JPH03220220A - Production of phenolic resin and can coating agent - Google Patents
Production of phenolic resin and can coating agentInfo
- Publication number
- JPH03220220A JPH03220220A JP1363690A JP1363690A JPH03220220A JP H03220220 A JPH03220220 A JP H03220220A JP 1363690 A JP1363690 A JP 1363690A JP 1363690 A JP1363690 A JP 1363690A JP H03220220 A JPH03220220 A JP H03220220A
- Authority
- JP
- Japan
- Prior art keywords
- phenol
- resin
- component
- phenolic resin
- water
- 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.)
- Pending
Links
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 21
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 13
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000011248 coating agent Substances 0.000 title abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 7
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000003973 paint Substances 0.000 claims description 20
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 7
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- -1 NaOH) Chemical class 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011134 resol-type phenolic resin Substances 0.000 description 1
- 239000010979 ruby Substances 0.000 description 1
- 229910001750 ruby Inorganic materials 0.000 description 1
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はエポキシ−フェノール系塗料に利用されるフェ
ノール樹脂の製造方法及びそれを配合した缶塗料の製造
方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a phenol resin used in epoxy-phenol paints and a method for producing can paints containing the same.
より詳細には、缶用水性塗料中の硬化剤として使用され
た場合に、ＫＭｎＯ４消費量、密着性、硬化性に優れた
塗膜が得られ、かつ得られた！！膜が淡色である缶塗料
配合用フェノール樹脂及び缶塗料の製造方法に関するも
のである。More specifically, when used as a curing agent in a water-based paint for cans, a coating film with excellent KMnO4 consumption, adhesion, and curability was obtained! ! The present invention relates to a phenolic resin for use in can paint formulations having a light-colored film and a method for producing the can paint.
［従来の技術〕
周知のようにエポキシ−フェノール系塗料の性能は、硬
化剤であるフェノール樹脂の性質によって大きく影響さ
れる。実際には用いられるフェノール成分の種類と組成
比、触媒の種類と量、ホムルアルデヒド量、エポキシ／
フェノール比等によって性能のバランスを変化させ、そ
れぞれの用途に応じた種々のレゾール型フェノール樹脂
が利用されている。しかしながら従来の方法により製造
されるフェノール樹脂は遊離フェノール成分が多く残存
し、エポキシ−フェノール系水性塗料の硬化剤に用いた
場合、Ｋ Ｍ ｎ Ｏ４消費量が高く、密着性に劣ると
いうような欠点があった。[Prior Art] As is well known, the performance of epoxy-phenolic paints is greatly influenced by the properties of the phenolic resin that is the curing agent. In reality, the type and composition ratio of the phenol component used, the type and amount of the catalyst, the amount of formaldehyde, the epoxy/
Various resol-type phenolic resins are used depending on the purpose, with the balance of performance changing depending on the phenol ratio, etc. However, the phenolic resin produced by the conventional method has many remaining free phenol components, and when used as a curing agent for epoxy-phenolic water-based paints, it has drawbacks such as high KM n O4 consumption and poor adhesion. was there.
本発明者は、缶塗料配合用フェノール樹脂について、従
来から要求されてきたエポキシ−フェノール系水性塗料
の塗膜のＫＭｎＯａ消費量の低下と密着性の向上、淡色
化について鋭意研究を行っり結果、特定のフェノール類
とホルムアルデヒドを特定の割合で、アルカリ金属の水
酸化物を触媒として反応させて得られるフェノール樹脂
がきわめて有効であ゛るとの知見を得た。The present inventor has conducted extensive research on phenolic resins for can paint formulations to reduce KMnOa consumption, improve adhesion, and lighten the color of epoxy-phenol water-based paints, which have been traditionally required. It has been found that phenolic resins obtained by reacting specific phenols and formaldehyde in specific ratios with an alkali metal hydroxide as a catalyst are extremely effective.
その目的とするところは缶塗料用エポキシーフェノール
系水性塗料の硬化剤として使用した場合、Ｋ Ｍ ｎ
Ｏｓ消費量が小さく、密着性にすぐれ、硬化性がよい、
塗膜が淡色であるといった性能を塗膜に付与することが
可能なフェノール樹脂及び、それを用いた缶塗料を提供
することにある。Its purpose is that when used as a curing agent for epoxy phenolic water-based paints for can paints, K M n
Low Os consumption, excellent adhesion, and good curing properties.
An object of the present invention is to provide a phenol resin capable of imparting properties such as a light color to a paint film, and a can paint using the same.
本発明の要旨は、フェノールとビスフェノール類をモル
比１：０．１−１：０．５の割合で混合したフェノール
１モルとホルムルデヒド４．０〜６゜０モルとをアルカ
リ金属の水酸化物触媒の存在下で反応させ、遊離フェノ
ール成分をレジン固形分に対して０．１％以下にするこ
とを特徴とするフェノール樹脂の製造方法である。The gist of the present invention is to hydroxylate an alkali metal by mixing 1 mole of phenol and bisphenols in a molar ratio of 1:0.1 to 1:0.5 with 4.0 to 6.0 moles of formaldehyde. This is a method for producing a phenol resin, which is characterized in that the reaction is carried out in the presence of a chemical catalyst, and the free phenol component is reduced to 0.1% or less based on the solid content of the resin.
本発明において用いられるビスフェノール類は、ビスフ
ェノールＡ及びビスフェノールＦに代表されるビスフェ
ノール類である。The bisphenols used in the present invention are bisphenols represented by bisphenol A and bisphenol F.
フェノールとビスフェノール類の混合比はフェノール１
モルに対してビスフェノール類を０．１〜０．５モルが
好ましい、ビスフェノール類が多くなるとメチロールフ
ェノール成分が少なくなり分子量的に大きくなるため、
水性エマルシヨンとの相溶性が悪くなるので好ましくな
い。The mixing ratio of phenol and bisphenols is phenol 1
Preferably, the amount of bisphenols is 0.1 to 0.5 mole per mole, because as the amount of bisphenols increases, the methylolphenol component decreases and the molecular weight increases.
This is not preferable because the compatibility with the aqueous emulsion becomes poor.
また触媒として用いるアルカリ金属の水酸化物は、例え
ば水酸化ナトリウム、水酸化カリウム等が挙げられる０
反応触媒中に存在させるべきアルカリ金属の水酸化物の
量としては、通常フェノール１モルに対して０．５〜１
．０モル程度、好ましくはフェノール１モルに対して０
．７〜０．９モル程度である。触媒のモル比が０．５よ
りも小さいと、樹脂中のメチロール基が少なく塗料とし
た場合に硬化が遅く、相溶性、Ｋ Ｍ ｎ Ｏ４消費量
が悪くなり実用的でなくなる。逆に触媒のモル比が１．
０モルよりも大きいと反応の制御が困難となる。In addition, examples of the alkali metal hydroxide used as a catalyst include sodium hydroxide, potassium hydroxide, etc.
The amount of alkali metal hydroxide that should be present in the reaction catalyst is usually 0.5 to 1 per mole of phenol.
．． About 0 mole, preferably 0 per mole of phenol
．． It is about 7 to 0.9 mol. If the molar ratio of the catalyst is less than 0.5, there are few methylol groups in the resin, and when used as a coating material, curing is slow and compatibility and K M n O4 consumption are poor, making it impractical. Conversely, if the molar ratio of the catalyst is 1.
If it is larger than 0 mol, it becomes difficult to control the reaction.
触媒は添加時の発熱を抑えるために、反応開始時に全量
の２／３を添加し内温安定後残りの１／３を添加するの
が好ましい。In order to suppress heat generation during addition of the catalyst, it is preferable to add 2/3 of the total amount at the start of the reaction and add the remaining 1/3 after the internal temperature has stabilized.
反応条件としては、初期反応時の温度が４５〜５５℃、
時間が２〜４時間であって、２次反応時の温度が６０℃
〜８０℃、時間が２〜５時間が好ましい。The reaction conditions include a temperature of 45 to 55°C during the initial reaction;
The time is 2 to 4 hours, and the temperature during the secondary reaction is 60°C.
Preferably, the temperature is 80° C. and the time is 2 to 5 hours.
反応後、生成した樹脂を中和後水洗を行い、常圧又は減
圧下で水分を除去するとよい。After the reaction, the resulting resin is preferably neutralized and then washed with water to remove moisture under normal pressure or reduced pressure.
本発明で得られたフェノール樹脂は常法によりエポキシ
樹脂を主成分とするエマルジ４ンと混合される。このエ
マルシヨンは、エポキシ樹脂にアクリル酸、メタクリル
酸、スチレン等を付加重合させたものも好ましく使用さ
れる。エポキシ樹脂に対するフェノール樹脂の割合は、
通常固形分換算で２〜ＩＯ重置％である。The phenolic resin obtained in the present invention is mixed with an emulsion containing an epoxy resin as a main component by a conventional method. Preferably, this emulsion is one obtained by addition polymerizing acrylic acid, methacrylic acid, styrene, etc. to an epoxy resin. The ratio of phenolic resin to epoxy resin is
It is usually 2 to IO weight percent in terms of solid content.
以下に、実施例を掲げて本発明の詳細な説明する。なお
実施例中の１部」は「重量部」を「％」は「重量パーセ
ント」を示す。The present invention will be described in detail below with reference to Examples. In the examples, "1 part" indicates "part by weight" and "%" indicates "percent by weight."
ｒ実施例ｚＪ
フェノール２２５部（２，３９モル）及びビスフェノー
ルＡ ７５部（０，３３モル）に３７％ホルマリン１
２９２部（１１，９５モル）を加え、触媒として２５％
水酸化ナトリウム水溶液２００部（１，２５モル）を添
加し５０℃にて１時間反応する。rExample zJ 225 parts (2,39 mol) of phenol and 75 parts (0,33 mol) of bisphenol A in 1 part of 37% formalin
Added 292 parts (11,95 mol), 25% as catalyst
200 parts (1.25 mol) of sodium hydroxide aqueous solution is added and reacted at 50°C for 1 hour.
ついで２５％水酸化ナトリウム水溶液１００部（０，６
２５モル）を新たに添加し５０℃でさらに１．５時間反
応させた後７０℃に昇温し２．５時間反応させた０反応
終了後３５％硫酸２１６部（０，７７モル）を添加して
中和し、生成した樹脂をブタノール４５０部、酢酸エチ
ル１１０部を加えて溶解させ４０℃で３回水洗を行った
。水洗後、共沸脱水で水分を除去し目的とするフェノー
ル樹脂を得た。Next, 100 parts of a 25% aqueous sodium hydroxide solution (0.6
25 mol) was added and reacted for another 1.5 hours at 50°C, then heated to 70°C and reacted for 2.5 hours. After the completion of the reaction, 216 parts (0.77 mol) of 35% sulfuric acid was added. The resulting resin was dissolved by adding 450 parts of butanol and 110 parts of ethyl acetate, and washed with water three times at 40°C. After washing with water, water was removed by azeotropic dehydration to obtain the desired phenol resin.
この時の樹脂の粘度は１２０ｃｐｓ／２５°Ｃ１不揮発
が４１％、遊離フェノ−成分がレジン固形第１表
と同様の方法でフェノール樹脂を製造した。得られたフ
ェノール樹脂の物性を第１表に併せて示す。The viscosity of the resin at this time was 120 cps/25 DEG C. The non-volatile content was 41%, and the free phenol component was resin solid.A phenol resin was produced in the same manner as shown in Table 1. The physical properties of the obtained phenol resin are also shown in Table 1.
〔塗膜性能試験］
上記実施例１〜３および比較例１〜３で得られたフェノ
ール樹脂を用いて下記のように水性塗料第
を調整し、その塗料をアルし倹に塗布後焼付けを行い、
ＫＭｎＯ，消費量、密着性、外観チエツクなどの試験を
行った。[Coating film performance test] Using the phenolic resins obtained in Examples 1 to 3 and Comparative Examples 1 to 3 above, water-based paints were prepared as shown below, and the paints were aluminized, applied sparingly, and then baked. ,
Tests were conducted on KMnO, consumption, adhesion, appearance check, etc.
各種試験方法を下記に示し、その試験結果を第２表に示
す。Various test methods are shown below, and the test results are shown in Table 2.
水性エマルシヨンの調
■ エピコート１００９ １００．（１部■
ブチルセロソルブ １００．０ 部■ メタ
クリル酸 ５０．０ 部■ スチレン
１６．７ 部■ 過酸化ベンゾイル
４．６７部■ ブチルセロソルブ
１４．２ 部■ ジメチルアミノエタノール
１４．３ 部■ イオン交換水 ４５０．
０ 部反応容器に■■を入れ、１１５℃にて完全に溶
解させた後■〜■の混合物を１時間にわたって滴下する
０滴下後１１５℃で２時間反応を行い、反応終了後■を
加えて１００℃まで内温を下げる。Aqueous emulsion formula ■ Epicote 1009 100. (Part 1■
Butyl cellosolve 100.0 parts ■ Methacrylic acid 50.0 parts ■ Styrene
16.7 parts ■ Benzoyl peroxide 4.67 parts ■ Butyl cellosolve
14.2 parts ■ Dimethylaminoethanol
14.3 parts ■ Ion exchange water 450.
0 parts Put ■■ into a reaction container, and after completely dissolving at 115℃, add the mixture of ■～■ dropwise over 1 hour. Lower the internal temperature to 100℃.
ついで■を加えた後■をすこしずつ添加したところ、固
形分２３．８％、粘度８５ｃｐｓ／２５℃の乳白色の水
性エマルジョンを得た。Then, (1) was added and then (2) was added little by little to obtain a milky white aqueous emulsion with a solid content of 23.8% and a viscosity of 85 cps/25°C.
水性塗料の調整
上記水性エマルジョンと実施例、比較例で得られたフェ
ノール樹脂の固形分の重量比が１９対１となるように混
合し安定な水性塗料を得た。Preparation of water-based paint The above-mentioned water-based emulsion and the phenol resins obtained in Examples and Comparative Examples were mixed so that the solid content weight ratio was 19:1 to obtain a stable water-based paint.
（１） Ｋ Ｍ ｎ Ｏａ消費量
上記の方法で調整した各水性塗料を５ＣＩＸ２０１のア
ルミ枚にバーコーターで焼付は後の膜厚が５〜７μとな
るように塗布した。(1) K M n Oa consumption Each of the water-based paints prepared in the above manner was applied to a 5CIX201 aluminum sheet using a bar coater so that the film thickness after baking was 5 to 7 μm.
その試験片を２００℃で５分間焼付は後、水道水２００
ｄが入った５０（ｌｄ）−ルビー力に入れてアルミニウ
ム箔でフタをし、１３０℃で３０分のレトルト処理を行
った。このようにして得られた試験水について食品衛生
法記載実験法（厚生省４３４号）に準じて測定した。After baking the test piece at 200℃ for 5 minutes,
The mixture was placed in a 50 (ld) ruby strainer containing 100 ml of chlorine, covered with aluminum foil, and subjected to retort treatment at 130° C. for 30 minutes. The test water thus obtained was measured in accordance with the experimental method described in the Food Sanitation Act (Ministry of Health and Welfare No. 434).
（２）密着性
上記Ｋ Ｍ ｎ Ｏａ消費量の測定に用いる試験片と同
様の塗布焼付を行い、１００°Ｃの水に１時間浸漬する
処理をした。その後試験片の塗膜面にカッターナイフを
使用して約１閣の幅で縦、横それぞれ１１本の切り目を
基盤目に入れた。セロハン粘着テープでばくり試験を行
い、未剥離数を分子に示した。(2) Adhesion The test piece was coated and baked in the same manner as the test piece used for measuring the K M n Oa consumption above, and immersed in water at 100°C for 1 hour. Thereafter, using a cutter knife, 11 vertical and horizontal cuts were made on the coated surface of the test piece, each having a width of about one square. A peeling test was performed using cellophane adhesive tape, and the number of unpeeled pieces was shown in the numerator.
第２表
〔発明の効果〕
本発明の方法により製造されるフェノール樹脂を缶用エ
ポキシ−フェノール系塗料の硬化剤として用いた場合、
Ｋ Ｍ ｎ Ｏａ消費量が少なくかつ密着性に優れた淡
色の塗膜を得ることができる。Table 2 [Effects of the Invention] When the phenolic resin produced by the method of the present invention is used as a curing agent for an epoxy-phenolic paint for cans,
A light-colored coating film with low K M n Oa consumption and excellent adhesion can be obtained.
Claims (2)
１〜１：０．５の割合で混合したフェノール類１モルと
ホムルアルデヒド４．０〜６．０モルとをアルカリ金属
の水酸化物触媒の存在下で反応させ、遊離フェノール成
分をレジン固形分に対して０．１％以下にすることを特
徴とするフェノール樹脂の製造方法。(1) Phenol and bisphenols in a molar ratio of 1:0.
1 mole of phenols mixed at a ratio of 1 to 1:0.5 and 4.0 to 6.0 moles of formaldehyde are reacted in the presence of an alkali metal hydroxide catalyst, and the free phenol components are converted into resin solids. A method for producing a phenolic resin, characterized in that the amount is 0.1% or less.
エポキシ樹脂を主成分とする水性エマルジョンに配合す
ることを特徴とする缶塗料の製造方法。(2) A method for producing a can paint, which comprises blending the phenol resin obtained by the method according to claim 1 into an aqueous emulsion containing an epoxy resin as a main component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1363690A JPH03220220A (en) | 1990-01-25 | 1990-01-25 | Production of phenolic resin and can coating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1363690A JPH03220220A (en) | 1990-01-25 | 1990-01-25 | Production of phenolic resin and can coating agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03220220A true JPH03220220A (en) | 1991-09-27 |
Family
ID=11838722
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1363690A Pending JPH03220220A (en) | 1990-01-25 | 1990-01-25 | Production of phenolic resin and can coating agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03220220A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06287261A (en) * | 1993-04-06 | 1994-10-11 | Kanebo Nsc Ltd | Method for purifying novolak resin |
| JPH06287262A (en) * | 1993-04-06 | 1994-10-11 | Kanebo Nsc Ltd | Method for purifying novolak resin |
-
1990
- 1990-01-25 JP JP1363690A patent/JPH03220220A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06287261A (en) * | 1993-04-06 | 1994-10-11 | Kanebo Nsc Ltd | Method for purifying novolak resin |
| JPH06287262A (en) * | 1993-04-06 | 1994-10-11 | Kanebo Nsc Ltd | Method for purifying novolak resin |
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