WO2020110641A1 - Polyacetal resin composition and method for producing polyacetal resin composition - Google Patents
Polyacetal resin composition and method for producing polyacetal resin composition Download PDFInfo
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- WO2020110641A1 WO2020110641A1 PCT/JP2019/043493 JP2019043493W WO2020110641A1 WO 2020110641 A1 WO2020110641 A1 WO 2020110641A1 JP 2019043493 W JP2019043493 W JP 2019043493W WO 2020110641 A1 WO2020110641 A1 WO 2020110641A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
- C08G2/18—Copolymerisation of aldehydes or ketones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
- C08L59/02—Polyacetals containing polyoxymethylene sequences only
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
- C08L59/04—Copolyoxymethylenes
Definitions
- the present invention relates to a polyacetal resin composition having excellent mechanical properties and a method for producing the polyacetal resin composition.
- Polyacetal resin has excellent properties in mechanical properties, thermal properties, electrical properties, slidability, moldability, etc., and is mainly used as electrical materials, automobile parts, precision machinery as structural materials and mechanical parts. Widely used for parts and so on. However, with the expansion of fields in which polyacetal resins are used, required properties tend to become more sophisticated, complex, and specialized. As such required properties, further improvement is required for improving rigidity and suppressing generation of formaldehyde while maintaining the excellent slidability, appearance, etc. originally possessed by the polyacetal resin.
- the rigidity is improved without substantially impairing the slidability and the appearance, but in the method of reducing the comonomer, the toughness decreases.
- the thermal stability of the polymer is also deteriorated and other problems occur, and it is not always possible to meet the demand.
- Patent Document 1 Attempts have also been made to improve the rigidity by blending a polyacetal copolymer having a branched structure introduced therein (Patent Document 1), but at the time of polymerization of the polyacetal copolymer having a branched structure introduced, a cationic polymerization catalyst, depending on the type of comonomer, In particular, when a protonic acid is used as the polymerization catalyst, the initiation of the polymerization may be delayed and the polymerization may suddenly and explosively occur, which is a problem from the viewpoint of production stability.
- Patent Document 2 a copolymer prepared by copolymerizing trioxane and a compound having two or more glycidyl ether groups in one molecule has been proposed (Patent Document 2).
- Patent Document 2 a compound having a plurality of epoxy groups represented by glycidyl ether groups and ether oxygen as functional groups for polymerization.
- a protic acid is used as a polymerization catalyst, polymerization does not occur at a low catalyst amount, and increasing the catalyst amount causes a phenomenon in which a sudden violent polymerization reaction occurs after an irregular induction period, which makes polymerization control difficult. ing.
- the object of the present invention is to provide a polyacetal resin composition having an improved level of mechanical properties.
- the present inventor as a result of extensive studies in order to achieve the above object, based on a polyacetal resin as a base, a triacetal and a specific compound having a trioxane copolymerizable functional group and an alkoxysilyl group are copolymerized with a polyacetal copolymer. It has been found that the incorporation of the coalescent compound can improve mechanical properties that have not been predicted previously, and has reached the present invention described below.
- At least one trioxane copolymerizable functional group selected from the group consisting of trioxane (a), epoxy group and cyclic acetal group and alkoxysilyl group per 100 parts by mass of the polyacetal resin (A), and the trioxane copolymerizable functional group.
- a polyacetal resin composition obtained by mixing 100 parts by mass.
- the copolymer (B) is a polyacetal copolymer (B) obtained by copolymerizing (c) a cyclic acetal compound having an oxyalkylene group having 2 or more carbon atoms in the ring as a comonomer 1 or 2.
- the compound (b) is at least one selected from 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)-ethyltriethoxysilane.
- Polyacetal resin composition of. 6 The polyacetal resin composition according to claim 1, wherein the polyacetal resin (A) is an acetal copolymer.
- At least one trioxane copolymerizable functional group selected from trioxane (a), an epoxy group and a cyclic acetal group and an alkoxysilyl group are contained, and the trioxane copolymerizable functional group and the alkoxysilyl group have a carbon-carbon bond.
- a method for producing a composition A method for producing a polyacetal resin composition, wherein the copolymer (B) is a polyacetal copolymer (B) obtained by using at least one selected from perfluoroalkanesulfonic acid, heteropolyacid, and isopolyacid as a polymerization catalyst.
- the polyacetal resin composition of the present invention has a polyacetal resin (A), trioxane (a), a trioxane copolymerizable functional group and an alkoxysilyl group, and the trioxane copolymerizable functional group and the alkoxysilyl group are carbon-carbon.
- the compounding amount of the polyacetal copolymer (B) is 0.1 to 100 parts by mass, preferably 0.5 to 100 parts by mass, relative to 100 parts by mass of the polyacetal resin (A). It is a department.
- the polyacetal resin (A) which is the substrate of the resin composition of the present invention, is a polymer compound having an oxymethylene unit (—CH 2 O—) as a main constituent unit, and an acetal homopolymer (for example, manufactured by DuPont in the United States, (Trade name "Delrin” and the like), and acetal copolymers containing other comonomer units in addition to the oxymethylene group (for example, trade name "Duracon” manufactured by Polyplastics Co., Ltd.) are included.
- oxymethylene unit —CH 2 O—
- acetal homopolymer for example, manufactured by DuPont in the United States, (Trade name "Delrin” and the like
- acetal copolymers containing other comonomer units in addition to the oxymethylene group for example, trade name "Duracon” manufactured by Polyplastics Co., Ltd.
- the comonomer unit has an oxyalkylene unit having about 2 to 6 carbon atoms (preferably about 2 to 4 carbon atoms) (for example, oxyethylene group (—CH 2 CH 2 O—), oxypropylene group, oxy). (Eg, a tetramethylene group).
- the content of the comonomer unit is an amount that does not significantly impair the crystallinity of the resin, for example, 0.01 to 20 mol% as a proportion of the constitutional unit of the polyacetal polymer, and preferably, It can be selected from the range of about 0.03 to 10 mol %, and more preferably about 0.1 to 7 mol %.
- the acetal copolymer may be a copolymer composed of two components, a terpolymer composed of three components, or the like.
- the acetal copolymer may be a random copolymer, a block copolymer, a graft copolymer, or the like.
- the degree of polymerization, branching degree and crosslinking degree of the polyacetal resin (A) are not particularly limited as long as they can be melt-molded.
- an acetal copolymer is particularly preferable in terms of its thermal stability and the like.
- the polyacetal copolymer (B) of the present invention has a trioxane (a), a trioxane copolymerizable functional group and an alkoxysilyl group, and the trioxane copolymerizable functional group and the alkoxysilyl group have carbon-carbon bonds or An alkoxysilyl group obtained by copolymerizing a compound (b) bonded only by a bond chain selected from an ether bond and optionally a cyclic acetal compound (c) having an oxyalkylene group having 2 or more carbon atoms in the ring; It is a polyacetal copolymer (B) containing.
- the trioxane used in the present invention is a cyclic trimer of formaldehyde, which is generally obtained by reacting an aqueous formaldehyde solution in the presence of an acidic catalyst, and is used after being purified by a method such as distillation. ..
- the component (b) used in the present invention has at least one trioxane copolymerizable functional group selected from an epoxy group and a cyclic acetal group and an alkoxysilyl group, and the trioxane copolymerizable functional group and the alkoxysilyl group are , A compound bonded only by a bond chain selected from a carbon-carbon bond or an ether bond.
- the trioxane copolymerizable functional group and the alkoxysilyl group are bonded only by a bond chain selected from a carbon-carbon bond or an ether bond. That is, it means that only a carbon chain or an ether bond exists between the trioxane copolymerization functional group and the alkoxysilyl group.
- the distance is preferably 2 to 20 carbon atoms, and the number of ether bonds is preferably 0 to 5, more preferably 0 to 2.
- the component (b) can be easily obtained as a silane coupling agent.
- the preferred compounds are exemplified below.
- Me represents a methyl group
- Et represents an ethyl group.
- the most preferable compound is b-1 (2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane) or b-2 (2-(3,4-epoxycyclohexyl)) from the viewpoint of polymerization yield.
- -Ethyltriethoxysilane 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane
- b-2 (2-(3,4-epoxycyclohexyl)
- the component (b) is preferably used in an amount of 0.01 to 5 parts by mass, more preferably 0.03 to 1 part by mass based on 100 parts by mass of the trioxane (a). It is a range.
- the cyclic acetal compound having an oxyethylene group having 2 or more carbon atoms in the ring of the present invention is a compound generally used as a comonomer in the production of a polyacetal copolymer, specifically, 1,3-dioxolane ( DO), 1,3,6-trioxocane, 1,4-butanediol formal (abbreviated as BDF) and the like.
- DO 1,3-dioxolane
- BDF 1,4-butanediol formal
- the component (c) is preferably used in an amount of 0.01 to 20 parts by mass, more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of trioxane. .
- the method for polymerizing the polyacetal copolymer (B) of the present invention comprises (a) trioxane, (b) at least one trioxane copolymerizable functional group selected from an epoxy group and a cyclic acetal group, and an alkoxysilyl group, A compound in which the trioxane copolymerizable functional group and the alkoxysilyl group are bonded only by a bond selected from a carbon-carbon bond or an ether bond, and optionally (c) an oxyalkylene group having 2 or more carbon atoms in the ring
- the cyclic acetal compound having the formula (1) is copolymerized.
- ⁇ Cationic polymerization catalyst As the cationic polymerization catalyst, a known polymerization catalyst in cationic copolymerization containing trioxane as a main monomer can be used. Typically, a Lewis acid and a protic acid are used. In particular, the following protic acids are preferable.
- Examples of the protonic acid include perfluoroalkane sulfonic acid, heteropoly acid and isopoly acid.
- Specific examples of perfluoroalkanesulfonic acid include trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, tridecafluorohexanesulfonic acid, pentadecafluoro Examples thereof include heptane sulfonic acid and heptadecafluorooctane sulfonic acid.
- Heteropolyacid refers to a polyacid produced by dehydration condensation of different oxygen acids, which is a mononuclear or multinuclear compound formed by condensation of a condensed acid group having a specific heterogeneous element in the center and sharing an oxygen atom. It has complex ions.
- the isopoly acid is also referred to as iso-polyacid, homonuclear polycondensation acid or homopolyacid, and refers to a high molecular weight inorganic oxygen acid composed of a condensate of an inorganic oxygen acid having a single V- or VI-valent metal. .
- the heteropoly acid examples include phosphomolybdic acid, phosphotungstic acid, phosphomolybdotungstic acid, phosphomolybdovanadic acid, phosphomolybdo tungstovanadic acid, phosphotungstovanadic acid, silicotungstic acid, silicomolybdic acid, silicomolybd.
- the heteropolyacid is preferably selected from silicomolybdic acid, silicotungstic acid, phosphomolybdic acid, and phosphotungstic acid.
- isopolyacids include paratungstic acid, isopolytungstic acid exemplified by metatungstic acid, paramolybdic acid, isopolymolybdic acid exemplified by metamolybdic acid, metapolyvanadate, isopolyvanadate. Etc. Among them, isopolytungstic acid is preferable from the viewpoint of polymerization activity.
- Lewis acid examples include boron, tin, titanium, phosphorus, arsenic, and antimony halides, and specifically, boron trifluoride, tin tetrachloride, titanium tetrachloride, phosphorus pentafluoride, phosphorus pentachloride. , Antimony pentafluoride and complex compounds or salts thereof.
- the amount of the polymerization catalyst is not particularly limited, but it is preferably 0.1 ppm or more and 50 ppm or less, more preferably 0.1 ppm or more and 30 ppm or less, based on the total of all monomers. Particularly preferably, it is 0.1 ppm or more and 10 ppm or less. (Hereafter, all units of ppm are mass standards.)
- the polymerization method of the polyacetal copolymer of the present invention is not particularly limited.
- the polymerization apparatus is not particularly limited, and a known apparatus is used, and any method such as batch type and continuous type is possible.
- the polymerization temperature is preferably maintained at 65°C or higher and 135°C or lower. It is preferable to use the cationic polymerization catalyst after diluting it with an inert solvent that does not affect the polymerization.
- Deactivation of the polymerization catalyst after the polymerization can be performed by a conventionally known method.
- a basic compound or an aqueous solution thereof may be added to the reaction product discharged from the polymerization machine or the reaction product in the polymerization machine.
- the basic compound for neutralizing and deactivating the polymerization catalyst is not particularly limited. After polymerization and deactivation, washing, separation and recovery of unreacted monomers, drying and the like are further performed by a conventionally known method, if necessary.
- the polyacetal copolymer (B) obtained as described above preferably has a weight average molecular weight (polymethyl methacrylate conversion value measured by size exclusion chromatography) of 10,000 to 500,000, particularly preferably 20,000 to It is 150,000.
- the amount of hemiformal terminal group detected by 1 H-NMR is preferably 0 to 4 mol/kg, and particularly preferably 0 to It is 2 mmol/kg.
- the amount of impurities, especially water, in the total amount of monomers and comonomer to be used for polymerization is 20 ppm or less, particularly preferably 10 ppm or less.
- the stabilizer used here include any one or more of hindered phenol compounds, nitrogen-containing compounds, alkali or alkaline earth metal hydroxides, inorganic salts, and carboxylates. it can.
- thermoplastic resin for example, weathering (light) stabilizer, colorants such as dyes and pigments, lubricants, nucleating agents, release agents, electrostatic charging
- colorants such as dyes and pigments
- lubricants such as dyes and pigments
- nucleating agents such as dyes and pigments
- release agents such as electrostatic charging
- electrostatic charging One or more kinds of inhibitors, surfactants, organic polymer materials, inorganic or organic fibrous, powdery, plate-like fillers and the like can be added.
- the polyacetal resin and the polyacetal copolymer (B) used in the examples and comparative examples are as follows.
- the polyacetal resin was prepared as follows. A twin-screw paddle type continuous polymerization machine was continuously fed with a mixture of 96.7% by mass of trioxane (TOX), 3.3% by mass of 1,3-dioxolane (DO), and 800 ppm of methylal, and used as a catalyst for trifluoride. Polymerization was carried out by adding 20 ppm of boron chloride. The polymer discharged from the discharge port of the polymerization machine was immediately deactivated by adding an aqueous solution containing 1000 ppm of triethylamine, pulverizing and stirring the mixture. Then, the polymer was recovered by centrifugation and dried to obtain a polyacetal resin.
- TOX trioxane
- DO 1,3-dioxolane
- 800 ppm of methylal methylal
- the polyacetal copolymer (B) was prepared as follows. 300 g of trioxane (TOX) (a) was placed in a closed autoclave having a jacket through which a heat medium can be passed and a stirring blade, and the compounds shown in Table 1 as the component (b) and 1,3 as the component (c). -Dioxolane (DO) or 1,4-butanediol formal (BDF) was added so as to be the mass parts shown in Table 1, respectively.
- TOX trioxane
- DO 1,4-butanediol formal
- the catalyst solution (phosphotungstic acid solution in methyl formate, trifluoromethanesulfonic acid solution in cyclohexane) is shown in Table 1.
- Polymerization was initiated by adding in such a manner that the catalyst concentration indicated (relative to all monomers) was obtained. After 5 minutes, 300 g of water containing 1000 ppm of triethylamine was added to the autoclave to stop the reaction, and the contents were taken out and pulverized to 200 mesh or less. Then, after washing with acetone, it was dried to obtain a polyacetal copolymer.
- Examples and Comparative Examples> The various components shown in Table 1 were added and mixed in the proportions shown in Table 1, and melt-kneaded with a vented twin-screw extruder to prepare pelletized compositions.
- 100 parts by weight of the total amount of the components (A) and (B) were mixed with ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-) during the melt kneading Hydroxy-m-tolyl)propionate] (IRGANOX245 manufactured by BASF) and 0.08 part by weight of melamine were added.
- composition of the present invention has excellent mechanical properties (flexural modulus).
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Abstract
The purpose of the present invention is to provide a polyacetal resin composition which has improved mechanical properties. The present invention has been achieved by a polyacetal resin composition which is obtained by mixing 0.1-100 parts by mass of a polyacetal copolymer (B) with 100 parts by mass of a polyacetal resin (A), said polyacetal copolymer (B) being obtained by copolymerizing at least a trioxane (a) and a compound (b) which has an alkoxysilyl group and at least one trioxane copolymerizable functional group that is selected from among epoxy groups and cyclic acetal groups, with the trioxane copolymerizable functional group and the alkoxysilyl group being bonded only by a bond chain that is selected from among a carbon-carbon bond and an ether bond.
Description
本発明は、機械物性に優れたポリアセタール樹脂組成物およびそのポリアセタール樹脂組成物の製造方法に関する。
The present invention relates to a polyacetal resin composition having excellent mechanical properties and a method for producing the polyacetal resin composition.
ポリアセタール樹脂は、機械的特性、熱的特性、電気的特性、摺動性、成形性等において、優れた特性を持っており、主に構造材料や機構部品等として電気機器、自動車部品、精密機械部品等に広く使用されている。しかし、ポリアセタール樹脂が利用される分野の拡大に伴い、要求特性は益々高度化、複合化、特殊化する傾向にある。そのような要求特性として、ポリアセタール樹脂が本来有する優れた摺動性、外観等を維持したまま、剛性改良、ホルムアルデヒドの発生抑制に対し一層の向上が要求される。
Polyacetal resin has excellent properties in mechanical properties, thermal properties, electrical properties, slidability, moldability, etc., and is mainly used as electrical materials, automobile parts, precision machinery as structural materials and mechanical parts. Widely used for parts and so on. However, with the expansion of fields in which polyacetal resins are used, required properties tend to become more sophisticated, complex, and specialized. As such required properties, further improvement is required for improving rigidity and suppressing generation of formaldehyde while maintaining the excellent slidability, appearance, etc. originally possessed by the polyacetal resin.
これに対し、単に剛性を向上させるだけの目的であれば、ポリアセタール樹脂に繊維状フィラー等を充填する方法が一般的であるが、この方法では、繊維状フィラー等の充填による成形品の外観不良や摺動特性の低下等の問題、更には靱性低下の問題がある。
On the other hand, for the purpose of merely improving the rigidity, a method of filling the polyacetal resin with a fibrous filler or the like is generally used, but in this method, the appearance of the molded product is poor due to the filling of the fibrous filler or the like. There are problems such as deterioration of sliding characteristics and sliding properties, and further deterioration of toughness.
また、ポリアセタール共重合体では、コモノマー量を減少させることにより、摺動性や外観を実質的に損なうことなく剛性を向上させることが知られているが、コモノマー減量の手法においては、靱性が低下するのみならずポリマーの熱安定性も低下する等の問題が生じ、必ずしも要求に応え得るものではなかった。
In addition, in the polyacetal copolymer, it is known that by reducing the amount of comonomer, the rigidity is improved without substantially impairing the slidability and the appearance, but in the method of reducing the comonomer, the toughness decreases. However, the thermal stability of the polymer is also deteriorated and other problems occur, and it is not always possible to meet the demand.
分岐構造導入したポリアセタール共重合体を配合した剛性向上も試みられているが（特許文献１）、分岐構造を導入したポリアセタール共重合体の重合の際に、コモノマーの種類によっては、カチオン重合触媒、特にプロトン酸を重合触媒とする場合に、重合開始が遅れ、突然爆発的に重合が起こってしまうことがあり、生産安定性の面からも課題があった。
Attempts have also been made to improve the rigidity by blending a polyacetal copolymer having a branched structure introduced therein (Patent Document 1), but at the time of polymerization of the polyacetal copolymer having a branched structure introduced, a cationic polymerization catalyst, depending on the type of comonomer, In particular, when a protonic acid is used as the polymerization catalyst, the initiation of the polymerization may be delayed and the polymerization may suddenly and explosively occur, which is a problem from the viewpoint of production stability.
例えば、ポリアセタール共重合体に関して、トリオキサンと、１分子中にグリシジルエーテル基を２個以上有する化合物とを共重合させた共重合体が提案されている（特許文献２）。しかし、グリシジルエーテル基に代表されるエポキシ基とエーテル酸素を官能基として複数個有する化合物を重合に使用する場合、重合安定性に課題が残っている。特にプロトン酸を重合触媒に使用した場合、低触媒量では重合が起こらず、触媒量を上げると、不定期な誘導期ののち、突然激しい重合反応が起こる現象が発生し、重合制御を難しくしている。
For example, regarding a polyacetal copolymer, a copolymer prepared by copolymerizing trioxane and a compound having two or more glycidyl ether groups in one molecule has been proposed (Patent Document 2). However, when using a compound having a plurality of epoxy groups represented by glycidyl ether groups and ether oxygen as functional groups for polymerization, there remains a problem in polymerization stability. Especially when a protic acid is used as a polymerization catalyst, polymerization does not occur at a low catalyst amount, and increasing the catalyst amount causes a phenomenon in which a sudden violent polymerization reaction occurs after an irregular induction period, which makes polymerization control difficult. ing.
本発明の目的は、機械物性のレベルを向上させたポリアセタール樹脂組成物を提供することにある。
The object of the present invention is to provide a polyacetal resin composition having an improved level of mechanical properties.
本発明者は、前記目的を達成するために鋭意検討した結果、ポリアセタール樹脂を基体とし、これにトリオキサンとトリオキサン共重合性官能基ならびにアルコキシシリル基を持つ特定の化合物とを共重合したポリアセタール共重合体を配合することにより、従来予知されなかったほどの機械物性の向上が可能であることを見出し、以下の本発明に達した。
The present inventor, as a result of extensive studies in order to achieve the above object, based on a polyacetal resin as a base, a triacetal and a specific compound having a trioxane copolymerizable functional group and an alkoxysilyl group are copolymerized with a polyacetal copolymer. It has been found that the incorporation of the coalescent compound can improve mechanical properties that have not been predicted previously, and has reached the present invention described below.
１．ポリアセタール樹脂（Ａ）１００質量部に対して
少なくともトリオキサン（ａ）、エポキシ基および環状アセタール基から選ばれる少なくとも一種のトリオキサン共重合性官能基ならびにアルコキシシリル基を有し、該トリオキサン共重合性官能基と該アルコキシシリル基は、炭素－炭素結合またはエーテル結合から選択される結合連鎖のみによって結合している化合物（ｂ）とを共重合して得られるポリアセタール共重合体（Ｂ）を０．１～１００質量部を混合して得られるポリアセタール樹脂組成物。 1. At least one trioxane copolymerizable functional group selected from the group consisting of trioxane (a), epoxy group and cyclic acetal group and alkoxysilyl group per 100 parts by mass of the polyacetal resin (A), and the trioxane copolymerizable functional group. 0.1 to 10% of the polyacetal copolymer (B) obtained by copolymerizing the above-mentioned alkoxysilyl group with a compound (b) in which the alkoxysilyl group is bonded only by a bond chain selected from a carbon-carbon bond or an ether bond. A polyacetal resin composition obtained by mixing 100 parts by mass.
少なくともトリオキサン（ａ）、エポキシ基および環状アセタール基から選ばれる少なくとも一種のトリオキサン共重合性官能基ならびにアルコキシシリル基を有し、該トリオキサン共重合性官能基と該アルコキシシリル基は、炭素－炭素結合またはエーテル結合から選択される結合連鎖のみによって結合している化合物（ｂ）とを共重合して得られるポリアセタール共重合体（Ｂ）を０．１～１００質量部を混合して得られるポリアセタール樹脂組成物。 1. At least one trioxane copolymerizable functional group selected from the group consisting of trioxane (a), epoxy group and cyclic acetal group and alkoxysilyl group per 100 parts by mass of the polyacetal resin (A), and the trioxane copolymerizable functional group. 0.1 to 10% of the polyacetal copolymer (B) obtained by copolymerizing the above-mentioned alkoxysilyl group with a compound (b) in which the alkoxysilyl group is bonded only by a bond chain selected from a carbon-carbon bond or an ether bond. A polyacetal resin composition obtained by mixing 100 parts by mass.
２．前記共重合体（Ｂ）が、パーフルオロアルカンスルホン酸、ヘテロポリ酸、イソポリ酸から選ばれる１種以上を重合触媒として得られるポリアセタール共重合体（Ｂ）である１記載のポリアセタール樹脂組成物。
３．前記共重合体（Ｂ）が、コモノマーとしてさらに（ｃ）炭素数２以上のオキシアルキレン基を環内に有する環状アセタール化合物を共重合して得られたポリアセタール共重合体（Ｂ）である１または２記載のポリアセタール樹脂組成物。
４．前記アルコキシシリル基が、トリアルコキシシリル基およびジアルコキシシリル基から選ばれる少なくとも一種である１～３記載のポリアセタール樹脂組成物。 2. 2. The polyacetal resin composition according to 1, wherein the copolymer (B) is a polyacetal copolymer (B) obtained by using at least one selected from perfluoroalkanesulfonic acid, heteropolyacid and isopolyacid as a polymerization catalyst.
3. The copolymer (B) is a polyacetal copolymer (B) obtained by copolymerizing (c) a cyclic acetal compound having an oxyalkylene group having 2 or more carbon atoms in the ring as a comonomer 1 or 2. The polyacetal resin composition according to 2.
4. 4. The polyacetal resin composition according to 1 to 3, wherein the alkoxysilyl group is at least one selected from a trialkoxysilyl group and a dialkoxysilyl group.
３．前記共重合体（Ｂ）が、コモノマーとしてさらに（ｃ）炭素数２以上のオキシアルキレン基を環内に有する環状アセタール化合物を共重合して得られたポリアセタール共重合体（Ｂ）である１または２記載のポリアセタール樹脂組成物。
４．前記アルコキシシリル基が、トリアルコキシシリル基およびジアルコキシシリル基から選ばれる少なくとも一種である１～３記載のポリアセタール樹脂組成物。 2. 2. The polyacetal resin composition according to 1, wherein the copolymer (B) is a polyacetal copolymer (B) obtained by using at least one selected from perfluoroalkanesulfonic acid, heteropolyacid and isopolyacid as a polymerization catalyst.
3. The copolymer (B) is a polyacetal copolymer (B) obtained by copolymerizing (c) a cyclic acetal compound having an oxyalkylene group having 2 or more carbon atoms in the ring as a comonomer 1 or 2. The polyacetal resin composition according to 2.
4. 4. The polyacetal resin composition according to 1 to 3, wherein the alkoxysilyl group is at least one selected from a trialkoxysilyl group and a dialkoxysilyl group.
５．前記（b）化合物が、２-(３、４-エポキシシクロヘキシル)-エチルトリメトキシシランおよび２-(３、４-エポキシシクロヘキシル)-エチルトリエトキシシランから選ばれる少なくとも１種である１～３記載のポリアセタール樹脂組成物。
６．ポリアセタール樹脂（Ａ）がアセタールコポリマーである請求項１～５記載のポリアセタール樹脂組成物。 5. 1 to 3, wherein the compound (b) is at least one selected from 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)-ethyltriethoxysilane. Polyacetal resin composition of.
6. The polyacetal resin composition according to claim 1, wherein the polyacetal resin (A) is an acetal copolymer.
６．ポリアセタール樹脂（Ａ）がアセタールコポリマーである請求項１～５記載のポリアセタール樹脂組成物。 5. 1 to 3, wherein the compound (b) is at least one selected from 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)-ethyltriethoxysilane. Polyacetal resin composition of.
6. The polyacetal resin composition according to claim 1, wherein the polyacetal resin (A) is an acetal copolymer.
７．ポリアセタール樹脂（Ａ）１００質量部に対して、
少なくともトリオキサン（ａ）、エポキシ基および環状アセタール基から選ばれる少なくとも一種のトリオキサン共重合性官能基ならびにアルコキシシリル基を有し、該トリオキサン共重合性官能基と該アルコキシシリル基は、炭素－炭素結合またはエーテル結合から選択される結合連鎖のみによって結合している化合物（ｂ）とを共重合して得られるポリアセタール共重合体（Ｂ）を０．１～１００質量部を混合して得られるポリアセタール樹脂組成物の製造方法であって、
該共重合体（Ｂ）が、パーフルオロアルカンスルホン酸、ヘテロポリ酸、イソポリ酸から選ばれる１種以上を重合触媒として得られるポリアセタール共重合体（Ｂ）であるポリアセタール樹脂組成物の製造方法。 7. With respect to 100 parts by mass of the polyacetal resin (A),
At least one trioxane copolymerizable functional group selected from trioxane (a), an epoxy group and a cyclic acetal group and an alkoxysilyl group are contained, and the trioxane copolymerizable functional group and the alkoxysilyl group have a carbon-carbon bond. Alternatively, a polyacetal resin obtained by mixing 0.1 to 100 parts by mass of a polyacetal copolymer (B) obtained by copolymerizing the compound (b) bonded only by a bond chain selected from an ether bond. A method for producing a composition,
A method for producing a polyacetal resin composition, wherein the copolymer (B) is a polyacetal copolymer (B) obtained by using at least one selected from perfluoroalkanesulfonic acid, heteropolyacid, and isopolyacid as a polymerization catalyst.
少なくともトリオキサン（ａ）、エポキシ基および環状アセタール基から選ばれる少なくとも一種のトリオキサン共重合性官能基ならびにアルコキシシリル基を有し、該トリオキサン共重合性官能基と該アルコキシシリル基は、炭素－炭素結合またはエーテル結合から選択される結合連鎖のみによって結合している化合物（ｂ）とを共重合して得られるポリアセタール共重合体（Ｂ）を０．１～１００質量部を混合して得られるポリアセタール樹脂組成物の製造方法であって、
該共重合体（Ｂ）が、パーフルオロアルカンスルホン酸、ヘテロポリ酸、イソポリ酸から選ばれる１種以上を重合触媒として得られるポリアセタール共重合体（Ｂ）であるポリアセタール樹脂組成物の製造方法。 7. With respect to 100 parts by mass of the polyacetal resin (A),
At least one trioxane copolymerizable functional group selected from trioxane (a), an epoxy group and a cyclic acetal group and an alkoxysilyl group are contained, and the trioxane copolymerizable functional group and the alkoxysilyl group have a carbon-carbon bond. Alternatively, a polyacetal resin obtained by mixing 0.1 to 100 parts by mass of a polyacetal copolymer (B) obtained by copolymerizing the compound (b) bonded only by a bond chain selected from an ether bond. A method for producing a composition,
A method for producing a polyacetal resin composition, wherein the copolymer (B) is a polyacetal copolymer (B) obtained by using at least one selected from perfluoroalkanesulfonic acid, heteropolyacid, and isopolyacid as a polymerization catalyst.
以下、本発明の具体的な実施形態について、詳細に説明するが、本発明は、以下の実施形態に何ら限定されるものではなく、本発明の目的の範囲内において、適宜変更を加えて実施することができる。
Hereinafter, specific embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and is appropriately modified within the scope of the object of the present invention. can do.
＜ポリアセタール樹脂組成物＞
本発明のポリアセタール樹脂組成物はポリアセタール樹脂（Ａ）とトリオキサン（ａ） 、トリオキサン共重合性官能基ならびにアルコキシシリル基を有し、該トリオキサン共重合性官能基と該アルコキシシリル基は、炭素－炭素結合またはエーテル結合から選択される結合連鎖のみによって結合している化合物（ｂ）及び場合により炭素数２以上のオキシアルキレン基を環内に有する環状アセタール化合物（ｃ）を共重合して得られるポリアセタール共重合体（Ｂ）とを含有するポリアセタール樹脂組成物である事を特徴とするものである。本発明の樹脂組成物において、かかるポリアセタール共重合体（Ｂ）の配合量は、ポリアセタール樹脂（Ａ）１００質量部に対し、０．１～１００質量部であり、好ましくは０．５～１００質量部である。 <Polyacetal resin composition>
The polyacetal resin composition of the present invention has a polyacetal resin (A), trioxane (a), a trioxane copolymerizable functional group and an alkoxysilyl group, and the trioxane copolymerizable functional group and the alkoxysilyl group are carbon-carbon. A polyacetal obtained by copolymerizing a compound (b) bound only by a bond chain selected from a bond or an ether bond and a cyclic acetal compound (c) optionally having an oxyalkylene group having 2 or more carbon atoms in the ring It is characterized by being a polyacetal resin composition containing a copolymer (B). In the resin composition of the present invention, the compounding amount of the polyacetal copolymer (B) is 0.1 to 100 parts by mass, preferably 0.5 to 100 parts by mass, relative to 100 parts by mass of the polyacetal resin (A). It is a department.
本発明のポリアセタール樹脂組成物はポリアセタール樹脂（Ａ）とトリオキサン（ａ） 、トリオキサン共重合性官能基ならびにアルコキシシリル基を有し、該トリオキサン共重合性官能基と該アルコキシシリル基は、炭素－炭素結合またはエーテル結合から選択される結合連鎖のみによって結合している化合物（ｂ）及び場合により炭素数２以上のオキシアルキレン基を環内に有する環状アセタール化合物（ｃ）を共重合して得られるポリアセタール共重合体（Ｂ）とを含有するポリアセタール樹脂組成物である事を特徴とするものである。本発明の樹脂組成物において、かかるポリアセタール共重合体（Ｂ）の配合量は、ポリアセタール樹脂（Ａ）１００質量部に対し、０．１～１００質量部であり、好ましくは０．５～１００質量部である。 <Polyacetal resin composition>
The polyacetal resin composition of the present invention has a polyacetal resin (A), trioxane (a), a trioxane copolymerizable functional group and an alkoxysilyl group, and the trioxane copolymerizable functional group and the alkoxysilyl group are carbon-carbon. A polyacetal obtained by copolymerizing a compound (b) bound only by a bond chain selected from a bond or an ether bond and a cyclic acetal compound (c) optionally having an oxyalkylene group having 2 or more carbon atoms in the ring It is characterized by being a polyacetal resin composition containing a copolymer (B). In the resin composition of the present invention, the compounding amount of the polyacetal copolymer (B) is 0.1 to 100 parts by mass, preferably 0.5 to 100 parts by mass, relative to 100 parts by mass of the polyacetal resin (A). It is a department.
＜（Ａ）ポリアセタール樹脂＞
以下、本発明のポリアセタール樹脂組成物の構成について詳細に説明する。
本発明の樹脂組成物の基体であるポリアセタール樹脂（Ａ）とは、オキシメチレン単位（－ＣＨ２Ｏ－）を主たる構成単位とする高分子化合物であり、アセタールホモポリマー（例えば米国デュポン社製、商品名「デルリン」等）、オキシメチレン基以外に他のコモノマー単位を含有するアセタールコポリマー（例えば、ポリプラスチックス（株）社製、商品名「ジュラコン」等）が含まれる。 <(A) Polyacetal resin>
Hereinafter, the constitution of the polyacetal resin composition of the present invention will be described in detail.
The polyacetal resin (A), which is the substrate of the resin composition of the present invention, is a polymer compound having an oxymethylene unit (—CH 2 O—) as a main constituent unit, and an acetal homopolymer (for example, manufactured by DuPont in the United States, (Trade name "Delrin" and the like), and acetal copolymers containing other comonomer units in addition to the oxymethylene group (for example, trade name "Duracon" manufactured by Polyplastics Co., Ltd.) are included.
以下、本発明のポリアセタール樹脂組成物の構成について詳細に説明する。
本発明の樹脂組成物の基体であるポリアセタール樹脂（Ａ）とは、オキシメチレン単位（－ＣＨ２Ｏ－）を主たる構成単位とする高分子化合物であり、アセタールホモポリマー（例えば米国デュポン社製、商品名「デルリン」等）、オキシメチレン基以外に他のコモノマー単位を含有するアセタールコポリマー（例えば、ポリプラスチックス（株）社製、商品名「ジュラコン」等）が含まれる。 <(A) Polyacetal resin>
Hereinafter, the constitution of the polyacetal resin composition of the present invention will be described in detail.
The polyacetal resin (A), which is the substrate of the resin composition of the present invention, is a polymer compound having an oxymethylene unit (—CH 2 O—) as a main constituent unit, and an acetal homopolymer (for example, manufactured by DuPont in the United States, (Trade name "Delrin" and the like), and acetal copolymers containing other comonomer units in addition to the oxymethylene group (for example, trade name "Duracon" manufactured by Polyplastics Co., Ltd.) are included.
アセタールコポリマーにおいて、コモノマー単位には炭素数２～６程度（好ましくは、炭素数２～４程度）のオキシアルキレン単位（例えば、オキシエチレン基（－ＣＨ２ＣＨ２Ｏ－）、オキシプロピレン基、オキシテトラメチレン基等）が含まれる。
In the acetal copolymer, the comonomer unit has an oxyalkylene unit having about 2 to 6 carbon atoms (preferably about 2 to 4 carbon atoms) (for example, oxyethylene group (—CH 2 CH 2 O—), oxypropylene group, oxy). (Eg, a tetramethylene group).
また、コモノマー単位の含有量は、樹脂の結晶性を大幅に損なわない程度の量、例えば、ポリアセタール重合体の構成単位に占める割合として、一般的には０．０１～２０モル％、好ましくは、０．０３～１０モル％、更に好ましくは、０．１～７モル％程度の範囲から選択できる。
The content of the comonomer unit is an amount that does not significantly impair the crystallinity of the resin, for example, 0.01 to 20 mol% as a proportion of the constitutional unit of the polyacetal polymer, and preferably, It can be selected from the range of about 0.03 to 10 mol %, and more preferably about 0.1 to 7 mol %.
アセタールコポリマーは、二成分で構成されたコポリマー、三成分で構成されたターポリマー等であってよい。アセタールコポリマーは、ランダムコポリマーの他、ブロックコポリマー、グラフトコポリマー等であってよい。
The acetal copolymer may be a copolymer composed of two components, a terpolymer composed of three components, or the like. The acetal copolymer may be a random copolymer, a block copolymer, a graft copolymer, or the like.
また、このようなポリアセタール樹脂（Ａ）の重合度、分岐度や架橋度も特に制限はなく溶融成形可能であればよい。本発明において配合するポリアセタール樹脂（Ａ）としては、その熱安定性等の点で特にアセタールコポリマーが好ましい。
The degree of polymerization, branching degree and crosslinking degree of the polyacetal resin (A) are not particularly limited as long as they can be melt-molded. As the polyacetal resin (A) blended in the present invention, an acetal copolymer is particularly preferable in terms of its thermal stability and the like.
＜（Ｂ）ポリアセタール共重合体＞
本発明のポリアセタール共重合体（Ｂ）は、トリオキサン（ａ）、トリオキサン共重合性官能基ならびにアルコキシシリル基を有し、該トリオキサン共重合性官能基と該アルコキシシリル基は、炭素－炭素結合またはエーテル結合から選択される結合連鎖のみによって結合している化合物（ｂ）及び場合により、炭素数２以上のオキシアルキレン基を環内に有する環状アセタール化合物（ｃ）とを共重合したアルコキシシリル基を含むポリアセタール共重合体（Ｂ）である。 <(B) Polyacetal copolymer>
The polyacetal copolymer (B) of the present invention has a trioxane (a), a trioxane copolymerizable functional group and an alkoxysilyl group, and the trioxane copolymerizable functional group and the alkoxysilyl group have carbon-carbon bonds or An alkoxysilyl group obtained by copolymerizing a compound (b) bonded only by a bond chain selected from an ether bond and optionally a cyclic acetal compound (c) having an oxyalkylene group having 2 or more carbon atoms in the ring; It is a polyacetal copolymer (B) containing.
本発明のポリアセタール共重合体（Ｂ）は、トリオキサン（ａ）、トリオキサン共重合性官能基ならびにアルコキシシリル基を有し、該トリオキサン共重合性官能基と該アルコキシシリル基は、炭素－炭素結合またはエーテル結合から選択される結合連鎖のみによって結合している化合物（ｂ）及び場合により、炭素数２以上のオキシアルキレン基を環内に有する環状アセタール化合物（ｃ）とを共重合したアルコキシシリル基を含むポリアセタール共重合体（Ｂ）である。 <(B) Polyacetal copolymer>
The polyacetal copolymer (B) of the present invention has a trioxane (a), a trioxane copolymerizable functional group and an alkoxysilyl group, and the trioxane copolymerizable functional group and the alkoxysilyl group have carbon-carbon bonds or An alkoxysilyl group obtained by copolymerizing a compound (b) bonded only by a bond chain selected from an ether bond and optionally a cyclic acetal compound (c) having an oxyalkylene group having 2 or more carbon atoms in the ring; It is a polyacetal copolymer (B) containing.
≪（ａ）トリオキサン≫
本発明において用いられるトリオキサンとは、ホルムアルデヒドの環状三量体であり、一般的には酸性触媒の存在下でホルムアルデヒド水溶液を反応させることによって得られ、これを蒸留等の方法で精製して用いられる。 <<(a) Trioxane>>
The trioxane used in the present invention is a cyclic trimer of formaldehyde, which is generally obtained by reacting an aqueous formaldehyde solution in the presence of an acidic catalyst, and is used after being purified by a method such as distillation. ..
本発明において用いられるトリオキサンとは、ホルムアルデヒドの環状三量体であり、一般的には酸性触媒の存在下でホルムアルデヒド水溶液を反応させることによって得られ、これを蒸留等の方法で精製して用いられる。 <<(a) Trioxane>>
The trioxane used in the present invention is a cyclic trimer of formaldehyde, which is generally obtained by reacting an aqueous formaldehyde solution in the presence of an acidic catalyst, and is used after being purified by a method such as distillation. ..
≪（ｂ）エポキシ基および環状アセタール基から選ばれる少なくとも一種のトリオキサン共重合性官能基ならびにアルコキシシリル基を有し、該トリオキサン共重合性官能基と該アルコキシシリル基は、炭素－炭素結合またはエーテル結合から選択される結合連鎖のみによって結合している化合物≫
本発明で使用する（ｂ）成分は、エポキシ基および環状アセタール基から選ばれる少なくとも一種のトリオキサン共重合性官能基ならびにアルコキシシリル基を有し、該トリオキサン共重合性官能基と該アルコキシシリル基は、炭素－炭素結合またはエーテル結合から選択される結合連鎖のみによって結合している化合物であることを特徴とする。 «(B) Having at least one trioxane copolymerizable functional group selected from an epoxy group and a cyclic acetal group and an alkoxysilyl group, wherein the trioxane copolymerizable functional group and the alkoxysilyl group are carbon-carbon bonds or ethers. Compounds that are bound only by the bond chains selected from the bonds >>
The component (b) used in the present invention has at least one trioxane copolymerizable functional group selected from an epoxy group and a cyclic acetal group and an alkoxysilyl group, and the trioxane copolymerizable functional group and the alkoxysilyl group are , A compound bonded only by a bond chain selected from a carbon-carbon bond or an ether bond.
本発明で使用する（ｂ）成分は、エポキシ基および環状アセタール基から選ばれる少なくとも一種のトリオキサン共重合性官能基ならびにアルコキシシリル基を有し、該トリオキサン共重合性官能基と該アルコキシシリル基は、炭素－炭素結合またはエーテル結合から選択される結合連鎖のみによって結合している化合物であることを特徴とする。 «(B) Having at least one trioxane copolymerizable functional group selected from an epoxy group and a cyclic acetal group and an alkoxysilyl group, wherein the trioxane copolymerizable functional group and the alkoxysilyl group are carbon-carbon bonds or ethers. Compounds that are bound only by the bond chains selected from the bonds >>
The component (b) used in the present invention has at least one trioxane copolymerizable functional group selected from an epoxy group and a cyclic acetal group and an alkoxysilyl group, and the trioxane copolymerizable functional group and the alkoxysilyl group are , A compound bonded only by a bond chain selected from a carbon-carbon bond or an ether bond.
本発明の（ｂ）成分において、トリオキサン共重合性官能基とアルコキシシリル基は、炭素－炭素結合またはエーテル結合から選択される結合連鎖のみによって結合している。
すなわちトリオキサン共重合官能基とアルコキシシリル基の間には、炭素鎖またはエーテル結合だけが存在することを意味する。
その距離は、炭素数として２～２０であることが好ましく、エーテル結合の数は、０～５であることが好ましく、０～２であることがさらに好ましい。 In the component (b) of the present invention, the trioxane copolymerizable functional group and the alkoxysilyl group are bonded only by a bond chain selected from a carbon-carbon bond or an ether bond.
That is, it means that only a carbon chain or an ether bond exists between the trioxane copolymerization functional group and the alkoxysilyl group.
The distance is preferably 2 to 20 carbon atoms, and the number of ether bonds is preferably 0 to 5, more preferably 0 to 2.
すなわちトリオキサン共重合官能基とアルコキシシリル基の間には、炭素鎖またはエーテル結合だけが存在することを意味する。
その距離は、炭素数として２～２０であることが好ましく、エーテル結合の数は、０～５であることが好ましく、０～２であることがさらに好ましい。 In the component (b) of the present invention, the trioxane copolymerizable functional group and the alkoxysilyl group are bonded only by a bond chain selected from a carbon-carbon bond or an ether bond.
That is, it means that only a carbon chain or an ether bond exists between the trioxane copolymerization functional group and the alkoxysilyl group.
The distance is preferably 2 to 20 carbon atoms, and the number of ether bonds is preferably 0 to 5, more preferably 0 to 2.
（ｂ）成分は、シランカップリング剤として容易に入手することができる。
下記に好ましい化合物を例示する。なお、Ｍｅはメチル基、Ｅｔはエチル基を表す。これらのうち、最も好ましい化合物は重合収率の観点から、ｂ-1（２-(３、４-エポキシシクロヘキシル)-エチルトリメトキシシラン）またはｂ-２（２-(３、４-エポキシシクロヘキシル)-エチルトリエトキシシラン）である。 The component (b) can be easily obtained as a silane coupling agent.
The preferred compounds are exemplified below. In addition, Me represents a methyl group and Et represents an ethyl group. Among these, the most preferable compound is b-1 (2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane) or b-2 (2-(3,4-epoxycyclohexyl)) from the viewpoint of polymerization yield. -Ethyltriethoxysilane).
下記に好ましい化合物を例示する。なお、Ｍｅはメチル基、Ｅｔはエチル基を表す。これらのうち、最も好ましい化合物は重合収率の観点から、ｂ-1（２-(３、４-エポキシシクロヘキシル)-エチルトリメトキシシラン）またはｂ-２（２-(３、４-エポキシシクロヘキシル)-エチルトリエトキシシラン）である。 The component (b) can be easily obtained as a silane coupling agent.
The preferred compounds are exemplified below. In addition, Me represents a methyl group and Et represents an ethyl group. Among these, the most preferable compound is b-1 (2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane) or b-2 (2-(3,4-epoxycyclohexyl)) from the viewpoint of polymerization yield. -Ethyltriethoxysilane).
本発明において、（ｂ）成分は、トリオキサン（ａ）１００質量部に対して０．０１～５質量部の範囲となるように使用するのが好ましく、さらに好ましくは０．０３～１質量部の範囲である。
In the present invention, the component (b) is preferably used in an amount of 0.01 to 5 parts by mass, more preferably 0.03 to 1 part by mass based on 100 parts by mass of the trioxane (a). It is a range.
≪（ｃ）炭素数２以上のオキシエチレン基を環内に有する環状アセタール化合物≫
本発明の炭素数２以上のオキシエチレン基を環内に有する環状アセタール化合物とは、ポリアセタール共重合体の製造においてコモノマーとして一般に使用される化合物である、具体的には、１，３－ジオキソラン（ＤＯ）、１，３，６－トリオキソカン、１，４－ブタンジオールホルマール（ＢＤＦと略す）等が挙げられる。 <<(c) Cyclic acetal compound having oxyethylene group having 2 or more carbon atoms in the ring>>
The cyclic acetal compound having an oxyethylene group having 2 or more carbon atoms in the ring of the present invention is a compound generally used as a comonomer in the production of a polyacetal copolymer, specifically, 1,3-dioxolane ( DO), 1,3,6-trioxocane, 1,4-butanediol formal (abbreviated as BDF) and the like.
本発明の炭素数２以上のオキシエチレン基を環内に有する環状アセタール化合物とは、ポリアセタール共重合体の製造においてコモノマーとして一般に使用される化合物である、具体的には、１，３－ジオキソラン（ＤＯ）、１，３，６－トリオキソカン、１，４－ブタンジオールホルマール（ＢＤＦと略す）等が挙げられる。 <<(c) Cyclic acetal compound having oxyethylene group having 2 or more carbon atoms in the ring>>
The cyclic acetal compound having an oxyethylene group having 2 or more carbon atoms in the ring of the present invention is a compound generally used as a comonomer in the production of a polyacetal copolymer, specifically, 1,3-dioxolane ( DO), 1,3,6-trioxocane, 1,4-butanediol formal (abbreviated as BDF) and the like.
本発明において、（ｃ）成分は、トリオキサン１００質量部に対して０．０１～２０質量部の範囲となるように使用するのが好ましく、さらに好ましくは０．０５～５質量部の範囲である。
In the present invention, the component (c) is preferably used in an amount of 0.01 to 20 parts by mass, more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of trioxane. .
＜ポリアセタール共重合体（Ｂ）の重合方法＞
本発明のポリアセタール共重合体（Ｂ）の重合方法は、（a）トリオキサン、（b）エポキシ基および環状アセタール基から選ばれる少なくとも一種のトリオキサン共重合性官能基ならびにアルコキシシリル基を有し、該トリオキサン共重合性官能基と該アルコキシシリル基は、炭素－炭素結合またはエーテル結合から選択される結合のみによって結合している化合物、および場合により(c)炭素数２以上のオキシアルキレン基を環内に有する環状アセタール化合物とを、カチオン重合触媒の存在下、共重合させることを特徴とする。 <Polymerization method of polyacetal copolymer (B)>
The method for polymerizing the polyacetal copolymer (B) of the present invention comprises (a) trioxane, (b) at least one trioxane copolymerizable functional group selected from an epoxy group and a cyclic acetal group, and an alkoxysilyl group, A compound in which the trioxane copolymerizable functional group and the alkoxysilyl group are bonded only by a bond selected from a carbon-carbon bond or an ether bond, and optionally (c) an oxyalkylene group having 2 or more carbon atoms in the ring In the presence of a cationic polymerization catalyst, the cyclic acetal compound having the formula (1) is copolymerized.
本発明のポリアセタール共重合体（Ｂ）の重合方法は、（a）トリオキサン、（b）エポキシ基および環状アセタール基から選ばれる少なくとも一種のトリオキサン共重合性官能基ならびにアルコキシシリル基を有し、該トリオキサン共重合性官能基と該アルコキシシリル基は、炭素－炭素結合またはエーテル結合から選択される結合のみによって結合している化合物、および場合により(c)炭素数２以上のオキシアルキレン基を環内に有する環状アセタール化合物とを、カチオン重合触媒の存在下、共重合させることを特徴とする。 <Polymerization method of polyacetal copolymer (B)>
The method for polymerizing the polyacetal copolymer (B) of the present invention comprises (a) trioxane, (b) at least one trioxane copolymerizable functional group selected from an epoxy group and a cyclic acetal group, and an alkoxysilyl group, A compound in which the trioxane copolymerizable functional group and the alkoxysilyl group are bonded only by a bond selected from a carbon-carbon bond or an ether bond, and optionally (c) an oxyalkylene group having 2 or more carbon atoms in the ring In the presence of a cationic polymerization catalyst, the cyclic acetal compound having the formula (1) is copolymerized.
＜カチオン重合触媒＞
カチオン重合触媒としては、トリオキサンを主モノマーとするカチオン共重合において公知の重合触媒が使用できる。代表的には、ルイス酸、プロトン酸が挙げられる。特に、以下に示すプロトン酸であることが好ましい。 <Cationic polymerization catalyst>
As the cationic polymerization catalyst, a known polymerization catalyst in cationic copolymerization containing trioxane as a main monomer can be used. Typically, a Lewis acid and a protic acid are used. In particular, the following protic acids are preferable.
カチオン重合触媒としては、トリオキサンを主モノマーとするカチオン共重合において公知の重合触媒が使用できる。代表的には、ルイス酸、プロトン酸が挙げられる。特に、以下に示すプロトン酸であることが好ましい。 <Cationic polymerization catalyst>
As the cationic polymerization catalyst, a known polymerization catalyst in cationic copolymerization containing trioxane as a main monomer can be used. Typically, a Lewis acid and a protic acid are used. In particular, the following protic acids are preferable.
≪プロトン酸≫
プロトン酸としては、パーフルオロアルカンスルホン酸、ヘテロポリ酸、イソポリ酸が挙げられる。
パーフルオロアルカンスルホン酸の具体例として、トリフルオロメタンスルホン酸、ペンタフルオロエタンスルホン酸、ヘプタフルオロプロパンスルホン酸、ノナフルオロブタンスルホン酸、ウンデカフルオロペンタンスルホン酸、トリデカフルオロヘキサンスルホン酸、ペンタデカフルオロへプタンスルホン酸、ヘプタデカフルオロオクタンスルホン酸が挙げられる。 ≪Protonic acid≫
Examples of the protonic acid include perfluoroalkane sulfonic acid, heteropoly acid and isopoly acid.
Specific examples of perfluoroalkanesulfonic acid include trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, tridecafluorohexanesulfonic acid, pentadecafluoro Examples thereof include heptane sulfonic acid and heptadecafluorooctane sulfonic acid.
プロトン酸としては、パーフルオロアルカンスルホン酸、ヘテロポリ酸、イソポリ酸が挙げられる。
パーフルオロアルカンスルホン酸の具体例として、トリフルオロメタンスルホン酸、ペンタフルオロエタンスルホン酸、ヘプタフルオロプロパンスルホン酸、ノナフルオロブタンスルホン酸、ウンデカフルオロペンタンスルホン酸、トリデカフルオロヘキサンスルホン酸、ペンタデカフルオロへプタンスルホン酸、ヘプタデカフルオロオクタンスルホン酸が挙げられる。 ≪Protonic acid≫
Examples of the protonic acid include perfluoroalkane sulfonic acid, heteropoly acid and isopoly acid.
Specific examples of perfluoroalkanesulfonic acid include trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, tridecafluorohexanesulfonic acid, pentadecafluoro Examples thereof include heptane sulfonic acid and heptadecafluorooctane sulfonic acid.
ヘテロポリ酸とは、異種の酸素酸が脱水縮合して生成するポリ酸をいい、中心に特定の異種元素が存在し、酸素原子を共有して縮合酸基が縮合してできる単核又は複核の錯イオンを有する。イソポリ酸とは、イソ多重酸、同核縮合酸、同種多重酸とも称され、Ｖ価又はＶＩ価の単一種類の金属を有する無機酸素酸の縮合体から成る高分子量の無機酸素酸をいう。
Heteropolyacid refers to a polyacid produced by dehydration condensation of different oxygen acids, which is a mononuclear or multinuclear compound formed by condensation of a condensed acid group having a specific heterogeneous element in the center and sharing an oxygen atom. It has complex ions. The isopoly acid is also referred to as iso-polyacid, homonuclear polycondensation acid or homopolyacid, and refers to a high molecular weight inorganic oxygen acid composed of a condensate of an inorganic oxygen acid having a single V- or VI-valent metal. .
ヘテロポリ酸の具体例として、リンモリブデン酸、リンタングステン酸、リンモリブドタングステン酸、リンモリブドバナジン酸、リンモリブドタングストバナジン酸、リンタングストバナジン酸、ケイタングステン酸、ケイモリブデン酸、ケイモリブドタングステン酸、ケイモリブドタングステントバナジン酸等が挙げられる。特に、重合活性の観点から、ヘテロポリ酸は、ケイモリブデン酸、ケイタングステン酸、リンモリブデン酸、リンタングステン酸から選択されることが好ましい。
Specific examples of the heteropoly acid include phosphomolybdic acid, phosphotungstic acid, phosphomolybdotungstic acid, phosphomolybdovanadic acid, phosphomolybdo tungstovanadic acid, phosphotungstovanadic acid, silicotungstic acid, silicomolybdic acid, silicomolybd. Examples thereof include tungstic acid and silico molybdenum tovanadic acid. In particular, from the viewpoint of polymerization activity, the heteropolyacid is preferably selected from silicomolybdic acid, silicotungstic acid, phosphomolybdic acid, and phosphotungstic acid.
イソポリ酸の具体例として、パラタングステン酸、メタタングステン酸等に例示されるイソポリタングステン酸、パラモリブデン酸、メタモリブデン酸等に例示されるイソポリモリブデン酸、メタポリバナジウム酸、イソポリバナジウム酸等が挙げられる。中でも、重合活性の観点から、イソポリタングステン酸であることが好ましい。
Specific examples of isopolyacids include paratungstic acid, isopolytungstic acid exemplified by metatungstic acid, paramolybdic acid, isopolymolybdic acid exemplified by metamolybdic acid, metapolyvanadate, isopolyvanadate. Etc. Among them, isopolytungstic acid is preferable from the viewpoint of polymerization activity.
≪ルイス酸≫
ルイス酸としては、例えば、ホウ素、スズ、チタン、リン、ヒ素及びアンチモンのハロゲン化物が挙げられ、具体的には三フッ化ホウ素、四塩化スズ、四塩化チタン、五フッ化リン、五塩化リン、五フッ化アンチモン及びその錯化合物又は塩が挙げられる。 <<Lewis acid>>
Examples of the Lewis acid include boron, tin, titanium, phosphorus, arsenic, and antimony halides, and specifically, boron trifluoride, tin tetrachloride, titanium tetrachloride, phosphorus pentafluoride, phosphorus pentachloride. , Antimony pentafluoride and complex compounds or salts thereof.
ルイス酸としては、例えば、ホウ素、スズ、チタン、リン、ヒ素及びアンチモンのハロゲン化物が挙げられ、具体的には三フッ化ホウ素、四塩化スズ、四塩化チタン、五フッ化リン、五塩化リン、五フッ化アンチモン及びその錯化合物又は塩が挙げられる。 <<Lewis acid>>
Examples of the Lewis acid include boron, tin, titanium, phosphorus, arsenic, and antimony halides, and specifically, boron trifluoride, tin tetrachloride, titanium tetrachloride, phosphorus pentafluoride, phosphorus pentachloride. , Antimony pentafluoride and complex compounds or salts thereof.
重合触媒の量は特に限定されるものでないが、全モノマーの合計に対して０．１ｐｐｍ以上５０ｐｐｍ以下であることが好ましく、０．１ｐｐｍ以上３０ｐｐｍ以下であることがより好ましい。特に好ましくは０．１ｐｐｍ以上１０ｐｐｍ以下である。（以下、単位のｐｐｍは全て質量標準である。）
The amount of the polymerization catalyst is not particularly limited, but it is preferably 0.1 ppm or more and 50 ppm or less, more preferably 0.1 ppm or more and 30 ppm or less, based on the total of all monomers. Particularly preferably, it is 0.1 ppm or more and 10 ppm or less. (Hereafter, all units of ppm are mass standards.)
本発明のポリアセタール共重合体の重合方法は、特に限定されるものではない。製造するにあたり、重合装置も特に限定されるものではなく、公知の装置が使用され、バッチ式、連続式等、いずれの方法も可能である。また、重合温度は６５℃以上１３５℃以下に保つことが好ましい。
カチオン重合触媒は、重合に影響のない不活性な溶剤で希釈して使用することが好ましい。 The polymerization method of the polyacetal copolymer of the present invention is not particularly limited. In the production, the polymerization apparatus is not particularly limited, and a known apparatus is used, and any method such as batch type and continuous type is possible. The polymerization temperature is preferably maintained at 65°C or higher and 135°C or lower.
It is preferable to use the cationic polymerization catalyst after diluting it with an inert solvent that does not affect the polymerization.
カチオン重合触媒は、重合に影響のない不活性な溶剤で希釈して使用することが好ましい。 The polymerization method of the polyacetal copolymer of the present invention is not particularly limited. In the production, the polymerization apparatus is not particularly limited, and a known apparatus is used, and any method such as batch type and continuous type is possible. The polymerization temperature is preferably maintained at 65°C or higher and 135°C or lower.
It is preferable to use the cationic polymerization catalyst after diluting it with an inert solvent that does not affect the polymerization.
重合後の重合触媒の失活は従来公知の方法で行うことができる。例えば、重合反応後、重合機より排出される生成反応物、重合機中の反応生成物に塩基性化合物又はその水溶液等を加えて行うこともできる。
重合触媒を中和し失活するための塩基性化合物は、特に限定されるものでない。重合及び失活の後、必要に応じて更に、洗浄、未反応モノマーの分離回収、乾燥等を従来公知の方法にて行う。 Deactivation of the polymerization catalyst after the polymerization can be performed by a conventionally known method. For example, after the polymerization reaction, a basic compound or an aqueous solution thereof may be added to the reaction product discharged from the polymerization machine or the reaction product in the polymerization machine.
The basic compound for neutralizing and deactivating the polymerization catalyst is not particularly limited. After polymerization and deactivation, washing, separation and recovery of unreacted monomers, drying and the like are further performed by a conventionally known method, if necessary.
重合触媒を中和し失活するための塩基性化合物は、特に限定されるものでない。重合及び失活の後、必要に応じて更に、洗浄、未反応モノマーの分離回収、乾燥等を従来公知の方法にて行う。 Deactivation of the polymerization catalyst after the polymerization can be performed by a conventionally known method. For example, after the polymerization reaction, a basic compound or an aqueous solution thereof may be added to the reaction product discharged from the polymerization machine or the reaction product in the polymerization machine.
The basic compound for neutralizing and deactivating the polymerization catalyst is not particularly limited. After polymerization and deactivation, washing, separation and recovery of unreacted monomers, drying and the like are further performed by a conventionally known method, if necessary.
上記のようにして得られるポリアセタール共重合体（Ｂ）は、その重量平均分子量（サイズ排除クロマトグラフィにて測定したポリメタクリル酸メチル換算値）が１００００～５０００００であることが好ましく、特に好ましくは２００００～１５００００である。また、末端基については、１Ｈ－ＮＭＲにより検出されるヘミホルマール末端基量（例えば、特開２００１－１１１４３公報記載の方法による）が０～４ｍｏｌ／ｋｇであることが好ましく、特に好ましくは０～２ｍｍｏｌ／ｋｇである。
The polyacetal copolymer (B) obtained as described above preferably has a weight average molecular weight (polymethyl methacrylate conversion value measured by size exclusion chromatography) of 10,000 to 500,000, particularly preferably 20,000 to It is 150,000. Regarding the terminal group, the amount of hemiformal terminal group detected by 1 H-NMR (for example, according to the method described in JP 2001-11143 A) is preferably 0 to 4 mol/kg, and particularly preferably 0 to It is 2 mmol/kg.
ヘミホルマール末端基量を上記範囲に制御するためには、重合に供するモノマー、コモノマー総量中の不純物、特に水分を２０ｐｐｍ以下にするのが好ましく、特に好ましくは１０ｐｐｍ以下である。
In order to control the amount of hemiformal terminal groups within the above range, it is preferable that the amount of impurities, especially water, in the total amount of monomers and comonomer to be used for polymerization is 20 ppm or less, particularly preferably 10 ppm or less.
＜その他成分＞
上記の如き本発明の樹脂組成物には、必要に応じて選択される各種安定剤を配合するのが好ましい。ここで用いられる安定剤としては、ヒンダードフェノール系化合物、窒素含有化合物、アルカリ或いはアルカリ土類金属の水酸化物、無機塩、カルボン酸塩等のいずれか１種または２種以上を挙げることができる。 <Other ingredients>
It is preferable to add various stabilizers selected as necessary to the resin composition of the present invention as described above. Examples of the stabilizer used here include any one or more of hindered phenol compounds, nitrogen-containing compounds, alkali or alkaline earth metal hydroxides, inorganic salts, and carboxylates. it can.
上記の如き本発明の樹脂組成物には、必要に応じて選択される各種安定剤を配合するのが好ましい。ここで用いられる安定剤としては、ヒンダードフェノール系化合物、窒素含有化合物、アルカリ或いはアルカリ土類金属の水酸化物、無機塩、カルボン酸塩等のいずれか１種または２種以上を挙げることができる。 <Other ingredients>
It is preferable to add various stabilizers selected as necessary to the resin composition of the present invention as described above. Examples of the stabilizer used here include any one or more of hindered phenol compounds, nitrogen-containing compounds, alkali or alkaline earth metal hydroxides, inorganic salts, and carboxylates. it can.
更に、本発明を阻害しない限り、必要に応じて、熱可塑性樹脂に対する一般的な添加剤、例えば耐候（光）安定剤、染料、顔料等の着色剤、滑剤、核剤、離型剤、帯電防止剤、界面活性剤、或いは、有機高分子材料、無機または有機の繊維状、粉体状、板状の充填剤等を１種または２種以上添加することができる。
Further, as long as it does not impair the present invention, if necessary, general additives to the thermoplastic resin, for example, weathering (light) stabilizer, colorants such as dyes and pigments, lubricants, nucleating agents, release agents, electrostatic charging One or more kinds of inhibitors, surfactants, organic polymer materials, inorganic or organic fibrous, powdery, plate-like fillers and the like can be added.
以下、実施例により本発明を具体的に説明するが、本発明がこれらに限定されるものではない。
実施例および比較例で使用したポリアセタール樹脂およびポリアセタール共重合体（Ｂ）は以下の通りである。 Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.
The polyacetal resin and the polyacetal copolymer (B) used in the examples and comparative examples are as follows.
実施例および比較例で使用したポリアセタール樹脂およびポリアセタール共重合体（Ｂ）は以下の通りである。 Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.
The polyacetal resin and the polyacetal copolymer (B) used in the examples and comparative examples are as follows.
＜ポリアセタール樹脂（Ａ）＞
ポリアセタール樹脂は、次のようにして調製した。
二軸パドルタイプの連続式重合機にトリオキサン（ＴＯＸ）９６．７質量％と１，３－ジオキソラン（ＤＯ）３．３質量％と８００ｐｐｍのメチラールの混合物を連続的に供給し、触媒として三フッ化ホウ素２０ｐｐｍを添加し重合を行った。
重合機吐出口より排出された重合体は、直ちにトリエチルアミン１０００ｐｐｍ含有水溶液を加えて粉砕、攪拌処理を行うことにより触媒の失活を行った。次いで、遠心分離により重合体を回収し、乾燥を行うことによりポリアセタール樹脂を得た。 <Polyacetal resin (A)>
The polyacetal resin was prepared as follows.
A twin-screw paddle type continuous polymerization machine was continuously fed with a mixture of 96.7% by mass of trioxane (TOX), 3.3% by mass of 1,3-dioxolane (DO), and 800 ppm of methylal, and used as a catalyst for trifluoride. Polymerization was carried out by adding 20 ppm of boron chloride.
The polymer discharged from the discharge port of the polymerization machine was immediately deactivated by adding an aqueous solution containing 1000 ppm of triethylamine, pulverizing and stirring the mixture. Then, the polymer was recovered by centrifugation and dried to obtain a polyacetal resin.
ポリアセタール樹脂は、次のようにして調製した。
二軸パドルタイプの連続式重合機にトリオキサン（ＴＯＸ）９６．７質量％と１，３－ジオキソラン（ＤＯ）３．３質量％と８００ｐｐｍのメチラールの混合物を連続的に供給し、触媒として三フッ化ホウ素２０ｐｐｍを添加し重合を行った。
重合機吐出口より排出された重合体は、直ちにトリエチルアミン１０００ｐｐｍ含有水溶液を加えて粉砕、攪拌処理を行うことにより触媒の失活を行った。次いで、遠心分離により重合体を回収し、乾燥を行うことによりポリアセタール樹脂を得た。 <Polyacetal resin (A)>
The polyacetal resin was prepared as follows.
A twin-screw paddle type continuous polymerization machine was continuously fed with a mixture of 96.7% by mass of trioxane (TOX), 3.3% by mass of 1,3-dioxolane (DO), and 800 ppm of methylal, and used as a catalyst for trifluoride. Polymerization was carried out by adding 20 ppm of boron chloride.
The polymer discharged from the discharge port of the polymerization machine was immediately deactivated by adding an aqueous solution containing 1000 ppm of triethylamine, pulverizing and stirring the mixture. Then, the polymer was recovered by centrifugation and dried to obtain a polyacetal resin.
＜ポリアセタール共重合体（Ｂ）＞
ポリアセタール共重合体（Ｂ）は、次のようにして調製した。
熱媒を通すことのできるジャケットと撹拌羽根を有する密閉オートクレーブ中に３００gのトリオキサン（ＴＯＸ）（ａ）を入れ、さらに（ｂ）成分として表１に記載の化合物、（ｃ）成分として１，３－ジオキソラン（ＤＯ）または１，４－ブタンジオールホルマール（ＢＤＦ）を、それぞれ表１に示した質量部になるように添加した。これら内容物を撹拌し、ジャケットに８０℃の温水を通して内部温度を約８０℃に保った後、触媒溶液（リンタングステン酸はギ酸メチルの溶液、トリフルオロメタンスルホン酸はシクロヘキサンの溶液）を表１に示す触媒濃度（対全モノマー）になる様に加えて重合を開始した。
５分後にこのオートクレーブへトリエチルアミン１０００ｐｐｍを含む水３００gを加えて反応を停止し、内容物を取り出して２００メッシュ以下に粉砕した。次いで、アセトンで洗浄した後に、乾燥を行うことによりポリアセタール共重合体を得た。 <Polyacetal copolymer (B)>
The polyacetal copolymer (B) was prepared as follows.
300 g of trioxane (TOX) (a) was placed in a closed autoclave having a jacket through which a heat medium can be passed and a stirring blade, and the compounds shown in Table 1 as the component (b) and 1,3 as the component (c). -Dioxolane (DO) or 1,4-butanediol formal (BDF) was added so as to be the mass parts shown in Table 1, respectively. After stirring the contents and passing warm water of 80°C through the jacket to keep the internal temperature at about 80°C, the catalyst solution (phosphotungstic acid solution in methyl formate, trifluoromethanesulfonic acid solution in cyclohexane) is shown in Table 1. Polymerization was initiated by adding in such a manner that the catalyst concentration indicated (relative to all monomers) was obtained.
After 5 minutes, 300 g of water containing 1000 ppm of triethylamine was added to the autoclave to stop the reaction, and the contents were taken out and pulverized to 200 mesh or less. Then, after washing with acetone, it was dried to obtain a polyacetal copolymer.
ポリアセタール共重合体（Ｂ）は、次のようにして調製した。
熱媒を通すことのできるジャケットと撹拌羽根を有する密閉オートクレーブ中に３００gのトリオキサン（ＴＯＸ）（ａ）を入れ、さらに（ｂ）成分として表１に記載の化合物、（ｃ）成分として１，３－ジオキソラン（ＤＯ）または１，４－ブタンジオールホルマール（ＢＤＦ）を、それぞれ表１に示した質量部になるように添加した。これら内容物を撹拌し、ジャケットに８０℃の温水を通して内部温度を約８０℃に保った後、触媒溶液（リンタングステン酸はギ酸メチルの溶液、トリフルオロメタンスルホン酸はシクロヘキサンの溶液）を表１に示す触媒濃度（対全モノマー）になる様に加えて重合を開始した。
５分後にこのオートクレーブへトリエチルアミン１０００ｐｐｍを含む水３００gを加えて反応を停止し、内容物を取り出して２００メッシュ以下に粉砕した。次いで、アセトンで洗浄した後に、乾燥を行うことによりポリアセタール共重合体を得た。 <Polyacetal copolymer (B)>
The polyacetal copolymer (B) was prepared as follows.
300 g of trioxane (TOX) (a) was placed in a closed autoclave having a jacket through which a heat medium can be passed and a stirring blade, and the compounds shown in Table 1 as the component (b) and 1,3 as the component (c). -Dioxolane (DO) or 1,4-butanediol formal (BDF) was added so as to be the mass parts shown in Table 1, respectively. After stirring the contents and passing warm water of 80°C through the jacket to keep the internal temperature at about 80°C, the catalyst solution (phosphotungstic acid solution in methyl formate, trifluoromethanesulfonic acid solution in cyclohexane) is shown in Table 1. Polymerization was initiated by adding in such a manner that the catalyst concentration indicated (relative to all monomers) was obtained.
After 5 minutes, 300 g of water containing 1000 ppm of triethylamine was added to the autoclave to stop the reaction, and the contents were taken out and pulverized to 200 mesh or less. Then, after washing with acetone, it was dried to obtain a polyacetal copolymer.
比較として下記ジグリシジル化合物（グリシジルエーテル基が２個のもの）を本発明の（ｂ）成分に替えて使用したポリアセタール共重合体の製造を試みた。
For comparison, an attempt was made to produce a polyacetal copolymer using the following diglycidyl compound (having two glycidyl ether groups) in place of the component (b) of the present invention.
＜実施例および比較例＞
表１に示す各種成分を表１に示す割合で添加混合し、ベント付き二軸の押出機で溶融混練してペレット状の組成物を調製した。
なお、全ての試料において、溶融混錬の際に（Ａ）成分と（Ｂ）成分の合計量１００質量部に対してエチレンビス（オキシエチレン）ビス[３－(５－ｔｅｒｔ―ブチル－４－ヒドロキシ－ｍ－トリル）プロピオネート]（ＢＡＳＦ製 ＩＲＧＡＮＯＸ２４５）０．３５質量部とメラミン ０．０８質量部を添加した。 <Examples and Comparative Examples>
The various components shown in Table 1 were added and mixed in the proportions shown in Table 1, and melt-kneaded with a vented twin-screw extruder to prepare pelletized compositions.
In all the samples, 100 parts by weight of the total amount of the components (A) and (B) were mixed with ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-) during the melt kneading Hydroxy-m-tolyl)propionate] (IRGANOX245 manufactured by BASF) and 0.08 part by weight of melamine were added.
表１に示す各種成分を表１に示す割合で添加混合し、ベント付き二軸の押出機で溶融混練してペレット状の組成物を調製した。
なお、全ての試料において、溶融混錬の際に（Ａ）成分と（Ｂ）成分の合計量１００質量部に対してエチレンビス（オキシエチレン）ビス[３－(５－ｔｅｒｔ―ブチル－４－ヒドロキシ－ｍ－トリル）プロピオネート]（ＢＡＳＦ製 ＩＲＧＡＮＯＸ２４５）０．３５質量部とメラミン ０．０８質量部を添加した。 <Examples and Comparative Examples>
The various components shown in Table 1 were added and mixed in the proportions shown in Table 1, and melt-kneaded with a vented twin-screw extruder to prepare pelletized compositions.
In all the samples, 100 parts by weight of the total amount of the components (A) and (B) were mixed with ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-) during the melt kneading Hydroxy-m-tolyl)propionate] (IRGANOX245 manufactured by BASF) and 0.08 part by weight of melamine were added.
なお、比較例２および３では、ポリアセタール共重合体（Ｂ）に関し、表１記載の条件では、他の重合条件は実施例と同一にしても、重合反応は観測されなかった。
In Comparative Examples 2 and 3, regarding the polyacetal copolymer (B), no polymerization reaction was observed under the conditions shown in Table 1 even if the other polymerization conditions were the same as those of the examples.
＜評価＞
実施例における特性評価項目及び評価方法は以下の通りである。
[曲げ試験]
機械物性としてＩＳＯ１７８に準拠した曲げ弾性率（ＦＭ）を測定した。測定室の条件は、２３℃５５％ＲＨとした。 <Evaluation>
The characteristic evaluation items and evaluation methods in the examples are as follows.
[Bending test]
As a mechanical property, a flexural modulus (FM) according to ISO178 was measured. The conditions of the measuring chamber were 23° C. and 55% RH.
実施例における特性評価項目及び評価方法は以下の通りである。
[曲げ試験]
機械物性としてＩＳＯ１７８に準拠した曲げ弾性率（ＦＭ）を測定した。測定室の条件は、２３℃５５％ＲＨとした。 <Evaluation>
The characteristic evaluation items and evaluation methods in the examples are as follows.
[Bending test]
As a mechanical property, a flexural modulus (FM) according to ISO178 was measured. The conditions of the measuring chamber were 23° C. and 55% RH.
表１から、本発明の組成物において、機械物性（曲げ弾性率）に優れていることがわかる。
It can be seen from Table 1 that the composition of the present invention has excellent mechanical properties (flexural modulus).
Claims (7)
- ポリアセタール樹脂（Ａ）１００質量部に対して、
少なくともトリオキサン（ａ）、エポキシ基および環状アセタール基から選ばれる少なくとも一種のトリオキサン共重合性官能基ならびにアルコキシシリル基を有し、該トリオキサン共重合性官能基と該アルコキシシリル基は、炭素－炭素結合またはエーテル結合から選択される結合連鎖のみによって結合している化合物（ｂ）とを共重合して得られるポリアセタール共重合体（Ｂ）を０．１～１００質量部を混合して得られるポリアセタール樹脂組成物。 With respect to 100 parts by mass of the polyacetal resin (A),
At least one trioxane copolymerizable functional group selected from trioxane (a), an epoxy group and a cyclic acetal group and an alkoxysilyl group are contained, and the trioxane copolymerizable functional group and the alkoxysilyl group have a carbon-carbon bond. Alternatively, a polyacetal resin obtained by mixing 0.1 to 100 parts by mass of a polyacetal copolymer (B) obtained by copolymerizing the compound (b) bonded only by a bond chain selected from an ether bond. Composition. - 前記共重合体（Ｂ）が、パーフルオロアルカンスルホン酸、ヘテロポリ酸、イソポリ酸から選ばれる１種以上を重合触媒として得られるポリアセタール共重合体（Ｂ）である請求項１記載のポリアセタール樹脂組成物。 The polyacetal resin composition according to claim 1, wherein the copolymer (B) is a polyacetal copolymer (B) obtained by using at least one selected from perfluoroalkanesulfonic acid, heteropolyacid, and isopolyacid as a polymerization catalyst. .
- 前記共重合体（Ｂ）が、コモノマーとしてさらに（ｃ）炭素数２以上のオキシアルキレン基を環内に有する環状アセタール化合物を共重合して得られたポリアセタール共重合体（Ｂ）である請求項１または２記載のポリアセタール樹脂組成物。 The copolymer (B) is a polyacetal copolymer (B) obtained by copolymerizing (c) a cyclic acetal compound having an oxyalkylene group having 2 or more carbon atoms in the ring as a comonomer. The polyacetal resin composition according to 1 or 2.
- 前記アルコキシシリル基が、トリアルコキシシリル基およびジアルコキシシリル基から選ばれる少なくとも一種である請求項１～３記載のポリアセタール樹脂組成物。 The polyacetal resin composition according to claim 1, wherein the alkoxysilyl group is at least one selected from a trialkoxysilyl group and a dialkoxysilyl group.
- 前記（ｂ）化合物が、２-(３、４-エポキシシクロヘキシル)-エチルトリメトキシシランおよび２-(３、４-エポキシシクロヘキシル)-エチルトリエトキシシランから選ばれる少なくとも１種である請求項１～３記載のポリアセタール樹脂組成物。 The compound (b) is at least one selected from 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)-ethyltriethoxysilane. The polyacetal resin composition according to item 3.
- ポリアセタール樹脂（Ａ）がアセタールコポリマーである請求項１～５記載のポリアセタール樹脂組成物。 The polyacetal resin composition according to claims 1 to 5, wherein the polyacetal resin (A) is an acetal copolymer.
- ポリアセタール樹脂（Ａ）１００質量部に対して、
少なくともトリオキサン（ａ）、エポキシ基および環状アセタール基から選ばれる少なくとも一種のトリオキサン共重合性官能基ならびにアルコキシシリル基を有し、該トリオキサン共重合性官能基と該アルコキシシリル基は、炭素－炭素結合またはエーテル結合から選択される結合連鎖のみによって結合している化合物（ｂ）とを共重合して得られるポリアセタール共重合体（Ｂ）を０．１～１００質量部を混合して得られるポリアセタール樹脂組成物の製造方法であって、
該共重合体（Ｂ）が、パーフルオロアルカンスルホン酸、ヘテロポリ酸、イソポリ酸から選ばれる１種以上を重合触媒として得られるポリアセタール共重合体（Ｂ）であるポリアセタール樹脂組成物の製造方法。
With respect to 100 parts by mass of the polyacetal resin (A),
At least one trioxane copolymerizable functional group selected from trioxane (a), an epoxy group and a cyclic acetal group and an alkoxysilyl group are contained, and the trioxane copolymerizable functional group and the alkoxysilyl group have a carbon-carbon bond. Alternatively, a polyacetal resin obtained by mixing 0.1 to 100 parts by mass of a polyacetal copolymer (B) obtained by copolymerizing the compound (b) bonded only by a bond chain selected from an ether bond. A method for producing a composition,
A method for producing a polyacetal resin composition, wherein the copolymer (B) is a polyacetal copolymer (B) obtained by using at least one selected from perfluoroalkanesulfonic acid, heteropolyacid, and isopolyacid as a polymerization catalyst.
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