JP2002309064A - Polyoxymethylene resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyoxymethylene resin composition exhibiting good affinity and dispersibility of a polyoxymethylene resin and a styrene resin, a polycarbonate resin and a polyolefin resin, having excellent dimensional stability, mechanical properties such as impact resistance and thermal stability and giving a molded article having excellent surface state. SOLUTION: The objective polyoxymethylene resin composition is produced by compounding 100 pts.wt. of a polyoxymethylene resin obtained by the copolymerization of trioxane and 1,3-dioxolane in the presence of a cationic active catalyst, using 7.1-11.0 mol% of 1,3-dioxolane based on trioxane and having a crystallization time of 30-600 sec at 148 deg.C with 0-100 pts.wt. of at least one kind of resin selected from styrene resin, polycarbonate resin and polyolefin resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molding resin composition in which a polystyrene resin, a polycarbonate resin or a polyolefin resin is blended with a polyoxymethylene resin. And a polyoxymethylene resin composition having excellent mechanical properties such as dimensional stability and impact resistance, and excellent thermal stability.

[0002]

2. Description of the Related Art Polyoxymethylene resins have excellent properties in mechanical properties, thermal properties, electrical properties, slidability, moldability, and the like. Widely used for parts, precision machine parts, etc.

However, polyoxymethylene resin has high crystallinity and therefore has a high molding shrinkage, and in parts requiring high dimensional accuracy, there is a problem that it is difficult to obtain the required dimensional accuracy due to warpage or deformation. . Also, mechanical properties such as impact resistance may not be sufficient, and further improvement is often required depending on the application.

[0004] In general, in modifying the physical properties of a thermoplastic resin, it is common practice to compensate for the defect by blending another resin having a property to supplement the physical properties, and the purpose is often achieved.

However, polyoxymethylene resins are different from general thermoplastic resins, and when other thermoplastic resins are blended, the mutual compatibility and dispersibility between the resins are particularly poor, and the adhesion at the interface between the two phases is insufficient. In this case, phase separation occurs at the interface, and when a molded product is formed, surface layer peeling may occur, and it is extremely difficult to modify such a resin by means of compounding.

[0006] Styrene-based resins and polycarbonate-based resins are thermoplastic resins which are amorphous and have a small molding shrinkage.
Polyolefin resins are particularly suitable for weight reduction due to their low specific gravity. However, blending with these resins is no exception, and the adhesion between the two phases is insufficient, and phase separation at the interfaces is not sufficient. And practical problems such as easy peeling of the surface layer when formed into a molded product.

For this purpose, for the purpose of improving the affinity between polyoxymethylene resins and these resins, for example, a method in which the ratio of the melt flow values of the polyoxymethylene resin and the styrene resin is set to a specific range (Japanese Patent Application Laid-Open No. Sho 64) -38463), a method of blending a polyoxymethylene resin with a polyolefin resin containing a reactive glycidyl group in its molecular structure (JP-A-59-64654), and a method of grafting an unsaturated carboxylic acid. A method of blending a modified α-olefin polymer obtained by polymerization (JP-A-59-204652) has been proposed, but has not yet been sufficiently improved.

Further, it is known that polyoxymethylene resin has poor thermal stability due to its molecular structure and is easily decomposed by depolymerization from a polymer terminal or cleavage of a main chain by a thermal oxidation reaction. Further, such a thermal oxidative decomposition reaction is promoted during, for example, melt-kneading with another resin, and may greatly impair the thermal stability of the polyoxymethylene resin.

[0009]

The problem to be solved by the present invention is that the affinity and dispersibility of a polyoxymethylene resin and a styrene resin, a polycarbonate resin or a polyolefin resin are good and the surface of the molded article is good. An object of the present invention is to provide a polyoxymethylene resin composition which is excellent in state, has excellent mechanical properties such as dimensional stability and impact resistance, and has excellent thermal stability.

[0010]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, when trioxane is copolymerized with a specific amount of 1,3-dioxolan, a specific polymerization time is required. The above object is achieved by blending at least one selected from a styrene resin, a polycarbonate resin and a polyolefin resin with a polyoxymethylene resin having a crystallization time in a specific range obtained by This led to the completion of the present invention.

That is, the present invention relates to trioxane and 1,3-
In copolymerizing dioxolane using a cationically active catalyst, 1,3-dioxolane is obtained using 7.1 to 11.0 mol% based on trioxane, and the crystallization time at 148 ° C. is 30 to 600 seconds. The present invention relates to a polyoxymethylene resin composition obtained by mixing 0 to 100 parts by weight of at least one selected from styrene-based resins, polycarbonate-based resins and polyolefin-based resins with respect to 100 parts by weight of a certain polyoxymethylene resin. is there.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The polyoxymethylene resin used in the present invention is prepared by combining trioxane which is a cyclic trimer of formaldehyde as a raw material monomer and 1,3-dioxolane as a comonomer in the presence of a cationic polymerization catalyst. It is obtained by polymerizing. 1,3 in this case
-The amount of dioxolane added is 7.
1 to 11.0 mol%. If the amount of 1,3-dioxolan used is less than this, the dispersibility of the resins as intended in the present invention is poor, and if it is too large, the inherent properties of the resin are lost, which is not preferred.

As the polymerization catalyst, a general cation-active catalyst is used. Such cationically active catalysts include Lewis acids, especially halides such as boron, tin, titanium, phosphorus, arsenic and antimony, such as boron trifluoride, tin tetrachloride, titanium tetrachloride, phosphorus pentachloride, pentafluoride. Compounds such as phosphorus arsenide, arsenic pentafluoride and antimony pentafluoride, and complexes or salts thereof, protic acids such as trifluoromethanesulfonic acid, perchloric acid, esters of protic acids, especially perchloric acid and lower aliphatic alcohols Esters, protonic anhydrides, especially mixed anhydrides of perchloric acid and lower aliphatic carboxylic acids, or triethyloxonium hexafluorophosphate, triphenylmethylhexafluoroarsenate, acetylhexafluoroborate, heteropolyacid Or its acid salt, isopoly acid or its Such as gender salts. Particularly, a compound containing boron trifluoride, or a hydrate of boron trifluoride and a coordination complex compound are preferable, and boron trifluoride diethyl etherate and trifluoride, which are coordination complexes with ethers, are preferred. Borobium dibutyl etherate is particularly preferred.

The polyoxymethylene resin can be polymerized by the same equipment and method as in the conventionally known trioxane copolymerization. That is, any of a batch method and a continuous method is possible, and the present invention is also applied to bulk polymerization and a polymerization method performed in the presence of an organic solvent such as cyclohexane. In batch type, a reaction tank with a stirrer can be used.In continuous bulk polymerization, rapid solidification during polymerization, strong stirring capacity capable of coping with heat generation, precise temperature control, and prevention of scale adhesion Apparatuses such as a kneader having a self-cleaning function, a twin-screw type continuous extrusion kneader, and a twin-screw paddle type continuous mixer are preferably used.

In the polymerization of polyoxymethylene resin,
It is important to control the polymerization temperature before and after the polymerization yield of 60-90% (defined as the boundary yield). The boundary yield is preferably between 65 and 90%, more preferably between 70 and 90%, and most preferably between 80 and 90%. The polymerization temperature is preferably 60 to 120 ° C., preferably 6 ° C., until the polymerization yield reaches the boundary yield.
It should be kept in the range 0-110 ° C, more preferably 60-100 ° C, most preferably 60-90 ° C. When the polymerization yield is equal to or higher than the boundary yield, 0 to 1
00 ° C, preferably 0-80 ° C, more preferably 0 ° C.
It should be kept at ~ 70C, most preferably in the range of 0-60C. If the polymerization temperature until the polymerization yield reaches the boundary yield is higher than this, the thermal stability decreases and the polymerization yield also decreases. When the temperature is low, the thermal stability is maintained, but the polymerization yield also decreases in this case. If the polymerization temperature above the boundary yield is higher than this, the thermal stability will decrease,
When it is low, problems such as an increase in the torque of the stirring power of the polymerization machine occur. Also, the polymerization temperature above the boundary yield must not be higher than the temperature to reach the boundary yield. If this were reversed, thermal stability would be reduced.

In the polymerization of polyoxymethylene resin,
A polymerization time of 3 to 120 minutes is selected, and particularly preferably 10 to 60 minutes. If the polymerization time is shorter than this, the thermal stability will decrease.

The polyoxymethylene resin obtained by the polymerization reaction may be used alone or in an aqueous solution or an organic solution of a deactivator such as a trivalent organic phosphorus compound, an amine compound, or a hydroxide of an alkali metal or an alkaline earth metal. The catalyst is deactivated and removed by a known method used in the form. Among these, a trivalent organic phosphorus compound and a tertiary amine are particularly preferably used.

The polyoxymethylene resin in which the polymerization catalyst has been deactivated can be directly sent to the subsequent stabilization step. However, if further purification is necessary, washing, separation and recovery of unreacted monomers, It can undergo drying and the like. In the stabilization step, an antioxidant,
Stabilizers such as a heat stabilizer are blended and melt-kneaded by a twin-screw extruder or the like, and the mixture is stabilized.

The antioxidant which can be used in the stabilization treatment includes triethylene glycol-bis-3- (3
-T-butyl-4-hydroxy-5-methylphenyl)
Propionate, pentaerythrityl-tetrakis-3
Sterically hindered phenols such as-(3,5-di-t-butyl-4-hydroxyphenyl) propionate. Examples of the heat stabilizer include melamine, methylol-melamine, benzoguanamine, cyanoguanidine, N, N-
Examples include amine-substituted triazines such as diarylmelamine, polyamides, urea derivatives, urethanes, and the like, and inorganic salts, hydroxides, and organic acid salts of sodium, potassium, calcium, magnesium, and barium.

The crystallization time of the obtained polyoxymethylene resin at 148 ° C. is 30 to 600 seconds. By adjusting the crystallization time of the resin used in the present invention to this range, a good resin composition is obtained. If the crystallization time is short, the effect of the present invention is not sufficiently exhibited, and if it is too long, the properties of the polyoxymethylene resin are impaired.

The styrene resin used in the present invention includes aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene and p-hydroxystyrene and derivatives thereof alone. Polymers, random, block, or graft copolymers of two or more of these, or derivatives thereof such as α, β-unsaturated acids such as acrylic acid and methacrylic acid or esters thereof, acrylonitrile, methacrylonitrile And random, block, or graft copolymers comprising one or more of these derivatives or comonomer components such as vinyl esters such as vinyl acetate, vinyl ethers such as vinyl methyl ether, and derivatives of these vinyl compounds. The degree of polymerization, the presence or absence and degree of side chains and branches, It does not matter how, such as the composition ratio.

Of these, styrene copolymer resins are particularly preferred. Copolymers having an effect on dimensional stability include, for example, styrene-acrylonitrile copolymer, styrene-copolymer
Acrylic acid methyl ester copolymer, styrene / methacrylic acid methyl ester copolymer, styrene / acrylonitrile / butadiene copolymer, hydrogenated product of styrene / acrylonitrile / butadiene copolymer, styrene / acrylonitrile / ethylene copolymer, etc. No.
Further, those having an effect on impact resistance include styrene / acrylonitrile / butadiene copolymer, hydrogenated product of styrene / acrylonitrile / butadiene copolymer, styrene / butadiene block copolymer, and styrene / butadiene block copolymer. And styrene-acrylonitrile-ethylene copolymers.

The polycarbonate resin is obtained by a phosgene method or a transesterification method in which a divalent hydroxy compound and a carbonic acid diester are used as raw materials and melt polycondensation is carried out. Furthermore, it can be obtained by a solid phase polymerization method, but is not limited by these production methods. Basically, it has a repeating carbonate group of (-OCOO-),
Aliphatic, aromatic, aliphatic-aromatic polycarbonates can be used. Usually, the aromatic polycarbonate resin is
A 2,2-bis (4-hydroxyphenyl) propane polycarbonate resin known as a bisphenol A type polycarbonate resin is preferred. The polycarbonate resin preferably has a viscosity average molecular weight of 10,000 to 40,000 in consideration of mechanical strength and moldability.

Examples of the polyolefin resin include homopolymers of α-olefins such as ethylene, propylene, butene, hexene, octene, nonene, decene and dodecene, and random, block or graft copolymers composed of two or more of these. Or 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2
Non-conjugated dienes such as -norbornene and 2,5-norbonadiene, conjugated diene components such as butadiene, isoprene and piperylene, α, β-unsaturated acids such as acrylic acid and methacrylic acid and derivatives such as esters thereof, acrylonitrile,
Styrene, an aromatic vinyl compound such as α-methylstyrene, or a vinyl ester such as vinyl acetate, a random containing at least one of comonomer components such as vinyl ethers such as vinyl methyl ether and derivatives of these vinyl compounds, Examples thereof include block or graft copolymers, regardless of the degree of polymerization, the presence or absence or degree of side chains or branches, and the copolymer composition ratio.

The amount of these components is 1 to 100 parts by weight, preferably 10 to 90 parts by weight, based on 100 parts by weight of the polyoxymethylene resin. If the amount is too low, the effects of the present invention will not be sufficiently exhibited, and if it is too high, the properties of the polyoxymethylene resin will be impaired.

The resin composition of the present invention has various additives known in the art for imparting desired properties, for example, various stabilizers such as antioxidants, heat stabilizers, weather (light) stabilizers, and hydrolysis stabilizers. , Lubricants, lubricants, nucleating agents, coloring agents such as dyes and pigments, release agents,
An antistatic agent, a plasticizer, a flame retardant and the like can be blended. Further, other thermoplastic resins may be further compounded within a range not to impair the scope of the present invention.

The polyoxymethylene resin composition of the present invention can be prepared by various known methods. For example, a method in which each component is mixed with a blender such as a turn bull mixer or a Henschel mixer and then kneaded with a single or twin screw extruder, a bumper mixer, a roll, or the like is appropriately selected. Each component is preferably dried before kneading.

[0028]

EXAMPLES The present invention will be described in more detail with reference to the following Examples and Comparative Examples, which by no means limit the scope of the present invention. The terms and measurement methods in the examples and comparative examples are shown below.

Confirmation of dispersibility and interfacial adhesiveness: Observe the fracture surface of the molded piece with an electron microscope, and clarify the interface (the clearer, the poorer the dispersibility and interfacial adhesiveness), the particle dispersion form (particle shape) , Size) and the condition of the fracture surface. These were combined to rank excellent, good, and bad. Surface layer peeling test: After sticking Cellotape (registered trademark) on the surface of the test piece and peeling it off under a certain condition, the peeling state of the molded product surface layer was visually evaluated. △, those markedly peeled off ×
And Izod impact test: Notched impact strength (thickness 3.2 mm) was measured according to ASTM D256. Molding Shrinkage Measurement: The shrinkage of the molded article was measured according to ASTM D955. Retention heat stability: Using an injection molding machine having a mold clamping pressure of 75 tons, the resin was kept in the cylinder at a cylinder temperature of 240 ° C. for a certain period of time, and the required residence time until silver streak was generated was measured. The higher the value, the better the thermal stability. Crystallization time: measured by a polymer crystallization rate measuring device (MK-701 manufactured by Hexa Chemical Co., Ltd.) that optically detects a change in birefringence due to crystallization. A film sample having a thickness of about 50 μm formed by hot pressing was heated and melted at 200 ° C. for 2 minutes, immersed in an oil bath at 148 ° C., and passed through a polarizing plate (polarizer) to transmit the light. The amount of light after passing through a polarizing plate (analyzer) was detected by a light receiving element, and the time required for crystallization was measured based on the time change of the amount of light. Here, the total of the induction period time from the start of measurement at 148 ° C. to the start of crystallization and the half-crystallization time (half the time required from the start of crystallization to the end of crystallization) were measured, and this was defined as the crystallization time. did. Polymerization yield: After immersing 20 g of the copolymer in which the catalyst has been deactivated, in 20 ml of acetone, the mixture is filtered, and acetone is added.
After washing twice, vacuum drying was performed at 60 ° C. until the weight became constant. Thereafter, the mixture was precisely weighed, and the polymerization yield was determined by the following equation. Polymerization yield = M ₁ / M ₀ × 100 (however, M ₀ : weight before acetone treatment, M ₁ : weight after acetone treatment and drying)

Examples 1 to 12, Reference Examples 1 and 2 100 parts by weight of trioxane and 1,3-
Using dioxolane as a catalyst with boron trifluoride diethyl etherate as a catalyst and using 60 ppm as BF _{3 with} respect to all monomers (trioxane + 1,3-dioxolane), and using methylal as a chain transfer agent with 500 ppm with respect to all monomers, Polymerization was carried out in a biaxial kneader (having a jacket around) having intermeshing paddles, with the jacket temperature (polymerization temperature) set at 65 ° C. After the polymerization time shown in Table 1, the catalyst was deactivated by a 5% by weight benzene solution of triphenylphosphine twice as much as the amount of the catalyst, and pulverized to obtain a polyoxymethylene copolymer. The polymerization yield is 90% or more, and the intrinsic viscosity at 60 ° C. in p-chloroform (α-pinene added) is 1.
It was 1-1.5 dl / g. Also, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Geigy, trade name Irga) was added to 100 parts by weight of the obtained copolymer. Knox 245) 0.3 parts by weight, melamine 0.1 parts by weight, and magnesium hydroxide 0.05 parts by weight were added, and premixed using a Henschel mixer. Thereafter, the mixture was fed to a vented twin-screw extruder, melt-kneaded at 200 ° C. under a reduced pressure of 160 Torr, and pelletized. The crystallization time of the obtained pellets was measured, and the results are shown in Table 1. The resin composition was prepared by blending the styrene-based resin of the type shown in Table 1 with the pellets in the proportions shown in Table 1 and premixing with a Henschel mixer. The mixture was melt-kneaded at a temperature of 190 ° C. and pelletized. Next, a test piece was prepared by injection molding using the pellet, and the evaluation was performed. In the case where no styrene-based resin was blended, evaluation was made in the same manner as in Examples 1 to 14. The results are shown in Table 1.

Comparative Examples 1 to 9 The same procedures as in Examples 1 to 14 were carried out except that the amounts of 1,3-dioxolane, polymerization time, and the amounts of polyoxymethylene resin and styrene resin shown in Table 1 were used. The results are shown in Table 1.

Examples 15 to 18 The same amount of 1,3-dioxolane, polymerization time, polyoxymethylene resin and ABS resin as in Example 3 or Example 10 were used by changing the amount of ABS resin in the proportions shown in Table 2. And performed in the same manner as in Example 3 or Example 10. The results are shown in Table 2.

Comparative Examples 10 to 13 The same procedures as in Examples 15 to 18 were carried out except that the amounts of 1,3-dioxolane and the polymerization time shown in Table 2 were used. Table 2 shows the results
It was shown to.

Examples 19 to 30 In place of the styrene resin, a polycarbonate resin (Iupilon S-Plate manufactured by Mitsubishi Engineering-Plastics Corporation) was used.
3000), the amount of 1,3-dioxolan shown in Table 3, the polymerization time, the polyoxymethylene resin, and the polycarbonate resin were blended in the proportions shown in Table 3 while changing the amount of the polycarbonate resin. Performed similarly to Nos. 1-14. However, the resin composition was prepared by melt-kneading at a cylinder temperature of 220 ° C. using a vented twin-screw extruder to form pellets. The results are shown in Table 3.

Comparative Examples 14 to 22 The same procedures as in Examples 1 to 12 were carried out except that the amounts of 1,3-dioxolane, polymerization time, and the amounts of polyoxymethylene resin and polycarbonate resin shown in Table 3 were used. The results are shown in Table 3.

Examples 31 to 42 Instead of the styrene resin, a polyolefin resin was used, and the amounts of 1,3-dioxolan, polymerization time, and blending amounts of the polyoxymethylene resin and the polyolefin resin shown in Table 4 were obtained. Other than that, it carried out similarly to Examples 1-14.
The results are shown in Table 4.

Comparative Examples 23 to 31 The procedures were performed in the same manner as in Examples 31 to 42 except that the amounts of 1,3-dioxolane, the polymerization time, and the amounts of the polyoxymethylene resin and the polyolefin resin shown in Table 4 were changed. The results are shown in Table 4.

Examples 43 to 46 The same amount of 1,3-dioxolane, polymerization time, polyoxymethylene resin and polypropylene resin as in Example 32 or Example 38 were used by changing the amount of polypropylene resin in the proportions shown in Table 5. And carried out in the same manner as in Example 32 or Example 38. The results are shown in Table 5.

Comparative Examples 32 to 35 The same procedures as in Examples 43 to 46 were carried out except that the amount of 1,3-dioxolane and the polymerization time shown in Table 5 were used. Table 5 shows the results
It was shown to.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

[Table 3]

[0043]

[Table 4]

[0044]

[Table 5]

[0045]

The polyoxymethylene resin of the present invention is a molding resin composition containing at least one selected from a styrene resin, a polycarbonate resin and a polyolefin resin, and has particularly good dispersibility. The surface condition of the molded article is excellent, and it has characteristics such as dimensional stability, mechanical properties such as impact resistance, and excellent thermal stability.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) (C08L 59/04 C08L 23:00 69:00) (C08L 59/04 23:00) (72) Inventor Isamu Masumoto F-term (reference) 4J002 BB002 BB032 BB052 BB062 BB102 BB122 BB142 BB152 BB172 BB192 BC022 BC042 BC052 BC062 BC072 BP022 BC092 BP022 BP032 CB001 CG002 CG012 GM00 GN00 GQ00 4J032 AA05 AA34 AB06 AC32 AC42 AC43 AD37 AD41 AF08

Claims (6)

[Claims] Claims: 1. A method for copolymerizing trioxane and 1,3-dioxolane using a cationically active catalyst, comprising the steps of:
-Dioxolane to 7.1 to 11.
Polyoxymethylene resin 100 obtained using 0 mol% and having a crystallization time at 148 ° C. of 30 to 600 seconds.
A polyoxymethylene resin composition comprising 0 to 100 parts by weight of at least one selected from a styrene-based resin, a polycarbonate-based resin, and a polyolefin-based resin with respect to parts by weight. 2. The polyoxymethylene resin composition according to claim 1, wherein the polymerization time is 3 minutes or more. 3. The polyoxymethylene resin composition according to claim 1, wherein the cationic active catalyst is boron trifluoride or a coordination compound thereof. 4. The method according to claim 1, wherein the polymerization temperature is 60 to 120 ° C. until the polymerization yield reaches the boundary yield. 5. The polyoxymethylene resin composition according to claim 1, wherein the styrene resin is a copolymer resin of styrene and another copolymerizable vinyl monomer. 6. The styrene copolymer resin is a copolymer of styrene and at least one selected from acrylonitrile, butadiene, ethylene, acrylic acid or methacrylic acid and their alkyl esters, and derivatives thereof. The polyoxymethylene resin composition according to claim 5, wherein