JP3944217B2 - Polymerization initiator and method for producing cured resin using the same - Google Patents

Description

Using energy such as UV (ultraviolet rays), EB (electron beams), infrared rays, X-rays, visible rays, lasers such as argon, CO ₂ and excimers, solar rays, heat rays such as radiation and radiation, and energy such as heat It relates to the manufacturing method of the resin Polymerization initiator or a resin cured product Ru is quickly cured. In particular, energy rays are attenuated or absorbed by the resin, and the hardening action is significantly reduced, and the thick resin that cannot be hardened deeply is formed, or fillers such as carbon fiber, metal fiber, and glass fiber are used to increase the strength. ) Or a resin molding method that uses metallic inserts or the like as a reinforcing material. As a result, the energy rays are shielded by these reinforcing materials, so this can be cured when the shadow is not fully cured. about the polymerization initiator to. The present invention relates to a resin system (for example, carbon fiber reinforced composite (CFRP), carbon / metal / inorganic) in which a substance (for example, carbon, carbon fiber (CF), metal, or other inorganic filler) having extremely high energy ray shielding properties is contained. Containing resin) also relates to a method for producing a novel resin cured product that enables energy ray curing . The polymerization initiator and the production method are effective regardless of the presence or absence, length, size, and shape of the UV shielding property of the fiber or filler, and the fields of use include adhesives, sealing materials, varnishes in addition to composite materials. It can be applied to fields such as paints, coating materials, inks, and toners.

In recent years, energy ray curable resins typified by UV curable resins have been used in various fields and applications, but such resins have a feature that only a portion irradiated with a certain amount or more of energy rays is cured. On the other hand, energy rays typified by UV are attenuated in the process of passing through the resin, so it is difficult to reach the deep part of the resin, or there is a feature such as large attenuation and absorption by substances that absorb the same wavelength as the energy rays. Have. Therefore, the photo-curing resin only cures the surface layer of several μm to mm where the energy rays reach, and the deep part is uncured, so that it is difficult or impossible to apply to thick materials, In the case of a resin containing a filler or the like, there is a problem that curing inhibition easily occurs and the resin cannot be cured, and the range of use is mainly in the fields of photoresist, coating, paint, adhesive, varnish and the like.
Typical examples of solutions for such problems include high UV curable resins (Mitsubishi Rayon Co., Ltd., active energy ray curable composition, see Patent Document 1) and UV / heat combination curable resins (Asahi Denka Kogyo). Co., Ltd .: Optomer KS series, Hitachi Chemical Co., Ltd .: Radicure, Toyobo: UE resin, see Patent Document 2) and the like. However, the problem remains that the high UV curable resin cannot be cured when the energy beam is blocked by a filler or the like. In addition, the UV / heat combination type resin that is heated after UV irradiation has the same level of curing ability by energy rays as the conventional photo-curing resin, and the problems of thick-wall curing and filler-containing curing have not been solved at all. In the present situation, it is possible to cope with thermal curing by heating performed after photocuring (only the surface layer), and this problem cannot be solved.

  If a technology that can rapidly cure thick resin that contains the energy ray shielding substances mentioned above, or that attenuates and absorbs energy rays, can be established. Thus, it can be applied to various other fields that have been impossible to apply until now, and one of them is application to FRP, particularly CFRP matrix resin. Conventionally, various processing methods and manufacturing methods are used for FRP, but most of the matrix resin is thermosetting or thermoplastic resin. Problems in molding FRP, particularly CFRP, include that the temperature control is complicated and a long time is required for curing, so that the processing cost is high, a large heating furnace is required when curing a large FRP, In the case of a resin that can be cured in a short time, it cannot be used for a large FRP that requires a long time for molding, the resin impregnation state changes due to the temperature change of the resin viscosity, the molding is difficult, and the resin is cured by the residual solvent Occasionally, voids are generated and the quality of the molded product is deteriorated.

  Recently, the use of a photocurable resin as a matrix resin has attracted attention as a solution to this problem. As a typical example of such a matrix resin curing method, a filament winding molding method using a combination of UV curing and heat curing of Loctite Corporation (Loctite Corporation, fiber / resin composition and preparation method thereof, see Patent Document 3) is specifically exemplified. be able to. However, the FRP molding method using such a composition is that the uncured FRP impregnated with resin is irradiated with UV to cure the surface and extremely thicken (gel) the inside to maintain the shape and impregnation state. Is made possible to some extent, and is then completely cured by heating. Therefore, the temperature change of the resin viscosity is extremely small compared to the conventional thermoplastic or thermosetting resin manufacturing method and handling after impregnation is easy, but complete curing requires a heat curing process. There are unsolved problems such as processing costs due to utility costs and work time required for heat curing, problems that require a long time to complete curing, and the need for a large heating furnace to form a large FRP.

JP-A-8-283388 Japanese Examined Patent Publication No. 61-38023 Japanese National Patent Publication No. 7-507836 JP-A-6-157624 Japanese Patent Laid-Open No. 7-82283 "Journal of Polymer Science": Part A: "Polymer Chemistry" Vol. 29, 1675-1680 (1991), "Polymer" Volume 40 December (1991), 794-797

In view of the above-mentioned drawbacks of the conventional energy ray curable resin and the disadvantages of FRP, particularly CFRP, the present inventors have earnestly studied the energy ray curing of the thick resin containing the energy ray shielding material and the energy ray hardening of FRP, particularly CFRP. As a result of the research, the present invention has been achieved, and the object of the present invention is a resin system including a substance having a very high energy ray shielding property, such as carbon, carbon fiber (CF), metal, and other inorganic fillers. , for example, carbon fiber reinforced composite material (CFRP), also in carbon / metal compound / inorganic-containing resin, a polymerization initiator that enables energy ray, and to provide a method for producing a cured resin. Another object of the present invention is to provide a photopolymerization initiator (reaction catalyst system) comprising a specific binary system or more in a resin composition having a high energy ray shielding property such as carbon fiber reinforced composite material (CFRP). In this case, the resin composition is completely cured to the shadow and deep part only by irradiating energy rays such as UV and EB.

The above object can be effectively achieved by the inventions summarized below.
(1) When energy is applied to the resin composition, energy different from the energy from the energy source is self-generated within the resin, and the resin composition is cured by the energy or the energy and energy from the energy source. A resin curing method characterized by the above.
(2) When energy is applied to the resin composition, energy different from the energy from the energy source is self-generated inside the resin, and the generated energy is continuously generated, and the energy or the energy is generated. And a resin curing method, wherein the resin composition is cured by energy from an energy source.

( 1 ) It consists of two or more systems comprising a photopolymerization initiator and a light / thermal polymerization initiator that initiates polymerization with both light and heat as components, and with respect to 100 parts by weight of the photopolymerizable oligomer or monomer, 0.5 to 6.0 parts by weight, a polymerization initiator having a weight ratio of the photo / thermal polymerization initiator / the photo polymerization initiator of 1 to 4, and
Curing is started by irradiation of energy rays to generate curing reaction heat, and the curing reaction proceeds in a chain by the curing reaction heat to continuously generate curing reaction heat, and the energy ray shielding substance in the resin composition. A polymerization initiator having the property of causing the curing reaction to proceed in a chain manner by the self-generated heat of the curing reaction without irradiation of energy rays, regardless of the presence or absence of. Needless to say, it is possible to continue irradiation with energy rays after the start of curing.

(2) In addition, the heavy initiator according to (1) formed by adding a thermal polymerization initiator.
( 3 ) Two or more of photopolymerization initiators, thermal polymerization initiators, and photo / thermal polymerization initiators are radical polymerization initiators as described in ( 1) or ( 2) above heavy initiator.

(4) a photopolymerization initiator, thermal polymerization initiator, or two or more of the light-thermopolymerization initiator, according to the above (1) or (2), characterized in that an anionic polymerization initiator heavy initiator.
(5) a photopolymerization initiator, thermal polymerization initiator, two or more of the light-thermopolymerization initiator, according to the above (1) or (2) characterized in that it is a cationic polymerization initiator heavy initiator.

Wherein allene compound type and at least one sulfonic acid ester type, - as (6) a photopolymerization initiator, diazonium salt type, an iodonium salt type, pyridinium salt type, phosphonium salt type, sulfonium salt type, iron
As photo / thermal polymerization initiators , sulfonium salts represented by the following general formulas (I), (II), (II) ′, (III), (IV), (V), (VI) and (VII) Polymerization initiators according to (5), characterized in that it comprises at least one.

(Where R ¹ is hydrogen, methyl group, acetyl group, methoxycarbonyl group, R ² and R ³ are independently hydrogen, halogen, or C ₁ -C ₄ alkyl group, R ⁴ is hydrogen, halogen, A methoxy group, R ⁵ represents a C _{1 to} C ₄ alkyl group, and A represents SbF ₆ , PF ₆ , AsF ₆ , or BF ₄ .

(In the above formula (II) or (II ′), R ⁶ is a hydrogen atom, halogen atom, nitro group, methyl group, R ⁷ is a hydrogen atom, CH ₃ CO, CH ₃ OCO, A is SbF ₆ , PF ₆ , BF ₆ and AsF _6. )

(In the above formula, R ⁸ represents a hydrogen atom, CH ₃ CO, CH ₃ OCO, and B represents SbF ₆ , PF ₆ , BF ₆ , AsF ₆ , and CH ₃ SO _4. )

[In the formula (a), R ⁹ is a C ₁ -C ₁₈ aliphatic group, R ¹⁰ is a C ₁ -C ₁₈ aliphatic group or a C ₆ -C ₁₈ substituted or unsubstituted aromatic group, R ⁹ and R ¹⁰ may be bonded to each other to form a ring].

[In the formula (b), R ¹¹ is a C ₁ -C ₁₈ aliphatic group, R ¹² is a C ₁ -C ₁₈ aliphatic group or a C ₆ -C ₁₈ substituted or unsubstituted aromatic group, R ¹¹ and R ¹² may be bonded to each other to form a ring], a hydrogen atom, a halogen atom, a nitro group, an alkoxy group, a C _{1 to} C ₁₈ aliphatic group, or C _{A 6 to} C ₁₈ substituted or unsubstituted phenyl, phenoxy or thiophenoxy group; In the formula (IV), n and m are each independently an integer of 1 to 2, Z is a formula MQ ₁ or MQ _1-1 OH (M is B, P, As or Sb, Q is a halogen atom, l is an integer of 4 or 6.

(Wherein R ^13, R ¹⁴ independently represent hydrogen or an alkyl group of C ₁ -C _4, A is. Indicating an _{SbF 6, PF 6, AsF 6} )

(Wherein R ¹⁵ is any one of ethoxy, phenyl, phenoxy, benzyloxy, chloromethyl, dichloromethyl, trifluoromethyl, and trifluoromethyl; R ¹⁶ and R ¹⁷ are independently hydrogen, halogen, Any one of C _{1 to} C ₄ alkyl groups, R ¹⁸ represents hydrogen, methyl group, methoxy group, or halogen, R ¹⁹ represents hydrogen, methyl group, methoxy group, or halogen, R ¹⁹ Represents a C _{1 to} C ₄ alkyl group, and A represents SbF ₆ , PF ₆ , BF ₄ , or AsF ₆ .

(Wherein Q is a methoxycarbonyloxy group, acetoxy group, benzyloxycarbonyloxy group, dimethylamino group, R ²⁰ and R ²¹ are independently hydrogen, and any one of C ₁ -C ₄ alkyl groups is R ²² , R ²³ independently represents any of a C _{1 to} C ₄ alkyl group, and A represents SbF ₆ , PF ₆ , AsF ₆ , or BF ₄ .

(7) as a photopolymerization initiator comprises at least one aryl sulfonium salt type,
As the light-heat polymerization initiator, Polymerization initiators described in the general formula (I), (II) or above, characterized in that it comprises at least one sulfonium salt type represented by (III) (6).
(8) as a thermal polymerization initiator, Polymerization initiator according to any one of the above, which comprises at least one compound of formula (VIII) and (IX) (2) ~ (7).

( 9 ) A method for producing a cured resin using the polymerization initiator according to any one of (1) to (8) .

(10) The method of producing the cured resin described above (9), characterized in that to facilitate cure more by warming at a temperature range that does not cure the pre Me resin composition.

  In the above-described method of the present invention, energy (for example, heat energy) is self-generated inside the resin, or energy is continuously generated by the generated energy, particularly by the methods (1) to (13). In order to enable curing, specifically, at least a binary photopolymerization initiator system (reaction catalyst system) using a photopolymerization initiator and a photo / thermal polymerization initiator as a polymerization reaction catalyst is used for the above curing method. enable.

  That is, the present invention can be further summarized as a photopolymerization initiator system comprising a novel resin curing mechanism that enables energy beam curing of CFRP and energy ray shielding material thick resin and a binary system or more that enables such curing mechanism ( Reaction catalyst system) and a composition containing the same, and in particular the photopolymerization initiator is a diazonium salt type, iodonium salt type, pyridinium salt type, phosphonium salt type, sulfonium salt type, iron-allene compound type, sulfonate ester Photopolymerization initiator (reaction catalyst system) comprising at least one of the types and at least one of the sulfonium salts represented by the general formulas (I) to (VII) as the photo / thermal polymerization initiator. Are preferably used. Further, the photopolymerization initiator contains an aryl sulfonium salt type (triarylsulfonium salt), and the photo / thermal polymerization initiator contains at least one of the sulfonium salts represented by the general formulas (I), (II), and (III). It is preferable to use a photopolymerization initiator (reaction catalyst system) comprising at least a binary system.

  Further, a thermal polymerization initiator represented by the chemical formulas (VIII) and (IX) may be added to the photopolymerization initiator composed of these binary systems or more. Furthermore, the present invention relates to a composition ratio of a specified photopolymerization initiator system composed of two or more binary systems, a resin composition and a resin composition ratio and a molded product that enable a novel resin curing mechanism, and such a curing mechanism and a resin composition. The present invention relates to a utilization method, an FRP production method using such a resin as a matrix resin, a resin composition, and a molded product.

  First of all, the present inventors cannot cure energy rays of energy ray shielding substance-containing resins, such thick resins, and such application examples of FRP and CFRP because the energy represented by UV is (1) Substance (resin ) Is attenuated when passing through (FIG. 1), (2) it is easily shielded by a substance that absorbs the same wavelength (FIG. 2), and energy represented by UV curable resin Pay attention to the fact that (3) the cured resin has a feature that only the part where energy rays of a certain amount or more are transmitted (Fig. 3), and (1) and (2) are changes based on the principle Considering that this is a difficult event, earnest research on a new resin curing mechanism capable of securing energy required for curing, avoiding shielding of energy necessary for curing, and curing non-transparent sites of energy rays did As a result, when the resin composition is irradiated with energy rays or energy is applied to the resin composition, another energy is self-generated within the resin, and the energy or the energy and energy ray source, or the energy from the energy source. A new resin curing mechanism for curing the resin composition was clarified and a resin curing method based on this mechanism was developed.

FIG. 1 shows the state in which the intensity of UV energy is gradually attenuated when energy rays from the UV lamp pass through the resin composition (indicated by waveforms in the figure). In FIG. 2, the UV energy is easily blocked because there is an energy ray shielding material such as a carbon cloth material. FIGS. 3 (a) and 3 (b) each show a state in which only a portion through which a certain amount or more of energy rays are transmitted is cured when UV energy is transmitted through the liquid resin (the hatched portion on the right side of the drawing). (B) indicates that the energy ray shielding material such as the carbon cloth material is present, and the curing is blocked by the shielding material. Examples of the energy rays include electron rays, X-rays, infrared rays, sunlight rays, visible rays, lasers (excimer laser, O ₂ laser, etc.), heat rays (radiation, radiation, etc.), and the like. Further, the energy to be applied may be heat or the like in addition to light and electromagnetic waves.

  Based on this, further research has been carried out. Continuous generation of self-generated energy, application of thermal energy as self-generated energy, continuous generation of thermal energy, application of curing reaction heat (curing exothermic heat), cation, Use of radicals and anions, improvement of curability by preheating, use of polymerization initiators, etc. are found, and when the resin composition is irradiated with energy rays, cations and heat of curing reaction (curing heat generation) are actively generated inside the resin. In addition, the resin is further reacted in a chain reaction with cations and heat of curing reaction to continuously generate cations and heat of curing reaction (curing exotherm), regardless of the presence or absence of the energy linear shielding substance in the resin composition. , A new resin curing mechanism in which the resin composition is cured by reaction heat energy or reaction heat energy and energy from an energy ray source (FIG. 4), Bikakaru resin curing method was developed.

  FIGS. 4A and 4B are schematic diagrams for explaining the resin curing mechanism (light + curing reaction heat and cation curing system) according to the present invention. When the resin composition is irradiated with energy rays, cations are formed inside the resin. This shows a state in which the curing reaction heat is positively generated and the resin is further cured by a chain reaction by the cation and the curing reaction heat. (A) shows the initial state, and (b) shows the state in which the reaction thermosetting proceeds to the lowermost resin composition. In either case, the curing reaction proceeds regardless of the presence or absence of the carbon cloth material. In this example, cations are used together with the heat of curing reaction in the polymerization, but as is well known, radicals and anions can also be used in the present invention as those responsible for resin polymerization. Furthermore, the curing mechanism of the present invention enables the same curing with heat or the like in addition to energy such as light and electromagnetic waves.

  These newly developed resin curing mechanisms are greatly different from the resin curing mechanisms (Fig. 5 and Fig. 6) of high UV curable resins and UV / heat curable resins that are representative of the prior art. Thus, the novel resin curing mechanism of the present invention does not have the disadvantages of the prior art such as poor curing of the filler-containing material and necessity of heating after irradiation with energy rays. FIGS. 5A and 5B show a resin curing mechanism of a conventional high UV curable resin. When an energy ray shielding substance is not present as in FIG. 5A, the cured film thickness can be increased. Although there is an advantage, when the shielding material is present, the curing reaction does not proceed as shown in (b).

  6 (a) and 6 (b) show the resin curing mechanism of a conventional UV / heat combination curable resin, and curing by UV energy irradiation in (b) does not proceed due to the presence of an energy ray shielding substance. Therefore (in the case of the lower figure), as shown in (a), it is necessary to advance curing by using heating together after irradiation with energy rays. When an energy ray shielding material such as a carbon cloth material is present, the problems of conventional UV curing cannot be solved without heating. In both cases (a) and (b), the upper figure shows the case where the shielding object is not present, and the lower figure is present.

  Next, as a result of intensive studies on the above-described novel resin curing mechanism and a polymerization reaction initiator that enables such a resin curing method, the present inventors have found that light / heat that initiates polymerization with both a photopolymerization initiator and light and heat. The present inventors have found that at least a binary photopolymerization initiator system (reaction catalyst system) using a polymerization initiator is useful for achieving the object of the present invention.

  Here, as a photopolymerization initiator, for example, a diazonium salt type compound as shown in Table A below, an iodonium salt type compound as shown in Table B, and the following general formula

  A compound of a pyridinium salt type as shown in FIG. 5, a compound of a phosphonium salt type as shown in Patent Documents 4 and 5, a compound of a sulfonium salt type as shown in Table C below (see Example Table 1 below), Initiator (9) shown in Table 1 (in the present specification, the initiator and oligomer numbers are indicated by numbers with (), but are indicated by circled numbers in the tables and figures). It is preferable to combine at least one of a compound and a sulfonic acid ester type compound and at least one sulfonium salt represented by the general formulas (I) to (VII) as a photo / thermal polymerization initiator.

  Further, as the radical photoinitiator, those shown in the following Table D and Table E are used.

Specific examples of the compounds represented by the general formulas (I) to (III) include photopolymerization initiators (1) to (3) used in Examples described later (see Non-Patent Document 1). .
Specific examples of the compound represented by the general formula (IV) include bis [4- (dimethylsulfonio) phenyl] sulfide bis-hexafluorophosphate, dimethyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate, and the like. . Specific examples of the compound represented by the general formula (V) include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, and specific examples of the compound represented by the general formula (VI) include benzyl-4- ( Ethoxycarbonyloxy) phenylmethylsulfonium hexafluoroantimonate, and a specific example of the compound represented by the general formula (VII) is 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate.

  As yet another combination, at least one kind of aryl type sulfonium salt type compound as shown in Table C (triarylsulfonium salt, for example, photoinitiator (6) in Table 1) as shown in Table C is used as a photopolymerization initiator. Preferred examples of the thermal polymerization initiator include a photopolymerization initiator system (reaction catalyst system) comprising at least one of the above-described sulfonium salts represented by the general formulas (I) to (III). It is done.

  Further, as a result of the further progress of the above research, the inventors of the present invention have developed photo / thermal polymerization initiators having high catalytic action against heat as photo / thermal polymerization initiators, such as those represented by the general formulas (I) to (III). The compounds (photoinitiators (1) to (3) in Table 1) are preferably used, and examples of the thermal polymerization initiator include prenyl tetramethylenesulfonium hexafluoroantimony represented by the chemical formula (VIII). We have found that it is preferable to use the 2-butynyltetramethylenesulfonium hexafluoroantimonate represented by the formula (IX).

  Finally, the following findings were obtained as a result of intensive studies on the above-described novel resin curing mechanism and the resin composition enabling the resin curing method. That is, it turned out that the resin composition which consists of a photoinitiator which consists of a binary system or more, a photopolymerizable oligomer, a photopolymerizable monomer, and such a molding are useful. In particular, application of a cationic photopolymerizable oligomer, a cationic photopolymerizable monomer, a photopolymerizable epoxy oligomer, or a photopolymerizable epoxy monomer is preferable. Examples of this type of photopolymerizable oligomer include alicyclic epoxy, glycidyl ether type epoxy, epoxidized polyolefin, epoxy (meth) acrylate, polyester acrylate, vinyl ether compound, etc., and examples of photopolymerizable monomers include epoxy. Monomers, acrylic monomers, vinyl ethers, cyclic ethers and the like can be mentioned. Among these, a photopolymerizable alicyclic epoxy oligomer and a photopolymerizable alicyclic epoxy monomer are preferable. As the photopolymerizable alicyclic oligomer, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate is particularly preferable. preferable.

  In particular, as the photopolymerization initiator, at least one of aryl sulfonium salt types (triarylsulfonium salts such as the photoinitiator (6) in Table 1) as shown in Table C and the photo / thermal polymerization initiator described above are used. A photopolymerization initiator system comprising at least a binary system containing at least one sulfonium salt represented by the general formulas (I) to (III), and 3,4-epoxycyclohexylmethyl-3,4- A resin composition comprising at least one photopolymerizable epoxy monomer or oligomer such as epoxycyclohexanecarboxylate and a molded product obtained therefrom are preferred.

  In the present invention, a preferable composition ratio of the resin composition is that a photopolymerization initiator system (reaction catalyst system) component consisting of a binary system or more with respect to 100 parts by weight of a photopolymerizable resin component (photopolymerizable oligomer or monomer). 0.5 to 6.0 parts by weight, preferably 1.5 to 3.5 parts by weight, and the weight ratio of photo / thermal polymerization initiator / photopolymerization initiator constituting the photopolymerization initiator system component is 1 to 1. 4, preferably 1.3 to 2.8. If the proportion of the photopolymerization initiator composed of two or more systems is less than 0.5 parts by weight, the effect is hardly obtained, and since the amount relative to the whole is small, the function itself is difficult to function. The curing function itself does not change. If the weight ratio of the photo / thermal polymerization initiator / photopolymerization initiator is smaller than 1, heat generation at the initial stage of curing is difficult to obtain, and the curing function that is a feature of the present invention is difficult to be exhibited, so only the resin surface is cured, If the number exceeds 4, the curing characteristics, particularly the heat generation characteristics, are abnormally increased, so that there is a problem that the resin is foamed by rapid heat curing. (Related data: Table 3, FIG. 9 and Table 4, FIG. 10).

  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 and other commonly used additives can be added.

  Furthermore, when manufacturing FRP, in particular CFRP, the high processing cost is caused by a (long-time) heat-curing process, and the size of the apparatus / equipment cannot be reduced. The reason why a heating furnace is necessary, that a short time curing resin cannot be used for a large FRP is that the curing start time cannot be controlled arbitrarily, and it is difficult to maintain the impregnation state and molding is difficult in the manufacturing process. Focusing on the fact that the viscosity of the resin changes due to heating, and that the generation of voids, which is a cause of quality degradation, is caused by the residual solvent. As a result of diligent research on a method for producing FRP, particularly CFRP, which can be arbitrarily controlled and does not require a solvent, the resin composition of the present invention is used as a matrix resin. After impregnating the fiber, using the novel resin curing mechanism and resin curing method of the present invention, FRP and CFRP production method for curing FRP and CFRP with energy rays typified by UV, and such products developed. In the present invention, a product means a product that can be artificially manufactured other than a building or a structure and is within the scope of the present invention.

  In the filament winding molding method using both UV curing and heat curing, which is representative of the prior art, UV curing is concerned only with surface curing and internal thickening, and eventually the entire curing is cured by heating as in the prior art. Therefore, the conventional technology still has unsolved various problems such as processing cost and working time related to the heat curing process and the necessity of a large heating furnace when molding a large FRP. Such FRP and CFRP manufacturing methods of the invention do not have such problems.

  Moreover, as for the FRP using the present invention, any fiber that is used as a reinforcing fiber of normal FRP such as carbon fiber, glass fiber, and organic fiber can be used as the reinforcing fiber, and the form of the fiber is also used. It can be in any form, such as aligned in one direction and woven and knitted. Further, carbon fiber and glass fiber or carbon fiber and a hybrid thereof may be used, and are not particularly limited. Furthermore, FRP molding methods (Figs. 7 and 8) include hand lay-up, spray-up, filament winding, tape winding, roll winding, pultrusion molding, roll press continuous molding, etc., including normal FRP molding methods. It is.

The invention will now be described in more detail by way of examples, which are not intended to be limiting.
[Example 1] ERL-4221 (manufactured by Union Carbide Co., Ltd .: alicyclic epoxy resin; 3,4-cyclohexylmethyl-3,4-epoxycyclohexanecarboxylate) 100 parts by weight of sun aid SI-80L (three Shin Chemical Co., Ltd .: Cationic photo / thermal polymerization initiator; 1.75 parts by weight of general formula (II)), DAICAT11 (Daicel Chemical Industries, Ltd .: Cationic photopolymerization initiator; aryl sulfonium salt) 0.75 part by weight was blended. (A)
Next, the resin concerning a glass container (φ40 mm × H80 mm) whose surroundings other than the upper part were covered with black paper was poured to the upper end of the glass container. (B)
This was irradiated with UV for 60 seconds. 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 19 cm. (C)
After UV irradiation, the resin in the glass container was completely cured within a few minutes, and the thickness of the resin was 80 mm (maximum value measured), which is the limit of the glass container.

[Examples 2 to 245 and Comparative Examples 1 to 187] The same conditions as in Example 1 were used except that the resin compositions shown in Table 1 were used and the tests were conducted at the composition ratios shown in Tables 2 and 3. And tested. The test results were as shown in Tables 2 and 3 and Tables 4 and 9. Moreover, the resin temperature measurement data by the heat_generation | fever of hardening became the result of FIG.

[Example 246] A resin composition similar to that in (A) of Example 1 was prepared, and a sample was prepared by the same method as in (B).
Irradiation distance: UV was irradiated under the same conditions as in (C) of Example 1 except for 25 cm. After UV irradiation, the resin in the glass container was completely cured within a few minutes, and the thickness of the resin was 80 mm (maximum measured value), which is the limit of the glass container (related figure: FIG. 11).

[Example 247] A resin composition similar to that in (A) of Example 1 was prepared, and a sample was prepared by the same method as in (B).
Irradiation distance: UV was irradiated under the same conditions as in Example 1 (C) except for 20 cm. After UV irradiation, the resin in the glass container was completely cured within a few minutes, and the thickness of the resin was 80 mm (maximum measured value), which is the limit of the glass container (related figure: FIG. 11).

Example 248 A resin composition similar to that in (A) of Example 1 was prepared, and a sample was prepared by the same method as in (B).
Irradiation distance: UV was irradiated under the same conditions as in (C) of Example 1 except for 15 cm. After UV irradiation, the resin in the glass container was completely cured within a few minutes, and the thickness of the resin was 80 mm (maximum measured value), which is the limit of the glass container (related figure: FIG. 11).

Example 249 A resin composition similar to that in (A) of Example 1 was prepared, and a sample was prepared by the same method as in (B).
UV irradiation device: UVL-3500M2 (Ushio Electric Co., Ltd.), lamp type: metal halide lamp, lamp intensity: 120 W / cm, lamp length: 250 mm, atmosphere / temperature / pressure: in air / room temperature / atmospheric pressure, irradiation distance: The sample was irradiated with UV under the conditions of 19 cm and irradiation time: 60 sec. (D)
After UV irradiation, the resin in the glass container was completely cured within a few minutes, and the thickness of the resin was 80 mm (maximum value measured), which is the limit of the glass container.

[Example 250] A resin composition similar to that in (A) of Example 1 was prepared, and a sample was prepared by the same method as in (B).
Lamp intensity: UV was irradiated under the same conditions as in Example 247 (D) except for 200 W / cm. After UV irradiation, the resin in the glass container was completely cured within a few minutes, and the thickness of the resin was 80 mm (maximum value measured), which is the limit of the glass container.

[Example 251] A resin composition similar to that in (A) of Example 1 was prepared, and a sample was prepared in the same manner as in (B).
Lamp intensity: UV was irradiated under the same conditions as in Example 247 (D) except for 280 W / cm. After UV irradiation, the resin in the glass container was completely cured within a few minutes, and the thickness of the resin was 80 mm (maximum value measured), which is the limit of the glass container.

[Example 252] A prepreg was prepared by impregnating an 18 cm x 18 CF cloth with a matrix resin obtained by preparing the same resin composition as in Example 1 (A). (E) 40 sheets of this prepreg were laminated (about 8 mm) and sandwiched between glass plates via a bag film, and then weighted from above to prepare a prepreg laminated sample (FIG. 12). (E)
UV irradiation was performed under the same conditions as in Example 1 (C) except for irradiation time: 3 min and irradiation distance: 15 cm. After UV irradiation, the laminate was fully cured and good CFRP was obtained (related data: Table 5).

[Example 253] A prepreg laminated sample was produced in the same manner as in Example 252 (E) except that the reinforcing fiber was impregnated with 18 x 18 GF cloth (lamination thickness: about 8 mm). UV was irradiated under the same conditions as in Example 252. After UV irradiation, the laminate was fully cured and good GFRP was obtained (related data: Table 5).

[Example 254] A prepreg laminated sample was prepared in the same manner as in Example 252 (E) except that 100 prepregs were laminated (about 20 mm). UV was irradiated under the same conditions as in Example 252. After UV irradiation, the laminate was completely cured and a good CFRP was obtained.

[Example 255] A prepreg laminated sample was prepared in the same manner as in Example 252 (E) except that the resin composition of Example 13 was used as the matrix resin. UV was irradiated under the same conditions as in Example 252. After UV irradiation, the laminate was completely cured and a good CFRP was obtained.

Example 256 A prepreg laminated sample was produced in the same manner as in Example 252 (E). An electron beam (EB) was used as the energy beam. Irradiation conditions were as follows: irradiation apparatus: Linac (High Voltage Arco Co., Ltd., beam energy: 10 MeV, scan frequency: 4 Hz, pulse repetition rate: 60 Hz, scan width: 20 cm, pulse width: 4 μsec, radiation dose: 50 kGy. After UV irradiation, the laminate was completely cured and a good CFRP was obtained.

[Example 257] A matrix resin was prepared by the same method as in Example 252 (E), impregnated with carbon fiber, and then wound at a winding speed of 30 cm / sec (filament winding method). CFRP cylindrical laminated material was molded (thickness 3 mm) (F)
After complete winding, the cylindrical laminate was irradiated with UV from all directions (irradiation conditions were the same as in Example 252). After the UV irradiation, the laminate was completely cured, and a good filament winding CFRP was obtained.

[Example 258] A cylindrical laminate made of GFRP was formed (plate thickness: 3 mm) in the same manner as in Example 257 (F) except that glass fiber was used as the reinforcing fiber. After complete winding, the cylindrical laminate was irradiated with UV from all directions (irradiation conditions were the same as in Example 252). After the UV irradiation, the laminate was completely cured, and a good filament winding GFRP was obtained.

Example 259
For 100 parts by weight of Celoxide 2021P (oligomer [1], manufactured by Daicel Chemical Industries, Ltd .: alicyclic epoxy resin; 3,4-cyclohexylmethyl-3,4-epoxycyclohexanecarboxylate), Sun Aid S1-80L (light Initiator [2], manufactured by Sanshin Chemical Co., Ltd .: Cationic photo / thermal polymerization initiator; 1.50 parts by weight, general formula (II)), DAICAT11 (photoinitiator [6], Daicel Chemical Industries, Ltd.) Manufactured by: Cationic photopolymerization initiator; aryl sulfonium salt) 0.50 parts by weight, 4,4′-bis [di (竈 -hydroxyethoxy) phenylsulfonio] phenyl sulfide-bis-hexafluoroantimonate (light initiator [13]) 0.50 parts by weight, 2-butynyl tetramethylene sulfonium hexafluoroantimonate (thermal initiators [15]: general formula (IX)) 0.50 Except for testing a resin composition containing an amount unit was tested under the same conditions as in Example 1. After UV irradiation, the resin in the glass container was completely cured within a few minutes, and the thickness of the resin was 80 mm (maximum value measured), which is the limit of the glass container.

Example 260
For 100 parts by weight of Celoxide 2021P (oligomer [1], manufactured by Daicel Chemical Industries, Ltd .: alicyclic epoxy resin; 3,4-cyclohexylmethyl-3,4-epoxycyclohexanecarboxylate), Sun Aid SI-80L (light Initiator [2], manufactured by Sanshin Chemical Co., Ltd .: Cationic photo / thermal polymerization initiator; 1.50 parts by weight, general formula (II)), DAICAT11 (photoinitiator [6], Daicel Chemical Industries, Ltd.) Manufactured: Cationic photopolymerization initiator; aryl sulfonium salt (1.00 part by weight) and prenyltetramethylenesulfonium hexafluoroantimonate ( thermal initiator [14]: general formula (VIII)) (0.50 part by weight) The test was performed under the same conditions as in Example 1 except that the test was performed using the resin composition. After UV irradiation, the resin in the glass container was completely cured within a few minutes, and the thickness of the resin was 80 mm (maximum value measured), which is the limit of the glass container.

[Comparative Examples 188 to 190] All tests were conducted by the methods of Examples 246 to 248 except that the composition of Comparative Example 1 was used as the resin composition. The thickness of the resin after UV irradiation was about 1 mm and the inside was uncured. (Related diagram: FIG. 11).

[Comparative Example 191] A prepreg laminated sample was prepared in the same manner as in Example 252 (E) except that the resin composition of Comparative Example 1 was used for the matrix resin. UV was irradiated under the same conditions as in Example 252. CFRP after UV irradiation cured only the surface layer portion of the first irradiated surface, and the resin interior was completely uncured.

[Comparative Example 192] A prepreg laminated sample was prepared in the same manner as in Example 253 except that the resin composition of Comparative Example 1 was used as the matrix resin. UV was irradiated under the same conditions as in Example 252. The GFRP after UV irradiation cured only to the 2nd to 3rd layer portions of the irradiated surface, and the inside of the resin was completely uncured.

[Examples 261 to 282] Tests were performed under the same conditions as in Example 1 except that the resin compositions shown in Table 1 were used and the tests were conducted at the resin composition ratios shown in Table 6 (continued from Table 2). The test results are shown in Table 6.

Example 283 A resin composition similar to that in (A) of Example 1 was prepared, and a sample was prepared by the same method as in (B). Instead of irradiating the prepared sample with energy rays, it was heated in an oven maintained at 150 ° C. The resin in the glass container was sufficiently cured from the start of heating, and the thickness of the resin was 80 mm (maximum value measured), which is the limit of the glass container.

[Example 284] A resin composition similar to that in (A) of Example 1 was prepared, and a sample was prepared in the same manner as in (B). The prepared sample was put in an oven adjusted in a temperature range (60 ° C. in this example) where curing does not start, and held until the resin temperature became equal to the atmosphere temperature in the oven. Thereafter, the sample was taken out of the oven and tested under the same conditions as in Example 1. After UV irradiation, the resin in the glass container was completely cured within a few minutes (shorter time than Example 1), and the thickness of the resin was 80 mm (maximum measurement value), which is the limit of the glass container.

〔The invention's effect〕
[Resin Composition Enabling New Resin Curing Mechanism] From the test results of Examples 1 to 60, Examples 259 to 282 and Comparative Examples 1 to 20 described in Tables 1 to 3 and Table 6. It can be seen that the composition of the present invention equipped with a novel resin curing mechanism is excellent in energy beam curability, particularly thick-wall curability. Furthermore, from Example 284, it can be seen that curing with an energy beam after heating the composition of the present invention in advance (temperature range at which it does not cure) is more effective for curing. Moreover, it confirmed that the composition of this invention which contains the photoinitiator which consists of a binary system or more from Example 283 in a composition hardens | cures in a short time also by a heating.

[A Photopolymerization Initiator System Consisting of Two or More Binary Systems Enabling a New Resin Curing Mechanism and Its Appropriate Ratio] Examples 1 to 245 and Comparative Examples 1 to 1 described in Tables 1 to 3 and FIG. From the test results of Comparative Example 187, the effectiveness and appropriate ratio of a photopolymerization initiator system comprising a binary system or more that enables a novel resin curing mechanism is clear.

[Verification of New Resin Curing Mechanism] Among the results of Examples 1 to 245 and Comparative Examples 1 to 187, the resin temperature rise due to the heat of curing of the resin when irradiated with the energy rays of the compositions described in Table 4 The curve is shown in FIG. Further, FIG. 11 shows resin temperature rise curves due to the heat generated by curing the resin during energy ray irradiation in Examples 246 to 248 and Comparative Examples 188 to 190. 10 and 11, the resin composition of the present invention has energy different from the energy from the energy ray source, in this case, heat energy due to curing reaction heat (curing heat generation) is self-generated inside the resin, and heat due to the curing reaction. It is clear that this is due to a novel resin curing mechanism in which the resin composition is cured by energy and energy from an energy beam source. Further, from the test results of Example 246 to Example 251, it can be confirmed that the novel resin curing mechanism according to the present invention is effective even if the irradiation condition of the energy beam is changed.

[Verification of CFRP (Energy Ray Shielding Substance-Containing Thick Resin) and GFRP Curability] From the results of Examples 252 to 258 and Comparative Examples 191 to 192, the novel resin curing mechanism of the present invention and this The photo-polymerization initiator system and the resin composition composed of two or more binary systems that enable the photo-curing (energy-ray curing) of CFRP (energy beam shielding substance-containing thick resin), which could not be achieved with conventional photo-curing resins, and It is clear that photocuring (energy ray curing) such as GFRP is realized. Further, from Example 256, the novel resin curing mechanism according to the present invention, a photopolymerization initiator system and a resin composition comprising two or more systems enabling this, and the FRP (CFRP) production method using the present invention are as follows. It can be confirmed that the present invention can also be applied to EB curing of FRP (CFRP). Furthermore, from Example 257, it is clear that the FRP (CFRP) manufacturing method according to the present invention can be applied not only to the lay-up method but also to other FRP manufacturing methods such as the filament winding method.

[CFRP and GFRP Molded Articles Produced by the Present Invention] The basic physical properties of CFRP and GFRP produced in Examples 252 to 253 were measured and are shown in Table 5. It turns out that it is a favorable sample from Table 5.

  The curing method of the present invention, the composition therefor, the molded product and the molding method are effective regardless of the presence or absence, length, size, and shape of the UV shielding property of the fiber or filler. In addition, it can be applied to fields such as adhesives, sealants, varnishes, paints, coating materials, inks, and toners.

The schematic diagram which shows the state of attenuation | damping of the UV energy which permeate | transmits a resin composition. The schematic diagram which shows the state of attenuation | damping of the UV energy which permeate | transmits the resin composition containing a carbon cloth material. The schematic diagram which shows the UV hardening state of the resin composition in FIG.1 and FIG.2. The schematic diagram for demonstrating the resin hardening mechanism (light + hardening reaction heat and cation hardening system) which concerns on this invention. Explanatory drawing of the hardening model of high UV curable resin. Explanatory drawing of the hardening model of UV and heating combined use curable resin in the conventional method. It is process drawing which shows the example of a FRP shaping | molding method. (1) A layup method is shown. It is process drawing which shows the example of FRP molding method. (2) Drawing method, (3) Filament tape roll / winding molding method, (4) Roll press continuous molding method. The graph which shows the appropriate ratio range of the photoinitiator type | system | group in this invention. The graph which shows the relationship between the elapsed time 60 seconds after UV irradiation in this invention, and resin temperature. The graph which shows the relationship between the UV irradiation distance in this invention, and the resin temperature 60 seconds after UV irradiation. Explanatory drawing which shows the condition which produces the prepreg laminated sample by this invention.

Claims (10)

It consists of a binary system having a photopolymerization initiator and a light / thermal polymerization initiator that initiates polymerization with both light and heat as components, and 0.5 parts per 100 parts by weight of the photopolymerizable oligomer or monomer. -6.0 parts by weight, a polymerization initiator having a weight ratio of the photo / thermal polymerization initiator / the photopolymerization initiator of 1 to 4, and
Curing is started by irradiation of energy rays to generate curing reaction heat, and the curing reaction proceeds in a chain by the curing reaction heat to continuously generate curing reaction heat, and the energy ray shielding substance in the resin composition. A polymerization initiator having the property of causing the curing reaction to proceed in a chain manner by the self-generated heat of the curing reaction without irradiation of energy rays, regardless of the presence or absence of . Furthermore, Polymerization initiator according to claim 1 comprising adding a thermal polymerization initiator. Photopolymerization initiator, thermal polymerization initiator, two or more of the light-thermopolymerization initiator, Polymerization initiator according to claim 1 or 2, characterized in that a radical polymerization initiator. Photopolymerization initiator, thermal polymerization initiator, two or more of the light-thermopolymerization initiator, Polymerization initiator according to claim 1 or 2, characterized in that an anionic polymerization initiator. Photopolymerization initiator, thermal polymerization initiator, two or more of the light-thermopolymerization initiator, Polymerization initiator according to claim 1 or 2, characterized in that a cationic polymerization initiator. As a photopolymerization initiator , at least one of a diazonium salt type, an iodonium salt type, a pyridinium salt type, a phosphonium salt type, a sulfonium salt type, an iron-allene compound type, and a sulfonic acid ester type is included .
As photo / thermal polymerization initiators , sulfonium salts represented by the following general formulas (I), (II), (II) ′, (III), (IV), (V), (VI) and (VII) Polymerization initiator according to claim 5, characterized in that it comprises at least one.

(Where R ¹ is hydrogen, methyl group, acetyl group, methoxycarbonyl group, R ² and R ³ are independently hydrogen, halogen, or C ₁ -C ₄ alkyl group, R ⁴ is hydrogen, halogen, A methoxy group, R ⁵ represents a C _{1 to} C ₄ alkyl group, and A represents SbF ₆ , PF ₆ , AsF ₆ , or BF ₄ .

(In the above formula (II) or (II ′), R ⁶ is a hydrogen atom, halogen atom, nitro group, methyl group, R ⁷ is a hydrogen atom, CH ₃ CO, CH ₃ OCO, A is SbF ₆ , PF ₆ , BF ₆ and AsF _6. )

(In the above formula, R ⁸ represents a hydrogen atom, CH ₃ CO, CH ₃ OCO, and B represents SbF ₆ , PF ₆ , BF ₆ , AsF ₆ , and CH ₃ SO _4. )

[In the formula (a), R ⁹ is a C ₁ -C ₁₈ aliphatic group, R ¹⁰ is a C ₁ -C ₁₈ aliphatic group or a C ₆ -C ₁₈ substituted or unsubstituted aromatic group, R ⁹ and R ¹⁰ may be bonded to each other to form a ring].

[In the formula (b), R ¹¹ is a C ₁ -C ₁₈ aliphatic group, R ¹² is a C ₁ -C ₁₈ aliphatic group or a C ₆ -C ₁₈ substituted or unsubstituted aromatic group, R ¹¹ and R ¹² may be bonded to each other to form a ring], a hydrogen atom, a halogen atom, a nitro group, an alkoxy group, a C _{1 to} C ₁₈ aliphatic group, or C _{A 6 to} C ₁₈ substituted or unsubstituted phenyl, phenoxy or thiophenoxy group; In the formula (IV), n and m are each independently an integer of 1 to 2, Z is a formula MQ ₁ or MQ _1-1 OH (M is B, P, As or Sb, Q is a halogen atom, l is an integer of 4 or 6.

(Wherein R ^13, R ¹⁴ independently represent hydrogen or an alkyl group of C ₁ -C _4, A is. Indicating an _{SbF 6, PF 6, AsF 6} )

(Wherein R ¹⁵ is any one of ethoxy, phenyl, phenoxy, benzyloxy, chloromethyl, dichloromethyl, trifluoromethyl, and trifluoromethyl; R ¹⁶ and R ¹⁷ are independently hydrogen, halogen, Any one of C _{1 to} C ₄ alkyl groups, R ¹⁸ represents hydrogen, methyl group, methoxy group or halogen, R ¹⁹ represents C _{1 to} C ₄ alkyl group, A represents SbF ₆ , PF ₆ , BF ₄ and AsF ₆ are shown.)

(Wherein Q is a methoxycarbonyloxy group, acetoxy group, benzyloxycarbonyloxy group, dimethylamino group, R ²⁰ and R ²¹ are independently hydrogen, and any one of C ₁ -C ₄ alkyl groups is R ²² , R ²³ independently represents any of a C _{1 to} C ₄ alkyl group, and A represents SbF ₆ , PF ₆ , AsF ₆ , or BF ₄ . As a photopolymerization initiator , it contains at least one aryl sulfonium salt type,
As the light-heat polymerization initiator, the general formula (I), Polymerization initiator according to claim 6, characterized in that it comprises at least one sulfonium salt type of formula (II) or (III). As a thermal polymerization initiator, Polymerization initiator according to any one of claims 2-7, characterized in that it comprises at least one compound of formula (VIII) and (IX).

The manufacturing method of the resin cured material using the polymerization initiator of any one of Claims 1-8 . Method for producing a resin cured product according to claim 9, characterized in that to facilitate cure more by warming at a temperature range that does not cure the pre Me resin composition.

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