KR20210093056A - Size composition and glass fiber reinforcement using the same - Google Patents

Abstract

The present invention relates to a size composition having excellent impact strength and focusing power, and a glass fiber reinforcing material manufactured by using the same. The present invention is the size composition comprising a film former and an organosilane coupling agent, in which an organic resin and an organic polysiloxane resin are contained in a weight ratio of 50 : 50 to 98 : 2.

Description

Size composition and glass fiber reinforcement using the same

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

Glass fibers are used for various purposes in various industrial fields due to their characteristics such as high strength, insulation, non-combustibility, dimensional stability, and chemical resistance. In particular, E-Glass Fiber has excellent electrical properties and weathering resistance, and is used as a strength reinforcing material for building materials and polymer materials using electrical insulation properties.

In general, after melting various oxides that form glass, thin filaments of glass are extracted through bushings, coated with a size composition, and braided to form strands. Next, it is processed into various shapes and applied to various fields. For example, glass fibers are processed in the form of chopped strands cut to a length of 3 to 20 mm, and used as a reinforcing material for manufacturing a thermoplastic plastic molded article. In general, glass fibers are uniformly dispersed in the molten thermoplastic through a compounding process to prepare glass fiber-reinforced plastic pellets, and then, by injecting them, a glass fiber-reinforced thermoplastic plastic molded article of a desired shape is manufactured.

The interfacial adhesive size composition has excellent compatibility and reactivity with engineering plastics, and when a glass fiber reinforcement coated with the size composition is applied as a reinforcement for engineering plastics, strong bonding is formed at the interface between glass fibers and engineering plastics. . Due to these properties, the interfacial adhesive size composition has been widely applied as a reinforcing material for improving the tensile strength and heat resistance of engineering plastics. For example, Korean Patent Publication No. 10-1812894, etc. discloses a glass fiber composite material composition that maximizes the interfacial adhesion between glass fibers and engineering plastics.

However, the strong adhesion between the glass fiber and the engineering plastic excessively increases the hardness of the glass fiber reinforced engineering plastic, thereby reducing the impact strength. In particular, in the case of a non-crystalline polymer such as polycarbonate, it has excellent impact strength due to high viscoelasticity, but there is a problem in that the impact strength is extremely reduced when reinforced with an interfacial adhesive glass fiber reinforcing material.

The present invention provides an interfacial non-adhesive size composition that exhibits excellent impact strength and thermal stability.

In addition, the present invention provides a size composition applicable as a thermoplastic reinforcing material, which has excellent collection speed and exhibits excellent workability during an extrusion operation that is mixed with a thermoplastic plastic.

The present invention also provides a glass fiber reinforcement coated with the size composition described above.

The present invention provides a size composition comprising an organic resin and an organic polysiloxane resin in a weight ratio of 50:50 to 98:2, and a film former and an organosilane coupling agent.

In addition, the present invention provides a glass fiber reinforced material coated with the above-mentioned size composition and a glass fiber reinforced thermoplastic polymer composite material comprising the same.

The non-adhesive size composition of the present invention exhibits excellent impact strength and thermal stability due to its interfacial non-adhesive properties when applied as a thermoplastic reinforcing material. In addition, the non-adhesive size composition of the present invention exhibits excellent workability during extrusion operation to be mixed with engineering plastics by having an excellent collection rate.

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

<size composition>

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

As used herein, "number average molecular weight" and "weight average molecular weight" are measured by a conventional method known in the art, and may be measured by, for example, a gel permeation chromatograph (GPC) method. A functional group such as "acid value" may be measured by a conventional method known in the art, for example, may represent a value measured by a method of titration.

film former

The film former serves to coat the surface of the glass fibers and impart adhesion between the glass fibers to strengthen the focusing between the glass fibers.

In the present invention, the film former may exhibit non-adhesive properties through lowering of compatibility with engineering plastics, which are typically polar polymers. In the case of a non-crystalline polymer such as polycarbonate, it has excellent impact strength due to high viscoelasticity, but when reinforced with an interfacial adhesive glass fiber reinforcing material, the impact strength may be reduced. When the non-crystalline polymer is reinforced with a glass fiber reinforcing material to which a size composition exhibiting non-adhesive properties is applied, the impact strength can be improved.

The film former may include an organic resin and an organic polysiloxane resin.

The organic resin may be a water-soluble organic resin, and non-limiting examples of the water-soluble organic resin include water-dispersed polyurethane resin, water-dispersed epoxy resin, water-soluble polypropylene resin, water-soluble maleic acid-modified polypropylene resin, water-dispersed maleic acid-modified polyethylene /polypropylene copolymer resin, water-soluble maleic acid/fatty acid modified polypropylene resin, polyester resin, acrylic emulsion resin, etc. are mentioned. These can be used individually or in mixture of 2 or more types. For example, the organic resin may be a maleic acid-modified polypropylene resin or a maleic acid-modified polyethylene/polypropylene copolymer resin.

The organic resin may be included in an amount of 45 to 98% by weight, for example, 60 to 90% by weight, based on the total solid content of the size composition. If the content of the organic resin is less than 45% by weight, the bundling property between the glass fibers may be reduced, and if it is more than 98% by weight, the impact strength may be reduced by increasing the interfacial bonding strength with the engineering plastic molecule.

As the organic polysiloxane resin, an organic polysiloxane resin having non-polar and inert properties may be used. The organic polysiloxane resin is oriented on the outermost side of the glass fiber reinforcement coated with the size composition to make the glass fiber coating layer non-polar and inactivated, thereby imparting non-adhesive properties between the interface between the thermoplastic engineering plastic and the glass fiber during the extrusion kneading process. .

For example, the organic polysiloxane resin may be a methyl group-substituted polysiloxane resin, such as a polymethylsiloxane resin or a polydimethylsiloxane resin.

The organic polysiloxane resin may have a number average molecular weight (Mn) of 3,000 to 10,000 g/mol, for example, 3,000 to 5,000 g/mol, and a weight average molecular weight (Mw) of 15,000 to 50,000 g/mol, for example 15,000. to 25,000 g/mol, and the acid value may be 1 to 20 mgKOH/g, for example, 5 to 10 mgKOH/g. When the physical property value of the organic polysiloxane resin falls within the above-mentioned range, it is suitable for application as a coating material due to excellent film formation.

The organic polysiloxane resin may be included in an amount of 1 to 50% by weight, for example, 5 to 30% by weight, based on the total solid content of the size composition. When the content of the organic polysiloxane resin is less than 1% by weight, adhesive properties between the size coating layer and the thermoplastic engineering plastic may be expressed, and when the content of the organic polysiloxane resin is more than 50% by weight, the bundling property may be inferior.

The organic resin and the organic polysiloxane resin may be blended in a weight ratio of 50: 50 to 98: 2, for example, 60: 40 to 95: 5, in another example, 80: 20 to 90: 10 by weight. When the organic resin and the organic polysiloxane resin are used in a blending ratio within the above range, it is possible to further improve the impact strength by enhancing the focusing between the glass fibers and at the same time exhibiting an interfacial non-adhesive property to the engineering plastic. When the mixing ratio of the organic resin and the organic polysiloxane resin is less than 50: 50 weight ratio, the bundling property may be inferior, and when the mixing ratio exceeds 98: 2 weight ratio, the adhesive property between the size coating layer and the thermoplastic engineering plastic is expressed and the impact strength is reduced can be inferior

organosilane coupling agent

The organosilane coupling agent serves to impart adhesion between the inorganic glass and the organic film former or thermoplastic engineering plastic. In the organosilane coupling agent, the alkylsiloxane group is hydrolyzed in water and oriented in the form of an organosilanol by an ionic bond with the silanol group on the surface of the glass fiber, and then a siloxane bond is formed through a high-temperature dehydration condensation reaction. In this case, the organosilane coupling agent is oriented or bonded to the surface of the glass fiber, and serves to protect the glass surface and serve as a coupling agent for providing interfacial adhesion between the film former and the glass.

The organosilane coupling agent is not particularly limited as long as it is commonly used in the art. Non-limiting examples of the organosilane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxy Propyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltrime Toxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxysilane, dimethyldimethoxysilane, vinylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxy Silane, γ-acryloxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxy silane, γ-isocyanatopropyltrimethoxysilane, and γ-isocyanatopropyltriethoxysilane, and these may be used alone or in combination of two or more. For example, the organosilane coupling agent may be γ-aminopropyltriethoxysilane.

The organosilane coupling agent may be included in an amount of 1 to 10% by weight, for example, 3 to 7% by weight, based on the total solid content of the size composition. When the content of the organosilane coupling agent is less than 1% by weight, the bundling property of the glass fiber bundle is inferior, and workability during extrusion may be poor. When the content of the organosilane coupling agent is greater than 10% by weight, an excess of organic functional groups during extrusion processing The impact strength can be inferior by increasing the interfacial adhesion strength with plastic molecules.

additive

The size composition of the present invention may optionally further include additives commonly used in the size composition within a range that does not impair the intrinsic properties of the size composition. Non-limiting examples of additives usable in the present invention include a focusing auxiliary resin for improving the bundling properties of glass fibers, a lubricant for imparting surface lubricity, a buffer for adjusting pH, a color stabilizer, and the like. These may be used alone or two or more may be used in combination.

Such additives may be added within a 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 size composition. 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 size composition described above.

The glass fiber substrate usable in the present invention is not particularly limited as long as it is known in the art. For example, E-glass, D-glass, S-glass, NE-glass, T-glass, Q-glass, etc., but are not limited thereto.

The fiber diameter of the glass fiber may be 5 to 20 μm, for example, 8 to 15 μm. If the fiber diameter is less than the above range, excessive fiber damage may occur during the extrusion and injection process, and the strength of the glass fiber reinforced thermoplastic engineering plastic molded article may be inferior. If the fiber diameter exceeds the above range, the glass fiber may be damaged due to a decrease in the surface area of the glass fiber. The strength reinforcement effect may be reduced.

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 occurring during the extrusion and injection process, and if it exceeds the above range, the input of the fiber reinforcement material during the extrusion process is poor. The uniform dispersion of the glass fiber reinforcement may be poor and the strength reinforcement effect may be poor.

The coating method of the size composition is not particularly limited, and for example, there are dipping method, roll coating method, die coating method, gravure coating method, spray coating method, flow coating method, etc., but is not limited thereto. For example, when the size composition is applied to the glass fiber substrate by an immersion method, the immersion time may be about 0.5 seconds to 1 minute.

The application amount (usage amount) of the size composition is not particularly limited, but may be 0.1 to 2 parts by weight, for example, 0.3 to 1.5 parts by weight, based on 100 parts by weight of the solid content of the glass fiber reinforcing material. If the content of the size composition is less than the above range, there is a problem that the focusing force of the glass fiber bundle is inferior, so that workability in the extrusion process may be reduced, and if it exceeds the above range, compatibility with engineering plastics may be inhibited .

Glass fibers coated with the size composition are typically in the form of filaments, and several strands (eg, 4000 pieces) are braided to form strands. These strands are processed into various shapes through various processing processes, and can be applied to various fields. For example, by chopping the strand, cutting it to a predetermined length (eg, 2 to 5 mm) and drying it, it can be obtained in the form of chopped strands. Since the chopped strand has good discoloration due to heat and excellent chemical resistance, color, and mechanical strength, various electrical and electronic products, automobile parts, mechanical parts, etc. together with a thermoplastic resin or a thermosetting resin such as polycarbonate resin can be applied to

<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 reinforcing material. At this time, the mechanical strength of the thermoplastic resin is strengthened by the glass fiber, the mechanical strength of the composite material can be improved. These composite materials can be processed into various shapes and applied to various fields such as airplane parts, ship parts, automobile parts, sporting 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, polycarbonate or the like. Polycarbonate has excellent impact strength due to the non-crystalline nature of the resin itself, but the impact strength is lowered when the interfacial adhesive glass fiber reinforcement is used. When the glass fiber reinforcing material coated with the size composition according to the present invention is applied for reinforcing a thermoplastic plastic, excellent impact strength can be secured.

The mixing ratio of the glass fiber and the thermoplastic resin is not particularly limited, and for example, a weight ratio of 5: 95 to 50: 50, or 5: 95 to 15: 85 in another example may be used. When the mixing ratio of the glass fiber and the thermoplastic resin falls within the aforementioned range, mechanical properties such as impact strength may be further improved.

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

size composition preparation

[Example 1-9]

According to the composition of Table 1 below, the size composition of Examples 1-9 was prepared, respectively. Table 1 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 corresponding to twice the actual amount of the film former and stirred to prepare a diluent of the film former. The organosilane coupling agent was added to deionized water in an amount corresponding to 10 times the actual amount of the organosilane coupling agent added, followed by stirring to perform hydrolysis. After the silane stirring solution was completely hydrolyzed until transparent, the hydrolyzed silane was added to the prepared diluent film forming agent and stirred for 30 minutes to mix completely. Thereafter, the size compositions of Examples 1-9 were prepared by adding deionized water so that the total solid content of the size composition was 5 wt%.

[Comparative Example 1-2]

Except according to the composition of Table 2 below, a size composition of Comparative Example 1-2 was prepared in the same manner as in Examples 1-9.

Coupling agent 1: γ-aminopropyltriethoxysilane (solid content: 62%)

Coupling agent 2: γ-aminopropyltrimethoxysilane (solid content: 81%)

Organic resin 1: water dispersion maleic acid-modified polyethylene/polypropylene copolymer resin (weight average molecular weight (Mw) 44,000 mol/g, number average molecular weight (Mn) 35,000 mol/g, acid value 9 mgKOH/g, solid content 34%)

Organic resin 2: water-dispersible polyurethane resin (solids 35%, pH 9.1, viscosity (20 °C) 25 cps)

Organic polysiloxane resin 1: polydimethylsiloxane resin (number average molecular weight (Mn): 3,400 g/mol, weight average molecular weight (Mw): 18,500 g/mol, acid value: 10 mgKOH/g)

Organic polysiloxane resin 2: polydimethylsiloxane resin (number average molecular weight (Mn): 4,700 g/mol, weight average molecular weight (Mw): 23,000 g/mol, acid value: 9 mgKOH/g)

Organic polysiloxane resin 3: polydimethylsiloxane resin (number average molecular weight (Mn): 1,800 g/mol, weight average molecular weight (Mw): 10,000 g/mol, acid value 9: mgKOH/g)

Manufacture of glass fiber reinforcement and thermoplastic polymer composite material

[Experimental Example 1-9]

Each of the size compositions prepared in Examples 1-9 was applied, and the glass fiber fiberized to a diameter of 13±1 μm through a bushing was treated by a roll coating method, cut to a length of 4 mm, and a chopped strand type experiment The glass fiber reinforcement of Examples 1-9 was prepared. Based on 100 parts by weight of the solid content of the glass fiber reinforcement, 0.5 to 0.6 parts by weight of the size composition was used.

10 parts by weight of each prepared glass fiber reinforcement and 90 parts by weight of a thermoplastic polycarbonate resin (LUPOY PC1300, LG Chem) were mixed and extruded, and then an injection specimen was prepared according to ASTM D256 standard and applied properties were measured.

[Comparative Experimental Example 1-2]

Except for using the size composition prepared in Comparative Example 1-2, the glass fiber reinforcement of Comparative Example 1-2 and a thermoplastic polymer composite material to which it was applied were prepared in the same manner as in Experimental Example.

[Comparative Experimental Example 3]

Except for using a commercially available interfacial adhesive glass fiber reinforcing material (CS321, KCC, glass fiber reinforcing material to which an organic functional group-containing organosilane and interfacial adhesive size composition was applied), the thermoplastic of Comparative Experimental Example 3 was used in the same manner as in Experimental Example. A polymer composite material was prepared.

[Experimental example: evaluation of physical properties]

The physical properties of the glass fiber reinforcement material and the thermoplastic polymer composite material prepared in each Experimental Example and Comparative Experimental Example were measured by the following method, and the results are shown in Table 3 below.

organic content

The organic matter content applied to the glass fiber was measured according to the ISO 1887 standard.

Evaluation criteria: 0.5% to 0.7% - good

focus

After putting 700 g of iron beads and 150 g of glass fiber reinforcement into a 1.7 liter stainless steel barrel, and rotating and translating for 120 seconds, the amount (wt%) of the generated fuzz was measured to measure the focusing force between the glass fibers. As the amount of generated fuzz increases, it means that the focusing force decreases, and workability may be deteriorated due to the generation of fuzz in the extrusion process.

Evaluation criteria: Less than 5% - Excellent, 5% or more and less than 10% - Good, 10% or more and less than 20% - Poor, 20% or more - Poor

impact strength

Impact strength was measured according to ASTM D256.

Evaluation criteria: 12 or more - Excellent, 11 or more and less than 12 - Good, 10 or more and less than 11 - Poor, less than 10 - Poor

From the results of Table 3, it can be confirmed that the glass fiber reinforcement coated with the size composition of Examples 1-9 according to the present invention has excellent focusing power, and the glass fiber reinforced thermoplastic polymer composite material to which it is applied exhibits excellent impact strength. there was. On the other hand, the glass fiber reinforcing material coated with the size composition of Comparative Example 1-2 or the glass fiber reinforcing material of Comparative Example 3 and the glass fiber-reinforced thermoplastic polymer composite material using the same were the glass fiber reinforcing material and the glass fiber-reinforced thermoplastic polymer using the size composition of Examples. It was confirmed that it exhibited inferior physical properties compared to the composite material.

Claims (7)

A size composition comprising an organic silane coupling agent and a film former comprising an organic resin and an organic polysiloxane resin in a weight ratio of 50:50 to 98:2. According to claim 1, wherein the organic resin is water-dispersed polyurethane resin, water-dispersed epoxy resin, water-soluble polypropylene resin, water-soluble maleic acid-modified polypropylene resin, water-dispersed maleic acid-modified polyethylene/polypropylene copolymer resin, water-soluble maleic acid/fatty acid-modified poly At least one size composition selected from the group consisting of a propylene resin, a polyester resin, and an acrylic emulsion resin. The organic polysiloxane resin according to claim 1, wherein the organic polysiloxane resin has a number average molecular weight (Mn) of 3,000 to 10,000 g/mol, a weight average molecular weight (Mw) of 15,000 to 50,000 g/mol, and an acid value of 1 to 20 mgKOH/g. size composition. The size composition according to claim 1, wherein the organopolysiloxane resin is a methyl group-substituted polysiloxane resin. The size composition according to claim 1, comprising 45 to 98% by weight of an organic resin, 1 to 50% by weight of an organic polysiloxane resin, and 1 to 10% by weight of an organosilane coupling agent, based on the total solid content of the size composition. A glass fiber reinforcement surface-treated with the size composition according to any one of claims 1 to 5. A glass fiber reinforced thermoplastic polymer composite material comprising the glass fiber reinforcement according to claim 6 .