JPH0543711A - Glass-reinforced poly(arylenesulfide) composition - Google Patents

Abstract

PURPOSE: To improve the lateral tensile strength and hydrolysis stability of a poly(arylene sulfide) thermoplastic composite material reinforced by a glass fiber fabric or nonwoven fabric.

CONSTITUTION: Before a composite material is produced by subjecting a fabric or nonwoven fabric comprising continuous glass fibers arranged in one direction to pultrusion or compression molding together with a thermoplastic resin, if glass fibers being a reinforcing material is impregnated with silane of a certain kind or glass fibers, silane and a thermoplastic resin are simultaneously and integrally combined to be molded, a composite material having improved lateral tensile strength and hydrolysis stability can be obtained.

COPYRIGHT: (C)1993,JPO

Description

Detailed Description of the Invention

The present invention relates to fiber reinforced thermoplastic materials.

The production of unidirectional glass fiber reinforced poly (arylene sulfide) resin thermoplastic materials by pultrusion has been previously disclosed. See, for example, U.S. Pat. No. 4,680,224. At least one strand of fibers (a bundle of a certain number of fibers) of continuous filaments is contacted with the poly (arylene sulfide) resin in powder or slurry form. The impregnated strand (s) is then pulled through a temperature controlled die to produce a composite material in the form of, for example, tape, bar or sheet.

The glass fiber reinforced prepreg tape produced in this manner is useful for applications such as structural members, aircraft parts, doctor blades and the like.

Aliphatic sulfide type silanes have been used in glass reinforced poly (phenylene sulfide) compositions to improve hydrolytic stability. These silanes have not previously been used in continuous unidirectional fiber reinforced poly (phenylene sulfide) and have not addressed the purpose of improving the transverse tensile properties of prepreg tapes.

In some applications, continuous fiber reinforced thermoplastic prepreg tapes would be more useful if they had improved transverse tensile strength and improved hydrolytic stability. For example, doctor blades used to process aqueous substances require structural materials with good hydrolytic stability. Similarly, structural members that are highly loaded from multiple directions require, among other properties, excellent lateral tensile strength. Good lateral tensile strength also avoids microcracks in the composite material of continuous fibers and mitigates microcrack propagation under loaded conditions.

[0006] By means of a laminating method,
It is well known in the art to produce materials consisting of woven glass fiber fabrics impregnated with (arylene sulfide) resins. These materials have been used in applications such as structural components and aircraft parts. These materials can also benefit from both improved hydrolytic stability and core layer strength.

According to the summary one embodiment of the present invention, passing through a roving of glass fibers of a single warp slurry bath containing the matrix material and polysulfide organosilane poly (arylene sulfide) A prepreg tape of glass fiber reinforced poly (arylene sulfide) is prepared by.

According to another embodiment of the present invention, a woven glass fiber fabric is impregnated with a composition of poly (arylene sulfide) and silane.

[0009] Composite materials manufactured according to the detailed description of the Invention The present invention has an improved adhesion and / or improved hydrolytic stability of the resin to the glass as measured by the lateral tensile strength. Such materials with good transverse tensile strength also show a reduced level of microcracking.

Examples of poly (arylene sulfide) resins that are considered useful in making the compositions of the present invention include, for example:
U.S. Pat. No. 3,354,129 issued to Edmonds and Hill on November 21, 967, 1977.
As described in U.S. Pat. No. 3,919,177 issued to Campbell on Nov. 11, 2013. A presently preferred polymer is poly (phenylene sulfide).

The technical term poly (arylene sulfide) includes homopolymers (homopolymers) and usually solid arylene sulfide copolymers (copolymers), terpolymers.
(Terpolymer), and the melting point or softening point is at least about 150 ° C, more preferably from about 200 ° C to about 400 ° C. Poly (arylene sulfide)
Other examples of substances are poly (4,4-biphenylene sulfide), poly (2,4-tolylene sulfide), and copolymers made from p-dichlorobenzene, 2,4-dichlorotoluene and sodium sulfide. Is.

The term poly (phenylene sulfide) includes homopolymers and copolymers containing aryl groups and ortho-, meta-, and / or para-phenylene linkages in the polymer backbone. Also included are aryl substituted derivatives of these materials. Similarly, poly
(Arylene sulfide sulfone), poly (arylene sulfide ketone) and poly (arylene sulfide diketone).

Organosilanes that are considered useful in making the compositions of the present invention include aromatic polysulfide silanes of the formula:

[0014]

The number of sulfur atoms (S) linking the two aromatic groups is determined by the value of n representing a positive integer in the range 1-30. Subgenera within the scope of this invention have n from 1 to
It is represented by Formula I in the range of 10. The preferred value of n is 1-5.

Each of R ₁ and R ₂ is hydrogen or has 1 carbon atom.
To 30 alkyl groups. R ₅ , R ₆ , R ₇ , R ₈ ,
Each of R ₉ and R ₁₀ is an alkyl group having 1 to 30 carbon atoms. Alkyl groups associated with R ₁ , R ₂ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are linear (eg n
-Propyl) or branched (eg tertiary butyl). Examples of alkyl groups within the scope of this invention include, but are not limited to:

[0017]

[0018]

Within the scope of the present invention is a subgenus of formula I wherein each of R ₁ and R ₂ is hydrogen or an alkyl group having 1 to 10 carbon atoms and R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀
Is a substance of formula I wherein each of the is an alkyl group having 1 to 10 carbon atoms. Preferably, each of R ₁ and R ₂ is hydrogen or an alkyl group having 1 to 5 carbon atoms, R ₅ ,
Each of R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ has 1 to 5 carbon atoms.
Is an alkyl group. In one embodiment of the invention R ₁
And R ₂ each represent a methyl group (--CH ₃ ), and R ₅ , R ₆ , R
Each of ₇ , R ₈ , R ₉ and R ₁₀ represents an ethyl group (—CH ₂ CH ₃ ).

Each of the letters x and y represents either a 1 or a 0. When x = 0, R ₃ disappears from Formula I and the Si bond extends to the carbon member of the corresponding aromatic ring. For x = 1, R ₃ is as defined below. Similarly, y =
When 0, R ₄ disappears from formula I and the Si bond extends to the carbon member of the corresponding aromatic ring. For y = 1, R ₄ is as defined below.

If there is any (that is, x = 1, y = 1
, Each of R ₃ and R ₄ is an alkylene group having 1 to 30 carbon atoms. The alkylene group may be linear or branched. Examples of alkylene groups within the scope of this invention include, but are not limited to:

[0022]

[0023]

A subgenus within the scope of this invention is that in formula I each of R ₃ and R ₄ (if present) has 1 carbon atom.
Compounds of formula I, wherein the alkylene groups are -10. Preferably, each of R ₃ and R ₄ (if present) is an alkylene group having 1 to 5 carbon atoms. In one embodiment of the invention, each of R ₃ and R ₄ is present (ie x = 1.
And y = 1), both are ethylene groups (ie, —CH ₂ C
H _2- ).

R ₁ and R ₃ (or Si when x = 0) can be bonded to any carbon atom in the vicinity of the corresponding aromatic ring, but they are both atoms of the same ring. It is to be understood that it cannot be bound to or to the ring atom to which sulfur is bound. The position of R ₁ with respect to the sulfur substituent can be either ortho, meta or para. R ₃ (or x for the sulfur substituent)
When = 0, the position of Si) may be either ortho, meta or para. Similarly, R ₂ and R ₄ (or Si when y = 0) can be attached to any carbon atom near the corresponding aromatic ring, provided that they are both atoms of the same ring. It should be understood that it cannot be bonded, or cannot be bonded to the ring atom to which the sulfur is bonded. The position of R ₂ with respect to the sulfur substituent may be ortho, meta or para. R for sulfur substituents
_{The 4} (or Si when y = 0) position can be either ortho, meta or para. Examples of arrangements of various atomic groups (substituents or groups) within the scope of the present invention include, but are not limited to:

[0026]

[0027]

The preferred silane compounds of the present invention are defined by the following chemical formula:

[0029]

In the above formula, n is an integer of 1-5. This includes all regioisomers of the above formula. Examples include, but are not limited to:

[0031]

[0032]

[0033]

The composition may include one or more silanes within its structural formula through Formulas I through IX. As a non-limiting example, the poly (arylene sulfide) composition can include compounds VII, VIII and IX described above. In one embodiment of the present invention, the poly (arylene sulfide) composition comprises two or more silanes defined by the formula:

[0035]

In the above formula, the average value of n for the mixture is from about 2 to about 4, preferably about 2.8.

For the time being, preference is given to R _{1 in} the above formula.
And R _{2 are} —CH ₃ , R ₃ and R _{4 are} —CH ₂ CH ₂ —, and R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R _{10 are} —CH ₂ CH ₃
, X = 1 and y = 1, and the average value of n is about 2.
8 is a silane. This material is Ucarsil® R
Commercially available from Union Carbide as C-2 or Y-9194.

Fiber-Reinforced Pultruded Thermoplastic Plus
Tics The improved glass-reinforced thermoplastic polymers produced by the method of the present invention have many features that represent various improvements over the prior art, in that they are exposed to humid environments for extended periods of time. It also includes improved properties to retain its properties while being retained and improved transverse tensile properties of the material with respect to the fiber orientation direction. The microcracks are virtually eliminated.

The pultruded fiber reinforced thermoplastic of the present invention is basically composed of a poly (arylene sulfide) resin, a glass reinforcement, and at least one polysulfide organosilane.

A presently preferred composition is a substantially linear poly (phenylene sulfide) having a melt flow in the range of about 1 to about 800 g / 10 minutes, a unidirectional continuous glass fiber reinforcement, a glass. Of about 0.01 to about 5.0 weight percent, more preferably about 0.05 to about 0.5 weight percent silane, based on the weight of, and having improved transverse tensile strength.

However, the scope of the invention covers a much wider area, the only requirement being that it increases the tensile strength in the transverse direction or improves the hydrolytic stability of the resulting composition. That is, a sufficient amount of silane should be used.

The content of poly (arylene sulfide) resin in the pultruded composite material is from about 20% to about 90%, preferably from about 25% to about 60%, most preferably based on the weight of the composition. Is in the range of about 25% to about 35%.

The amount of glass reinforcement in the pultruded composite material is from about 80% to about 1 based on the weight of the total composition.
It is in the range of 0%, preferably about 40% to about 75%, and most preferably about 65% to about 75%.

Continuous glass fibers that are regularly arranged in one direction in one warp roving are considered to be suitable reinforcing materials. Glass fibers can be found on the market. Examples of commercially available glass fibers include Certainteed 70C surface sized E-glass and Certained 70D-11.
However, the latter is preferred for the moment. However, the fibers considered useful in the present invention are not limited to single warp rovings, but may be conventional or assembled rovings. Also, these examples should not be considered to impose a constraint on the diameter of the fibers that would be useful in the present invention.

The method of making a unidirectional fiber reinforced thermoplastic material of the present invention comprises any or all of the following steps: (1) A continuous glass fiber selected from a specific silane (single) Or a plurality of); and then (2) through a spray, slurry or other means for impregnating the treated glass fibers with a thermoplastic matrix material; (3) treated and impregnated The obtained glass fiber is passed through an oven; (4) Final shaping is performed as a composite material in a heated mold.

Another method of making the unidirectional fiber reinforced thermoplastic material of the present invention comprises any or all of the following steps: (1) a thermoplastic resin, one or more selected A slurry or emulsion comprising silane and optionally other additives if necessary; (2) passing continuous glass fibers through the slurry of step (1); (3) treated and impregnated. The obtained glass fiber is passed through an oven; (4) Final shaping is performed as a composite material in a heated mold.

Preferably, the oven will maintain the temperature of the poly (arylene sulfide) at least as high as the melting point of the poly (arylene sulfide).

The examples which follow the description of the glass fiber nonwoven reinforced thermoplastics will provide more detailed information on the procedures and test methods used, as well as the properties obtained.

Thermoplastic plastic reinforced with woven glass fiber fabric
Stick Another embodiment of the present invention provides the following manufacturing methods (a) to (c): (a) Modified to make a woven thermoplastic of glass fiber of the present invention A method for producing an impregnated woven fabric; (b) a method for producing a reinforced glass fiber reinforced thermoplastic using glass from (a) above; (c) a resin and one or more polysulfide organo A method of making a woven glass fiber reinforced thermoplastic using a mixture of silanes.

One method for making a woven glass fiber reinforced thermoplastic composite material of the present invention optionally comprises any or all of the following steps: (1) glass fiber Completely incinerate any organic material on the woven fabric of (2) a woven fabric of glass fibers with one or more selected silanes by a known method such as dipping or spraying into a solvent or slurry. Impregnation with or without liquid; and (3) compression molding of a woven glass fiber treated with a selected thermoplastic to produce a laminate.

Furthermore, it is also possible to combine the selected silane with the initially selected thermoplastic resin before the thermoplastic resin is combined with the woven glass fiber fabric in the compression molding or laminating process.

Similarly, the thermoplastic resin, the woven fabric of glass fiber, and the silane can be combined at the same time by using the technique of pultrusion. In that case, for example, the woven fabric may be passed through a slurry bath containing both the thermoplastic resin and the selected silane. Alternatively, a woven glass fiber fabric can be combined with the silane of choice first and then pultruded through a slurry of thermoplastic resin.

The silanes described above are suitable for use in making the impregnated glass woven fabrics of the present invention. Woven fiberglass fabrics that are considered useful in the present invention include any that are used or available for such applications as plain weave or satin weave glass fiber fabrics. good.

The poly (arylene sulfide) resin described above is used to make a thermoplastic composite material reinforced with a glass woven fabric using either a glass fiber woven fabric or a silane impregnated glass fiber woven fabric. Suitable for use in making slurries, emulsions or mixtures.

The woven glass fiber reinforced thermoplastic composite material of the present invention comprises from about 20 weight percent to about 60 weight percent poly (arylene sulfide) resin, preferably from about 30 weight percent to about 5 weight percent.
0 weight percent, most preferably about 35 weight percent to about 45 weight percent; glass fiber from about 40 weight percent to about 80 weight percent, preferably about 50 weight percent to about 70 weight percent, and most preferably about 55 weight percent to about 65 weight percent; and the silane is from about 0.01 weight percent to about 5 weight percent, more preferably from about 0.05 weight percent to about 1 weight percent, and most preferably based on the weight of the glass. Preferably about 0.2
5 weight percent to about 0.5 weight percent.

A thermoplastic reinforced with a non-woven glass fiber
Non- wovens of plastic glass fibers can also be used according to the invention for producing composites of glass fiber reinforced thermoplastics. Glass fiber nonwovens can be used in compression molding or laminating to make glass fiber reinforced thermoplastic composites. The glass fibers can be impregnated with one or more selected silanes prior to compression molding or laminating to make the composite material. Or alternatively, silane / to form a glass fiber reinforced thermoplastic composite
One or more selected silanes may be combined with the thermoplastic resin prior to using the resin mixture.

The composite material of a thermoplastic reinforced with a non-woven glass fiber, as in the case of the above-mentioned reinforced thermoplastic with a woven glass fiber,
The ratio of thermoplastic resin to glass fiber and the weight percentage of thermoplastic resin, silane and glass fiber have similar things.

[0058]

Example 1 This example illustrates the preparation and quality of a continuous unidirectional glass fiber reinforced poly (phenylene sulfide). Compound 6, listed in Table 1 below, is a former commercial grade product of unidirectional continuous glass fiber reinforced poly (phenylene sulfide) made from assembled glass fiber rovings. However, in this case, it is made from poly (phenylene sulfide) without addition of silane as in the present invention, and its properties and preparation method are also different from those of the poly (phenylene sulfide) used in this invention. It's a little different. This is included in this example to represent the "level of technology" at the time the present invention was done.

With the exception of compound 6 described above, all compounds listed in the table below are disclosed in US Pat.
Made using the techniques disclosed in 680,224. However, in that case, the technique was modified and used to include a curtain sprayer and a rolling bar for orientation in the slurry bath wherever the glass was wet. Similarly, all compounds except compound 6 used either Certainteed 70-C surface sized E-glass with a diameter of 20 microns and an area factor (yield) of 250 or a diameter of 14 microns and an area factor of 450. I made it. Finally, all except compound 6 are 0.5 weight percent in the slurry bath (for Table 1) or specified weight percent (for Table 2, both are based on the weight of resin in the slurry bath). And the percentage)
The specific silane and the melt flow value are about 50 to 1
50 g / 10 min (measured using ASTM D1238-79, Procedure B, Condition 315 / 5.0, modified to use 5 min instead of the 6 min preheat time stated in the test method). )) Poly (phenylene sulfide). For the preparation of poly (phenylene sulfide) for testing, see US Pat. Nos. 3,919,177 and 4,801,6.
No. 64 and / or 4,415,729. The techniques disclosed in each specification were used. Only one lot of poly (arylene sulfide) (of the same melt flow rate and same preparation method) was used of any of the test comparisons described below, so that the comparison was valid.

The composite material of unidirectional prepreg tape prepared as detailed above was converted to a test piece by compression molding into a laminate using a heated step press. For the lateral pull test, a water-cooled saw with a diamond blade was used to cut the laminate into 10 inch by 10 inch plates into suitable ASTM test pieces. For hydrolysis stability testing, do the same for 14 inches x 14 inches
In (± 45) ₃ s plate {(± 45) in the ₃ s, the convention of using the + sign and over symbols is equal in magnitude is adjacent layers (unidirectional tape) of the sign is opposite It means that it is oriented at an angle. Next, for “(± 45) ₃ s”, the first is +4
It is defined that there are 3 layers (6 sheets) of the unidirectional tape alternately laminated at an angle of 5 ° and then −45 ° (90 ° to each other). "S" is [+45, -45, + 45, -4 with respect to the mid-plane of the final stack of 12 sheets.
5, +45, -45 / -45, +45, -45, +45, -4
5, +45], which indicates that symmetry is formed}. For both types of laminate,
Molding conditions include contact at 625 ° F for 10 minutes, opening and closing of the press to release pressure at 40, 80 and 120 psi, respectively, 20 minutes at 150 psi and 400 ° without pressure. Included a 2 hour hold at F.

The data in Table 1 below shows the effect of the use of different silanes in the slurry bath during composite preparation on the transverse tensile strength of the resulting composite. The data also show that when no silane is used in the slurry bath,
Other factors, such as glass fiber type, are enhanced as seen in composites (Composite 1) which have better transverse tensile strength than the commercial products described (Composite 6). It is shown that it contributes to the nature. For the tests of composite materials 1 to 5 shown in Table 1,
Glass fiber having an ed 70C and an area coefficient of 450 was used.

However, the most striking effect clearly seen from the data in Table 1 is that the lateral tensile strength of the product made with the polysulfide silane in the slurry bath during the preparation of the composite material is significantly superior. That is. As the data in Table 1 show, the product made with RC-2 silane has a transverse tensile strength almost three times that of the product made without silane, which is It shows a high value of about 6 times that of poly (phenylene sulfide) reinforced with unidirectional glass fiber.

Table 1 Cured compound of silane given to lateral tensile strength of air-cured resin, flushed, compound silane lateral tensile strength, no ksi 1 3.4 2 A-189 ¹ 6.3 3 3 Prosil 2107 ² 0. 6 4 Prosil 2210 ³ 3.9 5 RC-2 9.1 6 (commercial product) 1.5 Note) ¹ Mercapto commercially available from Union Carbide
Organosilanes with functional groups ² Trialkoxy-modified epoxysilanes commercially available from PCR, Inc., Gainesville, Florida ³ Ditto

[0064]

Example 2 This example demonstrates the effect of the use of the composition of the present invention on the hydrolytic stability of continuous unidirectional glass fiber reinforced poly (phenylene sulfide) composites.

The composite material and the test piece were prepared and tested in the same manner as in Example 1, with the following exceptions: (1) The glass fiber used was Certainteed
70D-11, diameter 20 microns, area coefficient 250,
(2) Poly (phenylene sulfide) was prepared using the technique described in Example 1 with a melt flow of approximately 80-120 g / 10 minutes. Differences from Example 1: The polymer was partially cooled from the polymerization mixture and first recovered from the mixture by adding additional N-methyl-2-pyrrolidone.

Table 2 shows that not only does the use of the silanes of the present invention yield initial high tensile strength composites, but composites containing silanes do not exhibit silanes of the present invention after exposure to high humidity conditions. Shows that it retains a higher percentage of the initial tensile strength than the corresponding composite material made without.

Table 2 Effect of silanes on hydrolysis stability Tensile strength Compound silane addition level ¹ Initial strength ² Final strength ³ Residual rate ⁴ 7 None 49.11 34.52 70 8 0.5 68. 91 58.11 84 Note) ¹ Indicated by weight percent based on resin ² Strength before exposure to hydrolysis conditions, units are ksi, 1ksi =
Strength after exposure to 95 psi relative humidity at 1000 psi ³ 160 ° F for 14 days in units of ksi ⁴ hydrolysis conditions "%"% residual "first" tensile strength after exposure to the specified time

[0068]

Example 3 This example demonstrates the preparation and properties of continuous unidirectional glass fiber reinforced poly (phenylene sulfide sulfone). Certainteed 70C, diameter 1
4 micron glass fiber with an area factor of 450 was used.
The compounds listed in Table 3 below were made using the techniques and materials disclosed in Example 1, except that the thermoplastic resin used was, for example, US Pat. It was a poly (phenylene sulfide sulfone) made using the technique disclosed in US Pat. No. 6,016,145. The data in Table 3 below shows the effect of using RC-2 in the slurry bath during composite preparation on the transverse tensile strength of the resulting composite. It can be seen that the transverse tensile strength of the product made with silane in the slurry bath during the preparation of the composite material is clearly superior to that of the product made without silane.

Table 3 Composite compound silane lateral tensile strength made from poly (phenylene sulfide sulfone) , ksi 16 no 6.1 17 RC-2 8.2

[0070]

Example 4 In this example, poly (phenylene sulfide) is used.
The preparation, testing and properties of a poly (phenylene sulfide) composite material reinforced with a woven glass fiber reinforcement made by previously treating the glass fiber with silane prior to impregnation with are shown. Poly containing RC-2 silane on glass
A comparison is made between the (phenylene sulfide) composite and the silane-free poly (phenylene sulfide) composite on glass.

The glass fabric used was a type 7781 E-glass woven fabric available from several different suppliers. The commercially available glass fabric was first heat treated to "burn" any organic material that may be present on it as-is. A portion of this was set aside on a woven glass fabric for the preparation of unsilanized composites. RC-2 silane was added to the rest of the heat treated glass fiber woven fabric. The weight percent of RC-2 incorporated into the glass was determined by testing a sample of the treated woven fabric using the "loss on ignition" technique.

Laminates of woven glass fibers impregnated with poly (phenylene sulfide) of the same type used in the unidirectional glass fiber reinforced composites of Examples 1 and 2 had alternating glass and polymer. It was prepared by autoclaving the stacked layers. The typical conditions used in this process were as follows: The alternating layers of glass and polymer were heated to 600 ° F in an autoclave for 95 minutes and held at this temperature for 55 minutes. At the beginning of the warm-up period, the pressure was increased to about 20 psig over about 5 minutes. Twenty-five minutes into the 600 ° F. hold, the pressure was gradually increased at the rate required to reach 150 psig after 15 minutes. This pressure was maintained until the end of the 600 ° F hold period. At the end of the 600 ° F hold period, the pressure is 5
It takes 0 minutes to reach zero psig, and the temperature takes 73 minutes to reach about 1
The contents of the autoclave were cooled by simultaneously lowering the pressure and temperature at rates up to 20 ° F. After cooling, the lid of the autoclave was opened and the laminate was taken out.

ASTM test specimens were cut from the laminates made using the above process and the specimens were tested using the four point interlaminar shear test method. This test method is ASTMD-23
If the short beam shear test method of 44 did not work,
Another test method for producing the desired interlaminar shear failure mode in thin beam graphite / epoxy laminates is 198
It was introduced by Browning, Abrams and Whitney in three years. (American Society for Testing and Materials, 1983, C.
Edited by E. Browning, pages 54-74, Composites: Quality Assurance
Processing, Browning, C. as described in ASTM STP 797 .
See E., Abrams, FL, Whitney, JM., "Four-Point Shear Test Method for Graphite / Epoxy Composites". This test method is useful for interlaminar shear fracture evaluation of thermoplastic composites such as PPS composites because the short beam shear test method does not yield consistent test results. The four-point shear strength test method is a four-point bending test method, ASTM-, in which the supporting beam used to cause interlaminar shear failure is only half of the supporting beam used in the bending test.
It is a modification of D790.

According to ASTM-D790, a four point load system utilizes two load points equidistant from adjacent support points, the distance between load points (load span) being 1/3 of the support span. It has become.

Table 4 RC-2 Silane treated glass woven / PPS composite interlaminar shear Interlaminar shear tensile strength, unit ksi RC-2 Level ¹ Before ² After ³ Longitudinal direction ⁴ Lateral direction ⁵ Zero 2.77 2.15 195 195 0.1 5.52 5.48 195 215 0.2 7.43 4.54 195 245 0.3 6.99 4.15 195 235 0.4 6.46 5.97 220 245 0.5 6.92 5.32 210 235 Note) ¹ Weight percent of silane on glass woven fabric before combined with PPS resin. Measured by "loss on ignition" ² Four-point interlaminar shear strength before heat-wet exposure (unit: ksi) ³ Four-point interlaminar shear strength after heat-wet exposure by boiling for 2 hours in water (unit: ksi) ⁴ Tensile strength of glass fiber woven fabric in the warp direction (unit: ks
i) Tensile strength in the weft direction of ⁵ glass fiber woven fabric (unit: ks
i)

The data in Table 4 show that a silane treated glass fiber woven reinforced thermoplastic composite material was made of unfibered glass fiber before and after exposure to hydrolysis conditions. It shows that it has significantly superior interlaminar shear strength.

[0077]

Example 5 This is when making a composite material reinforced with continuous glass fiber, before using the silane / resin mixture.
6 is an example showing how polysulfide silane is mixed with a poly (arylene sulfide) thermoplastic resin.

The slurry concentration and the amount of slurry required to produce the composite will vary depending on factors such as the size of the slurry bath (s), the process speed and the nature of the fibers to be impregnated. .. This is 30 ± 2 weight percent of resin and 70 ± of glass in the finished composite material.
It was empirically determined to produce an amount of slurry that would be 2 weight percent.

The main bath is 20.5 weight percent poly.
The (phenylene sulfide) resin was included and the additional bath contained 30 weight percent poly (phenylene sulfide) resin.

Approximately that amount of water was weighed into a large container and the pH was adjusted to approximately 4 with acetic acid.

The silane selected was RC-2 of Ucarsil ™, a polysulfide aliphatic silane belonging to Formula I in the introduction to the "Detailed Description of the Invention" section above. Ucars
il ™ RC-2 was used at a concentration of 0.5% based on the weight of poly (phenylene sulfide) resin.

The surfactant used was Neodol 91-6 at a concentration of 0.26% based on the weight of poly (phenylene sulfide) resin. Approximately that amount of surfactant was weighed out and added to the silane and manually agitated until the mixture was homogeneous.

The silane / surfactant mixture was added to the water with very vigorous mixing. After the entire amount of the silane / surfactant mixture was added to the water, vigorous stirring was continued for 4 hours, albeit less than before. No vigorous stirring is necessary after the emulsion is formed.

The poly (phenylene sulfide) resin was then added to the water / silane / surfactant mixture.

The resulting slurry was very dense.
(The slurry should not be used for 48 hours after mixing in order to adsorb the silane onto the poly (phenylene sulfide) resin). The mixture was stirred twice or thrice a day until used.

Table 5 below shows Certainteed 70D-1
1. A transverse tensile strength test result for a composite material prepared and tested in the same manner as described in Example 1 using unidirectional continuous glass fibers having a diameter of 20 microns and an area coefficient of 250 was obtained. Show.

Various silanes were used at a level of 1.0 weight percent based on the weight of resin. RC-2, T
When using 2905 and B2494, an emulsion was formed rather than a solution. DSC-18 was a solid. A-1160 was water soluble.

[0088] Note) ¹ Coupling agent used at 1.0 weight percent based on the weight of resin ² Polymer mercaptosilane commercially available from Harwick Chemical Company ³ Commercially available as Ucarsil ™ RC-2 from Union Carbide Company Test silane ⁴ Commercially available from Union Carbide Alcoholic solution of γ-ureidopropyltriethoxysilane ⁵ Commercially available from Petrarch Systems z- (trimethoxysilyl) ethylphenylsulfonyl azide ^{6 From} Petrarch Systems Commercially available bis [3- (triethoxysilylpropyl] tetrasulfide

The data in Table 5 show that the type of silane used has a significant effect on the amount of lateral tensile strength of the product, and among the tested ones, RC-2 is the most improved lateral tensile strength. It shows that the tensile strength was given.

[0090]

EXAMPLE 6 This is a woven fabric made of poly-fiber to form a composite material of thermoplastic reinforced with a woven fabric of glass fibers.
This is an example of making a batch of a laboratory scale emulsion of silane used to treat a woven glass fiber fabric prior to compression molding with an (arylene sulfide) resin.

A quantity of doubly distilled water was weighed into a blender and the blender was rotated at low speed. Surfactant Triton X-100 was added dropwise to 500 ml of water and blended for 40 seconds. 0.3 based on the weight of the glass
Enough R to achieve ignition loss of ~ 0.5%
C-2 was added to the surfactant and water mixture and blended at low speed for 5 minutes, then left for 25 minutes, then blended again at low speed for 10 minutes.

Although products, compositions of matter, and methods of the invention have been described in detail, the products, compositions, and methods of the invention should not be construed as limited thereby. This patent intends that all changes and modifications be covered within the spirit and scope of the invention.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C08L 81:00 7167-4J

Claims (21)

[Claims] 1. A glass-reinforced poly (arylene sulfide) composition comprising (a) poly (arylene sulfide) (b) at least one polysulfide organosilane; and (c) continuous glass fiber. object. 2. The poly (arylene sulfide) is poly.
The composition according to claim 1, which is (phenylene sulfide). 3. The poly (arylene sulfide) is a poly (arylene sulfide).
The composition according to claim 1, which is (phenylene sulfide sulfone). 4. The organosilane has the formula: (In the formula, n is an integer of 1 to 30; each of R ₁ and R ₂ is
Hydrogen or an alkyl group having 1 to 30 carbon atoms;
Each of R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ is an alkyl group having 1 to 30 carbon atoms; x is 0 or 1; y
Is 0 or 1; and each of R ₃ and R ₄ is an alkylene group having 1 to 30 carbon atoms: _4. The composition according to any one of claims 1 to 3. 5. n is an integer of 1 to 10; each of R ₁ and R ₂ is hydrogen or an alkyl group having 1 to 10 carbon atoms; R ₅ , R ₆ , R ₇ , R ₈ , Each of R ₉ and R ₁₀ is an alkyl group having 1 to 120 carbon atoms; x = 1; y = 1; and each of R ₃ and R ₄ is an alkylene having 1 to 10 carbon atoms. The composition according to claim 4, which is a group. 6. n is an integer of 1 to 5; each of R ₁ and R ₂ is hydrogen or an alkyl group having 1 to 5 carbon atoms;
Each of R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ is an alkyl group having 1 to 5 carbon atoms; and each of R ₃ and R ₄ has 1 to 5 carbon atoms. The composition according to claim 5, which is an alkylene group. 7. R ₁ and R ₂ are each —CH ₃ ; R ₅ ,
Each of R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ is —CH ₂ CH ₃ ; x = 1; y = 1; and each of R ₃ and R ₄ is —CH ₂ CH ₂ The composition according to any one of claims 4 to 6, which is 8. The component (b) comprises a plurality of silanes within the formula; and the average value of n for the plurality of silanes is from about 2 to about 4. 7. Composition. 9. The composition of claim 8 wherein the average value for n is about 2.8. 10. The amount of component (a) is in the range of about 20 to about 90 weight percent based on the weight of the composition;
The amount of component (b) is in the range of about 0.01 to about 5 weight percent based on the weight of the continuous glass fiber; and the amount of component (c) is about 80 based on the total weight of the composition.
To about 10 weight percent.
The composition according to any one of 1. 11. A continuous glass fiber is passed through a slurry bath containing a mixture of poly (arylene sulfide) and at least one polysulfide organosilane to impregnate the glass fiber; and (b) the impregnated glass. A method of making a continuous glass fiber reinforced thermoplastic composite material comprising heating and shaping the fibers. 12. (a) impregnating continuous glass fibers with at least one polysulfide organosilane; (b) subsequently impregnating the continuous glass fibers with poly (arylene sulfide); and (c) impregnating the same. Heating and shaping continuous glass fibers;
A process for producing a composite material of a continuous glass fiber reinforced thermoplastic comprising: 13. A glass fiber woven fabric is impregnated with at least one silane; and (b) one or more of the glass fiber woven fabrics are thereafter compression molded with poly (arylene sulfide). Do: A process for producing a composite material of a glass fiber reinforced thermoplastic. 14. A glass fiber-reinforced thermoplastic composite comprising laminating one or more woven glass fiber fabrics together with a mixture of poly (arylene sulfide) and said at least one polysulfide organosilane. Material manufacturing method. 15. (a) impregnating a glass fiber nonwoven with at least one silane; and (b) compressing one or more glass fiber nonwovens impregnated with poly (arylene sulfide). A method for manufacturing a composite material of glass-reinforced thermoplastic. 16. A method for producing a composite material of glass-reinforced thermoplastic, comprising compression molding one or more layers of a glass fiber non-woven fabric together with a mixture of poly (arylene sulfide) and at least one silane. 17. The mixture contains about 20 to about 60 weight percent poly (arylene sulfide), based on the weight of the mixture of the poly (arylene sulfide) and the glass fibers; and the mixture comprises the glass. 17. The method of claim 14 or 16 having from about 0.02 to about 5 weight percent of the silane, based on the weight of fiber. 18. Any organic residue from the glass fabric prior to impregnating the glass fabric with the silane or compression molding with the mixture of the poly (phenylene sulfide) and the silane. The method according to any one of claims 13 to 17, wherein the method is incineration. 19. A method according to claim 11, wherein glass fibers are treated with the components of the composition according to any one of claims 2 to 10. 20. A composite material reinforced with a woven or non-woven glass fiber fabric and a woven glass fiber fabric comprising the composition according to any one of claims 1 to 10. 21. The composite material comprises from about 20 weight percent to about 60 weight percent of the poly (arylene sulfide) and from about 80 weight percent to about 40 weight percent of the glass fiber, based on the total weight of the composite material. 21. The composite material of claim 20, wherein said composite material comprises about 0.01 weight percent to about 5 weight percent of said silane, based on the weight of said glass fiber.