JP2016030822A - Reinforced fiber resin composite and method for producing structure reinforced using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reinforced fiber resin composite which is suitable as a stickable prepreg and has excellent storage stability.SOLUTION: There is provided a reinforced fiber resin composite obtained by impregnating a resin composition in a reinforced fiber resin. The resin composition comprises an epoxyprepolymer compound (a), a vinyl chloride resin (b) and an unreacted latent epoxy curing agent (c). The vinyl chloride resin (b) is compatible with the epoxyprepolymer compound (a) or is swollen in the epoxyprepolymer compound (a). In the resin composition, 1 pt.wt. or more and 70 pts.wt. or less of the vinyl chloride resin (b) can be incorporated based on 100 pts.wt. of the epoxyprepolymer compound (a).SELECTED DRAWING: Figure 1

Description

The present invention relates to a reinforced fiber resin composite. More specifically, the present invention relates to a prepreg applicable to concrete repair.
Furthermore, this invention relates to the manufacturing method of the structure using the said reinforced fiber resin composite. More specifically, the present invention relates to a method for repairing a concrete structure or piping using a prepreg.

  Epoxy resins are used in a wide variety of applications because their cured products are excellent in performance such as mechanical properties, electrical properties, thermal properties, chemical resistance, and adhesiveness. For example, there are uses such as insulating materials for electric and electronic materials, adhesives, coating agents for civil engineering and construction, matrix resins for reinforcing fiber composites for putty, vehicle structural members, and the like.

  The aspect of the epoxy resin composition which is currently mainstream is a so-called two-component type in which two components of an epoxy resin and a curing agent are mixed at the time of use. The two-part epoxy resin composition stores the epoxy resin and the curing agent separately, and it is necessary to weigh and mix the two each time they are used. . Therefore, the frequency of blending work is inevitably increased, and it is inevitable that work efficiency is lowered and yield is deteriorated.

  In addition, the two-component epoxy resin composition can be cured in a room temperature environment, but has a problem that the curing time is long. In particular, when it is used for applications that are affected by the outside temperature, such as civil engineering and construction, if the outside temperature is low, it takes a very long time to cure. It was.

In order to solve these problems, a one-component epoxy resin composition has been proposed. The one-part epoxy resin composition is a mixed system of an epoxy resin and a latent curing agent, and examples of the latent curing agent include dicyandiamide, BF ₃ -amine complex, modified imidazole compound, and onium salt polymerization initiator. Examples of the compound and a hardener compound that can be used in these compounds or in two-part form are microencapsulated or clathrated.

  The reinforcing fiber composite, which is one of the uses of the epoxy resin, is handled in a state in which the resin composition is impregnated into the reinforcing fiber and semi-cured, which is referred to as a prepreg, before the epoxy resin composition is completely cured. It is known that In such a prepreg, a one-component epoxy resin composition is often employed as a matrix resin.

  For example, JP 2007-270136 A (Patent Document 1) discloses a sheet molding compound (SMC) molding material for heat compression molding using an onium salt thermal cationic polymerization initiator as a curing agent. It is shown that the molding material can be molded in a short time such as a mold temperature of 130 to 160 ° C., an in-mold pressure of 5 to 10 MPa, and a molding time of 1 to 3 minutes.

  Japanese Laid-Open Patent Publication No. 01-297532 (Patent Document 2) discloses the use of carbon fiber prepregs for reinforcing concrete structures. Patent Document 2 mentions diaminodiphenyl sulfone and diaminodiphenylmethane as curing agents contained in the carbon fiber prepreg, and describes that they are stored at -20 ° C to 0 ° C.

  Further, in order to obtain a semi-cured state having adhesiveness required as a prepreg, for example, an acrylic resin powder like a heat compression molding material composition described in JP-A No. 11-181245 (Patent Document 3). Is generally used as a thickener.

  In JP-A-55-127469 (Patent Document 4), a coating composition comprising an epoxy prepolymer compound, polyvinyl chloride dispersible with respect to the epoxy prepolymer compound, and a photopolymerization initiator is disclosed. It is disclosed. It is described that the coating composition is cured to a tack-free state by light irradiation after coating, and then the polyvinyl chloride is melted by baking.

JP 2007-270136 A JP-A-01-297532 Japanese Patent Laid-Open No. 11-181245 JP-A-55-127469

  In the SMC molding material of patent document 1, in order to obtain a semi-hardened state, it processed for 20 minutes-1 hour in 70-90 degreeC atmosphere, and the onium salt type | system | group thermal cationic polymerization initiator is made to react. For this reason, the activated initiator remains in the prepreg. That is, sufficient storage stability cannot be obtained. In particular, application as a prepreg on the premise of room temperature storage and outdoor use for several months, such as civil engineering and building applications, is virtually impossible.

  The carbon fiber prepreg described in Patent Document 2 requires a low temperature of about −20 ° C. to 0 ° C. as the storage temperature. Therefore, it is obvious that storage stability cannot be obtained because it cannot withstand room temperature storage that is assumed in civil engineering and building applications. Assuming a prepreg for processing a large area such as civil engineering and construction, even if it is stored in low temperature conditions in a roll shape to accommodate such a processing area, the required storage capacity is It is enormous and is not practical considering the utility cost for maintaining the low temperature and the conveyance maintaining the low temperature storage state.

  The heat compression molding material composition described in Patent Document 3 can withstand a storage environment of about 6 days under 25 ° C. conditions, but is assumed to be stored outdoors as in civil engineering applications, and for several months. Therefore, it is practically difficult to apply as a prepreg that is required to maintain flexibility.

  The coating composition described in Patent Document 4 is used for light irradiation and subsequent melting. In the first light irradiation, the initiator is decomposed to start polymerization of the epoxy prepolymer material, and tack-free. There is a need to. In other words, it is necessary to have a state without adhesiveness. In order to obtain such a tack-free state, it is necessary to include polyvinyl chloride in an unswelled dispersion state in the epoxy prepolymer material. Therefore, it is impossible to construct a prepreg that can be attached.

  Accordingly, an object of the present invention is to provide a reinforced fiber resin composite suitable as an attachable prepreg and having excellent storage stability.

As a result of intensive studies, the present inventor has achieved the above object by including a vinyl chloride resin in a compatible or swollen state in an epoxy prepolymer compound and including a latent curing agent in an inactive state. It has been found that this has been achieved, and the present invention has been completed.
The present invention includes the following inventions.

(1)
The reinforcing fiber resin composite of the present invention is obtained by impregnating a reinforcing fiber resin with a resin composition. The resin composition includes an epoxy prepolymer compound (a), a vinyl chloride resin (b), and a latent epoxy curing agent (c). The vinyl chloride resin (b) is compatible with the epoxy prepolymer compound (a) or swelled in the epoxy prepolymer compound (a).

  In the above, “compatible” means that the epoxy prepolymer compound (a) and the vinyl chloride resin (b) are completely mixed at the molecular level. Swelling means that the epoxy prepolymer compound (a) has entered between the molecules of the vinyl chloride resin (b) to increase the intermolecular distance. The swollen vinyl chloride resin (b) usually has a particulate form.

  With this configuration, the reinforced fiber resin composite is suitable as an attachable prepreg, and is excellent in storage stability. Specifically, since the vinyl chloride resin (b) is used in the resin composition impregnated in the reinforcing fiber resin, it is suitable as a prepreg having toughness and low cost. In addition, the vinyl chloride resin (b) may be a part of the curing action by the latent epoxy curing agent (c) or assist the curing action when the reinforced fiber resin composite is completely cured.

  The vinyl chloride resin (b) is compatible with the epoxy prepolymer compound (a) or swelled in the epoxy prepolymer compound (a), so that it can be attached to an object. Have. Furthermore, by including the latent epoxy curing agent (c) (that is, the curing agent in an activated state is not substantially contained), the storage stability is also excellent.

(2)
In the resin composition, the vinyl chloride resin (b) can be contained in an amount of 1 to 70 parts by weight with respect to 100 parts by weight of the epoxy prepolymer compound (a).

  As a result, the reinforced fiber resin composite becomes more suitable as a prepreg that can be attached. Specifically, when the content is 1 part by weight or more, it becomes easy to obtain toughness and low cost, and it is easy to obtain tackiness that is not too strong suitable for handling. When the content is 100 parts by weight or less, it is easy to obtain a tackiness that is not too weak and suitable for the application.

(3)
The average degree of polymerization of the vinyl chloride resin (b) may be 400 or more and 1500 or less.

  When the average degree of polymerization is 400 or more, it is easy to obtain preferable physical properties (for example, toughness), and it is easy to obtain adhesiveness suitable for use with an appropriate addition amount. When the average degree of polymerization is 1500 or less, an aspect of compatibility or swelling can be easily obtained for the epoxy prepolymer compound.

  The average degree of polymerization refers to a resin obtained by dissolving a vinyl chloride resin in tetrahydrofuran, removing insoluble components by filtration, and then removing the tetrahydrofuran in the filtrate by drying, and using JIS K-6721 “vinyl chloride” as a sample. The average degree of polymerization measured in accordance with “resin test method”.

(4)
In the resin composition, the latent epoxy curing agent (c) can be contained in an amount of 0.01 to 5 parts by weight with respect to 100 parts by weight of the epoxy prepolymer compound (a).

  When the content is 0.01 parts by weight or more, it is easy to obtain the effect of the latent epoxy curing agent. By being 5 parts by weight or less, the efficiency for obtaining the effect of the latent epoxy curing agent is good, and the cost is excellent.

(5)
The resin composition constituting the reinforced fiber resin composite preferably has a viscosity of 500 Pa · s to 8000 Pa · s at 30 ° C, and 1 Pa · s to 500 Pa · s at 80 ° C.

By setting the viscosity to 500 Pa · s or higher in a working environment typified by 30 ° C., it is possible to suppress exudation of the liquid component from the reinforced fiber resin composite and to ensure appropriate releasability. On the other hand, when the viscosity is 8000 Pa or less, surface tackiness suitable for the application can be obtained.
The viscosity in the above (5) is a viscoelasticity measuring device (MCR102 manufactured by Anton Paar), the radius of the parallel plate is 25 mm, the distance between parallel is 1 mm, the measurement frequency is 0.5 Hz, and the temperature is 2 ° C./min. This is the value obtained from the complex viscosity η when the temperature is raised at.

(6)
The reinforcing fiber resin composite is preferably formed in a sheet shape, and a release sheet is preferably laminated on at least one surface.

  Thereby, it is possible to stack or wind up the reinforcing fiber resin composite through the release sheet. Therefore, it is excellent in handling when not used for the use of the reinforcing fiber resin composite, such as during storage and transportation, and can be used by peeling the release sheet.

(7)
The latent epoxy curing agent (c) is preferably a cationic polymerization initiator.

  Since the cationic polymerization system is not oxygen-inhibited, it has excellent surface curability in indoor and outdoor environments (air environments) and has low curing shrinkage when the reinforced fiber resin composite is completely cured. In addition, the work efficiency is good due to the excellent curing efficiency.

(8)
The latent epoxy curing agent (c) may be a thermal polymerization initiator that reacts at a temperature of 90 ° C. or higher and 200 ° C. or lower.

  By being a thermal polymerization initiator, the complete curing reaction of the reinforcing fiber resin composite becomes possible regardless of whether the reinforcing fiber is transparent or not. When the temperature is 90 ° C. or higher, it is suitable for outdoor storage, and it is not necessary to use a special temperature adjusting device for storage, and thus it has excellent storage stability. By being 200 ° C. or less, complete curing can be performed under relatively mild conditions, and even if a low boiling point substance is contained in the epoxy prepolymer compound, complete curing can be performed without generating bubbles. Can do.

(9)
The latent epoxy curing agent (c) may be a photopolymerization initiator.
Thereby, it is excellent in storage stability in that it can be stored regardless of temperature.

(10)
The latent epoxy curing agent (c) can contain both a thermal polymerization initiator and a photopolymerization initiator.

  Thereby, since a combination polymerization reaction system is constructed at the time of complete curing of the reinforced fiber resin composite, good curability can be obtained. For this reason, it can be preferably adapted even when the reinforcing fiber resin composite is large.

(11)
The latent epoxy curing agent (c) has the following general formula (I):
(In the formula, R ₁ represents an alkyl group having 1 to 4 carbon atoms, and R ₂ , R ₂ ′, and R ₂ ″ may be the same as or different from each other, a hydrogen atom or 1 to 4 carbon atoms. R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₄ represents an alkyl group having 1 to 4 carbon atoms or an optionally substituted phenyl group, X ^- the Hammett acidity function represents the -12 anion superacid).
It may be a thermal acid generator or an energy ray acid generator represented by:

In this case, since the sulfonium compound represented by the above formula (I) can efficiently generate an acid, the reaction efficiency of cationic polymerization is good. The thermal acid generator or energy ray acid generator is a substance that generates a super strong acid using heat or energy rays as a trigger, and decomposes in an autocatalytic manner using an acid as a trigger to increase the acid concentration nonlinearly. Different from acid proliferators.
Furthermore, by combining the sulfonium compound with another polymerization initiator, a frontal polymerization system can be constructed at the time of complete curing of the reinforced fiber resin composite. For example, thermal decomposition of the sulfonium compound and generation of acid can be induced by reaction heat from the other polymerization initiator, and the polymerization reaction can be propagated in a self-promoting manner. Therefore, even when the thickness of the fiber resin composite is large, good curability can be exhibited.

(12)
The reinforced fiber resin composite of the present invention is obtained by heating and mixing the epoxy prepolymer compound (a) and the vinyl chloride resin (b). The vinyl chloride resin (b) is obtained by combining the epoxy prepolymer compound (a) with the epoxy prepolymer compound (a). The latent epoxy curing agent (c) under conditions that maintain the latent epoxy curing agent (c) inert to the heat-mixed resin, which is compatible or swollen with the epoxy prepolymer compound (a). ) Is added to the reinforcing fiber and the fluid curable resin composition is obtained.

  Thus, in the reinforced fiber resin composite of the present invention, the vinyl chloride resin (b) is compatible with the epoxy prepolymer compound (a) or swelled in the epoxy prepolymer compound (a). It has the adhesiveness which can be stuck on a target object. Furthermore, since it is a thing obtained without going through the process of activating the latent epoxy curing agent (c), it is excellent in storage stability.

(13)
The reinforced cementitious structure of the present invention is a completely cured body in which the reinforced fiber resin composite of the above (1) to (12) is completely cured, and a cemented structure in which the completely cured body is fixed to the surface,
including.

Since the reinforced fiber resin composite of (1) to (12) is excellent in sticking property and storage stability, the cemented structure that is stuck and fully cured on the surface of the cemented structure is preferably reinforced. Yes.
In addition, in this invention, reinforcement includes both repair reinforcement with respect to the abnormality which arose in the cementitious structure, and the prevention reinforcement which prevents generation | occurrence | production of the abnormality which may arise in a cementitious structure.

(14)
The method for producing a reinforced fiber resin composite of the present invention includes a heating and mixing step, a curing agent addition step, and an impregnation step.
In the heating and mixing step, the epoxy prepolymer compound (a) and the vinyl chloride resin (b) are heated and mixed to obtain a heated mixed resin. The heating is performed until the vinyl chloride resin (b) is in a state compatible with the epoxy prepolymer compound (a) or swollen in the epoxy prepolymer compound (a).
In the curing agent addition step, a fluid curable resin composition is obtained in which the latent epoxy curing agent (c) is added to the heat-mixed resin. In this case, the latent epoxy curing agent (c) is added under conditions that keep it inert.
In the impregnation step, the reinforcing fiber is impregnated with the fluid curable resin composition to obtain a reinforcing fiber resin composite.

  With the above configuration, a reinforced fiber resin composite that is suitable as a prepreg that can be attached and that is excellent in storage stability can be obtained. The vinyl chloride resin (b) is compatible with the epoxy prepolymer compound (a) or swelled in the epoxy prepolymer compound (a), so that it is suitable for the surface of the reinforced fiber resin composite. It can be thickened to a viscosity that can impart tackiness. Furthermore, since the latent epoxy curing agent (c) is added under the inert conditions and does not include a step of actively activating the latent epoxy curing agent (c), the storage stability is also excellent. A reinforced fiber resin composite can be obtained.

  When the latent epoxy curing agent (c) does not contain a thermal polymerization initiator, the heat mixing step and the curing agent mixing step may be performed simultaneously or separately in this order. . When the latent epoxy curing agent (c) contains a thermal polymerization initiator, the heating mixing step and the curing agent mixing step are performed separately in this order.

(15)
The vinyl chloride resin (b) is preferably particulate.
Thereby, in the heating and mixing step, it is easy to obtain a state in which the vinyl chloride resin (b) is compatible with the epoxy prepolymer compound (a) or a state swollen in the epoxy prepolymer compound (a). Moreover, it is excellent in handling property.

  In the heat mixing step, the heat mixed resin may be obtained as the viscosity adjusted by a diluent. For example, when the use ratio of a low molecular weight epoxy compound (for example, monomer, oligomer) is small or not used as the epoxy prepolymer compound (a), or when a vinyl chloride resin (b) having a high degree of polymerization is used or A diluent can be used to increase the use ratio. Thereby, an impregnation process can be performed easily.

(17)
When the latent epoxy curing agent (c) includes at least a thermal polymerization initiator, in the curing agent addition step, the heated mixed resin is cooled to a temperature lower than the reaction temperature of the latent epoxy curing agent (c), and then the latent potential is increased. Add epoxy curing agent (c).

  Thus, a reinforced fiber resin composite can be obtained in a state in which the thermal polymerization initiator is unreacted while including a production process subjected to heating conditions.

(18)
The viscosity of the flowable curable resin composition under temperature conditions in the impregnation step is preferably 1 Pa · s or more and 500 Pa · s or less.

  By increasing the viscosity to such a value, resin impregnation into the reinforcing fiber can be easily performed.

(19)
The manufacturing method of the reinforced cementitious structure of the present invention includes a pasting step and a curing step.
In the sticking step, the reinforcing fiber resin composites of the above (1) to (13) are stuck on the surface of the cementitious structure. In addition, when the release sheet is laminated | stacked, the release sheet of a sticking surface is peeled previously.
In the curing step, the affixed reinforcing fiber resin composite is subjected to the active conditions of the latent epoxy curing agent (c) to cure the epoxy prepolymer compound (a) to obtain a reinforced cementitious structure. .

  Since the reinforcing fiber resin composites (1) to (12) are excellent in sticking property and storage stability, they are stuck on the surface of the cementitious structure and completely cured. Therefore, the above cementitious structure can be preferably reinforced.

It is the graph which monitored thermal decomposition about one of the sulfonium compounds used by this invention.

[Reinforced fiber resin composite]
The reinforcing fiber resin composite of the present invention is a reinforcing fiber impregnated with a matrix resin. The impregnated matrix resin is maintained in a pregelled state. The pregelled state means a state in which the resin can maintain its own shape without going through a curing reaction step. The surface of the reinforced fiber resin composite has adhesiveness due to the thickened matrix resin. Therefore, a release sheet may be provided on one or both of the surfaces of the reinforcing fiber resin composite.

  The resin composition that causes the adhesion of the surface of the reinforced fiber resin composite is 500 Pa · s or more and 8000 Pa · s or less, preferably 800 Pa · s or more and 8000 Pa · s or less at 30 ° C, and 1 Pa · s or more and 500 Pa · s or less at 80 ° C. It may have a viscosity of s or less. When the resin viscosity is equal to or higher than the above lower limit, leaching of the liquid component from the composite is suppressed, and when the release sheet is laminated on the surface of the composite, the release sheet is good. Peelability can also be obtained. When the resin viscosity is not more than the above upper limit, it is possible to obtain adhesiveness that is not too weak and suitable for use. Therefore, a preferable application state is maintained at the time of application to an object. Moreover, the adhesiveness which is not too strong suitable for handling can also be obtained.

[Resin composition]
The matrix resin is composed of a resin composition containing an epoxy prepolymer compound (a), a vinyl chloride resin (b), and a latent epoxy curing agent (c). When the latent epoxy curing agent is a cationic polymerization initiator of the epoxy prepolymer compound (a), a cationic polymerizable compound other than the epoxy prepolymer compound (a) can further be included.

[(A) Epoxy prepolymer compound]
The epoxy prepolymer compound is a molecule having an epoxy group having one or more functions, preferably two or more functions. Specifically, it means at least one of a monomer having an epoxy group, an oligomer having an epoxy group, and a polymer having an epoxy group. Since the viscosity is preferably increased by using a vinyl chloride resin described later in combination, the epoxy prepolymer compound preferably contains at least a monomer or an oligomer, and may be only a monomer or an oligomer.
Furthermore, examples of the epoxy prepolymer compound include a glycidyl ether type, a glycidyl amine type, a glycidyl ester type, and an alicyclic epoxy compound.

  The glycidyl ether type, glycidyl amine type and glycidyl ester type epoxy compounds can be obtained from a halide having a glycidyl alkyl group and an active hydrogen compound (alcohol, amine, carboxylic acid, respectively).

  Examples of glycidyl ether type epoxy compounds include bisphenol A type epoxy compounds, bromides of bisphenol A type epoxy compounds, hydrogenated products of bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bromides of bisphenol F type epoxy compounds, and bisphenol F type epoxies. Hydrogenated compounds, bisphenol S type epoxy compounds, o-, m-, p-cresol novolak type epoxy compounds, phenol novolac type epoxy compounds, naphthalene ring-containing epoxy compounds, biphenyl type epoxy compounds, biphenyl novolak type epoxy compounds, di Cyclopentadiene type epoxy compounds, phenol aralkyl type epoxy compounds, dihydroxypentadiene type epoxy compounds, and triphenylmethane type epoxidation Things like, and phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, and allyl glycidyl ether.

Examples of the glycidylamine type epoxy compound include tetraglycidyldiaminodiphenylmethane, triglycidylaminophenol, tetraglycidylxylenediamine, glycidylaniline, glycidyl o-toluidine, and the like.
Examples of the glycidyl ester type epoxy compound include phthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, dimer acid diglycidyl ester, and the like.

  An alicyclic epoxy compound is a compound having an aliphatic ring and an epoxy group, and more specifically, an alicyclic epoxy group (an epoxy composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring). And a compound having an epoxy group directly or indirectly bonded to an aliphatic ring.

  The compound having an alicyclic epoxy group is preferably a compound in which two alicyclic epoxy groups are linked by a single bond or a divalent linking group. Examples of the alicyclic epoxy group include a cyclohexene oxide group. Examples of the divalent linking group include a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and a group in which a plurality of these are linked. For example, 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (for example, Celoxide 2021P manufactured by Daicel Corporation), ε-caprolactone modified 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxy A rate (for example, Celoxide 2081 manufactured by Daicel Corporation) is preferable. Other examples of the compound having an alicyclic epoxy group include 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000 manufactured by Daicel Corporation) and 3-methacryloyloxymethylcyclohexene having one alicyclic epoxy group. Examples thereof include oxide, 3-acryloyloxymethylcyclohexene oxide, and 3-vinylcyclohexene oxide.

  Examples of the compound having an epoxy group directly or indirectly bonded to an aliphatic ring include epoxy norbornene (for example, Celoxide 3000 manufactured by Daicel Corporation), 1,2-bis (hydroxymethyl) -1-butanol, Examples include 2-epoxy-4- (2-oxiranyl) cyclohexane adduct (for example, EHPE3150 manufactured by Daicel Corporation).

[Other cationic polymerizable compounds]
In the present invention, when the epoxy prepolymer compound (a) is used as a cationic polymerizable compound, a compound having an oxetanyl group and a compound having a vinyl ether group may be used in combination as the other cationic polymerizable compound. A cationically polymerizable compound refers to a substance that is polymerized or cured by an acid.

  Other cationically polymerizable materials can be monomers or oligomers. By using another cationically polymerizable compound, the cation curability (growth reaction rate) of the epoxy prepolymer compound (a) can be improved, so that the curing rate of the reinforced fiber resin composite can be increased.

A compound having a vinyl ether group has a relatively high cationic curability and excellent performance in terms of productivity. Furthermore, flexibility can be imparted to the completely cured product.
A compound having an oxetanyl group has high cationic curability and is superior in performance in terms of productivity. Furthermore, excellent physical strength can be obtained in a completely cured product.

  Examples of the compound having an oxetanyl group include 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol) (for example, OXT-101 manufactured by Toa Gosei Co., Ltd.), 2-ethylhexyloxetane (for example, OXT-212 manufactured by Toa Gosei Co., Ltd.), Renbisoxetane (XDO: for example, OXT-121 manufactured by Toa Gosei Co., Ltd.), 3-ethyl-3 {[((3-ethyloxetane-3-yl) methoxy] methyl} oxetane (eg, OXT-221 manufactured by Toa Gosei Co., Ltd.) Oxetanylsilsesquioxetane (eg, OXT-191 manufactured by Toa Gosei Co., Ltd.), phenol novolac oxetane (eg, PHOX produced by Toa Gosei Co., Ltd.) and 3-ethyl-3-phenoxymethyloxetane (POX: eg, OXT- manufactured by Toa Gosei Co., Ltd.) 211) at least one selected from the group consisting of Compounds.

  Examples of the compound having a vinyl ether group include hydroxybutyl vinyl ether (for example, HBVE manufactured by ISP), vinyl ether of 1,4-cyclohexanedimethanol (for example, CHVE manufactured by ISP), and triethylene glycol divinyl ether (for example, DVE manufactured by ISP). -3), at least one compound selected from the group consisting of dodecyl vinyl ether (for example, DDVE manufactured by ISP) and cyclohexyl vinyl ether (for example, CVE manufactured by ISP).

  These other cationically polymerizable compounds are used in a proportion of 0.01 to 5 parts by weight, preferably 0.03 to 3 parts by weight, based on 100 parts by weight of the epoxy prepolymer compound (a). can do. By being at least the above lower limit value, the effect of promoting the curing rate can be preferably obtained, and by being at most the above upper limit value, generation of residual stress due to excessive acceleration of the curing rate and resin deterioration due to overheating are preferably prevented. Can do.

[(B) Vinyl chloride resin]
The vinyl chloride resin is not particularly limited, and may be a homopolymer of a vinyl chloride monomer, for example, a copolymer of a vinyl chloride monomer and a polymerizable monomer other than a vinyl chloride monomer, Examples thereof include a graft copolymer obtained by grafting a vinyl chloride monomer or a vinyl chloride resin to a polymer other than the vinyl resin. Furthermore, chlorinated vinyl chloride resins obtained by chlorinating these vinyl chloride resins are also included. These vinyl chloride resins may be used alone or in combination of two or more.

  Although it does not specifically limit as a polymerizable monomer in the copolymer of a vinyl chloride monomer and polymerizable monomers other than a vinyl chloride monomer, It is C2-C16 alpha-olefin (For example, ethylene , Propylene, and butylene); vinyl esters of aliphatic carboxylic acids having 2 to 16 carbon atoms (for example, vinyl acetate and vinyl propionate); alkyl vinyl ethers having 2 to 16 carbon atoms (for example, butyl vinyl ether and cetyl vinyl ether) Alkyl (meth) acrylates having 1 to 16 carbon atoms (for example, methyl (meth) acrylate, ethyl (meth) acrylate and butyl acrylate); aryl (meth) acrylate (for example, phenyl methacrylate); aromatic vinyl (for example, Styrene and α-substituted Ethylene (eg, α-methylstyrene)); vinyl halides (eg, vinylidene chloride and vinylidene fluoride); and N-substituted maleimides (N-phenylmaleimide and N-cyclohexylmaleimide). These polymerizable monomers may be used alone or in combination of two or more.

  As a polymer that gives a graft copolymer together with a vinyl chloride monomer or a vinyl chloride resin, any polymer can be used, regardless of whether it is a homopolymer or a copolymer, as long as it is a polymer that can be graft polymerized to a vinyl chloride monomer. It is. For example, copolymer of α-olefin and vinyl ester (for example, ethylene-vinyl acetate copolymer); copolymer of α-olefin, vinyl ester and carbon monoxide (for example, ethylene-vinyl acetate-monoxide) Carbon copolymer); copolymer of α-olefin and alkyl (meth) acrylate (for example, ethylene-methyl methacrylate copolymer and ethylene-ethyl acrylate copolymer); α-olefin and alkyl (meth) acrylate Copolymer with carbon monoxide (eg, ethylene-butyl acrylate-carbon monoxide copolymer); Copolymer of two or more different α-olefins (eg, ethylene-propylene copolymer); Unsaturated nitrile And diene copolymers (eg, acrylonitrile-butadiene copolymers); And chlorinated polyolefins (eg, chlorinated polyethylene and chlorinated polypropylene). These polymers may be used independently and 2 or more types may be used together.

  The polymerization method of the polyvinyl chloride resin is not particularly limited, and for example, a bulk polymerization method, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method and the like are used.

  The chlorine content of the chlorinated vinyl chloride resin is not particularly limited. For example, the chlorine content is 65 wt% or more and less than 68 wt%, preferably the chlorine content is 66 wt% or more and less than 68 wt%, more preferably 66 wt% or more and 67 wt%. % By weight or less. When the chlorine content is not less than the above lower limit value, the effect of improving the heat resistance can be sufficiently obtained, and when it is not more than the above upper limit value, the workability can be easily obtained favorably. The chlorine content can be measured according to JIS K 7229.

  The chlorinated vinyl resin can be obtained by chlorinating the vinyl chloride resin already described. The chlorination method is not particularly limited, and examples thereof include a thermal chlorination method and a photochlorination method.

  The average degree of polymerization of the vinyl chloride resin (b) is not particularly limited, but is, for example, 400 or more and 1500 or less, preferably 600 or more and 1300 or less. When the average degree of polymerization is not less than the above lower limit, preferred physical properties (for example, toughness) due to the vinyl chloride resin (b) can be easily obtained, and adhesiveness suitable for the application can be easily obtained with an appropriate addition amount. When the average degree of polymerization is not more than the above upper limit value, a compatibility or swelling mode can be easily obtained with a small amount of addition to the epoxy prepolymer compound (a). Since the above-mentioned characteristics are influenced by the composition of the epoxy prepolymer compound (a), even an average degree of polymerization exceeding the above range may be appropriately selected by those skilled in the art.

The content of the vinyl chloride resin (b) is not particularly limited, but is, for example, 1 to 70 parts by weight, preferably 5 to 30 parts by weight, with respect to 100 parts by weight of the epoxy prepolymer compound (a). It is. When the epoxy prepolymer compound (a) is a cationic polymerizable compound and the latent epoxy curing agent (c) described later is a cationic polymerization initiator, the epoxy prepolymer compound (a) and other cationic polymerizable compounds For example, the amount is 1 to 70 parts by weight, preferably 5 to 30 parts by weight, with respect to the total amount of 100 parts by weight. By being content more than the said lower limit, while it becomes easy to obtain toughness and low cost property, it is easy to obtain the adhesiveness which is not too strong suitable for handling. Moreover, the exudation of the epoxy prepolymer compound (a) can also be suppressed. By being content below the said upper limit, it is easy to obtain the adhesiveness which is not too weak suitable for a use. Further, when impregnating the reinforcing fibers, the viscosity does not become too high even in an allowable high temperature state, and it is difficult to cause insufficient impregnation. Thus, by setting the amount of the vinyl chloride resin (b) to an appropriate amount, it is possible to obtain good fast curing performance, ultimate polymerization conversion rate, suppression of bursting of the polymerization reaction, and storage stability.
Since the above-mentioned characteristics are influenced by the composition of the epoxy prepolymer compound (a), even a content exceeding the above range may be appropriately selected by those skilled in the art.

  The epoxy prepolymer compound (a) (and other cationic polymerizable monomers and oligomers) and the vinyl chloride resin (b) are completely mixed (compatible) at the molecular level, or vinyl chloride The epoxy prepolymer compound (a) (and other cationic polymerizable monomers and oligomers) enter between the molecules of the system resin (b), and the intermolecular distance is increased (swelled). Thereby, the surface of the reinforced fiber resin composite can have adhesiveness.

[(C) Latent epoxy curing agent]
The latent epoxy curing agent (c) is not particularly limited, and the heating fiber mixing condition and the reinforcing fiber of the above-mentioned epoxy prepolymer compound (a) (and other cationic polymerizable compounds) and the vinyl chloride resin (b) What is necessary is just to have latency under both the storage conditions of the resin complex. The latent epoxy curing agent (c) may be a compound activated by the action of active energy rays such as light (particularly ultraviolet rays), electromagnetic waves (particularly X-rays), and electron beams, or the action of heat. It may be a compound activated by. Moreover, as the latent epoxy curing agent (c), both a compound activated by the action of active energy rays and a compound activated by the action of heat may be combined.

In the present invention, the latent epoxy curing agent (c) is dicyandiamide, BF ₃ -amine complex, modified imidazole compound, onium salt, these compounds and other curing agents are microencapsulated or clathrated with an organic polymer. The thing which was done is mentioned. From the viewpoint of storage stability and fast curing performance, an onium salt polymerization initiator and a microencapsulated polymerization initiator are preferable.

In the present invention, the latent epoxy curing agent (c) is preferably a cationic polymerization initiator. Since the cationic polymerization system is not oxygen-inhibited, it has excellent surface curability in indoor and outdoor environments (air environments) and has low curing shrinkage when the reinforced fiber resin composite is completely cured. In addition, the work efficiency is good due to the excellent curing efficiency.
In this case, another cationic polymerizable compound may be used in combination with the epoxy prepolymer (a), and the latent epoxy curing agent has a curing action on the other cationic polymerizable compound.

  As the cationic polymerization initiator, a substance that is activated by the action of active energy rays such as light (particularly ultraviolet rays), electromagnetic waves (particularly X-rays) and electron beams, or heat to generate a Lewis acid or a protonic acid is used. Examples include Lewis acid diazonium salts, Lewis acid iodonium salts, Lewis acid sulfonium salts, Lewis acid selenonium salts, onium salts such as aluminum chelate compounds, sulfonic acid esters, iron-arene compounds, silanol-aluminum complexes, etc. And various compounds. More preferable cationic polymerization initiators from the viewpoints of storage stability and fast curing performance include aromatic iodonium salt compounds of Lewis acids and aromatic sulfonium salt compounds of Lewis acids.

Examples of the aromatic iodonium salt compound of Lewis acid include compounds represented by the following formula (II-1).

In the above formula (II-1), R ⁵ and R ⁶ represent any one of a hydrogen atom, an alkyl group, and an alkoxy group, and each R ⁵ and R ⁶ may be the same or different. R ⁷ , R ⁸ , R ⁹ and R ^{10 each} represent a hydrogen atom or an alkyl group, and R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be the same as or different from each other. Further, X represents any one of B (C ₆ F ₅ ) ₄ , SbF ₆ , AsF ₆ , PF ₆ , BF ₄ , CF ₃ SO ₃ , FSO ₃ , ClO ₄ , and F ₂ PO ₂ .
Examples of these iodonium salts include WPI-113 and WPI-116 manufactured by Wako Pure Chemical Industries, Ltd., PHOTOINITIATOR 2074 manufactured by Rhodia Japan, IRGACURE 250 manufactured by Ciba Japan, and CI-5102 manufactured by Nippon Soda.

  Examples of the aromatic sulfonium salt compound of Lewis acid include compounds represented by the following formulas (II-2), (II-3), and (I).

In the above formula (II-2), R ¹¹ , R ¹² and R ¹³ are each an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, or an alkylcarbonyloxy group having 1 to 4 carbon atoms ( Carbonyl group carbon is not included). R ¹¹ , R ¹² and R ¹³ may be the same as or different from each other. Further, X represents any one of B (C ₆ F ₅ ) ₄ , SbF ₆ , AsF ₆ , PF ₆ , BF ₄ , CF ₃ SO ₃ , FSO ₃ , ClO ₄ , and F ₂ PO ₂ .
Examples of these sulfonium salts include Sun-Aid SI-60L, Sun-Aid SI-80L, and Sun-Aid SI-100L (all manufactured by Sanshin Chemical Industry Co., Ltd.).

In the above formula (II-3), X represents B (C ₆ F ₅ ) ₄ , SbF ₆ , AsF ₆ , PF ₆ , BF ₄ , CF ₃ SO ₃ , FSO ₃ , ClO ₄ , F ₂ PO ₂ , (CF ₃ CF ₂ ) ₃ PF ₃ is shown.
Examples of these sulfonium salts include CPI-101A, CPI-100P, CPI-210S, CPI-200K manufactured by San Apro Co., Ltd., DTS-102, DTS-103 manufactured by Midori Chemical Co., Ltd., and the like.

  In addition to the above, examples of the aromatic sulfonium salt compound of Lewis acid include SP-150 and SP-170 manufactured by Adeka Corporation.

In the above formula (I), R ₁ represents an alkyl group having 1 to 4 carbon atoms. R ₂ , R ₂ ′, and R ₂ ″ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, which may be the same or different from each other. R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ₄ represents an alkyl group having 1 to 4 carbon atoms or an optionally substituted phenyl group. The substituent in the phenyl group which may be substituted is an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, or an alkylcarbonyloxy group having 1 to 4 carbon atoms (carbon number). May not include carbon of a carbonyl group.

Further, X ⁻ represents an anion of a super strong acid having a Hammett acidity function of −12 or less. More specifically, X represents any one of B (C ₆ F ₅ ) ₄ , SbF ₆ , AsF ₆ , PF ₆ , and BF ₄ .

The sulfonium compound of the present invention represented by the above formula (I) is a sulfide compound that can be synthesized from the corresponding 3-halogenopropiophenone and thiol, R ₁ -L (L is chlorine, bromine, iodine, etc.) A halogen atom, or a leaving group such as tosylate, triflate, mesytilate, etc.) is converted to a sulfonium salt having L- as a counter anion, and then an alkali of a super strong acid having a Hammett acidity function of -12 or less. It can be synthesized by conducting an anion exchange reaction with a metal salt.

  Specific examples of the sulfonium compound represented by the above formula (I) include compounds represented by the following formula.

  In the aromatic sulfonium salt represented by the above formula (I), elimination of the proton at the α-position of the carbonyl group is promoted by having 2 carbon atoms between the sulfur atom and the carbonyl group. This promotes the generation of acid. That is, it is presumed that a reaction by the mechanism shown below is likely to occur.

The sulfonium compound represented by the above formula (I) is excellent in storage stability and functions as a so-called latent curing agent. It may be a compound activated by the action of active energy rays such as light (especially ultraviolet rays), electromagnetic waves (especially X-rays) and electron beams (that is, protons are released and acids are generated). It may be a compound activated by action. In particular, when the compound is activated by the action of active energy rays, the substituent R ₄ is preferably a phenyl group which may be substituted.

  The sulfonium compound represented by the above formula (I) can be used in combination with the other cationic polymerization initiator described above. When another cationic polymerization initiator is used in combination, the sulfonium compound represented by the above formula (I) and the other cationic polymerization initiator are appropriately combined with those having different activation conditions. For example, one can be configured as a compound activated by the action of active energy rays, and the other as a compound activated by the action of heat. Each of them is a compound that is activated by the action of either an activation energy ray or heat, and the other curing agent may be activated under milder conditions.

  When another cationic polymerization initiator is used in combination, the sulfonium compound represented by the above formula (I) is a compound activated by the action of heat, and the other cationic polymerization initiator is activated by the action of active energy rays. Preferably, the compound is activated. In this case, a frontal polymerization system exemplified in the following scheme can be easily constructed. For this reason, acid is first generated from the other cationic polymerization initiator by active energy rays, and the cationic polymerizable compound is polymerized, and the heat of reaction causes the thermal decomposition of the sulfonium compound represented by the above formula (I) and the acid. Generation is induced and the polymerization reaction can be propagated in a self-promoting manner. Therefore, the energy for generating the acid (that is, both the active energy ray and the heat) is not continuously applied from the outside, and the heat energy necessary for the sulfonium compound alone represented by the above formula (I) is externally supplied. Without giving, the resin composition can be efficiently cured up to the deep part. Therefore, even when the thickness of the fiber resin composite is large, good curability can be exhibited.

  When other cationic polymerization initiators are used in combination, the content of the other cationic polymerization initiators is not particularly limited and can be appropriately determined by those skilled in the art according to the purpose of the other cationic polymerization initiators. For example, it is 0.01 times or more and 100 times or less, preferably 0.1 times or more and 10 times or less on a molar basis with respect to the sulfonium compound represented by the above formula (I). By being above the above lower limit value, an appropriate curing rate can be obtained, and by being below the above upper limit value, the storage stability of the curable resin composition is excellent, and residual stress is generated by excessive acceleration of the curing rate. And it is easy to prevent resin deterioration due to overheating.

  The amount of the latent epoxy curing agent (c) is, for example, 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, with respect to 100 parts by weight of the epoxy prepolymer compound (a). It is. When the latent epoxy curing agent (c) is a cationic polymerization initiator, for example, 0.05 parts by weight or more and 5 parts by weight with respect to 100 parts by weight of the total amount of the epoxy prepolymer compound (a) and other cationic polymerizable compounds. Parts by weight or less, preferably 0.1 parts by weight or more and 3 parts by weight or less. By being more than the said lower limit, preferable quick-curing performance and polymerization conversion rate can be obtained. It is preferable that it is not more than the above upper limit value from the viewpoint of suppression of sudden occurrence of polymerization reaction and storage stability.

[Other additives]
In the present invention, a filler may be added from the viewpoint of reducing the curing stress due to the use of the reinforced fiber resin composite or curing shrinkage. Examples of the filler include calcium carbonate, magnesium carbonate, barium sulfate, mica, talc, kaolin, clay, celite, barlite, baryta, silica, silica sand, dolomite limestone, gypsum, hollow balloon, alumina, glass powder, aluminum hydroxide , Zirconium oxide, antimony trioxide, titanium oxide, molybdenum dioxide, iron powder and the like.
In the present invention, it is preferable that the reinforced fiber resin composite does not substantially contain an acrylic resin. “Acrylic resin substantially not included” means that even if it does not contain at all, or even if it is included, an amount less than the minimum amount at which the acrylic resin can exhibit the effect as a thickener is allowed. Say something.

[Reinforcing fiber]
The fiber for reinforcing resin is not particularly limited, but inorganic fiber such as glass fiber, ceramic fiber, boron fiber, and basalt fiber; carbon fiber such as PAN (polyacrylonitrile) -based carbon fiber and pitch-based carbon fiber; and aramid, polyester , Synthetic organic fibers such as polyethylene, nylon, vinylon, polyacetal, PBO (polyparaphenylene benzoxazole), high-strength polypropylene, polyamide, polyarylate, and polyester; and natural fibers such as kenaf and hemp. These fibers can be used alone or as a hybrid fiber in which a plurality of types are combined.

When the matrix resin is cured by cationic polymerization, it is preferably a fiber having acid resistance.
When importance is attached to the strength of the reinforced fiber resin composite, or when a compound that does not require light for activation is used as the latent epoxy curing agent (c), carbon fiber is preferable.
When importance is attached to the transparency of the reinforced fiber resin composite, or when a compound activated by light is used as the latent epoxy curing agent (c), it may be an inorganic fiber or a synthetic organic fiber having transparency. preferable.

  The form of the resin reinforcing fiber (for example, weaving method, bundling method, etc.) is not particularly limited, and when the reinforcing fiber resin composite is a prepreg for civil engineering construction, the loss in the reinforcing design is minimized. From the viewpoint, it is usually preferable that the fabric is a unidirectional material. Moreover, when giving the anti-peeling performance which needs to give punching strength, when giving priority to the design property of a product surface, you may use the textile fabric which is a bi-directional material. Further, the fiber basis weight and the resin content can be appropriately determined by those skilled in the art according to the use of the reinforced fiber resin composite.

[Method for producing reinforced fiber resin composite]
The reinforcing fiber resin composite is manufactured by a heating and mixing process, a curing agent adding process, and an impregnation process.
In the heating and mixing step, the epoxy prepolymer compound (a) and the vinyl chloride resin (b) are heated and mixed to obtain a heated mixed resin. In this case, the epoxy prepolymer compound (a) is thickened by the vinyl chloride resin (b). By heating and mixing, the vinyl chloride resin (b) is in a state of being compatible with the epoxy prepolymer compound (a), or in a state of being swollen in the epoxy prepolymer compound (a). In the compatible state, transparency can be confirmed by visual observation. In the swollen state, cloudiness can be confirmed. In addition, when the vinyl chloride resin (b) is merely dispersed without being swollen, it can be confirmed by not thickening.

  The vinyl chloride resin (b) is preferably particulate. This makes it easy to obtain the above-mentioned compatible state or swollen state, and is excellent in handling properties. From the viewpoint of more preferably obtaining these states, the average particle size of the vinyl chloride resin (b) may be 0.2 μm or more and 200 μm or less. The average particle diameter is a volume-based 50% cumulative distribution diameter measured by a dynamic scattering method using laser light.

  The heating temperature may be a temperature at which a compatible or swollen state is obtained. For example, it is 120 ° C. or higher, preferably 150 ° C. or higher. Thereby, at least the swollen state can be easily obtained. On the other hand, the higher the temperature, the easier it is to obtain a compatible state. Furthermore, the heating temperature is, for example, 220 ° C. or less, preferably 180 ° C. or less. As for the heating temperature, it is possible to achieve either a compatible state or a swollen state, considering the boiling point of the epoxy prepolymer compound (a), the heat resistance of the vinyl chloride resin (b), etc. Those skilled in the art can appropriately adjust the upper limit of the temperature.

In addition, it is permitted to add a low boiling point solvent as a diluent for adjusting the viscosity of the heat-mixed resin. Examples of the low boiling point solvent include organic solvents such as tetrahydrofuran and acetone. For example, when the use ratio of a low molecular weight epoxy compound (for example, monomer, oligomer) is small or not used as the epoxy prepolymer compound (a), or when a vinyl chloride resin (b) having a high degree of polymerization is used or When the usage rate is increased (for example, for the purpose of imparting greater toughness), the viscosity of the heat-mixed resin tends to increase. For this reason, those skilled in the art can appropriately determine whether or not the diluent is used or the amount of use in consideration of the molecular structure and usage ratio of the epoxy prepolymer compound (a) and the vinyl chloride resin (b).
When a diluent is used, a paste obtained by dissolving the vinyl chloride resin (b) in the diluent in advance may be mixed with the epoxy prepolymer compound (a).

  In the curing agent addition step, a fluid curable resin composition is obtained in which the latent epoxy curing agent (c) is added to the heat-mixed resin. This step is performed under conditions that keep the latent epoxy curing agent (c) inert. Accordingly, when the latent epoxy curing agent (c) contains a thermal polymerization disclosure agent, the heated mixed resin is once cooled until the activation temperature of the latent epoxy curing agent (c) is below. In this case, the specific cooling temperature depends on the activation temperature of the latent epoxy curing agent (c), but the fluidity of the resin composition is not impaired (the hindrance to the subsequent impregnation step). It is preferable that the liquidity is as high as possible.

  On the other hand, when the latent epoxy curing agent does not contain a thermal polymerization initiator (when the latent epoxy curing agent is a photopolymerization initiator), the above cooling is not necessarily required. Therefore, in this case, the heating and mixing step and the curing agent adding step may be performed simultaneously or separately. When performed separately, as long as the temperature conditions of this step consider the boiling point of the epoxy prepolymer compound (a), the heat resistance of the vinyl chloride resin (b), the heat resistance of the latent epoxy curing agent (c), etc. The above-mentioned heating and mixing process temperature may be exceeded, may be equal to the heating and mixing process temperature, or may be lower than the heating and mixing process temperature and higher than the activation temperature of the thermal polymerization initiator. Of course, it is good also as temperature conditions equivalent to the case where a thermal polymerization initiator is contained in a latent epoxy hardening | curing agent (c). However, in these cases, this step is performed under conditions that exclude light conditions that can activate the latent epoxy curing agent (c).

  Thus, since a hardening | curing agent addition process is performed on the conditions which maintain a latent epoxy hardening | curing agent (c) inactive, a flowable curable resin composition is obtained, without producing a hardening reaction. The viscosity of the fluid resin composition is, for example, 1 Pa · s to 500 Pa · s, preferably 1 Pa · s to 300 Pa · s, under the condition of 80 ° C. That the viscosity is equal to or higher than the lower limit is preferable in terms of easily obtaining appropriate tackiness of the surface of the reinforced fiber resin composite, and is preferable in terms of easy subsequent impregnation step by being equal to or lower than the upper limit. .

  In the impregnation step, the reinforcing fiber is impregnated with the fluid curable resin composition to obtain a reinforcing fiber resin composite. The temperature condition permitted in the impregnation step is the same as the temperature condition permitted in the curing agent addition step. In order to improve the impregnation property of the fluid resin composition, the temperature of the fluid resin composition may be increased within an allowable temperature range. On the contrary, according to the heat resistance of the reinforcing fiber, the fluid resin composition may be cooled and lowered to a temperature lower than the heat resistant temperature of the reinforcing fiber. Preferably, the temperature of the fluid curable resin composition is adjusted to 60 ° C. or higher and 90 ° C. or lower.

The impregnation technique is not particularly limited and is appropriately selected by those skilled in the art. A method capable of impregnating a highly viscous resin composition is preferably selected. For example, it is possible to efficiently impregnate using a technique such as a fiber handling process or a pressure change process such as pressurization or vacuum. In addition, you may impregnate on a release sheet at the time of an impregnation.
In addition, when a fluid curable resin composition contains a low boiling point solvent as a diluent, the low boiling point solvent is removed after impregnation. The removal of the low boiling point solvent can be performed by drying or reduced pressure treatment.

  The obtained reinforcing fiber resin composite can be provided with a release sheet on at least one surface as necessary. Moreover, it may be divided into predetermined dimensions and sizes, or may be wound into a roll shape.

[Method for producing reinforced structure]
The reinforcing fiber resin composite of the present invention can be used for reinforcing a structure. This produces a reinforced structure.
Examples of the structure to be reinforced include cement-based structures and piping.

The cement-based structure is a structure such as a building and a building material made of a material containing cement. Materials mixed with cement include fine aggregates such as sand, coarse aggregates such as gravel and crushed stone, and admixtures, and materials containing cement generally include mortar and concrete.
The pipe may be an existing pipe that requires rehabilitation. Examples include aging sewer pipes, water supply pipes, and agricultural water pipes. The material of the pipe may be concrete, metal, or resin.

The reinforcement of the structure includes a pasting process and a curing process.
In the affixing step, for example, a reinforced fiber resin composite is affixed so as to cover abnormal parts (cracking, deterioration, etc.) that have occurred in the structure in order to repair the structure. Alternatively, as a preventive reinforcement that prevents the occurrence of an abnormality that may occur in the structure, a reinforcing fiber resin composite is pasted so as to cover a portion where a reinforcing effect is expected. The reinforced fiber resin composite after application may be appropriately constrained to an appropriate shape using a mold or the like.
It should be noted that the surface to be affixed may be smoothed by removing the surface in advance or may be treated with a primer.

In the curing step, the reinforced fiber resin composite in a stuck state is subjected to the active conditions of the latent epoxy curing agent (c). Thereby, the matrix resin in the reinforced fiber resin composite is completely cured. Therefore, the structure is reinforced in a state where the completely cured body of the epoxy resin is firmly fixed on the surface.
In the case of reinforcement of piping, the tubular resin composite is pressed against the inner peripheral surface of the pipe using fluid pressure, and the curable resin composite supported on the resin composite under the active condition of the curing agent is By completely curing, a lining layer can be formed on the inner surface of the pipe.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. Further, the amount represented by “parts by weight” is an amount relative to 100 parts by weight of the epoxy prepolymer unless otherwise specified.

<Reference Example 1>
(Creation of test sample)
Polyvinyl chloride (100 parts by weight of an epoxy prepolymer in which bisphenol A diglycidyl ether (jER828, manufactured by Mitsubishi Chemical Corporation) and an alicyclic epoxy compound (Celoxide 2021P, manufactured by Daicel Chemical Industries, Ltd.) are mixed at an equal weight are used. 15 parts by weight of Tokuyama Sekisui Chemical Co., Ltd. (640M) was added and mixed by heating at 140 ° C. for 3 minutes to obtain a molten resin. Thereafter, the molten resin was cooled to 80 ° C., and 0.5 parts by weight of a thermal cationic polymerization initiator (Sun Aid SI-100L manufactured by Sanshin Chemical Co., Ltd.) was added and mixed to obtain a fluid resin composition. Using a bar coater, the fluid resin composition was applied onto a release-treated PET film so as to have a thickness of 500 microns, and further covered with the PET film of the same material from above, and allowed to cool to room temperature. . This gave a test sample.

(Releasability)
The PET film was peeled from the test sample. As a result, there was no transfer of resin on the peeled PET surface, and good peelability was confirmed.

(Adhesive)
The film on one side of the test sample was peeled off, stuck on the surface of the glass plate, and allowed to stand so that the test sample faced downward. As a result, good adhesion was obtained without causing self-weight peeling.

(Thermosetting)
The affixed test sample was heat-treated at 180 ° C. for 30 seconds using an iron over a PET film. Thereafter, the PET film was peeled off. The PET film could be easily peeled off. The resin composition affixed to the lower surface of the glass plate was fixed as a completely cured body and had a pencil hardness of 2H or higher.

(Storage stability)
A separately prepared test sample was placed in a circulation oven at 40 ° C. and left for 1 month. As a result, the flexibility of the test sample after standing was the same as the flexibility of the test sample one month ago.

<Reference Example 2>
(Creation of test sample)
For 100 parts by weight of epoxy prepolymer in which bisphenol A diglycidyl ether (jER828 manufactured by Mitsubishi Chemical Co., Ltd.) and alicyclic epoxy compound (Celoxide 2021P manufactured by Daicel Chemical Industries, Ltd.) are mixed in equal weight, chlorinated polychlorinated 15 parts by weight of vinyl (HA58K manufactured by Tokuyama Sekisui Chemical Co., Ltd.) was added and mixed by heating at 200 ° C. for 3 minutes to obtain a molten resin. Thereafter, 0.5 part by weight of a cationic photopolymerization initiator (CPI-100P manufactured by San Apro Co., Ltd.) was added and mixed to obtain a fluid resin composition. The flowable resin composition was applied onto a release-treated PET film so as to have a thickness of 100 microns using a bar coater, and was further sandwiched by the same material PET film from above to be cooled to room temperature. This gave a test sample.

(Releasability)
The PET film was peeled from the test sample. As a result, there was no transfer of resin on the peeled PET surface, and good peelability was confirmed.

(Adhesive)
The film on one side of the test sample was peeled off, stuck on the surface of the glass plate, and allowed to stand so that the test sample faced downward. As a result, good adhesion was obtained without causing self-weight peeling.

(Photo-curing)
The PET film was further peeled from the above-mentioned test sample, and the resin composition was directly irradiated with a gallium halide lamp so that the energy was about 50 mJ / cm ² . The resin composition affixed to the lower surface of the glass plate was fixed as a completely cured body and had a pencil hardness of 2H or higher.

(Storage stability)
A separately prepared test sample was placed in a circulation oven at 70 ° C. and left for 1 month. As a result, the flexibility of the test sample after standing was the same as the flexibility of the test sample one month ago.

<Example 1>
(Creation of carbon fiber prepreg)
Using the heating roller, the flowable resin composition obtained in Reference Example 1 was adjusted to 80 parts by weight with respect to 100 parts by weight of unidirectional carbon fiber cloth (UT70-30G manufactured by Toray Industries, Inc.). The carbon fiber cloth was impregnated under the condition of ° C. The impregnated carbon fiber cloth was sandwiched between the release-treated PET films and cooled to room temperature. As a result, a carbon fiber prepreg was obtained.

  About carbon fiber prepreg, when the release property, adhesiveness, photocurability, and storage stability were confirmed similarly to the reference example 1, the same favorable result as the reference example 1 was obtained.

<Example 2>
(Creation of glass fiber prepreg)
Using a heating roller, the flowable resin composition obtained in Reference Example 2 was 60 parts by weight with respect to 100 parts by weight of acid-resistant glass fiber cloth (ARG-LW110 manufactured by Nippon Electric Glass Co., Ltd.). The glass fiber cloth was impregnated at 130 ° C. The impregnated acid-resistant glass fiber cloth was sandwiched between the release-treated PET films and cooled to room temperature. As a result, a visually transparent glass fiber prepreg was obtained.

  About the glass fiber prepreg, when the mold release property, adhesiveness, photocurability, and storage stability were confirmed similarly to Reference Example 2, the same good results as Reference Example 2 were obtained.

<Reference Example 1 for comparison>
(Creation of test sample)
To 100 parts by weight of an epoxy prepolymer obtained by mixing bisphenol A diglycidyl ether (jER828, manufactured by Mitsubishi Chemical Corporation) and an alicyclic epoxy compound (Celoxide 2021P, manufactured by Daicel Chemical Industries, Ltd.) with equal weight, modified polymethyl 20 parts by weight of methacrylate fine particles (Zefiac F303 manufactured by Aika Kogyo Co., Ltd.) and 0.5 parts by weight of thermal cationic polymerization initiator (Sun Aid SI-100L manufactured by Sanshin Chemical Co., Ltd.) were added to obtain a fluid resin composition. . Using a glass cloth tape, a square bank with a height of about 0.5 mm is made on the release-treated PET film, and a flowable resin composition is poured into it, and the same material PET from above. Covered with film and sandwiched. The test sample which became translucent was obtained by heating at 80 degreeC for 30 minutes.

(Releasability)
The PET film was peeled from the test sample. As a result, there was no transfer of resin on the peeled PET surface, and good peelability was confirmed.

(Adhesive)
The film on one side of the test sample was peeled off, stuck on the surface of the glass plate, and allowed to stand so that the test sample faced downward. As a result, good adhesion was obtained without causing self-weight peeling.

(Thermosetting)
The attached test sample was heat-treated at 180 ° C. for 10 minutes using an iron through a PET film. Thereafter, the PET film was peeled off. Resin transfer occurred in the PET film. The resin composition affixed to the lower surface of the glass plate was found to be tacky (sticky) when touched with a finger and was found to be insufficiently cured.

(Storage stability)
A separately prepared test sample was placed in a circulation oven at 40 ° C. and left for 1 month. As a result, the flexibility of the test sample after standing was the same as the flexibility of the test sample one month ago.

<Reference Example 3>
(Synthesis of PRTAG-PF ₆ )
First, the reaction shown in the following scheme was performed to synthesize an intermediate.

  7.5 g (53.6 mmol) of 4-methoxybenzenethiol (compound a) was dissolved in 20 mL of tetrahydrofuran, 10.8 g (107 mmol) of triethylamine was added, and the mixture was stirred for 24 hours under ice cooling. A solution prepared by dissolving 10.2 g (53.9 mmol) of 3-chloropropiophenone (compound b) in 20 mL of tetrahydrofuran was added thereto and reacted at room temperature for 24 hours while stirring. Since precipitation of a white solid was confirmed in the reaction solution, this solid was removed by filtration. The obtained filtrate evaporated the solvent to precipitate a solid. This solid was dissolved in chloroform, and a 5 wt% hydrochloric acid aqueous solution, a saturated sodium bicarbonate aqueous solution, and a saturated sodium chloride aqueous solution were subjected to liquid separation in this order, and water in the solution was removed using magnesium sulfate. Magnesium sulfate was filtered and the solvent was evaporated, followed by washing with hexane, and the solid was collected and dried under reduced pressure. As a result, 6.8 g (yield 55%) of intermediate compound 2 as a white solid was obtained.

The intermediate compound was measured by ¹ H-NMR. The identification data is as follows.
NMR (δ value)
3.2-3.3 ppm (m, 4H, —CCH ₂ —)
_{3.80 (s, 3H, -OCH 3} )
6.84 (d, 2H, Ar-H)
7.4-7.6 (m, 5H, Ar-H)
7.89 (d, 2H, Ar-H)

Next, the reaction shown in the following scheme was performed to synthesize PRTAG-Tf.

  4.0 g (14 mmol) of the intermediate compound was dissolved in 40 mL of dichloromethane and stirred under ice cooling. To this, 2.4 g (14 mmol) of methyl trifluoromethanesulfonate dissolved in 10 mL of dichloromethane was added and reacted for 5 hours under ice cooling. Thereafter, hexane washing was performed, and the solid was collected and dried under reduced pressure. As a result, 4.3 g (yield 68%) of PRTAG-Tf was obtained.

PRTAG-Tf was subjected to ¹ H-NMR measurement and ESI-MS measurement. The identification data is as follows.
NMR (δ value)
3.41 (s, 3H, S- CH 3)
3.52 (m, 2H, S—CH ₂ —)
3.84 (m, 1H, S—CH ₂ —)
3.86 (s, 3H, O-CH ₃ )
3.99 (m, 1H, S- CH 2 -)
7.25 (d, 2H, Ar-H)
7.53 (t, 2H, Ar-H)
7.67 (t, 2H, Ar-H)
7.93-8.01 (m, 4H, Ar-H)
ESI-MS
{C ₁₇ H ₁₉ O ₂ S ⁺ } 287.1093 (theoretical value 287.1100)
{CF ₃ SO ₃ ⁻ } 148.9526 (theoretical value 148.9533)

Finally, the reaction shown in the following scheme, was synthesized PRTAG-PF _6.

PRTAG-Tf 0.57 g (1.3 mmol) was dissolved in 700 mL of ion-exchanged water and stirred at room temperature for 10 minutes. A solution in which 0.33 g (2.0 mmol) of sodium hexafluorophosphate was dissolved in 10 mL of ion-exchanged water was added thereto, followed by stirring at room temperature for 30 minutes. As a result, a white solid was precipitated. The precipitated solid was filtered, washed with hexane and then dried under reduced pressure to obtain 0.4 g (yield 70%) of the target product PRTAG-PF ₆ .

PRTAG-PF ₆ was subjected to ¹ H-NMR measurement and ESI-MS measurement. The identification data is as follows.
NMR (δ value)
3.47 (s, 3H, S- CH 3)
3.52 (m, 2H, S—CH ₂ —)
3.84 (m, 1H, S—CH ₂ —)
3.86 (s, 3H, O- CH 3)
3.99 (m, 1H, S- CH 2 -)
7.25 (d, 2H, Ar-H)
7.53 (t, 2H, Ar-H)
7.67 (t, 2H, Ar-H)
7.93-8.01 (m, 4H, Ar-H)
ESI-MS
{C ₁₇ H ₁₉ O ₂ S ⁺ } 287.1078 (theoretical value 287.1100)
{PF ₆ ⁻ } 148.9533 (theoretical value 144.9642)

<Reference Example 4>
Synthesis was performed in the same manner as in Reference Example 3 except that 0.52 g (2.0 mmol) of sodium hexafluoroantimonate was used instead of 0.33 g (2.0 mmol) of sodium hexafluorophosphate during the anion exchange reaction. Went. As a result, 0.40 g (yield 59%) of PRTAG-SbF ₆ represented by the following formula was obtained.

PRTAG-SbF ₆ was subjected to ¹ H-NMR measurement and ESI-MS measurement. The identification data is as follows.
NMR (δ value)
3.35 (s, 3H, S- CH 3)
3.53 (m, 2H, S—CH ₂ —)
3.86 (m, 1H, S—CH ₂ —)
3.87 (s, 3H, O—CH ₃ )
3.99 (m, 1H, S—CH ₂ —)
7.26 (d, 2H, Ar-H)
7.54 (t, 2H, Ar-H)
7.68 (t, 2H, Ar-H)
7.94-8.02 (m, 4H, Ar-H)
ESI-MS
{C ₁₇ H ₁₉ O ₂ S ⁺ } 287.1100 (theoretical value 287.1100)
{SbF ₆ ⁻ } 234.8947 (theoretical value 234.8948)

<Reference Example 5>
A DMSO-d ₆ solution (internal standard: mesitylene) was prepared so that the PRTAG-SbF ₆ obtained in Example 4 had a concentration of 7.6 mM, and the resulting solution was put in an NMR tube and sealed. The NMR tube was heated in an oven to 120 ° C., and the time course of the ¹ H-NMR spectrum was followed.

The results of tracking are shown in FIG. In FIG. 1, the horizontal axis indicates the heating time (minutes), and the vertical axis indicates the normalized peak intensity of PRTAG-SbF ₆ and the conversion rate (%) to the decomposition product. As shown in FIG. 1, under the heating condition at 120 ° C., PRTAG-SbF ₆ rapidly decomposes within 60 minutes (see the round dot in the figure), and at the same time, the generation of the decomposition product D1 shown in the following formula (square dot in the figure) And the generation of decomposition product D2 (see triangular dots in the figure) was confirmed.

<Reference Example 6>
1 g of 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Delcel Chemical Industries, Ltd. Celoxide 2021P), 1 g of 1,2-epoxycyclohexane, diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimo 0.024 g of natto and 0.040 g of PRTAG-SbF ₆ obtained in Reference Example 4 were stirred until uniform to obtain a curable resin composition. The obtained curable resin composition was put in a test tube having a diameter of 5 mm and a length of 40 mm, irradiated with light of 254 nm for 100 seconds, and then irradiation was stopped. The curing reaction proceeded even after the irradiation was stopped, and the entire curing of the resin in the test tube was completed in about 280 seconds from the start of exposure.

  Preferred embodiments of the present invention are as described above, but the present invention is not limited to them, and various other embodiments are possible without departing from the spirit and scope of the present invention. Furthermore, the operations and effects described in this embodiment are merely examples, and do not limit the present invention.

Claims (19)

Epoxy prepolymer compound (a),
A vinyl chloride resin (b) compatible with the epoxy prepolymer compound (a) or swollen in the epoxy prepolymer compound (a), and a latent epoxy curing agent (c),
A resin composition comprising:
A reinforcing fiber impregnated with the resin composition;
A reinforced fiber resin composite.   The reinforced fiber resin composite according to claim 1, wherein the vinyl chloride resin (b) is contained in an amount of 1 to 70 parts by weight with respect to 100 parts by weight of the epoxy prepolymer compound (a).   The reinforced fiber resin composite according to claim 1 or 2, wherein the vinyl chloride resin (b) has an average degree of polymerization of 400 or more and 1500 or less.   The said latent epoxy hardening | curing agent (c) is 0.01 weight part or more and 5 weight part or less with respect to 100 weight part of the said epoxy prepolymer compound (a), It is any one of Claim 1 to 3 Reinforced fiber resin composite.   5. The resin composition according to claim 1, wherein the resin composition has a resin viscosity at 30 ° C. of 500 Pa · s to 8000 Pa · s and a resin viscosity at 80 ° C. of 1 Pa · s to 500 Pa · s. Reinforced fiber resin composite.   The reinforcing fiber resin composite according to any one of claims 1 to 5, wherein the reinforcing fiber resin composite is formed in a sheet shape and a release sheet is laminated on at least one surface.   The reinforcing fiber resin composite according to any one of claims 1 to 6, wherein the latent epoxy curing agent (c) is a cationic polymerization initiator.   The reinforced fiber resin composite according to any one of claims 1 to 7, wherein the latent epoxy curing agent (c) is a thermal polymerization initiator that reacts at a temperature of 90 ° C or higher and 200 ° C or lower.   The reinforced fiber resin composite according to any one of claims 1 to 7, wherein the latent epoxy curing agent (c) is a photopolymerization initiator.   The reinforcing fiber resin composite according to any one of claims 1 to 7, wherein the latent epoxy curing agent (c) includes both a thermal polymerization initiator and a photopolymerization initiator. The latent epoxy curing agent (c) is represented by the following general formula (I):
(In the formula, R ₁ represents an alkyl group having 1 to 4 carbon atoms, and R ₂ , R ₂ ′, and R ₂ ″ may be the same as or different from each other, a hydrogen atom or 1 to 4 carbon atoms. R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₄ represents an alkyl group having 1 to 4 carbon atoms or an optionally substituted phenyl group, X ^- the Hammett acidity function represents the -12 anion superacid).
The reinforced fiber resin composite according to any one of claims 7 to 10, which is a thermal acid generator or an energy ray acid generator represented by: An epoxy prepolymer compound (a) and a vinyl chloride resin (b) are mixed by heating. The vinyl chloride resin (b) is compatible with the epoxy prepolymer compound (a) or the epoxy prepolymer. In the heated mixed resin swollen by the polymer compound (a),
A flowable curable resin composition obtained by adding the latent epoxy curing agent (c) under a condition of maintaining the latent epoxy curing agent (c) in an inert state,
A reinforcing fiber resin composite obtained by impregnating reinforcing fibers. A fully cured body of the reinforcing fiber resin composite according to any one of claims 1 to 12,
A cement-based structure in which the completely cured body is fixed to the surface;
Reinforced cementitious structures including The epoxy prepolymer compound (a) and the vinyl chloride resin (b) are heated and mixed, and the vinyl chloride resin (b) is compatible with the epoxy prepolymer compound (a), or the epoxy prepolymer compound ( a heating and mixing step to obtain a heated and mixed resin swollen in a);
Addition of a curing agent to obtain a flowable curable resin composition in which the latent epoxy curing agent (c) is added to the heat-mixed resin under the condition of maintaining the latent epoxy curing agent (c) inactive Process,
A method for producing a reinforced fiber resin composite comprising impregnating a reinforcing fiber with the fluid curable resin composition to obtain a reinforced fiber resin composite.   The method for producing a reinforced fiber resin composite according to claim 14, wherein the vinyl chloride resin (b) is in the form of particles. The latent epoxy curing agent (c) includes at least a thermal polymerization initiator,
In the curing agent addition step, the heated mixed resin is cooled to a temperature lower than the reaction temperature of the latent epoxy curing agent (c), and then the latent epoxy curing agent (c) is added. 15. A method for producing a reinforced fiber resin composite according to 15.   The reinforced fiber resin composite according to any one of claims 14 to 16, wherein a viscosity of the flowable curable resin composition under temperature conditions in the impregnation step is 1 Pa · s or more and 500 Pa · s or less. Body manufacturing method. A sticking step of sticking the reinforcing fiber resin composite according to any one of claims 1 to 12 to the surface of a structure to be reinforced,
A curing step in which the reinforced fiber resin composite affixed is subjected to an active condition of the latent epoxy curing agent (c) to cure the epoxy prepolymer compound (a) to obtain a reinforced structure;
A method for manufacturing a reinforced structure, comprising:   The manufacturing method of the reinforced structure of Claim 18 whose said structure to be reinforced is a cement-type structure or piping.