TWI519405B - Glass fiber reinforced plastic and its manufacturing method - Google Patents

Description

Glass fiber reinforced plastic and manufacturing method thereof

The invention relates to a glass fiber reinforced plastic and a manufacturing method thereof, in particular to a glass fiber reinforced plastic which is filled with components by using a first modified vinyl ester resin and/or a second modified vinyl ester resin. And its manufacturing method.

The production of high value-added yachts is often accompanied by a high technical content. Due to the strict requirements on the quality of the finished surface, the yachting industry spends a lot of time and cost to achieve high surface quality. The phenomenon of print through is named after the regular internal fibers, core grooves, and reinforcing materials are observed on the surface of the finished product. The reason for this is that the resin itself is a heterogeneous material during the curing process. . The phenomenon of uneven shrinkage caused by heterogeneous materials, and the curing mechanism of the resin commonly used in the yacht industry, accompanied by considerable shrinkage, and no effective blocking mechanism can be effectively solved. Since this phenomenon has been around for a long time, and so far the industry has not completely avoided the method, if it can overcome this problem will be an important direction to determine the development of the industry.

However, at present, the manufacture of composite yachts, whether at home or abroad, suffers from the phenomenon of print through phenomenon on the surface of composite laminates, and there is no completely effective improvement method. Surface defects caused by phenomena can cause surface reversal The image is obviously distorted and blurred. If this phenomenon occurs in the shipyard, the manufacturer must remove the block where the thread printing phenomenon occurs and re-spray the rubber casing. If it occurs after delivery, it will be necessary to send someone to solve the problem abroad, or to pay the repair cost of the owner abroad, no matter which situation, the cost of the shipyard will increase, or the goodwill will be damaged.

The glass fiber reinforced plastic (FRP) on the mold after the mold release surface will show the resin shrinkage, the main reason is that the strength of the glass fiber reinforced plastic during the establishment of the resin will shrink, due to the glass fiber reinforced plastic For non-homogeneous materials, the pattern of shrinkage will depend on the composition of the interior of the fiberglass reinforced plastic.

Therefore, there is a need to provide a glass fiber reinforced plastic and a method of manufacturing the same to solve the aforementioned problems.

It is an object of the present invention to provide a method of making a glass fiber reinforced plastic that can control the threading to be within an acceptable range.

In order to achieve the above object, the present invention provides a method for manufacturing a glass fiber reinforced plastic, comprising the steps of: providing a mold, the mold comprising a cavity; providing a laminate in the cavity; and providing a flow guiding resin mesh to the laminate a vacuum bag is disposed on the flow guiding resin mesh, and covers the cavity, the flow guiding resin mesh, the laminated layer is sealed between the vacuum bag and the die; and a resin is injected into the cavity; Heating the resin; wherein the resin is a first modified vinyl ester resin and/or a second modified vinyl ester resin, the first modified vinyl ester resin comprises: a resin mixture, a hardener And a polymerization initiator, wherein the resin mixture comprises a modified epoxy resin represented by the following Chemical Formula 1, and a diluent

In the above Chemical Formula 1, n is an integer of 0 to 300; and Q and L are each selected from Wherein R1 and R2 are each a hydrogen atom or a methyl group; and M is selected from a hydrogen atom, Wherein R1 and R2 are each a hydrogen atom or a methyl group; and A is selected from the group consisting of: , wherein R 4 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the substituents on each benzene ring are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen; the second modified ethylene The ester resin comprises: a resin mixture; a hardener; and a polymerization initiator, the resin mixture comprising: at least one epoxy resin selected from the group consisting of bisphenol A epoxy Resin, bisphenol F epoxy resin, polyfunctional epoxy resin epoxy resin, Novolac epoxy resin, Brominated type epoxy resin, adjacent a Cresol-Novolac epoxy resin and a rubber toughened epoxy resin; and at least one unsaturated compound selected from the group consisting of unsaturated polyester resins, vinyl ester resins, and benzene Styrene, p-vinyltoluene, dichlorostyrene, 2-Hydroxyethyl methacrylate phosphate, acrylic acid Acrylate, methacrylate e), diallyl phthalate, Hexamethylene diacrylate, Tripropylene Glycol Diacrylate (TPGDA), triallyl cyanurate (Triallyl) Cyanurate), trimethylol propane trimethacrylate (TMPTMA), trimethylol propane triacrylate (TMPTA), glycidyl methacrylate (Glycidyl Methacrylate), allylic Allyl glycidyl ether and cyclohexane vinyl monoxide.

The method for producing a glass fiber reinforced plastic according to the above, wherein the resin is heated to a temperature of between 30 and 120 degrees Celsius.

The method for producing a glass fiber reinforced plastic according to the above, wherein the flow guiding resin net comprises a release cloth.

The above method for manufacturing a glass fiber reinforced plastic further comprises the steps of: providing a cement between the vacuum bag and the mold.

The method for producing a glass fiber reinforced plastic according to the above, wherein the first modified vinyl ester resin and/or the second modified vinyl ester tree are injected Before the step of the grease in the cavity, the method further comprises the steps of: extracting air inside the cavity.

In the above method for manufacturing a glass fiber reinforced plastic, the step of disposing the laminate in the cavity includes: disposing a core material and a fiber material in the cavity, and the fiber material covers the core material to form the Laminated.

In the above method for producing a glass fiber reinforced plastic, the laminate is a core material or a fiber material.

In order to achieve the above object, the present invention further provides a glass fiber reinforced plastic comprising: a laminate; and a first modified vinyl ester resin and/or a second modified vinyl ester resin mixed in the core material And the fibrous material, the first modified vinyl ester resin and the second modified vinyl ester resin are as described above.

The glass fiber reinforced plastic of the present invention and the method for producing the same are mainly used for member infusion using a first modified vinyl ester resin and/or a second modified vinyl ester resin. It is mainly used for vacuum infusion of large fiber composite parts and has excellent surface flatness. The properties of the resin have long gelation time, short hardening time, low heat release, high glass transition temperature and low shrinkage, and excellent impregnation properties for glass fibers and carbon fibers. After the infusion is performed by using the first modified vinyl ester resin and/or the second modified vinyl ester resin, the heating and hardening operation is performed, and the resin strength is established by controlling the heating temperature, and the resin shrinkage is established. The thread displayed is within acceptable limits.

The above and other objects, features, and advantages of the present invention will become more apparent from the accompanying drawings.

110‧‧‧Mold

111‧‧‧ cavity

120‧‧‧ core material

130‧‧‧Fiber

140‧‧‧vacuum bag

141‧‧‧Flower Resin Net

142‧‧‧vacuum suction holes

143‧‧‧ resin injection hole

150‧‧ ‧ Mud

160‧‧‧Vacuum evacuation tube

170‧‧‧ resin injection tube

180‧‧‧Resin

181‧‧‧ arrow

200‧‧‧dotted arrow

300‧‧‧glass fiber reinforced plastic

S100~S110‧‧‧Steps

1 is a flow chart showing a method of manufacturing a glass fiber reinforced plastic according to an embodiment of the present invention.

2 to 5 are schematic cross-sectional views showing a manufacturing process of a glass fiber reinforced plastic according to an embodiment of the present invention.

1 is a flow chart showing a method of manufacturing a glass fiber reinforced plastic according to an embodiment of the present invention. The method for manufacturing the glass fiber reinforced plastic comprises the following steps:

Step S100: providing a mold. Referring to FIG. 2 at the same time, in this step, the mold 110 includes a cavity 111, which is a partial shape of the glass fiber reinforced plastic.

Step S102: setting a layer in the cavity. In this step, the laminate may be composed of a core material and/or a fiber material, that is, the laminate disposed in the cavity 111 may be the core material 120, the fiber material 130 or the core material 120 and the fiber. A combination of materials 130. In this embodiment, the laminate is composed of the fibrous material 130 covering the core material 120. The material of the core material 120 may be a foam material or a wood material, and the fiber material 130 may be carbon fiber, glass fiber or Kevlar fiber. The woven form of the fibrous material 130 may be a plain weave, a satin weave or a twill weave or a knit material.

Step S104: setting the flow guiding device on the laminate. In this step, the flow guiding resin mesh 141 mainly assists the flow of the resin. The flow guiding resin mesh 141 may include a release cloth which allows the tree during the resin infusion process. The grease flows through and can be easily removed after the completion of the filling, and then the resin injection tube 170 and the vacuum evacuation tube 160 can be disposed first in the flow guiding resin web.

Step S106: setting a vacuum bag on the flow guiding resin net and covering the cavity 111. In this step, the mold 110 is adhered to the periphery of the vacuum bag 140 with the glue 150. The inside of the vacuum bag 140 has a resin injection hole 143 and a vacuum suction hole 142. The resin injection pipe 170 passes through the resin injection hole 143. The vacuum exhaust pipe 160 passes through the vacuum suction hole 142. Then, the vacuum pump is connected to the vacuum exhaust pipe 160 to extract the air in the cavity 111, so that the cavity 111 is in a vacuum state. The vacuum evacuation hole 142 has a gas permeable membrane underneath. The gas permeable membrane has the particularity that the resin cannot pass through but the gas can be extracted, so that the resin cannot be extracted and the vacuum can be continuously maintained. Moreover, the vacuum bag 140 can withstand one atmosphere and does not generate Any slight leaks can withstand the heating during the post-hardening process. After the vacuum pressure requirement is reached, the vacuum bag 140 is kept closed, and the vacuum pump is turned off to perform a leak test operation to ensure that the inside of the vacuum bag 140 meets the airtightness requirement, and then the resin infusion operation can be prepared.

Step S108: injecting a resin into the cavity. Referring to FIG. 3 at the same time, in this step, the resin 180 may be a first modified vinyl ester resin and/or a second modified vinyl ester resin. The resin 180 is injected into the cavity 111 by the direction of the arrow 181 until the resin 180 is entirely filled with the cavity. Because of the action of the gas permeable film, air can be continuously extracted into the cavity, and the resin 180 can not be extracted to maintain the vacuum, so that the resin 180 can be prevented from flowing inside the fiber 130 and the core 120, and the resin 180 Does not produce a falling pendant.

The first modified vinyl ester resin includes: a resin mixture, a hardener, and a polymerization initiator, wherein the resin mixture includes a modified epoxy resin represented by the following Chemical Formula 1, and a diluent In the above Chemical Formula 1, n is an integer of 0 to 300; and Q and L are each selected from Wherein R1 and R2 are each a hydrogen atom or a methyl group; and M is selected from a hydrogen atom, Wherein R1 and R2 are each a hydrogen atom or a methyl group; and A is selected from the group consisting of: And R4 and R5 are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the substituents on each benzene ring are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen.

The modified epoxy resin represented by Chemical Formula 1 in the resin mixture is hardened by the first modified vinyl ester resin of the present invention since it has both an epoxy functional group and an unsaturated carbon-carbon double bond functional group. In the process, the modified epoxy resin can control the gelation time, the exothermic peak temperature, and the viscosity of the first modified vinyl ester resin.

The diluent is used to adjust the first modified vinyl ester tree The viscosity of the grease, the gelation time, and the mechanical properties of the member made of the first modified vinyl ester resin.

In the resin mixture, the diluent is preferably mixed in a ratio of 50 to 3 weight percent, more preferably, relative to 50 to 97% by weight of the modified epoxy resin represented by Chemical Formula 1. Up to 95 weight percent of the modified epoxy resin, the diluent is mixed in a ratio of 30 to 5 weight percent. When the content of the modified epoxy resin is less than the above range, so that the relative content of the diluent is higher than the above range, the mechanical properties of the member obtained from the first modified vinyl ester resin are not good, and vice versa. When the content of the modified epoxy resin is higher than the above range, such that the relative content of the diluent is lower than the above range, the viscosity of the first modified vinyl ester resin is too high, resulting in difficulty in processing. .

More specifically, the modified epoxy resin is preferably selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, and polyfunctional epoxy resin epoxy resin. a group consisting of a Novolac epoxy resin, a Brominated type epoxy resin, a Cresol-Novolac epoxy resin, and a rubber-toughened epoxy resin. At least one epoxy resin is obtained by esterification reaction with at least one organic unsaturated acid. Wherein, the epoxy resin selected is preferably a bisphenol A epoxy resin, and the organic unsaturated acid is preferably Methacrylic acid, but the ring selected for the esterification reaction is selected. The oxygen resin and the organic unsaturated acid are not limited thereto. Next, the equivalent ratio of the epoxy functional group of the epoxy resin selected to the carboxyl group of the organic unsaturated acid is 10 to 1. Furthermore, the modified epoxy obtained by the esterification reaction In the resin, the molar equivalent ratio of the reactive epoxy functional group to the unsaturated carbon-carbon double bond functional group is from 0.1 to 30.

The esterification reaction for synthesizing the modified epoxy resin is carried out by adding a catalyst which determines the reaction rate and may also affect the hardening time of the first modified vinyl ester resin.

Further, the diluent is preferably selected from, but not limited to, at least one compound selected from the group consisting of Octylene oxide, Butyl glycidyl ether, and monooxygen. Dipentene monoxide, Phenyl glycidyl ether, p-butyl phenyl glycidyl ether, Cresyl glycidyl ether, 3- 3-(pentadecyl)phenyl glycidyl ether, Butadiene dioxide, Dimethyl pentane dioxide, Diglycidyl Ether), Butanediol diglycidyl ether (BDGE), Diethylene glycol diglycidyl ether, Vinyl cyclohexene dioxide, cerium dioxide (Limonene dioxide), Bis(2,3-epoxy cyclopentyl)ether, 3,4-epoxy-6-methylcyclohexylmethyl 3,4 -3,4-epoxy-6-methylcyclohexylmethyl 3,4-epoxy me Thylcyclohexane carboxylate), Divinyl benzene dioxide, 2-glycidyl phenyl glycidyl ether, 2,6-dipropylene oxide phenyl glycidyl ether 2,6-diglycidyl phenyl glycidyl ether), styrene (Styrene), P-vinyltoluene, dichlorostyrene, 2-Hydroxyethyl methacrylate phosphate, acrylate, Methacrylate, diallyl phthalate, Hexamethylene diacrylate, Tripropylene Glycol Diacrylate (TPGDA), cyanuric acid Triallyl cyanurate, trimethylol propane trimethacrylate (TMPTMA), trimethylol propane triacrylate (TMPTA), glycidyl methacrylate (Glycidyl) Methacrylate), Allyl glycidyl ether, Cyclohexane vinyl monoxide, and mixtures of the foregoing. Further, it is preferable to use styrene (Styrene) as the diluent.

The second modified vinyl ester resin includes: a resin mixture; a hardener; and a polymerization initiator, the resin mixture including: a resin mixture, a hardener, and a polymerization initiator, the resin mixture including : at least one epoxy resin is blended with at least one unsaturated compound, and the at least one epoxy resin is preferably selected from the group consisting of bisphenol A epoxy resin, bisphenol F ( Bisphenol F) epoxy resin, polyfunctional epoxy resin epoxy resin, Novolac epoxy resin, Brominated type epoxy resin, o-cresol type (Cresol -Novolac) epoxy resin and rubber toughened epoxy resin, and the epoxy resin is preferably selected from bisphenol A epoxy resin; Preferably, the at least one unsaturated compound is selected from the group consisting of unsaturated polyester resins, vinyl ester resins, styrene, p-vinyltoluene, dichlorobenzene. Dichlorostyrene, 2-Hydroxyethyl methacrylate phosphate, acrylate, methacrylate, diene phthalate Diallyl phthalate, Hexamethylene diacrylate, Tripropylene Glycol Diacrylate (TPGDA), Triallyl cyanurate, Trimethylolpropane III Trimethylol propane trimethacrylate (TMPTMA), trimethylol propane triacrylate (TMPTA), Glycidyl Methacrylate, Allyl glycidyl ether And cyclohexane vinyl monoxide, and the unsaturated compound is preferably styrene or styrene and trimethylolpropane a mixture of acrylates.

Wherein, depending on the viscosity required for the second modified vinyl ester resin and the mechanical properties required for the member made of the second modified vinyl ester resin, the selected epoxy resin and unsaturated compound The weight ratio is 0.2 to 35. Further, the molar equivalent ratio of the reactive epoxy functional group to the unsaturated carbon-carbon double bond functional group in the mixture is from 0.1 to 20.

In the first and second modified vinyl ester resins according to the present invention, the hardener is used to harden an epoxy functional group in the first and second modified vinyl ester resins.

The content of the hardener is preferably from 1 to 100% by weight, more preferably from 5 to 60% by weight, based on the total mass of the resin mixture.

In one of the first and second modified vinyl ester resins according to the present invention, the polymerization initiator is used to make the unsaturated carbon-carbon double in the first and second modified vinyl ester resins The bond functional group undergoes a hardening reaction.

The content of the polymerization initiator is preferably from 0.1 to 5% by weight, more preferably from 0.5 to 2% by weight, based on the total mass of the resin mixture.

The following table compares the linear shrinkage of the resin of the first modified vinyl ester resin and the general vinyl ester resin of the present invention:

The table below shows the comparison of the strength, hardness, temperature and other characteristics of the first modified vinyl ester resin with the requirements of the Norwegian Classification Society (DNV) and the relevant international standard test regulations number:

Step S110: heating the resin. Please also refer to FIG. 4, in this step, the resin 180 is heated (indicated by the dashed arrow 200 in FIG. 4) to between 3 and 30 degrees Celsius for baking, and maintained for 12 hours to establish The establishment of the strength of the resin 180. Until the surface hardness of the resin 180 reaches a Barcol Hardness of more than 30, it means that the glass fiber is completed. Reinforce the plastic and then perform the release work. As shown in FIG. 5, the mold release operation means removing the flow guiding resin mesh 141, the vacuum bag 140, the resin injection pipe 170, and the vacuum exhaust pipe 160 (as shown in FIG. 2), and then separating the glass fiber reinforced plastic 300 and The mold 110 completes the glass fiber reinforced plastic 300.

In the past, in order to solve the problem of thread printing, the method of adding a non-woven fabric to absorb the shrinkage of the resin during the construction of the yacht, but this method is not effective, the stability is not good, and the working time is also increased. , construction period, and increase weight. However, by taking the 90-inch hull made by the above steps S100 to S110 as an example, the manufacturing method of the present invention can save 43% of production time and 37% of labor compared with the prior art. Because of the lack of non-woven materials, the weight is reduced by 5 percent.

The glass fiber reinforced plastic of the present invention and the method for producing the same are mainly used for member infusion using a first modified vinyl ester resin and/or a second modified vinyl ester resin. It is mainly used for vacuum infusion of large fiber composite parts and has excellent surface flatness. The properties of the resin have long gelation time, short hardening time, low heat release, high glass transition temperature and low shrinkage, and excellent impregnation properties for glass fibers and carbon fibers. After the infusion is performed by using the first modified vinyl ester resin and/or the second modified vinyl ester resin, the heating and hardening operation is performed, and the resin strength is established by controlling the heating temperature, and the resin shrinkage is established. The thread displayed is within acceptable limits.

In the above, it is merely described that the present invention is an embodiment or an embodiment of the technical means for solving the problem, and is not intended to limit the scope of implementation of the present invention. That is, in accordance with the text of the scope of the patent application of the present invention, Equivalent changes and modifications made in accordance with the scope of the invention are covered by the scope of the invention.

S100~S110‧‧‧Steps

Claims (6)

A method for manufacturing a glass fiber reinforced plastic, comprising the steps of: providing a mold, the mold comprising a cavity; providing a laminate in the cavity; providing a flow guiding resin mesh on the laminate; and providing a vacuum bag Conducting a resin mesh, covering the cavity, sealing the flow-through resin mesh, the laminate between the vacuum bag and the die; injecting a resin into the cavity; and heating the resin to a temperature of 30 degrees Celsius Between 70 degrees; wherein the resin is a first modified vinyl ester resin and/or a second modified vinyl ester resin, the first modified vinyl ester resin comprises: a resin mixture, a hardener and a polymerization initiator, wherein the resin mixture comprises a modified epoxy resin represented by the following Chemical Formula 1, and a diluent In the above Chemical Formula 1, n is an integer of 0 to 300; and Q and L are each selected from Wherein R1 and R2 are each a hydrogen atom or a methyl group; and M is selected from a hydrogen atom, Wherein R1 and R2 are each a hydrogen atom or a methyl group; and A is selected from the group consisting of: , wherein R 4 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the substituents on each benzene ring are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen; the second modified ethylene The ester resin comprises: a resin mixture; a hardener; and a polymerization initiator, the resin mixture comprising: at least one epoxy resin selected from the group consisting of bisphenol A epoxy Resin, bisphenol F epoxy resin, polyfunctional epoxy resin epoxy resin, Novolac epoxy resin, Brominated type epoxy resin, adjacent a Cresol-Novolac epoxy resin and a rubber toughened epoxy resin; and at least one unsaturated compound selected from the group consisting of unsaturated polyester resins, vinyl ester resins, and benzene Styrene, p-vinyltoluene, dichlorostyrene, 2-Hydroxyethyl methacrylate phosphate, acrylic acid Acrylate, methacrylate e), diallyl phthalate, Hexamethylene diacrylate, Tripropylene Glycol Diacrylate (TPGDA), triallyl cyanurate (Triallyl) Cyanurate), trimethylol propane trimethacrylate (TMPTMA), trimethylol propane triacrylate (TMPTA), glycidyl methacrylate (Glycidyl Methacrylate), allylic Allyl glycidyl ether and cyclohexane vinyl monoxide. The method for producing a glass fiber reinforced plastic according to the above aspect of the invention, wherein the flow guiding resin net comprises a release cloth. The method for manufacturing a glass fiber reinforced plastic according to claim 1, further comprising the step of: providing a cement between the vacuum bag and the mold. The method for producing a glass fiber reinforced plastic according to the first aspect of the invention, wherein the step of injecting the first modified vinyl ester resin and/or the second modified vinyl ester resin into the cavity Previously, the following steps were included: the air inside the cavity was extracted. The method for manufacturing a glass fiber reinforced plastic according to the first aspect of the invention, wherein the step of providing the laminated layer in the cavity further comprises: providing a core material and a fiber material in the cavity, and the fiber material The core material is coated to form the laminate. The method for producing a glass fiber reinforced plastic according to the first aspect of the invention, wherein the laminate is a core material or a fiber material.