TW200909624A - Solution comprising blended material and solvent, fiber comprising the blended material, sheet-like material comprising the fiber, method for production of the fiber, and method for production of the sheet-like material - Google Patents

Abstract

Disclosed are: a solution comprising a blended material and a solvent, wherein the blended material comprises a resol resin having a weight average molecular weight of 3,000 to 50,000 and a poly(vinyl butyral) having a solution viscosity of 10 to 100 mPa s blended in the resol resin in an amount of 0.5 to 5 wt% relative to the total weight of the blended material; a fiber comprising the blended material; a sheet-like material comprising the fiber; a method for producing the fiber; and a method for producing the sheet-like material. It becomes possible to improve the poor spinnability of a conventional resol resin and also improve the brittleness of a fiber produced from the resol resin. Thus, it becomes possible to provide a fiber and a sheet-like material both mainly composed of a resol resin and having improved handling properties.

Description

200909624 IX. Description of the Invention: [Technical Field] The present invention relates to a fiber and a sheet composed of a blend of a resole phenolic resin having improved spinnability or brittleness. [Prior Art] In recent years, the use of fiber materials in industrial materials has been continuously promoted, and insoluble and infusible heat-resistant fibers which are excellent in chemical properties, and which are not melted at high temperatures, and heat-resistant sheets thereof have attracted much attention. . " As such a heat-resistant sheet, paper made of meta-aramid fiber is widely used, but there is a problem of high price. On the other hand, as a low-cost heat-resistant polymer, it is considered that a cross-linking type is applicable. The polymer is also studied, and the melamine fiber disclosed in Patent Document 1 and the like. However, since the equipment cost of the solution treatment such as thirst = spinning = or the cross-linking treatment is complicated, it does not seem to be widely industrialized. In the case of the raw material of the activated carbon fiber, in the case of the patent document 2 or the like, the same as the heat-resistant polymer, the phenol is crosslinked by a methylol component or the like, and the balance is 'insoluble and infusible. The resin is roughly divided into: a "hot resin" and a thermosetting type of a soluble resin, and then a solution by a crosslinking agent in a solution or the like, preferably a soluble (tetra) resin. = The actual production of the fat has a low molecular weight, so the spinnability is extremely low. If it is, the soluble secret tree monomer is difficult to fibrillate. Furthermore, even if the system can be used, the resin can be very brittle, and the 97117792 200909624 cannot be bent, which is a fatal defect that is very difficult to handle. Hereinafter, a conventional technique for fiberization of a resin will be described. Patent Document 3 discloses that an island-in-the-sea fiber in which a soluble (tetra) resin is used as an island component and polyvinyl alcohol (hereinafter sometimes referred to as "pvA") is used as a sea component, and a sea polymer is removed therefrom. This obtains a fiber composed of a soluble acid resin. However, it is a fiber composed of a soluble resin monomer, and therefore is very brittle and is degraded as <M: and is also poor in soil m m _ 铞. Further, since it is necessary to carry out the step of removing the sea agglomerates, it is a major cause of cost increase. Further, in Patent Document 4, it is disclosed that: a mixture of a secret varnish (4) and a soluble resin is electrospun (eleetrQ_spinning) (hereinafter referred to as ESP), thereby obtaining an acid varnish resin and a soluble resin. A sheet composed of a very fine fiber of the blend. It is also a poorly operated person. Further, it is disclosed in Non-Patent Document i that a coffee with a small amount of polyvinyl butyric acid is blended for the purpose of improving the brittleness of the acid varnish tree. The operability seems to be improved. However, due to the use of the secret varnish resin, it is necessary to carry out the treatment for cross-linking in the solution in consideration of the actual production process. Therefore, the equipment is complicated and costly, and the production efficiency is also poor. . As described above, there is no fiber or sheet of a resole resin which is low in cost and excellent in enthalpy and excellent in workability. (Patent Document 1) Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei 2__43997 (Patent Document 4) Japanese Patent Application Laid-Open No. Hei. 2__526() No. 85 (Non-Patent Document 1) The 6th Annual Meeting of the Fiber Society Annual Meeting, p 97117792 200909624 357 (2006) [Disclosure] (The problem to be solved by the invention) = The object of the present invention is to provide: By improving the brittleness of the conventionally-known soluble relatives, the fibers and the sheet having the operability of the fibers are used as the main body; The composition of the Loose solution; and the fiber and the sheet (the means to solve the problem) 俜: Solution: The second subject 'The solution of the blend of the present invention and the solvent is heavy! The average molecular weight is 3, _~5 〇, _; = relative to the blend as a whole. The ratio of .5 to 5 wt% is blended with a solution viscosity of 10 to 100 mPa · * ^ ^ mouth as the upper, f 4 s of polyvinyl butyral. It is preferred to use an amine-based catalyst as a catalyst, and in the second:: ^ ~ (10) mPa.s ^ ^ ratio blended with a solution viscosity of 0.001 ~ 1 () ^ dingjun blend, and the fiber diameter is one. As the above-mentioned resol resin, it is preferable to use a fee-based catalyst as a catalyst. Further, it is preferred to use a scalloped aldehyde resin having a weight of a knife and a 3,000 to 50,000. In the case where the sheet of the present invention contains the above-mentioned fibers in the form of a sheet, the method for producing the fiber of the present invention is a solution of the blend and the solution of the solvent 9717792 200909624. The electric field of i~3 kv/cm is composed of a method of electrospinning. Further, the method for producing a sheet of the present invention is characterized in that a solution of the above-mentioned blend and/or a medium is electrospun by an electric field of 1 to 3 kV/cm to be fibrillated, and It is composed of a method of collecting the fibers in a sheet form. (Effect of the Invention) The fiber composed of the solution and the blend containing the blend of the resol resin and the polyvinyl butyral according to the present invention and the sheet containing the fiber can improve the conventional resol resin. There is a problem that the spinnability is poor, and the brittleness of the fiber is improved, and the heat-resistant fiber and the heat-resistant sheet # excellent in handleability can be obtained at low cost. These fibers and sheets can be efficiently produced by electrospinning under an electric field of appropriate strength. [Embodiment] Hereinafter, the present invention will be described in detail in conjunction with preferred embodiments. The phenol resin as used in the present invention refers to a polymer having a phenol and/or a phenol derivative (hereinafter collectively referred to as a phenol) as a constituent unit, and usually contains a suitable: AST:. The resin is insoluble insoluble matter which is excellent in drug (four) properties or heat resistance by appropriate cross-linking treatment after molding. The age-sensitive varnish resin needs to be cured after the forming and then cross-linking in the solution of the parent. The wW is more refined, and the resol phenolic resin is only treated by heat treatment P. .月 直 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋Therefore, it has the advantage that it can be hardened only by heat treatment, and on the other hand, the poor spinnability is often used as a impregnated polymer or a component of a paper or a porous plate. Also, there is a defect that the polymer itself is very brittle. r Soluble acid/resin is usually obtained by reacting a expectant with an acid in the presence of an organic catalyst. The phenol is not particularly limited, and examples thereof include the following. That is, phenol; indophenol, m-cresol, p-cresol and other indophenols; 2, 3-xylenol, 2, 4-dioxanol, 2, 5-xylenol, 2,6-xylenol , 2'4-xylenol, 3,5-nonanol and other diterpene phenols; o-ethylphenol, m-ethyl phenol, ethyl phenol such as ethyl phenol; isopropyl phenol, butyl phenol, Butyl phenol such as third butyl phenol; alkyl phenol such as p-octyl phenol, p-octyl phenol, p-nonyl phenol, p-geraniol; fluorophenol, chlorophenol, bromophenol, iodine, etc. Phenol; substitution of monophenols such as phenylphenol, aminophenol, nitrophenol, dinitrophenol, trinitrophenol, etc.; and 1-naphthalene, 2-naphthene, etc. , resorcinol, o-styrene, catechol, alkyl o-diphenol, hydroquinone, alkyl hydroquinone, phloroglucinol, bisphenol A, bisphenol F, Bisphenol s, di-, naphthalene and other polyphenols, etc., may also use xylene-formaldehyde polycondensate or make-cyclopentadiene, p-trimethylene alcohol derivative, tung oil, pine oil equal to acidic conditions and The person who obtained the reaction was obtained. These may be used alone or in combination of two or more. Among these, phenol, cresol, and bisphenol A can be preferably used from the viewpoint of easily obtaining high mechanical properties. Further, the aldehyde is not particularly limited, and examples thereof include the following. That is, formic acid __, Γ polymethine, tri-β, etc., trioxane, jun, propylene, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, 97117792 200909624 butyraldehyde, caproaldehyde, acrolein, benzaldehyde, crotonaldehyde, acrolein (acr〇lein), tetraformaldehyde, phenylacetaldehyde, o-toluene furfural, salicylaldehyde and the like. These may be used alone or in combination of two or more. Among these, from the viewpoint of the reactivity of σ, it is preferable to use formaldehyde or trioxane. In the present invention, 'as a basic catalyst, from the viewpoint of reactivity, it is preferable to use an amine system such as ammonia water or a tertiary amine (triethylamine or the like) or hexamethylenetetramine to form an acid phase. The molar ratio of the reaction is not particularly limited to that of the phenolic im 〇 1, the aldehyde is 〇 5 〜 is the aldehyde is 0.7 to 2.5. The more soluble resin can be added by the following method, The system will be insured; for the Buddha point 2 and = get two: the child will be set to a high temperature, or extended time,

C is soluble. If the curing time is controlled, it is possible to further control the crosslinking reaction, which is preferable. If the curing temperature is set to be high, the ratio of the two is preferably two. Considering the available soluble 2 parameters, because == the evaporation rate of the medium is the weight of fibrosis

The mouth is more suitable for selecting an appropriate vapor, and it is preferably an alcohol such as methanol or ethanol or isopropanol. Specifically, in the case where the temperature is set to a high temperature, a high boiling point / a medium can be used as the achievable in the solution of the present invention:::=. J molecular weight can improve the formability, spinnability or;;: If the sub-inclusion is the weight average of the polystyrene (10) conversion, brittleness, so make 10 knives 1 'better 3, 〇〇〇~ 97117792 200909624 50,000. If the weight average molecular weight is 4,000 〜1 〇, 〇〇〇, the spinnability can be further improved, and the solubility in the solution is also improved, so the weight average molecular weight is gel permeation. Chromatography (hereinafter, abbreviated as GPC) was carried out, and the GPC host was calculated in the ps conversion under the following conditions: HLC-8120 analytical column manufactured by T0S0H: G1000HLX root, G2〇2, G3000HLX manufactured by T0S0H Root λ dissolution solvent: tetrahydrofuran (hereinafter, referred to as butyl HF) Flow rate: 1 · 0 mL / min Column temperature: 40 °C Only W detector. Not bad refractometer and 'if soluble phenolic resin If the amount of methyl ketone contained in the Japanese product is less, it is better in the step or the system, and it is better. More specifically, it is: i% by weight or less. The phenolic resin as a whole, preferably two' can not impair the blending ratio of the soluble age polymer: two other polymers. As other sputum, it is 1% by weight or less, more preferably, and further preferably η tongue 0/ Alumina is a 5-weight 1% polymer, which can be listed as a plate, and::; Polymerization of thermosetting heat of polymerization, heat resistance, and resistance of other materials such as photocurable grease or epoxy resin: In view of the softness of the textile, it is considered to be a low-quality phenolic varnish of the coffee resin. For example, ketone, cellulose, cellulose derivative, high heat resistant polythene 97117792 200909624 4, polyester, liquid crystal polyester, polyketone, para-aromatic polyamine, 夭 夭 poly, 趟酉, polyfluorinated acid amidoxime, etc.. Among them, cubic fragrance polyamine, polyimine, the same solvent. Among these, low-cost and cross-linking self-heat resistance, chemical resistance A varnish resin, an epoxy resin, etc. are preferred examples. The method is carried out by taking ethylene butyraldehyde (hereinafter, :: vine-based main component 'containing a copolymer of a base group and a small amount of ethyl ruthenium = == ethylene glycol (PVA) butyl (four). In the present invention, even if it reacts with other acids, it is preferred to use B from the viewpoint of improving the spinnability of the soluble resin. 'The expression of butyric acid is also used. From the viewpoint of improving the spinnability or brittleness of the soluble resin, the degree of butyralization is preferably from 5 to 816, more preferably from 60 to 68 m which can further improve the spinnability. 〇1%. Further, for the molecule, s, from the viewpoint of improving the spinnability or brittleness of the resol resin, it is preferably a high molecular weight, and the molecular weight is preferably 50,000 to 1,000,000, more preferably 8 In addition, the viscosity of the solution reflects the molecular weight or the degree of polymerization. It is easier to manage the viscosity of the solution from the step management. In the present invention, the viscosity of the solution of PVB is in the concentration of 5% by weight in ethanol. Dissolve PVB and determine the viscosity of the solution under the following conditions. The manufactured cone-and-plate type rotational viscometer (E-type viscometer ELD) was measured at 25 ° C. The taper angle was set to φ Κ 34, the number of revolutions of the rotor was 100 rpm, and the shear rate was 383 sec - 1. Further, for ethanol 97117792 12 200909624 For the solution viscosity of PVB with insufficient solubility, a mixed solvent of ethanol/toluene = 1/1 can be used. In this case, the PVB of both ethanol and mixed solvent is well corrected. The calibration curve caused by the solvent is converted to the viscosity of the solution in ethanol. As the viscosity of the solution of PVB used in the present invention, from the viewpoint of improving the spinnability or enthalpy of the soluble (tetra) resin, it is important that 10 ~l〇〇mPa· s. The more the spinnability of the viscosity-soluble resin of PVB is increased, so it is better to be as good as ^^ "Shu 2 is 50mpa· S or more. On the other hand, if the viscosity of PVB is changed In the case of over-south, the blend solution is excessively viscous. In electrospinning, the spinnability may decrease or the fiber diameter may become coarse or the fiber diameter may become uneven. The viscosity of the solution of PVB is preferably 8 〇 mPa · s or less. Point rate 'self-improving soluble _ resin spinnability View, and Lu, the important thing is 0.5% by weight or more. Also, if it is the preferred 4 soil, it is 1.5% by weight or more. The other heat resistance of Taihe Road resin is excellent, and the compatibility rate of the drug army is low. What is required is 5 weights two:: two: lower. In addition, especially for electrospinning Xiali/〇 is 3% by weight or less, the m-slip ratio is set to ^ to reduce the tendency of fiber diameter unevenness, so佺 可 可 可 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于Reducing the blending of the soluble (tetra) resin and the PVB in the total amount of the invention. The present invention solves the defect of the 97117792 13 200909624 soluble bismuth resin by the small amount of the soluble resin, and the reason is not clear, but it is presumed that as follows. That is, the reason why the soluble acid resin is poor in spinnability or brittleness is recognized. The bathing resin is a low molecular weight body, and is partially crosslinked when it is used as a raw material for spinning. Therefore, a molecular chain such as a linear polymer. Less cross-linking. = If the mixture is less i Ρνβ, the molecular bond length is prolonged not only by the sound of pVB: the chain extension of the soluble resin, but also, the numerous fluffy butyraldehyde groups can inhibit the molecules of the resol resin. The chain is over-regular, which increases the coordination of deformation and improves the spinnability or brittleness. The raw material p V A of the house = P V B does not have the effect of p v B. The reason can be: 、, 疋. PVA side chain is mostly hydroxyl, its chain-free effect instead promotes cross-linking, as the molecular chain is difficult to extend, and does not have fluffy side chains such as butyl group, so it is difficult to express as m The effect. From this point of view, it can be considered that 1 is made into a composition of PVB, and the degree of buttization is also in an appropriate range. That is, if the degree of rhodamine is too low, the fluffy butyric acid group inhibits the separation of the soluble resin: the effect of excessive agglomeration of the chain is decreased, and if the degree of cleavage is too high, the y is reduced by the soil. The chain linking effect of the resol phenolic resin is lowered. Further, the reason why the use of the butadiene in the butyric acid is higher than the use of acetic acid to improve the spinnability or the improvement in the dimensional unevenness is considered to be that the effect of the butyl group acts. The blend described in the present invention is composed of a soluble (tetra) resin and _, and may be either a solid or a liquid. The blend is made into a fiber, and is not only a raw material of a sheet but also a free structure as a heat-resistant fiber, and is widely used. Further, it is used by forming a sheet; = heat-resistant sheet. 97117792 14 200909624 The di-blend is dissolved in a suitable solvent to make a solution which can be used as a raw material for electrospinning. At this time, the polymer used for the solvent and the m may be both:: the cold solution contains soluble (four) tree wax, the celluloid, the second f group two:: alcohol, ketone, test Aa (DMS0), etc., and other 盥-methyl acetamide (DMA), medium. Among these, it is preferable to use a mixture of a non-polar solvent such as a ring-shaped Weiben, and the like, and it is preferable that the alcohol or the solvent is electrospun, and it is easy to produce. Quickly choose the appropriate evaporation rate. Therefore, it is preferable to select an alcohol or the like. Also, from the viewpoint of Ρνβ, 1 Μ is the solubility of methanol, ethanol or isopropyl ==::,: (four) degrees::= or:]-like formability or can be reduced to two's good, yet fierce "Intermediate, the right viscosity is lower, the spinnability becomes good, and the fiber diameter is also easy to be thin, which is referred to as '〇, ^, direction. Specifically, it is preferably 7; (3) minus >, the fiber diameter is not more than the tilt, and further preferably t 5 Ρ. It is more preferable that the solution viscosity measuring device for self-forming or spinning can be prepared for the "3" h liquid from the viewpoint of easy connection, and can be prepared as _·S or more. Further, the device can be applied to users in PVB. It is preferred if it is used for fiber use. Bai Xu M is used in various soft points of view: the unique role of glutinous resin, the L/D of soft ratio is increased to 10, and the fiber is preferably used as the length and diameter. The thickness of the sheet to be described later is not particularly limited, and is preferably 50 _ or more from the viewpoint of easy shape. Further, the softness is improved from 97117792 15 200909624 and the degree is ensured. ~ ίο 二特. Sexual view of the self, it is important that the diameter of the fiber is preferably 5 (four), more preferably 3 2 and the second fiber as the lower limit of the fiber diameter, from the root of the two = point Preferably, it is 〇·_ above the father's early second = "the view of the uniformity of the characteristics and the second private recognition is also self-clothing into a sheet when the average δ 'more than the diameter of the 5 (four). More preferably, it is 5 to 3, and the soil is 0.1 to the state of the surface. Further, the fiber composed of the blend of the present invention is made. :: Hair: Medium: Heat-resistant sheet or bee structure (4) ^ The skin described in the present invention is flat, and can be referred to as a two-dimensional planar structure as a main body, non-woven fabric, etc., due to the shape of fine fibers The effect is (breaking, so better) the improvement of the solubility - the peculiar brittleness of the resin: the preferred manufacturing method of the invented sheet has no special electrospinning (10)) method, and the sheet can be efficiently produced. Shape: , better. In addition, the non-woven fabric or paper formed by the ESP method can be easily produced by making a very fine and continuous fiber. Therefore, the film produced by the solution casting method can be extremely fine. - Steps to improve the brittleness of soluble secret tree materials. Softness of ''. The ESP method will be described in detail below. The so-called ESp method, is: I ^: / shows, the following spinning method: between the solution and the phase f; between the electrodes: a high electric field of about .3 kV / cm, in the course of the solution 'due to evaporation and elongation of the solution, Splitting of the solution, etc. and 97117792 200909624 Fiber: It is used as a non-woven fabric or a paper-like material composed of extremely fine fibers. If the fiber and/or sheet is used in the production method, the amine-based catalyst is used. Helmet, the medium as a catalyst' and the weight average molecular weight is 3, 〇〇〇~, dan, can be prepared in the phenolic resin, and the solution is blended with respect to the whole blend as a whole. The viscosity is 10~10 ◦ mPa · S change, the solution two electric fields. ·ι:3 The main component of the polymer is composed of Hrf, which is made into a soluble material, which is made into a raw material, Shizheng nn, which is a solution of the blend of the present invention and a solvent. If the average molecular weight is high, then it can be improved. It is important that the softness of the sheet is preferred. More specifically and preferably, the weight average molecular weight q Λλλ of the phenolic phenolic resin is preferably 4,000 to 3,000 in order to blend 0.5% by weight or more μ, and for the m bonding ratio, by root撼所'Γ Get sufficient spinnability for Esp. It is easy to produce beads: the viscosity of the Γνβ species or the blend solution is added, and sometimes the production of the beads is inhibited by appropriately adjusting the push rate or applying the electric field as shown by the electric field. As shown in Fig. 2, which will be described later, the defect of ESP is a fiber bond, and sometimes it is made into a droplet shape, which is not fibrillated. Therefore, it is impossible to eject the compound into a (4) excessive blending ratio. Changed to two. Wherein the '97117792 邾夂 邾夂 耆 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , As a solution for discharging raw materials. . Or stable, the importance of sex, preferably the method of using the nozzle: there is no particular limitation, but if it is too thick, the excess solution will be vaporized, etc. = the rule is easy to occur due to solvent evaporation: the right is based on the solution The type or application of voltage "this must be the point of view, in the present invention, the appropriate nozzle is obtained directly. From '~Nozzle: Π Use the equivalent of 18~24_ solution to directly apply voltage 4 out of the night' Π Do not use the nozzle, by virtue of the problem. The liquid 'has can solve the nozzle clogging at this time: it is the force to directly pull the polymer solution, so the liquid does not produce the coffee. (4) It cannot be absorbed from the nozzle, so it is important that the selection will cause the discharge to be dangerous. 0.1~3 k"cra. Preferably, "the important thing in the present invention is that the surface of the solution can be overcome by 茫6 to v/cm. Further, if the electric field strong liquid viscosity or the surface surface msp of the solution is applied, it is preferable, especially in the direction of dissolution. If the force is applied + ^A, it is sometimes seen that such a tilt seems to exist ^ field strength' is usually easy to obtain fine fibers. However, the force and the applied electric field, that is, the traction polymer dissolves *, if the electric field is too strong An electric field showing a minimum value of the fiber diameter is now shown. As the trapping device, the unevenness of the fiber diameter is increased. It is preferable to select a rotating roller, and only the plate can be used according to the desired shape. , and then rotate the disc or set the gap 97117792 18 200909624 = two by: set = can: 4 rows of continuous production, by rotating the round 'can also make the fine fiber alignment,, the field is not arbitrary capture Paper-like and other data; suitable for selection (4) thin enamel, etc. in the obtained paper, non-woven fabric, textile, (four) or release paper, thin; mosquito holding sheet, preferably:: c device There is no special restriction on the distance, but if it is too close and it is easy to be caught, it is difficult. In addition, it is a fibrous bead or a particle. On the other hand, if it is too far, the dielectric 2r is applied, so that it is safe for the company. These are also compared with the vapor pressure; ^ethanol, isopropanol, etc.) or acetone, or the solvent 'and the amount of discharge per nozzle is G. 01~G. 20 cmV =, the distance between the nozzle and the trap is preferably the ambient temperature of ... Or the ambient humidity is also related to the evaporation of the solvent. The ambient temperature is preferably 5 to 40 C, and the ambient humidity is preferably 1 to 75% RH. The same voltage is used in the method. Therefore, from the viewpoint of preventing leakage In addition, the humidity is preferably 75% RH or less. On the other hand, from the viewpoint of preventing ignition of the evaporation solvent caused by static electricity, the humidity is preferably (10) or more. In any case, it is important because of the use of high voltage. It is basically prevented from circulating current by actually grounding or incorporating a large resistance. It is important to use a solution of the above-mentioned invention to dissolve the liquid of 97117792 19 200909624. For this case, the resole phenolic resin is relative to the solution as a whole. In terms of rich production, if it is thick, it can improve ESP. Producing, if the nozzle is difficult to block, and because of the low viscosity, the fiber is extremely fine, and it is easy to reduce the fiber straightness unevenness. Moreover, the high concentration also has the restriction of solubility. In the case of a solvent of a resol resin, it is preferably Μ Μ Μ, and the amount is %. Further, when an alcohol is used for a relative resol phenol resin, "the concentration may be lower than a certain critical concentration, and the solubility may decrease. Compare = reselect the concentration. X, when blending with a soluble acid resin as the main body:: From the viewpoint of easy dissolution and blending, it is preferred to: mix the solution after the respective solutions. Further, if the pvB is in a large amount, and the medium is in a medium, the PVB may be in a state of only swelling-like gel, and it is preferable to dissolve the PVB-point into a solvent. Further, ς is the viscosity of the solution of the raw material, the spinnability is low, the fiber diameter is also easy to be thinned, and the fiber diameter unevenness is also reduced: However, if the viscosity is too low, the spinnability is also lost. Specifically, ° ' l 150 mPa · s ' is preferably 30 mPa · s or less, and further preferably i "pa · s or less. Also, the solution is easy to phase at the time of self-forming or spinning, preferably 9 mPa (Example) The following method is used to describe the measurement method of the present invention based on the detailed description of the method of "9 mPa....". The weight average molecular weight of the A. resole phenol resin was calculated by using GPC under the following conditions as a weight average molecular weight. 97117792 20 200909624 GPC host: HLS-8120 manufactured by TOSOH Co., Ltd. Analytical column: 1 G1000HLX manufactured by TOSOH Co., Ltd., G2000HLX 2, G3000HLX 1 Dissolved solvent: tetrahydrofuran flow: 1. 0 mL/min column temperature: 40 °C Detector: Differential Refractometer B. Solubility of Polymer Solution 'The viscosity of the solution of the polymer is determined by the cone-plate type rotational viscometer (E-type viscometer ELD) manufactured by Toki Sangyo Co., Ltd. . Set to cone angle Φ1 34, rotor rotation number 1 〇〇 rpm 'shear speed Ds = 383 sec. Further, the solution viscosity of pvb was measured by a 5 wt% ethanol solution. C. Scanning electron microscopy (SEM) was performed to deposit a platinum-palladium alloy on the fiber, and the s_4〇〇〇 type manufactured by Hitachi, Ltd. (SEM) was observed. The acceleration voltage at this time was η kv. D. The state of the fiber was SEM. Observe the H Chan private + * ^ obtained by electrospinning

For the granules, count the number, and evaluate the beads without the following: the number of beads is 〇 some _· the number of beads is 1~ more: the number of beads is 21 or more 97117792 21 200909624 The liquid shown in Fig. 3, which will be described later, and the person who is affixed to the date, are evaluated as particles in the form of a polymer-like polymer #% & The carcass was not taken as the fiber diameter of the fiber. The surface of the sheet obtained by electrospinning was observed by SEM. The fiber diameter was measured from the photo. The minimum fiber diameter in the field of view was the difference in fiber diameter as the fiber diameter. Further, in the case where the diameter of the most linear dimension exceeds 5 /z m, the measurement is carried out using 5QQ ^ , F. spinnability (4) 5 and w.

The spinnability was evaluated in the following manner, and the above was regarded as acceptable. No beads: ◎ Some Xu: 〇 多: △ Mixture of particulate and fibrous: x is only particulate: XX G· Self-supporting G for release paper used for electrospinning and sheet collection The peelability and the shape retention were evaluated, and the above was considered as pass. The sheet is easy to peel off from the release paper, and it is difficult to break. The sheet is barely peeled off from the release paper, but the breakage is: △ It cannot be peeled off from the release paper as a sheet: χ Reference Example 1 (Resolvable phenolic) Synthesis of resin) In a reaction vessel equipped with a stirring device, a reflux condenser and a thermometer, 1000 parts of phenol, 1 550 parts of 37% of formalin, and 32 parts of ammonia with a concentration of 27% were added to the reaction. hour. Thereafter, dehydration is carried out at 65 如 如 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 According to Gpc, the result of the knife in the eight-fold knife is 45〇〇, and the residual formaldehyde is 〇·4%. 1%。 Reference Example 2 (Resin phenolic resin synthesis). Between the tree and the same as in Reference Example 1 to obtain a soluble _ 2, the average molecular weight of 2800, the amount of residual formaldehyde was 1.1%.翏Test Example 3 (Synthesis of Resole Phenolic Resin) (Tree: Mie's the same method as in t test 1 to obtain the average molecular weight of the solubilized sputum s s s. [Examples 1 to 9] = The resin of the weight average molecular weight side synthesized in Reference Example i was dissolved in methanol, and the viscosity of the solution was determined to be the heart of the product = (Shuishui Chemical Industry Co., Ltd., s β . βΗ = methanol, the preparation of soluble _ lipid concentration of 29 Μ: the concentration of ρνβ of the sum of the resin and PVB is the desired value, j (and again, the calculated molecular weight of the PVB used is u The value is 10,000, and the degree is 65 mol%. In addition, the value of the product of the S-LEG series of the Computational Molecular Co., Ltd. *The value recorded by the Sekisui Chemical Co., Ltd. 胄... used in the children's book (胤.2〇05) The ESp nightmare manufactured by KATO TECii, please use the environment humidity 4G. At this time: use a 21 G needle (the front end is cut by the cutter), and make the == and width "spin" Attached to the second report, the rotation is performed at 66 rpm. The amount of discharge is U5craV minutes. Following 97117792 23 200909624 and (four) product = Becomes on the release paper and becomes self-supporting =,::: = Capacity: = The brittleness of the molded paper system is greatly improved. In addition, the SEM observation of the second table = the formation of fine fibers, the spinnability is greatly improved (Figure 1 shows The observation of Example 4 = the result, Fig. 2 shows the observation result of the embodiment!) wherein, in the embodiment 3 having a low combination rate, in Examples 4 to 7 in which the blending ratio is high as shown in Fig. 2 As shown in Fig. ==, to the beads, when the blending ratio of m is high, the tendency of excellent spinnability is exhibited. / The middle shouting is as in the case of Example 2, even if the blending ratio of m is low, no beads are observed. It may be caused by the following reasons: in the first embodiment, the electric field is relatively weak in spinnability relative to the compound, so that electrospinning is unstable, and in Example 3, the opposite field is too spinnable relative to the polymer, so electrospinning It is unstable, and the electric field is suitable for the spinnability of the polymer. Moreover, even if the m blending ratio is low, the solvent can be completely f-spread by expanding the distance between the nozzle and the trap as in the eighth embodiment. 'Inhibition of the occurrence of beads. On the other hand, if the m blend is high, no beads are observed, and the spinnability is improved, but the solution viscosity of the raw material is However, the polymer is difficult to elongate, so that the fiber diameter tends to be large. Further, in the examples 6 and 7 in which the PVB blending ratio is high, the fiber diameter unevenness is also large, which may be caused by the following reasons: The spinnability of the polymer was too strong. [Comparative Examples 1 to 3] PVB was blended in the resol resin synthesized in Reference Example 1 to prepare a methanol solution having a concentration of 29 wt%. ESP was carried out in the same manner as in the practice of 9717792 24 200909624 Example 1 and the polymer was sprayed only to the collection in a spot shape: it was not in the form of a sheet. When the electric field is strengthened, there is a slight improvement in the direction of the speckle pattern, but the sub-aluminum is a uniform sheet as in the embodiment. Further, the SEM observation: surface, fiberization itself was not realized, only the solvent evaporates from the droplet _ M f Fig. 1 shows the observation result of Comparative Example 1). Further, the above-mentioned "can be phenolic resin" cannot be peeled off from the release paper and becomes self-supporting. Ub is compared with Example 4] f 2 medium & methanol/acetone = 1/3. 8 (volume ratio) In the mixed solvent, the phenol:resin concentration was set to 19 wt%, and in the same way as the comparative example, the polymer was sprayed onto the trap only in the form of spots, and there was no loss. The tendency to improve the speckle pattern, but the application of the patch is flaky. Also, look at the surface of the surface, but not itself. It is only a particle that evaporates from the droplets. It is soluble in ESP. (4) The resin cannot be peeled off from the release paper and becomes a solution viscosity of 5 mPa·3 from 25 1 97117792 200909624 (Shuishui Chemical Industry Co., Ltd. ==, S_LE": is the same as Example 5, the second of the 4, As a result, the fiberization itself was not realized, and only the solvent was from the droplet strips to the pellets. Further, the calculated molecular weight used therein was 19,000, and the degree of butyraldehyde was 63 ra〇p/Q.

97117792 26 200909624 [I <] Self-supporting 〇〇〇〇〇〇〇〇〇 XXXXXX ! Spinnability 1 〇 ◎ 〇 ◎ ◎ ◎ ◎ ◎ ◎ XXXXXXXXX There are no beads, some discs, some discs, etc. #. Particle-like particle-like particle i-particle-like fiber diameter / μια L〇_6~1.7 I 1·1 〜1.8 L〇.6 ～1.7 1 CO <> il 0.9~3. 5 1 Λ od l οα Η 1.2~5. 8 0.6 1.7 1.7 1.5~2. 8 1 1 1 I 1 electric field/kv/cm LO 〇> CD 1 i Ο τ—Η LO 〇>〇> 1—Η Bu C3> cz> r ~H CO Γ11 1 CD 1—H ο τ—Η Applied voltage /kV ◦ LO s C3? Ο LO s LO C3 ◦ LO S LO ο Distance /cm τ—Η 〇> CD CZ5 CZ5 cz> LTD id ◦ CD C3 LO ο Solution viscosity 2 /mPa · s 05 inch CD 03 σϊ CT5 inch τ—Η CO CO CO 03 c〇 solution viscosity 1 /mPa · s LO CO LO CD LO CO LO CO LO ς〇LO CO LO CO LO CD LO CD 1 1 I 1 LO PVB addition amount / wt% i - HT - ^ i - H 1 < LO od CO CO CO CO CO CO H T " ~ H LO oi Disc CO CO Example 1 Example 2 | Implementation Example 3] | Example 4 1 1 Example 5 1 | Example 6 j | Example 7 I Example 8 | Example 9 1 | Comparative Example 1 Comparative Example 2 | Comparative Example 3 | Comparative Example 4 1 Comparative Example 5 ^筱赵焕wCQAd : 1^珐耱uaiwSH铋#*铼韹靼

LZ 200909624 [Comparative Example 6] Esp was carried out in the same manner as in Example 4 using the resin having a weight average molecular weight of 28 Å prepared in Reference Example 2, and as a result, the fiber itself was not realized, and only the solvent was liquid. The droplets evaporate in the form of particles. [Comparative Example 7] Γ The PVB blending ratio was set to 7% by weight. ESP' was fibrillated, but it was also as rough as in Example 6. [Example 11], in the same manner as in Example 6, in the occurrence of nozzle clogging, the fiber diameter blending was dissolved in the "synthesized phenolic resin synthesized in the ", and the PVB used in Example 1 was dissolved. For methanol, the concentration of the solvent is 3 G wt%, and the PVB concentration of the sum of the soluble resin discs is 〇·7 wt% (solution viscosity is i2 —· = Esp device manufactured by Guan Tech Co., Ltd. At the ambient temperature MC, the ambient humidity is 50% RH, the distance is 1 〇 (10), the voltage is applied 15 ′, and the Esp is performed at a volume of U25 cmV. At this time, it is used as a trap for the root needle (front end cutter). The release paper is attached to a rotating roller having a diameter of 0 cm and a width of 33 。. Further, the rotating roller is rotated at 12 rpm... (10) The result of the obtained sheet is observed, and the (IV) acid resin blend can be used for fiberization. It has not been found that the bead is produced and exhibits good spinnability. Moreover, the fiber diameter is finer g. = the diameter is not uniform. Further, the fiber can be easily peeled off from the release paper and f is a self-supporting piece. But it is slightly brittle compared to the sheets obtained in Examples 1 to 4. 97117792 28 200909624 [Example 12] The PVB wave was set to 〇wt% (solution viscosity was 22 coffee. ESP was performed in the same manner as in Example 11. The flaky lipid blend obtained by SEM observation was used for fibrosis, and no Found beads "~3/spunability. In addition, the fiber diameter is finer., :m, and the fiber diameter is not uniform. Further, the fiber can be peeled off from the release paper to become a self-supporting sheet. Example 13] ί The PVB concentration was set to 3. 〇 (4) (the solution viscosity was 123 and the voltage was set to n kv, and the discharge amount was set to .01): The same way as in the case of Example 11 who PCD was in the form of Xingbeiwan As a result, ESP was introduced, and as a result, the cotton material was deposited in a sheet form on the eucalyptus wood, which did not become a perfect sheet as in Example 12. The cuttable liquid was low in the amount of discharge and the applied electric field was high, so that the second development was excessively fine. In the case of high solvent odor, it is preferred from this point of view that as a result of the cotton obtained by the solution sticking, no bead formation can be observed by the voltage or sp. EMEM. (4) The lipid blend is fibrillated. Also, the fiber diameter is finer. 7~3 ί Further, the fiber can be easily peeled off from the release paper. [Example 14] The applied voltage was set to ίη 1 v to 10 kV, and the discharge amount was set to 0.050 cm 3 /min, which was the same as that of the case of Example 13 In the form of flakes, the results and Example 13 did not further reduce the applied electric field. Sa: The reason was that the amount of spit was increased, and the suppression of the solution was suppressed to inhibit the evaporation of the solvent 97117792 29 200909624. The result of the product was 纤维 总 / / 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Sex. Further, the fiber diameter is 可, which can be spun 〜13, and the fiber is not directly protected: slightly thicker than the embodiment 11, the fiber red unevenness is also small. Further, the fibers can be easily peeled off to become a self-supporting sheet.夂,,··[Example 15] 4===L3mPa.s of Sekisui Chemical Industry Co., Ltd. “S-LEC B BH-6 (calculated molecular weight of 92,000 for 69 _) as _, with In the same manner as in Example η, the m concentration of the resole phenolic resin was 3 (the viscosity of the liquid was $91 _·small in the same manner as in Example U, the applied voltage was 10 kV, and the discharge amount was 0.038 cm3. /sp Esp, h 4 tablets 'have good spinnability. 'The fiber diameter is smaller, and the field 1.3~2.6 fiber diameter unevenness is also small. Further, the fiber I can be easily released from the mold The paper was peeled off to form a self-supporting sheet. [Example 16] Esp was carried out in the same manner as in Example 15 by setting the PVB concentration to 2 wt% (solution viscosity: 56 mPa·s). As a result, although fibrosis can be achieved, there are a few beads (number of beads π). The degree of butyralization used in the present example is 69% 别% (different 6) compared to the degree of butyralization. 65 m〇l% of PVB (BH-3) used in Example 9 is sometimes unfavorable for spinnability. It can be considered that the reason is that: by the lotus, the butyric acid group is decreased, and the soluble phenol is inhibited. The effect of agglomeration of the resin is also reduced by 9717792 30 200909624. Furthermore, the fiber diameter is finer, and the fiber can be easily self-extracted. 3. 〇βηι. Further [Example 17] & s-LEC B manufactured by Sekisui Co., Ltd. having a solution viscosity of 63 mPa.s, (calculating a molecular weight of 1 〇 == 66 mol% (wherein, a copolymer of butyl hydration degree acetal)) as PVB, In the same manner as in Example 11, a solution having a concentration of lw« with respect to the oxime was prepared (the solution viscosity was the same as in the case of Example 11, the voltage was applied, and the discharge amount was 0.05 cm/min. As a result of observing the obtained sheet, the soluble resin blend was fiberized, and no beads were produced, showing good spinnability. However, the fiber diameter was 2 〇~61 ", slightly thicker than

Example 12 'The fiber diameter unevenness is also slightly larger. It can be considered that the reason is that the copolymerization in PVB has a partial acid reduction, so the bulkiness of pVB is lowered, and the inhibition can be suppressed.

The effect of agglomeration of the phenolic resin decreases. [Example 18] The applied voltage was set to 12 kV, and ESP ° was observed in the same manner as in Example 17 as a result of observing the obtained sheet by SEM, and the resol-type phenol resin blend was subjected to fiberization to produce no beads. Presents good spinnability. However, the fiber diameter is slightly thicker. 6~9. 2 # m, the fiber diameter unevenness is also slightly larger. Further, the fiber can be easily peeled off from the release paper to become a self-supporting sheet. [Comparative Example 8] PVA (manufactured by Nippon Synthetic Chemical Co., Ltd., Gohsenol GM-14L) 97117792 31 200909624 was used instead of PVB' to prepare a solution with respect to soluble phenol = day and m in the same manner as in the example u phase aldoxime I ρπ Λ A solution with a PVA concentration of "wt%. In the same manner as in the case of Example 11, the ESP was performed with an applied voltage of 15 kV and a discharge amount of 心25. As a result of observing the obtained sheet by SEM, the blend was in the form of particles, which could not be fibrillated. [Comparative Example 9]

ESP was carried out in the same manner as in Comparative Example 8, except that the discharge amount was set to cm. 05 cm3/min. As a result of observing the obtained sheet by SEM, the blend was in the form of particles, which could not be fibrillated.

97117792 32 2 099 ^#-3⁄43⁄4 U4] Self-supporting 〇〇〇〇〇〇〇〇 XX Spinnability 1 ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ XXX With or without beads 1 #. m Disc with some particles i Particles Fiber diameter / /zm 0·8 〜1.6 | 0.7~1.3 0 7 〜3.1 | 1.8~3. 3 I 1.3~2. 6 0_6 〜3_0 1 2· 0~6.1 σι ι CO cr> 1 1 Electric field/kv/ Cm LO LO H 卜t Ή 〇CZ> Ο τ—Η LO τ-Η C<J Η LO τ—H LO i-1 Applied voltage/kV LO LO CD CD ο cr> LO οα LO LO Discharge amount/cm3/ Minutes I 0.025 1 LO g CZ> 1 o.oio 1 S od οο S ο οο CO ο CD Ο s C) ο S LO C<l cr> CD osc=> Solution viscosity 2 , /mPa · s CNI 1 i CV3 CO C<! τ—Η CO oa S CD LO LO LO 1 1 PVB Addition/wt% Bu CZ5 o C3 CO CD CO CO CD CD i H ι—Η Bu C5 Bu <Z5 Solution Viscosity 1 /mPa · s LO CO LO CD LO CO LO CO CO CV3 CO C<I CO CO CO CO 1 1 PVB type L________ BH-3 | BH-3 [BH-3 I | BH-3 1 " ΒΗ-6 1 Γ ΒΗ-6 I 1 BX-1 I 1 BX-1 1 |Example ill |Example lTl Example 13 Example 14 1 Implementation Example 15] Example 16 Example 17 1 Example|Comparative Example|Comparative Example 9 1 璩 璩 效 效 ^ ^ ^ 龚 龚 命 荪 荪 荪 荪 荪 荪 荪 荪 荪 荪 荪 荪 荪 荪 荪 荪 荪 荪 荪 荪 荪 荪 荪 荪 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 1 ο ] The PVA (Nippon Synthetic Chemical Co., Ltd.'s Gohsenol ΝΜ-11) > gluten is dissolved in the β-test of sterol, but it is almost insoluble, and the soluble phenolic acid synthesized in Reference Example 1 cannot be produced. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing the result of observing the surface of the sheet of Example 4 by SEM (without beads). Fig. 2 is a view showing the sheet of Example 1 observed by SEM. A graph of the results obtained on the surface of the object (some beads). Fig. 3 is a view showing the result of observing the surface of Comparative Example 1 by SEM.

L 97117792 34

Claims (1)

200909624 X. Patent application scope: 1. A solution which is contained in a resol resin having a weight average molecular weight of 3, 〇〇〇~50,000, is blended in a ratio of 0.5 to 5% by weight relative to the whole blend. A blend of polyvinyl butyric acid with a solution viscosity of 1 〇 1 〇〇 mPa · s and a solvent. 2. The solution according to claim 1, wherein the above-mentioned resol resin is formed by using an amine-based catalyst as a catalyst. 3. A fiber derived from a resole phenolic resin blended with a solution having a viscosity of 1 〇 1 〇〇 mPa · s in a ratio of 0.5 to 5% by weight based on the total of the blend. a blend having a fiber diameter of 〇· 〇〇ι~1〇# m ° 4. The fiber of the third aspect of the patent application, wherein the above-mentioned soluble phenolic resin is formed by using an amine-based catalyst as a catalyst. . 5. A sheet comprising the fibers of claim 3 of the patent application. 6. The manufacturing method of the fiber is the dissolution of the scope of the patent application. Electrospinning with an electric field of 0.1 to 3 kV/cmi (eiectr〇spinning 7·-------------------------------------------------------------------------------------------- kV/cm 曰, ν μ 电 电 仃 仃 仃 仃 纤维 纤维 纤维 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 A brief description of the symbol of the representative figure: Yi i ί VIII. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: 97117792 4