KR102225655B1 - UV curable sheet resin composition for repairing concrete and waterproof sheet and preparation mehtod thereof - Google Patents

Abstract

The present invention is a vinyl ester resin oligomer obtained by reacting an epoxy resin, a dicarboxylic acid, an unsaturated carboxylic acid, a reaction catalyst and an amine catalyst; Reactive diluents; Polyester resin; And a photoinitiator; wherein the epoxy resin relates to a resin composition for preparing a photocurable sheet comprising a low molecular weight epoxy resin having an epoxy equivalent of 150 to 250 and a high molecular weight epoxy resin having an epoxy equivalent of 400 to 550.

Description

Resin composition for manufacturing photo-curable sheet for repairing concrete and waterproof lining, and manufacturing method thereof {UV curable sheet resin composition for repairing concrete and waterproof sheet and preparation mehtod thereof}

The present invention relates to a resin composition for manufacturing a photocurable sheet for concrete repair and waterproof lining, and a method for manufacturing the same.

Vinyl ester resin is a resin dissolved in styrene, a reactive monomer by reacting an unsaturated monobasic acid with an epoxy resin, and has good corrosion resistance, adhesion, and excellent mechanical strength, so it is widely used in corrosion-resistant tanks, ducts, and pipes.

In addition, vinyl ester resin is similar in curing method and operation method to unsaturated polyester resin, and it is easy to work at room temperature, fast curing time, and has excellent glass fiber impregnation, workability, and adhesion, so that corrosion-resistant floor linings, corrosion-resistant plastic structures, and adhesive molds It is widely used in products such as UV rays and electronic curing paints using an unsaturated group in the molecule.

However, in general, vinyl ester resins have low resin viscosity and good compatibility with glass fibers, so they are mainly used for reinforced plastic (FRP), concrete corrosion-resistant lining, and waterproof lining, which are mainly used by mixing accelerators and hardeners by hand lay-up. As a thermosetting resin, it has many disadvantages such as curing time, working environment, and manufacturing cost compared to photocurable resins. Therefore, it works in the manufacture of sheet molding compounds (SMC) or cured sheets suitable for UV curing using vinyl ester resins. In order to improve the properties and curability, and to reduce the manufacturing cost, there is a need to develop a technology for providing excellent photocuring properties to the vinyl ester resin, thickening of the resin to be manufactured as a sheet for SMC, and curing with ultraviolet rays.

Republic of Korea Patent Publication No. 10-2011-0111734

An object of the present invention is to provide a resin composition for manufacturing a photocurable sheet capable of improving a complex work process, excellent processability, and curing in a short time.

It is an object of the present invention to provide a resin composition for manufacturing a photocurable sheet capable of producing a photocurable sheet having excellent physical properties such as tensile strength, flexural strength, compressive strength and Barcol hardness.

The resin composition for producing a photocurable sheet according to the present invention includes a vinyl ester resin oligomer obtained by reacting an epoxy resin, a dicarboxylic acid, an unsaturated carboxylic acid, a reaction catalyst, and an amine catalyst; Reactive diluents; Polyester resin; And a photoinitiator; includes,

The epoxy resin includes a low molecular weight epoxy resin having an epoxy equivalent of 150 to 250 and a high molecular weight epoxy resin having an epoxy equivalent of 400 to 550.

In the resin composition for manufacturing a photocurable sheet according to an embodiment of the present invention, the epoxy resin may include bisphenol A.

In the resin composition for preparing a photocurable sheet according to an embodiment of the present invention, the low molecular weight epoxy resin and the high molecular weight epoxy resin may be low molecular weight bisphenol A and high molecular weight bisphenol A, respectively.

In the resin composition for preparing a photocurable sheet according to an embodiment of the present invention, the weight ratio of the low molecular weight bisphenol A: the high molecular weight bisphenol A may be 1:0.7 to 3.

In the resin composition for manufacturing a photocurable sheet according to an embodiment of the present invention, the epoxy resin may further include a phenol noblock epoxy resin.

In the resin composition for preparing a photocurable sheet according to an embodiment of the present invention, the resin composition for preparing a photocurable sheet is 10 to 20 parts by weight of low molecular weight bisphenol A and 8 to 35 parts by weight of high molecular weight bisphenol A based on 100 parts by weight of phenol noblock epoxy resin. It may include.

In the resin composition for preparing a photocurable sheet according to an embodiment of the present invention, the reactive diluent may include one or more selected from a compound containing a vinyl group and a compound containing an acrylic group.

In the resin composition for preparing a photocurable sheet according to an embodiment of the present invention, the reaction catalyst may be one or two or more selected from alkyl ammonium salt, triphenylphosphine, triphenylantimony, and dimethylaminopyridine.

In the resin composition for preparing a photocurable sheet according to an embodiment of the present invention, the amine-based catalyst may be one or two or more selected from triethylamine, ethyltrimethylammonium bromide, dimethylbenzylamine, and di-n-butylamine.

The present invention also provides a photocurable sheet manufacturing method, and the photocurable sheet manufacturing method according to the present invention comprises a first resin composition layer by applying a resin composition for manufacturing a photocurable sheet according to an embodiment of the present invention to a first carrier film. A first step of forming;

A second step of supplying fibers to the first resin composition layer;

A third step of cutting the fibers to form a fibrous layer;

A fourth step of forming a second resin composition layer by applying the resin composition for manufacturing a photocurable sheet according to an embodiment of the present invention to a second carrier film;

A fifth step of preparing a sheet by bonding the first carrier film and the second carrier film to contact the second resin composition layer with the fibrous layer; And

And a sixth step of performing photocuring by irradiating light on the sheet.

In the method for manufacturing a photocurable sheet according to an embodiment of the present invention, the fibers may be one or two or more selected from glass fibers, carbon fibers, and aramid fibers.

The resin composition for manufacturing a photocurable sheet according to the present invention includes a low molecular weight epoxy resin having an epoxy equivalent of 150 to 250 and a high molecular weight epoxy resin having an epoxy equivalent of 400 to 550, and curing through photocuring, thereby reducing a complex work process. There is an advantage of being improved, excellent processability, and rapid curing, and further, there is an advantage that the photo-cured sheet to be manufactured has excellent physical properties.

1 is a schematic diagram of a method of manufacturing a photocurable sheet according to an embodiment of the present invention.
Figure 2 shows the concrete adhesion after curing of the photocurable sheet according to an embodiment of the present invention.

Advantages and features of the embodiments of the present invention, and a method of achieving them will be apparent with reference to the embodiments described later in detail together with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in a variety of different forms, and only these embodiments make the disclosure of the present invention complete, and are common knowledge in the technical field to which the present invention pertains. It is provided to completely inform the scope of the invention to those who have, and the invention is only defined by the scope of the claims. The same reference numerals refer to the same elements throughout the specification.

In describing the embodiments of the present invention, if it is determined that a detailed description of a known function or configuration may unnecessarily obscure the subject matter of the present invention, a detailed description thereof will be omitted. In addition, terms to be described later are terms defined in consideration of functions in an embodiment of the present invention, which may vary according to the intention or custom of users or operators. Therefore, the definition should be made based on the contents throughout the present specification.

The resin composition for producing a photocurable sheet according to the present invention includes a vinyl ester resin oligomer obtained by reacting an epoxy resin, a dicarboxylic acid, an unsaturated carboxylic acid, a reaction catalyst, and an amine catalyst; Reactive diluents; Polyester resin; And a photoinitiator; includes,

The epoxy resin is characterized in that it includes a low molecular weight epoxy resin having an epoxy equivalent of 150 to 250 and a high molecular weight epoxy resin having an epoxy equivalent of 400 to 550.

The resin composition for producing a photocurable sheet according to the present invention includes a vinyl ester resin oligomer obtained by reacting an epoxy resin, a dicarboxylic acid, an unsaturated carboxylic acid, a reaction catalyst, and an amine catalyst; Reactive diluents; Polyester resin; And a photoinitiator; by controlling the viscosity, there is an advantage of excellent processability and workability, and further, it is possible to achieve the effect of improving the work process through photocuring. In addition, the resin composition for producing a photocurable sheet according to the present invention includes a low molecular weight epoxy resin having an epoxy equivalent of 150 to 250 and a high molecular weight epoxy resin having an epoxy equivalent of 400 to 550 at the same time, thereby exhibiting high mechanical properties.

In the resin composition for producing a photocurable sheet according to an embodiment of the present invention, the epoxy resin is not particularly limited as long as it is an epoxy resin containing two or more epoxy groups, but may include at least one resin selected from phenol noblock epoxy resin and bisphenol A. I can.

Preferably, in the resin composition for preparing a photocurable sheet according to an embodiment of the present invention, the epoxy resin may preferably contain bisphenol A, and more preferably, the low molecular weight epoxy resin and the high molecular weight epoxy resin are each low molecular weight bisphenol A. And high molecular weight bisphenol A. The resin composition for preparing a photocurable sheet according to an exemplary embodiment of the present invention simultaneously includes the low molecular weight bisphenol A and the high molecular weight bisphenol A as described above, thereby securing an appropriate level of viscosity and remarkably improving workability.

Specifically, the weight ratio of the low molecular weight bisphenol A: high molecular weight bisphenol A may be 1:0.7 to 3, preferably 1:1 to 2.5, and a small amount of high molecular weight bisphenol A is added in the above-described range so that the viscosity is too low. Problems can be prevented, and further, physical properties such as tensile strength of the manufactured photocurable sheet can be improved.

In the resin composition for manufacturing a photocurable sheet according to an embodiment of the present invention, the epoxy resin may further include a phenol noblock epoxy resin, and preferably, the phenol noblock epoxy resin may have an epoxy equivalent of 170 to 190. As a result, one of the preferred embodiments of the present invention is that the epoxy resin may include a low molecular weight bisphenol A, a high molecular weight bisphenol A, and a phenol noblock epoxy resin, and by including such a resin composition, processability and workability without problems such as stickiness It is possible to manufacture this excellent resin composition for producing a photocurable sheet.

In the resin composition for producing a photocurable sheet according to an embodiment of the present invention, the epoxy resin may contain 10 to 20 parts by weight, preferably 11 to 18 parts by weight, based on 100 parts by weight of the phenol noblock epoxy resin, and low molecular weight bisphenol A, It may contain 8 to 35 parts by weight of high molecular weight bisphenol A relative to 100 parts by weight of the phenol noblock epoxy resin, and has the advantage of securing a viscosity of at least a certain level in this range, lowering the risk of gel formation during synthesis, and having high releasability.

The dicarboxylic acid compound contained in the resin composition for producing a photocurable sheet according to an embodiment of the present invention is a compound containing two carboxyl groups in a molecule and acts as a ring-opening material for opening the epoxy group of the epoxy resin. Although not limited, it may be one or two or more selected from adipic acid, isophthalic acid, terephthalic acid, itaconic acid, and phthalic acid.

In the resin composition for producing a photocurable sheet according to an embodiment of the present invention, the unsaturated carboxylic acid reacts with the epoxy resin to form a vinyl group at the end of the vinyl ester resin, thereby radically curing. Usable unsaturated carboxylic acids include acrylic acid and meta. Acrylic acid, methyl (meth)acrylic acid, beta-carboxy ethyl acrylate (BETA-CarboxyEthyl Acrylate), 2-Acryloyloxy Ethyl Succinate, 2-acryloyloxy ethyl hexahydrophthalate (2 -Acryloyloxy Ethyl Hexa Hydro Phthalate), 2-Acryloyloxy Ethyl Phthalate (2-Acryloyloxy Ethyl Phthalate) and 2-Acryloyloxy Ethyl Tetra Hydro Phthalate (2-Acryloyloxy Ethyl Tetra Hydro Phthalate) It may be, and more specifically, may be methacrylic acid.

In the resin composition for preparing a photocuring sheet according to an embodiment of the present invention, the amine-based catalyst may be any one or more selected from the group consisting of triethylamine, ethyltrimethylammonium bromide, dimethylbenzylamine, and di-n-butylamine. , Specifically, it may be triethylamine.

The reaction catalyst and storage stabilizer may be one or two or more selected from alkyl ammonium salt, triphenylphospin, triphenylantimony, and dimethylaminopyridine, preferably triphenyl antimony.

In the resin composition for manufacturing a photocurable sheet according to an embodiment of the present invention, the vinyl ester resin oligomer may further include a polymerization inhibitor. When the vinyl ester resin further includes a polymerization inhibitor, there is an advantage of preventing gelation of the resin being reacted and improving stability at room temperature. At this time, the polymerization inhibitor is hydroquinone, toluhydroquinone, methylhydroquinone, hydroquinone methyl ether, benzoquinone, methyl-p-benzoquinone, t-butylcatechol, 2,6-di-t-butyl-4- It may be one or two or more selected from methylphenol, 4-methoxyphenol, and phenothiazine, and the polymerization inhibitor may be added in an amount of 0.5 to 2 parts by weight based on 100 parts by weight of the epoxy resin.

The resin composition for producing a photocurable sheet according to the present invention further includes a reactive diluent in addition to the vinyl ester resin oligomer. The reactive diluent may decrease the viscosity of the resin to a certain extent and may be a low viscosity monomer including one or more functional groups capable of polymerization reaction, and specifically, the polymerizable reactor may be a vinyl group or an acrylic group.

More specifically, the reactive diluent is styrene, halogenated styrene, vinyltoluene, divinylbenzene, alpha methylstyrene, bisphenol A di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate methyl (meth) acrylate , Ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, methylcyclohexyl (meth) acrylate, It may be one or more selected from isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, di (meth) acrylate and ethoxylated bisphenol adi (meth) acrylate.

The resin composition for producing a photocurable sheet according to the present invention further includes a polyester resin. The resin composition for producing a photocurable sheet according to the present invention has the advantage of having a high binding strength with fibers such as glass fibers to be mixed later by including polyester together with the above-described vinyl ester resin, and shortening the curing time. The polyester resin may be a polyester-ether block copolymer containing polyethylene terephthalate, polytetramethylene terephthalate, polybutylene terephthalate, a hard portion of polyester and a soft portion of polyester.

The resin composition for producing a photocurable sheet according to the present invention includes a photoinitiator, and the photoinitiator serves to initiate photocuring of the resin composition. In the resin composition for producing a photocurable sheet according to an embodiment of the present invention, the photoinitiator may be a short-wavelength photoinitiator exhibiting light absorption in the range of 200-350nm and a long-wavelength photoinitiator exhibiting light absorption in the range of 300-480nm. When a short wavelength photoinitiator is used, it is advantageous for the production of a thin cured product, and when a long wavelength initiator is used, it is advantageous for the production of a thick cured product. When using a long-wavelength photoinitiator, the long-wavelength photoinitiator can be used alone, but it can also be mixed with a short-wavelength photoinitiator in an appropriate composition ratio. However, in the case of mixing the photoinitiators, it is preferable to mix and use two or more photoinitiators having different absorption wavelength ranges. This is because the light energy can be efficiently used and the curing speed can be further increased. As the short wavelength photoinitiator, any known in the art may be used, such as 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy -1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone, methylbenzoylformate α,α-dimethoxy-α-phenylacetophenone, 2-benzoyl-2-( Dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl) -1-propanone, etc., and currently marketed products include BASF's Irgacure 184, Darocur1173, Irgacure 2959, Darocur MBF, Irgacure 651, Irgacure 369, Irgacure 907, and the like.

In addition, any known long-wavelength photoinitiator may be used, for example 2-benzyl-2-dimethylamino-1-butanone, diphenyl (2,4,6-trimethylbenzoyl)-phosphine oxide, bis( 2,4,6-trimethylbenzoyl)-phenylphosphine oxide, benzyl dimethylketal,2,4,6-trimethylbenzophenone, oligo(2-hydroxy-2-methyl-1-(4-(methylvinyl)phenyl) Propane),2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4-diethylthioxantoin, 3,3-dimethyl-4-methoxy-benzophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, bis(2,6-dichlorbenzoyl )-Phenylphosphine oxide, bis(2,6-dichlorbenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,6-dichlorbenzoyl)-4-ethoxyphenylphosphine oxide, bis( 2,6-dichlorbenzoyl)-4-propylphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyl-di Phenylphosphine oxide and the like are mentioned, and as commercially available products, Irgacure819 Irgacure369, Irgacure2020, Irgacure 2022, Irgacure 2100, Irgacure784, Lucirin TPO, Darocur 4265, etc. of BASF in Switzerland can be used.

The resin composition for preparing a photocurable sheet according to an embodiment of the present invention includes 0.5 to 7 parts by weight of dicarboxylic acid, 30 to 55 parts by weight of unsaturated carboxylic acid, 0.3 to 3 parts by weight of reaction catalyst, and 0.05 to 0.5 parts by weight based on 100 parts by weight of the epoxy resin. Parts of an amine-based catalyst, and 80 to 200 parts by weight of a reactive diluent. More preferably, the resin composition for preparing a photocurable sheet according to an embodiment of the present invention may contain 0.8 to 4 parts by weight of dicarboxylic acid, 35 to 50 parts by weight of dicarboxylic acid, based on 100 parts by weight of the epoxy resin, and the reactive diluent May be included in a weight ratio of 1:0.1 to 8 in the ratio of the vinyl group-containing compound: the acrylic group-containing compound. Since the resin composition for manufacturing a photocurable sheet according to an embodiment of the present invention satisfies the above-described range, it is possible to manufacture a photocurable sheet having excellent physical properties such as printing strength, flexural strength, and compressive strength.

The present invention also provides a method for producing a resin composition for producing a photocurable sheet. The method for manufacturing a resin composition for manufacturing a photocurable sheet according to the present invention may be a manufacturing method for manufacturing the above-described photocurable sheet. A first step of adding an epoxy resin, a dicarboxylic acid, an unsaturated carboxylic acid, a reaction catalyst, and an amine-based catalyst to the reactor, and heating the reactor to 90 to 120°C; And

And a second step of cooling the reactor to 60 to 80° C. after the first step, and adding a reactive diluent, a polyester resin, and a photoinitiator. The resin composition for manufacturing a photocurable sheet manufactured through the above-described process has the advantage of excellent processability, improved complex working process, and easy curing. In addition, the specific substances and addition amounts of the epoxy resin, dicarboxylic acid, unsaturated carboxylic acid, reaction catalyst, amine catalyst, reactive diluent, polyester resin and photoinitiator added in the first and second steps are in the resin composition for producing a photocurable sheet. It is the same as described, and detailed description is omitted for redundant description.

The present invention also provides a method for manufacturing a photocurable sheet using the resin composition for preparing a photocurable sheet prepared by the method for preparing a resin composition for preparing a photocurable sheet described above. The photocurable sheet manufacturing method according to the present invention includes a first step of forming a first resin composition layer by applying a resin composition for preparing a photocurable sheet according to an embodiment of the present invention to a first carrier film;

A second step of supplying fibers to the first resin composition layer;

A third step of cutting the fibers to form a fibrous layer;

A fourth step of forming a second resin composition layer by applying the resin composition for manufacturing a photocurable sheet according to an embodiment of the present invention to a second carrier film;

A fifth step of preparing a sheet by bonding the first carrier film and the second carrier film to contact the second resin composition layer with the fibrous layer; And

And a sixth step of performing photocuring by irradiating light on the sheet.

In this case, the fiber is not limited if it is a fiber that is typically applied to a photocurable sheet, but may be specifically one or two or more selected from glass fiber, carbon fiber, and aramid fiber, and more specifically, may be glass fiber. The invention is not limited thereto.

When the above-described photocurable sheet manufacturing method is described in more detail, when the first carrier film 1 is supplied from the first film supply unit 10, the first resin supply unit 20 on the first carrier film 1 A resin composition for manufacturing a photocurable sheet (hereinafter referred to as a resin composition) according to an embodiment of the present invention is supplied to form a first resin composition layer. The fiber supply unit 30 on the first resin composition layer supplies fibers such as glass fibers, and cuts the fibers supplied from the first fiber cutting unit 40 and the second fiber cutting unit 50.

Separately, while supplying the second carrier film 2 from the second film supply unit 70, the second resin supply unit 60 supplies the resin composition on the second carrier film 2 to provide a second resin composition. To form a layer. The second carrier film on which the second resin composition layer is formed moves through a roll and is transferred to the first carrier so that the first resin composition layer and the second resin composition layer come into contact with each other. The transferred first carrier film and the second carrier film are bonded to each other to form a sheet, and curing is completed by irradiating the sheet with light in the light irradiation unit 80, and the sheet manufactured in the winding unit 90 is wound and stored. do.

Hereinafter, the present invention will be described in detail by examples and comparative examples. The following examples are only intended to aid understanding of the present invention, and the scope of the present invention is not limited by the following examples.

1. Preparation of vinyl ester oligomer and verification of physical properties

Phenol noblock resin (Kukdo Chemical Co., Ltd. YDPN-638), low molecular weight bisphenol A (Kukdo Chemical Co., Ltd. YD-128), high molecular weight bisphenol A (Kukdo Chemical Co., Ltd. YD-011), Toluhydroguinone, adipic acid, triethylamine, triphenylantimony , Styrene monomer, methacrylic acid, malelicanhydride and 4-tert-butylcatechol were mixed in the amounts shown in Table 1 to prepare a vinyl ester oligomer.

Styrene monomer, 2-hydroxyethyl methacrylate, IGRACURE 754 (photoinitiator), (Darocure TPO) and saturated polyester CBL-420A produced by Chembase were added to the prepared vinyl ester oligomer in the composition of Table 2 and mixed. Thus, a resin composition for producing a photocurable sheet was prepared.

Epoxy equivalent Manufacturing Example 1 Manufacturing Example 2 Manufacturing Example 3 Manufacturing Example 4 Manufacturing Example 5 Phonoblock type 170-190 27.499 30.969 24.962 42.531 29.668 Bisphenol A type 450-500 4.061 4.245 3.495 Bisphenol A type 175-190 6.679 2.613 8.687 10.920 Toluhydroguinone 0.041 0.043 0.038 0.054 0.052 Adipic Acid 1.144 0.826 0.799 Triethylamine 0.074 0.078 0.060 0.050 0.045 Triphenyl antimony 0.049 0.052 0.050 0.062 stylene monomer 7.864 8.220 7.988 methacrylicacid 16.673 16.000 15.476 19.670 19.779 malelicanhydride 2.860 2.404 1.996 4-tert -butylcatechol 0.006 0.005 0.004 0.004 0.005 stylene monomer 21.448 22.418 23.464 37.629 39.531 2-hydroxyethyl Methacrylate 11.602 12.127 12.982 Sum 100.000 100.000 100.000 100.000 100.000

Acid And viscosity check

The acid value at the end of the reaction of the vinyl ester oligomers prepared in Preparation Examples 1 to 5, the viscosity immediately after preparation, the viscosity after 30 minutes, and the viscosity after 16 hours were measured, and are shown in Table 2.

At this time, the acid value is after mixing 1 g of the vinyl ester resin composition of Preparation Examples 1 to 5 with 30 g of a neutral solvent, stirring until the sample is completely dissolved, adding 1% by weight of phenolphthalein solution, and titrating with 0.1N KOH solution. The acid value was measured, and the viscosity was measured using a Brookfield viscometer based on 25°C. The thickening viscosity is measured after 30 minutes in a 30°C thermostat, after adding 0.33 parts by weight of moisture and 2 parts by weight of magnesium hydroxide to 100 parts by weight of the resin, mixing for 1 minute by high-speed stirring (1000 rpm), and then measuring after 30 minutes in a 30°C thermostat, and then leaving it in a 45°C thermostat for 16 hours It is the result of measuring the viscosity.

Manufacturing Example 1 Manufacturing Example 2 Manufacturing Example 3 Manufacturing Example 4 Manufacturing Example 5 End reaction acid value KOH mg/l 24.5 25.3 28.5 7.8 8.3 Resin viscosity cps 2200 1850 2600 500 600 Thickening viscosity cps after 30 minutes 8000 7500 12500 550 700 Thickening viscosity cps after 16 hours 230000 300000 390000 550 710 SMC manufacturing possibility possible possible possible Impossible Impossible

Referring to Table 2, the vinyl ester oligomers prepared in Preparation Examples 1 to 3 have a viscosity of 30 minutes after preparation and a viscosity after 16 hours of preparation for a sheet molding compound, but the vinyl ester oligomers prepared in Preparation Examples 4 and 5 have viscosity Is too low, it can be confirmed that it is difficult to apply it to the sheet molding compound.

Curability measurement

The vinyl ester oligomers prepared in Preparation Examples 1 to 5 were allowed to stand in an unshaded place with a UV Index of 3 to 7 for 20 minutes to proceed with curing.

As a result, it can be seen that in the case of the vinyl ester oligomers of Preparation Examples 1 to 3, curing was completed without flowing down or sticky, but in the case of the vinyl ester oligomers of Preparation Examples 4 and 5, stickiness and flowing down phenomenon occurred. Based on this, it can be seen that the vinyl ester oligomer according to an embodiment of the present invention can be easily cured with only UV included in natural light, and can be constructed without a separate UV facility.

2. Preparation of photocurable sheet using resin composition for photocuring sheet manufacturing and verification of physical properties

Photocuring Measurement of physical properties of resin composition for sheet manufacturing

The vinyl ester oligomers of Preparation Examples 1 to 3 were mixed in the composition of Table 3, and cured at UV indexes 3 to 7 for 20 minutes, and after curing, the Barcol hardness was measured and indicated at the bottom of Table 3.

Example 1 Example 2 Example 3 Example 4 Example 5 Production Example 1 Resin 750 500 750 Production Example 2 Resin 750 Production Example 3 Resin 750 Polyester low shrinkage agent 250 250 250 500 250 IGRACURE 754 0.1 0.3 0.2 Darocure TPO 0.50 0.30 0.70 0.50 0.30 Barcol hardness (J/m) 45 46 48 30 38

Referring to Table 3, it can be seen that Examples 1 to 3 exhibit higher Barcol hardness, which seems to be the effect of mixing the photoinitiator.

Photocuring Sheet property measurement

The resin of Examples 1 to 3 was used, but before curing, aluminum hydroxide, an internal release agent, and glass fiber were mixed in the composition of Table 4 and cured at UV indexes 3 to 7 for 20 minutes to prepare a photocurable sheet. The tensile strength, flexural strength (ASTM D790), compressive strength (ASTM 365), Barcol hardness, water absorption and flame retardant test results of the photocured sheet are shown in FIG. 5.

Example 7 Example 8 Example 9 Example 1 resin 35.84 Example 2 resin 35.84 Example 3 resin 35.84 Aluminum hydroxide 43.01 Internal release agent
(Zn-St, Shinwon Industrial Co., Ltd. Hi-FLOW) 1.43 Glass fiber chop Fiber 19.71

Referring to Table 5, the photocured sheet according to an embodiment of the present invention has excellent mechanical properties such as tensile strength, flexural strength, compressive strength, and Barcol hardness, and can secure a high flame retardant grade by mixing with a flame retardant. can confirm.

How to measure Example 7 Example 8 Example 9 The tensile strength MPa ASTM D 3039 72.3 69.8 71.8 Flexural strength MPa ASTM D 790 95,3 96.3 94.9 Compressive strength MPa ASTM D 695 108 102 106 Barcol hardness J/m ASTM D 2583 54 56 55 moisture
Transmittance g/㎡·h·mmhg ASTM E96 0.016 0.018 0.017 Flame retardant test ranking UL94-VFlammability test V-O V-O V-O

1 First carrier film 2 Second carrier film
3 sheet 4 photocurable sheet
10 First film supply unit 20 First resin supply unit
30 Fiber supply part 40 First fiber cutting part
50 Second fiber cutting section 60 Second resin supply section
70 Second film supply unit 80 Light irradiation unit
90 winding

Claims (11)

Vinyl ester resin oligomers obtained by reacting an epoxy resin, a dicarboxylic acid, an unsaturated carboxylic acid, a reaction catalyst, and an amine catalyst; Reactive diluents; Polyester resin; And a photoinitiator; includes,
The epoxy resin includes a low molecular weight epoxy resin having an epoxy equivalent of 150 to 250 and a high molecular weight epoxy resin having an epoxy equivalent of 400 to 550,
The epoxy resin contains 11 to 18 parts by weight of low molecular weight bisphenol A and 8 to 35 parts by weight of high molecular weight bisphenol A, based on 100 parts by weight of phenol novolac epoxy resin,
0.5 to 7 parts by weight of dicarboxylic acid, 30 to 55 parts by weight of unsaturated carboxylic acid, 0.3 to 3 parts by weight of reaction catalyst and 0.05 to 0.5 parts by weight of amine catalyst, 80 to 200 parts by weight of a reactive diluent based on 100 parts by weight of the epoxy resin, ,
A resin composition for producing a photocurable sheet, characterized in that the viscosity is 1850 to 2600 cps. delete delete The method of claim 1,
The weight ratio of the low molecular weight bisphenol A: high molecular weight bisphenol A is 1:0.7 to 3, characterized in that the resin composition for producing a photocurable sheet. delete delete The method of claim 1,
The reactive diluent comprises one or two or more selected from a compound containing a vinyl group and a compound containing an acrylic group. The method of claim 1,
The reaction catalyst is one or two or more selected from alkyl ammonium salt, triphenylphospin, triphenylantimony and dimethylaminopyridine resin composition for producing a photocurable sheet. The method of claim 1,
The amine-based catalyst is one or two or more selected from triethylamine, ethyltrimethylammonium bromide, dimethylbenzylamine and di-n-butylamine resin composition for producing a photocurable sheet. A first step of forming a first resin composition layer by applying the resin composition for preparing a photocurable sheet according to any one of claims 1, 4, and 7 to 9 on a first carrier film;
A second step of supplying fibers to the first resin composition layer;
A third step of cutting the fibers to form a fibrous layer;
A fourth step of forming a second resin composition layer by applying the resin composition for manufacturing a photocurable sheet of any one of claims 1, 4, and 7 to 9 on a second carrier film;
A fifth step of preparing a sheet by bonding the first carrier film and the second carrier film to contact the second resin composition layer with the fibrous layer; And
A photo-curing sheet manufacturing method comprising a; a sixth step of performing photo-curing by irradiating light to the sheet. The method of claim 10,
The fiber is one or two or more selected from glass fiber, carbon fiber and aramid fiber photocurable sheet manufacturing method.

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