Glass fiber-reinforced propylene resin composition

Abstract

The present invention provides a material for manufacturing a glass fiber reinforced molded product that suppresses the use amount of a dispersant and suppresses the generation of white haze. The solution is a glass fiber reinforced propylene resin composition containing 10 to 50 parts by mass of glass fiber, 50 to 90 parts by mass of propylene resin (the total of both is 100 parts by mass.), 0.3 parts by mass or more of carbon black, and polyolefin wax having an average particle diameter of 1 to 40 μm, the mass ratio of the polyolefin wax to the carbon black being 0.75 to 1.5.

Description

Technical Field

[0001] This invention relates to a glass fiber reinforced acrylic resin composition. Background Technology

[0002] Fiber-reinforced resin molded parts are lightweight and have excellent rigidity and heat resistance, so they have been used in a variety of fields such as electrical equipment, automobiles, residential equipment, and medical devices.

[0003] As fiber-reinforced resin molded parts, for example, molded parts using reinforcing fibers such as glass fiber and thermoplastic resins such as polyamide and polypropylene are known. Such fiber-reinforced resin molded parts are used in the automotive field for components requiring high rigidity and heat resistance, such as fan covers in engine compartments and propeller fans.

[0004] For example, Patent Document 1 describes a vehicle exterior trim part formed from a glass long fiber reinforced polyolefin composition containing glass long fiber reinforced polyolefin resin granules, polyolefin resin, antioxidant, light stabilizer, and ultraviolet absorber, and also describes that carbon black, wax, etc., can be added to the composition. Furthermore, Patent Document 2 describes a glass long fiber reinforced polyolefin composition containing glass long fiber reinforced polyolefin resin granules, polyolefin resin, and a pigment containing zinc sulfide, and also describes that carbon black, wax, etc., can be added to the composition.

[0005] Patent document 3 describes a colorant composition containing olefin resin, carbon black and glass fiber, and also describes that a dispersant and polyethylene wax as a lubricant can be added to the composition.

[0006] Patent document 4 describes a composite material comprising: a polymer resin; and glass fiber strands containing glass fibers coated with an aqueous grouting composition disposed in the polymer resin, and the grouting composition may contain carbon black, polypropylene wax, etc.

[0007] On the other hand, Patent Document 5 describes a long-fiber reinforced propylene resin composition incorporating an ethylene-based polymer with a density, melting point, and heat of fusion within a specified range. It also describes how this composition can suppress the occurrence of appearance defects such as white haze on the surface of the molded article (hereinafter also referred to as "white haze generation") and can form a molded article with excellent mechanical properties.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Application Publication No. 9-207233

[0011] Patent Document 2: Japanese Patent Application Publication No. 9-183869

[0012] Patent Document 3: Japanese Patent Application Publication No. 2002-53711

[0013] Patent Document 4: Japanese Patent Publication No. 2014-512323

[0014] Patent Document 5: International Publication No. 2020 / 091051 Summary of the Invention

[0015] The technical problem that the invention aims to solve

[0016] From the perspective of suppressing white fog generation, there is room for further improvement in the molded articles obtained from existing glass fiber reinforced acrylic resin compositions.

[0017] The inventors of this invention have discovered that white haze can be improved by incorporating carbon black into glass fiber reinforced acrylic resin compositions and using metal soap as a dispersant for the carbon black. However, from the viewpoint of reducing the amount of dispersant used, there is room for further improvement.

[0018] Therefore, the object of the present invention is to provide a material suitable for manufacturing glass fiber reinforced molded articles that suppress the amount of dispersant used and suppress the generation of white fog.

[0019] Technical solutions for solving technical problems

[0020] The gist of this invention is as follows. [1]

[0022] A glass fiber reinforced acrylic resin composition comprising:

[0023] 10-50 parts by weight of glass fiber;

[0024] 50-90 parts by weight of acrylic resin (wherein, the total of glass fiber and acrylic resin is set at 100 parts by weight);

[0025] 0.3 parts by weight or more of carbon black; and

[0026] The polyolefin wax has an average particle size of 1 to 40 μm, and the mass ratio of the polyolefin wax to the carbon black is 0.75 to 1.5. [2]

[0028] The glass fiber reinforced acrylic resin composition described above [1] is wherein the polyolefin wax is a polypropylene wax. [3]

[0030] The glass fiber reinforced acrylic resin composition as described in [1] or [2] above, wherein the content of the carbon black is 2 parts by mass or less. [4]

[0032] The glass fiber reinforced acrylic resin composition of any one of [1] to [3] above, wherein the acrylic resin contains modified polypropylene. [5]

[0034] A method for manufacturing an injection-molded article, wherein the injection-molded article is composed of a glass fiber reinforced acrylic resin composition of any one of [1] to [4] above, wherein the manufacturing method includes:

[0035] A process for manufacturing granules from part or all of the aforementioned acrylic resin and the aforementioned glass fiber;

[0036] The process of dry-mixing the granules obtained from the above steps, the carbon black, the polyolefin wax, and any portion of the acrylic resin to obtain the composition; and

[0037] The process of injection molding the above composition.

[0038] Invention Effects

[0039] Using the glass fiber reinforced acrylic resin composition of the present invention, it is possible to manufacture glass fiber reinforced molded articles that suppress the amount of dispersant used and suppress the generation of white fog. Attached Figure Description

[0040] Figure 1 This is a schematic diagram of a pellet manufacturing device. Detailed Implementation

[0041] The present invention will now be described in more detail.

[0042] [Glass fiber reinforced acrylic resin composition]

[0043] The glass fiber reinforced acrylic resin composition of the present invention is characterized by containing glass fiber, acrylic resin, carbon black and specified polyolefin wax.

[0044] Glass fiber

[0045] The glass fiber reinforced acrylic resin composition of the present invention contains glass fibers.

[0046] As for glass fibers, examples include long filament fibers made by melt spinning of various glasses such as E glass (Electrical glass), C glass (Chemical glass), A glass (Alkali glass), S glass (High strength glass), and alkali-resistant glass.

[0047] In this invention, long glass fibers are typically used as the glass fiber. Continuous glass fiber bundles, which are commercially available in the form of glass rovings, are typically used as the raw material for the long glass fibers. The average fiber diameter is typically 3–30 μm, preferably 13–20 μm, more preferably 16–18 μm, and the number of filaments in the bundle is typically 400–10,000, preferably 1,000–6,000, more preferably 3,000–5,000.

[0048] In addition, as described in Japanese Patent Application Publication No. 6-114830, it is also possible to bundle multiple fiber bundles together for use.

[0049] Functional groups can be introduced onto the surface of glass fibers through various surface treatment methods, such as electrolytic treatment or condenser treatment. Condensers are preferred in surface treatment, and condensers containing coupling agents are particularly preferred. Using surface-treated glass fibers improves the adhesion between the glass fibers and the resin components, resulting in molded products with good strength and appearance.

[0050] Examples of tethering agents include the tethering agent containing a coupling agent described in Japanese Patent Application Publication No. 2003-253563.

[0051] Examples of coupling agents include silane-based coupling agents such as aminosilanes and epoxysilanes, and titanium-based coupling agents.

[0052] In addition, as a binding agent, it preferably contains a resin emulsion in addition to a coupling agent for ease of handling.

[0053] Resin emulsions contained as condensing agents include, for example, polyurethane-based, olefin-based, acrylic-based, nylon-based, butadiene-based, or epoxy-based resin emulsions, among which polyurethane-based or olefin-based resin emulsions are preferred.

[0054] Acrylic Resins

[0055] The glass fiber reinforced acrylic resin composition of the present invention contains acrylic resin.

[0056] The aforementioned propylene resins are polymers containing structural units derived from propylene as their main structural units. Examples of such polymers include propylene homopolymers, propylene-α-olefin random copolymers, and propylene block copolymers (hereinafter, they are also collectively referred to as "unmodified propylene resins"), as well as modified polypropylene.

[0057] Examples of the above-mentioned propylene-α-olefin random copolymers include random copolymers of propylene with at least one olefin selected from α-olefins having 2 carbon atoms (i.e., ethylene) and α-olefins having 4 to 8 carbon atoms. Examples of the above-mentioned α-olefins include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, and 1-octene; ethylene and 1-butene are preferred examples; and ethylene is particularly preferred. The proportion of propylene structural units in the above-mentioned random copolymers is preferably 90 mol% or more, more preferably 95 mol% or more.

[0058] The aforementioned propylene-based block copolymer preferably consists of a propylene homopolymer portion and a propylene-α-olefin random copolymer portion. The specific configuration of the propylene-α-olefin random copolymer portion is the same as that of the aforementioned propylene-α-olefin random copolymer.

[0059] When the aforementioned propylene-based block copolymer undergoes n-decane solvent separation, it is separated into a component soluble in n-decane at 23°C (hereinafter also referred to as "decane-soluble fraction") and a component insoluble in n-decane at 23°C (hereinafter also referred to as "decane-insoluble fraction"). The content of the decane-soluble fraction is typically 5–30% by mass, preferably 5–25% by mass, more preferably 8–18% by mass, and the content of the decane-insoluble fraction is typically 70–95% by mass, preferably 75–95% by mass, more preferably 82–92% by mass.

[0060] The modified polypropylene described above can be obtained by acid modification of polypropylene. Commonly known modification methods include grafting and copolymerization. Unmodified propylene resins described above can be used as examples of the polypropylene to be modified.

[0061] As modifiers for modification, examples include unsaturated carboxylic acids and their derivatives. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, nadic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, sorbic acid, succinic acid, angelic acid, and phthalic acid. Examples of their derivatives include acid anhydrides, esters, amides, imides, and metal salts. Specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, nadic anhydride, phthalic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, monoethyl maleate, acrylamide, maleic acid monoamide, maleimide, N-butylmaleimide, sodium acrylate, and sodium methacrylate. Among these, unsaturated dicarboxylic acids and their derivatives are preferred, and maleic anhydride and phthalic anhydride are more preferred.

[0062] The amount of acid addition to the modified polypropylene, in other words, the proportion of the structure derived from the aforementioned acid in the modified polypropylene, is preferably 0.1 to 14% by weight, more preferably 0.3 to 8% by weight. Regarding the amount of acid addition, the IR spectrum of the resin can be measured based on a 1670 cm⁻¹ spectral density. -1 ~1,810cm -1 The area of ​​the peak is used to determine this.

[0063] In the case where the glass fiber and the acrylic resin are used to form the glass fiber reinforced resin granules described later, the modification of polypropylene can be carried out before manufacturing the glass fiber reinforced resin granules or during the melt mixing process when manufacturing the glass fiber reinforced resin granules.

[0064] When modified polypropylene contains residual modifiers or volatile components derived from them (hereinafter, they are also collectively referred to as "volatile components"), haze may sometimes occur on the surface of the molded article formed from the glass fiber reinforced acrylic resin composition. Therefore, it is preferable to have low levels of the aforementioned volatile components, and the content of volatile components in the modified polypropylene as defined by the formula described in International Publication No. 2020 / 091051

[0039] is preferably 9000 ppm or less, more preferably 7000 ppm or less. The amount of volatile components can be reduced by vacuum drying of the modified polypropylene, etc.

[0065] From the viewpoint of improving the affinity between glass fiber and the aforementioned unmodified propylene polymer, and increasing the strength or heat resistance of the manufactured molded articles, fatty acid anhydride-modified polypropylene is preferred, and maleic anhydride-modified polypropylene is particularly preferred.

[0066] The melt flow rate of the modified polypropylene (based on ISO 1133-1, 230°C, 2.16 kg load) is preferably 50 g / 10 min or more, more preferably 80 g / 10 min or more, and the upper limit can be, for example, 1000 g / 10 min. When the melt flow rate of the modified polypropylene is within this range, the glass fiber reinforced propylene resin composition of the present invention has flowability suitable for injection molding.

[0067] Furthermore, from the viewpoint of forming a molded body with excellent mechanical properties through injection molding with good processability, the melt flow rate (based on ISO 1133-1, 230°C, 2.16 kg load) of the above-mentioned acrylic resin as a whole is preferably 25 to 500 g / 10 min, more preferably 50 to 400 g / 10 min.

[0068] (Glass fiber reinforced resin granules)

[0069] In the glass fiber reinforced acrylic resin composition of the present invention, a portion or all of the acrylic resin (hereinafter also referred to as "acrylic resin (P1)") and the glass fiber can be formed into granules (hereinafter also referred to as "glass fiber reinforced resin granules").

[0070] In the propylene resin (P1) contained in the granules, the melt flow rate of the unmodified propylene resin (based on ISO 1133-1, 230°C, 2.16 kg load) is preferably 20 g / 10 min or more, more preferably 30 g / 10 min or more, and even more preferably 40 g / 10 min or more, with an upper limit of, for example, 300 g / 10 min. When the melt flow rate is within this range, the composition of the present invention has flowability suitable for injection molding.

[0071] The fiber length of the glass fibers in the glass fiber reinforced resin granules is usually 4 to 10 mm, preferably 5 to 8 mm, and the fiber diameter is usually 10 to 20 μm, preferably 13 to 18 μm.

[0072] In glass fiber reinforced resin granules, the glass fibers are arranged roughly parallel to the length direction of the granules, and the fiber length of the glass fibers is usually substantially the same as the particle length of the granules (i.e., the length of the granules in the length direction).

[0073] The glass fiber content in the glass fiber reinforced resin granules is preferably 40 to 70% by mass, more preferably 45 to 60% by mass, relative to 100% of the glass fiber reinforced resin granules. When the glass fiber content is above the lower limit mentioned above, the glass fiber reinforced resin granules can be manufactured with good productivity. When the glass fiber content is below the upper limit mentioned above, the resin can be fully impregnated in the fiber bundles of glass fibers.

[0074] The amount of modified polypropylene in the glass fiber reinforced resin granules is preferably 1 to 5% by mass, more preferably 1.5 to 3.5% by mass, relative to 100% by mass of the glass fiber reinforced resin granules. When the amount of modified polypropylene is above the lower limit mentioned above, the adhesion between the glass fiber and the resin component is good. When the amount of modified polypropylene is below the upper limit mentioned above, the molecular weight of the modified polypropylene does not become too low, and therefore the molded articles manufactured from the compositions of the present invention have good strength.

[0075] Glass fiber reinforced resin granules are typically columnar in shape.

[0076] The particle length (length in the longitudinal direction) of the glass fiber reinforced resin granules is typically 4 to 10 mm, preferably 5 to 8 mm. When the particle length of the glass fiber reinforced resin granules is above or above the aforementioned lower limit, the molded articles manufactured from the glass fiber reinforced acrylic resin composition of the present invention exhibit excellent mechanical properties. Furthermore, when the particle length of the glass fiber reinforced resin granules is below or above the aforementioned upper limit, the moldability of the glass fiber reinforced acrylic resin composition of the present invention is excellent.

[0077] In glass fiber reinforced resin granules, the glass fibers are typically arranged roughly parallel to the length direction of the granules.

[0078] Because the glass fibers in the glass fiber reinforced resin granules have a large aspect ratio, the molded articles formed from the glass fiber reinforced acrylic resin composition of the present invention containing the above-mentioned glass fiber reinforced resin granules have excellent mechanical strength.

[0079] Glass fiber reinforced resin granules can be manufactured using known forming methods such as drawing. Specifically, a roving consisting of thousands of glass fibers is introduced into an impregnation mold, where acrylic resin is melted. The molten resin (hereinafter also referred to as "molten resin") is then uniformly impregnated between the filaments, and finally cut into the desired length, thus readily obtaining the desired product.

[0080] In this method, for example, the following approach can be used: molten resin is supplied to an impregnation die located at the front end of the extruder using an extruder, and a continuous glass fiber bundle is passed through it. After the molten resin is impregnated in the glass fiber bundle, it is drawn through a nozzle to granulate to the required length.

[0081] Alternatively, the following method can be used: dry-mix unmodified propylene polymers, unsaturated carboxylic acids or their anhydrides with organic peroxides and feed them into the hopper of an extruder, so that modification can be carried out simultaneously while feeding.

[0082] There are no particular limitations on the method for impregnating molten resin into glass fiber rovings, and the method described in International Publication 2010 / 137305

[0036] can be cited as an example.

[0083] During the resin melting process, an extruder with two or more feed sections can be used, with resin and a decomposing agent fed through the top feed port and other resins fed through the side feed port. Organic peroxides are preferred as the decomposing agent. Alternatively, two or more extruders (extrusion sections) can be used, with the decomposing agent fed into at least one of them. Resin, unsaturated carboxylic acids or their derivatives, and a decomposing agent can also be fed into at least one part of the extruder.

[0084] (In addition to glass fiber reinforced resin granules, acrylic resins can also be added)

[0085] In the case where the acrylic resin (P1) contained in the above-mentioned glass fiber reinforced resin granules is a part of the above-mentioned acrylic resin, the glass fiber reinforced acrylic resin composition of the present invention contains, in addition to the acrylic resin (P1), a balance of acrylic resin (hereinafter also referred to as "acrylic resin (P2)").

[0086] The aforementioned propylene resin (P2) is a polymer containing structural units derived from propylene as the main structural units. Examples of such polymers include propylene homopolymers, propylene-α-olefin random copolymers, and propylene block copolymers.

[0087] The details of the above-mentioned propylene-α-olefin random copolymer and the above-mentioned propylene-based block copolymer are as described above.

[0088] The melt flow rate of the acrylic resin (P2) (based on ISO 1133-1, 230°C, 2.16 kg load) is preferably 10–300 g / 10 min, more preferably 20–250 g / 10 min, and even more preferably 20–200 g / 10 min. When the melt flow rate of the acrylic resin (P2) is within this range, the molded articles formed from the glass fiber reinforced acrylic resin composition of the present invention exhibit excellent mechanical properties.

[0089] Examples of the shapes of acrylic resins (P2) include powders and granules.

[0090] Carbon Black

[0091] The glass fiber reinforced acrylic resin composition of the present invention contains carbon black.

[0092] The carbon black content in the composition of the present invention is 0.3 parts by mass or more, preferably 0.3 to 2 parts by mass, relative to the total of 100 parts by mass of the glass fiber and the acrylic resin. When the carbon black content is within the above range, the reinforced fiber molded body made from the glass fiber reinforced acrylic resin composition can suppress the generation of white fog. On the other hand, when the content is less than 0.3 parts by mass, the generation of white fog may not be suppressed. In addition, when the content is below the above upper limit, the interfacial adhesion between the glass fiber and the acrylic resin is good.

[0093] Examples of carbon black include furnace black, acetylene black, pyrolysis black, and channel black.

[0094] Polyolefin wax

[0095] The glass fiber reinforced acrylic resin composition of the present invention contains a polyolefin wax with an average particle size of 1 to 40 μm, preferably 5 to 20 μm. This average particle size is a volume-based particle size distribution (D0) obtained by laser diffraction.50 .

[0096] When the average particle size of the polyolefin wax is within this range, it can be effectively configured between carbon black particles, preventing carbon black particles from agglomerating and improving the dispersibility of carbon black in the resin component. It can also suppress the formation of white haze in the molded body. On the other hand, if the average particle size is too small compared to the lower limit, it is sometimes difficult to manufacture polyolefin wax; if the average particle size is too large compared to the upper limit, the dispersibility of carbon black decreases, and it is sometimes impossible to suppress the formation of white haze in the molded body.

[0097] In techniques for suppressing white fog formation in molded articles composed of glass fiber reinforced acrylic resin compositions by incorporating ethylene polymers, a tendency for the mechanical properties of the molded article to decrease can sometimes be observed as the amount of ethylene polymer increases. However, with the present invention, white fog formation is suppressed by incorporating carbon black and polyolefin wax, thus eliminating the concerns associated with the aforementioned incorporation of ethylene polymers.

[0098] The number-average molecular weight (Mn) of the polyolefin wax, determined by gel permeation chromatography (GPC) under the conditions described below or the same, is preferably 2,000 to 10,000, more preferably 3,000 to 4,000.

[0099] Apparatus: Gel permeation chromatography Alliance GPC2000 (manufactured by Waters Corporation)

[0100] Solvent: o-dichlorobenzene

[0101] Pillars: 2 TSKgel GMH6-HT pillars, 2 TSKgel GMH6-HTL pillars (all manufactured by Tosoh Corporation)

[0102] Flow rate: 1.0 ml / min

[0103] Sample: 0.15 mg / mL o-dichlorobenzene solution

[0104] Temperature: 140℃

[0105] The mass ratio of polyolefin wax to carbon black (mass of polyolefin wax / mass of carbon black) is 0.75 to 1.5, preferably 0.80 to 1.0. When the mass ratio is within this range, the polyolefin wax can be effectively distributed among the carbon black particles, preventing the carbon black particles from agglomerating, improving the dispersibility of carbon black in the resin component, and suppressing the formation of white haze in the molded article. On the other hand, if the mass ratio is too small compared to the lower limit mentioned above, the dispersibility of carbon black is low, and sometimes it is impossible to suppress the formation of white haze in the molded article.

[0106] Polyethylene wax and polypropylene wax are preferred as polyolefin waxes, with polypropylene wax being more preferred.

[0107] Polyolefin waxes can be used alone or in combination with two or more types.

[0108] Other Ingredients

[0109] In the glass fiber reinforced acrylic resin composition of the present invention, polymers other than those described above may be included as needed, without impairing the effects of the present invention. Examples of such polymers include ethylene polymers, and examples of ethylene polymers include those described in paragraphs

[0054] to

[0060] of International Publication No. 2020 / 091051.

[0110] In addition to the components described above, the glass fiber reinforced acrylic resin composition of the present invention may, as needed, include, within a range that does not impair the effects of the present invention (e.g., a proportion of 5% or less relative to 100% by mass of the above composition), additives such as heat stabilizers, antistatic agents, weather stabilizers, light stabilizers, anti-aging agents, antioxidants, copper passivators, fatty acid metal salts, softeners, dispersants (excluding the above-mentioned polyolefin waxes), fillers, colorants, pigments, and foaming agents. These components may also be masterbatches.

[0111] (Glass fiber reinforced acrylic resin composition)

[0112] The glass fiber reinforced acrylic resin composition of the present invention contains:

[0113] 10 to 50 parts by weight, preferably 15 to 45 parts by weight, more preferably 20 to 40 parts by weight of the above-mentioned glass fiber;

[0114] 50 to 90 parts by weight, preferably 55 to 85 parts by weight, more preferably 60 to 80 parts by weight of the above-mentioned acrylic resin (wherein the total of glass fiber and acrylic resin is set at 100 parts by weight).

[0115] 0.3 parts by weight or more, preferably 0.3 to 2 parts by weight, of the above-mentioned carbon black; and

[0116] The above-mentioned polyolefin wax,

[0117] The mass ratio of the polyolefin wax to the carbon black is 0.75 to 1.5, preferably 0.80 to 1.0.

[0118] When the content of each component is within the above range, it is possible to manufacture a molded body that suppresses the generation of white fog.

[0119] (Method for manufacturing glass fiber reinforced acrylic resin composition)

[0120] The glass fiber reinforced acrylic resin composition of the present invention can be manufactured by mixing the glass fiber, the acrylic resin, the carbon black, the polyolefin wax and any of the additives, for example by dry mixing.

[0121] The acrylic resin and the glass fiber are preferably mixed in the form of glass fiber reinforced resin granules.

[0122] [Glass fiber reinforced molded body]

[0123] The glass fiber reinforced molded body involved in this invention is composed of a composition containing the above-mentioned glass fiber, the above-mentioned acrylic resin, the above-mentioned carbon black, the above-mentioned polyolefin wax and any of the above-mentioned additives.

[0124] Unless otherwise specified, the details of each component are as described above. Furthermore, unless otherwise specified, the content and technical significance of each component in the above composition are the same as those of each component in the glass fiber reinforced acrylic resin composition of the present invention.

[0125] The length of the glass fibers in the molded articles of the present invention is generally different from the length of the glass fibers in the glass fiber reinforced acrylic resin compositions of the present invention. This is because the glass fibers shorten due to breakage during molding. Regarding the length of the glass fibers in the glass fiber reinforced molded articles according to the present invention, a predetermined number (1000) of glass fibers are extracted from the molded articles, and the length of each fiber is measured. When expressed as the weight-average fiber length calculated based on the following formula, it is generally 0.5 to 5 mm, preferably 0.8 to 3 mm.

[0126] Weight-average fiber length = Σ(fiber length) 2 / Σ Fiber Length

[0127] The glass fiber reinforced molded body according to the present invention can be manufactured by molding a resin composition containing the above-mentioned glass fiber, the above-mentioned acrylic resin, the above-mentioned carbon black, the above-mentioned polyolefin wax and any of the above-mentioned additives, such as the glass fiber reinforced acrylic resin composition according to the present invention.

[0128] As a molding method, known molding methods such as injection molding, extrusion molding, blow molding, compression molding, injection compression molding, gas injection injection molding, or foam injection molding can be applied without particular limitations. Among these, injection molding, compression molding, and injection compression molding are particularly preferred. From the viewpoint of manufacturing molded bodies with excellent appearance (i.e., suppressing the generation of white fog), injection molding is preferred.

[0129] The molded body of this invention can be applied to various fields such as automotive interior and exterior trim parts and home appliance parts. As an example of automotive interior and exterior trim parts, the interior material of the rear door can be cited.

[0130] Example

[0131] The present invention will now be described in more detail based on embodiments, but the present invention is not limited to these embodiments.

[0132] (Determination Method)

[0133] The methods for determining or evaluating various physical properties are described below.

[0134] [Mel flow rate]

[0135] Based on ISO 1133-1, the melt flow rate of the raw resin was determined at 230°C and 2.16 kg load.

[0136] [Average Particle Size]

[0137] The average particle size of the dispersant was determined using the D-value of the particle size distribution on a volume basis, measured by laser diffraction. 50 .

[0138] [Appearance of the molded object]

[0139] The appearance of the molded articles manufactured in the following benchmark evaluation examples, etc.

[0140] ○: The white fog is almost invisible;

[0141] △: White mist can be seen, but compared to ×, it is difficult to see;

[0142] ×: The state where the white fog is clearly visible.

[0143] (Raw materials used)

[0144] The raw materials used in the examples are as follows.

[0145] Acrylic Resins

[0146] Commercially available products of propylene homopolymers having the following properties.

[0147] (Unmodified acrylic resin)

[0148] ·PP1 (propylene homopolymer (MFR (230℃, 2.16kg load) = 200g / 10min)).

[0149] ·PP2 (propylene homopolymer (MFR (230℃, 2.16kg load) = 30g / 10min)).

[0150] (Modified polypropylene)

[0151] • mPP1 (manufactured by Adivant, trade name: POLYBOND3200 (MFR (230℃, 2.16kg load) = 200g / 10 minutes)).

[0152] Glass fiber

[0153] •GF (4000 bundles of glass roving with a fiber diameter of 17μm after surface treatment with aminosilane, manufactured by Nippon Electric Glass Co., Ltd., trade name: T-431N).

[0154] Carbon Black

[0155] Commercially available products.

[0156] Dispersants

[0157] • Calcium stearate (commercially available product with an average particle size of 11 μm).

[0158] • Polypropylene wax (commercially available product with an average particle size of 267 μm).

[0159] • Micronized polypropylene wax (commercially available product with an average particle size of 10 μm).

[0160] (Preparation of glass fiber reinforced resin composition)

[0161] [Manufacturing Example 1]

[0162] use Figure 1 The granulation apparatus shown manufactures glass fiber reinforced resin granules.

[0163] exist Figure 1 In this apparatus, 10 is a die, 20 is an extruder that supplies molten resin to the die, 30 is a roll of fiber bundle F, 40 is a tensioning roller assembly that applies a certain tension to the fiber bundle F introduced into the die, 50 is a cooling unit for cooling the molten resin-impregnated fiber bundle pulled out of the die, 60 is a fiber bundle pull-out roller, and 70 is a granulator for cutting the pulled-out molten resin-impregnated fiber bundle. In this apparatus, molten resin is simultaneously impregnated in three separate fiber bundles F.

[0164] The specific manufacturing conditions are as follows.

[0165] • Mold: Installed at the front end of a 50mφ extruder, with 4 rods arranged in a straight line in the impregnation section.

[0166] • Fiber bundle: A glass roving made of 4,000 glass fibers with a diameter of 17 μm that have been surface treated with aminosilane (manufactured by Nippon Electric Glass Co., Ltd., trade name: T-431N).

[0167] Preheating temperature: 200℃.

[0168] • Resin: It is made by mixing propylene polymer PP1 and maleic anhydride modified polypropylene mPP1 in a mass ratio of PP1:mPP1 = 48:2.

[0169] • Melting temperature: 280℃.

[0170] • Rods: Four rods, each 6mm (diameter) x 3mm (length).

[0171] Under the above conditions, the amount of fiber bundle is adjusted by tensioning rollers and fed into the mold for impregnation. Then, it is pulled out of the mold and cooled. Glass fiber reinforced resin granules with a particle length of 8 mm, a reinforcing fiber length of 8 mm, and a reinforcing fiber content of 50% by mass are produced by a granulator.

[0172] [Comparative Example 1]

[0173] A glass fiber reinforced resin composition was prepared by dry mixing 60 parts by weight of the glass fiber reinforced resin granules (hereinafter also referred to as "GFMB") manufactured in Manufacturing Example 1, 40 parts by weight of PP2, 0.2 parts by weight of carbon black, and 0.2 parts by weight of calcium stearate.

[0174] Next, using an injection molding machine, a molded body (color plate) was manufactured from the glass fiber reinforced resin composition under the following conditions, and its appearance was evaluated.

[0175] Mold: 90mm×50mm×2mm, with creases 15μm deep.

[0176] Molding temperature: 240℃.

[0177] Mold temperature: 45℃.

[0178] The evaluation results are shown in Table 1.

[0179] [Comparative Example 2]

[0180] The glass fiber reinforced resin composition and its molded articles were prepared by replacing 0.2 parts by weight of calcium stearate with 0.2 parts by weight of polypropylene wax, otherwise the same procedure as in Comparative Example 1. The evaluation results are shown in Table 1.

[0181] [Comparative Example 3]

[0182] The glass fiber reinforced resin composition and its molded articles were prepared by replacing 0.2 parts by weight of calcium stearate with 0.2 parts by weight of micronized polypropylene wax, otherwise following the same procedure as Comparative Example 1. The evaluation results are shown in Table 1.

[0183] [Comparative Example 4]

[0184] The amount of carbon black and calcium stearate was changed to 0.4 parts by mass, and the glass fiber reinforced resin composition and its molded article were manufactured in the same manner as in Comparative Example 1. The evaluation results are shown in Table 1.

[0185] [Comparative Example 5]

[0186] The amount of carbon black and polypropylene wax was changed to 0.4 parts by weight, and the glass fiber reinforced resin composition and its molded articles were manufactured in the same manner as in Comparative Example 2. The evaluation results are shown in Table 1.

[0187] [Example 1]

[0188] The amount of carbon black was changed to 0.4 parts by weight, and 0.2 parts by weight of calcium stearate was changed to 0.4 parts by weight of micronized polypropylene wax. Otherwise, the glass fiber reinforced resin composition and its molded articles were manufactured in the same manner as in Comparative Example 1. The evaluation results are shown in Table 1.

[0189] [Comparative Example 6]

[0190] The amount of carbon black and calcium stearate was changed to 0.8 parts by mass, and the glass fiber reinforced resin composition and its molded article were manufactured in the same manner as in Comparative Example 1. The evaluation results are shown in Table 1.

[0191] [Comparative Example 7]

[0192] The amount of carbon black and polypropylene wax was changed to 0.8 parts by weight, and the glass fiber reinforced resin composition and its molded articles were manufactured in the same manner as in Comparative Example 2. The evaluation results are shown in Table 1.

[0193] [Example 2]

[0194] The amount of carbon black and the amount of micronized polypropylene wax were changed to 0.8 parts by weight, and the glass fiber reinforced resin composition and its molded articles were manufactured in the same manner as in Example 1. The evaluation results are shown in Table 1.

[0195] [Comparative Example 8]

[0196] The amount of carbon black and calcium stearate was changed to 1.2 parts by mass, and the glass fiber reinforced resin composition and its molded articles were manufactured in the same manner as in Comparative Example 1. The evaluation results are shown in Table 1.

[0197] [Comparative Example 9]

[0198] The amount of carbon black and polypropylene wax was changed to 1.2 parts by weight, and the glass fiber reinforced resin composition and its molded articles were manufactured in the same manner as in Comparative Example 2. The evaluation results are shown in Table 1.

[0199] [Example 3]

[0200] The amount of carbon black and the amount of micronized polypropylene wax were changed to 1.2 parts by weight, and the glass fiber reinforced resin composition and its molded articles were manufactured in the same manner as in Example 1. The evaluation results are shown in Table 1.

[0201] [Comparative Example 10]

[0202] The amount of carbon black and calcium stearate was changed to 1.6 parts by mass, and the glass fiber reinforced resin composition and its molded article were manufactured in the same manner as in Comparative Example 1. The evaluation results are shown in Table 1.

[0203] [Comparative Example 11]

[0204] The amount of carbon black and polypropylene wax was changed to 1.6 parts by weight, and the glass fiber reinforced resin composition and its molded articles were manufactured in the same manner as in Comparative Example 2. The evaluation results are shown in Table 1.

[0205] [Example 4]

[0206] The amount of carbon black and the amount of micronized polypropylene wax were changed to 1.6 parts by weight, and the glass fiber reinforced resin composition and its molded articles were manufactured in the same manner as in Example 1. The evaluation results are shown in Table 1.

[0207] [Table 1]

[0208]

[0209] Symbol Explanation

[0210] 10 dies, 20 extruders, 30 fiber bundle rolls, 40 tensioning rollers, 50 cooling units, 60 pull-out rollers, and 70 granulators.

Claims

1. A glass fiber reinforced acrylic resin composition, characterized in that, contain: 10-50 parts by weight of glass fiber; 50 to 90 parts by weight of acrylic resin, wherein the total of glass fiber and acrylic resin is set at 100 parts by weight; Carbon black of 0.3 parts by weight to 2 parts by weight; and The polyolefin wax has an average particle size of 1–40 μm, wherein the mass ratio of the polyolefin wax to the carbon black is 0.75–1.5, and the average particle size is the D-value of the volume-based particle size distribution obtained by laser diffraction. 50 .

2. The glass fiber reinforced acrylic resin composition according to claim 1, characterized in that: The polyolefin wax is a polypropylene wax.

3. The glass fiber reinforced acrylic resin composition according to claim 1 or 2, characterized in that: The propylene-based resin contains modified polypropylene.

4. A method for manufacturing an injection-molded article, wherein the injection-molded article is composed of the glass fiber reinforced acrylic resin composition according to any one of claims 1 to 3, the method being characterized in that it comprises: The process of manufacturing granules from a portion or all of the acrylic resin and the glass fiber; The process of dry-blending the granules obtained from the above steps, the carbon black, the polyolefin wax, and any portion of the acrylic resin to obtain the composition; and The process of injection molding the composition.

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