WO2010035351A1 - Composition de résine polyacétal - Google Patents

Composition de résine polyacétal Download PDF

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Publication number
WO2010035351A1
WO2010035351A1 PCT/JP2008/068123 JP2008068123W WO2010035351A1 WO 2010035351 A1 WO2010035351 A1 WO 2010035351A1 JP 2008068123 W JP2008068123 W JP 2008068123W WO 2010035351 A1 WO2010035351 A1 WO 2010035351A1
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WO
WIPO (PCT)
Prior art keywords
polyacetal resin
weight
hydroxyl group
resin composition
compound
Prior art date
Application number
PCT/JP2008/068123
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English (en)
Japanese (ja)
Inventor
久保田豊
霜田暁英
川口邦明
Original Assignee
ポリプラスチックス株式会社
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Publication date
Application filed by ポリプラスチックス株式会社 filed Critical ポリプラスチックス株式会社
Priority to CN2008801308489A priority Critical patent/CN102131865A/zh
Priority to PCT/JP2008/068123 priority patent/WO2010035351A1/fr
Publication of WO2010035351A1 publication Critical patent/WO2010035351A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J159/00—Adhesives based on polyacetals; Adhesives based on derivatives of polyacetals

Definitions

  • the present invention relates to a polyacetal resin composition having excellent mechanical properties and hot water resistance.
  • An object of the present invention is to solve such problems and to provide a polyacetal resin composition capable of responding to higher mechanical properties and hot water resistance required in recent years with the expansion of the field of use of polyacetal resins.
  • the present inventors have intensively studied to obtain a reinforced polyacetal resin composition having excellent mechanical properties and hot water resistance.
  • the present invention relates to a polyacetal resin composition
  • a polyacetal resin composition comprising 100 parts by weight of a polyacetal resin component (A) and 3 to 200 parts by weight of a glass-based inorganic filler (B), and a boric acid compound (C) 0.001 to 1.0 part by weight is further blended, and the polyacetal resin component (A) is added to 99.9 to 80 parts by weight of a polyacetal resin (A1) having a hydroxyl group of 0 to 20 mmol / kg in the molecule, and 30 parts in the molecule.
  • the present invention relates to a polyacetal resin composition
  • a polyacetal resin composition comprising 0.1 to 20 parts by weight of a modified polyacetal resin (A2) having a hydroxyl group of ⁇ 2000 mmol / kg.
  • A2 modified polyacetal resin
  • the present invention relates to a polyacetal resin composition reinforced by blending a glass-based inorganic filler, and as a polyacetal resin component (A), a polyacetal resin (A1) having a hydroxyl group of 0 to 20 mmol / kg in the molecule, And a modified polyacetal resin (A2) having a hydroxyl group of 30 to 2000 mmol / kg in combination with a boric acid compound (C).
  • the polyacetal resin (A1) used in the present invention is a polymer compound having an oxymethylene group (—CH 2 O—) as a main constituent unit, and contains a small amount of other constituent units in addition to the polyoxymethylene homopolymer and the oxymethylene group. It may be a copolymer (including a block copolymer).
  • a homopolymer is a homopolymer of anhydrous formaldehyde or a general formula (CH 2 O) n [However, n is an integer of 3 or more] and is produced by polymerization of a cyclic oligomer of formaldehyde, particularly trioxane, which is a cyclic trimer of formaldehyde, and usually stable against thermal decomposition by the end cap of the polymer. It has become.
  • Copolymer about 85 to 99.9 mol% -CH 2 O-repeating group, the general formula: Wherein R 1 and R 2 are each selected from the group consisting of hydrogen, lower alkyl and halogen substituted lower alkyl groups, and R 3 is methylene, oxymethylene, lower alkyl and haloalkyl substituted methylene, and lower alkyl and haloalkyl. Selected from the group consisting of substituted oxymethylene groups, m is an integer of 0 to 3, and each lower alkyl group is of 1 to 2 carbon atoms).
  • a high molecular compound having a number average molecular weight of 5000 or more generally formaldehyde or a cyclic oligomer of formaldehyde represented by the general formula (CH 2 O) n (where n is an integer of 3 or more)
  • a compound selected from cyclic ether and cyclic formal by copolymerizing trioxane with a compound selected from cyclic ether and cyclic formal.
  • Decomposition removes the terminal unstable portion and stabilizes against thermal decomposition.
  • the cyclic ether compound and the cyclic formal compound mentioned here do not include a cyclic ether compound having a hydroxyl group, a cyclic formal compound having a hydroxyl group, and derivatives thereof.
  • cyclic ether compounds or cyclic formal compounds for copolymerization examples include ethylene oxide, 1,3-dioxolane, diethylene glycol formal, 1,4-butanediol formal, and the like.
  • a component for adjusting the molecular weight is used in combination to adjust the molecular weight of the resulting polymer.
  • a chain transfer agent that does not form an unstable terminal that is, an alkoxy group such as methylal, methoxymethylal, dimethoxymethylal, trimethoxymethylal, or oxymethylene di-n-butyl ether is used. 1 type or 2 types or more of the compound which has is illustrated.
  • hydroxyl groups are introduced into the molecules of the polyacetal resin by the action of moisture, methanol, etc. contained as impurities in the monomer components and comonomer components used in the reaction. Is done. Therefore, in order to set the amount of hydroxyl groups introduced into the molecule to 0 to 20 mmol / kg, the total amount of water and the total amount of methanol contained in the components (monomer component, comonomer component, etc.) used for polymerization are determined by polymerization. It is necessary for each component to be 30 ppm or less, preferably 20 ppm or less, and particularly preferably 15 ppm or less.
  • the polyacetal resin (A1) used in the present invention is a polyacetal (co) polymer prepared in this way and having a hydroxyl group introduced into the molecule of 0 to 20 mmol / kg.
  • the polyacetal resins produced in this category belong to this category.
  • Such a polyacetal resin (A1) used in the present invention is preferably a polyacetal copolymer, and among them, a copolymer obtained by copolymerizing trioxane and a compound selected from cyclic ether and cyclic formal having no hydroxyl group. preferable.
  • the modified polyacetal resin (A2) used in the present invention has a hydroxyl group of 30 to 2000 mmol / kg in the molecule, and preferably has a hydroxyl group of 50 to 500 mmol / kg.
  • the number average molecular weight of the modified polyacetal resin (A2) is from 1,000 to 100,000.
  • the quantitative determination of the hydroxyl group of the polyacetal resin can be performed, for example, by the method described in JP-A-2001-11143.
  • the modified polyacetal resin (A2) used in combination with the polyacetal resin (A1) is a modified polyacetal resin with a small amount of introduced hydroxyl groups
  • the glass-based inorganic filler which is the object of the present invention is blended.
  • the modified polyacetal resin (A2) having a hydroxyl group as described above can be produced by various methods. For example, in the presence of a compound having a hydroxyl group and acting as a chain transfer agent, a modified polyacetal having a hydroxyl group attached to the end of the polymer by a method of copolymerizing trioxane with a compound selected from cyclic ether and cyclic formal Resin (A2) can be obtained.
  • Examples of the compound having a hydroxyl group include polyhydric alcohols, compounds obtained by esterifying a part of hydroxyl groups of polyhydric alcohols, polyhydric alcohols or compounds obtained by adding alkylene oxide to esters thereof, water, and the like. .
  • the cyclic ether and cyclic formal those having no hydroxyl group are used.
  • a hydroxyl group is imparted to the side chain of the polymer by a method of copolymerizing trioxane, a compound selected from cyclic ether and cyclic formal having no hydroxyl group, and a polymerizable compound having a hydroxyl group.
  • Modified polyacetal resin (A2) can be obtained.
  • Examples of the polymerizable compound include a hydroxyl group-containing cyclic formal, a hydroxyl group-containing glycidyl ether, a hydroxyl group-containing oxetane, a hydroxyl group-containing styrene, and a hydroxyl group-containing vinyl compound.
  • the hydroxyl group of the polymerizable compound having a hydroxyl group is previously protected with an appropriate protecting group, for example, an acyl group such as formyl group, acetyl group or silyl group, and then subjected to polymerization. After the copolymerization, the hydroxyl group is protected.
  • the method of releasing to form a hydroxyl group is more preferable.
  • a basic compound in the case of an acyl group and with an acidic compound in the case of a silyl group a part or all of the acyl group or silyl group is decomposed to form a hydroxyl group.
  • a copolymer having a desired hydroxyl group is obtained.
  • the modified polyacetal resin (A2) having a hydroxyl group used in the present invention can be prepared by the method as described above.
  • the former method of introducing a hydroxyl group by utilizing chain transfer is preferable, but the latter method of introducing a hydroxyl group by copolymerization and, if necessary, post-treatment after copolymerization is preferable.
  • the polymerizable compound having a hydroxyl group used for modification a hydroxyl-containing cyclic formal is preferable, and glycerol formal is more preferable from the viewpoint of polymerization activity and introduction rate.
  • a method in which a hydroxyl group-containing cyclic formal is copolymerized using a compound protected by acylation or silylation and then post-treated to obtain a copolymer having a hydroxyl group is particularly preferable.
  • the cyclic formal having a protected hydroxyl group glycerol formal acetate is particularly preferred from the viewpoint of polymerization activity and hydroxyl group introduction rate.
  • the modified polyacetal resin (A2) used in the present invention can be used by removing the unstable portion present at the polymer terminal after polymerization by hydrolysis, or can be used directly without hydrolysis treatment. is there.
  • the hydroxyl protecting group introduced in the pretreatment of the polymerization is After the copolymer is prepared by polymerization, it must be treated with a basic compound and deprotected.
  • a basic compound for deprotecting the protecting group of the hydroxyl group amines such as ammonia, trimethylamine, triethylamine, tributylamine, or alkali metal or alkaline earth metal hydroxide salts are used.
  • the modified polyacetal resin (A2) is less than 0.1% by weight or more than 20% by weight, any improvement in mechanical properties is insufficient.
  • the degree of modification of the modified polyacetal resin (A2) (hydroxyl introduction rate) and the amount of hydroxyl groups of the polyacetal resin (A1) are used. It is preferable to adjust the ratio of A1 / A2. That is, when the modified polyacetal resin (A2) having a low hydroxyl group introduction rate is used, it is appropriate to increase the mixing ratio, and when using the modified polyacetal resin (A2) having a high hydroxyl group introduction ratio, it is appropriate to reduce the mixing ratio. . When the amount of hydroxyl groups in the polyacetal resin (A1) is small, the mixing ratio of the modified polyacetal resin (A2) is increased.
  • the polyacetal resin component (A) contains a small amount of a polyacetal resin (A3) having a branched or crosslinked structure, thereby further improving mechanical properties and hot water resistance. It will be excellent.
  • the proportion of the polyacetal resin (A3) is preferably 0.01 to 3 parts by weight per 100 parts by weight of the polyacetal resin component (A).
  • the polyacetal resin (A3) having such a branched or cross-linked structure is a monofunctional glycidyl ether compound having a substituent such as an alkyl group or an aryl group, or butanediol diglycidyl ether in the production of the polyacetal resin (A1) described above. It can manufacture by adding polyfunctional glycidyl ether and polymerizing.
  • the glass-based inorganic filler (B) used in the present invention fibrous (glass fiber), granular (glass bead), powder (milled glass fiber), plate (glass flake) and hollow ( There are no particular restrictions on the particle size, fiber length, etc., and any known material can be used.
  • these fillers can be used in combination according to the purpose.
  • these glass-based inorganic fillers can be used even if they are untreated, but inorganic fillers that have been surface-treated with a surface treatment agent such as a silane-based or titanate-based coupling agent can be used. It is preferable to use it.
  • a surface treatment agent such as a silane-based or titanate-based coupling agent
  • the silane coupling agent include vinyl alkoxy silane, epoxy alkoxy silane, amino alkoxy silane, mercapto alkoxy silane, and allyl alkoxy silane.
  • vinylalkoxysilane examples include vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris ( ⁇ -methoxyethoxy) silane, and the like.
  • epoxyalkoxysilane examples include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, and the like.
  • aminoalkoxysilane examples include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropyltrimethoxysilane, and N-phenyl- ⁇ -aminopropyltrimethoxy. Silane etc. are mentioned.
  • mercaptoalkoxysilanes include ⁇ -mercaptopropyltrimethoxysilane and ⁇ -mercaptopropyltriethoxysilane.
  • allylalkoxysilane examples include ⁇ -diallylaminopropyltrimethoxysilane, ⁇ -allylaminopropyltrimethoxysilane, ⁇ -allylthiopropyltrimethoxysilane, and the like.
  • titanate-based surface treatment agents include titanium-i-propoxyoctylene glycolate, tetra-n-butoxy titanium, tetrakis (2-ethylhexoxy) titanium, and the like.
  • the amount of the surface treatment agent used is 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, particularly preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the inorganic filler.
  • the glass-based inorganic filler (B) is a glass fiber
  • those using a polymer binder, an adhesion promoter, other auxiliaries, etc. as a sizing agent are preferably used.
  • the polymer binder generally known materials such as organic materials such as water-dispersible / water-soluble polyvinyl acetate, polyester, epoxide, polyurethane, polyacrylate or polyolefin resin, and mixtures thereof are preferably used.
  • the compounding amount of the glass-based inorganic filler (B) is 3 to 200 parts by weight, preferably 5 to 150 parts by weight, particularly preferably 10 to 100 parts by weight, based on 100 parts by weight of the polyacetal resin component (A). Part.
  • examples of the boric acid compound (C) used in the present invention include orthoboric acid, metaboric acid, tetraboric acid, and diboron trioxide, and commercially available products can be used.
  • the compounding amount of the boric acid compound (C) is 0.001 to 1.0 part by weight with respect to 100 parts by weight of the polyacetal resin component (A).
  • the boric acid compound (C) used in the present invention acts synergistically with the structure of the polyacetal resin component (A) described above, particularly the modified polyacetal resin (A2) having a hydroxyl group of 30 to 2000 mmol / kg in the molecule. It improves the adhesion between the polyacetal resin and the glass-based inorganic filler (B), and enables excellent mechanical strength and hot water resistance. If the amount of the boric acid compound (C) is less than 0.001 part by weight, the desired effect cannot be obtained, and if it exceeds 1.0 part by weight, thermal stability becomes a problem.
  • the amount is preferably 0.005 to 0.5 parts by weight, particularly preferably 0.01 to 0.2 parts by weight, based on 100 parts by weight of the polyacetal resin component (A).
  • the polyacetal resin composition of the present invention may further contain various known stabilizers / additives.
  • a stabilizer any one or two of a hindered phenol compound, a nitrogen-containing compound such as melamine, guanamine, hydrazide, urea, an alkali or alkaline earth metal hydroxide, an inorganic salt, a carboxylate, etc. The above can be mentioned.
  • the additive used in the present invention is a general additive for thermoplastic resins, for example, any of coloring agents such as dyes and pigments, lubricants, nucleating agents, release agents, antistatic agents, and surfactants. 1 type or 2 or more types can be mentioned.
  • it is a fiber, plate, powder, etc. of known inorganic, organic, and metal other than glass-based inorganic fillers. It is also possible to mix one or more fillers such as these in combination. Examples of such fillers include talc, mica, wollastonite, carbon fiber and the like, but are not limited thereto.
  • the method for preparing the composition of the present invention is not particularly limited, and it can be easily prepared by a known facility and method generally used as a conventional resin composition preparation method. For example, i) a method in which each component is mixed and then kneaded and extruded by an extruder to prepare pellets, and then molded, ii) pellets having different compositions are once prepared, and the pellets are mixed in a predetermined amount for molding. Any method can be used, such as a method of obtaining a molded product having a desired composition after molding, or a method of directly charging one or more of each component into a molding machine. Further, mixing a part of the resin component as a fine powder with other components and adding it is a preferable method for uniformly blending these components.
  • the resin composition according to the present invention can be molded by any of extrusion molding, injection molding, compression molding, vacuum molding, blow molding, and foam molding.
  • the resulting polymer was deactivated by introducing it into an aqueous solution containing 0.05% by weight of triethylamine, and further separated, washed and dried to obtain a crude polyacetal resin. Subsequently, 3 parts by weight of a 5% by weight aqueous solution of triethylamine, 0.15 part by weight of melamine, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl) with respect to 100 parts by weight of the obtained crude polyacetal resin.
  • the obtained polyacetal resin was a copolymer having a melt index (MI) of 27.0 g / 10 min, a number average molecular weight of 41000, and a hydroxyl group content of 5 mmol / kg.
  • the obtained polyacetal resin was a copolymer having a melt index (MI) of 9.0 g / 10 min, a number average molecular weight of 58,000, and a hydroxyl group content of 5 mmol / kg.
  • MI melt index
  • A2-1 Modified Polyacetal Resin
  • boron trifluoride (BF 3 ) 20 ppm (based on the total monomers) was added as a reaction initiation catalyst for polymerization.
  • the resulting polymer was deactivated by introducing it into an aqueous solution containing 0.05% by weight of triethylamine, and further separated, washed and dried to obtain a crude polyacetal resin.
  • 100 parts by weight of the obtained crude polyacetal resin and 2000 parts by weight of a 5% by weight triethylamine solution were put into a reaction kettle and heat-treated at 150 ° C. for 1 hour and at 170 ° C. for 0.5 hour, thereby causing unstable parts. And the protected hydroxyl group was deacetylated.
  • the triethylamine solution was prepared so that the volume ratio of methanol and water was 8: 1. Further, the heat-treated solution was cooled to 20 ° C. to obtain a powdery polyacetal resin.
  • the obtained modified polyacetal resin had a number average molecular weight of 34500 and a hydroxyl group of 100 mmol / kg.
  • Examples 1-4, Comparative Examples 1-2 A polyacetal resin (A1-1), a modified polyacetal resin (A2-1 or A2-2 or A2-3), a glass fiber (B-1), and a boric acid compound are blended in the proportions shown in Table 1, and the cylinder temperature is 200.
  • a pellet-shaped composition was prepared by melt-kneading with an extruder at 0 ° C. Next, a test piece was molded from the pellet-shaped composition using an injection molding machine, and physical properties were evaluated by the evaluation methods shown below. The results are shown in Table 1. On the other hand, for comparison, a pellet-like composition was prepared in the same manner even when the modified polyacetal (A2) was not added or when the boric acid compound was not added, and physical properties were evaluated.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention porte sur une composition de résine polyacétal, contenant une charge inorganique en verre, qui présente une adhérence améliorée entre la charge inorganique en verre et une résine polyacétal, ce qui permet d'obtenir de cette manière d'excellentes caractéristiques en termes de résistance mécanique et de résistance à l'eau chaude. De façon précise, l'invention porte sur une composition de résine polyacétal qui est obtenue par mélange de 3 à 200 parties en poids d'une charge inorganique en verre (B) dans 100 parties en poids d'une résine de polyacétal (A). Dans cette composition de résine polyacétal, de 0,001 à 1,0 partie en poids d'un composé de l'acide borique (C) est en outre mélangé. Le composant résine polyacétal (A) est composé de 99,9 à 80 parties en poids d'une résine polyacétal (A1) qui présente de 0 à 20 mmol/kg de groupes hydroxy dans une molécule et de 0,1 à 20 parties en poids d'une résine polyacétal modifiée (A2) qui présente de 30 à 2 000 mmol/kg de groupes hydroxyles dans une molécule.
PCT/JP2008/068123 2008-09-29 2008-09-29 Composition de résine polyacétal WO2010035351A1 (fr)

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CN2008801308489A CN102131865A (zh) 2008-09-29 2008-09-29 聚缩醛树脂组合物
PCT/JP2008/068123 WO2010035351A1 (fr) 2008-09-29 2008-09-29 Composition de résine polyacétal

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PCT/JP2008/068123 WO2010035351A1 (fr) 2008-09-29 2008-09-29 Composition de résine polyacétal

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2441786A1 (fr) * 2010-10-14 2012-04-18 Ticona GmbH Polyoxyméthylène renforcé par fibre de verre
WO2012049293A1 (fr) * 2010-10-14 2012-04-19 Ticona Gmbh Polyoxyméthylène renforcé par fibre de verre couplée
US8865805B2 (en) 2011-10-14 2014-10-21 Ticona Gmbh Tribologically modified glass-fiber reinforced polyoxymethylene
US9062183B2 (en) 2012-12-20 2015-06-23 Ticona Gmbh Fiber reinforced polyoxymethylene composition with improved thermal properties
US9540553B2 (en) 2012-04-17 2017-01-10 Ticona Gmbh Weather resistant polyoxymethylene compositions
WO2017169120A1 (fr) * 2016-03-31 2017-10-05 ポリプラスチックス株式会社 Composition de résine polyacétal
US10196577B2 (en) 2015-09-30 2019-02-05 Celanese Sales Germany Gmbh Low friction squeak free assembly
US11015031B2 (en) 2017-06-16 2021-05-25 Celanese Sales Germany Gmbh Reinforced polyoxymethylene composition with low emissions

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017169438A1 (fr) * 2016-03-31 2017-10-05 ポリプラスチックス株式会社 Composition de résine de polyacétal
JP7222678B2 (ja) * 2018-11-28 2023-02-15 ポリプラスチックス株式会社 ポリアセタール樹脂組成物およびポリアセタール樹脂組成物の製造方法

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9303145B2 (en) 2010-10-14 2016-04-05 Ticona Gmbh Coupled glass-fiber reinforced polyoxymethylene
WO2012049293A1 (fr) * 2010-10-14 2012-04-19 Ticona Gmbh Polyoxyméthylène renforcé par fibre de verre couplée
CN103228692A (zh) * 2010-10-14 2013-07-31 提克纳有限公司 偶联玻璃纤维增强的聚甲醛
US8829085B2 (en) 2010-10-14 2014-09-09 Ticona Gmbh Glass fiber-reinforced polyoxymethylene
US10731027B2 (en) 2010-10-14 2020-08-04 Celanese Sales Germany Gmbh Coupled glass-fiber reinforced polyoxymethylene
EP2441786A1 (fr) * 2010-10-14 2012-04-18 Ticona GmbH Polyoxyméthylène renforcé par fibre de verre
US8865805B2 (en) 2011-10-14 2014-10-21 Ticona Gmbh Tribologically modified glass-fiber reinforced polyoxymethylene
US9540553B2 (en) 2012-04-17 2017-01-10 Ticona Gmbh Weather resistant polyoxymethylene compositions
US9062183B2 (en) 2012-12-20 2015-06-23 Ticona Gmbh Fiber reinforced polyoxymethylene composition with improved thermal properties
US10196577B2 (en) 2015-09-30 2019-02-05 Celanese Sales Germany Gmbh Low friction squeak free assembly
JP2017179265A (ja) * 2016-03-31 2017-10-05 ポリプラスチックス株式会社 ポリアセタール樹脂組成物
WO2017169120A1 (fr) * 2016-03-31 2017-10-05 ポリプラスチックス株式会社 Composition de résine polyacétal
US11142637B2 (en) 2016-03-31 2021-10-12 Polyplastics Co., Ltd. Polyacetal resin composition
US11015031B2 (en) 2017-06-16 2021-05-25 Celanese Sales Germany Gmbh Reinforced polyoxymethylene composition with low emissions

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