Reactive composition for highly transparent thermosetting resin, and glass fiber composite comprising same

Abstract

The present invention relates to a glass fiber composite comprising a reactive composition, and a manufacturing method therefor. Specifically, the reactive composition comprises an aromatic monomer and an acrylate monomer, and the refractive index of a cured product of the reactive composition is similar to that of a glass fiber. Therefore, the glass fiber composite prepared from the reactive composition and the glass fiber can have excellent transmittance and visibility.

Description

Reactive composition for highly transparent thermosetting resins and glass fiber composite including the same

[0001] The present invention relates to a reactive composition for a highly transparent thermosetting resin and a glass fiber composite comprising the same.

[0002] Recently, environmental regulations have been tightening globally, and the mobility sector, in particular, is being significantly affected by these regulations. Consequently, there is a growing trend of research on lightweighting to increase fuel efficiency in mobility. In the case of a typical automobile, over 1,000 parts utilize polymer materials, with approximately 15 wt% of the polymer material applied in the form of plastics, rubber, and fibers. Attempts are being made to apply fiber-reinforced plastic (FRP) to various mobility applications. This material can replace glass and various transparent parts, and by mixing glass fibers into transparent plastic, the strength of the existing plastic can be significantly increased.

[0003] However, due to the difference in refractive index between the plastic mixed with glass fibers, the manufactured FRP may experience light reflection and refraction, resulting in low transmittance and insufficient visibility. Furthermore, as it is difficult to achieve high transparency while simultaneously securing sufficient strength, there are still many challenges remaining to be resolved before it can replace current transparent components.

[0004] The present invention aims to provide a reactive composition and a cured product thereof that can be applied as a highly transparent composite material, having a small difference in refractive index from glass fibers and superior visibility and transmittance.

[0005] Specifically, the purpose is to provide a reactive composition comprising an unsaturated polyester resin, an aromatic monomer, and a functional monomer, wherein the cured product of the same has a small difference in refractive index with glass fibers of ±0.005 or less, ±0.004 or less, ±0.003 or less, ±0.002 or less, and ±0.001 or less, and exhibits an Abbe number of 35 to 60, 35 to 50, and 35 to 40, thereby enabling balanced control of dispersion characteristics while maintaining a high refractive index, and a reactive composition and a cured product thereof.

[0006] Another objective of the present invention is to provide a glass fiber composite manufactured by including the reactive composition and glass fibers described above. Specifically, the invention aims to provide a glass fiber composite that satisfies a 589 nm transmittance of 85% or more, or 85 to 90%, as measured according to ASTM D1003.

[0007] In order to solve the above problem, the inventors discovered a reactive composition with a refractive index very similar to that of glass fiber, and by mixing the reactive composition with glass fiber, they came to invent a glass fiber composite capable of providing excellent transmittance and visibility.

[0008] One aspect of the present invention provides a reactive composition comprising an unsaturated polyester resin, an aromatic monomer, and a functional monomer, wherein the unsaturated polyester resin is prepared from a polymerizable composition comprising a diol compound including ethylene glycol (EG), propylene glycol (PG), and neopentyl glycol (NPG); and two or more carboxylic acid compounds selected from phthalic anhydride (PA), maleic anhydride (MA), and succinic acid (SA); and the functional monomer comprises either one selected from fluorene-based monomers and halogen-containing monomers or a mixture thereof.

[0009] According to one embodiment, the diol compound may comprise 25 to 60 parts by weight of ethylene glycol and 1 to 10 parts by weight of neopentyl glycol with respect to 100 parts by weight of propylene glycol.

[0010] According to one embodiment, the carboxylic acid compound may comprise 25 to 60 parts by weight of succinic acid and 30 to 100 parts by weight of maleic anhydride, based on 100 parts by weight of phthalic anhydride.

[0011] According to one embodiment, the reactive composition may comprise 20 to 80 parts by weight of an aromatic monomer per 100 parts by weight of an unsaturated polyester resin.

[0012] According to one embodiment, the reactive composition may comprise 1 to 100 parts by weight of a functional monomer per 100 parts by weight of an unsaturated polyester resin.

[0013] According to one embodiment, the reactive composition may further comprise one or more (meth)acrylate-based monomers selected from the group consisting of alicyclic (meth)acrylate monomers, aromatic thio(meth)acrylate monomers, and di(meth)acrylate monomers containing ether groups.

[0014] According to one embodiment, the alicyclic (meth)acrylate monomer comprises a C5 to C8 alicyclic group, the aromatic thio(meth)acrylate comprises a phenylthio(meth)alkyl acrylate, and the di(meth)acrylate comprising an ether group may be a di(meth)acrylate comprising an alkyleneoxy group or a polyethylene glycol di(meth)acrylate having a molecular weight of 200 to 1000. The molecular weight may be a weight-average molecular weight, and the unit is g / mol. The weight-average molecular weight may be measured by a conventional method using gel permeation chromatography (GPC).

[0015] According to one embodiment, the reactive composition may comprise 1 to 100 parts by weight of a (meth)acrylate-based monomer per 100 parts by weight of an unsaturated polyester resin.

[0016] According to one embodiment, the cured product obtained by curing the reactive composition may have an Abbe number of 35 to 60.

[0017] According to one embodiment, the cured product obtained by curing the reactive composition may have a refractive index of 1.55 to 1.57 measured at 589 nm in accordance with ASTM D1218.

[0018] Another aspect of the present invention may provide a cured glass fiber composite comprising a reactive composition according to one aspect; a curing agent; and glass fibers.

[0019] According to one embodiment, the glass fiber composite may comprise 5 to 200 parts by weight of glass fibers per 100 parts by weight of the reactive composition.

[0020] According to one embodiment, the curing agent may be any one or more mixtures selected from the group consisting of methyl ethyl ketone peroxide (MEKPO), benzoyl peroxide (BPO), tert-butyl peroxy-2-ethylhexanoate (TBPEH), tert-butyl peroxybenzoate (TBBPB), and tert-butyl peroxide (TBPO).

[0021] According to one embodiment, the curing agent may be included in an amount of 0.5 to 5 parts by weight per 100 parts by weight of the reactive composition.

[0022] According to one embodiment, the glass fiber composite may have a transmittance of 85% or more measured in the 589 nm wavelength range in accordance with ASTM D1003.

[0023] According to one embodiment of the present invention, a reactive composition can provide a glass fiber composite with excellent transparency and visibility, in which the transmittance of a cured product containing glass fibers is 85% or higher, by having a small difference in refractive index with glass fibers and providing an appropriate Abbe number.

[0024] According to one embodiment of the present invention, a glass fiber composite can provide not only excellent mechanical properties but also superior transmittance and visibility.

[0025] The present invention will be described in more detail below. However, the following specific examples or embodiments are merely references for the detailed explanation of the present invention and are not limited thereto, and the present invention may be implemented in various forms.

[0026] Furthermore, unless otherwise defined, all technical and scientific terms have the same meaning as generally understood by one of the art to which the present invention pertains. The terms used in the description of the present invention are merely for the purpose of effectively describing specific embodiments and are not intended to limit the present invention.

[0027] Additionally, the singular form used in the specification and the appended claims may be intended to include the plural form unless specifically indicated otherwise in the context.

[0028] Furthermore, when it is stated that a part "includes" a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but may include additional components.

[0029] Additionally, units used herein without special reference are based on weight, and, for example, units of % or ratio mean weight % or weight ratio, and weight % means the weight percentage of any one component of the total composition that occupies the composition, unless otherwise defined.

[0030] Additionally, the numerical ranges used in this specification include lower and upper limits and all values ​​within the range, increments logically derived from the form and width of the defined range, all of which are limited values, and all possible combinations of upper and lower limits of numerical ranges defined in different forms. Unless otherwise specifically defined in this specification, values ​​outside the numerical range that may occur due to experimental error or rounding are also included in the defined numerical range.

[0031] Furthermore, unless otherwise specifically defined in the present invention, when a layer or member is described as being located "on" another layer or member, this includes not only cases where a layer or member is in contact with another layer or member, but also cases where another layer or member exists between the two layers or members.

[0032] Furthermore, in this specification, "~-type monomer" is a broad concept that includes all "derivatives of ~-type monomers."

[0033] Additionally, in this specification, '(meth)acrylic' includes both methacrylic and acrylic.

[0034] Additionally, in this specification, the acrylate monomer includes both the methacrylate monomer and the acrylate monomer.

[0035] Additionally, terms used herein such as “about,” “substantially,” etc., are used to mean at or near the stated value when inherent manufacturing and material tolerances are presented in the stated meaning, and are used to prevent unscrupulous infringers from unfairly exploiting the disclosed content in which precise or absolute values ​​are mentioned to aid in understanding the invention.

[0036] The inventors of the present invention have completed the invention by discovering that by combining an unsaturated polyester resin polymerized using a specific combination of a diol compound and a specific combination of a carboxylic acid compound with one or more functional monomers selected from monomers having an aromatic structure, fluorene-based monomers, and / or halogen-containing monomers, it is possible to provide a glass fiber composite with excellent transparency and visibility, having a very small difference in refractive index with glass fibers and a transmittance of 85% or more.

[0037] The present invention provides a reactive composition comprising an unsaturated polyester resin, an aromatic monomer, and a functional monomer, wherein the unsaturated polyester resin is prepared from a polymerizable composition comprising a diol compound including ethylene glycol (EG), propylene glycol (PG), and neopentyl glycol (NPG); and two or more carboxylic acid compounds selected from phthalic anhydride (PA), maleic anhydride (MA), and succinic acid (SA); and the functional monomer comprises either one selected from fluorene-based monomers and halogen-containing monomers or a mixture thereof.

[0038] According to one embodiment, the unsaturated polyester resin may be an unsaturated polyester prepared from a diol compound and a dicarboxylic acid compound (described with the same meaning as a carboxylic acid compound). Preferably, it may be prepared by reacting a diol compound with a dicarboxylic acid compound containing an unsaturated dicarboxylic compound.

[0039] In addition, the above diol compound and dicarboxylic acid compound can be prepared by polymerizing in a molar ratio of 1:0.5 to 2 or 1:0.8 to 1.2.

[0040] According to one embodiment, the diol compound may be used in combination with propylene glycol, ethylene glycol, and neopentyl glycol, and the desired transmittance and visibility can be achieved by including them simultaneously. If any one of these is excluded, the desired transmittance and visibility of 85% or more cannot be simultaneously satisfied.

[0041] According to one embodiment, the diol compound may comprise ethylene glycol in an amount of 25 parts by weight or more, 30 parts by weight or more, 35 parts by weight or more, 60 parts by weight or less, 55 parts by weight or less, 50 parts by weight or less, or any value between the above values, with respect to 100 parts by weight of propylene glycol. For example, with respect to 100 parts by weight of propylene glycol, the ethylene glycol may comprise 25 to 60 parts by weight, 25 to 55 parts by weight, 25 to 50 parts by weight, 30 to 50 parts by weight, or 30 to 40 parts by weight.

[0042] According to one embodiment, the diol compound may contain, with respect to 100 parts by weight of propylene glycol, neopentyl glycol in an amount of 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or less, 9 parts by weight or less, 8 parts by weight or less, or any value between the above values. For example, with respect to 100 parts by weight of propylene glycol, neopentyl glycol may be contained in an amount of 1 to 10 parts by weight, 2 to 9 parts by weight, 2 to 8 parts by weight, or 5 to 8 parts by weight.

[0043] According to one embodiment, the carboxylic acid compound may include phthalic anhydride and maleic anhydride, may include phthalic anhydride and succinic acid, or may include maleic anhydride and succinic acid, or may include all of phthalic anhydride, maleic anhydride, and succinic acid.

[0044] According to one embodiment, the carboxylic acid compound may comprise succinic acid in an amount of 25 parts by weight or more, 28 parts by weight or more, 30 parts by weight or more, 60 parts by weight or less, 55 parts by weight or less, 50 parts by weight or less, 45 parts by weight or less, 40 parts by weight or less, or any value between the above values, with respect to 100 parts by weight of phthalic anhydride. For example, it may comprise 25 to 60 parts by weight, 25 to 50 parts by weight, 30 to 50 parts by weight, or 30 to 40 parts by weight of succinic acid with respect to 100 parts by weight of phthalic anhydride.

[0045] According to one embodiment, the carboxylic acid compound may comprise maleic anhydride in an amount of 30 parts by weight or more, 35 parts by weight or more, 40 parts by weight or more, 45 parts by weight or more, 100 parts by weight or less, 90 parts by weight or less, 80 parts by weight or less, 70 parts by weight or less, 60 parts by weight or less, 50 parts by weight or less, or any value between the above values, with respect to 100 parts by weight of phthalic anhydride. For example, maleic anhydride may comprise 30 to 100 parts by weight, 35 to 80 parts by weight, 40 to 80 parts by weight, or 40 to 60 parts by weight with respect to 100 parts by weight of phthalic anhydride.

[0046] When including an unsaturated polyester resin manufactured to satisfy the above combination and composition range, it may be advantageous for controlling the refractive index of the reactive composition, and is particularly preferred as it can have a refractive index very similar to that of glass fiber, but is not limited thereto.

[0047] According to one embodiment, the unsaturated polyester resin may have an acid value of 10 to 30 KOH mg / g, 15 to 30 KOH mg / g, or 20 to 30 KOH mg / g, or 25 to 28 KOH mg / g, but is not limited thereto.

[0048] According to one embodiment, the aromatic monomer may be an aromatic monomer such as styrene, alpha-methylstyrene, vinyl naphthalene, etc., and is not limited to as long as it has transparent properties and undergoes a polymerization reaction with an unsaturated polyester.

[0049] According to one embodiment, the reactive composition may contain an aromatic monomer in an amount of 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 80 parts by weight or less, 70 parts by weight or less, 60 parts by weight or less, or any value between the above values, with respect to 100 parts by weight of unsaturated polyester resin. For example, it may contain 20 to 80 parts by weight, 50 to 70 parts by weight, or 50 to 60 parts by weight of the aromatic monomer with respect to 100 parts by weight of unsaturated polyester resin.

[0050] According to one embodiment, the functional monomer may include any one selected from the group consisting of fluorene-based monomers and halogen-containing monomers, or a mixture thereof. By including the functional monomer, transmittance may be further improved and visibility may be enhanced.

[0051] According to one embodiment, the functional monomer may include a fluorene-based monomer. A glass fiber composite prepared with the reactive composition may have excellent transmittance and visibility.

[0052] According to one embodiment, the fluorene-based monomer may be used without limitation as long as it is a monomer containing a fluorene structure and a polymerizable functional group such as an acrylic group or a vinyl group. Specifically, the fluorene-based monomer may be represented by the following chemical formula 1.

[0053] [Chemical Formula 1]

[0054]

[0055] In the above chemical formula 1,

[0056] L is a direct bond, an alkylene, an arylene, or a combination thereof, and

[0057] The carbon of the above alkylene can be optionally substituted with a heteroatom, and

[0058] The hydrogen of the above alkylene can be optionally substituted with -OH, -COOH, or -NH2, and

[0059] X is a vinyl group or a (meth)acrylic group.

[0060] The above heteroatom may be one or more of nitrogen (N), oxygen (O), sulfur (S), or phosphorus (P).

[0061] According to one embodiment, the fluorene monomer may be represented by the following chemical formula 1-1.

[0062] [Chemical Formula 1-1]

[0063]

[0064] In the above chemical formula 1-1,

[0065] L1 and L2 are identical to the above definition of L, and X1 and X2 are identical to the above definition of X.

[0066] According to one embodiment, in the formula 1 or 1-1, L, L1 and L2 may independently be directly bonded, C1-15 alkylene, C6-30 arylene, or a combination thereof, the carbon of the alkylene may optionally be substituted with oxygen or nitrogen, and the hydrogen of the alkylene may optionally be substituted with -OH.

[0067] According to one embodiment, the fluorene monomer may be represented by the following chemical formula 1-2.

[0068] [Chemical Formula 1-2]

[0069]

[0070] In the above chemical formula 1-2,

[0071] Ar1 and Ar2 are independently arylenes, and

[0072] L3 and L4 are independently alkylenes, and

[0073] The carbon of the alkylene can be optionally substituted with oxygen or nitrogen, and the hydrogen of the alkylene can be optionally substituted with -OH, and

[0074] X is a vinyl group or a (meth)acrylic group.

[0075] According to one embodiment, in the formula 1-2, Ar1 and Ar2 may independently be directly bonded or C6-120 arylenes, L3 and L4 may independently be C1-7 alkylenes, the carbon of the alkylene may optionally be substituted with oxygen, and the hydrogen of the alkylene may optionally be substituted with -OH.

[0076] According to one embodiment, the fluorene-based monomer is, without limitation, 9-fluorenyl acrylate, 9-fluorenyl vinyl acrylate, 9-fluorenyl ethyl acrylate, 9-fluorenyl propyl acrylate, 9-fluorenyl butyl acrylate, 9-fluorenyl methacryloyl ester, 9-fluorenyl hydroxyacrylate, 9-fluorenyl benzoyl methacrylate, 9-fluorenyl acrylic acid, 9-fluorenyl 2-acryloyloxypropanol, 9-fluorenyl methacrylate, 9,9-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]fluorene, 9,9-bis[4-(2-hydroxy-3-acryloyloxypropyl)phenyl]fluorene, 9,9-Bis[4-(2-hydroxy-3-methacryloyloxypropyl)phenyl]fluorene, 9,9-Bis[4-(2-hydroxy-3-acryloyloxyethyl)phenyl]fluorene, 9,9-Bis[4-(2-hydroxy-3-methacryloyloxyethyl)phenyl]fluorene, 9,9-Bis[4-(2-hydroxy-3-acryloyl)phenyl]fluorene, 9,9-Bis[4-(2-hydroxy-3-acryloylmethyl chloride)phenyl]fluorene, 9,9-Bis[4-(2-hydroxy-3-methacryloylmethyl chloride)phenyl]fluorene, 9,9-Bis[4-(2-hydroxy-3-acryloylcyclohexane)phenyl]fluorene, 9,9-Bis[4-(2-hydroxy-3-acryloylcyclohexane)phenyl]fluorene, 9,9-Bis[4-(2-hydroxy-3-methacryloylcyclohexane)phenyl]fluorene, 9,9-Bis[4-(2-hydroxy-3-acryloyloxypropoxy)phenyl]fluorene, 9,9-Bis(4-vinyloxyphenyl)fluorene, 9,9-Bis(4-methacryloyloxyphenyl)fluorene, 9,9-Bis(4-butyloxyphenyl)fluorene, 9,9-Bis(4-isobutyloxyphenyl)fluorene, 9,9-Bis(4-hexyloxyphenyl)fluorene, 9,9-Bis(4-pentacryloyloxyphenyl)fluorene, 9,9-Bis(4-acryloyloxyphenyl)fluorene, 9,9-Bis(4-propyloxyphenyl)fluorene, 9,9-Bis(4-isopreneroxyphenyl)fluorene, 9,9-Bis(4-methacryloyloxypropyl)fluorene, 9,9-Bis(4-allyloxyphenyl)fluorene, 9,9-Bis[(methacryloyloxy)methyl]fluorene, 9,9-Bis[(acryloyloxy)ethyl]fluorene, 9,9-Bis[(methacryloyloxy)ethyl]fluorene, 9,9-Bis[(acryloyloxy)propyl]fluorene, 9,9-Bis[(methacryloyloxy)propyl]fluorene, 9,9-Bis[(acryloyloxy)butyl]fluorene, 9,9-Bis[(methacryloyloxy)butyl]fluorene, 9,9-Bis[(acryloyloxy)hexyl]fluorene, 9,9-Bis[(methacryloyloxy)hexyl]fluorene, 9,9-Bis[(acryloyloxy)isobutyl]fluorene, 9,9-Bis[(acryloyloxy)methyl]fluorene, ethoxylated 9,9-bis[4-(2-methacryloyloxyethoxy)phenyl]fluorene, ethoxylated 9,9-bis[4-(2-acryloyloxypropylethoxy)phenyl]fluorene, ethoxylated 9,9-bis[4-(2-methacryloyloxypropylethoxy)phenyl]fluorene, ethoxylated 9,9-bis[4-(2-acryloyloxyethylethoxy)phenyl]fluorene, ethoxylated 9,9-bis[4-(2-methacryloyloxyethylethoxy)phenyl]fluorene, ethoxylated 9,9-bis[4-(2-acryloyloxymethylethoxy)phenyl]fluorene, ethoxylated 9,9-bis[4-(2-methacryloyloxymethylethoxy)phenyl]fluorene, ethoxylated 9,9-bis[4-(2-methacryloyloxymethylethoxy)phenyl]fluorene, It may be one or more selected from the group consisting of ethoxylated 9,9-bis[4-(2-acryloyl)phenyl]fluorene, ethoxylated 9,9-bis[4-(2-methacryloyl)phenyl]fluorene, ethoxylated 9,9-bis[4-(2-acryloyl]fluorene, and ethoxylated 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, etc.

[0077] According to one embodiment, the reactive composition may contain the fluorene monomer in an amount of 1 part by weight or more, 2 parts by weight or more, 3 parts by weight or more, 5 parts by weight or more, 7 parts by weight or more, 8 parts by weight or more, 100 parts by weight or less, 95 parts by weight or less, 90 parts by weight or less, 80 parts by weight or less, 75 parts by weight or less, or any value between the above values, with respect to 100 parts by weight of unsaturated polyester. For example, the fluorene monomer may be included in an amount of 1 to 100 parts by weight, 5 to 80 parts by weight, 5 to 75 parts by weight, or 8 to 75 parts by weight with respect to 100 parts by weight of unsaturated polyester.

[0078] According to one embodiment, the functional monomer may include a halogen-containing monomer. The halogen-containing monomer may be a monomer containing one or more halogens, including the group consisting of F, Br, Cl, and I, and the halogen-containing monomer may be used without limitation as long as it is a monomer containing the halogen and including a polymerizable functional group. The polymerizable functional group may be one or more selected from the group consisting of (meth)acrylic groups, vinyl groups, acryloyl groups, amine groups, alcohol groups, carboxyl groups, and epoxy groups.

[0079] According to one embodiment, the halogen-containing monomer may be a fluorine-based monomer. The fluorine-based monomer may be used without limitation as long as it is a monomer containing F (fluorine) and including a polymerizable functional group.

[0080] According to one embodiment, the halogen-containing monomer may be represented by the following chemical formula 2.

[0081] [Chemical Formula 2]

[0082]

[0083] In the above chemical formula 2,

[0084] L 22 is a directly linked, substituted, or unsubstituted alkylene, and

[0085] X 22 is -CF3, -CHF2, or CH2F.

[0086] According to one embodiment, in the above formula 2, L 22 It may be a C1-30 alkylene in which some of the hydrogen is substituted with fluorine (F).

[0087] According to one embodiment, the fluorinated monomer is, without limitation, 2,2,2-trifluoroethyl methacrylate, 2-fluoroethyl acrylate, 2,2,2-trifluoromethyl acrylate, 2,2,2-trifluoroethyl vinyl acrylate, 1,1,1-trifluoroethyl acrylate, 2,2,2-trifluoroethyl ethyl acrylate, 2,2,2-trifluoroethyl propyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoromethyl methacrylate, 2,2,2-trifluoropropyl methacrylate, 2-fluoroethyl methacrylate, 2,2,2-trifluoromethyl methacrylate, hexafluoroisopropyl acrylate, hexafluoroisopropyl methacrylate, 2,2,2-trifluoroisopropyl methacrylate, hexafluoromethyl methacrylate, trifluoromethyl methacrylate, 2,2,2-Trifluoroisopropyl acrylate, 1H,1H,2H,2H-Heptadecafluorodecyl acrylate, 1H,1H,2H,2H-Hexafluorodecyl methacrylate, 1H,1H,2H,2H-Heptadecafluoromethacrylate, 1H,1H,2H,2H-Heptadecafluorodimethyl methacrylate, 1H,1H,5H-Octafluoropentyl acrylate, 1H,1H,5H-Octafluoropentyl methacrylate, 1H,1H,5H-Octafluorovinyl methacrylate, 1H,1H,5H-Octafluorophenyl methacrylate, 1H,1H,5H-Octafluoromethyl methacrylate, 1H,1H,5H-Octafluorobutyl methacrylate, 1H,1H,5H-Octafluoroisopropyl It may be one or more selected from the group consisting of methacrylate, 1H,1H,5H-octafluoroacrylate, 1H,1H,5H-octafluoroethyl methacrylate, 1H,1H,5H-octafluorotrifluoromethyl methacrylate, and 1H,1H,5H-octafluorostearyl methacrylate.

[0088] According to one embodiment, the halogen-containing monomer may be a chlorine-based monomer. The chlorine-based monomer may be used without limitation as long as it is a monomer containing Cl (chlorine) and including a polymerizable functional group.

[0089] According to one embodiment, the chlorinated monomer is, without limitation, 2,2,2-trichloroethyl methacrylate, 2-chloroethyl acrylate, 2,2,2-trichloromethyl acrylate, 2,2,2-trichloroethyl vinyl acrylate, 1,1,1-trichloroethyl acrylate, 2,2,2-trichloroethyl ethyl acrylate, 2,2,2-trichloroethyl propyl acrylate, 2,2,2-trichloroethyl acrylate, 2,2,2-trichloromethyl methacrylate, 2,2,2-trichloropropyl methacrylate, 2-chloroethyl methacrylate, 2,2,2-trichloromethyl methacrylate, hexachloroisopropyl acrylate, hexachloroisopropyl methacrylate, 2,2,2-trichloroisopropyl methacrylate, hexachloromethyl methacrylate, trichloromethyl Methacrylate, 2,2,2-Trichloroisopropyl acrylate, 1H,1H,2H,2H-Heptadecachlorodecyl acrylate, 1H,1H,2H,2H-Hexachlorodecyl methacrylate, 1H,1H,2H,2H-Heptadecachloromethacrylate, 1H,1H,2H,2H-Heptadecachlorodimethyl methacrylate, 1H,1H,5H-Octachloropentyl acrylate, 1H,1H,5H-Octachlorovinyl methacrylate, 1H,1H,5H-Octachlorophenyl methacrylate, 1H,1H,5H-Octachloromethyl methacrylate, 1H,1H,5H-Octachlorobutyl methacrylate, 1H,1H,5H-Octachloroisopropyl methacrylate, It may be one or more selected from the group consisting of 1H,1H,5H-octachloroacrylate, 1H,1H,5H-octachloroethyl methacrylate, 1H,1H,5H-octachlorotrichloromethyl methacrylate, and 1H,1H,5H-octachlorostearyl methacrylate.

[0090] According to one embodiment, the halogen-containing monomer may be a bromine-based monomer. The bromine-based monomer may be used without limitation as long as it is a monomer containing Br (bromine) and including a polymerizable functional group.

[0091] According to one embodiment, the brominated monomer is, without limitation, 2,2,2-tribromoethyl methacrylate, 2-bromoethyl acrylate, 2,2,2-tribromomethyl acrylate, 2,2,2-tribromoethyl vinyl acrylate, 1,1,1-tribromoethyl acrylate, 2,2,2-tribromoethyl ethyl acrylate, 2,2,2-tribromoethyl propyl acrylate, 2,2,2-tribromoethyl acrylate, 2,2,2-tribromomethyl methacrylate, 2,2,2-tribromopropyl methacrylate, 2-bromoethyl methacrylate, 2,2,2-tribromomethyl methacrylate, hexabromoisopropyl acrylate, hexabromoisopropyl methacrylate, 2,2,2-tribromoisopropyl methacrylate, Hexabromomethyl methacrylate, Tribromomethyl methacrylate, 2,2,2-Tribromoisopropyl acrylate, 1H,1H,2H,2H-hephthalecabromodecyl acrylate, 1H,1H,2H,2H-hexabromodecyl methacrylate, 1H,1H,2H,2H-hephthalecabromomethacrylate, 1H,1H,2H,2H-hephthalecabromodimethyl methacrylate, 1H,1H,5H-octabromopentyl acrylate, 1H,1H,5H-octabromovinyl methacrylate, 1H,1H,5H-octabromophenyl methacrylate, 1H,1H,5H-octabromomethyl methacrylate, 1H,1H,5H-octabromobutyl It may be one or more selected from the group consisting of methacrylate, 1H,1H,5H-octabromisopropyl methacrylate, 1H,1H,5H-octabromoacryl methacrylate, 1H,1H,5H-octabromoaethyl methacrylate, 1H,1H,5H-octabromoatribromomethyl methacrylate, and 1H,1H,5H-octabromostearyl methacrylate.

[0092] According to one embodiment, the halogen-containing monomer may be an iodine-based monomer. The iodine-based monomer may be used without limitation as long as it is a monomer containing I (iodine) and including a polymerizable functional group.

[0093] According to one embodiment, the iodine-based monomer is, without limitation, 2,2,2-triiodoethyl methacrylate, 2-iodoethyl acrylate, 2,2,2-triiodomethyl acrylate, 2,2,2-triiodoethyl vinyl acrylate, 1,1,1-triiodoethyl acrylate, 2,2,2-triiodoethyl ethyl acrylate, 2,2,2-triiodoethyl propyl acrylate, 2,2,2-triiodoethyl acrylate, 2,2,2-triiodomethyl methacrylate, 2,2,2-triiodopropyl methacrylate, 2-iodoethyl methacrylate, 2,2,2-triiodomethyl methacrylate, hexaiodoisopropyl acrylate, hexaiodoisopropyl methacrylate, 2,2,2-triiodoisopropyl methacrylate, Hexa-iodomethyl methacrylate, Tri-iodomethyl methacrylate, 2,2,2-Triiodoisopropyl acrylate, 1H,1H,2H,2H-Heptadeca-iododecyl acrylate, 1H,1H,2H,2H-Hexa-iododecyl methacrylate, 1H,1H,2H,2H-Heptadeca-iodomethacrylate, 1H,1H,2H,2H-Heptadeca-iododimethyl methacrylate, 1H,1H,5H-Octa-iodopentyl acrylate, 1H,1H,5H-Octa-iodovinyl methacrylate, 1H,1H,5H-Octa-iodophenyl methacrylate, 1H,1H,5H-Octa-iodomethyl methacrylate, 1H,1H,5H-Octa-iodobutyl It may be one or more selected from the group consisting of methacrylate, 1H,1H,5H-octa-iodoisopropyl methacrylate, 1H,1H,5H-octa-iodoacrylate, 1H,1H,5H-octa-iodoethyl methacrylate, 1H,1H,5H-octa-iodotriiodomethyl methacrylate, and 1H,1H,5H-octa-iodostearyl methacrylate.

[0094] According to one embodiment, the reactive composition may contain a halogen-containing monomer in an amount of 1 part by weight or more, 2 parts by weight or more, 3 parts by weight or more, 5 parts by weight or more, 7 parts by weight or more, 8 parts by weight or more, 100 parts by weight or less, 95 parts by weight or less, 90 parts by weight or less, 80 parts by weight or less, 75 parts by weight or less, or any value between the above values, with respect to 100 parts by weight of unsaturated polyester. For example, the composition may contain 1 to 100 parts by weight, 5 to 80 parts by weight, or 5 to 50 parts by weight of the halogen-containing monomer with respect to 100 parts by weight of unsaturated polyester.

[0095] According to one embodiment, the functional monomer may include a fluorene-based monomer and a halogen-containing acrylate.

[0096] According to one embodiment, the reactive composition may contain a functional monomer in an amount of 1 part by weight or more, 2 parts by weight or more, 3 parts by weight or more, 5 parts by weight or more, 7 parts by weight or more, 8 parts by weight or more, 100 parts by weight or less, 95 parts by weight or less, 90 parts by weight or less, 80 parts by weight or less, 75 parts by weight or less, or any value between the above values, with respect to 100 parts by weight of unsaturated polyester. For example, the functional monomer may be included in an amount of 1 to 200 parts by weight, 5 to 150 parts by weight, or 5 to 100 parts by weight with respect to 100 parts by weight of unsaturated polyester. A glass fiber composite prepared with a reactive composition containing a functional monomer within the above range may have excellent transmittance and visibility, which is preferred but is not limited thereto.

[0097] According to one embodiment, the reactive composition may further include a (meth)acrylate-based monomer containing an acrylic group.

[0098] According to one embodiment, the reactive composition may comprise, with respect to 100 parts by weight of unsaturated polyester, a (meth)acrylate monomer in an amount of 1 part by weight or more, 2 parts by weight or more, 3 parts by weight or more, 5 parts by weight or more, 7 parts by weight or more, 8 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 100 parts by weight or less, 95 parts by weight or less, 90 parts by weight or less, 80 parts by weight or less, 75 parts by weight or less, 60 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, or any value between the above values. For example, with respect to 100 parts by weight of unsaturated polyester, the (meth)acrylate monomer may comprise 1 to 100 parts by weight, 5 to 60 parts by weight, 10 to 50 parts by weight, 10 to 40 parts by weight, or 10 to 30 parts by weight.

[0099] According to one embodiment, the (meth)acrylate monomer may include a (meth)acrylate monomer having one, two, or three or more (meth)acrylate groups, and preferably may include a di(meth)acrylate monomer having two acrylate groups. In addition to the di(meth)acrylate monomer, it may include one or more mixtures selected from alicyclic (meth)acrylate monomers, aromatic thio(meth)acrylate monomers, and di(meth)acrylate monomers containing ether groups.

[0100] According to one embodiment, the alicyclic (meth)acrylate monomer comprises a C5 to C8 alicyclic group, the aromatic thio(meth)acrylate comprises a phenylthio(meth)alkylacrylate, and the di(meth)acrylate comprising an ether group may be a di(meth)acrylate comprising an alkyleneoxy group or a polyethylene glycol di(meth)acrylate having a molecular weight of 200 to 1000.

[0101] The above (meth)acrylate-based monomer may further comprise, as a non-limiting example, one or more selected from 1,4-butanediol diacrylate, 1,3-propanediol diacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, 1,2-hexanediol diacrylate, triethylene glycol diacrylate, dimethyltoluenediamine diacrylate, picroloic acid diacrylate, benzenediol diacrylate, dimethylcarboxylate diacrylate, tetrahydrofurfuryl methacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol (ethoxy)1 diacrylate, 1,6-hexanediol (ethoxy)2 diacrylate, polyethylene glycol 600 diacrylate, 2-(phenylthio)ethyl acrylate, etc., but is not limited thereto. does not.

[0102] According to one embodiment, the cured product obtained by curing the reactive composition may have an Abbe number of 35 or more, 36 or more, 37 or more, 60 or less, 55 or less, 50 or less, 45 or less, 40 or less, 39 or less, 38 or less, or 37 or less, and may be any value between the above values. For example, it may be 35 to 60, 35 to 50, 35 to 40, 35 to 38, or 35 to 37. In the above range, excellent dispersibility may be achieved, and visibility may be further improved.

[0103] According to one embodiment, the cured product obtained by curing the reactive composition may have a refractive index of 1.55 or higher, 1.56 or higher, and 1.57 or lower, and may be any value between these values. For example, it may be 1.55 to 1.57 or 1.55 to 1.56. Within this range, the difference in refractive index from glass fibers is small, and high transmittance can be provided. In addition, physical properties with excellent visibility can be provided at the same time. The refractive index may be measured after curing the reactive composition at 80 to 100°C and 1 to 3 bar for 1.5 to 4 hours. For example, it may be measured using an Abbe refractometer in accordance with ASTM D1218, and may be measured at 486 nm, 589 nm, and 656 nm. In addition, the Abbe number may be calculated using the measured refractive index as Vd = (nd - 1) / (nF - nC).

[0104] According to one embodiment, the difference between the refractive index of the cured product obtained by curing the reactive composition and the refractive index of the glass fiber may be ±0.005 or less, ±0.004 or less, ±0.003 or less, ±0.002 or less, or ±0.001 or less, and the difference in Abbe number may be 20 or more, 21 or more, 30 or less, 25 or less, or any value between the above values. For example, the difference between the refractive index of the cured product obtained by curing the reactive composition and the refractive index of the glass fiber may be ±0.001 to ±0.005, and the difference in Abbe number may be 20 to 30, 20 to 25, or 21 to 24. When satisfying the above ranges, excellent transmittance of 85% or more and excellent visibility can be provided. The present invention may provide a glass fiber composite composition comprising the above-described reactive composition; a curing agent; and a glass fiber.

[0105] The present invention can provide a cured glass fiber composite comprising the above-described reactive composition; a curing agent; and glass fiber.

[0106] According to one embodiment, the glass fiber is not limited to any commonly used glass fiber, and the refractive index of the glass fiber may be 1.5500 to 1.5700 at a wavelength of 589 nm.

[0107] According to one embodiment, the glass fiber may be a glass fiber monofilament, a glass fiber strand composed of a plurality of glass fiber monofilaments, a glass fiber yarn obtained by twisting the glass fiber strand, a glass fiber fabric, etc. The glass fiber fabric may be in the form of a thick sheet of plain weave roving cloth, which is woven into yarn by winding the glass fiber strand into a bundle without twisting, but is not limited thereto. For example, if the glass fiber is a sheet-shaped roving cloth, the glass fiber composite according to one embodiment of the present invention may be manufactured into a sheet by impregnating the roving cloth with a reactive composition according to one embodiment of the present invention, and then curing it. Additionally, the roving cloth may be used in a single layer, at least two layers, or three layers laminated together, but is not limited thereto.

[0108] According to one embodiment, the glass fiber may have an average diameter of 1 to 50 μm, 1 to 20 μm, 2 to 10 μm, or 2 to 5 μm, but is not limited thereto. The average diameter can be measured using conventional methods.

[0109] In addition, when using the above-mentioned glass fiber fabric, the thickness of the glass fiber fabric may be 0.1 to 1 mm, 0.2 to 0.8 mm, or 0.3 to 0.5 mm, but is not limited thereto. In addition, the basis weight of the glass fiber fabric is, for example, 100 g / m² 2 Above, 200 g / m² 2 Above, 300 g / m²2 Above, 400 g / m² 2 Above, 500 g / m² 2 Above, 1000 g / m² 2 Below, 900 g / m² 2 It may be less than or equal to, and may be any value between the above figures.

[0110] According to one embodiment, the glass fiber may comprise 5 to 200 parts by weight or 10 to 150 parts by weight of glass fiber per 100 parts by weight of the reactive composition, but is not limited thereto.

[0111] According to one embodiment, the curing agent may be any one or more mixtures selected from the group consisting of methyl ethyl ketone peroxide (MEKPO), benzoyl peroxide (BPO), tert-butyl peroxy-2-ethylhexanoate (TBPEH), tert-butyl peroxybenzoate (TBBPB), and tert-butyl peroxide (TBPO).

[0112] According to one embodiment, the curing agent may be included in an amount of 0.5 to 5 parts by weight, 0.8 to 3 parts by weight, 0.8 to 2 parts by weight, or 1 to 1.5 parts by weight per 100 parts by weight of the reactive composition. A glass fiber composite containing a curing agent within the above range is preferred as it may have excellent transmittance, visibility, and mechanical properties, but is not limited thereto.

[0113] According to one embodiment, the glass fiber composite may be manufactured by impregnating the glass fibers into a composition comprising a reactive composition and a curing agent. If the glass fibers are in the form of sheets, the composite may be manufactured by laminating one, two, or three or more sheets and then impregnating them into the composition.

[0114] According to one embodiment, the glass fiber composite may be formed by impregnating the glass fibers in a composition comprising a reactive composition and a curing agent, and then curing it at 80 to 100°C and 1 to 3 bar for 1.5 to 4 hours.

[0115] According to one embodiment, the glass fiber composite may have a transmittance of 85% or more, 86% or more, 87% or more, 88% or more, 95% or less, 90% or less, or any value between the above values, measured in the 589 nm wavelength range according to ASTM D1003. For example, it may be 85 to 95%, 85 to 90%, 86 to 90%, or 86 to 89%.

[0116] In addition, the glass fiber composite described above can provide good or excellent physical properties in a visibility evaluation of a glass fiber composite measuring 700 mm in width, 700 mm in length, and 4 mm in thickness, which is manufactured by layering three layers of roving cross (basis weight 300 g / m²) woven from glass fibers with an average diameter of 3 μm and a thickness of 0.4 mm, and impregnating them with a composition including a reactive composition and a curing agent according to one embodiment of the present invention. The visibility evaluation is performed by placing the manufactured glass fiber composite on paper with text written in Malgun Gothic, 12 pt font size, at intervals of 1.5 cm and 15 cm, and observing how the text visible through the glass fiber composite is evaluated. Ten researchers visually observe and evaluate the composite, and the average value is measured based on a 10-point scale. Good is when the characters are observed at a distance of 1.5 cm and 15 cm, and the characters are clearly visible at the 1.5 cm distance but appear slightly blurry at the 15 cm distance, and the visual evaluation score is an average of 5 points or higher. Excellent is when the characters are clearly visible at both the 1.5 cm and 15 cm distances, and the visual evaluation score is an average of 8 points or higher.

[0117]

[0118] The present invention will be explained in more detail below based on the following examples and comparative examples. However, the following examples and comparative examples are merely illustrative of the present invention and are not intended to limit the present invention.

[0119] [measurement method]

[0120] 1. Measurement of Refractive Index and Abbe Number

[0121] In accordance with ASTM D1218, the refractive indices and Abbe numbers at 486 nm, 589 nm, and 656 nm were measured using an Abbe refractometer (Excellence R5; METTLER TOLEDO).

[0122] 2. Transmittance Measurement

[0123] A specimen with a width of 50 mm, a length of 50 mm, and a thickness of 3 mm was measured in the wavelength range of 340 to 760 nm according to ASTM D1003 using a spectrophotometer (CM-36dG, KONICA MINOLTA), and the transmittance at 589 nm was recorded.

[0124] [Preparation Example 1]

[0125] An unsaturated polyester resin with an acid value of 27 mgKOH / g was prepared by esterifying a diol compound of 17 mol% ethylene glycol (EG), 38 mol% 1,2-propylene glycol (PG), and 2 mol% neopentyl glycol (NPG) with a carboxylic acid compound of 20 mol% phthalic anhydride (PA), 15 mol% maleic anhydride (MA), and 8 mol% succinic acid (SA) while stirring at 200 °C.

[0126] [Comparative Manufacturing Example 1]

[0127] An unsaturated polyester resin with an acid value of 26.5 mgKOH / g was prepared in the same manner as in Preparation Example 1, except that neopentyl glycol was not used as the diol compound and 18 mol% ethylene glycol and 39 mol% 1,2-propylene glycol were used.

[0128] [Comparative Manufacturing Example 2]

[0129] An unsaturated polyester resin with an acid value of 26.5 mgKOH / g was prepared in the same manner as in Preparation Example 1, except that 1,2-propylene glycol was not used as the diol compound, and 18 mol% ethylene glycol and 39 mol% neopentyl glycol were used.

[0130]

[0131] [Example 1]

[0132] A reactive composition was prepared by mixing 50 parts by weight of styrene monomer, 25 parts by weight of 1,6-hexanediol diacrylate, and 75 parts by weight of 9-fluorenyl methacrylate with 100 parts by weight of the unsaturated polyester resin prepared in Preparation Example 1 above at 80°C.

[0133] [Example 2]

[0134] A reactive composition was prepared by mixing 51 parts by weight of styrene monomer, 19 parts by weight of 1,6-hexanediol diacrylate, and 19 parts by weight of 9-fluorenyl methacrylate with 100 parts by weight of the unsaturated polyester resin prepared in Preparation Example 1 above at 80°C.

[0135] [Example 3]

[0136] A reactive composition was prepared by mixing 52 parts by weight of styrene monomer, 18 parts by weight of 1,6-hexanediol diacrylate, and 9 parts by weight of 9-fluorenyl methacrylate with 100 parts by weight of the unsaturated polyester resin prepared in Preparation Example 1 above at 80°C.

[0137] [Example 4]

[0138] A reactive composition was prepared by mixing 52 parts by weight of styrene monomer, 18 parts by weight of 1,6-hexanediol diacrylate, and 9 parts by weight of 1H,1H,5H-octafluoropentyl methacrylate with 100 parts by weight of the unsaturated polyester resin prepared in Preparation Example 1 above at 80°C.

[0139]

[0140] [Comparative Example 1]

[0141] A reactive composition was prepared by mixing 50 parts by weight of styrene monomer and 17 parts by weight of 1,6-hexanediol diacrylate with 100 parts by weight of the unsaturated polyester resin prepared in Preparation Example 1 above at 80°C.

[0142] [Comparative Example 2]

[0143] A reactive composition was prepared in the same way as in Example 1, except that the unsaturated polyester resin used was that of Comparative Example 1.

[0144] [Comparative Example 3]

[0145] A reactive composition was prepared in the same way as in Example 1, except that the unsaturated polyester resin used was that of Comparative Example 2.

[0146]

[0147] (Measurement of refractive index and Abbe number of a cured reactive composition)

[0148] For 100 parts by weight of the reactive compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 3 above, 1 part by weight of a tert-butyl peroxy-2-ethylhexanoate (TBPEH) curing agent was mixed, and then molded and cured using a vacuum mold at 95°C, 1.2 bar, for 1.5 hours. The refractive index and Abbe number of the cured product were measured and are shown in Table 1 below. The cured product specimens were prepared with dimensions of 5 cm in width, 5 cm in length, and 5 mm in thickness.

[0149]

[0150] (Evaluation of transmittance of glass fiber composites)

[0151] Roving cloth (basis weight 300 g / m²) 0.4 mm thick, woven from glass fibers with an average diameter of 3 µm in a mold 2 ) One layer was added, and the composition was impregnated with 1 part by weight of tert-butyl peroxy-2-ethylhexanoate (TBPEH) curing agent mixed with 100 parts by weight of the reactive composition prepared in Examples 1 to 4 and Comparative Examples 1 to 3.

[0152] Afterwards, it was molded and cured at 95 ℃ and 1.2 bar for 1.5 hours. Then, it was post-cured at 80 ℃ for 2 hours and at 100 ℃ for 2 hours to produce a glass fiber composite with a width of 700 mm, a length of 700 mm, and a thickness of 4 mm.

[0153] The transmittance of the manufactured single-layer glass fiber composite was measured and is shown in Table 1 below.

[0154]

[0155] (Evaluation of the visibility of glass fiber composites)

[0156] Preparation of the specimen:

[0157] Roving cloth (basis weight 300 g / m²) 0.4 mm thick, woven from glass fibers with an average diameter of 3 µm in a mold 2 ) 3 layers were added, and impregnated into a composition in which 1 part by weight of tert-butyl peroxy-2-ethylhexanoate (TBPEH) curing agent was mixed with 100 parts by weight of the reactive composition prepared in Examples 1 to 4 and Comparative Examples 1 to 3.

[0158] Afterwards, it was molded and cured at 95 ℃ and 1.2 bar for 1.5 hours. Then, it was post-cured at 80 ℃ for 2 hours and at 100 ℃ for 2 hours to produce a glass fiber composite with a width of 700 mm, a length of 700 mm, and a thickness of 4 mm.

[0159] The visibility of the manufactured 3-layer glass fiber composite was evaluated and is shown in Table 1 below.

[0160] Visibility evaluation method:

[0161] The above-mentioned manufactured glass fiber composites were placed on paper with text of Malgun Gothic, 12 pt font size at intervals of 1.5 cm and 15 cm, and how the text visible through the glass fiber composites was observed. Visibility was evaluated by 10 researchers through visual observation, and the average value was based on a 10-point scale as follows.

[0162] Excellent: When observing the letters with a gap of 1.5 cm and 15 cm, the letters are clearly visible in both cases, and the visual evaluation score is an average of 8 points or higher.

[0163] Good: When observing the letters with a distance of 1.5 cm and 15 cm, the letters are clearly visible at the 1.5 cm distance but appear slightly blurry at the 15 cm distance, and the visual evaluation score is an average of 5 points or higher.

[0164] Defective: When observing the characters with a gap of 1.5 cm and 15 cm, the characters are not clearly visible and appear blurry in both cases, and the visual evaluation score is less than 4 points on average.

[0165]

[0166] Refractive Index Abbe Number Transmittance Visibility 486nm 589nm 656nm Example 1 1.566 1 1.555 3 1.55 1 1 37.087.7% Excellent Example 2 1.566 0 1.555 1 1.55 1 0 37.088.0% Excellent Example 3 1.565 9 1.555 2 1.55 09 37.088.2% Excellent Example 4 1.574 3 1.562 8 1.55 82 35.086.6% Good Comparative Example 1 1.569 5 1.55 86 1.55 4 3 36.884.3% Poor Comparative Example 2 1.576 4 1.564 5 1.567 23 5.784.9 Poor Comparative Example 31.56111.55151.540836.183.2 Defective glass fiber1.55461.55781.564158.7--

[0167] In Table 1 above, the glass fibers are the physical properties of a roving cloth with a thickness of 0.4 mm woven from glass fibers with an average diameter of 3 μm.

[0168] As shown in Table 1 above, when comparing Comparative Example 1, which did not use a functional monomer, with the composites of Examples 1 to 4, which used a functional monomer, the transmittance of Examples 1 to 4 was 85% or higher, specifically 86 to 89%, showing excellent transmittance.

[0169] In addition, regarding the refractive index measured at each wavelength, the difference in refractive index between the cured product of the reactive composition and the glass fiber was found to be 0.005 or less, confirming that refractive index matching was effectively achieved.

[0170] In addition, the above-mentioned cured material exhibits an Abbe number of 35 to 37, confirming that dispersion characteristics are balancedly controlled while maintaining a high refractive index.

[0171] Accordingly, it was found that the reactive composition according to the present invention exhibits excellent optical properties, such as reduced light scattering and improved transmittance, compared to the comparative example.

[0172] In addition, as seen in Examples 1 to 3 and Example 4, it was confirmed that the transmittance was slightly reduced in Example 4, which has an Abbe number of 35, compared to Examples 1 to 3, which have an Abbe number of 37.

[0173] In addition, as seen in Comparative Examples 2 and 3, it was confirmed that when manufacturing an unsaturated polyester resin containing functional monomers, if ethylene glycol, 1,2-propylene glycol, and neopentyl glycol are not used in combination as diol compounds and any one component is excluded, the transmittance cannot satisfy 85% or more, and it was also confirmed that the clarity is significantly reduced in the visibility evaluation.

[0174] On the other hand, as seen in Examples 1 to 4, when an unsaturated polyester resin and a functional monomer were used in combination, prepared using a combination of ethylene glycol, 1,2-propylene glycol, and neopentyl glycol as diol compounds, an excellent transmittance of 85% or more, specifically 86 to 89%, was observed, and it was confirmed that the image clarity was significantly improved compared to Comparative Examples 1 to 3, resulting in excellent visibility.

[0175]

[0176] As described above, the present invention has been explained by specific details and limited embodiments; however, this is provided merely to aid in a more comprehensive understanding of the invention, and the invention is not limited to the above embodiments. Those skilled in the art can make various modifications and variations from this description.

[0177] Accordingly, the scope of the present invention is not limited to the described embodiments, and all things equivalent to or having equivalent variations to the claims set forth below, as well as the claims set forth below, shall be considered to fall within the scope of the concept of the present invention.

Claims

1. A reactive composition comprising an unsaturated polyester resin, an aromatic monomer, and a functional monomer, wherein The above unsaturated polyester resin is prepared from a polymerizable composition comprising a diol compound including ethylene glycol (EG), propylene glycol (PG), and neopentyl glycol (NPG); and two or more carboxylic acid compounds selected from phthalic anhydride (PA), maleic anhydride (MA), and succinic acid (SA). A reactive composition comprising the above functional monomer, which is selected from the group consisting of fluorene-based monomers and halogen-containing monomers, or a mixture thereof.

2. In Paragraph 1, The above diol compound is a reactive composition comprising 25 to 60 parts by weight of ethylene glycol and 1 to 10 parts by weight of neopentyl glycol per 100 parts by weight of propylene glycol.

3. In Paragraph 1, The above carboxylic acid compound is a reactive composition comprising 25 to 60 parts by weight of succinic acid and 30 to 100 parts by weight of maleic anhydride, based on 100 parts by weight of phthalic anhydride.

4. In Paragraph 1, The above reactive composition comprises 20 to 80 parts by weight of an aromatic monomer per 100 parts by weight of an unsaturated polyester resin.

5. In Paragraph 1, The above reactive composition comprises 1 to 100 parts by weight of a functional monomer per 100 parts by weight of an unsaturated polyester resin.

6. In Paragraph 1, The above reactive composition further comprises one or more (meth)acrylate monomers selected from the group consisting of alicyclic (meth)acrylate monomers, aromatic thio(meth)acrylate monomers, and di(meth)acrylate monomers containing ether groups.

7. In Paragraph 6, A reactive composition wherein the above-mentioned alicyclic (meth)acrylate monomer comprises a C5 to C8 alicyclic group, the above-mentioned aromatic thio(meth)acrylate monomer comprises phenylthio(meth)alkylacrylate, and the above-mentioned di(meth)acrylate monomer comprising an ether group is a di(meth)acrylate comprising an alkyleneoxy group or a polyethylene glycol di(meth)acrylate having a molecular weight of 200 to 1000.

8. In Paragraph 6, The above reactive composition comprises 1 to 100 parts by weight of a (meth)acrylate-based monomer per 100 parts by weight of an unsaturated polyester resin.

9. In Paragraph 1, A cured product obtained by curing the above reactive composition is a reactive composition having a refractive index of 1.55 to 1.57 measured at 589 nm according to ASTM D1218.

10. In Paragraph 1, The cured product obtained by curing the above reactive composition is a reactive composition having an Abbe number of 35 to 60.

11. A cured glass fiber composite comprising a reactive composition selected from any one of claims 1 to 10; a curing agent; and glass fiber.

12. In Paragraph 11, The above glass fiber composite comprises 5 to 200 parts by weight of glass fibers per 100 parts by weight of a reactive composition.

13. In Paragraph 11, The above curing agent comprises one or more selected from the group consisting of methyl ethyl ketone peroxide (MEKPO), benzoyl peroxide (BPO), tert-butyl peroxy-2-ethylhexanoate (TBPEH), tert-butyl peroxybenzoate (TBBPB), and tert-butyl peroxide (TBPO), forming a glass fiber composite.

14. In Paragraph 11, The above glass fiber composite comprises 0.5 to 5 parts by weight of a curing agent per 100 parts by weight of a reactive composition.

15. In Paragraph 11, The above glass fiber composite is a glass fiber composite having a 589 nm transmittance of 85% or more as measured according to ASTM D1003.

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