JP4821213B2 - Thermoplastic resin composition - Google Patents

Description

  The present invention relates to a thermoplastic resin composition, and particularly provides a thermoplastic resin composition having excellent mechanical properties. The molded article using the thermoplastic resin composition of the present invention is suitably used for electrical / electronic equipment, OA equipment, home appliances or automobile parts, internal members, and housings.

  A fiber reinforced composite material composed of a reinforced fiber and a matrix resin is lightweight and has excellent mechanical properties, and thus is widely used in sports equipment applications, aerospace applications, and general industrial applications.

  Reinforcing fibers used in these fiber-reinforced composite materials reinforce molded products in various forms depending on the intended use. These reinforcing fibers include metal fibers such as aluminum fibers and stainless fibers, organic fibers such as aramid fibers and PBO fibers, inorganic fibers such as silicon carbide fibers, and carbon fibers. Carbon fibers are preferred from the viewpoint of the balance between rigidity and lightness, and among them, polyacrylonitrile-based carbon fibers are suitably used.

  In order to improve the mechanical properties of these molded articles, the content of reinforcing fibers such as carbon fibers may be increased. However, increasing the amount of carbon fiber increases the viscosity of the material, which makes it difficult to knead in the compounding process or makes injection molding difficult, reducing the mechanical properties such as strength and rigidity of the resulting molded product. Or the appearance of the molded product often deteriorates.

  Therefore, as a means for improving the mechanical properties without impairing the appearance of the molded product, there is a method of improving the interfacial adhesion between the reinforcing fiber and the thermoplastic resin and consequently improving the mechanical properties of the molded product.

  For example, there is a method in which a reinforcing functional fiber is subjected to a surface oxidation treatment to give a reactive functional group to improve adhesion with a thermoplastic resin. However, in this case, when the surface treatment amount is increased, the strength of the reinforcing fiber itself is lowered, which has a problem of affecting the mechanical properties of the molded product. Further, general thermoplastic resins have poor reactivity, and there is a problem that sufficient adhesion cannot be obtained only by surface modification of the reinforcing fibers.

  Then, the method of adding an adhesive improvement component other than a reinforced fiber and a thermoplastic resin has been tried. As an adhesion improving component, for example, a method using an epoxy, polyimine, or polyallylamine having high affinity with a reinforcing fiber has been proposed (see Patent Documents 1, 2, and 3). However, in this case, the affinity with the reinforcing fiber is good, but the affinity with the thermoplastic resin is insufficient, and there is a problem that a molded product having excellent mechanical properties cannot be obtained.

Thus, the present condition is that the adhesive component which fully satisfies affinity with both a reinforced fiber and a thermoplastic resin is not found.
JP-A-61-66616 (Claims) Japanese Patent Laid-Open No. 03-65311 (Claims) JP 07-266462 A (Claims)

In view of the problems in the prior art, the present invention provides a thermoplastic resin composition capable of enhancing the adhesiveness between carbon fibers , which are reinforcing fibers , and a thermoplastic resin, and sufficiently improving the mechanical properties of a molded product. It is intended to do.

  The present inventors have used in combination a compound having an amino group and a compound having one or more functional groups capable of reacting with the amino group and having a good compatibility with a thermoplastic resin serving as a matrix. The inventors have found that the mechanical strength of a molded article can be specifically improved when added to a reinforced thermoplastic resin, and have arrived at the present invention.

That is,
(1) The component (D) is added to the component (C) to which the following components (A) and (B) are added, and the solubility parameter δ _B (SP value) of the compound of the component (B) and ( A thermoplastic resin composition characterized in that the absolute value of the difference in solubility parameter δ _D (SP value) of the thermoplastic resin of component D) is 3 or less.
(A) Compound amine value is 5 mg eq / g or more (B) a carboxyl group, one selected from an acid anhydride group and an epoxy group or Ranaru group or polyolefin-based polymer containing two or more functional groups (C) Carbon fiber (D) Polyolefin polymer (2) The thermoplastic resin composition according to (1), wherein the compound of component (A) is a compound represented by the following structural formula (1).

m1, m3: an integer of 0 to 20 m2: an integer of ₁ to 20 R ₁ , R ₂ , R ₃ : an alkyl group having a linear or branched structure represented by C _n H _2n , where n is 1 to 20 (3) The compound of the component (A) is a compound having a hydrocarbon skeleton containing 50 to 100 mol% of a unit represented by the following structural formula (2) or the following structural formula (3) in the compound. (1) The thermoplastic resin composition as described.

R ₄ : an alkyl group having a straight chain or branched structure represented by —H or —C ₁ H _{21 + 1} (wherein 1 represents an integer of 1 to 4), and p is a value of 0.01 to 10

  (4) The thermoplastic resin composition according to (2), wherein the compound of component (A) is polyethyleneimine.

  (5) The thermoplastic resin composition according to (3), wherein the compound of component (A) is polyallylamine.

  (6) The thermoplastic resin composition as described in any one of (1) to (5) above, wherein the compound (A) is a compound having a number average molecular weight of 200 to 100,000.

  (7) The ratio (R value) between the number average molecular weight of the compound of the component (A) represented by the following formula (1) and the amine value (mg eq / g) (R value) is 5 to 5,000. The thermoplastic resin composition according to any one of (6).

R value = number average molecular weight / amine value (mg eq / g) -------- (1)
(8) The thermoplastic resin composition according to any one of (1) to (7), wherein the component (B) is a compound containing at least a carboxyl group, and the acid value thereof is 10 to 150 mgKOH / g.

  (9) The thermoplastic resin composition according to any one of (1) to (7), wherein the component (B) is a compound containing at least an acid anhydride group, and the saponification value thereof is 10 to 500 mgKOH / g.

  (10) The thermoplastic resin composition according to any one of (1) to (7), wherein the component (B) is a compound containing at least an epoxy group, and the epoxy value thereof is 10 to 500 mgKOH / g.

  (11) The thermoplastic resin composition according to any one of (1) to (10), wherein the compound (B) has a number average molecular weight of 500 to 200,000.

( 12 ) The surface oxygen concentration ratio O / C determined by X-ray photoelectron spectroscopy of the carbon fiber of the component (C) is 0.05 to 0.50, or any one of (1) to (11). Thermoplastic resin composition.

( 13 ) The weight ratio (A) / (C) of the component (A) to the component (C) is 0.005 to 0.1, and the weight ratio of the component (B) to the component (C) (B) / (C). There 0.005, and in any of (D) the weight ratio of component (C) (D) / the (C) is 0.14 to 100 (1) - (12) The thermoplastic resin composition as described.

( 14 ) The proportion of the compound of component (A) is 0.1 to 10% by weight, the proportion of the compound of component (B) is 0.1 to 10% by weight, and the proportion of carbon fiber of component (C) Is a thermoplastic resin composition according to any one of the above (1) to ( 13 ), wherein the ratio of the thermoplastic resin of component (D) is 10 to 98.8% by weight.

According to the present invention, a fiber reinforced thermoplastic resin composition for producing a molded article having excellent adhesion between carbon fibers as reinforcing fibers and a thermoplastic resin, and extremely excellent mechanical properties such as bending strength and bending elastic modulus. Since a product can be obtained, a molded article using this thermoplastic resin composition can be suitably used for electrical / electronic equipment, OA equipment, home appliances or automobile parts, internal members, and housings.

  Hereinafter, the best mode for carrying out the thermoplastic resin composition of the present invention will be described in more detail.

The basic composition of the thermoplastic resin composition of the present invention comprises the following components (A) to (D), the solubility parameter δ _B (SP value) of the compound (B) and the heat of the component (D). The thermoplastic resin composition is characterized in that the absolute value of the difference in solubility parameter δ _D (SP value) of the plastic resin is 3 or less.
(A) Compound amine value is 5 mg eq / g or more (B) a carboxyl group, one selected from an acid anhydride group and an epoxy group or Ranaru group or polyolefin-based polymer containing two or more functional groups (C) Carbon fiber (D) polyolefin polymer The thermoplastic resin composition of the present invention comprises (C) carbon fiber and (D) a fiber reinforced thermoplastic resin composition containing a polyolefin polymer , and (C) carbon. Combining (A) component with good adhesion to fiber and (D) component that is compatible with (D) polyolefin polymer and that can react with (A) component to form a chemical bond. Can improve the adhesion between (C) carbon fibers and a matrix resin (mixture of (A) component (B) component (D) polyolefin polymer ) and improve the mechanical properties of the molded product to an unprecedented level. What we can do It is what I found. That is, the thermoplastic resin composition of the present invention is obtained by adding the component (D) to the component (C) to which the components (A) and (B) are added.

As the component (A) used in the present invention, a compound having an amine value of 5 mg eq / g or more is used from the viewpoint of adhesion to the carbon fiber (C). When the amine value is less than 5 mg eq / g, the affinity with the carbon fiber surface is reduced, and sufficient interfacial adhesion between the carbon fiber and the resin cannot be obtained. A more preferable range of the amine value is 10 to 1,000 mg eq / g, more preferably 15 to 500 mg eq / g, and still more preferably 20 to 300 mg eq / g.

  The amine value is an index indicating the total amount of 1,2,3 and tertiary amines measured according to ASTM D2074, and is expressed in mg of KOH equivalent to hydrochloric acid required to neutralize 1 g of component (A).

  The component (A) in the present invention preferably has a structure having a unit represented by the following structural formula (1).

(In the formula, m1 and m3 are integers of 0 to 20, and m2 is an integer of 1 to 20. Each of R ₁ , R ₂ and R ₃ represents a linear or branched structure represented by C _n H _2n. And n represents an integer of 1 to 20.)
The component (A) is typically represented by [Chemical Formula 1], but the branched branch may be further branched.

  The component (A) having the unit represented by the structural formula (1) includes, for example, polyethyleneimine, polypropyleneimine, polybutyleneimine, N-acetylpolyethyleneimine, N-propionylpolyethyleneimine, 1,1-dimethylethyleneimine, 1,1-dimethyl-2-methylethyleneimine, 1,1-dimethyl-2-propylethyleneimine, N-butyrylpolyethyleneimine, N-valerylpolyethyleneimine, N-hexanoylpolyethyleneimine, N-stearoylpolyethyleneimine, Examples thereof include polyamines such as polybenzaldoimine and derivatives thereof, mixtures thereof, and modified and copolymerized polyimine resins. Among these, polyethyleneimine is particularly preferable.

  In addition, the component (A) in the present invention preferably has a structure having a hydrocarbon skeleton containing 50 to 100 mol% of a structural unit represented by the following structural formula (2) or structural formula (3).

(In the formula, R ₁ represents —H or —C ₁ H _{2l + 1} (l represents an integer of 1 to 4), and p represents a value of 0.01 to 10.)
The component (A) having the unit represented by the structural formula (2) is composed of 50 to 100 mol% of a carboxyl group-containing unsaturated monomer such as acrylic acid or methacrylic acid, and unsaturated such as acrylic acid ester or methacrylic acid ester. After solution polymerization of 0 to 50 mol% of the monomer in a suitable organic solvent, the carboxyl group present in the molecule of the produced polymer has 1 to 3 carbon atoms such as ethyleneimine and propyleneimine. It can be produced by reacting an alkyleneimine having an alkyl group. Note that p is not limited to an integer because it has a distribution in the number of bonds due to the reaction and is expressed as an average value.

  Examples of the component (A) having the unit represented by the structural formula (3) include polyallylamine, and those in which a part of the amine in the side chain of polyallylamine is converted to hydrochloride. Allylamine is preferred.

  Polyallylamine can be synthesized using, for example, a method disclosed in JP-A-58-201811. That is, an inorganic acid salt of a monoallylamine compound is polymerized in a polar solvent in the presence of a radical initiator containing an azo group and a group having a cationic nitrogen atom in the molecule, and then the inorganic acid of the polymerized polyallylamine compound The salt can be prepared by removing the inorganic acid through a strongly basic ion exchange resin or dialyzing an aqueous neutralized salt solution made of alkali (eg, caustic soda).

The compound (A) in the present invention preferably has a number average molecular weight of 200 to 100,000. When the number average molecular weight is less than 200, the component (A) cannot uniformly cover the carbon fiber surface, and the adhesion effect may be reduced. When the number average molecular weight exceeds 100,000, the layer made of the component (A) covers the carbon fiber surface thickly, and the interface may become fragile. From this viewpoint, the more preferable range of the number average molecular weight is 250 to 80,000. The number average molecular weight of the component (A) was calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column packed with polystyrene cross-linked gel (for example, shodex GPC K-804; manufactured by Showa Denko KK) and chloroform as a GPC solvent were used.

In addition, the compound of the component (A) in the present invention is preferably a compound having an R value which is a ratio of the number average molecular weight and the amine value represented by the following formula (1) to 5 to 5,000. When the R value is less than 5, the resin in the vicinity of the surface of the carbon fiber coated with the component (A) becomes excessively active, and the interface between the surface of the carbon fiber and the resin may become fragile. Moreover, when R value exceeds 5,000, the reactivity of the surface of a carbon fiber and the interface of resin becomes scarce, and the adhesive effect may be reduced.

R value = number average molecular weight / amine value (mg eq / g) -------- (1)
In addition, the weight ratio (A) / (C) of the component (A) and the component (C) in the present invention is preferably 0.005 to 0.1 from the viewpoint of adhesiveness at the interface between the carbon fiber and the resin ( When the weight ratio (A) / (C) between the component A) and the component (C) is less than 0.005, the component (A) cannot be uniformly covered on the carbon fiber surface, and the adhesion effect may be reduced. is there. Moreover, when a ratio exceeds 0.1, an interface may become brittle. More preferably, it is 0.007-0.05, More preferably, it is 0.01-0.04.

  Moreover, it is preferable that the ratio of the component (A) with respect to the thermoplastic resin composition of this invention is 0.1 to 10 weight%. More preferably, it is 0.3-5 weight%, More preferably, it is 0.6-2 weight%.

(B) component in the present invention needs to have reactivity with the amino groups of component (A), from this point of view, a carboxyl group, acid anhydride group, one or two elements selected or epoxy group et al Polyolefin polymers having the above functional groups are used.

The number average molecular weight of the component (B) compound used in the present invention is preferably 500 to 200,000. When the number average molecular weight is less than 500, the adhesion between the reinforcing fiber and the thermoplastic resin becomes insufficient. When the number average molecular weight exceeds 200,000, the reactivity with the amino group of the component (A) decreases, and the reinforcing fiber. In some cases, the adhesion at the interface between the carbon fiber and the polyolefin polymer as the thermoplastic resin becomes poor. A more preferable range of the number average molecular weight is 1,000 to 100,000. The number average molecular weight of the component (B) was calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column packed with polystyrene cross-linked gel (for example, shodex GPC K-804; manufactured by Showa Denko KK) and chloroform as a GPC solvent were used.

Specific examples of the component (B) in the present invention are, for example, polyethylene (PE), polypropylene (PP) and that the polyolefin such as polybutylene (PB) was modified with an acid anhydride or epoxy groups, or, mosquitoes carboxyl Polyolefin polymers having side chains are preferably used. Modified with an acid anhydride group or epoxy group, or the proportion of introduction of the side chain of mosquitoes carboxyl is based on the monomeric units, the reactivity of the amino group that is the component (A) is 1 to 30 mol% From the viewpoint of

  In addition, when the component (B) is a compound containing at least a carboxyl group in the side chain of polyolefin such as polyethylene (PE), polypropylene (PP), and polybutylene (PB), the acid value thereof is the component (A) From the viewpoint of reactivity with the amino group therein, those having 10 to 150 mgKOH / g are more preferable. The acid value is more preferably 20 to 100 mgKOH / g, and further preferably 30 to 80 mgKOH / g. When the acid value is less than 10 mgKOH / g, the reaction with the amino group in the component (A) becomes insufficient, and as a result, the interfacial adhesion is insufficient and the strength of the molded product may be lowered. When the acid value exceeds 150 mgKOH / g, the reaction with the amino group in the component (A) proceeds, the interface becomes strong, and as a result, the molded product may become brittle.

  The acid value is expressed in mg of KOH required to neutralize 1 g of the component (B) containing a carboxyl group, and was measured according to JIS K0070 (1992).

  When the component (B) is a compound containing at least an acid anhydride group in the side chain of polyolefin such as polyethylene (PE), polypropylene (PP), and polybutylene (PB), the saponification value is (A From the viewpoint of reactivity with the amino group in the component, a compound having a content of 10 to 500 mgKOH / g is more preferred. The saponification value is more preferably 20 to 300 mgKOH / g, and still more preferably 20 to 100 mgKOH / g. When the saponification value is less than 10 mgKOH / g, the reaction with the amino group in the component (A) becomes insufficient, and as a result, the interfacial adhesion is insufficient and the strength of the molded product may be lowered. When the saponification value exceeds 500 mgKOH / g, the reaction with the amino group in the component (A) proceeds, the interface becomes strong, and as a result, the molded product may become brittle.

  The saponification value is expressed in mg of KOH required for saponifying 1 g of component (B) containing an acid anhydride group, and was measured according to JIS K0070 (1992).

  In addition, when the component (B) is a compound containing at least an epoxy group in the side chain of polyolefin such as polyethylene (PE), polypropylene (PP), and polybutylene (PB), the epoxy value is the component (A) From the viewpoint of reactivity with the amino group therein, those having 10 to 500 mgKOH / g are more preferred. The epoxy value is more preferably 20 to 300 mgKOH / g, and still more preferably 30 to 100 mgKOH / g. When the epoxy value is less than 10 mgKOH / g, the reaction with the amino group in the component (A) becomes insufficient, and as a result, the interfacial adhesion is insufficient and the strength of the molded product may be lowered. When the epoxy value exceeds 500 mgKOH / g, the reaction with the amino group in the component (A) proceeds, the interface becomes strong, and as a result, the molded product may become brittle.

  The epoxy value was converted to mg by multiplying the reciprocal of the epoxy equivalent (weight of a sample containing 1 equivalent of an epoxy group) measured according to JIS K7236 (2001) by the molecular weight (56) of KOH.

In the present invention, the weight ratio (B) / (C) of the component (B) to the component (C) is 0.005 to 0.1. The carbon fiber that is a reinforcing fiber and the polyolefin resin that is a thermoplastic resin. It is preferable from the viewpoint of adhesiveness at the interface of the polymer . When the weight ratio (B) / (C) of the component (B) to the component (C) is less than 0.005, the component (B) cannot be uniformly covered on the carbon fiber surface, and the bonding effect is reduced. There is. Moreover, when a ratio exceeds 0.1, an interface may become brittle. More preferably, it is 0.007-0.05, More preferably, it is 0.01-0.04.

Moreover, it is preferable that the ratio of the component (B) with respect to the thermoplastic resin composition of this invention is 0.1 to 10 weight%. The ratio is more preferably 0.3 to 5% by weight, and still more preferably 0.6 to 2% by weight.
Moreover, it is preferable to control the weight ratio (A) / (B) of the component (A) and the component (B) in the range of 0.1 to 10 in the present invention. By controlling within the above range, a strong chemical bond can be formed at the interface between the carbon fiber as the reinforcing fiber and the polyolefin polymer as the thermoplastic resin, and as a result, a molded product having excellent mechanical properties can be obtained. it can. (A) / (B) is more preferably 0.2-5, and still more preferably 0.3-3.3. Carbon fiber is a reinforcing fiber component (C) used in the present invention, for example, port polyacrylonitrile-based, rayon-based, or carbon fiber lignin and pitch-based, a graphite fiber. Among these, specific strength, specific stiffness, in view of the balance of light weight and conductivity, polyacrylonitrile-based carbon fiber is preferably used especially.

  The carbon fiber has a surface oxygen concentration {O / C} which is a ratio of the number of oxygen (O) and carbon (C) atoms on the fiber surface measured by X-ray photoelectron spectroscopy of 0.05 to 0.5. Is preferable, more preferably 0.06 to 0.3, and still more preferably 0.07 to 0.2. When the surface oxygen concentration {O / C} is 0.05 or more, the amount of polar functional groups on the surface of the carbon fiber can be secured, and the affinity with the thermoplastic resin composition can be increased to obtain stronger adhesion. it can. Moreover, when the surface oxygen concentration {O / C} is 0.5 or less, it is possible to reduce a decrease in strength of the carbon fiber itself due to oxidation.

The amount of the oxygen-containing functional group of the carbon fiber is determined according to the following procedure by X-ray photoelectron spectroscopy. First, after cutting the carbon fiber from which the sizing agent adhering to the surface of the carbon fiber with a solvent was removed and spreading it on a copper sample support table, using A1Kα1,2 as the X-ray source, Keep at 1 × 10 ⁸ Torr. The kinetic energy value (KE) of the main peak of C _1s is adjusted to 1202 eV as a peak correction value associated with charging during measurement. C _1s peak area E. Is obtained by drawing a straight base line in the range of 1191 to 1205 eV. O _1s peak area E. Is obtained by drawing a straight base line in the range of 947 to 959 eV. Here, the oxygen-containing functional group amount is calculated as an atomic ratio from the ratio of the O _1s peak area to the C _1s peak area using a sensitivity correction value unique to the apparatus. As an X-ray photoelectron spectroscopy apparatus, model ES-200 manufactured by Kokusai Electric Inc. was used, and the sensitivity correction value was set to 1.74.

  The means for controlling the surface oxygen concentration {O / C} to 0.05 to 0.5 is not particularly limited. For example, techniques such as electrolytic oxidation treatment, chemical oxidation treatment, and vapor phase oxidation treatment are used. Can take.

The carbon fiber of component (C) used in the present invention preferably has a total fineness of 50 to 5,000 tex. More preferably, it is 500-3,500 tex. When it is less than 50 tex, the efficiency of the cutting work is deteriorated, and the productivity may be lowered. On the other hand, if it exceeds 5,000 tex, the convergence of the bundle is poor at the time of cutting, and fluffing may occur.

Moreover, it is preferable that the number of the carbon fiber of (C) component used by this invention is 1,000-70,000. Preferably, it is 12,000-48,000. When the number is less than 1,000, the efficiency of the cutting work is deteriorated, and the productivity may be reduced. However, if the number exceeds 70,000, the bundling property is poor at the time of cutting, and fluffing may occur.

Moreover, it is preferable to cut and use the carbon fiber of (C) component used by this invention in the length of 1-60 mm, and it is a more preferable aspect that it is cut into the length of 3 mm-50 mm. . If the cut length is shorter than 0.1 mm, the reinforcing effect tends to be lowered. On the other hand, if the cut length is longer than 60 mm, the fluidity at the time of molding is lowered and the formability is deteriorated.

In addition, the form of the carbon fiber of the component (C) used in the present invention is not particularly limited, but a knitted fabric, a woven fabric, a web, a nonwoven fabric, a felt, or a mat shape is preferably used.

  The carbon fiber or graphitized fiber of the reinforcing fiber used in the present invention has a strand strength of 4 to 7 GPa, preferably 4.5 to 6.5 GPa, and a strand elastic modulus of 200 to 500 GPa. It is particularly suitable for structural materials.

The strand strength is obtained by impregnating a bundle of carbon fiber or graphitized fiber with a resin having the following composition and curing it at a temperature of 130 ° C. for 35 minutes, followed by a tensile test method specified in JIS R-7601. be able to.
(Resin composition)
-Alicyclic epoxy resin (3,4-epoxycyclohexylmethyl-3,4-epoxy-cyclohexyl-carboxylate) 100 parts by weight-3 parts by weight of boron trifluoride monoethylamine-4 parts by weight of acetone A tensile test can be performed by the same method as the above strand strength measuring method, and it can be determined from the slope of the load-elongation curve.

The carbon fiber used in the present invention is blended with a polyolefin polymer which is a thermoplastic resin as a woven fabric, long fiber roving or chopped strand, but the carbon fiber is cut into a length of 1 to 60 mm and used. It is preferable that it is cut into a length of 5 mm to 30 mm. If the cut length is shorter than 1 mm, the reinforcing effect tends to be lowered. On the other hand, if the cut length is longer than 60 mm, the fluidity at the time of molding is lowered and the formability is deteriorated. Moreover, the form of the carbon fiber is not particularly limited.

The proportion of the carbon fiber of the component (C) in the thermoplastic resin composition of the present invention can be arbitrarily set according to the physical properties required for the thermoplastic resin composition, but from the viewpoint of moldability and mechanical properties of the molded product Therefore, the content is preferably 1 to 70% by weight. More preferably, it is 5-50 weight%, More preferably, it is 10-40 weight%.

And min (D) formed is used in the present invention, heat is thermoplastic resin Po Riechiren (PE), polypropylene (PP), from the viewpoint polyolefin polymer is a general purpose of the cost and general industries, such as polybutylene Used. These copolymers, modified products, and resins obtained by blending two or more types may be used .

  The proportion of the component (D) in the thermoplastic resin composition of the present invention is preferably 10 to 98.8% by weight from the viewpoint of the mechanical properties of the molded product. More preferably, it is 30-90 weight%, More preferably, it is 50-80 weight%.

The thermoplastic resin composition of the present invention has an absolute difference between the solubility parameter δ _B of the component (B) compound and the solubility parameter δ _D (SP value) of the thermoplastic resin (D) from the viewpoint of enhancing the mechanical properties. It is essential that the value is 3 or less.

(B) if the absolute value of the difference between the solubility parameter [delta] _D solubility parameter [delta] _B and component (D) of the thermoplastic resin component of the compound is greater than 3, the compatibility of both components is low, the carbon is reinforced fiber In some cases, the adhesiveness at the interface between the fiber and the polyolefin-based polymer that is a thermoplastic resin is lowered. A more preferable range of the absolute value is 2.5 or less, and more preferably 2 or less.

A preferable range of the solubility parameter δ _B of the compound (B) is 5 to 20. The solubility parameter δ _B is more preferably 8-15. When the solubility parameter δ _B is less than 5, the reactivity with the component (A) becomes poor, and the adhesion improving effect is reduced. When the solubility parameter δ _B exceeds 20, the binding force with the component (A) is increased, and the interface may be fragile. The solubility parameter δ _B of the component (B) can be controlled by the type and number of polar functional groups (carboxyl group, acid anhydride group, epoxy group) and molecular weight contained in the compound.

A preferred range of the solubility parameter δ _D of the component (D) compound is 5-20. The solubility parameter [delta] _D more preferably is 8 to 15. If the solubility parameter [delta] _D is less than 5, (A) component and (B) compatibility poor becomes adhesion improving effect of the component is reduced. If the solubility parameter [delta] _D is more than 20, it may become poor wettability to the carbon fiber surface, the impregnation insufficient. The solubility parameter δ _D of the component (D) can be controlled by the type and number of polar functional groups (carboxyl group, acid anhydride group, epoxy group, isocyanate group, amide group, etc.) and the molecular weight contained in the compound. it can.

  The solubility parameter δ (SP value) refers to the value of the repeat unit of the polymer at a temperature of 25 ° C. determined by the method of Fedors. The method is described in F.A. Fedors, Polym. Eng. Sci. 14 (2), 147 (1974).

  The thermoplastic resin composition of the present invention may contain other components other than the above components (A) to (D), depending on the application, etc., as long as the mechanical properties are not impaired. Fillers, additives and the like may be included. As fillers or additives, inorganic fillers, flame retardants, conductivity imparting agents, crystal nucleating agents, ultraviolet absorbers, antioxidants, vibration damping agents, antibacterial agents, insect repellents, deodorants, coloring inhibitors, heat There are stabilizers, mold release agents, antistatic agents, plasticizers, lubricants, colorants, pigments, foaming agents and coupling agents.

  In particular, the addition of a flame retardant for applications that require flame retardancy, and the addition of a conductivity imparting agent for applications that require electrical conductivity are preferably employed. Examples of the flame retardant include flame retardants such as halogen compounds, antimony compounds, phosphorus compounds, nitrogen compounds, silicone compounds, fluorine compounds, phenol compounds, and metal hydroxides. Among these, from the viewpoint of suppressing environmental burden, phosphorus compounds such as ammonium polyphosphate, polyphosphazene, phosphate, phosphonate, phosphinate, phosphine oxide, and red phosphorus can be preferably used.

  Examples of the conductivity imparting agent that can be used include carbon black, amorphous carbon powder, natural graphite powder, artificial graphite powder, expanded graphite powder, pitch microbeads, vapor-grown carbon fiber, and carbon nanotube.

  The thermoplastic resin composition of the present invention is formed into a molded product by a molding method such as press molding, injection molding, blow molding, rotational molding, extrusion molding, transfer molding, and filament winding molding.

  Next, the manufacturing method of the fiber reinforced thermoplastic resin composition of this invention is demonstrated.

The manufacturing method of the fiber reinforced thermoplastic resin composition of the present invention comprises at least the following first step, second step and third step.
-1st process: The process of processing the carbon fiber of (C) component into fabrics, such as a knitted fabric, a woven fabric, a web, a nonwoven fabric, felt, or a mat,
-2nd process: The compound whose amine value of (A) component is 5 mgeq / g or more to 1-70 weight% of cloth | dough obtained at the said 1st process in (A) / (C) weight ratio. after the application so that from 001 to 0.1, the polyolefin comprises one or more functional groups selected from the component (B) carboxyl group, acid anhydride group and an epoxy group or Ranaru group weight A step of applying the coalesced so that the weight ratio (B) / (C) is 0.001 to 0.1.
Third step: A step of heating and melting the polyolefin polymer of component (D) to the base material to which components (A) and (B) have been applied to give 10 to 98% by weight to be combined.

In the first step, a conventionally known method is used as a method of processing the carbon fiber of the component (C) into a fabric such as a knitted fabric, a woven fabric, a web, a nonwoven fabric, a felt, or a mat.

  In the first step, in addition to the carbon fiber of the component (C), 0 to 50% by weight of the polyolefin polymer of the component (D) may be previously mixed with the dough.

The form of the polyolefin polymer of the component (D) used in the present invention is preferably a film form, a particulate form or a non-woven form.
In the second step, the components (A) and (B) may be imparted to the carbon fiber of the component (C) by separately or sequentially forming each component as a solution or an emulsion (C ) A method of evaporating the solvent or the dispersion medium after adhering to the component carbon fiber is preferably used. As a method of attaching the components (A) and (B), a conventionally known method such as a spray method or a dip method is used. Examples of the solvent that dissolves the components (A) and (B) include water, methanol, ethanol, dimethylformamide, dimethylacetamide, acetone, and the like. However, it is preferable because it is easy to handle and does not ignite when evaporated. Water is preferred. In the case of a compound that is insoluble or hardly soluble in the solvent, an emulsifier, a surfactant or the like can be added and used as an emulsion. Specifically, as an emulsifier and a surfactant, an anionic emulsifier such as styrene-maleic anhydride copolymer, olefin-maleic anhydride copolymer, naphthalene sulfonate formalin condensate, polyacrylic acid soda, Nonionic emulsifiers such as cationic emulsifiers such as polyethyleneimine and polyvinylimidazoline, nonylphenol ethylene oxide adducts, polyvinyl alcohol, polyoxyethylene ether ester copolymers, sorbitan ester ethyl oxide adducts, etc. can be used. Nonionic emulsifiers that have a small interaction with the olefin are preferred.

  Moreover, in said 2nd process, after provision of (A) component or after provision of (B) component, it may be hot-air dried at the temperature of 100-200 degreeC for 0.1 to 90 minutes as needed. Good.

In the third step, as a specific example of the method of (D) heating and melting and applying the polyolefin-based polymer , the base material obtained in the second step is coated with a film-like or nonwoven-like (D) polyolefin. After sandwiching the polymer, a method of impregnating with heat and pressure using a double belt press or flat plate press, or impregnating the base material obtained in the second step with a particulate polyolefin polymer , A method of impregnating with heat and pressure using a belt press or a flat plate press can be exemplified.

  Examples of the form of the fiber-reinforced thermoplastic resin composition obtained through the third step (compositing step) include stampable sheets and prepregs. Furthermore, by cutting them, they can be made into pellets or flakes, and can be used for general injection molding.

  Examples of uses of the molded article made of the thermoplastic resin composition of the present invention include personal computers, displays, OA equipment, mobile phones, personal digital assistants, facsimile machines, compact discs, portable MDs, portable radio cassettes, PDAs (electronic notebooks) Portable information terminals, etc.), video cameras, digital still cameras, optical equipment, audio, air conditioners, lighting equipment, recreational goods, toy products, other household appliances and other electrical and electronic equipment casings and internal components such as trays and chassis And building materials such as cases, mechanical parts and panels, motor parts, alternator terminals, alternator connectors, IC regulators, potentiometer bases for light deer, suspension parts, exhaust gas valves and other valves, fuel related, exhaust system or intake system Various pie , Air intake nozzle snorkel, intake manifold, various arms, various frames, various hinges, various bearings, fuel pump, gasoline tank, CNG tank, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, Oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake butt wear sensor, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine Bain, wiper motor related parts, distributor, starter switch, starter relay, tiger Wire harness for transmission, window washer nozzle, air conditioner panel switch board, coil for fuel related electromagnetic valve, connector for fuse, battery tray, AT bracket, headlamp support, pedal housing, handle, door beam, protector, chassis, frame, armrest , Horn terminal, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, noise shield, radiator support, spare tire cover, seat shell, solenoid bobbin, engine oil filter, ignition device case, under cover, scuff plate, pillar trim , Propeller shaft, wheel, fender, fascia, bumper, bumper beam, bonnet, Aero parts, platforms, cowl louvers, roofs, instrument panels, spoilers and various modules, automobile related parts, parts and skins and landing gear pods, winglets, spoilers, edges, ladders, elevators, failings, ribs Aircraft related parts such as, members and skins.

[Evaluation / Measurement Method]
(1) Solubility parameter δ (SP value)
In the structural formula of the desired compound, it was determined by the following formula from the evaporation energy and molar volume data of atoms and atomic groups.
δ = (ΣΔei / ΣΔvi) ^1/2
(However, in the formula, Δei and Δvi represent the evaporation energy and molar volume of the atom or atomic group, respectively.)
In addition, the structural formula of the compound to be determined can be determined using ordinary structural analysis techniques such as IR, NMR, and mass spectrum.

The components used in the following examples and comparative examples are as follows.
<(A) component>
A-1: Polyethyleneimine “Epomin (registered trademark)” SP-003, manufactured by Nippon Shokubai Co., Ltd.
Amine value 21mg eq / g
Number average molecular weight 300
-A-2: Acrylic polymer "Polyment (registered trademark)" SK-1000 manufactured by Nippon Shokubai Co., Ltd.
Amine value 85 mg eq / g (converted to mg by multiplying the reciprocal of amine hydrogen equivalent 650 g / eq by the molecular weight of KOH (56))
Weight average molecular weight 50,000
A-3: Polyallylamine Nittobo Co., Ltd. PAA-10C
Amine value 770 mg eq / g
Number average molecular weight 15,000
A-4: Polyethyleneimine “Epomin (registered trademark)” P-1000 manufactured by Nippon Shokubai Co., Ltd.
Amine value 18mg eq / g
Number average molecular weight 70,000
A-5: Polyethyleneimine “Epomin (registered trademark)” SP018 manufactured by Nippon Shokubai Co., Ltd.
Amine value 19mg eq / g
Number average molecular weight 1,800
-A-6: Polyoxypropyleneamine PTI Japan Co., Ltd. D-2000
Amine value 116mg eq / g
Number average molecular weight 2,000
<(B) component>
B-1: maleic anhydride modified polypropylene Maruyoshi Kasei Co., Ltd. MGP-055
SP value 8.3
Saponification value 40mgKOH / g
Number average molecular weight 20,000
B-2: Epoxy-modified polyolefin Sumitomo Chemical Co., Ltd. “Bond First (registered trademark)” 7M
SP value 8.1
Epoxy value 35mgKOH / g
Number average molecular weight 20,000
B-3: Acrylic acid-modified polyethylene Maruyoshi Kasei Co., Ltd. MYE30E5
SP value 8.2
Acid value 40mgKOH / g
Number average molecular weight 20,000
B-4: Unmodified polypropylene Sanyo Chemical Industries, Ltd. “Biscol (registered trademark)” 330-P
SP value 8.0
Number average molecular weight 15,000
<(C) component>
C-1: PAN-based carbon fiber Carbon fiber "Torayca (registered trademark)" manufactured by Toray Industries, Inc.
Mass per unit length 0.8 g / m
Specific gravity 1.8 g / cm ³
Tensile strength 4.9 GPa
Tensile modulus 230.0 GPa
O / C 0.10
<(D) component>
D-1: Polypropylene resin Sumitomo Mitsui Polyolefin Co., Ltd. J104WA
SP value 8.0
(2) Molded plate evaluation method A bending strength test piece having a length of 130 ± 1 mm and a width of 25 ± 0.2 mm was cut out from the carbon fiber reinforced composite material obtained in Examples or Comparative Examples. According to the test method prescribed in ASTM D-790, the support span was set to 100 mm using a three-point bending test jig (indenter 10 mm, fulcrum 10 mm), and the bending strength was measured at a crosshead speed of 5.3 mm / min. In this example, “Instron (registered trademark)” universal testing machine 4201 type (manufactured by Instron) was used as a testing machine. The number of measurements was n = 5, and the average value was the bending strength.

Hereinafter, the present invention will be specifically described by way of one embodiment, but the present invention is not particularly limited thereto.
Example 1
・ First step:
Water and polyoxyethylene-octylphenyl ether (trade name: “Triton” (registered trademark) x-100) were introduced into a cylindrical container having a diameter of 150 mm to obtain a 0.1 wt% aqueous solution. Into this, 9 g of the above (C-1) PAN-based carbon fiber cut to a length of 6 mm was added and stirred for 4 minutes. After stirring, the web was dehydrated to obtain a nonwoven web.
・ Second step:
After adding 50 g of the above-mentioned (A-1) polyethyleneimine previously adjusted to a 5% by weight aqueous solution from the top of the nonwoven web obtained in the first step, the emulsion was previously adjusted to a 5% by weight emulsion. Further, 50 g of the above-mentioned (B-1) maleic anhydride-modified polypropylene was added by spraying. After the dehydration treatment, hot air drying was performed at 140 ° C. for 60 minutes.
-Third step:
On the stainless steel plate, 9 g of the (D-1) unmodified polypropylene is placed, another stainless steel plate is stacked thereon, and a 0.5 mm spacer is placed between the plates. The pressing temperature is 210 ° C., the pressure is 1 kgf / cm ² , and the pressure is maintained for 10 minutes to obtain a polypropylene film having a thickness of 0.5 mm × 20 cm × 20 cm. The substrate nonwoven web obtained in the second step is placed thereon. Furthermore, the other polypropylene film is placed from above and placed at a temperature of 200 ° C. for 30 minutes to obtain a carbon fiber reinforced sheet having a thickness of 1.2 mm.

Next, the four carbon fiber reinforced sheets obtained were stacked, a spacer with a thickness of 4 mm was placed, and held at a temperature of 200 ° C. for 20 minutes under a pressure of 1 kgf / cm ² by a heating press molding machine, A flat carbon fiber reinforced composite material of 20 cm × 20 cm × 4 mm is obtained.

The proportion of the component (A) in the obtained carbon fiber reinforced composite material is 1% by weight, the proportion of the component (B) is 1% by weight, the proportion of the component (C) is 50% by weight, and the proportion of the component (D) is It was 48% by weight.
(Example 2)
In the second step of Example 1, the carbon fiber reinforced composite material was prepared in the same manner as in Example 1 except that (A-2), which was previously adjusted to a 5 wt% emulsion, was added as the component (A). Obtained.

The proportion of the component (A) in the obtained carbon fiber reinforced composite material is 1% by weight, the proportion of the component (B) is 1% by weight, the proportion of the component (C) is 50% by weight, and the proportion of the component (D) is It was 48% by weight.
(Example 3)
In the second step of Example 1, a carbon fiber reinforced composite material was obtained in the same manner as in Example 1 except that (A-3), which was previously adjusted to a 5% by weight aqueous solution, was added as the component (A). It was.
The proportion of the component (A) in the obtained carbon fiber reinforced composite material is 1% by weight, the proportion of the component (B) is 1% by weight, the proportion of the component (C) is 50% by weight, and the proportion of the component (D) is It was 48% by weight.
Example 4
In the second step of Example 1, a carbon fiber reinforced composite material was obtained in the same manner as in Example 1 except that the above (A-4) previously adjusted to a 5 wt% aqueous solution was added as the component (A). It was.
The proportion of the component (A) in the obtained carbon fiber reinforced composite material is 1% by weight, the proportion of the component (B) is 1% by weight, the proportion of the component (C) is 50% by weight, and the proportion of the component (D) is It was 48% by weight.
(Example 5)
In the second step of Example 1, carbon fiber reinforcement was performed in the same manner as in Example 1 except that (B-2), which was previously adjusted to a 5% solids aqueous dispersion, was added as component (B). A composite material was obtained.

The proportion of the component (A) in the obtained carbon fiber reinforced composite material is 1% by weight, the proportion of the component (B) is 1% by weight, the proportion of the component (C) is 50% by weight, and the proportion of the component (D) is It was 48% by weight.
(Example 6)
In the 2nd process of Example 1, after adding said (A-5) previously adjusted to 5 weight% aqueous solution as (A) component, solid content 5 weight% emulsion previously as (B) component A carbon fiber reinforced composite material was obtained in the same manner as in Example 1 except that the (B-3) prepared above was added.

The proportion of the component (A) in the obtained carbon fiber reinforced composite material is 1% by weight, the proportion of the component (B) is 1% by weight, the proportion of the component (C) is 50% by weight, and the proportion of the component (D) is It was 48% by weight.
(Example 7)
In the second step of Example 1, a carbon fiber reinforced composite material was prepared in the same manner as in Example 1 except that the above (A-6) previously adjusted to a 5 wt% ethanol solution was added as the component (A). Obtained.

The proportion of the component (A) in the obtained carbon fiber reinforced composite material is 1% by weight, the proportion of the component (B) is 1% by weight, the proportion of the component (C) is 50% by weight, and the proportion of the component (D) is It was 48% by weight.
(Comparative Example 1)
In the second step of Example 1, a carbon fiber reinforced composite material was obtained in the same manner as in Example 1 except that the components (A) and (B) were not used.

The proportion of component (C) in the obtained carbon fiber reinforced composite material was 50% by weight, and the proportion of component (D) was 50% by weight.
(Comparative Example 2)
In the second step of Example 1, a carbon fiber reinforced composite material was obtained in the same manner as in Example 1 except that the component (A) was not added.

The proportion of the component (B) in the obtained carbon fiber reinforced composite material was 2% by weight, the proportion of the component (C) was 50% by weight, and the proportion of the component (D) was 48% by weight.
(Comparative Example 3)
In the second step of Example 1, a carbon fiber reinforced composite material was obtained in the same manner as in Example 1 except that the component (B) was not added.

The proportion of component (A) in the obtained carbon fiber reinforced composite material was 2% by weight, the proportion of component (C) was 50% by weight, and the proportion of component (D) was 48% by weight.
(Comparative Example 4)
In the second step of Example 1, as the component (B), the carbon fiber reinforced composite material was prepared in the same manner as in Example 1 except that (B-4) previously adjusted to a 5 wt% aqueous dispersion was added. Obtained.

  The proportion of the component (A) in the obtained carbon fiber reinforced composite material is 1% by weight, the proportion of the component (B) is 1% by weight, the proportion of the component (C) is 50% by weight, and the proportion of the component (D) is It was 48% by weight.

  A bending test was performed on each sample of Examples 1 to 7 and Comparative Examples 1 to 4 described above. The results are shown in Table 1. As can be seen from Table 1, the carbon fiber reinforced composite material (molded product) obtained from the thermoplastic resin composition according to the present invention has excellent bending strength, and adhesion at the interface between the reinforced fiber and the thermoplastic resin. It can be seen that the properties are good.

The thermoplastic resin composition of the present invention is excellent in adhesion between carbon fibers that are reinforcing fibers and polyolefin polymer that is a thermoplastic resin , and can sufficiently improve the mechanical properties of a molded product. The molded article using the thermoplastic resin composition of the invention is suitably used for electrical / electronic equipment, OA equipment, home appliances or automobile parts, internal members, and casings, and is useful.

Claims (14)

The component (D) is added to the component (C) to which the following components (A) and (B) are added, and the solubility parameter δ _B (SP value) of the compound of the component (B) and the component (D) A thermoplastic resin composition, wherein an absolute value of a difference in solubility parameter δ _D (SP value) of the thermoplastic resin is 3 or less.
(A) Compound amine value is 5 mg eq / g or more (B) a carboxyl group, one selected from an acid anhydride group and an epoxy group or Ranaru group or polyolefin-based polymer containing two or more functional groups (C) Carbon fiber (D) Polyolefin polymer The thermoplastic resin composition according to claim 1, wherein the compound (A) is a compound represented by the following structural formula (1).

m1, m3: an integer of 0 to 20 m2: an integer of ₁ to 20 R ₁ , R ₂ , R ₃ : an alkyl group having a linear or branched structure represented by C _n H _2n , where n is 1 to 20 Integer The heat according to claim 1, wherein the compound of component (A) is a compound having a hydrocarbon skeleton containing 50 to 100 mol% of a unit represented by the following structural formula (2) or the following structural formula (3) in the compound. Plastic resin composition.

R ₄ : an alkyl group having a straight chain or branched structure represented by —H or —C ₁ H _{21 + 1} (wherein 1 represents an integer of 1 to 4), and p is a value of 0.01 to 10

The thermoplastic resin composition according to claim 2, wherein the compound of component (A) is polyethyleneimine.   The thermoplastic resin composition according to claim 3, wherein the compound of component (A) is polyallylamine.   The thermoplastic resin composition according to any one of claims 1 to 5, wherein the compound (A) is a compound having a number average molecular weight of 200 to 100,000. The ratio (R value) of the number average molecular weight and the amine value (mg eq / g) of the compound of the component (A) represented by the following formula (1) is 5 to 5,000. The thermoplastic resin composition described in 1.
R value = number average molecular weight / amine value (mg eq / g) -------- (1) The thermoplastic resin composition according to any one of claims 1 to 7, wherein the component (B) is a compound containing at least a carboxyl group, and the acid value thereof is 10 to 150 mgKOH / g. The thermoplastic resin composition according to any one of claims 1 to 7, wherein the component (B) is a compound containing at least an acid anhydride group, and the saponification value thereof is 10 to 500 mgKOH / g.   The thermoplastic resin composition according to any one of claims 1 to 7, wherein the component (B) is a compound containing at least an epoxy group, and has an epoxy value of 10 to 500 mgKOH / g.   The number average molecular weight of the compound of (B) component is 500-200,000, The thermoplastic resin composition in any one of Claims 1-10. The thermoplastic resin composition according to any one of claims 1 to 11, wherein the surface oxygen concentration ratio O / C determined by X-ray photoelectron spectroscopy of the carbon fiber of component (C) is 0.05 to 0.50. . The weight ratio (A) / (C) of the component (A) to the component (C) is 0.005 to 0.1, and the weight ratio (B) / (C) of the component (B) to the component (C) is 0.00. The thermoplastic resin composition according to any one of claims 1 to 12 , wherein the weight ratio (D) / (C) of the component (D) and the component (C) is 0.14 to 100. object. The proportion of the compound (A) is 0.1 to 10% by weight, the proportion of the compound (B) is 0.1 to 10% by weight, and the proportion of the carbon fiber (C) is 1 to 10% by weight. The thermoplastic resin composition according to any one of claims 1 to 13 , which is 70% by weight and the ratio of the thermoplastic resin as the component (D) is 10 to 98.8% by weight.