CN104995254A - Polyacetal resin composition, and manufacturing method for same - Google Patents
Polyacetal resin composition, and manufacturing method for same Download PDFInfo
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- CN104995254A CN104995254A CN201480007090.5A CN201480007090A CN104995254A CN 104995254 A CN104995254 A CN 104995254A CN 201480007090 A CN201480007090 A CN 201480007090A CN 104995254 A CN104995254 A CN 104995254A
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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
- C08G2/10—Polymerisation of cyclic oligomers of formaldehyde
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/56—Polyacetals
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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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
-
- 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
- C08G4/00—Condensation polymers of aldehydes or ketones with polyalcohols; Addition polymers of heterocyclic oxygen compounds containing in the ring at least once the grouping —O—C—O—
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2359/00—Characterised by the use of polyacetals containing polyoxymethylene sequences only
- C08J2359/02—Copolyoxymethylenes
Abstract
Provided is a polyacetal resin composition that can meet the demands for high level and varied mechanical properties that are required in accordance with the expansion of the field of use for polyacetal resin. The polyacetal resin composition according to the present invention comprises: 30-95 weight% of polyacetal resin (A); 5-50 weight% of a glass inorganic filler (B) that has been subjected to silane coupling treatment; 0.1-10 weight% of a trifunctional isocyanate compound (C); and 0.01-0.5 weight% of a nitrogen compound (D) having formaldehyde reactivity. If component (B) is glass fibres or similar, the tensile strength thereof is at least 120MPa, and if component (B) is glass beads or similar, the tensile strength is at least 60MPa. This resin composition is obtained by mixing the other components into component (A) which has been pre-dried until the water content thereof is not more than 1000ppm.
Description
Technical field
The present invention relates to polyacetal resin composite and manufacture method thereof.
Background technology
Polyacetal resin has excellent characteristic in the dimensional stability etc. of mechanical characteristics, thermal property, electrical characteristic, sliding, formability, products formed, is widely used in electric installation, trolley part, precision mechanical part etc. as structured material, mechanical part.And, in order to improve mechanical characteristics, such as intensity, the rigidity of polyacetal resin, the strongtheners such as known compounding glass system inorganic filling material.
But polyacetal resin lacks active, and glass system inorganic filling material also lacks activity, therefore, only in polyacetal resin compounding glass system inorganic filling material and melting mixing time, both adaptation becomes not enough, and most cases can not get the raising of the mechanical characteristics of expectation degree.Therefore, the adaptation proposed for improving polyacetal resin and glass system inorganic filling material carrys out the various methods of improved mechanical properties.
Such as, known in polyacetal resin compounding glass fibre and phenoxy resin (with reference to patent documentation 1); Glass fibre, superoxide and silane series coupling agent (with reference to patent documentation 2) is added in polyacetal resin; In polyoxymethylene (polyacetal resin), compounding polyaminoester emulsion has carried out the glass fibre of starching, and containing silane coupling agent (with reference to patent documentation 3) in polyaminoester emulsion; In polyoxymethylene (polyacetal resin), compounding preferred silane coupling agent has carried out surface-treated glass fibre and sheet glass (with reference to patent documentation 4); In polyacetal resin, add glass system inorganic filler and boronic acid compounds, and with specific silane compound, surface treatment (with reference to patent documentation 5) is carried out to this glass system inorganic filler; In polyacetal resin, add glass system inorganic filling material and hydroxy carboxylic acid compound, and with specific silane compound, surface treatment (with reference to patent documentation 6) etc. is carried out to this glass system inorganic filling material.
Prior art document
Patent documentation
Patent documentation 1: Japanese Laid-Open Patent Publication 49-98458 publication
Patent documentation 2: Japanese Laid-Open Patent Publication 60-219252 publication
Patent documentation 3: Japanese Laid-Open Patent Publication 61-236851 publication
Patent documentation 4: Japanese Laid-Open Patent Publication 62-91551 publication
Patent documentation 5: Japanese Unexamined Patent Publication 9-151298 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2002-371168 publication
Summary of the invention
the problem that invention will solve
But, although these methods are all chemically reactive in order to improve glass system inorganic filling material and play a role, but be only like this, when using forcing machine that chemically inactive polyacetal resin and glass system inorganic filling material are reacted, the composition that the sufficient reacting being difficult to obtain polyacetal resin and glass system inorganic filling material carries out, may not be abundant in order to reach excellent physical strength.
The object of the invention is to solve above-mentioned problem, provide to meet and utilize the higher level required by the expansion in field and the polyacetal resin composite of various mechanical characteristics in recent years with polyacetal resin.
for the scheme of dealing with problems
The present inventor etc. further investigate repeatedly in order to solve above-mentioned problem, found that: polyacetal resin is predrying until become below specified moisture content, hybrid glass system inorganic filling material, specific isocyanate compound and there is the nitrogen compound of formaldehyde reaction in this polyacetal resin, the fiber reinforcement polyacetal resin composite that intensity is high, hot water resistance, creep properties are also excellent can be obtained thus, thus complete the present invention.Specifically, the invention provides following scheme.
(1) the present invention is a kind of polyacetal resin composite, it contains: (A) polyacetal resin 30 % by weight ~ 95 % by weight, (B) through the glass system inorganic filling material 5 % by weight ~ 50 % by weight of silane coupled process, (C) trifunctional isocyanates compound 0.1 % by weight ~ 10 % by weight, (D) there is the nitrogen compound 0.01 % by weight ~ 0.5 % by weight of formaldehyde reaction, described (B) glass system inorganic filling material is glass fibre, milled fibre, any number of in granulated glass sphere or sheet glass (glass flake), described (B) glass system inorganic filling material is glass fibre or Fiber Aspect Ratio L/D when being the milled fibre of more than 50, by the tension test sheet according to ISO3167 making at 23 DEG C, place under the condition of 50%RH 48 little constantly, the tensile strength carrying out testing according to the test rod of the use thickness 4mm in the tension test at 23 DEG C of ISO527 is more than 120MPa, described (B) glass system inorganic filling material is granulated glass sphere, during milled fibre less than 50 of sheet glass or Fiber Aspect Ratio L/D, tensile strength is more than 60MPa.
(2) in addition, the present invention is the polyacetal resin composite described in (1), and wherein, the water content utilizing karl fischer method to measure of described (A) polyacetal resin is below 1000ppm.
(3) in addition, the present invention is the polyacetal resin composite described in (1) or (2), wherein, described (A) polyacetal resin contains (A1) and has in fact the polyacetal resin 0.05 % by weight ~ 10 % by weight that the polyacetal resin 30 % by weight ~ 95 % by weight of the molecular structure of straight chain and (A2) have side chain or crosslinking structure.
(4) in addition, the present invention is the polyacetal resin composite described in (3), wherein, the polyacetal resin that described (A1) has in fact the molecular structure of straight chain contains Copolyacetal, described Copolyacetal by (A11) trioxymethylene 80.00 % by weight ~ 99.95 % by weight, with (A12), not there is substituent cyclic ether compound and/or cyclic formals compound 0.05 ~ 20.0 % by weight copolymerization and obtain.
(5) in addition, the present invention is the polyacetal resin composite described in (4), wherein, described (A12) does not have substituent cyclic ether compound and/or cyclic formals compound can enumerate oxyethane, 1,3-dioxolane, Diethylene Glycol formal, 1,4-butyleneglycol formal, 1,3-dioxane, propylene oxide etc., especially comprise and be selected from by oxyethane, 1, more than a kind compound in the group of 3-dioxolane, BDO formal or Diethylene Glycol formal composition.
(6) in addition, the present invention is the polyacetal resin composite described in any one in (3) ~ (5), wherein, described (A2) has the polyacetal resin of side chain or crosslinking structure is the polyacetal resin with crosslinking structure.
(7) in addition, the present invention is the polyacetal resin composite described in (6), wherein, the described polyacetal resin with crosslinking structure is crosslined polyacetal resin, and (A21) trioxymethylene 88.00 % by weight ~ 99.89 % by weight, (A22) are not had substituent simple function cyclic ether compound and/or simple function cyclic formals compound 0.05 ~ 20.0 % by weight and (A23) polyfunctional glycidyl ether compound 0.01 ~ 2.00 % by weight copolymerization and obtain by this crosslined polyacetal resin.
(8) in addition, the present invention is the polyacetal resin composite described in (7), wherein, described (A22) does not have substituent simple function cyclic ether compound and/or simple function cyclic formals compound can enumerate oxyethane, 1,3-dioxolane, Diethylene Glycol formal, 1,4-butyleneglycol formal, 1,3-dioxane, propylene oxide etc., especially comprise and be selected from by oxyethane, 1, more than a kind compound in the group of 3-dioxolane, BDO formal or Diethylene Glycol formal composition.
(9) in addition, the present invention is the polyacetal resin composite described in (7) or (8), wherein, described (A23) polyfunctional glycidyl ether compound comprises and is selected from by more than the a kind compound of trihydroxymethylpropanyltri diglycidyl ether, T 55 or tetramethylolmethane four in the group that forms of glycidyl ether.
(10) in addition, the present invention is the polyacetal resin composite described in any one in (1) ~ (9), wherein, described (C) trifunctional isocyanates compound comprises and is selected from 4,4 '-Methylene bis phenyl isocyanic ester, isophorone diisocyanate, 1, more than a kind compound in the tripolymer of 6-hexamethylene diisocyanate, 2,4 toluene diisocyanate or 2,6-tolylene diisocyanate.
(11) in addition, the present invention is the polyacetal resin composite described in any one in (1) ~ (10), wherein, described (D) has the nitrogen compound of formaldehyde reaction is the compound with triazine skeleton and the nitrogen-containing functional group with formaldehyde reaction.
(12) in addition, the present invention is the polyacetal resin composite described in any one in (1) ~ (11), the organometallic compound 0.05 % by weight ~ 1.0 % by weight that it also comprises (E) containing the above metal of at least one be selected from Sn, Zn, Pb.
(13) in addition, the present invention is the manufacture method of polyacetal resin composite, comprising: drying process, by dry for polyacetal resin until the water content utilizing karl fischer method to measure becomes below 1000ppm; And mixed processes, carrying out mixing in described dried polyacetal resin 30 % by weight ~ 95 % by weight through the glass system inorganic filling material 5 % by weight ~ 50 % by weight of silane coupled process, trifunctional isocyanates compound 0.1 % by weight ~ 10 % by weight and the nitrogen compound 0.01 % by weight ~ 0.5 % by weight with formaldehyde reaction.
the effect of invention
According to the present invention, can be provided in that intensity is high, polyacetal resin composite that aspect that hot water resistance, creep properties are also excellent can meet the mechanical characteristics of height.
Embodiment
Below, describe concrete embodiment of the present invention in detail, but the present invention is not by any restriction of following embodiment, can add and suitably change and implement in the scope of object of the present invention.
< polyacetal resin composite >
Polyacetal resin composite of the present invention contains (A) polyacetal resin 30 % by weight ~ 95 % by weight, (B) have formaldehyde reaction nitrogen compound 0.01 % by weight ~ 0.5 % by weight through the glass system inorganic filling material 5 % by weight ~ 50 % by weight of silane coupled process, (C) trifunctional isocyanates compound 0.1 % by weight ~ 10 % by weight and (D).And, by the tension test sheet made according to ISO3167 23 DEG C, place under the condition of 50%RH 48 little constantly, the tensile strength carrying out testing according to the test rod of the use thickness 4mm in the tension test at 23 DEG C of ISO527 is more than 120MPa.
[(A) polyacetal resin]
The kind of (A) polyacetal resin is not particularly limited, as long as there is in fact the polyacetal resin of the molecular structure of straight chain for (A1).From the aspect further can improving mechanical characteristics, (A) polyacetal resin preferably comprises (A1) to be had in fact the polyacetal resin 30 % by weight ~ 95 % by weight of the molecular structure of straight chain, has the mixture of the polyacetal resin 0.05 % by weight ~ 10 % by weight of side chain or crosslinking structure with (A2).
((A1) has in fact the polyacetal resin of the molecular structure of straight chain)
To (A1) as long as the polyacetal resin in fact with the molecular structure of straight chain is with Oxymethylene (-CH
2o-) being the macromolecular compound of essential building blocks, being not particularly limited, both can be polyacetal homopolymer, also can for also having the Copolyacetal (comprising segmented copolymer) of other structural units a small amount of beyond deoxygenation methylene radical.In addition, as required, can different two or more (A1) composition of mixed characteristic and using.
In the present invention, from the viewpoint such as formability, thermostability, preferably use Copolyacetal.As described Copolyacetal, preferably will (A11) trioxymethylene 80.00 % by weight ~ 99.95 % by weight, not there is substituent cyclic ether compound and/or cyclic formals compound 0.05 ~ 20.0 % by weight copolymerization and the multipolymer that obtains with (A12), be more preferably the multipolymer above-mentioned (A11) composition 90.0 ~ 99.9 % by weight and above-mentioned (A12) composition 0.1 ~ 10.0 % by weight copolymerization obtained.
As the object lesson of above-mentioned (A12) composition, oxyethane, 1 can be enumerated, 3-dioxolane, Diethylene Glycol formal, 1,4-butyleneglycol formal, 1,3-dioxane, propylene oxide etc., especially more than a kind compound in the group comprising and be selected from and be made up of oxyethane, DOX, BDO formal or Diethylene Glycol formal can be enumerated.
The preparation method of (A1) composition is not particularly limited, known method can be used to be prepared.
((A2) has the polyacetal resin of side chain or crosslinking structure)
Although not necessarily form, (A) polyacetal resin can have the polyacetal resin of side chain or crosslinking structure containing (A2).(A2) composition obtains as follows: add further in the raw material used when the manufacture of (A1) composition can with the copolymerization such as formaldehyde, trioxymethylene and the compound that can form branching units or crosslink unit via copolymerization to carry out copolymerization, thus to obtain.
Such as, there is substituent monofunctional glycidyl compound (such as phenyl glycidyl ether, butylglycidyl ether etc.) carry out copolymerization by adding further in (A11) composition and (A12) composition, the polyacetal resin with branched structure can be obtained.In addition, carrying out copolymerization by adding polyfunctional glycidyl ether's compound in (A11) composition and (A12) composition, the polyacetal resin with crosslinking structure can be obtained.
In the present invention, when adding (A2), from the view point of improving mechanical characteristics, as (A2) composition, preferred use has the polyacetal resin of crosslinking structure, wherein, the crosslined polyacetal resin preferably (A21) trioxymethylene 88.00 % by weight ~ 99.89 % by weight, (A22) not being had substituent simple function cyclic ether compound and/or simple function cyclic formals compound 0.05 ~ 20.0 % by weight and (A23) polyfunctional glycidyl ether compound 0.01 ~ 2.00 % by weight copolymerization and obtain.And, be more preferably the crosslined polyacetal resin (A21) composition 96.50 % by weight ~ 99.28 % by weight, (A22) composition 0.7 % by weight ~ 3.0 % by weight and (A23) composition 0.02 % by weight ~ 0.5 % by weight copolymerization obtained.
As the object lesson of above-mentioned (A22) composition, oxyethane, 1 can be enumerated, 3-dioxolane, Diethylene Glycol formal, 1,4-butyleneglycol formal, 1,3-dioxane, propylene oxide etc., especially more than a kind compound in the group comprising and be selected from and be made up of oxyethane, DOX, BDO formal or Diethylene Glycol formal can be enumerated.
From the view point of improving mechanical characteristics, above-mentioned (A23) composition is preferably the compound in 1 molecule with 3 ~ 4 glycidyl ethers, as object lesson, can enumerate to comprise and be selected from by more than the a kind compound of trihydroxymethylpropanyltri diglycidyl ether, T 55 or tetramethylolmethane four in the group that forms of glycidyl ether.
The preparation method of (A2) composition is not particularly limited, known method can be utilized to be prepared.
(A2) the compounding amount of composition is preferably less than 10 % by weight relative to (A1) composition 30 % by weight ~ 95 % by weight.If more than 10 % by weight, then the variation such as molding processibility, result mechanical characteristics also becomes insufficient, therefore not preferred.Because (A2) composition is not required, so be not particularly limited lower limit, in order to fully pass add (A2) become assign to improve the such effect of mechanical characteristics, relative to (A1) composition 30 % by weight ~ 95 % by weight, the compounding amount of (A2) composition is preferably made to be more than 0.05 % by weight.
(water content)
(A) water content utilizing karl fischer method to measure of polyacetal resin is preferably below 1000ppm.It should be noted that, unless otherwise specified, then " water content " recorded in this specification sheets refers to the water content utilizing karl fischer method to measure.
Water content does not need to be always below 1000ppm, as long as be that it is enough for below 1000ppm being (B) composition ~ (D) composition etc. with other compositions when mixing.When mixing with other compositions under more than the state of 1000ppm, use the synthetic resin of mixed resin combination cannot become the products formed with sufficient tensile strength, set out from the side not preferred.
In order to make the water content of (A) polyacetal resin be below 1000ppm, can carry out predrying to (A) polyacetal resin before mixing with other compositions.
(melting index)
In addition, from the view point of formability, 190 DEG C, measure under load 2.16kg time the melting index of (A) polyacetal resin be preferably 1 ~ 50g/10 minute.
[(B) is through the glass system inorganic filling material of silane coupled process]
Then, be described through the glass system inorganic filling material of silane coupled process for (B).
(B) composition silane coupling agent carries out pre-treatment.If do not carry out silane coupled process, then likely decline with the adaptation of polyacetal resin, therefore not preferred.The kind of silane coupling agent is not particularly limited, from the view point of the adaptation with polyacetal resin, is preferably selected from more than a kind in aminosilane, epoxy radicals silicone hydride, methacryloyl base silane or vinyl-benzylamino silane.
(B) addition of glass system inorganic filling material is 5 ~ 50 % by weight, is preferably 5 ~ 25 % by weight.If addition is less than 5 % by weight, then show the effect that packing material strengthens hardly, therefore not preferred.In addition, if more than 50 % by weight, then extrude processibility and significantly reduce, in fact can not manufacture composition, therefore not preferred.
[(C) trifunctional isocyanates compound]
Then, (C) trifunctional isocyanates compound is described.So-called (C) trifunctional isocyanates compound refers to compound cyanate ester based containing 3 different (sulfo-) in 1 molecule.Isocyanate compound needs for trifunctional.If below two senses, then the adaptation of polyacetal resin and glass system inorganic filling material is likely made to reduce, therefore not preferred.
As long as isocyanate compound is trifunctional, be not particularly limited, from the view point of acquired, preferably be selected from 4,4 '-Methylene bis phenyl isocyanic ester, isophorone diisocyanate, 1, more than a kind in the tripolymer of 6-hexamethylene diisocyanate, 2,4 toluene diisocyanate or 2,6-tolylene diisocyanate.
(C) the compounding amount of trifunctional isocyanates compound is 0.1 ~ 10 % by weight, is preferably 1.0 ~ 3.0 % by weight.If compounding quantity not sufficient 0.1 % by weight, then to improve effect through the adaptation of the glass system inorganic filling material of silane coupled process insufficient for (A) polyacetal resin and (B), not preferably.In addition, if compounding amount is more than 5 % by weight, then the thickening of (A) polyacetal resin advances, and extrudes processibility very low, therefore not preferred.
[(D) has the nitrogen compound of formaldehyde reaction]
Then, illustrate that (D) has the nitrogen compound of formaldehyde reaction.(D) composition for be reduced by with the formaldehyde reaction contained by polyacetal resin and shaping time etc. the foreign odor experienced and react with other added ingredientss and improve adaptation.
(D) nitrogen compound with formaldehyde reaction does not preferably cause the dysgenic nitrogen compound such as variable color, decomposition to (A) polyacetal resin, is particularly preferably the trimeric cyanamide, substituted melamine, guanamine compound etc. with triazine skeleton.
(D) the compounding amount of composition is 0.01 ~ 0.5 % by weight.If compounding quantity not sufficient 0.01 % by weight, then fully do not show and use the effect of (A) composition ~ (D) composition, therefore not preferred.If compounding amount is more than 0.5 % by weight, then may there is the variable color of (A) polyacetal resin, oozing out from synthetic resin, therefore not preferred.
[(E) organometallic compound containing the above metal of at least one be selected from Sn, Zn, Pb]
In addition, although optional composition, but polyacetal resin composite of the present invention, except (A) composition to (D) composition, can also comprise (E) organometallic compound containing the above metal of at least one be selected from Sn, Zn, Pb.Improve (A) polyacetal resin with (B) when the adaptation of the glass system inorganic filling material of silane coupled process with (C) trifunctional isocyanates compound, (E) composition has the function of booster action.
(E) composition does not preferably cause the dysgenic composition such as variable color, decomposition to (A) polyacetal resin, from this viewpoint, is preferably Zinic stearas, di-n-butyltin dilaurate etc.
(E) the compounding amount of composition is preferably in the scope of 0.05 ~ 1.0 % by weight.If compounding quantity not sufficient 0.05 % by weight, then likely fully cannot obtain the combined effect with (C) composition, if more than 1.0 % by weight, then may there is the variable color of (A) polyacetal resin and the reduction of resin properties.
[(F) other compositions]
In addition, polyacetal resin composite of the present invention can comprise as (F) other compositions, improve the stablizer of thermostability, UV light absorber, lubricant, releasing agent, comprise the tinting material, tensio-active agent etc. of dyestuff, pigment.
[tensile strength]
For polyacetal resin composite of the present invention, when (B) glass system inorganic filling material be glass fibre or Fiber Aspect Ratio L/D is the milled fibre of more than 50, there is the high tensile strength of more than 120MPa, when (B) glass system inorganic filling material is milled fibre less than 50 of granulated glass sphere, sheet glass or Fiber Aspect Ratio L/D, there is the high tensile strength of more than 60MPa.In this specification sheets, unless otherwise specified, then tensile strength refer to by the tension test sheet made according to ISO3167 23 DEG C, place under the condition of 50%RH 48 little constantly, according to value during testing with the test rod of thickness 4mm in the tension test at 23 DEG C of ISO527.
The manufacture method > of < polyacetal resin composite
The polyacetal resin composite with above-mentioned tensile strength can as described belowly obtain.First, by dry for (A) polyacetal resin until the water content utilizing karl fischer method to measure becomes below 1000ppm.Then, carrying out mixing in dried (A) polyacetal resin 30 % by weight ~ 95 % by weight (B) and to have through the glass system inorganic filling material 5 % by weight ~ 50 % by weight of silane coupled process, (C) trifunctional isocyanates compound 0.1 % by weight ~ 10 % by weight and (D) nitrogen compound 0.01 % by weight ~ 0.5 % by weight of formaldehyde reaction.Operation like this, can obtain the polyacetal resin composite with above-mentioned tensile strength.
For the preparation of polyacetal resin composite, utilize and can easily prepare as the normally used known method of existing resin combination preparation method.Such as, following any means can be used: after the mixing of each composition, use forcing machine mixing extrusion and prepare the method for particle; The particle that temporary transient preparation composition is different, mixes this particle for shaping with specified amount, obtains the method for the products formed of target composition after shaping; The one kind or two or more method etc. of each composition is directly dropped in forming machine.
Embodiment
Below, illustrate the present invention by embodiment, but the present invention is not limited to these embodiments.
The preparation > of < (A) polyacetal resin
((A1) has in fact the preparation that the polyacetal resin of the molecular structure of straight chain and (A2) have the polyacetal resin of side chain or crosslinking structure)
[table 1]
Before the polyacetal resin composite obtaining embodiment and comparative example, preparation (A1) has in fact the polyacetal resin that the polyacetal resin of the molecular structure of straight chain and (A2) have side chain or crosslinking structure.Use and there are 2 almost parallel turning axles, with the parallel double-shaft whipping appts of the agitating vane given prominence to along these 2 turning axles radial direction separately, the warm water of 70 DEG C is passed in chuck, the mode becoming 150rpm with the revolving circumferential velocity of the front end making agitating vane makes 2 turning axles rotate in the same direction with the speed of regulation, trioxymethylene (principal monomer) is added continuously according to the ratio shown in table 1, 1, 3-dioxolane (comonomer), and trihydroxymethylpropanyltri diglycidyl ether (comonomer), formal (molecular weight regulator) and boron trifluoride (polymerizing catalyst), carry out the copolymerization of trioxymethylene and comonomer thus.The reaction product of discharging from parallel double-shaft whipping appts being passed through crusher rapidly, afterwards, in order to make boron trifluoride (polymerizing catalyst) inactivation, adding the aqueous solution of 60 DEG C containing 0.05wt% triethylamine (deactivator).And then, through being separated, washing and drying, obtain thick polyacetal resin.
Then, relative to this thick polyacetal resin 100 weight part, add triethylamine 5 % by weight aqueous solution 3 % by weight, tetramethylolmethane four (3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester) 0.3 % by weight, use twin screw extruder melting mixing at 210 DEG C, remove l fraction.Thus, obtain granular (A1) and there is in fact the polyacetal resin that the polyacetal resin of the molecular structure of straight chain and (A2) have side chain or crosslinking structure.For (A1) and (A2), be determined at 190 DEG C, melting index under load 2.16kg, result as described in Table 1.
(drying of polyacetal resin)
[table 2]
| Treatment condition | Water content after process | |
| (A1a) | In drying machine, (80 DEG C × 12 hours) place | 161ppm |
| (A1b) | In drying machine, (60 DEG C × 4 hours) place | 711ppm |
| (a1a) | 23 DEG C, 50%RH × 30 day placement | 1760ppm |
| (a1b) | In constant temperature and humidity cabinet, (60 DEG C, 80%RH × 12 hour) place | 6520ppm |
| (A2a) | In drying machine, (80 DEG C × 12 hours) place | 172ppm |
Granular (A1) is had in fact 4 kinds of conditions shown in (A1a) of the polyacetal resin with table 2 of the molecular structure of straight chain, (A1b), (a1a) and (a1b) to place.In addition, the polyacetal resin granular (A2) with side chain or crosslinking structure is placed with the condition shown in (A2a) of table 2.Then, for 5 kinds of samples after placement, utilize karl fischer method to measure water content respectively.Show the result in table 2.
When by granular polyacetal resin, in drying machine, (80 DEG C, 12 hours or 60 DEG C, 4 hours) carry out drying, water content drops to below 1000ppm.On the other hand, when to be placed in air-conditioning room in (23 DEG C, 50%RH, 30 days) or constant temperature and humidity cabinet (60 DEG C, 80%RH, 12 hours), water content is more than 1000ppm.
Below, use symbol (A1a), test sample that (A1b), (a1a), (a1b) and (A2a) symbol distinguish polyacetal resin.
< embodiment 1 ~ 6, comparative example 1 ~ 3 >
Use glass fibre etc. are as the situation of (B) glass system inorganic filling material
First, the polyacetal resin composite that intensity is high in order to provide, hot water resistance, creep properties are also excellent, is described for the situation using glass fibre etc. to obtain polyacetal resin composite as (B) glass system inorganic filling material.
[table 3]
In table 3, each composition is as follows.
(A1) there is in fact the polyacetal resin of the molecular structure of straight chain
(A1a), (A1b), (a1a) and (a1b) that obtain in the preparation > of above-mentioned < (A) polyacetal resin
(A2) there is the polyacetal resin of side chain or crosslinking structure
(A2a) that obtain in the preparation > of above-mentioned < (A) polyacetal resin
(B) glass system inorganic filler
(B1) glass fibre CS03MA409B (Owens Corning Corporation manufactures)
(C) trifunctional isocyanates compound
Isophorone diisocyanate trimer Vestanat T1890/100 (manufacture of Degussa Japan Co., Ltd.)
(D) there is the nitrogen compound of formaldehyde reaction
Trimeric cyanamide (Mitsui Chemicals, Inc's manufacture)
(E) organometallic compound
Zinic stearas SAK-CS-G (manufacture of Pin Chuan Chemical Co., Ltd)
(B1) composition that table 3 records, (C) composition, (D) composition and (E) composition is added according to the ratio shown in table 3 in the polyacetal resin that table 3 is recorded, forcing machine barrel temperature being adjusted to 200 DEG C is used to carry out melting mixing, the granular polyacetal resin composite of preparation embodiment 1 ~ 6 and comparative example 1 ~ 3.
[evaluation]
For embodiment and comparative example, evaluate tensile strength and the elongation of the formed body of polyacetal resin composite.Make test film according to ISO3167 by the polyacetal resin composite of embodiment and comparative example, use this test film, carry out 23 DEG C, place under the condition of 50%RH 48 little constantly, according to the tension test at 23 DEG C of ISO527.The thickness of the test rod in tension test is 4mm.Tensile strength in this tension test and elongation are shown in table 4.
[table 4]
Confirm when dry until water content become in (A) polyacetal resin 30 % by weight ~ 95 % by weight of below 1000ppm mix (B) through the glass fibre etc. 5 % by weight ~ 50 % by weight of silane coupled process, (C) trifunctional isocyanates compound 0.1 % by weight ~ 10 % by weight and (D), there is nitrogen compound 0.01 % by weight ~ 0.5 % by weight of formaldehyde reaction, by the formed body that mixed polyacetal resin composite is shaping, there is more than 120MPa tensile strength high like this (embodiment 1 ~ 6).Thus, the polyacetal resin composite that intensity is high, hot water resistance, creep properties are also excellent aspect can meet the mechanical characteristics of height is confirmed to be provided in.
In addition, by comparing of embodiment 1 and embodiment 5, confirm to comprise further (E) containing the above metal of at least one be selected from Sn, Zn, Pb organometallic compound 0.05 % by weight ~ 1.0 % by weight time, compared with situation about not containing, tensile strength improves.
In addition, by comparing of embodiment 1 and embodiment 6, confirm to combinationally use (A1) when there is in fact polyacetal resin that the polyacetal resin of the molecular structure of straight chain and (A2) have side chain or a crosslinking structure as (A) polyacetal resin, compared with the situation that (A1) composition is independent, tensile strength improves.
On the other hand, confirm when use not talkative be fully dry (A) polyacetal resin, even if the ratio of each composition is suitable, also cannot obtain the high tensile (comparative example 1 and 2) of degree of the present invention.In addition, confirm, when not containing (C) composition and (D) composition, even if use fully dry (A) polyacetal resin, also cannot obtain the high tensile (comparative example 3) of degree of the present invention.
< embodiment 7,8, comparative example 4 >
Use granulated glass spherees etc. are as the situation of (B) glass system inorganic filling material
Then, helping reduce anisotropic polyacetal resin composite to provide, being described for the situation using granulated glass sphere etc. to obtain polyacetal resin composite as (B) glass system inorganic filling material.
[table 5]
In table 5, (B) glass system inorganic filler uses granulated glass sphere EGB731B (manufacture of Potters-Ballotini Co., Ltd.).Other compositions are identical with the above embodiments 1 etc.
In the polyacetal resin that table 5 is recorded, (B2) composition that table 3 records, (C) composition, (D) composition and (E) composition is added according to the ratio shown in table 5, forcing machine barrel temperature being adjusted to 200 DEG C is used to carry out melting mixing, the granular polyacetal resin composite of preparation embodiment 7,8 and comparative example 4.
[evaluation]
For embodiment and comparative example, with tensile strength and the elongation of the formed body of the method evaluation polyacetal resin composite identical with the above embodiments 1 etc.Show the result in table 6.
[table 6]
Confirm when dry until water content become in (A) polyacetal resin 30 % by weight ~ 95 % by weight of below 1000ppm mix (B) through the granulated glass sphere etc. 5 % by weight ~ 50 % by weight of silane coupled process, (C) trifunctional isocyanates compound 0.1 % by weight ~ 10 % by weight and (D), there is nitrogen compound 0.01 % by weight ~ 0.5 % by weight of formaldehyde reaction, reduced by the anisotropy of the shaping formed body of mixed polyacetal resin composite, and there is the high tensile (embodiment 7,8) of more than 65MPa.
On the other hand, confirm when use not talkative be fully dry (A) polyacetal resin, even if the ratio of each composition is suitable, also cannot obtain the high tensile (comparative example 4) of degree of the present invention.
Claims (13)
1. a polyacetal resin composite, it contains:
(A) polyacetal resin 30 % by weight ~ 95 % by weight,
(B) through silane coupled process glass system inorganic filling material 5 % by weight ~ 50 % by weight,
(C) trifunctional isocyanates compound 0.1 % by weight ~ 10 % by weight and
(D) there is the nitrogen compound 0.01 % by weight ~ 0.5 % by weight of formaldehyde reaction,
Described (B) glass system inorganic filling material is any number of in glass fibre, milled fibre, granulated glass sphere or sheet glass,
Described (B) glass system inorganic filling material is glass fibre or Fiber Aspect Ratio L/D when being the milled fibre of more than 50, to the tension test sheet made according to ISO3167, carry out 23 DEG C, place under the condition of 50%RH 48 little constantly according to the tension test at 23 DEG C of ISO527, the tensile strength using the test rod of thickness 4mm to carry out testing in described tension test is more than 120MPa
When described (B) glass system inorganic filling material is milled fibre less than 50 of granulated glass sphere, sheet glass or Fiber Aspect Ratio L/D, tensile strength is more than 60MPa.
2. polyacetal resin composite according to claim 1, wherein, the water content utilizing karl fischer method to measure of described (A) polyacetal resin is below 1000ppm.
3. polyacetal resin composite according to claim 1 and 2, wherein, described (A) polyacetal resin contains (A1) and has in fact the polyacetal resin 0.05 % by weight ~ 10 % by weight that the polyacetal resin 30 % by weight ~ 95 % by weight of the molecular structure of straight chain and (A2) have side chain or crosslinking structure.
4. polyacetal resin composite according to claim 3, wherein, the polyacetal resin that described (A1) has in fact the molecular structure of straight chain contains Copolyacetal, described Copolyacetal by (A11) trioxymethylene 80.00 % by weight ~ 99.95 % by weight, with (A12), not there is substituent cyclic ether compound and/or cyclic formals compound 0.05 ~ 20.0 % by weight copolymerization and obtain.
5. polyacetal resin composite according to claim 4, wherein, described (A12) does not have substituent cyclic ether compound and/or cyclic formals compound can enumerate oxyethane, 1,3-dioxolane, Diethylene Glycol formal, 1,4-butyleneglycol formal, 1,3-dioxane, propylene oxide etc., especially comprise and be selected from by oxyethane, 1, more than a kind compound in the group of 3-dioxolane, BDO formal or Diethylene Glycol formal composition.
6. the polyacetal resin composite according to any one in claim 3 ~ 5, wherein, the polyacetal resin that described (A2) has side chain or crosslinking structure is the polyacetal resin with crosslinking structure.
7. polyacetal resin composite according to claim 6, wherein, the described polyacetal resin with crosslinking structure is crosslined polyacetal resin, and (A21) trioxymethylene 88.00 % by weight ~ 99.89 % by weight, (A22) are not had substituent simple function cyclic ether compound and/or simple function cyclic formals compound 0.05 ~ 20.0 % by weight and (A23) polyfunctional glycidyl ether compound 0.01 ~ 2.00 % by weight copolymerization and obtain by this crosslined polyacetal resin.
8. polyacetal resin composite according to claim 7, wherein, described (A22) does not have substituent simple function cyclic ether compound and/or simple function cyclic formals compound can enumerate oxyethane, 1,3-dioxolane, Diethylene Glycol formal, 1,4-butyleneglycol formal, 1,3-dioxane, propylene oxide etc., especially comprise and be selected from by oxyethane, 1, more than a kind compound in the group of 3-dioxolane, BDO formal or Diethylene Glycol formal composition.
9. the polyacetal resin composite according to claim 7 or 8, wherein, described (A23) polyfunctional glycidyl ether compound comprises and is selected from by more than the a kind compound of trihydroxymethylpropanyltri diglycidyl ether, T 55 or tetramethylolmethane four in the group that forms of glycidyl ether.
10. the polyacetal resin composite according to any one in claim 1 ~ 9, wherein, described (C) trifunctional isocyanates compound comprises and is selected from by 4,4 '-Methylene bis phenyl isocyanic ester, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 2, more than a kind compound in the tripolymer of 4-tolylene diisocyanate or 2,6-tolylene diisocyanate.
11. polyacetal resin composites according to any one in claim 1 ~ 10, wherein, the nitrogen compound that described (D) has formaldehyde reaction is the compound with triazine skeleton and the nitrogen-containing functional group with formaldehyde reaction.
12. polyacetal resin composites according to any one in claim 1 ~ 11, the organometallic compound 0.05 % by weight ~ 1.0 % by weight that wherein, it also comprises (E) containing the above metal of at least one be selected from Sn, Zn, Pb.
The manufacture method of 13. 1 kinds of polyacetal resin composites, it comprises:
Drying process, by dry for polyacetal resin until the water content utilizing karl fischer method to measure becomes below 1000ppm; With
Mixed processes, is carrying out mixing in described dried polyacetal resin 30 % by weight ~ 95 % by weight through the glass system inorganic filling material 5 % by weight ~ 50 % by weight of silane coupled process, trifunctional isocyanates compound 0.1 % by weight ~ 10 % by weight and the nitrogen compound 0.01 % by weight ~ 0.5 % by weight with formaldehyde reaction.
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| JP2013019487A JP6105305B2 (en) | 2013-02-04 | 2013-02-04 | Polyacetal resin composition and method for producing the same |
| PCT/JP2014/050837 WO2014119394A1 (en) | 2013-02-04 | 2014-01-17 | Polyacetal resin composition, and manufacturing method for same |
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| CN108219356A (en) * | 2016-12-21 | 2018-06-29 | 宝理塑料株式会社 | The manufacturing method of polyacetal resin composite |
| CN110494491A (en) * | 2017-06-30 | 2019-11-22 | 宝理塑料株式会社 | Polyacetal resin composite |
| CN112194776A (en) * | 2020-09-30 | 2021-01-08 | 上海交通大学 | Preparation method of hydroxyl polyurethane |
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| JP5955424B1 (en) * | 2015-02-06 | 2016-07-20 | ポリプラスチックス株式会社 | Method for producing polyacetal resin composition |
| JP6998122B2 (en) * | 2017-03-30 | 2022-01-18 | ポリプラスチックス株式会社 | Polyacetal resin composition |
| JP7240469B1 (en) | 2021-10-04 | 2023-03-15 | ポリプラスチックス株式会社 | Polyacetal resin composition |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108219356A (en) * | 2016-12-21 | 2018-06-29 | 宝理塑料株式会社 | The manufacturing method of polyacetal resin composite |
| CN108219356B (en) * | 2016-12-21 | 2022-04-08 | 宝理塑料株式会社 | Method for producing polyacetal resin composition |
| CN110494491A (en) * | 2017-06-30 | 2019-11-22 | 宝理塑料株式会社 | Polyacetal resin composite |
| TWI763816B (en) * | 2017-06-30 | 2022-05-11 | 日商寶理塑料股份有限公司 | Polyacetal resin composition |
| CN110494491B (en) * | 2017-06-30 | 2023-01-06 | 宝理塑料株式会社 | Polyacetal resin composition |
| CN112194776A (en) * | 2020-09-30 | 2021-01-08 | 上海交通大学 | Preparation method of hydroxyl polyurethane |
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| JP2014148637A (en) | 2014-08-21 |
| WO2014119394A1 (en) | 2014-08-07 |
| JP6105305B2 (en) | 2017-03-29 |
| CN104995254B (en) | 2018-09-21 |
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