CN1923740A - Enhancement soakage agent for thin glass fiber bulked yarn - Google Patents
Enhancement soakage agent for thin glass fiber bulked yarn Download PDFInfo
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- CN1923740A CN1923740A CN 200610041537 CN200610041537A CN1923740A CN 1923740 A CN1923740 A CN 1923740A CN 200610041537 CN200610041537 CN 200610041537 CN 200610041537 A CN200610041537 A CN 200610041537A CN 1923740 A CN1923740 A CN 1923740A
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Abstract
The invention discloses a bulky spinning wetting agent, which comprises the following parts: 2.0-3.5% soluble film former, 0.64-1.05% lubricant, 0.2-0.5% organic silane coupling agent, 0.1-0.22% pH value adjusting agent. The agent can be allocated and used under normal temperature.
Description
Technical field
Enhancement soakage agent for thin glass fiber bulked yarn belongs to the glass fiber infiltration agent field, relates in particular to the voluminous yarn treating compound.
Background technology
Bulked glass yarn is by glass continuous filament yarn, the glass fiber yarn of a kind of soft fluffy that is formed by expanded (distortion) under the high pressure draft effect.It has not only kept the general property of common continuous glass fibre, and has both the fluffiness of staple fibre, be a kind of heatproof, corrosion resistant, low heat conduction, low unit weight, can weave, novel glass fiber goods that filtration resistance is little, soft.It can be used as various wrapping material, decorative material for wall surface and replaces the strongthener of asbestos as friction goods, also can be used as high-temperature-resistant filtering material, fiber reinforced plastic materials etc., and Application Areas is very extensive.
Glass fibre owing to be subjected to the fierce impact of high pressure draft, can produce the intensive friction between fiber and air-flow, fiber and the fiber in puffing process.Want to make glass fibre in puffing process, to produce lousiness, few being fractureed less as far as possible, smoothly by expanded operation, the bulked glass yarn of producing can reach fiber softening, rub resistance, warping strength, easy filoselle, lubricate technical requirementss such as good, this removes outside the Pass filament diameter, twist size with voluminous yarn itself have, and used treating compound then is one of The key factor in the production process.
Domestic and international existing thin glass fiber voluminous yarn adopts starch-type treating compound and paraffin sizing material mostly with treating compound, and this two classes treating compound is non-fiber size for reinforcemeent.When using this two classes treating compound, also have the problem of the following aspects at present: at first their blending process complexity also needs high temperature steaming, and storage vessel and transport pipe also need omnidistance continuous the insulation; The moiety for the treatment of compound own influences voluminous yarn and combines with the interface of product substrate, also needs thermal treatment when it is used for strongthener, thereby causes the waste of the energy, the pollution of environment and the decline of composite material strength; All do not contain coupling agent in these two kinds of sizing systems, so voluminous yarn combines weak effect with the interface of product substrate.
Also there is part producing producer to attempt adopting existing fiber size for reinforcemeent to produce the glass burky yarn treating compound both at home and abroad, but the application of this treating compound only limits to the slightly production of the alkali free glass fibre voluminous yarn of the pultrude process special use of diameter fibers (Fibre diameter is more than 14 microns), when it is used for thin diameter glass fibers voluminous yarn below 11 microns and produces, its rub resistance, warping strength performance just can not satisfy its after-processing technology requirement, influence its product properties, up to the present, still there is not special-purpose fiber size for reinforcemeent for the glass voluminous yarn production below 11 microns with treating compound.
Summary of the invention
At the problem of above-mentioned existence, the present invention proposes a kind of thin glass fiber voluminous yarn fiber size for reinforcemeent that is applicable to 6～11 microns, it can be finished preparation at normal temperatures and use.When this glass voluminous yarn is used for the reinforced thermoplastics(RTP) goods, can be directly and thermoplastic resin compound, do not need thermal treatment, saved the energy, reduced environmental pollution.Get togather with the interface junction of product substrate, the intensity height.
Technical solution of the present invention is: it contains water-soluble film forming agent, is the lubricant system of assisting and regulates dispersive organosilicon alkanes coupling agent through the PH conditioning agent that based on fatty acid ester, cats product this treating compound is composed as follows:
Water-soluble film forming agent accounts for 2.0～3.5% for the treatment of compound gross weight;
Lubricant accounts for 0.64～1.05% for the treatment of compound gross weight;
Organo silane coupling agent accounts for 0.2～0.5% for the treatment of compound gross weight;
Be dispersed with the PH conditioning agent that machine silane coupling agent uses and account for 0.1～0.22% for the treatment of compound gross weight;
All the other are water.
In water-soluble film forming agent, the weight ratio of water-soluble epoxy resin and water-soluble unsaturated polyester resin is 1.33: 1～2.8: 1.
Water-soluble unsaturated polyester resin in water-soluble film forming agent, be total molar ratio of alcohol to acid by 1.15: 1～1.25: 1 amounts of getting, molecular weight is 400 or 600 polyoxyethylene glycol and the mol ratio cis-butenedioic anhydride that is 1: 3 and the reaction synthetics of hexanodioic acid.Water-soluble epoxy resin in water-soluble film forming agent is meant that bisphenol A epoxide resin and the diethanolamine of oxirane value between 0.51～0.44 is to carry out the water-soluble epoxy resin of modification in 1: 1～2: 1 according to oxirane value and amino mol ratio.
Lubricant system composition formation is that the weight ratio of fatty acid ester series lubricant agent and cats product is 20: 1～7: 1.
The fatty acid ester series lubricant agent is that the polymerization degree of 18 carbon fatty acids is 9～14 macrogol ester.
Cats product can be one of following material: the alkyl cationic quaternary ammonium salt of 9～18 carbon; The alkyl positively charged ion acid amides of 9～18 carbon.
Organosilicon alkanes coupling agent can be selected one of following material for use: organosilane is a γ-An Bingjisanyiyangjiguiwan; Vinyltriethoxysilane; γ-glycidyl ether oxygen base propyl trimethoxy silicane; γ-methacryloxypropyl trimethoxy silane.
Be dispersed with the PH conditioning agent that machine silane coupling agent uses and select one of following material for use: Glacial acetic acid; Citric acid.
It is mainly used in makes 6～11 microns middle alkali or alkali-free thin glass fiber voluminous yarn.
Water-soluble film forming agent among the present invention contains the water soluble resin of polyester, two kinds of different chemical structures of epoxy, contains more ether tendon and ester tendon in the Polyester Resin Water Soluble structure.The existence of ether tendon and ester tendon makes membrane-forming agent have wetting ability and polarity preferably; And water-soluble epoxy resin is that alkylamine by containing reactive hydrogen is to epoxy resin modification, make the part or all of epoxide group in the epoxy resin structural become wetting ability and all stronger hydroxyl of polarity, so this resinoid and reinforced thermoplastics(RTP) base material have good affinity.Adopting based on fatty acid ester, cats product among the present invention is the lubricant system of assisting, be because fatty acid ester contains more polar group, cats product has lubricated preferably usefulness, so the use of this lubricant system can be satisfied the double requirements of the lubricated and interface performance for the treatment of compound simultaneously.What the coupling agent among the present invention adopted is organosilicon alkanes coupling agent, and they are silicoorganic compound that a class has special construction, and they can be represented with following general formula: Y-R-SiX
3, Y is the group that can react with organic compound in the formula, as vinyl, amino, epoxy group(ing) etc.; R is the short chain alkylene base, can couple together Y and Siliciumatom by it; X is the group that can be hydrolyzed and react and generate Si-OH, as alkoxyl group, acetoxyl group etc.X is the different active groups of two class response characteristics with Y, the X group easily produces firm combining with inorganic materials (glass fibre), therefore pass through silane coupling agent, can between the interface of inorganic materials and organic materials, erect " molecule bridge ", the material of two kinds of character great disparities is linked together, increase bonding strength, improved performance of composites.The PH conditioning agent that the organic silane coupling agent of dispersion among the present invention is used can be with Glacial acetic acid or citric acid, Glacial acetic acid preferably, because Glacial acetic acid is cheap and easy to get, and in use volatilizable, less to the loss of strength of glass voluminous yarn.
Composition among the present invention is water-soluble substances, so blending process of the present invention is simple, and storage vessel and transport pipe do not need insulation.The present invention especially is suitable for the production of 9～11 microns middle alkali or 6～9 microns thin increasing diameter strong type of alkali-free bulked glass yarns.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
The concrete prescription of embodiment sees Table 1, and each prescription is all to dispose 100 kilograms treating compound calculating.Each amounts of components that wherein relates to, no specified otherwise are butt (non-volatile part) content." under the agitation condition " wherein is meant that stirring velocity is not to produce bubble for well.Its blending process be with fill a prescription 1, prescription 2, prescription 4 be the example schematic illustration.The blending process of all the other each embodiment, the component in constituting according to prescription, reference formulation 1 or fill a prescription 2 or 4 the blending process of filling a prescription carry out.For example:
1) additional proportion of the PH conditioning agent of coupling agent KH-560, KH-570, A-151 is 20% of a coupling agent consumption, and it is 2% that coupling agent disperses concentration, and pH value is 2-4
2) the PH conditioning agent additional proportion of coupling agent KH-550 is 60% of a coupling agent consumption, and it is 2% that coupling agent disperses concentration
3) lubricant MO-400, MO-600 using method are identical
4) lubricant MS-400, MS-600 using method are identical
5) 681,682, the NBR-280 using method is identical
6) SR-1, SR-2, NBR-110 using method are identical
The blending process of A, prescription 1
1) dispersion of KH-550 coupling agent: take by weighing 12.5 kg of water, add 150 gram Glacial acetic acid, under agitation condition, slowly add the KH-550 of 250 grams, be stirred to till the aqueous solution clear.
2) dispersion of KH-570 coupling agent: take by weighing 12.5 kg of water, add 50 gram Glacial acetic acid, under agitation condition, slowly add the KH-570 of 250 grams, be stirred to till the aqueous solution clear.
3) take by weighing 1.0 kilograms of MO-400, fully dilute evenly with 20 kg of water.
4) take by weighing 1631 of 50 grams, fully dilute evenly with 2.5 kilogram of 80～100 water of spending, the cold water that adds 7.5 kilograms stirs.
5) take by weighing 2.0 kilograms of water-soluble epoxy resin 681 membrane-forming agents, the water that adds 10 kilograms stirs.
6) take by weighing 1.0 kilograms of Polyester Resin Water Soluble SR-2 membrane-forming agents, the water that adds 10 kilograms stirs.
7) successively material is added in the preparing tank according to above-mentioned dilution order, water is supplied weight to 100 and kilogram is stirred and can use.
The blending process of B, prescription 2
1) dispersion of KH-560 coupling agent: take by weighing 12.5 kg of water, add 50 gram citric acid powder, treat that it dissolves fully after, under agitation condition, slowly add the KH-560 of 250 grams, be stirred to till the aqueous solution clear.
2) dispersion of A-151 coupling agent: take by weighing 12.5 kg of water, add 50 gram citric acid powder, treat that it dissolves fully after, under agitation condition, slowly add the A-151 of 250 grams, be stirred to till the aqueous solution clear.
3) take by weighing 0.8 kilogram of MO-600, fully dilute evenly with 20 kg of water.
4) take by weighing the 80 Ction X that restrain, fully dilute evenly with 3.0 kilogram of 60～70 water of spending, the cold water that adds 8.0 kilograms stirs.
5) take by weighing 1.6 kilograms of water-soluble epoxy resin 682 membrane-forming agents, the water that adds 10 kilograms stirs.
6) take by weighing 1.0 kilograms of Polyester Resin Water Soluble SR-1 membrane-forming agents, the water that adds 10 kilograms stirs.
7) successively material is added in the preparing tank according to above-mentioned dilution order, water is supplied weight to 100 and kilogram is stirred and can use.
The blending process of C, prescription 4
1) dispersion of KH-560 coupling agent: take by weighing 15 kg of water, add 60 gram Glacial acetic acid, under agitation condition, slowly add the KH-560 of 300 grams, be stirred to till the aqueous solution clear.
2) dispersion of KH-570 coupling agent: take by weighing 10 kg of water, add 40 gram Glacial acetic acid, under agitation condition, slowly add the KH-570 of 200 grams, be stirred to till the aqueous solution clear.
3) take by weighing 0.56 kilogram MS-600, fully dissolve evenly, adds 10 kilograms of cold water and dilute even with 10 kilogram of 80～100 degree water.
4) take by weighing the 80 Ction X that restrain, fully dilute evenly with 3.0 kilogram of 60～70 water of spending, the cold water that adds 8.0 kilograms stirs.
5) take by weighing 2.0 kilograms of water-soluble epoxy resin 682 membrane-forming agents, the water that adds 10 kilograms stirs.
6) take by weighing 0.8 kilogram of Polyester Resin Water Soluble SR-2 membrane-forming agent, the water that adds 10 kilograms stirs.
7) successively material is added in the preparing tank according to above-mentioned dilution order, water is supplied weight to 100 and kilogram is stirred and can use.
Table 1
Claims (10)
1, enhancement soakage agent for thin glass fiber bulked yarn, it is characterized in that: it contains water-soluble film forming agent, is the lubricant system of assisting and regulates dispersive organosilicon alkanes coupling agent through the PH conditioning agent that based on fatty acid ester, cats product this treating compound is composed as follows:
Water-soluble film forming agent accounts for 2.0～3.5% for the treatment of compound gross weight;
Lubricant accounts for 0.64～1.05% for the treatment of compound gross weight;
Organo silane coupling agent accounts for 0.2～0.5% for the treatment of compound gross weight;
Be dispersed with the PH conditioning agent that machine silane coupling agent uses and account for 0.1～0.22% for the treatment of compound gross weight;
All the other are water.
2, enhancement soakage agent for thin glass fiber bulked yarn according to claim 1 is characterized in that: in water-soluble film forming agent, the weight ratio of water-soluble epoxy resin and water-soluble unsaturated polyester resin is 1.33: 1～2.8: 1.
3, enhancement soakage agent for thin glass fiber bulked yarn according to claim 2, it is characterized in that: water-soluble unsaturated polyester resin be total molar ratio of alcohol to acid by 1.15: 1～1.25: 1 amounts of getting, molecular weight is 400 polyoxyethylene glycol and the mol ratio cis-butenedioic anhydride that is 1: 3 and the reaction synthetics of hexanodioic acid.
4, enhancement soakage agent for thin glass fiber bulked yarn according to claim 2, it is characterized in that: water-soluble unsaturated polyester resin be total molar ratio of alcohol to acid by 1.15: 1～1.25: 1 amounts of getting, molecular weight is 600 polyoxyethylene glycol and the mol ratio cis-butenedioic anhydride that is 1: 3 and the reaction synthetics of hexanodioic acid.
5, enhancement soakage agent for thin glass fiber bulked yarn according to claim 2, it is characterized in that: water-soluble epoxy resin is meant the bisphenol A epoxide resin of oxirane value between 0.51～0.44 by the diethanolamine modification, and the mol ratio of oxirane value after the modification and amino is 1: 1～2: 1 a water-soluble epoxy resin.
6, enhancement soakage agent for thin glass fiber bulked yarn according to claim 1 is characterized in that: the lubricant system composition constitutes: the weight ratio of fatty acid ester series lubricant agent and cats product is 20: 1～7: 1.
7, enhancement soakage agent for thin glass fiber bulked yarn according to claim 5 is characterized in that: the fatty acid ester series lubricant agent is that the polymerization degree of 18 carbon fatty acids is 9～14 macrogol ester.
8, enhancement soakage agent for thin glass fiber bulked yarn according to claim 5 is characterized in that: cats product can be one of following material: the alkyl cationic quaternary ammonium salt of 9～18 carbon; The alkyl positively charged ion acid amides of 9～18 carbon.
9, enhancement soakage agent for thin glass fiber bulked yarn according to claim 1 is characterized in that: organosilicon alkanes coupling agent can be selected one of following material for use: organosilane is a γ-An Bingjisanyiyangjiguiwan; Vinyltriethoxysilane; γ-glycidyl ether oxygen base propyl trimethoxy silicane; γ-methacryloxypropyl trimethoxy silane.
10, enhancement soakage agent for thin glass fiber bulked yarn according to claim 1 is characterized in that: be dispersed with the PH conditioning agent that machine silane coupling agent uses and can select one of following material for use: Glacial acetic acid; Citric acid.
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