JPS6011063B2 - resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition having excellent blend compatibility and containing polyphenylene sulfide (hereinafter abbreviated as PPS) as one component.

Many blend compositions of PPS and polyarylates, polysulfones, polyphenylene oxides, polyetherketones, polyimides, etc. are known. but,
Most of these compositions have insufficient compatibility, and have problems such as moderately reduced bending, impact resistance, and mechanical strength, and deterioration of the surface condition of molded products. However, it is difficult to say that this blend achieves its purpose. As a result of intensive studies, the present inventors have found that the compatibility between the P tower and these resins is dramatically improved by interposing an epoxy resin, and the hard but brittle properties of P are improved, while the compatibility with other resins is improved. It has been found that the characteristics of each component of the blended polymer can be exhibited, such as improved molding processability of the resin, and a highly practical molding material can be provided.

That is, according to the present invention, 99 to 1 part by weight of KazeP resin, at least one resin 1 to 9 selected from the group consisting of polyarylate, polysulfone, polyphenylene oxide, polyetherketone, and polyimide. Insect weight part,
and (C) Epoxy resin (total of A and B above 1
0 parts by weight) of 0.5 to 3 parts by weight.

It is preferable that the P-oxide used in the present invention contains 70 mol% or more of the structural unit represented by the general formula; if the amount is less than 70 mol%, it is difficult to obtain a composition with excellent properties.

Polymerization methods for this polymer include polymerization of p-dichlorobenzene in the presence of sulfur and sodium carbonate, and polymerization of p-dichlorobenzene in the presence of sodium sulfide, sodium bisulfide and sodium hydroxide, or hydrogen sulfide and sodium hydride in a polar solvent. Examples include polymerization methods such as self-condensation of p-chlorothiophenol, and the reaction of sodium sulfide and p-dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfonic solvent such as sulfolane. An appropriate method is to At this time, in order to adjust the degree of polymerization, it is a preferable method to add an alkali metal salt of carboxylic acid or sulfonic acid, or to add alkali hydroxide. As a copolymerization component, if it is less than 30 mol%, meta bonds ( ), ortho bonds ( ), ether bonds ( ), sulfone bonds), biphenyl bonds ( ), substituted phenyl sulfide bonds ( ), where R is alkyl group, nitro group, phenyl group, toalkoxy group, carboxylic acid group or metal base of carboxylic acid)
, trifunctional bonds (), etc., as long as they do not significantly affect the crystallinity of the polymer, but preferably the copolymerization component contains 1
It is preferably 0 mol% or less.

. In particular, when trifunctional or higher functional phenyl, biphenyl, naphthyl sulfide bonds, etc. are selected for copolymerization, the amount is preferably 3 mol% or less, more preferably 1 mol% or less. Such PPS
For example, [1] Reaction of a halogen-substituted aromatic compound with an alkali sulfide (US Pat. No. 25
No. 131, Special Publication No. 44-27671 and Special Publication No. 4
5-33 Iso), '2' condensation reaction of thiophenols in the presence of an alkali catalyst or steel salt, etc. (see US Patent No. 3,274,165 and British Patent No. 116,066), [3' Aromatic compound Examples include a condensation reaction with sulfur chloride in the presence of a Lewis acid catalyst (see Japanese Patent Publication No. 46-27255 and Belgian Patent No. 29437).

P-sea resin is currently available on the market from Phillips Vetroream under the trade name Ryton PPS.

Depending on its crosslinking density and viscosity, Ryton P.
There are grades V-1, P-2, P-3, P-4 and R-6. However, when blended with other resins, Ryton V-1 has a low crosslinking degree and too low viscosity. When such PPS is blended with the other thermoplastic resin and epoxy resin, the epoxy resin is effective in increasing the molecular weight of PPS.

In the present invention, it is possible to suitably use PPS, which has a low degree of coloration and has omitted the oxidative crosslinking process, which could not be used due to its low viscosity. In order to facilitate compatibility, which is the main objective of the present invention, PPS with fewer crosslinked structures is preferred. The degree of crosslinking of PPS is determined by the melt viscosity of the polymer (X)
It can be expressed by the relationship between and non-Newtonian coefficient (N), and generally, the larger N is, the higher the degree of crosslinking is. That is, in the PPS used in the present invention, the logarithmic values of the shear rate and shear stress obtained during viscosity measurement are blotted, and the slope of the tangent line at a shear rate of 200 (1/sec) at 300°C is expressed as a non-Newtonian coefficient. (N) and the melt viscosity (×) are particularly preferable.Furthermore, in the present invention,
High molecular weight PP with low sealing properties disclosed in No. 44495
S can also be suitably used. Next, the thermoplastic resin to be blended with P will be described.

Polyarylates are polyesters synthesized from bisphenols or derivatives thereof and dibasic acids or derivatives thereof.

Examples of bisphenols include 2,2-bis(4-
hydroxyphenyl)-propane, 4,4'-dihydroxy diphenyl ether, 4,4'-dihydroxy-
3,3-dimethyldiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, 4
, 4-dihydroxydiphenyl sulfide, 4,4'
-dihydroxy-diphenyl sulfone, 4,4'-dihydroxy-diphenyl ketone, bis(4-hydroxyphenyl)-methane, 1,1-pis(4-hydroxyphenyl)-ethane, 1,1-bis(4-hydroxy) phenyl)-n-butane, di(4-hydroxyphenyl)-cyclohexylmethane, 1,1-bis(4-hydroxyphenyl)-2,2,2-trichloroethane, 2,2-bis(4-hydroxy- Examples include 3,5-dibromophenyl)-propane, 2,2-bis-(4-hydroxy-3,5-dichlorophenyl)-propane, and particularly preferred one is 2,2-bis(4-dichlorophenyl)-propane.
Hydroxyphenyl)-propane, or bisphenol A. Examples of dibasic acids include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, bis-(4-carboxy)-diphenyl, bis-(4-carboxyphenyl)-ether, bis-(
4-carboxyphenyl)-sulfone, bis-(4-carpoxyphenyl)-carbonyl, bis-(4-carpoxyphenyl)-methane, pisu(4-carpoxyphenyl)-dichloromethane, 1,2- and 1,1 -bis-(4-carboxyphenyl)-ethane, 1,2- and 2,2-bis-(4-carboxyphenyl)-propane, 1,2- and 2,2-bis-(3-carboxyphenyl)-propane, 2 , 2-pis(4-carboxyphenyl)-1,1-dimethylpropane, 1,1- and 2,2-bis-(4-carboxyphenyl)-butane, 1,1- and 2,2-bis-(4- carboxyphenyl)-bentane, 3,3-bis-(4-carboxyphenyl)-heptane, 2,2-bis-(4-carboxyphenyl)-heptane; and aliphatic acids such as oxic acid, adipic acid, succinic acid, malonic acid, Examples include sebacic acid, glutaric acid, azelaic acid, suberic acid, etc., but isophthalic acid and terephthalic acid or mixtures of these derivatives are preferred.

Polysulfone is defined as a polyarylene compound in which arylene units are located in a disordered or ordered manner, together with ether and sulfone bonds, such as the following
Examples include those having the structural formula (in the formula, n' represents an integer of 10 or more), but preferably those having the structure ■ or ■. Polyphenylene oxide is
It is also called polyphenylene ether, for example, the general formula [
1] (wherein R and R2 represent hydrogen, halogen, alkyl having 4 or less carbon atoms, haloalkyl, alkoxy, allyl derivative having 9 or less carbon atoms, aralkyl group,
n represents the number of repeating units and is an integer of 10 or more.

), a polymer of 2,6-disubstituted phenol, 2,
Polymer with 6-disubstituted phenol
(see No. 65) etc., and usually has a molecular weight of 2000 or more,
Preferably it is 10,000 to 35,000.

Such resins are generally prepared by combining phenols such as phenol, 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-diisopropylphenol, 2-methyl-6-methoxyphenol, etc. with metal noamines, metal chelates, etc. It is obtained by dehydration reaction with oxygen in the presence of a co-catalyst such as a basic organic compound, but any production method may be used as long as the resin satisfies the above conditions. do not have. Specific examples include 2,6-dimethylphenylene oxide polymer, 2,6-dimethylphenol/pisphenol A (former/latter = 95/5 molar ratio) copolymer, and 2,6-dimethylphenylene oxide polymer.
Examples include dimethylphenylene oxide polymer.
It is also possible to use PPO grafted with styrene. The polyetherketone contains a repeating unit of formula [1] and/or a repeating unit of formula [2] alone or together with other repeating units, and has an intrinsic viscosity (1.V.) of 0.7.
This is a tough crystalline thermoplastic aromatic polyetherketone.

Other repeating units other than formula [1] and/or formula [2] include formula [3] [wherein A is a direct bond, oxygen, sulfur, -S
02, monoCO- or a divalent hydrocarbon group.

] and formula [4]; further, as copolymerized units, formula [5] and formula [6] [wherein the oxygen atom or child of the subunit is orthogonal to the group Q or Q' or para position, Q and Q' are the same or different, are one CO- or one S02-, Ar' is a divalent aromatic group, and n is 0, 1, 2 or 3. .

] Contains repeating units indicated by.

Polyimide is a divalent penzenoid group represented by the general formula [wherein R is a tetravalent aromatic group or aliphatic group containing at least one carbon 6-membered ring, R2 is a divalent group selected from the formula and R3 and R4 are selected from the group consisting of alkyl and aryl groups, and n is at least 2 or more such that the polymer is thermally stable at about 20 and 0. is an integer.

] or a polyimide having a repeating unit represented by the general formula [wherein Ra represents 10% to 90% of the repeating units, and/or represents the remainder of the repeating units, and n represents at least about 200oo] An integer of 2 or more that makes the polymer thermally stable.

] or a polyimide having a repeating unit represented by the general formula [where Ar is a trivalent aromatic group containing at least one carbon 6-membered ring, and R is a divalent aromatic and/or aliphatic residue. , R' is hydrogen, methyl group or phenyl group,
and n is an integer of 2 or more.

] includes polyamideimide having a repeating unit represented by the following.

The epoxy resin used in the present invention contains one or more epoxy groups, and can be in liquid or solid form.

For example, bisphenol A, resorsilyl, hydroquinone, pyrocatechol, bisphenol F, saligenin, 1,3,5-trihydroxybenzene, bisphenol S, trihydroxy-diphenyldimethylmethane, 4,4'-dihydroxybiphenyl, 1,5-dihydroxynaphthalene, cashewphenol, 2,2,5,
Glycidyl ethers of bisphenols such as 5-tetrakis(4-hydroxyphenyl)hexane, halogenated bisphenols instead of bisphenols, glycidyl ethers such as butanediol diglydyl ether, and glycidyl phthalate esters. Glycidyl epoxy resins such as glycidyl ester type such as glycidyl ester type such as glycidyl amine type such as N-glycidylaniline, linear type such as epoxidized polyolefin and epoxidized soybean oil, and cyclic type such as vinyl cyclohexide and dicyclobentadiene dioxide. Examples include non-glycidyl epoxy resins. A preferred epoxy resin in the present invention is a borac type epoxy resin.

A novolak type epoxy resin contains two or more epoxy groups, and is obtained by reacting a novolak type phenol resin with epichlorohydrin. Novolac type phenolic resin is obtained by a condensation reaction between phenols and formaldehyde. There are no particular restrictions on the phenols used as raw materials, but they include phenol, o-cresol,
m-cresol, p-cresol, bisphenol A,
Resorcinol, p-sarybutyl phenol,
Pisphenol F, pisphenol S and mixtures thereof are particularly preferably used. Furthermore, epoxides of poly-p-vinylphenol and halides of these epoxy resins can be used in the same way as novolac type epoxy resins. These epoxy resins may be used alone or in combination.
It may be used as a mixture of more than one species. Epoxy resins are generally formed by blending curing agents such as amines, acid anhydride polysulfides, and phenolic resins, but in the present invention, no curing agents are used at all, or even if they are used, they are not used. It is desirable that the molar ratio of the active hydrogen group to the epoxy group component is less than half.

When used together with a normal amount of curing agent, epoxy resin and P
This is because not only the reaction between the epoxy resin and the curing agent is inhibited, but also a stable increase in melt viscosity such as the formation of a crosslinked network due to the reaction between the epoxy resin and the curing agent cannot be expected. The effect of the combined use of a curing agent is expected to be that it prevents deterioration in bleeding properties and thermal properties due to the addition of an epoxy resin. The mixing ratio of each of the above components varies depending on the desired properties, but the weight ratio of P and at least one resin selected from the group consisting of polyarylate, polysulfone, polyphenylene oxide, polyimide, and polyetherketone is generally 99-1/1-99 preferably 90-10/10
~90. If the weight ratio is less than 1/9 degrees Celsius or more than 99/1, the desired effects of the present invention will be reduced, which is not preferable. The amount of the epoxy resin added is 0.1 to 3 parts by weight, preferably 0.5 to 20 parts by weight, per 10 parts by weight of the total amount of the polymer. The suitable amount of epoxy resin to be added varies depending on the molecular weight of the resin and the intended use, and generally a large amount of epoxy resin is required for low molecular weight towers or extrusion molding compositions that require high viscosity. If it is less than 0.1 part by weight, the effect will be small, and if it exceeds 3 parts by weight, the mechanical properties will be impaired, and depending on the epoxy resin added, it may bleed onto the surface of the molded product or affect the melt flow stability of the composition. This is not preferable as it may significantly reduce the

The composition of the present invention includes fibrous reinforcing agents such as glass fibers, carbon fibers, potassium titanate, asbestos, silicon carbide, ceramic fibers, metal fibers, and silicon nitride; barium sulfate, calcium sulfate, kaolin, clay, and gyrophyllant. , bentonite, sericite, zeolite, mica, mica, nephelinsinite, talc, atalbalzite, wollastonite, PMF, ferrite, calcium citrate, calcium carbonate, magnesium carbonate, dolomite, ammonium trioxide, zinc oxide, oxide Inorganic fillers such as titanium, magnesium oxide, iron oxide, molybdenum dioxide, graphite, gypsum, glass beads, glass balloons, quartz powder; organic reinforcing agents such as aramid fibers up to 8% by weight of the composition. It can be made to contain.

When adding these reinforcing agents or fillers, known silane coupling agents can be used. In addition, the composition of the present invention may contain small amounts of template agents, colorants, heat stabilizers, ultraviolet stabilizers, foaming agents, key fuel agents, scale fuel additives, rust preventive agents, etc. without departing from the purpose of the present invention. can be made to contain.

The composition of the invention can be prepared in various known ways.

For example, the raw materials can be placed in a tumbler or Henschel mixer in advance.
After uniformly mixing with a mixer such as the following, supplying it to a single-screw or twin-screw extruder and melt-kneading at 230 to 400°C,
You can use the method of making it into a pellet. Further, when performing extrusion kneading, it is preferable to divide the epoxy resin into two or more times and perform the extrusion operation two or more times in order to promote the reaction between the P tower and the epoxy resin. It is also possible to dry blend PPS and novolak type epoxy resin and melt and strain in an injection molding machine. Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited only to these Examples.

Example 1 Terephthalic acid dichloride and isophthalic acid dichloride (
methylene chloride solution and 2,2-bis(4
-Hydroxyphenyl)-propane and a caustic soda aqueous solution, the polyarylate polymer (the abundance ratio of terephthalic acid groups, isophthalic acid groups, and bisphenol A groups is 1:1:2, phenol/ 5 parts by weight of PPS (Ryton V-1 (manufactured by Phillips Petroleum Company) and dried for 0/8 hour using a hot air dryer.

After cooling, novolac type epoxy resin (Epicron N-6
95 (manufactured by Dainippon Ink & Chemicals Co., Ltd.) was added thereto, mixed uniformly, and extruded to 30 mm using a 2-ball extruder on the 30 side.
It was filtered and made into a beret. When a test piece was molded from this pellet using an injection molding machine, the molded product had a cream-colored appearance and had good compatibility.

When the physical properties were measured, the bending strength was ok9/ground, the uneven impact strength (notched) was 6k9/low/good, and the heat distortion temperature (18.6k9/g) was 148qo. Additionally, a PCT test (12
When the retention rate of bending strength was measured after being left in pressurized steam at 3°C for 5 hours, it showed a high retention rate of 83% (see Table 1). Examples 2 to 3 In Example 1, the weight ratio of the polyarylate polymer and PR was changed to 30/70 and 70/30.

As shown in Table 1, the results were superior to those of Example 1 and the same machine. Comparative Example 1 When no epoxy resin was added in Example 1, the appearance of the molded product had poor compatibility and a pearl-like luster.

The physical properties were measured, and as shown in Table 1, the bending strength was 3.
60k9/ground, Izod impact strength (with notch) is 2k
The strength retention rate after the hydrolysis resistance test was also low at 32%. Table 1 Example 4 Polyether sulfone (VICTREX20 Misaki, ICI
Parts by weight of P-Kyo (Ryton V-1) 5 and Nopolac type epoxy resin (Epicron N-695)
) 5 parts by weight were uniformly premixed and then kneaded at 320° C. using a 30-pan, 2-bag extruder.

A test piece was molded from this mixture using an injection molding machine at a cylinder temperature of 300°C and a mold temperature of 100°C. The molded product had a cream-colored appearance, good compatibility, and excellent surface gloss.

When the physical properties were measured, the bending strength was 950k9/mass, and the Izod impact strength (notched was 4 [9/mass])
(See Table 2). Examples 5 to 6 In Example 4, the weight ratio of polyethersulfone and PPS was changed to 30/70 and 70/30.

The results were as excellent as in Example 4, as summarized in Table 2. Comparative Example 2 When no epoxy resin was added in Example 4, the molded product had poor compatibility and a pearly luster.

The physical properties were measured, and the bending strength was ok9/ground, and the Izod impact strength (notched) was 2k9. It was as low as the top of the earth (see Table 2). Comparative Example 3 Only polyether sulfone was used at a cylinder temperature of 32 pi○.
When the molded product was injection molded at a mold temperature of 120 qo, flow marks were observed on the surface and the gloss was poor (see Table 2).

Example 7 5 parts by weight of polysulfone (P-1700, manufactured by Nissan Chemical Co., Ltd.), 5 parts by weight of PM (Ryton V-1), and 5 parts by weight of Noporac type epoxy resin (Epicron N-695) were uniformly prepared in advance. After mixing, use a 3-hiho twin-screw extruder to
It was kneaded at 20oo.

A test piece was molded from this mixture using an injection molding machine at a cylinder temperature of 300° C. and a mold temperature of 100 qo. The molded product had a cream-colored appearance, good compatibility, and excellent surface gloss. When the physical properties were measured, the bending strength was 880k9/c, and the Izod impact strength (notched) was 4k9/c (Table -
(see 2). Table 2 Example 8 50 parts by weight of a polymer having molecular structural units of polyphenylene oxide and having an intrinsic viscosity of 0.65, P
After uniformly premixing 5 parts by weight of PS (Ryton V-1) and 5 parts by weight of novolac type epoxy resin (Epicron N-695), 31000 g
It was kneaded with

A test piece was molded from this mixture using an injection molding machine. The appearance of the molded product was cream-colored and had good compatibility.

When the physical properties were measured, the bending strength was 810k9/s, the Izod impact strength (with notch) was 4.5kg/arc/arc,
The heat distortion temperature (18.6k9/su) was 146qo (see Table 3). Examples 9-10 In Example 8, the weight ratio of polyphenylene oxide and PR was 30'70.
and changed to 70/30.

The results were as excellent as in Example 8, as summarized in Table 3. Comparative Example 4 When no epoxy resin was added in Example 8, the molded product had poor compatibility and a pearl-like luster.

The physical properties were measured, and the bending strength was 460 kg/ground, and the impact strength (with notch) was low at 2k9.ga/ga (see Table 3). Table 3 Example 11 Parts by weight of 5 parts by weight of polyetheretherketone (a general molding grade product made by ICI having the molecular structure unit of N-695)
After uniformly premixing 5 parts by weight, the mixture was kneaded at 330° C. using a 30 Yanagi 2 ball extruder.

A test piece was molded from this mixture using an injection molding machine at a cylinder temperature of 320°C and a mold temperature of 100°C. The appearance of the molded product had good compatibility and excellent surface gloss.

When the physical properties were measured, the bending strength was 950 k9 / arc, and the Izod impact strength (notched) was 3 k9 / skin / arc (see Table 4). Examples 12-13 In Example 11, the weight ratio of polyether ether ketone and PPS was changed to 30/70 and 70/30.

As shown in Table 4, the results were as good as in Example 11. Comparative Example 5 When no eboxy resin was added in Example 11, the appearance of the molded product had poor lacquer reciprocity and a pearl-like luster.

The physical properties were measured, and the bending strength was 9/2 with spots, and the Izod impact strength (with notch) was as low as 2 kg/2 kg (see Mugi-4). Comparative Example 6 Only polyetheretherketone was used at a cylinder temperature of 35
When the molded product was injection molded at 0qo and a mold temperature of 120°C, flow marks were observed on the surface and the gloss was poor (see Table 4).

Table 4 Example 14 5 parts by weight of polyamideimide (Torlon 40m, manufactured by Amoco), 5 parts by weight of P-Ko (Ryton V-1), and 3 parts by weight of novolac type epoxy resin (Epicron N-695) were uniformly added. After preliminary mixing, the mixture was mulled at a total temperature of 0°C using a three-sided twin-screw extruder.

From this mixture, using an injection molding machine, a cylinder temperature of 3.
A test piece was molded at 30° C. and a mold temperature of 13 mm.
The appearance of the molded product was uniform and had excellent compatibility.
When the physical properties were measured, the bending strength was 830k9/ground, and the heat distortion temperature (18.6kg/ground) was as high as 185°C (see Table 5). Examples 15 to 16 In Example 14, the weight ratio of polyamidimide and P resin was changed to 30/70 and 70'30.

As shown in Table 5, the results were as excellent as in Example 14. Comparative Example 7 When no epoxy resin was added in Example 14, the molded product had poor compatibility and a pearly luster.

The molded product was so brittle that test pieces could not be obtained, and physical properties could not be measured (see Table 5). Example 17 5 parts by weight of polyimide ("Polyimide" 2080, manufactured by Up John), 50 parts by weight of P-Ore (Ryton V-1) and /Polack type epoxy resin (Epicron N-695)
) 3 parts by weight were uniformly premixed and then kneaded at 320°C using a 3-neck twin-screw extruder.

A test piece was molded from this mixture using an injection molding machine at a cylinder temperature of 330°C and a mold temperature of 130°C. The molded product had a uniform appearance and good compatibility.

When the physical properties were measured, the bending strength was 640k9/ground, and the heat distortion temperature (18.6k9/ground) was as high as 235°C (see Table 5). Table-5

Claims (1)

[Claims] 1 99 to 1 part by weight of polyphenylene sulfide resin (A), 1 to 99 parts by weight of at least one resin selected from the group consisting of polyarylate, polysulfone, polyphenylene oxide, polyetherketone, and polyimide (B) , and 0.1 to 30 parts by weight of an epoxy resin (C) per 100 parts by weight of the total of resins (A) and resins (B).