KR102613741B1 - Sizing composition and glass fiber using the same - Google Patents

Abstract

The present invention relates to a sizing composition for glass fiber and glass fiber manufactured using the same.

Description

Sizing composition and glass fiber using the same}

The present invention relates to a sizing composition for glass fiber and glass fiber manufactured using the same.

Glass fiber is used for various purposes in various industrial fields due to its characteristics such as high strength, insulation, non-flammability, dimensional stability, and chemical resistance. In particular, long glass fiber (E-Glass Fiber) has excellent electrical properties and weathering resistance, and is used as a building material and as a strength reinforcement for polymer materials using electrical insulation properties.

Typically, after melting various oxides that form glass, thin glass filaments in the form of threads are extracted through bushing, coated with a sizing composition, and then braided to form strands. , it is processed into various forms and applied to various fields. For example, glass fiber is processed into chopped strands cut to a length of 3 to 20 mm and used as a reinforcing material in manufacturing thermoplastic or thermosetting plastic molded products. In general, glass fiber is uniformly dispersed in molten thermoplastic or thermosetting plastic through a compounding process to produce glass fiber reinforced plastic pellets, and then the glass fiber reinforced thermoplastic or thermosetting plastic molded product of the desired shape is manufactured by injection or molding.

The sizing composition is coated on the surface of glass fiber and serves to increase the adhesion between the glass fiber and plastic interface during compounding. The sizing composition consists of a film former, a coupling agent, and other additives. In order to realize excellent mechanical properties such as tensile, impact, and flexural strength, research and development continues on sizing compositions containing film formers and coupling agents of various compositions. It is becoming. For example, Korean Patent Publication No. 10-2018-0067592 discloses a coating composition for reinforced fibers using a film former containing one or more of polyvinylpyrrolidone, polyvinylacetate, and polyurethane. However, a small amount of coupling agent is used in the coating composition, and there are limitations in realizing sufficient physical properties.

The present invention provides a sizing composition for coating glass fibers.

Additionally, the present invention provides glass fibers coated with the above-described sizing composition, which serves to improve the tensile strength, impact strength and flexural strength of polymer composite materials.

The present invention provides a first film former comprising a polyurethane resin; A second film forming agent comprising at least one resin selected from block isocyanate resin, carbodiimide resin, and oxazoline resin; and a silane coupling agent, wherein the mixing ratio (weight ratio based on solid content) of the first film former and the second film former is 98:2 to 80:20, based on the total solid content of the sizing composition. A sizing composition containing 20 to 60% by weight of the silane coupling agent is provided.

Additionally, the present invention provides glass fiber coated with the above-described sizing composition and a polymer composite material containing the same.

Polymer composites comprising glass fibers coated with the sizing composition according to the present invention exhibit excellent tensile, impact and flexural strengths. In particular, the sizing composition of the present invention is suitable for various types of thermoplastic or thermosetting resins (e.g., polyamide, polysulfone, polyethersulfone, polyimide, polyetherimide, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, It can be applied to modified polyphenylene oxide (mPPO) resin, liquid crystal polymer (LCP), etc., and can provide a glass fiber-reinforced polymer composite material with excellent physical properties.

Hereinafter, the present invention will be described in detail. However, it is not limited to the following content, and each component may be variously modified or selectively mixed as needed. Accordingly, it should be understood to include all changes, equivalents, and substitutes included in the spirit and technical scope of the present invention.

The “glass transition temperature” used in this specification is measured by a common method known in the art, and can be measured, for example, by differential scanning calorimetry (DSC). “Number average molecular weight” or “weight average molecular weight” is measured by a common method known in the art, and can be measured, for example, by a GPC (gel permeation chromatograph) method. “Elongation” is measured by a common method known in the art. For example, a specimen molded into a dogbone or dumbbell shape can be measured using a universal testing machine (UTM). .

<Sizing composition>

The sizing composition according to the invention comprises a film former and a silane coupling agent.

film former

The sizing composition according to the present invention forms a second film comprising a first film former comprising a polyurethane resin as a film forming agent and at least one resin selected from block isocyanate resin, carbodiimide resin, and oxazoline resin. Includes provisions.

first film former

The first film former includes a polyurethane resin. Polyurethane resin acts alone or in combination with silane to provide mechanical strength and cohesion between glass fiber filaments and to prevent fuzz.

The polyurethane resin is produced by the reaction of polyol and isocyanate.

As the polyol, conventional polyols used in the synthesis of urethane resins in the art can be used without particular restrictions. Non-limiting examples of the polyol include polyether polyol, polyester polyol, polycarbonate polyol, and acryl polyol, such as polyethylene adipate polyol and polybutylene adipate. There are pate polyol, polyethylene butylene adipate polyol, polycaprolactone polyol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyether polyester polyol, etc. The above-mentioned ingredients can be used alone or two or more types can be mixed.

For example, the polyol may be polyester polyol, polyether polyol, polycarbonate polyol, or a mixture thereof. Polyester polyol has excellent heat resistance, but its hydrolysis resistance may be weak. On the other hand, polyether polyol may have inferior heat resistance compared to polyester polyol, but has excellent hydrolysis resistance. On the other hand, polycarbonate polyol may have superior heat resistance and hydrolysis resistance than polyester polyol or polyether polyol. Therefore, it is necessary to select the composition of the polyol according to the intended use.

As the isocyanate, common isocyanate compounds used in the synthesis of urethane resins in the art can be used without limitation. Non-limiting examples of the isocyanate include methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HMDI), and isophorone diisocyanate. , IPDI), metaxylene diisocyanate (MXDI), tetramethylxylene diisocyanate (TMXDI), diisocyanate made alicyclic by adding hydrogen to the benzene ring of the MDI (H12 MDI), xylene diisocyanate (XDI) ), etc. include diisocyanate (hydrogenated The above-mentioned ingredients can be used alone or two or more types can be mixed.

For example, the isocyanate may be an aliphatic isocyanate, for example, one or more types selected from isophorone diisocyanate, 1,6-hexamethylene diisocyanate, and 4,4-dicyclomethane diisocyanate.

The polyurethane resin formed by the reaction of the above-described polyol and isocyanate may contain unreacted isocyanate groups, and in this case, the unreacted isocyanate groups may be reacted with an appropriate blocking agent for use. As the blocking agent, common compounds used as blocking agents in the art can be used without limitation. For example, oximes, pyrazoles, malonates, phenols, caprolactam, and alcohols, etc. Block topics can be used.

The polyurethane resin may be used in a dispersed form in water, and may contain an ionic or non-ionic emulsifier for dispersion stability. The pH of the water-dispersed polyurethane resin may be 6.0 to 10.0, for example, 6.5 to 9.0. If the pH is below the above-mentioned range, the dispersion stability may decrease when the polyurethane resin is dispersed in water, and if it exceeds the above-mentioned range, the stability of the sizing solution containing the silane coupling agent may be reduced due to silane condensation. .

The polyurethane resin may be a soft polyurethane resin with excellent toughness.

The glass transition temperature of the polyurethane resin may be 0°C or lower, for example, -70 to 0°C. If the glass transition temperature of the polyurethane resin exceeds 0 ℃, the ductility of the polyurethane resin may decrease and external forces may not be effectively absorbed or transmitted at the interface between the glass fiber and the base resin, resulting in glass fiber reinforced composite materials. The mechanical strength may decrease.

The weight average molecular weight of the polyurethane resin may be 30,000 to 1,000,000 g/mol, for example, 30,000 to 500,000 g/mol. If the molecular weight of the polyurethane resin is less than the above-mentioned range, the mechanical properties of the urethane resin itself may deteriorate when forming a film, which may deteriorate the physical properties, and if it exceeds the above-mentioned range, the film forming ability is poor and the mechanical strength of the final composite product is reduced. may deteriorate.

The tensile elongation of the polyurethane resin may be 400% or more and less than 1,300%, for example, 400% or more and less than 1,000%. If the tensile elongation of the polyurethane resin is less than the above-mentioned range, the ductility of the polyurethane coating layer may be insufficient and the mechanical strength properties of the composite material may be reduced, and if it exceeds the above-mentioned range, the ductility may be sufficient but heat resistance or mechanical rigidity may be weakened. The mechanical properties of composite materials may deteriorate.

The first film former may be included in an amount of 25 to 80% by weight, for example, 40 to 60% by weight, based on the total solid content of the sizing composition. If the content of the first film former is less than the above-mentioned range, the focus of the glass fiber may be reduced, resulting in deterioration of workability, such as generation of fuzz, and if it exceeds the above-mentioned range, mechanical strength may not be sufficiently developed. there is.

secondary film former

The second film former includes at least one resin selected from block isocyanate resin, carbodiimide resin, and oxazoline-based resin. The second film former acts alone or in combination with the silane and the first film former to improve mechanical strength and hydrolysis resistance. Therefore, by mixing the first and second film formers, the mechanical properties of the composite material can be further improved.

Block isocyanate resin

Block isocyanate resin serves as a bridge between the polyurethane resin and the coupling agent. Block isocyanate resin exists in a deactivated form in the sizing composition, but when the sizing composition is applied to glass fiber and dried, the blocking agent dissociates and becomes activated and reacts with the reactive group in the coupling agent or the hydroxyl group of polyurethane, or A cured structure can be formed by reacting isocyanate groups with each other. On the other hand, if the de-blocking temperature of the blocking agent is higher than 150 ℃, the isocyanate group may remain in an undissociated state even after drying the glass fiber, and then dissociate at high temperature when compounding glass fiber and engineering plastic. The activated isocyanate group can react with the functional group of the base resin to form a covalent bond. As a result, the mechanical strength of the glass fiber reinforced plastic material can be increased.

The blocked isocyanate can be prepared by blocking an isocyanate resin with an isocyanate group blocking agent, and can be used in a form dispersed in water.

Non-limiting examples of the isocyanate resin include methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI), hexa methylene diisocyanate (HMDI), and isophorone diisocyanate (Isophorone). Di-isocyanate, IPDI), meta-xylene diisocyanate (MXDI), tetramethylxylene diisocyanate (TMXDI), diisocyanate made into an alicyclic form by adding hydrogen to the benzene ring of the MDI (H12 MDI), xylene diisocyanate There are diisocyanates (hydrogenated The above-mentioned ingredients may be used alone or two or more types may be used in combination.

As the blocking agent, common compounds used as blocking agents in the relevant technical field can be used without limitation. For example, oximes, pyrazoles, malonates, phenols, caprolactam, and alcohols, etc. Block topics can be used.

The isocyanate group content (NCO%) of the isocyanate resin may be 3 to 30%, for example, 5 to 20%, based on solid content. If the isocyanate group content (NCO%) of the isocyanate resin is less than the above-mentioned range, the isocyanate content may be too low and an effective cross-linking reaction may become impossible, and if it is greater than the above-mentioned range, the isocyanate content may be excessive than necessary, reducing the efficiency of the cross-linking reaction. This may result in reduced mechanical strength.

Carbodiimide Resin

Carbodiimide resin effectively reacts with carboxylic acid groups and acts as a crosslinking agent for polyurethane resins with carboxylic acid groups in the sizing composition, thereby increasing the water resistance of polyurethane resins and improving the mechanical strength of composite materials. .

The carbodiimide resin can be prepared by condensing an isocyanate compound at 40°C to 200°C in a catalytic atmosphere.

As the isocyanate, conventional isocyanate compounds used in polycarbodiimide resin synthesis in the art can be used without limitation. Non-limiting examples of the isocyanate include methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HMDI), and isophorone diisocyanate. , IPDI), metaxylene diisocyanate (MXDI), tetramethylxylene diisocyanate (TMXDI), diisocyanate made alicyclic by adding hydrogen to the benzene ring of the MDI (H12 MDI), xylene diisocyanate (XDI) ), etc. include diisocyanate (hydrogenated The above-mentioned ingredients can be used alone or two or more types can be mixed.

As a catalyst used in producing the polycarbodiimide, any catalyst commonly used in the art can be used without limitation. Non-limiting examples of the catalyst include phosphorus-based compounds such as phospholene, phospholane, phospholene oxide, phospholane oxide, phosphopolidine or phospholine oxide, amines, metal salts of carboxylic acids, or organo-metal compounds. These can be used alone or two or more types can be used together.

The carbodiimide resin can be used in dissolved or dispersed form in water. The pH of the carbodiimide resin solution or dispersion may range from 5 to 13. If the pH is outside the above range, storage may be poor due to the reactivity of the carbodiimide group.

The equivalent weight (molecular weight per mole of carbodiimide) of the carbodiimide group (N=C=N) in the carbodiimide resin may be 300 to 600. If the equivalent weight of the carbodiimide group in the carbodiimide resin is outside the above-mentioned range, an effective crosslinking reaction between the carboxylic acid group and the carbodiimide in the film forming agent becomes impossible, and mechanical strength and hydrolysis resistance may be reduced. .

Oxazoline-based resin

Oxazoline-based resins can effectively react not only with carboxylic acid groups but also with aromatic thiol groups or aromatic alcohol groups to form amide ester groups. Therefore, mechanical strength can be increased by cross-linking with the polyurethane resin containing carboxylic acid groups in the sizing composition or by reacting with the functional groups of the aromatic base resin during compounding, thereby increasing the surface adhesion of the glass fibers in the composite material. .

The oxazoline-based resin can be prepared by copolymerizing a monomer having an oxazoline group, or by changing the side chain functional group to contain an oxazoline group after preparing the polymer, and can be used in a form dispersed in water.

The polymer skeleton of the oxazoline-based resin is not particularly limited, but may include, for example, one or more types selected from styrene-based, (meth)acrylic-based, olefin-based, ester-based, and carbonate-based skeletons. The oxazoline group may include, for example, 2-oxazoline group, 3-oxazoline group, 4-oxazoline group, etc.

The oxazoline group content in the oxazoline-based resin may be 100 to 600 equivalents (molecular weight per mole of oxazoline group). If the content of oxazoline groups in the oxazoline-based resin is outside the above-mentioned range, effective crosslinking reaction between the functional groups of the film former or base resin and the oxazoline group may become impossible, resulting in reduced mechanical strength and hydrolysis resistance.

The second film former may be included in an amount of 1 to 20% by weight, for example, 3 to 15% by weight, based on the total solid content of the sizing composition. If the content of the second film former is less than the above-mentioned range, the improvement of mechanical properties may be insufficient, and if it exceeds the above-mentioned range, the efficiency of the crosslinking reaction may be reduced and the mechanical strength may be reduced, and the concentration between the glass fiber filaments may be reduced. This may result in poor workability.

The mixing ratio (weight ratio, solid content basis) of the first film former and the second film former may be 98:2 to 80:20, for example, 97:3 to 85:15. If the mixing ratio of the second film former to the first film former is less than the above-mentioned range, the adhesion between the glass fiber and the plastic interface may not be sufficient and the mechanical properties may be relatively inferior, and if the mixing ratio of the second film former to the first film former is greater than the above-mentioned range, urethane As the content decreases, the focus between glass fiber filaments becomes poor, which may reduce workability, and the efficiency of the cross-linking reaction may decrease, which may actually reduce mechanical strength.

Silane coupling agent

Silane coupling agents serve to provide adhesion between inorganic glass and organic film formers or thermoplastic engineering plastics. The silane coupling agent has an alkoxy group hydrolyzed in water to form silanol and forms a siloxane bond through a dehydration condensation reaction with the silanol group on the surface of the glass fiber. At this time, the silane coupling agent is oriented or bonded to the surface of the glass fiber and serves as a coupling agent to protect the glass surface and provide interfacial adhesion between the film former and the glass.

The silane coupling agent is not particularly limited as long as it is commonly used in the relevant technical field. Non-limiting examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, and γ-acryloxypropyl. Trimethoxysilane, γ-acryloxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxy Silane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxysilane, dimethyldimethoxysilane, vinylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane , γ-acryloxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane , γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, etc., and these can be used alone or in a mixture of two or more types. For example, the silane coupling agent may include one or more of amino-based, ureido-based, and epoxy-based silane coupling agents. In particular, when an amino-based silane coupling agent is used, the adhesion between glass and thermoplastic engineering plastic is more effective. It can be improved.

The silane coupling agent may be included in an amount of 15 to 60% by weight, for example, 25 to 55% by weight, based on the total solid content of the sizing composition. When the content of the silane coupling agent is within the above-mentioned range, excellent tensile strength, impact strength, and flexural strength can be imparted to a thermoplastic polymer composite material including glass fibers coated with the sizing composition. If the content of the silane coupling agent is less than the above-mentioned range, the coupling effect between the glass fiber and the film former or the glass fiber and the plastic may not be sufficient, resulting in inferior mechanical strength, and if it exceeds the above-mentioned range, the coupling effect between the glass fiber and the film former or the glass fiber and the plastic may be insufficient. Dispersion of glass fibers may become poor, and the amount of film former may be insufficient, resulting in poor glass fiber focusing. Additionally, excessive silanol groups may not participate in the condensation reaction with the surface of the glass fiber, which may reduce mechanical strength.

additive

The sizing composition of the present invention may further include additives commonly used in the relevant technical field, within a range that does not impair the inherent properties of the sizing composition. Non-limiting examples of additives that can be used in the present invention include a bundling auxiliary resin that improves the bundling properties of glass fibers, a lubricant that provides surface lubricity, a buffering agent for adjusting pH, and a color stabilizer. These may be used alone or two or more types may be used together.

Such additives may be added within the content range known in the art, for example, 0.1 to 10% by weight, for example, 0.1 to 1% by weight, based on the total solid content of the sizing composition.

<Glass fiber>

The present invention provides glass fibers surface treated with the above-described sizing composition.

The glass fiber substrate usable in the present invention is not particularly limited as long as it is known in the relevant technical field. For example, E-glass, D-glass, S-glass, NE-glass, T-glass, etc., but are not limited to these.

The fiber diameter of the glass fiber may be 5 to 20 ㎛, for example, 8 to 15 ㎛. If the fiber diameter is less than the above range, the cutting occurrence rate may increase during the glass fiber manufacturing process, which may lead to a problem of reduced productivity, and if it exceeds the above range, the strength reinforcing effect of the glass fiber may be reduced due to a decrease in the surface area of the glass fiber.

The fiber length of the glass fiber may be 1 to 20 mm, for example, 2 to 10 mm. If the fiber length is less than the above range, the strength reinforcing effect of the final glass fiber reinforced thermoplastic composite material may be reduced due to fiber breakage that occurs during the extrusion and injection process, and if it exceeds the above range, the input of the fiber reinforcement material during the extrusion process may be poor. Uniform dispersion of glass fiber reinforcement may be poor, resulting in poor appearance.

The application method of the sizing composition is not particularly limited and includes, but is not limited to, dipping, roll coating, die coating, gravure coating, spray coating, and flow coating. In one example, the sizing composition can be applied to a glass fiber substrate using a dipping method, where the dipping time is from a few milliseconds to a few seconds.

The application amount (based on solid content) of the sizing composition is not particularly limited, but may be 0.1 to 1.5 parts by weight, for example, 0.3 to 1.0 parts by weight, based on 100 parts by weight of solid content of glass fiber. If the content of the sizing composition is less than the above range, the focusing power of the glass fiber bundle may be poor, which may deteriorate workability in the extrusion process. If the content of the sizing composition exceeds the above range, gas generation during compounding extrusion and injection may cause changes in appearance, color, etc. This may cause problems with product quality.

The glass fiber coated with the sizing composition is usually in the form of a filament, and several strands (e.g., 4,000 pieces) are braided to form a strand. These strands can be processed into various forms through various processing processes and applied to various fields. For example, the strand can be chopping, cut to a certain length (eg, 3 to 20 mm), and dried to obtain the form of chopped strands. The chop strand is easy to process when compounding, and can be used in thermoplastic or thermosetting resins (e.g., polyamide, polysulfone, polyethersulfone, polyimide, polyetherimide, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide) , modified polyphenylene oxide (mPPO) resin, liquid crystal polymer (LCP, Liquid Crystal Polymer), etc.) or thermosetting resin, it can be applied as a reinforcing material for various electrical and electronic products, automobile parts, and mechanical parts.

<Glass fiber reinforced polymer composite material>

The present invention provides a glass fiber reinforced polymer composite material containing the above-described glass fibers. The mechanical strength of the thermoplastic or thermosetting resin can be strengthened by the glass fiber coated with the sizing composition according to the present invention, thereby improving the mechanical strength of the composite material. The composite material can be processed into various forms and applied to various fields such as airplane parts, ship parts, automobile parts, sporting goods, and electrical and electronic products.

The thermoplastic or thermosetting resin is not particularly limited as long as it is known in the art, and includes, for example, polyamide, polysulfone, polyethersulfone, polyimide, polyetherimide, polyethylene terephthalate, polybutylene terephthalate, and polyphenylene sulfide. , modified polyphenylene oxide (mPPO) resin, liquid crystal polymer (LCP), etc.

The mixing ratio of the glass fiber and thermoplastic or thermosetting resin is not particularly limited, and may be, for example, a weight ratio of 5:95 to 60:40, and another example, 10:90 to 50:50.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are only intended to aid understanding of the present invention and do not limit the scope of the present invention to the examples in any way.

Sizing composition preparation

[Production Example 1-14]

The sizing composition of each production example was prepared according to the compositions in Tables 1 to 3 below. Table 1-3 below shows only the solid content of each component (unit: weight %), and the actual input amount is the content converted according to the solid content of each component.

The film former was added to deionized water in an amount equivalent to twice the actual amount of the film former and stirred to prepare a diluted film former. The silane coupling agent was added to deionized water in an amount equivalent to 10 times the actual amount of the silane coupling agent and stirred to perform hydrolysis. After complete hydrolysis was performed until the silane stirring solution became transparent, the hydrolyzed silane was added to the film former dilution solution prepared above and stirred for more than 3 hours. Thereafter, the sizing composition of each production example was prepared by adding deionized water so that the solid content of the entire sizing composition was 5.1% by weight.

In this example, the sizing composition of each production example was prepared by the above method, but as long as the solid content of each component satisfies the conditions of Table 1-3, the dehydrator used in dilution of the film former and hydrolysis of the silane coupling agent was used. The amount of ionized water can be changed.

Polyurethane Resin 1: Polyurethane dispersion (polyether-polyol, Tg -40 ℃, Mw 200,000 g/mol, elongation 1,000%)

Polyurethane Resin 2: Polyurethane dispersion (polyester-polyol, Tg -20 ℃, Mw 260,000 g/mol, elongation 800%)

Polyurethane Resin 3: Polyurethane dispersion (polyester-polyol, Tg -30 ℃, Mw 340,000 g/mol, elongation 600%)

Polyurethane Resin 4: Polyurethane dispersion (polyester-polyol, Tg 10°C, Mw 780,000 g/mol, elongation 300%)

Acrylic resin: SAN emulsion (styrene acrylonitrile-based acrylic resin, Mn 75,000 g/mol, Mw 4,900,000 g/mol)

Blocked isocyanate 1: NCO 10%, de-blocking temp. 170℃

Blocked isocyanate 2: NCO 18%, de-blocking temp. 200℃

Blocked isocyanate 3: NCO 2.5%, de-blocking temp. 170℃

Carbodiimide resin: V-02-L2 (Nishinbo), NCN content 385 g/eq

Oxazoline-based resin: K-2010E (Nippon Shokubai), oxazoline content 550 g/eq

Epoxy resin: Epoxy emulsion (phenol novolac epoxy, KEM-1020-55 (Kukdo Chemical), EEW 210 g/eq)

Silane coupling agent: γ-aminopropyltriethoxysilane (Momentive)

Manufacturing of glass fiber and polymer composite materials

[Experimental Example 1-14]

The sizing composition prepared in each production example was applied, and the glass fibers fiberized to a diameter of 10 ± 1 ㎛ were treated with a roll coating method through a bushing, cut into 4 mm lengths, and the glass of each experimental example in the form of a chopped strand was formed. Fiber was manufactured. The sizing agent content in the manufactured glass fiber is 0.4 to 0.6 parts by weight based on 100 parts by weight of glass fiber (based on solid content).

After extrusion by mixing 40 parts by weight of each manufactured glass fiber and 60 parts by weight of modified polyphenylene oxide (PPO (BLUESTAR LXR035)/HIPS (Hyundai EP S834), 60/40 wt%), injection specimens were made according to ASTM D256 standard. was produced.

The physical properties of the polymer composite materials prepared in each experimental example were measured by the following method, and the results are shown in Tables 4 to 6 below.

robbery

Tensile strength, impact strength, and flexural strength were measured according to ASTM D638, D256, and D790.

Pressure Cooker Test (PCT) strength

After aging each specimen for 144 hours at 120°C and 100% RH, the tensile strength was measured according to ASTM D638. Hydrolysis resistance was confirmed from the tensile strength retention rate.

As confirmed from the results in Tables 4 to 6, the sizing compositions of Preparation Examples 1-9 according to the present invention showed excellent initial strength, PCT strength, and PCT retention rate.

On the other hand, Preparation Example 10 in which an acrylic resin was used instead of a polyurethane resin as the first film former, Preparation Example 11 in which an epoxy resin was used instead of the resin according to the present invention as the second film former, and the content of the silane coupling agent was outside the scope of the present invention. Preparation Example 12, in the case of the sizing compositions of Preparation Examples 13 and 14 in which the mixing ratio of the first film former and the second film former is outside the scope of the present invention, the initial strength or PCT strength compared to the sizing composition of Preparation Examples 1-9 The physical properties were found to be inferior.

Claims (8)

A first film former comprising a polyurethane resin; A second film forming agent comprising at least one resin selected from block isocyanate resin, carbodiimide resin, and oxazoline resin; And a sizing composition comprising a silane coupling agent,
Based on the total solid content of the sizing composition, the silane coupling agent is included in an amount of 25 to 55% by weight,
A sizing composition wherein the polyurethane resin has a glass transition temperature of -70 to 0° C., a weight average molecular weight of 30,000 to 1,000,000 g/mol, and a tensile elongation of 400% to 1,300%. delete The sizing composition according to claim 1, wherein the isocyanate group content (NCO%) of the block isocyanate resin is 3 to 30% based on solid content. The sizing composition according to claim 1, wherein the equivalent weight (molecular weight per mole of carbodiimide) of the carbodiimide group (N=C=N) in the carbodiimide resin is 300 to 600. The sizing composition according to claim 1, wherein the oxazoline group content in the oxazoline-based resin is 100 to 600 equivalents (molecular weight per mole of oxazoline group). The sizing composition of claim 1, comprising 40 to 60% by weight of the first film former and 3 to 15% by weight of the second film former, based on the total solids of the sizing composition. Glass fiber surface treated with the sizing composition according to any one of claims 1 and 3 to 6. A glass fiber reinforced thermoplastic or thermoset polymer composite material comprising the glass fiber according to claim 7.