JPH04275368A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having remarkably improved adhesive properties to an epoxy resin and excellently maintaining its essential properties by blending polyphenylene sulfide resin with a filler and a polyalkylene ether compound. CONSTITUTION:With (A) 100 pts.wt. polyphenylene sulfide resin, (B) 0-400 pts.wt. fibrous and/or non-fibrous filler is mixed and (C) 1.2-15 pts.wt. polyalkylene ether compound is blended with 100 pts.wt. above-obtained mixture (A)+(B). As the above-mentioned component (C), polyethylene glycol, polytetramethylene glycol, etc., having 20000-5000000 number-average molecular weight is preferable.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyphenylene sulfide resin composition having improved adhesion to epoxy resins.

0002

[Prior art] Polyphenylene sulfide resin (hereinafter referred to as P
PS resin (abbreviated as PS resin) has properties suitable for engineering plastics, such as excellent heat resistance, flame retardance, rigidity, and chemical resistance, and is used mainly for injection molding, as well as various electrical parts, mechanical parts, and automobile parts. used in

However, PPS resin has relatively low adhesive strength with other resins, particularly with epoxy resins. Therefore, when bonding PPS resins together using epoxy adhesives, bonding PPS resins with other materials, or sealing electrical and electronic components with epoxy resins, this PP
The low adhesive strength between S resin and epoxy resin is often a problem, and is one of the reasons for hindering the expansion of demand for PPS resin.

[0004] As an example of studies on improving the adhesion between PPS resin and epoxy resin, there is a method of adding carnauba wax to PPS resin (Japanese Unexamined Patent Publication No. 2-272063).

[0005]

[Problems to be Solved by the Invention] However, in the method described in JP-A-2-272063, the effect of improving tensile shear adhesive strength by adding carnauba wax is at most about 20% compared to the case without addition, which is not satisfactory. It is hard to say that it is at a good level.

[0006] Therefore, the present invention aims to provide P with high mechanical strength.
PPS whose adhesion with epoxy resin has been sufficiently improved without significantly impairing the excellent properties originally possessed by PS resin.
The challenge is to obtain a resin composition.

[0007]

[Means for Solving the Problems] That is, the present invention provides (A
) 100 parts by weight of polyphenylene sulfide resin, (B
) 0 to 400 parts by weight of fibrous and/or non-fibrous filler and (C) polyalkylene ether compound (A
)+(B) in an amount of 1.2 to 15 parts by weight per 100 parts by weight. The polyphenylene sulfide resin (A) used in the present invention has a repeating unit represented by the structural formula (I).

[0008]

[Chemical formula 1]

[0009] It is a polymer containing 70 mol% or more, more preferably 90 mol% or more of the above-mentioned repeating unit.If the content of the repeating unit is less than 70 mol%, heat resistance will be impaired, which is not preferable. Furthermore, less than 30 mol% of the repeating units in the PPS resin can be composed of repeating units having the following structural formula.

0010

[Case 2]

The melt viscosity of the PPS resin used in the present invention is not particularly limited as long as it can be melt-kneaded, but it is usually 5.
0 to 20,000 poise (320℃, shear rate 10se
c-1) is used.

[0012] In the present invention, (
B) Fibrous and/or non-fibrous fillers include glass fibers, carbon fibers, potassium titanate whiskers, zinc oxide whiskers, alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, gypsum fibers, metal fibers, etc. Fibrous fillers, silicates such as wollastenite, sericite, kaolin, mica, clay, bentonite, asbestos, talc, alumina silicate, alumina, silicon oxide,
Metal compounds such as magnesium oxide, zirconium oxide, titanium oxide, and iron oxide, carbonates such as calcium carbonate, magnesium carbonate, and dolomite, sulfates such as calcium sulfate and barium sulfate, glass beads, ceramic beads, boron nitride, Examples include non-fibrous fillers such as silicon carbide and silica, which may be hollow, and it is also possible to use two or more of these fillers in combination. Further, it is more preferable to use these fibrous and/or non-fibrous fillers after being pretreated with a coupling agent such as a silane type or a titanate type from the viewpoint of mechanical strength.

The fibrous and/or non-fibrous filler (B) in the present invention is not an essential component, but may be added in an amount of up to 400 parts by weight per 100 parts by weight of the PPS resin (A), if necessary. (A) PPS in the sense of obtaining higher mechanical properties, dimensional stability, etc.
It is preferable to mix 40 to 350 parts by weight of the fibrous and/or non-fibrous filler (B) with respect to 100 parts by weight of the resin.

The polyalkylene ether compound (C) used in the present invention is a compound represented by the following general formulas (II) to (IV).

[0015]

[Chemical formula 3]

(Here, R1 represents a linear and/or side chain alkylene group having 2 to 10 carbon atoms;
2 to R5 represent a hydrogen atom, an aliphatic, alicyclic, aromatic hydrocarbon group having 1 to 20 carbon atoms, or an acyl group, and R2 to R5 may be the same or different from each other. Further, m represents an integer of 2 or more, and n, f, g, and h each represent an integer of 0 or 1 or more. However, the general formula (I
In II), n, g, h are not all 0 at the same time, and in general formula (IV), n, f, g,
h cannot all be 0 at the same time. ) The alkylene group having a straight chain and/or side chain having 2 to 10 carbon atoms represented by R1 includes, for example, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a 1,1-dimethylethylene group, a pentamethylene group. , 2,2-dimethyltrimethylene group, hexamethylene group, 2,2-dimethyltetramethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, etc., of which two or more types are present in one molecule. may be mixed.

Examples of the aliphatic, alicyclic, aromatic hydrocarbon group or acyl group having 1 to 20 carbon atoms as R2 to R5 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, and isobutyl group. group, s-butyl group, t
-Butyl group, pentyl group, isopentyl group, neopentyl group, t-pentyl group, 1-methylbutyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, octadecyl group, cyclohexyl group, cyclohexylmethyl group , phenyl group and its alkyl group, substituents such as halogen, formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, hexanoyl group, octanoyl group, decanoyl group, cyclohexylcarbonyl group, benzoyl group, etc. , two or more types of these may be mixed in one molecule.

Specific examples of these polyalkylene ether compounds include polyethylene glycol, 1,2-
Polypropylene glycol, 1,3-polypropylene glycol, polytetramethylene glycol, polyoxyethylene/propylene, polyoxyethylene/tetramethylene, polypentamethylene glycol, polyhexamethylene glycol, polyhepta Methylene glycol, polyoctamethylene glycol, glycerol mono, di, tri(polyoxyethylene) ether, glycerol mono, di, tri(polyoxypropylene) ether,
Mono-, di-, tri-(polyoxytetramethylene) ether of glycerol, mono-, di-, tri-, tetra(polyoxyethylene) ether of pentaerythritol, mono-, di-, tri-, tetra(polyoxypropylene) ether of pentaerythritol, pentaerythritol Mono-, di-, tri-, tetra(polyoxytetramethylene) ethers of erythritol and monoethers derived from these polyols,
Examples include diether, triether, tetraether, monoester, diester, triester, and tetraester compounds. Among these, polyethylene glycol, 1,2-polypropylene glycol, 1,3-
Polypropylene glycol, polytetramethylene glycol, polyoxyethylene/propylene, polyoxyethylene/tetramethylene and derivatives thereof are preferred, especially polyethylene glycol, polypropylene glycol, polyoxyethylene/propylene and polytetramethylene glyco - is particularly preferably used from the viewpoint of improving adhesiveness.

The number average molecular weight of the polyalkylene ether compound (C) used in the present invention is not particularly limited, but in order to obtain better moldability and higher adhesive strength, it is recommended that the number average molecular weight be 500. It is preferably at least 10,000, particularly preferably at least 10,000, and more preferably from 20,000 to 5,000,000.

The blending amount of (C) polyalkylene ether compound used in the present invention is 1.2 to 15 parts by weight based on 100 parts by weight of (A) PPS resin + (B) fibrous and/or non-fibrous filler. Parts by weight are selected, more preferably 2 to 10 parts by weight. If the amount is less than 1 part by weight, a sufficient effect of improving adhesion cannot be obtained, and if the amount exceeds 15 parts by weight, the mechanical strength will be significantly impaired, which is not preferable.

[0021] With the above structure, the PPS resin composition of the present invention has improved adhesion to an epoxy resin. The epoxy resin mentioned here is not particularly limited, and examples include bisphenol A, bisphenol F, bisphenol S, bisphenol AF, bisphenol AD, 4,4'-dihydroxybiphenyl, resorcinol, saligenin, trihydroxydiphenyldimethylmethane, and tetraphenylol. Ethane, halogen-substituted and alkyl-substituted products of these, butanediol, ethylene glycol, erythritol, novolak, glycerin, polyoxyalkylene, etc., which are synthesized from compounds containing two or more hydroxyl groups in the molecule, and epichlorohydrin, etc. Synthesized from glycidyl ethers, glycidyl esters such as phthalic acid glycidyl ester, primary or secondary amines such as aniline, diaminodiphenylmethane, metaxylene diamine, 1,3-bisamiminimethylcyclohexane, and epichlorohydrin. Examples include glycidyl epoxy resins such as glycidyl amine type, non-glycidyl epoxy resins such as epoxidized soybean oil, epoxidized polyolefin, vinyl cyclohexene dioxide, dicyclopentadiene dioxide, and the like. These epoxy resins may be used alone or as a mixture of two or more. Further, these epoxy resins are generally used after being cured with a curing agent. Examples of curing agents include amines, polyamides, amino resins, acid anhydrides, polyhydric phenols, phenolic resins, polysulfides, isocyanates, and the like.

The PPS resin composition of the present invention may contain antioxidants, heat stabilizers,
Conventional additives such as lubricants, plasticizers, nucleating agents, UV inhibitors, colorants, flame retardants, etc. can be added. Also,
The PPS resin composition of the present invention may contain polyamide, polyphenylene oxide, polysulfone, polytetrafluoride, polyetherimide,
May contain resins such as polyamideimide, polyimide, polycarbonate, polyether sulfone, polyether ketone, polyether ether ketone, epoxy resin, phenol resin, polyethylene, polystyrene, polypropylene, ABS resin, polyester, etc. .

[0023] The PPS resin composition of the present invention contains γ-glycidoxypropyltrimethoxysilane, γ- Glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ- ureidopropyltrimethoxysilane and γ-(2-ureidoethyl)aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ
-isocyanatopropylmethyldimethoxysilane, γ-
Organic silane compounds such as isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, and γ-isocyanatopropyltrichlorosilane can be added.

The method for preparing the composition of the present invention is not particularly limited, but the raw material mixture may be melted using a commonly known melting method such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, or a mixing roll. Examples include a method in which the mixture is supplied to a mixer and kneaded at a temperature of 280 to 380°C. Furthermore, there is no particular restriction on the mixing order of the raw materials, and after dry blending the PPS resin, fibrous and/or non-fibrous filler, and polyalkylene ether compound, melt-kneading is performed by the method described above. method, or PPS resin,
A typical method is to dry blend and melt-knead two of the fibrous and/or non-fibrous filler and the polyalkylene ether compound, and then melt-knead this and the remaining one.

The present invention will be explained in more detail with reference to Examples below.

[0026]

[Example] The bending strength, Izod impact strength, and tensile shear adhesive strength described in the Examples and Comparative Examples were each measured according to the following methods.

Bending strength: ASTM-D790 Izod impact strength: ASTM-D256 Tensile shear adhesive strength: AS
Divide the TM1 dumbbell piece into two and use spacers (thickness 1
mm, adhesion area 2.52 cm2) was sandwiched and fixed, and epoxy resin was poured in. Harden this to 1mm/m
The tensile strength was measured at a speed of in , and the maximum value of the strength was divided by the adhesive area to obtain the tensile shear adhesive strength.

Reference Example 1 (Synthesis method of polyphenylene sulfide) PPS-1: Sodium sulfide 3 was placed in an autoclave.
．． 26Kg (25mol, including 40% water of crystallization), 4g of sodium hydroxide, 1.19Kg of sodium acetate trihydrate
(approximately 8.8 mol) and 7.9 kg of NMP were charged, the temperature was gradually raised to 205°C while stirring, and 1.36 kg of water was added.
Approximately 1.5 liters of distillate containing water were removed. 1 to the residual mixture
3.75 kg (25.5 mol) of 4-dichlorobenzene and 2 kg of NMP were added, and the mixture was heated at 265°C for 3 hours. The reaction product was washed 5 times with hot water at 70°C and incubated at 80°C for 24 hours.
After drying under reduced pressure for an hour, the melt viscosity was approximately 600 poise (310°C).
About 2 kg of powdered polyphenylene sulfide (PPS-1) with a shear rate of 1000 seconds-1) was obtained.

PPS-2: 3.26 kg of sodium sulfide (25 mol, containing 40% crystal water) in an autoclave,
Sodium hydroxide 4g, sodium acetate trihydrate 1.2
Prepare 2Kg (approximately 9 mol) and 7.9Kg of NMP,
Gradually raise the temperature to 205℃ while stirring, and add water to 1.36K.
Approximately 1.5 liters of distilled water containing g was removed. 1 in the residual mixture
,4-dichlorobenzene 3.75Kg (25.5mol)
and 2 kg of NMP were added and heated at 265° C. for 3.7 hours. The reaction product was washed 5 times with 70°C warm water and then heated to 80°C.
Dry under reduced pressure for 24 hours to achieve a melt viscosity of approximately 900 poise (3
About 2 kg of powdered polyphenylene sulfide (PPS-2) was obtained at 10°C and a shear rate of 1000 sec-1).

As PPS-3, M2100 manufactured by Toray-Philips Petroleum Co., Ltd. was used.

Examples 1 to 8 After dry blending PPS resin, polyalkylene ether compound and filler in the proportions shown in Table 1,
The mixture was melt-kneaded using a screw extruder set at a temperature of ~320°C and then pelletized. The obtained pellets were used to mold test pieces for measuring mechanical properties and tensile shear adhesive strength.

Table 3 shows the bending strength, Izod impact strength, and tensile shear adhesive strength measured for the obtained test piece.

Comparative Examples 1 to 2 PPS resin and filler were dry blended in the same manner as in Examples 1 and 2 except that no polyalkylene ether compound was added, and then the temperature was set at 280 to 320°C. The mixture was melt-kneaded using a screw extruder and then pelletized. The obtained pellets were used to mold test pieces for measuring mechanical properties and tensile shear adhesive strength.

Table 4 shows the bending strength, Izod impact strength, and tensile shear adhesive strength measured for the obtained test piece.

Comparative Examples 3 to 4 After dry blending PPS resin, polyalkylene ether compound and filler in the proportions shown in Table 2,
The mixture was melt-kneaded using a screw extruder set at a temperature of ~320°C and then pelletized. The obtained pellets were used to mold test pieces for measuring mechanical properties and tensile shear adhesive strength.

Table 4 shows the bending strength, Izod impact strength, and tensile shear adhesive strength of the test pieces obtained.

As described above, if the amount of the polyalkylene ether compound added is 0.5 parts by weight, sufficient adhesive strength cannot be obtained, and if the amount added is 18 parts by weight, the mechanical strength is significantly impaired, which is not preferable.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

[Table 3]

[0041]

[Table 4]

[0042]

Effects of the Invention The polyarylene sulfide resin composition of the present invention is a polyphenylene sulfide resin composition that has improved adhesion to epoxy resin without substantially impairing mechanical strength such as impact resistance. Suitable for cases involving secondary processing such as bonding with adhesives or sealing of electrical/electronic parts with epoxy resin.

Claims (1)

[Claims] Claim 1: (A) 100 parts by weight of polyphenylene sulfide resin, (B) 0 to 400 parts by weight of fibrous and/or non-fibrous filler, and (C) polyalkylene ether compound (A) + (B) 1 per 100 parts by weight
．． A polyphenylene sulfide resin composition containing 2 to 15 parts by weight.