyclohexane dimetatool, bisphenol A1 and hydrogenated bisphenol A are the most common, but trimethylolethane, methylolpropane,
Polyvalent acetate with 6 or more valences such as glycerin and pentaerythritol? Lecole can also be used as appropriate as long as gelation does not occur.
前記酸成分、多価アルコール成分以外にこれらと反応可
能な少量の単量体例えばビニル化合物も使用可能である
。In addition to the acid component and polyhydric alcohol component, small amounts of monomers capable of reacting with these components, such as vinyl compounds, can also be used.
本発明の飽和ポリエステル樹脂の製造に当っては、通常
用いられる任意の方法が採用される。代表的には酸成分
１モルに対して多価アルコール成分を１．′５〜２．５
モルの割合で一括又は順にエステル化触媒と共に撹拌機
、全縮器、分縮器及びトルクメータの付設された反応缶
に仕込み、温度１５０〜２３０℃でエステル化を行う。In producing the saturated polyester resin of the present invention, any commonly used method can be employed. Typically, the amount of polyhydric alcohol component is 1.0 molar per mole of acid component. '5~2.5
The mixture is charged in molar proportions together with the esterification catalyst into a reaction vessel equipped with a stirrer, a total condenser, a partial condenser, and a torque meter, and esterification is carried out at a temperature of 150 to 230°C.
エステル化触媒としてはジグチルチンオキサイド、酢酸
亜鉛等が使用される。その後、安定剤０重縮合触媒の存
在下１岬珈に減圧して温度２４０〜２８０℃で重縮合反
応を行う。安定剤としてはリン酸、トリエチルリン酸、
重結合触媒としては酸化ゲルマニウム、二酸化プンチモ
ン、テトラブチルチタネート等が挙げられる。Digtyltin oxide, zinc acetate, etc. are used as the esterification catalyst. Thereafter, in the presence of a stabilizer and a polycondensation catalyst, the pressure is reduced to 1 Misaki and the polycondensation reaction is carried out at a temperature of 240 to 280°C. Stabilizers include phosphoric acid, triethyl phosphate,
Examples of the heavy bond catalyst include germanium oxide, puntimone dioxide, and tetrabutyl titanate.
飽和ポリエステル樹脂に添加されるポリイソシアネート
化合物は、ポリエステル＊脂に対して水酸基／イソシア
ネート基が２〜０．１（モル比）の範囲で使用する。か
かる範囲外では接着力の低下が認められる。ポリイソシ
アネート化合物としては２．４−トリレンジイソシアネ
ート、２．６−）リレンジイソシアネート、２．４及び
２．６− ）リレンジイソシアネート混合物、４．４’
−ジフェニルメタンジイソシアネート、メタープエニレ
ンジイソシアネート、キシリレンジイソシアネート、テ
トラメチレンジイソシアネート、ヘキサメチレンジイソ
シアネート、リジンジイソシアネートエステル、１．４
−シクロヘキシレンジイソシアネート、４，４−ジシク
ロヘキシルメタンジイソシアネート、１．５−ナフタレ
ンジイソシアネート等が例示される。但し、本発明のポ
リイソシアネート化合物がこれらに限定されるものでは
ない。The polyisocyanate compound added to the saturated polyester resin is used in a range of 2 to 0.1 (molar ratio) of hydroxyl groups/isocyanate groups based on the polyester resin. Outside this range, a decrease in adhesive strength is observed. Examples of polyisocyanate compounds include 2.4-tolylene diisocyanate, 2.6-) lylene diisocyanate, a mixture of 2.4 and 2.6-) lylene diisocyanate, and 4.4'
-Diphenylmethane diisocyanate, metapenylene diisocyanate, xylylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate ester, 1.4
Examples include -cyclohexylene diisocyanate, 4,4-dicyclohexylmethane diisocyanate, and 1,5-naphthalene diisocyanate. However, the polyisocyanate compound of the present invention is not limited to these.
本発明の組成物は飽和ポリエステ／１／樹脂及びポリイ
ソシアネート化合物のいずれにも不活性な溶剤に溶解さ
せて用いられる。該溶剤としてはメチルセロソルブアセ
テート、エチルセロソルブアセテート、トルエン、酢酸
エチル、メチルエチルケトン等が単独で又は混合して用
いられる。The composition of the present invention is used by dissolving both the saturated polyester/1/resin and the polyisocyanate compound in an inert solvent. As the solvent, methyl cellosolve acetate, ethyl cellosolve acetate, toluene, ethyl acetate, methyl ethyl ketone, etc. are used alone or in combination.
尚、本発明の組成物には乾燥促進剤としての金属石ケン
やその他塗料用として公知の助剤を添加しても差交えな
い。又各種メラミン樹脂、エポキシ樹脂を併用しても良
い。Incidentally, metal soap as a drying accelerator or other known auxiliary agents for paints may be added to the composition of the present invention. Also, various melamine resins and epoxy resins may be used in combination.
上塗り塗料としては不飽和ポリエステル樹脂塗料が最も
有利に使用されるが、その他、酢酸ビニｌし樹脂塗料、
酢酸ビニル／アクリル酸エステル樹脂塗料、アクリル樹
脂塗料等任意の塗料の使用が可能である。As the top coat, unsaturated polyester resin paint is most advantageously used, but vinyl acetate resin paint,
Any paint such as vinyl acetate/acrylic ester resin paint or acrylic resin paint can be used.
本発明の下地塗料組成物は塩化ビニル系樹脂成型物、特
にフィルム、シート、タイ？し等の表面に任意の方法で
塗布される。刷毛塗り、ローラー塗り、スプレー法等が
行われる。塗布量は特に限定はないが固形分換算で０．
１〜１０ｙ／ｌｔｆが適当である。The base coating composition of the present invention can be applied to polyvinyl chloride resin molded products, especially films, sheets, ties, etc. It is applied by any method to the surface of the surface. Brush coating, roller coating, spraying, etc. are used. There is no particular limitation on the amount of application, but it should be 0.
1 to 10y/ltf is appropriate.
次に実例を挙げて本発明の組成物を更に具体的に説明す
る。Next, the composition of the present invention will be explained in more detail by giving examples.
実例１
テレフタル酸０．５モル、イソフタル酸０．５モル、エ
チレンクリコール０．６モル、ネオペンチルクリコール
０．４モルからなる水酸基価８ＫＯＨη／ｙの飽和ポリ
エステル樹脂の６０重量％酢酸エチル溶液を調製した。Example 1 A 60% by weight ethyl acetate solution of a saturated polyester resin with a hydroxyl value of 8KOHη/y consisting of 0.5 mol of terephthalic acid, 0.5 mol of isophthalic acid, 0.6 mol of ethylene glycol, and 0.4 mol of neopentyl glycol. was prepared.
これにポリイソシアネート（バイエル社製のＤｅｓｍｏ
ｄｕｒＬ−７５） ５部を配合し下地塗料組成物を得た
。厚さ２００μの半硬質塩化ビニル樹脂シートに該塗料
をグラビアロールコータ−により固形分換算４／ｍ’
となる様に塗布した。Polyisocyanate (Desmo manufactured by Bayer) was added to this.
5 parts of durL-75) were blended to obtain a base coating composition. The paint was applied to a semi-rigid vinyl chloride resin sheet with a thickness of 200μ using a gravure roll coater at a solid content of 4/m'.
It was applied so that
１２０℃で３分向乾燥し硬化させた。It was dried and cured at 120° C. for 3 minutes.
続いて無水フタル酸肌５モル、無水マレイン酸０．５モ
ル、エチレングリコール０．５モル、１．２−プロピレ
ングリコール０．５モルよりなる不飽和ポリエステル樹
脂の８０％スチレン溶液にワックス、パーオキサイド触
媒を配合した塗料をナチュラルコーターで塗布、乾燥さ
せた。Next, wax and peroxide were added to an 80% styrene solution of an unsaturated polyester resin consisting of 5 moles of phthalic anhydride, 0.5 moles of maleic anhydride, 0.5 moles of ethylene glycol, and 0.5 moles of 1,2-propylene glycol. A paint containing a catalyst was applied using a natural coater and dried.
得られた被覆シートは外観に異常はなく、クロスカット
入りセロテープ剥離テストによる密着性テストでは充分
なる接着力が得られた。The obtained covering sheet had no abnormality in appearance, and sufficient adhesion strength was obtained in an adhesion test using a cross-cut Sellotape peel test.
実例２〜３
次表に示す如き組成の下地塗料を用いて実例１に準じて
実験を行った。その結果を表に示す。Examples 2 and 3 Experiments were conducted in accordance with Example 1 using base paints having the compositions shown in the following table. The results are shown in the table.
対照例１〜３
実例１においてポリイソシアネートの使用を省略したと
ころ密着力は０であった。Comparative Examples 1 to 3 When the use of polyisocyanate was omitted in Example 1, the adhesion was zero.
実例１において不飽和ポリエステル樹脂（無水マレイン
酸とエチレングリコールとの縮合）を使用したところ密
着力は不良であった。In Example 1, when an unsaturated polyester resin (condensation of maleic anhydride and ethylene glycol) was used, the adhesion was poor.
Claims (1)
ル樹脂とポリインシアネート化合物とからなる塩化ビニ
ル系樹脂成型物用の下地塗料組成物。A base coating composition for a vinyl chloride resin molded article, comprising a saturated polyester resin having a hydroxyl value of 5 to 250 KOHwq/7 and a polyincyanate compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11862183A JPS6011535A (en) | 1983-06-29 | 1983-06-29 | Primer composition for vinyl chloride resin molding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11862183A JPS6011535A (en) | 1983-06-29 | 1983-06-29 | Primer composition for vinyl chloride resin molding |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6011535A true JPS6011535A (en) | 1985-01-21 |
| JPH043423B2 JPH043423B2 (en) | 1992-01-23 |
Family
ID=14741063
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11862183A Granted JPS6011535A (en) | 1983-06-29 | 1983-06-29 | Primer composition for vinyl chloride resin molding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6011535A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5315867A (en) * | 1976-07-28 | 1978-02-14 | Hitachi Ltd | Thermister thermometer for water of automobile |
-
1983
- 1983-06-29 JP JP11862183A patent/JPS6011535A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5315867A (en) * | 1976-07-28 | 1978-02-14 | Hitachi Ltd | Thermister thermometer for water of automobile |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH043423B2 (en) | 1992-01-23 |
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