JP2005264101A - Polyacetal resin - Google Patents

Polyacetal resin Download PDF

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Publication number
JP2005264101A
JP2005264101A JP2004082304A JP2004082304A JP2005264101A JP 2005264101 A JP2005264101 A JP 2005264101A JP 2004082304 A JP2004082304 A JP 2004082304A JP 2004082304 A JP2004082304 A JP 2004082304A JP 2005264101 A JP2005264101 A JP 2005264101A
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polyacetal resin
weight
ppm
heated
formaldehyde
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JP2005264101A5 (en
Inventor
Yukiyoshi Sasaki
Noritaka Tanimura
幸義 佐々木
徳孝 谷村
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Asahi Kasei Chemicals Corp
旭化成ケミカルズ株式会社
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Abstract

<P>PROBLEM TO BE SOLVED: To improve high-temperature resistant creep characteristics at a high level without substantially deteriorating molding processing characteristics of a polyacetal resin at all. <P>SOLUTION: The polyacetal resin has 10-100 wt.ppm of the total amount of volatile organic compounds except formaldehyde released when heated at 90&deg;C for 30 min. The polyacetal resin comprises a sterically hindered phenol as an antioxidant, a compound and/or a polymer containing a formaldehyde-reactive nitrogen as a heat stabilizer and a formic acid scavenger. <P>COPYRIGHT: (C)2005,JPO&amp;NCIPI

Description

  The present invention relates to a polyacetal resin or molded article having a high improvement in high-temperature creep resistance without substantially impairing the molding processing characteristics of the polyacetal resin.

  Polyacetal resin has well-balanced mechanical properties and is excellent in fatigue resistance, creep resistance, and frictional wear resistance, so it is used in a wide range of applications such as automobiles, electrical and electronic equipment, and building materials. ing. However, as the use of polyacetal resin expands, the demand for quality is becoming increasingly sophisticated. One of the required properties is to improve molding processability such as fluidity, mold release and mold deposit resistance without deteriorating mechanical properties and creep resistance. As a method for improving the fluidity and releasability of polyacetal resins, it is common practice to add lubricants and mold release agents typified by aliphatic alcohol esters and polyalkylene glycols to polyacetal resins. Yes.

It has also been proposed to balance fluidity and thermal stability by containing a specific polyacetal oligomer and fluorine. (For example, refer to Patent Document 1) However, mold deposit resistance, which is another important element of moldability, is often sacrificed in exchange for improvement in fluidity and mold release. Furthermore, there arises a problem that the mechanical properties are lowered and the creep resistance is greatly lowered. As a method for improving the creep resistance, it is generally possible to increase the molecular weight of the polyacetal resin, but the moldability is greatly reduced in exchange for the improvement of the creep resistance.
Japanese Patent No. 3108791

  An object of the present invention is to highly improve the high temperature creep resistance without substantially impairing the molding characteristics of the polyacetal resin.

As a result of intensive studies to solve the above problems, the present inventors have made a polyacetal resin in which the total amount of volatile organic compounds excluding formaldehyde released when heated at 90 ° C. for 30 minutes is 10 to 100 ppm by weight. The inventors have found that the object can be achieved by using powder, pellets, or a molded body, and have reached the present invention based on this finding.
That is, the present invention
1. A polyacetal resin, wherein the total amount of volatile organic compounds excluding formaldehyde released when heated at 90 ° C. for 30 minutes is 10 to 100 ppm by weight,
2. The polyacetal resin according to 1 above, wherein the amount of formaldehyde released when heated at 60 ° C. for 3 hours is 10 ppm by weight or less,
3. The polyacetal resin contains at least one sterically hindered phenol as an antioxidant, at least one compound and / or polymer containing formaldehyde-reactive nitrogen as a heat stabilizer, and at least one formic acid scavenger. The polyacetal resin according to the above 1 or 2, characterized in that
4). 4. The polyacetal resin according to 3 above, wherein the formic acid scavenger is an alkaline earth metal carboxylate,
5). The polyacetal resin according to any one of the above 1 to 4, wherein the polyacetal resin is a polyoxymethylene copolymer,
6). A molded body obtained from the polyacetal resin according to any one of 1 to 5,
7). A molded product characterized in that the total amount of volatile organic compounds excluding formaldehyde released when the molded product is heated at 90 ° C. for 30 minutes is 10 to 100 ppm by weight;
8). The molded product according to 6 or 7 above, wherein the molded product is an automobile part,
About.

  The polyacetal resin powder, pellets, and molded product of the present invention have a high improvement in high temperature creep resistance without substantially deteriorating the molding processing characteristics of the polyacetal resin. Therefore, it is suitable for automobile-related parts in which these performances are particularly required, particularly fuel-related parts such as a fuel tank flange, and seat-belt-related parts such as a seat belt retracting mechanism.

Hereinafter, the present invention will be specifically described.
The polyacetal resin of the present invention is a polyoxygen comprising substantially repeating oxymethylene units produced using a formaldehyde monomer or a cyclic oligomer such as a trimer (trioxane) or tetramer (tetraoxane) as a raw material. Oxyalkylene units having 2 to 8 carbon atoms produced from methylene homopolymer or the above raw materials and cyclic ethers such as ethylene oxide, propylene oxide, epichlorohydrin, 1,3-dioxolane, glycol formal, diglycol formal, etc. 0.1 to 20% by weight, preferably 0.2 to 10% by weight oxymethylene copolymer, further having a cross-linked or branched molecular chain, oxymethylene unit, oxyethylene unit, oxypropylene unit, methylene unit, propylene Units, etc. The polyoxymethylene block copolymer etc. which have a repeating unit different from a ximethylene unit are included. Moreover, the mixture of various polyacetal resin mentioned above may be sufficient.

The polyacetal resin of the present invention may be in the form of powder or pellet. In the present invention, the total amount of volatile organic compounds excluding formaldehyde released when the polyacetal resin of these shapes is heated at 90 ° C. for 30 minutes is 10 to 100 ppm by weight, preferably 15 to 50 ppm with respect to the polyacetal resin. It is essential that the weight is ppm. The total amount of released volatile organic compounds can be determined by GC (Gas Chromatography) -MS (Mass Spectrometer) analysis (separated by gas chromatography and then quantified with toluene as a standard substance by a mass spectrometer). When the total amount of volatile organic compounds is less than 10 ppm by weight, fluidity and mold release properties are lowered. When the total amount is more than 100 ppm by weight, mold deposit resistance is deteriorated and high temperature creep resistance is lowered. In the present invention, it is preferable from the viewpoint of improving mold deposit resistance that the amount of formaldehyde released when heated at 60 ° C. for 30 minutes is 10 ppm by weight or less with respect to the polyacetal resin. The amount of formaldehyde released can be determined by absorbing the formaldehyde released from the polyacetal resin in water in a sealed container and quantitatively analyzing it by the acetylacetone method.
Moreover, the molded object obtained from the polyacetal resin of this invention also has the effect of this invention. That is, in the molded article of the present invention, the total amount of volatile organic compounds excluding formaldehyde released when heated at 90 ° C. for 30 minutes is 10 to 100 ppm by weight with respect to the molded article obtained from the polyacetal resin.

  As the antioxidant, hindered phenol antioxidants are preferable. For example, n-octadecyl-3- (3′5′-di-t-butyl-4′-hydroxyphenyl) -propionate, n-octadecyl-3- (3′-methyl-5′-t-butyl-4′- Hydroxyphenyl) -propionate, n-tetradecyl-3- (3'5'-di-t-hydroxyphenyl) -propionate, 1,6-hexanediol-bis- (3- (3,5-di-t-butyl) -4-hydroxyphenyl) -propionate, 1,4-butanediol-bis- (3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, triethylene glycol-bis- (3- ( 3-t-butyl-5-methyl-4-hydroxyphenyl) -propionate).

Tetrakis- (methylene-3- (3′5′-di-t-butyl-4′-hydroxyphenyl) -propionate methane, 3,9-bis (2- (3- (3-t-butyl) -4-hydroxy-5-methylphenyl) propionyloxy) 1,1-dimethylethyl) 2,4,8,10-tetraoxaspiro (5,5 ') undecane, N, N'-bis-3- (3 '5'-di-t-butyl-4-hydroxyphenol) priionyl hexamethylenediamine, N, N'-tetramethylenebis-3- (3'-methyl-5'-t-butyl-4-hydroxy Phenol) pripionyldiamine, N, N′-bis-3- (3 ′, 5′-di-t-butyl-4-hydroxyphenol) prepionyl) hydrazine, N-salicyloyl-N′-salicylidenehydrazine, 3- (N-salicyloyl) amine-1,2,4-triazole, N, N′-bis- (2- (3- (3,5-di-butyl-4-hydroxyphenyl) propionyloxy) ethyl) oxyamide Etc.

  Among these hindered phenolic antioxidants, triethylene glycol-bis- (3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) -propionate), tetrakis- (methylene-3- ( 3'5'-di-t-butyl-4'-hydroxyphenyl) -propionate methane is preferred. These antioxidants are 0.01-3 parts by weight, preferably 100 parts by weight of polyacetal resin. It is used in the range of 0.05 to 2 parts by weight, more preferably 0.1 to 1 part by weight.

  Thermal stabilizers include compounds and polymers containing formaldehyde-reactive nitrogen such as dicyanamide, melamine, melamine and formaldehyde compounds, polyamide resins (eg, nylon 46, 6, 66, 610, 612, 12 66-6, 66-66-10, 66-12, etc.), poly-β-alanine, polyacrylamide, urea derivatives such as urea and hydantoin, allantoin, acid imides such as succinimide, hydrazide compounds and the like. Among these, a cocondensate of melamine and formaldehyde, a polyamide resin, poly-β-alanine, and polyacrylamide are preferable, and a polyamide resin and poly-β-alanine are more preferable. These are 0.001-5 weight part with respect to 100 weight part of polyacetal resin, Preferably it is 0.005-3 weight part, More preferably, it is 0.01-2 weight part.

  Examples of formic acid supplements include alkali metal or alkaline earth metal hydroxides, inorganic acid salts and carboxylate salts, such as hydroxides such as sodium, potassium, magnesium, calcium or barium, and carbonic acid of the above metals. Examples include salts, phosphates, silicates, and borates. Specifically, calcium salts are most preferred, and are calcium hydroxide, calcium carbonate, calcium phosphate, calcium silicate, calcium borate, and fatty acid calcium (calcium stearate, calcium myristate, etc.), and these fatty acids are substituted with hydroxyl groups. It may be. Of these, fatty acid calcium salts (calcium stearate, calcium myristate) are preferred. These alkali metal or alkaline earth metal hydroxides, inorganic acid salts and carboxylates are used in an amount of 0.01 to 3 parts by weight, preferably 0.03 to 1 part by weight, more preferably 100 parts by weight of the polyacetal resin. Is 0.03 to 0.5 parts by weight.

The composition of the present invention includes known heat stabilizers, antioxidants, formic acid scavengers, weathering (light) stabilizers, and crystals of lubricants, talc, boron nitride, etc., as long as the effects of the present invention are not impaired. Nucleating agents, pigments, reinforcing materials, conductive materials, thermoplastic resins, thermoplastic elastomers and the like can be added.
A polyoxymethylene copolymer that is preferable as the polyacetal resin of the present invention is described in, for example, Japanese Patent Application Laid-Open No. 2001-81281. Hereinafter, the polyacetal resin powder or pellet of the present invention is exemplified by using a polyoxymethylene copolymer as an example. Or the method of obtaining a molded object is demonstrated. In order to obtain a polyoxymethylene copolymer for practical use, first, typically, a trioxane and a cyclic ether such as 1,3-dioxolane or a cyclic formal are converted into a Lewis acid such as boron trifluoride di-n-butyl ether. And a protic acid such as trifluoromethanesulfonic acid as a catalyst.

  The polymerization method is not particularly limited, but bulk polymerization can be given as a representative example. As the polymerization apparatus, a self-cleaning reactor such as a kneader is generally used. In the bulk polymerization, the monomer in a molten state changes to a solid bulk as the polymerization proceeds, and this is pulverized by a kneader to obtain a powdery polymer. Next, the polymer obtained by copolymerization is brought into contact with a triethylamine aqueous solution or the like to neutralize and deactivate the polymerization catalyst, and is washed and dried as necessary. Thereafter, the thermally unstable terminal portion present in the polymer is removed by melt hydrolysis with an extruder or the like in the presence of a basic compound such as triethylamine or a quaternary ammonium salt, and an antioxidant as necessary. And put to practical use after adding heat stabilizers.

Components detected when the polyacetal resin thus obtained is heated at 90 ° C. for 30 minutes include residual monomers such as trioxane and 1,3-dioxolane, reaction intermediates such as tetraoxane and trioxepane, Examples thereof include linear or cyclic low molecular weight formaldehyde polymers and amine compounds having an average molecular weight of 500 or less, mainly 300 or less. In particular, since amine compounds are likely to cause malodor, they are preferably 50 ppm or less, more preferably 20 ppm or less, relative to the polyacetal resin.
As a method of making these components 10 to 100 ppm by weight of the present invention, a method of reducing the residual monomers by making the polymerization yield close to 100%, a method of washing or drying the polymer obtained by the polymerization , A method of devolatilization and removal from a vent during melt hydrolysis or additive kneading using an extruder with a vent, etc., a method of drying or washing the obtained pellets or powder obtained by pulverizing them, injection Examples thereof include a method of heating or washing a molded product obtained by molding, gas injection molding, extrusion molding, compression molding, or the like, and a combination of these methods.

  In the present invention, the method for reducing the volatile organic compound is not particularly limited, and any method may be selected. When the polyacetal resin powder, pellet, or molded product to be used is heated at 90 ° C. for 30 minutes. The volatile organic compound excluding formaldehyde released into the substrate may be 10 to 100 ppm by weight. More specifically, the amount of volatile organic compounds when heated at 90 ° C. for 30 minutes under various conditions such as washing and drying temperature and time, melting temperature, number of times of melting and devolatilization, and vent pressure is measured and complicated. The optimum conditions that fall within the scope of the present invention are selected from various combination conditions.

The present invention will be described based on examples and comparative examples.
First, the evaluation methods used in Examples and Comparative Examples are shown below.
(1) Fluidity (SF = Spiral Flow Distance: mm)
Using a Nestal injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., molding was performed using a spiral mold having a cylinder temperature of 200 ° C., an injection pressure of 100 MPa, an injection speed of 30%, a mold temperature of 80 ° C., a thickness of 1 mm, and a width of 6 mm. F. D (filled length: mm) is measured. S. F. The longer D, the better the fluidity.

(2) Release force (N)
Using a SH-75 injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., cylinder temperature 200 ° C., injection pressure 30 MPa, injection speed 30%, injection time 25 seconds, cooling time 15 seconds, mold temperature 95 ° C., height 50 mm A bottomed cylindrical molded body having an outer diameter of 50 mm and a thickness of 2 mm is continuously molded, and the resistance force applied to the projecting pin when the molded body is ejected from the mold and released from the mold is measured with a load cell. The measured resistance force was averaged from the 10th shot to the 20th shot after the start of molding to obtain a release force.

(3) Mold deposit resistance Using a Ti-30G injection molding machine manufactured by Toyo Machine Metal Co., Ltd., cylinder temperature 200 ° C., injection pressure 50 MPa, injection speed 50%, injection time 10 seconds, cooling time 5 seconds, mold temperature A molded product of 35 mm × 14 mm × 2 mm was continuously molded at 30 ° C., and after 2000 shots, the state of the mold deposit adhering to the mold was observed with the naked eye and evaluated according to the following criteria.
○: Almost no mold deposit is observed Δ: Mold deposit is slightly recognized

(4) High temperature creep resistance (destruction time)
Using an IS-80A injection molding machine manufactured by Toshiba Corporation, cylinder temperature 200 ° C., injection pressure 50 MPa, injection speed 30%, injection time 15 seconds, cooling time 25 seconds, mold temperature 70 ° C., dimensions 110 mm × 6. A 5 mm × 3 mm strip-shaped test piece was prepared, and a tensile stress of 20 MPa was applied to the test piece and left in air at 80 ° C., and the time until the test piece was broken was measured. The longer the time until destruction, the better the creep resistance.

(5) Total amount of volatile organic compounds excluding formaldehyde released when heated at 90 ° C. for 30 minutes (weight ppm)
Several tens mg of polyacetal resin is heated in a sealed container at 90 ° C. for 30 minutes, and then the gas in the container is introduced into GC (Gas Chromatography) -MS (Mass Spectrometer), and each detected component is quantified using toluene as a standard substance. And the sum was calculated | required about components other than formaldehyde. The lower limit of detection was 1 ppm by weight.
(6) Amount of formaldehyde released when heated at 60 ° C. for 3 hours (weight ppm)
About 20 g of polyacetal resin was suspended in a sealed container filled with 50 g of water so as not to be immersed in water, heated at 60 ° C. for 3 hours to absorb the released formaldehyde, and this water was analyzed by the acetylacetone method.

[Examples 1-3, Comparative Examples 1-2]
First, 0.1% by weight of nylon 6-6 as a heat stabilizer and ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate as an antioxidant] Obtained by copolymerization of 0.045 mol of 1,3-dioxolane as a comonomer with respect to 1 mol of trioxane, with 0.3 wt% of 0.1 wt% of calcium distearate as a formic acid scavenger. = 9.8 g / 10 min polyacetal copolymer pellets were obtained. The amount of formaldehyde released when heated at 60 ° C. for 3 hours and the total amount of volatile organic compounds excluding formaldehyde released when heated at 90 ° C. for 30 minutes were 15 ppm by weight and 120 wt. ppm. (Comparative Example 1) This polyoxymethylene copolymer was melted and devolatilized as many times as necessary with a twin-screw extruder equipped with a vacuum vent to obtain the polyacetal resin pellets of the present invention. The pellets were dried at 80 ° C. for 3 hours and then used for each evaluation. The evaluation results are summarized in Table 1.

  The polyacetal resin of the present invention is used for parts that require good molding characteristics and creep resistance, especially automobile-related parts, especially fuel-related parts such as fuel tank flanges, and seatbelt winding mechanisms. Suitable for parts.

Claims (8)

  1. A polyacetal resin, wherein the total amount of volatile organic compounds excluding formaldehyde released when heated at 90 ° C. for 30 minutes is 10 to 100 ppm by weight.
  2. The polyacetal resin according to claim 1, wherein the amount of formaldehyde released when heated at 60 ° C for 3 hours is 10 ppm by weight or less.
  3. The polyacetal resin contains at least one sterically hindered phenol as an antioxidant, at least one compound and / or polymer containing formaldehyde-reactive nitrogen as a heat stabilizer, and at least one formic acid scavenger. The polyacetal resin according to claim 1 or 2, wherein the polyacetal resin is used.
  4. 4. The polyacetal resin according to claim 3, wherein the formic acid scavenger is an alkaline earth metal carboxylate.
  5. The polyacetal resin according to any one of claims 1 to 4, wherein the polyacetal resin is a polyoxymethylene copolymer.
  6. The molded object obtained from the polyacetal resin in any one of Claims 1-5.
  7. A molded article, wherein the total amount of volatile organic compounds excluding formaldehyde released when the molded article is heated at 90 ° C for 30 minutes is 10 to 100 ppm by weight.
  8. The molded body according to claim 6 or 7, wherein the molded body is an automobile part.
JP2004082304A 2004-03-22 2004-03-22 Polyacetal resin Pending JP2005264101A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007112959A (en) * 2005-10-24 2007-05-10 Polyplastics Co Agent for decomposing and treating unstable terminal group, stabilized polyacetal resin using the same, production method, composition and molded article
CN105585813A (en) * 2014-11-06 2016-05-18 旭化成化学株式会社 Polyacetal resin particle and molded body

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62119219A (en) * 1985-11-12 1987-05-30 Celanese Corp Removal of voltile component of molten oxymethylene polymer
JPH0649155A (en) * 1992-07-28 1994-02-22 Toray Ind Inc Production of oxymethylene copolymer
JPH07207118A (en) * 1994-01-12 1995-08-08 Polyplastics Co Polyoxymethylene composition
WO1995025761A1 (en) * 1994-03-22 1995-09-28 Asahi Kasei Kogyo Kabushiki Kaisha Method of stabilizing molecular ends of oxymethylene copolymer
JPH07324155A (en) * 1994-04-07 1995-12-12 Asahi Chem Ind Co Ltd Polyacetal resin composition
JP2001081281A (en) * 1999-09-13 2001-03-27 Asahi Kasei Corp Polyacetal resin composition and molded product therefrom
WO2005044917A1 (en) * 2003-11-07 2005-05-19 Polyplastics Co., Ltd. Polyacetal resin composition and molded article thereof
JP2005264102A (en) * 2004-03-22 2005-09-29 Asahi Kasei Chemicals Corp Polyacetal resin

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62119219A (en) * 1985-11-12 1987-05-30 Celanese Corp Removal of voltile component of molten oxymethylene polymer
JPH0649155A (en) * 1992-07-28 1994-02-22 Toray Ind Inc Production of oxymethylene copolymer
JPH07207118A (en) * 1994-01-12 1995-08-08 Polyplastics Co Polyoxymethylene composition
WO1995025761A1 (en) * 1994-03-22 1995-09-28 Asahi Kasei Kogyo Kabushiki Kaisha Method of stabilizing molecular ends of oxymethylene copolymer
JPH07324155A (en) * 1994-04-07 1995-12-12 Asahi Chem Ind Co Ltd Polyacetal resin composition
JP2001081281A (en) * 1999-09-13 2001-03-27 Asahi Kasei Corp Polyacetal resin composition and molded product therefrom
WO2005044917A1 (en) * 2003-11-07 2005-05-19 Polyplastics Co., Ltd. Polyacetal resin composition and molded article thereof
JP2005264102A (en) * 2004-03-22 2005-09-29 Asahi Kasei Chemicals Corp Polyacetal resin

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007112959A (en) * 2005-10-24 2007-05-10 Polyplastics Co Agent for decomposing and treating unstable terminal group, stabilized polyacetal resin using the same, production method, composition and molded article
CN105585813A (en) * 2014-11-06 2016-05-18 旭化成化学株式会社 Polyacetal resin particle and molded body

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