KR102114399B1 - Polyurethane resin and sizing composition containing the same - Google Patents

Abstract

The present invention relates to a polyurethane resin excellent in heat resistance and strength and a sizing composition comprising the same.

Description

Polyurethane resin composition and sizing composition using same {Polyurethane resin and sizing composition containing the same}

The present invention relates to a polyurethane resin excellent in heat resistance and strength and a sizing composition comprising the same.

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

In general, after melting various oxides forming a glass, a thin filament-like glass filament is extracted through a bushing, coated with a sizing composition, and then combined to prepare a strand. Next, it is processed in various forms and applied to various fields. Glass fibers are processed into chopped strands cut into lengths of 3 to 20 mm to be used to manufacture thermoplastics as reinforcements. In general, glass fibers are uniformly dispersed in a molten thermoplastic through a compounding process to produce glass fiber reinforced plastic pellets, and then injected to produce glass fiber reinforced thermoplastic plastic molded articles of a desired shape.

At this time, when the compatibility or interfacial adhesion between the glass fiber surface and the thermoplastic is poor, the reinforcing effect of the glass fiber is lowered, resulting in a problem that the strength of the final molded product is poor. In addition, the compounding and injection processes are performed at a high temperature of 200 ° C. or higher, and when the heat resistance of the sizing composition used for the surface treatment of glass fibers is poor, there are problems such as deterioration of strength and color change (yellowing) of molded products due to thermal decomposition. Occurs.

Efforts have been made to solve these problems, and for example, Japanese Patent No. 3,844,840 discloses a composition for sizing glass fibers containing a polyurethane dispersion in which an ionic emulsifier and a nonionic emulsifier are mixed. However, due to the high equivalent of the polyether-based nonionic emulsifier contained in the polyurethane dispersion, the heat resistance of the dispersion is poor, and there is a problem that yellowing easily occurs in the glass fiber-containing plastic to which the sizing composition is applied. Therefore, there is still a need for a sizing composition that satisfies both the compatibility and mechanical properties of the glass fiber and the thermoplastic polymer resin.

The present invention provides a polyurethane resin composition having excellent compatibility and heat resistance with glass fibers and thermoplastic polymer resins, and a sizing composition comprising the same. In addition, the sizing composition of the present invention suppresses thermal decomposition in an extrusion and injection process performed at a high temperature of 230 ° C. or higher, and has excellent mechanical strength and low color fluctuation. Provided is a fiber-reinforced thermoplastic polymer composite material.

The present invention includes a polyol compound, an isocyanate compound, an ionic compound, a nonionic compound and a chain extender, and the nonionic compound provides a polyurethane resin composition that is a compound containing an isocyanate trimer.

In addition, the present invention provides a sizing composition comprising the aforementioned polyurethane resin composition.

In addition, the present invention provides a glass fiber reinforced thermoplastic polymer composite material including the glass fiber reinforcement treated with the aforementioned sizing composition.

The sizing composition comprising the polyurethane resin composition of the present invention provides a glass fiber reinforcement and a glass fiber reinforced thermoplastic polymer composite material having excellent color and strength by suppressing thermal decomposition.

Hereinafter, the present invention will be described in detail. However, it is not limited only by the following contents, and each component may be variously modified or selectively mixed as necessary. Therefore, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

<Polyurethane resin composition>

The polyurethane resin composition according to the present invention includes a polyol compound, an isocyanate compound, an ionic compound, a nonionic compound and a chain extender. Looking at the composition of the polyurethane resin composition of the present invention as follows.

Polyol compounds

A polyol compound means a compound having two or more hydroxyl groups (OH) in a molecule. Examples of the polyol compound include polyether-based polyols such as polypropylene glycol and polytetramethylene glycol; A compound polymerized by polycondensation of dihydric or higher alcohol components such as ethylene glycol, propanediol, butanediol, and trimethylolpropane with acid components such as adipic acid, phthalic acid, isophthalic acid, and terephthalic acid; Polyester polyols polymerized by ring-opening reaction of cyclic monomers such as caprolactone; And a carbonate-based polyol having a carbonate-based continuous structure in the main chain, but is not limited thereto.

The hydroxyl value (OH Value) of the polyol compound may be in the range of 30 to 150 mgKOH / g, for example, in the range of 50 to 120 mgKOH / g. When the hydroxyl value of the polyol compound exceeds 150 mgKOH / g, focusability and workability may be deteriorated due to over-hardening of the polyurethane resin, and when it is less than 30 mgKOH / g, the strength of the glass fiber reinforced thermoplastic may be reduced.

The content of the polyol compound may be 40 to 75 parts by weight, for example, 50 to 70 parts by weight based on 100 parts by weight of the total solid content of the polyurethane resin composition. When the polyol compound is used in an amount in the above-described range, it exhibits an appropriate level of glass fiber focusing property, and can express excellent glass fiber reinforced thermoplastic plastic strength.

Isocyanate compounds

The isocyanate compound reacts with the polyol to form a urethane bond. Typically, as an isocyanate compound used to form a urethane bond, a compound having two or more isocyanate groups per molecule is used.

The isocyanate compound is one of toluene diisocyanate (TDI), methylene diphenyl isocyanate (MDI), meta-tetramethyl xylene diisocyanate (TMXDI), isophorone diisocyanate (IPDI), methylene dicyclodiisocyanate (H12MDI) The above may be used, but is not limited thereto. For example, the isocyanate compound may include one or more of meta-tetramethyl xylene diisocyanate (TMXDI), isophorone diisocyanate (IPDI), and methylene dicyclodiisocyanate (H12MDI).

The content of the isocyanate compound may be 15 to 40 parts by weight, for example, 20 to 30 parts by weight based on 100 parts by weight of the total solid content of the polyurethane resin composition. When the isocyanate compound is used in an amount in the above-mentioned range, it exhibits an appropriate level of glass fiber focusing property, and can express excellent glass fiber reinforced thermoplastic plastic strength.

Ionic compounds

An ionic compound means a compound having one or more anionic or cationic functional groups per molecule. The anionic functional group may be, for example, one or more of carboxylic acid, sulfonic acid and phosphate, and the cationic functional group may be, for example, a quaternary amine or a protonated amine.

As the ionic compound, a conventional ionic compound used in the art may be used. For example, the ionic compound includes a polyhydric alcohol containing at least one of dimethylolpropionic acid, dimethylolbutanoic acid, phosphoric acid or sulfonic acid, or a polyvalent alcohol containing at least one of ammonium salt, sulfonate or phosphate Alcohol or the like can be used. The polyhydric alcohols may be used alone or in combination of two or more.

The content of the ionic compound may be 2 to 10 parts by weight, for example, 3 to 8 parts by weight based on 100 parts by weight of the total solid content of the polyurethane resin composition. When the content of the ionic compound is less than 2 parts by weight, the water dispersion stability is poor, so storage stability such as sedimentation of solids during storage may be inferior. When it exceeds 10 parts by weight, the viscosity of the water-dispersed urethane resin is increased and the size is produced. Stability may be inferior.

Nonionic compounds

Conventional nonyl phenol ethoxide (Nonyl phenol ethoxide) -based non-ionic compound was used, but its use is legally limited due to toxicity to the living body. Alkyl ethoxyde-based and octyl phenol ethoxylate-based nonionic compounds were used as substitute materials, but the final glass fiber reinforced thermoplastic due to low compatibility with polyurethane resin and poor heat resistance There is a problem in that yellowing occurs in the polymer composite material and the strength is lowered.

The polyurethane resin composition of the present invention uses a compound containing an isocyanate trimer (Isocyanurate) as a nonionic compound. Since the isocyanate trimer structure has thermal stability and chemical stability, the polyurethane resin containing the same may have excellent heat resistance and strength characteristics as well as pH stability. In addition, since the isocyanate trimer structure has excellent compatibility with the polyurethane resin, it serves to provide excellent heat resistance and non-yellowing property to the polyurethane resin composition. In addition, the nonionic compound of the present invention has an isocyanate functional group in the molecule, thereby forming a urethane polymer having a nonionic emulsifier in the molecule by chemically bonding to the terminal of the polymerized urethane polymer. Therefore, problems such as a decrease in heat resistance and a decrease in strength due to the retention of a non-reactive nonionic compound can be significantly improved.

For example, the nonionic compound may be a compound represented by Formula 1 below.

<Formula 1>

In the above formula,

R1 is toluene, alkylenediphenyl having 1 to 3 carbons, isophorone, or alkyl having 1 to 10 carbons,

R2 is an alkyl group having 1 to 5 carbon atoms,

n is a number between 1 and 25.

In the compound represented by Formula 1, R 1 may be toluene, alkylene diphenyl having 1 to 3 carbons, isophorone, or alkyl having 1 to 10 carbons, for example, toluene, methylenediphenyl, isophorone, and hexyl It may be one selected from the group consisting of, other examples may be isophorone or hexyl. R2 may be an alkyl group having 1 to 5 carbon atoms, for example, a methyl group or an ethyl group. The polyether polymerization degree (n) may be a number between 1 and 25, for example between 5 and 20, and in other examples between 7 and 15. If n is less than 1, the liquid stability of the polyurethane resin is poor, and when n is more than 25, the strength of the glass fiber reinforced thermoplastic may be poor.

The nonionic compound may include 0.3 to 2.0 isocyanate functional groups per molecule, such as 0.6 to 1.8, and 0.9 to 1.5 as another example. The isocyanate functional group can form a bond with the polyurethane resin, and as a result, it can impart excellent strength and heat resistance to the polyurethane resin. When the number of isocyanate functional groups per molecule is less than 0.3, the strength of the glass fiber injection product is inferior, and when it is more than 2.0, the viscosity of the polyurethane resin is too high and stability may be inferior.

The content of the nonionic compound may be 3 to 15 parts by weight, for example, 4 to 10 parts by weight based on 100 parts by weight of the total solid content of the polyurethane resin composition. When the nonionic compound is less than 3 parts by weight, the stability of the sizing composition is lowered, and when it is more than 15 parts by weight, the strength of the glass fiber reinforced thermoplastic may be lowered.

Chain extender

The chain extender serves to extend the chain of residual isocyanate end groups of the polymer. As the chain extender, conventional compounds used in the art may be used. For example, the chain extender may be a compound having two isocyanate reactive groups, and the isocyanate reactive group may be active hydrogen.

As the chain extender, for example, a material having a molecular weight of 200 or less and having two or more active hydrogens in the molecule can be used. As the chain extender, chain extenders belonging to amine-based compounds and diol-based compounds may be used without particular limitation, but are not limited thereto. For example, one or more selected from ethylene glycol, diethylene glycol, triethylene glycol, cyclohexanediol, ethylenediamine, diethanolamine, monoethanolamine, isophoronediamine, and adipic dihydrazide may be mixed.

The content of the chain extender may be 0.1 to 7 parts by weight, for example, 1 to 5 parts by weight based on 100 parts by weight of the total solid content of the polyurethane resin composition. When the content of the chain extender is less than 0.1 part by weight, the strength of the thermoplastic plastic may be lowered due to a decrease in the molecular weight of the urethane resin, and if it is more than 7 parts by weight, there may be a problem of viscosity rise and size stability of the water-dispersible urethane resin. Can be.

The polyurethane resin composition may be prepared by a method known in the art, for example, may be prepared by the following manufacturing process. After preparing a mixture of a polyol compound, an isocyanate compound, an ionic compound, a nonionic compound and a chain extender, it can be prepared by dispersing it in water in a uniform particle form.

<Sizing composition>

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

The film forming agent serves to strengthen the focus between the glass fibers and impart compatibility with the thermoplastic resin. As the film forming agent, the aforementioned polyurethane resin composition may be used. In addition, if necessary, one or more of other types of polyurethane resin, water-soluble epoxy resin, water-soluble polypropylene resin, water-soluble maleic acid-modified polypropylene resin, water-soluble maleic acid / fatty acid-modified polypropylene resin, water-soluble polyester resin, acrylic emulsion resin You can add

-(아미노에틸)-

-아미노프로필트리에톡시실란, 디메틸디메톡시실란, 비닐메틸디메톡시실란, γ-메타크릴록시프로필메틸디메톡시실란, γ-아크릴록시프로필메틸디메톡시실란, γ-글리시독시프로필메틸디메톡시실란, γ-글리시독시프로필메틸디메톡시실란, γ-아미노프로필메틸디메톡시실란, γ-우레이도프로필트리메톡시실란, γ-우레이도프로필트리에톡시실란, γ-이소시아네이토프로필트리메톡시실란, γ-이소시아네이토프로필트리에톡시실란, 페닐트리에톡시실란 및 페닐트리메톡시실란으로 이루어진 군에서 선택된 1종 이상일 수 있다.The organosilane coupling agent serves to impart interfacial adhesion between the glass fiber surface and the organic material. Non-limiting examples of the organosilane coupling agent are methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ -Methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, β- (3,4-epoxycyclo Hexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-

-(Aminoethyl)-

-Aminopropyltriethoxysilane, dimethyldimethoxysilane, vinylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane , γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-isocyanatopropyltrime It may be at least one selected from the group consisting of oxysilane, γ-isocyanatopropyl triethoxysilane, phenyltriethoxysilane and phenyltrimethoxysilane.

The sizing composition may include 30 to 92 parts by weight of the film former and 5 to 15 parts by weight of the organosilane coupling agent based on 100 parts by weight of the total solids of the sizing composition. When the content range of the film-forming agent and the organosilane coupling agent satisfies the above-described range, the focusing force of the glass fiber may be enhanced, and compatibility with the polymer resin may be secured.

The sizing composition of the present invention may further include additives commonly used in the sizing composition within a range that does not impair the intrinsic properties of the sizing composition. Non-limiting examples of additives usable in the present invention include a focusing auxiliary resin for improving the focusability of glass fibers, a lubricant for imparting surface lubricity, a buffer for adjusting pH, a color stabilizer, etc., which are used alone. Or two or more of them can be used in combination.

Such additives may be appropriately added within a content range known in the art, for example, about 0.1 to 10 parts by weight based on 100 parts by weight of the total solids of the sizing composition, and may be about 0.1 to 1 parts by weight. When the content of the additive is within the aforementioned range, the appearance and hardness of the glass fiber may be improved.

<Glass fiber reinforcement>

The present invention provides a glass fiber reinforcement surface-treated with the aforementioned sizing composition.

The glass fiber substrate usable in the present invention is not particularly limited as long as it is known in the art. Examples include, but are not limited to, E-glass, D-glass, S-glass, NE-glass, T-glass, Q-glass, and the like.

The glass fiber may have a fiber diameter of 5 to 20 μm, for example, 8 to 15 μm. When the fiber diameter is less than the above range, excessive fiber damage may occur during the extrusion and injection process of the glass fiber, and when it exceeds the above range, the strength reinforcement effect of the glass fiber may be deteriorated due to a decrease in the surface area of the glass fiber. The fiber length of the glass fiber may be 0.5 to 20 mm, for example, 1 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 occurring during the extrusion and injection process, and when it exceeds the above range, the dispersion of the glass fiber reinforcing material becomes poor and strength reinforcement The effect may be poor.

The method for applying the sizing composition is not particularly limited, and for example, there is an immersion method, a roll coating method, a die coating method, a gravure coating method, a spray coating method, a flow coating method, and the like. For example, when the sizing composition is applied to the glass fiber substrate through the immersion method, the immersion time may be about 0.5 seconds to 1 minute.

The application amount (usage amount) of the sizing composition is not particularly limited, but may be 0.1 to 2 parts by weight, for example, 0.5 to 1.5 parts by weight based on 100 parts by weight of the solid content of the glass fiber reinforcement material. When the content of the sizing composition is less than the above range, the adhesive strength between the glass fiber reinforcement and the thermoplastic resin may be inferior, and the focusing force of the glass fiber bundle may be inferior. On the other hand, if it exceeds the above range, the glass fiber bundle becomes excessively large, resulting in poor workability, and the strength of the glass fiber-reinforced thermoplastic polymer composite material may be inferior.

The glass fiber coated with the sizing composition is usually in the form of a filament, and several strands (for example, 4000 pieces) are joined to form a strand. These strands are processed in various forms through various processing processes, and can be applied to various fields. For example, the strand may be chopped strands by chopping and cutting to a certain length (eg, 2 to 5 mm) and drying. The 촙 strand has good color discoloration due to heat, and has excellent chemical resistance, color, and mechanical strength, and thus is applied to various electrical and electronic products, automobile parts, and mechanical parts together with thermoplastic resins or thermosetting resins, such as polyamide resins. Can be applied in the field.

<Glass fiber reinforced thermoplastic polymer composite material>

The present invention provides a glass fiber-reinforced thermoplastic polymer composite material comprising the above-described glass fiber reinforcement. At this time, the mechanical strength of the thermoplastic resin is strengthened by the glass fiber, so that the mechanical strength of the composite material can be improved. These composite materials can be processed into various forms and applied to various fields, such as airplane parts, ship parts, automobile parts, sports goods, electrical and electronic products, and the like.

The thermoplastic resin is not particularly limited as long as it is known in the art, and for example, polyamide. Since polyamide has excellent compatibility with glass fibers coated with the sizing composition, the mechanical strength of the composite material may be further improved.

The mixing ratio of the glass fiber and the thermoplastic resin is not particularly limited, and may be, for example, 30:70 to 50:50 weight ratio. When the mixing ratio of the glass fiber and the thermoplastic resin is the aforementioned ratio, mechanical properties such as tensile strength and impact strength may be further improved.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are only to aid the understanding of the present invention, and the scope of the present invention is not limited to the examples in any sense.

[Production Example A]-Preparation of nonionic compound 1

871.5 g of hexamethylene diisocyanate trimer (NPU, N3300) was added to a round bottom flask equipped with a stirring device, a temperature control device, and a nitrogen supply device, and the temperature was raised to 60 ° C. 1,428 g of methoxypolyethylene glycol M500 (Clariant, molecular weight: 500) and 0.5 g of phosphoric acid were added, maintained at 90 ± 5 ° C for 5 hours, and then confirmed that the residual NCO% was 2.9% to complete the reaction to terminate the nonionic compound 1 Got In the nonionic compound 1, in Formula 1, R1 is a hexyl group, R2 is a methyl group, the polyether polymerization degree (number average value; n) is 11, and the number of isocyanate functional groups per molecule is 1.3.

[Production Example B]-Preparation of nonionic compound 2

828.7 g of hexamethylene diisocyanate trimer (NPU, N3300) was added to a round bottom flask equipped with a stirring device, a temperature control device, and a nitrogen supply device, and the temperature was raised to 60 ° C. After adding 970.9 g of methoxy polyethylene glycol M350 (Clariant, molecular weight: 350) and 0.5 g of phosphoric acid, and maintaining it at 90 ± 5 ° C. for 5 hours, confirming that the residual NCO% is 3.4% to complete the reaction to terminate the nonionic compound 2 Got In the nonionic compound 2, in Formula 1, R1 is a hexyl group, R2 is a methyl group, the polyether polymerization degree (number average value; n) is 7.6, and the number of isocyanate functional groups per molecule is 1.2.

[Comparative Preparation Example]-Preparation of Nonionic Compound 3

215 g of hexamethylene diisocyanate trimer (NPU, N3300) was added to a round bottom flask equipped with a stirring device, a temperature control device, and a nitrogen supply device, and the temperature was raised to 60 ° C. After adding 785 g of methoxy polyethylene glycol MPEG-2000 (Hanchon Chemical Co., Ltd., molecular weight: 2,000) and 0.5 g of phosphoric acid, and maintaining it at 90 ± 5 ° C. for 5 hours, confirming that the residual NCO% was 2.9%, the reaction was completed to complete the ratio. The ionic compound 3 was obtained. In the nonionic compound 2, in Formula 1, R1 is a hexyl group, R2 is a methyl group, the polyether polymerization degree (number average value; n) is 45, and the number of isocyanate functional groups per molecule is 2.3.

[Production Example 1]-Preparation of polyurethane resin 1

486.1 g of polyester polyol (OH Value: 56.1) obtained through condensation reaction of 1,4-butanediol, adipic acid, and isophthalic acid in a round bottom flask equipped with a stirring device, a temperature control device and a nitrogen supply device, dimethylolpropionic 29.3 g of acid and 71.4 g of N-methylpyrrolidone were added, heated to 80 ° C., maintained for 1 hour, and then cooled to 60 ° C. 53.0 g of isophorone diisocyanate and 145.6 g of methylene dicyclodiisocyanate were added, heated to 85 ± 5 ° C, maintained for 4 hours, and after confirming that the residual NCO% was 3.5%, nonionic compound 1 of Preparation Example 5 was 52.0. g was added and cooled to 40 ± 3 ° C. After the cooling was completed, 23.2 g of triethylamine was added and maintained for 10 minutes. After completion of the maintenance, 970.7 g of 30 ± 3 ° C deionized water was uniformly added for 10 minutes to disperse it, and 139.7 g of a 20% solution of isophorone diamine was added, and then maintained at 35 ± 5 ° C until all residual NCO disappeared. Polyurethane resin 1 (solid content: 40.2%, viscosity: 180 cps) was obtained.

[Production Example 2]-Preparation of polyurethane resin 2

Polyurethane resin 2 (solid content: 40.4%, viscosity: 210 cps) was obtained in the same manner as in Production Example 1, except that the nonionic compound 2 of Production Example B was used instead of the nonionic compound 1 of Production Example A.

[Comparative Production Example 1]-Preparation of polyurethane resin 3

Polyurethane resin 3 (solid content: 40.1%, in the same manner as in Production Example 1), except that an Octyl phenyl polyethoxylate-based nonionic compound (OP-30, Hannong Chemical Co., Ltd.) was used instead of Nonionic Compound 1 of Preparation Example A. Viscosity: 130 cps).

[Comparative Production Example 2]-Preparation of polyurethane resin 4

Polyurethane resin 4 (solid content: 40.1%, viscosity: 95 cps) was obtained in the same manner as in Production Example 1, except that Nonionic Compound 3 of Comparative Production Example was used instead of Nonionic Compound 1 of Production Example A.

[Example 1-4 and Comparative Example 1-2]-Preparation of sizing composition

Using the polyurethane resin prepared according to Preparation Example 1-2 and Comparative Preparation Example 1-2, the sizing compositions of Examples 1-4 and Comparative Examples 1-2 were prepared according to the composition of Table 1 below. The solid content is measured by treating the sizing composition at 150 ° C for 30 minutes and measuring the proportion of solid content remaining.

γ-aminopropyltriethoxysilane (A1100, Momentive, 62% solids)

[Experimental Example-Property evaluation]

Using the sizing composition prepared in Examples 1-4 and Comparative Examples 1-2, the fiberglass fiberized to a diameter of 10 ± 1 μm through a bushing was treated with a roller coating method and cut into 3 mm lengths to form a strand strand. A glass fiber reinforcement was prepared. The thus prepared glass fiber reinforcement was applied to a polyamide-6 (nylon 6) matrix resin to prepare a glass fiber reinforced thermoplastic polymer composite material.

The physical properties of the glass fiber reinforced material and glass fiber reinforced polyamide-6 composite material prepared by the above method were measured by the following method, and the results are shown in Table 2 below.

Organic matter content

촙 The strand sample was treated at 650 ° C. for 30 minutes to measure the proportion of organics removed.

House speed

A certain amount of chopped strand sample was sealed in a container containing iron beads to measure the rate of fiberglass cotton wool generated after 3 minutes of high-speed translation. The smaller the rate of cotton wool generation, the better the focusing speed.

Glass fiber content

After the glass fiber reinforced polyamide 6 composite material was heat treated at 650 ° C. for 3 hours, the content of the remaining glass fibers was measured.

The tensile strength

Tensile strength was measured according to ASTM D638.

Impact strength

Impact strength was measured according to ASTM D790.

Yellowing

The color index (Yellow index) of the glass fiber-reinforced thermoplastic plastic molded article was measured using a colorimeter (KONICA MINOLTA, DP-400). The higher the value, the higher the yellowness.

From the results of Table 2, it was confirmed that the glass fiber-reinforced thermoplastic polymer composite material to which the sizing composition of Example 1-4 according to the present invention was applied exhibits excellent strength and yellowing inhibitory effect. On the other hand, the glass fiber-reinforced thermoplastic polymer composite material to which the sizing composition of Comparative Example 1-2 was applied was inferior in tensile strength and impact strength compared to the example, and it was confirmed that yellowing progressed severely.

Claims (6)

A polyurethane resin composition comprising a polyol compound, an isocyanate compound, an ionic compound, a nonionic compound and a chain extender,
The isocyanate compound is a compound that does not contain an isocyanate trimer,
The nonionic compound is a polyurethane resin composition that is a compound containing an isocyanate trimer. The polyurethane resin composition according to claim 1, wherein the nonionic compound is a compound represented by Formula 1 below:
<Formula 1>

In the above formula,
R1 is a residue excluding the diisocyanate group from toluene diisocyanate, a residue excluding the diisocyanate group from alkylene diphenyl diisocyanate having 1 to 3 carbon atoms, a residue excluding the diisocyanate group from isophorone diisocyanate, or an alkyl diisocyanate having 1 to 10 carbon atoms. Residues excluding diisocyanate groups,
R2 is an alkyl group having 1 to 5 carbon atoms,
n is a number between 1 and 25. The polyurethane resin composition according to claim 1, wherein the nonionic compound is a compound having 0.3 to 2.0 isocyanate functional groups per molecule. According to claim 1, Based on 100 parts by weight of the total solids of the polyurethane resin composition, 40 to 75 parts by weight of polyol compound, 15 to 40 parts by weight of isocyanate compound, 2 to 10 parts by weight of ionic compound, 3 to 3 parts of nonionic compound A polyurethane resin composition comprising 15 parts by weight and 0.1 to 7 parts by weight of a chain extender. A film former and an organosilane coupling agent,
The sizing composition wherein the film-forming agent comprises the polyurethane resin composition according to any one of claims 1 to 4. The sizing composition of claim 5, comprising 30 to 92 parts by weight of the film former and 5 to 15 parts by weight of the organosilane coupling agent, based on 100 parts by weight of the total solids of the sizing composition.