TWI763816B - Polyacetal resin composition - Google Patents

Abstract

[Problem] To provide a polyacetal resin composition having excellent mechanical properties such as tensile strength, tensile elongation, flexural strength, and impact resistance, and particularly excellent creep properties. [Solution] A polyacetal resin composition containing, with respect to 100 parts by mass of the (A) polyacetal resin: (B) a compound selected from the group consisting of a blocked isocyanate compound, a polyurethane resin, and a silane coupling agent At least one surface-treated glass-based inorganic filler of 1 to 100 parts by mass; (C) 0.1 to 10 parts by mass of polyfunctional isocyanate compounds; (D) 0.001 to 3 parts by mass of boric acid compounds; and (E) 0.002 to 10 parts by mass of the triazine derivative having a nitrogen-containing functional group.

Description

Polyacetal resin composition

The present invention relates to a polyacetal resin composition.

Polyacetal resin has excellent properties in mechanical properties, thermal properties, electrical properties, sliding properties, formability, impact resistance, dimensional stability of molded products, etc., and is widely used as structural materials and mechanical parts in electrical equipment, automobiles parts, precision mechanical parts, etc. In addition, it is known to mix reinforcing materials such as glass-based inorganic fillers in order to improve the mechanical properties of polyacetal resin, such as strength and rigidity. Reinforcing materials such as inorganic fillers.

However, since the polyacetal resin lacks activity, and the glass-based inorganic filler also lacks activity, simply mixing the glass-based inorganic filler with the polyacetal resin and only melting and kneading the two will not have sufficient adhesion. It is often impossible to achieve the expected improvement in mechanical properties. Here, various methods for improving the adhesion between the polyacetal resin and the glass-based inorganic filler and improving the mechanical properties are proposed.

For example, it is known that a glass-based inorganic filler and a boric acid compound are added to a polyacetal resin, and the glass-based inorganic filler is further surface-treated with a specific silane compound (see Patent Document 1). A glass-based inorganic filler surface-treated with a urethane-based resin is added, and the pH is adjusted using phosphorous acid (see Patent Document 2) and the like. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. Hei 09-151298 [Patent Document 2] Japanese Patent Publication No. 2000-335942

[Problems to be solved by the invention]

However, these methods all increase the chemical activity of the glass-based inorganic filler and obtain mechanical properties such as tensile strength, tensile elongation, and flexural strength. In recent years, in addition to these mechanical properties, the provision of polyacetal resins that exhibit impact resistance, durability, and especially creep properties has also been demanded. Conventional polyacetal resins are required to improve durability such as creep properties. There is also room for improvement in sexuality.

The present invention was made to solve the above-mentioned problems, and an object thereof is to provide a polyacetal resin composition excellent in mechanical properties such as tensile strength, tensile elongation, flexural strength, and impact resistance, and particularly excellent in creep properties. [Technical means to solve the problem]

In order to solve the above-mentioned problems, the inventors of the present invention have found, as a result of diligent research, that with respect to polyacetal resins, by using specific glass-based inorganic fillers, polyfunctional isocyanate compounds, boric acid compounds, and nitrogen-containing functional groups An azine derivative can maintain high mechanical properties and can improve creep properties, thereby completing the present invention. The present invention is as follows.

1. A polyacetal resin composition containing, relative to 100 parts by mass of (A) a polyacetal resin: (B) at least one selected from the group consisting of a blocked isocyanate compound, a polyurethane resin, and a silane coupling agent; 1 to 100 parts by mass of a surface-treated glass-based inorganic filler; (C) 0.1 to 10 parts by mass of a polyfunctional isocyanate compound; (D) 0.001 to 3 parts by mass of a boric acid compound; and ( E) 0.002 to 10 parts by mass of a triazine derivative having a nitrogen-containing functional group.

2. The polyacetal resin composition according to the above 1, wherein the (C) polyfunctional isocyanate compound is selected from the group consisting of 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, 1,6-hexanol A compound of at least one of methylene diisocyanate, 2,4-toluene diisocyanate, and 2,6-toluene diisocyanate.

3. The polyacetal resin composition according to the above 1, wherein the (C) polyfunctional isocyanate compound is selected from the group consisting of 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, 1,6-hexanol A compound of at least one of methylene diisocyanate, 2,4-toluene diisocyanate, and a polymer of 2,6-toluene diisocyanate.

4. The polyacetal resin composition according to the above 1, wherein the (C) polyfunctional isocyanate compound is selected from the group consisting of 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, 1,6-hexanol A compound of at least one of a trimer of methylene diisocyanate, 2,4-toluene diisocyanate, and 2,6-toluene diisocyanate.

5. The polyacetal resin composition according to any one of 1 to 4 above, wherein the (D) boric acid compound is orthoboric acid.

6. The polyacetal resin composition according to any one of the aforementioned 1 to 5, wherein the aforementioned (E) triazine derivative having a nitrogen-containing functional group is selected from melamine, benzoguanamine and CTUguanamine. at least one compound. 7. The polyacetal resin composition according to any one of 1 to 6, wherein the (B) glass-based inorganic filler is at least one selected from the group consisting of glass fibers, glass beads, ground glass fibers, and glass flakes glass-based inorganic fillers. [Inventive effect]

According to the present invention, a polyacetal resin composition can be provided which is excellent in mechanical properties such as tensile strength, tensile elongation, flexural strength, and impact resistance, and in particular, is excellent in creep properties.

Specific embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present invention.

<Polyacetal resin composition> The polyacetal resin composition of the present invention contains, with respect to 100 parts by mass of the (A) polyacetal resin: (B) a compound selected from the group consisting of blocked isocyanate compounds and polyurethane 1 to 100 parts by mass of a glass-based inorganic filler in which at least one of the resin and the silane coupling agent is surface-treated; (C) 0.1 to 10 parts by mass of a polyfunctional isocyanate compound; (D) 0.001 parts by mass of a boric acid compound parts to 3 parts by mass; and (E) 0.002 to 10 parts by mass of the triazine derivative having a nitrogen-containing functional group.

In the present invention, (A) the reactive terminal group of the polyacetal resin and (B) a glass-based system surface-treated via at least one selected from the group consisting of blocked isocyanate compounds, polyurethane resins, and silane coupling agents The composite reaction of inorganic fillers is further promoted by the synergistic effect of the coexistence of (C) polyfunctional isocyanate compound, (D) boronic acid compound and (E) triazine derivative having a nitrogen-containing functional group As a result, it is presumed that the creep characteristics are improved.

<(A) Polyacetal resin> The (A) polyacetal resin of the present invention is a polymer compound having an oxymethylene group (—CH ₂ O—) as a main constituent unit, and may be a polyoxymethylene group. base homopolymer, or one of copolymers, terpolymers or block polymers containing oxymethylene as the main repeating unit and a small amount of other constituent units, among which other The constituent unit is, for example, a comonomer unit of ethylene oxide, 1,3-dioxolane, 1,4-butanediol formal (1,4-butanediol formal), and the like.

In addition, the molecules of the polyacetal resin are not only linear, but may be copolymerized with a comonomer having a glycidyl ether structure to have a branched or cross-linked structure, or may be a known modified polymer into which other organic groups are introduced. Formaldehyde may also be a mixture of a linear resin and a resin having a branched and cross-linked structure.

The degree of polymerization of the polyacetal resin is not particularly limited, as long as it has melt molding processability (for example, a melt flow rate value (MFR) at 190° C. under a load of 2160 g) of 1.0 g/10 minutes or more and 100g/10min or less).

<(B) Glass-based inorganic filler surface-treated with at least one selected from the group consisting of blocked isocyanate compounds, polyurethane resins, and silane coupling agents> (B) The glass-based inorganic filler is selected from A glass-based inorganic filler surface-treated with at least one of a self-blocking isocyanate compound, a polyurethane resin, and a silane coupling agent. When the glass-based inorganic filler is surface-treated with a plurality of compounds, the timing of the surface treatment with the individual compounds is not considered.

For example, the glass-based inorganic filler may be surface-treated with a blocked isocyanate compound or polyurethane resin, and then surface-treated with other components, or may be surface-treated with a silane coupling agent, and then treated with other components. Ingredients are surface treated.

Whether the glass-based inorganic filler is surface-treated with at least one selected from the group consisting of blocked isocyanate compounds, polyurethane resins, and silane coupling agents, and the polymer contained in the glass-based inorganic filler is extracted by solvent. The acetal resin composition can be distinguished by analyzing the components.

<<Blocked Isocyanate Compound>> The isocyanate compound used as a raw material of the blocked isocyanate compound of the present invention is not particularly limited and can be used as long as it is a polyfunctional isocyanate compound having two or more isocyanate groups in one molecule.

For example, aliphatic and aromatic isocyanate compounds are mentioned, and an aliphatic isocyanate compound is particularly preferred from the viewpoint of compatibility or suitability with polyacetal resins. In particular, bifunctional aliphatic isocyanate compounds and polyisocyanates obtained by polymerizing such diisocyanates are preferred.

Examples of the aliphatic diisocyanate include linear, branched, and alicyclic compounds, and the linear and branched isocyanates are preferably those having 4 to 30 carbon atoms, and more preferably those having 5 to 10 carbon atoms. . Specifically, tetramethylene-1,4-diisocyanate, pentamethylene-1,5-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene Methyl-1,6-diisocyanate, lysine diisocyanate, etc.

Moreover, as an alicyclic diisocyanate, it is preferable that it is carbon number 8 or more and 18 or less, and it is more preferable that it is carbon number 10 or more and 15 or less. Specifically, isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 4,4'- dicyclohexylmethane diisocyanate, etc. are mentioned.

As aromatic diisocyanate, xylylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, etc. are mentioned.

Further, examples of polyisocyanates include compounds having at least two isocyanate groups per molecule, such as various aromatic diisocyanates such as tolylene diisocyanate or diphenylmethane diisocyanate; Diisocyanates, various aralkyl diisocyanates of α,α,α',α'-tetramethylm-xylylene diisocyanate; such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate or isophor Aliphatic diisocyanates of ketone diisocyanates, prepolymers containing isocyanate groups obtained by addition reaction with polyols, and prepolymers with uretdione rings obtained by cyclizing dimerization of various diisocyanates mentioned above Polymers, prepolymers with isocyanurate rings obtained by cyclizing and trimerizing the aforementioned various diisocyanates, or prepolymers with a biuret structure obtained by reacting the aforementioned various diisocyanates with water Adducts, polyisocyanates, etc.

Among them, hexamethylene diisocyanate, biuret of hexamethylene diisocyanate, and cyclic dimer are preferred from the viewpoints of impact resistance and durability of the obtained composition, and ease of industrial availability. , or a cyclic trimer of hexamethylene diisocyanate. Furthermore, the above-mentioned compounds may be used in combination of two or more.

Furthermore, as the blocked isocyanate compound of the present invention, there is no particular limitation and can be used as long as the reactive group of the above-mentioned isocyanate compound is blocked by a conventional method with a known blocking agent.

Specific examples of the blocking agent include oxime-based blocking agents such as methyl ethyl ketoxime, acetone oxime, cyclohexanone oxime, acetophenone oxime, and benzophenone oxime; m-cresol , phenol-based end-capping agents such as diphenol; alcohol-based end-capping agents such as methanol, ethanol, butanol, 2-ethylhexanol, cyclohexanol, ethylene glycol monoethyl ether; ε-caprolactone Lactamide-based end-capping agents such as amide; diketone-based end-capping agents such as diethyl malonate, acetylacetate, etc.; methylmercaptan-based end-capping agents such as thiophenol; Urea-based end-capping agents such as thiourea; pyrazole-based end-capping agents such as dimethylpyrazole; imidazole-based end-capping agents; carbamic acid-based end-capping agents; bisulfite, but not limited to these. Among them, lactamide-based end-capping agents, oxime-based end-capping agents, diketone-based end-capping agents, and pyrazole-based end-capping agents are preferably used.

<< Urethane Resin>> The urethane resin used in the present invention is preferably composed of organic diisocyanate, polymer polyol, Furthermore, if necessary, a chain extender and/or a crosslinking agent is conventionally known, and it is preferably used in the form of an aqueous dispersion such as emulsification and dispersion. Specific examples of the organic diisocyanate include, for example, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene Diisocyanate, 4,4'-dibenzyldiisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, o-xylylene diisocyanate , Aromatic diisocyanates such as m-xylyl diisocyanate and p-xylyl diisocyanate, aliphatic diisocyanates such as ethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, etc., isophorone Alicyclic diisocyanates such as diisocyanate and 4,4'-dicyclohexylmethane diisocyanate. Preferable specific examples of the polymer polyol include, for example, polyethylene adipate diol, polybutylene adipate diol, and polyethylene butylene adipate diol. , polyneopentyl adipate diol, polyneopentyl phthalate diol, poly(ε-caprolactone) diol, polyvalerolactone diol, polyhexamethylene Polyester polyols such as carbonate diols, polyethylene glycol, polypropylene glycol, polyoxyethylideneoxypropylene glycol, polyoxytetramethylene glycol, bisphenol-based ethylene oxide and/or cyclic Polyether polyols such as oxypropane adducts. As the chain extender and/or the crosslinking agent, an active hydrogen-containing compound having a number average molecular weight of 60 to 500 is preferable, and examples thereof include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4- Butanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, neopentyl glycol, 1,4-bis(hydroxymethyl)cyclohexane, 1,4-bis( Divalent alcohols such as hydroxyethyl)benzene and 2,2-bis(4,4-hydroxycyclohexyl)propane, trivalent alcohols such as glycerol and trimethylolpropane, pentaerythritol, diglycerol, α-methylglucose Polyvalent alcohols such as glycosides, sorbitol, dipentaerythritol, 4-8 valent alcohols such as glucose, polyvalent phenols such as pyrogallol, catechol, hydroquinone, bisphenol A, Bisphenols such as bisphenol F and bisphenol S, aliphatic polyamines such as ethylenediamine, hexamethylenediamine, and diethylenetriamine, isophoronediamine, 4,4 Alicyclic polyamines such as '-dicyclohexylmethanediamine, aromatic polyamines such as 4,4'-diaminodiphenylmethane, and aromatic alicyclic polyamines such as xylylenediamine Polyamines such as amines. In the present invention, among the organic isocyanates listed above, tolylene diisocyanate or xylylene diisocyanate is preferably used as the isocyanate component, and the polyol component of the polyurethane is higher than the above-mentioned organic isocyanates. Among the molecular polyols, polycaprolactone diol is preferred. In addition, chopped fibers using a polyurethane resin composed of toluene diisocyanate or xylylene diisocyanate and poly(ε-caprolactone) glycol are more preferable because they have extremely high bundling properties.

<<Silane Coupling Agent>> The silane coupling agent of the present invention only has a functional group (for example, vinylalkoxysilane, epoxyalkoxysilane, mercaptoalkoxysilane, allylalkoxysilane, amine silane) can exert the effect of the present invention, but it is preferably an amino silane coupling agent. The aminosilane coupling agent is a compound containing, in one molecule, a functional group bonded to a silicon atom and a nitrogen atom of an alkoxy group.

Specific examples of the aminosilane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, and γ-aminopropyltriethoxysilane. -Aminopropylmethyldiethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-amino Propyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, N ,N'-bis[3-(triethoxysilyl)propyl]ethylidene diamine, N,N'-bis[3-(methyldimethoxysilyl)propyl]ethylidene Diamine, N,N'-bis[3-(trimethoxysilyl)propyl]hexamethylenediamine, N,N'-bis[3-(triethoxysilyl)propyl]hexamethylene Methylenediamine, etc.

As the above-mentioned aminosilane coupling agent, among them, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, and γ-aminopropylmethyldimethoxysilane are preferably mentioned. Silane, γ-aminopropylmethyldiethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, and N-(β-aminoethyl)-γ -Aminopropyltriethoxysilane, more preferably γ-aminopropyltrimethoxysilane and γ-aminopropyltriethoxysilane.

Moreover, these silane coupling agents can be used individually or in combination of 2 or more types.

Other silane coupling agents having functional groups (for example, vinylalkoxysilane, epoxyalkoxysilane, mercaptoalkoxysilane, allylalkoxysilane) may be used in combination.

"Glass-based inorganic fillers"

The glass-based inorganic fillers used in this embodiment include fibrous (glass fibers), granular (glass beads), granular (polished glass fibers), plate-shaped (glass flakes), and hollow fillers , and there are no special restrictions.

In operation, the glass fiber is preferably cut into chopped fibers of about 2 mm to 8 mm. Moreover, as a diameter of a glass fiber, it is suitable to use what is 5 micrometers - 15 micrometers normally, Preferably it is 7 micrometers - 13 micrometers.

The surface treatment amount of the blocked isocyanate is 0.1 to 5 parts by mass, preferably 0.3 to 3 parts by mass, relative to 100 parts by mass of the glass-based inorganic filler. The surface treatment amount of the polyurethane resin is 0.1 to 5 parts by mass, preferably 0.2 to 2 parts by mass, relative to 100 parts by mass of the glass-based inorganic filler. The surface treatment amount of the silane coupling agent is 0.005 to 10 parts by mass, preferably 0.01 to 5 parts by mass, relative to 100 parts by mass of the glass-based inorganic filler.

The compounding amount of the (B) glass-based inorganic filler is 1 part by mass to 100 parts by mass, preferably 5 parts by mass to 80 parts by mass, and particularly preferably 10 parts by mass to 60 parts by mass relative to 100 parts by mass of the polyacetal resin share. The content of the glass-based inorganic filler can be appropriately selected according to the improvement of the creep characteristics of the molded product and the ease of molding.

When the glass-based inorganic filler is subjected to surface treatment, a known method can be used. Generally, at least one selected from a blocked isocyanate compound, a polyurethane resin, and a silane coupling agent is used as a solution dissolved in an organic solvent. , used as an opalescent dispersion or dispersed in water.

<(C) Polyfunctional isocyanate compound> As the (C) polyfunctional isocyanate compound of the present invention, any polyfunctional isocyanate compound having two or more isocyanate groups in one molecule can be used without particular limitation, and can be used as The isocyanate compound of the raw material of the blocked isocyanate compound of this invention.

Among them, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 2,4-toluene diisocyanate or 2,6-toluene diisocyanate are preferred The polymer, especially the trimer. Creep characteristics can be sharply improved by being more than a trimer. Furthermore, the above-mentioned compounds may be used in combination of two or more. The compounding quantity of a polyfunctional isocyanate is 0.1-10 mass parts with respect to 100 mass parts of polyacetal resins, Preferably it is 0.3-3 mass parts.

<(D) Boric acid compound> The type of the (D) boric acid compound of the present invention is not particularly limited, and may be one of orthoboric acid, metaboric acid, tetraboric acid, and the like. Among them, orthoboric acid is preferred. The compounding amount of the (D) boric acid compound is 0.001 to 3.0 parts by mass relative to 100 parts by mass of the polyacetal resin, and preferably 0.005 to 0.2 parts by mass in consideration of creep characteristics.

<(E) Triazine Derivative Having Nitrogen-Containing Functional Group> The (E) triazine derivative having a nitrogen-containing functional group of the present invention has the effect of improving not only creep resistance but also thermal stability. The (E) triazine derivatives having a nitrogen-containing functional group used in the present invention are specifically melamine, N-butyl melamine, N-phenyl melamine, N,N'-diphenyl melamine, N, N'-diallylmelamine, N,N',N''-triphenylmelamine, benzoguanamine, methylguanamine, 2,4-diamino-6-butyl-sym-triazine , diamide cyanurate, 2,4-diamino-6-benzyloxy-sym-triazine, 2,4-diamino-6-butoxy-sym-triazine, 2, 4-Diamino-6-cyclohexyl-sym-triazine, 2,4-diamino-6-chloro-sym-triazine, 2,4-diamino-6-mercapto-sym-triazine, 2,4-Dihydroxy-6-amino-sym-triazine [another name (ammelide)], 1,1-bis(3,5-diamino-2,4,6-triazinyl) ) methane, 1,2-bis(3,5-diamino-2,4,6-triazinyl)ethane [another name (succinoguanamine)], 1,3-bis(3,5-diamino) -2,4,6-triazinyl) propane, 1,4-bis(3,5-diamino-2,4,6-triazinyl) butane, methylene melamine, ethylidene Dimelamine, triguanamine, 3,9-bis[2-(3,5-diamino-2,4,6-triazaphenyl)ethyl]-2,4,8,10-tetra Oxaspiro[5.5]undecane (CTUguanamine), 3,9-bis[1-(3,5-diamino-2,4,6-triazaphenyl)methyl]- 2,4,8,10-Tetraoxaspiro[5.5]undecane, 3,9-bis[2-(3,5-diamino-2,4,6-triazaphenyl) -2-Methylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 3,9-bis[1-(3,5-diamino-2,4 ,6-Triazaphenyl)-1,1-dimethylmethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 3,9-bis[3- (3,5-Diamino-2,4,6-triazaphenyl)-1,1-dimethylpropyl]-2,4,8,10-tetraoxaspiro[5.5] Undecane, 3,9-bis[3-(3,5-diamino-2,4,6-triazaphenyl)-2,2-dimethylpropyl]-2,4,8 , 10-Tetraoxaspiro[5.5]undecane, melamine cyanurate, ethylene dimelamine cyanurate, triguanamine cyanurate, etc.

One type of these melamine derivatives may be used, or two or more types may be used in combination. Preferred are benzoguanamine, CTU guanamine, and melamine, and particularly preferred is melamine.

The compounding amount of the (E) triazine derivative having a nitrogen-containing functional group of the present invention is preferably 0.002 to 10 parts by mass, more preferably 0.01 to 2 parts by mass relative to 100 parts by mass of the polyacetal resin , particularly preferably 0.03 part by mass to 1 part by mass.

<Other additives> The polyacetal resin composition of the present invention may further contain a glass-based inorganic filler surface-treated with a known coupling agent other than a silane coupling agent. The coupling agent is used to improve the wettability or adhesion between the glass-based inorganic filler and the polyacetal resin, and is, for example, a titanate-based, aluminum-based, chromium-based, zirconium-based, or borane-based coupling agent.

Furthermore, as long as the performance of the molded article, which is the object of the present invention, does not significantly degrade, one or two or more kinds of known inorganic, organic, and metallic fibrous fillers other than glass-based inorganic fillers may be compounded and blended. , plate, powder and other fillers. As an example of such a filler, talc, mica, wollastonite, carbon fiber, etc. are mentioned, but it is not limited to these.

Furthermore, various known stabilizers and additives can be blended. Examples of the stabilizer include any one or two or more of hindered phenol-based compounds, hydroxides and carbonates of alkali or alkaline earth metals, and the like. The additives are general additives to thermoplastic resins, for example, any one or two or more of colorants such as dyes and pigments, lubricants, nucleating agents, release agents, antistatic agents, and surfactants.

<The manufacturing method of a polyacetal resin composition> The manufacture of the polyacetal resin composition of this invention can be easily manufactured by the well-known method generally used as a conventional resin composition manufacturing method. For example, it is possible to use a single-screw or twin-screw extruder to knead and extrude after mixing the ingredients to prepare pellets, and then to form the method to prepare pellets (master batches) with different compositions first, This pellet is mixed (diluted) in a predetermined amount, and is subjected to molding, and any method such as a method of obtaining a molded product of the desired composition after molding.

In addition, in the production of the polyacetal resin composition, a preferred method is to powder a part or all of the polyacetal resin serving as the matrix, mix it with other components, and then perform extrusion or the like to disperse the additives. Sex is good. [Example]

The following examples are shown to describe the present invention more specifically, but the present invention is not limited to the following examples. In addition, unless otherwise stated, each evaluation was performed in the environment of 23 degreeC and 55%RH.

<Production of polyacetal resin composition> In 100 parts by mass of the (A) polyacetal resin composition, (B) a glass-based inorganic filler and (C) were blended in the amounts shown in Tables 1 and 2. The polyfunctional isocyanate compound, (D) boric acid compound and (E) triazine derivative having a nitrogen-containing functional group were melt-kneaded in an extruder with a cylinder temperature of 200°C to produce granular polycondensation of Examples and Comparative Examples. Formaldehyde resin composition. The various materials used are as follows.

[(A) Polyacetal resin]

(A1) Polyacetal resin (polyacetal copolymer obtained by copolymerizing 96.7 mass % of trioxane and 3.3 mass % of 1,3-ditetrahydrofuran (melt index (measured at 190° C., load 2160 g)): 9 g/ 10min)).

[(B) 100 parts by mass of surface-treated glass-based inorganic filler]

(B1) Via polyurethane resin (reaction product of xylylene diisocyanate and polycaprolactone diol) 0.8 parts by mass, silane coupling agent (γ-aminopropyl triethoxysilane) 0.02 Parts by mass of chopped fibers having a surface-treated diameter of 13 μm.

(B2) Conducted via 0.8 parts by mass of polyurethane resin (reaction product of toluene diisocyanate and polycaprolactone diol) and 0.02 part by mass of silane coupling agent (γ-aminopropyltriethoxysilane) Surface-treated chopped fibers with a diameter of 10 μm.

(B3) Via polyurethane resin (reaction product of xylylene diisocyanate and polycaprolactone diol) 0.3 parts by mass, silane coupling agent (γ-aminopropyl triethoxysilane) 0.02 Parts by mass, 1.2 parts by mass of blocked isocyanate of methyl ethyl ketoxime-terminated hexamethylene diisocyanate, surface-treated chopped fibers having a diameter of 10 μm.

(B4) The chopped fiber of diameter 10 micrometers surface-treated via 0.7 mass part of polyurethane resin (reaction material of toluene diisocyanate and polycaprolactone diol).

(B5) A chopped fiber having a diameter of 10 μm that was surface-treated via 1.2 parts by mass of the blocked isocyanate of the methyl ethyl ketoxime-terminated hexamethylene diisocyanate trimer.

[Surface Treatment Method for Glass-Based Inorganic Fillers]

At least one selected from a blocked isocyanate compound, a polyurethane resin (opalescent), and a silane coupling agent is mixed alone or in combination to obtain a surface treatment agent for a glass-based inorganic filler. This surface treatment agent is coated and dried on a glass-based inorganic filler to obtain a surface-treated glass-based inorganic filler. Furthermore, when the glass-based inorganic filler is glass fiber, the glass fiber bundle is cut into a length of 3 mm to prepare chopped fibers. In addition, the glass-based inorganic filler (B3) is a chopped fiber surface-treated with a polyurethane resin (opaque) and a silane coupling agent once, and further coated with a blocked isocyanate twice. Cloth, dry to prepare.

[(C) Polyfunctional isocyanate compound] (C1) Isophorone diisocyanate trimer (manufactured by Evonik, VESTANAT T1890/100) (C2) 4,4'-diphenylmethane diisocyanate [(D) Boronic acid Compound] (D) Orthoboric acid [(E) Triazine derivative with nitrogen-containing functional group] (E1) Melamine (E2) Benzoguanamine (E3) CTUguanamine

<Evaluation of Physical Properties> The granular compositions of Examples and Comparative Examples were formed into test pieces using an injection molding machine. Then, the tensile strength and tensile elongation were measured according to ISO527-1, 2, the bending strength was measured according to ISO178, and the Charpy impact strength (notched, 23°C) was measured according to ISO179∙1eA. <Evaluation of Creep Resistance> Using a tensile test piece conforming to ISO3167, a load of 80° C. and 40 MPa in the air as high temperature and high load conditions was applied to a creep tester, and the time until the test piece broke was measured. The evaluation results are shown in Tables 1 and 2. The unit of composition is parts by mass.

[第2表]

[Table 1]

[Table 2]

From Tables 1 and 2, it can be seen that the mechanical properties and creep properties are improved in the present invention.

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none.

Claims (7)

A polyacetal resin composition containing, relative to 100 parts by mass of (A) polyacetal resin: (B) at least one selected from the group consisting of blocked isocyanate compounds, polyurethane resins and silane coupling agents 1 to 100 parts by mass of the surface-treated glass-based inorganic filler; (C) 0.1 to 10 parts by mass of a polyfunctional isocyanate compound; (D) 0.001 to 3 parts by mass of a boric acid compound; and (E) 0.002 to 10 parts by mass of the triazine derivative having a nitrogen-containing functional group. The polyacetal resin composition according to claim 1, wherein the (C) polyfunctional isocyanate compound is selected from the group consisting of 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, 1, A compound of at least one of 6-hexamethylene diisocyanate, 2,4-toluene diisocyanate, and 2,6-toluene diisocyanate. The polyacetal resin composition according to claim 1, wherein the (C) polyfunctional isocyanate compound is selected from the group consisting of 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, 1, A compound of at least one of 6-hexamethylene diisocyanate, 2,4-toluene diisocyanate, and a multimer of 2,6-toluene diisocyanate. The polyacetal resin composition according to claim 1, wherein the (C) polyfunctional isocyanate compound is selected from the group consisting of 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, 1, A compound of at least one of 6-hexamethylene diisocyanate, 2,4-toluene diisocyanate, and a trimer of 2,6-toluene diisocyanate. The polyacetal resin composition according to claim 1, wherein the (D) boric acid compound is orthoboric acid. The polyacetal resin composition according to claim 1, wherein the (E) triazine derivative having a nitrogen-containing functional group is at least one selected from the group consisting of melamine, benzoguanamine and CTUguanamine compound of. The polyacetal resin composition according to claim 1, wherein the (B) glass-based inorganic filler is at least one glass-based inorganic filler selected from the group consisting of glass fibers, glass beads, ground glass fibers, and glass flakes Inorganic fillers.