JPH03252488A - Uv curing type precise adhesive - Google Patents
Uv curing type precise adhesiveInfo
- Publication number
- JPH03252488A JPH03252488A JP4950290A JP4950290A JPH03252488A JP H03252488 A JPH03252488 A JP H03252488A JP 4950290 A JP4950290 A JP 4950290A JP 4950290 A JP4950290 A JP 4950290A JP H03252488 A JPH03252488 A JP H03252488A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy
- adhesive
- resin
- pts
- intramolecular
- 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
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 38
- 239000000853 adhesive Substances 0.000 title claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 15
- 239000004593 Epoxy Substances 0.000 claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 11
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 10
- 239000011342 resin composition Substances 0.000 claims abstract description 9
- 239000000945 filler Substances 0.000 claims abstract description 6
- 238000012663 cationic photopolymerization Methods 0.000 claims abstract description 5
- 239000003999 initiator Substances 0.000 claims abstract description 5
- 230000009257 reactivity Effects 0.000 abstract description 17
- 229920000647 polyepoxide Polymers 0.000 abstract description 11
- 239000003822 epoxy resin Substances 0.000 abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 229910002012 Aerosil® Inorganic materials 0.000 abstract description 2
- 125000003700 epoxy group Chemical group 0.000 abstract description 2
- 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 2
- 238000002156 mixing Methods 0.000 abstract 2
- 238000001723 curing Methods 0.000 description 16
- 125000002091 cationic group Chemical group 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 125000002723 alicyclic group Chemical group 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000012952 cationic photoinitiator Substances 0.000 description 2
- 238000010538 cationic polymerization reaction Methods 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- -1 glycidyl ester Chemical class 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- IDSLNGDJQFVDPQ-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-yl) hexanedioate Chemical compound C1CC2OC2CC1OC(=O)CCCCC(=O)OC1CC2OC2CC1 IDSLNGDJQFVDPQ-UHFFFAOYSA-N 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は反応性が高く、かつ低硬化収縮率と低線膨張率
を有するカチオン重合系の紫外線硬化型精密接着剤に関
する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a cationic polymerization type ultraviolet curable precision adhesive that is highly reactive and has a low curing shrinkage rate and a low linear expansion coefficient.
エポキシ系ベースレジンを用いたカチオン重合系紫外線
硬化樹脂は、反応性が低く、したがって、硬化時に大き
な紫外線エネルギを必要とした。そのため、高紫外線エ
ネルギ照射装置を必要としたり、照射時間が長くかかる
という欠点があった。また、低硬化収縮率化と低線膨張
率化を図るために、無機系粉末を多量に充てんすると、
更に極ｔて反応性が低くなるという欠点があった。Cationic polymerization type ultraviolet curing resins using epoxy base resins have low reactivity and therefore require large amounts of ultraviolet energy during curing. Therefore, there are disadvantages in that a high ultraviolet energy irradiation device is required and the irradiation time is long. In addition, in order to lower the curing shrinkage rate and linear expansion rate, if a large amount of inorganic powder is filled,
Furthermore, there was a drawback that the reactivity was extremely low.
このようなカチオン系紫外線硬化樹脂の反応の低さを向
上させるための方法として、脂環式エポキシをベースレ
ジン又は希釈剤として用いる方法などが知られている。As a method for improving the low reactivity of such cationic ultraviolet curable resins, a method using an alicyclic epoxy as a base resin or a diluent is known.
しかし、ラジカル系紫外線硬化樹脂の反応速度に比べる
と遅い。However, the reaction rate is slower than that of radical ultraviolet curing resins.
また、入手できる脂環式エポキシの種類は限られており
、実用性能を満足できるように配合することが難しい。Furthermore, the types of alicyclic epoxies that are available are limited, and it is difficult to formulate them in a manner that satisfies practical performance.
一方、実用性能を満足できるように配合すると、反応性
が低下するという欠点があり、反応性と実用性能を両立
させることが困難である。例えば、入手できる脂環式エ
ポキシを用い、反応性を低下させないように配合すると
、比較的もろく、伸びかです実用上不充分となる。On the other hand, if they are blended in a manner that satisfies practical performance, there is a drawback that the reactivity decreases, making it difficult to achieve both reactivity and practical performance. For example, if an available alicyclic epoxy is used and blended without reducing reactivity, it will be relatively brittle and elastic, which is insufficient for practical use.
これを改善するために、柔軟性を付与する目的で、−船
釣な柔軟性付与剤を添加すると反応性が低下するという
欠点があった。また、低硬化収縮率化と低線膨張率化を
有する精密接着剤を実現するために、無機系粉末を多量
に充てんすると、反応性が更に低下し、実用的な配合物
はできないという欠点があった。In order to improve this problem, adding a specific flexibility imparting agent for the purpose of imparting flexibility has the disadvantage of reducing reactivity. Furthermore, in order to create precision adhesives with low curing shrinkage and low coefficient of linear expansion, filling a large amount of inorganic powder will further reduce reactivity, making it impossible to create a practical formulation. there were.
本発明の目的は、エポキシ系ベースレジンと無機系粉末
充てん剤を用いたカチオン系紫外線硬化型樹脂組成物の
反応性の低さを改良した紫外線硬化型精密接着剤を提供
することにある。An object of the present invention is to provide an ultraviolet curable precision adhesive that improves the low reactivity of a cationic ultraviolet curable resin composition using an epoxy base resin and an inorganic powder filler.
本発明を概説すれば、本発明のカチオン系紫外線硬化型
精密接着剤は、エポキシ系ベースレジン１００重量部に
対して、無機系粉末充てん剤５０〜３００重量部及びカ
チオン系光重合開始剤からなる樹脂組成物に、分子内エ
ポキシ変性ポリブタジェンを３〜２０重量部含有してい
ることを特徴きする。To summarize the present invention, the cationic ultraviolet curable precision adhesive of the present invention consists of 50 to 300 parts by weight of an inorganic powder filler and a cationic photopolymerization initiator based on 100 parts by weight of an epoxy base resin. It is characterized in that the resin composition contains 3 to 20 parts by weight of intramolecularly epoxy-modified polybutadiene.
本発明のカチオン系紫外線硬化型精密接着剤は、分子内
エポキシ変性ポリブタジェンを含有するため、エポキシ
系ベースレジンに無機系粉末を多量に充てんしても、反
応性が高く、かつ実用性能も十分であるという特徴を有
する。従来のカチオン系紫外線硬化型接着剤あるいは無
機系充てん剤を多量に充てんしたカチオン系紫外線硬化
型精密接着剤は、反応性が低く、実用的でない。Since the cationic UV-curable precision adhesive of the present invention contains epoxy-modified polybutadiene in its molecules, it has high reactivity and sufficient practical performance even when the epoxy base resin is filled with a large amount of inorganic powder. It has the characteristic of being. Conventional cationic ultraviolet curable adhesives or cationic ultraviolet curable precision adhesives filled with large amounts of inorganic fillers have low reactivity and are not practical.
本発明において使用するエポキシ系ベースレジンとして
は、ビスフェノールＡ系エポキシ樹脂、グリシジルエス
テル系エポキシ樹脂あるいはフッ素や臭素を含有するエ
ポキシ樹脂、あるいはそれらの変成物、又はその他の特
殊なエポキシ樹脂、若しくは、それらの混合物などを用
いることができる。また、脂環式エポキシ樹脂として、
３．４−エポキシシクロへキシル−３，４エポキシシク
ロヘキサン力ルポキシレート、２−（３，４−エポキシ
シクロへキシル−５，５スピロ−３，４−エポキシ）シ
クロヘキサン−メタ−ジオキサン、ビス（３，４−エポ
キシシクロヘキシル）アジペートなど、あるいはそれら
の変成物、若しくは、それらの混合物などを用いること
ができる。The epoxy base resin used in the present invention includes bisphenol A epoxy resin, glycidyl ester epoxy resin, epoxy resin containing fluorine or bromine, modified products thereof, or other special epoxy resins, or A mixture of these can be used. In addition, as an alicyclic epoxy resin,
3.4-Epoxycyclohexyl-3,4epoxycyclohexane lupoxylate, 2-(3,4-epoxycyclohexyl-5,5spiro-3,4-epoxy)cyclohexane-meth-dioxane, bis(3, 4-epoxycyclohexyl) adipate, modified products thereof, or mixtures thereof can be used.
本発明において使用する分子内エポキシ変性ポリブタジ
ェンとしては、主鎖に、下記の構造のエポキシ基を含む
ものを言う。The intramolecular epoxy-modified polybutadiene used in the present invention is one containing an epoxy group having the following structure in its main chain.
例えば、Ｐｏ１ｙ ｂｄＲ−４５ＢＰＩ ＜：ｆ−ポキ
シ当量２００、出光石油化学社製）があるが、それ以外
の分子内エポキシ変性ポリブタジェンでも用いることが
できる。For example, there is Po1y bdR-45BPI <: f-poxy equivalent 200, manufactured by Idemitsu Petrochemical Co., Ltd.), but other intramolecular epoxy-modified polybutadienes can also be used.
分子内エポキシ変性ポリブタジェンの添加量としては、
３〜２０重量部が適当である。３重量部未満では、反応
性が向上しない。一方、２０重量部を超えると、硬化物
の特性低下、特に、硬化収縮率や線膨張率が大きくなっ
てしまう。The amount of intramolecular epoxy-modified polybutadiene added is as follows:
3 to 20 parts by weight is suitable. If it is less than 3 parts by weight, the reactivity will not improve. On the other hand, if it exceeds 20 parts by weight, the properties of the cured product will deteriorate, particularly the curing shrinkage rate and linear expansion rate will increase.
本発明において使用する無機系粉末充てん剤としでは、
コージェライト粉末あるいはタルク粉末あるいはシリカ
系微粉末あるいはそれらの混合粉末を使用すること適切
であるが、それ以外に、カオリン、β−スボジュメン、
β−ニークリプト、セリサイト、マシナブルセラミック
粉末、マイカなどの粉末が使用できる。なお、シリカ系
微粉末として、アエロジル微粉末を用いると、粘度調節
が自由にできるので、作業状況に合せ、適切な粘度の接
着剤が容易に調製できる。The inorganic powder filler used in the present invention includes:
It is appropriate to use cordierite powder, talc powder, silica-based fine powder, or a mixed powder thereof, but in addition, kaolin, β-subodumene,
Powders such as β-nycrypt, sericite, machinable ceramic powder, and mica can be used. Note that when Aerosil fine powder is used as the silica-based fine powder, the viscosity can be freely adjusted, so that an adhesive having an appropriate viscosity can be easily prepared according to the working situation.
本発明において使用するカチオン系光重合開始剤として
は、市販されているカチオン系光開始剤のジアゾニウム
塩、ハロニウム塩、スルホニウム塩などを使用すること
ができる。As the cationic photoinitiator used in the present invention, commercially available cationic photoinitiators such as diazonium salts, halonium salts, and sulfonium salts can be used.
また、必要の場合は、希釈剤、顔料などを添加すること
もできる。Further, if necessary, a diluent, a pigment, etc. can also be added.
分子内エポキシ変性ポリブタジェンを添加すると、反応
性の低いエポキシベースレジンを使用したカチオン系紫
外線硬化樹脂組成物の紫外線による反応性を向上するこ
とができる。Addition of intramolecular epoxy-modified polybutadiene can improve the ultraviolet reactivity of a cationic ultraviolet curable resin composition using an epoxy base resin with low reactivity.
以下、本発明を実施例により更に具体的に説明するが、
本発明はこれらに何ら限定されない。Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these in any way.
実施例１〜４
第１表に示した配合成分を用い、カチオン系紫外線硬化
性樹脂組成物を調製し、光反応性（表面硬化時間、接着
固定時間）、接着強度、硬化収縮率、線膨張率、耐水接
着性などの評価を行った０
光反応性の評価法：第１図に示したような、７６Ｘ２６
ｍｍのスライドガラスに、接着剤を塗布、また、７Ｘｉ
３ｍｍの小ガラス片を接着剤樹脂で貼る。その後、紫外
光を所定量照射して硬化性を観察した。表面硬化時間は
、接着剤の塗布部を綿棒でこすり、綿が付着しない状況
になった時を表面硬化時間とした。また、接着固定時間
は、小ガラス片に、約３ ｋｇｆのせん断力を加えてず
れなくなった時間として評価した。すなわち第１図は光
反応性評価用サンプルの形状を示す図であって、第１−
１図は平面図、第１２図は側面図である。また、各図に
おいて、左側のサンプル２個は表面硬化性評価用、右側
のサンプル３個は接着固定評価用である。Examples 1 to 4 A cationic ultraviolet curable resin composition was prepared using the ingredients shown in Table 1, and the photoreactivity (surface curing time, adhesive fixation time), adhesive strength, curing shrinkage rate, and linear expansion were evaluated. Evaluation method for photoreactivity: 76 x 26 as shown in Figure 1.
Apply adhesive to a slide glass of mm, and also
Attach a small piece of 3mm glass with adhesive resin. Thereafter, curability was observed by irradiating a predetermined amount of ultraviolet light. The surface curing time was defined as the time when the area to which the adhesive was applied was rubbed with a cotton swab and no cotton adhered to it. The adhesion fixation time was evaluated as the time it took for the small glass pieces to stop slipping after applying a shearing force of about 3 kgf. That is, FIG. 1 is a diagram showing the shape of a sample for photoreactivity evaluation, and FIG.
1 is a plan view, and FIG. 12 is a side view. In each figure, the two samples on the left are for surface hardening evaluation, and the three samples on the right are for adhesive fixation evaluation.
接着強度の評価法；第２図に示したような張り合せ接着
片を作製（接着剤硬化条件は、約１０ｍＷ／ｃｕｔのメ
タルハライドランプ、５分間照射）した。測定は、第２
図に示したような試料ホルダーに接着片を入れ、引張試
験機で、速度５ＩｎＩＩｌ／分で圧縮プレートにより圧
縮、せん断接着強度を測定した。すなわち第２図は接着
強度の評価方法を示す図であって、第２−１図は全体の
断面概略図、第２−２図は試験片を示す図である。Evaluation method for adhesive strength: A laminated adhesive piece as shown in FIG. 2 was prepared (adhesive curing conditions were irradiation with a metal halide lamp of about 10 mW/cut for 5 minutes). The measurement is the second
The adhesive piece was placed in a sample holder as shown in the figure, and the compression and shear adhesive strength was measured using a compression plate using a tensile tester at a speed of 5 InII/min. That is, FIG. 2 is a diagram showing a method for evaluating adhesive strength, FIG. 2-1 is a schematic cross-sectional view of the whole, and FIG. 2-2 is a diagram showing a test piece.
硬化収縮率の評価方法：硬化前後の密度を測定して、硬
化収縮率を算出した。Evaluation method for curing shrinkage rate: The density before and after curing was measured to calculate the curing shrinkage rate.
線膨張率の評価方法：熱機械分析装置により測定した。Evaluation method for linear expansion coefficient: Measured using a thermomechanical analyzer.
耐水接着性の評価法：第３図に示したような、７６ｘ２
６−スライドガラスに、７×１３ルの小ガラス片を接着
剤で固定した試料を作製した。Water resistant adhesion evaluation method: As shown in Figure 3, 76x2
6 - A sample was prepared by fixing a small piece of glass measuring 7 x 13 squares with adhesive to a glass slide.
この試料を１０時間煮沸後、接着界面部のはく離、気泡
発生を観察して、耐水性を評価した。After boiling this sample for 10 hours, peeling at the adhesive interface and generation of bubbles were observed to evaluate water resistance.
すなわち第３図は耐水接着性評価用サンプルの形状を示
す図であって、第３−１図は平面図、第３−２図は側面
図である。That is, FIG. 3 is a diagram showing the shape of a sample for evaluating water-resistant adhesive properties, with FIG. 3-1 being a plan view and FIG. 3-2 being a side view.
得られた結果を第１表に示す。The results obtained are shown in Table 1.
第
表
注） Ｂｐ−８２８： 油化シェル社製ビスフェノール
型エポキシ樹脂
ＥＡＲＬ−４２２１： Ｕ ＣＣ製脂澁エポキシ樹脂Ｂ
ＲＬ−４２３４： Ｕ ＣＣ製脂環エポキシ樹脂Ｒ−４
５ＢＰＩ ： ｆｆｌ光石油化学製エポキシ変性ポリブ
タジェン
ＢＲＬ−４２０６： ＩＪ ＣＣ製脂環エポキシ樹脂希
釈剤
５ｐ−１７０’無電化社製カチオン系光重合開始剤
＾−１８７： 日本コニカ製エポキシ系シランカップリ
ング剤
〔光硬化性〕メタルハライドランプ使用、◎：接着固定
、表面硬化（タック
フリー）、○：接着固定、表面
未硬化、△：接着固定不十分、
表面未硬化、Ｘ：接着未固定、
表面未硬化
〔接着強度〕Ｂに−７ガラス接着、せん断接着強度
〔耐水性〕
スライドガラス接着片、１０時
間煮沸後、◎：はく離、気泡能、
○：極僅か気泡、はく熱発生、
△ニ一部はく離、気泡発生、×
：完全は（離
比較例１〜３
第２表に示した配合成分を用い、カチオン系紫外線硬化
性樹脂組成物を調製し、光反応性（表面硬化時間、接着
固定時間）、接着強度、硬化収縮率、線膨張率、耐水接
着性などの評価を行った。Table Note) Bp-828: Bisphenol-type epoxy resin manufactured by Yuka Shell Co., Ltd. EARL-4221: U CC manufactured epoxy resin B
RL-4234: U CC alicyclic epoxy resin R-4
5BPI: ffl Epoxy-modified polybutadiene manufactured by Hikari Petrochemical Co., Ltd. BRL-4206: Alicyclic epoxy resin diluent manufactured by IJ CC 5p-170' Cationic photopolymerization initiator manufactured by Mudenka Co., Ltd.^-187: Epoxy-based silane coupling agent manufactured by Nippon Konica Co., Ltd. [Photocuring] Metal halide lamp used, ◎: Adhesive fixed, surface hardened (tack free), ○: Adhesive fixed, surface uncured, △: Adhesive fixed insufficient, surface uncured, X: Adhesive not fixed, surface uncured [Adhesive strength] -7 glass adhesion to B, shear adhesive strength [Water resistance] Slide glass adhesive piece, after boiling for 10 hours, ◎: Peeling, bubble ability, ○: Very few bubbles, heat generation, △D part Peeling, generation of bubbles, ), adhesive strength, curing shrinkage rate, linear expansion coefficient, water resistant adhesion, etc. were evaluated.
得られた結果を第２表に示す。The results obtained are shown in Table 2.
第
表
〔発明の効果〕
以上、説明したように、本発明のエポキシ系樹脂をベー
スレジンとして、無機系粉末を充てんし、分子内エポキ
シ変性ポリブタジェンを含有している紫外線硬化型精密
接着剤は、反応性の高いラジカル系紫外線硬化樹脂組成
物に比べてもそん色ない程、反応性が高（、かつ接着性
や耐水性等の実用性能も十分であり、かつ硬化収縮率や
線膨張率が小さいという特徴を有する。Table 1 [Effects of the Invention] As explained above, the ultraviolet curable precision adhesive which uses the epoxy resin of the present invention as a base resin, fills with inorganic powder, and contains intramolecular epoxy-modified polybutadiene is as follows: Its reactivity is comparable to that of highly reactive radical-based ultraviolet curable resin compositions (and its practical performance such as adhesion and water resistance is sufficient, and its curing shrinkage rate and linear expansion rate are low). It has the characteristic of being small.
これらのことから、本発明の紫外線硬化型精密接着剤を
精密部品、例えば、小さい光部品や電子部品の組立など
に適用すると、ラジカル系紫外線硬化樹脂組成物の欠点
である酸素阻害のだ約の表面未硬化もなく、反応性も高
く、かつ実用性能も良好な接合・接着固定部を実現でき
、その効果は極めて有用なものであり、当業界における
価値は高い。For these reasons, when the ultraviolet curable precision adhesive of the present invention is applied to the assembly of precision parts, such as small optical parts and electronic parts, it is possible to overcome oxygen inhibition, which is a drawback of radical ultraviolet curable resin compositions. It is possible to realize a bonding/adhesive fixing part with no uncured surface, high reactivity, and good practical performance.The effect is extremely useful and has high value in the industry.
第１図は光反応性の評価用サンプルの形状を示す図であ
って、第１−１図は平面図、第１−２図は側面図、第２
図は接着強度の評価方法を示す図であって、第２−１図
は全体の断面概略図、第２−２図は試験片を示す図、第
３図は耐水接着性評価用サンプルの形状を示す図であっ
て、第３−１図は平面図、第３−２図は側面図である。FIG. 1 is a diagram showing the shape of a sample for evaluating photoreactivity, in which FIG. 1-1 is a plan view, FIG. 1-2 is a side view, and FIG.
The figures show the method for evaluating adhesive strength, in which Figure 2-1 is a schematic cross-sectional view of the whole, Figure 2-2 is a diagram showing a test piece, and Figure 3 is a shape of a sample for evaluating water-resistant adhesion. FIG. 3-1 is a plan view and FIG. 3-2 is a side view.
Claims (1)
機系粉末充てん剤５０〜３００重量部及びカチオン系光
重合開始剤からなる樹脂組成物に、分子内エポキシ変性
ポリブタジエンを３〜２０重量部含有していることを特
徴とする紫外線硬化型精密接着剤。1. A resin composition consisting of 100 parts by weight of an epoxy base resin, 50 to 300 parts by weight of an inorganic powder filler and a cationic photopolymerization initiator contains 3 to 20 parts by weight of intramolecular epoxy-modified polybutadiene. UV-curable precision adhesive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4950290A JP2676047B2 (en) | 1990-03-02 | 1990-03-02 | UV curable precision adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4950290A JP2676047B2 (en) | 1990-03-02 | 1990-03-02 | UV curable precision adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03252488A true JPH03252488A (en) | 1991-11-11 |
| JP2676047B2 JP2676047B2 (en) | 1997-11-12 |
Family
ID=12832914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4950290A Expired - Lifetime JP2676047B2 (en) | 1990-03-02 | 1990-03-02 | UV curable precision adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2676047B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5403869A (en) * | 1992-08-17 | 1995-04-04 | Hitachi Chemical Company, Ltd. | Adhesive of epoxy resins, epoxy-modified polybutadiene and photoinitiator |
| JP2002057416A (en) * | 2000-08-10 | 2002-02-22 | Sony Chem Corp | Flexible wiring board for both-side connection |
| WO2004076522A1 (en) | 2003-02-28 | 2004-09-10 | Kuraray Co., Ltd. | Curable resin composition |
| JP2006199778A (en) * | 2005-01-19 | 2006-08-03 | Hitachi Chem Co Ltd | Adhesive composition, adhesive for use in circuit connection, method for connecting circuits using the same, and connected body |
| JP2012041544A (en) * | 2011-09-28 | 2012-03-01 | Hitachi Chem Co Ltd | Adhesive for connecting circuit, method for connecting circuit using the same, and connected body |
| JP2012046757A (en) * | 2011-09-28 | 2012-03-08 | Hitachi Chem Co Ltd | Adhesive for connecting circuit, and circuit connection method and connection body using the same |
| JP2012046756A (en) * | 2011-09-28 | 2012-03-08 | Hitachi Chem Co Ltd | Adhesive for connecting circuit, and circuit connection method and connection body using the same |
| DE102011075401A1 (en) | 2011-05-06 | 2012-05-03 | Carl Zeiss Jena Gmbh | Adhesive, which is curable by UV radiation, useful for bonding components in optical systems e.g. lighting devices, comprises an epoxide resin, a reactive diluent, an adhesion promoter, a UV polymerization initiator, and nanoscale filler |
-
1990
- 1990-03-02 JP JP4950290A patent/JP2676047B2/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5403869A (en) * | 1992-08-17 | 1995-04-04 | Hitachi Chemical Company, Ltd. | Adhesive of epoxy resins, epoxy-modified polybutadiene and photoinitiator |
| JP2002057416A (en) * | 2000-08-10 | 2002-02-22 | Sony Chem Corp | Flexible wiring board for both-side connection |
| WO2004076522A1 (en) | 2003-02-28 | 2004-09-10 | Kuraray Co., Ltd. | Curable resin composition |
| US7632895B2 (en) | 2003-02-28 | 2009-12-15 | Kuraray Co., Ltd. | Curable resin composition |
| JP2006199778A (en) * | 2005-01-19 | 2006-08-03 | Hitachi Chem Co Ltd | Adhesive composition, adhesive for use in circuit connection, method for connecting circuits using the same, and connected body |
| DE102011075401A1 (en) | 2011-05-06 | 2012-05-03 | Carl Zeiss Jena Gmbh | Adhesive, which is curable by UV radiation, useful for bonding components in optical systems e.g. lighting devices, comprises an epoxide resin, a reactive diluent, an adhesion promoter, a UV polymerization initiator, and nanoscale filler |
| JP2012041544A (en) * | 2011-09-28 | 2012-03-01 | Hitachi Chem Co Ltd | Adhesive for connecting circuit, method for connecting circuit using the same, and connected body |
| JP2012046757A (en) * | 2011-09-28 | 2012-03-08 | Hitachi Chem Co Ltd | Adhesive for connecting circuit, and circuit connection method and connection body using the same |
| JP2012046756A (en) * | 2011-09-28 | 2012-03-08 | Hitachi Chem Co Ltd | Adhesive for connecting circuit, and circuit connection method and connection body using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2676047B2 (en) | 1997-11-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1076296A (en) | Photo-polymerizable dental restorative and tooth coating composition comprising an oligomeric resin, an acrylate monomer, an organic peroxide and a photosensitizer | |
| JP2010018797A (en) | Curable composition for optical parts, adhesive agent for optical parts, and sealing agent for organic electroluminescence element | |
| JP5153498B2 (en) | Resin composition | |
| KR20070103204A (en) | Photocuarable resin composition having high thermal conductivity | |
| JP2008308588A (en) | Curable composition and optical device | |
| JPH03252488A (en) | Uv curing type precise adhesive | |
| KR20000064990A (en) | UV curing composition | |
| JP2011111598A (en) | Photocurable resin composition for touch panel and touch panel | |
| JP2010132918A (en) | Cation-curable resin composition containing polymer with two or more oxetanyl groups | |
| JP4170861B2 (en) | Photocurable resin composition | |
| JPS59147016A (en) | Mixture of epoxy containing organic substance | |
| JPH0657103A (en) | Photocurable resin composition | |
| CA1197400A (en) | Dental adhesive system | |
| JP2008308589A (en) | Curable composition and optical device using the same | |
| JP7063684B2 (en) | Adhesives for optical imaging devices and their cured products | |
| JPH04266985A (en) | Photo-setting bonding composition | |
| JPH02296879A (en) | Photocurable adhesive composition | |
| JPS62143922A (en) | Photopolymerizable composition based on epoxy and hydroxyl-containing organic substance | |
| KR20060130396A (en) | Radiation curable adhesive resin composition and the article bonded by radiation curing with the composition | |
| JP2002060484A (en) | Photocurable composition, bonding method using the same and bonded product | |
| JP4713704B2 (en) | Active energy ray-curable resin composition | |
| JP3996334B2 (en) | Photo-curable epoxy resin composition | |
| JPH07118369A (en) | Uv-curable resin composition | |
| US20030105179A1 (en) | Photopolymerizable epoxy composition | |
| JP4395577B2 (en) | Energy ray curable adhesive composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20070725 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080725 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080725 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090725 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090725 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100725 Year of fee payment: 13 |
|
| EXPY | Cancellation because of completion of term | ||
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100725 Year of fee payment: 13 |