JPH11116695A - Manufacturing method of molded products - Google Patents

Abstract

(57) [Abstract] [PROBLEMS] To improve the quality of molded products by plasticizing and stabilizing the measurement during the molding of crystalline thermoplastic resin, and to increase the crystallization speed of the resin, improve mold release, and mold. To shorten the cycle. SOLUTION: On a particle surface of a crystalline thermoplastic resin (A), for example, a polyarylene sulfide resin or a thermoplastic polyester resin, a specific organic phosphate metal salt (B) having a metal of Group II of the periodic table on a particle surface; For example, a method for producing a molded article in which a powder of a zinc salt of octadecyl phosphate is adhered and then molded by injection molding or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a molded article by molding such as injection molding. More specifically, after the specific organic phosphate metal salt is uniformly attached to the surface of the crystalline thermoplastic resin particles and then molded, the plasticization measurement during molding is remarkably stabilized, and the quality of the molded article is improved. Improve the dispersion, and significantly increase the crystallinity of the crystalline thermoplastic resin, improve the releasability, shorten the molding time, and further improve the surface finish of the molded product. And a method for producing a molded article having a high hardness.

[0002] The production method of the present invention significantly improves the moldability of a crystalline thermoplastic resin and can be used in a wide range of molding fields such as electric and electronic parts, automobile parts, machine parts and industrial parts. Things.

[0003]

2. Description of the Related Art In recent years, demands for molded articles, especially injection molded articles, have tended to be complicated, precise, and miniaturized. For example, in injection molding, the plasticization measurement process becomes unstable due to poor biting of resin. However, this causes short shots and uneven filling, which causes problems such as a decrease in strength of the molded product and deterioration of the surface appearance. In addition, as molds become more complicated, problems such as deterioration of releasability at the time of molding and a prolonged molding cycle are caused.

[0004] Under such circumstances, methods for solving this problem include a release agent, a lubricant, a crystal nucleating agent (nucleating agent).
It is generally known to employ an addition method such as an internal addition method of uniformly dispersing the inside of the molten thermoplastic resin inside, and an external addition method of uniformly adhering around the thermoplastic resin.
Examples of the release agent and lubricant used herein include olefin waxes such as polyethylene wax and polypropylene wax; higher fatty acid esters such as butyl stearate, monoglyceride stearate, sorbitan stearate, and montanic aliphatic dihydric alcohol ester, and the like. Aliphatic ester waxes such as partially saponified products; bisamide-based lubricants such as ethylene bisamide; metal soaps such as sodium stearate and calcium stearate are mainly used. As the nucleating agent, talc, ceramic powder, kaolin, clay, zeolite and other inorganic substances, alkali metals, alkaline earth metals, organic compounds containing metals such as aluminum, alkali metals, alkaline earth metals are contained. Organic phosphate metal salts and the like are mainly used.

[0005] In particular, polyarylene sulfide resin, which is a crystalline thermoplastic resin having excellent heat resistance and chemical resistance, requires a long molding cycle time due to a low crystallization rate, and a serious problem is that the productivity is low. It has become. As a method for solving this problem, a method similar to the above method, for example, a method of adding an inorganic crystal nucleating agent such as kaolin, zeolite or talc (JP-A-63-245463, JP-A-6-245463).
No. 57137), a method of adding a specific phosphoric acid ester (Japanese Patent Application Laid-Open No. 62-230850, Japanese Patent Application Laid-Open No.
JP-A-225660, JP-A-3-91563, etc .; alkylmercaptans and inorganic nucleating agents
140451), low molecular weight phenylene thioether (JP-A-5-5061), polyalkylene glycol (JP-A-3-250049), metal salts of aliphatic carboxylic acids having 22 or more carbon atoms (JP-A-5-501). 78
575), a specific alkali metal salt of an organic phosphoric acid or an organic metal salt of an organic phosphonic acid (JP-A-2-14285).
Numerous proposals have been made, for example, a method of adding the compound of JP-A No.

[0006] Similarly, the addition of a release agent, a lubricant, and a nucleating agent to a thermoplastic polyester resin, which is also a crystalline thermoplastic resin, is known. Particularly, among thermoplastic polyesters, polyethylene terephthalate has a high crystallization rate. It is extremely slow and it is essential to improve the formability.

[0007]

However, in the above-mentioned prior art, the crystallization speed is not sufficiently improved, and the releasability and the molding cycle are hardly reduced. Insufficient stabilization of weighing and unstable quality. In addition, engineering plastics such as polyarylene sulfide resin and thermoplastic polyester resin, which are crystalline thermoplastic resins, have high molding processing temperatures, and in the above-mentioned conventional technology, most of them have extremely poor heat resistance, and are decomposed during molding. There is a problem that gas is generated, which adversely affects the moldability. In addition, in recent years, while the cost reduction has been intensely progressing, the cost reduction by inexpensive raw materials is approaching its limit, and the plasticization and stable measurement of the quality at the time of molding (improvement of the yield), There is an increasing demand for shortening the molding cycle (reducing the molding cost) by improving the crystallization speed, and these improvements are indispensable issues.

[0008] The problem to be solved by the present invention is a serious drawback at the time of molding a crystalline thermoplastic resin represented by a polyarylene sulfide resin or a thermoplastic polyester resin. Improvement of product quality,
Another object is to increase the crystallization speed of the resin, improve the releasability, and shorten the molding cycle.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies to solve these conventional disadvantages and found that a specific organic phosphate metal salt having a metal belonging to Group II of the periodic table can be converted into a crystalline thermoplastic phosphate. When adhered to the surface of the resin particles and supplied to a molding machine having an extruder such as an injection molding machine, an extrusion molding machine, a hollow molding machine or the like and molded, the plasticization and measurement during molding are remarkably stabilized, and It has been found that the crystal characteristics can be improved, and the present invention has been completed.

That is, according to the present invention, (1) an organic phosphate metal salt (B) represented by the following general formula (I) and / or (II) is adhered to the particle surface of the crystalline thermoplastic resin (A). After the method, a method for manufacturing a molded article characterized by being molded,

[0011]

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(In the formula, R ₁ and R ₂ are the same or different hydrocarbon groups, and M is a metal atom of Group II of the periodic table.)

(2) The method according to the above (1), wherein 0.001 to 2.000 parts by weight of the organic phosphoric acid ester metal salt (B) is adhered to 100 parts by weight of the particles of the crystalline thermoplastic resin (A). ,

(3) The production method according to the above (1) or (2), wherein R ₁ and R _{2 in the} general formulas (I) and (II) are the same or different aliphatic hydrocarbon groups.

(4) M in the general formulas (I) and (II)
Is the one or more metals selected from the group consisting of magnesium, calcium and zinc,

(5) The method according to (1), (2), (3) or (4), wherein the crystalline thermoplastic resin (A) is a polyarylene sulfide resin or a thermoplastic polyester resin. ,as well as,

(6) The production method according to any one of (1) to (5), wherein the production method is performed by injection molding.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION As the crystalline thermoplastic resin (A) used in the present invention, a thermoplastic resin having a distinct peak of heat of fusion when subjected to thermal analysis by a differential thermal analysis method can be mentioned. , Specifically, polybutylene terephthalate,
Thermoplastic polyester resins such as polyethylene terephthalate and aromatic polyester liquid crystalline resin; thermoplastic polyamides such as nylon 6 and nylon 66; polyarylene sulfide resins such as polyoxymethylene and polyphenylene sulfide; high density polyethylene; syndiotactic polypropylene; Tactic polypropylene, syndiotactic polystyrene and the like are preferable, and polyarylene sulfide resin, thermoplastic polyester resin, thermoplastic polyamide and the like are preferable. Among them,
Polyarylene sulfide resins and thermoplastic polyester resins are particularly preferred.

Among the above-mentioned crystalline thermoplastic resins (A), polyarylene sulfide resins include, for example, those represented by the general formula [A
r-S] (wherein, Ar represents a divalent aromatic group containing at least one carbon 6-membered ring), and a polymer containing 70 mol% or more of a repeating unit. Examples thereof include polyphenylene sulfide resins containing a repeating unit represented by the structural formula [Ph-S] (wherein Ph represents a phenyl group) in an amount of 70 mol% or more.

The polyarylene sulfide resin is generally known to have a substantially linear molecular structure having no branched or crosslinked structure and a structure having a branched or crosslinked structure according to the present invention. Is effective for both types.

The preferred polyarylene sulfide resin for use in the present invention includes a repeating unit of 70 mol%
Polymers containing the above and having a melt viscosity of 1 to 10 ⁶ poise at 316 ° C. and a shear rate of 100 sec ^-1 are exemplified.

Further, the polyarylene sulfide resin used in the present invention may contain less than 30 mol% of other copolymerized structural units. As a typical example, in the case of polyphenylene sulfide resin, the copolymer which may be contained therein As the structural unit, for example, a metaphenylene sulfide unit, a diphenyl ketone sulfide unit, a diphenyl sulfone sulfide unit, a diphenyl ether sulfide unit, 2,
6-naphthalene sulfide unit, trifunctional unit and the like.

The thermoplastic polyester resin of the crystalline thermoplastic resin (A) used in the present invention includes, for example, terephthalic acid or esters thereof, ethylene glycol, propylene glycol, butanediol, pentanediol, neopentyl glycol, Hexanediol, octanediol, decanediol, cyclohexanedimethanol, hydroquinone, bisphenol A, 2,2-bis (4-hydroxyethoxyphenyl)
And terephthalic acid-based thermoplastic polyesters obtained from glycols such as propane, 1,4-dimethyloltetrabromobenzene, and ethylene oxide adduct of tetrabromobisphenol A.

The thermoplastic polyester resin includes:
For example, polyethylene terephthalate, polybutylene terephthalate, polynaphthalene terephthalate and the like can be mentioned. These are usually mechanical strength, fluidity when molten,
Since the surface gloss and the like are good, the intrinsic viscosity [η] measured at 30 ° C. in a mixed solvent of phenol and ethane tetrachloride at a weight ratio of 6: 4 is in the range of 0.3 to 1.5 dl / g. Use something.

Further, as the thermoplastic polyester resin, polyesters mainly containing p-hydroxybenzoic acid, polyesters mainly containing aromatic hydroxycarboxylic acids such as 6-hydroxy-2-naphthoic acid, terephthalic acid and hydroquinone , Polyester comprising p-hydroxybenzoic acid and a polyethylene terephthalate component, polyester comprising p-hydroxybenzoic acid and an aromatic diol such as 4,4-dihydroxybiphenyl, p-hydroxybenzoate Acids, aromatic diols, and polyesters containing aromatic dicarboxylic acids such as 3,3-diphenyldicarboxylic acid as main components, and polyester copolymers containing two or more components selected from the above components That can form an anisotropic molten phase such as A ester-based liquid crystalline resin is exemplified. In these polyester-based liquid crystal resins, isophthalic acid, m-hydroxybenzoic acid, 4,4-dicarboxydiphenyl ether, 2,6-dihydroxynaphthalene, 6-hydroxy-2-naphthoic acid, 4,4 -Dihydroxybiphenyl, 2-phenylhydroquinone, 2,2-bis (4-
In addition to aromatic components such as hydroxyphenyl) propane, 4,4-hydroxydiphenylsulfone, 2,2-bis (4-β-hydroxyethoxyphenyl) propane and bis (4-β-hydroxyethoxyphenyl) sulfone, malonic acid Succinic acid, spearic acid, adipic acid, azelaic acid, sebacic acid, dodecandioic acid, tetradecandioic acid, eicosantioic acid, trimethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol , Triethylene glycol, aliphatic components such as polyethylene glycol,
It may contain an alicyclic component such as 1,4-cyclohexanedicarboxylic acid or 1,4-cyclohexanedimethanol as a suitable copolymerization component.

The production method and the shape of the particles of the crystalline thermoplastic resin (A) used in the present invention are not limited. For example, fillers and additives may be added to the crystalline thermoplastic resin (A) if necessary. Additives, coloring agents, other resins, etc., and shaped into pellets, beads, granules, etc., and pulverized ones.

The organic phosphate metal salt (B) used in the present invention is an organic phosphate metal salt represented by the following general formula (I) or (II).

[0028]

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R ₁ and R ₂ in the formula are the same or different hydrocarbon groups and include, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,
Octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, peptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl,
Docosyl, tricosyl, tetracosyl, triacontyl, tetracontyl, pentacontyl, hexacontyl, vinyl, propenyl, allyl, butenyl, pentenyl, ethynyl, cyclopropyl, cyclopentyl, cyclohexyl And aliphatic hydrocarbon groups including alicyclic hydrocarbon groups such as cyclohexenyl group; phenyl group, diphenyl group, tolyl group, xylyl group, mesityl group, camenyl group, benzyl group, phenethyl group, methylbenzyl group, diphenylmethyl Group, a triphenylmethyl group, a styryl group, a cinnamyl group, an aromatic hydrocarbon group such as a biphenylyl group, a naphthyl group, an antilyl group, and a phenanthryl group. Among them, an aliphatic hydrocarbon group is preferable because of easy dispersion. .

M in the formula is a metal atom belonging to Group II of the periodic table, of which Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium) and Zn (zinc) are preferred. Especially Mg, Ca, Zn
Is preferred.

Specific examples of the organophosphate metal salt (B) include those represented by R in the general formula (I) or (II).
Is an aliphatic hydrocarbon group, all of which are represented by the above general formula (I) or (II), Mg phosphate, Mg salt, Ca salt, Sr salt of methyl phosphate,
Ba salt, Zn salt, Mg salt of phosphoric acid ethyl ester, Ca
Salt, Sr salt, Ba salt, Zn salt, Mg salt of propyl phosphate, Ca salt, Sr salt, Ba salt, Zn salt, Mg salt of isopropyl phosphate, Ca salt, Sr salt, Ba
Salt, Zn salt,

Mg salt and Ca salt of butyl phosphate,
Sr salt, Ba salt, Zn salt, Mg salt of isobutyl phosphate, Ca salt, Sr salt, Ba salt, Zn salt, phosphoric acid se
Mg salt, Ca salt, Sr salt, Ba of c-butyl ester
Salt, Zn salt, Mg of phosphoric acid tert-butyl ester
Salt, Ca salt, Sr salt, Ba salt, Zn salt, Mg salt of pentyl phosphate, Ca salt, Sr salt, Ba salt, Zn salt,
Mg salt, Ca salt, Sr of isopentyl phosphate
M of salt, Ba salt, Zn salt, neopentyl phosphate
g salt, Ca salt, Sr salt, Ba salt, Zn salt, Mg salt of hexyl phosphate, Ca salt, Sr salt, Ba salt, Zn
Salt, Mg salt of heptyl phosphate ester, Ca salt, Sr
Salt, Ba salt, Zn salt, Mg of octyl phosphate
Salt, Ca salt, Sr salt, Ba salt, Zn salt,

Mg salt, Ca salt of nonyl phosphate,
Sr salt, Ba salt, Zn salt, Mg of decyl phosphate
Salt, Ca salt, Sr salt, Ba salt, Zn salt, Mg salt of undecyl phosphate, Ca salt, Sr salt, Ba salt, Zn
Salt, dodecyl phosphate Mg salt, Ca salt, Sr salt,
Ba salt, Zn salt, Mg salt of tridecyl phosphate,
Ca salt, Sr salt, Ba salt, Zn salt, Mg salt of tetradecyl phosphate, Ca salt, Sr salt, Ba salt, Zn salt,
Mg salt, Ca salt, Sr of pentadecyl phosphate
M of salt, Ba salt, Zn salt, hexadecyl phosphate
g salt, Ca salt, Sr salt, Ba salt, Zn salt, Mg salt of peptadecyl phosphate, Ca salt, Sr salt, Ba salt, Z
n salt, Mg salt of octadecyl phosphate, Ca salt,
Sr salt, Ba salt, Zn salt,

Mg salt of nonadecyl phosphate, Ca
Salt, Sr salt, Ba salt, Zn salt, Mg salt of eicosyl phosphate, Ca salt, Sr salt, Ba salt, Zn salt, Mg salt of hen eicosyl phosphate, Ca salt, Sr salt, B
a salt, Zn salt, Mg salt of docosyl ester phosphate, Ca
Salt, Sr salt, Ba salt, Zn salt, Mg salt of tricosyl phosphate, Ca salt, Sr salt, Ba salt, Zn salt, Mg salt of tetracosyl phosphate, Ca salt, Sr salt, Ba
Salt, Zn salt, Mg salt of triacontyl phosphate,
Ca salt, Sr salt, Ba salt, Zn salt, Mg salt of tetracontyl phosphate, Ca salt, Sr salt, Ba salt, Zn
Salt, pentacontyl phosphate, Mg salt, Ca salt,
Sr salt, Ba salt, Zn salt, Mg salt of hexacontyl phosphate, Ca salt, Sr salt, Ba salt, Zn salt,

Mg and Ca salts of vinyl phosphate,
Sr salt, Ba salt, Zn salt, Mg salt of 1-propenyl phosphate, Ca salt, Sr salt, Ba salt, Zn salt, Mg salt of allyl phosphate, Ca salt, Sr salt, Ba salt, Z
n-salt, Mg salt of isopropenyl phosphate, Ca
Salt, Sr salt, Ba salt, Zn salt, Mg salt of 1-butenyl phosphate, Ca salt, Sr salt, Ba salt, Zn salt, Mg salt of 2-butenyl phosphate, Ca salt, Sr salt , B
a salt, Zn salt, Mg of 2-pentenyl phosphate
Salt, Ca salt, Sr salt, Ba salt, Zn salt,

Mg salt of ethynyl phosphate, Ca
Salt, Sr salt, Ba salt, Zn salt, Mg salt of cyclopropyl phosphate, Ca salt, Sr salt, Ba salt, Zn salt, Mg salt of cyclopentyl phosphate, Ca salt, Sr
Salt, Ba salt, Zn salt, Mg salt of cyclohexyl phosphate, Ca salt, Sr salt, Ba salt, Zn salt, phosphoric acid 1-
Mg salt, Ca salt, Sr salt of cyclohexenyl ester,
Ba salt, Zn salt and the like;

In the metal salt of an organic phosphoric ester wherein R in the general formula (I) or (II) is an aromatic hydrocarbon group,
In each case, Mg salt, Ca salt, Sr salt, Ba salt of phosphoric acid phenyl ester represented by the above general formula (I) or (II)
Salt, Zn salt, Mg salt of phosphoric acid diphenyl ester, Ca
Salt, Sr salt, Ba salt, Zn salt, Mg salt of o-tolyl phosphate phosphate, Ca salt, Sr salt, Ba salt, Zn salt, Mg salt of m-tolyl phosphate phosphate, Ca salt, Sr salt, Ba
Salt, Zn salt, Mg salt of phosphoric acid p-tolyl ester, Ca
Salt, Sr salt, Ba salt, Zn salt, Mg salt of 2,4-xylyl phosphate, Ca salt, Sr salt, Ba salt, Zn salt,
Mg salt of phosphoric acid 2,4,6-mesityl ester, Ca
Salt, Sr salt, Ba salt, Zn salt,

Mg salt of o-camenyl phosphate, C
a salt, Sr salt, Ba salt, Zn salt, Mg salt of m-camenyl phosphate, Ca salt, Sr salt, Ba salt, Zn salt, Mg salt of p-camenyl phosphate, Ca salt, Sr salt,
Ba salt, Zn salt, Mg salt of benzyl phosphate, C
a salt, Sr salt, Ba salt, Zn salt, Mg salt of phenethyl phosphate, Ca salt, Sr salt, Ba salt, Zn salt, Mg salt of α-methylbenzyl phosphate, Ca salt, Sr
Salt, Ba salt, Zn salt, Mg salt of phosphoric acid diphenylmethyl ester, Ca salt, Sr salt, Ba salt, Zn salt, Mg salt of phosphoric acid triphenylmethyl ester, Ca salt, Sr salt,
Ba salt, Zn salt,

Mg salt of styryl phosphate, Ca
Salt, Sr salt, Ba salt, Zn salt, Mg salt of cinnamyl phosphate, Ca salt, Sr salt, Ba salt, Zn salt, Mg salt of 2-biphenylyl phosphate, Ca salt, Sr salt,
Ba salt, Zn salt, M of phosphoric acid 3-biphenylyl ester
g salt, Ca salt, Sr salt, Ba salt, Zn salt, Mg salt of 4-biphenylyl phosphate, Ca salt, Sr salt, Ba
Salt, Zn salt, Mg salt of 1-naphthyl phosphate, C
a salt, Sr salt, Ba salt, Zn salt, Mg salt of 2-naphthyl phosphate, Ca salt, Sr salt, Ba salt, Zn salt, Mg salt of 1-anthryl phosphate, Ca salt, Sr
Salt, Ba salt, Zn salt, Mg salt of 2-anthryl phosphate, Ca salt, Sr salt, Ba salt, Zn salt, phosphoric acid 9-
Mg salt, Ca salt, Sr salt, Ba of antilyl ester
Salt, Zn salt, Mg salt of phenanthryl phosphate phosphate,
Examples thereof include Ca salts, Sr salts, Ba salts, and Zn salts. In addition, other than the above, metal salts of organic phosphoric acid esters having another metal of Group II of the periodic table as the metal can also be mentioned.

Among the above-mentioned organophosphate metal salts (B), particularly preferred are Mg salts, Ca salts, and Zn salts of ethyl phosphate represented by the above general formula (I) or (II). M of salt and butyl phosphate
g salt, Ca salt, Zn salt, Mg salt of octadecyl phosphate,
Ca salt, Zn salt, tetracosyl phosphate Mg
Salt, Ca salt, Zn salt, Mg salt of triacontyl phosphate, Ca salt, Zn salt, Mg salt of pentacontyl phosphate, Ca salt, Zn salt and the like.

The organic phosphoric acid ester metal salt (B) can be used alone or in combination of two or more. Also, various release agents and lubricants can be mixed. The amount added is 100 parts by weight of particles of the crystalline thermoplastic resin (A) [including components other than the crystalline thermoplastic resin (A) such as fillers, additives, coloring agents, and other resins. ), The crystallization rate is high and the mechanical strength is hardly reduced, so that the crystalline thermoplastic organic phosphoric acid ester metal salt (B) is 0.001 to 2.00.
It is preferably in a range of 0 parts by weight, especially 0.001 to
A range of 1.0001 parts by weight is particularly preferred.

The method of attaching the metal organic phosphate (B) to the surface of the particles of the crystalline thermoplastic resin (A) used in the present invention is as follows. The powder, liquid, solution or emulsion of the metal salt (B) is converted into a crystalline thermoplastic resin composition (A).
, A method of mixing uniformly using a tumbler, various mixers and other devices, a method of continuously mixing with a quantitative addition device, and a method of mixing the strand of the melt of the crystalline thermoplastic resin (A) with the above organic phosphoric acid A method of immersing in a liquid, solution or emulsion of the ester metal salt (B) for a certain period of time and then granulating is generally used, but the method is not limited as long as it can be uniformly attached to the surface. It does not do. As the organic phosphoric acid ester metal salt (B) used here, a powder having a bulk density of 0.8 g / cm ³ or less is preferable.
Among them, a powder of 0.05 to 0.3 g / cm ³ is particularly preferable.

The crystalline thermoplastic resin (A) used in the present invention
Various kinds of inorganic and organic fillers can be added to the particles of the above-mentioned one or two or more kinds in combination depending on the purpose.
Specifically, silica, diatomaceous earth, dolomite, γ-alumina, alumina other than γ, titanium oxide, iron oxide, zinc oxide, magnesium oxide, antimonic acid, antimony oxide, barium ferrite, strontium ferrite,
Oxides such as beryllium oxide, pumice, pumice balloon, lead oxide, bismuth oxide, and zirconium oxide; zinc hydroxide,
Hydroxides such as aluminum hydroxide, magnesium hydroxide and basic magnesium carbonate; carbonates such as lithium carbonate, calcium carbonate, magnesium carbonate and dawsonite; sulfates or sulfites such as calcium sulfate, barium sulfate, ammonium sulfate and calcium sulfite Talc, clay, mica, asbestos, glass fiber, glass balloon, glass beads, silicates such as calcium silicate, montmorillonite, bentonite, and hydrotalcites; other carbon black, graphite, molybdenum sulfide, boron fiber, silicon carbide Fiber, potassium titanate, titanic acid, lead zirconate, zinc borate, barium metaborate, calcium borate, sodium borate, and other inorganic filler particles, fibers, whiskers, spheres, and hollows; Good Family polyamide fibers, polytetrafluoroethylene, and an organic filler such as silicone rubber. The preferable addition amount of the filler is 0.1 to 80% by weight in the composition of the present invention.

Further, other particles can be added to the particles of the crystalline thermoplastic resin (A) as long as the object of the present invention is not impaired. As the other resin, for example, polyphenylene ether, modified polyphenylene ethers such as styrene graft, polyarylate, polyamide,
Polybutylene terephthalate, polyethylene terephthalate, poly 1.4-cyclohexane dimethylene terephthalate, polycarbonate, various liquid crystal polymers, polysulfone, polyether sulfone, polyallyl sulfide, polyallyl sulfone, polyether ketone, polyether ether Ketone, polyethylene, polypropylene, polymethylpentene, polystyrene, hydrogenated styrene butadiene rubber, ethylene propylene rubber, polyisoprene, polyisobutylene, polybutene, phenoxy resin, epoxy resin, polyimide, polyamideimide, urea resin, phenol resin, diallyl phthalate resin ,
A thermoplastic or thermosetting resin such as a silicone resin may be used.

Further, the particles of the crystalline thermoplastic resin (A) may be added to other known additives, for example, a surface treating agent such as a silane, titanate, zirconate, zircoaluminate, aluminum chelate compound-based coupling agent, or bromo. Flame retardants such as halogenated epoxy resins, brominated polycarbonates, brominated polystyrenes, etc., phosphorus-based flame retardants,
Antimony trioxide, antimony tetroxide, antimony pentoxide and other antimony compounds, flame retardant aids, antioxidants, heat stabilizers, corrosion prevention of alkali metal or alkaline earth metal oxides, hydroxides or carbonates Agents, various release agents, lubricants, coloring agents, crystal nucleating agents other than the present invention, glass fibers, fibrous reinforcing materials such as carbon fibers, mica, talc, inorganic fillers such as calcium carbonate, etc. to the composition of the present invention. Can be added as needed.

The molding method used in the present invention may be any method in which the particles of the crystalline thermoplastic resin (A) are continuously melted and then molded. For example, injection molding, extrusion molding, and hollow molding may be used. Molding and the like. Among them, injection molding methods such as a screw in-line method and a plunger method are preferable, and particularly, the injection molding method of a screw in-line method is particularly preferable since the plasticized state is likely to be uniform. Further, it is particularly preferable that auxiliary equipment is installed for automation of a take-out robot, a belt conveyor, a blower, a take-out confirmation sensor and the like.

The kneading temperature condition and the injection molding temperature condition are, for example, 280 to 3 in the case of polyarylene sulfide resin.
The range of 70 ° C. is appropriate, but particularly preferably 280 to 330 ° C., and in the case of a thermoplastic polyester resin, 230 ° C.
The temperature range is suitably from 300 to 360 ° C, particularly preferably from 300 to 360 ° C for liquid crystalline polyester resins and from 230 to 270 ° C for other polyester resins. The temperature of the mold at the time of injection molding of the polyarylene sulfide resin is preferably in the range of 50 to 200 ° C.

[0048]

The present invention will be further described with reference to examples and comparative examples. Note that the present invention is not limited to only the embodiments. Parts in the examples are parts by weight.

Examples 1 to 5 and Comparative Examples 1 to 5 The melt viscosity at 316 ° C. and a shear rate of 100 sec ^-1 was 40.
0 poise linear polyphenylene sulfide resin, glass fiber (Asahi Fiberglass, 10 μm in diameter)
After uniformly mixing with the composition shown in Table 1 (part 1) to (part 3), the mixture was melt-kneaded with a twin-screw extruder set at a barrel temperature of 300 ° C., and the extruded strand was cooled, solidified, and then cut. A pellet was obtained. The obtained pellets are mixed with the following organic phosphate metal salts 1, 2, 3, 4, sodium stearate, polyethylene wax (PE Hoechst Chemical Co., Ltd., PE
-190) at room temperature at a ratio shown in Tables 1 (1) to (Part 3) using a tumbler.

The organic phosphoric acid ester metal salts 1, 2, 3, and 4 used here are the following compounds (the same applies hereinafter). Organophosphate metal salt 1 = Compound represented by the following structural formula (1) Bulk density 0.6 g / cm ³ Organophosphate metal salt 2 = Compound represented by the following structural formula (2) Bulk density 0.3 g / cm ³ organophosphate metal salt 3 = compound represented by the following structural formula (3) Bulk density 0.2 g / cm ³ organophosphate metal salt 4 = compound represented by the following structural formulas (4) and (5) Equimolar mixture of bulk density 0.2 g / cm ³

[0051]

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The pellets were subjected to a 1.6 mm thick AST using a screw in-line injection molding machine with a molding pressure of 50 t.
Created M4 dumbbell. At this time, the plasticizing weighing time for each shot was recorded. The injection molding conditions were as follows: molding temperature: 300 ° C., mold temperature: 150 ° C., injection speed: medium speed, injection pressure: primary pressure / secondary pressure = 140/50 (kg /
cm ² ), molding cycle: injection / cooling = 7/20 (second)
It is. The tensile strength was measured using this dumbbell.
The less the plasticization measurement time and the tensile strength change due to the shot, the more stable the moldability. The temperature of the center of the dumbbell was raised from room temperature to 350 ° C. at a rate of 20 ° C./min from a room temperature with a DSC (differential operation calorimeter, DSC7 manufactured by Perkin Elmer) and held at 350 ° C. for 3 minutes.
After cooling at a rate of −20 ° C./min, a peak temperature of an exothermic peak of crystallization was measured as a crystallization temperature. It is generally said that the higher the crystallization temperature, the faster the crystallization. The results are shown in Tables 1 (1) to (3).

[0053]

[Table 1]

[0054]

[Table 2]

[0055]

[Table 3]

As is clear from the results of Tables 1 (part 1) to (part 3), in the molding method of the present invention, the crystallization temperature is high and the crystallization is remarkably fast. Also, the change in tensile strength and weighing time for each shot is extremely small and stable.

Examples 6 to 11 and Comparative Examples 6 to 11 Polybutylene terephthalate resin having an intrinsic viscosity [η] of 0.9 dl / g, a brominated epoxy resin (Platherm EP200 manufactured by Dainippon Ink and Chemicals, Inc.), trioxide Antimony (manufactured by Suzuhiro Chemical Co., average particle diameter 0.75 μm, antimony trioxide content: 99.75%), and glass fiber (manufactured by Denki Glass Fiber Co., Ltd., diameter: 13 μm) are shown in Tables 2 (1) to (3). And then melt-kneaded at 250 ° C. with a single screw extruder to obtain pellets. The obtained pellets were treated with organic phosphate metal salts 1, 2, 3, 4, sodium stearate, and ester wax ("Hoechst Wax EP" manufactured by Hoechst Chemical Co., Ltd.) in Table 2 (part 1) to
Using a tumbler at room temperature at the ratio shown in (Part 3), the particles were uniformly attached to the surface.

The pellets were screwed with a molding pressure of 50 t.
-ASTM 1.6mm thick with in-line injection molding machine
Created No. 4 dumbbell. At this time, plasticity for each shot
The chemical weighing time was recorded. The injection molding conditions are as follows: molding temperature:
250 ° C, mold temperature: 80 ° C, injection speed: medium speed, injection
Outlet pressure: primary pressure / secondary pressure = 140/50 (kg / c
m ^Two), Molding cycle: injection / cooling = 7/20 (second)
is there. The tensile strength was measured using this dumbbell. Ma
The center of the dumbbell was connected to a DSC (differential operation calorimeter,
Perkin Elmer DSC7), from room temperature to 20 ° C /
The temperature is raised to 250 ° C at the speed of min, and 250 ° C for 3 minutes
After holding, cooling at a rate of -20 ° C / min.
The exothermic peak temperature of crystallization is measured as the crystallization temperature.
Was. The results are shown in Tables 2 (1) to (3).

[0059]

[Table 4]

[0060]

[Table 5]

[0061]

[Table 6]

As is clear from the results of Tables 2 (1) to (3), in the molding method of the present invention, the crystallization temperature is high and the crystallization is remarkably fast. Also, the change in tensile strength and weighing time for each shot is extremely small and stable.

Examples 12 to 16 and Comparative Examples 12 to 16 Liquid crystalline polyester resin (Econol manufactured by Sumitomo Chemical Co., Ltd.)
E-6000) and glass fibers (13 μm in diameter, manufactured by Denki Glass Fiber Co., Ltd.) were uniformly mixed with the composition shown in Tables 3 (1) to (3), and then mixed at 340 ° C. using a twin-screw extruder. The mixture was melt-kneaded to obtain pellets. The organic pellet metal salts 1, 2, 3, 4, sodium stearate, and ester wax ("Hoechst Wax EP" manufactured by Hoechst Chemical Co., Ltd.) are added to the obtained pellets in proportions shown in Tables 3 (1) to (3). At room temperature using a tumbler to uniformly adhere to the surface.

The pellets were subjected to a 1.6 mm thick ASTM using a screw in-line injection molding machine with a molding pressure of 50 t.
Created No. 4 dumbbell. At this time, the plasticizing weighing time for each shot was recorded. The injection molding conditions are as follows: molding temperature:
330 ° C, mold temperature: 120 ° C, injection speed: medium speed,
Injection pressure: primary pressure / secondary pressure = 140/50 (kg / cm
² ), molding cycle: injection / cooling = 7/20 (sec). The tensile strength was measured using this dumbbell. The results are shown in Tables 3 (1) to (3).

[0065]

[Table 7]

[0066]

[Table 8]

[0067]

[Table 9]

As is apparent from the results of Tables 3 (1) to (3), the molding method of the present invention is stable with extremely little change in tensile strength and weighing time for each shot.

[0069]

According to the method for producing a molded article of the present invention, plasticization and metering are extremely stable, quality is excellent, and crystallization is remarkably fast as compared with conventional molding of a crystalline thermoplastic resin. Since the molding cycle is shortened, it is suitable for molding various functional parts and the like, particularly for injection.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 101/12 C08L 101/12

Claims (6)

[Claims] An organic phosphoric acid ester metal salt (B) represented by the following general formula (I) and / or (II) is adhered to the particle surface of a crystalline thermoplastic resin (A), and then molded. A method for producing a molded article characterized by the following. Embedded image (In the formula, R ₁ and R ₂ are the same or different hydrocarbon groups, and M is a metal atom of Group II of the periodic table.) 2. Particles 100 of the crystalline thermoplastic resin (A)
The organic phosphoric acid ester metal salt (B) was added in an amount of 0.0
2. The production method according to claim 1, wherein the amount is from 0.01 to 2.000 parts by weight. 3. R ₁ and R in the general formulas (I) and (II)
_{3. The} method according to claim 1, wherein ₂ is the same or different aliphatic hydrocarbon group. 4. The method according to claim 3, wherein M in the general formulas (I) and (II) is one or more metals selected from the group consisting of magnesium, calcium and zinc. 5. The method according to claim 1, wherein the crystalline thermoplastic resin (A) is a polyarylene sulfide resin or a thermoplastic polyester resin. 6. The production method according to claim 1, wherein the molding is performed by injection molding.