KR100275897B1 - Matrix using hybrid system of epoxy/unsaturated polyester resin - Google Patents

Abstract

The present invention provides a matrix comprising a composition obtained by hybridizing 90 to 98% by weight of an epoxy resin and 2 to 10% by weight of an unsaturated polyester resin, and a method of preparing the same. The matrix according to the present invention is excellent in thermal hardening and workability as well as thermal, mechanical and chemical properties by hybridizing an existing thermosetting resin epoxy resin and unsaturated polyester resin in a specific mixing ratio.

Description

Matrix using hybrid system of epoxy / unsaturated polyester resin

The present invention relates to a matrix using a hybrid system of epoxy / unsaturated polyester resins. More specifically, the present invention relates to a new matrix in which physical properties are improved by hybridizing an epoxy and an unsaturated polyester, which are existing thermosetting resins.

Epoxy resins are widely used in coating materials, electrical insulation materials, composite matrixes, civil engineering and building materials, automotive aircraft, etc. because of their excellent thermal, mechanical and chemical resistance properties.

Unsaturated polyester resins are various in type and are easy to cure. Especially for organic building composites, they are applied to building panels, swimming pools, interior doors, flooring, and simple building materials. It is in the spotlight as an alternative matrix.

In recent years, new capabilities for matrices are required, and the development of matrices that meet these needs is urgently needed. New matrix development methods include the development of the matrix itself and the selection of existing matrices and hybridization of them to take advantage of the advantages of individual matrices and to compensate for the disadvantages to create matrices with improved physical properties. In the former case, a lot of research time and research costs are required, so the latter is attracting attention.

An object of the present invention is to hybridize an epoxy resin and an unsaturated polyester resin, which are existing thermosetting resins, in a specific mixing ratio, to prepare a matrix for a composite material having excellent thermal, mechanical and chemical resistance properties as well as fast curing and workability.

1 is a view showing the tensile strength according to the content of unsaturated polyester in the hybrid system of epoxy / unsaturated polyester resin.

2 is a view showing the flexural strength and flexural modulus according to the content of unsaturated polyester in a hybrid system of epoxy / unsaturated polyester resin.

3 is a view showing the impact strength according to the content of unsaturated polyester in a hybrid system of epoxy / unsaturated polyester resin.

Conventionally, fillers, additives, thermoplastic resins, and the like have been added to epoxy resins in order to improve the mechanical properties of the epoxy resins. However, in the related art, it is not easy to select a monomer for an epoxy resin and a side reaction may occur due to an additive, which may adversely affect workability. The present inventors have studied to solve these shortcomings, and as a result, hybridization of epoxy and unsaturated polyester at a specific ratio improves mechanical properties as well as fast curing and ease of use, which simplifies the work process and greatly shortens working time. To discover and complete the present invention.

In addition, according to the present invention there is an advantage that can greatly reduce the cost of the matrix by adding a cheap unsaturated polyester.

According to the present invention, when the unsaturated polyester is hybridized to the epoxy, the matrix may be prepared by thermosetting or room temperature curing.

The present invention provides a matrix comprising a composition of a hybrid of 90 to 98% by weight epoxy resin and 2 to 10% by weight unsaturated polyester resin.

As shown in Figs. 1, 2 and 3, when the content of unsaturated polyester exceeds 5% by weight, the flexural strength, flexural modulus and tensile strength drop rapidly, and when the content of unsaturated polyester is less than 10% by weight, Falls slightly. In the case of impact strength, when the unsaturated polyester content exceeds 10% by weight, it drops sharply.

The present invention also provides a method for producing a composite material by applying a composition obtained by hybridizing 90 to 98% by weight of an epoxy resin and 2 to 10% by weight of an unsaturated polyester resin to a fiber reinforcement by a roller.

The composite material according to the present invention can be made by applying the composition according to the present invention to a fiber reinforcement in order to act as a binder. It is preferable to use glass fiber as a fiber reinforcing material.

The composite material according to the present invention is produced by applying a composition obtained by hybridizing 90 to 98% by weight of an epoxy resin and 2 to 10% by weight of an unsaturated polyester resin to a fiber reinforcement by a roller. The matrix composition is post-cured at 100 ° C. to 150 ° C. for 1 to 2 hours to increase physical properties.

Post-cure system is one of the methods carried out to increase the properties of the cured cured product. The purpose is to increase the physical properties by removing the solvent or other impurities present in the cured product by artificially applying thermal energy and adding energy to the unreacted material that may be present in a small amount.

Hereinafter, although an Example demonstrates this invention in more detail, this Example does not limit the scope of the present invention.

Example 1

Low viscosity C ₁₂ -C ₁₄ -A-modified bisphenol type diglycidyl ether of (Diglyckdyl Ether of Bisphenol-A, "DGEBA") based epoxy "YD-114" [Kukdo Chemical Co., Ltd. product; a trough having a Matrix composition comprising ortho-phthalic acid unsaturated polyester " R-235 " [manufactured by Sewon Chemical Co., Ltd.] at 0, 2, 5, 10, 100 wt% Was prepared.

The content of the amine epoxy curing agent triethylenetetramine (TETA) and unsaturated polyester initiator methylethyl ketone peroxide (MEKP) used at this time was fixed to 20 phr and 0.5 phr, respectively. As a result of measuring the tensile strength using a universal testing machine (Instron # 1125) and fixing the cross-head speed of the matrix composition according to the prepared unsaturated polyester content change to 5 mm / min, as shown in Figure 1 Likewise, when 2% by weight and 5% by weight of unsaturated polyester were added, the tensile strength of the epoxy itself increased by about 4% and 9%.

In order to track these results, the viscosity change according to the unsaturated polyester content of the matrix resin used in the present invention was analyzed by a rheometer and a spectroscopic measuring instrument (FT-IR), and the result showed an increase in tensile strength. When the polyester was added at 2% by weight and 5% by weight, the viscosity increase and carbonyl peak shift could be confirmed.

Example 2

Ortho-phthalic acid unsaturated polyester "R-235" manufactured in two-part type with low viscosity in DGEBA-based epoxy "YD-128" [product of Kukdo Chemical Co., Ltd.] with a medium viscosity, and quickening property. )] Was hybridized as in Example 1 to prepare a matrix composition. The strain rate was fixed at 2 mm / min, and the ratio between the support and the specimen thickness was fixed at 16: 1, and then flexural strength and flexural modulus were measured using a universal testing machine. As a result, when 2% by weight of unsaturated polyester was also added, the flexural strength and the flexural modulus were increased by about 10% and 4%, respectively, as shown in FIG. 2.

Example 3

Ortho-phthalic acid unsaturated polyester "R-235" produced in low viscosity and fast curing two-component type DGEBA epoxy "YD-134" [product of Kukdo Chemical Co., Ltd.] having high viscosity. Hwaseong Co., Ltd.] was hybridized as in Example 1 to prepare a matrix composition. Impact strength was measured using a plastic impact tester. As a result, when 2% by weight and 5% by weight of unsaturated polyester, respectively, as shown in Figure 3, the impact strength was increased by about 4% and 21% than the epoxy itself.

Example 4

Having a low viscosity of the C ₁₂ -C ₁₄ DGEBA type epoxy-modified type "YD-114" [Kukdo Chemical Co., Ltd. product; a low viscosity and on the ortho made of two-component-phthalic unsaturated polyester "R-235" [ Sewon Hwaseong Co., Ltd.] hybridized as in Example 1 to prepare a matrix composition, and then applied to the three-dimensional glass fabric manufactured by Parabeam BV of the Netherlands used as a fiber reinforcement using a self-made aluminum roller made of a specimen Prepared. The deformation rate of the fiber reinforced composite material according to the prepared matrix was fixed at 5 mm / min, and the compressive strength was measured using a universal testing machine. As a result, 2 wt% and 5 wt% of unsaturated polyester was added to the matrix, respectively. In the case of using, the increase in compressive strength when using the epoxy itself as a matrix was about 3% and 5%.

Example 5

Ortho-phthalic acid unsaturated polyester "R-235" made of two-part type with low viscosity in DGEBA-based epoxy "YD-114" [product of Kukdo Chemical Co., Ltd.] which has a medium viscosity, and quick curing property. ) Product] was hybridized as in Example 2 to prepare a specimen as in Example 4. The deformation rate of the fiber reinforced composite material according to the prepared matrix was fixed at 5 mm / min, and the compressive strength was measured using a universal testing machine. As a result, 2% by weight and 5% by weight of unsaturated polyester were added to the matrix. In the case of using, the epoxy resin showed an increase of about 2% and 5% compared to the compressive strength when the epoxy itself was used as the matrix.

Example 6

Ortho-phthalic acid unsaturated polyester "R-235" produced in low viscosity and fast curing two-component type DGEBA epoxy "YD-134" [product of Kukdo Chemical Co., Ltd.] having high viscosity. Hwaseong Co., Ltd.] was hybridized as in Example 3 to prepare a specimen as in Example 4. The deformation rate of the fiber reinforced composite material according to the prepared matrix was fixed at 5 mm / min, and the compressive strength was measured using a universal testing machine. As a result, 2 wt% and 5 wt% of unsaturated polyester was added to the matrix, respectively. In the case of using the epoxy resin, the compressive strength was increased by about 3% and 6% compared to the compressive strength when the epoxy itself was used as the matrix.

Example 7

Produced by the two-component system of C ₁₂ -C ₁₄ DGEBA-type epoxy-modified "YD-114" is a low viscosity in the Kukdo Chemical Co., Ltd. product; having a low viscosity in the curable with ortho-phthalic unsaturated polyester "R -235 "(Sewon Chemical Co., Ltd. product) was hybridized as in Example 1 to prepare a matrix composition, followed by post-curing at 100 ° C for 1 hour. In the present invention, the matrix after the post cure was measured in the same manner as in Example 1. As a result, as shown in FIG. 1, when 2% by weight and 5% by weight of unsaturated polyester were added, the tensile strength of the epoxy itself was about 1% and 4%, respectively.

(Example 8)

Ortho-phthalic acid unsaturated polyester "R-235" manufactured in two-part type with low viscosity in DGEBA-based epoxy "YD-128" [product of Kukdo Chemical Co., Ltd.] with a medium viscosity, and quickening property. )] Was hybridized in the same manner as in Example 1 to prepare a matrix composition, and then subjected to post-curing at 120 ° C. for 1 hour and 30 minutes. The matrix after postcure was measured in the same manner as in Example 2. As a result, as shown in FIG. 2, when 2% by weight and 5% by weight of unsaturated polyester were added, the tensile strength of the epoxy itself was increased by about 1% and 2%, and the flexural modulus of the epoxy itself was about. 2% and 4% increase.

Example 9

Ortho-phthalic acid unsaturated polyester "R-235" produced in low viscosity and fast curing two-component type DGEBA epoxy "YD-134" [product of Kukdo Chemical Co., Ltd.] having high viscosity. Hwaseong Co., Ltd.] was hybridized as in Example 1 to prepare a matrix composition, followed by post-curing at 150 ° C. for 2 hours. The matrix after curing was measured in the same manner as in Example 3. As a result, as shown in FIG. 3, when 2% by weight, 5% by weight and 10% by weight of the unsaturated polyester were added, the impact strength of the epoxy itself increased by about 4%, 21% and 5%.

The matrix according to the present invention is excellent in thermal hardening and workability as well as thermal, mechanical and chemical resistance by hybridizing an existing thermosetting resin epoxy resin and unsaturated polyester resin in a specific mixing ratio.

Claims (6)

A matrix for composite materials comprising a composition of a hybrid of 90 to 98% by weight of epoxy resin and 2 to 10% by weight of polyunsaturated polyester resin. A composite material comprising a fiber reinforcement in a hybridized matrix according to claim 1. The matrix according to claim 1, wherein the unsaturated polyester resin is an ortho-phthalic acid system prepared in two-part form. The composite material according to claim 2, wherein the fiber reinforcing material is glass fiber. A method of producing a composite material by applying a composition obtained by hybridizing 90 to 98% by weight of an epoxy resin and 2 to 10% by weight of an unsaturated polyester resin to a fiber reinforcement by a roller. The method of claim 5, wherein the epoxy resin is post-cured at 100 to 150 ° C. for 1 to 2 hours and then unsaturated polyester is added.