Thermosetting composite resin composition having superior surface smoothness and mechanical properties and method of manufacturing automobile shell plate using same

Abstract

Disclosed is a thermosetting composite resin composition including a thermosetting resin, particularly an unsaturated polyester resin, a low-profile additive and an inorganic filler, and to a method of manufacturing an automobile shell plate using the same. The thermosetting composite resin composition can be used to manufacture not only automobile shell plates having low specific gravity and superior surface smoothness and mechanical properties but also structural parts such as interior parts for airplanes or railways.

Claims

1. A thermosetting composite resin composition, comprising: about 22 to 28 wt % of a thermosetting resin, wherein the thermosetting resin comprises an unsaturated polyester comprising a polymer of a glycol and an acid, and having a degree of unsaturation of about 47 to 50%; about 10 to 15 wt % of a low-profile additive (LPA) comprising epoxy and one or more selected form the group consisting of saturated polyester, polyvinyl acetate (PVAc) and polyurethane (PU); and about 30 to 35 wt % of an inorganic filler comprising one or more selected from the group consisting of glass bubbles, calcium carbonate (CaCO.sub.3) and aluminum hydroxide (Al(OH).sub.3), wherein the inorganic filler has a compressive strength of about 6000 to 6300 psi, wherein the inorganic filler is surface-treated with a silane compound selected from the group consisting of ester-silane, amino-silane, and methacryl-silane, all the wt % based on the total weight of the thermosetting composite resin composition.

2. The thermosetting composite resin composition of claim 1, further comprising: a thickening agent; and a fibrous reinforcement.

3. The thermosetting resin composite resin of claim 2, wherein the thickening agent is present in an amount of 0.7 to 1.5 wt % and the fibrous reinforcement is present in an amount of about 28 to 37 wt %, all the wt % based on the total weight of the thermosetting resin composite resin composition.

4. The thermosetting composite resin composition of claim 1, wherein the glycol comprises propylene glycol, neopentyl glycol or combinations thereof.

5. The thermosetting composite resin composition of claim 4, wherein the thermosetting resin comprises a polymer of propylene glycol, neopentyl glycol and an acid, and a weight ratio of the propylene glycol, the neopentyl glycol and the acid is about 2.5 to 4.5: 1: 4.5 to 6.5.

6. The thermosetting composite resin composition of claim 1, further comprising an additive comprising a dispersant, a separation inhibitor or combinations thereof.

7. The thermosetting composite resin composition of claim 2, wherein the thickening agent comprises a magnesium oxide (MgO), wherein the magnesium oxide is in a form of powder or paste.

8. The thermosetting composite resin composition of claim 2, wherein the fibrous reinforcement comprises a glass fiber.

9. A method of manufacturing an automobile shell plate, comprising: forming a sheet using the thermosetting composite resin composition of claim 1; and pressing the sheet through molding.

10. The method of claim 9, wherein the automobile shell plate has a specific gravity of about 1.27 to 1.37.

11. The method of claim 9, wherein the automobile shell plate has a tensile strength of 65 to 90 MPa, a tensile modulus of 8.0 to 9.0 GPa, an elongation of 1.35 to 1.5%, a flexural strength of 180 to 200 MPa, or a flexural modulus of 8.5 to 10 GPa.

12. The method of claim 9, wherein the automobile shell plate has a long-term waviness (LTW) of 8 to 15.

13. An automobile shell plate manufactured by the method of claim 9.

14. A vehicle comprising the automobile shell plate of claim claim 13.

Description

DETAILED DESCRIPTION

(1) The above and other objectives, features and advantages of the present invention will be more clearly understood from the following preferred embodiments taken in conjunction with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed herein, and may be modified into different forms. These embodiments are provided to thoroughly explain the invention and to sufficiently transfer the spirit of the present invention to those skilled in the art.

(2) It will be further understood that the terms “comprise”, “include”, “have”, etc., when used in this specification, specify the presence of stated features, integers, steps, operations, elements, components, or combinations thereof, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof. Also, it will be understood that when an element such as a layer, film, area, or sheet is referred to as being “on” another element, it can be directly on the other element, or intervening elements may be present therebetween. Similarly, when an element such as a layer, film, area, or sheet is referred to as being “under” another element, it can be directly under the other element, or intervening elements may be present therebetween.

(3) Unless otherwise specified, all numbers, values, and/or representations that express the amounts of components, reaction conditions, polymer compositions, and mixtures used herein are to be taken as approximations including various uncertainties affecting measurements that essentially occur in obtaining these values, among others, and thus should be understood to be modified by the term “about” in all cases. Unless specifically stated or obvious from context, as used herein, the term “about” is understood as within a range of normal tolerance in the art, for example within 2 standard deviations of the mean. “About” can be understood as within 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.05%, or 0.01% of the stated value. Unless otherwise clear from the context, all numerical values provided herein are modified by the term “about.”

(4) Furthermore, when a numerical range is disclosed in this specification, the range is continuous, and includes all values from the minimum value of said range to the maximum value thereof, unless otherwise indicated. Moreover, when such a range pertains to integer values, all integers including the minimum value to the maximum value are included, unless otherwise indicated.

(5) It is understood that the term “vehicle” or “vehicular” or other similar term as used herein is inclusive of motor vehicles in general such as passenger automobiles including sports utility vehicles (SUV), buses, trucks, various commercial vehicles, watercraft including a variety of boats and ships, aircraft, and the like, and includes hybrid vehicles, electric vehicles, plug-in hybrid electric vehicles, hydrogen-powered vehicles and other alternative fuel vehicles (e.g. fuels derived from resources other than petroleum). As referred to herein, a hybrid vehicle is a vehicle that has two or more sources of power, for example both gasoline-powered and electric-powered vehicles.

(6) In one aspect, provided is a thermosetting composite resin composition may include a thermosetting resin, a low-profile additive (LPA) and an inorganic filler. The thermosetting composite resin composition may further include a thickening agent and a fibrous reinforcement.

(7) The thermosetting composite resin composition may suitably include an amount of about 22 to 28 wt % of the thermosetting resin, an amount of about 10 to 15 wt % of the low-profile additive, an amount of about 30 to 35 wt % of the inorganic filler, an amount of about 0.7 to 1.5 wt % of the thickening agent and an amount of about 28 to 37 wt % of the fibrous reinforcement, all the wt % based on the total weight of the thermosetting composite resin composition.

(8) Unless otherwise indicated, it is to be stated in advance that the amount of each component of the thermosetting composite resin composition described below is based on total weight of the thermosetting composite resin composition. If the criterion for determining the amount thereof is changed, the new criterion will always be specified, and thus those skilled in the art will be able to clearly understand the criterion on which the amount is based.

(9) (1) Thermosetting Resin

(10) The thermosetting resin may be a main component for the thermosetting composite resin composition, and any thermosetting resin may be used without limitation and may include any material it has a fast reaction time, low price, superior mechanical properties and high surface smoothness.

(11) The thermosetting resin may include unsaturated polyester, epoxy, phenol, and the like, and preferably includes an unsaturated polyester resin, which may include a polymer of glycol and acid. Here, the unsaturated polyester resin may have a degree of unsaturation of about 47 to 50%. The glycol may include propylene glycol, neopentyl glycol and combinations thereof.

(12) The thermosetting resin may suitably include a polymer of propylene glycol, neopentyl glycol and acid. For example, when the neopentyl glycol is used as the glycol, the flowability of the thermosetting composite resin composition and the surface of a product derived therefrom may be improved.

(13) The weight ratio of propylene glycol to neopentyl glycol to acid may suitably be about 2.5 to 4.5:1:4.5 to 6.5. Here, when the weight ratio of these components is within the above range, the flowability and the surface quality of the thermosetting composite resin composition may be substantially improved, for example, due to the neopentyl glycol.

(14) The amount of the thermosetting resin may be suitably of about 22 to 28 wt % based on the total weight of the thermosetting composite resin composition. When the amount thereof is less than about 22 wt % or greater than about 28 wt % based on the total weight of the thermosetting composite resin composition, mechanical properties and strength may deteriorate.

(15) (2) Low-Profile Additive

(16) The low-profile additive is not limited, and may include any material capable of reducing shrinkage when the thermosetting composite resin composition of the present invention is cured, relieving inherent stress, decreasing microcracks, and increasing surface smoothness.

(17) The low-profile additive may suitably include a thermoplastic homopolymer or copolymer such as polystyrene, polymethyl methacrylate, polyvinyl acetate, and the like, and may preferably include an epoxy-modified low-profile additive. For example, epoxy and one or more selected from the group consisting of saturated polyester, polyvinyl acetate (PVAc), and polyurethane (PU) may be chemically bonded with each other.

(18) Particularly, the low-profile additive in which the epoxy and the polymer such as the saturated polyester described above are chemically bonded may be suitably used, thereby greatly increasing the impact strength of a product made using the thermosetting composite resin composition.

(19) The amount of the low-profile additive may be suitably of about 10 to 15 wt % based on the total weight of the thermosetting composite resin composition. When the amount thereof is less than about 10 wt % or greater than about 15 wt % based on the total weight of the thermosetting composite resin composition, mechanical properties and strength may deteriorate.

(20) (3) Inorganic Filler

(21) The inorganic filler is not limited, and may include any material capable of controlling the specific gravity, surface smoothness, strength, flame retardancy and shrinkage rate of the product.

(22) The inorganic filler may suitably include calcium carbonate as a nonfunctional filler, and may suitably include glass bubbles or calcium carbonate (CaCO.sub.3) as a functional filler. Preferably, the inorganic filler may be surface-treated with a silane compound in order to prevent damage upon compounding and molding and to protect the outer appearance, thereby increasing capability of binding to the resin to thus enhance strength. The compressive strength of the inorganic filler surface-treated with the silane compound may fall in the range of about 6000 to 6300 psi, and the silane compound may suitably include one or more selected from the group consisting of ester-silane, amino-silane, and methacryl-silane. For example, the glass bubbles may be surface-treated with ester-silane, similar to the component of the main resin.

(23) Particularly, the inorganic filler, having a compressive strength of about 6000 psi or greater, particularly of about 5900 to 6300 psi, may be used, whereby a thermosetting composite resin composition is not damaged upon compounding and/or molding. Accordingly, the appearance of the product is greatly improved.

(24) Moreover, the present invention is characterized in that the inorganic filler surface-treated with the silane compound is used to thus increase the capability of binding between the inorganic filler and other components, particularly a thermosetting resin, thereby greatly enhancing the strength of products derived from the thermosetting composite resin composition.

(25) The amount of the inorganic filler may be suitably of about 10 to 15 wt % based on the total weight of the thermosetting composite resin composition. When the amount thereof is less than about 10 wt % or greater than about 15 wt % based on the total weight of the thermosetting composite resin composition, mechanical properties and strength may deteriorate.

(26) (4) Fibrous Reinforcement

(27) The fibrous reinforcement is not limited, and may include any material capable of exhibiting superior mechanical properties and dimensional stability. The fibrous reinforcement may suitably include carbon fiber, boron fiber, glass fiber, and the like, and may suitably include glass fiber, which generates economic benefits and has superior mechanical properties and dimensional stability.

(28) The amount of the fibrous reinforcement may suitably be of about 28 to 37 wt % based on the total weight of the thermosetting composite resin composition. When the amount thereof is less than about 28 wt % or greater than about 37 wt % based on the total weight of the thermosetting composite resin composition, mechanical properties and strength may deteriorate.

(29) (5) Thickening Agent

(30) The thickening agent is not limited, and may include any material capable of increasing the properties of the thermosetting composite resin composition, such as precipitation prevention or flow prevention, and the consistency thereof to thus form the liquid resin into a semisolid resin to thereby improve workability. The thickening agent may suitably include MgO, Mg(OH).sub.2, CaO, Ca(OH).sub.2, and the like, and preferably includes a magnesium oxide (MgO) that is able to facilitate the formation of a semisolid resin. For example, the magnesium oxide may be in a form of powder or paste.

(31) The amount of the thickening agent may preferably be of about 0.7 to 1.5 wt % based on the total weight of the thermosetting composite resin composition.

(32) (6) Additive

(33) The additive is not limited, and may include any material capable of imparting the thermosetting composite resin composition with various functionalities, such as improvement in dispersibility and separation prevention. The thermosetting composite resin composition may further include an additive depending on the functions required thereof, and preferably may suitably include a dispersant, a separation inhibitor, and the like.

EXAMPLE

(34) A better understanding of the present invention will be given through the following examples, which are merely set forth to illustrate the present invention but are not to be construed as limiting the present invention.

Example

(35) A thermosetting composite resin composition was prepared using components in the amounts shown in Table 1 below. The thermosetting resin was a polyester resin having a degree of unsaturation of 50% resulting from polymerizing propylene glycol, neopentyl glycol and an acid at a weight ratio of 4:1:5, a low-profile additive was a product resulting from chemically bonding epoxy and saturated polyester, polyvinyl acetate, polyurethane or combinations thereof, and an inorganic filler was glass bubbles having a compressive strength of 6000 to 6300 psi resulting from surface-treating calcium carbonate (CaCO.sub.3) with ester-silane at a weight ratio of 100:1.

(36) Moreover, a thickening agent was an MgO powder (MgO paste), a fibrous reinforcement was glass fiber for typical SMC cut to a length of 25.4 mm, and as additives, a dispersant and a separation inhibitor were used at a weight ratio of 1:1.

Comparative Example 1

(37) A thermosetting composite resin composition was prepared using the same components and the same specific gravity as in Example, with the exception that the amount of the resin was increased, the amount of the low-profile additive was decreased, the amount of the filler was decreased and the amount of the reinforcement was increased.

Comparative Example 2

(38) A thermosetting composite resin composition was prepared using the same components and the same specific gravity as in Example, with the exception that the amount of the resin was decreased, the amount of the low-profile additive was increased, the amount of the filler was increased and the amount of the reinforcement was decreased.

Comparative Example 3

(39) A thermosetting resin composition was prepared using 4.2 wt % of an unsaturated polyester resin-1 (OS-108, available from Aekyung Chemical), 5.0 wt % of an unsaturated polyester resin-2 (OS-980, available from Aekyung Chemical), 6.0 wt % of a crystalline unsaturated polyester resin (C772, available from Scott Bader, UK) and 1.5 wt % of a monomer (styrene). The low-profile additive was LPV-40, and the inorganic filler was Scotchlite Glass Bubble K-37 (bulk density=0.37, available from 3M).

(40) Furthermore, the thickening agent was calcium oxide (CaO), and as the fibrous reinforcement, roving-type glass fiber (RS4800-433, available from Owens-Corning Korea) was cut to a length of 2.54 mm and used, and as additives, 0.5 wt % of an initiator (t-butyl perbenzoate) and 1.0 wt % of a release agent (zinc stearate) were used.

Comparative Example 4

(41) A thermosetting composite resin composition was prepared using the same components in the same amounts as in Comparative Example 3, with the exception that different components were used for the thermosetting resin and the low-profile additive. The thermosetting resin was a polyester resin having a degree of unsaturation of 50% resulting from polymerizing propylene glycol, neopentyl glycol and an acid at a weight ratio of 4:1:5, and the low-profile additive was saturated polyester.

Comparative Example 5

(42) A thermosetting composite resin composition was prepared using the same components in the same amounts as in Comparative Example 3, with the exception that different components were used for the thermosetting resin, the low-profile additive and the inorganic filler. The thermosetting resin was a polyester resin having a degree of unsaturation of 50% resulting from polymerizing propylene glycol, neopentyl glycol and an acid at a weight ratio of 4:1:5, the low-profile additive was saturated polyester, and the inorganic filler was glass bubbles having a compressive strength of 6000 to 6300 psi resulting from surface-treating calcium carbonate (CaCO.sub.3) with ester-silane at a weight ratio of 100:1.

(43) TABLE-US-00001 TABLE 1 Comparative Comparative Comparative Comparative Comparative Example Example 1 Example 2 Example 3 Example 4 Example 5 Thermosetting 23 28 20 26 26 26 resin [wt %] Low-profile 8 5 13 10.5 10.5 10.5 additive [wt %] Inorganic filler 30 25 38 26 26 26 [wt %] Thickening agent 1 1 1 1 1 1 [wt %] Fibrous 35 38 25 35 35 35 reinforcement [wt %] Additive [wt %] 3 3 3 1.5 1.5 1.5 Total 100 100 100 100 100 100

Test Example

(44) The results of evaluation of test specimens manufactured from the thermosetting composite resin compositions of Example and Comparative Examples are shown below.

(45) TABLE-US-00002 TABLE 2 Comparative Comparative Comparative Comparative Comparative Items Unit Example Example 1 Example 2 Example 3 Example 4 Example 5 Specific — 1.35 1.36 1.35 1.35 1.27 1.28 gravity.sup.1) G/F content.sup.2) % 35 28 38 35 35 35 Tensile MPa 90 56 76 68 52 64 strength.sup.3) Tensile GPa 8.6 7.9 7.7 — 5.9 5.4 modulus.sup.4) Elongation.sup.5) % 1.4 1.2 1.3 — 1.1 1.3 Flexural MPa 200 170 175 156 143 152 strength.sup.6) Flexural GPa 9.8 8.1 7.2 10 7.3 6.8 modulus.sup.7) Long-term waviness.sup.8) — 10 35 15 — 32 28 Note) .sup.1)Specific gravity: ASTM D792 .sup.2)G/F content: self-measurement (washing with sulfuric acid aqueous solution after combustion) .sup.3)Tensile strength: ASTM D638 .sup.4)Tensile modulus: ASTM D638 .sup.5)Elongation: ASTM D638 .sup.6)Flexural strength: ASTM D790 .sup.7)Flexural modulus: ASTM D790 .sup.8)Fong-term waviness (LTW): BYK Wave Scan DOI

(46) As is apparent from Table 2, the test specimen manufactured using the thermosetting composite resin composition of Example had:

(47) i) a specific gravity of 1.35, which corresponds to a low specific gravity of 1.8 or less, similar to conventional low-specific-gravity SMC (Comparative Examples 3 to 5), such that the low specific gravity is capable of reducing the weight by 30 to 40% compared to an existing steel hood and by 10% compared to an aluminum hood;

(48) ii) a tensile strength of 90 MPa and a flexural strength of 200 MPa, corresponding to mechanical properties (change rate ≤5%) very similar to those of general-specific-gravity SMC (a specific gravity of 1.85 to 1.95), as well as a low specific gravity of 1.8 or less, similar to conventional low-specific-gravity SMC (Comparative Examples 3 to 5); and

(49) iii) a long-term waviness (LTW) of 10, thus exhibiting superior surface quality compared to conventional low-specific-gravity SMC (Comparative Examples 3 to 5) in which LTW is difficult to maintain at 30 or less.

(50) Briefly, the test specimen manufactured using the thermosetting composite resin composition of Example according to the present invention had a low specific gravity of 1.8 or less similar to conventional low-specific-gravity SMC, superior mechanical properties very similar to those of general-specific-gravity SMC, and low long-term waviness.

(51) In contrast, Comparative Example 1 exhibited a tensile strength of 90 MPa or less, a tensile modulus of 8.6 Gpa or less, an elongation of 1.4% or less, a flexural strength of 200 Mpa or less and a flexural modulus of 9.8 Gpa or less. Accordingly, it can be confirmed that the mechanical properties were inferior compared to Example, and in particular, the LTW was 30 or more and thus surface smoothness was deteriorated compared to the other Comparative Examples.

(52) Comparative Example 2 exhibited a tensile strength of 90 MPa or less, a tensile modulus of 8.6 Gpa or less, an elongation of 1.4% or less, a flexural strength of 200 Mpa or less and a flexural modulus of 9.8 Gpa or less. Accordingly, it can be confirmed that the mechanical properties were inferior compared to Example, but the LTW was 30 or less, and thus surface smoothness was good.

(53) Comparative Example 3 is a technology corresponding to the background art, and it can be confirmed that when the specific gravity is reduced, mechanical properties are typically decreased. Compared to Example of the present invention, a tensile strength of 90 MPa or less, a tensile modulus of 8.6 Gpa or less, an elongation of 1.4% or less, a flexural strength of 200 Mpa or less and a flexural modulus of 9.8 Gpa or less were exhibited, indicating that the specific gravity was similar to that of Example but that the mechanical properties were low.

(54) Comparative Example 4 exhibited a tensile strength of 90 MPa or less, a tensile modulus of 8.6 Gpa or less, an elongation of 1.4% or less, a flexural strength of 200 Mpa or less and a flexural modulus of 9.8 Gpa or less. Accordingly, it can be confirmed that the mechanical properties were inferior compared to Example, and the LTW was 30 or more and thus surface smoothness was deteriorated compared to the other Comparative Examples.

(55) Comparative Example 5 exhibited a tensile strength of 90 MPa or less, a tensile modulus of 8.6 Gpa or less, an elongation of 1.4% or less, a flexural strength of 200 Mpa or less and a flexural modulus of 9.8 Gpa or less. Accordingly, it can be confirmed that the mechanical properties were inferior compared to Example, and the LTW was close to 30 and thus surface smoothness was deteriorated compared to the other Comparative Examples. In particular, in Comparative Example 5, when the amount of the filler was greatly reduced, the composition balance was varied, indicative of low mechanical properties.

(56) Therefore, according to the various exemplary embodiments of the present invention, it is possible to obtain an automobile shell plate, in which weight reduction can be realized due to the low specific gravity, mechanical performance required for the function as a structural material and mechanical properties necessary for crash performance can be ensured, and surface smoothness suitable for the appearance required of parts for automobile shell plates can be attained.

(57) Although the exemplary embodiments of the present invention have been described with reference to the accompanying drawings, those skilled in the art will appreciate that the present invention may be embodied in other specific forms without changing the technical spirit or essential features thereof. Thus, the exemplary embodiments described above should be understood to be non-limiting and illustrative in every way.