JP2006117950A - Energy ray-curing resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a highly curable energy ray-curing resin composition which has an extremely higher curing ability than conventional energy ray-curing resins, is simple, and has a high design flexibility. <P>SOLUTION: This composition contains an epoxy resin having a cyclic ether structure in its molecular structure as a photopolymerizable resin component, a photo-initializing agent component which enables the cure of the photopolymerizable resin component by an energy ray radiation, and a curing agent component using for the ambient temperature or high temperature cure of the photopolymerizable resin component. As the photo-initializing agent component, a predetermined sulfonium salt is contained. The curing agent is an acid anhydride. The content of the curing agent is 0.1-1.4 mol against 1 mol of the photopolymerizable resin component that can react with the curing agent. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

Contains resin components, UV (ultraviolet rays), EB (electron beam), infrared rays, X-rays, visible rays, argon, CO ₂ or excimer lasers, solar rays, and heat rays such as radiation and radiation The present invention relates to a highly curable energy beam curable resin composition in a so-called energy beam curable resin composition. In particular, the present invention relates to a resin composition having improved curability based on an energy ray curable resin composition, a method for producing such a composition having improved curing ability, and the like.
Here, the energy ray curable resin composition is effective irrespective of the photosensitizer, photosensitizer, reactive diluent, other fillers and additives used, and the photopolymerization initiator. By using an appropriate component (for example, a photo / thermal polymerization initiator or a chain-curing photopolymerization initiator component), the shape of the filler or additive, the presence or absence of UV shielding, the film thickness or shape of the cured product In addition to general molding materials and casting materials, it is effective regardless of paste materials, composite materials, grinding stone materials, adhesives, sealants, varnishes, paints, inks, toners, coating materials, etc. It is applicable to various fields that can be handled.

  In recent years, in various fields, considering cost reduction, easy molding, workability improvement, productivity improvement, workability improvement, workability improvement, energy saving, space saving, safety improvement, environmental conservation improvement, etc. Application of an energy beam curable resin having a characteristic of energy beam curing typified by UV curing has been studied, but a lack of ability of energy beam curing can be cited as a factor that hinders application. The energy ray curable resin represented by the UV curable resin has a feature of curing only a portion irradiated with an energy ray of a certain amount or more, and the energy ray represented by the UV passes through the resin. Therefore, the phenomenon of energy ray curing has a feature that it is greatly influenced by the curing ability of the resin itself, the intensity of the energy rays, the irradiation time, the attenuation characteristics, and the like. In the future, in order to expand the use of this technology and to apply it to various fields, there are many cases where high curing ability is required. However, as a conventional method for improving energy beam curing ability, , Improvement of the performance of the photoinitiator, increase of the intensity of the energy beam to be irradiated, increase of the irradiation time, change of the type of the energy beam, and the like.

  However, when the above method is employed, there are problems such as time and cost for development of the initiator on the resin composition side, or high cost of the resin composition. On the energy beam irradiation equipment / equipment side, there are problems such as larger equipment, increased energy consumption, increased running costs, reduced productivity, specialized radiation sources, expensive equipment / equipment, and reduced safety. was there. For this reason, unless problems such as loss of advantages of energy beam curing and increase in total cost are not solved, the above method itself is difficult to use and apply. For example, the cured film thickness of a general energy beam curable resin is the number of surface layers that an effective energy beam reaches, and the effective energy beam does not reach when the transmission distance of the energy beam becomes long. is there. When considering the improvement of the curing ability, it is possible to change the resin composition, increase the intensity of irradiated energy rays, change the radiation source, etc. It becomes. Therefore, the energy ray curing application field so far has centered on limited areas such as photoresists, coatings, paints, adhesives and varnishes.

Typical examples of improved energy ray curing ability include high UV curable resins (Mitsubishi Rayon Co., Ltd., active energy ray curable composition, Patent Document 1: JP-A-8-283388) and UV / heating. Combination curing type resins (Asahi Denka Kogyo Co., Ltd .: Optomer KS series, Hitachi Chemical Co., Ltd .: Radicure, Toyobo: UE resin, Patent Document 2: Japanese Patent Publication No. 61-38023, etc.) and the like. However, conventional high-curing energy beam curable resins represented by high UV curable resins have been developed with new photopolymerization initiators effective for energy beam curing, or new photopolymerizability, although there are few examples. This was due to the development of the oligomer, and it was difficult to say that it was possible to easily obtain a composition suitable for the application, including the above-mentioned problems. In addition, UV / heating combined curable resins are characterized by having a wider range of curing conditions, but the above-mentioned problems of conventional high-curing energy ray curable resins remain as they are. Because of the necessity, a heating device and equipment are required, so that the advantages of energy ray curing have been impaired in the direction of the equipment and equipment.
JP-A-8-283388 Japanese Examined Patent Publication No. 61-38023

  Therefore, the present inventors have taken into consideration the above-described drawbacks of the conventional energy beam curable resin and the necessity of improving the curing ability, and the novel drawbacks of the conventional highly curable energy beam curable resin and the curing ability improvement method. We have intensively studied high-curable energy ray-curable resin compositions. As a result, in addition to the photopolymerizable resin component and the photopolymerization initiator component, the present inventors have a novel high curability containing a curing agent component that cures the photopolymerizable resin component by a method other than energy beam irradiation. According to the energy ray curable resin composition and, further, the energy ray curable resin composition containing a curing accelerator component that accelerates the curing when cured by a method other than the energy ray irradiation, the curing ability is higher than that of the conventional energy ray curable resin. It has been found that the above-mentioned problems that the energy ray curable resin has can be solved. The present invention has been completed from such a viewpoint.

That is, the object of the present invention can be effectively achieved by having the following configuration.
(1) A photopolymerizable resin component that can be cured by irradiation with energy rays, such as a photopolymerizable oligomer or a photopolymerizable monomer, and photopolymerization that enables curing of the photopolymerizable resin component when irradiated with energy rays. An initiator component and a curing agent component that can be used to cure at least one of the photopolymerizable resin components by a method other than energy ray curing such as room temperature curing or heat curing. Energy ray curable resin composition,
(2) A curing accelerator component that accelerates the curing when curing at least one of the photopolymerizable resin components and the curing agent component by a method other than energy ray irradiation such as room temperature curing or thermal curing. An energy ray curable resin composition according to the above (1), comprising:

(3) The energy ray curable resin composition according to (1) or (2), wherein the photopolymerizable resin component includes an epoxy resin component having a cyclic ether structure in the molecular structure, (4) The energy beam curable resin according to any one of the above (1) to (3), wherein the curing agent component comprises an acid anhydride or a derivative of an acid anhydride such as dicarboxylic acid or an esterified product thereof. Composition, (5) The energy ray curable resin composition according to any one of (1) to (3) above, which contains a monovalent or polyvalent alcohol as the curing agent component,

(6) The said hardening | curing agent component or the said hardening accelerator component contains an acid anhydride or its derivative (s), and monohydric or polyhydric alcohol, The said (2) or (3) characterized by the above-mentioned. Energy ray curable resin composition,
(7) The above (3) to (3), wherein the curing agent component or the curing accelerator component is composed of a compound that can react with the epoxy resin component and does not have a nitrogen atom in the molecular structure. 6) The energy beam curable resin composition according to any one of

(8) The energy beam according to any one of the above (3) to (7), wherein the photopolymerizable resin component includes 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate. Cured resin composition,
(9) The energy ray curable resin composition according to any one of (4) or (6) to (8) above, wherein maleic anhydride or a derivative thereof is included as the acid anhydride or a derivative thereof. ,
(10) The energy ray curable resin composition according to any one of the above (5) to (8), which contains polyethylene glycol as the alcohol.

(11) The above (1) to (10), wherein the curing agent component is contained in a ratio of 0.1 mol to 1.4 mol with respect to 1 mol of the photopolymerizable resin component capable of reacting with the curing agent component. The energy beam curable resin composition according to any one of
(12) The above (2), (3) or (6) to (11), wherein the curing accelerator component is contained in a ratio of 0.04 mol to 0.6 mol with respect to 1 mol of the curing agent component. The energy beam curable resin composition according to any one of

(13) The energy ray curable resin composition according to any one of (1) to (12) above, which contains a cationic photopolymerization initiator component as the photopolymerization initiator component, (14) As a photopolymerization initiator component, the following general formula (I), (II) or (III)

An energy ray curable resin composition according to any one of the above (1) to (13), comprising an iron-allene compound represented by:
(15) The photopolymerization initiator component includes a photo / thermal polymerization initiator capable of initiating polymerization with both light and heat, as described in any one of (1) to (14) above Energy ray curable resin composition,
(16) As the photopolymerization initiator component, the following general formula (IV), (IV ′) or (V)

An energy ray-curable resin composition according to any one of the above (1) to (15), comprising a sulfonium salt represented by
(17) The above (1) to (16), wherein the photopolymerization initiator component includes a polymerization initiator component comprising a binary system or more including a photopolymerization initiator and a photo / thermal polymerization initiator. The energy beam curable resin composition according to any one of

(18) The polymerization initiator component composed of the binary system or more is an aryl sulfonium salt or an iron-allene compound represented by the above general formula (I), (II) or (III) as a photopolymerization initiator. The energy ray curable resin according to (17) above, comprising at least one of the sulfonium salts represented by the general formula (IV) or (V) as a photo / thermal polymerization initiator. Composition,
(19) The above (17) or (18), wherein the polymerization initiator component comprising the binary system or more contains a photo / thermal polymerization initiator in a ratio of 10 to 100% by weight. Energy beam curable resin composition, and
(20) The above (characteristic), wherein the photopolymerization initiator component is in a ratio of 0.1 parts by weight to 6.0 parts by weight with respect to 100 parts by weight of the total weight of the components other than the photopolymerization initiator component. It is an energy beam curable resin composition in any one of 1)-(19).

  Although the said resin composition shows a high hardening characteristic by having the structure of said (1)-(20), these characteristics (effects) are other by having the structure of said (1)-(20). It can be applied to any energy ray curable resin composition. Generally, the energy ray curable resin composition includes a photocurable resin component and a photopolymerization initiator component. Therefore, in the above (1) to (20), the components (for example, the photopolymerizable resin component and the photopolymerization initiator component) contained in the energy beam curable resin composition are replaced with the energy beam curable resin composition, By satisfying (1) to (20), it is possible to give the same characteristics to other energy ray curable resin compositions (for example, imparting high curing characteristics). Specifically, for example, (i) at least one photopolymerizable resin component of the energy beam curable resin composition is applied to the energy beam curable resin composition by a method other than energy beam irradiation such as room temperature curing or heat curing. By adding a curing agent component that can be used for curing to the energy ray curable resin composition, the curing ability is improved, and (ii) the energy ray curable resin composition is added to the curing agent according to (i) above. When curing the component, at least one photopolymerizable resin component of the energy beam curable resin composition, and the curing agent component by a method other than energy beam irradiation such as room temperature curing or heat curing, the curing is performed. The curing ability is improved by adding a curing accelerator component that promotes the curing to the energy beam curable resin composition, and (iii) the energy beam curable resin composition has a cyclic structure in the molecular structure. When the epoxy resin component having a tellurium structure is contained, the curing agent component used for curing at least one of the epoxy resin components by a method other than energy ray irradiation such as room temperature curing or heat curing is used. The curing ability is improved by adding to the resin composition, and further, a curing accelerator component that accelerates the curing when curing at least one of the epoxy resin component and the curing agent component is added to the energy ray curable resin. Adding to the composition improves the curing ability,

  (Iv) Curing ability improves because the hardening | curing agent component as described in said (i)-(iii) contains an acid anhydride or its derivative (v) The hardening | curing agent as described in said (i)-(iii) When the component contains a monovalent or polyhydric alcohol, the curing ability is improved, and (vi) an acid anhydride or a derivative thereof as the curing agent component or the curing accelerator component described in (ii) or (iii) above And a monovalent or polyhydric alcohol, the curing ability is improved, and (vii) the curing agent component or curing accelerator component described in (iii) to (vi) above is an epoxy resin component. Curing ability is improved by comprising a compound that can react and does not have a nitrogen atom in the molecular structure,

  (Viii) Curing ability is improved by including maleic anhydride or a derivative thereof as the acid anhydride or derivative thereof described in (iv) or (vi), and (ix) (v) or (vi) above In addition to the above (i) to (ix), a photo / thermal polymerization initiator is added to the energy ray curable resin composition because polyethylene glycol is included as the alcohol described in 1. Curing ability is improved by adding to the energy ray curable resin composition.

The composition has the following uses.
(21) An energy beam obtained by curing the energy beam curable resin composition according to any one of (1) to (20) above by some curing means such as energy beam irradiation, room temperature curing, or heat curing. Cured resin molded body (mainly an energy beam curable resin molded body according to the present invention, including a cured resin, a resin product, etc.),
(22) Paste material (magnetic paste, conductive paste, solder, metal paste, inorganic paste, (thin film) containing the energy ray curable resin composition according to any one of (1) to (20) above Including rib paste etc.),
(23) A composite molding material (molding material, casting material, filler (inorganic filler, organic filler, or the like) characterized by containing the energy ray-curable resin composition according to any one of (1) to (20) above. Including metal fillers) filler materials, fibers (glass fibers, carbon fibers, inorganic fibers, organic fibers, metal fibers, etc.) reinforced composite materials, grinding stone materials (abrasive binder), etc.),

(24) An adhesive (including a sealing material) containing the energy ray curable resin composition according to any one of (1) to (20), and (25) (1) ) To (20) a coating material (varnish (insulating varnish etc.)), sealing material (diode, IC, capacitor, electronic substrate etc.) characterized by containing the energy ray curable resin composition according to any one of Paint, toner or ink).

  That is, in summary, the invention described in the present specification includes at least one of the photopolymerizable resin component in addition to the photopolymerizable resin component and the photopolymerizable initiator component, which are essential components of the energy ray curable resin composition. A highly curable energy ray curable resin composition containing a curing agent component as an essential component that can be used when the seed is cured by a curing method other than energy ray curing such as room temperature curing or heat curing, and in addition to this resin composition When curing by a curing method other than energy beam curing such as room temperature curing or heat curing, a highly curable energy beam curable resin composition containing a curing accelerator component that is a component that enables acceleration of the curing reaction, And energy energy such as room temperature curing or thermosetting at least one resin component of the energy beam curable resin composition. By adding a curing accelerator component that can be used for curing by a method other than irradiation, and a curing accelerator component that can accelerate the curing reaction between the resin component and the curing agent component, an energy ray curable resin Methods for improving the energy ray curing ability of the composition, as well as resin moldings and application materials (paste materials, composite materials, adhesives, coating materials, etc.) using these specific energy ray curable resin compositions, and applications It relates to possible materials. In particular, an epoxy resin with excellent physical properties as a photopolymerizable resin component and abundant types of curing agents, an acid anhydride or an acid anhydride derivative typified by maleic anhydride as a curing agent component, and a curing accelerator component It is preferable to include monohydric or polyhydric alcohols represented by polyethylene glycol. The present invention also relates to a composition ratio of the curing agent component and a composition ratio of the curing accelerator component.

Further, the photopolymerization initiator component is particularly preferably a cationic photopolymerization initiator, a photo / thermal polymerization initiator, or a photopolymerization initiator comprising a binary system of a photopolymerization initiator and a photo / thermal polymerization initiator. The system is used. In particular, the iron-allene compound type, phosphonium salt type, sulfonium salt type of the above general formula (I) to general formula (III), the photo / thermal polymerization initiator of the above general formula (IV) to general formula (V), , At least one of the above-described general formula (I) to general formula (III) iron-allene compound type, sulfonium salt type, aryl sulfonium salt type (triarylsulfonium salt), and general formula (IV) to general formula ( Those containing a photopolymerization initiator comprising at least one binary system including at least one of the photo / thermal polymerization initiators V) are suitably used. The present invention also relates to a composition ratio of a photopolymerization initiator system comprising the above binary system or more.
The present invention further improves the curing ability of the energy ray curable resin composition by adding the above specific component to the constituent components of the resin composition, and curing of the resin composition using the resin composition. The present invention relates to a product, a molded product, a product, and a utilization method such as production by the resin composition or energy beam curing method.

    According to the present invention, various cured products, molded products, and manufactured products can be obtained by using an energy beam curable resin that has an extremely high curing capability than conventional energy beam curable resins, is simple, and has a high degree of design freedom. Can do. The energy ray curable resin used can also be used for molding materials, fiber reinforced composite materials, carbon fiber reinforced composite materials, other composite materials, adhesives, sealants, varnishes, paints or coating materials, inks or toners, etc. It is.

  First, the inventors of the present invention require a long time and cost to develop a resin composition, the resin composition is expensive, and it is difficult to easily obtain a suitable resin composition for each application. The disadvantages of this are due to the development of new photopolymerization initiators and related photosensitizers, the development of photosensitizers, and the development of new photopolymerizable oligomers. Paying attention to the fact that the curing mechanism is the same as before, and that it is easy to impair the advantages of energy beam curing if the improvement of the curing capacity is burdened on the equipment, photopolymerization initiator, photosensitizer, photosensitizer, photopolymerization Improvement of curing ability by resin composition components other than the conventionally developed target components such as functional oligomers, improvement of curing ability by combination of new components to the resin composition, provision of curing ability other than conventional photocuring mechanism, inexpensive curing ability improvement composition, Easy resin characteristics for each application As a result of intensive research on the above, the following problems are associated with the conventional high-curing energy beam curable resin, which has higher curing ability than the conventional energy beam curable resin, the resin composition is inexpensive, and the resin characteristics can be easily controlled. A new high-curing energy ray-curable resin composition that has been solved and a method for improving the energy ray-curing ability that is simple and has a high degree of design freedom have been developed.

Examples of the energy rays include electron rays, X rays, infrared rays, sunlight rays, visible rays, various lasers (excimer laser, CO ₂ laser, argon laser, etc.), heat rays (radiation, radiation, etc.) and the like. In addition, the developed high-curing energy beam curable resin composition can be cured by heat or the like as light or electromagnetic waves as the energy to be applied, as shown by the characteristics of the resin composition containing a curing agent component. Furthermore, it is effective to improve the energy ray curing characteristics by preheating the resin composition to such an extent that the resin composition is not cured from the characteristics of the resin composition.

  First, as a highly curable energy ray curable resin composition, a so-called photopolymerizable resin component that can be used for energy ray curing such as a photopolymerizable oligomer or a photopolymerizable monomer, and energy ray curing of the resin component are possible. A photopolymerization initiator component to be cured and a curing agent component that can be used when curing at least one of the resin components by a curing method other than energy ray curing, such as room temperature curing or heat curing, as essential components Energy ray curable resin composition, and curing accelerator capable of accelerating the curing reaction when the resin component and the curing agent component are cured by thermal curing or the like in addition to the highly curable energy ray curable resin composition A high-curing energy beam curable resin composition, an energy beam curable resin composition (for example, an existing energy beam curable resin composition or A continuous material, a new energy ray curable resin composition, etc.) are cured by a method other than energy ray irradiation, such as room temperature curing or thermosetting, at least one of the resin components of the energy ray curable resin, particularly the photopolymerizable resin component. A curing agent component that can be used as an essential component to improve the curing ability of the energy ray curable resin composition, and curing when the resin component and the curing agent component are cured by thermal curing or the like A method of improving the curing ability of the energy ray curable resin composition by adding a curing accelerator component that enables the acceleration of the reaction to the energy ray curable resin composition has been developed. In the present invention, it is also effective for those obtained by adding an appropriate photoinitiator component to a cured resin composition (including related materials) to impart energy ray curing characteristics. In addition, with the above composition, the material design by the photopolymerizable resin component and the fillers and additives, which has been the center of the conventional physical property control method of the energy ray curable resin, is the heat of physical property control by a curing agent and a curing accelerator. It is possible to combine general material design techniques for curing, which broadens and facilitates the material design techniques.

  The reason why the curing ability of the energy ray curable resin composition having each of the above components is improved is considered as follows. First, when an energy beam is irradiated to the resin composition, the photopolymerizable resin component is cured by the photopolymerization initiator component, and at this time, heat is dissipated by heat generated by curing. Next, receiving this heat, thermosetting occurs between the photopolymerizable resin component and the curing agent component. The different curing mechanisms of energy beam curing and thermal curing as described above function almost simultaneously and, in some cases, make up for insufficient curing, so that the present invention improves the overall curing capability compared to energy beam curing alone.

  Here, as a photopolymerizable resin component, for example, various acrylates represented by epoxy acrylate, epoxidized oil acrylate, urethane acrylate, polyester acrylate, polyether acrylate, vinyl / acrylate, polystyrylethyl methacrylate, and alicyclic type Various photopolymerizable oligomers such as epoxy, glycidyl ether type epoxy, bisphenol type epoxy, novolak type epoxy, etc., unsaturated polyester, polyene / thiol, silicon, polybutadiene, vinyl ether compound, epoxidized polyolefin, etc. Although various photopolymerizable monomers, such as a monomer, an acrylic monomer, vinyl ether, and cyclic ether, can be illustrated, it is not limited to this. As the photopolymerization initiator component, the suitability differs depending on the target photopolymerizable resin component such as a radical photopolymerization initiator, a cationic photopolymerization initiator, an anionic photopolymerization initiator, etc. Diazonium salt type compounds as shown, iodonium salt type compounds as shown in Table 2, the following general formula

Compounds of the pyridinium salt type as shown in FIG. 6, phosphonium salt type compounds as shown in JP-A-6-157624, JP-A-7-82283, and sulfonium salt type compounds as shown in Table 3 to be described later Compound, iron-allene compound type compound represented by the above general formulas (I), (II), (III), sulfonate type compound, light / heat represented by the above general formulas (IV), (V) Polymerization initiator, P1-type photopolymerization initiator shown in Table 4 below, and P2-type photopolymerization initiator shown in Table 5 below, Co-amine min complex, O-acyl oxime, benzyloxycarbonyl derivative, formamide Examples of such a photobase generator include, but are not limited to.

Recently, anionic tetrakis cationic photopolymerization initiator _{(pentafluorophenyl) borateB (C 6 F} 5) 4 - hitherto typical (e.g. hexafluoroantimonate SbF ₆ ^-) of that in the comparison performance is reported good Therefore, further improvement in performance can be expected. For details on these resin components, photopolymerization initiator components, and fillers and additives described below, the General Technical Center (February 28, 1989) issued by the author, Kiyomi Kato “UV Curing System”, edited by the Society of Polymer Science "Volume 6 Optical Functional Materials" Kyoritsu Publishing Co., Ltd. (June 15, 1991), Lecturer Kiyomi Kato "Trends and How to Select and Use Photoinitiators for UV Curing" Workshop Text Organized by Techno Forum Co., Ltd. ( November 27, 1992 (Friday)), Lecturer Masahiro Tsunooka “Recent Trends in Photocrosslinking Systems and Their Applications: Chemistry of Photoacid / Base Generators and Applications in Polymer Materials” You can refer to the documents and documents listed in the Association for Corporate Training (Tuesday, September 17, 1996).

  The curing agent component differs depending on the resin component as a partner, and examples thereof include epoxies and isocyanates when the photopolymerizable resin component contains a hydroxyl group, and amines, acid anhydrides, polyols and the like when the epoxy group contains. However, it is not limited to this. What is important here is that a curing (chemical reaction) other than energy ray curing such as room temperature curing or heat curing is possible between at least one of a curing agent component and a photopolymerizable resin component as essential components. It is true. Each of the curing agent component, the photopolymerizable resin component, and the photoinitiator component may be a plurality of components. In some cases, even if the photopolymerizable resin component is positioned as a curing agent component by switching the positional relationship between the curing agent component and the photopolymerizable resin component (usually the main component of the composition is the resin component and the subcomponent is The hardener component is reversed, but the main component of the composition is the hardener component and the subcomponent is a photopolymerizable resin component (in this case, the photoinitiator component is related to the subcomponent) )) As long as the above relationship is established, there is no problem even if the curing agent component of one kind of photopolymerizable resin component is a photopolymerizable resin component. In particular, when both the main agent component and the curing agent component are photopolymerizable resin components, the photopolymerization initiator component suitable for at least one of the main agent component and the curing agent component may be used. In addition, it is possible to design materials with a wide range of energy beam curing characteristics. Further, other components may be added to the resin composition of the present invention comprising each essential component, for example, other photopolymerizable resin components unrelated to the essential curing agent component and photopolymerization initiators related thereto. Ingredients may be added.

  The curing accelerator component also differs depending on the photopolymerizable resin component and the curing agent component. For example, monovalent or polyhydric alcohols for amines, monohydric or polyhydric alcohols for acid anhydrides such as acid anhydrides, etc. The amine can be exemplified, but is not limited thereto. What is important here is that the curing accelerator component as an essential component accelerates a curing reaction (chemical reaction) that can occur between the above-described essential curing agent component and at least one of the photopolymerizable resin components. It has a function. Here, as in the case of the curing agent component, the other component and the curing accelerator component may each be a plurality of components, and in some cases, the curing accelerator component functions as a curing agent component or a photopolymerizable resin component. It can be considered that the photopolymerization initiator component has the function of the curing agent component defined in the present invention (in this case, the curing agent component may not be provided separately). As long as it has an accelerating function, it is the present invention. Generally, in the case of components (substances) that function as both a curing agent component and a curing accelerator component, the positioning of the component (substance) is often distinguished by the proportion of the content contained in the composition. For example, taking the above (6) as an example, when the proportion of acid anhydride or the like is large, the acid anhydride or the like acts as a curing agent component, and the alcohol acts as a curing accelerator. On the other hand, when the proportion of alcohols is large, alcohols act as curing agent components, and acid anhydrides and the like act as curing accelerators. When the amount of both is large, both have both functions. In addition, when both the curing accelerator component and the curing agent component can react with at least one of the photopolymerizable resin components, easier curing can be expected. In addition, other components may be added to the resin composition of the present invention composed of the above components, for example, other photopolymerizable resin components unrelated to the curing agent component and the curing accelerator component, and light related thereto. A polymerization initiator component may be added.

  Specific examples of highly curable energy ray curable resin compositions include, for example, epoxy acrylate (photopolymerizable resin component), radical photopolymerization initiator (photopolymerization initiator component), acid anhydride (curing agent component). ) And polyol (curing accelerator component), epoxy acrylate and epoxy resin (photopolymerizable resin component), radical photopolymerization initiator and cationic photopolymerization initiator (photopolymerization initiator component) and acid Resin composition containing anhydride (curing agent component), epoxy resin (photopolymerizable resin component), cationic photopolymerization initiator (photopolymerization initiator component), acid anhydride (curing agent component), and polyol (curing acceleration) Resin component, epoxy resin (photopolymerizable resin component), anionic photopolymerization initiator (photopolymerization initiator component), amines (curing agent component) and acid anhydride (curing accelerator) Resin composition comprising a component), but it can be given, but is not limited thereto. As a precaution for the above material design, it is important not to cause curing inhibition between various components in the resin composition, particularly not to cause curing inhibition between the photopolymerization initiator component and other components, For example, amines that are curing inhibitors of cationic photoinitiator components should be avoided when using cationic photoinitiator components.

  In particular, the epoxy resin component is preferred as the photopolymerizable resin component from the viewpoint that the types of the curing agent component and the curing accelerator component are abundant and the physical properties of the cured product are good, and in particular, 3,4-epoxycyclohexylmethyl-3, 4-Epoxycyclohexanecarboxylate is preferred. In particular, as the curing agent component or the curing accelerator component, acid anhydrides or acid anhydride derivatives, monovalent or polyhydric alcohols are preferable. For example, examples of the acid anhydride include compounds shown in Table 6, and examples of the monovalent or polyvalent alcohols include compounds having a hydroxyl group in a chemical structure such as phenol, novolak, glycol, alcohol, polyol, and the like. It is also preferable in the case of the epoxy resin component.

  When the epoxy resin component is used as the photopolymerizable resin component, the curing agent component and the curing accelerator component include a functional group capable of reacting with an epoxy group (an carboxylic anhydride group, a carboxylic acid group, a hydroxyl group, an amine group, an amide group). , Urethane groups, urea groups, isocyanate groups, other functional groups described in Table 7 and the like), but generally, amines, amides (polyamides), acid anhydrides as curing agent components Examples of curing accelerator components such as phenols and the like include acid anhydrides, polyols, and amines. In particular, an acid anhydride or an acid anhydride derivative and a monovalent or polyhydric alcohol are preferred. Further, a compound that does not contain a nitrogen atom in the molecular structure of such a component is preferable in designing a material because it hardly causes inhibition of curing when combined with a cationic photopolymerization initiator. For details on the types and combinations of epoxy resin components, curing agent components and curing accelerator components, published by Hiroshi Kakiuchi “Epoxy Resins”, Shoshodo Co., Ltd., Editor Hiroshi Kakiuchi “Epoxy Resins—Recent Advances” Issued books such as Shosodo Co., Ltd. (May 30, 1990) can be referred to.

  In particular, as the acid anhydride, maleic anhydride or a derivative thereof is preferable from the viewpoint of cost, reactivity, and characteristics, and in particular, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and maleic anhydride or A resin composition containing the derivative and a cationic photopolymerization initiator is preferred. In particular, as the monovalent or polyhydric alcohols, polyethylene glycol is preferable from the viewpoint of reactivity control, molecular weight control, and characteristic control, particularly 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, A resin composition containing maleic anhydride or a derivative thereof, polyethylene glycol, and a cationic photopolymerization initiator is preferable.

  Furthermore, the composition ratio of the resin composition is preferably a ratio of 0.1 to 1.4 mol of the curing agent component with respect to 1 mol of the resin component capable of reacting with the curing agent component, and in particular, reacting with the curing agent component. It is preferable that the ratio of the curing agent component is 0.3 to 1.0 mol with respect to 1 mol of the possible resin component. In the case of thermosetting, the ratio between the resin component and the curing agent component can be determined to some extent stoichiometrically, and when the range is exceeded, it becomes difficult to obtain a cured product having good physical properties. On the other hand, in the case of energy ray curing, curing proceeds with the resin component alone by the photopolymerization initiator. The present invention has features of both energy ray curing and heat curing. Accordingly, if the amount of the curing agent component is too small outside the above range, the curing ability improvement effect by the curing mechanism other than the energy beam irradiation, which is a feature of the present invention (different curing mechanism of energy beam curing and thermal curing by curing heat generation at that time) Are difficult to achieve, and insufficient curing is difficult to achieve. On the other hand, if too much is used, the amount of resin components required for energy beam curing will be relatively small, resulting in a decrease in energy beam curing capability and a decrease in the amount of heat generated by curing. Boil hardening characteristics are reduced. If the amount exceeds the stoichiometric limit, it becomes difficult to obtain a cured product having good physical properties. Moreover, it is preferable that a hardening accelerator component is a ratio of 0.04-0.6 mol with respect to 1 mol of hardening | curing agent components, and 0.08-0.4 mol of hardening accelerator components are especially with respect to 1 mol of hardening | curing agent components. It is preferable that the ratio is If the amount is too small outside the above range, the curing reaction cannot be promoted.On the other hand, if the amount is too large, the curing reaction cannot be promoted more than when an appropriate amount is added. This is not preferable in that it causes waste of the amount of heat generated by curing.

As the photopolymerization initiator component as an essential component, a cationic photopolymerization initiator is particularly preferable. In particular, the iron-allene compounds represented by the general formulas (I), (II), and (III) are resins of the present invention. When it is contained in the composition, it is preferable because the curing characteristics are greatly improved. For example, a resin composition containing 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, maleic anhydride, and the above general formula (I) is cured to the extent that it is easily cured by sunlight. Ability improves and shows high curability. It is also preferable to use a photo / thermal polymerization initiator. In particular, the sulfonium salt represented by the general formula (IV), (IV ′) or (V) has a large curing property when included in the resin composition of the present invention. The chain curing reaction, which has been difficult without conventional binary photopolymerization initiators, can be improved even with a single polymerization initiator. For example, a resin composition containing 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, maleic anhydride, and a compound such as general formula (IV) is represented by general formula (IV) or the like. As the compound shown is only contained in an amount of about 0.5 wt%, the curing ability increases and the curability increases as the chain curing reaction occurs.

Furthermore, a photopolymerization initiator comprising a photopolymerization initiator and a light / thermal polymerization initiator as a component is also preferable. In particular, an aryl sulfonium salt type or the general formulas (I), (II), (III And at least one of the iron-allene compounds represented by the formula (IV), and at least one of the sulfonium salts represented by the general formula (IV), (IV ′) or (V). When this photopolymerization initiator is used in the resin composition of the present invention, the curing characteristics are greatly improved. For example, a resin composition comprising 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, maleic anhydride, and a photopolymerization initiator composed of the above binary system has a curing ability. Because it improves and exhibits high curability, it undergoes chain curing reaction easily. Also suitable for photopolymerization initiators, photo / thermal polymerization initiators, polymerization initiator components composed of the above two or more systems, etc., such as prenyl, tetramethylenesulfonium, hexafluoroantimonate, etc. The photopolymerization initiator component to which is added is also preferable, and easier curing can be expected from the improvement of the thermosetting ability.

  Furthermore, the composition ratio of the resin composition is such that the photopolymerization initiator component is 0.1 to 6.0 parts by weight relative to 100 parts by weight of the total weight of the other components other than the photopolymerization initiator component. Particularly preferred is 0.5 to 3.0 parts by weight. If the ratio of the photopolymerization initiator component is less than 0.1 parts by weight, the effect is hardly obtained, and the amount of the photopolymerization initiator component is less likely to function because the amount thereof is small. On the other hand, even if it exceeds 6.0 parts by weight, the photocuring function itself does not change. Further, the weight ratio of the light / thermal polymerization initiator light constituting the initiation of photopolymerization consisting of a binary system or more is preferably 10 to 100 wt%, and particularly preferably 20 to 80 wt%. In conventional photopolymerization initiators composed of two or more binary systems, a light / thermal polymerization initiator light weight ratio of 50 to 80 wt% was preferred. In the present invention, the chain curing function is exhibited even at the above ratio. However, when the weight ratio is small, it is difficult to exhibit the characteristics of chain curing, and when the weight ratio is large, chain curing tends to be difficult to control.

  Furthermore, as an additive that can be added to the above resin composition within a curable range, energy ray shielding substances (for example, carbon and carbon fibers (short fibers, long fibers, continuous fibers, carbon cloth, etc.), Inorganic fillers, metal powders, etc.) and various fillers, organic components, photosensitizers, reactive diluents, photosensitizers, acidifiers and other commonly used additives can be added. Inventive resin composition and method for improving curing ability include various cured products, molded products, manufactured products such as molding materials, casting materials, filler filler amounts, fiber reinforced composite materials, carbon fiber reinforced composite materials, and other composite materials. , Paste materials, adhesives, sealing materials, varnishes, paints or coating materials, inks or toners.

Next, the manufacturing method of the energy-beam curable resin composition which concerns on this invention is demonstrated.
Examples of the method for producing the resin composition of the present invention include the production flow 1 shown in FIG. 1 or the production flows 2 to 4 shown in FIG. 2, but the production method of the resin composition of the present invention is limited to these. Is not to be done. In other words, any resin composition that finally contains the essential components of the present invention may be used. For example, depending on the components and characteristics of the resin composition to be produced, the temperature, stirring time, presence / absence of light shielding, the order of addition, etc. may be appropriately determined. it can. When the reactivity of each component of the curing agent component, curing accelerator component, photopolymerization initiator component, and photopolymerizable resin component is high, especially when the reactivity to temperature is high and curing is possible at room temperature in a short time Is preferably stirred at a low temperature so that the reaction does not proceed. In addition, when stirring a solid or a component that is difficult to dissolve, it is preferable to perform a long-time stirring or a solution such as dissolving in a solvent in advance to make it liquid. When the photopolymerization initiator component can be easily photoreacted in the production environment, or when it takes a long time from the photopolymerization initiator component to the end of production, it is effective to block the light or change the order of injection. . In addition, since the curing reaction may start and proceed or a side reaction may occur depending on the charging order, it is effective to change the charging order in this case as well. Since the resin composition employed in the present invention is highly curable and can be cured by both heat and energy rays, it is important to determine the production conditions so that no curing reaction occurs.

  Below, an example of a manufacturing method is demonstrated based on the manufacturing flow 1 of FIG. Each component used for manufacture of the resin composition used in the present invention is represented as Component A, Component B, Component C, Component D, Component E and Component F, where Component A is a photopolymerizable resin component and Component B is a curing agent component. , Component C is a photopolymerization initiator component, component D is a curing accelerator component, component E is a photosensitizer, photosensitizer, other additive components such as a stabilizer, component F is a reactive diluent, diluted Other components such as agents, pigments and fillers are shown. Among these, since components A to C are essential components, if manufacturing flow 1 is taken as an example, all the mixed components after mixed component 2 are the resin composition of the present invention. In addition, since each component may be composed of a plurality of types, each component is represented by the number of lowercase letters of each component as many as the number of types constituting each component. For example, when component A is composed of three types, Shown as a1, a2, and a3, respectively. In the production flow 1, all components are assumed to be composed of three types for convenience. Here, in order to facilitate understanding of the production method, a more specific production procedure and use apparatus will be shown, but the production method of the resin composition employed in the present invention is limited by the method and apparatus used here. It is not a thing.

  First, a predetermined amount of component B (b1, b2, b3) is put into a flask at a time into a predetermined amount of component A (a1, a2, a3), about 1 hr at room temperature with a propeller-type stirring blade at a rotation speed of 300 rpm. Stir to dissolve completely (mixed component 1). Of course, after preparing component A and component B in advance in one each, stirring with a propeller-type stirring blade at room temperature and rotation speed of about 300 rpm until component B is completely dissolved, Alternatively, a method may be used in which the mixture is stirred with a propeller-type stirring blade at room temperature at a rotation speed of 300 rpm until component B is completely dissolved. When component A and component B can be cured at room temperature, especially when it can be cured in a short time, the component A, component B and their mixed components are kept at a temperature (for example, 0 ° C. or lower) at which curing can be prevented and suppressed. Is good. In addition, it is better to gradually introduce.

  Next, a predetermined amount of c1, c2, c3 is sealed in a sample bottle together with a good solvent so as to have a concentration of 50 wt%, shielded with a stirrer, and stirred for 1 hr at room temperature to completely remove c1, c2, c3. Dissolve and prepare in advance, add it to the mixed component 1 at once, shield it with a propeller-type stirring blade, stir at room temperature for about 0.2 hr, and rotate at 300 rpm for complete dissolution (mixing) Ingredient 2). Of course, a predetermined amount of component C (c1, c2, c3) is added to mixed component 1 at a time, or component C is added to mixed component 1 in various ways, for example, shielded by a propeller-type stirring blade, Alternatively, a method of stirring until the component C is completely dissolved at a rotational speed of 300 rpm may be used. Further, as in the case of adjusting the mixed component 1, when the reactivity of the mixed component 1 and the component C is high, particularly when the component C contains a photo / thermal polymerization initiator and the reactivity to heat is high, the mixed component 1 It is better to keep the component C and the mixed component at a temperature (for example, 0 ° C. or less) at which the curing can be prevented and suppressed. In addition, it is better to gradually introduce.

  Then, a predetermined amount of d1, d2, and d3 is stirred with a propeller-type stirring blade at room temperature for about 0.5 hr and at a rotation speed of 300 rpm to prepare one in advance. Then, the mixture is shielded from light with a propeller type stirring blade, stirred at room temperature for about 0.2 hr, at a rotation speed of 300 rpm, and completely dissolved (mixed component 3). Of course, a predetermined amount of component D (d1, d2, d3) is added to the mixed component 2 at once, or the component D is added to the mixed component 2 in various ways, for example, shielded by a propeller type stirring blade, Alternatively, a stirring method may be used until the component D is completely dissolved at a rotation speed of 300 rpm. In addition, when the mixed component 2 and the component D are highly reactive, or when the mixed component 2 contains a photo / thermal polymerization initiator and has high reactivity to heat, the reaction of the mixed component is easily started by adding the component D. In this case, it is better to keep the mixed component 2 or component D and the mixed component at a temperature (for example, 0 ° C. or lower) at which curing can be prevented and suppressed. In addition, it is better to gradually introduce.

  Furthermore, a predetermined amount of e1, e2 (when e3 is used as a stabilizer) is sealed in a sample bottle together with a good solvent so as to have a concentration of 50 wt%, shielded with a stirrer, and stirred for 1 hr at room temperature to e1, e2 is completely dissolved and prepared in advance, and it is added to the mixed component 3 at once. The mixture is light-shielded with a propeller-type stirring blade, and stirred at room temperature for about 0.2 hr and at a rotation speed of 300 rpm. Dissolve. This was charged with e3 (when e3 was used as a stabilizer), shielded with a propeller-type stirring blade, and stirred at room temperature at a rotation speed of 300 rpm until e3 was completely dissolved (mixed component 4). Of course, a predetermined amount of component E (e1, e2, e3) is added to the mixed component 4 at a time, a predetermined amount of e1, e2 is added to the mixed component at a time and then e3 is added, or the component E is added. For example, a method may be used in which the components are separately added to the mixed component 3 and light-shaded with a propeller-type stirring blade, and stirred until the component E is completely dissolved at room temperature and a rotational speed of 300 rpm. In addition, when the reactivity of the mixed component 3 and the component E is high, or when the mixed component 3 contains a photo / thermal polymerization initiator and the reactivity to heat is high, the reaction of the mixed component is easily started by adding the component E. In this case, it is better to keep the mixed component 3 or component E and the mixed component at a temperature (for example, 0 ° C. or lower) at which curing can be prevented and suppressed. In addition, it is better to gradually introduce. Furthermore, the order in which the components D and E are charged is changed so that the component E is added to the mixed component 2 and then the component D is added. Alternatively, the order in which the component E is added at the same time as the component C is conceivable. These stabilizers are intended to suppress the reactivity of the resin composition under storage and improve pot life, and should be added at the end to prevent extreme inactivation of curing reactivity and stability effects. It may be preferable.

  Finally, a predetermined amount of the component F (f1, f2, f3) is added to the mixed component 4 at once, light-shielded with a propeller-type stirring blade, and stirred at room temperature for about 1 hr at a rotation speed of 300 rpm to obtain a resin composition. . Of course, a predetermined amount of the component F is prepared in advance and then added to the mixed component 2, or the component F is added to the mixed component 4 in various ways, for example, shielded with a propeller-type stirring blade, at room temperature, and rotated. A method of stirring for about 1 hour at several 300 rpm may be used. In addition, when the reaction start by the introduction and stirring of the component F, for example, the reaction start by heat generation during stirring, can be considered, the temperature at which the mixed component 4 or the component F and the mixed component can be prevented and suppressed from being cured (for example, It is better to keep it below 0 ° C. In addition, it is better to gradually introduce. In addition, component F is a component necessary when actually used in various applications by taking advantage of the characteristics of the resin composition of the present invention, and may be a method of adding just before actual use.

  The amount of each component is charged, but the amount to be charged differs depending on the component to be charged and the reactivity at the time of production. If the reactivity is high, gradually add while paying attention to the temperature rise of the mixture. Basically, the mixture is kept at a low temperature, and if the reactivity is low, there is no problem even if it is added at once. However, as an example of a method of mixing highly reactive solutions, there is a method of preventing the reaction by instantaneously dispersing by high-speed stirring or the like. In addition, when adding / adding multiple types of components, whether multiple types are added one by one, or multiple types are mixed together before being added together, multiple types are added simultaneously. However, depending on the type and application, it may be better to add a stabilizer or a reactive diluent for final viscosity adjustment. In some cases, it may be better to dissolve them. Regarding light shielding, basically, all those containing a photoreactive component should be performed. For production flows 2 to 4, the order of addition of production flow 1 was changed. Basically, the temperature was a low temperature in consideration of the reaction not proceeding, and the stirring time was until the components were completely dissolved in each stirring step. The presence or absence of light shielding is from the addition of the photoreactive substance to the end of production. However, in the production flow 3, since component C (photopolymerization initiator component) is added to a highly curable mixed component, it is considered that a curing reaction is likely to occur compared to other components. For example, it is preferable to add gradually as 0 ° C. or less.

  Further, when the practical use of the resin composition according to the present invention is considered, the final may be a resin composition containing essential components intended by the present invention by the time when the resin composition is actually cured. Therefore, instead of preparing a one-component resin composition containing essential components from the beginning, the resin composition is initially manufactured by dividing it into two or more different compositions. You may stir, mix and harden before using. Examples of the component division are shown in Table 8 below, but are not limited thereto, and various cases are conceivable from the types and ratios of the components used, storage conditions, manufacturing conditions, and the like.

なお、表中、樹脂組成物の構成成分および構成種は、成分Ａ（構成種ａ１，ａ２）、成分Ｂ、成分Ｃ、成分Ｅとする。また、成分Ｆを追加する場合、基本的は配合量が多い成分Ａを含有する方に追加するが、逆の場合もある。

In the table, the constituent components and constituent species of the resin composition are component A (constituent species a1, a2), component B, component C, and component E. Moreover, when adding the component F, it adds to the direction containing the component A with much compounding quantity fundamentally, However, the reverse may be sufficient.

  Dividing the components has the advantage of improving the storage stability as in the case of the conventional two-component curable resin, but increases the labor of stirring in actual work. EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Example 1
To 1 mol of Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd .: alicyclic epoxy resin; 3,4-cyclohexylmethyl-3,4-epoxycyclohexanecarboxylate), 0.65 mol of maleic anhydride is added and stirred and dissolved. Irgacure 261 (manufactured by Ciba Geigy Co., Ltd .: iron-allene photopolymerization initiator; general formula (I)) 1.5 parts by weight was blended with 100 parts by weight of the sauce. (A) 50 g of (A) was poured into a glass container (φ40 mm × H50 mm). This was applied to sunlight (April, 1 pm, fine weather). (B) The sample was completely cured within 10 min.

Example 2
To 100 parts by weight of 0.65 mol of maleic anhydride added to 1 mol of Celoxide 2021P and stirred and dissolved, Sun-Aid SI-80L (manufactured by Sanshin Chemical Co., Ltd .: cationic photo / thermal polymerization initiator; general formula (IV) 50 wt% + solvent 50 wt%, additive trace amount) 1.0 part by weight was blended. (C) 50 g of (C) was poured into a glass container (φ40 mm × H50 mm). This was irradiated with UV for 3 min. UV irradiation conditions are UV irradiation apparatus: UVL-1500M2 (Ushio Electric Co., Ltd.), lamp type: metal halide lamp, lamp intensity: 120 W / cm, lamp length: 125 mm, atmosphere / temperature / pressure: in air / room temperature / atmospheric pressure The irradiation distance was 15 cm. (D) The sample was completely cured in a few minutes while chain curing.

Example 3
In Example 2 (C), 0.5 part by weight of Sun-Aid SI-60 (manufactured by Sanshin Chemical Co., Ltd .: cationic photo / thermal polymerization initiator; general formula (IV)) instead of Sun-Aid SI-80L The same test as in Example 2 was performed except that. The sample cured completely in a few minutes while chain curing.

Example 4
To 100 parts by weight of 1.05 parts by weight of Irgacure 261, Sun Aid SI-60L (manufactured by Sanshin Chemical Co., Ltd .: Cationic light) -Thermal polymerization initiator: 1.0 part by weight of general formula (IV) / solvent = 1/2, a small amount of additive was blended. (E) 50 g of (E) was injected into a glass container (φ40 mm × H50 mm) and exposed to sunlight in the same manner as in Example 1 (B). The sample cured completely in a few minutes while chain curing.

Example 5
50 g of (E) in Example 4 was injected into a glass container (φ40 mm × H50 mm), and UV was irradiated in the same manner as in Example 2 (D). The sample cured completely in a few minutes while chain curing.

Example 6
Example 4 (E) photoinitiator compounding amount was changed to 1.0 part by weight of Irgacure 261 and 0.5 part by weight of Sun-Aid SI-60L, and 50 g was injected into a glass container (φ40 mm × H50 mm). UV was irradiated in the same manner as 2 (D). The sample cured completely in a few minutes while chain curing.

Example 7
Example 4 (E) photoinitiator compounding amount was changed to 0.5 parts by weight of Irgacure 261 and 1.0 parts by weight of Sun-Aid SI-60L, and 50 g was injected into a glass container (φ40 mm × H50 mm). UV was irradiated in the same manner as 2 (D). The sample cured completely in a few minutes while chain curing.

Example 8
In the resin composition of Example 4 (E), 0.65 mol of maleic anhydride was changed to 0.3 mol, and 50 g was injected into a glass container (φ40 mm × H50 mm), and the same method as in Example 2 (D) With UV irradiation. Although the sample took longer to cure than Example 5, it was completely cured in several minutes while chain curing.

Example 9
In the resin composition of Example 4 (E), 0.65 mol of maleic anhydride was changed to 0.65 mol of hexahydrophthalic anhydride, and 50 g was injected into a glass container (φ40 mm × H50 mm). UV was irradiated in the same manner as in D). Although the sample took longer to cure than Example 5, it was completely cured in several minutes while chain curing.

Example 10
In the resin composition of Example 4 (E), 0.65 mol of maleic anhydride was changed to 0.3 mol of polyethylene glycol 300 (molecular weight average 300), and 50 g was injected into a glass container (φ40 mm × H50 mm). UV was irradiated in the same manner as 2 (D). The sample cured completely in a few minutes while chain curing.

Example 11
The photoinitiator component (E) of Example 4 was 0.3 parts by weight of DAICAT11 (manufactured by Daicel Chemical Industries, Ltd .: aryl sulfonium salt type / solvent = 1/1), 0.7 parts by weight of Sun-Aid SI-80L Then, 50 g was injected into a glass container (φ40 mm × H50 mm) and irradiated with UV in the same manner as in Example 2 (D). The sample cured completely in a few minutes while chain curing.

Example 12
Celacide 2021P / maleic anhydride / polyethylene glycol 300 (molar ratio 1.0 / 0.65 / 0.17) 100 parts by weight, Irgacure 261 1.0 part by weight, Sun Aid SI-60L 1.0 part by weight were blended. . (F) 50 g of (F) was injected into a glass container (φ40 mm × H50 mm) and irradiated with UV in the same manner as in Example 2 (D). The sample cured completely in a few minutes while chain curing easier than in Example 5.

Example 13
In the resin composition of Example 12 (F), the molar ratio of polyethylene glycol 300 was changed to 0.085, and 50 g was injected into a glass container (φ40 mm × H50 mm), and the same method as in Example 2 (D). Irradiated with UV. Although the sample took longer to cure than Example 12, it cured completely in a few minutes while chain curing easier than Example 5.

Example 14
In the resin composition of Example 12 (F), the molar ratio of polyethylene glycol 300 was changed to 0.65, and 50 g was injected into a glass container (φ40 mm × H50 mm), and the same method as in Example 2 (D). Irradiated with UV. The sample cured completely in a few minutes while chain curing. Compared with Example 12, the cured sample had low hardness and strongly exhibited rubber properties.

Example 15
Celoxide 2021P / Celoxide 2000 (Daicel Chemical Co., Ltd .: photopolymerizable diluent; cyclohexene vinyl monooxide) / maleic anhydride / hexahydrophthalic anhydride / polyethylene glycol 300 (molar ratio 0.95 / 0.05 / 0.48 mol / 0.16 mol / 0.145 mol) and 100 parts by weight of Irgacure 261 0.072 parts by weight, DAICAT11 0.288, and Sun Aid SI-60 0.504 parts by weight were blended. At the time of preparation, polyethylene glycol 300 was added last. (G) 50 g of (G) was injected into a glass container (φ40 mm × H50 mm) and irradiated with UV in the same manner as in Example 2 (D). The sample cured completely in a few minutes while chain curing.

Example 16
A resin composition was prepared in the same manner except that the photoinitiator component (G) in Example 15 was changed to 0.1 parts by weight of Irgacure 261, 0.2 parts by weight of DAICAT11, and 0.7 parts by weight of Sun-Aid SI-60L. Then, 50 g was injected into a glass container (φ40 mm × H50 mm) and irradiated with UV in the same manner as in Example 2 (D). The sample cured completely in a few minutes while chain curing.

Example 17
A resin composition was prepared in the same manner except that the photoinitiator component (G) of Example 15 was changed to 0.2 parts by weight of Irgacure 261, 0.8 parts by weight of DAICAT11, and 1.4 parts by weight of Sun-Aid SI-60. did. (H) 50 g of (H) was injected into a glass container (φ40 mm × H50 mm) and irradiated with UV in the same manner as in Example 2 (D). The sample cured completely faster than Example 15 with intense chain curing.

Example 18
A resin composition was prepared in the same manner as in Example 17 except that the ceroxide 2021P of (H) was changed to ARALDITE AER 260 (Asahi Ciba Co., Ltd .: bisphenol A type liquid epoxy resin), and a glass container (φ40 mm × H50 mm) 50 g was injected and UV was irradiated in the same manner as in Example 2 (D). The sample cured completely in a few minutes while chain curing.

Example 19
UV was irradiated in the same manner as in Example 2 (D) except that (G) of Example 15 was poured into a glass test tube (φ15 mm × H150 mm) to a height of 120 mm and the irradiation distance was 10 cm. The sample cured completely in a few minutes while chain curing.

Example 20
A resin composition similar to (H) of Example 17 was poured into a copper tube (φ19 mm × L500 mm) filled with a carbon fiber nonwoven fabric, and one end was sealed with a rubber stopper. Irradiation was performed in the same manner as in Example 2 (D) except that the irradiation distance was 10 cm and the irradiation time was 5 min. The sample cured completely within a few hours while chain curing.

Example 21
(G) of Example 15 was poured into a copper tube (φ19 mm × L500 mm) filled with a carbon fiber nonwoven fabric, and one end was sealed with a rubber stopper. This was placed in an oven maintained at 70 ° C. for 2 hours and then taken out. The sample was cured by heat.

Comparative Example 1
A resin composition of 100 parts by weight of Celoxide 2021P and 1.5 parts by weight of Irgacure 261 (a composition obtained by removing maleic anhydride from (A) of Example 1) was prepared, and 50 g was injected into a glass container (φ40 mm × H50 mm). did. This was exposed to sunlight in the same manner as in Example 1 (B). Even when the sample was exposed to sunlight for 5 hours, it was uncured.

Comparative Example 2
A resin composition of 100 parts by weight of Celoxide 2021P and 1.0 part by weight of Sun Aid SI-80L (composition construction excluding maleic anhydride from (C) of Example 2) was prepared, and a glass container (φ40 mm × H50 mm) 50 g was injected. This was irradiated with UV in the same manner as in Example 2 (D). In the sample, chain curing did not occur, only the surface layer was cured, and the rest was uncured.

Comparative Example 3
A resin composition of 100 parts by weight of Celoxide 2021P and 1.0 part by weight of Sun-Aid SI-60 (composition construction excluding maleic anhydride from the resin composition of Example 3) was prepared, and a glass container (φ40 mm × H50 mm) 50 g was injected. This was irradiated with UV in the same manner as in Example 2 (D). In the sample, chain curing did not occur, only the surface layer was cured, and the rest was uncured.

Comparative Example 4
Prepare 100 parts by weight of Celoxide 2021P, 1.0 part by weight of Irgacure 261, and 0.5 parts by weight of Sun-Aid SI-60L (excluding maleic anhydride from the resin composition of Example 6). 50 g was poured into a glass container (φ40 mm × H50 mm). This was irradiated with UV in the same manner as in Example 2 (D). In the sample, chain curing did not occur, only the surface layer was cured, and the rest was uncured.

Comparative Example 5
A resin composition of 100 parts by weight of Celoxide 2021P, 0.3 parts by weight of DAICAT11, and 0.7 parts by weight of Sun-Aid SI-80L was prepared (excluding maleic anhydride from the resin composition of Example 11). 50 g was poured into a glass container (φ40 mm × H50 mm). This was irradiated with UV in the same manner as in Example 2 (D). The above sample clearly had lower curing ability when compared with Example 11.

Comparative Example 6
A resin composition of 100 parts by weight of Celoxide 2021P / Celoxide 2000 (molar ratio 0.95 / 0.05), 0.072 parts by weight of Irgacure 261, 110.288 of DAICAT, and 0.504 parts by weight of Sun-Aid SI-60 (comparative object: Example 15) was prepared and 50 g was poured into a glass container (φ40 mm × H50 mm). This was irradiated with UV in the same manner as in Example 2 (D). The above sample clearly had lower curing ability when compared with Example 15.

Comparative Example 7
100 parts by weight of Celoxide 2021P / Celoxide 2000 (molar ratio 0.95 / 0.05), 0.1 part by weight of Irgacure 261, 0.2 part by weight of DAICAT11, 0.7 part by weight of Sun Aid SI-60L ( Comparative object: Example 16) was prepared and 50 g was injected into a glass container (φ40 mm × H50 mm). This was irradiated with UV in the same manner as in Example 2 (D). The above sample clearly had lower curing ability when compared to Example 16.

  From the results of the above Examples 1 to 21 and Comparative Examples 1 to 7, it can be seen that according to the resin composition, an excellent energy beam curable resin molded article can be easily obtained.

FIG. 1 is a diagram showing an example (manufacturing flow 1) of a manufacturing flow when manufacturing a resin composition according to the present invention. FIG. 2 is a diagram showing another example of the production flow when producing the resin composition according to the present invention, (a) production flow 2, (b) production flow 3, and (c) production flow 4.

Claims (12)

A photopolymerization initiator component that includes an epoxy resin having a cyclic ether structure in the molecular structure as a photopolymerizable resin component, and further allows the photopolymerizable resin component to be cured when irradiated with energy rays; A curing agent component used for curing the resin component at room temperature or heat curing,
As the photopolymerization initiator component, the following general formula (IV), (IV ′) or (V)

Including a sulfonium salt represented by
The curing agent component is an acid anhydride, and the curing agent component is in a ratio of 0.1 to 1.4 mol with respect to 1 mol of the photopolymerizable resin component capable of reacting with the curing agent component,
Energy characterized in that the photopolymerization initiator component is in a ratio of 0.1 to 6.0 parts by weight with respect to 100 parts by weight of the total weight of other components other than the photopolymerization initiator component in the resin composition. A wire curable resin composition.   2. The energy ray curing according to claim 1, further comprising a curing accelerator component that accelerates the curing when at least one of the photopolymerizable resin component and the curing agent component are cured at room temperature or heat. Resin composition.   The energy ray curable resin composition according to claim 2, comprising a monovalent or polyhydric alcohol as the curing accelerator component.   The said hardening | curing agent component or the said hardening accelerator component consists of a compound which can react with the said epoxy resin component, and does not have a nitrogen atom in molecular structure. Energy ray curable resin composition.   The energy ray curable resin composition according to any one of claims 1 to 4, comprising 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate as the photopolymerizable resin component.   6. The energy ray curable resin composition according to claim 1, comprising maleic anhydride or a derivative thereof as the acid anhydride.   The energy ray curable resin composition according to any one of claims 1 to 6, wherein the alcohols include polyethylene glycol.   An energy beam curable resin molded article obtained by curing the energy beam curable resin composition according to claim 1.   A paste material comprising the energy ray curable resin composition according to claim 1.   A composite molding material comprising the energy beam curable resin composition according to claim 1.   An adhesive comprising the energy ray curable resin composition according to claim 1.   A coating material comprising the energy beam curable resin composition according to claim 1.

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