JPH0668087B2 - Ink composition - Google Patents
Ink compositionInfo
- Publication number
- JPH0668087B2 JPH0668087B2 JP1344660A JP34466089A JPH0668087B2 JP H0668087 B2 JPH0668087 B2 JP H0668087B2 JP 1344660 A JP1344660 A JP 1344660A JP 34466089 A JP34466089 A JP 34466089A JP H0668087 B2 JPH0668087 B2 JP H0668087B2
- Authority
- JP
- Japan
- Prior art keywords
- methylpentene
- chlorination
- resin
- chlorinated
- chlorine
- 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.)
- Expired - Fee Related
Links
- 239000000203 mixture Substances 0.000 title claims description 6
- 239000011347 resin Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 20
- 238000005660 chlorination reaction Methods 0.000 claims description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 17
- 239000000460 chlorine Substances 0.000 claims description 17
- 229910052801 chlorine Inorganic materials 0.000 claims description 17
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 239000012736 aqueous medium Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000976 ink Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000001678 irradiating effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001256 steam distillation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、インキ用組成物として可撓性と耐熱性を有す
る塩素化４−メチルペンテン−１系樹脂に関するもので
ある。The present invention relates to a chlorinated 4-methylpentene-1 resin having flexibility and heat resistance as an ink composition.
塩素化４−メチルペンテン−１系樹脂は、ポリ・４−メ
チルペンテン−１および／またはα−オレフィン・４−
メチルペンテン−１ポリマーを塩素化して製造される物
質である。これ等塩素化４−メチルペンテン−１樹脂
は、耐候性，耐水性，耐薬品性等に優れているばかりで
なく、従来の塩素化ポリオレフィン類に比べ耐熱性が非
常に優れた樹脂で、高速印刷インキ用バインダーとして
巾広く用いられている。Chlorinated 4-methylpentene-1 resin is poly-4-methylpentene-1 and / or α-olefin-4-
It is a substance produced by chlorinating methylpentene-1 polymer. These chlorinated 4-methylpentene-1 resins are not only excellent in weather resistance, water resistance, chemical resistance, etc., but also very excellent in heat resistance as compared with conventional chlorinated polyolefins, Widely used as a binder for printing inks.
しかし、従来の製造法である耐塩素溶媒中で塩素化され
た塩素化４−メチルペンテン−１系樹脂は、均一塩素化
合物ゆえに、インキ被膜を形成した際、硬くてもろいの
で耐屈曲性に劣る点が指摘されている。However, a chlorinated 4-methylpentene-1 resin chlorinated in a chlorine-resistant solvent, which is a conventional manufacturing method, is inferior in bending resistance because it is hard and brittle when an ink film is formed because of a uniform chlorine compound. Points are pointed out.
この耐屈曲性を改良するために従来から種々の改良策が
提案されている。例えば特開昭58−45266は塩素化ポリ
・４−メチルペンテン−１にアクリル系モノマーを重合
し可撓性を付与する事を開示している。あるいは実用時
に可塑剤等の柔らかい樹脂を併用する事で物理的に可撓
性を与えている実用例もある。しかしこれ等可撓性を付
与する方法は、塩素化４−メチルペンテン−１系樹脂の
特徴である耐熱性を実質的に低下させる事となり、満足
される改良策には至っていない。In order to improve this bending resistance, various improvement measures have been conventionally proposed. For example, JP-A-58-45266 discloses that chlorinated poly-4-methylpentene-1 is polymerized with an acrylic monomer to give flexibility. Alternatively, there is a practical example in which a soft resin such as a plasticizer is also used in practice to impart physical flexibility. However, these methods of imparting flexibility have substantially not lowered the heat resistance, which is a characteristic of chlorinated 4-methylpentene-1 resin, and have not been a satisfactory improvement measure.
本発明は上記実情に鑑み、耐熱性を低下させる事なく、
可撓性を付与した塩素化４−メチルペンテン−１系樹脂
を用いたインキ用組成物を提供しようとするものであ
る。In view of the above situation, the present invention does not reduce heat resistance,
It is intended to provide an ink composition using a chlorinated 4-methylpentene-1 resin having flexibility.
本発明者等は、種々検討した結果、ポリ・４−メチルペ
ンテン−１および／またはα−オレフィン・４−メチル
ペンテン−１ポリマーを塩素化する段階において、水性
媒体中で行なえば粉体樹脂の表面から塩素化され、不均
一反応体が形成されやすい事に着目し、本発明に至っ
た。As a result of various studies, the inventors of the present invention have found that, in the step of chlorinating the poly-4-methylpentene-1 and / or the α-olefin-4-methylpentene-1 polymer, the powder resin is The present invention has been accomplished, focusing on the fact that a heterogeneous reactant is easily formed by chlorination from the surface.
すなわち、従来の耐塩素溶媒中で塩素化された塩素化４
−メチルペンテン−１ポリマーは、均一反応ゆえに分子
量巾が狭く、従って硬い被膜が形成される樹脂となって
いたが水性媒体中で塩素化を行なえば不均一反応体が形
成され、塩素化度に巾を持たせる事ができ、合せて分子
量巾が広くなる事より可撓性のある塩素化樹脂が得られ
る訳である。その際懸濁液を循環ポンプで循環し、ある
いは循環液の途中にボールミル等を配置し、機械的に粉
体樹脂表面を剥離更新しつつ塩素化すれば、その度合い
によって耐熱性を損う事なく任意に可撓性を与えた塩素
化４−メチルペンテン−１系樹脂が得られる訳である。That is, chlorinated 4 chlorinated in conventional chlorine resistant solvent
-Methylpentene-1 polymer had a narrow molecular weight range due to the uniform reaction, and thus it was a resin that forms a hard coating. However, if chlorination is performed in an aqueous medium, a heterogeneous reactant is formed, and the degree of chlorination increases. The width can be increased, and the molecular weight width can be widened accordingly, so that a flexible chlorinated resin can be obtained. At that time, if the suspension is circulated by a circulation pump, or a ball mill or the like is placed in the middle of the circulating liquid to mechanically separate and renew the powder resin surface for chlorination, the heat resistance may be impaired depending on the degree. That is, it is possible to obtain a chlorinated 4-methylpentene-1 type resin which is arbitrarily given flexibility.
本発明に採用される樹脂はその重合体の粒子内部に多く
の空隙を持つか、粒子粒径が小さければ必要以上の不均
一塩素化が免れ、本発明の効果を出す上で好ましい条件
となる。The resin used in the present invention has many voids inside the particles of the polymer, or if the particle size is small, it avoids unnecessary heterogeneous chlorination, which is a preferable condition for exerting the effect of the present invention. .
本発明で塩素含有量50重量％以上としたのはそれ以下で
は本発明の特徴である耐熱性が得られないからである。In the present invention, the chlorine content is set to 50% by weight or more because the heat resistance, which is a feature of the present invention, cannot be obtained below that.
以下、実施例及び比較例を挙げ、本発明の詳細を説明す
るが、本発明はこれ等の実施例に限定されるものではな
い。Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
実施例１ ガラス製反応器に500部の純水と、MIが8g／10min（ASTM
D1238−65T）の４−メチルペンテン−１ホモポリマー
100部を投入し、容器内を撹拌しつつ窒素パージを行な
った後、常圧で光を照射しつつ、90℃で塩素を吹き込み
塩素化を行なった。その時樹脂粒子の団塊化を防ぐ目的
で懸濁液を循環ポンプで循環し、かつ循環系の途中にボ
ールミルを設置して機械的に粉体樹脂表面を剥離更新し
つつ塩素化を行なう方法をとり、反応中連続的に粉砕処
理を行なった。平均塩素含有率が54重量％に達した時塩
素化反応を停止し、残存塩素を除去した後、乾燥して試
料を得た。Example 1 500 parts of pure water in a glass reactor, MI 8g / 10min (ASTM
D1238-65T) 4-methylpentene-1 homopolymer
After adding 100 parts and performing nitrogen purge while stirring the inside of the container, chlorine was blown at 90 ° C. to perform chlorination while irradiating light at normal pressure. At that time, in order to prevent the agglomeration of resin particles, the suspension is circulated by a circulation pump, and a ball mill is installed in the middle of the circulation system to mechanically separate and renew the powder resin surface for chlorination. The crushing treatment was continuously performed during the reaction. When the average chlorine content reached 54% by weight, the chlorination reaction was stopped, residual chlorine was removed, and the sample was dried to obtain a sample.
実施例２ ガラス製反応器に、500部の純粋と、デセン−１を15mol
％含むMIが36g／10min（ASTM D1238−65T）の４−メチ
ルペンテン−１コポリマー100部を投入し、容器内を撹
拌しつつ窒素パージを行なった後、常圧で光を照射しつ
つ、90℃で塩素を吹き込み塩素化を行なった。その時樹
脂粒子の団塊化を防ぐ目的で懸濁液を循環ポンプで循環
し、かつ循環系の途中にボールミルを設置して機械的に
粉体樹脂表面を剥離更新しつつ塩素化を行なう方法をと
り、反応中２時間サイクルで１時間の粉砕処理を行なっ
た。平均塩素含有率が62重量％に達した時塩素化反応を
停止し、残存塩素を除去した後、乾燥して試料を得た。Example 2 A glass reactor was charged with 500 parts of pure and 15 mol of decene-1.
% MI containing 36 g / 10 min (ASTM D1238-65T) 100 parts of 4-methylpentene-1 copolymer was charged, and nitrogen purging was performed while stirring the inside of the container, then while irradiating with light at normal pressure, 90 Chlorination was performed by blowing chlorine at ℃. At that time, in order to prevent the agglomeration of resin particles, the suspension is circulated by a circulation pump, and a ball mill is installed in the middle of the circulation system to mechanically separate and renew the powder resin surface for chlorination. During the reaction, crushing treatment was performed for 1 hour in a 2-hour cycle. When the average chlorine content reached 62% by weight, the chlorination reaction was stopped, residual chlorine was removed, and the sample was dried to obtain a sample.
実施例３ ガラス製反応器に500部の純水と、エチレン10mol％含む
MIが70g／10min（ASTM D1238−65T）のエチレン・４−
メチルペンテン−１コポリマー100部を投入し、容器内
を撹拌しつつ窒素パージを行なった後、常圧で光を照射
しつつ、90℃で塩素を吹き込み塩素化を行なった。平均
塩素含有率が68重量％に達した時塩素化反応を停止し、
残存塩素を除去した後、乾燥して試料を得た。Example 3 A glass reactor contains 500 parts of pure water and 10 mol% of ethylene.
MI 70g / 10min (ASTM D1238-65T) ethylene 4-
100 parts of methylpentene-1 copolymer was added, nitrogen purging was performed while stirring the inside of the container, and then chlorine was blown at 90 ° C. to chlorinate while irradiating light at normal pressure. When the average chlorine content reaches 68% by weight, the chlorination reaction is stopped,
After removing the residual chlorine, it was dried to obtain a sample.
比較例１ MIが54g／10min（ASTM D1238−65T）の４−メチルペン
テン−１ホモポリマー100gをとり５リットルの四塩素化
炭素に溶解し、常圧下85℃で十分に溶解した後、光を照
射しつつ塩素化を行なった。塩素含有率が60重量％に達
した時塩素化反応を停止し、残存塩素を除去した後、水
蒸気蒸留する事によって白色の粉末を取出した。Comparative Example 1 100 g of 4-methylpentene-1 homopolymer having MI of 54 g / 10 min (ASTM D1238-65T) was dissolved in 5 liters of carbon tetrachloride and sufficiently dissolved at 85 ° C. under normal pressure. Chlorination was performed while irradiating. When the chlorine content reached 60% by weight, the chlorination reaction was stopped, residual chlorine was removed, and steam distillation was carried out to obtain a white powder.
比較例２ デセン−１を15mol％含むMIが36g／10min（ASTM D1238
−65T）の４−メチルペンテン−１コポリマー100gをと
り５リットルの四塩素化炭素に溶解し、2kg／cm2の圧力下11
0℃で十分に溶解した後、光を照射しつつ塩素化を行な
った。塩素含有率が65重量％に達した時塩素化反応を停
止し、残存塩素を除去した後、水蒸気蒸留する事によっ
て白色の粉末を取出した。Comparative Example 2 MI containing 15 mol% of decene-1 was 36 g / 10 min (ASTM D1238
-65T) of 4-methylpentene-1 copolymer (100 g) was dissolved in 5 liters of carbon tetrachloride, and the pressure of 2 kg / cm 2 was applied.
After sufficiently dissolving at 0 ° C, chlorination was performed while irradiating with light. When the chlorine content reached 65% by weight, the chlorination reaction was stopped, residual chlorine was removed, and steam distillation was carried out to obtain a white powder.
実施例１〜３及び比較例１〜２で得られた試料について
の溶液粘度，平均分子量，分子量分散度，軟化温度及び
耐熱分解性の各分析、さらに各試料の20％トルエン溶液
をみがき軟鋼板（SPCC JIS3141冷間圧延B,0.8×50×15
0m／ｍ）へ塗工、１昼夜風乾後、耐屈曲性，耐衝撃性試
験を行なった結果を表−１に示す。また、各試料を用い
てグラビア印刷インキを調製した。即ち、樹脂18gとト
ルエン72gで20％トルエン溶液を調製しこれに顔料（カ
ーミン6BN:東洋インキ製造KK品）10gを加えサンドミル
により２時間混練した後、インキの固形分を一定にして
コート紙状に塗工し５〜７μのインキ膜を形成した。こ
れを室温で十分に乾燥後、発色性，耐熱性，インキの保
存安定性の各試験を行なった結果を表−２に示す。Analysis of solution viscosity, average molecular weight, molecular weight dispersity, softening temperature and thermal decomposition resistance of the samples obtained in Examples 1 to 3 and Comparative Examples 1 to 2, and 20% toluene solution of each sample was brushed to a mild steel plate. (SPCC JIS3141 cold rolling B, 0.8 × 50 × 15
Table 1 shows the results of bending resistance and impact resistance tests after coating to 0 m / m) and air-drying for 24 hours. A gravure printing ink was prepared using each sample. That is, a 20% toluene solution was prepared from 18 g of resin and 72 g of toluene, and 10 g of pigment (Karmin 6BN: KK product of Toyo Ink Mfg. Co., Ltd.) was added and kneaded in a sand mill for 2 hours. And an ink film of 5 to 7 μm was formed. After sufficiently drying this at room temperature, each test of color development, heat resistance and ink storage stability is shown in Table 2.
〔発明の効果〕 表−１及び表−２から本発明組成物は自己可撓性を持
ち、その他の物性は従来の均一塩素化法で得られた物質
と遜色のない性状を有するものである事が判る。 [Effects of the Invention] From Table-1 and Table-2, the composition of the present invention has self-flexibility, and has other physical properties comparable to those obtained by the conventional homogeneous chlorination method. I understand.
Claims (2)
たはα−オレフィン・４−メチルペンテン−１ポリマー
を水性媒体中に懸濁させ、粉体樹脂表面を剥離更新し
て、塩素含有率50重量％以上に塩素化して得られる可撓
性と耐熱性を有する塩素化４−メチルペンテン−１系樹
脂を用いた可撓性を有する耐熱性インキ用組成物。1. A poly-4-methylpentene-1 and / or α-olefin-4-methylpentene-1 polymer is suspended in an aqueous medium, and the powder resin surface is peeled and renewed to give a chlorine content of 50. A flexible heat-resistant ink composition using a chlorinated 4-methylpentene-1 resin having flexibility and heat resistance, which is obtained by chlorinating to a weight percent or more.
たはα−オレフィン・４−メチルペンテン−１ポリマー
の懸濁液を循環しあるいは循環液の途中で粉砕処理を行
ないつつ塩素化させる、請求項１記載の組成物。2. A method in which a suspension of poly-4-methylpentene-1 and / or an α-olefin-4-methylpentene-1 polymer is circulated or pulverized in the circulating liquid while chlorination is performed. Item 1. The composition according to Item 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1344660A JPH0668087B2 (en) | 1989-12-27 | 1989-12-27 | Ink composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1344660A JPH0668087B2 (en) | 1989-12-27 | 1989-12-27 | Ink composition |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3651694A Division JP2665879B2 (en) | 1994-02-09 | 1994-02-09 | Composition for OP varnish |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03199275A JPH03199275A (en) | 1991-08-30 |
| JPH0668087B2 true JPH0668087B2 (en) | 1994-08-31 |
Family
ID=18370995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1344660A Expired - Fee Related JPH0668087B2 (en) | 1989-12-27 | 1989-12-27 | Ink composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0668087B2 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5426839A (en) * | 1977-08-02 | 1979-02-28 | Osaka Soda Co Ltd | Preparation of chlorinated polyethylene solution |
| JPS5817553B2 (en) * | 1978-05-24 | 1983-04-07 | 大阪曹達株式会社 | Chlorinated polyethylene paint composition |
-
1989
- 1989-12-27 JP JP1344660A patent/JPH0668087B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03199275A (en) | 1991-08-30 |
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