JP2021147519A - Fiber-reinforced resin composition and molding containing the same - Google Patents

Abstract

To provide a resin composition which is excellent in heat deformation resistance under a high load, and in a balance between heat deformation resistance and tensile creep resistance while containing a compatibilizer.SOLUTION: A fiber-reinforced resin composition contains a polyolefin resin (A), at least one resin (B) selected from a polyamide resin (B1) and a polyester resin (B2), a fiber (C) obtained by surface-treating a reinforcement fiber with an urethane-based sizing agent, and a modified polyolefin resin (D). In 100 pts.mass of the total contents of the resin (A), the resin (B) and the fiber (C), a content of the resin (A) is 5-60 pts.mass, a content of the resin (B) is 5-60 pts.mass, and a content of the fiber (C) is 10-70 pts.mass. Based on 100 pts.mass of the total contents of the resin (A), the resin (B) and the fiber (C), a content of the modified polyolefin resin (D) is 0.05-0.95 pts.mass.SELECTED DRAWING: None

Description

The present invention relates to a fiber reinforced resin composition and a molded product containing the same.

A fiber-reinforced resin in which various reinforcing fibers are dispersed in a thermoplastic resin has high strength, rigidity, impact resistance, and heat resistance, and is used for various purposes. Patent Document 1 discloses that a fiber-reinforced resin composition containing polypropylene, polyamide or polyphenylene sulfide, and aminosilane-treated glass fiber in a specific ratio in combination exhibits a high thermal deformation temperature.

Japanese Unexamined Patent Publication No. 2003-231758

In material applications where a large force is applied over a long period of time, the fiber reinforced resin composition is required to have the property that the material does not deform even when used for a long period of time. However, in the fiber-reinforced resin composition of Patent Document 1, the thermal deformation temperature under a high load is not sufficiently high. Further, Patent Document 1 describes that when a compatibilizer such as a modified polypropylene resin is added to the fiber-reinforced resin composition, the thermal deformation temperature may not be improved. However, when a compatibilizer is not added, long-term physical properties (for example, tensile creep resistance) may be inferior.

An object of the present invention is to provide a resin composition having excellent heat-resistant deformability under a high load and having an excellent balance between heat-resistant deformation and tensile creep resistance while containing a compatibilizer.

As a result of studies for solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by the fiber-reinforced resin composition described below, and have completed the present invention. The present invention relates to the following [1] to [8].

[1] A polyolefin resin (A), at least one resin (B) selected from a polyamide resin (B1) and a polyester resin (B2), and a fiber (C) in which reinforcing fibers are surface-treated with a urethane-based sizing agent. A fiber-reinforced resin composition containing the modified polyolefin resin (D) and the resin (A), the resin (B), and the fiber (C) in a total of 100 parts by mass. The content of A) is 5 to 60 parts by mass, the content of the resin (B) is 5 to 60 parts by mass, the content of the fiber (C) is 10 to 70 parts by mass, and the resin. The content of the modified polyolefin resin (D) is 0.05 to 0.95 parts by mass with respect to a total of 100 parts by mass of the contents of (A), the resin (B) and the fiber (C). Fiber reinforced resin composition.
[2] The fiber-reinforced resin composition according to the above [1], wherein the resin (B) is the polyamide resin (B1).
[3] The fiber-reinforced resin composition according to the above [1] or [2], wherein the polyamide resin (B1) is a polyamide 6.
[4] Of the above [1] to [3], the content of the resin (B) is 8 to 92 parts by mass in the total content of the resin (A) and the resin (B) of 100 parts by mass. The fiber reinforced resin composition according to any one.
[5] The fiber-reinforced resin composition according to any one of [1] to [4] above, wherein the resin (A) is polypropylene.
[6] The fiber-reinforced resin composition according to any one of [1] to [5] above, wherein the reinforcing fiber is at least one selected from glass fiber and carbon fiber.
[7] A molded product containing the fiber-reinforced resin composition according to any one of the above [1] to [6].
[8] The molded product according to the above [7], which is an automobile part.

According to the present invention, it is possible to provide a resin composition having excellent heat-resistant deformability under a high load and having an excellent balance between heat-resistant deformation and tensile creep resistance while containing a compatibilizer.

Hereinafter, the present invention will be described in more detail.
The numerical range represented by using "~" in the present specification means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.

[Fiber reinforced plastic composition]
The fiber-reinforced resin composition of the present embodiment (hereinafter, also referred to as “composition (I)”) is
Polyolefin resin (A) and
With at least one resin (B) selected from polyamide resin (B1) and polyester resin (B2),
Fibers (C) whose reinforcing fibers are surface-treated with a urethane-based sizing agent, and
Contains the modified polyolefin resin (D).

<Polyolefin resin (A)>
The polyolefin resin (A) (hereinafter, also referred to as “resin (A)”) is, for example, a polymer of olefins such as α-olefin, cyclic olefin, non-conjugated diene, and aromatic olefin, and contains α-olefin as a main component. The polymer is preferable. With respect to the polymer containing α-olefin as a main component, the content of the constituent unit derived from α-olefin in the polymer is preferably 50 mol% or more, more preferably 60 mol% or more, still more preferably 70 mol%. It means that it is the above. The content of the structural unit ^{can be measured by, for example, 13} C-NMR method.

Examples of the α-olefin include an α-olefin having 2 to 20 carbon atoms, preferably an α-olefin having 2 to 10 carbon atoms, and more preferably an α-olefin having 2 to 8 carbon atoms. Specific examples thereof include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 3-methyl-1-butene and 4-methyl-1-pentene. One kind or two or more kinds of α-olefins can be used.

Examples of the polyolefin resin (A) include ethylene homopolymers, polyethylenes such as ethylene and other α-olefin copolymers, and polypropylene such as propylene homopolymers and propylene and other α-olefin copolymers. Preferably, polypropylene is more preferred, and propylene homopolymers are particularly preferred. The content of the ethylene-derived structural unit in polyethylene is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more. The content of the propylene-derived structural unit in polypropylene is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more.

As the polyolefin resin (A), polypropylene is preferable. The melting point measured by a polypropylene differential scanning calorimeter (heating rate: 10 ° C./min) is preferably 130 ° C. or higher, more preferably 140 ° C. or higher, preferably 180 ° C. or lower, and more preferably 170 ° C. or lower. Is.

The melt flow rate (MFR; JIS K7210 compliant, 2.16 kg load) of the polyolefin resin (A) is preferably 0.01 g / 10 min or more, more preferably 0.1 g / 10 min or more, still more preferably 1 g / 10 min or more. It is even more preferably 10 g / 10 min or more, preferably 500 g / 10 min or less, more preferably 300 g / 10 min or less, still more preferably 100 g / 10 min or less. The measurement temperature of MFR varies depending on the polymer type, for example, in the case of polypropylene, it is usually 230 ° C., and in the case of polyethylene, it is usually 190 ° C.

One kind or two or more kinds of resin (A) can be used. That is, the resin (A) may use one kind of the olefin polymer, or may be a mixture of two or more kinds of the olefin polymer.

<Resin (B)>
The resin (B) is at least one resin selected from the polyamide resin (B1) and the polyester resin (B2), and the polyamide resin (B1) is preferable. The resin (B) is a component that improves the heat resistance, long-term durability, and mechanical characteristics of the molded product containing the composition (I).

≪Polyamide resin (B1) ≫
Examples of the polyamide resin (B1) include a polymer of at least one amino acid-based monomer selected from a compound having an amino group and a carboxy group and a dehydration condensate thereof, a polymer of a diamine and a dicarboxylic acid, and the above. Examples thereof include a copolymer of an amino acid-based monomer, a diamine and a dicarboxylic acid.

Examples of the amino acid-based monomer include amino acids such as aminocaproic acid, aminoundecanoic acid, aminododecanoic acid, and paraaminomethylbenzoic acid; and lactams such as ε-caprolactam, undecanlactam, and ω-lauryllactam. One or more of the above amino acid-based monomers can be used.

Examples of the diamine include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, and 1 , 10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecan, 1, , 17-diaminoheptadecan, 1,18-diaminooctadecane, 1,19-diaminononadecan, 1,20-diaminoeikosan, 2-methyl-1,5-diaminopentane (2M-5), 2-methyl- Aliper diamines such as 1,8-diaminooctane (2M-8); alicyclic diamines such as cyclohexanediamine and bis- (4-aminocyclohexyl) methane; xylylene diamines (p-phenylenediamine, m-phenylenediamine, etc.) ) And other aromatic diamines. One kind or two or more kinds of diamines can be used.

Examples of dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brushphosphate, tetradecanedioic acid, and pentadecane. Examples thereof include aliphatic dicarboxylic acids such as diacid and octadecanedioic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid. One kind or two or more kinds of dicarboxylic acids can be used.

Specific examples of the polyamide resin (B1) include polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 614, polyamide 11, polyamide 12, polyamide 6T, polyamide 6I, polyamide 9T, polyamide M5T, polyamide 1010, and polyamide. 1012, Polyamide 10T, Polyamide MXD6, Polyamide 6T / 66, Polyamide 6T / 6I, Polyamide 6T / 6I / 66, Polyamide 6T / 2M-5T, Polyamide 9T / 2M-8T. Among these, polyamide 6 and polyamide 66 are preferable, and polyamide 6 is more preferable.

The MFR (JIS K7210 compliant, 2.16 kg load) of the polyamide resin (B1) is preferably 1 g / 10 min or more, more preferably 5 g / 10 min or more, still more preferably 10 g / 10 min or more, still more preferably 20 g / 10 min or more. It is preferably 500 g / 10 min or less, more preferably 300 g / 10 min or less, and further preferably 100 g / 10 min or less. The measurement temperature of MFR differs depending on the polymer type. For example, in the case of polyamide 6, it is usually 230 ° C., and in the case of polyamide 66, it is usually 270 ° C.

The melting point of the polyamide resin (B1) measured by a differential scanning calorimeter (heating rate: 10 ° C./min) is preferably 200 ° C. or higher, more preferably 210 ° C. or higher, still more preferably 220 ° C. or higher, and is preferable. Is 300 ° C. or lower, more preferably 280 ° C. or lower, still more preferably 270 ° C. or lower.
One type or two or more types of polyamide resin (B1) can be used.

≪Polyester resin (B2) ≫
The polyester resin (B2) is a copolymer of at least one selected from polycarboxylic acid and its anhydride and a polyol, and has a hydrophilic group in the molecular skeleton including the terminal, and is a resin by a known method. Can be manufactured. Examples of the hydrophilic group include a polyalkylene oxide group, a sulfonate group, a carboxy group, and a neutralizing salt thereof.

Examples of the polycarboxylic acid and its anhydride include aromatic dicarboxylic acids, sulfonate-containing aromatic dicarboxylic acids, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, trifunctional or higher functional polycarboxylic acids, and anhydrides thereof. Can be mentioned.

Examples of the aromatic dicarboxylic acid and its anhydride include phthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and phthalic anhydride.

Examples of the sulfonate-containing aromatic dicarboxylic acid include sulfoterephthalate, 5-sulfoisophthalate, and 5-sulfoortophthalate.
Examples of aliphatic dicarboxylic acids and alicyclic dicarboxylic acids and their anhydrides include fumaric acid, maleic acid, itaconic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, and 1,4-cyclohexanedicarboxylic acid. Acids, succinic anhydride and maleic anhydride can be mentioned.

Examples of the trifunctional or higher functional polycarboxylic acid and its anhydride include trimellitic acid, pyromellitic acid, trimellitic anhydride, and pyromellitic anhydride.
Examples of the polyol include diols and trifunctional or higher functional polyols. Examples of the diol include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, polybutylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and poly. Examples thereof include tetramethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, and alkylene oxide adducts of bisphenol A. Examples of trifunctional or higher functional polyols include trimethylolpropane, glycerin, and pentaerythritol.

The polyester resin (B2) may be a polymer of at least one monomer selected from a compound having a hydroxy group and a carboxy group and a dehydration condensate thereof. Examples of the compound having a hydroxy group and a carboxy group include lactic acid.

Specific examples of the polyester resin (B2) include polybutylene terephthalate, polyethylene terephthalate, polybutylene succinate, polyethylene succinate, and polylactic acid.

The MFR (JIS K7210 compliant, 2.16 kg load) of the polyester resin (B2) is preferably 0.1 g / 10 min or more, more preferably 1 g / 10 min or more, still more preferably 10 g / 10 min or more, and preferably 500 g / 10 min or more. It is 10 min or less, more preferably 300 g / 10 min or less, still more preferably 100 g / 10 min or less. The measurement temperature of MFR varies depending on the polymer species, for example, in the case of polybutylene terephthalate, it is usually 230 ° C., and in the case of polyethylene terephthalate, it is usually 270 ° C.

The melting point of the polyester resin (B2) measured by a differential scanning calorimeter (heating rate: 10 ° C./min) is preferably 200 ° C. or higher, more preferably 210 ° C. or higher, preferably 300 ° C. or lower, more preferably. Is 280 ° C. or lower.
One type or two or more types of polyester resin (B2) can be used.

<Fiber (C)>
The composition (I) contains the fiber (C) obtained by surface-treating the reinforcing fiber with a urethane-based sizing agent (urethane-based surface treatment agent).
As the reinforcing fiber, either an organic fiber or an inorganic fiber may be used. For example, glass fiber; carbon fiber; aluminum fiber, aluminum alloy fiber, copper fiber, brass fiber, steel fiber, stainless steel fiber, titanium fiber and other metal fibers; cotton fiber, silk fiber, wood fiber, cellulose fiber and other natural fibers. Ceramic fibers such as silicon carbide fiber, silicon titrated fiber, alumina fiber, zirconia fiber; Total aromatic polyamide (aramid), Total aromatic polyester, Total aromatic polyesteramide, Total aromatic polyether, Total aromatic polycarbonate, Total aromatic polyazomethine, polyphenylene sulfide, polyparaphenylene benzobisoxazole, poly (para-phenylene benzobisthiazole), polybenzoimidazole, polyether ether ketone, polyamideimide, polyimide, polytetrafluoroethylene, polyvinyl alcohol, polyolefin, Examples thereof include synthetic fibers made of synthetic resins such as polyarylate and fluorine-based polymers. Among these, glass fiber and carbon fiber are preferable, and glass fiber is more preferable.

The reinforcing fibers may be short fibers or long fibers. The short fibers may be chopped fiber (cut fiber) -like short fibers or pulp-like short fibers having fibrils. Further, the reinforcing fiber may be a single fiber, or may be a twisted plurality of single fibers.

The average fiber length of the reinforcing fibers is preferably 0.01 mm or more, more preferably 0.1 mm or more, further preferably 1 mm or more, preferably 100 mm or less, more preferably 50 mm or less, still more preferably 30 mm or less. In such an embodiment, the effect of reinforcing the mechanical properties of the reinforcing fibers tends to be sufficiently exhibited, and the dispersibility of the reinforcing fibers in the composition tends to improve the appearance. The ratio of the number of fibers having a fiber length of less than 0.1 mm to the total number of reinforcing fibers is preferably 18% or less.

The average fiber diameter of the reinforcing fibers is preferably 1 μm or more, more preferably 5 μm or more, preferably 30 μm or less, and more preferably 20 μm or less. In such an embodiment, the reinforcing fibers are less likely to be damaged during molding, the impact strength of the obtained molded product tends to be high, the appearance of the molded product is improved, and the rigidity and heat resistance of the molded product are improved. There is a tendency to obtain a sufficient reinforcing effect on mechanical properties such as properties.

For the average fiber length and average fiber diameter, for example, a photograph of the reinforcing fibers was taken with an optical microscope, and the lengths or diameters of 100 randomly selected reinforcing fibers were measured in the obtained photographs, and each was calculated as an arithmetic average. It can be obtained by doing.

Examples of the glass fiber include fibers having a glass composition such as A glass, C glass, D glass, E glass, and S glass, and a fiber having a glass composition of E glass (non-alkali glass) is particularly preferable.

The glass fiber may be a single fiber, or may be a twisted plurality of single fibers. The form of glass fiber is, for example, "glass roving" in which a single fiber or a plurality of twisted fibers are continuously wound, "chopped strand" in which the length is cut to 1 to 10 mm, and crushed to a length of about 10 to 500 μm. It may be any of the above-mentioned "milled fiber".

As the carbon fiber, various known carbon fibers can be used, for example, polyacrylic nitrile-based, rayon-based, pitch-based, polyvinyl alcohol-based, regenerated cellulose-based, pitch-based produced from mesophase pitch, and the like. Carbon fiber can be mentioned. The carbon fiber may be a general-purpose fiber or a high-strength fiber. Further, the carbon fiber may be a long fiber, a short fiber, or a recycled fiber.

By using the fiber (C) whose reinforcing fiber is surface-treated with a urethane-based sizing agent, the interface between the resin (B) and the fiber (C) can be stabilized, and therefore, the molded product containing the fiber-reinforced resin composition can be used. While maintaining high heat resistance, it is possible to improve tensile creep resistance, which is a long-term physical property. For example, when the reinforcing fiber is a fiber whose surface is treated with an acid-modified polypropylene-based sizing agent, the interface between the polyolefin resin (A) and the fiber (C) is stabilized, and the heat resistance tends to be low.

Urethane-based sizing agents include, for example, urethane resins derived from polymeric polyols, organic diisocyanates, and optionally chain extenders and / or crosslinkers.
Examples of the high molecular weight polyol include polyester polyols such as polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyneopentyl adipate diol, polyneopentyl terephthalate diol, polycaprolactone diol, and polyvalerolactone diol; Examples thereof include polyether polyols such as polypropylene glycol, polyoxyethylene oxypropylene glycol, polyoxytetramethylene glycol, and alkylene oxide adducts having 2 to 4 carbon atoms of bisphenols. One kind or two or more kinds of high molecular weight polyols can be used.

Examples of the organic diisocyanate include 2,4'-or 4,4'-diphenylmethane diisocyanate (MDI), 2,4- or 2,6-tolylene diisocyanate (TDI), 4,4'-dibenzyl diisocyanate, 1 , 3- or 1,4-phenylenediocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate and other aromatic diisocyanates; ethylene diisocyanate, hexamethylene diisocyanate (HDI), lysine diisocyanate and other aliphatic diisocyanates; isophorone diisocyanate (isophorone diisocyanate) IPDI), alicyclic diisocyanates such as 4,4'-dicyclohexylmethane diisocyanate can be mentioned. One kind or two or more kinds of organic diisocyanates can be used.

Examples of the chain extender and the cross-linking agent include active hydrogen-containing compounds having a number average molecular weight of 60 to 500, such as polyhydric alcohols, polyhydric phenols, and polyamines. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, neopentyl glycol, and 1,4. Dihydric alcohols such as −bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxyethyl) benzene, 2,2-bis (4,4′-hydroxycyclohexyl) propane; trihydric alcohols such as glycerin and trimethylolpropane Examples thereof include 4- to 8-valent alcohols such as pentaerythritol, diglycerin, α-methylglucoside, sorbitol, xylit, mannit, dipentaerythritol, glucose, fructose and sucrose. Examples of the polyhydric phenols include polyhydric phenols such as pyrogallol, catechol and hydroquinone; and bisphenols such as bisphenol A, bisphenol F and bisphenol S. Examples of the polyamine include aliphatic polyamines such as ethylenediamine, hexamethylenediamine and diethylenetriamine; aliphatic polyamines such as isophoronediamine and 4,4′-dicyclohexylmethanediamine; aromatic polyamines such as 4,4′-diaminodiphenylmethane; Arocyclic ring-containing aliphatic polyamines such as xylylene diamine; hydrazines and derivatives thereof can be mentioned. The chain extender and the cross-linking agent can be used alone or in combination of two or more.

Urethane-based focusing agents include silane-based coupling agents, titanate-based coupling agents, aluminum-based coupling agents, zirconium-based coupling agents, borane-based coupling agents, curing catalysts, lubricants, fillers, as necessary. Tixo-imparting agent, tackifier, wax, heat stabilizer, light-resistant stabilizer, fluorescent whitening agent, foaming agent, pH adjuster, leveling agent, antigelling agent, dispersion stabilizer, antioxidant, radical trapping agent, Heat resistance imparting agent, inorganic filler, organic filler, plasticizing agent, reinforcing agent, antibacterial agent, fungicide, rust preventive, thermoplastic resin, thermosetting resin, pigment, dye, conductivity imparting agent, antistatic Agents, moisture permeability improvers, water repellents, oil repellents, hollow foams, crystalline water-containing compounds, flame retardants, water absorbents, hygroscopic agents, deodorants, foam stabilizers, antifoaming agents, fungicides, preservatives , At least one component selected from antifungal agents, pigment dispersants, antiblocking agents, antioxidants and the like may be contained.

The content of the urethane resin in the urethane-based sizing agent is preferably 0.5 to 5.0% by mass. When the content of the urethane resin is 0.5% by mass or more, the urethane resin can sufficiently cover the entire reinforcing fiber, and a desired effect tends to be obtained. On the other hand, when the content of the urethane resin is 5.0% by mass or less, there is little possibility that decomposition gas is generated during molding.

Examples of the solvent that can be used in the urethane-based sizing agent include water, methanol, ethanol, dimethylformamide, dimethylacetamide, and acetone. The urethane-based sizing agent may be a solution or emulsion containing the urethane resin and the solvent.

Examples of the surface treatment method for reinforcing fibers using a urethane-based sizing agent include a method of applying a urethane-based sizing agent to the surface of the reinforcing fibers with an applicator or the like, a method of immersing the reinforcing fibers in a urethane-based sizing agent, and a urethane-based sizing agent. Examples thereof include a method of atomizing the agent and spraying it on the reinforcing fibers, and a method of contacting the reinforcing fibers with a roller to which a urethane-based sizing agent is attached. Further, the surface treatment method may be either a batch method or a continuous method.

The mass ratio of the urethane-based sizing agent in the fiber (C), that is, the loss on ignition is preferably 0.1 to 1.5% by mass. The mass ratio (ignition loss) of the urethane-based sizing agent is measured for the fiber obtained by completely volatilizing the volatile substance by applying the urethane-based sizing agent to the reinforcing fibers with an applicator or the like and drying the fibers. NS. When the ignition loss of the urethane-based sizing agent applied to the surface of the reinforcing fiber is 0.1% by mass or more, the interface between the resin (B) and the fiber (C) described above can be stabilized, and the heat resistance can be improved. It is preferable because it can be expressed. On the other hand, when the ignition loss of the urethane-based sizing agent applied to the surface of the reinforcing fibers is 1.5% by mass or less, physical properties such as heat resistance are improved, which is preferable.

The ignition loss of the urethane-based sizing agent in the fiber (C) is a value measured according to JIS R 3420 (2006) 7.3.2.
The reinforcing fibers after the surface treatment may be focused to a predetermined number, wound, cut and / or crushed as necessary, and processed into chopped strands, milled fibers, yarns, rovings and the like.
One type or two or more types of fibers (C) can be used.

<Modified polyolefin resin (D)>
The modified polyolefin resin (D) improves the interoperability between the polyolefin resin (A) and the resin (B) (for example, acts as a compatibilizer between the resin (A) and the resin (B)), and the composition ( It is a component that improves the heat-resistant deformation resistance and tensile creep resistance of the molded product containing I).

The modified polyolefin resin (D) is, for example, a resin obtained by modifying a polyolefin resin (D1) with at least one component (D2) selected from an unsaturated carboxylic acid and a derivative thereof.

As the polyolefin resin (D1), for example, the polyolefin resin described in the item <Polyolefin resin (A)> can be used, and polypropylene is preferable. One type or two or more types of polyolefin resin (D1) can be used.

Examples of unsaturated carboxylic acids include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, sorbic acid, and angelic acid; maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, tetrahydrophthalic acid, and the like. Examples thereof include unsaturated dicarboxylic acids such as norbornene dicarboxylic acid and bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic acid. Examples of the derivative of the unsaturated carboxylic acid include acid anhydrides, acid halides, esters, amides, imides, and metal salts of unsaturated carboxylic acids, and specific examples thereof include maleic anhydride, itaconic anhydride, and anhydrous. Citraconic acid, tetrahydrophthalic anhydride, bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic acid anhydride, malenyl chloride, methyl acrylate, methyl methacrylate, ethyl acrylate, propyl acrylate, Butyl acrylate, monomethyl maleate, monoethyl maleate, dimethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itacone, diethyl citraconate, dimethyl tetrahydrophthalate, bicyclo [2.2.1] hept-2-ene Examples thereof include dimethyl-5,6-dicarboxylate, acrylamide, maleic acid amide, maleimide, sodium acrylate, and sodium methacrylate. Among these, unsaturated dicarboxylic acid and its derivative are preferable, unsaturated dicarboxylic acid and its anhydride are more preferable, and maleic acid and maleic anhydride are further preferable. The component (D2) may be used alone or in combination of two or more.

As the above-mentioned modification method, a conventionally known method can be used, and examples thereof include a method of grafting a component (D2) on a polyolefin resin (D1). Specifically, the component (D2) is grafted onto the polyolefin resin (D1) serving as the main chain of the graft in the presence of a radical polymerization initiator.

As the grafting method, a conventionally known method can be used, and examples thereof include a solution method and a melt-kneading method. For example, a method in which a polyolefin resin (D1) is suspended or dissolved in a solvent, and a component (D2) and a radical polymerization initiator are added and mixed, and graft-polymerized, usually at a temperature of 80 to 200 ° C.; Examples thereof include a method in which the component (D2) and the radical polymerization initiator are brought into contact with each other under melt-kneading at a temperature equal to or higher than the melting point of (D1), for example, 180 to 300 ° C.

Examples of the solvent used in the solution method include aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane and decane; and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. Hydrogen-based solvent; Chlorinated hydrocarbon-based solvent such as trichloroethylene, perchloroethylene, dichloroethylene, dichloroethane, chlorobenzene; aliphatic alcohol-based solvent such as ethanol and isopropanol; ketone solvent such as acetone, methylisobutylketone and methylethylketone; methyl acetate , Ethyl acetate, butyl acetate and the like, and ester-based solvents can be mentioned. One kind or two or more kinds of solvents can be used.

Examples of the radical polymerization initiator include organic peroxides and azo compounds. Examples of the organic peroxide include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-trioil peroxide, di-t-butyl peroxide, dicumyl peroxide, and (2,5-dimethyl-2). , 5-bis (t-butylperoxy) hexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexin-3, lauroyl peroxide, t-butylperoxyacetate, 2,5- Dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxybenzoate, t-butylperoxyisobutyrate, t-butylperoxyphenylacetate, t-butylperoxy-s-octate, t- Butyl peroxypivalate, cumylperoxypivalate, t-butylperoxyethyl acetate can be mentioned. Examples of the azo compound include azoisobutyronitrile and dimethylazoisobutyrate. Radical polymerization initiators include azoisobutyronitrile and dimethylazoisobutyrate. One type or two or more types can be used.

The modified polyolefin resin (D) can also be obtained, for example, by copolymerizing an olefin with the component (D2). As the olefin, the olefin for forming the above-mentioned polyolefin resin (D1) can be used. As the above-mentioned copolymerization method, for example, a conventionally known radical copolymerization method can be used.

The content of the structure derived from the component (D2) in the modified polyolefin resin (D) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and preferably 5% by mass or less, more preferably. Is 1% by mass or less. In the case of a maleic acid-modified polyolefin resin, for example, the above content can be determined from a calibration curve prepared separately based on a peak area of ^{1670 to 1810 cm -1 by measuring the infrared absorption spectrum of the resin.} Even when a component (D2) other than maleic acid is used, the above content can be determined by infrared absorption spectroscopy or the like.

As the modified polyolefin resin (D), at least one resin selected from modified polypropylene and modified polyethylene is preferable, and at least one selected from maleic acid-modified polypropylene, maleic anhydride-modified polypropylene, maleic acid-modified polyethylene and maleic acid-modified polyethylene anhydride. One kind of resin is more preferable, and at least one kind of resin selected from maleic acid-modified polypropylene and maleic anhydride-modified polypropylene is further preferable.
The modified polyolefin resin (D) can be used alone or in combination of two or more.

<Other ingredients>
The composition (I) may contain other components other than the above as long as the object of the present invention is not impaired. Other components include, for example, thermoplastic resins other than polyolefin resin (A), resin (B) and modified polyolefin resin (D), flame retardants, flame retardant aids, fillers, colorants, antibacterial agents, and the like. Antistatic agents can be mentioned. These can be used alone or in combination of two or more.

Other thermoplastic resins include, for example, styrene-butadiene-styrene copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), styrene-ethylene / butylene-styrene copolymer (SEBS), styrene-. Examples thereof include styrene-based thermoplastic elastomers such as ethylene / propylene-styrene copolymer (SEPS).

Examples of the flame retardant include a halogen-based flame retardant (eg, halogenated aromatic compound), a phosphorus-based flame retardant (eg, nitrogen-containing phosphate compound, phosphoric acid ester), and a nitrogen-based flame retardant (eg, guanidine, triazine). , Melamine and derivatives thereof), inorganic flame retardants (eg metal hydroxides), boron flame retardants, silicone flame retardants, sulfur flame retardants, red phosphorus flame retardants.

Examples of the flame retardant aid include various antimony compounds, metal compounds containing zinc, metal compounds containing bismuth, magnesium hydroxide, and clay silicates.
Examples of the filler include glass components (eg, glass beads, glass flakes), silica, graphite, silicic acid compounds (eg, calcium silicate, aluminum silicate, kaolin, talc, clay), metal oxides (eg, iron oxide, etc.). Examples thereof include carbonates and sulfates of metals such as titanium oxide, zinc oxide, antimony oxide, and alumina), calcium, magnesium, and zinc.
Examples of the colorant include pigments and dyes.

<Contents of each component>
By using the composition (I), it is possible to produce a molded product having excellent tensile creep resistance, flexural modulus and bending strength while maintaining high heat-resistant deformation under a high load.
The preferable content of each component in the composition (I) is as follows.
Of the total content of the resin (A), the resin (B) and the fiber (C) of 100 parts by mass, the content of the resin (A) is 5 parts by mass or more, preferably 10 parts by mass or more, more preferably 15 parts by mass. 60 parts by mass or less, preferably 50 parts by mass or less, more preferably 40 parts by mass or less, still more preferably 33 parts by mass or less, and particularly preferably 27 parts by mass or less. When the content of the resin (A) is 5 to 60 parts by mass, the cost and specific gravity are excellent.

Of the total content of the resin (A), the resin (B) and the fiber (C) of 100 parts by mass, the content of the resin (B) is 5 parts by mass or more, preferably 10 parts by mass or more; 60 parts by mass. Hereinafter, it is preferably 50 parts by mass or less. When the content of the resin (B) is 5 to 60 parts by mass, the obtained molded product is excellent in heat resistance and tensile creep resistance.

Of the total content of the resin (A), the resin (B) and the fiber (C) of 100 parts by mass, the content of the fiber (C) is 10 parts by mass or more, preferably 20 parts by mass or more, more preferably 30 parts by mass. More than parts, more preferably 35 parts by mass or more; 70 parts by mass or less, preferably 60 parts by mass or less. When the content of the fiber (C) is 10 to 70 parts by mass, the obtained molded product is excellent in flexural modulus and bending strength.

The content of the modified polyolefin resin (D) is 0.05 parts by mass or more, preferably 0.1 parts by mass, with respect to a total of 100 parts by mass of the contents of the resin (A), the resin (B) and the fiber (C). More than parts; 0.95 parts by mass or less, preferably 0.7 parts by mass or less, more preferably 0.5 parts by mass or less. When the content of the modified polyolefin resin (D) is 0.05 to 0.95 parts by mass, high heat-resistant deformability under a high load of the molded product is maintained as compared with the case where the content is outside this range. Moreover, the tensile creep resistance of the molded product is improved.

Of the total content of the resin (A) and the resin (B) of 100 parts by mass, the content of the resin (B) is preferably 8 parts by mass or more, more preferably 20 parts by mass or more, still more preferably 33 parts by mass or more. , More preferably 45 parts by mass or more, particularly preferably 55 parts by mass or more; preferably 92 parts by mass or less, more preferably 80 parts by mass or less, still more preferably 75 parts by mass or less. When the content of the resin (B) with respect to the total of the resin (A) and the resin (B) is 8 to 92 parts by mass, the obtained molded product is excellent in heat resistance and tensile creep resistance.

The total content of the resin (A), the resin (B), the fiber (C) and the modified polyolefin resin (D) in 100% by mass of the total composition (I) is preferably 70% by mass or more, more preferably 80% by mass. % Or more, more preferably 90% by mass or more.

<Manufacturing method of fiber reinforced resin composition>
The composition (I) can be produced by melt-kneading each of the above-mentioned components. The melt-kneading temperature is, for example, 5 to 100 ° C. higher than the temperature at which the contained component resin (eg, resin (A), resin (B), resin (D)) melts, and is preferably among the contained component resins. The temperature is 10 to 60 ° C. higher than the melting point of the resin having the highest melting point. The melt-kneading treatment time is, for example, 30 seconds or more and 15 minutes or less, preferably 1 to 10 minutes.

The composition (I) may be a short fiber reinforced resin pellet or a long fiber reinforced resin pellet.
When the composition (I) is a short fiber reinforced resin pellet, each of the above components can be well melt-kneaded and dispersed in an extruder or the like with a roll mill, a Banbury mixer, a kneader or the like. It may be dry-blended with a tumbler type blender, a Henschel mixer, a ribbon mixer or the like, and melt-kneaded with a uniaxial extruder, a twin-screw extruder or the like to form a pellet-shaped molding material. In this method, the fiber (C) may be fed from either the top or the side of the extruder. Further, in this method, all or a part of each component other than the fiber (C) may be separately melt-kneaded and then melt-kneaded with the fiber (C).

When the composition (I) is a long fiber reinforced resin pellet, it can be produced by a known method such as a drawing method. After a part of each of the above-mentioned components is separately melt-kneaded, the remaining components may be added and melt-kneaded. For example, glass fiber roving can be guided to an impregnated die, uniformly impregnated with molten resin between filaments, and then pelletized by cutting to a required length.

[Molded product]
The composition (I) can be processed into a molded product by a molding method such as ordinary injection molding, extrusion molding, or press molding. In the case of injection molding, for example, injection molding can be performed using the above-mentioned short fiber reinforced resin pellets or long fiber reinforced resin pellets. In that case, when feeding the short fiber reinforced resin pellets or the long fiber reinforced resin pellets from the hopper of the injection molding machine, other resins, for example, the polyolefin resin described in the item of <polyolefin resin (A)> may be further added. can. In addition, short fiber reinforced resin pellets or long fiber reinforced resin pellets are side-fed from the bend port of the injection molding machine, and other resins, for example, the polyolefin resin described in the item of <polyolefin resin (A)> are fed from the hopper. Then, it can be mixed and molded in the injection molding machine.

Further, the polyolefin resin (A), the resin (B), the fiber (C) and the modified polyolefin resin (D) are melt-kneaded in the injection molding machine without passing through the short fiber reinforced resin pellets and the long fiber reinforced resin pellets. Molding can also be performed. In that case, the fiber (C) may be fed from the hopper of the injection molding machine, or may be side-fed from a vent port or the like.

The molded product of this embodiment contains the composition (I). For example, the molded product of the present embodiment may be entirely formed from the composition (I), or may include a portion formed from the composition (I).

The molded product is used in a wide range of applications from household products such as daily necessities and recreational products to general industrial products and industrial products. For example, home appliance material parts, communication equipment parts, electrical parts, electronic parts, automobile parts, vehicle parts other than automobiles, ships, aircraft materials, mechanical mechanism parts, building material related parts, civil engineering parts, agricultural materials, power tool parts, food Examples include containers, films, sheets and fibers.

As automobile parts, it can be deployed in various parts such as power train parts due to improved heat resistance, mechanical parts due to improved tensile creep resistance, and outer panel parts due to improved bending characteristics, but other parts. It can also be applied to sites. Specific parts names include intake manifolds, oil pans, cylinder heads, cylinder head covers, engine covers, shrouds, mirror brackets, interior consoles, sun roofs, sun roof frames, front doors, back doors, sliding doors, front end modules, etc. Door modules, fenders, foil caps, gasoline tanks, belts, ceiling upholstery, compatible tops, armrests, door trims, rear package trays, sun visors, foil covers, mattress covers, airbags, insulation, wire coverings, electrical insulation, Examples include overlay materials, floor materials, corner walls, deck panels, covers, plywood, ceiling boards, partition boards, side walls, wallpaper, wall coverings, exterior materials, interior materials, roofing materials, soundproof boards, and heat insulating boards.

Examples of home appliance material parts, communication equipment parts, electrical parts, and electronic parts include printers, personal computers, word processors, keyboards, small information terminals (PDAs), headphone stereos, mobile phones, telephones, facsimiles, copying machines, and electronic money. Office / OA equipment such as registration machines (ECR), calculators, electronic notebooks, electronic dictionaries, cards, holders, stationery; home appliances such as washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting equipment, game machines, irons, and sardines. AV equipment such as TVs, VTRs, video cameras, radio cassette recorders, tape recorders, mini discs, CD players, speakers, liquid crystal displays; connectors, relays, capacitors, switches, printed boards, coil bobbins, semiconductor encapsulation materials, electric wires, cables, Examples include transformers, deflection yokes, distribution boards, and clocks.

Examples of daily necessities include daily necessities such as plywood, synthetic fiber boards, buckets, containers, bags, cases, goggles, skis, rackets, tents, bicycles, and musical instruments.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following description, "parts" represents "parts by mass".
[Example 1]
Polypropylene [PP, manufactured by Prime Polymer Co., Ltd., product number "J137G", melting point 160 ° C., MFR (230 ° C., 2.16 kg load) = 30 g / 10 min] 21 parts as polyolefin resin (A), and polyamide as polyamide resin (B1) 6 [PA6, manufactured by Ube Kosan Co., Ltd., product number "1013B", melting point 225 ° C., MFR (230 ° C., 2.16 kg load) = 40 g / 10 min] 39 parts, and maleic acid-modified polypropylene [modified as modified polyolefin resin (D)] PP, manufactured by Mitsui Chemicals, product number "AT2606", content of structure derived from maleic acid 0.3% by mass] 0.1 part was mixed in advance by dry blending, and a twin-screw melt-kneading extruder (Japan Steel Works, Ltd.) It was supplied to a hopper manufactured by "TEX25αIII-52.CW-4V", screw diameter 26 mm, L / D = 53). On the other hand, 40 parts of glass fiber chopped strands (GF1, length 4 mm, filament diameter 13 μm) surface-treated as fibers (C) with a urethane-based surface treatment agent were supplied from the side of the twin-screw melt-kneading extruder. A fiber-reinforced resin composition was prepared by heat-melting and kneading at a temperature of 250 ° C. Here, the reason why the glass fibers are supplied from the side of the twin-screw melt-kneading extruder is to prevent the glass fibers from being crushed by the melt-kneading and to keep the fiber length as long as possible.

The fiber-reinforced resin composition obtained above is injection-molded using an injection molding machine (manufactured by Toshiba Machine Co., Ltd., "EC75XIII") under injection conditions of a set temperature of 250 ° C. and a mold temperature of 60 ° C., and the fiber-reinforced resin is formed. A strip test piece for evaluation test (length 80 mm × width 10 mm × thickness 4 mm) and a dumbbell type test piece for evaluation test (based on JIS K7139 (ISO 3167)) made of the composition were prepared.

[Examples 2 to 10, Comparative Examples 1 to 12]
A fiber-reinforced resin composition and a test piece were prepared under the same conditions as in Example 1 except that the compounding composition was changed as shown in Tables 1 to 3. In Tables 1 to 3, the numerical values of each component are based on parts by mass. GF2 is a glass fiber chopped strand (length 4 mm, filament diameter 13 μm) surface-treated with an acid-modified PP surface treatment agent, and CF is a urethane-based surface treatment. A carbon fiber chopped strand (length 4 mm, filament diameter 7 μm) surface-treated with an agent.

<Evaluation of thermal deformation temperature>
Using a strip test piece for evaluation test (length 80 mm x width 10 mm x thickness 4 mm), in accordance with ISO 751-1 (0.45 MPa load and 1.8 MPa load), "Automatic HDT" manufactured by Toyo Seiki Seisakusho Co., Ltd. The thermal deformation temperature was measured with a "testing machine".

<Evaluation of bending test>
The bending test was carried out in accordance with ISO 178 using a strip test piece for evaluation test (length 80 mm x width 10 mm x thickness 4 mm), and the flexural modulus FM (MPa) and bending strength FS in the stress-strain curve. (MPa) was determined.

<Evaluation of tensile creep strain>
The tensile creep strain was measured using the above-mentioned evaluation test dumbbell type test piece of JIS K7139 as a test piece under the conditions of an initial stress of 5.0 MPa, a test temperature of 80 ° C., and a test time of 100 hours.

Claims (8)

Polyolefin resin (A) and
With at least one resin (B) selected from polyamide resin (B1) and polyester resin (B2),
Fibers (C) whose reinforcing fibers are surface-treated with a urethane-based sizing agent, and
A fiber-reinforced resin composition containing a modified polyolefin resin (D).
The content of the resin (A) is 5 to 60 parts by mass in a total of 100 parts by mass of the contents of the resin (A), the resin (B) and the fiber (C), and the content of the resin (B) is 5 to 60 parts by mass. The content is 5 to 60 parts by mass, and the content of the fiber (C) is 10 to 70 parts by mass.
The content of the modified polyolefin resin (D) is 0.05 to 0.95 parts by mass with respect to a total of 100 parts by mass of the contents of the resin (A), the resin (B) and the fiber (C). be,
Fiber reinforced resin composition. The fiber-reinforced resin composition according to claim 1, wherein the resin (B) is the polyamide resin (B1). The fiber-reinforced resin composition according to claim 1 or 2, wherein the polyamide resin (B1) is polyamide 6. The invention according to any one of claims 1 to 3, wherein the content of the resin (B) is 8 to 92 parts by mass in a total of 100 parts by mass of the contents of the resin (A) and the resin (B). Fiber reinforced resin composition. The fiber-reinforced resin composition according to any one of claims 1 to 4, wherein the resin (A) is polypropylene. The fiber-reinforced resin composition according to any one of claims 1 to 5, wherein the reinforcing fiber is at least one selected from glass fiber and carbon fiber. A molded product containing the fiber-reinforced resin composition according to any one of claims 1 to 6. The molded product according to claim 7, which is an automobile part.