JPS63146939A - Stamping molding sheet - Google Patents

Abstract

PURPOSE:To obtain a molding sheet capable of giving stamping molded articles of outstanding mechanical properties and heat resistance, by integrating a matrix resin made up of polyphenylene sulfide, polyamide and epoxy resins and fiber reinforcer into a composite. CONSTITUTION:The objective molding sheet can be obtained by integrating a matrix resin made up of (A) polyphenylene sulfide (pref., containing >=70mol% of a structural unit of formula), (B) polyamide (pref., nylon-6), and (C) epoxy resin (pref., novolak type epoxy resin) pref. in such amounts as to be 99-20pts. wt. for the component A, 1-80pts.wt. for the component B, and 0.1-20pts.wt. per 100pts.wt. of the components A+B for the component C and pref. 25-100wt% based on said matrix resin, of fiber reinforcer (pref., carbon fiber) into a composite.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a sheet for stamping molding that can provide stamping molded products with excellent mechanical properties and heat resistance.

<Prior art and its problems> A resin sheet is preheated to a temperature higher than the melting point or softening point of the resin, and is compressed by applying rapid pressure between a pair of molds of a predetermined shape. The so-called stamping molding method, which involves cooling, can be molded in a short time and is attracting attention as a method that can produce large molded products with excellent productivity. In particular, as a matrix resin,
Because thermoplastic resin is used, the molding cycle is short, similar to the molding of metal fittings, and productivity lags behind.

Stamping molded products obtained from materials reinforced with a cloth-like material made by knitting and weaving long fibers of glass fiber or charcoal fiber (hereinafter referred to as carbon fiber cloth) are excellent. It has good mechanical properties. The thermoplastic resin used in this case is mostly polypropylene resin or nylon resin, but attempts have also been made to use reed, polyphenylene sulfide resin, etc.

In recent years, in fields where there is a demand for lighter structural materials such as automobiles and aerospace, materials with even higher mechanical properties and
Heat resistance is required, but conventional stamping molded products with a matrix of polypropylene resin or nylon resin have limitations.

Furthermore, polyphenylene sulfide has excellent heat resistance and is attracting attention as a matrix resin for stamping molding sheets. However, polyphenylene sulfide has problems with adhesion and impregnation with reinforcing materials.
Sufficient performance cannot be obtained.

In view of the above-mentioned situation, the inventors of the present invention conducted intensive studies to obtain a sheet for stamping molding that can impart mechanical properties and heat resistance, and found that polyphenylene was used as the matrix resin. The inventors have discovered that it is effective to use a composition consisting of sulfide, polyamide, and epoxy resin, and have arrived at the present invention.

That is, the present invention provides a sheet for stamping molding, which is characterized in that it is formed by compositely integrating a matrix resin (A) made of polyphenylene sulfide, polyamide, and epoxy resin and a fiber reinforcing material CB).

In the present invention, since a composition consisting of polyphenylene sulfide, polyamide, and epoxy resin is used as the matrix resin, the problems with polyphenylene sulfide can only be speculated, but the adhesion with the fiber reinforcement material and the matrix resin This seems to be due to its own toughness.

As the polyphenylene sulfide used in the present invention, it is preferable to use polyphenylene sulfide because it provides a composition with excellent properties.

Polyphenylene sulfide can be polymerized by polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate, or by polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate, or by polymerizing sodium sulfide or sodium bisulfide and sodium hydroxide or hydrogen sulfide and sodium hydroxide in a polar solvent. Examples include polymerization in the presence of IJ-aminoalkanoate, self-condensation of p-chlorothiophenol, and N-methylpyrrolidone,
A common method is to react sodium sulfide and p-dichlorobenzene in an amide solvent such as dimethylacetamide or a sulfone solvent such as sulfolane. At this time, an alkali metal salt of carboxylic acid or sulfonic acid or an alkali hydroxide may be added to adjust the degree of polymerization. The copolymerization component may contain a 30mophenyl group, an alkoxy group, a carboxylic acid group, or a carboxyl group as long as it does not significantly affect the crystallinity of the polymer, but preferably the copolymerization component should be 10 mol% or less. . In particular, when trifunctional or more functional phenyl, biphenyl, naphthyl sulfide bonds, etc. are selected for copolymerization, the amount is preferably 6 mol% or less, more preferably 1 mol% or less.

As a specific method for producing such PPS, for example, (1)
Reaction of a halogen-substituted aromatic compound with an alkali sulfide (see U.S. Patent No. 2,513,188, Japanese Patent Publication No. 44-27671 and Japanese Patent Publication No. 45-3368), (2) In the coexistence of an alkali catalyst or copper salt of thiophenols, etc. (3) condensation reaction of an aromatic compound with sulfuric acid chloride in the presence of a Lewis acid catalyst (see Japanese Patent Publication No. 46-27255 and Belgian Patent No. No. 29437), (4) Process for producing high molecular weight pps (Special Publication No. 52-12,
240, Special Publication No. 54-8719, Special Publication No. 55-25.5
88, JP 57-334, JP 55-43, 139
, USP4.350,810, USP4,324,8
86) etc.

In the present invention, any of the above polyphenylene sulfides may be used, but from the viewpoint of ease of molding and mechanical performance, A8TM D-1238-74 is preferred.
Generally, a range of 1α000 to 100, preferably a range of 5.000 to 500, is used as a melt flow rate measured at 315.6° C. and 5 kl?load.

Various well-known polyamides can be used as the polyamide used in the present invention. For example, sulfuric acid, adipic acid, superric acid, sebacic acid, terephthalic acid, isophthalic acid,
1゜Dicarboxylic acids such as 4-cyclohexyldicarboxylic acid and ethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine, 1,4
- Polyamides obtained by polycondensing diamines such as cyclohexigludiamine and m-xylylene diamine; Polyamides obtained by polymerizing cyclic lactams such as caprolactam and laurinlactam; or cyclic lactams, dicarboxylic acids, and diamines. Examples include polyamides obtained by copolymerizing salts with. Among these polyamides, 6-nylon, 66 nylon,
6/10 nylon, 66/6/10 nylon, 6/66
Nylon, 12 nylon, 11 nylon, 6/6 nylon (a copolymer of a salt of caprolactam, terephthalic acid, and hexamethylene diamine), etc., and particularly preferred are 6 nylon and 66 nylon.

The epoxy resin used in the present invention may contain one or more epoxy groups, and may be liquid or solid. For example, bisphenol A rsorcinol, hydroquinone, pyrocatechol, bisphenol F1 saligenin, 11315-to'J hydroxybenzene, bisphenol S1 trihydroxy-
Glycidyl ethers of bisphenols such as diphenyldimethylmethane, 4,4'-dihydroxybiphenyl, 15-dihydroxynaphthalene, cashew phenol, 21215.5-tetrakis(4-hydroxyphenyl)hexane, and non-loginated bisphenols in place of bisphenol. , glycidyl ether threads such as diglycidyl ether of butanediol, glycidyl ester threads such as phthalic acid glycidyl ester, glycidyl amine threads such as N-glycidylaniline, etc. Glycidyl epoxy resin 2 epoxidized polyolefin, epoxidized soybean oil, etc. Examples include non-glycidyl epoxy resins with cyclic threads such as vinyl cyclohexene dioxide, dicyclopentadiene dioxide, and the like.

A particularly preferred epoxy resin in the present invention is a novolac type epoxy resin. Novolac type epoxy resin is
It contains two or more epoxy groups and is usually obtained by reacting novolac-type phenol m8k with epichlorohydrin.Novolac-type phenol resin can also be obtained by a condensation reaction with phenols and toformaldehyde. There are no particular restrictions on the phenols used as this raw material, but phenol, 0-cresol, m-cresol, p-cresol, bisphenol A rsorcinol, p-tert-butylphenol, bisphenol F1, bisphenol S, and mixtures thereof are particularly preferably used. . Furthermore, an epoxidized product of poly-p-vinylphenol can also be used in the same manner as the novolac type epoxy resin. In addition, these novolac type epoxy resins contain halogen,
It may have a hydroxyl group, etc., and may be used alone or as a mixture of two or more.

Generally, epoxy resins contain amines, acid anhydrides, polysulfides,
It is molded by adding a hardening agent such as phenolic resin,
In the present invention, it is desirable that no curing agent be used at all, or even if it is used, the molar ratio of the active hydrogen groups to the epoxy group component is less than half. If a normal amount of a curing agent is used together, the reaction between the epoxy resin and PP8 will be inhibited, or the reaction between the epoxy resin and the curing agent will produce a crosslinked network, resulting in a stable increase in melt viscosity. Because it will disappear. The effect of the combined use of a curing agent is expected to be to prevent deterioration of bleeding properties and thermal properties due to the addition of an epoxy resin.

The matrix resin constituting the stamping molding sheet of the present invention is a composition consisting of three components: the above-mentioned polyphenylene sulfide, polyamide, and epoxy resin. The mixing ratio of each component is not particularly limited, but generally 99 to 20 parts by weight of polyphenylene sulfide and 1 to 1 part by weight of polyamide.
80 parts by weight, 0.1 to 20 parts by weight of epoxy resin for a total of 100 parts by weight of polyphenylene sulfide and polyamide.
Parts by weight are appropriate. Incidentally, if the polyamide content is too small, thermal cracks are likely to occur, causing gullies, whereas if the polyamide content is too large, the heat resistance will decrease. Epoxy resin can be effective even in a relatively small amount, but if it is less than α1 part by weight, the effect will not be recognized. If the amount is too high, the mechanical performance may deteriorate, and depending on the type of epoxy resin added, it may bleed onto the surface of the molded product or the stability of the meltability of the molding sheet may be impaired.

In the present invention, for example, in order to obtain an excellent molded product of carbon fiber, glass fiber, ceramic fiber, metal fiber, asbestos fiber, etc., inorganic fiber such as carbon fiber or glass fiber is used. , particularly preferably carbon fibers are used. The carbon fiber may be of any type, such as rayon, polyacrylonitrile, or pitch yarn. These fiber reinforcing materials can be used in any form such as yarns, rovings, cut fibers, woven fabrics, knitted fabrics, or braided fabrics, but from the viewpoint of mechanical properties, fibrous fabrics are preferable.

Further, the matrix resin used in the present invention may optionally contain mica, talc, calcium carbonate, magnesium carbonate, calcium silicate, dolomite, potassium titanate, silicon carbide, silicon nitride, barium sulfate, calcium sulfate, kaolin, Clay, pyrophyllite, bentonite, sericite, zeolite, nephelinsinite,
Inorganic fillers such as atalpulgite, wollastonite, PMF, ferrite, antimony trioxide, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, glass beads, glass balloons, quartz powder, etc. Various additives such as a silane coupling agent, a mold release agent, a coloring agent, a heat stabilizer, an ultraviolet stabilizer, a flame retardant, and a rust preventive can be used in combination without departing from the purpose of the present invention.

In the present invention, the matrix resin and the reinforcing material are integrated into a composite, but if the ratio of the reinforcing material to the matrix resin is too small, the reinforcing effect will be insufficient and the mechanical performance will deteriorate, while if it is too large, the moldability will deteriorate. tends to get worse. The proportion of the reinforcing material used varies depending on the shape, size, molding conditions, etc. of the stamping molded product, but generally it is 20 to 200% by weight, preferably 25 to 200% by weight, based on the matrix resin.
It is 100% by weight.

The method for producing the stamping molding sheet of the present invention is not particularly limited, and there are various methods. For example, (11) a method in which a woven fiber material, a reinforcing fiber mat, and a matrix resin sheet are laminated in a predetermined arrangement, heated to a temperature higher than the melting point or softening point of the matrix resin, and integrated under pressure; (2) There are two methods: (1) heating and melting IJ Lux resin in advance and impregnating it with the fiber reinforcing material, and (3) spreading the resin powder as uniformly as possible on the fiber reinforcing material and then heating it.

The heating temperature in producing the stamping sheet of the present invention is generally in the range of 270 to 650°C.

M) When impregnating with IJ Tux oil, it is also possible to impregnate each component of the matrix resin and various additives used in combination as necessary with only tri-blend.
From the viewpoint of homogeneity of the composition, it is preferable to melt and knead in advance using an extruder or the like and then impregnate.

<Effects of the Invention> The stamping molding sheet of the present invention having the above-mentioned configuration can provide a stamping molded product that is easy to mold and has excellent mechanical performance and heat resistance.
It is suitable as a structural material for automobiles, aerospace, etc., and can also be used as a member of devices and machines that require heat resistance.

<Example> Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 Melt flow rate (ASTM D-1238-74
,315,6℃,5kl? load) is 2800 (g/10
90 parts by weight of polyphenylene sulfide, 10 parts by weight of 6.6 nylon with a molecular weight of approximately 25,000, and 6 parts by weight of phenol novolak type epoxy resin were melt-kneaded at 290°C using a 65-mm-screw extruder, and the matrix side I got some nice pellets.

Using the pellet, a sheet with a thickness Q of 3 ymn was produced using a press molding machine.

Next, carbon fiber mounting materials (manufactured by Bundle ■, trading card T-300 vertical/horizontal 1:1 cross) a3) were laminated alternately so that the cross-sectional configuration was CB+-(5)-(8). The molded material was then fed between parallel molds on a press molding machine set at 290°C, heated and pressed at 60°C +7/α for 2.3 minutes, and then cooled to room temperature using a cooling press to form a mold with a thickness of approx. A composite sheet of 4 layers was obtained. The sheet had approximately 50 weight percent return fiber to matrix resin.

Note that no cracks were observed from the appearance of the sheet.

Next, the above composite sheet was preheated for 6 minutes in a dryer set at 280°C, then put into a square mold set at 150°C, and pressed at approximately 60°C +7/cIn2 for 20 seconds to obtain a thickness of 6cm.
A flat plate was obtained.

No cracks were observed in this flat plate.

The bending strength of the specimen cut from the above flat plate was 86 to 9/
wn2, the heat distortion temperature was 260°C or higher.

Comparative Example 1 A composite sheet was obtained in the same manner as in Example 1, except that the polyphenylene sulfide of Example 1 was used alone as the matrix resin. There were slight cracks in the sheet. Note that the carbon fiber content relative to the matrix resin was approximately 50% by weight.

Then, in the same manner as in Example 1, Taira was obtained. Slight cracks were also observed in this flat plate. The strength of the song is 18 kg/
rran” and the strength was uneven.

The heat distortion temperature was 260°C or higher.

Example 2 60 parts by weight of polyphenylene sulfide with a melt flow rate of 5000 (g/10 minutes), molecular weight approximately 20,00
40 parts by weight of 0.6.6 nylon and 1 part by weight of cresol novolac type epoxy resin were melt-kneaded at 280°C using a 65 mm-shaft extruder to obtain pellets of IJ lux resin, which were further crushed to finely powder. It was made into powder.

Next, the above-mentioned fine powder was uniformly sprinkled on a randomly oriented glass fiber mat (manufactured by Asahi Fiberglass ■, basis weight: 300#/m"), and fed between flat molds on a press molding machine set at 280 ° C. Heat and press for 2.2 minutes at 9/cIn.
A composite sheet of trm was obtained. The glass fiber to matrix resin of the sheet is about 70 weight percent;
No cracks were observed on the sheet appearance.

After preheating the above composite sheet in a dryer set at 275°C for 4 minutes, two composite sheets were stacked and put into a flat mold set at 140°C, approximately 50kl? /m2 for 15 seconds to obtain a flat plate with a thickness of 3 strips. No cracks were observed on the flat plate.

The bending strength of the specimen cut from the above flat plate was 56 kg.
/ran2, the heat distortion temperature was 260°C or higher.

Comparative Example 2 A composite sheet was obtained in the same manner as in Example 2, except that the polyphenylene sulfide of Example 2 was used alone as the matrix resin. The sheet had about 65 weight percent glass fiber to matrix resin.

Moreover, many cracks occurred in the sheet, making it difficult to use it for stamping molding.

Claims (1)

[Claims] Matrix resin (A) consisting of polyphenylene sulfide, polyamide and epoxy resin and fiber reinforcement material (B)
A sheet for stamping molding characterized by being formed by integrating the above.