JPH04173840A - Composite thermoplastic-resin material with high strength - Google Patents

Abstract

PURPOSE: To provide a thermoplastic resin composite material that is highly strong, has an improved adhesiveness between the resin matrix and carbon fiber, and is useful for minute ion sensors, by combining carbon fiber, a poly(arylene sulfide) and another resin component.

CONSTITUTION: The desired material comprises (A) carbon fiber, (B) an amine- terminated poly(arylene sulfide) as a resin component, and (C) a second resin component comprising a poly(arylene sulfide), polyolefin, polysulfone, polyethersulfone, polyetherimide, polytherketone, polyetheretherketone, polyetherketoneketone, liquid crystal polymer, or a mixture of these resins, and is reinforced by the component A. The component A is preferably present in an amount of about 10-80% based on the amount of the whole resins in the material.

COPYRIGHT: (C)1992,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates generally to poly(arylene sulfide) composites, and more particularly to poly(arylene sulfide) composites having improved adhesion between the resin matrix and carbon fibers in the composite.
arylene sulfide)/carbon fiber composite material.

It has long been recognized that there is a need for good adhesion between resin matrices and reinforcing fibers used in composite materials. A common means used to increase adhesion between the fibers and the resin matrix has been to use a sizing agent to coat the fibers prior to consolidation with the resin matrix.

Sizing compositions generally act in one of two ways to aid adhesion. The sizing composition is sometimes chemically active and acts to form chemical bonds between the fibers and the resin matrix, or allows the matrix to spread over the fibers more easily.
Either it creates a more compatible surface on the fibers to facilitate adhesion to the fibers. When the reinforcing fibers have been glass fibers, compositions containing silanes have been successfully used as sizing agents to bind the glass fibers and the resin matrix.

The use of carbon fibers in composite materials has led to a variety of different approaches. Many proprietary sizing compositions have been used with varying degrees of success in the preparation of well-known and older thermoset matrix/carbon fiber composites.

In recent years, there has been increasing interest in composite materials using thermoplastic matrices and carbon fibers. Much of the interest is due to the generally better processability and longer shelf life of thermoplastics compared to thermosets, as well as the fact that poly(
This is because thermoplastic resins such as arylene sulfide have greater chemical resistance and moisture resistance.

The well-known poly(arylene sulfide) is a poly(arylene sulfide).
phenylene sulfide) and poly(phenylene sulfide/sulfone), which are commercially available from Phillips Petroleum Company, Puddle Spill, Oklahoma, under the registered trademark RYTON. Such resins have stiffness, heat resistance, and
Due to its excellent electrical resistance, it is particularly suitable for use in composite materials.

However, thermoplastic resins pose a number of problems in obtaining composite materials with good adhesion to reinforcing carbon fibers. The same chemical resistance and relatively low chemical activity that make thermoplastics such as poly(phenylene sulfide) and poly(phenylene sulfide/sulfone) attractive for use in composites combine with the chemical bonding of carbon fibers. prevents effective adhesion of the resin to. Most thermoplastics have a higher viscosity than thermosets and therefore do not physically spread onto carbon fibers in the same way as thermosets. Similarly, most of the sizing agents traditionally used in thermoset composites degrade at the temperatures required to process thermoplastics such as poly(arylene sulfide). Therefore, a method for producing thermoplastic/carbon fiber composites with improved adhesion between the thermoplastic matrix and carbon fibers, and composites so produced, particularly poly(arylene sulfide), is proposed. ) resin and poly(arylene sulfide/sulfone) resin.

The present invention provides a carbon fiber reinforced thermoplastic composite material with improved adhesion between carbon fibers and their surrounding resin matrix, measured as improvement in transverse tensile strength and compressive strength, and The above needs are met by providing a method of manufacturing a composite material.

Composite materials basically consist of carbon fibers, a poly(arylene sulfide) first resin component having an amine group at the end of the molecular chain, and poly(arylene sulfite), polyolefin, polysulfone, polyether-sulfone, polyetherimide, polyetherketone, polyetheretherketone, polyetherketoneketone, liquid crystal polymer,
and a second thermoplastic resin component selected from the group consisting of mixtures of these resins. In the most preferred embodiment, the second component comprises poly(phenylene sulfide) resin.

The poly(arylene sulfide) first resin component having amine end groups is prepared by adding an amino-organothiol compound to the blend of the poly(arylene sulfide) polymerization recipe before the polymerization is substantially complete. Polymers with terminal amine groups thus prepared were tested (using a 1,250-inch orifice, ASTM D
-1238, measured according to condition 31710.36)
Melt flow is about 10g/10 minutes to about 5000g/1
0 minutes and serves to improve the adhesion of the thermoplastic matrix to the carbon fibers in composite materials containing carbon fibers. Generally, such improved adhesion and improved composite materials are achieved even when the amine-terminated poly(arylene sulfide) component is present in the thermoplastic resin matrix in an amount of only about 0.5% of the total resin weight. If you do, it will come.

The method of the present invention for producing the improved thermoplastic/carbon fiber composite material described above basically consists of the components used in the composite material, namely carbon fibers, poly(( arylene sulfide) and a thermoplastic resin second component, and then forming a composite material from the mixture. A variety of techniques can be used to combine the carbon fiber and thermoplastic components and form a composite material therefrom, including injection molding and pultrusion. A preferred method of the invention is a pultrusion technique in which a roving of continuous fibers is pulled through a resin matrix consisting of a mixture of a first component of poly(arylene sulfide) terminated with amine groups and a second component of a thermoplastic resin. Take advantage of.

The fiber rovings are impregnated with a resin matrix and then pulled through a heated forming die to consolidate the carbon fibers and resin matrix into a composite material. A variation of the pultrusion process involves impregnating the carbon fibers with a poly(arylene sulfide) component by pulling it through a poly(arylene sulfide) component that has amine groups at the ends, and then transferring the impregnated rovings to a thermoplastic material. The method includes depositing the second component resin onto the roving by drawing it through a second component of resin, and then passing the roving through a heated forming die.

As stated above, the thermoplastic/carbon fiber composite material of the present invention having improved adhesion of the thermoplastic to carbon fibers and thus improved structural strength is characterized by
The first component is a poly(arylene sulfide) resin with an amine group at the end that serves to improve adhesion, as well as poly(arylene sulfite), polyolefin, polysulfone, polyether sulfone, polyetherimide, polyether ketone, poly A second component of a thermoplastic resin selected from the group consisting of ether ether ketone, polyether ketone ketone, liquid crystal polymer, and mixtures of such thermoplastic resins.

Poly(arylene sulfide) with amine group at the end
The resin component provides improved bonding to the reinforcing carbon fibers through amine end groups, while the polymeric portion is bonded to the second thermoplastic resin component used. In addition to such chemical bonding, the amine-terminated poly(arylene sulfide) component allows the thermoplastic matrix of the second component to extend over the fibers and more easily adhere to them. A surface is introduced onto the carbon fiber.

The terms "poly(arylene sulfide)" and "poly(arylene sulfite) resin" are used herein to refer broadly to arylene sulfite polymers, whether homopolymers, copolymers, terpolymers, etc., or blends of such polymers. used to refer to. Poly(arylene sulfide) resins particularly suitable for use in accordance with the present invention include poly(phenylene sulfide) resins and poly(arylene sulfide) resins.
phenylene sulfide/sulfone) resin.

Poly(phenylene sulfide) resins suitable for use in accordance with the present invention are disclosed in U.S. Pat.
Published on November 21, 967): No. 3,919.177
Issue (issued on November 11, 1975): No. 4,038,
No. 261 (issued on July 26, 1977): and No. 4,
656.231 (issued on April 7, 1987) as described in each specification. A preferred commercially available poly(phenylene sulfide) resin is a poly(phenylene sulfide) resin manufactured by Phillips Petroleum Company, Purdle Spill, Oklahoma, and sold under the registered trademark RYTON. Item is ASTM D1238, condition 31515
．． The melt flow measured by 0 has a value of about 10 g/10 min to about 1000 g/10 min.

Poly(phenylene sulfide/sulfone) resins and methods for their production are described in U.S. Pat. No. 4,016,145 (1977).
No. 4,127,713 (issued on April 5, 2017);
(issued on November 28, 2013) are described in each specification. These patents are incorporated herein by reference. A preferred commercially available poly(phenylene sulfide/sulfone) resin is poly(phenylene sulfide/sulfone) manufactured by Phillips Petroleum Company and sold under the registered tradename RYTON S and conforms to ASTM D1238, Condition 34315. Melt flow measured by .0 is approximately 0.5 g/10 minutes to approximately 350
g/10 minutes.

Poly(arylene sulfide) with amine group at the end
Resins, especially poly(phenylene sulfide) resins and poly(
To prepare phenylene sulfide/sulfone) resins, the basic manufacturing method described in the above-cited patents can be used, in which polyhalo substitution of sulfur compounds in a polar organic solvent is used. React with aromatic compounds. Additionally, alkali metal carboxylates such as, for example, sodium acetate can be included in the reaction mixture to produce higher molecular weight polymers.

Compounds found to be useful as sulfur sources in manufacturing processes generally include alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfide. Suitable alkali metal sulfides include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide. Suitable alkali metal bisulfides include lithium bisulfide, sodium bisulfide, potassium bisulfide, rubidium bisulfide, and cesium bisulfide. As suitable first sulfur sources, sodium sulfide and sodium bisulfide are preferred in this case. It is often convenient for the process of the present invention to use these first sulfur sources as an aqueous solution or dispersion.

Polyhalo-substituted aromatic compounds that can be used include:
A compound in which a halokene atom is bonded to a carbon atom in an aromatic ring. Preferably, the polyhalo-substituted aromatic compound is selected from the group consisting of p-dihalobenzene having the formula; m-dihalobenzene having the formula; and O-dihalobenzene having the formula. However, in the above formula, X is a halogen selected from the group consisting of chlorine, bromine, and iodine, and R is hydrogen or an alkyl group having 1 to 4 carbon atoms. The use of dichlorobenzene is preferred, and p-dichlorobenzene is particularly preferred, because of its availability and generally good results. Mixtures of suitable polyhalo-substituted aromatic compounds can also be used.

Additionally, polyhalo-substituted aromatic compounds having two or more halokene substituents per molecule can be used. These compounds are represented by the formula R' (X)n.

However, X is as defined above and R' has 6 carbon atoms.
It is a polyvalent aromatic radical with a valence of ~16,
n is an integer from 3 to 6. Generally, the polyhalo-substituted aromatic compound of the formula R' (X)n is an optional component used in small amounts in combination with the appropriate dihalo-substituted aromatic compound when used in accordance with the present invention.

Examples of some suitable polyhalo-substituted aromatic compounds include:
1.4-dichlorobenzene, 1.3-dichlorobenzene, 1,3.5-1-dichlorobenzene, 1゜2-dichlorobenzene, 1.4-dibromobenzene, 1.4-shortbenzene, 1-chloro- 4-bromobenzene, 1-
Bromo-4-iodobenzene, 2,5-dichlorotoluene, 2,5-dichloro-p-xylene, 1-ethyl-4
-isopropyl-2,5-dibromobenzene, 1,2,
4.5-tetramethyl-3,6-dichlorobenzene, 1
, 2.3-trichlorobenzene, 1゜2.4-trichlorobenzene, 1.3-dichloro-5-bromobenzene,
2,4.6-trichlorotoluene, hexachlorobenzene, 2.2', 4.4'-tetrachlorobiphenyl, 2.2', 6.6'-tetrabromo-3,3'
, 5.5'-tetramethylbiphenyl, 4.4'-dichlorobiphenyl and the like.

The relative amount of polyhalo-substituted aromatic compound to the total amount of sulfur source compounds can vary over a wide range, but generally the amount used ranges from about 0.5 mole percent excess of aromatic halide with respect to total sulfur source compounds to aromatic There may be up to about a 10 mole percent excess of group halide. 2
A ˜3 mole percent excess is preferred.

Polar organic compounds that can be used include organic amides, lactams, ureas, sulfones, and the like. Examples of suitable polar organic compounds include N-methyl-2-pyrrolidone, N-methylcaprolactam, hexamethylphosphoramide, tetramethylurea, N,N'-ethylenedipyrrolidone, pyrrolidone, caprolactam, N-ethylcaprolactam. , 1,3-dimethyl-2-imidazolidinone, tetramethylene sulfone, diphenyl sulfone, N-
Included are ethyl-2-pyrrolidone, 1-methyl-4-isopropyl-2-piperazinone, 1,4-dimethyl-2-piperazinone, and mixtures thereof. N-methyl-2-pyrrolidone is a preferred polar organic compound because of its ready availability, stability, and good results. The amount of polar organic compound used can be expressed in terms of the molar ratio of polar organic compound to total sulfur source compounds.

The molar ratio will therefore be from about 1°5=1 to about 25=1, preferably from about 2:1 to about 8:1.

The reaction temperature at which the polymerization is carried out can vary within a wide range;
Generally it will be in the range of about 25°C to about 375°C, preferably in the range of about 175°C to about 350°C. Reaction times can vary widely, depending in part on the reaction temperature, but will generally range from about 6 minutes to about 72 hours, preferably from about 1 hour to about 8 hours. The pressure must be sufficient to keep the organic components of the reaction mixture substantially in the liquid phase. The produced arylene sulfide polymer is prepared from the reaction mixture by conventional procedures such as filtering the polymer followed by washing with water, or diluting the reaction mixture with water followed by filtration and washing the polymer with water. can be separated by

Poly(arylene sulfide) with amine group at the end
To produce the resin, an aminoorganothiol compound is added to the polymerization reaction mixture. The addition can be made before the polymerization conditions are established or as the polymerization reaction progresses. The produced poly(arylene sulfide) having an amine group at the end meets ASTM D1238, Condition 317.
10.36 from about 10 g/10 minutes to about 50
It should have a melt flow in the range of 00 g/'10 minutes.

The amino-organothiol compound has the formula Z-8-R" (wherein,
Z is a cyclic amino organic group with no halogen substituents and preferably contains a total of about 5 to about 25 carbon atoms. ). Z can be selected from amino-carbocyclic groups and amino-heterocyclic groups (containing 1 to 4 heteroatoms as ring members). The heteroatoms are each selected from the group consisting of nitrogen, oxygen, and sulfur.

Halogen-free cyclic amino-organic radicals Z are the same (also the group consisting of alkyl, cycloalkyl, aryl, alkoxy, aryloxy, acyl, aroyl, alkoxycarbonyl, alkanamido, alkylamino, and alkylsulfonyl). The -8-R' moiety of the Z-3-R' compound is directly bonded to the carbon atom that is a ring member of Z.

R' is selected from the group consisting of metal M selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, and barium, and hydrogen.

Thus, the amino-organothiol compound can be used as the thiol itself or as its metal salt, ie, metal thiolate, with the proviso that the metal is selected from those listed above. When using metal thiolates according to the invention, the thiolates are prepared in situ (i
n 5itU) (provided that the metal is selected from those listed above). metal thiolate in 5
Examples of suitable metal compounds used to form itu include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, lithium hydride, sodium hydride, magnesium oxide, calcium oxide,
There are strontium oxide and barium oxide.

Suitable examples of halogen-free cyclic amino-organic groups Z in the amino-organothiol compound Z-S-R' include 2- and 4-aminophenyl, 2- and 4'-aminobiphenyl, Contains aminonaphthyl and aminopyridyl.

As mentioned above, the amino-organothiol compound can be added to the polymerization reaction mixture in various ways and at various times. However, it is particularly convenient to add the amino-organothiol compound in admixture with a portion of the polar organic compound component used before carrying out the polymerization reaction.

The amount of amino-organothiol compound used can be expressed in terms of the molar ratio of amino-organothiol compound used to the inorganic sulfur source. This ratio is approximately 0°000
It is in the range of 1:1.00 to about 0.10:1.00. As previously mentioned, the amine-terminated polymers produced should have melt flows in the range of about Log/10 minutes to about 5000 g/10 minutes, depending on the amino-organothiol compound used. The amount can be varied to obtain such desired melt flow.

Generally, the polymerization reaction is conducted at a temperature ranging from about 25°C to about 375°C, preferably from about 75°C to about 350°C. Reaction times can vary widely depending, in part, on reaction temperature, but generally reaction times will range from about 6 minutes to about 72 hours, preferably from about 1 hour to about 8 hours. The reaction pressure must be sufficient to maintain the organic components of the reaction mixture substantially in the liquid phase. Once the reaction is complete, the produced arylene sulfide polymer with terminal amine groups can be processed by conventional procedures, e.g.
The polymer can be separated from the reaction mixture by procedures such as filtering and washing with water, or diluting the reaction mixture with water and then filtering and washing the polymer.

As readily understood by those skilled in the art,
Poly(arylene sulfide/terminated with amine group)
When producing sulfone) resins, the methods described above can be used, except that dihaloaromatic sulfones are used in the polymerization reaction. Dihaloaromatic sulfones that can be used are represented by the following formula: where xl is selected from the group consisting of fluorine, chlorine, bromine and iodine; Z' is a divalent group selected from the group consisting of: , m is 0 or 1
n is 0 or 1; A is selected from the group consisting of oxygen, sulfur, sulfonyl, CR2''°; and each R'° is selected from the group consisting of hydrogen and an alkyl group having from 1 to about 4 carbon atoms; selected, the total number of carbon atoms in all R'' groups in the molecule is from 0 to about 12.

Examples of some dihalo-aromatic sulfones that can be used include:
Bis(p-fluorophenyl)sulfone, bis(p-chlorophenyl)sulfone, p-chlorophenylp'-bromophenylsulfone, bis(2,5-dipropyl-4
-chlorophenyl) sulfone, etc.

The carbon fibers used in the composite materials of the present invention can take a variety of forms depending on the particular method used to manufacture the composite material. For example, when a composite material is injection molded using an injection molding machine, carbon fibers are chopped into
) to be done. When the composite material is made by pultrusion, long carbon fibers can be used, but continuous carbon fibers are most preferred. The carbon fibers are in the form of individual rovings or bundles. Woven carbon fiber fabrics can also be used.

Whatever form the carbon fibers take, they are generally present in the composite in an amount of about 10% to about 80% by weight of the composite.

The second thermoplastic resin component can be, and is preferred, a poly(arylene sulfide) resin prepared as described above, but in this case the resin does not have amine end groups. Particularly preferred are poly(phenylene sulfide) resins or poly(phenylene sulfide/sulfone) resins or mixtures of these resins. however,
Other thermoplastic resins can also be used, such as polyolefins, polysulfones, polyethersulfones, polyetherimides, polyetherketones, polyetheretherketones, polyetherketoneketones, liquid crystal polymers and mixtures of these resins. Various resins can be used individually, in combination with each other, or in combination with poly(
It may be used in combination with (arylene sulfide) resin.

Generally, the two thermoplastic resin components are present in the composite materials of the present invention in an amount totaling from about 20% to about 90% by weight of the composite material. Of the total amount of thermoplastic resin used in the composite material, poly(arylene sulfide) resin with amine end groups accounts for about 0.5% to about 99.5% of the total resin weight.
can be included in an amount of Preferably, the amine-terminated poly(arylene sulfide) resin comprises from about 0.5% to about 50% of the total resin weight of the total resin used.
present in amounts ranging from .

As mentioned above, the amine-terminated poly(arylene sulfide) component of the composite can be applied to the carbon fibers prior to impregnating the carbon fibers with the second thermoplastic resin component. However, when using this technique, the amount of poly(arylene sulfide) resin with amine end groups is typically about 0.5% of the weight of the composite material produced.
cannot exceed. This is because 0.5 on the fiber
This is because if the resin exceeds 5%, it will cause the fibers to stick to each other. A more preferred technique is to use a poly(arylene sulfide) first component resin having amine end groups as described above in combination with a large amount of a second component resin.

Although a variety of methods can be used to produce the improved composite materials of the present invention, such methods essentially involve bonding carbon fibers to a poly(arylene sulfide) resin having amine end groups. and poly(arylene sulfide) resins, polyolefin resins, polysulfones, polyethersulfones, polyetherimides, polyetherketones, polyetheretherketones, polyetherketoneketones, liquid crystal polymers, and mixtures of these resins. mixing with a thermoplastic second component; then consolidating the mixture into a shaped composite material.

A preferred method of manufacturing the composite materials of the present invention utilizes pultrusion techniques. There, a roving of carbon fibers is pulled through a bath of thermoplastic resin, thereby impregnating the roving with thermoplastic resin. The impregnated roving is then pulled through a heated forming die, and the thermoplastic matrix and carbon fibers are consolidated into a composite material. The pultrusion technique for producing such composite materials was developed by 0°Conn.
or) in US Pat. No. 4,680,224, which is incorporated herein by reference. The thermoplastic resin bath may be a mixture of a first poly(arylene sulfide) resin component having an amine end group and a second thermoplastic resin component, or separate resin baths may be used for each component; in the latter case, The method is to first pull the roving through a resin bath of a first polymer component having amine end groups, and then through a resin bath containing a thermoplastic resin second component.

The terms "consolidate" and "con-solidating" are used herein to describe the process by which a resin mixture and carbon fibers are combined in the presence of heat into a desired state in which the carbon fibers are uniformly disposed within a resin matrix. means to form a composite material into a shape.

The following examples are presented to further illustrate the improved composite material of the present invention and its method of manufacture. The specific reactants, conditions, ratios, and formulations and components employed are for the purpose of illustrating the invention and are not intended to limit it in any way.

Example 1 6.15 moles of para-dichlorobenzene and 0.04538 moles of 4-aminobenzenethiol (based on sulfur) in 6 moles of sodium bisulfide, 16.56 moles of N-methyl-2-pyrrolidone. 0.76 mol%) and 6.035 mol of sodium hydroxide to prepare a poly(phenylene sulfide) resin having an amine group at the terminal. The polymerization reaction was carried out continuously for 1 hour at a rotation speed of 60
It was carried out with stirring at 0 rpm. That is, the first hour was at 235°C, the second hour was at 265°C, and the third hour was at 280°C. The obtained polymer is
ASTM D12 using a 1.250 inch long orifice
38, the melt flow measured under conditions 31710.36 was 87.7 g/10 minutes.

The composite material was made using carbon fiber manufactured under the trade designation AS-12 by Hercules Inc., Wilmington, P.O. Such carbon fibers include No. 1-Cruz
Some were coated with a size by ink (Hercules Inc.) (named G-sized fibers), but were used in the same way as the same carbon fibers without sizing. The carbon fiber roving is pulled out from the creel by Philip Petroleum Co.
hills Petroleum C.

A stirred aqueous solution consisting of approximately 87 wt. The resulting resin-impregnated roving was passed through a drying chamber at a temperature of 740°F, then through an over-and-under die, and finally through a heated forming die at a temperature of 628°F. The resulting consolidated composite material was cut into several pieces and pressed into test laminates.

The strength properties of both laminates made from sized and unsized carbon fibers were tested. That is, the longitudinal tensile strength is ASTM D
-638, lateral tensile strength is ASTM D-6
Compressive strength was determined according to ASTM D3410 (IT
Bending strength is ASTM D-79 according to RI I method)
Determined according to 0.

The results of such strength tests are shown in the table below.

"" G~Size treatment 232.67 2.31 No size treatment 260.90 4.42 G-Size treatment 123.30 216.22 No size treatment 135.60 260.59 What are the transverse tensile strength and compressive strength of the laminate? , is the best indicator of adhesion between the carbon fiber and thermoplastic matrix of the laminate. From the results in Table I, it can be seen that laminates made according to the invention using unsized carbon fibers had the best adhesion.

Example 2 This example shows that in comparing commercially sized and unsized carbon fibers, the drying temperature of resin-impregnated unsized rovings was 760°F instead of 780°F. Example 1 except for 'F'
Follow the steps.

The strength test procedure was the same (same as in Example 1).

Poly(phenylene sulfide) with amine group at the end
In preparing the resin, the mole percent of the 4-aminobenzenethiol compound used in the reaction was adjusted to 3.78 mole percent (
as described in Example 1, except that the melt flow of the resulting polymer was 2358 g/10 min.

The results of the strength test of the manufactured laminate are shown in Table 1 below.

Table ■ G-size processing 241.10 2.55 No size processing 226.33 3.29 G-size processing 1
41.03 224.62 No size processing 126
．． 30 235.95 Example 3 In this example, an amine-terminated poly(phenylene sulfide) resin was used with a different amino-organothiol compound, namely 2-aminobenzenethiol, but in the amount of Example 2. , ie 3.78 mole percent (based on sulfur). The carbon fiber used did not contain a sizing agent. The manufacture of the laminate and its strength testing were the same as in Example 1. The amine terminated polymer had a melt flow of 1838 g/10 min. The prepared laminate has an average longitudinal tensile strength of 225.50 KSI and an average transverse tensile strength of 21
5 KSI, average compressive strength is 137.07 KSI.

The average bending strength was 229.48 KSI.

Example 4 In this example, the 2-aminobenzeniol of Example 3 was used in the amount of Example 1, namely 0.76 mole percent (based on sulfur). The carbon fibers did not contain sizing agents. The preparation of the laminate and its strength testing were as in Example 1. The melt flow of the resulting poly(phenylene sulfide) polymer with amine end groups was 6
It was 4.3g/10 minutes. The average longitudinal tensile strength of the prepared laminate was 252.77 KSI and the average compressive strength was 133
The average bending strength was 223.52 KSI. Average transverse tensile strength was not measured.

Example 5 As a control, the composite material described in Example 1 was prepared from a composite comprising G-sized carbon fibers and a matrix of RYTON poly(phenylene sulfide) resin (PRO9) without amine-terminated polymers. The procedure was used to make the laminate. The strength test results of these laminates showed an average longitudinal tensile strength of 255.63 KSI and an average transverse tensile strength of 4.
Q3KSI.

Average vertical compressive strength 113.87 KSI, average vertical bending strength 2
It gave 69.70 KSI.

It can be seen from the above examples that the best results in terms of improved transverse tensile strength and compressive strength are obtained from carbon fibers that have not been presized compared to presized ones. Similarly, the examples demonstrate that the use of amine-terminated poly(phenylene sulfide) in a resin matrix in accordance with the present invention improves adhesion between the resin matrix and carbon fibers.

In view of the foregoing, the present invention is well suited to carry out the above objects and achieve the results and benefits as well as inherent advantages set forth above. Although a preferred embodiment of the invention has been described for the purposes of this specification, it will be appreciated that variations in the components and execution of steps will readily occur to those skilled in the art. , all variations thereof are included within the spirit of the invention as defined by the appended claims.

(4 other people)

Claims (1)

[Claims] 1. Carbon fiber; poly(arylene sulfide) having an amine group at the end as one resin component; and poly(arylene sulfide), polyolefin, polysulfone,
A second resin component which is polyethersulfone, polyetherimide, polyetherketone, polyetheretherketone, polyetherketoneketone, liquid crystal polymer, or a mixture of these resins: Thermoplastic composite material. 2. The carbon fiber accounts for about 10% of the total resin weight in the composite material.
The composite material of claim 1, wherein the composite material is present in an amount ranging from about 80%. 3. The first resin component of poly(arylene sulfide) having an amine group at its end is present in an amount ranging from about 0.5% to about 99.5% by weight of the thermoplastic resin of the composite material. Composite material according to item 1 or 2. 4. The poly(arylene sulfide) resin having an amine group at the end has a melt flow value of about 10 g/10 min as measured according to ASTM D1238, condition 317/0.36 using an orifice with a length of 1.250 inches. Approximately 50
Composite material according to any one of claims 1 to 3, in the range of 00 g/10 minutes. 5. The composite material according to any one of claims 1 to 4, wherein the poly(arylene sulfide) resin having an amine group at the end is a poly(phenylene sulfide) resin having an amine group at the end. 6. The composite material according to any one of claims 1 to 5, wherein the poly(arylene sulfide) resin having an amine group at the end is a poly(phenylene sulfide/sulfone) resin having an amine group at the end. 7. The composite material according to any one of claims 1 to 6, wherein the second resin component is one or more poly(arylene sulfide) resins. 8. The second resin component is poly(phenylene sulfide)
resin, poly(phenylene sulfide/sulfone) resin,
The composite material according to any one of claims 1 to 6, which is a mixture of these resins. 9. Consisting of mixing carbon fibers with a first resin component and a second resin component having an amine group at the end, and solidifying the mixture into a composite material in which carbon fibers are embedded in a resin matrix. A method for producing a high-strength thermoplastic resin/carbon fiber composite material according to any one of claims 1 to 8. 10. Impregnating a continuous carbon fiber roving with a thermoplastic resin mixture consisting of the first resin component and the second resin component, and pulling the impregnated roving through a heated forming die to impregnate it. Claims 1 to 8 comprising integrally cementing the roving to the composite material.
A method for producing a high-strength thermoplastic resin/carbon fiber composite material according to any one of the above. 11. The method of claim 10, wherein the amount of carbon fibers present in the impregnated roving is within the range of about 50% to about 80% by weight of the impregnated roving. 12. The continuous carbon fiber roving is impregnated with the resin mixture by pulling the roving through a bath containing the resin mixture.
The method described in. 13. the continuous carbon fiber roving is pulled through a bath containing the first resin component and then passing the roving through a second bath containing the second resin component; 12. A method according to claim 10 or 11, wherein the resin mixture is impregnated by stretching.