Technology areas

[0001]

The present invention relates to the urea-modified novolak type phenolic resin manufacture method and obtained it by urea modified novolak type phenolic resin and resin can be obtained by using the dependency, preferably used as caking in particular, as the resin or resin coated urea modified novolak type phenolic resin and its effective production method, obtained further uses such as novolac phenolic resin.

His innovations.

[0002]

In addition to species-specific effects given by nitrogen compounds from the traditional and functional industrial reasons such as cost, such as urea and melamine, modified phenolic resin has used extensive. In many industries, and also improves the flame-retardant properties of modified polymer obtained, especially urea, phenol resin manufacturing, compared to phenol reaction rates increase when benefits, are widely used.

[0003]

BTW, making resol type phenolic resins, urea-modified phenolic resin, phenol and formaldehyde urea plus react and get a urea modified resol type phenolic resin technique is well known, for example, open 2009-84382 issue bulletin, 1 case has been revealed. Occurrence of cracks caused by condensed water is urea-modified resol type phenolic resin obtained, however, so in addition to moisture problems occur during forming and Formaldehyde gas by issue, difficult in practical was in its use.

[0004]

In the case of novolak type phenolic resins under acidic conditions, on the other hand, reacted to formaldehyde to phenol compounds, produced reactions of the urea who, they many be the percentage of the total amount of phenolic compounds when reacting with phenolic compounds and formaldehyde, urea, producing both condensation resins, solvent for those 3 ingredients does not progress smoothly, especially, and urea urea 10% by weight or more of usage and For manufactured highly modified by urea urea modified novolak type phenolic resin with different kinetics for phenolic compounds with urea formaldehyde, urea alone of in purpose and induced Gelation, polymerization and formaldehyde (condensation) to induce both condensation resins manufacturing itself would be difficult. Also, to demonstrate the desirable qualities of the resins, urea-denatured and resulting higher viscosity of the resin produced in such reactions, even if made of resin and was in difficult.

[0005]

Its main objective has been to suppress the odor of formaldehyde by reaction with unreacted formaldehyde residual generated by technology, especially open 58-37020 issue bulletin, using urea manufacturing of novolak type phenolic resin have been revealed, but in there after the reaction of formaldehyde and phenols, the reaction products in the urea added novolak type phenolic resins and urea; In effective methods of urea-modified novolak type phenolic resin to get advanced open 58-37020 issue bulletin, "is obviously is not.

Prior art documents

Patent documents

[0006]

Patent literature 1: open 2009-84382 issue public report
Patent literature 2: special opening of the Akira 58-37020 Gazette

Summary of the invention

Inventors are trying to solve a problem

[0007]

Is, further, mould characteristics superior to in such circumstances in the background, done in the invention, to solve problems and provides stable produce urea modified novolak type phenolic resin with low viscosity, easy-handling that can also provide a method in large amounts of urea-modified novolak type phenolic resin bearing manufacturing and get exercise to provide resin get gotten.

Means for resolving problems

[0008]

And listed below to resolve the issues mentioned above in the invention, or problems identified by the description of the entire specification and drawings to such should be suitably be carried out in different aspect, but also follows each aspect of any combination of can be adopted in is. That is in the description of the entire statement and what there get are recognized based on the disclosed invention idea, embodiment of the invention or technical features, the following stated that "rather than being limited to be understood.

[0009]

(1) until you reach the amount scheduled for wherein both condensed wherein urea or urea MetroCall said phenolic compounds and aldehydes wherein contact to manufacture urea-modified novolak type phenolic resin, phenolic compounds and aldehydes, urea or urea methylol including with condensation when the reaction of their progress on the other hand, reaction, continuously or intermittently little gradually added, with the addition of urea or urea MetroCall Feature to to with condensed ordered wherein phenolic compounds and aldehydes such as urea modified novolak type phenolic resin production methods.
(2) wherein urea or urea Metrocall, the addition of reaction in the form of aqueous solution or suspension to be getting above aspect (1) mentioned urea modified novolak type phenolic resin production methods.
(3) continuously added by constant additive speed reaction wherein urea or urea MetroCall said aspect (1) or the above-mentioned manner (2) mentioned urea modified novolak type phenolic resin production methods.
(4) intermittent addition of _said_ urea or urea methylol constant intervals, carried out at a certain amount per said embodiment (1) or the above-mentioned manner (2) mentioned urea modified novolak type phenolic resin production methods.
(5) in any one of the said urea or urea methylol solid above aspect (1) to such aspect (4) mentioned urea modified novolak type phenolic resin production methods.
(6) in any one of the initiated wherein urea or urea methylol additives made initial condensation wherein phenolic compounds and aldehydes said after the initial condensate for the above-mentioned manner (1) to the previous embodiment (5) mentioned urea modified novolak type phenolic resin production methods.
(7) the above aspect (6) addition of the urea or urea MetroCall is initiated, was equal to the amount scheduled for wherein urea or urea MetroCall said both condensed amount of aldehydes, wherein the initial condensation of trapped when mentioned urea modified novolak type phenolic resin production methods.
(8) one obtained by the manufacturing method of any of the above aspect (1) to such aspect (7) urea-modified novolak type phenolic resin.
(9), manufactured by phenolic compounds and aldehydes, urea or urea methylol with condensation, to feature urea-modified novolak type phenolic resin.
(10) with condensed phenolic compounds and aldehydes, urea or urea methylol heat absorption, manufactured by the urea modified novolak type phenolic resin, with its thermal decomposition is 5 ~ 200 J / g to feature wherein mode (9) mentioned urea modified novolak type phenolic resin.
(11) both condensed phenolic compounds and aldehydes, urea or urea MetroCall in heat absorption, manufactured by the urea modified novolak type phenolic resin, with the differential scanning calorimeter by thermal decomposition of 280 ° C ~ having absorption peak of 400 ° C range to feature the above aspect (9) or the above aspect (10) mentioned urea modified novolak type phenolic resin.
(12) the molar ratios f phenolic compounds (P) and aldehydes (F), urea or methylol urea (U) and (P+U) is the 0. 50-0. In any one of the above aspect (9) characteristics to be 75 or above aspect (11) mentioned urea modified novolak type phenolic resin.
Melt viscosity was measured at 160 ° C (13) using a cone and plate viscometer is 500-4,500 mPa-s not to feature the above aspect (9)-wherein aspect (12) any one mentioned urea modified novolak type phenolic resin.
(14) the weight average molecular weight (Mw) 550-to any of the above aspect (9) features to be 2,500 or above aspect (13) one mentioned urea modified novolak type phenolic resin.
(15) (U+P)-phenol compounds with urea or methylol urea (U) (P) urea denaturation: 5-to any one feature to 50% above aspect (9)-wherein aspect (14) mentioned urea modified novolak type phenolic resin.
(16) resin, coated with refractory particles using a urea modified novolak type phenolic resin one obtained by the manufacturing method of any of the above aspect (1) to such aspect (7), to feature.
(17) that characterized by any of the above aspect (9)-wherein aspect (15) one mentioned urea modified novolak type phenolic resin using a refractory particles coated with resin.

Advantageous effects of invention

[0010]

Will, and those with condensation reactions of novolak type phenolic resin for manufacture of urea modified novolak type phenolic resin according to this invention, phenolic compounds and aldehydes, and urea or urea MetroCall is all at once or from where it is supplied to reach rather than collectively, added, bit by bit continuously or intermittently split are added, scheduled with condensation for usage Where was that in addition to that which becomes the effective formation of urea modified novolac resin of relatively low viscosity, and thus, such as plastic manufacturing and handling is easy, to demonstrate the properties of urea-modified novolak type phenolic resin in favor.

[0011]

That it takes, and the adoption of the method of Division in a small percentage of such as urea or urea methylol with condensation reactions of phenolic compounds and aldehydes, and urea or urea methylol stable progress is gotten get urea or urea MetroCall's final supply amount (with condensation) to more the principles, that can get better in large amounts of urea-modified novolak type phenolic resin.

[0012]

With usage of interdiffusion with condensation reaction of phenolic compounds and aldehydes, in contrast, urea or urea Metrocall, all at once or or induced Gelation reacted by supplying the bulk if the rising heat of reaction, reaction temperature is rapidly rising gotten hydrolysis of urea and urea alone polymerization (condensed) will be induced by the molecular weight increases associated with this also, Or undermined the quality stability of urea-modified novolak type phenolic resin obtained, and the reaction products of very high viscosity, can bear with the practical problems inherent in.

[0013]

Also, such as get practical easy mold strength expressed in resin, urea-modified novolak type phenolic resin obtained according to the present invention has a heat absorption was proportional to its nitrogen content, because it has a high flame retardant characteristics are, such as resins, urea denaturation refractory particles caking or coating resin used as together the mould characteristics, e.g. sink marks is in and assist casting of nest failure problems and improvement of the collapse of the mold, etc..

A brief description of the drawings

[0014]

With a graph showing the results of a urea modified novolak type phenolic resin obtained in [Fig. 1] example 3, example 4, and comparing examples 3 infra-red (IR) spectra.
In the DSC curve indicates the measurement of the heat absorption of the urea modified novolak type phenolic resin resulting in a [Fig.2] example 3, example 4, and comparing examples 3.

For carrying out the invention

[0015]

BTW, raw materials give a urea modified novolak type phenolic resin is produced according to the present invention in phenolic compounds as is the phenol itself, for example, alkyl phenol, cresol, xylenol, butylphenol, Nonylphenol and Bisphenol F, resorcinol and Bisphenol-A multi made known of polyhydric phenols and their mixture to give the them used a combination of phenolic compounds alone or from time to time.

[0016]

Specifically, as the alkyl phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol and p-ethylphenol, 2, xylenol - xylenol, 3, 5 - 3, 2, 5 - xylenol, 3,4 - xylenol, 2 - propyl phenol, 2 - isopropylphenol, 3 - propylphenol, 3 - isopropylphenol, 4 - isopropyl phenol, 4 - propylphenol, 2-sec-butylphenol, is 2-tert-butylphenol, 3-sec-butylphenol, 3-tert-butylphenol, 4-sec-butylphenol, 4-tert-butylphenol, 2 - cyclohexilphenol, 3 - cyclohexylphenol, Nonylphenol 4 - cyclohexylphenol, 2 - and 3 - nonylphenol, 4 - nonylphenol, 2 - dodesylphenol, 3 - dodesylphenol, 4 - dodesylphenol, 2 - octadesylphenol, 3 - octadesylphenol, 4 - octadesylphenol, 2 - isopropyl-5 - methylphenol, 2-tert-butyl-4 - methylphenol, 3 - methyl - 6-tert--butylphenol, 2, 3, and 5 - trimethylphenol, 2, 3, 5 - triethylphenol be used.

[0017]

Are known, in the present invention, phenolic compounds as traditionally in the manufacture of phenolic resins used come various adopted from time to time, for example, various types of many of polyhydric phenols and bisphenols, condensed-ring phenols phenolic of refinery residues known to be.

[0018]

Also, as the aldehydes in the other stuff being gotten reactions to these phenolic compounds give a urea-modified novolak type phenolic resin according to the present invention, for example, compounds of known such as formaldehyde, formaldehyde, paraformaldehyde, trioxane, acetaldehyde, paraldehyde, propionaldehyde is selected accordingly to the used; Is possible through a combination of 2 or more such as aldehydes, alone, as well as phenolic compounds mentioned above, can be used.

[0019]

When you mentioned above in addition to phenolic compounds and aldehydes are reacted to the novolak type phenolic resin, used traditionally known various acid catalysts; For example, you can more oxalic acid, hydrochloric acid, sulfuric acid, maleic acid, organic acids such as phosphoric acid, inorganic acid catalyst used preferably using compounds such as zinc oxide, zinc chloride, zinc acetate, lead acetate, zinc Borate, magnesium oxide of Divalent metal salt or oxide. Furthermore, such as acid catalyst usage would be depending on the type of catalyst in the amount of scope of publicly sited appropriately, but in General, for the total amount of phenolic compounds with urea or urea MetroCall's 0. 01-10 mass %, preferably a 0. 1-1 mass % percent get adopted in.

[0020]

And MetroCall urea should be mentioned earlier in the present invention, phenolic compounds and aldehydes and acid-catalyzed reaction systems, as a third component, urea or urea methylol who can make condensation reactions to them three novolac resins of co condensation, which produces urea-modified novolak type phenolic resin, is used here is the monomac roll urea, dimethylol urea, trimethylol roll urea, urea tetramethy role. Also, should that bring reaction in aqueous solution or suspension of invention, because there are cases methylol urea and urea as a third component, in aqueous solution, suspension, or solid form, getting gotten addition reaction is to put solid in reaction, such as solid melt heat degradation kinetics of lead the. Take the third component of the urea is used in aqueous solutions in the form of General, MetroCall urea without dissolved in water completely, and therefore used as a suspension or be used as a solid.

[0021]

Also, can be used to get such as urea modified novolak type phenolic resin, phenolic compounds (P) and aldehydes (F) urea or methylol urea (U) in the molar ratio of the F/P generally, 0. 40-2. Preferably, 00 0. 50-1. You'll be 95 and value, and the F / (P+U) (molar ratio) in General, 0. 40-0. Preferably 80, 0. 50-0. Will be in proportion to 75 and interdiffusion them tripartite response. May cause more difficult and to be used for the intended usage of the resin viscosity rise due to the increase in molecular urea modified novolak type phenolic resin, take F/P and F / (P+U) values are too large to aim and in melting point, in some cases to cause the gel and resin production itself be a difficult. On the other hand, those raises problems difficult and molecular urea modified novolak type phenolic resin F / (P+U) and the F/P value is too small, and aims to reduce PROLI, reduces the melting point and the gel time is longer, to be used in applications such as resin.

[0022]

Further, of phenolic compounds with urea or urea Metrocall, third component of endothermic effects of urea modified novolak type phenolic resin urea or urea methylol usage is too low, and urea denaturation drops and get to fully demonstrate and difficult and, also, in using applications such as resin resin case, bad casting (sink marks nests, etc.) of collapse due to suppression or fully to contribute to improving difficult will be far from, generally, Mass standards, the percentage of urea for the total amount of phenolic compounds (P) as urea or methylol urea (U) or methylol urea (U) is adjusted and the rate of 5% or more. Will be used is urea, here, methylol urea consumption is used in the formation of it. Indicates the properties of urea resin, damping and characteristics of urea modified novolak type phenolic resin, on the other hand, the use of urea or urea methylol obtained, from the General, that the total mass of phenolic compounds with urea or urea methylol percentage of urea or urea MetroCall is 80% less than the preferably be adjusted to 50% less than that. It becomes difficult to use MetroCall urea and urea rates in excess of this limit and reduces the toughness and water resistance, heat resistance and increases hardness and brittleness, as resin and resin to be used.

[0023]

3 component, i.e. phenol compounds and aldehydes, and urea or urea methylol reaction, producing resins, urea-modified novolak with condensed type when the invention mentioned in the reactions of phenolic compounds and aldehydes, and the third component of addition (gradually) little by little until you reach the amount destined to the condensation with urea or urea Metrocall, the addition of urea or urea methylol phenol based compounds and aldehydes, sequentially, What to do with condensation to be.

[0024]

And allows usage of methylol urea urea condensation, such as both being gotten so over the course of the reaction, get little addition reaction heat of neutralization on the addition of the heat of condensation reaction under acid catalyzed phenol compounds and aldehydes, urea or urea methylol occurs rapidly, reaction temperature rises to effectively suppress or prevent getting other categories, hold down the hydrolysis of urea and urea MetroCall The acidic reaction should be able to encourage in favor to get longer retention time by eutectic reaction of phenolic and urea or urea metrocall.

[0025]

Here, urea and urea Metrocall, the aqueous solution pH = 7... Cause urea hydrolysis would 5 or weak alkaline and, further, the solution is heated to temperatures of over 100 ° C and a pH value will soar due to ammonia and then as a result of the study on reaction temperature and pH value in the present invention, before the addition of urea or urea MetroCall added time, generally, reaction of pH value is neutral pH from acidic (pH = 4 or less) (pH = 7-8 or so) to be in advance, preferably pH = 7. Can be up to 5 and, further, added as an additive time starting from 1. 5-is preferable to the addition of about 2 hours.

[0026]

Also in the present invention a little methylol urea and urea additive would be done continuously or intermittently, but not a continuous addition method constant additive speed (constant speed for a certain amount of) been adopted in favor the addition of reaction, can be carried out in a certain amount of each open intervals in the intermittent addition method of urea and urea Metrocall, desirable. Intermittent, spaced this addition method, for example, cases can bring out a certain amount, the amount of usage of urea and urea MetroCall is gradually dropping reaction it every 10 minutes, the system, including adopting feasible.

[0027]

After the from, where the reaction between urea and phenol and hydroxymethyl derivatives of them, and caused preferentially by phenol hydroxymethyl group with condensation with urea and also reacts preferentially and urea hydroxymethyl group under acidic conditions, the respect the pH dependence of the reaction medium, under strongly acidic or under alkaline conditions are single polymerization of urea, i.e. urea and aldehyde condensation reaction is induced to be in the present invention, phenolic compounds and aldehydes, and the early condensation. The obtained initial condensate for the addition of urea or urea MetroCall is initiated, takes urea and urea methylol interdiffusion with condensed phenolic compounds and aldehydes, turn so that is desirable.

[0028]

Molar amount of aldehydes in particular, used solvent in the third component of easier and induced increase of novolac resins to generate larger than molar amount of urea in urea or methylol cases, that relationship or hold in reaction and molecular weight and viscosity rises from the invention, first, phenol based compounds and aldehydes, and initial condensation has gotten, and obtained initial condensate in residual unreacted aldehydes amount (moles) In addition takes urea or urea MetroCall is initiated, was equal to the amount of urea or urea methylol (scheduled for copolymerization usage mole) when that is desirable.

[0029]

Additives such as phenolic compounds and aldehydes, and after initial condensation, urea or urea MetroCall's timing is, in the presence of a given amount of acid catalyst in place phenolic compounds (P) and aldehydes (F) in the molar ratio of condensation reaction done, over by the relationship between residual aldehyde (unreacted) residual aldehyde content was obtained and measure time (y) and reaction time (x) determining, as, for example, exponential approximation equation and using the equation It becomes possible to calculate the added time of urea or urea methylol start time of the solvent, in other words.

[0030]

For example, in the condensation reaction between phenol and formalin as an acid catalyst, oxalic acid, 0... 5 mass % (vs. phenolic) using the molar ratio of (F/P = 0. 65, 0. 69, 0. 84, 1. 00, and 1. 23, 1. 54) in response to progress should be getting exponential approximation of formaldehyde residual (y) as shown in table 1 below, by measuring the amount of residual formaldehyde, getting, and reaction time (x). And below that obtained exponential approximation than the A of table 1 and should get is easy to calculate reaction times to reach the equivalent of formalin (formaldehyde residual) as the amount of substance (mole) of urea in the reaction of F (h).

[0031]

Calculation of the reaction start time (h) would be done in the following steps. Namely, first, the following expression:
Formaldehyde residual (y) =
Amount of substance (mole) of urea / formalin substances amount (moles) × 100
In easily obtainable by calculating the x in, and compute residual formalin (y), then the resulting formaldehyde residual (y), y of the equation in table 1 below and substitute the equivalent condensation with urea or urea methylol interdiffusion start reaction time (h).

[0032]

[Table 1]

[0033]

In addition, urea modified novolak type phenolic resin obtained according to the present invention techniques is both a condensation product of urea derivatives and phenolic compounds, explains about the reaction mechanism. Namely, first, under acidic conditions, generates hydroxymethylphenol due to condensation reactions of phenolic compounds and aldehydes, and, in the early stages of hydroxymethylphenol and phenol and relatively low molecular weight of reaction products formed. That would be followed by the added time given the methylol urea and urea reaction at a predetermined rate little by little be prevent the reaction temperature and also inhibits the hydrolysis of urea and urea Metrocall, while the pH of the reaction rise peacefully, but acidic, induced preferential reaction between urea and hydroxymethylphenol, formed a common condensate and want to.

[0034]

And obtained urea modified novolak type phenolic resin like anyway, can advantageously be used for various applications, the handling is easy, and in large amounts of urea get gotten modified by that relatively low viscosity of proportionally to its nitrogen content, 350-365 ° C region with greater heat absorption effect, also would be increased flame retardant, and this advantageously used for various purposes.

[0035]

Is urea modified novolak type phenolic resin described above, is in the manufacturing process or additive after its manufacture, any compound or resin, for example, epoxy resin, melamine resin, urea resin, xylene resin, polyvinyl acetate, polyamide resin, Melamine compound, epoxy compounds, cashew nut oil, etc., seshimetari mixing, or to react, using various modified novolak type phenolic resin as possible.

[0036]

And the urea modified novolak type phenolic resin according to the present invention thus obtained, is according to its characteristics, be used for various purposes, but especially the invention is used preferably as the caking of the mould resin or resin coated.

[0037]

Method for coated urea modified novolak type phenolic resin takes various known method, for example hot may ring, according to information produced by resin using a urea modified novolak type phenolic resin, according to the present invention, a place of fire resistance of particles to be adopted. As a amount of urea-modified novolak type phenolic resin used for fireproof grain 100 mass part 0... 4-preferably in proportion to become a 5 weight of about 0. 5-4 mass of degree, such as percentages, a mixture of refractory particles, coated surface of the fire resistance of particles.

[0038]

Is used as refractory particles as used here, is a variety of well-known, even particles of natural, man-made particles even better, is not particularly limited. For example, in quartz, olivine sand, zircon sand, chromite sand, alumina sand, ferrochrome slags, Ferro-nickel slag, LD converter slag, mullite based artificial particles (can you get for example, Itochu ceratech co., Ltd. from the product name "cerabeads", etc.), these recycled sand, etc. cited be used, combined with a kind of these or more than 2.

[0039]

And in casting using mold molding using the obtained resin like anyway, sink marks in casting such as nest of bad get suppressed effectively, also features excellent mold casting after the collapse of the.
Implementation example

[0040]

And needless to say that the one below shows some embodiments of the present invention, invention more specifically, obviously, but the invention such cases, any constraints also affected by that time. Also, should be understood that the invention the above further addition to the examples below, specific descriptions in addition to not deviating from the purpose of the invention, based on the knowledge of the skilled added various changes, fixes, improvements, etc.. F, shown below, P and U, respectively, are used as abbreviations of formalin, phenol, and urea.

[0041]

-Example1 - urea denaturation 5% novolac resin [molar ratio (F / (P+U)) = 0. 60] of the manufacturing
I flasks, thermometers, bacuemsthaler and cooling tube with 3000 ml, phenolic 1200 g (12. 77 mol) and formalin 47% aqueous 527 g (8. 26 mol), and as a catalyst of oxalic acid 6. 3 g (0. 07 mol) then housed and stir mixture while gradually reflux reaction vessel temperature (98-105 ° C) until the temperature increases, and did the initial reaction by heat and agitate for 22 minutes.

[0042]

Subsequently, the obtained initial condensation reaction for the advance in 90 ml of distilled water dissolved urea 60 g (1. 00 mol), after 120 minutes to complete the addition of dripping, for about 60 minutes heating and stirring, and wrangle further reaction progress. And by reducing concentration and heating ensure that takes heat and agitate reaction after the pH 7, formalin is consumed, then stir mixture and reaction temperature (temperature) and approx. 180 ° C until the, got the yellow transparent solid urea modified novolac resin (urea-modified novolak type phenolic resin).

[0043]

-Example 2 - urea denaturation rate 9% novolac resin [molar ratio (F / (P+U)) = 0. 60] of synthesis
I flasks, thermometers, bacuemsthaler and cooling tube with 3000 ml, phenolic 1200 g (12. 77 mol) and formalin 47% aqueous 566 g (8. 86 mol), and as a catalyst of oxalic acid 3. 8 g (0. 04 mol) then housed and stir mixture while gradually reflux reaction vessel temperature (98-105 ° C) until the temperature increases, and did the initial reaction by heat and agitate for 22 minutes.

[0044]

Then, the obtained initial condensation reaction for the prior 180 ml distilled water dissolved in urea 120 g (2. 00 mol), stir heated for 60 minutes after 120 minutes to complete the addition of dripping and wrangle further reaction progress. And got a yellow transparent solid urea modified novolak resin by vacuum concentration and heating ensure that after the reaction by heating stirrer pH 7, formalin is consumed, then stir mixture and reaction temperature (temperature) and approx. 180 ° C until the,.

[0045]

-Example 3 - urea denaturation rate 20% novolac resin [molar ratio (F / (P+U)) = 0. 60] of synthesis
I flasks, thermometers, bacuemsthaler and cooling tube with 3000 ml, phenolic 960 g (10. 21 mol) and formalin 47% aqueous 544 g (8. 53 mol), and as a catalyst of oxalic acid 6. 0 g (0. 07 mol) then housed and stir mixture while gradually reflux reaction vessel temperature (98-105 ° C) until the temperature increases, and did the initial reaction by heat and agitate for 22 minutes.

[0046]

Subsequently, the obtained initial condensation reaction for the advance 360 ml distilled water dissolved in urea 240 g (4. 00 mol), stir heated for 60 minutes after 120 minutes to complete the addition of dripping and wrangle further reaction progress. And got a yellow transparent solid urea modified novolak resin by vacuum concentration and heating ensure that after the reaction by heating stirrer pH 7, formalin is consumed, then stir mixture and reaction temperature (temperature) and approx. 180 ° C until the,.

[0047]

-Example 4 - urea denaturation 30% novolac resin [molar ratio (F / (P+U)) = 0. 60] of synthesis
I flasks, thermometers, bacuemsthaler and cooling tube with 3000 ml, phenolic 840 g (8. 94 mol) and formalin 47% aqueous 572 g (8. 96 mol), and as a catalyst of oxalic acid 6. 0 g (0. 07 mol) then housed and stir mixture while gradually reflux reaction vessel temperature (98-105 ° C) until the temperature increases, and did the initial reaction by heat and agitate for 30 minutes.

[0048]

Subsequently, the obtained initial condensation reaction for the advance 540 ml distilled water dissolved in urea 360 g (6. 00 mol), stir heated for 60 minutes after 120 minutes to complete the addition of dripping and wrangle further reaction progress. And got a yellow transparent solid urea modified novolak resin by vacuum concentration and heating ensure that after the reaction by heating stirrer pH 7, formalin is consumed, then stir mixture and reaction temperature (temperature) and approx. 180 ° C until the,.

[0049]

-Example 5 - urea denaturation rate 40% novolac resin [molar ratio (F / (P+U)) = 0. 60] of synthesis
I flasks, thermometers, bacuemsthaler and cooling tube with 3000 ml, phenolic 720 g (7. 66 mol) and formalin 47% aqueous 599 g (9. 39 mol), and as a catalyst of oxalic acid 6. 0 g (0. 07 mol) then housed and stir mixture while gradually reflux reaction vessel temperature (98-105 ° C) until the temperature increases, and did the initial reaction by heat and agitate for 32 minutes.

[0050]

Subsequently, the obtained initial condensation reaction for the advance 720 ml distilled water dissolved in urea 480 g (7. 99 mol), stir heated for 60 minutes after 120 minutes to complete the addition of dripping and wrangle further reaction progress. And got a yellow transparent solid urea modified novolak resin by vacuum concentration and heating ensure that after the reaction by heating stirrer pH 7, formalin is consumed, then stir mixture and reaction temperature (temperature) and approx. 180 ° C until the,.

[0051]

-Example 6 - urea denaturation rate 50% novolac resin [molar ratio (F / (P+U)) = 0. 60] of synthesis
I flasks, thermometers, bacuemsthaler and cooling tube with 3000 ml, phenolic 600 g (6. 38 mol) and formalin 47% aqueous 627 g (9. 82 mol), and as a catalyst of oxalic acid 6. 0 g (0. 07 mol) then housed and stir mixture while gradually reflux reaction vessel temperature (98 to 105 ° C) until the temperature. Next, after this temperature rise, the advance in 900 ml of distilled water dissolved urea 600 g (9. 96 mol), after 120 minutes to complete the addition of dripping, 60-minute heating by stirring a reaction brought about progress. And confirmed that takes heat and agitate reaction after the pH 7, formalin is consumed. Got a yellow transparent solid urea modified novolak resin can then stir mixture and until approx. 180 ° C and the temperature of the reaction mixture (fluid temperature), heating and vacuum concentration. Use of urea to launch in this example, the amount of formaldehyde from 0. Unlike the 14 mol for each example above, did not conduct the initial reaction.

[0052]

Examples - 7 - urea denaturation 5% novolac resin [molar ratio (F / (P+U)) = 0. 60] of synthesis
I flasks, thermometers, bacuemsthaler and cooling tube with 3000 ml, phenolic 1200 g (12. 77 mol) and formalin 47% aqueous 527 g (8. 26 mol), and as a catalyst of oxalic acid 6. 3 g (0. 07 mol) then housed and stir mixture while gradually reflux reaction vessel temperature (98 to 105 ° C) until the temperature. 60 g urea followed by the previously dissolved in 90 ml of distilled water (1. 00 mol), after 120 minutes to complete the addition of dripping, 60-minute heating by stirring a reaction brought about progress. And confirmed that takes heat and agitate reaction after the pH 7, formalin is consumed. Got a yellow transparent solid urea modified novolak resin can then stir mixture and until approx. 180 ° C and the temperature of the reaction mixture (fluid temperature), heating and vacuum concentration.

[0053]

-Example 8 - urea denaturation 30% novolac resin [molar ratio (F / (P+U)) = 0. 70] of synthesis
I flasks, thermometers, bacuemsthaler and cooling tube with 3000 ml, phenolic 840 g (8. 94 mol) and formalin 47% aqueous 667 g (10. 5 mol), and as a catalyst of oxalic acid 6. 0 g (0. 07 mol) then housed and stir mixture while gradually reflux reaction vessel temperature (98-105 ° C) until the temperature increases, and did the initial reaction by heat and agitate for 88 minutes.

[0054]

Subsequently, the obtained initial condensation reaction for the advance 540 ml distilled water dissolved in urea 360 g (6. 00 mol), stir heated for 60 minutes after 120 minutes to complete the addition of dripping and wrangle further reaction progress. And got a yellow transparent solid urea modified novolak resin by vacuum concentration and heating ensure that takes heat and agitate reaction after the pH 7, formalin is consumed, then stir mixture and reaction temperature (temperature) and approx. 180 ° C until the,.

[0055]

-Examples 9 - urea denaturation 30% novolac resin [molar ratio (F / (P+U)) = 0. 50 ' of synthesis
I flasks, thermometers, bacuemsthaler and cooling tube with 3000 ml, phenolic 840 g (8. 94 mol) and formalin 47% aqueous 476 g (7. 5 mol), and as a catalyst of oxalic acid 6. 0 g (0. 07 mol) then housed and stir mixture while gradually reflux reaction vessel temperature (98-105 ° C) until the temperature increases, and did the initial reaction by heat and agitate for 10 minutes.

[0056]

Subsequently, the obtained initial condensation reaction for the advance 540 ml distilled water dissolved in urea 360 g (6. 00 mol), stir heated for 60 minutes after 120 minutes to complete the addition of dripping and wrangle further reaction progress. And got a yellow transparent solid urea modified novolak resin by vacuum concentration and heating ensure that takes heat and agitate reaction after the pH 7, formalin is consumed, then stir mixture and reaction temperature (temperature) and approx. 180 ° C until the,.

[0057]

– Example 10 - monomac roll urea denaturation rate 20% novolac resin [molar ratio (F / (P+U)) = 0. 60] of synthesis
First of all, 1000 ml flask, urea 240 g (4. 00 mol), 240 ml distilled water and 47% formalin solution 255 g (4. 00 mol) housing and pH = 9-adding NaOH until the 10 to react, liquid suspension got muddled form monomac roll urea. And transferred to the Roth-liquid suspensions obtained monomac roll urea.

[0058]

4 mouth flask attached-liquid Roth followed, featuring bacuemsthaler and cooling tubes, thermometers, housed above methylol urea suspension in addition to 3,000 ml, phenolic 960 g (10. 21 mol) and formalin 47% aqueous 289 g (4. 52 mol), and as a catalyst of oxalic acid 6. 0 g (0. 07 mol) then housed and stir mixture while gradually reflux reaction vessel temperature (98-105 ° C) until the temperature increases, and wrangle after dripping to complete the addition in 120 minutes monomac roll urea suspension-fluid Roth and then 60 minutes heat and agitate that the reaction progress. And confirmed that takes heat and agitate reaction after the pH 7, formalin is consumed. Got a yellow transparent solid urea modified novolak resin by heating and pressure concentrated then stir mixture and until approx. 180 ° C and the temperature of the reaction mixture (fluid temperature), the.

[0059]

-Examples 11 - monomac roll urea denaturation rate 30% novolac resin [molar ratio (F / (P+U)) = 0. 50 ' of synthesis
First of all, for 1000 ml flask, 360 g of urea (6. 00 mol), 540 ml distilled water and 47% formalin solution 382 g (6. 00 mol) housing and pH = 9-adding NaOH until the 10 to react, liquid suspension got a white solid forms dated monomac roll urea. And into this obtained monomac roll urea suspension-fluid Roth, with a condensation reaction with phenol.

[0060]

4 mouth flask attached-liquid Roth followed, featuring bacuemsthaler and cooling tubes, thermometers, housed above methylol urea suspension in addition to 3,000 ml, phenolic 840 g (8. 94 mol) and formalin 47% aqueous 96 g (1. 51 mol), and as a catalyst of oxalic acid 6. 0 g (0. 07 mol) then housed and stir mixture while gradually reflux reaction vessel temperature (98-105 ° C) until the temperature increases, and wrangle after dripping to complete the addition in 120 minutes monomac roll urea suspension-fluid Roth and then 60 minutes heat and agitate that the reaction progress. And confirmed that takes heat and agitate reaction after the pH 7, formalin is consumed. Can be heated and evaporated and the residue then stir mixture and until approx. 180 ° C and the temperature of the reaction mixture (fluid temperature), got a yellow transparent solid urea modified novolak resin.

[0061]

-Implementation example 12 - monomac roll urea denaturation rate 30% novolac resin [molar ratio (F / (P+U)) = 0. 60] of synthesis
First of all, for 1000 ml flask, 360 g of urea (6. 00 mol), 360 ml distilled water and 47% formalin solution 382 g (6. 00 mol) housing and pH = 9-adding NaOH until the 10 to react, liquid suspension got muddled form monomac roll urea. And transferred to the Roth-liquid suspensions obtained monomac roll urea.

[0062]

4 mouth flask 3000 ml-liquid Roth followed, featuring bacuemsthaler and cooling tubes, thermometers, even housed above methylol urea suspension installed, phenol 840 g (8. 94 mol) and formalin 47% in water 190 g (2. 97 mol), and as a catalyst of oxalic acid 6. 0 g (0. 07 mol) then housed and stir mixture while gradually reflux reaction vessel temperature (98-105 ° C) until the temperature increases, and wrangle after dripping to complete the addition in 120 minutes monomac roll urea suspension-fluid Roth and then 60 minutes heat and agitate that the reaction progress. And confirmed that takes heat and agitate reaction after the pH 7, formalin is consumed. Got a yellow transparent solid urea modified novolak resin by heating and pressure concentrated then stir mixture and until approx. 180 ° C and the temperature of the reaction mixture (fluid temperature), the.

[0063]

-Implementation example 13 - dimethylol urea denaturation rate 20% novolac resin [molar ratio (F / (P+U)) = 0. 50 ' of synthesis
First of all, 1000 ml flask, urea 240 g (4. 00 mol), 360 ml distilled water and 47% formalin solution 453 g (7. 10 mol) houses, and pH = 9 and got a white solid dimethylol urea with suspended sediment by adding NaOH until the 10 to respond.

[0064]

I flask followed by a thermometer, bacuemsthaler and cooling tube with 3000 ml, phenolic 960 g (10. 21 mol), and as a catalyst of oxalic acid 6. 0 g (0. 07 mol) then housed and stir mixture while gradually reflux reaction vessel temperature (98-105 ° C) until the temperature increases, and obtained by the above dimethylol urea with suspended sediment, spent 10 minutes at the interval, 120 minutes, was split up at a constant rate. By 60 minutes between the heat and agitate, the reaction to wrangle the progress. And confirmed that after such reaction, pH 7, formalin is consumed. Got a yellow transparent solid urea modified novolak resin by heating and pressure concentrated then stir mixture and until approx. 180 ° C and the temperature of the reaction mixture (fluid temperature), the.

[0065]

-Implementation example 14 - dimethylol urea denaturation rate 20% novolac resin [molar ratio (F / (P+U)) = 0. 60] of synthesis
First of all, 1000 ml flask, urea 240 g (4. 00 mol), 360 ml distilled water and 47% formalin solution 544 g (8. 53 mol) houses, and pH = 9 and got a white solid dimethylol urea with suspended sediment by adding NaOH until the 10 to respond.

[0066]

I flask followed by a thermometer, bacuemsthaler and cooling tube with 3000 ml, phenolic 960 g (10. 21 mol), and as a catalyst of oxalic acid 6. 0 g (0. 07 mol) then housed and stir mixture while gradually reflux reaction vessel temperature (98-105 ° C) until the temperature increases, and obtained by the above dimethylol urea with suspended sediment, spent 10 minutes at the interval, 120 minutes, was split up at a constant rate. By 60 minutes between the heat and agitate, the reaction to wrangle the progress. And confirmed that after such reaction, pH 7, formalin is consumed. Got a yellow transparent solid urea modified novolak resin by heating and pressure concentrated then stir mixture and until approx. 180 ° C and the temperature of the reaction mixture (fluid temperature), the.

[0067]

-Comparative example 1 - urea denaturation by urea imports 30% novolac resin [molar ratio (F / (P+U)) = 0. 60] of synthesis
Urea dissolved in 120 ml of distilled water beforehand I flask of 500 ml with thermometer, bacuemsthaler and cooling tube 90 g (1. 50 mol) and phenol 210 g (2. 13 mol) and formalin 47% aqueous 139 g (2. 18 mol), and as a catalyst of oxalic acid 1. 5 g (0. 02 mol) and later housed and stir mixture while gradually reflux reaction vessel temperature (98-105 ° C) to wrangle a condensation reaction by temperature and thermal agitation to a further approx. 240 minutes. And, after such reaction, stirring mixture and heated and concentrated under reduced pressure, while reaction temperature (temperature) and gel at about 150 ° C,, had solidified.

[0068]

-Comparative example 2 - monomac roll urea denaturation 6% novolac resin [molar ratio (F / (P+U)) = 0. 68] of synthesis
Equipped with thermometers, bacuemsthaler and cooling tube 500 ml flask, first of all, the urea 12 g (0. 20 mol) and formalin 47% aqueous 23 g (0. 36 mol) and houses, 150 minutes at 50 ° C heat and agitate the phenol 188 g (2. 00 mol), and as a catalyst of oxalic acid 0. 94 g (0. 01 mol) and accommodate a reflux a reaction vessel gradually while stirring and mixing temperature (98-105 ° C) until the temperature increases, and stirred for 60 minutes, reacted. In addition to formalin 47% aqueous 73 g (1. 14 mol) and oxalic acid 0. 6 g (6. 00 mmol) in addition, 120 min reflux with stirring and reaction brought about progress. At around 150 ° C reaction temperature (temperature) gel so far after such reaction, stirring mixture and heated and enriched by the vacuum, and had solidified.

[0069]

-Comparing examples 3 - novolac resins [molar ratio (F/P) = 0. 60] of synthesis
I flask equipped with thermometers, bacuemsthaler and cooling tube 3000 ml, phenolic 1200 g (12. 77 mol) and formalin 47% aqueous 490 g (7. 68 mol), and as a catalyst of oxalic acid 3. 6 g (0. 04 mol) then housed and stir mixture while gradually reflux reaction vessel temperature (98-105 ° C) to wrangle a condensation reaction by temperature and thermal agitation to a further 240 minutes. And got a yellow transparent solid of novolak type phenolic resin can take reaction after the stirring and mixing, reaction temperature (temperature) until approx. 180 ° C, heating and vacuum concentration.

[0070]

[Performance evaluation 1]
Above various urea modified novolac resin composition for the following measurement methods, respectively, various properties were measured. And results obtained the following table 2 and table 3 parallel combination shown.

[0071]

-Determination of weight-average molecular weight (Mw) the number average molecular weight (Mn), amount of unreacted phenol--
Determination of urea modified novolak resin composition the weight average molecular weight (Mw) and the number-average molecular weight (Mn) is sought as a molecular weight of phenol conversion measured by gel permeation chromatography (GPC). The GPC apparatus apparatus, (East saw co., Ltd. made the product name:HLC8320GPC) used and also on the column, mixed polistylengelcolumn (East Tosoh Corporation, product name:G1000HXL, G2000JXL) using. Also, the GPC method at the same time take obtained amount of unreacted phenol.

[0072]

-Determination of nitrogen content-
Nitrogen content of urea-modified novolak resins each sought by Kjeldahl nitrogen determination method.

[0073]

-The measure of Gelation time, melting point-
Each urea modified novolak resin flow, Gelation time and melting point are conform to JIS K 6910 and measured.

[0074]

-Measurement of viscosity
Each urea modified novolak resin viscosity is a cone and plate viscometer (TOA industry co., Ltd., product name:CV1S) used the samples of 0. 15 g of the plate temperature: drove by at 160 ° C and measure the melt viscosity.

[0075]

-Calorific value measurement
Heat absorption resins, urea-modified novolak each differential scanning calorimeter (DSC) by the thermal decomposition of the measured as follows.

[0076]

I.e. the differential scanning calorimeter as the product name:DSC8230 journal, using the powdered sample 5. 00 mg hexamethylenetetramine up 0. measured temperature absorption heat chromatogram observed from absorption heat curve (DSC curve) associated with the resolution obtained by mixing 75 mg, from under a nitrogen atmosphere, 25 ° C to 500 ° C in 5 ° C per minute to increase the temperature of the heat absorption is also calculated from above DSC curve. Vertex of the curve curve DSC curves measured at this time would be curved vertical heat rises gradually with increase in temperature on the horizontal axis, in particular temperature range due to heat absorption heat once to descend, descend to this heat on absorption peak (Figure 2 example 3 and example 4 300 ° C-400 ° C range curve).

[0077]

[Table 2]

[0078]

[Table 3]

[0079]

Structure analysis of [performance evaluation 2] urea modified novolak resin
--Determination of methylene coupling in urea-modified novolak resin bonding and Ortho-para-(o/p) combined ratio-
Nuclear magnetic resonance measurements of bonding resins, urea-modified novolak each methylene coupling and coupling o/p is (United States: manufactured by Varian; INOVA 400) using the 13 c-NMR (100 MHz, solvent: heavy pyridine-d5) measure, [o, o-phenol - CH2 -phenol] joins the [o, p-phenol - CH2 -phenol] joins the [p, p-phenol - CH2 -phenol] joins the [ o-phenol - CH2 -NHCO-] join [p-phenol - CH2 -NHCO-] combined, [-NH-CH2 hydrazones, join the present density the calculated coupling ratio of each. Resin, used for this measurement is in example 4, examples 11 & 14 implementation examples. As a result, shown in table 4.

[0080]

[Table 4]

[0081]

-Infra-red (IR) absorption spectrum measurement-
Resins, urea-modified novolak each infrared (IR) spectra of the infrared spectrometer is (made by JASCO products company; FT/IR-4200) and measured by NH coupling characteristic absorption band (1450 cm-1), CH2 bond characteristic absorption bands (1300-1400 cm-1), characteristic absorption bands of the C = O bond (1700 cm-1) of confirmed the existence. You can recognize that in there, in particular, due to the presence of the C = O bond, urea-modified novolak resin is formed. Resin, used for this measurement is in example 3, example 4, and comparing examples 3. And the result is shown in Figure 1.

[0082]

In addition, for urea modified novolac resin obtained in example 3, example 4, and comparing examples 3, due to the thermal decomposition of urea-modified novolak resins each using differential scanning calorimeter (DSC) DSC curves, the result is shown in Figure 2.

[0083]

In urea modified novolak type phenolic resin according to this invention, manufactured by the structural analysis of these resins, urea-modified novolak phenolic compounds and aldehydes, urea or urea methylol with condensation, by showing the example 1 and represented by the following general formula (1). Furthermore, the m 0-20 integer that indicates.
[Of 1]

[0084]

Using resins, urea-modified novolak obtained then, like the shells of shell mold for resin coatedtsand (RCS) (samples 1-15), respectively, produced according to the following method.

[0085]

-Sample 1-15 manufacturing and evaluation-
Experimental speed mixer for 150-7000 g 180 ° C preheated refractory particles (Flatley) and example 1-14 or comparison sample 3 of each resin 140 g (2. 0% fire resistance of particles) and by 60 seconds in the mixer to knead and then put on a fireproof surface wrangle liquid coating resins, urea-modified novolak each. Next, in a mixer, hexamethylenetetramine curing agent 21 g (15. 0% resin) cooling water: 105 g (1. 5% fire resistance of particles) to hexamethylenetetramine aqueous will melt, and the fan-cooled after the calcium stearate 7 g (0. 1% refractory particles) by adding various RCS (sample 1-15) got. Obtained sample 1-15, we were measurements of its characteristics according to the following test method. Results shown in table 5 below.

[0086]

Evaluation [3]
-Determination of the splicing points--
Using a variety of phenolic resins for RCS was manufactured in the above, JACT law compliance with the respectively measured.

[0087]

-Easy mold strength measurement-
Using a variety of phenolic resins for RCS made above, according to JIS-K-6910, respectively, JIS type piece (width: 10 mm × thickness: 10 mm x length: 60 mm, baking conditions: 250 ° C×60 seconds between) prepared and evaluated as easy mold strength that obtained JIS type test pieces (below, just say piece and TP), cold strength (MPa) measured according to the JACT test method:SM-1.

[0088]

[Table 5]

[0089]

Table 2 above-from the results shown in table 5 get modified novolac resins, urea (urea-modified novolak type phenolic resin) and let our condensation with urea or urea MetroCall is clear focus on comparative example 1-example 1 2, bulk loading, total amount of urea or urea MetroCall and gelled, good resin is not formed according to the invention-14, addition rate percentage in the urea or urea Metrocall, a little by adding better convenience, Where you can get the urea modified novolac resin with low viscosity.

[0090]

Also implementation example 1 results as evidenced by the phenol with formaldehyde ago reacting (initial condensation reaction), urea, a little slowly accepted may be more advantageous to lowering the viscosity of resin by launching. Be able to realize stable makes a mole of unreacted formaldehyde residual amount of urea addition, and that stands for the same amount of time to start the introduction of urea, urea-modified novolak resin viscosity by bearing.

[0091]

In addition to the molar ratio (F / (P+U)) up 0. 5-0. That's where can good manufacturing of resins, urea-modified novolak aims, within the range of 7 to be easily understood. Take the molar ratio is 0. Exceeding 8 resin viscosity is too high for the mole ratio limit is 0. Up to 8, 0 for range of molar ratios more suitable. 50-0. Considered a 75.

[0092]

Urea modified novolak type phenolic resin according to the present invention, the phenolic compounds with urea or methylol urea (U) (P) urea denaturation (U / (U+P)) are 5-should be within the range would be 50 percent favor making. From table 5 in particular, obvious like, urea denaturation 5-where you can get mold manufactures for phenolic resin coatedtsand (RCS), using it had obtained 30% of urea modified novolak type phenolic resin, the resulting RCS made a mold, with a strong mold. Here, urea denaturation needed for mass standards, and would also require urea denaturation the U value of urea amount (mass) of cases based on MetroCall urea was used in the synthesis.

[0093]

Also urea-modified novolak type phenolic resin according to the present invention is [phenol - CH2 -NHCO-] bond numbers, [-NH-CH2 hydrazones, bond number, and [phenol - CH2 -phenol] of the total number of joins [phenol - CH2 -NHCO-] is the average percentage of the combined number 25-has about 35%, and proportion to nitrogen absorption heat and flame resistance can be proven. Is that in addition to heat such as resin absorption is more than 5 J / g, more suitable for the 5-200 J / g that, due to the endothermic action this sink mark nest and casting can minimize malfunction. Further, weighted average from the examples presented in table 2 and 3 molecular weight (Mw) 550-2,500 around the cone and plate viscosity is 500-get 4,500 mPa-s degree, that would be easier to handle than will prove fit in. And BTW that can express the considered application of mold applications such as urea modified novolak type phenolic resin mold strength that can be used are clear.

claims:

[Paragraph 1]

Phenolic compounds and aldehydes, urea or urea methylol with condensation, when producing urea-modified novolak type phenolic resin
Contact wherein phenolic compounds and aldehydes said the reaction of their progress on the other hand, wherein urea or urea methylol scheduled wherein both condensed for consumption to reach the reaction system, continuously or intermittently little increments to feature was added so that the addition of urea or urea MetroCall said phenolic compounds and aldehydes such sequential with condensation to urea modified novolak type phenolic resin production methods.

[Paragraph 2]

Claim 1 wherein urea or urea methylol interdiffusion additives in the form of aqueous solution or suspension reaction mentioned urea modified novolak type phenolic resin production methods.

[Invoice section 3]

Continuously added by constant additive speed reaction wherein urea or urea methylol claim 1 or claim 2 mentioned urea modified novolak type phenolic resin production methods.

[Paragraph 4]

In the intermittent addition of _said_ urea or urea methylol constant intervals, carried out at a certain amount per claim 1 or claim 2 mentioned urea modified novolak type phenolic resin production methods.

[Bill 5]

(1) any claim 1 wherein urea or urea MetroCall is on the solid to claim 4 of the mentioned urea modified novolak type phenolic resin production methods.

[Bill 6]

(1) any claim 1 wherein phenolic compounds and aldehydes said initial condensation made after the initial condensate for additive wherein urea or urea MetroCall is initiated to claim 5 of the mentioned urea modified novolak type phenolic resin production methods.

[Billing paragraph 7]

In claim 6, was equal to the amount scheduled for wherein urea or urea MetroCall said both condensed amount of aldehydes, wherein the initial condensation of trapped when initiated the addition of the urea or urea MetroCall listed urea modified novolak type phenolic resin production methods.

[Claim 8]

Either claim 1 or claim 7 in paragraph (1) obtained by the manufacturing method of urea-modified novolak type phenolic resin.

[Billing paragraph 9]

Urea modified novolak type phenolic resin, manufactured by phenolic compounds and aldehydes, urea or urea methylol with condensation, to feature.

[Claim paragraph 10]

Absorptions due to thermal degradation, urea modified novolak type phenolic resin, manufactured by phenolic compounds and aldehydes, urea or urea methylol with condensation, which is 5 ~ to claim 9 200 J / g to feature mentioned urea modified novolak type phenolic resin.

[Section 11 claim]

Measurement of heat due to the differential scanning calorimeter by thermal decomposition and urea modified novolak type phenolic resin, manufactured by phenolic compounds and aldehydes, urea or urea methylol with condensation, absorption, 280 ° C and having absorption peak of 400 ° C range to claim 9 or claim 10 mentioned urea modified novolak type phenolic resin.

[Billing paragraph 12]

Phenolic compounds (P) and aldehydes (F), urea or methylol urea (U) molar ratios f / (P+U) is 0. 50-0. (1) any claim 9 features to be 75 to claim 11 of the mentioned urea modified novolak type phenolic resin.

[Billing section 13]

Cone and plate viscometer was measured at 160 ° C viscosity is 500-in any of the features to be 4,500 mPa-s claim 9 to claim 12 wherein the paragraph mentioned urea modified novolak type phenolic resin.

[Billing paragraph 14]

The weight average molecular weight (Mw) 550-to (1) any claim 9 features to be 2,500-claim 13 mentioned urea modified novolak type phenolic resin.

[Billing paragraph 15]

(U+P)-phenol compounds with urea or methylol urea (U) (P) urea denaturation: 5 – (1) any claim 9 features to 50 percent to claim 14 of the mentioned urea modified novolak type phenolic resin.

[Billing section 16]

Features requiring to be covered with fire-resistant particle, using urea-modified novolak type phenolic resin either claim 1 or claim 7 in paragraph (1) obtained by the manufacturing method of resin.

[Claim 17]

Features requiring that any claim 9 to claim section 15 paragraph (1) mentioned urea modified novolak type phenolic resin using a refractory particles coated with resin.