JP2005281606A - Epoxy resin composition for radiation curing - Google Patents
Epoxy resin composition for radiation curing Download PDFInfo
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- JP2005281606A JP2005281606A JP2004100805A JP2004100805A JP2005281606A JP 2005281606 A JP2005281606 A JP 2005281606A JP 2004100805 A JP2004100805 A JP 2004100805A JP 2004100805 A JP2004100805 A JP 2004100805A JP 2005281606 A JP2005281606 A JP 2005281606A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 59
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 59
- 239000000203 mixture Substances 0.000 title claims abstract description 24
- 238000003847 radiation curing Methods 0.000 title claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 51
- 239000011347 resin Substances 0.000 claims abstract description 51
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 14
- 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 claims description 22
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 12
- 229920003986 novolac Polymers 0.000 claims description 8
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 6
- 239000011342 resin composition Substances 0.000 claims description 6
- 229930185605 Bisphenol Natural products 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229920005992 thermoplastic resin Polymers 0.000 claims description 4
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 3
- 239000013034 phenoxy resin Substances 0.000 claims description 3
- 229920006287 phenoxy resin Polymers 0.000 claims description 3
- LYPJKORWSCCJIB-UHFFFAOYSA-N CC1=CC=CC=C1CC(C)(I)C1=CC=CC=C1 Chemical group CC1=CC=CC=C1CC(C)(I)C1=CC=CC=C1 LYPJKORWSCCJIB-UHFFFAOYSA-N 0.000 claims 1
- 230000005855 radiation Effects 0.000 abstract description 10
- 239000002131 composite material Substances 0.000 abstract description 8
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 4
- 229920006231 aramid fiber Polymers 0.000 abstract description 4
- 239000004917 carbon fiber Substances 0.000 abstract description 4
- 230000009257 reactivity Effects 0.000 abstract description 4
- 239000002657 fibrous material Substances 0.000 abstract description 2
- 230000005251 gamma ray Effects 0.000 abstract description 2
- 230000001678 irradiating effect Effects 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract 1
- 229910052796 boron Inorganic materials 0.000 abstract 1
- 125000005520 diaryliodonium group Chemical group 0.000 abstract 1
- 230000003014 reinforcing effect Effects 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 13
- 238000010894 electron beam technology Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- -1 urethane modified bisphenol A. Chemical class 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 239000004697 Polyetherimide Substances 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 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 3
- 239000003999 initiator Substances 0.000 description 3
- 229920001601 polyetherimide Polymers 0.000 description 3
- 239000012783 reinforcing fiber Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical compound [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 229920004738 ULTEM® Polymers 0.000 description 1
- 231100000987 absorbed dose Toxicity 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 238000011074 autoclave method Methods 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012952 cationic photoinitiator Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
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- Epoxy Resins (AREA)
Abstract
Description
本発明は、電子線、ガンマー線、Ｘ線等の放射線で硬化するエポキシ樹脂組成物に関する。 The present invention relates to an epoxy resin composition that is cured by radiation such as electron beams, gamma rays, and X-rays.
近年、炭素繊維、ガラス繊維、アラミド繊維等の繊維材料は、各種のマトリックス樹脂と複合化され、得られる強化繊維複合材料は種々の分野・用途に広く利用されるようになってきた。特に最近では、高度の機械的特性や耐熱性等を要求される航空・宇宙分野で、優れた構造部材・部品として用いられるようになってきた。かかる用途のための複合材料・部材の製造法としては、熱硬化性樹脂と強化繊維材料とからなるプリプレグを、多数積層し、オートクレーブ成形により加熱・加圧硬化させるという方法が一般的に行われている。しかしながら、この方法は、一般的に成形コストが高く、成形に要する消費エネルギーも多いという問題点がある。 In recent years, fiber materials such as carbon fibers, glass fibers, and aramid fibers have been combined with various matrix resins, and the resulting reinforcing fiber composite materials have been widely used in various fields and applications. Recently, in particular, it has come to be used as an excellent structural member / part in the aerospace field where high mechanical properties and heat resistance are required. As a method for producing a composite material / member for such an application, a method of laminating a large number of prepregs composed of a thermosetting resin and a reinforcing fiber material, and heating and pressure-curing by autoclave molding is generally performed. ing. However, this method has a problem that the molding cost is generally high and a large amount of energy is required for molding.
そこで、オートクレーブ法に替わる製造技術の開発が進められているが、その一つとして、光重合開始剤（触媒）を添加した樹脂に電子線を照射して架橋反応を起こさせ硬化させる方法がある。かかる方法は、省エネルギー化や処理時間の短縮など多くの利点が期待できる方法である。
しかしながら、従来知られている樹脂と触媒の組合わせ、例えば、エポキシ樹脂とカチオン系の光反応開始剤の組合わせでは、両者の反応性が必ずしも十分ではなく、省エネルギー化や処理時間の短縮化などのメリットを生かしながら、架橋樹脂が十分な硬化度を達成するようにすることは困難であった。 However, conventionally known combinations of resins and catalysts, for example, combinations of epoxy resins and cationic photoinitiators, are not necessarily sufficiently reactive, saving energy and shortening processing time, etc. It was difficult to make the crosslinked resin achieve a sufficient degree of curing while taking advantage of this.
本発明は、特に航空・宇宙分野で利用可能な複合材料・部材を成形するための、反応性に優れた放射線硬化用エポキシ樹脂組成物を提供することを目的とする。 An object of the present invention is to provide a radiation-curable epoxy resin composition having excellent reactivity for molding composite materials and members that can be used particularly in the aerospace field.
本発明の目的は、エポキシ樹脂を主体とする樹脂成分と、該樹脂成分１ｋｇ当たり０．００５〜０．５モルの下記式（１）で表される重合開始剤とからなる、放射線硬化用エポキシ樹脂組成物によって達成される。
本発明の放射線硬化用エポキシ樹脂組成物は、反応性が高いので、照射線量が少なくて済み、従って消費電力量が少なくコスト的に有利である。更に使用する触媒の量も少なくて済むのでコスト的に有利である。そしてこの樹脂と炭素繊維やアラミド繊維等の繊維強化材とからなるプリプレグを用いて、放射線照射により成形された複合材料・部材は、十分な硬化度を有し、機械的あるいは熱的性質に非常に優れたものである。 Since the radiation curing epoxy resin composition of the present invention has high reactivity, it requires only a small amount of irradiation, and therefore has low power consumption and is advantageous in terms of cost. Further, since the amount of the catalyst used is small, it is advantageous in terms of cost. Composite materials and members molded by radiation irradiation using prepregs made of this resin and fiber reinforcements such as carbon fibers and aramid fibers have a sufficient degree of curing and are extremely mechanical or thermal. It is an excellent one.
本発明は、エポキシ樹脂を主体とする樹脂成分と、該樹脂成分１ｋｇ当たり０．００５〜０．５モルの前記式（１）で表される重合開始剤とからなる、放射線硬化用エポキシ樹脂組成物である。エポキシ樹脂としては、具体的には、グリシジルアミン型エポキシ樹脂、ノボラック型エポキシ樹脂、ナフタレン型エポキシ樹脂、ジシクロペンダジエン型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ウレタン変性ビスフェノールＡ型エポキシ樹脂、脂環式エポキシ樹脂などがある。これらは単独又は２種以上混合して用いることが出来る。エポキシ樹脂の中でも、特にビスフェノール型エポキシ樹脂、脂環式エポキシ樹脂、ノボラック型エポキシ樹脂、ナフタレン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂又はこれらの混合物が好ましい。 The present invention is a radiation curable epoxy resin composition comprising a resin component mainly composed of an epoxy resin and 0.005 to 0.5 mol of a polymerization initiator represented by the formula (1) per 1 kg of the resin component. It is a thing. Specific examples of the epoxy resin include glycidylamine type epoxy resin, novolac type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, urethane modified bisphenol A. Type epoxy resin and alicyclic epoxy resin. These can be used alone or in admixture of two or more. Among epoxy resins, bisphenol type epoxy resin, alicyclic epoxy resin, novolac type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin or a mixture thereof is particularly preferable.
本発明においては、前記エポキシ樹脂が主成分として少なくとも５０％存在していれば良く、目的・用途に応じてその他の樹脂、例えば、フェノール樹脂、ビニルエステル樹脂、エポキシアクリレート樹脂、ウレタンアクリレート樹脂、フェノキシ樹脂、アルキド樹脂、ウレタン樹脂等の熱硬化性樹脂や、ポリエーテルエーテルケトン（ＰＥＥＫ）樹脂、ポリエーテルイミド（ＰＥＩ）樹脂、ポリアクリレート樹脂、ポリスルフォン樹脂、ナイロン樹脂、ポリエステル樹脂、ＡＢＳ樹脂、アクリル樹脂、ポリエチレン樹脂、ポリスチレン樹脂、ポリプロピレン樹脂、ポリ塩化ビニール樹脂、ポリカーボネート樹脂、ボリエーテルスルホン樹脂、ポリアミドイミド樹脂、ポリエーテルイミド樹脂、熱可塑ポリイミド樹脂等の熱可塑性樹脂の１種又は２種以上を、最大５０％まで混合して用いることが出来る。 In the present invention, it is sufficient that the epoxy resin is present as at least 50% as a main component, and other resins such as phenol resin, vinyl ester resin, epoxy acrylate resin, urethane acrylate resin, phenoxy are used depending on the purpose and application. Thermosetting resin such as resin, alkyd resin, urethane resin, polyether ether ketone (PEEK) resin, polyether imide (PEI) resin, polyacrylate resin, polysulfone resin, nylon resin, polyester resin, ABS resin, acrylic One type of thermoplastic resin such as resin, polyethylene resin, polystyrene resin, polypropylene resin, polyvinyl chloride resin, polycarbonate resin, polysulfone resin, polyamideimide resin, polyetherimide resin, thermoplastic polyimide resin The two or more kinds can be mixed up to 50%.
本発明において特に好ましい樹脂成分の組み合わせは、ビスフェノールＡ型エポキシ樹脂６０〜９９重量部と熱可塑性樹脂４０〜１重量部とからなるものである。また、ビスフェノールＡ型エポキシ樹脂６０〜９９重量部と、熱硬化性樹脂の一つであるフェノキシ樹脂４０〜１重量部とからなる組合せも好ましい。かかる樹脂組成物の場合には、特に、放射線の照射量が少なくても、非常に硬化度の高い架橋樹脂が得られる。 In the present invention, a particularly preferred combination of resin components consists of 60 to 99 parts by weight of a bisphenol A type epoxy resin and 40 to 1 parts by weight of a thermoplastic resin. Moreover, the combination which consists of 60-99 weight part of bisphenol A type epoxy resins and 40-1 weight part of phenoxy resin which is one of the thermosetting resins is also preferable. In the case of such a resin composition, a crosslinked resin having a very high curing degree can be obtained even when the radiation dose is small.
本発明においては、上記エポキシ樹脂を主体とする樹脂成分に、前記式（１）で表される重合開始剤が添加混合して用いられる。用いる量は、樹脂成分１ｋｇ当たり０．００５〜０．５モル、好ましくは０．０１〜０．１モルである。本発明においては、この重合開始剤を用いる限りその他、硬化剤や硬化促進剤等を特に用いる必要はないが、必要があれば適量用いてもかまわない。また、通常の難燃剤や難燃助剤、粉末状の補強材、着色剤等は必要に応じて用いることが出来るのは言うまでもない。 In the present invention, the polymerization initiator represented by the formula (1) is added to and mixed with the resin component mainly composed of the epoxy resin. The amount to be used is 0.005 to 0.5 mol, preferably 0.01 to 0.1 mol, per 1 kg of the resin component. In the present invention, as long as this polymerization initiator is used, it is not necessary to use a curing agent, a curing accelerator or the like, but an appropriate amount may be used if necessary. It goes without saying that ordinary flame retardants and flame retardant aids, powdery reinforcing materials, colorants and the like can be used as necessary.
前記式（１）において、Ｒ１、Ｒ２はそれぞれ独立に水素又はアルキル基である。アルキル基としては、炭素数に特に制限はないが、メチル基、エチル基又はイソプロピル基等の低級アルキル基が好ましい。また、Ｘはペンタフルオロフェニル基、パラトリフルオロメトキシフェニル基又はジメタ（トリフルオロメチル）フェニル基を表す。本発明においては、式（１）においてＲ１がイソプロピル基、Ｒ２がメチル基、ＸがＣ６Ｆ５基である（トリルクミル）イオドニウム テトラキス（ペンタフルオロフェニル）ボレエートが特に好ましい。 In the formula (1), R 1 and R 2 are each independently hydrogen or an alkyl group. The alkyl group is not particularly limited in the number of carbon atoms, but a lower alkyl group such as a methyl group, an ethyl group or an isopropyl group is preferable. X represents a pentafluorophenyl group, a paratrifluoromethoxyphenyl group, or a dimeta (trifluoromethyl) phenyl group. In the present invention, (triylcumyl) iodonium tetrakis (pentafluorophenyl) borate wherein R 1 is an isopropyl group, R 2 is a methyl group, and X is a C 6 F 5 group in the formula (1) is particularly preferable.
前記した様なエポキシ樹脂を主体とする樹脂成分と、この樹脂成分１ｋｇ当たり０．００５〜０．５モルの前記式（１）で表される重合開始剤とからなる樹脂組成物を、繊維強化材に含浸せしめるとプリプレグが得られる。これに放射線を照射して樹脂を架橋・硬化させると、複合材料・部品とすることができるが、プリプレグ中の樹脂成分の含有量は、通常１０〜７０重量％、好ましくは２０〜５０重量％である。 A resin composition comprising a resin component mainly composed of an epoxy resin as described above and 0.005 to 0.5 mol of a polymerization initiator represented by the formula (1) per 1 kg of the resin component, When the material is impregnated, a prepreg is obtained. When this is irradiated with radiation to crosslink and cure the resin, it can be made into a composite material / part, but the content of the resin component in the prepreg is usually 10 to 70% by weight, preferably 20 to 50% by weight. It is.
本発明において、放射線とは、電子線、ガンマー線、Ｘ線等の電離放射線を意味する。本発明においては、電子線が特に好ましく用いられる。本発明のエポキシ樹脂組成物は反応性が高いので、かかる放射線を照射する場合、低照射線量でも高い硬化度の架橋樹脂となる。特に、エポキシ樹脂がビスフェノール型、脂環型、ノボラック型、ナフタレン型、ジシクロペンタジエン型の中から選ばれるいずれか一つ、または二つ以上の混合物の場合には、少なくとも５kGy（ジュール／ｋｇ）の照射線量で９０%以上の硬化度を得ることができる。 In the present invention, radiation means ionizing radiation such as electron beam, gamma ray, X-ray. In the present invention, an electron beam is particularly preferably used. Since the epoxy resin composition of the present invention has high reactivity, when it is irradiated with such radiation, it becomes a crosslinked resin having a high degree of curing even at a low irradiation dose. In particular, when the epoxy resin is any one selected from bisphenol type, alicyclic type, novolak type, naphthalene type, dicyclopentadiene type, or a mixture of two or more, at least 5 kGy (joule / kg) A curing degree of 90% or more can be obtained with an irradiation dose of.
以下、具体的な実施例により本発明を説明する。各実施例及び比較例において、硬化度は、（硬化後の発熱量）／（硬化前の発熱量）と定義し、示差走査熱量分析に基づき評価される残存発熱量から算出した。示差走査熱量分析は、窒素雰囲気中（窒素流量１００ｍｌ／ｍｉｎ）で昇温速度１０℃／ｍｉｎの条件で行った。 Hereinafter, the present invention will be described with reference to specific examples. In each of the examples and comparative examples, the degree of cure was defined as (calorific value after curing) / (calorific value before curing) and calculated from the residual calorific value evaluated based on differential scanning calorimetry. The differential scanning calorimetry was performed in a nitrogen atmosphere (nitrogen flow rate 100 ml / min) at a temperature increase rate of 10 ° C./min.
[実施例１〜４]
ビスフェノールＡ型エポキシ樹脂（低分子量タイプ、ジャパンエポキシレンジン社製エピコート834）（樹脂−１）の３００ｇに対して、重合開始剤としての（トリルクミル）イオドニウム テトラキス（ペンタフルオロフェニル）ボレエート（Rhodia社製RHODORSIL
PHOTOINITIATOR 2074）（重合開始剤−１）を所定量添加混合し、樹脂組成物を作成した。これをポリプロピレン製容器 (φ２７ mm×高さ５０ mm)に厚さ１ｃｍとなるように注入し供試体を作成した。得られた供試体に、原子燃料工業株式会社製の電子線照射装置（加速電圧１０ＭｅＶ、制動Ｘ線変換装置搭載）を用いて、表１に示した所定量の電子線（２〜３０ｋＧｙ）を照射した。なお、樹脂の吸収線量が同じであれば、電子の加速方法（連続波、パルス波）や加速電圧が異なっても硬化度は同じになる。得られた架橋樹脂の硬化度（％）を測定し、その結果を表１に示した。
[Examples 1 to 4]
For 300 g of bisphenol A type epoxy resin (low molecular weight type, Epicoat 834 manufactured by Japan Epoxy Rangen) (resin-1), (trircumyl) iodonium tetrakis (pentafluorophenyl) borate (RHODORSIL manufactured by Rhodia) as a polymerization initiator
A predetermined amount of PHOTOINITIATOR 2074) (polymerization initiator-1) was added and mixed to prepare a resin composition. This was poured into a polypropylene container (φ27 mm × height 50 mm) to a thickness of 1 cm to prepare a specimen. A predetermined amount of electron beam (2 to 30 kGy) shown in Table 1 was applied to the obtained specimen using an electron beam irradiation device (acceleration voltage 10 MeV, braking X-ray conversion device installed) manufactured by Nuclear Fuel Industries Co., Ltd. Irradiated. If the absorbed dose of the resin is the same, the degree of cure will be the same even if the electron acceleration method (continuous wave, pulse wave) and the acceleration voltage are different. The degree of cure (%) of the obtained crosslinked resin was measured, and the results are shown in Table 1.
[比較例１〜４]
重合開始剤の種類を、本発明のものではないものに変更する以外は、実施例１〜４の場合と同様な実験を行った。そして、得られた架橋樹脂の硬化度を測定し、その結果を表１に示した。表１において、重合開始剤−２は、ヨードニウム塩型光重合開始剤（式２）（チバスペシャルケミカルズ社製IRAGACURE 250）、重合開始剤−３は、ヨードニウム塩型光重合開始剤（式３）（日本曹達社製ＣＩ5102）である。本発明の重合開始剤−１の場合は、その他の重合開始剤の場合に比較して、低照射線量でも硬化が起こっていることがわかる。
[Comparative Examples 1-4]
Experiments similar to those in Examples 1 to 4 were performed except that the type of the polymerization initiator was changed to that not of the present invention. Then, the degree of cure of the obtained crosslinked resin was measured, and the results are shown in Table 1. In Table 1, polymerization initiator-2 is an iodonium salt photopolymerization initiator (formula 2) (IRAGACURE 250 manufactured by Ciba Special Chemicals), and polymerization initiator-3 is an iodonium salt photopolymerization initiator (formula 3). (CI5102 manufactured by Nippon Soda Co., Ltd.). In the case of the polymerization initiator-1 of the present invention, it can be seen that curing occurs even at a low irradiation dose as compared with the case of other polymerization initiators.
[実施例５〜１３]
樹脂成分を変更し、重合開始剤−１を０．０１ｍｏｌ／ｋｇに固定して、それ以外は実施例１〜４との場合と同様な実験を行った。そして、得られた架橋樹脂の硬化度を測定し、その結果を表２に示した。本発明の樹脂組成物は、低照射線量でも硬化が起こっていることがわかる。
[Examples 5 to 13]
The resin component was changed, the polymerization initiator-1 was fixed at 0.01 mol / kg, and the other experiments were performed in the same manner as in Examples 1 to 4. Then, the degree of cure of the obtained crosslinked resin was measured, and the results are shown in Table 2. It can be seen that the resin composition of the present invention is cured even at a low irradiation dose.
表２において、樹脂の種類は以下のものを示している。
樹脂−２：ビスフェノールＡ型エポキシ樹脂（低分子量タイプ、ジャパンエポキシレンジン社製エピコート828）、樹脂−３：ビスフェノールＡ型エポキシ樹脂（低分子量、低塩素濃度タイプ、大日本インキ社製850Ｓ）、樹脂−４：ナフタレン型エポキシ樹脂（大日本インキ社製ＨＰ−4032）、樹脂−５：ビスフェノールF型エポキシ樹脂（ジャパンエポキシレンジン社製エピコート807）、樹脂−６：ノボラック型エポキシ樹脂（ジャパンエポキシレンジン社製エピコート152）、樹脂−７：ノボラック型エポキシ樹脂（ジシクロペンタジエン骨格含有）（大日本インキ社製ＨＰ-7200Ｌ）、樹脂−８：ノボラック型エポキシ樹脂（日本化薬社製ＥＰＰＮ-501ＨＹ）、樹脂−９：ノボラック型エポキシ樹脂（ビフェニル骨格含有）（日本化薬社製ＮＣ3000）、樹脂−10：脂環式エポキシ樹脂（ダイセル・ユーシーシー社製セロキサイド2021）。
In Table 2, the types of resin are as follows.
Resin-2: Bisphenol A type epoxy resin (low molecular weight type, Epicoat 828 manufactured by Japan Epoxy Rangen), Resin-3: Bisphenol A type epoxy resin (low molecular weight, low chlorine concentration type, 850S manufactured by Dainippon Ink Co., Ltd.), resin -4: Naphthalene type epoxy resin (HP-4032 manufactured by Dainippon Ink Co., Ltd.), Resin-5: Bisphenol F type epoxy resin (Epicoat 807 manufactured by Japan Epoxy Rangen), Resin-6: Novolak type epoxy resin (Japan Epoxy Rangen Co., Ltd.) Epicoat 152), Resin-7: Novolac type epoxy resin (containing dicyclopentadiene skeleton) (HP-7200L manufactured by Dainippon Ink Co., Ltd.), Resin-8: Novolac type epoxy resin (EPPN-501HY manufactured by Nippon Kayaku Co., Ltd.), Resin-9: Novolac-type epoxy resin (containing biphenyl skeleton) (NC3000 manufactured by Nippon Kayaku Co., Ltd.) Resin -10: alicyclic epoxy resin (manufactured by Daicel Yu CC Co. Celloxide 2021).
[実施例１４〜１５]
樹脂成分としてビスフェノールＡ型エポキシ樹脂（樹脂−１）１００部（重量単位）と熱可塑性樹脂（日本ジーイープライチック社製ウルテム1000-1000）(樹脂−11)３０部との混合物、及び樹脂−１の１００部とフェノキシ樹脂（InChem社製ＰＫＨＰ-200）（樹脂−12）の３０部との混合物を用い、重合開始剤−１を０．０１ｍｏｌ／ｋｇに固定して、それ以外は実施例１〜４との場合と同様な実験を行った。そして、得られた架橋樹脂の硬化度を測定し、その結果を表３に示した。照射線量が１５ｋＧｙでも、硬化度が９０％以上に達していることがわかる。
[Examples 14 to 15]
As a resin component, a mixture of 100 parts (by weight) of a bisphenol A type epoxy resin (resin-1) and 30 parts of a thermoplastic resin (Ultem 1000-1000 manufactured by Nippon Gee-Plic Corporation) (resin-11), and resin-1 Example 1 was used except that a mixture of 100 parts of phenoxy resin (PKHP-200 manufactured by InChem) (30 parts of resin-12) was used, and polymerization initiator-1 was fixed at 0.01 mol / kg. Experiments similar to those for ˜4 were performed. The degree of cure of the obtained crosslinked resin was measured, and the results are shown in Table 3. It can be seen that even when the irradiation dose is 15 kGy, the curing degree reaches 90% or more.
本発明の放射線硬化用エポキシ樹脂組成物は、炭素繊維やアラミド繊維等の強化繊維材料に含浸させてプリプレグを製造するのに用いることができる。そして、これに放射線を照射して成形された複合材料・部材は、十分な硬化度を有し機械的あるいは熱的性質に優れている。従って、得られた複合材料・部材は、航空・宇宙分野はもちろん、その他の一般産業分野に広く使用される。
Claims (8)
The epoxy resin is any one selected from bisphenol type, alicyclic type, novolak type, naphthalene type, dicyclopentadiene type, or a mixture of two or more, and cured at 90% or more with an irradiation dose of at least 5 kGy. The epoxy resin composition for radiation curing according to claim 1, wherein the degree can be obtained.
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| WO2007034679A1 (en) * | 2005-09-22 | 2007-03-29 | Toho Tenax Co., Ltd. | Resin composition for radiation curing and prepreg |
| JP2008088277A (en) * | 2006-09-30 | 2008-04-17 | Toho Tenax Co Ltd | Resin composition for heat or radiation curing and prepreg |
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| JP2000186106A (en) * | 1998-12-22 | 2000-07-04 | Sekisui Chem Co Ltd | Polymerization of photo cation polymerizable composition |
| JP2002062649A (en) * | 2000-08-21 | 2002-02-28 | Ngk Spark Plug Co Ltd | Photosensitive resin composition for printed wiring board and printed wiring board |
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| JP2000186106A (en) * | 1998-12-22 | 2000-07-04 | Sekisui Chem Co Ltd | Polymerization of photo cation polymerizable composition |
| JP2002062649A (en) * | 2000-08-21 | 2002-02-28 | Ngk Spark Plug Co Ltd | Photosensitive resin composition for printed wiring board and printed wiring board |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2007034679A1 (en) * | 2005-09-22 | 2007-03-29 | Toho Tenax Co., Ltd. | Resin composition for radiation curing and prepreg |
| JP2008088277A (en) * | 2006-09-30 | 2008-04-17 | Toho Tenax Co Ltd | Resin composition for heat or radiation curing and prepreg |
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