JPH0135003B2 - - Google Patents
Info
- Publication number
- JPH0135003B2 JPH0135003B2 JP55140591A JP14059180A JPH0135003B2 JP H0135003 B2 JPH0135003 B2 JP H0135003B2 JP 55140591 A JP55140591 A JP 55140591A JP 14059180 A JP14059180 A JP 14059180A JP H0135003 B2 JPH0135003 B2 JP H0135003B2
- Authority
- JP
- Japan
- Prior art keywords
- paint
- monomer
- acrylic resin
- weight
- acrylic
- 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
Links
- 239000003973 paint Substances 0.000 claims description 36
- 239000000178 monomer Substances 0.000 claims description 15
- 239000004925 Acrylic resin Substances 0.000 claims description 14
- 229920000178 Acrylic resin Polymers 0.000 claims description 14
- 229920006395 saturated elastomer Polymers 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- 239000000049 pigment Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001308 synthesis method Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 229920000180 alkyd Polymers 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- -1 methacryloyl group Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920000728 polyester Chemical group 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は、良好な性能を有する塗料用アクリル
系樹脂の製造方法に関するものである。更に詳し
くは、優れた顔料分散安定性および塗膜性能を有
する有機溶剤に可溶な塗料用アクリル系樹脂の製
造方法に関するものである。
従来より、塗膜の耐汚染性、耐薬品性、耐候性
などの点で優れた性能を有する塗料用樹脂とし
て、アクリル系樹脂が広く使用されている。しか
し、一般的にアクリル系樹脂は顔料分散安定性に
劣り、例えば、凝集による顔料沈降、色分かれな
どのトラブルを起こしやすいという欠点がある。
こうした欠点を改良する為に、例えば、アクリル
系樹脂に動植物油変性アルキド樹脂や不飽和オイ
ルフリ−アルキド樹脂をグラフト重合することが
検討されているが、これらの方法では第2成分と
してアルキド樹脂を導入する為、アクリル系樹脂
のもつ優れた塗膜性能(例えば耐汚染性、耐薬品
性など)を維持することが困難になるという問題
がある。特に、昨今市場より要求されている省資
源・低公害型塗料の一つである有機溶剤使用量の
少ない高不揮発分型塗料を従来の方法で得ようと
すると、その顔料分散安定性と塗膜性能を同時に
満足させることが更に極めて困難となる。尚、こ
こで言う高不揮発分型塗料とは、塗装時の塗料中
の不揮発分が60重量%以上である塗料を意味す
る。
本発明者らは、こうした欠点を克服する塗料用
のアクリル系樹脂を得るべく研究を行つた結果、
上記の問題点を解決しうる塗料用アクリル系樹脂
の製造方法を見出だして本発明を完成するに至つ
た。即ち、本発明の塗料用アクリル系樹脂の製造
方法は
一般式
(但し、式中R1は水素原子又はメチル基を示し、
−X1O−および−X2O−はそれぞれ飽和二価アル
コール残基を示し、互いに異なつていても同一で
もよく、−COYCO−O−は飽和二塩基酸残基を
示し、lは1〜3の整数を示し、mは1〜3の整
数を示し、nは1〜3の整数を示す。)
で示される単量体()1〜90重量部と、単量体
()以外の(メタ)アクリル系単量体を10重量
%以上含有するビニル系単量体()99〜10重量
部とを有機溶剤中でラジカル共重合させる事を特
徴とするものである。尚、本明細書において、
(メタ)アクリロイル基とはアクリロイル基とメ
タアクリロイル基を(メタ)アクリル系単量体と
はアクリル系単量体とメタアクリル系単量体を、
(メタ)アクリル酸とはアクリル酸とメタアクリ
ル酸を、(メタ)アクリレートとはアクリレート
とメタアクリレートを、それぞれ総称するものと
する。
単量体()は、上記一般式で表わされる通
り、(メタ)アクリロイル基と、末端にヒドロキ
シ基を有するポリエステル基とからなる単量体で
ある。単量体()は、公知の合成方法により製
造されるが、そのような方法として例えば次の(a)
項及び(b)項に記す方法を挙げることができる。し
かし、これらの方法により本発明の範囲が限定さ
れるものではない。
(a) (メタ)アクリル酸と飽和二塩基酸無水物と
の混合物に飽和モノエポキサイドを反応させる
方法(以下、合成法(a)という。)
(b) ビドロキシアルキル基をもつ(メタ)アクリ
レートと飽和二塩基酸無水物との混合物に飽和
モノエポキサイドを反応させる方法(以下、合
成法(b)という。)
合成法(a)又は(b)で使用される飽和二塩基酸無水
物としては、例えば、無水フタル酸、テトラヒド
ロ無水フタル酸、テトラクロロ無水フタル酸、無
水ヘツト酸、無水コハク酸などがあげられる。
合成法(a)又は(b)で使用される飽和モノエポキサ
イドとしては、例えば、エチレンオキサイド、プ
ロピレンオキサイド、スチレンオキサイド、ブチ
ルグリシジルエーテルなどがあげられる。
合成法(b)で使用されるヒドロキシアルキル基を
もつ(メタ)アクリレートとしては、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)アクリレートなどが
あげられる。
第1表に単量体()についていくつかの具体
例を示した。しかし、これによつて本発明の範囲
が限定されるものではない。
The present invention relates to a method for producing an acrylic resin for paint having good performance. More specifically, the present invention relates to a method for producing an acrylic resin for paints that is soluble in organic solvents and has excellent pigment dispersion stability and coating performance. Conventionally, acrylic resins have been widely used as paint resins that have excellent performance in terms of stain resistance, chemical resistance, weather resistance, etc. of paint films. However, acrylic resins generally have poor pigment dispersion stability, and have the disadvantage that they tend to cause problems such as pigment sedimentation and color separation due to aggregation, for example.
In order to improve these drawbacks, for example, graft polymerization of animal and vegetable oil-modified alkyd resins or unsaturated oil-free alkyd resins to acrylic resins has been considered, but in these methods, alkyd resins are introduced as a second component. Therefore, there is a problem that it becomes difficult to maintain the excellent coating film performance (for example, stain resistance, chemical resistance, etc.) of acrylic resin. In particular, when trying to obtain a high non-volatile paint with a low amount of organic solvent, which is one of the resource-saving and low-pollution paints demanded by the market these days, the pigment dispersion stability and paint film It becomes even more difficult to satisfy the performance requirements at the same time. The term "high non-volatile paint" as used herein means a paint in which the non-volatile content of the paint at the time of coating is 60% by weight or more. The present inventors conducted research to obtain an acrylic resin for paint that overcomes these drawbacks, and as a result,
The present invention has been completed by discovering a method for producing an acrylic resin for paint that can solve the above problems. That is, the method for producing the acrylic resin for paint according to the present invention has the following general formula: (However, in the formula, R 1 represents a hydrogen atom or a methyl group,
-X 1 O- and -X 2 O- each represent a saturated dihydric alcohol residue and may be different or the same, -COYCO-O- represents a saturated dibasic acid residue, and l is 1 represents an integer of ~3, m represents an integer of 1-3, and n represents an integer of 1-3. ) 1 to 90 parts by weight of a monomer () represented by the formula () and 99 to 10 parts by weight of a vinyl monomer () containing 10% by weight or more of a (meth)acrylic monomer other than monomer () It is characterized by radical copolymerization of and in an organic solvent. In addition, in this specification,
(Meth)acryloyl group refers to acryloyl group and methacryloyl group. (Meth)acrylic monomer refers to acrylic monomer and methacrylic monomer.
(Meth)acrylic acid is a general term for acrylic acid and methacrylic acid, and (meth)acrylate is a general term for acrylate and methacrylate, respectively. As represented by the above general formula, the monomer () is a monomer consisting of a (meth)acryloyl group and a polyester group having a hydroxyl group at the end. The monomer () is produced by a known synthesis method, such as the following (a).
Examples include the methods described in paragraphs and (b). However, the scope of the present invention is not limited by these methods. (a) A method in which a mixture of (meth)acrylic acid and a saturated dibasic acid anhydride is reacted with a saturated monoepoxide (hereinafter referred to as synthesis method (a)) (b) (meth)acrylate having a bidroxyalkyl group A method of reacting a saturated monoepoxide with a mixture of and a saturated dibasic acid anhydride (hereinafter referred to as synthesis method (b)) The saturated dibasic acid anhydride used in synthesis method (a) or (b) is Examples include phthalic anhydride, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, hectic anhydride, and succinic anhydride. Examples of the saturated monoepoxide used in synthesis method (a) or (b) include ethylene oxide, propylene oxide, styrene oxide, butyl glycidyl ether, and the like. As the (meth)acrylate having a hydroxyalkyl group used in the synthesis method (b), for example, 2
-Hydroxyethyl (meth)acrylate, 2-
Examples include hydroxypropyl (meth)acrylate. Table 1 shows some specific examples of monomers (). However, the scope of the present invention is not limited thereby.
【表】【table】
(白色塗料)
〔樹脂溶液1〕〜〔樹脂溶液4〕および〔比較
樹脂溶液1〕〜〔比較樹脂溶液3〕のそれぞれに
白色顔料“タイペークR−820”(石原産業社製、
ルチル型酸化チタン)を樹脂/顔料=1/1(重
量比)になるように加え、ボールミルにて48時間
混練した。これをキシレン/ソルベツソ−150/
酢酸ブチル=1/1/1(重量比)のシンナー
(以下、単に「シンナー」とよぶ。)にて塗料粘度
が20秒(フオード・カツプNo.4、25℃。尚、以下
についても同様。)になるように稀釈したものを
試料とした。
(黒色塗料)
〔樹脂溶液1〕〜〔樹脂溶液4〕および〔比較
樹脂溶液1〕〜〔比較樹脂溶液3〕のそれぞれ
に、黒色顔料“FW−200”(デグツサ社製、カー
ボンブラツク)を樹脂/顔料=1/0.04(重量比)
になるように加え、ボールミルにて48時間混練し
た。これを、前記の白色塗料を調整する場合と全
く同様にしてシンナーにて稀釈したものを試料と
した。
(青色塗料)
〔樹脂溶液1〕〜〔樹脂溶液4〕および〔比較
樹脂溶液1〕〜〔比較樹脂溶液3〕それぞれに、
青色顔料“リゾマブルーZ”(小西顔料(株)製)を
樹脂/顔料=1/0.16(重量比)になるように加
え、ボールミルにて48時間混練した。これを、前
記の白色塗料を製造する場合と全く同様にしてシ
ンナーにて稀釈したものを試料とした。
〔調色塗料の調整〕
各樹脂溶液を用いて得られた上記白色・黒色お
よび青色の3種の原色塗料を用いて、下記の配合
比率で配合したものを調色塗料の試料とした。
グレー色:白色塗料/黒色塗料=95/5(重量
比)
ライトブルー色:白色塗料/青色塗料=95/5
( 〃 )
(White paint) White pigment “Tiepeque R-820” (manufactured by Ishihara Sangyo Co., Ltd.,
Rutile type titanium oxide) was added at a resin/pigment ratio of 1/1 (weight ratio), and the mixture was kneaded in a ball mill for 48 hours. Add this to xylene/Solbetso-150/
Paint viscosity is 20 seconds (Food Cup No. 4, 25°C) using butyl acetate = 1/1/1 (weight ratio) thinner (hereinafter simply referred to as "thinner").The same applies to the following. ) was used as a sample. (Black paint) Black pigment "FW-200" (manufactured by Degutsa, Carbon Black) was added to each of [Resin solution 1] to [Resin solution 4] and [Comparative resin solution 1] to [Comparative resin solution 3]. /pigment=1/0.04 (weight ratio)
The mixture was added to the mixture and kneaded in a ball mill for 48 hours. This was diluted with thinner in exactly the same manner as when preparing the white paint, and a sample was prepared. (Blue paint) [Resin solution 1] to [Resin solution 4] and [Comparative resin solution 1] to [Comparative resin solution 3], respectively.
A blue pigment "Rizoma Blue Z" (manufactured by Konishi Pigment Co., Ltd.) was added at a resin/pigment ratio of 1/0.16 (weight ratio), and kneaded in a ball mill for 48 hours. This was diluted with thinner in exactly the same manner as in the production of the white paint described above, and used as a sample. [Adjustment of toning paint] Using the three primary color paints of white, black, and blue obtained using each resin solution, the following blending ratios were used to prepare samples of toning paints. Gray color: white paint/black paint = 95/5 (weight ratio) Light blue color: white paint/blue paint = 95/5
( 〃 )
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
実施例 6
実施例5で得られた7種類の白色塗料を用いて
塗膜性能を評価した。但し、〔樹脂溶液2〕〜
〔樹脂溶液4〕および〔比較樹脂溶液2〕〜〔比
較樹脂溶液3〕をそれぞれ用いて調製した白色塗
料については、それぞれに“スーパーベツカミン
J−820”(大日本インキ化学(株)製のブチル化メラ
ミン樹脂の50%溶液。)を樹脂/メラミン樹脂
(不揮発分比)=75/25の比率になるように配合
し、シンナーにて塗料粘度が20秒になるように稀
釈したものを試料とした。結果は第4表に示した
通りであつた。
尚、被覆基材としてパーカー#144処理の施さ
れた厚さ0.6mmのダル鋼板を用い、これに各白色
塗料を手吹きスプレー塗装し、室温で1週間放置
又は160℃の温度で20分間焼付けたものをテスト
ピースとした。
第4表に示すように、本発明の塗料用アクリル
系樹脂を用いた塗料は、良好な塗膜性能を有して
いる。[Table] Example 6 The seven types of white paints obtained in Example 5 were used to evaluate coating film performance. However, [resin solution 2] ~
For the white paints prepared using [Resin Solution 4] and [Comparative Resin Solution 2] to [Comparative Resin Solution 3], each was treated with "Super Betsucomin J-820" (manufactured by Dainippon Ink Chemical Co., Ltd.). A 50% solution of butylated melamine resin) was mixed at a ratio of resin/melamine resin (non-volatile content) = 75/25, and diluted with thinner to a paint viscosity of 20 seconds. And so. The results were as shown in Table 4. In addition, a 0.6 mm thick dull steel plate treated with Parker #144 was used as the coating base material, and each white paint was hand-sprayed onto this plate and left at room temperature for one week or baked at a temperature of 160°C for 20 minutes. This was used as a test piece. As shown in Table 4, the paint using the acrylic resin for paint of the present invention has good film performance.
【表】【table】
Claims (1)
−X1O−および−X2O−はそれぞれ飽和二価アル
コール残基を示し、互いに異なつていても同一で
もよく、−COYCO−O−は飽和二塩基酸残基を
示し、は1〜3の整数を示し、mは1〜3の整
数を示し、nは1〜3の整数を示す。) で示される単量体()1〜90重量部と、単量体
()以外の(メタ)アクリル系単量体を10重量
%以上含有するビニル系単量体()99〜10重量
部とを有機溶剤中でラジカル共重合させる事を特
徴とする有機溶剤に可能な塗料用アクリル系樹脂
の製造方法。 2 塗料用アクリル系樹脂の数平均分子量が1000
〜6000の範囲である請求項1記載の塗料用アクリ
ル系樹脂の製造方法。[Claims] 1. General formula (However, in the formula, R 1 represents a hydrogen atom or a methyl group,
-X 1 O- and -X 2 O- each represent a saturated dihydric alcohol residue and may be different or the same; -COYCO-O- represents a saturated dibasic acid residue; represents an integer of 3, m represents an integer of 1 to 3, and n represents an integer of 1 to 3. ) 1 to 90 parts by weight of a monomer () represented by the formula () and 99 to 10 parts by weight of a vinyl monomer () containing 10% by weight or more of a (meth)acrylic monomer other than monomer () A method for producing an acrylic resin for paints that can be used in an organic solvent, characterized by radical copolymerization of and in an organic solvent. 2 The number average molecular weight of acrylic resin for paint is 1000
The method for producing an acrylic resin for paint according to claim 1, wherein the acrylic resin has a molecular weight of 6,000 to 6,000.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14059180A JPS5765709A (en) | 1980-10-09 | 1980-10-09 | Acryl resin for coating |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14059180A JPS5765709A (en) | 1980-10-09 | 1980-10-09 | Acryl resin for coating |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5765709A JPS5765709A (en) | 1982-04-21 |
JPH0135003B2 true JPH0135003B2 (en) | 1989-07-21 |
Family
ID=15272241
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP14059180A Granted JPS5765709A (en) | 1980-10-09 | 1980-10-09 | Acryl resin for coating |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5765709A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3020890U (en) * | 1995-07-24 | 1996-02-06 | 株式会社光彩工芸 | Tie bar |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60215008A (en) * | 1984-04-10 | 1985-10-28 | Denki Kagaku Kogyo Kk | High-energy ray-curable resin composition |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS502761A (en) * | 1973-05-10 | 1975-01-13 |
-
1980
- 1980-10-09 JP JP14059180A patent/JPS5765709A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS502761A (en) * | 1973-05-10 | 1975-01-13 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3020890U (en) * | 1995-07-24 | 1996-02-06 | 株式会社光彩工芸 | Tie bar |
Also Published As
Publication number | Publication date |
---|---|
JPS5765709A (en) | 1982-04-21 |
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